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FUNDAMENTALS OF SEMICONDUCTOR PHYSICS AND DEVICES

Rolf Enderlein

ihmboldt-bhiuemity BerEin Universi?yof Sao Pauh

NommJ.M. Horing

stewwas Institute o Technology f

Hoboken, NJ

World Scientific

Singapore New Jersey London Hong Kong

Puhli.dzed hy

World Scientific Publishing Co. Re. Ltd.

P 0 Box 128, Farrer Road, Singapore 912805 USA oflice: Suite 1 H, 1060 Main Streei, River Edge, NJ 07661 UK oflcficer 57 Shelton Street, Covcnt Garden, London WCZH 9IiE

British Library Catalogiiing-in-PublicationData A catalogue recurd fur this book is available from the British Library.

First published 1997 Reprinted 1999

**FUNDAMENTALS OF SEMICONDIJC'IOK PHYSICS AND DEVICES
**

Copyright 0 1997 by World Scicntific Publishing Co Pte. Ltd.

All rights reserved. Th.is book, or parts thrreof, may ~ O be reprudrtced in any jurwi or by ony m e w s , I electmnir or rnerhirnicirl, incIudinx photocopying. recording or any information storage and retrieval sys:slew now known or m be ii-zvmted, without written permissionfrom !he Publisher.

For photocopying of material in this volume, please pay a copying fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive. Danvers, MA 01923, U S A . In this casc pcmission to photocopy i s not required from the publisher.

ISBN 981-02-2387-0

Printed in Singapore.

Dedication

This book is dedicated to the memory of Adele and Werner Enderlein (par ents of R.E.), and to t h e memory of Joseph and Esther Morgenstern (hfor ganstein)(grandparents of N.J. M. 11.).

Vii

Preface

People come to technical books with a vast array of daerent needs and requirements, arising from their differing educational backgrounds, professional orientations and career objectives. This is particularly evident in the field of semiconductors, which stands at the juncture of physics, chemistry, electronic engineering, material science and mathematics. No longer just an academic discipline. this field is at the heart of an ongoing revolution in communications, computation and electronic device applications, that innovate many fields and change modern life in myriad ways, large and small. Its profound impact and further potential command interest and attention from all corners of the earth. and from a wide variety of students and researchers. The clear need to address a broadly diversified and variously motivated readership has weighed heavily in the authors’ considerations. It poses a pedagogical problem faced by many teachers of intermediate level courses on semiconductor physics. Generally speaking, every student has previously studied about half of the course materiaL The difficulty lies in the fact that each student’s exposure is likely to have been to a &fleerent half, depending on which lower level courses and teachers they have had, and where the emphasis lay. To accommodate readers with varied backgrounds we start from first principles and provide fully detaiIed explanations and proofs, assuming only that the reader is familiar with the Schrodinger equation. This intensively tutorial treatment of the electronic properties of semiconductors includes recent fundamental developments and is carried through to the physical principles o device operation, to meet the needs of readers interf ested in engineering aspects of semiconductors, as well as those interested in basic physics. Clarity of explanation and breadth of exposure relating to the electronic properties of semiconductors, from first principles to modern devices, are our principal objectives in this fraddy pedagogical book. We offer full mathematical derivations to strengthen understanding and discuss the physical significance of results. avoiding reliance on ‘hand waving arguments alone. To support the reader’s introduction to the physics of semiconductors, we provide a thorough grounding in the basic principles of solid state physics, assuming no prior knowledge of the field on the part of the reader. An ele mentary discussion of the crystal structure, chemical nature and macroscopic properties characterizing semiconductors is given in Chapter 1. Moreover, we also include an extensive appendix to guide the reader through group theory and its applications in connection with the symmetry properties of semiconductors, which are of major importance. Beside spatially homogeneous bulk semiconductors, we undertake a full exposition of inhomogeneous semiconductor junctions and heterostructures because of their crucial role

Preface

iu

The book has emerged from lectures which the authors presented for physics students at the Humboldt-University of Berlin. Germany, and the State University of Sao Paulo, Brazil, and for physics and engineering physics students at the Stevens Institute of TeFhnology in Hoboken, New Jersey, C.S.A. Part of the book has similarities with the german book "Grundlagen der Halbleiterphysik" ("Fundamentals of Semiconductor Physics") which was written by one o us (R. E.) together with A. Schenk. We are thankful to Dr. Schenk f (now at ETH Zurich) for allowing us to use part of his work in the present volume. In writing this book we have had excellent suppoIt from many of our colleagues at our own and other Universities. We are particularly r thankful to Prof. D . J. Auth (Humboldt-Lniversity Berlin), Prof. Dr. F. Bechstedt (Friedrich-Schiller University Jena), Prof. Dr. W. A. Harrison (Stanford University), Prof. Dr. M. Scheffler (Fritz-Haber Institut, Berlin), Prof. Dr. J. R. b i t e , Prof. Dr. A. Fazzio, and Prof. D . J. L. Alves r el (State University Sao Paulo), as w l as to Prof. Dr. H. L. Cui, Prof. Dr. G. Rothberg, Mr. G. Lichtner (Stevens Institute of Technology), and Prof. Dr. G . Gumbs (Hunter College, CWNY, New York), who read parts of the manuscript and contributed helpful suggestions and critical remarks. The technical assistance of Mrs. Hannelore Enderlein is gratefully acknowledged.

RoIf Enderlein

Sao Paulo October 1996

Norman J.M. Horing Hoboken, N J

X i

Contents

1 Characterization of sernicond uct ors

Inlrnduclion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 Atomic structure of ideal crystals . . . . . . . . . . . . . . . . 1.2.1 Cryst.al latlices . . . . . . . . . . . . . . . . . . . . . . 1.2.2 Point groups of equivalent directions arid crystal classes 1.2.3 Space groups and crystal structures . . . . . . . . . . 1.2.4 Cubic semiconductor structures . . . . . . . . . . . . . 1.2.5 Hexagoiial semiconductor st.ructures . . . . . . . . . . 1.3 Chemical nature of semiconductors. Material classes . . . . . 1.3.1 Group IV elemental semiconductors . . . . . . . . . . 1.3.2 111-V semiconductors . . . . . . . . . . . . . . . . . . . 1.3.3 11-VI semiconductors . . . . . . . . . . . . . . . . . . . 1.3.4 Group \ elemental semiconductors . . . . . . . . . . ' I 1.3.5 IV-VI semiconductors . . . . . . . . . . . . . . . . . . 1.3.6 Other compound semiconductors . . . . . . . . . . . . 1 4 hlacroscopic properties and their microscopic implications . . . 1.4.1 Electrical conductivity . . . . . . . . . . . . . . . . . . 1.4.2 Depenclenre of conductivity on the semiconductor state 1.4.3 Optical absorption spectrum and the band modcl of srmicoiiductors . . . . . . . . . . . . . . . . . . . . . . 1.4.4 Electrical conductivity in the band model . . . . . . . 1.4.5 The Hall effect and the existence of positively charged freely mobile carriers . . . . . . . . . . . . . . . . . . . 1.4.6 Seinicondiictors far from thermodynamic equilibrium .

1.1

1 1

5

6

12

14 16

22

28 29 30 31 31

32

32

33 34

35

38

43

45

49

51 51 54

54

2 Electronic structure of ideal crystals 2.1 Abcimic cores and vdcnce electrons . . . . . . . . . . . . . . . 2.2 The ciynaniical problem . . . . . . . . . . . . . . . . . . . . . 2.2.1 Schriidiiiger equation for the interacting core and valence dwtl-on system . . . . . . . . . . . . . . . . . . . 2.2.2 Adiabatic approximation . Lattice dynamics . . . . . . 2.2.3 Oneparticle approximation . Oneparticle Schriidinger equation . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 General properties of stationary one-rlectron states in a crystal 2,3.1 Syinrnctry properties of the one-electron Schrtidinger equation . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.2 R b c h theorem . . . . . . . . . . . . . . . . . . . . . . 2.3.3 Reciprocal v e c h space and the reciprocal latt.ice . . . 2.3.4 Relation between energy eigenvalues and quasi-wave vector . . . . . . . . . . . . . . . . . . . . . . . . . . .

57

66

82

82

85

89

94

xii

Contents

2.4

2.5

2.6

2.7

2.8

Schrodinger equation solution in the nearly-freeelectron approximation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 2.4.1 Kon-degenerate perturbat. t.heory . . . . . . . . . . 100 ion 2.4.2 Degenerate perturbation theory . . . . . . . . . . . . . 103 Bandstructure . . . . . . . . . . . . . . . . . . . . . . . . . . 105 2.5.1 Brillouin zones . . . . . . . . . . . . . . . . . . . . . . 105 2.5.2 Degeneracy of energy bands . . . . . . . . . . . . . . . 116 2.5.3 Critical points and effective masses . . . . . . . . . . . 119 2.5.4 Density of states . . . . . . . . . . . . . . . . . . . . . 123 2.5.5 Spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 2.5.6 Calculational methods for band structure determination133 Tight binding approximation . . . . . . . . . . . . . . . . . . 140 2.6.1 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . 140 2.6.2 TB theory- of diamond and zincblende type semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . 148 2.6.3 sp3-hybrids, total energy and chemical bonding . . . . 165 k . p-met.hod . . . . . . . . . . . . . . . . . . . . . . . . . . . 179 2.7.1 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . 179 2.7.2 Valence bands of diamond structure semiconductors without spin-orbit interaction . . . . . . . . . . . . . 184 . 2.7.3 h t t i n g eT-Kohn model . . . . . . . . . . . . . . . . . . 189 2.7.4 Kana model . . . . . . . . . . . . . . . . . . . . . . . . 200 Band structure of important semiconductors . . . . . . . . . . 211 2.8.1 Silicou . . . . . . . . . . . . . . . . . . . . . . . . . . . 212 2.8.2 Germanium . . . . . . . . . . . . . . . . . . . . . . . . 218 2.8.3 111-V semiconductors . . . . . . . . . . . . . . . . . . 219 2.8.4 IGVI semiconductors . . . . . . . . . . . . . . . . . . . 221 2.8.5 IV-\'I semiconductors . . . . . . . . . . . . . . . . . . 224 2.8.6 Tellurium and selenium . . . . . . . . . . . . . . . . . 224

3 Electronic s t r u c t u r e of semiconductor crystals with p e r t u r bations 225 f 3.1 Atomic structure o red semiconductor crystals . . . . . . . . 226 3.1.1 Classification of perturbations . . . . . . . . . . . . . . 226 3.1.2 Point perturbations . . . . . . . . . . . . . . . . . . . . 227 3.1.3 Formation of point perturbations and their movenient 235 3.1.4 h e and planar defects . . . . . . . . . . . . . . . . . 240 3.2 One-electron Schrodinger equation for point perturbations . . 241 3.2.1 Electron-core interaction . . . . . . . . . . . . . . . . . 242 3.2.2 Electron-elw?c.lron interaction . . . . . . . . . . . . . . 245 3.3 Effective mass equation . . . . . . . . . . . . . . . . . . . . . 252 3.3.1 Effectivemass equation for a single band . . . . . . . 253 3.3.2 Multjband effective mass equation . . . . . . . . . . . 259

Contents

Xlll

...

3.4 Shallow levels. Donor and acceptor states . . . . . . . . . . . 265 3.4.1 Hydrogen model . . . . . . . . . . . . . . . . . . . . . 266 3.4.2 Improvements upon the hydrogen model . . . . . . . . 272 3.5 Deeplevds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281 3.5.1 General characterization of deep levels . . . . . . . . . 281 3.5.2 Defect molecule model . . . . . . . . . . . . . . . . . .285 3.5.3 Solution methods for the oneelectron Schriidinger q u a tion of a crystal with a point perturbation . . . . . . . 293 3.5.4 Correlation effects . . . . . . . . . . . . . . . . . . . . 301 3.5.5 Resu1t.s for se1ecDed deep centtas . . . . . . . . . . . . 308 3.6 Clean semiconductor surfaces . . . . . . . . . . . . . . . . . . 334 3.6.1 The concept of clean surfaces . . . . . . . . . . . . . . 334 3.6.2 Atomic structure of clean surlaces . . . . . . . . . . . 336 3.6.3 Electronic structure of crystals with a surface . . . . . 354 3.6.4 htomic and electronic structure of particular surfaces 371 3.7 Semiconductor microstructures . . . . . . . . . . . . . . . . .388 3.7.1 Neterojunctions . . . . . . . . . . . . . . . . . . . . . . 388 3.7.2 Microstructures; Fabrication, classifications, examples 396 3.7.3 h*lethodsfor electronic structure calculations . . . . . 409 3.7.4 Elcctronic structure of particular microstructures . . . 420 3.8 Macroscopic electric fields . . . . . . . . . . . . . . . . . . . . 433 3.8.1 Effective mass equation and stationary electron states 434 3.8.2 Non-stationary states . Bloch oscillations . . . . . . . . 437 3.8.3 Interband tunneling . . . . . . . . . . . . . . . . . . . 440 3.8.4 Photon assisted interband tunneling . . . . . . . . . . 442 3.9 Macroscopic magnetic fields . . . . . . . . . . . . . . . . . . . 443 3.9.1 Effective mass equation in a magnetic field . . . . . . 444 3.9.2 Solution of the effective mass equation . . . . . . . . . 452

4

Electron system in t herrnodynamic equilibrium 457 4.1 Fundamentals of the statistical description . . . . . . . . . . . 457 4.2 Calculation of average particle numbers . . . . . . . . . . . . 460 4.2.1 Configuration-independent oneparticle states . . . . . 460 4.2.2 Configuration-dependent one-particle states . . . . . . 462 4.3 Density of states . . . . . . . . . . . . . . . . . . . . . . . . . 469 4.3.1 Total electron concentration . . . . . . . . . . . . . . . 469 4.3.2 Density of states of ideal semiconductors . . . . . . . . 470 4.3.3 Density of states of real semiconductors . . . . . . . . 474 4.4 Free carrier concentrations . . . . . . . . . . . . . . . . . . . . 477 4.4.1 Conservation of total electron number . . . . . . . . . 477 4.4.2 Free carrier concentration dependence on Fermi energy. Law of mass action . . . . . . . . . . . . . . . . . 478 4.4.3 Intrinsic semiconductors . . . . . . . . . . . . . . . . . 482

xiv

Contents

4.4.4 4.4.5 4.4.6

5

Extrinsic semiconductors . . . . . . . . . . . . . . . . 484 Compensation of donors and acceptors . . . . . . . . . 489 More complex cases . . . . . . . . . . . . . . . . . . . 492

Non-equilibrium processes in semiconductors 499 5.1 Fundamentals of the statistical description of non-equilibrium processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500 5.2 Systematics of non-equilibrium processes in semiconductors . 505 5.2.1 Temporal inhomogeneity and spatial homogeneity . . 505 5.2.2 Spatial inhomogeneity and temporal homogeneity . . . 506 5.2.3 Space and time inhomogeneities . . . . . . . . . . . . 508 5.3 Generation and annihilation of free charge carriers . . . . . . 509 5.3.1 Generation processes . . . . . . . . . . . . . . . . . . . 510 5.3.2 Unipolar annihilation of free charge carriers: capture 511 at deep centers . . . . . . . . . . . . . . . . . . . . . . 5.3.3 Bipolar annihilation of carriers at deep centers . . . . 517 5.4 Drift current . . . . . . . . . . . . . . . . . . . . . . . . . . . 523 5.5 Diffusion and annihilation of free carriers . . . . . . . . . . . 527 5.6 Equilibrium of free carriers in inhomogeneously doped semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 530

6 Semiconductor junctions in thermodynamic equilibrium 535 6.1 pn-junction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537 6.1.1 Establishment of thermodynamic equilibrium . . . . . 539 6.1.2 Diffusion voltage . . . . . . . . . . . . . . . . . . . . . 541 6.1.3 Spatial variation of the electric and chemical potentials: Schottky approximation . . . . . . . . . . . . . . 542 6.2 Heterojunctions . . . . . . . . . . . . . . . . . . . . . . . . . . 549 6.2.1 Equilibrium condition . . . . . . . . . . . . . . . . . . 550 6.2.2 Electrostatic potentid . GaAs/Gal-,Al, As heterojunction as an example . . . . . . . . . . . . . . . . . . . . 552 6.3 Metal-semiconductor junctions . . . . . . . . . . . . . . . . . 557 6.3.1 Energy level diagram before establishing equilibrium . 357 6.3.2 Electrostatic potential . . . . . . . . . . . . . . . . . . 559 6.3.3 Schottky barrier . . . . . . . . . . . . . . . . . . . . . 563 6.4 Insulator-semiconductor junctions . . . . . . . . . . . . . . . . 567 6.4.1 Thermodynamic equilibrium . . . . . . . . . . . . . . 567 6.4.2 Influence of interface states . . . . . . . . . . . . . . . 570 6.4.3 Semiconductor surfaces . . . . . . . . . . . . . . . . . 572

7 Semiconductor junctions under non-equilibrium conditions 573 7.1 pn-junction in an external voltage . . . . . . . . . . . . . . . 574 7.1.1 Electrostatic potential profile . . . . . . . . . . . . . . 576

Contents

xv

Mechamism of current transport through a pn-junction 577 Chemical potential profiles for electrons and holm . . 580 Dependence of current density on voltage . . . . . . . 583 Bipolar transistor'. . . . . . . . . . . . . . . . . . . . . 585 7.1.6 T u n e 1 diode . . . . . . . . . . . . . . . . . . . . . . . 593 7.2 yn-junction in interaction with light . . . . . . . . . . . . . . 595 7.2.1 Photocffect at a pn-junction . Photodiode and photovoltaic element . . . . . . . . . . . . . . . . . . . . . . 595 7.2.2 Laser diode . . . . . . . . . . . . . . . . . . . . . . . . 599 7.3 Metal-semiconductor junction in an external voltage. Rectificrs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606 7.4 hwulator-semiconductor junction in an external voltage . . . 612 7.4.1 Field effect . . . . . . . . . . . . . . . . . . . . . . . . 612 7.4.2 Inversion layers . . . . . . . . . . . . . . . . . . . . . . 614

7.1.2 7.1.3 7.1.4 7.1.5

7.4.3 MOSFET . . . . . . . . . . . . . . . . . . . . . . . . .

620

Appendices

A Group theory for applications in semiconductor physics

623 A.1 Definitions and concepts . . . . . . . . . . . . . . . . . . . . . 623 A . l .1 Group definition . . . . . . . . . . . . . . . . . . . . . 623 A.1.2 Concepts . . . . . . . . . . . . . . . . . . . . . . . . . 624 A.2 Rigid displacements . . . . . . . . . . . . . . . . . . . . . . . 627 A.2.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . 621 A.2.2 Translations . . . . . . . . . . . . . . . . . . . . . . . . 628 A.2.3 Orthogonal transformations . . . . . . . . . . . . . . . 629 A.2.4 Geometrical interpretation . . . . . . . . . . . . . . . . 631 -4.2.5 Screw rotations and glide re3ections . . . . . . . . . . 632 A.3 Translation. point and space groups . . . . . . . . . . . . . . 635 A.3.1 Lattice translation groups . . . . . . . . . . . . . . . . 635 -4.3.2 Point groups . . . . . . . . . . . . . . . . . . . . . . . 636 A.3.3 Space groups . . . . . . . . . . . . . . . . . . . . . . . 654 A.4 Representations of groups . . . . . . . . . . . . . . . . . . . . 655 A.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . 655 A.4.2 Irreducible representations . . . . . . . . . . . . . . . . 661 4.4.3 Products of representations . . . . . . . . . . . . . . . 667 A . 5 Representations of the full rotation group . . . . . . . . . . . 673 4.5.1 Vector representation of the rotation group and generators of infinitesimal rotations . . . . . . . . . . . . 674 A.5.2 Representations for dimensions other than three . . . 676 A.6 Spinor representations . . . . . . . . . . . . . . . . . . . . . . 682 A.6.1 Space-dependent spinors . . . . . . . . . . . . . . . . . 682

mi

Cootents

A.6.2 Representation V I . . . . . . . . . . . . . . . . . . . . 683 2 A.6.3 Irreducible spinor representations . . . . . . . . . . . . 684 A.6.4 Double group method . . . . . . . . . . . . . . . . . . 685 A.7 Projective representations . . . . . . . . . . . . . . . . . . . . 687 A.7.1 Factor systems . . . . . . . . . . . . . . . . . . . . . . 687 A.7.2 Definitions and theorems . . . . . . . . . . . . . . . . 689 A.7.3 Construction of projective representations . . . . . . . 692 A.8 Time reversal symmetry . . . . . . . . . . . . . . . . . . . . . 692 A.8.1 Time reversal operator . . . . . . . . . . . . . . . . . . 693 A.8.2 Additional degenerac!?~of energy eigenvalues . . . . . 694 A.8.3 Additional selection rules for matrix elements . . . . . 697 A.9 Irreducible representations of space groups . . . . . . . . . . . 698 A.9.1 Representations of translation groups . . . . . . . . . 698 A.9.2 Star of wavevectors . . . . . . . . . . . . . . . . . . . . 700 A.9.3 Small point groups and their projective representations 702 A.9.4 Representations of the fufl space group . . . . . . . . . 704 A.9.5 Spinor representations of space groups . . . . . . . . . 706 A.9.6 Implications of time reversal symmetry . . . . . . . . 707 A.9.7 Compatibility . . . . . . . . . . . . . . . . . . . . . . . 712 A.10 Irreducible representations of small point groups . . . . . . . 712 A.10.1 Character tables . . . . . . . . . . . . . . . . . . . . . 712 A.10.2 Multiplication tables . . . . . . . . . . . . . . . . . . 731 A.10.3 Compatibility relations . . . . . . . . . . . . . . . . . 734

**B Corrections to the adiabatic approximation
**

C Occupation number representation

Bibliography

737

'741

747

Index

757

FUNDAMENTALS OF SEMICONDUCTOR PHYSICS AND DEVICES

1

Chapter 1

Characterization of semiconductors

1.1

Introduction

Semiconductors are identified as a unique material group on the basis of their common macroscopir properties, as is done for metals, dielectrics and magnetic materials. The name ‘semiconductor’ stems from the fact that such materials have moderately good conductivity, higher than that of insulators, and lower than that of metals. However, if this were the only property which these materials had in common, the term ‘semiconductor‘ would have only a very weak foundation. But such is not the case. In fact, many materials having conductivity between that of metals and insulators. display simultaneously a series of further common properties. In particular, their conductivity depends very strongly on material staie, for example, on temperature and chemical purity, much more so than in the case of metals. For sufficiently pure semiconductors, the conductivity decays by orders of magnitude while cooling down from room temperature to liquid helium temperature. ,4t absolute zero temperature, semiconductor conductivity almost vanishes, in contrast to the conductivity of metals, which rises modestly with falling temperature. The conductivity of metals reaches its maximum at low temperature, and for superconductors it effectively becomes infinitely large. In regard to the dependence of semiconductor conductivity on the degree of purity, it has been found that a given semiconductor in a very pure state can resemble an insulator. while in a highly polluted state it acts like a metal, among other peculiarities. Furthermore, irradiation with light can cause a transition from insulator-like behavior to metal-like behavior of one and the same semiconductor. There are yet other optical properties shared by semiconductors: The op-

Actually. For the moment. which exhibit conductivity values of the right order of magnitude. for example. For example. To be specific. The discussion also partially applies to amorphous and liquid sexniconductors. since the formation of energy bands with gaps between them is most likely to occur in the crystalline phase. This criterion excludes ionic conductors. beyond the ones already discussed. a series of amorphous semiconductors has also been found silicon and selenium being important examples. and what internal connections may exist among them. which are the main reprcsentatives. For instance. Nevertheless. Other semiconducting materials. It is this common microscopic feature which underlies the totality of macroscopic material properties that uniquely define a semiconductor. silicon and germanium. a semiconductor i s characterized by having only completely occupied and completely empty energy bands (no partially filled bands). In this book we restrict our considerations to solid crystalline semiconductors. good luminescence properties in the visible and infrared spectral range are also characceristic of many semiconductors. the identification of a semiconductor material involves several characteristic properties. it is not yet obvious why just the above properties are selected as defining features while others are not.2 Chapter I. e. It also provides the basis for uncovering yet other common macroscopic features of this class of materials. the permissible energy levels of a semiconductor form bands which are separated by forbidden regions. and the Characteristic electron population of allowed energy levels is such that. it may be expected that semiconductors should be predominantly solid crystalline materials. we invite the reader to join us in the recognition that all macroscopic properties involved in the definition of a semiconductor can be traced back to a common microscopic origin. while above it the light is strongly absorbed. Even the basic . are metals in the liquid phase.below the threshold frequency. Characterization of semiconductors tical absorption spectra of semiconductors exhibit a threshold . One has a semiconductor only if all such properties apply.. Thus. not just the one of moderately good electrical conduction. Liquid semiconductors are also possible. with melted tellurium among them. light can pass through practically without losses. A full answer can only be given by means of a microscopic theory of semiconductor properties which will be developed systematically in the chapters to follow. in addition to solid crystalline semiconductors. amorphous and liquid semiconductors cannot be completely rxcluded since a certain regularity of the relative positions of neighboring atoms also exists in the amorphous and liquid phases. Moreover.g. One may justifiably question the extent to which this definition of a semiconductor really makes sense. but in most cases modifications are necessary. but do not display the characteristic temperature dependence. namely the nature of the spectrum of allowed energy levels and the particulars of their population by electrons. at absolute zero temperature.

Interested readers are referred to the extensive literature on this subject (see. Knowledge of thc mxistence of a distinct material group ‘semiconductors’ developed. 1984. Mott and Davis. clean fabrication of the materials in the laboratory and the controlled incorporation of chemical elements played a crucial role from the very beginning. The exponential form of this increase was discovcrcxl by Hittorf in 1851. but semiconductors attracted attention for the Erst time only a century and a half ago. It was necessary to raise the accuracy of chemical composition control to a level wherein one could measure one millionth of a mole haction instead of one thousandth. Accordingly. This is in fact true semiconductors may be composed of a large variety of chemical elements and compounds. Natural diamondrr. historically. and a proper treatment of amorphous and liquid materials cannot be acconimodated within the framework of this introduction to semiconductor physics. Enderlein.e. 11979. initially. The trerm ‘semiconductor’ was introduced in 1911 by Konigsberger and Weiss after a similar term of about the same context had already been employed by Ebert (1789) and Bromme (1851). 1983. on the presence 0’1 absence o certain chemical elements.1. which amounts to one atom in one hundred f thousand or less. T h e microscopic definition discussed above contains no recognizable constraints with regard to the chemical nature of semiconductors. Since such accuracy was achieved ~ ~ . Adhr. is primarily due to the circnnistance that the characteristic properties of semiconductors depend strongly on their degree of purity. F r h s c h e and Ovahinsky. for example. The late and. Bunch-Bruevich. excccdcd the accuracy that prevailed in chemistry at the t h e by orders of magnitude. One may expect. i. for example? Elliot. This is also f the reason that many semiconducting materials in their natural form as minerals do not display the typical properties of a semiconductor they are too heavily polluted and have too many structural defects. The most fully expAored candidates and those used for technical applications today arc crystalline semiconductors consisting of relatively small chemical u n i t s . therefore. either dements or binary and ternary compounds.1. The first reference to a characteristic semiconductor property dates back to Faraday who in 1833 observed an increase of the electric conductivity of silver sulfide with temperature. only relatively late. relatively slow development of semiconductor physics. Ewer. 1985). more precisely. Keiper. are semiconductors only in rare cases. The lack of such control in preparation presented fundamental difficulties which had to be overcame in the early days of semiconductor rasearch. that semiconductors should be distinguished by having a large chemical diversity. MPtals have been used by men since antiquity. Mironov. and Xvyagin. only in this way could reliable results be achieved with semiconductors. The necessary accuracy o composition control. Introduction 3 concept o f the quantum mechanical energy spectrum uf electrons has to be defined in tl different way.

Characterization of semiconductors only gradually. this effect has also been used practically in the selenium photocell. luminescence physics partially merged with semiconductor physics. Among these first materials were metal sulfides. One can mark these point contact rectifiers as the first semiconductor devices. a similar role was played by compounds involving elements of the third and fifth groups of the periodic table. Braun discovered that contacts between certain metal sulfides and metal tips fxhibited different electrical resistance upon reversal of the polarity of the applied voltage. this property was discovered as early as 1852 by Hittorf. In the mid-nineteen-thirties. The Geld could develop only to the extent that good samples could be made available. The first practical application of copper oxide in photocells was accomplished in 1932 by Lang. were the invention of the germaniumbased bipolar transistor in 1949. followed by rectifiers using selenium. which turned out to be decisive for the whole further development of semiconductor physics. the first samples weie either materials which could b r fabricated relatively cheaply or materials which occurred in nature in a suitable form.4 Chapter 1. Similar rectifying action was also found for selenium and copper oxide. was confronted with apparently mysterious phenomena and contradictory results. Such point contact structures were used in radio receivers as rectifiers at the beginning of our century. For selenium. For example. Since the beginning of the 20-th century. in its early history. selenium and copper oxide were the first semiconductors to be subjected to more detailed physical investigations. until the recognition that the impurity concentrations of certain elements were too large to achieve semiconducting properties. In 1874. silicon and germanium were first thought to be metals. the stage was set for the development of semiconductor microelectronics. the search for a solid-state-based electronic switching element which could replace the vacuum tube was extended to the elemental semiconductors germanium and silicon. which like lead sulfide in its mineral form as Galena and copper oxide (CuzO) and selenium in their artificially grown form. With the introduction of silicon. Moreover. selenides and tellurides were already known earlier because of their good luminescence properties. Naturally. Because of their technological importance. albeit not ideal. In the further exploration of these materials’ semiconducting behavior. Later. and the realization of the field effect transistor with the help of silicon at the end of the nineteen-fifties. From the very beginning semiconductor physics research was impeded by the need for expensive fabrication of material samples. a large change of electrical conductivity could also be achieved in these materials through irradiation by light. semiconductor physics. The most important results of this research. The first technical use of copper oxide as a rectifier was accomplished in 1926 by Grondahl. The semiconducting metal sulfides. displayed good semiconducting properties even with relatively strong pollution and structural imperfections. like gallium .

In this regard. as they are treated in this book. this will have to be done in a heuristic way. It is well established that semicondnctors arc exceptionally well-suited for necessary functions in electronics and electrical engineering. Naturally. which is termed long-range order. are crystals. This . atomic structure will be discuss4 in section 1. 1. but we will also use them to motivate the microscopic model of semiconductors introduced above.4. including amorphous ones. The great technical importance of semiconductors has made thorough physical investigation of these materials necessary. which permits the controlled variation of characteristic matprial properties by external means over a wide range of parameters. often in the most distinctive way. The term short-range order is uscd for this property. Semiconductor materials. The neighbors of a particular atom form its short-range order complex. a multitude of physical phenomena which occur in other solid state materials may also be observed in semiconductors. the neighbors of an arbitrarily selected atom are ordered in a regular way. Moreover.1. chemical nature in section 1. The presentation of the microscopic principles of semiconductor physics will occupy most of this book. which we have touched upon above. This is by no means accidental. For this reason studies of semiconductors can also provide knowledge of other solid state mattrials. but it has also justified the high cost involved in their fabrication and study. In dealing with macroscopic properties we will not restrict ourselves to mere description.2. will be continued in Chapter 1. The characterization of semiconductors by means of their unique macroscopic features. In this connection. making possible the development of semiconductor optoelectronirs. but is due to the microscopic nature of semiconductors. and many questions postponed until later. Atornic structure of ideal m y s t a h 5 arsenide or phosphide. The full presentation of the microscopic principles of semiconductor physics will follow in later chapters.2. just as in a molecule. we will make the first step towards a microscopic theory of semiconductors in section 1. Owing to both of these aspects semiconductors are thc best explored and understood materials of condensrd matter today.3 and macroscopic physical properties in section 1.2 Atomic structure of ideal crystals In all solid state materials. The introductory first chapter lies outside of this framework because it involves discussion of the results on a phenomenological basis. The latter are distinguished by yet another order.4. apart from short-range. The broad technical application of its results distinguishes semiconductor physics now from its early days. ‘Sheir atomic structure is approximately that of ideal crystals. Semiconductors have in fact become model systems for basic research in condensed matter physics.

primitive unit cell may be written as the triple scalar product of al. 'l'hp crystal is considered t o be inhitely large in this context. as long 8s it remains finite. there are remote atoms possessing the same short-range order complexes as the original atom. . The point set defined by the vectors R forms a spatial lattice called the crystal lattice. the vectors Al. rand that the positions of the remote atoms are related to the position of the origina1 atom by sirnple transformations. The volume 00of a ag. The parallelepipeds of the crystal spanned by the particular displacement vectors Ak. Ro = a . Az. are termed primitive lattice vectors. 121 . then the short-range order merges into the long-range order.a2. r 3 transforms the crystal into itself. The vectors al. but rather how small. r2.w. The parallelepiped spanned by these vectors is a primitive unit cell.. and can in fact be taken arbitrarily large. If there is only one atom per cell.. but chemically identical atoms need not necessarily be equivalent. for a given atom. The pertinent question is not how large a unit cell can be. it has several atoms. A2. A2. & f are some minimal vectors a l . A3 with arbitrary integer coefficients t l . t3. By putting unit cells together the wholc crystal may be constructed. ' h e size of a unit cell and the number of atoms in it is not fixed by the above definition. I the unit cell is taken to be a primitive one. but as a rule. One refers to this property as the trunslation~lsymmetry of the crystal.t 2 . Each translation by a vector R o the form f case with integer coefficients r l . az. Equivalent atoms are necessarily of the same chemical species. Atoms having identical short-range order complexes are termed equivalent. a. [ag x l a]. The answer to this question leads us t o the definition of the primitive unit cell and the crystal lattice. A3 are called unit cells. Crystal lattices The transformations displacing atoms into equivalent ones are translations of the crystal by vectors T which form linear combiaations of three non-coplanar vectors Al. Characterization of semiconductors means that.6 Chapter 1. Definition The smallest possible unit cell is called a primitive unit cell In the extreme this cell can contain only 1atom.

a group. Atomic structure of ideal cestals 7 While the lattice of a crystal and the volume Qo of its primitive unit cell are well defined. there is a second class of transformations fitting this description. Any set of linear combinations of the primitive vectors al. is again a primitive unit cell. Point symmetry of lattices We now ask whether there are other possible spatial transformations. such as rotation-reflections.a3 and also it is not true for the form of its primitive unit cell. Appendix A provides a thorough discussion of groups as needed in this book. as there are also other forms possible. as well as all products which are compounded from them.a2. this is not the case for its primitive lattice vectors al. i. Further properties of a set forming a group are listed in A p pendix A. besides translations. the translations are through lattice vectors R. This term describes a mathematical set of elements among which a 'multiplication' is defined that results in products which are also elements of the set. An especially compact primitive unit cell is the socalled Wzgner3eit. In particular. rotatton-znverstonsand znverszon itself. in fact.2.a2. Translations which transform a crystal into itself.z cell. The 'parallelepiped form is also not imperative. besides translations. These differ from translations inasmuch as they leave one or several lattice points unchanged. mgzd drsplacernents of the lattice (see Appendix A). called lattice tramtations The set of all lattice translations forms a group. and the inverse of an element must also be an element of the set. group or simply the tramlation group. do the same for the lattice of the crystal. In the case of translations the 'multiplication' is the consecutive application of two of these transformations. Groups of symmetry elements play a central role in the description of the atomic structure and other microscopic properties of crystals. while the remaining points are shifted by vectors depending on . and also the requirements of Appendix A are satisfied. by definition. the set of all lattice translations of a crystal forms.a3 which yields a triple scalar product equal to the volume Qo is again a set of primitive lattice vectors. namely rotatoom and reflectzons.e. The center of this cell lies on a lattice point and its surface is formed by the perpendicular bisector planes which divide in half the line segments joining the center to adjacent lattice points. called the translation symmetrg. which transform lattices into themselves. The corners of the parallelepipeds do not necessarily have to lie on lattice points. One can show that. shifted arbitrarily in space. they are termed orthogonal traasfomattom. and the parallelepiped spanned by them forms a primitive unit cell. From the outset it is clear that the only transformations which may be considered are those that do not change the distances between lattice points. there must be an identity element. Taken together. Since two consecutive lattice translations constitute yet another lattice translation. Each parallelepiped. Here.1.

1 or 2. equation (1. the relation + + + p . Therefore.hat. all uf these point groups must contain the inversion transformation with r e q e t t to the lattice point R = 0. Characterkstion of semiconductors their positions. Moreover. Rotations transform right-hand4 Cartesian coordinate systems into right-handed systems. First. The same holds for the sum Cnf i Cg'f ol t. In a t.4) has only the trivial solution n = I . If. It turns out that there are orthogonal transformations which transform lattices into themselves.. This completes the proof concerning rotation symmetv opexations. = 1 l h e solulion is n = 6 . be a rotation about such an axis t.-2. The set of all point symmetry operations of a lattice forms a group..hrough an angle 2?r/n.f CF'f must be an integer multiple of f.f. C. This may be seen as fullows: Inversion with respect to 0 transforms a lattice point R into -EL Considered joiutly with R. and a rotation by .ranslation. They are called point symmetry operations of lattices.F with pn . 3-.f CGLf represents a vector parallel to f. as does the set of all lattice translations.f and C i l f are vectors of the plane lattice. Groups of point symmetry operations are termed point gvoups. The multiglicslion of two of these operations is again understood to represent their consecutive application.1).and more-fold axes are not compatible with the translation symmetry of the lattice.and 6-fold while ri. them s n d o a C. We consider a lattice plane perpendicular to this axis and denote a primitive lattice vector of the corresponding planar lattice by f (see Figure 1. Not all of the various point groups listed in Appendix A are allowed as symmetry groups of crystal lailices.0 it follows that n = 4 and for p . -7-3 as integer coefficients.2 equation (1. with no points fixed. This means that C. Cmbelongs to the point group of the lattice. One may prove this as follows: Let C. = 2COS (?) 1 must hold for p.8 Chapter 1 . This is indicative t. but only parlicular ones which are called holohedral point groups. all points are shifted by the same vector.4) yields n 2.one has Cnf f C'L'f = p. for pn .2 ? r / R transforms it into Cqlf. Rotating it through 2a/a. In Appendix A we describe thwn in detail. which do not exhibit an exact translation symmetry. Thus both C. -LO.he two vectors. rotations . Second. 7. the point -R is a lattice point having -q. 4. Since the largest possible length of Cnf Cg'f can only he 2 / f J . inversion with respect to 0 transforms an arbitrary lattice into itself. it becomes C. -r2. but the application of reflections and inversion to right-handed system results in left-handed ones. For so-caIled gvasi-crystals. For pn -= -1 one has n = 3. For ppI. We will derive them now by demonstrating that lhey must have three special properties. For p n = -2.'. it turns out that rotation symmetry axes Ohrough lattice points can only be 2-. It follows immediately that inversion with respect l o any other lattice point will do h e same. as w e suppose.

e. Bravais lattices Within a given crystal system. These differences give rise to diflerenf lattice types. The point group notations used here are those of Schonflies and the international notations are given in brackets.1: On the multiplicity of the rotation axes of crystal lattices. Even these simple lattices are not unambiguously &ermined by their ‘point symmetry. the point symmetry remains unchanged. multiplies all lattice vectors by the same real number. orthorhombic ( D z h ) .or 6-fold axes of rotation must also necessarily contain mirror planes parallel to each of these axes.monoclinic. the above results mean that exactly seven different point groups are possible for spatial lattices. They define the seven crystal systems: triclinic (Ct). In the tetragonal system the height of the . but they may differ otherwise. In summary. namely c%(i). for instance. stretches or compresses the lattices evenly on all sides.$). $ ) .2 visualizes them by means of their unit cells. hexagonal (DGh). z ) and Oh ($3. The simplest lattices ef a given point symmetry are represented at the far l f of each row et in Figure 1. In less symmetrical crystal system one may even change certain length relationships or angles between primitive lattice vectors without disturbing the point symmetry. ( C 2 h ) . Third. > D4h(&. trigonal ( D 3 d ) . Atomic structure of ideal crystals 9 Figure 1. ~ 2 h9( 2 q e ) ~ 3 & $ ) > cZ~( g. If one. D ~ h ( $ . Both systems of notation are explained in Appendix A. The explicit proof of this assertion will not be presented here.2. All three required properties described above are satisfied by each of exactly se’i. 4. and cubic (Oh). They axe called primitive lattices.). i. several different types of lattices may exist. Figure 1. one finds that point groups of lattices having 3-.1.2. Their common property is that they all have the same point symmetry. tetragonal (D*h). about &fold and other axes are also possible.en point groups.

one obtains a new point set having the same point symmetry as the original lattice. I the lattices cannot be transformed into each f other by such a transformation. If the answer is positive.e. but may be thought of as the union of several lattices placed within each other. Neither the spacecentered nor the face-centered cubic lattices can be transformed back to a primitive cubic lattice by means of a continuous and symmetry preserving transformation. Whether this happens or not is a question which must be explored separately in each case. Generally speaking. equivalent refers to positions which are either identical or that differ by a lattice vector. Analogous considerations have to be made for the other 6 primitive Iattices. According to this definition two Bravais lattices are of the same type if they may be transformed into each other by a continuous and point symmetry preserving transformation. we consider the different Bravais lattices in the case of the cubic crystal system. i.e. then the new point set forms again a primitive cubic lattice. the primitive lattices are determined only up to continuous point transformations preserving their point symmetries. thus it does not represent a cubic lattice of a new Bravais type. starting from a primitive lattice one can produce other sets of regularly ordered points by adding new points to each primitive unit cell in equivalent positions. in general. The same holds if the added points are the centers of the faces of the primitive unit-cell-cubes instead of the body centers. with a lattice constant equal to half of that of the original lattice. the body-centered (bc). It may be transformed back to the original primitive cubic lattice by means of a continuous and symmetry preserving transformation. Characterization of semiconductors rectangular parallelepiped in relation to its basis may be changed arbitrarily. snch as the centers of the primitive unit cells. If one adds both face and body centers to the primitive cubic lattice. It turns out that both cases may occur. no longer forms a lattice. then this implies that there are two different types of lattices with the same point symmetry. . those which are transformed into themselves or equivalent points by the point symmetry operations. Altogether one finds three different cubic Bravais lattices. otherwise they are Bravais lattices of different types.10 Chapter 1. one has to examine whether the lattice is only another realization of the original primitive lattice. however. If one adds the body centers of the primitive unit-cellcubes as additional points to a primitive cubic lattice. i. Moreover. As before. nor can the two centered lattices be transformed into each other by such a transformation. If one places the new points in symmetrical positions. the resulting point set has the cubic point symmetry and it forms again a lattice. whether or not it can be brought back to the original one by a continuous and symmetry preserving transformation. however. the primitive (p). In some special cases. and the face-centered (fc) ones. One calls them different Bmvais types or Bravais latttices. The new point set. the result may still be a primitive lattice. they represent cubic lattices of two new Bravais types. As an example. Therefore.

.‘\ # I Triclinic Monocfinic P Monoclinic 1 @ Trigonal R Trigonal and hexagonal P Figure 1.2.2: Common unit cells o the 14 Bravais lattices. .1. f . Atomic structure of ideal crystals 11 Cubic P Cuhic 1 Chic F Tetragonst I pj$.

will differ from the relation before rotat. in general. the crystal may be generated in such a way that one multiples its crystal lattice L-fold. then shifts the resulting sublattices relative to t. A crystal without basis may thiis be describd as a laltice whosp points are dl occupied by ahoms.ions of the two vectors may be different. Lattice points do not necessarily have to be occupied by atoms. is drscribed by a vrcbor The position R of this atom relative t o the i origin is then given by Ri=Rti.1.. . Generally. without changing their relative orientation.ed lattices. With only one atom per primitive unit cell! any point symmetry operation of the lattice will ncccssatily transform the whole crystal into itsdf. 2 . If the primitive unit cell canlains only 1 atom. where L is the total number of atoms in a primitive unit cell. the vectors 6 . respectively. For L 2 2 the set of all L atoms is called the basis uf the crystal. For this reason it is n meaningful to consider. which may be bum1 at general points of the primitive unit cells. L .5) Without loss of generality one may always set onr of the vectors il. Charactm‘zation of semiconductors In this w q . . If E and j are transformed from their original directions reht. For cryst. Generally. relative to the corner R of a primitive unit cell.12 Chapter I . also orthogonal transformations which map physically equivalent direchns of Ihe crystal into each other. in totul. without necessarily bringing the crystal back onto itself. The assignment ol Iht. . and finally occupies the points of the . We denote them here by an atom index 1 which t. Analogous statements hold for reflections and rotation-reflections..?I. (1. L. The Bravais lattices themsehps are shown in Figure 1.akes the values 1 . because of crystal snisotropy. equal to zero. however.. this is not true i general. . .he species 2.one finds that.hat the crystal has no basis. it may be placed in o m o f the roriiers of the cell. We explain the meaning of ‘physical equivalence’ by using the example of the relation between the vectors of the electric current density j and the electric field strength E in a crystal. with atoms of t. 1. the direct.ion. a primitive unit cell contains several atoms which may be either chemically identical or different. respcctivcly.om.g. the relation betwccn the new j and E. .2. If tbcre are orthogonal transformations . In the case I. For L 2 2.1 . shift. j is a non-lincar fimrtioii of E and.2 Point groups of equivalent directions and crystal classes The lattice of a crystal serves as a conceptional basis for the illustration of its translation symmetry. i l . besides the point symmetry operations of the crystal lattice.he first by. e. ‘I’he position of the 1-th at. . = 1 one says t.ive to the crystal into new ones.2.alswith basis.. 14 diEerriit Bravais lattices are possible in the 7 crystal systems.sr lattices to the crystal systems is indicated in Table 1. .

primit. Atomic structure of ideal crystals 13 Table 1.2. ! I 1 1 1 '2h rhombic trigonal tetragonal I hexagonal cubic I ) p bc fc . bfc .body centered.1. bc . ~ Crystal system tnclinic monoclinic + group lattk c 1 Holohedral Braiais Crystal class Number of space groups r C. fc face centered. The following abbreviations are used p .basis face centered.1: Symmetry classification of crystals.ive.

which follows a rotation about an n-fold axis in a screw-rotation. Each crystal class corresponds to a particular point group of equivalent directions. Characterization of semiconductors which leave the relation between the two vectors unchanged .the original and the transformed directions are called ‘physically equivalent’. the atoms of the crystal are not necessarily also trausformed into equivalent atoms. It may be necessary to add to a rotation yet another translation parallel to its axis (screw-rotation). found in at least one crystal system. several in more than one. is called the point group of equivalent directions. rotationreflection or rotation-inversion which transforms a particular direction into a physically equivalent one.14 Chapter 1. There are as many different point groups of equivalent directions. This follows immediately if one . or crystal classes. reflection.after carrying out s rotation. This consists of the set of all rigid displacements which transform the atoms of the crystal into identical or equivalent positions. however. In crystals without basis the point group of equivalent directions coincides with the holohedral point group.3 Space groups and crystal structures It remains for us to explore the symmetry of the crystal as a whole.the point group which defines the crystal class has to be a subgroup of the holohedral group of the crystal lattice. In assigning the crystal classes to the different crystal systems one proceeds as follows: A class which exists in several systems is attributed to the one with the lowest common symmetry. It defines the crystal class. which states that every rigid displacement which is not a pure translation or an orthogonal transformation. The converse. must be an integer multiple of one n-th of the smallest lattice vector in the direction of the axis. 1. or to add to a reflection a displacement parallel to the mirror plgraetglide-re~ection). Each crystal class is.1. In this way one obtains the assignment between crystal systems and crystal classes shown in Table 1.which ultimately must be verified experimentally .1). is not always true . That one records in this way all conceivable symmetry operations follows from a theorem proven in Appendix A. It is obvious that symmetry operations which transform equivalent atoms into each other must necessarily also do the same with physically equivalent directions. The parallel displacement P. must be a screw-rotation or a glidereflection. For crystals with a basis this is no longer true in general.or to add both in the case of rotation-reflections and rotation-inversions. The group of orthogonal transformations which map physically equivalent directions of a crystal into each other. and the point groups of equivalent directions are generally subgroups of the holohedral groups. as there are different subgroups of the 7 holohedral groups. Using Appendix A one can easily show that their number amounts to 32 (see Table 1. however.2. Not all crystal classes can be realized in all crystal systems .

a rotation by 27r. It is called a space group. then its space group necessarily contains the point group of equivalent directions as a subgroup. Atomic structure of ideal crystals 15 considers the n-th power of the screw-rotation. At each stage of counting only the newly occurring space groups are added. moving in the direction of increasing symmetry. The total is 230. This describes an n-fold repetition of the rotation by 27r/n. The set of all symmetry operations on a crystal forms a group. The set of all possible space groups of crystals may be obtained in the following way: One considers. In summary. i. The symbol 63. . The latter do not contain the point group of equivalent directions of the crystal.there are only two.1. means a 6-fold screw axis with a parallel displacement by half the shortest lattice vector in the direction of the axis. Bravais lattices and crystal systems. Each of these 230 possible space groups corresponds to a particular crystal structure. for changes of the distances between atoms and of angles between lines connecting atoms which do not affect the symmetry. we may state that the symmetry operations on a crystal are of the following types: translations by lattice vectors. of course. except. proper rotations. first of all. Each element of a symmorphic space group is the product of an element of its translation group and an element of the point group of equivalent directions. In this case only the primitive Bravais lattice is possible. it is necessarily a multiple of the shortest lattice vector in this direction. For a glidereflection one can similarly show that the translation in the mirror plane must be a superposition of multiples of halves of the smallest linearly independent lattice vectors in this plane. In this way one obtains the numbers indicated in Table 1. In the international notation system the multiplicity is described by a lower index a f b e d to the symbol for the rotation axis. Five are especially important: Their designations in the international system are Fd3m (diamond structure).1. all combinations of these transformations are allowed. Such space groups are called symmorphic. Furthermore. or no rotation at all. Space groups with screw-rotations or glide reflections are called non-symmorphic. Similarly one proceeds with all other combinations of crystal classes. The corresponding space groups may easily be determined . rotary reflections. the vector n times p’ must be a whole lattice vector. F W m +. for example. the structure of a crystal is uniquely determined. This also indicates that the axis is not an ordinary one but a screw axis (with right-handed thread). As it points in the direction of the screw axis. The majority of semiconductors belong to a small selection of the possible crystal structures or space groups. By specifying its space group. reflections. which is also a symmetry element as well. If the crystal has no screw-rotations or glidereflections as symmetry operations.e. crystals of the triclinic system.2. followed by the translation n times Since the crystal must pass into an equivalent position by such a transformation. rotation-inversions as well as screw-rotations and glide-reflections.

3). namely the face centered cubic. therefore. nor the distance between two atoms in a crystal with this structure (which is &/4). A silicon crystal of volume 1 cm3. Characterization of semiconductors (zincblende st ruct ure) .3. ey. P63m c (wurt zite st ructure). which deals with the chemical nature of semiconductors. We consider this connection in more detail in the next section. For the volume Ro of the primitive unit cell one obtains the value u3/4 from equation (1.2.. Table 1. but also have the same Bravais lattice. This is done by the basis of the crystal. The five crystal structures above belong to just two different crystal systems . in which respect the three cubic semiconductor structures differ. The lattice constant a is the distance between the lattice points of a primitive cubic reference lattice. . are taken in the directions of the cubic crystal axes. The lattice does not determine the positions of the atoms. Each of these crystal structures is more or less closely tied to a particular material group. and P3121 or P3221 (selenium structure). zincblende and rocksalt structures belong to the cubic system and the wurtzite and selenium structures belong to the hexagonal system. abbreviated as fcc. which is obtained from the fcc lattices by omitting the face centers.e.4 Cubic semiconductor structures Crystals having diamond.5 x primitive unit cells. The fcc lattice is commonly described in a Cartesian coordinate system whose unit vectors e.00 x cm3.t h e diamond. zincblende and rocksalt structures not only belong to the same crystal system. F m3m (rocksalt st ruct ure) . The primitive lattice vectors al. We start with the three cubic structures. In the case of silicon this yields Ro = 4. contains 2. We stress that the cubic lattice constant is neither the distance between two lattice points (it is u / f i for the fcc lattice).16 Chapter 1.* of the fcc lattice may be chosen in the form The lattice constants for a series of semiconductors with fcc lattices are listed in Table 1.a2.2 summarizes their properties 1.

Diamond Zincblende Itocksalt Wiirtzite Seleniuni F#m P3121 P3221 fy . 0 < C < h.2.1.3. Atomic structure of ideal crystals 17 Table 1. More details are given in the text. 4 2 43m Gmm 32 Bravais lattice cubic fc cubic fc cubic fc hexagonal P hexagonal P Primitive lattice vectors Basis I I I .2: Characteristicz of the five most comnion structure types of seniiconduc tors. 0 < n < $.

70 MgS 5. the basis consists of two atoms which.61 a cla Selenium structure Se 4.62 I AlN 3.47 1.18 Chapter 1.66 ZnS 5.45 SnTc 6. respectively.53 1.31 1. Characterization of semiconductors Table 1.14 1.36 Te 4.46 Wurtzite structure ZnS 3.14 ZnSe 5.20 MgSe 5.12 PbTe 6.87 5.14 cl a Diamond and zincblende structure For diamond and zincblende structures.37 1: I Rocksalt structure PbS 5. The two atoms are shifted with respect to each other in the direction of the body diagonal of the primitive reference cube by a quarter of its side. I a-Sn 6.43 Zincblende structure 1: Ge 5.82 1.62 CdSe 4. then the position of atom 2 is given by .64 I MgTe 4.3 CdO 4.42 HgSe 6.08 IlgTe 6.65 .05 InSb 6.47 ZnTc 6.33 a 1.37 5.19 1.54 AlP 4.11 1.65 6. Diamond structure C Si 5.3: Lattice constants of semiconductors of various types of structures.08 CdTe 6.93 PbSe 6.47 RlAs 5.60 CdS 4.62 InN 3.63 GaN 3.13 InAs 6.45 Cans CaSb Id’ 5. have the same or different chemical natures.46 I GaN 4.66 Gal’ 5.54 1.43 AlSb 6. If the basis atom 1 is put at a lattice point.

0 1A 02 8 3A 0 4B P (1111 6 Cmll 3 cfm a IA r. Crystals with diamond and zincblende structures may also be described as a composite of two interpenetrating superposed fcc lattices displaced with 2 respect to each other by the vector ? and with their lattice points occupied by. chemically equivalent or different atoms.4 one can readily see that for both crystal structures the cubic axes put through an atom form 4-fold mirror-rotation or inversion rotation axes (which are the same in this drawing). respectively. From Figure 1.3 and 1. Atoms of the same size and darkness lie in the same plane. In the diamond structure all atoms arc of the same chemical clement. a 3-dimensional representation and a plane projection. in the zincblendc structure the atoms are of two different chemical elements. respectively. and that for the (111) plane after 6 layers.4 in. 2 0 3A 40 * 5A 60 (J Figure 1.2. 1.4: Projection of a crystal having diamond and zincblende structure in a (100) plane (left) and a (111) plane (right). The sequence for the (100) plane is repeated after 4 layers.1. Spatial model of a crystal having diamond (a) and zincblende structure (b). The body diagonals through an atom are %fold axes of . Atomic structure of ideal crystals 19 Figure 1.3. The vertical sequence of atomic layers is indicated on the right hand side of the projections. The geometric relations are depicted in Figures.

and the space group turns out to be symmorphic. One. the diamond and zinchlmde structiires. For the zincblende structure there are no further point symmetry operations which transform equivalent directions into each other. In the raw of diamond structure. This yields the full cubic group Oh. rotation. and the planrs through opposite cube dges are mirror planes. see Appendix A). It may be described as reflection in a plane perpendicular to a cubic axis. namely by adding the inversion operation. say e. It is denoted by F13m. Both structures are theiefore tramformd into themselves by the point group T d . For future reference we bear in mind that for the diamond and zincblende structures. The group o h can be generated from t h e tetrahedral group in yet anothcr way. It follows that their point groups of equivalent directions are at least T d . therefore.20 Chapter I . inversion must be relative to the site of an atom and be followed by a tradation through the vector T or -?zr depaid2 ing on whether m c considers a 1. Characterization of semiconductors Figuw 1. has a glidereflection as additional symmetry dement.. The point group of equivalent directions is therefore T d . which cuts the connecting line bel w r n two atoms at its center. namely that which transforms the two chemically equivalent atoms of the basis into cach other. followrd hy a translation in that plane by (e/4) (ex ey). respectively. as one can easily determine by means of the stereograms o the f Iwo groups rn Figure 1. inversion always involves an exchange of the two sublattims. As an element of the space group. The space group of diamond structure becomw non-symmorphir in this way The point group of directions of this structure may be obtained from the point group T d of the zincblende structure by adding the reflections in planes perpmdicular to the thrw cubic axes. + We now extend our discussion to thc neighborhood-relations in the two crys- .5: Stereograms of the paint groups Oh (left) and 7'6 (right) of.or 2-atom.5 (for a n introduction to the stereograms of point groups. the symmetry group of a tetrahcdron. thew i s yet another symmptry operation.

four nearest neighboring 2 atoms. n Rocksalt structure The basis of this crystal structure consists. relative to the central atom.7. ( a / 2 ) ( f e y f e z ) .i). but naturally they lie in three other primitive unit cells. f ey). the displawmcnl i s not. This means that each 1-atom has. whence .(e/4)(T. the so-called coordmatatm Consider atom 1 of thc Lesis of the unit cell at R = 0. altogether. 1. (a/4) (1.l).21 Figure 1.1.6: Spatial model of a crystal with rocksalt structure. of course. tal structures. the mme also holds with respect to a %atom. however. They are located at thc nearest-neighbor lattice points of the fcc lattice. The four nearest neighbor atoms lie at the corners of a tetrahedron. whose center is occupied by the atom itself (see Figure 1.3). for both structures. 1. Therefore. a quarter but half of the length o€ the space diagonal of the reference cube. This means that thew are 12 second nearest neighbors i each slructurr. thus their positions are ( u / 2 } ( * e 9 f ef). The basis atom 2 of this cell is one of its nearebt neighbors. l). Since it would also have been possible to start from a 2-atom in this consideration. of two atoms of diffprent chemical nature which arc displaced relative to each other in the direction of the space diagonal of the reference cube. Thr distanrc betwrrn nearest neighbor atoms is &a/4. then the basis atom 2 of the primitive unit cell at R = 0 gives rise t o three more basis atoms of type 2. (a/4)(1. like that of zincblende structure. In contrast to zincblende structure. The second nearest npighbors belong to the same sublattice. They are a l at the same distance l from atom 1 as thP 2-atom first considered. Their relative positions are given by the vectors (a/4)(1. independently of whether t h 2-atom is of the same chemical nature as the 1-atom (diamond structure) or is not (zincblende structure). and. they arc atoms of thP same chemical species. If all rotation-reflections are executed with respect to the axis through atom I. (a/2)(*e.l). For silicon this is 2+35 A .

--ex a h 2 a + -&e. As one can see horn these drawings.and 2-atoms alternating. the crystal has the full symmetry of the primitive reference cube. 2 ce. as in the zincblende structure. In Ihe direction of a cubic axis. The point group of equivalent directions is therefore the full cubic group o h (see Figure 1. has 6 nearest neighbors. h Here ek. and with their lattice points occupied by chemically different atoms.2. The vertical sequences of atomic layers is shown on the right hand side of the projections. these atoms are ncarest neighbors.22 Chapter 1. I$. The two primitive lattice vectors a1 . Accordingly. a crystal having rocksalt structure can be described as a composite of two fcc lattices.5). In the (LOO) case the stacking repeata itself after 4 Iayem. Their number amounts to 12.7. e." are unit vectors of a cubic coordinate system whose z-axis points in the direction of the c-axis of the hexagonal lattice and whose z-axis is identifird arbitrarily with one of the three symmetric lattice directions in the plane perpendicular to the c-axis. The space group is symmorphic and is denoted by FmSm.a. with 1. h a2 . 1.". Since shorter distances do not occur.6 and 1. displaced with respect to ~ a c h other by the vector ?. Each atom. ' z This structure is illustrated in Figures 1. Characterization of semiconductors (1111 1A 01B 4 2A 0 28 1A 028 0 - 3A 48 5A 0 6B Figure 1. therefore. the atoms are separated by a distance of a / 2 .7: Projection of a crystal having rocksalt structure in the (100) plane (left) and the (111) plane (right).5 Hexagonal semiconductor structures The primitive lattice vectors of the hexagonal lattice may be written in the form ai y.. The second nearest neighbors are the nearest neighboring atoms of the same fcc sublatticp. and in the (111) case after 6 layers. The relative positions are also the same as in this structure. e.

2. correspondingly. The two M-lattices are displaced relative to each other by F M ~ . The volume 52 of a primitive unit cell is &a2c/2. The space group of the wurtzite structure is nonsymmorphic and is denoted by P6amc. In order that all four be at the same distance from M I . The c-axis through the center of one of the empty hexagons in Figure 1. Each pair of these atoms.9 these relations are illustrated in. while the two pairs are of different elements M and X. then the position vectors of the three others are fx1= cc e. Consider the atom M I in the unit cell at R .8 and 1. The corresponding point group of directions is c 6 v (see Figure 1.-c$.9 forms a 6-fold screw axis 63: a 2n/6-rotation about this axis must be connected with a parallel displacement by c/2 in order to transform the crystal into itself.likewise as the two X-lattices. X 2 ) on the other hand. Mz and X 2 .10). among them three proper reflection planes and three glide-reflection planes joined with translations by c/2 in the direction of the c-axis.9). one obtains from Xz two additional X-atoms at the same distance but in other unit cells. the c-axis through atom M i is a %fold symmetry axis (sep Figure t. on the one hand. This also mean8 that this axis represents a %fold proper axis of rotation. In Figures 1. The displacement of the XI-lattice with respect to the MI-lattice is Fx1. spatial and planar displays. M2.1. From these figures one can easily determine the symmetry of the wurtzite structure. namely M I . respectively. We denote them by M I . ( is a parameter which may take any value between 0 and 1/2. and two of them by atoms of species X. and.0. The M-atoms are shown in black and the X-atoms in white. all four be . The axis contains six inequivalent mirror planes." .h I Fxz of the unit cell at R .3. Its neighbor in the same unit cell is atom X 1 at the site ?XI. If atom M I is sited at a lattice point. X I .10) Here. Wurtzite structure The basis of crystals with wurtzite structure consists of 4 atoms. Atomic structure of ideal crystals 23 and a in this plane have equal lengths and form an angle of 2x13 with 2 each other. and XI. The lattice -0 constants a and c of some semiconductors with a hexagonal lattice are listed in Table 1. are chemically equivalent. Altogether. there are four neighboring X-atoms. with the lattice points of two of them occupied by atoms of chemical species M. (1. Another neighbor of M I is Since the atom Xz at the site -ce. A wurtzite type crystal can be understood as a composite superposition of four interpenetrating hexagonal lattices.

11) If it is fiilfilled. This means that the four nearest neighbors of an atom are sited at the corners of a slightly deformed tetrahedron which surrounds the central atom symmetrically.8: Spatial model of a crystal with ideal wurtzite structure. In semiconductor crystals of the wurtzite type. the distance 1 7x1 I between M I and X I must be equal to the distance I -ce. the condition (1.24 Chapter 1 . (1. This results in the condition c = . and . the atom Mi has four nearest neighboru of chemical species X . Characterization of semiconductors Figure 1.9." t F x 2 I between Mi and X2 in the unit cell at R = -ce!. Projectionof a crystal with ideal wurtzite structure in the plane normal to the c-axis. with the interchange of M and X . c6~of the wurtzite of M I . 19 ( . The vertical sequence of atoniic layers is shown on the right herid side.11) is always satisfied almosl perfectly.1) t .10: Stereograms of the point group structure. dito for X I and Xa. nearest neighbors Figure 1. 0 1 A 028 3A 0 4B Figure 1. The same statement is true for M I .

11).12) Table 1. The volume &a2c/2 of a primitive unit cell oi“ the ideal wurtzitc structure is d 3 / 2 . If one multiplies the lattice constants a. The uppermost C’ double layer A’ of the zincbbnde structure in Figure 1. the nearest neighbor atoms are positioned at exactly the same sites as in a crystal having zincblende structure with lattice constant 4 a. For the deformation to vanish. this does not at all mean that the wurtzite structurc may be traced back to lhe zincblende slruclure.t.9). For the two distances to be equal. of thc wurtzitc type crystals in Table 1. the actual positions of the second nearest neighbors differ in the two crystal structures. The degree of deformation depends on the ratio cla. This result means that in a crystal having wurtzite structure which fuEUs conditions (1. This yields = 3(1/2-<) or = 318 which. taken together with equation (l. Atomic structure of ideal crystals 25 which is compressed or stretched in the direction of the c-axis. Indeed. (1. B’. In the wurtzite structure the vertical stacking repeats itself after two double layers of nearest neighbor atoms.2 by 4.12).and XI-lattice planes perpendicular to the c-axis must be three times the distance between the X I . one says that it has an ideal w u r t z i t e structure.ll). 1. -t e$ . by stacking one upon another two different double layers A and B. The wurtzik structure can be set up.12).and M2-lattice planes perpendicular to this axis. results in < < (z) fi= = 1.2 shows that all wurtzite type semiconductors listed there also satisfy this condition quite well. but in the zincblende structure only after three.t e (see Figure .1. just as in the zincblende structure.13) must hold. Of course. which is twice that of thc zincblende reference structure given by 8 1 4 . (see Figure 1. although they are all at the same distances a = a’/& This may be seen most easily from the projections of the two crystals on the plane perpendicular to the c-axis (see Figure 1.11) and (1. the equation a’= h a (1.llb coincides with the . the zincblende structiire by stacking three double layers A’.4) or to the space diagonals e.then one in fact obtains values which fit well witahthe cubic lat.2. The corresponding distance in the wurtzite structure is Cc = (3/8)@ a. This indicates that the ordering of the nearest neighbors in the wurtzite structure is almost the same as in the zincblende structure. The distance between two nearest neighbor atoms in the zincblende structure is &all4 with a‘ the cubic lattice constant. If a wurtzite crystal exactly obeys conditions (1.iccconstants of the zincblendc structure crystals of this table. therefore. the distance between the M I .633.11) and (1.

By examining the layers in Figure 1. In stacking. The stacking sequence is depicted on the upper right. while B’ and C’ differ from B.11 we also note the different locations of some of the second nearest neighbor atoms of the two crystal structures.26 Chapter 1.B’ -A . In Figure 1. . in the ideal wurtzite structure.B’ A’ Figure 1. in a solid. uppermost double layer A of the wurtzite structure in Figure L l l a . From this observation we may conclude that. Atoms shown by full circles form the upper part of a double layer. Characterizrrtion of semiconductors A B -A * -B .11 this fact is illustrated by emphasis on the second nearest neighbor atoms mentioned. and atoms shown by open circles form the lower part of such a layer.Thus the second nearest neighbor sites are partially different in the wurtzite and the ideal zincblende structures. -A’ - -C’ : .11: Construction of a crystal having wurtzite structure (top) and zincblende structure (bottom) by stacking of double layers of nearest-neighbor atoms. Those in double layer B are not in the same positions as those in double layer B’. A comparison of the two crystal structures shows that the same ordering of the nearest neighbor atoms may be consistent with different orderings of more remote atoms. M h e r explanations are given in the text.C’ -B -A’ . while in the zincblende structure three second nearest neighbors are in the C’-layer above and three in the B’-layer below. Among the 12 second nearest neighbors of an atom in an A = A’-layer. the nets shown in each of the double layers must be placed at the same positions. three are found in the upper B-layer and three in the lower B-layer.

in which successive atomic positions are rotated with respect to each other by an angle of 120' (see Figure 1.h. rotations are allowed with respect to the three inequivalent 2-fold axes perpendicular to the caxis.2. to transform the crystal into itself. The vectors of the basis may be written in the form ~3 = -2craez + . in both cases. This is just what is observed in amorphous silicon and other amorphous semiconductors. Atomic structure of ideal crystals 27 Figure 1. the selenium structure may also have symmetry corresponding to the space group P322. These rotation axes pass through the %fold screw axis and through one of the three surrounding atoms. It contains one %fold screw axis parallel to the c-axis which goes through a center of one of the empty triangles in Figure 1.13).e. Beside these screw operations.1. The space group can be determined from the projection of the crystal on the plane perpendicular to the c-axis (see Figure 1.14) where a is a parameter ranging between 0 and 112. it should be emphasized that these struc- . Selenium structure The basis of trigonal selenium and tellurium crystals consists of three atoms. The point group of directions is. the long-range order could be perturbed without significantly changing the short-range order of the corresponding crystal. A rotation by 120° or 240' must be followed by a displacement by c/3 or 2c/3 in the direction of the c-axis. where the spiral differing from P312 has not a right-handed thread. The atoms are ordered on parallel spirals.14). Concluding this discussion of the characterization of the most common semiconductor crystal structures.13.12). but a left-handed one. D3 (see Figure 1. Beside this. 3 2c (1. The symmetry operations mentioned correspond to the space group P312.12: Spatial model of a crystal with selenium structure.

in the context of the electronic f structure o yprturbrrl semiconductors. Such defects will be considered in detail in Chapter 3. The vertical sequence of atomic layers is shown on the right hand side. Material classes According to their chemical nature.14: Stereograms of the point group D3 of the selenium structure. vacancies. In thiv book. Examples of organic semiconductors indude anthracene. In 'l'able 1. organic semiconductors are also of interest for science and tcchnology. Figure 1. Characterization of semiconductors (00011 o c c 3 Figure 1. naphthaline and polyacetylcne. . tures apply to the ideal case of infinite. and chemically absolutely pure materials. . The best way to get an overview of the different &sues of inorganic semiconducting materials is to examine thP periodic table of elements.4. Nevertheless. 1. In the next section we will discuss the chemical composition of idea1 semiconductor crystals. because these are much bettcr understood and haw much greater twhnolagical iniporttznce than semiconductors of the organic type. most semiconductors are inorganic materials. or atoms on interstitial crystal sites. Real crystals deviate from this ideal case in varying degrees. a part of the periodic table is shown with which many elemental and compound semiconductors are associated. There are structural defects such as stacking faults. W e start with the clernenld semiconductors of group IV. structurally perfect.13: Projection of a ciystal having selenium structure on the plane normal to the c-axis.we restrict our considerations to inorganic semiconductors.28 Chapter 1 .or screw-dislocations.3 Chemical nature of semiconductors. step.

silicon (Si).4: Part of the periodic table t o which Inany element.1 Group IV elemental semiconductors Semiconductors of this group are.weezl metals and insulators. and of finding Ge is x.he alloy. germanium (Ge). or Sil-. In the case of Sil-.3.1.Ge. much like a metal. 1. on the contrary.3. with this. These are crystals with the same geomcbric order of atom sites as in the case of the alloy components here that of diamond in both CBSW.Ge). The regular crystal sites are occupied. Material classes 29 3 Mg c Si Ge N 0 S A1 Ga In T1 P As Sb Bi Zn Se Cd Sn 're Hg Pb Table 1. l Beside the pure elemental semiconductors Si a i d Ge. It is weUknown that silicon is the material of preference in microelectronics and. randamly by Si or Ge atoms.and optoelectronics. All cited semiconductors of this group crystallize into the structure of diamond. the probability of finding Si is 1 .2.als.&& play an essential role in micro. to indicate the rpspcctive mole fractions 1 . Retween them one has the two typical semicondnctors silicon and germanium. According to their structure. The lattice constants of inixcd cryst. Chemical nature of semiconductors. the alloys may be identified as mixed crystals. in t. starting at the top of column IV? carbon (C) in the form as diamond.z and z of the two alloy components. The notation for such alloys is (Si.al and compound semiconductors are associated. i many n ~ . They differ from each other in regard to their position Let. one of the most important materials in d modern technology. however. and tin (Sn) in its gray modification known as a-Sn. Both mat. T'he probability of finding a particular el* ment on a given site is determined hy the mole frclctiou of this element.Ce. Diamond behaves much like an insulator! and tin. alloys of bath materials also have semiconducting properties.

for example. The principal applications of the 111-V semiconductors and their alloys lie in the field of optoelectronics. Using this result. Actually the GI-V compounds (with a few exceptions) do crystallize into the zincblende structure.3.30 Chapter 1 . A mixed crystal strongly deviates from an ideal crystal. Except for the nitrides all these compounds crystallize into the zincblende structure. It became possible to tailor materials with desired properties.Al)As and Ga(As. the mixed crystals made of binary 111-V compounds also have semiconducting properties. besides the zincblende structure. The common feature of the elements of the main group IV of the periodic table is that there are four electrons in the outer shell of their electron clouds. follow from the lattice constants of the constituents by means of Enear interpolation.Ga)(As. In the case of ILVI-compounds the wurtzite structure can also occur. It was recognized at the beginning of the sixties in (Si. however. The primitive unit cell. ZnN.where asi and a& are the cubic lattice con. Characterization of semiconductors cases. the so-called valence shell. Ge) alloys. just by varying the alloy elements and mole fractions. AlK. BP. since the crystals of these compounds also have 8 electrons per primitive unit cell. BAS.z)asi Z U G ~ . InAs and InSb. and from main groups 1 and VI of the periodic table should also be semiconductors. therefore contains 8 electrons. The two structures are. so that semiconducting behavior may be expected also in their case.P). GaSb. one may conclude that compounds of elements from main groups III and V. + 1.P) are used. Gap. pro1 vided they have zincblende structure. GaAs.2 111-V semiconductors The conjecture that the 111-V compounds should be semiconductors is amply confirmed. and by no means obvious. which here has two atoms. in light emitting diodes (LEDs) and laser diodes for the near infrared t o green spectral region. Ga(As. InP. as has been pointed out above.ce) a Sil-. is given by the relation ~ ( s i =~ ). AlSb. GaN. This is important. Just. respectively. but the semiconducting property of the two pure crystals is often retained in the mixed crystal. The nitrides are stable in the wurtzite structure. very similar. BY and GaN also have metastable zincblende phases. Alp. The discovery of semiconducting alloys significantly expanded the family of semiconductor materials. Examples are (Ga. as in the case of the elemental semiconductors of group IV. one obtains the following compound semiconductors: BN. Following the group III and group V columns of the periodic table from the top down. (1 stants of Si and Ge. alloy. Al)As. (In. Later we will prove that semiconducting properties are related to the crystal structure and the number of valence electrons per primitive unit cell. This result is known as Vegard’s rule. P).Ge. (Ga. GaN .Ga)As and (In. Later it was also shown to be true in many other material combinations. The cubic lattice of constant a(si. AlAs. €or example.

3 11-VI semiconductors This group includes compounds like ZnS. ZnTe. in fact. which crystallize into the zincblende structure.1. Some semiconductors of this material class. GaAs and. e. MgS and MgSe form crystals with rocksalt structure.Se).55 p m wavelengths. e. Cd(S. As in the case of the 111-V compounds a large number of semiconducting alloys may also be realized from the IT-V1 compounds. lately. like ZnS. Before the introduction of power rectifiers based on silicon. Zn(S. Both crystallize into the same trigonal chain structure. For most of these materials the one of the two structures which has not been mentioned corresponds to a metastable phase. The quaternary alloy system (Ga. (Hg. for example. Up to now. to photocopying where the photosensitive layer of the photostatic cylinder may be made of selenium or a selenium alloy. HgSe and HgTe. It is utilized for detectors of radiation in the medium infrared spectral region. which is characteristic of these materials (see Table 1. and the hexagonal phase is the mineral ururtzite. and compounds like CdS. an alternative to the traditional vacuum-tube. stable. also (Gtr.3. CdTe. technical applications involve mainly (Hg. Material classes 31 is a promising material for blue LEDs and laser diodes. and for ZnS both structures are. The cubic phase of ZnS is the mineral zincblende. They make it possible to fabricate largearea electroluminescence displays.Se) and others.4 Group VI elemental semiconductors Selenium and tellurium are likewise good semiconductors. 1. the photoelectric properties of selenium are exploited. CdS. In)(As.g. CdO. CdSe and MgTe which have the wurtzite structure.Cd)Te. Chemical nature of semiconductors. P ) is used in making laserx and pholodiodes for optical fiber communications at 1.3. 1. BN and GaN can be used for electronic devices to be operated at high temperatures. It i s from these mineral names that the designations of the two crystal structures are derived. ZnSe.3. selenium ones were used. . which provides maximum transmission for SiOa-based fibers. This applies. are good luminescent materials. Other such compounds. above all. The operation of blue-green LEDs and injection lasers made of 11-VI compound semiconductors was demonstrated very recently. have very good photoelectric properties and are used accordingly. HgS (vermilion) has a rocksalt-like structure.2). Today. which is of particular interest since the emission maximum of the thermal radiation of bodies lies in this region for a broad range of temperatures.g.Cd)Te.Al)As are employed for transistors with extremely short time delay. Selenium has a long history of practical use.

1. and selenides of the semimetals As. orthorhombic and monoclinic crystal systems have been observed.v ~compounds. and Bi are among them. however. One also finds semiconducting properties in compounds composed of elements of groups V and VI with the stoichiometric composition V2-VI3. including GeS.3. which possess both tetragonal and cubic crystalline phases. of the zincblende or wurtzite type.Se). S i c OCCUIS in many crystal a structures. there is a second group of semiconducting IV-IrI compounds which display an orthorhombic structure. Examples are ZmAsz and CdsAsz. Characterization of semiconductors 1. Examples are G ~ q S e 3 ~ GazTe3 or In2Se3. PbSe. one also finds semiconductors among III-VI compounds. which all crystallize into the rocksalt structure. which distinguish themselves by having a (ordered or disordered) network of cation vacancies. which makes it possible to fabricate electronic devices for high temperature and high power applications. The elements of groups I1 and V may form semiconducting 1 I 3 . and GaTe are ex- . Different structure types of the trigonal. Electroluminescence w s observed in this material as earlier as 1907. The reason is the good thermal stability of Sic.5 IV-VI semiconductors EIements of groups IV and VI can also form semiconducting compounds. The layer-structures GaS. PbTe and SnTe.32 Chapter 1. a relatively large diversity exists among these compounds. These vacancies are necessary to make possible a stoichiometry which deviates h m that of the basic structure. Among the semiconducting 111-VI compounds. much activity is now being devoted to this materiai. They crystallize into so-called defect stmctuws. Finally. there are also those with 1:l-stoichiometry. GeSe.Sn)Te and Pb(S. among them the zincblende and wurtzite structures. GeTe is an exception as it crystallizes into a rhombohedra1 structure. which display a 2:3-stoichiometry. In particular. sulfides. These semiconductors are now used primarily for the generation and detection of radiation in the medium infrared spectral region.3. for example. SnS and SnSe. Important semiconducting alloys of such compounds are (Pb. GaSe. After a long period of only moderate interest in Sic. the oxides. Examples are PbS. The very good thermoelectric properties of Bi2Se3 and BizTq have long been used for cooling elements. These are modifications of certain basic crystallographic structures as. With regard to crystal structure. In addition. It is one of the longest known semiconductors of all. It seems that S i c is the only stable compound of this kind. Sb.6 Other compound semiconductors It is to be expected that a combination of two elements of group IV will be a semiconductor.

The reason for this relation between chemical composition and atomic structure is by no means obvious. We will undertake this discussion in greater detail in the next subsection. Semiconductors are also counted among the II-IV-V2 compounds. in particular. 1 4 Macroscopic prapert ies and their microscopic . A semiconductor of this group displaying ferromagnetic properties is EuSe. On the other hand. it will stimulate our intuition later in this book when we are going to derive the microscopic physics of semiconductors. as a riile. meaning. one has. Macroscopic properties and their microscopic implications 33 amples. we add two more general remarks. they must often be intentionally polluted with certain chemical elements. ZnSiPa as an example. the I-111-VTz materials which crystallize. Firstly. Absolute chemical purity. the distribution of the allowed electron energy levels in the form of bands being separated by forbidden energy regions. in particular. the same crystallographic structure. Ilowever. It is closely connected with the electronic structure of crystals which we will treat in Chapter 2. The crystal structure is also of chalcopyrite type. occiirs in nature just as seldom as absolute crystallographic perfection.bear in mind what has been said about this point in the introduction. irnplicat ions In this section we describe characteristic macroscopic properties of semiconductors and w e them as a guide to reveal some important microscopic features of these materials as.1. from first principles. their impurity concentrations must not to be too large .4. semiconductors can not to be too pure. In order that crystals composed of such materials really be semiconductors. chemically pure materials. it has to b r remeinherd that we have stated the chemical composition of ideal semiconductor crystals. In order to have a sufficiently large electric conductivity. including their band structure. . for example. into the chalcopyrite structure belonging to the hexagonal crystal system. Secondly. Concluding this survey of the most important semiconducting material classes. however. So far we have exclusively considered bznary compound semiconductors. Among the ternary I-IIEVI compounds. thcrc are also semiconductors generated from ternary and qua ternary compounds. Although the microscopic model of a semiconductor obtained in this way cannot be more than a lucky guess. such as CuGaSz. Each real semiconductor material contains chemical impurities. it is striking that the semiconducting substance classes which were defined pritnarily by their chemical nature also display.

5: Electrical conductivity 0 and charge carrier concentrations for metals. 1 To construct an explanation. Then a current of 1 A will flow if ern-'. serniconduct. n jcm-3 < 10-10 1021 .ors.16) The mobility p is defined as the ratio of the magnitude of the average velocit.u. semiconductors. and insulators’ are assembled in Table 1. The latter is defined in terms of the proportionality factor between the current density j and the electric field E in Ohm’s law j=uE (1.and insulators.1 Electrical conductivity As already mentioned.15) Here.4. Characterization of semiconductors Table 1.16) for the Conductivity o shows that its variations may.5. namely their electrical conductivity. and the electric charge -e of an electron. 1o1O 1.. be caused either by different values of the mobility p and/or by different electron concentrations n. the term ‘semiconductor’ refers t o a characteristic macroscopic property of these materials. One ex- .y of an electron to the strength of the electric field driving it (for a derivation see Chapter 5). The mobility is actually determined by the scattering processes which electrons undergo due to the perturbations of the crystal lattice. we use the known representation of the s electrical conductivity IT a the product of the electron concentration n. The order of magthe cube material has a conductivity of (T = 1 nitude ranges spanned by the U-values of the three material classes ‘metals. The striking features of this table are the large changes both between the three classes of substances as well as within the ‘semiconductor’ material class.34 Chapter 1. and apply a voltage of 1 V between two of its opposite planes. (1. . the mobility . Formula (1. u = enp. The question arises how these sharp changes may be understood 0 1a physical basis. Material class Metal Semiconductor Insulator lo3. in principle. . it is assumed that anisotropies either do not exist or are negligible. The following example gives an idea of the order of magnitude of the conductivity: Consider a cube with edge length of 1 cm.

which amounts to approximately 10” electrons per m 3 .2 Dependence of conductivity on the semiconductor state The large range of conductivity values of semiconductors. One calls this process doping wzth impup.ity atoms.one c d s this an int~ninsicsemiconductor. The orders of magnitude of the mobilities ME. Formula (1. from the chemical diversity of semiconductors. In Table 1. rrg is a factor which depends only weakly on temperature. the temperature.-values are listed for some import ant semiconductors. (1.15 the dependence of the conductivity on temperature is shown for very pure silicon and germanium samples. the doped semiconductor materials are called extrinsic semiconductors. semiconductors. save that the values for cro and E. As an example we choose silicon.17) This conjecture is confirmed by experiment.5 yield the electhen tron concentrations of semiconductors and insulators listed in this table. 1. k is the Boltzmann constant and Eg is an energy of about 0. In this context. should be more or less the same: P M E E? P S C =” P I S . between lo-’ 0-l c m . but variations by several orders of magnitude are very unlikely. the conductivity values in Table 1.7 eV in the case of germanium and 1. namely to intentionally pollute it with atoms of certain chemical elements. must be changed.4. firstly. respectively. Considering first the change of the conductivity with temperature. By ‘state‘ we mean.1. If one assumes for metals one free electron per atom. as one might suppose.18) also describes the temperature dependence of the conductivity for other pure semiconductor materials fairly well at sufficiently high temperatures. In Figure 1. The conductivity increases with rising temperature according to the exponential law (1. and consequently it follows that the large conductivity differences between the three material groups are essentially due to their different electron concentrations. and secondly the Concentrations of certain impurities. There is a second way of varying the conductivity of a semiconductor over a wide range.1el’ in the case of silicon. psc and in normal metals. and insulators. we note that it is particularly pronounced if the semiconductor contains practically no impurities .4. semiconductors and insulators.18) Here. doped with arsenic a t o m . of course. but is primarily due to the fact that a given semiconductor material covers the entire range of cr-values by itself if its macroscopic state is varied.l and lo3 R-’ m-’ . differences with respect to the strengths of these processes in metals.6 the &. does not arise. IlIacrascopic properties and their microscopic implications 35 pecks.

27 GaAs 1.56 ZnSe 2. (Ajter Figure 1.14 IrlSb 0.8 Te 0.) Material E.95 AlN AIP 2.y u of As-doped Si a t 1 = 300 X ' an tlic arsenic concentration ~VD.15: Temperature dependence of the conductivity a of very pure (intrinsic) Ge and Si. (After Epzianov.O-SiC 2. Characterization of semiconductors Figure 1. GaN 3.0 .(Aftar Lundoldt-Bumstein.66 . Again.36 3.71 Iiub 0.37 0. 1954.33 0.2 InN 1.2 BN 6.16: Dependence of the conduc tivit.) Morin and Makta. the conductivity rises monotonically with doping ronrrntration.6: E.16 the change of conductivity is shown with N o varying from 1014 up to crnA3.30 GaP 2. In Figure 1.26 Material E. a change of several orders of magnitude i s exhibited. At temperature 300 K corraponding to the data of Figure 1.16. Table 1.50 CdTe 1.-values for several semiconductor materials at 300 K (in eV).45 AlAs 3.5 6.11 Ge 0. Material E.36 Chapter 1.26 03 .18 AlSb 1.00 PbS PbSe PbTe Se 1. 1979.63 ZnS 1 5.28 IriP 1.67 CdS 2.1 of concentration N D . 1982.43 HgTe 0.43 (Mh 0. C: Si 1.

Each curv-e in this figure corresponds to a particular concentration of arsenic atoms.} b The trmperalurr dependence of the conductivity is substantially weaker for doped silicon than for pure as may be seen from Figure 1.15). 195d. and for the highest doping it completely vanishes.2.7x lo1’ cm ’.5-2. In this regard.3 x 1017.17: Temperature dependence of conductivity u of As-doped silicon for different arsenic concentrations N D : 1 1.1.31. The rise of curve 1 above 400 K indicates thcrt the corresponding [relatively pure) material starts to behave like an intrinsic semiconductor (see Figure 1.4.75 x 101*. The temperature rise becomes weaker with increasing doping. (After Morin and Maita.17. namely optical absorption. The origin of the difference i temperature characteristics of the conn ductivity of pure and d o p d semiconductors remains to be addressed. z . .1 1015.4-1. At higher temperatures. Macroscopic properties and their microscopic implications 37 Figure 1.75 x 1014.6-2. it even turns downward in a decrease that is more pronounced for purer materials.2 x 101B. it will be helpful to discuss yet another rnacrosropic property of semiconductors.

18: Absorption coefficient a of Si BS II fimction of photon energy Bw. lhen its energy increases to the value E . The absorption hw is in the allowed range can. are allowed.18 showing a ( h w ) as a function of the photon energy hw.38 Chapter 1 . can be explained if the energy values between E. (Ajter Philipp and Taft. of electron energies. The representation of these values as a function + + + . . that an intimate relation i s strongly suggested.e. i s characteristic of all semiconductors. the vaniahing of absorption for E < E .3 Optical absorption spectrum and the band model of semiconductors The measured values of the absorption coefficient of silicon are displayed in Figure 1. be the maximum energy which an electron may have m such a semiconductor. in semiconductors. The values of the optical threshold energies coincide so well with the Eg-values known from the temperature dependence of the electrical conductivity (see Table L6). Characterization of semiconductors Figure 1. hw. Consider a semiconductor in thermodynamic equilibrium at absolute zero temperature. If an electron of that energy absorbs a photon of energy h w . the steep rise at this energy up to valurb which are larger by orders of magnitude. For atoms these are the energies corresponding to the various Bohr orbitals. however.19. if the energy values E' > E. In turn. and absorbing above it. The particular shape of this spectrum.. and the weak decrease from these high values with further increase of photon energy. 1960. only occur if the energy E. absorption may be non-vanishing ' abovc h g only if the electrons can take energy values E > E . and let E. i. but only specific energies which are eigenvalues of the Hamiltonian. Thus. one may say that semiconductors are transparent below the threshold photon energy. It is well-known that in quantum mechanics not all energies arc allowed. namely the vanishing of a below a threshold energy.E* E. Such a distribution of allow4 energy values is shown schematically in Figure 1.4. In simplified terms. Below we will analyze this relation in greater detail.) f 100 -' 10-2~ 1 2 ' 4 I 102040 hw/eV I ' m m ' I - 1. and & are forbidden.

.19: Ordering of the allowed e n e r a v d i m o an ideal semicnnducf tor (band model). and the upper is the conduction band. Macroscopic properties and their microscopicimpIications 39 Valence bond O0 X--- H L 0 1 f [El--) Figure 1. The regions with closely clustered allowed energy values and electron states extended over the whole crystal are called energy bands. and EF has been set at E. for the explanation of the observed absorption spectrum of semiconductors.20: Fermi distribution function f ( E ) as a function of energy at different temperat#ur&. T h e spatial extension of the corresponding electron states is also illtlstrnted. then no electron could be excited tu this band. A straight line across the whole crystal from 0 to d means that the electron at this energy is spread out over the whole crystal. If there were no electrons available with energies in the valence band. according t o the P a d exclusion principle. on the other hand. the conduction band could host no further electrons.I . Between these two bands lies a region of forbidden energy values. called the forbidden zone or the energy gap. The existence of energy bands done is not in itself siifficient.The energy unit is E. The lower band in Figure 1. all states of the conduction band were to be occupied.4. then there would &o be no electrons to absorb a photon to make the transition to the conduction band possible. For this it i also necessary that the valence band be occupied by electrons s and the conduction band be empty.. however. If. Figure 1. of electron coordinate is intended to illustrate the degree of localization of the electron.P.19 is the valcrice band. and no photon absorb4 in such a transition since.

EFI >> k T . The probability of orcupation of a particular energy value E: depends decisively on the relative position of E with respect to the Fermi energy. If. A more detailed treatment of the Fermi distribution function will he given in Chapter 4.E F J>> kT. on the contrary. The shape of f(E)is shown schematically in Figure 1. and in addition J E.20 we have also implied that Pi. lies below E F and E. E > E F and again IE . This function represents the probability of finding an electron in an energy levcl E . Qccesionally. The width of the e n e r a region where the transition horn 1 to 0 takes place is cf the order of magnitude kT. on the right for T > 0 K. Characterization of semiconductors 0 0 X - L 0 X L 4 Figure 1. the more abrupt this transition becomes. 111 Figure 1. above E F . The population of energy levels by electrons at equilibrium is determined by the lkrrnz distribution f i n r t i o n f ( B ) . On the left for T = 0 K . then f ( E ) is approximately zero. This means that . Like temperature. the Fermi energy is an intensive thermodynamic state variable.19) Here E F is the so-calld Fwmz mevyy.40 Chapter I . and it is given by the expression (1.20. If E < E F holds. which melts at higher temperatures. namely the free enthalpy per particle or the chemical potential. At T = 0 K thc transition is steplike. one says that f(E) has the form of an ‘iceblock’ at T 0 K . The lower the temperature.21: Distribution of electrons of an ideal semiconductor over the valence and conduction bands.then f ( R ) essentially has the value 1. in order for the valence bend to be almost completely occupied and the conduction band to be almost empty.

. 1 4 4 Electrical conductivity in the band model . sufficiently far away from the two band edges (measured in units of kT). In this. 0 X--L L the Fermi energy must be located within the energy gap between Ev and E. but the gap of insulators is typically larger than that of semiconductors.22: Absorption of photons by electron transitions from vaIence to conduction band.. The explanation is illustrated in Figure 1. the Fermi levels are found in the energy gap in both cases. This means that the strong exponential T-dependence of CT must be due to the electron concentration IZ. The electrons are distributed over the two bands as shown in Figure 1. We will now show that the temperature dependence of the electric conductivity of pme semiconductors also follows from the energy band scheme discussed above and the position of the Fermi level in it. In metals the Fermi level l e within the is conduction band. in essence. one has an insulator.21. T .5 e V . Insulators do not differ from semiconductors qualitatively with respect to their Fermi level positions.18. Again.1.. Their Fermi level lies in the energy gap between the valence and conduction bands. This knowledge provides a complete explanation of the absorption spectrum in Figure 1. If Eg > 3.22 and needs no further comment.e. we have described an essential microscopic property of pure semiconductors. hfacroscopic properties and their microscopic implications 41 Figure 1. The differences in the properties of semiconductors and metals may be traced back. i.4. we employ the relation u = enp. The mobility p can be assumed to be a relatively weakly varying function of temperature. as a rule. to the different positions of the Fermi levels in these two different types of materials.

Their concentration can be easily calculated.21) into the integrand of (1.21) The concentration of energy levels in the conduction band having energies between E and E dE is p c ( E ) d E . Since all valence states are occupied. This means that the T = 0 K state will remain unchanged in 8 1 electric Eeld.23) where (1.24) . the electrons of intrinsic semiconductors are statistically dip tributed over the valence and conduction bands in accordance with the Fermi distribution function f(E). where pc(E) is the so-called density of states of the conduction band. f i. As we know.42 Chapter 1. In Chapter 2 we will calculate this quantity explicitly. Characterization of semiconductors and comparison with equation (1. The reason for this is again the Pauli principlc. in the Fermi distribution function j ( E ) of ecpation (l.~ depending weakly on temperature. according t o which an electron state may be occupied by only one electron. For a pure semiconductor Ec . energies with E > EC Iu so doing. here its mere existence suffices. and x consequently no current will flow. the Boltzmann distribution function 7 (1. which describes the number of states per unit energy and unit volume. In terms of p . one obtains. approximately (1.e.20) with n o as a factor of dimension ~ r n . approximately.ing the electrons. no stste change is possible in the valence band by redistribut.22) If one substitutes f(E)from (1. a current will arise from the relatively few clectrons which.EF > 6T holds. according to thc Fermi distribution function: are populating the conduction band at ftnite temperature. The electrons in the fully occupied valence band cannot contribute to carrier transport.out3 m a y neglect the ‘1’ o the denominator for emrgies E in the conduction band. However. and the conduction band is completely empty. it follows that (1. ( E ) one may write the electron concentration n of the conduction band in the form + (1.18j yields. At T 0 K the valence band is fully occupied.l!J). > Thus.221.

finite temperatures. For this reason. namely the fifth valence elcctron of an arsenic atom replacing a silicon atom having only four valence electrons (see Figure 1. At temperature T = 0 K each of these levels is occupied by one dectron. Strictly speaking.ian hand edge.23) for n. Another inaccuracy of the above consideration that. then the conductivity becomes independent of T. Macroscopic properties and their microscopic implications 43 may be understood as the effectiae density of states of the conduction band. Wc will later prove (see Chapter 3) that each of the arsenic impurity atoms g i v ~ to an energy level in the rise forbidden gap. The temperature dependence of this contribution is roughly the same as that of the conduction band. we will first clarify how one may understand the strong change of conductivity with impurity concentration in extrinsic semiconductors. i. however.e.19 for an ides1 semiconductor. we have marked these levels in Figure 1. The corrections at higher temperatures are.23). The electric charge transport due to the electrons of a not-completely-occupied valence band will be considered more fully later. E F = Ev 1 + -E 2 g ' (1. which we will discuss below. become freely mobile electrons (see Figure 1.20) and (1. the Ferini level lies exactly in the middle between the valence and condiistion bands.E F )= Eg/2. one has R = N D .1. these electrons are excited into the conduction band.e. just below the conduct.16 and 1. then this model has to be altered. For this purpose we again m e the energy band model of Figure 1. If arsenic impurity atoms are present in a silicon crystal. we or identify no = N . the valence band population also changes.he electrons of the valence band also make a contribution to the current. If temperature i s increased. However. then practically all arsenic atoms are ionized and the concentration n of free electrons is equal to the that of the arsenic atoms.24) which can contribute to transport. bound electrons which formerly could not participate in carrier transport. If the carrier which at sufficiently high temperatures T i s concentration has Ihe value NLI> actually the caw. and they can bc ignored here.4. In this way. this is only true for T = 0 K .25) i. If the concentration N D of arsenic atoms is not too large: and the temperature 7' not too law. It is this relatively weak temperature effect which shows up . quite smaI1. Under these circumstances t.17. The only remaining source of a temperature dependence for u is the T-dependence of the mobility p. This corresponds to the approximate proportionality between cr and N o observed in Figures 1.23 by short line segments. and that the electrons in these levels are localized at the site of the impurity atom. To ensure the consistency of the expressions (1. as we will see later. we have ignored is that. and ( E c . so that no longer are all states of this band ocmpied. It is connetted with a remarkable observation of the Hall effect. at.

I n t a. OIL the right for T > 0 K . With this. We now proceed to the Hall effect.44 Figure 1. 7 . T-0 T. G Eg a P W W 2 a I 0 0 X--c L in Figure 1.17 at high T . at least in principle. Distribution of the electrons of a silicon crystal doped with arsenic over the allowed energy values.23: Ordering of the allowed energy values of electrons in a silicon crys- tal doped with arsonic (schematically). Each arsenic atom correspond# to 1 locslized energy level.24. 011the left for T 0 K . the experimental observations relating to carrier transport in semiconductors are explained microscopically.0 0 XX - L Figure 1.

25). For both samples it has the same direction. with different types of doping. a current component I H perpendicular to both the electric field E and the magneliu field B will arise. To be specific. Consider. 1. as shown in Figure 1. the Hall effect will be observed in such circumstances. we assume two silicon samples.5 The Hall effect and the existence of positively charged freely mobile carriers We consider two semiconductor samples of the extrinsic type hoth madf of the Same material. one doped with phosphorus as a group V dement. 2 5 ~and d). Gnder the wndilforts . the ~ I I I P two sarriples in a niagnPtic Geld B ( ~ e e Figure 1 . namely from '+' to '-'. As is well-known.25: nlrlstration of the Hall effect in two silicon smrples.45 *)U 1Phosphorus doped Si Current 4 ua) Current- Boron doped Si Current - Current- bl Phosphorus doped Si ~ a i current i H ~ Icurrent I + Cl HOII current + fie'd Hall current d) Figurc 1.e. i.25a and b. ROW. however.4. Applying a voltage to both samples. and the other with boron. a current I will Bow. and the other with bnroii as a group 111 element (see Figiiie 1. one doped with phosphorus.

but by positive ones.as we will do later explicitly . The Hall effect can also be measured in metals. This means that the corresponding Hall currents flow in opposite directions. which depends directly on the sign of the charge. has. then the Hall current flows upwards in the boron-doped sample. leaving behind unoccupied states. and the boron atonis are electrically neutral. If we assume that the magnetic field is directed normal to the plane of the figure and that it points into this plane. For the boron-doped sample this means a Hall current directed upwards.that boron atoms whi& substitute silicon atoms in tf silicon crystal.46 Chapter 1. namely upwards. give rise to energy levels in the forbidden zone just above the valence band edge.experiences the Lorentz force F=4[vxS]. the Lorentz force F. or occupation hole3 in the valence band. C (1. Characterization of semiconductors of Figure 1. the current in the boron-doped sample is not carried by negative charge carriers but by positive ones. At very low temperatures these states are not occupied. but in the phosphorusdoped sample the Hall current is downwards. This is illustrated in Figure 1. At finite temperatures electrons from the valence band are excited into the boron levels (Figure 1. We . in addition to the electrons as negative freely mobile charge carriers. In other words. and therefore there will be a voltage UH such that the current caused by it will just compensate the Hall current. in contrast to metals and the phosphorus-doped silicon sample. In this way the experimental observations of the Hall effect reveal a remarkable general property of semicondiictors: For doping with certain atoms. In this case the direction of the Hall current is the same as in the silicon sample doped with phospho- How can the dlfemnt behauiior o thesiicon sample dupd with born f be understood? The explanation is quite clear if one assumes that. Experimentally one finds that the Hall voltage UH has different polarities in the two samples. Electrons in such energy levels are localized at the sites of the boron atoms.26) Since negative charges move to the left. for both charge signs the same direction. the current is not carried by negative charges as one would expect considering the negative charge of electrons.27).25 no current can flow in this direction.25d. since in this case the charge carriers are negative. A charge q . This is illustrated in Figure 1. This is just the observed behavior. which means that the assumption of positive freely mobile charge carriers is successful in explaining the unusual sign of the Hall current in boron-doped silicon. which moves with velocity v in a magnetic field B. One may This surprising observation may be understood as ~OUQWS. and downward in the phosphorus-doped one. demonstrate .26. one also has positive ones in semiconductors under certain conditions. and positive ones to the right.

the hole is at the outermost left position. Each boron atom corresponds to 1 locali d energy level. Rut only the electron neighboring the hole on its right hand side can follow this force. whether they are electrons or holes. placed at the upper band edge. In the first case one speaks of a n-typr semzcondurtov (the n stands for ‘negative’). 111 the next time interval this process is repeated. As we have seen above. The population of the bend edge is shown in Figure 1. The electron immediately on the right hand side of the hole. The antranszc semiconductors intro- . moves into the hole and leaves behind another hole to the right of the first one. the sign of the Hall voltage tells one whether the free carriers of an extrinsic semiconductor are negatively or positively charged. in the second of a p-type semarondector ( p for ‘positive’).26: Ordering of the allowed energy values of electrons in a silicon crystal doped with boron (schematically). Macroscopic properties and their microscopic implications 47 Figure 1. Le. since all other electrons are blocked because the states to their left are already occupied.28 at different points of time. This qualitative introduction of the concept of holes will later be elaborated by more quantitative considerations. t immediately recognize that these occupation holes of the valence band behave jubt like freely mobile positive charge carriers in an applied electric field. At the beginning. This is illustrated in Figure 1. Thus. For simplicity only one hole is assumed to be in an otherwisr rompletely occupied valence band. The hole has thus moved one site further to the right in this way. in an electric field. and the hole again moves one site further to the right etc. holes in the valence band behave like freely mobile positive charge carriers. as if carrying a positive charge. The adjacent electrons experience a force which tends to move them to tho left.4. but in the opposite dirwtion. the hole moves like a freely mobile electron. In summary.1.28.

a few electrons occur in p t y p e materials with mob1 of the carriers being holes. Holes are also present in n-type semiconductors.rons of allowed energy values. in very small numbers compared to elwtrons. but. Analogously. The Hall effect can also be used for purposes other than the determination of whethrr an extrinsic semiconductor is n. Their mobile electrons arr generated by thermal excitation of bound electrons from the valence band to the rondiiction band.48 Chapter 1. Their number is equal to that of the mobile electrons. a silicon crystal doped with boron over Figure 1.or p-type. Since each excited electron leaves behind a hole in the valence bmd.28: Empty states (halefi) in Ihe valence band behaye like freely mobile poriitive charge carriem in an electric field. one also has mobile holes in intrinsic semiconductors.27: Distribution of elect. One calls the many mobile carriers of extrinsic semiconductors m a j o n l y cariwrs and the few mobile carriers mzrrortty earners. Characterization d semiconductors L X- 0 X- 1 Figure 1. The absolute . duced earlier haw neither electrons nor holes from impurity atoms.

which permits us l o rewrite equation (1.27) This is the same force caused by the electric field E ~ I F/(-e). 'far' means that characteristic macroscopic propexties of the semiconductor deviate strongly from those in equilibrium. assuming realistic conditions. Thin. in accordance with the relatively low carrier concentration of an intrinsic semiconductor in thermodynamic equilibrium. We will veTify this assertion for an n . Evidently. When the exposure of the sample t o light ceases. shielded against unwanted influence of light. We can write an analogous expression for holes. With b as the width of the sample normal to j and 3.26) as F=-[j RC 1 X B ] .28) where Rff = PrtC 1 (1. However. onr ran also det.t y p ~semicondiictor. expression below for U x the follows: (1.22). its conductivity decreases to the original low dark value. 1. hy measuring thc Hall vultagr.29. Here. electrons in the conduction band and holes in the valence band were created by irradiation with light to such an extent that their equilibrium values were exceeded by orders of magnitude. If. depending on the intensity of the light and the magnitude of the absorption coefficient. In this case the rurrcnt density j can be expressed in the form j =. one obtains a relatively small value. A simple estimate for Figure 1. (1. This is shown schematically in Figure 1. we examine the example of photo-conduction. However. Consider a sample of an intrinsic semironductor. To be more specific about these qualitative statements. only the electron concentration has to be replaced by the hole concentration p . in this 'dark state' the conductivity is measured.29) is the so-called Hall constant. The = voltage corresponding t.. if one irradiates the sample with light which is absorbed by the semiconductor (see Figure 1.4.ermine the majority carrier concentration. semiconductors may easily be driven into states far from equilibrium.29 .valup of the Hall voltage determines the concentration of majority carriers.o EH is by dehition the Hall voltage Ufi.6 Semiconductors far from thermodynamic equilibrium All properties considered hitherto were for semiconductors in a state of thermodynamic equilibrium or in close proximity.--env. the conductivity will rise more or less strongly.

