P. 1
semiconductor physics

semiconductor physics

|Views: 531|Likes:
Published by Mahek Mehta
semiconductor physics by Norman
semiconductor physics by Norman

More info:

Published by: Mahek Mehta on Jan 28, 2013
Copyright:Attribution Non-commercial


Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less






  • 1.2 Atomic structure of ideal crystals
  • 1.2.2 Point groups of equivalent directions and crystal classes
  • 1.2.4 Cubic semiconductor structures
  • 1.2.5 Hexagonal semiconductor structures
  • 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 VI elemental semiconductors
  • 1.3.5 IV-VI semiconductors
  • 1.3.6 Other compound semiconductors
  • 1.4. Macroscopic properties and their microscopic implications 33
  • 1.4.1 Electrical conductivity
  • 1.4.2 Dependence of conductivity on the semiconductor state
  • 1.4.6 Semiconductors far from thermodynamic equilibrium
  • Electronic structure of ideal crystals
  • Adiabatic approximat ion. Lattice dynamics
  • equation
  • 2.3 General properties of stationary one-electron states in a crystal
  • vector
  • 2.4.2 Degenerate perturbation theory
  • 2.5 Band structure
  • 2.5.1 Brillouin zones
  • 2.5.2 Degeneracy of energy bands
  • Critical points and effective masses
  • 2.5.4 Density of states
  • 2.5.5 Spin
  • 2.5.6 Calculational methods for band structure determina- tion
  • 2.6 Tight binding approximation
  • 2.6.1 Fundamentals
  • 2.6.3 sp3-hybrids, total energy and chemical bonding
  • 2.7.1 Fundamentals
  • 2.7.4 Kane model
  • 2.8. Rand structure of important seniiconductors
  • 2.8 Band structure of important semiconductors
  • 2.8.2 Germanium
  • 2.8.3 111-V Semiconductors
  • 2.8.4 11-VI semiconductors
  • 2.8.5 IV-VI semiconductors
  • 2.8.6 Tellurium and Selenium
  • 3.1 Atomic structure of real semiconductor crys- t als
  • 3.1.1 Classification of perturbations
  • 3.1.2 Point perturbations
  • Formation of point perturbations and their movement
  • 3.1.4 Line and planar defects
  • 3.2. One-electron Schriidinger equation for point pcrturbations 24 1
  • 3.2 One-electron SchrGdinger equation for point perturbations
  • 3.2.1 Elect ron-core interact ion
  • 3.3 Effective mass equation
  • Effective mass equation for a single band
  • 3.3.2 Multiband effective mass equation
  • 3.4. Shallow levels. Donor and acceptor states 265
  • 3.4 Shallow levels. Donor and acceptor states
  • 3.4.1 Hydrogen model
  • General characterization of deep levels
  • 3.5.2 Defect molecule model
  • 3.5.4 Correlation effects
  • 3.6 Clean semiconductor surfaces
  • The concept of clean surfaces
  • 3.6.3 Electronic structure of crystals with a surface
  • 3.6.4 Atomic and electronic structure of particular surfaces
  • 3.7 Semiconductor microstructures
  • 3.7.1 Heterojunctions
  • 3.7.2 Microstructures: Fabrication, classifications, examples
  • 3.7.3 Methods for electronic structure calculations
  • 3.7.4 Electronic structure of particular microstructures
  • 3.8 Macroscopic electric fields
  • 3.8.1 Effective mass equation and stationary electron states
  • 3.8.3 Interband tunneling
  • 3.8.4 Photon assisted interband tunneling
  • 3.9 Macroscopic magnetic fields
  • Effective mass equation in a magnetic field
  • Solution of the effective mass equation
  • Electron system in t herrnodynamic equilibrium
  • 4.1 Fundamentals of the statistical description
  • 4.2 Calculation of average particle numbers
  • 4.2.1 Configuration-independent one-particle states
  • 4.2.2 Configuration-dependent one-particle states
  • 4.3 Density of states
  • 4.3.1 Total electron concentration
  • 4.3.2 Density of states of ideal semiconductors
  • 4.3.3 Density of states of real semiconductors
  • 4.4 Free carrier concentrations
  • Conservation of total electron number
  • 4.4.3 Intrinsic semiconductors
  • 4.4.4 Extrinsic semiconductors
  • Compensation of donors and acceptors
  • 4.4.6 More complex cases
  • Non-equilibrium processes in semiconductors
  • 5.2. Systematics of non-equilibrium processes in semiconductors 505
  • 5.2 Systematics of non-equilibrium processes in semiconductors
  • Temporal inhomogeneity and spatial homogeneity
  • Spatial inhomogeneity and temporal homogeneity
  • 5.2.3 Space and time inhomogeneities
  • 5.3. Generation and annihilation of free charge carriers 509
  • 5.3 Generation and annihilation of free charge carriers
  • 5.3.1 Generation processes
  • 5.3.3 Bipolar annihilation of carriers at deep centers
  • 5.4 Drift current
  • 5.5. Diffusion and annihilation of free carriers 52 7
  • 5.5 Diffusion and annihilation of free carriers
  • Semiconductor junctions in thermodynamic equilibrium
  • 6.1 pn-junction
  • 6.1.1 Establishment of thermodynamic equilibrium
  • 6.1.2 Diffusion voltage
  • The diffusion voltage
  • e6.2 Heterojunctions
  • 6.2.1 Equilibrium condition
  • 6.3. Metal-semiconductor junctions 557
  • 6.3 Metal-semiconductor junctions
  • 6.3.2 Electrostatic potential
  • 6.3.3 Schottky barrier
  • 6.4. Insulator-semiconductor junctions 567
  • 6.4 Insulator-semiconductor junctions
  • 6.4.1 Thermodynamic equilibrium
  • 6.4.2 Influence of interface states
  • 6.4.3 Semiconductor surfaces
  • Semiconductor junctions under non-equilibrium conditions
  • 7.1 pn-junction in an external voltage
  • 7.1.1 Electrostatic potential profile
  • 7.1.2 Mechanism of current transport through a pn-junction
  • Chemical potential profiles for electrons and holes
  • Dependence of current density on voltage
  • 7.1.5 Bipolar transistor
  • 7.2. pn-junction in interaction with light
  • 7.2 pn-junction in interaction with light
  • 7.2.2 Laser diode
  • 7.4 Insulator-semiconductor junction in an exter- nal voltage
  • 7.4.1 Field effect
  • 7.4.2 Inversion layers
  • 7.4.3 MOSFET
  • Group theory for applications in semiconductor physics
  • A.l Definitions and concepts
  • A.l.l Group definition
  • A.1.2 Concepts
  • A.2 Rigid displacements
  • A.2.2 Translations
  • A.2.3 Orthogonal transformations
  • A.2.4 Geometrical interpretation
  • A.3 Translation, point and space groups
  • A.3.1 Lattice translation groups
  • A.3.2 Point groups
  • A.3.3 Space groups
  • A.4. Representations of groups 655
  • A.4 Representations of groups
  • A.4.1 Introduction
  • A.4.2 Irreducible representations
  • A.4.3 Products of representations
  • A.5. Representations of the full rotation group 673
  • A.5 Representations of the full rotation group
  • Representations for dimensions other than three
  • A.6 Spinor representations
  • A .6.1 S pace-dependent spinors
  • A.6.2 Representation D+
  • A.6.3 Irreducible spinor representations
  • A.6.4 Double group method
  • A.7 Projective represent at ions
  • A.7.1 Factor systems
  • A.7.2 Definitions and theorems
  • A.7.3 Construction of projective representations
  • A.8 Time reversal symmetry
  • A.8.1 Time reversal operator
  • A.8.2 Additional degeneracies of energy eigenvalues
  • A.8.3 Additional selection rules for matrix elements
  • A.9 Irreducible representat ions of space groups
  • A.9.1 Representations of translation groups
  • A.9.2 Star of wavevectors
  • A.9.3 Small point groups and their projective representa- tions
  • Representations of the full space group
  • Spinor representations of space groups
  • Implications of time reversal symmetry
  • A.9.7 Compatibility
  • A.10 Irreducible representations of small point groups
  • A. 10.2 Multiplication tables
  • A. 10.3 Compatibility relations
  • Corrections to the adiabatic approximat ion
  • Bibliography
  • Index


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

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.

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.).


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



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

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


14 16

28 29 30 31 31


33 34



51 51 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 . . . . . . . . . . . . . . . . . . . . . . . . . . .












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




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

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



4.4.4 4.4.5 4.4.6

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



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 . . . . . . . . . . . . . . . . . . . . . . . . .


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



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






Chapter 1

Characterization of semiconductors



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-

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

1985). clean fabrication of the materials in the laboratory and the controlled incorporation of chemical elements played a crucial role from the very beginning. Introduction 3 concept o f the quantum mechanical energy spectrum uf electrons has to be defined in tl different way. 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. historically. Mott and Davis. Mironov. Knowledge of thc mxistence of a distinct material group ‘semiconductors’ developed. Bunch-Bruevich. MPtals have been used by men since antiquity. i. One may expect. Accordingly. for example? Elliot.1. is primarily due to the circnnistance that the characteristic properties of semiconductors depend strongly on their degree of purity.e. only in this way could reliable results be achieved with semiconductors. 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. which amounts to one atom in one hundred f thousand or less. Keiper. Natural diamondrr. The lack of such control in preparation presented fundamental difficulties which had to be overcame in the early days of semiconductor rasearch. T h e microscopic definition discussed above contains no recognizable constraints with regard to the chemical nature of semiconductors. 11979. Ewer. more precisely. for example. relatively slow development of semiconductor physics.1. excccdcd the accuracy that prevailed in chemistry at the t h e by orders of magnitude. initially. Adhr. Enderlein. either dements or binary and ternary compounds. 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). and Xvyagin. F r h s c h e and Ovahinsky. The late and. therefore. on the presence 0’1 absence o certain chemical elements. Since such accuracy was achieved ~ ~ . Interested readers are referred to the extensive literature on this subject (see. only relatively late. 1983. The necessary accuracy o composition control. and a proper treatment of amorphous and liquid materials cannot be acconimodated within the framework of this introduction to semiconductor physics. 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 . This is in fact true semiconductors may be composed of a large variety of chemical elements and compounds. that semiconductors should be distinguished by having a large chemical diversity. are semiconductors only in rare cases. The exponential form of this increase was discovcrcxl by Hittorf in 1851. 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. 1984. but semiconductors attracted attention for the Erst time only a century and a half ago.

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

‘Sheir atomic structure is approximately that of ideal crystals. The presentation of the microscopic principles of semiconductor physics will occupy most of this book. The introductory first chapter lies outside of this framework because it involves discussion of the results on a phenomenological basis. Semiconductor materials. This is by no means accidental. but is due to the microscopic nature of semiconductors. which we have touched upon above. Atornic structure of ideal m y s t a h 5 arsenide or phosphide. a multitude of physical phenomena which occur in other solid state materials may also be observed in semiconductors. The great technical importance of semiconductors has made thorough physical investigation of these materials necessary. atomic structure will be discuss4 in section 1.3 and macroscopic physical properties in section 1. as they are treated in this book. Moreover. In dealing with macroscopic properties we will not restrict ourselves to mere description. which is termed long-range order. but we will also use them to motivate the microscopic model of semiconductors introduced above. In this regard. we will make the first step towards a microscopic theory of semiconductors in section 1. including amorphous ones. and many questions postponed until later. The latter are distinguished by yet another order. In this connection. Owing to both of these aspects semiconductors are thc best explored and understood materials of condensrd matter today. The characterization of semiconductors by means of their unique macroscopic features. but it has also justified the high cost involved in their fabrication and study. Semiconductors have in fact become model systems for basic research in condensed matter physics. It is well established that semicondnctors arc exceptionally well-suited for necessary functions in electronics and electrical engineering. This . The broad technical application of its results distinguishes semiconductor physics now from its early days. this will have to be done in a heuristic way. which permits the controlled variation of characteristic matprial properties by external means over a wide range of parameters.4.2 Atomic structure of ideal crystals In all solid state materials. Naturally.2. will be continued in Chapter 1. the neighbors of an arbitrarily selected atom are ordered in a regular way.1. are crystals. For this reason studies of semiconductors can also provide knowledge of other solid state mattrials. The full presentation of the microscopic principles of semiconductor physics will follow in later chapters. apart from short-range. 1. just as in a molecule. The term short-range order is uscd for this property. often in the most distinctive way. The neighbors of a particular atom form its short-range order complex.2.4. making possible the development of semiconductor optoelectronirs. chemical nature in section 1.

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

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

and more-fold axes are not compatible with the translation symmetry of the lattice.4) has only the trivial solution n = I .f. Groups of point symmetry operations are termed point gvoups.hrough an angle 2?r/n. C. Rotations transform right-hand4 Cartesian coordinate systems into right-handed systems. which do not exhibit an exact translation symmetry.-2. We will derive them now by demonstrating that lhey must have three special properties. For ppI.F with pn . it turns out that rotation symmetry axes Ohrough lattice points can only be 2-. In Appendix A we describe thwn in detail. be a rotation about such an axis t. One may prove this as follows: Let C. For so-caIled gvasi-crystals. Second. Rotating it through 2a/a.ranslation. Since the largest possible length of Cnf Cg'f can only he 2 / f J . but the application of reflections and inversion to right-handed system results in left-handed ones.f CGLf represents a vector parallel to f.8 Chapter 1 .he two vectors. The same holds for the sum Cnf i Cg'f ol t. Moreover.'. Not all of the various point groups listed in Appendix A are allowed as symmetry groups of crystal lailices.. For pn -= -1 one has n = 3.4) yields n 2. It turns out that there are orthogonal transformations which transform lattices into themselves.1).and 6-fold while ri. First. -LO. They are called point symmetry operations of lattices.hat. all points are shifted by the same vector.f and C i l f are vectors of the plane lattice. Thus both C. for pn . 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. = 1 l h e solulion is n = 6 . them s n d o a C. In a t. and a rotation by .one has Cnf f C'L'f = p. equation (1. 1 or 2.f CF'f must be an integer multiple of f. The set of all point symmetry operations of a lattice forms a group. 3-. the point -R is a lattice point having -q. it becomes C. all uf these point groups must contain the inversion transformation with r e q e t t to the lattice point R = 0. This may be seen as fullows: Inversion with respect to 0 transforms a lattice point R into -EL Considered joiutly with R. as w e suppose. as does the set of all lattice translations. -7-3 as integer coefficients. It follows immediately that inversion with respect l o any other lattice point will do h e same. This is indicative t. -r2. but only parlicular ones which are called holohedral point groups. = 2COS (?) 1 must hold for p. This means that C. the relation + + + p .. The multiglicslion of two of these operations is again understood to represent their consecutive application.2 ? r / R transforms it into Cqlf.2 equation (1. Characterkstion of semiconductors their positions. rotations . For p n = -2. 4. with no points fixed. If. 7. inversion with respect to 0 transforms an arbitrary lattice into itself. This completes the proof concerning rotation symmetv opexations. Therefore. Cmbelongs to the point group of the lattice.0 it follows that n = 4 and for p .

> D4h(&. The explicit proof of this assertion will not be presented here. They define the seven crystal systems: triclinic (Ct). In summary.e. orthorhombic ( D z h ) . multiplies all lattice vectors by the same real number. Their common property is that they all have the same point symmetry. All three required properties described above are satisfied by each of exactly se’i. tetragonal (D*h). i. the above results mean that exactly seven different point groups are possible for spatial lattices.or 6-fold axes of rotation must also necessarily contain mirror planes parallel to each of these axes. The simplest lattices ef a given point symmetry are represented at the far l f of each row et in Figure 1. several different types of lattices may exist. but they may differ otherwise. one finds that point groups of lattices having 3-. Both systems of notation are explained in Appendix A. z ) and Oh ($3. Even these simple lattices are not unambiguously &ermined by their ‘point symmetry. If one. The point group notations used here are those of Schonflies and the international notations are given in brackets. and cubic (Oh). In less symmetrical crystal system one may even change certain length relationships or angles between primitive lattice vectors without disturbing the point symmetry.en point groups.2.2 visualizes them by means of their unit cells. stretches or compresses the lattices evenly on all sides. D ~ h ( $ . They axe called primitive lattices. Figure 1. the point symmetry remains unchanged.1: On the multiplicity of the rotation axes of crystal lattices.$). hexagonal (DGh). trigonal ( D 3 d ) . ~ 2 h9( 2 q e ) ~ 3 & $ ) > cZ~( g. Atomic structure of ideal crystals 9 Figure 1. In the tetragonal system the height of the . about &fold and other axes are also possible. These differences give rise to diflerenf lattice types. 4. for instance.2.). Bravais lattices Within a given crystal system. ( C 2 h ) . Third.1. $ ) . namely c%(i).monoclinic.

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. In some special cases. i. The new point set. i. no longer forms a lattice. the primitive lattices are determined only up to continuous point transformations preserving their point symmetries. one obtains a new point set having the same point symmetry as the original lattice. If one adds both face and body centers to the primitive cubic lattice. they represent cubic lattices of two new Bravais types. Analogous considerations have to be made for the other 6 primitive Iattices. one has to examine whether the lattice is only another realization of the original primitive lattice.e. however. equivalent refers to positions which are either identical or that differ by a lattice vector. As before. in general. . If one places the new points in symmetrical positions. I the lattices cannot be transformed into each f other by such a transformation. those which are transformed into themselves or equivalent points by the point symmetry operations. Whether this happens or not is a question which must be explored separately in each case. snch as the centers of the primitive unit cells. If the answer is positive. Therefore. thus it does not represent a cubic lattice of a new Bravais type. then the new point set forms again a primitive cubic lattice. It turns out that both cases may occur. If one adds the body centers of the primitive unit-cellcubes as additional points to a primitive cubic lattice. 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. One calls them different Bmvais types or Bravais latttices. the result may still be a primitive lattice. Altogether one finds three different cubic Bravais lattices. the resulting point set has the cubic point symmetry and it forms again a lattice.e. the primitive (p). Moreover. Generally speaking. with a lattice constant equal to half of that of the original lattice. It may be transformed back to the original primitive cubic lattice by means of a continuous and symmetry preserving transformation. however. and the face-centered (fc) ones. nor can the two centered lattices be transformed into each other by such a transformation.10 Chapter 1. whether or not it can be brought back to the original one by a continuous and symmetry preserving transformation. the body-centered (bc). but may be thought of as the union of several lattices placed within each other. As an example. then this implies that there are two different types of lattices with the same point symmetry. otherwise they are Bravais lattices of different types. Characterization of semiconductors rectangular parallelepiped in relation to its basis may be changed arbitrarily. we consider the different Bravais lattices in the case of the cubic crystal system. The same holds if the added points are the centers of the faces of the primitive unit-cell-cubes instead of the body centers. 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.

Atomic structure of ideal crystals 11 Cubic P Cuhic 1 Chic F Tetragonst I pj$.2. .‘\ # I Triclinic Monocfinic P Monoclinic 1 @ Trigonal R Trigonal and hexagonal P Figure 1. f .1.2: Common unit cells o the 14 Bravais lattices. .

in totul. with atoms of t.one finds that.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. (1. . . then shifts the resulting sublattices relative to t. The assignment ol Iht.akes the values 1 .. . = 1 one says t. . If tbcre are orthogonal transformations . the relation betwccn the new j and E. the vectors 6 . which may be bum1 at general points of the primitive unit cells. j is a non-lincar fimrtioii of E and. respectively. L . also orthogonal transformations which map physically equivalent direchns of Ihe crystal into each other.ions of the two vectors may be different. . . If the primitive unit cell canlains only 1 atom.ion. where L is the total number of atoms in a primitive unit cell. respcctivcly. because of crystal snisotropy. 14 diEerriit Bravais lattices are possible in the 7 crystal systems. 2 . We denote them here by an atom index 1 which t. a primitive unit cell contains several atoms which may be either chemically identical or different.sr lattices to the crystal systems is indicated in Table 1. In the case I. Charactm‘zation of semiconductors In this w q . A crystal without basis may thiis be describd as a laltice whosp points are dl occupied by ahoms. the direct.he species 2. and finally occupies the points of the . relative to the corner R of a primitive unit cell. 1. however. is drscribed by a vrcbor The position R of this atom relative t o the i origin is then given by Ri=Rti. without changing their relative orientation. ‘I’he position of the 1-th at.hat the crystal has no basis.he first by. e. The Bravais lattices themsehps are shown in Figure 1.alswith basis. If E and j are transformed from their original directions reht. equal to zero. in general. the crystal may be generated in such a way that one multiples its crystal lattice L-fold.5) Without loss of generality one may always set onr of the vectors il. For L 2 2 the set of all L atoms is called the basis uf the crystal.1 . shift. . without necessarily bringing the crystal back onto itself. For this reason it is n meaningful to consider.2.12 Chapter I . With only one atom per primitive unit cell! any point symmetry operation of the lattice will ncccssatily transform the whole crystal into itsdf. For cryst.ed lattices. besides the point symmetry operations of the crystal lattice. L. Generally. will differ from the relation before rotat.om. Analogous statements hold for reflections and rotation-reflections. Lattice points do not necessarily have to be occupied by atoms.ive to the crystal into new ones. For L 2 2.1.. 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.. i l . this is not true i general.2. it may be placed in o m o f the roriiers of the cell. . Generally.g.

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

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

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

2.16 Chapter 1.2 summarizes their properties 1. therefore. Table 1. contains 2. in which respect the three cubic semiconductor structures differ.. P63m c (wurt zite st ructure). We consider this connection in more detail in the next section. We start with the three cubic structures. F m3m (rocksalt st ruct ure) . A silicon crystal of volume 1 cm3.t h e diamond. which is obtained from the fcc lattices by omitting the face centers.00 x cm3. The lattice does not determine the positions of the atoms. Characterization of semiconductors (zincblende st ruct ure) . abbreviated as fcc. This is done by the basis of the crystal. The primitive lattice vectors al.a2. nor the distance between two atoms in a crystal with this structure (which is &/4). We stress that the cubic lattice constant is neither the distance between two lattice points (it is u / f i for the fcc lattice). namely the face centered cubic. but also have the same Bravais lattice. The five crystal structures above belong to just two different crystal systems . For the volume Ro of the primitive unit cell one obtains the value u3/4 from equation (1. ey. which deals with the chemical nature of semiconductors. and P3121 or P3221 (selenium structure). The fcc lattice is commonly described in a Cartesian coordinate system whose unit vectors e.3).4 Cubic semiconductor structures Crystals having diamond. In the case of silicon this yields Ro = 4.5 x primitive unit cells. 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.e. .3. Each of these crystal structures is more or less closely tied to a particular material group.* 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. zincblende and rocksalt structures not only belong to the same crystal system. zincblende and rocksalt structures belong to the cubic system and the wurtzite and selenium structures belong to the hexagonal system.

0 < C < h. 4 2 43m Gmm 32 Bravais lattice cubic fc cubic fc cubic fc hexagonal P hexagonal P Primitive lattice vectors Basis I I I . Atomic structure of ideal crystals 17 Table 1.1. 0 < n < $.2.3.2: Characteristicz of the five most comnion structure types of seniiconduc tors. More details are given in the text. Diamond Zincblende Itocksalt Wiirtzite Seleniuni F#m P3121 P3221 fy .

66 Gal’ 5.70 MgS 5.61 a cla Selenium structure Se 4.37 1: I Rocksalt structure PbS 5.13 InAs 6. have the same or different chemical natures. then the position of atom 2 is given by .65 6.3: Lattice constants of semiconductors of various types of structures.33 a 1.93 PbSe 6.65 .54 1.45 Cans CaSb Id’ 5.3 CdO 4.66 ZnS 5.87 5.47 ZnTc 6.31 1.42 HgSe 6. the basis consists of two atoms which.46 I GaN 4.14 1.53 1.08 IlgTe 6.12 PbTe 6.47 1. Diamond structure C Si 5.36 Te 4.46 Wurtzite structure ZnS 3.19 1. 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.60 CdS 4.54 AlP 4.62 I AlN 3.43 AlSb 6. If the basis atom 1 is put at a lattice point.20 MgSe 5.18 Chapter 1. respectively. Characterization of semiconductors Table 1.14 ZnSe 5.14 cl a Diamond and zincblende structure For diamond and zincblende structures.37 5.43 Zincblende structure 1: Ge 5. I a-Sn 6.64 I MgTe 4.05 InSb 6.45 SnTc 6.82 1.62 CdSe 4.63 GaN 3.62 InN 3.08 CdTe 6.47 RlAs 5.11 1.

and that for the (111) plane after 6 layers. respectively.3 and 1. The vertical sequence of atomic layers is indicated on the right hand side of the projections. Atomic structure of ideal crystals 19 Figure 1. In the diamond structure all atoms arc of the same chemical clement. 1.2. chemically equivalent or different atoms. 0 1A 02 8 3A 0 4B P (1111 6 Cmll 3 cfm a IA r. 2 0 3A 40 * 5A 60 (J Figure 1. 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. Spatial model of a crystal having diamond (a) and zincblende structure (b).1.3.4 in. From Figure 1. The sequence for the (100) plane is repeated after 4 layers. respectively.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). The geometric relations are depicted in Figures. a 3-dimensional representation and a plane projection.4: Projection of a crystal having diamond and zincblende structure in a (100) plane (left) and a (111) plane (right). in the zincblendc structure the atoms are of two different chemical elements. The body diagonals through an atom are %fold axes of . Atoms of the same size and darkness lie in the same plane.

+ We now extend our discussion to thc neighborhood-relations in the two crys- . 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. has a glidereflection as additional symmetry dement. It is denoted by F13m. The group o h can be generated from t h e tetrahedral group in yet anothcr way. thew i s yet another symmptry operation. In the raw of diamond structure. The point group of equivalent directions is therefore T d . Characterization of semiconductors Figuw 1.5: Stereograms of the paint groups Oh (left) and 7'6 (right) of. the symmetry group of a tetrahcdron. followrd hy a translation in that plane by (e/4) (ex ey). It may be described as reflection in a plane perpendicular to a cubic axis. say e. For future reference we bear in mind that for the diamond and zincblende structures. One. therefore. Both structures are theiefore tramformd into themselves by the point group T d . rotation. which cuts the connecting line bel w r n two atoms at its center.or 2-atom. the diamond and zinchlmde structiires. This yields the full cubic group Oh.5 (for a n introduction to the stereograms of point groups. For the zincblende structure there are no further point symmetry operations which transform equivalent directions into each other. see Appendix A). namely that which transforms the two chemically equivalent atoms of the basis into cach other. inversion always involves an exchange of the two sublattims. respectively. and the space group turns out to be symmorphic. namely by adding the inversion operation.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. as one can easily determine by means of the stereograms o the f Iwo groups rn Figure 1. and the planrs through opposite cube dges are mirror planes. It follows that their point groups of equivalent directions are at least T d ..

a quarter but half of the length o€ the space diagonal of the reference cube.6: Spatial model of a crystal with rocksalt structure. This means that each 1-atom has. the displawmcnl i s not. altogether. independently of whether t h 2-atom is of the same chemical nature as the 1-atom (diamond structure) or is not (zincblende structure). the so-called coordmatatm Consider atom 1 of thc Lesis of the unit cell at R = 0. tal structures. Their relative positions are given by the vectors (a/4)(1. they arc atoms of thP same chemical species. They are located at thc nearest-neighbor lattice points of the fcc lattice. 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. This means that thew are 12 second nearest neighbors i each slructurr. for both structures. whose center is occupied by the atom itself (see Figure 1. and. the mme also holds with respect to a %atom.3). The basis atom 2 of this cell is one of its nearebt neighbors. Therefore. four nearest neighboring 2 atoms.l).i).l). Since it would also have been possible to start from a 2-atom in this consideration. then the basis atom 2 of the primitive unit cell at R = 0 gives rise t o three more basis atoms of type 2. If all rotation-reflections are executed with respect to the axis through atom I.1. but naturally they lie in three other primitive unit cells. 1.7. For silicon this is 2+35 A . In contrast to zincblende structure. relative to the central atom. l). (a/2)(*e. The second nearest npighbors belong to the same sublattice. of course. f ey).(e/4)(T. (a/4) (1. ( a / 2 ) ( f e y f e z ) . (a/4)(1. The four nearest neighbor atoms lie at the corners of a tetrahedron. 1. n Rocksalt structure The basis of this crystal structure consists. however. whence . They are a l at the same distance l from atom 1 as thP 2-atom first considered. thus their positions are ( u / 2 } ( * e 9 f ef). like that of zincblende structure.21 Figure 1. Thr distanrc betwrrn nearest neighbor atoms is &a/4.

h Here ek.and 2-atoms alternating. with 1. these atoms are ncarest neighbors. h a2 . The point group of equivalent directions is therefore the full cubic group o h (see Figure 1.5).7: Projection of a crystal having rocksalt structure in the (100) plane (left) and the (111) plane (right).7. The second nearest neighbors are the nearest neighboring atoms of the same fcc sublatticp. I$. Each atom. 2 ce. Since shorter distances do not occur.--ex a h 2 a + -&e. a crystal having rocksalt structure can be described as a composite of two fcc lattices. e.6 and 1.. As one can see horn these drawings. The vertical sequences of atomic layers is shown on the right hand side of the projections.5 Hexagonal semiconductor structures The primitive lattice vectors of the hexagonal lattice may be written in the form ai y.a.". Accordingly. ' z This structure is illustrated in Figures 1. has 6 nearest neighbors. displaced with respect to ~ a c h other by the vector ?. The space group is symmorphic and is denoted by FmSm.2. 1. In Ihe direction of a cubic axis. the crystal has the full symmetry of the primitive reference cube. The relative positions are also the same as in this structure.22 Chapter 1. The two primitive lattice vectors a1 . e. therefore. and in the (111) case after 6 layers. Characterization of semiconductors (1111 1A 01B 4 2A 0 28 1A 028 0 - 3A 48 5A 0 6B Figure 1. In the (LOO) case the stacking repeata itself after 4 Iayem. and with their lattice points occupied by chemically different atoms. Their number amounts to 12." 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. as in the zincblende structure. the atoms are separated by a distance of a / 2 .

We denote them by M I . A wurtzite type crystal can be understood as a composite superposition of four interpenetrating hexagonal lattices. If atom M I is sited at a lattice point. all four be . spatial and planar displays. The M-atoms are shown in black and the X-atoms in white. and. and XI. This also mean8 that this axis represents a %fold proper axis of rotation.8 and 1. with the lattice points of two of them occupied by atoms of chemical species M." . The displacement of the XI-lattice with respect to the MI-lattice is Fx1.9). correspondingly. while the two pairs are of different elements M and X.10) Here.2.10). namely M I . Another neighbor of M I is Since the atom Xz at the site -ce. In order that all four be at the same distance from M I .-c$.0. The c-axis through the center of one of the empty hexagons in Figure 1. Each pair of these atoms.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. In Figures 1.9 these relations are illustrated in. respectively. Atomic structure of ideal crystals 23 and a in this plane have equal lengths and form an angle of 2x13 with 2 each other. one obtains from Xz two additional X-atoms at the same distance but in other unit cells. ( is a parameter which may take any value between 0 and 1/2. The space group of the wurtzite structure is nonsymmorphic and is denoted by P6amc. The volume 52 of a primitive unit cell is &a2c/2. among them three proper reflection planes and three glide-reflection planes joined with translations by c/2 in the direction of the c-axis. Mz and X 2 . X 2 ) on the other hand. From these figures one can easily determine the symmetry of the wurtzite structure. X I . the c-axis through atom M i is a %fold symmetry axis (sep Figure t.1.h I Fxz of the unit cell at R . are chemically equivalent. M2.likewise as the two X-lattices. The corresponding point group of directions is c 6 v (see Figure 1. Consider the atom M I in the unit cell at R . on the one hand.3. (1. The two M-lattices are displaced relative to each other by F M ~ . and two of them by atoms of species X. Altogether. Its neighbor in the same unit cell is atom X 1 at the site ?XI. there are four neighboring X-atoms. Wurtzite structure The basis of crystals with wurtzite structure consists of 4 atoms. then the position vectors of the three others are fx1= cc e. The lattice -0 constants a and c of some semiconductors with a hexagonal lattice are listed in Table 1. The axis contains six inequivalent mirror planes.

1) t ." t F x 2 I between Mi and X2 in the unit cell at R = -ce!.9. 19 ( . 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. dito for X I and Xa. This results in the condition c = . the condition (1. nearest neighbors Figure 1. 0 1 A 028 3A 0 4B Figure 1.24 Chapter 1 .8: Spatial model of a crystal with ideal wurtzite structure.10: Stereograms of the point group structure. and . with the interchange of M and X . Projectionof a crystal with ideal wurtzite structure in the plane normal to the c-axis. Characterization of semiconductors Figure 1. (1. The same statement is true for M I . The vertical sequence of atoniic layers is shown on the right herid side.11) If it is fiilfilled. In semiconductor crystals of the wurtzite type.11) is always satisfied almosl perfectly. the atom Mi has four nearest neighboru of chemical species X . the distance 1 7x1 I between M I and X I must be equal to the distance I -ce. c6~of the wurtzite of M I .

which is twice that of thc zincblende reference structure given by 8 1 4 . (see Figure 1.1. The volume &a2c/2 of a primitive unit cell oi“ the ideal wurtzitc structure is d 3 / 2 .11) and (1.t e (see Figure . the zincblende structiire by stacking three double layers A’.t. This result means that in a crystal having wurtzite structure which fuEUs conditions (1. The corresponding distance in the wurtzite structure is Cc = (3/8)@ a.633. Of course.13) must hold. the nearest neighbor atoms are positioned at exactly the same sites as in a crystal having zincblende structure with lattice constant 4 a.iccconstants of the zincblendc structure crystals of this table.11). 1.4) or to the space diagonals e.9). This yields = 3(1/2-<) or = 318 which.2 by 4. B’.12). Indeed. taken together with equation (l.ll).and M2-lattice planes perpendicular to this axis.llb coincides with the . by stacking one upon another two different double layers A and B. If one multiplies the lattice constants a. one says that it has an ideal w u r t z i t e structure. of thc wurtzitc type crystals in Table 1. The uppermost C’ double layer A’ of the zincbbnde structure in Figure 1. the actual positions of the second nearest neighbors differ in the two crystal structures.2. If a wurtzite crystal exactly obeys conditions (1. For the deformation to vanish. The degree of deformation depends on the ratio cla. (1.12). therefore. the distance between the M I . 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 1.2 shows that all wurtzite type semiconductors listed there also satisfy this condition quite well.then one in fact obtains values which fit well witahthe cubic lat.12) Table 1. The distance between two nearest neighbor atoms in the zincblende structure is &all4 with a‘ the cubic lattice constant. the equation a’= h a (1.11) and (1. -t e$ . this does not at all mean that the wurtzite structurc may be traced back to lhe zincblende slruclure. This indicates that the ordering of the nearest neighbors in the wurtzite structure is almost the same as in the zincblende structure. For the two distances to be equal. results in < < (z) fi= = 1. just as in the zincblende structure. The wurtzik structure can be set up. Atomic structure of ideal crystals 25 which is compressed or stretched in the direction of the c-axis. but in the zincblende structure only after three.and XI-lattice planes perpendicular to the c-axis must be three times the distance between the X I . In the wurtzite structure the vertical stacking repeats itself after two double layers of nearest neighbor atoms.

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

it should be emphasized that these struc- .e.1. The space group can be determined from the projection of the crystal on the plane perpendicular to the c-axis (see Figure 1. the long-range order could be perturbed without significantly changing the short-range order of the corresponding crystal.12). 3 2c (1. in which successive atomic positions are rotated with respect to each other by an angle of 120' (see Figure 1. Concluding this discussion of the characterization of the most common semiconductor crystal structures. Atomic structure of ideal crystals 27 Figure 1. The point group of directions is. The atoms are ordered on parallel spirals. These rotation axes pass through the %fold screw axis and through one of the three surrounding atoms. to transform the crystal into itself.h.14) where a is a parameter ranging between 0 and 112. Selenium structure The basis of trigonal selenium and tellurium crystals consists of three atoms.12: Spatial model of a crystal with selenium structure. Beside these screw operations. in both cases. but a left-handed one. The vectors of the basis may be written in the form ~3 = -2craez + .13. 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.13).2. Beside this. This is just what is observed in amorphous silicon and other amorphous semiconductors.14). D3 (see Figure 1. The symmetry operations mentioned correspond to the space group P312. rotations are allowed with respect to the three inequivalent 2-fold axes perpendicular to the caxis. where the spiral differing from P312 has not a right-handed thread. the selenium structure may also have symmetry corresponding to the space group P322. 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.

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

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

It became possible to tailor materials with desired properties. in light emitting diodes (LEDs) and laser diodes for the near infrared t o green spectral region.P) are used. follow from the lattice constants of the constituents by means of Enear interpolation. as in the case of the elemental semiconductors of group IV. just by varying the alloy elements and mole fractions. one obtains the following compound semiconductors: BN. + 1.Ga)(As. InP. (In. ZnN. and by no means obvious. It was recognized at the beginning of the sixties in (Si. so that semiconducting behavior may be expected also in their case. Later it was also shown to be true in many other material combinations.P). Alp. GaN. Except for the nitrides all these compounds crystallize into the zincblende structure. Using this result. besides the zincblende structure. The cubic lattice of constant a(si.30 Chapter 1 . The nitrides are stable in the wurtzite structure. is given by the relation ~ ( s i =~ ).3. AlAs. 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.Ge. Al)As. Following the group III and group V columns of the periodic table from the top down.where asi and a& are the cubic lattice con. The two structures are. Characterization of semiconductors cases.z)asi Z U G ~ . as has been pointed out above.Ga)As and (In. The principal applications of the 111-V semiconductors and their alloys lie in the field of optoelectronics. BAS. In the case of ILVI-compounds the wurtzite structure can also occur. €or example. and from main groups 1 and VI of the periodic table should also be semiconductors. GaSb. respectively. the mixed crystals made of binary 111-V compounds also have semiconducting properties. one may conclude that compounds of elements from main groups III and V. The discovery of semiconducting alloys significantly expanded the family of semiconductor materials. Examples are (Ga. for example. the so-called valence shell. but the semiconducting property of the two pure crystals is often retained in the mixed crystal. This result is known as Vegard’s rule. pro1 vided they have zincblende structure. therefore contains 8 electrons. AlK. Actually the GI-V compounds (with a few exceptions) do crystallize into the zincblende structure. This is important. Ga(As. A mixed crystal strongly deviates from an ideal crystal. alloy. (1 stants of Si and Ge. Later we will prove that semiconducting properties are related to the crystal structure and the number of valence electrons per primitive unit cell. Just. however.2 111-V semiconductors The conjecture that the 111-V compounds should be semiconductors is amply confirmed. The primitive unit cell. (Ga. very similar. P). Gap. BY and GaN also have metastable zincblende phases. GaN .Al)As and Ga(As. InAs and InSb. AlSb. BP. since the crystals of these compounds also have 8 electrons per primitive unit cell. which here has two atoms.ce) a Sil-. GaAs. Ge) alloys.

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

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

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

The question arises how these sharp changes may be understood 0 1a physical basis. serniconduct. 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.16) The mobility p is defined as the ratio of the magnitude of the average velocit. The following example gives an idea of the order of magnitude of the conductivity: Consider a cube with edge length of 1 cm.u. semiconductors. the mobility . 1 To construct an explanation. .5: Electrical conductivity 0 and charge carrier concentrations for metals. 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 (1.1 Electrical conductivity As already mentioned.ors. Then a current of 1 A will flow if ern-'. Characterization of semiconductors Table 1. Material class Metal Semiconductor Insulator lo3. 1o1O 1.16) for the Conductivity o shows that its variations may. and insulators’ are assembled in Table 1. and the electric charge -e of an electron.15) Here. be caused either by different values of the mobility p and/or by different electron concentrations n. we use the known representation of the s electrical conductivity IT a the product of the electron concentration n.y of an electron to the strength of the electric field driving it (for a derivation see Chapter 5). One ex- . in principle. .34 Chapter 1. namely their electrical conductivity. u = enp. (1. and apply a voltage of 1 V between two of its opposite planes.and insulators. 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. n jcm-3 < 10-10 1021 .4.. the term ‘semiconductor’ refers t o a characteristic macroscopic property of these materials. The mobility is actually determined by the scattering processes which electrons undergo due to the perturbations of the crystal lattice. it is assumed that anisotropies either do not exist or are negligible. Formula (1.5.

6 the &. from the chemical diversity of semiconductors. By ‘state‘ we mean. If one assumes for metals one free electron per atom.18) also describes the temperature dependence of the conductivity for other pure semiconductor materials fairly well at sufficiently high temperatures. The orders of magnitude of the mobilities ME. the temperature. but variations by several orders of magnitude are very unlikely.4. 1. As an example we choose silicon.ity atoms.4. 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. The conductivity increases with rising temperature according to the exponential law (1. and insulators. and secondly the Concentrations of certain impurities. the conductivity values in Table 1. of course. IlIacrascopic properties and their microscopic implications 35 pecks. rrg is a factor which depends only weakly on temperature. the doped semiconductor materials are called extrinsic semiconductors. respectively. One calls this process doping wzth impup. In this context. as one might suppose. does not arise.17) This conjecture is confirmed by experiment. differences with respect to the strengths of these processes in metals. Formula (1. k is the Boltzmann constant and Eg is an energy of about 0.one c d s this an int~ninsicsemiconductor.15 the dependence of the conductivity on temperature is shown for very pure silicon and germanium samples. which amounts to approximately 10” electrons per m 3 . doped with arsenic a t o m . namely to intentionally pollute it with atoms of certain chemical elements. save that the values for cro and E. should be more or less the same: P M E E? P S C =” P I S .1.7 eV in the case of germanium and 1.2 Dependence of conductivity on the semiconductor state The large range of conductivity values of semiconductors. must be changed.1el’ in the case of silicon. semiconductors and insulators.l and lo3 R-’ m-’ . we note that it is particularly pronounced if the semiconductor contains practically no impurities . There is a second way of varying the conductivity of a semiconductor over a wide range. firstly. (1. semiconductors. In Figure 1. and consequently it follows that the large conductivity differences between the three material groups are essentially due to their different electron concentrations. In Table 1. psc and in normal metals.18) Here.5 yield the electhen tron concentrations of semiconductors and insulators listed in this table. Considering first the change of the conductivity with temperature.-values are listed for some import ant semiconductors. between lo-’ 0-l c m .

a change of several orders of magnitude i s exhibited.-values for several semiconductor materials at 300 K (in eV).15: Temperature dependence of the conductivity a of very pure (intrinsic) Ge and Si.30 GaP 2. 1954.1 of concentration N D . the conductivity rises monotonically with doping ronrrntration.71 Iiub 0. GaN 3.14 IrlSb 0. Material E.67 CdS 2.43 (Mh 0.) Material E.36 3. 1979.26 03 .y u of As-doped Si a t 1 = 300 X ' an tlic arsenic concentration ~VD.45 AlAs 3.5 6.18 AlSb 1.2 InN 1.66 .95 AlN AIP 2. (Ajter Figure 1.6: E. In Figure 1.11 Ge 0.16.28 IriP 1. Characterization of semiconductors Figure 1.O-SiC 2.00 PbS PbSe PbTe Se 1.37 0.63 ZnS 1 5.50 CdTe 1. Table 1.16: Dependence of the conduc tivit.16 the change of conductivity is shown with N o varying from 1014 up to crnA3.) Morin and Makta.26 Material E.8 Te 0.36 Chapter 1.33 0.27 GaAs 1. At temperature 300 K corraponding to the data of Figure 1. 1982.56 ZnSe 2. (After Epzianov.2 BN 6.0 . C: Si 1.43 HgTe 0. Again.(Aftar Lundoldt-Bumstein.

1 1015. z . The rise of curve 1 above 400 K indicates thcrt the corresponding [relatively pure) material starts to behave like an intrinsic semiconductor (see Figure 1.17.75 x 101*.31.2.} b The trmperalurr dependence of the conductivity is substantially weaker for doped silicon than for pure as may be seen from Figure 1. 195d.1.5-2.7x lo1’ cm ’.17: Temperature dependence of conductivity u of As-doped silicon for different arsenic concentrations N D : 1 1. (After Morin and Maita.75 x 1014. At higher temperatures. In this regard.15).4-1. namely optical absorption.2 x 101B. The temperature rise becomes weaker with increasing doping. The origin of the difference i temperature characteristics of the conn ductivity of pure and d o p d semiconductors remains to be addressed. and for the highest doping it completely vanishes. Macroscopic properties and their microscopic implications 37 Figure 1. . it even turns downward in a decrease that is more pronounced for purer materials. Each curv-e in this figure corresponds to a particular concentration of arsenic atoms. it will be helpful to discuss yet another rnacrosropic property of semiconductors.4.6-2.3 x 1017.

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

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

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

If Eg > 3. In metals the Fermi level l e within the is conduction band. In this. in essence. but the gap of insulators is typically larger than that of semiconductors. The electrons are distributed over the two bands as shown in Figure 1. to the different positions of the Fermi levels in these two different types of materials. Insulators do not differ from semiconductors qualitatively with respect to their Fermi level positions. T . Their Fermi level lies in the energy gap between the valence and conduction bands. we employ the relation u = enp.4. sufficiently far away from the two band edges (measured in units of kT). one has an insulator. The differences in the properties of semiconductors and metals may be traced back. The explanation is illustrated in Figure 1. 1 4 4 Electrical conductivity in the band model . 0 X--L L the Fermi energy must be located within the energy gap between Ev and E. This means that the strong exponential T-dependence of CT must be due to the electron concentration IZ.22: Absorption of photons by electron transitions from vaIence to conduction band. i. Again.. The mobility p can be assumed to be a relatively weakly varying function of temperature. This knowledge provides a complete explanation of the absorption spectrum 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.1.21. we have described an essential microscopic property of pure semiconductors. as a rule.5 e V ..e. .18.22 and needs no further comment. the Fermi levels are found in the energy gap in both cases. hfacroscopic properties and their microscopic implications 41 Figure 1.

20) with n o as a factor of dimension ~ r n .22) If one substitutes f(E)from (1. energies with E > EC Iu so doing. it follows that (1. approximately. the electrons of intrinsic semiconductors are statistically dip tributed over the valence and conduction bands in accordance with the Fermi distribution function f(E). a current will arise from the relatively few clectrons which.21) The concentration of energy levels in the conduction band having energies between E and E dE is p c ( E ) d E .EF > 6T holds. and x consequently no current will flow.24) . approximately (1. Their concentration can be easily calculated.42 Chapter 1. In terms of p . Characterization of semiconductors and comparison with equation (1. The electrons in the fully occupied valence band cannot contribute to carrier transport. one obtains. However. no stste change is possible in the valence band by redistribut.~ depending weakly on temperature. As we know. the Boltzmann distribution function 7 (1. The reason for this is again the Pauli principlc. where pc(E) is the so-called density of states of the conduction band. At T 0 K the valence band is fully occupied.l!J). For a pure semiconductor Ec .ing the electrons. > Thus. This means that the T = 0 K state will remain unchanged in 8 1 electric Eeld. ( E ) one may write the electron concentration n of the conduction band in the form + (1. according t o which an electron state may be occupied by only one electron.221. according to thc Fermi distribution function: are populating the conduction band at ftnite temperature. f i.21) into the integrand of (1.23) where (1. In Chapter 2 we will calculate this quantity explicitly. and the conduction band is completely empty. which describes the number of states per unit energy and unit volume.18j yields. here its mere existence suffices. in the Fermi distribution function j ( E ) of ecpation (l. Since all valence states are occupied.out3 m a y neglect the ‘1’ o the denominator for emrgies E in the conduction band.e.

then the conductivity becomes independent of T. this is only true for T = 0 K . these electrons are excited into the conduction band. If arsenic impurity atoms are present in a silicon crystal. however. namely the fifth valence elcctron of an arsenic atom replacing a silicon atom having only four valence electrons (see Figure 1. as we will see later. we have ignored is that. one has R = N D . 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. which we will discuss below.16 and 1.he electrons of the valence band also make a contribution to the current. the Ferini level lies exactly in the middle between the valence and condiistion bands. This corresponds to the approximate proportionality between cr and N o observed in Figures 1.E F )= Eg/2. For this purpose we again m e the energy band model of Figure 1. i. then practically all arsenic atoms are ionized and the concentration n of free electrons is equal to the that of the arsenic atoms. The only remaining source of a temperature dependence for u is the T-dependence of the mobility p.23).e. just below the conduct. In this way. However. become freely mobile electrons (see Figure 1.1. and that the electrons in these levels are localized at the site of the impurity atom. It is connetted with a remarkable observation of the Hall effect.20) and (1. It is this relatively weak temperature effect which shows up . If the carrier which at sufficiently high temperatures T i s concentration has Ihe value NLI> actually the caw. For this reason. then this model has to be altered. Another inaccuracy of the above consideration that. we will first clarify how one may understand the strong change of conductivity with impurity concentration in extrinsic semiconductors. E F = Ev 1 + -E 2 g ' (1. and they can bc ignored here.e. The corrections at higher temperatures are. we have marked these levels in Figure 1. Strictly speaking. Under these circumstances t. at.17. If the concentration N D of arsenic atoms is not too large: and the temperature 7' not too law. the valence band population also changes.24) which can contribute to transport. and ( E c . Macroscopic properties and their microscopic implications 43 may be understood as the effectiae density of states of the conduction band. bound electrons which formerly could not participate in carrier transport.25) i. The electric charge transport due to the electrons of a not-completely-occupied valence band will be considered more fully later. If temperature i s increased. finite temperatures. we or identify no = N . To ensure the consistency of the expressions (1. so that no longer are all states of this band ocmpied. At temperature T = 0 K each of these levels is occupied by one dectron. quite smaI1.19 for an ides1 semiconductor.4. The temperature dependence of this contribution is roughly the same as that of the conduction band.ian hand edge.23 by short line segments.23) for n.

With this. We now proceed to the Hall effect. OIL the right for T > 0 K .0 0 XX - L Figure 1.17 at high T . T-0 T.44 Figure 1.23: Ordering of the allowed energy values of electrons in a silicon crys- tal doped with arsonic (schematically). Distribution of the electrons of a silicon crystal doped with arsenic over the allowed energy values. G Eg a P W W 2 a I 0 0 X--c L in Figure 1. Each arsenic atom correspond# to 1 locslized energy level. 011the left for T 0 K . 7 . the experimental observations relating to carrier transport in semiconductors are explained microscopically. I n t a. at least in principle.24.

1. one doped with phosphorus. a current I will Bow.25a and b. we assume two silicon samples. i. For both samples it has the same direction. As is well-known. Consider. ROW. however. Gnder the wndilforts . a current component I H perpendicular to both the electric field E and the magneliu field B will arise.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. the Hall effect will be observed in such circumstances. and the other with bnroii as a group 111 element (see Figiiie 1.5 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. with different types of doping. Applying a voltage to both samples. and the other with boron.4. To be specific. namely from '+' to '-'. as shown in Figure 1.25: nlrlstration of the Hall effect in two silicon smrples. 2 5 ~and d). one doped with phosphorus as a group V dement.25).e. the ~ I I I P two sarriples in a niagnPtic Geld B ( ~ e e Figure 1 .

that boron atoms whi& substitute silicon atoms in tf silicon crystal. in addition to the electrons as negative freely mobile charge carriers. One may This surprising observation may be understood as ~OUQWS. Experimentally one finds that the Hall voltage UH has different polarities in the two samples. give rise to energy levels in the forbidden zone just above the valence band edge. one also has positive ones in semiconductors under certain conditions. which depends directly on the sign of the charge. and the boron atonis are electrically neutral. In other words. 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. This is illustrated in Figure 1. At very low temperatures these states are not occupied.26) Since negative charges move to the left. Characterization of semiconductors of Figure 1.25 no current can flow in this direction.as we will do later explicitly . leaving behind unoccupied states. The Hall effect can also be measured in metals. In this way the experimental observations of the Hall effect reveal a remarkable general property of semicondiictors: For doping with certain atoms. For the boron-doped sample this means a Hall current directed upwards. or occupation hole3 in the valence band. but by positive ones. namely upwards. the current is not carried by negative charges as one would expect considering the negative charge of electrons. which moves with velocity v in a magnetic field B. and downward in the phosphorus-doped one.experiences the Lorentz force F=4[vxS]. This is just the observed behavior. then the Hall current flows upwards in the boron-doped sample.27). the current in the boron-doped sample is not carried by negative charge carriers but by positive ones. 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. the Lorentz force F. This is illustrated in Figure 1. A charge q . We . C (1. and positive ones to the right. since in this case the charge carriers are negative. This means that the corresponding Hall currents flow in opposite directions. in contrast to metals and the phosphorus-doped silicon sample.46 Chapter 1. and therefore there will be a voltage UH such that the current caused by it will just compensate the Hall current. has. Electrons in such energy levels are localized at the sites of the boron atoms.26.25d. but in the phosphorusdoped sample the Hall current is downwards. demonstrate . If we assume that the magnetic field is directed normal to the plane of the figure and that it points into this plane. At finite temperatures electrons from the valence band are excited into the boron levels (Figure 1. for both charge signs the same direction.

The population of the bend edge is shown in Figure 1. in the second of a p-type semarondector ( p for ‘positive’). Macroscopic properties and their microscopic implications 47 Figure 1. placed at the upper band edge. 111 the next time interval this process is repeated. and the hole again moves one site further to the right etc.1. The hole has thus moved one site further to the right in this way. the hole moves like a freely mobile electron.26: Ordering of the allowed energy values of electrons in a silicon crystal doped with boron (schematically). the sign of the Hall voltage tells one whether the free carriers of an extrinsic semiconductor are negatively or positively charged. in an electric field. The antranszc semiconductors intro- . For simplicity only one hole is assumed to be in an otherwisr rompletely occupied valence band. Each boron atom corresponds to 1 locali d energy level. In the first case one speaks of a n-typr semzcondurtov (the n stands for ‘negative’). Thus. At the beginning. the hole is at the outermost left position. since all other electrons are blocked because the states to their left are already occupied. In summary. Rut only the electron neighboring the hole on its right hand side can follow this force. but in the opposite dirwtion. The electron immediately on the right hand side of the hole. holes in the valence band behave like freely mobile positive charge carriers. whether they are electrons or holes. This is illustrated in Figure 1.4. As we have seen above.28 at different points of time. This qualitative introduction of the concept of holes will later be elaborated by more quantitative considerations.28. The adjacent electrons experience a force which tends to move them to tho left. Le. moves into the hole and leaves behind another hole to the right of the first one. as if carrying a positive charge. t immediately recognize that these occupation holes of the valence band behave jubt like freely mobile positive charge carriers in an applied electric field.

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

4.26) as F=-[j RC 1 X B ] . However. in accordance with the relatively low carrier concentration of an intrinsic semiconductor in thermodynamic equilibrium. if one irradiates the sample with light which is absorbed by the semiconductor (see Figure 1. 1. we examine the example of photo-conduction. one obtains a relatively small value. shielded against unwanted influence of light.27) This is the same force caused by the electric field E ~ I F/(-e).o EH is by dehition the Hall voltage Ufi. With b as the width of the sample normal to j and 3.valup of the Hall voltage determines the concentration of majority carriers. We will veTify this assertion for an n . However. Here. which permits us l o rewrite equation (1. onr ran also det.22). 'far' means that characteristic macroscopic propexties of the semiconductor deviate strongly from those in equilibrium.29 . (1. semiconductors may easily be driven into states far from equilibrium. in this 'dark state' the conductivity is measured.t y p ~semicondiictor.. To be more specific about these qualitative statements. Consider a sample of an intrinsic semironductor. the conductivity will rise more or less strongly.29) is the so-called Hall constant. depending on the intensity of the light and the magnitude of the absorption coefficient.6 Semiconductors far from thermodynamic equilibrium All properties considered hitherto were for semiconductors in a state of thermodynamic equilibrium or in close proximity.28) where Rff = PrtC 1 (1. A simple estimate for Figure 1. Evidently.29.ermine the majority carrier concentration. assuming realistic conditions. expression below for U x the follows: (1. hy measuring thc Hall vultagr.--env. We can write an analogous expression for holes. In this case the rurrcnt density j can be expressed in the form j =. 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. The = voltage corresponding t. This is shown schematically in Figure 1. only the electron concentration has to be replaced by the hole concentration p . its conductivity decreases to the original low dark value. Thin. If. When the exposure of the sample t o light ceases.

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

the kind of changes contemplated may be characterized as follows: There is no doubt that the electrons of the outer shells. will react most strongly in assembling the isolated atoms of a crystal.e. The periodic ordering of the atoms of a crystal in space is crucial for this proof. Atomic cores and valence electrons Qualitatively.1). In this process the electron states of the atoms will change.e. i. by chemical bonding of previously isolated individual atoms. the electron states of the crystal will also depend on the initial electron states of the isolated atoms prior to crystal formation. which we heuristically introduced in section 1.4. the valence electrons.3 of the preceding chapter we discussed the spatial order and chemical nature of the atoms in ideal semiconductor crystals. This is immediately understandable if one imagines that the crystal is grown from the gas phase. We will show how the simple model of electronic structure of a crystal. The substance of this subject is summed up under the designation electronic structure. and to what extent the electrons of the inner shells also change their states.2 and 1. can be rigorously deduced from the Schrodinger equation. Whether. for they are the primary agents which bind the atoms into the crystal state (Table 2.e.51 Chapter 2 Electronic structure of ideal crystals In sections 1. It will also be seen that the eigenstates of electrons in a crystal devolve upon the electron states of the free unbound atoms. i. The present chapter is focused on the quantum mechanical energy eigenvalues and corresponding eigenstates of electrons in such crystals. One may suppose that such inner shell changes will be comparatively slight. but the resulting states. the energy band model. of course. i. at least for those inner shells which lie much lower energetically than the valence shells (Ta- . 21 . is harder to predict.

if the gown crystal is expoard to certain extrrrial perturbations . This allows one to consider the atomic nuclei and . the inner electrotla threby serve as probes. 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. 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. elwtromagnetir fields .the states of the electrons of the inner shells and those of IhenucIeoas frequently do not change. however.1: Characterization of atomic cores and valence electrons of main group elements from which semiconducting mat. they feel potential changes produced by siirrouuding atoms as being almost uniform. prrssure. Strictly speaking. Their eneqy levels shift. Electronic structure of id& crystsls Table 2.52 Chapter 2. we arc intermtd in the electronic strizrture of crystals. 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. this means that the wavefunctions of these electrons are essentially unaltered. in determining the elertronic stricture of sanironductor crystals and the influence of exterruel perturbations on them. Therefore. which remain practically unaffected. 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. the states of the inner electron shells and those of thc nuclei.2). specifically by the change of the constant potential value arross their localization region. The term d i d d a t P shtjts is iised for t h e s ~ shifts of the inner electron levels.erialsmay be formed. can be assumcd to be the same as those of the free atoms. For the e x h n a l perturbations which are of p r i m interest in semiconductor physics. Furthermore. Here. In B way.heat. as a rule. this is even generally true.

there arc exceptions.he core. In this case the d-electrons significantly participate in chemical bonding and can no longer be included in t. Moreowr. The structure is.) Atom -tp 3 6.iou. The frozen nature of the electron states of the cores of a crystal! and their lack of rcsponse to external influences.E . generally prevails.1 and 2. Since the crystal aIso contains valence electrons as independent particles. rather close t.6 12.7 9. but as always.omiccores and valence electrons. All energies are given in el/.4 7. as the frozen-core a p p ~ ~ ~ i i m Int i ~ ~ ~ a Table 2.1 Ga 4. t 23.5 P 8.5 17. ~ W R the states of the nuclei of the crystal atoms change.ure which is fundamental for the further analysis .9 7.5 5.7 -ec 291 116 182 -cP 6. which is iinchangeahle by definit. so to speak.an. the inner shell eledrons of crystals can be excited by means of electromagnetic radiation in thc far UV and X-ray region.1 A1 4.o them as atom.1 405 537 10.00 11.5 195 C N 0 14.9 95 . 1963.1 the division into core8 and valence electrons is indicated for some elements from which semiconductor crystals arc made. and SkiIlman. In this sense t.5 -.al as system composed of at.ic ~ 0 : ~ s .hc subsystcms composed of atomic iuiclei and inner electrons are elementary building blocks of the crystal. 3.o the oubar valence shells (see Tables 2.8 Zn 3. In heavy metals such like zinc. Somctirnes one refers to this concept.he inner &shells are.1.9 Si 6. 03 20. One rekm t. frozen.4 S 1. .7 5. Atomic cores and valence eJectrons 53 Table 2. of the shallouwt core electrons for some chemical elements which may occur in semiconducting materials.2 8.2.1 147.8 the inner shcll drrctruns jointly as subsystems of the crystal.4 4.4 20.6 3. whose intrrnal structure i s of no further interest sirire it does nut change.0 29. we arrivr at a yic:i. This can also occur by means of an electron beam In solid state nuclear reactions.2). energetically.2: Energy levels -E.4 31.3 17. and -4 of the valence electrons and .9 11.the picture of a cryst. t.1 87. (Afcer Herm.6 8.5 13.

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

The dynamical problem 55 L 0 / .The j-th core mass will be denoted by Mj. 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. 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.1). there are only as many dif€erent values of M j as there are chemically different types of atoms in the crystal. which is further assumed to be point-like {see Figure 2.2.and that of the i-th electron pi. We use Xj t o denote the center-of-mass coordinates of the j-th atomic i core. which depends-on the coordinates x of all electrons and Xj of all atomic cores. In the case of electrons we can omit the index i from their masses since they have the common mass m. Of course. i. The momentum of the j-th core is called P3. by means of the relation . so most of the Mj-values are identical. + 0 \ 0 Figure 2.e. such that We are interested in the motion of the interacting atomic cores and valence electrons of the infinite crystal. Since we assume periodicity of the motion with respect to a periodicity region.2.1: 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). The state of the system is described by a en i wavefunction @. as well as on the time t. The state of the particles in the remaining periodicity regions can then be described by means of a periodic continuation of this function. they will encompass all types of motions of an infinite crystal with desired accuracy. and x for the position of the i-th electron. which can only be adequately treated by m a s of quantum mechanics. ciently large.

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

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

13) Corrmpondingly. Writing (M.Xz. i.e. in the form of a product q x . (2.58 Chapter 2. then the average kinetic e n p r o of a core would be approximately (3/2) h7'.. we replace the N-component sequence o€ the vectors (XI. XJ). 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.. I . we write by x = (XI. .. This remains true when the interactions between the electrons and coresi which were omitted above.~ the Frrmi e n e r a EF i~of the order of m~gnit~ude e V .12) (2. if (2. (2. on statistical average. we thus have -2 X j > < and it. if they did not interact.15) The necessary normalization (2. ie. Electronic structure of ideal cry&& smaller than that of a valence electron. 2 1 7 1 . X) with respect to a periodicity region is assured if each oI the two factors of (2. are taken into account. .11) of the total wavefunction *(x. To simplify the notation.14) To take advantage of the slow motion of the cores we write the solution q{x. follows that Mj < -<xq>. and the J-component sequence of vectors x2. ' (2.X ) = $(x..1 eV below the melt of mg point of the crystal.e.XJ) X. The daerence between the average kinetic energies of the two types of particles arises from the fact that the electrons obey Fermi statistics. . (X\. X ) ' @(XI./2) X > and (m/2) < x > as the < : : avrragP kinetic enmgies of a core and an electron in a crystal. The average kinetic energy of a core is therefore generally smdlcr than that of an electron. x = (XI. whereas atomic cores obey Boltzmann statistics..10) for the total crystal.X) of the Schrodinger equation (2. one may say that.15) is normalized with respect to this region. This observation plays an important role in the following considerations.16) . . 'l'his can be seen in the following way: If the cores and valence electrons were fwe particles. xz. . . i. the cores move much slower than the electrons. X N )by x. . .xz. For typical concentrations of valence electrons in a crystal of about 10" C W L . while kT reaches only about 0. XN).

An analogous statement holds for the periodicity condition (2. The ‘Ansatz’ (2.17) are assumed.. To assure overall periodicity with respect to a periodicity and region we assume it for +(x.15) satisfy a Schrodinger equation in which the coordinates of electrons do not appear.but merely splits off a factor +(X) @(x. T+ + VCCI +(x.15) becomes non-trivial if we proceed as follows: Firstly. while retaining the full dependenre on both Coordinates in thr second factor +(x. for brevity. Secondly. we demand that the split-off factor. and applying the product rule for differentiation we get.2.O)= E&!+t++ c (2. = (2.21) is valid. first of all.2) of @(x. if the identity ($’4’lTe + T + v&ec + Vccl$.2. X). Therefore. we have set and U(X)is in the nature of an electron energy eigenvaliie.18) where.e. . It turns out that such an equation cannot be derived rigorously.20) The set {$4) of the eigenfunctions of the Schriidinger equation (2. 1% + v.X) which depends only on one variable. X).20) is satisfied if it holds for the Fourier type coefficients relative to all basis functions Q’d’ of this set. i.. Yet without any approximation we have [ e Tc + K .. 4(X). X. but only in a special approximation . relation (2.15) is always possible since it does not assert separability of the from the wavefunction variables x and X. .X)+(X) E $ ( x . X)4(X). Using relation (2.X)= U(X)@(X. we assume that $(xiX)is the solution of a Schrodinger equation for electrons. An ‘Ansatz’ of the form (2. The dynarnical problem 59 (2.the adiabatic approximation which was mentioned above.X) 4(X)separately.20) forms an orthonormalized basis set in the Hilbert space of the crystal. (2. of the total wavefunction (2. X). The necessary simplification concerns the matrix element ($’4’(Tc I$4) of the kinetic energy of cores in this equation.4) between Tc and the squares Pj of core momenta.c] $(x.

