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P R O P E R T I E S

O F

E d i t e d

T I M
U n i v e r s i t y

IEE

b y

S E A R L E
o f

Sheffield,

U K

INSPEC

Published by: INSPEC, The Institution of Electrical Engineers,


London, United Kingdom
1998: The Institution of Electrical Engineers

This publication is copyright under the Berne Convention and


the Universal Copyright Convention. All rights reserved. Apart
from any fair dealing for the purposes of research or private
study, or criticism or review, as permitted under the Copyright,
Designs and Patents Act, 1988, this publication may be
reproduced, stored or transmitted, in any forms or by any
means, only with the prior permission in writing of the
publishers, or in the case of reprographic reproduction in
accordance with the terms of licences issued by the Copyright
Licensing Agency. Inquiries concerning reproduction outside
those terms should be sent to the publishers at the
undermentioned address:
The Institution of Electrical Engineers,
Michael Faraday House,
Six Hills Way, Stevenage,
Herts. SG1 2AY, United Kingdom
While the author and the publishers believe that the
information and guidance given in this work is correct, all
parties must rely upon their own skill and judgment when
making use of it. Neither the author nor the publishers assume
any liability to anyone for any loss or damage caused by any
error or omission in the work, whether such error or omission
is the result of negligence or any other cause. Any and all
such liability is disclaimed.
The moral right of the author to be identified as author of this
work has been asserted by him/her in accordance with the
Copyright, Designs and Patents Act 1988.

British Library Cataloguing in Publication Data


A CIP catalogue record for this book
is available from the British Library
ISBN 0 85296 922 8

Printed in England by Short Run Press Ltd., Exeter

Introduction
Research into amorphous silicon began, in England, nearly thirty years ago, but the major
development, the demonstration of doping and the subsequent implementation of devices, was
made in Scotland by Spear and LeComber. The history of their attempts to persuade UK
industry of the utility of the new material would make a casebook study of British managerial
and financial short-termism. Since then the physics and applications of amorphous silicon
have been vigorously pursued in America, Asia and Europe, but only the Japanese have
established large scale device production.
Amorphous silicon is now, through the efforts of this worldwide community, a mature
electronic material, in the sense that most of its properties are well known, and reasonably well
understood. There are problem areas, of course: for example, there are uncertainties over
fundamentals like the mobility edge, little understood results like the sign anomalies of the Hall
effect, and detailed problems like the existence of exponential regions in the density of states or
the origin of the width and shape of the luminescence spectrum. Lists like these tend to grow
as you type, but nonetheless, there is an 'industry standard' model, generally accepted, that
qualitatively describes most aspects very well. The days of major new experimental
breakthroughs are almost certainly over, except perhaps in the less well explored alloys.
Amorphous silicon has found its applications role in large area devices: solar cells, xerography
and TFT arrays for matrix addressed displays.
This book follows two previous EMIS volumes on amorphous silicon, and has the same
intention as its predecessors: to provide a compact source of numerical information on different
aspects of the material. The detailed and integrated explanation of possible models was not the
main aim, though all contributors have provided enough background for the reader to
understand the data and its significance. All the Datareviews are new, though some of the
authors have contributed before. My aim as editor was to set out a structure for the book, and
then to persuade leaders in the various specialised areas that they could find the time in their
busy schedules to distil their expertise into a Datareview. There are topics that I had hoped
would be covered, like novel methods of preparation, for which I was unable to find able and
willing authors in time to meet the publisher's schedule, but on the whole the original plan was
fulfilled. Thus, any lacunae are my responsibility. I believe that the assembled Datareviews
give a useful and up-to-date summary of the state of knowledge of amorphous silicon.
Those familiar with the earlier editions will notice that the appearance has changed for the
better, since text is not now restricted by the limitations of a character based screen, and for the
same reason it is now possible to include graphs.
Finally, I would like to thank all contributors to the book. It is their knowledge which gives it
what value it has. I would also like to thank John Sears at the IEE for his help throughout, for
suggestions of names in areas less familiar to me, and for his continual prodding and harrying
of contributors (and occasionally the editor) who were perhaps sometimes heard to wonder why
they had said "yes".
Tim Searle
University of Sheffield
August 1998

Contributing Authors
G. Adriaenssens

Katholieke Universiteit Leuven, Lab. Halfgeleiderfysica,


Celestijnenlaan 200D, B-3001 Heverlee-Leuven, Belgium

4.2

F. Alvarez

Universidade Estadural de Campinus, Instituto di Fisica,


Unicamp 13083-970, Campinus, Sao Paulo, Brazil

3.8

W. Beyer

ISI-PV, Forschungszentrum Juelich, Juelich D-52425,


Germany

C. Bittencourt

Universidade Estadural de Campinus, Instituto di Fisica,


Unicamp 13083-970, Campinus, Sao Paulo, Brazil

3.8

R. Brueggemann

University of Abertay, Dept. Electrical Engineering, Bell St.,


Dundee, DDl IHG, Scotland

4.4

D.E. Carlson

Solarex, Thin Film Development, 826 Newtown-Yardley Road,


Newtown, PA 18940, USA

5.5

A. Catalano

MV Systems Inc., 17301 W. Colfax Avenue, Ste#3O5,


Golden, CO 8041, USA

7.1

J.D. Cohen

University of Oregon, Dept. Physics and Materials


Science Institute, Eugene, OR 97403, USA

3.9

U. Coscia

Polytechnic of Turin, Physics Dept. & INM,


C. so Duca degli Abruzzi 24, 10129 Turin, Italy

3.6

R. Durny

Slovak Technical University, Dept. Physics,


Fac. Electrical Engineering, Ilkovicova 3, Bratislava 812 19,
Slovak Republic

3.5

F. Finger

ISI-PV, Forschungszentrum Juelich, Juelich D-52425,


Germany

E.M. Fortunato

Uninova - Cemop, Quinta da Torre, 2825 Monte de


Caparica, Portugal

F. Giorgis

Polytechnic of Turin, Physics Dept. & INM,


C. so Duca degli Abruzzi 24, 10129 Turin, Italy

2.6, 2.7
3.6, 3.7

F. Giuliani

Polytechnic of Turin, Physics Dept. & INM,


C. so Duca degli Abruzzi 24, 10129 Turin, Italy

2.6, 2.7
3.6, 3.7

D. Goldie

University of Dundee, Dept. Applied Physics, Dundee,


DDl 4HN, Scotland

T.A. Hayes

Oregon State University, Dept. Mechanical Engineering,


Corvallis, OR 97331, USA

1.3, 1.4

1.3, 1.4

6.1

4.1

8.2-8.5

D.I. Jones

University of Dundee, Dept. Applied Physics, Dundee,


DDl 4HN, Scotland

M.E. Kassner

Oregon State University, Dept. Mechanical Engineering,


Corvallis, OR 97331, USA

8.2-8.5

D. Kruangam

Chulalongkom University, Dept. Electrical Engineering,


Bangkok 10330, Thailand

6.3, 7.5

L. Ley

Universitaet Erlangen, Institut fuer Technische Physik,


Erwin-Rommel-Strasse 1, D-91058 Erlangen, Germany

3.1,3.2

A.H. Mahan

NREL, 1617 Cole Blvd., Golden, CO 8041, USA

2.1

C. Main

University of Abertay, Dept. Electrical Engineering, Bell St.,


Dundee, DDl IHG, Scotland

4.5

Uninova - Cemop, Quinta da Torre, 2825 Monte de


Caparica, Portugal

6.1

Slovak Academy of Science, Institute of Physics,


Dubravska cefta 9, Bratislava 842 28, Slovak Republic

3.4

R. Martins

V. Nazdazy

H. Ohsaki

P.D. Persans

E. Pincik

Central Research Center, Asahi Glass Co. Ltd.,


Hazawa-cho, Kanagawa-ku, Yokohama 221, Japan
Rensselaer Polytechnic Institute, Troy, NY 12180-3590,
USA
Slovak Technical University, Dept. Physics,
Fac. Electrical Engineering, Ilkovicova 3, Bratislava 812 19,
Slovak Republic

4.3

8.1, 8.6-8.8

6.2

3.5

CF. Pirri

Polytechnic of Turin, Physics Dept. & INM,


C. so Duca degli Abruzzi 24, 10129 Turin, Italy

2.6, 2.7
3.6, 3.7

V. Rigato

Polytechnic of Turin, Physics Dept. & INM,


C. so Duca degli Abruzzi 24, 10129 Turin, Italy

2.6

P. Roca i Cabarrocas Laboratoire de Physique des Interfaces et des Couches


Minces, Ecole Polytechnique (UPR 258 du CNRS),
F-91128 Palaiseau Cedex, France

1.1, 1.2

MJ. Rose

University of Dundee, Dept. Applied Physics, Dundee,


DDl 4HN, Scotland

7.2

T.M. Searle

University of Sheffield, Dept. Physics, Hicks Building,


Sheffield, S3 7RH, UK

5.1-5.4

I. Shimizu

Tokyo Institute of Technology, The Graduate School,


4259 Nagatsuta, Midori-ku, Yokohama City 227, Japan

7.4

S. Shirai

Canon Ecology Research & Development Center, Canon Corp.,


411 Kizugawadai, Kizu-cho, Souraku-gun, Kyoto 619-02,
Japan

M. Stutzmann

Technische Universitaet Muenchen, Walter Schottky Institut,


Am Coulombwall, D-85748 Garching, Germany

2.3-2.5

K. Suzuki

Toshiba Corporation, Res. Lab. 1, Materials & Devices Labs.,


33, Shin Isogo-cho, Isogo-ku, Yokohama 235, Japan

6.4, 7.3

R. Swanepoel

Rand Afrikans University, Dept. Physics, PO Box 524,


Johannesburg 2006, South Africa

8.9

Y. Tatsumi

Shinshu University, Dept. Physics, Inst. Higher Education,


Nishi-Nagano, Nagano 380, Japan

8.1

P.C. Taylor

University of Utah, Dept. Physics, Room 201,


115 South 1400 East, Salt Lake City, UT 84112-0830, USA

3.3

I. Thurzo

Slovak Academy of Science, Institute of Physics,


Dubravska cefta 9, Bratislava 842 28, Slovak Republic

3.4

E. Tresso

Polytechnic of Turin, Physics Dept. & INM,


C. so Duca degli Abruzzi 24, 0129 Turin, Italy

D.L. Williamson

Colorado School of Mines, Dept. Physics, Golden,


CO 80401, USA

2.2

S. Zandolin

Polytechnic of Turin, Physics Dept. & INM,


C. so Duca degli Abruzzi 24, 10129 Turin, Italy

2.6

7.4

2.6, 2.7
3.6, 3.7

Abbreviations
The following abbreviations are used in this book:
AC
ASAXS

alternating current
anomalous small angle X-ray scattering

BBL
BC
BIS
BM

bottom blocking layer


bond-centre
bremstrahlen isochromat spectroscopy
black matrix

CB
CBT
CCD
CF
CFSYPS
CMOS
CPM
CxV
CVD
CW

conduction band
conduction band tail
charge coupled device
colour filter
constant field state photoemission yield spectroscopy
complementary metal oxide semiconductor
constant photocurrent method
current-voltage measurements
chemical vapour deposition
continuous wave

DB
DBR
DC
DLTS
DMR
DOS
DRAM
DSC
DV

dangling bond
distributed Bragg reflector
direct current
deep level transient spectroscopy
deuteron magnetic resonance
density of states
dynamic random access memory
differential scanning calorimetry
direct view

ECR
EL
ERD
ERDA
ESR
EXAFS

electron cyclotron resonance


electroluminescence
elastic recoil detection
elastic recoil detection analysis
electron spin resonance
extended X-ray absorption fine structure

FF
FWHM

fill factor
full width at half maximum

GD
GD

gas discharge
glow discharge

HD
HMC

high dilution (with hydrogen)


heterojunction-monitored capacitance

HOMOCVD
HTI
HW
HWCVD

homogeneous chemical vapour deposition


hot carrier tunnelling injection
hot-wire
hot-wire chemical vapour deposition

IBS
ICTS
IPE
IR
ITO
IxV

ion beam sputtering


isothermal capacitance transient spectroscopy
internal photoemission spectroscopy
infrared
indium tin oxide
current-voltage measurements

LA
LC
LCD
LED
LESR
LEYS
LO
LPCVD

longitudinal acoustical
liquid crystal
liquid crystal display
light emitting diode
light-induced electron spin resonance
low energy yield spectroscopy
longitudinal optical
low pressure chemical vapour deposition

MBE
MIS
MOS
MPC
MPG

molecular beam epitaxy


metal-insulator-semiconductor
metal oxide semiconductor
modula
ted photocurrent
modulated/moving photocarrier grating

NMR

nuclear magnetic resonance

ODMR
ODOS
OEIC
OMS
OPC

optically detected magnetic resonance


occupied density of states
optoelectronic integrated circuit
optically modulated spectroscopy
organic photoconductor

PA
PAS
PCVD
PDOS
PDS
PE
PECVD
PEP
PES
PID
PJ
PL
PPES

photoinduced absorption
photoacoustic spectroscopy
plasma chemical vapour deposition
partial density of states
photothermal deflection spectroscopy
photoelectron
plasma enhanced chemical vapour deposition
photolithography and etching process
photoelectron spectroscopy
photo-induced discharge
projection
photoluminescence
photo-pyroelectric spectroscopy

PTTOF
PV
PVD

post transit time of flight


photovoltaic
plasma vapour deposition

QFRS

quadrature frequency resolved spectrum

R
RBS
RF
RF
RP
RT

Raman
Rutherford backscattering
radio frequency
reflective mode
remote plasma
room temperature

SANS
SAS
SAW
SAXS
SCLC
SCL-TOF
SIMS
SP
SR
SSPC
SSPG
SW

small angle neutron scattering


small angle scattering
surface acoustic waves
small angle X-ray scattering
space charge limited current
space charge limited time of flight
secondary ion mass spectrometry
sputtering
spectral response
steady state photoconductivity
steady state photocarrier grating
Staebler-Wronski

TA
TBL
TCO
TEM
TFLED
TFPD
TFT
TO
TOF
TPC
TSC
TSCAP
TSD

transverse acoustical
top blocking layer
tin copper oxide
transmission electron microscopy
thin film light emitting diode
thin film photodiode
thin film transistor
transverse optical
time of flight
transient photoconductivity
thermally stimulated current
thermally stimulated capacitance
thermally stimulated desorption

UHV
UPS
UV

ultra high vacuum


ultraviolet excited photoelectron spectroscopy
ultraviolet

VB
VB-DOS
VBM
VBT

valence band
valence band density of states
valence band maximum
valence band tail

VFP
VGA
VHF
VHN
VL

voltage-filling pulse
video graphic array
very high frequency
Vickers hardness number
vacuum level

XES
XPS
XPS

X-ray emission spectroscopy


X-ray photoelectron spectroscopy
X-ray photoemission spectroscopy

Contents

Introduction ............................................................................................................

vii

Contributing Authors ..............................................................................................

viii

Abbreviations .........................................................................................................

xi

1.

Preparation ....................................................................................................

1.1

Growth of Undoped a-Si:H by PECVD ...............................................................

1.2

Growth of Doped a-Si:H by PECVD ...................................................................

13

1.3

Growth of a-Si:Ge:H Alloys by PECVD Gas Sources, Conditions in the


Plasma and at the Interface ................................................................................

20

Growth of a-Si:Ge:H Alloys by PECVD Optimization of Growth


Parameters, Growth Rates, Microstructure and Material Quality .......................

30

Structural and Vibrational Properties .........................................................

37

2.1

Structural Information on a-Si:H from IR and Raman Spectroscopy ..................

39

2.2

Structural Information on a-Si:H and Its Alloys from Small Angle Scattering
of X-Rays and Neutrons .....................................................................................

47

2.3

Data on Hydrogen in a-Si:H from IR and Raman Spectroscopy .........................

56

2.4

Data on Hydrogen in a-Si:H from NMR ..............................................................

61

2.5

Data on Hydrogen in a-Si:H from Diffusion and Effusion Studies .......................

66

2.6

Structural Information on a-SiC:H from IR and Raman Spectroscopy ................

74

2.7

Structural Information on a-SiN:H from IR and Raman Spectroscopy ................

85

Electronic Structure .....................................................................................

91

1.4

2.

3.

3.1

Conduction and Valence Band Density of States of a-Si:H


Photoemission, Inverse Photoemission and Core Level Absorption
Spectroscopy ......................................................................................................

93

3.2

Band Tails of a-Si:H Photoemission and Absorption Data .............................. 113

3.3

Information on Gap States in a-Si:H from ESR and LESR ................................. 139

3.4

Information on Gap States in a-Si:H from Thermal Defect Spectroscopies ........ 143

3.5

Information on Gap States in a-Si:H from Photoinduced Absorption .................. 151

3.6

Information on Gap States in a-SixC1-x:H from ESR, LESR, Constant


Photocurrent and Photothermal Deflection Spectroscopies ............................... 161

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vi

4.

5.

6.

7.

8.

Contents
3.7

Information on Gap States in a-Si1-xNx:H from ESR, LESR and


Photothermal Deflection Spectroscopies ............................................................ 168

3.8

Valence Band Offsets of a-Si1-xCx on c-Si and a-Si:H ........................................ 174

3.9

Electronic Structure of a-Si:Ge:H ....................................................................... 180

Electronic Transport ..................................................................................... 189


4.1

Dark Conductivity in Undoped a-Si:H Deposited by Plasma-Enhanced


CVD Methods ..................................................................................................... 191

4.2

Mobilities in a-Si:H .............................................................................................. 199

4.3

Thermoelectric Power and Hall Effect in a-Si:H .................................................. 209

4.4

Steady State Photoconductivity in a-Si:H and Its Alloys ..................................... 217

4.5

Transient Photoconductivity in a-Si:H and Its Alloys .......................................... 227

Recombination of Excess Carriers ............................................................. 235


5.1

Luminescence of a-Si:H ..................................................................................... 237

5.2

Luminescence of a-Si:N:H .................................................................................. 245

5.3

Luminescence of a-Si:C:H .................................................................................. 252

5.4

Luminescence of a-Si:Ge:H ................................................................................ 259

5.5

Light-Induced Defects and the Staebler-Wronski Effect in a-Si:H ...................... 264

Junctions and Thin Film Transistors .......................................................... 271


6.1

Schottky a-Si:H Devices ..................................................................................... 273

6.2

a-Si:H/a-Si:X:H Multilayers and Evidence for Quantum Confinement ................ 284

6.3

Electroluminescence from a-Si:H p-i-n Junctions and a-Si:X:H


Heterojunctions ................................................................................................... 293

6.4

a-Si:H Thin Film Transistors ............................................................................... 305

Photoelectronic Devices .............................................................................. 311


7.1

Amorphous Silicon Solar Cells ........................................................................... 313

7.2

Amorphous Silicon Photodetectors .................................................................... 319

7.3

Amorphous Silicon Large Area Displays ............................................................ 325

7.4

Amorphous Silicon Xerographic Applications ..................................................... 331

7.5

Amorphous Silicon Alloy LEDs ........................................................................... 337

Macroscopic Data ......................................................................................... 347


8.1

Density of a-Si, a-SiNx, a-SiC and a-SiGe .......................................................... 349

8.2

Elastic Constants of a-Si and a-Si:H .................................................................. 359

8.3

Hardness and Wear of a-Si and a-Si:H .............................................................. 363

8.4

Intrinsic Stress in a-Si and a-Si:H Films ............................................................. 367

8.5

Thermal Expansion Coefficient of a-Si and a-Si:H ............................................. 370

8.6

Specific Heat of a-Si, a-Si:H and a-SiNx ............................................................. 372


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Contents

vii

8.7

Thermal Conductivity of a-Si, a-SiNx and a-SiC ................................................. 376

8.8

Melting Point of a-Si and a-Si:H ......................................................................... 383

8.9

Optical Functions of Amorphous Silicon ............................................................. 386

Index ..................................................................................................................... 405

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CHAPTERl

PREPARATION
1.1
1.2
1.3
1.4

Growth of undoped a-Si:H by PECVD


Growth of doped a-Si:H by PECVD
Growth of a-Si:Ge:H alloys by PECVD - gas sources,
conditions in the plasma and at the interface
Growth of a-Si: Ge:H alloys by PECVD - optimisation of
growth parameters, growth rates, microstructure and
material quality

1.1

Growth of undoped a-Si:H by PECVD


P. Roca i Cabarrocas
August 1997

INTRODUCTION

Hydrogenated amorphous silicon thin films have been the subject of extensive research in the
past thirty years, boosted by applications and the challenging fimdamental issues related to this
disordered semiconductor (structure, doping, stability etc.) [1,2]. Here we focus on the growth
processes of a-Si:H, which determine, to a large extent, its optoelectronic properties and the
performance of related devices. The optimisation of a-Si:H deposition conditions implies a
complete understanding of the processes involved in its growth as well as the correlation
between the deposition conditions and the optical, structural and transport properties [2].
Because of the disordered nature of a-Si:H, the detailed characterisation of the film properties
and the correlation between the structure and the optoelectronic properties is still in progress
[I]. As a consequence, the optimisation of a-Si.H has been mostly achieved by trial and error,
and supported by fundamental studies which offer a better understanding of the growth
mechanisms and the necessary framework for a further improvement of this material. FIGURE
1 schematically describes such a framework, which can be decomposed into four steps: (i) the
dissociation of the gas precursors; (ii) the plasma physics and chemistry, which determine the
flux and nature of reactive species to the substrate; (iii) the plasma-surface interactions; and
Electrical Power
Electron density
Energy distribution

Pump

Plasma processes

SiH 4 FlOw

Primary
reactions

Increasing
RF power,
Pressure,
Geometry,
Flow

Secondary
reactions

Clusters, Polymers
Powder

Surface and
Bulk
Processes

Ions, Radicals, Photons,...

Growth zone
Bulk

Surface mobility
Chemical equilibrium

Substrate Temperature
FIGURE 1 Schematic representation of the processes involved in a-Si:H deposition.

(iv)the reactions taking place in a growth-zone where cross-linking reactions result in the
formation of the film.
B

DEPOSITION METHODS

The search for a-Si:H with improved properties (low defect density, higher carrier mobility,
enhanced stability, etc.) has led researchers to explore a large number of deposition methods
and, within each of them, the effects of each process parameter. Amorphous silicon films
produced by evaporation of a silicon target or by sputtering in the absence of hydrogen, have a
high density of defects which render them useless for electronic applications. In contrast, the
films produced by the dissociation of hydride gases have a low defect density which allows
doping [3]. It took a few years to recognise the fundamental role of hydrogen in the passivation
of silicon dangling bonds and thus in reducing the density of defects in the gap of the
semiconductor. Today, the role of hydrogen is largely recognised and a-Si:H is considered in
some aspects as a hydrogen glass [4] in which hydrogen plays a key role during growth as it
determines the structure of the film [5]. Different methods have been used to dissociate the gas
precursors, all variants of a CVD process: HOMOCVD, PECVD, PHOTOCVD etc. [6-8].
Among PECVD methods, different excitation modes and geometry of the reactor have been
explored [6,9]. RF (13.56 MHz) glow discharge is the most widely used deposition technique
because it combines low temperature operation, thanks to the plasma dissociation, and the
possibility of scaling-up the size of the substrates. Even though the use of higher excitation
frequencies has been studied as a way to increase deposition rate [10], high rates are also
achieved at 13.56 MHz, the standard frequency for industrial applications. As a matter of fact,
whatever the technique, the increase of the gas dissociation will favour secondary reactions
(FIGURE 1), leading to the formation of polymers, clusters and powder, which will be in most
cases the limiting factor to the increase of the deposition rate [H]. In the following we will
focus on RF glow discharge processes even though most of the discussion can be applied to
deposition by other techniques.

GAS PHASE PROCESSES

Silane is the most common source in a-Si:H deposition even though other hydrides (Si2H6,
Si3H8) [12], fluorides (SiF4, Si2F6) [13], chlorides (SiCl4, SiH2Cl2) [14], SiH3F and SiH2F2 [15]
source gases have been used. The claimed benefits associated with the use of these gases
(higher deposition rates, or improved stability) are however a subject of controversy [12].
Indeed, many reactions are involved in the growth process and it is not straightforward to
impute an improvement in the a-Si:H properties to the gas precursor.
The production of reactive species can result from either primary or secondary reactions
(FIGURE 1). By primary reactions one understands inelastic collisions between the electrons
and the gas molecules. The energy of the electric field is coupled to the electrons through four
basic mechanisms: (i) secondary electron emission, (ii) stochastic heating, (iii) wave-riding, and
(iv) Joule heating [9]. The results of the primary reactions are the radicals and ions responsible
for a-Si:H deposition [16]. At low pressure, low silane dissociation and temperatures above
2000C primary reactions alone are sufficient to describe a-Si:H deposition. Under these
conditions, SiH3 radicals can account for a large fraction of the deposition [17] even though this

has been a subject of controversy [18]. Understanding of plasma chemistry has been achieved
through plasma diagnostics:
(i)

Langmuir probes and electrostatic analysers [19,20] which provide information on the
electron and ion densities and distribution functions.

(ii)

Mass spectrometry which provides information on the reactive species: radicals (SiH3,
SiH2, SiH, Si), as well as the positive and negative ions reaching the substrate [21].

(iii)

Optical techniques such as optical emission spectroscopy, actinometry, optical


absorption, and laser induced fluorescence, giving information on the neutral and excited
species of the discharge [21]. Light scattering techniques have been recently developed
to study particles in plasmas [22].

Thanks to these diagnostic techniques, a set of cross sections for the different reactions as well
as the constant rates have been tabulated [23,24]. They are essential for modelling silane
dissociation and a-Si:H deposition processes [25]. Nowadays, modelling a-Si:H deposition
under conditions dominated by primary processes is satisfactory and allows prediction of a-Si.H
deposition rates [26]. However, applications push towards high deposition rates and/or low
substrate temperatures. In those cases, secondary reactions are no longer negligible and they
may completely determine the film quality. In contrast to the primary reactions, secondary
reactions are less well characterised and therefore the predictions of a-Si:H deposition models
become less reliable when secondary reactions are dominant.
The effect of secondary reactions has been mainly addressed through the formation of powders.
Powder formation in silane plasmas was recognised from early studies as a factor limiting film
quality [23,27], even though low defect density a-Si:H films can be deposited at high rates
under powder conditions [H]. More recently, dusty plasmas have been the subject of
workshops [28]. Even though the detailed mechanisms leading to powder formation in silane
plasmas are not completely known, strong evidence has been given for anions being the
precursors of powder [29]. The effect of powders on film properties has not been completely
elucidated. Large powders are negatively charged and therefore confined in the plasma until
other forces (thermophoresis, gravity, ion drag, gas flow, etc.) can overcome the electrostatic
confinement [30]. When powders overcome the electrostatic confinement, they can be
incorporated in the a-Si:H thin film and produce macroscopic defects like pin-holes. To avoid
these problems, schemes like a progressive decrease of RF power, total pressure, or an increase
of the gas flow have been suggested in order to sweep the powders out of the discharge, and
impede them from falling on the substrate [9]. Rather than avoid powder formation, there is a
tendency to live1 with powders because their presence favours the coupling of the RF power
into the discharge and therefore the achievement of high deposition rates [31]. Finally, recent
reports focus on the role of small particles on a-Si:H properties. While some reports suggest
that these nanoparticles will have a negative effect [32], there is experimental evidence that the
incorporation of these nanoparticles in a-Si:H films can result in nanostructured silicon thin films
with improved properties compared to a-Si:H [33,34].
This short review of the gas phase processes highlights the complexity of the plasma processes
involved in a-Si:H growth. Indeed, depending on the process conditions (FIGURE 1), the

growth of a-Si:H will be a consequence of primary reactions, secondary reactions, or both of


them, resulting in a wide variety of a-Si:H materials.

SURFACE AND BULK PROCESSES

Gas phase processes are important because they determine the nature of the reactive species
contributing to a-Si:H deposition. However, a-Si:H growth cannot be considered just as a
condensation of radicals on the substrate. Indeed, while the radicals and ions responsible for
a-Si:H deposition are highly hydrogenated, a-Si:H films contain 10% hydrogen. Therefore
cross-linking reactions must take place at the film surface or in a growth-zone [23]. One could
ask whether the a-Si:H properties are determined by the film precursors (gas phase reactions) or
by the reactions of these precursors on the film surface. As for the plasma processes, diagnostic
techniques have been developed to monitor in-situ the growth processes and the optical and
electrical properties of the films/devices. UV-visible ellipsometry provides real-time information
on the optical properties of the films, and through the use of effective medium theories allows
one to get a clear picture of the effects of the different process parameters on the growth
mechanisms (homogeneous growth, nucleation, interaction with the substrate) and the evolution
of the film properties during growth [35,36]. The extension of ellipsometry to the infrared
wavelengths [35,37] or the use of other IR techniques [38] provides information on the
hydrogen bonding and therefore on the cross-linking reactions resulting in the formation of the
film. The transport properties can also be measured in-situ by the use of other techniques such
as the Kelvin probe which provides information on the effects of doping and the evolution of the
potential at interfaces [39], optogalvanic photoemission which gives information on the work
function of the layer [40], and time resolved microwave conductivity which can provide
information on the majority carrier mobility and lifetime [41].
While the use of these techniques helps the optimisation of the deposition process and gives a
deep insight into the growth mechanisms, the important parameters for the surface reactions are
not always directly accessible. Among them are the substrate temperature, the surface mobility
and the sticking coefficient of the film precursors.
The effects of substrate temperature on the growth and properties of a-Si:H thin films have been
widely studied. However, the temperature at the surface of the growing film cannot be easily
measured and is affected by the plasma conditions and reactor geometry [42,30]. As a
consequence, and because substrate temperature affects not only surface reactions but also the
plasma processes [43,44], different and/or opposite trends can be found for the deposition rate
or in a-Si:H properties (see FIGURE 2).
The mobility of the radicals at the growing a-Si:H surface is often considered an important
factor for the deposition of high quality a-Si:H films [45-47]. The combination of surface
mobility and hydrogen coverage can account for example for the usually observed optimum
substrate temperature around 2500C. At lower substrate temperature, surface mobility would
be too low for an optimum growth to occur, while at higher temperature the depletion of
hydrogen at the film surface would produce surface defects and a decrease of the surface
mobility. This concept of surface mobility goes along with the sticking coefficient of the
radicals. The sticking coefficient of SiH3 has been measured to be 0.2 - 0.3 [48,49], which is
equivalent to a high surface diffusion. In contrast, because they have more than one unsatisfied

bond, a sticking coefficient close to 1 is attributed to SiH2, SiH and Si radicals; i.e. they have
low surface mobility. Based on these ideas, it is commonly accepted that SiH3 is the good
a-Si:H precursor. This distinction between radicals with a low sticking coefficient (high surface
mobility) and radicals with high sticking coefficient (low surface mobility) has also been used to
distinguish between CVD-like and PVD-like processes [50].
CVD-like processes usually lead to low deposition rates. As the plasma parameters are changed
in order to increase the deposition rate, it is generally found that the substrate temperature has
to be increased to obtain low defect density a-Si:H [47,51]. Indeed, in the framework of
models based on the mobility of the film precursors, the increase of the deposition rate should
be accompanied by the supply of more energy to the growing surface in order to enhance the
diffusion of the film precursors and favour cross-linking reactions. Alternative models in which
chemical reactions take place in a growth-zone have been proposed. Under the hypothesis that
growth reactions take place under equilibrium conditions, Winer proposed that optimal growth
occurs when the deposition rate is equal to the rate of hydrogen diffusion from the growth-zone
[51]. As in the case of the surface models in which only the mobility of the film precursors is
taken into account, these equilibrium models account for the shift of the optimum substrate
temperature to higher values when the deposition rate increases. These equilibrium models
have been further elaborated by taking into account the evolution of the chemical potential of
hydrogen in the plasma and in the growing film [5]. Models based on surface mobility or on
chemical equilibrium reactions in a growth-zone give a good description of the optimum
substrate temperature for a-Si:H growth, but are limited to growth from SiH3. However, low
defect density a-Si:H films have been deposited even at 500C [52] and/or under conditions of
high pressure and RF power, under which other radicals or even silicon nanoparticles contribute
to the growth [33,34]. Why can low defect density a-Si:H films be deposited under such
conditions? The weakness of surface models lies in the underlying hypothesis: growth from
SiH3 radicals and process controlled by substrate temperature and deposition rate. Indeed,
other parameters than the substrate temperature can modify the diffusion rate of hydrogen [53].
As an example, besides radicals, positive ions also contribute to a-Si:H deposition and even
though the ratio of ions to radicals is generally smaller than 0.1, their effect on film properties is
very important, in particular under non-optimised deposition conditions [54]. As a matter of
fact, ion bombardment has been found to have effects comparable to an increase of the surface
temperature [55].

OPTIMISATION OF DEPOSITION CONDITIONS

The optimisation of a-Si:H growth has been one of the main subjects in this field. The effects of
different plasma conditions (FIGURE 1), reactor geometry, excitation frequency and dilution of
the silane on a-Si:H properties have been widely studied [7]. The difficulty of optimising a-Si:H
growth is related to the fact that these parameters are correlated. Indeed, the important aspects
for the growth are the rate of production of reactive species, their interaction during their
diffusion to the walls (substrates) and their reactions at the growing surface.
Increasing the RF power, for example, increases the dissociation rate and therefore the
deposition rate. However, the higher dissociation may result in a change in the species involved
in the growth because of an increasing importance of secondary reactions [56].

An increase of the pressure may produce similar effects: enhanced dissociation because of the
increased electron-silane collisions, enhanced secondary reactions and deposition rate, along
with a change in the nature of film precursors [12,57].
The dilution of silane in inert gases (argon, helium, xenon) can affect the electron distribution
function, the rate of silane dissociation and therefore the deposition rate [58]. While inert gases
do not play a role in the cross-linking reactions taking place at the film surface or in the growthzone, the use of hydrogen dilution strongly modifies them. The use of hydrogen dilution has
been reported as an excellent way to improve a-Si:H properties [59]. As a matter of fact, the
interaction of hydrogen in the growth-zone allows a change from a-Si:H to microcrystalline
silicon growth [60].
Changing the reactor geometry, in particular the inter-electrode distance, strongly affects the
flux of particles to the substrate [24,61,62]. To some extent, the increase of inter-electrode
distance is equivalent to an increase of the total pressure (Paschen's law [19]).
The substrate temperature, whose effects have been mainly discussed in terms of surface
reactions [45-47], also has a strong effect on plasma reactions [44], in particular on the
formation of powders [43].

Deposition rate (AJs)

As an example of the interdependence of the deposition parameters, FIGURE 2 shows the


deposition rate as a function of the substrate temperature for a-Si:H films deposited in the same
reactor [42] under different plasma conditions.

Substrate temperature (0C)


FIGURE 2 Effect of the substrate temperature on the deposition rate of a-Si:H films deposited under different
plasma conditions. Series A: pure silane, 40 mtorr, low RF power (0.5 W) and inter-electrode distance, d,
of 2.8 cm. Series B: 40% silane in helium gas mixture, 550 mtorr, 10 W, d = 12 mm. Series C: same
conditions as series B but d = 28 mm. Series D: same conditions as series C but 15 W.

Series A (open circles) correspond to a-Si:H films produced by the dissociation of pure silane at
low pressure (40 mtorr) and low RF power (0.5 W), with the reactor having an inter-electrode
distance of 28 mm. Under these conditions there is no formation of powder in the reactor. The

increase of the deposition rate in this so-called a-regime [57] has been explained by the
temperature dependence of gas phase reactions [44],
Series B (filled circles) corresponds to a-Si:H films produced by the dissociation of 40% silane
in helium gas mixture at high pressure (550 mtorr) and high RF power (10 W)9 with the reactor
having an inter-electrode distance of 12 mm. We observe the same dependence of the
deposition rate on the substrate temperature as for series A, except for the factor of 4 increase
in deposition rate, which can be explained by the higher RF power and the smaller interelectrode distance.
Deposition under the same plasma conditions as in series B but with an inter-electrode distance
of 28 mm (open squares, series C) completely changes the temperature dependence of the
deposition rate. In this case the plasma is in the so-called y-regime [12,57] in which the RF
power is more efficiently coupled to the plasma because of the formation of powders. The
increase of deposition rate between 1500C and 2500C can be attributed to the reduction of
powder formation and therefore to a decrease in the losses to the pumps [56]. Above 2500C,
the further reduction in powder formation makes the plasma switch to the a-regime. Finally,
under the same conditions as in series C, but with an RF power of 15 W (series D, filled
squares), the deposition rate shows a similar trend but with higher absolute values.
These changes in deposition rate are accompanied by changes in the optical, structural and
electronic properties of the films [11,53]. FIGURE 3 shows the defect density as a function of
the substrate temperature for the above series of samples. For each series there is a temperature
above which the defect density sharply decreases. The higher the deposition rate, the higher the
temperature threshold, in qualitative agreement with models taking into account the mobility of
the radicals at the film surface or the diffusion of hydrogen in the growth zone. However, the
films of series B have about the same threshold temperature as the films of series A, despite the
factor of 4 higher deposition rate, while the samples of series C have a higher threshold
temperature despite a smaller deposition rate. Therefore, other factors than deposition rate and
temperature determine the optimal growth conditions. This is emphasised by the two stars at
100 and 500C corresponding to films deposited at similar growth rate to series A, but at lower
pressure (1000C) or from a silane-hydrogen mixture (500C). In both cases the lower defect
density at these temperatures can be explained by the enhanced ion bombardment which
increases the surface temperature and avoids the polymerisation at the film surface [52].
Therefore plasma and/or surface polymerisation appear as limiting factors for the growth of low
defect density a-Si:H at low substrate temperatures. Indeed, while it is not clear whether
polymerisation takes place in the gas phase or at the film surface, it is well established that
silicon polymers are thermally dissociated above 2000C [63], which could explain why the
optimal growth temperature is often reported to be above 2000C as well as the sharp decrease
in defect density (FIGURE 3). While SinH1n polymers result in highly hydrogenated and
disordered films with a high defect density, the growth of a-Si:H films under conditions close to
the formation of powders can result in low defect density films with enhanced microstructure
and stability [33,34]. As an example, the samples of series C and D in FIGURE 3 were
deposited under powder conditions. However, except for the films deposited below 2000C,
corresponding to the temperature necessary to avoid polymers, the defect density is low.
However the films have a larger microstructure as can be defined from the hydrogen bonding
for example [53]. Under these conditions of high deposition rate the models based on surface
mobility and chemical equilibrium reactions still apply. Indeed, as the deposition rate increases

Defect density (cm"3)

(series D versus series C), the threshold substrate temperature shifts to higher temperature.
However, the sharp transition between high and low defect density films suggests that also the
nature of the film precursors changes. Therefore, deposition under powder conditions can
result in a-Si:H films with low defect density. This is further validated by recent studies on the
growth of a-Si:H films under conditions where silicon nanoparticles as well as radicals
contribute to the growth [33].

A
B
C
D

Substrate temperature (0C)


FIGURE 3 Effect of substrate temperature on the defect density of a-Si:H films produced
under different plasma conditions. Same symbols as in FIGURE 2.

CONCLUSION

The growth of a-Si:H thin films by the dissociation of gas precursors in a glow discharge is a
complex process in which gas phase reactions as well as surface reactions have to be
considered. In-situ diagnostic techniques of the plasma phase and of the growing film provide
valuable information to understand the growth mechanisms and help to optimise the deposition
conditions. These in-situ techniques are complemented by ex-situ characterisation methods
providing complementary information on the optical and electronic properties of the films.
Deposition rate and substrate temperature are the main parameters which determine the
properties of a-Si:H. While many models based on the surface mobility of the film precursors or
on the existence of chemical equilibrium reactions at the growing film surface describe the
growth under conditions where SiH3 radicals are the main film precursors, the ability to deposit
low defect density a-Si:H films down to 500C or under conditions where other radicals than
SiH3 or even nanoparticles contribute to deposition suggests that ion bombardment and
secondary reactions taking place in the gas phase also play a crucial role in a-Si:H quality.
As a conclusion, a-Si:H is a new thin film which, pushed by its applications, has experienced
extraordinary development in the last thirty years. The understanding acquired of the plasma
and growth processes allows us to foresee further developments of this material.

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1.2

Growth of doped a-Si:H by PECVD


P. Roca i Cabarrocas
September 1997

INTRODUCTION

Doping of amorphous semiconductors was unexpected as it is against Mott's 8-N rule [1]
stating that atoms in an amorphous solid should have a coordination of min[N, 8-N], where N is
the number of valence electrons. Thus boron and phosphorus should be threefold coordinated,
i.e. non-dopant. However in 1975 Spear and Le Comber reported on the substitutional doping
of amorphous silicon films, produced by the decomposition of silane [2]. Of course, the
question as to why it is possible to dope a-Si:H drew a large amount of attention raising the
possibility of various applications. Review articles on the doping of a-Si:H can be found in
[3-6].

DOPING EFFICIENCY AND DOPING MECHANISMS

Even though the predictions of non-dopability of a-Si:H were demonstrated to be wrong [2], it
appeared that most of the dopants in a-Si:H are threefold coordinated, as expected from the
8-N rule, i.e. doping efficiency (r\) is very low. Indeed, only extended X-ray absorption fine
structure (EXAFS) [7] measurements on a-Si:H films doped with either P or As gave, at the
most, a 20% fraction of fourfold coordinated atoms, while nuclear magnetic resonance
measurements on boron-doped a-Si:H revealed only threefold coordinated boron [8]. Detailed
studies by Street using a charge sweep-out experiment [9] confirmed this low doping efficiency
(IO"3 < T] < 10"1), which is inversely proportional to the square root of the concentration of
dopants in the gas phase [6,10]:
(1)
where k is a constant and Cg is defined by the ratio of the dopant gas flow rate to the silane flow
rate. The low values of r\ suggest that most of the dopant atoms satisfy the 8-N rule and only a
small fraction of them are fourfold coordinated.
Different models have been developed to explain doping in a-Si.H. In particular, the formation
of valence-alternation-pairs has been suggested as the mechanism responsible for doping
[11,12]. However, it was the extension of the 8-N rule to charged impurity states by Street that
allowed for a better understanding of doping of a-Si:H [10]. According to Street, doping by
phosphorus can be described by a solid state chemical equilibrium reaction:
(2)
where the equilibrium between threefold and fourfold coordinated phosphorus atoms is
balanced by defects (silicon dangling bonds). This reaction, first proposed to take place at the

film growing surface, was extended to describe bulk dopant equilibrium [13]. As a direct
consequence of this model doping of a-Si:H is accompanied by an increase of the defect density.
Moreover the application of the law of mass action to EQN (2) leads to the square root
dependence of the doping efficiency (EQN (I)) and is in agreement with most of the
experimental results concerning doping in a-Si:H and a-Ge:H [3].
Surprisingly, the deposition conditions are not taken into account in EQN (2); i.e. doping is
considered independently of the plasma parameters. While the importance of solid-phase
reactions is supported by a large number of studies concerning thermal equilibrium and
metastability in a-Si:H thin films [6], some experimental results cannot be explained, in
particular the presence of neutral defects and the fact that the dopant efficiency is dependent on
the gas phase concentration and not on the solid phase concentration [14]. This has led some
authors to extend Street's approach to specific chemical reactions taking place at the a-Si:H
surface during growth [15,16]. Further progress in understanding doping of a-Si:H will be
obtained by a better understanding of a-Si:H growth processes [14].

DOPANT SOURCES

Interestingly, with the growth of a-Si:H by PECVD dopants can be mixed with silane in a
controlled way to achieve the desired doping level. Indeed, even though other techniques such
as ion implantation or diffusion from a solid source have been used [17,18], the direct addition
of the dopant gases to the silane remains the easiest way to achieve doping. While phosphine
and diborane are the most common dopants, other gases have been used to reduce the toxicity
or to improve the doping efficiency. In particular, doping with diborane is difficult to control
because of the thermal CVD at low temperature [19]. Trimethylboron has attracted much
attention because of its higher stability and lower toxicity [20]. Moreover, doping with
trimethylboron is accompanied by the incorporation of carbon in the a-Si:H network [21] which
can be exploited for the growth of low absorption layers. Boron trifluoride [22],
trimethylgallium [20,23], trimethylaluminium, and triethylboron [24] have been studied as
p-type dopants, while liquid organic sources have been used for n-type doping [25]. Impurities
at low concentration have also been reported to act as dopants in a-Si:H, with particular reports
of the donor-like effects of oxygen [26,27] and nitrogen [28]. In the following we will focus on
the doping of a-Si:H by phosphine or diborane.

EFFECTS OF DOPANTS ON a-Si:H GROWTH

Few studies have been devoted to the effect of dopants on the plasma chemistry. However,
both B2H6 and PH3 have ionisation potentials below 11 eV and may modify the plasma
composition in a similar way to Ar and Kr dilution [29]. Mass spectrometry studies have shown
that while silane and silane-phosphine discharges are similar, the addition of diborane results in
a modification of the discharge because of the higher dissociation of diborane and the formation
of diboron-type ions [30].
The effects of dopants on a-Si:H growth have been widely studied. It is well established that
the addition of diborane results in an increased deposition rate for deposition from silane
precursors [31], while the addition of phosphine has a small effect or produces a reduction in

the deposition rate [32]. The enhancement of the deposition rate by diborane has been
discussed in terms of a catalytic effect of diborane [33]. However, when a-Si:H is obtained
from halogenated silicon reactants (SiCU and SiF4), the addition of diborane decreases the
deposition rate, while phosphine increases it [34]. This opposite effect of dopants on the
deposition rate has been explained by the effect of the surface band-bending on the
chemisorption of silicon radicals.
In-situ ellipsometry studies have been used to monitor the growth of a-Si:H films, the effects of
doping with diborane on the initial stages of deposition [35], and the thermal CVD of diborane
[19]. Moreover, the in-situ Kelvin probe has been proved an excellent technique to control
changes in the Fermi-level position during a-Si:H doping with either phosphine or diborane
[36].
The studies of a-Si:H growth clearly indicate that the addition of a small amount of dopant to
the discharge results in dramatic changes in the growth processes, especially in the case of
diborane.

EFFECTS OF DOPANTS ON a-Si:H PROPERTIES

The main effect of doping is the change of the Fermi level position within the gap of the
semiconductor. In a-Si.H, p-type doping allows the Fermi level to be moved down to 0.3 eV
from the valence band, while n-type doping allows the Fermi level to be moved up to 0.2 eV
from the conduction band. These changes in the Fermi level position are accompanied by a
change of more than eight orders of magnitude in the dark conductivity [2]. However, contrary
to crystalline silicon, degenerate doping is not observed in a-Si:H. This is due to the existence
of band-tails and deep defects in the gap of a-Si:H, and to the creation of midgap defects along
with doping.
Besides doping, the effects of dopants on the growth processes are also reflected by changes in
the structure and properties of a-Si:H films. Those changes have been found to strongly depend
on the doping level. For Cg < 10"3 (doping regime) the addition of PH3 or B2H6 to silane results
in an increase of the hydrogen content and of the optical gap of the films, while for Cg > 10"3
(alloy regime) the addition of dopants leads to a decrease of the hydrogen content and of the
optical gap [37,38]. These effects have been mostly studied in the case of boron doping
[39-42]. In particular, an optimum doping level in the range OfB2H6ZSiH4 flow rates 10"4 10"3 has been observed and correlated with an improvement in the open circuit voltage of solar
cells [43].
Structural changes are also often reported, in particular for boron doped a-Si.H films wherein
an inhomogeneous morphology has been observed [44]. The presence of microstructural
inhomogeneities in boron doped films, supported by the observation of boron clustering [45], is
also inferred from hydrogen evolution measurements which show that boron, contrary to
phosphorus, results in a low temperature hydrogen evolution [46-48]. This effect is also
supported by annealing studies which show large changes of the optical and electrical
properties. As annealing temperature is increased the hydrogen content decreases, dark
conductivity increases, and hydrogen accumulates in internal voids as H2 molecules, even for
annealing temperatures below the deposition temperature [49]. This evolution of hydrogen at

low temperatures can be responsible for the thickness dependence of the properties of boron
doped films [5].
The addition of dopants in a-Si:H results in an increase of the defect density of the films as
shown by the decrease of photoluminescence [6] and measured by a wide range of techniques
[3,50,51]. Moreover, it is found that the density of defects is about a factor often higher than
the concentration of fourfold coordinated dopant atoms [52]. The changes in defect density are
also reflected in strong changes of the photoconductivity, transport and deep trapping [53-57].
Overall, doped a-Si:H films have high defect density and poor transport properties, which limits
their use as active layers in a device. However they are widely used as contacts with intrinsic
a-Si:H films.

EFFECTS OF GROWTH PARAMETERS

As discussed above, the doping efficiency is inversely proportional to the square root of the
concentration of dopants in the gas phase. However, this refers to films deposited under the
same plasma conditions [14]. Change of the discharge conditions affects a-Si:H deposition and
the chemical reactions at the film surface, and should therefore affect doping.
The substrate temperature has been one of the most studied parameters as it strongly affects the
properties of intrinsic a-Si:H. For both phosphorus and boron doped films, the decrease of the
substrate temperature results in a decrease of the dark conductivity [5,58,59]. Nevertheless,
highly conductive boron and phosphorus doped films have also been obtained at 500C [60].
Moreover, changing substrate temperature also affects the incorporation of hydrogen and of
dopants in the film [59,61], which makes it difficult to correlate process conditions and doping
efficiency.
The effect of ion bombardment has attracted particular attention in the study of anode versus
cathode deposited samples [39,46] or through the effect of a bias voltage applied to the anode.
In the case of intrinsic a-Si:H, ion bombardment improves the quality of the material [62].
However, quite different effects have been reported on doped films [63,64].
As for the substrate temperature, the plasma parameters such as pressure, gas flow rate, power
etc. affect both dopant and hydrogen incorporation [61]. As a matter of fact, the simultaneous
changes in hydrogen and dopant concentration suggest that hydrogen incorporation is governed
by the Fermi level position [65]. Moreover, hydrogen plays a crucial role in determining the
doping efficiency in a-Si:H, particularly in boron doped films where the formation of boronhydrogen complexes, as observed in crystalline silicon [66], may result in the decrease of the
doping efficiency [67]. The passivation of boron by hydrogen has also been observed in a-Si:H
through in-situ studies [68] and is supported by nuclear magnetic resonance measurements
which indicate that about half of the boron and phosphorus atoms in a-Si:H form H-dopant
complexes [69]. Moreover, the importance of hydrogen in the metastability of phosphorus and
boron doped a-Si:H films has also been studied [70,71]. However, while light-soaking of
phosphorus doped a-Si:H films produces a decrease of the fourfold coordinated P atoms
[72,73], light-soaking in boron doped a-Si:H results in an increase of the film conductivity [74],
which suggests that in this case light favours the formation of fourfold coordinated boron
atoms. This difference is in agreement with recent models which show that, contrary to

phosphorus doping, the doping efficiency in boron doped a-Si.H is limited by H passivation
[75]. Light-induced dopant activation has also been observed in the p-layer of p-i-n solar cells,
which results in an increase of the open circuit voltage of the devices [76].

CONCLUSION

Substitution^ doping in a-Si:H is against the 8-N rule of bonding in amorphous


semiconductors. Nevertheless, a small fraction of dopants in a-Si:H (IO"2 - 10"3) violates this
rule and is fourfold coordinated. However, doping is accompanied by the creation of defects
and results in highly defective films. Models based on chemical equilibrium reactions taking
place at the growing surface or in the bulk of the material account for most of the observed
effects of doping. This contrasts with the poor knowledge of the effects of dopants in the
plasma chemistry and growth processes.
Incorporation of phosphorus or boron in a-Si:H has quite different effects on the material
properties. While phosphorus doping is quite well understood, doping with diborane still needs
further research as it results in large structural changes of the a-Si:H matrix, which are
correlated to the changes in the incorporation of hydrogen forming boron-hydrogen complexes.
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1.3

Growth of a-Si:Ge:H alloys by PECVD - gas sources,


conditions in the plasma and at the interface
F. Finger and W. Beyer
September 1997

INTRODUCTION

The preparation of amorphous hydrogenated and/or fluorinated silicon germanium alloys


(a-Si:Ge:(H,F)) with a large variety of deposition techniques has been given great attention
since it was shown that by admixture of Ge and Si the optical gap can be shifted continuously
between the value for a-Si:H (1.7 - 1.8 eV) and that for a-Ge:H (1.1 - 1.2 eV) [I]. This makes
the material an interesting candidate for meeting the requirements of, for example, stacked solar
cells and optoelectronic devices where a certain bandgap, a variety of different bandgaps or
other material properties are needed. Si-based thin film solar cells including a-Si:Ge:H layers
have the highest stable efficiency of 13% [2], and other applications like multispectral colour
sensors have been successfully developed [3]. Research into preparation techniques for
a-Si:Ge:H alloys is necessary because together with alloying and the required shift of the optical
gap other material properties are also influenced - often in a way which is detrimental for
technical applications. Research activities have thus concentrated on investigating the growth
process and proposing and testing alternative deposition techniques in order to control the
material properties according to specified optimisation parameters, believed to be responsible
for or correlated with desirable performance for applications.
The understanding and interpretation of deposition processes of a-Si:Ge:H is not conclusive.
An obvious complication is that optimised growth conditions on the Si- and the Ge-rich side,
respectively, might be quite different. While most studies approach from the Si-side, some
reports start on the Ge-side. Several seemingly partly contradictory requirements for optimised
growth conditions have been postulated or concluded including (among others):
(1)

choose only neutral radicals with long lifetime [4], reduce short lifetime radicals through
reaction with H2 or avoiding depletion OfGeH4 [5];

(2)

enhance surface diffusion of Ge related radicals by hydrogen coverage [6];

(3)

use an alternative Ge dangling bond terminator [7,8];

(4)

need of no [4,9,10], versus moderate [11], versus high energy ion bombardment (or high
ion bombardment at high deposition rate [12]) to reduce heterogeneities and obtain
optimum performance [13-15];

(5)

use higher electron temperatures in the PECVD process to obtain favourable discharge
chemistry [15];

(6)

need of low [ 16,17] versus high [18,19] deposition rate.

In this Datareview the concepts of different PECVD based preparation techniques for a-Si:Ge:H
are summarised. The reader is referred to review articles and data collections on a-Si:Ge:H
preparation techniques and properties. These review articles have summarised in the past
certain stages of development or special preparation techniques and related material issues of
a-Si:Ge:H. Most of these review articles contain a large amount of additional literature. The
authors represent some of the important research groups involved with a-Si:Ge:H.
Early work is summarised in [20] and [21].
An important stage in optimisation with hydrogen dilution and triode systems is reported by
Matsuda and Tanaka [22].
Bullot [23], and in much detail Tsuo and Luft [24] and Luft and Tsuo [25], compare and
describe different preparation techniques for a-Si:Ge:H and collect results obtained from the
different techniques. The latter two are the most comprehensive works found to date on
preparation techniques for a-Si:Ge:H.
A detailed study of the plasma chemistry in
silane/germane and disilane/germane mixtures is reported by Doyle et al [26]. Also [27]
contains data on the preparation and the properties of a-Si:Ge:H alloys.
Among the reports which deal with the end-point of the alloy system (a-Ge:H) summaries are
given in [28,29].
Data on the alloying effect on the density of states and the electronic transport and
recombination in a-Si:Ge:H material is reported in [30-35].
Materials from different preparation techniques ( different source gases) are also compared in
[36,37], emphasising the importance of microstructure, and the direction for future research is
discussed in [37].
Finally, the widest collection of selected properties (photosensitivity, slope of the optical
absorption edge and defect density) as a function of the optical gap in a-Si:Ge:H prepared by
different techniques is given by Ichikawa and Sasaki [38]. We use this data collection as a
reference for the present Datareview (see FIGURES 1 to 3 in Datareview 1.4 in this book). By
far the most data found for photosensitivity, slope of the optical absorption edge and defect
density in the literature falls in the envelope spanned by this collection. We want to stress that
for the present Datareview more than 400 articles in journals, conference proceedings and
books dealing with a-Si:Ge:H dating back to 1977 have been searched. Among them about 200
report on details of the preparation techniques. Thus the data collections given in [24], [25] and
[38], together with the individual data points quoted in this Datareview, should give a complete
overview.

DEPOSITION TECHNIQUES

The simplest 'original1 deposition technique for a-Si:Ge:H is an RF (13.56 MHz) glow discharge
in a diode type reactor with gas mixtures of SiH4 and GeH4. Starting from this basic technique,
where results have been described in the early review articles [20,21], the following alternatives
to the standard PECVD process have been used and described in the literature:

(1)
(2)
(3)
(4)

(5)
(6)
(7)
(8)
(9)

Hydrogen dilution
Fluorinated gases
Disilane
Variation of deposition reactor
(i)
Triode reactor
(ii)
DC plasma
(iii)
Cathodic deposition
Helium, argon and other dilution gases
Microwave, ECR, remote plasma, VHF
Special gases
Other techniques and combinations
Substrate temperature

In addition, photo-CVD, sputtering, thermal CVD, catalytic CVD and evaporation have been
used, which will not be considered here. References on these methods are to be found in
[24,25].
Bl

Hydrogen Dilution

The concept of hydrogen dilution of the process gases SiH4 and GeH4 for deposition of
a-Si:Ge:H was first introduced by Matsuda et al in 1986 [6]. Hydrogen dilution was also used
in earlier work but not systematically to improve the material properties (see early review
articles). The concept is based on the ideas that (1) Ge related radicals might have smaller
surface diffusion coefficients on the film growing surface than Si-related radicals, and (2) H
atoms bonding with Ge are thermally evolved at lower temperatures compared with H on Si,
which causes a higher density of free bonds on the growing surface of Ge-rich a-SiGe alloys [6].
By adding hydrogen in the discharge it was believed that the H radical density increases, leading
to a better surface coverage and thus a higher surface diffusion coefficient. Furthermore, the H2
dilution was thought to reduce the density of highly reactive species GeHy (y = 0 - 2).
Although it was found later that in fact upon hydrogen dilution the H radical density decreases
in an SiH4ZH2 discharge [39], and thus the role of hydrogen dilution had to be reinterpreted [5],
the H2-dilution method was very successful in improving the electronic properties at a given
optical gap. H2-dilution is also the method most widely used to date in combination with other
methods (triode reactor, fluorinated gases, disilane, microwave frequencies etc.). Generally the
improvements reported by the numerous studies confirm the trends already reported in the
original work [6]. Data are collected in [25,38]. An effect considered as a disadvantage for
technical applications is the decrease in deposition rate upon dilution.
As an offshoot of the hydrogen dilution method one can consider the hydrogen plasma
annealing method where a thin deposited a-Si:Ge:H layer is exposed to a hydrogen plasma and
this step is repeated many times. The idea is to relax the SiGe network and to passivate
dangling bond states. Marked improvement over other techniques was not achieved [40-42].
Most recent reports using hydrogen dilution of process gases are given in [12,15,17,42-47].

B2

Fluorinated Gases

On the basis of the preferential attachment effect of hydrogen to silicon in SiH4-GeH4 mixture
based a-Si:Ge:H alloys, Paul et al [7,20] proposed in 1981 the use of fluorinated gases (or the
incorporation of oxygen) for a-Si:Ge:H deposition. Fluorine (and oxygen) was considered to
saturate Ge dangling bonds more effectively than hydrogen. The use of fluorine had already
been proposed earlier for the improvement of a-Si films [48]. a-SiGe film deposition using
fluorinated gases was first reported by Nozawa et al [8] in 1983 who characterised the film
quality predominantly by photo- and dark conductivity measurements. While a mixture of SiF4
and GeF4 did not result in an enhancement of photoconductivity compared to hydrogenated
reference samples, a considerable improvement was reported for gas mixtures OfGeF4, SiF4 and
H2 as well as GeH4, SiF4 and H2. These results were confirmed by other researchers [49].
Subsequently, it was recognised by the Shimizu group [50] using IR absorption and XPS
measurements that little (less than 1%) fluorine was incorporated into their good quality SiGe
films suggesting that the improvement of the fluorinated films compared to the hydrogenated
samples was not due to fluorine incorporation. Oda et al [50] attributed the improvement to
plasma chemical effects. Based on the reported improvement of photoconductivity and on the
fact that fluorinated gases are much safer and easier to handle, several groups started
programmes to investigate SiF4(SiHt)-GeF4-H2 based alloys [49,51-53]. While mostly RF
glow-discharge was applied, Aljishi et al [53] reported results for both RF and DC glowdischarge deposition. In a comprehensive article, Mackenzie et al [54] compared the properties
of (SiF4, GeF4, H2) and (SiH4, GeH4) based plasma grown a-Si:Ge:H,F films with Eg = 1.4 - 1.5
eV. They noted in the substrate temperature range between 200 and 35OC a much smaller
influence of Ts on hydrogen content and optical gap for fluorinated material than for
hydrogenated a-SiGe. The higher photoconductivity (about an order of magnitude) in
fluorinated material was attributed to a changed microstructure rather than to the saturation of
dangling bonds by fluorine. A particularly wide range of parameters was investigated by Morin
et al [55,56]. For gas mixtures of purely fluorinated gases with H2 they reported some
disadvantages: a rather low deposition rate (e.g. r = 0.6 A/s at E g = 1.25 eV), a strong
preferential incorporation of Ge, which had also been reported by Oda et al [50] and can give
rise to sample inhomogeneity [54], and a tendency for the films to become microcrystalline.
Better results (deposition rate of 3 - 5.5 A/s, no preferential Ge incorporation and no tendency
toward microcrystallinity) were obtained for SiH4-GeF4-H2 mixtures yielding device-grade
material for Eg > 1.5 eV according to defect density and photosensitivity. Using the initial
defect density as a figure of merit, best films were grown at a process gas pressure between
0.05 torr and 0.1 torr, a substrate temperature of between 300 and 35OC, an RF power (13.56
MHz) between 7.5 and 10 W, an H2 flow between 5 and 20 seem, a GeF4 flow between 2 and
10 seem, an SiH4 + SiF4 flow of 6.8 seem and an SiF4 flow below 1 seem [55]. Guha et al [57]
reported high quality a-Si:Ge:H,F material according to PDS and SCLC measurements using
gas mixtures of Si2H6, GeH4, SiF4 and H2 at substrate temperatures exceeding 225C and with
flow ratios of Si2H6-H2 > 1:10.
B3

Disilane

An advantage of using Si2H6 instead of SiH4 for a-Si:Ge:H deposition is the very similar
dissociation rates OfGeH4 and Si2H6 in RF plasma [57]. Chatham and Bhat [58] report that the
dissociation rates for germane and monosilane differ by about a factor of two whereas the
dissociation rates for germane and disilane differ by a factor of 0.8. For a gas flow ratio of

GeH4/(Si2H6 + GeH4 + SiF4) = 0.5 and hydrogen dilution, Guha et al [57] obtained a germanium
content of about 40 at.%. Using SCLC measurements, the latter authors reported a density of
states near the Fermi level of 3 x 1016 cm"3 eV"1 for a bandgap of 1.5 eV and about 1017 cm"3
eV 1 for Eg = 1.25 eV. Improvement of a-Si:Ge:H alloys by using low power disilane-germane
discharges without hydrogen dilution was recently reported by Matsuda et al [5]. Under their
deposition conditions they find no influence of hydrogen dilution on Urbach tail width and
defect absorption. It is argued that the improvement is due to an increase of the relative
contribution of long lifetime precursors (SiH3, GeH3) compared to short lifetime radicals (SiHx,
GeHx, x = 0,1,2) to film growth. In another recent report [46] use of disilane together with
strong hydrogen dilution is compared with various other preparation concepts and the lowest
absorption tail slopes, defect densities and microstructure factors (see Datareview 1.4) are
found with the disilane source gas.
B4

Variation of Deposition Reactors

B4.1

Triode reactor

The deposition of a-Si:Ge:H films using a triode RF plasma reactor was first reported by
Matsuda et al [4]. The aim was to reduce or eliminate the impingement of ionic species on the
growing surface so that only neutral radicals with long reaction lifetimes contribute to the
growth of the film. An improved film microstructure was expected. Indeed, an increased
photoconductivity as well as less dihydride, according to IR absorption and hydrogen effusion
peaks shifted to higher temperature, was observed for SiH4-GeH4 based a-Si:Ge:H films.
Matsuda's results were confirmed by Ichimura et al [59] who reported a better
photoconductivity, a lower density of dangling bonds and a very sharp Urbach tail as compared
with films produced in a conventional diode system. These improved electronic properties were
associated with a more compact structure according to IR absorption, hydrogen effusion and
transmission electron microscopy. The effect of ion bombardment during growth on structural
and electronic properties of triode RF plasma deposited a-Si:Ge:H was studied by Perrin et al
[H]. While the Ge and Si composition of the material did not change when the ion
bombardment was changed, structural and optoelectronic properties as well as the deposition
rate changed drastically at low deposition temperatures. Ion bombardment at a moderate
energy of about 50 eV was found to decrease hydrogen concentration and optical gap, reduce
the preferential attachment of hydrogen to silicon in favour of germanium and to improve the
film microstructure as well as the photoconductivity.
B4.2

DC plasma

DC plasma for a-Si:Ge:H deposition was applied as early as 1981 by Paul et al [7]. Aljishi et al
[53] reported data for a-Si:Ge:H,F films deposited by both RF and DC plasma. Results for
diode and triode reactors using DC plasma were compared by Weller et al [60,61]. Using
undiluted SiH4-GeH4 mixtures, they reported for a-Si:Ge:H of Eg = 1.4 - 1.5 eV a considerable
improvement of photoconductivity when they switched from the diode to the triode reactor.
Both reactor types gave even better results in the whole mixture range when employing
hydrogen dilution. Beyer et al [62] found this latter material to be compact according to
hydrogen effusion and diffusion.

B4.3

Cathodic deposition

Deposition on the cathode, i.e. on the powered electrode on a capacitively coupled diode glowdischarge system, results in ion bombardment of the growing film due to the RF self bias.
Wickboldt et al [15] applied this method, which had previously been used for a-Ge:H deposition
[13,28], to the preparation of Ge-rich a-Si:Ge:H films. An improvement of the steady state
photoconductivity and the ambipolar diffusion length compared to a-SiGe:H alloys grown on
the grounded electrode (anode) is reported. This improvement is primarily attributed to a
reduction of the long range structural heterogeneity and of the midgap state density.
In another approach the ion energies have been varied in an ion-gun chemical vapour deposition
system [14] which delivers high ion currents in the range 6 0 - 1 0 0 eV. While considerable
influence of ion energies is found, the optoelectronic properties could not be improved.
B5

Helium, Argon and Other Dilution Gases

Similar to hydrogen dilution, helium dilution was used in some earlier work, not with the
particular aim of improving material properties but for technical reasons like reducing hazard
through pre-mixed process gases or controlling the process pressure. In [33] the properties of
a-Si:Ge:H material with Ar, Ne, He, and H2 dilution is discussed. It was found that dilution
leads to higher defect densities in all cases and no distinctive improvement upon dilution is
reported.
More recently Tsuo et al [63,64] compare H2, He and Ar dilution and find an improved
mobility-lifetime product and ambipolar diffusion length with He dilution but unaltered
photoconductivity and sensitivity. Ar dilution is reported to lead to poor material [46,63].
Tsuo et al [63] also use XeF2 to enhance etching of Ge-related species (compare Section B2).
No improvement of properties is found.
Middya et al [17] compare effects OfH 2 and He dilution and different deposition rates (at
different temperatures). They find similar electronic properties but different structure. H2
dilution results in less polyhydride i.e. less porosity. Hazra et al [19] propose the use of He
dilution for operation in a high power regime where structural relaxation is achieved through
de-excitation of ionic He species. They report high quality (low defect density) low gap
(1.36 eV) material obtained at higher deposition rate (through variation of discharge power and
temperature).
B6

Microwave, ECR, Remote Plasma, VHF

Microwave and, in particular, ECR plasmas allow high plasma densities. Usually, remote
plasma arrangements are applied, separating the growth process from the plasma generation
process. This allows independent control of ion bombardment and hydrogen radical density
[24]. In a modification, hydrogen is excited in a microwave plasma and is fed into an RF plasma
of SiF4ZGeF4 or reacts with fluorinated radicals from a thermal source [65]. Watanabe et al [66]
studied Ar and H2 plasma streams from an ECR plasma discharge and reported deposition rates
as high as 13 A/s using the H2 stream. The improved quality of these a-SiGe:H samples was
attributed by Perrin et al [11] to ion bombardment during film growth. Saito et al [67] obtained
with microwave deposited a-Si:Ge:H of 100 A/s deposition rate a triple solar cell of 11.6%

efficiency. Guha et al [68] reported an 11.44% efficient tandem solar cell with the same
deposition rate. Application of low pressure (10 mtorr) remote electron-cyclotron-resonance
for a-SiGe:H films was recently reported by Kaushal et al [69]. By using H2 and He as the
discharge gas, a-SiGe.H of quite different hydrogen content was deposited. At a growth
temperature of 35OC, the authors obtained a hydrogen content of 6 to 8% for H2 discharge and
of 3 to 5% for He discharge as the (Tauc) bandgap varied from 1.4 to 1.7 eV. Using Hedischarge, high photosensitivities and low Urbach energies and sub-gap defect densities were
obtained. The film growth rate was 1.3 to 1.5 A/s. Discharge frequencies in the VHF range
have been used for preparation of a-Ge:H by Zedlitz et al [70] and of a-Si:Ge:H by Lundszien et
al [46] without achieving remarkable improvement.
B7

Special Gases

The use of silylgermane gases for deposition of a-Si:Ge:H was first reported by Fieselmann et al
[71]. For a bandgap of about 1.5 - 1.6 eV an enhancement of photoconductivity by about an
order of magnitude compared to SiH4-GeH4 mixtures was observed for monosilylgermane
(GeH3-SiH3) based a-Si:Ge:H. Improved efficiencies of p-i-n solar cells were also reported.
The synthesis of tetrasilylgermane Ge(SiH3)4 [72] and of various organo-silylgermanes [73,74]
for the purpose of a-Si:Ge:H deposition was reported by Sundermeyer and co-workers.
B8

Other Techniques and Combinations

In many preparation procedures combinations of the above listed deposition concepts are used
such as different source gases and dilutions in triode systems, remote plasmas, microwave
plasmas etc.
B9

Substrate Temperature

Many studies of the preparation of a-Si:Ge:H alloys include a variation of substrate


temperature. Related to the problem of surface mobility of growth species and desorption of
hydrogen, the temperature is found to be an important preparation parameter [18]. Generally it
is found that the temperature has to be optimised for each individual process and alloy
composition. Commonly temperatures in the range 200 - 3000C are used and optimised
conditions are found in this range. Here we only cite the most recent publications addressing
the substrate temperature.
Kutznetsov et al [45] have studied the temperature range 150 - 3300C (H2-dilution) and find an
optimum for the photosensitivity at 250 - 2800C. Ikeda et al [18], using disilane-germane
mixtures, have varied the substrate temperature between 150 and 4000C and find a maximum
for the photosensitivity at 2000C. Middya et al [17] vary the substrate temperature in the range
150 - 2500C for H2 and He dilution. Different behaviour is found for the two dilution gases.
They report that conditions can be set to obtain optimised material at 1800C. Terakawa et al
[47] vary the substrate temperature between 120 and 3200C and find the best 1.32 eV-gap
material at 2300C. Guha et al [68] use a microwave plasma and vary the temperature between
250 and 5000C. With very high deposition rates they find optimum solar cell performance for
a-Si:Ge:H deposition at 4500C.

CONCLUSION

A wide range of preparation techniques for a-Si:Ge:H alloys has been used in the past in order
to control and improve the material properties. While a considerable variation (improvement)
of selected properties and related device applications is achieved by some of these preparation
techniques, an overall deterioration of the optoelectronic properties as a function of the Ge
content is a persistent obstacle. It appears that this deterioration might be an intrinsic alloying
effect rather than a matter of non-optimised preparation conditions. To date the most
successful and most used approaches include hydrogen dilution of process gases and the use of
disilane-germane mixtures.

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1.4

Growth of a-Si:Ge:H alloys by PECVD - optimisation of


growth parameters, growth rates, microstructure and
material quality
F. Finger and W. Beyer
September 1997

INTRODUCTION

The possible reasons for the variation and deterioration of the properties of a-Si:Ge:H as a
function of the optical bandgap are manyfold and details are still not understood. The most
popular ideas which have been discussed in this context are:
(1)

a preferential attachment of H to Si over Ge which leads to an increase in Ge-DB


density;

(2)

development of microstructure or heterogeneities (voids, clustering);

(3)

thermal equilibrium effects as discussed in the defect pool model which result in higher
defect densities for low bandgap materials.

All of the above should affect the electronic performance through influence on the charge
carrier mobility-lifetime product.
Based on these ideas various concepts for alternative preparation techniques (see Datareview
1.3 in this book) and various optimisation parameters are suggested and used. Unless only
quantities such as the optical gap, the conductivity, the carrier mobility etc. are considered,
there is no clear situation as to which optimisation parameter can reliably predict the material
performance for a certain application. Thus a large variety of optimisation parameters are in
use, which makes comparison between different publications difficult. We will list the most
common optimisation parameters here and refer the reader to some previously published
reviews.

OPTIMISATION PARAMETERS

The following parameters have been used in the past for optimisation of a-Si:Ge:H material
preparation:
(1)
(2)
(3)

photoconductivity or the mobility-lifetime product


ratio of photo- to dark conductivity, also called photosensitivity
defect density determined by
- constant photocurrent method
- photothermal deflection spectroscopy
- electron spin resonance

(4)

(5)
(6)
(7)
(8)
(9)
(10)

- other techniques
microstructure as defined by
- the ratio of Si-H absorption bands at 2100 and 2000 cm"1
- the small angle X-ray scattering (SAXS) intensity
- structural features in TEM view graphs
- the FWHM of Raman scattering lines
hydrogen content, type of hydrogen bonding and thermal stability
band tail slope Eu from a deconvolution of optical absorption spectra
carrier mobility
ambipolar diffusion length
stability under light exposure
solar cell efficiency

and very important for technical applications:


(11)

growth rate.

Most commonly and usefully in most cases, the optimisation parameters are plotted as a
function of the optical bandgap. Frequently also the Ge content is used as the abscissa, which
seems inadvisable as the optical gap also depends strongly on the hydrogen content [1,2].
However the use of the optical bandgap has an additional complication: the optical bandgap Eg
in amorphous semiconductors is not well defined. Very popularly the intercept of a plot of
(ahv) 5 versus hv which assumes a density of states proportional to an E0 5 band profile above
the fundamental absorption edge [3] is used which becomes particularly problematic at higher
Ge contents where higher defect densities overlap with the tail absorption. Therefore the
energy where the absorption coefficient has a certain value (104, 1035) is also used as a
reference energy for the optical gap. Again this makes comparison between different
publications difficult.
The most complete data collection for a-Si:Ge:H properties (photosensitivity, defect density and
slope of the optical absorption edge versus optical gap) has been reported by Ichikawa and
Sasaki [4] covering data from 1977 to 1993 from journals and conference proceedings. All
quantities are found to spread over a wide range as a function of the optical gap and the
different preparation techniques. The present Datareview has compared more recent
publications with this report. It is found that in by far the most cases new data fall in the range
spanned by the data collection from Ichikawa and Sasaki [4]. Therefore individual data will not
be presented here.
The data collected by Ichikawa and Sasaki [4] for the photosensitivity, the defect density and
the slope of the optical absorption edge are shown in FIGURES 1 - 3 . One can summarise the
following trends. (1) the ratio of photo-to-dark conductivity drops over many orders of
magnitude with decreasing Eg but also varies considerably at a given Eg; (2) the defect density
increases strongly with decreasing Eg: again large variations can be found at a given Eg; and
(3) the band tail slope - as a measure of disorder - shows no clear correlation with the bandgap.
Another recent review which compares results from different preparation techniques for
a-Si:Ge:H can be found in [5].

A M 1 . 5

A M 1
ECD
Konagai
Hiroshima(Cat)
Solarex
Fuji(Triode)
Fuji(Diode)

Fuji(HCD)
Fuji(PD)
Fuji(HighVac)
Sanyo
Hltachi(ECR)
Hitachi(RF)

<yph/crd

ETL(H2 DiI.)
ETL(Triode)
ETL(Diode)
Sharp
URI
Stuttgart

Eg

(eV)

FIGURE 1 The ratio of photoconductivity (measured under AMI or AMI.5 conditions) to dark conductivity
(i.e. photosensitivity) of a-Si:Ge:H alloys prepared by different methods as a function of the optical bandgap [4].

P D S

Fuji(Triode)
IACS(ESR)
Sumitomo
Kanazawa(F)
Hiroshima(Cat)

Sanyo
Hitachi(ECR)
Wagner(DC)
Wagner(RF)
Wagner(SiH4)

Siemens
Oregon
Capacitance

Nd

(cm'3)

Solarex
Fuji(High Vac.)
Stuttgart
ECD
Kaiserslautern

C P M

E S R

E g

(eV)

FIGURE 2 The defect density in a-Si:Ge:H alloys prepared by different methods, determined by photothermal
deflection spectroscopy (PDS), electron spin resonance (ESR) or the constant photocurrent method (CPM),
as a function of the optical bandgap [4].

C P M

Solarex
Fuji(Triode)
Fuji(Diode)
Fuji(High Vac.)
IACS
Stuttgart
ECD
Hiroshima(Cat)
Kaiserslautern

Sanyo
Hitachi(ECR)
Wagner(DC)
Wagner(RF)
Wagner(SiH4)
Kanazawa(Hitachi)
Siemens
Oregon
(Capacitance)

Eu

(meV)

P D S

E g

(eV)

FIGURE 3 The slope of the optical absorption edge E11 of a-Si:Ge:H alloys prepared by different methods,
deduced from constant photocurrent method (CPM) or photothermal deflection spectroscopy (PDS) spectra,
as a function of the optical bandgap [4].

The deposition rates, when using SiH4ZGeH4 gas mixtures, generally increase with increasing
GeH4 content due to the higher decomposition rate of GeH4. Typical values are between 0.5
and 5.0 A/s. Deposition techniques like use of hydrogen dilution, triode electrode geometry and
remote plasmas lead to a strong decrease of the deposition rate. Means to maintain high
deposition rates are therefore required. Higher values are usually obtained with microwave or
ECR techniques with deposition rates in the range of 10 A/s. Outstanding are the deposition
rates achieved by Saito et al [6] and Guha et al [7] who use microwave excitation and obtain
100 A/s.