1M . their niodifications by impurity atoms and other deviations from the ideal crystal. semiconductor which previously had been isolated by a thin insulating layer from one of the electrodes. 6 and 7. The ability to c r e at. thermodynamic equilibrium i s reestablished by so-called wxnnbinaiion. -by light of intensity 10 Wcm-'. Almost all applicat. This applies to the stationary electron states of an ideal semiconductor (Chapt. 'lhis follows from the fact that continuous irradiation leads to tt stalionary conductivity value. the basic concept.%ers. from the observat. In the first part of the book. such as electric rect.? extreme non-equilibrium states in semiconductors i s extensively used in electsonic devices. will be developed from first principles. and. discussed above in a heuristic way. Rwidr irradiation with light.ime.50 Chapter 1. will be dealt with in the second part of this book. as well as by external fields (Chapter 3) and t h e statistical distribution of charge carriers over aiergy levels in thermodynamic equilibrium (Chapter 4). Non-equilibrium processes in semiconductors and the most important scmiconductor devices based o n them.he carrier concentration was increased from about 10'' cm4 (equilibrium value) up to c ~ n . tunnel diodes. bipolar and unipolar transistors.er 2). on the other hand. or by applying voltage to a.~ 1~-7 - 10-4 I I I 10-3 lo-7 10-1 ma r]' I h o t t om* --+ shows that t.s. .29: Conductivity of an intrinsic semiconductor irradiated with light as a function of intensity I of the absorbed radiation (schematically). by putting an n-type semiconductor in contact with a p t y p e semiconductor or with a metal. The 1at. i. extreme nun-equilibrium states in semiconductors can also be created in other ways. Characterization of semiconductors Figiire 1. The ~ electron-hole pairs created by the radiation decay. photodetectmu: solar cells. after a short t.ionthat the conducbjvity decays down to the dark value after switching off the light source.ter observat. for example. p7nuesses. and lienre a constant carricr concentration. as well as luminescence and laser diodes. in Chapters 5 . however.ionsof semiconductors in such devices rest on this uniquc pQssibility-.ion means that.e.

but the resulting states.e. This is immediately understandable if one imagines that the crystal is grown from the gas phase.4. The substance of this subject is summed up under the designation electronic structure. We will show how the simple model of electronic structure of a crystal. In this process the electron states of the atoms will change. Whether. the electron states of the crystal will also depend on the initial electron states of the isolated atoms prior to crystal formation. of course. the valence electrons. and to what extent the electrons of the inner shells also change their states. by chemical bonding of previously isolated individual atoms. the kind of changes contemplated may be characterized as follows: There is no doubt that the electrons of the outer shells. is harder to predict. 21 . i. at least for those inner shells which lie much lower energetically than the valence shells (Ta- .51 Chapter 2 Electronic structure of ideal crystals In sections 1. Atomic cores and valence electrons Qualitatively. for they are the primary agents which bind the atoms into the crystal state (Table 2. It will also be seen that the eigenstates of electrons in a crystal devolve upon the electron states of the free unbound atoms.e. i.2 and 1.e. One may suppose that such inner shell changes will be comparatively slight. The periodic ordering of the atoms of a crystal in space is crucial for this proof.3 of the preceding chapter we discussed the spatial order and chemical nature of the atoms in ideal semiconductor crystals. which we heuristically introduced in section 1.1). the energy band model. can be rigorously deduced from the Schrodinger equation. i. The present chapter is focused on the quantum mechanical energy eigenvalues and corresponding eigenstates of electrons in such crystals. will react most strongly in assembling the isolated atoms of a crystal.

dnd in this regard the pertinent feature is that the wavefunctions of the inner shcll plectrons 01 the atoms in the crystal undeigo only weak changes. This allows one to consider the atomic nuclei and . Therefore.the states of the electrons of the inner shells and those of IhenucIeoas frequently do not change. In B way. the inner electrotla threby serve as probes. this means that the wavefunctions of these electrons are essentially unaltered. they feel potential changes produced by siirrouuding atoms as being almost uniform.1: Characterization of atomic cores and valence electrons of main group elements from which semiconducting mat. By measuring these shifts m e can obtain information about the chemical nature and geometric striicturc of the environnient of an atom in B solid. however. specifically by the change of the constant potential value arross their localization region. which remain practically unaffected. Atom Nucleus Core Core electrons Valenw electrons B C N 6+ 5+ 18 222p 2922p2 2s22p3 323p 132222p6 323p2 3s23p3 7f A1 St 14+ 13+ 153 1+ P Ga 424p ls22s22p633s23p63d10 3s24p2 4Ap3 Ge AS 323 3+ ble 2.2). as a rule. can be assumcd to be the same as those of the free atoms.erialsmay be formed. The term d i d d a t P shtjts is iised for t h e s ~ shifts of the inner electron levels. in determining the elertronic stricture of sanironductor crystals and the influence of exterruel perturbations on them.52 Chapter 2. This statement is even better justifid for the wavefiinctions of the nucleons in the atomic nuclei. Because the electrons of these deep shells are localized so close to tlirir rrspertive nuclei. elwtromagnetir fields . Their eneqy levels shift. if the gown crystal is expoard to certain extrrrial perturbations . Here. the states of the inner electron shells and those of thc nuclei. we arc intermtd in the electronic strizrture of crystals. prrssure. Strictly speaking. Electronic structure of id& crystsls Table 2.heat. this is even generally true. Furthermore. For the e x h n a l perturbations which are of p r i m interest in semiconductor physics.

1963.ure which is fundamental for the further analysis . In this case the d-electrons significantly participate in chemical bonding and can no longer be included in t. whose intrrnal structure i s of no further interest sirire it does nut change. Somctirnes one refers to this concept.8 the inner shcll drrctruns jointly as subsystems of the crystal. the inner shell eledrons of crystals can be excited by means of electromagnetic radiation in thc far UV and X-ray region.4 31.9 95 . In this sense t. 03 20.9 11.al as system composed of at.5 13.o the oubar valence shells (see Tables 2. (Afcer Herm.5 17. Atomic cores and valence eJectrons 53 Table 2.9 Si 6.) Atom -tp 3 6.an. All energies are given in el/.5 -.he inner &shells are. generally prevails. and SkiIlman.the picture of a cryst. rather close t.1 Ga 4. t.ic ~ 0 : ~ s . 3.4 S 1.2: Energy levels -E.iou.1 the division into core8 and valence electrons is indicated for some elements from which semiconductor crystals arc made. energetically. .7 5.2 8.o them as atom.5 5.5 195 C N 0 14. Moreowr.hc subsystcms composed of atomic iuiclei and inner electrons are elementary building blocks of the crystal.1 405 537 10.3 17. and -4 of the valence electrons and .0 29. as the frozen-core a p p ~ ~ ~ i i m Int i ~ ~ ~ a Table 2.1 147. In heavy metals such like zinc.5 P 8.4 20.he core. t 23.1.4 7. This can also occur by means of an electron beam In solid state nuclear reactions.2). Since the crystal aIso contains valence electrons as independent particles. One rekm t.1 A1 4.4 4.6 3.E .9 7. of the shallouwt core electrons for some chemical elements which may occur in semiconducting materials.omiccores and valence electrons. we arrivr at a yic:i.00 11.8 Zn 3.2. but as always. The structure is.6 12. there arc exceptions. The frozen nature of the electron states of the cores of a crystal! and their lack of rcsponse to external influences. frozen.7 -ec 291 116 182 -cP 6. so to speak. ~ W R the states of the nuclei of the crystal atoms change.7 9. which is iinchangeahle by definit.1 and 2.6 8.1 87.

G a with G a large integer.6. we imagine the infinite crystal to be divided into parallelepipeds of macroscopic size in such a way.only finite sets of J cores and N valence electrons need be considered. The crystal itself was imagined to extend to infinity. In this way. as was done before. Electronic structure of ideal crystals 2. First. Second. and it suffices to describe the motion of the J cores and N electrons of this particular region. is now no longer assumed to be empty.. Of all possible motions of the particles of the infinite crystal. of course. we replace the point-like picture of atoms by introducing spatially extended atomic cores and take their centers of gravity as the atom sites. the cores.e. we now select those particular ones for which the cores and electrons in different periodicity regions have the same positions relative to the origin of their own region. we also account for the fact that the atomic cores in crystals can execute oscillations around their equilibrium positions. that their edges are parallel to the primitive lattice vectors a. Thirdly. Both should start with 1 and run upwards. specifically at points which are consistent with the existence of a lattice and a unit cell. and that only these equilibrium positions form an ideal crystal. If the periodicity regions are made s a - . In this way the infinite crystal becomes a periodic continuation of one particular periodicity region. but we acknowledge that valence electrons are present there. We now consider a more realistic model of a crystal. and also have the same speeds. and the valence electrons by an integer subindex d.. we recognize that the centers of gravity can also move to other positions than those prescribed for the ideal crystal. The assumption of infinite extension of the crystal which. One calls these parallelepipeds periodicity regions. To understand this. Gaz. reaching arbitrarily large values since we are considering an infinite crystal. In dealing with the atomic structure of crystals in Chapter 1. As far as the electrons are concerned. By means of a conceptual device which we are about to introduce notwithstanding the infinite extent of the crystal . will be addressed at a later stage. the space between the massive elements of the crystal.2 The dynamical problem Schrodinger equation for the interacting core and valence electron system 221 . is also not exact. these effects are treated in section 3. In this. i. These edges are to be given by the vectors Gal.54 Chapter 2. we found that their atoms are not located at arbitrary positions but at well d e h d locations. The atomic cores will be marked by an integer subindex 3 .az. Each of these parallelepipeds should contain an equal number J of cores and N of electrons. the atoms were assumed to be point-like and the space between them was empty.W of the crystal. This assumption excludes effects due to the existence of bounding surfaces.

so most of the Mj-values are identical. which is further assumed to be point-like {see Figure 2. Of course.The j-th core mass will be denoted by Mj. The momentum of the j-th core is called P3. and x for the position of the i-th electron. which can only be adequately treated by m a s of quantum mechanics.and that of the i-th electron pi. The dynamical problem 55 L 0 / . In the case of electrons we can omit the index i from their masses since they have the common mass m. there are only as many dif€erent values of M j as there are chemically different types of atoms in the crystal. The state of the particles in the remaining periodicity regions can then be described by means of a periodic continuation of this function. The state of the system is described by a en i wavefunction @. it suffices to consider @ as a function of the coordinates xi of the N-electrons and the coordinates Xj of the J cores of only one periodicity region.e. Since we assume periodicity of the motion with respect to a periodicity region. which depends-on the coordinates x of all electrons and Xj of all atomic cores. ciently large. by means of the relation . as well as on the time t.1). The concept of the periodicity region makes it possible to pass from the original infinite space problem of motion to a finite one without thereby losing the translational symmetry of the infinite crystal. We use Xj t o denote the center-of-mass coordinates of the j-th atomic i core. i. + 0 \ 0 Figure 2.2. such that We are interested in the motion of the interacting atomic cores and valence electrons of the infinite crystal. they will encompass all types of motions of an infinite crystal with desired accuracy.1: 13escription of the positiom o the atomic cores ( 0 ) and valence elm f trons {a) {left part) as well as the interactions between these particles (right part).2.

X N . 2 . x1. ‘H =. . % : C . Electronic structure of ideal crystals G. v t = vec(X1. . It depends only on the locations of the atomic cores. (3) The mutual interaction of cores. which at sufficiently large distances is again of Coulomb type. it is evidently additive. . . we define V ( X ~ .6) where Vc(xi. energy will be denoted by V. X2 t G&. X i . . x ..XJ). We will now wt up the Hamiltonian 7-l of the system of the N-electrons and J atomic cores of a periodicity region. . as given by (2) The interaction of the electrons with the atomic cores due to their mutually attractive Coulomb forces. The corresponding potential encrgy is denoted by Vce. ran be expressed in terms of the momenta Pj and pa of the cores and electrons as fOllOW8: (2. XJ) to be the potential energy of the system. XI 1 C%. .. repulsive forces of quantum mechanical origin also occur. . e 1 . The electron-core interaction potential energy V. .. and xz. (2. a..X J t G+. which become effective if the valence electron wavefunctions overlap the inner electron shells of the atomic cores.x2.3) The kinetic energies Xc and T.XN. . i. depends on the locations of both the electrons and cores. . t ) with CY 1 . . . and also due to (repulsive) forces of quantum mechanical origin. . .. . x2. . X2. . .Tc Te + + V.e. XJ) is the potential energy of the i-th electron in the field of all cores. . If the distances become small. . The core-core interaction potential . It depends only on the coordinates of the electrons.1): (1) ‘lhe repulsive Coulomb interaction of the electrons with each other. With respect to the electrons. We use Tc and ‘reto denote the kinetic energies of the atomic cores and of the electrons. X I . . respectively.XZ.e. The Harniltonian is the sum of the kinetic and potential energy operators. .X2. . .4) The potential energy is due to three interactions (see Figure 2. 3 . XN i G%.56 @(XI I Chapter 2. .. ~ x2 1 . XJ)= I vc (xz. (2. i.

8) which determines the dynamical problem of the crystal uniquely. . e.2 Adiabatic approximat ion. The dynamical problem 57 vcc VCr(X1. and in mercury 368 thousand times. on average. Fat whose solution may be determined in terms of the eigeiivalue problem for the Hamilt. . In addition.onittn 7f. a system with about 10” electrons and a similar number of atomic cores.11) Attempts to solve this eigenvalue problem exactly are hopeless from the very beginning. . XN. . XL ’ ‘ ’ 9 XJ). We begin with the adiabatic approximation. d 3 x J p q X 1 . i.. .in Si. it takes advantage of the fact that in a crystal the kinetic energy of an atomic core is. and secondly. (2.7). allow for a proper decoupling of the electron and core motions. . because it involves a macroscopic system. the motions of which are mutually coupled in a rather complex way. Lattice dynamics The adiabatic approximation (also known as the Born-Oppenheimer approximation) is based on the fact that the mass of the atomic cores is many tens of thousands of times larger than that of the electrons . .7) Summing the three potential parts (2. . and the first by the ‘one-particle approximation’.X I . t (2. 2. This problem i s described by the time-dependent Schrodinger equation i3 i Le = H6. 52 thousand times.6) and (2. .2. These two approximations will be elaborated below. . . (2. + v. xZ.e..x2. %IJ! = EQ. . and in the course of the discussion it will also become clear how the somewhat unexpected designation of the latter arises. which is given by the time-independenl Schrodinger equation v - v + v. (2. one gets the total potential (2.10) The normalization condition for the wavefunction with refereiicc to a pcriodicity region is (@I*) d3X1.g. One must therefore resort to approximations. Such approximations must first provide the means to reduce the gigantic number of electrons. The second simplification is achieved by the so-called ‘adiabatic approximation’.2. .5). xj.2.) l 2 = 1.

This observation plays an important role in the following considerations.16) . (X\. one may say that.15) The necessary normalization (2. X N )by x. This remains true when the interactions between the electrons and coresi which were omitted above./2) X > and (m/2) < x > as the < : : avrragP kinetic enmgies of a core and an electron in a crystal.~ the Frrmi e n e r a EF i~of the order of m~gnit~ude e V . 'l'his can be seen in the following way: If the cores and valence electrons were fwe particles.. That of a valencp dzctron would be about (3/6) Eli where E F is defined as the Fwmi energy of an electron gas of the same density.XJ) X.12) (2. The average kinetic energy of a core is therefore generally smdlcr than that of an electron. . x = (XI. I . we write by x = (XI. on statistical average. The daerence between the average kinetic energies of the two types of particles arises from the fact that the electrons obey Fermi statistics.10) for the total crystal. we thus have -2 X j > < and it. XJ). in the form of a product q x . and the J-component sequence of vectors x2. . For typical concentrations of valence electrons in a crystal of about 10" C W L .Xz. XN). i. follows that Mj < -<xq>.58 Chapter 2. then the average kinetic e n p r o of a core would be approximately (3/2) h7'. To simplify the notation.. ie. . .e. X ) ' @(XI. . .11) of the total wavefunction *(x.e. i.xz. we replace the N-component sequence o€ the vectors (XI. ' (2. . 2 1 7 1 .X ) = $(x...15) is normalized with respect to this region. X) with respect to a periodicity region is assured if each oI the two factors of (2.. whereas atomic cores obey Boltzmann statistics.14) To take advantage of the slow motion of the cores we write the solution q{x.X) of the Schrodinger equation (2. if they did not interact. are taken into account. if (2. Writing (M. . xz.1 eV below the melt of mg point of the crystal. (2. Electronic structure of ideal cry&& smaller than that of a valence electron. (2. the cores move much slower than the electrons.13) Corrmpondingly. while kT reaches only about 0.

2.2) of @(x. Yet without any approximation we have [ e Tc + K . if the identity ($’4’lTe + T + v&ec + Vccl$. we have set and U(X)is in the nature of an electron energy eigenvaliie. The dynarnical problem 59 (2.X) 4(X)separately.e. .17) are assumed. X).the adiabatic approximation which was mentioned above. X)4(X).4) between Tc and the squares Pj of core momenta.. Secondly.20) forms an orthonormalized basis set in the Hilbert space of the crystal.2. To assure overall periodicity with respect to a periodicity and region we assume it for +(x.. X).15) satisfy a Schrodinger equation in which the coordinates of electrons do not appear. and applying the product rule for differentiation we get. for brevity. we assume that $(xiX)is the solution of a Schrodinger equation for electrons. we demand that the split-off factor.15) is always possible since it does not assert separability of the from the wavefunction variables x and X. The ‘Ansatz’ (2.c] $(x.20) The set {$4) of the eigenfunctions of the Schriidinger equation (2. The necessary simplification concerns the matrix element ($’4’(Tc I$4) of the kinetic energy of cores in this equation. first of all. i.15) becomes non-trivial if we proceed as follows: Firstly. An analogous statement holds for the periodicity condition (2. (2. X). X.18) where. 4(X). Using relation (2. An ‘Ansatz’ of the form (2. of the total wavefunction (2. but only in a special approximation . Therefore. relation (2. = (2. 1% + v. T+ + VCCI +(x.20) is satisfied if it holds for the Fourier type coefficients relative to all basis functions Q’d’ of this set.21) is valid..X) which depends only on one variable.X)+(X) E $ ( x . It turns out that such an equation cannot be derived rigorously. . while retaining the full dependenre on both Coordinates in thr second factor +(x.but merely splits off a factor +(X) @(x.X)= U(X)@(X.O)= E&!+t++ c (2.

26) This rcpresents the SchrGdinger equation for the atomic cores in which the coordinates x of thc electrons do not appear. The two equations (2.24) are of fundamental importance in crystal dynamics. In summary. In this way. With this the operator T. Electronic strncture of ideal crystals The first two terms on the right-hand side of this q u a t i o n turn out to be small compared to thr kinetic cuergy term of elwtrons in equation c2. enters this equation.X)9(X)l E=r ${x. forming the scalar product with VI. One has the order of magnitude relations (2. which obeys a Schrijdinger equahion in which the coordinates of the cores enter only as parameters in the potential. The terms of rplativeorders of magnitude (rn/M)1/2 2 lov2 and ( m / h f )w l W 4 .& as if the cores were at.(X)+ U ( X ) \ d ( X )= Ern(X).20) for the crystal. Therefore we present the proof of thwc equations in Appendix B. occur despite its neglect with respect to electron motion.In view of this relation we reconsider the SrhriidingFr equation (2.26).25) This means that T. This originsles in the interaction of the electrons with .ing system of atomic cores and electrqns: The subsystemof electrons is describcd by R separate wavefunction qi(x.n/E is a typird value of the core masses M. of course. red. viewed as an interact.hr kinetic energy. namely via its energy U(X)which plays the role of a potential (referred to as adiabatze potential). T h e potential of this q u a t i o n contains.24) Here .23) (2. Finally.18) in terms involving the electron energy eigenvalue U ( X ) .20).l$(x. X j W G q .60 Chapbrr 2. we h a w reached the following description of the total crystal. (2. X). besides the core-core interaction energy. is described by the wavefunction &(XIand the Schrodinger equation (2. because they are ultimately responsible for the drroupling of rloctron dynamics from the dynamics of the cores. replaring the terms which still depend on x by means of the electron Schrodinger equation (2. The state of the elcctron system. Here we proceed a n the assumption that these relations are proven. for the rambined kinetic energies of all cores satisfies the approximate relation Tc[. the motion 01 the electrons is treat. effectively does not act on V(X.23) and (2. we obtain the relation (Tc + VC. X). will be nPglatrd henceforth. a second contribution IJ(X). which does. Core motion. (2. however. but do not occur as differential operators in t..

X). The potential contribution U(X) caused by the electroncore interaction does not depend.18) and (2. it is clear why this ratio must be small for the two Schrodinger equations (2. That exactly this situation is described by equation (2. according to (2.18) follows.26) to hold jointly in an approximate sense.26). which could be omitted.26). whereas from the point of view of the cores one obtains equation (2.2. without any transitions to other states. If terms of the order of magnitude ( m / M ) I 1 2 are omitted.ec(X)l+(X)).26) for 4(X) thus contains the same namely that the cores move much assumption as equation (2. in the quantum mechanical understand- .27) One can alternatively express this as follows: The electrons move so fast that they are no longer seen by the cores as point-like particles. Equation (2.24) of relative order of magnitude ( m / M ) l I 2 .28) and quantum mechanical transitions between the different eigenstates $14 and $’+’ of the crystal are recognized to occur.2. at since equation (2. but as smeared out over all space. In quantum mechanics. In so far as this feature is seen from the point of view of the electrons. may be seen from (2.13).then the total Hamiltonian 7-t of the crystal has non-vanishing off-diagonal elements (2. equation (2.24). It remains yet to clarlfy what effects are neglected because of the above approximation and why this approximation is called ‘adiabatic’. (2. The dynamical problem 61 the cores. It is an average value over all their positions X. which themselves evolve slowly from the initial onset of time variation. Since the relation between the velocities of the cores and the electrons. This is equivalent to the assumption that the core motion be adiabatically slow. one understands adiabatic temporal changes of potentials in the sense that the changes proceed so slowly that no quantum mechanical transitions will occur between the discrete quantum states of the potential. The state of the system thus conforms continuously to the evolving new potential values as a function of time. however. slower than the electrons.X)1’ d 3 N ~ of finding the electron system in a volume element d 3 N ~ the position x. on the electron coordinates.18) implies that u(X) = (+(X)ITe + vee. then the quantum transitions due to core motion are also neglected. is determined by the inverse ratio of their masses. These transitions are caused by the kinetic energy of the cores exclusively.18) and (2.18) for + ( x . The weight with which the various positions x enter this average over the probability I + ( x . for without such an interaction the eigenvalue U in the electron Schrodinger equation (2. If one considers the previously neglected term in (2.18) would be a constant independent of X.

and the electron equation can be fully d e h e d . X) are known. also effects for which this does not hold. The direct way to overcome this difficulty would be the following: One assumes a particular spatial ordering X’of the The latcores and uses it to determine for them the potential Ve.X’).18) one obtains the value of the adiabatic potential U at the position X’ of the cores.3). It contains additional approximations.-(x.ec(x.. notably electric current transport. The fact that the electric conductivity of an absolutely pure crystal does not become excessively large is due in large part to the scattering of carriers from the oscillations of the atomic cores. one ignores the motion of the atomic cores completely and assumes that they are resting in certain equilibrium positions Xq. Also. as it will be the subject of the next subsection. Therefore.the one for the cores contains the adiabatic potential U(X). a simplified procedure is necessary. but has the advantage of being feasible in practical terms. in the recombination of electron-hole pairs mentioned in Chapter 1. however. It follows that the dynamical problem for the crystal as a whole is solved. However. Since such core motion. this procedure is unsuccessful. ter is then used to solve the electron Schrodinger equation (2. these transitions play a decisive role. Electronic structure of i d 4 crystals ing of this term. which can be known only after the equation for the electrons has been solved.18) and (2. 2. There are. are. as we will see below.-. X)q(X). only as long as transitions between different eigenstates $$ play no important dynamical role. This approximation is useful. From the solution of the Schrodinger equation (2.e. The term ‘adiabatic’ thus refers to the essential character of the approximation in neglecting (rn/M)’/’. reality. also known as ’phonon’ excitations. represents a superposition of lattice oscillations. due to . with the lattice of atomic cores absorbing the energy which is released during recombination. In reality. This equation can then be used to calculate the core wavefunction t#(X).62 Chapter 2. Formally. The problem is that both equations. The same procedure is then applied to all other possible positions X.18) (we will not discuss here how this is accomplished.. whereby the adiabatic potential U(X) and the Schrodinger equation (2. this interaction is called the electTon-phonon interactaon We have yet to explore how the two Schrodinger equations (2. they execute oscillations around these positions with amplitudes that become smaller as the temperature of the crystal decreases. one may understand non-adiabatic transitions as the result of an interaction between the electrons and the motion of the atomic cores. of course. however. not completely determined . In this approach. however. This is actually the case in regard to many crystal properties and phenomena. X)= y(x. i. only if the positions X o cores in the f potential Vee.2.26) for the electrons and cores can be actually solved. to non-adiabatic quantum transitions between different electron and core states. since one would know its eigenfunctions @(x. at the outset.26) for the cores are completely determined. In One cannot solve the electron Schrodinger equation for all possible core positions.

The equilibrium positions Xq are unknown at the outset. One can determine them by demanding that the total energy Vo(X) = U(X) VC(X) (2.2. Equivalent to this is the requirement that the forces -VxVo(X) on the cores.X" 63 I.v.xeq0. = (2.ke. we may employ the iteration process below for the solution of the two coupled adiabatic equations (see Figure 2. The dynamical problem x o .30) Bearing this in mind.Xn) ? v.2): In this pro- . such motion remains finite even at absolute zero temperature. vanish at the equilibrium positions: --vxvo(x)~x.2: Iterative calculation of the equilibrium positions of the atomic cores.ec(X. the quantum mechanical phenomenon of zero-point oscillations.2. the so-called Hellman-Feynman forces.29) of the crystal in equilibrium have a minimum at Xq.(xy -0 ? no xn+1 I + J Figure 2.

Si haas the diamond structure. These oscillations may be describd easily using the S&rodinger eqriatiou (2. Electronic structure of ideal crystah cess. including a series of semiconductor cryst. In this: it suffices to expand the potential I/o in a Taylor series with respect to hhe displacements X .26) for @(XIreads .als. one can determine these forces without numerically calculating Lhe potentid in the environment of X. It determines the probability distribution for the positions of the atomic cores.he Hcllman-Feynman forces will.In this way one reaches a very important result.64 Chapter 2.neglecting ternis beyond the square term. one assumes ccrtain trial equilibrium positions Xo. taken jointly with appropriate analytical transformations. the determination of the atomic structure of the crystal. it can he shown. t. in g~neral. However. enters them in the Ts h electron Schrodinger equation.not yet vanish. i solution is then used to determine the potential Vo(Xo) and the liellmaiiF e y m m forces. The linear term of this expansion vanishes since the potential energy has a minimum at Xq. ]. x (2. the wavehnction 9 itself contains considerably more information. These can be understood as average values (Q I X 14) of the core positions X with respect to the core wavcfmction 4 .Xq from the equilibrium positions Xq.18)! to calculate a new eigenvalue U(X1).29) for the cores. Thanks to the Fe'egrman theorem. With regard to semiconductors.49 A. and determines the eigerivalue U(Xo). 'The new positions are then substituted again onto the electron Schrudinger equation (z. That the probabilities of the cores being removed from their equilibrium positions are non-zero is tbe quantum mechanical indication of the existence of lattice oacdllatioru. The corresponding core positions are then the equilibrium positions XeQ. This procedure is to be repeated until the forces become zero.ermines new trial positions XI.31) With this potential the Schriidinger equation (2. and that its Lattice constant a iR 5.at tice oscillations a6 atomic structure is concernedd: ouly the equilibrium positions of the atomic cores are of interest. that under normal conditions. After the ' first iteration cycle. Such structure calculations are successfully carried out currently fw many solid state systems. By nieans of the non-vanishing f o r c e one det. Thus one obtains I so far n VO(X) = vo(xeQ) ' ( X i2 . for instance. and the latter determines the corresponding Heban-Feynrnan forces. signifying that thc cmes arc still not at equilibrium posibians.X e ~ ) V ~ v X r ~ ' o ( X ~x)e(4 1.

more generally.18) for electrons. Conversely.into non-interacting components of motion . The phonons or. while the atomic cores or.2. Using the eigenvectors and eigenvalues of the matrix of restoring forces (actually. for example. more generally.and their excitation quanta are phonom. of a crystal. Their motions are called normal mode osciliataom or lattace oscillations. e..in our case of the atomic cores of a crystal .the motion of the atomic cores. or quasi-particles. This concept is based on the possibility of decomposing the motion of a system of mutually interacting particles .g.2. Vo(Xeq) = 0 has been assumed. The concept we have in mind here is identified by the terms elementary excztatzons or quast-particles (both terms are commonly used). The restoring forces are determined by the second derivatives of the potential Vo(X).g.. Readers who are particularly interested in phonons are referred to other books (see.in the electron Schriidinger equation (2. the elementary excitations are. is a superposition of all normal mode oscillations or phonons. Bonch-Bruevich and Kalashnikov. one can easily transform to a system of uncoupled harmonic oscillators. 1968. the motion of an individual structural element is a superposition of all elementary excitations . form the ~ ~ T U C ~ U T . As far as the latter are concerned. for simplicity. of the so-called dynamical matrix which also includes the kinetic energy term). 1982). .413elementary excitation involves coordinated motion of all structural elements of the system. the phonons are the most important elementary excitations. the actual particles. by means of X-ray diffraction. Taking this approach.Q ~ elements of the system. Besides the oneelectron and one-hole excitations. so to speak. 1979.18) is well-defined from the very beginning. the potential b’=. including the many-electron system of a crystal which will engage us in the next subsection. e.2. To .. Phonons are a good example of the introduction of a concept which is of fundamental importance for the dynamics of many body systems. we approximate the core positions X by their equilibrium values Xeq. we take the point of view that they are known from experimental structure investigations. For common semiconductor crystals this is in fact true in all cases. The dynamical problem 65 where. Relevant phonon information will simply be cited without detailed justification. Equation (2. Bilz and Kress. O w choice of subject matter here is conditioned by the fact that electrons and holes are much more important for understanding the properties of semiconductors as they are used in electronic devices. the elements of n o t z o n of the system. In this book we will deal mainly with electronzc elementary excitations.32) describes a system of coupled harmonic oscillators. since a thorough development of the theory of phonons is beyond the scope of this book. and will include phonons only if it is otherwise impossible to properly describe electron dynamics. than are phonons. In the sense of Figure 2. Born and Huang.phonons in ow case. We return now to the Schrodinger equation (2.

: stat. X N ) = Ull(X1. as Usingequations (2. taken to be periodic with respect to a periodicity region. The of p I I ( x ) .. .(x). This will be done by developing a oneparticle Schrijdinger equation whose solutions are rdated to those of the true many electron Schrodinger equation in a welldefined and sdiciently simple way.v = 1. x2.e. ~ Hartree approximation In keeping with the remarks above. .(x).Z. . The goal of this subsection is to provide an approximate description which allows one to reduce the number of particles down to minimum number 1. . . . Electronic structure of ideal crystals simplify the notation.XN) must be periodic and normalized with respect to a periodicity region. x2. (2. We Brst associate each of the N electrons with a particular .. m . as the wavefunction @(XI. the N-electron Schrodinger equation (2.331.34) is impossible to solve directly since it describes an interacting system of electrons having a tremendously large number of particles of order loz2. we suppress the core coordinates X in the potential = V + V.35) Secondly.. The Schrodinger equation (2. the Hamiltonian H = Te V e .5) and (2. from which the stationary .18 j takes the explicit form + 2.66 Chapter 2. . xp.$(xl.. .19). of the N-electron system in equation (2. we a s s m e the existence of an infinite set of one-particle wavefunctions q ~ l~ 2 . .XN) the N-electron system may be constructed. WP write . writing Vec(x. (z -34) The wavefunction ~+4(XI. . they are assumed to form a complete orthonormal set of functions in Hillert space. they . sylribolically (CPv~lPv) = 6uhr. . .36) Employing pY(x)we form wavefunctions for the N-electron system in the folIowing way. . (2. satisfy the condition pv(x)= pu(x Cajj + j = 1.. r1. . 'pm. Similarly. . ) = v. XN). are.X) $:. xN) itself... One-particle Schrodinger equation With the Hamiltonian H of (2. henceforth. i.. x2). .3 One-particle appraximation. firstly. . .6). 3.2.2.18) can be written as HVj.x2.(Xl. X the electron wavefunction @(x.

definea the state of the N-electron system uniquely if we understand that the h s t number in this set refers to the state of particle 1. not at all . Due to the Pauli exclusion principle. Henceforth. VN). Here we take a slightly different approach.. WP may say that we occupy state pw with particle 1.pm may occur among the papdated ones lpy.w )by (. ' . . we label a particular electron i.37).if not rigorously.(xj) in such a way that the product statc +ivi obeys the Schriidinger equation H${V)(Xl* x2. etc. each state can host only 1 particle. we abbreviate the configuration ( V l . This procedure has the advantage that one ran ai. . To address this question one may use the variational principle of quantum mechanics.termed configzsvz.38). Most of the states will not even orcur o n r ~ i.x2.e.' ' I X N ) = ~ { V } ~ { Y } ( X lX72 r . . Thirdly.2. . In this procedureI the oneparticle wavefunctions pV. i.(XN) .e. XN) which is given by the bllowing product of oneparticle wavefunctions: I I ${y}(xl. the product (2.. 'py. .37) Disregarding the miitual interaction of the electrons for the moment. .(xJ) energy eigenstates of the individual o n e are electron subsystem Hamiltonians.38) for the fully interacting N-electron system ..I. (q. . V a l . ratzon. p2. .37) forms an eigenstate of the N-electron system if the oneparticle wavefunctions pV. particle 1 with state pull particle 2 with state puL. . . These states remain unoccupied. Considering an M-electron system.37). the second to the state of particle 2 etc.(xj) are determined such that the expectation value of the N-electron Hamiltonian H becomes a minimum for N-eIecctran states of the product form (2. =~LpvJx3)j (2. up to partick N which is associated with the state. Thus a given state p1. particle 2. then at least in some reasonable approximation. we assign to each configuration (IJ)the N-electron system a of wavefunction $(y)(xl. and start from the Schrodinger equation (2. This suggests t h e question whether a similar result might be possible for interacting electrons. . ignoring spin (which we do at this stage). etc..pVN not more than once. The set of quantum numbers... . . IP. 1 XN) (2. state p with .2.XN)= 'pvl(XL)Lp65(X2). . . y Alternatively. (bear in mind that there is an i n h i t e number of them). whether it will be possible to choose the py.x21.a.o . i. The Hilbert space of the . . once determine whether there is a suitable approximation in which d ~ { may ~ } be written in the product form (2. and also barn the nature of that approximation. and this index can take all values between 1 and N. The dynamical problem 67 oneparticle state pv[x).

Thus equation (2.e.40) may be neglected.40) involves only the diagonal terms with p 3 = vj for each 1 # 2 . if = q . co .1remaining elect. In this way we integrate over all XI. left-hand side of equation (2.39) and x2.he N . p~ = v w holds..his equation by the complex conjugated product function (2.. In this remaining Hilbert space we form the Fourier-type coefficients of the Schrodinger equation (2. XN with the exception of xz. However. . more accurate oneparticle approximation. . Strictly speaking.. and correspondingly takes the form The diagonal elements in this equation can easily be evaluated as .. independently of each other. i.381.. .I of H cannot be written exactly as a product {2.40) differs from zero if p J f v3 for one or several I # t .pcl.i .1. obtain (2. pz-l = ~ ~ . ... . ... p o + l .40) Due to the orthogonality of the qv. i.37) of oneparticle wavefunctions. it is the simplest variant of a oneparticle approximation. . of product functions + 1.68 Chapter 2. which means that the eigenfunctions ${. will be discussed below. . . the so-called Hartwe appronmatzoa. . pz-l. It is called a one-partzcle approozamatton. t h e right-hand side of this equation differs from zero only if the pvalues coincide with the v-values.2. .. This is only possible under the condition that the non-diagonal elements of the Hamiltonian operator on the left-hand side of (2. i . by the set. . . . called 4 the Hartree-Fock apprommatzoa..+l = v.38) cannot hold rigorously. It is this approximation which makes possible the reduction of the N-particle wavefunctions to products of oneparticle wavefunctions. . Electronic structure of ideal crysWs system of t. the 1 .. pjv ranging over all possible values 1.+l.rons 1.. ..N is spanned with P I ... we multiply t. Within the framework of the Hartree approximation the equation system (2.e.2.

(2. Beside the potential energy ITc(&) due t o the atomic #}x) It is caused by the cores.47) .42) On the right-hand side of this equation only the first three terms depend on the electron coordinates x1 while the last two are constants in this regard. then the last two terms can be grouped together with U{'(.)reads %{. and is commonly called the Hartree p o t e n t d In explicit form.2.is is its energy eigenvalue. mutual interaction of electrons. V'Iv}(x.. ITH I (x. If one substitutes the expression (2.46) has the form of a Schrodinger equation for the 7-th particle where V'{(")(xp) the potential energy of this particle and EV.41) as The final relation (2.2. The dynamical problem 69 (2.41).44) (2.45) we rewrit.42) into equation (2.) also contains the contribution \'(.}to h m the new eigenvalur Using the abbreviation (2.e (2.

The one-particle Schrdinger equation (2.i . and also on the index i of the particle which was removed.(x’)l2 the reof maining particles.48) For brevity. If one considers.5) does not occur in expressions (2. This difference will now be removed.. the Hartree potential Vrj“}(x) for the configuration {v) is almost the same as that for the ground state configuration {v’}.47) for the potential V. We argue as follows: If the number A. as in the case of the electron system of a crystal.45) and (2. of electrons is macroscopically large. The answer to the former question is ‘under normal conditions.47) for the Hartree potential since each electron pair contribntes only once. e. such as semiconductors which are displaced to a highly excited state by intense laser irradiation. what is it. on the othcr hand. one may also neglect the {v)-dependence of the potential and replace V{”}(x) by the value for a representative configuration {vo). The Hartree putential V~‘”’(X~) describes the potential energy of the i-tb particle in the Coulomb potential produced by the charge distribution --e Ck+% i(oV.46) derived above for the i-th elpctron. we set . and correspondingly we have 4 (2.[”’(x. the Hartree potential and the corresponding energy cigenvalues depend OB the configuration { v } of the N-electron system. Then the 2-dependence o the potential no longer exists. Excluding such extreme cases. we have the state of the N-electron system with lowest total energy. Obviously. Electronic structure of ideal crystals Here the integration runs over a periodicity region. only with a somewhat different potential. For a ‘representative configuration’ in the abovementioned sense. the socalled ground state. Under normal conditions the states of the N-electron system which occur in semiconductors. and also in other solids.. deviate very little from the ground state. and if we consider only oneparticle states which are spatially spread out more or less evenly aver the entire crystal. The factor of the electron-electron interaction potential (2. Non-normal conditions are associated with large deviations. yes’. there is no signifkant difference if we extend the sum over k in equation (2. and the states with energies above are empty. In this state a l one-particle states p” with energies l Ev below a special energy value (the Fermi energy) are occupied. and if so.)t o include k .g. The emor thereby incurred is f of relative order of magnitude l/N. only states ( v } of the &--electron system which are similar to each other. does such a representative codguration exist in the case of a semiconductor.70 Chapter 2. together with the dependence of the H a r t r e potential on the configuration {v} of the N-electron system. holds for each other electron as well. The question is.

planewavelike oneparticle states of an ideal crystal this approximation works better than for the localized oncpartick states of a real semiconductor. Equation (2.50). TJsing the oneparticle Hamiltonian ff = P ' 2. I v(x). For the extended.52) this equation becomes H'Pdx) = Evcpv(x). We may therefore omit the index i in equation (2. one gets approximate solutions of the N-electron Schrodinger equation.37). 'lhis assumption has in fact been made at the outset.. the discussion above has shown the following: Within the framework of the oneparticle approximation.2. and it is natural l o assume that its eigenfunctions form a complete orthonormal set in Hilbert space.50) The extent to which the approximation of a Configuration independent Hartree potential is valid again depends on the kind of one-particle states involved.46) becomes (2.XN) are eigenstates of the N-electron system provided that the oneparticle wavefunctions of the product functions satisfy the oneparticle Schrodinger equation (2. with respect to the oneparticle states cpu(x) forming the product wavefunctionu of the N-electron system. elements of thc Hamiltonian. the product wavefunctions $ J { ~ } ( X x2.e. (2. Using (2. . devoid of any reference to a particular particle or configuration of the N-electron system.53) The Hamiltonian H of equation (2. (2.52) is Hermitian. In summary. . (2. Solving this equation and forming thc product wavefunction (2.51).) = V&) t VH(Xt). In this way we have reached the goal which was formulated at the outset to replace the N-electron problem by a oneparticle problem whose .51) The Hamiltonian of this equation is the same for all particles and no longer depends on the configuration of the N-particle system. In the latter case the configuration dependence of the potential may become essential (see Chapter 3 for further discussion).53).2. The dynamlcal problem 71 V(X.. neglecting non-diagonal ~. the Schrodinger equation (2.51) is therefore the oneparticle Schrodinger equation par excellence. i.

( x ) as states of quasi-particles or elementary excitations of the N-electron system. and the total energy U{. These states of motion are not mutually coupled. Using the terminology introduced in that context one may consider the states q . This may be made clear as follows. contain a certain portion of interaction energy with other electrons. the motion of a particular electron is always tied to the motion of all others. The latter statement manifests itself clearly in relation (2. Using the one-particle Schrodinger equation. i. and the energy of an electron is also. and once in summing over their interaction partners. energy of interaction. If one adds to the N-electron system (which we will assume to be in the ground state) one more electron. leading to The energy of the N-particle system is therefore not just the sum of all oneparticle energies. of one-particle energies. This shows that the ( . once in summing over the particles the sum themselves. x may be interpreted as states of single elecp() trons only in a generalized sense. The oneparticle wavefunctions pV of the N-electron system therefore also approximately describe the elementary excitations of the system of ( N 1) electrons. In reality the (py(x) describe stationary states of the motion of the N-electron system in which all electrons are involved. This means that an eigenstate of the ( N 1)-electron system may be realized by keeping the previously available N electrons in their one- xi + + + . automatically. are energies of single electrons. The idea that the (py(x)are energy eigenstates and the E . Because of the electron-electron interaction. one can re-express the terms on the right-hand side of equation (2. underlying the above consideration. Therein is reflected the fact that the E. First of all.} of the N-electron system. Electronic structure of ideal crystals solution has a well defined and sufficiently simple connection with the solution of the N-electron problem. as in the case of normal oscillations of a system of interacting atomic cores. however. a qualitative difference between these elementary excitations of the electron system and the normal oscillations of a crystal.72 Chapter 2. are the corresponding quasi-particle or excitation energies. needs to be made more precise. in part. which we will explore in more detail. To correct this. then the one-particle Hamiltonian (2.52) does not change within the framework of the approximations made above. which is done in E. if one passes over to a ( N 1)-electron system. The E. it can be further simplified.43) between the one-particle energies E. It is necessary to subtract the Coulomb interaction energy of the particles.e. one must subtract the Coulomb interaction energy. This is doubly counted in E .43) by one-particle eigenvalues. There is.

This means that the eigenvalue Ev* of the one-particle Ilamiltonian may be understood as the energy of an electron added to the system. etc. as always. they determine the potential in which this movement occurs. + It. On the other hand.2. v. while the others play a passive role. These are states in which. The energy difference with respect to the ground state amounts to EV. and to their energies as one-particle excitations energies or.53). This statement is called Koopman h e o r e m .F 0 . which will be considered in more detail below. in short. there are no others than the ones considered above. . . It therefore represents an additional one-particle excitation. at least as long as one ignores spin and the magnetic interaction between electrons. From it. The missing clectron corresponds to a hole in a previously occupied oneparticle state ( p y ~ . v k ) into state (v.. but not all in the same way. The dynamical problem 73 particle states and adding the ( N 1)-th electron in one of the oneparticle states pu* of the N-electron system which were previously not occupied. Y:. and the hole in state p 0 .2. In addition to the one-particle excitations considered above there may yet be others. If one excites a second electron from state v1 'p o into state p. the energy difference with respect to the ground state is u!2 (Eq . the energy of the system rises approximately by Ey*. It corresponds 5 to the excitation energy of a11 electron-hole-pair with the electron in state pu. Thus. one-particle energies. these functions can only be obtained by solving this equation. which did not occur among the oneparticle excitations considered above. I&). more specifically the Hartree part VH(X)..Ey:) (By. One must know these functions in order to write down the potential and thus define the oneparticle Schrodinger equation. One therefore refers to these states as one-particle excitations of the N-electron system. The excitation energy of the hole is -EvO. E e ) ...is now appropriate to clarify how the oneparticle wavefunctions cpv(x) (2. . by adding an electron. This is valid only within the one-particle approximation.... As far as the one-particle excitations are concerned.. The potential in Uhis equation. The excitation energies of the N-electron system can thus be written as a linear superposition of oneparticle energics. . In a strict seiisc one also has many-particle excitations. If an electron is removed from state vy and simultaneously an electron is added in state then this corresponds to the excitation of the N-electron system : from state ($. Only one of the electrons is moving in such states. This can be confirmed by taking a (N -1)-electron system instead of the ( N 1)-electron system. all electrons of the system are involved. . + + vT.. The situation is similar to that in the preceding section on the coupled Schrodinger equations for the interacting system of electrons and 111wbe calculated from the Schrodinger equation . dcpends on the wavcfunctions pV(x)which are involved in the construction of the ground state of the N-electron system. one can learn more about the kind of elementary excitations of the N-electron system that are described by the p.

With the latter one recalculates the eigenfunctions p:(x) etc. and use this to solve the one-particle Schrodinger equation (2. we may also solve the present problem iteratively (see Figure 2. form the total potential Vo(x) by means of (2. and with them also the potential in the following iteration step. As was done there. Electronic structure of ideal crystals d? - n P U V"(X) = t'c(x) VG(X) + Figure 2. an internal angular momentum with the two possible values rC/2 and --7i/2 in a given direction. We employ one-particle wavefunctions pf(x) close to the true stationary oneelectron states. The eigenfunctions and potential are then said to be determined self-consistently. Spin a n d spin-orbit interaction At this point in our treatment of the oneelectron approximation. no longer change within a specified limit of accuracy. i.53). atomic cores. it is a p propriate to recognize that electrons h w e a spin. One continues this iterative procedure until the eigenfunctions. The solutions vt(x)are then substituted into formula (2.74 Chapter 2.491.3).e. This is to say that electrons are capable of a motion in spin space. r s i n g cp:(x) we determine a POtential t$(x) according to equation (2.50).3: Self-consistent solution of the oneparticle Schrijdinger equation. thereby determining new potentials TG(x) and V l ( x ) .49). beside .

px(x.)} in the product space of the ordinary Hilbert spare and tht. a so-called two-component spinor. two-component spin space. s) can then be written as i). i. this may be done by specifying another quantum number u for the spin motion along with the quantum number v of the orbital motion. As orbital motion involves dependence of the wavefunction p ( ~on the space coordinate x.e.( i0 - 0') 1 3 0 (2.yo($)} which does not change in coordinate space. The dynamical problem 75 their motion in coordinate space. (7.2.50)) and 3 is the vector whose three components are Pauli's spin matrices. (2. can then be represented as a product of only one spatially varying function py(x)and a spinor .57) Taking account of spin and the spin-orbit interaction. the orbital and spin motions are coupled. i)} (~~(4)~ (2. s) on the spin variable s which may take the two possible values s = and s = .. in consideration of spin. on the other hand. In spin space one usually refers all quantities to the basis X I = (1. as before. o where u may take the two values T (spin up) and 1 (spin down).56) Here V(x) denotes. This is mainly due to the fact that. u y . in the oneelectron Hamiltouian: H. and that.X I = ( 0 .v .=(. In quantum theory it i s shown that this interaction.-[VV(X) 4m c Tz x p] . The spinor {px(x.2. If the latter i s independent of the state in coordinate space. 'I'hus.55) in Hartree approximation t.0).). i). the quantum number X which defines the statr must also specify the spin state. . the spin motion is accompanied by a magnetic moment of the electron. The two spirior components cpx(x. i). l ) . can be represented by the following additional term H.akes the form . which is called spin-ovhit intemction. To determine the spinor state of an electron uniquely. however. the periodic crystal potential of equation (2. p(x. the orbital motion gives rise to a magnetic field which couples that magnetic moment.spin motion involves a dependence of p(x. the wavefunction of an elcrtron changes from an ordinary vector p(x) in Hilbert space to an element {~(x. Then the components of are u..z1 - 4 (below the latter value will be written as =_ -. which in this context is called orbatal m o ) tion. the one-particle Schrodingw equation (2. fiLnrtion. by setting . . on the one hand.55) In general.

the spin of the electrons has to be considered.he energy specha of many serniconduct. automatically enforcd by the use of the det.. If t. Employing such SlaPer determinants as N-particle wavefunctions. .76 Chapter 2. The antisymmetric linear . In conjunction with this. 'l'his means that no states of the N-electron system are allowed with two electrons in the same oneparticle state.59) In this determinant. but the potential in this equation ia .37) of the Ilartree state by a linear combination of product wavefunctions with exchaiigd partirle indices and altered signs.wo of the quantum numbers XI. such that the wavefunction of the t-th particle is given by the spinor p ~ . a one-particle Schriidinger equation far pv(x) may be derivd in the same way as before. AN are q u a l .tcn in t h e form of a so-called Slater determinant (2. "his is just the Pauli principle. Hartree-Fock approximation An obvious drawback of the Hartree approximation is that the wavefunction of the IV-particle system is not antisymmetric with respect to the exchange of two particles. 'l'his defect can be easily remedied by replacing h e product wavefiinction (2.alform of the N-part. then two colunms 01bhP determinant are identical and vanishes. Electronic structure of ideal crystals (2. ( x . . as opp o s d to simple producls. X2. cornhatiom of the product waverunctions may he arit.he variables of two electrons leads to the exchange of the two corresponding rows. .si).58) Spin-orbit interaction i s in fact an important consideration in determination of t. The sign of the determinant thereby changes. a requirements of the Pauli exclusion principle.icle wawfunr tion.erminant. SO that the Slater determinant actually has the requisite aiitisymmnctry propcrty.ors. an exchange of t.

The effect of the exchange potential on the wavefunction p ( ) is represented by an integral operator. The improved oneparticle Schrodinger equation with the potential of (2. the exchange potential acts only between electrons of the same spin. the exchange potential . firstly. and the spin state by a separate cpiantum number m i .x is non-local. that for the ground state with total spin 0. In this way the magnitude of the exchange potential is influenced by the existence of electron spin. The dyynmiicd problem 77 somewhat different than that in the Hartree equation.60) In the case of negligibly small spin-orbit interaction. the so-called exchange potential Vay(x). which underlies it. the Hartree and exchange potentials are understood as those for the . The sum VH(X) Vx(x) of the Hartree and cxchange potentials can then be written in a relatively simple form.60) and (2.37) does not account for the exchange hole. The factor of 2 results from summing over the t. are of thr 8%) form (2. and.61) also shows that. This lowering of electron density in the vicinity of an electron results in an attractive potential in addition to the repulsive Hartree potential since the total Hartree wavefunction (2.2. and the oneparticle approximation. and half are in spin-up states.and the total potential reads V(X) = K(x) + VH(4 + W X ) . It contains an additional contribution. In actual calculations one often uses a local approximation for Vx(x).55) in such circumstances. The second term corrcsponds to the exchange potential. is called Hartvee-Fock approximation Thereby. the orbital state may be characterized by a separate quantum number v t . The exchange potential proofs to be attractive. Formally.heHartree potential. It can be shown thilt theii action on the coordinate dependent factor of the oncparticle wavefunction cpl. Equation (2. although its value is the same for spin-up and spin-down states.59) of the total wavefunction ${A} means that the probability of finding two electrons with the same spin at the same position is zero so that one has an ‘exchange hole’ around each electron. secondly.61) The Erst term on the right-hand side of this cquation is t. unlike the Hartree potential. (2. half of the electrons are in spin-down states.61) is called the Hartree-Fock equation.2.. The factor of $ reflects the fact that.(x.(x)takes the form + (2. it differs from the first term by exchanging the states at ’ the two positions x and x . T h c spinor components cp~.wo spin states associated with each wavefunction cpvk(x). which is to be expected: the anti-symmetric form (2.

t i a m of an electron system. They form a direct electronic analogy to the lattice vibratious of the atomic cores of a crystal. Ziman. since their separation by a distance of about a Bohr radius is more probable than all others. which are still neglected within the HartreeFock approximation with configuration independent Hartree and exchange potentials. The excitation energy of such a hound electron-hole pair.eigenalates of the N-elwtrronsystem n are not oneparticle excitations! but many-particle excitetians. 1974. The consideration of correlation effects stands along the most difficult problems of solid state thmry which. but. m n f s e in the fact that the true oneaietd particle excitation energies of an N-electron system differ from those in the Hartree-Fock approximation. is smaller than that of the excitation energy of a free electron and hole pair. I other terms.78 Chapter 2. there are non-vanishing offdiagonal elements. 1981). This interpretation presents the correct concept of correlation in other cases also the states of the electrons are no longer independent o each other. are called correlation effects. Harrison. Readers who are particularly interested in correlation effects will find discussions in a number of textbooks (see. these excitation energies depend on the configuration of the system. differing by the binding energy of the pair. Collective many-particle excitations are excitations of states in which all electrons of the system participate in comparable measure. configuration dependence. Correlation effects Correlation effects are. Madelung. In particular. the so-called ezcitan. one has tt. 1978. Below we summarize some results ~ . Callaway. The exact eigenstates of the total Hamiltonian are linear combinations of diflerent Slater determinants. the exart. as had been the case for individual Slater determinants. first of all. Slater determinants which in Hartree-Fock approximation are considered to be eigenstates of the total Hamiltonian. md Dzyaloshinski. 1971. e . Examples include the plasma o s c i l . Electronic structrrre of idea? crystah ground state configuration v i of the N-electron system. The reason for the designnation ‘correlation effect’ for this phenomenon is obvious: binding may be understood as a correlation between the positions of the electron and the hole. g . Fetter and Walecka. Secondly. Examples of many-particle excitations include two-particle ezcitation. 1976. and the corresponding energy eigenvaluea are no longer s u m of oneparticle excitation energies. A comprehensive analysis of this problem i s far beyond the scope of the present book. even today. in fact do not diagonalize tbis Harniltouian ezactlv. The effects of the electron-electron interaction. Their excitation quanta are called plasmons. hbrikosov. an effect which is termed configuration interaction. Gorkw. are correlated contrary to the assumptions implicit in the f oneparticle approximation. is not completely solved. 1963.5 of an electron and a hole which are bound together by their Coulomb Interaction.

Another method which works well for oneparticle states involved in the ground state of the many-particle system is known as density functional theory. the external potential energy E c [ n ( x ) ] the Hartree energy E w [ n ( x ) ]and the . with respect to which the common derivative is taken.2.(cp. through an integral over X .e. .63) In this functional derivative the value of cp:t(x) at a certain point x is taken as an independent variable. The dynamical problem 79 which will be needed in Chapter 3. Density functional theory. are populated by electrons z = 1. individual electrons and holes moving in the force field of all other electrons as well as in the force field of the atomic cores.62) where cpvi(x) denote the one-particle states which. which ensures that the ground state energy Eo of an interacting electron system in an external potential Vc(x) is a functional E o [ n ( x ) ]of the total electron density n(x) of the ground state alone. The one-particle Green's function is governed by the Dyson equation. Correlation effects on one-particle excitations. the total envrgy Eo[n(x)]is minimized. This method relies on a theorem. where the factors E . first of all. This implies. Correlation effects on one-particle excitations may be treated by means of the Green's function theory of many particle-systems. while keeping their norms (cpudlqv. moreover. namely. The oneparticle wavefunctions determine the ground state density by means of the equation (2. the Hohenberg-Kohn theorem. and the imaginary parts are the lifetime broadening energies of the one-particle excitations).) constant.. of The total energy functional Eo[n(x)] the ground statr may be decomposed into several energy contributions.. that the density enters at every point x. therefore -xi (2. we will concentrate on oneparticle excitations. N. The poles of the o n e particle Green's function in the complex energy plane represent oneparticle excitation energies (more strictly speaking. i.2.(x) adjust so that. the kinetic energy E ~ & ( x ) ] .(x)and.) with respect to p:*(x). . the real parts of these poles are the energy levels. According to the variational principle of quantum mechanics. are variational parameters. that the total energy E o [ n ( x ) ]depends on the oneparticle wavefunctions only through the ground state density n. which contains correlation effects through the so-called mass or self-energy operator. in the ground state of the N-electron system. This requires the vanishing of the variational derivative of the functional E o [ n ( z ) ] E..Ip.2. In doing so. the wavefunctions cpv.

we have (2.(x) iu given by (2. n ( x ) Ix' . By definition.65) E ~ [ n ( x =] ) 2 // R R d3x'd3x n(x') .64) and E ~ [ n ( x are easily obtained as )] The functionals E c [ n ( x ) ] (2. the kinetic energy fuIictiona1 E:k.67) has Finally.69) For the rcmaining functional derivatives. and E x c ( n ) reduces to an ordinary function of n. The total exchangecorrelation energy Exc(n) of a weakly inhomogeneous electron gas of density n ( x ) should then be given approximately by the expression (2. Electronic structure of ideal crystals exchange and correlation energies which are usually summed in the exchangecorrelation energy E x c [ n ( x ) ] .70) . For the waluation of the variational equation (2.68) Although this expression does not look like a functional of n ( x ) il is indeed possible l o transform it into such a form because all other terms in the total energy functional Eo[n(x)]of (2. In this case the density n ( x ) is a constant n in space.66) The functional E x c [ n ( x ) ]is less obvious. need the explicit functional form of EkznIn(x)l.64) are functionals of n ( x ) . It is usually taken in a local approximation called the local density approximation (LDA). per ) electron. and the Hohenberg-Kohn theorem enforces this for E & t ( x ) ] .63) we do not.68) suffices.tn[n(x)] to be specified. it follows that (2. expression (2. however.80 Chapter 2. The LDA starts with the homogeneous electron system without any external potential.. Its variational derivative with respect to p. Dividing E x c ( n ) by the total number nR of electrons yields the exchange-correlation energy E X C ( ~of the free electron gas.Thus Eo[n(x)] Ekin[n(x)l Ec[n(x)l &dn(x)l = + + + Exc[n(x)l.XI ' (2. (2.

A misinterpretation of this kind may lead to large errors. with the potential V(x) given by (2.4s rompnred t o the oneeleclron potential V(X) of the Hartrw ur Hartret-Fock equations. Suhstitiiting i n h q u a t i o n (2.7734 z In with z .2. This dependence can hr obtained by calcrilatnumerically for tfifkrent values of n and then lilting the data ing E>yc(n) to appropriate explicit functions.75). defining the energy gap.2. various Pxchang+ correlation potentials have been proposed.76) as an effective one-elcrtron potential. The latter can be determined if the exchange-correlatiou energy E x c ( n )of the homogeneous electron gas is known as fniictio~iof n.76). for exaniylr Lkc(x). as it is possible for the eigenvalues of the IIartree or HartrePFock quations according to Koapman's theoiern. TJsing this procedure. in particular.75) with v(x) = VC(X) I Vrr(X) + i<Tc:(x) (2. Relation (2.rS/2l. however. . where rS = and CI. is known as Kohn-Sham equatzon. However. This applies. Generally. The physical significance of tlir solutions of the Kohn-Sham equation is. 1971).73) denotes the ~xcliangPcnrrelation potential. The resulting erroneous gaps are about 50% smaller than the experimental values.71) (2. the eigcnvalucs of the Kohn-Sham equation cannot be understood in the sense of oneparticle excitation energies of the N-electron system. The dynamicd problem 81 (2. to electron-hole excitation energies in senlimnductor crystals. the .B the Bohr radius (Hedin.- ( : ) 1/3 e2n1j3[x)[I + 0. Lundqvist. one arrives at (2. that of the Kohn-Sham equation additionally accounts €or correlation effects. less direct than that of the solutions of thP llartree or Hartrw-Fock equations. Th? electron ind~x has heen omitted a here bwauw thP equation is the bame for all electrons.72) where (2.63) t h e frlnctionrtl drrivatives obtained above.

It turns out that the results derived for symmorphic space groups arc also valid.3. on the positions of atomic cores. The oneparticle excitation energies may be obtained as the differences of the total energies of the ( N t 1)-or ( N . reflections as well as rotation-reflections.1)-electron system for hole excitations. The general case of non-symmorphic space groups.77) . However. on the other hand. Minimizing the total energy with respect to the core positions yields the atomic structure of the crystal.53) is endowed with corresponding symmetry properties.1 Symmetry properties of the one-electron Schrodinger equation For simplicity.64). while screw rotations and glide-reflections are excluded.82 Chapter 2. reflections and rotation-reflections of the point group of directions transform a given crystal direction into a physically equivalent one. with minor modifications.1)-electron systems. and with it the particularly iniyortant case of the diamond structure. tRx =x + R. Electronic structure of ideal crystals eigenvalues and eigenfunctions of the Kohn-Sham equation can be properly used to calculate the total energy of the ground state of the N-electron system by means of the total energy functional (2. for non-symmorphic ones. These are groups which contain solely translations. In doing so. We use the symbol t R to denote the lattice translation operator which causes a translation of all points x through a lattice vector R. rotations. Rotations.53) is specified by the form of the potential V(x) which is different for crystals of different chemical composition and atomic strurlure. also can be obtained in this way. a crystal remains invariant under a transformation by an element of i t s space group. As we already know. we restrict our considerations here to crystals their space groups are symmorphic. Consequently. and the N-electron system. The symmetry of the crystal is transferred directly to the potential V(x). We shall first describe these and then explore their implications for the stationary oneelectron states cpu(x). + 23 . the Schrsdinger equation (2. General properties of stationary one-electron states in a crystal The oneelectron Schrodinger equation (2. there are certain general properties of V(x) which do no1 depend on the particular material nature of the crystal. on the one hand. The dependence of the total energy on external parameters as. for example. where the ( N 1)-electron system applies for electlan excitations and the ( N . 2. we initially neglect electron spin. (2. i s treated in Appendix A.

81) from which it follows that the transformation a . i. xj are the com- (2.e. the utJ arc not iu general orthogoual matrices. we also assign operators to rotations. lh coordinate counter-transformation takes place with the . their inverse matrices are the same as their transposed ones. Indeecl. this holds only for the primitive cubic lattice. For the symrnorphic space groups considered here.80) j we may rewrite this relation in the form (2.may also i be understood as a counter-tra~sformation thc coordinates with fixed basis of vectors. However. the translation gioup is B subgroup of the space group which. By means of this relation each opeiator a is uniquely associakd with a corresponding matrix aV. by definition: contains all symmetry elements of the crystal. and is not true fur all other 13 Binvais btticrs. which was ariginaIly defined as a transformation of the basis vectors a with fixed coordinates zz.a 2 and a3. and W P denote them by the symbol a and call them point symmetry operataorw.78) with ov as real coefficimts. As in the case of translations. t or t ~ r of a translcttion t~ and a point syrnrnetrg operation a. These operators also art on the spatial vectors x. which we already encountered in Chapter 1.2. Thus. The ponents of x with respect to these vectors. the uaJform orthogonal niatriw$. The effect of a on an arbitrary position vector x may easily be d e t e r m i n d by ~ n e a n s i t s decomposition of x -czja3 t (2.79) with respect to the three primitive lattice vectors aj. each element y may be thought of as a product 0 . lattice vectors a are orthogonal and of the same length. We define (see Appendix A} (2. Applying a . Since the lattice translation operators are symmetry dements of the crystal. it suffices to s p e d y the &ect l of a on these.3. Since an ~ r arbitrary position vector x may be represented in a basis spanned by the three primitive lattice vectors a . reflections and rotation-reflmtions of the point group of directions. If the thee primitive . General properties o f stationary oneelectron states in B crystal 83 The set of all lattice translation operators forms the translation group.

in contradistinction to the transformation (2.v(x). the kinetic enerw operator ?' = p2/2m. Applying these 2 definitions to the potential V ( x ) and simultaneously requiring crystal symmetry.83) and (2. This is the Sam?. B ] = A B . Formally the definitions (2. with IA.78) of the basis vectors.l x .89) (2.83) (2. (2. This is t o say that (2.84) a S ( x )= S ( a . because ( q c q ) .l x ) . the relations ) (2. as the proprrty o f t h e original crystal at the inverse transformd position.W) follow.' .B A as abbreviation for the commutator of two operators A and 3.84 Chapter 2. Further application of these opwatm relations to a wavefunction p(x) one obtains and since ~ ( xmay be chosen arbitrarily.rtl a -1 . One says that t~ and 1y commute with the potential V ( x ) . To express this fact formally.82) remains invarianl under the transformations t R and a .85) (2. The rhosen deftnition strms from the rrcognition that the transformed property is that of the transfarmrcl crystal at the original position x. Such cornmutivity also holds for the uthcr contribution of the Hamiltonian. w r have tnv(x) = V(t.84) giiarantee the correct multiplication order of two no11 commuting operators -1 under the fiinction symbol. but not by k ~ or c k x . UV(X)= V ( d X ) (2. howewr.lX) .86) = v(xj. then this mist also hold for the potential V(x) with which the tramformed crystal acts on an electron at position x. we &fine the operation of t~ and n on an arbitrary position dependent scab1 crystal function S(x) as follows: If the crystal tf$(x) = S ( t R ' X ) . For t~ this follows directly . as one might hme x expectd. It is striking that the operators t~ and a act on S(x) in such a way that x ifireplaced by tR1x or m . Electronic structure of ideal crystals transpose matrix a j i of aij.

rotation or reflection.53)holds. The commutivity of t~ and a with H has the consequence that.961. the symmetry group.ates to follow. one has . (2.1 = 0. Then the stationary Schrodinger equation (2.uE(x) and g p ~ ( x are ) eigenfunctions of H having ihe same cigenvalue E . We will use it extensively in the analysis of symmetry properties of stationary oneelectron st. ] = 0.95) In addition. .89) and (2. these relations yield [ t R . along with cp~(x). [tR. which at the outset includes an infinite number of lattice translations. ]u. (2.90). Thus. also t ~ p ~ ( x ) . one also has The latter relation expresses in h a 1 form the implication of crystal symmetry for the Schrodinger equation. Thus. while for a it follows from the fact that p2 is the square of the length of the momentum vector. HVEW = EPE(4.HI = 0. 2 - (2.2 Bloch theorem Let p~ be an cigenfunction of H having eigenvalue E . H (2.91) Taken together with ('2.2. is reduccd to the finite subgraup containing only those translations t R which do not fall outside the periodicity region. General properties of s i a i h n a r y oneelectron s&atwin a crystal 85 from the relations p = .2. and V = V x + ~ . 2.96) and t h e normalization condition Through the periodicity condition (2.i h V . whrrc the state index v has been replaced by E . as w l as from the observation that the length of a vector is not changed by a el translation.92) (2. one has the periodicity condition with respect to a periodicity region VE(X -k G a j ) = ( P E ( X ) 1 J .3.3.TI = [a. w.93) Since the elements g of a symmorphic space group may be written as products of t~ and C Y . 3.

( P E may be transloorrued (d-1) x I into a new basis (p~. This result will not.. su functionstRpE. no longer irreducible. . Electronic structure of id& crystah (2.'plh. . ~ 2 . . for symmetry reasons. Analogous equations hold for all o t h a functions t ~ l p b . group. It is of special importance that the translation group is a group of Abehan type: The resiilt of two translations t~~ and t~~ does not depend on the sequence in which they are executed. IpE& They . 'I'his means are that thp t p p itself may be written in the form ~ tRcPE(x) = c(R)rFE(x) (2. with t~ an arbitrary element of the translation group. 2 . apart from spmial cases. . ' p E . . .. Formally this is expressed by the equation (2. all irreducible representations of Abelian groups are 1 dimensional.. d equals the number of different elements m of the point group. This is to say that the eignvalue E. The same statement also follows for each subgroup of this group. . in general. particularly for the subgroup of all translations. odered along the diagonal. the totality of vectors g p spans a subspace of ~ the Hilbert space w l i o s ~ dimension d i s in general larger than 1.(pk. ( p ~ d :thus also provides B representation of the translation . . howevpr. In terms of the concept of rmducible represenfatema of groups (an introduction is provided in Appendix A). The space spanned by r p ~ lP E T . . . . we may alternatively express this observation by saying that the eigenfunctions of H for a particular eigenvalue E give rise to a &dimensional irreducible representation of the space group.pE tation matrices of all translation operators t~ written in the new basis are constructed from lower dimensional matIices. .86 Chapter 2. tR&.. (d-1) x I Each of the basis functions &. and then the d basis functions of the subspace may be chosen in the form with Q ranging over the entire point group. However.101) As is demonstrated in Appendix A. . . be usrd in what follows and the basis funrtions will be written in the general form p ~ lp.p .. is d-fold degenerate. This is equivalent to the statement that the cho- . l ~ ~ That means that the original basis p ~ p . span that subspace of the Hilbert space which contains the eigenfunctions of the Hamiltonian with the eigenvalue E .. this representation is. According to i t s construction this space is invariant under the operation of an arbitrary element g of the space group. It can be shown that.c therefore forms a represrtntation space of the translation group by itself. This means that the lower dimensional matrices along the diagonals of the tH-representation matrices are 1-dimensional. . in such a way that the represen. are linearly dependent on p~ and dl functions t ~ & linearly dependent on & etc. Thus.102) where r(R) is a complex coefficient..100) Consider now the eigcnfunction g i p p If the symmetry operation g ranges over the whole space g o u p .

This holds only for specially chosen c p ~ .104) Here. The pair of eigenvalues El c ( R ) is therefore not sufficient to uniquely characterize the eigenstates of H and of the group of operators t R . also proceed without the tools of group theory.2. Although it forms the most appropriate proof. using a mathematical theorem which eos u e s that two commuting Hermitian or unitary operators have a common set of eigenfunctions. however. Quantities which provide such unique characterization have yet to be identified. E z .103) P k 1 k 2 k 3 ( R )= (-2r)(hri + ~ Y+ z ' 3 ) h . k3 which allow one to distinguish the different irreducible representations of the translation group of the crystal. .&.103) we first show .3. kz. General properties of stationary oneelectron states in a crystal 87 sen ( P E . To understand this we must examine these representations in greater detail.102) of the translation operators.The Bloch theorem insures that such a choice is always possible. we will show that the eigenvalues c k l k 2 k 3 ( R ) of this equation may be written in the form (2. For the symmetry operations a of the point group. (2. It. turns out that there are three real numbers k l . The factor L 2 ~is introduced to simplify expressions which later will arise. This result forms the content of the Bloch theorem: The eigenfunctions p~ of the Hamiltonian H of a crystal can be chosen such that they are simultaneously eigenfunctions of the lattice translation operators of the crystal The particular energy eigenfunctions whose existence is stated by this theorem are termed Bloch functions. To prove equation (2.'pk. for example. The Bloch theorem is of such great importance that several remarks are appropriate. . it does not hold. H and t R . one may. In reality there are alwtLys several. . k3 are the above mentioned real numbers which determine 1 the representations uniquely. the theorem does not say that every conceivable eigenfunction of W is also necessarily an eigenfunction of t R . which means that in general the eigenfunctions of H cannot be chosen to be simultaneous eigenfunctions of the operators u of the point group. are eigenfunctions of the translation operator. which in general do not commute. it has to be emphasized that this theorem is an immediate consequence of the commutivity of translations. the E l . In the first place. Secondly. They are defined by the eigenvalue equation (2. respectively. The proof of the Bloch theorem sketched above relies in an essential way on features of group representations. this theorem also does not imply that only one eigenfunction exists for particular eigenvalues E and c(R) of. Thirdly. T o start.

such that. On the other hand.107) Considering (2. Employing (2.88 Chapter 2.112) (2. . we show that c(R1+ R2) = c(R1) .106) and (2. (2. This means that P(R) is a homogeneous linear function of the components TI. I I (2. As such P ( R ) must have the form (2. c(R2) must hold.107) together.103) is verified at once. r3 of R.1) t P(R2).102) that (tRLPE tR(PE) I -I c(R) l2 (PaE I P E ) .97). 7-2. We now proceed to the eigenfunctions of the translation operator.103).104). . we claim that pEklkzks(x) can be written in the form (2. Electronic structure of ideal crystals (2.106) This holds because the translation t~ of the integration variable through R in ( t ~ p t ~ p may be absorbed by a change of variables jointly with an I ) application of the periodicity of the wavefunction p(x) with respect to the periodicity region. which leads to (tR(PE t R P E ) = ( P E (PE). Ic3 on c(R) and P(R) will be suppressed temporarily). whence (2.113) P(Ri t R2) = P(R. The proof is based on the normalization of p~ according to equation (2. Secondly.108) now yields exp[iP(Rl+ Rdl = exp[iP(R~)I~xP[WWI. Employing ( ~ ~ k(x)to denote the eigenfunction having eigenvalue Ck1kzk3 ( R ) ~ k ~ k ~ of equation (2. equation (2.108) Comparison of the last two relations immediately shows that (2.103) for c(R). To prove this. we use the following obvious relations: (2. it follows from relation (2.114) where u ~ k ~ k ~ k denotes a lattice-periodic function. for any ~ ( x ) lattice vector R.105) (the subscript indices k l . (2.108) is also true. k2.

we may express the Bloch theorem in a somewhat more specific form than we did above: The ezgenfinctions of the one-electron Hamiltonaan of a crystal can be chosen i n the f o r m (2.k2. the translation operator t R with eigenvalue e ~ p [ i P k ~ k ~ k ~ ( a -Evaluating . 2.. General properties of stationary oneelectron states in a crystal 89 UEklkzk3(X .3.122. as we will soon see. g k l k Z k 3 ( x ) is also an eigenfunction of the translation operator and.117) ~ ) . The real numbers kl. what eigenvalue of t R pertains to it.f3klkZ~3(a-1R) explicitly using equations (2.3. k2.114). if so. we have . k3 At the outset. it is clear from equation (2.115) The factor l/& with 0 = G300is introduced in (2. Transformation properties of kl.114) are referred ~ x ) to as Bloch functions and the factors u ~ k ~ k + ~ (as )Bloch factors. ( ~ ~ ~ ~ R ) l ~ ~ ' ~ ~ k ~ k(2. k ~ k . k3 characterizing the various Bloch functions may he understood as components of a vector. Recalling x k ( ~ ) that the p ~ k ~ k ~ are~also simultaneously eigenfunctions of the Hamiltonian.~ ) ) = e x ~ l i P k .R) = UEk1kzk3(X)' (2. However.2. This will now be explored.114) in order that the normalization integral of UEklkzk3 (x) with respect to a primitive unit cell be 1.104) and (2.114) may be carried out by verifying that functions of the form (2. we form tRfffpEklkzk3 = t ~ p ~ k ~ k ~ k ~ (and 'obtain the equation a . this is not a vector in coordinate space. The functions p ~ k ~ k ~ k of ((2. but one in a space which is reciprocal to coordinate space.99) that both p ~ k ~ k ~ k andx ~ ( a q E k l k z k 3 (X) are degenerate eigenfunctions of the Hamiltonian H with the same eigenvalue E .82). In order to answer this question. The question arises whether a p . This results in which we know to he true.102). The proof of (2. k3 is their transformation law under point symmetry transformations a in coordinate space.3 Reciprocal vector space and the reciprocal lattice The starting point for understanding the nature of the components k l . ~ k ~ ( k ~ ( ~ ) The latter relation means that a p ~ k ~ k ~ is indeed an eigenfunction of ~R)].114) obey equation (2.

This is to say that (2. should now be understood to operate on the real numbers kl. but rather it is the transposed inverse . The transformation properties of the kj thusly defined are similar. those of vector components.az. which hitherto operated on the vector components of R.or space is determined by a basis bl.a2.119) must hold.he new interpretation cannot change the value of the expression (2. We will now prove that this is exactly the way the components matrix a of a vector transform in a space reciprocal to the ordinary space of position \-=tors x.118) j i This expression is subject to an interpretation which differs from the previous one and which has important consequences for later developmentu. . k~ inslead. t. The corresponding reciprocal vect. respectively. b3 said to be reciprocal to the original basis a1. The differenceliea in the fact that it ia not the matrix arj itself that multiplies the column vector of the components. .122) These equations state that the vectors of the T & P T Q C ~ basis me normal to. but not identical to. To assnre this.118). b2.a. One may therefore write (2. Definition of the reciprocal vector space l h e space of position vectors x is defined through its basis al. Of course..121) 3 This equation means that the transformation a. which applies in the case of the components ~j of R. ' . the kj must transform according t. k.90 Electronic structure of ideal C S ~ S ~ A I S (2.The reciprocal basis is defined by the set of equations EQ ' bj = 2 ~ 5 i j (2.k z . which werp initially introduced as real numbers without any particular transformation behavior.o the transposed matrix ' .w.which originally operated on the wavefunction p ~ k ~ l f a k ~ ( has been transposd to operate 021 the x). The new interpretation is that the transformation. a of' a j n s t e d of the matrix a i j . one of the three planes spanned by pairs of direct basis vectors.

3. The lengths of the reciprocal basis vectors bj are determined by the three equations which follow from (2.'. Using this result. since the recipaz. this induces the same rotation or reflection of the rwiprocal basis. i = cxk. the matrix LY which describes i the rotation or reflection of the a is different from that which transforms the bj. aa follows: bl= -[a2 x q]. which can be written as (2.124) i As we know.122) for j = a. Consider now an arbitrary vector k of reciprocal vector space. Using equation (2.103) of the translation operator in the more compact form . bz 00 2x 27r 00 x a1 1 . Since the transformation of the reciprocal basis calls for the inverse matrix. (2. the inverse matrix describes the same rotation OF reflection of the reciprocal basis a the s transposed matrix docs fur the direct basis.that is. bz. the equation set (2. as follows immediately from the defining equations (2.122) or (2. [a2x a 1 is the volume of a primitive unit cell of the crystal 1 3 lattice. Because of these relations the 'reciprocal' basis (bl.125) The reciprocal vector k of (2. b3) is rigidy joined with the direct basis (al: ag) a2. with the inverse matrix a. we obtain kkb.121)describes the transformation of the components of a reciprocal vector. Altogether. the vector components themselves transform in accordance with the transpose of the transformation of the basis vectors. the a are mutually non-orthogonal.4mong themselves. and will transform when the latter is tranaformd However.124) may be used to express the phase . This verifies our earlier assertion that quation (2. b3 : -[a1 2x Qo x az] .a3) are orthogonal rocal basis is different from the direct one (only if (al. In other words. If one s u bj et s the direct basis to a rotation or reflection.123) Here Ro = a . unit vectors are the two basis sets the same).122) determines the reciprocal basis vectors bj uniquely.2.123).&kka(R) of the eigenvalue (2. the components bi will transform with the transposed inverse matrix 05'. General properties of stationary oneelectron states i a crystal n 91 .123) one may easily show that the bj are transformed with the transposed inverse of the transposed matrix u p which transforms the q . (2. the bj are in general non-orthogonal to the extent that .

128) may be understood as travelling waves. it remains constant only under translations through lattice vectors.126) Using this expression the eigenvalue of t. of equation (2.131) This is just the well-known result that the stationary states of a €reeelectron may be taken as plane waves o a given wavwwtor k If the potentid is not f . and t. For this p u r p o s ~ first assume the potential V(X) to be a constant we independent of x. (2.hP treiistntion operator (2. that these states are necessarily modulated tmvellzng plane waves.That the stationary oneelectron states may be chosen in this form. of modulated spdiallJ by thr latticeperiodic Bloch factor U E ~ ( X ) . in this caw. (2. of roursc. the dimension of the quasi-wsvevector is also that of a reciprocal length. consequently. for they do not change the potential and.129) A further consideration illuminates the physical meaning of the reciprocal vector k. completely constant but.103) becomes which provides a more compact notation fm thp Bloch We may write (2.128) with u ~ k ( x as a short notatinii for the Bloch factor u ~ l .92 Chapter 2. ~ k ~ k ~ Because ) (x).130) for arbitrary vectors r. just as t h e stationary states . Rut thrrp is m o m In this caw translations through arbitrary vectors r and rotations about any axis and through arbitrary angles are symiwtry opcrations.115) one has ~ g k ( X - R) UEk(X) .he eigenfunctious of the HamiItonian are of the form (2. the meaning of k as wavevector is largely prwervd. All the abovementioned r e s u l t s hold. This mcans that the Bloch factor ugk(x) is a cons t w t . is the content of Bloch~ thwrpm. R. as happens in a crystal. The Bloch functions y ~ k ( x ) (2. This theorem d o e riot say. appropriate to a free electron. Therefore. also leave the Hamilt onian innriant. Electronic structure of ideal crystah Bklkpl~3(R) -k. howevrr. It is thrrefore called a qaasa-wavevector: Of course. "Ekb - 4= " E k W (2.

states in a crystd 93 of a free electron need not be travelling plane waves.123) aa its . (2. 3 .G with 4 BS 1 lj. so small because of the large size of C that k can pract. to assure satisfaction of the requirement The k-vectors defined by (2. In this context.. Fortunately. The Ebch fuucfions V E ~ ( X )obey the relation if and only if the components k j of the k-vector are of the form k. the so-called mciprocal lattice i s especially useful.2. This approximationwill be used later extensively. The k-space thus has a discrete structure. however.. j = 1!2 .3. sphrriral waves d c . The only permissible k-vectors must be points of this net since the Bloch functions are periodic with respect to the Periodicity region.bz. it can be satisfied very simply. Reciprocal lattice Just t t h in direct spaw.b3 of (2.4).96) for the eigenstates of the Hamiltonian has largely been ignored so far.4: Mesh of allowed points in k-space due to the periodic boundary conditions in a 2-dimensional model.133) form a finely meshed net in k-space (see Figure 2. It is dehed by taking the reciprocal basis vectors bl. One ran also h a m standing plane waves. The distance betwren different k-vectors is. General properti= of stationary one-electron Figure 2. one may also consider a point lattice in reciprocal space. Discretization of k-space 'The periodicity condition (2.133) arbitrary integers.ically be treat4 as it continuously varying quantity despite its discrete character. its set of points is countable.

Some general properties of E(k) follow.128) into the Schriidinger equation (2. (ii) The reciprocal lattice of a reciprocal lattice is the direct lattice.136) The k-dependence of the operator in this equation transfers to the eigenvalue E. As in coordinate space. The following properties can be verified easily: (i) A reciprocal lattice has the same point symmetry as the direct lattice with which it is associated.4 Relation between energy eigenvalues and quasi-wavevector We have not as yet directed attention to the question if there may be a connection between the quasi-wavevector k and the energy eigenvalue E : and what form it might take. one has E(k) = (H2/2m)k2. and it will now be explored in some detail. primitive lattice vectors. (2. The Bravais types of primitive direct lattices are the same as those of their reciprocal lattices.one obtains the following eigenvalue equation for U E ~ ( X ) : Izm -P ( 1 t rzk)2 -1. The specific form of the function E(k) is determined by the particular shape of the periodic potential V(x).95). That a Bloch function p ~ for a given wavevector k cannot be art eigenk f 1 function o I for an arbitrary energy eigenvalue E may be yeen as follows. a face centered cubic reciprocal lattice corresponds to a body centered cubic direct lattice.94 Chapter 2 Electronic structure of ideal crystals . The reciprocal lattice of a centered direct lattice is also centered. For example. while the Bravais types of centered direct lattices and of their reciprocal lattices differ in certain cases. In the case of a free particle with V(x) = 0. and. The reciprocal lattices bear a close relation to the corresponding direct lattices. In fact such B connection does e x i s t . a body centered cubic reciprocal lattice corresponds to a face centered cubic direct lattice. conversely. then the same holds for the corresponding reciprocal lattice.135) with arbitrary integers K j .e. (iii) If the direct lattice is primitive.3. If one substitutes i p ~ k ( x )(2. i. E becomes H function E = E(k) of the quasi-wavevector k. 2. of course. more compljcated dependencies than this. A reciprocal lattice vector K is then given by the relation K =CKjbj 3 (2. .v(x) 1 UE&) = EUEk(X). one also has 14 different 4 lattice types in reciprocal space. namely the 1 Bravais lattices. For a crystal one expects.

just from the space and time symmetry of V(x). be identical with ( P E ~ ~ ( x ) . for the quasi-wavevector k.120) and (2.138) The relations (2. and a comparison of (2. There is an exception for those special k values for which ak does not differ from k or from a vector k K equivalent to k for all a.138) then yields E(k) = E ( a k ) .3. mean that U p E k is an eigenfunction of H for quasi-wavevector ak. We will discuss this now. where TY i s taken to be an arbitrary element of the point group of the crystal: (2.137) and (2. on the other hand. (2. In order for the Schrodinger equation to remain unchanged under time reversal. a c p ~ k ( x must. beginning with point symmetry.137) and. ) because ( P E ~ ~ ( is )by x definition the eigenfunction for a k . on the one hand. which we initially take to be the case. (2. General properties of stationary one-electron states in a crystal 95 however.140) The assumption that there is only one eigenfunction of the Hamiltonian for the quasi-wavevector k holds for almost all k. but with an application of the transformation (Y as follows HWEdX) E(kbPEk(X). + Time reversal symmetry A property of the Hamiltonian H which we have not employed thus far is its invariance under time reversal.95). for the quasiwavevector crk. If there is only orbe eigenfunction for a given wavevector.2. the time reversed wavefunction must be defined as the complex conjugate of the original wavefunction. but we exclude symmetrical k-vectors at this point. Point symmetry We consider the Schrodinger equation (2. Thus.5. the fact that there is only one eigenfunction of H . derived in the preceding subsection.124). For non-symmetrical k-vectors. whose implications are relatively easy to examine. Then the . One refers to such vectors as symmetrical kvectors. They will be considered in section 2. follows from the onedimensionality of the irreducible representations of the translation group (see Appendix A).

only then. This disadvantage is eliminated if the selection of the region over which k varies is not fitted to the energy E ( k ) but rather to the ck(R) eigenvalues of the translation operator.E(-k). However. and T % as integers. since one encounters the same eigenvaliie an infinite number of times. Specifically. (2. namely all those which follow frotn E ( k ) by means of the prescription . Since both Bloch functions have the same eigenvalue.R1 (2. the energy cigenvalues g ( k ) do differ. have the same eigenvalue of thc translation operator. the latter is -2k.141) This relation has additional significance. if the point group of the crystal does not contain the inversion. however. The k-vectors of any other primitive unit cell differ from these by a reciprocal lattice vector K and thus do not lead to new eigenvalues of the translation operator. i. Therefore we obtain the full spwtrum of eigenvalues of t R if k varies within a particular primitive unit cell of k-space. so that E(k1) f h’(k1-t. one obtains E ( k ) . This asymmetry with respect to the k-dependence of rk(R) and E(k) is the reason for the introduction of two different representation schemes for the energy eigenvalue function E(k). Independently of the actual value of K. Electronic structure of ideal crystals time reversed Bloch function of wavevector k has wavevector -k. Translation symmetry: Extended and reduced zone schemes The lattice translation invariance of H has a remarkable consequence for the eigenvalue function E(k).e. Table 2. and to each vector k we associate only one k-dependent energy function E(k). if k is allowed to vary only over a primitive unit cell rather than over the whole k-space.96 Chapter 2. this description i s highly redundant. The corresponding k-vectors will br denoted by kl.K ) holds in general. With respect to the eigenvalues of the translation operator. all wavefunctions (PEk+K with K . Then we must accept. In the representation scheme employed thus far.. k varies over the entire reciprocal space. any reciprocal lattice vector. It arises in conjunction with the degeneracy of the eigenvalues ck(R) of the translation operator tR.140) obtained by means of spatial symmetry.R (2.142) Ck+K(R) = e which follows directly from the relation K .3 illustrates these connections. beyond that of relation (2.143) with K . that an infinite number of different energy eigenvalues are assigned to each k-vector.

its point group is that of the crystal lattice and. One cells the representation involving the entire k-space the extended zone scheme. one may then inquire whether one can choose the primitive unit cell of the reduced scheme at K 0 in such a way that the discontinuities of the branches EK(k) do not occur in the interior.3: Representation of band structure in the cxtcnded and reduced zonc schemes. An analogous statement holds for the eigenfunctions of the Hamiltonian.3. is not continuous everywhere but has discontinuities at certain kplanes. Gcnmd propertic3 of stationary oneelectron states in a crystal 97 Table 2. Of course. R] k from Infinite Space 1 Extended k = kl from Unit Cell ' Reduced Zone Scheme ~ Zone Scheme whme kl is a vector of the primitive unit cell at K 0. This nieans that only the Wigner-Seitz cell of the reciprocal lattice is a possible candidate for siich a primitive unit cell. ~ . For most problems in semiconductor physics the reduced scheme is more convenient than the extended scheme.140). R] E(k + K) ~ X P ~ exp [-ikl . as a function over all k-space. Each Bloch function p. and that involving the primitive unit call at K = 0 t h e w d u d zonw schpme.2. In this way the singlevalued function E(k) over all k-space is transformed to an infinitely multi-valued function EK(k1) over a primitive unit cell. If such a special primitive unit cell exists at all. but only on the surface of the primitive unit cell. Anticipating this. Later.pqkl+Iqkl+I{(x). it must have at least the symmetry of the point group of direclionb. larger than the requisite point group of directions. theIefore. I Wavevector Eigenvalue of tR Eigenvalue of H Represent at ion I General [-ik.yk over all k-space corresponds to an infinite number of different Bloch functions pEKkl(x) . we will demonstrate that the energy E(k). as followb from the symmetry reletion (2.

4 Schr6dinger equation solution in the nearlyfree-electron approximation It is well known that the Schrodinger equation can be solved approximately if the potential. or a part of it. If one takes the periodic potential as a perturbation. At this point. however. P2 H o = -. 2m (2. i + is then the periodic potential H I = V(x). Moreover. we thus arrive at the important conclusion that the spectrum of allowed energy values of crystal electrons will have the form of energy bands. i. that lattices have fewer point groups than there are point groups of equivalent crystal directions. the solution of the unperturbed problem must be known. represents a small effect which may be treated by means of perturbation theory. We will prove that this is indeed the case for the branch Eo(kl) in the next section. 2. One calls these continuous branches energy bands and the Wigner-Seitz cell of the reciprocal lattice at K = 0 is the f i r s t Brillouin zone.e. The corresponding Hamiltonian Ho is simply the kinetic energy of the electron. it will be shown that the other branches EK(k1) of the infinitely multi-valued function E(k) may be redefined in terms of new branches such that each single-valued branch is also continuous over the Wigner-Seitz cell at K = 0. we will treat the entire periodic potential by means of perturbation theory.145) The perturbing operator H I .147) . then the unperturbed problem is that of a completely free electron. Even if it is not to be expected that this will yield results which are quantitatively accurate. (2. The issue in question thus revolves upon whether the function branches EK(k) are continuous in the interior of the Wigner-Seitz cell of the reciprocal lattice at K = 0. some qualitative understanding can be gained in this way. To apply this procedure.146) H = Ho H . Having started from general considerations and obvious conjectures.98 Chapter 2. We will discuss the concept of ‘Brillouin zones’ along with the still outstanding proof of the continuity of E(k) over these zones more fully in the next section. Electronic structure of ideal crystals We know. which together with Ho forms the total Hamiltonian (2. and that these energy bands arise by varying the quasi-wavevector k over the first Brillouin zone. The next-lower lattice point group would not contain the needed point group of directions.

The validity of the orthonormality relation (2. the zero-th order solutions must form a complete orthonormal set of functions. (2. that this holds for k-values for which the perturbation operator V has non-vanishing matrix elements (pi! I V I ~ p g )with any vector k’. Cpk and eigenvalues E ( k ) E(k) = Eo(k) 6E1(k) + + 6E2(k)+ . The two relations (2. (2.4. E (k) = -k2 0 Ti2 . Schriidinger equation solution i the nearly-freeelectron approximation n 99 In perturbation theory.151) may be easily verified by direct calculation.149) with respect to the perturbation potential. where the energy is a unique function of the quasi-wavevectors k. and the completeness relation (2.152) must hold. the exact eigenfunctions are expanded in power series. This leads to no ambiguity since we work in the extended zone scheme. .152) is proved in the theory of Fourier series.2. .150).152) is extended over all points of the infinite finely meshed net of Figure 2. we suppress the energy index E of the eigenfunctions for the sake of brevity. It is not possible to exclude degeneracy completely because wavevectors k of the same length lead to the same energy eigenvalue (2.4. = Eo(k)Cpg. more exactly. such that and -yCpp(x’)Cp. In this discussion.154) 2m We will assume at the outset that this eigenvalue is not degenerate.153) are in fact valid for the solutions (2.150) In order that the perturbation theory be applicable.154). here with respect to the periodic potential V(x).(x) = 6(x’ . The k-summation of (2. The zero-th order terms obey the equation Hop.x) k (2. The energy eigenvalue Eo(k) of zero-th order for pg is (2.153) of equation (2.152) and (2.

the correction 6 ~ : the wavefunction takes the form to (2.157) Because of the lattice periodicity of V(x) we can transform the integral over the periodicity region in (2.1 Chapter 2.159) (2.155) (2. (2.156) are given by (z. This value may be set equal to zcro.157) into a sum o f integrals over the primitive unit cell Qo(0) at R = 0: Noling that (2.162) and the total wavvcfunclion pk = ‘ ! p t 6pk is given in this approximation as .156) The energy correction 6E1(k) of the first order i s the average value (cpg I V I pi) of the periodic potential.100 2. we have (2.160) we arrive at the result Using this result. Electronic structurc of ideal crystals Non-degenerate perturbation theory h accordance with the procedures of quantum mechanical perturbation t h e ory.1551. The off-diagonal matrix element of the potential involved in (2.4.

0. The non-degenerate perturbation-theoretic results discussed above may be interpreted quite clearly if one regards the problem of the calculation of the eigenfunctions in the periodic potential as a scattering problem.2. (2. just such a degeneracy exists if equation (2.161) as (2. (2 166) In such a case.4. Moreover. the denominator may even vanish when E"(k).16 4) The second order energy correction E2(k) may be determined using (2. It is obvious from Figure 2. That the perturbation theory according to formula (2. SchrMingw equation solution in the nearly-fieet3-electronapproximation 101 One recognizes that this has the expected Bloch form (2. Such planes are familiar from the theory of X-ray diffraction by crystal lattices. 1 k.5 that the tIps of the corresponding k-vectors lie on a plane perpendicular to the vectors K or -K. we will accommodate this case and discuss the corresponding degenerate perturbation theory.165) The corrections to the eigenfunctions (2. (2. with the states 9 and cp:-K degenerate with each other.166) holds. namely that there be no degeneracy among the unperturbed energy cigenvalues for those k-values fur which the matrix elements of V ( x ) do not vanish.166) is fulfilled.Eo(k I K ) . since 1 k If jk KI. However. but first we analyze the k-values for which the condition (2.154) for E o ( k ) . and correspondingly they are not capable of significant constructive interference. Using (2.K+ -IK + . I ~ basic premise for validity of non-degenerate perturbation P theory is violated.162) and the enerffi eigmvtrlues (2. 6 ~ corresponding to the scattered part of the latter.16 7) 2 This equation can be solved geometrically. : Below. In this.151) 12= 0. the unperturbed eigenfunctions p: are thought of as incoming waves and : the perturbed eigenfunctions 9 k as outgoing waves.165) will become large if the denommator in these expressions becomes srnall.128) b r energy eigenfunctions of the crystal Hamiltonian. Actually. They aTe called Bmgg reflectam planes.we get from (2. yields only minor corrections to the unperturbed eigenfunctions is related in this picture to the fact that the incoming and scattered plane waves in\-olve different wavelengths.163) yields the Bloch factor as (2.162). with this plane intersecting the vector -K at its half-length.

If k is located exactly on the Bragg reflection plane.5. according to formula (2. have almost the same wavelengths.167). is that the amplitudes of the refiected and incoming waves should be comparable. of Bragg Figure 2. become idnitely large formally What is expectd. This interpretation can be universally applied to the propagtltion of plane waves of any kind in a system of scattering centers periodically ordered on a lattice.6: Illustration of perturba tion theory with respect to the periodic crystal potential in the vicinity of a Bragg reflection plans where the zeroth order energy levels are degenerate.102 Chapter 2. For k-vectors which obey the Bragg condition (2. . however. Actually. For incoming waves with k-vectors close to the Bragg reflection plane of the reciprocal vector -K. the above results for elwtron waves were discoverd iisinE X-ray radiation. the scattered part dpk contains a p a r t i d a r l y large hs plane wave component of wavevector k + K. one may understand the scattered wave with wavevector k K as the plane wave reflected at this plane in the sense of geometrical optics. in this case. This follows immediately from the construction of the k h g g reflection plancs in Figure 2. They are thus rapable of tor k constructive interference w i h strongly enhances the amplitude of this parhc ticular scattered wave. + + + The amplitudes of plane waves reflected at Bragg planes. the incoming plane wave and the Ecaltered wave of wavevecK. w h h is no longer applicable under the conditions of reflection. Electronic structure of ideal crystals -& \ -K f Figure 2. including X-rays. w h c h makes it the refkected wave (bear in mind that in the wave picture reflection represents an interference phenomenon).162).5: Construction reflection planes. T i is due t o the fact that. one must apply degenerate perturbation theory. The scattered wave of wavevector k K is strengthened by interference. This contradiction arises from the misuse of non-degenerate perturbation theov.

6 ) .2.172) (2. We denote a small deviation from ko by Ak where 'small' means that I A k I<<] K I. writing + ci p ( I o x= cocp:(x) PF ( ) +C K d + K ( X ) (2. one proceeds as follows. so that 1 ko. According to quantum mechanical perturbation theory for the case of degenerate zero-th order states.173) For further evaluation of this expression. The two solutions are E = Ek(k) with 1 Ek(k) -.Eo(k + K)]*+ 4 I V(K) I*.E V(K) = 0 V(K)* Eo(k+ K ) . Schrdinger equation solution in tho nearly-free-electronapproximation 103 2.171) V(K) Eo(k$ K ) .6.. The same holds for the vector k K. (2. we assume that Ak is directed parallel to K (see Figure 2 .2 Degenerate perturbation theory Let ko be a point on a Bragg reflection plane. the Schriidinger equation leads to the following set of equations. its determinant must vanish.E must hold.169) is then a vector close the Bragg plane involved.168) holds for a particular reciprocal lattice vector K. A vector k of the form k=ko+Ak (2.4.170) with co and CK coefficients to be determined. as it lies close to the parallel plane in Figure 2. The perturbed eigenfunctions cpk are sought as linear combinations of the two (almost) degenerate eigenfunctions and (p& in zero-th order. we find 1 + Eo(k + K)] f -\/[Eo(k) . Expanding the square root in powers of I Ak I and terminating the series with the second order. In the lowest non-vanishing order of perturbation theory.K+ .174) .4. 2 E*(k) = Eo(ko)f I V(K) I 4 li2 [ jpK2 1 f 2m I V(K) I] Ak2.[Eo(k) 2 (2.E V(K)* (2.E For the set to have a non-trivial solution. whence ( Eo(k) . Eo(k) .IK 2 12= 0 (2.

the relation (2. The latter observation follonrs from (2.7).174) since the applicability of perturbation theory is restricted in validity by 1 V(k) I << h 2 K 2 / 2 m .e. and the lower with a negative one. for Ak = 0. In regard to the shape of the function E*(k) close to the Bragg planes. In the formerly continuous energy spectrum a gap arises at this plane (right part of the figure).174) provides the following picture (see Figure 2. This means that. This occurs at all Bragg reflection planes. discontinuities occur and the energy spectrum exhihts gaps. i. + The remarkable feature of this result is that the 2-fold degenerate energy eigenvalue Eo(ko) = Eo(ko K ) at the Bragg reflection plane.7). Except for the Bragg planes. with the exceptzon of the Bragg reflectLon planes where. The result derived here by means of perturbation theory is also valid well beyond the framework of validity of this approximation. The two branches E+(k) and E-(k) approach Ak = 0 with horizontal tangents to the limiting values Eo(k) IV(K)I and Eo(k). the upper branch with positive curvature. respectively. splits into two different eigenvalues which are shifted by IV(K)I to higher and lower energies. + The energy f u n c h o n E(k) LS continuous everywhere in k-space. The following statement remains true also in the general case.7: The degeneracy of the two energy parabolas E(k + Ak) and E(k K + Ak) at the Bragg reflection plane Ak = 0 (left part of figure) is removed by the periodic crystal potential. Electronic structure of ideal crystals Figure 2. in the formerly continuous energy spectrum of the free electron.which means that the sign + . an energy gap appears as a result of the periodic potential. provided that the corresponding Fourier components I'(K) of the periodic potential do not vanish. Between them there is a region of width 2 I V ( k ) I where no allowed energy values may exist (see Figure 2.ll'(K)I.104 Chapter 2. 271 generat. the function E ( k ) and the energy spectrum remain continuous.

namely Bragg planes.1 Brillouin zones Definition Consider. The reason for this is that the non-central Wigner-Seitz cells are cut by Bragg planes. namely that it have discontinuities only at Bragg reflection planes and otherwise be continuous. In this. in k-space. It contains the .5.5 Band structure The perturbation-theory calculations of the preceding section were carried out in the extended zone scheme for E(k}. with E(k)continuous in the interior.4) makes it immediately clear that the Wigner-Seitz cell of the reciprocal lattice at K = 0 has the desired property . Alternatively. centro-symmetric bodies which contain the origin and are entirely bounded by parts of Bragg reflection planes. The prescription for the construction of the Bragg planes (see section 2.5.174) is always determined by the second term.it is bounded completely by planes which obey equation (2. and in its interior it is devoid of such planes. is equivalent to the question of whether there exists a primitive unit cell which is bounded by Bragg planes. in which the quasi-wavevector k varies o d y over a primitive unit cell of reciprocal space. However.1671. there is also the reduced scheme introduced in section 2. next-largest body.3. These bodies are arranged and enumerated according to their volume. The second. is described as simply as possible. 2. Band structure 105 of the angular bracket in (2. but has no other such planes in its interior. The question of whether there is a primitive unit cell which guarantees that. we will determine the choice of primitive unit cell of the reciprocal lattice in such a way that the desired property of the function E(k} discussed above.2. The correct procedure goes back to Brillouin and will be described below. each of an infinite number of choices for this cell can be used. Simplicity of the description calls for the discontinuities of E ( k ) to occur only on the boundaries of the unit cell. it remains to be clarified how the rest of k-space can be reduced t o the WignerSeitz cell at K = 0 in such a way that the resulting new function branches for E(k) are also continuous over this celL It is clear that this cannot be done by simply dividing k-space into Wiper-Seitz cells and then translating all cells not containing the origin through reciprocal lattice vectors back to the cell at K = 0. has the volume of two Wigner-Seitz cells. as one may easily demonstrate. This means that within the Wiper-Seitz cell of the reciprocal lattice at K = 0. The smallest will be the Wigner-Seitz cell at K = 0. 2. the function E(k) is continuous. Here.

These difference bodies are called Brdloum zones (abbreviated 8 8 s ) . then one obtains a hollow body of the volume of one Wigner-Seitz cell.8: The first.175) . the first B Z . The v-th body i s called the v-th R%.8 the first 10 Brillouin zones are shown for a 2-dimensional square reciprocal lattice. but contains no siirh planes in i t s interior.K(k.106 Chapter 2. and has no such planes in its interior. 10 Rrillouin zones or H sqimre plane 1al. the frr lattice and the hexagonal lattice.) represents a vector kl of the first + BZ. lattice is attached k such that k.tic:e. the Wigner-Seitz cell at K = 0 is. . . In Figure 2. which is bounded by Bragg planes inside and outside. We will derive the shape of the first of them below. first body jointly with the Bragg planes bonnding i t . a v e t o r K(k.K(k. .9. Electronic structure of ideal crystals ZONE 1 2 3 4 5 6 7 8 9 1 0 Figme 2. If one removes the first body from the second. 1953). It i s boiindd by Bragg planes. k =k l .) of the reciprocal . are shown in Figure 2.). i. The first B Z for two important 3dimensional lattices. Removing the v-th body from the (v 1)-th one again obtains a hollow body having the volume of the primitive unit cell in k-space.e. accordingly. (2. (After Brillouin. This conhtruction may be carried further. Focusing on a point k of the v-th R Z .

K ( k l ) shall be a vector of the first B Z . (right) the hexagonal lattice of wurtzite and selenium structures. instead of k. The set of reciprocal lattice vectors K(k. The correspondence of the points of the v-th B Z to points of the first B Z given by equation (2.175) is unambiguous in both directions . and each kl exactly to one k.. by folding the v-th B Z into the first.each k. If. During such folding or displacing. another reciprocal lattice vector K(kh) may be necessary in order that kh . another point kh of the v-th B Z is chosen. zincblende and rocksalt structures. The unique function E(k) over the whole k-space is mapped into the multivalued function E. this is expressed by . defined above by relation (2. the external or internal boundary planes of v-th B Z may be translated to the interior of the first B Z . By this assignment a multi-valued function E.. Its validity in the general 3-dimensional case is clearly plausible. which arises if k. K(kL). The term ‘displacing’ would probably provide a better description. is just the set of K-vectors which defines the internal boundary planes of the v-th B Z . We omit the formal proof for this important result here.175) provides the mechanism for changing from the extended description of the energy function E ( k ) over all infinite k-space to the reduced description within the first B Z . The folding operation (2.9: The first Brillouin zones of the two Bravais lattices which apply to many semiconductors: (left) the face centered cubic lattice of diamond.10.(kl) within the first B Z . For the square lattice it follows immediately from Figures 2. One terms this correspondence ‘folding’ of the v-th B Z into the first. This means that original kl-vectors which lie immediately to the right and to the left of such planes will involve different reciprocal lattice vectors. It states that the value E(k) at a point k = k. .).(kl) is defined within the first BZ. of the v-th B Z is assigned to that particular point of the first B Z which arises from k. they border on other boundary planes of the v-th B Z .8 and 2. . . corresponds exactly to one kl. The transfer of the function values is. There. Formally.5.144). varies over the whole v-th B Z .2. Band structure 107 Figure 2.

11 we illustrate the band structurc using the model of a 1-dimensional lattice. I / is the so-called band andm Between the various function branches. One recognizes that energy gaps orcur not only on the boundaries of the first BZ .176) We maintain that the branches E. for in penetrating such a kl-plane the original vector k . the validity of this assertion is obvious. Each of the function branches F.(kl) is referred to collectively as thr band structure. or energy bands. Electronic structure of ideal crystals Figure 2.108 Chapter 2. (After Brillouin.9. . which defines this boundary plane.(kl) of the multi-valued function are continuous within their entire range of ddinition. continuity is not immediately . within the fust B Z . For those psrticiilar kl-planes srising from a bo~iirlaryplane of the v-th B Z .E ( k i + K(k. However. energy regions may exist in which no energy eigenvalues occur. 1953)).(k) are also continuous on the particular planes in question.(kl)-values is thus obvious.)) E(kv).10: Folding of the second through ninth Rrillouiri zones into the first R Z for the plane square lattice of Figure 2.) in the extended zone scheme as may be seen by means of the degenerate perturbation tbwry in swtion 2. These regions are called forbidden zone8 or energy gaps. (2.4. l'he whole s r t of functions R. evident. this jump does not affect the energy eigenvalue E(k..(kl) defined above encompasses some finite interval of values on the energy scale. the equation Ev(ki). of the Yth R Z jumps by the negative of the rcciprocal latticc vector. The term energy hnnd for the set of E. The solid curves correspond l o a rornplelely free electron. In Figure 2. and the dashed ones to an elwtzon in a weak periodic potential. Thus the functions E. i.e. For points kl which correspond to points k of the interior of the v t h B Z .

The changes caused by a weak. therefore. This is due to the fact that. The first Brillouin zone is. Band striictiire 109 Figure 2. Let p v k l denote the Bloch function of energy E.(kl). Unless otherwise specified. ) k v ( x ) . in particular. E.(k) instead of E.(kl) over the first B Z is by far the most common and frequently used description of the energy spectrum of a crystal. the quasiwavevector will henceforth always be understood to lie in the first B Z . but also at its center at k = 0. The Schrodinger equation for an electron in a crystal then takes the form . Thus. surface points of the first B Z are displaced to the B Z center. and the energy gaps from those points also appear at the center. The folding procedure into the first B Z must also be carried out for the eigenfunctions of the Harniltonian. Thus we will write k instead of kl. which means. periodic lattice potential are indicated by dashed lines. In the extended scheme the same wavefunction reads q q k .2.11: Rcduction of the energy parabola of a free electron into the first B Z of a 1-dimensional lattice. during folding. The representation of E(k) as a multi-valued function E.(kl) and of reduced wavevector kl. of outstanding importance in solid state physics.5.