X). Finally. will be nPglatrd henceforth. which obeys a Schrijdinger equahion in which the coordinates of the cores enter only as parameters in the potential. In summary. red. which does.23) and (2. X). This originsles in the interaction of the electrons with . occur despite its neglect with respect to electron motion.24) Here . With this the operator T.24) are of fundamental importance in crystal dynamics. for the rambined kinetic energies of all cores satisfies the approximate relation Tc[. of course.20).. (2. however. is described by the wavefunction &(XIand the Schrodinger equation (2.23) (2.18) in terms involving the electron energy eigenvalue U ( X ) .20) for the crystal.hr kinetic energy. T h e potential of this q u a t i o n contains.& as if the cores were at. the motion 01 the electrons is treat. Core motion. enters this equation.26) This rcpresents the SchrGdinger equation for the atomic cores in which the coordinates x of thc electrons do not appear.l$(x. In this way. a second contribution IJ(X). 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. X j W G q . but do not occur as differential operators in t. One has the order of magnitude relations (2. we h a w reached the following description of the total crystal. Here we proceed a n the assumption that these relations are proven. besides the core-core interaction energy. effectively does not act on V(X. namely via its energy U(X)which plays the role of a potential (referred to as adiabatze potential).60 Chapbrr 2.In view of this relation we reconsider the SrhriidingFr equation (2. The two equations (2.n/E is a typird value of the core masses M.(X)+ U ( X ) \ d ( X )= Ern(X). The terms of rplativeorders of magnitude (rn/M)1/2 2 lov2 and ( m / h f )w l W 4 . The state of the elcctron system. forming the scalar product with VI. viewed as an interact.25) This means that T.ing system of atomic cores and electrqns: The subsystemof electrons is describcd by R separate wavefunction qi(x. we obtain the relation (Tc + VC. Therefore we present the proof of thwc equations in Appendix B.X)9(X)l E=r ${x. because they are ultimately responsible for the drroupling of rloctron dynamics from the dynamics of the cores.26). (2. replaring the terms which still depend on x by means of the electron Schrodinger equation (2.

18) and (2.18) implies that u(X) = (+(X)ITe + vee. The potential contribution U(X) caused by the electroncore interaction does not depend. in the quantum mechanical understand- . That exactly this situation is described by equation (2.26) to hold jointly in an approximate sense. This is equivalent to the assumption that the core motion be adiabatically slow.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. may be seen from (2. The weight with which the various positions x enter this average over the probability I + ( x . It remains yet to clarlfy what effects are neglected because of the above approximation and why this approximation is called ‘adiabatic’.28) and quantum mechanical transitions between the different eigenstates $14 and $’+’ of the crystal are recognized to occur. slower than the electrons. It is an average value over all their positions X.2.ec(X)l+(X)). according to (2. whereas from the point of view of the cores one obtains equation (2. which could be omitted. The state of the system thus conforms continuously to the evolving new potential values as a function of time. at since equation (2. equation (2.X)1’ d 3 N ~ of finding the electron system in a volume element d 3 N ~ the position x. Since the relation between the velocities of the cores and the electrons. on the electron coordinates. (2.24).13). is determined by the inverse ratio of their masses.24) of relative order of magnitude ( m / M ) l I 2 . If terms of the order of magnitude ( m / M ) I 1 2 are omitted. for without such an interaction the eigenvalue U in the electron Schrodinger equation (2.18) for + ( x . 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.18) and (2.then the total Hamiltonian 7-t of the crystal has non-vanishing off-diagonal elements (2.18) would be a constant independent of X. it is clear why this ratio must be small for the two Schrodinger equations (2. but as smeared out over all space.18) follows. If one considers the previously neglected term in (2. In so far as this feature is seen from the point of view of the electrons.2. without any transitions to other states.26).X). then the quantum transitions due to core motion are also neglected. These transitions are caused by the kinetic energy of the cores exclusively. The dynamical problem 61 the cores.26). which themselves evolve slowly from the initial onset of time variation. In quantum mechanics. however. Equation (2.26) for 4(X) thus contains the same namely that the cores move much assumption as equation (2.

of course. represents a superposition of lattice oscillations. In this approach. they execute oscillations around these positions with amplitudes that become smaller as the temperature of the crystal decreases. 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. This approximation is useful. Also. only as long as transitions between different eigenstates $$ play no important dynamical role.18) (we will not discuss here how this is accomplished. one ignores the motion of the atomic cores completely and assumes that they are resting in certain equilibrium positions Xq. which can be known only after the equation for the electrons has been solved.62 Chapter 2.3). It contains additional approximations. this interaction is called the electTon-phonon interactaon We have yet to explore how the two Schrodinger equations (2.X’). to non-adiabatic quantum transitions between different electron and core states. this procedure is unsuccessful. There are. with the lattice of atomic cores absorbing the energy which is released during recombination. are. reality. however. In One cannot solve the electron Schrodinger equation for all possible core positions. In reality.the one for the cores contains the adiabatic potential U(X). since one would know its eigenfunctions @(x.26) for the electrons and cores can be actually solved. also effects for which this does not hold.18) one obtains the value of the adiabatic potential U at the position X’ of the cores.-(x. as it will be the subject of the next subsection. notably electric current transport.e. one may understand non-adiabatic transitions as the result of an interaction between the electrons and the motion of the atomic cores.2. these transitions play a decisive role. X)q(X). The problem is that both equations.ec(x. i. Electronic structure of i d 4 crystals ing of this term. ter is then used to solve the electron Schrodinger equation (2. It follows that the dynamical problem for the crystal as a whole is solved. The term ‘adiabatic’ thus refers to the essential character of the approximation in neglecting (rn/M)’/’. at the outset. This is actually the case in regard to many crystal properties and phenomena.26) for the cores are completely determined. Therefore. however. whereby the adiabatic potential U(X) and the Schrodinger equation (2. From the solution of the Schrodinger equation (2. X) are known. also known as ’phonon’ excitations. and the electron equation can be fully d e h e d . however... due to . not completely determined . in the recombination of electron-hole pairs mentioned in Chapter 1. 2.18) and (2. However. Formally. The same procedure is then applied to all other possible positions X. This equation can then be used to calculate the core wavefunction t#(X). as we will see below. 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. but has the advantage of being feasible in practical terms.-. only if the positions X o cores in the f potential Vee. Since such core motion. a simplified procedure is necessary. X)= y(x.

2: Iterative calculation of the equilibrium positions of the atomic cores.30) Bearing this in mind.v.2. we may employ the iteration process below for the solution of the two coupled adiabatic equations (see Figure 2.ke. such motion remains finite even at absolute zero temperature. vanish at the equilibrium positions: --vxvo(x)~x. the so-called Hellman-Feynman forces.Xn) ? v.X" 63 I. = (2.29) of the crystal in equilibrium have a minimum at Xq.xeq0.2.ec(X. The equilibrium positions Xq are unknown at the outset.2): In this pro- .(xy -0 ? no xn+1 I + J Figure 2. One can determine them by demanding that the total energy Vo(X) = U(X) VC(X) (2. Equivalent to this is the requirement that the forces -VxVo(X) on the cores. The dynamical problem x o . the quantum mechanical phenomenon of zero-point oscillations.

After the ' first iteration cycle.X e ~ ) V ~ v X r ~ ' o ( X ~x)e(4 1. These can be understood as average values (Q I X 14) of the core positions X with respect to the core wavcfmction 4 . it can he shown. signifying that thc cmes arc still not at equilibrium posibians. in g~neral. ]. i solution is then used to determine the potential Vo(Xo) and the liellmaiiF e y m m forces. By nieans of the non-vanishing f o r c e one det.als.not yet vanish. With regard to semiconductors.64 Chapter 2. 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. that under normal conditions. The linear term of this expansion vanishes since the potential energy has a minimum at Xq. enters them in the Ts h electron Schrodinger equation. and determines the eigerivalue U(Xo).49 A. Electronic structure of ideal crystah cess. the wavehnction 9 itself contains considerably more information. It determines the probability distribution for the positions of the atomic cores. Thus one obtains I so far n VO(X) = vo(xeQ) ' ( X i2 . including a series of semiconductor cryst. and the latter determines the corresponding Heban-Feynrnan forces. the determination of the atomic structure of the crystal.neglecting ternis beyond the square term.In this way one reaches a very important result.18)! to calculate a new eigenvalue U(X1).Xq from the equilibrium positions Xq.he Hcllman-Feynman forces will. 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. taken jointly with appropriate analytical transformations. for instance.29) for the cores. one assumes ccrtain trial equilibrium positions Xo. one can determine these forces without numerically calculating Lhe potentid in the environment of X. x (2. The corresponding core positions are then the equilibrium positions XeQ.31) With this potential the Schriidinger equation (2.26) for @(XIreads .ermines new trial positions XI. t. These oscillations may be describd easily using the S&rodinger eqriatiou (2. This procedure is to be repeated until the forces become zero. In this: it suffices to expand the potential I/o in a Taylor series with respect to hhe displacements X . Si haas the diamond structure. Such structure calculations are successfully carried out currently fw many solid state systems. However. 'The new positions are then substituted again onto the electron Schrudinger equation (z. Thanks to the Fe'egrman theorem.

including the many-electron system of a crystal which will engage us in the next subsection. form the ~ ~ T U C ~ U T .18) for electrons. Relevant phonon information will simply be cited without detailed justification. Born and Huang. The concept we have in mind here is identified by the terms elementary excztatzons or quast-particles (both terms are commonly used). The dynamical problem 65 where.into non-interacting components of motion . of a crystal.2.g. e. The phonons or.18) is well-defined from the very beginning. is a superposition of all normal mode oscillations or phonons. Taking this approach. Equation (2.2. . one can easily transform to a system of uncoupled harmonic oscillators.and their excitation quanta are phonom. e. the actual particles.phonons in ow case. 1968. more generally. 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. while the atomic cores or. the phonons are the most important elementary excitations. of the so-called dynamical matrix which also includes the kinetic energy term). the elements of n o t z o n of the system. 1982). 1979. the potential b’=. To . Their motions are called normal mode osciliataom or lattace oscillations. Vo(Xeq) = 0 has been assumed. than are phonons. and will include phonons only if it is otherwise impossible to properly describe electron dynamics. for simplicity.413elementary excitation involves coordinated motion of all structural elements of the system. As far as the latter are concerned. Readers who are particularly interested in phonons are referred to other books (see. the motion of an individual structural element is a superposition of all elementary excitations . Using the eigenvectors and eigenvalues of the matrix of restoring forces (actually. This concept is based on the possibility of decomposing the motion of a system of mutually interacting particles .Q ~ elements of the system.2. since a thorough development of the theory of phonons is beyond the scope of this book. Phonons are a good example of the introduction of a concept which is of fundamental importance for the dynamics of many body systems..the motion of the atomic cores. for example.. The restoring forces are determined by the second derivatives of the potential Vo(X). Bonch-Bruevich and Kalashnikov. by means of X-ray diffraction. we approximate the core positions X by their equilibrium values Xeq.in our case of the atomic cores of a crystal . In this book we will deal mainly with electronzc elementary excitations. In the sense of Figure 2. the elementary excitations are. or quasi-particles.32) describes a system of coupled harmonic oscillators. Conversely. more generally. We return now to the Schrodinger equation (2.. Bilz and Kress. For common semiconductor crystals this is in fact true in all cases. we take the point of view that they are known from experimental structure investigations.in the electron Schriidinger equation (2. Besides the oneelectron and one-hole excitations.g. so to speak.

xp. We Brst associate each of the N electrons with a particular . x2. .$(xl. .(Xl.x2. (z -34) The wavefunction ~+4(XI. . . . we suppress the core coordinates X in the potential = V + V. satisfy the condition pv(x)= pu(x Cajj + j = 1...e. : stat.(x). .18 j takes the explicit form + 2. writing Vec(x.19). 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. we a s s m e the existence of an infinite set of one-particle wavefunctions q ~ l~ 2 ... . Similarly. firstly. The goal of this subsection is to provide an approximate description which allows one to reduce the number of particles down to minimum number 1.6). .34) is impossible to solve directly since it describes an interacting system of electrons having a tremendously large number of particles of order loz2. ) = v. The Schrodinger equation (2. are. from which the stationary .18) can be written as HVj. the Hamiltonian H = Te V e . . The of p I I ( x ) .Z.XN) must be periodic and normalized with respect to a periodicity region.35) Secondly. One-particle Schrodinger equation With the Hamiltonian H of (2.3 One-particle appraximation.. . henceforth. .XN) the N-electron system may be constructed.. the N-electron Schrodinger equation (2.(x). of the N-electron system in equation (2. . m . X N ) = Ull(X1. 3.5) and (2. . .2. 'pm. i. xN) itself. as Usingequations (2. . (2. WP write .v = 1.36) Employing pY(x)we form wavefunctions for the N-electron system in the folIowing way. Electronic structure of ideal crystals simplify the notation. taken to be periodic with respect to a periodicity region. they . . ~ Hartree approximation In keeping with the remarks above. .2. . x2.. X the electron wavefunction @(x. sylribolically (CPv~lPv) = 6uhr.X) $:.66 Chapter 2. (2. they are assumed to form a complete orthonormal set of functions in Hillert space..331. x2). XN). r1. as the wavefunction @(XI.

38). (q. we assign to each configuration (IJ)the N-electron system a of wavefunction $(y)(xl. we label a particular electron i.. up to partick N which is associated with the state.x21. then at least in some reasonable approximation..XN)= 'pvl(XL)Lp65(X2).37) Disregarding the miitual interaction of the electrons for the moment. 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. . =~LpvJx3)j (2. WP may say that we occupy state pw with particle 1. y Alternatively.(xJ) energy eigenstates of the individual o n e are electron subsystem Hamiltonians. Due to the Pauli exclusion principle. 'py.(XN) . Thus a given state p1. . Here we take a slightly different approach. The dynamical problem 67 oneparticle state pv[x).if not rigorously. .e.2.I.. particle 2. etc. i. Thirdly. the second to the state of particle 2 etc. VN). . . and also barn the nature of that approximation. .. we abbreviate the configuration ( V l .w )by (. ratzon. ignoring spin (which we do at this stage). (bear in mind that there is an i n h i t e number of them). . and this index can take all values between 1 and N. and start from the Schrodinger equation (2.38) for the fully interacting N-electron system .2. particle 1 with state pull particle 2 with state puL. In this procedureI the oneparticle wavefunctions pV.37) forms an eigenstate of the N-electron system if the oneparticle wavefunctions pV. This procedure has the advantage that one ran ai. . ' ..termed configzsvz. . To address this question one may use the variational principle of quantum mechanics.o .pm may occur among the papdated ones lpy. state p with . XN) which is given by the bllowing product of oneparticle wavefunctions: I I ${y}(xl. . . V a l . This suggests t h e question whether a similar result might be possible for interacting electrons.37). These states remain unoccupied. . The Hilbert space of the .e. . Henceforth. once determine whether there is a suitable approximation in which d ~ { may ~ } be written in the product form (2. etc. Most of the states will not even orcur o n r ~ i.(xj) are determined such that the expectation value of the N-electron Hamiltonian H becomes a minimum for N-eIecctran states of the product form (2. not at all . .' ' I X N ) = ~ { V } ~ { Y } ( X lX72 r . . Considering an M-electron system. IP.(xj) in such a way that the product statc +ivi obeys the Schriidinger equation H${V)(Xl* x2.x2.. whether it will be possible to choose the py. p2. The set of quantum numbers. .pVN not more than once.37).a. 1 XN) (2. i. each state can host only 1 particle. the product (2.

.+l = v. i . . . .37) of oneparticle wavefunctions.i ..2. the so-called Hartwe appronmatzoa. . . . . It is called a one-partzcle approozamatton. . of product functions + 1..1remaining elect.40) differs from zero if p J f v3 for one or several I # t . pz-l. p~ = v w holds. called 4 the Hartree-Fock apprommatzoa. This is only possible under the condition that the non-diagonal elements of the Hamiltonian operator on the left-hand side of (2. . . Thus equation (2. .he N . and correspondingly takes the form The diagonal elements in this equation can easily be evaluated as . by the set. pz-l = ~ ~ . co . Within the framework of the Hartree approximation the equation system (2. .. i....his equation by the complex conjugated product function (2..40) Due to the orthogonality of the qv..40) may be neglected.e. In this way we integrate over all XI.38) cannot hold rigorously.68 Chapter 2.N is spanned with P I . Strictly speaking. left-hand side of equation (2.+l. we multiply t. obtain (2. Electronic structure of ideal crysWs system of t. the 1 .. .. pjv ranging over all possible values 1..e. independently of each other.. if = q .40) involves only the diagonal terms with p 3 = vj for each 1 # 2 . In this remaining Hilbert space we form the Fourier-type coefficients of the Schrodinger equation (2.I of H cannot be written exactly as a product {2..rons 1.pcl. it is the simplest variant of a oneparticle approximation.2.39) and x2.381. However. It is this approximation which makes possible the reduction of the N-particle wavefunctions to products of oneparticle wavefunctions.. p o + l . which means that the eigenfunctions ${. t h e right-hand side of this equation differs from zero only if the pvalues coincide with the v-values.. . will be discussed below..1. XN with the exception of xz. . more accurate oneparticle approximation. i.

41).is is its energy eigenvalue.2.42) 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.42) into equation (2. The dynamical problem 69 (2. ITH I (x.)reads %{.) also contains the contribution \'(. V'Iv}(x.45) we rewrit. then the last two terms can be grouped together with U{'(.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. (2. Beside the potential energy ITc(&) due t o the atomic #}x) It is caused by the cores.44) (2.41) as The final relation (2..47) . mutual interaction of electrons.e (2.}to h m the new eigenvalur Using the abbreviation (2. and is commonly called the Hartree p o t e n t d In explicit form. If one substitutes the expression (2.

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

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

once in summing over the particles the sum themselves. as in the case of normal oscillations of a system of interacting atomic cores.e. i. leading to The energy of the N-particle system is therefore not just the sum of all oneparticle energies. one can re-express the terms on the right-hand side of equation (2. This may be made clear as follows. If one adds to the N-electron system (which we will assume to be in the ground state) one more electron. then the one-particle Hamiltonian (2. 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 + + + . needs to be made more precise. Using the one-particle Schrodinger equation. and once in summing over their interaction partners. Therein is reflected the fact that the E. automatically.} of the N-electron system. are the corresponding quasi-particle or excitation energies. In reality the (py(x) describe stationary states of the motion of the N-electron system in which all electrons are involved. it can be further simplified. Because of the electron-electron interaction. and the total energy U{. contain a certain portion of interaction energy with other electrons. The latter statement manifests itself clearly in relation (2. a qualitative difference between these elementary excitations of the electron system and the normal oscillations of a crystal. The E. energy of interaction.43) by one-particle eigenvalues. of one-particle energies. To correct this. however. The idea that the (py(x)are energy eigenstates and the E .52) does not change within the framework of the approximations made above.72 Chapter 2. x may be interpreted as states of single elecp() trons only in a generalized sense. which is done in E. in part. one must subtract the Coulomb interaction energy. It is necessary to subtract the Coulomb interaction energy of the particles. ( x ) as states of quasi-particles or elementary excitations of the N-electron system.43) between the one-particle energies E. This shows that the ( . This is doubly counted in E . There is. First of all. if one passes over to a ( N 1)-electron system. Using the terminology introduced in that context one may consider the states q . are energies of single electrons. the motion of a particular electron is always tied to the motion of all others. and the energy of an electron is also. These states of motion are not mutually coupled. Electronic structure of ideal crystals solution has a well defined and sufficiently simple connection with the solution of the N-electron problem. The oneparticle wavefunctions pV of the N-electron system therefore also approximately describe the elementary excitations of the system of ( N 1) electrons. which we will explore in more detail. underlying the above consideration.

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

Spin a n d spin-orbit interaction At this point in our treatment of the oneelectron approximation. i. and use this to solve the one-particle Schrodinger equation (2.3: Self-consistent solution of the oneparticle Schrijdinger equation. With the latter one recalculates the eigenfunctions p:(x) etc.491. beside . an internal angular momentum with the two possible values rC/2 and --7i/2 in a given direction. The eigenfunctions and potential are then said to be determined self-consistently. We employ one-particle wavefunctions pf(x) close to the true stationary oneelectron states. The solutions vt(x)are then substituted into formula (2. we may also solve the present problem iteratively (see Figure 2. One continues this iterative procedure until the eigenfunctions. atomic cores.50). Electronic structure of ideal crystals d? - n P U V"(X) = t'c(x) VG(X) + Figure 2. As was done there. form the total potential Vo(x) by means of (2.53). r s i n g cp:(x) we determine a POtential t$(x) according to equation (2. and with them also the potential in the following iteration step. This is to say that electrons are capable of a motion in spin space. it is a p propriate to recognize that electrons h w e a spin.49).e. no longer change within a specified limit of accuracy. thereby determining new potentials TG(x) and V l ( x ) .74 Chapter 2.3).

In spin space one usually refers all quantities to the basis X I = (1. .( i0 - 0') 1 3 0 (2. If the latter i s independent of the state in coordinate space. i).X I = ( 0 . the periodic crystal potential of equation (2. The spinor {px(x. the quantum number X which defines the statr must also specify the spin state. The dynamical problem 75 their motion in coordinate space. the spin motion is accompanied by a magnetic moment of the electron. px(x. by setting .. on the one hand. i)} (~~(4)~ (2. (7.-[VV(X) 4m c Tz x p] .. To determine the spinor state of an electron uniquely. This is mainly due to the fact that. a so-called two-component spinor.56) Here V(x) denotes.57) Taking account of spin and the spin-orbit interaction. which in this context is called orbatal m o ) tion.2. the orbital motion gives rise to a magnetic field which couples that magnetic moment. o where u may take the two values T (spin up) and 1 (spin down). i). two-component spin space. p(x. s) on the spin variable s which may take the two possible values s = and s = . In quantum theory it i s shown that this interaction. i.).akes the form . on the other hand. the wavefunction of an elcrtron changes from an ordinary vector p(x) in Hilbert space to an element {~(x. the orbital and spin motions are coupled.2. as before. and that. the one-particle Schrodingw equation (2.yo($)} which does not change in coordinate space.50)) and 3 is the vector whose three components are Pauli's spin matrices.v . l ) . can then be represented as a product of only one spatially varying function py(x)and a spinor . The two spirior components cpx(x.0).spin motion involves a dependence of p(x. in consideration of spin. . which is called spin-ovhit intemction. As orbital motion involves dependence of the wavefunction p ( ~on the space coordinate x. (2. can be represented by the following additional term H. however.e. this may be done by specifying another quantum number u for the spin motion along with the quantum number v of the orbital motion. 'I'hus. in the oneelectron Hamiltouian: H.)} in the product space of the ordinary Hilbert spare and tht.55) In general. u y .=(. s) can then be written as i). Then the components of are u.55) in Hartree approximation t.z1 - 4 (below the latter value will be written as =_ -. fiLnrtion.

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

T h c spinor components cp~.61) The Erst term on the right-hand side of this cquation is t. 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 (2.37) does not account for the exchange hole. that for the ground state with total spin 0.61) also shows that. The exchange potential proofs to be attractive. although its value is the same for spin-up and spin-down states. In actual calculations one often uses a local approximation for Vx(x).x is non-local.55) in such circumstances.and the total potential reads V(X) = K(x) + VH(4 + W X ) . the exchange potential . the exchange potential acts only between electrons of the same spin.2. Equation (2. the Hartree and exchange potentials are understood as those for the . and. It can be shown thilt theii action on the coordinate dependent factor of the oncparticle wavefunction cpl. and half are in spin-up states.(x. are of thr 8%) form (2. The factor of $ reflects the fact that. is called Hartvee-Fock approximation Thereby. which is to be expected: the anti-symmetric form (2. Formally.60) In the case of negligibly small spin-orbit interaction. unlike the Hartree potential. The effect of the exchange potential on the wavefunction p ( ) is represented by an integral operator. the orbital state may be characterized by a separate quantum number v t . The second term corrcsponds to the exchange potential. The dyynmiicd problem 77 somewhat different than that in the Hartree equation.heHartree potential. firstly.61) is called the Hartree-Fock equation. secondly. and the spin state by a separate cpiantum number m i . (2. The sum VH(X) Vx(x) of the Hartree and cxchange potentials can then be written in a relatively simple form.(x)takes the form + (2.60) and (2. the so-called exchange potential Vay(x).2. half of the electrons are in spin-down states. which underlies it. In this way the magnitude of the exchange potential is influenced by the existence of electron spin..wo spin states associated with each wavefunction cpvk(x). and the oneparticle approximation. The improved oneparticle Schrodinger equation with the potential of (2. It contains an additional contribution.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. it differs from the first term by exchanging the states at ’ the two positions x and x . The factor of 2 results from summing over the t.

g .t i a m of an electron system. Their excitation quanta are called plasmons. 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. Examples of many-particle excitations include two-particle ezcitation. Collective many-particle excitations are excitations of states in which all electrons of the system participate in comparable measure. Fetter and Walecka. are correlated contrary to the assumptions implicit in the f oneparticle approximation. the so-called ezcitan. hbrikosov. A comprehensive analysis of this problem i s far beyond the scope of the present book. Madelung. in fact do not diagonalize tbis Harniltouian ezactlv. Secondly. Callaway. 1974. 1976. are called correlation effects. there are non-vanishing offdiagonal elements. one has tt. Electronic structrrre of idea? crystah ground state configuration v i of the N-electron system. the exart. Readers who are particularly interested in correlation effects will find discussions in a number of textbooks (see. They form a direct electronic analogy to the lattice vibratious of the atomic cores of a crystal. even today. In particular. Below we summarize some results ~ . 1981). I other terms. is not completely solved. these excitation energies depend on the configuration of the system. e . configuration dependence. The consideration of correlation effects stands along the most difficult problems of solid state thmry which. but. since their separation by a distance of about a Bohr radius is more probable than all others. Harrison.5 of an electron and a hole which are bound together by their Coulomb Interaction. The excitation energy of such a hound electron-hole pair. first of all. The effects of the electron-electron interaction. Examples include the plasma o s c i l . is smaller than that of the excitation energy of a free electron and hole pair. an effect which is termed configuration interaction.eigenalates of the N-elwtrronsystem n are not oneparticle excitations! but many-particle excitetians. This interpretation presents the correct concept of correlation in other cases also the states of the electrons are no longer independent o each other. differing by the binding energy of the pair.78 Chapter 2. The exact eigenstates of the total Hamiltonian are linear combinations of diflerent Slater determinants. Correlation effects Correlation effects are. 1978. Gorkw. 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. Ziman. 1971. which are still neglected within the HartreeFock approximation with configuration independent Hartree and exchange potentials. as had been the case for individual Slater determinants. md Dzyaloshinski. Slater determinants which in Hartree-Fock approximation are considered to be eigenstates of the total Hamiltonian. and the corresponding energy eigenvaluea are no longer s u m of oneparticle excitation energies. 1963.

e. are variational parameters. while keeping their norms (cpudlqv.(x)and. therefore -xi (2. This requires the vanishing of the variational derivative of the functional E o [ n ( z ) ] E. of The total energy functional Eo[n(x)] the ground statr may be decomposed into several energy contributions. the Hohenberg-Kohn theorem. N.) constant. The one-particle Green's function is governed by the Dyson equation. Density functional theory. .63) In this functional derivative the value of cp:t(x) at a certain point x is taken as an independent variable. This method relies on a theorem. The oneparticle wavefunctions determine the ground state density by means of the equation (2.2. the real parts of these poles are the energy levels. that the density enters at every point x.. through an integral over X . we will concentrate on oneparticle excitations. namely. the total envrgy Eo[n(x)]is minimized. the wavefunctions cpv. where the factors E . Correlation effects on one-particle excitations may be treated by means of the Green's function theory of many particle-systems.(cp. moreover. which contains correlation effects through the so-called mass or self-energy operator. the external potential energy E c [ n ( x ) ] the Hartree energy E w [ n ( x ) ]and the . that the total energy E o [ n ( x ) ]depends on the oneparticle wavefunctions only through the ground state density n. i.62) where cpvi(x) denote the one-particle states which. are populated by electrons z = 1.. Another method which works well for oneparticle states involved in the ground state of the many-particle system is known as density functional theory.) with respect to p:*(x). and the imaginary parts are the lifetime broadening energies of the one-particle excitations). Correlation effects on one-particle excitations. with respect to which the common derivative is taken. According to the variational principle of quantum mechanics. This implies. the kinetic energy E ~ & ( x ) ] . . in the ground state of the N-electron system. The poles of the o n e particle Green's function in the complex energy plane represent oneparticle excitation energies (more strictly speaking.Ip.(x) adjust so that. The dynamical problem 79 which will be needed in Chapter 3. In doing so. 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. individual electrons and holes moving in the force field of all other electrons as well as in the force field of the atomic cores.2.. first of all.2.

expression (2. and the Hohenberg-Kohn theorem enforces this for E & t ( x ) ] .tn[n(x)] to be specified. By definition. For the waluation of the variational equation (2. 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. per ) electron. In this case the density n ( x ) is a constant n in space. (2. Electronic structure of ideal crystals exchange and correlation energies which are usually summed in the exchangecorrelation energy E x c [ n ( x ) ] . The total exchangecorrelation energy Exc(n) of a weakly inhomogeneous electron gas of density n ( x ) should then be given approximately by the expression (2.80 Chapter 2. it follows that (2. and E x c ( n ) reduces to an ordinary function of n.67) has Finally.Thus Eo[n(x)] Ekin[n(x)l Ec[n(x)l &dn(x)l = + + + Exc[n(x)l. need the explicit functional form of EkznIn(x)l.(x) iu given by (2. The LDA starts with the homogeneous electron system without any external potential.68) suffices.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 (2.69) For the rcmaining functional derivatives.. however. Its variational derivative with respect to p. n ( x ) Ix' .65) E ~ [ n ( x =] ) 2 // R R d3x'd3x n(x') . we have (2. It is usually taken in a local approximation called the local density approximation (LDA).70) .66) The functional E x c [ n ( x ) ]is less obvious.64) are functionals of n ( x ) .XI ' (2.63) we do not.64) and E ~ [ n ( x are easily obtained as )] The functionals E c [ n ( x ) ] (2. the kinetic energy fuIictiona1 E:k.

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. A misinterpretation of this kind may lead to large errors.2. one arrives at (2.B the Bohr radius (Hedin. 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. with the potential V(x) given by (2.2. This applies. the . in particular. various Pxchang+ correlation potentials have been proposed.4s rompnred t o the oneeleclron potential V(X) of the Hartrw ur Hartret-Fock equations. the eigcnvalucs of the Kohn-Sham equation cannot be understood in the sense of oneparticle excitation energies of the N-electron system. Th? electron ind~x has heen omitted a here bwauw thP equation is the bame for all electrons. The dynamicd problem 81 (2.75). However.rS/2l. as it is possible for the eigenvalues of the IIartree or HartrePFock quations according to Koapman's theoiern. The resulting erroneous gaps are about 50% smaller than the experimental values. for exaniylr Lkc(x). however. Lundqvist.72) where (2. is known as Kohn-Sham equatzon.63) t h e frlnctionrtl drrivatives obtained above. 1971).76). defining the energy gap. Relation (2. Suhstitiiting i n h q u a t i o n (2. Generally.71) (2. TJsing this procedure.75) with v(x) = VC(X) I Vrr(X) + i<Tc:(x) (2.76) as an effective one-elcrtron potential. that of the Kohn-Sham equation additionally accounts €or correlation effects.7734 z In with z . . The physical significance of tlir solutions of the Kohn-Sham equation is.73) denotes the ~xcliangPcnrrelation potential. where rS = and CI. to electron-hole excitation energies in senlimnductor crystals. less direct than that of the solutions of thP llartree or Hartrw-Fock equations.- ( : ) 1/3 e2n1j3[x)[I + 0.

The symmetry of the crystal is transferred directly to the potential V(x).53) is endowed with corresponding symmetry properties. where the ( N 1)-electron system applies for electlan excitations and the ( N .82 Chapter 2. Consequently. for example. and the N-electron system. with minor modifications. also can be obtained in this way. there are certain general properties of V(x) which do no1 depend on the particular material nature of the crystal. we restrict our considerations here to crystals their space groups are symmorphic. on the positions of atomic cores. i s treated in Appendix A. while screw rotations and glide-reflections are excluded. on the one hand. As we already know. 2. However. The dependence of the total energy on external parameters as. rotations. 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. + 23 .53) is specified by the form of the potential V(x) which is different for crystals of different chemical composition and atomic strurlure. for non-symmorphic ones.1)-electron systems.64). Rotations. In doing so. reflections as well as rotation-reflections. a crystal remains invariant under a transformation by an element of i t s space group. the Schrsdinger equation (2. we initially neglect electron spin.77) . It turns out that the results derived for symmorphic space groups arc also valid. The oneparticle excitation energies may be obtained as the differences of the total energies of the ( N t 1)-or ( N . reflections and rotation-reflections of the point group of directions transform a given crystal direction into a physically equivalent one. Minimizing the total energy with respect to the core positions yields the atomic structure of the crystal.1)-electron system for hole excitations. 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. and with it the particularly iniyortant case of the diamond structure. tRx =x + R. General properties of stationary one-electron states in a crystal The oneelectron Schrodinger equation (2. These are groups which contain solely translations. on the other hand.3. The general case of non-symmorphic space groups. (2.1 Symmetry properties of the one-electron Schrodinger equation For simplicity. We shall first describe these and then explore their implications for the stationary oneelectron states cpu(x).

the uaJform orthogonal niatriw$.80) j we may rewrite this relation in the form (2. by definition: contains all symmetry elements of the crystal. For the symrnorphic space groups considered here. reflections and rotation-reflmtions of the point group of directions. By means of this relation each opeiator a is uniquely associakd with a corresponding matrix aV. As in the case of translations. we also assign operators to rotations. If the thee primitive . However. which we already encountered in Chapter 1.81) from which it follows that the transformation a . 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.e.may also i be understood as a counter-tra~sformation thc coordinates with fixed basis of vectors. the translation gioup is B subgroup of the space group which.3. These operators also art on the spatial vectors x.78) with ov as real coefficimts. i. We define (see Appendix A} (2. and W P denote them by the symbol a and call them point symmetry operataorw. t or t ~ r of a translcttion t~ and a point syrnrnetrg operation a. Applying a . xj are the com- (2. the utJ arc not iu general orthogoual matrices. Since an ~ r arbitrary position vector x may be represented in a basis spanned by the three primitive lattice vectors a .a 2 and a3. this holds only for the primitive cubic lattice. Since the lattice translation operators are symmetry dements of the crystal. Thus. General properties o f stationary oneelectron states in B crystal 83 The set of all lattice translation operators forms the translation group. each element y may be thought of as a product 0 . which was ariginaIly defined as a transformation of the basis vectors a with fixed coordinates zz. their inverse matrices are the same as their transposed ones.79) with respect to the three primitive lattice vectors aj. it suffices to s p e d y the &ect l of a on these.2. lh coordinate counter-transformation takes place with the . Indeecl. lattice vectors a are orthogonal and of the same length. The ponents of x with respect to these vectors. and is not true fur all other 13 Binvais btticrs.

as the proprrty o f t h e original crystal at the inverse transformd position.W) follow. One says that t~ and 1y commute with the potential V ( x ) .B A as abbreviation for the commutator of two operators A and 3.89) (2. It is striking that the operators t~ and a act on S(x) in such a way that x ifireplaced by tR1x or m .lX) . To express this fact formally.l x . This is the Sam?. Formally the definitions (2.82) remains invarianl under the transformations t R and a .85) (2. 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 ) . UV(X)= V ( d X ) (2. the kinetic enerw operator ?' = p2/2m.v(x).rtl a -1 .86) = v(xj. because ( q c q ) .78) of the basis vectors. Electronic structure of ideal crystals transpose matrix a j i of aij. B ] = A B . Applying these 2 definitions to the potential V ( x ) and simultaneously requiring crystal symmetry. then this mist also hold for the potential V(x) with which the tramformed crystal acts on an electron at position x. with IA.' . For t~ this follows directly . as one might hme x expectd. but not by k ~ or c k x . w r have tnv(x) = V(t. (2. Further application of these opwatm relations to a wavefunction p(x) one obtains and since ~ ( xmay be chosen arbitrarily.83) (2.84 Chapter 2.l x ) . in contradistinction to the transformation (2. Such cornmutivity also holds for the uthcr contribution of the Hamiltonian. This is t o say that (2.84) a S ( x )= S ( a .84) giiarantee the correct multiplication order of two no11 commuting operators -1 under the fiinction symbol.83) and (2. howewr. The rhosen deftnition strms from the rrcognition that the transformed property is that of the transfarmrcl crystal at the original position x. the relations ) (2.

2 Bloch theorem Let p~ be an cigenfunction of H having eigenvalue E . while for a it follows from the fact that p2 is the square of the length of the momentum vector.92) (2.1 = 0. Then the stationary Schrodinger equation (2. as w l as from the observation that the length of a vector is not changed by a el translation.96) and t h e normalization condition Through the periodicity condition (2. 3.91) Taken together with ('2.ates to follow.2. the symmetry group. also t ~ p ~ ( x ) .i h V .961.53)holds. (2.TI = [a. one has the periodicity condition with respect to a periodicity region VE(X -k G a j ) = ( P E ( X ) 1 J . 2. . H (2. these relations yield [ t R . We will use it extensively in the analysis of symmetry properties of stationary oneelectron st.2.HI = 0.uE(x) and g p ~ ( x are ) eigenfunctions of H having ihe same cigenvalue E . ] = 0. Thus.95) In addition. whrrc the state index v has been replaced by E . (2. and V = V x + ~ .3.3. rotation or reflection. HVEW = EPE(4. one also has The latter relation expresses in h a 1 form the implication of crystal symmetry for the Schrodinger equation. 2 - (2. one has .90). ]u. [tR. along with cp~(x). Thus. w. The commutivity of t~ and a with H has the consequence that. which at the outset includes an infinite number of lattice translations.89) and (2.93) Since the elements g of a symmorphic space group may be written as products of t~ and C Y . 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 = .

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

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

I I (2. The proof is based on the normalization of p~ according to equation (2.103) for c(R). it follows from relation (2. Employing (2. we claim that pEklkzks(x) can be written in the form (2.88 Chapter 2.107) together. Ic3 on c(R) and P(R) will be suppressed temporarily).103) is verified at once.108) Comparison of the last two relations immediately shows that (2. whence (2.114) where u ~ k ~ k ~ k denotes a lattice-periodic function. On the other hand. equation (2. As such P ( R ) must have the form (2. r3 of R. Secondly. k2. Electronic structure of ideal crystals (2.108) is also true. such that.103). 7-2.108) now yields exp[iP(Rl+ Rdl = exp[iP(R~)I~xP[WWI. for any ~ ( x ) lattice vector R.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. We now proceed to the eigenfunctions of the translation operator. .106) and (2. This means that P(R) is a homogeneous linear function of the components TI. (2. . c(R2) must hold.105) (the subscript indices k l . which leads to (tR(PE t R P E ) = ( P E (PE). we show that c(R1+ R2) = c(R1) . we use the following obvious relations: (2. To prove this.1) t P(R2).107) Considering (2.112) (2.104). Employing ( ~ ~ k(x)to denote the eigenfunction having eigenvalue Ck1kzk3 ( R ) ~ k ~ k ~ of equation (2.102) that (tRLPE tR(PE) I -I c(R) l2 (PaE I P E ) .97).113) P(Ri t R2) = P(R. (2.

k3 At the outset. what eigenvalue of t R pertains to it. The real numbers kl. General properties of stationary oneelectron states in a crystal 89 UEklkzk3(X . This results in which we know to he true. we form tRfffpEklkzk3 = t ~ p ~ k ~ k ~ k ~ (and 'obtain the equation a . k ~ k .k2. k3 is their transformation law under point symmetry transformations a in coordinate space.102).f3klkZ~3(a-1R) explicitly using equations (2. The question arises whether a p .114). In order to answer this question. 2.114) in order that the normalization integral of UEklkzk3 (x) with respect to a primitive unit cell be 1.~ ) ) = e x ~ l i P k .3 Reciprocal vector space and the reciprocal lattice The starting point for understanding the nature of the components k l . if so.114) are referred ~ x ) to as Bloch functions and the factors u ~ k ~ k + ~ (as )Bloch factors.117) ~ ) .115) The factor l/& with 0 = G300is introduced in (2. g k l k Z k 3 ( x ) is also an eigenfunction of the translation operator and. However..2. Recalling x k ( ~ ) that the p ~ k ~ k ~ are~also simultaneously eigenfunctions of the Hamiltonian. as we will soon see. The proof of (2.99) 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 . This will now be explored. it is clear from equation (2.82). ~ k ~ ( k ~ ( ~ ) The latter relation means that a p ~ k ~ k ~ is indeed an eigenfunction of ~R)]. the translation operator t R with eigenvalue e ~ p [ i P k ~ k ~ k ~ ( a -Evaluating . but one in a space which is reciprocal to coordinate space.3.3.104) and (2.R) = UEk1kzk3(X)' (2. k2. k3 characterizing the various Bloch functions may he understood as components of a vector. The functions p ~ k ~ k ~ k of ((2. we have . Transformation properties of kl.114) may be carried out by verifying that functions of the form (2. 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. ( ~ ~ ~ ~ R ) l ~ ~ ' ~ ~ k ~ k(2.122.114) obey equation (2. this is not a vector in coordinate space.

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

that is. bz. i = cxk. the matrix LY which describes i the rotation or reflection of the a is different from that which transforms the bj. unit vectors are the two basis sets the same).124) may be used to express the phase . The lengths of the reciprocal basis vectors bj are determined by the three equations which follow from (2. bz 00 2x 27r 00 x a1 1 . Consider now an arbitrary vector k of reciprocal vector space.&kka(R) of the eigenvalue (2. (2. the components bi will transform with the transposed inverse matrix 05'. this induces the same rotation or reflection of the rwiprocal basis. with the inverse matrix a.122) or (2. b3) is rigidy joined with the direct basis (al: ag) a2. In other words. since the recipaz. Using this result.124) i As we know. the inverse matrix describes the same rotation OF reflection of the reciprocal basis a the s transposed matrix docs fur the direct basis.2. we obtain kkb.123) Here Ro = a .a3) are orthogonal rocal basis is different from the direct one (only if (al. the vector components themselves transform in accordance with the transpose of the transformation of the basis vectors. aa follows: bl= -[a2 x q]. which can be written as (2.'.122) for j = a.103) of the translation operator in the more compact form .125) The reciprocal vector k of (2. [a2x a 1 is the volume of a primitive unit cell of the crystal 1 3 lattice. the a are mutually non-orthogonal. Since the transformation of the reciprocal basis calls for the inverse matrix.4mong themselves. Using equation (2. and will transform when the latter is tranaformd However.122) determines the reciprocal basis vectors bj uniquely.3. Because of these relations the 'reciprocal' basis (bl.123) one may easily show that the bj are transformed with the transposed inverse of the transposed matrix u p which transforms the q . as follows immediately from the defining equations (2. (2. b3 : -[a1 2x Qo x az] . General properties of stationary oneelectron states i a crystal n 91 . the equation set (2.121)describes the transformation of the components of a reciprocal vector.123). This verifies our earlier assertion that quation (2. the bj are in general non-orthogonal to the extent that . Altogether. If one s u bj et s the direct basis to a rotation or reflection.

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

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

and it will now be explored in some detail.95). For example. (ii) The reciprocal lattice of a reciprocal lattice is the direct lattice. and. then the same holds for the corresponding reciprocal lattice. 2. conversely. namely the 1 Bravais lattices.v(x) 1 UE&) = EUEk(X). (2.e. 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. one has E(k) = (H2/2m)k2. If one substitutes i p ~ k ( x )(2.one obtains the following eigenvalue equation for U E ~ ( X ) : Izm -P ( 1 t rzk)2 -1.3. of course.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. i. In fact such B connection does e x i s t .136) The k-dependence of the operator in this equation transfers to the eigenvalue E. primitive lattice vectors. The reciprocal lattices bear a close relation to the corresponding direct lattices.135) with arbitrary integers K j . a face centered cubic reciprocal lattice corresponds to a body centered cubic direct lattice. more compljcated dependencies than this. The Bravais types of primitive direct lattices are the same as those of their reciprocal lattices. E becomes H function E = E(k) of the quasi-wavevector k. 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. A reciprocal lattice vector K is then given by the relation K =CKjbj 3 (2.128) into the Schriidinger equation (2.94 Chapter 2 Electronic structure of ideal crystals . Some general properties of E(k) follow. For a crystal one expects. The reciprocal lattice of a centered direct lattice is also centered. . one also has 14 different 4 lattice types in reciprocal space. 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. (iii) If the direct lattice is primitive. As in coordinate space. The specific form of the function E(k) is determined by the particular shape of the periodic potential V(x). a body centered cubic reciprocal lattice corresponds to a face centered cubic direct lattice.

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

k varies over the entire reciprocal space. It arises in conjunction with the degeneracy of the eigenvalues ck(R) of the translation operator tR.e. Translation symmetry: Extended and reduced zone schemes The lattice translation invariance of H has a remarkable consequence for the eigenvalue function E(k). the latter is -2k.K ) holds in general. this description i s highly redundant. the energy cigenvalues g ( k ) do differ. Then we must accept. Since both Bloch functions have the same eigenvalue. that an infinite number of different energy eigenvalues are assigned to each k-vector. and to each vector k we associate only one k-dependent energy function E(k). any reciprocal lattice vector. With respect to the eigenvalues of the translation operator.R (2. Specifically.96 Chapter 2.140) obtained by means of spatial symmetry. and T % as integers. Independently of the actual value of K. if k is allowed to vary only over a primitive unit cell rather than over the whole k-space.3 illustrates these connections. if the point group of the crystal does not contain the inversion. 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.. Electronic structure of ideal crystals time reversed Bloch function of wavevector k has wavevector -k.141) This relation has additional significance. have the same eigenvalue of thc translation operator. In the representation scheme employed thus far. since one encounters the same eigenvaliie an infinite number of times. Therefore we obtain the full spwtrum of eigenvalues of t R if k varies within a particular primitive unit cell of k-space. all wavefunctions (PEk+K with K . namely all those which follow frotn E ( k ) by means of the prescription .R1 (2. 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). so that E(k1) f h’(k1-t. The corresponding k-vectors will br denoted by kl. however. beyond that of relation (2.143) with K . i. (2. one obtains E ( k ) . Table 2. 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.E(-k).142) Ck+K(R) = e which follows directly from the relation K .

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

that lattices have fewer point groups than there are point groups of equivalent crystal directions. P2 H o = -. the solution of the unperturbed problem must be known. and that these energy bands arise by varying the quasi-wavevector k over the first Brillouin zone. or a part of it.4 Schr6dinger equation solution in the nearlyfree-electron approximation It is well known that the Schrodinger equation can be solved approximately if the potential. Moreover. Even if it is not to be expected that this will yield results which are quantitatively accurate.147) . The next-lower lattice point group would not contain the needed point group of directions. however. we thus arrive at the important conclusion that the spectrum of allowed energy values of crystal electrons will have the form of energy bands. Electronic structure of ideal crystals We know. Having started from general considerations and obvious conjectures. some qualitative understanding can be gained in this way.145) The perturbing operator H I . At this point. 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 prove that this is indeed the case for the branch Eo(kl) in the next section. 2. which together with Ho forms the total Hamiltonian (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.98 Chapter 2.e. To apply this procedure. then the unperturbed problem is that of a completely free electron. represents a small effect which may be treated by means of perturbation theory. 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. If one takes the periodic potential as a perturbation. The corresponding Hamiltonian Ho is simply the kinetic energy of the electron. i. 2m (2. i + is then the periodic potential H I = V(x). we will treat the entire periodic potential by means of perturbation theory. 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 = 0.146) H = Ho H . (2.

152) is proved in the theory of Fourier series. such that and -yCpp(x’)Cp. Schriidinger equation solution i the nearly-freeelectron approximation n 99 In perturbation theory. more exactly. . the exact eigenfunctions are expanded in power series. = Eo(k)Cpg. The k-summation of (2. In this discussion.4.152) and (2. Cpk and eigenvalues E ( k ) E(k) = Eo(k) 6E1(k) + + 6E2(k)+ . The energy eigenvalue Eo(k) of zero-th order for pg is (2.154) 2m We will assume at the outset that this eigenvalue is not degenerate. This leads to no ambiguity since we work in the extended zone scheme.154).151) may be easily verified by direct calculation. the zero-th order solutions must form a complete orthonormal set of functions.153) are in fact valid for the solutions (2.(x) = 6(x’ .4. we suppress the energy index E of the eigenfunctions for the sake of brevity. here with respect to the periodic potential V(x).149) with respect to the perturbation potential.152) is extended over all points of the infinite finely meshed net of Figure 2. E (k) = -k2 0 Ti2 . The zero-th order terms obey the equation Hop. The two relations (2.152) must hold. where the energy is a unique function of the quasi-wavevectors k.153) of equation (2.x) k (2. (2. The validity of the orthonormality relation (2. and the completeness relation (2.150).2. It is not possible to exclude degeneracy completely because wavevectors k of the same length lead to the same energy eigenvalue (2. (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’. .150) In order that the perturbation theory be applicable.

the correction 6 ~ : the wavefunction takes the form to (2.160) we arrive at the result Using this result.156) are given by (z.1551.159) (2. (2. The off-diagonal matrix element of the potential involved in (2.100 2.157) into a sum o f integrals over the primitive unit cell Qo(0) at R = 0: Noling that (2.157) Because of the lattice periodicity of V(x) we can transform the integral over the periodicity region in (2.162) and the total wavvcfunclion pk = ‘ ! p t 6pk is given in this approximation as . Electronic structurc of ideal crystals Non-degenerate perturbation theory h accordance with the procedures of quantum mechanical perturbation t h e ory.156) The energy correction 6E1(k) of the first order i s the average value (cpg I V I pi) of the periodic potential. This value may be set equal to zcro. we have (2.1 Chapter 2.155) (2.4.

: Below. (2 166) In such a case. However.4.0. 1 k.128) b r energy eigenfunctions of the crystal Hamiltonian.161) as (2.151) 12= 0.162) and the enerffi eigmvtrlues (2.2. since 1 k If jk KI. (2.16 7) 2 This equation can be solved geometrically. and correspondingly they are not capable of significant constructive interference. (2. It is obvious from Figure 2.165) The corrections to the eigenfunctions (2. That the perturbation theory according to formula (2.162). we will accommodate this case and discuss the corresponding degenerate perturbation theory.154) for E o ( k ) .5 that the tIps of the corresponding k-vectors lie on a plane perpendicular to the vectors K or -K. 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. In this. Such planes are familiar from the theory of X-ray diffraction by crystal lattices.16 4) The second order energy correction E2(k) may be determined using (2. 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. 6 ~ corresponding to the scattered part of the latter. Actually. 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. the denominator may even vanish when E"(k).166) holds.we get from (2.Eo(k I K ) . SchrMingw equation solution in the nearly-fieet3-electronapproximation 101 One recognizes that this has the expected Bloch form (2. 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. with the states 9 and cp:-K degenerate with each other. just such a degeneracy exists if equation (2.163) yields the Bloch factor as (2. but first we analyze the k-values for which the condition (2.166) is fulfilled. with this plane intersecting the vector -K at its half-length.K+ -IK + . I ~ basic premise for validity of non-degenerate perturbation P theory is violated. Moreover. They aTe called Bmgg reflectam planes. Using (2.

5: Construction reflection planes. 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. including X-rays. however. For k-vectors which obey the Bragg condition (2. Electronic structure of ideal crystals -& \ -K f Figure 2.6: 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. is that the amplitudes of the refiected and incoming waves should be comparable. of Bragg Figure 2. They are thus rapable of tor k constructive interference w i h strongly enhances the amplitude of this parhc ticular scattered wave.167). become idnitely large formally What is expectd. have almost the same wavelengths. If k is located exactly on the Bragg reflection plane.102 Chapter 2. 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. Actually.162). This follows immediately from the construction of the k h g g reflection plancs in Figure 2. T i is due t o the fact that. . one must apply degenerate perturbation theory. in this case. w h c h makes it the refkected wave (bear in mind that in the wave picture reflection represents an interference phenomenon). the incoming plane wave and the Ecaltered wave of wavevecK. the above results for elwtron waves were discoverd iisinE X-ray radiation. + + + The amplitudes of plane waves reflected at Bragg planes. w h h is no longer applicable under the conditions of reflection. according to formula (2. The scattered wave of wavevector k K is strengthened by interference. For incoming waves with k-vectors close to the Bragg reflection plane of the reciprocal vector -K.5. This contradiction arises from the misuse of non-degenerate perturbation theov.

173) For further evaluation of this expression. one proceeds as follows.IK 2 12= 0 (2. the Schriidinger equation leads to the following set of equations. whence ( Eo(k) .6. (2.4. Expanding the square root in powers of I Ak I and terminating the series with the second order. we find 1 + Eo(k + K)] f -\/[Eo(k) . Schrdinger equation solution in tho nearly-free-electronapproximation 103 2.E V(K)* (2. so that 1 ko.E For the set to have a non-trivial solution. 2 E*(k) = Eo(ko)f I V(K) I 4 li2 [ jpK2 1 f 2m I V(K) I] Ak2. The perturbed eigenfunctions cpk are sought as linear combinations of the two (almost) degenerate eigenfunctions and (p& in zero-th order.172) (2.174) .171) V(K) Eo(k$ K ) . The same holds for the vector k K.[Eo(k) 2 (2.E V(K) = 0 V(K)* Eo(k+ K ) . we assume that Ak is directed parallel to K (see Figure 2 .170) with co and CK coefficients to be determined.4. The two solutions are E = Ek(k) with 1 Ek(k) -. According to quantum mechanical perturbation theory for the case of degenerate zero-th order states.168) holds for a particular reciprocal lattice vector K.2.169) is then a vector close the Bragg plane involved. In the lowest non-vanishing order of perturbation theory. its determinant must vanish. writing + ci p ( I o x= cocp:(x) PF ( ) +C K d + K ( X ) (2.2 Degenerate perturbation theory Let ko be a point on a Bragg reflection plane. We denote a small deviation from ko by Ak where 'small' means that I A k I<<] K I.Eo(k + K)]*+ 4 I V(K) I*. Eo(k) . 6 ) .. A vector k of the form k=ko+Ak (2. as it lies close to the parallel plane in Figure 2.K+ .E must hold.

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).104 Chapter 2.174) provides the following picture (see Figure 2. with the exceptzon of the Bragg reflectLon planes where. the function E ( k ) and the energy spectrum remain continuous. the upper branch with positive curvature.e. The following statement remains true also in the general case. and the lower with a negative one.ll'(K)I.7). i. provided that the corresponding Fourier components I'(K) of the periodic potential do not vanish. for Ak = 0. 271 generat. In regard to the shape of the function E*(k) close to the Bragg planes. The result derived here by means of perturbation theory is also valid well beyond the framework of validity of this approximation. an energy gap appears as a result of the periodic potential.7). the relation (2. This occurs at all Bragg reflection planes. This means that. + The energy f u n c h o n E(k) LS continuous everywhere in k-space.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. splits into two different eigenvalues which are shifted by IV(K)I to higher and lower energies. respectively. Except for the Bragg planes. discontinuities occur and the energy spectrum exhihts gaps.174) since the applicability of perturbation theory is restricted in validity by 1 V(k) I << h 2 K 2 / 2 m . The latter observation follonrs from (2.which means that the sign + . + The remarkable feature of this result is that the 2-fold degenerate energy eigenvalue Eo(ko) = Eo(ko K ) at the Bragg reflection plane. In the formerly continuous energy spectrum a gap arises at this plane (right part of the figure). in the formerly continuous energy spectrum of the free electron. Between them there is a region of width 2 I V ( k ) I where no allowed energy values may exist (see Figure 2. Electronic structure of ideal crystals Figure 2.

1 Brillouin zones Definition Consider. in which the quasi-wavevector k varies o d y over a primitive unit cell of reciprocal space.3. 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. Simplicity of the description calls for the discontinuities of E ( k ) to occur only on the boundaries of the unit cell. each of an infinite number of choices for this cell can be used.5. The smallest will be the Wigner-Seitz cell at K = 0. The prescription for the construction of the Bragg planes (see section 2. It contains the . 2.1671. namely that it have discontinuities only at Bragg reflection planes and otherwise be continuous. as one may easily demonstrate.4) makes it immediately clear that the Wigner-Seitz cell of the reciprocal lattice at K = 0 has the desired property . 2. Band structure 105 of the angular bracket in (2. These bodies are arranged and enumerated according to their volume. there is also the reduced scheme introduced in section 2. but has no other such planes in its interior.5 Band structure The perturbation-theory calculations of the preceding section were carried out in the extended zone scheme for E(k}. The reason for this is that the non-central Wigner-Seitz cells are cut by Bragg planes. next-largest body. This means that within the Wiper-Seitz cell of the reciprocal lattice at K = 0. However. is equivalent to the question of whether there exists a primitive unit cell which is bounded by Bragg planes. The question of whether there is a primitive unit cell which guarantees that. is described as simply as possible.5. the function E(k) is continuous. Alternatively. and in its interior it is devoid of such planes.it is bounded completely by planes which obey equation (2. centro-symmetric bodies which contain the origin and are entirely bounded by parts of Bragg reflection planes. In this.174) is always determined by the second term. has the volume of two Wigner-Seitz cells. The correct procedure goes back to Brillouin and will be described below.2. namely Bragg planes. Here. The second. 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. with E(k)continuous in the interior. in k-space.

These difference bodies are called Brdloum zones (abbreviated 8 8 s ) . 10 Rrillouin zones or H sqimre plane 1al.175) .). . The first B Z for two important 3dimensional lattices. If one removes the first body from the second. This conhtruction may be carried further. lattice is attached k such that k. the frr lattice and the hexagonal lattice. In Figure 2. then one obtains a hollow body of the volume of one Wigner-Seitz cell. 1953).K(k.) of the reciprocal .tic:e.) represents a vector kl of the first + BZ. . are shown in Figure 2. accordingly.8 the first 10 Brillouin zones are shown for a 2-dimensional square reciprocal lattice. The v-th body i s called the v-th R%.e. We will derive the shape of the first of them below. but contains no siirh planes in i t s interior.K(k. Electronic structure of ideal crystals ZONE 1 2 3 4 5 6 7 8 9 1 0 Figme 2. (2. Focusing on a point k of the v-th R Z .106 Chapter 2. 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. It i s boiindd by Bragg planes. the first B Z .9.8: The first. and has no such planes in its interior. . the Wigner-Seitz cell at K = 0 is. i. (After Brillouin. a v e t o r K(k. which is bounded by Bragg planes inside and outside. first body jointly with the Bragg planes bonnding i t . k =k l .

each k. (right) the hexagonal lattice of wurtzite and selenium structures.(kl) is defined within the first BZ.. 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. Band structure 107 Figure 2. another reciprocal lattice vector K(kh) may be necessary in order that kh .175) is unambiguous in both directions ..8 and 2.2. Formally. We omit the formal proof for this important result here. The unique function E(k) over the whole k-space is mapped into the multivalued function E. By this assignment a multi-valued function E. . this is expressed by . defined above by relation (2. . The correspondence of the points of the v-th B Z to points of the first B Z given by equation (2. instead of k.(kl) within the first B Z . another point kh of the v-th B Z is chosen. is just the set of K-vectors which defines the internal boundary planes of the v-th B Z .144). K(kL).5.K ( k l ) shall be a vector of the first B Z . corresponds exactly to one kl. For the square lattice it follows immediately from Figures 2. . The term ‘displacing’ would probably provide a better description. The folding operation (2. If. There.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 . It states that the value E(k) at a point k = k.). zincblende and rocksalt structures. which arises if k. Its validity in the general 3-dimensional case is clearly plausible. varies over the whole v-th B Z . the external or internal boundary planes of v-th B Z may be translated to the interior of the first B Z . The transfer of the function values is. The set of reciprocal lattice vectors K(k.9: The first Brillouin zones of the two Bravais lattices which apply to many semiconductors: (left) the face centered cubic lattice of diamond. During such folding or displacing. and each kl exactly to one k.10. by folding the v-th B Z into the first. they border on other boundary planes of the v-th B Z . of the v-th B Z is assigned to that particular point of the first B Z which arises from k.

) in the extended zone scheme as may be seen by means of the degenerate perturbation tbwry in swtion 2.. continuity is not immediately . These regions are called forbidden zone8 or energy gaps. for in penetrating such a kl-plane the original vector k . (After Brillouin. which defines this boundary plane. . For those psrticiilar kl-planes srising from a bo~iirlaryplane of the v-th B Z . One recognizes that energy gaps orcur not only on the boundaries of the first BZ . I / is the so-called band andm Between the various function branches.E ( k i + K(k.9.e. the validity of this assertion is obvious. evident. However.176) We maintain that the branches E. (2.(kl)-values is thus obvious.(k) are also continuous on the particular planes in question.4. i.(kl) defined above encompasses some finite interval of values on the energy scale. of the Yth R Z jumps by the negative of the rcciprocal latticc vector. For points kl which correspond to points k of the interior of the v t h B Z . In Figure 2. and the dashed ones to an elwtzon in a weak periodic potential. the equation Ev(ki).)) E(kv). or energy bands.11 we illustrate the band structurc using the model of a 1-dimensional lattice. Thus the functions E. The solid curves correspond l o a rornplelely free electron.(kl) of the multi-valued function are continuous within their entire range of ddinition. The term energy hnnd for the set of E. 1953)).108 Chapter 2. within the fust B Z . this jump does not affect the energy eigenvalue E(k. Electronic structure of ideal crystals Figure 2.10: Folding of the second through ninth Rrillouiri zones into the first R Z for the plane square lattice of Figure 2. l'he whole s r t of functions R. Each of the function branches F.(kl) is referred to collectively as thr band structure. energy regions may exist in which no energy eigenvalues occur.

of outstanding importance in solid state physics. but also at its center at k = 0. Let p v k l denote the Bloch function of energy E. Unless otherwise specified.2. The folding procedure into the first B Z must also be carried out for the eigenfunctions of the Harniltonian. E. ) k v ( x ) . surface points of the first B Z are displaced to the B Z center.5. Thus. The changes caused by a weak. during folding. This is due to the fact that.(k) instead of E. periodic lattice potential are indicated by dashed lines. in particular. The first Brillouin zone is.(kl).11: Rcduction of the energy parabola of a free electron into the first B Z of a 1-dimensional lattice. Band striictiire 109 Figure 2. and the energy gaps from those points also appear at the center. the quasiwavevector will henceforth always be understood to lie in the first B Z . Thus we will write k instead of kl. which means.(kl) over the first B Z is by far the most common and frequently used description of the energy spectrum of a crystal.(kl) and of reduced wavevector kl. The Schrodinger equation for an electron in a crystal then takes the form . The representation of E(k) as a multi-valued function E. In the extended scheme the same wavefunction reads q q k . therefore.

The relation between the reciprocal and the direct lattices was discussed in section 2. -(I. which ah0 means 14 different first B Z s . I).178) The first RZ is the fully symmetric primitive unit cell of the reciprocal lattice. -(I. According to Table 1.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.180) a a a a = -(O. a a a 27r 2s -(1.Z). the primitive vectors of this lattice may be chosen in the form (2. Electronic structure of ideal crystals ff~v/c(x) = &(k)pvk(x).0).i. T). b2 = -(l. 1.2. I). 1.2. b3 = -(I. a (2.T.9.i). I. O 27r -(0.I). O . although not necessarily of the same Rravais type. 1.bl = -(I. 1.181) (2) 6 lattice vectors having the next-smallest possible length: 27r -4%) . -(I.3.( l . Two of them.179) . a 27r 2x . 2 2 2 The corresponding basis vectors of the reciprocal lattice follow from equation (2.l). -(T. Empty-lattice band s t r u c t u r e In Figure 2. T.T). 1.182) . a2 = .2n -(I. Accordingly. there are 14 different reciprocal Bravais lattices. which means the smallest possible length overall. T. (2. 1. These vectors read: 2n -(i. 1. (2. Similar representations are possible in 3 dimensions. are shown in Figure 2. where it was seen that each of the 14 direct Bravais lattices corresponds to a particular reciprocal lattice of the same symmetry. 2n 27r (2. -(I. a 0. a 0.T). with the result 27r 27r 2n .123). a 2n -(O.I ) . 1.T).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. a 3 = -(I.1). I). Below we demonstrate this for the face centered cubic lattice which applies to crystals of the diamond and zincblende structures.110 Chapter 2. the two that are most important for semiconductors.

the second and third BZ's are folded into the first. a 2?r 0. We will now reduce the energy parabola E(k) = (fi2/2m)k2 of a free electron along the A-line.185) With lattice constant a of 5 A.) in this relation. a 2R o . and latin letters to symmetry points on its surface (see Figure 2. the point at which a cubic axis cuts the B Z surface is X . Perpendicular to the three cubic axes it is bounded by squares. It is common to denote the symmetry points of the first BZ by capital letters. for points r = 2R o.(k) we have 71 E u . 1) (2.e. The center of the B Z . a A = -(o. and the connecting line between I? and X is A. a value of 5. Greek letters are assigned to symmetry points in the interior of the first BZ. In the reduced zone scheme we have E.12: Symmetry points and irreducible parts of the first BZ of the fcc lattice (left) and the hexagonal lattice (right). ~v(k).9 eV follows for Eo. for example.12). and set E. is I?.5. (2.184) 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.o) -(o.(k) = -k h2 ( 2m +K ( ~ Y ) ) ~ . and normal to the four space diagonals by hexagons. (2. x = -(o.183) with 0 < C < 1.9. Band structure 111 Figure 2. The first B Z of the fcc lattice obtained by means of these reciprocal lattice vectors is shown in Figure 2. ~ ) . For ty(k) .2. i.

i.e. 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. one can plot the band structure along other symmetry lines in the interior and on the boundary of the first B Z . were chosen in the above procedure. in the sense that we could have also chosen any other of the 14 Bravais lattices. and not &fold as for the fcc lattice at E = 4Eo. Also. Again. although for real fcc crystals the degeneracy at maximum can be only 3-fold. along with the band structure parallel to the A-line between 0 and L not given in Table 2. Such representations are. It is also consistent that the energetically high-lying bands display a relatively high degeneracy at the I?-point.4 we show the reduced energy functions ty(<) for the 14 vectors K. This was an arbitrary choice.(C) is obtained for 4 different K. a definite lattice. which is identically zero in this case.. a fcc lattice whose lattice points are not occupied by atoms. this result is not too far from the actual widths in fcc crystals. For a vanishing potential V(x).(k) over planes in k-space. i. Electronic structure of ideal crystals (2. since the latter would create a non-zero periodic potential V(x)if they were present.13 is that of an ‘empty’ fcc lattice.11 is about Eo.. the fcc lattice. In some cases the same value of the function E. 2nla.4. not caused by symmetry. The band structure shown in Figure 2. then we cannot take any empty lattice band structure but must chose the one for the lattice applying to the crystal under consideration. In Table 2. Nevertheless. one recognizes that there are k-points associated with the same energy value several times. Kvy. in units of where the K. i. uncom- .112 Chapter 2. together with those for 0. are the components of the vectors K. however. definite lattice exists because of its arbino trary translation symmetry. meaning that the corresponding energy bands are 4-fold degenerate.and A-lines. 6 eV. for example. A complete representation of the functions E. if we want the empty lattice band structure to resemble the band structure of a really existing crystal. In Figure 2.186) K.’s.e.e. In the 3-dimensional space available to us it is only possible to represent bands E.(k) over the points of 3-dimensional k-space would require a Cdimensional space.13 the content of Table 2. However. The width of the lowest energy band in Figure 2. one of them crossing another band at the X-point. Later we will verify that the band structures of real crystals and the pertinent empty lattice band structures have in fact common features.4 is illustrated graphically.11 such features are. and a definite lattice constant. but by the particular values of the potential. In Figure 2. as we will verify below. and not 8-fold as for the empty fcc lattice at the energy E = 3&. and any other lattice constants. As with the reduction along A. A degeneracy higher than %fold turns out be accidental.

as in Figure 2.2. one plots the energy against lines in k-space. Band structure 113 (KV&V. The question of what valws the energy band functions E.K. -4s a rulc.5.(k) were "L A r A Wavevector X Figure 2.(k) take outside the first B Z does not arise or is meaningless.) 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.13: Band structure of an empty fcc lattice. . since the E.13.