CONCLUSION

For the preparation of a-Si:Ge:H alloys a large variety of optimisation parameters have been
used. It is found that in general the various optimisation parameters do not correlate well with
each other and with device performance, a problem which itself has been addressed in the
literature (see e.g. [4,8,9]). In the case of solar cell applications no single optimisation
parameter can be considered at present a sufficient indicator for optimised device performance.
It seems to be clear, however, that certain optimisation parameters such as a small
microstructure factor, small slopes of the optical absorption edge and high photosensitivity are
very likely to be necessary requirements.

REFERENCES
[1]
[2]
[3]
[4]

W. Beyer [J Non-Cryst. Solids (Netherlands) vol.97&98 (1987) p. 1027 ]


A. Terakawa et al [ Jpn. J Appl Phys. (Japan) vol.32 (1993) p.4894 ]
J. Tauc, R. Grigorovici, A. Vancu [ Phys. Status Solidi (Germany) vol.15 (1966) p.627 ]
Y. Ichikawa, T. Sasaki [ Technical Digest of the 8th Sunshine Workshop on Thin Film Solar
Cells Eds J. Shimizu, Y. Ichikawa, A. Matsuda, S. Tsuda, T. Kikuchi (New Sunshine Program
Promotion Headquarters, MITI and New Energy and Industrial Technology Development
Organisation, Tokyo, 1995) p.27 ]

[5]
[6]
[7]
[8]
[9]

W. Luft, Y.S. Tsuo [ Hydrogenated Amorphous Silicon Alloy Deposition Processes Applied
Physics Series (Marcel Dekker Inc., New York, 1993) ]
K. Saito, M. Sano, K. Ogawa, I. Kajita [ J. Non-Cryst. Solids (Netherlands) vol. 164-166
(1993)p.689]
S. Guha, X. Xu, J. Yang, A. Banerjee [Appl. Phys. Lett. (USA) vol.66 (1995) p.595 ]
X. Xu, J. Yang, S. Guha [Appl. Phys. Lett. (USA) vol.62 (1993) p. 1399 ]
D. Lundszien, J. Folsch, F. Finger, H. Wagner [ Proc. 14th European Photovoltaic Solar
Energy Conference and Exhibition Barcelona (1997) ]

CHAPTER 2

STRUCTURAL AND VIBRATIONAL


PROPERTIES
2.1
2.2
2.3
2.4
2.5
2.6
2.7

Structural information on a-Si:H from IR and Raman


spectroscopy
Structural information on a-Si:H and its alloys from
small-angle scattering of X-rays and neutrons
Data on hydrogen in a-Si:H from IR and Raman
spectroscopy
Data on hydrogen in a-Si:H from NMR
Data on hydrogen in a-Si:H from diffusion and effusion
studies
Structural information on a-SiC:H from IR and Raman
spectroscopy
Structural information on a-SiN:H from IR and Raman
spectroscopy

2.1

Structural information on a-Si:H from IR and Raman


spectroscopy
A.H. Mahan
August 1997

INTRODUCTION

Structural information on hydrogenated amorphous silicon (a-Si:H) can take several forms.
From infrared (IR) spectroscopy, information on the different types of H bonding, and the total
amount of bonded H contained within the a-Si lattice, can easily be obtained. In some cases,
structural information can be obtained directly from IR analysis, but normally relating IR
analysis to the (micro) structure of the material requires additional kinds of measurements. One
scenario relates the information obtained from IR analysis directly to structural changes
occurring within the lattice, as observed for example by such measurements as film density
changes, H evolution measurements and scanning electron micrographs, and this approach will
be used in the present Datareview. On the other hand, structural information obtained from
Raman spectroscopy can stand alone, since this is thought to be one of the few measurements
that can uniquely determine the structure of the a-Si:H on the scale of short range order.
Whenever possible, attempts to relate the IR and Raman measurements will be made.

INFRARED ANALYSIS - GENERAL

Before relating the information obtained from IR analysis to structural information on the
a-Si:H itself, the vibrational modes of H in a-Si:H needed to be identified to determine the local
bonding sites of the H, and the total amount of bonded H present in the lattice (CH) had to be
quantified. Brodsky et al [1] presented the first comprehensive IR measurements on a-Si:H,
and distinguished the IR active regions of the so-called stretching (2000 - 2100 cm"1), scissorswagging (845 - 890 cm"1), and bending-rocking (630 cm"1) modes. They also determined that at
high substrate temperatures (Ts = 2500C) the films contained only Si-H groups, and at either
lower Ts or at 'non-optimal' deposition regimes (such as with Ar dilutions), higher order
bonding groups appeared. Lucovsky et al [2] confirmed and extended the assignments of [1] to
include Si-H2, (Si-H2),, and SiH3 groups. These findings have been nicely summarised by
Cardona [3]. The simple picture thus obtained was complicated only by the fact that some
samples showed absorption in the 2070 - 2100 cm"1 range without appreciable absorption in the
region of the scissors-wagging modes located at 845 - 890 cm"1. This spurred an intense debate
[3,4] within the a-Si:H community. One solution [5] to this controversy was provided by the
observation that Si-H bonded on c-Si surfaces (or equivalently, on the internal surfaces of
microvoids) can also oscillate in this frequency range.
The amount of bonded H contained within the lattice (CH) has also been obtained from IR. By
normalising the IR data to CH as determined for example by the nuclear reaction technique,
Shanks et al [6] obtained the first values of the proportionality constant A, which relates the
integrated IR absorption to the actual number of H atoms in the material. Since the value for

the bending-rocking vibrations at 640 cm'1 was found to be independent of CH as well as film
preparation method, this mode was used to determine CR. Langford et al [7] later amended this
value. Attempts to use this method to separately determine the amount of H in, for example,
the 2000 cm"1 and the 2090 cm"1 modes have been hindered by the three types of IR vibration in
this region. This issue has been addressed by several authors [3,6-8], and no definitive
agreement has been reached.
Since analysis of the 845 - 890 cm"1 modes will always be discussed in conjunction with the
stretch modes at 2090 cm"1, no separate discussion of these modes will be made. The same
holds for the 640 cm"1 mode whose analysis, as previously mentioned, is insensitive to film
preparation method and thus reveals no new structural information, other than a determination
of CR. On the other hand, a localised IR mode centred at 210 cm"1 as well as a broad band in
the region between 4000 and 5500 cm"1 will be discussed.

IR ANALYSIS AND FILM STRUCTURE - STRETCH BANDS AT 2000 cm 1

The interpretation of this band is straightforward. Since the bonding peak for Si-H in the bulk
occurs at -2000 cm"1, it is therefore shifted down by about 100 cm"1 with respect to both H
adsorbed on Si (111) surfaces and also Si-H vibrations observed in the gas phase (for the
molecule (Si)3-Si-H) [3]. This H was initially proposed to sit in a (fully hydrogenated)
monovacancy [6,9], and the downward frequency shift was accounted for by using a
depolarising field produced by a vibrating Si-H dipole in a spherical cavity inside the solid.
However, recent IR and film density measurements have indicated that a more logical bonding
configuration may be a fully hydrogenated divacancy. In particular, FIGURE 1 shows the
variation in film density versus CH [10]. For films containing typically <10 at.% H, only Si-H
IR bonding is observed. As can be seen, without any bonded H, the film density approaches
that of c-Si, being lower only by the increased average length of the Si-Si bond with respect to
its crystalline value [11], and becoming reduced with the addition of Si-H bonded hydrogen.
The solid curve is based upon a theoretical model where four H atoms replace a single Si atom
(monovacancy); better agreement is observed by comparing the experimental data to the
dashed curve, where six H atoms replace two Si atoms (divacancy). These predicted local
configurations must be weighed, however, against 1H NMR measurements showing linewidths
which are certainly too narrow to be accounted for by monovacancies, and perhaps by
divacancies as well [12]. On the other hand, model calculations including local relaxation could
possibly resolve this discrepancy, particularly in the case of the divacancy.
As seen in FIGURE 1 and noted in an earlier work [13], where films which contained
predominantly higher values of CH were examined, the only discernible change in film structure
with increased Si-H bonding is observed in the film density. No appreciable changes (other than
the density) in film structure are observed, as small angle X-ray scattering (SAXS)
measurements of 'optimally prepared1 device quality a-Si:H suggest a negligible micro void
density [14], and the material is still considered to be compact [5].

Mass Density p (gm/cm 3)

fit to data
4 H replace 1 Si
6 H replace 2 Si

c-Si
HW
GD
VHF

Hydrogen Content (at.%)


FIGURE 1 Measured mass density of a series of a-Si:H samples, deposited by the hot filament method,
versus CH. Reference data points for c-Si and also for glow discharge deposited a-Si:H are shown for
comparison. The solid and dashed curves are theoretical predictions based on local H bonding
configurations, and are discussed in the text.

IR ANALYSIS AND FILM STRUCTURE - STRETCH BANDS AT 2090 cm 1

If this IR signature occurs without the accompanying modes in the 845 890 cm"1 region, then
the local bonding structure proposed is that of a Si-H bond located in a microvoid (i.e., much
larger than a monovacancy). On the other hand, if this mode is accompanied by either the 860
cm'1 mode or the doublet modes, this signifies formation of either isolated Si-H2 or (Si-H2)n
respectively. Models involving (Si-H2)n are not abundant, but those that have been proposed
also involve (larger) microvoid creation [15].
It should be noted that the appearance in the IR of the higher ordered (Si-H2 and (Si-H2)n)
groups can be 'generated1 in many ways in film depositions. It is perhaps fair to group these
'generation1 methods. In the first group, when the deposition conditions have been optimised to
produce device quality material containing primarily Si-H, the occurrence of Si-H2 and then
(Si-H2)n is seen to be a function of CH. This trend was initially noted by a variety of research
groups [2,16,17], and was later refined and quantified for various deposition processes [18-20].
For all processes examined to date, the transition from Si-H to the higher ordered groups is
roughly in the 10 at.% range. In the second group, the appearance of Si-H2 and/or (Si-H2)n in
the IR also happens readily, for a wide variation in CH, when non-optimal deposition conditions
are used. These conditions include high silane dilution in a heavy noble gas [1], the use of high
plasma discharge powers, resulting in increased film deposition rates [2], and, among the newer
deposition methods, products of chamber pressure and filament to substrate distances which lie
outside the normal range [21].
Details about changes in film structure with the appearance of Si-H2 groups are sketchy, but
with the advent of (Si-H2)n formation, many indicators of bulk film structure change, and are

quite consistent with the introduction of microvoids into the a-Si:H lattice. Among these
indicators, SAXS measurements show an increasing microvoid density [22], film densities
continue to decrease, perhaps at an even faster rate than that observed with the introduction of
Si-H to the lattice [13,22], H evolution measurements show the appearance of a low T peak,
which is interpreted as being due to (molecular) H rapidly traversing the sample through an
interconnected microvoid structure [16,17], and scanning electron micrographs of fracture
surfaces show a columnar microstructure [23]. FIGURE 2 shows the a-Si:H dielectric constant
plotted versus CH [24]. Also plotted are the values that would be obtained, as calculated using
the Bruggemann effective medium approximation, without microvoids present in the samples.
Because so many indicators of structural quality change in this region of CH, it is difficult to
define some factor which can quantify these changes. One such factor which has been used
with some success has been the microstructure factor R = J I(2090)/( J 1(2090) + / 1(2000)),
where the integrals are performed over the respective absorption peaks in the IR modes centred
at 2090 cm"1 and 2000 cm"1 [25]. Several correlations were made between this microstructure
factor and film electronic quality [26,27].

Dielectric Constant

no voids

NH (1021Cm"3)
FIGURE 2 a-Si:H film dielectric constant versus CH. The dotted line reflects the value neglecting
microvoids, and the solid line serves as a guide to the eye through the measured points.

ANALYSIS OF THE IR MODE CENTRED AT 210 cm 1

This peak in the IR spectrum [3] is strong and relatively sharp. Although its intensity is roughly
linear in CH, it shows only a very small frequency shift upon deuteration. Hence, it must involve
mainly vibrations of a Si atom. Several different interpretations of this mode have been
proposed, including one in which a Si-H pair vibrates, with the rest of the neighbouring atoms
assumed not to move. This could happen if this oscillating Si-H pair is located on the surface of
a microvoid.

ANALYSIS OF THE BROAD IR MODE IN THE 4000 - 5500 cm 1 REGION

This mode has been identified [28] as being due to collision induced IR absorption of the
fundamental vibrational band of high pressure (-2000 atm) molecular hydrogen (H2) located in
microvoids. The amount of this H2 is seen to depend on the sample Ts [29]; a relatively larger
amount OfH2 is observed in samples deposited at high Ts as opposed to those deposited at low
Ts. This finding is consistent with the fact that the high Ts samples are 'compact' structures
which can readily trap H2 in microvoids, while the low Ts samples are observed to be relatively
open, void-rich, oriented structures [14] through which H2 can readily travel. Note that
wedged substrates and low observation temperatures are necessary to observe this IR band.

RAMAN SPECTROSCOPY - GENERAL

Raman spectra of unhydrogenated a-Si were first published by Smith et al [30], who observed
broad bands in the spectrum that were centred quite near the frequencies corresponding to the
well known excitational modes (the transverse optical (TO), the longitudinal acoustical and
optical (LA and LO) and the transverse acoustical (TA)) of c-Si. Indeed, this agreement in
feature position is so close that a spectrum almost identical to that observed by Smith et al for
a-Si (and for a-Si:H) can be generated by taking the vibrational density of states spectrum for
c-Si and convoluting it [31] with a Gaussian of full width at half maximum of 60 cm"1. This
suggests that the short range order in the amorphous and crystalline phases of Si is very similar.
In addition, since most reports have shown that the bond lengths in a-Si are typically within 1%
of the value for c-Si [12], the short range order, and its variations, must be due to (variations in)
the average bond angle deviation (AG).

RAMAN SPECTROSCOPY - CORRELATIONS WITH FILM STRUCTURE

Although a wide variety of correlations between Raman parameters and a-Si:H material
properties were made, including the effects of sample annealing [32-34], it soon became
apparent that the TO mode was particularly sensitive to variations in short range order.
Modelling calculations [35,36] using continuous random network models first showed that the
width of the TO peak changed significantly with small changes in AG, being broader for higher
values of AO, and this broadening was accompanied by a shift of the peak position to lower
frequencies. Theoretical studies [36,37] have explored the relationship between the half width
at half maximum (172) of the Raman TO peak and AO, and agree on the general trend, but not
on the quantification [31]. However, there is universal agreement that a fundamental
relationship does exist between 172 and AG, and relative variations in YIl with changes in
a-Si:H deposition (and process) parameters are used at the present time as perhaps the main
indicator of a-Si:H short range order.
To date, the narrowest TIl for a-Si:H, indicating the smallest AG and thus exhibiting the best
short range order, is in the 31 - 33 cm"1 range [31,32,38,39]. The existence of this maximum
has been discussed by Tsu [40], and is observed in samples containing only Si-H IR bonding.
For samples deposited by almost any method that are prepared away from the optimum
conditions, TIl is observed to increase. At higher Ts, for samples still containing only Si-H, TIl
increases [31], with the notable exception being samples deposited by the hot filament method

[31,39] which still exhibit device quality electronic properties for low CH. At lower T8 (higher
CH), with the introduction of the higher order IR bonding groups, T 12 again increases, the
change being larger than that observed at higher T8. The observed correlation, with decreasing
T8, between higher 172 values and an increased IR microstructure factor R, as seen in FIGURE
3, is readily apparent [31]. Schubert et al [38] also observed an increase in Y12 with increased
substrate bombardment, while going from a remote plasma to a triode configuration, and finally
to a diode reactor.

NH(at.%)

(a)

T8(0C)

(b)

T8(0C)

172 (cm *1)

(C)

T8(0C)

FIGURE 3 (a) CH, (b) the microstructure parameter R, and (c) the Raman half width T/2, versus Ts.
The different symbols refer to films deposited using different deposition conditions and different
reactors. For a more detailed explanation, see [31].

Finally, two words of caution should be noted. First, Raman experiments have typically utilised
either 488 or 514.5 nm radiation from an Ar-ion laser, and because of the high absorption of aSiH in this wavelength region, Raman spectroscopy using this radiation is inherently a surface
sensitive measurement technique. This poses no problem except when high sample annealing or
high deposition temperatures are used. In these cases, care must be taken to avoid depleting the
surface of H, in which case the Raman measurements may not reflect the properties of the bulk
material [32,39,40]. Secondly, other types of order (e.g. medium range order) have recently
been observed in a-Si:H [39] (and also for a-Ge [41]) using other techniques, and do not
necessarily correlate with changes in short range order as probed by Raman spectroscopy. At
this time, it is an open question as to whether these two types of order correlate in any way.

CONCLUSION

Structural information can readily be obtained on a-Si:H from both IR and Raman
spectroscopy. In general, a-Si:H films prepared under the optimum conditions used by any
particular deposition technique display predominantly IR Si-H bonding and the best short range
order as observed by Raman. When moving away from these optimum conditions, either by
variations in Ts or by purposely changing crucial deposition parameters, higher order IR
bonding modes are almost always observed, and this is accompanied by changes in the film
structure and a worsening of the Raman short range order. Models of the local H bonding
configurations have been presented when possible.

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[I]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
II1]
[12]
[13]
[14]
[15]
[16]
[17]

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[19]
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[21]
[22]
[23]
[24]
[25]
[26]
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[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
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[41]

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A.H. Mahan, P. Menna, R. Tsu [ Appl. Phys. Lett. (USA) vol.51 (1987) p. 1167 ]
YJ. Chabel, C.K.N. Patel [ Phys. Rev. Lett. (USA) vol.53 (1984) p.210 ]
HV. Lohneysen, HJ. Schink, W. Beyer [ Phys. Rev. Lett. (USA) vol.52 (1984) p.549 ]
J.E. Smith Jr., M.H. Brodsky, B.L. Crowder, M.I. Nathan [ Proc. 2nd Int. Con/, on Light
Scattering in Solids (1971) p.330 ]
AJM. Bemtsen [ PhD Thesis, Physics Department, Utrecht University, Utrecht, The
Netherlands, 1993 ]
R. Tsu, J. Gonzalez-Hernandez, J. Doehler, SR. Ovskinsky [ Solid State Commun. (USA)
vol.46 (1983) p.79 ]
Y. Hishikawa, K. Watanabe, S. Tsuda, M. Ohnishi, Y. Kuwano [ Jpn. J. Appl. Phys. (Japan)
vol.24 (1985) p.385]
N. Maley, J.S. Lannin [ Phys. Rev. B (USA) vol.36 (1987) p. 1146 ]
R. Alben, D. Weaire, J.E. Smith Jr., M.H. Brodsky [ Phys. Rev. B (USA) vol. 11 (1975) p.2271 ]
D. Beeman, R. Tsu, M.F. Thorpe [ Phys. Rev. B (USA) vol.32 (1985) p.874 ]
CK. Wong, G. Lucovsky [Mater. Res. Soc. Symp. Proc. (USA) vol.70 (1986) p.77 ]
M.B. Schubert, H.D. Mohring, E. Letter, G.H. Bauer [ IEEE Trans. Electron Devices (USA)
vol.36 (1989) p.2863 ]
A.H. Mahan, D.L. Williamson, T.E. Furtak [ Mater. Res. Soc. Symp. Proc. (USA) vol.467
(1997) in press]
R. Tsu [ in Disordered Semiconductors (Plenum Press, 1987) p.479 ]
JM. Gibson, MMJ. Treacy [Phys. Rev. Lett. (USA) vol.78 (1997)p. 1074 ]

2.2

Structural information on a-Si:H and its alloys from smallangle scattering of X-rays and neutrons
D.L. Williamson
August 1997

INTRODUCTION

Several aspects of the structure of a-Si:H and its alloys can be probed with the small-angle
scattering (SAS) of radiation such as X-rays (SAXS) or neutrons (SANS) [I]. Any source of
fluctuations in electron density (seen by SAXS) or neutron scattering-length density (seen by
SANS) in the films will produce scattering of the incident radiation whose angle dependence
and intensity can be related to the size scale of the. fluctuations and their abundance,
respectively. Examples of density fluctuations include voids, H-rich clusters, columnar
microstructure, alloy segregation, and surface roughness. The sizes of fluctuations accessible
by SAS range from the atomic-scale to a few hundred nanometres, depending on the apparatus.
Reviews of the application of SAXS to a-Si:H, a-SiGe:H and a-SiC:H prior to 1995 [2] and
SANS to a-Si:H prior to 1988 [3] are available. Here we summarise the results of this research
and describe the most recent data, focusing on device-quality material.

SOME BASICS OF SAS METHODS

The usual configuration in SAS experiments is transmission geometry such that the momentum
transfer vector q lies in the plane of the sample film. This allows study of density fluctuations
parallel to q with sizes of the order of 1/q. The SAS intensity is collected over a range of q and
plotted versus the magnitude q = (47t/A,)sin0, where 29 is the scattering angle and A, is the
neutron or X-ray wavelength. Anisotropic scattering due to non-spherical scattering objects
that have a preferred orientation in the sample can be revealed with two-dimensional detectors
or by tilting the sample in the beam so that q no longer lies in the plane of the sample. There
are numerous methods of inversion of the SAS intensity I(q) from momentum space to real
space to extract structural details of the features causing the scattering such as their shape, size
distribution, preferred orientation, and spatial correlation [I].
To interpret the intensity from small-angle scattering experiments it is convenient to divide it
into three components:
(1)
where we now assume there is no preferred orientation of the scattering objects so that only the
magnitude of q is needed. IL(q) represents the intensity from large-scale objects that are so
large that their primary scattering occurs well below the lowest angle accessible by the
experimental apparatus. Thus only the 'tail' of the scattering curve is seen from these large
objects and usually exhibits a well-known power-law dependence (Porod law) in the case that
the objects have sharp boundaries, i.e.

(2)
where A is a constant related to the total surface area of the objects and s = -4 for point-focus
SAS systems and s = -3 for line focus systems [I].
IN(q) is of primary interest and represents the intensity due to nanostructural features in the size
range readily accessible by SAS (typically from about 1 run to 100 nm). If the scattering object
is a well-defined 'particle1 of volume v and uniform electron or neutron scattering length density
rip imbedded in a matrix of nm, then IN(q) for a single particle can be expressed in terms of a
form factor P(q) determined by the shape of the particle:
(3)
where C is a constant depending on choice of radiation and units. A wide variety of particle
shapes and their associated form factors have been considered in the interpretation of smallangle data [I]. The total intensity from a distribution of particles of the same shape is obtained
by superposition via EQN (3). If the particle density is high or the particles are correlated in
position due to some type of interaction, then interparticle interference will influence lN(q) and a
pair correlation structure factor S(q) should be included [I]. Experimental evidence for this
effect is a maximum or 'shoulder' in I(q) not expected from P(q) alone.
We have found that most of the SAXS-detected features in the examined films can be modelled
as either spherical- or ellipsoidal-shaped objects using the appropriate P(q). The latter can
mimic rod-like or plate-like objects through appropriate choice of major-to-minor axis ratio,
while a preferred orientation will lead to readily observed and modelled anisotropies in the
SAXS [2]. Alternative data interpretation models based on correlation functions [1] or fractal
concepts [4] can be applied.
There are two special techniques to vary the density scattering contrast in SAS experiments and
extract more information on the nanostructure term, lN(q). The contrast in an SANS
experiment can be altered dramatically through isotopic substitution. The major advantage of
this is that one can tune the contrast in a system and not influence the thermodynamic
interactions between species in multicomponent studies. This ability to tune contrast motivates
the use of deuterated materials to highlight the nature of the hydrogen nanostructure [3]. In the
case of X-ray scattering, the method of anomalous SAXS (ASAXS) allows tuning of the
contrast by varying the wavelength close to the absorption edge of a particular element and
thereby highlighting any nanostructure associated with that particular element [5]. This method
has recently been applied to a-SiGe:H alloys to search for Ge composition fluctuations [6].
The third term contributing to the SAS intensity (EQN (I)) is that due to diffuse scattering, ID.
It has a variety of sources, all of which are at the atomic scale so that there is little or no q
dependence over typical experimental ranges. Although ID is weak for X-ray scattering, it is
readily detectable in our experiments by either a nearly q-independent intensity over a wide
range of q or the approach to a constant intensity level at high q. Sources for this intensity
include thermal diffuse scattering, static disorder scattering, Compton incoherent scattering and
Laue monotonic scattering [2]. Theoretical expressions for the latter effect suggest that
information on alloy randomness may be extracted [2]. The diffuse scattering component in
SANS is typically more significant than in SAXS and arises primarily from the incoherent

scattering of nuclei with spin. This contribution to the total scattering is particularly important
in materials composed of significant quantities of hydrogen but can be dramatically reduced
through deuterium substitution [1,3].

SUMMARY OF MAJOR RESULTS FROM SAXS RESEARCH

During the last six years, a large array of a-Si-related materials has been examined by SAXS
using a system installed on the rotating-anode X-ray generator housed in the Physics
Department at the Colorado School of Mines. The samples have been supplied by expert film
and device makers from around the world [2]. All of the SAXS intensities presented in the
FIGURES below are in absolute electron units (electrons/atom = e/a), calibrated with the
known scattering from H2O [2], thereby allowing direct comparison of the SAXS intensities
from the different materials of different thicknesses. Careful sample and experimental
measurement design, coupled with theoretical considerations of the various mechanisms leading
to the SAS, have led to the following major results.
Cl

a-Si:H

The a-Si:H intrinsic layers that have been incorporated into solar cells yielding high efficiencies
(-10%) have no detectable nanovoids or other nanostructural features with volume fractions
above 0.01%. This includes cells made with PECVD and hot wire (HW) (also called hot
filament CVD) intrinsic films [2,7] and the typical SAXS data from such materials are shown in
FIGURE 1. Note that the diffuse component, ID, and the larger-scale component, IiXq), are
clearly visible in the data when compared with a c-Si wafer. The ID for the HW film is lower
since it contains significantly less H than the PECVD film. The IiXq) is associated with residual
columnar-like features (particularly if anisotropic behaviour is observed in the IiXq) by tilting the
sample in the beam) or surface roughness [2]. An extremely small volume fraction of H-rich
regions associated with columnar-like structure can account for the observed IiXq) Cells made
with intentionally large void fractions in the 1 nm size range are clearly inferior [8]. FIGURE 2
shows the strong SAXS from an HW sample made at a high deposition rate of 4 nm/s with a
nanovoid content of 1.0 vol.% and a spherical size distribution shown in the inset.
A search for any light-induced changes in the SAXS-detected nanostructure of a-Si:H was
negative [9]. This experiment was done with extreme care to look for any small difference
between a 1000-hr light-soaked state, and the annealed state (annealing done in-situ without
moving the sample) in a set of four different samples, three high-quality PECVD films made by
three different groups and a device-quality HW film.
The thermal stability of the a-Si:H network depends on the total H content. Samples with 11
and 20 at.% H are unstable to H2 nanobubble formation above 3000C, while samples with 3 to 4
at.% H remain stable in the range from 300 to 4500C even though H is difliising at these
temperatures [10,11]. These results suggest a solubility limit for H in the a-Si:H network.

SAXS Intensity

(e/a)

PECVD a-Si:H
HW a-Sl:H
c-SI wafer
0.1 vol% voids
(DIam = 2 nm)

q (nm"" )
FIGURE 1 SAXS from device quality a-Si:H films made by PECVD and hot filament CVD. A theoretical
curve based on EQN (3) for spherical voids is shown to demonstrate that nanovoids, if present, are at the
0.01 vol.% level

Fraction

SAXS Intensity

(e/a)

HW a-S!:H
distribution fit
depos. rate: 4 nm/s
substrate T: 400C

R (nm)

q (nm

FIGURE 2 SAXS from a hot filament CVDfilmprepared at a high deposition rate. Afitwas made
with a volume distribution of spherical nanovoids of radii shown in the inset. The total volume
fraction in the film is 1.0%.

Cl

a-SiGe:H

The PECVD a-Sii.xGex:H alloys incorporated into recent solar cells to absorb the lower energy
photons have significant nanostructural features [2] whose origin remains unclear. They can be
highly oriented as shown in FIGURE 3, suggesting columnar-like structure. The tilt behaviour
is consistent with highly elongated scattering centres with the long axes parallel with the film
growth direction. Such orientation may be less detrimental since it is parallel to the conduction
path in the solar device configuration. The preliminary ASAXS results suggest that the SAXS
is due in part to a non-random Ge distribution [6], a surprising result in view of the complete
miscibility of Si and Ge in the crystalline state. It seems that better performance may be
possible if this inhomogeneous nanostructure in a a-SiGe:H is eliminated or reduced. This is
based on recent observations that devices made with a high-deposition-rate microwave
technique were significantly improved by ion bombardment [12] and the latter process, induced
by a substrate bias, eliminated nanostructural features as shown in FIGURE 4. However, cells
made from the best microwave-deposited material remain inferior to those made from the
lower-deposition-rate PECVD films. The significant diffuse scattering from the SiGe matrix
seen in FIGURES 3 and 4 (ID 7 0 - 1 0 0 e/a) is much larger than from a-Si:H (FIGURES 1 and
2, ID 4 -10 e/a) and is readily accounted for by Laue monotonic diffuse scattering [2].

SAXS Intensity

(e/a)

(low H2 dilutfon)
(high H2 dilutfon)

TIIt Angle (deg)

(nm

FIGURE 3 Illustration of anisotropic SAXS from device-quality a-SiGe:H films prepared by PECVD from GeH4
and SiH4 with different amounts of hydrogen dilution. The data in the inset was obtained by tilting the films at
the angles shown relative to the incident X-ray beam at the q indicated by the dashed line.

A recent detailed investigation of high-Ge alloys (x > 0.6) [13] has demonstrated improved
optoelectronic quality compared to previous studies of this alloy regime. This is attributed to
the higher levels of ion bombardment associated with the film deposition on the powered
electrode (cathode) of a PECVD system. Both a lower midgap density of states and improved
homogeneity detected by SAXS are associated with the improved film quality [13].

SAXS Intensity

(e/a)

Microwave-deposited aSlt_KGex:H
<R>
dep.rate
X
f

bias off

bias on

q (nm

FIGURE 4 Demonstration of the dramatic reduction in SAXS via ion bombardment during high-rate
deposition of a-SiGe alloys. The Ge contents (x), nanovoid volume fractions (f), average void
radii (<R>) and deposition rate are indicated for the four films.

C3

a-SiC:H

All a-Sii-xCx:H films examined in our research to date have high volume fractions (-1% and
greater) of nanovoids only about 1 nm in diameter, most likely originating from high
incorporation of CH3 groups [2]. The high density of scattering centres typically leads to a
well-defined 'shoulder1 or even a maximum in the SAXS curve as shown in FIGURE 5. This
feature is modelled by a hard-sphere pair-correlation structure factor [2], indicated by the solid
line fits in FIGURE 5. The correlation length (hard-sphere diameter) and nanovoid radius for
the two films are 1.6 nm, 0.55 nm for x = 0.06 and 2.3 nm, 0.60 nm for x = 0.23. The largescale contribution, IL(q), is about a factor of 10 larger in the RF-sputtered film. The
performance of devices utilising the PECVD high bandgap material remains inferior. The latest
record efficiency multijunction solar cell avoided the a-SiC:H material, using instead an H-rich
a-Si:H layer for the top cell [7].
Other researchers have recently demonstrated by SAXS that the deposition of high C material
(x - 0.5) by PECVD also leads to high volume fractions of extremely small scattering centres
[14,15]. In one case the appearance of a well-defined peak in the SAXS (obtained with pointfocus geometry) was modelled with a correlation function yielding a characteristic size of 2 nm
and a correlation length of about 2.5 nm, both of which were relatively independent of
preparation conditions [15]. The similar position of this maximum near q = 3 nm"1 and the
peaks in FIGURE 5 are consistent with the similar correlation lengths extracted from the model

SAXS Intensity

(e/a)

(rf-sp)
(PECVD)

S(q) model fits

q (nm

FIGURE 5 Typical SAXS data from a-SiC:H alloys, one prepared by reactive RF-sputering of a Si target
in the presence of CH4 and the other by conventional PECVD with SiH4 and CH4. The fits are based on
a hard-sphere pair-correlation model with structure factor S(q).

fits. However, the sizes of the scattering features obtained from the two models differ by a
factor of 2 for the low x (~1 nm) and high x (-2 nm) materials.

SUMMARY OF MAJOR RESULTS FROM SANS RESEARCH

It is noteworthy that very few experiments have been done with SANS of a-Si:H/a-Si:D [3,16]
and we are not aware of any experiments on a-SiGe:H or a-SiC:H alloys. This is due in part to
the requirement that unusually thick samples are typically needed for SANS. The first
experiments [17] were done with an area detector and demonstrated clear anisotropic SANS
from non-device-quality, PECVD material (deposited at 25C under high power conditions),
consistent with the expected columnar-like growth under such conditions. The only devicequality sample examined did not yield any detectable SANS signal. The range of momentum
transfer covered (up to 0.9 nm"1) did not allow detection of features at the 1 nm scale. The
recent SANS work at larger q [16] did detect such small features (radius 0.65 nm) at a
volume fraction level of about 1%, probably associated with the high deposition rate used as
well as the high H or D content (>20 at.%). The use of D substitution allowed the identification
of these features as fmicrocagesf containing H2 (or D2) molecules at pressures in the 10 kbar
range. Precipitated H2-nanobubbles of a similar small size have been seen recently by SAXS in
annealed a-Si:H with high H content [10]. In both of these SANS studies [16,17], there was
strong scattering in the lower q range, demonstrating that significantly larger scattering features
(>5 nm) were present as well. These are well represented by the IL(q) term in EQN (2) with
s = -4.

Earlier experiments [3] with D substitution for H were based on sputter-deposited films of 20 or
30 nm thickness (several of these were then stacked for the SANS measurements). Although a
high substrate temperature of 4000C was used, the optoelectronic quality of the material was
not documented. Scattering features specifically associated with the H nanostructure were
detected with a range of sizes characterised by radii from 4 to 15 nm. An intriguing experiment
was done by this group [3], in which a correlation between the Staebler-Wronski effect and the
SANS was detected. Again using a-Si:H made by reactive sputtering (onto 3000C substrates), a
25% increase in the SANS intensity was seen upon illumination for 4 hours in visible light.
Annealing at 1800C then reduced the intensity by about 25%. The size scale on which the
changes occurred was 10 nm. These remarkable results have been described by a domain
model involving H redistribution [3].

CONCLUSION

It is clear that the a-Si:H incorporated as an intrinsic layer into solar cells has extremely small
nanovoid volume fractions (<0.01%). High deposition rates, reduced substrate temperatures or
high H content typically lead to increased heterogeneity due to nanovoid or nanobubble
formation and columnar-like microstructure. The present state-of-the-art a-SiGe:H intrinsic
materials typically have significant nanostructural features which are likely to be a combination
of nanovoids and Ge composition fluctuations, both with non-spherical structure and significant
preferred orientation within the film. Conditions have not been discovered for the deposition of
a-SiC:H that prevent the formation of high densities of 1-nm-sized inhomogeneities.

REFERENCES
[I]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[II]
[12]
[13]
[14]
[15]

See e.g. L.A. Fegin, D.I. Svergun [ Structure Analysis by Small-Angle X-Ray and Neutron
Scattering (Plenum, New York, 1987) ]
D.L. Williamson [Mater. Res. Soc. Symp. Proc. (USA) vol.377 (1995) p.251 ]
R. Bellissent [ in Amorphous Silicon and Related Materials Ed. H. Fritzsche (World Scientific,
Singapore, 1988) p.93 ]
S. Muramatsu et al [ Jpn. J. Appl Phys. (Japan) vol.28 (1989) p.L1092 ]
J.E. Epperson, P. Thyagarajan [ J. Appl. Crystallogr. (Denmark) vol.21 (1988) p.652 ]
G. Goerigk, D.L. Williamson, H.-G. Haubold [ HASYLAB Annual Report (1996) p.628 ]
J. Yang, A. Banerjee, S. Guha [Appl Phys. Lett. (USA) vol.70 (1997) p.2975 ]
S. Guha, J. Yang, SJ. Jones, Yan Chen, D.L. Williamson [ Appl Phys. Lett. (USA) vol.61
(1992) p. 1444]
D.L. Williamson [ unpublished (1997) ]
S. Acco et al [ Phys. Rev. B (USA) vol.53 (1996) p.4415 ]
S. Acco, D.L. Williamson, S. Roorda, W.GJ.H.M. van Sark, A. Polman, W.F. van der Weg
[Int. Conf. on Amorphous and Microcrystalline Semiconductors, Budapest, 1997,
unpublished ]
S. Sugiyama, X. Xu, J. Yang, S. Guha [Mater. Res. Soc. Symp. Proc. (USA) vol.420 (1996)
p. 197-202]
P. Wickboldt et al [ J. Appl. Phys. (USA) vol.81 (1997) p.6252 ]
M.N.P. Carreno, I. Pereyra, M.C.A. Fantini, H. Takahashi, R. Landers [ J. Appl Phys. (USA)
vol.75 (1994) p.538]
J.S. Ridgen, CD. Algar, RJ. Newport, A.N. North, F. Ibrahim, J.I.B. Wilson [ J. Non-Cryst.
Solids (Netherlands) vol.190 (1995) p.276 ]

[16]
[17]

CA. Guy, A.F. Wright, R.N. Sinclair, RJ. Stewart, F. Jansen [ J. Non-Cryst. Solids
(Netherlands) vol.196 (1996) p.260 ]
AJ. Leadbetter, A A M . Rashid, RM. Richardson, A.F. Wright, J.C. Knights [ Solid State
Commun. (USA) vol.33 (1980) p.973 ]

2.3

Data on hydrogen in a-Si:H from IR and Raman


spectroscopy
M. Stutzmann
January 1998

INTRODUCTION

The concentration and state of bonding of hydrogen in a-Si:H have a major influence on the
structural and electronic properties of this material. Important examples are the variation of the
average structural disorder (as measured by the degree of bond length and bond angle
deviations), the optical gap, and the density of dangling bonds with the amount of hydrogen in
a deposited film. In addition, details of hydrogen bonding are discussed in the context of
thermal stability and the well known metastability phenomena ('Staebler-Wronski-effect'), but
also in view of deposition and etching processes in hydrogen containing plasmas.
Experimentally, infrared (IR) absorption is the predominant method to characterise the amount
and the bonding configurations of hydrogen incorporated in a-Si:H thin films. Complementary
Raman scattering has been used in order to obtain additional information, especially
concerning depth profiles and the correlation of hydrogen with other structural properties. A
Datareview emphasising the more general structural and morphological information about
hydrogenated amorphous silicon deduced from such IR and Raman measurements is provided
(Datareview 2.1). Here I will concentrate more on information about hydrogen in a-Si:H itself.

SPECTROSCOPY OF BONDED HYDROGEN IN a-Si:H

Hydrogen in principle can be present in a-Si:H in a number of different bonding configurations


as described by detailed theoretical studies [1-8]. Experimentally, however, only the dominant
bonding configurations with hydrogen concentrations in the 1 to 10 at. % range will be clearly
observable in a direct manner. In most cases, such structurally selective spectroscopic methods
are infrared absorption, Raman scattering or nuclear magnetic resonance (see Datareview 2.4).
Complementary information about the total hydrogen content and the binding energy of
different structural species is available from nuclear techniques (elastic recoil detection, ERD,
secondary ion mass spectrometry, SIMS, etc.) or from thermal effusion studies (see Datareview
2.5).
Historically, vibrational (IR or Raman) spectroscopy has been the first and subsequently most
widely used experimental method to study hydrogen in semiconductors in general, and in
a-Si:H in particular [9-15]. The underlying concept is that hydrogen which bonds to the a-Si
network produces a local vibrating dipole because of the electronegativity difference between
the H-atom (slightly negatively charged) and the neighbouring silicon atom (slightly positively
charged). In the harmonic oscillator picture, this Si-H dynamic dipole moment is changed when
a resonant infrared photon is absorbed by the oscillator, exciting it to the next higher vibrational
state with a larger dynamic dipole moment due to the increased vibrational amplitude. This
change of the dynamic dipole moment between the initial and the final state and the number of

bonded hydrogen atoms contributing to a specific spectral line determine the intensity of the
corresponding infrared absorption.
In contrast, the relatively weak Raman activity of hydrogen is due to the indirect change of the
electronic polarisability of nearby silicon atoms induced by a vibrating hydrogen atom. Because
a hydrogen atom itself has only one strongly bound valence electron, its own polarisability in the
excitation energy range of standard Raman spectrometers (photon energies between 2 and
4 eV) is negligible. Instead, the vibrations of hydrogen atoms are seen in Raman spectroscopy
because they modulate the polarisability of neighbouring Si atoms, which have a much larger
scattering cross section in this energy range.

THE DOMINANT H-RELATED VIBRATIONAL MODES IN a-Si:H

State-of-the-art amorphous silicon contains hydrogen mainly in the form of Si-H (monohydride)
and Si-H2 (dihydride) bonds, i.e. one or two hydrogen atoms replace one or two of the four
silicon nearest neighbours typical for the tetrahedral short range order of a-Si:H.
The characteristic vibrational modes of these two bonding configurations are shown in FIGURE
1.

resonant

stretch

bend

stretch (sym.) stretch (asym.) "scissors"

rock

wag

twist

FIGURE 1 Vibrational modes of monohydride and dihydride bonding units.

Other configurations such as Si-H3 (trihydride), (Si-H2)N (polysilane), or H2 (interstitial


molecular hydrogen) are generally observed in a-Si:H prepared under non-optimal deposition

conditions (e.g. large deposition rates at low substrate temperatures; see Datareview 2.1).
TABLE 1 summarises the main vibrational frequencies of the most relevant modes. Although
according to theory most of these localised modes are both IR and Raman active, only the
resonant mode and the stretch modes are easily seen in Raman spectra. The reason appears to
be that the Si-H bending modes modulate the polarisability of the nearest neighbour Si-atom
much less than the corresponding stretching modes. Moreover, second order Raman features of
pure silicon mask the weak Si-H bending contribution at 640 cm 1 . Because of these difficulties,
Raman spectroscopy of hydrogen in a-Si:H is only advantageous in special cases, e.g. when
non-transparent substrates have to be used or when a depth profile of bonded hydrogen (using
different Raman excitation wavelengths) is needed.
TABLE 1 Approximate vibrational frequencies of different hydrogen bonding configurations in a-Si:H.
Crosses for IR and R indicate whether a given mode is in principle IR or Raman active.
Modes observed in device quality a-Si:H are emphasised by x!.
Vibrational mode
Wavenumber (cm 1 )
Resonant ('piggy back')
210
Si-H bend
640
Si-H2 rock and wag
640
Si-H2 twist
640
(Si-H2)N rock
640
(Si-H2)N wag
845
Si-H3 bend
860
Si-H2 scissors
880
(Si-H2)N scissors
890
Si-H3 wag
910
Si-H stretch (bulk)
2000
Si-H stretch (surface)
2090
Si-H2 stretch (sym. & asym.)
2095
(Si-H2)N stretch
2090-2140
SiH3 stretch
2120-2150
H2
4150
H2 (collision-induced)
4000-5400

IR
x!
x!

X
X

x!

x!

X
X

The vibrational frequencies given in TABLE 1 are valid for measurements performed at room
temperature and below. For higher temperatures, in particular the stretching modes around
2000 cm"1 exhibit a noticeable mode softening of approximately 0.035 Cm-1ZK [16] attributed to
a decay of the localised modes into silicon lattice vibrations. Other effects such as
anharmonicity of the stretching vibrations or dielectric damping appear to be too small. Note
that the dielectric damping model (modification of the Si-H stretch vibration by the surrounding
Si-network, [17]) is usually invoked to explain the difference between the Si-H stretch
frequency of 2095 cm"1 on a hydrogen terminated Si (111) surface and the frequency of 2000
cm"1 for the same vibrational mode in dense a-Si:H.

DETERMINATION OF THE HYDROGEN CONTENT FROM IR SPECTRA

Apart from the investigation of the main hydrogen bonding configurations in a-Si:H, IR
absorption measurements in a-Si:H have been widely used to estimate the total concentration of
bonded hydrogen in this material. The main idea is that the integrated absorption strength of a
given mode should be proportional to the density N(H) of absorbing Si-H configurations:

(i)
The proportionality constant A depends on the effective dynamical charge e* of the Si-H
dipoles (i.e. the derivative of the dipole moment induced by the infrared radiation with respect
to the displacement of the hydrogen atom) and is given by [14]:
(2)
In EQN (2), c is the velocity of light, n the refractive index, [i the reduced mass of the vibrating
atom, CO0 (in cm'1) the centre frequency of the mode, and A is obtained in units of cm'2 if atomic
units are used for c, m and e*. For a determination of the hydrogen content from IR absorption
spectra, a calibration of the proportionality factor A by quantitative H concentration
measurements is necessary (e.g. via nuclear reaction analysis, SIMS, hydrogen effusion (see
Datareview 2.5), etc.). Such calibrations have been performed by several groups with
somewhat different results. The most commonly used values for different vibrational modes are
summarised in TABLE 2.
TABLE 2 Literature values of the proportionality constant A
in EQN (1) for different vibrational modes in a-Si:H.
Vibrational mode Wavenumber (cm 1 ) A(10 19 cm" 2 ),ref[14] A(10 19 cm" 2 ),ref[18]
Si-H bend
640
1.6
2.1+0.2
Si-H2 wag
860-890
2.0
Si-H2 scissors
Si-H3 bend
2000
2.2
9.0 + 1.0
Si-H stretch
2090
17
Si-H stretch
22 2
Si-H2 stretch
9.1
2095
22 2

There are quite large variations in particular for the stretch vibrations. Using the value of A for
the 640 cm"1 bending modes given in [18], a determination of the concentration of bonded
hydrogen within a relative accuracy of 10% should be possible, provided that the IR absorption
coefficient a in EQN (1) is correctly derived from the primary IR transmission data. According
to Maley [19], this requires the explicit treatment of coherent multiple reflections, especially in
films thinner than about 1 |im. Moreover, it has to be expected that the effective dynamical
charge e* and, consequently, also the A values depend to a certain degree on the structural
properties of a-Si.H (density, impurities, defects, etc.). Thus, Oguz et al have reported
reversible changes of the IR oscillator strength of Si-H vibrations due to defect creation via ion
bombardment [20]. Similar changes have been observed during light-induced degradation of aSi:H ([21] and references therein). The latter authors have argued that light-soaking gives rise
to a real change in the density of bonded hydrogen rather than a change of the effective
dynamical charge. At present, however, it remains unknown to what extent e* might be
affected by different structural and electronic properties of hydrogenated amorphous silicon, so
that particular care should be exercised when interpreting small changes in the IR absorption
strength. This caveat is even more valid for samples with high impurity (C, N, O) or doping
levels, where so far no quantitative analysis has been reported in the literature.

Next Page

CONCLUSION

Infrared absorption data and, to a lesser extent, also Raman scattering spectra can provide
valuable information about the bonding states and the concentration of hydrogen in a-Si:H. The
quantitative analysis of IR and Raman data requires great care due to the spectral overlap of
vibrational modes originating from different bonding configurations and the relatively large
uncertainties (>10%) in the proportionality factors relating infrared absorption strength and
concentration of the various hydrogen bonding configurations.

REFERENCES
[I]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
II1]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]

G. Lucovsky, RJ. Nemanich, JC. Knights [ Phys. Rev. B (USA) vol. 19 (1979) p.2064 ]
R. Zacher, LC. Allen, DC. Licciardello [ J. Non-Cryst. Solids (Netherlands) vol.85 (1986)
p.13]
YJ. Chabal, C.K.N. Patel [ Rev. Mod. Phys. (USA) vol.59 (1987) p.835 ]
KJ. Chang, DJ. Qadi'[Phys- Rev Lett. (USA) vol.62 (1989) p.637 ]
SB. Zhang, W.B. Jackson [ Phys. Rev. B (USA) vol.43 (1991) p.12142 ]
E. Tamow, R.A. Street [ Phys. Rev. B (USA) vol.45 (1992) p.3366 ]
PA. Fedders [ Phys. Rev. B (USA) vol.52 (1995) p. 1729 ]
B. Tuttle, JB. Adams [Phys. Rev. B (USA) vol.56 (1997)p.4565 ]
G.A.N. Connell, J.R. Pawlik [ Phys. Rev. B (USA) vol. 13 (1976) p.787 ]
M.H. Brodsky, M. Cardona, JJ. Cuomo [ Phys. Rev. B (USA) vol. 16 (1977) p.3556 ]
E.C. Freeman, W. Paul [ Phys. Rev. B (USA) vol.18 (1978) p.4288 ]
J.C. Knights, G. Lucovsky [ Crit. Rev. Solid State Sci. (USA) vol.9 (1980) p.211 ]
S.C. Chen, CJ. Fang, M. Cardona [ Phys. Status Solidi B (Germany) vol. 101 (1980) p.451 ]
M. Cardona [ Phys. Status Solidi B (Germany) vol. 118 (1983) p.463 ]
M. Cardona [ J. MoI. Struct. (Netherlands) vol. 141 (1986) p.93 ]
O. Grimal, D.P. Masson, L. Bertrand, A. Yelon [ Phys. Rev. B (USA) vol.49 (1994) p. 10242 ]
H. Wieder, M. Carona, CR. Guarnieri [ Phys. Status Solidi B (Germany) vol.92 (1979) p.99 ]
AA. Langford, ML. Fleet, BP. Nelson, WA. Lanford, N. Maley [ Phys. Rev. B (USA) vol.45
(1992) p. 13367]
N. Maley [ Phys. Rev. B (USA) vol.46 (1992) p.2078 ]
S. Oguz, D.A. Anderson, W. Paul, HJ. Stein [ Phys. Rev. B (USA) vol.22 (1980) p.880 ]
Z. Yiping, Z. Dianlin, K. Guanglin, P. Guangqin, L. Xianbo [ Phys. Rev. Lett. (USA) vol.74
(1995) p.558]

Previous Page

2.4

Data on hydrogen in a-Si:H from NMR


M. Stutzrnann
January 1998

INTRODUCTION

Nuclear magnetic resonance (NMR) of hydrogen (proton NMR) or deuterium (deuteron


magnetic resonance, DMR) is widely used in organic chemistry to investigate structural details
and absolute concentrations of H or D in different bonding configurations. Since a-Si:H or its
isotope exchanged form a-Si:D usually contains protons and/or deuterons in concentrations of
several atomic percent, these techniques can also be applied to amorphous silicon, in order to
obtain microscopic information about hydrogen bonding complementary to that obtained by
other techniques such as infrared absorption (see Datareviews 2.1 and 2.3). The structural
information which can be obtained from NMR follows from the general form of the Hamiltonian
describing the interaction of a given nuclear spin I with its environment:
H = - gn ^tn I (1 - a) H 0 + I Z (Dj Ij ) + I Q I

(1)

In EQN (1), the first term describes the nuclear Zeeman-interaction of I, which is proportional
to the nuclear Lande-factor gn, the nuclear magneton Jin, and the externally applied magnetic
field, Ho. In solids, this Zeeman-interaction is modified by the chemical shift tensor a, caused
by the interaction of the nucleus with the magnetic-field-induced polarisation of the electronic
spins in the surrounding orbitals. The second term describes the dipolar interaction of nucleus I
with nearby nuclei Ij. Finally, the last term in EQN (1) is due to the quadrupole interaction of
nuclei with spins I > 1A with electric field gradients produced by surrounding charge
distributions. This term is zero for protons with I = 1A , but plays a dominant role for deuterons
with I = I : hence the qualitative difference between proton-NMR and DMR in amorphous
silicon.
According to the spin-Hamiltonian (1), the following structural information can be ideally
expected from nuclear magnetic resonance measurements of hydrogenated or deuterated
amorphous silicon:
(i)

information about the total hydrogen content by a suitable integration over all detected
nuclei I,

(ii)

classification of different lattice sites according to their chemical or electric field


environment,

(iii)

correlations between similar or dissimilar nuclei based on their dipolar interaction


(i.e. clustering of hydrogen, polyhydride species, etc.),

(iv)

dynamic properties of the nuclear spin system based on spin-lattice relaxation times, spin
diffusion, motional narrowing, etc.

All of these possibilities have indeed been used for the investigation of hydrogen or deuterium in
amorphous silicon and have led to the results described in this Datareview.

PROTON-NMR IN a-Si:H

A typical NMR spectrum obtained from device-quality a-Si:H is shown in FIGURE 1. The
spectrum consists of a narrow central line with a Lorentzian shape, a broader Gaussian
component, and a so called cPake doublet9 due to molecular hydrogen. This latter component
usually can only be observed in sufficiently large samples or samples with a high concentration
ofH 2 molecules, e.g. after annealing at about 50O0C. As first pointed out by Reimer et al [1] as
well as Carlos and Taylor [2], this structure of NMR spectra is quite universal for hydrogenated
amorphous silicon prepared under various conditions. Different samples mainly differ by the
relative intensities and specific widths of the different lines. More details are given in TABLE 1
and in the review by Taylor [3].
(a)

(b)
X50

(V-V0) (kHz)

FIGURE 1 Low temperature NMR spectrum of device-quality undoped a-Si:H showing a


narrow central Lorentzian line and a broad Gaussian component (a). Under sufficient
amplification, a weak Pake doublet can also be resolved (b). From [4].
TABLE 1 Main NMR features of different hydrogen bonding units in a-Si:H. Width corresponds
either to the FWHM {Lorentzian or Gaussian) or to the splitting (Pake doublet). See text for details.
The respective concentrations of the different hydrogen states are deduced from the integrated
intensity of the corresponding lines.
Shape
Lorentz
Gauss
Pake doubl.
Pake doubl.

Structural origin
Width (kHzL Concentration (at.%)
0-5
isolated Si-H bonds
3-5
0-25
clustered Si-H bonds
25-35
0-1
H2 molecules
175 10
isolated Si-H2 bonds
14

The structural interpretation of the different NMR components is as follows. The narrow
central Lorentzian line is due to isolated Si-H bonds. Isolated in the sense of the NMR spectral

features means that the dipolar interaction with other hydrogen atoms nearby is smaller than the
Lorentzian linewidth, which in turn is given by the finite lifetime of the proton spin state (see
Section E). For the dipolar interaction to remain smaller than e.g. 3 kHz, the separation
between two hydrogen atoms must be larger than approximately 1 nm (the dipolar broadening
decreases with inter-nuclear distance r as r"3). Therefore, by placing all hydrogen atoms on a
cubic lattice, one can estimate the maximum concentration of isolated protons to be about
5 at.%, in good agreement with the experimental observations. Additional hydrogen entering
the amorphous network, therefore, will contribute necessarily to hydrogen clusters with
internuclear spacings below the critical separation estimated above. This leads to the
appearance of a second, inhomogeneously broadened Gaussian NMR line with an FWHM
above 10 kHz in all a-Si:H films with a total hydrogen concentration exceeding the critical value
of 5 at.%. (Note that the reverse is not generally true, i.e. films with hydrogen concentrations
below 5 at.% still may exhibit a broad Gaussian NMR signal due to clustered hydrogen.)
As far as the detailed structure of the clustered hydrogen phase in a-Si:H is concerned, standard
NMR measurements are unable to provide further clarification, since the typical FWHM of the
Gaussian line does not follow simply from structural models such as hydrogenated vacancies,
Si-H2 or Si-H3 bonds, or polysilane chains [I]. Instead, the clustered phase appears to be a
superposition of many different conceivable bonding structures. More details can be deduced
from multiple quantum NMR measurements discussed in Section C of this Datareview.
A more definitive assignment has been possible only in two cases, where the observation of a
resolved Pake-doublet has provided a reasonably accurate determination of the H-H-distance
(see TABLE 1). The most obvious case is the occurrence of hydrogen molecules with a
characteristic Pake doublet splitting of 175 kHz (FIGURE l(b)). The concentration of H2
molecules is usually too low for their direct observation via NMR, but is sometimes possible in
large volume samples at temperatures below 10 K, i.e. below the melting temperature of H2
(14 K). However, the H2 concentration can be significantly enhanced by annealing a-Si.H at
about 5000C. During such an anneal, Si-H bonds are thermally broken and some of the
liberated hydrogen atoms diffuse towards each other, forming hydrogen molecules which remain
trapped in internal voids under elevated pressure [4,5].
The second case of a positive structural assignment is that of Si-H2 bonds with an internuclear
distance of 0.23 nm, giving rise to a Pake doublet with a peak separation of approximately
14 kHz. The corresponding NMR signal has been observed in a-Si:H films deposited at room
temperature and thus containing an unusually large concentration of polyhydride units [6].

MULTIPLE QUANTUM NMR

More detailed information concerning the structure of the clustered hydrogen phase giving rise
to the broad Gaussian line discussed in the preceding section comes from multiple quantum
NMR experiments [7,8]. In these experiments, specific RF pulse sequences are employed to set
up a phase coherence among different proton spins coupled by dipolar interaction. This allows
the detection of higher order NMR transitions (Ami = 2, 4, 6 etc.), corresponding to the
simultaneous spin flip of 2, 4, 6 etc. coupled protons. The highest order of such transitions then
provides a measurement for the average number of hydrogen atoms forming a typical hydrogen
cluster. In device quality a-Si:H deposited above 2000C, such clusters were found to comprise

approximately six hydrogen atoms on average (e.g. a hydrogenated divacancy). As the


hydrogen density is increased, e.g. by deposition at lower substrate temperatures, the number of
interacting hydrogen atoms increases to more than twenty, but distinct clusters with 6 - 8
hydrogen atoms still can be detected. Multiple quantum NMR also indicated a principal
difference between the influence of deposition temperature and annealing temperature on the
clustering behaviour of hydrogen. Thus, samples deposited close to 3000C mainly exhibit
cluster sizes around 6 H atoms, whereas samples deposited at 1000C and then annealed at
3000C have much larger clusters, although the overall hydrogen content in both cases can be
almost identical. As a rule of thumb, the total hydrogen concentration in a-Si:H depends
primarily on the highest (deposition or annealing) temperature experienced by a given sample,
whereas the hydrogen microstructure is determined mainly by the deposition temperature.

DEUTERATED AMORPHOUS SILICON

In contrast to hydrogen, deuterium (D) has a nuclear spin I = I and therefore is sensitive to
electric field gradients via the quadrupole term in EQN (1). In a-Si:H, such electric field
gradients are primarily due to the charge transfer between hydrogen and silicon atoms because
of the slightly higher electron affinity of hydrogen. As a consequence, deuteron magnetic
resonance (DMR) spectra of amorphous silicon show very different spectral features than
proton NMR spectra [9,10]. The most prominent signature of DMR spectra in a-Si:D,
accounting for the majority of deuterium atoms, is a quadrupolar Pake doublet with a
characteristic splitting of 66 1 kHz due to Si-H and Si-H2 bonds in a tetrahedral bonding
environment. The corresponding electric field gradient is determined on one hand by the
Si-to-H charge transfer mentioned above, and by the well-defined Si-H bond length on the other
hand. In addition to this Pake doublet, as-deposited device quality a-Si:D samples also exhibit a
broad central line (FWHM of approximately 30 kHz at low temperatures), which has been
assigned to deuterium in more disordered regions at or close to microvoids. The concentration
of deuterium contributing to this disordered phase typically varies between 1 and 5 at.%. Upon
annealing above 3500C, the DMR spectra change dramatically: first the broad central resonance
and then the quadrupolar Pake doublet disappear and merge into a narrow central resonance,
whose FWHM of about 1 kHz (at 300 K) is caused by motional narrowing of mobile D 2
molecules in microvoids. At lower temperatures, some of these molecules become physisorbed
at internal surfaces, causing an increase of the corresponding DMR FWHM to about 10 kHz
[10].

MOLECULARHYDROGEN

It has generally been observed that the spin-lattice relaxation of protons and deuterons in aSi:H,D is determined by a small fraction of H2 or D 2 molecules trapped in the film. A
characteristic minimum of the spin lattice relaxation time Ti of bonded hydrogen or deuterium
around 30 K has been successfully explained by spin diffusion towards such molecules, which
can act as efficient relaxation centres due to their rapid rotational motion [11,3]. In device
quality amorphous silicon, the density of molecules trapped in the Si network is of the order of
0.1 at.%. In this case, the molecules are dispersed throughout the lattice and well separated
from each other. Upon annealing at around 5000C, Si-H bonds are thermally dissociated and
some of the liberated hydrogen atoms can recombine with each other, thus forming additional

H2 molecules. This can increase the concentration of hydrogen molecules to about 1 - 2 at.%,
with most of the molecules clustered in internal voids under considerable pressure (up to
2kbar). Below 10 K9 these hydrogen bubbles form solid hydrogen, giving rise to the
characteristic Pake doublet shown in FIGURE 1 [4]. As the temperature is increased, these
solid hydrogen inclusions first melt, adding spectral weight to the broad central NMR line
(between 10 K and 20 K). At even higher temperatures, the hydrogen molecules move fast
enough so that their spectral weight now appears in the narrow central component of the NMR
spectra due to motional narrowing. This can lead to an overestimation of the density of isolated
Si-H bonds (see Section B) in samples with a high density of molecular hydrogen and
measurements performed above 20 K.

CONCLUSION

Hydrogen NMR is a very useful experimental method to study the absolute concentrations of
hydrogen in different bonding states. The most prominent bonding configurations of hydrogen
observed by proton NMR in a-Si:H are isolated Si-H and Si-H2 bonds, hydrogen clusters
containing typically 6 to 8 hydrogen atoms, and hydrogen molecules, which are observed mainly
after annealing at elevated temperatures (approximately 5000C). Multiple quantum NMR and
deuteron magnetic resonance (DMR) can provide complementary information helping to
unravel the complex hydrogen microstructure of amorphous silicon.

REFERENCES
[I]

J.A. Reimer, R.W. Vaughan, J.C. Knights [ Phys. Rev. B (USA) vol.24 (1981) p.3360 ]

[2]
[3]
[4]
[5]

W.E Carlos, P.C. Taylor [ Phys. Rev. B (USA) vol.26 (1982) p.3605 ]
P.C. Taylor [ Semicond. Semimet. (USA) vol.21 part C (1984) p.99 ]
J.B. Boyce, M. Stutzmann [ Phys. Rev. Lett. (USA) vol.54 (1985) p.562 ]
J.B. Boyce, S.E. Ready, M. Stutzmann, R.E. Norberg [ J. Non-Cryst. Solids (Netherlands)
vol.114 (1989) p.211]
J.B.Boyce [NATO ASISer. B, Phys. (USA) vol.136 (1986) p. 101 ]
J. Baum, K.K. Gleason, A. Pines, A.N. Garroway, J.A. Reimer [ Phys. Rev. Lett (USA) vol.56
(1986) p. 1377]
K.K. Gleason, M.A. Petrich, J.A. Reimer [ Phys. Rev. B (USA) vol.36 (1987) p.3259 ]
DJ. Leopold, P.A. Fedders, R.E. Norberg, J.B. Boyce, J.C. Knights [ Phys. Rev. B (USA) vol.31
(1985)p.2642]
V.P. Bork, P.A. Fedders, DJ. Leopold, R.E. Norberg, JB. Boyce, J.C. Knights [Phys. Rev. B
(USA) vol.36 (1987) p.9351 ]
M.S. Conradi, R.E. Norberg [Phys. Rev. B (USA) vol.24 (1981)p.2285 ]

[6]
[7]
[8]
[9]
[10]
[II]

2.5

Data on hydrogen in a-Si:H from diffusion and effusion


studies
M. Stutzmann
February 1998

INTRODUCTION

The hydrogen bonding structure has a profound influence on the thermal stability of
hydrogenated amorphous silicon. Long before the Si network atoms start to move, the lightweight hydrogen atoms can diffuse within a sample, giving rise to a number of subtle structural
changes, such as defect annealing, dopant passivation or activation, and most likely also lightinduced metastability. A detailed and quantitative model for hydrogen diffusion is, therefore, a
prerequisite for a better understanding of such thermally or optically induced changes of the
electronic density of states. At temperatures close to or exceeding the deposition temperature,
a significant amount of the bonded hydrogen will also start to leave the a-Si:H material in the
form of H2 molecules, a process known as hydrogen effusion which, obviously, is of
fundamental importance for the maximum temperature a sample can be exposed to before
irreversible structural changes will occur. Historically, hydrogen diffusion and effusion in
a-Si:H have originally been used as an analytical tool to study different hydrogen bonding
structures and their thermal stability [1,2]. More recently, attention has focused on possible
connections between hydrogen diffusion and electronic instabilities [3,4].

THE ENERGETICS OF HYDROGEN BONDING IN a-Si:H

The main quantity determining the diffusion and effusion behaviour of hydrogen in amorphous
silicon is the average binding energy of a hydrogen atom with respect to the lowest energy
transport path in the amorphous network. It is now widely accepted that this lowest transport
path is the motion of a single hydrogen atom via the so-called cbond-centre' (BC) site. In this
case, the hydrogen atom inserts itself symmetrically between two nearest neighbour silicon
atoms. This is identical to the case of crystalline silicon, where the BC site has been identified
as the lowest energy state of hydrogen in a defect free crystal by a number of theoretical studies.
If one also allows the complexing of hydrogen with lattice defects or with each other, a much
more complicated situation evolves, as indicated by the schematic configurational model in
FIGURE 1 and the approximate binding energies given in TABLE 1.
For the following discussion of diffusion and effusion in a-Si:H one therefore has to keep in
mind that, theoretically, hydrogen can exist in the amorphous silicon network in a large number
of different bonding configurations covering a wide binding energy range: from 1 eV for the
isolated neutral hydrogen interstitial at the bond-centre site to 3.4 eV for a neutral hydrogen
atom trapped at an isolated, pre-existing dangling bond. Intermediate H binding energies occur
due to complexing of two or more Si-H bonds.

FIGURE 1 Possible structural configurations of isolated and clustered hydrogen in


a-Si:H: monohydride (Si-H), dihydride (Si-H2), polysilane ((Si-H2)J, interstitial
molecules (H2 and H2*), and hydrogenated voids (dashed circle).
TABLE 1 Approximate binding energies Ebind per hydrogen atom in different structural configurations.
For details see [5-8] and references therein.
Notation
H0
BC
H2*
H 2 (int)
H 2 (void)

E b ind(eV) Configuration or comment

(H 2 *) n
Si-H..H-Si

0
1.0
1.7
1.9
2.3
1.9-2.5
2.5-3.0

VH 4
Si-H

3.1
3.4

neutral hydrogen atom in vacuum (reference level)


bond centred hydrogen: Si-H-Si three centre bond
Si-H bonding/ antibonding pair [6]
interstitial hydrogen molecules (isolated)
hydrogen molecules in large voids
complexes of H2*
Si-Si bond broken by insertion of two H atoms
(and complexes of this specific (Si-H)2 configuration)
relaxed hydrogenated vacancy
single H atom binding to a pre-existing Si dangling bond
(e.g. at an internal void or surface)

HYDROGEN DIFFUSION IN AMORPHOUS SILICON

Cl

Diffusion in Undoped a-Si:H

The temperature dependence of the hydrogen difliision coefficient DH in amorphous silicon has
been determined by a number of groups using different experimental methods: secondary ion
mass spectrometry (SIMS) of a-Si:H/a-Si:D/a-Si:H sandwich structures [1,9], hydrogen
effusion [2,10, and Section D], or profiling of hydrogen concentrations near the surface with
different methods [11,12]. The experimental data are usually fitted by the Arrhenius-type
expression:
0)

where D0 is the exponential prefactor and ED the apparent activation energy of the diffusion
coefficient. Values for these two parameters obtained by different experimental methods and
for differently prepared amorphous silicon samples are given in TABLE 2. The typical
temperature range for diffusion measurements in a-Si:H is between 200 and 6000C.
TABLE 2 Pre-exponential factors D 0 and activation energies E D of hydrogen or deuterium
diffusion in undoped amorphous silicon. T dep is the deposition temperature.
D 0 (Cm2S"1)

1.2 x
4.7 x
IO 3 1 0.2

10"
IO 3
IO 2
x IO 2

io- 3
io- 3
3 - 4 x IO2
0.5 - 3000
3.5
120
10"4 - IO2

ED (eV)
1.53
1.5
1.4-1.5
1.51+0.2
1.4
1.4
1.66
1.94-2.44
1.85
2.26
1.4-2.1

Deposition technique
DC glow discharge
RF glow discharge
RF glow discharge
RF glow discharge (different variants)
Evaporation
RF glow discharge
RF glow discharge, 9 at.% H
RF sputtered, 2 at.% H
Amorphisation by ion implantation, >5 at.% H
Amorphisation by ion implantation, <2 at.% H
RF glow discharge at different temperatures

Ref
315
[1]
420 - 450 [2]
230
[9]
280 - 300 [10]
300
[H]
300
[12]
[13]
[13]
[14]
[14]
200 - 600 [15]
T d ep(C)

It is obvious from TABLE 2 that the experimental values for the relevant diffusion parameters
fall within a wide range. In particular, the systematic investigation by Beyer on glow-discharge
deposited a-Si:H with hydrogen concentrations varying between 0.1 and 14 at.% has shown that
there is a clear tendency of both D 0 and ED to increase with decreasing hydrogen content [15].
In addition, a correlation exists between the different values of the exponential prefactor and the
apparent activation energy of the diffusion process. As pointed out by Shinar et al, the available
experimental data can be summarised by a Meyer-Neldel type relation between D0 and ED [13]:
(2)
with

and

The present interpretation of these experimental results is based on the trap-limited diffusion of
a chemically reactive species (hydrogen) within a flexible host lattice (silicon). The main
concept of this mechanism, namely the existence of a low energy trapping site (e.g. hydrogen at
Si dangling bond) together with a well defined transport path (e.g. hydrogen moving via
interstitial BC sites) with a low activation energy for migration (e.g. 0.5 eV in the case of
BC-to-BC migration in crystalline or amorphous silicon), has already been anticipated early on
by Zellama et al [2]. Direct experimental evidence for a simple case of trap-limited diffusion of
hydrogen comes from the investigation of acceptor passivation in crystalline silicon, where a
substitutional acceptor such as boron acts as a well-defined trap for hydrogen introduced via the
sample surface by H-plasma exposure [16]. However, the situation in a-Si:H is much more
complicated and has not yet converged to a single unifying model. Thus, we present here only a
preliminary view of the present understanding in terms of basic statements, with the caveat that
some of these statements are not generally accepted and also will be subject to change in the
future.

Without the presence of deep traps, hydrogen would diffuse in amorphous silicon quite
similarly to the case of crystalline silicon, e.g. via BC-to-BC site hopping with an
activation energy of about 0.5 eV.

The structural disorder of amorphous silicon introduces a large density of deep traps for
isolated hydrogen. These deep traps capture H in the form of single Si-H bonds and
give rise to the strongly bound, isolated hydrogen phase observed in nuclear magnetic
resonance (see Datareview 2.4). The binding energy of hydrogen in this phase is about
3.4 eV, as shown in TABLE 1. The solubility of hydrogen in this phase is limited to
about 4 at.% [15,18].

Additional hydrogen atoms incorporated in the a-Si:H network in excess of the solubility
limit mentioned above give rise to a clustered hydrogen phase with a lower specific
binding energy of about 2.0-3.0 eV, depending on the specific cluster configuration.

A further basic observation concerning hydrogen diffusion in a-Si:H is that the diffusion
process is dispersive, i.e. the effective diffusion constant D at a given temperature
decreases with increasing diffusion time [7,9,13]. A straightforward explanation of this
experimental fact is that in the as-deposited state the hydrogen bonding configurations in
a-Si:H are not in a thermal equilibrium situation. Upon thermal annealing, the diffusing
hydrogen atoms try to relax towards thermal equilibrium, which means that on average a
released H-atom will become retrapped at a new site with a higher binding energy. This
gives rise to an explicit time-dependence of the H-diffusion coefficient D according to:
DCt) = D(O) {cotr

(3)

where is the hydrogen attempt-to-diffuse frequency and a is a temperature dependent


dispersion parameter:
a=l-T/T0

(4)

In other words, hydrogen diffusion in a-Si:H performed at a constant temperature will


slow down as time progresses, due to the interaction of mobile hydrogen with a
distribution of hydrogen traps with a characteristic energetic width of about kT0. A
direct consequence of this explicit time dependence is that the activation energy ED for
hydrogen diffusion according to EQN (2) should be determined only under the
additional boundary condition of a constant diffusion length. The microscopic nature of
the various hydrogen bonding states giving rise to this dispersive hydrogen diffusion in
a-Si:H is not clear yet. For a detailed account of different aspects of this problem the
reader is referred to [7,13,15,17,19].
C2

Influence of Free Carriers and Illumination

An important observation for all practical applications of a-Si:H is the fact that the diffusion of
hydrogen in undoped amorphous silicon is considerably enhanced in the presence of electronic
excitation, e.g. strong illumination [20,21]. Thus, strong illumination (with intensities of about
10 W cm"2) at 2500C gives rise to an increase of the deuterium diffusion coefficient by about a
factor of 10, from 3 x 10"17 to 3 x 10'16 Cm2S"1, mainly due to a decrease of the diffusion

activation energy to about 1 eV under intense illumination. Similarly, the diffusion of hydrogen
is suppressed under conditions where electronic carriers are removed, such as in the space
charge region of a reverse-biased diode [22]. The present interpretation of these experimental
results is that the trapping of excess electrons or holes in the antibonding or bonding states of
Si-H bonds decreases the activation energy of Si-H bond dissociation. However, details of the
underlying mechanism remain to be established. It should be noted that the observed lightinduced enhanced hydrogen diffusion does not provide a direct explanation for the light-induced
metastability in a-Si:H (Staebler-Wronski-effect: see Datareview 5.4); extrapolating the
experimental data of [20] to a temperature of 400C and illumination intensities below 1 W cm"2
leads to a hydrogen diffusion coefficient below 10~21 Cm2S"1 under these conditions. For a lightsoaking time of typically 105 s, the average hydrogen diffusion length is then clearly below
0.1 nm, i.e. less than a Si-H bond length.
C3

Hydrogen Diffusion in Doped a-Si:H

A different way of increasing the density of excess charge carriers in a-Si:H is substitutional
doping with boron or phosphorus. As a matter of fact it was reported by Street et al [9] that
doping with either P or B gives rise to a significantly enhanced hydrogen diffusion at all relevant
temperatures. However, these authors do not observe a direct relation between the hydrogen
diffusion coefficient and the excess electron or hole density. Thus, boron-doped a-Si:H has a
lower density of thermally excited holes compared to excess electrons in P-doped amorphous
silicon, yet the hydrogen diffusion coefficient in B-doped samples is significantly higher. Also,
in the case of P-doped a-Si:H it was observed that doping in excess of 100 ppm does not give
rise to a further enhancement of hydrogen diffusion, whereas the density of free electrons still
increases. TABLE 3 summarises the experimental results from [9] for a diffusion temperature
of 2400C.
TABLE 3 Influence of substitutional doping with phosphorus and/or boron
in a-Si:H on the hydrogen diffusion coefficient DH at 2400C [9].
Doping level
DH at 240C(cmV) H diffusion energy (eV)
1.4-1.5
0
10 17
4
1.3
10" B
10 15
1.3
10"2B
10 14
10 -i6
1.2
10"4P
10 -i6
1.2
10"2P
3
3
1.4
compensated (10 P + 10" B)
io- 17

The exact reason for the strong influence of doping on the diffusion behaviour of hydrogen in
a-Si:H is not yet clear. As mentioned above, a direct relation with the density of thermally
excited free electrons or holes seems improbable. Street et al have suggested that dopinginduced dangling bond defects could provide a lower energy path for the movement of
hydrogen through the a-Si:H network, but it is not straightforward to understand the order of
magnitude differences between strongly B-doped and P-doped material in this approach. A
different possibility is that B-H complexes, which are well known from doped hydrogenated
crystalline silicon, provide a reservoir of weakly bound hydrogen in B-doped a-Si:H and cause
the overall enhancement of the diffusion coefficient in the context of the trap-limited diffusion
model [17,19]. Further work will be necessary to answer these basic questions.

HYDROGEN EFFUSION

In a typical H effusion experiment (also known as thermally stimulated desorption, TSD), a


sample is placed within a vacuum vessel and is heated with a linear temperature ramp with a
slope of approximately 10 K s"1. At temperatures above the deposition temperature, bonded
hydrogen will start to emanate from the sample in the form OfH2 molecules, which then can be
easily detected by, for example, a quadrupole mass spectrometer. The basic information
obtained from such TSD experiments concerns the binding energy of the effused species either
within the sample or on the surface, and the total concentration of the corresponding atoms in
the initial sample. For an introduction to the method and the data analysis see e.g. [23].

H Partial Pressure (mbar)

A typical example of a hydrogen effusion spectrum obtained in standard a-Si:H is shown in


FIGURE 2. The main features of such a spectrum are two more or less pronounced effusion
peaks located at approximately 4000C and 500 - 6000C for a heating rate of 20 K s"1 [24,25].

a-Si:H, undoped
p = 20K/min

Temperature (0C)
FIGURE 2 A typical hydrogen effusion spectrum obtained for an undoped a-Si:H sample (about
1 fxm thick) deposited at 2500C. The sample was heated with a linear rate of 20 K s"1.
The sharp peak at about 7000C is due to thermal crystallisation of the sample.

It was shown by Beyer [25] that the exact location of the high temperature effusion peak
strongly depends on the sample thickness (increasing approximately linearly from 5000C for a
sample thickness below 200 nm to 6000C for samples with a thickness in excess of 1500 nm).
In contrast, the position of the low-temperature effusion peak does not depend on sample
thickness; however, such a peak is only observed in a-Si:H samples deposited under nonoptimum conditions, in particular at low substrate temperatures.
For the microscopic interpretation of the H-eflusion spectra, the following overall picture has
emerged:

Hydrogen effusing at low temperatures (weakly bound hydrogen) is associated with the
clustered hydrogen phase already known from NMR or IR experiments (see
Datareviews 2.3 and 2.4). The thermal desorption is facilitated by the energetically
favourable formation of H2 molecules from neighbouring Si-H bonds, in particular the
Si-H2 dihydride configurations. After H2 formation, the molecules diffuse rather freely
to the surface of the film and are emitted into the vacuum without further interaction.