2n -(I.l).T). 1.( l . 1. b3 = -(I. (2.1).110 Chapter 2. 1. Two of them.182) . (2. 1. a 3 = -(I. The relation between the reciprocal and the direct lattices was discussed in section 2.179) . b2 = -(l. Similar representations are possible in 3 dimensions.i. -(I. a 27r 2x .2. a 0. These vectors read: 2n -(i. According to Table 1. 2 2 2 The corresponding basis vectors of the reciprocal lattice follow from equation (2. Electronic structure of ideal crystals ff~v/c(x) = &(k)pvk(x).I ) . a 0.180) a a a a = -(O. I. the two that are most important for semiconductors.181) (2) 6 lattice vectors having the next-smallest possible length: 27r -4%) . where it was seen that each of the 14 direct Bravais lattices corresponds to a particular reciprocal lattice of the same symmetry. 1. I). -(I. T.T).I). although not necessarily of the same Rravais type. there are 14 different reciprocal Bravais lattices. a 2n -(O. a2 = .T). 0) 1 The first BZ is bounded by the 14 planes perpendicular to the following reciprocal lattice vectors: (1) 8 lattice vectors having the length of the primitive lattice vectors given above. -(I. 1. 1.i). I). T. which means the smallest possible length overall.2. a a a 27r 2s -(1.0).T). I).123).3. -(T. 1.bl = -(I. Accordingly. 2n 27r (2. Empty-lattice band s t r u c t u r e In Figure 2.T. Below we demonstrate this for the face centered cubic lattice which applies to crystals of the diamond and zincblende structures.9. T). O . O 27r -(0.11 the energy E ( k ) of a free electron moving in 1 dimension has been represented over the first B Z of R I-dimensional lattice. with the result 27r 27r 2n .Z). which ah0 means 14 different first B Z s .178) The first RZ is the fully symmetric primitive unit cell of the reciprocal lattice. the primitive vectors of this lattice may be chosen in the form (2. are shown in Figure 2. -(I. a (2.

a A = -(o.12: Symmetry points and irreducible parts of the first BZ of the fcc lattice (left) and the hexagonal lattice (right).(k) we have 71 E u . a 2?r 0.9 eV follows for Eo. (2. is I?. 1) (2.(k) = -k h2 ( 2m +K ( ~ Y ) ) ~ . the second and third BZ's are folded into the first. (2. and normal to the four space diagonals by hexagons. and the connecting line between I? and X is A.184) Using the above listed 14 reciprocal lattice vectors K(k. For convenience we as introduce Eo = ( T ~ ' / 2 m ) ( 2 7 r / a ) ~ an energy unit. for points r = 2R o. a value of 5. We will now reduce the energy parabola E(k) = (fi2/2m)k2 of a free electron along the A-line.5.e. In the reduced zone scheme we have E. Greek letters are assigned to symmetry points in the interior of the first BZ. The center of the B Z . the point at which a cubic axis cuts the B Z surface is X . For ty(k) . and latin letters to symmetry points on its surface (see Figure 2.183) with 0 < C < 1. It is common to denote the symmetry points of the first BZ by capital letters. Band structure 111 Figure 2. for example. Perpendicular to the three cubic axes it is bounded by squares.o) -(o. The first B Z of the fcc lattice obtained by means of these reciprocal lattice vectors is shown in Figure 2.) in this relation. a 2R o . ~v(k).12). i.2. ~ ) .9.185) With lattice constant a of 5 A. x = -(o. and set E.

In some cases the same value of the function E.(k) over the points of 3-dimensional k-space would require a Cdimensional space. i. as we will verify below.(k) over planes in k-space.. A complete representation of the functions E.and A-lines. Also.4 is illustrated graphically. 6 eV.e. one can plot the band structure along other symmetry lines in the interior and on the boundary of the first B Z .11 is about Eo. in units of where the K. Electronic structure of ideal crystals (2. are the components of the vectors K. Nevertheless. uncom- .13 is that of an ‘empty’ fcc lattice.13 the content of Table 2.112 Chapter 2.. The band structure shown in Figure 2. and a definite lattice constant. For a vanishing potential V(x). and any other lattice constants. Such representations are. i. In the 3-dimensional space available to us it is only possible to represent bands E. a definite lattice. although for real fcc crystals the degeneracy at maximum can be only 3-fold. the appearance of the lowest energy eigenvalue at the I?-point and the development of several non-degenerate energy bands from this level along the A-line. along with the band structure parallel to the A-line between 0 and L not given in Table 2. and not 8-fold as for the empty fcc lattice at the energy E = 3&.4 we show the reduced energy functions ty(<) for the 14 vectors K. The width of the lowest energy band in Figure 2. As with the reduction along A.11 such features are. since the latter would create a non-zero periodic potential V(x)if they were present. 2nla. definite lattice exists because of its arbino trary translation symmetry.e. one recognizes that there are k-points associated with the same energy value several times. However.4. then we cannot take any empty lattice band structure but must chose the one for the lattice applying to the crystal under consideration. i. and not &fold as for the fcc lattice at E = 4Eo.’s. one of them crossing another band at the X-point. together with those for 0. meaning that the corresponding energy bands are 4-fold degenerate. A degeneracy higher than %fold turns out be accidental. Kvy. which is identically zero in this case. a fcc lattice whose lattice points are not occupied by atoms. not caused by symmetry. in the sense that we could have also chosen any other of the 14 Bravais lattices. if we want the empty lattice band structure to resemble the band structure of a really existing crystal. It is also consistent that the energetically high-lying bands display a relatively high degeneracy at the I?-point. This was an arbitrary choice.186) K. Again. the fcc lattice. Later we will verify that the band structures of real crystals and the pertinent empty lattice band structures have in fact common features.e. this result is not too far from the actual widths in fcc crystals. In Table 2. In Figure 2. but by the particular values of the potential.(C) is obtained for 4 different K. In Figure 2. were chosen in the above procedure. however. for example.

-4s a rulc. The question of what valws the energy band functions E.(k) take outside the first B Z does not arise or is meaningless. Band structure 113 (KV&V.K.5.) cy(c) Notation Degree of Degeneracy ( i i i ) (iii) (111) (iii) 2 + (6 + I)* 4 I cz c2 F3 4 (zoo) (200) (020) (020) 4 mon.as in Figure 2. one plots the energy against lines in k-space.13: Band structure of an empty fcc lattice. since the E.13. .(k) were "L A r A Wavevector X Figure 2.2.

the boundary condition (‘2.114 Chapter 2. (2. The value of E. then kb cannot also belong to it.(k) if one approaches the point kb coming from the interior of the first B Z . defined only over the first B Z .188) where k is in the interior of the first B8. obey the boundary condition lim E. Tising continuity of the function &(k) defined over all kspace. reason why one continues the e n e r a bend fiinctions R ( ) which actually . The most natural manner to do this is the periodic continuation.e.(k) are just different descriptions of the same property. this property may be expressed in a more convenient way.187) where k is a point of the first B Z . By periodic continuation.(k) outside of the first B Z . it is equal to E. a necessary condition for continuity of the periodically continued function is that the original function.(ko). one has to define them there. Periodic continuation In this context. because a primitive unit cell contains only nonequivalent points. In order to have continuity. Electronic structure of ideal crystals just defined by transferring the function values from other B Z s to the first one.(k) = k k& - E. since the continuity of the periodically continued function E. If ko belongs to the first BZ. as such. the periodically continued function will not be continuous in the entire k-space. These conditions follow from the fact that the boundary of the first B Z consists of pairs of equivalent parallel planes (see Figure 2. For this reason.as we will assume. The question is what analytic properties does this function have? If one considers an arbitrary function.6). and the continuity of the periodically continued function E.188) for the function E. Thus. i. and kb denotes the equivalent point on the other plane of the pair. one can of course extend each function originally defined only within the first B Z to the entire k-space.k. If one wishes to also consider the functions E.(k) must satisfy certain conditions on the boundary of the first B Z .(k) defined over the first R E . discontinuities will occur on the boundaries of the Wigner-Seitz cells. thix value must coincide with the limiting value of E. the E. We denote a point on one plane of such a pair by ko.(k) implies that equation (2. E.188) holds.(kb) is defined by the periodic continuation and.(k) in Wigner-Seitz cells having centers at K # 0 are defined by the relation (2. the values of E. This condition is also siifFicient. In order for the periodically continued func%iorrt o be continuous.(k) already encompass the entire spectrum of eigenvalues as k varies over the first B Z . This is the .(ko). Therefore.

The continuity of the periodically repeated energy band functions E. To this end. and symmetric k-points were excluded. If one replaces the column and row indices K‘and K . That it also exhibits the periodicity of the reciprocal lattice.(k) are identical.188).(k). one obtains the matrix at the original k-vertor.(k) are the eigenvalues of the matrix of coefficients of this system of equations and their k-dependence i s determined by that of the matrix.2.3. The latter is manifpstly continiioiis.178) takes the form (2. on the one hand. We will now prove that the energy bands E. nand structure 115 have meaning only within the first BZ. This i s particularly important for the theory of the optical proprrties of semiconductors.5. one may verify as follows. This was discussed above in the extended zone scheme.189) Using this result.(k) actually obey the boundary condition (2. the Schrodinger equation (2. by K’+K” and K K”. This implies that the eigenvalues Ev(k t K”) and E.190) The E.178) for the eigenvalues E. namely the implications of point symmetry for band structure. are continuous everywhere as periodically continued functions. Consider the coefficient matrix of (2. + + + + . respcctively. One could also forego this. as stated. as follows: + (2. where K is an arbitrary reciprocal lattice vector. NOW we USP the reduced zone scheme description and concentrate on symmetric k-vectors.188) directly. and use the condition (2. The above proof employs only the lattice translation symmetry of the potential V(X).(K’IVIK).190) at the point k K” with K” an arbitrary reciprocal lattice vector. we use the Schrodinger equation (2.(k) is often very useful. It ensures.k(x) may be expanded in plane waves with wavevectors k K .periodically over the entire k-space.(k) may be npproximctted fairly closely by a Fourier series with relatively few terms. We return now to a question which was previously explored in section 2. that the E. mathematical theorems dealing with the types and numbers of extrema of periodic analytic functions may also be applied. On the other hand. using the relation (K’ K”IVJK K”) . and thus.(k) in the entire reciprocal space is therefore an immediate consequence of the periodicity of V(x) in the direct lattice. The corresponding Bloch functions p. The continuity of the periodically rontinued function E.

as the Wiper-Seitx cell of the reciprocal lattice. For k-vectors on symmetry lines or planes. the point symmetry of band structure as given by equation (2. Using the terminology above. This set forms a subgroup pk of P . which underlies the extended zone scheme. vectors which are transformed by at least one element o f the point group 1’ of equivalent directions.e. also cxhibits the point synmelry of this lattice which. The first B Z of the fcc lattice has.191) may also be described by saying that the energy of a particular band has the same value at all points of the star of a wavevector. b3. A general k-vector bas no point symmetry. The center of the first BZ is special: all elements of P arc also dements of Z’k. The energy bands likewise have a particular point symmetry. and is called the s n ~ a l l poznt group of k.5. It may.12 marked with Iargr greek or latin letters are among them. be transferred immediately to the reduced scheme.2 Degeneracy of energy bands The first B Z . and the number of different star points of k by S k . inlo a vector crk equivalent to k which differs from k only by a reciprocal lattice vector K. bp. ‘The latter statement follows directly from the definition (2. The points of the first B Z in Figure 2. The latter rase occurs for the diamond structure. In section 2. The second subset contains all those elements of P which transform k neither into itself nor into a vector equivalent to k. however. Electronic structure of ideal crystals 2. were excluded.140). at points on the surface of the first B Z . whence p k = 1 and A k = p . p k has a value between 1 and p . This is expressed by quation (2. and its point group is Oh(m3m). 7 . This group is generally smaller than the point symmetry group of the lattice. for its part. The set of all different and non-equivalent vectors a k is called the star ofk. is the same as the point bymmetry of the corresponding direct lattice.116 Chapter 2. so that we may also write &(k) = E v ( a k ) . so that pk = p and S k = 1. the number pk of elements of the small point gToup P is given by k the relation p k p l s k . Since each star point has the same point symmetry. In r q a r d to their effect on symmetric kvectors. where the point group of equivalent crystal directions is likewise o h . i. We denote the number of elements of the point group P by p . therefore.3.19 1) where a is an element of the point group of equivalent directions of the crystal. namely that of the equivalent directions of the crystal. into themselves or into an equivalent vector. The Erst contains those elements which transform k into itself or. the elements cr of P split into two subsets.123) of the reciprocal basis bl. (2. is a symmetry point. but in special circumstances it can also be the same. symmetric k-vectors. Now we also admit such k-vectors to consideration. A wavevector whose small point group does not consist of only the unity element. the point symmetry of a cube.

(k) need to be calculatcd only for a scction of the first B Z which covers the region between adjacent star points (Figure 2.k(x) = cpVk(cr-’x) is also an eigenfunction of the Haniiltonian H with the same eigcnvalue B. then one also knows what degrees of degeneracy of the energy bands are possible at k.(k). or change it only by a reciprocal lattice vector. . Band structure 117 Y~UT Onc therefore also calls this symmetry the degunrrucy OJ e n e r g y bands.(k) i s d. The functions are then likewise eigenfunctions with the eigenvalue E.2.r. Bmause of star degeneracy. t h e are several linearly independent eigenfunctions for a given band index 11 and wavevector k. Thus. .k. As such.12). In Appendix A we explain that the matrices D p l ( a ) form a r e p r e s e n t a t z o n of the small point group of the wavevector k. in the case of diamond structure.duk. the energy band functions E. If the clegeneiacy of the energy eigenvalues i s only due to the symmetry of the Hamiltonian. . lor the case in which not all wp. into an eigenfunction cp. This relation between degeneracy and symmetry . The dimension of this reprcsentation. is 48. One calls this kind of degeneracy band degeneracy. Those elements a of this group which also do not change the wavevector k. If one knows all irreducible representations of the small point group Pk. the dimension of its matrices.192) each element a of the sniall point group is associated with t~ matrix D p l ( a ) . will thus transform an eigenfiinction pvk(x) of a particular Land v and k-vector.k(x) are linearly dependent.(k). then this representation is arreducihle. acp. the number p of elements of the point group 0 . We employ q l k ( x ) .3 it was shown that for any eigenfunction (p. We may say that the eigcnfimctions of the Hamiltonian for a particular k-vector and band-index v span a subspace in Hilbert space which gives rise to an irreducible representation of the small point group. i.1 . The energy eigmvulues for the remainder of the first B Z are obtained by means of the symmetric continuation (2. Through relation (2. whence crcplk(x) (2. to denote a basis set in the subspace 1 of eigenfunctions or H having the eigenvalue E.5.k-fold degenerate at the point k. . In section 2. they can be expressed as linear combint\tions of the basis functions pVk(x). provided (1 belongs to the symmetry group of 11.k(~u-~x) of the same band and the same k-vector.k(x).191) of the values of the irreducible part.(k). Let their number be d. The irreducible part is the p-th part of the first BZ. corresponds to the degree of degeneracy of the energy band for the k-vrctor mider consideration. One calls such a section an zrrediiczble part of the first R E . If one considers that. one can appreciate how greatly the 1 description of band structure is simplified by exploiting the point symmetry of crystals. This means that t h e energy band E.192) with Dpl(a) as expansion coefficients. 2 .

i.118 Chapter 2 Electronic structure of ideal crystals . T and Td(332) of the cubic h crystal system.and 3-dimensional. For the point f groups of equivalent directions. the irreducible representations can be only 1-. supplemented by subscripts.5: Irreducible representations (notations and dmensions) of the smaLl point groups of symmetry points and lines of the fist B Z o the fcc lattice for f crystals with the diamond structure. A X - - c K is quite remarkable.I112.2.e. r15. It holds not only for the energy bands o crystals. l-dimensional for small groups. For the I?-point and diamond structure. as are the dimensions o the representations. we consider some s p a i d k-vectors of the first BZ of the fcc lattice. 2-dimensional only for groups that are 'not too small'. For the point X. At the center r. b i t e . the irreducible representations are denoted by rl. with o h . ~ The number of distinct irreducible representations of an arbitrary finite group is. the irreducible representations of the small point groups are denuted by the same capital greek or latin letters which stand for the k-vectors. the small point group is identical with the full point group P for crystals of diamond structure. & somewhat strange indexing refers back to the so-call& compatibility rela- . specifically for Oh(m3m). In the context of energy band theory. I?$. To illustrate these somewhat abstract statements and to prepare for the discussion of actual band structures in section 2. and I. Table 2.8.r25.the theory of groups has immediate physical consequences. ? . and 3-dimcnsional only for the largest point groups. (See Append& A ) . It is a good example how a relatively abstract mathematical theory .0(43m). f but for the eigenvalues of any Hsmiltonisn in quantum mechanics. the projective irreducible representations are given in the crystallographic factor system.Tz. This I.

n . have the same energy. If a particular symmetry point ko of the first BZ is transformed into itself under the action of a point symmetry operation a . 2. The degeneracy is thus n2-fold for the hydrogen atom. which is the small point group of r for crystals with the diamond structure. 2 . which will lead us to the concept of critical points and effective masses. . At X there are 2-fold degenerate bands exclusively. the symmetry-related degeneracy is still not the full degeneracy. The primes indicate that the involved representations differ from the unprimed ones only by a minus sign for the inversion matrix. We proceed now to another consequence of this symmetry. However. In the case of the hydrogen atom. Band structure 119 tions between different representations (see Appendix A for more detail). In Table 2. In addition to the symbols of the representations.1. The dimensions of the irreducible representations of this group are determined by the angular momentum quantum number I . In the latter case the degeneracy is likewise a consequence of rotation and reflection symmetries.1.00. save only for a scalar factor (see Appendix A). then points ko 6k in the vicinity of ko are necessarily transformed into points close to ko. This peculiarity is due to the fact that the space group of the diamond structure is non-symmorphic. all irreducible representations of the point group o h . Amounting to 21 1. the point group contains an infinite number of elements. . arbitrary rotations and reflections are possible in this case..and %fold degenerate bands at the center of the first BZ. all odd numbers are possible as dimensions of irreducible representations. the irreducible representations of the small point group of X involve a factor system.2. The irrek ducible representations of the small point groups P of the symmetry points A. Thus all eigenstates corresponding to a given n .5.5. X .5. their dimensions are given. In such circumstances. 1 .. . and hence also as the multiplicities of energy eigenvalues. . In addition. i. are listed. is a direct consequence of the symmetry of these points. where 1 can take the values 0.5. + .2.e. A and L for crystals having the diamond structure are also indicated in Table 2. + 2. one has an accidental degeneracy caused by the particular shape of the Coulomb potential. it is understandable that 1-dimensional representations may not be possible. .3 Critical points and effective masses The degeneracy of energy bands at symmetry points of the first BZ which we treated in the preceding subsection. According to this table. ' The degeneracy at I may be compared with that of a free atom. In this case the energy eigenvalues differ only for different principal quantum numbers n. . one has both 1-. If. which means that multiplication of two representation matrices yields the matrix of the product element.while at all other points only 1and 2-fold degeneracies occur for crystals which have diamond structure. with their various 1-values 0. In this case.

then points of the form ko 6 k e.(k) be a regular function at k.(k) vanish simultaneously. will transform into ko . One can easily prove (and we will do so in section 3. thrrr the b. however. Because of the symmetry relation (2.(k) with respect to the three wavevwtor components vanish at symmetry points. namely those with respect to the normal plane. then the average momentum in the corresponding Bloc11 state is also zero.(k) will have the same value before and afler the reflection. are defined formally by the equation (2. E. apart from a constant factor. What is being demonstrated here using the example of mirror planes has a general significance: some or all of the first derivatives of the energy band functions E. From this it follows that the first derivative of the function EV(k) with respect to k. with ex as unit vector in x-direction.120 Chapter 2. without..one may approximate it in the neighborhood of k by a Taylor expansion to second . If ko also simultazlcously lies on a second mirror plane perpendicular to the first. nainrly the one in the normal direction. This also explains the name of these points.6 k . we may say that at symmetry centers all three fiist clerivativcs are zero. With some ambiguity of expression. the remaining first derivative parallel to thv line also vanishes. depending on the degree of symmetry.191) for energy bands. These points are called crztical points.(k) vanishes. at symmetry lines two vanish. also has to vanish. equal to the expectation value of the momentum operator p in a Bloch Btate. ex. one perpendicular to the y-axis. a i s a reflection with respect to u plane normal to the x-axis.(k) will also be zero. Critical points k. We will later see that the so-called denszty of + d a t w possesses singilnrities at energies whose constant energy surfaces contain critical points. for reasons that have nothing to do with symmetry. wheie.3) that they are.194) With the requirement that E. .-derivativp of f!!. e. being generally identical to them. The critical points h a w a close connection with symmetry points.193) If VkE. Electronic structure of ideal crystals for example. and on symmetry planes one derivative vanishes. On a symmetry line there are also often special points. then the derivative with respcrt to k. The first derivatives of the function Ey(k) with respect to k have a direct physical meaning. If ko i s even more symmetric and involves a third mirror plane normal to the z-axis. must vanish at the mirror plane. thus + (2.g. These are occasions which warrant special consideration and examination of points the first B Z in which all first derivatives of E.

of M. Actually one can obtain the expression (2. . i. An analogous statement holds for the inverse..196) IJsing this tensor. Thus. Therein the crystal potential manifests itself.197) Thc tensor components cnter this expression in a manner similar to the way the reciprocal mass rn-l enters the energy dispersion relation of a free electron. the expansion (2.195) of E.2. but with coefficients M. for the case of an electron in a crystal they represent u tensor ML$ with non-vanishing off-diagonal elements and general diagonal elements. the effective mass is a tensorial quantily. One therefore calls M u the effectzve mas8 tensor. In contrast to the free electron case. Only in the vicinity of critical points does the quadratic drprndenre persist. which differ from those of the flee electton. a scalar quantity. in general. as the cffective mass tensor M.197) by Erst taking the energy zero at E u ( k c ) which is unimportant. The term ‘effective’ refers to the fact that the electrons of a crystal are not free elcctrons but arc subject to the influencc of thc periodic potential.p. They are eflectztw coefficients which involvc the effrct of the periodical potmtial. Then.154) for the energy of a free electron from (2. where the coeficients form a multiple rn-l of the unit tensor 6. and then by substituting (2. T h e presence of this potential mandates that the wavevector of the free electron be repIared by the quasi-wavevwtot k..e.g defined by the equation of a second rank tensor M L 1 (2. and that the quadratic dppendenre of the energy on k become a more complicated dependence. In special c‘ase‘s one ran approximate the effertive mass by a scalar quantity rn.$.’ accordingly have the dimension of a mass.5. Band structure 121 order Here. generally generating different mass values in different spatial directions.198) The components of the invrrsr tensor M . we introduce the components M: .(k) may be written in the form (2. the difference between the mass of the free electron and that of the crystal electron reduces to the different magnitudes of the two masses.

i. (2 203) For the frequentIy observed case of a symmetry point at the center of the first BZ!i. general differs from mZI. The same applies to thc inverse quantities. lies on a symmetry center of the . then E . one has ms' The m. in :. and that this is simultaneously one of the principal axes. F12 (2. As is well-known from linear algebra. such a real symmetric tensor cau be brought l o diagonal form by a coordinate transformation.202) The corresponding element for the symmetrical principal axis m:3 E m . i. as componenls of k in the principal axis system.y follows directly from the defining equation (2. With the principal diagonal elements of M l l in this system. to the principal axis system. with k = 0.z 22 Chapter 2.e. 2m.201) If all three effective masses are positive.199) This propat. one gets the simple dispersion law . then all three elements are in fact identical.e. we have (2. Taking k. however. If k.and if all three are negative it is a maximum.(k) = E v( 0) + -k2. the energy function E w ( k ) has a minimum at the critical point kc.196) for M&. With LY = 3 for the symmetrical principal axis we thus have mC1 = m t 2 (2. the two principal tensor elements normal to this axis must be equal. first B Z .' are real. E.e. ( k ) has a saddle point.. In general. Electronic structure of id& crystals The mathematical description of effective mass can be simpl%d by exploitMv:. in our case o the f being components of the k-vector. the effective masses r k n themselves. for symmetry reasons.204) . by using the relation ing the symmetry of the tensor (2. Then. If the three effective masses do not all have the same sign. with rcsppct to an exchange of its indices a and 3. they can take both positive and negative f values. l e on a 4is Consider the particular case in which the critical point fold symmetry axis of the first 3 2 .

a knowledge of the density of states is enough to calculate important macroscopic properties of semiconductor crystals. one has + 2 ~ ( E ) A E.A z ( E ) .205) O i is called the density of states (DOS) of the system. In the following subsection we will again deal with band structure in its general form E. The quantity p ( E ) = . that p ( E ) does represent the number of o n e particle states of energy E per unit energy and volume. The sum in (2. therefore. (2. . cannot be set equal to zero for all bands by changing the zero of energy. We will show that this designation is justified. = 51 (2. the number A z ( E )of states having energy in this interval.(k). obtaining + 2 P(E)AE = FL E+AE dE'6(E' .5. 2 (2. its eigenstates (disregarding spin) by li)..e. each state i whose energy lies between E and E A E contributes '1' to the sum on i. i.5.Ei) = 1 for E < E i < E + A E 0 otherwise . .E i ) . We will introduce the so called density of states that encompasses essential information on band structure in just one function of energy. Considering spin. appears instead of the free mass and that the energy at k = 0 assumes a value E.. Often.C 6 ( E .4 Density of states Definition We first consider an arbitrary infinite oneelectron system. .206) The integral on the right hand side yields JEE+AE dE'6(E' .206) equals. 2 . To this end we integrate equation (2.Ei). Periodicity of the eigenstates is assumed with respect to a periodicity region of volume 51. (2. with no contributions from all other states.208) .205) over a small energy interval E < E' < E A E . and its energy eigenvalues by Ei.2.207) Thus. 2. 00.(O) which depends on the band index and. i = 1 . Its Hamiltonian will be denoted by H . therefore. Band structure 123 This differs from that of a free electron only in that the effective mass rn.

equals + p ( E ) = --Im 7T Tr (2. One must divide by this volume in writing the sum as an integral.210) uk The k-sum is over all points of the finely meshed net of Figure 2. for energies in the v-th band.is defined by the expression (2..205) for an ideal crystal. (2.r.. The L)OS expression (‘2.124 Chapter 2. Because of the fineness of this network. one can easily prove that p ( E ) of (2. We now consider the DOS p ( E ) defined by (2. and the DOS p ( F ) therefore reads p(E)- 2 -C 6 ( E - ’ (2.205) may br written in a more compact form which will be used in Chapter 3 in the derivation of important general results.205).205). in this case.209) transforms immediately into (2.213) and it differs from zero only for energy values for which the argument of the 6-function may brrome zero. p u ( E ) . expression (2. i.212) which is independent of the volume R of the system.211) The factor f l / 8 m 3 in front of the integral ocrurs because the volume of a mesh element is the G3-th part of the volume 8n3/Slo of a primitive unit cell of the reciproral lattice. The density of states follows as (2..214) .209) where trace sytxho1 ‘Tr’ denotes the sum over all diagonal elements with respect to any basis set in Hihert space. Summing over d l bands one again obtains the entire density of states (2. the result of the summation is almost identical to that of an integration. whirh is 87r3//n.. If this set is identified with thr eigmstatcs 12) of ff. The cigenstates li) are Rloch states Ivk). Noting that the 6-function 6 ( & ) is the imaginary part of -(1/7r)l/(E ie) with t a small positive number.= -1 R k 8T3 d3k .4 which lie within the first B Z . except for a factor R. Electronic structure of idcal crystals confirming the designation of p ( E ) as DOS. The substitution of the s m by an integral is done in accordance with the prescription c. The density of states restricted to the u-th energy band.

(k.(k) is given by the expression (2.216) i s only justified within its limits of validity. thus obtaining (2. i. obtaining (2. The inteErand l/IVkF. ( E ) may be transformed into a surface integral over the constant energy surface &(k) -= E using the rules of calculation for the &function. from the edge of lhe first B Z to infinity. If we further replace E. For such energies it so happens that the value of p . in other words. then the expression for &(k) becomes (2.e. singularities of the density of states as a function of energy are to be expected. apart from a factor TL. at a critical point. we suppose that the function E. i. i.(k) close to the minimum E d . Parabolic energy bands We aasunie an isotropic parabolic energy band.0.2.) by E N .e. The critical point k. the longer an electron stays at it. We transfer this limit. is taken to be positive. The use of the dispersion law (2. we transform to new variables x. be relied upon.e. along all three main axes. for simplicity. E. ( E ) does not depend on the upper limit of integration.’. formally..(k) should have a minimum at k = 0. The effective mass rn.(k)l . They are called van Hove singularitiee.(k)l is. the larger is its contribution to the density of states.213) for p .is taken as the origin 0. If (VkE. execute the integration over z using the rule . infinitely large.201) with the sainc effective mass rn.216). ( E ) from equation (‘2. The smaller this velocity is at a particular k-point on the constant energy surface or. the reciprocal absolute value of the group velocity of an electron in the Bloch state Ivkq).5.e. i.2 16) We use this to calculate the density of states p . z To start we. for energy values E.(k) -= E .213).215) with df as element of the constant energy surface E.y. the contribution is. From this it follows that for energy values E whose iso-energy surfaces contain critic81 points. Only for these E-values can the density of states as calculated by means of (2.2 17) In this integral. Rand structure 125 Expression (2.

z 2 ) = .Euo) = 1 f o r E > Euo 0 for E < Euo (2./E . This is one of the already mentioned van Hove singularities of the DOS.y2 . These singularities occur not only at energies where a particular band E. as in the . It has.2 It follows that where B(E . and the density of states again falls off to 0 there.E& - > 0.the first derivative with respect to E is 0 if one approaches the edge from the forbidden zone.x 2 .y2 f o r E . instead of an isotropic parabolic band.126 Chapter 2. The sudden square root-like increase of the DOS at the band edge reflects the fact that the function p(E) has singularities at these energies . Electronic structure of ideal crystals 1 E . In reality the band edge lies at finite energies.222). ~ x 2 . (2.220) the density of states of a parabolic band with m*. .(k) has a minimum. but m: must be replaced as follows (2.E . qualitatively. an anisotropic one with three different effective masses m:l. According to expression (2. m:2. This may be seen immediately if one reviews the calculation for the isotropic case.222) by the so-called density-of-states-mass m b . If one considers.EA . then the density of states is again given by expression (2.the factors for the 3 components are different and lead to the modification indicated in equation (2.2 = .221) is the Heaviside unit step function. and continues following a square root law up to infinitely large energies. the shape shown by the dashed curve of Figure 2.[S(z .14. The anisotropic effective mass involves a change only upon substitution of the variables for the components of the k-vector .ZO) 2zo with Zo +6(z+ ZO)] (2.220). m:3 corresponding to the principal axes of the effective mass tensor. > 0 exhibits square root-like behavior at the lower band edge. The latter property is a consequence of our untenable assumption of parabolic dispersion up to the upper band edge and the replacement of this edge by the point at infinity. and it is +CXJ if one approaches it from the interior of the band.

Such k-Bpaces have physical (as well as mathematical) meaning. The n m b r r A Z of b m d states with energy between E and E .and thickness Ak which. (2.o = 0.2. has radius k~ 6: &. These kvalues lie in a thin spherical shell in k-space [see Figure 2. -AE. Band structure 127 Figure 2.223) For the volume AV of this shell. 1 fi (2. unlts) case considered here.and 1D density of s t a t e s The square root enerw dependence of the density of states in the case of a parabolic dispersion law may also be demonstrated in the following.5. ( 4%. and omit factors which do not depend on k or E. Counting states: 3D. since Ah' CK k&k. 2D. thus also at maxima and saddle points. is given by Ak 0.15) which. in particular for electron systems whose free .his interval. more vivid way (also see Figure 2. the number of k-points in the spherical shell is proportional to its volume AV. k2.f A E is the number of different k-points of the finely meshed net which yield energy values in t. Hence AZ cy v%AE and p(E) o. (22 2 5) Such considerations can easily be applied to energy bands in 2-dimensiouel (2D) and 1-dimensional (1D)k-spaces. because E o(. it follows that AV m k L A k cc A A E . The dashed curve shows the DOS of a more realistic band.14: DOS of a parabolic isotropic band in the vicinity of its minimum (solid curve).224) Since the density of the finely meshed net of k-points of the first BZ i s the same everywhere.15). For simplicity we set E. 5- I I I I c < vl 4- = 321- I 0 0 1 2 0 -1 0 3 4 Energy lorb. but at a l energies corresponding to critical points of l the energy bands.

and (c) 1D k-space.228) . Electronic structure of ideal crystals b C Figure 2. : (2. is taken into account. and electrons in a homogeneous magnetic fieId for the 1D-case. Therefore. that spin and spin-orbit interaction play an important role in most semiconductors. motion is confined to one or two dimensions of 3-dimensional space. For 2 0 k-space. (b) 2D.surfaces and quantum wells for the 2D-case.227) 2. 1 fi (2.15: Counting states in (a) 3D.226) The density of states of a 2D-electron system is therefore independent of E. the volume of the spherical shell is replaced by the area A F of a circular ring.128 Chapter 2. the question arises as to how the results derived above for scalar wavefunctions change when electron states are no longer scalar but spinor functions and the spin-orbit interaction H . however.5 Spin Thus far. p ( E ) DC -AE.58) with spin.5. Thus. spin has been omitted from our discussion of the general properties of stationary oneelectron states of crystals. The starting point to address this question is the one-electron Schrodinger equation (2. which may be written in the following short form (2. We wiU encounter examples of such systems in Chapter 3 . It turns out. such that A F a k E A k L A E and X p ( E ) 3 const. In the case of a I k-space: AV is replaced by the length Ak of the k-interval D itself.

5 6 ) ) .5. In t.2. If k is restricted to the first B Z . s) of a spinor transforin i d e r thr operations g of the space group. Spatial symmetry Inspecting the explicit form of the spin-orbit interaction operator ( b e y formula ( 2 . It.hc components of a spinor is discussed in Appendix -4. we have In t. where I ~ X ~ [ X . the cornmulivity of the HanliltoIlittn with translations gave rise to the Bloch theorrm. The results of Appendix A are applied here in the form .hr Schrodingeer equation (2. g] = 0 . Since the i one same holds for the spin free part H of the total Hamiltonian ! + has Iff + H. Band structure 129 The first point we will consider is that of spatial symmetry in the presence of spin. (2. are the spin-dependent Bloch factors..he absence of spin. we consider point symmetry operations u . its validity may be also demonstratd here in the pwsrnrr of spin. Thus it colrimutes with all elements 9 of the space group. then E x ( k ) rrprwents a continuous function of k Thc band .229) To exploit this symmetry property of thv total Hamiltonian w e mu61 know how thc components p(x. whose action in tramforming t. zti) Second. y ~ ( xf)}of . one readily recognizes that TKso has thc full symrwtry of the crystal.he same way that this theorem was proved without spin above. t. Considering translations first.228) for the eigenvalue E A ( ~ ) be chosen in can the form of Bloch type spinor functions with a particiilar quasi-wavevecbor k as 4). index X here refers to both the state of the orbital motion and also to spin state. stdates that the solutions { p ~ k ( x .

in short. 2 then all spinor representations are obtained. s). These give rise to spinor representations of the (full) orthogonal group which differ. in coordinete space. the already discussed connection between the eigenfunctions of the crystal Hamiltonian for a given eigenvalue and the irreducible representations of its symmetry group may be generalized in the following way: ~ The spinor eigenfunctions of the crystal Hamiltonian W H . Thus the representations of the full orthogonal group in the space of two-component spinors are not representations in the ordinary sense. Indeed. having the same energy eigenvalue span a representatdon space of a n irreducible spinor + . The set of a l orthogonal transforniations cy. representation Vi x Vv.a change of the angles cp or $J in (2. but in a generalized sense. here. Up to this point we have only given attention to the transformations of spinors in spin space. Electronic structure of ideal crystals In this. or. if a spinor field (P. They form projective representatiom with a special factor system (see Appendix A). Through relation (2. A peculiarity of thm mapping is that it is not unique 1 . $. encompasses all vcctor representations. The spinor representations are those representations of the double group which do not occur among the ordinary representations of the single g ~ o u p (for the derivation of this result see Appendix A). D. with s = fk. This gives rise to multiplication rules for the representation matrices which deviate from those of the group itself.233) by 27r leads to a change of the sign of the associated matrix. By means of the so-called double group. of the fill1 orthogonal group twice. the transformation just reduces to multil plication by the matrix D r ( a ) . B and p are the Euler angles of the orthogonal transformation a. even though this signifies the identity transformation.233) this group is assigned a matrix group D i ( a ) . Using the concept of spinor representations. once in the original form. 2 forins an (infinite) group. transforms according to a certain ordinary representation D. and once multiplied with a rotation through 27r. spinor representatiom. The states of electrons are described by spinor fields having positional dependence.(x. one may trace back the spinor representations to ordinary representations. If the spinor is spatially constant. The totality of spinor representations may be obtained from the ordinary irreducible representations V. One may say that under a rotation through 27r a spinor does not transform into itself. but into its negative. from D i . in general. and the particular spinor representation D1 of the full 2 orthogonal group. then its transformation in coordinate spin space is governed by the product If. which includes each element.130 with Chapter 2.

This means that.. + H. two irreducible spinor representations ra and r 7 of the point group T d of I where rs is of dimension 4 and r of dimensiun 2. are generally reducible. but as an accidental rather than a symmetry induced degeneracy. the space The product representations Dr. .2. without this interaction. Band structure 13 1 Table 2. degeneracy persists. We consider the valence band of zincblende type semiconductors which is triply degenerate at I The .x V v .5. The following example illustrates the removal of degeneracy.6 the irreducible spinor representations are shown for some symmetry paints of the first BZ of diamond type semiconductors. It decomposes into the a ' . the triply degenerate r15-valence band without spin splits into the $-fold degenerate rs-band and the 2-fold degenerate r7band. accounting for the effects of spin. ' product representation in this case is Di x 1-15. due 7 to the spin-orbit interaction. The magnitude of the energy splitting depends on the spinorbit interaction. This means that bands which are degenerate without spin by reason of spatial symmetry. representation of the full symmetry group of H group of the crystal). taken as representations of the sman point groups of a particular wavevector rather than for the full orthogonal group. (namely. In Table 2. may split if spin is taken into account.6: Irreducible spinar representations (notations and dimensions) of the small point groups of symmetry points and lines of the firat B Z of the fix lattice for crystala with the diamond structure. A systematic treatment of these representations is given in Appendix A.

Let {cpxk(x.$)} must be replaced by K{cpx(x. the effect of timc reversal on H . case. then the eigenfunction {cpx-k(x. i)} i)} i).234) To prove this assertion. cpx(x. i). The question. and p into -p. The vector a' then transforms into -a*. so that the net change in Hso is the replacement of d by a'*. since i). is given by the relation i). under what conditions time reversal symmetry includes degeneracy of eigenfunctions not accounted for by spatial symmetry alone. two linearly independent eigenstates of the same energy have the wavevector k. K must have the form given above in equation (2. at reversed time. cpxk(x. First. Electronic structure of ideal crystals Time reversal symmetry As the consequences of spatial symmetry are altered by the phenomenology of spin.. one executes the time reversal operation on the spin-orbit interaction operator H. . of equation (2. cpx(x. The time reverse of the Bloch function {cpx-k(x. as one may easily show by evaluating the scalar product (here. i). i). due to time reversal symmetry. on the other hand.234). corresponds to the same eigenvalue Ex(k) -= Ex(-k). $). Here we deal only with a specjal cp~(x. cpx-k(x.180) to remain valid. may be expressed in terms of the similarity For the two expressions to be identical. i). Employing the operator K . i)} (2. into the spinor K{cpx(x. one also has to sum over the spin coordinate s ) . cp~(x. We consider a non-symmetric wavevector k.. If the point group of directions contains the inversion. . $)}. be an eigenfunction with energy Ex(k). Since k was chosen arbitrarily.K-'. apart from a phase factor which remains undetermined.56) explicitly.we $)} will show that the operator K which transforms a spinor {cpx(x. Thus. cpx(x. The wavefunction {cpx(x. $)} likewise has energy Ex(k) and wavevector k. $)} for the Schrodinger equation (2. is treated in Appendix A in full generality. It is linearly independent of {(Px~(x. transformed operator KH. all bands of inversion-symmetric crystals are at least twofold degenerate. cpx-k(x. so is the action of time reversal symmetry changed by spin.132 Chapter 2. it follows that.

i. The f i s t is the Coulomb interaction with the atomic nuclei . It depends on the very same eigenfunctions that are to be calculated. Band structure 133 2.6 Calculational methods for band structure determination There are many methods.e. the aid of empirical data and calculate the band structure from first pnnczples. the determination of thc cffectivc oncclcctron potential V ( x ) . quasi-analytic and numerical. Methods which proceed in this way are referred to as ab znztzo methods.5. for calculating the band structure of crystals.c. These potentials are described by expressions which are completely analogous to those for the valence electronvalence electron interaction derived in section 2.5. with the solution of the Schrodinger equation whose potential is known. In band structure calculations one is confronted with two problems. we only address some further dctails of this problem. firstly with the formulation of the one-elcctron Schrodingcr equation. The second is interaction with the (frozen) core electrons . Hcre we will deal mainly with the second problem. The effective one-electron potential V ( x ) of the crystal must then be known as a function of x. Here. and secondly with finding the eigenvalues and eigenfunctions of that equation. V(x) describes three interactions of a valence electron.2. this evasion is unacceptable. In the following we will give an overview. the calculation of the band structure must be done self-consistently.2. Determination of the effective one-electron potential The simplcst way of dealing with thc oneelectron potential V ( x ) is to treat its matrix elements with respect to a particular basis set as empirical parameters rather than integrals to be evaluated from a knowledge of the particular profile of V ( x ) . Because of this. We will provide examples below. It includes the Hartree and exchange potentials as well as the correlation potential of the valence electron-core electron interaction. Within the frozen core approximation. The third part of the periodic crystal potential accounts for the effect of the remaining valence electrons on the valence electron specifically considered. where we dealt with the one-electron approximation for the many-electron system of a crystal.this part is not problematic.the energy levels and eigenfunctions of the core states of the free atoms have to be determined in advance for us to be able to write down this potential contribution explicitly. In many . The various methods of band structure calculation differ in the manner in which thcsc two problcms are resolved. has in principle brcn solved in section 2. If one wants to forego. however. i. one has an empzmcal methodof band structure calculation. with the determination of the effective periodic oneelectron potential V ( x ) of the crystal. Having done that.2. The first problem.

From the physical point of view. We add two further remarks. of course. firstly! the matrix methods. the decomposition of the total electron system into valence and core electrons need not to be made in the literal sense of these terms. as already mentioned in section 2. may spin and the spin-orbit interaction of the valence electrons be ignored.2. it does not reproduce the correct d u e of the fundamental energy gap. In particular. such as Ge. therefore.g. but it fails if applied to the conduction bands. This approach is now being applied more frequently under the name puma-particle method (see. for example. The solution of this problem involves an extraordinary large numerical effort. The latter are ‘valence electrons’ in a more general sense. Within this framework the self-eneqy operator is often taken in the so-called GW -approximation [‘G’ stands for ‘Green’s function’ and ‘W’ for the Coulomb potential). Electronic structure of ideal crystaIs cases.. all electrons are treated as ‘valence electrons’. Bechstedt. In the extreme case. Secondly. Then one has the so-called call electron problem. they can also include d-electrons which. do not belong to the valence shell of one of the two elements involved. secondly. e. only for relatively light atoms such as C or Si. related to the potential of the atomic cores. In 111-V semiconductors. What counts is which electrons are frozen in their atomic states and. this interaction is essential and must be incorporated in the effective one-electron potential. so that such all-electron band structure calculations have been performed in o d y a few cases to date. and which electrons must be. A procedure which avoids this failure is the Gmen’s functzon method mentioned in section 2. With increasing computing power they will become ever more important. The LDA-method yields very good results as far as valence bands are concerned. they are the most satisfying.2. need not be treated self-consistently. For the heavier atoms. Matrix methods In the application of matrix methods one represents Bloch type eigenfunctions of a given quasi-wavevector k in a particular basis set consisting of a finite number of functions of the Bloch type. Firstly. one way this can be done is by means of the dematy finctional theory in its local approximation (local density approximation or LDA). and thirdly. As indicated in section 2. 1992). the Hartree and HartreeFock approximations fail to give satisfying results. the muffin-tin methods. so that correlation effects must also be inchided.134 Chapter 2. the cell methods.2. Solution of the Schrodinger equation The solution procedures can be divided into three groups. The Hamiltonian of the crystal is thereby represented by a k-dependent complex Hermitian matrix which .

C(cklk C + + K ) Ick) (2. referred to as Luttznger-Kohn funetzons. because with fewer basis vectors the eigenfunctions are necessarily approximated more crudely than with a larger number . The following basis functions prove to be of practical use: -Plane waves Iki-K) with k being a vector of the first BZ and K a reciprocal lattice vector.237) in order to satisfy the orthogonality condition (2.in the extreme. the core band eigenfunctions (ck) may be taken as Bloch sums of the core states of single atoms. Such expressions are extremely useful to achieve a physical understanding of band structure. ~ Bloch functions with Bloch factors for a special wavevector. The so-called k .236) holds. K ) . One would like to manage with the fewest possible functions. Within the frozen core approximation. p-method uses these functions.5. ~ Bloch sums of atomic orbitals. Therefore. The linear combinations to be subtracted are chosen such that the OPW's are orthogonal to all core eigenstates. Making the expansion functions orthogonal to the core eigenstates accounts for the fact that . so that (2. This constitutes a generalization of the nearly free electron approximation. An OPW-function IOPW~+K) is obtained from n plane wave Ik+K) by subtracting a certain linear combination of core band eigenfunctions Irk) of the crystal Hamiltonian.236). The calculation of band structure is thus traced back to the determination of the eigenvalues and eigenvectors of a k-dependent Hamiltonian matrix. The OPW's must have the form l O l ' W k + ~ )= Ik. we treat these two methods in greater detail below (sections 2. - Orthogonalized plane waves. the tight binding and k pmethods may be used to derive analytic expressions for the k-dispersion of energy bands. to minimize the numerical effort.2. For a fixed number of basis functions the level of precision achieved is higher for basis functions which are better adjusted to represent the eigenstates. also called LCAO's (Lznear Combznatzons of Atomzc Orbatuls). The basis sets employed differ by the number and kinds of functions they contain. Rand structure 135 has as many columns and rows as the basis set has functions per k-vector. In some circumstances. The price for this is a loss of precision.6 and 2.7). This includes the tight binding met hod. or of other localized functions. one needs an i n h i t e number of functions. called OY W's.

A further development of the OPW-method is the pseudopotential method. This means that the sought-after eigenstates of the valence electrons of the crystal for a given quasi-wavevector k must be orthogonal to the core eigenstates having the same quasi-wavevector k.241) Surprisingly. Consider the core electrons. for which we have + H i c k ) = E.lck). just like the valence electrons. Electronic structure of ideal crystals eigenstates of the Hamiltonian for different energies are always mutually orthogonal. by applying of H to $I% one immediately Ends that ~$g~ . the artificial wavefunctions are in fact eigenfunct ions of a particular Hamiltonian H p s . having the same eigenvalue E to which the a eigenfunctions $ of H correspond. Because of of this reinterpretation of the oneelectron Hamiltonian H . In fact.237) from the OPW's to the one-electron Hamiltonian H of the crystal. to be independent particles.238) The valence band eigenvalues E and eigenfunctions ~a similarly satisfy the eigenvalue equation The expansion of ~ $ m respect to the OPW's with reads Removal of the core states from the expansion functions mandates changing from the eigenfunctions $ato other functions v p i that have the same expansion coefficients.136 Chapter 2. correspondingly one needs fewer O P W ' s than plane waves to accurately represent the valence eigenfunctions. (2. which we have hitherto taken jointly with the atomic nuclei to form the cores. but is added to the eEective o n e electron potential 1 ' ~ 15-c the electron-electron interaction. This transfer is done as follows. its eigenstates now also include core states. For this reason the O P W ' s are much better adjusted to represent the eigenfunctions of the valence electrons than are pure plane waves. Pseudopotential method The idea underlying the pseudopotential method is to transfer the core state orthogonality term in equation (2. This means that the potential created by the core electrons is no longer included in the core potential Vc. but plane waves as expansion functions: (2.

+ v p2 2m H + Vxc + Vc+ C ( E .243) The Hamiltonian HPS is a well-defined linear operator.e. for example. It can he made even smoother if one exploits a property of V. they are not also eigenvalues of HPS since the pseudo-wavefunctions of the core states vanish. the eigenvalues of the pseudo-Schrodinger equation (2. the representation matrix of the pseudo-Hamiltonian HPS is small and easy to diagonalize. One can show that it largely compensates the variation of the core potential V.241) of the pseudo-wavefunction to terms having small reciprocal lattice vectors K.244) The last two terms in this expression jointly constitute the so-called pseudopotential V. in these regions. although it is nonlocal and depends on the eigenvalue E itself.2.p" is relatively smooth throughout the cores. Band structure 137 (2.p" in equation (2. but the reverse statement does not hold. It is called a pseudo-Hamiltonian The are termed pseudo-wavefunctions. Because of this. indicating that it repels valence and conduction band electrons away from the cores.245) The second term on the right is significant only in the core regions. considers the core electrons no longer as independent particles which enter the effective one-electron potential VH Vxc of the electron-electron interaction.242) rem i the same.E. such as. i. (2. norm-conservation of the pseudo-wavefunctions. and also fulfill other requirements. While core levels E.E. The pseudo-Hamiltonian HPS may be written in a form which clarifies its meaning.E. This is the reason . The smoothness of the pseudoptential makes it possible to restrict the planewave expansion (2.242) H P S= H + E ( E .. are eigenvalues of H . This freedom may be an used to make the pseudopotential still smoother.)lck)(ckl C .245). Then HPS takes the form $gk + HPs= . (2. We refer to the non-uniqueness of the repulsive part of V.)lck)(ckl C . Each eigenvalue of HP" is simultaneously an eigenvalue of H .)(ckl in (2. the pseudopotential V. To begin with one revokes the re-interpretation of the Hamiltonian H . There. If there the bra-vectors (E . it is preferentially positive.p" (2.5.245) are r e placed by completely arbitrary functions (while keeping the ket-vectors Ick) unchanged). but includes them again into the atomic cores making them contributors to the core potential V. only the pseudo-wavefunctions change.p" which has not yet heen discussed. Consequently.

In cell methods? one first determines linearly independent solutiona of the Schrodinger equation within a primitive unit cell for arbitrary energies. This method suffers from the arbitrariness of t.245).p"i s replaced by approximate expressions which range from empirical local pseudopotentials with adjustable parameters up to non-local pseudoyotentiah including core states of s-! p. In principle it can be determined from the defining equation (2. The most natural choice of unit cell is the Wigner-Seitz cell. A completely different approach to solving the oneelectron Schrodinger equation is taken in the so-called cell methods.lie choice of the unit cells and the difficulty of satiseying the boundary conditions over the whole surface. and leaves some empty space around them. no longer applies. one constructs the solution for the total crystal.s main advantage in having the pseudoeigenfunctions built up from a relatively small number of plane waves. The require ments that these functions.ial method is generally successful if the true valence band eigenfunctions are also sufficiently smooth outside ol the core region. the pspudopotential V. be continuous at the boundaries of the unit cells determines the energy eigenvalues and eigenfunctiuns.ribute to these states in an essential manner. because it. i. if the d-electrons of the atoms are sigmficantly involved in t. A further development. Muf&n-tin methods In the present method one delimits spheres around the atoms. If d-orbitals cont. Forming Bloch sums with them. the psendopotential must be known explicitly.and p-orbitals. This i s the c a ~ e long as the valence band states are composed mainly as of atomic 3. in a sense. i. of cell methods lies. Thus may occur in trhe rase of TII-V and 11-VI wmpound semiconductors whose cations have flat d-levels as in the case of Zn. for exmaple (see Table 2. Cell methods These methods are 3-dimensional generalizations of the method of matching conditions usually employed in solving thr Schrodinger equation for the square well potential and other 1-dimensional potentials. In order to apply this method.s.he chemical bonding of the cryshl. with core levels and wavefunctions taken from atomic calculations. then the pseudopotential method becomes problematic. The crystal then looks something like . and their first derivatives. F k t m n i c structure of ideal crystals that the pseudopotential method is very helpful in calculating valence and conduction band structures of semiconductors. The pseudopotent. of course.e.2). and with bra-vectors (ckl substituted by appropriate functions.138 Chapter 2. in the mufin-tin methods.and d-symmetr y. at an infinite number of points. In practical applications.

Gaussian functions are used instead of the angular momentum eigenfunctions. called the Komnga-Kohn-Rostoker (KKR)-metho$. trnd in the surrounding regions one takes the potential to be uniform. some of the methods listed above are used more frequently than others. is particularly important.5. the empirical versions of the tight binding and of the pseudopotential methods. in addition to angular momentum quantum numbers. which takes advantage of the formal scattering theory of quantum mechanics in the Green‘s function formulation. Among the ab initio procedures. the solutions of the Schriidinger equation within the spheres are expanded with respect to angular momentum eigsnfunctians. . but the matrix elements are. Of practical importance among the empirical procedures are. one speaks of rnuff-tin orbitals (MTO ’s). also the APW and LMTO methods are used. Often. In a special mufin-tin method. in constructing the APW’s. If. upon which the MTO and LMTO methods rest. above d l .ions within the spheres mist join continuausly with the solutions outside. as a consequence of the use of better adjusted ban sis functions. a linearized energy dependence of the matrix element. The radial parts of the expansion are determined by the radial Schrijdinger equation. unlike the Hamiltonian in matrix nielhoads. In contradistinction to bhe basis functions used in matrix methods. In another muffin-tin method.he soliit. They are. the A PW-matrices are i general smaller. funcbiom of energy. Within the spheres one uses the spherimlly syuunelric potentials of the atoms.he augmented plane wave ( A P W)-method. as in matrix methods. t. the still unknown expansion coefficients are determined by the requirement that t. Band structure a muffin-tin. but m a y be taken as a basis for them. of course not eigenfunctions of the oneelectron Schrdinger equation of the crystal. The functions constructed in this way are called augmented plane wawes {APW’s). the APW’Ystill depend on the unknown energy eigenvalues. Then. mainly in their linearized forms. + The different APW’s are indexed by reciprocal lattice vectors K. However. This is solved for the various angular momentum quantum numbers numerically. l o B homogenwus set of equations €or the expansion coefficients. In addition. whence 139 thc method’s narnp.2. An rigenfunction expansion with respect to APW’s leads.s yields useful results in the linearized APW o r LAPW method. the pseudopotentid method combined with density functional theory in its local approximation. The latter are plane waves of some wavevector k K. the expansion functions are also angular momentum eigenfunctions between the spheres. and lately with the Greens’s function method. In band structure calculations for semiconductors.

This approximation is callcd a tzght b m d m g (TB) appro. is particularly important because it allows us to deal with only the valence electrons of the free atoms. In this section we will develop the basic principles of the TB approximation. to be exact.e. while the core electrons are incorporated in the atomic cores. when the tight binding approximation is not applicable. 2. The approximation of nearly free electrons will work very poorly in this case. the eigenstates of the one-electron Hamiltonian of a crystal are represented by a superposition of plane waves. i. The term ‘exact’ here means within the framework of the simplifications made earlier.140 Chapter 2. These principles will be applied to semiconductors of the diamond and zincblende type. biit it does not correspond to the reality one should expect for valence electrons if one considers the crystal to be n formed from previously isolated atoms.e. Thus the eigenstates are weakly disturbed plane waves in which lhe electrons are spread out almost uniformly over the whole crystal. of the atoms composing the crystal under consideration. Electronic structure of ideal crystals 2. Results which are obtained from both these approximations may be considered to be independent of any particular approximation. i. the approximation of frozen cores introduced in section 2. Although this localization must be partially breached in the crystal. This suggests a more appropriate approximation which takcs atomic wavefunctions as the basis set and treats the non-diagonal elements with respect to these functions as small perturbations. the valence electrons are l o c a l i d at their respeclive atomic cores. more strictly. These eigenfunctions are called . One of these simplifications. The non-diagonal matrix elements of the periodic potential with respect to these functions are treated as a small perturbation. in order for chemical bonding to take place.6.1 Fundamentals Atomic Orbitals The basis functions of the TB approximation are the one-particle eigenfunctions of the valence electrons of the free atoms. an almost complete deloralization such as is assumed in the nearlyfree-electron approximation is not to be expected. while it gives good results if the electrons are weakly localized. I free atoms.1.mmntzon The errors of this approximation are expected to be small if the valence electrons of the crystal are well localized at the atoms.6 Tight binding approximation In the nearly-free-electron approximation. In this sense the two approximations are complementary. Such a distribution might be valid for drctrons of tho conduction band. but it also provides insight into their chemical bonding and atomic structures. and it will be shown that the TB approximation not only is capable of explaining the valence band structure of these crystals.

which turns out to be decisive for the TB approximation. The spinor character of the orbitals may be taken into account. The latter i s determined by the symmetry of the Hartree o i HartrecFock potentials of the atomic cores. one needs. The irreducible representation of a given quantum number 1 is (21 1)-fold degenerate. For the elemental semiconductors of the fourth group of the periodic table the valence shell orbitals are formed by the four ns- .1 and + l . Within the TB approximation one takes only these orbitals into account. it is assumed that the tttorriir core is located iit the coordinate origin x = 0. This is not due to the spatial symmetry of the potcntial but to its purr Coulomb form. + + + (2.6. 'l'ht. 'l'he largest contributions are to be expccted from orbitals forming the valence shells of the free atoms.246) Here. In this way the energy levels E. and the corresponding eigenfunctions dnlm(x)depend on thrw quantum numbers r ~I . A wavefunction with the quantum number I = 0 is called an s-orbital. Thus we may assume isotropic core potentials.2. Here this additional degeneracy may not be assumed. Tight binding approximation 141 atomic oibatnls.. rigorously speaking. only matrix clcmerits between valence orbitals are considered while those involving other orbitals are neglected. In order to represent the eigenstates of the valence electronb: of a crystal. These potentials are isotropic if all core shells are fully populated by electrons. not all of these contribute in an essential manner. one with 1 = 1 a p-orbital. and the atomic orbitals of given energy eigcnvalues form basis sets of irrediicible representations of the full orthogonal symmetry group. For each value o l lhe quantum number 1 one has an infinite set of different energy eigenvalues. The mobt important property of the orhit&. nll orbitals of the cores of its atoms since only the totality of all orbitals forms a complete basis set in Hilbert space. The energy spectrum of the free atom is degenerate with respect to m. with 1 .2 a d-orbital etc. The 21 1 basis functions are distinguished by the magnetic quantum niimbcr 7n which takes all integei values between .l of an atom depend on thc two yuanturn numbers r~ and 1 . but we will omit it here brevity. this condition is always satisfirul. These are distinguished by the mdin quantum number n which may take all intcgcr values horn 1 1 to 00. However. This corresponds to a perturbation-theoretic treatment of the Hamiltonian matrix with respect to the atomic orbital basis. These representations are characterizd by an angular momentum quantum number 1 which may assume all non-negative integral values. is their spatial symmetry. Foi the hydrogen atom there is also a d c generacy with respect to 1.jrn(x) can be written as products of the radial wavefunctions &(I x I) and spherical harmonics Km(xl I x I). In the case of atoms forming diamond and zincblende type semiconductors. eigcnfunctions &. m.

two of the three porbitals are empty.and 4sstates. n = 3 for Si.. the eigenstates are candidates for posstble population. will also not be completely populated. besides the abovementioned 4s. Instead of drill and d ~ ~ 1 . For body-centered cubic metals such as Cu and Ni.142 Chapter 2. Similarly. For Si. eigenfunctions &oo. which will be calculated later by means of the T B approximation. but it is by no means the only possibility. be populated by electrons in the case of the free atoms.1 with respect to the magnetic quantum number m.1 it was already mention4 that d-states may contribute to the valence shell of 11-VI semiconductors with heavy metal atoms such as Zn.and lip-states of Ga. In the case of semiconductors composed of different elements. &i-i may be formed .and p-states. For the sake of uniformity. In section 2. n = 4 for Ge. on the temperature of the crystal In the examples considered above the valence shells of the atoms are formed by s. of course. IV. Whether they are popdated or not. for example. according to equation (2. For GaP one bas. e. one sets . The corresponding spherical harmonics X.g.and p-states need to be taken as basis functions. the one 3s-state and the three Spstates of P. Electronic structure of ided crystals and np-states with n = 2 for C . for example. especially if one also includes other material classes.cll. The valence shell orbitals used as basis functions need not. As this applies to quantum mechanics in general. we wiU exclusively consider semiconductor materials for which only s. For GaAs that means the one 4s-state and the three 4p-states of Ga. Here. and the one 4sand t h e Q-states of As. This is the typical case for tetrahedral semiconductors composed of elements of the main groups 11. the eigenstates of the crystal. the valrnce shell orbitals of the various atoms must be considered. and VI of the periodic table. &lo. and n = 5 for a-Sn. $n. depends on the macroscopic state of the system.(X/ I x 1) are Using these harmonics.246). the valence shells are formed by 3d.1one may use the linear combinations The latter are also energy eigenfunctions because of the degeneracy of qbn1l aiid 0 ~ 1 .

The orbitals considered above are orthonormalized. The latter are visualized in Figure 2..16: Polar diagrams of the atomic s-and p. 6 . one has ($a’ I $fZ) ‘af. Although the two orbitals are localized in different spatial regions.251) If the atomic core is not located at the coordinate origin.16. it may not be n e glected because its influence on the energy eigenvalues is of the same order of magnitude as the matrix elements of the Hamiltonian between orbitals at different centers. z. are also orthogonal ‘ to each other.orbitals in Cartesian representation. The latter elements are essential because they are r e sponsible for the bonding between atoms in a crystal and for the splitting of the atomic energy levels into bands.246) to (2. and those of (2.250) as Carte3ian orbitak. z of the Cartesian. as well as n.e. Tight binding approximation 143 Figure 2. They may be traced back to the orbitals &(x) of atoms located at the origin by shifting their arguments in accordance with Two different orbitals & f j f R ‘ ( X ) and & ~ R ( x ) with identical values of R’ and R as well 8s of j ’ and j . y. as has been assumed thus far.6.249). the so-callcd ovcrlap integral. by writing down and solving the eigenvalue problem for the crystal Hamiltonian in the non-orthogonal basis set of the atomic orbitals. (2.2. for orbitals at different centers. The eigenfunctions of equations (2. turns out to be relatively small. (2. i. but different values of a and a. but at a particular lattice position R+G. the corresponding orbitals will be denoted by &j~(x). For R’ f R or j’ # j . and the integral over the product of the two.248) will be referred to as spherical orbitals.e. will be abbreviated by a general index a. This procedure . The quantum numbers nlm of the spherical orbitals. The non-orthogonality overlap integrals must therefore also be taken into account. no such orthogonality exists. i. This may be done directly.

the d U 3 ~ ( obey the relation x) (2. is convenient to transform the latter into Bloch type ) orbitals puJk(x). such that (&!jrR( I O a j R ) = bo'abj'$R'R. each set heing chara c t w i d by a particular angular morrieriturri quantum miniber 1. 'suitable' means that . Koster. 1954). The orbitals q a j ~ ( xare now. again..250).2 56) . That there are indeed linear combinations of atomic orbitals possessing these properties. As before. Consequently. by definition.254) one may readily verify that (2. they will not be given here since thcy are nut. likewise form basis sets of irreducible representations of the full orthogonal group. but their indices n E nlm will retain the meaning they previously had for the ordinary atomic orbitals.255) The sum over R extends over all lattice points of the periodicity region. This is done by means of the k-dependent unitary transformat ion (2. Slater. Schrodinger equation in matrix representation Consider. hlthough explicit expressions for the G w d i n orbitals & j ~ ( x )can in principle be providd. quite inconvenient becaiise the matrix of overlap integrals has to be calculated explicitly and diagonalized together with the Hamiltonian matrix. To represent the Bloch type eigenfunctions by means of atomic orbitals o a J ~ ( xit . no longer given by the expressions [2.144 Chapter 2.ants.246) to (2.75) of the crystal.253) With Ro as an arbitrary lattice vector. the eigenfunctions of this equation are taken in the form of Bloch functions pyk(x). We will iise this theorem below. It is more useful to employ a set of orthoganalizd orbitals by forming suitable h e a r combinations of the q a j ~ ( x )Here. forms the content of Liimdin. By means of (2. aIso orthogonal for different centers. e. the new orbitals should have t. n m d d if one proceeds in thc manner to be discussed below. ties that allow the matrix elements of the Ilamiltonian to be reduced to a few const. The orbitals m U j ~ ( xwhich thus far have been )! taken as ordinary atomic orbitals. Iiowcvcr. The Lowdin orbitals arc. will henceforth be understood as atomic ) orbitals in the sense of Ldwdin's theorem. Ektranic structure of ideal crystds is.g.'<sthcowm (we.he same spatial symmetries a s thc original atomic nrhitrals Q U j ~ ( xbecause these symmetries are the essential proper). the new orbitals must. the Schrodinger equation (2.254) Bloch sums. (2. of course.

259) where the matrix elements of the Hamiltonian are given by the expressions with (aj0 I H I a’j’R’) = s d 3 x ~ ! J : ( x? ~ ) H ~ . the use of the Bloch sums (2. i. the second nearest neighbor atoms only.2.5. so that it suffices in most cases to extend the sum on R’ in (2. The integrals ( a j 0 I H I a’j’R’) in (2. R] = 1. Obviously. Employing this representation in the Schrodinger equation (2. (2. the eigenfunctions C p v k ( x ) of the Schrodinger equation are written as linear combinations cPvlc(x) = x ( ’ J j k I c P v k ) c P a j k ( x ) jQ (2. through them.I. Once the integrah ( a j 0 I H I a’j’R’)and.260). because of the relation exp[iK. (2. it suffices to take k in the first B Z .261) describe the interaction of electrons in orbitals a and a’. the (ajk I H I a’j’k) form a square matrix with a finite number of rows and columns. ( (2. Therefore.261) In deriving equation (2.257) In the TB approximat.6. Tight binding approximation 145 which identifies the & j k ( x ) as Bloch functions of quasfwavevector k. For a given wavevector k.258) of Bloch sums q 5 a j k ( x ) .). These integrals substantially decrease with increasing distance between the atoms.260) over the nearest. ‘number J of atoms per primitive unit cell times number A of orbitals per atom’. where one of ’ the orbitals belongs to the atom at ? and the other to the atom at R’+ ?. also the matrix elements (ajk 1 H 1 a’j’k) are known. The orthogonality of the Lowdin orbitals & ~ R ( x ) results in the orthogonality of their Bloch sums 4 a j k ( X ) . we obtain x(ajk I H j’a‘ I a’j’k)(a’j’k I V v k ) = Ev(k)(ajk I cPvk). the energy eigenvalues and eigenfunctions of . such that (‘#‘alk’j’ I ‘#‘ajk) 6a’a6j1j6k1k.75).ion. the original wavefunction is reproduced expect for an unimportant phase factor. If one replaces k in &jk by a wavevector which differs from k by a reciprocal lattice vector K then. the lattice translational symmetry of H has been used.255) automatically puts us in the reduced zone scheme. j k ( X ) are called Bloch sums of atomic orbitals. or if need be. the same as the number of different orbitals per primitive unit cell which were used for the representation of the eigenfunctions. I -xR’ . The 4 .e.

the main quantum number n will be allowed to take not just one value. They will be partially degenerate if symmetrical k-vectors are considered. the matrix element (nslk IH I nslk) of (2.O. The ( j . With increasing distance between the atoms. If k varies over the first B Z . can in any case. The value of E. as previously assumed.1). be done numerically. and Pns. the J x A energy eigenvalues form J x A energy bands.BnS depends on the overlap of the ns-orbitals localized at adjacent atoms.a) + cos(kya) + cos(k. in a crude approximation.260) at the nearest neighbor atoms. 2 . In evaluating the matrix element (nslk IH I nslk). In terms of E.s = (O. With J = 1 and A .. such that a = ns. In this context. Electronic structure of ideal crystals the Schriidinger equation may be obtained by calculating the eigenvalues and eigenvectors of the ( J x A ) x ( J x A)-dimensional IIamiltonian matrix of equation (2. .z = (fa..O). we have employed the fact that. The value of .260). The latter are located at R1. (2.O). The atoms are placed at the lattice points R. Consider a crystal having a primitive cubic lattice and 1 atom per primitive unit cell . . For the matrix elements occurring in equation (2. with set of atomic orbitals will be restricted to one ns-orbital only. all six neighbor atoms give rise to the same value of the integral (2. a matrix of size 1 x 1 = 1 is obtained. in fact.262) (2..a)] . Here.fa). but. This the solution of thP eigenvalw problem is. (nslO I H (2.. trivial. may be identified with the energy of the ns-level of the free atom.0. for reasons of symmetry.fa. we will terminate the R’-sum in expression (2. & approaches 0.263) I nslRt) = pns. . t = 1 .R3.O. to gain insight into the formation of energy bands.260). For each k one has J x A eigenvalues and eigenvectors.261).146 Chapter 2. we use the notation (nslO I H I nslO) = ens.(k).1.. 6 . (2.4 = (O. Simple example: cubic crystal composed of s-atoms We will illustrate the above discussion with a simple model.264) t=l 6 It follows that the energy eigenvalues Ens(k) of the Schrodinger equation are Ens(k) = ern + pns2 [cos(k. This is an easily solvable task which occasionally can be treated analytically.265) It is of interest to further discuss the eigenvalues e.Rs. .260) is given by (nslk I H I n s l k ) = ens + &sxeik’Rt.

0. If the above conditions are met.17: Energy bands in Tight-Binding ayproxirnat.k.2 positive.. as has been . If the distance between nearest neighbor atoms increaees. for n . for n . The width of these bands amounts to 4&. In addition. To justify the application of the results obtained above in the present case.2. Their widths decrease with growing n. This behavior reflects the differing numbers of nodes of thc atomic wavefiinctions for different values of n. Each level ens of the free atom gives rise to an energy band of the crystal. always be larger than 4Pns.6.17. such that for n = 1 l it is taken to be negative.O. corresponding to the larger values which the ns-orbitals with larger n have at the nearest neighbor aloms. The separation between adjacent energy levels cn8 should. however. then the parameters fins of equation (2. and that the sign of pns alternates.263) decrease because of decreasing ovrrlap of the orbitals.) l-r a but several. We assume this to be true. The bands are separated by forbidden energy regions. the energy band dispersion along the line (0. kz) of the first B Z of the simple cubic lattice under consideration. This means that the valence electrons in the free atom do not occupy only one 5 level.3 negative etc. k s P3s P 2s PlS -IT - D 0 Wavevector (O. we suppose that ens is negative for a l n. has the form shown in Figurr 2.ion for the simple s-atom crystal described in the text. but several s-levels ens differing in the value of n. The absolute values of Pns are expected to increase with growing n . Tight binding approximation 147 Figure 2. thus increasing with increasing n. the matrix elements of H between s-orbitals having different values of n must be negligibly small.

Comparison of the two approximation procedures reveals the difference between the underlying concepts . ens. Electronic structure of ideal crystals pointed out above. corresponding to . is present at the outset in the latter approach. If the infinitely remote atoms again approach each other. Only nearest neighbor interactions will be taken into account because this introduces considerable simplification and nevertheless gives results of reasonable accuracy. electron states with different values of the wavevector component k. among them one s-orbital([ = 0) and three porbitals ( I = 1). then the .nz. Correspondingly. For the p-orbitah.6. in this way. In the latter case. On the other hand. so that the orbital index a takes the values ns.the TB approximation emphasizes the atoms and the short-range ordered complexes of the crystal. where the occurrence of energy gaps calls for an explanation.ny and n z . the degeneracy of electron states with different kz is removed. They approach the discrete levels ern of free atoms as this distance becomes infinitely large. in the form of the infinitely broad energy continuum of the free electron. because of the onset of overlap of neighboring orbitals. since the discrete atomic levels are separated by energy gaps from the outset. Figure 2. we choose the Cartesian form. This stands in contrast to the approximation of nearly free electrons. The same holds for the widths of the energy bands. It will be developed in the present subsection. 'bandwidth'. and the discrete levels of the free atoms spread into bands. have the same energy.148 Chapter 2. therefore. The application of the TB method to this specid case is of particular importance. The Cartesian components I . These levels are. while the approximation of nearly free electrons focuses on the crystal as a whole and the long-range ordering of the atoms. Such comparison also shows that the short-range and long-range order concepts are equivalent in the sense that they result in the same characteristic features of the electronic structure of crystals -both concepts predict the existence of energy bands separated by gaps. how discrete energy levels of the free atoms transform into energy bands of the crystal. = 0. they become narrower if the distance between neighboring atoms grows.-values become finite. The gaps induced into the energy continuum were seen to arise because of the strong perturbation of plane wave states by the periodic lattice array of atomic coTes fox wavevectors on the Bragg reflection planes.&.2 TB theory of diamond and zincblende type semiconductors Semiconductors of the diamond and zincblende type are tetrahedrally coordinate cubic crystals with two atoms per primitive unit cell and four valence shell orbitals per atom. The TB approximation quite naturally explains.&. The gaps between the bands occur naturally in this approach. highly degenerate. 2. y r z refer .18 depicts the manner in which the bands and gaps arise in the two approximations.

ween orbitals at equivalent atoms.18: Illustrat. although not necessarily the same. Since o is the symmetry group of H . As a first step we determine the 8 x 8Hamiltonian matrix for diamond type crystals. and we denote . ( a j k 1 H I a'jk) becomes independent of k. the two atoms J = 1 and J = 2 of the primitive unit cell are of the same chemical nature. in general. ' only the term with R = 0 needs to be considered in the R'-sum of formula (2. Thereby.6. Tight binding approximation 149 Figure 2. The eigenfunctions I s l O j and I zlO). thus their matrix elements will be identical. In the case of diamond type crystals.wo atoms. Since we are restricting ourselves to nearest neighbor interactions. Matrix elements between orbitals at equivalent atoms These are elements of the general form ( a j k 1 H 1 a'jk). according to the unit representation rl and the vector representation I1 of the cubic '5 h point group Oh.ion of the origin of energy bands and gaps in the enerw spectrum of a crystal. the matrix element ( s l k I H 1 s j k ) likewise belongs to the unity representation. \ 210) transform.2. Later: it will be generalized to zincblende type structures. is non-zero. 1 ylO). According to Appendix A this means that its value.260). Hamiltonian matrix We start with matrix elements bet. The main quantum number n will be suppressed below because it may assume only one value here for each of the t. respectively. to the cubic crystal axes.

i.2.e.260) may be restricted to the 4 lattice points &. the R'sum in (2.260) becomes 4 (ujk I H I a'j'k) = x e i k ' ( R t f 5 f . For j = 1 one has j' = 2.3. The four nearest neighbors of a 1-atom are located in the primitive unit cells at R = 0. j = 1. according to Appendix A.(.19). The calculation of the matrix elements (a10 I H I a'2Rt) between the different Cartesian orbitals and the four different values of Rt is .150 Chapter 2. because the second may determined from the first with minor changes. as in the case of c8. R 4 = -a3.j' = 2. )~ j IH I U ' j ' R t ) . Again. these elements must vanish. The non-diagonal p -p-matrix elements must be zero according to the above symmetry analysis. Then.266) Matrix elements between orbitals at non-equivalent atoms In evaluating the matrix elements between orbitals at non-equivalent atoms. which means that the p .t = 1. 1 R = -al. i. the unit representation occurs exactly once. which does not contain the unit representation. 0 t=1 (2. We will restrict ourselves to the first case.% .p-matrix contains exactly one independent constant. the value of cp is roughly the energy of the correspondingp-orbital of the free atom.27). we have (2. 2 R 3 = -a2.268) (see Figure 2.and p-orbitals at the same atom transform according to the representation rlx I'l x r 1 5 = r15. . With this simplification the Hamiltonian matrix of (2. and for j = 2 then j' = 1. es is the energy of the s-orbital of the free atom. Summarizing. In a crude approximation. whose primitive unit cells host the 4 nearest neighbor atoms.e. The matrix elements between s. A more detailed analysis shows that this constant corresponds to the three non-vanishing and mutually identical elements (210 I H I s10) = (y10 I H I y10) = (210 I H I 210) = E. The matrix elements between p.4. Electronic structure of ideal crystals it by E ~ . Here. (2.and p-orbitals belong to the representation r 1 5 x I ' l x r 1 5 = X'1+r12+I'i5+I'b5 (see Table A. elements of the general form (ujk 1 H I a'j'k) with j # j ' .267) The values of j and j' are complementary to each other because the nearest neighbor atoms lie in the other respective sublattice.

( h l O 1 N 1 l‘m20) BmmrV~ppn 12 . so that (Lm1O I H I I’m’20) = & . the neighbor atom 21 which lies in the same unit cell as the 1 central 1-atom. because they refer to different pair-related coordinate systems. I has B different direction. somewhat laborious. (2.19).269) The Cg. To distinguish between this z-axis and the crystal-related cubic z-axis. however. The matrix elements (a10 I H I a‘2Rt) between the so-defined orbitals are equal for all four nearest neighbors.2. in particular. This yields diagonality of these elements with respect to the magnetic quantum numbers rn. The orbitals differ.6. R = 0. It will be carried out in several (five) steps. Consider.19: Atom of sublattice 1 and its four nearat neighbors in sublattice 2. The corresponding Z-axis represents a %fold symmetry axis of the crystal which contains three mirror symmetry planes.-symmetry of the Hamiltonian H holds with respect t o the nearest . Tight binding appmxhation 15 1 24 #’ Figure 2. we denote the former by 2. In evaluating the matrix elements (Im10 I H I I’rn’20) one may therefore use the fact that the Hamiltonian exhibits the symmetry of the point group C h with respect to the Z-axis. i) Spherical orbitals in the pair-related coordinate system The spherical orbitals are related to a spherical coordinate system whose z-axis is in the direction o the line connecting the central 1-atom and its f nearest neighbor atom 2t in the unit cell at & (see Figure 2. In the first step we determine the matrices (a10 I H I a’2Rt) between spherical orbitals. For each of the four next neighbor atoms. . m’. Here. .

in an approximate sense. Vm. however. then the integrand of the matrix elements (Im10 I H I l’m’20) has the full axial symmetry. Taking account of the strength of the overlap of the orbitals .152 Chapter 2...R” . The matrix elements of H between orbitals at different renterrs jR and J’R‘ thereby decompose into bums over all centers JI’R’‘.. Rwauw of that. m‘ if the R’-sum is extended to the swond-warest or more remote atoms. (2.270) The three matrix elements (0010 (0010 (2. the symmetry of H is smaller. non-diagonal with respect to m.272) are identicaL These elements are illustrated in Figure 2.(x .271) (1010 are independent of each other: and the two elements (1110 I H I 1120) = ( i i i o I H I 1720) = v & (2. so that these dements become diagonal with respect to m. m’.252) lcsd t o the relation (lrn10 I H I I‘m20) = (l‘m20 1 H I lm10).273) Since the atomic orbitals under consideration are those of bound states. which may be seen as foHows. IT&. in general. One has 1 l’m20) behave if the two atoms 1 and (2. The diagonality holds. Eiectronic structure of ideal crystals neighbor dirwtions. This figure also shows how the elements (In110I H 2 are interchanged. the matrix elements (alk I H I a’2k) of equation (2. The largest contributions will arise from t a m s where the center index j“R” coincides either with 1R or with J’R‘. and since the eigenvalues of the Hamiltonian for bound orbitals are generally negative. For the second-nearest neighbor directions. If one considers only such twecenter terms and neglects all threecenter contributions. vji.i y ) of potential contributions of all the individual atomic cores of the crystal. one may expect negative values for k<3n. The periodic potential V(x) in H represents a sum &.20. and positive ones for Ifaw.260) are. The hermiticily of the Hamiltonian and the particular form of the wavefunctions in (2..

Tight binding approximation 153 12 v s su = 21 vuG = vssu 21 =V p p u = 21.20: Illwtratiori of tight binding matrix elements.2. VPPT =Vppcr Figure 2.6. .

154 Chapter 2. The pair-related . ( .and y-axes lie in the plane normal to the z-axis. the matrix elements of this operator with respect to the Cartesian orbitals.20. apart from an irrelevant rotation about this axis. The corresponding 2. (510 I H 17/20) = (g10 I H 1.520). 0 H I 520) = ( . (110 I H 1220) = (510 I H 1520) = Vw. V .275) To develop the representation of the Hamiltonian matrix (2. (2. We determine these elements in the third step. (110 I H I 520) etc.10I H I 520). such as (310 I H I 220) and (120 1 H I . (3. are listed only once. Since the C a r t e sian orbitals are defined in terms of spherical orbitals by equations (2. (2. (2. The z-axis of the Cartesian coordinate system is taken t o be the same as that of the spherical coordinate system used above.orbital with respect to the cubic-axes system.267). incides with the 8. 3 1I 31 (3.10 I H I 120). the matrix elements of H between Cartesian orbitals in the pair-related system read (310 I H I 3. The coordinates in the pair-related Bystem will be denoted by 2 . (El0 I H 1. ii) Cartesian orbitals with respect to the pair-related coordinate system The matrix elements (lm10 I H I I’m’flO)of H with respect to spherical orbitals calculated above will be used to derive.(3. one can conclude that the absolute values of these elements should obey the relations I VPPO I ’I v I ’I VSSU I >I .ax is points in the direction of the connecting line between atom 10 and atom 21.10 I H I .20) = VSScr.10 I H I 220) = VSF. This means that the z . .274) These expectations are in fact valid in most cases. In terms of this notation.249).lo). the matrix elements between Cartesian orbitals can also be related to those between spherical orbitals. 0 H I 520) = 0. we need the elements (a10 I H 1 a’2Rt) of H between Cartesian orbitals which refer to the three cubic crystal axes rather than to the pair-related ones. The relations read (310 I H I 3. in the second step. The pair-related Cartesian coordinate system thus defined differs from the formerly introduced crystal-related system which is given by the three cubic crystal axes.250). 5. I. Electronic structure of ideal q y s t d s in Figure 2.220) = Vppu. The corresponding relations are given below.(3.520) = (210 I H 1120) = 0.-orbital co2. Elements which are complex conjugates due to hermiticity of the Hamiltonian.(110 I H I 120).20).

Tight binding approximation 155 iii) Cartesian orbitals i the crystal-related system n To this end.y. (2.e.277) Using equations (2.2.cos 6 sin $ 0 sin 0 sin $ c o ~ e c o ~ ~ -sinecos$) sin 0 cos e (i). without any loss of generality.276) Below.6. These are the elements of the third column of the rotation matrix in equation (2. q1 = .276).31) transforms the coordinates before rotation into the rotated one. 6 and 'p. As noted in Appendix A.q1. To determine this relation.Z. be set equal to zero. Z are understood here in the sense of basis vectors. the rotation matrix A of equation (A. z related to the cubic-axes system must be expressed in terms of the pair-related Cartesian orbitals ?. we consider a rotation which transforms the crystal-related axes system into the pair-related one.y. which. the Cartesian orbitals 2. i. r1 = cos 0. the Euler angle 'p may.277). p l = sin 0 sin $.c. z and ?.sin 6 cos $. is also the inverse matrix. Since the 2 .y. in the present case of rotation. The transformation is characterized by Euler angles $. (2. we have (:) cos @ = (sin@ . we will see that the direction cosines (PI. The basis vectors are transformed by the transposed matrix. the matrix elements in the crystal-related system are evaluated as One obtains . 71) of the pair-related 2 -axis with respect to the crystal-related cubic z-axis play an important role. Since the orientation of the pairrelated system is defined only up to an arbitrary rotation about the Z-axis.275) to (2.

only one relation will be given..TI. The unknown matrix elements (a10 I H I a‘2Rt) for t = 2. m. 1.1. t=l t=1 . such that dt = Rt .267).4 follow from the elements (a10 I H 1 a’2R1) in equation (2. In particular.268) for Rt and the explicit form of the primitive lattice vectors of the face-centered cubic lattice. qt.156 Chapter 2.3. From these elements we may determine the elements with the nearest neighbor atoms of different unit cells. ri) by ( p t .7.4. again. (PI.1) = ( l / f i ) ( L 1. . v) fifth step The elements (a10 I H I a’2Rt) determined above are used to calculate the k-dependent matrix elements (alk I H I a’2k) between Bloch sums. 4 2 .-1.278) by replacing the direction cosines (PI.xeik. r t ) in them. the two sublattices are displaced with respect to each other by the vector (a/4)(1.1).d f ( s 1I0H I s2Rt) = V. qt. The vectors pointing from the central 1-atom to the four nearest neighbor atoms will be denoted by dt. Electronic structure of ideal crystals These relations are valid for matrix elements involving the two nearest neighbor atoms belonging to the same unit cell at R = 0. 4 4 4 4 U (2. For the diamond structure.1. d2 = -(1. we obtain + dl = a a a(l.d3 = -(l.2.l) a ( etc. With the help of equation (2.1.1). P Z . l ) . This will be done in the next step.280) t=l 4 (slk 1 H I 22k) = x e i k . For complex conjugate elements. iv) fourth step. t = 1.l). t=l 4 (2. r t ) of the connecting lines between the central 1-atom and the nearest neighbor atoms 2t. d t ( s 1 0 I H 1 22Rt) = Vswxeik-dtpt.3. d4 = -(l.dt.. Using equation (2. 7 2 ) = (l/fi)(LI. we obtain 4 4 (slk I H 1 s2k) = ~ e i k .1).I).279) These relations determine the direction cosines ( p t .

6.s in these expressions are commonly abbreviated by The seven different t-sums which enter t.he matrix elements (2.2. Tight binding approximation 4 4 157 4 The combinations of matrix e1ement. The four independent sums are .280) may be reduced to just four because of the obvious relations ptpt = r t . p t r t = qt. and qtrt = p t .

I 22k). one calculates the eigenvalues of the Hamiltonian matrix (ajk I H I a’j’k). epr E.ik. E.ik.d~ I .d4 9 4 0 4 = . I y2k).E. Electronic structure of ideal crystals 9l(k) = eikdi + . 92.d4.e ik-dz . g3.ik.ik. material properties. I z l k ) . First of all. . are related to .ik.280) and (2. .dn: + . E.. I z l k ) ..ik+d2 .ik.dz + .. one also may forego the calculation of these Hamiltonian matrix elements and considers them as empirical parameters. Ez(k).dl + . (2. Arranging the eight basis functions 1 ajk) in the sequence I s l k ) ..ik. Then one measures the band energies at these points 01calculates them by some other . I y l k ) . However. E. e p . one has to calculate the eight eigenvalues El(k). and E .282) g2(k) = eik. and E.g4 in (2. these constants can be calculated from the n defining equations (2. this matrix is given by Band structure.... we c an write down the Hamiltonian matrix (ajk I H I a’j’k) between Bloch sums in explicit form. Es(k) of the Hamiltonian matrix (2.ds Finally. The k-dependence of the eigenvalues stems from the factors 91. E.158 Chapter 2.283) at the various points k of the first BZ..282).261) between atomic orbitals.. at least 6 special k-points as at functions of the unknown parameters cg.d3 + .dz + .. I s2k)..281) and the Hamiltonian matrix elements (2. Their values may obtained as follows.ik.&. I principle.ik. In quantum chemistry one often proceeds in this way.ik. .ds . .. which are universal functions of k. Empirical TB method To obtain the band structure of diamond type crystals.. .dl .d3 9 3 0 4 = ..d4 .ik. I z2k). The constants r.

36 4. leaving only the inter-atomic constants E. In this case it serves as an extrapolation method. because it helps to extrapolate from the electronic structure of the ideal crystal to that of the perturbed one. one often takes the inter-atomic matrix elements V.79 Table 2.97 -4. 1987..38 -6. f9RO. Equating the TB eigenvalues with those measured or known from other calculations. Once these are determined.55 -6.91 10. Together with c3 and e p . Tight binding approximation 159 Table 2.68 2.. as independent parameters. ESP. For instance.20 -0. which will be treated in Chapter 3.E. one is able to calculate the band structure at all k-points.92 1.52 -1..50 5.04 Ge -14. and a .54 2. Instead of EsS.2.1 type semiconductors (in ~i 6s EP VsSa V v vma -17. (see Table 2. E . each of these parameters may be expressed in terms of the material-dependent nearest neighbor distance do of the crystal. one obtains a system of equations which determines the unknown parameters uniquely. the intra-atomic matrix elements t 3 and tp may be identified with the atomic s..7). they are referred to as tight binding parameters.) m i -1. There are other variants of this procedure. and V. and Eppfor the fitting procedure. it may be seen that. Inspecting the inter-atomic TB parameters listed for the various diamond type semiconductors in Table 2.) 1 1 1 1 1 1 1.7: Tight binding matrix elements for diamond eV).60 -13.41 -2. The whole procedure may therefore be considered to be an interpolation of band energies between special points of the first B Z . (After Harrason.. It is called the empirical tight binding (ETB)-method..6.8: Universal inter-atomic TB parameters. Vspo..55 method..38 1.36 -1. This method can also be applied to the calculation of the electronic structure of perturbed semiconductors.15 -1.47 4.and p-energies..52 -8. (After Majewski and Vogl.93 2. V. within an appropriate error limit.7. and Epp E.

resulting in c l o d analytical expressionh for the energy hand lev& at special k-points of the first BZ.8.(fi/4a). Harrison. The intra-atomic matrix elements e g and c p corresponding to the set of universal inter-atomic TB parameters ql+. As a unnsequmce of this.) n universal material-independent factor qltm. Ultimately.284) has been jntroducd in order to make the universal factors qzpm dimensionless.9 for a series of atoms forming diamond and zincblende type semiconduc- .284) signifying that the inter-atomic matrix elements of the Hamiltonian scale ) with the inversesquare of the nearest neighbor distance. the 5ame k-points. The TB band structure follows by diagonalizing the T H Hamiltonian (2.8.2 by ineans of the relation do --.160 Chapter 2.8 are shown in Table 2. Their solutions stale with the inverse-square of the lattice constant a because the empty lattice band levels do so. If these expressions are identified with the empty lattice band levels at. in 'lable 2. This approximate relation is (2. Electronic structure of ideal crystals Table 2. The eigenstates of this operator are plane waves and its eigenvalues are proportional to the inversesquare of the wave length of i t s eigenstates.8 which have been derived from more precise band structure data (the meaning of figpa wiU be explained below in connection with zincblende type semiconductors).283). respectively. (Source same as i Table 2.9: Intra-atomic TB parameters (in eV) to be used in conjunction with the universal inter-atomic TB parameters of Table 2.284) originates from the kinetic energy operator of the crystal Harniltonian (li'royen. They are close t o the values listed in Table 2. The nrarest neighbor distances dg follow from the cubic lattice constants a in Table 1. the empty lattice band structure scales with the inverse square of the latlice constmt. hlormver. the empirical do'-dependence in equation (2. linear eqiiations for the TB parameters ctre obtained.62 eVA2 in equation (2. The factor ( f i 2 / m = 7. numerical valiies for the universal TB parameters q ~ follow~from these ' equations. 1979).

.T. the energetic ordering of the lwels is determined by the relatiom El@) < ER(O). 1 EzOj = ( I / f i ) ( O . o j . i. 0. I E ~ O. the triply degenerate level 6 2 ( 0 ) = E3(0)= E 4 ( 0 ) lies below the triply degcneratc level Rs[0)= Fe(O) = E 7 ( 0 ) .o. 0.1.. o ) .0.7(0). i . A k-point of prtictilar interest is the €32 center k = 0.0.o. .0.0.o. ) ) (2.6. 1 .o. 8 . both have negative values. i . The components of the corresponding eigenfunctions I EiO) read as follows: 1 E10) = (l/&)(l. The constants E~ and E. The results me the following 8 eigenvalues I &(a).and p-level energies which deviate somewhat horn the energy levels given in Table 2.2~17) E s ( 0 ) .o.o. 0.o.(1/&)(0.( i / ~ ) ( 0 .(i/fi){o. Thm+nrP. o. This means that E l ( 0 ) is the deepest of the foul levels. Tight binding approximation 161 tors. Here.283) may br o b tained ~ I closed analytic form.. iii) &(O) < &(0) < &(o) ru-sn. I EGO) (1/&)(0.0. LO.0.i). 0. therefore the El(O)-hvel is lower than the Es(O)-level.286) Since cP is negative and EZzpositive. 1 E40) 0) (i/&j[o.2.O. 1.o. For the pmitinn of the &(O) lcvcl.oj. Owing to the fact that the atomic s-energy eS lies below thp pencrgy cp7 the pigPnvahx9 E l ( 0 ) is also smaller than the deeper of the two Zriyly degenerate levels. o.1. namely : i) &(0] > &(O) > E s ( 0 ) . 1. o.for C and Si. I.o. i = 1. I R 5 O ) = (1/&)(1. o. o. They represent atomic s. ~ ~. i . I E ~ O. 01.o. 1. there are still three pussibilitks (important malerials to whirl1 the three possible cases apply are listed alongside the cases). the eigenvalues and eigenfunctions of the Hamilton matrix (2.2. o. E l ( 0 ) < E z ( 0 ) . ~ These relations Inem that the E'c.&. o . o .o.(O)-level moves down with respect to the other two levels as the size of the atoms increases. 0 .0. - ii) E3(0) < & ( 0 ) < & ( 0 ) Ge. O).l.o).ij. O . .0.0.E3(0) = E4(0) < E5(0) (2. .

Electron population of the ground state of the crystal. the eigenfunctions for & ( 0 ) and &(O) each belong to 1dimensional representations. the four lowest bands are populated.&(k). For k = 0 this group coincide8 with the full point group of cquivalent crystal directions.e. The above band assignment allows us to determine the symmetry of the valence and conduction band states at r. This means that in the case of C . Each of the elements of the second part of 01. we will term .162 Chapter 2. In the ground state of the crystal. Es(k) are the empty conduction bands. E4(k). together with two of the three bands E2(k). not all of the bands are expected to be populated. each k-value corresponds to 2 eigenstates of opposite spin. E3(k). G3 allowed k -values (see section 2. it is useful to decompose oh into two parts. In order to determine its transformation properties under the operations of the point group Oh. A simple energy band therefore has 2 x G3 states. the tetrahedron subgroup ‘ > I containing only elements which are not involved with an exchange of the two h sublattices 1 and 2. Since it is degenerate at k = 0 with the highest valence band. E2(k). therefore. just as the s. The remaining band of the three is a conduction band. Electronic structure of ideal crystals It turns out that the ordering of the eight energy bands at k = 0 remains the same over the entire first BZ. This is important because the positions of the energy bands relative to each other determine the likelihood of their population by electrons. E3(k). E7(k). and the four highest bands are empty. Symmetry of valence a n d conduction band states at r We know that degenerate eigenst ate8 of the crystal Hamiltonian having the same energy value form a set of basis functions for an irreducible representation of the small point group for the wavevector k. El(k) and &(k) form valence bands. i. As already mentioned at the beginning of this section. For a . whch. at temperature T = 0 . For brevity. as does every primitive unit cell of reciprocal space. here. the remainder of o which is composed of all elemfxttb of T d multiplied by the inversion. The dimensions of the irreducible representations are the same as the degrres of degeneracy of the corresponding energy levels. and secondly.286).3).Sn. Therefore. and those of E2(0) = &(o) = E4(0) and E s ( 0 ) = E s ( 0 ) = E r ( 0 ) each belong to 3-dimensional representations. may be obtained as follows: For a simple band. exchanges the two sublattices. For a periodicity region of volume Q = G3Ro. the energy gap of a-Sn vanishes. and Es(k). is oh. firstly. Four such bands are necessary to host the (2 x 4) G3 = 8G3 valence electrons of a periodicity region. the first B Z contains. According to equation (2.and p-levels of the free atom whose orbitals were used as basis functions were not completely filled. the deepest valence bend level Ei(0) ha5 the eigenfunction (l/fi)[Is10)+ I s20)]. E l ( k ) . E4(k) are the populated valence bands. Si and Ge.

For LY . We summarize the results of our TI3 band structure calculations as follows: For crystals which have the diamond structure. is partially a conduction band. thus it belongs to the unit representasl0). It follows from the character table of the irreducible representations of Oh given in Appendix A. the highest valence band is 3-fold degenerate and belangs to the irreducible representation of the point group oh. i. The lowest conduction band at r exhibits either a similar %fold degeneracy. Under the action of the non-exchanging elements of oh. for C. The s eigenfunction (l/&)[l 1 0 ) + 1 sZO)] for E l ( 0 ) transforms into itself under the action of both types of elements. it has to be recognized that the between orbitals at the mme center depend on matrix elements E~ and whether the center is an atom of chemical species 1 or 2.(1/&)[1 y 1 0 ) + I Y ~ O ) ](. Si). in which case it belongs to the repraentation f 1 5 (C.21.I d o ) ] .283). Inversion. . l / f i ) { Yloj. that this transformation corresponds to the representation r.. For the eigenfunction (l/fi){l transformation into itself occurs only under the action of non-exchanging elements. This means that two different s. the F2-band lies below the I'g ' i -band. In order to apply the TB approximation to semiconductors having the zincblende structure. these functions transform like vector components. Firstly.2.I s 2 0 ) ] of the Es(O)-level.t i in the block at the upper left. the Hamiltonian matrix [Z. one finds that the eigenstates (1/&)[1x10)+ I d o ) ] . Extension t o semiconductors of zincblcnde t y p e Band structures of diianioand type semiconductors calculated by means of the empirical TB method reflect the essential features of the real valence bands of these materials quite well.E7(O). and e .ZS3) must be modified as follows.Sn. or i t is non-degenerate and belongs t o the representation I (Ge). :t . The character table of the irreducible representations of Oh in Appendix A shows that this transformation is characteristic of the representation J&. Similarly.e. as a rule.. Si. which in this way. 1 / f i ) [ I zl0j-t I ZZO)] belonging to the eigenvalues E s ( 0 ) = E e ( 0 ) . The upper valence band level E z ( 0 ) = E3(O) = E4(0) possesses the three eigenstates ( ~ / f i ) [ l 1 220)]. and the exchange of the two sublattices also reverses the sign of the whole eigenfunctions. while a factor -1 is generated in the case of exchanging elements. which is part of the exchanging elements. transform according to the irrcduciblc representation rl.6.I Y ~ o )(1/])[1. The three eigenfunctions therefore transform as they w o d d under the action of the corresponding non-exchanging elements. Tight binding approximation 163 the latter elements 'exchanging'. 210)( l & ~ 1 0 ) . reverses the sign of the vector components. Ge.and p-energies have to be inserted into the two 4 x 4 diagonal blocks of the matrix (2. r&.ti. and the former ones 'non-exchanging'. These results are illustrated graphically iu Figure 2. the tion rl.

’ - r. Secondly. and the p-state to a 2-atom.’ 6. while for the s-state belongs to a 2-atom. r. (the parameters iSw Table 2.8 are associated with in by meany of equation (2. the s-state belongs to a 1 atom. With these two changes.. diamond structure - 6 - zinblende structure Figure 2.283) the TB Hamiltonian matrix for zincblende type semiconductors becomes z. - conduction bands valence bands r.284) remain valid because they refer to matrix elements whose orbitals at the two different atoms belong to the same state. Therefore. V & is given by an independent constant rather than by -V:$. in equation (2.164 Chapter 2..273) cannot be used in the zincblende case because it rests on the chemical identity of lhe two atoms of A unit cell. -espc csF . - 6. thr matrix element. Elect. the relation V$$ -V:$ G -V3w of equation (2.284).ronic structure of ideal crystals r.21: Ordering of energy bands at the center 1 of the fint B Z for semicon’ ductors of diamond and zincblende type. The other excliangr relations in (2. - r. and the p-state to a 1-atom. For the matrix element l 2 . in that at the lower right.

The wprPsPntaliun ri. all paints k of the f i d BZ. Tight binding approximation 165 with ESP= (l/fi)c&. strictly speaking. they are not energy eigenfunctions of the atoms. In contrast to diamond type crystals. Formula (2. However.2. one must introduce further simplifications. total energy and chemical bonding Once the bald stnicture is known.the rl-band being the deepest.6. its deviation from the total energy of the valence electrons of the free atoms which were brought together to form the crystal. one has practically 15 only one energetic ordering of the conduction bands here .rons are the only parts of the atoms whose stat= change when the crystal is formed. 2.z l R ) . which was found for diamond type crystals above. of by Oh thereby becomes the representation r 5 of T d . remains ri5. YIPspatial symmetry of the eigcnstatcs a t thr R Z rentpr is similar to thtlf. the band structure and the eigenstates of zincblende type semiconductors may be calculated.and p orbitals as basis functions. the total energy of the valence electrons ran be calculated.esion energy of the crystal. The total energy of the vakncr elwtrons of the crystal or. A starting point for this is a formulation of the 'I'B approximation which employs certain linear combinations of 8. the TB approximation in the form developed above produces such expressions only at particular symmetry points. and 1 ' s i r . These linear combinations are callcd sp'--hgrhr%d orbitals.I hslR) of a 1-atom in Ih the unit cell at R are defind by the equations . I i replaced by rl. In contrast to the atomic orbitals.6. This definition is reasonable because the valence elect. defines the energy gain due t o chemical bonding. rather than the atomic orhihals of definite angular momentum quantum numbers I ! which were used above. One hw to sum the energy levels of all valence electrons! and subsrquently remove the doubly counted electronelectron Coulomb interaction energy from this sum. known as coh.54) of section 2 . I hslR). except that the point group Ott has to he r ~ p l a r d the tetrahedron group T d . In order to obtain the total e n e r a in closed analytic form. one needs explicit mathematical expressions for the valence band energies st. To find them everywhere.. sp3-hybrid orbitals The four hybrid orbitals I h~lR).3 sp3-hybrids. TTsing this matrix. 1 indicates how this may be done for the ground state of the crystal.

g. Electronic structure of ideal crystals 23 23 23 23 Figure 2.166 Chapter 2. e.22: Illustration of the wavefunctions involved in chemical bonding i n tetrahedrally coordinated semiconductors: sp3-hybridorbitals (a. The orbitals resemble clubs pointing to one of the nearest neighbor atoms in the sublattice 2.$zlR(X) 1 I h d R ) = 5 [ $ s ~ R ( x. b).. I hllR) to atom 21. 1 h z l R ) to atom 22 etc.4 z d X ) . .&lR(X) + d'. I h31R) = 5 [dslR(X) .zlR(X) 1 ) 1 1 1 I Figure 2.22 the probability distributions of the four sp3-hybrid orbitals are n shown in the form of polar diagrams. bonding orbitals (c) and anti-bonding orbitals (d).# z l r t ( X ) -tb y d x ) .

2. are defined by the relations These orbitals point to an atom of type 1. as there are 8 atomic hybrid orbitals 1 &jR)with t = 1. As such. of course.290) of the hybrid orbitals in terms of atomic orbitals. From the hybrid orbitals of a given sublattice one may form Bloch sums I htjk) by means of the relation (2. it has the same eigenvalues and eigenfunctions as the original matrix.2. the four sp3-hybrid orbitals I h12R). this matrix may be understood as arising horn the above mentioned unitary transformation of the known Hamiltonian matrix ( a j k I H I a'j'k) with respect to the basis daJk. I h32R).and porbitals from which they are constructed.2.I h22R). beyond those already made earlier.291) in complete analogy to the Bloch sums q b ~ involving atomic orbitals in equak tion (2. The implementation of the TB method by means of hybrid orbitals instead of atomic orbitals having a definite angular momentum quantum number is therefore nothing but the solution of the same eigenvalue problem in another representation.3. orthogonality also holds for hybrid orbitals at different centers. Hybrid orbitals at the same center are orthonormalized with respect to each other. These approximations facilitate the derivation of simple analytical . However. I h 2 2 R 2 f R) at atom 22. The same holds for the Hamiltonian matrix ( h t j k I H I htrg'k) with respect to the basis I htj k). I h42R) at a 2-atom in the unit cell at R. This statement holds.and I h42&+ R)at atom 24. only as long as equivalent approximations are made in the two representations.4 orbitals for the two free atoms of a unit cell. Tight binding approximation 167 Similarly.255). the Bloch sums I h t j k ) may be thought to arise ~ from the Bloch sums # a 3 of atomic orbitals by means of a unitary transformation. If the latter are understood in the sense of Liiwdin. For each unit cell there are 8 associated and j = 1.6. I h32R3+ R)at atom 23.289) and (2. The following four orbitals are directed to the 1-atom in the unit cell at R: orbital 1 h12Rl+ R) at atom 21. the hybrid orbital representation is well s u i t e d for further approximations. Due t o the definitions (2. as the s.

The former elements do not depend on t and R. . t'. In consequence of this. Thc non-diagonal elements ( ~ Q 1R 1 h t . An analogous result holds for the diagonal elements (&jR 1 H 1 ht3R) at the same center. (2.290). (2. this result is the same as for the matrix elements ( h u k 1 H 1 h u k ) between the corresponding Uloch sums. Hamiltonian in hybrid-orbital representation Here.294) with e3 and ep defined in equation (2. (2. we describe the most important additional approximation available in hybrid orbital representation. Approximately. ~ R have thc samc value for all R and orbital quantum numbers t . while all others may be neglected.290) and equations (2. Their common value ctt is ~h (htjRI H I h y R ) = -(~g 4 1 -t- kp).271) to (2.290) the expression Vl 5 ( k t j R 1 H 1 ht.) 1 4 t # t' . Since only nearest neighbor atoms are considered.289). the Hamiltonian matrix elements ( h t l R I H I ht2 R t R) between these orbitals will be the largest.273) as + The corresponding matrix elements (h+lk I H I ht2k) between the Bloch sums of hybrid-orbitals follow from VJ by multiplying this quantity with the factor et eak. Numerical values for th. are listed in Table 2. For the common value V1 one finds by means of (2.289).295) Again. along with values of Vi and VL. (2.E ~ . one has to distinguish between diagonal and non-diagonal eleIf ) ments. may be determined from (2. the rrvult is the same as for the matrix element ( h y k I ZI I h t f jk) between the corresponding Rlocli sums. which utilizes the fact that those particular hybrid orbitals at nearest neighbor atoms which point toward one another will also overlap one another more strongly than all others.266).( c S . Electronic structure of ideal crystals expressions for the eigenvalues and eigenvectors which may be used to explicitly determine the total energy of the valence electrons of a crystal in closed analytical form.289).168 Chapter 2.jR) - . (2. one need only consider these elements. as can be seen from the explicit expressions for the hybrid orbitals (2. denoted by V2. Their common value.10.dt (2 293) ~ In the casc of Hemiltonian matrix elements between hybrid orbitals at the same center.