By periodic continuation. a necessary condition for continuity of the periodically continued function is that the original function.(k) must satisfy certain conditions on the boundary of the first B Z . This condition is also siifFicient.(kb) is defined by the periodic continuation and. defined only over the first B Z . the values of E. because a primitive unit cell contains only nonequivalent points.e.(ko).6). discontinuities will occur on the boundaries of the Wigner-Seitz cells.(ko). (2. In order to have continuity. These conditions follow from the fact that the boundary of the first B Z consists of pairs of equivalent parallel planes (see Figure 2. the E. it is equal to E. If one wishes to also consider the functions E. Tising continuity of the function &(k) defined over all kspace. as such.188) holds.114 Chapter 2. The most natural manner to do this is the periodic continuation. the periodically continued function will not be continuous in the entire k-space.as we will assume. We denote a point on one plane of such a pair by ko. This is the . thix value must coincide with the limiting value of E.(k) outside of the first B Z . obey the boundary condition lim E.188) where k is in the interior of the first B8. the boundary condition (‘2. Periodic continuation In this context. Therefore. then kb cannot also belong to it. since the continuity of the periodically continued function E. Electronic structure of ideal crystals just defined by transferring the function values from other B Z s to the first one.(k) if one approaches the point kb coming from the interior of the first B Z .(k) defined over the first R E . The question is what analytic properties does this function have? If one considers an arbitrary function.187) where k is a point of the first B Z . i.k.(k) = k k& - E. E. this property may be expressed in a more convenient way. reason why one continues the e n e r a bend fiinctions R ( ) which actually . and kb denotes the equivalent point on the other plane of the pair.(k) implies that equation (2.188) for the function E.(k) in Wigner-Seitz cells having centers at K # 0 are defined by the relation (2. Thus. one can of course extend each function originally defined only within the first B Z to the entire k-space. The value of E. and the continuity of the periodically continued function E.(k) are just different descriptions of the same property. If ko belongs to the first BZ. For this reason. one has to define them there.(k) already encompass the entire spectrum of eigenvalues as k varies over the first B Z . In order for the periodically continued func%iorrt o be continuous.

(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. mathematical theorems dealing with the types and numbers of extrema of periodic analytic functions may also be applied. We return now to a question which was previously explored in section 2. That it also exhibits the periodicity of the reciprocal lattice.periodically over the entire k-space.(k) is often very useful. one obtains the matrix at the original k-vertor. nand structure 115 have meaning only within the first BZ. To this end. that the E. The latter is manifpstly continiioiis. The continuity of the periodically rontinued function E. are continuous everywhere as periodically continued functions. one may verify as follows. where K is an arbitrary reciprocal lattice vector. and thus. This i s particularly important for the theory of the optical proprrties of semiconductors.3.(k) in the entire reciprocal space is therefore an immediate consequence of the periodicity of V(x) in the direct lattice. The continuity of the periodically repeated energy band functions E. + + + + . on the one hand. as stated. respcctively.188) directly.178) for the eigenvalues E.(k) may be npproximctted fairly closely by a Fourier series with relatively few terms. by K’+K” and K K”. Consider the coefficient matrix of (2. It ensures. namely the implications of point symmetry for band structure. we use the Schrodinger equation (2.k(x) may be expanded in plane waves with wavevectors k K .178) takes the form (2. the Schrodinger equation (2.188).(k) are identical.5. This implies that the eigenvalues Ev(k t K”) and E. We will now prove that the energy bands E. NOW we USP the reduced zone scheme description and concentrate on symmetric k-vectors.(k). and symmetric k-points were excluded.190) The E.(K’IVIK). as follows: + (2. The corresponding Bloch functions p.190) at the point k K” with K” an arbitrary reciprocal lattice vector. using the relation (K’ K”IVJK K”) . The above proof employs only the lattice translation symmetry of the potential V(X). and use the condition (2. One could also forego this.(k) actually obey the boundary condition (2. This was discussed above in the extended zone scheme. On the other hand. If one replaces the column and row indices K‘and K .189) Using this result.2.

It may.12 marked with Iargr greek or latin letters are among them. The points of the first B Z in Figure 2.e. Using the terminology above. inlo a vector crk equivalent to k which differs from k only by a reciprocal lattice vector K.140). The Erst contains those elements which transform k into itself or. This is expressed by quation (2. Electronic structure of ideal crystals 2. p k has a value between 1 and p .5. This set forms a subgroup pk of P . however. In r q a r d to their effect on symmetric kvectors. The center of the first BZ is special: all elements of P arc also dements of Z’k. also cxhibits the point synmelry of this lattice which. 7 . were excluded. This group is generally smaller than the point symmetry group of the lattice. so that pk = p and S k = 1. the point symmetry of a cube.3. and its point group is Oh(m3m). which underlies the extended zone scheme. The set of all different and non-equivalent vectors a k is called the star ofk. (2. as the Wiper-Seitx cell of the reciprocal lattice. and is called the s n ~ a l l poznt group of k. symmetric k-vectors. ‘The latter statement follows directly from the definition (2. is a symmetry point. whence p k = 1 and A k = p . bp.116 Chapter 2. For k-vectors on symmetry lines or planes. i. A general k-vector bas no point symmetry. The first B Z of the fcc lattice has. b3. namely that of the equivalent directions of the crystal. The energy bands likewise have a particular point symmetry.19 1) where a is an element of the point group of equivalent directions of the crystal. where the point group of equivalent crystal directions is likewise o h . be transferred immediately to the reduced scheme. Since each star point has the same point symmetry. therefore. The latter rase occurs for the diamond structure. into themselves or into an equivalent vector. We denote the number of elements of the point group P by p . at points on the surface of the first B Z . for its part.123) of the reciprocal basis bl. but in special circumstances it can also be the same. the elements cr of P split into two subsets.2 Degeneracy of energy bands The first B Z . the number pk of elements of the small point gToup P is given by k the relation p k p l s k . In section 2. so that we may also write &(k) = E v ( a k ) . A wavevector whose small point group does not consist of only the unity element. is the same as the point bymmetry of the corresponding direct lattice.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. vectors which are transformed by at least one element o f the point group 1’ of equivalent directions. Now we also admit such k-vectors to consideration. the point symmetry of band structure as given by equation (2. and the number of different star points of k by S k . The second subset contains all those elements of P which transform k neither into itself nor into a vector equivalent to k.

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

I?$.0(43m).e.r25. T and Td(332) of the cubic h crystal system. l-dimensional for small groups.8. r15.5: 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.and 3-dimensional. specifically for Oh(m3m).2. f but for the eigenvalues of any Hsmiltonisn in quantum mechanics.the theory of groups has immediate physical consequences. the projective irreducible representations are given in the crystallographic factor system.Tz. we consider some s p a i d k-vectors of the first BZ of the fcc lattice. as are the dimensions o the representations. It holds not only for the energy bands o crystals. the small point group is identical with the full point group P for crystals of diamond structure. At the center r.I112. ~ The number of distinct irreducible representations of an arbitrary finite group is. A X - - c K is quite remarkable. the irreducible representations can be only 1-. i.118 Chapter 2 Electronic structure of ideal crystals . the irreducible representations are denoted by rl. For the I?-point and diamond structure. the irreducible representations of the small point groups are denuted by the same capital greek or latin letters which stand for the k-vectors. supplemented by subscripts. To illustrate these somewhat abstract statements and to prepare for the discussion of actual band structures in section 2. Table 2. (See Append& A ) . ? . and I. This I. For the point X. For the point f groups of equivalent directions. In the context of energy band theory. and 3-dimcnsional only for the largest point groups. & somewhat strange indexing refers back to the so-call& compatibility rela- . It is a good example how a relatively abstract mathematical theory . with o h . 2-dimensional only for groups that are 'not too small'. b i t e .

.. ' The degeneracy at I may be compared with that of a free atom. Band structure 119 tions between different representations (see Appendix A for more detail). it is understandable that 1-dimensional representations may not be possible. . If a particular symmetry point ko of the first BZ is transformed into itself under the action of a point symmetry operation a .while at all other points only 1and 2-fold degeneracies occur for crystals which have diamond structure.1. The irrek ducible representations of the small point groups P of the symmetry points A. Thus all eigenstates corresponding to a given n .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. In addition.1. The degeneracy is thus n2-fold for the hydrogen atom. In the latter case the degeneracy is likewise a consequence of rotation and reflection symmetries. . are listed.5.e. In this case. which is the small point group of r for crystals with the diamond structure. X . which means that multiplication of two representation matrices yields the matrix of the product element. the point group contains an infinite number of elements. the symmetry-related degeneracy is still not the full degeneracy. .2. In addition to the symbols of the representations. 1 . We proceed now to another consequence of this symmetry. . is a direct consequence of the symmetry of these points. A and L for crystals having the diamond structure are also indicated in Table 2. The primes indicate that the involved representations differ from the unprimed ones only by a minus sign for the inversion matrix. + . In such circumstances. save only for a scalar factor (see Appendix A). have the same energy. one has an accidental degeneracy caused by the particular shape of the Coulomb potential. In the case of the hydrogen atom. . their dimensions are given.2. . This peculiarity is due to the fact that the space group of the diamond structure is non-symmorphic. where 1 can take the values 0. and hence also as the multiplicities of energy eigenvalues. In Table 2. In this case the energy eigenvalues differ only for different principal quantum numbers n.5.and %fold degenerate bands at the center of the first BZ. the irreducible representations of the small point group of X involve a factor system. 2 . arbitrary rotations and reflections are possible in this case. all irreducible representations of the point group o h . The dimensions of the irreducible representations of this group are determined by the angular momentum quantum number I . which will lead us to the concept of critical points and effective masses.5.5. However. Amounting to 21 1. 2. one has both 1-. If. then points ko 6k in the vicinity of ko are necessarily transformed into points close to ko. all odd numbers are possible as dimensions of irreducible representations.00. with their various 1-values 0. i. According to this table. At X there are 2-fold degenerate bands exclusively. + 2.n .

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

. as the cffective mass tensor M. but with coefficients M. in general. of M.’ accordingly have the dimension of a mass. Therein the crystal potential manifests itself. In contrast to the free electron case. Actually one can obtain the expression (2. They are eflectztw coefficients which involvc the effrct of the periodical potmtial. Only in the vicinity of critical points does the quadratic drprndenre persist.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.197) by Erst taking the energy zero at E u ( k c ) which is unimportant.2. where the coeficients form a multiple rn-l of the unit tensor 6. the difference between the mass of the free electron and that of the crystal electron reduces to the different magnitudes of the two masses.g defined by the equation of a second rank tensor M L 1 (2. An analogous statement holds for the inverse. i.e. .. which differ from those of the flee electton.(k) may be written in the form (2. for the case of an electron in a crystal they represent u tensor ML$ with non-vanishing off-diagonal elements and general diagonal elements. a scalar quantity. we introduce the components M: .$.5. In special c‘ase‘s one ran approximate the effertive mass by a scalar quantity rn. 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.154) for the energy of a free electron from (2.198) The components of the invrrsr tensor M . Band structure 121 order Here. Then.196) IJsing this tensor. T h e presence of this potential mandates that the wavevector of the free electron be repIared by the quasi-wavevwtot k. and then by substituting (2.195) of E.p. Thus. One therefore calls M u the effectzve mas8 tensor. and that the quadratic dppendenre of the energy on k become a more complicated dependence. the effective mass is a tensorial quantily. the expansion (2. generally generating different mass values in different spatial directions.

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

a knowledge of the density of states is enough to calculate important macroscopic properties of semiconductor crystals. 00.A z ( E ) . Considering spin.205) over a small energy interval E < E' < E A E .Ei) = 1 for E < E i < E + A E 0 otherwise . To this end we integrate equation (2. its eigenstates (disregarding spin) by li). = 51 (2.E i ) . We will introduce the so called density of states that encompasses essential information on band structure in just one function of energy. 2.207) Thus. appears instead of the free mass and that the energy at k = 0 assumes a value E. obtaining + 2 P(E)AE = FL E+AE dE'6(E' .206) equals.5. . Band structure 123 This differs from that of a free electron only in that the effective mass rn.C 6 ( E . In the following subsection we will again deal with band structure in its general form E. The quantity p ( E ) = . (2. and its energy eigenvalues by Ei. that p ( E ) does represent the number of o n e particle states of energy E per unit energy and volume.206) The integral on the right hand side yields JEE+AE dE'6(E' .. .5. Its Hamiltonian will be denoted by H . therefore.208) . each state i whose energy lies between E and E A E contributes '1' to the sum on i. Often. i.(k).Ei).(O) which depends on the band index and.e. cannot be set equal to zero for all bands by changing the zero of energy. 2 (2. We will show that this designation is justified. i = 1 . with no contributions from all other states.2.205) O i is called the density of states (DOS) of the system. the number A z ( E )of states having energy in this interval.4 Density of states Definition We first consider an arbitrary infinite oneelectron system. therefore. The sum in (2.. 2 . . (2. one has + 2 ~ ( E ) A E. Periodicity of the eigenstates is assumed with respect to a periodicity region of volume 51.

The cigenstates li) are Rloch states Ivk).205) for an ideal crystal.. expression (2. One must divide by this volume in writing the sum as an integral. The L)OS expression (‘2..212) which is independent of the volume R of the system.4 which lie within the first B Z . (2. the result of the summation is almost identical to that of an integration..213) and it differs from zero only for energy values for which the argument of the 6-function may brrome zero. Noting that the 6-function 6 ( & ) is the imaginary part of -(1/7r)l/(E ie) with t a small positive number. for energies in the v-th band. equals + p ( E ) = --Im 7T Tr (2. one can easily prove that p ( E ) of (2. and the DOS p ( F ) therefore reads p(E)- 2 -C 6 ( E - ’ (2.is defined by the expression (2.209) where trace sytxho1 ‘Tr’ denotes the sum over all diagonal elements with respect to any basis set in Hihert space. p u ( E ) . except for a factor R. whirh is 87r3//n.209) transforms immediately into (2.r.205)..210) uk The k-sum is over all points of the finely meshed net of Figure 2.211) 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. Because of the fineness of this network.= -1 R k 8T3 d3k . Summing over d l bands one again obtains the entire density of states (2. The substitution of the s m by an integral is done in accordance with the prescription c. in this case.214) .205). We now consider the DOS p ( E ) defined by (2. i.124 Chapter 2. The density of states follows as (2. The density of states restricted to the u-th energy band. If this set is identified with thr eigmstatcs 12) of ff. Electronic structure of idcal crystals confirming the designation of p ( E ) as DOS.205) may br written in a more compact form which will be used in Chapter 3 in the derivation of important general results.

The effective mass rn.e. infinitely large. For such energies it so happens that the value of p .213). we transform to new variables x.. i. ( E ) does not depend on the upper limit of integration. formally.(k) close to the minimum E d .(k.216).(k) -= E . for simplicity.201) with the sainc effective mass rn. i. obtaining (2. in other words.e.2.y.e. The smaller this velocity is at a particular k-point on the constant energy surface or.is taken as the origin 0. thus obtaining (2. along all three main axes.216) i s only justified within its limits of validity. singularities of the density of states as a function of energy are to be expected. we suppose that the function E. i.213) for p .(k) should have a minimum at k = 0. at a critical point.) by E N . then the expression for &(k) becomes (2. E. the contribution is. Parabolic energy bands We aasunie an isotropic parabolic energy band. is taken to be positive. The critical point k.(k)l is. apart from a factor TL.2 17) In this integral. the larger is its contribution to the density of states. If we further replace E. If (VkE. execute the integration over z using the rule .2 16) We use this to calculate the density of states p . ( E ) may be transformed into a surface integral over the constant energy surface &(k) -= E using the rules of calculation for the &function.e. z To start we. for energy values E. the longer an electron stays at it. Rand structure 125 Expression (2. the reciprocal absolute value of the group velocity of an electron in the Bloch state Ivkq). We transfer this limit.’. i.0.(k)l . The inteErand l/IVkF. Only for these E-values can the density of states as calculated by means of (2. They are called van Hove singularitiee. be relied upon.5. The use of the dispersion law (2.215) with df as element of the constant energy surface E.(k) is given by the expression (2. ( E ) from equation (‘2. From this it follows that for energy values E whose iso-energy surfaces contain critic81 points. from the edge of lhe first B Z to infinity.

~ x 2 .220) the density of states of a parabolic band with m*./E .220).2 It follows that where B(E . and continues following a square root law up to infinitely large energies. (2.14. and the density of states again falls off to 0 there.Euo) = 1 f o r E > Euo 0 for E < Euo (2. as in the .z 2 ) = . This may be seen immediately if one reviews the calculation for the isotropic case.(k) has a minimum. m:2.2 = . 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.ZO) 2zo with Zo +6(z+ ZO)] (2.221) is the Heaviside unit step function.E . Electronic structure of ideal crystals 1 E . the shape shown by the dashed curve of Figure 2. These singularities occur not only at energies where a particular band E. The anisotropic effective mass involves a change only upon substitution of the variables for the components of the k-vector .[S(z . .EA .E& - > 0.126 Chapter 2. > 0 exhibits square root-like behavior at the lower band edge. instead of an isotropic parabolic band.x 2 . This is one of the already mentioned van Hove singularities of the DOS. qualitatively.the first derivative with respect to E is 0 if one approaches the edge from the forbidden zone. In reality the band edge lies at finite energies.222). If one considers.y2 f o r E . According to expression (2. but m: must be replaced as follows (2.222) by the so-called density-of-states-mass m b . and it is +CXJ if one approaches it from the interior of the band.the factors for the 3 components are different and lead to the modification indicated in equation (2.y2 . then the density of states is again given by expression (2. It has. 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 . m:3 corresponding to the principal axes of the effective mass tensor. an anisotropic one with three different effective masses m:l.

because E o(. -AE.2. 1 fi (2. thus also at maxima and saddle points. (2. 2D.his interval. Such k-Bpaces have physical (as well as mathematical) meaning. The dashed curve shows the DOS of a more realistic band. in particular for electron systems whose free .15). and omit factors which do not depend on k or E. the number of k-points in the spherical shell is proportional to its volume AV. k2. it follows that AV m k L A k cc A A E . unlts) case considered here. These kvalues lie in a thin spherical shell in k-space [see Figure 2. but at a l energies corresponding to critical points of l the energy bands. (22 2 5) Such considerations can easily be applied to energy bands in 2-dimensiouel (2D) and 1-dimensional (1D)k-spaces. Hence AZ cy v%AE and p(E) o. 5- I I I I c < vl 4- = 321- I 0 0 1 2 0 -1 0 3 4 Energy lorb.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. For simplicity we set E. Band structure 127 Figure 2.15) which. ( 4%.f A E is the number of different k-points of the finely meshed net which yield energy values in t. is given by Ak 0. The n m b r r A Z of b m d states with energy between E and E . more vivid way (also see Figure 2. since Ah' CK k&k.223) For the volume AV of this shell.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. Counting states: 3D.5.and thickness Ak which. has radius k~ 6: &.o = 0.

and electrons in a homogeneous magnetic fieId for the 1D-case. It turns out. For 2 0 k-space. is taken into account. and (c) 1D k-space.surfaces and quantum wells for the 2D-case. Therefore.15: Counting states in (a) 3D. 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 . 1 fi (2. : (2. We wiU encounter examples of such systems in Chapter 3 . however. that spin and spin-orbit interaction play an important role in most semiconductors.228) .227) 2. such that A F a k E A k L A E and X p ( E ) 3 const. which may be written in the following short form (2.58) with spin.226) The density of states of a 2D-electron system is therefore independent of E. Thus. Electronic structure of ideal crystals b C Figure 2. (b) 2D. p ( E ) DC -AE.5. spin has been omitted from our discussion of the general properties of stationary oneelectron states of crystals. the volume of the spherical shell is replaced by the area A F of a circular ring. In the case of a I k-space: AV is replaced by the length Ak of the k-interval D itself. motion is confined to one or two dimensions of 3-dimensional space.128 Chapter 2. The starting point to address this question is the one-electron Schrodinger equation (2.5 Spin Thus far.

y ~ ( xf)}of . stdates that the solutions { p ~ k ( x . It. we have In t.he same way that this theorem was proved without spin above. Thus it colrimutes with all elements 9 of the space group. zti) Second. t. are the spin-dependent Bloch factors.hc components of a spinor is discussed in Appendix -4.hr Schrodingeer equation (2.2. then E x ( k ) rrprwents a continuous function of k Thc band . index X here refers to both the state of the orbital motion and also to spin state. The results of Appendix A are applied here in the form .. If k is restricted to the first B Z . we consider point symmetry operations u . Band structure 129 The first point we will consider is that of spatial symmetry in the presence of spin. 5 6 ) ) . one readily recognizes that TKso has thc full symrwtry of the crystal. its validity may be also demonstratd here in the pwsrnrr of spin.he absence of spin.5. Since the i one same holds for the spin free part H of the total Hamiltonian ! + has Iff + H. where I ~ X ~ [ X . s) of a spinor transforin i d e r thr operations g of the space group.229) To exploit this symmetry property of thv total Hamiltonian w e mu61 know how thc components p(x. the cornmulivity of the HanliltoIlittn with translations gave rise to the Bloch theorrm. whose action in tramforming t. In t. (2. Spatial symmetry Inspecting the explicit form of the spin-orbit interaction operator ( b e y formula ( 2 . g] = 0 .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). Considering translations first.

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

the space The product representations Dr. We consider the valence band of zincblende type semiconductors which is triply degenerate at I The . A systematic treatment of these representations is given in Appendix A.x V v . The following example illustrates the removal of degeneracy. This means that bands which are degenerate without spin by reason of spatial symmetry. + H. taken as representations of the sman point groups of a particular wavevector rather than for the full orthogonal group.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. without this interaction. It decomposes into the a ' . 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. may split if spin is taken into account. Band structure 13 1 Table 2. accounting for the effects of spin. This means that. are generally reducible.. due 7 to the spin-orbit interaction.5.6 the irreducible spinor representations are shown for some symmetry paints of the first BZ of diamond type semiconductors. but as an accidental rather than a symmetry induced degeneracy. (namely. ' product representation in this case is Di x 1-15. .2. In Table 2. The magnitude of the energy splitting depends on the spinorbit interaction. the triply degenerate r15-valence band without spin splits into the $-fold degenerate rs-band and the 2-fold degenerate r7band. degeneracy persists. representation of the full symmetry group of H group of the crystal).

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

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

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

or of other localized functions. One would like to manage with the fewest possible functions. we treat these two methods in greater detail below (sections 2. Within the frozen core approximation.236). Making the expansion functions orthogonal to the core eigenstates accounts for the fact that . because with fewer basis vectors the eigenfunctions are necessarily approximated more crudely than with a larger number .237) in order to satisfy the orthogonality condition (2. The basis sets employed differ by the number and kinds of functions they contain. The linear combinations to be subtracted are chosen such that the OPW's are orthogonal to all core eigenstates.6 and 2. This includes the tight binding met hod. ~ Bloch functions with Bloch factors for a special wavevector. to minimize the numerical effort. referred to as Luttznger-Kohn funetzons. The price for this is a loss of precision.7).C(cklk C + + K ) Ick) (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. 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. Rand structure 135 has as many columns and rows as the basis set has functions per k-vector.2.5. called OY W's. The calculation of band structure is thus traced back to the determination of the eigenvalues and eigenvectors of a k-dependent Hamiltonian matrix.236) holds. the tight binding and k pmethods may be used to derive analytic expressions for the k-dispersion of energy bands. This constitutes a generalization of the nearly free electron approximation. so that (2. the core band eigenfunctions (ck) may be taken as Bloch sums of the core states of single atoms. also called LCAO's (Lznear Combznatzons of Atomzc Orbatuls). Such expressions are extremely useful to achieve a physical understanding of band structure. The so-called k . K ) . In some circumstances. ~ Bloch sums of atomic orbitals. 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. one needs an i n h i t e number of functions. The OPW's must have the form l O l ' W k + ~ )= Ik. Therefore.in the extreme. p-method uses these functions. - Orthogonalized plane waves.

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

p" (2. but the reverse statement does not hold. such as.E. (2.245) The second term on the right is significant only in the core regions.245). the pseudopotential V.242) H P S= H + E ( E . only the pseudo-wavefunctions change. To begin with one revokes the re-interpretation of the Hamiltonian H . This is the reason .242) rem i the same. are eigenvalues of H . indicating that it repels valence and conduction band electrons away from the cores. Consequently.+ v p2 2m H + Vxc + Vc+ C ( E . Band structure 137 (2.245) 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.243) The Hamiltonian HPS is a well-defined linear operator.e. they are not also eigenvalues of HPS since the pseudo-wavefunctions of the core states vanish. although it is nonlocal and depends on the eigenvalue E itself.E. i. it is preferentially positive. Each eigenvalue of HP" is simultaneously an eigenvalue of H .2. We refer to the non-uniqueness of the repulsive part of V. (2. There.p" in equation (2.244) The last two terms in this expression jointly constitute the so-called pseudopotential V.E. Because of this. The smoothness of the pseudoptential makes it possible to restrict the planewave expansion (2.p" is relatively smooth throughout the cores. While core levels E.p" which has not yet heen discussed. considers the core electrons no longer as independent particles which enter the effective one-electron potential VH Vxc of the electron-electron interaction. the eigenvalues of the pseudo-Schrodinger equation (2. It is called a pseudo-Hamiltonian The are termed pseudo-wavefunctions. the representation matrix of the pseudo-Hamiltonian HPS is small and easy to diagonalize. This freedom may be an used to make the pseudopotential still smoother. One can show that it largely compensates the variation of the core potential V.)(ckl in (2. in these regions. Then HPS takes the form $gk + HPs= . for example. and also fulfill other requirements. norm-conservation of the pseudo-wavefunctions. If there the bra-vectors (E .5.241) of the pseudo-wavefunction to terms having small reciprocal lattice vectors K..)lck)(ckl C . The pseudo-Hamiltonian HPS may be written in a form which clarifies its meaning.)lck)(ckl C . It can he made even smoother if one exploits a property of V.

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.s main advantage in having the pseudoeigenfunctions built up from a relatively small number of plane waves. If d-orbitals cont.138 Chapter 2. the psendopotential must be known explicitly. of cell methods lies. In cell methods? one first determines linearly independent solutiona of the Schrodinger equation within a primitive unit cell for arbitrary energies.and p-orbitals. then the pseudopotential method becomes problematic.2). 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. This method suffers from the arbitrariness of t. The most natural choice of unit cell is the Wigner-Seitz cell. because it.e. for exmaple (see Table 2. This i s the c a ~ e long as the valence band states are composed mainly as of atomic 3.s. if the d-electrons of the atoms are sigmficantly involved in t. The crystal then looks something like . in a sense. i. be continuous at the boundaries of the unit cells determines the energy eigenvalues and eigenfunctiuns. and with bra-vectors (ckl substituted by appropriate functions. with core levels and wavefunctions taken from atomic calculations. The require ments that these functions.245). and their first derivatives. at an infinite number of points. of course. In order to apply this method. the pspudopotential V.he chemical bonding of the cryshl.ribute to these states in an essential manner. no longer applies. The pseudopotent. A completely different approach to solving the oneelectron Schrodinger equation is taken in the so-called cell methods. In practical applications. in the mufin-tin methods. 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. A further development.ial method is generally successful if the true valence band eigenfunctions are also sufficiently smooth outside ol the core region. Muf&n-tin methods In the present method one delimits spheres around the atoms. Forming Bloch sums with them. In principle it can be determined from the defining equation (2. one constructs the solution for the total crystal. i.and d-symmetr y.lie choice of the unit cells and the difficulty of satiseying the boundary conditions over the whole surface.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. and leaves some empty space around them.

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

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

only matrix clcmerits between valence orbitals are considered while those involving other orbitals are neglected.6.. Here this additional degeneracy may not be assumed. This is not due to the spatial symmetry of the potcntial but to its purr Coulomb form. eigcnfunctions &. These representations are characterizd by an angular momentum quantum number 1 which may assume all non-negative integral values. This corresponds to a perturbation-theoretic treatment of the Hamiltonian matrix with respect to the atomic orbital basis. not all of these contribute in an essential manner. In this way the energy levels E. The irreducible representation of a given quantum number 1 is (21 1)-fold degenerate. one with 1 = 1 a p-orbital. but we will omit it here brevity. 'l'ht. with 1 . nll orbitals of the cores of its atoms since only the totality of all orbitals forms a complete basis set in Hilbert space. one needs. is their spatial symmetry. These potentials are isotropic if all core shells are fully populated by electrons. These are distinguished by the mdin quantum number n which may take all intcgcr values horn 1 1 to 00.1 and + l . The spinor character of the orbitals may be taken into account. Within the TB approximation one takes only these orbitals into account. For the elemental semiconductors of the fourth group of the periodic table the valence shell orbitals are formed by the four ns- . The 21 1 basis functions are distinguished by the magnetic quantum niimbcr 7n which takes all integei values between . 'l'he largest contributions are to be expccted from orbitals forming the valence shells of the free atoms. In the case of atoms forming diamond and zincblende type semiconductors. and the atomic orbitals of given energy eigcnvalues form basis sets of irrediicible representations of the full orthogonal symmetry group.2. The energy spectrum of the free atom is degenerate with respect to m. A wavefunction with the quantum number I = 0 is called an s-orbital. + + + (2. The mobt important property of the orhit&. rigorously speaking. In order to represent the eigenstates of the valence electronb: of a crystal. Foi the hydrogen atom there is also a d c generacy with respect to 1. Tight binding approximation 141 atomic oibatnls. it is assumed that the tttorriir core is located iit the coordinate origin x = 0. The latter i s determined by the symmetry of the Hartree o i HartrecFock potentials of the atomic cores. m.l of an atom depend on thc two yuanturn numbers r~ and 1 . this condition is always satisfirul. However. and the corresponding eigenfunctions dnlm(x)depend on thrw quantum numbers r ~I . which turns out to be decisive for the TB approximation. For each value o l lhe quantum number 1 one has an infinite set of different energy eigenvalues.jrn(x) can be written as products of the radial wavefunctions &(I x I) and spherical harmonics Km(xl I x I). Thus we may assume isotropic core potentials.246) Here.2 a d-orbital etc.

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

and the integral over the product of the two. by writing down and solving the eigenvalue problem for the crystal Hamiltonian in the non-orthogonal basis set of the atomic orbitals. Although the two orbitals are localized in different spatial regions. as has been assumed thus far. Tight binding approximation 143 Figure 2.249). The latter are visualized in Figure 2. for orbitals at different centers. y. but different values of a and a.2. 6 . The eigenfunctions of equations (2. z of the Cartesian. 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. This may be done directly. This procedure .16.248) will be referred to as spherical orbitals. For R’ f R or j’ # j . The non-orthogonality overlap integrals must therefore also be taken into account. i. one has ($a’ I $fZ) ‘af. turns out to be relatively small. 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 .6.e. i. no such orthogonality exists. z. are also orthogonal ‘ to each other. The quantum numbers nlm of the spherical orbitals. but at a particular lattice position R+G. and those of (2. 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.246) to (2.250) as Carte3ian orbitak. the so-callcd ovcrlap integral. as well as n.orbitals in Cartesian representation. the corresponding orbitals will be denoted by &j~(x). The orbitals considered above are orthonormalized.16: Polar diagrams of the atomic s-and p.e.251) If the atomic core is not located at the coordinate origin. (2. (2. will be abbreviated by a general index a..

(2. To represent the Bloch type eigenfunctions by means of atomic orbitals o a J ~ ( xit . but their indices n E nlm will retain the meaning they previously had for the ordinary atomic orbitals. Ektranic structure of ideal crystds is. As before.144 Chapter 2. e. That there are indeed linear combinations of atomic orbitals possessing these properties. they will not be given here since thcy are nut. no longer given by the expressions [2. Slater. forms the content of Liimdin. such that (&!jrR( I O a j R ) = bo'abj'$R'R.2 56) . is convenient to transform the latter into Bloch type ) orbitals puJk(x). the eigenfunctions of this equation are taken in the form of Bloch functions pyk(x).ants. the d U 3 ~ ( obey the relation x) (2.254) Bloch sums. This is done by means of the k-dependent unitary transformat ion (2. again.he same spatial symmetries a s thc original atomic nrhitrals Q U j ~ ( xbecause these symmetries are the essential proper). 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. hlthough explicit expressions for the G w d i n orbitals & j ~ ( x )can in principle be providd. of course. ties that allow the matrix elements of the Ilamiltonian to be reduced to a few const. Iiowcvcr.255) The sum over R extends over all lattice points of the periodicity region. Consequently. The Lowdin orbitals arc. Schrodinger equation in matrix representation Consider. the Schrodinger equation (2.253) With Ro as an arbitrary lattice vector. the new orbitals should have t. each set heing chara c t w i d by a particular angular morrieriturri quantum miniber 1. aIso orthogonal for different centers.'<sthcowm (we. We will iise this theorem below. 1954). by definition. quite inconvenient becaiise the matrix of overlap integrals has to be calculated explicitly and diagonalized together with the Hamiltonian matrix. likewise form basis sets of irreducible representations of the full orthogonal group.254) one may readily verify that (2. will henceforth be understood as atomic ) orbitals in the sense of Ldwdin's theorem. n m d d if one proceeds in thc manner to be discussed below.. 'suitable' means that . The orbitals m U j ~ ( xwhich thus far have been )! taken as ordinary atomic orbitals. By means of (2. The orbitals q a j ~ ( xare now.246) to (2.75) of the crystal.250).g. the new orbitals must. Koster.

the (ajk I H I a’j’k) form a square matrix with a finite number of rows and columns. the same as the number of different orbitals per primitive unit cell which were used for the representation of the eigenfunctions. Tight binding approximation 145 which identifies the & j k ( x ) as Bloch functions of quasfwavevector k. (2. Once the integrah ( a j 0 I H I a’j’R’)and. The 4 . it suffices to take k in the first B Z . or if need be. the lattice translational symmetry of H has been used. ( (2. 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). Therefore.261) describe the interaction of electrons in orbitals a and a’.). also the matrix elements (ajk 1 H 1 a’j’k) are known. the second nearest neighbor atoms only. 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. because of the relation exp[iK. through them.6.258) of Bloch sums q 5 a j k ( x ) . R] = 1.75). such that (‘#‘alk’j’ I ‘#‘ajk) 6a’a6j1j6k1k. j k ( X ) are called Bloch sums of atomic orbitals.2.260) over the nearest. These integrals substantially decrease with increasing distance between the atoms. (2.261) In deriving equation (2.255) automatically puts us in the reduced zone scheme. the use of the Bloch sums (2.5.257) In the TB approximat.I.e. i. I -xR’ . so that it suffices in most cases to extend the sum on R’ in (2. Employing this representation in the Schrodinger equation (2.260). the energy eigenvalues and eigenfunctions of .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 ~ . ‘number J of atoms per primitive unit cell times number A of orbitals per atom’. Obviously. If one replaces k in &jk by a wavevector which differs from k by a reciprocal lattice vector K then. where one of ’ the orbitals belongs to the atom at ? and the other to the atom at R’+ ?. the original wavefunction is reproduced expect for an unimportant phase factor. The integrals ( a j 0 I H I a’j’R’) in (2. For a given wavevector k.ion.

264) t=l 6 It follows that the energy eigenvalues Ens(k) of the Schrodinger equation are Ens(k) = ern + pns2 [cos(k. we have employed the fact that. (2.fa.a) + cos(kya) + cos(k. with set of atomic orbitals will be restricted to one ns-orbital only.O. With increasing distance between the atoms. (2.262) (2. In evaluating the matrix element (nslk IH I nslk). the matrix element (nslk IH I nslk) of (2.z = (fa.s = (O. can in any case.. a matrix of size 1 x 1 = 1 is obtained.. 2 .260) at the nearest neighbor atoms.fa). as previously assumed. all six neighbor atoms give rise to the same value of the integral (2.R3. Here. In this context. may be identified with the energy of the ns-level of the free atom..1).0.263) I nslRt) = pns.. In terms of E. Consider a crystal having a primitive cubic lattice and 1 atom per primitive unit cell . the J x A energy eigenvalues form J x A energy bands. and Pns. such that a = ns.O. The value of .260). we use the notation (nslO I H I nslO) = ens. This is an easily solvable task which occasionally can be treated analytically.260).260) is given by (nslk I H I n s l k ) = ens + &sxeik’Rt.(k). the main quantum number n will be allowed to take not just one value. The value of E. trivial. The latter are located at R1.Rs. to gain insight into the formation of energy bands.146 Chapter 2.265) It is of interest to further discuss the eigenvalues e. .261). in fact. 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. t = 1 . For the matrix elements occurring in equation (2.BnS depends on the overlap of the ns-orbitals localized at adjacent atoms. The atoms are placed at the lattice points R. we will terminate the R’-sum in expression (2. be done numerically. If k varies over the first B Z .a)] . 6 . . & approaches 0. For each k one has J x A eigenvalues and eigenvectors.4 = (O.O).1. for reasons of symmetry. Simple example: cubic crystal composed of s-atoms We will illustrate the above discussion with a simple model.O). This the solution of thP eigenvalw problem is. but. . in a crude approximation. They will be partially degenerate if symmetrical k-vectors are considered. The ( j . .. (nslO I H (2. With J = 1 and A .

k s P3s P 2s PlS -IT - D 0 Wavevector (O. Each level ens of the free atom gives rise to an energy band of the crystal. This means that the valence electrons in the free atom do not occupy only one 5 level. for n . however. The bands are separated by forbidden energy regions.. Tight binding approximation 147 Figure 2. We assume this to be true.k. The separation between adjacent energy levels cn8 should. In addition.263) decrease because of decreasing ovrrlap of the orbitals. corresponding to the larger values which the ns-orbitals with larger n have at the nearest neighbor aloms. the energy band dispersion along the line (0.) l-r a but several. such that for n = 1 l it is taken to be negative. then the parameters fins of equation (2. always be larger than 4Pns.17: Energy bands in Tight-Binding ayproxirnat.O. the matrix elements of H between s-orbitals having different values of n must be negligibly small. To justify the application of the results obtained above in the present case. Their widths decrease with growing n.ion for the simple s-atom crystal described in the text. we suppose that ens is negative for a l n. The width of these bands amounts to 4&.3 negative etc. as has been . for n .6. If the above conditions are met.2 positive. The absolute values of Pns are expected to increase with growing n .17. and that the sign of pns alternates. but several s-levels ens differing in the value of n. 0. kz) of the first B Z of the simple cubic lattice under consideration. This behavior reflects the differing numbers of nodes of thc atomic wavefiinctions for different values of n. has the form shown in Figurr 2. If the distance between nearest neighbor atoms increaees. thus increasing with increasing n.2.

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

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

For j = 1 one has j' = 2.266) Matrix elements between orbitals at non-equivalent atoms In evaluating the matrix elements between orbitals at non-equivalent atoms.p-matrix contains exactly one independent constant. R 4 = -a3. these elements must vanish. es is the energy of the s-orbital of the free atom.260) becomes 4 (ujk I H I a'j'k) = x e i k ' ( R t f 5 f . With this simplification the Hamiltonian matrix of (2. The matrix elements between p.and p-orbitals at the same atom transform according to the representation rlx I'l x r 1 5 = r15. according to Appendix A. 0 t=1 (2.4. because the second may determined from the first with minor changes. )~ j IH I U ' j ' R t ) .% . Electronic structure of ideal crystals it by E ~ . Summarizing. the unit representation occurs exactly once.150 Chapter 2.260) may be restricted to the 4 lattice points &.268) (see Figure 2.j' = 2. 2 R 3 = -a2. as in the case of c8.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. and for j = 2 then j' = 1. Here. elements of the general form (ujk 1 H I a'j'k) with j # j ' . the value of cp is roughly the energy of the correspondingp-orbital of the free atom.27). whose primitive unit cells host the 4 nearest neighbor atoms. We will restrict ourselves to the first case.2.t = 1. 1 R = -al. 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. j = 1. In a crude approximation.(. i. i. 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 .3. The four nearest neighbors of a 1-atom are located in the primitive unit cells at R = 0. which does not contain the unit representation.267) The values of j and j' are complementary to each other because the nearest neighbor atoms lie in the other respective sublattice. The matrix elements between s.19). . Again. The non-diagonal p -p-matrix elements must be zero according to the above symmetry analysis. (2.e. Then. we have (2. which means that the p .e. the R'sum in (2.

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

260) are. however. m’. and since the eigenvalues of the Hamiltonian for bound orbitals are generally negative. This figure also shows how the elements (In110I H 2 are interchanged. the matrix elements (alk I H I a’2k) of equation (2.270) The three matrix elements (0010 (0010 (2. Eiectronic structure of ideal crystals neighbor dirwtions. vji.152 Chapter 2. Vm. Rwauw of that.. in an approximate sense.20. then the integrand of the matrix elements (Im10 I H I l’m’20) has the full axial symmetry.(x . 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 positive ones for Ifaw.273) Since the atomic orbitals under consideration are those of bound states. Taking account of the strength of the overlap of the orbitals . The diagonality holds. The hermiticily of the Hamiltonian and the particular form of the wavefunctions in (2.272) are identicaL These elements are illustrated in Figure 2. The matrix elements of H between orbitals at different renterrs jR and J’R‘ thereby decompose into bums over all centers JI’R’‘. (2.252) lcsd t o the relation (lrn10 I H I I‘m20) = (l‘m20 1 H I lm10). If one considers only such twecenter terms and neglects all threecenter contributions. the symmetry of H is smaller. m‘ if the R’-sum is extended to the swond-warest or more remote atoms. in general. non-diagonal with respect to m.R” . one may expect negative values for k<3n.. For the second-nearest neighbor directions. One has 1 l’m20) behave if the two atoms 1 and (2. so that these dements become diagonal with respect to m.. The periodic potential V(x) in H represents a sum &.i y ) of potential contributions of all the individual atomic cores of the crystal.. IT&. which may be seen as foHows.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.

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

(El0 I H 1. . the matrix elements of H between Cartesian orbitals in the pair-related system read (310 I H I 3.and y-axes lie in the plane normal to the z-axis. The corresponding 2. the matrix elements of this operator with respect to the Cartesian orbitals. 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.-orbital co2.ax is points in the direction of the connecting line between atom 10 and atom 21.orbital with respect to the cubic-axes system.274) These expectations are in fact valid in most cases. apart from an irrelevant rotation about this axis. one can conclude that the absolute values of these elements should obey the relations I VPPO I ’I v I ’I VSSU I >I . In terms of this notation. 0 H I 520) = ( . such as (310 I H I 220) and (120 1 H I . the matrix elements between Cartesian orbitals can also be related to those between spherical orbitals. 5.10 I H I 120). Electronic structure of ideal q y s t d s in Figure 2.520). (2.154 Chapter 2. (2. (510 I H 17/20) = (g10 I H 1. The relations read (310 I H I 3. Since the C a r t e sian orbitals are defined in terms of spherical orbitals by equations (2.520) = (210 I H 1120) = 0. 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.(110 I H I 120). (110 I H I 520) etc.20). The z-axis of the Cartesian coordinate system is taken t o be the same as that of the spherical coordinate system used above. 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.267). The pair-related .250). (2.(3. 0 H I 520) = 0. The corresponding relations are given below.220) = Vppu.20) = VSScr. The coordinates in the pair-related Bystem will be denoted by 2 . (3.lo). 3 1I 31 (3. ( . (110 I H 1220) = (510 I H 1520) = Vw.249).10 I H I . V .20. We determine these elements in the third step.275) To develop the representation of the Hamiltonian matrix (2. incides with the 8. This means that the z . in the second step.10I H I 520).(3. Elements which are complex conjugates due to hermiticity of the Hamiltonian.10 I H I 220) = VSF. are listed only once. I.

r1 = cos 0.276). Since the orientation of the pairrelated system is defined only up to an arbitrary rotation about the Z-axis. To determine this relation. z related to the cubic-axes system must be expressed in terms of the pair-related Cartesian orbitals ?. Since the 2 . p l = sin 0 sin $. The basis vectors are transformed by the transposed matrix. These are the elements of the third column of the rotation matrix in equation (2.q1. in the present case of rotation.275) to (2. Tight binding approximation 155 iii) Cartesian orbitals i the crystal-related system n To this end.276) Below. be set equal to zero.277).c. the Euler angle 'p may. 71) of the pair-related 2 -axis with respect to the crystal-related cubic z-axis play an important role.cos 6 sin $ 0 sin 0 sin $ c o ~ e c o ~ ~ -sinecos$) sin 0 cos e (i). 6 and 'p. which. we will see that the direction cosines (PI. (2. the rotation matrix A of equation (A.sin 6 cos $.y.31) transforms the coordinates before rotation into the rotated one. As noted in Appendix A.6. The transformation is characterized by Euler angles $. the Cartesian orbitals 2.y.277) Using equations (2. we have (:) cos @ = (sin@ . z and ?. q1 = .2. the matrix elements in the crystal-related system are evaluated as One obtains . we consider a rotation which transforms the crystal-related axes system into the pair-related one. is also the inverse matrix.e.Z. i. (2. Z are understood here in the sense of basis vectors. without any loss of generality.y.

.1). such that dt = Rt .d f ( s 1I0H I s2Rt) = V.dt. qt. For complex conjugate elements. P Z . r t ) of the connecting lines between the central 1-atom and the nearest neighbor atoms 2t.278) by replacing the direction cosines (PI. For the diamond structure. l ) . again. Using equation (2. only one relation will be given. 1.1).-1. . d4 = -(l.279) These relations determine the direction cosines ( p t . 7 2 ) = (l/fi)(LI. 4 4 4 4 U (2. r t ) in them.280) t=l 4 (slk 1 H I 22k) = x e i k . we obtain 4 4 (slk I H 1 s2k) = ~ e i k . This will be done in the next step. the two sublattices are displaced with respect to each other by the vector (a/4)(1.1) = ( l / f i ) ( L 1.7.d3 = -(l. ri) by ( p t . d t ( s 1 0 I H 1 22Rt) = Vswxeik-dtpt.268) for Rt and the explicit form of the primitive lattice vectors of the face-centered cubic lattice. 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.156 Chapter 2. The vectors pointing from the central 1-atom to the four nearest neighbor atoms will be denoted by dt. In particular.3. The unknown matrix elements (a10 I H I a‘2Rt) for t = 2.xeik. (PI.3. d2 = -(1.4. t=l t=1 .. With the help of equation (2.TI. qt.l).267). m.2.1).l) a ( etc.I). From these elements we may determine the elements with the nearest neighbor atoms of different unit cells. 4 2 . follow from the elements (a10 I H 1 a’2R1) in equation (2. t = 1. 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. t=l 4 (2. we obtain + dl = a a a(l. iv) fourth step.

280) may be reduced to just four because of the obvious relations ptpt = r t .6. p t r t = qt. Tight binding approximation 4 4 157 4 The combinations of matrix e1ement.2. The four independent sums are .s in these expressions are commonly abbreviated by The seven different t-sums which enter t.he matrix elements (2. and qtrt = p t .

ik.282). I 22k).e ik-dz . The constants r..ik. I y2k). Ez(k). I s2k). E.ik..d~ I . Electronic structure of ideal crystals 9l(k) = eikdi + . I z l k ) .ds .ik. Then one measures the band energies at these points 01calculates them by some other ..E. at least 6 special k-points as at functions of the unknown parameters cg. . epr E..261) between atomic orbitals.282) g2(k) = eik. which are universal functions of k. Es(k) of the Hamiltonian matrix (2.281) and the Hamiltonian matrix elements (2.. I z l k ) .. The k-dependence of the eigenvalues stems from the factors 91.158 Chapter 2.ik.ik.. (2.d4 9 4 0 4 = ..dl + .ik. E. are related to .ik.&. I principle...d3 9 3 0 4 = . material properties. Empirical TB method To obtain the band structure of diamond type crystals. I z2k). these constants can be calculated from the n defining equations (2.dz + . In quantum chemistry one often proceeds in this way.280) and (2.g4 in (2.ik. I y l k ) . one also may forego the calculation of these Hamiltonian matrix elements and considers them as empirical parameters. Their values may obtained as follows. . e p . and E . g3. 92.ik.d4.ds Finally.. .ik. E.. we c an write down the Hamiltonian matrix (ajk I H I a’j’k) between Bloch sums in explicit form. First of all..ik+d2 . and E..d4 . one has to calculate the eight eigenvalues El(k). However. .dl .dz + .d3 + . one calculates the eigenvalues of the Hamiltonian matrix (ajk I H I a’j’k). .dn: + . this matrix is given by Band structure. Arranging the eight basis functions 1 ajk) in the sequence I s l k ) . E.283) at the various points k of the first BZ.

Inspecting the inter-atomic TB parameters listed for the various diamond type semiconductors in Table 2. which will be treated in Chapter 3. as independent parameters. one obtains a system of equations which determines the unknown parameters uniquely.36 -1.52 -8..7. (After Majewski and Vogl. Vspo.1 type semiconductors (in ~i 6s EP VsSa V v vma -17.54 2.50 5.. Once these are determined.38 1. it may be seen that.79 Table 2.. For instance. ESP. Tight binding approximation 159 Table 2.52 -1. In this case it serves as an extrapolation method.47 4. the intra-atomic matrix elements t 3 and tp may be identified with the atomic s.. V.91 10. one often takes the inter-atomic matrix elements V.. It is called the empirical tight binding (ETB)-method. and Epp E.. f9RO.55 -6. and a .93 2.15 -1. each of these parameters may be expressed in terms of the material-dependent nearest neighbor distance do of the crystal. There are other variants of this procedure...) 1 1 1 1 1 1 1.04 Ge -14.2.41 -2.55 method. one is able to calculate the band structure at all k-points. they are referred to as tight binding parameters. (After Harrason.8: Universal inter-atomic TB parameters.38 -6. Instead of EsS.E.68 2.20 -0.6.36 4.. E .60 -13. because it helps to extrapolate from the electronic structure of the ideal crystal to that of the perturbed one.and p-energies. (see Table 2. 1987. Together with c3 and e p .92 1.97 -4.7: Tight binding matrix elements for diamond eV). This method can also be applied to the calculation of the electronic structure of perturbed semiconductors. and Eppfor the fitting procedure.) m i -1. Equating the TB eigenvalues with those measured or known from other calculations.7). The whole procedure may therefore be considered to be an interpolation of band energies between special points of the first B Z . and V. within an appropriate error limit. leaving only the inter-atomic constants E.

resulting in c l o d analytical expressionh for the energy hand lev& at special k-points of the first BZ.) n universal material-independent factor qltm. hlormver. Their solutions stale with the inverse-square of the lattice constant a because the empty lattice band levels do so.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).284) has been jntroducd in order to make the universal factors qzpm dimensionless. The nrarest neighbor distances dg follow from the cubic lattice constants a in Table 1. They are close t o the values listed in Table 2. Ultimately. respectively.8 are shown in Table 2. As a unnsequmce of this. (Source same as i Table 2.284) signifying that the inter-atomic matrix elements of the Hamiltonian scale ) with the inversesquare of the nearest neighbor distance. the empirical do'-dependence in equation (2.283).8. the empty lattice band structure scales with the inverse square of the latlice constmt.(fi/4a). Harrison. Electronic structure of ideal crystals Table 2. the 5ame k-points.9: Intra-atomic TB parameters (in eV) to be used in conjunction with the universal inter-atomic TB parameters of Table 2. This approximate relation is (2. 1979). numerical valiies for the universal TB parameters q ~ follow~from these ' equations.2 by ineans of the relation do --. in 'lable 2.160 Chapter 2. The factor ( f i 2 / m = 7. The intra-atomic matrix elements e g and c p corresponding to the set of universal inter-atomic TB parameters ql+.62 eVA2 in equation (2. The TB band structure follows by diagonalizing the T H Hamiltonian (2. If these expressions are identified with the empty lattice band levels at.9 for a series of atoms forming diamond and zincblende type semiconduc- . 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. linear eqiiations for the TB parameters ctre obtained.284) originates from the kinetic energy operator of the crystal Harniltonian (li'royen.

o .T. 0.(1/&)(0.0.1. iii) &(O) < &(0) < &(o) ru-sn. The constants E~ and E..for C and Si. i . The results me the following 8 eigenvalues I &(a). o . 8 . LO. A k-point of prtictilar interest is the €32 center k = 0.0. namely : i) &(0] > &(O) > E s ( 0 ) . . 0.1. - ii) E3(0) < & ( 0 ) < & ( 0 ) Ge. Tight binding approximation 161 tors. They represent atomic s. 01. ~ These relations Inem that the E'c. 0 . o. I E ~ O. o. . I E ~ O.(O)-level moves down with respect to the other two levels as the size of the atoms increases.o. there are still three pussibilitks (important malerials to whirl1 the three possible cases apply are listed alongside the cases).7(0). the energetic ordering of the lwels is determined by the relatiom El@) < ER(O). . I. i.and p-level energies which deviate somewhat horn the energy levels given in Table 2.l. i . Here.2.o. the eigenvalues and eigenfunctions of the Hamilton matrix (2.( i / ~ ) ( 0 . For the pmitinn of the &(O) lcvcl. I R 5 O ) = (1/&)(1.0. 1 . The components of the corresponding eigenfunctions I EiO) read as follows: 1 E10) = (l/&)(l. o j . therefore the El(O)-hvel is lower than the Es(O)-level.0.0.o. 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.0..6. O . O). 1 EzOj = ( I / f i ) ( O . i .286) Since cP is negative and EZzpositive. ~ ~.(i/fi){o. i = 1. Thm+nrP. 0. 1.2~17) E s ( 0 ) . E l ( 0 ) < E z ( 0 ) .E3(0) = E4(0) < E5(0) (2.283) may br o b tained ~ I closed analytic form.o. 1 E40) 0) (i/&j[o.0.O.i). o.o. . o ) .ij. both have negative values. 0. I EGO) (1/&)(0. o. o.o).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 ) .oj. ) ) (2.&.0.o.o.o. o.0. This means that E l ( 0 ) is the deepest of the foul levels.o. 1.2. 1.

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

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

With these two changes. while for the s-state belongs to a 2-atom.. thr matrix element. - conduction bands valence bands r.’ - r. Therefore. r. Secondly.284) remain valid because they refer to matrix elements whose orbitals at the two different atoms belong to the same state.273) cannot be used in the zincblende case because it rests on the chemical identity of lhe two atoms of A unit cell.’ 6.8 are associated with in by meany of equation (2.21: Ordering of energy bands at the center 1 of the fint B Z for semicon’ ductors of diamond and zincblende type. Elect. (the parameters iSw Table 2. diamond structure - 6 - zinblende structure Figure 2.. the relation V$$ -V:$ G -V3w of equation (2. and the p-state to a 2-atom.ronic structure of ideal crystals r. The other excliangr relations in (2. the s-state belongs to a 1 atom. V & is given by an independent constant rather than by -V:$. in equation (2.164 Chapter 2. - 6.284). - r. For the matrix element l 2 .283) the TB Hamiltonian matrix for zincblende type semiconductors becomes z. and the p-state to a 1-atom. in that at the lower right. -espc csF .

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

.$zlR(X) 1 I h d R ) = 5 [ $ s ~ R ( x. bonding orbitals (c) and anti-bonding orbitals (d).22: Illustration of the wavefunctions involved in chemical bonding i n tetrahedrally coordinated semiconductors: sp3-hybridorbitals (a. e. 1 h z l R ) to atom 22 etc.22 the probability distributions of the four sp3-hybrid orbitals are n shown in the form of polar diagrams. The orbitals resemble clubs pointing to one of the nearest neighbor atoms in the sublattice 2.4 z d X ) .# z l r t ( X ) -tb y d x ) .zlR(X) 1 ) 1 1 1 I Figure 2. b). I hllR) to atom 21. I h31R) = 5 [dslR(X) ..&lR(X) + d'.166 Chapter 2.g. Electronic structure of ideal crystals 23 23 23 23 Figure 2.

The same holds for the Hamiltonian matrix ( h t j k I H I htrg'k) with respect to the basis I htj k). beyond those already made earlier. These approximations facilitate the derivation of simple analytical .6. This statement holds. only as long as equivalent approximations are made in the two representations.289) and (2. However.3.290) of the hybrid orbitals in terms of atomic orbitals. the hybrid orbital representation is well s u i t e d for further approximations.4 orbitals for the two free atoms of a unit cell. I h 2 2 R 2 f R) at atom 22. the four sp3-hybrid orbitals I h12R).and porbitals from which they are constructed. it has the same eigenvalues and eigenfunctions as the original matrix. I h32R).255).291) in complete analogy to the Bloch sums q b ~ involving atomic orbitals in equak tion (2.2. 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. The following four orbitals are directed to the 1-atom in the unit cell at R: orbital 1 h12Rl+ R) at atom 21. For each unit cell there are 8 associated and j = 1.and I h42&+ R)at atom 24. Tight binding approximation 167 Similarly.2. orthogonality also holds for hybrid orbitals at different centers. as there are 8 atomic hybrid orbitals 1 &jR)with t = 1. As such. Hybrid orbitals at the same center are orthonormalized with respect to each other. I h42R) at a 2-atom in the unit cell at R. 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. as the s. If the latter are understood in the sense of Liiwdin. Due t o the definitions (2.I h22R). From the hybrid orbitals of a given sublattice one may form Bloch sums I htjk) by means of the relation (2. of course. 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.2. I h32R3+ R)at atom 23. are defined by the relations These orbitals point to an atom of type 1.

one has to distinguish between diagonal and non-diagonal eleIf ) ments. may be determined from (2.E ~ . 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. Approximately. Their common value. (2. while all others may be neglected. this result is the same as for the matrix elements ( h u k 1 H 1 h u k ) between the corresponding Uloch sums. we describe the most important additional approximation available in hybrid orbital representation. An analogous result holds for the diagonal elements (&jR 1 H 1 ht3R) at the same center.290) the expression Vl 5 ( k t j R 1 H 1 ht.295) Again.271) to (2.) 1 4 t # t' .290) and equations (2.273) 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.289). one need only consider these elements.289). are listed in Table 2. the Hamiltonian matrix elements ( h t l R I H I ht2 R t R) between these orbitals will be the largest. denoted by V2. Hamiltonian in hybrid-orbital representation Here. 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.10. (2. Thc non-diagonal elements ( ~ Q 1R 1 h t . as can be seen from the explicit expressions for the hybrid orbitals (2. 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. In consequence of this. (2. along with values of Vi and VL. Their common value ctt is ~h (htjRI H I h y R ) = -(~g 4 1 -t- kp). For the common value V1 one finds by means of (2.jR) - .168 Chapter 2.( c S . The former elements do not depend on t and R.289). (2. t'.294) with e3 and ep defined in equation (2. Numerical values for th.266). ~ R have thc samc value for all R and orbital quantum numbers t . Since only nearest neighbor atoms are considered.290).dt (2 293) ~ In the casc of Hemiltonian matrix elements between hybrid orbitals at the same center. . (2.

we arrange the eight basis functions in the sequence I h l l k ) .6.296) This matrix is also known as the Weare-l‘horpe Uarniltonian.we havve Table 2.37 -2.01 -2. Then the matrix ( h t j k I H I httj’k) takes the form . its 8 eigenvalues can be obtained in closed analytical form. I hzlk). I h Z W . Denoting them : by E.7 (in eV).b. i = 1 . 2 .76 -2.98 Ge -8.76 . Remarkably. I h 4 W .10: Hybrid matrix elements calculated from the TB parameters in Table 2. 3 . 4 . I h s W . (2. I h32k). -8. I h l W .27 -1. Tight binding approximation 169 In writing down the Bamiltonian matrix (htjk I H I hrj’k) in the hybridorbital representation. E.2. I h 4 W .

c.23 also illustrates how the different bands emerge from the atomic s-and p-1evrlb due to the two interactions V and V z . It . Vz determines the distance be1 tween the cpnters of gravity of the valence and conduction band complexes. Electronic structure of ideal crystals r wovevector X Figure 2. Figure 2. The actual positions and k-dispersions of the bands (2. In this regard.297) are determined by the parameters th. and V1 the width of thpse bands. Here gl(k) is the structuredependent factor d e b 4 in equation (2.ure of Si calculated by meam of equations (2. the ralcuIatjon of the total energy of the crystal.b(k)determined above must be summed over all i and k. arid thP 4 bands indicated by u lie above it.282). Now wc return to the main goal of this subsection. Roughly speaking. T i means that i the ground hs n state of t h e crystal.297). To accomplish this. Using the values for S i given i Table n 2-10. the &lands are fully populated by electrons.170 Chapter 2. and the a-bands are complekly empty.23. thus they are the conduction bands. they form the valence bands. and the validity of the magnitude relation I V 1>1 “2 I between the absolute values of and Vz. the energy values of the four valence bands E. i. one obtains t h bnrrd structure shown in trhf right hmd part of Figure ~ 2.23: Evolution OF the energy bards of semiconductors with the diamond slructura within the TB approximation The right-hand part shows the band struct. Essential features of these relationships are the 1 negative sign of V2. 1’1 and Vz. the 4 bands indicakl by b lie below the energy gap.

297).O.296) are calculated without taking account of the VI-terms.0. this leads to the reduction of the enerffi bands to the two dispersionless levels givw by 5k) belonging t o q.0. have the components bik) (l/fi)[l. (ht2k I aqk) = ( l / & ) ( O . As may he scen from formula (2.e. O . O . 0: O . Bond orbital approximation To introduce this approximation. 0). 1. we review the already solved problem of diagonalizing the Hamiltonian (2. In the case of &states the hybrid orbitals are added.O. carried out in two steps.0.0'. -. In the first step... 1.296).O). is made.0.0.0: -ez. i. O . Yi'ghht binding approximation 171 turns out that this task may even be carried out analytically if a suitable additional approximation. O. and the 4 eigenfunctions I atk) belonging to E.O. e : ) .e. O . D. a Bloch sum of the linear combinations of these orbitals.I. but procwd in a sompwhat different way.299) (htlk 1 b4k) = ( l / J z ) ( O . and the corresponding linear combinations I btR) are given by .O. O . l . have the components (ht2k I agk) = (l/&)(O.2. the eigenvalues and rigenvectors of the matrix (2. (2. equivalently. Each of the eigenfunctions I btk) and 1 atk) is a linear combination of Bloch sums of two hybrid orbitals pointing toward one another. temporarily setting Vl to zero. the so-called bond orbital approsirnation. The diagonalization will now bt. or.

3 . R ) are given by The polar diagrams of these functions are shown in Figure 2.1 .300) were compensated by the et-factors of the Bloch sums. With the help of bonding and anti-bonding orbitals the eigenfunctions of the Hamiltonian matrix (2.0 may be written in the form 1 ' I btk) - aR 1 eik'R I b t R ) . This results in the (8 x 8)-matrix (2. (2.296) with b -. t .296) is transformed iuto the basis set of the previously calculated eigenvectors 1 btk) and 1 atk). In the case of a-states the hybrid orbitals are subtracted.22.172 Chapter 2.303) (2.301) Thc exponential factors eF of the eigenvectors (2.299) and (2. and the corresponding linear combinations I a . 1 . one refers to the orbitals I h t R ) as bondiny and to the orbitals 1 arR)as anhi-bonding orbitals.11 h t l 1/2 1 R)+ I h2Rt + R)].1 . Electronic structure of ideal crystah I kR)= . 2 .305) with the (4 x 4) -matrices . The Hamilton matrix (2. 3 . For reasons which will be clarified later. 4 .304) In the second step of the diagonalization procedure the Vl-terms are included. (2. 4 . 2 .

T h e latter may be calculated by means of formnla (2. This suggests treating them as perturbations. The structure factors g t p and &) in (2.ding states. follows from that €or H & if in the f latter q.307) are defined as follows: The (4 x 4)-matrix H M couples the various bonding states. is referred to as the b o d ovbital approximation.310) as diagonal elements of H M between eigenstates.e. It gives rise to corrections to ’ the eigenvalues of relative order of magnitude I 11 I /2 I V2 I. The factor 2 accounts for the two spin states. i.309) where E d means the Coulomb energy of the interacting valence electrons which is counted twice in summing upon all band states. is replaced by E. the complete neglect of the interaction between bonding and anti-bonding states.. The zero-th approximation. and note that within the bond orbital approximation the eigenstates for a given wavevector k are linear . Tight binding approximation 173 {2. Considering the actual values of V1 and V2. with the result (2.6.310) To pro>*ethis relation. The expression for I.307) as block elements.54) which expresses the total energy of an interacting electron system by means of its one-particle energies. the i-sum in (2. The non-diagonal matrix Hab describes the interaction between the two types of states. couples the various anti-bop. One has Er$&f’= 2 k z E:(k) -Ecd (2. Within the bond-orbital approximation. and H. we write the eigenvalues @(k) in (2.306) and (2. To calculate the total energy of the crystal one needs the total energy of all valence electrons.309) may be carried out in closed form.2. the former by diagonalizing the matrix Hbbq the latter by diagonalizing Hw. Within this approximation the valence and conduction bands follow from separate eigenvalue equations. these corrections are rather small..