The high temperature effusion peak is mainly due to monohydride bonds, which are
dominant in state-of-the-art samples. In this case, single Si-H bonds are thermally
broken and the liberated atomic hydrogen diffuses through the amorphous network until
it recombines with a second hydrogen atom to form a molecule. An obvious place for
this molecule formation to occur in a dense film is the sample surface.

The basic consequences of this model are discussed in [25]. In particular, the diffusion of
atomic hydrogen has been tested by examining the effusion from H/D/H sandwich structures.
The amount of hydrogen contributing to the low-temperature effusion peak increases linearly
with hydrogen concentrations in excess of about 10 at.%, which is close to the maximum
concentration of isolated hydrogen soluble in an amorphous silicon network. Deposition of
a-Si:H at low substrate temperatures leads to a strong increase of the low-temperature effusion
peak, in accordance with the increase in the concentration of clustered hydrogen observed in IR
and NMR experiments [26]. Finally, it has been observed that boron doping gives rise to a
pronounced lowering of the hydrogen effusion temperature in a-Si:H, whereas phosphorus
doping has much less influence [25]. Again, this is in good agreement with the behaviour
expected from the diffusion measurements mentioned above.

CONCLUSION

The experimental results obtained from diffusion and effusion studies of hydrogen or deuterium
in amorphous silicon support a general two-phase structural model, distinguishing between
clustered and isolated hydrogen bonding configurations. This separation is most obvious in the
case of thermal effusion studies, where weakly (clustered) and strongly bound (isolated)
hydrogen gives rise to two distinct thermal effusion peaks. In diffusion experiments, the
complex interaction of interstitial hydrogen with a broad spectrum of different shallow or deep
structural traps produces a complicated scenario, involving aspects such as trap filling,
dispersive hydrogen diffusion, or electronically enhanced processes. It is very likely that the
present state of understanding will be subject to considerable change due to new experimental
results and theoretical models.

REFERENCES
[1]
[2]
[3]
[4]
[5]

D.E. Carlson, CW. Magee [Appl Phys. Lett. (USA) vol.33 (1978) p.81 ]
K. Zellama, P. Geraiain, S. Squelard, B. Bourdon, J. Fontenille, R. Danielou [ Phys. Rev. B
(USA) vol.23 (1981) p.6648 ]
W.B. Jackson, J. Kakalios [ Phys. Rev. B (USA) vol.37 (1988) p. 1020 ]
P.V. Santos, N.M. Johnson, R.A. Street [ Phys. Rev. Lett. (USA) vol.67 (1991) p.2686 ]
CG. VandeWalle, P.J.H. Denteneer, Y. Bar-Yam, ST. Pantelides [Phys. Rev. B (USA) vol.39
(1989) p. 10791]

[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]

S.B. Zhang, W.B. Jackson, DJ. Chadi [ Phys. Rev. Lett. (USA) vol.65 (1990) p.2575 ]
W.B. Jackson, CC. Tsai [ Phys. Rev. B (USA) vol.45 (1992) p.6564 ]
CG. Van de Walle, RA. Street [ Phys. Rev. B (USA) vol.49 (1994) p. 14766 ]
R.A. Street, C C Tsai, J. Kakalios, W.B. Jackson [ Philos. Mag. B (UK) vol.56 (1987) p.305 ]
W. Beyer, H. Wagner [ J. Appl. Phys. (USA) vol.53 (1982) p.8745 ]
A.V. Dvurechenskii, LA. Ryazantsev, LS. Smimov [ Sov. Phys.-Semicond. (USA) vol.16
(1982) p.400 ]
M. Reinett, S. Kalbitzer, G. Miiller [ J. Non-Cryst. Solids (Netherlands) vol.59&60 (1983)
p.169]
J. Shinar, R. Shinar, X-L. Wu, S. Mitra, RF. Girvan [ Phys. Rev. B (USA) vol.43 (1991)
p.1631]
S. Acco, W. Beyer, E.E. van Faassen, W.F. van der Weg [ J. Appl. Phys. (USA) vol.82 (1997)
p.2862 ]
W. Beyer [ Phys. Status Solidi A (Germany) vol. 159 (1997) p.53 ]
CP. Herrero, M. Stutzmann, A. Breitschwerdt, PV. Santos [ Phys. Rev. B (USA) vol.41 (1990)
p. 1054]
P.V. Santos, W.B. Jackson [ Phys. Rev. B (USA) vol.46 (1992) p.4595 ]
S. Acco et al [ Phys. Rev. B (USA) vol.53 (1996) p.4415 ]
M. Kemp, H.M. Branz [ Phys. Rev. B (USA) vol.52 (1995) p.13946 ]
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[ Phys. Rev. B (USA) vol.53 (1996) p.3804 ]

2.6

Structural information on a-SiC:H from IR and Raman


spectroscopy
F. Giorgis, F. Giuliani, CF. Pirri, V. Rigato, E. Tresso and S. Zandolin
March 1997

INTRODUCTION

Infrared (IR) and Raman spectroscopies are perhaps the most widely used techniques to
understand the structure of a-Sii_xCx:H films since they are easily performed, non-destructive
and yield information about the bonding configurations of atoms and network order.
The integrated intensity of the IR peaks is related to the concentration of bonds. The integrated
absorption is given by the relationship

0)
where a(co) is the infrared absorption coefficient, and the integration is performed over the
deconvoluted infrared peaks after subtraction of the baseline.
Some attempts have been made to obtain an absolute evaluation of bond concentration in
a-Sii-xCx:H films by IR spectroscopy in order to get information on elemental composition.
However, with some caution IR spectroscopy is useful only to study relative concentrations of
hydrogen, since an absolute calibration is very difficult. Nuclear measurements are the most
reliable techniques for this and, combining them with IR and Raman data, it is possible to have a
complete quantitative picture of microscopic structural properties of a-Sii_xCx:H films.

INFRARED SPECTROSCOPY

Bl

a-Sii-xCz:H Infrared Spectra

Composition of a-Sii-xCx:H alloy can be varied from a-Si:H to a-C:H, that is from a completely
tetrahedrally coordinated material to a more complex structure, since the carbon can be bonded
in either trigonal or tetrahedral coordination.
In a-Si:H at x = 0 the film network is due to Si-Si and Si-H bonds. IR spectra of a-Si:H consist
of three absorption regions [1-3]:
(a)

The band at 2000 - 2100 cm"1 is formed by the 2000 cm"1 stretching mode, commonly
attributed to isolated monohydrides, Si-H, and the 2100 cm"1 mode, attributed to
dihydrides, SiH2, as well as (SiH)n in microvoids.

(b)

The doublet at 845 - 880 cm"1 is due to dihydride bending or scissoring modes.

(c)

The mode at 630 cm'1 is attributed to SiHn wagging modes.

TABLE 1 reports the assignments of the IR vibrational modes for a-Si:H [3]. It is expected
that these assignments can be applied with small modifications to the spectra of a-Sii_xCx:H
containing low carbon concentrations in the silicon network.
TABLE 1 Infrared absorption bands in a-Si:H and their assignment [3].
Bonding
SiH
SiH2

(SiH)n

Frequency
(cm 1 )
2000
630
2090
880
630
2090-2100
880
845
630

Assignment
stretching
wagging
stretching
bending-scissoring
rocking
stretching
bending-scissoring
wagging
rocking

For a-C:H, at x = 1, from the analysis of the fine structure of the vibrational IR spectra it has
been deduced that, in hard a-C:H, hydrogen is mainly incorporated as monohydride, whereas in
soft polymeric films a larger hydrogen concentration is present in CH2 or CH3 forms [4]. The
most meaningful infrared absorption bands and their assignments for a-C:H films are reported in
TABLE 2 [4]. Remarkable information on the total amount of bonded hydrogen and on the
type of bonding (carbon hybridisation) can be deduced by the analysis of the C-H stretching
bands in the range 2800 - 3100 cm"1 [5]. Most assignments can be attributed also to the bands
in the IR spectra of very carbon-rich a-Sii-xCx:H alloys [6].
TABLE 2 Infrared absorption bands in polymeric-like a-C:H and their assignment [4].
Bonding Frequency Assignment
(cm 1 )
1
3300
stretching
CH sp
3060
stretching
CH sp2
3000
stretching
CH sp2
1445
bending
CH sp2
1280
bending
CH sp2
3025
stretching
CH2Sp2
1450
bending
CH2 sp2
1110
bending
CH2 sp2
2945
stretching
CH2 sp3
2875
stretching
CH2 sp3
2850
stretching
CH2sp3
1030
bending
CH2Sp3
2970
stretching
CH3Sp3
1490
bending
CH3Sp3
1450
bending
CH3Sp3
1325
bending
CH3 sp3
1075
bending
CH3 sp3

In a-Sii-xCx:H films, all the IR vibrational structures characteristic of Si-H, C-H, Si-C and C-C
bonds are observed. FIGURES l(a) and l(b) show typical IR absorption spectra of a-Sii_xCx:H

absorptance [arb. un.]

films, grown by PECVD in SiH4 + CH4 and SiH4 + C2H2 mixtures [7]. In TABLE 3 the
infrared vibrational frequencies detected in a-Sii.xCx:H films are reported.

SH
i waggn
ig
SC
i stretchn
ig
SC
i H3 waggn
ig / SC
i stretching CH4
SH
i 2 bendn
ig
SiHn stretching
CHn waggnig
SC
i Hn bendn
ig

CHn stretching

absorptance [arb. un.]

wavenumber [cm"1]

x=C/(C+S)i

SC
i stretching
SC
i H3 waggn
ig / SC
i stretcShiH
ingstretching
SH
i waggn
ig
n
SH
i 2 bendn
ig
CHn stretching
CHn waggn
ig
C2H2
SC
i Hn bendn
ig

wavenumber [on" ]

x=C/(C+S)i

FIGURE 1 Infrared absorption spectra for a-Sii_xCx:H films grown by


PECVD in SiH4 + CH4 and SiH4 + C2H2 gas mixtures [7,9].

The IR spectra of a-Sii-xCx:H alloys can be divided into six regions:


(a)

The region between 2800 and 3100 cm"1 is due to CHn stretching modes both in sp3 and
sp2 configurations. In films grown from SiH4 + CH4 gas mixtures there are two resolved
peaks at about 2960 cm"1 and at about 2880 cm"1. The peak at 2960 cm"1 can be
attributed to asymmetrical stretching vibrations of CH3 groups in sp3 configuration and
the peak at 2880 cm"1 can be attributed both to symmetrical stretching vibrations OfCH3
groups and to stretching vibrations of CH2 groups in sp3 configuration [8-11]. In films
grown from SiH4 + C2H2 [7] or SiH4 + C2H4 [8] gas mixtures a broader band is
observed, which can be deconvoluted into four peaks at 2860 cm"1 (sp3 CH2 symmetric

TABLE 3 Infrared absorption bands in a-Sii_xCx:H films and their assignment [4,6].
Bonding
CH, CH2 sp2
CH3Sp3
CH2 sp3
CH3Sp3
CH2 sp3
C-SiH, SiH2, (SiH)n
SiH
C=C
Si-CH2-Si
CH2, CH sp2
CH2 sp3
Si-CH3, CH2
Si-CH3
CHn
(SiH2)n
Si-CH3, Si-C
Si-C
SiH

Frequency
Assignment
(cm 1 )
3000
stretching
2960
stretching (asymmetric)
2920
stretching (asymmetric)
2880
stretching (symmetric)
2860
stretching (symmetric)
stretching
2090-2100
stretching
2000
stretching
1500 - 1600
scissoring
1450
bending
1450
bending,
scissoring
1400
bending
(asymmetric),
wagging
1350
bending
(symmetric)
1250
wagging, rocking
950-1100
bending
800 - 900
wagging,
stretching
750 - 800
stretching
650 - 700
wagging
630 - 650

vibrations), at 2880 cm"1 (sp3 CH3 symmetric and CH2 stretching vibrations), at 2920
cm"1 (sp3 CH2 asymmetric vibrations) and at 2960 cm"1 (sp3 asymmetric vibrations)
[8,11,4,12,13]. For films with carbon content C/C + Si > 0.65 a peak at 3000 cm"1
attributed to CH2 or CH stretching vibrations in sp2 configuration can be observed in
poor electronic quality materials [4].
(b)

The mode at 2100 cm"1 is attributed by Wieder et al [11,14] to the stretching vibrations
of single Si-H bonds with one, two or three carbon atoms attached to silicon. Other
authors [2,15,16], as for a-Si:H, attribute this peak to a shift of the SiH stretching mode
at 2000 cm"1 towards 2100 cm"1 due to the formation of SiH1 groups.

(c)

The region between 1500 cm"1 and 1600 cm"1 is attributed to C-C stretching vibrations
[5,17,18].

(d)

The region between 1200 cm"1 and 1500 cm"1 is attributed to the CHn bending or
scissoring modes [8,9]. The 1250 cm"1 peak is due to the symmetric bending mode of
CH3 attached to silicon [11,19,20]. The doublet at 1350 cm"1 and 1400 cm"1 can be
attributed to Si-CH3 asymmetric bending vibrations [8,11], or to CH2 wagging (1350
cm"1) [6] and CH2 scissoring or bending (1400 cm"1) [8,11,13]. In C-rich films grown in
SiH4 + C2H2 gas mixtures the peak at 1350 cm"1 is not observed. In such films another
peak at 1450 cm"1 attributed to CH2 scissoring in Si-CH2-Si configuration [8,13] or to
CH2ZCH bending in sp2 configuration [4] is present.

(e)

The region between 950 and 1100 cm"1 is assigned to CHi rocking or wagging
vibrations [6].

(f)

The mode at 670 cm"1 is attributed to Si-C stretching vibrations [11] and the strong
feature at 780 cm 1 is assigned to the Si-CH3 rocking or wagging mode [11] or to the
Si-C stretching mode [21].

B2

Hydrogen Determination by IR

For bonding types such as Si-H and C-H the concentration of oscillators is given by [22]
(2)
where a(co) is the absorption coefficient of the 2000 - 2100 cm'1 band for Si-H and the 2800 3100 cm"1 band for C-H. Several determinations of the ASJ-H and Ae-H constants have been
performed [2,23-26]. It was also determined that ASJ-H = 1.5 x 1020 cm"2 (constant) for a-Si:H
films is also valid for a-Sii-xCx:H films [27]. In contrast the use of a single AC-H = 1.2 x 1021
cm"2 constant independent of carbon content and of film structure was found to be unreliable
[11] for the determination of C-H bond concentrations in a-Sii-xCx:H films.
So for the determination of absolute concentrations of hydrogen bonded to carbon or silicon a
particular procedure was used [7]. From EQN (2) the densities of silicon hydrogen oscillators
NsiH can be calculated. The total hydrogen density can be deduced by ERDA measurements
[28]. To deduce the C-H bond concentration, for the sake of avoiding the use of a single ACH
infrared constant, the difference between total hydrogen obtained from ERDA measurements
and Si-H bond concentration obtained by IR spectroscopy can be calculated. This procedure
can be considered correct since from effusion measurements [29] in a-Sii-xCx:H films it was
evaluated that the amount of free hydrogen is only some atomic percent.
B3

sp2/sp3 Ratio by IR

Since the presence of sp2 C hybridised atoms is one of the main reasons for the decrease of
electronic properties of a-Sii-xCx:H films, the determination of the fraction of C atoms not
tetrahedrally coordinated is useful. The IR mode at 3000 cm"1 has been assigned to the
stretching vibration of CHn sp2 groups. This mode has been used for the evaluation of the
fraction of C atoms in the sp2 configuration [7,30,31]. The contribution of the CH sp2 mode is
detected only for C/C + Si values higher than 0.6, starting from an sp2 percentage of about
4.5% and saturating at values of about 15% for carbon fractions above 0.9 [7].

RAMAN SPECTROSCOPY

The structure of amorphous silicon carbide can be investigated by Raman spectroscopy which is
complementary to the infrared spectroscopy discussed above. Because of the loss of long-range
order, the wave vector selection rule relaxes in amorphous semiconductors, and thus the first
order Raman spectra reproduce the one-phonon density of states weighted by frequency
dependent coupling matrix elements [32].

a-Sii.xCx:H films have been investigated in the range of 100 - 3500 cm'1 [33-37]. For films
deposited by PECVD [37] and x in the range 0 - 0 . 6 the Raman spectra show the following
features:
(a)

A band around 160 cm"1 is ascribed to the transverse acoustic-like (TA) phonon branch
of the amorphous silicon matrix. A broad band around 480 cm"1 is attributed to the
convolution of transverse optical-like, longitudinal optical-like and longitudinal acousticlike (TO, LO, LA) phonon branches of the amorphous silicon matrix. They broaden for
increasing atomic carbon fraction and disappear for films approaching stoichiometry,
denoting the absence of silicon clusters or a relative number below the Raman
detectivity limit.

(b)

The bands around 640 - 680 cm"1 and around 2000 - 2100 cm"1 in silicon-rich films are
attributed respectively to Si-H wagging and stretching vibrations. In particular, the shift
of the latter mode from 2000 cm"1 to 2100 cm"1 for increasing carbon content, that is in
accordance with infrared measurements [7], has been ascribed to the presence of SiH2
groups [38] or to SiH monohydride with the silicon atoms backbonded to carbon [H].

(c)

A band around 900 - 1000 cm"1 can be ascribed to second order TO scattering of the
amorphous silicon network.

(d)

A broad baseline, due to the room temperature photoluminescence activity of siliconcarbon films, is observable [39,40].

(e)

No reliable detection of an optical-like mode of heteropolar Si-C bonds at 780 cm"1 is


reported in the literature, even in carbon-rich samples. This can be explained by the
very low Raman scattering efficiency for Si-C bonds [41].

(f)

Another strong feature of Raman spectra concerning carbon-rich a-Sii.xCx:H is a large


band around 1500 cm"1 that represents the phonon density of states of amorphous
graphite weighted by a matrix element [42]. Such a mode does not appear in PECVD
a-Sii-xCx:H even for higher carbon content, suggesting that the possible carbon clusters
are mainly characterised by the sp3 configuration as postulated by [39].

FIGURE 2(a) reports typical Raman spectra of samples deposited by PECX7D using SiH4 + CH4
with atomic carbon fraction x ranging from 0 to 0.61 [37].
For films deposited by PECVD at x > 0.6 no Raman signal is detected. It has to be emphasised
that at high carbon content the room temperature photoluminescence is so high that weak
Raman signals could easily be masked, so the absence of carbon clusters in sp2 configuration
cannot be excluded.
Only for a-C:H films deposited at temperatures higher than 3000C is a double peak evident
around 1330 cm"1 and 1610 cm"1 ascribed respectively to Ai8 and E2g graphitic modes where the
former is typical of a development of graphitic medium-range order within the sp2 bonded
layers.

Raman intensity [arb. un.]

Raman intensity [arb. un.]

Raman shift [cm1]


(a)

Raman shift [cm*1]


(b)

FIGURE 2 (a) Raman spectra of a-Sii_xCx:H samples deposited by PECVD. (b) Raman spectra
of a-Sii-xCx:H samples deposited by RF sputtering. The anomalous baseline of the upper fraction
of the spectrum is due to an interference fringe of the photoluminescence activity.

In the case of a-Sii_xCx:H grown by sputtering [37], where room temperature


photoluminescence is weaker than in a-Sii-xCx:H grown by PECVD, the graphitic mode is
detectable even for samples slightly over stoichiometry, denoting the presence of carbon
clustering in the sp2 configuration. It becomes more evident by increasing the carbon content,
as is clearly shown in FIGURE 2(b), in which the Raman spectra of c-Si substrates (first and
second order at 520 cm"1 and 900 - 1000 cm'1 respectively) appear superimposed on those of
the deposited films.
Information on structural order has been extracted from Raman spectroscopy by analysing the
peaks ascribed to the convolution of LA, LO and TO phonon bands in the range 250 - 650 cm"1
[33,37]. The band enlarges on increasing the carbon content and seems to shift to a lower
frequency. This last feature could also be due to the predominance of the LO band. Indeed, the
effective down-shifting and broadening of the TO band in a-Si:H have been attributed to an
increase of the tetrahedral bond angle fluctuation [43] and an increase in local strain [33]. The
full width at half maximum (FWHM) of the TO band slowly enlarges from 60 cm"1 for x = 0 up
to 68 cm"1 for x = 0.35, after which it sharply increases to 104 cm"1 for x = 0.42 [37,44]. This
can be interpreted as a decreasing of short range order related to the silicon network in siliconrich films and to silicon clusters in silicon based alloys approaching stoichiometry.

MICROSTRUCTURE BY IR-RAMAN SPECTROSCOPIES AND NUCLEAR


MEASUREMENTS

The microstructure of a-Sii-xCx:H films is still an open question. A large number of reports
have appeared in the literature where a random distribution of bonds [11], or a moderated
[45,46] or even a complete chemical ordering were claimed [47,48]. The structure of the alloys
is very sensitive to the distribution of silicon, carbon and hydrogen atoms and their natural
bonding. Infrared and Raman spectroscopies, combined with nuclear measurements [28,49-51]
for the determination of the absolute elemental composition, are powerful techniques for
deducing microstructural properties of a-Sii.xCx:H films. A number of structural models have
been developed for a-Sii-xCx:H alloys [48,52-54]. From the experimental point of view it has
been shown that the structure of the a-Sii_xCx:H alloys changes markedly around x = 0.6 [7,55].
Two different compositional regimes can be attributed to these alloys [56]:
(a)

In the first regime (x < 0.6), at first Si-Si bonds dominate, and the Si-C bond
contribution increases slightly with increasing carbon content. Carbon is mostly bonded
to silicon and hydrogen. The films can be described as cross-linked carbon and
hydrogen substituted polysilicon [57].

(b)

In the second regime (x > 0.6) C-C bonds dominate, and silicon atoms are multiply
bonded to carbon atoms in a combined threefold graphitic and fourfold coordinated
matrix. The films can be described by an almost fiilly cross-linked silicon and hydrogen
substituted polycarbon.

On the other hand [6], since C-C bonds are thermodynamically more stable than Si-Si and Si-C
bonds, it is possible to find C-C bonds in the films with carbon content below 0.5 - 0.6. At
carbon concentration higher than 0.6 it is possible to find clusters which are expected to contain
carbon atoms in sp2 configurations. In a recent work [7,44] it has been shown that in films with
carbon content in the range 0.2 - 0.3 the carbon atoms are incorporated in preference as
Si-CH3. The CH2 and CH bonds become important for carbon content higher than 0.4. Only
for films deposited by PECVD operating in particular plasma conditions, hydrogen dilution of
standard carbon gas sources [58] or exotic feedstocks [59-61], was it possible to decrease the
CH3 groups in all the compositional range. FIGURE 3 shows carbon hydrogenation, as
obtained by IR and nuclear measurements, for PECVD deposited a-Sii_xCx:H samples [7,58].
On the same samples the hydrogenation of silicon atoms was evaluated as around 10 - 15%.
Information about chemical ordering could be given by the trend of Si-C bonds as a function of
the C/C + Si ratio. In fact, a maximum of the Si-C bond concentration around stoichiometry
should be expected for a complete chemical order. However, there is some ambiguity
concerning the assignment of Si-C stretching modes. The 780 cm 1 feature is ascribed to the SiC stretching vibration [21], which shifts to 800 cm"1 due to collective TO-like bands, in
unhydrogenated samples deposited by sputtering and annealed at 10000C [62], On the other
hand Wieder et al [11] attribute the 780 cm"1 feature to Si-CH3 rocking or wagging modes
assigning the 670 cm"1 frequency to the Si-C stretching vibration. These assertions are
confirmed by a mode found around 700 cm"1 in unhydrogenated a-Sii-xCx [63].
In summary, in heterogeneous material like a-Sii-xCx:H it is very difficult to extract Si-H and
Si-CH3 wagging and Si-C stretching modes because of a possible frequency distribution of such

[CH]/[C] ratio

C/(C+Si)
FIGURE 3 C-H and C concentration ratio for a-Sii_xCx:H films grown by PECVD in SiH4 + CH4(H-H2)
and SiH4 + C2H2 gas mixtures as a function of carbon to (carbon + silicon) ratio [7,58].

modes in the range 640 - 800 cm"1. Thus, IR analysis cannot be used to get any quantitative
information about chemical order in hydrogenated silicon carbon alloys.
What can be argued from a careful examination of IR spectra of a-Sii-xCx:H in all the
compositional range is the following. For C/C + Si < 0.5 a tetrahedral Si-Si network dominates
and both randomly distributed Si-C bonds and ordered Si-C clusters could be present. For
C/C + Si > 0.6 - 0.7, the C-C network becomes dominant with the presence OfCHn groups in
sp2 configuration and aromatic C-C clusters.

CONCLUSION

In this Datareview infrared and Raman spectroscopies applied to a-Sii-xCx:H have been
reviewed. Both the techniques, combined with nuclear measurements for compositional data,
are able to give information on the alloy structure. Data on bonded hydrogen configurations,
sp2 carbon fractions, and the Si-C and C-C bonding typology can be extracted.
Quantitative analysis of bond concentrations by IR spectroscopy is possible but has to be
carefully treated, because of the difficulty of integrated absorption calibrations. On the other
hand, Raman spectroscopy allows only a qualitative insight into network order and bonding
configurations.
The lack of final conclusions on chemical order in a-Sii-xCx:H indicates the need for further
work.

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2.7

Structural information on a-SiN:H from IR and Raman


spectroscopy
F. Giorgis, F. Giuliani, CF. Pirri and E. Tresso
March 1997

INTRODUCTION

Stoichiometric silicon-nitride is a material typically used as an insulator in optoelectronic


technology. However, in amorphous structure a-Sii_xNx:H can be grown with every
composition (0 < x < 0.57). Experimental and theoretical work has been done on the evaluation
of structural properties of a-Sii.xNx:H material close to stoichiometry and with variable nitrogen
content [1-17].
Infrared and Raman spectroscopy are powerful tools for the determination of bond
configurations and structure of a-Sii_xNx:H alloy in all its compositional range, from a-Si:H to
stoichiometric, a-Si3N4:H? silicon nitride. The aim of this Datareview is to give an updated
summary of infrared and Raman spectroscopy applied to a-Sii_xNx:H films to obtain information
on their network structure. It is also shown how both the vibrational spectroscopies, combined
with nuclear measurements [18-20] for the determination of the absolute elemental composition
of the films, can give an accurate and complete picture of a-Sii_xNx:H network structure.

INFRARED SPECTROSCOPY

Bl

Infrared Bands

Infrared spectroscopy performed on a-Sii_xNx:H films in the range 400 - 4000 cm'1 reveals three
types of bonding vibration [1,12,13,21]:
(a)

The SiHn groups have vibrational modes located at 630 - 650 cm"1 for wagging
vibrations and at 2000 - 2300 cm"1 for stretching vibrations.

(b)

The NHn groups vibrate at 1150 cm'1 and 1540 cm"1 respectively for NH and NH2
bending modes [13,15] and at 3340 cm"1 and 3450 cm"1 for NH and NH2 stretching
modes.

(c)

The SiN bonds are located in a band at 750 - 1050 cm"1 for stretching vibrations.

Typical IR spectra of a-Sii_xNx:H films are reported in FIGURE 1 for samples taken from [21]
having nitrogen content x = 0.25, x = 0.33 and x = 0.57.

NH stretching
NH2 stretching

SiNn stretc.
NSi3 asymm. stretch.
H-SiN3 stretching
NH bending
NH2 bending
SiH2, SiH stretching
HSiN2Si, H2SiNSi stretching
H2SiN2, HSiN3 stretching

SiH wagging
NSi 3 symm. stretch.

un.]
Normalized abs. coeff. [arb.

W a v e n u m b e r [cm"1]
FIGURE 1 Infrared spectra of a-Sii_xNx:H films having variable nitrogen content, deposited by PECVD [21].

The SiH stretching vibrational band, at 2000 - 2300 cm'1, has been attributed to the vibrations
of different configurations, reported in TABLE 1.
TABLE 1 Si-H stretching vibrational frequencies in different configurations [13].
Wavenumber I
Attribution

2005 I 2065 I 2100 I 2140 I 2175 I 2220


(cm 1 )
(cm 1 )
(cm 1 )
(cm 1 )
(cm 1 )
(cm 1 )
H-Si-Si3
H2-Si-Si2 H-Si-NSi2 H-Si-N2Si H2-Si-N2
H-Si-N3
2

1 H -Si-NSi I

The absorption peaks of N-H bonds at 1150 cm"1 and at 1540 cm'1 [13,15] have shown that
monohydrate nitrogen prevails over dihydrate nitrogen which is detected only for samples
grown by PECVD at temperatures below 2500C for film compositions close to stoichiometry.
The Si-N vibrational modes in the spectral region 490 - 1020 cm"1 can be deconvoluted into
four peaks: at 490 cm"1 and 850 cm"1, attributed respectively to the symmetric and asymmetric
stretching vibrations of NSis chemically ordered configurations [9,12]; at 790 cm"1, attributed to
SiNn stretching vibrations of chemically disordered or distorted configurations [13,15,22]; and
at 1020 cm"1, attributed to the Si-N stretching vibrations of H-SiNs groups [15].

B2

Determination of Bond Concentration

By IR spectroscopy the concentration of hydrogen bonded to nitrogen and silicon can be


evaluated from the integrated intensities of the absorption peaks at 1150 cm"1 - 1540 cm'1 and in
the band 2000 - 2300 cm"1, using calibration constants determined in [13].
The [SiH] + [NH] concentrations of bonded hydrogen, obtained by IR spectroscopy, were
compared to the total hydrogen concentrations in the films, obtained by ERDA [18], and the
two results were found to be in good agreement [21,23,24]. The [SiH] concentrations for
samples deposited by PECVD in SiH4 + NH3 gas mixtures at 2200C show at first an increase as
x increases from 0.1 to 0.4, then stay constant for x in the range 0.40 - 0.55, and then decrease
as stoichiometry is reached. The hydrogen dilution of the gas mixtures seems to decrease the
[SiH] concentrations in the compositional region above x = 0.3 up to stoichiometry. For
substrate temperature higher than 3000C in H2 diluted gas mixtures the [SiH] concentration is
lower than in samples deposited at lower temperatures, becoming nil at stoichiometry [23].
The bonding configuration of the a-Sii-xNx:H alloy is simpler if compared to other tetrahedral
alloys such as a-SiC:H. In fact, in the a-Sii-xNx:H network only Si-Si, Si-N, N-H and Si-H
bonds are allowed with the prevalence of silicon tetracoordinated and nitrogen tricoordinated.
N-N bonds are unlikely due to their low stability [8]. By IR spectroscopy it is possible to
determine also the [SiN] bond concentrations by using calibration constants reported in [13,15].
The general trend is a monotonic increase of such concentrations as the nitrogen content
increases [23].

RAMAN SPECTROSCOPY

Raman spectroscopy has been applied to a-Sii_xNx:H thin films in all the compositional range
( 0 < x < 0 . 5 7 ) [25-28].
The spectra yield the following features:
(a)

A band around 160 cm"1 and a broad structure around 480 cm"1 ascribed respectively to
the transverse acoustic-like (TA) phonon branch and to the convolution of transverse
optical-like, longitudinal optical-like and longitudinal acoustic-like phonon branches of
the amorphous silicon matrix. Such a convolution broadens for increasing atomic
nitrogen fraction and disappears for films approaching stoichiometry.

(b)

A band around 640 - 680 cm"1 and around 2000 - 2220 cm"1 attributed respectively to
Si-H wagging and stretching vibrations. The shift towards higher frequency of the latter
mode has been attributed to the changing surrounding environment from silicon-rich to
nitrogen-rich alloying composition [13] and to the forthcoming stress in the deposited
films [26].

(c)

A band around 900 - 1000 cm"1 ascribed to second order TO scattering of the
amorphous silicon matrix in silicon-rich samples.

(d)

A broad baseline, because of the incoming room temperature photoluminescence signal


for x > 0.2. The ratio of the Raman signal ITA/ITO increases as the nitrogen content
increases [25] and this can be due to structural disorder in a medium range beyond
second neighbour atoms in the silicon matrix [29]. Moreover, the foil width at half
maximum (FWHM) of the silicon TO band has an almost linear trend with the sample
nitrogen content. The FWHM starts from values of about 60 cm"1, typical of a-Si:H,
reaching 120 cm"1 for x = 0.44, the maximum nitrogen content for which the Raman
signal of the silicon matrix is still detectable in a-Sii_xNx:H deposited by PECVD [27,28].
Such a behaviour is correlated with a strong decrease of the short-range structural order
related to the silicon network in silicon-rich films and to silicon clusters in nitrogen-rich
ones. The higher disorder of silicon tissue even at low nitrogen content is easily
explainable taking into account that nitrogen and silicon have respectively a threefold
and fourfold coordination, so a small amount of atomic nitrogen can be responsible for a
coordination mismatching, that is to say a distorted silicon network.

DISCUSSION ON a-SiixNx:H
COMPOSITIONAL DATA

STRUCTURE

FROM

IR-RAMAN

AND

By combining IR and Raman data with those obtained by nuclear measurements, with the
assumption that no N-N bond is present in the film owing to the very low stability [8,13], a
complete picture of the a-Sii_xNx:H bonding configuration and structure has been obtained
[21,23,24].
The [NH]/[N] and the [SiH]/[Si] concentration ratios have been evaluated [21,23]. In
a-Sii_xNx:H, grown in SiH4 + NH3 gas mixtures, the hydrogenation of nitrogen atoms is low and
most of the hydrogen is incorporated bonded to silicon. The whole can easily be understood by
taking into account the bonding energy of nitrogen, silicon and hydrogen atoms, reported in
TABLE 2 [30]. Si-N bonds are so strong that nitrogen is preferentially incorporated in its NSi3
stoichiometric configuration, giving the network a tendency to chemical order.
The
coordination mismatching between silicon and nitrogen atoms, which is able to strain the
material introducing disorder and stress, is released by hydrogenation of silicon atoms, which
increases as films approach stoichiometry and the silicon network tends to disappear [8], as
confirmed by Raman spectroscopy [21,27,28]. Recently hydrogen dilution of SiH4 + NH3 gas
mixtures has been shown to favour the formation of Si-N bonds by enhancing network density
and decreasing Si-H bonds [23,24]. Increase of the deposition temperature acts in the same
way, with a quenching of Si-H bonds taking place so that at stoichiometry all the remaining
hydrogen is bonded only to nitrogen.
TABLE 2 Bonding energy of N, Si and H atoms [30].
Bond
Si-N
Si-Si
N-H
Si-H
N-N

Energy
(kcal/mol)
105
76
75
71
39

By using IR and nuclear measurement data the mass density of a-Sii_xNx:H films was evaluated
[13,23]. For silicon-nitrogen films deposited by PECVD in SiH4 + NH3 gas mixtures at 2200C
the mass densities increase from 1.8 to 2.5 g cm"3 for x values between 0.01 and 0.45, after
which they decrease to reach 1.5 g cm"3 at x = 0.57. For hydrogen diluted gas mixtures, for
deposition temperatures in the range 200 - 35OC, the mass density is higher in all the
compositional range.

THERMAL STABILITY

Amorphous silicon-nitrogen alloys are metastable materials, which can degrade if operating at
high current density and at high temperature. Therefore the thermal stability or evolution of
a-Sii.xNx:H film properties under thermal treatments has been determined in view of their
application in electronic devices operating at high current and high temperature. Annealing
experiments under vacuum were performed in order to investigate the structural and optical
stability of the films [23,31,32]. Samples of a-Sii.xNx:H have been annealed in the temperature
range 200 - 5000C. No changes in infrared and optical properties have been detected up to
annealing temperatures of 4000C.
The main features have been observed for annealing at 5000C and they are related to the
decrease of hydrogen bonded to silicon or nitrogen, with different behaviour depending on
alloying composition.
(a)

For the compositional range far from stoichiometry, x below 0.38, where [8] has
reported that the film structure is dominated by a network of amorphous silicon with
embedded SiN clusters, N-H bonds disappear at 5000C and hydrogen bonded to silicon
is reduced by about 50%. In contrast, the integrated intensities of Si-N bonds are
practically unchanged.

(b)

For larger nitrogen content in the films, x = 0.53, a higher stability of both N-H and Si-H
bonds has been revealed. In this compositional regime the network is composed of a
silicon-nitride tissue with embedded silicon clusters. As the annealing temperature
reaches 5000C, the Si-H and N-H integrated intensities are reduced by about 30%, while
Si-N intensities increase by about 10%.

(c)

Near-stoichiometric films have only a very small reduction of N-H bonds and in the
compositional range x > 0.53 the Si-N integrated intensities are enhanced as annealing
temperature approaches 5000C.

CONCLUSION

Infrared and Raman spectroscopy data on a-Sii_xNx:H films have been reported and reviewed.
IR spectroscopy, combined with ERDA and RBS techniques, gives a complete picture of the
bonding distribution of Si, N and H atoms.

Few papers have been published on Raman spectroscopy, even though it could give valuable
information about silicon-network order for off-stoichiometric films and about silicon clusters
for near-stoichiometric films.

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G. Giorgis et al [ Philos. Mag. B (UK) (1997) in press ]
A. Morimoto, A. Oozora, M. Kumeda, T. Shimizu [ Solid State Commun. (USA) vol.47 (1983)
p.773]
Y. Okada, S. Nakajima [Appl. Phys. Lett. (USA) vol.59 (1991) p.1066 ]
F. Giorgis [ Defect and Diff. Forum (Switzerland) vol. 134-135 (1996) p.33 ]
F. Giorgis, CF. Pirri, P. Rava, E. Tresso, V. Rigato, S. Zandolin [ Physica B (Netherlands)
(1997) in press ]
A.P. Sokolov, AP. Shebanin, OA. Golikova, MM. Mezdrogina [ J. Non-Cryst. Solids
(Netherlands) vol.137/138 (1991) p.99 ]
RC. Weast [ Handbook of Chemistry and Physics (CRC Press, USA, 1976) ]
S.C Wang, RG. Cheng, MW. Qi, P.X. Cai [ J. Non-Cryst. Solids (Netherlands) vol.97/98
(1987) p. 1039]
J.B. Bernstein, E.F. Gleason, P.W. Waytt [Mater. Res. Soc. Symp. Proc. (USA) vol.258 (1992)
p.66]

CHAPTER 3

ELECTRONIC STRUCTURE
3.1

3.2
3.3
3.4
3.5
3.6

3.7
3.8
3.9

Valence and conduction band density of states in


a-Si:H: photoemission, inverse photoemission and
core level absorption spectroscopy
Band tails of a-Si:H: photoemission and absorption data
Information on gap states in a-Si:H from
ESR and LESR
Information on gap states in a-Si:H from thermal defect
spectroscopies
Information on gap states in a-Si:H from photoinduced
absorption
Information on gap states in a-Sii_xCx:H from ESR,
LESR, constant photocurrent and photothermal
deflection spectroscopies
Information on gap states in a-Sii_xNx:H from ESR,
LESR and photothermal deflection spectroscopies
Valence band offsets of a-Sii_xCx on c-Si and a-Si:H
Electronic structure of a-Si:Ge:H

3.1

Valence and conduction band density of states in a-Si:H:


photoemission, inverse photoemission and core level
absorption spectroscopy
L. Ley
January 1998

INTRODUCTION

Optical spectroscopy in the form of reflectivity or ellipsometry measurements is among the


principal sources of information about the electronic structure of crystalline semiconductors.
Pronounced structures in the reflectivity or the imaginary part of the dielectric constant are
related to singularities in the so-called joint density of'states which can in most cases be
identified with direct, i.e. k-vector conserving, optical transitions between occupied valence and
empty conduction states at points of high symmetry in the Brillouin zone of the crystal. The
knowledge of the transition energies at these special points in k-space is in most cases sufficient
to construct a reliable and accurate band structure of the semiconductor with the help of
sophisticated band structure calculations.
In amorphous materials the concept of a band structure and of k-conserving transitions fails due
to the lack of translational symmetry. Consequently, optical spectra of a-Si:H in the
fundamental absorption regime (~2 - 10 eV) are featureless and 82(0), the imaginary part of the
dielectric constant, exhibits a single asymmetrically broadened maximum at about 3.7 eV (see
FIGURE 1) [1-3]. The position and amplitude of the maximum changes with deposition
conditions of the a-Si:H film, the position by no more than +0.2 eV and the amplitude between
15 for low density material and about 32 for material deposited at 4000C [2,3]. The amplitude
of 82 is thus sensitive to the density of the material in a surface layer of thickness o f ^ a w ) =
a"x(3.6 eV) 10"6 cm where a(o max ) is the optical absorption coefficient of a-Si.H at the
maximum of 82. This sensitivity is used routinely to monitor the progress during the growth of
a-Si:H films and their surface quality [4-6]. The shape of 82(0) is the result of all energy
conserving transitions of energy ho between valence and conduction states without the
requirement of k-conservation. It constitutes thus the convolution of the valence (NV(E)) and
conduction (N0(E)) density of states weighted by an average energy dependent optical matrix
element P2(ha>,E)
0)
The shape of 82(00) results from the monotonically increasing convolution of Nv and Nc and the
matrix element that drops with increasing hco above -3.4 eV [7-9].
The state densities are defined through
(2)

where the sum extends over all eigenstates of the system with energy Ei (either occupied or
empty) contained in the volume V. As such, the densities of states (DOS) remain well defined
quantities even in a disordered system without translational symmetry. They have been
calculated for various models of the structure of amorphous silicon (a-Si) and amorphous
hydrogenated silicon (a-Si:H) [10-13]. It is, however, not possible to derive them from e2(co)
due to the lack of structure in S2(G)). Thus information about Nv and Nc for a-Si:H has to be
obtained by direct spectroscopic methods. These are photoelectron spectroscopy (PES) or
photoemission [7,14,15] and X-ray emission spectroscopy (XPS) [16,17] for the valence bands
and inverse photoemission or bremstrahlen isochromat spectroscopy (BIS) [18] and core level
absorption spectroscopy [15,19] for the conduction bands.

sample 5a annealed at 350*C


for 2 hours

hu> (eV)
FIGURE 1 Imaginary part of the dielectric constant e2(co) for a-Si:H films prepared at different
temperatures Ts. The maximum in S2(G>) increases with decreasing hydrogen content From [2].

DENSITY OF VALENCE STATES AS OBTAINED FROM PHOTOELECTRON


SPECTROSCOPY

In a photoemission experiment, monoenergetic light of energy ko impinges on the sample


surface and the kinetic energy distribution I(Ek,hco) of the emerging photoelectrons is measured
by means of an electrostatic energy analyser. Rigorous theories of photoemission are usually
cast into the three-step model in which the photoemission process is treated as a sequence of
events as follows (see FIGURE 2):
(i)

Electrons are optically excited from occupied states below the Fermi level Ep to empty
states high above the vacuum level VL.

(ii)

The hot electrons travel to the surface with the possibility of inelastic scattering by other
electrons.

(iii)

They escape through the sample surface into vacuum.

metal

(a)

(b)

FIGURE 2 One-electron energy scheme for the interpretation of photoelectron energy distributions (b) in terms
of initial state energies e (a). The abbreviations have the following meaning. C: core level; VB: valence band;
CB: conduction band; EF: Fermi level; VL: vacuum level; OA: analyser work function. From [14].

The energy distribution I(Ek,feo)) is consequently a sum of a primary distribution of electrons


Ip(Ek?ko) that have not suffered any inelastic collisions and a background of secondary electrons
Is(Ek,ko) due to inelastically scattered electrons:

(3)
The primary current which will be of sole interest in what follows is factorised according to the
three-step model into a distribution of photoexcited electrons J(E,hco)? a transmission function
T(E), and an escape function D(E):

(4)
where the 5-function expresses the fact that the energy analyser selects those electrons which
have after escape into vacuum the kinetic energy Ek. Under the commonly made assumption
that the inelastic scattering probability can be characterised by an isotropic electron mean free
path X6(E), T(E) is given by

(5)

The penetration depth of the photons which equals the inverse of the absorption coefficient
a"1(h) exceeds one hundred A at the photon energies employed in PES (>20 eV). The
electron mean free path A,e(E) is given by the graph in FIGURE 3. FIGURE 3 is based on A,e(E)
values measured for Si by a number of authors. The same energy dependence of Xe holds within
a factor of about two for most materials and FIGURE 3 thus represents what is termed the
'universal curve' of A*(E). For the electron energies of interest here (10 eV < E k < 1500 eV), Xe

Electron mean free path X e ( A )

'universal curve1 of K(E). For the electron energies of interest here (10 eV < E k < 1500 eV), Xe
is seen to vary between about 4 and 20 A so that T(E) is <0.05 and a slowly varying function of
energy.

180 A

a(Si)

Electron energy above EF (eV)


FIGURE 3 The electron mean free path X9 in silicon as a function of electron energy.
The two curves below 100 eV reflect the scatter in measured values of Xe. The line
labelled a(Si) marks the lattice constant of c-Si. From [14].

The short mean free path of the photoelectrons effectively limits the sampling depth of PES to
~2 to 20 atomic layers. It should be kept in mind, however, that the genuine surface electronic
structure extends no more than two to three atomic layers into the bulk so that the PE spectrum
will normally represent largely bulk properties. On the other hand, with the proper choice of E
around the minimum in Xe, PES can be turned into a sensitive probe of the surface electronic
structure.
The factor D(E), finally, takes into account that the electrons encounter a surface barrier as they
escape into vacuum. D(E) thus takes the quantum mechanical reflection at the surface potential
step into account. The gist of the three-step model is that T(E) and D(E) are slowly-varying
functions of E so that the structure in the primary photocurrent Ip(E,ho)) reflects the structure in
J(E,fe). It is the latter quantity, therefore, that one considers implicitly where reference is
made to the photoemission spectrum.
The advantage of PES over optical spectroscopy is evident if we evaluate J(E,ho) in terms of
the state densities N v and Nc:
(6)
Since the final state density NC(E) is structureless at the energies encountered in PES
(E > 10 eV) (see Section C), J(E,ko) is a direct replica of the valence density of states
NV(E - ho) weighted by the transition matrix element P2(hco,E).
The photon energies employed in PES of a-Si and a-Si:H are the characteristic emission lines of
helium discharges at 20.1 (He I) and 40.8 eV (He II) and the K lines of Al at 1486.6 eV and to
a lesser extent of Mg at 1253.6 eV. At these - compared to optical spectroscopy - high photon

and, of course, on the photon energy. It is thus common practice to divide N v , at least
conceptually, into partial densities of states (PDOS). The PDOSs are defined as

(7)
where the \|/i are eigenstates of the system with energy Si, cpa a particular atomic orbital, and the
sum extends over all atoms j that contribute with their orbital <pa to the valence density of states.
That is, N va is part of the DOS that is due to atomic orbitals (pa. For a-Si:H, Nv(E) can thus be
considered the sum of the Si 3s, Si 3p and H Is derived PDOS: NV(E) = N38(E) + N 3p (E) +
N H ( E ) . Neglecting interference terms the primary photocurrent is given by
(8)
where the sum extends over the Si 3p, 3 s, and H i s PDOSs. The photoemission cross-sections
a(a,ko) are the atomic equivalent of the optical matrix element and they determine the relative
contribution of the different PDOSs to the PE spectrum at a given energy. They have been
calculated and it turns out that they depend differently on photon energy [20].
At
bm = 1486 eV (Al Ka) a(Si 3s)/a(Si 3p) = 3 whereas the same ratio is only about 0.2 at
hv = 40.8 eV (He II). Similarly, a(H Is) is negligible compared to a(Si 3p) above - 2 0 0 eV
photon energy whereas it is comparable to a(Si 3p) at h = 20 - 40 eV. These differences are
of considerable analytical value in unravelling the atomic origin of structure in the PE valence
band spectra as we shall see below.
Finally, a word about energy scales in PES. The energy E B = h o - Ekin - <t>A, where <|>A is the
work function of the analyser, is referred to as binding energy. The binding energy so defined
has its origin at the Fermi energy E F which is the energy level that sample and analyser have in
common provided they are in ohmic contact. As the term suggests, E B is independent of
photon energy and PE spectra plotted versus EB can be directly compared independently of the
photon energy they were obtained with.
The first PE spectra of amorphous unhydrogenated silicon (a-Si) were obtained by Pierce and
Spicer using excitation by UV light (ultraviolet excited PES, UPS) [1] and by Ley et al [21]
using Al K excitation (XPS) and by X-ray emission spectroscopy involving transitions from the
valence bands of a-Si by Wiech and Zopf [22].
FIGURE 4 gives a comparison of the densities of states of c-Si and of a-Si as obtained with
XPS after correction for differences in photoemission cross-section across the valence bands.
The four valence electrons of Si are distributed among three peaks in the valence-band density
of states (VB-DOS) in such a way that the area under peak I corresponds to two electrons, and
the areas under peaks II and III to one electron per Si atom each. States at the top of the
valence bands are predominantly 3p-like and those at the bottom (peak III) are mainly of 3 s
character, with peak II of mixed Si 3 s, 3p origin. A comparison of the densities of states of c-Si
and a-Si may be summarised as follows:

Nv (arb. units)

ENERGY (eV)

= EV

FIGURE 4 Valence densities of states of c-Si and a-Si as derived from X-ray induced
photoemission spectra [21] after correction for inelastically scattered electrons and
photoemission cross-sections: dashed line c-Si; solid line a-Si. From [14].

(1)

The overall appearance of the DOS is similar for the amorphous and crystalline
materials. We find in particular that the total width of the valence bands remains
unchanged as well as the valley between the region of predominantly s-derived states
(peaks II and III) and the p-like peak at the top of the DOS.

(2)

The fine structure due to critical points in the DOS of c-Si is washed out. This is
particularly evident in the high resolution spectrum of FIGURE 5 [I]. -

d2 N(E)AlE2

N(E) (electrons/photon eV)

SILICON
tWIO.2eV

EF

INITIAL ENERGY <V)


FIGURE 5 UV-excited valence band spectra of c-Si (c) and a-Si (a). Due to the low photon energy of 10.2 eV
only the p-partial density of states at the top is accessible. Notice the fine structure in the spectrum of c-Si that
is due to direct wave vector conserving transitions and that is absent in the spectrum of a-Si. From [I].

(3)

The two lower lying peaks (corresponding to the Li and L2 critical points in the crystals)
merge into one hump. Since the edges of this hump do not broaden, one has to
conclude that the one-hump structure occurs as a result of states that fill the dip
between Li and L2 rather than through a mere broadening of the two peaks.

(4)

The centroid of peak I shifts toward the top of the valence bands by about 0.4 eV. This
results in a distinct steepening of the leading edge in the DOS of the amorphous samples
(see also FIGURE 5).

The shift in peak I is responsible for the red shift in the maximum of 82(a>) in a-Si compared to
c-Si that cannot be accounted for by the loss of k-conservation alone [1,2,7]. The first point
emphasises the fact that the principal features of the DOS are to a large extent determined by
the tetrahedral environment of a Si atom, the number of nearest neighbours, and the interatomic
distance, all of which remain unchanged in the amorphous modifications [23]. The considerable
density deficit of up to 20% in amorphous group IV semiconductors has consequently no
influence on the DOS, as was first assumed by Herman and van Dyke [24], because it is due to
voids [25-27] and not to a dilatation of the lattice. The loss of long-range order is obviously of
secondary importance for the VB-DOS. It introduces some broadening (-0.5 eV in peak I) into
the VB-DOS as demonstrated in FIGURES 4 and 5 and reproduced in calculations by Kramer
[28] and Brust [29]. This broadening is, however, not able to reproduce the characteristic blue
shift of peak I and the filling of the valley between peaks II and III.
Peaks II and III in the DOS of c-Si are related to the presence of sixfold rings in the diamond
structure [30,31]. In models of the amorphous network the topological freedom of the atoms
allows for five-, seven- and perhaps eightfold rings while preserving the basic tetrahedral units.
The most common fivefold ring, for example, can be formed with only a slight adjustment of the
tetrahedral bond angle. It has been suggested by Weaire and Thorpe [30] that fivefold rings
should introduce states between those of peaks II and III and thereby fill the gap. This
conjecture has been confirmed by a series of calculations involving either simple models
[30,31], or complex crystalline polytypes of Si and Ge containing five-, six- and sevenfold rings
[31-34]. In summary, the featureless appearance of the lower portion of the a-Si DOS is most
likely due to an averaging of a variety of local bonding topologies, i.e. a distribution of rings of
bonds.
As a result of the same calculations [31], it was concluded that the blue shift of peak I is due
largely to bond-angle variations. The electrons in this part of the valence band are mainly
localised in the bond region between atoms. Deviations from the equilibrium tetrahedral bond
angle lead, on the average, to an increase in the energies of these states as a result of increasing
Coulomb repulsion between neighbouring bond charges. Such an increase in the energies of
bonding states corresponds, of course, to a weakening of the bonds with a concomitant
reduction of the Penn gap, i.e. the difference between the average energies of bonding and
antibonding states [35].
A different point of view is held by Yonezawa and Cohen [36] and by Singh [37]. They showed
that the states at the top of the valence bands are strongly affected by variations in the dihedral
angle and thus cause at least some of the observed changes in the shape and position of peak I.

In the last few years realistic models of amorphous silicon have been constructed using
molecular dynamics calculations and appropriate interatomic potentials to minimise the energy
of the model cluster [38-40], State-of-the-art models for a-Si and a-Si:H are to be found in the
work of Holender and Morgan which involve up to 105 atoms for a-Si [41] and 1540 Si atoms
and 450 H atoms to model a-Si.H with a hydrogen concentration of 23% [13]. The
corresponding densities of states reproduce the measured photoemission spectra for a-Si in all
essential features [12,42].

INTENSITY (Q.u.)

It is also clear from these calculations that even the addition of 20 at.% hydrogen to a-Si does
not change the overall density of valence states (and of conduction states for that matter) in an
appreciable way despite the profound influence it has on the mid-gap dangling bond states [13].
This fact is, of course, also borne out experimentally. In FIGURE 6 the XPS valence band
spectra of unhydrogenated a-Si and of glow discharge a-Si:H are compared. Within the
experimental resolution (-0.7 eV) the two spectra are very similar indeed. This is not surprising
in view of the fact that even 20 at.% hydrogen introduces only 5% H i s states into the silicon
dominated VB-DOS. A clear picture of the H Is PDOS is, however, afforded if one goes to
lower photon energies where the H Is photoexcitation cross-section exceeds that of the Si 3s
and 3p states [15,43].

BINDING ENERGY (eV)


FIGURE 6 Comparison of the X-ray excited valence band spectra of a-Si and a-Si:H. The spectra are
uncorrected for a background of inelastically scattered electrons. They constitute in both cases - aside
from a preferential weighting of the 3s-states - the Si-derived partial density of states because of the
negligible photoemission cross-section for H Is states at 1486.6 eV photon energy. From [14].

The addition of hydrogen to a-Si introduces Si-H bonding states between approximately 5 and
11 eV below the top of the valence bands. FIGURE 7 shows a series of valence band spectra
obtained with photon energies of 21.2 eV (He I) and 40.8 eV (He II) [43]. The spectra are for
reactively sputtered films of a-Si prepared at room temperature with increasing amounts of
hydrogen in the sputter gas (argon) as indicated in the figure. In the absence of hydrogen the
spectrum is dominated by emission from Si 3p states at the top of the valence bands that
correspond to peak I in FIGURE 4 (notice that the energy scale in the UV photoelectron
spectroscopy spectra runs in a direction opposite to that of FIGURE 4). The contribution from
the Si 3 s states shows up as the structureless hump between 5 and 14 eV binding energy in the
He II spectrum, but it is lost in the steeply rising background of secondary electrons in the He I
spectrum.

Number of Photoelectrons (arbitrary units)

calcul

Binding Energy (eV)

Binding Energy (eV)

FIGURE 7 (a) He I and (b) He II valence-band spectra of amorphous silicon films prepared by reactive
sputtering in an argon-hydrogen mixture with increasing amounts of hydrogen. The hydrogen
concentrations are those of the sputter gas. The dashed curve reproduces the spectrum for
hydrogen adsorbed on a Si(111) surface in the form of SiH3 [43]. From [7].

With the addition of hydrogen, two new peaks labelled A and B appear with an intensity that is
roughly proportional to the hydrogen concentration in the sputter gas. Peak B is hidden in the
background of the He I spectrum. The binding energies (relative to EF) are 5.9 eV (10% H2)
and 6.2 eV (50% H2) for peak A and 10.2 eV (10% H2) and 11.2 eV (50% H2) for peak B. The
full width at half maximum (FWHM) of peak A increases from 1.2 eV to 1.9 eV. The width of
peak B is 2.2 eV in the spectrum with 50% H2. The intensity ratio I(A):I(B) is approximately
2:1 for hv = 40.8 eV.
The A-B structure - ascribed to the polyhydride configuration (see below) - is the one always
observed for specimens deposited below ~300C [15,43,44]. In FIGURE 8 we compare the He
II spectra of sputtered a-Si:H with that of a glow-discharge (GD) sample, both prepared at
room temperature [44]. Peak A lines up almost perfectly for both specimens. The width of
peak A in the glow-discharge sample is slightly (-0.2 eV) narrower. Peak B on the other hand
is noticeably wider, somewhat skewed towards the low-binding-energy side, and has a binding
energy of 10.8 eV, which is 0.4 eV lower than that in the sputtered film.
Specimens of a-Si:H sputtered onto substrates held at 3500C exhibit a distinctly different
photoemission spectrum (FIGURE 9). Two small peaks at 5.3 eV (peak C) and 7.3 eV (peak

PHOTOEMISSION SPECTRA AND DENSITY OF STATES (arbitrary units)

pure
(a)

A
k sputtered

with
50'/.H 2

glow discharge
(b)

SiH3 (theory)

(O
Id)

,(theory)

He)
E B (eV)

FIGURE 8 Curves a-c: He II valence band spectra of pure and hydrogenated amorphous silicon samples
prepared at room temperature by reactive sputtering (curves a, b), and by the glow discharge decomposition
of silane (curve c). Curves d, e: calculated local densities of hydrogen derived states in a-Si:H, for different
bonding geometries by Ching et al [52]. The calculated spectra have been shifted by 1.8 eV towards lower
binding energy so that peaks A line up [44]. From [7].

D) take the place of peak A. Instead of peak B a similar broad peak E at -10.3 eV below E F is
observed. This form of the spectrum for T D = 35OC is independent of the hydrogen
concentration in the sputter gas as long as it exceeds 10 vol.%. The spectra for GD a-Si:H
films prepared at 350 0 C are again virtually identical with the C-D-E structure, which is
somewhat less well-defined than that in the sputtered sample. On annealing, the A-B structure
transforms into the C-D-E structure around T A = 300 0 C - 350 0 C. Further annealing to ~600C
removes all hydrogen from the film and the spectrum of unhydrogenated a-Si is recovered. It
has been argued that the transition A-B -> C-D is not merely due to a loss of hydrogen from
polyhydride configurations until only Si-H configurations (structure C-D) remain but that some
of the polyhydride configurations actually transform into the monohydrides [44]. A similar
transition from polyhydride to monohydride configurations has also been observed by PES
when GD a-Si:H is subjected to H-atom etching [45]. This abstraction of hydrogen bonded in
polyhydride configurations is the basis for the so-called chemical annealing process utilised in
the growth of high quality a-Si:H at comparatively low temperatures [46].

The first identification [43] of the hydrogen-induced features in terms of specific Si-H bonding
configurations was based on the photoemission spectra of hydrogenated c-Si surfaces and their
interpretation in terms of tight binding of pseudopotential calculations [47-49]. The spectrum
of a c-Si (111) surface saturated with hydrogen in the Si-H3 configuration shows indeed a
remarkable similarity to that of the low-temperature phase of a-Si:H (FIGURE 7, the dashed
line) [47,50]. The energy separation between A and B is, however, reduced at the surface
compared to that of a-Si:H.
Based on these calculations, the origin of peaks A and B as Si 3p-H Is and Si 3s-H Is bonding
states has been established. The partial (i.e. H Is derived) densities of states have been
calculated by Ching et al [51,52] for several possible types of Si-H bonding configuration, each
of them embedded in an amorphous silicon cluster. These are Si-Hx (x = 1, 2, 3) units, a
(SiH2)2 chain fragment, and Si-H H-Si (a broken Si-Si bond with two H atoms taking the place
of the broken bond). Some of these results are compared in FIGURES 8 and 9 with the UP
spectra.
It is apparent from this comparison that in addition to Si-H3 (FIGURE 8), Si-H2 (not shown)
and (SiH2)2 also have a similar two-peak structure with a splitting of about 5 eV that could
correspond to peaks A and B. Furthermore,
A
the two examples - given for the silane
GO- sample
<>
/
fragment (SiH2)2 in FIGURE 8 - emphasise
as deposited at 250'C
C
how sensitively the exact splitting and the
13
B
shape of the PDOS depend on the model
CO
parameters. Under these circumstances it
C
D
GO-sample
appears at present impossible to assign a
S
annealed
particular polyhydride configuration to a given
at 35O-C
CO
L
L
spectrum. We may at best comment on the
O (a)
tendency of the A-B splitting to increase with
>- (by
Sputtered at 350 *C
increasing hydrogen content that we mentioned
Hwith hydrogen
CO
before. The calculations of Ching et al [51,52]
Z
C
D
UJ
indicate a splitting that is -0.3 eV larger for SiQ
E
<
H3 than for SiH2 or (SiH2)2. That would
or
i
indicate that the increase in the A-B splitting is
o
U
J
associated with a shift from (Si-H2)x (x = 1, 2)
Q_
SiH (theory)
CO (O
to Si-H3 with increasing hydrogen content.
"Z.
O
CO

to
There is ample evidence both from hydrogen
adsorbed on c-Si [50,53] and from a number of
UJ
(d)
calculations [51,52,54-57] that the C-D-E
O
structure signals hydrogen bonded as
a.
monohydride Si-H. The theoretical result of
E 8 (eV)
Ching et al [51], obtained for an isolated Si-H
FIGURE
9
Curves
a-c:
He II valence band spectra of
unit in a Si cluster, is shown in FIGURE 9.
hydrogenated a-Si annealed or deposited at elevated
The agreement with the measured spectra is temperatures. Curve d: calculated local density of
seen to be good if we assume that the two states for Si-H; configuration obtained by Ching et al
leading peaks in the PDOS are masked by the [52]. The theoretical spectrum has been shifted by
Si 3p emission between 0 and 5 eV. The 1.8 eV towards higher energy to line up peaks C [44].
From [7].
PDOS calculated for the broken-bond model

(Si-H H-Si) can similarly be made to agree well with experiment, although the peak positions
depend on the parameters used for the bond lengths [52]. For this configuration a strong peak
in the DOS appears at the bottom of the valence bands at ~14 eV. Such a resonance appears to
be characteristic of strongly interacting Si-H units, as they are present also in the PDOS
calculated for hydrogenated vacancies [54]. The corresponding peak is not observed in the
photoemission spectra. A number of other calculations on monohydride configurations give
two peaks in reasonable agreement with peaks C and D but fail to reproduce peak E [54,56].
An estimate of the hydrogen concentration within the sampling depth of photoemission is
possible, based on a comparison of the intensities of peak A for a-Si:H and for Si-H3 units
formed upon chemisorption of H on c-Si. Crystalline silicon (111) saturated with SiH3 has a
surface density of hydrogen of 8 x 1014 cm"2. This corresponds to an effective bulk
concentration ratio, [H]/[Si], of-35 to 50 at.% assuming an average escape depth of 10 2 A
(see FIGURE 3). Inspection of FIGURE 7 indicates a comparable hydrogen concentration in
a-Si:H films prepared at room temperature. It has been demonstrated, however, that most of
the hydrogen is concentrated in one or two surface layers [14]. The high concentration of
hydrogen and the Si-H bonding configurations determined from photoemission spectra are thus
not always representative of the bulk of a-Si:H, a conclusion that is supported by the hydrogen
etching results of [45].

CONDUCTION BAND DENSITY OF STATES

As mentioned in the introduction, the density of empty conduction states in a-Si(:H) has been
measured by X-ray absorption spectroscopy [15,16,19] and by inverse photoemission [8,18].
Inverse photoemission spectroscopy is based - as the term suggests - on the time reversed
photoemission process [58]. A beam of monoenergetic electrons of energy Ei impinges on the
sample and a small fraction of them undergoes optical transitions from states with energy Ei to
final unoccupied states with energy Ef. The energy difference Ei - Ef is carried away by a
photon that is detected. In [8,18] the photon energy detector is set to a fixed energy of
1486.6 eV and the energy of the electron is varied such that the photon flux monitors the
transition rate from Ei to states at Ef within a few eV of the conduction band minimum. This is
the so-called bremstrahlen isochromat spectroscopy (BIS). Under simplifying assumptions that
are similar to those made in the case of PES the photon flux at energyfecoas a function of
electron energy Ei is proportional to the density of final states Nc(Ef) at an energy Ef = Ei - ho.
Alternatively optical absorption from sharp core levels into the unoccupied conduction states
gives direct information about the energy distributions Nc(Ef). Using the Si Is core level as
initial state the K-absorption spectra of a-Si and a-Si:H were measured by Senemaud et al [16].
Within the first 4 eV of the conduction band edge the two absorption spectra are virtually
identical. These spectra are hampered, however, by a rather poor resolution of ~1 eV due to
the inherent width of the Si Is core level.
Much better resolution is achieved if the Si 2p core levels are used as the initial states. Here the
initial state width is less than 200 meV [59]. Since the Si 2p core levels have a binding energy
of ~99 eV, such experiments require synchrotron radiation. The absorption coefficient of
a-Si:H was, however, not determined from conventional transmission measurements but was
measured indirectly via the yield of secondary electrons that follow the decay of the Si 2p core

hole left behind after the Si 2p conduction band transition has taken place. This has the
advantage that this so-called partial yield can be measured with the sample experimental setup
that is used for photoemission measurements [60]. As long as the escape depth of the electrons
does not exceed the penetration depth of the light, the secondary electron yield is proportional
to the absorption coefficient.

YIELD (arb.units)

The Si 2p > conduction band (CB) optical absorption spectra for c-Si and a-Si have been
measured by Brown and Rustgi [61] and the corresponding yield spectra by Gudat and Kunz
[62]. In FIGURE 10 we present the Lm(Si 2p3/2 -> CB) partial yield spectra of c-Si, a-Si? and
a-Si:H (50 vol.% H2 in sputter gas, deposited at room temperature), all three taken under
identical conditions [19]. The spectra in FIGURE 10 have been corrected for contributions
from the overlapping Ln(Si 2pi/2 DB) transitions. The silicon 2p3/2 - 2pi/2 spin-orbit splitting
is 0.60 0.05 eV [59]. The threshold of the Lm(2p3/2) absorption (point of maximum slope, Ex)
is 99.90 0.05 eV for c-Si and 99.85 0.05 eV for sputtered a-Si. In a-Si:H it is shifted by
0.2 eV to 100.10 eV. The values obtained by Brown and Rustgi [61] from direct absorption
measurements are 99.84 0.06 eV for c-Si and a-Si. The structures between 100 and 103 eV
in the spectrum of c-Si are in reasonable agreement with those obtained by Brown and Rustgi
who identify them with transitions to maxima in the conduction DOS [63] (dotted line in
FIGURE 10). These critical points are, of course, absent in the spectra of the non-crystalline
modifications. The complete loss of structure in these spectra - aside from the 1.3 eV-wide
hump at the onset - is in keeping with all band structure calculations: the loss of long-range
order is sufficient to wipe out all structure in the conduction DOS. A very similar set of partial
yield spectra of the Si 2p -> CB transitions albeit with a somewhat poorer resolution has been

E (eV)
FIGURE 10 The Lm (Si 2p3/2 -> conduction band) partial yield spectra of c-Si, a-Si, and a-Si:H. The
amorphous films were prepared by reactive sputtering without and with 50 vol.% H2, respectively.
Energies above threshold (Ex) are given for characteristic features in the spectrum of c-Si and the
corresponding values obtained by Brown and Rustgi [61] are added in parentheses. The dotted line is
the density of conduction states calculated for c-Si by Kane [63]. The dashed line indicates an estimate
of the one-electron density of conduction states appropriate for a-Si and a-Si:H [19]. From [14].

PARTIAL ELECTRON YIELD (orb. units)

measured by Wesner and Eberhardt [15] for a series of hydrogenated and unhydrogenated
samples annealed at different temperatures. Their results are shown in FIGURE 11.

NO ANNEAL

NO ANNEAL

PHOTON ENERGY (eV)

FIGURE 11 Lni partial yield spectra for a-Si and a-Si:H specimens annealed at different temperatures.
The samples were prepared by reactive sputtering in argon with and without 25 vol.% H2. From [15].

It has been pointed out by Brown and Rustgi [61] that the initial rise and the region up to about
1 eV above threshold are greatly enhanced over the density of states in the Ln^m spectrum of
c-Si. They ascribe this enhancement to the strong Coulomb interaction between the core hole
and conduction electron (core level exciton) - a view that has been subsequently confirmed by
the calculations of Altarelli and Dexter [64]. Thus the spectra of FIGURES 10 and 11 do not
represent the one-electron density of conduction states. For a-Si a more realistic shape would
be a simple step function as indicated by the dashed line in FIGURE 10.
BIS is free of the electron-hole interaction and gives thus the most direct picture of the
conduction band density of states of a-Si:H. FIGURE 12 reproduces the corresponding
spectrum of a-Si:H measured with a resolution of 0.8 eV [18]. Again, a rather structureless
density of states is obtained with a broad - 4 eV wide maximum at the conduction band edge.
This maximum disappears after the sample is annealed, a fact that suggests that antibonding H
Is states are responsible for the maximum [18].

N(E) STATES/(eV atom)

UNANNEALED

~EF

A N (E)

E-EF

(eV)

FIGURE 12 BIS spectra for c-Si and a-Si:H after different annealing steps. The ordinate was obtained
by normalising the a-Si:H and c-Si spectra at energies -200 eV above the conduction band edge and
estimating the c-Si DOS using band structure calculations. The inset shows the difference
between the as-deposited sample and that annealed at 3100C. From [18].

A remarkable result is the complete lack of discernible hydrogen-derived antibonding states in


the partial yield spectra of a-Si:H in FIGURES 10 and 11. The antibonding states have
predominantly Si sp3 character since the bonding states are mainly H Is derived. They are
expected to lie at the bottom of the conduction bands [51,52,54]. According to the calculation
of Ching et al [52], the hybridisation of the antibonding states is such that the Si 3p partial DOS
exceeds the Si 3 s one by a factor of about 4 to 5. The Si-H antibonding states are therefore
expected to be weak in the 2p yield spectrum according to the dipole selection rule. It is
therefore not unlikely that the weak Si-H antibonding states are hidden under the initial hump in
the yield spectrum of a-Si:H.
On the other hand, Si 2p absorption spectra of condensed solid silane (SiH4) do have a very
sharp peak at the onset of the absorption around 102.7 eV [65]. Also, the Si-F antibonding
states show up on the Si 2p absorption spectra of a-Si:F at ho = 106.4 eV [66].
Realistic band structure calculations of a-Si(:H), finally, do exhibit the initial conduction band
hump for hydrogenated and hydrogen free a-Si models alike [12,13,42]. An altogether
satisfying view of the contribution of H-Si antibonding states to the conduction band DOS is
thus still lacking.

VALENCE AND CONDUCTION BAND EDGES AS A FUNCTION OF


HYDROGEN CONTENT

The spectra of FIGURE 7 reveal an increasing separation of the valence band edge from the
Fermi level with the addition of hydrogen to a-Si. When measured at the point of maximum
slope, this shift amounts to 1 eV as indicated in FIGURE 7 for the sample with 50 at.%
hydrogen. Von Roedern et al [43] proved that the shift is the result of a recession of the
valence band edge and not a shift of EF within the gap because no comparable change in the
binding energy of the Si 2p core levels was observed. They also showed that the correlation
between optical gap and hydrogen concentration could be explained by the recession of the
valence band alone [44]. The position of the valence band maximum (VBM), of Ep, and the Lm
threshold ET have been simultaneously measured using synchrotron radiation [19]. The results
of these measurements are summarised in the form of energy diagrams in FIGURE 13.

surface states

E-E (Si2p3/2)(eV)
FIGURE 13 The energies of the valence band maximum (VBM)9 the Fermi level (EF), and the photoemission
threshold (E1) plotted for four samples relative to the binding energy of the Si 2p3/2 core level. The value of Eg
was obtained according to Eg = E x - VBM + Ex, where Ex is the core level exciton binding energy. The hydrogen
concentrations (CH) are deduced from the intensities of the chemically shifted Si 2p lines [19]. From [14].

All energies are given relative to the unshifted component of the Si 2p3/2 core level. In this way,
mere Fermi level shifts within the gap can be distinguished from changes in the VBM and ET
brought about by a redistribution of states near the band edges. The VBM is defined in the
usual way through the extrapolation of the steepest descent of the leading edge of the valence
band spectrum, and the definition of E T has been explained in the previous section. Also given
in FIGURE 13 is the value of the gap Eg? which is defined as
(9)
where a value of 150 meV for the core level exciton binding energy ExC derived from partial
yield spectra of c-Si was used [19].

The energy levels so defined are plotted in FIGURE 13 for four amorphous silicon films and for
the (111) surface of c-Si. The first three amorphous samples are a hydrogen-free film sputtered
at room temperature (sample A) and two films sputtered at RT with different amounts of H2 in
the sputter gas (samples B and C). Finally, film D is sample C after it has been annealed at
3500C for -20 min. The hydrogen concentrations CH in FIGURE 13 were obtained from the
intensities of the chemically shifted Si 2p lines as explained in [7] and [59]. Sample D has H
only in monohydride configurations. The results of FIGURE 13 may be summarised as follows:
(i)

The top of the valence bands recedes by as much as 0.7 eV with increasing hydrogen
content. This is 0.3 eV less than the recession measured at a point halfway up the
leading edge (compare FIGURE 7) because the slope of the leading edge decreases also
with hydrogenation.

(ii)

The conduction band edge (ET) is by comparison little affected. The maximum
recession is 0.2 eV compared to its position in unhydrogenated a-Si. In fact, the
position of ET is within that same margin equal in a-Si and c-Si. This result was also
obtained by Wesner and Eberhardt from their Si 2p absorption spectra [15] (compare
FIGUREIl).

(iii)

The Fermi level is pinned near VBM in a-Si films. The distance between EF and VBM
may vary between 0 and 0.2 eV for undoped specimens. The smallest amount of
hydrogen added to the film frees EF to move toward the middle of the gap. Further
addition of hydrogen results only in minor movements of EF in such a way that the
difference ET - EF remains virtually constant at 0.52 + 0.07 eV, corresponding to an
energy of 0.67 eV below the conduction band edge after correction for the exciton
binding energy, a result that is again in quantitative agreement with [15].

As a consequence, EF-VBM increases with hydrogen content CH approximately linearly


according to EF - VBM (eV) = 0.65 + (0.0119 0.0014) cH (at.%) as demonstrated in FIGURE
14 [66]. The recession of the VBM with hydrogenation is in agreement with the results of most
calculations [51,52,55,67-69]. This recession is ascribed to the replacement of the Si-Si bond
with the stronger Si-H bond that moves states from the top of the valence bands to a position
deep inside the valence bands where they are observed as peaks A-E. The depletion of states is
not limited to the Si atoms bonded directly to H. According to DiVincenzo et al [68,69], the
presence of hydrogen on a dangling bond reduces the bonding charge associated with valence
states in the top 0.25 eV of the valence bands out to the third nearest neighbour. That is the
reason why one observes an actual recession of the VBM even for small hydrogen
concentrations and not just an attenuation in the emission near the top of the valence bands that
is due to the few atoms bonded directly to H. The bottom of the conduction bands is little
affected by the addition of H, which is in agreement with the calculations [54,68,69], and the
shift in VBM accounts for almost all the change in the optical gap EG with hydrogen content.
The proportionality factor between cH and the optical gap is 0.019 [7].

VBM-EF (eV)

Hydrogen content (at %)


FIGURE 14 Separation of Fermi energy (EF) from the valence band maximum (VBM) as a function of hydrogen
content CH. The data points are from photoelectron spectra of GD a-Si:H. The triangles show the recession of
the VBM with cH according to the calculation of [54]. The straight line is the linear relationship between
Ep-VBM and cH as given in the text. The initial 0.6 eV jump in EF-VBM reflects the depinning of E F and
not a recession of the VBM. From [66].

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Previous Page

3.2

Band tails of a-Si:H: photoemission and absorption data


L. Ley
November 1997

INTRODUCTION

FIGURE 1 shows the optical absorption spectrum cc(hv) of glow discharge a-Si:H [1,2]. Also
shown for comparison are the absorption spectra of c-Si [3] and hydrogen-free a-Si [4]. We are
concerned here with the steeply rising part of the absorption spectrum of a-Si:H that extends
from 1.4 eV to just below the Tauc gap of a-Si:H at about 1.8 eV and covers up to four orders
of magnitude in a (region B in FIGURE 1). As indicated by the dashed line, the absorption
constant depends strictly exponentially on photon energy in this regime with a logarithmic slope

that equals 50 meV for the sample of FIGURE 1. This so-called Urbach edge is observed in all
high quality a-Si:H samples independent of their mode of preparation as long as the defect
absorption below 1.3 eV (regime C in FIGURE 1) does not interfere with the exponential part
of the absorption edge as is the case for a-Si in FIGURE 1. The width or slope of the Urbach
edge, defined through E0, does vary, however, with preparation conditions between 40 meV
and more than 100 meV.