10: Hybrid matrix elements calculated from the TB parameters in Table 2. 2 .37 -2. 4 . E. -8. I h 4 W . I h s W . Remarkably. i = 1 . I hzlk).2. I h l W .27 -1.98 Ge -8.296) This matrix is also known as the Weare-l‘horpe Uarniltonian. its 8 eigenvalues can be obtained in closed analytical form.6. (2.we havve Table 2.76 . I h 4 W . Tight binding approximation 169 In writing down the Bamiltonian matrix (htjk I H I hrj’k) in the hybridorbital representation.b. I h32k). 3 .76 -2. Denoting them : by E.7 (in eV). we arrange the eight basis functions in the sequence I h l l k ) . Then the matrix ( h t j k I H I httj’k) takes the form . I h Z W .01 -2.

the energy values of the four valence bands E.23 also illustrates how the different bands emerge from the atomic s-and p-1evrlb due to the two interactions V and V z .c.23: Evolution OF the energy bards of semiconductors with the diamond slructura within the TB approximation The right-hand part shows the band struct.ure of Si calculated by meam of equations (2. one obtains t h bnrrd structure shown in trhf right hmd part of Figure ~ 2. T i means that i the ground hs n state of t h e crystal. Roughly speaking. Figure 2. and the validity of the magnitude relation I V 1>1 “2 I between the absolute values of and Vz. To accomplish this.282). Now wc return to the main goal of this subsection. Vz determines the distance be1 tween the cpnters of gravity of the valence and conduction band complexes. the &lands are fully populated by electrons. the 4 bands indicakl by b lie below the energy gap. thus they are the conduction bands. The actual positions and k-dispersions of the bands (2. they form the valence bands. Electronic structure of ideal crystals r wovevector X Figure 2. Essential features of these relationships are the 1 negative sign of V2. Here gl(k) is the structuredependent factor d e b 4 in equation (2. and V1 the width of thpse bands.b(k)determined above must be summed over all i and k.297).23. the ralcuIatjon of the total energy of the crystal.170 Chapter 2.297) are determined by the parameters th. In this regard. and the a-bands are complekly empty. i. It . Using the values for S i given i Table n 2-10. arid thP 4 bands indicated by u lie above it. 1’1 and Vz.

the so-called bond orbital approsirnation. l . equivalently. carried out in two steps. 1.0. O .O. and the corresponding linear combinations I btR) are given by . temporarily setting Vl to zero.e. Yi'ghht binding approximation 171 turns out that this task may even be carried out analytically if a suitable additional approximation. O . 0: O .296) are calculated without taking account of the VI-terms.0'.0.. 0). the eigenvalues and rigenvectors of the matrix (2. Each of the eigenfunctions I btk) and 1 atk) is a linear combination of Bloch sums of two hybrid orbitals pointing toward one another.296). and the 4 eigenfunctions I atk) belonging to E. e : ) .O. or.2. we review the already solved problem of diagonalizing the Hamiltonian (2.0. this leads to the reduction of the enerffi bands to the two dispersionless levels givw by 5k) belonging t o q. D. Bond orbital approximation To introduce this approximation.0: -ez. In the first step.299) (htlk 1 b4k) = ( l / J z ) ( O .e. i. The diagonalization will now bt. In the case of &states the hybrid orbitals are added. a Bloch sum of the linear combinations of these orbitals. (2.O.. have the components (ht2k I agk) = (l/&)(O. 1.O). O . -. (ht2k I aqk) = ( l / & ) ( O . O . but procwd in a sompwhat different way. is made. have the components bik) (l/fi)[l.I.297).0.0. As may he scen from formula (2.O. O . O.

and the corresponding linear combinations I a . one refers to the orbitals I h t R ) as bondiny and to the orbitals 1 arR)as anhi-bonding orbitals.0 may be written in the form 1 ' I btk) - aR 1 eik'R I b t R ) .299) and (2. (2.301) Thc exponential factors eF of the eigenvectors (2. 4 .296) is transformed iuto the basis set of the previously calculated eigenvectors 1 btk) and 1 atk). With the help of bonding and anti-bonding orbitals the eigenfunctions of the Hamiltonian matrix (2.172 Chapter 2.1 . This results in the (8 x 8)-matrix (2.303) (2. R ) are given by The polar diagrams of these functions are shown in Figure 2. 2 . (2. The Hamilton matrix (2.11 h t l 1/2 1 R)+ I h2Rt + R)]. 1 . In the case of a-states the hybrid orbitals are subtracted.22. Electronic structure of ideal crystah I kR)= .300) were compensated by the et-factors of the Bloch sums. t . For reasons which will be clarified later.304) In the second step of the diagonalization procedure the Vl-terms are included. 4 .305) with the (4 x 4) -matrices .296) with b -.1 . 3 . 3 . 2 .

is referred to as the b o d ovbital approximation. and H. One has Er$&f’= 2 k z E:(k) -Ecd (2.. we write the eigenvalues @(k) in (2. the former by diagonalizing the matrix Hbbq the latter by diagonalizing Hw. The expression for I. follows from that €or H & if in the f latter q. couples the various anti-bop. Tight binding approximation 173 {2.310) as diagonal elements of H M between eigenstates.306) and (2.309) where E d means the Coulomb energy of the interacting valence electrons which is counted twice in summing upon all band states. Within the bond-orbital approximation. i. the complete neglect of the interaction between bonding and anti-bonding states. T h e latter may be calculated by means of formnla (2. with the result (2.54) which expresses the total energy of an interacting electron system by means of its one-particle energies. and note that within the bond orbital approximation the eigenstates for a given wavevector k are linear . the i-sum in (2. is replaced by E.310) To pro>*ethis relation. Considering the actual values of V1 and V2. The zero-th approximation.ding states.307) as block elements.307) are defined as follows: The (4 x 4)-matrix H M couples the various bonding states. The non-diagonal matrix Hab describes the interaction between the two types of states. To calculate the total energy of the crystal one needs the total energy of all valence electrons.e. The factor 2 accounts for the two spin states. these corrections are rather small.2. Within this approximation the valence and conduction bands follow from separate eigenvalue equations. The structure factors g t p and &) in (2. This suggests treating them as perturbations.309) may be carried out in closed form.6. It gives rise to corrections to ’ the eigenvalues of relative order of magnitude I 11 I /2 I V2 I..

and that the nearest neighbor distance will have the experimentally observed value. this coefficient repre sents the negative of the sum of all diagonal elements. crystallize into the diamond structure. as well as the energy of the atomic cores and their mutual electrostatic interaction energy. however. Electronic structure of ideal crystals combinations of the bonding states I bik) only. confirming the validity of equation (2. In other words. If one sums the eigenvalues @(k) over all i .310). one obtains from the relations (2. The distance d between the nearest neighbor atoms will now be chosen. one must also show that no other crystal structure can yield a lower total energy minimum.f'(d)of the valence electrons of a crystal with G3 unit cells. therefore. -4q.. in this structure. One may also prove this relation in another way. The total energy E. i.298) the value (2. using Vieta's theorem. In the case of the characteristic polynomial of a matrix. as above. q.th degree term. under normal conditions. for that was assumed a priori. Total energy and covalent bonding We proceed on the assumption that the atoms are arranged. in the form of a diamond type crystal. To verify this. then the diagonal elements of Hw with respect to the eigenvectors become the diagonal elements of this matrix with respect to the bonding states. the energy of the atomic cores must be . In this matter.306).310). as is stated in relation (2. Our considerations here have the sole purpose of understanding why. (2. which indicates that elements of the fourth group of the periodic table. The total energy of this fictional diamond type crystal represents a function EEfAt"l(d) of d.f$a'(d) of the crystal is composed of the energy of the valence electron system in the field of the atomic cores.1). This result constitutes a theoretical proof that the atoms bind themselves into the form of a crystal. here.311) To get the total energy of the crystal. the total energy reaches a minimum at a finite distance d = do. we want to understand why chemical bonding should occur at all between atoms of group IV.310) and (2. We will not address this question. but rely on experience.309).174 Chapter 2.e. We will demonstrate that E Z Z t a Z ( d )reaches its absolute minimum at the finite distance d = do. the linear combinations are generated by the unitary transformation which diagonalizes the Hermitian matrix H a of (2. to have a value different from the do-value of the actual crystal. This does not prove the correctness of the diamond structure of the crystal. and takes advantage of unitarity. For the total energy EE$. which states that the sum of all zeros of a polynomial of degree n equals the negative of the coefficient of the (n .

we compare the total energy E g t p l ( d ) of the crystal with the total energy E f $ T of 2G3 free atoms.311). again.313) where Eo. For large d.6. one has (2. For the elements of the fourth group of the periodic table with their two electrons in atomic €.the hybrid energies Eh have d-dependence as they are defined by the diagonal matrix elements of the Hamiltonian H between Lowdin orbitals which contain overlap integrals between s.312) The d-dependence of this energy is due to the fact that both Eh and V z depend on d . Tight binding approximation 175 added to the energy value of equation (2. Finally. one may again use the fact that the core states of the crystal do not differ from those of the free atoms.313) represents the cohesion eriergy of the crystal. This means that the initially free atoms will not remain free but form a diamond type crystal with nearest neighbor distance do. the total energy E z l b l ( d ) of the crystal varies with d as shown in Figure 2.2. the total energy of the crystal is given by (2. The corecore interaction energy approximately cancels. It is given by the expression .-levels and two in atomic cp-levels.24 schematically.312) and (2. corresponding to an attractive force between the atoms. corresponding to a repulsive force.orbitals of adjacent 2 atoms. of valence electrons therefore. the repulsion dominates over the attraction. Overall. At the equilibrium distance do. The negative difference of the two energies (2. This means that only the mutual electrostatic interaction of the cores results in a structuredependent energy contribution. approximately. The core-core interaction energy has. it takes its absolute minimum value. accounts for the energy of the atomic cores. the same value as the electron-electron interaction energy E d between the valence electrons on different atoms. while the internal core energies sum to a constant Eo. V2 decreases with decreasing distance d. In order to provide a better physical understanding of the nature of covalent chemical bonding.and p . and V because this quantity is the matrix element of H between hybrid orbitals at nearest neighbor atoms. They experience what is called covalent chemical bonding. against the negative Coulomb energy -E. increases as d decreases.1 in expression (2. and for small d. In doing so.311). the attraction dominates over the repulsion. The hybrid energy q. This is true because the valence electron charge of an atom equals its core charge for the crystals considered here.

depending on whether bonding or anti-bonding states are considered. In the casc of constructive interference. The latter difference may he understood as the energy increase of an atom if one of itb two . Elecbronic structure of ideal crystals Figure 2. their kinetic energy decreases considerably. In this process.176 Chapter 2. This can be constructive or destructive. covalent bonding between neutral atoms Lannot bc understood in terms of classical physics. the energy of the two electrons decreases. the probability amplitude becomes relatively large in the region between the two atoms and the two electrons of the interfering sp3-4ybrjds undergo a delocalization (see Figure 2.24: Dependence of energy difference Eza?''' ( d ) -E::+Ts on f.e. a larger positional uncertainty. i.he inter-atomic crystal atom Etotol -Eta. Unlike the bonding of electrically diflerent charged ions. Altogether. However. if the condition 4 I V2 I> ( e p . in a bonding state. the potential energy of the Coulomb interaction of the two electrons among themselves and with the atomic cores remains almost unchanged. quanturti rtieclianical phenonienology is essential in the interpretation of this behavior. it is energetically favorable for covalent chemical bonding to occur.ral distance d (schematically). If it exceeds the energy necessary for promoting an atom into its sp'-state. the electrons of adjacent atoms are capable of pronounced interference. b e cause of constructive interference. Formally. corresponds to a smaller momentum uncertainty and. if its four valence electrons a x put into four sp'-kybrid orbitals rathe1 than into two s.22). equivalently. In sp'--hybrid states. and that I 4 2 I exceeds the energy v differericc (cP . i. The energy gain per atom amounts to 4 I Vz 1.e.+electrons i s lifted into a p-state or. As we have seen. the occurrence of a positive cohesion energy is due to the fact that the matrix element V2 o l H bctween hybrid oxbitals at adjacent atoms pointing toward one another is negative. .and two p-orbitals. to a smaller kinetic ene~gy.F ~ ) holds.cs). therefore. This may be imderstood in terms of the Heisenberg TTncertainty Principle which tells us that a weaker localization. One calls this population the promoted configuration of the atom.

and atom 2 is the negative anion. With this replacement. ! then I!?. Ionic bonding The ionic contributions to chemical bonding will now be calculated for mat.art' positive. A s is well-known. in the ground state.The c:ondition necessary for thc occiirrcnce of bonding eigenstates able to host all vrtlprrcp electrons is the ordering of the newest. so to speak.317) represent the probabiMes of finding an elrctron in the bonding state at atom 1 or 2. the bonding and anti-bonding energy levels become EL where =c i Thr energy separation betwren the two levels is larger than that of diamond type crystals. For the Ilamiltonian matrix (2.305). In this way thc above consideration also justifies focming on the tetrtlhedral crystal structure of diamond type crystals. neigIi1.Vs/dV. the transit. The atomic structure follows. . where we set a p . respectively. One calls aP the polarity uj bonding orbitals or simply the polardty of bonding. from the electronic structure. In this way the polarity of bonding orbitals is such that. If f f f is deeper than c i . The bonding and anti-bonding oibilals arp given by the expressions !+. i. and also up. whcre the electrons occupy only boxrding orbitals. This results in an enlargement of the energy gap betwcm the valence and conduclion hands. which was merely assumed at the outset. . the diamond structure of the crystal.ion from the diamond to the zincblendc structure means that ch in the upper left (4 x 4)-block has to be replaced by the hybrid energy of the 1-atom? and in the lower (4 x 4 )-block by the hybrid energy e i of the 2-atom. the previously electrically neutral atoms heconie charged.+ rials having the zincblende structure. The electron prpferpntially stays at atom 2 . Atom I becomes the positive cation. The charge of the cation is given by c Z * with Z' = (Z.a p ) and (1/2)(1+ctp) in ('2.316) and (2.4 t $ap). T h e f d o r s {1/2)(1. ~8. a scries of 111-V and 11-VI compound semiconductors form crystals of this type.e.where 21 is the number of valence electrons at + bp.ors of an atom on the comers of a tetrahedron.

Since the bonding is then pdrtially due l o attractive forces between ions. Owing to this redistribution of electron charge.4 . the total The Madelung energy is negative. i. therefore. One therefore sets (2. and on the other hand. in passing from the 111-V through the IIVI to the I-VII compounds. 11-VI and I-VII compounds. With energy of the crystal is EMad. The anion charge is -e(Zz . The absolute value of the Madelung energy is. It is. shifted in the same way with respect to each other as in the rocksalt . the n-values are listed for crystal structures which are observed in materials composed of group IV elements as well as 111-V. The cesium chloride structure follows from the rocksalt structure by replacing the two facecentered cubic sublattices by two primitive cubic sublattices.11. on the one hand. The latter depends on crystal structure and can easily be calculated numerically. because of double counting. OTW refers to it as partially zonzc bondzng.e. i. The value for the wurtzite structiirp in Table 2.The general expression for E M a d iu where the sum extends over a periodicity region. one observes a transition from the zincblende structure through the wurtzite to the rocksalt and cesium chloride structures. takes a different.320) with cy as the so-called Madelung constant. Electronic structure of ideal crystals thc free 1-atom. In Table 2. This results in a tendency of compounds with larger 8* valiirs to crystallize in structures with Madelung constants larger than that of the zincblende structure. the electron-electron interaction energy to be subtracted from the sum of oneparticle energies. This leads to an additional contribution to the total energy of the crystal which may be interpreted as the electrostatic interaction cnergy between anions and cations. Onc calls it the Madelony energy E M & . no longer completely compensated by the electrostatic interaction energy between atomic cores. proportional to the number GT of unit cells. inversely proportional to the distance d between two adjacent ions. it strengthens chemical bonding. Therefore.e.e Z * . The contribution of the Madelung energy to the total cnergy of a given compound will be larger for larger effwtive charge number Z* of the compound.178 Chapter 2. value.4 a p ) = .11 corresponds to the ideal tetrahedral case with an equivalent cubic lattice constant &a (see Chapter 1). the unit cell is neutral.

no longer depends on the crystal structure. i. Then the crystal consists of positive ions of the group I atoms.e.7 2.1 k . which represents an essentia1 part of the bonding energy and forms the driving force for the formation of ions. As we know these functions of (which will be denoted below by (xluk) instead of q y k ( x ) ) are the product of an exponential factor exp(ik. as mentioned above.7. One refers to such crystals as tonac crystals. p-method rests on a particular property of the BIoch type eigenfunctions pV.x) and the latticeperiodic BIoch factor uvk(x). k . the energy gain due to the transfer of electrons from cations to anions. and negative ions of the group VII atoms whose valence shells are completely filled. Zincblende U’urtzite Rocksalt 1. the energy gap becomes larger. 2. Therefore.6381 1.7. which have lost all their valence electrons. This structure is determined by the hladelung energy only.7476 structure. In the case of the I-VII compounds. then the resulting functions . This implies that almost all valence electrons of the compound stay at the anion.2. ionic crystals exhibit structures with particularly large hladelung energies.p -method Fundamentals Luttinger-Kohn functions The k.e.+(x) the crystal Hamiltonian H . by ( a / 2 . p -method 179 Table 2. rocksalt and cesium chloride structures. i. a / 2 .6410 1. the absolute values of V3 are so large in comparison with V that the bonding polarity op is approximately 2 unity. In this case. With growing polarity of the bonding. a/2).11: Madelung constants for several crystal structures. This explains the transition from the semiconducting properties of the group IV crystals to the insulating nature of the I-VII compound crystals. while retaining k in the exponential factor. If one replaces the wavevector k in uYk(x) by a constant ko.

The (xlvkko) are referred tu as LuftmgGgP7. e.6 v l u 6 k ~ k .as often occurs. ) uk (2 322) (2. to icienliljr ko with k . but they do form a complete orthonarmalizPc1 basis set in Hilbert space. as wcll as the Bloch functions. These elements arc. we expand thP Bloch functions (xjuk}with respect to Luttinger Kohn functions (xjpk’ko). then the Hamiltonian matrix in the Luttinger-Kohn basis is completely determined. p-method takw advantage of this properky of the Luttinga-Kohn functions. hes.321) are no longer eigenfunctions of H of course. On\y terms with k’ = k occur in this expansion because of the lattice translation symmetry of both functions.x).323) Thp vdidily of these relations f d o w b directly from the rorripletenyss and orthonormality of the Bloch functions. The k . However.K u h fiLa~t7onu. In this method. In order to accomplish the ahove program. If k. by the matrur elements of H between the Bloch factors Uyk(X) for k = ko. Tllis means that the k p-method allows 0 1 to calrulate.g.e. to extrapolate from thc particular point ko t o t h e entire first BZ.b(x‘ . as we will s e e later. of course. one represents the Srhriidinger quation for R crystal electron in terms of the complete orthonormaIized set of these functions. in the vicinity of the valence band ninxinium or the coridurtion band minimimi. h y arp determined by the Blorh factors u V k ( x ) T for the special wavevector ko in contrast to the Bloch functiom which require full knowledge u l u. ko should still be considered an arbitrary point of the first HZ. just as little known as the Bloch factors themselves. ()€ten one is only interested in solutions in the vicinity of a critical point k. at the center . one has ko = 0. one may take them as empirical parameters. If one does so and inserts values for the parameters. This choice will be used later. whence . Then it is expedient. whence ~ (v’k’ko(vkko). The rpsulting matrix elcments of H can be expressed. Uiagonalizing this matrix yields the eigenvalues and eigenfunctions of the crystal Hamiltonian H for all valiies of k. although not necessary.k(x) lor all wavevectors k.1x0 [2. of the 6rst BZ. for example.i. At the outset. 1 r from the Bloch matrix elements at only one point kol the eigenr-alues and cigenfunctions over the entirc first €32. ~ ( x ’ l v k k o ) ( v k k o l x-.

Hamiltonian ‘l’hematrix elements (pkko I H I p’k‘ko) of the llarniltonian bptween T.328) The matriv on the right-hand side of (2.eik-x] = eik-x (p2 f 2fik.(ko) Ti2 + -(k 2m - ko)2.327) has been transferred to the new Hamiltonian Hk.327) allows for an important rewriting.7. p! (2.p(k) in the k-independent partial Bloch basis lpkoko) = jpko) for the wavevector k = ko.178) in the Luttinger-Kohn representation bmomes k . k . (2.p(k) on the right-hand side.p(k) = Ho(k) h + -(k na . (2. p + h2k2) . with this new Hamilt onian. if one uses the easily provcn commutation relation [p2.(k)lP’ko).2.325).uttingpr Kohu functions can he t r a d back to matrix elements (pko I p j p’ko) ol the momentum operator p between Bloch functions.p .33 1) The latter relation means that the actual Hamiltonian matrix W in the kdependent Luttinger-Kohn basis Ipkko) equals the representative matrix of a fictional k-dependent Harniltonian Hk.ko) .. If one defines Hk.329) with (PkkolfflP’kko) = (PkoIHk. (2.326) which yields where we have set E:(k) = E. The k-dependence of the Luttinger-Kohn basis on the left hand-side of equation (2. The SchrGdinger equation (2. p -method 181 With this expansion. the Schriidinger equation (2. reads .

order perturbation theory the eigenvalue E$(k) arising from EE(k) is given by the relation (2.(k) of the exact band energies E . although the operator Hk. one can treat this interaction with the help of quantum mechanical perturbation theory. this entails a power series expansion of the energy bands E.182 Chapter 2. are degenerate or not. For k-vectors sufficiently close to ICO. one calls it the k . are not bands in the sense of the eigenvalues of the actual crystal Hamiltonian H . We will first consider the simpler case of non-degenerate bands. Application to non-degenerate bands.e. p-term in Hk.(ko). = VkEb(k)lb. The form of the perturbation theoretical expansion depends on whet her the unperturbed bands. Since this interaction results from the (k . As the point k in Hk.no approximation is needed to obtain the relation OkE. the bands which are mutually coupled. one may interpret these non-vanishing elements as arising horn an interaction between different bands. p-interaction tends to zero.333) and the Bloch function Ivk)' arising from 1.(k) in k . For k = ko this matrix is automatically diagonal.they are fictional bands E:(k) defined by equation (2.(k)Ip'ko) has off-diagonal elements with respect to the band indices. Apart fkom the square term in (k . by virtue of the fact that Bloch functions Ipko) are eigenfunctions of the Hamiltonian Hk.(k)lk. Effective masses In first.p(k).&).k)' E Ivkko) by the relation Since the f m t derivatives VkE. Solution of the Schrodinger equation (2. ( k ) at ko depend only on linear expansion terms of E. the Ipko) states are no longer eigenfunctions of Hk.332) involves the diagonalization of the matrix (pkolHkE. In this.(k)lp'ko)..332) refer to the LuttingerKohn basis Ipkko).p(k)is represented in the Bloch basis Ipko).328).. the eigenvalues E.ko) . Eiectronic structure of ideal crystals The components of the eigenvectors Ivk) in (2. so that the matrix (pkolHk. Considering .(k) approaches ko.(k) with respect to (k . For k # ko.ko) about the point ko.the latter are uncoupled by definition . Formally. pinteractian.p(kO) = Ho.ko) already present in E:(k).ko. i. the k .

As far as the band separations are concerned (only for them can one make an easy estimate).' with respect to the principal axis system. therefore. we will later find conhmation of this tendency in all concrete cases. p method 183 (2. One expects small effective masses for large momentum matrix elements and small band separations. we call M L 1 the effective mass tensor at the critical point k. This .193) used above without proof. One must proceed to the second order to get a non-vanishing contribution from the k p-perturbation.e. In particular. This holds the same content as equation (2. i.3331. one obtains from (2.2. The tendency indicated is that the absolute values of the effective masses become larger for smaller momentum matrix elements and larger band separations. and the energetically lower a mass of the same large absolute value but of negative sign. We rewrite this expres- mz' Generalizing the terminology introduced in section 2. For pairs of bands which are closer to each other than to all other bands and. if ko is a critical point kc. if V&.338) allows one to also draw a conclusion about the signs of the effective masses.337) the relation This relation connects the effective masses with the matrix elements of the momentum operator between different bands and with the energy separation of bands at the critical point. because ko may be an arbitrary point of the first B Z .7.. k . for brevity. this exact relation yields V&v(k)lb = ( h / r n ) ( v b l p l v h ) . whose mutual interaction is stronger than that with all other bands. For the diagonal elements .p-correction vanishes in first order perturbation theory. we set (I& sion in the form I p I pkc) = (v 1 p I p ) . then the k . = 0 holds.6. According to it. The result reads where. relation (2. of At.(k)\k. the energetically higher of the two bands should have a large positive effective mass.

z of the position vector itself transform in accordance with the irreducible representation I5 o Oh.3.g. If this happens. The maximum is 3-fold degenerate.y. By diagonalizing this matrix one obtains the eigenvalues in second order perturbation theory. zx.184 Chapter 2. we set & = 0. In quantum mechanics. This approximation is valid for semiconductor materials composed of light elements only. Si. where m can assume the values 2.7. including. Band degeneracy Critical points are often symmetry centers or lie on symmetry lines. p-perturbation matrix between the degenerate unperturbed states vanishes.S~~~S conclusion also proves to be valid in all cases in which the assumptions of this calculation apply. in general. 2. is the valence band maximum of semiconductors with diamond structure. but between the (also degenerate) eigenstates of first order of perturbation theory. In doing so. and at these symmetry points.2.the matrix of the perturbing Hamiltonian operator between the degenerate states has to be diagonalized (we remind the reader of the nearly free electron approximation in section 2. y of the components 2. Electronic structure of ideal CFZ. According to section 2. these eigenfunctions belong to the irreducible represent ation l?b5 of the cubic group oh. as is commonly done. one must carry out second order k. This case will now be investigated. For other materials this procedure serves as a zero-order approximation which can be used to proceed further (as we will do below). and IvzO) with zy. w e initially neglect the spin-oIbit interaction. no longer degenerate. degeneracy of the energy bands often occurs. One must therefore choose a variant of perturbation theory for degenerate energies which works in second order. To this end. We denote the three pertinent Bloch functions by IvmO). Therefore. These are.4). This procedure does not apply here because the perturbation matrix at critical points vanishes in first order. a basis of this repz resentation is formed by the products yz.6. The vector components 2. we may identify IvzO) with yz. ' 1 f . IvyO) with zz. Therefore. for example.pperturbation theory €or degenerate bands. with regard to their transformation properties under the action of elements of o h .2 Valence bands of diamond structure semiconductors without spin-orbit interaction As we know from section 2. z of position vector x.y. one constructs the matrix of the perturbation operator not between degenerate unperturbed eigenstates. As indicated in Appendix -4. An important case in which the k . the valence band maximum of diamond type semiconductors is located at the center r' of the first B Z . perturbation theory for degenerate energy levels is c o m o n l y of first order .

332) are needed to first order in the k . anticipated above. In particular.. the three degenerate states ( v I O ) . wherein the identity representation does not occur. The resulting matrix is 'almost' diagonal. z insofar as their transformation behavior is concerned.. 2. and the degenerate valence band energy E J O ) is denoted by Ev. pperturbation. The states Ivmk)' and Ipk)' with p # t m will now be used as a basis set to represent the IIamiltonian H .339) where we set E. x (rh ri2 I'15 r 2 5 ) . These elements give rise to corrections of the valence band energies which are only of third order and can be neglected. may easily be demonstrated using the pertinent criterion for such vanishing given in Appendix A: The operator p transforms according to the irreducible representation I'15 of oh. Expressions of tlic form (2. but we omit an explicit presentation of them here.339) also hold for the approximate Bloch functions Ipk)' of the remaining bands p with p f urn.(O) = for brevity. = I?. IuyO). the solutions of Schrodingers equation (2. In the case of the diamond structure. The matrix (umOlplvm'0) therefore belongs to the reducible representation x r 1 5 x rl. For the orthonormalieed Rloch valence band eigenstates (vmk)l one finds (2. less obvious cases. tlir value 11 = 7 m does not need to be 1 specifically excluded because the matrix elements ( p I p I vm') for p = 117n vanish anyway. because the basis functions are 'almost' eigenfunctions. z are merely a short hand notation. IuzO) of the valence band maximum may therefore be associated with I.7. p -perturbation theory t o second order with degeneracy In order to apply degenerate second order perturbation theory. p -method 185 For the subgroup T d of oh the two representations F15 and r h 5 coincide. (:onsidering the sum on p . + + + k . the submatrix of the three velence bands is coupled to the remainder of the matrix only by elements of second order in the k . as we will see immediately below.y.2. The vanishing of the matrix (vmOlplum'0) of the momentum operator between valence band states at I?.339) guarantees the normalization. We have chosen the somewhat more troublesome method of proof because it may also be applied in other. . According to Appendix A this means that the matrix (umOlplvm'0) must vanish. The third term in (2. p-perturbation. For semiconductors having the zincblende structure. k . One can also obtain this result by means of inversion symmetry alone.y.

339) for the perturbed states Ivrnk)'. namely '(vmklH!vm'k)l l(wn'kl&:y)= E ' .-k 5T'k5 The tensor D z L .345) one can see that D Z k . transforms under symmetry operations of the cubic group Oh according to the $-fold product representation [rb5 ri5]a [1'1~ x l ? 1 ~ ] . Electronic structure of ideal crystals In second order perturbation theory. is symmetric. one may write (2. m' it is IIermitiaa From equation ('2. then contains as many independent elements as the L?zk.340) can be obtained by means of expression (2.342) in the more compact form With respect to the indices a r P lthe tensor D z i . rn.340) The initial occurrence of interaction betwren the valence band and the r e maining bands is incorporated in the matrix (u>m I H I wn'k) in first order k perturbation theory..186 Chapter 2. Since the states I p ) = 1 P O } are eigenfunctions of H with eigenvalue EEl= E. which yields [rk5 r& x [rI5 rl& = 3r1 rz 4r12 x x 3 . c one can show that these correspond t o the three types of non-vanishing + + + + + . therefore has three independent components.lrn x I115Is. Using Appendix A . A short calculation yields where is a fourth-rank tensor. '(vrnklE. x x where the index s denotes the fiyrnmetrical part of the product. the valence band energies Ev and Forresponding Rloch states I&.).) therefore follow from an rigenvalue equation which is decoupled from the remaining bands.(O). number of times the identity representation occurs in the product [I?& x riE. According to Appendix A. Harniltonian m a t r i x The (3 x 3)-Hamiltonian matrix '(vmklHlvm'k)' of equation (2. (2. one finds [I'15 rl5Is [& x r&lS x [I'Is x = I = r1 r12 ra. and with respect to the indices m .

they are invariant.The Hamiltonian matrix reprewrits an element in the product space of Ihe two spaces which is invariant under transformations of the point group Oh. Since QB a l remaining matrix elements Dmm. L .f-fi of the components of the vwtor k.p -method 187 matrix elements D z z . In the product spacc k. The elements L. (considered in Appendix Iz A ) and their products. k. To find the most general Hamiltonian matrix compatible with the symmetry oh. one obtains .344) can also be derived in a somewhat different way. and N = D$ f D g . M and N to IIP empirical parameters (as indicated at the outset) and use their connection with the Bloch factors only to identify some general properti=. each of which belongs to a particular irreducible representation of Oh. the corresponding scalar products belong to the. As seen in Appendix A. By & tion [ decomposing it into i t s irmliicible parts. I.] of the point group oh. In the absence of this informalion. Such a matrix basis can easily be constructed by means of the 3dimrnsionel angular niomenturn matrices Iz. but is formally more dernanding. One uses the fact that the Hamiltonian matrix l(vmklHlum'k)l can be represented as a linear combination of the 9 matrices of a basis in the product space 1 vmO) (iirn'O 1 which transforms according to the repreaentaI x r:. Such invariant elements of the product space can be produced by forming scalar pruducts of subbases of the two spaces whi& transform according to the same irreducible repre sentation.7. that is to say. one has to determine all invariants of the product space. we consider L . One determimes a basis from subbases which transform according to the irreducible parts of the representation [I'15 x r15Iy.€ one then multiplies each by a real scalar factor and sums them all. the Hamiltmian matrix of the l valence band has the form Method of invariants The Hamiltonian matrix (2. such as the fact that they can be chosen real. whirh leads to the goal more quickly. M and can be calculated if the Bloch factors are known. and D Z . however. This representation is reducible. m e obtains a basis which consists of subbases. since it is known how these matrices transform. vanish. one proceeds in a similar way.2. We introduce the abbreviations L l& D g . hl = D$$. namely according to the pseudovector representation I':s.identity representation.Iv.

(2.2(k) = .346) E. in general. but evidently. and it quickly leads to the goal if one considers spin and spin-orbit interaction. E.3(k) = L k 2 .l/a(k) of equations (2.9) or the interaction with mechanical strain. It also allows one to determine the matrices for perturbing Hamiltonians other than that of the k . All bands are parabolic. [lll]and [110] the dispersion curves are determined by simple analytical expressions as follows: E.68 in units of ( h 2 / 2 m ) .25).347) 1 2 + M + N]k2. Using these values. the two degenerate bands E. such as the interaction between the angular momentum of Bloch electrons and an external magnetic field (see section 3.[ L 1 (2.N]k2.3(k) = . In this book. Electronic structure of ideal crystals the most general invariant of the product space and thus the most general Hamiltonian matrix compatible with Oh symmetry. E. For the three symmetric k-directions [loo].l(k). Valence b a n d s t r u c t u r e The eigenvalues of the matrix (2.348) Along the two directions [loo] and [lll].[ L 3 + 2M . splits into two bands.345) 1 E.lp(k) = .n(k).3(k) = . not isotropic. E. This indicates a %fold splitting of the valence band for such k. the valence band.3(k). we will only use the method of invariants occasionally.lp(k) = M k 2 . no degeneracy remains. (2. In the [llO]-direction and also for all more asymmetric k-vectors.64. p-interaction. In the case of Si. one has L = -5.188 Chapter 2. one 2-fold degenerate and one nondegenerate (see Figure 2. (2.344) form three valence bands E.[ L 3 + 2M + 2 N ] k 2 .345) . E. One speaks of a warping of energy bands. 1 E.N]k2.l(k) = M k 2 . This process is called the method of invariants.60.[ L 2 +M . It is applicable to arbitrary symmetry groups and degrees of degeneracy. being triply degenerate at r. M = -3. E. A comprehensive outline of the method with several applications i s given by Bir and Pikus (1974). N = -8.

Then.2. anisotropy grows stronger as the difference between the masses of the two types of holes becomes larger. Isotropy exists only if N = 0 and L = M .346) have smaller curvatures than the third band E. We now proceed to consider the effects of spin-orbit interaction. k . the valence band structure is significantly influenced by this interaction (in the case of Si it is small. -r . The results discussed above were obtained without consideration o l spinorbit interaction. augmented by multiplication with the eigenfunctions ( s l u ) of the z-component of the spin operator. hut often not negligible). or (2. Conversely.7. Then. However. p method 189 Figure 2.25: Valence band dispersion for diamond type semiconductors in the vicinity of the I'i5-maximum for different k-directions. A set of basis functions for representation of the electron states in coordinatespin space may be formed lrom the Bloch functions (xlpk) or the Luttingw-Kohn functions (xlpkO) without spin.s(k) in these equations. for most of the diamond and zincblende type semiconductors. by definition. and on the spin-coordinate 3.7. Here u means the spin quantum number which can have the two values u (spin up) and cr =I (spin down). The electron states then depend on both the position coordinate x. We denote the product functions by (sxlpk) or (sx(pkO).respectively.3 Lut t inger-K ohn model Including of spin-orbit interaction To include spin-orbit interaction the electrons must be treated as particles with spin. there also is no longer any distinction between light and heavy holes. and the quantum numbers of the electron states contain provision for both the motion in coordinate and spin state u describing the spin motion. Thus the first two bands correspond to the heavy holes and the third band to the light holes of Si. 2.

329) (for ko = 0) by the operator Hk.352) with ii = p 1 + ---[a 4m c= (2. but not of fi + f l W . m x VV(X)]. (2. Electronic structure of ideal crystah The total Hamiltonian of the system is obtained by adding the spin-orbit interaction H to the Hamiltonian H in its absence. ) .351) In calcuhting the matrix of H t H.56) as (2. a.. ) . where Hgo is given by ..3501 One has to be aware that the (sxlvuk) are eigenfunctions of H .) .T h e matrix repre senlation of the Schrtdinger equation with respect to the spin-dependent Luttinger-Kahn basis reads + x(prkOtH pW + H.~ (2. Correspondingly. (2. The additional term can be taken into account by replacing the operator Ht.x = H o ( k ) Tl + -k . of (2..355) Up to this point. = P’U’ (2. the (xlvuko) signify the spin-dependent Luttinger-Kohn functions of H .p of equation (2. This term has the same form as the (A/rn)k. except that the p-operator is replaced by the operator p+(1/4rnc2)[5 x OV(x)]. ( p n k O l E .351)) an additional k-dependent term appears in comparison with the spin-less case.E .190 we have Chapter 2. but not of H H. Ip’v‘kO)(p’u’kOIE l . equation (2.~ + HsoIp‘u’O)(p’u‘kOIEu) E . (pu kO IE. ~. as a consequence of the fact that H ..353) becomes With this the Luttinger-Kohn representation of H (pukOlH + H.351)) takes the form C(~(TOIH~.354) and the Schrodinger equation (2. Now we wish t o explore the particular consequences of spin-orbit interaction for the previously . we have kept the discussion general. + H80/p’a’kO) = ( ~ u O I H+ Hso{p‘u‘O). p-term arising from H . contains the momentum operator.

358) 0 . / ~ = ( V Z O l PV(XjXp1ytvrO).the matrix (avmOlH. Ivy 7 0 ) = ly tj.7.e.a H .i . To this end.356) = ) O I 4m c To evaluate the matrix element (vmOl[OV(x) x p]]vm’Oj in coordinate space we make use of crystal symmetry. between the spin-dependent Bloch states of Ivm 0 . . The tenin sor (vmO ! [VV(x) x p] I vm’O) consequently contains one independent constant. I ~ ~ ’ U ’ O ~ ( v v ~ [VV(X)x p] Ium‘O) x (aldld).357) and the explicit form of the spin matrices given in (2.. . are therefore also those + . A 3 (2. k p method 191 considered valence band states.i i 0 0 0 1 0 0 0 0 0 . Spinz s orbit interaction couples orbital states and spin states to each other. 0 )namely. which the identity representation occurs exactly once. ~ F.Ivm.4 (vmaOp.357) Below.= rl..57). we set h 4m c . Because the Bloch factors are real? these elements are pure imaginary..1 i o i 0 0 (2.. We denote the value of (vyOl[VV(x) x p].. i. At k = 0 the expressions E:(k) and k ii are both zero. It)z 1 0 ) 3 1 1). The entire third-rank tensor (vrnOI[VV(x) x p]lvrn’O) therefore 1 belongs to the reducible representation I’b5 x Ti.jvzO) by (4m2c2/h)(i/3)A. . we will see that the constant A is the energy splitting of the valence band at J? due to spin-orbit interaction. The eigenenergies and eigenfunctions of the total Hamiltonian Hk. as was done before. x (r2 r 2 T’i5+I7L5). x P2. Applying equation (2. ( u ~ u O I H . This constant coincides with the matrix elements (vyOl[VV(x) x pIz I v z O j = (vzO I [VV(xj x plXI vyO) = (vzOI [VV(x) x p]ylvzO). in the calculation of the matrix elements of the momentum operator p. The operator [VV(x) x pi is a pseudovector and transforms according to the irreducible representation ri5of oh.2.lvzO) holds. ~ o ) where (vxOl[VV(x) x plz I u y O ) = -(uyO I [VV(x) x p]. we need the matrix elements (vrnuO~Hso~wm’u’O)H.’u’O) =- A 3 0 0 0 0 . (2.I a’w m ‘0j becomes 0 .Ol[V(X)XPl*l v y 0 ) = (WYOI [ w x ~ x P l . as well as + + (~.(uyO~[VV(x)x plrlvzO) = i . .i o 1 0 Here the rows end columns are associated with the basis functions in the sequence Ivz T O j = I t).1 i 0 0 0 0 0 .

J y I). 0 . alone.o. .d3 (2.1.361) have a simple meaning. w6 . 0. Jz O. i. . Acrording to Appendix A. Electsonic structure of ideal crystals of H. i.O).----(--I. The lEvl). = Eigenfunctions at r. The matrix (2.355) at k .. 1). 0 .lvm'a'O)(vm'a'O~E) E(wamO(E). O ) .363) The components of the eigenvectors given by (2. 1. 6 of (2.O.o. o). O . O.i . Iz i). . o.192 Chapter 2.IEv3). 12 I). using basis functions IvmaO).0 becomes (2.361) and a 2-fold degenerate eigerivslue Ev5/6 - --A 2 3 (2.360) with the four corresponding eigenstates. l I ) .2. IEv4) = -(O.i . If we abbreviate these by Ima) I T).i . so thsl the Schrfidinger equation (2.IEvz). 1.363) refer l o the IwmaO). (2. 2 ) . the cigcnvcctors take the form z y The eigenvectors lEvt). IEv4) are basis functions of the irreducible representation of the cubic group o h . . respectively.359) u'm' c (vmaO~H. fi 1 i E 0. Iz J). IE ) ~ v1 - 1 T ( 1 .361) to (2. IEv2) Jz - IEv3) = 1 i z(l.. these representations . Angular momcntum basis. 1 ) . o. 1.355) has a 4-fold degenerate eigenvalue Ev1/2/3/4 = 1 p (2. .3 62) with the two corresponding eigenstates IEv5) - -(o.i. .

. r ing to Appendix A .366) henceforth as the angular momentum basis. as Di x T = Y$ +I ' . respectively: from the states with positive momentum. .3621. The six valence hand states at transform in accordance with the &dimensional representation Dl x .and -$ L One therefore denotes the first four eigenfunctions of (2.IE. We refer to the functions Ijmj) of (2. k p -method 193 emerge from the representation 213 of the full rotation group if. According to (2. eigenstates having the same eiggmvalue of the the angular momentum squared.365) I--)2 2 3T = -[& I.360) and (2.365) and (2. The lEvs). and of the z-component J z of J for the eigenvalues m j = 3 2. These representations do not arise from any representation V3 of the full orthogonal group. . i.). =. Therefore one also uses the angular momentum notation €or the last two eigenfunctiona of (2. The valence band: being B-fold degenerate at the r-point if spin is not taken into account. in particular not from a representation for J = (this happens with in the case of Oh or r:) in the case of T d . 2 . D Dis taken ~ as a representation of the subgroup o with +1 for inversion. 1 by means of time reversal. ' I 3.e. 4. The size of the splitting is given .364) by + 4. but the expectation values of J2 and J z are the same as those in the Dl basis. J2.iy T) +2/2 111%I--) Jz -iY I).2. 22 (2. i e .s) are basis functions of the irreducible representation I'y of o h . accord.-o)rhitqditting must occiir? one can recognize just by means of a grnnp theoretical analysis of the problem.1 . by forming the comphx conjugate of the original eigenvector and subsequently multiplying it by rP. one with j : and one with j = if the spin-orbit interaction is considcrccl. ?. which is chosen heie such that the states with negative total angular I): $I. Tlicse representations are reducible. I--)2 4 2 1 = -"-2Iz i fi t) + la: + iY 1 1 1 7 33 i = 1. I--)2 2 33 = -1rz 31 + iy t).7.ynin.): 1 follow.also have the same energy eigenvalue.366) is determined only up to a phase factor. It has also been h shown that the basis functions of this representation are the simultaneous 5 eigenfunctions of the angular-momentum-squared ' €or the eigenvalue j ( J 1) (in units R 2 ). therefore splits into two bands.366 and (2. 1 . I$$). while the rncrgy eigenvalues differ if states with different eigcnvalues of J' are consitirrrd. total angular mornenturn. 1 . . That such a . of Oh.I ) . one sets rt 4 Each of the dgenvectors (2.3641.

In analogy to equation (2. Therefore A is called spin-orbit splitting energy. Electronic structure of ideal crystaJs by the constant A. It will be omitted below.339). but not to states from other bands.355) in this representation reads The spin-dependent term of k . .e.194 Chapter 2. We have seen how this can be done approximately in the preceding section. also only couples the valence band states among themselves. One may interpret A as the difference of the spin-orbit interaction energy between the states with 3 j = 3 and those with j = As one should expect. i.339).367) d e scribes the change of the k .. without consideration of spin.p-interaction due to spin-orbit interaction.7i in the eigenstates Ivmcrk)' of (2. Since H. where we use the same abbreviations as in (2. Then we have. one finds for the valence band states Ivmcrk)' the expression r. Off this interaction is no longer zero and must be taken into account in addition to the spin-orbit interaction. i. where the k p-interaction vanishes. Valence band structure off r The above statements refer to valence band states at the center r of the first B Z . with different projections Jz of total angular momentum on the z-axis. '5'ince t. States with different m j . The submatrix with respect to the valence band states (vmmk)' is decoupled from the remainder of the matrix in second order perturbation theory. the Schrdinger equation (2. The functions Ipgk)' form a complete orthonormal set in t a m s of which the Hamiltonian H may be represented.he two interactious are supposed to be weak.352) i first n order perturbation theory. approximately. Analogous relations hold for the states of the other bands.have the same spinorbit interaction energies. which determines the strength of the spin-orbit interaction. but the same J2. the states with larger angular momentum l e energetically above the states with smalIer angular i momentum. this change i s second order small. Therefore the degeneracy of these states remains. The method used there indicates the following procedure in the presence of spin and spin-orbit interaction: One determines the functions Ipok)' which diagonalhe the operator H k q of (2.

qolvm’a’O). k p -nrt.th<>d 9 195 (vmakIH.372) 0 .(vm’a’O) takes the diagonal form (hjlff.355).365) and (2. One has (2.371) If one applies this transformation to the Schrodinger equation (2.370) can be readily The corresponding unitary transformation matrix UmjmJ obtained from the rclations (2.366).365) and (2. is diagonal in the angular momentum basis Ijmj) of (2.lv7n’a’k)’ (vmaOlH.. then the matrix (vmaOlH. Now we use the fact that H.7. It is clear that this basis follows from Ivma0) E Imu) by a unitary transformation ~ j m j ) C U r r m j m j Ima).olj’m.2.) = o $ o o o o + o o o o g 0 0 0 0 - 0 0 0 9 0 0 0 ’ (2... ma (2.366).

196 Chapter 2.I~ ~ u. The difference in form is. The magnitude of the latter can be estimated as the larger of the two terms Nlki2 or IL .I~ c e)::I . These matrices arp given in Appendix A.AIl}lk12 << A holds. . above all. Among them.and one (2 x 2)-block for the basis vectors of the representation The rsf-matrix reads I't.ILM1}]21k14/A. ~ ~. one needs the angular momentum matricrs for spin J = as well aa their products with earh other. S. Under the assumptions made. that the new matrix is already diagonal at k = 0.)::I thc 1 multiplying A/3 is thc (4 x 4) unity matrix. Here. then a perturbation theoretical treatment IL is possible. It has the same eigenvalues as the original matrix. To do this. That means that the 3-off-diagonal elements of the transformed Hamiltonian matrix can be neglected if the k-vectors are sufficiently close to r. even though its form deviates from that of the original. It yields an energy correction of order of magnitude [ M a r { N . . Neglecting ]-offdiagonal elements the Hamltonian decomposes into two blocks. one (4 x 4) -block conesponding to the basis vectors of the representation I'i. .T stand for the fobwing expressions. The 4. although the Luttinger-Kohn model also covers the general case of a (6 x 6 ) -Hamiltonian matrix.): ]. R The Hamiltonian matrix of thr rz-valence band can also be derivcd using the method of iiivarinnts. Electronic structure o ideal crystds f The sum of the two matrices (2. the elements between basis vectors ] j m 3 ) [ j ' r n $ ) with m3 # m i . and the quantities & ? . but = 3' play a different role than the ones with .373) is the new Hamiltonian matrix. 9 . While the influence of the 2-diagonal elements on the eigenvalues is independent of the size of the spin-orbit splitting A. which was discuss& at an earlier stagc. We will assume below that this is the case. Kon-diagonal elements and occur for k # 0. therows a n d c o l u r r ~ u a r e o r d e r e d i n t . . If one assumes that l L f a ~ ( ~ V .f j'. this is small compared to A. it does depend on it for the j off-diagonal elements.372) and (2.Mllkl'.

a similar %fold degencratc band Ep.7. The 2-fold degeneracy of ixll band6 is a consequence of time reversal symmetry jointly with spatial inversion symmetry (see Appendix A). 3 (2. . 2 Using the explicit expressions for Q. 1 3T . Correspondingly. 7 3 called Luttznger parameters.2. the heavy and light hole states are linear combinations of all four basis functions ) :. .C. The matrix (2. C 2 3 7 1 -[N2 . . = 0. this also does not play an important role. R .374) has the two 2-fold degenerate eigenvalues E&(k).). = k-. The E&-band has weaker curvature. eigenfunctions are I$$) and. 7 2 . Instead of the latter.) 'l'hc EFa-band is that of the Zzght holes. this yields (2. 122) and. two 2-fold degenerate bands Erf. B = 1 . of (2.( L . This means that the neglect of the coupling terms between the spin-orbit and k p-interactions has no influence on the general form of the r$-Hamiltonian matrix. B.which lies at an energy separation A below.362).360) is 4fold degenin erate at I?.) The described structure of the valence band around r represents what is called the Lallznger-Kohn modal.26) evolves off of r.M)')]. : 1 The eigenfunctions for k. the pertinent . M . Only the Z : explicit expressions for the constants L . Since these arc understood as empirical parameters.374).1 For arbitrary kdirections.Ad). . The particular form of the bands is determined by the three consttlnts A . k . Even with this additional approximation one obtains the most general I'8+-Hamiltonian compatible with the symmetry of the crystal. For k-. .( L .378) : Thc 'T (2 x 2)-matrix block of the full (6 x 6)-matrix is already diagonal.(k) (see Figure 2. 1 and .0 read) .(k) arise off of I?. T. . S.k. it corresponds to the band of heavy holas. Its 2-fold degenerate eigenvalue Er7(k) is given by The energy level Eo1/2/3/4 Bra(0) equation (2. one can use the dimensionless parameters 7 1 . I I) :. p +method 197 resulting Bamiltonian matrix agrees exactly with that of equation (2.343) are affected.376) A = -(L 3 1 + 2M). and starting from the 2-fold ckgenerdte level Ew5/6 = Ey7(0) r in at (2. defined by : - . N in the matrix D. .

377) not with respect to the components of k. This would not have resulted if the interaction between the rBf-states.e. the point k = 0 is a singularity of the energy band functions Erf. Electronic structure of ideal crystals I I I s. The effective mass tensor. N . In their case one again has a warping of energy bands as discussed above (see Figure 2. The constants L .12. the spin-orbit-split band Er7(k) is isotropic. is not defined in such circumstances.2~. by averaging . II [loo] G+l 5. Instead.but with respect to Ikl. For C # 0. ha Lni h2 C2 = ---12(7.26: Valence band structure of diamond and zincblende type semiconductors in the Luttinger-Kohn model.2 2m .196). as given by equation (2. If the warping of energy bands is ignored. In the case C = 0. one can define an anisotropic effective mass. The constant C measures the strength of warping. they are parabolic. and the spin-orbit-split r.(k) in that the second derivatives with respect to the components of k depend on the direction from which one approaches the point k = 0. B 2m = -.26). M . i. by differentiating in equation (2. had not been neglected as it in fact was. while the heavy and light f hole bands Er8(k) are not..198 Chapter 2.(k) depend on the square of Ikl.f states. II [ l] Il Figure 2. A h2 -----TI. which were originally used. may be expressed in terms of the Luttinger parameters by the relations: Both energy band functions E&(k) and Er. for instance. (23 8 0 ) Values of the Luttinger parameters are listed in Table 2. the warping vanishes. Concerning the dependencies on the direction of k. The dispersion for the two k-directions is different (band warping).7:).

08 over all directions.30 0.2 6. E i . The most important requirement for the Luttinger-Kohn model to be valid is .42 1. The reason for this is the absence of inversion symmetry in the zincblende structure. as a rule.4 A 0 0. The values for 71.S n 0.12 therefore also contains Luttinger-Kohn parameters for semiconductors of the zincblende type.344)).69 16. provided the other requirements which underlie this model are satisfied.8 35.23 0.52 26.7. IvrnO).38 4.3 Ei 5. The non-vanishing matrix elements (omOlplvrn'0) give rise to terms linear with respect t o k in the I1 valence band Hamiltonian. k. where the unity representation does not occur in the corresponding I x r15 x ' i . 1982. ready present in the diamond case (see equation (2.2 2.94 4.7 22. Formally.p-band parameters for selected diamond and zincblende type serniconductors.56 5.67 10. for materials having the zincblende structure.8 25.70 0. (After Landoldt-Bomstein.8 Ep 0.3 39 GaAs 2. The Luttinger-Kohn model was described above for the case of diamond type semiconductors.) Material 71 yz 73 C Si Ge cz .4 21. besides the quadratic terms which are are al'5 However. and E .08 4.90 -0.98 0.53 8.03 15.29 0. product. in eV.8 0. 7 3 are adjusted to the Luttinger-Kohn model.4 1.1 0. Temperature below 70 K . as distinguished from diamond type semiconductors.2.35 19.64 0. E p = ( 2 m / h 2 ) P 2s a measure of constant P in i Kane's band model.34 0.044 0. the k-linear terms are small. this yields the ordinary isotropic heavy and light hole masses but in the sense of an average. and the Luttinger-Kohn model also applies to zincblende type materials. are in general non-zero: These states transform according to the vector representation r15 of the tetrahedral group T d r and the matrix '5 '5 1.8 12.91 1.23 1.2 17.85 11.12: k .6 0. the model does not apply because the matrix elements of the momentum operator p between the triply degenerate valence band states without spin.5 GaSb InSb ZnSe HgTe 4. A.18 2.p -method 199 Table 2.25 13.26 13.9 5.67 -0. yz.26 16.8 0.48 3. elements (vrnOlplvm'0) belong to the product representation I1 x I1 x r 5 The latter contains the unity representation. Table 2.

Simultaneously.p-inleiaction among the three r15-valence bands which. T addition. giving risr to k-linmr terms in the Hamiltonian. the spin-orbit splitting energy A becomes i relatively large in some of the zincblende type materials. which we will now discuss.200 Chapter 2. does not rigorously vanish for zincblenrle type crystals. those of zinrldende type EM well as those of diamond type. at r the spiuless valcnce band should have the symmetry T 5 and 1. 2. we will simplify further and neglwt this interaction COHIn plelely. it is assumed that the k. even becomes negative. P’zrstly.4 Kane model The Kane model is based on the following assumptions. p-interaction of the valence band with the deqest conduction band at 1’ is so strong that it must bc treated exactly. Ef. while taking iuto account only the energetically closer conduction band by means of perturbation theory. the spinlesu conduction band should have the symmetry rl. Describing of l h e valence band of such semiconductors by means o l the Luttingrr-Kohn model would entail treating the effect of the remote spin-orbit-split band exactly. clearly lies below those for C. should thc need arise. In the latter case. In this matler. This involves a spwialization of the results. more appropriate description. It turns out that the latter approximation is valid in most cases. for example. so that even A > / $ holds. we will also neglect the direct k . This assumption corresponds to the situation which actually exists in semiconductors of Llncblendc type. so that it rriay be treated by perturbation theory. Such a procedure is not meaningful and one must seek a different. which may be casily done. and no longer the cubic group o h as above. thercby encompessing both typeb of semiconduclois. Si and Ge. A model which is tailored exactly to such circumstances is the Kana model. inversion symmetry still has to be added. the interaction of the valence and conduction bands with all remaining bands (referrcd to as ~ e m o t is ) ~ assumed to be srrrall. Secondly. In the case of a-Sn and HgTe. Thirdly. This is justified as long as the encrgy separation EF from the lowest condiiclion band and the I&-valenre band (not to be confused with the fimdamental cnergy gap) is siifficiently large. Here. we asbume that the point group of equivalent directions is the tetrahedral group ‘rh. One expects deviations from the Luttinger-Kohn model to become noticeable if E i is sinall Table 2. similar l o the Lultinger-Kohn model in which the interaction of the valence band with all other bands was treated in this way.12 shows thal the EF-value for InSb. . Electrunic structrrre of ideal crystals the validity of the assumption that the k p-interaction of the valence band with thc deepest conduction band is weak enough to be treated by means of perturbation theory.7. as mentioned above.

z. (2. k.)-k 2m (wmOlHo(k)IcsO)= 0. ri2 2m 2 (2. above. The conduction band index c will be augmented by 3 . The pertinent spin-dependent Bloch functions at k . idirating the 3. As such. the matrix does not haw to vanish. it contains exactly one independed rlcnwnt. rmpectively.0 are IvmuO) and I c s v O ) . one may chose ( c s O l p . ni . .WP may neglect thc spin-dqwndcnt part by virtue of the same arguments as in the Luttingerkohn model. l v d ) and set it equal t o z ( m / h ) P . ~ .384) Iii the otkw o p ~ a t o r term of A V ~ . We again denote the thrw valence band indices by urn. and the reader should keep the dxerent meaning of s dearly in mirid to avoid confusion). considering spin md spinorbit interaction horn the outset. but unavoidable. namely {Fa/m)k-.383) h2 (csdlHo(k)lcsdO) = 6. The three needed matrix elements of this operatw may then be determined as (2.382) (2. Since the unity representation is contained in it = Fl + exactly once.I..p -methad 201 Neglect of interaction with remote bands We analyzr the generally valid Ychrbdinger equation (2.385) The matrix elements (vmOtplzlm'0) of p between the valence band states are wglectctcd in accordance with the assumptions madr above.?i. The matrix elements {cs01plvmO) between valence and conduction band states tranuform according to the produrt representation r x I115 x r15 1 trls i l725.2.or rl-synlm&-y of the conduction band state at (the coincidence of this notation s with that of the s p h variable 9 is unfortunate. The matrix elements of the term Ho(k] of f f k X are given by r (vmaO)Ho(k)jvm'dO)= bmm~6umi-k2 . The nun-vanishing matrix elements of p are then given by the relation .351) using the assumptions and approximations discussed.7.u. The diagonal rlemenl (csOlplcs0) of p in the conduction band state IcsO) vanishes exactly.

1). thp Hamiltonian matrix (pu01Hk . because l’i5 coincides with I’15 for the tetrahedral group. 0 0 where thr lines and columns arp ordprcd in the sequence I2 I). 12 1). -iPkg -iPk.F. whence + (um. Finally ihe matrix demerits (puO1Hsolp‘m‘O) nl t h e spiri-orbit interaction operator ITrn haw to lie detrrminpd. -iPk.386) The factor 2 giiarantws that P i s real.)~ = ~ (v ) ~ -o m (2. The unity representation does not oc cur here. l rztj . iYk. IY 11. (2.202 Chapter 2.. Ig I).lwm’a’O). The other factor (m/Ta)was introduced for convenience in the final dispersion rclations.I’z+ I’15 r25. For the Flj-vaknrc band rlernents (wmcrOlH. Electronic strr1c:ture of ideal crystals ~ c s o ~ p .lrsa’O) and (csuQIH.olcsdO) belongs to the product representation rlx r 2 5 x r : arid must therefore likewise wnish. 0 0 0 0 0 I ] /s 0 0 0 0 0 0 -iPk. . a th I. one can adopt the results which were formerly derived for the valence band. lz 1). if the Bloch factors are real as we assume.oj cscr‘0) involving the conduction band states. l I). .3861.iPk.I csa‘O). 0 0 0 0 0 E C 0 0 0 0 0 0 -iPk. 0 0 0 0 iPk. There are new matrix elPrnents (vmuOlH. 0 0 0 iPk.aOlHs”Icsrr’0)= 0. 0 0 0 0 0 0 0 0 0 0 0 iPk. ~ ~= ti . With the moinentiim matrix elements of (2.(k)lp’u’O) takes the form (2.387) Ec --iPk..388) The caordinatedeyendrnt factor of (csuOlH. ~ 7~~r r8o~~~ p v = I c syo~/ p . The coordinatedependent factor of the first matrix element transforms according to the representation r15 x l?25 x I’l . thus this factor vanishes and with it the whole matrix element (umaOIH.

however.A i$ 0 0 o 0 0 o 0 0 -A 3 0 -- -27 $ i+ iPk.7. the order of rows and columns is the same as in (2.A -+ i+ o 0 0 0 0 0 . o iPk.391) . that one can also obtain the secular equation directly. The eigenfunctions at k . T h {2 x 2)-co. We will do t h s .. -iPkY -iPk. -iPkg -iPk.. The (6 x G)-vdencr band block is identical with the matrix of the spin-orbit interaction operator H. Ec -iPk.490) at k # 0. 0 -2z O . is gken by the following matrix . iPk.A 0 Here. The eigenfunctioiis of the two blocks arc simultaneously also e i g e h c t i o n s of the total matrix. p -method 203 Thus.350) for the Luttinger-Kohn model.T representation + H. k .and B (6 x 6)-block for the valence band. To diminate the free elmtron part ( h 2 / 2 m ) k 2from the eigenvalues Elk). 0 0 0 \ iPkz 0 0 a 3 0 0 2 5 --iPk.366). i.2. 0 0 0 0 Ec 0 0 0 O 0 0 ? 0 -ig A 0 . For k = 0 and vanishing Ec. before we h r t h w consider the angular momentum basis.387). we write them in the form T 1) of ihe ctngpubr momentum basis (2.390) at k .390) is.c. 1s t) and 1s J] are eigenhnctions of the Hamiltonian matrix (2. the total Hamiltonian Hk. indeed. this matrix reduces to the spin-orbit interaction opcrator WSw If one rearranges the rows and columns of this matrix in such a way that those relating to the conduction band states 1s 1) and 1s J) occur in the left upper corner.nduction band block is already diagonal. side by side. of (2. then the matrix decomposes into a (2 x 2)block for the conduction bt~ncl.0. E(k) : E’(k) -I--k2 where E’(k) satisfies the following h2 2m (2. The matrix (2.0 here are therefore also the vectors 1$ms) and i$rn The latter basis should be particularly suitable for solution of the eigenvalue problem for the Hamiltonian matrix (2. iPk. so simple. iPk.

204

Secular equation

Chapter 2. Electronic structure of ideal crystals

(2.392)

The fact that the two factors in round brackets appear squared, signifies an at least 2-fold degeneracy of all eigenvalues. The reason for this is. again, time reversal symmetry jointly with spatial inversion symmetry (we remind the reader that the term of the Hamiltonian which can break inversion symmetry in the case of Td-symmetry has been neglected). Accordingly, one has in general four 2-fold degenerate bands Ei(k).Ei(k),E$(k),Ei(k). It is also noteworthy that in the secular equation (2.392). k enters only in the form of k2. This means that all four bands are isotropic, in contrast to the LuttingerKohn model where a warping of the valence bands occurs. In the case of k = 0, the energy levels of (2.392) are given by

One may draw conclusions from these expressions in regard to the meaning of the four energy bands E,(k): El(k) is the J?s-conduction band. E z ( k ) 2nd Es(k) are the two upper degenerate rs-valence bands at r. and E4(k) corresponds to the spin-orbit-split rT-valence band. The energy separation E of the r6-conduction band and the I'g-valence bend at. r is obtained as L

(2.394)

As long as E: is positive, it represents the energy gap E , at I?. The case of negative E' is discussed below. For one of the two upper valence bands - the , one which arises from the vanishing of the first factor of the secular equation (2.392) and which is denoted by i = 2 - the energy El(k) does not depend on k. For E$(k).a k-dependence follows with finite negative curvature, as we will soon see. Thus E;(k) corresponds to a band of (infinitely) heavy holes, and Ei(k) to a band of light holes. If one adds the (Ti2/2m)k2-term, then the band Ez(k) displays a positive curvature. It is relatively small because of the large free electron mass, but the positive sign contradicts what is to be expected for a valence band. This unexpected prediction for E z ( k ) results from the fact that the interaction of the valence band with all remaining bands, except with the deepest conduction band, was completely neglected. In order to treat the heavy hole band correctly, the interaction with remote bands must also be considered at least by perturbation theory as in the Luttinger-Kohn model. This will be done below.

205

Interaction with remote bands

According to the assumptions made at the outset. the interaction with r e mote bands is weak and may be taken into account by means of second order k. p perturbation theory. The 8 x 8 Hamiltonian matrix of cquatiori (2,390) for the conriuclion-valence band complex contains two 4 x 4 blocks of definite spin with rows and columns referring to the conduction band s state and the three 2--, y--, z-valence band statrs without spin, respectively. To include the inteTactjori with remote bands. RII additional 4 x 4 matrix o€ second order in k has to be added to each of these 4 x 4 blocks. Since the interaction bctween conduct ion and valrncc b a l d states contributes alrpady in first order, second order corrections occurring at $2--,sy-, s z - , and zs--, ys-, zs-positions may be omitted. For the ss-element and the 3 x 3 valence band submatrix, second order corrections beconie import ant. Their genpral forms follow from symmetry arguments as above. The correction of the ss-element may be written in the form Ack2, with A , a constant. The perturbation correction to the 3 x 3 valence band submatrix has the general form of the 3 x 3 matrix in qiiation (2.344) with parameters L , M. N &fin-1 like the matrix elements D E , D g in equation (2.341), however, with the conduction band excluded from the summation over { t bewuse this band is not reinotc. The 4 x 4 matrix block thus determined is added to carti of the two 4 x 4 diagonal blocks already present in the 8 x 8 matrix (2.390). Finally, the whole 8 x 8 matrix is subjected to a unitary transformation into a basis set in which the spin-orbit interaction part of the Hamiltonian becomes diagonal. The latter requirement is evidently satisfied by a basis which, as in the Luttinger-Kohn model. contains the 6 angular momentum eigenfunctions I$:), I$$), I:!),;I ,): I%+). I;$), and in addition the two conduction band states 1s 1) and 1s 1). This corresponds to a 8 x 8 unitary transformation matrix composed of a 2 x 2 unity matrix block for the two conduction band states, and the 6 x 6 matrix block from equation (2.371) for the six valence band states. Carrying out the unitary transformation one obtains the general 8 x 8 Kane Hamiltonian which applies to any diamond or zincblende type materials, including those which are already well described by the Luttinger-Kohn model. However, even in these cases the Kane model is more precise than the Luttinger-Kohn model, because the valence-conduction band interaction is treated exactly rather than approximately like in the Luttinger-Kohn model. If one uses the Kane model in cases in which the Luttinger-Kohn model already works well. one has to be aware that generally the parameters 71, 7 2 , 73 have different Values in the two models since those of the Luttinger-Kohn model contain the valenceconduction band interaction while those of the Kane model do not so. The general 8 x 8 Kane Hamiltonian is given by rather lengthy expres-

206

Chapter 2. EIwtronic structure of ideal crystals

sions. To avoid these below, the 4 x 4 block matrix of the remote band interaction will be reduced to a special case before proceeding further. We put L = M -- A,, and N = 0, which means physically that the remote bands affect heavy and light holes in the same way, and do not disturb the isotropy of the bands. -Ordering rows and columns in the sequence 1s t), 1s l),I);:, I;$), . . . , I$$), the transformed 8 x 8 Hamiltonian matrix with simplified remote band interaction becomes

U

0

0 U

0

aP,

D

-&

0

0

0

-iP-

V

0

0

0

0 0

O

-fiP-i&

0 0

V

0

D

0

0

-i$&P,

v

0 0

0

0 0

W 0

0

U '

(2.3

where the notations l'h = (1/&)P(kz f ik,), Pz = Pk,, U = Ec A&', V = (1/3)A A,k2, and W = -(2/3)A A,k2 are used. The eigenvalues of this matrix follow from the secular equation

+

+

+

E'(k) + -A i 3

2

- A,k2

I-i

E'(k) +

3

This equation only differs from equation (2.392) in that the factors whose vanishing define the conduction and valence bands contain, respectively, the additional terms A,k2 and A,k2.

Solution of the secular equation in limiting cases

The zeros of the h s t factor in (2.396) yield, as seen previously, the I's-band of heavy holes (i = 2). However, the dispersion relation for it now reads

En(k) = -

A 3

ii2 + A , k 2+ -k2 2m

(2.397)

2.7.

k.p -metbod

207

By choosing a negative value for of appropriate magnitude A,, the dispersion for heavy holes can be brought into agreement with experimental findings. The zeros of the second factor in (2.396) determine the dispersion of the Fa-conduction band ( i = l ) ,the rs-band of light holes (i = 3), and the spin-orbit-split I'T-band (i = 4). For the conduction band, the dispersion is changed due to the A,k2-term, and for the two valence bands due to the A,k2-term. But, here, these corrections are added to already existing strong dispersion terms. We will therefore neglect them in the following, as we neglected the weak dispersion duc to the free electron term (li2/2m)k2 earlier. Then the eigenvahe equation for the three bands i = I, 3,4reads

- [E'i(k)

+

$1

P2k2 = 0.

(2.398)

This equation will be solved approximately in three limiting cases with r e sped to the order of magnitude relations between the energy gap E i and spin-orbit splittiiig energy A, as w ~ l l with respect to the s i g n of E,'. as namely firstly for EF >> A, Eg > 0, secondly for EF -CK A, E; > 0, and thirdly for IEiI < A, E i < 0. The significance of a negative value of E i will be discussed while treating the third case. All three cases actually occur in zincblende type semiconductors, as a look at Table 2.12 immediately

shows. The first case corresponds to materials with wide energy gaps whose valence band complex could be described just as well by means of the LuttingerKohn model; the second case refers to semiconductors with narrow energy gaps; and the third to materials whose energy gaps vanish.

Case 1: E: z E , >> A,

EF

>o

We consider energy values Ei(k)in the various bands with energy separations IEi(k) - &(O)( from the respective band exbrema which are small compared with EF. For such energies, the conduction band El(k) approximately obeys the equation

[El(k)- E,]E, - P 2 k 2= 0.

and for the two valence bands E3(k) and E4(k) we have

(2.399)

bi(k) -

$1

bi(k)

+ TA

21

E,

+ [&(k) + -

I:

P2k2 = 0, i = 3 , 4 . (2.400)

From (2.399) it follows immediately that

208

Chapter 2. Electronic structure of ideal crystals

**(2.401) and from (2.400) we obtain
**

2

1 A E3/4(k) = -- [ 2 3

+

P2 -k E,

2]*ij[?f-Kk2]+m'

A

P2

8

(2.402)

Under the condition (P2/Eg)k2<< A, a parabolic approximation for the otherwise non-parabolic valence band E3/4(k) is possible, namely

E3/4(k) =

- (2/3)A

-(2 13)(P2/ k2 E,)

- (1/3)(P2/E, ) k2.

(2.403)

The structure of the four bands E1/2/3/4(k) is illustrated in Figure 2.27a. Case 2: Ef

= E, << A, Ef

>0

The energy values Ei(k) now have energy separations IEi(k) - Ei(O)I from the respective band extrema which are small compared to A. This means they can be comparable to E i . For the conduction band and the light hole band one then gets from (2.398), approximately,

= 0, i = 1,3,

(2.404)

from which

follows. In general, the dispersion laws for the electrons and light holes are again non-parabolic. Only for energy separations from the band extrema which are small compared to E,, more exactly for P2k2 << (8/3)E,, a k2dependence emerges, namely

\i

2.7. k . p -method

209

b)

7 A

r,

2 4

3

I

4

I

4

Figure 2.27: Valence band structure of zincblende type semiconductorsin the Kane model for limiting cases: (a) E, >> A, ( b ) E g<< A, E: > 0, ( c ) E , << A, E; < 0. Since the energy region of width Eg above the band extrema is relatively narrow for the narrow gap semiconductors considered here, one has in these materials, even at relatively small separations from the band edges, nonparabolicities in the dispersion laws of the electrons and light holes. As far as these particles are concerned, small energy gaps and non-parabolicities occur together. For the spin-orbit-split band, one obtains, without further approximat ions,

2 E4(k)= --A

3

- -k

PZ2 . 3A

(2.407)

The dispersion curves of all four bands in the limiting case considered here are depicted in Figure 2.27b. Case 3: IEil << A, E i < 0 According to equation (2.394), negative values of EF mean that the r 6

2 10

Chapter 2. Electronic structure of ideal crystals

conduction band level lies below the rglevel. The relation lEil << A guarantees that the spin-orbit-split r;.-level is found further below it (see Figure 2 . 2 7 ~ ) .If. again, only energy values are considered with separations IE,(k)- E,(O)I from the respective band extrema which are small compared to A, one obtains dispersion relations having the same form as in the previously considered case EF << A , E , > 0 (see equation (2.406). For electrons and light holes they yield. under the condition (P2/A)k2 << IEil, the approximate parabolic dispersion laws

Because of the negative sign of E:, band 1 now lies energetically lower and exhibits a negative effective mass, and band 3 lies higher and has a positive effective mass. For the spin-orbit-split band E4(k), equation (2.407) holds unchanged, and for the band E i ( k ) of the heavy holes, relation (2.397) also remains the same. Thus, the band E 3 ( k ) is, among all four bands, the highest ' , energetically with the exception of I where it degenerates with the band of the heavy holes. Since the 8 valence electrons of a zincblende type semiconductor are only enough to occupy 6 of the 8 bands of the I?;.--. FS-. ??&band complex - 2 electrons per unit cell are necessary to fill the deepest I's -valence band, omitted from consideration here - the E3[k) band remains empty. It becomes the conduction band, which is also in accord with its positive effective mass. At r, its separation from the uppermost valence band, the Ez(k) band of heavy holes, is zero. This means that the energy gap vanishes in this case. Negative d u e s of the parameter E i . which signifies the energy gap when it is positive, cause EF to lose this significance, and the real energy gap becomes zero. Materials with vanishing energy gap are called zero-gap semtconductors. Examples are HgTe as a zincblende type semiconductor, and D - SR as a semiconductor of the diamond type. In Table 2.13. the effective masses m t are listed for the three limiting cases considered above. Generally, one has 1m.I I 5 I rn31 < IrnZl. The effective masses of the electrons and light holes are proportional t o / E g l / P 2 throughout. The rule discussed above for degenerate bands is thereby confirmed to be valid also for non-degenerate bands wherein mass decreases as lEgl decreases and P increases. For IE,l << A the effective masses of the electrons and light holes are almost identical, for E, >> A the electrons are lighter than the light holes. For the spin-orbit-split band, the proportionality of the effective masses to IE,l/P2 exists only in the case E, >> A; for < A the mass mS becomes independent of Es and proportional to A. <

2.8. Rand structure of important seniiconductors

211

Band

EF>>A,E;>O

EL<A,h',r>O

EL

<< A, EF < 0

'

rdl)

rs(3)

1.(F,/P2)

-(3/2) . ( E g / P ' ) -3

'

(3/2). (E,/P2) -(3/2) . ( E S / f " )

-3

'

-(3/2)

(I

8; I / P 2 )

(3/2) . (I -Ei I / p 2 ) -3

'

rd4)

2.8

(E,/P2)

(A/Fs,)

(A/ I

q I)

Band structure of important semiconductors

In this section we discuss the band structures of some important semiconductors. In all cases, the results presented are based on both theoretical and experiment a1 investigations. Experimental data concerning band struct ure of semiconductors arc mainly obtained by means of optical reflectance spectroscopy. It turns out that characteristic structures of the reflectance spectra, like peaks or shoulders, are directly related to optical transitions at critical points of the energy difference between the initial and final bands involved. The frequencies of these structures are experimental measures of the energy separations between initial and final bands at critical points, To enhance the charactelistic spectral features, changes of the reflectance spectra are measured due to external perturbations, as, for example mechanical strain, clmtiic and magnetic fields, light, or heat. By modulating the perturbations periodically in time with frequencies in the kHz range, these spectral changes can be measured very precisely by means of frequency and phase scnsitive techniques. Exttniple5 of this socalled modulataon spectroscopy are electrorepectance (ER), pzezorejlectanw, thermarejlectance, and photoreflectance (PR) (for morc on elect roreflwtance see section 3.7). Details of the band structure at critical points, like effective masses of free carriers, may also be extracted from transport meaxmemenits. Again, external perturbations, in particular, magnetic fields, are applied to induce changes. Magnetotransport phenomena, like rnngnetoreuzutanc.r and Shubnzkov-dp-Haas effect are examples. In cyclotron rmonance one measures the absorption of microwave radiation by a semiconductor sample in the presence of a magnetic field to obtain the effective masses of electrons and holes (section 3.8). None of the experimental methods is capable of revealing the entire band strurture of a given semiconductor material at all poiutv of the first BZ. To

212

Chapter 2. Electronic structure of ideal crystds

obtain this. one is nhliged to carry out band structure calculations. Expaimeutal data enter thrse calculatiolis in various ways. Tlus is obvious if empirical methods are cmployed their results have to be fitted to experimental data, as, for example, to energy separations between bands at critical points obtained from modulation spectroscopy. Less obvious. but nevertheless existing, is the need o experimental data for ab-initio calculations. Although f these methods are free of fitting parameters, various approximations are involved which call for experimental confirmation or even corrections of the results. as, for example, in the case of the erroneous fundamental energy gap in the local density approximation. Below we represent the results of of uumprical hand structure calculations using one or mother of the methods described in section 2.5. We will not specify which particular method was applied since that is not of interest here. Our main concern is with the qualitative features of the energy bands. We will demonstratp that thew may be understood. at least partially, just by means of the general results derived in the preceding sections and in Appendix A. This is particularly true for features irivolving the degree of band degrnrracy at symmetry points of the first B Z , which follow from the i r r e dudble representations of the space group of the crystal under consideration (see Appendix A). The band structure models derived by the empty lattice approach. the k . p method, and the tight binding method in sections 2.4, 2.6 and 2.7, respectively. will also be helpful. We begin our discussion with silicon.

2.8J

Silicon

In Figure 2.28 the band structure of Si is shown. Spin-orbit interaction plays only a minor role for the ovcwJl behavior of energy bands in Si, 80 the energy levels may be classified by means of the ordinary irreducible representations of the small point groups of the wavevectors k. l'hesr are subgroups of the full point group 01, eqiiivalent dirrctions. According t o what we already of know about the dimensions of these representations at the various symmetry points of the first B Z (see Table 2.5 and Appendix A), one expcrts at most %fold degenerate levels at the symmetry center I only 2-fold a t the the ' , symmetry point X. and at most 2-fold on thp symmetry lines A, A and at L. This expectation is codinned by the band structure shown in Figure 2.28. The deepest energy level of the entire band structure occurs at r, i s non-degenerate. and belongs to the irreducible representation r' . The same 1 result was previously obtained in the band structure analysis of diamond type crystals by means of t h e empty lattice altd tight binding approaches in earlipr swtions (see, Figwrs 2.13 and 2.2L rcspectively). Also, off of l?, the numerical calculation of the PI-band of Figure 2.28 exhibits the behavior prdictfd by these simple approaches. DiEmmrw between the numerical

2.8. Band structure o important semiconductors f

2 13

**Figure 2.28: Rmid structure of Si. The energy unit i eV. (After Chelikowskp and
**

Cohen, 1974.j

and empty-lattice band structures occur at the second level at as may be seen from Figure 2.29. The second empty lattice has an 8-fold degeneracy In a real which exceeds what is compatible with the Oh-symmetry of

r

r.

diamond type crystal this degeneracy is removed. As indicated in Figure 2.29, a splitting into levels of rl-,I'b-, I'b5-, and r l 5 - s y m e t r y will occur. In this way the corresponding rk5-, rls-, and I'k-levels in Figure 2.28 could have emerged from the 8-fold degenerate empty lattice level. The tight binding analysis of the band structure of diamond type semiconductors in section 2.5 has already shown that the second level (from below) at I? has For the third level at r, the representations r 5 or 1 were symmetry possible, according to this analysis. 4 s Figure 2.28 shows, r15 applies in the case of Si, while the I'b-level is the fourth. A410ng the A- and A-lines, the two 3-fold degenerate let~ls L and r15 I' must split since only 1- and 2-dimensional irreducible representations are possible there. Both a %fold splitting into 3 simple bands as well its a 2-fold splitting in a 2-fold degenerate and a simple band are conceivable. From Figure 2.28 one sees that the latter case holds, both along the A and Alines. and for the I?&- and the I'ls-levels. Since there are only 2-dimensional representations at X (for an explanation see Appendix A), two simple bands along the A-line must merge at this point, as actually happens in Figure 2.28.

214

Chapter 2. Electronic structure of ideal crystals

Figure 2.29: Band structure of the empty fcc lattice. The energy unit is the same aa in Figure 2.28. The irreducible representations of the energy bands are also indicated. For comparison, the band structure of Si is shown in the same figure by dotted lines.

A

t lo

0

L

w - 8

m

C

cu

w 6

r, 62 5; r; 5' 5 5 6;

r 1

r

A

Wavevector

X

**A 2-fold degenerate band along A cannot merge with another band at X , but
**

miist terminate in a doubly degenerate level at X. From this it follows, for example, that the upper of the two bands arising from the I'k5-level along the A-line must be 2-fold degenerate, and the lower band must be simple. A look at Table 2.4 shows that the only 2-dimensional representation of the small point group of A is A5. At X this representation is compatible either with X 1 or X 3 (the compatibility relations between irreducible representations are derived I n Appendix A). Figure 2.28 shows that X 1 is correct in this case. In a similar way one may conclude that the representation of the lower level at X ,arising from the I'i,-level, must be X z . A similar analysis for the splitting of the rls-level along the A-line shows that the lower level is nondegenerate and belongs to the irreducible representation A l , and the upper level is 2-fold degenerate and belongs to .As. The intersection between the Ah-band emerging from the r!+vel, with the As-band emerging from the l'ls-level, is not due to symmetry, but reflects an accidental degeneracy.

Consider next the two bands arising from the l'$s-level on the A-line. The upper is the 2-fold degenerate As-baud, and the lower is the simple A1-band. The simple band does not merge with another simple band at L , but remains separated from it by a finite gap, in contrast to the band behavior at X. This is possible because at L there arc also 1-dimensional representations, L1 and L i , which give rise to the two lowest levels at L . The splitting of the rls-level along the A-line is quite similar to that of the l?~5-level; lower band is non-degenerate and belongs to A l , and the upper the

2.8. Band structure of important semiconductors

2 15

is 2-fold degenerate and belongs t o h ~ . The occupation of the energy bands of Si and other diamond type crystals has already been discussed in section 2.6, using the band structure which follows in tight binding approximation. In the ground state of the crystal, the band associated with the 1-fold I'&vel, and the bands arising from the %fold l?h5-1evd, are completely occupkd, while the above-lying r16- and rbbands are completely empty. Thus the rl- and r&-bands form the valence bands of Si. and the rls- and rb-bands. as well as a l higher bands form the l conduction hands. The two groups of bands are separated by k-dependent forbidden energy regions, marked by dashes in Figure 2.28. Moreover, there are forbidden energy values which occur at all k-vectors. This means that the bami structme calcidations for Si yield a finite energy gap, and, inded, they explain the semiconductor character of Si. While the absolute maximum of the uppermost valence band lies at r, the absolute minimum of the lowest conduction band is located on the A-line close to the edge of the h s t B Z , and its irreducible representation is ALSemiconductors with the absolute extrema of the valence and conduction bands located at different points of the first B Z , are called ipadiwct. Silicon is, therefore, an indirect aernicondurtor. If the extrema occur at the same point, the- semiconductor i s called dawct. The property of a semiconductor material in being direct or indirect (Table 2.14 contains information about this) has important physical and technological consequences. For example, indirect materials are in general not suitable for manufacturing light-emitting devices, unless one takes special measures such as a particular doping. Following the general lines of section 2.5, we will now examine the e€fective mass tensors of Si. We will restrict oursehes to the two critical points mentioned above, in which the conduction band has its absolute minimum and the valence band has its absolute maximum - the vicinities of these points are the regions of the first 32 which. under thermodynamic equilibrium conditions, host most of the free eIectrons and holes. The effective masses at these points are therefore the effective masses of the electrons and holes of silicon. Owing to the cubic symmetry of the band structure of Si, a minimum of the conduction band on a particular A-line is automatically accompanied by 5 other minima on the star of A-lines. This means that there are, altogether, 6 minima OT valleys, a term which is often used for the vicinities of the minima. Since Si has several valleys. one calls it a many-valley semiconductor. The valleys are centered at the points

with kc = 0.85(2n/a). The cubic axes are, simultaneously, the principal

2 16

Chapter 2. Electronic striictnre of ideal crystals

axe8 of the effective mass tensors of the various valleys. Each principal axis represents a Cfold rotation symmetry axis. To p r o r d further. we select, arbitrarily, the valley centered at (O,O, kJ. The band structure of this valley is given by the expressions (2.201) and (2.2@2), which are applicable here, as their conditions of validity are satisfied. Setting the band index v equal to c, which refers to thp coiiductioii band, the dispersion rdation EJk) of this band becomes

(2.409)

If t,hc zero point of the energy scale is put at. t h r valence band maximum, as we do here. then E , is t,he fundamental energy gap. In the vicinity of the valencc band maximum, the general results of the k . p-method of section 2.7 are applicable. Without spin-orbit interaction (see cqiiations (2.345) to (2.348)) one has two valence bands for each of the two symmetry directions A and A, an upper E,l,z(k) which is 2-fold degenerate, and a lower &(k) which i s non-degenerate. Along less symmdricnl k-directions E,l/z(k) split 5 into two bands. However, spin-orbit interaction cannot be neglected; although it has little effect on the overall band structure of Si, it inftuences the valence band structure considerably in an energy interval of several kI' below the rnaxiniurn at r, which is the energy region where most of the holes B r e located. Spin-orbit interaction makes the uppermost valence band level at r, which has a 6;-fold degeneracy in Si if spin i s considered, split into an uppm &fold degenerat.e I?$-level The splitting rncrgy amounts to and a lower 2-fold degenerate I';-lcvel. 44 m e V . Away from I?: the upper ra-level decomposes into the two bands Efp(k) of heavy and light holes according t o equation (2.377). The lower r$-levd givw rise to the spin-orbit-splitr;-band. The heavy and light hole bands are strongly warped and each exhibits %€oldspin-degeneracy, which is due to timc reversal syrrirriet,ryin coinbination wihh spatial inversion (see Appendix A). If warping i s neglected the two bands Era(k)can he described by isotropic effective mass# m$. 'I'hey are negative because of the maximum ' I at . Extracting the negative sign, we define the positive effective masses rnEh and m.G1of, respectively, heavy and light holeb;: setting m , = - m ; , and :, = - m l . For the heavy and light hole valence bands EF8(k) G E,h(k) and E&(k) = E,,,(k): we h a w

ntl

(2.410)

Numerical values for the effective hole masses of Si are given in Table 2.14. A vivid view of the conduction and valence band structure in the vicinity of the band edges is provided by the corresponding iso-enerm surfaces. These

2.8. B i d structure dimportant semiconductors

217

**Figure 2.30: Iso-energy surfaces of the electrons (on the left) and holes (on the right) for Si.
**

I

are obtained by k i n g a specific energy and then drawing all k-vectors for which the bands of equations (2.409) and (2.411) yield this energy value (see Figure 2.30). For the conduction band, the iso-energy surfaces are ellipsoids of revolution, pointing in the direction of the symmetry axis. Each of the six star points is the center of such an ellipsoid. For the valence bands, within the isotropic approximation, the iso-energy surfaces are concentric spheres ? centered at I. The inner sphere corresponds to the light hole band, and the outer to the heavy hole band. In reality the valence bands are not isotropic but have only cubic symmetry. Thus their iso-energy surfaces are warped, as shown in Figure 2.30. If the conduction band is populated by electrons up to a given energy, then the k-vectors of these electrons lie within the ellipsoid of revolution corresponding to this energy. Accordingly, the k-values of the holes lie within one of the two spheres or the two bodies bounded by the warped surfaces.

218

Chapter 2. Electronic structure of ideal crystals

**Figure 2.31: Band structure of Ge. The energy unit is eV. (After Chelikowsky
**

and Cohen, 1.974.)

2.8.2

Germanium

In Figure 2.31 the band structure of germanium is depicted. It is similar to that of silicon, owing to the fact that both materials have diamond structure. The differences between the two band structures are, apart from other reasom, due to the fact that the spin-orbit interaction is considerably larger in the case of Ge as compared to Si (see Table 2.14). This results from the larger orbital velocity of the valence electrons of Ge because of the larger atomic nucleus of this element. With the regard of spin-orbit interaction the valencp band maximum at r is formed by an upper 4-fold degenerate rsf-level and a lowcr 2-fold degenerate I';-level, separated from the upper level by 340 meV. Away from I',the upper I',f-level decompoaes into the two 2-fold degenerate bands of heavy and light holes of, respectively, A6 and A7 symmetry, As in the case of Si, the bands are warped but often considered in an isotropic approximation. The lowest conduction band level r, at 2 arises from the ri-level without ! spin, which was the second conduction band level in the case of Si. In Ge this level i s shifted down considerably so that it becomes lower than the r, and , doublet which arises from the I'15-level without spin. The most important ? I

43 0.3 r L 2.8 - -.2. ‘ 2.-levels arising from the &-band on the A-line which enters the r7f-level at I. effective masses in free electron masses. C-BlmdMimirnurn Energy Gap 1.50 0.43 2. and Se read i ~ 1 1 I (parallel. . the band structures are shown in Figure 2.67 0. GaAs. 1982. In Ce it does not occur on a A-line.07 5 0.03 0.32.8. and that of GaP in terms of ordinary representations.33 0.064 0. Temperature 300 K.66 hl II 0. ( A f t e r Candoldt-Blirnstein.3 111-V Semiconductors For the two 111-V compound semiconductors GaAs and Gap.044 0.27 0.028 0. Energies in e V .- difference between the conduction bands of Ge and Si is the location of the respective absolute minima. CdTe.4 0.) Milaterial i _ .087 0.8. and for CdS (hcxagonal phasc).29 0.1 0.1 1 0. since they have the same Bravais lattice.17 0.30 0. while for GaP it may be neglected.30 0.7 GaP CdTe HPn: CdY r r 1. the conduction band of Ge has 8 half-valleys instead of 6 full valleys in the case of Si.00 0. Thus the band structure of GaAs is described in terms of spinor representations.54 0. The minima at L are L. Gap.45 0.31 0. Te. Band structure of important semiconductors 219 Table 2.34 0.14: Characteristic data of the barid structure of selected semiconductors.1 PbTe 0. PbTe. the valence band maximum lies at Without spin and r. For both materials. Spin-orbit interaction is important for the overall band structure of GaAs.7 0. being the B Z boundary point of the A-line. v l (heavy.022 0.15 0.044 I _ Si G2 I GaAS A L 0. Their first B Z s are the same as that of Si and Ge. light holes). Ge. For Si. but at L . perpendicular to . Therefore.24 0. and IIgTe read i = u h . syniniebry axis).08 0.11 0. The full point group of equivalent directions is T d for both materials.3 r X 1.24 ‘k Se - H Z(?) 1.

Electronic structure of ideal crystals Figure 2. The energy unit is el’.j .32:Band structure of 111-V semiconductors GaAs (top) and GaP (hot tom). (AfLer Chelikousky rand Gohen. 1974.220 Chapter 2.

4 11-VI semiconductors The band structures of two typical IT-VI semiconductors with zincblcnde structure. Band structure o important serniconductors f 22 1 I i r 1 x U. splits i CaAs and Gap. the r15 vulence band maximum splits into an upper r8-level. t o Td. which means that the point symmdry of equivalent directions is rduccd from Of. Thus.X3.8. Since the valence band maximum resides at I’. The band structure of . the conduction band minimum occurs at X and belongs to the representation XI.4 eV above the absolute minimum atr r.I .33: Band structure of IT-VI sernimnductom Cd‘k (left) and IIgTe (right).observed in the case of Si and Ge. Patroff and Balkanski.and also 1-dimensional ordinary representations (XI X2.K r I -61 L A I r A XU. (After Chadi.2.33. 2. Xq) instead of only 2-dimensional ones ( X i . and a lower I’7-levd In the upper l’g-level. Therefore. CaAs has a dirwt energy gap.8.wn atoms n of the primitive unit cell are no longer identical.. One of the peculiarities of its condiiction band structure is the relative minimum at the L-point only about 0. GaP is an indirect semiconductor. the two 2-fold degenerate heavy and light hole bands mcrgr together as in the case of Ge and Si.‘. 2972. it belongs to the irreducible repre sentation I’l5 of the point group Ta which arises from the representation .K E rI Figure 2.-level gives rise to the 8-fold degenerale spin-orbit-split band. one also has 2-dimensional spinor representations ( X s .are shown in Figure 2.) s spin-orbit interaction (the case of Gap). Walter. ? of Oh if the latter is taken as a representation of Td. X z ! x3> Xq) in the case of Si and Ge (see Appendix A). Cohen. The conduction bend minirnnrn of GaAs occurs at the r-point and belongs to the spinor representation r7. CdTe and HgTe. The lower l”. The %fold degenpracy of the valence hands at X. ) in the case of Si and Ge. With spin-orbit interaction (the caw of GtrAs). In the case of Gap. The reason €or this is that the t. The energy unit i el. X:) instead of only one 4-dimensional ( X .

so that the energy gap vanishes. The reason for this is easy to understand.222 Chapter 2. is found below it in HgTe.7. and was also already discussed in section 2. the two bands touch each other at r. The 8 valence electrons per primitive unit cell therefore suffice t o occupy only one of the two rs-bands merging at I. but as mentioned in section 2.7: The r6-level which lies above the I‘s-level in CdTe. The same holds for HgTe. as also occurs in GaAs. Electronic structure of i d 4 crystah 8 6 L 2 a -2 CdTe is similar to that of GaAs. The second band remains unoccupied and becomes ? . in particular the conduction and valence band edges are located at the r-point.

.U I 4 r I Figure 2.35: Band structure of PbTe.34). As an example of a 11-VI semiconductor which does not exhibit the zincblende but rather the wurtzite structure. and the two bands r6 and I?7 into which the rg-band decomposes under the hexagonal deformation. CdS has a direct energy gap at r. Band structure of important semiconductors 223 lxc. The first B Z is that of the hexagonal Bravais lattice. (After Martinez. which is shown along with its symmetry points in Figure 2. 1975. because in semiconductors the valence and conduction bands must be separated by a finite energy gap. The latter effect is called crystal field splitting (see the right part of Figure 2.12. Schliiter and Cohen. the valence band is composed of 3 bands. Furthermore.34). L r X K. Since it is degenerate with the uppermost valence band at I'. this means that HgTe is no longer a semiconductor. The energy unit is eV. Thus. the valence band is additionally split off at r as compared to the cubic materials of diamond and zincblende structure.) the conduction band. It is more fitting to term HgTe a semimetal. the fundamental energy gap is zero. namely r7-band which is separated from the other two by spin-orbit interaction. According to the general definitions of Chapter 1. because of the hexagonal deformation of CdS.8.2. we chose the hexagonal CdS (see Figure 2.

and that of the valence band is probably at H.6 Tellurium and Selenium The band structures of tellurium and selenium are shown in Figure 2.2 e l F . The energy gap o PbTe is relatively small. both the valence band maximum and the conduction band minimum occur at the H-point of the first B Z . Therefore. The energy unit is eV. Stuff. PbTe.35. the two edges both lie outside of I-.5 IV-VI semiconductors The band structure of a typical IV-VI semiconductor.224 Chapter 2.) 2. thus. is depicted in Figure 2.z H K r Figure 2.36. Like InSb of the 111-V-compounds. that of the conduction band is probably at 2 . it f amounts to about 0. It crystallizes into the rocksalt structure.36: Band structure of Te (left) and Se (right). Its Bravais lattice is. 1 g71. PbTe belongs to the group of narrow gap semiconductors. Maachke and Laude. In the case of Te. The material is therefore direct. i973.8. This means that PbTe is a direct gap semiconductor with many valleys. Both materials have hexagonal Bravais lattices. a special feature which is hardly realized in any other semiconductor families apart from the IV-W compounds. again the fcc lattice and its first B Z is the same as that of the diamond and zincblende type crystals. Se has an indirect gap. The conduction band minimum and the valence band maximum both lie at the edge-point L of the first B Z . they have the same first B Z s as the hexagonal CdS. . 2. Electronic structure of idea[ crystals 12 8 4 0 -4 -8 r z H K r 1 . (After Maurhke.8.

will be developed in section 3. not the atomic structure which provides real semiconductor crystals with special scientific and technological importance.1. like the so-called deep centers.5.4 important theoretical method €or its solution.4. . in which potentials exhibit considerable change over the atomic length scale. With some justification one can even say that the particular scientific and technological importance of semiconductors rests on the peculiarities of the electronic structure of amperfeet semiconductor crystals. This equation allows one to determine the effects of perturbations whose interaction potentials with electrons are slowly varying over the atomic length scale. the so-called ~ effective mass theory. in particular to the so-called shallow centers which will be treated in section 3. for example.2. however. also other perturbations. This is also true for clean semiconductor surfaces considered in section 3. the increase of electrical conductirity by orders of magnitude. the source of the particular nature of their electronic structure.3. but require other methods. Interaction potentials of this kind apply to many perturbations of atomic structure. . They differ from ideal crystals in their atomic structure as they contain structural defects. The one-electron Schrodinger equation of imperfect semiconductor crystals will be derived in section 3. They cannot be treated by means of effective mass theory. however. to be dealt with in section 3. Nevertheless. This will be done in section 3. and their chemical cornpodmn is not exactly lhal of the correspondiug ideal crystals. but their peculiar electronic structure that is manifested in pronounced macroscopic effmts such as. It is.22 5 Chapter 3 Electronic structure of semiconductor crystals with perturbations Real semiconductor crystals are imperfect.6. one must also deal with the atomic structure of imperfect semiconductor crystals since that is. There are. ultimately.

In the case of elemental crystals.7) and semiconductors subject to an electric field {section 3. In this sense.providing the justification to speak of a crystal at all. or arbifmid atomic superstructures.1. mechanical strain. the latter may be characterized as follows: All regular sites Ri 7 rial + r2a2 + 7'3a3 + 6 (3. there is deviation from the ideal occupation at some of the regular and irregular sites. In all cases. In the first case. one can distinguish them on the basis of whether they are of a purely chemical nature. only regular sites of the crystal are occupied. which hosts the impurity atom. but. but these are not always positioned on regular crystal sites but also on irregular ones. 31 . This will include superlattices (section 3. are occupied by atoms of the 'correct' chemical species. The electronic structure of semiconductors in the presence of such macroscopic external perturbations is treated in the second part of this chapter. the effective mass theory plays a major part in our theoretical understanding. One refers t o this as chemical or cornpositzonal dzsorder. As discussed in Chapter I. A crystal formed from a chemical compound may also exhibit f compositional disorder without impurity atoms. namely because o a perturbed stoichiornetrical composition. not . again. only chemically 'correct' atoms are present. In this context the perturbed crystal.226 Chapter 3. is called the host crystal. 3. and other sites are empty. one then refers to the crystal as either perturbed or real. Atomic structure of real semiconductor cryst als The reference system for the description of the atomic structure of a real crystal is the ideal crystal. In the case of structural perturbations. albeit a perturbed one. not with chemically 'correct' atoms throughout. On the one hand. this characterization holds for the vast majority of regular and irregular sites . Furthermore. this kind of disorder necessarily means the presence of impuaty atoms.1 Classification of p e r t u r b a t i o n s The perturbations to be treated can be classified in accordance with several points of view.1) defined by the crystal structure. Electronic s-tnictirre of semiconductor crystals with perturbations Besidc the study of semironductor crystals having a perturbed atomic structiire. or mixed type. In a real crystal.8) or a magnetic fidd (section 3. 11 is also of interest to study semiconductors which are exposed to macroscopic external perturbations such as dectrir OT magnetic fields. or purely structural. However.9). This theory applies because the macroscopic perturbation potentials are naturally smooth over the atomic length scale.

A perturbation that is limited to one or a few neighboring regular or irregular crystal sites is called 0-dimensional or a poznt perturbatzon. the ~ynibol GaAs . ‘l’herefore. starting with point perturbations. form substitutional impurities.1. Since the impurity atom substitutes an atom of the host crystal (see Figure 3. end also the ‘correct’ atoms partially occupy ‘wrong’ sites. There may be smaller perturbations induced by that core which extend in three dimensions. impurity atoms which are chemically similar to atoms of the host crystal. which. As a rule. (1) We begin with an impurity atom on a regular crystal site. Below we will characterize the various perturbations in more detail. we describe the most important compositional and structural point perturbations of semiconductor crystals.2 Point perturbations Types of point perturbations In this subsection. or a sulphur atom in GaAs on a As-site. The third case is the most general one . in most cases.1. Deviations from an ideal crystal may. one may refer to structural point or line perturbations.regular or irregular sites of the crystal are partially occupied by rhrrnirnlly ‘wrong’ atoms. Examples are charged impurity atoms.lb)’ it is referred to as a substztutzonal vrnpuraty. are incorporated substitutionally. The substitutional incorporation.1. and in the second.3. Atomic structure of red semicoriductor crystals 227 all regular siles are occupied by atoms. compositional point perturbations etc. S A ~ . For this reason. Structural perturbations are also called strurtural & f w h or simply dpferts. An illustration is given in Figure 3. occurs on that lattice site which corresponds to the chemically most similar of the two atonis in the binary compound semiconductor. it is referred to as a 1-dimensional or lzne perturbatton and a 2-dimensional or planP perturbatton. If the perturbation extends over sites located on a line or a planc. change the potential energy of an electron even over distances large compared to the lattice constant. rpspert ively. To avoid a somewhat cumbersornc description. on the other hand. many elements of the mein group of the periodic table. in the first case one uses the symhol S I : P . The dimensions in the second classification scheme apply to the microscopic core of the perturbation. be distinguished according to the macroscopic extension of the perturbations. Combining the two classification schemes. due to their long-range Coulomb forces. Examples of substitutional impurities are a phosphorus atom in Si on a Si-site. some sites remain empty. if added l o group-IV elemental semiconductors as well as binary 111-V and 11-VI-compound semiconductors. the doping of GaAs with S leads to the above mentioned point perturbation . 3.

of course). In thc latter case t. This happens. as shown Figure 3 . as depicted in Figure 3.he crystal has bond centered interstitiah. and the anion vacancy by GaAs : VA*. one has an interstitial ampurity atom (Figure 3. the crystal should n not be packed too densely. the . the general symbol is V. It is quite clear that this will be satisfied for interstitial sites which either haw high local symmetry or which lie on a bond between two at'orns.he case of transition metal atoms in semiconductors composrd of elements of the main groups.. one n has to distinguish between cation and anion vacancies. in t. there are high symmetry sites with hcxagonal symmetry. The general symbol for an interstitial is I .Vacancies occur in all important semiconductor crystals.this is called a Ga-antisite defect. particularly in Si and Ge which have purely covalent b ondinE. An interstitid Fe atom in Si on a tetrahedral site is denoted by Si : I. vacancies and antisite defects are structural point perlurbations. i the case of tatrahedral semiconductors. In order for such a structural point defect to develop in a crystal. Ic. as f e t v u h c h l and hexagonal interatitiak The incorporation of impurity atoms on interstitial crystal sites is especially likely when the impurity atom deviates relatively strongly from the atoms of the host crystal as! for example.. G a A s : Sica (and not GaAs : S ~ A ~ ) . then an atom of the h s t may occupy a regular site of t h e sccond. (3)If the impurity atom does not occupy a repular crystal site but a site between regdar ones. T semiconductors made of binary chemical compoiinds. a Ga atom may be located ttt an h . i. and vice vcrsa Such point perturbations are called antisite defects. The compositional point perturbations.16).&. as i l h s t r a t d in Figure 3 . . Elcctronic structure of semiconductor crystah with perturbations C a A s : S A (and not GaAs : S G ~ )and the doping of GaAs with Si leads to ~ .e. i. for example. there must h e enough space between the host ntmns. 1 In the ~ case of CiaAs.s i t e this is called B I ~ As-antisite defect.le). (2) An unoccupied regular crystal site is called a vncuncy. In order for an impurity atom to stay at an interstfitrialsite. and tla As atom may occupy a Cia-site . for example. or point defects. ~ ~ Interstitials. 1 ~ .. The vacancy in Si is denoted by S i : c': the cation vacancy in C h 4 s by G a A s : T. The symbols are As& for the As-antisit>e defect. and G U Afor the Ga-antisite defect.e. it must have sufficiently low energy there.a crystal consists of two different chemical elements. one has a self-interstitial (as shown in Figure 3. ( 5 ) If. The high symmetry interstitial sites in t e t r a h d a l seniiconductors may be such with tetrahcdral local symmetry in the neighborhood of the cation or of the anion (for group IV elemental semiconductors the latter distinction is void.228 Chapter 3. (4) If a chemically 'correct' atom of the crystal occupics an interstitial site rather than a regular one. Moreover. One refers to these7 respectively.

3 .-Antisite B.-Antisite e) Figure 3.1: Illustration of the most important point perturbations in semiconductors using the example of a crystal with two atoms per unit cell of the same chemical element (left-hand side) and different chemical elements (middle and right-hand side). Atomic structure of real semiconductor crystals 229 Ideal crystal A -Atom 4 0 B-Atom Impurity atom Substitutional impurity (S) SA SB Vacancy (V) Interstitial ( I 1 Interst. 1 . impurlty -___ A. .

Classification of impurity atoms The division of elements into groups. The periodic table consists of two types of groups of elements. The energetically highest. in gen- . and thus in general.1 have in common the feature that electron shells with angular momentum quantum numbers 1 2 2 either do not occur at all or. the former are simultaneously also the outer shells of the atoms which are responsible for chemical bonding. One thus also speaks of sp-bonding elements. need to be further specified. and the transition groups. no partially filled shells of this kind occur. if they exist. This is not surprising because the incorporation of an impurity atom in a crystal indicates a more or less strong chemical bonding.3.and f-shells. they are completely filled or completely empty. thus. in which the s.2 and 3. The elements of the main groups in Table 3. the shells with 1 2 2 are energetically the highest and.e.and pshells are also completely occupied.230 Chapter 3.and p-shells in comparison with d. In the rightrnost column the respective closed shells are indicated. The rare gas elements are special cases. also proves to be helpful for the classification of impurity atoms in semiconductors. Because of the relatively large spatial extension of s. Therefore.and p-shells.1: Electron corifiguratiori of main group elements. 50 belong to the main groups and 48 to the transition groups. We summarize this group division of chemical elements below. which is commonly used in chemistry. the main groups. i. they are s. Of the first 98 elements. Electronic structure of semiconductor cxystals with perturbations Table 3. only partially filled shells of these elements either have 1 = 0 or 1 = 1. impurity atoms. This will be done next. For the elements of the transition groups presented in Tables 3.

Because of the relation R 2 I 1 between the main quantum number ?a and the angular mornenturn quantum numbe1 E. .3) only for n 2 4. the f-shells ( 1 .2) are possible only for n >_ 3. Accordingly. n ziSc =Ti 3d4~3~ 3d248' 23V Iron m o w 3d34s2 z4Cr 3d5& wMn 3d"4s2 mF'e 3's d42 z7cO Ni 3d64aa 3d74s2 3a23p6 era1 they are the not completely occupied oms. In the rightmost column the respective closed shells are shown. Table 3.3: Electron configuration of rare earths and actinides. etc. 6 4 Sf. Sf.&. 4f.3. fih ptc. Atomic structure of real semiconductor cry&& 231.s.2: Electron configuration o€ transition dernent. one has the shells 36. 69. In the right column the respective closed shells are indicated. the d-shells (I .1. 5d. Since among the first 98 elemmts of + Table 3.1g. Actinides .