309). the linear combinations are generated by the unitary transformation which diagonalizes the Hermitian matrix H a of (2. one obtains from the relations (2. this coefficient repre sents the negative of the sum of all diagonal elements.174 Chapter 2. In the case of the characteristic polynomial of a matrix. This result constitutes a theoretical proof that the atoms bind themselves into the form of a crystal.e. then the diagonal elements of Hw with respect to the eigenvectors become the diagonal elements of this matrix with respect to the bonding states.. in this structure. using Vieta's theorem. Total energy and covalent bonding We proceed on the assumption that the atoms are arranged. to have a value different from the do-value of the actual crystal.310) and (2.310). which indicates that elements of the fourth group of the periodic table. the energy of the atomic cores must be . (2. Our considerations here have the sole purpose of understanding why. and that the nearest neighbor distance will have the experimentally observed value.1). here. crystallize into the diamond structure. which states that the sum of all zeros of a polynomial of degree n equals the negative of the coefficient of the (n . To verify this. as above. -4q. for that was assumed a priori.311) To get the total energy of the crystal.th degree term. as well as the energy of the atomic cores and their mutual electrostatic interaction energy.306). The total energy of this fictional diamond type crystal represents a function EEfAt"l(d) of d. One may also prove this relation in another way. however. We will demonstrate that E Z Z t a Z ( d )reaches its absolute minimum at the finite distance d = do. In this matter. The total energy E. The distance d between the nearest neighbor atoms will now be chosen. we want to understand why chemical bonding should occur at all between atoms of group IV. and takes advantage of unitarity. For the total energy EE$.298) the value (2. in the form of a diamond type crystal. If one sums the eigenvalues @(k) over all i . but rely on experience.310).f$a'(d) of the crystal is composed of the energy of the valence electron system in the field of the atomic cores. This does not prove the correctness of the diamond structure of the crystal.f'(d)of the valence electrons of a crystal with G3 unit cells. one must also show that no other crystal structure can yield a lower total energy minimum. Electronic structure of ideal crystals combinations of the bonding states I bik) only. We will not address this question. as is stated in relation (2. i. In other words. the total energy reaches a minimum at a finite distance d = do. confirming the validity of equation (2. q. under normal conditions. therefore.

Finally. one may again use the fact that the core states of the crystal do not differ from those of the free atoms.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. the repulsion dominates over the attraction.and p . it takes its absolute minimum value. The hybrid energy q. the total energy E z l b l ( d ) of the crystal varies with d as shown in Figure 2. The corecore interaction energy approximately cancels. For large d. Overall. This means that only the mutual electrostatic interaction of the cores results in a structuredependent energy contribution.orbitals of adjacent 2 atoms.-levels and two in atomic cp-levels. against the negative Coulomb energy -E.1 in expression (2. This means that the initially free atoms will not remain free but form a diamond type crystal with nearest neighbor distance do. increases as d decreases. This is true because the valence electron charge of an atom equals its core charge for the crystals considered here. of valence electrons therefore. For the elements of the fourth group of the periodic table with their two electrons in atomic €. the same value as the electron-electron interaction energy E d between the valence electrons on different atoms. The negative difference of the two energies (2. They experience what is called covalent chemical bonding.312) The d-dependence of this energy is due to the fact that both Eh and V z depend on d . the attraction dominates over the repulsion. approximately. and V because this quantity is the matrix element of H between hybrid orbitals at nearest neighbor atoms.2.312) and (2. and for small d.311). The core-core interaction energy has. corresponding to a repulsive force.24 schematically. In order to provide a better physical understanding of the nature of covalent chemical bonding. At the equilibrium distance do. Tight binding approximation 175 added to the energy value of equation (2. the total energy of the crystal is given by (2. V2 decreases with decreasing distance d.313) where Eo. It is given by the expression . corresponding to an attractive force between the atoms. 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. In doing so.6. accounts for the energy of the atomic cores.313) represents the cohesion eriergy of the crystal. again. while the internal core energies sum to a constant Eo.311). one has (2.

22).ral distance d (schematically).24: Dependence of energy difference Eza?''' ( d ) -E::+Ts on f.+electrons i s lifted into a p-state or. the energy of the two electrons decreases. to a smaller kinetic ene~gy. However.e. As we have seen. b e cause of constructive interference. The latter difference may he understood as the energy increase of an atom if one of itb two . i.and two p-orbitals. corresponds to a smaller momentum uncertainty and. The energy gain per atom amounts to 4 I Vz 1. depending on whether bonding or anti-bonding states are considered. if the condition 4 I V2 I> ( e p . 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. quanturti rtieclianical phenonienology is essential in the interpretation of this behavior. the potential energy of the Coulomb interaction of the two electrons among themselves and with the atomic cores remains almost unchanged. it is energetically favorable for covalent chemical bonding to occur. If it exceeds the energy necessary for promoting an atom into its sp'-state.176 Chapter 2. equivalently. and that I 4 2 I exceeds the energy v differericc (cP . In this process. Formally. therefore. This can be constructive or destructive. i. Elecbronic structure of ideal crystals Figure 2. In sp'--hybrid states. their kinetic energy decreases considerably. One calls this population the promoted configuration of the atom.e. . the electrons of adjacent atoms are capable of pronounced interference. Altogether. 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. Unlike the bonding of electrically diflerent charged ions.F ~ ) holds. This may be imderstood in terms of the Heisenberg TTncertainty Principle which tells us that a weaker localization. in a bonding state. In the casc of constructive interference.cs).he inter-atomic crystal atom Etotol -Eta. if its four valence electrons a x put into four sp'-kybrid orbitals rathe1 than into two s. a larger positional uncertainty. covalent bonding between neutral atoms Lannot bc understood in terms of classical physics.

~8. neigIi1. which was merely assumed at the outset. the diamond structure of the crystal. One calls aP the polarity uj bonding orbitals or simply the polardty of bonding.317) represent the probabiMes of finding an elrctron in the bonding state at atom 1 or 2. The charge of the cation is given by c Z * with Z' = (Z.e. The atomic structure follows. from the electronic structure.316) and (2.where 21 is the number of valence electrons at + bp. where we set a p . . . The bonding and anti-bonding oibilals arp given by the expressions !+. a scries of 111-V and 11-VI compound semiconductors form crystals of this type. This results in an enlargement of the energy gap betwcm the valence and conduclion hands. and atom 2 is the negative anion. Ionic bonding The ionic contributions to chemical bonding will now be calculated for mat. the transit. Atom I becomes the positive cation.Vs/dV. whcre the electrons occupy only boxrding orbitals. The electron prpferpntially stays at atom 2 . i.art' positive.305).+ rials having the zincblende structure.ors of an atom on the comers of a tetrahedron. ! then I!?. so to speak. A s is well-known. respectively. With this replacement. In this way the polarity of bonding orbitals is such that. and also up.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. In this way thc above consideration also justifies focming on the tetrtlhedral crystal structure of diamond type crystals. If f f f is deeper than c i .a p ) and (1/2)(1+ctp) in ('2. in the ground state.4 t $ap). T h e f d o r s {1/2)(1.The c:ondition necessary for thc occiirrcnce of bonding eigenstates able to host all vrtlprrcp electrons is the ordering of the newest. 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. the previously electrically neutral atoms heconie charged.

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

+(x) the crystal Hamiltonian H . With growing polarity of the bonding.e. 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. This explains the transition from the semiconducting properties of the group IV crystals to the insulating nature of the I-VII compound crystals. the absolute values of V3 are so large in comparison with V that the bonding polarity op is approximately 2 unity.11: Madelung constants for several crystal structures. k .7. In the case of the I-VII compounds. This implies that almost all valence electrons of the compound stay at the anion. which represents an essentia1 part of the bonding energy and forms the driving force for the formation of ions. which have lost all their valence electrons. Then the crystal consists of positive ions of the group I atoms.e.7476 structure. by ( a / 2 .7. In this case. i. p -method 179 Table 2.6410 1. If one replaces the wavevector k in uYk(x) by a constant ko. This structure is determined by the hladelung energy only. One refers to such crystals as tonac crystals. 2.6381 1. Therefore.x) and the latticeperiodic BIoch factor uvk(x). i. Zincblende U’urtzite Rocksalt 1.2. while retaining k in the exponential factor. as mentioned above. rocksalt and cesium chloride structures.7 2. a / 2 . no longer depends on the crystal structure. a/2). ionic crystals exhibit structures with particularly large hladelung energies. the energy gap becomes larger. the energy gain due to the transfer of electrons from cations to anions.1 k .p -method Fundamentals Luttinger-Kohn functions The k. and negative ions of the group VII atoms whose valence shells are completely filled. p-method rests on a particular property of the BIoch type eigenfunctions pV. then the resulting functions .

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

7. p! (2.(ko) Ti2 + -(k 2m - ko)2. (2.p(k) = Ho(k) h + -(k na .327) allows for an important rewriting. reads .328) The matriv on the right-hand side of (2. If one defines Hk.2..Hamiltonian ‘l’hematrix elements (pkko I H I p’k‘ko) of the llarniltonian bptween T.329) with (PkkolfflP’kko) = (PkoIHk.326) which yields where we have set E:(k) = E.eik-x] = eik-x (p2 f 2fik. the Schriidinger equation (2.(k)lP’ko).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 -method 181 With this expansion.327) has been transferred to the new Hamiltonian Hk.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. (2. if one uses the easily provcn commutation relation [p2.ko) . The SchrGdinger equation (2.p(k) in the k-independent partial Bloch basis lpkoko) = jpko) for the wavevector k = ko.325).p .178) in the Luttinger-Kohn representation bmomes k . The k-dependence of the Luttinger-Kohn basis on the left hand-side of equation (2. p + h2k2) . with this new Hamilt onian. k .p(k) on the right-hand side. (2.

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

2. we call M L 1 the effective mass tensor at the critical point k. the energetically higher of the two bands should have a large positive effective mass. This holds the same content as equation (2. whose mutual interaction is stronger than that with all other bands. k . if V&. relation (2. According to it.' with respect to the principal axis system.3331.p-correction vanishes in first order perturbation theory.6. then the k .193) used above without proof. and the energetically lower a mass of the same large absolute value but of negative sign. p method 183 (2. this exact relation yields V&v(k)lb = ( h / r n ) ( v b l p l v h ) . The result reads where. In particular.(k)\k. i.. because ko may be an arbitrary point of the first B Z .7.337) 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. we set (I& sion in the form I p I pkc) = (v 1 p I p ) . for brevity. of At. = 0 holds. For pairs of bands which are closer to each other than to all other bands and. For the diagonal elements . One must proceed to the second order to get a non-vanishing contribution from the k p-perturbation. One expects small effective masses for large momentum matrix elements and small band separations. This .338) allows one to also draw a conclusion about the signs of the effective masses. As far as the band separations are concerned (only for them can one make an easy estimate). if ko is a critical point kc.e. therefore. We rewrite this expres- mz' Generalizing the terminology introduced in section 2. one obtains from (2. The tendency indicated is that the absolute values of the effective masses become larger for smaller momentum matrix elements and larger band separations. we will later find conhmation of this tendency in all concrete cases.

and at these symmetry points. in general. we set & = 0. we may identify IvzO) with yz. with regard to their transformation properties under the action of elements of o h . one must carry out second order k. Electronic structure of ideal CFZ. these eigenfunctions belong to the irreducible represent ation l?b5 of the cubic group oh. In quantum mechanics. y of the components 2. one constructs the matrix of the perturbation operator not between degenerate unperturbed eigenstates. The vector components 2. To this end. where m can assume the values 2.S~~~S conclusion also proves to be valid in all cases in which the assumptions of this calculation apply. An important case in which the k . perturbation theory for degenerate energy levels is c o m o n l y of first order . is the valence band maximum of semiconductors with diamond structure. z of position vector x. One must therefore choose a variant of perturbation theory for degenerate energies which works in second order. For other materials this procedure serves as a zero-order approximation which can be used to proceed further (as we will do below). zx. degeneracy of the energy bands often occurs.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 2.4). no longer degenerate. z of the position vector itself transform in accordance with the irreducible representation I5 o Oh. and IvzO) with zy. The maximum is 3-fold degenerate. In doing so. Si.y. ' 1 f . the valence band maximum of diamond type semiconductors is located at the center r' of the first B Z .g. a basis of this repz resentation is formed by the products yz. but between the (also degenerate) eigenstates of first order of perturbation theory.184 Chapter 2. p-perturbation matrix between the degenerate unperturbed states vanishes. 2. This approximation is valid for semiconductor materials composed of light elements only.7.6.2 Valence bands of diamond structure semiconductors without spin-orbit interaction As we know from section 2. As indicated in Appendix -4. as is commonly done. If this happens. We denote the three pertinent Bloch functions by IvmO). including.2. Band degeneracy Critical points are often symmetry centers or lie on symmetry lines. These are. This case will now be investigated. for example. Therefore. According to section 2. w e initially neglect the spin-oIbit interaction. This procedure does not apply here because the perturbation matrix at critical points vanishes in first order.y.pperturbation theory €or degenerate bands. Therefore. IvyO) with zz. By diagonalizing this matrix one obtains the eigenvalues in second order perturbation theory.3.

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

the valence band energies Ev and Forresponding Rloch states I&.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. c one can show that these correspond t o the three types of non-vanishing + + + + + . rn. '(vrnklE. transforms under symmetry operations of the cubic group Oh according to the $-fold product representation [rb5 ri5]a [1'1~ x l ? 1 ~ ] . (2. one finds [I'15 rl5Is [& x r&lS x [I'Is x = I = r1 r12 ra. number of times the identity representation occurs in the product [I?& x riE.342) in the more compact form With respect to the indices a r P lthe tensor D z i . A short calculation yields where is a fourth-rank tensor. therefore has three independent components. namely '(vmklH!vm'k)l l(wn'kl&:y)= E ' .(O)..340) can be obtained by means of expression (2.339) for the perturbed states Ivrnk)'. x x where the index s denotes the fiyrnmetrical part of the product.-k 5T'k5 The tensor D z L . is symmetric. then contains as many independent elements as the L?zk.345) one can see that D Z k . Since the states I p ) = 1 P O } are eigenfunctions of H with eigenvalue EEl= E. and with respect to the indices m .). Harniltonian m a t r i x The (3 x 3)-Hamiltonian matrix '(vmklHlvm'k)' of equation (2. one may write (2. which yields [rk5 r& x [rI5 rl& = 3r1 rz 4r12 x x 3 .186 Chapter 2. Using Appendix A .lrn x I115Is.) therefore follow from an rigenvalue equation which is decoupled from the remaining bands. According to Appendix A. m' it is IIermitiaa From equation ('2. Electronic structure of ideal crystals In second order perturbation theory.

and D Z . however. one proceeds in a similar way. namely according to the pseudovector representation I':s. (considered in Appendix Iz A ) and their products. the corresponding scalar products belong to the. L .identity representation. In the product spacc k. Since QB a l remaining matrix elements Dmm. whirh leads to the goal more quickly. m e obtains a basis which consists of subbases. one has to determine all invariants of the product space. such as the fact that they can be chosen real. vanish.] of the point group oh. 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=. since it is known how these matrices transform. To find the most general Hamiltonian matrix compatible with the symmetry oh. each of which belongs to a particular irreducible representation of Oh. hl = D$$. 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. one obtains . One determimes a basis from subbases which transform according to the irreducible parts of the representation [I'15 x r15Iy.Iv. The elements L. but is formally more dernanding.The Hamiltonian matrix reprewrits an element in the product space of Ihe two spaces which is invariant under transformations of the point group Oh. I. M and can be calculated if the Bloch factors are known. they are invariant. that is to say. In the absence of this informalion. 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 a matrix basis can easily be constructed by means of the 3dimrnsionel angular niomenturn matrices Iz. and N = D$ f D g .p -method 187 matrix elements D z z . k. This representation is reducible.2. By & tion [ decomposing it into i t s irmliicible parts. we consider L . We introduce the abbreviations L l& D g . As seen in Appendix A.€ 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 (2.344) can also be derived in a somewhat different way.f-fi of the components of the vwtor k.

(2. not isotropic. the two degenerate bands E. Valence b a n d s t r u c t u r e The eigenvalues of the matrix (2. This process is called the method of invariants. such as the interaction between the angular momentum of Bloch electrons and an external magnetic field (see section 3.l/a(k) of equations (2.3(k) = .lp(k) = . one has L = -5.n(k). one 2-fold degenerate and one nondegenerate (see Figure 2.9) or the interaction with mechanical strain. E. A comprehensive outline of the method with several applications i s given by Bir and Pikus (1974). Using these values. E. In this book. [lll]and [110] the dispersion curves are determined by simple analytical expressions as follows: E.[ L 1 (2.345) 1 E. (2. It also allows one to determine the matrices for perturbing Hamiltonians other than that of the k .347) 1 2 + M + N]k2. and it quickly leads to the goal if one considers spin and spin-orbit interaction. For the three symmetric k-directions [loo]. p-interaction.N]k2. we will only use the method of invariants occasionally. N = -8. in general. E.348) Along the two directions [loo] and [lll].lp(k) = M k 2 .[ L 3 + 2M . (2.3(k) = L k 2 . splits into two bands. It is applicable to arbitrary symmetry groups and degrees of degeneracy.2(k) = .l(k). One speaks of a warping of energy bands.[ L 2 +M . E. but evidently.64. In the case of Si.60.344) form three valence bands E.3(k) = . E.188 Chapter 2. the valence band. 1 E. M = -3. This indicates a %fold splitting of the valence band for such k.346) E. All bands are parabolic.345) .68 in units of ( h 2 / 2 m ) .l(k) = M k 2 .3(k). no degeneracy remains. Electronic structure of ideal crystals the most general invariant of the product space and thus the most general Hamiltonian matrix compatible with Oh symmetry.[ L 3 + 2M + 2 N ] k 2 . In the [llO]-direction and also for all more asymmetric k-vectors.N]k2.25). being triply degenerate at r.

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. Isotropy exists only if N = 0 and L = M . 2. p method 189 Figure 2. hut often not negligible).25: Valence band dispersion for diamond type semiconductors in the vicinity of the I'i5-maximum for different k-directions. anisotropy grows stronger as the difference between the masses of the two types of holes becomes larger. -r . We now proceed to consider the effects of spin-orbit interaction. Then. The electron states then depend on both the position coordinate x. the valence band structure is significantly influenced by this interaction (in the case of Si it is small. and the quantum numbers of the electron states contain provision for both the motion in coordinate and spin state u describing the spin motion. Conversely. or (2. We denote the product functions by (sxlpk) or (sx(pkO).7. Here u means the spin quantum number which can have the two values u (spin up) and cr =I (spin down). there also is no longer any distinction between light and heavy holes.2.7.3 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. for most of the diamond and zincblende type semiconductors. The results discussed above were obtained without consideration o l spinorbit interaction.s(k) in these equations.346) have smaller curvatures than the third band E. Then. by definition.respectively. However. augmented by multiplication with the eigenfunctions ( s l u ) of the z-component of the spin operator. k . and on the spin-coordinate 3. Thus the first two bands correspond to the heavy holes and the third band to the light holes of Si.

351)) an additional k-dependent term appears in comparison with the spin-less case. the (xlvuko) signify the spin-dependent Luttinger-Kohn functions of H . where Hgo is given by .. but not of H H. p-term arising from H . m x VV(X)]. (2..190 we have Chapter 2. = P’U’ (2. The additional term can be taken into account by replacing the operator Ht. of (2. except that the p-operator is replaced by the operator p+(1/4rnc2)[5 x OV(x)]. contains the momentum operator. Ip’v‘kO)(p’u’kOIE l .354) and the Schrodinger equation (2. This term has the same form as the (A/rn)k.~ + HsoIp‘u’O)(p’u‘kOIEu) E . but not of fi + f l W .. a. Now we wish t o explore the particular consequences of spin-orbit interaction for the previously . + H80/p’a’kO) = ( ~ u O I H+ Hso{p‘u‘O).353) becomes With this the Luttinger-Kohn representation of H (pukOlH + H.351)) takes the form C(~(TOIH~.p of equation (2. ) ..351) In calcuhting the matrix of H t H.3501 One has to be aware that the (sxlvuk) are eigenfunctions of H .) .355) Up to this point.~ (2.329) (for ko = 0) by the operator Hk.x = H o ( k ) Tl + -k .E . ) . equation (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. (pu kO IE. ( p n k O l E . ~. Correspondingly. we have kept the discussion general.352) with ii = p 1 + ---[a 4m c= (2. as a consequence of the fact that 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. (2.56) as (2.

i i 0 0 0 1 0 0 0 0 0 . in the calculation of the matrix elements of the momentum operator p.357) Below..2. x (r2 r 2 T’i5+I7L5).= rl. Ivy 7 0 ) = ly tj. . 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).a H . A 3 (2.1 i o i 0 0 (2. we need the matrix elements (vrnuO~Hso~wm’u’O)H.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 .358) 0 . (2.57).the matrix (avmOlH. . x P2. We denote the value of (vyOl[VV(x) x p].i . as was done before.e. At k = 0 the expressions E:(k) and k ii are both zero. are therefore also those + . k p method 191 considered valence band states.4 (vmaOp..7. Because the Bloch factors are real? these elements are pure imaginary.lvzO) holds. It)z 1 0 ) 3 1 1). The eigenenergies and eigenfunctions of the total Hamiltonian Hk. 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). / ~ = ( V Z O l PV(XjXp1ytvrO).jvzO) by (4m2c2/h)(i/3)A. The operator [VV(x) x pi is a pseudovector and transforms according to the irreducible representation ri5of oh. as well as + + (~.’u’O) =- A 3 0 0 0 0 . To this end.357) and the explicit form of the spin matrices given in (2. .i o 1 0 Here the rows end columns are associated with the basis functions in the sequence Ivz T O j = I t). we will see that the constant A is the energy splitting of the valence band at J? due to spin-orbit interaction.. ( u ~ u O I H . ~ F.Ivm.(uyO~[VV(x)x plrlvzO) = i . Applying equation (2. Spinz s orbit interaction couples orbital states and spin states to each other.Ol[V(X)XPl*l v y 0 ) = (WYOI [ w x ~ x P l . ~ o ) where (vxOl[VV(x) x plz I u y O ) = -(uyO I [VV(x) x p].. which the identity representation occurs exactly once..1 i 0 0 0 0 0 . 0 )namely. i. The entire third-rank tensor (vrnOI[VV(x) x p]lvrn’O) therefore 1 belongs to the reducible representation I’b5 x Ti.I a’w m ‘0j becomes 0 . we set h 4m c . .

1. i. 1. 0 .192 Chapter 2. Electsonic structure of ideal crystals of H. 2 ) . Iz J). The matrix (2.. o. .363) refer l o the IwmaO).359) u'm' c (vmaO~H. 1.3 62) with the two corresponding eigenstates IEv5) - -(o. The lEvl). the cigcnvcctors take the form z y The eigenvectors lEvt). 12 I).i . IEv2) Jz - IEv3) = 1 i z(l. using basis functions IvmaO). . 0. o.361) to (2. fi 1 i E 0. IEv4) = -(O. . Iz i). . Angular momcntum basis.O).361) have a simple meaning. respectively. 1 ) .355) at k .O. = Eigenfunctions at r.360) with the four corresponding eigenstates. O .i . 0 . alone. .lvm'a'O)(vm'a'O~E) E(wamO(E).o. 6 of (2.355) has a 4-fold degenerate eigenvalue Ev1/2/3/4 = 1 p (2. these representations . (2.. l I ) .i. O. 1). o). Jz O.1. IE ) ~ v1 - 1 T ( 1 . so thsl the Schrfidinger equation (2.----(--I. i.i . .o. O ) . w6 . J y I).IEvz).361) and a 2-fold degenerate eigerivslue Ev5/6 - --A 2 3 (2. If we abbreviate these by Ima) I T).IEv3). IEv4) are basis functions of the irreducible representation of the cubic group o h .0 becomes (2.d3 (2.363) The components of the eigenvectors given by (2.2. Acrording to Appendix A.

Therefore one also uses the angular momentum notation €or the last two eigenfunctiona of (2. D Dis taken ~ as a representation of the subgroup o with +1 for inversion. .). .3621. 1 by means of time reversal. r ing to Appendix A .ynin.7.e. . 4. total angular mornenturn. by forming the comphx conjugate of the original eigenvector and subsequently multiplying it by rP. of Oh. I--)2 4 2 1 = -"-2Iz i fi t) + la: + iY 1 1 1 7 33 i = 1. in particular not from a representation for J = (this happens with in the case of Oh or r:) in the case of T d . J2. The valence band: being B-fold degenerate at the r-point if spin is not taken into account. . one with j : and one with j = if the spin-orbit interaction is considcrccl. These representations do not arise from any representation V3 of the full orthogonal group. The size of the splitting is given .): 1 follow.365) and (2. while the rncrgy eigenvalues differ if states with different eigcnvalues of J' are consitirrrd.3641. 2 .and -$ L One therefore denotes the first four eigenfunctions of (2.366) is determined only up to a phase factor. 1 .iy T) +2/2 111%I--) Jz -iY I). ?. Tlicse representations are reducible. 1 .360) and (2. as Di x T = Y$ +I ' . eigenstates having the same eiggmvalue of the the angular momentum squared. respectively: from the states with positive momentum. I$$).366) henceforth as the angular momentum basis. We refer to the functions Ijmj) of (2. i e .IE.I ) .364) by + 4.1 . The lEvs).365) I--)2 2 3T = -[& I.-o)rhitqditting must occiir? one can recognize just by means of a grnnp theoretical analysis of the problem. therefore splits into two bands. which is chosen heie such that the states with negative total angular I): $I. accord.366 and (2. According to (2. i. That such a . The six valence hand states at transform in accordance with the &dimensional representation Dl x .also have the same energy eigenvalue. k p -method 193 emerge from the representation 213 of the full rotation group if. and of the z-component J z of J for the eigenvalues m j = 3 2. I--)2 2 33 = -1rz 31 + iy t). but the expectation values of J2 and J z are the same as those in the Dl basis.s) are basis functions of the irreducible representation I'y of o h . =.2. one sets rt 4 Each of the dgenvectors (2. ' I 3. 22 (2. 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 ).

194 Chapter 2. with different projections Jz of total angular momentum on the z-axis. also only couples the valence band states among themselves. The functions Ipgk)' form a complete orthonormal set in t a m s of which the Hamiltonian H may be represented. 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. one finds for the valence band states Ivmcrk)' the expression r. approximately. 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. i. The submatrix with respect to the valence band states (vmmk)' is decoupled from the remainder of the matrix in second order perturbation theory. Electronic structure of ideal crystaJs by the constant A.352) i first n order perturbation theory.p-interaction due to spin-orbit interaction. . but not to states from other bands. In analogy to equation (2. where we use the same abbreviations as in (2. which determines the strength of the spin-orbit interaction. We have seen how this can be done approximately in the preceding section.339). Off this interaction is no longer zero and must be taken into account in addition to the spin-orbit interaction. without consideration of spin. Therefore A is called spin-orbit splitting energy.he two interactious are supposed to be weak. Since H. Analogous relations hold for the states of the other bands. Valence band structure off r The above statements refer to valence band states at the center r of the first B Z . It will be omitted below.e. '5'ince t. Then we have.367) d e scribes the change of the k .7i in the eigenstates Ivmcrk)' of (2.339).. States with different m j . where the k p-interaction vanishes.355) in this representation reads The spin-dependent term of k . but the same J2. i.have the same spinorbit interaction energies. the Schrdinger equation (2. 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.

.(vm’a’O) takes the diagonal form (hjlff. Now we use the fact that H. k p -nrt.365) and (2.365) and (2.366)..7.olj’m.) = o $ o o o o + o o o o g 0 0 0 0 - 0 0 0 9 0 0 0 ’ (2.355).371) If one applies this transformation to the Schrodinger equation (2.qolvm’a’O). then the matrix (vmaOlH. One has (2. ma (2.366). is diagonal in the angular momentum basis Ijmj) of (2.lv7n’a’k)’ (vmaOlH.370) can be readily The corresponding unitary transformation matrix UmjmJ obtained from the rclations (2.th<>d 9 195 (vmakIH..372) 0 .2. 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).

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

it corresponds to the band of heavy holas. C 2 3 7 1 -[N2 .C. Its 2-fold degenerate eigenvalue Er7(k) is given by The energy level Eo1/2/3/4 Bra(0) equation (2. N in the matrix D. of (2.). B. 2 Using the explicit expressions for Q.k. p +method 197 resulting Bamiltonian matrix agrees exactly with that of equation (2. 1 and . B = 1 .343) are affected.2.( L . .378) : Thc 'T (2 x 2)-matrix block of the full (6 x 6)-matrix is already diagonal.1 For arbitrary kdirections. two 2-fold degenerate bands Erf. defined by : - . this yields (2. k . 3 (2. and starting from the 2-fold ckgenerdte level Ew5/6 = Ey7(0) r in at (2. I I) :. the pertinent .7.0 read) . eigenfunctions are I$$) and. : 1 The eigenfunctions for k.which lies at an energy separation A below. Instead of the latter.M)')].(k) arise off of I?. 7 2 .374) has the two 2-fold degenerate eigenvalues E&(k).( L . Only the Z : explicit expressions for the constants L . the heavy and light hole states are linear combinations of all four basis functions ) :. . . M . The 2-fold degeneracy of ixll band6 is a consequence of time reversal symmetry jointly with spatial inversion symmetry (see Appendix A). Since these arc understood as empirical parameters.376) A = -(L 3 1 + 2M). this also does not play an important role. = 0.360) is 4fold degenin erate at I?. S.(k) (see Figure 2. = k-.Ad). a similar %fold degencratc band Ep.) The described structure of the valence band around r represents what is called the Lallznger-Kohn modal. T. The particular form of the bands is determined by the three consttlnts A . R . . 1 3T . 7 3 called Luttznger parameters.374).26) evolves off of r. The E&-band has weaker curvature. . 122) and. Correspondingly. For k-.362). one can use the dimensionless parameters 7 1 . .) 'l'hc EFa-band is that of the Zzght holes. Even with this additional approximation one obtains the most general I'8+-Hamiltonian compatible with the symmetry of the crystal. The matrix (2. . 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.

The constant C measures the strength of warping. For C # 0. A h2 -----TI. is not defined in such circumstances. one can define an anisotropic effective mass. for instance.196). N . M .377) not with respect to the components of k.12. In the case C = 0.198 Chapter 2. ha Lni h2 C2 = ---12(7.2~. II [loo] G+l 5. The effective mass tensor.e.but with respect to Ikl. by averaging . The constants L . (23 8 0 ) Values of the Luttinger parameters are listed in Table 2.26). Electronic structure of ideal crystals I I I s. by differentiating in equation (2. This would not have resulted if the interaction between the rBf-states. II [ l] Il Figure 2. as given by equation (2.2 2m . the point k = 0 is a singularity of the energy band functions Erf. Concerning the dependencies on the direction of k. Instead. B 2m = -. which were originally used. may be expressed in terms of the Luttinger parameters by the relations: Both energy band functions E&(k) and Er. they are parabolic. In their case one again has a warping of energy bands as discussed above (see Figure 2. the spin-orbit-split band Er7(k) is isotropic.26: Valence band structure of diamond and zincblende type semiconductors in the Luttinger-Kohn model. i. while the heavy and light f hole bands Er8(k) are not. The dispersion for the two k-directions is different (band warping). 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.f states. the warping vanishes.(k) depend on the square of Ikl. had not been neglected as it in fact was.7:). If the warping of energy bands is ignored.

23 1.4 A 0 0. k.69 16. product.08 over all directions.3 Ei 5. Formally.8 35. E i .5 GaSb InSb ZnSe HgTe 4.18 2.7.p -method 199 Table 2.4 21.85 11.52 26. and the Luttinger-Kohn model also applies to zincblende type materials.64 0. 1982.23 0. yz.4 1.42 1. as distinguished from diamond type semiconductors. the k-linear terms are small.2 17.67 10. Temperature below 70 K .94 4.2.8 25. the model does not apply because the matrix elements of the momentum operator p between the triply degenerate valence band states without spin. where the unity representation does not occur in the corresponding I x r15 x ' i . for materials having the zincblende structure. ready present in the diamond case (see equation (2.56 5.35 19. The non-vanishing matrix elements (omOlplvrn'0) give rise to terms linear with respect t o k in the I1 valence band Hamiltonian.03 15.8 Ep 0. elements (vrnOlplvm'0) belong to the product representation I1 x I1 x r 5 The latter contains the unity representation.8 12.98 0.2 6.34 0.25 13.12: k .30 0.26 16. The reason for this is the absence of inversion symmetry in the zincblende structure.7 22.3 39 GaAs 2.044 0. The most important requirement for the Luttinger-Kohn model to be valid is . as a rule. and E .67 -0.8 0.26 13.91 1.29 0. 7 3 are adjusted to the Luttinger-Kohn model.48 3.1 0.08 4. (After Landoldt-Bomstein. The Luttinger-Kohn model was described above for the case of diamond type semiconductors.12 therefore also contains Luttinger-Kohn parameters for semiconductors of the zincblende type.70 0.8 0.90 -0.38 4. E p = ( 2 m / h 2 ) P 2s a measure of constant P in i Kane's band model. in eV.S n 0. this yields the ordinary isotropic heavy and light hole masses but in the sense of an average. The values for 71.2 2.) Material 71 yz 73 C Si Ge cz . besides the quadratic terms which are are al'5 However.6 0. provided the other requirements which underlie this model are satisfied. 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 1.344)). A.p-band parameters for selected diamond and zincblende type serniconductors.9 5. Table 2. IvrnO).53 8.

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

ni . the matrix does not haw to vanish.. z. and the reader should keep the dxerent meaning of s dearly in mirid to avoid confusion).0 are IvmuO) and I c s v O ) .WP may neglect thc spin-dqwndcnt part by virtue of the same arguments as in the Luttingerkohn model. idirating the 3.p -methad 201 Neglect of interaction with remote bands We analyzr the generally valid Ychrbdinger equation (2. ri2 2m 2 (2.)-k 2m (wmOlHo(k)IcsO)= 0. but unavoidable. The three needed matrix elements of this operatw may then be determined as (2.?i. considering spin md spinorbit interaction horn the outset. The diagonal rlemenl (csOlplcs0) of p in the conduction band state IcsO) vanishes exactly.I. As such.385) The matrix elements (vmOtplzlm'0) of p between the valence band states are wglectctcd in accordance with the assumptions madr above. namely {Fa/m)k-. The pertinent spin-dependent Bloch functions at k . rmpectively. The nun-vanishing matrix elements of p are then given by the relation . ~ . (2. l v d ) and set it equal t o z ( m / h ) P . The conduction band index c will be augmented by 3 .384) Iii the otkw o p ~ a t o r term of A V ~ . k.383) h2 (csdlHo(k)lcsdO) = 6. it contains exactly one independed rlcnwnt. Since the unity representation is contained in it = Fl + exactly once. 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 . We again denote the thrw valence band indices by urn. above.7. one may chose ( c s O l p .u.351) using the assumptions and approximations discussed.2.382) (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 {cs01plvmO) between valence and conduction band states tranuform according to the produrt representation r x I115 x r15 1 trls i l725. .

~ 7~~r r8o~~~ p v = I c syo~/ p . thus this factor vanishes and with it the whole matrix element (umaOIH. l rztj .F. because l’i5 coincides with I’15 for the tetrahedral group. IY 11.. . 0 0 0 iPk.I csa‘O).iPk. The unity representation does not oc cur here.388) The caordinatedeyendrnt factor of (csuOlH. 1).387) Ec --iPk. l I). 0 0 0 0 0 I ] /s 0 0 0 0 0 0 -iPk. 0 0 0 0 iPk. The other factor (m/Ta)was introduced for convenience in the final dispersion rclations. The coordinatedependent factor of the first matrix element transforms according to the representation r15 x l?25 x I’l . iYk. a th I.oj cscr‘0) involving the conduction band states. (2. 12 1). if the Bloch factors are real as we assume. 0 0 where thr lines and columns arp ordprcd in the sequence I2 I). With the moinentiim matrix elements of (2.I’z+ I’15 r25.202 Chapter 2. -iPk.. There are new matrix elPrnents (vmuOlH. 0 0 0 0 0 0 0 0 0 0 0 iPk. 0 0 0 0 0 E C 0 0 0 0 0 0 -iPk.3861. whence + (um. one can adopt the results which were formerly derived for the valence band. Ig I). Electronic strr1c:ture of ideal crystals ~ c s o ~ p .lwm’a’O). ~ ~= ti .aOlHs”Icsrr’0)= 0.386) The factor 2 giiarantws that P i s real.olcsdO) belongs to the product representation rlx r 2 5 x r : arid must therefore likewise wnish. For the Flj-vaknrc band rlernents (wmcrOlH.lrsa’O) and (csuQIH. -iPkg -iPk.)~ = ~ (v ) ~ -o m (2. thp Hamiltonian matrix (pu01Hk . lz 1). .(k)lp’u’O) takes the form (2. Finally ihe matrix demerits (puO1Hsolp‘m‘O) nl t h e spiri-orbit interaction operator ITrn haw to lie detrrminpd.

1s t) and 1s J] are eigenhnctions of the Hamiltonian matrix (2. 0 0 0 0 Ec 0 0 0 O 0 0 ? 0 -ig A 0 .. of (2. T h {2 x 2)-co. The (6 x G)-vdencr band block is identical with the matrix of the spin-orbit interaction operator H.490) at k # 0. Ec -iPk.366).A 0 Here.nduction band block is already diagonal. i.. we write them in the form T 1) of ihe ctngpubr momentum basis (2.7.2. indeed. the order of rows and columns is the same as in (2. o iPk. that one can also obtain the secular equation directly.T representation + H. is gken by the following matrix . p -method 203 Thus. side by side. The matrix (2. We will do t h s . -iPkY -iPk. so simple. For k = 0 and vanishing Ec. however. 0 -2z O .391) .c. To diminate the free elmtron part ( h 2 / 2 m ) k 2from the eigenvalues Elk). then the matrix decomposes into a (2 x 2)block for the conduction bt~ncl.390) at k . iPk. -iPkg -iPk. 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. E(k) : E’(k) -I--k2 where E’(k) satisfies the following h2 2m (2. iPk.390) is.387). the total Hamiltonian Hk.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. before we h r t h w consider the angular momentum basis. k .and B (6 x 6)-block for the valence band.350) for the Luttinger-Kohn model. The eigenfunctioiis of the two blocks arc simultaneously also e i g e h c t i o n s of the total matrix.A i$ 0 0 o 0 0 o 0 0 -A 3 0 -- -27 $ i+ iPk. The eigenfunctions at k .0. iPk. 0 0 0 \ iPkz 0 0 a 3 0 0 2 5 --iPk.A -+ i+ o 0 0 0 0 0 .

Secular equation

Chapter 2. Electronic structure of ideal crystals

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

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.


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-


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


0 U






0 0


0 0



0 0

0 0

W 0


U '

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


- A,k2


E'(k) +


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



k.p -metbod


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)



P2k2 = 0.


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,



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


bi(k) -



+ TA



+ [&(k) + -


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

From (2.399) it follows immediately that


Chapter 2. Electronic structure of ideal crystals

(2.401) and from (2.400) we obtain

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


P2 -k E,






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.


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

= E, << A, Ef


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,


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

2.7. k . p -method



7 A
2 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

- -k

PZ2 . 3A


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






<< A, EF < 0


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

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



8; I / P 2 )

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




(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


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.



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



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.


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.


t lo

w - 8


w 6

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

r 1




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


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


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


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

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.


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.)



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

-levels arising from the &-band on the A-line which enters the r7f-level at I. Ge. ( A f t e r Candoldt-Blirnstein.43 0. and that of GaP in terms of ordinary representations.30 0. and IIgTe read i = u h . but at L .087 0.45 0. For both materials.43 2.07 5 0.11 0.044 0. Te. and Se read i ~ 1 1 I (parallel. PbTe.08 0.17 0. syniniebry axis).54 0.14: Characteristic data of the barid structure of selected semiconductors.33 0.1 0.32. perpendicular to .29 0.1 PbTe 0.8 - -. ‘ 2. effective masses in free electron masses.064 0.3 r X 1. Temperature 300 K. 1982. For Si.66 hl II 0.34 0.15 0. Gap.7 GaP CdTe HPn: CdY r r 1. since they have the same Bravais lattice.3 r L 2. Thus the band structure of GaAs is described in terms of spinor representations.) Milaterial i _ .4 0.- difference between the conduction bands of Ge and Si is the location of the respective absolute minima. In Ce it does not occur on a A-line.022 0. while for GaP it may be neglected.50 0. C-BlmdMimirnurn Energy Gap 1. Therefore.1 1 0.2.3 111-V Semiconductors For the two 111-V compound semiconductors GaAs and Gap. and for CdS (hcxagonal phasc). Energies in e V .028 0. The minima at L are L.8. The full point group of equivalent directions is T d for both materials.67 0. v l (heavy.24 0. light holes).31 0. Their first B Z s are the same as that of Si and Ge. the conduction band of Ge has 8 half-valleys instead of 6 full valleys in the case of Si.00 0. Spin-orbit interaction is important for the overall band structure of GaAs. the valence band maximum lies at Without spin and r. being the B Z boundary point of the A-line.7 0.27 0. the band structures are shown in Figure 2.30 0. CdTe.8. GaAs.044 I _ Si G2 I GaAS A L 0.03 0. Band structure of important semiconductors 219 Table 2.24 ‘k Se - H Z(?) 1. .

32:Band structure of 111-V semiconductors GaAs (top) and GaP (hot tom). The energy unit is el’.220 Chapter 2. 1974. Electronic structure of ideal crystals Figure 2.j . (AfLer Chelikousky rand Gohen.

33. the conduction band minimum occurs at X and belongs to the representation XI. The energy unit i el.K E rI Figure 2.I . 2.4 eV above the absolute minimum atr r.8. (After Chadi. ) in the case of Si and Ge. One of the peculiarities of its condiiction band structure is the relative minimum at the L-point only about 0.-level gives rise to the 8-fold degenerale spin-orbit-split band. X z ! x3> Xq) in the case of Si and Ge (see Appendix A).8.‘. In the case of Gap. The lower l”.observed in the case of Si and Ge.4 11-VI semiconductors The band structures of two typical IT-VI semiconductors with zincblcnde structure. and a lower I’7-levd In the upper l’g-level. Since the valence band maximum resides at I’.2. which means that the point symmdry of equivalent directions is rduccd from Of. 2972.K r I -61 L A I r A XU. Cohen. it belongs to the irreducible repre sentation I’l5 of the point group Ta which arises from the representation . The band structure of . Walter. Band structure o important serniconductors f 22 1 I i r 1 x U. X:) instead of only one 4-dimensional ( X .33: Band structure of IT-VI sernimnductom Cd‘k (left) and IIgTe (right). the r15 vulence band maximum splits into an upper r8-level.) s spin-orbit interaction (the case of Gap). The reason €or this is that the t.are shown in Figure 2.wn atoms n of the primitive unit cell are no longer identical. CaAs has a dirwt energy gap. Therefore.and also 1-dimensional ordinary representations (XI X2. Thus. The %fold degenpracy of the valence hands at X.X3. With spin-orbit interaction (the caw of GtrAs). splits i CaAs and Gap. one also has 2-dimensional spinor representations ( X s . the two 2-fold degenerate heavy and light hole bands mcrgr together as in the case of Ge and Si. CdTe and HgTe.. ? of Oh if the latter is taken as a representation of Td. Xq) instead of only 2-dimensional ones ( X i . Patroff and Balkanski. GaP is an indirect semiconductor. The conduction bend minirnnrn of GaAs occurs at the r-point and belongs to the spinor representation r7. t o Td.

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

and the two bands r6 and I?7 into which the rg-band decomposes under the hexagonal deformation. we chose the hexagonal CdS (see Figure 2. the fundamental energy gap is zero.34). The energy unit is eV. CdS has a direct energy gap at r. . namely r7-band which is separated from the other two by spin-orbit interaction. The first B Z is that of the hexagonal Bravais lattice. Schliiter and Cohen. Thus.8. Furthermore. (After Martinez.12. As an example of a 11-VI semiconductor which does not exhibit the zincblende but rather the wurtzite structure. 1975.35: Band structure of PbTe. The latter effect is called crystal field splitting (see the right part of Figure 2.2. this means that HgTe is no longer a semiconductor. L r X K. because of the hexagonal deformation of CdS. which is shown along with its symmetry points in Figure 2. Since it is degenerate with the uppermost valence band at I'. It is more fitting to term HgTe a semimetal. Band structure of important semiconductors 223 lxc.) the conduction band. the valence band is composed of 3 bands. because in semiconductors the valence and conduction bands must be separated by a finite energy gap. According to the general definitions of Chapter 1. the valence band is additionally split off at r as compared to the cubic materials of diamond and zincblende structure.34).U I 4 r I Figure 2.

a special feature which is hardly realized in any other semiconductor families apart from the IV-W compounds. 1 g71.8. It crystallizes into the rocksalt structure.6 Tellurium and Selenium The band structures of tellurium and selenium are shown in Figure 2. Electronic structure of idea[ crystals 12 8 4 0 -4 -8 r z H K r 1 . both the valence band maximum and the conduction band minimum occur at the H-point of the first B Z . it f amounts to about 0. Like InSb of the 111-V-compounds. PbTe. . Its Bravais lattice is. i973.5 IV-VI semiconductors The band structure of a typical IV-VI semiconductor.z H K r Figure 2. In the case of Te. 2. they have the same first B Z s as the hexagonal CdS. and that of the valence band is probably at H.36.2 e l F . that of the conduction band is probably at 2 . the two edges both lie outside of I-. The conduction band minimum and the valence band maximum both lie at the edge-point L of the first B Z . The energy unit is eV.35. Se has an indirect gap. The energy gap o PbTe is relatively small. Maachke and Laude.8. PbTe belongs to the group of narrow gap semiconductors. The material is therefore direct. again the fcc lattice and its first B Z is the same as that of the diamond and zincblende type crystals.36: Band structure of Te (left) and Se (right). thus. (After Maurhke. is depicted in Figure 2.) 2. This means that PbTe is a direct gap semiconductor with many valleys.224 Chapter 2. Both materials have hexagonal Bravais lattices. Stuff. Therefore.

the so-called ~ effective mass theory. Interaction potentials of this kind apply to many perturbations of atomic structure. . also other perturbations. the source of the particular nature of their electronic structure. and their chemical cornpodmn is not exactly lhal of the correspondiug ideal crystals. in particular to the so-called shallow centers which will be treated in section 3.3.6. like the so-called deep centers. for example. The one-electron Schrodinger equation of imperfect semiconductor crystals will be derived in section 3. .1. not the atomic structure which provides real semiconductor crystals with special scientific and technological importance. but require other methods. They cannot be treated by means of effective mass theory. ultimately.22 5 Chapter 3 Electronic structure of semiconductor crystals with perturbations Real semiconductor crystals are imperfect.4 important theoretical method €or its solution. This is also true for clean semiconductor surfaces considered in section 3. They differ from ideal crystals in their atomic structure as they contain structural defects. one must also deal with the atomic structure of imperfect semiconductor crystals since that is. Nevertheless. There are. will be developed in section 3. 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. but their peculiar electronic structure that is manifested in pronounced macroscopic effmts such as. It is. however. This will be done in section 3.5.4. to be dealt with in section 3. however.2. This equation allows one to determine the effects of perturbations whose interaction potentials with electrons are slowly varying over the atomic length scale. in which potentials exhibit considerable change over the atomic length scale. the increase of electrical conductirity by orders of magnitude.

which hosts the impurity atom. not with chemically 'correct' atoms throughout. mechanical strain. 11 is also of interest to study semiconductors which are exposed to macroscopic external perturbations such as dectrir OT magnetic fields. but. but these are not always positioned on regular crystal sites but also on irregular ones. one can distinguish them on the basis of whether they are of a purely chemical nature. albeit a perturbed one. and other sites are empty. In the first case. In this sense.226 Chapter 3. 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. On the one hand. In a real crystal.1) defined by the crystal structure. In this context the perturbed crystal. A crystal formed from a chemical compound may also exhibit f compositional disorder without impurity atoms. However. This theory applies because the macroscopic perturbation potentials are naturally smooth over the atomic length scale. this characterization holds for the vast majority of regular and irregular sites .1.9). not . or mixed type. In the case of elemental crystals. The electronic structure of semiconductors in the presence of such macroscopic external perturbations is treated in the second part of this chapter. 31 . Electronic s-tnictirre of semiconductor crystals with perturbations Besidc the study of semironductor crystals having a perturbed atomic structiire. One refers t o this as chemical or cornpositzonal dzsorder. As discussed in Chapter I. there is deviation from the ideal occupation at some of the regular and irregular sites. are occupied by atoms of the 'correct' chemical species. Furthermore.providing the justification to speak of a crystal at all. one then refers to the crystal as either perturbed or real. only regular sites of the crystal are occupied. the latter may be characterized as follows: All regular sites Ri 7 rial + r2a2 + 7'3a3 + 6 (3. again. This will include superlattices (section 3.1 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. or purely structural. this kind of disorder necessarily means the presence of impuaty atoms. is called the host crystal. or arbifmid atomic superstructures.8) or a magnetic fidd (section 3. 3. In all cases. the effective mass theory plays a major part in our theoretical understanding. only chemically 'correct' atoms are present. namely because o a perturbed stoichiornetrical composition.7) and semiconductors subject to an electric field {section 3.

An illustration is given in Figure 3. be distinguished according to the macroscopic extension of the perturbations. S A ~ . many elements of the mein group of the periodic table.regular or irregular sites of the crystal are partially occupied by rhrrnirnlly ‘wrong’ atoms. the ~ynibol GaAs . rpspert ively. in the first case one uses the symhol S I : P . As a rule. if added l o group-IV elemental semiconductors as well as binary 111-V and 11-VI-compound semiconductors. Below we will characterize the various perturbations in more detail.lb)’ it is referred to as a substztutzonal vrnpuraty. one may refer to structural point or line perturbations. starting with point perturbations. The third case is the most general one . To avoid a somewhat cumbersornc description. form substitutional impurities. Examples of substitutional impurities are a phosphorus atom in Si on a Si-site. The dimensions in the second classification scheme apply to the microscopic core of the perturbation. The substitutional incorporation. on the other hand. If the perturbation extends over sites located on a line or a planc. or a sulphur atom in GaAs on a As-site.1. Atomic structure of red semicoriductor crystals 227 all regular siles are occupied by atoms. which.1. 3. due to their long-range Coulomb forces. the doping of GaAs with S leads to the above mentioned point perturbation . Structural perturbations are also called strurtural & f w h or simply dpferts. we describe the most important compositional and structural point perturbations of semiconductor crystals. Examples are charged impurity atoms. ‘l’herefore. some sites remain empty. are incorporated substitutionally. 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. in most cases.3.2 Point perturbations Types of point perturbations In this subsection. Combining the two classification schemes. For this reason. Deviations from an ideal crystal may. 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. end also the ‘correct’ atoms partially occupy ‘wrong’ sites. and in the second. compositional point perturbations etc. A perturbation that is limited to one or a few neighboring regular or irregular crystal sites is called 0-dimensional or a poznt perturbatzon. Since the impurity atom substitutes an atom of the host crystal (see Figure 3. (1) We begin with an impurity atom on a regular crystal site. change the potential energy of an electron even over distances large compared to the lattice constant.1.

.he crystal has bond centered interstitiah. as depicted in Figure 3. a Ga atom may be located ttt an h . then an atom of the h s t may occupy a regular site of t h e sccond. G a A s : Sica (and not GaAs : S ~ A ~ ) . (2) An unoccupied regular crystal site is called a vncuncy. Ic. vacancies and antisite defects are structural point perlurbations. one has a self-interstitial (as shown in Figure 3. 1 ~ .this is called a Ga-antisite defect. The symbols are As& for the As-antisit>e defect.&. . or point defects. 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. and vice vcrsa Such point perturbations are called antisite defects. The vacancy in Si is denoted by S i : c': the cation vacancy in C h 4 s by G a A s : T. one has an interstitial ampurity atom (Figure 3.Vacancies occur in all important semiconductor crystals. for example. as shown Figure 3 .e. In thc latter case t. and G U Afor the Ga-antisite defect. i. One refers to these7 respectively. (3)If the impurity atom does not occupy a repular crystal site but a site between regdar ones. the general symbol is V.le). Moreover. i.228 Chapter 3.16). there are high symmetry sites with hcxagonal symmetry. as i l h s t r a t d in Figure 3 . The general symbol for an interstitial is I . and the anion vacancy by GaAs : VA*. In order for an impurity atom to stay at an interstfitrialsite. 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. the . in t.e. the crystal should n not be packed too densely. of course). In order for such a structural point defect to develop in a crystal. i the case of tatrahedral semiconductors. one n has to distinguish between cation and anion vacancies. particularly in Si and Ge which have purely covalent b ondinE.. The compositional point perturbations. ~ ~ Interstitials. This happens. 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 ~ . it must have sufficiently low energy there. An interstitid Fe atom in Si on a tetrahedral site is denoted by Si : I. there must h e enough space between the host ntmns. and tla As atom may occupy a Cia-site . for example.he case of transition metal atoms in semiconductors composrd of elements of the main groups. 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. 1 In the ~ case of CiaAs.a crystal consists of two different chemical elements.s i t e this is called B I ~ As-antisite defect. T semiconductors made of binary chemical compoiinds.. (4) If a chemically 'correct' atom of the crystal occupics an interstitial site rather than a regular one. ( 5 ) If.

.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).-Antisite e) Figure 3.3 . impurlty -___ A.-Antisite B. 1 . 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.

In the rightrnost column the respective closed shells are indicated. the former are simultaneously also the outer shells of the atoms which are responsible for chemical bonding. they are s.and p-shells. in gen- . This will be done next. Electronic structure of semiconductor cxystals with perturbations Table 3. 50 belong to the main groups and 48 to the transition groups. This is not surprising because the incorporation of an impurity atom in a crystal indicates a more or less strong chemical bonding.and f-shells. which is commonly used in chemistry. thus. if they exist. We summarize this group division of chemical elements below. The energetically highest. The rare gas elements are special cases.1 have in common the feature that electron shells with angular momentum quantum numbers 1 2 2 either do not occur at all or. Therefore. only partially filled shells of these elements either have 1 = 0 or 1 = 1.1: Electron corifiguratiori of main group elements. no partially filled shells of this kind occur. and thus in general. The periodic table consists of two types of groups of elements. and the transition groups.and p-shells in comparison with d. For the elements of the transition groups presented in Tables 3. The elements of the main groups in Table 3. Of the first 98 elements.2 and 3. in which the s.230 Chapter 3. i. need to be further specified. they are completely filled or completely empty.and pshells are also completely occupied. Because of the relatively large spatial extension of s. One thus also speaks of sp-bonding elements. the main groups. impurity atoms.3. Classification of impurity atoms The division of elements into groups.e. the shells with 1 2 2 are energetically the highest and. also proves to be helpful for the classification of impurity atoms in semiconductors.

the d-shells (I .3) only for n 2 4.3: Electron configuration of rare earths and actinides. one has the shells 36. Because of the relation R 2 I 1 between the main quantum number ?a and the angular mornenturn quantum numbe1 E.2) are possible only for n >_ 3. 4f. 5d. Table 3. fih ptc.3. 69.1.s. Accordingly. In the right column the respective closed shells are indicated. 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.2: Electron configuration o€ transition dernent.&.1g. the f-shells ( 1 . etc. In the rightmost column the respective closed shells are shown. . 6 4 Sf. Atomic structure of real semiconductor cry&& 231. Since among the first 98 elemmts of + Table 3. Actinides . Sf.

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

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

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

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

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

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

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

A substitutional impurity atom migrates mainly with the aid of a vacancy. Conespondmgly. which diffuses substitutionally. and for the migration of a self-interstitial in these materials.H . intermediate states with larger total energies occur. the migration rate becomes proportional to the activation factor e x p ( . H. 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. Q is given by the sum of the migration mthalpy Hm and the formation enthalpy H f for a vacancy. For not-too-large gradients of the defect concentrations. the activation enthalpy Q equals the corresponding migration enthalpy H. At1 atoms in Si preferentially diffuse through interstitial sites. Atomic structure of real semiconductor crystals 239 perturbations. the diffusion of a particular kind of point perturbation may be traced back to just one material constant. it can move directly to an adjacent equivalent crystal site. / t T f . For P in Si. In the case of diffusion through interstitial sites. namely the diffusion coefficient D. 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. For diffusion through vacancies.. The temperature dppendence of the latter also exhibits an activation behavior.1. In order for migration to occur. amounts l a about 1e V . the diffusion coeficient at 1500 K is about lo-'' cm2 sec-'. The latter vacancy is displaced with respect to the original vacancy.4 the Q-values for substitutional and interstitial diffusion of some impurity atoms in Si are listed. . One calls it the magration barrier Em. it is smaller than 0. Substitutional impurity atoms preferentially diffuse through vacancies. with the pressure p held constant rather than the volume V . an interstitial impurity atom does not need the help of a vacancy for its migration. 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.25 el/. For the migration af a vacancy in Si and Ge. This means that ttn energy barrim has to be overcome in an elementary migration act. Between them. The initial and final states of an elementary migration act are relatively stable states of the crystal. In this way. + where Do is the limit of U at high temperatures. In Table 3. the lattice oscillations must provide the energy Em or the enthalpy Hm = Em p V . as comnionly OCCUTS. Migration constitutes the elementary microscopic event underlying the mtacroscopic process of diffusion. namdy by filling a neighboring vacancy site.3. the first Fick's law may be applied in many cases. The latter occurs then when the distribution of the migrating point perturbations is spatially inhomogeneous. In contrast to this.

indeed.240 Chapter 3.7 0.the grain boundary is the lattice plane at which these two half crystals meet.1. If one calculates the line integral over the path shown in Figure 3. For a screw dislocation one has to view the crystal as being cut by a semi-infinite lattice plane. In practice. 2-dimensional perturbations in contrast to the 0-dimensional ones considered above. Electronic structure of semiconductor crystals with perturbations impurity atom activation enthalpy (eV) B Ga P H Au Cu 3.the plane is occupied on one side of this line (representing the step dislocation line). deviations from crystal structure are. It is called the Burger’s vector. The microscopic core of the perturbation is limited. surfaces of crystals may also be considered as 2-dimensional perturbations. respectively. In a dislocation. . but certain lattice planes are twisted by an angle. The line integral about the screw dislocation line yields a vector parallel to this line. the occupation of a particular lattice plane breaks down along a line of lattice points . Then one has 1.4 Line and planar defects With an increase in the number of point perturbations. The most important representatives of a 1-dimensional perturbation are stepand screw dislocations.5 0. which is bounded by a line of lattice points representing the screw line. then the result will not be equal to zero. ordering on lines and planes occurs only for structural point perturbations. In a sense. not limited to a line as one could initially assume. however. to the dislocation line. a tendency arises for these perturbations to arrange themselves on lines or planes of macroscopic size.2. as would be the case for an ideal crystal.2 (left-hand side). right-hand side).39 0. the various lattice planes carrying the atoms are not stacked in the same way as in the ideal crystal. Then the lattice planes left and right of the cutting plane are shifted parallel to the screw dislocation line by a lattice vector. Slight atomic displacements (strain) occur in a finite macroscopic environment.43 3.2). Grain boundaries occur in crystals which in fact consist of two differently oriented half crystals .and. but equal to a non-zero vector perpendicular to the dislocation line. At a step dislocation. The two most important examples of 2-dimensional perturbations are stacking faults and grain boundaries. After that one reconnects the two crystal halves again (see Figure 3.7 3. In a crystal with stacking faults. but not on the other side (see Figure 3.9 3.

Fortunately.2: Illustration of a step dislocation {left-handside) and a screw dislocation (right-hand side). In analogy to equation (2. In this. also the potential V ~ " ( x of the perturbed crystal is the sum of three contributions.. 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.and 2-dimensional perturbations. we restrict.) Having surveyed of the atomic structure of real semiconductor crystals we will now proceed to the electronic structure of such crystals. therefore. while perturbations of higher dimensions are generally disruptive. just like the latter. ( A j L w f35w.2 One-electron SchrGdinger equation for point perturbations In regard to its geiwral form.3. The silicon bars used in microelectronics are now grown practically free of dislocations and grain boundaries. However.2. because they are less effective in increasing entropy. One-electron Schriidinger equation for point pcrturbations 24 1 Figure 3. 3. we excliide 1. ) the potential V ' c ? 7 L ( ~ ) caused by thf atomic cores of the perturbed crystal.76) we therefore have . the Hartret. 1990. yotentid I/Frt(x) of the valence electrons.76). In the following sect'ion we will formulat'e the Schrijdinger equation for the oneelectron states of a crystal with a point perturbation. The reason for this is that the derivation of the latter equation in section 2. the latter can also be more easily avoided than 0-dimensional perturbations. 'rhis is done in recognition of the fact that only point perturbations can play an important positive role in semiconductor devices. our considerations to crystals with compositional or structural point perturbations. and the exchangecorrelation potential V F : ( x ) of these electrons.2 never actually involved the periodicity of the ideal lattice. 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.

10) The point perturbations listed in section 3. (3. This case occurs. We denote the number of (positive) elementary charges of the core of the impurity atom by Z r . of We decompose it into a sum of the core potential Vc(x) for the ideal crystal.9) In further clisrussion. . Thus.7) With this.3). we assume that only one point perturbation exists in the crystal. the two atomic cores differ mainly through their different charges. initially. VC~'"X) = K ( X ) I V. if a P atom with only one additional proton and one addit. and the number of (positive) elementary charges of the core of the host atom by Z H . approximately. (3. and we procecd on the assumption that the potential VJx) falls off with increasing distance form the origin and finally approaches zero: V. 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. we discuss the potential VcPTt(x) the electron-core interaction.242 Chapter 3.'(x)which describes the change of the core potential due to the point perturbation. The center of this perturbation will be taken as the origin of our Cartesian coordinatc systcm. With this rqiiirement. above all.ional neutron substitutes a host atom of a Si-crystal (as illustrated in Figure 3. The potential energy of a valence electron of an impurity atom of the type described differs. Because of charge neutrality of the individual atoms. (3.1 Elect ron-core interaction First of all. One refers to them as isocoric impurity atoms.t(X)."'"x) L'() + Vg. then one has.2.1 differ as to how fast this decay proceeds.'(x) -+ 0 for Ix I + 00. We consider. ZI and ZH are simultaneously also the numbers of valence electrons of these atoms. and a potential V. If one considers the cores to be point-like and neglects spatial dispersion of dielectric screening.(x). Electronic structure of semiconductor crystals with perturbations VWTt(X) = V ? t X f V. by the change of Coulomb potential from the potential energy of an electron of the host atom. thc one-electron Schrodinger equation for the wave function $ l V ( x ) of an electron of the perturbed crystal reads 3. for example.

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

l n thc case of a vacancy.3a yields the potential profile of VJx) V. whicb in the context of the ibocoric impurity atoms abovc. pert -v.12) Short-range perturbation potmtials apply not only to isovelcnt. they are therefore described as short runqe.'(x) of the missing atom.'(x) as depicted in Figure 3. in fact. increasing distance fiorn the center than does tlic Coulomb potential of a point charge. can ultimately be solved only by numerical calculations. and the perturbation potential has the form shown in Figure 3 .3b. v Figure 3.244 Chapter 3. The exact &termination of the pertrirhatiori potential is a problem which. that the pet turbation potentials of isovdlenl impurity atoms differ horn zero substantially only over a distance of a few lattice constants. non-isocoiic substitutional impurities. These show. we have v(. These arc also the potential contributions.(x) (0 v'(x) 0 for I x I 5 a f e u lattice constants for all other Ix1 (3. gave rise to central cell corrections.3: Illustration of thc origin of long-range (left-hand side) and short-range (right-haritl side) core perturbation potentials._ _ _ Si Si_ _ _ Si Si Si Si v . like the determination of the periodic core potential of an ideal crystal. = v. the occurrence of a short-range perturbation potential is particiilatly obvioiis. The remuval o f a Si at<nrn from the chain of S i atoms in Figure 3. + . ncgative potential v. Consequently. but also to structural defects such a8 vacancies or interstitials. Electronic structure of semiconductor crystals with perturbations Si . 3 ~ The latter approximately represents the .

Just like the elwtron-core inteiaction potential. In these cases.e.””(x) and the exchangecorrelation potential V.11). 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. which accounts for the different core charges. 3. those within the bands and. first.’‘(x) also undergo changes in the prrsence of point perturbationb. The same bhort-range potential has a greater effect if the Coulomb potential.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. is stronger. superpositions .49). 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. thereby substituting a triply positively charged host atom core.2. This comes about because the stronger Coulomb potential pulls the electrons closer to the core. those with F I I C ‘ I eigenvalues within the energy gap ~~ between the valence and conduction bands. From the physical point of view it is quite clear that the prrtiirbed rrystal ~ H two kinds of stationary one-particle states. in higher approximations. while. due to a larger core charge difference between the impurity and host atoms. ‘The effects of the two potential contributions are not independent of each other.2 Elect ron-electron interaction Hartree potential The Hartree potential V r t ( x z ) of the r-th electron is. 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. those with energy S eigenvalues which were already allowed for the ideal crystal. Below.””((x) of the liartree-Fock approximation. the oneparticle states $ ( 2 here are not those of the ideal crystal. where the the short range potential is essential. i. given by the expression (3.”. The states of the first kind represent pure Bloch states only in zero-order approximation with respect to the perturbation potential. the perturbation potential represents a superpobition of the screened Coulomb potential (3. secondly. we describe these changes for the Hartrre potential V I y t ( ( x ) and the exchange potential V. the Hartree potential V.13) However.3. as before (see relation 2.11). .2. or Sn atoms with their Cfold core charge on a G&site in GaAs. Similar results can be derived for the exc~iaiig~rorrt~ation potential vzt(x)of the LDA mettiod.

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

their exchange interaction will be stronger than that of the extended electrons. It is therefore again expedient to decompose the entire exchange potential V. it follows that .P”t(x. 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 ~ (N .. the positional uncertainty is smaller than that of the extended ones. the probability amplitude o the extended states f is reduced close to the localized electrons of the center because of Coulomb repulsion. Accordingly. by definition. we set Vkm(-) --t VA<xi) and V r t d ( q ) V~(xi). For the localized electrons of the perturbed crystal.).f VX(Xi) = + Vfi(X2). (3.which an electron a localized at the center feels.td(&) and l r ~ ( x of.n occupied states are affected. This change may be accounted for by replacing the localized part VAm(xi)of the perturbed Hartree potential by a screened potential Vh(%).3.2).19) Using relation (2.n ) extended and n localized electrons.p”t(X. The change of the extended states is essential.2. however: because all N . 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). this replacement.+ Then it follows (3.2. 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. a positive excess charge arises in the vicinity of the localized electrons which screens the Coulomb potential of these electrons.17) where.. . we have v.61). x‘) is the inhomogeneous position-dependent screening function of the crystaL Exchange potential As we know from section 2. into the two parts V.‘ ( q . Hence. Accordingly. 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. VA(xi) is given by the expression where e . In this connection. )respectively.