Q-Si

a (cm* 1 )

C-Si

DIRECT ABS.
COLLECT EFF.
DIODE
COPLANAR PHOTOCOND.
C

hu> (eV)
FIGURE 1 Absorption edges of crystalline silicon (c-Si), amorphous unhydrogenated silicon (a-Si)
and state-of-the-art hydrogenated amorphous silicon (a-Si:H, data points). From L. Ley [ in
The Physics of Hydrogenated Amorphous Silicon, Springer Tracts Appl Phys. vol.56
Eds J.D. Joannopoulos, G. Lucovsky (Springer, Berlin, 1984) p. 141 (Figure 3.49) ]

There is general, but not unanimous, agreement that the Urbach edge reflects essentially the
exponentially falling density of states (DOS) that extends from the valence band edge towards
midgap and is not due to an exponentially varying optical matrix element. This valence band
tail, and a much steeper (in the case of a-Si:H) conduction band tail, are characteristic of all
amorphous semiconductors.
They are ideally absent in crystalline semiconductors as
demonstrated for c-Si in FIGURE 1 (see, however, [5]). The tail states reflect the structural
disorder of the material in a way to be discussed below. They further constitute a reservoir of
localised trap states and govern, as such, the transport properties of a-Si:H. There are,
furthermore, theories that relate the deep defect density in a-Si:H directly to the width of the
valence band tail. It is for these reasons that the width of both tails, again measured by their
logarithmic slopes Eov (valence band tail) and Eoc (conduction band tail), are of prime interest
for characterisation of a-Si:H samples. Since there is theoretical and experimental evidence that
the width of the conduction and that of the valence band have a common origin, and scale with
each other, it suffices to measure Eov, which is commonly done through the slope of the Urbach
edge in optical absorption, or more directly through photoyield spectroscopy. In particular,
optical spectroscopy in the sub-bandgap regime is therefore widely used to characterise the
structural quality of a-Si:H and other amorphous materials. Early measurements of the Urbach
tail using direct transmission spectroscopy and a variety of photoconductivity methods (primary
and secondary) are given in [1,2,6-10]. Reviews of the optical properties of a-Si:H with
extensive sections on the Urbach edge are to be found in [11] and [12].

DETERMINING THE VALENCE BAND TAIL BY OPTICAL METHODS

As mentioned in the previous section, the slope of the valence band tail as the wider of both
band tails is implicitly determined via the Urbach edge in the optical absorption spectrum.
Because the product of absorption constant a and film thickness d is small in the region of the
Urbach edge, conventional transmission spectroscopy is seldom used in this regime. Instead,
the absorptance A, which is proportional to the energy deposited in the amorphous film, is
determined directly. The generally applied techniques to determine A in a-Si:H are
photothermal deflection spectroscopy (PDS) [13] and a variant of secondary photoconductivity
termed the constant photocurrent method (CPM) [14-16].
PDS belongs to a class of experimental techniques whereby the temperature rise in the sample
due to the absorbed radiation energy is measured. Optically created excess energy in the
electronic system is transferred to the phonon system through radiationless recombination of
electron-hole pairs. Other less frequently used variants are the direct measurement of the
sample temperature rise [17] or photoacoustic spectroscopy (PAS), whereby the periodic
heating of a small gas volume through the sample which is illuminated by a chopped light beam
is detected as sound in an attached microphone [18-20]. In PDS, the temperature rise of the
sample is measured through the temperature gradient it produces in a gas or liquid immediately
in front of the sample surface. Connected with the temperature gradient is a gradient in the
refractive index of the liquid or gas that is detected through the deflection of a laser beam
(probe beam) passing just in front of the specimen. The theory of this process is given in
[13,21]. The quantity measured as a function of the power normalised monochromatic light of
frequency v impinging on the sample is the deflection S(hv) of the probe laser:

(1)
S is thus proportional to the absorptance A which is a function of the absorption coefficient a
and the film thickness d. The term in square brackets takes into account multiple reflections
within the a-Si:H film, in the incoherent limit; RF and RB refer to the reflectivities of the front
and back surface of the film, respectively. Expressions for A(hv), including Fabry-Perot
interferences, are given in [12,22-24]. A further, commonly adopted assumption is that RF and
RB are wavelength independent. In this case the absorptance 1 - e"0"1 is simply given by
(2)
where S^t is the saturation deflection that is obtained when the sample is opaque, i.e. ad 1.
Assuming wavelength independent reflectivities also alleviates the necessity to make corrections
for reflection losses of the pump beam at the front surface of the sample and allows the absolute
determination of ce(hv), once d is known. The errors introduced by these approximations are
claimed to be less than 20% over the range of absorption coefficients usually measured by PDS
[21]. The sensitivity of PDS is such that an absorptance of 10"5 can be measured readily [21]
which corresponds to a = 0.1 cm"1 for a 1 jam thick film. The influence of scattered light has
been dealt with in [25] and found to be negligible for measurements encountered in work on
a-Si:H. The influence of the inhomogeneous field distribution in the thin film sample as a result
of Fabry-Perot interferences and of inhomogeneities in the sample is discussed in [26-29]. The
effect interferences have on the determination of Eu in PDS measurements has been dealt with in
[30]. While PDS measurements are usually performed at room temperature, there has been a
report on measurements at 77 K using liquid nitrogen as the deflecting medium [31].
Photoconductivity is another sensitive and widely used method to determine ct(hv) in the region
of the Urbach tail and the deep defect absorption. If the photoinduced current IPh is measured
using non-blocking, i.e. ohmic contacts (secondary photoconductivity), IPh is proportional to the
applied voltage for a fixed photon flux and a photoconductivity aPh is, as usual, defined as the
ratio of photocurrent density and externally applied electric field. For uniform illumination and
unipolar photoconductivity, the relation between aPh and the absorptance A is given by [32-34]
(3)
where [i is the drift mobility, T the lifetime of the carriers which carry the photocurrent, and d
the thickness of the sample. The quantum efficiency r\ takes into account that not all optical
transitions lead to free carriers (r| < 1). <D is the photon flux (photons cm'2 s"1) that enters the
sample, i.e. after corrections for sample reflectivity have been made. Because x, the lifetime of
the carriers, depends on the concentration of electrons and holes, the photoconductivity is a
non-linear function of the generation rate AO:
(4)

with y between 0.5 and 1 [33-35]. The steady state secondary photoconductivity is thus, in
principle, ill suited to derive A(hv) from the spectral dependence of the photoconductivity. This
problem has been overcome by the dual beam technique in which an intense and constant bias
illumination in addition to the weak monochromatic photon flux is used to keep the
recombination kinetics, and thus T and y, constant [36]. In the constant photocurrent method
(CPM) the photon flux is adjusted to keep aPh constant as hv is varied [14-16]. This
automatically ensures a constant concentration of photogenerated carriers and thus a constant y,
and 1/O(hv) is proportional to T]A. In the weak absorption limit (ad 1), and making the
same assumptions concerning RF and RB as in EQN (1), T]oc(hv) is proportional to 1/O(hv) and
can be placed on an absolute scale by fitting it to a values determined by transmission
measurements at sufficiently high photon energies where T] = I (see below) [37] or more simply,
but less accurately, by placing the saturation level at Os* = Vd. The implicit assumption that |i is
independent of photon energy and photon flux has been discussed in [I].
The absorption coefficient cc(co) where co = 2nv is, in its most general form, related to the sum
over all energy conserving optical transitions between initial (index i) and final (index f) states in
the sample volume V (in SI units):
(5a)

where mo and e are, respectively, the mass and charge of the electron, c is the velocity of light,
n(o) is the frequency dependent refractive index, and e0 = 8.85 x 10"12 A s/V m, the dielectric
constant of free space. The factor 1/V normalises the sum to the sample volume and the
transitions from states |i> to states |f> are weighted by the square of the transition matrix
element

where the x-component of the momentum operator px equals

An equivalent expression for a is obtained if the momentum operator is replaced by the dipole
operator

(5b)

In crystals, the eigenfunctions are Bloch functions and the evaluation of the matrix elements
yields the k-selection rule and the strength of electromagnetic dipole transitions for pairs of
states belonging to the same k-vector. In amorphous solids where the k-vector is no longer a
good quantum number the sum over initial and final states is replaced by a convolution of
occupied (N0Cc(E)) and empty (Ncmp(E)) densities of states according to [38,39]:
(6a)

where N0Cc(E) = f(E)N(E), N ^ E ) = (1 - f(E))N(E) with f(E) the Fermi occupation function
and

the one-electron density of states (DOS). P2(co) is an average, in general energy dependent,
momentum matrix element squared and a3 the atomic volume [40]. An equivalent expression
for a(o) is obtained using the average dipole matrix element squared R2(o):
(6b)
Since the waveftmctions in an amorphous system are not known exactly, the matrix elements in
EQNS (6a) and (6b) cannot be calculated. Thus, attempts have been made to express them in
terms of their crystalline counterparts [40]. There appears to be agreement that the matrix
elements do not change drastically as long as at least one of the states involved in a transition is
delocalised [41,42]. The matrix elements are bound to decrease rapidly if both states are
localised due to spatial anticorrelation and the concomitant lack of overlap of the
wavefunctions. There have been theoretical arguments that either R2(co) or P2(G>) are
approximately constant at least below about 3 eV photon energy if delocalised states are
involved [11,41]. Neglecting the frequency dependence of the refractive index this yields
tractable relationships between the absorption coefficient and the densities of states of valence
and conduction bands (replacing by hv, as is usually done):
(7a)
in the dipole representation of the transition matrix element and
(7b)

in the momentum representation of the matrix element where we have abbreviated the
convolution of occupied and empty densities of states with J(hv). Note, that the material
independent prefactors in EQNS (7a) and (7b) correspond to a dimensionless constant of

Taking for a3 the atomic volume of Si in a-Si.H (a3 = 21.5 x 10"24 cm3) and an average
refractive index n 4.2 in the region of the absorption edge we obtain
(8a)
where CR has the value 2.0 x 10"24 cm3. A value of 6.2 x 10"25 cm3 has been adopted in [37] for
CR. The corresponding expression involving P 2 is
(8b)
with
A comparison of the absorption coefficient measured in the fundamental absorption region
between 1 and 10 eV photon energy with the convolution of experimentally determined valence
and conduction densities of states tends to favour a constant dipole matrix element (R2 10'15
cm2) below about 3.4 eV [12,42,43]. Nevertheless, the majority of papers dealing with the
interpretation of absorption edge data are performed following [42] by using EQN (8b) under
the assumption of a constant momentum matrix element instead [14-16,36,44-49]. In this case
cc(hv) = K J(hv)
hv

(9)

where the constant K = CP PW2 equals 1.8 x 10"38 eV2 cm5 if R2 = 10"15 cm2 is adopted following
[43]. The value usually taken is, however, 4 x 10"38 eV2 cm5. This value is obtained if the
absorption coefficient a at photon energies of about 2 eV, i.e. well above the edge, is compared
with the convolution of free-electron-like densities of states for the valence and conduction
band of a-Si:H [15,36].
Those authors that use EQN (8a) for their analysis of absorption data make the further
assumption that the product hv R2(hv) is constant [37,50-52] without any real justification
except that it simplifies the deconvolution of J(hv) in terms of the contributions from Nocc and

This deconvolution is performed at different levels of sophistication. In order to facilitate the


discussion, a typical density of states that is the basis for virtually all deconvolution procedures
is sketched in FIGURE 2. It consists of four parts:
(i)

a free electron conduction band DOS for e > Ect:

a free electron valence band DOS for 8 < Evt:

(iii)

a conduction band tail for 8 < Ect:

(iv)

a valence band tail for 8 > E^:

(v)

the Gaussian shaped defect band centred at ED with a width W

N(E) (cm"3eV1)

(ii)

energy (eV)
FIGURE 2 Model density of states for a-Si:H with parameters as given in the text.

The prefactors N c = Nv = 6.7 x 1021 are chosen such that the free electron part of the DOS
corresponds to the electron density of a-Si:H [35]. The state densities N0Vt and Noct and the
energies Ect and E* are chosen in such a way that the band tails join the free electron part of the
DOS smoothly, i.e. continuous and with continuous derivative. This condition gives

and

respectively. The corresponding points are indicated by circles in FIGURE 2 and it is obvious
that Ect and Evt differ from Ec and Ev only marginally. The logarithmic slopes E0V and EOc have
the values of 50 and 25 meV, respectively, in FIGURE 2, i.e. values that are appropriate for
undoped a-Si:H of good quality. The optical or Tauc gap EG = E c - Ev is 1.80 eV. The DOS
at Ec (4.5 x 1021 cm"3 eV"1) and at Ev (6.4 x 1021 cm"3 eV 1 ) lie in the range of state densities
accepted for the transition from localised to delocalised states (2 x 1021 according to [53]). It is
thus common practice in the evaluation of CPM data to equate EG with the mobility gap and set
it equal to 1.8 eV [15,16]. Also included in FIGURE 2 is a Gaussian distribution of defects
with NOD = 1018 cm"3 eV"1 and W = 0.2 eV centred at Ec - 0.9 eV.
As far as the Urbach tail is concerned two kinds of transitions are expected to contribute: those
from the occupied valence band tail (VBT) to extended states above Ec and those from
extended states below Ev to conduction band tail (CBT) states. In this respect there will be no
difference between PDS and CPM because tail to tail, i.e. localised to localised transitions have
a vanishing absorption coefficient; they are, however, included in the analysis in [45], for
example. Aside from the fact that the second class of transitions contribute considerably less to
the photoconductivity than the first class on account of the reduced hole mobility, both kinds of
spectra can thus, for our purpose, be dealt with on the same basis and r\ = 1 is assumed
automatically in CPM.
Indeed, whenever a direct comparison between transmission
measurements, PDS, and photoconductivity data was performed they agree in the range of the
Urbach edge [1,50,54].
The most rigorous simplification of the absorption process neglects the conduction band tail and
the energy dependence of N(e) and replaces both by a step function: N ^ e ) = Nco(e - Ec).
Combined with EQN (8a) and a constant R2 this allows us to determine Nocc(e) directly by
differentiating a(hv) with respect to hv [37,50,55]:
(10)
with M = (CR hv R2 Nc0)"1. This corresponds to M = 7 x 1016 cm"2 at hv = 1 eV using the
values for Nc0 and R2 given previously. Values for M of 1016 and 1017 have been used in
[37,50]. Clearly, this method has the advantage that it yields Nocc(Ec - hv) without further
assumptions once the rigorous approximations made for the final states have been accepted. In
particular, the valence band slope will be equal to the Urbach edge, i.e. Eov = Eu, according to
this analysis.
On the other extreme, the absorption coefficient is modelled using a DOS as depicted in
FIGURE 2 and adjusting all relevant parameters until the best agreement between measurement

and calculation is reached. This procedure has been applied to CPM measurements in
[15,44,51] and to PDS in [45], using in both cases EQN (8b), i.e. the constant momentum
matrix element approximation, except for [51]. Analyses that apply iterative procedures to
obtain N(E) from absorption data are described in [48,56] using different approximations for
the shape of the conduction band DOS (step-function or square root dependence on energy).

log (a /cm" 1 )

The absorption coefficient has been calculated analytically in [57] for the constant momentum
matrix element case and using constant DOSs for valence and conduction bands. The result
shows that the slope of the Urbach edge equals the broader of the two tail slopes in the DOS.
For a-Si:H that is, with few exceptions, the valence band slope [58]. It is thus expected that the
simple differentiation procedure of [37,50] yields the same slope parameters E0V as does the
deconvolution of [51] when applied to the same data, in this case CPM spectra. This
expectation is indeed borne out for the differently doped samples gathered in TABLE 1 except
for the most heavily doped samples. The corresponding CPM spectra for the P-doped samples
are shown in FIGURE 3.

Energy (eV)
Photon energy (eV)

FIGURE 3 CPM spectra of phosphorus doped a-Si:H samples. The PH3 concentration in the gas phase
increases up to 1 vol % from bottom to top. Circles: data points; line: fit to a model density of states [51].

A measure of the doping level in TABLE 1 is the position of the Fermi-level EF with respect to
the band edges (Ec - EF for n-type P-doping and EF - Ey for p-type B-doping). One notices the
general trend that Eu and E0V increase with doping from a minimum of 49 meV to about
140 meV. This range of E 0 and its dependence on doping is representative for a-Si:H samples.
Note in particular, that the defect density ND, as determined from the defect absorption below
-1.4 eV, increases substantially with doping as well. This hplds for P- and B-doping and there

is a definite correlation between the Urbach slope and the concentration of deep defects N D as
obtained from the analysis of the defect absorption below 1.4 eV (see Section F).
TABLE 1 Urbach slope Eu, valence band slope parameter E0V, and defect
density ND of differently doped a-Si:H samples according to [51].

P-doped
E c -E F (eV)
0.73
0.58
0.43
0.25
B-doped
E F -Ev(eV)
0.70
0.57
0.50
0.40

Numerical deconvolution
Differentiation of oc(hv)
according to EQN (10) [36] of oc(hv) according to [51]
ND (cm 3 ) E0V = E 1 1 ^eV) E0V (meV)
ND (cm"3)
x
x
x
x

1016
1017
1017
1019

49
58
62
105

50
58
62
82

1.0
1.6
6.0
1.7

x
x
x
x

1016
1017
1017
1019

3.8 x
2.1x
7.0 x
2.8 x

1016
1018
1018
1019

54
82
90
148

54
82
90
133

3.5
2.2
6.0
2.5

x
x
x
x

1016
1018
1018
1019

1.0
1.5
5.8
1.9

There is, however, not general agreement that the Urbach slope equals E0V in all cases [45,47].
Counter examples for the equality of E11 and E0V are given in [59,59b]. The analysis of CPM
spectra by deconvolution for differently prepared samples yields results for Eu that deviate from
E0V in proportion to the magnitude of Eu (see FIGURE 4); that is to say that E0V increases only
slightly. Unlike CPM, which is believed to be insensitive to highly defective surface and
interface layers on account of a reduced photoconductivity in these layers, the absorption
coefficient as measured by PDS contains contributions from these layers as well as from the
bulk. Thus the defect absorption below ~1.4 eV and the Urbach parameter depend on sample
thickness. The authors of [45] fit PDS data, obtained from a-Si:H films of different thickness,
to the canonical density of states given in FIGURE 2 using the constant momentum matrix
element approximation. Unlike other authors they do, however, include tail-to-tail transitions
with the same matrix element in their analysis. Again, there is a tendency for Eu and E0V to
increase for films with higher defect density (thinner films in this case). However, the
considerable difference between E11 and Eov which they obtain (see FIGURE 5) points again
towards difficulties in equating Eu with E0V on a general basis. We shall return to this point
below.

PHOTOELECTRON YIELD SPECTROSCOPY

Photoelectron yield spectroscopy (yield) is a variant of photoemission that allows the


unambiguous determination of the occupied density of states (ODOS) in amorphous materials
[60-63]. In yield the total number of photoelectrons emitted if a sample is illuminated with
monochromatic light is measured as a function of photon energy for photon energies in the
region of the photoemission threshold. The photoemission threshold is the energy difference
between the highest occupied state and the vacuum level at T = O. For a-Si:H this energy
difference is about 4 eV and depends on doping. Technically, the yield is measured by placing
the sample in an ultra high vacuum (UHV) chamber and counting the photoemitted electrons
after acceleration with the help of an electron multiplier and the appropriate counting

Defect Density Nb (cm*3)

series I
series Il
series III
(solid:E0 / open:ET)

Tail-parameter ( E 0 , E 1 ) (meV)

Urbach tail energy

[meV]

FIGURE 4 Urbach slope (E0 in this figure, full symbols) and valence band tail slope (ET, open symbols)
for differently prepared a-Si:H samples as obtained from a deconvolution of CPM spectra. On the
ordinate the density of deep defects is given as a parameter [59].

d [|im]
FIGURE 5 Comparison of the Urbach slope parameter Eu and the valence band slope E0V for
a-Si:H films of different thickness as obtainedfromthe analysis of PDS spectra [45].

electronics [64]. Yield is a rather surface sensitive method because the hot electrons that are
necessary to overcome the surface barrier have a very short mean free path of between 100 and
25 A, depending on their energy [62]. Together with the limited penetration depth of light in
the photon energy range of 3 to 6 eV, of typically 50 to 100 A, this results in the rather short
sampling depth of about 50 A achieved in yield spectroscopy on average. It is therefore
mandatory to deal with clean and well characterised surfaces in order to obtain reliable and
meaningful results [65].
The expression for the photoelectron yield Y(ho) defined as the number of electrons emitted
into vacuum per incident photon is closely related to the absorption coefficient a(hoo). The
absorption coefficient measures the energy deposited in the sample per unit time and volume
normalised to the photon energy flux density. Yield measures essentially the transition rate per
unit volume normalised to the photon number flux density. The factor ho that enters in going
from transition rates and number densities to energy rates and energy fluxes cancels, and we
have

(H)
with the additional provision that only optical transitions contribute to Y(ho) with final states
above the vacuum level I w In the dipole matrix element expression of EQN (7a) this reads
[62]:
(12)

with

All energy independent parameters and the refractive index and the sample reflectivity, which
are to a good approximation constant as well, are gathered in B. The factor T(E) corrects the
right hand side of EQN (12) for the finite escape probability of photoexcited hot electrons (Evac
is about 3 eV above the conduction band edge of a-Si:H). With the values for the electron
mean free path A,e(E) and the light penetration depth OL1QM*) given above, T(E) is a slowly
varying function of photon and electron energy of the order of 0.5, which is usually considered
constant as well.
The evaluation of the yield spectrum in terms of the occupied electron density of states N0Cc(E)
is straightforward. This is so because the density of final states is known to be constant >3 eV
above the conduction band edge [66-68] and the requirement that electrons escape into vacuum
sets a strict lower limit to the integral in EQN (12). N ^ E ) can thus be taken out of the
integral in EQN (12) and Y(hco) depends only on the density of occupied states and R2(hco).
According to [43], R 2 (ho) scales as (ho)"5 for photon energies above 3.4 eV. This yields, after
a change in variable (dE -> dhco, Evac = 0) and differentiation of EQN (12), the density of
occupied states

(13)

where the energy zero is now the vacuum level I w and increasing hco corresponds to states
deeper in the valence band [61,62]. A yield spectrum of undoped a-Si:H and the corresponding
density of states are shown in FIGURES 6 and 7, respectively [61]. The yield is usually
measured on a relative scale and, in order to determine the absolute magnitude of Nocc(h(o) that
is termed g v (ho) in FIGURE 7, a simple normalisation procedure has been applied that is
explained in [69]. Also indicated in FIGURE 7 is the position of the Fermi energy E F at 4.4 eV
below Evac that was independently determined using the Kelvin method [70].

Total Yield (arb. units)

Total Yield
undoped a-Si:H

300K

fico(eV)
FIGURE 6 Total photoelectron yield spectrum of intrinsic a-Si:H.
Note the logarithmic scale on the ordinate [61].

E0 = 51 meV

Top of the
Valence Band

ftco(eV)
FIGURE 7 Density of occupied states (gv(feco)) obtained from the
yield spectrum of FIGURE 6 using EQN (13) [61].

gv(M(1022ev-icm-3)

300K

gv(M

(eV-1cm-3)

Total Yield
undoped a-Si:H

The occupied density of states shows the characteristic features expected for a-Si:H: a linearly
increasing valence band with an extrapolated band edge at 5.55 eV below Evac (1.15 eV below
EF) followed by an exponential valence band edge with a logarithmic slope

and a band of defects centred about 0.4 eV above Ep. The valence band tail is exponential over
about two orders of magnitude in N0Cc(E). According to the data of FIGURE 7 and further
spectra on boron doped a-Si:H films [61] the exponential valence band tail can be described by

(14)
with N(M 3 x 1021 cm'3 eV"1 and E0V = (48 + 3) meV. E v corresponds to the energy of the
linearly extrapolated valence band edge at 5.6 eV below Evac in FIGURE 7 and the energy scale
in EQN (14) has the conventional meaning with E increasing towards EF: E = Evac - ho
(compare also FIGURE 2).
The high dynamic range of yield spectroscopy affords - for finite temperatures - the
spectroscopy of states with energies above EF(h(o - Evac < EF). For heavily phosphorus doped
a-Si:H the Fermi occupation function f(E) extends well into the conduction band tail and by
dividing the measured N0Cc(E) through f(E) the one electron density is obtained as illustrated in
FIGURE 8 [71]. An exponential conduction band tail extends up to about 1020 eV 1 cm"3 with a
slope parameter E00 = 37 meV. This is larger than expected for undoped a-Si:H (~25 meV from
transport data [72]) but so is Eov (103 meV). Both are apparently broadened due to P-doping.
Yield spectroscopy is the only spectroscopic method capable of measuring the conduction band
slope directly.

gv0M (eV-icm-3)

1000 ppm P-doped a-Si:H


Total Yield

300K
theor. Fermi cutoff
at 300K

ftco(eV)
FIGURE 8 One electron density of states obtained from a yield spectrum of heavily P-doped a-Si:H.
The conduction band tail (E0C = 37 meV) is obtained by dividing No^ko) by the Fermi function [71].

BAND TAILS AND DISORDER

The notion that band tails are the result of the disorder in amorphous systems originates in the
work of [73-76]. A direct correlation between the Urbach slope and a measure of structural
disorder in a-Si:H is shown in FIGURE 9 [77]. The Urbach slope parameter is strongly
correlated with the network disorder as expressed by the width of the bond angle distribution
A@b for differently doped a-Si:H samples. The A0 b s were obtained from Raman spectra of the
same samples. Differences in the sensitivity of Eu to bond angle deviations for P- and B-doped
samples are traced to differences in hydrogen incorporation [77]. A comprehensive discussion
of the relationship between disorder, Raman line width, Urbach slope, and annealing
temperature is given in [77a].

(b)

(a)
(meV)

undoped
P-doped

B-doped
N-doped
NR

(cm*)

A0 b

FIGURE 9 Urbach slope (E0) versus defect density (NR, left hand side) and bond
angle distortion A0 b (right hand side) for differently doped a-Si:H samples [77].

A particularly graphic description of the relationship between structural disorder and band tail
slope is given in [76]. The gist of the argument is that electronic states in the valence and
conduction band tail correspond pairwise to bonding configurations that are deviations from the
construction of an ideally bonded amorphous network. Let the band edges of such an ideal
network be at 8v and sc; then each pair of band tails at energies 8 - ev and ec - ef, respectively,
corresponds to a structural deviation with a formation energy F(s,sf) which we shall refer to for
simplicity as a weak bond. Under the further assumption that the formation energy is
proportional to E - sv, i.e. the expense in electron energy connected with the creation of a less
than ideal bond, we have:
(15)
where |s| < 1 is a parameter which takes lattice contributions to F(e,ef), not contained in the
simple one-electron picture, into account. In thermal equilibrium the density of weak bonds is
proportional to exp[-F(e,ef)/kT*] where T* is the lowest temperature at which the system is
able to achieve structural equilibrium. Together with EQN (15) this yields immediately the
exponential distribution of valence tail states with a logarithmic slope E0V = k Tv = k T*/(l + s).
The steeper conduction band tail is explained by the fact that the antibonding conduction band
states are less susceptible to structural disorder [76].

The variations of the valence band slope E0V, as obtained from yield spectroscopy [60], and the
Urbach energy slope Eu, from optical absorption using photoacoustic spectroscopy [78,79], are
illustrated in FIGURE 10 for undoped a-Si:H prepared at different substrate temperatures.
Similar results have been obtained in [80,81].

energy (meV)

Eu

T Dep ( C)
FIGURE 10 Valence band slope E0V and Urbach energy Eu as a function of deposition temperature
for undoped a-Si:H. The data are from [60] and [79] for E0V and Eu, respectively.

Both sets of data exhibit a characteristic parabolic dependence of the slope parameter on
deposition temperature with a minimum of - 5 0 meV (Eov) between 250 and 300 0 C. Not
surprisingly, this is the temperature which also yields the best material where electronic
properties are concerned. Considering a wide range of optical data the optimised Urbach slope
appears to follow a parabola as a function of deposition temperature T D [80]:
(16)
This relationship holds from room temperature up to the crystallisation temperature of a-Si:H at
about 600 0 C. Samples prepared under less than optimal conditions, such as by sputtering [82]
or high deposition rate [83], have Eu values that lie above this parabola. While there is general
agreement that annealing of a-Si:H prepared at suboptimal temperatures leads to an
improvement in electronic quality and often a reduction in Urbach tail width, the evidence for a
general relationship like that of EQN (16) that also covers annealing, as suggested in [80], is
controversial (see for example [79]).
The first thing to note in connection with FIGURE 10 and EQN (15) if one equates Eu with E0V
is that at the minimum of E0V versus T D the slope of the valence band tail corresponds closely to
kTnun = 4 2 - 5 0 meV, i.e. T1nIn = 224 - 307 0 C. This implies, after what has been said about the
origin of the band tails, that the a-Si:H network is in thermal equilibrium at the optimum
deposition temperature (T1M11 = T*) and that the formation energy of weak bonds is determined
mainly by the electronic contribution: F(e,sf) = e - Cy. On the basis of this model one would

expect a linear relationship between E0V (or Eu) and T D in either direction away from T1nIn that is
not observed experimentally. Eu, and thus implicitly E0V, increases quadratically with T - T1Hin,
and this behaviour has been linked to the role of hydrogen in a-Si:H [80]. In the hydrogen glass
model of a-Si:H [84] structural equilibration of the amorphous network is brought about by the
diffusive motion of highly mobile hydrogen that moves between Si-Si bonds and is able to break
strained bonds and saturate dangling bonds. Because the diffusion of hydrogen is thermally
activated, its motion is frozen in below about 1000C and the structure of the film and thus E0V is
determined by the deposition process for TD < 1000C which apparently yields much less ordered
material. On the other hand, above -350 0 C hydrogen starts to leave the material and the much
less efficient relaxation processes of the Si backbone determine E0V and thus Eu.
There are clearly problems with this model. One problem has to do with the smooth increase of
Eu between T1Hin and room temperature. One would expect first a decrease in E0V3 as long as
hydrogen is still mobile, and then a transition to a constant E0V as T D crosses the hydrogen
freeze out temperature o f - 1 0 0 0 C . A similar problem arises if one considers annealing above
Tmm. Here, one would expect an Urbach slope that is equal to or smaller than kTc above a
critical temperature Tc 500 0 C at which the hydrogen is present in insufficient quantity to
mediate the structural equilibration of the network. The equivalent Urbach temperature has
reached about 900 0 C at this point, however, according to EQN (15) and the data.
An entirely different approach to the relationship between disorder and the width of the Urbach
edge was taken by Cody et al [10,11]. It embodies the concept of the equivalence of structural
and thermal disorder as expressed in [85,86]. The approach is based on the observation that the
Urbach slope measured as a function of temperature (FIGURE 11) between 10 and 320 K, and
measured at a fixed temperature (300 K) as a function of annealing temperature, scales linearly
with the Tauc gap E G determined simultaneously (FIGURE 12) [10]:
(17)
where E G varies between 1.8 and 1.45 eV and Eu between ~50 and 100 meV. Because of this
remarkable linear relationship between E G and Eu Cody et al proceeded to apply established
theories for the temperature dependence of optical gaps in crystalline semiconductors to the gap
and the Urbach slope of a-Si:H. E G in crystalline semiconductors can be written as [87]:
(18)
where D is a second-order deformation potential and <u2>T the ensemble average of the
displacements u of the atoms from their equilibrium positions. The average of the zero point
motion <u2>0 has been added to EQN (18) so that EG(T) equals E G (0), the zero temperature
gap, for T = 0. An equivalent expression should describe the Urbach slope in the framework of
the model:
(19)
where the temperature independent term <u 2 > x has been added which takes into account the
contribution of disorder to the Urbach edge in the spirit of frozen-in phonons of mean square

displacement <u 2 > x . This equation also has been established as part of a more detailed theory
in [88]. Extending EQN (18) by the same term yields the experimentally observed linear
relationship between E G and Eu that covers temperature T and disorder X as it is changed by
annealing, for example:

(20)
Using the temperature dependence of Eu for fixed X and the Einstein approximation to calculate
<u2>T Cody obtains for the frozen-in phonon amplitude of a sample with E11 = 50 meV:

[ H ] . He argues that such a large value can only correspond to fluctuations in next-nearest
neighbour distance due to bond angle variations (root mean square) of ~2. The conclusion of
this analysis is therefore that Eu and E G are sensitive to bond angle variations and that this is the
principal aspect of disorder that governs these quantities. Further elaboration of this model is to
be found in [11,12]. Notice also the general, albeit not quantitative, agreement with the results
of FIGURE 9.

E0

(meV)

EG

(eV)

Ib)

(a|

T(K)
FIGURE 11 Temperature dependence of the Uibach slope (E0)
and the Tauc gap (EG) for undoped a-Si:H [10].

Ee

EG (eV)

(meV)

Cody et al.

SAMPLE
NO.
1
2
3

TEMP. OEPENOENCE
EVOLUTION
TEMP. OEPENOENCE
EVOLUTION

E0 (meV)
FIGURE 12 Correlation between Urbach
slope (E0) and Tauc gap EG. The data cover
measurements performed at different temperatures
as well as measurements at 300 K after annealing
of the a-Si:H samples [10].

E 0 (eV)
FIGURE 13 Urbach slope (E6) versus optical gap (E0)
of undoped a-Si:H as a function of annealing (Ta),
substrate (Ts), and measuring temperature (T). Also
indicated is the linear relationship between Ee and E 0
as obtained by Cody et al [10] for samples annealed
and measured at different temperatures [79].

Appealing as this model is, it is not generally supported by experiment as the data of FIGURE
13 demonstrate [79]. Here, the relationship between Urbach tail slope and Tauc gap as derived
for a-Si:H samples as a function of deposition, annealing, and measurement temperature are
contrasted with the result of Cody et al and there is little if any agreement. A comparison such
as that of FIGURE 13 and the discussion in connection with EQN (16) points towards a
principal problem one encounters when applying equilibrium arguments to a-Si:H; they neglect
the strongly non-equilibrium nature of the deposition process [53] and the chemical influence
that hydrogen has on the band edges and the pseudo gap of a-Si:H [12].

TEMPERATURE DEPENDENCE OF URBACH EDGE AND BAND TAILS

The temperature dependence of the Urbach slope in FIGURE 11 has been fitted to EQN (19)
by evaluating <U2>T in the Einstein approximation [H]:
(21)

where k 0 = k 400 K is the energy of the single phonon mode that is supposed to represent the
phonon spectrum of a-Si:H in the Einstein approximation. This expression corresponds in the
high temperature limit to a temperature coefficient of Eu equal to the Boltzmann constant
k = 8.6 x 10'5 eV K"1. This limit (T 0 ) is, however, never reached because annealing sets in
at about 600 K and the temperature coefficient between 200 and 400 K is closer to 5 x 10"5 eV
K"1. A linear increase of Eu with nearly the same temperature coefficient has been measured
between about 200 and 400 K by a number of authors [79,89-91]. Nevertheless, there have
also been reports of a constant Eu in a comparable temperature range [37,92]. The reasons for
these differences are not clear at present. It is argued in [91] that in some instances the
temperature dependence of E is better described by a theory that goes beyond the folding of
initial and final densities of states [93].

Bandtail Characteristic Energy (meV)

Temperature (K)

<a> E oc

1000 ppmPH3
50 ppm PH3
Undoped Sample 1
lOOppmPH a-Si. Ge:H

KBT (meV)

Temperature (K)

<b> Eov

Undoped Sample 1
Undoped Sample 2
100 ppmB2H6
10ppmB2H6
100 ppm B2H6 a-Si. Ge:H

K B T(meV)

FIGURE 14 Valence (Eov) and conduction band (Eoc) slopes as obtained from yield spectra versus
temperature. Results are shown for differently doped a-Si:H and one a-SiGe:H alloy [96].

The temperature dependence of valence and conduction band tails has been measured separately
by yield spectroscopy between 200 and 500 K [94-96]. The measurements of EOc and E0V as
shown in FIGURE 14 cover a range of doped and undoped samples as well as an amorphous
hydrogenated silicon-germanium alloy [96]. The surprising result is that EOc varies strongly
with T while the valence band slope remains comparatively constant. In fact, Eoc increases
linearly with T above a critical temperature T* with a slope AEoc/AkT between 1 and 2. The
value of E0V, by comparison, increases by about 6 meV between 100 and 500 K. This
corresponds, on average, to a temperature coefficient of -1.5 x 10'5 eV K"1 and is thus
substantially smaller than that of Eu. The implications of this result have been discussed in
[94-96]. The main conclusions are that the valence band is more susceptible to static disorder

than the conduction band while the opposite is true for the effect of dynamical, i.e. temperature
induced disorder. This clearly disagrees with Cody's model which treats static and thermal
disorder on the same basis [10]. The results agree much more closely with the arguments of
Bar-Yam et al [76] (compare previous section) which yield a linear dependence of EOc and E0V
with T above a 'freeze-in' temperature T* below which the deviations from an ideal random
network are frozen in. The freeze-in temperature T* is <3 00 K for the conduction band of
undoped a-Si:H according to FIGURE 14 and thus yields a conduction band slope of 25 meV
as observed for intrinsic samples by time of flight measurements [72,97]. Additional doping or
alloying raises T* without affecting the temperature coefficient of EOc. By the same token, the
freeze-in temperature of the valence band slope would be >500 K according to the data and that
raises the question as to what equilibration mechanisms are operative and how they could
possibly affect E00 and E0V so differently.

DEFECT DENSITY AND TAIL SLOPES

Defect density (cm " 3 )

There is abundant evidence from optical data that the Urbach slope Eu and the deep defect
density ND as measured, for example, by the defect absorption below -1.4 eV (region C in
FIGURE 1) are correlated. Examples are the entries of TABLE 1, and FIGURES 3, 4 and 9.
In all cases E11 is seen to increase with ND. In fact, most of the published data for Eu and the
deep defect density fall into the shaded region of the Eu versus ND diagram of FIGURE 15. The
correlation holds also for Eov versus
ND in cases where the valence band
slope has been deduced from optical
data by deconvolution (see FIGURE
4) and for E0V, ND pairs obtained
directly for P-doped a-Si:H from
yield measurements [60,98]. In these
cases the data points tend to lie on
the left hand border of FIGURE 14,
i.e. the variation of E0V with N D is
much less pronounced. Generally
speaking, the regime in the lower part
of FIGURE 14 (E0 < 90 meV, ND <
1018 cm"3) is covered by non-optimal
deposition conditions and mild
doping whereas defect densities and
Urbach slope energies above 1018
cm"3 and 90 meV, respectively, are
almost exclusively reached by heavy
doping (compare FIGURE 3 and
TABLE 1).
There have been
thermodynamic models which relate
Eu (meV)
the deep defect density to the
distribution of defect formation FIGURE 15 Correlation between the Urbach slope Eu and the
energies.
In their simplest form density of deep dangling bond defects. Published data for doped
and undoped a-Si:H prepared under a variety of deposition
defects are considered to arise from
conditions fall within the shaded area.
the
spontaneous
[80]
or

thermally activated [81] transformation of weak bonds into dangling bonds. The formation
energy is - in the one-electron approximation - equated with the difference of one electron
energies of weak bonds and dangling bonds.
For a fixed dangling bond energy the distribution function of the defect formation energies
equals the valence band tail density of states and the observed nearly exponential increase in ND
with E0V follows [80,81]. This weak bond-dangling bond conversion process has been
considered in more detail in [99] and it is able to describe quantitatively the correlation between
ND and E0V in the low defect regime which is covered essentially by variations in preparation
conditions such as deposition and annealing temperature.
It has been claimed that the same mechanism and thus the same functional relationship between
ND and E0V holds also for heavily doped material, i.e. for defect densities and Urbach slopes
greater than ~1018 cm"3 and 90 meV, respectively [80]. Such an extension of the weak bonddangling bond (wb-db) model would require that doping has directly, or indirectly, a
considerable influence on the structure of a-Si:H. The opposite appears to be true. Electron
and hole drift mobilities decrease so slowly with doping that the band tail slopes are increased
by no more than 10% for a gas phase dopant concentration of 10"4 [53]. This broadening is
insufficient to account for the drastic increase in Eu with doping and thus for ND according to
the wb-db model.
Most significant, however, are the results of yield measurements on boron doped a-Si:H shown
in FIGURE 16 [61]. Because the defects created in response to the boron doping are positively
charged, i.e. empty dangling bonds, they do not contribute to the yield signal. Instead, the
concentration of neutral defects is reduced with increasing boron concentration and that affords
an unobstructed view of the valence band tail with a slope that is unaffected by doping and
rather small (E0V = 45 meV). In contrast, optical spectra always exhibit a rapidly increasing
shoulder due to transitions from filled (P-doping) or into empty (B-doping) defect states that
rapidly obscures the real Urbach tail (compare FIGURE 3). What is taken as the Urbach edge
in heavily doped a-Si:H is thus the transition region from the exponential part of the absorption
edge to the power law regime. This, of course, yields a much greater 1E01 when fitted by an

gv(>M (eV-icm-3)

Total Yield
clean B-doped a-Si:H

gas phase diborane-^0


concentration

E0 = 45jneV

300K

/ko(eV)
FIGURE 16 Density of occupied states (gv(ko)) for differently boron doped a-Si:H samples as obtained
from yield spectroscopy. Notice the unchanged valence band tail slope of E 0 = 45 meV [61].

exponential and the correlation between Eu and ND shown in FIGURE 15 is thus likely to be an
artefact of the data analysis. The problem was realised by Roxlo et al [54] and hinted at in [15].
Depending on the deconvolution process and the degree of interference between absorption and
Urbach edge the values of E0V derived from optical data may or may not be affected. A
comparison of TABLE 1 and FIGURE 4 is instructive. Finally, it should be mentioned that
yield measurements of P-doped a-Si:H are prone to the same problems when E0V is determined
because emission from negatively charged defects interferes with the valence band tail unlike the
data for B-doped material. A true effect of doping on the valence band tail may be apparent in
compensated samples. Here, doping does not lead to the creation of compensating deep defects
and the moderate increase observed in E1, [83] or E0V [98] is thus likely to be due to dopant
induced disorder.
There is thus compelling evidence that the correlation between ND and Eu shown in FIGURE 15
for heavily doped a-Si:H is an artefact of the data analysis. Defects are created in direct
response to the incorporation of doping atoms as discussed in [53].

ACKNOWLEDGEMENT The author is most grateful to J. Ristein for many illuminating discussions and a
careful reading of the manuscript, to J. Kinsky for help with thefigures,and last but not least to Ulrike Dawson
for the patient and efficient typing of yet another draft.

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S. Aljishi, J.D. Cohen, Shu Jin, L. Ley [Mater. Res. Soc. Symp. Proc. (USA) vol.192 (1990)
p.157]
S. Aljishi, J.D. Cohen, Shu Jin, L. Ley [ Phys. Rev. Lett. (USA) vol.64 (1990) p.2811 ]
J.M. Marshall, R.A. Street, MJ. Thompson [ Philos. Mag. B (UK) vol.54 (1986) p.51 ]
S. Aljishi, Shu Jin, L. Ley [ J. Non-Cryst. Solids (Netherlands) vol. 137&138 (1991) p.387 ]
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3.3

Information on gap states in a-Si:H


from ESR and LESR
P.C. Taylor
April 1997

INTRODUCTION

Electron spin resonance (ESR) and optically- or light-induced ESR (LESR) are two standard
techniques that are used to probe localised electronic states occurring within the optical energy
gap in a-Si:H and related alloys. These two techniques provide information concerning the
wavefunctions of paramagnetic, localised electronic states primarily through two basic
interactions - the electronic Zeeman interaction including spin-orbit coupling and the hyperfine
interaction of the electronic spin with nearby nuclei of non-zero spin. The Zeeman interaction
is characterised by a gyromagnetic tensor, g, whose departures from the isotropic free-electron
value of g = 2.0023 yield information about the electronic wavefunction and the energy of the
electronic level with respect to the band edges. The hyperfine interaction is also characterised
by a tensor, A, whose values provide detailed information on the electronic wavefunction, as
for example on the s- and p-components. For technical reasons, especially when applied to
amorphous solids [1], ESR and LESR are most sensitive to electronic states that are localised
over at most a few atomic sites.
1Q
Without hydrogen a-Si exhibits a large ESR signal that corresponds to spin densities >10 cm"
[2]. This signal is attributed to a Si dangling bond - a single electron in a nearly sp
wavefunction on a silicon that is back-bonded to three silicon atoms. In a-Si:H the ESR signal
is much smaller (<1016cm~3) and is often due to surface contributions in films whose
thicknesses are < a few |nm. Optical experiments suggest that this neutral Si dangling-bond
state is near the middle of the optical gap. Optical excitation of a-Si:H produces an increase in
this ESR signal that is metastable (persists when the light is turned off) at temperatures below
about 1800C in most nominally undoped (intrinsic) samples [3]. (Strictly speaking, this signal
is light-induced ESR, but in keeping with common practice in the literature, we reserve the
term LESR for the transient signals that occur below about 150 K [4].) This metastable ESR,
which is also attributed to Si dangling bonds, has been tied to metastabilities that occur in the
photo- and dark conductivities - metastabilities that are called the Staebler-Wronski effect [5].
A detailed review of these two ESR responses, both of which have the same ESR lineshape, is
available elsewhere [6].
In doped samples ESR signals attributed to un-ionised donors (phosphorus or arsenic) have
been observed [7]. For reasons that are not understood, similar signals have not been observed
for acceptors such as boron. In sharp contrast to the situation in crystalline semiconductors, the
most commonly observed signals in doped samples are not due to un-ionised dopants. These
more commonly observed ESR signals are attributed to singly-occupied states deep in the
conduction and valence band tails for n- and p-type doping, respectively [8]. Similar signals,
although transient, are observed in LESR experiments in intrinsic a-Si:H below about 150 K. In
the LESR experiments the two signals, one for electrons deeply trapped in conduction band-tail

states and one for holes deeply trapped in valence band-tail states, usually occur with roughly
equal intensities. ESR signals due to impurities, including dopants, are often not observed in
a-Si:H unless the impurities occur at alloy concentrations (>1 at.%).

ESR

In a-Si and intrinsic a-Si:H only a single ESR signal is observed without optical excitation or
carrier injection. This signal, which is attributed to a silicon dangling bond, has characteristic
ESR parameters as shown in TABLE 1 and a characteristic ESR absorption lineshape as shown
in FIGURE l(a). The hyperfine interaction with 29Si indicates that approximately 70% of the
spin density for this defect consists of an sp3 hybrid on a three-fold-coordinated silicon atom [9].
The rest of the density is distributed approximately on the three back bonds. Pulsed ESR [10]
and low frequency ESR [11] experiments have shown that in a-Si:H the hydrogen atoms are no
closer to the silicon dangling bond than the equivalent of third-nearest neighbours. The
linewidth of this ESR signal (TABLE 1) at the most commonly used spectrometer frequency
(9 GHz) has two primary contributions: (1) an unresolved anisotropy in the g-tensor at a defect
site, and (2) an inhomogeneous distribution of g-values at different defect sites. The energy of
this defect with respect to the valence-band mobility edge, E v , is not well known but thought to
be about 1 eV.
TABLE 1 ESR parameters for characteristic defects in a-Si:H and doped a-Si:H.
Defect*

g-value

Linewidth @
9 GHzb (G)
8(1)

Band-tail
electron
Band-tail
hole
P40

2.004 (2)

Spin density
(cm 3 )
<1016
17
~10 light soaked
1014 to 1017

2.013 (5)

10 1 5 tol0 1 7

17(5)

<1017 c

65 (10)

As40

2.005 (5)

<1017 c

100 - 300 d

2.0055 (5)

2.003 (5)

Hyperfine
interaction (G)
[29Si]
A = 70 (5)

[31P]
A =240 (10)
[75As]
A =355 (10)

5(1)

a superscript denotes charge; subscript denotes coordination;


b peak-to-peak derivative linewidth;
c maximum value, depends on dopant concentration;
d depends on hyperfine transition.

Upon excitation with light of energy greater than or equal to the optical energy gap (commonly
referred to as light soaking in the literature), there is a metastable increase in the silicon
dangling-bond ESR response [3]. In intrinsic a-Si:H this signal saturates at approximately 1017
cm"3. These additional silicon dangling bonds are metastable at 300 K and anneal on a time
scale of minutes above about 350 K. There is a distribution of annealing times and activation
energies, but the average activation energy for annealing is approximately 1.5 eV. There are
many parallels in the kinetics for the production and annealing of this metastable ESR and the
Staebler-Wronski effect. There is also a scaling of this ESR with optical absorption that occurs
well below the exponential absorption edge (Urbach absorption). Finally, there is evidence that
rapid quenching from about 350 K or above also produces an increase in the silicon dangling-

bond ESR that is metastable at 300 K. The kinetics associated with light soaking and thermal
quenching do not exhibit unique time constants for growth or decay, but rather these processes
are dispersive and can be fitted phenomenologically by a stretched exponential function.

ESR (Arb. Units)

(a)

LESR (Arb. Units)

(b)

Magnetic Field (Gauss)


FIGURE 1 (a) ESR in a-Si:H, (b) LESR in a-Si:H.

In doped a-Si:H four additional ESR responses are observed [7,8]. As listed in TABLE 1, these
responses are attributed to electrons trapped in conduction-band-tail states, holes trapped in
valence-band-tail states, neutral phosphorus donors, and neutral arsenic donors. The latter two
signals are not commonly observed because the donors and acceptors are normally charged due
to compensation with charged silicon dangling bonds or occupied (charged) band tail states.
From the hyperfine interactions with phosphorus or arsenic, the neutral donor levels are
estimated to be about 100 meV below the conduction-band mobility edge. The analogous
signals for neutral acceptors, such as boron, have not been observed, presumably because the
energy levels lie so close to the valence-band mobility edge that they are always negatively
charged. Hyperfine interactions with 31P and 75As suggest that the neutral donors are
approximately 0.2 eV below the conduction-band mobility edge, much deeper than in crystalline
silicon. Although it is standard to assign the ESR signals in TABLE 1 to neutral phosphorus
and arsenic donors that are four-fold coordinated, other explanations have been proposed [12].

LESR

At temperatures below about 150 K there exists a transient LESR signal [4] as shown in
FIGURE l(b). The two components of this signal are the same as those observed in highly
doped samples where they are attributed to electrons and holes deeply trapped in band-tail
states (TABLE 1). Because the intensity of the LESR attributed to holes is usually about three

times that for electrons, some authors have suggested that these signals result from the optical
excitation of charged defects [13] (defect pool model [14]). From the LESR alone there is no
necessity to invoke the presence of a pool of charged defects in a-Si:H since there are several
technical reasons why the ratio of LESR intensities due to electrons and holes is not unity.
These reasons include differences in microwave saturation, localisation length, and various
relaxation times for electrons and holes in their respective band tails. The growth and decay
rates of the LESR are strongly temperature dependent and dispersive at any given temperature.
The intensities of the LESR depend on the temperature, the irradiation time, and the intensity of
the exciting light, but values from approximately 1015 cm"3 to 1017 cm"3 have been reported.

CONCLUSION

ESR and LESR are important probes of localised electronic states within the optical energy gap
in amorphous silicon and hydrogenated amorphous silicon. In a-Si the only ESR response is
that which is attributed to neutral silicon dangling bonds; there is no LESR. In a-Si:H, the ESR
signal due to silicon dangling bonds also occurs, albeit at much lower densities, and there exists
a metastable increase in the number of these defects after irradiation with light whose energy is
greater than that of the optical gap. There is also an LESR response in a-Si:H that consists of
two components whose densities are nearly equal. These two components are attributed to
electrons and holes trapped in conduction band-tail and valence band-tail states, respectively.
These two LESR lines are observed individually in ESR of n- and p-doped a-Si:H. Also, ESR
lines attributed to neutral donors are sometimes observed in heavily doped samples.

REFERENCES
[I]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[II]
[12]
[13]
[14]

CP. Poole Jr. [ Electron Spin Resonance, 2nd ed. (Wiley, New York, 1983) ]; CP. Slichter
[ Principles of Magnetic Resonance, 2nd ed. (Springer, New York, 1990) ]
M.H. Brodsky, R.S. Title [ Phys. Rev. Lett (USA) vol.23 (1969) p.581-5 ]
H. Dersch, J. Stuke, J. Biechler [Phys. Status Solidi B (Germany) vol.105 (1981) p.265-74 ]
J.C Knights, D.K. Biegelsen, I. Solomon [ Solid State Commun. (USA) vol.22 (1977) p. 133-7 ]
D.L. Staebler, CR. Wronski [ Appl Phys. Lett. (USA) vol.31 (1977) p.292-4 ]
P.C Taylor [ Semicond. Semimet. (USA) vol.21C (1984) p.99-154 ]
M. Stutzmann, D.K. Biegelsen, R.A. Street [ Phys. Rev. B (USA) vol.35 (1987) p.5666-701 ]
R.A. Street, D.K. Biegelsen, J.C Knights [ Phys. Rev. B (USA) vol.24 (1981) p.969-84 ]
D.K. Biegelsen, M. Stutzmann [ Phys. Rev. B (USA) vol.33 (1989) p.3006-11 ]
S. Yamasaki, J. Isoya [J. Non-Cryst. Solids (Netherlands) vol. 164-166 (1993) p. 169-72 ]
M. Stutzmann [Mater. Res. Soc. Symp. Proc. (USA) vol.467 (1997) p.37-42 ]
T. Shimizu, X. Xu, T. Ohta, M. Kumeda, N. Ishii [ Solid State Commun. (USA) vol.67 (1988)
p.941-4 ]
M. Favre, A. Shah, J. Hubin, E. Bustarret, M.A. Hachicha, S. Basrour [ J Non.-Cryst. Solids
(Netherlands) vol.137-138 (1991) p.335-8 ]
S.C Deane, MJ. Powell [ Phys. Rev. Lett. (USA) vol.70 (1993) p. 1654-7 ]

3.4

Information on gap states in a-Si:H from thermal defect


spectroscopies
I. Thurzo and V. Nadazdy
September 1997

INTRODUCTION

Information on the density of gap states in a-Si.H from thermal defect spectroscopies is yielded
via non-radiative transitions between defect levels and transport bands. There are several
measurable transient quantities (e.g. current or capacitance) that are due to charge carriers
emitted from deep levels after thermal stimulation. A temperature scan with usual temperature
limits 80 - 450 K allows probing of a wide range of thermal activation energies E because the
escape probability of carriers from trapping sites depends exponentially on the E/kT ratio.
Thus, these techniques are considered as spectroscopic ones, providing information on the basic
parameters of deep states: the thermal activation energy, the frequency factor and the
concentration. However, we cannot determine the microscopic physical and chemical nature of
gap states using such techniques.
All of the thermal defect methods used for a-Si.H are related to the space-charge layer of a
Schottky barrier, p-n junction or metal-insulator-semiconductor (MIS) structure. Early studies
reported on the measurement of temperature and/or frequency dependences of the capacitance
[1-3] and admittance [4,5] of an a-Si:H Schottky barrier. Considerable progress in the
characterisation of a-Si:H has been made by the application of thermal transient techniques,
thermally stimulated currents (TSC) [6-8], thermally stimulated capacitance (TSCAP) and deep
level transient spectroscopy (DLTS) [9]. Isothermal capacitance transient spectroscopy (ICTS)
[10] which processes the isothermal capacitance transient in a time domain at different
temperatures was also applied. The two latter methods seem to be the most effective tools for
investigating the gap states of both doped and undoped a-Si:H films. In fact no remarkable
study on a-Si:H has appeared in recent years which has employed thermal defect spectroscopies
other than DLTS or ICTS. Therefore, the following two summary sections will be restricted to
the results obtained with these two prominent methods.

DEEP-LEVEL TRANSIENT SPECTROSCOPY (DLTS)

The ability of the DLTS technique to monitor the effective one-electron density of gap states
g(E) in amorphous silicon was demonstrated in the classical paper by Lang et al [9]. Their
measurements on doped a-Si:H showed an extreme sensitivity of DLTS to changes in gap states
(see FIGURES 1 and 2). In the accompanying theory paper, Cohen and Lang [11] performed a
foil numerical analysis of the thermally stimulated transient response of a Schottky barrier
space-charge region for a semiconductor with arbitrary continuous density of gap states.
Although numerical calculations are needed for obtaining g(E) from the DLTS spectra, even the
raw DLTS data are in a form which is very close to the shape of g(E). This enables direct
comparison of the densities of states for different a-Si:H samples or for the same sample

prepared under different temperature, bias, and light-soaking conditions. In [9,11] special
attention was paid to the relative sensitivity of DLTS and other techniques, related to the
junction space-charge layer, to the interface. This point is crucial for reliably distinguishing
between the bulk and interface states, to facilitate a comparison with the results obtained by
other techniques (electron spin resonance or optical effects), which give information from the
bulk of samples. From the point of view of the relative sensitivity to the interface states, the
capacitance DLTS and dC/dV measurements rank with the techniques with a low sensitivity to
them. Current DLTS and steady-state low frequency capacitance measurements reach their
maximum sensitivity at the interface.

g(E)

(crrf3eV~1)

DLTS SIGNAL (pF)

SAMPLE 5
(152)

SAMPLE 5
(152)

ENERGY (eV)
FIGURE 1 Two g(E) curves used in the calculation
of measured DLTS spectra (after Lang et al [9]).

LASER PULSE

VOLTAGE
PULSE
TEMPERATURE (K)
FIGURE 2 Calculated DLTS spectra for the two g(E)
curves in FIGURE 1. Experimental data are depicted
with circles; solid and dashed lines correspond to the
respective solid and dashed curves in FIGURE 1
(after Lang et al [9]).

So far the DLTS method has been predominantly applied to doped a-Si:H films, especially to
n-type a-Si:H [12-15]. For a variety of n-type a-Si:H samples, a pronounced broad band of
g(E) in the lower half of the gap has been reported. The frequency factor vo, corresponding to
the energy of 0.85 eV, is of the order of 1013 s"1. The density of these gap states varies from
1017 to 1018 cm"3 eV 1 and increases with increasing dopant concentration. The upper half is
characterised by an apparent minimum (<1016 cm"3 eV"1) at about 0.4 - 0.5 eV below the
mobility edge E c . In spite of possible influence of dopant atoms on the measured distribution,
such a shape of g(E) is consistent with the prediction of the improved defect-pool model
[16-18] for n-type a-Si:H. DLTS measurements on p-type a-Si:H samples have not been
reported because of the difficulty in moving the Fermi level away from the midgap in p-type
samples.
However, for understanding the physics of a-Si:H, while excluding any modification of g(E) due
to dopants, a study of the undoped material is more convenient. The reason for few
applications of the DLTS technique to undoped a-Si:H film consists in the dielectric relaxation
time being too long for the capacitance measurement and in the high sensitivity of the transient
currents to the interface states. To overcome the difficulty with long relaxation times, Crandall

[19] performed capacitance measurements on p-i-n and n-i-p a-Si:H solar cells at temperatures
above room temperature. He investigated light- and current-induced metastable defects in
undoped a-Si:H layer with isothermal mode of the DLTS. After different modes of degradation,
the activation energies E and frequency factors v o of defects obtained for various samples fell
into three distinct groups: ( I ) E < 0.6 eV and v o < 1 x 105 s"1, (2) E around 1 eV and
v o < 1 x 1013 s\ and ( 3 ) E > 1.4 eV and v o > l x 1013 s\
Another approach to the DLTS measurements on undoped a-Si:H was based on the advantage
of the current DLTS version when the thermally excited carriers are detected directly in the
external circuit. This approach, mediated by overcoming two drawbacks (the loss of signal
amplitude with increasing delays of the sampling event and considerable influence of the leakage
current on the measured spectrum), has recently been reported by Nadazdy et al [20]. To
eliminate the loss of signal amplitude, they used charge DLTS [21] where the transient current
is integrated, yielding a charge transient. The integration eliminates the x"1 term in the
expression for the signal and makes the charge detection sensitivity independent of the time
constant x. The leakage current of samples under test was reduced by the presence of an
insulating layer prepared by bombardment of the a-Si:H surface with Ar atoms of an energy of
300 eV for 7 minutes before evaporation of gold electrodes. Thus, an MIS-like structure was
obtained, where quasi-Fermi levels are not considered and the surface Fermi level can easily be
shifted by the applied bias over the whole bandgap. Unlike thermally grown and deposited
insulating layers, this treatment does not induce a high density of interface states. Essentially,
the charge DLTS experiments on undoped a-Si:H [20] followed the experiment of Winer [22]
suggested for testing his defect-pool model which was further developed by other authors
[16-18]. According to this model, the shift of the Fermi level changes the defect potential and
creates conditions for a new equilibrium distribution of the density of states. The idea of the
experiment is to shift the Fermi level of an equilibrated a-Si:H film in an MIS sandwich by the
bias voltage, and to monitor the resulting change in the defect distribution as the film
re-equilibrates. The set of charge DLTS spectra in FIGURE 3 summarises this experiment.

AQ (pC)

E c -E(eV)

Temperature (K)
FIGURE 3 The charge DLTS spectra of undoped a-Si:H annealed at different bias voltages Uba and
equilibrium temperature of 490 K for 10 min. The spectra were measured with Ub = - 3 V bias
voltage, pulses to 0 V and rate window of 50 s 1 (after Nadazdy et al [20]).

There are three groups of the gap states with mean energies of 0.63, 0.82, and 1.25 eV,
respectively. The conditions for their creation as well as the energy values are in good
agreement with the improved defect-pool model developed by Powell and Deane [17]. As in a
previous paper [19], a variation in the frequency factor vo with the energy was observed. It
increases from 8 x 1011 s"1 for 0.63 eV to 3 x 1012 s"1 for 0.82 eV to 2 x 1016 s"1 for 1.25 eV.
Another way to correct for the parasitic charge due to leakage currents (the linear component of
the charge response with respect to time) is second order filtering [23]. It consists in sampling
the charge transients at three suitably defined points in time, thereby rejecting completely the
parasitic contribution to the spectrum. We have already used such an approach for determining
the flatband voltage and the electron threshold voltage of a TFT based on undoped a-Si:H [24].
The improved selectivity of this filter in resolving relaxation processes with different time
constants might also be profitable for detecting particular components of the total one-electron
density of states in undoped a-Si:H [17].

ISOTHERMAL CAPACITANCE TRANSIENT SPECTROSCOPY (ICTS)

Though it is possible to get equivalent DLTS peaks from deep levels while scanning the rate
window at a properly set constant temperature [19], the ICTS method developed by Okushi and
his group [25,26] has been profiting from defining the signal in such a way that its magnitude at
the peak position is proportional to the change in occupancy of the related trap level. As a
matter of fact, the square of a conventional p+-n or Schottky junction capacitance in depletion is
given by
C 2 (t) = qeA 2 N T (t) / 2(VD + V R )

(1)

where q is the electronic charge, 8 the dielectric constant, A the junction area, VD the built-in
potential and Nx(t) the net ionised donor-state density at a point in time t. The variation ANiotai
in the total space charge density of the ith trap level in response to a filling pulse is expressed as
(2)
where NTi is the density of the trap, and Ti is the time constant of the change in occupancy
(FIGURE 4(a)). The functions Fi are the electron occupations at times defined by respective
arguments. Then we get
(3)
If we plot S(t) = d [C(t)2] /d(ln(t)) = dANTotai/d(ln(t)) as a function of ln(t), a peak appears at
t = Ti, the reciprocal of the thermal emission rate e* = e,u + epi, a situation depicted in FIGURE
4(c). It is worth mentioning how to modify the formalism outlined above in the case of gap
states distributed in energy depth, while considering a uniform NT(E) throughout the space
charge region. Introducing parameter B = qeA2/2(VD+VR), Okushi [10] extended his ICTS to
semiconductors with gap states characterised by their distribution function g(E) by expressing
the response S(t) as

(4)
where D(E,t) = ent exp(-e,,t). In contrast to the routinely encountered practice of assigning the
gap states a constant frequency factor v (capture cross-section), he considered a relation
between the depth of traps at an energy E c - E(t) and v(E(t)) as follows:

AN Total (lin. scale)

(5)

TIME (logt)
(b)

S ( t ) (log.scale)

" A N Total( l i n S C Q l e )

TIME t
(a)

T,

^i

TIME (logt)
(c)
FIGURE 4 Schematic representation of the algorithm of ICTS.

This opens the way to deducing the energy dependence Gn(E) of the capture cross-section from
experimental data.
Without quoting further details, the latter dependence demands
measurement of refilling characteristics of gap states at different durations of the filling pulse
[10]. Irrespective of the phosphorus doping level applied, a bump in the gap state profile has
been found to be located at E c - E1n = 0.52 eV, while the frequency factor vo decreases with E
(FIGURE 5). The dominant states have been assigned to doubly occupied dangling bonds (D").
The standard ICTS applicability is restricted to doped a-Si:H of low resistivity due to the reason
mentioned in the previous section. An original solution to the problem was developed by
Matsuura [27] who applied ICTS to undoped a-Si:H/p-type crystalline Si heterojunctions. The
overall measured capacitance of the heterojunction can be represented by the depletion layer
capacitance of the crystalline Si connected in series with the geometric capacitance of the a-Si:H

(cm3eVH)
g(E)

Ec- E (eV)
FIGURE 5 Density of states distribution g(E) of P-doped a-Si:H
at 297 K for different H3ZSiH4 (after Okushi [10]).

g(E)

(cm~3eV~1)

layer. A balance has been assumed between the negative charge of ionised acceptors in the
p-type Si and that of donor-like gap states in a-Si:H at the end of the filling subperiod. After
the reverse bias has been applied for an interval longer than the dielectric relaxation time, the
space charge in the vicinity of the interface will redistribute itself in response to the applied
reverse bias. Under reverse biases much higher than the built-in voltage, relations similar to
those valid for the ICTS of Schottky junctions could be derived for data analysis [27]. A typical
g(E) in a-Si:H, as reconstructed from the heterojunction-monitored capacitance (HMC)
method, is replotted in FIGURE 6. The density of g(E) is a maximum at the energy of 0.84 eV
below Ec, V0 of 1 x 1011 s'1 and with state density of 2 x 1015 cm"3 eV"1. As to the origin of the
midgap states, it has been assigned to singly occupied dangling bonds (D).

E0- E (eV)
FIGURE 6 Density of states distribution g(E) as deduced from calculation that fits
experimental data obtained by the HMC method (after Matsuura [27]).

The structure employed with the HMC method has a serious drawback, in that it is necessary to
populate the ionised deep donor states through the undepleted fraction of the a-Si:H layer,
thereby making the filling subperiod too long for signal saturation (up to 50 s [27]). Moreover,
pulse-filling experiments are not feasible with this type of structure. The drawbacks have been
recognised by Chen et al [28] who advocated a novel metal/a-Si:H/n-type crystalline Si
structure for the ICTS. Now, the space charge region is entirely covering the a-Si:H film and
penetrating into the c-Si substrate. In addition, both charging and discharging of gap states
proceeds from the metal or c-Si so that the depletion layer capacitance, which reflects the space
charge in a-Si:H, can be measured at high frequency without the influence of the high resistance
of the a-Si:H. They found a peak of g(E) positioned at 0.66 eV below E c , corresponding vo of
1.6 x 1013 s"1, and state density of 6 x 1017 cm"3 eV"1. The peak has been correlated with the
doubly occupied dangling bond (D").

CONCLUSION

Though techniques mentioned here use the same physical principle, the distributions of g(E) in
a-Si:H as determined by them are ambiguous. This suggests that the remarkable dispersion of
distributions has its origin in the equilibrated charge state of defects in a-Si:H. The extensive
study of Crandall [19], who found the existence of three groups of defects in the gap dependent
on the sample treatment conditions, also supports this assumption. The evolution of the gapstate distribution after pre-equilibrium preparation by bias annealing [20] is an additional
argument. So far only the controversy of the a-Si:H ICTS and DLTS energy scales has been
interpreted in terms of the influence of the leakage current on the ICTS and DLTS signals
measured at low temperatures [29]. We assume that apart from the results on doped a-Si.H
obtained by ICTS [10], the remaining distributions can be understood within the framework of
the improved defect-pool model [16-18]. Its main conclusion is that there are three components
of gap state distribution in intrinsic a-Si:H, Dh, D z and De with thermal activation energies
around 0.6 eV, 0.8 eV and 1.2 eV, respectively. The change in the distribution takes place
when the duration of the defect chemical potential change is longer than the equilibration time
for defect creation [22]. This fact can be considered as the main reason for different
distributions g(E) reported in a number of papers [9,11-15,20,27,28]. Such a situation can be
created by the shift of the Fermi level irrespective of the origin of this shift. For example, the
condition for the creation of the dominant Dh component is fulfilled for samples measured by
Chen et al [28] where the 120 nm thick layer of intrinsic a-Si:H on a crystalline Si substrate is
completely depleted. The distribution obtained, with the maximum around the energy of
0.66 eV below E c , corresponds to this concept. As for the frequency factor vo, the large scatter
of experimental values indicates its dependence on energy. Whether vo(E) obeys the MeyerNeldel rule [19,20] or some other kind of energy dependence [10,28] is an open question.

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(Netherlands) vol. 66 (1984) p.217 ]

3.5

Information on gap states in a-Si:H from photoinduced


absorption
R. Durny and E. Pincik
October 1997

INTRODUCTION

In a-Si:H, the optical absorption spectrum, i.e. the absorption coefficient a (cm 1 ) versus hco
(eV) can be divided into three regions: (i) the high-absorption region (103 < a < 104), (ii) the
exponential tail, or the Urbach region (a ~ exp (hco/Ek)), and (iii) the weak absorption region
( a < 1 0 ) or so-called midgap absorption. The high-absorption region originates from the
fundamental absorption associated with transitions between extended states. The other two are
related to gap-states which can be divided into tail states and defect states originating from Si
dangling bonds. As for the Urbach region, it is believed that, in disordered systems, the Urbach
tail arises from an exponential energy dependence of the valence- and conduction-band densities
of states at the band edges and the slope parameter Eu is related directly to the extent of
disorder. The experimental evidence in the case of a-Si:H has been provided by Cody [I].
There are few reports on photoinduced changes in the Urbach tail for a-Si:H. The Urbach slope
Eu increases after bandgap illumination [2]. To return to the original annealed state, high
temperature annealing at 423 K is required. In the weak absorption region, metastable and
unstable optical absorptions have been induced [3]. While the former is annealed out at high
temperature (at around 420 K), the latter anneals out at 80 K. Although in this region the
measurements are made difficult by the limitation on sample thickness, d, to a few microns there
are several techniques which are able to overcome this difficulty, especially photothermal
deflection spectroscopy (PDS), the constant photocurrent method (CPM), and photoinduced
absorption (PA) measurements. These techniques are capable of measuring ad down to values
of about 10'5.

PHOTOTHERMAL DEFLECTION SPECTROSCOPY (PDS)

PDS measures the heat absorbed in the film, which is proportional to ad when ad 1. At
room temperature virtually all the recombination is non-radiative and generates heat by phonon
emission. A laser beam passing just above the surface of the sample, which is illuminated with
the appropriate wavelength of light, will be deflected by the thermal change in refractive index
of a liquid in which the sample is immersed. Fringes in the original absorption spectra have to
be removed by a suitable averaging procedure.
The first PDS measurements of the optical absorption edge and defect transitions of a-Si:H
samples deposited at different RF power were made by Jackson and Amer [4]. Results
demonstrate that the strength of the low energy absorption is directly proportional to the
g = 2.0055 electron spin resonance (ESR) spin density. FIGURE 1 shows midgap optical
absorption in a-Si:H measured by PDS before and after prolonged illumination [5]. The midgap

1
c*.(cm )

absorption resulting from room-temperature illumination increases with increasing intensity. To


return to the original annealed state, annealing at around 423 K is required.

ILLUMINATED
ANNEALED
Energy

(eV)

FIGURE 1 Midgap optical absorption in a-Si:H measured


by PDS before and after prolonged irradiation [5].

Favre et al [6] reported on a comparison of defect densities measured by two techniques, PDS
and ESR, on a large range of thickness (from 50 nm to 80 nm). The comparison shows that a
significant proportion of defects in a-Si:H must be charged. This conclusion is coherent with
the measured values of the dark conductivity activation energy and of Rose's power law
exponent y.
In order to improve the sensitivity of PDS, a double pass method has been proposed, in which a
pump beam is passed twice through the sample using a total reflector set behind the sample [7].
A one-dimensional theoretical analysis of this method is developed and is verified by PDS
measurements. The proposed method can determine lower optical absorption coefficients than
the conventional ones.
The amplitude of the interference fringes in optical absorption spectra for thin films has been
analysed in the range of low absorption coefficients and was found to be related to a depth
profile of absorbers, e.g. defects [8], This method has been applied to the subgap optical
absorption spectra measured by PDS. The analysis of interference fringes provides unique
information about surface and interface defects in a-Si:H. Grill and De Angelis [9] introduced
this technique to study surface/interface defects in a-Si:H and gave the analytical formula for
calculating explicitly the effect. The application of this equation readily gives the shape of
fringes for the case of interest [10]. The interference fringes represent a serious problem in the
process of PDS data evaluation.
The simultaneously determined PDS and transmittance spectra can be processed to eliminate
completely the interference induced oscillations in the spectra which are observed when the film
refractive index differs substantially from that of the substrate [H].
A better understanding of the effects of hydrogen incorporation and departure on the defects
and the disorder in undoped a-Si.H is of obvious importance. The results obtained by a
combination of several experimental techniques, including PDS, show a better stability of the

bonded hydrogen in the films deposited at high rates and are interpreted as a whole in terms of
specific local hydrogen bonding environments, related to different growth mechanisms [12].
PDS measurements can be performed also on a-Si:H based p-i-p-i and n-i-n-i doping
multilayers. Measurements yield PDS spectra nearly identical to those of bulk doped a-Si:H
[13].

CONSTANT PHOTOCURRENT METHOD (CPM)

Another sensitive measurement of ad is the technique of CPM. This technique detects


photocarriers and so is primarily sensitive to the optical transitions which excite electrons to a
conduction band, because electrons dominate the photocurrent. CPM uses background
illumination to ensure that the recombination lifetime does not depend on the photon energy and
intensity of the illumination. CPM was introduced in the field of a-Si:H by Vanecek et al [14]
and since then it has been widely used to determine the density of dangling bond defects.
FIGURE 2 illustrates CPM values of the subgap absorption coefficient of undoped a-Si:H with
lower density of states (DOS) (a) and higher DOS (b) before (A) and after (B) 15 hr
illumination [15].

b)

log oc (cm""1 )

log oc (cm** )

a)

Energy (eV)
FIGURE 2 Subgap optical absorption coefficient of (a) undoped a-Si:H with the higher DOS, (b) undoped
a-Si:H with lower DOS. 1A1 - sample annealed 3 hr at 165C, 1B1 - after 15 hr illumination [15].

Interpretation and modelling in the literature assume that CPM gives an accurate value for the
density of defects present. This, of course, is not always the case. The examination of the
CPM1S limitation as a function of several defect parameters, and particularly as a function of the
Fermi energy, in models consisting of one level, a Gaussian distribution of levels, two
independent levels, and the levels typical of a multivalent defect, etc., shows that a prerequisite
for reliably relating CPM-determined densities to actual defect densities is a knowledge of the
relative location of the equilibrium Fermi level and the energy level of the defect [16].

Recent measurements on lightly P- and B-doped a-Si:H samples have shown an unexpected
discrepancy between CPM and PDS on p-type samples. The CPM technique on lightly p-type
samples shows, in the low subgap range, higher absorption spectra in comparison to PDS [17].
This discrepancy does not indicate a higher defect density, but, that it is the result of a
supralinear, spectrally dependent Rose factor, which violates the basic condition of the CPM
technique.
A numerical model has been developed to simulate CPM spectra [18]. It takes into account the
position of the Fermi energy band and the full set of optical transitions between localised and
extended states under subbandgap illumination, capture, emission and recombination processes.
The comparison of simulated and measured spectra yields information about the density of
localised gap states in amorphous silicon, that is the valence band tail, the integrated defect
density, the defect distribution in energy and the charge state of the defect states. For n-type
a-Si:H, good agreement has been achieved between simulation and experimental data. In the
annealed state the defect absorption is dominated by a single defect peak which can be
attributed to D" states in the n-type material and D+ states in p-type a-Si:H. In undoped a-Si:H
we observed more charged than neutral defect states, confirming the predictions of the defectpool model. Furthermore, the simulations reveal that the defect chemical potential depends on
the Fermi level as postulated by the defect-pool model. In the light-soaked state, undoped
material shows an enhanced defect density. An increase in the density of both neutral and
charged defect states is observed. The charged-to-neutral defect ratio does not change upon
light soaking [19]. This conclusion is in accordance with the results of Schmidt et al [20] who
have found that in undoped a-Si:H the density of charged defects exceeds that of neutral
defects, their ratio DTD0 being approximately 2.6. This ratio is independent of the light
soaking.
The technique of CPM has been successfully applied also to a-Si:H based electronic devices
such as thin film transistors (TFTs) and solar cells [21,22]. For example, the changes in the
defect density of a-Si:H in TFT structures by prolonged bias stress or light soaking have been
studied by Park et al [21]. CPM absorptions due to defect absorptions do not change after
positive or negative bias stress. On the other hand, the CPM absorptions due to dangling bond
defects increase markedly after light soaking. We propose to modify their CPM experiments on
TFTs with regard to our recent charge deep level transient spectroscopy (DLTS) measurements
[23] performed on undoped a-Si:H. The proposed modification consists of replacing the SisN4
or SiC>2 gate insulator with a semi-insulating layer which is created by a low energy Ar
bombardment of the a-Si:H surface. This procedure provides a semi-insulating layer/a-Si:H
structure with low density of interface states which allows the Fermi level to be shifted over the
whole gap. Then the corresponding CPM experiment, after pre-equilibrium preparation of the
TFT by bias annealing [23], can provide another test of the improved defect-pool model.
There are efforts to improve the technique of CPM which, because of its simplicity, is widely
used. Sasaki et al [22] developed a new CPM system which improves the accuracy of the
measurements by suppressing the effect of optical interference.
Direct measurement of the deep defect density in thin a-Si:H films with the help of the 'absolute'
CPM has been demonstrated by Vanecek et al [24]. The optical absorption spectrum is
measured directly in absolute units (cm"1) without additional calibration and undisturbed by
interference fringes.
Computer simulations demonstrate the absolute precision of the

measurements and explain the residual interferences which are sometimes observed. The latter
are shown to be fingerprints of an inhomogeneous defect distribution.