Complexes of point perturbations. point perturbations also associate if the result is a state with lower energy. This leads to the formation of donor-acceptor paws. namely the d-shells 3 d . Bonding can occur between various point perturbations: between chemically identical or different impurity atoms. the mechanism for the formation of bound pairs can also be easily undertitood the (internal) surfacc of thc crystal i s reduced if two previously isolated vacancies move together to occupy neigh- . however. the palladium group in which the samc happens with the 4d. Among the transition metals. In comparison with the s. a n d a certain similarity of these elements with the elements of the main groups.and p-orbitals. The associates may consist of two or of several constituents. the pairs are stable at several possible distances.and multi-vacancies When there are two vacancies.and p-shells of the same main quantum number 7 ~ . and the platinum group where the 5d. the d . and among point defects themsclvcs. 4d.ystals with perturbations the periodic tablc.s-shells. they lie mostly within the s.and 4.and 5d-shells takes place in the series of transztzon metals (together with the Elling of the 4s-.and f-orbitals have a smaller extension in spacc. The 4f-shells are being filled in the rare earth elements. the lowering of total energy through the formation of a bound complex of associtlteb is particularly obvious the two point perturbations are differently charged and attract each other through electrostatic forces.232 Chaptcr 3. mainly s.and 3s-shells are being filled. and the f-shells 4f and 5 f . 5s.and p-electrons are involved in chemical bonding. one distinguishrs the iron groixp in which the 3d. Electronic slructure of semiconductor cr.and 6s-shells). The filling of the 3d-. only d.and 5s-shells are being Elled. In general. associatos Just as atoms arc bound in molecules when it is energeticaqy advantageous.and f-shells are to be considered. whirh gives rise to a variety of different donor-acceptor pair complexes. Di. the 5g-shell already remains unoccupied. and the 5f-shells in the actinides. This explains the remarkable chemical similarity of thc rare earth elements with each other. The diversity of these associates is comparably large to that of molcculcs in chemistry. 44 5 d . We give some examples below. 6 d . They are called poznt perturbatzoa complezeu or u8souutP8. between impurity atoms and point defectu. in which the donor and acceptor atoms occupy neighboring sites in the crystal. 'l'herefore. Donor-acceptor pairs In the case of an ionized donor and an ionized acceptor.

Coulomb forces. Of course.g. Analogous atatements holds for the association of more than two vacancies. There arr important puint perturbation complexes which occur only in a specific material or matrrial group. as commonly happens. It is found in GaAs and also in (Ga. The two ions attract each other by.5). to a donor atom which is incorporated interstitially but not substitutionally. Point perturbation complexes in G a A s A prominent defect associate in GaAs is the so-called RX-center. in a crystal. Oxygen in Si enters into bonding with a vacancy. Thereby the electron of the H atom is captured by the acceptor atom: which becomes singly negatively charged. which are called multrvarunczes. which results in the formation of a neutral ( H . for example. Originally. the DX-center is thought to be due to the donor atom alone. for more see section 3. hydrogen is often present in Si. among others the so-called thermal f d a m r s . it negatively charged B-ion and ti positively charged H-ion are formed in this way. One may also conclude that the acceptor expends i t h hound hole to the H atom ralher than to the valence band because it has lower energy there. Oxygpn is also involved in a wries o other defect complexes in Si. It is called a Freibel defprt.. forming a pair which probably constitutes the so called A-renter known from caparity 111ea~iremmtfi. an atom moves froin a regular site to an interstitial site. We now consider some examples for si snd G A S . then it h v e x behind a vacancy which attracts the interstitial. In p-type Si. One caIls this associate a ddvacancy. Atomic structure of red semiconductor crystah 233 boring cryYtal sites. B )pair. Se. Thus a defect pair is formed in this process which consists of a self-interstitial and a vacancy.1. the DX-center was attributed to a donor atom. the pair will not be able t o arcept an clcrtron which means that the B atom has lost its ability to act as an acceptor. bound t o another point perturbation whose nature was unhiowii at t!hHt time and. e Chalcogen atoms like S. more strictly. Currently. A1)As mixed crystals under appropriate conditions (e.3. was denoted by X. therefow. In B-doped Si. which are thusly named hPraiise of their origin in thwmal treatment. Frenkel defects If. and T are incorporated in S i not only as single atoms. Point perturbation complexes in Si Wr various reasons. which acts as a donor. Another . high pressure. H atoms undergo chemical bonding with the availablc wreptoi atoms. like S&. but tlBo as two-atom molecules.

Experimental information concerning the symmetry of lattice relaxation may be derivrd from observation of t. This is known as lattice relamtion (in Figure 3. if lattice relaxat. This eflect results in splitting of the degenerate energy levels of a point perturbation due to a symmetry-lowcring latt. in many cases. hardly more t. complete and reliable experimental data are available. This mag.in GaAs. oxygen or heavy metals in Si cryshls. by point perturbations bmome larger and reach mesoscopic size.1 this effect is omitted).o move t.he symmebry is known from experiment. for example.ructwes of ideal crystals described in Chapter 2.ion becomes important.one refers to them as aggw.5).u new equilibrium sitcs.he Jahn-TelEev efleet. they can be determined by means uf atomic structure calculatious for t h e perturbed crystal. the lattice rehxation can reduce the original tetrahedral symmetry T d to tetragonal symmetv D2d. Such spontaneous symmetry breaking occurs when it leads to lowering of the total energy of the crystal. However. The new rqiiilihriiim sites are initially tinknown.ronic structure. First. HoweveT. the ideal crystal sites.o the atomic structure of a crystal in the vicinity of a point perturbdion.hari t. for t. Complexes of macroscopic size such as. just as is done in self-consistmi. In principle. section 2. calcidations of the electronic and atomic st. In the case of a varaiicy: for example.L!Lcentei. These have t o be performed sirnultanmusly with calculations of the elect.he point perturbation has a c1rgenerat. this complex is believed to form t h e care of the so-called b.qates. the degenerate level will split off due to the symmetry lowering relaxation.omir:sbriictures must actually be carried out. . happen when.2. are called Latticc relaxation The forces on atoms in the irnmediatc vicinity of a point perturbation differ frorri those in lhr ideal crystal.e level which is only parhially occupied. of all.omic structure may be avoided since. They are non-xr?rol in general. in regard t.he latter. Point perturbation aggregates I€ the complexes formed precipitates. Thus the self-consktent calculation of the electronic and at. the calculation of at. Now. Hectronic structure of semiconductor crystals with perturhations typical defect associate in GaAs and other Ill-V semiconductors is the complex formed by an As-antisite defect (a Ga atom on an &-site) associated with an As-interstitial. According to perturbation theory. Thus the atoms are forced t. i.ice relaxation. For ideal crystals. This center manifests itself as deep level having strong influence OR the electrical and optical properties of GaAs (more detail on the EL2-rcnter may br found in section 3. at. in the unrelaxed state.234 Chapter 3. there is an impwtant difference between the two cases.

A1)As mentioned above (see section 3. for a b t a k with a nonvanishing concentration of structural defects.TS. therefore. i. the minimum of H is not necessarily coincident with a minimum of the Gibhs free energy G . If only the latter are predominantly occupied. the displacements of atoms are of the order of magnitude of one tenth of an Angstrom.T S can also be adjusted for a state of the crystal which is less advantageous with respect to enthalpy. This energy reduction can compensate the increase in total energy due to the removal of atoms from their equilibrium sites. but more advantageous with respect to entropy. along with levels shifted up. It is extremely improbable compared to the large number of states in which deviations from the ideal configuration of atoms appear as described above. Lets assume that there arc only chemically ‘correct’ atoms. there are also levels which are shifted down.3. The entropy S of the ideel crystalline state i s smaller. Atomic structure of real semiconductor crystals 235 this splitting proceeds such that the center of gravity of the levels remains unchanged. the most important and general being the second law of thermodynamics. depending on external conditions as. 3. Thus. and that these are randomly distributcd in space.1. for example.e. are observed at point perturbations for which different atomic structures are stable. Depending on temperature. than that of the imperfect crystalline states. There are various reasons for their occurrence. The system considered here is the totality of the atoms of the crystal.3 Formation of point perturbations and their movement Formation of structural defects All of the above mentioned defects of ideal crystal structure may in fact exist in real semiconductors. Then the idedl crystal is formed wherein the atoms move to the regular crystal sites. According to this law.e. In the case of the Jahn-Teller effect. i. The entropy of a macroscopic state is proportional to the logarithm of its microscopic realization probability (or ‘thermodynamic probability’) and the proportionality factor is given by Boltzmann’s constant k. This phenomenon is observed at the D X centers in GaAs and (Ga. they are relatively small. a minimum of G = H . is characterized by a minimum of the Gibbs free energy G = H . As a concrete examplcs we . the thcrrnodynamic cqiiilibrium state of a crystal at temperature T and pressure p . Since the entropy S takes larger values in other states. of the order of magnitude of one Angstrom. If this happens the relaxation is energetically favorable and will take place spontaneously. Larger displacements.5 for more detail). then the energy of the electrons localized at the point perturbation decreases. the position of the Fermi level. Here H is thc enthalpy and S the entropy of the system.1. This corresponds to a very special state of the system. The minimum of enthalpy II i s reached in the ideal crystalline state.

substantially change the defect concentrations The defects are frozrii in. hy thcir derivation. he taken into account is the enthalpy Rf necessary for the formation of n vacancy (at constant pressure). the gain of Gibbs free energy AG due to the formation of n. Efectronic structure o semiconductor crystals with perturbations consider a vacancy in an elemental semiconductor. In a more rigorous treatment. . however.n . one gels the value n = J x 5 x 10-l' from expression (3.r L + l)/nL The gain of entropy AS compared to the ideal cryatd t hrrefore mntnints to As=kln[ J! n!(J . Because J . vacancies becomes This expression Ims t o be minimized with respect to TL for a h e d value of T and p. Altogether.1400 K (roughly the crystalhdation temperature of Si).It)! 1. however. What must.m~ follows from this relation. Similar concentrations are ohtnincd for other point deferts. For each realization of the irlcal crystal one has. at which the c q s t d is grown. A vacancy is created w h m one of t h e atoms is removed from the crystal. J realizations of the crystal with B vacancy. the number o f realizations is . a varancy conrmtration of about 1013 crriL3 follows. For R independent vacancies the enthalpy requirement is n H f .s x cm-' (for Si). In an ideal crystal. Thew v a h s refer. J ( J .5). We will neglect this effect in what follows. the entropy of lattice oscillations has yet to bP considered in AS. therefore. Assuming H f = 2 5 el/ and T . From this one may conclude that the presence o a considerable number of point defects in f .I ) . to the high temperatures assumed above. there are J different possibilities for such a removal. as many as thme are atorns.f 236 Chapter 3. more accurately. the change of this entropy because of the alteration of the spectrum of lattice oscillations in the presence oI the vacancies. the ilctivalion 1. h { n ! )N n In(n) . Altogether. the periodicity region contains a number J of identical atorris. the minimum coiidition may be written as Since n << d can be assumed. ( J . Cooling down to room temperature often does not. According to of Stirling's formula. The enthalpy of formatiult HJ €or B vacancy typi d l y amounts to several c l ' . II n independent vacancies exist.

in the form of an upper limit. as a rule. for example.ration of impurity atoms in a crystal exists. The Si singlecrystal bars used in microelectronics its a material base. t>hesolubilities in semiconductors made of such elements are sub~ . one reduces the concentration of impurity atoms only to a level which is absolutely necessary for the application iinder consideration. Atomic struclore of real semiconductor crystals 237 crystals is essentially unavoidable. solubility values of lo2' c n ~ . The dissolving of A1 in GaAs. The latter depends on the chemical nature of the impurity atom and host crystal. In the extreme rase. the laws of thermodynamics in this case also act in a direction which leads away fro111 the absolute chemical purity of the ideal crystal. i.~ reached.1. For P in Si or Ge in G A S . High solubility values are achieved. However. one has relatively high solubility.the number of chemically 'wrong' atoms can be reduced. and it also differs for incorporations at differciit crystal sites like substitutional or interstitial ones. For transiare tion metal elements.e.ood as the formation enthalpy of the impurity. If the crystal consists of elements of tho main groups.rongly chemically from the main group elements.he solubility equals the concentration of the host crystal atoms. has smaller Gibbs free energy than that of the chemically absolutely pure crystal with all the impurity atoms confined to the remainder of the chamber. if the element of lhe impurity atom is chemically similar to at least one of the elements of the crystal. contain vacancies and interstitials in ~rn-~. which d i k r st. of course. as a rule. which i s the case for the majority of known semiconductor materials. especially for impurity atoms of these groups themselves. Incorporation at substitutional sites is preferred in this case. Of course. i. can only be effective to the extent that chemically 'wrong' atoms are available in the raw materials and the chamber in which the crystal is grown. t. Theoretically. In such cases. The state of a mure or less homogeneous distribution of impurity atoms in the whole chamber. however. the above estimated concentration of about Incorporation of impiirity a t o m s Chemical point perturbations are not as unavoidable as structural defects. by cleaning the raw materials and the growth chamber in thermodynamic terms by an extraction of entropy . no limit exists for the degree of purity achievable. which lie just a little below. an alloy will be formed with t. Therefore. results in a (Gtt. providcd H f is underst. crn-'. A boundary for the achievable concent. The solubility increases with rising temperature acrording to a law which is similar to that for the vacancy concentration of equation (3. Under thermodynamic equilibriiim conditions it is given by the solubility of the corresponding elements in the semiconductor crystal. This tendency.e. the state in which the growing crystal also contains impurity atoms.he impurity atoms.5). Al)As alloy. in fact.3. practically such td limit is set by the cleaning expenses.

and pshells are involved in chemical bonding. The solubilities of the rare earths are nevertheless relatively small.238 Chapter 3. Both the point perturbations themselves as well as the environment atoms are in permanent motion because of the lattice oscillations. to reach their equilibrium sites. Generally. This is referred to as a m i g r a t i o n of point . Another method proceeds in the solid state: the irnpurity atoms are ‘diffused-in’ from an outer source. Besides the two processes mentioned. In many cases. The heating also makes it possible for the impurity atoms. and 1017 ~ r n -in the case of thc compound semiconductors where. Small atoms. This may be understood by means of the fact that the not-yet-completed 4f-shells are smaller than the already filled 5pand 6s-shells. Due to the effects of these forces the perturbations move over to equivalent crystal sites in adjacent primitive unit cells. This results in more or less chaotic forces on the point perturbations. such as atoms of the transition metals. penetrate into the crystal where they are ‘implanted’. among them the so-called i o n i m p l a n t a t z o n In the latter. so that 3. just as in crystals of main group elements. the impurity atoms. like H. as a rule. This implantation process must be followed by heating of the crystal in order to heal out the defects which arise during implantation (annealzng). after they have initially been ionized and then accelerated by an electric field. may be interstitially incorporated in higher concentrations than larger atoms. Electronic structure of semiconductor crystals with perturbations stantially smaller. the surplus atoms are later excluded from the crystal to a certain extent (precipitation). where the transition metal atoms can be ~ incorporated both substitutionally and interstitially. Migration a n d diffusion of point perturbations Point perturbations interact with the atoms of the crystal surrounding them. &henthe melt is rooled down to cause crystallization. The easiest one exploits the growth of the crystal from the melt: the impurities are added to the melt of the host material. which introduce impurity atoms under equilibrium conditions. a relatively large number of surplus atoms remains in the crystal. There are various procedures to introduce impurity atoms into crystals. typical values being of the order of magnitude I 014 cm-3. substitutional incorporation is preferred. which were initially placed at sites relatively indiscriminately. They lie in the region between lOI4 cm-3 in the case of the elemental semiconductors. there are also non-equilibrium procedures to reach this goal. If the concentration of implanted impurity atoms should be larger than the equilibrium solubility. solubilities for interstitial impurities depend strongly on the sizes of the impurity atoms. the crystal is heated. which then is in a ‘frozen-in’ non-equilibrium state. To speed up diffusion. It is remarkable that rare earth atoms are predominantly incorporated substitutionally in tetrahedral semiconductors of the main group elements.

+ where Do is the limit of U at high temperatures. Conespondmgly. At1 atoms in Si preferentially diffuse through interstitial sites. The d i f f ~ scoefficient i~~ at 1500 K of about 2 x c m 2 scc-l exceeds that for P in Si by 6 orders of mappitude. amounts l a about 1e V . and for the migration of a self-interstitial in these materials. with the pressure p held constant rather than the volume V .. Migration constitutes the elementary microscopic event underlying the mtacroscopic process of diffusion. . The initial and final states of an elementary migration act are relatively stable states of the crystal. as comnionly OCCUTS.1. In Table 3.H . namdy by filling a neighboring vacancy site.3. For not-too-large gradients of the defect concentrations. H. an interstitial impurity atom does not need the help of a vacancy for its migration. For the migration af a vacancy in Si and Ge. Atomic structure of real semiconductor crystals 239 perturbations. This means that ttn energy barrim has to be overcome in an elementary migration act. Q is given by the sum of the migration mthalpy Hm and the formation enthalpy H f for a vacancy. Substitutional impurity atoms preferentially diffuse through vacancies. The temperature dppendence of the latter also exhibits an activation behavior. the migration rate becomes proportional to the activation factor e x p ( . A substitutional impurity atom migrates mainly with the aid of a vacancy.25 el/. namely the diffusion coefficient D. The latter occurs then when the distribution of the migrating point perturbations is spatially inhomogeneous. it can move directly to an adjacent equivalent crystal site. The latter vacancy is displaced with respect to the original vacancy. For diffusion through vacancies. The migration of a vacancy proceeds such that an equivalent neighboring atom moves to the vacancy site and leaves a vacancy behind at its former position. In the case of diffusion through interstitial sites. The reason for this hiigp d i k e n c e is thp siibstantially smaller activation enthalpy for interstitial diffusion as compand to substitutional. In contrast to this. Between them. which diffuses substitutionally. the diffusion coeficient at 1500 K is about lo-'' cm2 sec-'. the lattice oscillations must provide the energy Em or the enthalpy Hm = Em p V . For P in Si. the diffusion of a particular kind of point perturbation may be traced back to just one material constant. the activation enthalpy Q equals the corresponding migration enthalpy H. In order for migration to occur. In this way. the first Fick's law may be applied in many cases. it is smaller than 0.4 the Q-values for substitutional and interstitial diffusion of some impurity atoms in Si are listed. One calls it the magration barrier Em. intermediate states with larger total energies occur. / t T f .

Grain boundaries occur in crystals which in fact consist of two differently oriented half crystals . however. then the result will not be equal to zero.39 0. The two most important examples of 2-dimensional perturbations are stacking faults and grain boundaries. At a step dislocation.2).7 0. not limited to a line as one could initially assume. surfaces of crystals may also be considered as 2-dimensional perturbations. If one calculates the line integral over the path shown in Figure 3.9 3. ordering on lines and planes occurs only for structural point perturbations. Then one has 1. After that one reconnects the two crystal halves again (see Figure 3. indeed. The most important representatives of a 1-dimensional perturbation are stepand screw dislocations. but equal to a non-zero vector perpendicular to the dislocation line. deviations from crystal structure are. as would be the case for an ideal crystal. The microscopic core of the perturbation is limited. Electronic structure of semiconductor crystals with perturbations impurity atom activation enthalpy (eV) B Ga P H Au Cu 3. . It is called the Burger’s vector. Slight atomic displacements (strain) occur in a finite macroscopic environment.1. the occupation of a particular lattice plane breaks down along a line of lattice points . Then the lattice planes left and right of the cutting plane are shifted parallel to the screw dislocation line by a lattice vector.the plane is occupied on one side of this line (representing the step dislocation line).and.the grain boundary is the lattice plane at which these two half crystals meet. The line integral about the screw dislocation line yields a vector parallel to this line. In practice. to the dislocation line. For a screw dislocation one has to view the crystal as being cut by a semi-infinite lattice plane.2. but certain lattice planes are twisted by an angle.2 (left-hand side). 2-dimensional perturbations in contrast to the 0-dimensional ones considered above.43 3.7 3.4 Line and planar defects With an increase in the number of point perturbations. In a crystal with stacking faults.5 0. the various lattice planes carrying the atoms are not stacked in the same way as in the ideal crystal. right-hand side). In a dislocation. but not on the other side (see Figure 3. respectively. In a sense. which is bounded by a line of lattice points representing the screw line. a tendency arises for these perturbations to arrange themselves on lines or planes of macroscopic size.240 Chapter 3.

our considerations to crystals with compositional or structural point perturbations.2. thr ontLclectrou Schrodinger q u a t i o n for a crystal with point perturbations does not substantially differ from the o n e electron Schriidinger equation for an ideal crystal. 'rhis is done in recognition of the fact that only point perturbations can play an important positive role in semiconductor devices. yotentid I/Frt(x) of the valence electrons.76). the latter can also be more easily avoided than 0-dimensional perturbations. In analogy to equation (2.76) we therefore have . In this. the Hartret. However.3. we restrict. while perturbations of higher dimensions are generally disruptive. because they are less effective in increasing entropy. In the following sect'ion we will formulat'e the Schrijdinger equation for the oneelectron states of a crystal with a point perturbation. ) the potential V ' c ? 7 L ( ~ ) caused by thf atomic cores of the perturbed crystal.2 One-electron SchrGdinger equation for point perturbations In regard to its geiwral form.2 never actually involved the periodicity of the ideal lattice. ( A j L w f35w. and the exchangecorrelation potential V F : ( x ) of these electrons.2: Illustration of a step dislocation {left-handside) and a screw dislocation (right-hand side).and 2-dimensional perturbations. therefore. The reason for this is that the derivation of the latter equation in section 2. also the potential V ~ " ( x of the perturbed crystal is the sum of three contributions. Only the oue-elwtron potentid limrt(x) of the peTtriirbeclrrystal diffws from the rarresponding potential V ( x )of the ideal crystal given in equation (2. 3. we excliide 1. just like the latter. One-electron Schriidinger equation for point pcrturbations 24 1 Figure 3. 1990.) Having surveyed of the atomic structure of real semiconductor crystals we will now proceed to the electronic structure of such crystals. Fortunately.. The silicon bars used in microelectronics are now grown practically free of dislocations and grain boundaries.

then one has. of We decompose it into a sum of the core potential Vc(x) for the ideal crystal. VC~'"X) = K ( X ) I V. Electronic structure of semiconductor crystals with perturbations VWTt(X) = V ? t X f V. (3. We consider.1 Elect ron-core interaction First of all. for example.t(X).2. the two atomic cores differ mainly through their different charges. ZI and ZH are simultaneously also the numbers of valence electrons of these atoms. if a P atom with only one additional proton and one addit. we assume that only one point perturbation exists in the crystal. we discuss the potential VcPTt(x) the electron-core interaction. Because of charge neutrality of the individual atoms.10) The point perturbations listed in section 3. With this rqiiirement. The potential energy of a valence electron of an impurity atom of the type described differs. One refers to them as isocoric impurity atoms. thc one-electron Schrodinger equation for the wave function $ l V ( x ) of an electron of the perturbed crystal reads 3.ional neutron substitutes a host atom of a Si-crystal (as illustrated in Figure 3. above all. Thus. and we procecd on the assumption that the potential VJx) falls off with increasing distance form the origin and finally approaches zero: V. and a potential V. If one considers the cores to be point-like and neglects spatial dispersion of dielectric screening. by the change of Coulomb potential from the potential energy of an electron of the host atom.7) With this. initially.3). The center of this perturbation will be taken as the origin of our Cartesian coordinatc systcm.'(x) -+ 0 for Ix I + 00. (3.242 Chapter 3. This case occurs.'(x)which describes the change of the core potential due to the point perturbation. and the number of (positive) elementary charges of the core of the host atom by Z H .(x).1 differ as to how fast this decay proceeds.9) In further clisrussion. . We denote the number of (positive) elementary charges of the core of the impurity atom by Z r . approximately."'"x) L'() + Vg. the case of a substitutional impurity atom whose core contains almost the same numbers of protons and neutrons as the core of the host atom. (3.

This does not necessarily mean that the nuclei of the two atoms must have the same numbers of core electrons. as well as exchange and correlation contributions due to this difference. Both effects. on the other hand. isovalent impurity atom differs from the potential energy at the host atom not just by the screened Coulomb potential (3. but by the different core electron shells in the two cases. on the one hand. or N atoms substituting P atoms in Gap.or Ge-crystals. In close proximity to the center. bwansc there the spatial dispersion of dielwtric screening cannot be neglected. however. its variation over a primitive unit cell is relatively small. and also by exchange and correlation effects. are jointly termed central cell correcfzonu. that the numbers of valence electrons of the two atoms must coincide . because different numbers of protons of the atomic nuclei may compensate the difference of core electron charge. The potential energy of an electron at a non-isocoric. In fact each core has a iinite spatial extension because of its spatially extended r o w electrons (the nucleus of the core may be treated as a point charge).2. These additional forces are caused by higher moments of the core electron charge distribution. The perturbation potential b:(x) accordingly contains only electrostatic contributions of higher moments of the core electron charge distribution difference. We may state. In this context. Oneelectron Schrcdinger equation for pint perturbations 243 (3. that isocoric impurity atoms are approximately described by smooth or long-range perturbation potentials.3. it is called a long-range potential. The requirement of equal numbers of core charges implies. heside t h e elerlrostatic point charge forces already counted in [3. but also in other respects. The perturbation potential (3.as described by the term asovalent impuritr atoms. therefore. the additional core forces will also differ. which implies that it remains significant over a relatively large distances from the impurity atom compared to the lattice constant.11) where E is the static dielectric constant of the semiconductor material. because the core of thp impurity atom diffcrs not only by its charge number from that of the host atom. Examples for non-isocoric isovalent impurity atoms are C atoms in Si. If the cores of the host and impurity atoms differ. with the exclusion of a close environment of the impurity atom.10). the spatial dispersion of screening and the differpiirps of additioiiat rorc forces. whch always happens iI the atoms arc not identical. Both kinds of contributions decay more rapidly with . Consider first the case in which the charge eZf of the impurity atom core equals the charge eZH of the host atom core. the core electrons give rise to additional forces. The potentials which apply for non-isocoric impurity atoms are different.11) is distinguished in that. and. Deviations from this perturbation potential are to be expected in close proximity to the impurity atom.11).

l n thc case of a vacancy. = v. + . non-isocoiic substitutional impurities.(x) (0 v'(x) 0 for I x I 5 a f e u lattice constants for all other Ix1 (3._ _ _ Si Si_ _ _ Si Si Si Si v . we have v(.12) Short-range perturbation potmtials apply not only to isovelcnt. the occurrence of a short-range perturbation potential is particiilatly obvioiis.'(x) as depicted in Figure 3. like the determination of the periodic core potential of an ideal crystal.3a yields the potential profile of VJx) V. These show. 3 ~ The latter approximately represents the . Electronic structure of semiconductor crystals with perturbations Si . can ultimately be solved only by numerical calculations. The exact &termination of the pertrirhatiori potential is a problem which. v Figure 3. and the perturbation potential has the form shown in Figure 3 . gave rise to central cell corrections.244 Chapter 3. whicb in the context of the ibocoric impurity atoms abovc.'(x) of the missing atom. These arc also the potential contributions. pert -v.3: Illustration of thc origin of long-range (left-hand side) and short-range (right-haritl side) core perturbation potentials. Consequently. that the pet turbation potentials of isovdlenl impurity atoms differ horn zero substantially only over a distance of a few lattice constants. they are therefore described as short runqe. increasing distance fiorn the center than does tlic Coulomb potential of a point charge.3b. The remuval o f a Si at<nrn from the chain of S i atoms in Figure 3. but also to structural defects such a8 vacancies or interstitials. ncgative potential v. in fact.

first.11). i. superpositions . where the the short range potential is essential. due to a larger core charge difference between the impurity and host atoms.x) but those of the pertiirbed crystal and the summation runs over the o n e particle states u i occupied in the ground state of the pcrturbwl crystal.11). Just like the elwtron-core inteiaction potential. One-electron Schrljdinges equation for point perturbations 245 Finally we foiego the requirement that the core charges of the two nonisocoric atoms be the same.e. those with energy S eigenvalues which were already allowed for the ideal crystal. thereby substituting a triply positively charged host atom core. secondly.3.”. . Examples of this most general case are Cd atoms with their 2-fold core charge in a crystal of S i atoms with their 4fold core charge.2 Elect ron-electron interaction Hartree potential The Hartree potential V r t ( x z ) of the r-th electron is. The states of the first kind represent pure Bloch states only in zero-order approximation with respect to the perturbation potential. and a short-range potential which takes accoimt of all remaining differences bctween the cores d5 well as aspwts of the spatial dispersion of screening beyond those accounted for in equation (3. in higher approximations. those within the bands and. which accounts for the different core charges. Similar results can be derived for the exc~iaiig~rorrt~ation potential vzt(x)of the LDA mettiod.””(x) and the exchangecorrelation potential V. we describe these changes for the Hartrre potential V I y t ( ( x ) and the exchange potential V. ‘The effects of the two potential contributions are not independent of each other. those with F I I C ‘ I eigenvalues within the energy gap ~~ between the valence and conduction bands. the oneparticle states $ ( 2 here are not those of the ideal crystal.’‘(x) also undergo changes in the prrsence of point perturbationb. as before (see relation 2. From the physical point of view it is quite clear that the prrtiirbed rrystal ~ H two kinds of stationary one-particle states.2. the perturbation potential represents a superpobition of the screened Coulomb potential (3.2. The same bhort-range potential has a greater effect if the Coulomb potential. 3. given by the expression (3. Below. or Sn atoms with their Cfold core charge on a G&site in GaAs. is stronger. This comes about because the stronger Coulomb potential pulls the electrons closer to the core. In these cases.13) However. while.””((x) of the liartree-Fock approximation.49). the Hartree potential V.

and less localized if electrons are added. the extended part V. The first change causes a relative potential correction of order of magnitude 1 / N and thus can be omitted (a comparable ' . Vfi"(xi)becomes more repulsive if n is large. Second. and less so if n is small. we decompose the Hartree potential of the perturbed crystal into two parts. One says that the wavefunctions relax.14) with extd V g t d ( x i )= e2 / d3x' (3.&(xi) also differs from that of the ideal crystal. O. Electronic structure of semiconductor crystals with perturbations of other Bloch states have to be added due to scattering by the perturbation potential. We identify the extended states by and the localized states by quantum numbers doc. The states of the second kind. This assumption will also be maintained below. and the part V Z t d ( x i )stemming from electrons in extended states the part VAOC(xi) due to electrons in localized states v.4 and 3. are localized. quantum numbers v " ~ .16) k J and Here we assume that the electron i on which the potential acts is located at the center. C the remaining N . of The localized part VhOC(xi) the Hartree potential depends on the number n of electrons at the center.5). They become more localized if electrons are removed from the center. because the states of the extended electrons relax. For reasons similar to those causing the localized part VhOC(xi)of the Hartree potential of the perturbed crystal to depend on the number n of electrons at the center.n electrons are in extended states viztd ' Accordingly. in the ground state. because the number N of extended electrons is decreased by the localized ones and. The pure Bloch state property of being infinitely extended over the entire crystal also applies to these scattered states for most of the energies. Furthermore we assume that. First. There are two sources of this dependence. secondly. vrtd (3. the number of electrons which enter changes with n. at the position of the point perturbation (formal proofs of this will be given in sections 3. unlike the Bloch states. firstly.246 Chapter 3. which belong to energies in the forbidden zone of the energy spectrum of the ideal crystal. depend on n. n of the total number N of electrons of the perturbed crystal are found in localized states vO O. . the wave functions of localized occupied states v O over which the sum in (3. and .16) is L C extended.OC'.

into the two parts V. )respectively. this replacement. a positive excess charge arises in the vicinity of the localized electrons which screens the Coulomb potential of these electrons. the positional uncertainty is smaller than that of the extended ones. This change may be accounted for by replacing the localized part VAm(xi)of the perturbed Hartree potential by a screened potential Vh(%).61).19) Using relation (2.2. x‘) is the inhomogeneous position-dependent screening function of the crystaL Exchange potential As we know from section 2. In this connection. by definition. and simultaneously substituting the extended part V F d ( x i )of the perturbed Hartree ) potential by the Hartree potential V ~ ( x iof the ideal crystal.td(&) and l r ~ ( x of. the probability amplitude o the extended states f is reduced close to the localized electrons of the center because of Coulomb repulsion. Hence. One-electron Schriidinger eqmtim for point perturbations 247 approximation was employed previously in the derivations of the Hartree potential and of Koopman’s theorem in section 2. The change of the extended states is essential.f VX(Xi) = + Vfi(X2). We replace the extended part by the exchange potential V x ( x i ) of the ideal crystal and simultaneously With substitute the localized part by an effective exchange potential Vi(xz). VA(xi) is given by the expression where e .n occupied states are affected. the exchange potential describes the Coulomb interaction with the exchange hole which occurs because two electrons of the same spin cannot reside at the same position. .p”t(X. Accordingly.3. For the localized electrons of the perturbed crystal. their exchange interaction will be stronger than that of the extended electrons.2). (3.+ Then it follows (3.. we have v.17) where. however: because all N ..n ) extended and n localized electrons. we set Vkm(-) --t VA<xi) and V r t d ( q ) V~(xi). the ~ (N .which an electron a localized at the center feels.2.‘ ( q . It is therefore again expedient to decompose the entire exchange potential V. Accordingly. it follows that .).P”t(x.

Substituting trhe three potential parts (3. this expression may be written as . (3. Pert rirbation theory The Srhrodingrr equation of zcro th order reads [ H f q x ) ] ls'v(x) . they a e non zero and lead to corrections of the localized eigensolutions of ihe Schriictinger PqiiBtion (3. (3. is The occiirrenre of localized states at the center.p2/2na V(x).181.enerafly.20) where the summation over k inrlirdes only particles whose spin W k equals the spin LT? of particle i.60)occurs. I1 .91.).22) whcrt. 'I'hcse corrections will now be estimated by means of perturbation theory. tlip two othw potential parts L$(x%) and Vdk(x.)due to electron-electron interactions vanish completely.17) and (3. In gcnpral. equation (3.22) is exact.~ the rxpectation valri~ ($V. The index i is omitted because all electrons feel the same core perturbation potential.21) which rontaiiis L:(x) as the only potential. is maidy due to this potential contribution. If only one electron is localird at the center. 1 VAw I vv. [!ring (3. <. the core perturbation potential l<'(xz) the strangest. Hartree energy + The energy correction due to the Hartrcc potential for an electron z in localized stateqVt i s given in first order perturbation theory b . signifies the oneelectron Hamiltonian operator of the ideal ciystal. Electronic structure of semiconductor crystals with perturbations (3. the central feature of our considcrations above.19) into the oneelcctron Schrbdinger equation of the perturbed crystal. the various terms may bc arranged such that the effective oneelectron potential E(} of the 'x ideal crystal (2. If only one particle is localized at the center. The equation reads The three perturbativc potential parts in this equation have different ef fwts. as bcfore.248 Chapter 3.E U T h ( X ) .

multiplied by e 2 . One-electron Schrodinger equation for point perturbations 249 (3. The integral over X.211iIS) . (3. the expectation value of the perturbation of the Hartree potential becomes The energy Up' of ( 3 .24) With this.20) yields the expression "1 = . contrary to the ideal crystal case where the numbers of electrons with 'spin-up' and 'spin-down' are equal in ground state.(x'). . In terms of the total number n = n~+nl and the total spin projection M S = (1/2)(nT . (3. 2 4 ) is called the Hubbard energy. I ~ I'+v.28).e.26) 2 h l s ) . .2. it at an average position X in place of x The remaining x'-integral yields 1 because of the normalization of the wavefunction @. nl = -(n . and (3.23) We extract the factor ( ..( .) i -(no.. will be denoted by Uy.I ) J .3.( n + ( ~ v .28) is so-called the exchange integrcab The dependence of this integral on the orbital state v' = Uk has been ignored in expression (3. 2 2 For the expectation value (&. Exchange energy Next we will calculate the corresponding energy correction due to the perturof bation of exchange potential V%{x) (3. we set i. is the spin quantum number of the state v. the corresponding numbers n~ and nl of electrons localized at the center can differ. The latter depends on the spin of the electron because. equation (3."1) of the localized electrons.27) where g.. the two partial numbers ny and nl may be written in the form 1 1 (3. f o r not 2 1. x) I x-x' 1) from the x'-integral by evaluating E ' x '/ ' .) perturbation of the exchange 5 of the potential.t 1 1 I iu.19).

for example: which is installed in a si. Similarly. In thermodynamic equilibrium and at. i. thus. the paint perturbation enters into a more 01 less strong chemical bonding with the surroundiug atoms. This number is initially unknown. n the valence electrons in fact pass from the impurity atom to the surrounding crystal and the impurity atom is left behind as an Xv+-ion. 1bole is available I to occupy the states localized at the center. We assume the point perturbation to be elechically neutral. the .21) explicitly) the number R of electrons at the center must be known.and p-states of the P atom are involved in the formation of the valence band states of the crystal. Depending on i t s environment in the crystal. Electronic structure of semiconductor crystals with perturbations To solve the Schrodinger equation (3. have energies in the valence barid and not in the gap. This notation. Since the position of the Fermi level depends on the thermodynamic state of t. only 1 of the 5 valence electrons of the P atom i s available to occupy b c a l i z d states in the energy gap.1. The latter is denoted by X ” + . If a Si atom in a Si-crystal is substiluld by a boron atom. A phosphorus atom in a Si-crystal. of electrons at the center equals. for example. The number V of electrons of an impurity atom X involved in its bonding to the crystal and which.at-y charges at the atom without being such. T i means that n = 1 holds for the neutral hs phosphorus substitutional impurity in Si. I the latter. This question will now be addressed.c r y s t d on a regular crystal-site. we introduce some common not. the center is also a state dependent quantity. It can only be determined self-consistenbly because the Hamihonian which determines the states depends on it. Therefore. the number of electrons in localized states. of electrons at. which looks like the number of e1ernent. the number n. n -1 emerges if a P atom in P ZnS-cryst81 replaces an S atom.he semiconductor.e. Number of electrons at the center To say that an electron is at the center means occupying a state which is IocaIized there. and 4 of its 5 a2p3-valenceelectrons are hosted by these states. the same number of positive and negative elementary charges were added to the ideal crystal (as in the case of an impurity atom on an interstitial site): or removed from it (as in the case of a vacancy) : or removed and added (as in the case of a substitutional impurity atom). has the oxidation state P4+. A phosphorus atom. Therefore. The number n. is generally referred to as the oddation state of the atom. one has T = . Below.ations used in this context and estimate n for particular impurity atoms whose chemical bonding to the host crystal is known. This is no 7 .Y. is chemically bound like a Si atom. which means that in generating it.250 Chapter 3. temperature T = 0 K the number of electrons at the center may be found by self-consistently counting the number of localized states which belong to energy eigenvalues below the Fermi level. originates from its prior use for crystals and impurity atoms with pureIy ionic bonding. therefore.

The notations for the oxidation state and the charge state are summed up in the common symbol X('+Q)+(Q+). + + . therefore also the numbers n of electrons at the impurity atom.Of the 6 valence electrons of the S atom. Similar statements hold for structural defects. as before. 6 . are different in the two cases. Then some of the bonding electrons remain at the impurity atom. One-electron Schrodinger equation for point perturbations 25 1 longer true if the bonding is covalent or partially covalent. n = 8 (six electrons in 3d-orbitals and two in 4s-orbitals).V active electrons. denotes the number of valence electrons of the neutral impurity atom. positively or negatively charged ions can also be introduced into the crystal. Oxidation and charge states coincide in this case. Interstitial Fe atoms in Si are found in the oxidation state F e o f . amounts to Vi . the charge state of the impurity atom prior to its incorporation into the crystal was taken to be neutral.5 = 1 are available for occupation of localized energy levels in the gap. the distinction between the two can be expressed most easily: the charge state counts the elementary charges of the atom outside the crystal. i. The reason is that. are sometimes called active electrons. In the purely ionic case. the oxidation state of a center in charge state Q will be X('+Q)+ if the oxidation state of the neutral center is V . and the oxidation state counts its elementary charges inside..e. If a particular perturbation center X is not neutral for the lack of Q electrons. V Q valence electrons are not available for occupation of localized states. in the sense just specified.3. instead of 2 electrons in the case of the neutral center S4+(O+). substitutional in the oxidation state Fe4+. The oxidation states V and. For substitutional TM atoms. However. in this case. the number V of electrons of the T M atom which occupy bonding valence states.(V Q ) if V. and the true number of its elementary charges differs from V. is denoted by S5+(l+). for example. and atoms introduced in a neutral charge state can have electrons removed or added within the crystal.and other tetrahedral semiconductor crystals both substitutionally as well as interstitially.e. The n valence electrons of the impurity atom. and the number n of electrons at a TM atom equals the number of its valence electrons. In the first case. Transition metal (TM) atoms can be installed in Si. The charge state should not be confused with the oxidation state. and are available for occupation of the localized levels in the energy gap. one says that the charge state of X is Q and writes X ( Q ) (where negative Q mean surplus electrons). and in the second case the value of n = 4. Generally. A simply ionized sulphur atom in a Si-crystal. which remain after the departure of the V electrons into the bonds with the crystal. V equals the number of electrons which are left at the atom after it is bound to the crystal. i. In the case of an impurity atom with Vi valence electrons one has n = Vi .2. The number n of electrons which are available. The oxidation state is therefore T M o f . Interstitial impurity atoms are only weakly bound. the number of active electrons. is almost zero. So far.

he solutions qVof Ychrodinger equation (3. Which solution methods can be applied with succcss depends decisively on whethe1 lhe core yrrt iulmlion potential is long. Far hhe derivation which follows. For long-range potentials the dec iations from lattice trauslation symmetry are relatively weak. the POt.es to Ihe core part V ~ ( X of the pert.~.iirbation pot. Of course. For the latter? Vh(x) and Vk(x) may be treated as smooth external potdialii which. together with V.or short-range.entials Vf(x)are ruled out from the very beginning. 3.his wxmption.he smooth perturbation potential VieVt(x) a point of perturbelion.21) which are smooth if L’.21).21)!i.hpotential U ( x ) is allowed.ically smooth if V&(x) has this property because these potential parts are dctcrmined by t. The wwelunction dependence of Vh(x) and L’i(x) requires self-consistent solutions of the Schriidinger equation. T he latter is called the LPffective mass equation’.ant assumpt.pdurbations of the Hartree and exchange potentials l7L(x) the and ViCx). any smo0t. Point perturbations with Coihmbic core perturbation potentials are still allowed.urhatiozt potential V A T t ( x ) this equation. arc automat. which drastically simplifirs the bolution of t h ~ Schriidinger eqiiation hi the casr of an ideal crystal is perturbed by both kinds of potentials.3 Effective mass equation ure start with the Schrodinger equation (3. which we will derive in the following section. in a certain sense.t(xj of eqiiation (3. but only for short-rangepotentials in an e s s e a t d mannet-.(x) is also. In this case the Scfirodinger equation. it does not iulerfere with its derivation. In this section we do not intend to solve this quabion explicitly hut iclther to t.h t.With the background analysis set forth above. Althoiigh the self-consistency demand is transferred to the effective mass equation.ransform it into another equation.he effective mass equation. The other parts of thr t o l d perturbation potential V&. may be decomposed into two quations. t h r lattice translation symmetry. and one for the perturbation potential.8) of the perturbed crystal in the form (3.‘(x)! add lip l o form a smooth total perturbation potential i( ) ’x. although the Coilonib form of this potential is not necessary for the derivation of t. the cffective mass equation? aliith can be solved more easily.ential need not be t.because these caiinot be considered to I c smooth.ion we will make relat. iiriport. In conjunction wit. which was solved previously. we are now sufFiciently p r e pared to address t h e solution of the one-electron Schriidinger equation for the crystal with a point pcrturbation. The most. ) in This potential part is supposed to be smooth on the atomic length scale. one for the periodic potential of the ideal crystal. point pcrtiirhatioiis with shos-t-range core pert. This is important innsmuch as it becomes possible in this way to utilize the effective mass equalion not only €01 point perturbations with Coulombir core perturbation poten- .

Therefore. operator by the effective mass m:. In this mat. 3. . we rewrite the Schrodinger equdion (3. the energy of an electron of an ideal crystal depends quadratically on quasi-wavevector k.ter.29) for t. it is generally a tensor. results. one may suspect that the influence of a perturbation potential V(X) on an &&on of the cryisla1 can be calculated in an appr0ximat. The procedure described above needs.ivc mass includes the effects of interaction of the electron with the periodic potential of crystal. The e&ct. To provide this. open so far.3. ultimately: a mare easily solvable equation. in the same way that the energy of a free electron depends on its momentum.he fact that. However. so that.j(x)in order for bhe effectivp mass equation to be applicable.ion. how the wavefunction of the e f l d i v e mass equation reiates to the wavefunction of the original Schrodinger equation. The resulting Schrodinger equation represents the one-bend e#ective mass eyuatian in its simplest form It can be solved much more easily than the original Schrodinger equation? which includes the periodic crystal potential ill explicit form.he perturbed crystal in stages.ter generally differs horn the mass of a free electron.ion. For a siibstitutioiial P atom in Si. quest. the value of the lat.ions have to bc addressed which have been left.3. for example. Effective m 9 equation a5 253 tials. which are smooth on the atomic length scale by definition. hilt also for macroscopic perturbations. we will employ t. the free electron mass 7 n is replaced by the effective mms rnc of the particular band and critical point chosen. t. such 8s that associatd with an external electric Geld.e. for example. and the matter of what conditions must be placed on the perturbation potential V(x) and the wavefunction 7. of COZITSC. and if il can be reduced to a scalar maw.29) in the Bloch representation. Having in mind the effective mass description of the band energy versus quasi-wavevector k relat. further justificat. namely the effective mass equation.1 Effective mass equation for a single band To address these questions and derive the effective mass equation for a single band.he effective mass equation is twsentinlly the same a8 the Schrodiuger equation for the hydrogen atom whose solutions are already known. i.e way as follows: One eliminates the periodic potential of t h e oiic cltrtron Schrdinge~ equation for the perturbed crystal! while simultaneously replacing the free mass m in the kinetic energ). in the vicinity of critical points of a certain band v .3.. The goal of the following consideralions is l o simplify the oneelectron Schriidingcr eyiiation (3.

are small compared to the Fourier coefficients (kll. meaning over all Brillouin zones. the assumption made at the outset that U ( x ) should be a smooth potential. v‘k’ + (3.32) To transform this equation into the effective mass equation.33) is extended over the entire infinite k-space. they are non-zero only if k is a reciprocal lattice vector K differing from zero. This is done by assuming that the change of U ( x ) over a primitive unit cell is small in comparison with the change of the periodic crystal potential t ’ ( ~ ) such a cell.35) .30) with the expansion coefficients given by (vk I = d3xlpXx)~(x).31) Since the (pYk(x) are eigenfunctions of H with eigenvalue E. using the same notation introduced previously in Chapter 2. more strictly speaking. for large k-vectors. the Schrodinger equation (3. (3. To formulate the condition for smoothness in over this sense quantitatively. K # 0 .zero for for Ikl w ithin first 3 2 Ikl outside f i r s t BZ << I(KlV)l. (3. must be specified further. for kvectors outside of the first BZ. According to formula (2.34) The sum in (3.4.(k).’) of the periodic crysta1 potential V ( x ) . (3. We have (3.29) takes the following form: [ E y ( k ) 6 v f y f 6 k k ~ (vklUjv’k‘)] (Jk’lV) = E ( v k l $ ) . The latter components were calculated in section 2. Smooth functions U ( x ) in the above sense have Fourier coefficients (klU) which. we decompose U(x) in a Fourier series. Electronic structure of semiconductor crystals with perturbations expanding ~ ( xwith respect to the complete set of Bloch functions ) whence ‘pvk(x).254 Chapter 3.161). This means that the smoothness condition for U ( x ) may be expressed its essentially non .33) with Fourier coefficients (3.

the changes of U(x)over a primitive unit cell must be small compared to the energy gap. 0 the small energy deviations also correspond to small k-values.(k).q between the valence and conduction bands. ( k ) as a function which has yet to be determined.k(x) can be approximately replaced by their values at k=0: U v o k ( X ) ZS . (3. which according to (3.3. The right-hand side of (3.35) have to be considered exclusively. the only modification being the replacement. we assume that the wavefunction $(x) can be set up exclusively from Rloch functions of only one band YO. the inequillity (3. well BY of k by k . the band edge lies at k :. The restriction of the location of the band edge to k = 0 can be omitted. Secondly.36) is of the order of magnitude of the change of the perturbation potential U ( X ) over a primitive unit cell of the direct lattice. a1VUI with a as lattice constant.k in the corresponding equations.36) It states that. It turns out that this requirement has no contradictions if the perturbation potential is smooth. as . It is assumed that Fvo(k)differs from zero only for small k-vectors in the sense used in equation (3. (3.37) may be written as . i. and the derivation procedure can also be applied to band extrema other than the center of the first B Z . for a perturbation potential U ( x ) to be smooth and our first condition to be fulfilled.35).38) holds approximately. and relation (3.38) In the following subsection 3. it will be assumed that for small k-vectors.32).mo(x). Fourthly.35) can be estimated by a characteristic band structure energy.e. that $(x) should be of the form (3.3. additionally. If.38) the wavefunction (3. like the fundamental energy gap E. The thzrd requirement refers to the function F. Effective mass equation 255 The left-hand xlde of the inequality (3. The above four conditions will now be used to simplify the Schrodinger equation (3. Applying relation (3. With this.2 we will see that the two last requirements can be justified when eigenstates of the perturbed crystal exist having energy eigenvalues just above and below the edge of band vo. that is. of the R X center k = 0 by the non-central critical point k. the Bloch factors u W k ( x ) in the Bloch functions p. and if only these eigenstates are considered..35) takes the form alVUl << E g .37) with F .3.

Equation (3. (3. K (3. the envelope. O ( X ) ~ Y l ( X ) . make The two ronditions conccrning the smoothness of U(x) and Fvo(x) it possible to represent the matrix element (uk(l/(v’k’) the Schrodinger in equation (3.33) of U(x) and the product form of the Bloch functions p v k ( x ) .40) Therefore $ ( x ) may bc written as $44 = ~ . obtaining Furthermore.45) . A lattice point R is associated with each unit cell.32) in a substantially simpler form. The envelope function. (3. so that the sum runs over all lattice points of the periodicity region.k) .41) means that the truc wavefunction + ( x ) is obtained by enveloping the rapidly oscillating Bloch lactor uvgo(x) with the smooth cnvelope function Fuo ( X ) . by definition. only terms of the form exp [i(k’ k” . we transform the integral over the periodicity region into a sum of integrals over the unit cells of this region. whence F. We rewrite this element using thc Fourier representation (3.K.(x) of the function F. it follows that + C .43) K With this.44) f i wherein the notation for the so-called Bloch integral (3. Because of the lattice periodicity of the Bloch factors.42) takes the form (vklUlv’k’) 1 = - C ( k . With K as an arbitrary reciprocal lattice vector. i s a bmooth function. The summation over them can be executed easily.256 Chapter 3.(x) is termed the envelope functzon or.x. R] remain under the lattice sum. & k (3.k’ + KIU)Ci$’(K). expression (3.(x) = 1 -CFvo(k)eik.i(k’+k”-k)-R R = G3 Sklfk’l-k. Electronic structure of semiconductor crystals with perturbations Tihe k-sum is the Fourier transform F. in short.41) The function F.(k).

the Bloch integrals of equation (3. Substituting this relation in expression (3. Therefore we need the matrix elements (vklUlv’k’) only for small k and k .. ud(x) and uU.6 kk’ t.50) One can easily prove that this transformation is correct by expanding E. The Bloch components of the wavefunction @(x) in the Schrodinger equation (3. The Schrodinger equation now decomposes into separate equations for the various individual bands.(k) in a power series and by using the identity .47) (3.o(x). respectively.32) for the perturbed crystal has been done . and applying the orthogonality of the Bloch functions. To this end we multiply by ( /exp ( i k .32). differ from zero only for small k and k’ because of the smoothness of the envelope. (vkl$) and (v’k’lg). .. With regard to the smoothness requirement for the potential U(x)..(k): This equation will be transformed from k-space into coordinate space..37).46) Approximating the Bloch factors u. x) = (xlk) and sum over k. The coupling between different wavevectors remains in place. (3.(k)Fuo(k) k ( Ik) = X Ev0 (-iVz) Fvo(x). (3. the decisive step in simplifying the Schrodinger equation (3.the coupling between the different energy bands caused by the perturbation potential has been eliminated.3. We employ all results achieved up to now in the Schrodinger equation (3.32).44) we obtain (v kl U Iv’k’) w (kl U 1k’)6.44) for (vklUlv’k’) yield no significant contributions to the Schrodinger equation (3. (0) = . so that (vklUlv’k’) N -(k a 1 .k’lU)C$t’(O). and these equations can in fact be solved by a one-band ‘Ansatz’ of the form (3.k(x) and U v l k t ( X ) by.32) if K # 0. (3. This can be processed relatively easily. obtaining the following relation for F.45) c : ~ : ( o ) as follow c.. Effective mass equation 257 has been introduced (0 = G3Ro). the ’ terms in expression (3.3. The 1 a ) first term on the left-hand side thereby becomes C &.48) With this relation.

Also. Equation (3. Short-range perturbation potentials.258 Chapter 3. are not smooth. for example. Other problems which can be solved with the help of the effective mass equation include artificial superstructures in a crystal and external electric fields. it.(x) If one further replaces Evu(-iVz).55) is therefore the desired effective muss equation The eigenfunction Fvo(x) of this equation plays the role of an envelope function for the Uloch factor uvoo(x)in equation (3.) = E. ( x ) . These assumptions are decisive.his context .55) is a suitable instrument for the solution of a series of important problems of solid state physics.which results in the formation of excitons as pointed out in Chapter 2 - 1 (3. d O ) . as well as the k-independence of the Bloch factors. the effective mass equation (3. respectively. The essential requirements involved in the derivation of the effective mass equation were the smoothness of the perturbation potential. one finally gets the following equation for F..-a2 2m& h2 I U ( x ) F. the Coulomb attraction between electrons and holes . (3. Equations (3.52) and the right-hand side of (3.204). initially conjectured and now verified. These will be treated later in section 3. Point perturbations with smooth potentials are only one example of this. and assumes an isotropic effective mass m+. With this. Nevertheless.41) for the true wavefunction $J(x). 2mg (3. is quite clear that the influence of the perturbation potential can be approximakly determined from an equation in which the periodic potential no longer appears and the effective mass replaces the free electron mass. With the derivation of this equation.(x) = E F . ( x ) ..8.49) can be written in the form C ( x l k )(klU l k’Pm (k’) kk‘ U(x)Fm(x). in accordance with equation (2.7 and 3. by a quadratic function of -iVz7 which is justified because of the smoothness of F .55) are also called envelope function equatioas in t.55) . Electronic structure of semiconductor crystals with perturbations The second term on the left-hand side of equation (3.(-iV.(O) h2 + -(-iVx)2.53) or (3. then it follows that E.54) and [ L . ( x ) .49) inluiediately becomw E F . the smoothness of the wavefunction and its composition of Bloch functions from only one band. and are often not fulfilled.

53) in coordinate space is more complicated. in particular higher order differentia1 operators occur which make solution of the eigenvalue problem practically impossible.9.3.53). but the perturbation is introduced through boundary conditions. for example. or if no perturbation potential is present. The practical use of this equation depmds.(k) of the band under consideration. however. We will undertake this program now. therefore.3. As demonstrated in section 2. the effective maw equation has to be modified in a way which will be indicated later in section 3. Regarding the perturbation potential U ( x ) and the envelope function F ( x ) .e. no more difficult to solve than an ordinary Schrodinger equation with an external potential. As we have seen. IIowever. p-perturbation theory. The elements of this matrix are relatively simple linear and quadratic functions of the components of k. In the vicinity of the minima or maxima of non-degenerate bands of cubic crystals one has a purely parabolic and isotropic k-dependence. on the dispersion law E. In the case of degenerate bands this suggests.7 on k p-theory. we pose the same requirements . which are exact up to the first order in the k . Because of the non-parabolic and anisotropic dispersion laws in the case of degenerate bands. This does not involve a major difference if the one-band effective mash equation can be solved in k-space. p-perturbation (see formula (2. completely solves the eigenvalue problem for an electron in a crystal in the presence of a smooth perturbation potential. such as in the case of artificial superstructures like superlattices and quantum wells. the parabolic and anisotropic dispersion laws of degenerate bands occur in this theory through diagonalization of the matrix of the Hamiltonian with respect to a basis set of Bloch functions Ivk)'. the effective mass equation (3.3. This applies if basis functions other than plane waves are better adjusted to the symmetry of the perturbation potential as.49). as we have seen. A resolution of this situation is offered by k . and the effective mass equation is. not to take a onecomponent effective mass equation as starting point.2 Multiband effective mass equation The oneband effective mass equation in its general form (3. but a multi-component one which is obtained by writing the Schrodinger equation for the perturbed crystal in the approximate Bloch basis 1vk)l. the Coulomb potential of an impurity atom. in the form of equation (3. 3.339)). Effective m a w equation 259 may be treated by means of this equation. To account for external magnetic fields. for various reasons it can be necessary to transform the effective mass equation into coordinate space and to solve it there. i. derived in the preceding subsection. one then in general has non-parabolic and non-isotropic dispersion laws. This picture changes for bands which display degeneracy in the extreme.

57) The matrix ’(vklHIv’k’)’ of the unperturbed Hamiltonian H is diagonal with respect to k.29) in this representation takes the form ‘(vklH uk + Ulv’k’)’ ‘(v’k’l$) = E’(vk($).59) is valid independent of whether the two bands v and Y’ arc dcgeneratc . Thus the matrix elements of // with respect to first order Bloch functions Ivk)’ are approximately given by the relation (vkl U Idk’)’ = (klU Ik’)buu. (3. One obtains The factor at (klVWlk’) in equation (3. which expresses the first order Bloch functions Ivk)’ in terms of Luttinger-Kohn functions.59) which corresponds to relation (3. Terms of this order of magnitude are to be neglected within the framework of effective mass thpory. these are Bloch functions in zero-order k .3. For the wavefunction $(x) of the perturbed crystal.1. This is due to the k-dependence of the Bloch factors in )vk)l which has been omitted in subsection 3. In the terminology of section 2.48) of subsection 3.1. v’ with the blocks referring to degenerate bands.56) and the Schrodinger equation (3. This implies that the off-diagonal elements of U ( x ) are of the order of magnitude of the relative change of U ( x ) over a primitive unit cell.kl$)(xtvk)’.58) has the order of rnagiitudr of the lattice constant a. (3. unlike this ielation. However.48) which gives the elements of U with respect to approximate Bloch functions their Bloch factors u v k were replaced by u d .3.3. the expansion with respect to the approximate Bloch functions reads ?clW= c uk ‘(. it follows that the diagonal elements ’(vklUlvk’)’ arc the Fourier transforms (klUJk’). (3. thc matrix ’(vklU lv’k’)’ has also lion-vanishing off-diagonal elements with respect to I / . as can easily be seen replacing p by x by means of Heisenberg’s quation of motion.339).both should be smooth in the sense that they change much less over a primitive unit cell than the periodic crystal potential V ( x ) does.48) of subsection 3. The diagonal elements ’(vk(U(vk’)’ of the perturbation potential U may be calculated by means of relation (3. . and block-diagonal with respect to the band indices v . Note lhat equation (3.1.7. Electronic structure of semiconductor crystals with perturbations as in the previous subsection . The non-vanishing off-diagonal elerrienls ‘(vklU)v’k‘)’ may he calculated in the same manner as the diagonal elements before.260 Chapter 3. Using relation (2. 11’. just as in relation (3. p-perturbation theory or Luttinger-Kohn functions. k’.

Using the Ansatz (3.7 in second order k. we will examine the case of non-degenerate bands.336) for E?(k). vj(x)may be written as (3. The second term of @(x) of equation (3.631 for l(vk)H]vk)'. Non-degenerate bands WTeassume that p(x) can be expressed in terms of the approximate Bloch functions of only one band v g ? so that '(vkl@)= b. the Schrodinger equation (3.1. p perturbation theory. With the Ansatz (3. We therefore obtain the same expression V(x) as in equation (3.60) $(x) = CFw(k)(xlvok)l.62) does not occur in the corresponding equation (3. and the diagonal elements are the eigenvalues Ez(k) of H calculated in section 2.41) for +(x).3. ( x ) over a unit cell.60).61) Employing expression (2. Before simplifying the Schrodinger equation (3. it follows that where &(x) is the Fourier transform of F.(k) in coordinate space.41) above.we obtain where hi&8 are the elements of the reciprocal effective mass tensor according to formula (2. Again terms of this order of magnitude are again to be neglected within the framework of effective mass theory. its relative magnitude with respect to the first term is of the order of the relative change of the envelope function F .337).(k).57) is approximately diagonal with respect to the band indices. k (3.57) still further for the actually interesting case of degenerate bands. The Hamiltonian matrix '(vklHlv'k')' in (3. even degenerate bands are not coupled by perturbation potentials U if these potentials are smooth.3.3..59) for '(vklp) and expression (3. Mective mass equation 26 1 or not. In fact.F. which was neglected in subsection 3. This term is again due t o the k-dependence of the Bloch factor in Ivk)'. Employing expression (2.334) for the approximate Bloch functions jvok)'.57) yields .

1. an effective mass equation was obtained that did not yet contain this approximation. First we consider the : case without spin. however. we set (3. In the earlier derivation of subsection 3. we can represent $(x) as a superposition of the Bloch functions Ivrnk)' in first order k . b Rloch states of energy E w ( 0 ) ' T arc. The three degenerate . from the assumption of isotropy of the band structure.7). we have This equation is in agreement with the effective mass equation (3.(O) exists with either symmetry rhs or r depending on whether spin is omitted or not. we assume that at k = 0 a degenerate band level E.53) if the latter has E. If the effective mass tensor reduces to a scalar quantity ( l / m ~ & ) 6 ~ 0 . then (3. p perturbation theory thus produces this equation automatically in parabolic approximation. as before. which was invoked only later..3. it approximately follows that (3. If we are interested in eigcnstates $(x) of the Schrodinger equation of the perturbed crystal whose energy eigenvalues are expected to be near the valence band edge.262 Chapter 3. Thus.(--zV) replaced by a parabolic expression in the components of -iV. Electronic structure of semiconductor crystals with perturbations Fourier-transforming this equation into coordinate space. The derivation of the effective mass equation based on k .67) . Degenerate bands We direct our attention to the valence band maximum of semiconductors with diamond type structure (see section 2.distinguished. by an integer index m.66) As above. Accordingly.65)yields the effective mass equation in the form (3.refraining. The advantage of the derivation of the effective mass equation within the framework of k * p-perturbation theory is clearly manifested when degenerate bands are considered. which we will address next. in the case of non-degenerate bands.55).. p perturbation theory. The Bloch functions at k = 0 arc therefore written as ) o m O ) .

71) In the case of the & I valence band the Hamiltonian matrix is given by relat. Using equation (2.i. and F (x)for the vector (F. . With t.(x). explicitly.ion (2. Now.(x).(x) as the Fourier transform of F. With this. They vanish if v # wm'.(k) in coordinate representation.59).F. f l I ~ = (3.344). The matrix elen ments '(vklUlvrn'k')' of the perturbation potential U follow from equation (3. @ ~ ~ (3. the Schrodinger equation (3. the matrix elements '(vklHlvm'k')' may be written as where the coefficients D: . expression (3.341).51).3.ion (3.67) for '(ukl$) is substituted into the Schrodinger equat.! +$ 1 Fm'(X) = E F m ( x ) . the equation + Ci(X)h. are defined i equation (2.57).. For v = urn' they differ only from zero if m = m'.70) ($ follows.(x)).. EEective mass equation 263 with F.3.342).his equation may be written in matrix form as * Dm : . Using the notation D for the fourth-rank tensor for the unit matrix 6. The subspace of valence band states is approximately decoupled from the remainder of the Hilbert space. t.his. F.57) takes the form Transforming to coordinate space and taking account of relation (3. the envelope function equation then reads.

e.78) The energy origin in (3. ..77) v % .) * s = i-(& N 1 6 1 3 +Mp:.i& a.264 Chapter 3 . is to be added to the Hamiltonian operator H . .74) was moved to the valence band maximum.p becomes Hk. here are differential operators defined as follows: 1 Q = --(L 2 + nf)(a: + a.7. Using the arguments of section 2. derivatives of the type 62/6z2 are denoted by symbols like a. i ' one arrives at the following $-component envelope function equation: The quantities d. and assuming a sufficiently ' large spin-orbit splitting energy A.353).74) makes it possible to calculate acceptor states and hole bands in superlattices of the diamond and zincblende type semiconductors.76) (3. Electronic structure of semiconductor cry.) .Ma:.The envelope function equation then reads U It is advantageous to first transform this equation into the angular momenU tum basis l j m g ) .staLs with perturbations Here. If interference terms between the k ' p-interaction and the spin-orbit interaction H . Thereby.. the coupling between the Ii and r$ valence bands may be neglected. with j = $. . Hk. For the T valence band. 2 . therefore. One can derive a similar equation within the Kane model of the rs-valence-band-rs-conduction band complex of zincblende type semiconductors. The envelope equation (3. [3.) .75) + = --(L+ 5n/I)(d2+ a. and those of type a 2 / d r d y by symbols like a&. are neglected.B.=.] (L.-(2L (3. which was previously located at A/3. and secondly the spin-orbit interaction opers) ator H. .. also spin-dependent envelope functions Frrw(x. which has the consequence for D that the matrix elements of p are replaced by those of ii from equation (2. (3. $. i.in which the operator fiso is diagonal.2iNa.M ) ( a2 . Firstly.a. one has to use spindependent Bloch functions (sxlvmak0)' and.R . before one proceeds to solve it. Consideration of spin leads to two changes. the representation of the latter in the approximate Bloch basis leads to a * k-independent tensor Hs.

4. we may use the effective mass theory derived in section . Donor and acceptor states 265 3. For impurity atoms with lAZl > 1. We denote the difference of the core charge numbers of the impurity and host atoms by AZ = Z I .() 3. if it is smaller. The effect of a non-vanishing VA(x) will be discussed later. these potentials.3. In this sense we can speak of positive and negative point perturbations the point perturbation is positive if the core charge number of the impurity atom is larger than that of the host atom. In Chapter 1.() potential. it was pointed out that such changes occur at the bottom of the conduction band and the top of the valence band .4 Shallow levels.22). have the effect that only one electron or hole can be bound at the center.79) and assume that it is non-zero. V'X is itself the entire perturbation .() expression (3. For impurity atoms with only one valence electron more or less than the host atom. Shallow levels. effective mass equations must be written down for those critical points of energy bands where changes of the spectrum of energy eigenvalues dae to the perturbation potential are to be expected.3.21) for the perturbed crystal. To solve the one-electron Schrodinger equation (3. i.22) with the potential V ' x of (3.e. Below we will concentrate on such point perturbations. as a rule.80) In general. One still must add the Hartree potential Vh(x) and the exchange potential Vfr(x) caused by other electrons localized at the center.() the one-particle Schrodinger equation (3. i. For the pcrtiubation V'x of the core potential. The sign of AZ can be both positive as well as negative. (3.for impurity atoms with A 2 > 0 discrete levels appear in the energy gap just underneath the conduction band edge. The most important point perturbations of this kind are isocoric substitutional impurity atoms. V ' x does not yet represent the entire perturbation potential in .e. . the Hartree and the exchange parts of the perturbation potentials vanish. atoms from rows and columns of the periodic table which are close to the row and column of the host atom which is substituted.XI?. and the one-particle Schrodinger equation has the form (3. we m a y use .80). negative. Vb(x) and Vfr(x)do not vanish. For this one electron or hole.11) which here we write as (3. Donor and acceptor states We will now explore stationary states of a semiconductor crystal caused by point perturbations which givv rise to smooth long-range perturbation potentials V'(x). Here.

as effective masses of electrons and holes.81) Ti2 = -----k2. the k-dispersion of the two bands is assumed to be isotropic and parabolic in the vicinity of k = 0. The valence band edge zs found at that point for many semiconductors including the ones mentioned. therefore. we will initially proceed with the above simplifying assumptions. For reasons which will become clear below. both for the conduction band edge as well as for the valence band edge.83) (3. Electronic structure of semiconductor crystaIs with perturbations and for impurity atoms with A 2 < 0 one has such levels in the energy gap just above the valence band edge. In writing down these equations we start with a simple twc-band model.1 Hydrogen model For the hydrogen model we have the two effective mass equations (3. the conduction band edge does not lie at k = 0. Nevertheless. for many semiconductors such as Si and Ge. and ml.86) .4. In reality. and the maximum of the valence band (v.82) with rn.84) In the usual form of a Schrodinger equation they read (3. The minimum of the conduction band (vo = c ) . Furthermore. the model is often referred to as the hydrogen model 3. respectively. (3. = w) are assumed to be non-degenerate and to lie at k = 0. whence we have (3. The relevance and necessary improvements of this idealized model are yet to be discussed separately. &(k) 2m. Effective mass equations are needed. but there is degeneracy between heavy and light hole bands at k = 0.266 Chapter 3.

we get the discrete energy levels & of principal quantum niimher 71.E ~= .~ * / n ~ ) or (3. we know that h r an dttrtlclite potential. Thew dibcrele levels lie in the emrgy gap between the conduction and valence bands where. . there is a continuum of positive eiierpy eigmvalues and. as we know. .86)). With E g FY 13. n = I . The orders of magnitude of the energy Eg and the length ag can be estimated easily. angular mumedurn quantum number I 0 and magnetic quantum number m . We consider first the cwe of the conduction band. no energy eigenvalues can appear in an ideal crystal.(e'm//2ha) denotes the binding or Rydberg energy of the hydrogen atom. The m~av~fin~rtioii FTdm(x) for principal quantum number n = 1. and constant factors these are the Schrodinger equations for charged particleu in the potential of a point charge. From this it follows that for a positive point perturbation (upper sign in equations (3. just like in the case of the hydrogen atom. it follows lhat (3.90) where a g = ( h 2 / e 2 m )denotes the Bohr radius of the hydrogen atom. but no bound statrs at negative energies. and for negative point pertiirhations such levels are exppctpd just above the valence band edge.2. discrete e n e r a levels are to b e expected just below the conduction band edge. Conduction band Transferring results from the quantum mechanical treatment of the hydrogen atom to our present situation.6 eV. (3. . Fur repulbive potentials there are only pusitixe energy eigenvalues. Donor and acceptor states 267 Apart from notation.. ( m z / m )= 0. c = 11. in addition.91) . there ale discrete energy levels which occur for negative energies. 2 . Shallow leveb.: = 0.87) with (3. as ( E .4. From experience in quantum mechanics.5 A . .0 reads ~ (3. signs.4 and a = 1.88) where Ef .851.89) with (3.3.

4). This leads to a change of the density of states in the continuous part of the energy spectrum (the definition of the density of states is given in section 2.5). The smoothness requirement is therefore fulfilled very well. The designation shallow levels is used in this situation. localized electron states (see Figure 3. which we will discuss in the next section in somewhat greater detail. Between the center of the first B Z and its edge. For each bound state of negative energy a state of positive energy is therefore excluded from the energy spectrum. This means that the localization of an electron at an attracting impurity atom is weak if considered on the interatomic length scale of the crystal. Their amplitude at the positive center becomes larger..4). The localization radius a g is clearly larger than the distance between two crystal atoms. Even closer are the states with n = 2 .92) Compared with the width of the energy gap which is of order of magnitude 1 el/.4 (=) AM 29 A. In Figure 3. this change takes place such that the total number of all states in the presence of the perturbating potential. Exactly this is to be expected considering the smoothness requirement made at the outset. 3 . . They are manifested in the fact that the eigenstates. the discrete energy level El lies closely below the conduction band edge (see Figure 3. which are evenly spread out over the entire crystal.268 Chapter 3. The wavefunction for energy level El decays exponentially with distance from the core of the impurity atom with the characteristic decay length a g . which states that only Fourier components of small wavevectors k should contribute to the wavefunction. which is approximately 2. are scattered by the Coulomb potential. Fcloo(k) therefore falls off by about 4 powers of ten.5 11. remains the same as the total number of states without the perturbating potential. . and further away from the center it is smaller..5 A. In contrast to band states. therefore.4 the localization of the wavefunction in k-space is also indicated.93) At the edges of the first B Z one has k FY (./a) and a g k M w ( a g / a ) FY 10. Recalling the theory of the hydrogen atom. Electronic structure of semiconductor crystals with perturbations a g --" 0. Omitting a k-independent factor. We can also examine the validity of this requirement quantitatively. Changes also occur in the continuum of positive energy eigenvalues which are allowed even without Coulomb potential. including the bound states at negative energies. . it is known that the effect of an attractive Coulomb potential is not restricted to the formation of bound states with energy levels in the previously forbidden negative energy region. which were previously spherical waves. the Fourier transform of Fcloo(x)is given by the expression (4. (3. According to Levinson's theorem. we have. .

n = 1 and 1 = m = 0.^ for shallow impurity levels appended to an isotropic parabolic conduction band can be immediately iransferrd to an isotropic parabolic valence band.89) .95) The pcrtinent wavefunctions are localized at the perturbation center.3.e spat:e and in kspace far mibslitutional impurity atoms with either posit. The energies ol thew levels are given by the exprcssiorrs En . The levels act as donors of elwtctruns for A 2 > 0 and ss acceptors of electrons for A 2 < 0. The wavefunction of the ground state. Below. The occupation of the shallow levels by eI&rons is presented f in the lower part of the figure.y core charge nunthers and the h o d core charge numhers (upper part o figure). we will writs them down without further derival ion. S h d a w lev& Donor and acceptor fitates 269 AZ a 0 dZ.-' z.0 L 1 O k r\ O k Figure 3. Valence band For a negative point perturbation there appear discrete energy lpvels in the energy gap closely above the valence band d g r .ive or negative differences A 2 beOween the impuril.94) (3. The abovr-Inmtionfd result.4: Illmtration of shallow localized States in coordina1. EB (3.4. has the form (3.

according to the above results.according to Levinson’s theorem by one if only the n = 1-level is counted. With this. There.I. If the temperature is increased this electron can easily be excited from the shallow level to the conduction band. We will discuss this later more exactly. it is singly ionized. also one less valence electron than in the host atom. The impurity atom remains in the single positively charged state.96) as the effective Bohr radius.e. it is no longer localized but spread out uniformly over the whole crystal. For simplicity. with one positive elementary charge in the core and. one can proceed on the assumption that nothing will change due to the impurity atom regarding the number of states in the valence band. According to Levinson’s theorem. representing a freely mobile negative charge carrier. we consider an impurity atom with Z I = Z H . The additional impurity electron has to reside in the lowest unoccupied energy level.270 Chapter 3. First of all. i. The resulting occupation is shown in Figure 3. arises from the impurity atom. For A 2 2 2 one has doubly or multiply ionizable donors. That is the shallow n = 1-level just below the conduction band edge which. Electronic structure of semiconductor crystals with perturbations with (3. wc assume the case of a positive point perturbation. Due to the substitution of a host atom by such an impurity atom. The shallow energy level therefore functions as a donor of a free carrier. This consideration will lead us to a better understanding of the nature of these impurity states. can be placed in the valence band. i. One can also say that a donor atom (with AZ = 1) has one surplus valence electron which is bound relatively weakly and can be transferred easily by thermal excitation to the conduction band.4 (lower part) the energy levels and localization regions are shown schematically. i. we assume 21= ZH 1.e. Next.e. Although the population of energy levels by electrons will not be treated systematically until the next chapter. In Figure 3. One calls it a donor level and the impurity atom itself as a donor. Therefore. we can imagine it as a P atom in a Si-crystal. with this. 7’ = 0 K . we wish to deal now with a special case. the number of states in the valence band decreases . the number of valence band states is still large enough to host all + . Then the impurity atom also has one valence electron more than the host atom.. except for the additional electron. To be specific. which mandates that the total number of states must remain the same both with and without perturbation.. all the valence electrons of the host atoms and all those of the impurity atom.4. the core charge number 21 of the impurity atom is taken to be larger than the core charge number Z H of the host atom. namely with the occupation of the shallow impurity levels discussed above at absolute zero temperaturc.

but. as we know from section 3. Due to the existence of several valleys (dist. there remain no unoccupied states in the valence band. The n = 1-level in the energy gap remains empty at T = 0 X. and third. rather than with respect to the approximate Rloch function (xlck. Shallow Jevels. the one-component envelope function + + .kill1 for all mutu& degenerate minima ki. we can also say that. the band structure in the neighborhood of each individual minimum is anisotropic.2.3. also. whereas at T = 0 K the hole was bound to the acceptor. [k. Moreover. we treat corrections to the hydrogen model which can be traced back to the cited effects. the minimum lies outside of the center of the first BZ. cannot be directly applied to many semiconductor materials including Si.second. 3.4. the perturbation potential V’(x) has. the above hydrogen model of shallow impurities. to the appr0ximat.4. others only at acceptors. minimum k only Because of this. the wavefunction 01 the donor state $(XI to be expanded with respect. Donors The conduction band of Si and other indirect semiconductor differs in three ways from the simple isotropic hand model.kc])‘of one . Below. as we know from Chapter 1. for symmetry reasons.2 Improvements upon the hydrogen model As already indicated. Some of these corrections appear only at donors. behaves like a positive freely mobile charge carrier. for which the band extrema lie at the I? point and the bands are non-degenerate at r as well as isotropic and parabolic in its neighborhood. In the valence band itself. Donor and acceptor states 271 valence electrons. a hole remains which. Therefore. This picture corresponds to the model of a negatively charged point perturbation which binds a positive hole and transfers it to the valence band under excitation.inguished by a valley index i ) . we treat the two kinds of impurities separately. a short-range part as well as an electron-eIectron interaction part which are not considered in the hydrogen model. an electron from the valence band can easily be excited into the impurity level. under thermal excitation. it functions as an acceptor. First. The level accepts an electron. the acceptor transfers a hole to the valence band.c Bloch funchas tions (xlclri [k. Similar interpretations are available for doubly and multiply ionizable acceptors. the many-valley feature and the anisotropy of the band striiccture rln have such an effect. If the temperature is increased. While the off-center location of band minima has no direct effect on the donor binding enerm. in general. Consequently. The analogy to the positively charged donor center which binds an electron and donates it to the conduction band is obvious. one minimum carries the implication of several equivalent minima or valleys.

kilMC’lk’ .kj) = (3. because V’(x) contains a short-range part.(k) becomes a multi-component envelope function Fi(k).98) = EFi(k . because the screening of a point charge by the semiconductor is wavevector dependent.k j occurring in the former combined with the (l/lkl’)-dependence of (klV’) on k. because of the large wavevectors ki .99).ki and k‘ . the absolute values of the inter-valley Fourier components (kilV’1kj) are negligibly small in comparison with the intra-valley Fourier components. In zero-order approximation they may be omitted completely. (3. With i = j . For i # j . The effective mass equation (3.2. However. the matrix elements (kJV’Jk’)of the perturbation potential V’(x) can approximately be replaced by the k. k z ) . Both modifications can cause the inter-valley matrix elements (hlV‘Jkj) of V’(x) to take larger values. where M is the effective mass tensor of valley i.and k’-independent expressions (kilV’lkj). one obtains a separate effective mass equation for each valley from (3. and we have The envelope function equation in k-space reads rx k’ j - h2 (k . Electronic structure of semiconductor crystah with perturbations F. The latter can easily be transformed into coordinate space where they result in an additional 6-function-like potential. the matrix elements (kJV’Jk’)result in the perturbation potential V’(x) which is already present in the hydrogen model.ki). as was assumed. they still remain so small that they can be considered by means of perturbation theory. i. Thereby. Nevertheless. as we know from section 3. i The wavevectors k .99) If V’(x) is the screened Coulomb potential of equation (3. it reads.98) in coordinate space thus reads = EFi(X). In case of k. k and k’ are vectors near the respective minima ki and kj. the true perturbation potential V’(x) differs from the pure Coulomb potential.e.272 Chapter 3.ki) 2 [ 6ij6kkl + (klV’lk’)] Fj(k’ . and on the other hand. O . which cannot be traced back to the potential of a point charge in any way. = ( O .k j vary in a small neighborhood about the zero point. in coordinate space .80).

the calculation of eigenvalue corrections involves the diagonalization of the matrix O(kilV’lkj)lFj(0)12. one can replace the reciprocal effective mass rn: of the hydrogen model by the reciprocal effective mass (l/m:ll + 2 / m . that of the second excited state must be orthogonal to both previously calculated states. all valleys give rise to the same donor level.100) over all directions in k-space. ) / 3 obtained by averaging the direction-dependent reciprocal effective masses of (3. Using this representation one calculates the energy expectation value of the Ilamiltonian and varies the parameters until its absolute minimum is reached. Donor and acceptor states 273 Analogous equations hold for the other valleys. in addition. the inter-valley coupling in the effective mass equation (3. be orthogonal to the ground state wavefunction. The success of this approach thus depends in an essential way on the auxiliary functions used. Numerical results obtained by means of this procedure for the energy levels of the P-donor in Si are reproduced in Figure 3. Using the example of Si. Inter-valley coupling As a second corrective step. They should. in which the eigenfunctions are represented as linear combinations of niembers of a set of auxiliary functions whose general shapes are adjusted as well as possible to the real solution. etc.5. this calculation will now be . Anisotropic effective masties In contrast to the hydrogen model. which is better as the linear combination of auxiliary functions approximates the actual eigcnfunction.100) depends on direction in k-space. in particular) correctly reflect the symmetry of the actual eigenfunctions. analytical solutions arc not available. This minimiim value then yields an approximation for the ground state energy. In perturbation theory. one obtains energy levels for the simply ionizable donor in Si. but which still contain free parameters. One can also employ the variational process for the calculation of excited states. the effective mass of the envelope q u a tion (3. In this circumstance. This means that.5a.3. The binding energy E B is represented as 29 meV in this approximation. in the case considered here the symmetry of the ground state wavefunction. For a simple estimate of the anisotropy effect. which are shown in Figure 3. In this case the wavefunction of the first excited state must.99) will be considered. and one mist resort to approximations and numerical calculations. One possible approach is the application of a variational procedure. With this. neglecting inter-valley coupling. Shallow levels.4.

k.02 . From symmetry considerations it follows that f ( .274 Chapter 3. which lie on the cubic _ . ( ) 2 has the general form lkl'k)Ik01 O b b O b b c b b c b b c b b c 0 b b b O b b b O c b b b b b b c b b o 7 (3.. k . 1985.~ axes k.-c.. In this case one has 6 minima.) ..0'0° T > w I w CI.. and k. k.03 -0. k.103) . 1 .fold C.Ol ! -0. b) including effcctive mass anisotropy..fold (3. AEz = -2b + 2 fold AEg .04 -0.5: Ground state and first excited states of a phosphorus donor in Si: a) hydrogen model. close to the respective X-points. ( A f t w Rlakemore. Electronic: structure of semiconductor crystals with perturbations Figure 3. r = ~t(kzIv'lkz)l. c) including central cell corrections.05 performed explicitly. 2 -0. kzrk.. k .. The matrix (3. d) exxperimental results.101) has the three eigenvalues A&I = 4b + C. efferlive mass anisotropy arid intervalley coupling.101) b = fi(k~lv'lky)l~z(0)12. I . 3 .. V l . k.102) have been used. Lines and columns in (3.)IFz(0)12 (3. k..101) are written in the sequence -__ k.0.

Shallow lwels. been observed experimentally (Aggrawal and Ramdas. A E z = 3. If one considers only thc first of thc two abovementioned effects which result in matrix elernentv ol considerable size...8 meV to the binding energy of 29 meV without inter-valley interaction yields a corrected binding energy of 39. . This yields AEl = -10.8 meV.of z l o c a l i d states.2 met‘. a. y. ‘The notations A . Thus.99) for si. ) .therefore replaring the screened Coulomb potential V’(x) of equation (3.5 are even closer to the experimental values. it is clear that the symmetry of the AEI-state is A l .5). A 3-fold splitting of the P-donor ground state level in Si has. that of the two AETstatcs is E . for Si:P but still clearly below. The sphtting of the ground state donor lrvel in Si due to inter-valley coupling can also be predicted j u s t oti the basis of group theory. However. r 2 ( E ) and I’z5(Tz). One considers the representation of the symmetry group of the envelope e q u e h n (3.5 we list experimental binding energies for a number of singly . T are commonly used in the theor.36 mel’ and c as -1.. inter-valley coupling partially removes the 6-fold degeneracy among the valleys. The addition of A E l .80) by the bare Coulomb potential -(e2/IxI) in (ktlV’lkj). and WP will also employ thcm here. _ _ ) in the space of the 6 reciprocal vector compo_ of o h .6 met‘ and AE3 = 1.6 meV between the A l .and T2-levels. k. z .e. To demonstrate this one may employ the transformation rules of the vector components x . With this.2 meV.104) With this. one obtains b as -2. Z under the action of the clcments of o h (summarized in Table A. E . k. of 10.4. and that of the three AE3 states is 12. and of 1. The results of a numerical treatment of inter-valley coupling shown in Figure 3. nents k.7j. in fact. 1965). the agreement is not as good for the absolute position of the ground state level. Chemical shifts In Table 3.3 meV between the E .kj. The simple theoretical estimate presented above agrees remarkably well with the experimental splittings of 11. then it follows that (3. This representation is reducible.7 of Apprndix A). i.k. Then one easily 1 finds that the irreducible parts of this representation arc rl ( A . kg. k. i. the wavevector dependence of screening..e.8 meL’ which is closer to the experimental value of 45 meV.and T2-levels (not resolved in Figure 3.. realizing that these component? transform in the same way as thc reciprocal vector components considered here. Donor and acceptor states 275 with the degrees of degeneracy indicated. i. The size of the splitting depends on the inter-valley nitrtrix elemen1 of the perturbation yolmtial..e. and assumes that screening has become fully ineffective at large wavevectors k.3.

276 Chapter 3. there are also contributions which depend on the chemical nature of the donor. The effects of central ceE corrections are particularly large in the case of the 1s-ground state. to which all central cell corrections contribute. better agreement between experiment and the predictions of a theory omitting central cell effects occurs for the excited states with n = 2 . The latter are the main reason for the experimentally measured chemical shifts of the donor binding energies. there are dependencies of binding energies on the chemical nature of the impurity atoms. the correct perturbation potential of an impurity atom also contains a short-range part. One refers to these as chemical shifts. 3 . Ge and GaAs. as one can recognize from Figure 3.5 for the special case of the P-donor in Si. As we know from section 3. A weaker influence. but also the fact that they are not equal for donor or acceptor atoms of different chemicals stands out.2. 1982. Contrary to the prediction of the above theory. Electronic structure of semiconductor crystals with perturbations Table 3. . This is to be expected since the excited state wavefunctions have maxima that do not lie at the perturbation center x = 0 . . .. accordingly.5: Experimental binding energies of several shallow donors and acceptors in Si. (After Landoldt-Bornstein. Ge and GaAs. Among these.) Material Si Sb Ga In P Ge As Sb Bi 13 14 10 13 B A1 Ga In 153 11 11 11 12 GaAs ionizable donor and acceptor atoms in Si. and. The absence of chemical shifts in the calculated binding energies is a consequence of the approximation of the perturbation potential V’(x) as a purely Coulombic potential in the hydrogen model. Not only are the absolute values of these energies striking.

or the 4-fold degeneracies of the representations I?$ (diamond) or Ts (zincblende) in the space of twc-component spinor functions. In fact. Later this approximation needs to be corrected since E g is not much larger than A. * components F.5 for further discussion). respectively. they differ appreciably from the measured ground state binding energies shown in Table 3. Thus (3. If one also uses this approximation here. Below. Generally. y. In section 2. one for heavy holes and one for light holes. In the case of Ge. this maximum is degenerate: depending on whether spin-orbit interaction is important or not one has. z of the representation T .3. the occurrence of pronounced chemical shifts means that the perturbation center is no longer shallow and the effective mass theory is no longer applicable for its theoretical treatment (see section 3. This may be done by means of the multfband effective mass theory developed in the preceding section. ShalIow levels. as is assumed in the hydrogen model.7 these were approximated by two isotropic parabolic bands. the result is 17 meV for heavy holes. spin-orbit interaction initially will be neglected. Without spin and spin-orbit interaction the wavefunction ~ A ( x ) is a linear combination of the three Bloch functions (xlumO). Calculating acceptor binding energies by means of expression (3. which are enveloped by the i. the %fold degeneracies of the representations l'b5 (diamond) or (zincblende) in the space of scalar functions.95) in the case of Si yields 50 met7 for heavy holes which are expected to form the ground state. Electrons in the excited states are therefore less affected by changes of the potential in the central cell than are electrons in the ground state. However. One can hardy expect these values to be in agreement with experiment. one for each sort of holes. then there are two hydrogen-like series of acceptor le\-els. In the vicinity of r.m = x. non-parabolicity and anisotropy of the band structure play an essential role and must be taken into account in realistic calculations.5. the maximum of the valence band lies in the center r of the first B Z for all diamond and zincblende type semiconductors.4. we will explain the application of this theory to simply ionizable acceptors in Si. Acceptors Corrections to the simple hydrogen model are also necessary for acceptors. Donor and acceptor states 277 (which does happen in the case of the ground state) but further outside.(x) of the envelope function vector F (x).105) . Evidently. Of course. Owing t o the small spin-orbit splitting energy A of 44 meV and the relatively large acceptor binding energies E B (68 me\' for the isocoric impurity atom Al). this degeneracy splits off and one has ihree or two anisotropic valence bands.

. q l (x).72). FA^ transform separately. belong to a space which differs from the ordinary .ql(x). (3. It belongs to an irrdiicible reprc sentation r A of the point moup oh..atinns.105). . . Hilbert syaccr in that it is riot spanned hy oue-comyonent basis funrlious. in the case A 2 = -1.107) .. One has to use spproxinia tions and numerical calculations. U ( x ) is identified as the Coulomb potential. This function should have symmetry properties which fit the symmetry of the acceptor state @ A ( X ) to be calculated. . . in closed analytical form. actually transform according to the representation r ~ * * The FA^ (x). The meaning of this will be explained below. as has been supposed. fiinctions FA^. Electronic structure of semiconductor crystals with perturbations The corresponding effective mass equation of the I’b5-valence band is given by relation (3. One can easily show that the latter representation must +.. one obtains. The variational method again represents a reasonable way to proceed. denoted by $ A ~ ( x ) . forincd according to relation (3. The eiigenvalues and eigeuvectors of this complicated set of equations cannot be obtained.@m(x). must belong in order that . of course. A representation in this space is given by the product of two represt?nt. . FA^ (x). ~ A ~ ( x$~z(x):. . W e have to find the representation D A of =$O h to which the set of vectors F A ~ (x).278 Chapter 3. If. long to the representation r A . (3. We consider a particular acceptor level E n . it follows that . one of which corresponds to the 3D rqresentation according to which the components of each of the three= $ * component. . In this approach one starts with a choice of suitable auxiliary functions for the expansion of the multi-component enve=$ lope fundion F (x). 3 * . therein.b e be r A . of equation (3.q2(x)..105). so that $. formed from these vectors by meam ). ..80). and the other is the representation according to which the threecomponent functions transform among each other.. For the representation * * D A of FA^ (x):FA^ (x). FA? ( x ) . . . which in general will be degenerate. The corresponding aigenhnctions are . the wavefunctions T . but by three-component basis functions. and the pertinent multi-component envelope function by ~ . . .F A ~.

taking spin-orbit interaction into account. @ ~ ( X . Donor and acceptor states 279 This representation is reducible. the T'& valence band has to be replaced by the two rg. but with &dependent localization radii rl. 1977). Equation (3. More recent calculations. Owing to the large spin-orbit-splitting energy. the spin-orbit-split I'F-band can be omitted. Relation (3.107) yields a remarkable conclusion concerning the symmetry of acceptor states. According to (3. 1962). In order to also get their raand ri5-functions with diaI dependencies one expands the rl-. have resulted in a value of 44 mel/ (Baldereschi and Lipari.108) determines the symmetries of the three-component auxiliary functions under rotations.108) shown in Table A. of course. r12-. Since the wave function of the ground state will also be non-zero at x = 0: D A must contain the unity-representation if A is the ground state.5 but.107) this is only possible if the ground state has the symmetry Fh5.e. Spin has to be taken into account under such circumstances. therefore the angular dependencies of these functions. Calculations of acceptor binding energies have also been performed for materials like Ge whose spin-orbit splitting energies are large compared to the acceptor binding energies. which is very close to the experimental value of 45 meV for 3 in Table 3. The latter are treated as variational parameters. These are formed in analogy to the eigenfunctions for the Coulomb potential.27 of Appendix -4. rn and multiplies the expansion coefficients of different values of I by corresponding radial wavefunctions r1exp(-T/q). just like the Coefficients of the auxiliary functions belonging to different irreducible representations. Acceptor levels of other symmetry are necessarily excited states. i. Shallow levels. For the expansion of the 4component envelope function of the remaining rg-band one needs auxiliary functions of 2r15 2r25 symmetry (see Table x Ii = ri f ' k + + + + . The basis vector belonging to the unity-representation is the only one which does not vanish at the central site x = 0. respect to angular momentum eigenfunctions with the various quantum numbers 6.3. however.~only when the symmetry r-4 of these functions is I'h5. . a binding energy of 31 me&' is obtained (Schechter. Applying this procedure to the acceptor ground state of Si. tor eigenfunctions $ A ~ [ X ) .4. The symmetries of all t h r e e component basis functions involved in the construction of the ground state envelope function are given by the relation (3. does not account for the pronounced chemical shifts seen in this table. The irreducible components determine the symmetries of the three-component basis functions to be used for the r e p resentation of the threecomponent envelope function of the acceptor state under consideration.and r$-bands. An envelope function basis vector which transforms according to the unity-representation occurs in the expansion of the accep) .

By exciting one electron into the conduction band. both of which can be placed in the 1. The Hubbard correction (3.25) results in a shiit of the energy levels towards higher energies by an amount which depends on the number 'IL of electrons or holes bound at the center. In the calculations for Ge. Thus the point charge Coulomb potential which neglects central cell corrections giving rise to chemical shifts is expected to work much better for Ge than for Si. as it dow in fact. 3 or more electrons can be thermally excited into the conduction or valence bands. unlikr Si where these shifts were found to be very pronounced. an acceptor binding energy of 10 m e v is obtained. chemical shifts are very small in the case of Ge. Without this interaction the effective mass equat. In the ground state. which in this case is approximately given by is taken into account.ion for a non-degenerate isotropic band yields a hydrogenic s e ries of energy levels with binding energy increased by the factor lA21' in comparison with the corrcsponding energy for a simply ionizable donor or acceptor. but differ by 2. Then 2.or morefold ionized impurity atom. The binding e n e r a without H a r t r e potential is four times larger than that of the P-donor in this material.1 from those of the host atom. and 1. We illustrate these remarks using thc example of the S-donor in Si. reflecting the fact that the effective heavy hole mass in Ge is smaller than in Si. excited acceptor states in both Ge and Si are well described by the multi-band effective mass theory using a point charge perturbation potential (Balsderesrhi and Lipari. This implies that the acceptor wavefunctions of Ge have smaller amplitudes in the central cell than those of Si. E D is siihstantially srrialler than in Si. then the 1s-level is shifted up by just this energy Us.280 Chapter 3. close to the experimental values of 12 nieV for In and 11 meV for all other elements listed in Table 3. The interaction between the carriers bound at the center is described by the Hubbard energy of equation (3. Electronic structure of semiconductor crystals with perturbations (A. 2. 3. Multiply ionizable donors and acceptors Additional changes arc to be expected for substitutional impurity atoms whose core charge numbers do not differ by & A 2 . 1978).9-level because of 2-fold spindegeneracy. 2 electrons are bound at the S-donor. 2-. 3 or more.28)). the neutral S-donor . Obviously. 3 or more electrons or holes are weakly bound to the impurity atom at T . If the Hubbard correction. as we assumed above.0 K . For the same reason. leaving behind a 1-.25). The different behavior of acceptors in Ge and Si is undmstandable if one looks at the absolute magnitudes of their binding energies EB: in Ge.5.

however.hat the ionk-ation energy of the neutral S(O+) donor is 0.69 eV (see Figure 3. Deep lewls 28 1 S(D+) bccarnes a single positively charged S(1+) donor. that in the case of a 1-dimensional potential box. both ionization energies are suhstantially larger than the result. e g . for a 3-dimensional potential box of depth Vo and radius a.h. According to wction 3.4 as c e n l m l tell correcfioru. Thus this level i s shifted down by I/. bound states exist for arbitrarily small m d l depths sincc the 1ocalizat. on t. i. hhc potential of a point perturbat. For the I . for arbitrary magnitudes of the point charge and dielect. (Not.rengt.3. The concornit.e. in that localization due to the potential leads to a non-vanishing expectation value of momentum and 1. and the ionization energy of the S(1t) donor j s 0. The spatial extension of the eigenfunction is essentially given by the Bohr radius.31 eV.. consists of a long-range (Coulornbic] part and a short-rangp part. Evident. the two potential contributions differ substantially. in comparison with the 1s-level of tbc S(0 +-) atom. shallow levek ocrur for statps which are bound by a Coulomb potential.5 Deep levels 3+5.e. If t. ‘ l l i s donor is a deep center rather than a shallow me. i.h to he able to bind a stale. of 0.rir:cobstant. IIowever. Only if the dept8h of the potential box exceeds the expectation value of this kinetic energy! can t.a sld 01 h e S ( l 1 ) ioii thr shift in energy by Us do= not occur. This indicates already at t. Short-range potentials. generally. one finds t.hc potential prevent the partick from escaping the center. Exprrirneniully.1 General characterization of deep levels As we know from previous sc3ctions. In the case of the long-range Conlomb potential. must have a minimum st.he strength of the short-range .uli) must he fulfilled for a b a u d state to exist (see.8. by the long-range contribution of the total perturbation potential.he outset that 1-dimensional models of deep centers are ralher poor).28 eV may be deduced.4.12 eb’ which follows from the hydrogen model. for all possible potential strengths.ribution is ewedial in the case of the S-donor in Si. For example. 3..ion. the central cell short-range poteniid cont. the condition Vo > h2/(8w>. hound $Pates exist. ? Schiff.e. the average kinetic energy decreases sufficiently.ant short-range potential part does not suffice in this case for binding.hus also of kinelic energy of the particle. 4 x 0.hecontrary.ionand: with this. In regard to their ability to bind states. 1968). k1loa.03 el7 = 0. From thefie values a Hubbard energy I i .6). Heisenberg’s uncertainty principle manifests itself. In this.fast with decreasing well dept. it only leads to corrections of the binding energy and the eigenfunction of the ground state.ly.n from section 3.

namely smoothness of the perturbation potmtial and of the corrpsponding wavefunction. binding to the center will be dominated by the short-range potential contribution. in the case of deep levels the requirements of effective mass theory. . namely. that short-range potentials can dominate binding only if they exceed a minimum threahold potential strength . but by thr lattice constant. States which are primarily bound by the short range potential part. far away from the two band edges.derp levels can also be close t o or even wzthm one of the bands. Because of their strong localization. then a point will be reached at which the short range potential is itself able to bind states.282 Chapter 3. it anticipates. Literally. which are mainly determined by the short-range potential alone. these states cannot be s p t h e s i z d by Bbch functions of k-vectors drawn from a small vicinity of a rritical point. Actually. in combination with this. the location of deep levels deep in thr energy gap is only a particularly important special case. in particular. The essential features o deep levels are their binding f by a short-range potential and. and the chararter of the bound state will change. In a theory of deep states. results which are i n d d plausible. to the fundamental feature which distinguishes between shallow and deep levels. In this context one can say that skidow levels are eigenvalues of point perturbations which are capable of description by means of effective mass theory (the concomitant short-range potential contribution can be treated by rncans of perturbation thcorg in this rase). are termed d w p . nor can such a theory be based on a oneband equation. The discussion above is amply intuitive. The shallow levels can therefore be treated by means o an effective mass f equation. The Coulomb potential only leads to corrections to t h r binding energy and the cigmfunctions. Electrunin structiire of Bemiconductor crystals w i t h perturbations part of the potential increases. and the point perturbations at which they occur. in part. are called as deep centers. as there are also yet other case. are not fulfilled. The spatial cxtension of the f eigenfunctjon o the ground state is then no longer dekrrninml by the Bohr radius. Provided the pertinent binding energy i s Iargcr than that due l o the Coulomb potential. ‘ h e rorresponding la-& arc called deep levels. neither the effective mass is meaningful. but which have yet to be proven rigorously. their localization radius bring restricted to magnitude of the lattice constant. deep states resolve the spatially periodic fluctuations of the rrystal potential while the eigenfunctions of shallow levels average them out. the term ‘deep level’ refers to an energy eigenvalue that lies deep in the energy gap. while deep levels are eigcnvaliies whose treatment by effective mass theory is impossible. not even a degenerate multi-band equation. and also not from Bbch functions of only one-band. This applies. in contrast to shallow levels which lie close to one of these edges. therefore. Contrary to the assumptions of PEective mass theory. Attempts t o retain the effective mass concept and to consider solely ihe multi-band character of deep level theory met with little success.

4 Acceptors . . This difkrence can serve as a measure of the strength of the short-range potential. and acceptor energies to the valence band edge. There: the ionization emrgies of a series of substitutional impurity a t o m are plotted as a function of the difference! between the atomic valence shdl energy levels of the host and impurity atoms. An experimental proof of the threshdd behavior of short-range potentials in crystals may be taken from Figure 3.6.283 2 1 0 -2 -4 -6 . and valence shell p-level differences in the caae of acceptors.. Donor energies are reIative to the conduction band edge. measured in terms of valence shell s-level differences between impurity and host atoms in the case of donors.6 (eV) 2 1 -2 -4 -G -8 -1OleV) Atomic Electronegativity Figure 3.3 .5 .._ a: F .6: Ionization energy of substitutional impurity atoms in varioum tedrahedrally coordinate host semironductors as B function of the strength of the pcrturbation potential. 1981. the periodic potential of the crystal was omitted n from consideration. (After Vogl. The fact that for donor states .i the discussion above.- 2 . Reproduced from Boer. 1990.

On the other hand. and for acccptor states the differenre of p-levels. as in the case of fast transistors and photodetectors.284 Chapf. decp levels can also act as donors or acceptors (sometimes even as both of them). in addition to the neutral center. non-radiative recombination processes have to be avoided. The consequences of many-electron effects in the electronic structure of deep centers will be discussed in subsection 3. which are available there eithrr as equilibrium charge carriers due to n-doping. Centers which can capture both electrons as well as holes act as catalysts for the radiationless recombination of electron-hole pairs (see Chapter 5). in turn.Just like shallow levels. or ~ L non-eyujlibiium cariiers due to optical or other excitation of Y of the semiconductor. one has a c o m p e ~ w u t i o n the donors by the deep center (for more 5ee Chapter 4).5 we display experimental and theoretical results . generally less effective than shallow levels in enhancing the concentrations of free charge carriers. If one wants to enhance radiative recombination as strongly as possible. deep centers play a role of similar importance to that of shallow ones for semiconductor devices. shallow levels are not very effective. a manifestation of the fact that the short-range potential has takm over binding and the level has become deep. the so-called defect-molecule model. Due to their mostly larger separation from the hand edges they are.5.5. In section 3. one should intentionally introduce deep centers in order to enhance non-radiative recombination. which involves the elimination of the corresponding deep centers. They exhibit their greatest efiectiveness in just thp opposite process. . Electronic structure of semiconductor crystals with perturbations the diffrrence of 8-levels is taken.er3.5. the potential strength increases more or less continuously.5. is not important foi the present discussion (we will return to this point later).2 we will develop a simple model of a deep center. The ionization energies initially retain their small valucs characteristic of shallow lcvels. the lowering of free carrier concentrations for which. In subsection 3. In the first case.3 we treat some methods of solution of the one-electron Schrodinger equation for deep centers. and in the second case. plays an analogous role in regard to the compensation of acceptors and the capture of non-equilibrium holes. a cupture of non-equilibrium electrons by the center (see Chapter 5). the neutral center will capture electrons from the conduction land. if one is interested in having a short lifetime for non-equilibrium charge carriers. the single negatively charged center also forms a deep level in the gap with sufficient separation from the conduction band edge. In general. we now will treat their electronic structure. In subsection 3. With increasing horizontal scparation of the impurity atom from the host atom in the periodic table. although in a completely different way. A center which forms deep levels in the gap both in the neutral and simply positively charged state. however. such as in semiconductor light emitting diodes or laser diodes. If.4. they suddenly become substantially larger. Having discussed the general character and importance of deep centers. Starting at a threshold distanre.

we employed wavevector-dependent Bloch sums lukj) or ihtkj) formed from them. We will mainly use the model to demonstrate the existence of deep levels and to explore the symmetry of the pertinent eigenfunctions. This was advantageous because the translation symmetry of the crystal could be exploited in this way. the substitutional impurity at.2 Defect molecule model The 'Tight 3inding' (TB) method developed in section 2. the group of 3dtransition metals.7 shows part of a Si crystal containing a vacancy. but rather. we will apply this model to substitutional impurities from the main groups of the periodic table. many particle effects and lattice relaxation will be ignored.3. i. Also. Vacancy Figure 3. the TB method should be particulady well suited for such centers.the atomic n orbitals or hybrid orbitals IhtRj) were not used directly.oms of the main groups of the periodic table. 3. among them the vacancy in Si. Symmetry consid- . However. Later. In doing so. The simplest among these models is the so-called defect-molecule model. like the Bloch sums of hybrid orbitals in the case of an ideal crystal. can also be used without any loss. Unlike other methods it uses basis functions to represent the Hamiltonian which are localized on the atomic length scale. the method should be suited to the derivation of simple models that exhibit the essential physical features of real deep centers. and the results also cannot be expected to be very accurate in a quantitative sense. atomic or hybrid orbitals.5.e. Of course.6 represents one of the various procedures for calculating band structures of ideal crystals. The latter symmetry no longer exists in a crystal with a deep center. We introduce the defect molecule model using the vacancy as an example. Deep levels 285 for selected deep centers. an elemental semiconductor of group IV. which we will introduce below.like Si. we discuss the D X center and the EL2-center in GaAs. We select hybrid orbitals because these produce drastic simplifications of the Hamiltonian matrix which. one must chose the Hamiltonian matrix elements empirically in order t o arrive at useful practical results. so that localized basis functions. E the ideal crystal case considered in section 2. allow the eigenvahes of the Hamiltonian to be calculated in closed analytical form. Since the perturbation potentials of deep centers are localized on the same scale.5. in all cases. and the group of rare earths.6. At the outset we have to clarify which of the various tight binding basis sets should be used for the representation of the Hamiltonian in the case of a deep center. As the host crystal we take.

and second. the crystal with a vacancy decomposes into two partial systems which do not interact with each other. whether it originated by removal of a Si atom from sublattice 1 or from sublattice 2. The latter must be taken into account here in order to arrive at non-trivial results. no longer have a hybrid orbital of a 1-atom to which they can bind. one at each of the four atoms surrounding the vacancy.7). it ha6 the sense of second-nearest neighbor interaction. the partial system of the four interacting dangling hybrid orbitals. but. The hybrid orbitals at a pal ticular siirrounding 2-atom also interact among themselves. The three other hybrid orbitals at a surrounding 2-atom interact with inwardly directed hybrid orbitals at atoms lying still further away (these atoms are not shown in Figure 3. With some ambiguity . we consider the removal of an atom from sublattice 1. which means . 4 . They still interact only among themselves. including the one dangling hybrid at this atom.286 Chapter 3. 2 . and to be still more specific.6.e. Here. pointing inwards. Based on the approximations made above. i.cp. They are called danglzng hybmds. if the matrix element V1 introduced in section 2. from the primitive unit cell at R = 0. this interaction is not within the framework of Erst-nearest neighbor interaction which we have been exclusively considering in the treatment of an ideal crystal in section 2. the hybrid orbitals lht2Rt).e. rather. Electronic structure of semiconductor crystals with perturbations erations make clear that the origin of the vacancy is not important. the yarlial system of all remaining hybrid orbitals of the crystal with the vacancy. If interactions between hybrid orbitals at the same atom are omitted. This means that the dangling hybrids are coupled to the entire crystal through nearest neighbor interactions. the hybrid orbitals of all atoms which are not directly adjacent to the vacancy. then the dangling hybrids are decouplcd from the remainder of the crystal. Because of the removal of the 1-atom. and the three hybrids at each one of the four adjacent atoms which ~ &renot alrpady included in the first ptrrtial system. of the four surrounding 2-atoms in the unit cells Rt. The perturbation potential V’(x) is the negative of the potential produced by this atom in the crystal. Since the atoms at which these hybrids are located are second-nearest neighbors. 3 .6 is set to zero.t = 1 . i. first.

by creating a vacancy in sublattice 1) the two sublattices are no longer eqiiivalent. such that wit.e. Because of the predominantly negative values of the operator fI V’ acting on hybrid orbitals and the predominantly positive values of the hybrid orbital products. Nevertheless. this means that all non-diagonal elements are equal for symmetry reasons.b W as second-nearest neighbor interaction energy. The energy spertriim of the rest-ofcrystal is therefore identical with t . ‘I’he absolute value of W must be determined empirically. and the anti-bonding level E = E. Since. the symmetry of the crystal is no longer given by thr full cubic point group Oh.c. W is expect.IVzl. but rather by the tetrahedral group y d . the vacancy-molecule. h d of the infinite idea1 cryslal in bhe simplest TB approximation? consisting of the bonding level t b = th . Deep levels we can refer to the first partial system as a vacancy molecule: 287 and to the the ‘rest-of-crystal’. the same &om? i. of r/l. i. one has to recaIl the symmetry of the perturbed Hamiltonian H +V‘. The Hamiltonian matrix elements between the various pairs have the same value. In calculating the energy spectrum of the first partial system. The splitting of these highly . t‘ f t . the neglect.e are small. namely the value given above in equation (2.5. This designation also encompasses h e term defect molecule model for the tight binding approximation described above. we need the matrix elements of the pertarbed Hamiltanian H + V ’ of the crystal with vacancy.t2Rt(V‘ lht2Rt) of the vacancy potential V‘ between hybrid orbitals localized off the %mancy sit. The diagonal elements (ht2RtlH + V‘lht2Rt) are simply the hybrid energies ~h since the elements (h.292) defining matrix element T/2. For each hybrid of the rest-of-crystal another hybrid exists in the restof-crystal which points to it..+ I&I. degenerate levels into bands remains incomplete because of the neglect of Ihe interaction between hybrids at.ed to be negative. One therefore has second tts + In order to obtain the non-diitlgounel (second-nettrest neighbor) matrix elements ( h t 2 R t l H f V”lht32FQ) between different dangling hybrid orbitals t .3. The energy levels of the vacancy-molecule are obtained by diagonaliziug the matrix + .