~ the rxpectation valri~ ($V. tlip two othw potential parts L$(x%) and Vdk(x. <. (3.enerafly. Substituting trhe three potential parts (3. is The occiirrenre of localized states at the center. 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 . (3. they a e non zero and lead to corrections of the localized eigensolutions of ihe Schriictinger PqiiBtion (3.E U T h ( X ) .181. the core perturbation potential l<'(xz) the strangest. as bcfore.)due to electron-electron interactions vanish completely.19) into the oneelcctron Schrbdinger equation of the perturbed crystal.17) and (3. equation (3.60)occurs. If only one electron is localird at the center.22) whcrt. the various terms may bc arranged such that the effective oneelectron potential E(} of the 'x ideal crystal (2. is maidy due to this potential contribution. I1 . Pert rirbation theory The Srhrodingrr equation of zcro th order reads [ H f q x ) ] ls'v(x) . 1 VAw I vv.p2/2na V(x). In gcnpral.21) which rontaiiis L:(x) as the only potential. this expression may be written as .20) where the summation over k inrlirdes only particles whose spin W k equals the spin LT? of particle i. the central feature of our considcrations above.22) is exact. If only one particle is localized at the center. signifies the oneelectron Hamiltonian operator of the ideal ciystal. Electronic structure of semiconductor crystals with perturbations (3. The equation reads The three perturbativc potential parts in this equation have different ef fwts.). The index i is omitted because all electrons feel the same core perturbation potential. 'I'hcse corrections will now be estimated by means of perturbation theory.248 Chapter 3.91. [!ring (3.

28). (3.. (3. One-electron Schrodinger equation for point perturbations 249 (3. .) i -(no.211iIS) . f o r not 2 1.( . Exchange energy Next we will calculate the corresponding energy correction due to the perturof bation of exchange potential V%{x) (3. the corresponding numbers n~ and nl of electrons localized at the center can differ. it at an average position X in place of x The remaining x'-integral yields 1 because of the normalization of the wavefunction @.23) We extract the factor ( .I ) J . the two partial numbers ny and nl may be written in the form 1 1 (3.20) yields the expression "1 = . The latter depends on the spin of the electron because..26) 2 h l s ) .( n + ( ~ v . is the spin quantum number of the state v. multiplied by e 2 .(x'). 2 4 ) is called the Hubbard energy. In terms of the total number n = n~+nl and the total spin projection M S = (1/2)(nT .2.19). and (3. x) I x-x' 1) from the x'-integral by evaluating E ' x '/ ' ..) perturbation of the exchange 5 of the potential. will be denoted by Uy. 2 2 For the expectation value (&. equation (3. nl = -(n . contrary to the ideal crystal case where the numbers of electrons with 'spin-up' and 'spin-down' are equal in ground state. I ~ I'+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. we set i.e.t 1 1 I iu. the expectation value of the perturbation of the Hartree potential becomes The energy Up' of ( 3 .27) where g.24) With this."1) of the localized electrons. . The integral over X.3.

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

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

‘(x)! add lip l o form a smooth total perturbation potential i( ) ’x. which drastically simplifirs the bolution of t h ~ Schriidinger eqiiation hi the casr of an ideal crystal is perturbed by both kinds of potentials.ion we will make relat. Far hhe derivation which follows. 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- . in a certain sense.ransform it into another equation.h t.21) which are smooth if L’. although the Coilonib form of this potential is not necessary for the derivation of t.(x) is also. In conjunction wit. t h r lattice translation symmetry.t(xj of eqiiation (3.he solutions qVof Ychrodinger equation (3. For long-range potentials the dec iations from lattice trauslation symmetry are relatively weak. which we will derive in the following section. it does not iulerfere with its derivation.With the background analysis set forth above. For the latter? Vh(x) and Vk(x) may be treated as smooth external potdialii which. Which solution methods can be applied with succcss depends decisively on whethe1 lhe core yrrt iulmlion potential is long.es to Ihe core part V ~ ( X of the pert. T he latter is called the LPffective mass equation’.pdurbations of the Hartree and exchange potentials l7L(x) the and ViCx). the POt. ) in This potential part is supposed to be smooth on the atomic length scale. one for the periodic potential of the ideal crystal.21). The wwelunction dependence of Vh(x) and L’i(x) requires self-consistent solutions of the Schriidinger equation. Of course.hpotential U ( x ) is allowed. The other parts of thr t o l d perturbation potential V&. and one for the perturbation potential. In this section we do not intend to solve this quabion explicitly hut iclther to t. together with V.iirbation pot.~.ential need not be t. arc automat.entials Vf(x)are ruled out from the very beginning. The most.his wxmption. In this case the Scfirodinger equation.urhatiozt potential V A T t ( x ) this equation. Althoiigh the self-consistency demand is transferred to the effective mass equation. which was solved previously. but only for short-rangepotentials in an e s s e a t d mannet-.3 Effective mass equation ure start with the Schrodinger equation (3.21)!i.ically smooth if V&(x) has this property because these potential parts are dctcrmined by t. iiriport. Point perturbations with Coihmbic core perturbation potentials are still allowed. 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. point pcrtiirhatioiis with shos-t-range core pert.or short-range. 3.8) of the perturbed crystal in the form (3.because these caiinot be considered to I c smooth. may be decomposed into two quations. the cffective mass equation? aliith can be solved more easily. any smo0t.he effective mass equation.ant assumpt.he smooth perturbation potential VieVt(x) a point of perturbelion.

operator by the effective mass m:. such 8s that associatd with an external electric Geld.e.ter generally differs horn the mass of a free electron. hilt also for macroscopic perturbations. The procedure described above needs. for example.ion. we will employ t. However. The e&ct. The goal of the following consideralions is l o simplify the oneelectron Schriidingcr eyiiation (3.3. the free electron mass 7 n is replaced by the effective mms rnc of the particular band and critical point chosen. so that. how the wavefunction of the e f l d i v e mass equation reiates to the wavefunction of the original Schrodinger equation. To provide this.he perturbed crystal in stages.he effective mass equation is twsentinlly the same a8 the Schrodiuger equation for the hydrogen atom whose solutions are already known.ion. ultimately: a mare easily solvable equation.he fact that.ter. quest.3. In this mat. of COZITSC. for example. Therefore. which are smooth on the atomic length scale by definition.3. we rewrite the Schrodinger equdion (3. results. Effective m 9 equation a5 253 tials. the value of the lat. it is generally a tensor.ions have to bc addressed which have been left. Having in mind the effective mass description of the band energy versus quasi-wavevector k relat. one may suspect that the influence of a perturbation potential V(X) on an &&on of the cryisla1 can be calculated in an appr0ximat.1 Effective mass equation for a single band To address these questions and derive the effective mass equation for a single band. 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.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). and if il can be reduced to a scalar maw.29) in the Bloch representation. t. For a siibstitutioiial P atom in Si. 3. namely the effective mass equation.j(x)in order for bhe effectivp mass equation to be applicable. open so far. further justificat. in the same way that the energy of a free electron depends on its momentum.ivc mass includes the effects of interaction of the electron with the periodic potential of crystal.. in the vicinity of critical points of a certain band v . and the matter of what conditions must be placed on the perturbation potential V(x) and the wavefunction 7. i.29) for t. . the energy of an electron of an ideal crystal depends quadratically on quasi-wavevector k.

(k). the assumption made at the outset that U ( x ) should be a smooth potential. (3. they are non-zero only if k is a reciprocal lattice vector K differing from zero.32) To transform this equation into the effective mass equation. for kvectors outside of the first BZ. (3. This means that the smoothness condition for U ( x ) may be expressed its essentially non . The latter components were calculated in section 2. using the same notation introduced previously in Chapter 2. v‘k’ + (3.are small compared to the Fourier coefficients (kll.29) takes the following form: [ E y ( k ) 6 v f y f 6 k k ~ (vklUjv’k‘)] (Jk’lV) = E ( v k l $ ) . must be specified further.161).35) . To formulate the condition for smoothness in over this sense quantitatively. Electronic structure of semiconductor crystals with perturbations expanding ~ ( xwith respect to the complete set of Bloch functions ) whence ‘pvk(x).4.33) is extended over the entire infinite k-space.’) of the periodic crysta1 potential V ( x ) .zero for for Ikl w ithin first 3 2 Ikl outside f i r s t BZ << I(KlV)l. 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.31) Since the (pYk(x) are eigenfunctions of H with eigenvalue E. more strictly speaking. for large k-vectors. meaning over all Brillouin zones. We have (3. (3. According to formula (2.33) with Fourier coefficients (3. K # 0 . we decompose U(x) in a Fourier series.34) The sum in (3.254 Chapter 3. Smooth functions U ( x ) in the above sense have Fourier coefficients (klU) which.30) with the expansion coefficients given by (vk I = d3xlpXx)~(x). the Schrodinger equation (3.

and if only these eigenstates are considered..36) It states that.38) the wavefunction (3. like the fundamental energy gap E. (3. it will be assumed that for small k-vectors.37) with F . the inequillity (3. of the R X center k = 0 by the non-central critical point k. the changes of U(x)over a primitive unit cell must be small compared to the energy gap. The above four conditions will now be used to simplify the Schrodinger equation (3. the band edge lies at k :.k(x) can be approximately replaced by their values at k=0: U v o k ( X ) ZS . Fourthly.3.mo(x). and relation (3. With this. If. Applying relation (3. that is.37) may be written as . additionally.(k). The restriction of the location of the band edge to k = 0 can be omitted. and the derivation procedure can also be applied to band extrema other than the center of the first B Z .k in the corresponding equations.q between the valence and conduction bands. which according to (3. Effective mass equation 255 The left-hand xlde of the inequality (3. well BY of k by k . the Bloch factors u W k ( x ) in the Bloch functions p. Secondly. as . (3. that $(x) should be of the form (3.38) holds approximately. the only modification being the replacement.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.32). i. a1VUI with a as lattice constant. 0 the small energy deviations also correspond to small k-values. we assume that the wavefunction $(x) can be set up exclusively from Rloch functions of only one band YO.38) In the following subsection 3.35) can be estimated by a characteristic band structure energy.35) takes the form alVUl << E g . It turns out that this requirement has no contradictions if the perturbation potential is smooth. The thzrd requirement refers to the function F.3.3.35). It is assumed that Fvo(k)differs from zero only for small k-vectors in the sense used in equation (3.e. The right-hand side of (3. for a perturbation potential U ( x ) to be smooth and our first condition to be fulfilled.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. ( k ) as a function which has yet to be determined.35) have to be considered exclusively.

(x) is termed the envelope functzon or. in short. it follows that + C . by definition. Electronic structure of semiconductor crystals with perturbations Tihe k-sum is the Fourier transform F. obtaining Furthermore. & k (3.41) means that the truc wavefunction + ( x ) is obtained by enveloping the rapidly oscillating Bloch lactor uvgo(x) with the smooth cnvelope function Fuo ( X ) .41) The function F.K.43) K With this. O ( X ) ~ Y l ( X ) .k’ + KIU)Ci$’(K). We rewrite this element using thc Fourier representation (3.(x) of the function F. The envelope function. only terms of the form exp [i(k’ k” .32) in a substantially simpler form. so that the sum runs over all lattice points of the periodicity region.i(k’+k”-k)-R R = G3 Sklfk’l-k. K (3.x. whence F.42) takes the form (vklUlv’k’) 1 = - C ( k . The summation over them can be executed easily. A lattice point R is associated with each unit cell. 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 (3.45) .(k). Because of the lattice periodicity of the Bloch factors.k) .(x) = 1 -CFvo(k)eik. With K as an arbitrary reciprocal lattice vector. expression (3. we transform the integral over the periodicity region into a sum of integrals over the unit cells of this region.44) f i wherein the notation for the so-called Bloch integral (3. (3. Equation (3.256 Chapter 3. (3. R] remain under the lattice sum. i s a bmooth function. the envelope.33) of U(x) and the product form of the Bloch functions p v k ( x ) .40) Therefore $ ( x ) may bc written as $44 = ~ .

To this end we multiply by ( /exp ( i k .o(x)..44) for (vklUlv’k’) yield no significant contributions to the Schrodinger equation (3.45) c : ~ : ( o ) as follow c.32) for the perturbed crystal has been done . the Bloch integrals of equation (3.50) One can easily prove that this transformation is correct by expanding E.. ud(x) and uU.(k)Fuo(k) k ( Ik) = X Ev0 (-iVz) Fvo(x). The Schrodinger equation now decomposes into separate equations for the various individual bands.46) Approximating the Bloch factors u.32) if K # 0.6 kk’ t. The Bloch components of the wavefunction @(x) in the Schrodinger equation (3. (3. With regard to the smoothness requirement for the potential U(x).32). the decisive step in simplifying the Schrodinger equation (3. This can be processed relatively easily. x) = (xlk) and sum over k.47) (3. The coupling between different wavevectors remains in place. The 1 a ) first term on the left-hand side thereby becomes C &. Substituting this relation in expression (3.. .k(x) and U v l k t ( X ) by. and applying the orthogonality of the Bloch functions.32).(k) in a power series and by using the identity . Effective mass equation 257 has been introduced (0 = G3Ro).. (0) = .44) we obtain (v kl U Iv’k’) w (kl U 1k’)6. We employ all results achieved up to now in the Schrodinger equation (3. (3. so that (vklUlv’k’) N -(k a 1 .(k): This equation will be transformed from k-space into coordinate space. (vkl$) and (v’k’lg). Therefore we need the matrix elements (vklUlv’k’) only for small k and k .37).3. the ’ terms in expression (3.3.k’lU)C$t’(O). and these equations can in fact be solved by a one-band ‘Ansatz’ of the form (3. obtaining the following relation for F. (3. differ from zero only for small k and k’ because of the smoothness of the envelope..48) With this relation. respectively.the coupling between the different energy bands caused by the perturbation potential has been eliminated.

in accordance with equation (2.52) and the right-hand side of (3. These will be treated later in section 3. the effective mass equation (3. d O ) . and assumes an isotropic effective mass m+.258 Chapter 3. are not smooth. The essential requirements involved in the derivation of the effective mass equation were the smoothness of the perturbation potential.55) .49) can be written in the form C ( x l k )(klU l k’Pm (k’) kk‘ U(x)Fm(x). Other problems which can be solved with the help of the effective mass equation include artificial superstructures in a crystal and external electric fields.55) are also called envelope function equatioas in t...) = E.(x) If one further replaces Evu(-iVz). Point perturbations with smooth potentials are only one example of this.(x) = E F .his context .55) is a suitable instrument for the solution of a series of important problems of solid state physics. Equation (3. Also.53) or (3.54) and [ L . for example. 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.8. and are often not fulfilled. ( x ) . ( x ) . initially conjectured and now verified.-a2 2m& h2 I U ( x ) F. it. With this. With the derivation of this equation.(O) h2 + -(-iVx)2.55) 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. the Coulomb attraction between electrons and holes . 2mg (3.7 and 3. ( x ) . Nevertheless. These assumptions are decisive. (3.which results in the formation of excitons as pointed out in Chapter 2 - 1 (3.204). then it follows that E. Electronic structure of semiconductor crystals with perturbations The second term on the left-hand side of equation (3. the smoothness of the wavefunction and its composition of Bloch functions from only one band.41) for the true wavefunction $J(x). respectively.49) inluiediately becomw E F . one finally gets the following equation for F. Short-range perturbation potentials. as well as the k-independence of the Bloch factors. by a quadratic function of -iVz7 which is justified because of the smoothness of F .(-iV. Equations (3.

In the vicinity of the minima or maxima of non-degenerate bands of cubic crystals one has a purely parabolic and isotropic k-dependence. Effective m a w equation 259 may be treated by means of this equation. not to take a onecomponent effective mass equation as starting point. the effective mass equation (3.9. This picture changes for bands which display degeneracy in the extreme.49). IIowever. but a multi-component one which is obtained by writing the Schrodinger equation for the perturbed crystal in the approximate Bloch basis 1vk)l. Because of the non-parabolic and anisotropic dispersion laws in the case of degenerate bands. no more difficult to solve than an ordinary Schrodinger equation with an external potential. In the case of degenerate bands this suggests. The practical use of this equation depmds. as we have seen. or if no perturbation potential is present.53). This applies if basis functions other than plane waves are better adjusted to the symmetry of the perturbation potential as. on the dispersion law E. p-perturbation theory. 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)'. As we have seen.3. 3. As demonstrated in section 2. Regarding the perturbation potential U ( x ) and the envelope function F ( x ) . i.339)). therefore. in the form of equation (3. but the perturbation is introduced through boundary conditions. completely solves the eigenvalue problem for an electron in a crystal in the presence of a smooth perturbation potential. in particular higher order differentia1 operators occur which make solution of the eigenvalue problem practically impossible. derived in the preceding subsection. the effective maw equation has to be modified in a way which will be indicated later in section 3.3. A resolution of this situation is offered by k .3. and the effective mass equation is. we pose the same requirements . This does not involve a major difference if the one-band effective mash equation can be solved in k-space.e. p-perturbation (see formula (2. such as in the case of artificial superstructures like superlattices and quantum wells. however. for example. the Coulomb potential of an impurity atom.2 Multiband effective mass equation The oneband effective mass equation in its general form (3. We will undertake this program now.53) in coordinate space is more complicated.(k) of the band under consideration. one then in general has non-parabolic and non-isotropic dispersion laws.7 on k p-theory. The elements of this matrix are relatively simple linear and quadratic functions of the components of k. 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. which are exact up to the first order in the k .

1. (3. just as in relation (3.3.59) which corresponds to relation (3.58) has the order of rnagiitudr of the lattice constant a.48) which gives the elements of U with respect to approximate Bloch functions their Bloch factors u v k were replaced by u d . 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. 11’. which expresses the first order Bloch functions Ivk)’ in terms of Luttinger-Kohn functions. . The non-vanishing off-diagonal elerrienls ‘(vklU)v’k‘)’ may he calculated in the same manner as the diagonal elements before. Terms of this order of magnitude are to be neglected within the framework of effective mass thpory. However. Note lhat equation (3. This is due to the k-dependence of the Bloch factors in )vk)l which has been omitted in subsection 3.48) of subsection 3.kl$)(xtvk)’. it follows that the diagonal elements ’(vklUlvk’)’ arc the Fourier transforms (klUJk’). Electronic structure of semiconductor crystals with perturbations as in the previous subsection . unlike this ielation. One obtains The factor at (klVWlk’) in equation (3. (3.7.3. (3. p-perturbation theory or Luttinger-Kohn functions. as can easily be seen replacing p by x by means of Heisenberg’s quation of motion.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.1. thc matrix ’(vklU lv’k’)’ has also lion-vanishing off-diagonal elements with respect to I / . and block-diagonal with respect to the band indices v . The diagonal elements ’(vk(U(vk’)’ of the perturbation potential U may be calculated by means of relation (3. these are Bloch functions in zero-order k . 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.56) and the Schrodinger equation (3.339). In the terminology of section 2.57) The matrix ’(vklHIv’k’)’ of the unperturbed Hamiltonian H is diagonal with respect to k. the expansion with respect to the approximate Bloch functions reads ?clW= c uk ‘(.1. For the wavefunction $(x) of the perturbed crystal.260 Chapter 3.3.48) of subsection 3.29) in this representation takes the form ‘(vklH uk + Ulv’k’)’ ‘(v’k’l$) = E’(vk($). Using relation (2. v’ with the blocks referring to degenerate bands. k’.59) is valid independent of whether the two bands v and Y’ arc dcgeneratc .

62) does not occur in the corresponding equation (3. Mective mass equation 26 1 or not.61) Employing expression (2. Before simplifying the Schrodinger equation (3.336) for E?(k).41) for +(x). k (3.631 for l(vk)H]vk)'. and the diagonal elements are the eigenvalues Ez(k) of H calculated in section 2. its relative magnitude with respect to the first term is of the order of the relative change of the envelope function F .60) $(x) = CFw(k)(xlvok)l.57) still further for the actually interesting case of degenerate bands. even degenerate bands are not coupled by perturbation potentials U if these potentials are smooth. The Hamiltonian matrix '(vklHlv'k')' in (3. which was neglected in subsection 3. we will examine the case of non-degenerate bands.(k) in coordinate space.1. 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.. This term is again due t o the k-dependence of the Bloch factor in Ivk)'. With the Ansatz (3.334) for the approximate Bloch functions jvok)'.F.we obtain where hi&8 are the elements of the reciprocal effective mass tensor according to formula (2. Employing expression (2.60). Using the Ansatz (3. The second term of @(x) of equation (3.57) is approximately diagonal with respect to the band indices. ( x ) over a unit cell.57) yields . it follows that where &(x) is the Fourier transform of F.3.(k). In fact.337).41) above. the Schrodinger equation (3.59) for '(vklp) and expression (3. Again terms of this order of magnitude are again to be neglected within the framework of effective mass theory.7 in second order k.3. p perturbation theory.3. vj(x)may be written as (3. We therefore obtain the same expression V(x) as in equation (3.

by an integer index m. which we will address next. 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. 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. however.. which was invoked only later. In the earlier derivation of subsection 3.1. an effective mass equation was obtained that did not yet contain this approximation. The derivation of the effective mass equation based on k .7).66) As above. First we consider the : case without spin.. we set (3. Accordingly. from the assumption of isotropy of the band structure. p perturbation theory.67) . Thus. b Rloch states of energy E w ( 0 ) ' T arc. The Bloch functions at k = 0 arc therefore written as ) o m O ) .distinguished.65)yields the effective mass equation in the form (3. we assume that at k = 0 a degenerate band level E. in the case of non-degenerate bands.55).3. Electronic structure of semiconductor crystals with perturbations Fourier-transforming this equation into coordinate space.(--zV) replaced by a parabolic expression in the components of -iV.262 Chapter 3. Degenerate bands We direct our attention to the valence band maximum of semiconductors with diamond type structure (see section 2.(O) exists with either symmetry rhs or r depending on whether spin is omitted or not. If the effective mass tensor reduces to a scalar quantity ( l / m ~ & ) 6 ~ 0 . it approximately follows that (3.53) if the latter has E. then (3. p perturbation theory thus produces this equation automatically in parabolic approximation. we can represent $(x) as a superposition of the Bloch functions Ivrnk)' in first order k . The three degenerate . we have This equation is in agreement with the effective mass equation (3. as before.refraining.

With t. the envelope function equation then reads.(x) as the Fourier transform of F.3. the equation + Ci(X)h. @ ~ ~ (3.51).57) takes the form Transforming to coordinate space and taking account of relation (3.59). They vanish if v # wm'.ion (2. The subspace of valence band states is approximately decoupled from the remainder of the Hilbert space. For v = urn' they differ only from zero if m = m'. The matrix elen ments '(vklUlvrn'k')' of the perturbation potential U follow from equation (3.70) ($ follows. explicitly.F. and F (x)for the vector (F. F. f l I ~ = (3. t.344).342).(x)). expression (3.57)..(x).(x).i.. Now. .(k) in coordinate representation. With this.341).67) for '(ukl$) is substituted into the Schrodinger equat. Using the notation D for the fourth-rank tensor for the unit matrix 6.71) In the case of the & I valence band the Hamiltonian matrix is given by relat. the Schrodinger equation (3.3. Using equation (2.his equation may be written in matrix form as * Dm : .ion (3. EEective mass equation 263 with F. the matrix elements '(vklHlvm'k')' may be written as where the coefficients D: .! +$ 1 Fm'(X) = E F m ( x ) . are defined i equation (2.his.

If interference terms between the k ' p-interaction and the spin-orbit interaction H . and secondly the spin-orbit interaction opers) ator H. before one proceeds to solve it. which has the consequence for D that the matrix elements of p are replaced by those of ii from equation (2.74) was moved to the valence band maximum. Electronic structure of semiconductor cry.B. is to be added to the Hamiltonian operator H .in which the operator fiso is diagonal. i. 2 . here are differential operators defined as follows: 1 Q = --(L 2 + nf)(a: + a. the representation of the latter in the approximate Bloch basis leads to a * k-independent tensor Hs.R . i ' one arrives at the following $-component envelope function equation: The quantities d.) .75) + = --(L+ 5n/I)(d2+ a.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 ) . Using the arguments of section 2. one has to use spindependent Bloch functions (sxlvmak0)' and.a. . therefore.staLs with perturbations Here.] (L..i& a.76) (3. also spin-dependent envelope functions Frrw(x. with j = $. . One can derive a similar equation within the Kane model of the rs-valence-band-rs-conduction band complex of zincblende type semiconductors.) . derivatives of the type 62/6z2 are denoted by symbols like a. and those of type a 2 / d r d y by symbols like a&. which was previously located at A/3. For the T valence band. and assuming a sufficiently ' large spin-orbit splitting energy A.78) The energy origin in (3. are neglected. $.-(2L (3.=.) * s = i-(& N 1 6 1 3 +Mp:.353).e.. [3. The envelope equation (3.7.2iNa. (3. Firstly. Hk.264 Chapter 3 .p becomes Hk..74) makes it possible to calculate acceptor states and hole bands in superlattices of the diamond and zincblende type semiconductors.M ) ( a2 .Ma:. Thereby. . Consideration of spin leads to two changes.77) v % . . the coupling between the Ii and r$ valence bands may be neglected.

The effect of a non-vanishing VA(x) will be discussed later. if it is smaller. i. Donor and acceptor states 265 3. atoms from rows and columns of the periodic table which are close to the row and column of the host atom which is substituted. To solve the one-electron Schrodinger equation (3. we m a y use . Vb(x) and Vfr(x)do not vanish. have the effect that only one electron or hole can be bound at the center.79) and assume that it is non-zero.11) which here we write as (3. In Chapter 1. as a rule. For the pcrtiubation V'x of the core potential. Shallow levels.e. For this one electron or hole. i. these potentials. negative. V ' x does not yet represent the entire perturbation potential in .() the one-particle Schrodinger equation (3.() potential. For impurity atoms with only one valence electron more or less than the host atom. The sign of AZ can be both positive as well as negative. For impurity atoms with lAZl > 1.e.80).XI?.4 Shallow levels.22). 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). Below we will concentrate on such point perturbations. (3.() expression (3. Here. the Hartree and the exchange parts of the perturbation potentials vanish. 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.3.21) for the perturbed crystal.() 3.3. and the one-particle Schrodinger equation has the form (3. We denote the difference of the core charge numbers of the impurity and host atoms by AZ = Z I .22) with the potential V ' x of (3. One still must add the Hartree potential Vh(x) and the exchange potential Vfr(x) caused by other electrons localized at the center. .80) In general. 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. The most important point perturbations of this kind are isocoric substitutional impurity atoms. V'X is itself the entire perturbation .for impurity atoms with A 2 > 0 discrete levels appear in the energy gap just underneath the conduction band edge. we may use the effective mass theory derived in section . it was pointed out that such changes occur at the bottom of the conduction band and the top of the valence band .4.

= w) are assumed to be non-degenerate and to lie at k = 0. Effective mass equations are needed.86) . both for the conduction band edge as well as for the valence band edge.83) (3.266 Chapter 3. respectively. The relevance and necessary improvements of this idealized model are yet to be discussed separately.82) with rn. but there is degeneracy between heavy and light hole bands at k = 0. In reality. 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.4. Nevertheless. The valence band edge zs found at that point for many semiconductors including the ones mentioned.84) In the usual form of a Schrodinger equation they read (3. as effective masses of electrons and holes. Furthermore. whence we have (3. for many semiconductors such as Si and Ge. The minimum of the conduction band (vo = c ) . For reasons which will become clear below. the conduction band edge does not lie at k = 0. the model is often referred to as the hydrogen model 3. we will initially proceed with the above simplifying assumptions.81) Ti2 = -----k2. (3. In writing down these equations we start with a simple twc-band model. therefore. and ml. and the maximum of the valence band (v. &(k) 2m. the k-dispersion of the two bands is assumed to be isotropic and parabolic in the vicinity of k = 0.1 Hydrogen model For the hydrogen model we have the two effective mass equations (3.

91) . From experience in quantum mechanics. 2 . but no bound statrs at negative energies. discrete e n e r a levels are to b e expected just below the conduction band edge. we know that h r an dttrtlclite potential.~ * / n ~ ) or (3.3. . n = I .. Donor and acceptor states 267 Apart from notation.6 eV.89) with (3.(e'm//2ha) denotes the binding or Rydberg energy of the hydrogen atom. and constant factors these are the Schrodinger equations for charged particleu in the potential of a point charge.87) with (3.88) where Ef . Shallow leveb.0 reads ~ (3. ( m z / m )= 0. Thew dibcrele levels lie in the emrgy gap between the conduction and valence bands where.: = 0. signs. The orders of magnitude of the energy Eg and the length ag can be estimated easily. there ale discrete energy levels which occur for negative energies. With E g FY 13. Conduction band Transferring results from the quantum mechanical treatment of the hydrogen atom to our present situation. . we get the discrete energy levels & of principal quantum niimher 71. as we know. From this it follows that for a positive point perturbation (upper sign in equations (3. just like in the case of the hydrogen atom. there is a continuum of positive eiierpy eigmvalues and.4 and a = 1. We consider first the cwe of the conduction band. it follows lhat (3. and for negative point pertiirhations such levels are exppctpd just above the valence band edge. angular mumedurn quantum number I 0 and magnetic quantum number m .5 A . (3. The m~av~fin~rtioii FTdm(x) for principal quantum number n = 1.86)).90) where a g = ( h 2 / e 2 m )denotes the Bohr radius of the hydrogen atom.4. as ( E .2. .851. c = 11. in addition. Fur repulbive potentials there are only pusitixe energy eigenvalues.E ~= . no energy eigenvalues can appear in an ideal crystal. .

Omitting a k-independent factor. . .4 the localization of the wavefunction in k-space is also indicated. localized electron states (see Figure 3. we have.5 11. 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 2.4 (=) AM 29 A. are scattered by the Coulomb potential. For each bound state of negative energy a state of positive energy is therefore excluded from the energy spectrum. The designation shallow levels is used in this situation. Electronic structure of semiconductor crystals with perturbations a g --" 0.268 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 .4). which were previously spherical waves. Between the center of the first B Z and its edge./a) and a g k M w ( a g / a ) FY 10. 3 . including the bound states at negative energies. Changes also occur in the continuum of positive energy eigenvalues which are allowed even without Coulomb potential. Their amplitude at the positive center becomes larger. 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. remains the same as the total number of states without the perturbating potential. the Fourier transform of Fcloo(x)is given by the expression (4. (3. the discrete energy level El lies closely below the conduction band edge (see Figure 3.93) At the edges of the first B Z one has k FY (.92) Compared with the width of the energy gap which is of order of magnitude 1 el/. According to Levinson's theorem. Even closer are the states with n = 2 . Recalling the theory of the hydrogen atom. Exactly this is to be expected considering the smoothness requirement made at the outset. therefore. which are evenly spread out over the entire crystal. They are manifested in the fact that the eigenstates. . and further away from the center it is smaller. We can also examine the validity of this requirement quantitatively. which we will discuss in the next section in somewhat greater detail. In Figure 3. The localization radius a g is clearly larger than the distance between two crystal atoms.. In contrast to band states.5).5 A. which states that only Fourier components of small wavevectors k should contribute to the wavefunction. which is approximately 2. Fcloo(k) therefore falls off by about 4 powers of ten.4). . 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. this change takes place such that the total number of all states in the presence of the perturbating potential. The smoothness requirement is therefore fulfilled very well.

The energies ol thew levels are given by the exprcssiorrs En . The wavefunction of the ground state. Below.4.y core charge nunthers and the h o d core charge numhers (upper part o figure).0 L 1 O k r\ O k Figure 3.3.ive or negative differences A 2 beOween the impuril.^ for shallow impurity levels appended to an isotropic parabolic conduction band can be immediately iransferrd to an isotropic parabolic valence band.89) . has the form (3. The occupation of the shallow levels by eI&rons is presented f in the lower part of the figure.e spat:e and in kspace far mibslitutional impurity atoms with either posit.94) (3. n = 1 and 1 = m = 0. EB (3.95) The pcrtinent wavefunctions are localized at the perturbation center. Valence band For a negative point perturbation there appear discrete energy lpvels in the energy gap closely above the valence band d g r . S h d a w lev& Donor and acceptor fitates 269 AZ a 0 dZ.4: Illmtration of shallow localized States in coordina1. The levels act as donors of elwtctruns for A 2 > 0 and ss acceptors of electrons for A 2 < 0.-' z. we will writs them down without further derival ion. The abovr-Inmtionfd result.

96) as the effective Bohr radius. Although the population of energy levels by electrons will not be treated systematically until the next chapter. i. That is the shallow n = 1-level just below the conduction band edge which. we can imagine it as a P atom in a Si-crystal. also one less valence electron than in the host atom. i. with this. In Figure 3. For A 2 2 2 one has doubly or multiply ionizable donors. 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. we wish to deal now with a special case. With this.270 Chapter 3.4 (lower part) the energy levels and localization regions are shown schematically. with one positive elementary charge in the core and.e. The shallow energy level therefore functions as a donor of a free carrier. One calls it a donor level and the impurity atom itself as a donor. The impurity atom remains in the single positively charged state.according to Levinson’s theorem by one if only the n = 1-level is counted. except for the additional electron. Due to the substitution of a host atom by such an impurity atom. all the valence electrons of the host atoms and all those of the impurity atom. 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. which mandates that the total number of states must remain the same both with and without perturbation. it is singly ionized. 7’ = 0 K . namely with the occupation of the shallow impurity levels discussed above at absolute zero temperaturc.e. The additional impurity electron has to reside in the lowest unoccupied energy level.I. According to Levinson’s theorem. If the temperature is increased this electron can easily be excited from the shallow level to the conduction band. can be placed in the valence band. Therefore. we consider an impurity atom with Z I = Z H . one can proceed on the assumption that nothing will change due to the impurity atom regarding the number of states in the valence band. arises from the impurity atom. Electronic structure of semiconductor crystals with perturbations with (3. representing a freely mobile negative charge carrier. the number of valence band states is still large enough to host all + . For simplicity. This consideration will lead us to a better understanding of the nature of these impurity states. Next. the number of states in the valence band decreases . we assume 21= ZH 1. wc assume the case of a positive point perturbation. First of all. We will discuss this later more exactly.. Then the impurity atom also has one valence electron more than the host atom. The resulting occupation is shown in Figure 3. it is no longer localized but spread out uniformly over the whole crystal. according to the above results. To be specific.e. i. There..

as we know from section 3. in general. First. 3.2 Improvements upon the hydrogen model As already indicated. If the temperature is increased. the perturbation potential V’(x) has.2. also. the acceptor transfers a hole to the valence band. we can also say that. the above hydrogen model of shallow impurities. Donor and acceptor states 271 valence electrons.kill1 for all mutu& degenerate minima ki. to the appr0ximat. rather than with respect to the approximate Rloch function (xlck. The level accepts an electron. an electron from the valence band can easily be excited into the impurity level. Similar interpretations are available for doubly and multiply ionizable acceptors. it functions as an acceptor. Donors The conduction band of Si and other indirect semiconductor differs in three ways from the simple isotropic hand model.3. The analogy to the positively charged donor center which binds an electron and donates it to the conduction band is obvious. behaves like a positive freely mobile charge carrier. for symmetry reasons.4. but. 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. 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. under thermal excitation. as we know from Chapter 1. Due to the existence of several valleys (dist. Therefore. the one-component envelope function + + . a hole remains which. Shallow Jevels. cannot be directly applied to many semiconductor materials including Si. [k. minimum k only Because of this. Moreover. In the valence band itself. While the off-center location of band minima has no direct effect on the donor binding enerm. the many-valley feature and the anisotropy of the band striiccture rln have such an effect. we treat the two kinds of impurities separately.4. Some of these corrections appear only at donors. the minimum lies outside of the center of the first BZ. there remain no unoccupied states in the valence band. Below. The n = 1-level in the energy gap remains empty at T = 0 X. and third.c Bloch funchas tions (xlclri [k. we treat corrections to the hydrogen model which can be traced back to the cited effects. others only at acceptors. the wavefunction 01 the donor state $(XI to be expanded with respect. a short-range part as well as an electron-eIectron interaction part which are not considered in the hydrogen model. the band structure in the neighborhood of each individual minimum is anisotropic. whereas at T = 0 K the hole was bound to the acceptor.kc])‘of one . one minimum carries the implication of several equivalent minima or valleys.inguished by a valley index i ) .second. Consequently.

For i # j . because of the large wavevectors ki .98) = EFi(k .ki). (3.e. Electronic structure of semiconductor crystah with perturbations F. In case of k. i. and we have The envelope function equation in k-space reads rx k’ j - h2 (k . which cannot be traced back to the potential of a point charge in any way. where M is the effective mass tensor of valley i. Both modifications can cause the inter-valley matrix elements (hlV‘Jkj) of V’(x) to take larger values.kilMC’lk’ . they still remain so small that they can be considered by means of perturbation theory. the matrix elements (kJV’Jk’)result in the perturbation potential V’(x) which is already present in the hydrogen model.ki and k‘ . The latter can easily be transformed into coordinate space where they result in an additional 6-function-like potential.(k) becomes a multi-component envelope function Fi(k). O .99) If V’(x) is the screened Coulomb potential of equation (3.98) in coordinate space thus reads = EFi(X).80). one obtains a separate effective mass equation for each valley from (3. i The wavevectors k . the absolute values of the inter-valley Fourier components (kilV’1kj) are negligibly small in comparison with the intra-valley Fourier components.kj) = (3. Nevertheless. as we know from section 3. Thereby.99). as was assumed. In zero-order approximation they may be omitted completely. The effective mass equation (3.ki) 2 [ 6ij6kkl + (klV’lk’)] Fj(k’ .k j vary in a small neighborhood about the zero point. However.and k’-independent expressions (kilV’lkj).k j occurring in the former combined with the (l/lkl’)-dependence of (klV’) on k. k and k’ are vectors near the respective minima ki and kj. it reads. because V’(x) contains a short-range part.2. because the screening of a point charge by the semiconductor is wavevector dependent. the true perturbation potential V’(x) differs from the pure Coulomb potential. in coordinate space . = ( O . k z ) . the matrix elements (kJV’Jk’)of the perturbation potential V’(x) can approximately be replaced by the k. With i = j .272 Chapter 3. and on the other hand.

100) over all directions in k-space.3.5a. in addition. the inter-valley coupling in the effective mass equation (3.100) depends on direction in k-space. one can replace the reciprocal effective mass rn: of the hydrogen model by the reciprocal effective mass (l/m:ll + 2 / m . In perturbation theory. etc. Numerical results obtained by means of this procedure for the energy levels of the P-donor in Si are reproduced in Figure 3. They should. In this case the wavefunction of the first excited state must. Donor and acceptor states 273 Analogous equations hold for the other valleys. this calculation will now be . For a simple estimate of the anisotropy effect. 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.99) will be considered. which is better as the linear combination of auxiliary functions approximates the actual eigcnfunction.5. be orthogonal to the ground state wavefunction. ) / 3 obtained by averaging the direction-dependent reciprocal effective masses of (3. in particular) correctly reflect the symmetry of the actual eigenfunctions. Using the example of Si.4. the effective mass of the envelope q u a tion (3. but which still contain free parameters. One possible approach is the application of a variational procedure. With this. This minimiim value then yields an approximation for the ground state energy. Shallow levels. that of the second excited state must be orthogonal to both previously calculated states. one obtains energy levels for the simply ionizable donor in Si. Inter-valley coupling As a second corrective step. which are shown in Figure 3. and one mist resort to approximations and numerical calculations. In this circumstance. This means that. analytical solutions arc not available. Using this representation one calculates the energy expectation value of the Ilamiltonian and varies the parameters until its absolute minimum is reached. the calculation of eigenvalue corrections involves the diagonalization of the matrix O(kilV’lkj)lFj(0)12. Anisotropic effective masties In contrast to the hydrogen model. neglecting inter-valley coupling. all valleys give rise to the same donor level. in the case considered here the symmetry of the ground state wavefunction. One can also employ the variational process for the calculation of excited states. The binding energy E B is represented as 29 meV in this approximation. The success of this approach thus depends in an essential way on the auxiliary functions used.

. AEz = -2b + 2 fold AEg .0. k.02 . 1985. 1 . k .101) are written in the sequence -__ k.~ axes k. ( A f t w Rlakemore. ( ) 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 (3.274 Chapter 3. The matrix (3.04 -0. which lie on the cubic _ .-c. d) exxperimental results. k. 2 -0. close to the respective X-points. k. k. Lines and columns in (3.fold (3. From symmetry considerations it follows that f ( .5: Ground state and first excited states of a phosphorus donor in Si: a) hydrogen model. c) including central cell corrections. and k. r = ~t(kzIv'lkz)l..fold C.101) has the three eigenvalues A&I = 4b + C...102) have been used.101) b = fi(k~lv'lky)l~z(0)12.0'0° T > w I w CI. V l .05 performed explicitly. kzrk.. k. k . efferlive mass anisotropy arid intervalley coupling.Ol ! -0...03 -0. b) including effcctive mass anisotropy..)IFz(0)12 (3.) . In this case one has 6 minima. 3 . Electronic: structure of semiconductor crystals with perturbations Figure 3.103) . I ..

. The simple theoretical estimate presented above agrees remarkably well with the experimental splittings of 11. and assumes that screening has become fully ineffective at large wavevectors k. one obtains b as -2.e. i. The size of the splitting depends on the inter-valley nitrtrix elemen1 of the perturbation yolmtial. Chemical shifts In Table 3. .e. and WP will also employ thcm here.and T2-levels. ‘The notations A . This yields AEl = -10.e. Donor and acceptor states 275 with the degrees of degeneracy indicated.kj. k. A 3-fold splitting of the P-donor ground state level in Si has.. y.. If one considers only thc first of thc two abovementioned effects which result in matrix elernentv ol considerable size. z . The results of a numerical treatment of inter-valley coupling shown in Figure 3. To demonstrate this one may employ the transformation rules of the vector components x .4.2 met‘.6 meV between the A l .8 meV. Then one easily 1 finds that the irreducible parts of this representation arc rl ( A .. that of the two AETstatcs is E . kg. a. i. then it follows that (3.and T2-levels (not resolved in Figure 3.8 meL’ which is closer to the experimental value of 45 meV. of 10..6 met‘ and AE3 = 1. realizing that these component? transform in the same way as thc reciprocal vector components considered here. and that of the three AE3 states is 12.. k.104) With this. the agreement is not as good for the absolute position of the ground state level. r 2 ( E ) and I’z5(Tz).8 meV to the binding energy of 29 meV without inter-valley interaction yields a corrected binding energy of 39. A E z = 3. Thus. it is clear that the symmetry of the AEI-state is A l . Z under the action of the clcments of o h (summarized in Table A. been observed experimentally (Aggrawal and Ramdas. in fact. k. inter-valley coupling partially removes the 6-fold degeneracy among the valleys. _ _ ) in the space of the 6 reciprocal vector compo_ of o h .7 of Apprndix A).5 we list experimental binding energies for a number of singly . 1965). the wavevector dependence of screening.3 meV between the E . for Si:P but still clearly below. However. E .7j.99) for si.therefore replaring the screened Coulomb potential V’(x) of equation (3.2 meV. ) . T are commonly used in the theor. Shallow lwels. The addition of A E l . i.36 mel’ and c as -1.5).k.80) by the bare Coulomb potential -(e2/IxI) in (ktlV’lkj).5 are even closer to the experimental values. nents k. One considers the representation of the symmetry group of the envelope e q u e h n (3.3. 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. With this. This representation is reducible. and of 1.of z l o c a l i d states.

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

This may be done by means of the multfband effective mass theory developed in the preceding section. Later this approximation needs to be corrected since E g is not much larger than A.5 for further discussion).7 these were approximated by two isotropic parabolic bands. ShalIow levels. In fact. then there are two hydrogen-like series of acceptor le\-els. Of course. Donor and acceptor states 277 (which does happen in the case of the ground state) but further outside. z of the representation T . this degeneracy splits off and one has ihree or two anisotropic valence bands.m = x. If one also uses this approximation here. as is assumed in the hydrogen model. non-parabolicity and anisotropy of the band structure play an essential role and must be taken into account in realistic calculations. In section 2. they differ appreciably from the measured ground state binding energies shown in Table 3. Without spin and spin-orbit interaction the wavefunction ~ A ( x ) is a linear combination of the three Bloch functions (xlumO). or the 4-fold degeneracies of the representations I?$ (diamond) or Ts (zincblende) in the space of twc-component spinor functions. Below. y. we will explain the application of this theory to simply ionizable acceptors in Si.95) in the case of Si yields 50 met7 for heavy holes which are expected to form the ground state. Calculating acceptor binding energies by means of expression (3. respectively. Evidently. the %fold degeneracies of the representations l'b5 (diamond) or (zincblende) in the space of scalar functions. In the vicinity of r. However. one for each sort of holes. Thus (3. which are enveloped by the i. Acceptors Corrections to the simple hydrogen model are also necessary for acceptors. In the case of Ge. Generally. 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. One can hardy expect these values to be in agreement with experiment. one for heavy holes and one for light holes.105) . the maximum of the valence band lies in the center r of the first B Z for all diamond and zincblende type semiconductors.(x) of the envelope function vector F (x). * components F.4.5. the result is 17 meV for heavy holes. 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. spin-orbit interaction initially will be neglected. this maximum is degenerate: depending on whether spin-orbit interaction is important or not one has.3. 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).

. belong to a space which differs from the ordinary . .ql(x). . in closed analytical form. as has been supposed.. actually transform according to the representation r ~ * * The FA^ (x). . . One has to use spproxinia tions and numerical calculations. long to the representation r A .. . The meaning of this will be explained below. .F A ~.. The corresponding aigenhnctions are .278 Chapter 3.q2(x). forincd according to relation (3. The variational method again represents a reasonable way to proceed. but by three-component basis functions. therein. in the case A 2 = -1. . FA? ( x ) .. one of which corresponds to the 3D rqresentation according to which the components of each of the three= $ * component. the wavefunctions T . one obtains.107) . of equation (3. The eiigenvalues and eigeuvectors of this complicated set of equations cannot be obtained. Electronic structure of semiconductor crystals with perturbations The corresponding effective mass equation of the I’b5-valence band is given by relation (3.. U ( x ) is identified as the Coulomb potential. (3. of course. . .105). A representation in this space is given by the product of two represt?nt. denoted by $ A ~ ( x ) .. must belong in order that . formed from these vectors by meam ).@m(x). (3. For the representation * * D A of FA^ (x):FA^ (x). One can easily show that the latter representation must +. q l (x). it follows that . 3 * . and the other is the representation according to which the threecomponent functions transform among each other. We consider a particular acceptor level E n . FA^ (x).b e be r A . It belongs to an irrdiicible reprc sentation r A of the point moup oh. and the pertinent multi-component envelope function by ~ . . This function should have symmetry properties which fit the symmetry of the acceptor state @ A ( X ) to be calculated. If. FA^ transform separately.80). .atinns. fiinctions FA^.105). In this approach one starts with a choice of suitable auxiliary functions for the expansion of the multi-component enve=$ lope fundion F (x). which in general will be degenerate.72). Hilbert syaccr in that it is riot spanned hy oue-comyonent basis funrlious. W e have to find the representation D A of =$O h to which the set of vectors F A ~ (x). . so that $. ~ A ~ ( x$~z(x):.

These are formed in analogy to the eigenfunctions for the Coulomb potential. In order to also get their raand ri5-functions with diaI dependencies one expands the rl-. 1962).27 of Appendix -4. just like the Coefficients of the auxiliary functions belonging to different irreducible representations.~only when the symmetry r-4 of these functions is I'h5. however. Applying this procedure to the acceptor ground state of Si.108) shown in Table A. An envelope function basis vector which transforms according to the unity-representation occurs in the expansion of the accep) . r12-. Donor and acceptor states 279 This representation is reducible. According to (3. the T'& valence band has to be replaced by the two rg. respect to angular momentum eigenfunctions with the various quantum numbers 6. does not account for the pronounced chemical shifts seen in this table. Owing to the large spin-orbit-splitting energy. 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. therefore the angular dependencies of these functions. 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. 1977). of course. the spin-orbit-split I'F-band can be omitted. a binding energy of 31 me&' is obtained (Schechter. The latter are treated as variational parameters. . Shallow levels.107) yields a remarkable conclusion concerning the symmetry of acceptor states. Equation (3. The basis vector belonging to the unity-representation is the only one which does not vanish at the central site x = 0. Acceptor levels of other symmetry are necessarily excited states.4.and r$-bands. tor eigenfunctions $ A ~ [ X ) . Relation (3.5 but.108) determines the symmetries of the three-component auxiliary functions under rotations.107) this is only possible if the ground state has the symmetry Fh5. 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 + + + + . which is very close to the experimental value of 45 meV for 3 in Table 3. i. 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.e. @ ~ ( X . taking spin-orbit interaction into account. rn and multiplies the expansion coefficients of different values of I by corresponding radial wavefunctions r1exp(-T/q).3. More recent calculations. but with &dependent localization radii rl. have resulted in a value of 44 mel/ (Baldereschi and Lipari. Spin has to be taken into account under such circumstances. 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.

Electronic structure of semiconductor crystals with perturbations (A. 3 or more. Obviously. 1978). as it dow in fact. Without this interaction the effective mass equat.By exciting one electron into the conduction band. leaving behind a 1-.9-level because of 2-fold spindegeneracy. close to the experimental values of 12 nieV for In and 11 meV for all other elements listed in Table 3. 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. reflecting the fact that the effective heavy hole mass in Ge is smaller than in Si. 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. but differ by 2. and 1.28)).5. chemical shifts are very small in the case of Ge. then the 1s-level is shifted up by just this energy Us. 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 .25). This implies that the acceptor wavefunctions of Ge have smaller amplitudes in the central cell than those of Si. 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. In the calculations for Ge. 3 or more electrons can be thermally excited into the conduction or valence bands. 2-. Then 2. 2. 3. the neutral S-donor .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. unlikr Si where these shifts were found to be very pronounced. In the ground state.280 Chapter 3.1 from those of the host atom. as we assumed above. 2 electrons are bound at the S-donor. an acceptor binding energy of 10 m e v is obtained. We illustrate these remarks using thc example of the S-donor in Si.0 K .or morefold ionized impurity atom. 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. For the same reason.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. both of which can be placed in the 1. which in this case is approximately given by is taken into account. The interaction between the carriers bound at the center is described by the Hubbard energy of equation (3. The Hubbard correction (3. E D is siihstantially srrialler than in Si. 3 or more electrons or holes are weakly bound to the impurity atom at T . If the Hubbard correction.

In regard to their ability to bind states. In this. the central cell short-range poteniid cont. 3.hat the ionk-ation energy of the neutral S(O+) donor is 0. in comparison with the 1s-level of tbc S(0 +-) atom.e.n from section 3. generally. consists of a long-range (Coulornbic] part and a short-rangp part. i.rir:cobstant. 1968). Evident. for a 3-dimensional potential box of depth Vo and radius a. hound $Pates exist. k1loa.fast with decreasing well dept.hecontrary.ly.hc potential prevent the partick from escaping the center.e.ion. ? Schiff. The spatial extension of the eigenfunction is essentially given by the Bohr radius. This indicates already at t. the condition Vo > h2/(8w>. one finds t. must have a minimum st. of 0. however.uli) must he fulfilled for a b a u d state to exist (see.e. For the I . Short-range potentials. shallow levek ocrur for statps which are bound by a Coulomb potential. it only leads to corrections of the binding energy and the eigenfunction of the ground state. ‘ l l i s donor is a deep center rather than a shallow me. the average kinetic energy decreases sufficiently.5 Deep levels 3+5. by the long-range contribution of the total perturbation potential. In the case of the long-range Conlomb potential.a sld 01 h e S ( l 1 ) ioii thr shift in energy by Us do= not occur.ionand: with this. i. in that localization due to the potential leads to a non-vanishing expectation value of momentum and 1..12 eb’ which follows from the hydrogen model.6). 4 x 0. IIowever.h to he able to bind a stale..1 General characterization of deep levels As we know from previous sc3ctions. e g .8. for all possible potential strengths. If t.rengt. the two potential contributions differ substantially. (Not.03 el7 = 0. on t. For example.3. that in the case of a 1-dimensional potential box.4 as c e n l m l tell correcfioru. Heisenberg’s uncertainty principle manifests itself.hus also of kinelic energy of the particle.he outset that 1-dimensional models of deep centers are ralher poor). According to wction 3. From thefie values a Hubbard energy I i .4.ribution is ewedial in the case of the S-donor in Si. for arbitrary magnitudes of the point charge and dielect. bound states exist for arbitrarily small m d l depths sincc the 1ocalizat.ant short-range potential part does not suffice in this case for binding. and the ionization energy of the S(1t) donor j s 0. The concornit.31 eV. Only if the dept8h of the potential box exceeds the expectation value of this kinetic energy! can t.28 eV may be deduced. both ionization energies are suhstantially larger than the result.h. hhc potential of a point perturbat. Thus this level i s shifted down by I/. Exprrirneniully.69 eV (see Figure 3. Deep lewls 28 1 S(D+) bccarnes a single positively charged S(1+) donor.he strength of the short-range .

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

The fact that for donor states . . and valence shell p-level differences in the caae of acceptors. and acceptor energies to the valence band edge.i the discussion above.3 . Donor energies are reIative to the conduction band edge. An experimental proof of the threshdd behavior of short-range potentials in crystals may be taken from Figure 3.6. measured in terms of valence shell s-level differences between impurity and host atoms in the case of donors. 1981._ a: F . 1990.5 . Reproduced from Boer.. 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.- 2 .6 (eV) 2 1 -2 -4 -G -8 -1OleV) Atomic Electronegativity Figure 3. the periodic potential of the crystal was omitted n from consideration.283 2 1 0 -2 -4 -6 . (After Vogl.4 Acceptors .. This difkrence can serve as a measure of the strength of the short-range potential.6: Ionization energy of substitutional impurity atoms in varioum tedrahedrally coordinate host semironductors as B function of the strength of the pcrturbation potential.

The ionization energies initially retain their small valucs characteristic of shallow lcvels. In general. or ~ L non-eyujlibiium cariiers due to optical or other excitation of Y of the semiconductor.2 we will develop a simple model of a deep center. which are available there eithrr as equilibrium charge carriers due to n-doping. Electronic structure of semiconductor crystals with perturbations the diffrrence of 8-levels is taken. such as in semiconductor light emitting diodes or laser diodes. the potential strength increases more or less continuously. If. Starting at a threshold distanre. Due to their mostly larger separation from the hand edges they are. and in the second case. On the other hand. a cupture of non-equilibrium electrons by the center (see Chapter 5). in addition to the neutral center. the lowering of free carrier concentrations for which. generally less effective than shallow levels in enhancing the concentrations of free charge carriers. decp levels can also act as donors or acceptors (sometimes even as both of them). Having discussed the general character and importance of deep centers. they suddenly become substantially larger. and for acccptor states the differenre of p-levels. shallow levels are not very effective. In subsection 3. we now will treat their electronic structure. the neutral center will capture electrons from the conduction land. With increasing horizontal scparation of the impurity atom from the host atom in the periodic table. in turn. In the first case. a manifestation of the fact that the short-range potential has takm over binding and the level has become deep. which involves the elimination of the corresponding deep centers. non-radiative recombination processes have to be avoided.4. deep centers play a role of similar importance to that of shallow ones for semiconductor devices. although in a completely different way. one should intentionally introduce deep centers in order to enhance non-radiative recombination.284 Chapf. however. In subsection 3. In section 3.5.er3. A center which forms deep levels in the gap both in the neutral and simply positively charged state.3 we treat some methods of solution of the one-electron Schrodinger equation for deep centers. The consequences of many-electron effects in the electronic structure of deep centers will be discussed in subsection 3.5. They exhibit their greatest efiectiveness in just thp opposite process.Just like shallow levels. 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 .5. plays an analogous role in regard to the compensation of acceptors and the capture of non-equilibrium holes. is not important foi the present discussion (we will return to this point later). If one wants to enhance radiative recombination as strongly as possible. the so-called defect-molecule model. Centers which can capture both electrons as well as holes act as catalysts for the radiationless recombination of electron-hole pairs (see Chapter 5). . if one is interested in having a short lifetime for non-equilibrium charge carriers.5. the single negatively charged center also forms a deep level in the gap with sufficient separation from the conduction band edge. as in the case of fast transistors and photodetectors.

we will apply this model to substitutional impurities from the main groups of the periodic table. This was advantageous because the translation symmetry of the crystal could be exploited in this way. but rather. In doing so. However. in all cases. we employed wavevector-dependent Bloch sums lukj) or ihtkj) formed from them. the substitutional impurity at. we discuss the D X center and the EL2-center in GaAs. The simplest among these models is the so-called defect-molecule model. Of course. many particle effects and lattice relaxation will be ignored.7 shows part of a Si crystal containing a vacancy.6 represents one of the various procedures for calculating band structures of ideal crystals. We select hybrid orbitals because these produce drastic simplifications of the Hamiltonian matrix which.e.oms of the main groups of the periodic table. and the results also cannot be expected to be very accurate in a quantitative sense. Deep levels 285 for selected deep centers. allow the eigenvahes of the Hamiltonian to be calculated in closed analytical form. We introduce the defect molecule model using the vacancy as an example. Since the perturbation potentials of deep centers are localized on the same scale. We will mainly use the model to demonstrate the existence of deep levels and to explore the symmetry of the pertinent eigenfunctions. so that localized basis functions. As the host crystal we take. among them the vacancy in Si. the TB method should be particulady well suited for such centers. atomic or hybrid orbitals. i.like Si. an elemental semiconductor of group IV. 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. Symmetry consid- . the method should be suited to the derivation of simple models that exhibit the essential physical features of real deep centers.5. Also. E the ideal crystal case considered in section 2. Unlike other methods it uses basis functions to represent the Hamiltonian which are localized on the atomic length scale. one must chose the Hamiltonian matrix elements empirically in order t o arrive at useful practical results. The latter symmetry no longer exists in a crystal with a deep center. the group of 3dtransition metals.5. 3.the atomic n orbitals or hybrid orbitals IhtRj) were not used directly. which we will introduce below. Later. and the group of rare earths. like the Bloch sums of hybrid orbitals in the case of an ideal crystal.6. can also be used without any loss.2 Defect molecule model The 'Tight 3inding' (TB) method developed in section 2.3. Vacancy Figure 3.

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

W is expect. namely the value given above in equation (2..ed to be negative. but rather by the tetrahedral group y d .e.c. t‘ f t . i.5. 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 . and the anti-bonding level E = E. Deep levels we can refer to the first partial system as a vacancy molecule: 287 and to the the ‘rest-of-crystal’.e are small. The energy levels of the vacancy-molecule are obtained by diagonaliziug the matrix + . The splitting of these highly .t2Rt(V‘ lht2Rt) of the vacancy potential V‘ between hybrid orbitals localized off the %mancy sit.292) defining matrix element T/2. degenerate levels into bands remains incomplete because of the neglect of Ihe interaction between hybrids at.+ I&I. This designation also encompasses h e term defect molecule model for the tight binding approximation described above. one has to recaIl the symmetry of the perturbed Hamiltonian H +V‘. we need the matrix elements of the pertarbed Hamiltanian H + V ’ of the crystal with vacancy. Since. such that wit. by creating a vacancy in sublattice 1) the two sublattices are no longer eqiiivalent.b W as second-nearest neighbor interaction energy. of r/l.IVzl. In calculating the energy spectrum of the first partial system. the vacancy-molecule. The Hamiltonian matrix elements between the various pairs have the same value. Nevertheless. the neglect. the same &om? i. this means that all non-diagonal elements are equal for symmetry reasons. The diagonal elements (ht2RtlH + V‘lht2Rt) are simply the hybrid energies ~h since the elements (h. h d of the infinite idea1 cryslal in bhe simplest TB approximation? consisting of the bonding level t b = th . ‘I’he absolute value of W must be determined empirically. The energy spertriim of the rest-ofcrystal is therefore identical with t .3. 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. For each hybrid of the rest-of-crystal another hybrid exists in the restof-crystal which points to it. the symmetry of the crystal is no longer given by thr full cubic point group Oh.

8.Jh2R3)] ~ 1 v5 I 1 138"")= . The A1-level lies below the Tz-level because of the negative value of Vt-.-[ I ~ I ~ R I ) .6 of Bppendix 4 ) .116) (3. VaC Jz [IIZL~RI)IhaZRz)]. Whether it lies below or above the bonding level of the crystal depends on whether we have 31W1 < l\Jzl or 31WI > lF'21.[lh12R1). . the sp3-hybridization of the atomic orbitals in a Si crystal is removed at a vacancy. The eigenfunction of the A1-level resembles an atomic s-orbital of a Si atom. the valence band has shrunk to the bonding energy level. show that the -41level lies in the valence band. The states are more atom-like. which we will discuss later in more detail. (3.lh42R9)]. Experiment and more exact calculations. therein. and the 7'2-level in the energy gap. The question of whether it is found in the valence band or in the energy gap. IEY'). It is just as difficult to decide whether the Tz-level la i in the conduction bend or in the energy gap. 45 One can easily demonstrate that IEI") belongs to the irreducible representation A1 of the symmetry group Td of the vacancy. and the three Tz-eigenfunctions are similar to the three p-orbitals of such an atom.288 Chapter 3. and the three functions IE$uc). IEiWc)to the irreducible representation T2 of this group (see Table A. Electronic structurc of scmiconductor crystals with perturbalions Its eigenvalues Eyzz.113) (3. cannot be answered within the defect molecule model because.114) IEY)= IE. With this. Evidently. in consequence of the fact that the crystal potential is no longer fully effective in the vicinity of a vacancy.117) (3. In Figure 3.118) ) . 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.4 read (3.

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

E . namely In this. and second. although it influences the actual position of this level in the energy gap. first. This approximation does not affect the answer to the question of whether a particular impurity atom forms a deep level or not. We consider only the most important elements of this matrix.2. Xeglecting interactions between the hybrid orbitals at the host atoms.119) where j and j ’ take the values i and 2 independently of each other.290 Chapter 3. jht2Rt).t = 1.4.). into two partial systems. The energy spectrum of the rest-of-crystal again coincides with that of the ideal crystal within the framework of the approximations used here.3. The latter cannot be determined within the defect molecule model anyway. and c i signify. and the four hybrid orbitals of the host crystal pointing in the direction of this atom will be denoted by IhtzR.2.4. Electronic structure of semiconductor crystals with perturbations Figure 3. the defect molecule with the 8 orbitals jhtiO). the crystal with a substitutional impurity decomposes.3. the rest-of-crystal with all remaining orbitals. The Hamiltonian matrix of the defect molecule is composed of elements of the general form fhtjRtIH + 17’lht~j’R~~)~ (3.9: Defect molecule model of a substitutional main group &bonding impurity atom in a tetrahedrally coordinated semiconductor. just as before in the vacancy case. the hybrid energies of the impurity and host atoms. V2 corresponds to the matrix element of H of equation (2. The four sp3-hybrid orbitals of the impurity atom will be denoted by IhtiO).292) between hybrid orbitals at nearest-neighbor atoms of the ideal crystal .t = 1. respectively. L latter will be omitted from consideration below.

. This difference represents a measure of the strength of the short-range perturbation potential of the impurity atom. I@&). among them also the Vl-like elements (htzRt(H V’lht. with t’ f t. lh3iR3). In order to better understand the physical meaning of the energy levels derived above.b.i&. Deep levels 291 pointing toward each other. two simple and two triply degenerate. lh12R1)) lh22R2).E ) ..124) 0 W E k W W W W E k W 0 (0 0 0 v20 0 I $ w w w e. which . 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 . First. and W describes. With these approximations. All elements ( h t j R t l H V’lht‘J’Rt.O 0 0 0 vzo 0 6 i 0 v20 o a o v2a o o 0 v2o a o v2 € . whence EiT/b In Figure 3.5.125) and (3. the Hamiltonian matrix of the defect molecule may now be written down in explicit form. we assume the impurity atom to coincide with the host atom.3. This matrix has four distinct eigenvalues. it is helpful to consider two limiting cases. means t i = c If one also neglects the second nearest-neighbor interaction energy W . denoted as and E&Y:. then the energy spectrum of the perturbed crystal of equations (3. The corresponding energy levels are. and the Hamiltonian matrix is + + L i 0 0 0 0 0 0 1720 0 0 0 €e. between the hybrid energies of impurity and host atoms.) listed above are neglected.) between different hybrid orbitals at the impurity atom. lh32R3).126) must coincide with that of the ideal host crystal in the . and the two triply degenerate (again distinguished by indices b and a ) belong to the 3-dimensional irreducible representation T2 of T d . lh4iR4).e. In doing so the rows and columns are ordered in the sequence IhliRl). W W W (3. lh2iR2). the second nearest neighbor interaction between differing host atom hybrid orbitals not pointing toward the impurity atom.10 these levels are plotted as functions of the difference ( c i . as in the vacancy case. i. respectively.

Second.129) .10 encompass the energy gap of the host crystal.$ two undisturbed levels € h f IV21 in Figure 3. i. simplest TB approximation.e i ) . This is in fact the case. Electronic structure of semiconductor crystals with perturbations Figure 3. The . In the limit EiT.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 . respectively.128) and in the limit Ei 4 --oo we have EiT = tk + 3W. we consider the limiting case of ( E . -+ -00. to bonding and anti-bonding states of Tysymmetry.125) and (3. also means t i -+ +m or E . for a given host crystal. Horizontal lines indicate the bonding level t b and the anti-bonding level of the host crystal.. and the two energy levels EY . .292 Chapter 3.127) (3. E i + $00 equations (3. of the perturbed crystal Thus it is also clear that the two energy levels correspond to bonding and anti-bonding states of A1-symmetry.e.126) yield (3. = € h + IV21 must emerge. and an anti-bonding energy level E.tk) tending toward $00 or -00 which. (3. a bonding energy level q = ~ h IVzI.

A look at Figure 3.5. More rigorous calculations confirm this conjecture in that they find exactly these levels to be in the gap. while the two bonding levels and limit toward. the two anti-bonding levels and EkYZ of (3. Two remarkable differences were found in relation to an ideal crystal: First. and the anti-bonding A1-level if ( 6 . namely because t i + -00 means that there is a vacancy at the impurity site. while the anti-bonding levels limit toward the two A l .and Tzlevels.3 Solution methods for the one-electron Schrodinger equa. Deep levels zmp = Ezmp EAlb Tzb ~ 293 + --O0. depends on the electron poputhe effective one-electron potential VPert(x) lation of (localized) one-particle states. With E . In other words. For finite positive values of (EL .).8) for the crystal with a point perturbation.In section 3.3. (3. . This is understandable because the limiting case EL ---f +m means that no impurity hybrid energy level exists at finite energy and.e. there is also effectively no impurity atom.E. respectively. and for finite negative values of (tL-~k) the same can happen with the two anti-bonding Al. Thus the potential Vwrt(x) the center can also be considered to be known. 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. in many cases initially unknown and it must be selfconsistently calculated jointly with the electronic structure.and Tz-levels of the vacancy of equations (3. This occurs for the same reason as above in the limit t i -+ +m.6 . which participates in the determination of the pois tential Vwrt(x). Below.130) In the limiting case t i -+ +m.114). ) < 0 holds. leaving the energy spectrum on its high energy side.and Tz-levels can occur in the energy gap.5.113) and (3.and T2-levels of the vacancy of equations (3. the two Al. -+ -m the two bonding energy levels and E$T leave the energy spectrum at its low energy side. i.127) tend. forming deep levels there.114). there is a vacancy. therefore.2 this task already was addressed in general terms. In regard to the of . 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).113) and (3. we will describe such calculations and discuss methods for solving the one-electron Schrodinger equation (3.)i > 0 holds. the bonding Al. Below.10 shows that the most favorable candidate for an impurity level to be in the energy gap is the bonding Tz-level if ( ~ 6. toward 00. and second the atomic structure of the perturbed crystal. along with t i . EiT EiY EkYl EiY 3.