PHOTOEVDUCED ABSORPTION (PA)

2 -2
2
UodW), (cm eV )

The induced absorption mechanism appears to be associated with defect states in the gap. PA
in tetrahedrally bonded amorphous semiconductors was reported previously by O'Connor and
co-workers [25-28] and independently by Oliver et al [29]. The steady-state PA measurements
are usually carried out at room or low temperatures using continuous laser light, mechanically
interrupted by a chopper, as an excitation source. The detected transmitted intensity of the
second, also continuous, probe light can be changed due to the laser excitation of the
semiconductor by a value of AT which can be measured by lock-in techniques and a suitable
photodetector system. The probe light in the steady-state regime is usually obtained by a
monochromator system. The PA spectra correspond to (-AT/T) plotted as a function of photon
energy hco of the probe light. The ratio AT/T is determined by first measuring the transmission
T with the excitation laser off. Typical experimental PA spectra for two sputtered a-Si:H
samples [28] with the threshold energy of 0.38 eV are shown in FIGURE 3. The spectra were
plotted as (Aaho) 2 versus probe photon energy ho at 80 K.

Energy (eV)
FIGURE 3 Photoinduced absorption spectrum plotted as (Aahco)2 versus probe photon energy
of hco for two sputtered a-Si:H samples. Threshold energy is 0.38 eV [28].

Probably the most comprehensive paper dealing with the steady-state PA method is that by
O'Connor and Tauc [30]. It describes the measurements performed at 80 - 300 K. PA spectra
of a-Si:H are usually asymmetric bands having a relatively steep rise at low probe energies ho
and a gradual decline above the peak. They assume that this shape is consistent with optical
transitions from deep discrete traps to a band of extended states. Assuming a discrete density of
trap states g(E) = NT S(E-ET), a density of states which increases as the square root of the
energy g(E) = Nc (E-E c ) 12 , constant momentum matrix element, and transition energies
ho kT, then the electron photoionisation spectrum is given by:
(1)

ET ( e V )

where r\ is the index of refraction. If the distribution of states in the gap is broad rather than
discrete, then the induced absorption spectrum due to photoionisation of trapped centres is no
longer given by EQN (1). FIGURE 4 illustrates the temperature dependence of E T measured
and evaluated by O'Connor and Tauc [30].

T(K)
FIGURE 4 Temperature dependence of induced absorption threshold in a-Si:H [30],

Hirabayashi and Morigaki [31] investigated PA at 1.8 K and carried out line shape analysis for
various samples including vacuum annealed and light-soaked ones. They stated that their
experimental results obtained at 1.8 K were not well fitted by the O'Connor expression, EQN
(I) 9 but rather well reproduced by the 5-potential model for the deep level in crystals by
Lucovsky [32]:

(2)
where t is the effective thickness of the region excited by the laser, n is the density of trapped
carriers responsible for this process, a is the photoionisation cross-section, Eth is the threshold
energy for photoionisation transition and E is the probe photon energy. The results are
summarised in TABLE 1. O'Connor's relationship EQN (1) can be rewritten in a similar form:

(3)
TABLE 1 All samples were made by a capacitively coupled glow discharge system at
different sample temperatures, T8. Sample 927 was annealed at 5500C [31].
Sample
927
927 (annealed)
519
540
541

T8
(C)
230

H content
(at.%)
18.6

300
75
120

7
33
28

Spin density Ethi (A centre)


(an 3 )
(eV)
1.55 x 1015
0.25
5.0 x 1018
0.25
7.0 x 1015
0.25
2.9 x 1018
0.35
2.5 x 1017
0.25

Eth2 (P' centre)


(eV)
0.6
0.6
0.75

Both EQNS (2) and (3) have the position of the maximum EM at the same value corresponding
to 2Eth, but they have different decreasing asymptotic behaviour which is decisive for fitting the
experimental results. The value of the PA threshold energy of Hirabayashi's experiments

corresponds to that observed by O'Connor et al - see TABLE 1 and compare with FIGURE 3 at
1.8 K. The change in PA observed after light soaking is explained as a decrease in the A centre
hole excitation and appearance of the D" electron excitation. In the same paper the authors have
presented optically detected magnetic resonance (ODMR) results supporting this conclusion.
A similar experiment has been performed by Morigaki [33] where the creation of the dangling
bond centres by light soaking is assumed. In this paper, the typical PA spectra taken at 1.8 K
for a-Si:H samples are shown {N(dangling bond density) = 1018 cm"3} before and after
semiconductor illumination by 14 W/cm2 of krypton ion laser light (530.9 nm) for 30 min. The
PA spectrum has been interpreted in terms of the excitation of trapped holes at the A centres
into the valence band and that of additional electrons at doubly occupied dangling bond centres
(D) into the conduction band, whose threshold energies were estimated from PA spectra to be
0.35 eV and 0.75 eV, respectively. The electron contribution to PA is determined by the
competition between an increase of the number of the dangling bond centres by light exposure
and decrease of the number of trapped electrons due to the enhanced recombination with holes
via dangling bond centres. Morigaki concludes that his PA results support the idea that the
electron excitation from the D" centres into the conduction band is mainly observed.
Herreman et al [34] presented PA spectra measured by the method of optically modulated
spectroscopy. Their typical PA spectrum contains a broad maximum at 1.3 - 1.5 eV. The
authors attribute its origin to the electronic transitions between negatively charged dangling
bonds D" and the conduction band (CB). When the photon energy is large enough then the
transition from D 0 to CB can be induced. The following positions of the D" and D 0 states with
respect to the CB have been deduced: 0.84 eV and 1.33 eV, respectively, while E(g) = 1.68 eV.
They stated that the transitions involving the valence band (VB) were not observed.
Morigaki et al [35] have shown that the temperature variation of the photoluminescence (PL)
peak lying below 100 K is consistent with the temperature shift of a deep level position
estimated from photoinduced absorption measurements. Both the PL peak discussed and the
deep level observed were attributed to hole related processes.
Fefer at al [36] used a similar optical technique - surface photovoltage spectroscopy - for the
determination of the position of the deep defect state levels in the gap of the undoped 1 |am
thick a-Si:H layer deposited on a tin oxide coated glass substrate. They tried to identify the
deep levels measured and to investigate the influence of the light soaking on them and discuss
the origin of the following two levels: E(c) - 0.9 eV and E(v) + 1.1 eV, while E(g) = 1.74 eV.
They stated that, a priori, the method cannot distinguish between two possible assignments D"
or D 0 of the first state and D+ or D 0 of the second (E(v) + 1.1 eV ) one. Also, two additional
states, E(c)-1.26 eV and E(v) + 1.42 eV, observed in the thinner (0.42 |im) a-Si:H layer
deposited on stainless steel, are discussed.
The steady state version of the PA has not been frequently used for the determination of the
semiconductor gap states, e.g. no contribution dealing with the steady state PA method was
presented in the 17th International Conference on Amorphous and Microcrystalline
Semiconductors in Budapest (1997). Therefore, the results presented thus far differ also in the
interpretation. The main difficulty of this technique, possibly, is formation and annealing out of
the defects in the volume of the sample under irradiation by the exciting laser light beam.

During the period 1994-97 the PA measurements were realised almost exclusively in the nonsteady-state version to study ultrafast relaxation processes of photogenerated carriers in
semiconductors with picosecond and subpicosecond laser systems by measuring the temporal
decay of PA and/or photoinduced reflection. In such experiments, two laser beams are
employed: the pump-beam pulses excite the electrons in the film and probe-beam pulses monitor
the photoinduced changes in the transmittance AT or in the reflectivity AR as a function of the
time delay between the two kinds of pulse.
Esser et al [37] investigated the influence of deep defect states on the picosecond decay of PA
in a-Si:H using femtosecond laser pulses. They concluded that the recovery of PA is controlled
by an intrinsic bimolecular recombination process if device-quality a-Si.H with low density of
defects (N(D) = 1016 cm"3) is used. For a semiconductor with higher density of defect states
(N(D) = 1018 cm'3) the recovery is significantly faster and controlled by a recombination process
that involves deep defect states. Esser et al [37] pointed out that the increase of the recovery
rate in the unannealed a-Si:H can be better explained by an ultrafast non-radiative recombination
process similar to the bimolecular Auger process [38]. The following mechanism is assumed:
the recombination of an electron-hole (e-h) pair and the transfer of the recombination energy to
the D0 state. This energy can ionise the D0 state (production of D+ state) and release an
electron into the conduction band. Then the net absorption change is given by the difference
between the respective optical absorption cross-sections of both mentioned states. This means
an active role of the deeper defects is assumed in the control of the effects observed.
Recent papers have also dealt with the formation of the light induced defects in a-Si:H observed
by picosecond PA [39]; solving of the non-linear PA response taken at different excitation
photon energies [40]; elimination of the interference effects from photoinduced-transmission
decay curves of thin silicon films [41]; investigation of the picosecond photoinduced change in
the energy and time dependence of the complex dielectric constant [42]; exponential time
dependence of the photoinduced defect population growth [43]; and so on. These papers
usually do not explicitly consider a-Si.H gap states in the modelling of the processes observed.
For example, in [42] it has been stated that the photoinduced changes are consistent with a
model for injected carrier relaxation which combines extended-to-tail and tail-to-tail thermal
carrier transitions and which uses an optical probe sensitivity to carriers in the localised tail
states.

CONCLUSION

Values for the deep defect density determined from PDS or CPM measurements may vary
significantly on the same sample depending on the method of data analysis used. Experimental
conditions under which they yield comparable results should be used in order to obtain reliable
data. To our knowledge, in the papers devoted to a-Si:H, the steady state photoinduced
absorption technique has not been frequently used during the last years. Two approaches exist
for the theoretical description of the corresponding spectral behaviours. The first is applied for
the measurements performed above 80 K and the second for 1.8 K. The PA results are
interpreted in terms of the 'standard' defect model.

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Previous Page

3.6

Information on gap states in a-Sii_xCx:H from ESR, LESR,


constant photocurrent and photothermal deflection
spectroscopies
F. Giorgis, F. Giuliani, CF. Pirri, E. Tresso and U. Coscia
June 1997

INTRODUCTION

The electronic properties of a-Sii-xCx:H films are strongly dependent on band tails and defect
levels inside the pseudo-gap of the alloy. In high quality a-Si:H films Urbach energies as low as
45 meV and defect densities lower than 1016 cm"3 are obtained. The widening of the gap in
a-Sii-xCx:H, due to the addition of carbon to the a-Si:H network, is accompanied by
compositional and structural disorder. As a consequence, new localised states inside the gap
are created. Knowledge of the defect creation and the DOS within the gap of a-Sii-xCx:H alloys
is still very poor due probably to the complexity of carbon configurations. Skumanic et al [1]
report that the addition of carbon does not appreciably change the density of states in the gap at
the band edge. On the other hand, it has been shown that on alloying silicon and carbon the
films present a greater density of gap states [2,3-5]. The determination of the defect
distribution in the gap is an important step for the improvement of electronic properties of the
alloy. Many techniques such as space charge limited current (SCLC), deep level transient
spectroscopy (DLTS), time of flight (TOF), post transit time of flight (PTTOF), thermally
stimulated current (TSC), modulated photocurrent (MPC) and the constant photocurrent
method (CPM) cannot be conveniently applied to a-Sii_xCx:H films due to the low electrical
conductivity and photoconductivity of such films.
Until now, the most important techniques for inferring information on gap states in a-Sii-xCx:H
films have been electron spin resonance (ESR) [6], photothermal deflection spectroscopy (PDS)
[1,7-9], the constant photocurrent method (CPM) [10] and optical modulated spectroscopy
(OMS) [11] techniques, which have the ability to provide quantitative information on the
density of states. However, disagreements have been observed between values of defect density
obtained by optical techniques and by electron spin resonance (ESR); this can be attributed to
the more complex defect distribution in a-Sii-xCx:H alloys [12].

GAP STATES FROM ESR AND LESR

Electron spin resonance has been applied to a-Sii-xCx:H in all the compositional range in order
to extract the defect density present in the pseudo-gap [6,12,14,15]. Such a technique is
sensitive to all the paramagnetic states with unpaired spin. In a-Si:H the only paramagnetic
states are the silicon dangling bonds (sp3 defects). However, when carbon is incorporated it can
be bonded in the sp3 and sp2 configuration, yielding sp3 dangling bonds, C isolated sp2 dangling
bonds and odd sp2 C clusters [16].

Ns

[cm"3]

FIGURE 1 shows the spin densities N 8 as a function of carbon content for a-Sii_xCx:H films.
The spin density increases with increasing carbon content. For specimens of poor electronic
quality, there is a monotonic increase from values around 1016 cm"3 for x = 0 up to values of
1019 - 1020 cm'3 for x > 0.5. For device-quality a-Sii-xCx:H deposited by PECVD, N 8 sharply
increases for 0 < x < 0.2, after which it saturates around 1018 cm"3.

C/(C+Si)
FIGURE 1 Spin density as a function of carbon content for 3-Si^xCx films. Solid line with open circles and
dashed line with closed circles - Bullot et al [6]; closed squares - Giorgis et al [13]; + - Demichelis et al [18];
dashed line with open triangles - Liedtke et al [14]; dashed line with stars - Akita et al [15].

The Lande factor g shifts from 2.0055 - 2.0048 for Si-rich a-Sii-xCx:H to 2.0027 for C-rich
a-Sii-xCx:H due to defect topology and to surrounding composition around the paramagnetic
defects. Molecular orbital calculations show that C dangling bonds are more probable than Si
dangling bonds for C-rich alloys [ H ] . The magnetic field linewidth AH of ESR spectra strictly
depends upon the deposition conditions. For instance, in a-Sii-xCx:H deposited by PECVD
using SiH4 + C2H2 gas mixtures it is around 7 - 8 G for C-rich films, increases monotonically to
10 G for x - 0.5 and reaches values of about 17 G for C-rich films (x ~ 0.9). This could be due
to a wide g-value distribution resulting from structural inhomogeneity. In specimens grown by
PECVD using SiH4 + CH4 the linewidth starts at the same values as for Si-rich alloys,
decreasing to 4 - 5 G for x - 0.5. This can be attributed to the large presence of sp 2 defects,
which are much more delocalised than sp3 defects yielding narrower ESR lines [19].
An analysis of the magnitude of the ESR signal, corrected for the Curie law, versus sample
temperature in the range 140 - 300 K was performed on a-Sii.xCx:H (0.05 < x < 0.29). A
mid-gap gaussian shaped Si dangling bond DOS with correlation energy 0.3 eV and halfwidth
ranging from 0.11 to 0.25 eV was found [18].
A useful tool for detecting charged dangling bonds in tetrahedrally amorphous semiconductors
is light-induced ESR (LESR), because charged defects become neutral by capturing photoexcited carriers. Very poor results have been reported in the literature up to now on LESR in

a-Sii-xCx:H and the reports are limited to Si-rich specimens [20,21]. It was found that the
incorporation of C does not increase the fraction of charged defects.

GAP STATES FROM PDS AND CPM TECHNIQUES

a [cm*1]

FIGURE 2 reports typical PDS absorption coefficients versus photon energy for a-Sii-xCx:H
films grown by PECVD7 having carbon content x ranging from 0 to 0.9 [13]. The PDS and
CPM methods present some differences in the determination of absorption coefficients. PDS is
sensitive to all the electronic transitions, while CPM detects only transitions able to provide free
carriers in the conduction band [22]. Moreover CPM is a technique based on photocurrent
detection, so only a-Sii_xCx:H films having optical gap below 2.4 eV (x < 0.2) can be
successfully analysed.

E[eV]
FIGURE 2 Absorption coefficient spectra obtained by PDS for a-Sii_xCx:H having different carbon content
[13]. Closed squares - x = 0.21; x - x = 0.44; open circles - x = 0.58; open diamonds - x = 0.70.

It is possible to observe that the edge of the extended states to extended states transitions of the
absorption coefficient moves to higher energies as carbon increases. In all the spectra the three
typical regions, well known in a-Si:H, can be seen:
(a)
(b)
(c)

fundamental absorption region;


Urbach tail;
excess absorption region.

The gap defect density ND can be obtained by PDS or CPM spectra by calculating the integral
of the absorption coefficient in the low energy region, Ia, after subtracting the extended Urbach
tail absorption [23].

ND

[cm"3]

In a-Sii-xCx:H alloys the defects lying near the Fermi level can arise from unsaturated Si or C
bonds (Si3 or C3) or odd n clusters [16]. Ia can be related to the density of gap states close to
the Fermi level by ND = K Ia, where the calibration factor K is usually taken to be equal to that
of a-Si:H: KPDS = 0.95 x 1016 for the PDS technique [23] and KCPM = 1.9 x 1016 for the CPM
technique [24]. However, it was suggested that the use of a constant calibration factor K for
the evaluation of defect density by PDS has to be treated with some caution when carbon
alloying increases [12].

C/(C+Si)
FIGURE 3 Gap defect density evaluated by PDS for a-Sii-xQiH film versus carbon content x from: solid line
with closed squares - Baker et al [25] CH4; solid line with open squares - Baker et al [25] H2 + CH4; solid line
- Boulitrop et al [26] CH4; large dashed line - DellaSala et al [27] CH4; small dashed line - Schmidt et al [28]
CH4; solid line with closed triangles - Cicala et al [29] a-SiC:H,F; dotted line with closed triangles - DeSalvo
et al [30] CH4; dotted line with open triangles - DeSalvo e al [30] H2 + CH4; x - Giorgis et al [13] C2H2.

ND values obtained by excess absorption of PDS or CPM spectra are summarised in FIGURE 3
as a function of carbon content x for a-Sii-xCx:H films deposited by PECVD [5,25-31].
FIGURE 4 reports the Urbach tail energies as a function of carbon content x for the same
samples as in FIGURE 3, when available. We can observe three features:
(a)
(b)
(c)

the data have a large spread which indicates that a-Sii-xCx:H films have properties
strongly dependent on deposition conditions and processes;
Urbach tail energies increase as carbon content increases;
the defect density increases by orders of magnitude as carbon is incorporated into the
alloy, and consequently as the optical gap increases. Starting from a gap defect density
similar to that of device quality a-Si:H? around 1015 cm"3, for x < 0.05 the defects sharply
increase reaching values around 1017 cm"3 or above for x in the range 0.1 - 0.4.

[meV]
Eu

C/(C+Si)
FIGURE 4 Urbach energy evaluated by PDS for a-Sii_xCx:H film versus carbon content x from: solid line with
closed squares - Baker et al [25] CH4; solid line with open squares - Baker et al [25] CH4; solid line with closed
diamonds - Cicala et al [29] a-SiC:H,F; solid line - Boulitrop et al [26] CH4: dotted line with closed triangles DeSalvo et al [30] CH4; dotted line with open triangles - DeSalvo et al [30] CH4; x - Giorgis et al [13] C2H2.

The literature reports strong efforts devoted to the deposition of a-Sii_xCx:H materials having a
defect density closer to that of device-quality a-Si:H and to the understanding of the effects of
deposition techniques and parameters on defect formation in the alloy [32,33]. However, no
final results have yet been reached.
As mentioned above, PDS spectra contain contributions from optical transitions which are not
detected in CPM measurements [10,22,34]. The optical absorption coefficient is indeed the
convolution of the occupied and empty electron density of states [35]. CPM detects only the
electron transitions from the occupied states to the conduction levels, while PDS detects all the
electronic transitions. A deconvolutive procedure [36] has been applied to the sub-gap
absorption spectra of a-Sii_xCx:H films with x below 0.24 in order to get information on the
energy distribution of the occupied and empty electron density of states above and below the
Fermi level.

CONCLUSION

ESR, LESR, PDS and CPM techniques on a-Sii-xCx:H have been reviewed. They are powerful
tools for the determination of information on gap states.
By ESR the density and environment of unsaturated bonds have been studied, and by PDS and
CPM states close to the Fermi level and close to the valence and conduction edges have been
investigated.

All the studies performed confirm that a-Sii.xCx:H alloy is a material with a defect density and
structural disorder which increase as carbon is introduced into the amorphous network. Much
work is needed for the production of material suitable for electronic applications.
Few data are available for the LESR technique, and further work is encouraged.

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N. Ishi, M. Kumeda, T. Shimizu [ Solid State Commun. (USA) vol.41 (1982) p. 143 ]
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vol.205 (1996) p. 169]

3.7

Information on gap states in a-Sii_xNx:H from ESR, LESR


and photothermal deflection spectroscopies
F. Giorgis, F. Giuliani, CF. Pirri and E. Tresso
June 1997

INTRODUCTION

Silicon-nitrogen alloys have been mainly studied at stoichiometric composition for their
insulating and passivating properties. Only recently a-Sii-xNx:H with x ranging from 0 to 0.57,
corresponding to optical gaps from 1.8 to 5.2 eV, have been proposed as wide bandgap
semiconductors in place of a-Sii_xCx:H [1,2]. However the electronic quality of a-Sii-xNx:H is
still too poor for application in devices. Information on gap states is thus instrumental in
attempting a material optimisation. For instance, the presence of deep trapping centres in
stoichiometric nitride, depending on the particular device applications, can be either
advantageous (in memory devices) or deleterious (in thin film transistors). Electron spin
resonance (ESR), light-induced electron spin resonance (LESR) and photothermal deflection
spectroscopy (PDS) are the techniques applied most for gap state characterisation, even if few
data are available for material having low nitrogen content.

GAP STATES FROM ESR AND LESR

a-Sii-xNx:H films can have two kinds of defect: the silicon dangling bonds, threefold
coordinated, and the nitrogen dangling bonds, twofold coordinated. From a theoretical point of
view each defect centre is amphoteric, with three charge states -, 0 and + for sites respectively
doubly-, singly- and un-occupied.
The ESR technique is sensitive only to neutral states. The g value and the linewidth AH,
characteristics of the neutral silicon dangling bond signal, can be continuously varied from the
a-Si:H values (g = 2.0055, AH = 7 G) to those of stoichiometric nitride (g = 2.0025, AH = 12.5
G). Such a shift has been theoretically predicted considering the effect of replacing Si atoms by
N atoms as nearest neighbours of the spin site [3]. For Si rich alloys, different defect
configurations, consisting of dangling bonds lying on silicon atoms backbonded to three Si
atoms, or to two Si atoms and one N atom, or to one Si atom and two N atoms, or to three N
atoms, were verified to be simultaneously present through the investigation by ESR of the
metal-nitride-silicon structure under electrical bias [4], that gave an inhomogeneous distribution
of discrete components at different g values. Approaching stoichiometry, the Si dangling bond
centres mostly consist of unpaired spins on Si atoms backbonded to three N atoms, termed in
the literature K centres [5], which are the dominant defects responsible for the trapping
observed in a-Si3N4:H films used in non-volatile memory devices and a-Si.H thin film transistors
[6]. Silicon dangling bonds are observed in their neutral state in a-Sii_xNx:H films of all
compositions. FIGURE 1 shows the spin density versus the nitrogen content of samples
deposited by sputtering and PECVD [1,7,8].

Ns [cm*3]

X
FIGURE 1 Spin density of a-Sii_xNx:H films. Closed circles and x - sputtered a-SiN [7]; open circles and closed
triangles - PECVD a-SiN [7]; open triangles - sputtered a-SiN [8]; open diamonds and closed diamonds PECVD a-SiN [8], dotted line and open squares - PECVD a-SiN [I].

The ESR measurements underestimate the defect density; in fact, in Si-rich samples the addition
of nitrogen strongly increases the charged defects, ESR inactive, as revealed by LESR [9]. The
density of neutral silicon dangling bonds can be increased by UV illumination, for a-Sii-xNx:H in
the whole compositional range [10-12]; however, under irradiation, the spin creation time
strictly depends upon the film stoichiometry: it takes only 3 min to generate the maximum spin
density in stoichiometric film, 2 x 103 min for x = 0.33, and 105 min for x = 0 [11]. Thus, it is
argued that at least two different mechanisms are responsible for spin creation in N-rich and
Si-rich films. The spin density attributed to the K centre in stoichiometric films is
photobleachable with light having photon energy below the optical gap; such a phenomenon is
temperature independent and is reversible [13]. Thus, in N-rich films it is likely that during
irradiation, only optical rearrangements of the charges in pre-existing K defects occurs. Such an
idea is supported considering that no change in the infrared spectra during illumination occurs
as evidence of structural evolution [14]. On the other hand, in Si-rich films, some light-induced
changes in bonding structure have been observed [15] that could suggest models based on bond
breaking or hydrogen switching between N and Si atoms induced by UV irradiation.
Nitrogen dangling bonds are very easily distinguished from the silicon ones by their three-line
ESR hyperfine spectrum [16]. They appear in N-rich films, becoming the dominant
paramagnetic defects in a-SisN4:H, only after annealing at T = 600 - 7000C and subsequent UV
illumination [16,17]. Since the N centre photo-creation kinetics are independent of the
illumination temperature, following a stretched exponential function versus time, the spin
density increase is simply believed to be due to an induced neutralisation of pre-existing charged
defects.

For both the Si and N defects the sign of the correlation energy is still an open question. At
stoichiometry, Robertson et al [18] postulated the charging of N and K centres having a positive
correlation energy, owing to an electron transfer between K and N defects at equilibrium. The
K centre energy levels lie at the midgap without dependence on film composition. The N
centres are located slightly above the valence band edge Ev for films close to stoichiometry or
below Ev for x < 0.5, thus existing permanently in their fiilly-occupied ESR undetectable states
[19]. The annealing sharpening of the valence band tail makes the N dangling bonds level lie
deeper in the gap, stabilising such centres for stoichiometric films. The nitrogen dangling bonds
have never been detected by ESR in as-deposited UV irradiated a-Sii-xNx:H films at room
temperature. Instead, irradiation was found to create both K and N paramagnetic centres, with
K centres in excess, by performing the ESR measurement on as-deposited stoichiometric nitride
at low temperature (110 K), since the low temperature inhibits the N paramagnetic centre decay
by hole emission from the N centre [20].
Other groups obtained ESR and capacitance-voltage measurement results in favour of a
negative correlation energy for silicon dangling bonds [21]. On the other hand, a potential
fluctuation exceeding the positive correlation energy of Si and N defects, due to compositional
heterogeneity [22] or to random orientation of polar bonds [23], can justify charged and neutral
defect co-existence.

GAP STATES FROM PHOTOTHERMAL SPECTROSCOPY

Due to the presence of charged unsaturated defects and due to the difficulty in determining the
sign of the correlation energy for both nitrogen and silicon dangling bonds, it is very important
to measure the total and the charged defect densities in a-Sii.xNx:H. The total density of
Si-centred defects can be determined by photothermal deflection spectroscopy (PDS), which is
able to detect the optically induced electronic transitions from occupied to empty levels. In
addition, the PDS technique can give information on the band edge widening through the
Urbach energy. FIGURE 2 reports typical absorption coefficients obtained by PDS techniques
for a-Sii_xNx:H having different nitrogen content [24]. As for all the silicon based
semiconductors three typical regions can be detected:
(a)
(b)
(c)

fundamental absorption region;


Urbach tail;
excess absorption region.

The total Si-centred defect density ND has been evaluated for a-Sii-xNx:H by calculating the
energy integral of the excess absorption region Ia. The calibration factor between ND and Ia
has been taken to be similar to that of a-Si:H simply scaled for the refractive index [25-27]. On
the other hand, such a calibration factor is also affected by the oscillator strength and material
inhomogeneity, so that the total silicon defect density as extracted from Ia has to be treated
with caution. FIGURES 3 (a) and (b) show the total defect density ND and the Urbach energies
Eu for a-Sii-xNx:H with x ranging from 0 to 0.57 [24,26-28]. Unfortunately, only a few studies
on PDS determination of defect densities for a-Sii_xNx:H are available. We can observe that,
except for the data of [26] where ND ranges from about 3 x 1016 cm"3 at x = 0 to 2 x 1018 cm'3
close to stoichiometry, the defect density of a-Sii.xNx:H has been fixed at values below or
slightly higher than 1017 cm"3 up to stoichiometry, while the Urbach energies (FIGURE 3(b))

a [cm"1]

Photon energy

[eV]

FIGURE 2 PDS absorption spectra for a-Sii_xNx:H films [I]. Solid line - x = 0.05; small dashed
line - x = 0.32; solid line with open squares - x = 0.38; large dashed line - x = 0.42.

monotonically increase with the nitrogen content. Some groups [26,29] tried to decompose
PDS spectra for a-Sii-xNx:H (0 < x < 0.59) into a weak absorption region ((c) excess absorption
region), ascribed to defect-conduction band transitions, and an exponential region ((b) Urbach
tail), ascribed to valence band tail-conduction band transitions. They found that silicon dangling
bonds are located around midgap in all the compositional range. On the other hand, the defect
absorption region extends to photon energies much smaller the half the subgap [14,30].
Usually, in homogeneous amorphous semiconductors, transitions between localised states must
be excluded as the optical matrix element is too small for transitions between spatially
correlated states. However, assuming that a-Sii.xNx:H is a compositionally heterogeneous
material with spatial bandgap fluctuations [22], the localised states are spatially correlated
allowing optical transitions also between states lying in the subgap absorption region. Yet, a
spread in Si dangling bond energy levels is expected due to the gap centre fluctuations with
respect to the Fermi level and to the variation of defect levels relative to each local gap centre.
Such considerations justify the observed spread of the absorption level at low photon energy.
The Urbach edge and the bandgap transitions of different regions can overlap yielding the
unusually large apparent Urbach energy for films with high N content.

Ey [meV]

ND [cm3]

(a)

(b)

X
FIGURE 3 Total Si-centred defect density (a) and Urbach energies (b) for a-Si!_xNx:H films grown by PECVD.
Solid line - Iqbal et al [26]; dashed line - Steward et al [27]; open and closed symbols - Giorgis et al [24];
dashed-dotted line - Kanicki et al [28].

CONCLUSION

Information on gap states inferred from ESR, LESR and PDS measurements on a-Sii-xNx:H has
been reviewed.
By ESR the presence of neutral silicon dangling bonds was shown in all the compositional
range. UV irradiation creates further paramagnetic Si dangling bonds through charge
redistribution in pre-existing defects for films close to stoichiometry while for Si-rich specimens
real creation of Si defects is arguable.
N dangling bonds, owing to their energy level position close to the valence band edge, were
detected by ESR only at low temperature or after annealing the samples at 500 - 600 K.
The sign of the effective correlation energy for the defect centre is still an open question and
several models were proposed.
PDS measurements yield the absorption coefficient spectra. At photon energy below the
fundamental absorption an exponential absorption region is observed, due to valence band tailconduction band optical transitions (Urbach region), whose energy slope decreases with

increasing nitrogen content. The absorption curve exhibits a kink and flattens out for lower
photon energy (excess absorption region), due to optical transition involving defect centres,
whose magnitude does not have a defined trend versus the atomic composition.
The energy integral excess absorption Ia should yield the total defect density ND; on the other
hand, the calibration factor between ND and Ia could be strongly affected by refractive index,
oscillator strength and material heterogeneity.

REFERENCES
[I]
[2]
[3]
[4]
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[9]
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[12]
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[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]

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p.1730]
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D. Jousse, J. Kanicki, JH. Stathis [Appl. Phys. Lett. (USA) vol.54 (1989)p. 1043 ]
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M.S. Crowder, ED. Tober, J. Kanicki [Appl. Phys. Lett. (USA) vol.57 (1990)p.1995 ]
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vol.70 (1991) p.346]
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F. Giorgis et al [ Philos. Mag. B (UK) (submitted, 1997) ]
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J. Kanicki, W.L. Warren [ J. Non-Cryst. Solids (Netherlands) vol. 164-166 (1993) p. 1055 ]
H. Fritzsche, Y. Nakayama [ Philos. Mag. B (UK) vol.69 (1994) p.359 ]

3.8

Valence band offsets of a-Sii_xCx on c-Si and a-Si:H


C. Bittencourt and F. Alvarez
October 1997

INTRODUCTION

The most important parameters which can be controlled in a heterojunction interface are the
forbidden gaps of the two semiconductors, EgA and EgB. The difference, AEg = EgA - EgB, gives
rise to valence (AEy) and conduction (AEC) band discontinuities. These parameters play a
leading role in the transport and optical properties of the interface and, therefore, the device
performance. How is AEg shared between (AEv) and (AEC)? This is a fundamental question and
although the physical origins of the lineup are still elusive, it continues to be one of the most
important problems in heterojunction research [I]. Due to the great importance of band
discontinuity in heterojunction devices research, a variety of experimental techniques have been
applied to determine this fundamental parameter. These techniques are based on transport,
optical and photoemission measurements. A detailed description of these measurements can be
found in [I]. Among these techniques, photoemission spectroscopy is probably the most widely
used in bandgap discontinuities studies. Generally speaking, the limitations of photoemission
spectroscopy in the determination of the bandgap offset are the resolution and the signal
dynamic range of the apparatus. Recently, however, a modern version of photoelectric yield
spectroscopy that combines high resolution and a high dynamical range has been proposed and
successfully applied to determine the band lineups at semiconductor interfaces [2].
With regard to the energy band discontinuities discussed in this Datareview, it is important to
remark that very different conclusions are reported in the literature. Furthermore, even though
equivalent experimental methods are applied, different results are reported. Since band offsets
are notoriously difficult to measure, experimental inaccuracies play some role in those
divergences. Moreover, chemically absorbed species, microdiffusion, defects, contaminants and
interface reconstruction at the junction boundary influence the discontinuities, i.e. the
preparation conditions of the constituent materials and the cleanliness of the substrate surface
have a substantial influence on the final results. To overcome these inconveniences, some
authors studied the heterostructure by depositing and analysing the interface in situ.
In recent years, more attention has been devoted to studying hydrogenated amorphous
interfaces. This is because of the importance of amorphous interfaces in devices such as solar
cells, heterojunction bipolar transistors and the silicon dioxide interface widely used in the
microelectronics industry [3]. Moreover, the flexibility of the amorphous network allows the
bandgap of the heterostructure constituents to vary continuously without matching problems.
However, a variety of results of the bandgap offsets are also reported in amorphous
heterostructures. Indeed, since most of the experimental work provides very little information
about structural properties of the amorphous material (e.g. hydrogen content), a wide scatter in
the experimental results can explain the differences among authors. For instance, Van de Walle
and Yang [4] in a theoretical investigation of the band lineups between crystalline and
amorphous silicon showed that the calculated results are very sensitive to hydrogen content.
These authors reported a valence-band offset between c-Si and an unhydrogenated a-Si layer of

-0.25 eV. For a hydrogenated layer with H content of 11%, these authors found a value of
+0.20 eV for the valence band offset. The effect of hydrogen seems to be to lower the position
of the valence-band edge by about 0.04 eV for each % of incorporated hydrogen. However, the
authors point out that it is not clear to what extent this conclusion can be generalised [2]. For
all these reasons, the aim of this Datareview is to review a restricted number of interfaces that,
in our opinion, are fairly well documented.
Throughout this Datareview we shall use the following sign convention:
(a)

AEv > 0 if the valence band edge of the smaller bandgap material lies above the valence
band edge of the greater bandgap material;

(b)

AEC > 0 if the band edge of the greater bandgap material lies above the conduction band
of the smaller bandgap material.

With these assumptions, the difference in the bandgap, AEg, is the sum of the band offset values,
i.e. AEg = AEv+ AEC.

a-Si:H/c-Si INTERFACE

Cuniot and Marfaing [5] studied the c-Si/a-Si:H interface by internal photoemission in a range
of temperatures between -15C and -148C, reporting a value of AEv - 0 eV. The amorphous
layer was deposited by sputtering on a c-Si substrate. Using the same technique for analysis,
Lequeux and Cuniot [6] investigated these interfaces with the silicon amorphous layer deposited
by plasma enhanced chemical vapour deposition (PECVD), obtaining similar results. In a more
recent work, the same group obtained AEv ~ 0.20 eV by current-voltage and photocurrentvoltage measurements [7]. No reference to hydrogen content was reported by the authors.
Essick and Cohen [8] studied a-Si:H/c-Si heterojunction Schottky diodes obtained by depositing
the amorphous layer by PECVD on crystalline substrates and analysed by a voltage filling pulse
technique. The orientation of the c-Si and the hydrogen content were not specified by the
authors. These authors reported a near zero conduction band offset of AEC = 0.05 + 0.05 eV
and a valence band offset of AEv = 0.58 + 0.02 eV. In a more recent work, Essick et al [9]
deduced both conduction and valence band offsets on metal/a-Si:H/c-Si heterostructures by a
junction capacitance technique. Two types of samples deposited by PECVD were studied by
these authors, namely, the conventionally amorphous silicon (optical gap of -1.75 eV) and the
material obtained by heavily diluting the starting gases during the discharge (optical gap of
-1.77 eV). They found AEv = 0.67 eV and AEC = 0.01 eV for the heterostructure with 12%
hydrogen content deposited when using the conventional material glow-discharge deposition
process. On the other hand, for the heterostructure containing the material deposited under
heavily hydrogen diluted conditions, yielding a 14% hydrogen content, AEv = 0.65 eV and
AFx = 0.13 eV. Part of the difference in the measured offsets could be ascribed to differences in
optical gaps.
Mimura and Hatanaka [10] measured the band discontinuities by internal photoemission for
PECVD a-Si:H/c-Si heterojunctions. In order to minimise photocarrier generation, the
amorphous silicon film was deposited as thinly as possible. These authors obtained

AEv = 0.71 eV and AEC = 0.09 eV. They noted that the sum of their AEC and AEv values
exceeded the bandgap difference between their a-Si:H and c-Si. The discrepancy was attributed
to the fact that in amorphous semiconductors the band edge is not clearly determined.
Eschrich et al [11] were able to determine the valence and conduction bandgap offsets at the
a-Si:H/c-Si interface by the comparison of simulated current-voltage curves and bias-dependent
spectral response characteristics of solar cells. The devices were prepared at different substrate
temperatures by PECVD. The samples were grown on n-type c-Si (100) substrate by
depositing intrinsic a-Si:H and p-type a-Si:H layers. Values of AEv = 0.465 eV and
AEC = 0.15 eV were reported by these authors for samples deposited at 1500C. On the other
hand, for samples deposited at 2500C, values of AEv = 0.49 eV and AEC = 0.175 eV were
obtained.
Recently Sebastiani et al [12] reported in situ studies using low energy yield spectroscopy
(LEYS) of a-Si:H deposited on c-Si substrates. The substrate surface was cleaned and carefully
characterised before depositing the a-Si:H layer by PECVD. These researchers reported a value
of AEv = 0.44 eV for the valence band discontinuity.
The above results are summarised in TABLE 1.
TABLE 1 Experimental bandgap discontinuities for the a-Si:H/c-Si interface.
AEy(QV)

0
0
0.20
0.58
0.67
0.65
0.71
0.49
0.44

AEc(eV)

Deposition
technique

Measurement
technique
IPE(C)
IPE
IxV<d)
VFP(e)
CxV0

0.385
0.05
0.01
0.13
0.09
0.175

FECVD00
PECVD
PECVD
PECVD
PECVD (H2 dilution)
PECVD
PECVD

IPE
SR^ simulation

0.16

PECVD

CFSYPS00

Comment

[H] 12% content


[H] 14% content
Independent substrate
temperature
Deposition in situ

Ref
[5]
[6]
[7]
[8]
[9]
[10]
[10]
[H]
[12]

(a) Sputtering; (b) Plasma enhanced chemical vapour deposition; (c) Internal photoemission spectroscopy;
(d) Current-voltage measurements; (e) Voltage-filling pulse; (f) Capacitance-voltage measurements;
(g) Spectral response; (h) Constant final state photoemission yield spectroseopy.

The observed spread in the values of TABLE 1 probably stems from the quality of the surface
of the crystalline substrate, the different hydrogen content of the amorphous layer and, generally
speaking, different deposition conditions. Another important point to consider is that while
reasonable numbers of defects have been shown to have little effect on the lineup, dopant
impurities can be concentrated at the interface to give an appreciable local dipole, altering the
effective band lineup [I]. Moreover, most of the reported values were obtained by depositing
the silicon amorphous layer on crystalline substrates in standard vacuum systems. Therefore,
the heterojunctions are probably contaminated, accounting, in part, for the scattering in the
experimental results.

a-Sii_xCx:H/c-Si INTERFACE

Brown et al [13], using LEYS, reported a comprehensive study of the valence and conduction
band discontinuities at the interface a-Sii.xCx:H/c-Si(100) for 0 < x < 0.50 (TABLE 2). The
heterojunctions were grown in situ by PECVD on mirror-polished, p-type silicon (lOO)-oriented
substrates. Before deposition, the substrates were cleaned and characterised in a UHV system,
showing a 2 x 1 reconstruction.
TABLE 2 Values of AEV for the C-SiZa-Si1 ^CxM heterojunction [13].
The carbon concentration, x, and the optical gap, Eg, are also indicated
X

0.10
0.25
0.35
0.50

E g (eV)
1.8
1.9
2.1
2.3

AEv (eV)(a)
0.56
0.73
0.78
0.97

AEv (eV)^
0.56
0.72
0.75
1.00

AEc(eV)
0.14
0.10
0.22
0.23

(a) and (b) are related to different procedures used by the


authors in the determination of the band offset [13].

Cuniot and Lequeux [7], using current-voltage and photocurrent-voltage measurements,


reported a valence band discontinuity of AEv = 0.27 eV for a PECVD overlayer of a-Sii-xCx:H
having an optical gap of 1.9 eV.
Essick et al [9] inferred AEv values using a combination of junction capacitance techniques on
two sets of metal/a-Sii-xCx:H/c-Si heterostructure samples containing several carbon
concentrations (TABLE 3). The first set was deposited using the conventional PECVD process
and the second set by heavily diluting the starting gases with hydrogen during the glow
discharge deposition.
TABLE 3 Conduction (AEy) and valence-band (AEC) offset in a-Sii ^CxIHZc-Si interfaces [9].
The main deposition conditions, hydrogen content, H, and optical gap, Eg, are also indicated.
X

0.00(a)
0.06
0.07
0.00(a)
0.18
0.26

Deposition
conditions
HD^
HD
HD
GD(d)
GD
GD

H
(%)
14
26
27
12
38
43

(eV)
1.77
2.0
2.1
1.75

Deposition
temp. (0C)
200
200
200
260
260
260

AEv
(eV)
0.65
0.80
0.80
0.67
0.70
0.83

AEC
(eV)
0.13
0.12
0.20
0.01
0.07
0.10

(a) The zero carbon concentration results are included for completeness; (b) HD: High dilution
with hydrogen; (d) GD: Low hydrogen dilution (standard glow discharge).

A valence band offset AEv = 0.35 eV was determined by Magafas et al [14] from currentvoltage and capacitance-voltage measurements in free hydrogen overlayer samples. The
heterojunction studied by these authors was obtained depositing a material of 1.35 eV optical
gap by sputtering on p-type c-Si. The sputtering target consisted of a SiC alloy containing
66 wt.% Si and 34 wt.% C. Unfortunately, as the carbon content was not specified, it is not
possible to make a straightforward comparison with other results available in the literature.

a-Sii_xCx:H/a-Si INTERFACES

Fang and Ley [15] studied the a-Si/a-Sii-xCx:H heterojunction by the technique of indirect
photoemission. The films were deposited in situ at room temperature by DC sputtering. A
constant valence band discontinuity AEy = 0.8 + 0.1 eV is measured for 0 < x < 0.4. Above
x ~0.4, AEy increases linearly, extrapolating to AEv = 1.95 + 0.15 eV for x = 1. Upon
dehydrogenation by annealing at 6500C7 these authors reported AEv increasing from 0.25 eV
(x = 0) up to 1.5 eV for samples with x = 1.
Hirai et al [16], using X-ray photoelectron spectroscopy (XPS), inferred the valence-band
offsets of a-Sio.2Co.8:H/p-(a-Si:H) and a-Sio.2Co.8:H/n-(a-Si:H) heterojunctions. The samples
were prepared by PECVD and different doping levels of the a-Si:H overlayer. The values of
AEv for a-Sio.2Co.8:H/p-(a-Si:H) are estimated to vary from 1.2 to 1.5 eV on increasing
p-doping. On the other hand, for a-Sio.2Co.8:H/n-(a-Si:H), AEv - 0 . 7 eV. The conduction band
offset of a-Sio.2Co.8:H/p-(a-Si:H) heterojunctions, AEC, changes from 0 to 0.3 eV on decreasing
doping. Finally, for a-Sio.2Co.8:H/n-(a-Si:H), AEC was found to be 0.8 eV. The authors
suggested that a Fermi level pinning at the interface of heterojunctions probably has an
important role in the measured band offset.

CONCLUSION

The bandgap offset of heterojunction structures is an important parameter in determining the


performance of the devices. The valence-band and conduction-band offsets of some
amorphous/amorphous and amorphous/crystalline semiconductor heterojunctions are
summarised in this Datareview. The scattering of the reported data is probably due to different
hydrogen contents, surface contamination and/or preparation conditions of both substrate and
overlayer.

REFERENCES
[I]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[II]
[12]

M. Kim, HJ. Osten [ Appl. Phys. Lett. (USA) vol.70 (1997) p.2702 ]; G. Margaritondo,
P. Perfetti [ Heterojunction Band Discontinuities: Physics and Devices Applications Eds F.
Capasso, G. Margaritondo (North-Holland, New York, 1987) p.61 ]
M. Sebastiani, L. Di Gaspare, G. Capellini, C. Bittencourt, F. Evangelisti [ Phys. Rev. Lett.
(USA) vol.75 (1995) p.3352 ]
J. Robertson [ J. Non-Cryst. Solids (Netherlands) vol.97&98 (1987) p.863 ]
CG. Van de Walle, L.H. Yang [ J. Vac. Sci. Technol B (USA) vol.13 (1995) p. 1635 ]
M. Cuniot, Y. Marfaing [ J. Non-Cryst. Solids (Netherlands) vol.77&78 (1985) p.987 ]
N. Lequeux, M. Cuniot [ J. Non-Cryst. Solids (Netherlands) vol. 114 (1989) p.555 ]
M. Cuniot, N. Lequeux [ Philos. Mag. B (UK) vol.64 (1991) p.723 ]
J.M. Essick, J.D. Cohen [Appl. Phys. Lett. (USA) vol.55 (1989) p.1232 ]
J.M. Essick, Z Nobel, Yuan-Min, M.S. Bennet [ Phys. Rev. B (USA) vol.54 (1996) p.4885 ]
H. Mimura, Y. Hatanaka [ Appl. Phys. Lett. (USA) vol.50 (1987) p.326 ]
H. Eschrich, J. Bruns, L. Elstner, C. Swiatkowski [J. Non-Cryst. Solids (Netherlands) vol. 164166 (1993) p.717]
M. Sebastiani, L. Di Gaspare, G. Capellini, C. Brttencourt, F. Evangelisti [ Phys. Rev. Lett.
(USA) vol.75 (1995) p.3352 ]

[13]
[14]
[15]
[16]

T.M. Brown, C. Bittencourt, M. Sebastiani, F. Evangelisti [ Phys. Rev. B (USA) vol.15 (1997)
p.9904 ]
L. Magafes, N. Georgoulas, A. Thanailakis [ Semicond. Sd. Technol. (UK) vol.7 (1992)
p.1363]
R.C. Fang, L. Ley [ Phys. Rev. B (USA) vol.40 (1989) p.3818 ]
M. Hirai, M. Kusaka, M. Iwami, F. Akao, M. Yoshimoto, H. Matsunami [ Philos. Mag. B (UK)
vol.60 (1989) p.51]

3.9

Electronic structure of a-Si:Ge:H


J.D. Cohen
October 1997

INTRODUCTION

Shortly after the realisation that hydrogenated amorphous silicon (a-Si:H) afforded the promise
of an economical photovoltaic technology, investigations began into the alloys of this material,
predominantly with Ge and C, to provide optical gap tunability. The addition of Ge in
particular allows one to reduce the gap from the 1.7 - 1.8 eV value (EG) for pure a-Si:H
continuously down to 1.0 eV. As was first demonstrated by Chevallier et al [1], and
subsequently by numerous other studies, the optical gap, EG, of a-Sii-xGex:H varies with Ge
fraction x roughly as: EG(x) = EG - yx, with y lying in the range 0.7 to 0.9. On the other hand,
much of the work in the early 1980s also suggested that the electronic properties of
a-Sii-xGexiH deteriorated prohibitively once the Ge fraction, x, became appreciable. By the
latter part of the decade, however, alloys with quite respectable electronic properties were being
produced with Ge fractions as large as 50 at.%. Several comprehensive reports were published
roughly a decade ago which provide a good assessment of the state of the technology at that
time [2-4]. They also provide an excellent set of references to the earlier work on these alloys,
as does a more recent report by Paul et al [5]. Progress in improving the properties of the
a-Si,Ge:H alloys has continued, with significant advances over the last five years, such that
there is now some indication that a distinct level of optimisation has been achieved. Indeed,
these a-Si,Ge:H alloy materials are now being incorporated as an integral component in many
commercial photovoltaic modules based on a-Si:H related materials. In this Datareview I will
try to highlight some key aspects of the improvements that have occurred during this latter
period.

MOBILITY GAP STATE DISTRIBUTION

One popular method to assess the quality of the electronic properties in amorphous
semiconductors is via sub-bandgap optical absorption spectra and/or other sub-bandgap optical
spectroscopies (photocurrent methods, photocapacitance, etc.). This type of measurement can
be used to identify the optical gap and the bandtail slope, and to estimate the deep defect
density. Examples of such spectra for a-Si,Ge:H can be found in many studies [2-4,6-12]. The
value of the characteristic energy of the bandtail exponential distribution, called the Urbach
energy (Eu), provides a measure of the degree of disorder within the material [13-15]. In high
quality a-Si:H the value of Eu lies in the range 45 - 50 meV. Initially, much larger values were
found in the a-Si,Ge:H alloys [3,4,6,7]; however, recent progress, particularly at United Solar
Systems Corporation (TJni-Solar1) and at Harvard indicate that it is possible to obtain alloy
material with Urbach energies that are comparable to those of pure a-Si:H over nearly the entire
range of alloy compositions. These improvements seem to have resulted from varying gas
mixtures to employ disilane with high hydrogen dilution [16-18] and/or utilising alternative
electrode configurations to modify the degree of ion bombardment [5,12]. Examples of the
Urbach slope determined from sub-bandgap optical spectroscopy for different series of samples

URBACHENERGY (meV)

over the past decade are shown in FIGURE 1. The indicated low degree of structural disorder
of the Uni-Solar and Harvard a-Si,Ge:H samples has been corroborated by small angle X-ray
scattering (SAXS) measurements [5,11,18].
Xorox ff go
l w dtecharge
Princeton DC glow dtecharge
Princeton rf glow discharge
Stuttgart Triode system
IEC Pnoto-CVD
UnhSoa
l r rf GD
Harvard cathode GD .

GERMANIUM CONTENT

(at.%)

FIGURE 1 Urbach energies versus Ge content determined from sub-bandgap spectra for a-Si,Ge:H samples
taken from different studies. Sources for the data are: Xerox - [3], Princeton - [2], Stuttgart - [7], IEC - [8],
Uni-Solar - [9,10], Harvard - [11]. The dotted lines indicate the trend in Urbach energies from the studies
carried out before 1990, while the dashed lines indicate the range of values observed in high quality a-Si:H.

The sub-bandgap spectra exhibit a shoulder at lower optical energies which originates from
deep defects. This can usually be fit to a single Gaussian distribution to provide the energy
position and an estimate of the magnitude of this deep defect band within the gap. Several
studies indicate that the dominant optical transition associated with this band is centred within
about 50 meV of half the gap energy [4,8,9,11].

PROPERTIES OF THE DEEP DEFECTS

The nature of the deep defects is


indicated from the g-factor and
linewidth of the neutral defects that can
be detected by electron spin resonance
(ESR) measurements.
FIGURE 2
summarises the results of three studies
[3,19,20] that indicate a predominance
of Ge over Si dangling bonds by 1 to 2
orders of magnitude for a-Sii-xGe^H
alloys with x > 0.2. This is consistent
with the idea that some bonds will break
to relieve strain within the amorphous
network and that a lower energy is
needed to break a Ge rather than a Si
bond.

Ge/Si DANGLING BOND RATIO

Xerox GD
Marburg GD
JQIich/Calcutta GD

GERMANIUM CONTENT (at.%)


FIGURE 2 Ratios of germanium to silicon dangling bonds
determined from ESR studies of a-Si,Ge:H samples at
Xerox [3], Maiburg [19], andfroma recent
Mich/Calcutta collaboration [20].

DEFECT DENSITY

(cm*)

Quite a number of studies have shown that the number of deep defects increases nearly
exponentially with increasing Ge fraction, x. Densities of deep defects versus Ge content have
been determined from fitting the sub-bandgap spectra [2,4-6,11,16,21], from ESR [3,19,20],
and from junction capacitance profiling measurements [8-11,22]. Several examples of the
variation of defect density with Ge content obtained using the latter two methods are plotted in
FIGURE 3. The estimate of defect densities from the optical spectra, while useful within a
given series of samples, is less quantitative and so is probably not too reliable for comparison
between samples from different sources. Nonetheless, defect densities estimated from optical
spectra also agree quite well with the trend shown in FIGURE 3, indicating an exponential
increase, by roughly a factor of 300 overall, as x varies from 0 to 1 [2,4,5]. Theoretical
treatments based upon the thermodynamics of bond breaking and annealing have been able to
account for the observed exponential increase [2,23].

Xerox rf GD
Marburg rf GD
IEC photo-CVD
JGIich/CalcuttarfGD
Uni-Solar rf GD
Harvard cathodic GD
GERMANIUM CONTENT (at.%)

FIGURE 3 Defect densities versus Ge content determined from ESR measurements (open symbols)
and capacitance profiling studies (solid symbols). The sources of these data are given in the
captions for FIGURES 1 and 2. The dashed line is a guide to the eye.

FIGURE 3 also indicates that recent methods of a-Si,Ge:H production have led to a substantial
decrease in the density of deep defects. This seems to be directly linked to the general
improvement in network order reflected by the decrease in the Urbach energies (FIGURE 1).
One alternative model, the spontaneous bond breaking model of Stutzmann [24], has been
found to account very well both for the variation of defect density with the changes in Ge
fraction and also with Urbach energies at fixed Ge fraction [8,10,21]. It implies the simple
relation:

where ED is the energy position of the deep defect band within the gap (obtained, for example,
from the sub-bandgap optical spectrum), E* is a demarcation energy separating bandtail states
from deep defects, and N 0 is the density of states close to the valence band mobility edge. In
practice the parameters No and E* merely provide the freedom to adjust the overall magnitude
of the deep density to match experiment. However, a single choice of these parameters
provides very good agreement with the experimental data of FIGURE 3, as is illustrated in
FIGURE 4.

MEASURED DEFECT DENSITY

Xerox GD
IEC photo-CVD
Uni-Solar rf GD
Harvard cathodic GD

CALCULATED DEFECT DENSITY


FIGURE 4 Measured defect densities versus the value predicted from the spontaneous bond-breaking model
of [24]. The dashed line indicates perfect agreement. The data includes all the studies shown in FIGURE 3
for which the values of Urbach and optical gap energies were also available.

A final issue concerning basic deep defect properties concerns their charge state: specifically,
whether neutral defects prevail in intrinsic a-Si,Ge:H or whether there is a significant number of
positive and negative defects. Because of the increased likelihood of potential fluctuations in
the alloys, and the expected lower correlation energy for Ge versus Si dangling bonds, it is more
probable that charged defects would predominate in a-Si,Ge:H compared to a-Si:H. A couple
of research groups have recently been trying to address this issue by comparing different kinds
of sub-bandgap optical spectra within the same samples [25,26]. Some of this evidence for
charged defects seems reasonably compelling.

BANDTAILS

The Urbach energy derived from sub-bandgap optical spectroscopic measurements (discussed in
Section B) represents a convolution of the valence bandtail with the conduction bandtail and, as
is well known, reflects the bandtail with the broader distribution. This is the valence bandtail
and, in spite of some expected addition disorder due to alloying, it now appears possible to
produce a-Si,Ge:H material with valence bandtail widths as narrow as for pure a-Si:H (see
FIGURE 1).
The bandtails determine the effective carrier mobilities in amorphous semiconductors and,
indeed, studies of the temperature dependence of the electron and hole drift mobilities are the
most widely used methods to infer the conduction bandtail and valence bandtail distributions,
respectively [27]. Typically, it is found that the electron drift mobility decreases by about 2
orders of magnitude as the Ge content is increased to 0.4 [2,5,28-30]. Hole drift mobilities
have been more difficult to measure reliably; however, several studies indicate these are not
significantly different from values for pure a-Si:H [30,31], as is consistent with the nearly
identical Urbach energies in a-Si:H and the optimised a-Si,Ge:H alloys. Additional evidence for
a nearly constant value of the valence bandtail width over the full composition range has also
been obtained using total yield photoemission spectroscopy [32].

FIGURE 5 shows results of using the temperature dependence of the electron drift mobility to
obtain the conduction bandtail characteristic energy widths, EOc, for several a-Si,Ge:H samples
from different groups [28-30]. In contrast to the inferred nearly constant valence bandtail
widths, these results indicate a marked increase of EOc with Ge alloying, from about 25 meV for
x < 0.1 to 40 meV for x 0.5. An alternative approach, based upon the temperature
dependence of photoconductivity in a-Si,Ge:H samples from several sources, also concluded,
from the lack of thermal quenching of the photoconductivity at elevated temperatures, that the
conduction and valence bandtail must have similar widths [33].

Eoc

(meV)

ECD/Syracuse
Stuttgart
Siemens

OPTICAL GAP (eV)


FIGURE 5 Variation of the characteristic energy of the conduction bandtail with optical gap, taken from [30].
The dashed line is a guide to the eye. Sources of the data are: ECD/Syracuse - [30], Stuttgart - [29],
and Siemens- [28].

The inferred greater sensitivity of the conduction bandtail (compared to the valence bandtail) to
alloy disorder in a-Si,Ge:H alloys is an important and intriguing result which has been discussed
in some detail [5,30,34]. A few possibly related findings from studies of pure a-Si:H are (1) the
correlation between smaller optical gaps and larger Urbach parameters discussed by Cody [13],
(2) the apparently greater sensitivity of the conduction bandtail to thermal disorder as observed
in total yield photoemission studies [15], and (3) the dramatic decrease in drift mobility
observed in compensated material due to potential fluctuations [35]. Indeed, the likelihood that
long range potential fluctuations may have a dominant effect on the transport properties of the
alloys has been discussed by many authors [5,30,36-38]. A somewhat different explanation for
the lower electron mobility in the a-Si,Ge:H alloys is suggested from spin dependent
photoconductivity measurements [39] that show that significant densities of Ge related states
are incorporated into the conduction bandtail upon even a small (x = 0.1) amount of alloying.

LIGHT INDUCED DEGRADATION

An important aspect of the electronic structure in amorphous semiconductors is that it can


undergo (usually reversible) changes as a result of exposure to light [40]. Initially, such effects
were thought to be minimal in a-Si,Ge:H [41,42] but this was probably a result of the initially
quite poor electronic properties of these materials. As they have improved, light induced
degradation has been observed in a manner similar to a-Si:H, resulting in increased deep defect
densities and poorer photo-transport properties [2,16,25,43]. A number of recent studies

indicate that the stability in the a-Si,Ge:H can be enhanced by growth methods that decrease the
void fraction [44,45] or alter the hydrogen content [45-47].
While many of the issues of degradation in a-Si,Ge:H are essentially the same as in pure a-Si:H,
there are two aspects that seem noteworthy. First, there seems to be a total lack of degradation
in material with a high Ge fraction in spite of the fact that such alloys can now be grown with
defect densities significantly below 1017 cm"3. This is lower than the defect density in a-Si:H or
in the low Ge fraction alloys reached after degradation. It has been proposed [33,48,49] that
this is because the energy released through recombination becomes too small below a certain
optical gap energy to initiate the defect creation process. One study estimates this threshold to
be about 1.4 eV [48].
Secondly, there have been some fairly detailed studies to compare a-Si,Ge:H film properties
with photovoltaic device performance before and after light induced degradation [16,44]. It
was found that the degradation in device performance was more severe than could be accounted
for by the increase in defect density (disclosed via the changes in the sub-band-spectra). The
reasons for this are still unresolved but proposed explanations for this lack of correlation appeal
to effects due to voids or potential fluctuations [38], an increased role of charged defects [25],
or effects due to the variation of the Fermi level position across the device structures [50].

CONCLUSION

Improvements in quality of the a-Si,Ge:H alloys have resulted in materials with Urbach energies
as small as those for pure a-Si:H over the entire alloy range. Because the Urbach energy,
together with the gap energy, largely determine the deep defect density, this suggests that a
definite level of optimisation for these alloys has now been obtained. On the other hand,
aspects of the electronic properties of these alloys seem qualitatively different from pure a-Si:H.
These include: (1) a significantly decreased electron mobility possibly due to an increased role
of long range potential fluctuations, (2) more direct evidence for the presence of charged
defects, and (3) a lack of light-induced degradation for alloys with optical gaps below about
1.4 eV.
Space limitations mean that many other issues directly related to electronic structure,
particularly the many studies elucidating photo-transport and photoluminescence in the
a-Si,Ge:H alloys, have not been covered.

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CHAPTER 4

ELECTRONIC TRANSPORT
4.1
4.2
4.3
4.4
4.5

Dark conductivity in undoped a-Si:H deposited by


plasma-enhanced CVD methods
Mobilities in a-Si:H and its alloys
Thermoelectric power and Hall effect in a-Si:H
Steady state photoconductivity in a-Si.H and its alloys
Transient photoconductivity in a-Si:H and its alloys

4.1

Dark conductivity in undoped a-Si:H deposited by plasmaenhanced CVD methods


D.M. Goldie
July 1997

INTRODUCTION

The dark conductivity (a) of hydrogenated amorphous silicon (a-Si:H) is often determined to
evaluate the underlying electronic transport properties of thin-film samples. The experimental
measurement of a is normally performed using either a sandwich or coplanar electrode
configuration as illustrated schematically in FIGURE 1. Data collected as a function of
temperature T are conventionally plotted as log(a) against inverse temperature as shown
schematically in FIGURE 2 and analysed according to the Arrhenius expression:

(1)
where a o is the conductivity extrapolated to 1/T = 0 and kb is Boltzmann's constant. The
measured activation energy E a is normally interpreted as being equal to E* - Ef where Ef is the
Fermi energy and E* the energy at which majority carrier conduction occurs. Quoted
parameters from conductivity measurements are therefore the room-temperature conductivity
CJRT, O0 and E a . High-quality device grade a-Si:H is normally deposited by plasma enhanced
chemical vapour deposition (PECVD) methods. The particular conductance characteristics
displayed by PECVD a-Si:H are sensitive, however, to a number of factors and these are
summarised and reviewed in the following sections.

(a)

sub

(b)

V
sub

FIGURE 1 Electrode configurations for thin-film a-Si:H conductivity measurements,


(a) coplanar, (b) sandwich, V - supply voltage; A - current meter; sub - substrate.

Loga(S/cm)

slope =-E /k

1000/T(K" 1 )
FIGURE 2 Schematic illustration showing how the parameters aRT, E a and a o are extracted
from an analysis of a(T) data using EQN (1), RT - room temperature.

MEASUREMENT CONDITIONS

Bl

Experimental

The majority of conductance tests are performed using surface coplanar electrodes. Difficulties
with this arrangement have been highlighted by Dawson et al [1] who emphasise that for
particular contact geometries, carrier depletion in the a-Si:H film beneath the contact material
may distort the conductivity parameters deduced from a(T) data. To eliminate surface effects
arising from band-bending at interfaces in coplanar measurements, Meaudre et al [2] propose
the use of n+-i-n+ sandwich configurations to measure the true bulk conductivity properties of
a-Si.H. For radio-frequency (RF) PECVD material, they find a o < 700 S cm"1 from an analysis
of a(T) data. Similar ao magnitudes are found from field-effect measurements in TFT
structures [3,4] where the amount of band-bending may be externally controlled. Provided
sufficient care is taken to eliminate surface adsorption effects, the coplanar setup may still
provide realistic estimates of true bulk conductance parameters. This has been demonstrated by
Aker [5] who has evaluated the effect of chemisorption of ambient gas molecules on RF
PECVD a-Si:H films. This author demonstrated that under high vacuum conditions, the a-Si:H
surface possesses a hole accumulation layer caused by native surface oxides. Exposure to
ambient gases allows surface created electrons to tunnel through the oxide to a-Si:H gap states
and can result in a o increasing by almost 4 orders of magnitude. The effect of oxygen
ionosorption on the electrical properties of RF PECVD material has further been investigated
by Aoucher et al [6] who argue that oxygen may act as a donor or acceptor centre localised at
the film surface. This effect is shown to reduce GRT by a factor of 2 for undoped a-Si:H
specimens in which the majority carriers are electrons.

B2

Impurity Contamination

The role of oxygen unintentionally incorporated into the a-Si:H bulk during the deposition
process has been investigated by several groups [7-9] where it is generally agreed that oxygen
acts as a donor centre and increases <JRT. The increase in GRT is dependent upon the oxygen
concentration C(C^). As C(O2) increases from 1018 to 1021 cm"3, GRT is reported to increase
from 10"10 to 10"8 S cm"1 [7] and from 10"12 to 10"9 S cm"1 [8]. The increase in aRT is
accompanied by a corresponding decrease in E a . Shimizu et al [7] have additionally considered
the influence of nitrogen and carbon impurities on the electronic properties of their material and
find that nitrogen behaves in an analogous manner to oxygen, whereas carbon is, by
comparison, electronically inert.
B3

Thermal Metastability

The attempted extraction of E a (and a o ) conductance parameters by measuring the conductivity


as a function of temperature presents many potential difficulties. The majority of these derive
from the fact that a-Si:H prepared by plasma decomposition methods is believed to be
structurally far from equilibrium [10]. Some of the localised states are consequently not
permanently defined at the time of growth but may be placed in a glassy thermal equilibrium by
raising the material to high temperatures (>200C) for sufficiently long times (> few minutes).
It is, accordingly, possible to freeze-in specific high temperature states by rapid quench cooling
to room temperature where the re-equilibration time is much longer. Since the Fermi energy is
sensitive to the density of states (DOS) arising from such defect equilibration phenomena, E a
and the corresponding conductivity are expected to be sensitive to the thermal history imposed
during a(T) measurements. Fortunately, because the equilibration time is believed to be linked
to the movement of hydrogen in the a-Si:H lattice [11], the effect upon a(T) for undoped
material is relatively small. Convincing evidence of equilibration phenomena has nevertheless
been reported by Meaudre et al [12] on RF PECVD materials where GRT is found to decrease by
a factor of 3 following quench cooling from above 2300C and is accompanied by a detectable
increase in Ea of 0.02 eV. Interestingly, a second set of samples deposited under similar plasma
conditions, but using weak He dilution, displayed no evidence of equilibration from a(T) results
even after raising the sample temperature to 3000C.
The defect equilibration picture may possibly provide a unified explanation for high-temperature
'kink* effects reported in earlier studies of o(T) for RF PECVD a-Si:H [13-15]. This view
appears to have been experimentally confirmed by Toth et al [16] who performed a controlled
series of step-wise annealing experiments and demonstrated that the original high temperature
kink observed in as-deposited a-Si:H could eventually be removed provided sufficient time was
allowed for defect equilibration to be established at each annealing temperature.
B4

Light Induced Metastability

The defect DOS distribution in a-Si:H may also be modified as a consequence of the StaeblerWronski (SW) effect [17]. Prolonged light-soaking of undoped RF PECVD materials which
are n-type is reported to reduce GRT by several orders of magnitude and to increase E c by up to
0.3 eV as Ef is displaced towards mid-gap [18-20]. The defect states created by light exposure
are metastable and may be fully removed by high temperature annealing (>170C) for an
appropriate time period (>1 hr). Since the discovery of the phenomenon in 1977, considerable

effort has been directed towards understanding the microscopic origin of the defect generation
process (see [21] for an overview]). It has been suggested [22,23] that the creation of
metastable states relies upon the presence of impurities (O, C and N) but this is disputed by the
recent work of Kamei et al [24] who show that highly pure RF PECVD a-Si:H is still
susceptible to significant photodegradation effects. There are numerous claims in the literature
that the SW effect may be minimised by modifying either the plasma conditions [12,25,26] or
source gases [27-31] used during deposition. Several of these techniques have been observed
to influence the as-deposited dark conductivity characteristics of a-Si:H as discussed in Section
C.

SENSITIVITY OF a-Si:H CONDUCTIVITY PROPERTIES TO DEPOSITION


CONDITIONS

It is evident from the data reviewed in Section B that the dark conductivity of a-Si:H is sensitive
to post-deposition treatment. Early methods of depositing device-grade material were largely
confined to single chamber RF PECVD reactors operating at a fixed plasma excitation
frequency of 13.56 MHz where pure silane (SiH4) was used as a source gas. This basic
approach (often referred to as the glow-discharge method) has resulted in alternative PECVD
technologies emerging over the past ten to fifteen years. The influence of particular PECVD
deposition methods upon a for as-deposited a-Si:H is therefore considered in this section.
Cl

RF PECVD

It is universally accepted that the critical deposition parameter controlling the electronic
properties of RF PECVD deposited a-Si.H is the substrate temperature T8. Optimum devicequality material is usually produced from pure SiH4 if T8 is maintained between 2000C and
3000C. The dependence of a(T) on T8 has been extensively studied [14,31] where it was found
that GRT decreases from about 10"8 to 10"11 S cm"1 as T8 is reduced from 323C to 77C. This
fall in GRT was accompanied by a corresponding increase in a o between 102 and 10 7 S cm"1.
Similar findings have been reported by Cabarrocas et al [32] although a definite trend is less
easy to detect from the more recent work of Morin and Cabarrocas [33] where GRT for T8 =
3500C is already low and quoted as 3 x 10"11 S cm 1 . The conductance properties resulting
from the use of high T8 are reported by Golikova et al [34].
A number of groups have modified the operating cycle of RF PECVD reactors in an attempt to
produce high quality a-Si:H for T8 < 2000C [35-37]. The technique involves the deposition of a
number of thin sequential layers at a selected T8 with brief chemical annealing of each newly
deposited surface being performed using a hydrogen plasma. In this manner, the amount of
bonded hydrogen in the films may be accurately controlled for a selected T8 and the optical
bandgap Eg varied between 1.65 eV and 2.05 eV as desired. From conductivity measurements
it is found that E a ~ Eg/2 and aRT is correspondingly found to range over two to three orders of
magnitude. In a variation of the chemical annealing method, Marayama et al [38] investigated
the use of inert gas plasmas at a fixed T8 of 2000C. These workers find that CFRT decreases from
about 10"10 to 10"12 S cm"1 as the amount of bonded hydrogen is increased from 18 to 35 at.%.
Similar large changes are apparently not observed, however, if single-layer a-Si:H films are
exposed to hydrogen plasmas [39].

A number of groups [40-42] advocate the dilution of the SiH4 source gas in either hydrogen or
helium as a method of depositing device quality a-Si:H at very low Ts. The conductivities of
as-deposited samples using this approach exhibit some variation depending upon the amount of
SiH4 dilution [41] and the particular dilution gas employed [42]. An annealing process must be
performed to enhance the optoelectronic quality of specimens deposited by this method and this
is reported to alter GRT [40,42]. Dilution techniques have also been examined where
dichlorosilane (SiH2Cl2) is used as the source gas. The conductivity of a-Si:H(Cl) is reported to
decrease by about two orders of magnitude to values as low as 0 RT = 6 x 10"13 S cm"1 as the
ratio of SiH4ZSiH2Cl2 is reduced in the gas phase [27,43]. E c is observed to decrease by about
0.1 eV as GRT falls [43]. a-Si:H(Cl) films prepared from hydrogen diluted SiH2Cl2 plasmas
display similar conductivity magnitudes with aRT decreasing from 10"11 to 5 x 10"13 S cm"1 as the
dilution ratio of hydrogen to SiH2Cl2 is enhanced [44].
It is difficult to correlate the reported conductivity properties of a-Si:H with other RF PECVD
deposition variables such as chamber pressure or applied RF power. For instance, Wang and
Cheng [13] present results showing that GRT increases by a factor of about 2000 as the plasma
pressure is reduced from 1.2 to 0.5 ton*. This contrasts with the findings of Middya et al [45]
who observe GRT to decrease from 4 x 10"9 to 4 x 10"10 S cm"1 as the chamber pressure is
reduced from 2.2 to 0.5 torr for helium diluted discharges. The deposition rate was found to
increase with pressure in both of these latter cases so that a reconciliation of the apparently
disparate trends in terms of fundamental growth kinetics also appears implausible [46].
C2

VHF PECVD

The use of very high frequency (VHF) PECVD deposition methods is becoming increasingly
widespread in an effort to deposit device-quality a-Si:H films at enhanced deposition rates. By
increasing the plasma excitation frequency (f) to frequencies approaching 300 MHz, it is
possible to achieve almost an order of magnitude increase of deposition rate (Ra) compared to
conventional RF values of 2 - 3 A s"1 [47-50]. For a fixed Ts, most authors agree that the
conductivity parameters display little dependence upon either f or Rd [48,49] although the data
presented by Hautala et al [47] do appear to show aRT increasing from 10"10 to 10"8 S cm"1, and
E 0 decreasing from 0.86 eV to 0.74 eV, as Ra is increased from about 3 A s"1 to 20 A s"1. The
variation of <JRT with Ts under fixed 70 MHz VHF conditions is similar to that found under RF
excitation with aRT falling as Ts is reduced from 3000C to 500C [50-52]. The relative fall of aRT
with Ts is found to be larger for SiH4 diluted in hydrogen [51]. The trend is also less noticeable
in the data of Kroll et al [52] who focus on higher Ts materials between 2000C and 4000C. The
importance of VHF power and plasma pressure conditions on dark conductivity parameters has
been described by Oda and Yasukawa [53] who find that <JRT increases with VHF power, and
decreases with chamber pressure. They attribute the enhancement of CTRT with 144 MHz VHF
power to partial microcrystallisation within their samples.
C3

Remote Plasma CVD

It has been suggested that ion bombardment of the growing film surface in single chamber
deposition systems may, under certain operating conditions, degrade the electronic properties of
a-Si:H films [54]. Evidence to support this has been described by Cabarrocas et al [55] who
have monitored the effect of applying a negative bias to the substrate of films grown under RF
PECVD conditions. These authors find that aRT goes through a minimum, and E a

correspondingly goes through a maximum, as the substrate bias is decreased to -50 V. The
results are interpreted in terms of the estimated ion energies impinging on the film surface and it
is argued that moderate energies are beneficial in optimising the defect DOS in a-Si:H.
Attempts to minimise deleterious bombardment damage occurring in single chamber PECVD
reactors has forced many groups to consider generating the deposition plasma in a separate
location remote from the growing film surface. These methods may be categorised as remoteplasma (RP) CVD techniques. The remote-plasma is normally generated using hydrogen or
helium and may be induced by using either a standard RF excitation source [56,57], a DC
thermal arc [58,59] or an electron cyclotron resonance (ECR) chamber [28,29,60-64].
The use of an RF generated helium RP to dissociate SiH4 diluted with hydrogen is reported by
Kim et al [56]. By varying a substrate bias voltage between -100 V and +100 V, these authors
are able to reduce <TRT from 3 x 10'9 to 10"10 S cm"1, and correspondingly increase E a from
0.75 eV to 0.87 eV. A helium RP was used by the same group to deposit a-Si.H from SiH4
diluted in helium [57]. The principal conclusion of this study was that a large increase in aRT
results if the RP power is increased. This is attributed to the onset of microcrystalline
formation.
The use of a novel expanding thermal plasma as an RP source is described in the work of
Severns and co-workers [58,59]. For a-Si:H deposited by this method, GRT is approximately
2 x 10"11 S cm'1 for Ts = 3500C and decreases to almost 10"13 S cm"1 if Ts is set at 800C.
Remote plasmas generated by ECR techniques are becoming increasingly important for the
rapid deposition of high-quality a-Si:H. ECR hydrogen or helium plasmas may be sustained at
low pressures which results in a high degree of ionisation and consequently high values of Ra
(>10 A s"1). For a-Si:H deposited at Ra = 23 A s"1, GRT was measured to be about 3 x 10"10 S
cm"1 [60] and at Ra = 28 A s"1 is quoted to be 1 x 10"u S cm"1 [61]. A systematic study of the
dependence of the dark conductivity on Ra is described in the work of Zhang et al [62] who use
a remote ECR hydrogen plasma to dissociate SiH4 diluted in hydrogen or helium. For
T8= 2500C, they find that GRT increases with Ra in accordance with earlier work [60,61].
However, a separate study by Knox et al [63] concluded that aRT displayed no correlation to the
ECR plasma properties. aRT is still found to be strongly dependent upon the substrate
temperature under ECR conditions and was found to increase with Ts in a manner analogous to
RF PECVD material [64]. The group led by Azuma have produced a-Si:H(Cl) by using
SiH2Cl2 as the source gas in an ECR hydrogen plasma and report aRT values approaching 10"13
S cm"1 [28,29]. From a(T) measurements they find E a to lie between 0.9 eV and 1.0 eV which
suggests that Ef is located below mid-gap.

CONCLUSION

It is evident that the dark conductivity of a-Si:H prepared by plasma assisted CVD techniques is
highly sensitive to a number of factors which may profoundly influence the measured values of
CJRT, E a and ao. To realistically compare conductivity parameters, consideration must therefore
be given to the plasma deposition technique, any external post-deposition processes likely to
modify the DOS and the experimental conditions employed during the actual measurement of a.

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4.2

Mobilities in a-Si:H and its alloys


GJ. Adriaenssens
September 1997

INTRODUCTION

Carrier mobilities are amongst the most important semiconductor parameters, and are therefore
often used to characterise a-Si:H semiconducting properties. It has become a rule of thumb that
good-quality, undoped a-Si:H should have a room-temperature electron drift mobility, \i&e, of
about 1 cm2/V s, provided that this mobility is obtained from a time-of-flight (TOF) transient
photocurrent experiment. This proviso refers to the fact that drift mobility values have, at
times, been deduced from other experiments as well, and that it is not always clear as to what
extent the drift mobility definitions are compatible.
One therefore has to take the differences in experimental techniques into account when
comparing mobility values. For the carrier mobility in a thin-film transistor (TFT) context, a
common field-effect mobility is generally used, such that no problem arises. However,
determinations of the drift mobility as a material parameter have been reported on the basis of a
variety of opto- and acousto-electric experiments, and hence need to be compared with caution.
Even more care (or scepticism?) should be exercised in using literature values for the extendedstate mobility |io (also called free-carrier, or microscopic, or band mobility). It is a quantity
which cannot be measured in itself, but which is related to experimental values of the drift
mobility (id by the relationship
(1)
where nf and nt are the free and trapped carrier densities, respectively. Since the fraction
nf/(nf+nt) itself needs to be obtained through modelling from experimental transport data, |io
values will change with the assumptions made for that modelling. The physical basis for EQN
(1) is readily understood: for temperatures above -120 K, transport in a-Si:H can be described
by a multiple-trapping formalism (trap-limited band transport) whereby carriers are immobile
while trapped, and are moving with mobility \io when free.
In this Datareview, experimental drift mobility data will be presented first, with separate
discussions of the results for electrons and holes in undoped material, in doped materials, and in
silicon alloys. The more speculative results concerning the extended-state mobility will be
summarised next, and the present status of the field-effect mobility will conclude the survey.