288 Chapter 3. and the 7'2-level in the energy gap. the sp3-hybridization of the atomic orbitals in a Si crystal is removed at a vacancy.[lh12R1).113) (3. cannot be answered within the defect molecule model because.116) (3. 45 One can easily demonstrate that IEI") belongs to the irreducible representation A1 of the symmetry group Td of the vacancy.8. and the three Tz-eigenfunctions are similar to the three p-orbitals of such an atom. With this. and the three functions IE$uc).117) (3. The eigenfunction of the A1-level resembles an atomic s-orbital of a Si atom.4 read (3. the e n e r e spectrum of the defect molecule model of a vacancy is shown along with that of the rest-of-crystal. Whether it lies below or above the bonding level of the crystal depends on whether we have 31W1 < l\Jzl or 31WI > lF'21. IEiWc)to the irreducible representation T2 of this group (see Table A. (3. Electronic structurc of scmiconductor crystals with perturbalions Its eigenvalues Eyzz.-[ I ~ I ~ R I ) . It is just as difficult to decide whether the Tz-level la i in the conduction bend or in the energy gap. VaC Jz [IIZL~RI)IhaZRz)]. in consequence of the fact that the crystal potential is no longer fully effective in the vicinity of a vacancy. The A1-level lies below the Tz-level because of the negative value of Vt-. therein.6 of Bppendix 4 ) . . which we will discuss later in more detail. the valence band has shrunk to the bonding energy level.118) ) .Jh2R3)] ~ 1 v5 I 1 138"")= . In Figure 3. show that the -41level lies in the valence band. Evidently.114) IEY)= IE.lh42R9)]. IEY'). Experiment and more exact calculations. The states are more atom-like. The question of whether it is found in the valence band or in the energy gap.

Like Si. p Let the siibstituted Si atom be that of sublattice 1 in the primitive unit cell R = 0. IV. The perturbation potentials of these impurity atoms in an elemental semiconductor of group I V possess.5. of the rest-of-crystal. In any case it. which we can again imagine as a Si rrystal (see Figure 3. The distribution of thc 4 electtona of the defect molecule over the energy levels is also shown. The . Substitutional impurity a t o m s w i t h sp3-bonding We consider a substitutional impurity alom in an elemental semiconductor of ~ o u IV.each of the four dangling bonds yields one two must he hosted by this lcvcl while the other two occupy the A1-level in the ~ valence band. the T2-level is the actual deep level of the vacancy. both a short-range part and also a long-range Coulomb part.9).8: Energy spectrum of the defect molecule model of ~ 1 . IJsing the terminology introduced above.Si-vacancy along with that. the impurity atom should belong to one of the main groups 11. we may say that the oxidation state of the neutral vacancy is V2+.and p-orbitals. which all lie energetically higher than any other occupied orbitals (in contrast to rare earth atoms). or VI of the periodic table so that the valence shell is formcd by s. Refinements of this picture will be discussed further b e low. Deep levels 289 Figure 3. V. provides a qualitatively correct physical picture of the electronic structure of a vacancy in group-IV elemental semicondiictors.3. as we know.111. Of the four electrons of lhe neutral vacancy . The defect moleciile model of the vacancy reflects the actual relationships remarkably well. Here we treat a second example to illustrate the defect molecule model which emerges from the v.mancy by occupying its empty lattice site with an impurity atom.

3. although it influences the actual position of this level in the energy gap.9: Defect molecule model of a substitutional main group &bonding impurity atom in a tetrahedrally coordinated semiconductor. We consider only the most important elements of this matrix. jht2Rt). first.2. respectively. and c i signify.4.292) between hybrid orbitals at nearest-neighbor atoms of the ideal crystal .t = 1. V2 corresponds to the matrix element of H of equation (2.t = 1.3. The energy spectrum of the rest-of-crystal again coincides with that of the ideal crystal within the framework of the approximations used here. L latter will be omitted from consideration below.2. The Hamiltonian matrix of the defect molecule is composed of elements of the general form fhtjRtIH + 17’lht~j’R~~)~ (3.). the hybrid energies of the impurity and host atoms. E . Xeglecting interactions between the hybrid orbitals at the host atoms. This approximation does not affect the answer to the question of whether a particular impurity atom forms a deep level or not.4. Electronic structure of semiconductor crystals with perturbations Figure 3. and second. The latter cannot be determined within the defect molecule model anyway. The four sp3-hybrid orbitals of the impurity atom will be denoted by IhtiO). the rest-of-crystal with all remaining orbitals. the defect molecule with the 8 orbitals jhtiO).119) where j and j ’ take the values i and 2 independently of each other. into two partial systems. just as before in the vacancy case. the crystal with a substitutional impurity decomposes. namely In this.290 Chapter 3. and the four hybrid orbitals of the host crystal pointing in the direction of this atom will be denoted by IhtzR.

and W describes. . denoted as and E&Y:. respectively.e. W W W (3. whence EiT/b In Figure 3.3. as in the vacancy case. The eigenfunctions of the two simple levels (we distinguish them by indices b and a ) belong to the 1-dimensional irreducible representation A1 of the tetrahedral group T d .O 0 0 0 vzo 0 6 i 0 v20 o a o v2a o o 0 v2o a o v2 € . The corresponding energy levels are.) listed above are neglected. i.126) must coincide with that of the ideal host crystal in the . With these approximations. between the hybrid energies of impurity and host atoms.10 these levels are plotted as functions of the difference ( c i .5. with t’ f t. lh12R1)) lh22R2). In doing so the rows and columns are ordered in the sequence IhliRl). it is helpful to consider two limiting cases. we assume the impurity atom to coincide with the host atom. the Hamiltonian matrix of the defect molecule may now be written down in explicit form. among them also the Vl-like elements (htzRt(H V’lht. then the energy spectrum of the perturbed crystal of equations (3. lh32R3).b. means t i = c If one also neglects the second nearest-neighbor interaction energy W . lh4iR4). This matrix has four distinct eigenvalues. In order to better understand the physical meaning of the energy levels derived above. two simple and two triply degenerate.) between different hybrid orbitals at the impurity atom.E ) . and the two triply degenerate (again distinguished by indices b and a ) belong to the 3-dimensional irreducible representation T2 of T d . lh2iR2). which . This difference represents a measure of the strength of the short-range perturbation potential of the impurity atom. Deep levels 291 pointing toward each other. lh3iR3).124) 0 W E k W W W W E k W 0 (0 0 0 v20 0 I $ w w w e.125) and (3. and the Hamiltonian matrix is + + L i 0 0 0 0 0 0 1720 0 0 0 €e. the second nearest neighbor interaction between differing host atom hybrid orbitals not pointing toward the impurity atom.. I@&).i&. All elements ( h t j R t l H V’lht‘J’Rt. First.

e.e i ) .128) and in the limit Ei 4 --oo we have EiT = tk + 3W. In the limit EiT. also means t i -+ +m or E . Electronic structure of semiconductor crystals with perturbations Figure 3.10 encompass the energy gap of the host crystal. respectively.127) (3. Second.126) yield (3. simplest TB approximation. = € h + IV21 must emerge. of the perturbed crystal Thus it is also clear that the two energy levels correspond to bonding and anti-bonding states of A1-symmetry. -+ -00. we consider the limiting case of ( E . a bonding energy level q = ~ h IVzI. and an anti-bonding energy level E. . and the two energy levels EY . i.292 Chapter 3. E i + $00 equations (3.$ two undisturbed levels € h f IV21 in Figure 3. Horizontal lines indicate the bonding level t b and the anti-bonding level of the host crystal. This is in fact the case.tk) tending toward $00 or -00 which.. The .129) .125) and (3. to bonding and anti-bonding states of Tysymmetry.10: Energy levels Eimp of a substitutional main group sp3-bonding impurity atom in a tetrahedral semiconductor as function of the hybrid energy difference ( t i . for a given host crystal. (3.

This occurs for the same reason as above in the limit t i -+ +m. ) < 0 holds.5. toward 00. .113) and (3.3. Deep levels zmp = Ezmp EAlb Tzb ~ 293 + --O0.130) In the limiting case t i -+ +m. Two remarkable differences were found in relation to an ideal crystal: First. while the two bonding levels and limit toward. A look at Figure 3. and the anti-bonding A1-level if ( 6 .and Tz-levels of the vacancy of equations (3. we will eliminate such additional difficulties of electronic structure calculations for point perturbations by assuming that the population of the center and the atomic structure of the perturbed crystal are known. forming deep levels there.6 .2 this task already was addressed in general terms.114). Below. the two Al. there is a vacancy. leaving the energy spectrum on its high energy side. namely because t i + -00 means that there is a vacancy at the impurity site.3 Solution methods for the one-electron Schrodinger equa. while the anti-bonding levels limit toward the two A l .E.10 shows that the most favorable candidate for an impurity level to be in the energy gap is the bonding Tz-level if ( ~ 6.In section 3. along with t i . we will describe such calculations and discuss methods for solving the one-electron Schrodinger equation (3. respectively. tion of a crystal with a point perturbation The solution of the Schrodinger equation for a crystal with a point perturbation begins with the determination of the effective one-electron potential VPrt(x).114).8) for the crystal with a point perturbation. -+ -m the two bonding energy levels and E$T leave the energy spectrum at its low energy side.and Tzlevels.and Tz-levels can occur in the energy gap. More rigorous calculations confirm this conjecture in that they find exactly these levels to be in the gap. Below.113) and (3. In regard to the of . i. (3.)i > 0 holds. Thus the potential Vwrt(x) the center can also be considered to be known. This is understandable because the limiting case EL ---f +m means that no impurity hybrid energy level exists at finite energy and.127) tend. the bonding Al. which participates in the determination of the pois tential Vwrt(x).and T2-levels of the vacancy of equations (3. For finite positive values of (EL . In other words. in many cases initially unknown and it must be selfconsistently calculated jointly with the electronic structure.e. therefore. With E . there is also effectively no impurity atom.).5. the two anti-bonding levels and EkYZ of (3. depends on the electron poputhe effective one-electron potential VPert(x) lation of (localized) one-particle states. EiT EiY EkYl EiY 3. and for finite negative values of (tL-~k) the same can happen with the two anti-bonding Al. and second the atomic structure of the perturbed crystal.

the surface levels are lowered deep below the valence band edge and raised high above the conduction band edge.the possibilities include Hartree. the infinite crystal with a point perturbation is replaced by a finite part which contains the point perturbation at its center and which. one can add an additional cluster of the same kind. Supercell method At the boundary of a properly shaped ciuster. If one does this repeatedly and continues the whole proress ad infiniturn. The three most important procedures are the cluster method. no longer that of the crystal hosting the point perturbation. but it is the cluster. Because of the dependence of the potential on the eigenfunctions of the Schrodinger equation. this only means that on the functional dependence of this contribution to VpeTt(x) the eigenfunctions of the one-electron Schrodinger equation is known. is large enough that the band structure of the infinite crystal is almost completely devploprd and. To this end. I contrast to infinite n Lrystals. The cluster with the point pprturbatinn at its center is clearly just a large molecule.294 Chapter 3. clusters have a surface. on the one hand. The primitive unit cell of this crystal is now. far example. which in this context is called a supeveell Thp crystal is referred to as a supercrystal. Such statrs must be remowd in a suitable way in order for the cluster method to be applicable. one finally arrives at an infinite crystal. on the other hand. The form of this dependence is governed by the particular oneelectron approximation used in the calculations . Its atomic and electronic struclureb can be calculated ubing the methods of quantum chemistry for the determination of the structure o f molecules. Hartree-Fock. the replacement of the real potential by a pseudopotential . where they cause no further difficulty. This finite part of the crystal is called a rlwter. Electronic structure of semiconductor crystals with perturbations electron-electron interaction contribution to V P d ( x ) . the saturation of the dangling bonds at the surface by hydrogen atoms.a technique which has been \-cry successful for ideal crystals (see section 2.is also applied in the supercell and Green's function methods. is small enough that the Schrodinger equation for it can be solved easily. however. any solution procedure must be iterated repeatedly until self-consistency is achieved.5) . Correspondingly. The latter also acts as a perturbation of the periodic potential and can gi%erise to bound slates in the gap. but not its actual value. As a rule. Cluster method Employing the cluster method. Local-Density-Functional theory or the quasi-particle method. the supercell method and the Green's function method. The . different procedures h a w been proposed such as.

The retarded Green's finctaon O " ( E ) is defined by the equation GO@) = 1 Eti6-H' (3. First we consider the bound states. e.g.3.H1-l stands in close relation t o the Green's function of the unperturbed crystal. Results for the band structure of the ideal crystal are neither necessary nor useful in either method. the eigenvalues E which WP seek from this equation lie outside of the bands.. i. for k = 0. The appealing feature of the supercell method is that the whole apparatus of band structure calculations for ideal crystals can be exploited for the electronic and atomic structure determinations of deep centers. to be mare precise. In the third method for calculating the electronic structure of perturbed crystals.L@ ". Also. The inverse operator [ F . (3. [E .H1-l of the operator [ E .5. As tl preliminary we note that equation (3. this decomposition is essential.131) can be formally solved for @ by multiplying both sides by the inverse [E . Green's function method The Green's function method employs techniques and insights of quantum mechanical scattering theory. the decomposition of the entire effective oneelectron potential into that of an ideal crystal and a perturbation potential need not to be made. If the supercell is made large enough. of the cluster in the first method and of the supercrystal in the second.132) . Deep levels 295 periodic repetition of the point perturbation in the supercell method causes the discrete d w p levels to become k-dependent bands of h i t e widths. these widths are negligibly small and it suffices to calculate the band structure of the supercrystal for one k-point only. In the cluster and supercell methods one obtains the deep levels of the perturbed crystal by a process in which one numerically calculates the energy spectrum of a model system.131) Since we are interested in bound states. and the band structure of the ideal crystal is required.HI+ ..HI. Bound states: Kostcr-Slater method To explain this method we write down the Schrdinger (3.e. the Green's function method. in the iundamenlal energy gap between the highest valence band and the lowest conduction band. It provides results not only about bound states with energy levels in the gap of the ideal crystal.21)equation for the perturbed crystal once again in a somewhat modified form. but also on scattering states having energies in the allowed energy spectrum of the ideal crystal.

This p r o w dure is rcfrrred to as Koster Slater method. then the matrix representation of the (heen's opertrtoi is not as simple as in the Bloch basis. The matrix represenlation of d ' ( E ) in the Bloch basis reads (3.296 Chapter 3. Using G " ( E ) . in that the response occurs only after the system has been perturbed. Koster-Slater method in Wannier representation Wannirr functions are linear combinations of all Bloch functions for a given band index v of the form . These levels ran thus be determined by calculating the Green's function G o ( E )of the unperturbed crystal and solving equation (3. As our present interest is in deep levels in the forbidden part of the energy spectrum of the ideal crystal. The energy eigenvalues E satisfying this equation are deep levels. (3.132) in the range of E of interest to us.134) holds.134). i t would be more expcdicnt for the matrix representation of the perturbation potential to use localized wavefunctions as) for example. in an appropriate orthonormalized basis set. i. atomic orbitals.I]?) 1 0. if Uet[G"(E)V' 1 = 0 1 - (3.131) as KosterSlater equation The Green's operator @ ( E ) can be cdriilattul if the band structure E. vanishps. no singularities occur in G " ( E ) of equation (3.(k) and the Bloch functions of the ideal crystal are known. However. A particular compromise in choosing a basis set for the representation ol the eigenvalue equation (3.equation (3.131) may be formally rewritten as [@(E)V' .133) Non-trivial solutions me possible only for energies E for which the deter. Electronic structure of semiconductor crystals with perturbations where 6 is an infinitesimal positive imaginary part which is set to zero after serving to remove singularities at the energy eigenvalues of the unperturbed crystal. and equation (3.1 minant of the matrix of the operator [ C 0 ( E ) V ' 1 .134).134) is the use of so-called Wunnzer finctzons. not in changes of wavefunctions with energies in the already existing continuous part.135) With this we only need to know the matrix elements (uk(V'1u'k') of the perturbation potential V' in Bloch representation in order to determine the deep levels using equation (3. and we may ignore 6. If one does so.r. This procedure assures that the wavefunction response of the unperturbed crystal conforms to the causality principle.

e.140) For the particular lattice point R = 0 it reads { 3. and both are equal to the lattice vector of the cell which hosts the point perturbation.134) i s written in terms of this basis. the Wunnier h c t i o n s IvRJturn out to be well localized in the unit cell at the lattice point FL If the eigenvalue equation (3. . we assume & = 0.139)) equation (3.143) as The matrix elements of the potential (vRIV’jv’R’1 are particularly large if R and R‘ are identical.3. Neglecting all other elements we find Employing (3.138) and (3.5.137) becomes (3. all other components (vRI$) follow at once from equation (3. its determinant has to vanish separately.If the latter are chosen properly.141) forms a closed set of equations for the central cell compo) nents ( ~ O ~ I Jof $ only.141) Equation 13. rdls in a ppriodicity rcgioa.140).136) Here the summation is over the whole first BZ. If the latter are known.141) to exist.G“ is the number of primitive unit. For a non-trivial solution of the homogeneous system (3. As before. i. it reads The matrix elements of the Green’s operator G o ( E )may be obtained by means of (3. and ‘ t k are certain phase a~glru. Deep levels 297 (3.

142) are those which form the gap. If we consider only them and neglect all others equation (3. G:(E:) may be written as with Jrm (3.(k) ' v = c. the host Green's functions G:(E) and G : ( E ) .298 Chapter 3.138) as G.232 R . Below we calculate the host Green's functions for isotropic parabolic bands of finite widths.147) whrre p v ( E ) is the density of states per unit energy and spin state p.143) for G : ( E ) we rqlace the k-sum by an integraL This yields G0 E ) J = -.e.(E) 1 (vOlG*(E)IvO) 3 = G 1 Ic E+ir-EE.142) may be obtained from (3.E ) into this integral. as well the perturbation potential matrix elements. have t o be known.142) becomes or more explicitly To solve this equation.(k)' (3. The diagonal elements (vOIGo(E)IvO) G ! ( E ) of the Green's = operator in equation (3. i. In expression (3. the uppermost valence band u and the lowest conduction band c.i t . v = c. Electronic structure of semiconductor crystals with perturbations must hold.E.&(k]) h3 1..148) .146) st beiug the volume of a periodicity region.(E) : d3kd(E . Introducing the identity operator dE'd(b" . (3.w.143) The dominant bands in equation (3. v. (3. 1 G 3 8x3 ' d%i s t ~ 1 ~E -I.

we approximate the true valence and conduction bands by isotropic parabolic ones. We substitute these expressions into the Green’s function G . Later. . ~ . the G r m ’ s function method in Wannicr representation will be used to address the question of whether or not main group impurity atoms in tetrahedral semiconductors form deep levels in the gay. the host Green’s functions of OUT model depend on three parameters.147). This corresponds to the use of an effective mass for each band averaged over the whole first B Z . The E‘-integral is readily done. We avoid this because it is more convenient to handle the many-valued character of the In-function rather than that of the arctarz-function. This would hP obvious if we rcplaced the In-function by an arctan-function.Eg) B(E . they Eare in fact real.(E). and the two band widths A& and AE.. The imaginary part ofG.E.3.5. Deep levels 299 which differs from the DOS in equation (2. The bandwidths are introduced by putting the total number of states of the approximate isotropic parabolic bands equal to G3.TI’F] (3.152) Although complex numbers appear in these expressions.213) by a factor (0/2).(E) equals (-TI times pv(E). The real parts ReG:(E) and ReG:(E) are given by -I. Altogether. however. In evaluating p. Then it follows that (3.150) where B(E) is the unit step function. The latter are measure3 of the awrage kinetic energies of electrons in the vakncce or conduction bands large bandwidths mean large average kinetic energies (or small eEective masses). to be the same as those of the original bands..)] E [ O ( . taking their band widths A E . ( E ) of equation (3.149) 3 pc(E) = ~ G3 ~ ~ ~.AE. (3. the energy gap EB.

(3.158) .209). this relation is known as the D p o n equatzon Using thk equation and performing some simple calculations. E1wtmnic Btructure Scattering states of serniconductar crystals with perturbations The perturbation potential also gives rise to changes within the energy bands of the i d e a l rrystal. here thai of the crystal with the point perturbation.[H+ V ' ].156) as (3 157) G'(E)V'I.300 Chapter 3.155) and (3. A 1 d dE (3.156) ol t h r nos clue l o the point perturbation. 4. The Green's function of the p e r t u r b 4 crystal oLrys the equation G ( E )= G o ( E ) t G ' ( E ) V ' C ( E ) . This change may be obtained from (3.i6 .1533 of G'(E). E ) (3.I m -In D e t [ G ( E ) ] . and considering the fact that G ' ( f i ) vanishes for li: -+ f m .155) of the unperturbed crystal may be expressed in terms of the unperturbed Green's function Co(E). change within the energy hands of the ideal rrysttll IS indured by the perturbation in the form of a modified density nf allowed energy levels pcr unit mnergy.154) which follows at once from the definition (3. (3. Integrating A p ( E ) over this interval. Of course. so that in this rwpeet there is 110 change.e.153) According to formula (2. However. i. the DOS expression (2. the w e r g i a of t h e w bands are still allowed quantum mechanically in the presence of the perturbation.P O ( W (3. yields 1 d Ap(E) = --Irrt-lnDDet[l- x lm M ~ E A ~ (=. In quantum field tbwry. 1 G ( E ) . 0. We seek the change I an analogous way? the DOS P O ( ! ? ) n M E ) = P(E). dE This relation can be used to ralculatc the total change of the DOS i the n entire enerRy range between -oo and t o o . To calculat? this change it is expedient to introduce the Green's fiirirtion of the perturbed crystal.em.209) may be brought into the form p(E) . in the form of a modifid density ol statvs. the imaginary part Im T r [ G ( E ) of the trace ] represents (apart from a factor -1/ir) the density of states p ( E ) of the syst.I.

In regard to ‘configuration dependence’. even thosc calrulatcd by means of configuration dependent Hartrw and exchange potentials. ‘configuration dependenre’ and ‘configuration interact ion’. The deep states in the energy gap occur therefore at the expense of band states. the total number of states remains unchanged. as discussed in section 2. the DOS of the perturbed crystal can display maxima or minima. the eigenfunctions do not decay exponentially but oscillate with an amplitude decaying to zero arcording to a power law. namely. and there it was referred to as Levznson’s theorem. At certain energy values in the bands.3. a state is lost from a band. dBAp(E).ion of Levinson’s theorem.2 here.1). this theorem means that for each new state of the crystal created by the point perturbation. also applies for purely long-range potenlials. dEAp(h’:) - Lap. we have proven what was anticipated earlier in section 3.1.159) In the above derivat. Thus. that for each shallow level in the gap. are not exact eigenstates of the N-electron Hamiltonian. Since the corresponding localized level is degenrrate with the band energy continuum. the localization of resonance and anti-resonance states differs from that of deep level states in the gap . This theorem. This result already was used in section 3. an rffwt which is referred to as cor~fignralzon znteraetzon (see section 2. Here. One of thcse e f k t s is based on tlie configuration dependence of the Hartlee and exchange potentials.4 in lhe context of shallow levels. These states emcrge when the short-range perturbation polential can bind or ‘anti-bind’ states at band energies. Deep levels 30 1 This relation signiEes that under the action of the perturbation potential.5. Another results from the fact that Slater determinants. For each state occurring in the gap. The exact eigenstates are linear coinbinations of different Sl&r determinants. The two correlation effects. no assumptions about the spatial variation of the perturbation potential were made.with increasing distance from the center. One speaks of these as resonance and antz-resonance state. this result will play an important role. (3. we continue the general discussion of section 3.5. will be discussed helow for deep centers. . therefore.9. are important for the N electron system of a crystal with oneparticle states localized at a deep centel. In Chapter 4.4 Correlation effects Correlation effects.where we will calculate the electron population distribution over the energy levels in the gap and the bands in thermodynamic equilibrium. R stale is lost fiom a band. 3.4. a state which existed without perturbation must cease to exist.

1)electrons at the center. Electronic structure Configuration dependence of semiconductor crystals with perturbations For an ideal crystal. the energy eigenvalues E . summing by all occupied oneparticle energies. followed by subtraction of the electrostatic interaction energy of the electrons because the latter is doublecounted in forming the sum of one-particle energies.l ) of the oneparticle Schrodinger equation with. Like in section 2.the level EP-” is deeper than the level E p ) because the removal of an electron results in the positive core being less strongly screened. and the total energy E t o d ( { v } ’ ]in theground state {v}’. according to formula (2. but it is no longer true that I. Theionized state (v)” differs from the ground state (v)” in that a particle. however. If one further considers that the total energies of both systems enter in the definition (3. E . of the onepartick Schrijdinger equation have direct physical meaning.. The essential requirement for the validity of this theorem is the approximate population independence of the Hartree and exchange potentials or. Apart from their sign.541. In this regard. that of the relaxed system with (n.e. n and n .I . -I. of the one-particle Schrodinger equation of the crystal with a point perturbation. and that of the unrelaxed . of the effective one-particle potential. The equation E . We will denote these oneparticle energies by E:) henceforth to emphasize this dependence explicitly.160) of the ionization energy is also valid in this case. we say that the electrons at the center relax on the removal of an electron from the center. That this cannot hold is immediately clear if one recognizes that the eigenvalues IT?) and E P .2.302 Chapter 3. The total energy of the ground state follows. the definition (3..1 one says that a31 electron is removed from the system. The potentials depend on the number n of electrons occupying oneparticle states localized at the center.. is transferred to a oneparticle state of energy 0 corresponding to the vacuum level. = .160) of the total energy R t o ~ ( { v ) ” ) the N-electron system in the ionized stair of {v}”.1.. respectively.1 electrons at the center differ from each other . Of course. represents the ( negative oneparticle energy -E$. and so do the energy eigenvalues E . i. the ionization energy Iv is definned as difference (3..160) of I. more generally. according to section 2. is the content of Koopman’s theorem. for if taken literally i t misrepresents the charge neutrality of the system. so that the remaining electrons are more strongly attracted. which in the ground state of the system occupies a oneparticle state of energy E. they are the ionization energies I. This requirement is not satisfied for a crystal with a point perturbation. This expression has to he used with care. which was explained in section 2. of the corresponding eigenststes Y . In this situation.

In density functional theory.54). Firstly. an electron originally localized at the center may undergo a transition to the bottom of the conduction band. is only one of the various possible one-particle excitation processes of the N-electron system of a crystal having a perturbation center. so to speak.E ~ M ( { v } ' ) not equal to either one. during its removal. Applying equation (2.1 localized electrons. the two total energies follow more directly: one determines the eigenfunctions of the Kohn-Sham equation for the centers with n and n . feels. To carry out an exact calculation of the ionization energy of a center which. we are interested in excitation processes involving changes of the populations of one-particle states localized at the deep center.e. the potential with n localized electrons half of the time.16 1) As in the case of ionization.E. i. in its ground state. Deep levels 303 system with n electrons at the center.these oneparticle energies provide the total energy E b ~ ( { v } ' of the ground state. one may examine an ' ~ excited state { v } ~with an electron in a formerly unoccupied one-particle state Y of energy below the vacuum level. The corresponding excitation energy Iuiv is given by the total energy difference between the excited state { Y } ~ and the ground ' ~ state {}. and evaluates the total energy functional (2. ) but they cannot be used to calculate the total energy Etotal({v}v) of the ionized state with n .1) localized electrons there also half of the time. and a hole in a formerly occupied ' one-particle state v. exciting an electron to the vacuum level. Ionization. This is referred to as a donor transition Thirdly. in the final state. In reality. has n localized electrons. Here. Secondly. the excitation energy Iulv is not equal to the one-particle energy difference E.. all electrons may still be localized at the center. Such excitations are called internal transitions of the center.1/2) of electrons at the center.E ~ M ( { V } 'should be equal to the negative eigenvalue . There are different types of such processes. there is no way to explain why the ) energy difference E b t d ( { v } v ). the ionization energy E b t a l ( { v } v ) . Generally.64) using these densities. This is plausible because the electron. one also needs the one-particle energies EP-') of the N-electron system with n .i . To obtain the latter.1 electrons. and feels the potential with ( n .1 localized electrons at the center. but lies somewhere in is between the two. It can be shown that it is approximately given by the negative of the one-particle energy eigenvalue of the N-electron system with the fictitious number ( n .5. but with one electron having changed its localized one-particle state. an electron . then forms the corresponding ground state densities.3. the one-particle energy eigenvalues E P ) are not sufficient.E Z ) of the unrelaxed system and not equal to the negative ( eigenvalue -EP-') of the relaxed system. v' (3.

from the t.erna1vacuum Icvcls’ one 0ft. If one subjects the centex A(-) E D ( . The donor excitation level for a center D in the neutral charge state D(O) is denoted by n(O/+). In fact. one has donor and acceptor excitation lcvels =1 ~ 1 ~ . excitation levels E$V . t.y one-particle state Iocalized at the center. one has (3. As excitation energies of the N-electron syst.) and D ( .162) If one measures thc acceptor ionization level relative to the conduction b u d . If the donor excitation level D ( + / 2 + ) at t. If only the excitation level D ( O / + ) lies in the gap.m refers to donor and acceptor transitions as donor and acceptor ionizut.em of the perturbed crystal. The sum of the two ionizalion energies A ( O / . for an x:cept. therefore.E .wo-step ionization process of the center A(O). OT d o u h k donor.here are m d t i p k donors. Generally. ionizing a neutral acceptor center A(0) leaves this center in singly negative charge state A ( . and to & curraponding excitation energies as ionization lez~elx. and an electron appears at the conduction band edge. all transition energies discussed above may be plotted in the same energy scheme. the donor D ( 0 ) is simply ionizable. or a single donor.) .) t o a donor transition D ( .ation level for a center A in its neutral charge state A(0) is denoted by A ( O / . Viewing the hand edges as ‘int..nr A ( Q ) in charge state &. they are not: they are one-particle ezcitation levels. More strictly speaking./ O ) then the center returns t.11). an electron-bolc pair is excited while the state of the center has not changed.304 Chapler . (see Figure 3. The excitation energy for an electron from the t. just as if they.were oneelectron levels. ~2~ Below. Electronic structure of semiconductor crystals with perturbations Figure 3. In the general case. An analogous terminology i s used for acceptors. and the mceplor excit.ion band defines the energy gap.o its neutral charge slate D ( 0 ) A(O).he single positively chargcd donor center D ( + ) also lies in the gap. and a hole appear8 at the valcncc hand edge. As a resdt of this t. But.iuab. the gap energy E .op of the valence band to the bottom of the rnnduct. the (minimum) excitation energy of an electron-hole pair.11: Reletion between donor and acceptor ionazation levels. one has a dovhly i u n i m b k . we will use this terminology Acceptor ionization lcvcls may be traced back to donor ionization levels. namely./ O ) equals. This type of excitation is called an acceptor transition.) .op of thevalencr band may be transferred into a previously empt.7.

1)/Q) and the donor ionization energy X(Q/(Q 1))of an amphoteric center X(Q) is. + (c) if both levels X((Q .l ) / Q ) . both a donor and an acceptor or none of them. One therefore has + Since. The number of electrons bound at a center in thermodynamic equilibrium depends on the position of the Fermi level with respect to the ionization levels. for this conclusion to be valid. simultaneously. that This unified description of donor and acceptor excitation levels makes it possible to decide in simple way whether a given center X represents a donor. One has (a) a pure donor.3. i.l)). simultaneously.the charge state (Q 1) is realized. both levels have to be located in the gap.162) setting A’(&/(& .1))= Eg .1)/Q) does not. the Hubbard energy 1.1)/Q) and X(Q/(Q the center is neither a donor nor an acceptor. From the outset it i s clear that the ionization level X(Q/(Q + 1)) also marks that position of the Fermi level at which the charge state of the cenlei changes: if E p lies just above X(Q/(Q I l)). by definition. h o r n this observation one may conclude that the charge state Q occurs when the Fernii Pnergy lies above the ionization level X ( y / ( y t 1)) and simultaneously below the ionization level X((Q. an acceptor.the charge state Q is realized.e. the Hubbard energy U is positive.A(Q/(& . Deep levels 305 edge instead of the valence band edge (as is done in equation (3. thus then it follows from (3.l ) / Q ) . + 1))lies in the gap The difference between the acceptor ionization energy X ( ( Q .l ) / Q ) and X(Q/(Q 1)) are found in the gap. - + if neither of the two levels X((Q . Of course. X(Q/(Q 1))does not.l ) / Q ) lie in the gap and.5. + (b) a pure acceptor. + + + Configuration interaction If there is degeneracy among the various oneparticle states of an N-electron system. if X((Q . the acceptor ionization level commonly lies highcr in thc gap then the donor ionization level. if E F lies just below X(Q/(Q l ) ) . between the two levels X(Q/(Q 1)) and X((Q .162)). when the ionization level X(Q/(Q 1))lies in the gap and.J. coninionly. the center is both a donor and an acceptor. the ionization level X((Q . One then calls it amphoterzc. then there is also degeneracy between the Slater determinants formed .

The result of this removil can be derived by means of group theory. altogether. beside a non-degenerate state belonging to the irreducible representation A l . which differs for the two groups of states. 12) of the 7'2-state. namely and 3 antisymmetric two-particle wavefunctions. the first case applies if the total spin S is 0. namely These are. this degeneracy is removed. we concentrate on those degenerate one-particle states which are localized at the deep center. The existence of such degenerate states was demonstrated in subsection 3.2 electrons are in extended valence band states. Since a Slater determinant itself is antisymmetric with the respect to the exchange of two electrons. the Slater determinants for the two electrons of the deep center are products of coordinatedependent and spin-dependent wavefunctions.2 . and the second case if S = 1 (other values of the total spin are not allowed). one can combine 6 symmetric two-particle wavefunctions. we use a simple model: a deep center with 3 degenerate localized one-particle states of symmetry Tz. the remaining N . The extended electrons contribute to configuration interaction only little. for a system with two electrons. Neglecting spin-orbit interaction. strictly speaking. at least within the framework of the one-particle approximation. or the spin-dependent wavefunction is symmetric and the coordinate-dependent wavefunction antisymmetric. the symmetric and antisymmetric wavefunctions have slightly different energies because the exchange energy depends on total spin S . as one should expect. however. Using the three wavefunctions Iz). ly). we disregard them in our further discussion. occupied by 2 of the N valence electrons of the crystal. Within each group there is degeneracy.the vacancy in Si exhibits a %fold degenerate state transforming according to the irreducible representation T2 of the symmetry group T d of the vacancy. From quantum mechanics it is known that. 3' = 9. there are two possibilities for the behavior of the two factors in regard to particle exchange: either the spin-dependent wavefunction is antisymmetric and the coordinate-dependent wavefunction symmetric. If the configuration interaction is taken into account. Electronic structure of semiconductor crystals with perturbations from one-particle states of this type. If spin and exchange interaction are considered. .5. Here.306 Chapter 3. To analyze the consequences of configuration interaction.

As in the free atom case. the representations in oneparticle space are denoted by lower-case letters in this context.. tl. Below. instead by upper-case letters A l . F represent many-particle states.e. in the ground state configuration {aSt. In these relations. Deep levels 307 by means of the decomposition of symmetric and antisymmetric product representations into irreducible parts (see Appendix A). therefore.Tz etc. The splitting of the many-particle levels of deep centers of crystals has its counterpart in the fine structure of the many-particle energy levels of free atoms with more than one electron.e. Using the notations introduced above.p.and upper-case representations wherever an ambiguity might occur. for example.e. appended to the representation letter at its upper left. and if oneparticle states of different irreducible representations are involved as. having different total angular momenta J . . we may conclude the analysis of our model deep center by stating that configuration interaction will split its {t. as we will see below. we will employ the distinction between lower. This is in fact the case.}-configuration into the 4 different two-electron and 3T1. T I . should result in deep levels exhibiting pronounced fine structure splittings. Here. formed from one-particle states of given total spin S and orbital angular momentum L . that impurity atoms with unoccupied d. 'T2.(or. ' E . generally. and S.} of the neutralvacancy with 4 electrons. atoms of transition groups of the periodic table. One may expect. To avoid confusion. For the symmetric = A1 E 2 T2.. by a l . (Recall that the irreducible representations of the full rotation group. for d.and f-shells (as opposed to s. while on the righthand side one has representations in two-particle Hilbert space. The only difference is that the symmetric and antisymmetric products to be decomposed into irreducible parts have more than two factors and the factors are not necessarily the same. f represent oneparticle states. the factors on the left-hand sides are representations in oneparticle Hilbert space. where s. i. upper-case letters are used for two. multi-) particle representations. are distinguished by J . then the corresponding many-electron levels can be obtained in the same way as above. into which the products of the irreducible one-particle representations decompose. and every state on the right-hand side 2 electrons. many-particle states. ) This fine structure splitting has its largest effect for electron shells which are strongly localized. energy levels 'A1. P. d .and f-shells. i. and for the antisymmetric product one obtains (T2 x T Z } ~ product (2'2 x T2}a= T I . which are common in group theory. A2. For such atoms.e. This means that every state on the left-hand side can host 1electron. i. a2.5. the total spin S of the many-electron state is indicated by the spin-multiplicity 2s 1. + + + If more than two electrons are localized at the center.3.E .and p-shells). t2 etc. give rise to slightly different energy levels. D . This is chosen in accordance with the notation for free atoms.

Knowledge about these centers is. also spatial symmetries. in every. Experimental methods One can divide the experimental methods for investigation of deep centers into two groups. This results in an exponentially decaying current. thus. the case of deep acceptor levels may be treated analogously). methods which give experimental data on center properties in thermally or optically excited states. the electrons are freely mobile carriers and are immediately sucked up by the positive electrode at the nregion. These methods provide data concerning the total spin S of the centers and. This state does not occur suddenly. it adjusts exponentially through emission of electrons from the deep levels into the conduction band (we assume deep donor levels here. The decay time of the current and the rise time of the associated capacitance change are determined by the emission probability from . like Electron-Paramagnetic Resonance (EPR). and on the other hand. an increasing capacitance of the junction. The chemical identity of the centers can be determined (in addition to other methods) by means of mass spectroscopy or of Rutherford Backscattering (RBS). on the one hand. Measurements of the Extended-State X-ray Absorption Fine Structure (EXSAFS) provide data about the geometrical ordering of the atoms in the vicinity of a point perturbation. if anisotropy effects are measured. Electronic structure of semiconductor crystak with perturbations 3. Ionization energies can be determined by means of optical absorption spectroscopy and photoconductivity measurements.308 Chapter 3.5. we first present a short overview of the experimental methods. optical and electrical methods are available. The cross-sections of deep centers for emission of free charge carriers can be determined by means of time resolved current or capacitance measurements at pn-junctions or at other depletion layers. Since we have thus far treated only theoretical methods. however. In the conduction band. By suddenly applying a reverse bias at such a junction. To investigate the excitation properties of deep centers. Among the methods of the first kind are measurements of magnetic properties. the deep levels are lifted relative to the Fermi level The new equilibrium state of the junction corresponds to fewer electrons in the deep levels than previously.Electron-NuclearDouble Resonance (ENDOR) and magnetic susceptibility. which for its part leads to an increasing positive charging and. mainly in the infrared spectral region. case the product of combined experimental and theoretical investigations. methods which measure ground state properties of the centers.5 Results for selected deep centers Below we discuss the structure of several deep centers which are important either from the scientific or technological point of view.

so we initiate our discussion of particular deep centers with it. More rigorous calculations within one-particle approximation (3araff. The one-particle energies of these centers differ by the Hubbard energy U.12 (part b). many-body effects. A simple estimate yields 0. Measuring the capacitance rise time yields experimental values for the emission probability.1e V . is approximately justified. The recovery time for the capacitance change after a filling pulse has been switched off. configuration dependencies of one-particle energies: should be important in the case of the Si-vacancy. This fiinction exhibits maxima which.3 el’ for C3.4t maximum. and a description of the vacancy in terms of one-particle states. i’(O). including configuration mixing. wherein a reverse biased pnjunction is exposed to periodically repeted voltage pulses of forward {deep level filling) polarity. this can be 6.3 e V for U . and this lowers thc enerm of the finel stat?. Optical ionization occurs instantaneously. and at minimum 0. The t 2 -level can lie in the gap depending on how many electrons it hosts.13). no electrons are available . are small. smaller than optically measured values: the lattice has time to rrlax if ionization proceeds thermally. hence lattice relaxation is is not possible. Of particular importatice is the so-called Deep Level Trawaerat Spectroscopy (DLTS)./ 0 ) and V ( 2 /-1 are found there (as above the acceptor levels are counted relative to the conduction band edge). In charge state V(Z+). 1980.’(+). As such.3. Perhaps the best understood point perturbation is the vacancy in Si. t’(O/+). Ir(3-) and V(4-). It predicts the existence of two bound one-particle states. I. Thus. 1980) show that the al-level can be excluded as a deep state in the gap because it lies in the valence band (see Figure 3. the donor levels 5’(+/2+). and the acceptor levels V ( .5. Schliiter. a non-degenerate al-state. I?wp let& 309 the dttep centers. it may be expected that three or four ionization levels codd fit in the Si gap of about 1. it is fully occupied having two electrons. is measured as a fimrtion of temperature. Pantelides. calculated positions of these levels are shown. under certain conditions.2. as a rule. Bernholc. can be used to determine the ionization energies of the deep centers. . namely t7(2+).I. These are not yet final positions because lattice relaxation has not yet been considered. The latter leads to changes which are discussed below (see Figure 3. Thus there exist 7 charge states of the vacancy. Vacaricy in Si of the vscancy was treated in section 3. A4ctualIy.’(-).12a). more strictly speaking. The defwt molerule model Owing to the value of about 0. V(2-). albeit configuration dependent ones. and a tripiy degenerate t2-state. Ionization energy values from LILTS measurements and other thermal quililrrium technique are. Other many-body effects. In Figure 3.

Considering that the wavefunction of the deep vacancy levels extend as far as the nearest neighbor atoms. with Fermi energy lying above the V ( O / + )donor level and below the V ( .e.-distortion. The occurrence of an effectively negatke iJ at the vacancy in Si was first predicted theoretically (BarrafF. In order to gain additional energy. Through a further distortion of the vacancy. but the increase of ionization energy due to the Jahn-Teller effect on the V ( + / 2 + ) transition amounts to only about halfof that for the V(O/l+) transition since the Jab-Teller effect is absent at the V ( 2 + ) center.e. Schliiter. In charge state V ( 0 )the additional electron can also be hosted by the bz-level. population of the e-level begins. it will capture another hole passing into charge state V(2+). The bz-level lies energetically below the e-level and is single occupied. Of course. therefore no Jahn-Teller distortion of the vacancy occurs. without further change of the Fermi energy. The symmetry after the distortion is DM. This level can also still host the additional electron of the charge state V(2-). One therefore also calls the vacancy in Si a negatzwe-U center. and from there. with an increase of the C2. If one takes account of the energy shifts diie to Jahn-Teller distortion. i. In charge state V (-). A surprising result concerning the level positions in Figure 3./ O ) acceptor level. so that practically no spin-splitting of the vacancy levels occurs. i. . with subsequent lowering of the Fermi energy below the V ( O / + ) level. which reduces its symmetry from D M to CzVithe e-level splits into two levels and the additional electron is placed in the deeper of the two. 1980) and later found experimentally in correlated EPR and DLTS measurements.310 Chapter 3. spontaneously. this is understandable. In charge state V ( + ) . 1 2 ~ .'I'he exchange interaction evidently plays only a minor role.12~ that is the donor level V(O/+) l e below the donor Ievel V ( + / 2 + ) . If the vacancy was initially in the neutral state. This phenomenon has now been observed at a number of other deep centers. the 3-dimensional irreducible representation t 2 splits into the 1-dimensional representation 62 and the 2-dimensional representation c. For this group. the tetragonal Jahn-Teller distortion is strengthened. the interaction energy between two electrons at the center does not really change its sign. then the vacancy will initially capture a hole from the valence band and pass into charge state IT(+). Formally. the resulting level positions are as shown in Figure 3 . it seems as if the Hubbard energy U would be negative instead of positive for the transition V ( + / 2 + ) . Its energy can be degraded through a tetragonal Jahn-Teller distortion. Electronic structure of semiconductor crystals with perturbations for the population of the t 2 level. the tz-level is occupied by 1 electron. The usual is ordering of the ionization level of the more negative charge state above the ionization level of the less negative charge state is thus reversed.

(After Watkins. high.111-VI. include Jahn-Teller shifts. b) Levels of a) with Hubbard corrections. if the impurity atom is a nan-metal atom. It lies between 10" for chemically very similar systems such as GaAs. ) Main group impurity atoms in tetrahedral semiconductors The elements of the main groups of the periodic table are distinguished by the fact that their valence shells arise born 3. l S S 4 . respectively.5. through sp'-hybrids. therefore the anion site. Relow we refer to them as 'tetrahedral semiconductors'. That implies that the incorporation of impurity atoms should be mainly substitntional in such crystals. the cation site. diamond and zincblende structure in most caws. If main group elements appear as impurity atoms in such crystals. as well as thc IV-IV. then they are chemically bound in a manner similar to that o the hust crystal atoms which f they replace. The groupIV elements.12: Deep levels of avacsncy in Si: a) Calculated ionization levels without Hubbard corredions and lattice relaxation.and p-orbitals.Al.e. the lattice site which is prpferred is the one that belongs to the chemically most similar atom of the host crystal. form crystals with. The numbers give the level distances from the valence band edge in eV. i. if it is a metal atom. c ) Fsxperimetital ionization levels which. The solubility of the main group elements in tetrahedral senlicntiductors is. Deep levels 311 Figure 3. accordingly. in addition.and 11-VI binary compounds. In the case of a compound semiconductor. and.3. and l O I 5 ~ r n -for ~ .

Different charge states of the vacancy are shown. also a long-range Coulomb part. b. For isocoric impurity atoms. Si:Hg. i. this potential leads to shallow donor or acceptor levels. The perturbation polrntial of a main group impurity atom in a tetrahedral semiconductor contains. On the right-hand side. (After Watktns. besides the short-range part. the Coulomb potential is in general the main contribution.13: Defect molecule model of a vacancy in Si. l U U 4 . for inst ance.4. ) relatively different systems as. These are the levels principally involved if main group elements are used as doping atoms for .e. the basis functions of the irreducible representations of the deep k v e l ~are indicated (a. taking into account the torresponding Jtthn-Teller distortions. as a rule. atoms whose cores do not deviate too strongly from that of the host atom. Electronic structure of semiconductor crystals with perturbations cl v’ D2d - Dzd d) v-o+d -btc Figurr 3. c Bnd d bband for the dangling hybrids of the 4 surrounding atom). As shown in section 3.312 Chapter 3.

6). P.31 1 + 0.0. or ZnTe:O). Al. in particular cases.3. [Data compiled from Landoldt-Barnstein. Sn. Sb.20 Hg Ec . the general results obtained there also apply to compound semiconductors.0.) ?r Be B - C - hk Zn A1 E C Vac. Deep ler7ek 313 Table 3. Pb). the short-range potential dominates in general. 0. however. In E.14 P - 0 S Ec . Isovalent substitutional impurity atoms therefore lead either to deep levels (this occurs if the isovalent host and impurity atoms are chemically dissimilar.0.6: Experimental deep l e d positions of neutral main group substitutional impurity atoms in Si (in eV). Ga.25 T1 Pb ~ Bi - Po tetrahedral semiconductors. .15 E. Ge. If an impurity atom belongs to the same column of the periodic table as the host atom. The neutral vacancy (Vac. one says that the two atoms are isovcalent. t 0. Bi). . An important theoretical problem which has yet to be solved for maingroup impurity atoms in tetrahedral semiconductors is to understand why certain elements cause deep levels in the gap while others do not. which forms an alloy). As. and. as in the case of GaP:P. the Coulomb potential vanishes completely and the short-range potential remains as the only potential contribution. 1982. gives rise to deep levels in the gap (see Table 3.55 Ec . The impurity problem mentioned was treated above within the defect molecule modeL Although group-IV elemental semiconductors were assumed as host crystals.3 Te Cd E. An empty space means that the correspondingimpurity atom is either not incorporated substitutionally.0. For non-isocoric elements of the main groups. or that such states exist but are shallow (B.0.5.32 + Ga - Ge - As - E.) is shown for comparison. "Dash" indicates that no deep level occurs in the gap €or this particular substitutional impurity. .43 N Ec . Sn - Sb - + 0. In this case. meaning either that no localized state exists at all (C. or no localized levels OCCLU at all (this takes place for chemically very similar isovalent host and impurity atoms as in the case of Si:Ge.31 Se E1.0. or that there i no unambiguous experimental s data.

Wolford. Figure 3. are depicted in Figure 3. If the perturbation potential V ‘ takes increasingly positive values starting from zero.e.e. The data from both sources agree that no deep levels exist in the case of the isovalent group-IV atoms C. ER The above conclusions are essentially confirmed by the more accurate Green’s function tight binding calculations performed by Hjalmarson. the perturbation potential V’= . Among the group-V substitutional impurity atoms N. In the case of group-\’I atoms. Ge. Such levels are not well described in the TB calculations quoted above. which summarizes experimental results for this host crystal. then a deep level in the gap will evolve from the conduction band below a certain negative threshold value. V ’ has positive values (or is repelling) if the hybrid energy of the impurity atom is larger than that of the host atom. For the particular case of Si this can be seen by means of comparison of Figure 3. the deep level in the gap should be the bonding ta-level. and Dow (1980). Furthermore. one can guess its symmetry as folIows: The perturbation potential V’ = e t . then one expects a deep level to arise from the valence band above a certain positive threshold value. concerning allevels.14 agree surprisingly well with experiment. S.14. the perturbation potential is positive. Figure 3. Pb. like Ga or Zn. For impurity elements left of column IV of the periodic table. i. and Se. Some results of these authors. of these symmetries (see Figure 3. cannot be decided by means of the defect molecule model. i.10 indicates that for negative (attracting) perturbation potentials. ils.E: has negative values (or is attracting) if the hybrid energy of the impurity atom is lower than that of the substituted host atom. Electronic structure of semiconductor crystah with perturbations Accordingly.3 14 Chapter 3. by varying the impurity atom. while experimentally one also finds a deep level for substitutional Te. and the deep level in the gap is expected to be tz-like rather than al-like. P. they are plotted against the s-orbital energy of the impurity atoms in Figure 3. if the group number of the impurity atom is higher than that of the host atom. Which of these levels are located in the gap. a look at. Since the a1-levels arise mainly from atomic s-orbitals. Using this observation.14. Sb.10). the indications of Figure 3. only I gives rise to a deep level while all others result in Y shallow levels (even those do not exist for the isovalent group-IV atoms). a1 and t 2 symmetry. a substitutional sp3-bonding impurity atom in a sp3-bonding L host crystal will introduce two bonding levels E ? and E t T of. If.14 indicates deep levels for substitutional 0. . and which are not. Sn. and for positive (repelling) perturbation potentials. and two anti-bonding levels E:T and E ’ : . Concerning the question of whether or not a main group impurity atom gives rise to a deep level.E: takes increasingly negative values starting from zero.14 with Table 3. On the assumption that there is a deep level in the gap. Bi.6. respectively. the deep level should be the anti-bonding u1-leve1. for impurity atoms with lower group numbers than the host atom. Vogl.

1980) The fact that the perturbation potential is negative (attracting) for the antibonding al-level and positive (repelling) for the bonding &level allows an important conclusion on the nature of the deep impurity states: in both cases. see the main text. particularly. Dcep levels 315 0 Y >" QI -1 W -2 0 L I I I I I 11 I I I! Eandedge t > Q) A -1 - u w -2 Cation Site -3 I I I 1 I I A -30 -20 -10 0 s . Wolford. Quantitatively. Vogl. the al-level positions in Figure 3. For further discussion.14: Deep levels for main group substitutional impurity atoms of various tetrahedral semiconductors. and Dow.14 differ from the experimental ones.Orbital Energy (ev) Figure 3. The anti-bonding levels of al-symmetry are shown as a function of the s-orbital energy of the impurity atoms. we show in Figure 3. have been neglected. many-body effects. configuration dependencies of the one-electron levels. and lattice relaxation has not been taken into account (Scherz and Scheffler. the corresponding wavefunct ions have larger amplitudes at the surrounding host atoms than at the impurity atom. To get an idea how these effects would modify the results.15 the expected occupancy of the deep oneelectron levels in the particular case of Si as host crystal. In this sense these deep impurity states are more host-like than impurity-like. (After Hjalmarson.5.3. 1993). This is to be expected because of the great simplifications made in the calculations. using the level ordering suggested by the above-quoted calculations .

As in the vacancy case. Of the 9 electrons of a Sirgroup-1’ atom molecule (remember that only N results in a deep level in this case). Qualitative . 6 and 5 electrons. In a 5’t:groupVI atom molecule with 10 electrons. 2.V.VII. 2 occupy the al-level. f . d . -11 and -I atoms have. Electronic structure of semiconductor crystals with perturbations d) el fI Figure 3.15: Energy levels and their populations for sp3-bonding main group impurity atoms in elemental semiconductors of group IV. and 3 electrons to be placed in the bonding tz-state which forms the deep le\Tel in this case. and in the 3t:groty-VI atom molecule with 11 electrons.HI. respectively.I. The defect molecules of group-111. This state of the molecule will certainly not be stable.\’I. One may also say that this level hosts. c . respectively. 5. in addition 1 electron has to be placed into the anti-bonding tl-level. e .within the defect molecule model.11.316 Chapter 3. Of them 2 electrons are hosted by the bonding al-level in the valence band. b . and the defect molecule model. 8 are hosted by the four bonding states and the remaining electron occupies the anti-bonding al-state in the gap. 7. and 3 holes. a Jab-Teller distortion will occur which lowers the total energy. 4. The partial illustrations a) to h) correspond to impurity a t o m of groups I to VII as follows: a . a Jahn-Teller distortion will occur which removes the degeneracy of the ta-level and allows for a lower total energy by occupying levels shifted downwards. respectively. Again. There are. 1.

167) The factor in (3. of equations (2.303) and (2.166) where EL is the hybrid energy of the impurity atom. The Chen’s function in Wannier representation has already been determined above (see equations (3. Fiist. Analogoiisly. taking the difference .. in an approximate sense. V .. For the evaluation of the Koster-Slatcr equation (3. is the hybrid energy of a host atom.166) and (3. agdin taking Si as the host crystal.. of equations (3. Then. Foi these atoms..and matrix .152) we need the matrix elemeuts V. 1 + EL). the bonding and antibonding orbitals IbtR) and latR) are the Wannier functions of the eigenvalue equation (3. an expression for (vO1V’(wo) G V.166) arises because the Wannier function is equally spread out over the two atomic sites of a unit cell.5.152). (3..304). . matrix elementu of fI and IT I V’ between anti-bonding orbitals may be used to obtain an expression for (cO(V‘lc0)I_ v.5. V. Ag) or d. d-electrons participate in chemical bonding with the host crystal. the ILamiltonian of the ideal crystal is diagonalized by the bonding and anti-bonding Bloch functions Ibtk) and In&). We will discuss this problem in more detail in the context of the transition metal impuiity atoms. We will use thmn to grt explicit expressions for V. 3 .158) and (3. we write down the matrix representation of the unperturbed ..of the perturbation potential V ‘ in this representation.. Thus. t = 1 . The question of whether deep levels exist or not for a particular substi tutional impurity atom.and f-shells (Au). Siiicc none of the matrix elements of (3. 2 . one may identify IbtO) with the Wannier function of the uppermost valence band..165). 1 h (3. 4 . Deep levels 317 differences from this model occui for elements of the first main group which have no occupied p-states but relatively shallow closed d-shells (Cu. In the simplest veision of this upproximation.166) depend on t .Eh).159)).165) and (3.. one has t h e same matrix elements for all R and R’ with the exception of R R’= 0. while the substitution of a n atom occurs at only one site. ran he treated arralytzrally. The latter elements are (btOlH i V’lbtO) - S(E. It is given ’by (btRIHI4R’) fhGRR‘.v o . we will discuss it hclow. and V. h (3.3. Hamiltonian H between bonding orbitals. employing the Wannier representalion of the Green’s function derived above. To calculate them we use the results of the TR approximation of scction 2. follows SS vlf..165) where E.V.. For the perturbed Hamiltonian EZ fV’. As lhis calculation provides further physical insight into the formation of deep levels. v u s ( 6 th ..

in the case of negative VO. lV01 must exceed a minimum value J V O ) ~ ~ ~ given by (3. i.[./2. ..2. A&.169) takes the form (3. v ..171) to exist at all. For Vi -t +m. fi] (3. In order for a solution Et of equation (3.152) located in the gap.. i./2. (3.!(E) are zero: and equation (3. If one assumes.171) It has solutions Et only in the energy gap 0 < Et < E. El approaches the value E.v >> Eg.e. and the perturbation potential constant Vo. Electronic structure of semiconductor crystals with perturbations elements between bonding and anti-bonding orbitals yield the expression for (wO1V'lcO) V. It turns out that all elements are the same. i.171) may be written in the closed form . the solution of equation (3.1721.170) With this exprwsion! the deep level condition (3./=.152) transforms into Solutions of equation (3.168) We seek deep level solutions Et of the Koster-Slater equation (3.. the deep level is pinned at the midgap position. the gap energy Eg.Considering equation 13. with 0 < Et < EQ. This is evident if one considers the particular case AE. For such energies.e.318 Chapter 3. one necessarily has Ef > Eg/2. within which Et has to be restricted anyway because the deep level condition (3.then Re[G:(E) G:fE)] - + (F)-& . This corresponds to the pinning of & to the vacancy level discussed in subsection 3. = LG. for positive Vo. For negative Vo. which can be realized. The arguments of the logarithmic functions in G : ( E ) and G:(E) are close to 1 in thia case.170) is valid only there. and Et < E. the imaginary parts of G:(E'} and G.5. that A & = AEw. the two band widths AE.171) by identifying Et with the lowest possible deep level position in the gap namely Et = 0 in the case of positive Vo. in addition.169) within the gap do not exist for all possible values of the 4 parameters entering. and by identifying Et with the highest possible value of Et namely E.e. = v = v..e.172) This minimum value of (Vo(follows from equation (3. . and the logarithms themselves become negligibly small. i.

which militates against binding.91 Hg 1.99 -1. The latter are partially reproduced in Table 2.21 eV.18 Zn 1. = 3.3 eV is a reasonable choice. Comparison with experimental results €or deep levels of substitutional impurity atoms in Si shown in Table 3.2.08 A1 1. calculated by means of HermanSkillman s. the absolute value of the potential and the energy gap must be relatively large.03 Bi Po At -0.87 0.31 F -6.3.96 -1.41 Vac 8.7: Perturbation potential matrix elements Vo = (1/2)(~: .1 eV.21 eV.21 e V . are listed in Table 3. a deep level should exist for lV0l > 1.82 Cd 1.88 In 1. The perturbation potentials V-0 for impurity atoms of the main groups II to VI of the periodic table.42 -1.97 -2.71 c l -3.57 Mg 2. In this case one has Eg = 1. 1963.04 -4.35 Pb 0.167).24 -0.6 reveals that . EnIarging the gap and lowering the bandwidth increases the likelihood of forming a deep leveL The condition lVol > IV0lmifi may even serve as a quantitative guide.12 -2. as the following numerical example for impurity atoms in Si demonstrates.68 According to condition (3.8 P s -1.5.17 C -1.7.14 TI 1. = A E .47 N 0 -3. and AE.04 Sn 0.22 -2. so it should not be too small. According to our model. and the bandwidth relatively small.28 Ge -0.$) (in eV) for substitutional impurity atoms of main groups in Si.98 Sb Te I -0. Deep levels 319 Table 3.and p-orbital energies. That lVol needs to be large enough is obvious.05 Ga 0.) B e B 1. and should not exist for IVoi < 1. The gap is the energy range where the deep level has t o be placed.172) for a deep level to be formed. (After Herman and Skillman. calculated by means of equation (3. IVolmiplis 1.56 As Se Br -0. The bandwidth must be sufficiently small because it corresponds to the average kinetic energy. With these values.

and for M n in GaAs the solubility reaches as high as 10" ~ r n . due to its compensating effect! makes the crystals serui-insulitting. it is understood that. This is not surprising since the Thl elements are all chemically very similar. Go and Xi. try to minimize the contamination of the devicw by 3d-'I'M atoms. in the case of Cr in GaAs which. Them are the elements Sc! Ti. 1994).3arc? reached in tetrahedral compound semiconductors. or as capture centers for h e carriers which partially compensate the effect of dopant atoms. all three groups of TM atoms prefer substitutional incorporation on cation sites.he fact that their deep levels play an import. These effects are imclesirable in most caws. although. Transition metal impurity atoms The transition metal ('YM)-impurity atoms of the iron group. M Among them.ant part in electronic devices.found. Cr. Andersm. which are close to the border line of our model but still on thp side where no deep level6 exist. There are numcrouq experimental investigations on 3d-'l'h. In tetrehdral semiconductors. both interstitial and substitutional incvrpuretions are observed.and 3d1'4s2-confi~~ations. 3d-TM impurities can elso be useful. They can serve as recorrilrizlation centers through which the lifetime of non-equilibrium carriers is shortened. the levels of 'I'M-elements with closed 3d-shells (the so-called 3d-TM cleinents) are by far the bestst known. Fe. are incorporated in S crystals prdomi inantly on interstitial sites of tetrahedral symmetry.y &oms in tehahedral semiconductors (interested readers are referr4 to the book by Fkurov and Kikoin. (Zn. 1985 and 1990. the neighbors of Ni to the right in the periodic table. wc restrict our considerations to the 3d-TM atoms.hln)Te. while experimentally surh 1wrls art. deep levels also exist in their rasp (Beeler. Occasionally.I impurit. for example. for example. Special interest in the investigation of 3d-Thl atoms results mainly from t. In tetrahedral semiconductor crystals. Higher values in the range of 101frm. however.y atoms are observed. In III-V and 11-Vl semiconductors. CU and Zn? are also included. Sometimes. Electronic struetrue of semiconductor crystals with perturbations the rritprion is correct in all caws.In cerhizl 11-VI compound semicondudors. also is a transition metal which gives rise to alloys with R. owing t.o their respective 3d1'4s. Alves. Beside donor and acceptor transitions alsn internal transitions of the 3d-TM imp1irit. such a . these are not in fact transition metals. 1986). i. those with closed ad-shells (see Table 3. The solubility of most transition metal elements in Si is relatively small.e. Concerning 4d. pxrept for In and TI.2). they behave similarly. The position of t h e 4d-TM atoms in Si lies between the two. Sdief€lcr. Semiconduct. V.320 Chapter 3.e. b1n)Te s or (Cd. Mn. Here. Leihe. while the 5d-TM atoms prefer substitutional cation sites.and 5d-TM imyurily atoms. i.or alloys exist also with Fe and Co. lying in the range of rm-3. 'I'his happens. thus one must.~ . Below we . most of the T atmns form deep levels.

the donor and acceptor ionization levels of substitutional 3d-TM impurity atoms are now well understood. Neglecting bbP-type matrix elements. one triply degrnertlte bonding level Eb nnd one triply degenerate anti-bonding level Ea arise.6). band and an antibonding state deep in the conduction band. The two 01-orbitals interact with each othrr tand give rise to a bonding state dwp in the valenct. the same formulas apply 8s those which wmt' derived in section 2. The energies of these orbitals will be denoted by Ed. eS and eh. The case of free atoms is also striking in regard to the large Iyariations of ionization energies between different ionization states. In semiconductor crystals these variations are almost two orders of magnitude smaller so that. A simple oneparticle model which is supported by ab initio calculations. Considering the tetrahedral sgmme try of the impurity center.16 contains data related to this. Figure 3.174) where . ionization levels of several charge states may be found in the e n e r a gap. The two estates remain without bonding. their energy levels are likely to be found either in the gap or in the valence band. and hhe five d-states decompose into two states ).we decompose the four sp3-hybrid orbitals of the four surrounding cation atonis pointing lowdrdb the ThI atom into a state with A1-symmetry and three states Itah) with T2-symmetry.17). Considering the substantially stronger localization of d-electrons and the much weaker screening of their interaction in comparison with the valence electrons this is surprising and needs explanation. Denoting the Vpp. Deep levels 32 1 ' concentrate on the donor and acceptor transitions.3. Theoretically.5. we hwe (3. is a defect molecule with the 3d-TM atom on a substitutional cation site at its center (see Figure 3. as well as showing the ionization energies of the free 3d-TM ions.-type matrix elemen1 by V h d . and the representation of the crystal is embodied in the four sp3-hybrid orbitals of the four surrounding cation atoms pointing towards the TM atom. the TM atom is represented by the five 3d-orbitals and the one 4s-orbital of its valence shell. For these two levels.6 for interacting hybrids at nearest neighbor atoms of an ideal crystal. respectively. The two triply drgeiicratc 12 states Itah) and 1t2d) do interact mutually.1 with E symmetry and t h r w states It%) with Tz-symetry. In this model. as in the case of the Iacancy. We will return to this point later. The latter are larger than the ionization energies of the 3d-Thl atoms hosted by semiconductor crystals by more than one order of magnitude. 'rhe corresponding interaction matrix elements are of the type j r and bym {see section 2. The s-orbits1 of tlir TM atom is deformed by the crystal into an orbital of A1-symmetry.

177) . ) 2 A (3.4 The corresponding thecomponent wavefunctions It2b) and Itza) of.16: Experimental ionizatjon energjes of free 3dTzvl ions (lower part). are where we set a = -(I2 1 s a)' - 1 a 2 = .( l + .j d'o/d9 d'/do d%' d?d2 dyd' d%l' d?d5 d?da d%' d%ln I I I I I I I ' 1 11 GoAs to/2.. Electronic structure of semiconductor crystah with perturbations Figure 3. energy Eb and E.322 Chapter 3. (After Zernger. respectively. 1986. as well as donor and acceptor ionization energiea of 3d-TM impurity atoms and ions in various host semiconductors (upper five parts).s.

It turns out that the bonding tzb-level lies in the valence band.band Figure 3. These levels . the 2-fold degenerate e-level and the abovelying triply degenerate anti-bonding tp.175) are linear combinations of basis functions with tz-symmetry. and the anti-bonding tk-level is in the gap above the e-level or in the conduction band.17). meaning that the bonding tzb-level is mainly formed from the d-ststes of the TM atom. Lindfeldt. the non-bonding elevel in the valence band or the gay. Since the two bonding and anti-bonding eigenvectors Itzb) and Itza) of equation (3. If Ed lies deeper than Ch.18 the calculated oneparticle energy levels are shown for some 3d-TM atoms in Gap. they also have t2-symmetry (as already indicated by the notation). The most striking feature of the above description of the electronic structure of substitutional 3d-TM impurities is the existence of deep levels whose wavefunctions are spread out over the surrounding host atoms. In Figure 3.8 holds. Exactly this picture emerges from the above-mentioned Green’s function ab initio calculations (Zunger. therefore. while the anti-bonding tza-level. which forms the deep level. 1983). Deep levels 323 c -band t2a \ t2 4s 3d v . Explanations are given in the text. In regard to deep levels of the 3d-TM atom i s in the energy gap. Considering localization of the t a b and tn. arises to a considerable extent from the tz-components of the four sp3-hybrid orbitalb of the surrounding host crystal atoms. The eigenfunctions of the e-level are linear combinations of the &orbitals of the TM atom and are therefore strongly localized at the latter. the position of the two orbital energies F d and t h relative to each other is decisive.5.-level are candidates (see Figure 3.3.17: Energy level diagram of the defect molecule model for a substitutional 3d-TM impurity atom in a tetrahedral semiconductor.-leveh. then a! > .

i. which was long believed to be correct for substitutional TM atoms also. Substitutional Co in a 11-VI compound has the oxidation state Co2+ since one additional valence electron is provided by the group VI atom of the host crystal.e this we consider the example of a Co atom substituting the metal atom in a 111-V compound. it is assumed that an impurity atom X in the crystal has essentially the same electronic structure as the free X"+-ion. the non-bonding e-states and the anti-bonding t2-states. where V + means the oxidation state of the impurity atom in the crystal introduced above. Since 9 electrons are expected at a neutral Co atom.18: Calculated oneelectron energy levels of substitutional 3d-TM impurity atoms in Gap. and 6 by the bonding t 2 state). The energy levels and wavefunctions of this ion are weakly disturbed by the crystal field at the impurity site. Within ligand field theory. however. To demonstrat. an effect referred to as crystal field splitting. and 5 in the valence shell of the group V atom to which the Co atom binds. The oxidation states of ligand field theory are. Today there exists clear experimental evidence that this is not the case. While this model applies relatively well in the case of ionic crystals (where ch lies deeper than c d ) . (After Zunger and Lindtfelt. it evidently fails in the case of the covalent or partially covalent tetrahedral semiconductor crystals. In this model.324 Chapter 3. Electronic structure of semiconductor crystals with perturbations Figure 3. The ionic model is based on the so-called ligand field theory. also r e produced in the approach taken here. This picture stands in remarkable contrast to the so-called ionic model. S i x electrons remain for the population of the deep impurity states. the deep level is strongly localized at the TM atom.) 3 4a -3 -2 -jFq *\ 1- are host-like to a certain extent rather than purely TM atom-like. the oxidation state of Co in a 111-V compound is Co3+. There are 9 electrons in the 3d74s2 valence shell of Co. . 1983.e. 8 of these 14 electrons are hosted by bonding states of the deep center (2 by the bonding al-state. This entails an approach to the deep level problem for impurity atoms which differs fundamentally from the one used in this book.

Figure 3. 2984) Ligand field theory accounts for the fine structure of the deep impurity levels. Fazzio.19 demonstrates this in thc case of TM atoms in ZnS. which is not explainrd by the approach taken above.0 z w 1. The differences between the donor or acceptor ioniaation energies of a particular TM atom in different host crystals exhibit interesting behavior. particularly not for the internal transitions of the 3d-TM centers. in particular.19: Calculated inultiplet structure for substitutional 3d impurity atoms in ZnS. as we have scen above. Heinrich. this approach must be refined by including many-body effects. To be quantitatively correct. Experimentally one finds that these diffeiences are almost independent of the atom considered. it becomes important for T M impurity atoms with their strongly localized open d-shells (as was specultited in section 3. While the latter effect does not play an important role for main group impurity atoms. [After Faatio.4 using the analogy with frcc I'M atoms).o 0. Deep levels 325 3. 1984.3.0 Figure 3.5.20 this fact is shown for acceptor .0 I 2 55 LT W 2.5. 1985). the excitation energies it yields are not correct quantitatively. configuration interaction. In Figure 3. and Zungcr. Caldas. Although this approach provides qualitative understanding of deep 3d-TM centers in tetrahedral semiconductors. Therefore the ' ionization-encrgy-versus-'I'M atom curves' of different semiconductors are parallel t o each other and ran be translated to overlay by rigid displacements along the energy axis (Caldas. Langer. Zunger.

however. the Hubbsrd energies of the d. The rigid displacement along the energy axis has an important physical meaning as we will discuss further below.20: (a) Experimental acceptor ionization energies of 3d-TM impurities in 111-V semiconductors. respectively. (3. Here. : are. n d = nbu! 2 + nap2 in. and [Jd. 0 (3.) and donor ionization levels of a 3d-TM impurity atom in a series of I11 V and 11-VT compound semiconductors. respectively. we will provide a simple explanation for the similarity of the 'ionization-energy-versus-TM atom' curves in different semiconductors (Tersoff.. 0 tJh(nh . (After Langer and Heinrich.178) Here c :E denote the energy levels without charge transfer. the atomic d.25). Harrison. in addition. 1986).nh). in the linear approximation of equation (3. the dependence of the energy levels f d and Eh on their population will be taken into account in a self-consistent way. Let n d . n h and n:. the former after charge transfer between the impurity atom and the crystal has taken place.and sp3-hybrid orbitals. be denoted by rib and n. U h . 1985. Of the total number of electrons of the defect molecule. (b) Experimental donor (open symbols) and acceptor (filled symbols) ionization energies of 3d-TM atoms in IFVI semicoIiducton.179) . In this discussion we will use the defect molecule model of 3d-TM impurity atoms presented above. and the latter before. Electronic structure of semiconductor crystals with perturbations Figure 3. and the electron number for the estates by ne. The dependence of the levels Ed and ~h on population may. be written as Ed = td 0 + Ud(nd - r i0 ) .326 Chapter 3. respectively. The electron numbers in the bonding and anti-bonding ta-states will. n: be the electron numbers in. d Eh = €1.and the h-states of the sp3hybrids.

.e.B and n h are small.6 ) A - 1 ne .181) must practically vanish itself in order to satisfy this equation. is indepmrlent of Ch. its three states are therefore completely occupied and it holds n b = 6. also the energy separation tId-€h = 26 between the d. The difference 6 = (Ed .178) for the level positions t d and Eh are satisfied with values n d and n h from equations (3.and h-states adjusts self-consistently: if Eh increases. According to equation (3. Deep levels 327 are in d-states. with this. hence. it cannot vanish completely because adjustrrierii of the levels requiies a bit of rhargc to bc transferred). also . respectively.~ h ) / this condition 2 yields +uh where 260 = denotes the level distance without charge transfer.181). 0 (3. According to this relation. leading to the approximate rclation (E! " ci) . their clihtance from c h is independent of Eh.178). P2 from (3.a2 (3. This also holds for the anti-bonding tza-level dnd for thc non-bonding e-level.n d w 0. an increase of 6. Therefore. thus. The bonding T2-level Eb lies in the valence band. the d-level adjusts in the crystal in such a way that the charge transfer between the crystal and the d-shell practically vanishes (of course. the factor multiplying U d in equation (3. Self-consistency is then achieved if the two equations (3.also.6)-A . The crucial point at this juncture is that [ I d . and values a 2 .5. for the two levels which are candidatev fol deep levels in the gap .€ h ) / 2 between the d. For the ta.3. For the level difference 6 = ( € d . then 6 becomes small and. the self-consistent value of h and.n:)] 2 (3. and n h = n b P 2 +. and for the e-level from the fact that its position is determined by the location of the d-level in the c ~ y s tal.180). We thus arrive at the conclusion that the deep levels of 'I'M atoms in .and < h level. Since t h is the only quantity which changes substantially in the series of the 111-V and 11-VI-cornpound semiconductors. because of strong localization of the &electrons and wcak scrcening of their interaction.177).180) are in h-states. n d increases which. This adjustment is called the 'neutrality level'. has very large values (on the order of magnitude 10 e V ) .(nu 1 6 + 6 ) .179) and (3. the separation between Ed and Eh is the same in different semiconductors.-(nu .18 1) i ( ~ a 1 6 + 6 ) + s1( n u.182) which uniquely determines 6. according to (3. i. results in an increase of € d and. As a consequence of this.174).-level this follows from equation (3.

T i makes it somewhat difficult to identity the pure substitutional NM centers. the deep TM-levels are shifted up only by several tenths of an e V rather than 10 el. for example. Although the elements Cu. Fe or 3d-TM’s. Ag. and that the closed d-sheIl (Cu. Moreover. as will be discussed iu more delail i section 3. and.and p-shells of the host atoms are substantially smaller than those of the &orbitals of the Thl atoms. Since the Hubbard energies of the s. Au in Si These three elements (abbreviated below as ‘Nhl‘.177)). Au with 0. Electronic structure of semiconductor crystals wilh perturbations the gap are ‘pinned’ at the hybrid level F ? ~ the surrounding host anions. This means that electron charge density will flow from the Thl atom to the surrounding host atoms. Their incorporation in the host crystal is predominantly substitutional. in almost the same measure as was added t o the T M atom when the additional electron was placed in the deep ant i-bonding &-level. is occupied. but not the outer p-shell. the d-level of the latter will be shifted up and the bondmg tB-level will be depolarized ( a becoming smaller and /3 larger in equtliiori (3. This is understandable if one considers that for these elements only the outer s-shell. As impurity atoms. their behavior its impurity atoms in tetrahedral semicunductors resembles that of transition metals. as is their fast diffusion. with this. for noble metal) play an important part in silicon device technology.~ at melting temperature). 1976). Thls quantity has a close relation to the valence band discontinuity at a semiconductor heterostnicture.and f-shells . they constitute effective capture centers for non-equilibrium charge carriers. The rebUlt8 above explain lhe experimental finding that the ‘deeplevelversus-Thl atom-curves’ for two different semiconductors ran be tranbleted to overlay each other by rigid displacements.328 Chapter 3. so that levels of several charge states can fit in the gap. they associate the with the difference between the average hymagnitude of the displa~ements brid energies of the two semiconductors. Ag) or d . In fact. if an additional electron is put in the deep tzo-lwel. for the case of the free TM-ion if one more electron is p l a ~ e d the center (Haldan. the anion-hybrid energy Eh has to be replaced by the average cation-anion hybrid energy of the crystal. also part ofit IS added to the TM atom. The elements tend to form hs complexes with other elements. at Cu. Anderson. in to that the deep levels of TM atom8 depend only relatively weakly on their population. Their high solubility in Si is remarkable (in the region of cmd3 to ~ r n .8 n The large Hubbard energies of the atomic d-states of the ‘I’M impurity atoms and thFir pinning at lhc dangling hybrid lev& of the surrounding atoms are also contributo~y the striking phenomenology noted above. Ag and Au belong to the fast main group of the periodic table. of If the coupling hetwccn the anion-hybrids and the rest-of-crystal is taken into account.

for RE elements heavier than Nd. Eu. Sm. Th. U. in fact. . there is also strong shielding by the completely occupied 5s. only parts of the implanted atoms are optically or electrically active. P u . and of about 10l8 C W I . The equilibrium solubility of the RE atoms is.~ The technologically interesting luminescence discussed above is caused by internal transitions within the 4f shell of the RE atoms. this state arises from the interaction of the impurity-derived d-states (more exactly their tg-component) with the tg-components of the dangling bonds of the surrounding host atoms. Pr. more strictly speaking. the calculations result in a Nh/l(O/+) donor level.and 5p-shells lying outside the 4f-shells for these elements. several ionization levels can fit within the gap. generally. Because of the relatively weak localization of this deep impurity state. . While internal electron transitions within the 4f-shell have been studied already for a long time. For practical applications. however. and as in the latter case. impurity concentrations of about lo1’ ~ r n have been reported in Si. Ac. Furthermore.and p-shells. the amphoteric character has also been conhmed experimentally. non-equilibrium incorporation techniques like ion implant ation must be used. The investigation of RE impurities in Si as well as in the 111-V and 11-VI semiconductors has received new stimulus very recently. Caldas and Zunger (1985).5. strongly shielded by the 6s-electrons shutting out influences of the surrounding crystal.3. and Cm. For all three K M atoms.~ in Ga4s. between the various levels arising from the many-particle levels of the 4f-shell under the influence of the crystal field.3). again. including donor and acceptor transitions into conduction and valence band states of the crystal. This may be traced back to the fact that these orbitals are strongly localized and. moreover. rather small. although. The reason for this is the luminescence of RE impurity atoms in these crystals in the technologically interesting visible and infrared spectral regions. Pm. Np. and a NM(-/O) acceptor level. almost unchanged by installation of the RE atoms in the crystal. Deep levels 32 9 (Auj lie energetically relatively shallow below the s. Exceptions are Gd and Tb which have one 5d valence electron in addition. According to calculations by Fazzio. In the case of Ag and Au. its Hubbard energy is small so that. Pa. have been subjected to more detailed investigation only recently. Nd. transitions to energy levels outside of the 4f-shell. Am. Rare earth atoms The rare earth (RE) atoms are among the following elements: Ce. just as in the case of transition metals. the anti-bonding t 2 state lies in the energy gap. The 4f-orbitals remain. For Erbium (Er). In equilibrium the RE atoms are installed both substitutionally as well as interstitially. The valence shell configuration of the majority of these atoms may be described as 4fn6s2 with the number n of f-electrons varying from 2 for Ce to 14 for Yb (see Table 3.

330 Chapter 3. The 4forbitals. while the host and RE derived t2-states couple to each other forming bonding and anti-bonding tz-states. Because of this. In this model. nevertheless. The RE atom is represented by its 5d. 6 4 2 5 0 v P--2 g 4 -6 -8 k E(3+/4+) I -10 -12 1 I . and the 6s-orbital becomes a al-orbital under the influence of the tetrahedrally symmetric crystal field. respectively. The differences between 3d-TM and RE impurities are essentially of a quantitative nature. 1991). Electronic structure of semiconductor crystals with perturbations Ce P Nd F Sm Eu Gd T Dy Ho Er Tm Yb r m ' b 8 ! ' I ' I j 1 1 1 I " .and three t2-orbitals.and 6s-orbitals of the RE atom nor do they couple with the orbitals of the surrounding host atoms. are involved in forming deep states because electrons are transferred to or from them. The 5d-levels of the RE atoms are higher in energy and therefore closer to the hybrid levels at the neighboring atoms than are the 3d-levels in the 3d-TM case. The model is therefore largely analogous to that of 3d-TM atoms described above: The five 5d-orbitals decompose into two e-orbitals and three tz-orbitals. 1994. The four sp3-hybrid orbitals at the neighboring atoms pointing toward the RE atom split into one a l . the e-level and the anti-bonding tz-level of the RE atom (which may lie in the gap in the case of 3d-TM atoms) are lifted into the conduction band. the 4f-orbitals neither interact with the 5d. The e-states remain without bonding to the host crystal. ! I I Ce Pr Nd Rn Sm Eu Gd T Dy Ho Er Tm Yb b Figure 3. (After Delerue and Lannoo. The interaction between the two al-orbitals results in a bonding and an anti-bonding al-state lying deep in the valence and conduction bands.21: Donor ionization levels of substitutional rare earth impurity atoms in different semiconductors.and 6s-orbitals only. I ! I I I / I I . .) A rough but qualitatively correct picture of the electronic structure of substitutional RE impurity atoms in tetrahedral semiconductors may again be obtained by means of a defect molecule model (Delerue and Lannoo. The host crystal is described by the four sp3-hybrid orbitals at the four neighboring atoms pointing towards the RE atom.

p-type GaAs. In 11-VI compounds. Through deliberate use of its properties. The ionization levels of the 4J-shell calculated by means of the above defect molecule model are shown in Figure 3. the oxidation state RE3+ is stabk in most rasrs. and on the other hand. and 5 of them from the host crystal anion. while the RE(2 t/3+) ionization levels are above it.and t2-states host 2 f 6 = 8 electrons provided that they are energetically lower than the f-shell. which in fact turns out to be the case. for InP. the one f -electron and the two s-electrons in bonds with the host crystal. the 5d-levels are pinned at the average hybrid energy levels. Thus. or are in bonds between the RE atom and the crystal. The bonding al. because 3 electrons are missing at the RE atom. the oxidation state of a neutral RE atom should be RE2+ according to this consideration. This is reminiscent of the ionization energies of the 3d-TM atoms where the same feature is observed.21 for various RE atoms and host crystals. which normally arises in crystal growth. One recognizes that.1 electrons remain for the f-shell. have been assumed. since the host crystal anion delivers 6 electrons instead of 5.8 = JZ . Oxidation states can also be derived in a more direct way from the above defect molecule model.3. In a 111-V compound host crystal. these predictions are confirmed by experimental investigations. 2 n 5 .and the f-shell with its large Hubbard energy. + + + + + As-antisite defect i n G a A s (GaAs: A s G ~ ) The interest in this defect arises mainly from the fact that it is closely connected with the so-called EL2-center which is one of the most common point perturbations in GaAs. Deep levels 33 1 The position of the If-shell with respect to the above levels still has to be determined. In the model by Delerue and Lannoo this is done assuming that the distance between the 4f-shell and the average 5d-level in the crystal is the same as that between the 4f-shell and the 5d-shell in the free RE atom. RE3+ and RE2+. A striking feature of the ‘ionization-energy-versus-RE-atom-curves’ for different semiconductors in Figure 3. the 4f -levels are pinned electrostatically to the average 5d-levels by means of the self-consistent charge exchange between the d. the RE defect molecule has 2 n 5 electrons. the oxidation state RE2+ is found to be stable in most rases. because the RE(3-t /4 t ) ionization levels are still below the Fermi level. The oxidation state of a neutral RE atom is RE3+ in such circumstances. The reason is similar to that of the 3d-TM case: one the one hand. These electrons orrupy either states in the 4f-shell.5. For CdTe.21 is that they can be brought to overlie each other by rigid relative displacements. The EL2-center is a double donor and plays an important role in GaAs electronics. Two diffcrcnt oxidation states of the RE atom. 2 n of them from the HE atom. can be transformed into semi-insulating GaAs which is required for the manufacture of GaAs . With a few exceptions.

and the anti-bonding T2-level in the conduction band. can be explained in terms of the simple GaAs:Asc. Scheffler. a displacement away of one of the 4 nearest neighbor A s atoms towards an interstitial position about 0. are transferred to the conduction band giving rise to the doubledonor nature of the center. important properties of the EL2-center . one has a bonding and an anti-bonding A1-level. The remaining two electrons just suffice to fill the anti-bonding A1-level in the gap. in regard to materials for light emitting optoelectronic devices. Accordingly. between an . the defect molecule model was developed in subsection 3. Dabrowski.34 eV. a metastable interstitial state. is still somewhat controversial today. 1992. the barrier decreases siibstantially and a thermal transition into the metastable state is possible. Therefore it is not surprising that for the As atom other positions than the substitutional one may be more favorable for minimization of the total en ergy. However. the anti-bonding A1-level in the gap. the concentration of EL2-centers has to be kept as small as possible because EL2 acts to quench luminescence. In this state the center is not capable of capturing the electron whir11 was previously optically excited into the conduction baud. In the above mentioned ab initio calculations.22).332 Chapter 3. If onr of the two donor electrons at the substitutional center is optically excited. 1992). there exists. For the latter point perturbation. antisite defect may be viewed as a special case of a substitutional main group impurity atom with sp3-bonding in a tetrahedral semiconductor. in particular its structural metastability. In addition to the stable substitutional state of the defect. is really identical with the EL2-center. Thc stable state ia separated from the metastable by an energy barrier of about 0. This electron remains there resulting in the experimentally observed persistent photoconductivity.3. the population of the two anti-bonding states is energetically costly. or if it is only part of a complex which represents the EL2-center. wsiilts in a relative totdl energy minirrium which lies only 0. The GaAs:AsG. Only by heating the sample above toom tempwature can the As atom return to Its stable substitutional site. However. From ab initio calculations it is known that the bonding levels lie within the valence band. These are the two electrons which. The main reason for the relatively small energy difference between the substitutional and interstitial locations of the As atom iu that. Of the 10 electrons of the defect molecule. it was shown that a displacement of the As atom by about I A in [Ill]-direction.2 A below the plane spanned by the other three As atoms (see Figure 3. and a bonding and an anti-bonding T2-level. 8 can be placed into the two bonding levels within the valence band. antisite defect alone (Chadi. Nevertheless.25 eV above the absolute minimum of the substitutional As-site. Electronic structure of semiconductor crystals with perturbations MESFET’s and other electronic devices based on GaAs. by exciting the crystal.5. and in the reverse direction the barrier amounts to about 0. Whether the As-antisite defect GaAs: ASG. t h e r e fore.8 eV.

rong sy2-bonds can be formed similar to the bonds in the graphite structure of carbon and that of g a y As.he so-called L)X-cent. Deep levels 333 Direction Figure 3. but singly negatively charged. ailtisite defect is also observed at ot. the two remaining electrons are hosted by the dangling bond of t.t.3.hcr point perturbations.er.he total energy of thc interstif. it is clear t.ers in GaAs and (Ga. The reason for this energy balance is the sainc as in the E L 2 case. (and ev- .5.Al)As mixed crystals (Lang. It was only V clear that they were related to impurity atoms or the main groups l and VI of the periodic table which normally are incorporaled subst. and form shallow donors.22: Geometry of the stable and metastable state of the As-antisitc defect in GaAs. Logan. the DX-state is metastbble. Originally this transition was attributed to the formation of a defect complex involving the donor atom (a)and ti11 iinknown point. 1977). which lics rclatively high enmgetically. lTndcr certain conditions hydrostatic pressure or strong Ti-type doping in the case of GaAs. The non-bonding p-orbital of the A s atom. t. and AlAs mole fractions larger than 22% in the case of (Al.hat the D X center j u s t represents another state ol 1he shallow donor. 1992. Now..ial s h t e because it remains largely unoccupied. namely the energetically costly populalion of the anti-bonding A1-level at the shallow donor. In the singly negatively charged state which the donor takes under high doping. does not increase t. DX-centers A metastability similar to that of the C:aAs:AsG. thc rclalive total energy minimum of the DX-state lies only slightly (about 0. Ga)As deep levels emerge from these shallow donors. If the special Conditions mentioned above are not fuliilled.) interstitial As atom and Ohe three adjacent.2 e V ) above thc absolute minimum of the shallow donor state. among them at t.hen the shallow donor represents a stable state of the impurity atom. However. The microscopic nature of these centers was a puzzle for a long time. (After Dabrowski and SchrJ’ler.the donor atom of a DX-ccntcr is not neutral. and its installation does not occur at a substitutional site but at an interstitial site. In contrast to the lat.hc fourth remotc lying As atom. A s atoms. perturballon (X). st.itiitionally on cation and anion sitcs. as for the EL2-center. respectively.

1 Clean semiconductor surfaces The concept of clean surfaces Every solid is bounded by a surface. and the sp2. Whether or not a metastable state actually exists for a particular point perturbation can. 2 electrons must be hosted by this level.to be concrete we will identify it below with a Si atom . however. In the case of a silicon cube of 1 cm x 1 c m x 1 cm. evidently.22. where it can enter into sp2-bonding with the 3 surrounding As atoms. and the donor is not able to capture the excited electron from the conduction band. Why is this possible? The reason is.6. It remains there for a longer time and gives rise to persistent photoconducting. The nonbonding porbital of the Si atom remains largely unoccupied. that there are many. The donor atom . provided the solid is of macroscopic size. The energy costs thereby become so high that the DXstate is energetically more favorable for the impurity atom than the shallow donor state. 1993). many more atoms in the bulk of a solid than at its surface. for example.334 Chapter 3. Only after thermal excitation does the center return to its original metastable state. optical. Scheffler. but represents a relatively common phenomenon in tetrahedral semiconductors.6 3. either the sp3. 3.and EL2-centers is not restricted to these point perturbations. and. It arises. secondly. first.and p-orbitals of the impurity atom allow for a lower total energy of the perturbation center.the sp3-hybrids to the tetrahedral diamond structure. instead the more deeply lying dangling hybrid orbital of the fourth more remote lying As atom becomes occupied (Scherz. to which all the atoms of the solid contribute more or less to the same extent. Electronic structure of semiconductor crystals with perturbations idently also under the other above-cited conditions). By optically exciting an electron at the DX-center into the conduction band. the model of an infinite solid which neglects the presence of a surface works very well in many cases. from the fact that (depending on the number of electrons to be placed at the center). Therefore. . mechanical or thermal properties. the center passes into its neutral charge state. This model explains in a natural way why the DX-center exhibits persistent photoconductivity.orbitals to the graphite structure.moves into the interstitial position shown in Figure 3. such as transport. only be decided by ab initio calculations.or the sp2-hybridization of the s. The structural metastability observed at the DX. that in many cases one deals with properties. magnetic. This means that the substitutional shallow donor is a stable state of the point perturbation. Nonetheless. optical excitation transfers the DX-center into a shallow donor in its ground state. jointly with the fact that the two kinds of hybridizations lead to different atomic structures .

They were made by cutting or cleaving a semiconductor sample in air. be realized in practice. The surface is reduced to what it means ideally. it also implies structural perfection or atonzc smoothness. Braun in 1874). In the history of semiconductor physics. This means that the transport properties of such a semiconductor sample will depend on its surface. There are essentially t h r w ways to manufactwe clean surfaces. the model of an infinite solid does not apply. In these rases. bulk properties like transport are often not controlled by all atoms but only by dopant atoms. etching or catalysis. but not so microscopically. One calls such almost perfect surfaces clean. All thrw need ultrahigh vacuum (UHV). they were clean and smooth in a macroscopic sense. if it really could be made. of surface atoms. this was recognized at a very early stage. there are other properties or processes. and doping concentration N D . oxidation. in semiconductors. Although this term refers only to chemical composition. Perfwt surfaces in this sense cannot. and impurity atoms at and below the surface. and the unsuccessful attempts to build a field effect transistor in the late thirties of this century. Examples which demonstrate this are the electric rectification at a semiconductor-metal contact (discovered by F. like crystal growth.6. which are determined by the surface atoms only. the number N o x d of dopant atoms per c7n2 can easily become as small as the number IV. They exhibited surface roughness on the 100 nm scale. Perfect surfaces il of semiconductor crystals in this sense necessarily represent a particular lattice plane occupied only by chemically ‘correct’ atoms at regular sites. structural defwts on the 1 nm scale.3. pressures below Torr: (i) Treatment of imperfect surfaces by ion bombardment and thermal annealing (generally in several cycles). In the present section we wl deal with surfaces which are free of such imperfections. One may only try to approximate them so closely that the existing imperfections do not essentially change the properties of the surface as compared to the properties which a perfect surface would have. of course. Beside the above mentioned bulk properties. (ii) Cleavage under UHV conditions (only surfaces which are cleavagc planes . area 1 cm2. ‘l’he surfaces used in the early field effect experiments were far from perfect. the termination of the crystal. No impurity atoms are allowed above or below the surface. Clean semiconductor surfaces 335 one has 5 x loz2 bulk atoms and only 4 x 1015 surface atoms. The failure was caused by electron states localized at the surface which captured all the electrons induced by the extcrnal voltage. i.e. If at all. Moreover. Then the number N s of surface atoms per cni’ i s to be compared with the number of dopant atoms. of course. The surface states responsible for the difficulties of the early field effect transistor were due to these imperfections. For a semiconductor sample of thickness d .

b2. (111)means lattice plunes perpendicular to the space diagonal in the first octant of the cubic unit cell. 3.6. The (hkil) are sometimes termed Bravais ~ T L ~ ~ C C R .2 Atomic structure of clean surfaces A geometrical construction which is of special significance in describing crystal surfaces is that of lattice planes.2 for atomic structure and in subsection 3.7). It was already pointed out that these are the surfaces upon which epitaxial crystal growth proceeds in MUE. dcnotes lattice planes perpendicular to the cubic x-axis. jL3. Later.6. b3 of the reciprocal lattice introduced in scction 2. A particular geometrical plane can also be characterized by its normal direction. The symbol (loo). of course). To define lattice planes in this manner. k . 1 are the integer reciprocal axis intervals given by the intersections of the lattice planes with the three crystallographic axes. Although most surfaces used in practice are not clean but imperfect. are not independent of each other. which we will now describe.3 for electronic structure.4 taking Si and GaAs as examples.4. real imperfect surfaces may also be undeistood. This is due to the fact that imperfect surfaces are such complex subjects that it is very difficult to approach them directly. The first three. we will deal with the atomic and electronic structure of clean semiconductor surfaces. see section 3. howevei. (iii) Epitaxial growth of crystal layers by means of molecular beam epitaxy (MUE. The basic principles will be treated in subsection 3. for example. Ik2. important themselves. Clean surfaces are. four crystallographic axes are considered (three instead of two perpendicular to the c-axis).6. since i h k = 0. studies of clean surfaces are also of practical importance. it is convenient to write the normal direction as a linear combination of the primitive vectors bl.6.336 Chapter 3. with integer coefficients + + h l . The lattice planes then are characterized by four indices ( h k i l ) instead of three. In the case of trigonal and hexagonal lattices. . however. the complexities are introduced step by step and examined for changes. Particular suxfuces are discussed in subsection 3. In this section. Electronic structure of semiconductor crystals wilh perturbations of the crystal can be made in this way. Lattice planes of 3D crystals Such planes are usually denoted by Miller indices ( h k l ) where h. and (110) denotes lattice planes perpendicular to the face diagonal in the first quadrant of the ry-planc of the cubic unit cell. One first has to reduce the level of COEApleXity by considering clean surfaces for investigation. In this way.

obtained by multiplying the ( h k l ) with the matrix which transforms the three nun-primitive crystallographic axis vectors into thc three primitive lattice vectors. f2 may be expressed in terms of the primitive lattice . The primitive vectors of this lattice will be denoted by fi and f2. n form a right hand coordinate system. and the coefficienls ( h l h ~ h 3differ from the corrirnon Miller indices. f2. The ( h l h 2 h 3 ) are.10 + h2r20 + h3r30 = 0.122).182) Hrre. ) one can rasily switrh from one representation to the other.184) form a 2D lattice.185) of the infinite family of parallel plancs are obtained by replacing the right hand side of quation (3.a 2 . like the face rentrred cubic one.184) yields only a single plane. apart from a co~linion factor. however. In mathematics it is called a Dzophantin equation.183) of the lattice plane perpendicular to n which contains the zero point. h 2 . If the normal direction n is given. Then the coeffirients hi. Tf necessary. The f1. the roefkients ( h l h ~ h 3 ) are only determined up to a common integer factor.r2O1r3o are allomwl.186) The points of the lattice plane defined by equation (3.181) by arbitrary integers 1. One can show that all lattice planes Ri = w a l + v z a 2 +w a ~ (3. reciprocal lattice vectors are understood without the factor 27~ defin inition (2. We chose this factor such that h l . The latter are parallel to the piimitive lattice vectors only in the case of primitive Bravais lattices. equation (3. (3.6. r e ferring to the primitive lattice vectors al. a 3 as coordinate axes rather than to the crystallographic axes. the lattice points Ro = rloa1-k r20az + '7'30ag (3. (3.h l b l + h2bz +h ~ b 3 . (3. may be defined by the equation n & E h17. Using the above characterization of lattice planes by their normal direction n.184) The unique character of this equation lies in the fact that only integer solutions r10. Clean semiconductor surfaces 337 n .3. hs have no common divisor. h 3 are the Miller indices of the lattice plane under consideration. they have different directions. For centered laltires. Whereas the Miller indices definr an infinite family of parallel lattice planes. namely that member of the infinite family which contains the zero point. This i s done in such a way that the three vectors f1.h2.

the Diophantin equation (3. f2 and ailitrary integers ~ 1 ~ 5 the lattice plane given by relations (3. f2.185 and (3. The choice of $3 is not uniquc. Electronic structure of semiconductor cryst& with perturbations Table 3. This implies that the structure of a crystal ~ .187) The lattice planes R defined by equations (3. (3. and any vector fi which differs from f 3 hy a vector aithiii the latticr plan? can also be used. F3 of the 313 bulk lattice of the crystal. of course. n I Crpst'alStructures I1 Diamond. Selenium vectors a l . In order to determine the coefficients of this representation. (3. Rocksalt.by means of the Euclidean algorithm. IJsing thc lattice vectors fi. Zincblende. 1 WurtBite. BS the vectors Fi. Bechstrdt and Enderlein. We call f 3 the stacking vector because it determines how the lattice planes arc stacked in the crystal. q of the crystal under consideration.3 is a vcctor complementing F1 and f 2 to form a s ~ of primitive lattice t vrctors Fi.184) can bc represented as R = Slfi o + sgh.184) has to he s o l v d .186) for 1 1 in just the same way. 1988j. i .338 Chapter 3.fid were obtained above.8) for several Iow index lattice planes of the 5 common scrniconductor crystal structures. The vector €3 can br detcrinined from thr Diophantin equation (3. which ran be done by Incans of the Euclidean algorithm (set. The piirriitive vectors fi. a z . ~ .186) can be written r in the form where f.183) and 2. fz obtained in this way are shown in Table [3. The considerations above show that the primitive unit cell of a crystal may be chasm as a parallelrpiyed with one of its pair6 of parallel laws parallel to a gwen lattice plane.8: Primitive surface lattice \rectors and stacking vectors of low index surfaces of semiconductor crystals.

23). The crystal can therefore be thought of as consisting of successive primitive crystal slabs sitiihtcd one above the other..3. etc. In the figure. The second primitive crystal slab is followed by another J planes dlvplaced with respect to the first slab by 2f. A lattice plane occupied by atoms is referred to nb: a t o m i c layer. 'I'o be more specific. may be characterized as consisting or parallel lattice planes which are displaced with respect to each other and which are each o c c i i p i d hy atoms of a particular species (see Figure 3. the lattice plane Ro is occupied by atoms of species 1. The location of an individual atom can bc specified by the number 1 of the primitive crystal slab. s2 witahinthc lattice plane. in the vertical direction. is occupied by atoms of species 2. displaced by 6 with respect to the first onc. encompasses exactly one yrimitivc bulk unit cell. The second primitive crystal slab begins with a lattice plane occupied by atoms of species 1 and is displaced with respect to the zero-th plane of the first layer by the stacking vector f3.6. the last plane of the second primitive crystal slab being occupied by atoms of species J and displaced by f3 T'J. s2) of an atom j in crystal slab 1 can therefore be written as + + . Different planes may host different atoms if the crystal has a basis. followed by a plane with atoms of species 2 which is displaced by f3 t ?2 etc. the numbers j of the atomic sublattice and the integer coordinates s1. Clem semiconductor surfaces 339 Figure 3. The lattice plane Ro 7j completev the constsuction of a crystal slab which. and the plane displaced by FJ is occupied by atoms of type J .. Construrtion of a crystal from its lattice planes. It may happen that two OT more atoms of the basis are located at the same lattice plane. The lattice points of a given plane are occupicd by identical atoms. I . the next plane.23. a crystal with o~ily one atom per primitive unit cell is shown. This slab is callcd a p r i m i t i v e crystal slab.j instead of f3. each of which consists of atomic layers containing difkrmt types of atoms and which are laterally displaced with respect to onc another. In that case an ntomic layer consists of two or more basis atoms. The position R(j. s1.

340 Chapter 3. The atoms of a crystal given having an ideal surface are thus located at the positions R(j. The normal direction n is then. and all integer values from 1 to J for j .189). 5 2 ) = I + n . diminishes with increasing distance of atoms from the surface and we can thus assume that the forces acting on. the same as those in an infinite crystal.190) is 1 = 0 and = 0.189) The complete set of locations of atoms in an infinite 3D crystal can be obtained by assigning all possible integer values from --oo to +m for 1. Any choice of n yields the same crystal. however. These obey the relation n . The normal direction n. This is. s 2 . atoms deep inside the crystal bulk are. 1 . A solution of (3. A crystal having such a surface may be generated from an infinite crystal of infinite extension by removing all atomic layers above the surface and retaining those below. expect that the forces acting on atoms in a crystal with a surface should differ from those acting in an infinite crystal. s ~ ) by equation (3.190) The surface or first atomic layer is obtained if the left hand side of this relation is taken to be zero. and the forces acting on them are appreciably different. is arbitrary in the case of an infinite 3D crystal. 1. The exact meaning of ‘ideal’ in this context is explained immediately below. Since the forces acting on atoms situated beneath a lattice plane in an infinite crystal are also partially due to the atoms located above the plane. we can. We start with the description of a crystal having an ideal surface. however. only positions below the surface plane are occupied. . however. The deviation from the infinite case. fixed by the direction perpendicular to the surface. upon which the whole construction of lattice planes is based. R(j. We can immediately employ the above representation of an infinite crystal in describing a crystal with a surface. (3. s 1 . Here. to a good approximation. The term ideal surface is used to refer to this configuration. resulting in displacements of atomic positions with respect to those of the infinite crystal. Electronic structure of semiconductor crystals with perturbations (3. in general. We will discuss these displacements below. and hence the positions of. s 1 . Ideal crystal surfaces Regular crystal sites We consider a crystal surface given by a lattice plane perpendicular to n as defined by equation (3. the atoms at and immediately below the surface have the same positions as they would in an infinite crystal. however. correspondingly. ~ 1 . we assume that they are not present and. Tj 5 0. not true for atoms situated near the surface.184).

two topologically different (111) surfaces exist. Translation symmetry and lattices of ideal crystal surfaces The translation symmetry of a crystal with an ideal surface can be derived from the following observations: (i) Only translations within the surface lattice plane perpendicular to n are admissible. For other crystal structures and surfaces the situation is similar. Even if the basis atoms are chemically identical the surfaces may differ from each other in a topological sense. In each case a different surface is obtained. (ii) Only those translations are admissible which transform each atomic layer into itself. in the case of Si. although the crystal with surface is 3-dimensional in extent. layer by layer. The construction of a crystal. Then being zero themselves. 1 Ga atom and 1 As atom. generally. have a zero projection n . The distinguished role of atomic species 1 in the above considerations results from the choice of the origin . The latter surface is more stable than the former one and the latter is meant if one refers to a (111) surface. There may be other ?j beside ?I which. Of course. correspondingly. The symmetry group of translations and.3. as described above implies that if a particular translation transforms the first atomic layer into . for example. If topologically different surfaces exist for a given set of Miller indices. and in the case of GaAs. only 2-dimensional. in the case of (110) surfaces of diamond and zincblende type crystals. They are shifted with respect to the atoms of species 1 by a vector Tj parallel to the surface.3 the basis atoms of this species j are also located in the first atomic layer.it has been placed at an atomic site of species 1. Si atoms. We first consider the translation symmetry of an ideal surface and the corresponding lattice. Any translation leading out of this plane would alter the spatial location of the surface and thus would not transform the system ‘crystal with surface’ into itself. although not with respect to n. In the case of diamond type crystals. one with three nearest neighbors above and one below the surface and another with one above and three below. Thus. also the lattice of a crystal possessing a surface are.6. the 1 first atomic layer corresponds to the particular lattice plane perpendicular to n which goes through zero and whose lattice points are occupied by basis atoms of species 1. In this case one has two atoms in each primitive unit cell of the 2D lattice of a lattice plane. the coordinate system may be shifted in such a way that its origin coincides with the location of any other basis atom. for instance. Such multiple-species occupancy of an atomic layer occurs. for instance. Clean semiconductor surfaces 34 1 The latter condition signifies j = 1 since 7 = 0 is assumed. therefore. one of them is more stable than any other. and that is the one which is commonly realized in experiment and studied theoretically.