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

this decomposition is essential. in the iundamenlal energy gap between the highest valence band and the lowest conduction band. (3.H1-l stands in close relation t o the Green's function of the unperturbed crystal. 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. First we consider the bound states. 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.21)equation for the perturbed crystal once again in a somewhat modified form. of the cluster in the first method and of the supercrystal in the second. It provides results not only about bound states with energy levels in the gap of the ideal crystal. 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. for k = 0. the Green's function method.HI.5. As tl preliminary we note that equation (3.132) . these widths are negligibly small and it suffices to calculate the band structure of the supercrystal for one k-point only.3. The retarded Green's finctaon O " ( E ) is defined by the equation GO@) = 1 Eti6-H' (3. Green's function method The Green's function method employs techniques and insights of quantum mechanical scattering theory..L@ ". [E . e. the decomposition of the entire effective oneelectron potential into that of an ideal crystal and a perturbation potential need not to be made. the eigenvalues E which WP seek from this equation lie outside of the bands. Results for the band structure of the ideal crystal are neither necessary nor useful in either method.H1-l of the operator [ E .g. Also. In the third method for calculating the electronic structure of perturbed crystals. and the band structure of the ideal crystal is required.131) can be formally solved for @ by multiplying both sides by the inverse [E . to be mare precise.HI+ .. The inverse operator [ F . If the supercell is made large enough. i. but also on scattering states having energies in the allowed energy spectrum of the ideal crystal. Bound states: Kostcr-Slater method To explain this method we write down the Schrdinger (3.131) Since we are interested in bound states.e.

1 minant of the matrix of the operator [ C 0 ( E ) V ' 1 .296 Chapter 3. in that the response occurs only after the system has been perturbed. If one does so. no singularities occur in G " ( E ) of equation (3. The energy eigenvalues E satisfying this equation are deep levels.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. in an appropriate orthonormalized basis set.131) as KosterSlater equation The Green's operator @ ( E ) can be cdriilattul if the band structure E. As our present interest is in deep levels in the forbidden part of the energy spectrum of the ideal crystal.(k) and the Bloch functions of the ideal crystal are known. These levels ran thus be determined by calculating the Green's function G o ( E )of the unperturbed crystal and solving equation (3. However. Koster-Slater method in Wannier representation Wannirr functions are linear combinations of all Bloch functions for a given band index v of the form .134) holds. 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. The matrix represenlation of d ' ( E ) in the Bloch basis reads (3. (3. A particular compromise in choosing a basis set for the representation ol the eigenvalue equation (3. Using G " ( E ) . This procedure assures that the wavefunction response of the unperturbed crystal conforms to the causality principle. and equation (3. i. This p r o w dure is rcfrrred to as Koster Slater method.I]?) 1 0.r.134). then the matrix representation of the (heen's opertrtoi is not as simple as in the Bloch basis.133) Non-trivial solutions me possible only for energies E for which the deter. and we may ignore 6. if Uet[G"(E)V' 1 = 0 1 - (3.equation (3. not in changes of wavefunctions with energies in the already existing continuous part.131) may be formally rewritten as [@(E)V' . i t would be more expcdicnt for the matrix representation of the perturbation potential to use localized wavefunctions as) for example.134). vanishps.134) is the use of so-called Wunnzer finctzons.132) in the range of E of interest to us. atomic orbitals.

we assume & = 0.141) Equation 13. its determinant has to vanish separately.139)) equation (3. 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. .143) as The matrix elements of the potential (vRIV’jv’R’1 are particularly large if R and R‘ are identical.If the latter are chosen properly.136) Here the summation is over the whole first BZ.141) forms a closed set of equations for the central cell compo) nents ( ~ O ~ I Jof $ only. and ‘ t k are certain phase a~glru. i. all other components (vRI$) follow at once from equation (3.141) to exist. and both are equal to the lattice vector of the cell which hosts the point perturbation.140) For the particular lattice point R = 0 it reads { 3.5. Neglecting all other elements we find Employing (3. As before. If the latter are known. For a non-trivial solution of the homogeneous system (3. Deep levels 297 (3. it reads The matrix elements of the Green’s operator G o ( E )may be obtained by means of (3.140).137) becomes (3.138) and (3.134) i s written in terms of this basis.3.e. rdls in a ppriodicity rcgioa.G“ is the number of primitive unit.

v = c.E ) into this integral. Electronic structure of semiconductor crystals with perturbations must hold.143) for G : ( E ) we rqlace the k-sum by an integraL This yields G0 E ) J = -. as well the perturbation potential matrix elements. 1 G 3 8x3 ' d%i s t ~ 1 ~E -I.(E) 1 (vOlG*(E)IvO) 3 = G 1 Ic E+ir-EE.w.143) The dominant bands in equation (3. G:(E:) may be written as with Jrm (3.142) becomes or more explicitly To solve this equation.(E) : d3kd(E . Below we calculate the host Green's functions for isotropic parabolic bands of finite widths. (3. the host Green's functions G:(E) and G : ( E ) . In expression (3. the uppermost valence band u and the lowest conduction band c.142) may be obtained from (3.147) whrre p v ( E ) is the density of states per unit energy and spin state p. The diagonal elements (vOIGo(E)IvO) G ! ( E ) of the Green's = operator in equation (3.232 R .148) .e. i. If we consider only them and neglect all others equation (3. v.E..(k) ' v = c.138) as G.142) are those which form the gap. Introducing the identity operator dE'd(b" . (3.&(k]) h3 1.(k)' (3.146) st beiug the volume of a periodicity region.298 Chapter 3.i t . have t o be known.

they Eare in fact real. The E‘-integral is readily done. Then it follows that (3. Later. ~ . (3. 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). the energy gap EB.149) 3 pc(E) = ~ G3 ~ ~ ~. ( E ) of equation (3. and the two band widths A& and AE.(E). In evaluating p.147).5.TI’F] (3. to be the same as those of the original bands. taking their band widths A E .. The imaginary part ofG.213) by a factor (0/2).AE.3. Altogether. We substitute these expressions into the Green’s function G .. This corresponds to the use of an effective mass for each band averaged over the whole first B Z . . 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.(E) equals (-TI times pv(E). The bandwidths are introduced by putting the total number of states of the approximate isotropic parabolic bands equal to G3.)] E [ O ( . This would hP obvious if we rcplaced the In-function by an arctan-function.152) Although complex numbers appear in these expressions. however.E.150) where B(E) is the unit step function. The real parts ReG:(E) and ReG:(E) are given by -I.Eg) B(E . the host Green’s functions of OUT model depend on three parameters. we approximate the true valence and conduction bands by isotropic parabolic ones. Deep levels 299 which differs from the DOS in equation (2. 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.

(3. 4.I. so that in this rwpeet there is 110 change.i6 . A 1 d dE (3.155) of the unperturbed crystal may be expressed in terms of the unperturbed Green's function Co(E). In quantum field tbwry. this relation is known as the D p o n equatzon Using thk equation and performing some simple calculations.e. 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.154) which follows at once from the definition (3. Integrating A p ( E ) over this interval.P O ( W (3. To calculat? this change it is expedient to introduce the Green's fiirirtion of the perturbed crystal.[H+ V ' ]. (3. 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 . This change may be obtained from (3.300 Chapter 3.1533 of G'(E). 0. Of course. in the form of a modifid density ol statvs.156) ol t h r nos clue l o the point perturbation.em. here thai of the crystal with the point perturbation.158) .155) and (3.156) as (3 157) G'(E)V'I. E ) (3. i. and considering the fact that G ' ( f i ) vanishes for li: -+ f m .I m -In D e t [ G ( E ) ] .209) may be brought into the form p(E) . the w e r g i a of t h e w bands are still allowed quantum mechanically in the presence of the perturbation. yields 1 d Ap(E) = --Irrt-lnDDet[l- x lm M ~ E A ~ (=. We seek the change I an analogous way? the DOS P O ( ! ? ) n M E ) = P(E). 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 ) . 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. the DOS expression (2.153) According to formula (2. 1 G ( E ) . 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. However.209).

this result will play an important role.1). One speaks of these as resonance and antz-resonance state.5. we continue the general discussion of section 3.9. no assumptions about the spatial variation of the perturbation potential were made. a state is lost from a band. 3. One of thcse e f k t s is based on tlie configuration dependence of the Hartlee and exchange potentials. the localization of resonance and anti-resonance states differs from that of deep level states in the gap .ion of Levinson’s theorem. For each state occurring in the gap. even thosc calrulatcd by means of configuration dependent Hartrw and exchange potentials. namely. In regard to ‘configuration dependence’. Another results from the fact that Slater determinants.4 Correlation effects Correlation effects. These states emcrge when the short-range perturbation polential can bind or ‘anti-bind’ states at band energies. At certain energy values in the bands. This theorem.2 here. Thus. The deep states in the energy gap occur therefore at the expense of band states. the total number of states remains unchanged. . R stale is lost fiom a band.4. and there it was referred to as Levznson’s theorem. Deep levels 30 1 This relation signiEes that under the action of the perturbation potential. dBAp(E). we have proven what was anticipated earlier in section 3. will be discussed helow for deep centers. a state which existed without perturbation must cease to exist.159) In the above derivat. dEAp(h’:) - Lap. as discussed in section 2. an rffwt which is referred to as cor~fignralzon znteraetzon (see section 2.where we will calculate the electron population distribution over the energy levels in the gap and the bands in thermodynamic equilibrium. In Chapter 4.4 in lhe context of shallow levels. are not exact eigenstates of the N-electron Hamiltonian. The two correlation effects. Since the corresponding localized level is degenrrate with the band energy continuum. The exact eigenstates are linear coinbinations of different Sl&r determinants. this theorem means that for each new state of the crystal created by the point perturbation. the eigenfunctions do not decay exponentially but oscillate with an amplitude decaying to zero arcording to a power law. therefore.3. ‘configuration dependenre’ and ‘configuration interact ion’. are important for the N electron system of a crystal with oneparticle states localized at a deep centel. that for each shallow level in the gap.1. Here. This result already was used in section 3.with increasing distance from the center. the DOS of the perturbed crystal can display maxima or minima.5. also applies for purely long-range potenlials. (3.

is transferred to a oneparticle state of energy 0 corresponding to the vacuum level. but it is no longer true that I.160) of the ionization energy is also valid in this case.160) of I. n and n . of the one-particle Schrodinger equation of the crystal with a point perturbation. more generally. This expression has to he used with care. In this regard.541.. We will denote these oneparticle energies by E:) henceforth to emphasize this dependence explicitly. summing by all occupied oneparticle energies. The potentials depend on the number n of electrons occupying oneparticle states localized at the center. represents the ( negative oneparticle energy -E$. Apart from their sign. of the corresponding eigenststes Y . In this situation.l ) of the oneparticle Schrodinger equation with.1)electrons at the center. i.160) of the total energy R t o ~ ( { v ) ” ) the N-electron system in the ionized stair of {v}”.302 Chapter 3.e. respectively. -I. of the onepartick Schrijdinger equation have direct physical meaning. is the content of Koopman’s theorem. That this cannot hold is immediately clear if one recognizes that the eigenvalues IT?) and E P . and that of the unrelaxed . Electronic structure Configuration dependence of semiconductor crystals with perturbations For an ideal crystal. If one further considers that the total energies of both systems enter in the definition (3.1. which in the ground state of the system occupies a oneparticle state of energy E. the ionization energy Iv is definned as difference (3. they are the ionization energies I. followed by subtraction of the electrostatic interaction energy of the electrons because the latter is doublecounted in forming the sum of one-particle energies.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. Theionized state (v)” differs from the ground state (v)” in that a particle. which was explained in section 2. Of course. and the total energy E t o d ( { v } ’ ]in theground state {v}’. however. we say that the electrons at the center relax on the removal of an electron from the center. Like in section 2. The essential requirement for the validity of this theorem is the approximate population independence of the Hartree and exchange potentials or. = . The equation E .. The total energy of the ground state follows. and so do the energy eigenvalues E . that of the relaxed system with (n. E .2. for if taken literally i t misrepresents the charge neutrality of the system.1 one says that a31 electron is removed from the system. the energy eigenvalues E . according to section 2.. according to formula (2. of the effective one-particle potential. This requirement is not satisfied for a crystal with a point perturbation.. the definition (3.1 electrons at the center differ from each other .I . so that the remaining electrons are more strongly attracted..

one may examine an ' ~ excited state { v } ~with an electron in a formerly unoccupied one-particle state Y of energy below the vacuum level. but lies somewhere in is between the two.E ~ M ( { v } ' ) not equal to either one.E. v' (3. Such excitations are called internal transitions of the center. Generally. Secondly. ) but they cannot be used to calculate the total energy Etotal({v}v) of the ionized state with n .1/2) of electrons at the center.1 localized electrons at the center. Deep levels 303 system with n electrons at the center. one also needs the one-particle energies EP-') of the N-electron system with n . then forms the corresponding ground state densities.3. 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 . feels. Ionization. There are different types of such processes. In density functional theory. This is plausible because the electron. Firstly. all electrons may still be localized at the center. we are interested in excitation processes involving changes of the populations of one-particle states localized at the deep center.1 electrons. there is no way to explain why the ) energy difference E b t d ( { v } v ). the two total energies follow more directly: one determines the eigenfunctions of the Kohn-Sham equation for the centers with n and n . an electron .1) localized electrons there also half of the time. in its ground state. an electron originally localized at the center may undergo a transition to the bottom of the conduction band. during its removal. the one-particle energy eigenvalues E P ) are not sufficient.54).E Z ) of the unrelaxed system and not equal to the negative ( eigenvalue -EP-') of the relaxed system.these oneparticle energies provide the total energy E b ~ ( { v } ' of the ground state. in the final state. has n localized electrons. exciting an electron to the vacuum level. To carry out an exact calculation of the ionization energy of a center which.5. The corresponding excitation energy Iuiv is given by the total energy difference between the excited state { Y } ~ and the ground ' ~ state {}. and a hole in a formerly occupied ' one-particle state v. so to speak. and feels the potential with ( n . Applying equation (2.1 localized electrons. and evaluates the total energy functional (2.16 1) As in the case of ionization. i. To obtain the latter.E ~ M ( { V } 'should be equal to the negative eigenvalue . In reality.. is only one of the various possible one-particle excitation processes of the N-electron system of a crystal having a perturbation center. the ionization energy E b t a l ( { v } v ) . the potential with n localized electrons half of the time. the excitation energy Iulv is not equal to the one-particle energy difference E. Here. This is referred to as a donor transition Thirdly. but with one electron having changed its localized one-particle state.e.i .64) using these densities.

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

l ) / Q ) lie in the gap and.the charge state (Q 1) is realized.162)).e. simultaneously. Deep levels 305 edge instead of the valence band edge (as is done in equation (3. 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. 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)). the acceptor ionization level commonly lies highcr in thc gap then the donor ionization level. an acceptor.1))= Eg . the Hubbard energy U is positive. then there is also degeneracy between the Slater determinants formed .1)/Q) and X(Q/(Q the center is neither a donor nor an acceptor.l ) / Q ) . simultaneously.1)/Q) and the donor ionization energy X(Q/(Q 1))of an amphoteric center X(Q) is.162) setting A’(&/(& . when the ionization level X(Q/(Q 1))lies in the gap and.J. 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.3.the charge state Q is realized.5. + + + Configuration interaction If there is degeneracy among the various oneparticle states of an N-electron system. if X((Q . Of course. the Hubbard energy 1. 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. One then calls it amphoterzc. thus then it follows from (3.l ) / Q ) and X(Q/(Q 1)) are found in the gap. for this conclusion to be valid. if E F lies just below X(Q/(Q l ) ) . - + if neither of the two levels X((Q .1)/Q) does not. + (b) a pure acceptor. the center is both a donor and an acceptor. X(Q/(Q 1))does not. by definition. both levels have to be located in the gap. + 1))lies in the gap The difference between the acceptor ionization energy X ( ( Q . coninionly.l ) / Q ) . + (c) if both levels X((Q . both a donor and an acceptor or none of them. One has (a) a pure donor. between the two levels X(Q/(Q 1)) and X((Q .A(Q/(& . One therefore has + Since.l)). the ionization level X((Q . i.

at least within the framework of the one-particle approximation. 12) of the 7'2-state. however. we disregard them in our further discussion.2 electrons are in extended valence band states. If spin and exchange interaction are considered.306 Chapter 3. To analyze the consequences of configuration interaction. we concentrate on those degenerate one-particle states which are localized at the deep center. altogether. Within each group there is degeneracy. for a system with two electrons. Here. the Slater determinants for the two electrons of the deep center are products of coordinatedependent and spin-dependent wavefunctions. 3' = 9.5. . or the spin-dependent wavefunction is symmetric and the coordinate-dependent wavefunction antisymmetric. namely and 3 antisymmetric two-particle wavefunctions. we use a simple model: a deep center with 3 degenerate localized one-particle states of symmetry Tz. The extended electrons contribute to configuration interaction only little.2 .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. occupied by 2 of the N valence electrons of the crystal. Using the three wavefunctions Iz). The existence of such degenerate states was demonstrated in subsection 3. this degeneracy is removed. the symmetric and antisymmetric wavefunctions have slightly different energies because the exchange energy depends on total spin S . Since a Slater determinant itself is antisymmetric with the respect to the exchange of two electrons. the first case applies if the total spin S is 0. as one should expect. which differs for the two groups of states. one can combine 6 symmetric two-particle wavefunctions. namely These are. Neglecting spin-orbit interaction. the remaining N . ly). strictly speaking. If the configuration interaction is taken into account. 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. Electronic structure of semiconductor crystals with perturbations from one-particle states of this type. The result of this removil can be derived by means of group theory. beside a non-degenerate state belonging to the irreducible representation A l . and the second case if S = 1 (other values of the total spin are not allowed). From quantum mechanics it is known that.

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

the case of deep acceptor levels may be treated analogously). we first present a short overview of the experimental methods. optical and electrical methods are available. To investigate the excitation properties of deep centers. methods which give experimental data on center properties in thermally or optically excited states. The chemical identity of the centers can be determined (in addition to other methods) by means of mass spectroscopy or of Rutherford Backscattering (RBS). These methods provide data concerning the total spin S of the centers and. Ionization energies can be determined by means of optical absorption spectroscopy and photoconductivity measurements. The decay time of the current and the rise time of the associated capacitance change are determined by the emission probability from . an increasing capacitance of the junction. mainly in the infrared spectral region. Electronic structure of semiconductor crystak with perturbations 3.5. thus. also spatial symmetries. 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.308 Chapter 3. Experimental methods One can divide the experimental methods for investigation of deep centers into two groups. it adjusts exponentially through emission of electrons from the deep levels into the conduction band (we assume deep donor levels here.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. 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. and on the other hand. This state does not occur suddenly. 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. methods which measure ground state properties of the centers. This results in an exponentially decaying current. Among the methods of the first kind are measurements of magnetic properties. in every. In the conduction band. Since we have thus far treated only theoretical methods. which for its part leads to an increasing positive charging and. case the product of combined experimental and theoretical investigations. if anisotropy effects are measured. Knowledge about these centers is. like Electron-Paramagnetic Resonance (EPR). however. By suddenly applying a reverse bias at such a junction. on the one hand. the electrons are freely mobile carriers and are immediately sucked up by the positive electrode at the nregion.

I. Thus. Other many-body effects. More rigorous calculations within one-particle approximation (3araff. calculated positions of these levels are shown. t’(O/+). and a description of the vacancy in terms of one-particle states. can be used to determine the ionization energies of the deep centers. In Figure 3. wherein a reverse biased pnjunction is exposed to periodically repeted voltage pulses of forward {deep level filling) polarity. no electrons are available .3 e V for U . it is fully occupied having two electrons. albeit configuration dependent ones. Pantelides.4t maximum. smaller than optically measured values: the lattice has time to rrlax if ionization proceeds thermally. These are not yet final positions because lattice relaxation has not yet been considered. many-body effects. The recovery time for the capacitance change after a filling pulse has been switched off. It predicts the existence of two bound one-particle states. is measured as a fimrtion of temperature.’(-). and a tripiy degenerate t2-state. I. a non-degenerate al-state. Ir(3-) and V(4-). 1980. Of particular importatice is the so-called Deep Level Trawaerat Spectroscopy (DLTS).13). Thus there exist 7 charge states of the vacancy. The defwt molerule model Owing to the value of about 0. and this lowers thc enerm of the finel stat?. Ionization energy values from LILTS measurements and other thermal quililrrium technique are. more strictly speaking. under certain conditions. . the donor levels 5’(+/2+). hence lattice relaxation is is not possible. as a rule.5. namely t7(2+). Bernholc. so we initiate our discussion of particular deep centers with it. is approximately justified. Measuring the capacitance rise time yields experimental values for the emission probability. configuration dependencies of one-particle energies: should be important in the case of the Si-vacancy. Vacaricy in Si of the vscancy was treated in section 3. 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 3.3. A simple estimate yields 0. i’(O). Optical ionization occurs instantaneously. it may be expected that three or four ionization levels codd fit in the Si gap of about 1. As such.12a). This fiinction exhibits maxima which. In charge state V(Z+).2. including configuration mixing. V(2-). The t 2 -level can lie in the gap depending on how many electrons it hosts.1e V . this can be 6./ 0 ) and V ( 2 /-1 are found there (as above the acceptor levels are counted relative to the conduction band edge). A4ctualIy. The one-particle energies of these centers differ by the Hubbard energy U. The latter leads to changes which are discussed below (see Figure 3.12 (part b). are small.3 el’ for C3. and at minimum 0. and the acceptor levels V ( . Perhaps the best understood point perturbation is the vacancy in Si. I?wp let& 309 the dttep centers.’(+). Schliiter.

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

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

Si:Hg. On the right-hand side. Different charge states of the vacancy are shown. also a long-range Coulomb part. For isocoric impurity atoms. as a rule. These are the levels principally involved if main group elements are used as doping atoms for . ) relatively different systems as. this potential leads to shallow donor or acceptor levels. i.13: Defect molecule model of a vacancy in Si. besides the short-range part.312 Chapter 3. The perturbation polrntial of a main group impurity atom in a tetrahedral semiconductor contains.4. atoms whose cores do not deviate too strongly from that of the host atom. l U U 4 . the basis functions of the irreducible representations of the deep k v e l ~are indicated (a. the Coulomb potential is in general the main contribution. Electronic structure of semiconductor crystals with perturbations cl v’ D2d - Dzd d) v-o+d -btc Figurr 3. As shown in section 3. c Bnd d bband for the dangling hybrids of the 4 surrounding atom). (After Watktns. taking into account the torresponding Jtthn-Teller distortions. for inst ance. b.e.

which forms an alloy). Isovalent substitutional impurity atoms therefore lead either to deep levels (this occurs if the isovalent host and impurity atoms are chemically dissimilar.20 Hg Ec .) is shown for comparison. . Ga. as in the case of GaP:P. the short-range potential dominates in general. gives rise to deep levels in the gap (see Table 3. Al.31 1 + 0.3. .6: Experimental deep l e d positions of neutral main group substitutional impurity atoms in Si (in eV). If an impurity atom belongs to the same column of the periodic table as the host atom.14 P - 0 S Ec .5. meaning either that no localized state exists at all (C. 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. An empty space means that the correspondingimpurity atom is either not incorporated substitutionally.3 Te Cd E. however. Ge. For non-isocoric elements of the main groups. P.32 + Ga - Ge - As - E.) ?r Be B - C - hk Zn A1 E C Vac. Pb). in particular cases. The impurity problem mentioned was treated above within the defect molecule modeL Although group-IV elemental semiconductors were assumed as host crystals. Sn - Sb - + 0. the Coulomb potential vanishes completely and the short-range potential remains as the only potential contribution. Deep ler7ek 313 Table 3. Sb.6). Bi). or that such states exist but are shallow (B.0.55 Ec . In this case. and. 0. "Dash" indicates that no deep level occurs in the gap €or this particular substitutional impurity. [Data compiled from Landoldt-Barnstein. the general results obtained there also apply to compound semiconductors.43 N Ec .0. In E.15 E. As.0. or ZnTe:O).25 T1 Pb ~ Bi - Po tetrahedral semiconductors. or that there i no unambiguous experimental s data.0. one says that the two atoms are isovcalent. Sn. . t 0.31 Se E1. 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. The neutral vacancy (Vac. 1982.0.0.

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). and which are not. Using this observation. i. The data from both sources agree that no deep levels exist in the case of the isovalent group-IV atoms C. cannot be decided by means of the defect molecule model. P. Among the group-V substitutional impurity atoms N. and the deep level in the gap is expected to be tz-like rather than al-like. ER The above conclusions are essentially confirmed by the more accurate Green’s function tight binding calculations performed by Hjalmarson. Wolford.e. concerning allevels. for impurity atoms with lower group numbers than the host atom. a1 and t 2 symmetry.E: takes increasingly negative values starting from zero.E: has negative values (or is attracting) if the hybrid energy of the impurity atom is lower than that of the substituted host atom. and Se. the deep level in the gap should be the bonding ta-level. Pb.3 14 Chapter 3. Figure 3. if the group number of the impurity atom is higher than that of the host atom. Such levels are not well described in the TB calculations quoted above. and Dow (1980).6. the deep level should be the anti-bonding u1-leve1. Vogl. and for positive (repelling) perturbation potentials. Sb. Figure 3. the perturbation potential V’= . one can guess its symmetry as folIows: The perturbation potential V’ = e t . If. V ’ has positive values (or is repelling) if the hybrid energy of the impurity atom is larger than that of the host atom.e. like Ga or Zn. i. of these symmetries (see Figure 3. they are plotted against the s-orbital energy of the impurity atoms in Figure 3. Bi. For impurity elements left of column IV of the periodic table. For the particular case of Si this can be seen by means of comparison of Figure 3. by varying the impurity atom. are depicted in Figure 3. a substitutional sp3-bonding impurity atom in a sp3-bonding L host crystal will introduce two bonding levels E ? and E t T of. the indications of Figure 3. Furthermore.14. a look at. Concerning the question of whether or not a main group impurity atom gives rise to a deep level.14.14 agree surprisingly well with experiment. then a deep level in the gap will evolve from the conduction band below a certain negative threshold value.14 with Table 3. then one expects a deep level to arise from the valence band above a certain positive threshold value. . S.10 indicates that for negative (attracting) perturbation potentials. Some results of these authors. respectively.14 indicates deep levels for substitutional 0. Sn. Electronic structure of semiconductor crystah with perturbations Accordingly. while experimentally one also finds a deep level for substitutional Te. Ge. In the case of group-\’I atoms. which summarizes experimental results for this host crystal. Which of these levels are located in the gap.10). ils. On the assumption that there is a deep level in the gap. and two anti-bonding levels E:T and E ’ : . the perturbation potential is positive. If the perturbation potential V ‘ takes increasingly positive values starting from zero. Since the a1-levels arise mainly from atomic s-orbitals.

5.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. (After Hjalmarson.3. the corresponding wavefunct ions have larger amplitudes at the surrounding host atoms than at the impurity atom. 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. and lattice relaxation has not been taken into account (Scherz and Scheffler. Quantitatively. To get an idea how these effects would modify the results. particularly. Wolford. have been neglected. 1993). we show in Figure 3. using the level ordering suggested by the above-quoted calculations . the al-level positions in Figure 3.14: Deep levels for main group substitutional impurity atoms of various tetrahedral semiconductors. many-body effects. 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 .14 differ from the experimental ones. see the main text. This is to be expected because of the great simplifications made in the calculations.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. Vogl. For further discussion. configuration dependencies of the one-electron levels. and Dow.

8 are hosted by the four bonding states and the remaining electron occupies the anti-bonding al-state in the gap. respectively. and 3 holes. As in the vacancy case. and the defect molecule model.15: Energy levels and their populations for sp3-bonding main group impurity atoms in elemental semiconductors of group IV. The defect molecules of group-111. 7. d . 4.I. 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. e .HI. c . The partial illustrations a) to h) correspond to impurity a t o m of groups I to VII as follows: a . 2. a Jab-Teller distortion will occur which lowers the total energy. 1. f . Of them 2 electrons are hosted by the bonding al-level in the valence band. and in the 3t:groty-VI atom molecule with 11 electrons.V.VII. b . Qualitative . 5. 2 occupy the al-level.11. -11 and -I atoms have. One may also say that this level hosts. In a 5’t:groupVI atom molecule with 10 electrons. respectively. There are. 6 and 5 electrons.\’I.316 Chapter 3. This state of the molecule will certainly not be stable. Of the 9 electrons of a Sirgroup-1’ atom molecule (remember that only N results in a deep level in this case).within the defect molecule model. Again. and 3 electrons to be placed in the bonding tz-state which forms the deep le\Tel in this case. respectively. Electronic structure of semiconductor crystals with perturbations d) el fI Figure 3. in addition 1 electron has to be placed into the anti-bonding tl-level.

Thus. of equations (2.5.and f-shells (Au). Siiicc none of the matrix elements of (3.166) arises because the Wannier function is equally spread out over the two atomic sites of a unit cell.. v u s ( 6 th . taking the difference . one has t h e same matrix elements for all R and R’ with the exception of R R’= 0.304). 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. To calculate them we use the results of the TR approximation of scction 2. Fiist..165) and (3.. The latter elements are (btOlH i V’lbtO) - S(E..166) where EL is the hybrid energy of the impurity atom.167) The factor in (3. t = 1 . in an approximate sense.158) and (3. 2 .v o . We will discuss this problem in more detail in the context of the transition metal impuiity atoms. For the perturbed Hamiltonian EZ fV’. h (3.3. 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. The Chen’s function in Wannier representation has already been determined above (see equations (3. 4 . Foi these atoms.. . we write down the matrix representation of the unperturbed .V.152). follows SS vlf... an expression for (vO1V’(wo) G V.of the perturbation potential V ‘ in this representation. employing the Wannier representalion of the Green’s function derived above. the bonding and antibonding orbitals IbtR) and latR) are the Wannier functions of the eigenvalue equation (3. For the evaluation of the Koster-Slatcr equation (3. 1 + EL). It is given ’by (btRIHI4R’) fhGRR‘. Ag) or d. Then. and V. is the hybrid energy of a host atom... In the simplest veision of this upproximation. d-electrons participate in chemical bonding with the host crystal.159)).Eh).166) and (3. ran he treated arralytzrally. agdin taking Si as the host crystal. Hamiltonian H between bonding orbitals. 3 . 1 h (3. one may identify IbtO) with the Wannier function of the uppermost valence band.303) and (2. We will use thmn to grt explicit expressions for V.5.166) depend on t . of equations (3. we will discuss it hclow.. As lhis calculation provides further physical insight into the formation of deep levels. The question of whether deep levels exist or not for a particular substi tutional impurity atom..165) where E. V.. the ILamiltonian of the ideal crystal is diagonalized by the bonding and anti-bonding Bloch functions Ibtk) and In&). V .152) we need the matrix elemeuts V. while the substitution of a n atom occurs at only one site.165).and matrix . Analogoiisly. (3.

the two band widths AE./2.152) located in the gap. If one assumes. the imaginary parts of G:(E'} and G. fi] (3. v .169) takes the form (3.318 Chapter 3. For Vi -t +m. the solution of equation (3. For such energies. For negative Vo.169) within the gap do not exist for all possible values of the 4 parameters entering.[. that A & = AEw. This is evident if one considers the particular case AE. and the perturbation potential constant Vo.152) transforms into Solutions of equation (3.e. the deep level is pinned at the midgap position. and the logarithms themselves become negligibly small.171) to exist at all./2. It turns out that all elements are the same./=.171) may be written in the closed form . and Et < E. El approaches the value E.v >> Eg.Considering equation 13.170) is valid only there. Electronic structure of semiconductor crystals with perturbations elements between bonding and anti-bonding orbitals yield the expression for (wO1V'lcO) V. In order for a solution Et of equation (3. = LG. . in addition. for positive Vo. the gap energy Eg. A&. and by identifying Et with the highest possible value of Et namely E. with 0 < Et < EQ.e.!(E) are zero: and equation (3.171) by identifying Et with the lowest possible deep level position in the gap namely Et = 0 in the case of positive Vo.170) With this exprwsion! the deep level condition (3. The arguments of the logarithmic functions in G : ( E ) and G:(E) are close to 1 in thia case. one necessarily has Ef > Eg/2. in the case of negative VO.5. which can be realized..e.2. . i.then Re[G:(E) G:fE)] - + (F)-& ..168) We seek deep level solutions Et of the Koster-Slater equation (3. lV01 must exceed a minimum value J V O ) ~ ~ ~ given by (3.. i.172) This minimum value of (Vo(follows from equation (3... This corresponds to the pinning of & to the vacancy level discussed in subsection 3. within which Et has to be restricted anyway because the deep level condition (3. = v = v.171) It has solutions Et only in the energy gap 0 < Et < E.1721.e. i. (3. i.

71 c l -3.3 eV is a reasonable choice. and should not exist for IVoi < 1.3.) B e B 1.18 Zn 1.14 TI 1.$) (in eV) for substitutional impurity atoms of main groups in Si.05 Ga 0.7.99 -1. (After Herman and Skillman.35 Pb 0.47 N 0 -3. the absolute value of the potential and the energy gap must be relatively large. The perturbation potentials V-0 for impurity atoms of the main groups II to VI of the periodic table.24 -0. and AE.04 -4. The bandwidth must be sufficiently small because it corresponds to the average kinetic energy.97 -2. Deep levels 319 Table 3. Comparison with experimental results €or deep levels of substitutional impurity atoms in Si shown in Table 3.96 -1.41 Vac 8.87 0.7: Perturbation potential matrix elements Vo = (1/2)(~: . = 3. With these values. a deep level should exist for lV0l > 1.08 A1 1. calculated by means of equation (3. That lVol needs to be large enough is obvious. which militates against binding. so it should not be too small. and the bandwidth relatively small.172) for a deep level to be formed.98 Sb Te I -0. = A E .22 -2.17 C -1. In this case one has Eg = 1.42 -1. as the following numerical example for impurity atoms in Si demonstrates. calculated by means of HermanSkillman s.91 Hg 1.88 In 1.04 Sn 0.28 Ge -0.03 Bi Po At -0. IVolmiplis 1. The latter are partially reproduced in Table 2.68 According to condition (3.5.6 reveals that .167).12 -2. 1963. According to our model.57 Mg 2.82 Cd 1. are listed in Table 3.8 P s -1. The gap is the energy range where the deep level has t o be placed.1 eV.21 e V .21 eV.56 As Se Br -0.31 F -6. 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.21 eV.and p-orbital energies.2.

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

Figure 3.1 with E symmetry and t h r w states It%) with Tz-symetry. A simple oneparticle model which is supported by ab initio calculations. Considering the tetrahedral sgmme try of the impurity center. The two 01-orbitals interact with each othrr tand give rise to a bonding state dwp in the valenct. 'rhe corresponding interaction matrix elements are of the type j r and bym {see section 2. is a defect molecule with the 3d-TM atom on a substitutional cation site at its center (see Figure 3. respectively.16 contains data related to this.174) where . as in the case of the Iacancy. In this model. the TM atom is represented by the five 3d-orbitals and the one 4s-orbital of its valence shell. one triply degrnertlte bonding level Eb nnd one triply degenerate anti-bonding level Ea arise. the donor and acceptor ionization levels of substitutional 3d-TM impurity atoms are now well understood. The two triply drgeiicratc 12 states Itah) and 1t2d) do interact mutually. ionization levels of several charge states may be found in the e n e r a gap.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. For these two levels. and hhe five d-states decompose into two states ). 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. Deep levels 32 1 ' concentrate on the donor and acceptor transitions. We will return to this point later.6). their energy levels are likely to be found either in the gap or in the valence band. band and an antibonding state deep in the conduction band. as well as showing the ionization energies of the free 3d-TM ions. Denoting the Vpp. The latter are larger than the ionization energies of the 3d-Thl atoms hosted by semiconductor crystals by more than one order of magnitude. The case of free atoms is also striking in regard to the large Iyariations of ionization energies between different ionization states.-type matrix elemen1 by V h d .17). The energies of these orbitals will be denoted by Ed. The two estates remain without bonding.5. the same formulas apply 8s those which wmt' derived in section 2. Neglecting bbP-type matrix elements. eS and eh. Theoretically. 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.3.6 for interacting hybrids at nearest neighbor atoms of an ideal crystal. In semiconductor crystals these variations are almost two orders of magnitude smaller so that. we hwe (3. The s-orbits1 of tlir TM atom is deformed by the crystal into an orbital of A1-symmetry.

177) . Electronic structure of semiconductor crystah with perturbations Figure 3.322 Chapter 3.16: Experimental ionizatjon energjes of free 3dTzvl ions (lower part).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. (After Zernger.( l + . respectively. energy Eb and E. 1986. are where we set a = -(I2 1 s a)' - 1 a 2 = .4 The corresponding thecomponent wavefunctions It2b) and Itza) of. ) 2 A (3. as well as donor and acceptor ionization energiea of 3d-TM impurity atoms and ions in various host semiconductors (upper five parts).s..

therefore. Explanations are given in the text. Considering localization of the t a b and tn.18 the calculated oneparticle energy levels are shown for some 3d-TM atoms in Gap. meaning that the bonding tzb-level is mainly formed from the d-ststes of the TM atom.175) are linear combinations of basis functions with tz-symmetry.5. Lindfeldt. Exactly this picture emerges from the above-mentioned Green’s function ab initio calculations (Zunger. Deep levels 323 c -band t2a \ t2 4s 3d v . 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. arises to a considerable extent from the tz-components of the four sp3-hybrid orbitalb of the surrounding host crystal atoms.band Figure 3.8 holds. In regard to deep levels of the 3d-TM atom i s in the energy gap. It turns out that the bonding tzb-level lies in the valence band. If Ed lies deeper than Ch. while the anti-bonding tza-level.3.17).-level are candidates (see Figure 3. which forms the deep level. The eigenfunctions of the e-level are linear combinations of the &orbitals of the TM atom and are therefore strongly localized at the latter.-leveh. Since the two bonding and anti-bonding eigenvectors Itzb) and Itza) of equation (3. then a! > .17: Energy level diagram of the defect molecule model for a substitutional 3d-TM impurity atom in a tetrahedral semiconductor. 1983). the non-bonding elevel in the valence band or the gay. In Figure 3. and the anti-bonding tk-level is in the gap above the e-level or in the conduction band. they also have t2-symmetry (as already indicated by the notation). the 2-fold degenerate e-level and the abovelying triply degenerate anti-bonding tp. These levels . the position of the two orbital energies F d and t h relative to each other is decisive.

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

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.4 using the analogy with frcc I'M atoms). In Figure 3. 1984. this approach must be refined by including many-body effects. 1985). Experimentally one finds that these diffeiences are almost independent of the atom considered.20 this fact is shown for acceptor .5. 2984) Ligand field theory accounts for the fine structure of the deep impurity levels.o 0.3. it becomes important for T M impurity atoms with their strongly localized open d-shells (as was specultited in section 3. particularly not for the internal transitions of the 3d-TM centers. Zunger. configuration interaction. the excitation energies it yields are not correct quantitatively.0 z w 1.0 I 2 55 LT W 2. While the latter effect does not play an important role for main group impurity atoms. Figure 3. in particular.5.19 demonstrates this in thc case of TM atoms in ZnS. Heinrich. and Zungcr. as we have scen above. Deep levels 325 3.19: Calculated inultiplet structure for substitutional 3d impurity atoms in ZnS. Langer. which is not explainrd by the approach taken above. Caldas. The differences between the donor or acceptor ioniaation energies of a particular TM atom in different host crystals exhibit interesting behavior.0 Figure 3. To be quantitatively correct. [After Faatio. Although this approach provides qualitative understanding of deep 3d-TM centers in tetrahedral semiconductors. Fazzio.

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

18 1) i ( ~ a 1 6 + 6 ) + s1( n u. the self-consistent value of h and.178).180).n d w 0. According to this relation. 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. Since t h is the only quantity which changes substantially in the series of the 111-V and 11-VI-cornpound semiconductors. for the two levels which are candidatev fol deep levels in the gap .6)-A . and n h = n b P 2 +. For the level difference 6 = ( € d . The crucial point at this juncture is that [ I d . and values a 2 . results in an increase of € d and.181). also .(nu 1 6 + 6 ) . i.177). respectively. As a consequence of this.5. because of strong localization of the &electrons and wcak scrcening of their interaction.B and n h are small. is indepmrlent of Ch. their clihtance from c h is independent of Eh.180) are in h-states. an increase of 6. The bonding T2-level Eb lies in the valence band. Therefore. Self-consistency is then achieved if the two equations (3.-level this follows from equation (3.e.also.-(nu .3. the factor multiplying U d in equation (3. the separation between Ed and Eh is the same in different semiconductors.182) which uniquely determines 6. it cannot vanish completely because adjustrrierii of the levels requiies a bit of rhargc to bc transferred). This adjustment is called the 'neutrality level'. We thus arrive at the conclusion that the deep levels of 'I'M atoms in .n:)] 2 (3.and h-states adjusts self-consistently: if Eh increases.178) for the level positions t d and Eh are satisfied with values n d and n h from equations (3. then 6 becomes small and.181) must practically vanish itself in order to satisfy this equation. also the energy separation tId-€h = 26 between the d. Deep levels 327 are in d-states.€ h ) / 2 between the d. n d increases which.174). its three states are therefore completely occupied and it holds n b = 6.. thus.a2 (3. hence. According to equation (3. P2 from (3.6 ) A - 1 ne .and < h level. according to (3. 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. The difference 6 = (Ed . with this.~ h ) / this condition 2 yields +uh where 260 = denotes the level distance without charge transfer. 0 (3. leading to the approximate rclation (E! " ci) . For the ta. has very large values (on the order of magnitude 10 e V ) .179) and (3. This also holds for the anti-bonding tza-level dnd for thc non-bonding e-level.

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. 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. with this. Ag and Au belong to the fast main group of the periodic table. 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. Their incorporation in the host crystal is predominantly substitutional. Electronic structure of semiconductor crystals wilh perturbations the gap are ‘pinned’ at the hybrid level F ? ~ the surrounding host anions. if an additional electron is put in the deep tzo-lwel. Their high solubility in Si is remarkable (in the region of cmd3 to ~ r n . as is their fast diffusion.~ at melting temperature). their behavior its impurity atoms in tetrahedral semicunductors resembles that of transition metals. they associate the with the difference between the average hymagnitude of the displa~ements brid energies of the two semiconductors.and p-shells of the host atoms are substantially smaller than those of the &orbitals of the Thl atoms. also part ofit IS added to the TM atom. in to that the deep levels of TM atom8 depend only relatively weakly on their population. as will be discussed iu more delail i section 3.177)).328 Chapter 3. Thls quantity has a close relation to the valence band discontinuity at a semiconductor heterostnicture. Ag. Anderson.and f-shells . Ag) or d . Although the elements Cu. In fact. the anion-hybrid energy Eh has to be replaced by the average cation-anion hybrid energy of the crystal. Au with 0. Au in Si These three elements (abbreviated below as ‘Nhl‘. Since the Hubbard energies of the s. This means that electron charge density will flow from the Thl atom to the surrounding host atoms. for example. the deep TM-levels are shifted up only by several tenths of an e V rather than 10 el. and. for the case of the free TM-ion if one more electron is p l a ~ e d the center (Haldan. but not the outer p-shell. for noble metal) play an important part in silicon device technology. As impurity atoms. of If the coupling hetwccn the anion-hybrids and the rest-of-crystal is taken into account. Fe or 3d-TM’s. they constitute effective capture centers for non-equilibrium charge carriers. 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. and that the closed d-sheIl (Cu. T i makes it somewhat difficult to identity the pure substitutional NM centers. This is understandable if one considers that for these elements only the outer s-shell. at Cu. 1976). so that levels of several charge states can fit in the gap. is occupied. The elements tend to form hs complexes with other elements. Moreover.

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

! I I Ce Pr Nd Rn Sm Eu Gd T Dy Ho Er Tm Yb b Figure 3.21: Donor ionization levels of substitutional rare earth impurity atoms in different semiconductors. In this model. (After Delerue and Lannoo.) 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.and 6s-orbitals of the RE atom nor do they couple with the orbitals of the surrounding host atoms. 6 4 2 5 0 v P--2 g 4 -6 -8 k E(3+/4+) I -10 -12 1 I .and three t2-orbitals. The host crystal is described by the four sp3-hybrid orbitals at the four neighboring atoms pointing towards the RE atom. The 4forbitals. and the 6s-orbital becomes a al-orbital under the influence of the tetrahedrally symmetric crystal field. I ! I I I / I I . . The RE atom is represented by its 5d. 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. 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 " . the 4f-orbitals neither interact with the 5d. 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. are involved in forming deep states because electrons are transferred to or from them. 1991). respectively. 1994. The differences between 3d-TM and RE impurities are essentially of a quantitative nature.and 6s-orbitals only. 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. while the host and RE derived t2-states couple to each other forming bonding and anti-bonding tz-states.330 Chapter 3. nevertheless. Because of this. The four sp3-hybrid orbitals at the neighboring atoms pointing toward the RE atom split into one a l . The e-states remain without bonding to the host crystal.

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

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

However. respectively.Al)As mixed crystals (Lang.itiitionally on cation and anion sitcs.he total energy of thc interstif. In contrast to the lat.ial s h t e because it remains largely unoccupied. among them at t. Now.hat the D X center j u s t represents another state ol 1he shallow donor. In the singly negatively charged state which the donor takes under high doping. If the special Conditions mentioned above are not fuliilled. A s atoms. The microscopic nature of these centers was a puzzle for a long time. namely the energetically costly populalion of the anti-bonding A1-level at the shallow donor. Originally this transition was attributed to the formation of a defect complex involving the donor atom (a)and ti11 iinknown point. but singly negatively charged. and its installation does not occur at a substitutional site but at an interstitial site. does not increase t. thc rclalive total energy minimum of the DX-state lies only slightly (about 0. The reason for this energy balance is the sainc as in the E L 2 case. the DX-state is metastbble. ailtisite defect is also observed at ot. Deep levels 333 Direction Figure 3..hc fourth remotc lying As atom.he so-called L)X-cent.3. 1992. lTndcr certain conditions hydrostatic pressure or strong Ti-type doping in the case of GaAs. (and ev- . and AlAs mole fractions larger than 22% in the case of (Al.t. as for the EL2-center. 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.hcr point perturbations.) interstitial As atom and Ohe three adjacent. st.2 e V ) above thc absolute minimum of the shallow donor state. 1977). t.er. perturballon (X).hen the shallow donor represents a stable state of the impurity atom.the donor atom of a DX-ccntcr is not neutral. the two remaining electrons are hosted by the dangling bond of t. and form shallow donors. which lics rclatively high enmgetically.ers in GaAs and (Ga. (After Dabrowski and SchrJ’ler. The non-bonding p-orbital of the A s atom. it is clear t. Logan.rong sy2-bonds can be formed similar to the bonds in the graphite structure of carbon and that of g a y As.5.22: Geometry of the stable and metastable state of the As-antisitc defect in GaAs. Ga)As deep levels emerge from these shallow donors. DX-centers A metastability similar to that of the C:aAs:AsG.

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

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

studies of clean surfaces are also of practical importance. Although most surfaces used in practice are not clean but imperfect. 3.6. The basic principles will be treated in subsection 3.3 for electronic structure. . A particular geometrical plane can also be characterized by its normal direction. Electronic structure of semiconductor crystals wilh perturbations of the crystal can be made in this way. In this way. Particular suxfuces are discussed in subsection 3. 1 are the integer reciprocal axis intervals given by the intersections of the lattice planes with the three crystallographic axes.4.6. important themselves. the complexities are introduced step by step and examined for changes. we will deal with the atomic and electronic structure of clean semiconductor surfaces. In the case of trigonal and hexagonal lattices. it is convenient to write the normal direction as a linear combination of the primitive vectors bl. which we will now describe. dcnotes lattice planes perpendicular to the cubic x-axis. One first has to reduce the level of COEApleXity by considering clean surfaces for investigation. with integer coefficients + + h l . This is due to the fact that imperfect surfaces are such complex subjects that it is very difficult to approach them directly. since i h k = 0. To define lattice planes in this manner. k . Ik2. The lattice planes then are characterized by four indices ( h k i l ) instead of three. The (hkil) are sometimes termed Bravais ~ T L ~ ~ C C R . (iii) Epitaxial growth of crystal layers by means of molecular beam epitaxy (MUE. four crystallographic axes are considered (three instead of two perpendicular to the c-axis). howevei. Lattice planes of 3D crystals Such planes are usually denoted by Miller indices ( h k l ) where h.2 for atomic structure and in subsection 3. and (110) denotes lattice planes perpendicular to the face diagonal in the first quadrant of the ry-planc of the cubic unit cell.4 taking Si and GaAs as examples. Later. The symbol (loo).b2. (111)means lattice plunes perpendicular to the space diagonal in the first octant of the cubic unit cell. of course). jL3. b3 of the reciprocal lattice introduced in scction 2. The first three. In this section. however.6. real imperfect surfaces may also be undeistood. It was already pointed out that these are the surfaces upon which epitaxial crystal growth proceeds in MUE. Clean surfaces are. see section 3.2 Atomic structure of clean surfaces A geometrical construction which is of special significance in describing crystal surfaces is that of lattice planes.7). are not independent of each other.336 Chapter 3. for example.6.

181) by arbitrary integers 1. Whereas the Miller indices definr an infinite family of parallel lattice planes. the roefkients ( h l h ~ h 3 ) are only determined up to a common integer factor. they have different directions. namely that member of the infinite family which contains the zero point. and the coefficienls ( h l h ~ h 3differ from the corrirnon Miller indices. apart from a co~linion factor. h 3 are the Miller indices of the lattice plane under consideration.186) The points of the lattice plane defined by equation (3. a 3 as coordinate axes rather than to the crystallographic axes.3. r e ferring to the primitive lattice vectors al.122). ) one can rasily switrh from one representation to the other.182) Hrre. If the normal direction n is given. h 2 . Then the coeffirients hi. f2 may be expressed in terms of the primitive lattice . Clean semiconductor surfaces 337 n .6. the lattice points Ro = rloa1-k r20az + '7'30ag (3.184) yields only a single plane. 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. We chose this factor such that h l .a 2 . however.183) of the lattice plane perpendicular to n which contains the zero point. n form a right hand coordinate system. This i s done in such a way that the three vectors f1.10 + h2r20 + h3r30 = 0. Tf necessary. The latter are parallel to the piimitive lattice vectors only in the case of primitive Bravais lattices. One can show that all lattice planes Ri = w a l + v z a 2 +w a ~ (3.185) of the infinite family of parallel plancs are obtained by replacing the right hand side of quation (3. may be defined by the equation n & E h17. like the face rentrred cubic one.h l b l + h2bz +h ~ b 3 .r2O1r3o are allomwl. (3. (3. For centered laltires. reciprocal lattice vectors are understood without the factor 27~ defin inition (2. The ( h l h 2 h 3 ) are.184) form a 2D lattice. hs have no common divisor. In mathematics it is called a Dzophantin equation.h2.184) The unique character of this equation lies in the fact that only integer solutions r10. equation (3. The primitive vectors of this lattice will be denoted by fi and f2. The f1. f2. (3. Using the above characterization of lattice planes by their normal direction n.

We call f 3 the stacking vector because it determines how the lattice planes arc stacked in the crystal. a z .fid were obtained above. Rocksalt. Electronic structure of semiconductor cryst& with perturbations Table 3. n I Crpst'alStructures I1 Diamond. which ran be done by Incans of the Euclidean algorithm (set. The piirriitive vectors fi. (3.184) has to he s o l v d . f2. BS the vectors Fi.338 Chapter 3.8) for several Iow index lattice planes of the 5 common scrniconductor crystal structures. This implies that the structure of a crystal ~ . (3.187) The lattice planes R defined by equations (3.by means of the Euclidean algorithm.3 is a vcctor complementing F1 and f 2 to form a s ~ of primitive lattice t vrctors Fi. the Diophantin equation (3. 1 WurtBite. and any vector fi which differs from f 3 hy a vector aithiii the latticr plan? can also be used. f2 and ailitrary integers ~ 1 ~ 5 the lattice plane given by relations (3. of course. IJsing thc lattice vectors fi. The vector €3 can br detcrinined from thr Diophantin equation (3. Zincblende.183) and 2.186) for 1 1 in just the same way. In order to determine the coefficients of this representation. q of the crystal under consideration.186) can be written r in the form where f. 1988j. ~ . F3 of the 313 bulk lattice of the crystal. Selenium vectors a l . Bechstrdt and Enderlein. i . The choice of $3 is not uniquc.184) can bc represented as R = Slfi o + sgh. 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.185 and (3.

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

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

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

respectively. The highest value of n may be readily obtained from the derivation of the possible rotation symmetry axes of 3D crystals in Chapter 1. namely the 'body' centered . 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. f 2 are the primitive lattice vectors of the 2D lattice of the ideal surface. There are thus 4 different plane crystal systems . and 6. The point group of such a lattice is therefore C4v (4mm). Thus. or that of a rectangle. the three vectors f1. nmm). Only one new lattice is obtained in this way. the quadratic with holohedral point group 4mm and the hexagonal with holohedral point group 6mm (see Figure 3. Lattices with a 4-fold symmetry axis also possess 4 reflection lines which are rotated through 45' with respect to each other.the oblique with holohedral point group 2. the rectangular with holohedral point group 2mm. Similarly. As in the 3D case. (2mm). only even n are allowed. A lattice which only contains a 2-fold symmetry axis is either a completely general oblique lattice or a rectangular lattice. The lattice vectors r of a crystal possessing an ideal surface perpendicular t o the normal direction n are therefore those of equation (3. this also holds for any other layer. Thus. (nm.342 Chapter 3. lattices with a 6-fold axis have 6 reflection lines which meet at an angle of 30'.24). n 5 6 was found. and reflections at lines within the 2D lattice plane. C 2 (2) and C2. 2D lattices may be divided into crystal systems and Bravais lattices according to their symmetry with respect to rotations and reflections. ( n ) or C.4.8. one takes the four primitive lattices with unit cells which are parallelograms having either no particular symmetry. the point groups are either C . 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. a square or an equilateral hexagon. f2. We now consider the possible plane crystal systems and plane Bravais lattices. so that r =slf1+ s2f2 (3.191) holds.187). The primitive unit cell of the crystal with surface has the form of a prism bounded above by the parallelogram spanned by f1. For the low-index surfaces of the common semiconductor crystal structures. Electronic structure of semiconductor crystals with perturbations itself.. f 2 and extending to minus infinity in the direction of -f3. In this case the point group is c 6 v (6mm). f 3 are listed in Table 3. First. the possible multiplicities of rotation symmetry axis of plane lattices are n = 2. The vectors f1. There. Since the rotation through 180' is always a symmetry element of a plane lattice. The point groups of these lattices are. The possible plane Bravais lattices are obtained as follows. Their point symmetry elements are necessarily rotations about axes which are perpendicular to the 2D lattice plane.

nor in any other primitive lattice. point groups which transfer equivalent directions of a crystal with surface into one another and. rectangular lattice. on the other hand. In the latter case this implies that not only does the 2D lattice transform into itself. This lattice cannot be transformed by continuous and symmetry preserving transformations in the primitive rectangular lattice. We now turn our attention to the symmetries of crystals with surface as a whole. With the last statements we have completed the symmetry classification of the plane lattices of crystal surfaces. ~ 1 . the addition of points either leads back to the primitive lattice or results in no lattice at all (i. s and write .189).I .6. we denote the atomic positions by Rjl(s1. In all other cases. Point and space group symmetries of ideal crystal surfaces We wish to establish.24: The 5 plane Bravais lattices of the 4 plane crystal systems.9. To express the 2D nature of the translation symmetry of a crystal with a surface ~) explicitly. and again only the primitive in the quadratic and hexagonal cases (see Figure 3. These atoms are located at positions R(j. on the one hand.e. 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. The lattice types of the ideal low index surfaces of the common semiconductor structures are summarized in Table 3. s2) R(j.24). So it forms an additional Bravais lattice.I. it creates a crystal with a basis). sir92) given by equation (3.3. space groups which transform the crystal with a surface into itself. C e n semiconductor surfaces la 343 oblique P rectangular P quadratic P hexagonal P C Figure 3. the primitive and the centered in the rectangular case. but so do equivalent atoms occupying the primitive unit cells.

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. The point and space group elements of a crystal with surface must leave the surface invariant. i. The point groups of directions of crystals with plane surfaces are necessarily subgroups of the holohedral point groups of the plane lattices. i. we therefore also have the situation that. subgroups of the point groups 2. as in the case of translation symmetry.e. only 2D symmetry groups need to be taken into consideration. There are exactly . 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. respectively.344 Chapter 3. Electronic structure of semiconductor crystals with perturbations Table 3.2mm.9: Structural properties of ideal low index surfaces of the five common semiconductor crystal structures. Column 6 and 7 give. although a crystal bounded by a surface extends in three dimensions. This basis contains an infinite number of vectors corresponding to the infinite number of atoms in a primitive unit cell.e. 4mm and 6mm. its point and space groups are only 2-dimensional. the number of atomic layers of an irreducible crystal slab and the number of basis atoms per layer.

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

has the group p31m as a 13-th space group. This yields the additional space group p4mg. One should further note that the point group of directions of a crystal remains unchanged if. 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 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. One easily finds that this is not the case for the hexagonal crystal system. The additional space groups in the case of the .346 Chapter 3. 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.26: The 17 space groups of crystals with plane surface. a glide reflection line is substituted for an ordinary reflection line.I c-rectangular Figure 3. in its space group. 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.e.

In the case of crystals with plane surface. primitive rectangular crystal system are p l g l (from p l r n l ) and p2rng. Clean semiconductor surfaces 347 2mn c2mn p-square 4 4mn p4 p4mn I I I . Four or them involve glide reflections.3.-hexagonal 3 p3m1 I Figure 3.26: Continuation: The 17 space groups of crystals with plane surface. 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. they are non-symmorphic. the subgroups of the 3D groups which contain only those symmetry elements which transform lattice planes .e.p2gg (from p2mrn).6. in fact. The centered rectangular and the oblique crystal systems do not give rise to additional space groups. They are. there are therefore a total of 17 different space groups.

columns 4 and 5.s2) as they did in the infinite 3D crystal.27 such projections are shown for the three low index surfaces of diamond and zincblende type crystals. After some number of atomic layers (6 for (lll). Here. The 2D point and space groups of the three lowest index surfaces of the five common crystal structures are summarized in Table 3. and are thus subjected to displacements from their original sites in the crystal bulk. Electronic structure of semiconductor crystak with perturbations situated parallel to the surface into themselves. these forces are also subjected to changes accompanied by displacements in the second layer and so on for each successive layer. The point and space group symmetries of a crystal with an ideal surface are those of its irreducible crystal slab. 4.348 Chapter 3. and transform atomic layers located parallel to the surface into themselves if space groups are under consideration. 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. Atoms from different layers below the surface are illustrated differently with sizes as indicated. 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(s1.9.4 for (loo). the new positions of atoms in the crystal with surface and . they contain elements which transform directions in a lattice plane into equivalent directions in that plane as far as point groups are concerned. The atoms of the surface layer experience different forces than those acting in the bulk of the crystal. this assumption is actually not valid. A crystal slab which contains the minimum number of atomic layers necessary for completing the projection. As already noted. 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. Translation symmetry of relaxed and reconstructed surfaces We denote the displacements of atoms due to the formation of the surface by 6Rjl(sl. More precisely. The point and space group symmetry of an ideal crystal surface may also be derived from the projection of the crystal onto its surface. the projections repeat themselves. is called an irreducible crystal slab. if the former is generated from the latter by removing one half of it. In Figure 3. and 2 doubly occupied layers for ( l l o) ) . Since the forces acting on the atoms of the second layer are in part determined by the positions of the atoms in the first.

i.e.195) The displacements 6Rjl may be divided into two classes with regard to their effect on translation symmetry. 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. . If the latter is not affected. In this case equivalent atoms in different primitive unit cells are displaced in the same way. Then 6Rjl(sl.6. by R’j~(s1.27: Projections of a diamond or zincblende type crystal onto its low index surfaces.3. the displacements are termed r-e-eluzation. (3. sz).

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

f: and fi are parallel to f 1 . f 2 .e. The latter are. A formal proof of this assumption does not exist. 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. The two most common forms of this type of reconstruction have a special notation (Wood notation): (1) The non-diagonal elements vanish.e. They need to be rational if and only if the two lattices derived from f i . i. of the transformation matrix Q are. the coefficients Q i k . at the outset. We thus have . it is smaller than T. We thus arrive at the important conclusion that in the only case of practical interest (iii) above. it follows that the Qik must have integer values.3. of the surface slab. that particular reconstruction will take place which allows for maximum translation symmetry of the crystal with surface (the system ‘surface slab plus bulk slab’). in case (ii) above. i. Clean semiconductor surfaces 35 1 to T. (iii) translation symmetry exists and is the same as that of the surface slab. i. f 2 of the ideal surface. If one assumes that. i. and their lengths are integer multiples of the respective lengths of the latter. f 2 according to + 912f2 f.. i.198) (3. fi. by definition. as a rule. = Q2lfl + 922f2. i. respectively. surface reconstruction can be described by a 2 x 2 matrix with integer elements. it generally yields correct results. and it is probably not valid without exceptions. also the primitive lattice vectors of the bulk slab of the crystal with surface. If the coincidence lattice is identical to the lattice derived from fi. If T.199) Here. f i is simultaneously the lattice of the reconstructed surface.2.e.e. (ii) translation symmetry exists but is smaller than that of the surface slab. arbitrary real numbers. however.e.. is not a subgroup of Tb then T cannot be equal to T. the coincidence lattice is identical to the lattice T. f’2 have a coincidence lattice. They may be linearly composed of f 1 . In this case.. in the particularly interesting case (iii). among the various conceivable surface reconstructions with a given degree of translation symmetry. Let be fi and fi the primitive lattice vectors of the reconstructed surface slab. then only the third of the above possibilities can be realized. and is necessarily a proper subgroup of T. k = 1. f 2 and f ’ l . f: = Qllfl (3. the lattice derived from f : . 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.6.

201). Examples of both of the special reconstruction forms discussed. with a subsequent rescaling of f1. This can only take place. Thus. n x m is replaced by p .202). fi by a rotation through the same angle L(f. the modified notation applies only to this case.n x m notation is just a simpler description of a reconstruction of type (3. This means that the two vectors f1. and which can otherwise only be characterized by the 2 x 2 matrix Q itself. The lattice vectors fi = nfi and fi = mfz are then not necessarily primitive as originally assumed in the notation (3. in the notation (3. 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. are shown in Figure 3. which (! are in general not equal to each other. Electronic structure of semiconductor crystak with perturbations f: = nfi. fi) and L(f&fz).202). of a particular material C reconstructed in this way is characterized by the symbolic notation f..201) (2) The off-diagonal elements of Q are not equal zero.202) and The factors lf~l/lf~l lfil/lf21 are in general irrational in contrast to the qik. fi) . however. In the rectangular case the notation c . which in the case considered here are integers.201). (3. f& = mf2 . (3. and in addition to primitive ( p ) reconstructed surface lattices.. (3. lfil C(hkl) -x lfil 11 4 . i.n x m describes a type of reconstruction which is not covered by one of the two notations (3. are assumed to be equal in the case under consideration. also centered ( c ) ones are possible.e. (hlcl) surface respectively. f2 by the factors lfiI/fll and ~ f ~ ~ / ~ f ~ ~ A. as well as for the general reconstruction form in case (iii). This implies that the crystal with reconstructed surface belongs to a different plane . The point symmetry of a reconstructed surface lattice is generally lower than that of the ideal surface lattice from which it is derived. The primitive unit cell of the surface slab contains n x m primitive unit cells of the bulk slab. If21 (3.29.n x m or c . Sometimes. The angles Lf. f2 (with tails joined at the same point) can be transformed into the two corresponding vectors = L(f4. fi is not parallel to fi and/or fi is not parallel to f2. For square reconstructed lattices the c . although it is also sometimes used (formally incorrectly) for square lattices. for rectangular surface lattices.201).200) with n and m being integers.352 Chapter 3.a. f2) = a about an axis which is perpendicular to the surface.n x m.

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

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. If the surface slab consists of more layers than the irreducible crystal slab.354 Chapter 3. If this is the case. respectively. but also on the point and space symmetries of the relaxed or reconstructed surface slab. respectively. 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. 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. the only difference being that the cores and electrons of the removed semi-infinite crystal above the surface are missing. and the positions of the cores just below the surface . the point and space groups of the whole crystal with relaxed or reconstructed surface. Electronic structure of semiconductor crystals with perturbations Figure 3. 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. 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. Similarly like this was done for the translation symmetry group above.30: Symmetrically equivalent 2 x 1 reconstructions in the case of ideal surfaces belonging to the square (left) and hexagonal crystal systems. the point and space groups of the relaxed or reconstructed surface slab are. the point and space groups of whole crystal with relaxed or reconstructed surface.6.3 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.