DRIFT MOBILITY

A simple and direct way to measure the drift mobility of either electrons or holes in a-Si:H is
given by the standard TOF experiment [I]. With a several |im thick sample in a sandwich

configuration between blocking contacts, electron-hole pairs are generated just below one
(semi-)transparent electrode by a laser pulse, and one records the transit time, tr, of electrons or
holes (depending on the direction of the applied field F) through the sample of length L, to
obtain
(2)
Drift mobility is also, of course, a well-established concept in electrical transport theory.
Various ways have consequently been proposed to extract mobility values from transport
measurements, with each analysis making use of its own set of assumptions. One can thus find
mobility values based on (amongst others) surface acoustic waves (SAW) [2], modulated [3]
and moving [4] photocarrier gratings (MPG), photoconductive frequency mixing [5], or
photoconductive response-time measurements [6]. These results will be compared to the TOF
data below.
Bl

Electrons in Undoped a-Si:H

Bl.l

Time-of-flight results

The drift mobility in a-Si:H is influenced mainly by material quality (i.e. the density of localised
states) and by temperature, and to a lesser extent by the applied electric field. It has become
standard practice, therefore, to quote the room-temperature drift mobility and the mobility
activation energy, measured in a field near 104 V/cm, as representative values. For devicequality, standard plasma enhanced chemical vapour deposition (PECVD) material, current
values are roughly |ia(300 K) - 1-15 cm2/V s and E^1 - 0.14 eV [7], values which have not
changed much since the early reports by Tiedje et al [8] and Hourd and Spear [9]. Poorerquality samples (which includes sputtered a-Si.H [10]) do show progressively lower |id(300 K)
and higher E^1 values as their localised-state density increases. This observation seemingly
contradicts reports [11,12] that light soaking does not affect the TOF drift mobility, but only
seemingly so. The TOF transit time essentially reflects the distribution of tail states close to the
mobility edge (no more than -0.2 eV below E c ), which apparently is not changed noticeably by
light soaking, but which is influenced by preparation conditions.
In comparing TOF mobility values from different research groups, possible differences in the
way the transit time tT is defined have to be taken into account. Sometimes, as in [13], the
fastest carriers are emphasised, while mostly the average free carrier is taken as reference. Such
differing tr definitions, as well as the best corresponding theoretical expressions for modelling
purposes, have been examined in [14]; they would not account for more than 20% of the
difference in (id values for standard a-Si:H. The high |j.d(300 K) - 2.5 cm2/V s reported by
Marshall et al [13] are hence not due to a diverging tx definition. As discussed in [15], other
samples from the same series did have the usual 1 cm2/V s at room temperature. It is advisable,
therefore, not to use the drift mobility data set of Marshall et al [13] as typical for PECVD
a-Si:H, but to use, for instance, the one from Nebel and Bauer [16] that is reproduced here as
FIGURE l(a). Both data sets show the sizeable field dispersion of the mobility at temperatures
between 100 K and 300 K. Similar data sets, but with a smaller range of applied fields, can also
be found in [15,17,18]. Much stronger field dispersion is observed for higher fields at still
lower temperatures, as shown in FIGURE l(b) [19]. Such measurements require the use of

p-i-n diodes, with thin p+ and n+ layers acting as blocking contacts for the thick i layer, rather
than the Schottky diodes used in most of the earlier experiments.

10 Jim pin (b)

^D(cm2/Vs)

logoff /cm2 V1S-1J

(a)

1O3/T (K"1)

1000/T(K- 1 )

FIGURE 1 (a) Temperature dependence of the electron drift mobility in a 4.0 |xm thick Cr/a-Si:H/Al
Schottky diode, with electric fields - top to bottom - of 1.75 x 105, 1.5 x 105, 105, 7.5 x 104, 5 x 104,
2.5 x 104, and 5 x 103 V/cm [16]. (b) Analogous data set obtained with a 10 (a.m thick
p-i-n junction and higher fields [19].

The data in FIGURE l(b) also serve to rectify earlier reports [20-22] that below 80 K the
electron drift mobility rises back to values near 1 cm2/V s. As demonstrated by Kocka et al
[23], incomplete collection of the photogenerated charge (less than 1%) is obtained at low
temperatures when fields of less than 105 V/cm are used, as was the case in [20,21], and no
meaningful transit can be resolved from such incomplete charge collection. In [23] various
features of space-charge-limited TOF (SCL-TOF) were used to identify carrier transit times and
deduce the drift mobility. While the SCL-TOF technique is useful in enhancing weak signals
where small-signal TOF fails, its results do carry a larger uncertainty than the ones from
standard TOF [24].
Apparent room temperature electron drift mobility values up to |ide ~ 60 cm2/V s were reported
recently by Ganguly et al [25] for PECVD a-Si:H prepared under controlled ion bombardment.
While closer investigation revealed some flaws in the original analysis, with low charge
collection again providing a prime indication of error, adjusted results [26] still indicate higher
drift mobilities than in standard a-Si:H samples at comparable temperatures up to 213 K. The
low-field mobility activation energy E^1 is comparable to that of standard a-Si:H, but the field
dispersion is stronger. No data at higher temperatures are available currently.

B1.2

Other methods

Alternative methods are mostly used to circumvent the inability of standard TOF to deal with
highly conducting (doped) samples, but they also have been applied to undoped a-Si:H. Fuhs et
al [27] combined steady-state photoconductivity and response time data to extract ^ e values
that agreed very well with TOF results from contemporary 'glow discharge1 material. More
recent use of the method by Oktti et al [6] produced the same conclusion with respect to
current PECVD a-Si:H. This is somewhat surprising since it was subsequently shown [28] that
the measured response time actually differs from the theoretically intended one; measured and
intended times were obviously close enough in the above examples.
Photocarrier gratings, while primarily being used to measure the ambipolar diffusion length in
a-Si:H, can also yield information on carrier mobilities. However, as the relationships between
the various parameters are complex (see, e.g. [29] for a recent example), an extra time
dependence has been introduced, by either modulating [3] or moving [4] the grating, to
facilitate extraction of mobility values. The MPG electron mobilities that are obtained,
0.156 cm2/V s in [3] and 0.077 cm2/V s in [4], obviously refer to an ensemble of electrons that
differs from the one that defines the TOF drift mobility. Electric fields applied in MPG
experiments are very weak compared to those used in TOF. In addition, since the modulation
period in [3], or the times needed in [4] to move the grating over the width of an interference
line, are about an order of magnitude larger than a TOF transit time, the mobility difference
with respect to TOF presumably results from the fact that MPG will also sample slower states
located deeper in the gap.
The photomixing technique employed by Tang and Braunstein [5] to measure drift mobilities,
produces a high value of |ide(300 K) ~ 3 cm2/V s for standard PECVD a-Si:H, as well as for
hot-wire deposited material [3O]. Since photomixing frequencies of the order of 1 GHz were
used, only states which can respond faster than the usual TOF transit time will contribute to the
AC conductivity that is used to calculate fid. Similarly, high mobility values are also found by
Devlin et al [31] who used sub-nanosecond optical pump and probe techniques, and high
electric fields, to observe fast carrier transits, and by Juska et al [32] who placed their samples
in a coaxial waveguide to observe TOF transits under high field conditions.
B2

Holes in Undoped a-Si:H

A representative set of hole drift mobility values, as determined by Marshall et al [33] from
TOF measurements, is shown in FIGURE 2. It is obvious that the field dependence of the
mobility remains significant here at and above room temperature, and therefore data
specifications should include both temperature and electric field. The values |idh(300 K) = 4.0 x
10"3 cm2/V s and E ^ = 0.36 eV, at F = 104 V/cm, differ strongly from the corresponding ones
for electrons, confirming that in a-Si:H the holes are less mobile species, and that the valenceband tail is much wider than the one on the conduction band side. Highly similar results have
been reported for other a-Si:H samples [34,35].
Ganguly et al [25] reported room temperature hole mobilities as high as 1 cm2/V s for the
a-Si:H grown under controlled ion bombardment, but it is to be expected that upon
re-examination this value will come down, similarly to what has happened with the companion
electron values [26]. Hole mobilities have also been calculated on the basis of MPG

P 4 (CfTiV 1 S'')
103/T
FIGURE 2 Temperature dependence of the a-Si:H hole drift mobility at fields of top to bottom -150, 100, 80, 50, 30, 20, 10, 8, 5, 3, and 2 kV/cm [33].

experiments. There, the results, 9.4 x 10"4 cm2/V s in [3] and 2.4 x 10"4 cm2/V s for a field of
5 kV/cm in [36], are again well below the TOF mobility values, as was the case with MPG
versus TOF electron mobilities (see previous section).
B3

Doped a-Si:H Layers

The high conductivity of doped samples precludes the use of the TOF technique to determine
the drift mobility for all but the lowest doping levels. A decrease of the mobility upon doping
was mostly (although not universally) reported [10,37], in agreement with more extensive
results from other experiments. The decrease is smaller in n-type than in p-type material. The
effect of dopants upon the TOF drift mobility was further examined in [38] through the use of
compensated a-Si:H. Films prepared with 1, 10, or 100 p.p.m. of both B2H6 and PH3 added to
the SiH4, showed decreases of both electron and hole mobility on the order of 1, 2, and 3 orders
of magnitude respectively, with increased mobility activation energies accompanying the
decreasing mobility. These changes are much more pronounced than the corresponding ones
when only one type of dopant is used.
Drift mobilities were studied by Fritzsche and co-workers [2,39] with the SAW method for both
p-type (150 p.p.m. B2H6) and n-type (5 and 300 p.p.m. PH3) samples. At room temperature,
Hdh ~ 4.8 x 10"4 cm2/V s and |ide ~ (0.1 - 0.5) cm2/V s are obtained. Application of the SAW
method to undoped samples has shown that it gives mobility values that match TOF results (but
also that the method becomes unreliable below 100 K [40]).
The inability to apply TOF to most doped samples has led to the use of a number of alternative
transient experiments. Hoheisel and Fuhs [41] used the photoconductive response time method
to measure samples with doping levels between 0 and 1000 p.p.m. of PH3 or B2H6 in the gas
phase. They resolved room-temperature electron and hole mobilities which, for the undoped

and -30 p.p.m. samples, are roughly one order of magnitude below the SAW values cited
above, and then decreased by factors of three to ten for higher doping concentrations, all with
nearly unchanged mobility activation energies. Crandall [42] used the reverse bias current
transient from a Schottky junction (Pt on a-Si:H with 2000 p.p.m. PH3 in the gas phase) to find
a low |ide(300 K) = 6.5 x 10"3 cm2/V s, but with the standard activation energy of 0.13 eV.
More usual mobility values were found by Street et al [43] who combined DC conductivity and
carrier sweep-out measurements to study material with [PH3]Z[SiH4] ratios of 10"4 and 10"2.
Room temperature electron mobilities of -0.45 and -0.10 cm2/V s were obtained with an
activation energy of about 0.15 eV.
Values for both the drift mobilities and their activation energies, as reported by different
laboratories, show larger variations for the doped materials than they do for undoped a-Si:H.
This undoubtedly reflects differences of dopant incorporation, even when starting from the
same gas mixtures.
B4

Silicon Alloys

Alloying a-Si:H with Ge, C, or S reduces both electron and hole mobilities, increases the
activation energy of the electron mobility, but leaves the activation energy of the hole mobility
essentially unchanged. Most available data are the result of TOF measurements. For carbon
alloys, a set of electron mobilities obtained through photoresponse measurements [6] fully
agrees with those TOF results, while a photomixing result [5] (from an ill-defined specimen)
agrees in general.
Measurements of Hde in various a-Sii-xGe^H alloys [44-46] show a decrease of room
temperature mobility by one order of magnitude for x going from 0 to 0.25, with a parallel
increase of the activation energy from -0.15 to -0.35 eV. (Some reports only present data at
lower temperatures, but they all fit the same pattern.) Not unlike the hole mobility in unalloyed
a-Si:H, the electron mobility in the Ge alloys shows considerable field dispersion at room
temperature. Hole drift mobility is apparently difficult to measure in Ge alloys due to a failing
charge collection efficiency [44].
On a-Sii-xCx:H alloys, extensive data sets are available for both electron and hole mobilities
[47-49], but only for alloys with x < 0.1. Higher carbon concentrations result in too high defect
densities to allow the observation of a TOF transit. At x = 0.07, room temperature electron
drift mobility has already dropped to 3 x 10'2 cm2/V s with an activation energy E^ = 0.31 eV;
for holes the corresponding values are |a<ih ~ 1 5 x 10"3 cm2/V s and E ^ = 0.35 eV. These
mobilities are lower with respect to the corresponding ones from unalloyed a-Si:H by factors of
(about) 38 for electrons and 3 for holes. For smaller C concentrations intermediate values are
found. The correlation between decreasing electron mobility and increasing alloy content was
also noted in [50], but the concurrent claim that hole mobilities are not affected by alloying
should not be taken literally.
Only minimal information is available on carrier mobilities in a-Sii_xSx:H alloys. A sample with
x = 0.015 showed strong field dependence of the electron mobility [51], and (at 104 V/cm)
Hde(300 K) ~ 0.15 cm2/V s with E^ ~ 0.30 eV. For samples with x > 0.015 no TOF transit
could be resolved.

EXTENDED-STATE MOBILITY

Widely varying claims have been made concerning the extended-state mobility |j,o. As
mentioned in the introduction, much depends on the theoretical model for the transit time [14],
as well as on the interpretation of the ratio of free to total carrier densities of EQN (1). That
interpretation in turn depends on the model used for the density of localised states in the
bandgap. As a consequence, the a-Si:H TOF electron drift mobility data summarised above led
Hourd and Spear [9] to a (iOe = 7.3 cm2/V s, Silver et al [52] to a value of-500 cm2/V s, and
Michiel et al [53] to some 50 cm2/V s. Gradually, a value of |Ooe = 10 cm2/V s did become
broadly accepted.
The extended-state mobility on the valence band side was originally set at |^oh = 0.67 cm2/V s by
Tiedje et al [8]. As argued later by Marshall et al [33] that 10 cm2/V s would be a better value,
values between 1 and 10 cm2/V s have recently been used.
As for most of the results referred to in this Datareview, the above extended-state mobility
estimates are for standard PECVD a-Si:H and based on standard TOF experiments. However,
recent evidence from other sources suggests that the Hoe ~ 10 cm2/V s may be an overestimation. From time-resolved femtosecond spectroscopy it was concluded [54] that
6 cm2/V s would be an appropriate value, while a detailed analysis of transient
photoconductivity in the presence of optical bias in high-frequency deposited material [55]
produced extended-state mobility estimates of 4 - 7 cm2/V s for electrons and 1-3 cm2/V s for
holes.

jj. (cm2/Vs)

Lower values for the extended-state mobility


are also indicated by experiments carried out
at high fields and high temperatures. It is
anticipated that under such conditions the
ratio of free to total carrier densities of EQN
(1) will stay close to one during the average
carrier transit, and that |j.d will hence
approach |j,o- FIGURE 3 shows the results of
TOF measurements by Juska et al [56] as a
450K
410K
function of field and temperature, together
350K
with their estimate of the dependence of the
295K
396K
room temperature extended-state mobility on
electric field. It is seen that TOF mobilities
become field- and temperature-independent
at -500 K and - 5 x 105 V/cm. At high
F(MV/cm)
fields, M 3 0 0 K) ~ |Ooe ~ 3 cm2/V s and
E ^ O are found. The same |Xoe ~ 3 cm2/V s FIGURE 3 Electron drift mobility as a function of the
electric field at different temperatures for a 10 |im
is deduced from high-field data by Gu et al thick a-Si:H p-i-n sample. The lines are calculated
[57]; these authors suggest a |ioe which is curves for drift and extended-state mobilities; see [56].
independent of field and temperature, and a
field-dependent position of the mobility edge.
The temperature dependence of (J,oe in a-Si:H cannot be measured directly, but there is a general
agreement that there will be only a modest power-law dependence, |ioe - Tp. Over the years,

different arguments have been used to justify different values in the range -2 < p < 2. While
p = 0 was most widely used [7-9,...], p = -2 may be found in [58], p = -3/2 was used in [59],
p = -1/2 can be seen in [56], and even p = 2 (coupled to a Uoe(300 K) = 7 cm2/V s) was shown
to fit the drift mobility data in [15,18].

FIELD-EFFECT MOBILITY

The field-effect mobility UFE, which is used to characterise carrier mobility in TFTs, is defined in
the saturation region of the device from the conductance change with applied voltage and the
capacitance per unit surface area, C, as
(3)
This quantity reflects transport in the tail states, and is therefore comparable to the TOF drift
mobility, UFE values around 1.2 cm2/V s are hence regularly reported [60,61] for amorphous
TFTs, but much higher mobilities can be realised by depositing microcrystalline layers or by
laser re-crystallisation of the a-Si:H [62]. This fact will always have to be considered in
evaluating reports such as the one in [63], where a 4.9 cm2/V s mobility is reported for an
amorphous TFT.
One particular concern about the field-effect mobility is that high mobility values are generally
linked to low deposition rates [60]. It is noteworthy, therefore, that Meiling and Schropp [64]
succeeded in producing a hot-wire deposited TFT at a rate of 17 A/s, and with UFE = 0.6
cm2/V s.

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Previous Page

4.3

Thermoelectric power and Hall effect in a-Si:H


D.L Jones
March 1997

THERMOELECTRIC POWER

Al

Introduction

Measurement of the temperature dependence of the thermoelectric power, S, together with the
concurrent measurement of the (dark) conductivity, a, provides a sensitive and informative
approach to the study of transport processes occurring in amorphous semiconductors. The
thermoelectric power gives unambiguously the sign of the predominant carrier and, more
importantly, provides information on the possible conduction path(s) within the material.
A2

Earlier Experimental Results (pre-1985)

Measurements of S have been made on amorphous silicon prepared in various ways using
different deposition conditions. The earliest measurements were on amorphous silicon films
prepared by vacuum evaporation onto heated substrates and reported by Grigorovici et al [1]
and Beyer and Stuke [2]. The relative low room temperature conductivity (<10"8 Q"1 cm"1) of
undoped a-Si:H films prepared by decomposition of silane in a glow discharge, currently
referred to as plasma enhanced chemical vapour deposition (PECVD), severely restricted the
temperature range over which measurements could be made. By adding phosphine or diborane
to the silane Spear and LeComber [3,4] succeeded in producing n-type and p-type films with
room temperature conductivities as high as 10"2 Q"1 cm"1. This made possible the systematic
investigation of S and a over an extended temperature range for a wide range of doping levels
and led to renewed interest in a-Si:H which resulted in a number of investigations. These
include measurements on:
(a)
(b)
(c)
(d)
(e)

phosphorus doped films, Jones et al [5], Beyer et al [6], Beyer et al [7],


arsenic doped films, Jan et al [8],
boron doped films, Beyer and MeIl [9], Zimmer et al [10],
compensated films, Beyer et al [11] and
amorphous silicon doped by implantation with alkali or halogen ions, Beyer et al [12],
Beyer et al [13].

Van Dong and Hai [14] were the first to report measurements of S on sputtered films of Si
made more conducting by doping with antimony. Anderson and Paul [15] have reported
measurements on RF sputtered hydrogenated a-Si films doped with phosphorus.
A3

Theoretical Background

A universal feature of nearly all measurements of S and o is the difference in slope of their
respective activation energies, Es and ECT. Two main methods of analysis have been used to

interpret the experimental results. The first method used by Jones et al [5] for phosphorus
doped a-Si:H proposes two separate conduction paths, one in the extended electron or hole
states at higher temperatures and the other by hopping in a fairly narrow range of energies in tail
states. The observed conductivity under these conditions may be written

where

is the conductivity in extended states at energy Ei and

is the conductivity associated with hopping at energy E 2 where W denotes the average hopping
energy. EF is, of course, the Fermi energy.
The thermoelectric power will be the weighted average of the thermoelectric power for the
separate paths and given by

where Si and S2 are given by

where x = 1, 2 and A is a constant.


Beyer et al [12] introduced the function

which has the advantage that it is independent of any temperature shift of either the Fermi level
or the predominant conduction path which so often complicates the variation of both a and S
with temperature.
The two conduction path model leads to a non-linear variation of S, a and Q with inverse
temperature and has been used by several investigators (for example [5,8,10,15]) to explain
their results. Others, notably Beyer and co-workers, have observed a linear variation of Q with
inverse temperature. A significant development has been the work of Overhof and Beyer [16]
who explained the experimentally observed linear relation between Q and 1/T, for variously
doped a-Si:H films in terms of potential fluctuations. Potential fluctuations in an amorphous
film, first proposed by Fritzsche [17], can be caused by structural inhomogeneities and/or

internal electric fields created by a distribution of charge centres. Conduction is then assumed
to take place through a single conduction path in extended states above a mobility edge whose
energy is modulated by these in-built long-range static potential fluctuations.
Overhof and Beyer [16] used numerical model calculations to show that the dependence of Q
on 1/ T is given by

Here, G0 is the conductivity pre-exponential, and A is the magnitude of the potential


fluctuations, which can range from 10 to 250 meV.
Overhof and Beyer [18] explain the temperature and doping dependence of a, S and Q as
measured for phosphorus doped, boron doped and compensated samples by the effect of
potential fluctuations. For boron doped samples, however, they report a non-linearity in Q
versus 1/T which they ascribe to a second conduction path, namely hopping at the Fermi level
or in tail states. A comprehensive summary of their data is given by Beyer and Overhof [19].
In general,

where Qo = 10 1 and EQ
ranges between 0.05 eV and
0.25 eV for undoped and
doped films (Overhof and
Thomas [20]).

PPH5ZPSiH4

Furthermore, Overhof and


Beyer [18] having defined a
reduced temperature as T =
kT/A show that when Q is
plotted as a function of 1/T' all
data points for a-Si films,
whether
doped
with
phosphorus, boron or lithium,
as well as compensated films
fall on the same line with very
little scatter as shown in
FIGURES 1 and 2.
Dohler [21] suggests that
the
difference
between
thermopower and conductivity
activation energies Es and E0 is
caused by an indistinct
mobility edge and concludes
that doping induced changes
of mobility and density of

1/T'
FIGURE 1 Q versus reduced temperature for
a-Si:H doped with phosphorus [18].

states occur at the energies where transport takes place. He further suggests that the dominant
transport mechanism in a-Si:H is always hopping below the mobility edge even at temperatures
close to the recrystallisation point. To date, Dohler's suggestions have not enjoyed wide
acceptance and most data are interpreted in terms of the two conduction path model or the
potential fluctuation model.

1Cf3 P H 3

vr
FIGURE 2 Q versus reduced temperature for compensated a-Si:H for p-type
(open symbols) and n-type (closed symbols) films [18].

A4

Experimental Data (post-1985)

During recent years there have been relatively few reports of measurements on thermoelectric
power. These include measurements reported by Ghiassy et al [22] on boron doped films, by
Dusseau et al [23] on phosphorus doped films, by Chick et al [24] on thermal-LPCVD
amorphous silicon-boron films, and by Banerjee and Ray [25] on boron doped hydrogenated
amorphous silicon and silicon carbide films. Dyalsingh and Kakalios [26] in a recent paper on
a-Si:H have measured the thermoelectric current rather than the thermoelectric emf as a
function of temperature and reported no difference between E a and E s . This may not be
surprising because in both cases they generate a current, in the first case by applying an external
emf and secondly by using the internal thermoelectric emf.

A5

Thermoelectric Power and the Effect of Illumination

Hausechildt et al [27] have studied the effect of prolonged exposure to light on the Q function
and conclude that optically induced conductivity changes in a-Si:H films (Staebler-Wronski
effect [28]) are not merely caused by a shift in the Fermi level towards mid-gap but by a
modification of the current path at the mobility edge. Goesmann and Jones [29] have reported
measurements of photoconductivity and photo-thermoelectric power on undoped, boron doped
and phosphorus doped samples. The significant features of the results are that Q is independent
of illumination intensity and Q varies linearly with 1/T over a temperature range of 250 K or
more. For example, for an undoped film

A6

Conclusion

The temperature dependence of both the conductivity and thermoelectric power measured on
films prepared in different ways, or even the same way in different laboratories, can differ
considerably, but the differences can be ascribed to a variation in the position of the Fermi level.
When the possible shift of the Fermi level is taken into account there is a remarkable consistency
between published values. There still exists a difference of opinion between those who interpret
their results in terms of a single conduction path modified by potential fluctuations and those
who consider a two conduction path model to be more appropriate.

HALL EFFECT

Bl

Introduction

Hall effect measurements on undoped a-Si.H proved either difficult or impossible because of the
relatively low conductivity of the material and it was only after the doping of the material with
either phosphorus or boron that measurements were made. The first measurements on this
material, by LeComber et al [30], indicated that the sign of the predominant carrier as derived
by the Hall effect was opposite to that measured by thermoelectric power. Results on material
doped with phosphorus indicated the dominant carriers to be p-type whereas for boron doped
material the dominant carrier appeared to be n-type.
B2

Experimental Results

In lightly doped n-type samples the observed Hall mobility |aH has a magnitude of about 0.1 cm2
V"1 s"1, essentially independent of temperature as shown in FIGURE 3. On increasing the donor
density, [IH begins to show a temperature dependence which was analysed in terms of a model
with two conduction paths. The double sign reversal, noted in Section Bl, was confirmed by
Beyer et al [7] and Beyer and MeIl [9]. Dresner [31] measured the Hall mobility of undoped
a-Si:H under illumination and in the dark. He distinguishes two regions; below 360 K the Hall
mobility is fairly constant at about 0.1 cm2 V 1 s"1 but at higher temperatures it is activated with
an energy of 0.13 eV.

^HI

1
(Cm2V1SCc"1)

p-type

IO/T

(K"1)

FIGURE 3 The magnitude of the Hall mobility versus inverse temperature


for four n-type films and three p-type films [30].

Tong and Du [32] have carried out an extensive investigation of over 1000 samples prepared by
thermal low pressure chemical vapour deposition (LPCVD). By varying the substrate
temperature and the dopant gas ratio they were able to produce both amorphous and
microcrystalline films. Although their microcrystalline films show a normal Hall effect and most
amorphous films show the usual sign reversal, they report that it is possible to choose
deposition parameters so as to produce films, confirmed as amorphous by a number of different
structural measurements, which show the normal Hall effect with no anomalous sign reversal.
The Hall mobility of such films is 0.15 cm2 V 1 s"1 when doped with phosphorus and 0.11 cm2
V"1 s"1 when doped with boron.
Nebel et al [33] have observed normal signs of the Hall effect in boron doped and phosphorus
doped hydrogenated amorphous films. These results are ascribed to the presence of a small
fraction of nanocrystalline silicon which falls below the detection limit of their Raman
experiments.
B3

Theory

Several papers have been published attempting to explain the reversal of the sign of the Hall
effect. Friedman [34] has proposed a theory which predicts that the Hall mobility is
independent of temperature and always negative whether the carriers are electrons or holes and
thus fails to predict the double reversal of sign observed in a-Si:H. Emin [35] points out that
the sign anomaly in n-type silicon can be explained if the carriers form polarons which move in a
structure where odd membered rings predominate, but this explanation has not been generally
accepted. Mott [36] has proposed that the sign anomaly may be explained if the centres which
scatter electrons are Si-Si bonds, for example a stretched bond, in which the electron energies
differ from the majority so that scattering only occurs there. Holendar and Morgan [37] have
presented computer simulations of the Hall effect and have succeeded in verifying the double

sign anomaly. Kakalios [38] proposed that the sign anomaly can be understood in terms of
destructive interference effects when the electron phase coherence length is comparable to the
distance between transport states. Overhof [39] has extended his potential fluctuation model to
a calculation of Hall mobility and predicts the Hall mobility to be activated with energy
E H = E Q / 3 over the whole temperature range. In general, the measured Hall mobility varies
non-linearly with inverse temperature and, furthermore, the potential fluctuation model offers no
explanation for the double sign anomaly.
B4

Conclusion

There is widespread agreement regarding the magnitude of the Hall mobility UH at about 0.1
cm2 V 1 s"1. Although several explanations have been suggested for the double sign anomaly in
hydrogenated amorphous silicon the effect remains unexplained in terms of a straightforward
physical model.

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4.4

Steady state photoconductivity in a-Si:H and its alloys


R. Briiggemann
June 1997

INTRODUCTION

This Datareview discusses work on steady state photoconductivity in a-Si:H, including the
mobility-lifetime product1 indicator of material quality. The steady state photoconductivity
(SSPC) obtained from a measurement of photocurrent Iph is given by aph = q{(n-no)|in +
(p-po)m), where q is the elementary charge, n (p) the total free electron (hole) density, no (p0)
the thermal equilibrium electron (hole) density and [In ((J1,) the free electron (hole) mobility. If,
say, p-po is much larger than n-no, then aPh reduces to aPh = q(p-po)lV Depending on the excess
carrier density and mobility, either electrons or holes are the majority carriers or both carrier
types contribute to IPh. It is also possible that the majority carrier type may change for different
temperature T and generation rate G for one sample.
f

Generally, the dependence of photoconductivity on T, G and the position of the Fermi energy
EFO can be exploited to obtain more information on the physics of recombination. The
recombination lifetimes are defined by [1] (n-no)/tnr = (p-po)/V = G, so that the steady state
mobility lifetime products are given by
(1)
The |aT-product of the majority carrier is easily determined from aph whenever one carrier type
determines photoconduction. If electrons are the majority carriers, then (|ix)ns = aPh/qG. Note
the superscript S for labelling the steady state (ax-product. Alternatively, if G does not include
the quantum efficiency r\ for photogeneration, the r|[ix-product is determined.
The measurement of the steady state minority carrier fix-product has only advanced more
recently in amorphous silicon with the advent of the steady state photocarrier grating technique
(SSPG) [2-4], in which two laser beams create a photocarrier grating in the sample by
interference. The experimental and theoretical details can be found in the literature [2-6]. With
its increasing popularity SSPG also complemented the majority (|ix)s-products by the
measurement of minority (|ix) s for different germanium and carbon alloy decomposition [7-11],
light-induced degradation [12,13], temperature [8], photogeneration rate [13,14] and hightemperature annealing [15].
An important parameter, ($, is the ratio of IPh under the presence of the grating to IPh without a
grating, given theoretically by

where A is the grating period, and <>


| and LD are fit parameters. LD is the ambipolar diffusion
length from which the minority carrier jax-product can be calculated. In the case of holes
(^x)ps = (q/kT)LD2/2.
In the transient mode in time of flight (TOF) experiments [16,17], the |rc-products (|rc)nT,
(|aT)pT for electrons and holes are usually determined by a 'Hecht1 analysis. We note here that
(M-T)n1 may differ considerably from the steady state product (|ix)ns defined above. In the TOF
case, the [ax-product is deep-trapping limited as traversing carriers are deeply trapped during
transit, with eventual recombination or re-emission occurring at times longer than the duration
of the TOF experiment. Values for (|ix)nT are smaller than for the recombination-limited (|^x)ns,
which are typically above 10"7 cm2 V 1 for optimised material [18,19], even in lightly n-type
a-Si:H, where (|ix)ns can be as high as 10"3 cm2 V 1 .

EXPERIMENTAL RESULTS

Bl

Effects of the Fermi Energy Position

/XT (cm 2 /V)

Many groups reported on the relation between a significant increase in photoconductivity and
increasing dark conductivity (Anderson and Spear [20], Beyer and Hoheisel [21], Vanier [22])
which was later complemented by other groups with the SSPG-measurements of the minority
carrier (|ix)s [9,23]. FIGURE 1 shows the room temperature Fermi energy (EFo) dependence,
reflecting the dark conductivity of the (|ix)s-products [24]. With a decrease of E c - EFo, where
Ec denotes the conduction band edge, jax-products exhibit an anti-symmetric behaviour [23].
SSPC
SSPG
Anderson, Spear
Phil.Mag. 36 (1977) 695
Vanier
Solar Cells 9 (1983) 85

E c - E f o (eV)
FIGURE 1 Review of the Fermi energy dependence of the minority and majority (|xx)s-products,
after [24]. The full lines represent results from numerical modelling.

The products (|ax)ns and (|rc)ps can be taken as a measure of the quality of the material but
additional information is important as the values can be misleading. FIGURE 2 [25] illustrates
how LD and thus (|ax)ps become larger after degradation, although the density of defects
increases. The important parameter EFO changes upon degradation as has been reported in some
detail [26]. EFo moves away from E c upon degradation and although the defect density
increases, the density of effective recombination centres for holes decreases as the dangling

&

bonds (DB) become more positively charged. See also FIGURE 1 where a larger E c - EF0
value leads to a larger (|rc)ps.

degraded
L/)=:321 nm
annealed
LD = 1 7 3 nm

A (nrn)
FIGURE 2 Effect of light-induced degradation on the ambipolar diffusion length, from which
the minority (jj.x)s-product is deduced. The shift in Fermi energy is also given, after [25].

B2

Photoconductivity as a Function of Temperature

(a)
10 3 /T (K""1)

Hole fir product (cm /V)

Photoconductivity (CT1Cm l )

FIGURE 3 shows aPh, reflecting (MT)ns (a), and one of the first measurements of (M.T)PS (b), as a
function of T for a-Si:H [8]. The photoconductivity shows the typical local maximum and the
thermal quenching effect, i.e. oPh reduces with increasing T and runs through a minimum before
increasing again. No thermal quenching is observed for the (|ix)ps-product. On the contrary, a
monotonic increase is observed for the (|ix)ps-product with increasing temperature. The
T-dependence of aph varies significantly with doping and the position of EFo. Experimentally,
thermal quenching disappears with n-type doping [27,28]. If EFo moves toward mid-gap, aph
drops below the value for intrinsic a-Si:H and the dip in the aPh-(l/T) plot broadens [27,28].

0>)
10 3 /T (K"1)

FIGURE 3 Temperature dependence of the photoconductivity and hole


(|iT)s-product for different generation rates, after [8].

Dersch et al [29] and Han and Fritzsche [30] give examples for the different features in the
temperature dependence of degraded samples for which thermal quenching is suppressed.

B3

Photoconductivity as a Function of Excitation

Parameters for the dependence on G are often defined for electrons using aph QC G711, or
alternatively, (jrc)ns <x G711"1, and for holes by (|rc)ps QC G"*1 or LD x G s [31] or ((ix)ps X G^
[32]. Index yn drops from close to 1 for intrinsic samples to values around 0.5 as EFo shifts
toward E c ; several explanations exist for this behaviour, using for example charge neutrality
arguments, but different models exist [33-35].
Typically, X for (|ix)ps drops from around 0.15 to zero with decreasing E c - EFo [31,32]. The
value of zero at higher doping is easy to understand as most of the dangling bond recombination
centres (DB) are negatively charged and recombination for holes proceeds via capture by
negative dangling bonds. The density of these states does not change with G which explains the
monomolecular recombination behaviour of the holes. In undoped a-Si:H, the situation is not
yet clear. Different models exist [31,32] in order to explain the observed values of S (or X) for
which the reader is referred to the literature.
B4

Numerical Modelling

B4.1

General background

Numerical simulation of photoconductivity in a-Si.H has been reported by numerous authors


[33,36-43], providing qualitative insight into many of the experimental features mentioned
above, and also suitable values for many parameters such as capture cross sections in the
absence of direct measurements. Such simulations can take into account all possible capture
and emission processes between the bands and the localised band tail states, and the charged
and neutral states of the divalent dangling bonds, to determine the recombination rate R. The
simulation is based on solving R(n,p) = G together with the condition of charge neutrality,
taking into account the trapped carriers in the band tails and DB states. Typically such models
use exponential conduction and valence band tails, with characteristic energies of 0.025 and
0.045 - 0.05 eV for good quality material. Dangling bonds are represented by discrete or
Gaussian distributions of divalent states, with, in the so-called standard defect model for
undoped material, D+/o energy location about 0.1 eV below the middle of the gap, and a
correlation energy of 0.2 - 0.4 eV. Capture coefficient values for neutral tail states are typically
taken as around and slightly below 10"8 cm3 s"1, with similar but, as will be seen below, larger
values for neutral DB, and up to 30 times larger values for charged DB.
B4.2

Modelling temperature dependence

FIGURE 4 shows the simulated T-dependence of n and p together with experimental data
(triangles, provided by H. MeIl, Marburg, sample from PST, Putzbrunn, Germany) which were
used to optimise parameters for solar-cell simulation [41]. The arrows indicate the change in
the ratio R / = Cn/Cnv between 1, 3 and 10, where Cn0 (Cnv) is the capture coefficient of
electron capture into neutral DB (electron capture into trapped holes in the valence band tail
(VBT)). The value for Cn0 is fixed to 10"8 cm3 s'1 here, so that Cnv for electron capture into the
VBT varies. The total DB-density is 4 x 1015 cm"3. Thermal quenching, with negative
T-coefficient for n, as found experimentally, is only observed in the simulation if R / > 1.

density (cm"^)

1OOOK/T
FIGURE 4 Experimental (from photoconductivity) and simulated temperature dependence of electron
and hole densities, after [45,46]. The arrow indicates increase in R / (see text).

An increase in R / (decrease in Cnv) increases p as trapped holes become more safe from
electron capture. Only a plateau region is found if Cnv is equal to or larger than Cn0 as in Wang
and Schwarz [42] whose numerical simulation data cannot account for thermal quenching with
negative T-coefficient. Note that n > p at all temperatures with no sign that holes take over
conduction, being suggested as an explanation of thermal quenching by Fritzsche et al [44]. A
detailed account of the variation of parameters like capture coefficients and their effect on the
thermal quenching phenomenon is given by Abel [37].
The hole density p does not exhibit any thermal quenching, consistent with experimental results.
The drop in p in FIGURE 4 at high T should be given more consideration experimentally as the
experimental data of FIGURE 1 are not yet conclusive.
FIGURE 5(a) shows the different recombination paths via the conduction band tail (CBT), the
VBT, and the D +/o - and D0/"-transitions (after [45,46]). At low T recombination via the VBT
dominates, whereas at other T, recombination via DB determines the lifetimes. Note that the
sum of the above gives the total, G. FIGURE 5(b) shows the density of positive (D + ) and
negative (D") DB and the density of trapped carriers in the VBT and CBT, which determine
charge neutrality at low T. D + is equal to D" at high T. At intermediate T the trapped hole
density compensates the D" charge. Thermal quenching arises (see also [47] ) in this model as
the trapped hole density decreases as the quasi-Fermi energies move together (which defines the
part of the density of states which determines recombination) with increasing T. This reduces
the density of recombination centres in the VBT. It is now necessary that recombination via
DB becomes more efficient, to give the negative T-coefficient in n. The D" density decreases
slightly in this temperature region, increasing the density of D 0 , which act as more efficient
electron recombination centres than trapped holes in the VBT, as Cn0 > Cnv. The lifetime drops,
despite a narrowing of the energy range between the quasi-Fermi energies. The observation
that Cn0 > Cnv is necessary for a negative T-coefficient in aph(T) (see also [37]) is consistent
with the analysis by Main et al [33,35] who need a small capture probability of electrons into
the VBT for the simulation of aPh of their n-type samples.

1OOOK/T

density (cm~3)

rec.rate (cm 3s"1)

(a)

(b)
1OOOK/T

FIGURE 5 Simulated T-dependence of the recombination rates via different paths


(a) and the charge density (b), after [45,46].

As the quasi-Fermi energies move together with increasing T, no additional more effective
recombination path is opened for holes by the change in charge distribution, in contrast to the
electron case, leading to a steady increase in p.
Wang and Schwarz [42] measured mobility lifetime products of electrons and holes and
concluded that the main recombination path at room temperature is via the VBT for high quality
material, in contrast to the above picture where DBs dominate recombination for T above
thermal quenching.
B5

Hot-Wire Deposited a-Si: H

Amorphous silicon from hot-wire (HW) assisted chemical vapour deposition [48-54] has
attracted attention because of reported superior properties as compared to PECVD a-Si:H.
The ratio of photo(AMl) to dark conductivity, often used as a measure for the photoconductive
quality of the material, reached the typical values for device-quality a-Si:H of above 105.
Several groups characterised a-Si:H from HWCVD, often by the photo- to dark conductivity
ratio [54-57]. Crandall et al [52] investigated the dependence of electron and hole (ax-products
on the hydrogen content. They found the largest values in samples with hydrogen content
between 1 and 10 at.% with (|rc)ns ((|IT) P S ) in the range of 1 x 10"7 (4 x 1(T9) cm2 V"1 in the folly
light soaked state. Zedlitz et al [57] report electron (ax-products for the annealed and light
soaked (Xe-Flash) state. In comparison to the values for PECVD samples the reported values
for the degraded HW samples are slightly improved (although the defect density is comparable)
whereas the annealed HW samples gave somewhat smaller values for the electron |iT-products.
In agreement with earlier studies Unold et al [58] report (frc)ps-values around 8 x 10"9 cm2 V"1.
They report an improved stability for samples with hydrogen content smaller than 9 at.%.
Lubianiker et al [59] compare PECVD and HW material and report room temperature electron
jrc-products between 1 x 10"7 cm2 V"1 and 2 x 10"7 cm2 V"1 for both materials and hole [axproducts of (6-7) x 10'9 cm2 V 1 .

B6

Alloys

B6.1

a-Sii_xCx:H

Wide-gap alloys of a-Si:H are employed as p-doped window layers in p-i-n solar cells. The
effects of alloying carbon with amorphous silicon have been reported by several authors
[8,61-66]. As the carbon content is increased, the bandgap increases and both the dark- and
photo- conductivity fall. Typically, the photoconductivity under AMI illumination falls from
10"4 S cm"1 to 10"8-10"7 S cm'1 as the bandgap increases from 1.75 to 2.0 eV (at x ~ 0.15).
Matsuda et al [63,64] prepared alloys with H2 dilution, finding that at a bandgap of 2.0 eV,
cjph(AMl) is dramatically increased to 10"5 S cm"1, almost as high as for undoped a-Si:H. They
suggested that H2-dilution reduces the formation of defects in the growing film surface.
Desalvo et al [67] also reported an improvement of ((j,x)s-products by between 30 and 100 by
hydrogen dilution for optical gaps below 2.35 eV. Above 2.45 eV all (|ix)s-products were
about 10"11 cm2 V"1. Mohring et al report optimised mobility-lifetime products for electrons and
holes in alloys with a bandgap up to 1.95 eV [8]. The room temperature values were around
2 x 10"8 cm2 V"1 for electrons and (1-2) x 10"9 cm2 V"1 for holes at a gap of 1.94 eV. These
authors also report the disappearance of the thermal quenching effect upon alloying in the
T-dependence of the (|ax)ns-products [8] which they attribute to a widening of the conduction
band tail. Similar results are reported by Oktti et al [68] who report on improved
(|rc)ns-products for their lowest carbon content samples.
B6.2

a-Sii_xGex:H

Narrow gap alloys of a-Si.H are used for shifting the spectral sensitivity of optoelectronic
devices, such as multi-junction solar cells. Aljishi et al [65] and Xu and Wagner [66] and Paul
[69] review optoelectronic and transport properties of a-Sii-xGe^H alloys. It is found that aPh
(AMI) for optimised alloys, i.e. prepared with hydrogen dilution, falls from 10"4S cm"1 at an
optical gap Eopt = 1.65 eV to 10"5 S cm"1 at Eopt =1.2 eV. In un-optimised alloys, the fall is
much sharper, particularly between 1.7 and 1.6 eV, falling to 10"7 S cm"1 at Eopt =1.5 eV. The
ratio of photo- to dark conductivity drastically reduces for silicon germanium alloys because of
both the drop in aPh and an increase in dark conductivity. Care was taken in the determination
of the (nr)nS-products to adjust the photogeneration rate for monochromatic illumination for the
varying optical gap [70].
In line with the description in Section Bl the electron recombination lifetime is very sensitive to
the relative position of EFo in the gap. Alloys which have EFo at midgap have much lower
electron lifetimes than those whose EFo lies slightly above midgap. The Fermi energy position
was also monitored by Abel and Bauer [H]. By measuring SSPC and SSPG they determined
that the electron \xx drops by more than one order of magnitude to around 4 x 10"7 cm2 V 1
upon alloying with x = 0.43 whereas the hole (ax-product decreases by only a factor of 2 - 3,
slightly above 10"9 cm2 V"1. They conclude from the photoconductive properties that the
material is an appropriate candidate for photovoltaic applications if the Ge content is low
enough.
The photoconductivity in a-Sii-xGex:H alloys normally follows the relation aPh c G^ with
0.5 < yn < 1 [65]. For an alloy with Eopt =1.32 eV, such data allowed a reconstruction of the

gap DOS into a conduction band tail of characteristic energy 50 meV, and a defect with a
Gaussian distribution peaked at ~0.4 eV below Ec [71].
Wickboldt et al [72] report on RF glow discharge CVD deposited a-Sii.xGex:H of large x, using
cathodic deposition instead of the more common anodic deposition.
Steady-state
photoconductivity appears improved, with a quantum-efficiency-mobility-lifetime product t|ux
of (1-3) x 10-7 cm2 V"1 for 0.75 < x < 1.0, and (6-10) x IO'8 cm2 V 1 for 0.50 < x < 0.75. The
improvements are attributed in large part to the reduction of long range structural heterogeneity
observed in X-ray scattering and electron microscopy, and partly to the reduction in midgap
state density.
The thermal quenching effect in the T-dependence of the photoconductivity disappears upon
alloying which Bauer et al [73] discuss in relation to other results from transient
photoconductivity and numerical modelling, relating the effect to a wider conduction band tail
in the alloys.

CONCLUSION

This Datareview discusses some of the steady state photoconductive properties of PECVD and
hot-wire deposited a-Si:H and amorphous silicon carbon and germanium alloys, including the
temperature and doping dependence of the photoconductivity and the majority and minority
mobility-lifetime products in amorphous silicon. Numerical modelling techniques used in the
analysis of photoconductivity are reviewed, and typical parameter values in use in numerical
models are given.

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4.5

Transient photoconductivity in a-Si:H and its alloys


C. Main
May 1997

INTRODUCTION

Transient photoconductivity (TPC) is defined here as the photoconductive response to impulse


(or step) optical excitation, of a photoconductor. In the present case this normally means a
sample in thin film form, with coplanar or gap electrodes, or in a sandwich configuration, with
semitransparent electrodes. If the contacts are ohmic, replenishment of the carriers occurs and
secondary photocurrents are observed, with excess carriers being finally removed by
recombination. This contrasts with the use of blocking contacts in the related time-of-flight
(TOF) measurement [1] on transport phenomena. Excitation, usually with above-gap-energy
photons, is provided typically by a pulsed laser source, e.g. a nitrogen-pumped dye laser,
producing a density N of excess carriers. Measurement of the resulting transient photocurrent
Ai(t) is effected by use of a suitable series resistance - voltage amplifier combination, or by an
amplifier in transimpedance configuration. Design of such measurement systems is thus similar
in many respects to that of any sensitive photo-detector-amplifier system.
TPC in a-Si:H and related materials is influenced by states within the mobility gap; shallow band
tail states and deeper lying defects, which are present in continuous distributions with respect to
energy. At room temperature and above, excess carriers produced by the excitation interact
with these states via multi-trapping processes, and Ai(t) reflects transport by the fraction of
excess carriers in extended states. At low temperature (<100 K), the transient photocurrent will
also arise from excess carriers hopping between localised states. These observations raise the
possibility of using TPC as a means of studying transport and electronic structure, i.e. carrier
mobilities and density-of-states distributions.
TPC in the presence of multi-trapping has been described by a number of authors [2-4]. The
description by Tiedje and Rose [2], although restricted to the case of slowly varying exponential
band tails and a single carrier type, is particularly clear. In this model, after initial trapping of
most of the excess carriers, interchange between traps and the band occurs, by thermal release
and further trapping. The excess population 'thermalises' downward in energy in a 'packet'
which has a peak density at a 'demarcation' energy Ea(t) = kTln(vt) defined as the trap depth for
which the emission time equals the time elapsed since excitation, where v is the attempt to
escape frequency, assumed for simplicity to be energy independent. During this process, the
partition between free (An) and trapped (Ant) excess carriers changes. In the case of an
exponential band tail with distribution g(E) = g(Ec)exp(-E/Eo) the photocurrent decays in a
power law form Ai(t) - An(t) ~ t"*1""* where a = kT/Eo. From an alternative viewpoint, this
process can be described in terms of the effective instantaneous mobility of the entire excess
carrier group changing with time -Ai(t) ~ Hd(t)N ~ t"*1""*, i.e. anomalously dispersive transport.
We note that in the contrasting case of a single trap level dominating all others, the partition
between free and trapped carriers becomes constant, resulting in a plateau in the form of the
Ai(t) versus t relation.

Recombination finally removes excess carriers, normally at long times (although see Section
B 1.4 for the effects of very high excitation). It is important to note that the observed time to
recombination TR may be much longer than the mean recombination time To of a free carrier.
Many trapping and release events may occur before the carrier has spent an appropriate length
of time in extended states. In the case of anomalously dispersive transport, the decay of
photocurrent after the onset of recombination may be particularly protracted as release from
progressively deeper trapped charge must occur prior to recombination. Additionally, the
recombination may be monomolecular or bimolecular in nature. Pandya and Schiff [5] give a
detailed general account of these possibilities.
Many methods have been devised to extract information on trap distributions from the Ai(t)
versus t decay in a-Si:H and other materials, both in TPC and TOF measurements [1,2,6-8].
The essential problem is to identify the influence of traps at a given energy on Ai(t), when multitrapping involves simultaneous interaction with all of the gap-states. A review of techniques
used to find trap distributions is given by Marshall [I]. More recently, successful techniques
have been described by Main et al [9] and Naito et al [10], which respectively make use of
numerical Fourier or Laplace transforms of time sampled data.
Alternatives to impulse response measurement include the integration of the impulse response
[11], the measurement of the step response to the onset of constant excitation, or the decay
from steady state after excitation G has been removed [12].
Many authors have used this measurement to obtain information on the drift mobility (ID of the
dominant carrier, using the following argument. The steady-state photoconductivity Aa just
prior to the termination of illumination is given by Aa = Groqfio, where the product fioTo is the
free-carrier mobility-lifetime product. If the observed decay of photocurrent IPh has an initial
slope (it need not be exponential) dlph/dt, then it is possible to define an initial decay time X1 as
follows:

(1)

and the drift mobility [iD is then found using the relation [iDX{ = |XoTo. Although this result has
been used in work on a-Si:H and other materials for many years, its general validity has been
questioned in a number of recent papers [13,14]. The problem is in associating the initial decay
with the same complete ensemble of excess carriers to which the 'drift' mobility is ascribed.

TRANSIENT PHOTOCONDUCTIVITY IN a-Si:H

Bl

Elemental a-Si:H

Bl.1

Undoped a-Si:H

Photocurrent (A)

Typical traces of Ai(t) versus t are shown in FIGURE 1 for undoped a-Si:H at moderate
temperatures, i.e. in the multi-trapping regime, and at moderate impulse excitation (N < 1016
cm"3) [15]. It is thought that this reflects the electron photocurrent, since the Fermi energy E F
lies slightly above mid-gap in undoped a-Si:H, and the electron mobility is higher than the hole
mobility. Typically a value of 1012 Hz is assumed for v. After initial trapping in shallow bandtail states at very short times of around 1 ps - 1/v, below the time range of standard TPC
measurement, the photocurrent decays only slowly until about t - 100 ns, indicating rather nondispersive transport, with an effective mobility in the range 0.1 - 1.0 cm2 V 1 s"1, similar to that
found directly in TOF measurements.
The temperature dependence of this 'plateau1
photocurrent is activated, returning an energy of 0.12 - 0.20 eV on Arrhenius plots [16]. It has
been argued that this feature is caused by a trapping in a band tail which becomes very steep in
the depth range 0.12 - 0.15 eV. Since the free electron mobility is typically in the range 10-20
cm2 V"1 s"1, then in this time range, only 1 - 5% of excess electrons are free. Alternatively, this
region is indicative of a steep exponential conduction band tail with characteristic energy
around 0.025 eV [17].

A-SkH

T=300K

Time (s)
FIGURE 1 Transient photocurrent in a-Si:H; circles - experimental data points,
line - computer simulation fit to data (adapted from [15]).

At around 100 ns - 1 |is, Ai(t) begins to fall rapidly by up to two to three orders of magnitude.
This has been interpreted as resulting from deep trapping into neutral dangling bond defects. A
[XX product of around 10"7 cm2 V 1 is thus returned, using the 'plateau1 photocurrent just before
deep trapping and the observed trapping time, in agreement with other measurements on
undoped a-Si:H. We note here that a single TPC measurement cannot unambiguously
determine the trapping capture coefficients Cn of the shallow tail states or the deeper defect
states, nor an absolute density of states, but rather returns the product of the two.
At longer times, in the range 10"5 - 10"1 s, the decay of Ai(t) becomes shallow, typically of
approximately power law form, with an exponent of less than -1.0. This can easily be
misinterpreted as due to multi-trapping thermalisation in a featureless exponential distribution of
deep states, but Schiff [18] and Main et al [15] have demonstrated that a structured distribution
of defect states, peaking at 0.65 eV depth, can lead to such a decay. A final downturn due to
recombination occurs at very long times, typically >100 s at room temperature. It is thought
that the same defect states responsible for the deep trapping feature are involved in
recombination.
B1.2

n-Type a-Si:H

TPC has been reported for n-type a-Si:H by several authors [16,19]. The most obvious effect is
that the short-time plateau region extends to much longer times, typically to 10"4 s at room
temperature. There is no agreed interpretation of this phenomenon. Oheda [16] viewed the
slow decay as resulting from recombination of electrons via recombination centres occupied by
trapped holes, and with a wide distribution of electron capture times. Main et al [19] and
McMahon and Crandall [20] take the view that the rate limiting step to recombination via
dangling bond defects is the release to the valence band extended states of minority holes
trapped in a distribution of 'safe' hole traps which do not themselves act as recombination
centres. A third view is that the phenomenon is caused by upward band bending at the film's
free surfaces, separating the excess electrons from excess holes [21].
B1.3

Effect of optical bias

The influence of'background' steady optical excitation on the form of the TPC in undoped and
n-type a-Si:H has been reported by a number of authors [22-25]. There are two main effects of
this 'optical bias' on the transient. First, deep electron traps become occupied as a result of
steady excitation and become unavailable as traps. This has the effect of enhancing the transient
photocurrent over the time range in which these traps normally have an influence. At longer
times, however, the increased occupancy of recombination centres which also accompanies the
optical bias, means that the rapid turndown in the TPC associated with recombination occurs
earlier.
Bl.4

High excitation effects

At high pulse excitation levels, generating an excess carrier density of more than about 1017
cm"3, non-linear effects have been observed. The short-time photocurrent (t < 1 ns) becomes
sub-linear in optical pulse height. This has been interpreted as resulting from bimolecular or
Auger recombination of free and band-tail-trapped carriers [26], in a situation in which the
normal defect-mediated recombination channel is by-passed.

B2

Alloys

B2.1

a-Sii.xCx:H

There are relatively few detailed reports of impulse response TPC in a-Sii-xCx:H alloys. Bayley
and co-workers [27,28] report on TPC and TOF measurements on these alloys over a range of
values of x from 0.0 to 0.088. In general, as x increases, the short time current falls, and the
data are interpreted in terms of an overall increase in tail state density (although the tail slope
does not appear to change significantly) and an increase and broadening in the density of deeper
lying states. Similar results have been obtained by Briiggemann et al [29] who find that as the
optical gap increases to 1.93 eV, corresponding to gas phase ratio

the electron mobility obtained from the short time photocurrent at t = 50 ns falls from 0.52 cm2
V"1 s"1 for undoped a-Si:H, to 0.018 cm2 V"1 s"1. Densities of states computed from TPC for this
range of compositions indicate an overall increase in shallow tail state density, with an increase
in the density of a deep band of defect states at around 0.65 eV depth, from about 2 x 1016 cm"3
to 2 x 1018cm"3.
Oktu et al [30] report on decay from steady state in a-Sii-xCx:H alloys. The initial decay time Ti,
as defined in EQN (1) above, is activated, with activation energy -0.12 eV over the
temperature range 140 - 300 K, a value similar to that obtained for undoped a-Si:H [12].
Adriaenssens and Oktu [31] report on drift mobilities derived from such decay time
measurement. Drift mobilities generally fall with increasing carbon content. For an increase
from x = 0.0 to x = 0.08, the drift mobility decreases by a factor of 5 at room temperature, to
0.02 cm2 V*1 s"1, while the activation energy of the drift mobility increases, from 0.13 eV for
x = 0.0, to 0.26 eV. Other related measurements include TOF in space-charge limited mode by
Eliat et al [32] which indicate that the drift mobility falls to a somewhat lower value of around
10"3 cm2 V 1 s"1 as x is increased to 0.088. Previous TOF measurements by Gu et al [33] also
reveal that the electron drift mobility falls as carbon content increases and the bandgap rises
above about 1.75 eV.
B2.2

a-Sii_xGex:H

Xu and Wagner [34] and Alijishi et al [35] provide useful reviews of transient
photoconductivity in a-Sii_xGex:H alloys, albeit mostly dealing with TOF measurements.
Pre-transient currents, which are comparable to TPC currents, indicate that incorporation of Ge
even in small amounts removes the 'non-dispersive' plateau from the photocurrent impulse
response, switching the transient to a sloping, anomalously dispersive form on log (I)-log(t)
axes. As the optical gap is reduced from 1.7 eV to 1.6 eV, there is a striking reduction in the
electron drift mobility obtained from TOF measurement, from ~2 cm2 V"1 s"1 to less than 0.1
cm2 V 1 s"1. Several models, aided by computer simulation [36-38], have been proposed to
account for this behaviour. There is a rapid increase in the conduction band tail density, while
the anomalous dispersion in low gap alloys is basically due to the interaction of drifting
electrons with deep defects. Wang et al [39] examined TOF data with varying x, and with gap

spanning the range 1.47 - 1.72 eV, and conclude that the data may be accounted for using only
variations of conduction band tail width.
With initial Ge incorporation, the electron deep trapping time is reduced sharply. TOF
measurements indicate [35] a fall in the ux product from around 2 x 10"7 cm2 V 1 for a-Si:H,
gap 1.75 eV, to 10'9 cm2 V"1 for a gap of 1.6 eV. Additional alloying has a smaller effect. The
similarity of the fall in electron drift mobility and the jrc product tends to indicate that the
lifetime is independent of the optical gap.

CONCLUSION

This Datareview covers the multi-trapping description of transient photocurrents in a-Si:H,


experimental TPC methods and analysis of TPC data to estimate densities of states. Typical
TPC behaviour is outlined for undoped and doped material, and effects of optical bias and high
pulse excitation are also covered.

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CHAPTER 5

RECOMBINATION OF EXCESS CARRIERS


5.1
5.2
5.3
5.4
5.5

Luminescence of a-Si:H
Luminescence of a-Si:N:H
Luminescence of a-Si:C:H
Luminescence of a-Si:Ge:H
Light-induced defects and the Staebler-Wronski effect in
a-Si:H

5.1

Luminescence of a-Si:H
T.M. Searle
July 1998

INTRODUCTION

The basic spectroscopy of a-Si:H was established in the 1970s and early 1980s. Useful reviews
have been given by Street [1,2]. Photoluminescence (PL) is the usual approach, exciting films
grown on roughened substrates to avoid interference effects with light almost always above the
band edge, greater than 1.8 eV say. The 2.41 eV Ar+line is a typical choice, being absorbed in
the upper 10% of a 1 |nm film. The simplest measurements are made at liquid helium
temperatures.

SPECTRA

Typical spectra are shown in FIGURE 1, from [3]. The PL band is broad and structureless,
peaking at between 1.3 and 1.4 eV and having a width of about 280 meV. For material not best
considered as an alloy, i.e. with dopants present at levels measured in ppm and with hydrogen
levels less than say 10%, the spectra
E
change little from one material source to
peak
(eV)
another.

In poorer material, or in doped films


(doping introduces dangling bonds (DB)),
a second broad band appears at lower
energies, typically about 0.9 eV (FIGURE
2 from [4]), though the energy depends
somewhat on the doping type [5]. The
recombination path here is from band tail
to DB, which has an energy level near
mid-gap.

[eV)
RELATIVE PL INTENSITY

In good (low dangling bond density)


material, this band is the only feature.
The best estimates of the internal
efficiency at low temperature yield values
greater than 35%.
The transitions
involved are between the band tail states;
initially holes and electrons drop down
their respective tails until the radiative rate
becomes faster than the phonon-mitigated
downward rate.

TCK)

PHOTON ENERGY eV
FIGURE 1 PL spectra for PECVD a-Si:H between 10
and 240 K [3]. The inset shows the temperature
dependence of the peak position and width.

Relative luminescence intensity

R.f. sputtered
T= 2OK

Photon energy (eV)


FIGURE 2 PL spectra of a high quality sputtered a-Si:H film using above
and below gap excitation to enhance the 0.9 eV band [4],

EFFICIENCIES

Luminescence intensity

These same DBs, introduced by doping, quench the PL [1,6]: phosphine silane gas phase ratios
of about 1000 ppm, for example, lower the efficiency to less than 1% of the maximum.
FIGURE 3, from [6], shows the effect. A model involving tunnelling to the DBs from the tail
states [1] suggests the form exp(-VcN) for the efficiency, with N the DB density from ESR and
Vc a 'critical volume', and comparison with the data indicates that V c is about 6000 nm3. It is
worth noting that this expression is sometimes used as a diagnostic of this form of quenching:
this needs care, since the mathematical approximation used to get this simple form breaks down
at low efficiency [7].

Band edge transition


Defect peak

Luminescence
10K

[B2H6]

Undoped
Nominal doping

[PH3]

FIGURE 3 The effect of doping on the efficiency of


the band edge (1.4 eV) and defect (0.9 eV) bands [6].

TEMPERATURE AND EXCITATION INTENSITY EFFECTS

As the temperature is raised, the luminescence efficiency of the 1.4 eV band begins to fall
significantly above 100 K. The non-radiative process is an activated one, roughly described by
an activation energy E of around 130 meV, but with a spread of energies that can be described
by a temperature dependent activation energy. Thus one finds in the literature that both the
Boltzmann form exp(-E/kT) and the alternative form exp(-T/T0), where T0 is about 18 K, are
used to describe the fall in efficiency at temperatures well above 100 K [2,8]. Experimentally,
they are hard to separate.
The temperature dependence of the efficiency of good material is complicated [1,9] by an
excitation intensity dependent increase of efficiency as the temperature rises between 4 and
50 K. The stronger the excitation, the more pronounced this is; the low temperature efficiency
can be depressed to as little as 20% of its maximum value in this way (FIGURE 4, from [I]).
The effect is related to decreases in the radiative lifetime, and may well be the result of
increasing carrier mobility with temperature. This effect does not occur when the efficiency is
lowered by defects or doping. The efficiency of the 0.9 eV peak is also less sensitive to
temperature above 100 K than the 1.4 eV band, so that it is sometimes possible to see the
former become the stronger component near room temperature, e.g. in material with efficiencies
perhaps 10% of the best.

RELATIVE LUMINESCENCE INTENSITY

There are small shifts of the PL peak near 1.4 eV to higher energies ( 1 - 3 0 meV), though these
are not easy to measure because of temperature rises associated with high excitation powers.
There are also small shifts to the red with increasing temperature, with a thermal coefficient of
around 20 kB. The inset to FIGURE 1 shows the temperature shift, though the unresolved
0.9 eV band produces an exaggerated shift at higher temperatures.

EXCITATION
POWER ImWI

TEMPERATURE <K)
FIGURE 4 The temperature dependence of the luminescence intensity as a function of excitation intensity [I].
The PL was excited at energy Ex and detected at EL; the curves are offset vertically for clarity.

EXCITATION ENERGY EFFECTS

The efficiency of excitation largely follows the amount of light absorbed in the film,
1 - exp(-a d), where a is the absorption coefficient and d the film thickness. At low a d, this is
just proportional to a. There are red shifts of the 1.4 eV PL band caused by sub-gap excitation
energies Ex, but these are small compared with those seen in alloys. Shah et al [10] give the
magnitude of this shift as (Ex -1.8)/2 eV. It is also possible to enhance the 0.9 eV band by subgap excitation, via absorption in the DB related tail below the Urbach region as shown in
FIGURE 2 [4,11,12].

TIME DEPENDENCE

Early lifetime measurements [1,13] showed the existence of a wide range of time-scales, ranging
from nanoseconds to milliseconds; this is characteristic behaviour of the amorphous states.
Two kinds of process contribute: relaxation down tails, fast on the optical time scale but
slowing as the carriers fall to low tail state densities, and ranges of radiative lifetimes due to
tunnelling recombination over different distances. Several kinds of experiments are possible:
one can watch the spectra evolve with time, or record the integrated PL after a fast pulse.
Alternatively, one can work in the frequency domain with continuously modulated excitation.
The following observations are of the 1.4 eV band.
After pulse excitation, the peak can be followed moving to the red on the time scale 500 ps to
10 ms. At low temperatures the shift overall is about 250 meV, and is very roughly linear in
log(time), i.e. about 35 meV/decade. The data of Tsang and Street [14] show three regions: a
shift from 1.46 eV to 1.39 eV over the time range 10 ns to 1 [is, a time independent peak, at the
position observed under CW conditions up to 30 |as, followed by a faster decrease at long times.
The first two regions are less obviously differentiated in the data of Wilson et al [15]. The CW
halfwidth of 300 meV has developed by as early as 500 ps, which has implications for PL
models. The behaviour in the sub 30 {is region is interpreted as a switch from relaxation to
recombination. The slower, late region is now better understood from lifetime measurements.
The early lifetime measurements were done in the time domain. Because of the wide range of
lifetimes, lifetime distributions provide the best description of the decays. One can get these
from time domain data, but frequency domain experiments (QFRS), recording PL in quadrature
to a modulated excitation source, provide lifetime distributions directly, so long as these are
more than a decade wide. FIGURE 5 gives an example from [16]. The data of Searle et al [17]
show a broad maximum in the lifetime distributions close to 1 ms and some 1.5 decades (a
factor of 30) wide at half height. This feature is very sample independent, though best quality
films at low excitation densities show slightly longer times and wider peaks. Ambros et al [16]
find a low excitation limit on this peak of 2.5 ms, and a width of a factor of 70 at 2 K. There is
a second well defined maximum in the lifetime distribution at shorter times; the 8 \xs first
reported [17] seems to have been slightly bandwidth limited, according to Ambros et al who
used higher bandwidths [16] and found 3 |is. According to them, this peak has an FWHM of
about a factor 500, and, again because of their greater bandwidth, this value is likely to be more
reliable than the earlier one. All the lifetime distributions reported, whether taken in the time or
frequency domains, seem to show evidence for the two peaks at about 1 ms and 5 (is, though
this was not noticed before the QFRS work. One finds that the faster peak becomes the

dominant one as the temperature is increased above that where the efficiency is a maximum
(50 - 80 K), or as the excitation intensity is raised. It also dominates in low efficiency material,
though the two peaks are still well defined in, for example, a P-doped (500 ppm phosphine)
sample. Both peaks are associated with radiative processes [17].

intensity (r.u.)

T=2K

lifetime (s)
FIGURE 5 Distribution of lifetimes of a-Si:H at T = 2 K [16].

QFRS measurements have also been used to investigate the dependence of the c l ms5 peak on
excitation density, and to determine the onset of geminate decay. This recombination rate is
believed to depend chiefly on carrier spatial separation, which increases, slowing the rate, as the
photogenerated electron hole density (G) decreases. At the lowest densities, the recombination
rate should become generation rate independent when each electron recombines with its own
(geminate) hole. The non-geminate region according to Ambros et al begins at excitation fluxes
below about 6 x 1015 photons cm"2 s"1; Bort et al [18] find the limit at densities of about 1 x 1020
photons cm"3 s"1. These two numbers agree if the low temperature absorption coefficient at the
HeNe wavelength used in [18] is 1.7 x 104 cm"1, which is not unreasonable. There are some
conflicts in the data sets: above the geminate density limit, the lifetime roughly follows a power
law G"p, but Searle et al [17] find p = 0.5 and Bort et al [18] find 0.9. There is also a question
about the G dependence of the faster process, in that this lifetime also only depends on G above
a different threshold, presumably not related to geminate pairs.

CONFINEMENT

This is not the place to deal in detail with quantum confinement, but a comment is in order since
PL is sometimes cited as evidence for it. Over ten years after the first investigations, there is
still no agreement and the differences in position are exemplified by two papers [19,20]. The
Sheffield view, briefly summarised in [21], has long been that, whilst confinement effects may
occur in say a-(Si:N/Si/Si:N):H structures, one cannot determine this via PL. Because electron
coherence lengths are inevitably short, thin structures (about l n m o r less) are required; one
does see blue shifts in the PL but it does not seem possible to decide if these are due to
confinement or to interface alloying.

ERBIUM AND YTTERBIUM LUMINESCENCE

Until recently, these two broad intrinsic PL bands were the only features of PL from a-Si:H,
doped or not. Following the incorporation of erbium into crystalline silicon, there have been
recent studies of the emission from rare earth doped a-Si:H. The chief interest is in the Er +
transition at 1.54 (im? relevant to telecommunications, which is 4Ii3/2 -4Ii5/2. The first
successful production (by co-sputtering) of films in which the erbium PL could be observed was
by Oestereich et al [22]. More recently, ion implantation has been used by Vandenhoven et al
[23].
The spectra from a-Si:H:Er (FIGURE 6) are less sharp [22] than for erbium in crystalline
silicon, because of the greater site disorder, but comparable in width and Zeeman substructure
to erbium in insulating glass hosts. The erbium emission is much less strongly temperature
dependent than the 1.4 eV band; a fall in efficiency of about 15 is seen between helium and
room temperature. In contrast, Bressler et al [24] see no significant quenching. The tail state
ionisation which controls the 1.4 eV band does not operate directly on the rare earth, of course.
Vandenhoven et al estimate internal quantum efficiencies of around 10"3. Bressler et al note that
the efficiency of the amorphous films at room temperature is greater than that of the erbium
doped crystal at 2 K; the amorphous network may well accommodate erbium ions more easily.
Both Shin et al [25] and Coffa et al [26] note that the presence of oxygen suppresses the
quenching; Shin et al observed a decrease to a fall by a factor of 7 between 10 and 300 K.
Presumably the oxygens surround the erbium, as they would in a silicate glass.
The Er lifetime decreases with increasing temperature, presumably partly due to competition
with phonons as in other glasses. Shin et al find that the change in lifetime is sufficient to
explain the thermal quenching. However, Fuhs et al [27], who agree that quenching leads to a
factor 15 fall in efficiency, find only a factor 2.5 change in the lifetime, and so propose other
non-radiative mechanisms. Their excitation studies show that the erbium PL can be excited by
above gap or even tail state absorption, so that there it is important to look at the energy
transfer mechanism to the rare earth as well as the ion's internal efficiency. Coffa et al [26]
have demonstrated electrical excitation, probably via hot electron impact ionisation. Er3+
emission has been excited electrically in crystalline silicon LEDs [28].

Intensity (arb.u.)

Energy (meV)

Wavelength (/xm)
FIGURE 6 The E r * 4Ii 3/2 -> 4Ii 5/2 transition
in amorphous and crystalline silicon [22].

The only other report to date of rare earth doping of a-Si.H is with ytterbium [29] which has a
single 4f transition near 900 nm. It is worth noting that Yb is often used as a co-dopant in
insulating phosphors and glasses to promote energy transfer (a 'sensitiser'), because of the high
oscillator strength of this one transition.

REFERENCES
[I]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[II]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]

R.A. Street [Adv. Phys. (UK) vol.30 (1981) p.593 ]


R.A. Street [ HydrogenatedAmorphous Silicon (Cambridge, 1991) ]
IG. Austin, TS. Nashashibi, TM. Searle, P.G. LeComber, WE. Spear [ J. Non-Cryst. Solids
(Netherlands) vol.32 (1979) p.373 ]
P.K. Bhat, AJ. Rhodes, TM. Searle, LG. Austin, J. Allison [ Philos. Mag. B (UK) vol.47
(1983) p.L99 ]
RA. Street, D.K. Biegelsen, RL. Weisfield [ Phys. Rev. B (USA) vol.30 (1984) p.5861 ]
R.A. Street, D.K. Biegelsen, JC. Knights [ Phys. Rev. B (USA) vol.24 (1981) p.969 ]
T.M. Searle [ Philos. Mag. B (UK) vol.46 (1982) p.163 ]
T.M. Searle, W.A. Jackson [ Inst. Phys. Con/. Ser. (UK) no.95 (1989) ch.9 p.571 ]
T.M. Searle, M. Hopkinson, W.A. Jackson, A.J. Rhodes, GK. Diprose [Philos. Mag. B (UK)
vol.63 (1991) p. 179]
J. Shah, A. Pinczuk, F.B. Alexander, B.G. Bagley [ Solid State Commun. (USA) vol.42 (1982)
p.717]
R.W. Collins, MA. Peasler, G. Moddel, W. Paul [ J. Non-Cryst. Solids (Netherlands)
vol.35&36(1980)p.681]
S. Yi, S. Liu, S. Gangopadhyay, W. Herbst, B. Schroder [ J. Appl. Phys. (USA) vol.80 (1996)
p.4587-91 ]
B.A. Wilson [ in Disordered Semiconductors Eds M. Kastner et al (Plenum, New York, USA,
1987) p.349 ]
C. Tsang, RA. Street [ Phys. Rev. B (USA) vol. 19 (1979) p.3027 ]
BA. Wilson, TP. Kerwin, J.P. Harbison [ Phys. Rev. B (USA) vol.28 (1985) p.7953 ]
S. Ambros, R. Carius, H. Wagner [ J. Non-Cryst. Solids (Netherlands) vol.l37&138 (1991)
p.555]
T.M. Searle, M. Hopkinson, M. Edmeades, S. Kalem, IG. Austin, R.A. Gibson [ in Disordered
Semiconductors Eds M. Kastner et al (Plenum, New York, USA, 1987) p.357 ]
M. Bort, W. Funs, S. Liedtke R. Stachowitz, R. Carius [ Philos. Mag. Lett. (UK) vol.64 (1991)
p.227]
S.A. Koehler [ Philos. Mag. B (UK) vol.77 (1998) p.27-48 ]
K. Murayama, T. Toyama, S. Miyazaki, M. Hirose [ Solid State Commun. (USA) vol.104 no.2
(1997) p.l 19-23]
M. Hopkinson, T.M. Searle, P.G. LeComber, R.A. Gibson [ J. Non-Cryst. Solids (Netherlands)
vol.97&98(1987)p.883]
T. Oestereich, C. Swiatkowski, I. Broser [Appl. Phys. Lett. (USA) vol.56 (1990) p.446 ]
GN. Vandenhoven, JH. Shin, A. Polman, S. Lombardo, SU. Campisano [ J. Appl. Phys.
(USA) vol.78 (1995) p.2642 ]
M.S. Bresler et al [ Appl. Phys. Lett. (USA) vol.67 (1995) p.3599 ]
JH. Shin, R. Sema, GN. van den Hoven, A. Polman, W.G.J.H.M. vanSark, A.M. Vredenberg
[Appl. Phys. Lett. (USA) vol.68 (1996)p.46 ]
S. Coffa et al [ Nuovo Cimento D (Italy) vol. 18D ser. 1 (1996) p. 1131 ]
E.I. Terukov, AN. Kuznetsov, V.Kh. Kudoyarova, A. Shturm, V. Fus [ Pis 'ma Zh. Tekh. Fiz.
(Russia) vol.21 (1995) p.78-84; translated in Tech. Phys. Lett. (USA) vol.21 no.9 (1995) p.717 ]
H. Ennen, J. Schneider [J. Electron. Mater. (USA) vol.l4a (1985)p.ll5 ]

[29]

E.I. Terukov, AN. Kuznetsov, VKh. Kudoyarova, A. Shturm, V. Fus [ Tech. Phys. Lett. (USA)
vol.21 no.9 (1985) p.717-9]

5.2

Luminescence of a-Si:N:H
T.M. Searle
July 1998

INTRODUCTION

Like the carbides, the nitrides provide a system with a wide range of optical gaps and
photoluminescence (PL) band peak energies EL. Because the nitride chemistry is less
complicated than that of the carbides (there is no equivalent of the latter's mixture of sp2 and sp3
bonding), the relationship between EL and the gap is also simpler. As a result, the nitrides have
been used to explore the PL mechanism in amorphous semiconductors; overall, though, there
has been much less published on nitrides than on carbides, chiefly because the latter seem easier
to dope and contact for LED construction.

SPECTRA

Typically, a-SiNx:H films are grown from silane-ammonia plasmas, and compositions range
from x = 0 with a Tauc gap ET of 1.6 eV through to approximate stoichiometry (x = %) with ET
about 4.8 eV. The earliest studies [1-5] established most of the significant features of the PL.
Typical spectra, recorded at low temperatures, are shown in FIGURE 1. EL increases as the
increasing nitrogen content widens the gap, as seen in FIGURE 2. The results of Wakita et al
[7], who measured PL spectra in samples with gaps from about 2.3 eV to 4.8 eV, finding PL
peak energies up to 2.6 eV, fit a line EL = 0.37 ET + 0.87 eV very well.
FIGURE 2 also includes the FWHM AEL of the band which increases rapidly with x. Searle and
Jackson [6] showed that this increasing PL width was linearly related to the width of the
exponential (Urbach) absorption region, characterised by the Urbach energy U; i.e.