The highest value of n may be readily obtained from the derivation of the possible rotation symmetry axes of 3D crystals in Chapter 1. nmm). f 2 are the primitive lattice vectors of the 2D lattice of the ideal surface. the rectangular with holohedral point group 2mm. C 2 (2) and C2. There are thus 4 different plane crystal systems . so that r =slf1+ s2f2 (3. Their point symmetry elements are necessarily rotations about axes which are perpendicular to the 2D lattice plane. a square or an equilateral hexagon. ( n ) or C. f 3 are listed in Table 3. the possible multiplicities of rotation symmetry axis of plane lattices are n = 2. 2D lattices may be divided into crystal systems and Bravais lattices according to their symmetry with respect to rotations and reflections. In this case the point group is c 6 v (6mm). f 2 and extending to minus infinity in the direction of -f3. n 5 6 was found.24).. one takes the four primitive lattices with unit cells which are parallelograms having either no particular symmetry. f2. namely the 'body' centered . As in the 3D case. It immediately follows that the group of translations of a crystal with a surface is identical to the translation group of the first atomic layer. Since the rotation through 180' is always a symmetry element of a plane lattice. (2mm).the oblique with holohedral point group 2. First.8. There.4. Only one new lattice is obtained in this way. The vectors f1. We now consider the possible plane crystal systems and plane Bravais lattices. and 6. Then one adds additional points to each of the unit cells of these lattices in such a way that their point symmetries are not lowered. The point groups of these lattices are. A lattice which only contains a 2-fold symmetry axis is either a completely general oblique lattice or a rectangular lattice. the quadratic with holohedral point group 4mm and the hexagonal with holohedral point group 6mm (see Figure 3.187). Thus. Lattices with a 4-fold symmetry axis also possess 4 reflection lines which are rotated through 45' with respect to each other. or that of a rectangle. only even n are allowed. For the low-index surfaces of the common semiconductor crystal structures. Similarly. the three vectors f1. Thus. and reflections at lines within the 2D lattice plane. this also holds for any other layer. The lattice vectors r of a crystal possessing an ideal surface perpendicular t o the normal direction n are therefore those of equation (3.342 Chapter 3. the point groups are either C . lattices with a 6-fold axis have 6 reflection lines which meet at an angle of 30'. (nm. The possible plane Bravais lattices are obtained as follows. The primitive unit cell of the crystal with surface has the form of a prism bounded above by the parallelogram spanned by f1.191) holds. Electronic structure of semiconductor crystals with perturbations itself. respectively. The point group of such a lattice is therefore C4v (4mm).

Point and space group symmetries of ideal crystal surfaces We wish to establish.I. rectangular lattice. we denote the atomic positions by Rjl(s1.e. space groups which transform the crystal with a surface into itself.6. s and write .24).3. sir92) given by equation (3. but so do equivalent atoms occupying the primitive unit cells. The lattice types of the ideal low index surfaces of the common semiconductor structures are summarized in Table 3. We conclude that five plane Bravais lattices can be realized within the framework of the 4 plane crystal systems: only the primitive lattice in the oblique case. In the latter case this implies that not only does the 2D lattice transform into itself. ~ 1 .I . So it forms an additional Bravais lattice. These atoms are located at positions R(j. the addition of points either leads back to the primitive lattice or results in no lattice at all (i. C e n semiconductor surfaces la 343 oblique P rectangular P quadratic P hexagonal P C Figure 3. nor in any other primitive lattice. This lattice cannot be transformed by continuous and symmetry preserving transformations in the primitive rectangular lattice. the primitive and the centered in the rectangular case. We now turn our attention to the symmetries of crystals with surface as a whole. To express the 2D nature of the translation symmetry of a crystal with a surface ~) explicitly.189). s2) R(j. point groups which transfer equivalent directions of a crystal with surface into one another and. it creates a crystal with a basis). on the one hand. and again only the primitive in the quadratic and hexagonal cases (see Figure 3.9.24: The 5 plane Bravais lattices of the 4 plane crystal systems. In all other cases. on the other hand. With the last statements we have completed the symmetry classification of the plane lattices of crystal surfaces.

The point groups of directions of crystals with plane surfaces are necessarily subgroups of the holohedral point groups of the plane lattices. 4mm and 6mm. only 2D symmetry groups need to be taken into consideration. subgroups of the point groups 2. Bravais Lattice hexagonal square p-rectangular hexagonal square p-rectangular hexagonal square prectangular hexagonal Point Group 3m 2mm 2mm 3m 2mm m 3m 4mm 2mm 3m m m 1 Space Group p3ml p2mm p2mg p3m1 p2mm plml p3ml P h m p2mm p3ml plml P W Pl Irr. Here. The point and space group elements of a crystal with surface must leave the surface invariant. i. as in the case of translation symmetry.e. Electronic structure of semiconductor crystals with perturbations Table 3. the number of atomic layers of an irreducible crystal slab and the number of basis atoms per layer. This basis contains an infinite number of vectors corresponding to the infinite number of atoms in a primitive unit cell. i. respectively. There are exactly . Column 6 and 7 give.2mm.344 Chapter 3. Slab 6 Basis 1 I 4 2 6 4 2 2 1 I 2 6 1 2 2 4 4 4 2 2 1 2 4 (ioio) prectangular prectangular hexagonal 3 1 1 1 (ioio) (1120) p-rectangular p-rectangular 1 Pl P21 6 4 2 where represents the basis of the crystal with surface.9: Structural properties of ideal low index surfaces of the five common semiconductor crystal structures. we therefore also have the situation that. although a crystal bounded by a surface extends in three dimensions. its point and space groups are only 2-dimensional.e.

primitive and centered. p l m l . mm 4 @ ..hey bisect its edges. p 2 m m . The possible plane space groups can be found as follows (see Figure 3. In the latter case one . Their stereograms are shown in Figure 3. 6mm 6 0c3 1 (i I 4 m a @ 3m (I> 3 Figure 3. we find two further space groups.26).6. p 2 1 1 .25.3. p 3 m l . p 4 m m . Since the point groups of the rectangular crystal system are each associated with two Bravais lattices.25: The 10 point groups of equivalent directions of crystals with plane surface. To start with.. p 4 . as assumed in the case of p 3 m 1 . Clean semiconductor surfaces 345 a 2 @ . In the case of the point group 3 m .25. it is evident that each of the 10 point groups of equivalent directions combined with the corresponding associated lattice gives rise to a space group. 10 such groups. either through the vertices of the equilateral hexagon of the Wigner-Seitz cell. 2 mm . This implies the existence of 10 different crystal classes which are associated with corresponding crystal systems as indicated in Figure 3. or such that . there are two different possibilities of positioning the reflection lines relative to the hexagonal lattice vectors. c l m l and c 2 m m . p 6 and p 6 m m originate in this manner. The space groups p l . p 3 .

One should further note that the point group of directions of a crystal remains unchanged if. In the quadratic crystal system it is possible to substitute a system of glide reflection line for one but not both of the non-equivalent reflection line system. The additional space groups in the case of the .26: The 17 space groups of crystals with plane surface. One must therefore examine the 13 space groups already established to determine whether the substitution of a reflection line m by a glide reflection line g (i. a glide reflection line is substituted for an ordinary reflection line. Electronic structure of semiconductor crystals with perturbations crystal svstem oblique 2 LLZ Bravais lattice ooint soace 1 rect angular p-rect a n g ul o r 2mn 6 I I p'g' Ip.e. has the group p31m as a 13-th space group.346 Chapter 3. in its space group. a reflection in m in conjunction with a translation 7' by half of the shortest lattice vector parallel to m ) leads to a new space group. This yields the additional space group p4mg.I c-rectangular Figure 3. One easily finds that this is not the case for the hexagonal crystal system.

6. in fact. the subgroups of the 3D groups which contain only those symmetry elements which transform lattice planes .e. The centered rectangular and the oblique crystal systems do not give rise to additional space groups. primitive rectangular crystal system are p l g l (from p l r n l ) and p2rng. there are therefore a total of 17 different space groups.26: Continuation: The 17 space groups of crystals with plane surface.3. They are. Clean semiconductor surfaces 347 2mn c2mn p-square 4 4mn p4 p4mn I I I .-hexagonal 3 p3m1 I Figure 3. The 2D point and space groups of the various surfaces of a given crystal may be derived from the 3D point and space groups of the infinite crystal under consideration. i.p2gg (from p2mrn). they are non-symmorphic. In the case of crystals with plane surface. Four or them involve glide reflections.

is called an irreducible crystal slab. The 2D point and space groups of the three lowest index surfaces of the five common crystal structures are summarized in Table 3.9. the new positions of atoms in the crystal with surface and . All one can assume is that the displacements decrease from one layer t o the next and vanish altogether at a depth that is relatively far from the surface. The point and space group symmetry of an ideal crystal surface may also be derived from the projection of the crystal onto its surface. we present a more detailed description of the surfaceinduced displacements of atoms and discuss the resulting altered symmetries as compared to those of ideal crystal surfaces. As already noted. Relaxed and reconstructed surfaces Surface-induced atomic displacements In the preceding section the atomic structure of crystal surfaces was considered under the assumption that the atoms of the crystal bounded by a surface occupy the same positions Rjl(s1. and 2 doubly occupied layers for ( l l o) ) . More precisely. columns 4 and 5. Translation symmetry of relaxed and reconstructed surfaces We denote the displacements of atoms due to the formation of the surface by 6Rjl(sl. A crystal slab which contains the minimum number of atomic layers necessary for completing the projection.s2) as they did in the infinite 3D crystal. Atoms from different layers below the surface are illustrated differently with sizes as indicated. the projections repeat themselves. The point and space group symmetries of a crystal with an ideal surface are those of its irreducible crystal slab. In Figure 3. they contain elements which transform directions in a lattice plane into equivalent directions in that plane as far as point groups are concerned. Since the forces acting on the atoms of the second layer are in part determined by the positions of the atoms in the first. this assumption is actually not valid. and are thus subjected to displacements from their original sites in the crystal bulk.27 such projections are shown for the three low index surfaces of diamond and zincblende type crystals. and transform atomic layers located parallel to the surface into themselves if space groups are under consideration.4 for (loo). The atoms of the surface layer experience different forces than those acting in the bulk of the crystal. After some number of atomic layers (6 for (lll). Electronic structure of semiconductor crystak with perturbations situated parallel to the surface into themselves. 4.348 Chapter 3. if the former is generated from the latter by removing one half of it. these forces are also subjected to changes accompanied by displacements in the second layer and so on for each successive layer. Here.

Then 6Rjl(sl.3. In this case equivalent atoms in different primitive unit cells are displaced in the same way.e.6.195) The displacements 6Rjl may be divided into two classes with regard to their effect on translation symmetry. the displacements are termed r-e-eluzation. . (3. Clean semiconductor surfaces 349 (1111 (1101 (111) coiii (100) (110) 0 1 A 0 1 A 0 1 A O2B 0 2 6 016 0 3A 0 3A 2A Figure 3. s2) 4 0 f o r I -+ -m.27: Projections of a diamond or zincblende type crystal onto its low index surfaces. If the latter is not affected. by R’j~(s1. sz). i.

and a lower slab encompassing all other layers. the displacements are termed reconstruction. The translations which transform the crystal with surface into itself must belong to both groups of translations. The translation group T of the whole crystal with surface is thus the intersection T = Ts fl Tb (3. an upper slab containing the atomic layers with displaced atoms.e. If.28b). (3.28a). In describing reconstruction it is useful to divide the crystal with a surface into two slabs parallel to the surface. Both the basis and the lattice are changed. bRjl(s1. respectively.s2. Tsis a subgroup of Tb then T is equal .196) Only the vectors 6 of the basis are altered. There are two possibilities.s2) depends on sl. in which case one says that the two lattices derived from Ts and Tb are commensurate. s2) = 6Tji‘jl for all 51. If. in particular. respectively. the lattice vectors remain un1 changed in this case (see Figure 3. We first consider the changed lattice translation symmetry of reconstructed surfaces (see Figure 3. In this case equivalent atoms in different unit cells are not all displaced in the same manner.350 Chapter 3. Electronic structure of semiconductor crystals with perturbations Figure 3. one can say that T is the largest common subgroup of both groups Ts and Tb. A 2 x 2 reconstruction is shown in part (b). here we use the terms ‘surface slab’ and ‘bulk slab’ (or simply ‘bulk’) for the upper and lower slabs. The lattice associated with the T is called the coincidence lattice. Alternatively. which means that the lattices defined by Ts and Tb are non-commensurate and the crystal with surface does not possess any lattice translation symmetry.e. on the other hand. either T only consists of the identity translation. s2. the translation symmetry is altered.28: Surface relaxation (a) and surface reconstruction (b) extending up to the second atomic layer.197) of Ts and Tb. the plane translation symmetry groups of the surface and bulk slabs. The upper slab is sometimes called a ‘selvedge’. i. i. layers with non-displaced atoms. Ts as well as Tb. BRjl(s1. By Ts and Tb we denote. or T contains more elements than just the identity.

the coincidence lattice is identical to the lattice T.e. k = 1. i. it follows that the Qik must have integer values. The latter are. Let be fi and fi the primitive lattice vectors of the reconstructed surface slab. arbitrary real numbers. (ii) translation symmetry exists but is smaller than that of the surface slab. surface reconstruction can be described by a 2 x 2 matrix with integer elements. also the primitive lattice vectors of the bulk slab of the crystal with surface. then only the third of the above possibilities can be realized. f i is simultaneously the lattice of the reconstructed surface. f 2 . the coefficients Q i k . Using the above conclusions we are able to determine the primitive lattice vectors of the reconstructed surface in terms of the primitive lattice vectors f1. and it is probably not valid without exceptions. by definition. i.e. fi. We thus arrive at the important conclusion that in the only case of practical interest (iii) above. One can thus distinguish between the following three cases with regard to the translation symmetry of crystals having a reconstructed surface: (i) no translation symmetry.. among the various conceivable surface reconstructions with a given degree of translation symmetry. i.2. = Q2lfl + 922f2. respectively. is not a subgroup of Tb then T cannot be equal to T. as a rule. and their lengths are integer multiples of the respective lengths of the latter. f: and fi are parallel to f 1 . it generally yields correct results. They need to be rational if and only if the two lattices derived from f i . that particular reconstruction will take place which allows for maximum translation symmetry of the crystal with surface (the system ‘surface slab plus bulk slab’). i. the lattice derived from f : . f 2 of the ideal surface. In this case. f 2 according to + 912f2 f. of the transformation matrix Q are. of the surface slab.e. Clean semiconductor surfaces 35 1 to T. The two most common forms of this type of reconstruction have a special notation (Wood notation): (1) The non-diagonal elements vanish. in the particularly interesting case (iii). and is necessarily a proper subgroup of T. f’2 have a coincidence lattice. If T. i. f 2 and f ’ l . it is smaller than T. A formal proof of this assumption does not exist. If one assumes that. in case (ii) above.. however. If the coincidence lattice is identical to the lattice derived from fi. They may be linearly composed of f 1 .6.e. at the outset.3. i. (iii) translation symmetry exists and is the same as that of the surface slab.199) Here.e.198) (3. f: = Qllfl (3.. We thus have .

f2) = a about an axis which is perpendicular to the surface.201).201) (2) The off-diagonal elements of Q are not equal zero. however.202). (3. n x m is replaced by p . which in the case considered here are integers.n x m. (hlcl) surface respectively. f2 by the factors lfiI/fll and ~ f ~ ~ / ~ f ~ ~ A. f2 (with tails joined at the same point) can be transformed into the two corresponding vectors = L(f4. with a subsequent rescaling of f1.29. The lattice vectors fi = nfi and fi = mfz are then not necessarily primitive as originally assumed in the notation (3. This can only take place.n x m notation is just a simpler description of a reconstruction of type (3. f& = mf2 . and which can otherwise only be characterized by the 2 x 2 matrix Q itself. fi) .201). in the notation (3. lfil C(hkl) -x lfil 11 4 . This means that the two vectors f1.352 Chapter 3. are shown in Figure 3. although it is also sometimes used (formally incorrectly) for square lattices.200) with n and m being integers. and in addition to primitive ( p ) reconstructed surface lattices.e. which (! are in general not equal to each other.. (3. Electronic structure of semiconductor crystak with perturbations f: = nfi. This is said to constitute an n x m reconstruction An n x m reconstructed crystal surface of a particular material C parallel to a lattice plane with Miller indices (hlcl) (or ( h k i l ) in the case of hexagonal symmetry) is characterized by the symbolic notation C(hlc1) n x m. For square reconstructed lattices the c . Examples of both of the special reconstruction forms discussed. fi by a rotation through the same angle L(f. In the rectangular case the notation c . the modified notation applies only to this case. fi) and L(f&fz).202) and The factors lf~l/lf~l lfil/lf21 are in general irrational in contrast to the qik. The angles Lf.201). Thus. fi is not parallel to fi and/or fi is not parallel to f2. This implies that the crystal with reconstructed surface belongs to a different plane . The primitive unit cell of the surface slab contains n x m primitive unit cells of the bulk slab. If21 (3. The point symmetry of a reconstructed surface lattice is generally lower than that of the ideal surface lattice from which it is derived. for rectangular surface lattices.. Sometimes. i.n x m describes a type of reconstruction which is not covered by one of the two notations (3. of a particular material C reconstructed in this way is characterized by the symbolic notation f. as well as for the general reconstruction form in case (iii). (3. are assumed to be equal in the case under consideration.n x m or c . also centered ( c ) ones are possible.a.202).

the directions of the two primitive lattice vectors are symmetrically equivalent. the symmetrically equivalent vectors f2 and fi (Figure 3. Due to the domain structure. three symmetrically equivalent direction exist (Figure 3. respectively. having a hexagonal lattice and one of the point groups 6mm.30). The result is the formation of domains of otherwise identical. (c) general type. the 2 x 1 reconstruction of a square lattice leads to a rectangular lattice. For example.3. Clean semiconductor surfaces 353 Figure 3. The same holds for the 2 x 1 reconstruction of a hexagonal lattice which also results in a rectangular lattice.6. In this case. is equivalent to another reconstruction which does the same for. 6 . It follows from the point symmetry of the crystal with ideal surface itself. concerning the surface reconstruction itself. 3 m or 3.30). 412 = -1. (b) 3h x 31 -30°. they will take place simultaneously in different regions of the surface. but differently oriented. the matrix notation does with 411 = 5. Structural imperfections of a more local nature occur where the boundaries of such domains meet.29: Three different types of surface reconstructions: (a) 1 x 2. crystal system than the crystal with ideal surface. . If the latter belongs to the square crystal system. reconstructed unit cells. the overall translation symmetry of the surface is destroyed. If there is no physical reason which makes one of the different symmetrically equivalent reconstructions more likely than another. A particular reconstruction which increases the surface unit cell in the direction of fl by a factor n and in the direction of f 2 by a factor m . 422 = 2.e. if it has a square lattice and one of the two point symmetry groups 4 m m or 4. A further item is worth mentioning. 421 = 2. the Wood notation does not apply in this case. An analogous statement holds for an ideal surface of the hexagonal crystal system. i.

and the positions of the cores just below the surface . the point and space groups of the relaxed or reconstructed surface slab are. respectively. respectively. the point and space groups of whole crystal with relaxed or reconstructed surface. They do not only depend on the point and space symmetries of the irreducible crystal slab as in the case of an ideal surface. The point and space group elements of the thus extended surface slab which are simultaneously point and space group elements of the irreducible crystal slab form. the point and space groups of the whole crystal with relaxed or reconstructed surface. If the surface slab contains fewer layers than the irreducible crystal slab it is expedient to add further atomic layers (which then do not contain displaced atoms) to make up the difference. Electronic structure of semiconductor crystals with perturbations Figure 3. one may argue that the point and space groups of the relaxed or reconstructed surface slab should be subgroups of the point and space groups of the corresponding ideal surface.354 Chapter 3. If this is the case. but also on the point and space symmetries of the relaxed or reconstructed surface slab.3 Electronic structure of crystals with a surface The electrons and cores of a crystal with a surface undergo the same interactions as the electrons and cores of an infinite bulk crystal.6. Similarly like this was done for the translation symmetry group above. then its point and space groups can be taken to determine the point and space groups of the whole crystal with relaxed or reconstructed surface. 3.30: Symmetrically equivalent 2 x 1 reconstructions in the case of ideal surfaces belonging to the square (left) and hexagonal crystal systems. Point and space symmetries The point and space symmetries of relaxed or reconstructed surfaces are generally of lower degree than those of the corresponding ideal surfaces. the only difference being that the cores and electrons of the removed semi-infinite crystal above the surface are missing. If the surface slab consists of more layers than the irreducible crystal slab.

In many cases. Below. The most critical part of the total energy is the energy of the electron system. they are not known or only incompletely known from experimental investigations. namely. In order to obtain it.5 with respect to point defects.3. and in section 3. One-electron Schrodinger equation The one-particle Schrodinger equation for the wavefunction $E(x) of an . The remaining parts of the procedure for determining the atomic and electronic structures of surfaces. the calculation of the entire total energy including the core-core interaction energy. The minimum set gives the core positions which really apply. The two basic approximations of the theory of the interacting electron-core system of an infinite crystal. this can no longer be assumed. data of the electronic structure calculations. For crystals with a surface. In this case they are the infinite bulk positions.2 in general terms. the one-electron energies of the crystal with surface have to be calculated for assumed core positions. rather than input. In the electronic structure calculations of infinite bulk semiconductor crystals. the minimization of the total energy with respect to these sets. for these investigations are more difficult and less precise than X-ray diffraction in the case of bulk crystals (a short review of these methods will be given further below). the core positions commonly are taken as input data. The electronic structures of ideal surfaces are important as reference data for the electronic structures of relaxed and reconstructed surfaces. the calculation of stationary one-electron states for given core positions. this involves the same task as in the case of bulk crystals. are not influenced by these modifications. X-ray diffraction cannot be applied to surfaces because it lacks surface sensitivity.6. namely the adiabatic approximation and the one-electron approximation. Thus we will also deal with them. The way that this can be accomplished was discussed in section 2. Formally. first. The assumption of a priori known core positions is valid if ideal surfaces are considered. Clean semiconductor surfaces 355 differ from those in the infinite bulk. This is possible because these positions are crystal sites of high symmetry which are well-known from X-ray diffraction experiments. In such circumstances. the positions of atomic cores at surfaces are to be treated as output. It involves. second. will not be treated here because it is mainly a numerical task. and the minimization of the total energy with respect to the core positions. we will demonstrate how this problem can be solved in the case of crystals with surfaces. The positions of atoms in the surface layers of relaxed or reconstructed surfaces are crystal sites of lower symmetry. the calculation of the total energy of the electron-core system for a variety of different sets of core positions and. so they may also be used in the presence of a surface.

. 2 . The core potential Vc(x)and. and an effective one-electron any of the potential Ve(x)due to electron-electron interaction.1 may be used. J . -1. . (3. The oneelectron potential V(x) may be written as the sum of the electron-core interaction potential Vc(x). this symmetry can be used to derive the Bloch theorem. . Bloch theorem This theorem states that the energy eigenfunctions $E(x) of the Schrodinger equation (3. For Ve(x).53). . This allows one to write these functions in the form of Bloch functions @Q(x) with a 2D quasi-wavevector 4 = 91g1 + 9282. j = 1 . . defined by the relations .205) where q(x) is the potential of a core of species j located at R = 0..207) where q1. hence. -00. . also Ve(x)and V ( x ) have the translation symmetry of the 2D surface lattice. Using the surface adapted notation 5 If3 r for the position of the j-th basis atom of the primitive bulk unit cell at the bulk lattice point r If3. one-electron approximations introduced in section 2. Electronic structure of semiconductor crystals with perturbations electron in a crystal with surface has the same general form (3.92 are arbitrary real numbers... The follows from the corresponding expression for an infinite core potential Vc(x) crystal if the summation is restricted to cores within and below the surface. this leads to + + + -W J (3. 1 = 0.206) As in the 3D bulk case.203) may be chosen simultaneously as eigenfunctions of the surface lattice translation operators t.203) as in the case of an infinite bulk crystal (see equation 2. so that v(x)= V(x + r) .356 Chapter 3. . and gl and gz are the primitive lattice vectors of the reciprocal surface lattice. (3.

The latter equations are solved by the vectors g1 = N-lf2 x (3. gz of (3. although the number of different q-values within a given region of q-space is finite.(fi . The area RII of the periodicity region is G21f1 x f2l. As in the latter case. as we assume here. k = 1.4. q is practically continuous. As in the 3D bulk case it is convenient to introduce a region of macroscopic size with respect to which the eigenfunctions $J.203) depend on q. g2 = N-lfl x [f2 x fl] (3.208) [fl x f2]. The same statement applies to the 2D wavevector q.3. one may switch from the extended to the reduced zone scheme in which q varies only over a primitive unit cell of the reciprocal surface lattice. In the case of a crystal with surface this region forms a parallelogram spanned by the edge vectors Gfl. Surface Brillouin zones and surface energy bands The energy eigenvalues E of a particular Bloch type eigenfunction of equation (3.4. the wavevectors q must have the form (3. This means that the q-vectors must belong to a finely-meshed lattice similar to that of Figure 2. (3.fz) . with G being a large integer.e.2.pz as integers. f2)’] as normalization constant.210) where U Q ( X ) is the Bloch factor.. . This description corresponds to the extended zone scheme in the case of an infinite bulk crystal considered in section 2. which has the periodicity U E ~ ( X )= U E ~ ( X + r) of the surface lattice and is normalized with respect to a primitive surface of unit cell. The Bloch functions normalized to it may be written as Q. Any other point of the i n h i t e qspace may be written as q + g where g is a surface reciprocal lattice vector.210) with respect to the periodicity parallelogram. If g varies over the whole infinite space.Eq(x) -e2qx = 1 fi UEq(X). within the surface. The two vectors gl. Gf2.209) with N = (1/2n)[(f1 . fl)(fZ. i.E~(x) be assumed can to be periodic.6.211) with p1.209) lie in the plane spanned by the two primitive surface lattice vectors f1. fz. E represents a unique function E ( q ) of q. g k = 27T6&. To guarantee the periodicity of the Bloch functions $ ~ ~ ( x ) (3. i. For the macroscopically large values of G which we assume. Clean semiconductor surfaces 35 7 fi .

4. 5 different reciprocal surface lattices. Types of eigenstates Bulk states Consider an infinite bulk crystal. in fact. and cleave it into two semi-infinite crystals with a surface parallel to a particular lattice plane. Equation (3. These lines may be used to define 2D Brillouin zones in just the same way as was done in the 3D case in section 2. Electronic structure of semiconductor crystals with perturbations In the reduced scheme. regarding their relations to the energy bands of 3D bulk crystals without surface.31. in the extended scheme. the energy function E(q) has discontinuities. Using first order perturbation theory with respect to the periodic potential V(x). Below we characterize these differences in a qualitative way. except for the q-vectors with lql = lq + gl or + q . any higher surface B Z of order p may be reduced to the first surface B Z . As in the bulk case. as we will see below. there are also 5 different first surface B Z s . The surface B Z s of the square lattice have. Thus the energy function E(q) is continuous within these zones. the energy function E(q+ g) over the whole q-space is replaced by the manifold of functions E. free of Bragg reflection lines.(q) E ( q g ) defined only over a primitive unit cell. 1 2 (3.4 as an illustration for the 3D case. by definition. already been used in section 2. The first surface B Z s are. There. hence. and the energy function E(q) in the p-th surface B Z can be folded back to the first surface B Z . They are shown in Figure 3. On Bragg reflection lines. The spectra of energy . it forms a continuous function E. E(q) represents a continuous function of q everywhere. Since there are 5 different plane Bravais lattices and. g + . There are surface bands of different types. there is a distinguished choice of the primitive unit cell.212) defines lines in the 2D q-space which are analogous to Bragg reflection planes in the 3D k-space of a bulk crystal.g2 = 0. Furthermore. Of particular importance is the f i r s t surface B Z .212) where g is an arbitrary surface reciprocal lattice vector. one may demonstrate that. Their shapes are the same as those of the WignerSeitz cells of the corresponding direct lattices since the Bravais types of the direct and reciprocal surface lattices always coincide. Thus we may state that the energy eigenvalues of a crystal with surface form energy bands over the first surface BZ.358 Chapter 3. It may also be defined as the Wigner-Seitz cell of the reciprocal surface lattice. One speaks of surface Brillouin zones (BZs).(q) which is called a surface energy band.

This implies that each crystal with surface possesses an energy eigenvalue spectrum which partially is made up from energy eigenvalues of the infinite bulk crystals from which it is derived. i. The corresponding energy eigenvalues form bulk state surface energy bands Ep(q). These bands can be obtained by projecting the bulk bands E?"(k) of the infinite crystal onto the first surface B Z . Eigenstates of a crystal with surface exhibiting such properties are called bulk states. eigenvalues of the two semi-infinite crystals will contain all energy levels which were already eigenvalues of the infinite bulk crystal before cleaving.e. as do the eigenfunctions of the infinite bulk crystal (see Figure 3. will decay exponentially with increasing distance from the surface. they will exhibit undamped oscillations throughout the whole semi-infinite crystal.3.6. The eigenfunctions of the crystal with surface corresponding to these eigenvalues.32). and their notations are introduced. (c) c-rectangular. while inside they will practically be the same as those of the infinite crystal. (e) hexagonal. 'projecting' means that one assigns to a particular point q of the first surface B Z all bulk band energies EF"(k) corresponding to k-vectors of the first . (b) p-rectangular. (d) square.31: Surface B Z s of the 5 plane lattices: (a) oblique. Clesn semiconductor surfaces 359 t' tY Figure 3. Here. Symmetry lines and points are also shown. if examined at positions outside of the crystal.

360 Chapter 3. As kl varies continuously. In doing so. there are also q-vectors occurring for which certain energy values are forbidden. In addition to q-vectors for which all energy values are allowed.4. it represents a general feature of the projected bulk band structure. the infinitely large number of atoms in a primitive unit cell of the crystal with surface manifests itself. The band structure is taken from the empty lattice model introduced in section 2. @ also does. In the forbidden energy regions states may occur which are localized at the surface. In this way. one notes that part of the projected bulk B Z lies in the second surface B Z . . this can be expressed by the relations The bulk state surface band index p in (3. This peculiarity is found in other.32: The three different types of electron energy eigenstates of a crystal with surface below the vacuum level (schematically).32). bulk B Z having the same projection q on the surface B Z plane. but with various components kl perpendicular to it. This has to be folded back to the first surface B Z . Electronic structure of semiconductor crystals with perturbations W P x I -w 0 .33. together with its energy values. We illustrate the projection of bulk bands onto the surface B Z using the (100) surface of a diamond type crystal as an example. more realistic cases as well.213) replaces the bulk quantum numbers v k l .0 C f w C + C 3 W surface state 9- 0 x- Figure 3. the bulk B Z is to be projected onto the plane of the first surface B Z (see Figure 3. In this way we obtain the projections of the lowest three empty lattice bands shown in Figure 3. As a first step. Formally. This means that a particular band of the infinite bulk crystal gives rise to a continuum of surface bands.

sible degrees of degeneracy of surface energy bands Ep(q). Implications of symmetry for surface band structure The spatial symmetry of a crystal with surface has implications for the posp. Antiresonances are necessary in order to satisfy Levinson’s theorem.2 = 1 dimension.(q) are bound surface bands. Besides these.6. namely that perpendicular to the surface. ‘I Surface states Such states are to be expected for the same reason that localized states are observed in the case of point or 0-dimensional perturbations. surfaces constitute 2-dimensional perturbations. p = p. the decay of the eigenfunction towards the bulk proceeds exponentially (see Figure 3. They manifest themselves in an increase (resonance) or decrease (antiresonance) of the density of states.33: First (100) surface B Z (shaded area) together with the projected first bulk B Z for a crystal with fcc Bravais lattice. The latter occur at energies in the allowed region of the projected bulk band structure and give rise to resonant or antiresonant surface bands Ep(q). If bound surface states exist. Clean semiconductor surfaces 361 Figure 3.3.32). In contrast to the latter. only in 3 . therefore. the antiresonances must compensate the increase of the total DOS in the previously forbidden energy region. The localization occurs. If the energy lies in the forbidden region of the projected bulk band structure. which holds for surfaces as well as for point perturbations. at a . but decay less rapidly towards the bulk (according to a power law) than the exponentially decaying bound surface states. one has surface resonances and antiresonances. The eigenfunctions at these energies are also localized at the surface. The states are then called bound surface states and the corresponding energy bands E. (T.

(q) has the same value. Moreover. large enough. Then nontrivial factor systems arise for points q on the boundary of the first BZ. E. 2D representations are likely to occur in cases where the small point groups are. the irreducible representations of the space group of the given crystal with surface. the corresponding space groups contain glide reflections.(q) at the point q. Electronic structure of semiconductor crystals with perturbations Figure 3. Since the 10 possible point groups of equivalent directions have at most 12 elements (this happens in the case of C6v(6mm)). Such a representation may be characterized by the star {q} of the wavevector q and the irreducible representations of the small point group of q with the factor system of equation (A. K = ( 2 n / a ) ( l l l ) ( I = 1) and K = ( 2 n / a ) ( m ) ( I = -1) are considered.and since the small point groups of the symmetric q-points are in general even smaller than the corresponding point groups of equivalent directions. in analogy to the infinite bulk case. This is based on the fact that the eigenfunctions for a particular energy eigenvalue form a basis set of an irreducible representation of this group.362 Chapter 3. and on the other hand. C % 5 3 1 r K r given wavevector q. and it determines the spatial symmetries of the eigenfunctions $i)w(~). The key for such conclusions are. 1 u l 9 2 - 5 n W 7 E? a. only irreducible representations with dimensions equal to 1 or 2 will appear. . It also results in symmetry relations between the values of EF(q)for different q values. Three bulk bands with reciprocal lattice vectors K = 0 (1 = 0). The dimensions of the irreducible representations determine the possible degrees of degeneracy of an energy band E. on the one hand. at all points of the star {q}. 157).34: Projection of the empty lattice band structure of a fcc bulk crystal onto the first (100) surface B Z .

35: Symmetry and degeneracy of the surface energy bands for the 5 space groups of the p-rectangular Bravais lattice. and p l g l . The two 1D representations on the 2-line connecting these points belong to the same energy eigenvalue because of time reversal symmetry. the possible types of band structures are shown on certain symmetry lines of the p-rectangular surface B Z . one has 2D representations only at X and X'.--z. but the corresponding energy eigenvalues are degenerate because of time reversal symmetry. In the case of the space group p2mg. the representations at all symmetry points are 1D.--Z. Numerical methods for calculation of the electronic structure of surfaces A 3D crystal with surface may be characterized as a crystal with a 2D lattice and primitive unit cells extending infinitely in the direction perpendicular .- I x2 x1 x. only 2D representations exist at M and X .3.6. The representations on the connecting line X . which below will be studied as an example.X ' are lD.-&-z. p l m l .M . -A.- ~--A~.) and 1D representations might not be possible at all.-A.-M2-Z.2 .2' . In Figure 3.- ~r~r+-~2---~-~.-M. 1986. For the three remaining space groups p2mm. [After Terzibaschian and Enderlein.-X. This happens for 2 of the 5 space groups of the primitive rectangular Bravais lattice. -A\-x:-z.r.--M.35.-?. Clean semiconductor surfaces 363 pig1 r. For the space group p2gg. which applies for (110) surfaces of diamond type crystals.-zF- I I I Figure 3.--~.

in the direction perpendicular to the surface. An illustration of this model is given in Figure 3. The diagonal elements are (3. We consider the ideal (111) surface of a diamond type crystal which according to subsection 3. the orbital a localized at such a site is given by &(x .2 15) . Its combination with the tight binding method will be illustrated below by means of an example.. One possibility is to consider a slab of the crystal. 4 .r . Electronic structure of semiconductor crystals with perturbations to the surface. t = 1 .2 14) The number of different Bloch sums is infinitely large even if a finite number of orbitals is used per atom. The slab method may be combined with any band structure calculational method for infinite bulk crystals. the true semi-infinite crystal is replaced by a cluster (see Figure 3. rather than over all points R of the 3D bulk lattice. Consequently the Hamiltonian is given by an infinite matrix in the atomic orbital representation &jl.214) by ht.e. has a hexagonal Bravais lattice. because the integer 1 counting the primitive crystal slabs. This point of view gives rise to the so-called slab method for calculating the electronic structure of crystals with surfaces.364 Chapter 3.and three p-orbitals per atom we use the four hybrid-orbitals. Only nearest neighbor interactions are taken into account. with the exception that the dimensionality of the lattice has to be changed from 3 to 2.37. With the surface adapted notation. one of them being real (that of the semi-infinite crystal).36). i. one has to use Bloch sums of atomic orbitals &(x) over all points r of the 2D surface lattice. Some specific approximation is necessary to transform this to a finite matrix. for example. The latter has two plane surfaces. runs from 0 to -co. To get the matrix elements of the Hamiltonian H between Bloch sums. One may say that. we first need these elements between the localized hybrid orbitals +htjlT Ihtjlr).2.5 where the whole cluster surface is artificial. for a regular crystal site. we replace a in the Bloch sum (3.e. i. and the other one (obtained by cutting the semi-infinite crystal) not. Instead of the one s.(x).3 . 2 . This differs from the cluster method in the case of point defects discussed in section 3. 3 .6. Slab method The electronic structure of a crystal with a 2D lattice may be calculated by means of any of the methods known from band structure calculations of 3D crystals.(x). The corresponding Bloch sums &jlp(x)are defined as (3.. In the tight binding method. to cut off the semi-infinite crystal at a particular lattice plane parallel to the surface and discard the remainder. r+G+Zf3.1f3) E &jl.

1= 0. .215) and (3. 4 are equal to the parameter V2 introduced in equation (2.36: Illustration of the slab method for surface band structure calculations.6.216) are equal for atoms at the surface and in the bulk. Clean semiconductor surfaces 365 Figure 3. all nearest neighbor elements involving IhllOr) vanish.292). t # t’ .216) The two types of matrix elements in (3. Figure 3 . This is not true for elements between hybrids located at different atoms. pointing toward (htlOr).3. (3. and the non-diagonal elements between different hybrids at the same atom j = j ’ are = (htllrlH(htJ1lr) VI . 3 7 Defect molecule model of the ideal (111) surface of a crystal with diamond structure. Since no nearest neighbor hybrid exists for the hybrid )hllOr) pointing out of the surface. Let j = 1. designate the surface atom layer and consider the elements (ht10rJH]ht20rt)between the hybrid ht located at the surface atom 10r and the hybrid lht20x-t) at its nearest neighbor 20rt below the surface. The other three elements with t = 2 . 3 .

Then the 7 Bloch sums IhtlOq). t = 1. Thus an infinite matrix would occur if we would not restrict consideration to a slab. and (ht20q). lh420q). Electronic structure of semiconductor crystals with perturbations Using equations (3.240).215).216) and (3.3. 2 a d3 = -(lll).4. IhzlOq).4 . then the Hamiltonian matrix is (3. They are (htlOq(Hlht.214) may be formed.3. t # t’ . the matrix elements between the corresponding Bloch sums (3.2. In this way we arrive at a simplified model of the crystal with surface which effectively reduces it to the two first atomic layers and treats the atoms of the second layer only in an approximate way. (3.220) t = 2. are coupled to the other hybrids at these atoms. and these hybrids interact with hybrids at more remote atoms. 1 (htIOqlHlht20q) = etV2.219) (3. . lh320q). This model represents an analog of the defect molecule model in the case of a point perturbation.- d4 = a(TT1). h l o q ) . If the basis functions are arranged in the order IhllOq).31. 2 a .t = 2 .366 Chapter 3. h l o q ) . We have d2 = -(lTT). where e t is given by equation (2. lh220q). (3. are completely decoupled from the rest of the Bloch sums (see Figure 3.217).222) The eigenvalues of this matrix are plotted in Figure 3. 3 . as we in fact do. 4 . we will go one step further and neglect all couplings between the hybrids at the nearest neighbor atoms.67). Here.221) The hybrids lht201-i) at the nearest neighbor atoms pointing td the surface atom lor.38 for different symmetry lines of the first surface B Z of the hexagonal lattice of Figure 3.lOq)= v . with dt being a vector which points from the surface atom 10r toward its nearest neighbor atom 20rt in the direction of the hybrid t. 2 (3.

This structure may be considered to be an infinite repetition of the original crystal with surface.38 occur would be covered by more bulk state surface bands. More strictly. The three lowest and three highest bands are bulk state surface bands. It forms a bound surface band. which bind this atom back to its nearest neighbors in the second layer. They arise from the three hybrids of the surface atom. we similarly considered a . Supercell method The slab considered in the preceding subsection may be repeated periodically in the direction perpendicular to the surface.5. This arrangement represents a 3 D supercrystal composed of 1D supercells (bear in mind that in the case of point defects in section 3.98 e V .13 e V .39). The band in the gap is due to the dangling hybrid of the surface atom. The TB parameters are V1 = 2. each repetition being approximated by a finite slab of several atomic layers embedded between vacancy layers. while the bound surface band in the gap would hardly change. V2 = 6. the region where the bulk bands in Figure 3. Clean semiconductor surfaces 367 r M K r W avevec tor Figure 3. they correspond to the 3 back bonding and antibonding states. The hybrid energy Eh is used as the energy origin.3.6. simultaneously inserting several layers of vacancies between two neighboring slabs (see Figure 3. If we were to consider more than 2 atomic layers.38: Band structure of the ideal (111) surface of a diamond crystal within the defect molecule model.

Electronic structure of semiconductor crystals with perturbations Figure 3. provided the vacancy slabs are thick enough to suppress coupling between neighboring crystal slabs.368 Chapter 3. The band structure of the supercrystal is approximately the same as that of the original crystal with surface. then remove some number of neighboring atomic layers parallel to the surface under consideration or. 3D supercrystal composed of 3 D supercells). equivalently. This makes the supercell method particularly appealing. The latter are composed of crystal slabs embedded between vacancy layers. k l ) with respect to k l would indicate a coupling between the slabs. The significance of this characterization is the following: Consider first an ideal infinite 3 D crystal. The band structure of the supercrystal may be obtained by means of any 3 D band structure calculation method without modification. which has been excluded. Combined with the pseudopotential method. . In this. as well as the local density functional or quasi-particle approximations. Defect model and Green’s function method A crystal with surface may also be viewed as a 3 D crystal with a 2D perturbation.39: Supercrystal obtained by a periodic repetition of supercells. and the latter slabs are thick enough to simulate a semi-infinite crystal. it represents the most important calculational method for electronic and atomic structure determinations of surfaces. k l may be chosen arbitrarily because any dispersion of EF(k) = E F ( q . The bands Ep(q) of the crystal with surface are obtained from the bulk bands EF(k) of the supercrystal by plotting the latter on the surface B Z .

Wannier functions are again a possible choice. more strictly. and are identical with that of the considered crystal with surface. which we will assume.40: Illustration of the defect method for calculating surface energy band structure.1 (see equation (3. The electronic structures of the two semi-infinite crystals coincide. Here. As in the case of a single vacancy.3. For the analysis of the bound state condition (3. create the same number of vacancy layers (see Figure 3. It has the 2D lattice symmetry of the surface so that ~ ’ ( x= V’(X ) + r). one has to use a particular basis set. just as in the case of a point perturbation. the states bound at the defect may be obtained by means of the Greens function G o ( E )of the unperturbed 3D crystal. by the vanishing of the determinant of [Go(E)V’ .74). It is the negative of the sum of the potentials of the removed atoms or the sum of all vacancy potentials. a single layer of vacancies is enough to decouple the two semi-infinite crystals. but here they involve localization only in one direction.6. such that . Clean semiconductor surfaces 369 Figure 3. the perturbation potential 1 V’(x) represents the difference of the potential energy of an electron in the perturbed and unperturbed crystals. namely that perpendicular to the surface.223) If only nearest neighbor interactions are taken into account. (3. They do not interact provided the number of vacancy layers is large enough. What remains are two identical semi-infinite crystals which are only displaced with respect to each other.40).134)). We denote these functions by IvqRl) where RI is the component of a 3D lattice vector R perpendicular to the surface.

Transfer matrix method Finally..370 Chapter 3.e..1 take the form - with (3. still another method for surface band structure calculations should be mentioned.(q) .228) According to equation (3.94) for deep centers. (3. The relevant matrix elements (vqOIGoV1 1lvlqO) of GoV1. This dependence in the case of surfaces causes the eigenvalues in the gap to form ‘deep’ bands rather than deep levels (which was the case for point perturbat ions). The transfer matrix M ( E ) is formed from solutions of the Schrodinger equation upon one unit cell of the bulk crystal for particular boundary conditions in the direction perpendicular to the surface.229) If one compares this equation with the corresponding relation (3.6.] = 0..(q) = (vq01V’Jv’qO)has been used. Transferring the wave function from the surface unit cell to the .224) The matrix representation of the Green’s function Go(E) with respect to this basis set is For the perturbation potential V1(x) we take that of a single layer of vacancies located at RI = 0. It is based on the transfer matrix concept of quantum mechanics.227) must vanish for energy eigenvalues E in the gap of the ideal crystal. Then the matrix representation of V1(x) is where VL. Electronic structure of semiconductor crystals with perturbations (3.. Det [G:(E. it will be noted that the q-dependence which occurs here was absent there. the determinant of the matrix (3. q)VL.134). The energy E is arbitrary first of all. i.

the Si (100) surface. A t o m i c and e l e c t r o n i c structure of particular surfaces 3.6. as was pointed out earlier. It is advisable to treat the atomic structure together with the electronic structure because of the close relation between the two kinds of structures. The practical use of this method seems to be limited. The interaction of electrons with the atomic cores and the valence electrons of a crystal is significantly stronger than that of photons and neutrons. The crystal structure may be determined from the positions and intensities of these maxima. X-ray photons and neutrons interact only relatively weakly with the crystal.e. the (110) surface of GaAs and other 111-V compound semiconductors as well as the (111) and (100) surfaces of GaAs.1 e V are required for wavelengths in the d region. Electron energies in the region of 100 eV and neutron energies of 0. Since they are neutral particles. The various experimental methods differ primarily in the nature of the waves employed. including those at the surface. X-rays and neutrons thus yield information on all atomic layers of a crystal.t h power W ( E ) of M ( E ) . Experimental methods for surface s t r u c t u r e analysis Experimental methods for determining the atomic structure of bulk crystals are all based on the interaction of waves with the atomic cores and valence electrons of the crystal.th unit cell below the surface can be done by applying the n . however.6. Bound surface states are obtained for such energy values E for which M n ( E ) decays exponentially with n. They can pass through crystals of macroscopic thickness and be backscattered from them from macroscopic depths within them. Clean semiconductor surfaces 371 n . If the wavelength is of the order of the distance between the atoms. X-rays are by far the most important for determining the structure of bulk crystals. Electron and neutron waves are also diffracted by bulk crystals. again referring to both the atomic and electronic aspects. the crystal constitutes a 3D diffraction lattice and diffraction maxima will occur in prescribed directions in space. of the order of magnitude of 1 A.3. including the various reconstruction states of the Si (111) surface.4 In this subsection we will deal with the atomic and electronic structures of some important semiconductor surfaces. A wavelength in the region of 1 corresponds to a photon energy in the range of 10 k e V . the diffraction patterns are dominated by the bulk of the crystals. Electrons having energy less than 100 k e V can not pass through a crystal of . i. Since the number of surface layers is extremely small in comparison to the total number of layers. We begin with a short introduction to the experimental methods of surface structure analysis.

This is important because electrons scattered back from the surface have. is equal to the inelastic mean free path of the electrons.231) always exists for given vectors k and g (this is in remarkable contrast to coherent scattering of eleci trons from 3D bulk crystal. one therefore has only the backscattering available and then only elastically backscattered electrons can be employed in forming diffraction patterns.41.ll parallel to the surface differ from the parallel component kill of ki by a reciprocal surface lattice vector g. (3. to multiple scattering processes. The interaction with the crystal generates scattered waves with wavevectors k. experienced many scattering events. which can only occur if k.230) we have implicitly assumed that only one scattering event takes place. thus its Fourier components differ from zero only for vectors g of the reciprocal surface lattice. This means that only those scattered wavevectors k./= lkzl . hence (3. The electrons measured in LEED are elastically scattered.230) There is no relation between the components of k. Electron diffraction in this energy region is thus hardly suitable for examining bulk crystals but it can be readily employed in studying crystal surfaces. The solution of equations (3. One therefore has Ik. It is referred to as LEED (Low Energy Electron Diffraction). and ki perpendicular to the surface because there is no translation symmetry of the scattering potential in this direction. in contrast to X-ray photons which typically have been scattered only once. In writing down equation (3. The points at which the vertical lines passing through the reciprocal lattice points g intersect the . These originate at a depth which. The diffraction of low energy electrons in the region of 100 eV is in fact the most intensively used method for surface structure determination. The principle of LEED may be explained as follows. We consider an incident electron wave with the wavevector ki. (3.230). as a rule. however. The scattering potential has the translation symmetry of the surface lattice. lies on a Bragg reflection plane). This varies relatively independently of the particular crystal under consideration from 4 A to 10 for energies of 20 eV to 300 eV. can occur whose components k. This difference is due to the above mentioned fact that electrons interact with the crystal much more strongly than do X-ray photons. on average.230) and (3.231) can be readily carried out using the construction shown in Figure 3.231) A solution of the two equations (3.. Electronic structure of semiconductor crystals with perturbations macroscopic thickness. Experimentally.372 Chapter 3. This relation also applies.

known as ‘Re5ection High Energy Electron Diffraction’ ( M E E D ) . In this way it is relatively easy to determine the surface lattice by means of LEED. These methods include diffraction of energetic electrons in the region of some 10 k e V . in particular the bound surface states in the energy gap of the bulk crystal.41: LEED maxima. There is exactly one maximum for each reciprocal lattice point g. To obtain the actual positions of atoms is more diacult.] lkzl. there are other methods for surface structure analysis which. and the less bright points to the finer reciprocal lattice of the reconstructed surface. Scattering of energetic ions ( M 1 M e V ) is used in techniques like ‘Rutherford backscattering’ (RBS) and ‘ion channeling’. Clean semiconductor surfaces 373 Figure 3. Imaging procedures of significance are transmission electron microscopy (TEM). can supplement it. Some typical LEED images are shown in Figure 3. This method relies on the external photoeffect in which an electron is emitted from the crystal by . Besides LEED. determine the directions in which diffraction maxima oc= cur. The most powerful and universal method is photoemission spectroscopy (PES). Construction of sphere Jk. The bright points correspond to the reciprocal lattice of the ideal surface.3. and diffraction of slow Helium atoms (of M I00 meV). Like for atomic structure determinations. scanning tunneling microscopy (STM) and atomic force microscopy (AFM). diffraction of X-rays incident almost parallel to the surface. One needs additional experimental and theoretical information about the intensity of the diffraction maxima as a function of the energy of the incident electrons (dynamical LEED). The reciprocal surface lattice can thus be read immediately from the distribution of the diffraction maxima on the registration screen. The direct surface lattice is the reciprocal of the reciprocal surface lattice. although they are not a substitute for LEED. a variety of methods exist to study the electronic structure of surfaces. The latter two methods have become particularly important.6.42.

By measuring angular resolved photoemission spectra (ARUPS). These electron energies correspond to photon energies which are not substantially larger. The emitted photoelectrons are spectrally decomposed with respect to their kinetic energies.(After Drathen. Ranke and Jacobi. in the far ultraviolet region. The term UPS (Ultraviolet Photoemission Spectroscopy) is used in this context. To enhance surface states and discriminate bulk states.374 Chapter 3. i. the wavevector dispersion of the bound surface energy bands can be determined.e.42: LEED pictures of six differently prepared GaAs (100) surfaces. 1978. Electronic structure of semiconductor crystals with perturbations x6 Figure 3. photoelectrons with kinetic energies around 50 eV are used whose inelastic mean free path is only about 5 A and which can therefore only come from this depth below the surface. To study moccu- . The only practically suitable radiation source in this energy region is the electron synchrotron.) absorbing a photon of sufficiently high energy. The thus obtained energy spectrum of photoelectrons maps the density of states of occupied electron levels of the crystal.

The difference (typically some tenths of an e v ) can be measured by means of PES and UPS. On the other hand. If the model has optimized parameters and results in a lower total energy than other models it may be given preference over them. they can be calculated on the basis of a particular surface structure model. electrical transport.1) are an example. pied surface states one may use inverse PES in which electrons captured by such states emit photons. and capacity measurements.6.43: Geometry of the ideal Si (111) surface (left) and of the Si (111) 2 x 1 surface according to the buckling model (right). These shifts differ for atoms in the bulk and at the surface because of the altered atomic structure at the surface. surface states can be resolved spatially and energetically (scanning tunneling spectroscopy). Clean semiconductor surfaces 375 11101 hi01 Figure 3. any experimental technique which probes the electronic structure of bulk crystals can be employed for surface electronic structure investigations. This applies to optical reflectivity. and it may be used to determine the parameters which can be varied in such a model. a variety of other techniques exists which can provide data on surface states. can also provide data on the atomic structure. In principle. Experimental techniques like field effect measurements fulfill this requirement from the very beginning. Controlling the energy of tunneling electrons in scanning tunneling microscopy. Beside photoemission. The calculation of the total energy is a purely theoretical test of the validity of a particular surface structure model. provided it can be made surface-sensitive. The solid state shifts of core levels (see section 2. Experimental techniques which primarily measure the electronic structure. . as well as electron energy loss spectroscopy (EELS).3. photoconductivity. By comparing theory and experiment one can evaluate the feasibility of various models of surface structure.

. and one dangling bond per surface atom. The (111) surface is the cleavage plane of diamond type crystals....376 Chapter 3. one obtains a 2 x 1 reconstructed (111) surface.-I I iii r I I. the electron occupancy of the bound surface band in the fundamental gap. After annealing it at 500 C .44) and considers. The ideal Si (111) surface is metallic. Electronic structure of semiconductor crystals with perturbations Figure 3. in particular. . and can host 2 electrons per surface unit cell. By cleaving a Si crystal in UHV at room temperature. The surface lattice is hexagonal.. I ' O r *!:! t i -5 .. !ii ::I ..43 (left)..44: Surface band structure of an ideal Si (111) surface.. ll K r 2D wave vector Si surfaces (111) surface The geometry of the ideal (111) surface of diamond type crystals is illustrated in Figure 3.8. a 7 x 7 reconstruction state evolves. and the two primitive lattice vectors are fi...*. .. Thus this band remains only half-filled. f2 of Table 3. . which remains stable at room temperature. There is one surface atom per primitive unit cell. The occurrence of a 2 x 1 reconstruction immediately after cleavage is to be expected if one examines the band structure of the ideal (111) surface (see Figure 3. Since 3 of the 4 valence electrons of a surface atom are in bonds with second-layer atoms. . This band arises from dangling sp3-hybrids of surface atoms. only 1 electron per surface unit cell is left for the bound surface band.* ..

8 points in the direction [ l i O ] .43. right-hand side) which in the early days of clean semiconductor surface physics was believed to be correct. i. and each band of the latter gives rise two band in the former.and its long side parallel to [ 2 m . a direct and a back-folded one. buckling would take place spontaneously.and its short side.e the translation symmetry of the surface would spontaneously be lowered. its r .e.and p-like dangling hybrids are just the bands below and above the gap discussed before. In this. The lower s-like band can host all electrons of the dangling hybrids. This can be done by a buckling of the surface.M-direction. If the translation symmetry is broken. one speaks of a Peierls instability or a Peierls t r a n s i t i o n However. parallel to [2ii]. parallel to [Olq. the so-called buckling model (see Figure 3. i. surface reconstruction is likely to take place.5. while no electrons remain for the population of the upper p-like band. Clean semiconductor surfaces 377 This state is unlikely to be stable. The surface is still metallic. A gap arises if the so far formal 2 x 1 reconstruction is made real. The hexagonal lattice with doubled primitive unit cell forms a rectangular lattice with primitive lattice vectors 2f1 -tf2 and f2 The short side of the rectangular primitive unit cell. To introduce the buckling model we consider doubling of the primitive unit cell in the direction of primitive lattice vector fi. The corresponding first surface BZ is also a rectangle (see Figure 3.6. Below we discuss a particularly simple reconstruction model. as has been indicated at the outset. which according to Table 3. Later.31) with its long side. A similar spontaneous symmetry breaking. There. If the total energy of this state were in fact lower than that of the ideal surface.X-direction. is parallel to [Olq. i. and the dangling hybrid at this atom more s-like simultaneously lowering its energy. while the three back-bonding hybrids at a lowered atom become more sp2-like and the dangling hybrid at this atom more plike simultaneously raising its energy. i. it was realized that buckling is energetically advantageous only for 111-V compound semiconductor surfaces. by alternately raising and lowering atoms in rows parallel to f1 above the surface and below it (see Figure 3. while it is not advantageous for group-IV semiconductor surfaces including the (111) surface of Si. the Jahn-Teller effect.e. The two bound surface bands derived from these s. the three back-bonding hybrids of a raised atoms becomes more p-like. was discussed in the context of point perturbations in section 3. while no translation symmetry was involved. buckling turns out to be energetically not favorable in the case of Si (111) surfaces. as in the case of surface reconstruction. however. right).43.43 right.3. shown in Figure 3.e its X . the point symmetry was broken. Populating the lower s-like band with two electrons per primitive surface unit cell means transferring charge from the atoms lowered below the surface to the atoms .e. i. The rectangular BZ is half as big as the original hexagonal BZ. There is no gap between these two bands because they arise from the same band of the larger BZ.

378 Chapter 3.45: a-bonded chain model of the Si (111) 2 x 1 surface (After Pandey. 1982). Part (b) shows the same views of the surface as in part (a). The top view in the second row has been rotated with respect to the top view in the first row in order t o allow for the side view below. but after reconstruction has taken place. . Electronic structure of semiconductor crystals with perturbations r? 'P r[1?01 U [I101 Side view a) b) Figure 3. Part (a) shows the unreconstructed surface in top and side views.

This implies the creation of an electric dipole which is too costly in energy to actually take place. the 2-5 bond). Figure 3. Using the terminology of section 2. breaking their bonds with atoms in the third layer (for example. In this way s-bonded chains occur along the [ l O q direction (Pandey. the former shows alternating rings with 5 and 7 bonded atoms (Figure 3. This may be seen by taking the primitive lattice vectors of the ideal surface to be f 1 + f 2 and -f2.A peculiarity of the n-bonded chain model is that it has a different bonding topology in comparison with the ideal (111) surface and also with respect to the buckling model. The dangling bond of the new surface atom (say atom 2) is used to establish bonds with atoms of the first layer (the 2-1 bond in this case). 1982).45b.2 f 2 + (fi + f 2 ) = f 1 . illustrated in Figure 3.46 shows the wavevector dispersion of the two bound surface bands as obtained from ARUPS measurements together with the calculated dispersion of these bands. second layer atoms in rows parallel to fi f2. One expects strong dispersion along the chains and weak for the perpendicular direction. The agreement is quite satisfying. The reconstruction model which actually applies to the Si (111) surface is the so-called s-bonded chain model.3. more strictly speaking.f 2 so that the short side of the rectangle is parallel to the chain direction [lOT]. The dangling bonds left at the third layer atoms (for example.e. The surface is in fact 2 x 1 reconstructed. This is due to the fact that bonds existing at the ideal and buckled surfaces are broken and new bonds are established in the s-bonded chain model.46. and the long side perpendicular to it (parallel to [121]).6. + . the configuration dependence of oneelectron states. i. The strong dispersion of the bound surface band on the r-X-line and the weak dispersion on the X-M-line of the rectangular surface B Z is easily understandable: the long r-X-side of the rectangular unit cell in q-space corresponds to the short side of the rectangular unit cell in coordinate space.5 eV per surface atom). Its primitive lattice vectors are f1 + f 2 and . atom 3). In this model.45b by dashed lines.45a).45. Thus it represents a good candidate for the reconstruction of the (111) Si surface.45b) because the dangling bonds are perpendicular to the surface. Further evidence is provided by ARUPS and optical measurements.2 we may say that correlation effects of electron electron interaction. prevents the buckled Si (111) surface to be lower in energy than the ideal one. Doubling -f2 yields the rectangular lattice indicated in Figure 3. which is also the direction of the s-bonded chains. exactly what is seen in Figure 3. Clean semiconductor surfaces 379 raised above. along the [lo3 direction in Figure 3. atom 5) are saturated by hybrids of the first layer atoms which have been lowered down to the second layer (for example.45a (including atom number 2) are raised into the first layer as shown in Figure 3. While the latter exhibit rings with 6 mutually bonded atoms (see Figure 3. These can only be s-bonds (indicated by double lines in Figure 3.45b). The total energy of this model is clearly below that of the ideal surface (about 0.

Nannarone. 1985.) 0 93 0A .M line for the Si (111) 2 x 1 surface. Cri- 2 > W d t2 3 1 0 Q. 1971. a centi. Electronic structure of semiconductor crystals with perturbations Figure 3. Pastore and Chiaradia. Curves are calculated within the 7r-bonding chain model.) Y l W x g o -1 r X nf 20 wave vector Figure 3. 0s .X .47: Differential reflectivity spectrum of the Si (111) 2 x 1 surface (After Chiarotti. Energy (ev) $5 [ 7 .380 Chapter 3. (After Martensson. and Hansson. points are obtained by means from ARUPS measurements.46: Dispersion of the bonding (B) and antibonding (A) bound surface state bands along the r .

6. However. There is no doubt that the observed peak at 0. Such bands exist both in the buckling model as well as in the 7r-bonding chain model (in the latter one has 7r-bonding and x-antibonding bound surface bands).I-bonding chain model.48 is that predicted by .e.49). 1984. The model which accounts for all experimental data utilizes three structural disturbances of the ideal surface. According to the 7r-bonded chain model.48: Polarization dependence of the differential reflectivity spectrum of the Si (111) 2 x 1 surface of Figure 3.5 eV is due to optical transitions between occupied and unoccupied bound surface bands.47. these being dimers (D). transitions with light polarized parallel to the chains.) Support for the r-bonded chain model comes also from optical measurements. It rules out the buckling model. parallel to [lOq.45 (taken at its maximum). Besides the 2 x 1 reconstruction. adatoms (A) and stacking faults (S). i. Clean semiconductor surfaces 38 1 Figure 3. The complicated structure of this surface has finally been resolved by combining the results of various experimental methods including STM (see Figure 3. The differential reflectivity spectrum of the 2 x 1 reconstructed (111) surface of Si is shown in Figure 3. The experimentally observed polarization dependence shown in Figure 3. while this should be reversed for the buckling model. The solid curve is calculated using the x-bonded chain model. It is referred to as the DAS model . the two models differ in regard to their predictions on polarization dependence of optical reflectivity. The 7 x 7 reconstructed surface is the most stable one.3. there are other reconstruction states of the Si (111) surface. and the points are experimental data (After Del Sole and Selloni. the dashed curve using the buckling model. should be allowed and transitions for light polarized parallel to the perpendicular direction [121]should be forbidden.

Thus. and the surface lattice becomes rectangular. Each dangling bond is only half-filled as in the case of the (111)surface considered above. so that the surface is not yet stable. f2 given in Table 3. The surface lattice is a square one.50. (After Quate.49: Scanning tunneling microscopy (STM) image of the Si (111) 7 x 7 surface.8.) (Takayanagi. A state of lower total energy can be established by a 2 x 1 reconstruction as follows: The atoms of two neighboring rows parallel to [ O l i ] (or [Oll]) move slightly towards each other in order to allow bonding between two of their four dangling hybrids. 1984). Electronic structure of semiconductor crystals with perturbations Figure 3. however. 1986.51. The primitive lattice vector in the direction of f 1 doubles. the ideal surface is metallic. the lower bonding state being completely filled and the upper antibonding state being completely empty. . and this state is unlikely to be stable. and each atom has two dangling bonds which point out of the surface like ‘rabbit ears’ (see Figure 3. This dimerization of the surface gives rise to bonding and antibonding bound surface states. The geometry of the ideal (100) surface is shown in Figure 3. with primitive lattice vectors f 1 . thus a 2 x 1 reconstruction takes place. It is stabilized by buckling. The primitive unit cell has one surface atom.51a).382 Chapter 3. (100)surface The (100) surface is the surface of choice for electronic device applications of Si. The remaining two dangling bonds of a dimer are still half-filled. The DAS model of the 7 x 7 reconstructed (111) Si surface is shown in Figure 3.

being p-like. Due t o the two kinds of displacements. (After Takayanagi. The top view (b) shows a 7 x 7 surface unit cell and its surroundings.50: Dimer-Adatom-Stacking-Fault (DAS) model of the Si (111) 7 x 7 surface. the dimers become asymmetric. They only add displacements of the dimer atoms parallel to the surface in addition to the perpendicular ones.) which turns out to be energetically favorable in this case. while the dangling hybrid at the raised atom. takes a higher energy and is correspondingly empty. being s-like.3. 1984. solid circles are bulk atoms which do not undergo reconstruction. The dangling hybrid at the lowered atom. Clean semiconductor surfaces 383 a1 Figure 3. One of the two atoms of a dimer moves above the surface and one below. The small circles within shaded circles represent second layer atoms vertically below the adatoms. open circles are surface atoms of the first (large circles) and second (smaller circles) monolayer. takes a lower energy and is filled. The described 2 x 1 reconstruction of the Si (100) surface is therefore called the . The side view (a) is shown to identify the atoms: large shaded circles are adatoms. Rigorous structure calculations essentially confirm this simple tight binding picture.6.

2 x 2. c . c .51: Geometry of the ideal Si (100) surface (a). Although the 2 x 1 reconstruction is the most common superstructure of the Si (100) surface.4 x 2.2 x 2. for example. Electronic structure of semiconductor crystals with perturbations Top view (100) I-- 0 n 0'. Its surface geometry is shown in Figure . asymmetric dimer model. GaAs and other 111-V compounds (110) surfaces The (110) surface represents the cleavage plane of zincblende type crystals.-0 Side view It- ? 0 U 10113 U a) b) Figure 3. Most of these structures may be traced back to asymmetric dimers as building blocks.384 Chapter 3. other reconstructions are also observed. and of the asymmetric dimer model of this surface. The best understood (110) surface of all zincblende type 111-V semiconductors is the (110) surface of GaAs.

Thus one expects two bound surface bands. It can be enlarged by moving the As atom above the surface. and the higher Ga-like band is completely empty.53. Thus the ideal surface is semiconducting. and moving the Ga atom below . one Ga-like and one As-like.6. The surface lattice is p-rectangular.52: Geometry of the ideal GaAs (110) surface (a). The two dangling hybrids per unit cell have different energies since they belong to either a Ga. as the gap between the two bound surface states is too small. Nevertheless. 3. rendering its dangling hybrid more s-like and lowering its energy. There are two surface atoms in a primitive unit cell. The lower As-like bound surface band is completely occupied.52.8. one is directed back and one is dangling. Clean semiconductor surfaces 385 Top view (110) Ga o As 0 I ? I I I I I 1 I I 5 0 Y I I 1 I I I I I I I I I [?I0 1 Side view 0 c7 U [?I01 a) b) Figure 3.3. These are in fact seen in the band structure of the ideal (110) GaAs surface depicted in Figure 3.or an As atom. The primitive lattice vectors are given in Table 3. Two bonds of each surface atom lie within the surface. one Ga and one As atom. and of the same surface after relaxation (b). it does not yet represent the stable state.

The experimental value for the rotation angle w of a Ga-As bond with respect to the [ l i O ] direction is close to 30°. for example.54). These displacements do not change the translation symmetry of the surface because the two atoms belong to the same unit cell. and the Ga-like band merges into the conduction band.53: Band structure of the ideal GaAs (110) surface. in good agreement with structure calculations.52). Such states are in fact present at GaAs/insulator interfaces. This is consistent with LEED measurements. coverage by an insulator. relaxation moves the bound surface states out of the gap (see Figure 3.54. which do not show spots other than those due to the ideal prectangular lattice. can easily create surface states in the gap. They pin the Fermi level and preclude the possibility of making GaAs-based field effect transistors in the same way as the Si-based MISFET (see Chapter 7 for further discussion). One therefore has a relaxation instead of a reconstruction of the (110) surface. relaxation moves the bound surface bands completely out of the fundamental gap. the As-like band merges into the valence band. rendering its dangling hybrid plike and raising its energy (see Figure 3. This implies that perturbations of the surface such as. 1992. Electronic structure of semiconductor crystals with perturbations Ga As (111) (1101 (1001 -10 r M K r r x ' M X r r i ~ l r 2 D wave vector Figure 3. For all materials except Gap. Relaxations similar to that of the (110) surface of GaAs are also observed at the (110) surfaces of other 111-Vcompounds. (After Talwar and Ting. . Experiment and theory also agree in regard to an essential feature of the band structure of the relaxed (110) surface. As indicated in Figure 3.386 Chapter 3.) the surface.

) Other surfaces Besides the (110) cleavage surface.54: Energy level diagrams of bound surface states and bulk states of various 111-Vcompound semiconductors below the vacuum level.51. in Figures 3. nor (loo). respectively. Solid lines represent experimental results. Calandra.6. an electric dipole is created between a Ga-layer and an As-layer which is costly in energy. (100) is the preferred surface orientation of GaAs wafers used in device fabrication (partially because the (011) plane perpendicular to this surface represents the cleavage plane of GaAs). like in the case of group-IV materials. In forming a polar surface. and dashed regions represent dangling bond surface bands. The (111)and (100) surfaces of GaAs differ from the (110) surface of GaAs mainly in regard to the fact that two different surface terminations are possible in their case. 1978. (After Bertoni.43 and 3.3. and Manghi. One says that these surfaces are polar. in contrast to the (110) surface. For the polar surfaces. no stoichiometrical reasons which cause a surface termination by . but the non-polar (110) plane. Clean semiconductor surfaces 387 (110)cleavage face h GaP GaAs GaSb In P In As In Sb 2 A -3-4U n u 0 5 3 9 -5- w 3 -6x e E -7- g Figure 3. investigations have mainly been focused on the low index (111)and (100) surfaces of GaAs. In the latter case the 1:l ratio of Ga. The geometrical structures of the ideal surfaces are the same as those of the corresponding Si surfaces shown. one by Ga atoms and another by As atoms. F'ramed undashed regions indicate bulk bands. the cleavage plane is neither ( l l l ) . there are.and As atoms is strictly k e d by chemical stoichiometry. which is said to be non-polar. however. This explains why for GaAs and other 111-V compound semiconductors. Bisi.

Electronic structure of semiconductor crystals with perturbations only Ga. such effects might be important. depending on surface termination.42. Figure 3.55 shows an example. The microstructures to be considered in this subsection are composed of semiconductor heterojunctions.7 Semiconductor microstructures Semiconductors with a clean planar surface. and above it is the material 2. Thus. Free carrier effects on the electronic structure can be neglected in these circumstances. The structure of a particular polar GaAs surface depends decisively on its termination. For the Ga-stabilized surface. a 3.30° and reconstructions in addition. The structure of the GaAs (100) surface exhibits an even greater variety. before addressing microstructures we must deal with het eroj unct ions. Below the plane at z = 0 one has semiconductor material 1. 3.388 Chapter 3. say AlAs. we discuss the various stationary one-electron states of undoped heterostructures. . considered in the section above.23. omitting free carrier effects. which raises the As atoms close to the surface. In the case of heterostructures formed from doped semiconductors. They are treated in Chapter 6 in a systematic way. If the vacuum is replaced by a semiconductor material different from the first. x .7. say GaAs. The remaining first-layer Ga atoms and the second layer As atoms undergo a buckling.8 x 2 reconstruction is found to be stable. Below. the c .2 x 8 structure is found for an As-stabilized surface. which is important for MBE-growth because this commonly begins and ends with As-rich conditions. Some of the possible reconstruction states can be seen in the LEED pictures of Figure 3. may be thought of as units of two infinite half spaces. surface treatment and temperature. The two semiconductor materials are taken to be undoped. one filled with the semiconductor material. The c .1 Heterojunctions Below we describe the electronic structure of semiconductor heterojunctions. and the other being empty.4'' and for the As-rich case there are f i x 8.or only As atoms. and in order to define the surface uniquely one has to specify the percentage of Ga and As it contains. For the Ga-terminated 2 x 2 (111) surface. then one obtains a semiconductor heterojunction or single semiconductor heterostructure. a model has been proposed with a quarter of the surface atoms missing. A rough distinction is that between Ga-rich and As-rich surfaces. Both kinds of terminations can occur simultaneously at a given surface. For the Ga-rich (111) surface one finds a 2 x 2 reconstruction. The plane at z = 0 is called the interface.

n(ko) of material 2 does not coincide with any of the allowed energy levels E. then states extending over the whole heterojunction from -cc to f m will exist (Figure 3. it is not a priori clear what will happen. Vice versa. with E.a(kb) at dzflerent wavevectors ko and kb. If a matching of the corresponding two eigenfunctions and their derivatives at the interface turns out to be possible.a(k) of these materials. Just as in the surface case.56a by representing energy levels of this kind by lines extending from z = 0 to z = +co. If there are energy levels at ko which are identical in both materials. then the eigenfunction belonging to this level and quasi-wavevector will be localized in material 2.56b). i.e. it forms a bulk state of material 1. heterojunctions of the kind described above possess a 2-dimensional rather than a 3-dimensional lattice translation symmetry. Generally. an energy level E.7.If . Let us fix a particular quasi-wavevector ko.l(k) and E. at ko. What may change are the eigenfunctions of these energy bands. In the case of identical energy levels E.l(ko) at ko of material 1. if. the Bloch bands E. and may be represented by a line extending from z = -co to 0.3. their one-electron states cp(x) are Bloch states (Pk. i.l(ko) of material 1 does not coincide with any of the allowed energy levels E. ) in regard to their dependence on the position vector comz ponent XIIparallel to the interface. If an energy level E.l(ko) and E.it forms a bulk state of material 2. This is illustrated in Figure 3.56~). with 2-dimensional quasi-wavevectors kll. There. almost all energy eigenvalues of the two infinite bulk materials. Semiconductor microstructures 389 Stationary one-electron states As in the case of a crystal with a clean surface. The corresponding energy eigenvalues form bands in the 2-dimensional first B Z of the heterostructure.l(ko) = EA(ko)..z(ko) of material 2. its wavefunction is spread out uniformly over the whole semi-infinite crystal from z = 0 to z = +co.(xI(. are also energy eigenvalues of the heterojunction.e. the corresponding wavefunctions will extend over both materials (Figure 3.

One has a situation similar to that in the case of electromagnetic waves propagating between two semi-infinite dielectric media: for certain wavevectors they may propagate from one medium into the other. just like the bound surface states in the case of clean surfaces. there may be stationary states with energy eigenvalues which are allowed in none of the two materials. They are called bound interjuce states. as indicated in Figure 3 . 5 6 ~ . The wavefunctions of such states are localized at the interface between the two materials. Electronic structure of semiconductor crystals with perturbations Material 1 I Material 2 P a.390 Chapter 3. Besides bulk states. and for others they are internally reflected. no matching is possible. Figure 3. In analogy to the clean surface case. then the two eigenfunctions will remain localized in their respective material regions.56: Various bulk states of a semiconductor heterojunction. L . interface resonances .

the maximum energy of the valence band itself depends on the material under consideration. We will denote the valence band edge of a particular material i . This statement may seem to contradict the results of Chapter 2. is given by --E$ If the electron should escape by absorbing a photon. Semiconductor microstructures 391 may also occur. having a thickness of several atomic monolayers. the maximum energy of the valence band occurs at the center r of the first BZ. in general. thus lowering the total energy of the heterojunction. the infinite bulk values Etl and Et2 have only an indirect meaning. by E$. If the valence band maximum is taken as zero for one material. we select the vacuum level as the common energy origin. the energy origin could be chosen arbitrarily. Valence band discontinuity In many semiconductors. then -Eti is the minimum photon energy required (photo-t hreshold energy). then no bound interface states will be possible. an electric dipole layer develops at the interface. differ from zero for the other material. This level may be defined as the minimum energy which an electron in an infinite semiconductor sample must have in order to escape. and we took it to be at the valence band maximum.2.3. this was done in the context of dealing with the band structure of only o n e infinite bulk semiconductor at a time. For such a single semiconductor. but the energy origin of the heterojunction can be fmed only once. and it can also be analyzed in a more rigorous treatment: valence electron charge will flow from the material with the higher valence band edge into the material with the lower valence band edge. but the associated dipole . because the perturbation at the interface is too weak. referred to the vacuum level as origin. two semiconductor materials are involved. for each of the two semiconductors of a heterojunction the adjacent material is foreign and represents an external perturbation. Then the minimum energy which must be expended to remove a valence electron from material i . Even if no free charge carriers are available.7. where this energy was set to zero for all materials. If the two materials forming a heterojunction are composed of chemically similar atoms as in the case of GaAs and AlAs and in many other cases of practical importance. instead of setting it to zero for any material. How this occurs is quite clear physically. each of the semiconductors reacts to this perturbation by redistributing its electrons. their energy levels lie in one of the bands and their wave functions are weakly localized at the interface.55. i = 1. the spatial extension of the dipole layer is zero. in this case its bound valence band electrons. Below we will restrict ourselves to materials of this kind. Of course. For the actual positions of the valence band edges Evl and Ev2 at a heterojunction. as we assume. Macroscopically. In this way. In fact. In the heterojunction of Figure 3. However. it will. Here.

the band discontinuity also contains the dipole contribution -e[cpi-pg]. The latter generally depends on the properties of the interface.232) the valence band discontinuity AE. In formula (2. . As pointed out above. If one were to ignore this dipole contribution. The bonding energy level € b considered there forms a rough measure for the average valence band energy.232) The difference AE. As is well-known from electrostatics. The corresponding bonding orbitals IbtR) of equation (2.315)’ € b is given for a zincblende type semiconductor.6.E.233) Beside the pure bulk contribution [E$ .E&]. is expressed as (3. value of 2 .2] between the two valence band edges is called valence band discontinuity or valence band offset of the ‘material l/material 2’ heterojunction. In practice this ‘rule’ is rarely fulfilled. the charge transfer will result in an electrostatic potential difference at the interface. no charge transfer would occur. - ecp2. This is described by the relation + -1 ch .. If the hybrid energies were equal. valence electron charge will be transferred into the material with the lower .1 and E. A semiconductor material i composed of cations ci and anions ai.-values for a succession of two heterojunctions ‘1/2‘ and ‘213‘ should add up to the AE. the potential cp exhibits a discontinuity in passing through such a dipole layer. (3.234) .€2. forms a big molecule of the average hybrid energy 2 = (€2 &/2.1 . By means of equation (3. The potentials on either side of the interface will add to the average hybrid energies and diminish their difference. would obey the so-called ‘transitivity rule’ which states that the AE.ecpi = F. and the right one by 9 2 . The dipole contribution -e[cpl .cpz] may be estimated by means of the tight binding method developed in section 2. which points up the importance of the dipole contribution to A E. We denote the left boundary potential value by cp1. Electronic structure of semiconductor crystals with perturbations moment has a non-zero macroscopic magnitude. zz [E. . the average hybrid energy difference S i .316) describes the charge transfer from the cation c (there denoted by an upper index ‘1’)to the anion a (there denoted by an upper index ‘2’) in terms of the hybrid energy difference EL . Thus the charge transfer between material 1 and material 2 is governed by .2 If this difference is non-zero. Then the actual positions of the valence band edges E.392 Chapter 3. Charge will flow until the average hybrid energy difference has been equilibrated by the potential jump.2 at the heterojunction are given by the expressions (3.-value of the combination ‘1/3’. then AE.

. in many cases. optical or transport properties of heterojunctions. Experimental values for valence band discontinuities of several heterojunctions are shown in Table 3. different values are obtained by different methods or even by different authors using the same method. Often.Al)As alloys.T i ] . Semiconductor microstructures 393 i. ETM 2 .EVi. There.61 ~ ~ 1 .Sk. a great deal of effort is devoted to the task of obtaining more reIiable experimental and theoretical data for AE. calculated valence band discontinuities have also considerable uncertainty. This points up the experimental difficulties in determining valence band discontinuities. and also to the dependence of the discontinuities on the preparation of the heterojunctions. of the two materials.7. so that E ) = E k M .3. i = 1 . 2 . . Such an accuracy is difficult to achieve so that. Other experimental methods rely on measurements of photoemission. the lineups of all other energy levels at I and off I can be determined from the known bulk band structures of the two materials.237) This relation reduces the experimental determination of valence band discontinuities to measurements of deep level positions of TM atoms with respect to the valence band edge. . we denote these positions by E ) ~ .10. (3.1 eV. it was shown that the difference between the position E+M of a deep level of a particular TM atom in a semiconductor material 2.5. In order to obtain theoretical values for valence band discontinuities. O t h e r band discontinuities Knowing the lineup of the valence band edge at I? for a particular hetero' ' junction. Below we . At this point it is advisable to recall a result concerning deep levels of transition metal (TM) atoms obtained in section 3.721 to the valence band offset S matches I. and the position E&M of the same deep level in a semiconductor material 1. (3. To this day. hence AEIJ= [ETM 2 .1. and the potential contribution -e[cpl.236) Considering relations (3. the average hybrid energy levels on the two sides of the heterojunction align. the difference [ c $ ~ t+M] between the positions of the deep level in the two materials is just the valence band discontinuity A E . electronic structure calculations are required with an accuracy of less than 0. ~ 0 (3.235) Taking the deep level positions to be measured with respect to the valence band edges E& of the two infinite bulk materials. equals the average hybrid energy difference between the two materials. that being between GaAs and (Ga.236).234) to (3. even in the case of the most thoroughly explored heterojunction.E&M = 7.e.

The gap discontinuity AE.Al.Al.57 the valence and conduction band edges of the Gal-. Because of AE.l.As alloy are plotted as a function of x. and Q c = AE.e. it follows that AE. the two band offsets AE.Eg2 of the two infinite bulk materials. A E . Ec2 = E v 2 + Eg2.29 1. one has Q .2 of the two materials are obtained from the relation Ec1 = E v 1 + E ~ I . by means of the ratios Qv = AE.As heterojunction as an example.2 are the gap energies of the two materials.2 .As with x < 0. can be calculated by means of relation (3.81 0. and AEc are expressed in percent of the gap discontinuity AE. = E. If AE.239) where AE.Al.54 0. i.77 InAs/GaSb -0. the conduction band + + .46 0. Ec2 .239).238) where E. and AE.E1 is the discontinuity of the energy gap.96 0. follows from the gap energies Egl. for GaAs/AlAs or GaAs/Gal-. Often.42.39 1.42 is schematically plotted in Figure 3. In the f i s t case (x < 0.2 ..23 0. together with the lineup of the valence band edge..As heterojunctions with alloys having an indirect gap (z > 0. The lineup thus obtained for the conduction band edge of a GaAs/Gal_. Qc = 1.Ecl = -AEv + AEg. = AE.25 HgTe/CdTe 0. but the conduction band minimum at the B Z boundary point X .394 Chapter 3.24 1. AE.42 are direct semiconductors with both the valence band maximum and the conduction band minimum at I. are known. While GaAs and Gal-. Electronic structure of semiconductor crystals with perturbations Junction AE.43 demonstrate this taking the conduction band edges of a GaAs/Gal-.41 InP/CdS 1.Al. For the conduction band discontinuity AE.E. These two cases are also to be distinguished in aligning the conduction band edges of the heterojunction./AE. In Figure 3. (3.(eV) AEg(eV) Ge/GaAs 0.(eV) AE. alloys ‘ with z > 0.Al.02 1. .58a.63 -0. In the second case./AE. (3.35 GaAs/ZnSe 0.42).As heterojunction with x < 0. = E.42 and pure AIAs form indirect materials with the valence band maximum still at r. the conduction band edges Ec1.1 of the ‘material l/material 2’ heterojunction.

respectively.58: Conduction and valence band lineups for a GaAs/Gal-. GaAs and Gal-.AI. .4 -. The Fe(1 /2+) acceptor level is used as energy origin following the discussion in the main text. Semiconductor microstructures 395 Figure 3.- Fe(1+/2+) Composition x tc2 Ec2 X r I r r I Ev2 Ev2 Figure 3.) f c c 2.Al.7.42) the alloy gap is direct. .As are also plotted in the respective other material where they do not form the conduction band edge. 1985.!) the alloy gap is indirect.As heterojunction. In the latter case. the r and X levels forming the conduction band edges in.3.+ ---. ( A f t e r Langer and Heinrich.6 + 0.57: Valence band edge at r together with the lowest conduction band levels at I? and X for Gal-xA1xAs alloys of varying composition x. and in part (b) (x > 0 4 2 . In part (a) ( x < 0.0 3 1.

are. say of materiai 1. it becomes evident that it is no longer meaningful to plot the conduction band edge throughout the whole heterojunction as before. and also E. may lie below the conduction band edge of material 2. E. In this case the gap of material 1 is located entirely within the gap of material 2. below the two edges of material 2.1. the second material must be placed on top of a crystal made from the first by continuing the crystal growth. 3. one has a heterojunction of type II. What may be plotted is the lineup of the r and X levels forming the band edges in one of the two materials. Electronic structure of semiconductor crystals with perturbations edges of the two materials occur at different k-points.As alloy at X . that of GaAs at r. type ZZI heterojunctions are defined. Recalling the discussion about the stationary electron states of heterojunctions at the outset of this section. In the staggered case the heterojunction still has a gap. i = 1 .59).1 < Eva holds.As alloy region forms a barrier. This case is referred to as heterojunction of type I. The staggered type II heterojunction occurs when we have Ec2 < E.1. and the misaligned case applies if Ec2 > E. A look at Table 3. the Gal-. incapable of hosting electron and hole states which extend upon both materials. again 1.10 shows that the heterojunction 1 Ge/GaAs is of type I.396 Chapter 3.Al.i and Eci. InAs/GaSb of type 11-misaligned. examples Heterojunctions cannot be fabricated by simply putting together two separately made semiconductor samples with plane surfaces.2 Microstructures: Fabrication. polluted interface. a process referred to as epitaxial growth. respectively. If one would proceed in such a way the result would be a completely rough. There are several qualitatively different possibilities for the lineup of the two band edges E.1 < Ec2. the GaAs region does so.7. a property which has been assumed above and which turns out to be crucial for the electronic behavior of a heterojunction. classifications. These are heterojunctions of type I with zero energy gap in material 1. In actual practice. Types of heterojunctions Consider two direct gap semiconductors with the valence and conduction band edge at I?.staggered. This is done in Figure 3. CdS/InP of type 1 . while in the misaligned case the conduction band of material 1 overlaps with the valence band of material 2 so that the gap of the heterojunction disappears. and that of the Gal-. say. 2 (see Figure 3. The conduction band edge of one material. The illustration indicates that for the conduction band states of GaAs with wavevector r.Al. Sometimes. and HgTe/CdTe is of type 111. and for the conduction band states of the alloy at X .58b. If both the conduction and valence band edges of a particular material. In . while simultaneously the valence band edge of material 1 may lie above that of material 2.

a third layer on top of the second etc.60). The term superlattice is used if alternating layers of two materials are grown with equal thicknesses for layers of the same material (see Figure 3. this kind of growth the underlying crystal. namely Molecular Beam Epitaxy (MBE) and Metal Organic Vapor Deposition (MOCVD). For epitaxial growth to be possible. and their lattice constants must be close to each other. Semiconductor microstructures 397 W C + >r P W Type staaaered EC2 Ev2 tvi misaligned A 15 F x d 0 2 material 2 0 material 1 material 2 2 material 1 Figure 3. . to more complex structures by growing a second epitaxial layer of another material on top of the first. the two materials must have similar crystallographic structures.3. Two epitaxial growth techniques are particularly important in this context. Epitaxial growth The fabrication of heterojunctions by means of epitaxy suggests to proceed from simple structures consisting only of the substrate and the epitaxial layer. imposes its structure onto the growing layer. I1 and 111.59: Heterojunctions of type I. in contrast to ordinary deposition of an evaporated material which commonly results in a non-regularly structured layer.7. If one does so. the so-called substrate. one obtains double and multiple heterostructares.

and their shutters must be open at the same time. The principle of MBE is shown in Figure 3.61. for example. Doping of the layer may be achieved by opening a third effusion cell containing the dopant atoms. If one.g. multiple heterostructure (c). Herman and Sitter. In order to grow a GaAs/AlAs superlattice. double heterostructure (b).60: Heterostructures as grown by epitaxy: single heterostructure (a). Electronic structure of semiconductor crystals with perturbations Figure 3. the flux from the effusion cells. One may employ characterization techniques which require UHV. Thus the As partial pressure must be much larger than the Ga partial pressure in the epitaxy of GaAs on a GaAs substrate. or mass spectroscopy for analyzing the composition of the residual gas in the growth chamber (for more on MBE see.. The whole growth process takes place in a vacuum chamber under UHV conditions (typically about 2 x 10-l' T o w ) . In this chamber. MOCVD takes place in a chemical reactor at atmospheric . There are many parameters which influence the growth process. and the partial pressures of the various elements involved. e. 1989). The atoms or molecules from the effusion cells may have different sticking coefficients on the substrate. Unlike MBE. the temperature of the substrate. one needs a fourth cell with Ga. If one wants to proceed with a GaAs layer on top of the AlAs layer.398 Chapter 3. The fact that MBE proceeds entirely in UHV may be exploited in controlling the growth process. Arsenic atoms. such as RHEED for studying surface perfection. stick much less well on GaAs then Ga atoms. for example. one for A1 and one for As. in particular. wants to grow a AlAs layer on top of a GaAs substrate. the shutters of the Ga and A1 cells have to be opened and closed alternatively while the As shutter has to be kept open all the time. two cells are required. superlattice (d). the substrate is placed in front of a number of effusion cells which contain the various chemical elements to be deposited on the substrate.

After this the atoms are chemically bound to the substrate.) pressure or slightly below. say A1 and As. In order to proceed with a layer of different chemical composition. MBE is more universal and more responsive to control than MOCVD. but the atoms to be deposited are provided by the pyrolysis of . operates close to equilibrium conditions. are provided by metal-organic gases. say GaAs.7.[After Cho and Cheng. Al(CH3)3 has to be replaced by Ga(CH3)3 (trimethyl gallium) in the growth reactor. The growth velocity in MOCVD is typically somewhat larger than in MBE because more atoms are provided to the growing layer in MOGVD than in MBE.3. as in MBE. MOCVD. 1981. The advantages of both methods are combined in MOMBE (Metal organic MBE): the growth process takes place in an UHV chamber.61: Principle of MBE growth. unlike MBE. Semiconductor microstructures RHEED GUN 399 LIQUID NITROGEN COOLED SHROUDS / MAIN SHUTTER FLUORESCENT SCREEN TO VARIABLE SPEED MOTOR ANDSUBSTRATE HEATER SUPPLY Figure 3. The A1 and As atoms are liberated from their compounds by means of a pyrolytic process which takes place on top of the heated substrate. This makes MOCVD particularly suitable for producing devices based on heterostructures. The atoms to be deposited. Al(CH3)3 (trimethyl aluminum) and AsH3 (Arsin) in this case.

we will start with a qualitative discussion. One can grow layers up to several millimeter thicknesses and beyond but.As with z < 0.Al.62a. The latter is called a quantum well (QW) in this context. It turns out that the electronic structures of multiple heterostructures differ from those of the constituent materials if the layer thicknesses reach the nanometer range. Qualitatively. If. The same statement applies to holes in the case of the double heterostructure of Figure 3. The electron states of this heterostructure with energies close to the conduction band bottom will be spatially confined to the GaAs layer.4 we will prove this rigorously and describe the modified electronic structures in greater detail. The central layer in Figure 3. In subsection 3.Al.As double heterostructures.As barrier layer.62a).62b.4).As layers with x < 0.Al. both at the interface as well as in the bulk. from which they may tunnel through the following Gal_. one can also grow very thin layers. electrons and holes are no longer confined to layers of the same material. Another example of multiple heterostructures with modified electronic properties is provided by superlattices composed of alternating (and sufficiently thin) layers of GaAs and Gal-.Al.400 Chapter 3. just like for a particle in a potential box. and the alloy layers are referred to as barriers (for a systematic introduction of these concepts see subsection 3.7. By means of these and some other growth techniques it became possible to grow high-quality heterostructures of many elemental and compound semiconductors. In this case electrons from a GaAs well layer may tunnel through the neighboring Gal_. Electronic structure of semiconductor crystals with perturbations metal-organic compounds.As barrier layer reaching the next GaAs well. This leads to the formation of Bloch states and an additional energy band structure superposed upon the bulk band structure. meaning that the transition from one material to the other occurs essentially within one atomic layer. the same behavior is expected for su- . We consider a double heterostructure formed by a GaAs layer embedded between two Gal_. Here. The interfaces of these structures can be made almost abrupt. Unwanted impurities and structural defects can be excluded to a large extent. instead of type I GaAs/Gal-. an energy region exists where the stationary states of the double heterostructure are mixtures of the electron states of the two outermost layers and the hole states of the central layer.7. It is called a miniband structure.42 (see Figure 3.62c.Al. and so on. The confinement of electron states in the quantum well raises their energy and creates discrete levels.62b which forms a well for electrons is a barrier for holes. and the two outermost layers which are barriers for electrons are (semi-infinite) wells for holes. In the misaligned case of Figure 3. but to layers of different materials. as well as from semiconducting alloys.62d). as in MOCVD.c). what is more important from the physical point of view.42 (see Figure 3. we consider those of type I1 (see Figure 3. down to the ultimate limit of one atomic monolayer.

62: Double heterostructure of type I acting as a quantum well both for electrons and holes (a). It is not surprising that the layer thicknesses must lie in the nanometer range for the confinement and tunneling effects discussed above to occur: 1 nm = 10 A is close to the distance between nearest neighbor atoms in a natural crystal (in GaAs the nearest neighbor distance is about 2. Bloch states are formed from the electron and hole states of the respective wells. Heterostructures with such thin layers possess. so to speak. c). and of type I1 acting as a quantum well for electrons and a barrier for holes (b. an artificial atomic superstructure which is likely to result in a modified electronic structure. perlattices of the staggered type I1 shown in Figure 3. Parts (d).misaligned I P 5 c b Q. solely the gap becomes indirect in coordinate space in this case.5 A).62e. 2 2 Figure 3. Further discussion is given in the main text.Semiconductor microstructures 40 1 a) Type II-staggered d) Type I . For misaligned type I1 superlattices shown in part f of Figure 3.62. (e) and (f) of the figure show the correponding superlattices giving rise to minibands on top of the bulk band structure. In the misaligned case of type I1 (c) an energy region occurs where electrons and holes may coexist. .

The number of non-microstructured dimensions determines the number of spatial degrees of freedom of electrons and holes . High Electron Mobility Transistors ( H E M T s ) and Quantum Well (QW) laser diodes are tangible examples of this that already exist. Electronic structure of semiconductor crystals with perturbations The term artificial semiconductor microstructures or just semiconductor m i crostructures is therefore used in this context. these properties may be tuned to a certain extent by varying the layer thicknesses and chemical compositions of the materials. One refers to this as self-organized growth (Leonard. Moreover. and Weiman (1994). systems with a 2. one can use a diagram which plots the energy gaps of the various semiconductors against . The more appealing nutural growth of quantum wires and dots forms an area of active research at present.and optoelectronics. Hohenstein. we will present a short overview of the various kinds of planar semiconductor microstructures. and Petroff (1993). The term nanostructures is also common. Notzel. Reaves. the spatial variation of material composition is replaced by the spatial variation of doping. Before we examine the electronic structure of these systems in more detail. The possibility of tailoring their properties makes semiconductor microstructures extremely interesting subjects for micro. and 0-dimensionaL Quasi 1-dimensional systems are also referred to as quantum wires. Today. In these. Ledentsov.402 Chapter 3. which are by far the most important ones. Christen and Bimberg (1990). 1-. Butov. Compositional microstructures As a guide to finding material combinations from which compositional microstructures with modified electronic structure may be formed. H a p . In this book we concentrate on planar microstructures. Stutzmann (1995)). doping microstructures will also be covered. and Ploog (1991). investigations of artificial microstructures are the most active area of semiconductor physics. We start with microstructures composed of different materials. or with functions not accessible at all to elements made of bulk materials. Besides heterostructure systems discussed exclusively hitherto.or 3-dimensional microstructure are also investigated. and quasi 0-dimensional as quant u m dots. Such systems may be fabricated by means of an additional lateral structuring of epitaxially grown thin layers. Abstreiter.these systems are termed quasi %. Besides epitaxially grown planar heterostructures and superlattices having a 1-dimensional artificial microstructure (in the growth direction). The concept of semiconductor microstructures was first introduced by Esaki and Tsu (1970). Zrenner. Denbaars. The modified electronic structure of semiconductor microstructures r e sults in transport and optical properties which differ from those of the constituent bulk materials. Bom. Krishnamurthy. Devices may be created with performance data superior to those of conventional electronic components. Daweritz.

0 5.0 h ' ZnS ' I \ I I I I I I I MnSe _ .7. then at least one of the two band edges must also exhibit a discontinuity. Lines connecting two different materials indicate the gap energies of alloys made of these materials. occur. Lattice mismatch As the materials shown in Figure 3.63 are all of zincblende type.5 2. and dashed lines represent alloys with indirect gaps.4 6. 6. then band edge discontinuities may. but need not. the gap difference AE. If the gap discontinuity AE. both the valence and conduction band discontinuities AE. vanishes. provides some hints about their band edge discontinuities.5 3.- v 2 g 0 2. differ from zero and their magnitudes reflect the gap discontinuity to a certain extent.63 for elemental and compound semiconductors of diamond and zincblende structure. The composition of an alloy is related to its lattice constant by means of Vegard's rule which linearly interpolates between the lattice constants of the two alloy components. Full lines represent alloys with direct gaps. and AE.5 1. For two direct gap materials 1 and 2. their lattice constants.0 62 . their main .0 2 0. Semiconductor microstructures 403 3.6 Lattice constant ( LI Figure 3.6 5.8 6. In general.63: Energy gap versus lattice constant for diamond and zincblende type semiconductors.3.0 P w >r 1.4 5.5 0. If a gap discontinuity does exist. Such a diagram is shown in Figure 3.

The corresponding strain energy increases the total energy of the layer. a:! of the two materials are different. in epitaxial growth.. Because m t z ( i ) = 0. Suppose that a layer of a cubic material 2 is growing on a (100) surface of a layer of cubic material 1. Such layers may be the substrate and the epitaxial layer. (3. it follows from (3. but also a buffer layer on top of the substrate which is used to accommodate part of the lattice mismatch strain. it can be completely neglected.(i) ) and ayy(i)with aee(i) = ayy(i). The strain will then be released by the formation of dislocation lines (see section 3..2). The non-vanishing components of the stress tensors ~ ( i of the two layers i = 1 . in particular of dislocations. the accommodation of the lattice mismatch by strain becomes energetically more costly than the formation of lattice defects. Otherwise one has lattice mismatched heterostructures. only a few dislocations occur and the layer will have good structural perfection despite the strain. For a lattice misfit f of a few percent the critical thickness may reach values not much smaller than 100 A. and that the cubic lattice constants a l . As long as one stays below d. If they differ. One speaks of strained layers. The critical thickness depends on the magnitude of the lattice mismatch. The relative deviation f = (a:! . One says that the layer grows in a pseudomorphic phase.a l ) / a l of these constants is termed lattice misfit and measured in percent. but with a lattice constant parallel to the layers equal to that of the substrate. the layer material will not grow with exactly the same lattice parameters as would a free standing bulk crystal of this material. The adjustment of the parallel lattice constant creates a mechanical strain in the layer. 2 are a. If f is less than a few tenths of a percent. and this increase grows larger as the layer becomes thicker. the lattice mismatch has only little effect and. in many cases. We suppose again a layer of cubic material 2 which is growing on a (100) surface of a layer of cubic material 1. In order to grow lattice mismatched heterostructures it is important to know the distribution of strain between layers of different thicknesses. Past a critical thickness d. and the non-vanishing strain components are e x s ( i ) . eyY(i) and e z z ( i ) with e r X ( i ) = eyY(i). The independent stressstrain relations for a particular layer read “ 2 4 4 = cll(i)€zz(i) + c12(i)[err(i) + €yy(i)].240) with cll(i) and clz(i) being the elastic stiffness constants of the cubic layer of material i. the lattice constant a1 of the substrate (material 1)should be equal to the lattice constant a2 of the layer (material 2). Electronic structure of semiconductor crystals with perturbations structural differences lie in their different cubic lattice constants a.240) that . One speaks of lattice matched heterostructures.404 Chapter 3. Ideally.

242) The total strain E defined in equation (3. Semiconductor microstructures 405 (3.. that the substrate will be almost unstrained and the epitaxial layer will accommodate almost the whole misfit strain. The degenerate heavy-light hole valence band maximum of Si splits by 0. In this context. we consider a Si layer on top of a Ge substrate. Pikus. energy levels in different materials or at different points of the first B Z can shift in dserent ways. This was anticipated in the discussion above.E v y ( l ) = t. in particular. Another general point to be mentioned in the context of lattice mismatched heterostructures concerns the effect of strain on the band structure.244) Minimizing Eela with respect to txZ(2)(or ~ ~ ~ yields)the conditions ( 1 ) (3.Ki)Cl2(i)l. and e Z z = -0. . This means. (3. the total elastic energy Eda of the two layers may be calculated.242) equals the lattice misfit f divided by 100%.243) where c = i [Cll(i) + (1 .1 x 1011 dyn/crn2 and c12 = 6.04.&(1) = tyy(2). To produce the same splitting by means of uniaxial strain applied from outside. provided the elastic constants of the two layer materials are comparable. The strain becomes. To give an example. the thin layer is more heavily strained than the thick one.241) For the parallel strain components e z Z ( i ) and e y 3 / ( i ) one has 4 2 ) . 1974).31 el/ under this strain. From theoretical considerations and experimental studies it is well known that such effects can be quite large (Bir. ai (3. with the result (3.3. using the elastic stiffness constants c11 = 16. a pressure of 73 Kbar would be necessary. This example shows that considerable changes of the band structure are to be expected because of the lattice mismatch strain in heterostructures. The strain components in the Si layer are e X x = cyy = 0. so to speak. an additional degree of freedom for tailoring the properties of a heterostructure. corresponding to a lattice misfit of 4% (see below).ai . One may take advantage of this to adjust the band discontinuities of a heterostructure to specified conditions.4 x 1011 dynlcm’ of Si.03.7. Using the stress and strain components.245) According to these relations. t = a2 .

The critical thickness d.5) as epitaxial layers.65 A. one has staggered type I1 heterostructures. one has a misaligned type I1 heterostructure. amounts to about 30 A which is rather small. The conduction band edge of InAs is 0. Ge) alloys may also be used as substrates.082.Al. = 0. Superlattices based on InAsfGaSb heterostructures have been the subject of intensive basic research.Al. Consider.As) The Inl-. alloy layer is grown first.Al. Therefore. For Inl-.Al)As GaAs/Gal-. which has already been used above. In this case d.43 A and 5. The two band edges are lower in Inl-. a Sil-. can be 100 A or larger depending on the actual value of x. This gives the lattice mismatch of 4 %. GaAs/Gal-.14eV below the valence band edge of GaSb. including the trivial GaAs/GaAs homostructure. heterojunction bipolar transistors (HBPT). we add some quantitative estimates. Electronic structure of semiconductor crystals with perturbations Particular compositional microstructures GaAs/(Ga. these SLs exhibit metallic behavior. This gives A E . (Si.Al. and the conduction band discontinuity has the constant ratio Q.As/GaSbl-yAsy material system forms heterostructures of type 1 .As multiple heterostructures are the prototypes for lattice matched type I microstructures. Both layers are strained in this case. and QW laser diodes. (In. Beside providing model systems for basic research. respectively.406 Chapter 3.Ge. the strain in the alloy layer .Ga)As/Ga( Sb.As than in GaSbl-. For the gap discontinuity A E . + Si and (Si. 5.As microstructures are used in devices like HEMTs.As/GaSbl-yAsY heterostructures with larger x and y. Here.Ge) The lattice constants of Si and Ge are. The valence and conduction band edges of the Gal-. Perfect lattice matching is achieved if y = 0 . one also considers heterostructures between Si as substrate and Sil-. For 0 < y < x.As linearly with x according to the relation AE. for example.25 x x e V . the valence band discontinuity takes the constant ratio Q v = (45/125)% = 36% of the gap discontinuity.57.45 x x eV. 9 1 8 ~ 0.Ga. For small values of x and y.Ge. we have A E . as long as we consider the direct region x < 0.Gey substrate on which a Sil-.42. = 0. alloys with low Ge content (x < 0.Ga. With this. especially for InAs/GaSb with x = y = 0. The valence band heterojunction scales almost discontinuity A E v of the GaAs/Gal-. = 1.Ga.As alloys have already been discussed in the context of Figure 3.85 x x eV for the conduction band discontinuity.Asy 1 for all compositions x and y. Under certain conditions. for which the conduction band edges are above the valence band edges in both materials. followed by a pure Si layer. = 64%.

and that in the Si layer tensile. with both the highest valence band edge and the lowest conduction band edge in the alloy. but the conduction band edge of Si is shifted down below the conduction band edge of the alloy by the tensile strain in the Si layer. Blue-green laser diodes have been fabricated from such structures. the lattice constant of the alloy may be estimated as 6. Cd) (Se.Cd. Thus the Si/Si0.53Gao. one obtains a strained heterostructure of type I.Ge.35 eV for InP and 0. Semiconductor microstructures 407 is compressive. laser diodes and photodetectors may be fabricated for optical fiber communication at 1. covering light emission wavelengths down to the technologically important near infrared region.75Geo.S) /GaAs ZnSe and GaAs form an almost unstrained type I heterostructure. If a Znl-. embedded between other 11-VI-compound layers.75Ge0. + + + (Zn. alloy of a certain composition z . S. more strictly.y’. deposited on top of a GaAs substrate.Ge.53Gao.tCd+! SY!Sel-. y is combined with a Znl-. because here the free electrons are hosted by the pure Si layer.0. the lattice matched alloy transforms from pure InP to an Inl-. GaAs and Gap.Cd)Se/Zn (S.As.418 .y). The 1 type I1 Si/Sil-.z)y 5.AsyP1-y may be thought to be formed of the four binary compounds I d s .013~) y between 0 and 1.5heterostructure on top of a Si substrate. Because of the different strain distributions.47As/InP microstructures may be used to fabricate HEMTs. .5Ge0. The latter is of type I.53Gao.P)/InP Quaternary alloys of composition Inl--rGa. from Zn(S.55 p m wavelength.85 eV for Ino. Using Ino.3. the band alignment of a Si/Sio.5Ge0.5 heterostructure on top of a Sio.~ alloy of another composition x’. the whole mismatch strain occurs in the alloy layer while the Si layer remains unstrained. alloy varies almost linearly between 1. (1-z)(l-y).P1-. with composition ratios given.Ga. If the same Si/Sil-.869(1. The fundamental energy gap of the lattice matched Inl-.Se)/(Zn. The former still has its highest valence band edge in the alloy.451~(1.189y/(0.Sel-. (Ga. where the mobility is much higher than in the alloy layer. Lattice matched Ino.47As.25 substrate is of type 1 .5 heterostructure on Si0. Se) double heterostructures. respectively. double layer is grown on Si substrate. Generalizing Vegards rule.zy. and z(1-9).z)(1.Ga.~Ge0. It matches holds. therefore. heterostructures are better suited for applications in electronic devices (in particular HEMTs).058(1.As alloy with I = 0. Varying with that of InP if the relation z = 0. InP.25 substrate differs from the band alignment of the same Si/Si0.7. by (1-z)y.47. 6 5 3 ~ ~ 5.47As/InP based microstructures. which is the wavelength with minimum losses in quartz-based fibers.y) 5 .In)(As.