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

53). -00. The oneelectron potential V(x) may be written as the sum of the electron-core interaction potential Vc(x).206) As in the 3D bulk case. one-electron approximations introduced in section 2. 1 = 0... .203) may be chosen simultaneously as eigenfunctions of the surface lattice translation operators t. . this leads to + + + -W J (3..205) where q(x) is the potential of a core of species j located at R = 0. so that v(x)= V(x + r) . hence. . .207) where q1.203) as in the case of an infinite bulk crystal (see equation 2. and an effective one-electron any of the potential Ve(x)due to electron-electron interaction. 2 . (3. For Ve(x). .1 may be used. Bloch theorem This theorem states that the energy eigenfunctions $E(x) of the Schrodinger equation (3. defined by the relations . Electronic structure of semiconductor crystals with perturbations electron in a crystal with surface has the same general form (3.92 are arbitrary real numbers. also Ve(x)and V ( x ) have the translation symmetry of the 2D surface lattice. -1. J . 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. . (3. The core potential Vc(x)and. 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 allows one to write these functions in the form of Bloch functions @Q(x) with a 2D quasi-wavevector 4 = 91g1 + 9282. this symmetry can be used to derive the Bloch theorem.356 Chapter 3. . and gl and gz are the primitive lattice vectors of the reciprocal surface lattice. j = 1 .

within the surface.6.208) [fl x f2]. f2)’] as normalization constant. gz of (3.209) lie in the plane spanned by the two primitive surface lattice vectors f1. This means that the q-vectors must belong to a finely-meshed lattice similar to that of Figure 2.fz) . If g varies over the whole infinite space. As in the 3D bulk case it is convenient to introduce a region of macroscopic size with respect to which the eigenfunctions $J. Surface Brillouin zones and surface energy bands The energy eigenvalues E of a particular Bloch type eigenfunction of equation (3. To guarantee the periodicity of the Bloch functions $ ~ ~ ( x ) (3. In the case of a crystal with surface this region forms a parallelogram spanned by the edge vectors Gfl. . Clean semiconductor surfaces 35 7 fi .. Gf2.210) with respect to the periodicity parallelogram. For the macroscopically large values of G which we assume.Eq(x) -e2qx = 1 fi UEq(X). This description corresponds to the extended zone scheme in the case of an infinite bulk crystal considered in section 2. as we assume here. k = 1.pz as integers. 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. (3. As in the latter case. fz.4.210) where U Q ( X ) is the Bloch factor. although the number of different q-values within a given region of q-space is finite. 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. q is practically continuous. 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. i. The area RII of the periodicity region is G21f1 x f2l. The latter equations are solved by the vectors g1 = N-lf2 x (3. g2 = N-lfl x [f2 x fl] (3. g k = 27T6&.203) depend on q.(fi .e. the wavevectors q must have the form (3. E represents a unique function E ( q ) of q. with G being a large integer.3.E~(x) be assumed can to be periodic.209) with N = (1/2n)[(f1 . The same statement applies to the 2D wavevector q.4.211) with p1. i. The two vectors gl.2. fl)(fZ.

4 as an illustration for the 3D case. in the extended scheme. 1 2 (3. Types of eigenstates Bulk states Consider an infinite bulk crystal. There. Thus the energy function E(q) is continuous within these zones. there is a distinguished choice of the primitive unit cell. Electronic structure of semiconductor crystals with perturbations In the reduced scheme. and the energy function E(q) in the p-th surface B Z can be folded back to the first surface B Z . regarding their relations to the energy bands of 3D bulk crystals without surface. hence.g2 = 0. and cleave it into two semi-infinite crystals with a surface parallel to a particular lattice plane. free of Bragg reflection lines. The spectra of energy . As in the bulk case. Of particular importance is the f i r s t surface B Z . 5 different reciprocal surface lattices. One speaks of surface Brillouin zones (BZs).(q) E ( q g ) defined only over a primitive unit cell. one may demonstrate that.4. Using first order perturbation theory with respect to the periodic potential V(x). The surface B Z s of the square lattice have. They are shown in Figure 3. g + . Below we characterize these differences in a qualitative way. by definition. Thus we may state that the energy eigenvalues of a crystal with surface form energy bands over the first surface BZ. Equation (3.(q) which is called a surface energy band. It may also be defined as the Wigner-Seitz cell of the reciprocal surface lattice. The first surface B Z s are. E(q) represents a continuous function of q everywhere. There are surface bands of different types. Furthermore. 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. already been used in section 2.358 Chapter 3. in fact. except for the q-vectors with lql = lq + gl or + q .212) defines lines in the 2D q-space which are analogous to Bragg reflection planes in the 3D k-space of a bulk crystal. any higher surface B Z of order p may be reduced to the first surface B Z . it forms a continuous function E. On Bragg reflection lines.31. as we will see below.212) where g is an arbitrary surface reciprocal lattice vector. there are also 5 different first surface B Z s . Since there are 5 different plane Bravais lattices and. the energy function E(q+ g) over the whole q-space is replaced by the manifold of functions E. the energy function E(q) has discontinuities. 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.

Eigenstates of a crystal with surface exhibiting such properties are called bulk states. (e) hexagonal. 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.6. '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 . they will exhibit undamped oscillations throughout the whole semi-infinite crystal. Here. if examined at positions outside of the crystal. eigenvalues of the two semi-infinite crystals will contain all energy levels which were already eigenvalues of the infinite bulk crystal before cleaving. and their notations are introduced. i. (b) p-rectangular. The eigenfunctions of the crystal with surface corresponding to these eigenvalues.3.e. as do the eigenfunctions of the infinite bulk crystal (see Figure 3. while inside they will practically be the same as those of the infinite crystal.32). Symmetry lines and points are also shown. These bands can be obtained by projecting the bulk bands E?"(k) of the infinite crystal onto the first surface B Z . The corresponding energy eigenvalues form bulk state surface energy bands Ep(q). Clesn semiconductor surfaces 359 t' tY Figure 3.31: Surface B Z s of the 5 plane lattices: (a) oblique. will decay exponentially with increasing distance from the surface. (c) c-rectangular. (d) square.

. but with various components kl perpendicular to it. The band structure is taken from the empty lattice model introduced in section 2. it represents a general feature of the projected bulk band structure.360 Chapter 3. This has to be folded back to the first surface B Z . more realistic cases as well. As kl varies continuously. the bulk B Z is to be projected onto the plane of the first surface B Z (see Figure 3.32: The three different types of electron energy eigenstates of a crystal with surface below the vacuum level (schematically). together with its energy values.32). Electronic structure of semiconductor crystals with perturbations W P x I -w 0 . Formally. @ also does. this can be expressed by the relations The bulk state surface band index p in (3. We illustrate the projection of bulk bands onto the surface B Z using the (100) surface of a diamond type crystal as an example. This means that a particular band of the infinite bulk crystal gives rise to a continuum of surface bands. As a first step. In this way. In the forbidden energy regions states may occur which are localized at the surface. In addition to q-vectors for which all energy values are allowed. one notes that part of the projected bulk B Z lies in the second surface B Z . This peculiarity is found in other.4. In this way we obtain the projections of the lowest three empty lattice bands shown in Figure 3. the infinitely large number of atoms in a primitive unit cell of the crystal with surface manifests itself.213) replaces the bulk quantum numbers v k l . there are also q-vectors occurring for which certain energy values are forbidden. In doing so.0 C f w C + C 3 W surface state 9- 0 x- Figure 3.33. bulk B Z having the same projection q on the surface B Z plane.

Clean semiconductor surfaces 361 Figure 3. If bound surface states exist. only in 3 . therefore. at a . Antiresonances are necessary in order to satisfy Levinson’s theorem. p = p. which holds for surfaces as well as for point perturbations.(q) are bound surface bands. Implications of symmetry for surface band structure The spatial symmetry of a crystal with surface has implications for the posp. sible degrees of degeneracy of surface energy bands Ep(q). The eigenfunctions at these energies are also localized at the surface.6. The states are then called bound surface states and the corresponding energy bands E. ‘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. The localization occurs. If the energy lies in the forbidden region of the projected bulk band structure. (T. Besides these.32). the decay of the eigenfunction towards the bulk proceeds exponentially (see Figure 3.3.2 = 1 dimension. surfaces constitute 2-dimensional perturbations.33: First (100) surface B Z (shaded area) together with the projected first bulk B Z for a crystal with fcc Bravais lattice. but decay less rapidly towards the bulk (according to a power law) than the exponentially decaying bound surface states. namely that perpendicular to the surface. In contrast to the latter. 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). the antiresonances must compensate the increase of the total DOS in the previously forbidden energy region. They manifest themselves in an increase (resonance) or decrease (antiresonance) of the density of states. one has surface resonances and antiresonances.

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

--z. which below will be studied as an example. but the corresponding energy eigenvalues are degenerate because of time reversal symmetry. one has 2D representations only at X and X'.) and 1D representations might not be possible at all.--~. Clean semiconductor surfaces 363 pig1 r. [After Terzibaschian and Enderlein.3.-?. -A\-x:-z. The two 1D representations on the 2-line connecting these points belong to the same energy eigenvalue because of time reversal symmetry. which applies for (110) surfaces of diamond type crystals. For the three remaining space groups p2mm.- ~--A~.-&-z. This happens for 2 of the 5 space groups of the primitive rectangular Bravais lattice. 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 . In Figure 3. In the case of the space group p2mg. the representations at all symmetry points are 1D.--Z.-zF- I I I Figure 3.--M.X ' are lD.2' .-A.6. The representations on the connecting line X .-M2-Z. p l m l . the possible types of band structures are shown on certain symmetry lines of the p-rectangular surface B Z .35.- I x2 x1 x.35: Symmetry and degeneracy of the surface energy bands for the 5 space groups of the p-rectangular Bravais lattice. For the space group p2gg. -A.-X.r.M .-M.2 . only 2D representations exist at M and X . and p l g l .- ~r~r+-~2---~-~. 1986.

one of them being real (that of the semi-infinite crystal).. the orbital a localized at such a site is given by &(x . rather than over all points R of the 3D bulk lattice. With the surface adapted notation. with the exception that the dimensionality of the lattice has to be changed from 3 to 2. The corresponding Bloch sums &jlp(x)are defined as (3. 2 . in the direction perpendicular to the surface. i.and three p-orbitals per atom we use the four hybrid-orbitals.1f3) E &jl. To get the matrix elements of the Hamiltonian H between Bloch sums. Electronic structure of semiconductor crystals with perturbations to the surface. This point of view gives rise to the so-called slab method for calculating the electronic structure of crystals with surfaces. i.6.36). we first need these elements between the localized hybrid orbitals +htjlT Ihtjlr). 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).364 Chapter 3.2 15) . for example. and the other one (obtained by cutting the semi-infinite crystal) not. The latter has two plane surfaces. one has to use Bloch sums of atomic orbitals &(x) over all points r of the 2D surface lattice. Instead of the one s.e.(x). One may say that.5 where the whole cluster surface is artificial. 4 . r+G+Zf3. Some specific approximation is necessary to transform this to a finite matrix.3 . The slab method may be combined with any band structure calculational method for infinite bulk crystals. t = 1 . the true semi-infinite crystal is replaced by a cluster (see Figure 3. One possibility is to consider a slab of the crystal. 3 . The diagonal elements are (3. runs from 0 to -co. We consider the ideal (111) surface of a diamond type crystal which according to subsection 3..2 14) The number of different Bloch sums is infinitely large even if a finite number of orbitals is used per atom. for a regular crystal site.2. we replace a in the Bloch sum (3. Only nearest neighbor interactions are taken into account.37. Its combination with the tight binding method will be illustrated below by means of an example. to cut off the semi-infinite crystal at a particular lattice plane parallel to the surface and discard the remainder. has a hexagonal Bravais lattice.e.214) by ht.r . An illustration of this model is given in Figure 3. Consequently the Hamiltonian is given by an infinite matrix in the atomic orbital representation &jl. In the tight binding method. because the integer 1 counting the primitive crystal slabs. This differs from the cluster method in the case of point defects discussed in section 3.

Since no nearest neighbor hybrid exists for the hybrid )hllOr) pointing out of the surface.36: Illustration of the slab method for surface band structure calculations.292).216) The two types of matrix elements in (3. Let j = 1. all nearest neighbor elements involving IhllOr) vanish. 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. Clean semiconductor surfaces 365 Figure 3. 4 are equal to the parameter V2 introduced in equation (2. The other three elements with t = 2 . 3 .3. This is not true for elements between hybrids located at different atoms.215) and (3. 3 7 Defect molecule model of the ideal (111) surface of a crystal with diamond structure.6. pointing toward (htlOr). and the non-diagonal elements between different hybrids at the same atom j = j ’ are = (htllrlH(htJ1lr) VI .216) are equal for atoms at the surface and in the bulk. (3. t # t’ . . Figure 3 .1= 0.

2.4. 2 (3. lh320q).4 . We have d2 = -(lTT). h l o q ) . They are (htlOq(Hlht. lh220q). 2 a d3 = -(lll). Then the 7 Bloch sums IhtlOq). where e t is given by equation (2. Thus an infinite matrix would occur if we would not restrict consideration to a slab. If the basis functions are arranged in the order IhllOq).3. then the Hamiltonian matrix is (3.220) t = 2. as we in fact do.222) The eigenvalues of this matrix are plotted in Figure 3. and these hybrids interact with hybrids at more remote atoms. t # t’ . 4 . 2 a . we will go one step further and neglect all couplings between the hybrids at the nearest neighbor atoms. Here.216) and (3. (3.366 Chapter 3.- d4 = a(TT1). .31. and (ht20q). are completely decoupled from the rest of the Bloch sums (see Figure 3. are coupled to the other hybrids at these atoms.lOq)= v . the matrix elements between the corresponding Bloch sums (3. IhzlOq). 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. Electronic structure of semiconductor crystals with perturbations Using equations (3.217). (3.3.214) may be formed.t = 2 .215). lh420q). This model represents an analog of the defect molecule model in the case of a point perturbation. 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. 1 (htIOqlHlht20q) = etV2.67).219) (3.38 for different symmetry lines of the first surface B Z of the hexagonal lattice of Figure 3. h l o q ) .221) The hybrids lht201-i) at the nearest neighbor atoms pointing td the surface atom lor. t = 1. 3 .240).

This arrangement represents a 3 D supercrystal composed of 1D supercells (bear in mind that in the case of point defects in section 3.39).98 e V . while the bound surface band in the gap would hardly change.3. If we were to consider more than 2 atomic layers. which bind this atom back to its nearest neighbors in the second layer. The three lowest and three highest bands are bulk state surface bands. Supercell method The slab considered in the preceding subsection may be repeated periodically in the direction perpendicular to the surface.38: Band structure of the ideal (111) surface of a diamond crystal within the defect molecule model. the region where the bulk bands in Figure 3. They arise from the three hybrids of the surface atom. they correspond to the 3 back bonding and antibonding states. each repetition being approximated by a finite slab of several atomic layers embedded between vacancy layers.38 occur would be covered by more bulk state surface bands. The hybrid energy Eh is used as the energy origin. The band in the gap is due to the dangling hybrid of the surface atom.13 e V . V2 = 6. The TB parameters are V1 = 2. More strictly.5.6. we similarly considered a . simultaneously inserting several layers of vacancies between two neighboring slabs (see Figure 3. This structure may be considered to be an infinite repetition of the original crystal with surface. Clean semiconductor surfaces 367 r M K r W avevec tor Figure 3. It forms a bound surface band.

39: Supercrystal obtained by a periodic repetition of supercells. This makes the supercell method particularly appealing. then remove some number of neighboring atomic layers parallel to the surface under consideration or. The band structure of the supercrystal may be obtained by means of any 3 D band structure calculation method without modification. The band structure of the supercrystal is approximately the same as that of the original crystal with surface. The latter are composed of crystal slabs embedded between vacancy layers. as well as the local density functional or quasi-particle approximations. Combined with the pseudopotential method. which has been excluded. The significance of this characterization is the following: Consider first an ideal infinite 3 D crystal. equivalently. and the latter slabs are thick enough to simulate a semi-infinite crystal. 3D supercrystal composed of 3 D supercells). 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 . Electronic structure of semiconductor crystals with perturbations Figure 3.368 Chapter 3. k l may be chosen arbitrarily because any dispersion of EF(k) = E F ( q . provided the vacancy slabs are thick enough to suppress coupling between neighboring crystal slabs. Defect model and Green’s function method A crystal with surface may also be viewed as a 3 D crystal with a 2D perturbation. In this. it represents the most important calculational method for electronic and atomic structure determinations of surfaces. . k l ) with respect to k l would indicate a coupling between the slabs.

namely that perpendicular to the surface. such that . just as in the case of a point perturbation.134)). a single layer of vacancies is enough to decouple the two semi-infinite crystals. Clean semiconductor surfaces 369 Figure 3.223) If only nearest neighbor interactions are taken into account. and are identical with that of the considered crystal with surface.40). Wannier functions are again a possible choice. As in the case of a single vacancy.40: Illustration of the defect method for calculating surface energy band structure. create the same number of vacancy layers (see Figure 3. The electronic structures of the two semi-infinite crystals coincide.74).1 (see equation (3. For the analysis of the bound state condition (3.3. They do not interact provided the number of vacancy layers is large enough. the states bound at the defect may be obtained by means of the Greens function G o ( E )of the unperturbed 3D crystal. which we will assume. Here. the perturbation potential 1 V’(x) represents the difference of the potential energy of an electron in the perturbed and unperturbed crystals.6. by the vanishing of the determinant of [Go(E)V’ . It is the negative of the sum of the potentials of the removed atoms or the sum of all vacancy potentials. What remains are two identical semi-infinite crystals which are only displaced with respect to each other. one has to use a particular basis set. more strictly. We denote these functions by IvqRl) where RI is the component of a 3D lattice vector R perpendicular to the surface. It has the 2D lattice symmetry of the surface so that ~ ’ ( x= V’(X ) + r). but here they involve localization only in one direction. (3.

Then the matrix representation of V1(x) is where VL. i.. The energy E is arbitrary first of all. (3.. still another method for surface band structure calculations should be mentioned. the determinant of the matrix (3.228) According to equation (3. Det [G:(E.134). 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).1 take the form - with (3. it will be noted that the q-dependence which occurs here was absent there. The relevant matrix elements (vqOIGoV1 1lvlqO) of GoV1. Electronic structure of semiconductor crystals with perturbations (3.229) If one compares this equation with the corresponding relation (3. Transferring the wave function from the surface unit cell to the ..] = 0.(q) ..370 Chapter 3. q)VL.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.(q) = (vq01V’Jv’qO)has been used. Transfer matrix method Finally. 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.94) for deep centers. 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.6.e.

Since they are neutral particles. It is advisable to treat the atomic structure together with the electronic structure because of the close relation between the two kinds of structures. however. including those at the surface. X-ray photons and neutrons interact only relatively weakly with the crystal. The practical use of this method seems to be limited.4 In this subsection we will deal with the atomic and electronic structures of some important semiconductor surfaces. Electron energies in the region of 100 eV and neutron energies of 0. the diffraction patterns are dominated by the bulk of the crystals. again referring to both the atomic and electronic aspects.e. If the wavelength is of the order of the distance between the atoms. the crystal constitutes a 3D diffraction lattice and diffraction maxima will occur in prescribed directions in space. Electron and neutron waves are also diffracted by bulk crystals.6.3. Since the number of surface layers is extremely small in comparison to the total number of layers. of the order of magnitude of 1 A. A t o m i c and e l e c t r o n i c structure of particular surfaces 3. X-rays are by far the most important for determining the structure of bulk crystals. Electrons having energy less than 100 k e V can not pass through a crystal of . 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.t h power W ( E ) of M ( E ) . the (110) surface of GaAs and other 111-V compound semiconductors as well as the (111) and (100) surfaces of GaAs. X-rays and neutrons thus yield information on all atomic layers of a crystal. A wavelength in the region of 1 corresponds to a photon energy in the range of 10 k e V . The various experimental methods differ primarily in the nature of the waves employed. They can pass through crystals of macroscopic thickness and be backscattered from them from macroscopic depths within them. We begin with a short introduction to the experimental methods of surface structure analysis.6.th unit cell below the surface can be done by applying the n . including the various reconstruction states of the Si (111) surface. Bound surface states are obtained for such energy values E for which M n ( E ) decays exponentially with n. i. The crystal structure may be determined from the positions and intensities of these maxima. as was pointed out earlier. the Si (100) surface. Clean semiconductor surfaces 371 n . The interaction of electrons with the atomic cores and the valence electrons of a crystal is significantly stronger than that of photons and neutrons.1 e V are required for wavelengths in the d region.

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

The latter two methods have become particularly important.3. The most powerful and universal method is photoemission spectroscopy (PES). There is exactly one maximum for each reciprocal lattice point g. Some typical LEED images are shown in Figure 3.41: LEED maxima. Clean semiconductor surfaces 373 Figure 3. This method relies on the external photoeffect in which an electron is emitted from the crystal by .] lkzl. a variety of methods exist to study the electronic structure of surfaces.42. and the less bright points to the finer reciprocal lattice of the reconstructed surface. Like for atomic structure determinations. known as ‘Re5ection High Energy Electron Diffraction’ ( M E E D ) . To obtain the actual positions of atoms is more diacult. Besides LEED. Construction of sphere Jk. In this way it is relatively easy to determine the surface lattice by means of LEED. scanning tunneling microscopy (STM) and atomic force microscopy (AFM). diffraction of X-rays incident almost parallel to the surface.6. can supplement it. Imaging procedures of significance are transmission electron microscopy (TEM). 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). there are other methods for surface structure analysis which. although they are not a substitute for LEED. determine the directions in which diffraction maxima oc= cur. The direct surface lattice is the reciprocal of the reciprocal surface lattice. These methods include diffraction of energetic electrons in the region of some 10 k e V . The reciprocal surface lattice can thus be read immediately from the distribution of the diffraction maxima on the registration screen. The bright points correspond to the reciprocal lattice of the ideal surface. Scattering of energetic ions ( M 1 M e V ) is used in techniques like ‘Rutherford backscattering’ (RBS) and ‘ion channeling’. and diffraction of slow Helium atoms (of M I00 meV). in particular the bound surface states in the energy gap of the bulk crystal.

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

and it may be used to determine the parameters which can be varied in such a model. provided it can be made surface-sensitive. This applies to optical reflectivity. Experimental techniques like field effect measurements fulfill this requirement from the very beginning. By comparing theory and experiment one can evaluate the feasibility of various models of surface structure. On the other hand. . they can be calculated on the basis of a particular surface structure model. surface states can be resolved spatially and energetically (scanning tunneling spectroscopy). pied surface states one may use inverse PES in which electrons captured by such states emit photons. can also provide data on the atomic structure.1) are an example. In principle. These shifts differ for atoms in the bulk and at the surface because of the altered atomic structure at the surface. and capacity measurements. a variety of other techniques exists which can provide data on surface states.6. as well as electron energy loss spectroscopy (EELS). Beside photoemission.3. The difference (typically some tenths of an e v ) can be measured by means of PES and UPS. The calculation of the total energy is a purely theoretical test of the validity of a particular surface structure model. electrical transport. Clean semiconductor surfaces 375 11101 hi01 Figure 3. Controlling the energy of tunneling electrons in scanning tunneling microscopy.43: Geometry of the ideal Si (111) surface (left) and of the Si (111) 2 x 1 surface according to the buckling model (right). If the model has optimized parameters and results in a lower total energy than other models it may be given preference over them. Experimental techniques which primarily measure the electronic structure. any experimental technique which probes the electronic structure of bulk crystals can be employed for surface electronic structure investigations. photoconductivity. The solid state shifts of core levels (see section 2.

The ideal Si (111) surface is metallic..* . and can host 2 electrons per surface unit cell. .. the electron occupancy of the bound surface band in the fundamental gap. .8. 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.. . one obtains a 2 x 1 reconstructed (111) surface. only 1 electron per surface unit cell is left for the bound surface band. . f2 of Table 3. The surface lattice is hexagonal. in particular. This band arises from dangling sp3-hybrids of surface atoms. After annealing it at 500 C . a 7 x 7 reconstruction state evolves. There is one surface atom per primitive unit cell. and one dangling bond per surface atom..44) and considers. and the two primitive lattice vectors are fi.*.... . Thus this band remains only half-filled. !ii ::I . I ' O r *!:! t i -5 .44: Surface band structure of an ideal Si (111) surface.. which remains stable at room temperature. The (111) surface is the cleavage plane of diamond type crystals.43 (left)... Since 3 of the 4 valence electrons of a surface atom are in bonds with second-layer atoms.. By cleaving a Si crystal in UHV at room temperature..-I I iii r I I.376 Chapter 3. 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. Electronic structure of semiconductor crystals with perturbations Figure 3.

e the translation symmetry of the surface would spontaneously be lowered. The corresponding first surface BZ is also a rectangle (see Figure 3. one speaks of a Peierls instability or a Peierls t r a n s i t i o n However. its r . A similar spontaneous symmetry breaking. If the total energy of this state were in fact lower than that of the ideal surface.e.and its short side. Later. parallel to [Olq. There is no gap between these two bands because they arise from the same band of the larger BZ. buckling would take place spontaneously. Clean semiconductor surfaces 377 This state is unlikely to be stable. right). by alternately raising and lowering atoms in rows parallel to f1 above the surface and below it (see Figure 3. however. which according to Table 3.5. The surface is still metallic. 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. If the translation symmetry is broken.43. i. shown in Figure 3. There.and p-like dangling hybrids are just the bands below and above the gap discussed before.M-direction. the so-called buckling model (see Figure 3. while no electrons remain for the population of the upper p-like band. right-hand side) which in the early days of clean semiconductor surface physics was believed to be correct. is parallel to [Olq. Below we discuss a particularly simple reconstruction model. i. parallel to [2ii]. it was realized that buckling is energetically advantageous only for 111-V compound semiconductor surfaces. was discussed in the context of point perturbations in section 3. The two bound surface bands derived from these s. while no translation symmetry was involved.43. 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 . the three back-bonding hybrids of a raised atoms becomes more p-like. surface reconstruction is likely to take place. i. a direct and a back-folded one. as has been indicated at the outset.43 right. the Jahn-Teller effect. The rectangular BZ is half as big as the original hexagonal BZ.8 points in the direction [ l i O ] . i.e. A gap arises if the so far formal 2 x 1 reconstruction is made real. The lower s-like band can host all electrons of the dangling hybrids. 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.e its X . This can be done by a buckling of the surface. while it is not advantageous for group-IV semiconductor surfaces including the (111) surface of Si. the point symmetry was broken.e. as in the case of surface reconstruction.31) with its long side. and the dangling hybrid at this atom more s-like simultaneously lowering its energy. and each band of the latter gives rise two band in the former. i.3.6. To introduce the buckling model we consider doubling of the primitive unit cell in the direction of primitive lattice vector fi.X-direction.and its long side parallel to [ 2 m . In this. buckling turns out to be energetically not favorable in the case of Si (111) surfaces.

Electronic structure of semiconductor crystals with perturbations r? 'P r[1?01 U [I101 Side view a) b) Figure 3. . 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. Part (a) shows the unreconstructed surface in top and side views. Part (b) shows the same views of the surface as in part (a). but after reconstruction has taken place.45: a-bonded chain model of the Si (111) 2 x 1 surface (After Pandey. 1982).378 Chapter 3.

The dangling bonds left at the third layer atoms (for example.45b. the configuration dependence of oneelectron states.45b) because the dangling bonds are perpendicular to the surface.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.45b). Clean semiconductor surfaces 379 raised above. These can only be s-bonds (indicated by double lines in Figure 3.2 we may say that correlation effects of electron electron interaction. atom 3).46. 1982). which is also the direction of the s-bonded chains. In this way s-bonded chains occur along the [ l O q direction (Pandey.45a). While the latter exhibit rings with 6 mutually bonded atoms (see Figure 3. the former shows alternating rings with 5 and 7 bonded atoms (Figure 3. more strictly speaking.e. + .45b by dashed lines. The surface is in fact 2 x 1 reconstructed.2 f 2 + (fi + f 2 ) = f 1 . prevents the buckled Si (111) surface to be lower in energy than the ideal one.46 shows the wavevector dispersion of the two bound surface bands as obtained from ARUPS measurements together with the calculated dispersion of these bands. along the [lo3 direction in Figure 3. exactly what is seen in Figure 3. i. The agreement is quite satisfying. 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). Figure 3.3. The reconstruction model which actually applies to the Si (111) surface is the so-called s-bonded chain model. the 2-5 bond). This implies the creation of an electric dipole which is too costly in energy to actually take place.f 2 so that the short side of the rectangle is parallel to the chain direction [lOT].45a (including atom number 2) are raised into the first layer as shown in Figure 3. In this model. Doubling -f2 yields the rectangular lattice indicated in Figure 3. Using the terminology of section 2. breaking their bonds with atoms in the third layer (for example. and the long side perpendicular to it (parallel to [121]).45. Its primitive lattice vectors are f1 + f 2 and . 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. Further evidence is provided by ARUPS and optical measurements. This may be seen by taking the primitive lattice vectors of the ideal surface to be f 1 + f 2 and -f2. The total energy of this model is clearly below that of the ideal surface (about 0. One expects strong dispersion along the chains and weak for the perpendicular direction. 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. Thus it represents a good candidate for the reconstruction of the (111) Si surface.6.5 eV per surface atom). second layer atoms in rows parallel to fi f2. atom 5) are saturated by hybrids of the first layer atoms which have been lowered down to the second layer (for example. illustrated in Figure 3.

and Hansson. (After Martensson. Pastore and Chiaradia. Nannarone.M line for the Si (111) 2 x 1 surface. points are obtained by means from ARUPS measurements. 0s .) Y l W x g o -1 r X nf 20 wave vector Figure 3.X . Energy (ev) $5 [ 7 .46: Dispersion of the bonding (B) and antibonding (A) bound surface state bands along the r . 1985.47: Differential reflectivity spectrum of the Si (111) 2 x 1 surface (After Chiarotti. Cri- 2 > W d t2 3 1 0 Q.) 0 93 0A . Electronic structure of semiconductor crystals with perturbations Figure 3.380 Chapter 3. Curves are calculated within the 7r-bonding chain model. a centi. 1971.

The model which accounts for all experimental data utilizes three structural disturbances of the ideal surface.45 (taken at its maximum). these being dimers (D). and the points are experimental data (After Del Sole and Selloni. transitions with light polarized parallel to the chains.48: Polarization dependence of the differential reflectivity spectrum of the Si (111) 2 x 1 surface of Figure 3. The solid curve is calculated using the x-bonded chain model.e. It rules out the buckling model.48 is that predicted by .49). the dashed curve using the buckling model. Clean semiconductor surfaces 38 1 Figure 3. 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). The complicated structure of this surface has finally been resolved by combining the results of various experimental methods including STM (see Figure 3. the two models differ in regard to their predictions on polarization dependence of optical reflectivity. i. Besides the 2 x 1 reconstruction. 1984. There is no doubt that the observed peak at 0.3. The differential reflectivity spectrum of the 2 x 1 reconstructed (111) surface of Si is shown in Figure 3.6. parallel to [lOq.47. adatoms (A) and stacking faults (S).5 eV is due to optical transitions between occupied and unoccupied bound surface bands. should be allowed and transitions for light polarized parallel to the perpendicular direction [121]should be forbidden. According to the 7r-bonded chain model.I-bonding chain model. there are other reconstruction states of the Si (111) surface.) Support for the r-bonded chain model comes also from optical measurements. The 7 x 7 reconstructed surface is the most stable one. while this should be reversed for the buckling model. However. It is referred to as the DAS model . The experimentally observed polarization dependence shown in Figure 3.

Electronic structure of semiconductor crystals with perturbations Figure 3. The geometry of the ideal (100) surface is shown in Figure 3. . 1986. It is stabilized by buckling. and each atom has two dangling bonds which point out of the surface like ‘rabbit ears’ (see Figure 3. however. The primitive lattice vector in the direction of f 1 doubles. (After Quate.50. The DAS model of the 7 x 7 reconstructed (111) Si surface is shown in Figure 3. The surface lattice is a square one. and the surface lattice becomes rectangular.51a). (100)surface The (100) surface is the surface of choice for electronic device applications of Si. The primitive unit cell has one surface atom. the ideal surface is metallic. and this state is unlikely to be stable.49: Scanning tunneling microscopy (STM) image of the Si (111) 7 x 7 surface. with primitive lattice vectors f 1 . f2 given in Table 3. Each dangling bond is only half-filled as in the case of the (111)surface considered above.) (Takayanagi. Thus. thus a 2 x 1 reconstruction takes place.51. This dimerization of the surface gives rise to bonding and antibonding bound surface states.382 Chapter 3. so that the surface is not yet stable.8. The remaining two dangling bonds of a dimer are still half-filled. 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). the lower bonding state being completely filled and the upper antibonding state being completely empty.

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

and of the asymmetric dimer model of this surface. Electronic structure of semiconductor crystals with perturbations Top view (100) I-- 0 n 0'. for example.384 Chapter 3. c .-0 Side view It- ? 0 U 10113 U a) b) Figure 3.4 x 2. Its surface geometry is shown in Figure . other reconstructions are also observed. asymmetric dimer model. Most of these structures may be traced back to asymmetric dimers as building blocks. Although the 2 x 1 reconstruction is the most common superstructure of the Si (100) surface.2 x 2. c . GaAs and other 111-V compounds (110) surfaces The (110) surface represents the cleavage plane of zincblende type crystals. 2 x 2.51: Geometry of the ideal Si (100) surface (a). The best understood (110) surface of all zincblende type 111-V semiconductors is the (110) surface of GaAs.

and the higher Ga-like band is completely empty. rendering its dangling hybrid more s-like and lowering its energy. Thus the ideal surface is semiconducting. 3. The primitive lattice vectors are given in Table 3. and of the same surface after relaxation (b). one Ga and one As atom. The lower As-like bound surface band is completely occupied.6. one Ga-like and one As-like.8.52: 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.52. Thus one expects two bound surface bands. It can be enlarged by moving the As atom above the surface. The surface lattice is p-rectangular. 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 3.53. Two bonds of each surface atom lie within the surface. it does not yet represent the stable state. Nevertheless.or an As atom. There are two surface atoms in a primitive unit cell. These are in fact seen in the band structure of the ideal (110) GaAs surface depicted in Figure 3.3. one is directed back and one is dangling. and moving the Ga atom below . as the gap between the two bound surface states is too small.

These displacements do not change the translation symmetry of the surface because the two atoms belong to the same unit cell.386 Chapter 3. Such states are in fact present at GaAs/insulator interfaces.53: Band structure of the ideal GaAs (110) surface. relaxation moves the bound surface states out of the gap (see Figure 3. This implies that perturbations of the surface such as. for example. 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). rendering its dangling hybrid plike and raising its energy (see Figure 3.) the surface. can easily create surface states in the gap. in good agreement with structure calculations. Experiment and theory also agree in regard to an essential feature of the band structure of the relaxed (110) surface. coverage by an insulator. 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 3.54).54. Relaxations similar to that of the (110) surface of GaAs are also observed at the (110) surfaces of other 111-Vcompounds. the As-like band merges into the valence band.52). which do not show spots other than those due to the ideal prectangular lattice. and the Ga-like band merges into the conduction band. One therefore has a relaxation instead of a reconstruction of the (110) surface. This is consistent with LEED measurements. 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°. 1992. . As indicated in Figure 3. For all materials except Gap. (After Talwar and Ting. relaxation moves the bound surface bands completely out of the fundamental gap.

but the non-polar (110) plane. and dashed regions represent dangling bond surface bands. Solid lines represent experimental results. In forming a polar surface.) Other surfaces Besides the (110) cleavage surface.51. In the latter case the 1:l ratio of Ga. One says that these surfaces are polar. For the polar surfaces.3. in Figures 3.54: Energy level diagrams of bound surface states and bulk states of various 111-Vcompound semiconductors below the vacuum level. and Manghi. 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. like in the case of group-IV materials. Bisi. 1978. F'ramed undashed regions indicate bulk bands. nor (loo). This explains why for GaAs and other 111-V compound semiconductors. however. 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. in contrast to the (110) surface. no stoichiometrical reasons which cause a surface termination by .43 and 3. the cleavage plane is neither ( l l l ) . one by Ga atoms and another by As atoms. (After Bertoni.and As atoms is strictly k e d by chemical stoichiometry. there are. which is said to be non-polar. investigations have mainly been focused on the low index (111)and (100) surfaces of GaAs. an electric dipole is created between a Ga-layer and an As-layer which is costly in energy. respectively.6. The geometrical structures of the ideal surfaces are the same as those of the corresponding Si surfaces shown. (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). Calandra.

7. 3. and the other being empty. a 3. The structure of a particular polar GaAs surface depends decisively on its termination. The plane at z = 0 is called the interface. depending on surface termination. which raises the As atoms close to the surface. say AlAs. Below the plane at z = 0 one has semiconductor material 1.or only As atoms.4'' and for the As-rich case there are f i x 8. The structure of the GaAs (100) surface exhibits an even greater variety. omitting free carrier effects. which is important for MBE-growth because this commonly begins and ends with As-rich conditions. For the Ga-rich (111) surface one finds a 2 x 2 reconstruction. Both kinds of terminations can occur simultaneously at a given surface. and above it is the material 2. . The c . For the Ga-terminated 2 x 2 (111) surface. Below. we discuss the various stationary one-electron states of undoped heterostructures. Thus.7 Semiconductor microstructures Semiconductors with a clean planar surface. The microstructures to be considered in this subsection are composed of semiconductor heterojunctions. If the vacuum is replaced by a semiconductor material different from the first. Some of the possible reconstruction states can be seen in the LEED pictures of Figure 3. Figure 3.23. such effects might be important. say GaAs.2 x 8 structure is found for an As-stabilized surface. before addressing microstructures we must deal with het eroj unct ions. surface treatment and temperature. In the case of heterostructures formed from doped semiconductors.1 Heterojunctions Below we describe the electronic structure of semiconductor heterojunctions. and in order to define the surface uniquely one has to specify the percentage of Ga and As it contains.388 Chapter 3. a model has been proposed with a quarter of the surface atoms missing. Electronic structure of semiconductor crystals with perturbations only Ga.8 x 2 reconstruction is found to be stable. then one obtains a semiconductor heterojunction or single semiconductor heterostructure. A rough distinction is that between Ga-rich and As-rich surfaces.55 shows an example. The remaining first-layer Ga atoms and the second layer As atoms undergo a buckling.30° and reconstructions in addition. Free carrier effects on the electronic structure can be neglected in these circumstances. They are treated in Chapter 6 in a systematic way. For the Ga-stabilized surface. may be thought of as units of two infinite half spaces. The two semiconductor materials are taken to be undoped.42. considered in the section above. x . the c . one filled with the semiconductor material.

e. What may change are the eigenfunctions of these energy bands. the corresponding wavefunctions will extend over both materials (Figure 3. then the eigenfunction belonging to this level and quasi-wavevector will be localized in material 2. at ko. almost all energy eigenvalues of the two infinite bulk materials.z(ko) of material 2.l(k) and E. and may be represented by a line extending from z = -co to 0. with 2-dimensional quasi-wavevectors kll.a(k) of these materials. Let us fix a particular quasi-wavevector ko. In the case of identical energy levels E. are also energy eigenvalues of the heterojunction. an energy level E. Generally. with E. Semiconductor microstructures 389 Stationary one-electron states As in the case of a crystal with a clean surface. i.If .it forms a bulk state of material 2.n(ko) of material 2 does not coincide with any of the allowed energy levels E.l(ko) of material 1 does not coincide with any of the allowed energy levels E. the Bloch bands E. heterojunctions of the kind described above possess a 2-dimensional rather than a 3-dimensional lattice translation symmetry. If there are energy levels at ko which are identical in both materials.a(kb) at dzflerent wavevectors ko and kb.56a by representing energy levels of this kind by lines extending from z = 0 to z = +co.l(ko) at ko of material 1. If an energy level E. it is not a priori clear what will happen. i.. then states extending over the whole heterojunction from -cc to f m will exist (Figure 3.e. ) in regard to their dependence on the position vector comz ponent XIIparallel to the interface. its wavefunction is spread out uniformly over the whole semi-infinite crystal from z = 0 to z = +co. This is illustrated in Figure 3. Just as in the surface case.l(ko) and E.7.(xI(. their one-electron states cp(x) are Bloch states (Pk.56b). if.3. There.l(ko) = EA(ko). If a matching of the corresponding two eigenfunctions and their derivatives at the interface turns out to be possible. it forms a bulk state of material 1.56~). Vice versa. The corresponding energy eigenvalues form bands in the 2-dimensional first B Z of the heterostructure.

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

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

232) the valence band discontinuity AE. the average hybrid energy difference S i . and the right one by 9 2 . Electronic structure of semiconductor crystals with perturbations moment has a non-zero macroscopic magnitude. value of 2 . then AE. If one were to ignore this dipole contribution. This is described by the relation + -1 ch .232) The difference AE. As pointed out above. The potentials on either side of the interface will add to the average hybrid energies and diminish their difference. In formula (2. is expressed as (3.392 Chapter 3.233) Beside the pure bulk contribution [E$ . If the hybrid energies were equal. - ecp2. The latter generally depends on the properties of the interface..1 and E. (3. By means of equation (3. Thus the charge transfer between material 1 and material 2 is governed by .-value of the combination ‘1/3’. Charge will flow until the average hybrid energy difference has been equilibrated by the potential jump. A semiconductor material i composed of cations ci and anions ai. zz [E.ecpi = F.€2. We denote the left boundary potential value by cp1. valence electron charge will be transferred into the material with the lower .cpz] may be estimated by means of the tight binding method developed in section 2.6.E&]. would obey the so-called ‘transitivity rule’ which states that the AE. no charge transfer would occur. The dipole contribution -e[cpl .2 If this difference is non-zero. which points up the importance of the dipole contribution to A E. In practice this ‘rule’ is rarely fulfilled.1 .2 at the heterojunction are given by the expressions (3. the potential cp exhibits a discontinuity in passing through such a dipole layer. Then the actual positions of the valence band edges E. forms a big molecule of the average hybrid energy 2 = (€2 &/2. The bonding energy level € b considered there forms a rough measure for the average valence band energy. .2] between the two valence band edges is called valence band discontinuity or valence band offset of the ‘material l/material 2’ heterojunction. The corresponding bonding orbitals IbtR) of equation (2.234) .315)’ € b is given for a zincblende type semiconductor.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 .E.-values for a succession of two heterojunctions ‘1/2‘ and ‘213‘ should add up to the AE. As is well-known from electrostatics. . the band discontinuity also contains the dipole contribution -e[cpi-pg]. the charge transfer will result in an electrostatic potential difference at the interface.

Al)As alloys. i = 1 . so that E ) = E k M . Often.3.237) 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. even in the case of the most thoroughly explored heterojunction.e. the difference [ c $ ~ t+M] between the positions of the deep level in the two materials is just the valence band discontinuity A E .1. Such an accuracy is difficult to achieve so that. calculated valence band discontinuities have also considerable uncertainty. Semiconductor microstructures 393 i.236) Considering relations (3. we denote these positions by E ) ~ . optical or transport properties of heterojunctions.234) to (3. it was shown that the difference between the position E+M of a deep level of a particular TM atom in a semiconductor material 2.10. and the potential contribution -e[cpl. equals the average hybrid energy difference between the two materials.235) Taking the deep level positions to be measured with respect to the valence band edges E& of the two infinite bulk materials. of the two materials. ~ 0 (3.EVi.Sk.5.7. 2 . the average hybrid energy levels on the two sides of the heterojunction align. Experimental values for valence band discontinuities of several heterojunctions are shown in Table 3.61 ~ ~ 1 . At this point it is advisable to recall a result concerning deep levels of transition metal (TM) atoms obtained in section 3. (3.1 eV. O t h e r band discontinuities Knowing the lineup of the valence band edge at I? for a particular hetero' ' junction. . hence AEIJ= [ETM 2 . There. To this day. In order to obtain theoretical values for valence band discontinuities. electronic structure calculations are required with an accuracy of less than 0. that being between GaAs and (Ga. (3.236). different values are obtained by different methods or even by different authors using the same method. in many cases. and the position E&M of the same deep level in a semiconductor material 1.721 to the valence band offset S matches I. Other experimental methods rely on measurements of photoemission. and also to the dependence of the discontinuities on the preparation of the heterojunctions. .E&M = 7.. ETM 2 . Below we . 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. This points up the experimental difficulties in determining valence band discontinuities. a great deal of effort is devoted to the task of obtaining more reIiable experimental and theoretical data for AE.T i ] .

and AE. . = E.394 Chapter 3. Because of AE. by means of the ratios Qv = AE.As with x < 0. follows from the gap energies Egl.39 1.As heterojunction with x < 0.Ecl = -AEv + AEg. The lineup thus obtained for the conduction band edge of a GaAs/Gal_./AE.42 and pure AIAs form indirect materials with the valence band maximum still at r.2 . In Figure 3./AE. it follows that AE. The gap discontinuity AE.42. = E. While GaAs and Gal-..02 1.238) where E.(eV) AE.Al.54 0.42 are direct semiconductors with both the valence band maximum and the conduction band minimum at I.Al. i. Ec2 = E v 2 + Eg2. In the second case.42 is schematically plotted in Figure 3.Al. Qc = 1.As heterojunction as an example.l.43 demonstrate this taking the conduction band edges of a GaAs/Gal-.96 0. are known. but the conduction band minimum at the B Z boundary point X .239) where AE.As heterojunctions with alloys having an indirect gap (z > 0. = AE. (3. Ec2 .2 .E. and AEc are expressed in percent of the gap discontinuity AE.41 InP/CdS 1. (3.2 are the gap energies of the two materials.42).46 0.29 1. one has Q .e.81 0. together with the lineup of the valence band edge. alloys ‘ with z > 0.Eg2 of the two infinite bulk materials. the conduction band + + .(eV) AEg(eV) Ge/GaAs 0.58a. Electronic structure of semiconductor crystals with perturbations Junction AE. If AE. These two cases are also to be distinguished in aligning the conduction band edges of the heterojunction.Al. AE. for GaAs/AlAs or GaAs/Gal-.1 of the ‘material l/material 2’ heterojunction. Often. For the conduction band discontinuity AE.Al. and Q c = AE.25 HgTe/CdTe 0.E1 is the discontinuity of the energy gap. can be calculated by means of relation (3.57 the valence and conduction band edges of the Gal-. the conduction band edges Ec1. A E . the two band offsets AE.35 GaAs/ZnSe 0.2 of the two materials are obtained from the relation Ec1 = E v 1 + E ~ I .As alloy are plotted as a function of x.23 0. In the f i s t case (x < 0.77 InAs/GaSb -0.24 1..63 -0.239).

- Fe(1+/2+) Composition x tc2 Ec2 X r I r r I Ev2 Ev2 Figure 3. the r and X levels forming the conduction band edges in.58: Conduction and valence band lineups for a GaAs/Gal-. The Fe(1 /2+) acceptor level is used as energy origin following the discussion in the main text. In part (a) ( x < 0. .6 + 0. GaAs and Gal-.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.Al. and in part (b) (x > 0 4 2 . 1985.As are also plotted in the respective other material where they do not form the conduction band edge.7. ( A f t e r Langer and Heinrich.4 -. . In the latter case. respectively.) f c c 2.3.0 3 1.As heterojunction.42) the alloy gap is direct. Semiconductor microstructures 395 Figure 3.!) the alloy gap is indirect.+ ---.AI.

and also E. it becomes evident that it is no longer meaningful to plot the conduction band edge throughout the whole heterojunction as before. say. that of GaAs at r. A look at Table 3. the second material must be placed on top of a crystal made from the first by continuing the crystal growth.1. while simultaneously the valence band edge of material 1 may lie above that of material 2.As alloy region forms a barrier.1 < Eva holds.59).396 Chapter 3. below the two edges of material 2. and HgTe/CdTe is of type 111. i = 1 .staggered.58b. Sometimes. In this case the gap of material 1 is located entirely within the gap of material 2. are. respectively. Recalling the discussion about the stationary electron states of heterojunctions at the outset of this section.Al. one has a heterojunction of type II. examples Heterojunctions cannot be fabricated by simply putting together two separately made semiconductor samples with plane surfaces. classifications. These are heterojunctions of type I with zero energy gap in material 1. Types of heterojunctions Consider two direct gap semiconductors with the valence and conduction band edge at I?. If both the conduction and valence band edges of a particular material. The staggered type II heterojunction occurs when we have Ec2 < E.i and Eci. and the misaligned case applies if Ec2 > E. a property which has been assumed above and which turns out to be crucial for the electronic behavior of a heterojunction. say of materiai 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. 3.1. Electronic structure of semiconductor crystals with perturbations edges of the two materials occur at different k-points. and that of the Gal-. again 1.7. the GaAs region does so. This case is referred to as heterojunction of type I. In the staggered case the heterojunction still has a gap. E. type ZZI heterojunctions are defined. If one would proceed in such a way the result would be a completely rough.1 < Ec2. polluted interface. CdS/InP of type 1 . What may be plotted is the lineup of the r and X levels forming the band edges in one of the two materials. the Gal-. This is done in Figure 3.Al. The illustration indicates that for the conduction band states of GaAs with wavevector r. may lie below the conduction band edge of material 2. 2 (see Figure 3.10 shows that the heterojunction 1 Ge/GaAs is of type I. In . The conduction band edge of one material. In actual practice. incapable of hosting electron and hole states which extend upon both materials.As alloy at X . and for the conduction band states of the alloy at X . There are several qualitatively different possibilities for the lineup of the two band edges E. a process referred to as epitaxial growth.2 Microstructures: Fabrication. InAs/GaSb of type 11-misaligned.

in contrast to ordinary deposition of an evaporated material which commonly results in a non-regularly structured layer. a third layer on top of the second etc. this kind of growth the underlying crystal. . I1 and 111.59: Heterojunctions of type I. 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 so-called substrate. namely Molecular Beam Epitaxy (MBE) and Metal Organic Vapor Deposition (MOCVD). For epitaxial growth to be possible. 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. Two epitaxial growth techniques are particularly important in this context. the two materials must have similar crystallographic structures. imposes its structure onto the growing layer. one obtains double and multiple heterostructares. and their lattice constants must be close to each other.60).3. 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. If one does so.7.

If one wants to proceed with a GaAs layer on top of the AlAs layer. Herman and Sitter.60: Heterostructures as grown by epitaxy: single heterostructure (a). The fact that MBE proceeds entirely in UHV may be exploited in controlling the growth process. for example.398 Chapter 3. Thus the As partial pressure must be much larger than the Ga partial pressure in the epitaxy of GaAs on a GaAs substrate. Unlike MBE. The whole growth process takes place in a vacuum chamber under UHV conditions (typically about 2 x 10-l' T o w ) .g. Arsenic atoms. If one. for example. one needs a fourth cell with Ga. multiple heterostructure (c). such as RHEED for studying surface perfection. In order to grow a GaAs/AlAs superlattice.. stick much less well on GaAs then Ga atoms. Doping of the layer may be achieved by opening a third effusion cell containing the dopant atoms.61. and the partial pressures of the various elements involved. the flux from the effusion cells. The principle of MBE is shown in Figure 3. double heterostructure (b). wants to grow a AlAs layer on top of a GaAs substrate. the substrate is placed in front of a number of effusion cells which contain the various chemical elements to be deposited on the substrate. e. and their shutters must be open at the same time. superlattice (d). the temperature of the substrate. or mass spectroscopy for analyzing the composition of the residual gas in the growth chamber (for more on MBE see. two cells are required. Electronic structure of semiconductor crystals with perturbations Figure 3. 1989). 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. one for A1 and one for As. MOCVD takes place in a chemical reactor at atmospheric . In this chamber. There are many parameters which influence the growth process. The atoms or molecules from the effusion cells may have different sticking coefficients on the substrate. One may employ characterization techniques which require UHV. in particular.

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

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

so to speak. (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.62. For misaligned type I1 superlattices shown in part f of Figure 3. solely the gap becomes indirect in coordinate space in this case. Bloch states are formed from the electron and hole states of the respective wells. Further discussion is given in the main text. c). an artificial atomic superstructure which is likely to result in a modified electronic structure. 2 2 Figure 3. .5 A). perlattices of the staggered type I1 shown in Figure 3. and of type I1 acting as a quantum well for electrons and a barrier for holes (b.62e.Semiconductor microstructures 40 1 a) Type II-staggered d) Type I . 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 2.62: Double heterostructure of type I acting as a quantum well both for electrons and holes (a).misaligned I P 5 c b Q. Parts (d). Heterostructures with such thin layers possess.

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

then band edge discontinuities may.5 3. Semiconductor microstructures 403 3.6 Lattice constant ( LI Figure 3. 6.5 0.0 P w >r 1. their lattice constants.3. their main .4 5.0 5. For two direct gap materials 1 and 2.63 are all of zincblende type.63: Energy gap versus lattice constant for diamond and zincblende type semiconductors.- v 2 g 0 2. but need not. Full lines represent alloys with direct gaps. occur.0 2 0. Lattice mismatch As the materials shown in Figure 3.4 6. and AE.6 5. If the gap discontinuity AE. the gap difference AE.5 2.0 h ' ZnS ' I \ I I I I I I I MnSe _ . Lines connecting two different materials indicate the gap energies of alloys made of these materials. vanishes. and dashed lines represent alloys with indirect gaps.8 6. Such a diagram is shown in Figure 3. differ from zero and their magnitudes reflect the gap discontinuity to a certain extent. 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. If a gap discontinuity does exist.5 1.0 62 . In general. provides some hints about their band edge discontinuities.7.63 for elemental and compound semiconductors of diamond and zincblende structure. then at least one of the two band edges must also exhibit a discontinuity. both the valence and conduction band discontinuities AE.

but also a buffer layer on top of the substrate which is used to accommodate part of the lattice mismatch strain. Because m t z ( i ) = 0.a l ) / a l of these constants is termed lattice misfit and measured in percent. only a few dislocations occur and the layer will have good structural perfection despite the strain. One says that the layer grows in a pseudomorphic phase. in many cases. the accommodation of the lattice mismatch by strain becomes energetically more costly than the formation of lattice defects. Otherwise one has lattice mismatched heterostructures. If f is less than a few tenths of a percent. a:! of the two materials are different. For a lattice misfit f of a few percent the critical thickness may reach values not much smaller than 100 A. As long as one stays below d. it can be completely neglected. (3. Ideally. the layer material will not grow with exactly the same lattice parameters as would a free standing bulk crystal of this material. The strain will then be released by the formation of dislocation lines (see section 3. We suppose again a layer of cubic material 2 which is growing on a (100) surface of a layer of cubic material 1. 2 are a. in particular of dislocations. In order to grow lattice mismatched heterostructures it is important to know the distribution of strain between layers of different thicknesses. The relative deviation f = (a:! . If they differ. eyY(i) and e z z ( i ) with e r X ( i ) = eyY(i). but with a lattice constant parallel to the layers equal to that of the substrate. in epitaxial growth. the lattice constant a1 of the substrate (material 1)should be equal to the lattice constant a2 of the layer (material 2). and that the cubic lattice constants a l . Such layers may be the substrate and the epitaxial layer.240) with cll(i) and clz(i) being the elastic stiffness constants of the cubic layer of material i. and this increase grows larger as the layer becomes thicker.404 Chapter 3. The independent stressstrain relations for a particular layer read “ 2 4 4 = cll(i)€zz(i) + c12(i)[err(i) + €yy(i)]. the lattice mismatch has only little effect and. One speaks of lattice matched heterostructures.. and the non-vanishing strain components are e x s ( i ) . One speaks of strained layers. The critical thickness depends on the magnitude of the lattice mismatch.2). Electronic structure of semiconductor crystals with perturbations structural differences lie in their different cubic lattice constants a. Past a critical thickness d.. The non-vanishing components of the stress tensors ~ ( i of the two layers i = 1 . it follows from (3.240) that . The adjustment of the parallel lattice constant creates a mechanical strain in the layer. Suppose that a layer of a cubic material 2 is growing on a (100) surface of a layer of cubic material 1. The corresponding strain energy increases the total energy of the layer.(i) ) and ayy(i)with aee(i) = ayy(i).

This was anticipated in the discussion above.1 x 1011 dyn/crn2 and c12 = 6. 1974). In this context. From theoretical considerations and experimental studies it is well known that such effects can be quite large (Bir. provided the elastic constants of the two layer materials are comparable.31 el/ under this strain. Pikus. The degenerate heavy-light hole valence band maximum of Si splits by 0.7. Using the stress and strain components. The strain becomes. To produce the same splitting by means of uniaxial strain applied from outside. in particular.241) For the parallel strain components e z Z ( i ) and e y 3 / ( i ) one has 4 2 ) .04. . One may take advantage of this to adjust the band discontinuities of a heterostructure to specified conditions. using the elastic stiffness constants c11 = 16.E v y ( l ) = t.4 x 1011 dynlcm’ of Si. Semiconductor microstructures 405 (3.243) where c = i [Cll(i) + (1 . the thin layer is more heavily strained than the thick one.242) equals the lattice misfit f divided by 100%.&(1) = tyy(2).Ki)Cl2(i)l. This example shows that considerable changes of the band structure are to be expected because of the lattice mismatch strain in heterostructures. a pressure of 73 Kbar would be necessary.242) The total strain E defined in equation (3.245) According to these relations. and e Z z = -0. energy levels in different materials or at different points of the first B Z can shift in dserent ways. with the result (3.3.03. Another general point to be mentioned in the context of lattice mismatched heterostructures concerns the effect of strain on the band structure..ai . so to speak. ai (3. an additional degree of freedom for tailoring the properties of a heterostructure. This means. To give an example. corresponding to a lattice misfit of 4% (see below). The strain components in the Si layer are e X x = cyy = 0. the total elastic energy Eda of the two layers may be calculated. we consider a Si layer on top of a Ge substrate. (3. t = a2 .244) Minimizing Eela with respect to txZ(2)(or ~ ~ ~ yields)the conditions ( 1 ) (3. that the substrate will be almost unstrained and the epitaxial layer will accommodate almost the whole misfit strain.

amounts to about 30 A which is rather small. = 0. With this. one also considers heterostructures between Si as substrate and Sil-.As microstructures are used in devices like HEMTs.Asy 1 for all compositions x and y.25 x x e V . Superlattices based on InAsfGaSb heterostructures have been the subject of intensive basic research. For Inl-. especially for InAs/GaSb with x = y = 0. and the conduction band discontinuity has the constant ratio Q.406 Chapter 3.As multiple heterostructures are the prototypes for lattice matched type I microstructures. a Sil-.As linearly with x according to the relation AE.Gey substrate on which a Sil-. For the gap discontinuity A E .45 x x eV. Therefore. The two band edges are lower in Inl-.As than in GaSbl-. and QW laser diodes. Electronic structure of semiconductor crystals with perturbations Particular compositional microstructures GaAs/(Ga. The conduction band edge of InAs is 0. = 1. = 64%.Al. including the trivial GaAs/GaAs homostructure.As/GaSbl-yAsY heterostructures with larger x and y.Al. one has staggered type I1 heterostructures. alloys with low Ge content (x < 0. Ge) alloys may also be used as substrates.As alloys have already been discussed in the context of Figure 3. For 0 < y < x. Both layers are strained in this case. The critical thickness d. 9 1 8 ~ 0.5) as epitaxial layers. can be 100 A or larger depending on the actual value of x. For small values of x and y.85 x x eV for the conduction band discontinuity. Perfect lattice matching is achieved if y = 0 .42. Beside providing model systems for basic research. the valence band discontinuity takes the constant ratio Q v = (45/125)% = 36% of the gap discontinuity.Al.Ga. heterojunction bipolar transistors (HBPT).14eV below the valence band edge of GaSb. In this case d. (Si. The valence band heterojunction scales almost discontinuity A E v of the GaAs/Gal-. (In.Al. + Si and (Si.Ge. Consider. we add some quantitative estimates.Ga.65 A. GaAs/Gal-.Al)As GaAs/Gal-.082. Here. for which the conduction band edges are above the valence band edges in both materials. as long as we consider the direct region x < 0.Ga. The valence and conduction band edges of the Gal-.Ge) The lattice constants of Si and Ge are. This gives the lattice mismatch of 4 %. the strain in the alloy layer . one has a misaligned type I1 heterostructure. we have A E .As/GaSbl-yAsy material system forms heterostructures of type 1 . respectively. these SLs exhibit metallic behavior. alloy layer is grown first. followed by a pure Si layer. which has already been used above. 5. = 0. Under certain conditions.43 A and 5.57.Ga)As/Ga( Sb. This gives A E .Ge.As) The Inl-. for example.

7.53Gao. The 1 type I1 Si/Sil-. The former still has its highest valence band edge in the alloy.AsyP1-y may be thought to be formed of the four binary compounds I d s . Thus the Si/Si0.5 heterostructure on Si0.Cd.y’. with both the highest valence band edge and the lowest conduction band edge in the alloy.Ga.55 p m wavelength.418 .5Ge0. Generalizing Vegards rule.zy.~ alloy of another composition x’.5 heterostructure on top of a Sio.5heterostructure on top of a Si substrate. . the lattice matched alloy transforms from pure InP to an Inl-.Ge.z)(1. alloy varies almost linearly between 1. which is the wavelength with minimum losses in quartz-based fibers.47As/InP based microstructures.P1-. the lattice constant of the alloy may be estimated as 6. Varying with that of InP if the relation z = 0. because here the free electrons are hosted by the pure Si layer.013~) y between 0 and 1.53Gao. Because of the different strain distributions.Sel-. with composition ratios given. from Zn(S. (Ga. 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.058(1.In)(As. Se) double heterostructures.~Ge0. and that in the Si layer tensile.451~(1. where the mobility is much higher than in the alloy layer. Cd) (Se. more strictly.189y/(0.As.0.As alloy with I = 0. Blue-green laser diodes have been fabricated from such structures.y) 5 . deposited on top of a GaAs substrate. and z(1-9). 6 5 3 ~ ~ 5.tCd+! SY!Sel-. embedded between other 11-VI-compound layers.y). It matches holds. therefore. S.Ge. (1-z)(l-y). If the same Si/Sil-.53Gao.S) /GaAs ZnSe and GaAs form an almost unstrained type I heterostructure. respectively. The latter is of type I.5Ge0.P)/InP Quaternary alloys of composition Inl--rGa. alloy of a certain composition z . Semiconductor microstructures 407 is compressive. + + + (Zn.47. heterostructures are better suited for applications in electronic devices (in particular HEMTs). Using Ino. the band alignment of a Si/Sio.3.869(1. y is combined with a Znl-.75Ge0. If a Znl-. 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. The fundamental energy gap of the lattice matched Inl-.z)y 5. Lattice matched Ino. double layer is grown on Si substrate.47As/InP microstructures may be used to fabricate HEMTs.35 eV for InP and 0.85 eV for Ino.Se)/(Zn.25 substrate is of type 1 . by (1-z)y.47As.Cd)Se/Zn (S. one obtains a strained heterostructure of type I.Ga.25 substrate differs from the band alignment of the same Si/Si0.75Geo. InP. GaAs and Gap. the whole mismatch strain occurs in the alloy layer while the Si layer remains unstrained.

minibands arise just as in the compositional superlattices considered above.Te/PbTe have a potential for applications in infrared laser diodes.Te alloys the gap opens at 2 = 0.of type I11 for z = zo. can be applied in infrared detectors. Pbl-.4 %.Te/PbTe heterostructures are of type I for z < 20. generally. Thus. HgTe forms a type I11 heterostructure with CdTe. .Sn. one has zo M 0. the L$ state forms the valence band edge. Microstructures based on Pbl-. are shifted by the same amount of energy. for sufficiently small 2 .Te/CdTe forms type I heterostructures which. Pbl-. (Pb.15.Sn. Thus.Cd. Doping microstructures nipi-structures Semiconductor samples with alternating n. and the Lg-state forms the conduction band edge (see Figure 2.Sn)Te/PbTe The lattice misfit between PbTe and SnTe is about 2 %.Sn. Dohler.64a. with inverted band edges of the well material in this case. In Hgl-.02 e v ) .and p-layers. and again of type I for 2 > 2 0 . The most common nipi-structures are those based on GaAs. 1972). 1970. Being a zero gap material. For PbTe.408 Chapter 3. Sn.15 < 2 < 1 the alloys ' are direct gap materials with the valence and conduction band edges at. this level ordering is inverted.Cd)Te/CdTe HgTe and CdTe are lattice matched because the lattice misfit is smaller than 0.Te alloys must go through zero for some composition TO.Te alloys are direct gap materials with the conduction and valence band edges on the first B Z boundary at L. The oscillating space charge distribution gives rise to an oscillating electrostatic potential which modulates the valence and conduction band edges as shown in Figure 3.35). For 0.4. so that strain effects in Pbl-. however. For SnTe. Sn.and p-type doped layers may exhibit properties similar to those of superlattices composed of two different materials (Esaki. At 77 K . Depending on strain.Cd. Their periods.I In this range. at a given position.and np-junctions with alternating negatively and positively charged intrinsic (i) regions between the neutral n. Tsu. namely the electrostatic energy of an electron. type I1 situations also seem to be possible. If the modulation period approaches the nanometer range.Te/PbTe heterostructures are not negligible. Hgl-. Doping superlattices are principally of type I1 because the two band edges. The valence band offset turns out to be rather small ( M 0. the gap of Pbl-. cannot be made smaller than 10 nm because of the unavoidable diffusion of dopant atoms. Such doping superlattices may be thought of as periodic arrays of pn.structures. In this context they are sometimes referred to as nipi . Electronic structure of semiconductor crystab with perturbations (Hg.

spikes of dopant atoms of only a few nanometer width may be constructed in an otherwise undoped sample. and holes in the case of p-type &doping.3. is used for such a SL.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. 1994). 3.and As atoms. A GaAs layer of the SL contains a number 2n of (001) lattice planes alternatively occupied by Ga and As atoms. Schubert.. 6-doping structures are always of type 11. and p-type 6-doping by means of Be. 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.7. e.g.e. we will discuss this in the case of compositional superlattices (SLs).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. The notation (GaAs).64b).. One speaks of planar doping or 6-doping (see. by means of Si./(AlAs). The primitive unit cell of .7. In GaAs. Semiconductor microstructures 409 a) m + + + + I b) + + + + + + + + + + + + + + -1 z - - I I v Z Figure 3. Below. for example. i. The interface is taken to be parallel to a (001) lattice plane. e. &doping structures By means of MBE.g. 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. n-type &doping has been achieved. The potential well experienced by the majority carriers represents a barrier for the minority carriers. GaAs and AlAs. Like nipi-structures. electrons in the case of n-type &doping (see Figure 3.