Since U is generally regarded as being disorder driven, this strongly suggested that the same
was true for the PL width. Their analysis also ruled out alternative electron-phonon broadening
models. More detailed studies of the band shape [7] showed that the broadening was
accompanied by a decreasing third moment of the band; the ratio of half widths at half height
below and above EL drops from about 1.4 for x = 0 (i.e. a band with an extended tail to the
red), to 1 (symmetric bands) for high nitrogen contents.
It is important to note that all these spectra were produced by above gap excitation; see Section
E.

RELATIVE LUMINESCENCE INTENSITY

PHOTON ENERGY (eV)

PLfwhm(meV)

PL peak energy (eV)

FIGURE 1 a-SiNx:H PL spectra (6 K): excitation above the gap. The labels show the x values.

Tauc g a p (eV)
FIGURE 2 PL peak energy EL (circles) and FWHM AEL (squares) at 6 K versus Tauc gap Ex.

DANGLING BONDS AND PL EFFICIENCIES

The PL bands of FIGURE 1 come from inter-tail state transitions, like the familiar 1.4 eV band
in a-Si:H (x = 0). There is no sign at low temperatures of the defect band near 0.9 eV seen in
doped a-Si:H, so most nitrogen is incorporated into the network without large numbers of
accompanying dangling bonds (DBs). In the room temperature spectra of FIGURE 3, where
the inter-tail band is thermally quenched, the defect band is exposed in films with x < 0.3,
increasing in strength with nitrogen content. However, as x increases further, the defect band is
no longer detectable. It appears that at around this composition the nitride alloys become

RELATIVE LUMINESCENCE INTENSITY

T=ROOM TEMPERATURE

PHOTON ENERGY (eV)


FIGURE 3 PL spectra at room temperature, with excitation at 2.71 eV. The labels show x.

MAIN BAND EFFICIENCY

0-9eV BAND EFFICIENCY

properly 3-4 co-ordinated, as required by the nearest neighbour chemistry, avoiding the extra
DBs required by the predominately four-fold coordination of the x 0 limit. The room
temperature efficiency of this DB band is shown in FIGURE 4, where the triangles are upper
limits on the unseen band.

R=[NH3]ZtSiH4]
FIGURE 4 PL efficiency of the inter-tail band at 6 K, and the defect band at room temperature
versus nitrogen content. The latter is expressed in gas phase units; for these films, chemical
analysis shows that x 2R/(3+R). The inset shows the parameter T0 determined by fitting
these data to the form exp(-T/T0) at temperatures above about 130 K.

As a result of the low DB density in the alloys, the low temperature PL efficiency of the intertail band remains high, and is not less than 10% of the a-Si:H value in x = 0.8 (R = 2) films, as
shown on FIGURE 4. The efficiency plotted for the x = 1.1 (R = 3.8) material should be
regarded as an upper limit (see Section E) since it was measured using sub-gap light; the low
absorption of the film was allowed for.

TEMPERATURE DEPENDENCE OF THE INTER-TAIL BAND

RELATIVE PL PEAK EFFICIENCY

As in the carbides, alloying strongly reduces [3] the pronounced thermal quenching of PL seen
in a-Si:H. Examples are shown in FIGURE 5. For example, the efficiency falls by only 20%
between 10K and room temperature for a film with x = 1.1. The absolute internal room
temperature efficiency of such a film, with a spectrum extending into the green, is therefore at
least 1%. The reduced quenching in alloys is directly related to the broader tails of localised
states evident from the greater U; the result of the deeper tails is to increase the mean activation
energy to the mobility edge and hence to non-radiative centres.

T0

TEMPERATURE (K)
FIGURE 5 Temperature dependence of the PL efficiency. R, rather than x, is used
to describe the nitrogen content (see FIGURE 4). Note that the quenching in
the film with the greatest nitrogen content (R = 3.76, or x = 1.1) may be
exaggerated since sub-gap excitation was used.

The temperature dependence of the peak is small at low temperatures, but above about 100 K
becomes approximately linear with a coefficient a decreasing from -20 kB (a red shift) to about
-5 kB for x = 0.5 and almost zero for higher x. Apparent blue shifts (positive a) are the result of
sub-gap excitation [4], and can be qualitatively understood in terms of bandgap fluctuations see Section E.

EXCITATION ENERGY EFFECTS

PEAK POSITION, E L (eV)

Because of the large bandgaps, it is important to be aware of the excitation energy E x used in
PL measurements [4,5,7]. The results are most easily interpreted if E x > ET: in this range the
PL properties (spectra, temperature dependence, etc.) are independent of E x ; the data of
FIGURES 1 and 2 meet this criterion. When PL is excited with below gap light, EL and AEL
both depend linearly on E x , as shown in FIGURES 6 and 7; in this region the spectra are
essentially independent of nitrogen content x, and almost entirely (except near the x > 0 limit)
dependent on E x . There are also changes to the temperature dependence [4,5]. These effects
have been associated with the existence of spatial bandgap variations due to compositional
fluctuations, the effective gap and composition being picked out by the particular excitation
energy used.

EXCITATION ENERGY, Ex (eV)

F.W.H.M (eV)

FIGURE 6 E x dependence of EL at 6 K. R, rather than x, is used to describe the nitrogen content


(see FIGURE 4). The arrows show the room temperature Tauc gap.

EXCITATION ENERGY, Ex (eV)


FIGURE 7 E x dependence of AEL at 6 K. R, rather than x, is used to describe the nitrogen content
(see FIGURE 4). The arrows show the room temperature Tauc gap.

ANNEALING AND ILLUMINATION

Wakita et al [8] have looked at the effects of annealing on the PL spectra. The largest changes
occur at high anneal temperatures (>570 K, which is a typical growth temperature for a-Si:N:H)
where Si-H and N-H bonds are broken. In low nitrogen films the PL shifts to lower energies on
annealing at 670 K, but in higher x films the PL shifts to the blue.
There is one report of PL/ODMR in nitride films. Yamaguchi et al [9] report on the changes in
both after prolonged illumination, interpreting their data in terms of DB formation.

TIME DEPENDENCE

Seibert et al [9] and Searle et al [10] have reported PL lifetime measurements, both finding a
decrease of lifetime on alloying. Seibert et al measured lifetimes at 77 K following 10 ns pulse
excitation, finding broad, single-peaked lifetime distributions. In films with low nitrogen
contents, the most probable lifetime was about 50 |is, decreasing to 0.25 [is in material with an
efficiency of about 8% of that of the x = 0 samples. They do not give the nitrogen content of
this sample, but with this efficiency x > 0.8. They argued from an analysis of lifetime-efficiency
data that there must be a decrease in the radiative lifetime, and not just enhanced non-radiative
competition. Searle et al, working in the frequency domain at 4 K, were able to resolve the
lifetime distribution into two peaks very similar to those observed in a-Si:H, corresponding to
most probable lifetimes of about 1 ms and 8 |is (see note in Datareview 5.1). They also saw an
unresolved contribution located at shorter times. The differences between the two data sets are
readily understood in terms of the difference in bandwidth and the higher temperatures used by
Seibert et al, since the two peaks seen at low temperature merge into a single one, dominated by
the faster, as the temperature is raised.
Because the range of lifetimes is a function of PL energy, there are shifts in the position of the
PL band at different times after a pulse or, equivalently, at different excitation modulation
frequencies. These shifts are significantly greater in the nitride alloys [10]: changing the
modulation frequency from 30 Hz to 10 kHz shifts the PL peak to the blue by about 20 meV for
nitrogen-free films, but for x = 0.5 material the shift is about 90 meV. This behaviour is
probably associated with the greater band and localised tail widths: the PL FWHM is 280 meV
for x = 0 and 420 meV for x = 0.5.

REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]

H. Kurata, M. Hirose, Y. Osaka [ Jpn. J. Appl. Phys. (Japan) vol.20 (1981) p.L811 ]
R. Carius, K. Jahn, W. Seibert, W. Fuhs [ J Lumin. (Netherlands) vol.31&32 (1984) p.354 ]
LG. Austin, W.A. Jackson, T.M. Searle, P.K. Bhat, R.A. Gibson [ Philos. Mag. (UK) vol.52
(1985)p.271]
W.A. Jackson, T.M. Searle, I.G. Austin, R.A. Gibson [ J. Non-Cryst. Solids (Netherlands)
vol.77&79(1985)p.909]
T.M. Searle, W.A. Jackson, I.G. Austin [ J. Non-Cryst. Solids (Netherlands) vol.97&98 (1987)
p.991 ]
K. Wakita, S. Makimura, Y. Nakayama [ Jpn. J. Appl. Phys. 1 (Japan) vol.34 (1995) p.1425 ]
T.M. Searle, W.A. Jackson [ Philos. Mag. (UK) vol.60 (1989) p.237 ]

[8]
[9]
[10]

T.M. Searle, A. Dimba, T.-H. Wang, M. Sendova-Vassileva, F. Alvarez [ J. Non-Cryst Solids


(Netherlands) vol. 164-166 (1993) p.615 ]
W. Seibert, K. Jahn, W. Fuhs [ J. Non-Cryst Solids (Netherlands) vol.77&79 (1985) p.869 ]
T.M. Searle, M. Hopkinson, M. Edmeades, S. Kalem, LG. Austin, R.A. Gibson [ in Disordered
Semiconductors Eds M. Kastner et al (Plenum, New York, 1987) p.357-68 ]

5.3

Luminescence of a-Si:C:H
T.M. Searle
July 1998

INTRODUCTION

Alloying with carbon, as with nitrogen, produces wide gap films and brings the possibility of
applications which require visible luminescence. For this reason the carbides have received
considerable attention, and Datareview 7.5 deals with the development of thin film LEDs. The
carbides are also important for the window layer of tandem solar cells and for image sensor
arrays. Carbide alloys are more complex than their nitride counterparts, because of the ability of
carbon to occupy both planar (sp2) and tetrahedral (sp3) sites. From a PL point of view, this
may break the link between the lowest absorption edge and the PL peak, since the two
processes may be dominated by different complexes. The higher the carbon content, the more
likely this is. Such effects are familiar now from studies of a-C, but were not known to those
who made the early PL measurements.

SPECTRA

The first PL measurements on a-Sii.xCx:H [1] were made on material with distinct a-Si:H and
a-Si:C:H regions, with the result that the spectra consisted of two bands, one from each
component. Since then, usually only single broad bands assumed to be from inter-tail transitions
have been seen, qualitatively similar to those from other alloys, though from time to time with a
hint of substructure, for example in the form of weak shoulders. The spectra of Girginoudi and
Thanailakis [2] are rare exceptions, showing a weaker but clearly resolved second peak below
the inter-tail band in material that was not diphasic.
The most useful early work is that of Sussmann and co-workers [3,4], and that of the Marburg
group [5,6]. Both grew PECVD films from ethylene/silane mixtures. FIGURE 1, from Siebert
et al [5], shows the normalised spectra at 77 K moving from the peak position EL = 1.3 eV for
a-Si:H to just over 2.0 eV in a film with carbon fraction x = 0.87. These were taken using
excitation energies E x about equal to the E04 gap, which should ensure the absence of excitation
energy dependent spectral changes. The spectra of FIGURE 1 are very similar to the earlier
results of Sussmann and Ogden [3], except that the latter show a shoulder near the 1.4 eV peak
of a-Si.H for compositions around x = 0.4. The data of Nonomura et al [7] are also
qualitatively similar. It is worth remarking that, when samples are grown for a series of
measurements such as those of FIGURE 1, it is usual to keep parameters such as growth
substrate temperature fixed, so that the properties of, for instance, the x = 0 films may not be
quite optimal.
It is important to notice that, because of the possibility of different carbon containing
complexes, the carbon content does not uniquely control EL, any more than it uniquely controls
the gap. The carbon source gas has an important role in determining the latter; it seems that at
x < 0.5, but not beyond, the gap is approximately independent of it. With both methane and

intensity (rel. units)

energy (eV)

FIGURE 1 The normalised PL spectra of a-Sii_xCx.H films at 77 K [5].

ethylene (ethene) the gap reaches a maximum at around x = 0.6, but the 2.9 eV gap achieved at
x = 0.6 with methane is wider by about 0.25 eV than with ethylene sourced material. Nevin
et al [8] , in films grown from xylene and apparently built from a mixture of a-Si:C:H (sp3) and
7C-bonded carbon (sp2), find the gap shows no maximum but continues to increase to at least
3.5 eV at x = 0.87. Larger PL energies accompany larger gaps, so Vasil'ev et al [9], using
methane, find higher peak energies at high carbon content than Sussmann and Ogden or Siebert
et al; they report two films, both Si free (x = 1), with EL = 2.3 eV and 2.9 eV. Likewise, Nevin
et al [8] find a PL peak at about 2.6 eV, independent of x so long as x > 0.7. They interpret this
as meaning that the PL comes from the sp2 components. Tianfu et al [10] also report on xylene
sourced films, using higher RF powers and lower pressures than Nevin et al. Their most
significant observation is that, though in their films the Tauc gap is lower than seen in [8] for a
given x, the PL follows the gap, i.e. EL varies with x even up to x = 1 where it is about 2.75 eV,
enabling, in principle, LEDs composition tunable across the whole visible spectrum.
As mentioned above, we should only anticipate simple correlations between the PL peak energy
and the gap for low carbon alloys. Further, several authors note that the Tauc law holds over
smaller energy ranges in some carbide films than in other alloys, so that ET is not always well
defined. The work of Engemann and Fischer [1] suggested that there was a linear relationship
with EL = A Eg + B, and A 1. If one puts a line through the data of Sussmann et al [3], a
value of A 0.6 is obtained. In studies of films grown under hydrogen dilution, Street et al [11]
found A 0.5, though the highest EL was only 1.85 eV and the gap 2.6 eV. Over a still smaller
range of EL? from 1.4 eV to 1.6 eV, Hsiung-Kuang et al [12] found A 0.8.
FIGURE 2 shows how the FWHM AEL increases with x according to [5]. The blue shift and
increasing width with increasing x are qualitatively similar to the changes seen in a-Si:N:H (see
Datareview 5.2). Indeed, Magalhaes et al [13] have examined the relationship between AEL and
the Urbach energy U (the inverse logarithmic slope of the absorption tail) in low carbon content
hydrogen diluted material, and found that they are linearly related, with a coefficient 3 = 3.3. In
'low RF power5 Tessler and Solomon [14] found (J = 3.85 0.3 for x < 0.25. In a-Si:N:H the

energy (eV)

coefficient is 4.4 0.2 [15]. It seems that disorder, rather than phonons, broadens the PL in
both these wide gap alloys.

X
FIGURE 2 The FWHM of the films of FIGURE 1 versus composition (after [5]).

In a different approach to the connection between the PL and disorder, Chu et al [16] find a
convincing linear relationship linking EL and B, where B is the coefficient in the Tauc expression
for the absorption coefficient a near the band edge in the absence of k-conservation,
i.e. a = B (hv - ET)/2. The physics is not obvious.

EFFICIENCIES

IVn3,

integrated PL intensity (arb. units)

Both Sussmann and Ogden [3] and Siebert et al [5] report a nearly linear initial fall in the low
temperature PL efficiency with x for x < 0.5, as shown in FIGURE 3. Here the efficiency is
normalised to that of a-Si:H which is about 0.3. Both groups have one data point at high
carbon content which suggests an increase beyond 0.7, but that is not certain. The 77 K data of
Tessler and Solomon [14] do show a well defined minimum, though deeper (1% efficiency) and
at lower x (0.15).

77 K
300K

X
(a)

X
(b)

FIGURE 3 Efficiencies versus composition from (a) reference [5] at 77 K,


and (b) reference [14] at 77 K and 300 K.

There are similarities between these alloys and the nitrides, where the efficiency of the inter-tail
band does not fall below 10%. This contrasts with doped a-Si:H, where a few hundred ppm of

borane in the gas phase, or spin densities (of dangling bonds, DBs) of 1018 cm'3, bring the
efficiency down by nearly 1000. The reduced quenching in the carbides does not seem to be
due to lack of DBs, for Liedtke et al [6] find a spin density which peaks at about 1019 cm"3 near
x = 0.6; they argue that for x > 0.4, the spin population is increasingly due to carbon DBs,
rather than silicon ones, and that the former are, for unknown reasons, not effective
non-radiative centres. Street et al [11] also find this weak quenching, recording a minimum
efficiency of 0.05 at a spin density of 3 x 1018 cm"3; as they note, there is a lot of scatter in the
efficiency-spin density plot.

TEMPERATURE EFFECTS

In the nitride alloys, as in many a-Si:H films, the defect band can be seen in, for example, room
temperature spectra. It has not been reported in the carbides despite the large DB densities,
though equally there are no reports of a search for it. The nearest feature to it is the 1.0 eV
band seen by Girginoudi and Thanailakis [2], though its energy is higher than the defect band in
a-Si.H. This could be due to the opening gap, though it seems independent of x despite a
0.42 eV change in gap; it is also odd that it does not change in strength relative to the inter-tail
band at 1.60 - 1.65 eV, despite a 33 fold change in the (very high) spin densities. Bands around
1.0 eV have been reported in other alloys.

relative luminescence intensity

The carbides are like the nitrides in that the strong quenching of the inter-tail band seen in
a-Si:H decreases with alloying. FIGURE 4 shows the results of Liedtke, Lips et al [17]; the
room temperature efficiency increases monotonically with x, despite the decrease at 10 K. This
is presumably the result of widening band tails, and increasing activation energies to the band
edge, as it is in the nitrides. The increase of efficiency with temperature seen for x > 0.7 films
should be interpreted cautiously: increasing absorption coefficients at the excitation energy with
temperature could cause this effect, but it is also strongly reminiscent of the results of sub-gap
excitation in the nitrides [18]. The data of Vasil'ev et al [9] do not show the positive

temperature/K
FIGURE 4 Temperature of the PL for different compositions [17].

temperature coefficient, despite the higher gaps of their carbon rich samples; it is also
noteworthy that the strong thermal quenching starts only between x = 0.19 and x = 0.09 for
their methane grown films, compared with x around 0.5 for the ethylene films of [17]. The
300K efficiencies found by Tessler and Solomon [14] (FIGURE 3(b)) increase as
approximately 10"5 exp (x x 22.5), approaching the 77 K efficiencies from below.

EXCITATION ENERGY EFFECTS

One might expect to find spatial bandgap fluctuations due to local variations in carbon density,
or, especially at high carbon content, to variable sp2/sp3 ratio. In the nitrides, these show up as
a linear dependence of EL on E x once the latter is below E04, and such dependencies have been
observed in the carbides by Siebert et al [5]. They only show data for x = 0, 0.5 and 1, so one
cannot be sure if there is a region in which EL depends only on E x and not on x, though the data
sets for x = 0 and 0.5 appear co-linear. The slope is about 0.4, lower than in the nitrides. The
x = l sample also shows an approximately linear fall of EL with decreasing E x ; this certainly will
not fall on a common line with lower x material, as, for example, 1.9 eV excitation produces a
peak at about 1.5 eV in the x = 0.5 film but at 1.7 eV in the x = 1 material. Masumoto et al
[19], in contrast, find two linear regions in an EL versus E x plot for an x = 0.8 film, with a slope
at low energies of 0.75, which is similar to the nitrides.

TIME DEPENDENCE

Siebert et al [5] have measured the PL decay, derived lifetime distributions and also studied time
resolved spectra. The lifetime distributions show a single broad peak (at 77 K, the two peaked
structure certainly present at low temperatures in x = 0 material would not be obvious), which
broadens and moves to shorter times with alloying. The peak moves from about 30|nsinx = 0
films to 20 ns in x = 0.47 material. In the x = 0.37 film, the lifetime peak is about a factor 400
wide at half height, so that despite the 300 ns most probable lifetime, there are strong
contributions to the decay from, for example, 10 \is processes. At low temperatures the peak
near 1 ms seen in a-Si:H and the nitrides [20] is also present in the carbides [17].
The observations of Siebert et al [5] on the time dependent shift of the PL peak following
pulsed excitation also show significant changes on alloying (FIGURE 5). Such measurements
are generally interpreted as following the maxima of occupation of the tail states towards the
gap centre with time. However, for x greater than about 0.2, FIGURE 5 shows non-monotonic
behaviour, which clearly cannot result from thermalisation down a spatially uniform tail. Siebert
et al considered Coulombic interactions between increasingly distant and hence slower pairs as
an explanation, but gap fluctuations provide an alternative model.
There are measurements of decays at shorter times, e.g. a report of an exponential decay with a
time constant of 200 ps in x = 0.15 material [21]: since the authors observe an efficiency of
about 10%, they deduce a radiative lifetime of about 10 ns. They attribute a 300 meV red shift
during the first 400 ps to thermalisation.

delay time (s)


FIGURE 5 Time resolved spectroscopy at 77 K: E L versus time for films of different compositions [5].

Alloying tends to extend the range of lifetimes in amorphous alloys, and one should always be
aware that this range may extend beyond the capability of any particular measurement
technique.

REFERENCES
[I]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[II]
[12]
[13]
[14]
[15]
[16]

D. Engemann, R. Fischer, J. Knecht [Appl. Phys. Lett. (USA) vol.32 (1978) p.567 ]
D. Girginoudi, A. Thanailakis [ J. Appl. Phys. (USA) vol.69 (1991) p. 1490 ]
R.S. Sussmann, R. Ogden [ Philos. Mag. B (UK) vol.44 (1981) p. 137 ]
R.S. Sussman, E.H. Lauder [ J. Phys. Colloq. (France) vol.42 no.C-4 pt.2 (Oct. 1981) p.102932]
W. Siebert, R. Carius, W. Funs, K. Jahn [ Phys. Status Solidi B (Germany) vol.140 (1987)
p.311]
S. Liedtke, K. Jahn, F. Finger, W. Funs [ J. Non-Cryst. Solids (Netherlands) vol.97&98 (1987)
p.1083]
S. Nonomura, S. Hattori, S. Nhta [ Solid State Commun. (USA) vol.64 (1987) p. 1261 ]
WA. Nevin, H. Yamagishi, M. Yamaguchi, Y. Tawada [ Nature (UK) vol.368 (1994) p.529 ]
V.A. Vasil'ev et al [ Sov. Phys.-Semicond. (USA) vol.24 (1990) p.445 ]
Tianfu Ma, Jun Xu, Kunji Chen, Jiafang Du, Wei Li, Xinfan Huang [ Appl. Phys. Lett. (USA)
vol.72 (1998) p. 13]
R.A. Street, N.H. Nickel, CC. Tsai [J. Non-Cryst. Solids (Netherlands) vol.190 (1995) p.33 ]
Hsiung-Kuang Tsai, Wei-Liang Lin, Wen Jyh Sah, Si-Chen Li [ J. Appl. Phys. (USA) vol.64
(1988)p.l910]
C S . de Magalhaes, C. Bittencourt, L.R. Tessler, F. Alvarez [ J. Non-Cryst. Solids
(Netherlands) vol.164-166 (1993)p.lO27 ]
L.R. Tessler, I. Solomon [ Phys. Rev. B (USA) vol.52 (1995) p.10963 ]
T.M. Searle, WA. Jackson [ Philos. Mag. (UK) vol.60 (1989) p.237 ]
V. Chu et al [ J. Appl. Phys. (USA) vol.78 (1995) p.3164 ]

[17]
[18]
[19]
[20]
[21]

S. Leidtke, K. Lips, M. Bort, K. Jahn, W. Fuhs [ J. Non-Cryst Solids (Netherlands) vol.114


(1989)p.552]
T.M. Searle, W.A. Jackson, LG. Austin [J. Non-Cryst Solids (Netherlands) vol.97&98 (1987)
p.991 ]
Y. Masumoto, H. Kunitom, S. Shionoya, H. Munekata, H. Kukimoto [ Solid State Commun.
(USA) vol.51 (1984) p.209]
T.M. Searle, M. Hopkinson, M. Edmeades, S. Kalem, LG. Austin, R.A. Gibson [ Disordered
Semiconductors Eds M. Kastner et al (Plenum, New York, 1987) p.357-68 ]
E. Nakazawa, H. Munekata, H. Kukimoto [ Solid State Commun. (USA) vol.45 (1983) p.925 ]

5.4

Luminescence of a-Si:Ge:H
T.M. Searle
July 1998

INTRODUCTION

The germanium alloys are different from most other a-Si:X:H systems in that the gap decreases.
There has been interest in their application to photocells by absorbing photons of energies below
the gap of a-Si:H, and hence in their photoconductivity, but the photoluminescence (PL)
properties have also been explored.

SPECTRA

luminescence intensity (reiunits)

The first report was from Hauschildt et al [I]. FIGURE 1 shows the spectra as a function of
increasing Ge fraction y in Sii-yGey. As in other alloys, the low temperature spectra are
dominated by the inter-tail band. They reported a linear decrease of both the PL peak energy EL
and the PL FWHM AEL with y. EL increases from 0.67 eV for y = 1 to the low value of 1.2 eV
for y = 0. When comparing EL and the optical gap, it is worth noting that these authors use a
gap Eg defined via photoconductivity which is different from the usual E04 or E x . Their linear fit
(which underestimates EL at y = 0) gives EL = 1.13 - 0.47y eV, or EL = 0.65 Eg + 0.04 eV.

photon energy IeV)


FIGURE 1 Normalised PL spectra at 77 K. Labels show y values [I].

The PL width changes linearly from 230 meV to 300 meV. For y = 0 films this is a little greater
than the 270 - 280 meV found in the best material. Further, the peak position is low compared
with the usual 1.3 - 1.4 eV range, suggesting non-optimal material at this composition. This is
probably the consequence of the low substrate temperature (470 K), which is necessary in Ge
rich material, since for y = 1 hydrogen effusion occurs at 530 K. The optimum temperature for
a-Si:H is about 570 K.

The data of Giovanella et al [2] suggest a somewhat different relationship between EL and the
gap, i.e. EL = 0.9 ET - 0.25 eV. The difference seems to come from several factors: (a) they use
the Tauc gap, rather than that of Hauschildt et al; (b) their Tauc gaps are much higher than
normally observed, e.g. for a-Si:H they get 1.94 eV rather than the usual 1.6 eV; and (c) their
material seems to have been much more disordered even than that of Hauschildt et al, e.g. they
report widths for very Si rich films of 400 meV, which is much greater than seen in good quality
a-Si.H (280 meV is typical), (b) and (c) may be related, for very broad exponential tails may
distort the Tauc plot from which ET is determined. Their growth temperature was 460 K. They
also found very much narrower bands in high Ge films than Hauschildt et al, for example about
100 meV at y = 1; it is tempting to suggest micro-crystallinity in such films, for these widths are
comparable to those seen in micro-crystalline a-Si:H [3]; Ranganathan et al [4] show 10K
spectra from a y = 0.38 film with similar narrowness.

Luminescence-peak energy ( e V )

Street et al [5] have examined many films, mostly with y < 0.7, but including two near y = 1.
They find (FIGURE 2) EL = 1.4 - 0.8y eV with a fit to the y < 0.7 region; there is considerable
scatter, but an approximate linear fit to all points gives EL = 1.35 - 0.5y eV. Carius et al [6]
also plot values of E04, EL and AEL versus y, finding EL = 1.3 - 0.7y eV in substantial agreement
with [5] and [8]. They also agree with [1] and [8] on the weak compositional dependence of
the width. Wickboldt et al [7] have recently reported PL measurements on highly
photoconductive material, and they find 1.35 - 0.53y. As in other investigations of large
numbers of samples, there is significant scatter; for example, samples with the same E04 can
have EL values within a typical range of 50 meV.

Ge concentration (%)
FIGURE 2 EL versus Ge content y (10 K) [5].

Mackenzie et al [8] have looked at sputtered films, finding E L = 1.33 - 0.84y eV, or EL =
1.05E04 - 0.7 eV, over the range 0 < y < 0.65. They also noted that EL fell by about 0.1 eV as
the growth temperature was raised from 490 K to 630 K. Widths fell slightly with increasing
Ge content from 290 meV for y = 0 to 270 meV for y = 0.53.
Overall, there is substantial agreement between most authors that the PL peak moves linearly
between that observed in a-Si:H and the end of their compositional range. These linear fits are

sensitive to the range of compositions included, which probably explains the range of
coefficients found in the literature. The influence of measurement temperature, so long as this is
nitrogen or less (e.g. 10 K for Street et al [5] and 77 K for Carius et al [6]) can be neglected.
Most are also agreed that the width only decreases slightly with alloying. Wickboldt et al report
a fairly constant Urbach tail width U of about 43 meV in the higher Ge content films, some 17%
less than in a-Si:H; this is just the same as the change in width in their films between y = 0 and
y = 0.8 (290 meV to 240 meV), precisely as one would expect for disorder broadened peaks
and tails with U proportional to AEL. It should be noted that this is not the interpretation of
Wickboldt et al.

EFFICIENCIES

photoluminescence intensity / r.u.

Several of these groups report the variation of efficiency with y, though one should bear in mind
that this is by no means the sole controlling parameter. Growth conditions such as substrate
temperature may well affect the film quality. They show that the efficiency falls slowly at first
as Ge is introduced (Hauschildt et al [1] find a drop to about 20% up to y = 0.6), followed by a
rapid fall at higher Ge contents. The results of Carius et al [6] are shown in FIGURE 3, falling
rather more at low y than in [I]. Sputtered films are again different in detail, falling faster
beyond y = 0.4 and being about a factor 5 less efficient at y = 0.6 [6].

composition
FIGURE 3 PL efficiency versus Ge content y, the latter labelled 'composition' [6].

The results of [2] on a small number of films suggested that the efficiency might be controlled
solely by the DB density (as measured by ESR), and Carius and Finger [9] find a similar
monotonic fall; these data sets agree very well if the spin density found by Giovanella et al is
reduced by a factor of 2.2 or vice versa. Their results show an almost DB density independent
efficiency below 2 - 3 x 1017 cm"3 (using the densities of [9]), followed by a fall of over 100 as
the DB density increases by a factor of 10. As mentioned in Datareview 5.1, it is not possible to

test the non-radiative tunnelling model of Street by looking for a linear relationship between log
(efficiency) and spin density, since this is an approximation which works only at relatively high
efficiencies. It does seem that Si and Ge DBs have different cross-sections, the former being the
more effective non-radiative centres.
Street et al [5] showed that spin density was not the only parameter controlling the efficiency,
since materials of the same DB density but different composition could have efficiencies
separated by factors of up to 300.

TEMPERATURE DEPENDENT EFFECTS

Ranganathan et al [4] also report the temperature


dependence of the efficiencies of the two bands,
with the lower energy one becoming the stronger
above 130K (FIGURE 4). An interesting further
point made by FIGURE 4 is that the high
temperature slope of the log efficiency (or T0, from
the efficiency described by exp(-T/T0)) is essentially
the same for both bands, and unchanged by alloying
in this film with y = 0.38.
This suggests an
unchanged conduction band tail width, consistent
with the composition independent widths of [1,6,8],
but in apparent conflict with their own narrow PL
bands. The unchanged value of T0 in the Ge alloys
contrasts with its marked increase in wide gap
alloys. The intensity shows the downturn at low
temperatures seen in high efficiency a-Si:H under
high illumination; the efficiency of this material is
therefore high enough for the light induced nonradiative processes to compete with the dark nonradiative routes.

INTENSITY

Most of the above work was done either at He or N 2 temperatures. Measurements at higher
temperatures (up to about 200K) have been reported by Ranganathan et al [4], for
compositions with 0 > y > 0 . 5 . The PL spectra show that as the temperature increases, a
second component at about 0.8 - 0.9 eV emerges. In behaviour and position, this is strongly
reminiscent of the defect PL band seen in a-Si:H.
This band was also reported at temperatures
between 300 and 240 K by Carius et al [6], lying at
0.8 eV for 0 > y > 0.3, but moving at greater y to
0.6 eV.

TEMPERATURE (K)
FIGURE 4 Integrated PLfromthe inter-tail
band (open symbols) andfromthe defect band
(solid symbols) for y = 0 and y = 0.38 films.
The labels are 10Oy [4].

TIME DEPENDENCE

There has been rather little done on transient PL in the Ge alloys. References [5], [9] and [10]
contain brief reports. The decays show the characteristically wide range of lifetimes of a-Si:H

alloys, appearing roughly linear on log-log plots. The distribution shifts to shorter times as the
Ge content increases; as an example, the data of Street et al [5] show a decrease of about 30
between an a-Si:H film (y = 0) and one with y = 0.5. The latter has an efficiency relative to
a-Si:H of 4%, and hence it appears that in this compositional range the lifetime and efficiency
are controlled by the same non-radiative centres. There seem to be no data for the Ge rich
films, understandably in view of their low efficiencies and PL energies.

REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]

D. Hauschildt, R. Fischer, W. Fuhs [ Phys. Status Solidi B (Germany) vol. 102 (1980) p.563 ]
C. Giovanella, I. Hirabyashi, M. Yoshida, K. Morikagi [ J. Phys. (France) vol.45 (1984) p.7139]
P.K. Bhat, AJ. Rhodes, T.M. Searle, IG. Austin, J. Allison [ Philos. Mag. B (UK) vol.47
(1983) p.L99 ]
R. Ranganathan, M. Gal, JM. Viner, P.C. Taylor [Phys. Rev. B (USA) vol.35 (1987)p.9222 ]
R.A. Street, CC. Tsai, M. Stutzmann, J. Kakalios [ Philos. Mag. B (UK) vol.56 (1987) p.289 ]
R. Carius, F. Finger, W. Fuhs [ J. Non-Cryst. Solids (Netherlands) vol.97&98 (1987) p. 1067 ]
P. Wickboldt et al [ J Appl. Phys. (USA) vol.81 (1997) p.6252 ]
KD. Mackenzie, J.R. Eggert, DJ. Leopold, YM. Li, S. Lin, W. Paul [ Phys. Rev. B (USA)
vol.31 (1985) p.2198]
R. Carius, F. Finger [ J. Non-Cryst. Solids (Netherlands) vol. 114 (1989) p.549 ]
M. Gal, JM. Viner, PC. Taylor, R.D. Wieting [ Phys. Rev. B (USA) vol.31 (1985) p.4060 ]

5.5

Light-induced defects and the Staebler-Wronski effect in


a-Si:H
D.E. Carlson
August 1997

INTRODUCTION

The light-induced degradation of the optoelectronic properties of hydrogenated amorphous


silicon (a-Si:H) was first reported by Staebler and Wronski [1] in 1977 when they presented
data showing that the photoconductivity and dark conductivity of undoped a-Si:H decreased
with exposure to light. They also showed that the light-induced changes were reversible since
the original properties could be restored by annealing the films at about 2000C in the dark.
They hypothesised that the metastability might be associated with trapping of photogenerated
carriers at defect complexes or might be associated with hydrogen motion. They noted that the
activation energy for annealing out the light-induced defects was approximately the same as that
observed for hydrogen diffusion (-1.5 eV) [2].

LIGHT-INDUCED DEFECTS EV a-Si:H

The light-induced degradation of the optoelectronic properties of a-Si:H is accompanied by an


increase in the concentration of paramagnetic centres with g-values of 2.0055 as determined by
electron spin resonance (ESR) measurements [3]. These defects exhibit ESR characteristics
that are very similar to the intrinsic defects found in annealed a-Si:H films [4] and are associated
with dangling bonds on silicon atoms. However, Saleh et al [5] have detected differences in the
line shapes of transient light-induced ESR signals from intrinsic and light-induced defects
indicating that the local environment of the light-induced defect is somewhat different from that
of the intrinsic dangling bond. Kakinuma et al [6] have shown that the light-induced defects are
created throughout the bulk of the a-Si:H films when the films are illuminated with uniformly
absorbed light. The increase of metastable defects with light soaking is also evident from an
increase in sub-bandgap absorption as measured by photothermal deflection spectroscopy
(PDS) [7] or by the constant photocurrent measurement (CPM) technique [8]. The
concentration of light-induced defects increases with doping [7] and with high levels (>1020
cm"3) of impurities such as oxygen [9] and carbon [10]. However, recent studies of very pure
a-Si:H (impurity levels less than 1017 cm"3) show that impurities such as carbon, oxygen and
nitrogen cannot be directly responsible for the metastable defects since the density of metastable
defects saturates at ~5 x 1017 cm"3 after prolonged illumination [H].
Characterisation techniques such as deep level transient spectroscopy (DLTS) [12], thermally
stimulated currents [13] and dual-beam photoconductivity [14] have been used to determine the
density of states distribution for light-induced defects. Currently, many investigators believe
that the dangling bonds created by light soaking can exist in three different charge states with
different locations in the energy gap. Jiao et al [14] found that a self-consistent analysis of their
dual-beam photoconductivity data could only be obtained by assuming donor-like D+ states with
a peak 1.25 eV above the valence band edge, D0 states at 0.9 eV and acceptor-like D" states

a peak -1.25 eV above the valence band edge, D0 states at -0.9 eV and acceptor-like D" states
at -0.65 eV. The density of each defect state was in the range of 7 - 9 x 1015 cm"3 in the
annealed sample and increased to values in the range of 0.9 - 2.0 x 1017 cm"3 after exposure to 1
sun illumination for 1 hour. The density of metastable defects has been shown to increase as the
concentration of Si-H2 complexes increases, and this may be associated with an increase in
microvoids [15].

KINETICS OF METASTABLE DEFECT CREATION AND REMOVAL

The metastable defects increase with illumination intensity (G) and exposure time, and the
experimental data can usually be fitted with the expression: ND = const. G273 t1/3. This
expression can be derived by assuming that the defect creation rate is proportional to the
recombination rate and that the carrier densities at the band edges are proportional to G/ND
[16]. This model assumes that the metastable defects are associated with the breaking of weak
Si-Si bonds by the recombination of photogenerated carriers. The kinetics of metastable defect
formation have also been explained by assuming a fixed number of defect sites where metastable
centres can be created both thermally and by light and where the defects can be annealed by
both thermal and light-induced events [17]. There is some evidence that the light-induced
annealing of metastable defects is driven by the trapping of holes [18]. Studies of the kinetics of
the creation of light-induced defects show that the creation process is relatively independent of
temperature over a wide range (4.2 - 300 K) [19]. The annealing kinetics can usually be
described quite well by a stretched exponential indicating a distribution of energy levels [20].
Stretched exponentials have also been used to fit the kinetics associated with the structural
relaxation of a-Si.H when the material is cooled from elevated temperatures [21]. Other
experiments have shown that there is a good correlation between the structural relaxation
kinetics and the diffusion of hydrogen in a-Si.H [22]. If the annealing kinetics are analysed in
terms of a single activation energy, then values in the literature range from about 0.4 to 1.8 eV
with most data falling in the range of 1.0 to 1.5 eV [23].
The creation of light-induced defects causes changes in the transport properties of a-Si:H. The
extended state electron mobility [24], the electron lifetime [25], the electron diffusion length and
the hole diffusion length [26] all decrease with light soaking. However, Abramov et al [26]
observed that while the degradation of the photoconductivity and the electron diffusion length
showed a good correlation with the increase in the density of metastable defects, the hole
diffusion length remained constant for short exposure times before eventually starting to
decrease. Jiao et al [27] reported that large changes in the photoconductivity, electron mobility
lifetime products and forward bias currents occurred in the first few minutes of 1 sun
illumination without any corresponding increase in subgap absorption and explained the results
in terms of charged dangling bonds. There is clear evidence from a number of studies [28-30]
that the concentration of metastable defects in a-Si.H saturates at ~1017 cm"3 after the material
has been exposed to light for a long time (>1000 hours at room temperature). In some cases,
the saturation level appears to be associated with an equilibrium between the light-induced
defects and light-induced annealing of defects [29] while other studies indicate that the
saturation is associated with a fixed number of defect sites [28].

LIGHT-INDUCED STRUCTURAL CHANGES IN a-Si:H

There is considerable experimental evidence that prolonged exposure of a-Si:H to light causes
changes in the microstructure of the material. Several organisations have reported light-induced
changes in the Si-H vibrational modes in the infrared absorption [31-34]. Changes have also
been observed in infrared phase-modulated ellipsometry measurements with light soaking [35].
Another group has shown that prolonged illumination of a-Si:H can cause changes in smallangle neutron scattering that were attributed to increased clustering of hydrogen with light
soaking [36]. Hari et al [37] have observed changes in the proton NMR dipolar spin lattice
relaxation time of a-Si:H with prolonged exposure to light. Recently, Hata et al [38] performed
polarised electroabsorption experiments on a-Si:H and found that the ratio of the anisotropic to
isotropic component increases with light soaking indicating a structural change in the material.
Han et al [39] reported an increase in the Urbach edge of a-Si:H indicating that the chemical
bonding of the amorphous matrix changes with light soaking. While light soaking increases the
density of defects from about 1015 to 1017 cm"3, the structural changes must involve on the order
of 1020 bonds per cm3 and appear to be related to local restructuring of hydrogen bonds.

LIGHT-INDUCED DEGRADATION OF a-Si:H SOLAR CELLS

The first observation of light-induced degradation in a-Si:H solar cells was made by Staebler et
al in 1981 [40]. They also showed that the degradation could be suppressed by applying a
strong reverse bias to the cells while illuminated. The photogenerated carriers are apparently
swept out of the active region before they can recombine and create metastable defects. The
light-induced degradation of a-Si:H solar cells can be caused by increased recombination in the
bulk or in interface regions or by the distortion of the internal electric field by trapped charge
[41]; in optimised cells, the dominant mechanism is usually bulk recombination. Amorphous
silicon solar cells have been degraded in the dark by applying a forward bias so that electrons
and holes are injected into the a-Si:H and can apparently create metastable defects through
recombination events [42]. Appreciable degradation has even been observed in p-i-p structures
indicating that hole trapping can create metastable centres [43]. The degradation of the
photovoltaic parameters with light soaking can usually be described in terms of two
exponentials representing fast' and 'slow' defect states [44]. The stability of a-Si:H solar cells
can be improved by using discharges containing silane heavily diluted in hydrogen [45].
Hydrogen dilution appears to improve the stability by removing most of the 'slow' defects so
that the solar cells stabilise after about 100 hours of light soaking. The stability of a-Si:H solar
cells was shown to be strongly dependent on the thickness of the active layer by Hanak and
Korsun [46] so most commercial cells are made relatively thin (-300 nm) and utilise light
trapping configurations. The stability can also be improved by using multijunction structures
where the thicknesses of the individual junctions can be made even thinner (-100 - 200 nm).
While commercial single-junction cells might degrade about 25% before stabilising,
multijunction cells typically degrade about 14% [47]. Some recent work indicates that the
stability of a-Si:H solar cells is improved by replacing hydrogen with deuterium; the
improvement is attributed to changes in the microstructure [48]. There are also indications that
the stability of the solar cells can be improved by depositing the a-Si:H by hot-wire chemical
vapour deposition [49] or by using electron cyclotron resonance discharges with silane highly
diluted in hydrogen [50]. Recent work has shown that the light-induced degradation of
amorphous silicon (a-Si) p-i-n cells can be reversed relatively rapidly at moderate temperatures

by the application of a strong reverse bias while the cells are exposed to intense illumination
[51,52]. The rate of performance recovery increases with temperature, light intensity and field
strength; the activation energies associated with the field-enhanced recovery [53] are
comparable to those determined for hydrogen diffusion at elevated temperatures [54]. In
another recent study, Terakawa et al [55] showed that the degradation rate for a-SiGe:H alloys
decreased as the bandgap decreased, but the annealing rate did not depend on bandgap. Thus,
a-SiGe:H junctions with narrow bandgaps would tend to equilibrate at a higher steady state
performance at elevated temperatures.

MODELS FOR THE STAEBLER-WRONSKI EFFECT

There is at present no consensus about the fundamental mechanisms responsible for the
Staebler-Wronski effect. Since light-induced degradation has also been observed in a-Ge:H
[56] and in hydrogenated polycrystalline silicon [57], the mechanism appears to be associated
with local disorder and the presence of hydrogen. (In hydrogenated polycrystalline silicon, the
metastability appears to be associated with the disorder in the grain boundaries.) One of the
first models for the metastability was proposed by Adler [58] who suggested the defects could
consist of pairs of oppositely charged dangling bonds in the ground state. These Valencealternation1 pairs could trap photogenerated carriers creating neutral dangling bonds in the
metastable state. Another model proposed by Dersch et al [59] is based on the assumption that
the metastable complex consists of a weak Si-Si bond and a nearby Si-H bond in the ground
state. The recombination of photogenerated carriers could break the weak Si-Si bond and then
the nearby hydrogen atom could move to the broken Si-Si bond thus creating a new Si-H bond
and two separated dangling bonds. Pantelides [60] has suggested that the metastable defects
are associated with five-fold bonded Si atoms (floating bonds). Li and Biswas [61] proposed a
microscopic model where the metastable defects are controlled by the inherent bond length
variation of the amorphous network and short range hydrogen motion creates the defects by
insertion into weak Si-Si bonds. Recently, Carlson and Rajan [53] have proposed that the
metastability is associated with the capture of photogenerated carriers and the subsequent local
motion of a proton within a defect complex consisting of a weak Si-Si bond and a nearby Si-H
bond. Light-induced effects have even been observed in crystalline Si where light-induced
hydrogen motion has been associated with the activation of hydrogen-passivated donors [62]
and acceptors [63].

CONCLUSION

Prolonged exposure of a-Si:H to light creates on the order of 1017 cm"3 of metastable defects
that degrade the optoelectronic properties of the material. These defects are apparently
associated with silicon dangling bonds that can exist in the neutral, positively-charged and
negatively-charged states. There is also considerable experimental evidence that prolonged
illumination causes microstructural changes in a-Si:H that appear to be associated with local
rearrangements of the hydrogen bonding. While there is still no clear consensus about the
microscopic origins of the Staebler-Wronski effect, recent work tends to support the hypothesis
that the metastable defects are created by the trapping/recombination of photogenerated carriers
in combination with local hydrogen motion.

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CHAPTER 6

JUNCTIONS AND THIN FILM TRANSISTORS


6.1
6.2
6.3
6.4

Schottky a-Si:H devices


a-Si:H/a-Si:X:H multilayers and evidence for quantum
confinement
Electroluminescence from a-Si:H p-i-n junctions and
a-Si:X:H heterojunctions
a-Si:H thin film transistors

6.1

Schottky a-Si:H devices


E. Fortunato and R. Martins
October 1997

INTRODUCTION

The metal semiconductor barrier has been extensively studied since its discovery by Schottky,
Stormer and Waibel. The rectifying behaviour of this structure was independently interpreted
by Schottky [1] and Mott [2], in crystalline semiconductors. Concerning amorphous silicon
(a-Si:H) Schottky barriers, the behaviour expected is quite different from that observed in
crystalline semiconductors where the charge density in the depletion region is only determined
by shallow donors or acceptors. Here, the barrier behaviour is highly dependent on: (1) surface
finishing and the presence, or not, of a native oxide [3]; (2) shallow and bulk density of states
[4]; (3) charges associated with localised states in the gap; (4) carrier losses due to
inhomogeneities in the metal Schottky contact [5] and losses related to the neutral and depletion
regions.
The first set of a-Si:H Schottky devices was developed by Carlson and Wronski [6] who used
them to produce the first a-Si:H solar cells. Apart from this application a-Si:H devices have
been extensively used either to investigate the properties of undoped and doped a-Si:H films
and their alloys [7] or to produce diodes for applications such as in image sensor matrices and
colour sensors [8].

PHYSICAL MODEL OF THE a-Si:H SCHOTTKY BARRIER

The contact between a metal and a semiconductor leads to a transfer of charges across the
interface to bring the two Fermi energies (Ep) into alignment. The space charge in the metal
remains very close to the contact but extends much further in the semiconductor leading to band
bending of the semiconductor, as shown in FIGURE 1.
The charges are constrained to remain in the vicinity of the interface by the Coulomb attraction
forces [9] forming a dipole layer with a potential equal to the difference of the work functions
of the metal (Om) and of the semiconductor (O s ). The resulting contact has rectifying
properties that depend on the potential formed and on the characteristics of the a-Si:H
semiconductor (the density of states (DOS) and its distribution) that determine the width (W) of
the depletion region. Hence, the Schottky barrier is characterised by the barrier height OB, the
built-in potential VB and W:
(Ia)
where 1Fs is the electron affinity, defined as the energy separating the conduction band edge and
the vacuum energy, and q is the electron charge. Any additional dipole charge at the interface
(due to inhomogeneities of the Schottky contact, states at the interface above 1012 at. cm"3,

Vacuum

Vacuum

Deplection
layer W

XSidug

Metal

Semiconductor

Position

FIGURE 1 Illustration of a Schottky barrier, showing the charge


depletion layer extending into the semiconductor.

tunnelling or a thin surface oxide layer) add a potential difference across the junction that will
disturb OB. When the interface effects are included the barrier height is given by:
(Ib)
where oci is the reduction caused by the interface layer and a 2 is related to the density of surface
states and the presence of a thin oxide layer.
The potential of the depletion layer, V(x), is obtained by solving the Poisson equation [9]:
(2)
where ss 0 is the permittivity of the a-Si:H and the space charge p(x) arises from the ionisation
of the bandgap states which are raised above the equilibrium EF by the band bending, and is
related to the DOS distribution, N(E), by:
(3)

The solution of EQN (3), assuming p constant (donor like density in the gap), is given by:
(4a)

from which we obtain,

(4b)

where V 6 is the built-in potential and VA is the applied voltage.


Under a uniform DOS distribution in the gap for which p(x) = NV(x), we have:

(4c)

where the shape of the potential barrier is closely related to the experimentally observed DOS
distribution of the localised states in an a-Si:H semiconductor. The corresponding W is given
by:

(4d)
where the extent of the depletion layer is defined as being the point to which the potential is
~kT/q. Here, it is important to notice that a-Si:H has a smoothly varying DOS and so EQN
(4d) applies when the band bending is small compared with the width of the defect band, which
is about 0.2 eV. Otherwise, the charge depends on the shape of the DOS and W cannot be
easily calculated. The depletion layer has an associated capacitance (C) that, in agreement with
EQNS (4b) and (4d), is:
(4c)
or

(4f)

ELECTRICAL TRANSPORT ACROSS THE BARRIER

The barrier height can be determined from the J-V characteristics. The different transport
mechanisms across the barrier are illustrated in FIGURE 2. Thermionic emission refers to the
excitation of carriers over the top of the barrier, where the conduction band edge intersects the
interface. This process can be drift assisted by the electric field ascribed to the depletion region.
Tunnelling through the barrier reduces the apparent barrier height and is significant when the
internal field is large, which occurs when VA is high or W is narrow.

Thermionic
emission
Tunneling
Increasing

Energy

Field
emission

Position

FIGURE 2 Illustration of the 3 main transport mechanisms that can occur in a Schottky barrier. The dashed
lines show the changes in the potential profile within the semiconductor under a VA bias voltage.

Tunnelling into localised states at the band edge also causes a reduction in the barrier height.
Finally, there can be field emission from the EF at high reverse bias, possibly via gap states, or
even conduction due to field inhomogeneities caused by potential fluctuations due to
heterogeneities in the Schottky contact [4,5]. For simplicity, only electron transport across the
interface is considered, either due to thermionic emission or thermionic emission drift assisted.
Thus, the total current density (J0) at zero applied voltage is given by:
(5a)
where vR = AT2/qNc is the recombination velocity at the potential energy maximum, depending
on the Richardson constant (120 A/(cm2 K2)) and on the DOS of the conduction band edge
(Nc), and vD = J\xE is the drift velocity, depending on the product of the mobility (^) and the
electric field (E) near the edge of the depletion region, and a y factor (less than 1), which is a
function of the contact inhomogeneities. Thus, if vD vR, the thermionic emission component
dominates; otherwise, it is the drift component that dominates.
The application of VA changes the current from the semiconductor by a factor exp (qVA/kT),
because the EF is raised or lowered by qVA with respect to the metal EF. Thus, ideally
(5b)
where n is the ideality factor and is a phenomenological correction for the many possible
reasons why the current differs from the ideal model.
This ideal behaviour of the J-V characteristics is mainly conditioned by the type of surface
finishing of the semiconductor interface. If the surface of the semiconductor is not properly
cleaned and passivated, discrepancies are observed between the expected behaviour and the
experimental data, as can be seen in FIGURE 3, where the behaviour of Pd/a-Si:H Schottky
devices with and without surface passivation [3] is shown.

Current density (A/cm2)

Pd/a-Si:H Schottky diodes

With surface passivation


Without surface passivation

Voltage (V)
FIGURE 3 J-V characteristics of Pd/a-Si:H Schottky barrier produced by the plasma enhanced
vapour deposition technique (PECVD) with and without surface passivation, obtainedfrom[3].

CHARACTERISATION OF THE CURRENT VOLTAGE CHARACTERISTICS

Dl

Forward Bias

In addition to supplying information about the device performance the semilog plots of J versus
V give valuable information on the electrical characteristics of the semiconductor. When the
device is in forward bias (VF), at high voltages, the J-V characteristics should reflect the
behaviour of the quasi neutral region in the semiconductor of thickness d-W and with a bulk
voltage across it given by Vb = VF - Vj, where V, is the voltage drop across the depletion
region:
Vj = (nkT/q) In
In(VJ
(VJ00)

(6)

Thus, by plotting the variation of Vj and Vb as a function of VF we conclude that at low VF? Vb
is negligible while at high VF? Vb is no longer negligible and the junction characteristics are
controlled by the quasi-neutral bulk region, and so by its bulk resistivity (see FIGURE 4(a)). In
FIGURE 4(b) we plot the dependence of the forward current density, JF, on Vb through which
the bulk resistivity of the semiconductor can be obtained. However, the behaviour of JF and Vb
is not always ohmic.
When a non-linear behaviour is observed, this can be attributed to the presence of a space
charge limited current or to the injection of minority carriers [9], as is the case for the Pt curve
shown in FIGURE 4(b). If the excess carriers are due to the minority carrier injection from the
metal contact, a cross-over (conductivity modulation) at high JF can occur in the JF - VF
characteristics, as shown in FIGURE 5(a) [10]. Here the conductivity of the bulk material is

modulated by the injection of carriers from the metal, making it possible to define a forward
static conductivity as:
(7)
where A0 is the front metal contact area.

V. and Vb (V)

Pt/a-Si:H

V F (V)

JF (mA/cm2)

FIGURE 4(a) Dependence of the junction voltage (Vj) and the bulk voltage (Vb) on the forward voltage applied
(Vp), for a Pt/a-Si:H Schottky diode, following EQN (6) and that Vb = VF - Vj. The data were inferred from
the results shown in FIGURE 5(a) for the Pt Schottky diode and agree with the behaviour proposed in [10].

v 00

b
FIGURE 4(b) Dependence of the forward current density (JF) on the bulk voltage (Vb) for different Schottky
diodes. The data were inferred from the results shown in FIGURE 5(a) for the Pt Schottky diode. The data
for Ti and Mo Schottky diodes were taken from the results presented in [5].

Current density (A/cm2)

cross
over ,
point

Voltage (V)
FIGURE 5(a) J-V characteristics of different Schottky diodes produced by PECVD, showing
the cross-over point for the devices produced using the highest Om.

( UIO Jj) XjIApOnpUOO pJBMJOJ

JpCA/cm2)
FIGURE 5(b) Behaviour of the forward conductivity of the Pt/a-Si:H Schottky diode obtained following
EQN (7) applied to the experimental points of FIGURE 5(a) as a function of the forward current
density (JF), for different temperatures.

Now, by plotting JF as a function of a F in a bi-logarithmic scale (see FIGURE 5(b)) [7], the
region where a F is kept constant with increasing JF corresponds to the unmodulated static
conductivity of the a-Si:H. In general terms, JF in an a-Si:H Schottky diode can be given by:
(8)
where Rsh is the shunt resistance ascribed to the bulk of the semiconductor.

D2

Reverse Bias: Saturation Current Density

In an a-Si:H Schottky device Jo increases with the increase of doping/defects in the


semiconductor or when Om decreases, as revealed by FIGURE 5(a). In addition J0 has an
exponential behaviour with T, as shown by EQN (5a) and FIGURE 6(a). Thus, to determine
the main parameters that contribute to Jo, when the a-Si:H used in the Schottky diode has a low
DOS, we can plot J0 as a function of T"1, since the main transport mechanism is field emission
assisted. By doing so, the semilog plots are well fitted by a linear regression, as shown in
FIGURE 6(b). There, we see that, when the a-Si:H presents a low DOS and the surface was
properly passivated, the slope of the semilog plot leads to high Ob, agreeing with the expected
value, taking into account the Om of the metal used. On the other hand, if the surface of the
semiconductor where the barrier is established is not properly passivated, the value recorded for
O b is much lower than expected, reflecting the decrease of the barrier height due to surface
states and possible contact inhomogeneities, as also shown in FIGURE 6(b).

Current density (A/cm)

Pd/a-Si:H Shottky diodes

Voltage (V)
FIGURE 6(a) J-V characteristics of a Pd/a-Si:H Schottky diode with the surface passivated,
produced by PECVD, for different working temperatures, from [3].

In ideal cases, J0 should increase with VR, roughly as VR1/2. Such a dependence is not observed
in most a-Si:H Schottky diodes [3,5]. Generally, O b is a decreasing function of the electric field
inside the barrier. That is, increasing VR will induce a decrease of the barrier, making J0
increase as exp(AOb/kT), where A<Db is the barrier lowering by the reverse bias. Several authors
[6,7,10] found that this barrier height follows a dependence as:

(9)

J0 (A/cm2)

with surface passivation


without surface passivation

Pd/a-Si:HShottky diodes

1000/T(K 1 )
FIGURE 6(b) Dependence of J0 on T"1, for the Pd/a-Si:H Schottky diode
shown in FIGURES 3 and 6(a)? respectively.

where ed is the image force permittivity [9] and the other symbols have their usual meaning.
Experimentally, a dependence of lnJR on VR1/4 is observed, where the slope is directly dependent
on ND (the existing donor like states, for an n-type semiconductor), reflecting also the DOS in
the bulk of the semiconductor.
D3

Measurement of the Depletion Layer

Also under reverse bias it is possible to determine the depletion layer thickness (W) and its
dependence on VR through the C2 versus VR plot, at low frequencies (below 1 kHz, to have
bulk states responding to the voltage stimulus) [H]. From there, we obtain information about
the DOS distribution and the built-in potential. Nevertheless, the C"2 plot is not linear because
of the continuous distribution of the DOS. However, EQN (4f) represents a good approach to
the experimentally observed behaviour in high quality a-Si:H Schottky diodes [12]. The best
way to determine W independently is through time-of-flight measurements where holes are
immediately collected by the contact and electrons drift down the internal field of the depletion
layer, giving rise to a transient conductivity (a t = qn(j,i>E(t)) so that the field and the voltage
profiles may be calculated from the transient response, and hence W [9].
D4

Determination of the Barrier Height from Light Exposure Measurements

When the Schottky diode is under a light flux, electrons are optically excited from the metal
over the Schottky barrier, by the internal photoemission mechanism. Therefore, it is expected
that under reverse bias the photoresponse spectrum is [9]:
(10)
where E is half of the mobility gap energy [13]. Thus, from the work function of the metal used
and the state of the interfaces, it is possible to determine the different barrier heights [14]. O b
can also be determined from the photoresponse current, capacitance-voltage characteristics and
from the temperature dependence of the open circuit voltage:

(H)

DIODE IDEALITY FACTOR

The diode quality factor (n) is defined as:


(12)

where S = d lnJp/5 Vp and the other symbols have their usual meaning. In general, n is
influenced by the excess current due to tunnelling through the barrier, by local inhomogeneities
at the Schottky contact and by the presence of thin oxides in the surface [10-12]:
(13)

where the first term in brackets on the right side corresponds to the influence of the tunnelling
contribution (Eo is the characteristic tunnelling energy), and the second term corresponds to the
influence of the thin oxide layer of thickness di, permittivity 8i and diffusivity D88. The last term
in EQN (13) is a coefficient defining the degree of contact inhomogeneity [8]. Thus, by plotting
the dependence of nT as a function of temperature we can determine the type of conduction
mechanism that is present [10]. Typically, we should have a diffusion/drift field emission
process at low temperatures (below 2500C) and a diffusion/drift conduction mechanism at high
temperatures [7]. Under these conditions, it is expected that n should lie between 1 and 2, and
be a function of <Dm and of the interface defects in the barrier.

REFERENCES
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6.2

a-Si:H/a-Si:X:H multilayers and evidence for quantum


confinement
P.D. Persans
July 1997

INTRODUCTION

The demonstration that a-Si:H could be deposited in uniform ultrathin layers and multilayers
[1-5] has led to many studies aimed at understanding the nature of electronic states in
amorphous solids. In addition, the high density of reproducible interfaces in multilayer
structures has allowed researchers to study electronic defects at interfaces [6-8] and atomic
scale structure of interfaces [9-13], and to produce novel devices [14]. In this Datareview we
focus on evidence for electronic quantum confinement effects in amorphous silicon and related
materials.
The most convincing evidence for quantum confinement effects in ultrathin amorphous films is
reports of optical transitions between hole and electron sub-bands formed by wavefunction
confinement. Current-voltage characteristics consistent with tunnelling into sub-bands in
double-well structures have also been reported. There are many reports of a blue shift in the
optical absorption edge with decreasing film thickness (but with no sub-band structure) which
have also been taken as evidence for confinement. There remain issues with each of these
experimental approaches which will be discussed here as well.

STRUCTURE OF MULTILAYERS, ULTRATHIN FILMS AND INTERFACES

In order to analyse and interpret optical and transport measurements it is necessary to first
understand the structure of the ultrathin films and multilayers under study.
It is clearly possible to reproducibly deposit flat, uniform layers which are useful for quantum
confinement studies. Several transmission electronic microscope studies have shown that
significant areas of plasma-enhanced chemical vapour-deposited (PECVD) multilayers are flat
on a vertical scale of <1 nm with lateral correlation length of tens of nm [2,15-17]. Detailed
X-ray reflectivity studies show that interface roughness varies from <0.5 nm near the substrate
to ~2 nm at the top of a 1 micron thick film with a lateral correlation length of > 100 nm in
a-Si:H/a-Ge:H multilayers [18,19]. Interface roughness of only 0.28 nm has been inferred from
X-ray diffraction studies of a-Si:H/a-SiCx:H multilayers [20]. X-ray reflectivity measurements
on a-Si:H/a-SiNx:H multilayers prepared by various techniques also imply smooth interfaces
[1,11,21-23]. Photoemission studies show that a-Si:H and a-SiNx:H as well as a-Si:H and
a-SiOx:H cover one another uniformly on the scale of a monolayer [24,25]. In-situ real-time
spectroscopic ellipsometry studies of PECVD growth of a-Si:H films on SiC^ indicate that
nucleation and roughness depend on the details of gas mixing, RF power, substrate
temperature, and substrate history [26,27]. In high quality films Collins et al [26,27] deduce a
surface roughness thickness o f - 1 - 2 nm after 10 nm a-Si:H growth on a smooth substrate.
Similar surface roughness thicknesses were deduced from real-time polarised reflectivity studies

of PECVD a-Si:H/a-SiNx:H, a-Si:H/a-SiOx and a-Si:H/a-Ge:H multilayers [11,13,25,28]. The


lateral scale of the roughness cannot be determined by optical reflectivity probes. Although
images observed in transmission electron microscopy suggest specific defects (e.g. bifurcations
of layers [15,16]), the phase and density contrast mechanisms have not been sufficiently well
modelled to understand the structural implications of such images.
Compositional intermixing occurs only over a few monolayers closest to the interfaces in
PECVD ultrathin multilayer structures. Raman scattering studies show that PECVD a-Si:H/
a-Ge:H interfaces can be compositionally abrupt on a scale of one to two monolayers
[10,29,30]. A similar study on PECVD a-Si:H:F/a-Si,Ge:H:F multilayers also finds a very
narrow mixing region consistent with 1-2 monolayers [31].
Photoemission studies show that a-Si:H/a-SiNx:H and a-Si:H/a-SiOx:H interfaces can be made
abrupt except for a-SiOx:H on a-Si:H, which is graded over a 0.4 nm region due to plasma
oxidation [24,25].
Infrared and nuclear reaction studies show that H is not uniformly distributed in ultrathin films
[11,12,25]. A 1 - 2 nm thick interface region between a-Si:H and a-SiNx:H contains ~1015 cm"2
excess bonded H. Such large amounts of excess H will clearly affect the dielectric properties of
the a-Si:H in that region: excess H usually increases the apparent bandgap. Excess H is not
found at the interfaces in a-Ge:H/a-Si:H multilayers [32].
Raman studies of a-Si:H/a-SiNx:H show that there is a structurally disordered interface layer in
the a-Si:H which extends only a few monolayers [9,30,33,34] from the interface. Excess
disorder in bulk films decreases the apparent bandgap.

THE SEARCH FOR SUB-BANDS

Many research groups have attempted to observe sub-band structure either in optical spectra or
in electronic transport. Only a few have reported success with optical measurements. Several
groups take issue with evidence for confinement based on transport.
The most extensive reports of sub-band structure have come from Hattori and collaborators
[20,35-39]. Various modulation spectroscopy techniques including photothermal modulation
and electroabsorption were applied. Hattori et al reported the observation of up to three subband transitions for a series of PECVD a-Si:H/a-SiCx:H multilayers with a-Si:H well thickness
from 2 to 5 nm (see FIGURE 1). A blue shift of nearly 200 meV is reported for the lowest
transition in the 2 nm-well material. Similar shifts were reported using electroabsorption
spectroscopy [37,39]. Hattori et al also reported sub-band photothermal modulation structure
in ultrathin a-Si:H single layers. Hattori fit the positions of the sub-band transitions using an
effective mass model with m* = 0.3 n^ for the electron and m* = n^ for the hole. Roxlo et al
[40] had earlier reported unstructured bulk-like electroabsorption spectra in which the a-Si:H
structure shifted by 200 meV as the well thickness was reduced from 2 nm to 1 nm.
Ohta and Morigaki have reported a weak feature in the photoinduced absorption spectra of
a-Si:H/a-Si3N4:H multilayers with well widths of 3.6 nm and 1.8 nm [41].

(a.u.)
huS
SIGNAL
PTM

T = IOOK

PHOTON ENERGY

f u j (eV)

FIGURE 1 Photothermal modulation spectra reported by Hattori et al [35]


for a series of PECVD a-Si.H/a-SiCxiH multilayers.

Koehler and Fritzsche [42] recently reported careful optical transmission measurements on
single a-Si:H layers of nominal thickness from 2.5 to 20 nm. Although they reported a blue
shift of 120 meV in the apparent band edge, they did not observe any sub-band structure.
There are only a few reports of electronic tunnelling between sub-bands in double barrier
structures. Miyazaki et al [43] prepared single phosphorus-doped a-Si:H layers (1.3 to 4 nm
thick) sandwiched between two 4.6 nm thick a-Si3N4:H barriers. They reported weak structure
(up to 3 transitions for well width - 4 nm) in the current-voltage characteristics at 77 K which
shifted with well width. A shift of 200 meV is reported for a well width of 1.3 nm. Miyazaki et
al fit the observed transition energies with m* = 0.6 n^ for electrons in a-Si.H. Pereyra et al
[44,45] reported striking negative resistance characteristics in an a-Si:H/a-SiCx:H double barrier

structure. They found that the number of negative resistance features depended on the barrier
height.
Arsenault and collaborators argue that weak features such as those observed by Miyazaki et al
in the current-voltage characteristics of double barrier structures are due to a transition from
space charge limited conduction to high field hopping [46,47]. Driisedau [48] has analysed
temperature dependence and field dependence of perpendicular current in a-Si:H/a-Ge:H
multilayers and has found that the differential resistance of the a-Si:H barriers vanishes at high
field. He concludes that effects due to confinement at such fields are questionable. Bernhard
and collaborators [49] argue that hopping and filamentary conduction dominate current-voltage
characteristics of a-Si:H/a-SiNx:H structures.

BAND-EDGE TRANSPORT

Interpretation of band edge electronic transport in a-Si:H/a-SiNx:H multilayers is problematic.


First, interface defects contribute charge which shifts the chemical potential in the a-Si:H well
layers with thickness [5,50]. Transport perpendicular to the barriers is probably controlled by
defects or pinholes rather than sub-band tunnelling. When the nitride barrier layer is thin
enough for reasonable tunnelling transmission, the integrity of the barrier is questionable.
Several authors have questioned the interpretation of high field measurements [46-49].
There have been many reports of electronic transport parallel to and perpendicular to layers in
a-Si:H/a-Ge:H and a-Si:H/a-SixGei_x:H [51] multilayers. We focus here on a-Si:H/a-Ge:H
multilayers because the composition and hence the bandgap of the a-SixGei_x:H layers could not
be independently checked in multilayers [31]. The most extensive studies of transport in
a-Ge:H/a-Si:H were reported by Wronski and collaborators. They reported on a series of
multilayers in which the ratio of a-Ge.H to a-Si.H layer thickness was kept fixed and the repeat
distance was varied from 10 nm to 1 nm [52-54]. The room-temperature low-field conductivity
parallel to and perpendicular to the layers shown in FIGURE 2 is characteristic of such studies.
Wronski et al explain the decrease in parallel conductivity by a quantum confinement induced
shift in the conduction band mobility edge. The non-monotonic behaviour of the perpendicular
conductivity is explained by a combination of a shift upward in the a-Ge:H mobility edge and
increased tunnelling through the a-Si:H layers. Wronski and Hicks [55] also reported a shift in
the Schottky barrier height for various metals on a-Si:H/a-Ge:H multilayers which is equal to
the shift deduced from conductivity measurements.

THEOPTICALBANDGAP

Many researchers have reported significant shifts in the apparent optical absorption edge of
a-Si:H bounded by a-SiNx:H [1,2,4,5,23,34,56], a-SiOx:H, or a-SiCx:H [17,57]. Others have
reported shifts in the optical bandgap for a-Ge:H bounded by a-Si:H [32,53,54]. Many authors
take issue with measurements of the optical shift.
The definition of the optical gap in amorphous semiconductors has always been problematic.
Most reports have used one of the standard extrapolation rules. Tauc introduced a simple
extrapolation rule ((aE) 1/2 = C(E-EG)) which produces consistent results for many materials and

o (S cm-1)

d f (*>
FIGURE 2 Room temperature conductivity of a-Ge:H/a-Si:H multilayers
measured parallel to (cr^ and perpendicular to (a ) the layers [52].

Intensity [arbitrary units]

a-Si layer thickness

Wavelength [nm]
FIGURE 3 Room temperature photoluminescence spectra of MBE deposited
and oxidised (a-Si/a-SiO2) ioo multilayers with a-Si layer thickness as shown [64].

which is in very wide use. The line produced by such a plot for a-Si:H curves upward with
increasing energy and as a result the apparent bandgap increases by as much as 150 meV for
measurements of thinner films [58]. Cody proposed an extrapolation rule ((oc/E)1/2 = C(E-EQ))
which produces consistent values of EG for film thickness from a few tens of nm to several
hundred nm [59]. If amorphous multilayers have sub-band structure, such rules must be
modified.
Optical measurements of the bandgap of multilayers fall into two categories: (1) either well or
barrier width is varied while the other is fixed; (2) the ratio of well and barrier width is fixed
while repeat distance is varied. In the first case the overall composition of the film is varied
through a given series, complicating optical analysis. In the latter case the coupling between
wells and the confinement dimension are both changed, complicating the quantum
interpretation.
Many groups have reported large shifts in the Tauc gap of a-Si:H/a-SiNx:H with decreasing well
thickness and fixed barrier thickness. Typical shifts are 150 meV for 2 nm well thickness
[1,2,4,5,23,56,60].
Collins and Huang [61] pointed out three problems with such
measurements. First, as the volume fraction of a-Si:H decreased the effective total thickness of
the a-Si:H layer also decreased and the apparent Tauc gap increased due to the curvature of the
Tauc plot mentioned above. Second, the index of the barrier layer depends on photon energy
and the effective medium absorption coefficient will vary even if the layer absorption coefficient
does not. Third, most analyses assumed ideal layers but there is clearly some level of interface
roughness which changes the applicable effective medium theory. Collins and Huang argued
that the first two effects could explain most of the reported shifts.
A second group of experiments, performed on a constant well/barrier-ratio series of a-Si:H/
a-SiNx:H multilayers with fixed a-Si:H total thickness, showed a somewhat smaller (90 meV)
shift for 2.5 nm thick a-Si:H layers [34]. The optical analysis of these experiments avoids Tauc
extrapolation and index problems. We note that although the Si and N content of these films
changes abruptly over 0.5 nm at each interface, the H content is increased over a few nm near
interfaces by 10 - 20%. Such an increase in H content could explain the observed shift.
Large shifts in the band edge have also been reported for a-Si:H/a-Ge:H multilayers where the
well and barrier thicknesses are kept in constant ratio [32,54,62]. A shift of 100 meV is
reported for 2 nm thick a-Ge:H layers. It has been suggested [62] that interface roughness and
compositional mixing over 2 - 4 monolayers near each interface can explain the shift without
recourse to quantum confinement. Such a wide mixing region is large compared to results of
Raman analysis, but it is not out of the question.
There have been many reports of photoluminescence in all types of multilayers. Most of these
reports address band-tail to band-tail or defect to band-tail transitions, the energies of which are
not strongly affected by film thickness. One group [63,64] has recently reported visible light
emission from a-Si/a-SiC>2 superlattices in which a-Si is deposited by MBE and then oxidised.
The peak energy of the emission depends on a-Si layer thickness, varying from 1.7 eV for
2.8 nm a-Si layers to 2.3 eV for 1 nm layers, and has been interpreted by the authors as
band-edge emission from quantum-confined states in the a-Si.

CONCLUSION

Periodic amorphous multilayers and single layers based on amorphous silicon and related
materials can be reproducibly deposited with smooth, compositionally-abrupt interfaces. These
materials have been extensively explored for photovoltaic, thin film transistor, and other
applications. Ultrathin multilayers have permitted us to study structure and defects at
interfaces.
Researchers disagree on whether there is convincing evidence for quantum confinement.
Experiments interpreted as providing evidence for quantum confinement are: (i) blue shift in the
optical band edge with decreasing layer thickness; (ii) increase in band edge transport activation
energy parallel to layers with decreasing layer thickness; (iii) structure in the current-voltage
characteristics of double-barrier structures; (iv) structure in optical modulation spectra of
multilayers and single layers. Each of these experiments has been attacked. The way in which
the optical band edge is defined and the fact that many measurements were carried out in
systems in which the total well layer thickness was varied can lead to apparent blue shifts of the
same order as those reported. It has been suggested that compositional and structural variation
near interfaces as well as interface roughness interfere with band edge determination in
constant-composition multilayer series. Similar composition and inhomogeneity issues are
raised in the interpretation of band edge transport experiments. It has been argued that currentvoltage structures in double barrier systems can be explained by the transition from space
charge limited current to hopping limited transport and by filamentary conduction. Finally, the
strongest evidence for discrete quantum levels, structure in optical modulation spectra, has not
been widely reproduced.

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Previous Page

6.3

Electroluminescence from a-Si:H p-i-n junctions and


a-Si:X:H heteroj unctions
D. Kruangam
July 1997

INTRODUCTION

Electroluminescence is the emission of light at a rate far in excess of the thermal equilibrium rate
for the frequencies and temperatures involved under the application of an electric field to a
solid. There are generally two types of electroluminescence.
The first is 'intrinsic'
electroluminescence which is an effect of the electric field alone, the charge not being
exchanged between the electrodes and the semiconductors. This type of emission comes from
the excitation of the radiative recombination centres by inelastic collisions with thermally
generated charge carriers that have been accelerated to high energies under the electric field.
The second one is 'injection' electroluminescence in which luminescence is created in or near the
depletion layer of a p-n junction, formed within the semiconductor, through the recombination
of injected electrons and holes. In this Datareview, the focus will be placed on the latter type
which is the basic phenomenon for the light emitting diode (LED).

a-Si:H P-I-N JUNCTIONS

The benefits of studying the electroluminescence effect of a-Si:H p-i-n junctions are twofold.
One is the understanding of transport and recombination processes in a-Si:H solar cells since
they have the same p-i-n junction structure. The other is the knowledge for further
understanding of mechanisms for the development of a-Si:H and its alloy based light emitting
diodes.
Bl

Steady State EL in a-Si:H p-i-n Junctions

The first attempt to observe electroluminescence (EL) in a-Si:H forward biased p-i-n junctions
and Schottky barriers at liquid nitrogen temperatures was carried out in 1976 by Pankove and
Carlson [I]. The thickness of the i-layer is about 1 p.m. A forward bias of 33 V has to be
applied before a sufficient current can be achieved, because of the high resistivity of the i-layer
at 77 K. The emission comes from the radiative recombination of electrons and holes injected
from the n- and p-layers, respectively, into the i-layer. The light intensity increases with current,
at first linearly with an external power efficiency of 6 x 10"5 and external quantum efficiency of
1.5 x 10"3 and sublinearly at higher currents. The emission spectrum peaks at 1.28 0.08 eV in
a 0.2 eV broad band. In contrast, single crystalline Si emits inefficiently at 1.09 eV in a
narrower (0.02 eV) band. The position of the peak of the EL spectrum lies mostly at the same
energy as that of a PL spectrum. The EL has been interpreted in terms of the model of Spear
[2] as a transition mostly from a density of states near the conduction band to tail states near the
valence band, and most recently as the recombination of a trapped electron bound to a trapped
hole by Coulombic attraction.

Since then, the phenomenon has been reconfirmed by several groups. Nashashibi et al [3]
reported the measurement of EL in a Au/n(50 nm)-i(700 nm)-p(150 nm)/SUS structure. At a
temperature between 100 and 200 K, the forward voltage necessary for the current of 0.5 - 10
mA/cm2 is 6 - 12 V. The forward current varies as V 1 where n varies from 6 to 8 as the
temperature decreases. The high power law implies space charge and contact effects. The EL
spectrum peak is centred around 0.9 eV. The EL intensity varies as EL oc In where n varies
from 1.1 to 1.4 as T increases. FIGURE 1 shows a log-log plot of EL intensity versus forward
current at various temperatures for a-Si.H p-i-n junctions [4]. It has been considered that most
of the emission occurs at the regions near the i-p interface due to the short diffusion length of
holes. It was pointed out that the maximum internal quantum EL efficiency was about 0.03
times smaller than the PL (photoluminescence) efficiency [3]. FIGURE 2 shows a log-log plot
of EL intensity versus T"1. The efficiencies have been normalised to 80 K. It is seen that the EL
intensity at 200 K is 2 - 3 orders of magnitude lower than that at 77 K, which is similar to the
case of PL, providing further evidence for the similarity in EL and PL recombination processes.
(For further information and discussions on PL of a-Si:H, see Chapter 5.)
v>

EL Intensity (IL)

iinj (mA/cm2)
FORWARO BIAS CURRENT
FIGURE 1 Log-log plot of EL intensity (IEL) versus forward current (i^) at various temperatures,
showing IEL ^ iinjv for a-Si:H p-i-n junctions. The inset shows v as a function of temperature
between 100 and 200 K. i^ has been expressed as current density; device area ~0.1 cm2 [4].