Depending on strain. however.Te/PbTe heterostructures are of type I for z < 20. The valence band offset turns out to be rather small ( M 0.4. (Pb. the gap of Pbl-.and p-layers. Thus.02 e v ) . for sufficiently small 2 . Pbl-. can be applied in infrared detectors. one has zo M 0. Tsu.Sn. For PbTe. HgTe forms a type I11 heterostructure with CdTe.Te/PbTe have a potential for applications in infrared laser diodes.of type I11 for z = zo.Te alloys the gap opens at 2 = 0. Being a zero gap material. If the modulation period approaches the nanometer range. this level ordering is inverted.Te alloys are direct gap materials with the conduction and valence band edges on the first B Z boundary at L.408 Chapter 3.and p-type doped layers may exhibit properties similar to those of superlattices composed of two different materials (Esaki.Cd. minibands arise just as in the compositional superlattices considered above.64a. and again of type I for 2 > 2 0 . at a given position. Hgl-. generally.15 < 2 < 1 the alloys ' are direct gap materials with the valence and conduction band edges at. The most common nipi-structures are those based on GaAs.Cd.Te/CdTe forms type I heterostructures which. Pbl-. Doping superlattices are principally of type I1 because the two band edges. Doping microstructures nipi-structures Semiconductor samples with alternating n. Microstructures based on Pbl-. the L$ state forms the valence band edge. For 0.Sn. Sn. with inverted band edges of the well material in this case. 1972).Te alloys must go through zero for some composition TO.structures.4 %. type I1 situations also seem to be possible. In this context they are sometimes referred to as nipi . At 77 K . are shifted by the same amount of energy. Sn.35). Their periods. Electronic structure of semiconductor crystab with perturbations (Hg.Sn. cannot be made smaller than 10 nm because of the unavoidable diffusion of dopant atoms. The oscillating space charge distribution gives rise to an oscillating electrostatic potential which modulates the valence and conduction band edges as shown in Figure 3. 1970. Thus.15.Cd)Te/CdTe HgTe and CdTe are lattice matched because the lattice misfit is smaller than 0. Dohler.and np-junctions with alternating negatively and positively charged intrinsic (i) regions between the neutral n. and the Lg-state forms the conduction band edge (see Figure 2. Such doping superlattices may be thought of as periodic arrays of pn. For SnTe. .Sn)Te/PbTe The lattice misfit between PbTe and SnTe is about 2 %. so that strain effects in Pbl-. namely the electrostatic energy of an electron.I In this range. In Hgl-.Te/PbTe heterostructures are not negligible.

6-doping structures are always of type 11. In GaAs.g. 1994). The primitive unit cell of . and the AlAs layer contains a number 2m of (001) lattice planes alternatively occupied by Al. Bulk methods We consider SLs composed of two zincblende type materials as. spikes of dopant atoms of only a few nanometer width may be constructed in an otherwise undoped sample. 3.7.3 Methods for electronic structure calculations The theoretical methods which were developed to calculate the electronic structure of bulk crystals in Chapter 2 and of clean surfaces in Chapter 3 are also suitable for artificial semiconductor microstructures. One speaks of planar doping or 6-doping (see.3.64b). e. The interface is taken to be parallel to a (001) lattice plane.. e. The sheet of ionized dopant atoms forms an electrostatic potential well which binds the emitted free (majority) carriers. The energies of these carriers become quantized just as in the case of a quantum well. Below. electrons in the case of n-type &doping (see Figure 3. n-type &doping has been achieved. Semiconductor microstructures 409 a) m + + + + I b) + + + + + + + + + + + + + + -1 z - - I I v Z Figure 3. for example.and As atoms./(AlAs). is used for such a SL.. Like nipi-structures. GaAs and AlAs. and p-type 6-doping by means of Be.e. i. The notation (GaAs). by means of Si. &doping structures By means of MBE.g.7. and holes in the case of p-type &doping. The potential well experienced by the majority carriers represents a barrier for the minority carriers.64: Valence and conduction band lineup for doping microstructures in a direct gap material for a) a nipi-structure and b) a n-type &doping structure. we will discuss this in the case of compositional superlattices (SLs). A GaAs layer of the SL contains a number 2n of (001) lattice planes alternatively occupied by Ga and As atoms. Schubert.

referred to as minibands in regard to k-dispersion parallel t o the SL axis.ey). SL The stationary states of the SL are Bloch states with quasi-wavevectors k of the first SL B Z . the only difference being the larger size of the primitive unit cell. respectively. Electronic structure of semiconductor crystah with perturbations [IIO] 0 Ga OAs 8At Figure 3. the SL is spanned by the primitive lattice vectors of a (001) lattice plane.65: Primitive unit cell of a (GaAs)3/(AlAs)3SL. The energy eigenvalues form bands in this B Z . 4n B~ = (n The volume of the first B Z of the SL is a ( n m)-th fraction of that of the first bulk B Z .3As)3 is plotted along the r . The minigaps become wider for stronger perturbations of the bulk crystals due to the superlattice structure. The minibands arise from bulk bands folded back upon the first SL B Z . one bulk band gives rise to ( n m) SL minibands.67 shows the results of such a calculation performed by means of the TB method. = (u/2)(eZ . namely. i.e.246) + + . the wider the minigaps open. and the shorter the SL period is (as long as it does not become too short).410 Chapter 3. As the bulk B Z encompasses ( n m ) first SL B Z s . A1 = (a /2 )(e z ey). A3 may be taken as A = (a/2)(n+m)ez. All methods for determining band structure of bulk crystals can also be used to calculate the band structure of SLs. A2 Provided that (n+m) is an integer. the primitive unit cell and the first B Z of a (GaAs)g/(AlAs)~ as an example. The minibands are separated by m i n i g a p s which occur at the Bragg reflection planes of the reciprocal SL lattice perpendicular to the z-axis. In Figures 3. (3. Figure 3.and another vector A3.ey). 3 The pertinent primitive vectors of the reciprocal lattice are then given by + 2r 7 B1 2r 7 . The valence band dispersion of a (GaAs)a/(Ga0. and as subbunds if k-dispersion parallel to the SL layers is considered.Z symmetry SL + +m)a ez.65 and 3.~A10. B2 = -(ez a = -(ez a + ey). the larger the difference of the periodic potentials of the two bulk crystals.66we show.

in many cases the application of bulk methods to artificial microstructures is not appropriate.X line of the first bulk B Z . Bulk methods may also be used to calculate the electronic structure of non-periodic microstructures such as GaAs/AlAs single heterostructures or (Ga. In this way an SL is simulated whose electronic structure can be calculated by means of any of the bulk band structure calculation methods.68 for a (GaAs)7/(AlAs)T SL. Al)As/GaAs/(Ga.65. also along the r . A1)As layers. This illustrates the general discussion of subsection 3. Al)As/GaAs/(Ga. line of the first SL B Z and. Semiconductor microstructures 41 1 1". while in most cases only a small number of minibands are of interest because only these undergo changes in comparison with the back-folded bulk bands. even the .7. Important properties of the corresponding SL eigenfunctions are illustrated in Figure 3. In the case of the (Ga. A1)As double heterostructures.7. to demonstrate the folding character of the SL band structure. both AlAs-X-states and GaAs-r-states contribute to the conduction band states of the SL. The lowest valence and conduction band states are represented with respect to their spatial variations and symmetry characters. In these cases one may use a procedure similar to the slab method for surfaces: At the outset.66: First B Z of the (GaAs)3/(AlAs)3 SL of Figure 3. one embeds the GaAs layer between thick but finite (Ga. Moreover. While the valence band states are well localized in the GaAs layers and are dominantly composed of GaAs-r-states.1 about the existence of eigenstates of heterojunctions which arise from bulk states with different k-vectors in the two materials . These methods yield the totality of energy bands of a microstructure in all parts of the first B Z . A1)As double heterostructure. Figure 3. one defines a slab with a sufficiently thick but finite GaAs layer and forms a single heterostructure with a sufficiently thick but finite AlAs layer.3. and repeats the slab thusly formed periodically. and then repeats this slab periodically. However.

and plotted upon the r . Bechstedt.412 Chapter 3. exists in the shallow level case.if one would try to obtain these levels by means of a full bulk band structure calculation method the same difficulties would occur. where the kinetic energy is small enough to allow the perturbation potential to produce measurable effects.) changes of these few minibands are small. and Enderlein.7Alo. The situation is similar to the case of the shallow levels of impurity atoms . The bulk methods are often not accurate enough to reproduce them sufficiently well.67 Valence band structure of a (GaAs)3/(Gao. 1986. Hanke. It is particularly well tailored to calculate the small changes of electronic structure occurring at the conduction band minimum and the valence band maximum. Electronic structure of semiconductor crystals with perturbations - 3 . (After Riicker.-1 to -2 !i o l A W -3 -4 -F.2 symmetry line of the first SL B Z (left) and the I?-X line of the first bulk B Z (right). -€ Figure 3. namely the effective mass theory.3As)3SL calculated by means of the TB method. The situation in the case of artificial microstructures is comparable: the perturbation potential is relatively weak. and changes of the band structure are expected only for selected bands and in the vicinity . Fortunately. another method.

e. el = 1. We will address this question below (for a detailed discussion see. e3 = 1.g.77 eV. the difference of the periodic oneelectron potentials of the two m a t e rials of a heterostructure. There are.(After Rucker. h l = -0. The perturbation potential.11 eV.) of critical points.3 can in fact be applied to artificial microstructures. Burt. Semiconductor microstructures 413 GaAs A1As r X Figure 3. is far from being smooth on the atomic length scale.e. and are composed of both AlAsX-states and GaAs-I'-states. for a (GaAs)7/(A1As)7 While the valence band states are SL.19 e V .. also differences between the shallow level problem and the microstructure problem. conduction band states extend over both layers.7. the average potential difference has still an abrupt change at an interface.3.68: Localization of the lowest valence and conduction band states of the SL at the center r of the first SL B Z (left). however. . and the symmetry character of these states (right). i.h2 = -0. For this reason one has to determine at the outset whether or not the effective mass theory developed in section 3. 1992).e2 = 1. Even if one averages out the microscopic potential fluctuations over a unit cell.75 eV. 1985.88 eV. well localized in the GaAs layers and are dominantly composed of GaAs-r-states.

(3. Furthermore.may be written as The two envelope functions F. ~ ( x ) . There is no doubt that the effective mass theory may be applied to each of the two infinite half spaces of this structure filled with material 1 for z < 0 and with material 2 for z > 0. Accordingly.2 at f. Then these eigenstates are composed of only bulk states with k-vectors in the vicinity of r. F . the eigenfunctions & l ( x ) and $ 4of the) ~ two material regions 1 and 2 having energies. If the eigenstates were composed of bulk states from different parts of the B Z .l(x) = E.F. then the effective mass theory is applicable as well. however. If. all bulk band energy levels are far removed from the energies of the eigenstates under consideration. at critical points off r. close to the band edges Evl and E. just as is assumed in effective mass theory (in fact this theory assumes composition of bulk states from the ) vicinity of a particular critical point which need not necessarily be f . these equations may be written as one equation for the envelope function . Both edges should occur at the centers I? of the respective bulk B Z s .l(x) and Fv2(x) obey the effective mass equations F. which we will assume.249) Formally. respectively. x in m a t e r i a l 1.68. Electronic structure of semiconductor crystab with perturbations Effective mass theory for microstructures Consider a single heterostructure. x in m a t e r i a l 2. Non-degenerate band edges In the case under consideration.i(x). = (3. an eigenstate of the heterostructure may be formed only from bulk states at an off-center critical point like X .248) F V ~ ( X ) E . provided the conditions of validity of effective mass theory are satisfied in each of the two regions separately.2 of the two bulk materials. say from f and X as happens in the case of the conduction band states of the (GaAs)7/(AlAs)i. then the effective mass theory could not be applied. we suppose that.1 and E.414 Chapter 3. SL shown in Figure 3. The two band edges at are assumed to be non-degenerate and isotropic (the degenerate case will be treated separately). we restrict ourselves to eigenstates of the heterojunction having energies in the vicinity of the band edges E.

250) of the whole heterostructure by introducing a z-dependent effective mass m * ( z ) and a z-dependent band edge E.254) is the Bloch factor of the heterostructure.x be continuous everywhere. 0 Y. At z = 0. To this end we consider the interface behavior of the Bloch factor ud(x) in equation (3. which we will now discuss. Thus it determines the possible envelope function solutions for z < 0 and z > 0. we derive a condition for the change of the envelope function across the interface. To do so. Firstly.252) holds only within the two material half spaces.x (3.(x). Thus the condition Fv(z. the solutions for the two half spaces must be connected in an appropriate way to form an envelope eigenfunction for the entire heterostructure. If this factor was continuous at the interface.255) should hold in the limit 6 --+ 0.(z) defined.3.253) for the total wavefunction &. equation (3. respectively. Unfortunately. Clearly. 0 . the envelope function F. The only case in which such a continuity is assured is that of a 'heterostructure' composed of two identical materials.6 ) = F ( . Semiconductor microstructures 415 (3. Y.252) The true wavefunction $ ( ) of the heterostructure is given by the expression . .z +6) (3. matching conditions are required.(x) also would have to be continuous there since the total wavefunction @() must .7. but not at the interface. it is commonly . by We write this one equation as (3. Having this obvious result in mind. no general proof exists for the continuity of the Bloch factor at a heterostructure interface.253) (3.

there have been various attempts in the literature to justify the continuity condition (3. Thus. Without demanding satisfaction of this condition. does not seems to be necessary for the applicability of effective mass theory to heterostructures. Secondly. For an infinite bulk crystal. there exists a variety of solutions of equation (2. it is essential to realize that the Bloch factor ul/o(x) in equation (3. The other contribution arises from the gradient of the envelope function. Electronic structure of semiconductor crystals with perturbations argued that the Bloch factor should be continuous at an interface. In fact.252) occurs in an eigenfunction of the entire heterostructure rather than in an eigenfunction of the two infinite bulk crystals. that effective mass calculations based on envelope function continuity. In a heterostructure. we arrive at the conclusion that the first derivative of the wavefunction must obey the relation . and since the envelope function itself has this property because of relation (3. One is due to the gradient of the Bloch factor and it vanishes after averaging. however. in the case of GaAs/Gal-. function Fv(x)alone rather than to the total wavefunction & ( ) Since the average current density must be continuous at the interface. the two Bloch factors at the interface need not be periodic with respect to z because the lattice periodicity in the z-direction is perturbed. as is tacitly assumed in the above discussion. the Bloch factor is that particular solution of equation (2. This must also hold after averaging with respect to a primitive unit cell.e. This means that the average current density in state $v(x) is obtained by applying the quantum mechanical expression to the envelope .x. This freedom may be used to satisfy the continuity condition for the Bloch factor at the interface. if the two materials of the heterostructure are not too different from each other with respect to their energy band structures.416 Chapter 3. To this end we use the physically obvious fact that the probability current density joined with the total wavefunction $ J ~ ( X ) must be the same on the left and right of the interface. we derive a condition for matching the interface values of the first derivative of the envelope function with respect to t. It is multiplied by the squared modulus of the Bloch factor. In our opinion. for example. at least in an approximate sense. It turns out.136) which obeys the lattice periodicity condition.Al. which yields 1 after averaging because of normalization.255) without using the band structure similarity argument. i. Applying the well-known quantum mechanical expression for the current density one obtains two contributions. similarity of band structures.As heterostructures with sufficiently low z-values.255). also yield correct results for heterostructures made of materials with considerably different band structures. with respect to a region where the envelope function is almost constant. This happens. while being sufficient.136).

(3. by the hermiticity demand alone since there are also other ways to introduce hermiticity. as the average inverse effective mass (m. h2 (3. as any reasonable kinetic energy operator must be in order to avoid complex energy eigenvalues.261) with l/E.256). Its replacement by the right hand side of relation (3. In the effective mass equation (3.256) involves more than just the hermiticity of the kinetic energy operator.3. and since the effective mass does so also.256) cannot be justified.p.Vm*~(z)+m*~(z)Vm*~(z).258) the band edge plays the role of an external potential. y are real numbers obeying the relation (Y . Semiconductor microstructures 417 which is known as the BenDaniel-Duke boundary condition.B y = -1. therefore as + + (3. This implies that the boundary condition (3. however.- 2 m*(z) v.259) For F u ( z ) the Schrodinger equation follows as where EL is given by EL = E .252) is also applied at z = 0 after the kinetic energy term has been replaced in accordance with _- h2 2m*(z) v 2 -+ . one can easily demonstrate that any operator of the form -(F.252) becomes Integrating this equation with respect to z from -6 to +6 one obtains the boundary condition (3.2/4)[m*a(z)Vm*~(z).T1)/2.25 7) With this replacement the effective mass equation (3.7. This condit. The original form -[l/2m*(z)]V2 of the kinetic energy operator is not Hermitian.257) is Hermitian. - . h2 --v.Vm*a(z)] is Hermitian if a. In fact. . the dependence of the envelope function on the component XI[ of x parallel to the layers may be taken in the form of a plane wave of parallel wavevector kll.:' + m. and must be rejected. Since it depends only on z .i k 2m*.ion follows automatically if the Schrodinger equation (3. The kinetic energy operator of the Schrodinger equation (3.

Integrating the effective mass equation for this generalized Hamiltonian with respect to z over a small interval across the interface leads to the conclusion that the expressions ($ must be continuous at the interface z = 0. The boundary conditions for F v ( x ) at the interface follow in the same way as in the non-degenerate case.264) must be continuous at z = 0. To determine the condition for the derivative with respect to z . the effective mass equation (3. F U (z)lz=-6 = F u =+ * * (z)I~=+6 (3.73).263) may again be taken as a plane wave (3.418 Chapter 3.2.263) with DE$(z) = DYZAl for z < 0.ELl for z > 0. one defines the Hermitian Hamiltonian matrix (3.264) parallel to the layers.# 0.e.266) which exists for any value of z including z = 0 and equals H 1 for z < 0 and e H z for z > 0.74).263) becomes . i. are of the general form (3. Electronic structure of semiconductor crystals with perturbations Degenerate band edges In the case of degenerate band edges E v ( z ) . The solution of equation (3.265) must hold for 6 + 0. and the components Fym(X) of the envelope func* tions F~ ( x )obey the effective mass equations @ [-~g$r(z)aaaat + ~ v ( z ) 6 m m iFumt(x) = ~ v ~ v r n ( x z .. these general results are specified for the fourfold degenerate rs valence band edge of diamond and zincblende type materials. and Dg$l(z) = D.262) derived in equation (3. Using the 4 x 4 Luttinger-Kohn Hamiltonian of equation (3.the Hamiltonian’s H i of the two materials i = 1. The z-dependent * * factor F~ (2) of F. Below. ( x )in equation (3. ] ) m’ a d (3.

N in equations (3.72. Semiconductor microstructures 419 (3.3. ? ( z ) here are the differential operators k(z)= --a . L .272) The constants M .268) The quantities Q ( z ) .k i ) .2i73(z)k.kg] .381).75) to (3.g ( z ) .y3 using equations (2. From equation (3.f i ( z ) .78) have been replaced by the Luttinger parameters y1.7. [y2(zj(k: (3.267) one finds that the following combinations of the components F m ( z ) and their derivatives FLm(z) with respect to z must be continuous at the interface z = 0: .

The effective mass equation for the electron envelope function Fc(x) the of .42.Al. denoting their common value by m.420 Chapter 3. To be specific. the conduction bands ’ are non-degenerate and isotropic in the vicinity of I. These states are the ones which would host the free electrons of the SL.7. with d = d l d 2 ( s e e Figure 3.l and m:2 are different.As alloy for z < 0. we may associate ‘1’with GaAs.4 E l e c t r o n i c structure of particular microstructures Compositional superIat tices and q u a n t u m wells We consider a SL composed of two zincblende type semiconductor materials 1 and 2 with the conduction band edges Ecl and Ec2 located at r. Later. We suppose that there are none. if there were any. and the lattice constant in z-direction by d . + Electron states Effective mass equation and its solutions For the zincblende type materials we are considering. as we did before. The two effective electron masses m:l and mE2 generally differ.Al.69: Geometry of the SL whose stationary electron and holes states are calculated in the text.2 using the effective mass theory derived above.As this is a reasonable approximation. Electronic structure of semiconductor crystals with perturbations L XJ Figure 3. 3. but we will initially assume that they are equal. The thicknesses of the two material layers are denoted by d l and d 2 . we discuss the modifications which occur if m.69). We want to calculate the stationary electron states of this SL with energies in the vicinity of the conduction band edges Ecl and E.. In the case of SLs composed of GaAs and Gal_. and ‘2’ with a Gal-.

) in order to guaranty the periodicity of F&) with respect to the periodicity interval.252) if we set v = c and f o r Id Ec(z) = < z < ld+dl Egl +AE. (3. . The z-dependent factor F.260) describing a plane wave of wavevector kll parallel to the layers. Semiconductor microstructures 421 thus specified SL follows from equation (3. -co < 00.(ld dz d dz + 0).(z) = Fck(z) = L e ik r U c k ( z ) .(z) may be written as a lattice-periodically modulated plane wave F. f 2 . f o r Id + d l < z < (1 + l ) d .(ld + d l + 0 ) .(x)obeys the equation where E. . < 1 (3. i f (3.0 ) = F. (x)of equation . It must have the form ( 2 a / L d )x (0. d .274) Here 1 is the integer index of the various SL unit cells. The component k varies within the (1-dimensional) first B Z of the superlattice between .7. The Bloch factor U c k ( z ) of the superlattice has to be distinguished from the Bloch factor uco(x) of the two bulk .276) In solving this equation. Applying the Bloch theorem to the SL under consideration it follows that F.(ld -Fc(ld dz -F.x (3.0) = -F. - (3.277) +d l - have to be satisfied as well as the normalization condition with respect to 2 i the periodicity interval of length C = Ld ( L denotes the number of SL unit cells in a periodicity region of volume 0). and U c k ( z )is the superlattice Bloch factor.r / d and r l d . is given by EA = E . .3. The envelope function F ( ) may be taken in the form Fckl.(z) of Fckl.278) where k is the quasi-wavevector component parallel to z . f l . the boundary conditions Fc(ld d + d l .

We restrict ourselves to energy values 0 < E' < A E .422 Chapter 3. (3. For the wells 0 < z < d l . In the following we sketch its solution. = . Electronic structure of semiconductor crystals with perturbations materials defined in equation (3. (3. (7i2/2mr)ki. it is still much larger than that for material 2.282) where we have set . and bamiers for the layers of material 2. The latter problem constitutes an exercise of elementary quantum mechanics and is commonly used to demonstrate the existence of energy bands. and the Bloch condition (3. one uses the terms quantum wells for the layers of material 1.278) define an energy eigenvalue problem which differs from the well-known Kronig-Penney problem only by notation.281) and a l . If it hits the interface to material 2. as in classical mechanics.1 < E < E.276) yields + + F. but smaller. The total wavefunction &(x) &k(x) contains the product of both. the matching conditions (3. According to classical mechanics. an electron with such an energy cannot penetrate within the superlattice layers made of material 2.]F(z)is given by different expressions. then it will be reflected back to the interior of its material 1 layer. one due to the natural crystal structure. meaning energies below the lowest allowed energy in material 2 for a given value of kll.254). the reflection is not complete.]F(z)= ale iKZ + ble-iKz. In the case of SLs this exercise takes on real physical meaning. 0 < z < dl. It reads (3. For the barrier d l < z < d one has Fck(z)= a2enz + b2e-nz.1 AE.275). and one due to the artificial superstructure. As has already been mentioned. The occurrence of two different Bloch factors reflects the fact that two periodic potentials are present in a superlattice. there is a certain probability for the electron to tunnel through a material 2 layer and reach the next neighboring material 1layer. it will be confined to layers consisting of material 1.277). bl as coefficients which are still to be determined.280) with K as a real number which determines the energy E' by means of the relation I E . In quantum mechanics.h2 K2 2 m ~ ' (3. dl < z < d. Although the probability for an electron to stay in material 1 is not unity. Schrodinger's equation (3. In the wells and barriers the wavefunction F.279) The effective mass equation (3. or E.

. Thus equation (3. As we know from the solution of the latter.286) Unlike the Kronig-Penney problem. are termed minibands and minigaps. It coincides with that of the Kronig-Penney problem. b l . = Ecn(k) of the superlattice. They split into energy bands E&(k). (3. The kll or subband dispersion is due to the natural crystal structure. The effective masses of the minibands become negative at the boundaries of the superlattice B Z in the case of odd band numbers n.285). the sub.277).and &-valuesmust satisfy equation (3. In Figure 3. while the k or miniband dispersion follows from the artificial microstructure.70. but with varying values of k . Commonly. there are discrete energy eigenvalues EL.K~ +sin(Kd)l sinh(~d2) cos(kd).EL). (Ti2/2m*)kll to according to equation (3. these energy bands exhibit an additional dispersion with respect to the wavevector component kll along the SL layers. n = 1. for a given quasi wavenumber k. .2. Semiconductor microstructures 423 KE.283). The values of K and K are not independent of each other.1 E L ( k ) .276). if k varies within the first B Z . with the result + Em(k) = E&(k) h2 + Egi + -kll 2mr (3.285) Allowed K . ..283) The four coefficients a l . = 2Kn: (3. and at the center of the B Z for even n. separated by energy gaps. Ti2 .281) and (3.3. the energy bands and gaps for a fixed value of kll.7. both are determined by the energy E L through equations (3. a2. respectively. one still has to add E. the determinant of the matrix of exponentials must vanish. This yields the secular equation cos(Kd1) cosh(tid2) tc2 . . To obtain the total energy eigenvalues E. central part.= 2 2mE -(AE.285) represents a condition for EL. These equations read For this set to have a non-trivial solution. Bands which arise for fixed IF and varying kll are termed subbands. b2 are governed by a set of linear equations which follows from the 4 matching conditions (3.and minibands of a SL are schematically plotted.

They give rise to the energy eigenvalues 2 El = cn 2mE . Electronic structure of semiconductor crystals with perturbations Figure 3.. the minibands degenerate into discrete energy levels. The solutions of this equation are K-values of the general form K = (7r/dl)nwhere n is an integer. Obviously. and/or the barriers AE. In the lower part of the figure the wavefunctions are illustrated. (3.285) dominate over the cos(kd)-term on the right hand side which is responsible for the k-dispersion. . then the hyperbolic terms in equation (3.285) becomes sinKd1 = 0. 2 . One uses the term multiple quantum well for a superlattice in this limit. If the thickness d2 of the barriers between the wells becomes large. The electron states are almost completely confined within a well. and practically zero within the barriers. n = 1 .70 also shows two enlightening limiting cases.and subbands of a superlattice. Multiple quantum well versus superlattice behavior Figure 3. .70: Mini. the superlattice decomposes into isolated quantum wells in the limiting case under consideration. are high. These levels are just the discrete energy eigenvalues of a single quantum well.424 Chapter 3. .287) . termed sublevels. For infinitely high potential walls the secular equation (3. Neglecting the latter. Also shown are the two limiting cases of extremely wide and/or high barriers and of narrow and/or flat barriers.

or smaller than. They decrease with band number n.7. Semiconductor microstructures 425 and Bloch factors (3.067 m . This means that the ground state of the quantum well is shifted up by this energy amount as compared to the conduction band bottom of the infinite bulk crystal.. gaps are opened at the Bragg reflection points k = ( n n / d ) of the 1-dimensional reciprocal lattice of the SL. the minigaps are proportional to the conduction band discontinuity AE. In zero-th approximation the secular equation (3.70).3. The length scale turns out to be that of the de Broglie wavelength X of an electron. as distinguished by the coupling of quantum wells with one another. and the superstructure which distinguishes the superlattice from a natural crystal has no effect at all. For a conduction band electron of silicon. Assuming d l = 100 A and m = 0. The en- . for large n. We consider next the opposite limiting case. one gets A =" 20 nm. one gets a value of 57 meV for the first energy E level ELl. Similar values are obtained for other semiconductors. there are no substantial energy gaps even if sufficiently wide and high barriers exist. This proves and specifies the expectation stated at the outset of this section. that of extremely narrow and/or flat barriers (see Figure 3. One may say that for minigaps to occur the product of wavevector k = ( x n / d ) and superlattice period d should not be large compared to 1. This shift is a consequence of the localization of an electron within the quantum well which leads to a momentum uncertainty because of Heisenberg's uncertainty principle.4 yields E&+1 ( : ) -E L ( : ) = -AEc 7rn 1 sin ( y d g ) . In this limit the minigaps vanish completely. the superlattice period d should not be large in comparison with the electron wavelength X = 2 r / k corresponding to k. (3. In other words. the perturbation theory developed in section 2.285) takes the form k = K . that substantial changes of electronic structure are to be expected if the superstructure occurs on a sufficiently small length scale. having an energy equal to the average thermal energy $kT at room temperature. The limit of narrow and flat barriers is the true superlattice case. For the energy splitting between the two bands E&+l(n/d) and E & ( n / d ) . In the first non-vanishing approximation with respect to the SL potential. Thus the layer thicknesses of superlattices have to be on the order of. 10 nm in order that superlattice effects on free carriers may become important at room temperature.288) The confinement to the well region is complete in this limit.289) According to this expression. Thus.

being zero below the band bottom E L E g l . the staircase-like DOS transforms into the smooth square-root-like DOS p 3 ~ ( Eof an electron free to ) move in three dimensions. )2. the QW are taken to be infinite.426 Chapter 3. The summation in expression (3. To this end one has to replace the energy band structure E.212) for the density of states (DOS) p ( E ) of a 3D crystal may be immediately applied to a SL.e. One has so called r e s o n a n t tunneling. i. In a superlattice. Since there it encounters the same allowed energy value from which it may tunnel back. Such behavior of the DOS of an electron which is free to move only in two dimensions was already found in section 2. The heights of the steps have the constant value ( m * / n 2 h 2 ) ( n / d )while the step widths depend on n. the miniband dispersion EA(k) has to be known.5. Equation (3. 2 / 2 m E ) ( n ~ / d 1 and the step widths of the staircase scale with ( n / d ~ ) ~ . in contrast to multiple quantum wells where these values are almost zero. and the DOS of equation (3. If the barriers of . the tunneling will be amplified. Electron density of states of SLs and QWs The general expression (2. and non-zero but constant above. may tunnel from its quantum well through the barrier to the neighboring well.71.(k) in formula (2. of (3. For very wide QWs.212) by the expression given in equation (3.286).291) takes the form of the DOS P M Q W ( E ) a MQW structure.291) Each subband n gives rise to a step-like partial DOS.291) for p ~ over all subbands results in a staircase-like DOS as schematically ~ w shown in Figure 3.291) yields + (3. as in a Fabry-Perot resonator in the case of light. Then the DOS p s ~ ( Eof the SL is obtained as ) To evaluate this expression further.292) . then the energy levels EAn are given by ( h . an electron having a particular allowed energy. Electronic structure of semiconductor crystals with perturbations ergy eigenfunctions also have non-vanishing values within the barriers. In the particular case of isolated QWs the dispersion vanishes completely. in the limit d l -+ 00. It causes the discrete energy levels of isolated quantum wells to broaden into bands.

260). ~ This results in an additional contribution (h2/2)[mZ-'(z) . as may be seen from equation (3. have to be replaced by (m&'mal)K. / d z ) .. the following modifications will occur. For the secular equation (3. First. Another simplification made in the above treatment of the electron states of a SL.. and mE2 instead with mE. Finally. was the assumption that no electrons are available to occupy the SL . If this is not E the case. the kll-dispersion of the total energy eigenvalue in relation (3. respectively.285) this means that all K ' s except those which are factors in arguments of trigonometric functions.E ~ .71 are always below or at the limiting fractional 3D DOS f p j ~ ( E ) .283) between K and E i and.286) becomes different in the two material layers.71: Electron density of states PQW of a QW as function of energy. different mass factors will appear on the two sides of the interface and they will not cancel.' ] k to the SL potential. The additional term introduces a kll-dependence of the envelope function F& which otherwise depends only on the z-component k .277) for the derivative ( d F .3. The staircases of the DOS in Figure 3.(dl/d) being the geometrical fraction of material 1 regions in the infinite MQW. the effective masses mzl and m 2 were assumed to be the same in the two materials.The case when they are at the DOS occurs for energies E at the subband bottoms. in the boundary conditions (3. Semiconductor microstructures 427 4 7 3 3 0 1 Q 0 2 3 1 Figure 3. with f = limd.281) and (3. n and E' must be written with m. Refinements In the above treatment of the electron states of a SL. Second. the relations (3.7. in solving the secular equation.

(z): 0 E. The expressions derived for these potentials in Chapter 2 also apply here if the stationary states of the bulk crystal are replaced by the stationary states of the SL. this potential change may be decomposed into a Hartree and an exchange-correlation part.72 we show self-consistently calculated potential profiles and energy levels for a Alo. For a given number of electrons in SL states.5 x10’2cm-2 15 x10’2cm-2 . As the latter states are only known after the effective mass equation has been solved.7As QW of 100 A width. the potential seen by an electron will change due to its interaction with other electrons in the SL bands.rAs QW of 100 A width containing different numbers of electrons per cm-2. In Figure 3. The effective mass equation for the hole states of such a QW with energies close to the well bottom follows from equation (3. the inclusion of the Hartree and exchange-correlation potentials must be performed in a self-consistent way. As in the case of bulk semiconductors.72: Self-consistently calculated potential profiles and energy levels for a Alo. well bottom bends up with rising n s .~ . containing The different numbers ng of electrons per ~ r n .268) by installing there the valence band edge profle E. (3. If there are such electrons present. > d.aGao. The net effect of the two potential parts is repulsive. this flattening will be enhanced by greater localization of the electrons in the well regions. Hole states We consider a QW structure composed of zincblende type well and barrier materials which are both described within the Luttinger-Kohn model. thus the SL potential well will flatten.293) .3Gao. 6 xlO’*cm-* Figure 3..(z) = forO<z<d f o r z < 0 and z AE. It will be particularly pronounced for isolated QWs. Electronic structure of semiconductor crystals with perturbations t 0.428 Chapter 3. bands. and the energy levels are shifted to higher energies.

The alternating heavy.(kll). If the subbands of the QW are partially filled by holes. One can. Perpendicular starts stronger than that of to z .3Ga0. Subband structures calculated in this way are shown in Figure 3.273) is guaranteed for a given value of kll.73 for a A10. ( A f t e r Altarelli.73: Hole subbands of a 100 A wide Alo.7As QW of 100 A width. the bands repel each other leading to the anticrossing behavior seen in Figure 3.TAs QW.374). 0 < z < d and z < +m. will only be possible for certain discrete energy values E.sGao. Semiconductor microstructures 429 Figure 3. These are the subband energy eigenvalues which are sought. the curvature of the hhl subband at the Ihl subband. The lowest subband ( h h l ) in the vicinity of kll = 0 arises mainly from hole states of GaAs with the heavy hole mass parallel to z .and light-hole-like curvatures parallel and perpendicular to z are consequences of the Luttinger-Kohn Hamiltonian (2. numerically calculate normalized solutions for various values of E and kll. and Fasolino. if this were allowed.73.3. Matching these solutions in such a way that the continuity of the expressions (3.) In this way. Ekenberg. 1985. a set of second order differential equations for the four hole envelope function components arises. Thus the two bands would cross.. then hole-hole inter- . Solutions of this kind can be found in different ways. and the second level ( I h l ) mainly from hole states with the light hole mass parallel to z. The solutions must be normalized and must guarantee for the continuity of the expressions (3.273) at the two interfaces.7. In reality. valid in one of the three regions -m < 0. for example.

This implies that potential profiles and energy levels of doping microstructures cannot be calculated without taking carrier-carrier interaction into account. In Figure 3. require self-consistent calculations. 1996. be present (they were omitted above). The main effect of this interaction turns out to be the screening of the Coulomb potential created by the ionized dopant atoms. and Leite.) action effects become important which. as in the case of electrons. &doping structures Whereas in compositional microstructures free carriers may. The dopant atoms are taken to be completely ionized. Enderlein.74: Potential pofiles and energy levels of an isolated p-type &doping layer (left hand side) and an isolated n-type-&dopinglayer (right hand side) of the same sheet dopant concentration 8 x 10l2 ~ r n . &doping microstructures do not exist without such carriers because the doping layer would be neutral if none of the doping atoms would be ionized. (After Sipahi.0x 10” cm-* -50 -250 -200 -100 0 100 200 -200 -100 0 100 200 z (4 z (A) Figure 3. Scolfaro. but need not. Electronic structure of semiconductor crystals with perturbations : : : 50 p-type &well r-type &well 8. together with the sublevel and Fermi level energies.74 we show the resulting potential wells for an isolated p-type &doping layer (left hand side) and an isolated n-type 6doping layer (right hand side). The lower .430 Chapter 3.~The Fermi energy is shown by dotted . lines.

a sublinear increase of V d with E has been found above a critical field value. Consider a single electron in the lowest SL miniband EAl(b). has been confirmed in more rigorous calculations by Lei. i. Horing. Here we will give only two characteristic examples.) 100 > 80 a > 60 40 0 0 = 20 0 0 10 20 30 40 SO 60 70 I D E [kV/cml well depth in the p-type case as compared to the n-type case results mainly from the fact that heavy holes are more strongly localized at the ionized dopant sheet and thus are more effective in screening out the sheet potential then the lighter electrons. (After Lea. which originally was predicted by Esaki and Tsu (1970). Curves 1to 4 correspond to SLs of different miniband widths A.7. the drift velocity decreases with increasing field strength. The underlying physics can be understood easily. In the presence of an electric field parallel to the SL axis. 1991. the experimental V d versus E characteristics clearly reveals the negative differential drift velocity predicted by Esaki and Tsu. Such a behavior. as shown in Figure 3.3. the electron is accelerated . The more detailed treatment of these properties is beyond the scope of this volume.76.75: Calculated current-voltage characteristics of various GaAs/ AlAs SLs with the electric field parallel to the SL axes. Semiconductor microstructures 43 1 Figure 3.e. Experimentally. one concerning electric transport and another concerning optical properties. the differential conductivity becomes negative. Figure 3.75 shows the calculated drift velocity V d versus electric field characteristics of GaAs/ AlAs SLs with the electric field E directed along the SL axes. Macroscopic manifestations of the electron and hole states of semiconductor microstructures The modifications of electron and hole states of semiconductor microstructures manifest themselves in the macroscopic electronic properties of these structures. If corrected for effects of the Ohmic contacts and macroscopic electric field inhomogeneities. Horing and Cui (1991). and Cui. Above a critical field value at which the V d peaks to its maximum value.

further increase of the field strength will actually decrease the current. as the widening of the fundamental energy gap and the shift of the steps towards higher energies with decreasing well width. 1990. For low field strengths. which implies that more electrons populate k-points with a negative effective mass and less with a positive one.Gal-.As QW structures of different wen widths are shown. most of the electrons have low k-momenta and positive effective masses. the total current density of the gas increases if E is further increased. (After Sibille. populating the miniband E:(k).) 300K >- 5 - 2 4 BIAS (VI 6 0 3 until it reaches the inflection point of Eil(k). is due to the Coulomb . its velocity takes a stationary value in a dc field. can be clearly seen in the spectra of Figure 3. and Mollot. Electronic structure of semiconductor crystals with perturbations Figure 3. Thus. An example of an optical experiment is shown in Figure 3. The enhancement of absorption at the step edges. Also other features of the QW band structure observed above. causing deceleration instead of acceleration. which correspond to optical transitions from the tops of hole subbands to the bottoms of electron subbands. its effective mass becomes negative. However. Since the electron is inevitably scattered by phonons and impurities. Simultaneously.77.77. The latter increases with increasing field strength E if the corresponding k-value is below the inflection point. Thereafter.75. Wang. Palmier. the absorption spectra of GaAs/Al. The staircase-like shape of these spectra reflects the DOSs of the electron and hole subbands of a QW which above have been shown to be staircase-like as well. There. the electron gas is heated up by the electric field. If the subgroup of electrons having negative effective mass is sufficiently large. and it decreases with increasing E if the k-value of the electron is above this point. a superlattice contains a gas of many electrons. This reduces the current increase if E raises further because a larger subgroup of electrons is decelerated instead of being accelerated by the field increase.432 Chapter 3.76: Experimental current-voltage characteristics of various GaAs/AlAs SLs with the electric field parallel to the SL axes. This explains the negative differential drift velocity seen in Figure 3.

The electric transport properties and electro-optic effects are particularly well suited . and Henry. a QW emits light at shorter wavelength than the corresponding bulk material does.8. one observes mainly radiative transitions between the electron and hole ground state levels of an (undoped) QW because only these are considerably populated. Beside absorption spectra.77: Absorption spectra of GaAs/Al. photoluminescene spectra are extensively used for the experimental characterization of semiconductor microstructures. while a GaAs-quantum well of 50 A width emits visible red light. Macroscopic electric fields 433 Photon energy ( e v ) ---w Figure 3.As (After Dingle. if one applies an external electric field to a semiconductor sample. interaction between electrons and holes (excitonic effects). 1974.Gal-. Due to the enlarged energy separation of these levels. For instance. the response yields information about the band structure. In the case of GaAs this effect is particularly striking . 3.3. impurity states and other microscopic properties of the material. Wiegmann. In photoluminescene.the bulk crystal emits radiation in the non-visible infrared region.) QWs of various well widths.8 Macroscopic electric fields Macroscopic electric fields in semiconductors are the central focus of many device applications and give rise to important physical phenomena in these materials.

8. This potential is defined as the difference of the energy of a crystal electron in the presence of the electric field and without it. Moreover. either because of spatially inhomogeneous doping such as in the case of a pn-junction. the effective mass equation (3. Electronic structure of semiconductor crystals with perturbations to extract this information.294) As in the case of point perturbations considered in sections 3. The latter fact implies that.295) fulfills the smoothness condition of effective mass theory of section 3.3. In the following theoretical description. With this condition fulfilled.4 and 3. In addition to excluding spatial inhomogeneities of the electric field. The crystal in an electric field has to be treated as what it in fact is.5.295) e I E I a << E g . In practical terms. which here reads (3. 3.53) is applicable. Here it has the form . The presence of such a field can be described by adding a perturbation potential V’(x) to the one-electron Hamiltonian H of the ideal crystal. we will also exclude temporal changes in our discussion below. this means that the field should not change appreciably within a periodicity region. unlike to the case of point perturbations. This only means that the frequencies of these changes should be small compared with the characteristic frequencies of the electrons of the semiconductor. or because of other spatial inhomogeneities as surfaces or interfaces. Often. electric fields in semiconductors need not. If the field strength E is not too large then the perturbation potential (3. Since the limit of the infinitely extended semiconductor is effectively reached in good approximation with G M 100 the characteristic length need not to be larger than about 0. within a characteristic length of G x a.e. and thus is given by V’(x)= e E . an infinite crystal in a homogeneous electric field cannot be replaced by a perturbed supercell whose periodic repetition forms an unperturbed supercrystal. (3.2.1 and 3.01 . be applied externally as they are already present internally.urn. x. and no lattice symmetry along the field direction.434 Chapter 3. Fields which change only little over this very small distance can be considered as homogeneous.294) does not possess lattice translation symmetry.1 Effective mass equation and stationary electron states A semiconductor in a homogeneous external electric field E represents a perturbed crystal in the sense of sections 3. the source of the electric field will play a role only inasmuch as we assume that the field is spatially uniform. i. the perturbation potential V’(x)of equation (3. however. V’(x) diverges at infinity. namely an infinite system with 2-dimensional lattice symmetry perpendicular to the field.

(3.and y-directions is that of a free particle. ( x ) EvFv~. i. E Xe x.. 2m (3. as continuously varying quantum numbers of the .3.298) with E .e. stationary states X V C v ( z )and to assume normalization in terms of Dirac’s &function with respect to these energies. = E” l + -:il2 k. . The z-dependent envelope function factor X . and vary between -co and fco as a direct consequence of the unrestricted motion of the electron or hole in the field direction. ( t ) obeys the equation X.(z) =E ~ X . Assuming the z-axis of our Cartesian coordinate system parallel to the field direction. ~ ~ ( Z ) .i V ) + e E . the components of x and of the . This allows one to use the energies E . respectively.299) For the conduction and valence bands.. the charge of the hole is positive.300) (3. Thus the envelope function F.301) The second equation can be interpreted as the effective mass equation for a hole with (positive) mass Im:l and energy (. x } F V ~ . thus The solutions of the corresponding energy eigenvalue problems for electrons and holes read. ~ . = (3. ~ (3.300) and (3.(x) F ~ E . fe.297) where x l and kl denote.. the electron motion in 2.296) We consider this equation in the particular case of an isotropic and parabolic band. Macroscopic electric fields 435 { E y ( . in particular. equation (3. . As the equation shows.301) are continuous.298) reads (3.8. wavevector perpendicular to the field. x (2). The spectra of energy eigenvalues of equations (3.) -.(x).(x) can be written as F~E. in contrast to the electron with charge -e. respectively. ~ (= ) i k ~ ~ .

they are not eigenstates of the Hamiltonian but rather are non-stationary states cp. Thus. with momentum growing linearly in time. Note that stationary states X. that in addition to stationary states there will be yet other states which are better suited to the condition of a non-vanishing current.301) and their solutions (3.303) and (3.436 Chapter 3.78 for eC = eV = 0 and Bc = 0. a value of about 1013 s . On the decaying side.1 m . and oscillates in the classically allowed hole region with e E z > 0. (3. respectively. ( z ) are shown in Figure 3. and for he.304) describe.l . Although this does not mean that a current flow cannot be described at all by means of stationary states (if the electron system is characterized by a statistical ensemble with respect to stationary states. the expectation value of the current density operator in the field direction vanishes. stationary electron and hole states in an electric field. and with Ai as the Airy-function of first kind.. The electron function decays exponentially with increasing z for e E z > -Eg. Assuming E = lo4 Vlcm and m: = 0. Electrons or holes in such states do not carry an electric current. this region is classically forbidden. it decays within the hole barrier with e E z < 0. Electronic structure of semiconductor crystals with perturbations (3. one obtains for 0 . the total energy E g of an electron is smaller than its potential energy e E z . more strictly speaking. .(z) of conduction and valence band electrons exist at all energies ey between --oo and +m in the presence of an electric field rather than only at energies in the corresponding e n e r a bands without such a field. then non-zero non-diagonal elements will occur in the expectation value of the current density operator). The envelope function for holes behaves similarly. The envelope function is nonzero only because electrons tunnel into this barrier.304) with (3.303) (3.300). They correspond to the classical trajectories of an electron in an electric field.. . The profiles of the two envelope functions X E C ( z )and X . one may suspect.(x. it represents a potential barrier for electrons. t ) which devebp in time not only by means of a timedependent phase factor.305) as so-called electro-optic frequency. a value of 10 m e V . The Schrodinger equations (3. however.and oscillates with decreasing z for e E z < -Eg. Such states do in fact exist.

1 0.t)of these states are time-dependent.(x. on the right hand side is replaced by the operator i b ( a / a t ) .(x.306) To determine F. wherein the energy E.1 -0. The resulting equation reads {&.78: Envelope functions of stationary electron and hole states in an electric field. Oc = OU = 8.3 0. is given by a &function with respect to k. t = 0) = . z} Fv(x. so one has $v(x. t ) of equations (3.296).(x. the envelope function at t = 0 has been chosen such that its normalization integral with respect to the infinite interval over which the crystal in field direction extends. t + a at (3. The solution F.4 0 . = 0.2 Non-st at ionary states. 3. t ) ./C(X.a time-dependent effective mass equation is required.2 0. Then the initial condition for F.2 -Eg/eE 0 Z Figure 3.0 (D 0 W g e N rn g P c 2 rt v) Y -0.8.(x.8. t ) = ~ V O ( X ) F V ( Xt . Bloch oscillations The envelope functions F.) .(--iV) eE . Macroscopic electric fields 437 0. (3.t ) may be stated as pkx FJX. taken at energy cC = E.308) Here.307) and (3.308) is given by .x G ' (3.3.k(x. t = 0) s F.307) In solving this equation we assume that the electron was in a Bloch state ( . -ik. This may be obtained from the corresponding time-independent equation (3. ( ) at t = 0. ) = iTi-F.u g 3 Lc C 0. t ) .

3 10) This is readily verified by a straightforward calculation.311) states that the quasi-wavevector k of a Bloch state in the presence of an electric field changes with time in just the same way as does the ordinary wavevector of a free electron. hence the term Bloch oscillations. = (3. Differing from the latter.o as is done in effective mass theory.311) This important result may also be established without approximating the Bloch factor U v k by u. fi (3. The same holds for time points 2T.310) as (3. with increasing t . The time development of Bloch states in an electric field is therefore periodic.309) with kt = k . the reduced wavevector kT . Electronic structure of semiconductor crystals with perturbations (3.3T etc.310) results in kt-values which can also lie outside the first B Z .ZEt. According to the general considerations of Chapter 2. This means that in the above derivation we inadvertently changed from the reduced to the extended zone scheme. relation (3. This means that the time-dependent Bloch state (3. The period T of these oscillations may be obtained from (3.311) returns. the total non-stationary wavefunction & . the quasi-wavevector is restricted to the first B Z . one may recover the description in terms of the first B Z by subtracting a suitable reciprocal lattice vector K(t). with a at time-dependent quasi-wavevector kt. at t = T . The only approximation needed is the neglect of interband transitions induced by the electric field. However. there will be a particular point in time t = T(E) at which. Equation (3.309) and the previously made approximation U& Uuk. however.)of . k ( x . Owing to the envelope function (3. meaning that Bloch electrons execute periodic motion within their energy bands. to the Bloch state at t = 0 (not counting a phase factor).312) The Bloch oscillations affect not only the wavefunctions but also the pertinent energies E.(kt). For electric fields in symmetry directions of the first B Z . Oscillations also occur in the velocity of Bloch electrons.438 Chapter 3. defined by the quantum mechanical expectation value < ( d x / d t ) >= (qJvhI(dX/dt)IVvk. t ) evolving from a Bloch state (pvk(x) t = 0 remains a Bloch state for t > 0 also.K(T) equals the wavevector kt at t = 0 for the first time.

It is due to the fact that the time dependent Bloch states (3. To prove this statement we consider a field strength of lo4 V / c m and a primitive reciprocal lattice vector K typical of semiconductors.193) for the expectation value ((p. Thus. in the field direction. In such circumstances T may become larger than T~ and OF1. just as the time T. using the identity (dxldt) = ( l / m ) p . just due to the finite field induced lifetime. There is still another reason that Bloch oscillations cannot be observed in ordinary semiconductor crystals. This implies that. an electron starting a Bloch oscillation will soon be scattered and its momentum will be distributed randomly over all k-space. For zero wavevector component k.3. reported in section 3.311) decay in time by themselves since the exponential factor oscillates with increasing frequency. Bloch oscillations are not observable even without collisions. the exponential oscillates so fast that the time dependent Bloch states (3. between two collisions above was found to be small with respect to T . This may easily be seen for quasiwavevectors k close to a critical point. in actual crystals and under normal conditions. then the energy bands E. One may say that these states have a finite lifetime 0. which would otherwise be infinitely large. is the electro-optic frequency of equation 3. is small compared with the period T of Bloch oscillations. . e. impurities and other point perturbations. For the artificial superlattices considered in the previous section 3.. For not' too-large field strengths. If one considers only k-vectors close to critical points of the band structure. The time rv between two collisions is substantially smaller than T . the velocity < ( d x / d t ) > follows by means of the previously derived relation (2. If (1/3)0:t3 is considerably larger than 1. but also for the fact that an otherwise vanishing average current of a Bloch electron does not actually go to zero. also may be understood as a manifestation of Bloch oscillations. remains finite.' due to the electric field. The Bloch period T is of the order of magnitude lo-'' s in such circumstances.h)of the momentum operator p. it also vanishes. taken over a Bloch period. typically of the order of magnitude s. We conclude that collisions are not only responsible for the fact that the current of a free electrons.(k) can be taken in parabolic approximation. no periodic motion can develop in the presence of collisions. The negative differential electric conductivity of a superlattice parallel to its axis. That this is actually not the case is due to perturbations of the Bloch oscillations by collisions of electrons with phonons. turns out to be zero.7.8. The same result holds for the timeaveraged current of the electrons of a crystal in an external electric field. In other terms.7. the primitive lattice vectors and thus the periods T are much shorter than those in natural crystals.305).hJpJ(p. The timeaverage of the velocity < ( d x / d t ) > obtained in this way.311) average out to zero almost completely. Macroscopic electric fields 439 the velocity operator ( d x l d t ) with respect to the timedependent Bloch function Pvk. the phase of the exponential contains a term (1/3)e:t3 (0.and Bloch oscillations may in fact be observed.

305). with E. ) A i ( [ . the possibility of electric field induced coupling between the valence and conduction bands is neglected.313) With the neglect of collisions.. The .+ e E ~ ] / A e . Ec and wavevector components k l k.. in particular. ) A i ( [ . . (3. ) . as may be seen from Figure 3. values of z . It differs from the ordinary Newton’s equation in that the free electron mass is replaced by the effective mass of the respective band v. This explains why field induced interband transitions are referred to as i n t e r b a n d t u n n e l i n g (the term Z e n e r t u n n e l i n g is also used). approximately. The reason for the non-zero overlap is the tunneling of the valence and conduction band electrons into their respective barriers.e. for field induced interband transitions is proportional to the overlap integral between the two envelope functions F. e E z ] / ~ e . This integral is non-zero since valence and conduction band states having the same energies E = eC = 0 differ from zero simultaneously for almost all . the initial and final state energies E. transitions of electrons between the two band edges. the overlap integral has . behave like particles with positive charge e.) where 8. Performing the overlap integral of A i ( [ E . quantum mechanical probability W . the holes.l perpendicular to the field have to be equal . According to equation (3. of equation (3. 3. an equation similar to Newton’s law of motion m t -d 2 < x > = -eE.314) follows from (3. i. x. dt2 (3.e E z ] / A e . For reasons of energy and momentum conservation. The pertinent particles with positive mass. In reality such coupling exists due to the non-vanishing interband matrix elements of the potential V’(x) = e E . .296).e E z ] / A e .8. kc-. Electronic structure of semiconductor crystals with perturbations This yields. is a frequency analogous to the electro-optic frequencies e . = ec = 0 and kl = k l = 0. however with the reduced effective mass mT. Taking account of these off-diagonal elements yields a description of electrons undergoing quantum mechanical transitions between the valence and conduction bands.440 Chapter 3. in such a transition.3 Interband tunneling In the effective mass equation (3.106. to be taken with respect to the product Ai([E./he. formed here.313). = mZ. are considered.m:/(mz m:) of electrons and holes + + . For electrons from the valence band the effective mass is negative.vkvl(x) and FECkci(x) with identical values for E tC and k w l . If. .. ) with respect to z one arrives at an expression proportional to the square of the Airy-function Ai3(E.299) this means E = cC.

3.. (3. per second. In this.315) Therefore.8. One thus obtains the interband transition probability W . Expression (3. thus reads W . Macroscopic electric fields 441 instead of their simple effective masses m.3.8. may be ob..8. For realistic field strengths E. It is just the probability for this tunneling step which the Airy-function expression A i 2 ( E g / W . According to expression (3.) potential V'(x) does not enter this expression explicitly.315). The probability W.. to be nonzero. it occurs implicitly through the lattice constant a in T . oc A i 2 (z) .. reaches the upper band edge... which has the same order of magnitude as (p. from which it can tunnel into the conduction band. This is plausible since this frequency indicates how often a valence band electron.316) for the Airy-function applies. It is small if the condition fit'. is measurably larger than TLB.315). as W.315) for the transition probability W ...318) . the tunneling probability W.) by multiplying this expression with the frequency 1/T of Bloch oscillations.k).. ) represents. Without such an uncertainty interband tunneling would not be allowed by reason of energy conservation: the final state in the conduction band would differ in energy from the initial state in the valence band by the gap energy E./7iB. << Eg (3.kJeE. The non-stationary approach also provides a rough estimate of the proportionality factor in relation (3. (3.2. the asymptotic approximation (3.. To understand what this result means physically we may argue as follows. The same expression follows if one uses the nonstationary states of subsection 3.. The complete expression for W .317) Although the interband matrix element (p.*. the electro-optic energy Ti@. grows larger as the energy uncertainty hOCw approaches the gap energy E. as one would expect. l tained from Ai2(E. = -Ai2 1 T (2).k[xIp. may be understood as the energy uncertainty of an electron-hole pair due to its finite lifetime in the presence of an electric field. was derived using the stationary electron states in an electric field of subsection 3. The energy uncertainty relieves the need to satisfy energy conservation and permits the interband transition probability W . for an electron to tunnel per second from the valence into the conduction band at kl = k = 0.x p k of the perturbation l.

This means that W s t follows from W . kl. 1958. effectively lowering the gap (see Figure 3. This phenomenon is called the Franz-Keldysh effect (Franz. the absorption coefficient with electric field oscillates with photon energy about the absorption coefficient without field. Electronic structure of semiconductor crystals with perturbations holds. with energies eC = e.315) by replacing E. Besides the changes at the fundamental absorption edge considered above.. hence. owing to the tunneling of electrons and holes into their respective barriers. The inequality (3.295) are equivalent.4 Photon assisted interband tunneling As pointed out in Chapter 1. Keldysh.8. one also has changes of optical constants at any higher van Hove singularity of the joint density of states of the interband energy Ec(k)-E.318) transforms into the condition (3. It decays exponentially as hw decreases. of the semiconductor. In typical cases this condition is fulfilled sufficiently well for field strengths of the order of magnitude lo5 V / c m . 3. . 1959). Boer.kCl with identical values for k. while it is definitely not valid for field strengths close to the inner-atomic fields of 10' V / c m . so that the two conditions (3. 1958. in equation (3. but. The latter energy represents an average energy gap in effective mass approximation. In the presence of an electric field this condition no longer needs to be fulfilled. unlike the latter case. At least for such fields interband transitions are important.l. It has the same order of magnitude as E. and we have Franz-Keldysh oscillations (Tharmalingan.+hw. the optical absorption coefficient. Above the gap.442 Chapter 3. Hansch and Kummel. is also non-zero for photon energies below the gap.295) for the applicability of effective mass theory if the gap energy Eg is formally identified with (h2/2m5. holes are generated in the valence band and electrons in the conduction band.hw.79). but also in other optical constants including the real part of the complex refractive index. Field induced changes occw not only in the absorption coefficient. One therefore has (3.319) In an external electric field.318) and (3. just as in the case of field induced interband transitions.)1/a2. transitions of electrons from the valence into the conduction band can also be caused by photons provided their energy JLw exceeds the gap energy E. 1963).(k) . These diminish the resistivity of a semiconductor material and initialize other processes such as carrier heating and impact ionization of the valence band which may finally result in electric breakdown. The optical interband transition probability W z t between the two band edges is proportional to the overlap integral of (x) (x) the envelope functions FVevkvl and FCL. with E. By means of tunneling. the optical transition probability and.

( E. 1996). macroscopic magnetic fields also give rise to effects in semiconductors which provide experimental data concerning effective masses and other microscopic properties of electrons and holes.79: The same envelope functions as in Figure 3. Enderlein. 1969) as well as for the characterization of semiconductor heterostructures.9. 1967). For most purposes . The basis for theoretical understanding of these phenomena are the stationary one-electron states of a semiconductor crystal in the presence of a magnetic field.78. Macrmcopic magnetic fields 443 .3. (Aspnes.-ho)/eE 0 2 Figure 3. 3. Photon energies which give rise to strong electroreflectance signals correspond to optical transitions at critical points of the interband energy (see Figure 3. 1967. in which field induced changes of the reflectivity of a semiconductor sample are measured by means of a modulation technique. particularly galvanomagnetic phenomena such as the Hall effect. These can be used as input parameters for empirical band structure calculations (Cardona.80).9 Macroscopic magnetic fields Like electric fields. including superlattices and quantum wells (Pollak. 1994. Transport properties. Enderlein and Keiper. but with the energy of the electron exceeding that of the hole by the photon energy iiw. This fact is exploited in electrorefiectance spectroscopy. as well as magneto-optic properties. are of particular importance in this context. magnetoresitivity and cyclotron resonance. By measuring the electroreflectance spectra of semiconductors one obtains experimental data relating to their valenceconduction band separation at critical points.

) this field can be assumed to be homogeneous in space and time. 3. we consider spatially and temporally constant magnetic fields H exclusively.1 Effective mass equation in a magnetic field Initially.9. the role of the magnetic field in the Hamiltonian is fully subsumed in the kinetic energy operator (p2/2m) with the canonical momentum operator p replaced by the kinetic momentum operator p (e/c)A(x). temporal changes of the magnetic field in the M H z range are still admissible. the effective mass theory developed in section 3. Below. (After Seraphin and Hess.0 ’ I I I I I I 1. spin will be omitted from our considerations (it will be taken into account later).5 20 25 30 35 400 Energy ( e V ) 4s I Figure 3. and what it will look like if it is feasible. this again only means that the magnetic field is approximately constant on length and time scales which are large compared with corresponding microscopic length and time scales. save for the gradient of an arbitrary gauge + . Thus. The vector of the pertinent magnetic induction vector will be denoted by B. the microscopic time scale is given by the rotation period of an electron about the magnetic field axis which typically lies in the G H z range. Whether an effective mass equation can be derived at all with a magnetic field.3 is not directly applicable to this case. but must be described by the vector potential A of the magnetic induction B. The vector potential A(x) is determined by the magnetic induction vector B. In the case of cyclotron resonance.80: Electroreflectance spectrum of Germanium. In these circumstances. 1965. as usual. must be explored separately. Just as in the case of external electric fields.444 Chapter 3. Electronic structure of semiconductor crystals with perturbations -121 1. This matter will be addressed in the following subsection. Since the interaction of an electron with a magnetic field cannot be characterized by a scalar perturbation potential.

whence '(vk(H u'k' + L A ( x . p-perturbation theory. as in section 3. whence . we use the k .323) Components '(vkl$) with v # vo must vanish according to equation (3. mc p + 1 f) 2 A2(x)(uok')'Fw(k') = EF.e. i. In this sense.3. we consider a non-degenerate band extremum at k = 0.322). The expression (3. Macroscopic magnetic fields 445 function which we choose so that A ( x ) has the form A(x) = A[B x XI. t-hematrix elements of H with v # vo vanish. In order to satisfy the Schrodinger equation (3. the vector potential is presumed to be smooth.8 on electric fields.63) derived there is applicable here as well. (3.321) As in the derivation of the effective mass equation for perturbing scalar potentials in section 3. which were already evaluated above.60) for '(vkl$). Initially. the component with u = vo must obey the relation l(vok(H k ' + eA(x). The Schrodinger equation of a spinless crystal electron in a magnetic field reads + (3.p ) + mc l (:) 2 A2(x)IvAk')l '(vhk'lg) =E '(vkI$). Accordingly. we represent the Schrodinger equation in the approximate Bloch basis Iuk)'. (3. so that the order in which p and A(x) are multiplied in the expression [p (e/c)A(x)I2 is inconsequential.320) 2 This choice of gauge guarantees that p commutes with A(x).9. its matrix representation '(vkJAlv'k')' is approximately diagonal with respect to band indices. (3. To verify this we consider the matrix elements '(vklHlvok')' of the unperturbed Hamiltonian H . be limited by the condition that the associated vector potential changes only little over a unit cell in comparison with the energy gap..322) with this Ansatz.3. The strength of the magnetic field will. and assume the form (3.322) with H = (p2/2m) + V ( x ) as Hamiltonian of the crystal without a magnetic field. Because of the assumed smoothness of the vector potential A(x).(k).

323) and.p. p-perturbation operator. p between the Luttinger-Kohn functions (vokO) Ivok)’ which enter the first-order Bloch functions Ivok)’ of equation (2.325) What remains to be evaluated in the Schrodinger equation (3. We proceed in two steps. ( klA21k’) .plvok’)’ will now be rewritten in a more convenient form. we have (vokOleA.329) Here all terms depending on the magnetic field have been neglected since they only give rise to quadratic terms with respect to B in the matrix elements (3. Substituting relation (3. thus.326) This relation finally confirms the vanishing of the v # vo-components of the left hand side of Schrodinger’s equation (3.334) as unperturbed parts. p.p= -L. In the first step. B. mc Since (3.328) Here p~ = (eTi/2mc) denotes the Bohr magneton.446 Chapter 3. In the second step we consider the first-order corrections.327) (3.328). Electronic structure of semiconductor crystals with perturbations The diagonality of the matrix for A extends to the matrix for A2.323) now is only the matrix of the operator ( e / m c ) A . as well. = zap^ .”@pa for angular momentum components (c. and therefore one also has ’(vkl A2Iv’k’)’ M 6 1 . we obtain .B 2 with L = [xx p] as angular momentum operator.329) in expression (3. Just as the matrix representation of the latter with respect to the approximate Bloch basis (vk)’ is band-diagonal in second order perturbation theory. We have (3. pIvok’0) = pB(vokO(Ti-’LIvok’O) .328) for these elements. The matrix elements of L can be rewritten by means of Heisenberg’s equation of motion which approximately yields (3. This operator has the same structure as the k . (3. the same also holds for the matrix representation of the operator ( e / m c ) A . The band-diagonal elements (vokl e / m c A . and using the notation L . we determine the matrix elements of the operator ( e / m c ) A . First step 1 A. of ‘(vklq) with v # vo.Pr signifies the ordered triplet z y z or a cyclical permutation of it).

In order that it differ from zero. Here we find. as we do here.. namely (3. cubic materials it vanishes for symmetry reasons. In principle.Lp describes the kdependence of the band-index. Macroscopic magnetic fields 447 (3.3 we found that the symmetric tensor M. since it contains a rotational part about the atoms which form the crystal. Apart from a constant factor. Second step Beside the k-diagonal term discussed above.332) In section 3. determines the B-dependence of these elements. tor L. too.and k-diagonal Bloch matrix elements of the Hamiltonian (see equation (3. The tensor L .3. we used the fact that the interband matrix elements of the momentum operator are diagonal with respect to k and k’. that the antisymmetric tensor L . at least as long as only non-degenerate Bloch states IvoO) at the center of the first BZ are considered and spin and spin-orbit interaction are omitted from consideration.9.330) In this.lvokO) do not depend on k. This antisymmetric tensor bears a close relation to the reciprocal effective mass tensor M&La of equation (2. the . a pseudovec. the two quantities may be understood as real and imaginary parts of the same complex tensor. this is possible because the motion of a Bloch electron cannot in general be reduced to a translation. measures the average angular momentum of this rotation in the In Bloch state 1~00).337). The latter evidently describe the interaction of the magnetic moment of the orbital motion of a Bloch electron with the magnetic induction vector B. which describes the coupling of the magnetic field to the rotational part of the motion of a Bloch electron. the angular momentum of the Bloch state IvoO) must differ from zero. The situation is comparable with that for s-states of free atoms. in other terms. The matrix elements (vokO)L.63)). so we may use the relation The quantity L is an antisymmetric tensor or.

The assumption of a non-degenerate band vo will be adopted. Electronic structure of semiconductor crystals with perturbations Hamiltonian matrix of (3.IvokO)] of the approximate Bloch functions Ivok)’ (which was previously omitted) is taken into account.63). then transforming . i.h-1pBB.323).e. The complete result is given by [k. initially. the Schrodinger equation (3.323) still contains terms which are non-diagonal with respect to k. and simultaneously transforming from kspace to coordinate space.335) obtained in rewriting the Schrodinger equation (3. They occur through the formation of the matrix elements l(vok)(e/rnc)A.335) takes the form (3.e(k(Aa(k’) kp‘(kja.jk’)] . where the perturbed part [Ivok)’ .337) in the spin-dependent Luttinger-Kohn basis.p)lvok’)’. (3. as already mentioned. Using the same procedure employed in the spinless case. Then equation (3. Spin a n d spin-orbit interaction Considering the role of spin and spin-orbit interaction. L. vanishes in the spinless case considered here.321) may be written as where g is the gyromagnetic ratio of a free electron (g = 2. +1 2m + For a non-degenerate isotropic parabolic band the magnetic moment L. the following equation results for the envelope function Fvo(x) : 6kk.336) This equation changes if spin and spin-orbit interaction are taken into account. (3.0023).334) and (3. by first representing equation (3.334) 4 Summing the three terms (3. k’ and give rise to a coupling of B to the translational part of this motion.448 Chapter 3.

As one may see. Macroscopic magnetic fields 449 it into the spin-dependent approximate Bloch basis Ivak)' = Ivk)'lo). (3. and finally transforming it back to coordinate space. The matrix elements L.9. are matrices in the two-component spin space.(x. In regard to their transformation properties in coordinate space. the g-factor of the free elecE tron. obtaining In accordance with their definition. the effective mass equation for an isotropic parabolic band follows as = EF. this moment is always negative.339). With = guo 29. the L. is a multiple g. while the non-zero k-linear terms in these elements are negligible. we may write + h-lLm 1 + 2g cr' = i g & d . Ivoa'k)' of the spin-orbit interaction operator vanish at k = 0 for symmetry reasons.338) In obtaining (3. it represents a characteristic of an energy band vo at a particular critical point.353). As in a free atom. of the angular momentum operator emerge from the corresponding expressions (3. namely the vector of Pauli's spin matrices a.338). The deviation from 2 is determined by the induced magnetic moment of the orbital-motion component of a Bloch electron. in other words it results in a diamagnetic . Apart from a constant factor.-values for the conduction band minimum of several diamond and zincblende type semiconductors are listed. the effective mass equation (3.331) without spin-orbit interaction by replacing p in the latter with the spin-dependent operator ?i of equation (2.. (3. This means that L. we used the fact that the diagonal elements '(voaklH.Acr' of cr'. In Table 3. all values g are less than 2.s).330). (3. they are components of a pseudovector.338) takes the form The factor gEo is called an effective g-factor.3.340) Using this expression.. there is only one such pseudovector in the case of systems with the symmetry group oh.11 experimental g:. The constant gvo is determined by the matrix 1 elements of (3. Just like the effective mass.

The Bloch states at k = 0 are IvmO). Then the degeneracy is %fold. A negative effective g-value and hence a larger diamagnetic contribution occurs in Ge. the material with the smallest gap. : . and will address this below.450 Chapter 3.. The eigenfunction $(x) is given in terms of * the envelope function vector F .06 1. The same holds for the components L .339). we need an effective mass equation for degenerate bands. of the effective angular momentum of equation (3.m = 2. Electronic structure of semiconductor crystals with perturbations Table 3. increases if the gap decreases.y.15 contribution to the total magnetic moment of the Bloch electron. F. 1982. (x)= (Fwz(x).41 0.) GaAs GaSb InSb CdTe ZnSe -0.11: Effective g-factors gE of electrons and magnetic interaction constants and q of holes in diamond and zincblende type semiconductors. Degenerate bands We consider the valence band of a diamond and zincblende type semiconductor in the vicinity of the BZ center at k = 0 . and similar to the effective elec. z .20 0.04 0.333) which may be expressed as 0 matrices L~ with elements 04 . For Si. tron mass of expression (2. has the largest negative value of g To describe the top of the valence band of diamond and zincblende type materials.67).(x)) by equation Fw (3.. Spin and the spin-orbit interaction will be omitted initially.13 0. (After Landoldt- IC Bornstein.338). indicating that the diamagnetic contribution is small in this case. and the pertinent LuttingerKohn functions read (vmkO). The elements MGip of the effective mass tensor are 3 x 3 matrices D with elements DZ:.42 3. the effective electron g-value is close to 2. ( x ) . The same behavior of the effective g-factor for decreasing gap is observed among the 111-V compound semiconductors: InSb. This is to be expected since the diamagnetic moment is determined by the average angular momentum L which according to expression (3.

the various angular momentum states. is the pseudovector 9 9 9 9 9 I = (Iz. of the point group oh.+I'. The subset of matrices which transforms according to the representation I?:. valence band of a diamond type semiconductor.. = I?l +I?12+I':. (for the explicit form product representation of the angular momentum matrices see equations (A. The only change is the replacement of the wavevector k by the magnetic induction B. apart from certain constants. The same result for 9 H M follows for the I'l5-valence band of zincblende type semiconductors. Of course..143) of Appendix A). in the case of degenerate bands. Since the magnetic field B.343). which was formulated in section 2. belongs to the representation I?:. only subsets of matrices transforming according to the irreducible representation . and H M follows as - (3. To apply this method to the I?. the average angular momentum of all valence band states also vanishes in the degenerate case. are . The method of invariants.I y r IzLitself. However.9. Macroscopic magnetic fields 45 1 It follows that the envelope function vector of the degenerate valence band in a magnetic field satisfies the equation where the abbreviation (3.. averaging to zero in the absence of a magnetic field.? :I of Oh are allowed to form an hvari9 ant H M under the point group operations of oh. there is coupling of the orbital motion to the magnetic field which does not occur for non-degenerate bands.345) with K being a constant which has to be determined from band structure calculation or by means of experimental investigation. by means of the point symmetry of the crystal. as a pseudovector.7 for the k-dependent term 9 of the Hamiltonian. The above consideration shows that. Thus the scalar product (BI I ) emerges as the only invariant.3. The source of it is the non-vanishing of angular momentum matrix elements between the degenerate valence band states. Like the first tensor in equa9 tion (3. one needs a complete set of 9 linearly independent basis 9 9 9 I vectors in the 3 x 3-matrix space formed from the three matrices I z rI y r z of angular momentum quantum number j = 1 and from the six products of these matrices which transform according to the irreducible parts of the x I?. is also well suited for the B-dependent operator H M . the second tensor H M can also be determined.344) has been used for the angular momentum term.

Q = 2. . The latter can again be obtained by means of the method of invariants.. in the operators Q. namely I = ( Ix. 4 + + additional term H M in the Luttinger-Kohn Hamiltonian which describes the coupling of the magnetic field to the magnetic moment of the I'$-valence band states thus reads * (3. we take the magnetic field in the z-direction and employ the vector potential in the form A = (--By. comparable to that of a p-level in the case 1 of a free atom. have to be made. however.346) where K and q are again constants which must be determined either from band structure calculations or experimentally. In this. $.I z of quantum number of equation (A. : ' The effective mass equation for the I?$ band without a magnetic field is given by (3. but also a second constant q.f and I bands. band of diamond type semiconductors develops into the r.336) also holds. holds unchanged for materials with zincblende structure also.336). 3. Second. If one adds the effects of spin and spin-orbit interaction. that of a non-degenerate band without spin. then the I'b. --. We denote it symbolically by I . the new gauge lacks axial symmetry with respect to the magnetic field.2 Solution of the effective mass equation We demonstrate the solution of the effective mass equations in a magnetic field in the simplest possible case. The I. Unlike (3. That the presence of spin involves not only K .9.452 Chapter 3.74).74). The effective mass equation (3. In most (z cases q is negligibly small (see Table 3. f of equation (3.I y r z ) . band without spin. + ( i e / h c ) A .11).320) used in deriving the effective mass equation (3. 0.. Differing from 9 u u * the spinless case. one must find a complete set of 16 basis vectors of the 4 x 4-matrix space formed from ( $ @ @ . the three angular momentum matrices I ~ly. z . r. an angular momentum ($ term H M has to be added. is understandable because the orbital and spin motions have different gyromagnetic ratios.320).. Electronic structure of semiconductor crystals with perturbations differently affected by the magnetic field so that a magnetic splitting of the or r 5 valence band occurs. To apply this method in the present case. the replacements 8. invariants linear in B are possible only with subsets matrices of I'i5-symmetry. I 030303 *3 and also the triplet (Ix.346) for H M which has been derived here for diamond type semiconductors.$ d . The result (3.144) and their products which transform in accordance with the irreducible parts of the product representation r$ x I?$ = rl+ rz I'12 21'i5+I'k5 of oh. . Two changes are necessary in the presence of a magnetic field: First. I z ) .O). As in the case of the I'.y. there are now two such subsets. R . This gauge differs from that in expression (3.

336) for a non-degenerate band without spin takes the form 2.(x). 2 r z = -. mass lm&1 and eigenfrequency wcw. with the corresponding eigenenergies E L given by EL. Macroscopic magnetic fields 453 because for this gauge the vector potential A = (--By. the effective mass equation (3.349) associated with motion in y-direction through the relation (3. 0..352) .347) yields where we have set eB wcvD = Im:..347) commutes with the translation operators for arbitrary displacements in the x. For the eigenfunctions Xvo(y). eB liC (3.O) also commutes with the momentum operator p. as wavevector components in the x. [ +Pp +pq F d X ) = ( E .) of k. For X. .o)F. It follows from the partial eigenvalue ELo of equation (3.E. yo = rCk.(Pz + $Y)2 am:.3.348) with k . .9. .351) Equation (3. ~ These energies are called Landau levels.lc . 2T 7 (3. equation (3.343) for degenerate bands without as well as with spin. (3. and k . n - (3..and z-directions. which leads to 1 ' F vo (x)= -ez(kSzfkZa)X v o ( Y ) . of equation (3. 1 .. .and z-direction.350) The total energy eigenvalue E . its eigenfunctions can be chosen to also be simultaneously eigenfunctions of these operators. It is well-known that in this case the eigenstates can be described by integer quantum numbers n = 0 .349) describes a harmonic oscillator with center at yo.we have ( + a> . sgn(m&).00.(y). Using the present gauge. 2 .347) is a function Ew(k. The same holds for the more complex effective mass equation (3. E & = FAW.347) Since the Hamiltonian in (3.

In the z. taking the conduction band vo = c as an example.81. = E. is due to the fact that h k . In Figure 3. the of conduction band becomes. The physical meaning of the eigenstates (3. this frequency amounts to 140 G H z .. about its equilibrium position yo. i. One need only replace the quantum number i in (2. which exhibit non-zero dispersion in the k-direction parallel to the magnetic field. only k .. k. p c ~ ( E ) .353) and eigenenergies (3.353). and replace Ei by the set Ecn(k. k y . apart from a constant factor. a Hermitian polynomial of order n. The pertinent frequency is given by (3. it lies in the microwave region. Of the two wavevector components k . This unusual absence of k . enters the energy eigenvalue Euon.2 m and B = 1 Tesla.355).e.454 Chapter 3. the DOS decays like l / d G . It is enlightening to consider the density of states (DOS) of the energy spectrum of equation (3.354) For mC.(n corresponds to the minimum of a particular 1-dimensional Landau subband.and I-directions the electron propagates like a plane wave.352) and (3. It becomes infinitely large ) Each singularity at the uniformly spaced energies E . For energies slightly above E. = 0. .353) with H . According to equations (3. The inverse square root-behavior of the DOS of a single 1-dimensional parabolic band has already been discussed in section 2. represents the eigenvalue of the canonical momentum operator component + + i). however. hLw.. Then the DOS.355).352) of a Bloch electron in a magnetic field may be understood as follows. p c ~ ( Eis shown as a function of E.205) by the set of quantum numbers n . and k. the Landau subbands.) of Landau subbands from equation (3. Electronic structure of semiconductor crystals with perturbations (3. the spectrum of allowed energy values forms a set of 1-dimensional energy bands.5. This DOS can easily be calculated by means of the general definition of equation (2.205). Thus the electron executes an oscillation in y-direction with angular frequency wc.

the cyclotron frequency can be adjusted to match the fixed frequency of the microwave ra- + . p . and every arbitrary linear combination of eigenstates having different k. also larger energies ELan mean larger cyclotron radii.y plane..ron m o t i o n Such circular motion is a consequence of the axial symmetry of the magnetic field. then such linear combinations would have resulted in eigenstates which also execute oscillations with frequency wcvo in the 2-direction.values is again an eigenstate. I the vector potential would have been chosen f in the form (3. Since the eigenenergies Evan(kz)of these oscillations do not depend on the equilibrium positions. Such transitions are involved in cyclotron resonance: At a fixed frequency.350) it may be seen that k . Varying the magnetic field. This signifies circular motion in the plane perpendicular to the magnetic field. In classical mechanics. projected on I . From the expression for yo in equation (3. but phase shifted by 7rj2 with respect to the oscillations in the y-direction. By absorbing an energy quantum of an electromagnetic radiation field. a high degree of degeneracy exists with respect to k. with this.h (I .v) Y 455 Q- % 4 2 0 I 0 2 I I I 1 4 6 E .320) which is symmetric with respect to I and y. known as cyclot. an electron can make a transition from the n-th to the (n l)-th cyclotron orbit. + determines the equilibrium position of the harmonic oscillations along the yaxis. the absorption of microwave radiation is measured as a function of magnetic induction B. one also has circular orbits for the motion of an electron in a magnetic field.Eg(hwCc) 0 Figure 3. The radius of the cyclotron orbit depends on the quantum number n. larger values of n and. rather than that of the kinetic momentum operator component (pz :By).81: DOS in a magnetic field.

Using the position of this maximum on the magnetic field scale.82. Comparison with the theoretical results also yields values for the constants n and q. Measurement of cyclotron resonance is an important experimental method for the determination of effective masses of electrons and holes in semiconductors and metals.82. whereupon the absorption becomes a maximum. each of the doubly spin-degenerate heavy and light hole levels in the absence of a magnetic field splits into a doublet.74)) and H M from equation (3. . two corresponding to heavy and two to light holes. To understand the cyclotron resonance spectrum of holes. The holes show up in two well-resolved maxima in Figure 3.82) it is absent. as in the case of the harmonic oscillator. each value of n determines a group of four energy levels.343) with D from equation (3. Electronic structure of semiconductor crystals with perturbations Magnetic Induction/ Tesla 4 Figure 3. one due to heavy holes and the other due to light holes. the electrons give rise to several cyclotron resonance maxima. Because of the many valley structure of the conduction band.11 these values are listed for several semiconductors. Zeiger. the first peaks of the cyclotron resonance spectrum of germanium are shown. and Lax 1956. Each of the two hole peaks has a doublet structure which can be seen experimentally at higher resolution (in Figure (3. (After Dexter. but in contrast to this case.346).456 Chapter 3. By means of cyclotron resonance measurements these levels can be determined experimentally.82: Cyclotron resonance spectrum of Germanium at 4 K . the effective mass can be determined. In Figure 3. B e cause of broken time reversal symmetry in the presence of a magnetic field.) diation. In Table 3. One finds that the energy levels can always be characterized by an integer quantum number n . the energy eigenvalues of the rs-valence band in the presence of a magnetic field must CJ * be calculated from equation (3.

which of the various oneparticle states are involved in the construction of the corresponding Slater determinant. we have not yet addressed the question of whether the electron system is actually in a stationary state. This is equivalent to asking of which of the infinite number of possibilities will be realized for distributing the electrons of a periodicity region over the infinitely many one-particle states. in limiting cases. and if so. as it is by no means already answered or even addressed by the determination of all possible stationary states of the electron system. and the corresponding energies form energy bands. these energies were evaluated explicitly. while configuration dependencies due to Coulomb repulsion were found for the energies of localized states. We have yet to deal with this question. approximately. In the case of ideal semiconductor crystals the o n e particle states are spatially extended Bloch states. We also described calculational procedures used to determine the stationary oneparticle states and the corresponding energy bands and localized levels. The situation is similar to that in classical mechanics wherein the totality of all possible paths of a particle system. and. independent of the specific configuration of the manyelectron system. However.e. We found that these states could be represented. i. i. For real semiconductors with shallow and deep centers there are. in addition. the set of all possible solutions of the . by Slater determinants of stationary oneparticle states.e.457 Chapter 4 Electron system in t herrnodynamic equilibrium 41 . Fundamentals of the statistical description In the two preceding chapters we discussed the possible stationary quantum states of the electron system of a semiconductor. localized oneparticle states associated with energy levels in the gap between the valence and conduction bands. The energies of extended one-particle states were found to be independent of their occupation.

the presence of such a heat and particle bath mandates a description in terms of the grand canonical ensemble. If the state i does not occur. one needs additional information in the form of initial conditions or initial values of the constants of the motion. the temperature T . . Macroscopic systems are generally not described in a deterministic. b may be assumed to be diagonal with respect to a basis set of stationary quantum states. A particular diagonal element of j indicates how many individual systems of the ensemble are in the stationary state corresponding to the diagonal site under consideration. the initial value of its wavefunction is required. the Slater determinants can be described . A given one-particle state cannot occur more than once. but a statistical way. Furthermore. To find the actual path of the classical system. Using occupation numbers. This ensemble is characterized by two macroscopic state parameters. In statistical mechanics. But this is not the case. We number the possible one-particle states by an integer i which can take the values 1. In any case. In our case. Its statistical operator b is given by * p = e -(H-pfi)/kT where H and denote. may take place. but may be in different quantum states. . If a particular one-particle state i occurs in a Slater determinant one says that it is occupied or that its occupation number Ni is 1. If the latter is a thermodynamic equilibrium state. The diagonal elements are specified using further information on the macroscopic state of the system. then Ni is 0. we will introduce this representation (for more detail see Appendix C). Electron system in thermodynamic equilibrium mechanical equations of motion of the system. this information would be necessary if one were seeking for a deterministic description of the system. in the so called occupation number representation This representation is well suited to describe Slater determinants in a more compact way than was done in Chapter 2. the electron system may exchange energy with the atomic cores of the crystal.. This operator has to be chosen in accordance with the macroscopic state of the system. all of which have the same Hamiltonian as the original one. The properties of this ensemble on average are taken to be representative of the macroscopic properties of the system. In the case of a quantum system.2. This means that the system is understood to be supplanted by an ensemble of systems. The occupation numbers Ni can therefore only take the values 0 and 1. otherwise the Slater determinant vanishes in conformance with the Pauli exclusion principle for electrons. the Hamiltonian and the total particle number operators of the many-electron system. respectively. Before proceeding further. in particular to and from impurity atoms. and the chemical potential p. . The state of the ensemble is described by a socalled statistical operator b.458 Chapter 4. an electron transfer to and from these cores.m. in our case of Slater determinants. has been determined.

. . The Slater determinants IN1. . . . N 2 . configurationdependent. . j NilN1.2) and the total particle number operator summing the f i i over all i.) are. Fundamentals of the statistical description 459 as vectors IN1. N. (4. . . These vectors have. . as many Ni different from zero as the total number of electrons in the system. ' 7 Nw).4. (4. (4. These vectors may be used to represent an arbitrary many-electron operator. . N.1) is in fact diagonal with respect to the basis set of Slater determinants "1. If only extended oneparticle states are involved.3) imply that The occupation number vectors IN1. . like in the case of a real crystal having shallow and deep centers. the energies Ei are.. .) in the occupation number space. . i=l (4.) may be understood as eigenvectors of particle number operators i?i for the eigenvalue Ni (see Appendix C ) . .3) Moreover.1. N z . with the diagonal elements given by . . The IN1. . N. 00 k of the electron system follows by N = p i . .). like in the case of an ideal crystal. of course. fiiIN1. . N z . . .6) one may easily show that the occupation number space matrix representation of the equilibrium density matrix of equation (4.) form a complete basis set in Hilbert space of the many-electron system.2) to (4. Therefore. in general. the occupation number representation of k reads W H= i=l EiNi. N27. N. N z . N 2 . also eigenvectors of I so that ? Using equations (4. N w ) . N. If also localized oneparticle states exist. . N z . .5) where Ei are the configuration-independent oneparticle energies.2) and (4. altogether.

460 Chapter 4. as indicated in equation (4.10) can be written as products of sums over particle numbers for a particular state j . is formed in accordance with the relation Here. In the quotient.) as basis. We begin with configuration-independent oneparticle states. the symbol Tr[ . In doing so it is necessary to distinguish between configurationindependent extended one-particle states. like the average of any other operator of an observable quantity of the many-electron system. Each value of i represents only one state. . The two trace expressions in the numerator and denominator of equation (4. The two expressions (4.9) and (4.1 Configuration-independent one-particle states As above.I stands for 'Trace' and means the summation over . with different spin orientations corresponding to different values of i. since the matrices of 6 and Ni are known in this represent ation. Of course. where we have set p = l / k T for brevity. we will calculate average particle numbers in equilibrium by means of equation (4. . all diagonal elements of the operator within the brackets with respect to any basis in the Hilbert space of the many-particle system. it is advantageous to use the set of Slater determinants IN1. N z . Electron system in thermodynamic equilibrium The average value < fii > of the particle number operator fii. respectively. all factors cancel except the two with j = i. N. .8) become. we describe them by an integer quantum number i. .8). These remain and give rise to the expression . One may easily demonstrate that the value of the trace is independent of the particular basis chosen. 4.2. and localized one-particle states which do depend on the configuration of the many-electron system because of Coulomb repulsion effects.2 Calculation of average particle numbers Below. 4.10).

otherwise it is called degenerate. Substantial deviations from the Boltzmann distribution occur when E . The appearance of statistical degeneracy is a purely quantum mechanical effect . and the average particle number in it deviates from that in classical statistics in which the hosting capacity of states is not limited. A particle system is referred to as non-degenerate if it is described by the Boltzmann distribution. and uses the notation (4. The distribution function of classical statistics. If one identifies the chemical potential p with the Fermi energy E F .2. in the exchange of two identical elementary particles.12) The average particle number in the one-particle state i thus depends only on the energy of the state.13) for the Fermi distribution function previously introduced in Chapter 1. it follows that (4.it reflects the quantization of energy levels and the indistinguishability of electrons. Under this condition the average particle number in << the one-particle state is small compared to 1.EF is no longer large in comparison with k T and.15) follows from the Fermi distribution for energies E with E . just like for an ideal gas.14) We conclude that the average particle number for configuration-independent one-particle state i is given by the Fermi distribution. Statistical degeneracy applies to other elementary particles as well. In this case of substantial occupancy the limited capacity of a one-particle state to host electrons (remember the Pauli exclusion principle) becomes important. we obtain (4. f ( E ) no longer small compared to 1.4. the B o l t z m a n n distribution (4. This also means f(E) 1. Indistinguishability refers to the fact that.E F >> k T . The deviation of the average particle number in a oneparticle state from the value given by the Boltzmann distribution is called (statistical) degeneracy. . Calculation of average particle numbers 46 1 Since the particle number Ni may take only the values 0 and 1. and thus the state is almost unoccupied. therefore. the total wavefunction of the many-particle system transforms either into its negative (this holds in the case of electrons and leads to the Pauli exclusion principle and with it to the Fermi statistics).

but the quantization of energy yields a distribution function which also deviates from the Boltzmann distribution). u must also describe the spin state. we assume that both the band and spin quantum numbers I/ and u are compatible and meaningful simultaneously. In order that the wavefunction luk) really represent only one quantum state. in the latter case it is the Bose distribution function. or.2. Electron system in thermodynamic equilibrium or the total wavefunction transforms into itself (then the population of the oneparticle states is not limited. The simplest case in which localized states occur is that of a simply ionizable donor or acceptor center. the quantum number i is the pair vk of band index v and quasi-wavevector k.17) The Fermi distribution (4.(k)).14 ) yields 1 < fiuk6 > = f(E. As in Chapter 3. we must augment v to include a spin quantum number CT. equation (4. We use the latter description. However. In the latter case the above calculation of average particle numbers has to repeated. i. and a center with n hole ionization levels in the gap is referred to as an n-multiply ionizable acceptor. (4. which may be formally obtained from the Fermi distribution function (4. In such circumstances. alternatively. While the Fermi distribution emerges in the former case. taking account of the configuration dependencies of o n e particle energies because of Coulomb repulsion effects.16) + g). ff = f-. we will write the band states. the peculiarities of the occupancy statistics of localized states can be understood more easily in the case of double donors or acceptors. With this. This distribution cannot be applied to configuration-dependent one-particle states. This is only justified if the spin-orbit interaction plays no role and the two states (uk $) and lvk have equal energy E. henceforth.462 Chapter 4.e.13) by setting the chemical potential zero by and replacing ‘+l’ ‘-1’in the denominator. a center with n electron ionization levels within the energy gap is referred to as an n-multiply ionizable donor. Their states . Therefore.2 Configuration-dependent one-particle states We consider oneparticle states i localized at shallow or deep centers.(k). we start with them. 2 and the average particle number < NUk+& wavevector k follows as + NUk-+ > for band u and (4.14) solves the problem of determining the average equilibrium particle number < I?i > for one-particle states li) having energies which are independent of the configuration of the many-electron system. 4. which we take to be the case here. which is the case here. In the particular case of band states. in the form lvko).

denote the occupation numbers of ex&nded band states. We assume U > 0 so that EL > EL. thereby omitting all excited 1 f states. Calculation of average particle numbers 463 are described in oneparticle approximation with a configuration-dependent Hartree potential (see section 3. we first consider only the two 2-fold spindegenerate oneparticle ground states ID f . respectively. For simplicity.4 and 3. the following four configurations are possible: No. and the two spin-degenerate oneparticle ground states IDf 2 )2 = 1D)21 $) of the 2-fold occupied center. N o + = 1..16). N.Nm). of localized states. We have (4.. The details may be ascertained using first order perturbation theory with respect to the perturbation Vfi of the Hartree potential of equation (3.U = 2(E& . Double donor and acceptor centers We assume a double donor. ber operators Nou. thus they cancel. N0-i = 0. ND-1= 1. No+ = 2 . ND-l= 0. NJ..5). where N3. The one-particle states i are specified as follows. The total energy of the two electrons at the 2-fold occupied center is 2 E i . and consequently also only one type of particle numUsing the pertinent occupation numbers No. Due to the Coulomb repulsion between localized electrons.18) as was the case before. 3. The pertinent configuration-dependent one-particle energy levels are deno'ied by E b and E i . (4. u = fi.2.2). With this approximation. The simply ionizable donor and acceptor centers may be treated as limiting cases of double donors and acceptors. .4.2. = 0. the N-particle states of system may be characterized as IND+rNo-+.19) The factors referring to extended states are the same in the numerator and denominator of expression (4. as will be demonstrated below. To be specific. we have E L = E& U where U is the Hubbard energy of the 2-fold occupied center (see sections 3..8). .)' = 1D)'I f $) of the 1-fold occupied center. The ground state oneparticle of the donor center in the two occupancy wavefunctions (Da)' and states will also differ. No+ = 0. we can think in terms of a substitutional sulfur atom in a silicon crystal. we again have only one type of one-particle wavefunctions + I D a ) l % IDu)2 = p a ) . We use these N-particle states as a basis for the calculation of the average particle number < N 1 > in localized state IDa) D2 according to expression (4. but the difference will be neglected here.$ U ) 2 E E where E E means the ionization level of the 2-fold occupied donor. In the remaining factors referring to localized states.18)..

we have < I 1 f i D .< NA+ 4 NA-+ >). 1 or 2 for the average particle number at the center. N D . except that D2 the sudden changes which occur at zero temperature are smoothed out. which is never exceeded even if D-i p increases further.lb).464 Chapter 4. then < fi 1 ND-+ > increases to the value 2.la this number is shown as a function of chemical potential p for T = 0 K . equation (4. as in the case of band states (see Figure 4. If there were no Coulomb repulsion effects. If one replaces D by A . we will now discuss how the average number of particles localized at a center is influenced by configuration dependencies of one-particle energies due to Coulomb repulsion. is physically understandable: on a microscopic scale.~> = 0. If p exceeds EL. Considering these configurations and their energies specified = above. then E g = E& would hold and the 1-fold occupied state would cease to play a distinct role.i + + + . Electron system in thermodynamic equilibrium 1. which is maintained > + D. AT provided the energy levels EA and Eil in this expression are understood as electron rather than hole energies. The above results for a double donor may be readily transferred to a double acceptor. therefore. The method of calculating the average particle number at double donor and acceptor centers may be easily generalized to centers with more than D5 1 + kD-& suddenly increases to the value 1. When p becomes larger than E g .21) gives the average number < $ 1 > of electrons (rather than holes) at such a center. In Figure 4.~ 1. the variation of < N 1 kD-i> with p is qualitatively the same. the evaluation of expression (4.16) results in [. thermodynamic equilibrium is a dynamic state in which ionization (excitation) and de-excitation processes balance each other. In regard to dependence on chemical potential one has. 2 1 (4. the values 0. = f-.-2P(E2d-d] . As long ? as p < EA. For temperatures above zero Kelvin.-P(%-P) + .i 1 The average number of particles occupying the center is the sum of < I$ and < iD-+by >. Thus the average number of holes is (2.20) D. then < N as long as E b < p < E g holds. given > Using this expression. The fact that the ionization level E$ rather than the oneparticle level E$ of the 2-fold occupied donor center determines the probability for two electrons to be at the center.

E b plays the role of the binding energy E D of the simply ionizable donor. In the latter case one actually has a simply ionizable donor. are particularly important ones in semiconductors.4. and only E A is negative in case c) while E S tends to +m. Thus one obtains which may be written in the form (4.2. and take account of the fact that their oneparticle energies and ionization levels differ. In case b) there are effectively no configuration dependencies due to Coulomb repulsion which is actually only true for band states. ElD E ': ED= ED 1 21 E : ED+w 21 Figure 4. In calculating the average number of particles at such centers one must include all of them. both negative and equal in case b). Instead we turn to simply ionizabIe centers which. The energy levels E A and E$ are both negative but different from each other in case a). two ionization levels in the energy gap. from a practical point of view.23) . and all terms in equation (4. the transition from a double donor to a simply ionizable donor can be represented by E E becoming infinitely large.+ > according to formula (4. For n-fold ionizable centers one has n 1 charge states. We omit this calculation because it is rather cumbersome. In this case.1: Average electron number < N D 3 f i D .21) of a double donor for T ---t 0 K as a function of chemical potential p.21) involving E g automatically vanish. + + Simply ionizable donor and acceptor centers Formally. and does not provide new physical insight. Calculation of average particle numbers 465 .

It is appropriate to clarify the consequences of Coulomb repulsion effects here. and one arrives at ED) = 1 (see Figure 4 . The average hole number at the acceptor follows from this as (4. starting from equation (4. Alternatively.24) for f*(Eo)can be neglected.> according to the general D% expression (4. because in the non-degenerate case most of the localized levels are empty or simply occupied. equation (4.8). Dg. Therefore. then + + + becomes the average number of electrons at the acceptor. and Coulomb repulsion does not play a significant role.24) yields the Boltzmann distribution multiplied by 2. Electron system in thermodynamic equilibrium (4. N 1 = 1 and N D . This result is understandable. according to equation (4. but only takes into account the three states No. in which the ‘1’ in the denominators can be neglected and < N o + No-4 > << 1 holds. The latter can be interpreted as the probability that the simply ionizable donor is occupied by 1 electron. This procedure. The results derived above for simply ionizable donor centers are imme diately applicable to simply ionizable acceptors. if the localized levels are almost completely occupied.26) Here.24) as an effective distribution function.19). the one-electron energy E A of the acceptor state represents the binding energy E B of the hole at this level. on the other hand.466 with Chapter 4. The same average particle number is obtained in this limiting case for a doubly spin-degenerate band state. If statistical degeneracy exists. = 0 and N D . as well as N D f = 0 and No-+ = 1 = . In the limiting case of strong degeneracy. For band states.22). . 1 ~ ) . expression (4. If one replaces D by A in equation (4.8). the exponential term in the denominator of expression (4. then Coulomb repulsion limits the occupancy capacity of the localized states.22) can be obtained as follows. yields expression (4. the energy level localized at the donor can host only half of the particles which can be accommodated by a band level.l = 0. one obtains.~ 0. i. This carries the implication that f * ( E )has the same meaning for localized states of simply ionizable donor centers as f(E) for the doubly spin-degenerate has band states.23) . One again calculates the average value < N 1 kD-. In the non-degenerate limiting case. the average value < Nyik fiv-tk > = 2.e. under the same conditions.

24) if the ground state energy ED' is denoted by E D . The averaging involved has to be carried out over states of the N-electron system in which either no particle is found at the center. 1 . If the hole distribution is non-degenerate. We denote the wavefunctions by IDnlmu).24) is replaced by the temperature-dependent factor (4. there are.e. and the spin-quantum number c. with Cnlmu D ~ ~ ~ .e. for which the localized states are characterized by the three orbital quantum numbers n.26) becomes the Boltzmann distribution function.~ * ( E A ) 1. several such states.2. which is just the average particle number in the space of all states IDnlmc). and m . and the corresponding energy levels by ED. infinitely many at hydrogen-like donors and acceptors. beside the spin degenerate ground state. The roles of these states are similar for both kinds of centers. i. generally. i. and if the factor f multiplying the exponential term in the denominator in (4. w e seek the average number of electrons at the center. Then.-P) [ n (4.8) for the average value. g D n = 2n2. The degree of degeneracy of level n is denoted by gDn. would be hosted by a valence band state.. For the hydrogen atom. Below. Thus far. for E A .26) may be neglected.e. Calculation of average particle numbers 467 For a strongly degenerate hole distribution. and we will discuss the simpler case here. Centers with excited localized states We restrict our considerations here to simply ionizable centers. The latter factor reflects the fact that the population of the acceptor level by electrons is almost doubled due to the 2-fold spin degeneracy of the acceptor ground state. multiplied by f. < C n l m o N ~ d m o >. This is half of the number of holes which under the same conditions. the average particle numbers at localization centers have been calculated under the assumption that.27) This expression may be written in the form (4. expression (4.p >> k T . n . We examine a hydrogen-like donor. with CdmU I ) . the exponential term in the denominator of expression (4. or there is exactly one. 1. according to the N = . We refer to them as excited localized states.28) I-' gDne-fl(EDn-p). we obtain < C fiDnlnlmu > = 1 + C g D n e -P(ED. although there are also excited states for multiply ionizable centers. As we know from Chapter 3. general formula (4.4. = ~ ~ N ~ 0. no other energy levels exist with wavefunctions localized at the center. we will determine the average particle numbers at centers having such excited localized states. indeed. i. M and one gets 1 . however.

and the average particle number at the donor center is given by equation (4. At T = 0 K . so that an apparently strong influence of the excited states occurs at all temperatures T > 0 K .p >> kT holds.29) yields 4 4. 4 Since y* < the average particle number at the center is enlarged as compared to the case without excited states where y* = The excited states therefore lead to an increase of the average particle number at the center. the ground state is almost completely occupied. If. i. This inequality provides a simple criterion which helps decide whether or not the excited states are essential in the calculation of the average particle number at the center. 4. (4. if not through other factors such as finite sample size.28) into equation (4. y* retains the value even in the presence of excited states.468 With this we have Chapter 4 . however. Omitting the excited states in y*.29). = E. we obtain the value for y*. and correspondingly 4. which occurs when y* exp[P(ED .E D >> kT. then by the adjacent donor atoms .31) .24).ED]holds for all excited states n 2 2. so that the n . as long as kT << [ED. Electron system in thermodynamic equilibrium (4. . on the other hand.e.their distances from each other must be large compared to 2 U D n . This is physically understandable because more states are now available for occupancy than without excited states.t h electron shell may be formed unhindered by the adjacent donors. then one has y*exp[P(ED . 2UDn equals about 100 A x n .p ) ] << 1. The factor y* significantly influences the average particle number at a donor center only for weak occupation of the center. This value decreases only slightly with increasing temperature. ~ so that n must clearly be smaller than 10 and the overall influence of the excited states for T > 0 K is not so very great. . considering therefore only the term with n = 1 and g D 1 = 2. the orbital radii U D of the excited states ~ are limited. In silicon. The formal evaluation of the factor y* for hydrogen-like states with E D .29) The validity of this rewriting may be easily demonstrated by inserting y* of equation (4. 7*becomes smaller than provided the temperature T is larger than 0 K . p . whence equation (4.E g / n 2 and g D n = 2n2 at arbitrary temperature T > 0 K leads to the result y* = 0. For a donor concentration of 1015 ern-' this condition yields 2 u <<~1000 A.p ) ] >> 1 or E D. Considering the excited states. In reality.

32) This relation may also be understood as a condition which determines the chemical potential p in the statistical operator j which is used in the averaging procedure. Considering equation (4. The band states are assumed to be 2-fold spin-degenerate. is often not justified. we can now proceed to explore the distribution of the electrons of a semiconductor over these states. with high probability it will occupy the ground state. With this. and one over the localized states. Correlations between the two sets of states which disturb this decomposition are neglected. The localized states (7 f are taken to be the ground states of simply ionizable donors (y = D ) or acceptors (y = A ) at various positions in the crystal. With this. one over the band states. The generalization of the results to the case in which spin-orbit splitting has to be taken into account is straight forward. Density of states 469 so that one gets the same average particle number at the donor center as without excited states. 4.3. This is also physically clear immediately . and.32) (4. The i-sum of equation (4.3. (4. We assume that there are no excited localized states.3 Density of states Having determined the average particle numbers in single one-particle states and sets of such states. As in the case without excited states.because the donor can host only 1 electron. we presuppose that spin-orbit splitting is negligibly small which. so excited states play practically no role. as before. 4. as we know.4.3) for N as a sum of one-particle number operators f i i for the various one-particle states li).33) is decomposed in two partial sums. one obtains from equation (4. the results for donors can also be transferred directly to acceptors but we will not write down the corresponding expressions explicitly.1 Total electron concentration The total electron system is composed of the valence electrons of all atoms of the semiconductor. We denote their number by N b t a l . we obtain the expression i) i) i) . <N >= Nbtal. This number determines the average total particle number < fi > of the system.33) i= I The one-particle states l i ) comprise band states l v k f and localized states lyf where y abbreviates the orbital state quantum numbers and the position of the center.

39). > for 7F the various centers 7.24) and (4. i. Generally. the total electron concentration related to the volume of the periodicity region.25) we have Altogether. we obtain NtOta1= 2 C f ( E u ( k ) ) Cf*(E. the corresponding intensive quantity. Localized states will be taken into account in the next subsection dealing with real semiconductors. Electron system in thermodynamic equilibrium For the band part. for an ideal semiconductor. the expression . The localized part in equation as (4. i.3. + Using the effective distribution function f*(E)for localized states from equations (4. is of interest. It is defined by the expression nbtal = 0 ' nthl Ntotal (4. because they are independent of each other.39) in the absence of localized states.e.38) 7 The