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

These methods yield the totality of energy bands of a microstructure in all parts of the first B Z .66: First B Z of the (GaAs)3/(AlAs)3 SL of Figure 3. Important properties of the corresponding SL eigenfunctions are illustrated in Figure 3. Al)As/GaAs/(Ga. This illustrates the general discussion of subsection 3.1 about the existence of eigenstates of heterojunctions which arise from bulk states with different k-vectors in the two materials . in many cases the application of bulk methods to artificial microstructures is not appropriate. both AlAs-X-states and GaAs-r-states contribute to the conduction band states of the SL. 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.X line of the first bulk B Z . 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. A1)As double heterostructures. Semiconductor microstructures 41 1 1".68 for a (GaAs)7/(AlAs)T SL. A1)As layers. In the case of the (Ga. Moreover. In this way an SL is simulated whose electronic structure can be calculated by means of any of the bulk band structure calculation methods. The lowest valence and conduction band states are represented with respect to their spatial variations and symmetry characters. one embeds the GaAs layer between thick but finite (Ga. also along the r . In these cases one may use a procedure similar to the slab method for surfaces: At the outset. and then repeats this slab periodically. However. While the valence band states are well localized in the GaAs layers and are dominantly composed of GaAs-r-states. even the . Al)As/GaAs/(Ga. to demonstrate the folding character of the SL band structure. Bulk methods may also be used to calculate the electronic structure of non-periodic microstructures such as GaAs/AlAs single heterostructures or (Ga. Figure 3. and repeats the slab thusly formed periodically. A1)As double heterostructure. line of the first SL B Z and.

and plotted upon the r . 1986. The situation is similar to the case of the shallow levels of impurity atoms . exists in the shallow level case. and changes of the band structure are expected only for selected bands and in the vicinity . Fortunately. and Enderlein. Electronic structure of semiconductor crystals with perturbations - 3 .7Alo. -€ Figure 3. another method.if one would try to obtain these levels by means of a full bulk band structure calculation method the same difficulties would occur. namely the effective mass theory.3As)3SL calculated by means of the TB method. Bechstedt.412 Chapter 3.67 Valence band structure of a (GaAs)3/(Gao. where the kinetic energy is small enough to allow the perturbation potential to produce measurable effects. (After Riicker. The situation in the case of artificial microstructures is comparable: the perturbation potential is relatively weak.) changes of these few minibands are small. Hanke.-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). The bulk methods are often not accurate enough to reproduce them sufficiently well. It is particularly well tailored to calculate the small changes of electronic structure occurring at the conduction band minimum and the valence band maximum.

. and the symmetry character of these states (right).77 eV. the average potential difference has still an abrupt change at an interface. Semiconductor microstructures 413 GaAs A1As r X Figure 3.88 eV. well localized in the GaAs layers and are dominantly composed of GaAs-r-states.e2 = 1.e. Even if one averages out the microscopic potential fluctuations over a unit cell.75 eV.7. There are. The perturbation potential. is far from being smooth on the atomic length scale. the difference of the periodic oneelectron potentials of the two m a t e rials of a heterostructure. Burt.3. e3 = 1.h2 = -0.) of critical points. 1985.19 e V . for a (GaAs)7/(A1As)7 While the valence band states are SL. also differences between the shallow level problem and the microstructure problem. and are composed of both AlAsX-states and GaAs-I'-states. We will address this question below (for a detailed discussion see. For this reason one has to determine at the outset whether or not the effective mass theory developed in section 3.(After Rucker.g. e. i. el = 1. . h l = -0. conduction band states extend over both layers. however. 1992).3 can in fact be applied to artificial microstructures.11 eV.68: Localization of the lowest valence and conduction band states of the SL at the center r of the first SL B Z (left).

at critical points off r. Both edges should occur at the centers I? of the respective bulk B Z s . = (3.may be written as The two envelope functions F.l(x) and Fv2(x) obey the effective mass equations F. the eigenfunctions & l ( x ) and $ 4of the) ~ two material regions 1 and 2 having energies. If.248) F V ~ ( X ) E . ~ ( x ) .2 at f.i(x). we restrict ourselves to eigenstates of the heterojunction having energies in the vicinity of the band edges E. which we will assume. we suppose that. The two band edges at are assumed to be non-degenerate and isotropic (the degenerate case will be treated separately).1 and E. then the effective mass theory is applicable as well. Electronic structure of semiconductor crystab with perturbations Effective mass theory for microstructures Consider a single heterostructure. SL shown in Figure 3.F. say from f and X as happens in the case of the conduction band states of the (GaAs)7/(AlAs)i. provided the conditions of validity of effective mass theory are satisfied in each of the two regions separately.l(x) = E. these equations may be written as one equation for the envelope function . Furthermore. close to the band edges Evl and E. respectively.68. If the eigenstates were composed of bulk states from different parts of the B Z . Non-degenerate band edges In the case under consideration. 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. (3. an eigenstate of the heterostructure may be formed only from bulk states at an off-center critical point like X . Accordingly.414 Chapter 3. however.249) Formally. F . then the effective mass theory could not be applied. Then these eigenstates are composed of only bulk states with k-vectors in the vicinity of r. all bulk band energy levels are far removed from the energies of the eigenstates under consideration.2 of the two bulk materials. x in m a t e r i a l 1. x in m a t e r i a l 2. 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 .

At z = 0. 0 . matching conditions are required. Y. . which we will now discuss. no general proof exists for the continuity of the Bloch factor at a heterostructure interface.(x) also would have to be continuous there since the total wavefunction @() must . equation (3. The only case in which such a continuity is assured is that of a 'heterostructure' composed of two identical materials. the solutions for the two half spaces must be connected in an appropriate way to form an envelope eigenfunction for the entire heterostructure.250) of the whole heterostructure by introducing a z-dependent effective mass m * ( z ) and a z-dependent band edge E.3.6 ) = F ( . Semiconductor microstructures 415 (3.(x). by We write this one equation as (3.253) (3.254) is the Bloch factor of the heterostructure. the envelope function F. To do so.253) for the total wavefunction &. it is commonly . Unfortunately.z +6) (3. but not at the interface. respectively.x be continuous everywhere. Thus the condition Fv(z. we derive a condition for the change of the envelope function across the interface. If this factor was continuous at the interface.252) holds only within the two material half spaces. 0 Y. Firstly. Having this obvious result in mind. Clearly.255) should hold in the limit 6 --+ 0.7.(z) defined.x (3. To this end we consider the interface behavior of the Bloch factor ud(x) in equation (3. Thus it determines the possible envelope function solutions for z < 0 and z > 0.252) The true wavefunction $ ( ) of the heterostructure is given by the expression .

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

In the effective mass equation (3. h2 (3. as any reasonable kinetic energy operator must be in order to avoid complex energy eigenvalues. In fact. (3.Vm*a(z)] is Hermitian if a. and must be rejected.25 7) With this replacement the effective mass equation (3. This condit.3.261) with l/E. 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.256) involves more than just the hermiticity of the kinetic energy operator.259) For F u ( z ) the Schrodinger equation follows as where EL is given by EL = E . and since the effective mass does so also.256) cannot be justified.258) the band edge plays the role of an external potential. Its replacement by the right hand side of relation (3.252) is also applied at z = 0 after the kinetic energy term has been replaced in accordance with _- h2 2m*(z) v 2 -+ .- 2 m*(z) v. Since it depends only on z . . h2 --v. The kinetic energy operator of the Schrodinger equation (3. Semiconductor microstructures 417 which is known as the BenDaniel-Duke boundary condition. therefore as + + (3.B y = -1.257) is Hermitian.:' + m. by the hermiticity demand alone since there are also other ways to introduce hermiticity.2/4)[m*a(z)Vm*~(z). The original form -[l/2m*(z)]V2 of the kinetic energy operator is not Hermitian.252) becomes Integrating this equation with respect to z from -6 to +6 one obtains the boundary condition (3. This implies that the boundary condition (3. one can easily demonstrate that any operator of the form -(F.p. y are real numbers obeying the relation (Y . however.i k 2m*.256). as the average inverse effective mass (m.Vm*~(z)+m*~(z)Vm*~(z).7. - .ion follows automatically if the Schrodinger equation (3.T1)/2.

265) must hold for 6 + 0.264) must be continuous at z = 0. The z-dependent * * factor F~ (2) of F. To determine the condition for the derivative with respect to z .263) with DE$(z) = DYZAl for z < 0. one defines the Hermitian Hamiltonian matrix (3.263) becomes . these general results are specified for the fourfold degenerate rs valence band edge of diamond and zincblende type materials. The solution of equation (3. ] ) m’ a d (3. F U (z)lz=-6 = F u =+ * * (z)I~=+6 (3. and Dg$l(z) = D. Below.2.e.ELl for z > 0. Using the 4 x 4 Luttinger-Kohn Hamiltonian of equation (3. the effective mass equation (3.# 0. ( x )in equation (3.266) which exists for any value of z including z = 0 and equals H 1 for z < 0 and e H z for z > 0. i. 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 Hamiltonian’s H i of the two materials i = 1.418 Chapter 3..263) may again be taken as a plane wave (3.73).264) parallel to the layers.74).262) derived in equation (3. The boundary conditions for F v ( x ) at the interface follow in the same way as in the non-degenerate case. 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 . 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 ) .

y3 using equations (2. [y2(zj(k: (3. Semiconductor microstructures 419 (3.f i ( z ) .g ( z ) . L .75) to (3.2i73(z)k. N in equations (3.268) The quantities Q ( z ) . From equation (3.3.k i ) .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: .kg] .381).72.272) The constants M .7. ? ( z ) here are the differential operators k(z)= --a .78) have been replaced by the Luttinger parameters y1.

. In the case of SLs composed of GaAs and Gal_. + Electron states Effective mass equation and its solutions For the zincblende type materials we are considering. We suppose that there are none. denoting their common value by m. To be specific. The two effective electron masses m:l and mE2 generally differ.69: Geometry of the SL whose stationary electron and holes states are calculated in the text. and the lattice constant in z-direction by d . 3. we discuss the modifications which occur if m.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.42.69). Later. We want to calculate the stationary electron states of this SL with energies in the vicinity of the conduction band edges Ecl and E.As this is a reasonable approximation. These states are the ones which would host the free electrons of the SL. but we will initially assume that they are equal. and ‘2’ with a Gal-.420 Chapter 3. Electronic structure of semiconductor crystals with perturbations L XJ Figure 3. The thicknesses of the two material layers are denoted by d l and d 2 .As alloy for z < 0. if there were any.Al. the conduction bands ’ are non-degenerate and isotropic in the vicinity of I. with d = d l d 2 ( s e e Figure 3.l and m:2 are different. we may associate ‘1’with GaAs.7.2 using the effective mass theory derived above. as we did before.Al. The effective mass equation for the electron envelope function Fc(x) the of .

. f o r Id + d l < z < (1 + l ) d .(ld -Fc(ld dz -F.(ld + d l + 0 ) . The component k varies within the (1-dimensional) first B Z of the superlattice between .276) In solving this equation. It must have the form ( 2 a / L d )x (0. i f (3. -co < 00.277) +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). is given by EA = E .252) if we set v = c and f o r Id Ec(z) = < z < ld+dl Egl +AE. the boundary conditions Fc(ld d + d l .7.0 ) = F. f l .0) = -F. The z-dependent factor F.) in order to guaranty the periodicity of F&) with respect to the periodicity interval.r / d and r l d . The Bloch factor U c k ( z ) of the superlattice has to be distinguished from the Bloch factor uco(x) of the two bulk .x (3.260) describing a plane wave of wavevector kll parallel to the layers.278) where k is the quasi-wavevector component parallel to z .(z) of Fckl. . (x)of equation .(x)obeys the equation where E. d . .(z) may be written as a lattice-periodically modulated plane wave F. f 2 . Semiconductor microstructures 421 thus specified SL follows from equation (3. The envelope function F ( ) may be taken in the form Fckl. - (3. Applying the Bloch theorem to the SL under consideration it follows that F.274) Here 1 is the integer index of the various SL unit cells.(ld dz d dz + 0). and U c k ( z )is the superlattice Bloch factor.(z) = Fck(z) = L e ik r U c k ( z ) . < 1 (3. (3.3.

Electronic structure of semiconductor crystals with perturbations materials defined in equation (3.279) The effective mass equation (3. the matching conditions (3.277). It reads (3. an electron with such an energy cannot penetrate within the superlattice layers made of material 2.280) with K as a real number which determines the energy E' by means of the relation I E . According to classical mechanics. For the wells 0 < z < d l . and the Bloch condition (3. (7i2/2mr)ki. it will be confined to layers consisting of material 1.278) define an energy eigenvalue problem which differs from the well-known Kronig-Penney problem only by notation. We restrict ourselves to energy values 0 < E' < A E . bl as coefficients which are still to be determined. there is a certain probability for the electron to tunnel through a material 2 layer and reach the next neighboring material 1layer. or E.281) and a l . 0 < z < dl. but smaller. Although the probability for an electron to stay in material 1 is not unity. In quantum mechanics. As has already been mentioned.422 Chapter 3. In the case of SLs this exercise takes on real physical meaning. The total wavefunction &(x) &k(x) contains the product of both. If it hits the interface to material 2.1 < E < E. as in classical mechanics. dl < z < d. The occurrence of two different Bloch factors reflects the fact that two periodic potentials are present in a superlattice. it is still much larger than that for material 2. (3. Schrodinger's equation (3. = . and one due to the artificial superstructure.1 AE.275). one due to the natural crystal structure.]F(z)= ale iKZ + ble-iKz.254). the reflection is not complete. The latter problem constitutes an exercise of elementary quantum mechanics and is commonly used to demonstrate the existence of energy bands.282) where we have set . In the wells and barriers the wavefunction F. and bamiers for the layers of material 2. (3. one uses the terms quantum wells for the layers of material 1.276) yields + + F. then it will be reflected back to the interior of its material 1 layer. For the barrier d l < z < d one has Fck(z)= a2enz + b2e-nz. meaning energies below the lowest allowed energy in material 2 for a given value of kll. In the following we sketch its solution.]F(z)is given by different expressions.h2 K2 2 m ~ ' (3.

are termed minibands and minigaps. the sub. . there are discrete energy eigenvalues EL. Ti2 . these energy bands exhibit an additional dispersion with respect to the wavevector component kll along the SL layers. Bands which arise for fixed IF and varying kll are termed subbands. Semiconductor microstructures 423 KE.and &-valuesmust satisfy equation (3. a2.285).. . Commonly. the determinant of the matrix of exponentials must vanish. if k varies within the first B Z .= 2 2mE -(AE.1 E L ( k ) .2. for a given quasi wavenumber k. respectively. while the k or miniband dispersion follows from the artificial microstructure. one still has to add E.K~ +sin(Kd)l sinh(~d2) cos(kd). both are determined by the energy E L through equations (3. The values of K and K are not independent of each other. In Figure 3. n = 1. .283). These equations read For this set to have a non-trivial solution.281) and (3.285) Allowed K .283) The four coefficients a l .3. = 2Kn: (3.and minibands of a SL are schematically plotted. The effective masses of the minibands become negative at the boundaries of the superlattice B Z in the case of odd band numbers n.70. separated by energy gaps. They split into energy bands E&(k). This yields the secular equation cos(Kd1) cosh(tid2) tc2 .285) represents a condition for EL.7.. but with varying values of k . b l . As we know from the solution of the latter. the energy bands and gaps for a fixed value of kll. (Ti2/2m*)kll to according to equation (3.277). (3. b2 are governed by a set of linear equations which follows from the 4 matching conditions (3. To obtain the total energy eigenvalues E.276). = Ecn(k) of the superlattice.EL). with the result + Em(k) = E&(k) h2 + Egi + -kll 2mr (3. Thus equation (3. It coincides with that of the Kronig-Penney problem. and at the center of the B Z for even n.286) Unlike the Kronig-Penney problem. The kll or subband dispersion is due to the natural crystal structure. central part.

and/or the barriers AE. Also shown are the two limiting cases of extremely wide and/or high barriers and of narrow and/or flat barriers.. For infinitely high potential walls the secular equation (3.285) dominate over the cos(kd)-term on the right hand side which is responsible for the k-dispersion. and practically zero within the barriers.and subbands of a superlattice. 2 .287) . the superlattice decomposes into isolated quantum wells in the limiting case under consideration. . are high. They give rise to the energy eigenvalues 2 El = cn 2mE . then the hyperbolic terms in equation (3. In the lower part of the figure the wavefunctions are illustrated.424 Chapter 3. Neglecting the latter. the minibands degenerate into discrete energy levels. Obviously. (3. Multiple quantum well versus superlattice behavior Figure 3. n = 1 . . termed sublevels. Electronic structure of semiconductor crystals with perturbations Figure 3. . The solutions of this equation are K-values of the general form K = (7r/dl)nwhere n is an integer.285) becomes sinKd1 = 0. 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.70: Mini.70 also shows two enlightening limiting cases. These levels are just the discrete energy eigenvalues of a single quantum well.

the superlattice period d should not be large in comparison with the electron wavelength X = 2 r / k corresponding to k. Similar values are obtained for other semiconductors.70). 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. one gets A =" 20 nm. the perturbation theory developed in section 2. for large n. that of extremely narrow and/or flat barriers (see Figure 3.067 m . For a conduction band electron of silicon. In this limit the minigaps vanish completely.289) According to this expression. They decrease with band number n.. 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. 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. gaps are opened at the Bragg reflection points k = ( n n / d ) of the 1-dimensional reciprocal lattice of the SL. For the energy splitting between the two bands E&+l(n/d) and E & ( n / d ) . one gets a value of 57 meV for the first energy E level ELl. and the superstructure which distinguishes the superlattice from a natural crystal has no effect at all. In the first non-vanishing approximation with respect to the SL potential. In other words. This proves and specifies the expectation stated at the outset of this section. In zero-th approximation the secular equation (3.288) The confinement to the well region is complete in this limit. as distinguished by the coupling of quantum wells with one another.285) takes the form k = K . Thus.3. We consider next the opposite limiting case.4 yields E&+1 ( : ) -E L ( : ) = -AEc 7rn 1 sin ( y d g ) . the minigaps are proportional to the conduction band discontinuity AE. (3. The limit of narrow and flat barriers is the true superlattice case. that substantial changes of electronic structure are to be expected if the superstructure occurs on a sufficiently small length scale. Semiconductor microstructures 425 and Bloch factors (3. having an energy equal to the average thermal energy $kT at room temperature. or smaller than. Assuming d l = 100 A and m = 0. The length scale turns out to be that of the de Broglie wavelength X of an electron. 10 nm in order that superlattice effects on free carriers may become important at room temperature.7. The en- . there are no substantial energy gaps even if sufficiently wide and high barriers exist. Thus the layer thicknesses of superlattices have to be on the order of.

Electronic structure of semiconductor crystals with perturbations ergy eigenfunctions also have non-vanishing values within the barriers. i.291) Each subband n gives rise to a step-like partial DOS. Then the DOS p s ~ ( Eof the SL is obtained as ) To evaluate this expression further. Electron density of states of SLs and QWs The general expression (2. The heights of the steps have the constant value ( m * / n 2 h 2 ) ( n / d )while the step widths depend on n. In a superlattice. 2 / 2 m E ) ( n ~ / d 1 and the step widths of the staircase scale with ( n / d ~ ) ~ .212) by the expression given in equation (3.e. the miniband dispersion EA(k) has to be known. an electron having a particular allowed energy.291) for p ~ over all subbands results in a staircase-like DOS as schematically ~ w shown in Figure 3.(k) in formula (2. the tunneling will be amplified. For very wide QWs. of (3.286). The summation in expression (3. in the limit d l -+ 00.212) for the density of states (DOS) p ( E ) of a 3D crystal may be immediately applied to a SL. To this end one has to replace the energy band structure E.71. Such behavior of the DOS of an electron which is free to move only in two dimensions was already found in section 2. and the DOS of equation (3. and non-zero but constant above. One has so called r e s o n a n t tunneling. In the particular case of isolated QWs the dispersion vanishes completely. If the barriers of . as in a Fabry-Perot resonator in the case of light. the QW are taken to be infinite.291) yields + (3. being zero below the band bottom E L E g l . in contrast to multiple quantum wells where these values are almost zero. may tunnel from its quantum well through the barrier to the neighboring well. Since there it encounters the same allowed energy value from which it may tunnel back.5. then the energy levels EAn are given by ( h .291) takes the form of the DOS P M Q W ( E ) a MQW structure. Equation (3. It causes the discrete energy levels of isolated quantum wells to broaden into bands. the staircase-like DOS transforms into the smooth square-root-like DOS p 3 ~ ( Eof an electron free to ) move in three dimensions.426 Chapter 3. )2.292) .

Semiconductor microstructures 427 4 7 3 3 0 1 Q 0 2 3 1 Figure 3. with f = limd. For the secular equation (3. different mass factors will appear on the two sides of the interface and they will not cancel. First. Refinements In the above treatment of the electron states of a SL.286) becomes different in the two material layers.The case when they are at the DOS occurs for energies E at the subband bottoms.7. in solving the secular equation. ~ This results in an additional contribution (h2/2)[mZ-'(z) . The additional term introduces a kll-dependence of the envelope function F& which otherwise depends only on the z-component k .E ~ .260). The staircases of the DOS in Figure 3. have to be replaced by (m&'mal)K.(dl/d) being the geometrical fraction of material 1 regions in the infinite MQW. n and E' must be written with m.. and mE2 instead with mE. the following modifications will occur. Second.285) this means that all K ' s except those which are factors in arguments of trigonometric functions.' ] k to the SL potential.71: Electron density of states PQW of a QW as function of energy. If this is not E the case. the kll-dispersion of the total energy eigenvalue in relation (3. Finally. Another simplification made in the above treatment of the electron states of a SL. was the assumption that no electrons are available to occupy the SL . in the boundary conditions (3.283) between K and E i and. / d z ) . respectively.3..71 are always below or at the limiting fractional 3D DOS f p j ~ ( E ) . the effective masses mzl and m 2 were assumed to be the same in the two materials.281) and (3. the relations (3. as may be seen from equation (3.277) for the derivative ( d F .

For a given number of electrons in SL states.293) .aGao. The net effect of the two potential parts is repulsive.268) by installing there the valence band edge profle E. (3. bands. this potential change may be decomposed into a Hartree and an exchange-correlation part.3Gao. Hole states We consider a QW structure composed of zincblende type well and barrier materials which are both described within the Luttinger-Kohn model. It will be particularly pronounced for isolated QWs. If there are such electrons present. well bottom bends up with rising n s . containing The different numbers ng of electrons per ~ r n .7As QW of 100 A width. 6 xlO’*cm-* Figure 3.72: Self-consistently calculated potential profiles and energy levels for a Alo. and the energy levels are shifted to higher energies.(z): 0 E. the potential seen by an electron will change due to its interaction with other electrons in the SL bands. As in the case of bulk semiconductors.~ . The effective mass equation for the hole states of such a QW with energies close to the well bottom follows from equation (3. Electronic structure of semiconductor crystals with perturbations t 0. this flattening will be enhanced by greater localization of the electrons in the well regions.428 Chapter 3. thus the SL potential well will flatten. > d.(z) = forO<z<d f o r z < 0 and z AE.rAs QW of 100 A width containing different numbers of electrons per cm-2.. 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. the inclusion of the Hartree and exchange-correlation potentials must be performed in a self-consistent way. As the latter states are only known after the effective mass equation has been solved. In Figure 3.5 x10’2cm-2 15 x10’2cm-2 .72 we show self-consistently calculated potential profiles and energy levels for a Alo.

) In this way. for example.7.374)..273) at the two interfaces. Semiconductor microstructures 429 Figure 3. The solutions must be normalized and must guarantee for the continuity of the expressions (3. then hole-hole inter- . if this were allowed. 1985. Solutions of this kind can be found in different ways. numerically calculate normalized solutions for various values of E and kll. Matching these solutions in such a way that the continuity of the expressions (3. will only be possible for certain discrete energy values E. Subband structures calculated in this way are shown in Figure 3. and the second level ( I h l ) mainly from hole states with the light hole mass parallel to z.73. If the subbands of the QW are partially filled by holes. ( A f t e r Altarelli. Thus the two bands would cross.7As QW of 100 A width.and light-hole-like curvatures parallel and perpendicular to z are consequences of the Luttinger-Kohn Hamiltonian (2. The alternating heavy. and Fasolino.273) is guaranteed for a given value of kll. the bands repel each other leading to the anticrossing behavior seen in Figure 3.3Ga0. One can. the curvature of the hhl subband at the Ihl subband. In reality.73: Hole subbands of a 100 A wide Alo. Ekenberg. These are the subband energy eigenvalues which are sought. Perpendicular starts stronger than that of to z .(kll).sGao.3. valid in one of the three regions -m < 0. 0 < z < d and z < +m. a set of second order differential equations for the four hole envelope function components arises.73 for a A10. 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 .TAs QW.

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

The more detailed treatment of these properties is beyond the scope of this volume. as shown in Figure 3. Such a behavior.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. the experimental V d versus E characteristics clearly reveals the negative differential drift velocity predicted by Esaki and Tsu. i. Here we will give only two characteristic examples. Curves 1to 4 correspond to SLs of different miniband widths A.) 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.7. Horing. and Cui.75: Calculated current-voltage characteristics of various GaAs/ AlAs SLs with the electric field parallel to the SL axes. Figure 3. In the presence of an electric field parallel to the SL axis. one concerning electric transport and another concerning optical properties. Semiconductor microstructures 43 1 Figure 3. Experimentally. which originally was predicted by Esaki and Tsu (1970). Consider a single electron in the lowest SL miniband EAl(b).e. a sublinear increase of V d with E has been found above a critical field value. the differential conductivity becomes negative. Above a critical field value at which the V d peaks to its maximum value. the electron is accelerated . has been confirmed in more rigorous calculations by Lei. 1991. the drift velocity decreases with increasing field strength. The underlying physics can be understood easily.3. (After Lea. If corrected for effects of the Ohmic contacts and macroscopic electric field inhomogeneities. Horing and Cui (1991). 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.76.

(After Sibille.77. Electronic structure of semiconductor crystals with perturbations Figure 3. This explains the negative differential drift velocity seen in Figure 3.75. If the subgroup of electrons having negative effective mass is sufficiently large.432 Chapter 3. a superlattice contains a gas of many electrons. the electron gas is heated up by the electric field. its effective mass becomes negative. populating the miniband E:(k). which correspond to optical transitions from the tops of hole subbands to the bottoms of electron subbands. the total current density of the gas increases if E is further increased. 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. and it decreases with increasing E if the k-value of the electron is above this point. causing deceleration instead of acceleration. the absorption spectra of GaAs/Al. further increase of the field strength will actually decrease the current. can be clearly seen in the spectra of Figure 3. and Mollot. as the widening of the fundamental energy gap and the shift of the steps towards higher energies with decreasing well width. 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. its velocity takes a stationary value in a dc field. An example of an optical experiment is shown in Figure 3.76: Experimental current-voltage characteristics of various GaAs/AlAs SLs with the electric field parallel to the SL axes.Gal-.77. Since the electron is inevitably scattered by phonons and impurities.As QW structures of different wen widths are shown. The enhancement of absorption at the step edges. The latter increases with increasing field strength E if the corresponding k-value is below the inflection point. Wang. 1990. Palmier. which implies that more electrons populate k-points with a negative effective mass and less with a positive one. Thereafter. is due to the Coulomb .) 300K >- 5 - 2 4 BIAS (VI 6 0 3 until it reaches the inflection point of Eil(k). Simultaneously. For low field strengths. Also other features of the QW band structure observed above. However. Thus. most of the electrons have low k-momenta and positive effective masses.

) QWs of various well widths. if one applies an external electric field to a semiconductor sample.77: Absorption spectra of GaAs/Al. In photoluminescene. impurity states and other microscopic properties of the material. Wiegmann. a QW emits light at shorter wavelength than the corresponding bulk material does.As (After Dingle. and Henry.3.8. photoluminescene spectra are extensively used for the experimental characterization of semiconductor microstructures. Macroscopic electric fields 433 Photon energy ( e v ) ---w Figure 3.Gal-. 3.8 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. The electric transport properties and electro-optic effects are particularly well suited . In the case of GaAs this effect is particularly striking . while a GaAs-quantum well of 50 A width emits visible red light. interaction between electrons and holes (excitonic effects). Beside absorption spectra. the response yields information about the band structure.the bulk crystal emits radiation in the non-visible infrared region. one observes mainly radiative transitions between the electron and hole ground state levels of an (undoped) QW because only these are considerably populated. For instance. 1974. Due to the enlarged energy separation of these levels.

either because of spatially inhomogeneous doping such as in the case of a pn-junction. V’(x) diverges at infinity. 3. electric fields in semiconductors need not. (3. and thus is given by V’(x)= e E . With this condition fulfilled. In the following theoretical description.8.01 .2. which here reads (3. within a characteristic length of G x a. unlike to the case of point perturbations. or because of other spatial inhomogeneities as surfaces or interfaces. 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.urn.294) does not possess lattice translation symmetry. be applied externally as they are already present internally. an infinite crystal in a homogeneous electric field cannot be replaced by a perturbed supercell whose periodic repetition forms an unperturbed supercrystal. In practical terms. If the field strength E is not too large then the perturbation potential (3. this means that the field should not change appreciably within a periodicity region.5. Electronic structure of semiconductor crystals with perturbations to extract this information. The latter fact implies that. In addition to excluding spatial inhomogeneities of the electric field. Here it has the form .3. Fields which change only little over this very small distance can be considered as homogeneous.294) As in the case of point perturbations considered in sections 3.4 and 3.1 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. This only means that the frequencies of these changes should be small compared with the characteristic frequencies of the electrons of the semiconductor. the effective mass equation (3. Moreover. This potential is defined as the difference of the energy of a crystal electron in the presence of the electric field and without it. The crystal in an electric field has to be treated as what it in fact is. however.295) e I E I a << E g . Often.53) is applicable.e.434 Chapter 3. namely an infinite system with 2-dimensional lattice symmetry perpendicular to the field. x. and no lattice symmetry along the field direction. the perturbation potential V’(x)of equation (3.1 and 3. i.295) fulfills the smoothness condition of effective mass theory of section 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. the source of the electric field will play a role only inasmuch as we assume that the field is spatially uniform. we will also exclude temporal changes in our discussion below.

298) reads (3. ~ ~ ( Z ) . Assuming the z-axis of our Cartesian coordinate system parallel to the field direction. in contrast to the electron with charge -e.i V ) + e E . in particular. respectively.(x) can be written as F~E. Thus the envelope function F.296) We consider this equation in the particular case of an isotropic and parabolic band. . The spectra of energy eigenvalues of equations (3..299) For the conduction and valence bands. as continuously varying quantum numbers of the .298) with E . wavevector perpendicular to the field. ~ (= ) i k ~ ~ .300) and (3.301) The second equation can be interpreted as the effective mass equation for a hole with (positive) mass Im:l and energy (. E Xe x. x } F V ~ .300) (3. ~ (3.. ( x ) EvFv~. respectively. the charge of the hole is positive.(z) =E ~ X .297) where x l and kl denote. = E” l + -:il2 k. 2m (3. ~ . equation (3.e..and y-directions is that of a free particle. Macroscopic electric fields 435 { E y ( . = (3. ( t ) obeys the equation X.(x). fe. (3. and vary between -co and fco as a direct consequence of the unrestricted motion of the electron or hole in the field direction. i. the electron motion in 2. This allows one to use the energies E .8. .301) are continuous.3. the components of x and of the . x (2).(x) F ~ E . thus The solutions of the corresponding energy eigenvalue problems for electrons and holes read. The z-dependent envelope function factor X . As the equation shows.) -. stationary states X V C v ( z )and to assume normalization in terms of Dirac’s &function with respect to these energies.

The envelope function for holes behaves similarly.. stationary electron and hole states in an electric field. one obtains for 0 . they are not eigenstates of the Hamiltonian but rather are non-stationary states cp. ( z ) are shown in Figure 3. this region is classically forbidden.300).(x. On the decaying side. . and for he. it represents a potential barrier for electrons.301) and their solutions (3.436 Chapter 3.303) (3. Electrons or holes in such states do not carry an electric current. more strictly speaking.1 m . The envelope function is nonzero only because electrons tunnel into this barrier. 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 . The Schrodinger equations (3.305) as so-called electro-optic frequency. it decays within the hole barrier with e E z < 0.l . a value of about 1013 s . one may suspect. 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. a value of 10 m e V . The electron function decays exponentially with increasing z for e E z > -Eg. the expectation value of the current density operator in the field direction vanishes..and oscillates with decreasing z for e E z < -Eg.304) describe. t ) which devebp in time not only by means of a timedependent phase factor. Assuming E = lo4 Vlcm and m: = 0. however. respectively. then non-zero non-diagonal elements will occur in the expectation value of the current density operator).78 for eC = eV = 0 and Bc = 0. that in addition to stationary states there will be yet other states which are better suited to the condition of a non-vanishing current. the total energy E g of an electron is smaller than its potential energy e E z .303) and (3.(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. Thus. Such states do in fact exist. with momentum growing linearly in time. Note that stationary states X. and oscillates in the classically allowed hole region with e E z > 0.304) with (3. . (3. Electronic structure of semiconductor crystals with perturbations (3. and with Ai as the Airy-function of first kind.

taken at energy cC = E.3 0.0 (D 0 W g e N rn g P c 2 rt v) Y -0. Bloch oscillations The envelope functions F.306) To determine F. is given by a &function with respect to k. The solution F. t = 0) = . t = 0) s F. 3.2 Non-st at ionary states.307) and (3.u g 3 Lc C 0.a time-dependent effective mass equation is required./C(X.(x.k(x.(--iV) eE . (3.296). ( ) at t = 0. t ) = ~ V O ( X ) F V ( Xt . t + a at (3.(x.2 0. t ) of equations (3.308) Here.1 0.8.(x. This may be obtained from the corresponding time-independent equation (3.t ) may be stated as pkx FJX. 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.4 0 . t ) . Macroscopic electric fields 437 0. The resulting equation reads {&. Then the initial condition for F. -ik.(x. so one has $v(x.307) In solving this equation we assume that the electron was in a Bloch state ( .2 -Eg/eE 0 Z Figure 3. on the right hand side is replaced by the operator i b ( a / a t ) . ) = iTi-F. Oc = OU = 8.t)of these states are time-dependent.308) is given by . t ) .3.78: Envelope functions of stationary electron and hole states in an electric field. z} Fv(x.8.) .1 -0.x G ' (3. wherein the energy E. = 0.

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

also may be understood as a manifestation of Bloch oscillations.305). The negative differential electric conductivity of a superlattice parallel to its axis. If (1/3)0:t3 is considerably larger than 1. the velocity < ( d x / d t ) > follows by means of the previously derived relation (2.3. an electron starting a Bloch oscillation will soon be scattered and its momentum will be distributed randomly over all k-space. In other terms.7. That this is actually not the case is due to perturbations of the Bloch oscillations by collisions of electrons with phonons.. e. There is still another reason that Bloch oscillations cannot be observed in ordinary semiconductor crystals. 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. but also for the fact that an otherwise vanishing average current of a Bloch electron does not actually go to zero. For the artificial superlattices considered in the previous section 3.311) average out to zero almost completely. This implies that. Thus. Bloch oscillations are not observable even without collisions. then the energy bands E.7.h)of the momentum operator p.' due to the electric field. using the identity (dxldt) = ( l / m ) p . One may say that these states have a finite lifetime 0. If one considers only k-vectors close to critical points of the band structure. the phase of the exponential contains a term (1/3)e:t3 (0. in actual crystals and under normal conditions.311) decay in time by themselves since the exponential factor oscillates with increasing frequency. It is due to the fact that the time dependent Bloch states (3.and Bloch oscillations may in fact be observed.hJpJ(p. between two collisions above was found to be small with respect to T . The same result holds for the timeaveraged current of the electrons of a crystal in an external electric field.193) for the expectation value ((p. turns out to be zero. the exponential oscillates so fast that the time dependent Bloch states (3. The Bloch period T is of the order of magnitude lo-'' s in such circumstances. in the field direction. . taken over a Bloch period. The time rv between two collisions is substantially smaller than T . just as the time T. Macroscopic electric fields 439 the velocity operator ( d x l d t ) with respect to the timedependent Bloch function Pvk. just due to the finite field induced lifetime. typically of the order of magnitude s. To prove this statement we consider a field strength of lo4 V / c m and a primitive reciprocal lattice vector K typical of semiconductors. This may easily be seen for quasiwavevectors k close to a critical point. The timeaverage of the velocity < ( d x / d t ) > obtained in this way. is small compared with the period T of Bloch oscillations. impurities and other point perturbations. it also vanishes. For zero wavevector component k. In such circumstances T may become larger than T~ and OF1. the primitive lattice vectors and thus the periods T are much shorter than those in natural crystals. reported in section 3. For not' too-large field strengths. remains finite. no periodic motion can develop in the presence of collisions. is the electro-optic frequency of equation 3.8. which would otherwise be infinitely large.

are considered. Ec and wavevector components k l k. e E z ] / ~ e . an equation similar to Newton’s law of motion m t -d 2 < x > = -eE. in particular. The . the overlap integral has . (3.296). The pertinent particles with positive mass. is a frequency analogous to the electro-optic frequencies e . ) A i ( [ . If./he. 3. Electronic structure of semiconductor crystals with perturbations This yields. however with the reduced effective mass mT. Performing the overlap integral of A i ( [ E .8. For reasons of energy and momentum conservation.m:/(mz m:) of electrons and holes + + .305).. According to equation (3. .l perpendicular to the field have to be equal . to be taken with respect to the product Ai([E.106. dt2 (3. with E. ) .e E z ] / A e . kc-... the initial and final state energies E.) where 8. For electrons from the valence band the effective mass is negative. .e.vkvl(x) and FECkci(x) with identical values for E tC and k w l . formed here. Taking account of these off-diagonal elements yields a description of electrons undergoing quantum mechanical transitions between the valence and conduction bands. ) A i ( [ . The reason for the non-zero overlap is the tunneling of the valence and conduction band electrons into their respective barriers. for field induced interband transitions is proportional to the overlap integral between the two envelope functions F. the holes. .440 Chapter 3. quantum mechanical probability W . values of z .314) follows from (3. x. 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 .313).+ e E ~ ] / A e .313) With the neglect of collisions. 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). behave like particles with positive charge e. approximately. ) with respect to z one arrives at an expression proportional to the square of the Airy-function Ai3(E. as may be seen from Figure 3. = mZ.3 Interband tunneling In the effective mass equation (3. 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. the possibility of electric field induced coupling between the valence and conduction bands is neglected.e E z ] / A e . In reality such coupling exists due to the non-vanishing interband matrix elements of the potential V’(x) = e E . in such a transition. of equation (3.299) this means E = cC. = ec = 0 and kl = k l = 0. i. transitions of electrons between the two band edges.

(3. It is just the probability for this tunneling step which the Airy-function expression A i 2 ( E g / W ./7iB.. The same expression follows if one uses the nonstationary states of subsection 3. oc A i 2 (z) . The probability W.2. (3. may be ob. Expression (3. reaches the upper band edge.317) Although the interband matrix element (p.. In this. One thus obtains the interband transition probability W .k[xIp.) by multiplying this expression with the frequency 1/T of Bloch oscillations. ) represents.. This is plausible since this frequency indicates how often a valence band electron.. The complete expression for W .*. The energy uncertainty relieves the need to satisfy energy conservation and permits the interband transition probability W . from which it can tunnel into the conduction band. For realistic field strengths E. may be understood as the energy uncertainty of an electron-hole pair due to its finite lifetime in the presence of an electric field.315).. for an electron to tunnel per second from the valence into the conduction band at kl = k = 0.3..318) . According to expression (3. It is small if the condition fit'. = -Ai2 1 T (2). 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.. as one would expect. thus reads W .8. to be nonzero.315) Therefore.x p k of the perturbation l. grows larger as the energy uncertainty hOCw approaches the gap energy E.. Macroscopic electric fields 441 instead of their simple effective masses m.315). To understand what this result means physically we may argue as follows. is measurably larger than TLB.. The non-stationary approach also provides a rough estimate of the proportionality factor in relation (3. which has the same order of magnitude as (p. the asymptotic approximation (3.kJeE.8..) potential V'(x) does not enter this expression explicitly.316) for the Airy-function applies.8. l tained from Ai2(E..315) for the transition probability W . was derived using the stationary electron states in an electric field of subsection 3. << Eg (3. it occurs implicitly through the lattice constant a in T . per second.3.k). as W. the tunneling probability W. the electro-optic energy Ti@.

4 Photon assisted interband tunneling As pointed out in Chapter 1. the optical transition probability and. 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. just as in the case of field induced interband transitions. so that the two conditions (3. 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. 1958.kCl with identical values for k. Field induced changes occw not only in the absorption coefficient.8. and we have Franz-Keldysh oscillations (Tharmalingan. It has the same order of magnitude as E. Boer. the optical absorption coefficient.hw. In typical cases this condition is fulfilled sufficiently well for field strengths of the order of magnitude lo5 V / c m .295) for the applicability of effective mass theory if the gap energy Eg is formally identified with (h2/2m5. 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.315) by replacing E. Hansch and Kummel. while it is definitely not valid for field strengths close to the inner-atomic fields of 10' V / c m . of the semiconductor. 1959).l. but.+hw. One therefore has (3.318) transforms into the condition (3. 1963). 3. with E. holes are generated in the valence band and electrons in the conduction band.)1/a2.295) are equivalent. Electronic structure of semiconductor crystals with perturbations holds.318) and (3. but also in other optical constants including the real part of the complex refractive index. the absorption coefficient with electric field oscillates with photon energy about the absorption coefficient without field. Above the gap. At least for such fields interband transitions are important. 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. This means that W s t follows from W . The inequality (3. effectively lowering the gap (see Figure 3.442 Chapter 3. hence. is also non-zero for photon energies below the gap. kl. By means of tunneling. with energies eC = e. Keldysh. unlike the latter case. .. The latter energy represents an average energy gap in effective mass approximation.(k) .319) In an external electric field. This phenomenon is called the Franz-Keldysh effect (Franz. It decays exponentially as hw decreases. Besides the changes at the fundamental absorption edge considered above. 1958. in equation (3. owing to the tunneling of electrons and holes into their respective barriers.79). In the presence of an electric field this condition no longer needs to be fulfilled.

including superlattices and quantum wells (Pollak. These can be used as input parameters for empirical band structure calculations (Cardona. Enderlein. Enderlein and Keiper. in which field induced changes of the reflectivity of a semiconductor sample are measured by means of a modulation technique.80).9 Macroscopic magnetic fields Like electric fields. For most purposes . This fact is exploited in electrorefiectance spectroscopy. magnetoresitivity and cyclotron resonance. By measuring the electroreflectance spectra of semiconductors one obtains experimental data relating to their valenceconduction band separation at critical points. 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. 1994. as well as magneto-optic properties. 1967.3.79: The same envelope functions as in Figure 3.( E.9. Macrmcopic magnetic fields 443 . particularly galvanomagnetic phenomena such as the Hall effect. Photon energies which give rise to strong electroreflectance signals correspond to optical transitions at critical points of the interband energy (see Figure 3. are of particular importance in this context.78.-ho)/eE 0 2 Figure 3. Transport properties. 1969) as well as for the characterization of semiconductor heterostructures. 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. 1967). 1996). (Aspnes. 3. but with the energy of the electron exceeding that of the hole by the photon energy iiw.

In these circumstances. The vector of the pertinent magnetic induction vector will be denoted by B. In the case of cyclotron resonance.9. Below. 1965. 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. Electronic structure of semiconductor crystals with perturbations -121 1. Since the interaction of an electron with a magnetic field cannot be characterized by a scalar perturbation potential.3 is not directly applicable to this case.1 Effective mass equation in a magnetic field Initially. (After Seraphin and Hess. Thus. 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. temporal changes of the magnetic field in the M H z range are still admissible.) this field can be assumed to be homogeneous in space and time. 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. but must be described by the vector potential A of the magnetic induction B.80: Electroreflectance spectrum of Germanium. This matter will be addressed in the following subsection. Whether an effective mass equation can be derived at all with a magnetic field. 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).0 ’ I I I I I I 1. 3. as usual. the effective mass theory developed in section 3.444 Chapter 3. and what it will look like if it is feasible. we consider spatially and temporally constant magnetic fields H exclusively. save for the gradient of an arbitrary gauge + . The vector potential A(x) is determined by the magnetic induction vector B. must be explored separately. Just as in the case of external electric fields.

320) 2 This choice of gauge guarantees that p commutes with A(x). and assume the form (3. we represent the Schrodinger equation in the approximate Bloch basis Iuk)'. (3. be limited by the condition that the associated vector potential changes only little over a unit cell in comparison with the energy gap. as in section 3. so that the order in which p and A(x) are multiplied in the expression [p (e/c)A(x)I2 is inconsequential. t-hematrix elements of H with v # vo vanish. The Schrodinger equation of a spinless crystal electron in a magnetic field reads + (3. (3. Accordingly. The expression (3.8 on electric fields. p-perturbation theory. which were already evaluated above..322) with this Ansatz. the component with u = vo must obey the relation l(vok(H k ' + eA(x).321) As in the derivation of the effective mass equation for perturbing scalar potentials in section 3.323) Components '(vkl$) with v # vo must vanish according to equation (3.63) derived there is applicable here as well. i.(k). To verify this we consider the matrix elements '(vklHlvok')' of the unperturbed Hamiltonian H . In order to satisfy the Schrodinger equation (3.322) with H = (p2/2m) + V ( x ) as Hamiltonian of the crystal without a magnetic field. whence '(vk(H u'k' + L A ( x .p ) + mc l (:) 2 A2(x)IvAk')l '(vhk'lg) =E '(vkI$). (3.322). The strength of the magnetic field will. its matrix representation '(vkJAlv'k')' is approximately diagonal with respect to band indices. we consider a non-degenerate band extremum at k = 0.9. we use the k .3. Macroscopic magnetic fields 445 function which we choose so that A ( x ) has the form A(x) = A[B x XI. In this sense. whence . Because of the assumed smoothness of the vector potential A(x). the vector potential is presumed to be smooth. Initially.60) for '(vkl$).3. mc p + 1 f) 2 A2(x)(uok')'Fw(k') = EF.e.

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. and therefore one also has ’(vkl A2Iv’k’)’ M 6 1 .328). thus.334) as unperturbed parts. of ‘(vklq) with v # vo.p= -L. B. p.328) for these elements.Pr signifies the ordered triplet z y z or a cyclical permutation of it). We proceed in two steps. First step 1 A.325) What remains to be evaluated in the Schrodinger equation (3. We have (3. the same also holds for the matrix representation of the operator ( e / m c ) A . Just as the matrix representation of the latter with respect to the approximate Bloch basis (vk)’ is band-diagonal in second order perturbation theory. and using the notation L . The band-diagonal elements (vokl e / m c A . Substituting relation (3.326) This relation finally confirms the vanishing of the v # vo-components of the left hand side of Schrodinger’s equation (3. The matrix elements of L can be rewritten by means of Heisenberg’s equation of motion which approximately yields (3.323) and.p.327) (3. In the second step we consider the first-order corrections. = zap^ .446 Chapter 3. p-perturbation operator.B 2 with L = [xx p] as angular momentum operator.”@pa for angular momentum components (c.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. pIvok’0) = pB(vokO(Ti-’LIvok’O) . ( klA21k’) . In the first step. we obtain . This operator has the same structure as the k . mc Since (3.plvok’)’ will now be rewritten in a more convenient form.328) Here p~ = (eTi/2mc) denotes the Bohr magneton.329) in expression (3. we have (vokOleA. p between the Luttinger-Kohn functions (vokO) Ivok)’ which enter the first-order Bloch functions Ivok)’ of equation (2. we determine the matrix elements of the operator ( e / m c ) A . (3.

which describes the coupling of the magnetic field to the rotational part of the motion of a Bloch electron.332) In section 3. Here we find. The latter evidently describe the interaction of the magnetic moment of the orbital motion of a Bloch electron with the magnetic induction vector B. that the antisymmetric tensor L . The tensor L . since it contains a rotational part about the atoms which form the crystal. as we do here.3. This antisymmetric tensor bears a close relation to the reciprocal effective mass tensor M&La of equation (2. In principle. The matrix elements (vokO)L. too.and k-diagonal Bloch matrix elements of the Hamiltonian (see equation (3. so we may use the relation The quantity L is an antisymmetric tensor or. cubic materials it vanishes for symmetry reasons. this is possible because the motion of a Bloch electron cannot in general be reduced to a translation.330) In this. we used the fact that the interband matrix elements of the momentum operator are diagonal with respect to k and k’. measures the average angular momentum of this rotation in the In Bloch state 1~00). a pseudovec.lvokO) do not depend on k. The situation is comparable with that for s-states of free atoms. determines the B-dependence of these elements. 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.. Apart from a constant factor. Macroscopic magnetic fields 447 (3. tor L.9.337). In order that it differ from zero. the two quantities may be understood as real and imaginary parts of the same complex tensor.3 we found that the symmetric tensor M. namely (3. Second step Beside the k-diagonal term discussed above. the . the angular momentum of the Bloch state IvoO) must differ from zero.Lp describes the kdependence of the band-index.63)). in other terms.

+1 2m + For a non-degenerate isotropic parabolic band the magnetic moment L. as already mentioned.e(k(Aa(k’) kp‘(kja. then transforming .334) and (3. Electronic structure of semiconductor crystals with perturbations Hamiltonian matrix of (3. i.IvokO)] of the approximate Bloch functions Ivok)’ (which was previously omitted) is taken into account.63).p)lvok’)’. Using the same procedure employed in the spinless case.335) obtained in rewriting the Schrodinger equation (3. (3.323). vanishes in the spinless case considered here.448 Chapter 3.0023). where the perturbed part [Ivok)’ . the following equation results for the envelope function Fvo(x) : 6kk. L. initially.jk’)] .323) still contains terms which are non-diagonal with respect to k. They occur through the formation of the matrix elements l(vok)(e/rnc)A. The complete result is given by [k. k’ and give rise to a coupling of B to the translational part of this motion.h-1pBB.321) may be written as where g is the gyromagnetic ratio of a free electron (g = 2. Then equation (3. Spin a n d spin-orbit interaction Considering the role of spin and spin-orbit interaction.e. the Schrodinger equation (3.334) 4 Summing the three terms (3.336) This equation changes if spin and spin-orbit interaction are taken into account.335) takes the form (3. (3. by first representing equation (3.337) in the spin-dependent Luttinger-Kohn basis. The assumption of a non-degenerate band vo will be adopted. and simultaneously transforming from kspace to coordinate space.

-values for the conduction band minimum of several diamond and zincblende type semiconductors are listed.11 experimental g:. namely the vector of Pauli's spin matrices a. it represents a characteristic of an energy band vo at a particular critical point. the effective mass equation (3. we used the fact that the diagonal elements '(voaklH. of the angular momentum operator emerge from the corresponding expressions (3. and finally transforming it back to coordinate space.3. Ivoa'k)' of the spin-orbit interaction operator vanish at k = 0 for symmetry reasons. while the non-zero k-linear terms in these elements are negligible.338). In regard to their transformation properties in coordinate space. The deviation from 2 is determined by the induced magnetic moment of the orbital-motion component of a Bloch electron. The matrix elements L. all values g are less than 2. (3. the effective mass equation for an isotropic parabolic band follows as = EF. Just like the effective mass. is a multiple g. are matrices in the two-component spin space. (3.9. there is only one such pseudovector in the case of systems with the symmetry group oh.s). Apart from a constant factor. Macroscopic magnetic fields 449 it into the spin-dependent approximate Bloch basis Ivak)' = Ivk)'lo). they are components of a pseudovector. In Table 3.331) without spin-orbit interaction by replacing p in the latter with the spin-dependent operator ?i of equation (2. This means that L.338) In obtaining (3.339). As one may see.353).330). obtaining In accordance with their definition.Acr' of cr'. the L. in other words it results in a diamagnetic .. With = guo 29. As in a free atom..(x. we may write + h-lLm 1 + 2g cr' = i g & d . the g-factor of the free elecE tron. this moment is always negative. (3.338) takes the form The factor gEo is called an effective g-factor. The constant gvo is determined by the matrix 1 elements of (3.340) Using this expression.

of the effective angular momentum of equation (3.450 Chapter 3.67).42 3. the effective electron g-value is close to 2. The same holds for the components L . 1982. increases if the gap decreases. The elements MGip of the effective mass tensor are 3 x 3 matrices D with elements DZ:. and will address this below.339). ( x ) . (After Landoldt- IC Bornstein. we need an effective mass equation for degenerate bands.(x)) by equation Fw (3. and the pertinent LuttingerKohn functions read (vmkO).20 0..06 1. z . Electronic structure of semiconductor crystals with perturbations Table 3. indicating that the diamagnetic contribution is small in this case.y.333) which may be expressed as 0 matrices L~ with elements 04 . the material with the smallest gap. The eigenfunction $(x) is given in terms of * the envelope function vector F . : . (x)= (Fwz(x). tron mass of expression (2. Spin and the spin-orbit interaction will be omitted initially. has the largest negative value of g To describe the top of the valence band of diamond and zincblende type materials. F. The same behavior of the effective g-factor for decreasing gap is observed among the 111-V compound semiconductors: InSb..338).13 0.11: Effective g-factors gE of electrons and magnetic interaction constants and q of holes in diamond and zincblende type semiconductors.) GaAs GaSb InSb CdTe ZnSe -0. and similar to the effective elec. A negative effective g-value and hence a larger diamagnetic contribution occurs in Ge.m = 2. This is to be expected since the diamagnetic moment is determined by the average angular momentum L which according to expression (3. Degenerate bands We consider the valence band of a diamond and zincblende type semiconductor in the vicinity of the BZ center at k = 0 . Then the degeneracy is %fold.41 0. The Bloch states at k = 0 are IvmO).04 0.15 contribution to the total magnetic moment of the Bloch electron. For Si.

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

the new gauge lacks axial symmetry with respect to the magnetic field. 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'$-valence band states thus reads * (3.336) also holds. however. In this. band without spin.I z of quantum number of equation (A. holds unchanged for materials with zincblende structure also.9.O). The latter can again be obtained by means of the method of invariants. the three angular momentum matrices I ~ly. there are now two such subsets. The I.f and I bands. band of diamond type semiconductors develops into the r. + ( i e / h c ) A . . have to be made. .11). Electronic structure of semiconductor crystals with perturbations differently affected by the magnetic field so that a magnetic splitting of the or r 5 valence band occurs. we take the magnetic field in the z-direction and employ the vector potential in the form A = (--By. Two changes are necessary in the presence of a magnetic field: First. To apply this method in the present case.74). 3. In most (z cases q is negligibly small (see Table 3. We denote it symbolically by I . an angular momentum ($ term H M has to be added.. one must find a complete set of 16 basis vectors of the 4 x 4-matrix space formed from ( $ @ @ . That the presence of spin involves not only K . f of equation (3. the replacements 8. The effective mass equation (3. then the I'b. invariants linear in B are possible only with subsets matrices of I'i5-symmetry. I z ) . --. Differing from 9 u u * the spinless case. that of a non-degenerate band without spin. 0. The result (3.$ d . Second.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 effective mass equation for the I?$ band without a magnetic field is given by (3. This gauge differs from that in expression (3. Unlike (3.336). r. If one adds the effects of spin and spin-orbit interaction.I y r z ) .346) for H M which has been derived here for diamond type semiconductors.320) used in deriving the effective mass equation (3.. z .74). comparable to that of a p-level in the case 1 of a free atom. in the operators Q. namely I = ( Ix.452 Chapter 3. $.320).144) and their products which transform in accordance with the irreducible parts of the product representation r$ x I?$ = rl+ rz I'12 21'i5+I'k5 of oh. R . As in the case of the I'. but also a second constant q..346) where K and q are again constants which must be determined either from band structure calculations or experimentally. Q = 2. I 030303 *3 and also the triplet (Ix. is understandable because the orbital and spin motions have different gyromagnetic ratios.y.

. 1 . the effective mass equation (3.E. . Macroscopic magnetic fields 453 because for this gauge the vector potential A = (--By. and k .347) yields where we have set eB wcvD = Im:. as wavevector components in the x. 0.347) commutes with the translation operators for arbitrary displacements in the x.. eB liC (3. It is well-known that in this case the eigenstates can be described by integer quantum numbers n = 0 . yo = rCk.349) associated with motion in y-direction through the relation (3..3.347) Since the Hamiltonian in (3. .9. Using the present gauge. [ +Pp +pq F d X ) = ( E . equation (3..352) . its eigenfunctions can be chosen to also be simultaneously eigenfunctions of these operators.O) also commutes with the momentum operator p. with the corresponding eigenenergies E L given by EL. For X. 2T 7 (3. n - (3.and z-directions. 2 r z = -.00.348) with k .351) Equation (3. of equation (3.o)F.349) describes a harmonic oscillator with center at yo.(x).(Pz + $Y)2 am:. ~ These energies are called Landau levels. The same holds for the more complex effective mass equation (3. It follows from the partial eigenvalue ELo of equation (3. . (3.lc . sgn(m&).we have ( + a> . which leads to 1 ' F vo (x)= -ez(kSzfkZa)X v o ( Y ) . .(y). E & = FAW.350) The total energy eigenvalue E .343) for degenerate bands without as well as with spin.and z-direction.) of k. mass lm&1 and eigenfrequency wcw.347) is a function Ew(k. 2 . For the eigenfunctions Xvo(y).336) for a non-degenerate band without spin takes the form 2.

apart from a constant factor. is due to the fact that h k .5. enters the energy eigenvalue Euon. the spectrum of allowed energy values forms a set of 1-dimensional energy bands.81. it lies in the microwave region.e. and k.353) with H .353). This DOS can easily be calculated by means of the general definition of equation (2. however. i. the DOS decays like l / d G . Thus the electron executes an oscillation in y-direction with angular frequency wc. only k .355). This unusual absence of k . k. hLw.355). the Landau subbands.352) and (3. a Hermitian polynomial of order n. Electronic structure of semiconductor crystals with perturbations (3. The physical meaning of the eigenstates (3. about its equilibrium position yo. the of conduction band becomes. It is enlightening to consider the density of states (DOS) of the energy spectrum of equation (3.. p c ~ ( Eis shown as a function of E.353) and eigenenergies (3.354) For mC. It becomes infinitely large ) Each singularity at the uniformly spaced energies E . which exhibit non-zero dispersion in the k-direction parallel to the magnetic field. According to equations (3. k y .. taking the conduction band vo = c as an example. For energies slightly above E. Of the two wavevector components k . In the z. . In Figure 3. Then the DOS. One need only replace the quantum number i in (2.205) by the set of quantum numbers n . = 0. The pertinent frequency is given by (3.454 Chapter 3. p c ~ ( E ) .205). and replace Ei by the set Ecn(k.) of Landau subbands from equation (3.(n corresponds to the minimum of a particular 1-dimensional Landau subband. The inverse square root-behavior of the DOS of a single 1-dimensional parabolic band has already been discussed in section 2. this frequency amounts to 140 G H z . represents the eigenvalue of the canonical momentum operator component + + i).and I-directions the electron propagates like a plane wave.2 m and B = 1 Tesla. = E.352) of a Bloch electron in a magnetic field may be understood as follows..

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

(After Dexter. Measurement of cyclotron resonance is an important experimental method for the determination of effective masses of electrons and holes in semiconductors and metals.82. Electronic structure of semiconductor crystals with perturbations Magnetic Induction/ Tesla 4 Figure 3. One finds that the energy levels can always be characterized by an integer quantum number n .343) with D from equation (3.11 these values are listed for several semiconductors. The holes show up in two well-resolved maxima in Figure 3.346).) diation. In Table 3. whereupon the absorption becomes a maximum.456 Chapter 3. Comparison with the theoretical results also yields values for the constants n and q. the energy eigenvalues of the rs-valence band in the presence of a magnetic field must CJ * be calculated from equation (3.82: Cyclotron resonance spectrum of Germanium at 4 K . one due to heavy holes and the other due to light holes. . and Lax 1956. as in the case of the harmonic oscillator.82) it is absent. the first peaks of the cyclotron resonance spectrum of germanium are shown. In Figure 3. the effective mass can be determined.74)) and H M from equation (3. Zeiger. two corresponding to heavy and two to light holes. B e cause of broken time reversal symmetry in the presence of a magnetic field. By means of cyclotron resonance measurements these levels can be determined experimentally. each of the doubly spin-degenerate heavy and light hole levels in the absence of a magnetic field splits into a doublet. each value of n determines a group of four energy levels. the electrons give rise to several cyclotron resonance maxima.82. Each of the two hole peaks has a doublet structure which can be seen experimentally at higher resolution (in Figure (3. Because of the many valley structure of the conduction band. Using the position of this maximum on the magnetic field scale. To understand the cyclotron resonance spectrum of holes. but in contrast to this case.

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

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

) are. . . If only extended oneparticle states are involved. also eigenvectors of I so that ? Using equations (4. fiiIN1. (4. like in the case of a real crystal having shallow and deep centers. N.). N. (4. .6) one may easily show that the occupation number space matrix representation of the equilibrium density matrix of equation (4. The Slater determinants IN1.3) Moreover. N z . N z . 00 k of the electron system follows by N = p i . The IN1. as many Ni different from zero as the total number of electrons in the system. . These vectors may be used to represent an arbitrary many-electron operator. . .) in the occupation number space. Therefore.1.2) and (4. N w ) . .3) imply that The occupation number vectors IN1.5) where Ei are the configuration-independent oneparticle energies. . .) form a complete basis set in Hilbert space of the many-electron system. of course. . N. .2) to (4. . with the diagonal elements given by .) may be understood as eigenvectors of particle number operators i?i for the eigenvalue Ni (see Appendix C ) . . Fundamentals of the statistical description 459 as vectors IN1.2) and the total particle number operator summing the f i i over all i. .4. like in the case of an ideal crystal. ' 7 Nw). in general. N z .1) is in fact diagonal with respect to the basis set of Slater determinants "1. If also localized oneparticle states exist. . N z . N27. i=l (4. N 2 . N 2 . . . . the occupation number representation of k reads W H= i=l EiNi. j NilN1. (4. . . N.. configurationdependent. N. . These vectors have. the energies Ei are. altogether. .

I stands for 'Trace' and means the summation over . like the average of any other operator of an observable quantity of the many-electron system. and localized one-particle states which do depend on the configuration of the many-electron system because of Coulomb repulsion effects. N z . 4. all factors cancel except the two with j = i.) as basis. respectively. . Electron system in thermodynamic equilibrium The average value < fii > of the particle number operator fii. The two expressions (4. In the quotient. These remain and give rise to the expression .2.9) and (4. One may easily demonstrate that the value of the trace is independent of the particular basis chosen. 4. We begin with configuration-independent oneparticle states.10). as indicated in equation (4. . Each value of i represents only one state. since the matrices of 6 and Ni are known in this represent ation. the symbol Tr[ . is formed in accordance with the relation Here. The two trace expressions in the numerator and denominator of equation (4.8). we will calculate average particle numbers in equilibrium by means of equation (4. where we have set p = l / k T for brevity. with different spin orientations corresponding to different values of i.460 Chapter 4.10) can be written as products of sums over particle numbers for a particular state j . it is advantageous to use the set of Slater determinants IN1. . we describe them by an integer quantum number i. N. . all diagonal elements of the operator within the brackets with respect to any basis in the Hilbert space of the many-particle system.2 Calculation of average particle numbers Below.8) become. Of course.1 Configuration-independent one-particle states As above. In doing so it is necessary to distinguish between configurationindependent extended one-particle states.

Calculation of average particle numbers 46 1 Since the particle number Ni may take only the values 0 and 1. In this case of substantial occupancy the limited capacity of a one-particle state to host electrons (remember the Pauli exclusion principle) becomes important. in the exchange of two identical elementary particles. it follows that (4. therefore. f ( E ) no longer small compared to 1. 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). and thus the state is almost unoccupied. . Statistical degeneracy applies to other elementary particles as well. Substantial deviations from the Boltzmann distribution occur when E .it reflects the quantization of energy levels and the indistinguishability of electrons. The appearance of statistical degeneracy is a purely quantum mechanical effect .2. just like for an ideal gas. A particle system is referred to as non-degenerate if it is described by the Boltzmann distribution. the B o l t z m a n n distribution (4. we obtain (4. If one identifies the chemical potential p with the Fermi energy E F .14) We conclude that the average particle number for configuration-independent one-particle state i is given by the Fermi distribution. and the average particle number in it deviates from that in classical statistics in which the hosting capacity of states is not limited. otherwise it is called degenerate.4. Under this condition the average particle number in << the one-particle state is small compared to 1. and uses the notation (4. This also means f(E) 1. Indistinguishability refers to the fact that.EF is no longer large in comparison with k T and.13) for the Fermi distribution function previously introduced in Chapter 1.15) follows from the Fermi distribution for energies E with E .E F >> k T .12) The average particle number in the one-particle state i thus depends only on the energy of the state. The distribution function of classical statistics. The deviation of the average particle number in a oneparticle state from the value given by the Boltzmann distribution is called (statistical) degeneracy.

(4. This is only justified if the spin-orbit interaction plays no role and the two states (uk $) and lvk have equal energy E. The simplest case in which localized states occur is that of a simply ionizable donor or acceptor center. While the Fermi distribution emerges in the former case. 2 and the average particle number < NUk+& wavevector k follows as + NUk-+ > for band u and (4. As in Chapter 3. or. henceforth. 4. taking account of the configuration dependencies of o n e particle energies because of Coulomb repulsion effects. we assume that both the band and spin quantum numbers I/ and u are compatible and meaningful simultaneously. We use the latter description.14 ) yields 1 < fiuk6 > = f(E. ff = f-. which may be formally obtained from the Fermi distribution function (4.17) The Fermi distribution (4.462 Chapter 4. Electron system in thermodynamic equilibrium or the total wavefunction transforms into itself (then the population of the oneparticle states is not limited.e. Their states . In order that the wavefunction luk) really represent only one quantum state. in the form lvko). the peculiarities of the occupancy statistics of localized states can be understood more easily in the case of double donors or acceptors.13) by setting the chemical potential zero by and replacing ‘+l’ ‘-1’in the denominator. we must augment v to include a spin quantum number CT. u must also describe the spin state. However. This distribution cannot be applied to configuration-dependent one-particle states.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. in the latter case it is the Bose distribution function. and a center with n hole ionization levels in the gap is referred to as an n-multiply ionizable acceptor. which is the case here. alternatively. i. we start with them. the quantum number i is the pair vk of band index v and quasi-wavevector k. but the quantization of energy yields a distribution function which also deviates from the Boltzmann distribution).2. Therefore. In the latter case the above calculation of average particle numbers has to repeated. which we take to be the case here.(k)). we will write the band states.(k).16) + g).2 Configuration-dependent one-particle states We consider oneparticle states i localized at shallow or deep centers. With this. In the particular case of band states. a center with n electron ionization levels within the energy gap is referred to as an n-multiply ionizable donor. equation (4. In such circumstances.

as will be demonstrated below. For simplicity. we again have only one type of one-particle wavefunctions + I D a ) l % IDu)2 = p a ) . and consequently also only one type of particle numUsing the pertinent occupation numbers No. respectively. The pertinent configuration-dependent one-particle energy levels are deno'ied by E b and E i .. . (4. we first consider only the two