Moreover, Nashashibi, Rhodes and co-workers [3,5] reported that the EL efficiency could be
enhanced when a-Si.H junctions under forward bias are illuminated. In the limit of high
illumination, the EL intensity varies linearly with photocurrent, with a quantum efficiency four
to eight times larger than for dark currents. The reasons for this effect are not yet clarified.
FIGURE 3 shows typical EL spectra for a-Si:H p-i-n junctions and PL spectra for a-Si:H film
[4]Lim et al [6] reported success on the observation of EL from a-Si:H p-i-n and n-i-p junctions at
room temperature (RT). The EL spectrum measured at RT shows very broad band nature with
a peak at 1.31 eV. The external quantum efficiencies for the n-i-p and p-i-n junctions are 10~5%

Relative EL or PL Efficiency

EL efficiency (x)
PL efficiency (o)

IOVT

FIGURE 2 Log-log plot of EL intensity (at a constant forward current) versus T 1 (x) and a similar
plot of r|pL versus T* (open circles) for the same device, using argon 2.4 eV excitation through the
top contact. The efficiencies have been normalised to 80 K [4].

Laser

LUMINESCENCE INTENSITY

NOISE &
RESOLUTION

EL.PL

Stainless Steel

EL(OARK)

Photo enhanced EL
(PEL)

UOK

PHOTON ENERGY (eV)


FIGURE 3 PL, EL and photoenhanced EL spectra for a-Si:H p-i-n junctions at 140 K. All the data
have been plotted using the same vertical and horizontal scales to facilitate comparison. The EL
and photoenhanced EL were measured at the same total forward current (700 joA). The same
excitation intensity (1 mW cm"2) was used for the photoenhanced EL and PL measurements [4].

and 10"8%, at an injection current of 1 A/cm2, respectively. This has been interpreted as due to
the difference in the current transport mechanism of the two types. It has also been reported [6]
that doping the i-layer of the p-i-n junctions with a few v.p.p.m. of B2H^ led to stronger EL
intensity than the usual p-i-n junctions. Electroluminescence characteristics of various a-Si:H
and a-Si:X:H p-i-n junctions are summarised in TABLE 1.
TABLE 1 Summary of electroluminescence characteristics of various a-Si:H and a-Si:X:H p-i-n junctions.
Junctions

Glass/ITO/p a-Si:H/i a-Si:H/n a-Si:H/Al


ITO/p a-Si:H/i a-Si:H/n a-Si:H/Mo
ITO/n a-Si:H/i a-Si:H/p a-Si:H/Mo
Au/n a-Si:H/i a-Si:H/p a-Si:H/SUS
Au/n a-Si:H/i a-Si:H/p a-Si:H/SUS
Glass/ITO/p a-SiC:H/i a-SiC:H/n a-SiC:H/Al
Glass/ITO/a-SiC:H p-i-n/p-i-n/Al
Glass/ITO/p a-SiC:H/i a-SiC:H(superlattice)/n
a-SiC:H/Al
Glass/ITO/p a-SiC:H/HTI/i a-SiC:H/n
a-SiC:H/Al
Glass/ITO/p nc-SiC:H/i a-SiC:H/n a-SiC:H/Al
Glass/ITO/p a-SiC:H(superlattice)/i a-SiC:H/n
a-SiC:H/Al
ITO/p a-SiC:H/i a-SiC:H/n a-SiC:H/SUS
Glass/ITO/p a-SiC:H/i a-SiN:H/n a-SiC:H/Al
Glass/ITO/p a-SiC:H/i a-SiO:H/n a-SiC:H/Al
Glass/ITO/p m>SiO:H/i a-SiC:H/n a-SiC:H/Al

B2

Meas.
temp.
(K)

EL peak
(eV)

FWHM
(eV)

78
300
300
140
100
300
300
300

1.28 + 0.08

0.2

1.31
0.9
1.05
1.6- 1.9

0.5
0.3
0.2-0.3
0.4-0.6

1.9

0.3

300

1.9-2.1

300
300

1.9-2.1
1.7-2.0

0.3-0.5
0.4 - 0.6

1.8-2.2

0.5 - 5 cd/m2
0.2 - 0.6 0.2 - 0.5 cd/m2
0.1-0.2 cd/m2
10 cd/m2

300
300
300
300

External
quantum
efficiency
(or brightness)
1.5 x 10"3
5 x 10 8 %
1 x 10 5 %

Ref

10"2 (internal)
0.1-10cd/m 2
0.1-0.3cd/m 2
lcd/m 2

[1]
[6]
[6]
[3]
[51
[H]
[14]
[14]

5 - 20 cd/m2

[15]

2 -10 cd/m2
4 cd/m2

[H]
[19]
[17]
[12]
[13]
[13]

Time Resolved EL in a-Si:H p-i-n Junctions

Carius and co-workers [7-9] reported that time resolved electroluminescence and forward
current measurements show that at room temperature the forward current was first determined
by the space charge limited current of electrons, subsequently followed by the much larger
recombination current. FIGURE 4 shows typical transients of the forward bias current and the
EL signal after a forward bias voltage pulse at zero time of a-Si:H p-i-n junctions. At 78 K, the
forward bias current consists of two components: a fast rise and a slower rise. The decay time
is shorter than 100 ns. The EL also shows a rapid rise followed by a slower rise. The decay of
the EL is similar to the slow component of its rise time. It is non-exponential and a distribution
of lifetime is observed with a mean lifetime of a few hundred microseconds [10]. It is found
that at 200 K the radiative lifetime of about 30 (is yields a non-radiative lifetime of 3 x 10"7 s.
The radiative lifetime limits the frequency response of a light emitting device based on a-Si:H to
about 1 MHz. It is well accepted that the high radiative recombination rate near the p-i
interface is representative of the majority of the recombination processes.

200K

electroluminescence ( a. u. )

current density ( mA mm"2 )

78K

lime ( [JS)
FIGURE 4 Response of the forward bias current and the EL intensity of an a-Si:H
p-i-n diode to voltage pulses at zero time, repetition rate: 0.5 Hz [7].

a-SiC:H P-I-N HETEROJUNCTIONS

Cl

Basic Properties

The EL spectra from a-Si:H p-i-n junctions lie only in infrared regions. In order to obtain
visible light, one has to enlarge the optical energy gaps of the materials. This can be done by
alloying Si with certain elements, like C, O or N. Kruangam and co-workers [11-13] reported
that visible light emission could be observed from the p-i-n junctions of a-SiC:H [11], a-SiN:H
[12] and a-SiO:H [13]. It has been confirmed [13] that among these materials, a-SiC:H can
give the highest EL intensity.
FIGURE 5 shows the typical structure of a-SiC:H p-i-n junctions deposited on a glass
substrateATO (indium tin oxide). Al is deposited on the top as the back electrode. It has been
reported [11] that the thicknesses of the p-i-n layers for obtaining the highest EL intensity are
150 A, 500 A and 500 A, respectively. The p- and n-layers act as injectors of holes and
electrons, respectively, into the luminescent active i-layer. FIGURES 6(a) and 6(b) show band
diagrams of a-SiC:H p-i-n junctions in thermal equilibrium and in forward bias conditions,
respectively. The optical energy gaps of the p- and n-layers are generally kept constant at
2.0 eV to ensure the dark conductivity of the order of 10'6 (S cm"1). It has been reported [11]
that the optical energy gap of the luminescent i-layer necessary for obtaining visible light has to
be as large as 2.5 - 3.2 eV. Thus, there exist band discontinuities at the p-i and i-n interfaces.
Kruangam [11] pointed out that the band discontinuities govern both electrical and
electroluminescence properties of the a-SiC:H p-i-n junctions. Using the internal photoemission
measurement, it was found that the valence band discontinuity AEv at the p-i interface roughly
follows a relation AEv = 0.75 AEg, and that the conduction band discontinuity at the i-n interface

follows AEC = 0.25 AEg? where AEg is the bandgap difference of the i-layer and p- or n-layer.
Under a forward bias voltage, carriers are injected into the i-layer through the field tunnelling
effect of these band discontinuities.

Al

Glass substrate

FIGURE 5 Typical structure of a-SiC:H p-i-n junctions


deposited on a glass substrate/ITO [H].

(a) zero bias

(b) forward bias


FIGURE 6 Band diagrams of a-SiC:H p-i-n junctions (a) in thermal equilibrium
and (b) in forward bias conditions [11].

The EL intensity or brightness (B) varies with the injection current density J as B x f 7 where
the exponent n is close to unity for current density below 200 mA/cm2 and smaller than unity for
current above 300 mA/cm2 [H]. FIGURE 7 shows the dependence of the brightness on the
injection current density for several p-i-n junctions which have different optical energy gaps of
the i-layers. It is interesting to see that as the optical energy gap increases, the brightness
increases. The brightness of these junctions is in the range 0.1 - 10 cd/m2.
at 293K

BRIGHTNESS (cd/m 2 )

O
i layer thickness= 500A
E opt = 2.97(eV)
2.81(eV)-

INJECTION CURRENT J i n j (mA/cm2)


FIGURE 7 Dependence of the brightness on the injection current density for several
p-i-n junctions which have different optical energy gaps of the i-layers [H].

FIGURE 8 shows the EL spectra measured at room temperature as a function of the optical
energy gap of the i-layer in the range from 2.58 to 2.97 eV [H]. For the sample with an optical
energy gap of the i-layer = 2.58 eV, the EL spectrum peaks at 1.85 eV, with full width at half
maximum (FWHM) = 0.34 eV (red emission). The 2.68 eV sample exhibits a broad band
peaking around 1.90 eV with FWHM = 0.39 eV (orange emission). The 2.81 and 2.97 eV
samples have their peaks around 1.92 eV with FWHM = 0.40 eV (yellow emission).
FIGURE 9 summarises the dependence of the peak energy of EL spectra on the C2H4 gas
fraction during the preparation of the i-layer. For comparison, the corresponding optical energy
gap and peak energy of PL spectra are also shown in FIGURE 9. It is noted that the peak
energies of EL spectra are somewhat lower than those of PL spectra. It has been found that the
EL peak photon energy would be limited not only by the optical energy gap of the i-layer, but
also by the excitation energy of electron-hole pairs, i.e. the injection energy level of electrons
and holes from n- and p-layers.

PHOTON

ENERGY (eV)

at 293 K
EL INTENSITY (a.u.)

1.92 eV
(yellow)

i-layer gap(eV)

1.92eV
(yellow)
1.9OeV
(orange)
1.85 eV
(red)

WAVELENGTH (A)
FIGURE 8 EL spectra measured at room temperature as a function of the optical
energy gap of the i-layer in the range from 2.58 to 2.97 eV [11].

opt

PHOTON

PL
E

FWHM

EL

OF SPECTRA (eV)

ENERGY (eV)

Measured at 273 K

C2H4
C2IVSiH4
FIGURE 9 Summary of the dependence of the peak energy of EL spectra on the C2H4 gas
fraction during the preparation of the i-layer. For comparison, the corresponding optical
energy gap and peak energy of PL spectra are also shown [H].

The threshold voltage for sufficient current to observe the EL varies from 10 to 20 V,
depending on the optical energy gap and the thickness of the i-layer.
C2

Improvement of EL Intensity

In order to apply the a-SiC:H p-i-n junction device to a flat panel display, it is essential to
increase the brightness. The brightness that is necessary for a practical use for a display should
be more than 50 cd/m2. There have been several attempts to improve the brightness as can be
summarised as follows.
C2.1

Using a p-i-n/p-i-n tandem structure

The idea of the p-i-n/p-i-n tandem structure (FIGURE 10(a)) is to increase the thickness of the
i-layer. It has been reported [14] that the brightness of the tandem device is larger by about a
factor of two in comparison with the single device.
Al

Al

Glass

glass

substrate

(b)

(a)
HTi-layer

Glass Substrate

(d)

(C)

AL

ITO

OWI

DC
or

Buffer Layer
(IT0,Ti02,Ag)
Metal substrate

Pulse
Source

OWI
ITO

GLASS

(e)

(*)

FIGURE 10 Various structures of a-SiC:H p-i-n junctions: (a) p-i-n/p-i-n tandem [14], (b) superlattice
i-layer [14], (c) hot carrier tunnelling injection structure [15], (d) p-microcrystalline SiC injector [11],
(e) metal substrate [17] and (f) superlattice p-layer [19].

C2.2

Using the carrier confinement effect in a superlattice i-layer

In this structure, the i-layer consists of a-SiC: H multilayers (small bandgap well and large
bandgap barrier layers) as shown in FIGURE 10(b). When holes and electrons are injected into
the superlattice i-layer, these carriers will be confined within the well layers sandwiched by the
barrier layers. It has been reported [14] that the optimal thicknesses of each well and barrier
layer are 50 A and 100 A, respectively. The brightness is increased by a factor of 3 to 5,
compared with a conventional p-i-n device.
C2.3

Using a hot carrier tunnelling injection structure

FIGURE 10(c) shows the structure of a hot carrier tunnelling injection structure where there
exists a large optical energy gap a-SiC:H at the p-i interface and another one at the i-n interface
[15]. The principle is that when an electric field is applied to this device, the electric field will
be mainly distributed in the HTI layers. The high electric field in the HTI layers can allow
carriers to be easily injected with a high excitation energy into the conduction band and/or
valence band of the i-layer. The brightness of an HTI structure is higher by one order of
magnitude in comparison with a conventional device. With this new structure, the brightness is
about 20 cd/m2, with an injection current density of about 600 mA/cm2.
C2.4

Using a p-microcrystalline SiC injector

It has been reported [16] that the electron cyclotron resonance (ECR) plasma chemical vapour
deposition (CVD) method could provide very highly conductive p- and n-microcrystalline (|j,c)
SiC:H materials. The |ic-SiC:H having an optical energy gap of 2.25 eV exhibits a dark
conductivity as high as 20 (S cm"1), which is more than seven orders of magnitude higher than
the p- and n- a-SiC:H prepared by conventional RF plasma CVD. These wide gap materials
have been used as carrier injector layers in p |ic-SiC:H/i a-SiC:H/n (ac-SiC:H structures
(FIGURE 10(d)). The brightness was increased by a factor of 3 to 5 and, at the same time, the
EL spectra shift towards shorter wavelength [H]. These improvements are attributed to the
increase in the carrier injection efficiency.
C2.5

Using a metal substrate

Boonkosum et al [17] reported an effort to improve the brightness of the a-SiC.H LEDs by
using a high thermal conductivity metal (SUS) sheet substrate instead of a glass substrate
(FIGURE 10(e)). The results show that the threshold current for the observation of the
emission is half that for a glass substrate and the brightness is increased from 1 cd/m2 (for a
glass substrate) to about 5 cd/m2. The thermal conductivity of an SUS sheet (0.96 W/m K) is
higher than that of a glass sheet (0.5 W/m K). Therefore, the above improvement should, in
some part, arise from the enhancement of the internal quantum luminescence efficiency due to
the better thermal dissipation of the SUS sheet (heat sink effect) and may be due to a better
back mirror effect from the SUS surface.
C2.6

Using a p-microcrystalline SiO injector

It has been reported [18] that highly-conductive and wide bandgap p-type microcrystalline
silicon oxide (p |ic-SiO:H) could be prepared from the gas mixture of CO2 + SiH4 + B2H6 with

a high hydrogen dilution plasma CVD method and that these materials were useful for a window
layer in high efficiency a-Si:H solar cells. In the case of LEDs, Boonkosum et al [13] reported
that by using the p |ic-SiO:H (optical gap = 2.30 eV, conductivity = 10 S/cm) as a hole injector
layer, the brightness was increased by a factor of 5, compared with a conventional device.
C2.7

Using a superlattice p-layer

Hong et al [19] reported that by incorporating quantum well layers at the p-i interface (FIGURE
10(g)), the brightness was improved by a factor of 7 which is about 4 cd/m2 at the injection
current density of 2 A/cm2.
C3

Some Other a-Si:X:H Heterojunctions

Not only a-SiC:H but also some other wide bandgap materials like a-SiN: H and a-SiO: H could
be used as the luminescent i-layer. Kruangam and co-workers [12,20,21] reported the
observation of red to green colour emission from the glass/ITO/p a-SiC:H/i a-SiN:H/n
a-SiC:H/Al structures. The optical energy gap of the i a-SiN:H is changed within the range
2.5 - 3.0 eV. The brightness of the red device is 0.5 cd/m2 with a forward injection current of
2000 mA/cm2.
Recently Boonkosum et al [13] reported success in the fabrication of the p-i-n junction LED
where the i-layer was a-SiO:H. However, the brightness of 0.1 - 0.2 cd/m2 is the lowest,
compared with conventional a-SiC:H and a-SiN:H LEDs.

BRIGHTNESS DEGRADATION PROBLEMS

One of the weakest points of the EL properties in the a-Si:X:H heterojunctions is the large and
fast degradation of the EL intensity due to metastable properties under high current injection
[22]. The lifetime of such devices during a forward bias operation at an injection current
density greater than, for example, 1000 mA/cm2 is several hours or, in some cases, as short as
several minutes. There might be several reasons for such degradations: current induced defects,
current induced heat, high electric field induced breakdown, etc. Rizzoli et al [23] reported that
the degradation could be recovered by annealing and pulsed operation. The reduction of the
duty cycle also improves the performance of the devices.

CONCLUSION

Injection electroluminescence comes from the radiative recombination of excess carriers injected
from the electrodes into the luminescence layer. The structure of p-i-n junctions has been
reported to be the best basic structure to obtain the highest EL intensity. The devices can be
operated at both DC and pulsed current, while the pulsed current mode is known to extend the
lifetime of the devices. One of the main applications of the devices is a thin film light emitting
diode, the details of which will be described in Datareview 7.5.

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[2]
[3]
[4]
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R. Rizzoli et al [Mater. Res. Soc. Symp. Proc. (USA) vol.377 (1995) p.809 ]

6.4

a-Si:H thin film transistors


K. Suzuki
August 1997

INTRODUCTION

Since LeComber et al [1] reported a hydrogenated amorphous silicon thin film transistor (a-Si:H
TFT), many studies on a-Si:H TFTs have been reported. The research has intensified in
conjunction with the development of liquid crystal displays (LCDs), because the a-Si:H TFT
shows good reproducibility and uniform characteristics on a large-area glass substrate. An
active matrix LCD, in which each pixel has the a-Si:H TFT as a switching element, is superior in
picture quality and is now the major matrix-type LCD product [2,3]. The important TFT
parameters in LCD application are field-effect mobility, threshold voltage, steepness of currentvoltage characteristics from off- to on-state, switching ratio of on-current to off-current,
breakdown voltage, parasitic capacitance between electrodes and reliability under long time
operation. An X-ray sensor is another interesting device, where the TFT functions in a manner
similar to an LCD [4].

TRANSISTOR STRUCTURES

Among several types of TFT structures, three types of TFT have been practically applied to the
LCDs [2]. FIGURE 1 shows the cross-sectional views of these TFTs. All TFTs consist of an
a-Si:H layer, a gate dielectric layer, a gate electrode and source/drain electrodes. Type A TFT
has the gate electrode on the top side of the device, whereas in the case of the other two types
(B and C) it is on the bottom side. Based on these structures, several structures have been
developed to improve the device performances.
On-state performance, or charging
performance, of the TFT circuits can be expressed with the TFT parameters as follows [5]:
charging performance = \i-Cg8L-(L/2 + AL)

(1)

where \i is a field-effect mobility, Cg8 is a parasitic capacitance between the gate and source
electrodes, L is a channel length of the TFT and AL is an overlap length of the gate and source
electrodes which is a part of the origin OfCg8.
Byun et al [6] reported a circular shaped TFT in order to reduce Cg8, where the current flowed
from an outside drain electrode to a centre source electrode. In a type C TFT, a self-aligned
structure, in which the channel length is the same as the width of the gate electrode, was
realised using a backside photoresist exposure [7]. The self-aligned TFT minimises the value of
AL. However, the channel length is limited by a minimum spacing between the source and drain
electrodes. A fUlly self-aligned TFT structure was developed in order to reduce both AL and L
values using a silicide conducting layer in addition to the backside exposure technique [8]. The
silicide layer connected the electrode metal to the channel layer. A doped polycrystalline layer
was also used as a conducting layer, which was formed by laser irradiation from the backside of
the glass substrate with the gate electrode as a mask, and realised a fully self-aligned TFT [9].

Gate

Gate Insulator

(a) Type A
Source

Source

Drain

a-Si:H

a-Si:H

Drain

(b) Type B
Gate

Source

a-Si:H

Gate Insulator

Insulator
Drain

(c) Type C
Gate

Gate Insulator

FIGURE 1 Cross-sectional view of typical a-Si:H TFTs: (a) type A, (b) type B, (c) type C.

Selective deposition of n+a-Si:H film also realised a fully self-aligned TFT structure [10]. Using
a fUUy self-aligned structure, a sub-micron channel TFT was fabricated and the TFT with short
channel length showed a decrease of the field-effect mobility at less than 4 jam channel length
[H].
An a-Si:H TFT shows sufficiently low leakage current under dark conditions. The dark-state
leakage current was further decreased by an offset drain structure with an additional gate
electrode [12]. However, under illuminated conditions the leakage current greatly increases.
This was a serious problem in actual LCD application because many LCDs were used with a
backlight. The origin of photo-leakage current is generation of carriers in the a-Si:H film, and
therefore, some light shield structures have been developed. To prevent light incident from the
top side of the TFT, light-shield structures with the source/drain electrode [13] and with a
pigment dispersed organic layer were reported [14]. As for the bottom side, a reduced a-Si
island pattern [15], a metal light shield layer [16] and a Bi/SiOx cermet layer [17] were
developed.
The most suitable TFT structure should be selected from the above basic structures to meet the
specifications of each application.

PROCESS TECHNOLOGIES

In general, the highest temperature process is plasma chemical vapour deposition (PCVD) of
a-Si:H and SiNx films and the maximum temperature is typically less than 3500C. This allows
use of a glass substrate or a flexible steel-foil substrate [18]. Although a soda lime glass
substrate process was reported [19], in most cases a non-alkali glass is used.
A gate dielectric layer is one of the important materials affecting TFT performance, stability,
and manufacturing yield. Double-layered gate dielectric structures have been commonly used to
prevent pinhole defects. An anodised Ta2O5ZPCVD SiNx [20], an anodised Al2O3ZPCVD SiNx
[21], a PCVD SiOxZPCVD SiNx [22] and a PCVD SiNxZPCVD SiNx double layer structure [23]
were developed. Interface defects between a-Si.H and gate layers also affect the TFT
performance, and the SiOxZa-Si:H interface showed inferior electronic properties with respect to
threshold voltage and stability. Some plasma treatments of the surface of SiOx films were
effective for improving these properties, especially the plasma treatment using N 2 or NH3 gas
formed SiNx network at the surface [24]. As mentioned, the SiNx gate insulator is the most
popular interface to the a-Si:H layer. Other methods to form the gate dielectric film were also
reported using a liquid phase deposition of SiO2 [25] and a direct oxidation of the a-Si:H
surface [26].
Deposition of a-Si.H is another important process from the viewpoint of TFT performance [27],
and so far the PCVD method has been most commonly used to realise sufficient performance.
High deposition rate processes for higher productivity were developed by higher-frequency
plasma [28] and higher-density plasma under high-temperature deposition [29]. However, the
higher deposition rate resulted in the lower field-effect mobility. The cluster PCVD system is
widely used instead of the inline tools to improve throughput as well as to reduce dust [3O]. A
double-layer structure composed of high deposition rate a-Si:HZnormal rate a-Si:H suppressed
deterioration of TFT performance and achieved shorter processing time [31]. Another
composite structure composed of a-Si:HZmicrocrystalline SiH showed lower leakage current
[32]. Incorporation of Cl into a-Si:H film also realised low leakage current of the TFT [33].
Contact resistance as well as junction performance of an n+a-Si:H film also affects TFT
performance. Since doped microcrystalline Si has higher conductivity than doped a-Si:H film,
TFTs with doped microcrystalline Si:H film showed higher mobility [34]. The n+a-Si:H
formations using ion doping methods were reported with a post-annealing treatment [35] and
with laser-annealing [36]. The dependence of sourceZdrain metals on contact resistance to
n+a-Si:H layer was also investigated and Eu, Y and Mg showed lower contact resistance [34].

MODELLING AND DYNAMIC PERFORMANCE

Physical understanding of TFT operation is indispensable for improving TFT performance as


well as failure analysis in conjunction with the device structures and the film properties. The
low field-effect mobility of a-Si:H TFTs originates from the defect distribution in the energy
band diagram of the a-Si:H film and its spatial distribution within the film [37]. Defects at the
a-Si:H film interfaces and in the gate dielectric layer are also important [38]. As for the
dynamic characteristics, the time to fill the defects was reported to be of the order of ms [39].
However, on-current transient time was actually less than 10 ^s [40]. In the case of off-current

under illuminated conditions, it took ms times to reach steady state [41]. These dynamic
characteristics of the channel current, in addition to the frequency dependence of capacitancevoltage characteristics of the TFT [42], should be considered in designing LCDs. Temperaturedependent current-voltage characteristics under dark conditions [43] and under photoilluminated conditions [44] were investigated.
Bias-stress-induced instabilities of an a-Si:H TFT have been widely investigated, especially the
threshold voltage shift [45]. The shifts under positive and negative bias stresses were opposite
to each other. From these DC stress data, the threshold voltage shift in practical LCDs under
AC operation was estimated [46]. The origin of the instabilities was explained by trapping at
the interface of the SiNx gate dielectric layer [47] as well as the carrier induced defect
generation in the a-Si:H layer [48].

CONCLUSION

Recent developments of a-Si:H TFT technologies have achieved a new flat panel display market
and it is still growing rapidly. However, understanding of the basic operational principle is less
advanced that in the case of crystalline silicon MOS devices. Although the major focus of
research and development of a-Si:H TFTs has been productivity, if higher performance
sufficient for integrating driver circuits or driving flat panel displays other than LCDs were
realised, the impact on large-area device applications would be significant.

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P.G. LeComber, W E . Spear, A. Ghaith [Electron. Lett. (UK) vol.15 (1979)p.179 ]


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K. Suzuki [ Datareview in this book: 7.3 Amorphous silicon large area displays ]
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p.839]
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(Japan) (1994)?.\M]
[14]

M. Akiyama, T. Kiyota, Y. Ikeda, T. Koizumi, M. Ikeda, K. Suzuki [ SID Int. Symp., Dig
Tech. Pap. (USA) (1995) p. 158 ]

[15]

[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]

[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]

[43]
[44]
[45]
[46]

M. Akiyama, H. Toeda, H. Ohtaguro, K. Suzuki, H. Ito [ Int. Electron Devices Meet. Tech.
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[47]
[48]

MJ. Powell [ Appl. Phys. Lett. (USA) vol.43 (1983) p.597 ]


W.B. Jackson, D. Moyer [Mater. Res. Soc. Symp. Proc. (USA) vol.118 (1988) p.231 ]

CHAPTER 7

PHOTOELECTRONIC DEVICES
7.1
7.2
7.3
7.4
7.5

Amorphous
Amorphous
Amorphous
Amorphous
Amorphous

silicon solar cells


silicon photodetectors
silicon large area displays
silicon xerographic applications
silicon alloy LEDs

7.1

Amorphous silicon solar cells


A. Catalano and colleagues at V.P. Technology
August 1997

INTRODUCTION

Amorphous silicon solar cells have continued to show dramatic improvements in both efficiency
and stability as a direct result of better understanding of the material and its alloys. Recent
work has also led to far better understanding of the light induced degradation kinetics and its
relationship to film preparation. It is also especially noteworthy that a new deposition method,
hot wire chemical vapour deposition (HWCVD), has shown great promise in preparing films
with low defect levels as well as improved stability.

TRIPLE JUNCTION PERFORMANCE CHARACTERISTICS

Yang et al [1] have reported the highest initial and stabilised efficiencies to date (14.6% and
13.0%, respectively) using a triple junction, multi-bandgap design. Note that these efficiencies
are so-called 'active area5 values; TABLE 1 gives both active area and total area performance
as well as the other important performance characteristics of this record-setting device.
Improvements in performance appear to be the result of improvements in several areas:
(1) improved a-SiGe:H alloys and the design of the low bandgap cell, (2) the use of
microcrystalline doped layers throughout the device, including the tunnel junctions via an
improved process, (3) heavy hydrogen dilution during the plasma enhanced chemical vapour
deposition (PECVD) process, (4) the use of a highly reflecting, light scattering rear contact [2],
and (5) an optimised ITO top contact layer with improved light transmission. FIGURE 1 shows
a schematic cross-section of the device. The optical bandgap of the I-layers of the device
decreases from top to bottom. A unique feature of the device design is the use of a-SiGe alloys
in both the middle and lower junctions, and the absence of a-SiC:H alloy as the top, wide
bandgap device. Despite the lack of a-SiC:H in the top cell the device has been shown to
develop an open circuit voltage, V0C, of 1.011 V. The tunnel junctions interconnecting the three
junctions are a potential major loss of current, as the doped amorphous layers have a far
narrower gap than their undoped counterparts. Yang et al [1] minimise absorption losses
through the use of microcrystalline doped layers which presumably have a higher optical
transmission owing to the indirect optical bandgap of the material, while gaining a lower
resistance of the contact layer as a result of the far higher conductivity. Interestingly, the
authors report that a lower V00 results from the use of the microcrystalline doped layers due to
an intermixing of the dopants at the n/p interface and/or a band edge discontinuity between the
amorphous and microcrystalline layers. The use of a proprietary 'buffer layer' appears to
remove the problem.
a-SiGe:H, whose poorer electronic transport properties reduce
performance compared to a-Si:H, was improved by both optimising the hydrogen dilution of the
alloy as well as grading the Ge composition within the device [3]. The greater transmission that
results from the improvements discussed above leads to a strikingly high overall quantum
efficiency for the device as illustrated in FIGURE 2.

TABLE 1 Initial and stabilised performance of record triple junction solar cell [I]. The stabilised
performance is that measured after 1000 hr light soaking at one sun.

(V)

Isc
(mA)

FF
(%)

2.357
2.297

2.104
2.061

74.39
69.7

V0C

Tl

(Active area, %)

*1
(Total area, %)

14.5
13.0

13.5
12.1

Grid

Grid
ITO
P3
i3 a-Si alloy
n3
P2
i2 a-SiGe alloy
n2
P1
i1 a-SiGe alloy
n1
Zinc Oxide
Silver
Stainless Steel

FIGURE 1 Cross-section of high efficiency, triple junction device [I].

Initial
Stable

Jsc

Total area
(mA/cm2)
7.721
7.563

Wavelength (nm)
FIGURE 2 Quantum efficiency of triple junction device as a function
of wavelength (nm).

HYDROGEN DILUTION

As discussed above, hydrogen dilution plays a pivotal role in improving the stability of a-Si:H
and amorphous silicon-based alloys. The reason for the strong influence has gradually become
clear as a result of detailed studies of the kinetics of light induced degradation and recovery by
annealing at elevated temperatures. Initial experimental results on the degradation process were
explained by a simple self limiting bimolecular recombination mechanism [4]. Additional work
however showed that the kinetics of the degradation process could be fitted to a stretched
exponential function [5,6]. Accelerated degradation measurements performed at high intensity
(140 x AMI.5) as a function of temperature showed that the saturation of degradation is highly
dependent on temperature indicating that the competition between degradation and annealing
processes determines performance at any given set of conditions (e.g. time, intensity and
temperature) [7]. At relatively low temperature, 500C, and high intensity, the degradation of
p-i-n devices continued unabated and did not exhibit saturation, and the light intensity appeared
to follow a simple scaling law:
I 18 t = constant

(1)

where I is the light intensity and t is exposure time. At higher temperatures, such as 150 1900C, saturation quickly occurred, and lowering the light intensity increased the efficiency at
which stabilisation occurred. Taken together the data indicate that the competing processes of
degradation and annealing define performance in the degraded cell.
Further experiments [8], in which a cell degraded at high intensity was given additional low
intensity exposure (AM 1.5) and compared to an identical cell which was degraded for the first
time at normal AM 1.5 conditions, showed a surprising behaviour, as illustrated in FIGURE 3.
Although both cells were expected to approach a single performance value (the heavily
degraded cell increasing performance from low values, the undegraded cell from high values), it
was surprising to find that the more heavily degraded device actually improved beyond its
steady state value before finally decreasing and reaching a steady state value. This change in
sign of the rate of degradation was explained by a model in which two types of defects exist,
each characterised by its own generation and annealing kinetics. These two types of defects
have been characterised as 'fast' and 'slow', referring to the fast creation and annealing rate of
one type of defect and the relatively slow creation and annealing rate of the other.
Hydrogen dilution has been shown to have a profound effect on the relative concentration of
these 'fast' and 'slow' states [9]. The same experiments described above were performed on
solar cells deposited with hydrogen dilution and at lower temperature. As shown in FIGURE 4,
the hydrogen diluted/low temperature sample more quickly reached a steady state, and the
efficiency at which this steady state occurred was at a much higher conversion efficiency
compared to ordinary undiluted devices. Although it is tempting to associate the difference in
stability with the obvious structural changes known to occur with hydrogen dilution, namely
low microvoid density and reduced levels of silicon dihydride bonds, no such evidence was
found in the samples that were examined.
Further evidence of the effect of hydrogen dilution, and further insight into the nature of the
defects, was disclosed by careful electroluminescence measurements of undiluted and hydrogen
diluted p-i-n devices [10]. The electroluminescence spectra at 300 K of non-hydrogen diluted

Normalized Efficiency

Cell subjected to pre-soaking


Two-component model
Cell without pre-soaking
Two-component model

(a)

Exposure time (hours)

Normalized Efficiency

FIGURE 3 Normalised solar cell efficiency for two devices as a function of


1 sun exposure time. One cell (closed circles) was light soaked for 2 hr at
50 suns prior to 1 sun illumination and the other (open circles) started from
the as-deposited state. The dashed lines are computed from the model.

Cell subjected to pre-soaking


Two-component model
Cell without pre-soaking
Two-component model

Exposure time (hours)


FIGURE 4 Normalised solar cell efficiency for two cells
prepared with hydrogen dilution at low temperature.
Legend same as in FIGURE 3.

samples clearly show emission from the main band at 1.0 - 1.3 eV rising to a strong peak at 0.9
eV, and a smaller peak at about 0.75 eV. The peak at 0.75 eV is not observed in hydrogen
diluted samples. Upon light soaking, the main band is found to decrease while both the 0.75 eV
and 0.9 eV peak increase, although the former peak is still not resolved in the hydrogen diluted
samples. Plots of the intensity of these peaks show a rapid linear increase in the 0.9 eV peak,
followed by saturation at 100 hr (200 mW/cm2 illumination), while the 0.75 eV peak in the nonhydrogen diluted sample continues to grow. It is evident that these two defect levels at 0.9 eV
and 0.75 eV correspond to the 'fast' and 'slow' states discussed earlier. This remarkable result
not only confirms solar cell measurements, but also provides information on the energy levels of
the defects.
Although high conversion efficiency has been obtained with a-Si.H based small area devices
prepared by PECVD as discussed above, the intrinsic light induced degradation of a-Si:H
remains a serious limitation which compromises the attractiveness of the material for
widespread use in solar cells. The use of tandem and triple junction devices has provided an
engineering solution of sorts and permitted progress, because it allows the use of thin junctions
that can tolerate a lower carrier lifetime and reduce recombination, while at the same time
permitting efficient absorption of the solar spectrum. Despite advances in device design, and
materials improvements such as hydrogen dilution, the efficiency of modules is low, with
commercial products on the order of 8%. Moreover, the deposition rates needed for device
quality films remain poor ( 2 - 4 AJs) making for inefficient use of the feedstock gas and a high
capital cost for the deposition portion of the manufacturing line.

HOT WIRE CVD (HWCVD)

Although PECVD has been the most successful method of depositing a-Si:H, a new method,
hot wire chemical vapour deposition (HWCVD), has been shown to produce material with
properties that may rival those prepared by the former method. Although HWCVD has been
used for some years to produce diamond-like films [11], and Weizmann [12] has patented an
HWCVD process for preparing amorphous silicon, it remained for the work at NREL [13] to
demonstrate that HWCVD a-Si:H material was not only of device quality, but also had a much
improved stability, possibly due to the extremely low hydrogen content (1 - 2%) of the films.
These results have ignited interest world-wide in the HWCVD method.
In the HWCVD method silane gas or a mixture of silane and hydrogen is passed over a filament
comprised of tungsten or tantalum held at temperatures in a range of 1660 - 20000C. A heated
substrate, placed opposite the filament array, receives the deposited film.
A unique feature of a-Si:H films is the combination of low hydrogen content, in the range of
1 - 3%, and low defect density as measured by such techniques as the constant photocurrent
method (CPM). The best results have been obtained at high substrate temperatures on the
order of 350C, and despite high, 4 - 8 A/s deposition rates.
Attempts to make devices have demonstrated good stability with only a 10% loss in
performance after 887 hr light soaking [14]. Although not definitive, because of the modest
performance of the p-i-n device, the results are nonetheless quite encouraging. One difficulty in
fabricating devices is melding the PECVD process used to deposit the doped layers with the

HWCVD process. The surfaces of the exposed HWCVDfilmseasily lose hydrogen, and special
precautions must be taken to preserve the surface concentration. Even in these circumstances,
fill factors of only 0.6 are obtained. Because these are relatively simple devices, without graded
layers, optimised interfaces or doped layers, the full potential of devices based on the HWCVD
method has not yet been realised.

CONCLUSION

In conclusion, remarkable progress continues to be made in amorphous silicon solar cell


technology, with the better understanding of fundamental issues and new approaches providing
important useful information furthering device performance. We are hopeful that continued
research will advance this important technology.

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7.2

Amorphous silicon photodetectors


MJ. Rose
July 1997

INTRODUCTION

The silicon photodiode is the key element in most two-dimensional imaging systems and these
have spectacular successes in the charge coupled device (CCD) and complementary metal oxide
semiconductor (CMOS) photodiode technologies. Amorphous silicon (a-Si) allows a large area
sensing technology without the need for complex optics systems. In general, an imaging plate
will consist of an array of pixels of a-Si:H p-i-n (or n-i-p) diodes with a-Si:H thin film transistors
(TFTs) in an active matrix readout (an extension of linear arrays). The concept of an
amorphous silicon image plate was introduced by Street et al [1] of Xerox PARC as a potential
solution in non-scanning photocopying. It soon became apparent that such arrays could be used
in radiation imaging [2] either by direct detection in thick films [3] or by a converter phosphor
[4]. Such devices have potential for real time imaging and digital processing and storage.
Applications include particle detection [1], X-ray computed tomography [5], flat bed contact
imagers [6], colour and UV sensors and optically addressed spatial light modulators [7].

PHOTODIODES FOR 2D IMAGING

The p and n contact layers establish a built-in potential with a depletion width of 1 [xm under
zero bias conditions. Charge collection by light absorption in the depletion region is increased
with the device operating in reverse bias This depletion width has been shown to increase to at
least 50 (im in reverse bias and can be used in single particle detection. With the readout TFT
switched OFF, and the photodiode in reverse bias, incident light is converted to electron-hole
pairs, collected in the internal field and stored in the self capacitance. Charge is transferred by
activating the gate line to the output to external electronics and amplification. The goal is high
sensitivity and a fast response time.
Important parameters for the photodiode include conversion efficiency and collection, dark
current and reverse bias characteristics with a small contribution from charge by thermal
generation or injection and, in the array, sensitivity and readout speed, dynamic response and
signal-to-noise ratio. Wieczorek [8] has shown that the dynamic response is determined by the
trapping of electrons during illumination and their subsequent thermal release. The final image
quality will also depend on transistor and read-out parameters. Trapping at deep defects in
a-Si:H will affect array performance and lead to image lag.
The readout time for an array has been shown to increase as the square root of array area. A
1 \xm thick sensor gives a readout time of 5 ms with complete discharge in five time constants
giving video rate reading [I].

THICK DIODES - DIRECT DETECTION

There is a requirement for a high deposition rate, usually by very high frequency (VHF) plasma
enhanced chemical vapour deposition (PECVD). Using this method, thick i-layers up to
100 jam have been prepared at a deposition rate of 22 A s"1 providing detectors with leakage
currents of less than 4 nA cm"2 under a reverse bias of 100 V [9]. Chablotz et al [10] find a low
defect density and low stress centred around a plasma excitation frequency of 70 MHz for a
deposition temperature of 2000C. This has been related to modification of the plasma
characteristics as the sheath potential decreases.
Qureshi et al [11,12] have studied some material parameters affecting charge collection in thick
a-Si:H detectors. Transient photoconductivity measurement on devices up to 48 p,m thick,
typically with 5 - 1 O x 1014 ionisable dangling bonds per cm3, showed that around 30% of the
defects are ionised on biasing to deep depletion. The ionised dangling bond density determines
the thickness that can be depleted at operational bias.
A reduction in the required depletion voltage is obviously desirable and Drewery et al [13] have
demonstrated this by field profiling where insertion of p-layers in the intrinsic silicon reduced
the required bias by a factor of l/(n+l), where n is the number of p-layers with electron losses
within the layers less than 3%.
The thick diode approach in a new type of miniaturised cylindrical a-Si:H X-ray detector [14] is
being developed to allow absorbed dose measurement in-situ and to remove the problem of
signal variation in conventional planar structures. The diodes are the same as the a-Si.H flat
detector and show similar characteristics.

THIN DIODES WITH SCINTILLATOR - INDIRECT CONVERSION

Radiation detection using a-Si:H photodiodes coupled to a scintillator has been widely
researched and offers promise in medical imaging [1,15-18].
Prototype 64 x 40 arrays of two-dimensional a-Si:H photodiode arrays showed good uniformity
with a variation from linearity of 1%, and a 10% variation in dark current and a 25% charge
leakage on a 10 s integration time [19].
Arrays have now developed to 1536 x 1920 pixels with a pitch of 127 ^m giving an active area
of approximately 8" x 10" [18].
The imaging quality of these devices depends largely on the choice of scintillator and the diode
reverse characteristics. The largest response at peak p-i-n a-Si:H collection efficiency is with
Gd2O2S:Tb (Lanex) with peak emission at 550 nm. An outstanding problem in conversion is
light spreading in the scintillator leading to spatial resolution limitations [20].
The amount of charge collected before saturation is a function of the reverse bias voltage. A
linear dependence of this charge saturation is found with bias voltage [21]. As the performance
is governed by the magnitude of the reverse bias voltage, this places some importance on the
dark leakage current limiting sensitivity [22]. Measurements on these in 1 |a,m p-i-n

photodiodes have shown that currents in the range 10"11 to 10"9 A cm'2 are typical but are time
dependent with an exponential increase with the bias above 4 V [23].
The charge carried over to the next frame through deep state detrapping is also governed by the
reverse bias voltage [24]. For low bias the carry over charge is significant but this diminishes
with increasing bias voltage.
Linearity of response of these devices is another important parameter and is governed by the
reverse bias voltage. At low bias the response is linear over only a fraction of the full range. At
4 V, the signal is linear to within 1% over 80% of the range.
In a-Si:H photodiodes there is a slow photoconductivity rise on illumination and fast decay with
a residual current after switching off the illumination. These are determined by trapping of
photogenerated electrons in deep states with the transient current after illumination caused by
thermal emission.
Chevrier and co-workers [25,26] have studied the relative importance of generation currents
from deep level states and injection currents at doped/intrinsic interfaces.
Schiff et al [27] also described transient measurements on reverse bias currents in n-i-p sensors
to distinguish between generation currents and injection. Wieczorek [28] using isolated diodes
to avoid cross-talk effects used the noise spectrum revealed on reducing the reverse bias to zero
in non-optimised diodes to probe the photo- and recombination currents at low reverse bias,
concluding that 1/f noise is caused by recombination of electrons with trapped holes or by
injection and trapping at the n+ contact, switching on and off current filaments in this interface.
The area of the array that is sensitive to light, or 'fill factor5, is less than unity and decreases
with decreasing pixel size. Antonuk et al [29] and Street et al [22] have proposed an array with
pixellated lower electrodes defining the pixels and with the readout transistor under the sensor
with a continuous a-Si:H layer and top contact. Cross-talk in this configuration and charge
spreading is found to increase as the square root of time, affecting up to 5 pixels on long
integration and 2 pixels on a 40 ms frame time.
A new method of imaging has been proposed by Morton et al [30]. The sensor is based on a
two-dimensional array of capacitors with a-SiH TFT active matrix readout. To provide
sensitivity to the incident radiation, a radiation converter is placed in contact with the top plate
of the pixellated capacitors. The converter need not be a scintillator, but generates a pattern of
charge which creates a set of voltages proportional to the radiation intensities on the array of
capacitors. These voltages are sampled by external electronics to form the image. The
converter, forming the top capacitor, can be gas, organic or solid state. Using this dual
capacitor concept, a new a-Si.H 'focused photodiode' structure [31] has been fabricated and
simulated that uses the constraining effect of a shaped field using doped a-Si:H to create wells,
the field lines terminating on the capacitor plate. This concept solves the 'fill factor1 problem,
giving a 100% collection area and resultant sensitivity benefits that result in lower required
radiation dose.

COLOUR PHOTODETECTORS

Street et al [32], from Xerox, have described their imaging system used as a document scanner
allowing a scanning time of more than 10 frames per second. This page size sensor has 1536 x
1920 pixels and with colour filters with transmission at 450, 550 and 650 nm has produced
colour imaging with the entire range of colour variation from 440 to 650 nm, closely matching
the a-Si:H device spectral response.
a-Si.H, a-SiC:H or silicon-germanium alloys are being used as photodetectors sensitive in the
UV to IR spectral range. Two terminal a-Si:H photodiodes providing colour separation for
three colour detection show great promise for two-dimensional detectors. A number of a-Si:H
sensors have been developed. Rieve et al [33] have developed a sensor based on voltage
controlled spectral sensitivity in the visible range through the wavelength dependent absorption
coefficient in a-Si:H. A multilayer photodiode detector is integrated vertically with crystalline
silicon circuitry in a thin film on ASIC (TFA) sensor. Schottky, p-i-n and n-i-p-i-n diodes have
been used with a transparent conductor as a front electrode.
Bandgap engineering and field profiling allows voltage control to shift the main collection
region of photogenerated carriers in these devices. Different diode structures produce
differences in sensitivity, linearity and dynamic range and colour separation.
Steibig et al [34] report on the transient photocurrent response of an n-i-p-i-n diode that with
applied voltage in the steady state of-1.5 V, -0.6 V and 1.0 V shifts the responsivity from red to
green to blue, respectively, with peak wavelengths at 620 nm, 560 nm and 490 nm. The
response times on application of bias and light are generally around 20 ms.
Neidlinger et al [35] utilise an a-SiC:H/a-SiH p-i-i-n configuration which can be operated at
frequencies up to 20 kHz to overcome the speed limitations of the n-i-p-i-n structures.
A three-terminal device that offers improved colour separation has been reported. Topic et al
[36] reported TCO/p-i-n/TCO/p-i-n-p and TCO/p-i-n-i-p/TCO/p-i-n heterostructures. Both
structures exhibited a linear photocurrent/generation rate relationship with high rejection ratios
at peak wavelengths of 430 nm, 530 nm and 630 nm for applied bias between +1 V and - I V .
An a-Si:H/SiC:H p-i-n photodetector has been reported that has visible spectrum rejection but is
sensitive in the UV with the promise of large area 2D UV detection systems. The device has an
enhanced sensitivity in the UV with a quantum efficiency of 22% at 187 nm [37,38].

POSITION SENSITIVE DETECTORS - LATERAL PHOTO-EFFECT

a-Si:H p-i-n devices under reverse bias and non-uniform illumination lead to a carrier gradient
between the irradiated and non-irradiated regions where lateral diffusion rates of the
photogenerated carriers depend on the drift velocity of the carriers and their spatial distribution
and the magnitude of the reverse bias. This lateral photo-effect has been used to enable ID and
2D position sensitive devices. Fortunato and co-workers [39,40] have studied this effect for
optical inspection. The sensor provides a position resolution better than 20 \xm with a good

signal to noise ratio (above 5 dB) using 2 uW cm"2 light intensity with a response speed from
2 kHz to 1 MHz unaffected by background illumination or temperature changes of+100C.

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7.3

Amorphous silicon large area displays


K. Suzuki
August 1997

INTRODUCTION

The features of a liquid crystal display (LCD) are small thickness, low weight, flat screen and
low power consumption. Moreover, an LCD addressed by thin film transistors (TFTs) or twoterminal devices exhibits better picture quality. Therefore, TFT-LCDs have been widely applied
in personal computers, video cameras, portable TVs, projection TVs, etc. The basic concept of
a matrix LCD driven by active elements was proposed in 1971 by RCA Laboratories [I]. The
concept's viability was confirmed by fabrication of a CdSe TFT LCD [2]. LeComber et al [3]
announced the first a-Si:H TFT in 1979, and the first a-Si:H TFT LCD displaying a video image
was demonstrated in 1983 [4]. Since then, many LCDs with active elements including a twoterminal diode have been developed. Here, the recent development of LCDs with a-Si:H film
will be summarised.

TFT-LCD STRUCTURES

Each pixel has a TFT and a pixel electrode. The TFT functions as a switch to transfer image
signal to the pixel electrode and TFTs are driven by a line-at-a-time scheme controlled by
peripheral driver circuits which supply an electrical signal through the gate and data lines. A
colour display has a colour filter (CF) at the inner surface of the top glass plate and each pixel
has three sub-pixels corresponding to the primary colours of red, green and blue [5].
Specifications of the a-Si:H TFT for LCD applications are typically as follows [6]: a field effect
mobility of 0.5 cm2/V s, threshold voltage of about 3 V, and switching ratio, or the ratio of oncurrent to off-current, of 106. To ensure a grey scale image, the parasitic capacitance between
the gate and source electrodes must be small. Because of this, a self-aligned TFT is
advantageous for higher definition displays. There are basically three types of TFTs [7] which
are currently used in commercial products and all TFTs show a field effect mobility of 0.5 - 1.0
cm2/V s.
Power consumption is one of the issues of TFT-LCDs. Early products had only 3% light
transmittance, since the aperture ratio of the pixel was about 30 - 40% for a 10-inch VGA
(640 x 480 pixels). There have been many reports on improving the aperture ratio [8]. In the
case of most TFT-LCDs, the aperture is defined by a black matrix (BM) pattern which prevents
penetration of unmodulated light and the initial products form a BM pattern on the CF
substrate. Ueda et al [9] proposed a shield-electrode pixel structure, where data lines were used
as a part of a BM pattern and achieved aperture ratio of 58% for a 9.5-inch VGA, about 50%
higher than those of the conventional structures. This structure was further developed by
application of a storage capacitor on a gate line structure and achieved 70% aperture ratio for a
9.5-inch VGA [10].

The BM on an array configuration, where all BM patterns were formed on the array substrate,
was developed by using organic material containing pigments [11], a-SiGe:H [12] or Bi-SiOx
cermet thin films [13]. Toeda et al [14] used both the gate and data lines as a BM pattern with
the pixel electrode formed on the top layer and achieved 40% aperture for a TFT-LCD with
40 |am pixel pitch. This structure was further developed to realise a direct-view TFT-LCD
using thick organic material with a low dielectric constant as an intermediate insulator and
achieved 74% aperture ratio for a 10.4-inch VGA with 330 jam pitch [15].
Viewing angle is another technical issue for TFT-LCDs. Of the several LC modes so far
reported, the following require some change of pixel structure. A halftone grey scale mode
requires capacitively divided pixel electrodes [16], a dual-domain mode needs a BM pattern at
the divided portion of the pixel electrode [17], and an in-plane switching mode needs a parallel
electrode pattern to generate lateral electric field parallel to the substrate [18].
Because of a low field effect mobility of the a-Si:H TFT, integration of driver circuits is
inherently difficult. Akiyama et al [19] reported integrated gate driver circuits using a-Si:H
TFTs which operated up to 30 kHz. Stewart et al [20] demonstrated a 2.2-inch TFT-LCD with
fully integrated driver circuits using a-Si:H TFTs, which operated at a 1 MHz sampling
frequency. Aoyama et al [21] reported a hybrid TFT-LCD in which all pixels were driven by
a-Si:H TFTs and the driver portion was formed by laser annealed polycrystalline Si TFTs.

GATE LINE MATERIALS FOR TFT ARRAYS

For a large size TFT-LCD, selection of a gate line metal is important, particularly so for the
TFTs with a bottom gate structure. Gate pulse waveforms are deformed due to the resistance
and capacitance of the gate line, and this induces non-uniformity of the display image. Low
resistive materials such as Al or Cu are subject to problems in fabrication processes in view of
their poor durability against thermal processes and chemical solutions [22]. TABLE 1
summarises the typical materials used in TFT-LCDs with the bottom gate structure. Al is
widely used for the data line.
TABLE 1 Typical gate line materials of a-Si:H TFT-LCDs.
Notes on processing
Affiliation
Resist.
(^D cm)
36
Good
Toshiba
MoTa
25
Cr
Difficult in taper shaping
Good
Toshiba
Ta/TaN
25
Sharp
Ta/Nb
Good
25
Good
Toshiba
MoW
15
AlZr
Poor durability against chemical solution Matsushita
5
Poor durability against chemical solution Samsung
AlNd
5
IBM
MoTa/Mo/Al
Additional process steps required
6-20
Anodic oxidation indispensable
Hitachi
Al
3
IBM
Cu
Poor durability against chemical solution
3
Material

Ref
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]

TFT ARRAY FABRICATION TECHNOLOGIES

It is necessary to reduce production costs in order to expand the TFT-LCD market. Technical
issues for cost reduction are high productivity with low investment, high yield and low cost
modular parts [32]. As for the number of process steps, two or three photolithography and
etching process (PEP) steps were reported [33]. However, these techniques sometimes
deteriorate picture quality or yield. Ban et al [34] developed an indium tin oxide (ITO) data line
process, where the pixel electrodes were formed simultaneously. The minimum PEP number of
the practical production line is five [35]. However, in many cases six to nine PEPs are used.
Since the substrate contains millions of TFTs, production yield is important for cost reduction.
The defect density has to be one order lower than for 1 M DRAM line [36]. Therefore, many
redundant structures have been investigated. Clerc et al [37] proposed a non-crossing structure
where the data lines were formed on the CF substrate in order to avoid an electrical short
between the gate and data lines, and Yanai et al [38] successfully demonstrated the TFT-LCD
with this structure. Takeda et al [39] developed a redundant pixel configuration where each
pixel had a plural number of TFTs and the defective TFT was separated by a laser beam.
Kimura et al [40] developed the array tester to inspect all TFTs within tens of seconds. This
tool not only identified the defective pixels but also characterised TFT performance at any
position [41]. Electrostatic damage deteriorates TFT performance. To avoid this problem, selfdischarge TFT circuits were formed on the glass substrate [42].

TYPICAL TFT-LCD PANELS

TABLE 2 summarises typical LCDs using a-Si:H TFTs.


TABLE 2 Typical a-Si:H TFT-LCDs.
Type
DV
DV
DV
DV
DV
DV
DV
DV
DV
PJ
PJ
PJ
RF

Size
(inch)
40
(29 x 2)
20.1
17
16.1
15.5
15.1
13
11.3
10.5
3.3
3
2.8
5

Aper.
(%)
?

Year

Ref

Grey
scale
?

1997

[43]

Cr/Al-x
Ta/Al
Mo/Al
MoTa/Al
Cr/AlCu
?
Al
Cu
MoTa
Full
?
?

Analog.
3 bit
6 bit
6 bit
6 bit
2 bit
6 bit
?
Analog.
?
8 bit
3 bit

7
?
32%
30%
60%
26%
80%
35%
40%
60%
30%
80%

1996
1993
1995
1996
1997
1993
1996
1996
1993
1996
1996
1996

[44]
[45]
[46]
[47]
[48]
[49]
[50]
[31]
[14]
[51]
[52]
[53]

Pixel
numbers
800 x 400

Pitch
(Hm)
1000 x 1000

TFT

Gate
metal

1280 x 1024
1280 x 1024
1280 x 1024
1920 x 1035
1280 x 1024
1536 x 1024
800 x 600
1280 x 1024
1920 x 960
640 x 480
1024 x 768
320 x 234

312x312
264 x 264
249 x 249
180 x 180
234 x 234
180 x 180
288 x 288
162 x 162
40x40
95x95
55x55
320 x 320

B
C
C
C
?

C
A
C
C
B
B
C

Type: DV, direct view; PJ, projection; RF, reflective mode.


TFT: A, top gate type; B, backside etch type; C, etch-stopper type.

OTHER a-Si:H LCDs

Diode matrix LCDs have a simpler structure than TFT-LCDs. However, extremely uniform and
symmetrical current-voltage characteristics are absolutely required [5]. Although the pin diode
shows good uniformity, the forward voltage at which current flows is not large enough to drive
LC molecules. Yaniv et al [54] proposed a diode ring structure to solve this problem. Hartman
et al [55] improved the picture quality by using reset technology. A pin diode shows
temperature dependent characteristics and film quality also influences diode characteristics [56],
so that the diode matrix LCD needs precise control in fabrication as well as device design.
An a-Si:H film was also used for a projection display, where the film conductivity is modulated
by the incident light and controls the drive voltage of the adjacent LC layer. This system was
used for a light amplifier to produce a very large screen of more than 100-inch diagonal [57].

CONCLUSION

So far, the TFT-LCD market has been largely confined to portable PCs, portable audio-video
equipment and automobile applications. As for projection displays, polycrystalline TFT-LCDs
have been mainly used because of their small size. For large-area displays, a plasma display, a
plasma addressed LCD and a digital mirror device have been demonstrated. Although the
a-Si:H TFT-LCD has the potential to realise large size displays, more breakthroughs are needed
to expand its applications.

REFERENCES
[I]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[II]
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[14]
[15]
[16]

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T.P. Broddy, J.A. Asars, G.D. Dixon [ IEEE Trans. Electron Devices (USA) vol.ED-20 (1973)
p.995 ]
P.G. LeComber, W.E. Spear, A. Ghaith [ Electron. Lett. (UK) vol.15 (1979) p. 179 ]
K. Suzuki, T. Aoki, M. Ikeda, Y. Zohta, Y. Okada, K. Ide [ SID Int. Symp., Dig. Tech. Pap.
(USA) (1983) p. 146]
K. Suzuki [ in Amorphous and Microcrystalline Semiconductor Devices Ed. J. Kanicki (Artech
House, USA, 1991) p.77-139 ]
K. Suzuki [ SID Int. Symp., Dig. Tech. Pap. (USA) (1992) p.39 ]
K. Suzuki [ Datareview in this book: 6.4 a-Si thin film transistors ]
K. Suzuki [ SID Int. Symp., Dig. Tech. Pap. (USA) (1994) p. 167 ]
T. Ueda, J. Sugahara, H. Toeda, M. Akiyama, M. Ikeda, K. Suzuki [ SID Int. Symp., Dig. Tech.
Pap. rf/&4>)(1994)p.739]
T. Kitazawa et al [ Proc. Int. Display Res. Con/. (USA) (1994) p.365 ]
H. Yamanaka, T. Fukunaga, T. Koseki, K. Nagayama, T. Ueki [ SID Int. Symp., Dig. Tech.
Pap. (USA) (1992) p.7S9]
Y. Kato, Y. Hayashi [ SID Int. Symp., Dig. Tech. Pap. (USA) (1996) p.554 ]
H. Hirayama, K. Hidaka, N. Imai, T. Sakaguchi, N. Ibaraki [ SID Int. Symp., Dig. Tech. Pap.
(USA) (1991) p.\%0 ]
H. Toeda, Y. Tsuji, M. Murooka, A. Sugahara, M. Ikeda, K. Suzuki [ Int. Electron Devices
Meet. Tech. Dig. (USA) (1993)p.401 ]
J.H. Kim et al [ AM-LCD Int. Workshop Dig. Tech. Pap. (Japan) (1996) p. 153 ]
K.R. Sarma et al [ SID Int. Symp., Dig. Tech. Pap. (USA) (1991) p.555 ]

[17]
[18]
[19]
[20]

[21]
[22]
[23]
[24]

K.H. Yang [ Proc. Int. Display Res. Conf. (USA) (1991) p.68 ]
M. Ohta, M. Ohe, K. Kondo [ Proc. Int. Display Res. Conf. (Japan) (1995) p.707 ]
M. Akiyama et al [ Proc. Int. Display Res. Conf (Japan) (1986) p.212 ]
H. Lebrun, N. Szydlo, F. Maurice, RG. Stewart, S. Weisbrod, R. Huq [ SID Int. Symp., Dig.
Tech. Pap. (USA) (1996) p.677 ]; R.G. Stewart et al [ SID Int. Symp., Dig. Tech. Pap. (USA)
(1995) p.89 ]
T. Aoyama, K. Ogawa, Y. Mochizuki, N. Konishi [ IEEE Trans. Electron Devices (USA) vol.43
(1996)p.701]
M. Ikeda [ SID Int. Symp., Dig. Tech. Pap. (USA) (1995) p. 11 ]
M. Dohjo, T. Aoki, K. Suzuki, M. Ikeda, T. Higuchi, Y. Oana [ SID Int. Symp., Dig. Tech. Pap.
(USA) (1988) p.330 ]
M. Ikeda, M. Murooka, M. Higuchi, Y. Taniguchi, K. Nishimura [ Proc. Int. Display Res. Conf.

(USA) (\99\) p.93]


[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]

Y. Shimada, T. Yamamoto, M. Goto, H. Morimoto [ SID Int. Symp., Dig. Tech. Pap. (USA)
(1993) p.467 ]
M. Ikeda et al [ Proc. Int. Display Res. Conf (Japan) (1995) p.41 ]
M. Yamamoto et al [ Proc. Int. Display Res. Conf. (USA) (1994) p.142 ]
CW. Kim et al [ SID Int. Symp., Dig. Tech. Pap. (USA) (1996) p.337 ]
T. Tsujimura, H. Kitahara, A. Makita, P. Fryer, J. Batey [ Proc. Int. Display Res. Conf (USA)
(1994) p.424 ]
M. Tsumura et al [ SID Int. Symp., Dig. Tech. Pap. (USA) (1991) p.215 ]
P.M. Fryer et al [ SID Int. Symp., Dig. Tech. Pap. (USA) (1996) p.333 ]
Y. Oana [ SID Int. Symp., Dig. Tech. Pap. (USA) (1996) p.781 ]
F. Richou, F. Morin, M. LeContellec, A. Prolonge [ SID Int. Symp., Dig. Tech. Pap. (USA)
(1992)p.619]
A. Ban, Y. Nishioka, T. Shimada, M. Okamoto, M. Katayama [ SID Int. Symp., Dig. Tech. Pap.

(USA) {\996) p.93}


[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]

Y. Ugai, T. Yukawa, Y. Hatta, S. Aoki [ Jpn. J. Appl. Phys. (Japan) vol.35 (1996) p.L1027 ]
R.R. Troutman [ SID Int. Symp., Dig. Tech. Pap. (USA) (1990) p. 197 ]
J.F. Clerc, T. Leroux, B. Diem [ Proc. Int. Display Res. Conf. (Japan) (1986) p.84 ]
K. Yanai et al [ SID Int. Symp., Dig. Tech. Pap. (USA) (1991) p.26 ]
M. Takeda et al [ Proc. Int. Display Res. Conf (Japan) (1986) p.204 ]; Y. Nakai, M. Akiyama,
M. Ikeda, K. Suzuki [Proc. Int. Display Res. Conf. (USA) (1984) p.436 ]
S. Kimura, Y. Ichioka, K. Suzuki, RJ. Polastre [ SID Int. Symp., Dig. Tech. Pap. (USA) (1992)
p.628 ]
R.R. Troutman [ Proc. Int. Display Res. Conf. (USA) (1994) p.20 ]
T. Yanagisawa [ SID Int. Symp., Dig. Tech. Pap. (USA) (1993) p.735 ]
T. Shinomiya et al [ SID Int. Symp., Dig. Tech. Pap. (USA) (1997) p.497 ]
M. Watanabe, T. Watanabe, Y. Hirai, M. Suzuki, O. Sukegawa [ Proc. Int. Display Res. Conf.
(Euro-Display) (1996) p.587 ]
K. Kawai et al [ SID Int. Symp., Dig. Tech. Pap. (USA) (1993) p.743 ]
S. Hirano [ SID Int. Symp., Dig. Tech. Pap. (USA) (1995) p. 154 ]
T. Higuchi, T. Shimano, N. Nakayama, Y. Yamamoto, S. Hirota, T. Kitazawa [ SID Int. Symp.,
Dig. Tech. Pap. (USA) (1996) p.89 ]
Y. Numano, M. Mizunuma, M. Hayashi, M. Nishimura, K. Kobayashi, M. Morishita [ SID Int.
Symp., Dig. Tech. Pap. (USA) (1997) p. 11 ]
R. Martin et al [ SID Int. Symp., Dig. Tech. Pap. (USA) (1993) p.704 ]
M. Shinjou, H. Nakamura, Y. Hatta, T. Nakagawa, T. Yukawa, Y. Ugai [ AM-LCD Int.
Workshop Dig. Tech. Pap. (Japan) (1996) p.201 ]
M. Sakamoto, T. Ukita, A. Maeda, S. Ohi [ SID Int. Symp., Dig. Tech. Pap. (USA) (1996)
p.681 ]

[52]
[53]
[54]
[55]
[56]
[57]

H. Lebrun, N. Szydlo, F. Maurice, J.F. Teissier, W. Reintsbok [ Proc. Int. Display Res. Con/.
(Euro-Display) (1996) p.583 ]
Y. Itoh, N. Kimura, Y. Ishii, F. Funada, K. Awane [ AM-LCD Int. Workshop Dig. Tech. Pap.
(Japan) (1996) p.409 ]
Z. Yaniv, Y. Varon, V. Cannella, J. MacGill, A. Lien [ SID Int. Symp., Dig. Tech. Pap. (USA)
(1986)p.278]
R.A. Hartman, J.A. van Winsum, G.H. van Leeuwen [ SID Int. Symp., Dig. Tech. Pap. (USA)
(1991)p.24O]
C. Berkel, MJ. Powell, AR. Franklin, ID. French [ J. Appl. Phys. (USA) vol.73 (1993)
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W.P. Bleha [ Proc. Int. Display Res. Con/. (Japan) (1995) p.91 ]; T. Fujii, H. Kikuchi, M.
Kawakita, H. Fujikake, K. Takizawa [ Proc. Int. Display Res. Conf. (Euro-Display) (1996)
p.80]

7.4

Amorphous silicon xerographic applications


S. Shirai and I. Shimizu
August 1997

INTRODUCTION

In 1975, Spear and LeComber [1] reported that the hydrogenated amorphous silicon (a-Si:H)
conductivity could be controlled through doping with impurity elements such as boron and
phosphorus. They demonstrated that they could systematically vary the a-Si:H electrical
conductivity by over ten orders of magnitude by impurity doping. Since then, hydrogenated
amorphous silicon materials having excellent photoconductivity have been prepared. These high
quality materials have been applied to electro-photography photoreceptors [2,3].
So far, a-Si:H has compiled a considerable record in photoreceptor applications. Plain paper
copiers produced by Canon Inc. have been equipped with a-Si:H photoreceptor drums since
1984. In particular the Canon NP-9030 R (with a semiconductor laser light source) and
NP-7550 R (with a halogen lamp light source) plain paper copiers were first marketed in 1984.
Today, great progress has been made in the a-Si:H materials, the photoreceptor device designs,
and the production of these devices. For example, the photoreceptor drum life expectancies
presently exceed three million sheets. Because of the high quality of the a-Si:H electrophotographic imaging and the long life of the photoreceptor drum, a-Si:H materials can be
found in several high volume commercial copying machines. This Datareview will address the
present a-Si:H photoreceptor drum state-of-the-art.

DEVICE STRUCTURE AND ITS PERFORMANCES

In commercially available a-Si:H drums, the stable voltage of about 400 V in our copying
machines must be retained on the photosensitive layer after sensitisation by corona discharge.
In addition, the a-Si.H drums must simultaneously exhibit a high charge retention and a highly
sensitive, rapid discharge of the surface voltage with light exposure. For this purpose, a device
structure which blocks the charge from
the surface and electrode substrate is
Top blocking layer
(a-Si:C:H,0.5/im)
employed [2-6], and impurities such as
C, N and O in a-Si:H were minimised
to 10 ppm or less. In order to block
Photosensitive layer
electron and hole injection into the
(a-Si:H,
20-30/im)
photosensitive layer from both sides of
the electrodes, the Al substrate and the
corona electrode, the device structure
Bottom blocking layer
as illustrated in FIGURE 1 was
(a-Si:H(B,O),3/*m)
employed.
The drum structure is
Conductive substrate
(
Al,3~5mm)
designed
for
positive
corona
sensitisation and has a bottom blocking
FIGURE 1 A schematic cross-section of an a-Si:H drum.
layer (BBL) for electrons and a top

blocking layer (TBL) for holes. The BBL is doped with boron and oxygen, while the TBL is aSii-XCX:H (x > 0.65). The photoreceptor exhibited a high surface-charge retention depending
strongly on the polarity of the corona.
When the photoreceptor is charged with positive corona, the a-Si:H layer is brought to a
charge-depletion state with the dark discharging current controlled by carriers thermally emitted
from deep gap states. Impurities, O and/or N, were added to the BBL to reduce mechanical
stress in the a-Si:H/Al interface and to prevent peel-off of the thick photosensitive a-Si:H layer.

Surface Voltage [V]

The PID (photo-induced discharge) characteristics of the drum are shown in FIGURE 2.
Sensitisation by positive corona secures an acceptance voltage of 400 V or over. Obviously the
discharging rate (-dVs/dt), where Vs is the surface voltage, is constant and the photo-injection
limited regime is retained even in the low-field region of Vs < 50 V, supporting the existence of
a long carrier-range of [ix > 10"7 cm2/V in the photoconductive a-Si:H layer. This high
photoresponsivity is also confirmed even at high temperatures and high humidity. This is an
advantage of using the a-Si:H drum from the viewpoint of reliability.

Exposure [lux*sec]
FIGURE 2 PID characteristic for an a-Si:H drum.

The spectral response of the a-Si:H drum is shown in FIGURE 3. The light exposure necessary
for reducing the initial surface potential to one half, Ey2 (V cm2/|iJ), is plotted as a function of
wavelength for curve (a). Curve (b) is the normalised sensitivity plotted as a function of
wavelength. The high photosensitivities in the whole visible region originate from the strong
optical absorption of a-Si:H, and hence the a-Si:H drum could also be used for printers
equipped with laser diodes emitting about 780 nm beams. One specific aspect of the PED
characteristics is a low residual voltage (Vr) under light illumination, which is independent of
the wavelength, indicating that the carrier-ranges of holes and electrons are long enough
compared to the whole layer thickness. This is one of the expected advantages of an a-Si:H
drum. The increase in Vr is negligible after repeated cycles of charging and PID, so that the

(b)
(a)

(b) Arbitrary Unit

(a) Sensitivity Ei/KVcmV/i J)

appearance of ghost images due to the repeated imaging processes is completely avoided. The
residual voltage Vr observed in the PID characteristic curve (FIGURE 2) is induced by the
polarisation of the TBL and can be reduced to almost zero by optimising the deposition
conditions during its formation. The observed polarisation of Vr ~ 20 V causes no deterioration
of the sensitivity and image quality.

WavdengtKnm)
FIGURE 3 Spectral sensitivity for a commercial a-Si:H drum.

PRODUCTION AND ITS RELATED ISSUES

Cl

Increasing Deposition Rate

The a-Si:H photosensitive layer must have a film thickness of 20 - 30 jam to provide the
requisite receptor potential without excessively increasing the field strength of the
photosensitive layer. This means the deposition rate of a-Si:H photoreceptors must be
increased dramatically as compared with a-Si:H solar cells ( 2 - 5 A/s) if photoreceptors are to
be easily reproducible. By optimising the parameters during film formation (gas flow, discharge
power, substrate cylinder temperature, ratio of diluent gases, etc.), cells can be produced with
deposition rates of about 10 |im/hr (30 A/s). Unfortunately, if heating of the substrate cylinder,
film formation and cooling time are taken into consideration, this process requires about six
hours; when processing of byproducts of film formation (polysilane) is also included, the
production time for such film stretches far beyond that required for other types of
photoreceptor. There are also many other production impediments that need to be eliminated,
such as the high price and great size of plasma CVD equipment and the low efficiency (10 15%) of the use of the raw material gases.
In recent years, the growth techniques have enabled the a-Si:H photoreceptor a-Si:H drums to
be deposited at 20 - 30 \im/hr using a microwave (2.45 GHz) plasma assisted chemical vapour
deposition process. This process also provides excellent source gas utilisation. The new
microwave techniques utilise over 60% of the source gas as compared to less than 10% for the
techniques commonly used fifteen years ago. High source gas utilisation significantly reduces
the a-Si:H receptor drum manufacturing costs.

Through careful optimisation it was possible to identify growth conditions yielding high growth
rates, while avoiding the increased polysilane dust generation that typically plagued early
attempts to increase the growth rate. Dust generation decreases the production yields and the
quality of the electro-photographic imaging. Presently it is possible to prepare materials at
2 0 - 3 0 |im/hr that have properties equivalent to materials grown at the lowest growth rates. As
a consequence of this remarkable progress the cost of a-Si:H receptor drums has been
decreasing in recent years and is soon expected to be competitive with other materials used for
the low cost copying machine application.
C2

Image Blurring and Countermeasure

The surface of a photoreceptor is subjected to adsorption of chemically reactive molecules and


ions, contact or friction with other materials such as toner or paper, and the mechanical touch of
a cleaning blade. The process of duplicating images is composed of steps such as sensitisation,
individual image exposure, development, transfer, and cleaning. Under these conditions, stable
electrostatic latent images and toner images have to be duplicated on surfaces. Gas molecules
such as H2O, CO, O2 and NH3 are known to be adsorbed on a-Si:H surfaces, and to cause
delicate changes in the electronic states of the surface as well as large changes in surface
conductivity. This susceptibility of the surface markedly damages the stability and reliability of
photoreceptors, and should be eliminated by the TBL.
The a-Si:H surface reacts with active molecules such as O3 generated by corona discharge in
sensitisation, and forms a thin hydrophilic layer of SiOx on the surface. The existence of such a
layer causes image blurring. Accordingly, the conditions for fabricating the TBL from
a-Sii-xCx:H were optimised to obtain the chemical composition and structure which lead to
formation of SiOx by oxidation of the surface. The optimised a-Sii-xCx:H TBL is chemically
stable and has an excellent scratching strength and resistance to mechanical friction. Such a
stable surface is assured in a-Si:H drums used in practice, and a drum heater is equipped to heat
the photoreceptor up to around 400C for the purpose of attaining stability and reliability at high
temperatures and in humid environments.
C3

Appearance and Elimination of Image Defects

Any noise which reduces the quality of duplicated images must be completely removed. The
possible causes associated with image defects in a-Si:H drums are (1) localised structural
defects such as hills or pinholes formed by abnormal growth, (2) local peel-off of films, and (3)
damage to photoreceptors induced by localised breakdown under corona discharge. Causes (1)
and (2) are induced in the production of a-Si.H drums, and are problems in the manufacturing
technology, particularly in a-Si:H deposition. Cause (3) originates from localised changes on
the surface under corona discharge. However, image defects due to this cause have already
been eliminated by the optimised design of the corona chargers and the cleaning blade. Further
details of defect removal techniques are described below.
The abnormal growth proceeds conically toward the surface of the photoreceptor from a
nucleus on the Al cylinder, and forms a globular shape on the surface. It conspicuously
deteriorates the smoothness of the a-Si:H drum surface. It was found that image defects are
caused by a globular shape 30 \xm or more in diameter. The abnormal growth site is located on
the Al surface and the unusual nucleation on the cylinder is caused by surface impurities and

dust generated by cutting and cleaning of the cylinder. In addition, pumping of the reactor
becomes a source of defects, because fine particles are often generated.
C4

Durability

Surface Voltage(V)

One of the prominent features of a-Si:H photoreceptors is the high durability that can be
expected given their stable characteristics and high mechanical strength. In the thirteen years
since photocopiers containing a-Si:H photoreceptors went on the market, their durability has
been well proven. Most a-Si:H photoreceptors can produce from hundreds of thousands to one
million copies without replacement; some have been used for as many as three million copies.
After repeated contact with corona discharge, light and cleaning fluid over the course of one
million copies, the characteristics (charge capacity, sensitivity, etc.) of the a-Si:H
photoreceptors were measured. Absolutely no change was observed from the initial
characteristics. The PID characteristics of the drum are shown in FIGURE 4.

Exposure(lux*sec)

FIGURE 4 PID characteristics for an a-Si:H drum. The characteristics


initially (open circle) and after one million copies (filled circle).

The a-Si:H photoreceptors most often must be replaced because of some sort of damage, such
as scratches made during cleaning or gouges caused by paper clips or staples getting pulled into
the copier. Thus, if measures are taken to eliminate these situations, the life of the
photoreceptor should be equal to or greater than the life of the machine itself, and it will be
possible to consider the a-Si:H photoreceptors as simply another copier component.

CONCLUSION

Copying machines and laser printers equipped with a-Si:H photoreceptor drums have
established an excellent reputation for their capability to produce stable, high quality prints and
high durability. The development of novel production systems involving microwave plasmas is
successfully reducing the costs of a-Si:H photoreceptor drums by reducing the quantity of
costly materials consumed and by improving the throughput of the production equipment by
enhanced growth rate. Presently, the copying machine operating cost, i.e. the life of the drum
divided by the production cost, is considerably more for a-Si:H drums compared to that of OPC

drums as the OPC photosensitive drums have also made remarkable progress in achieving high
sensitivity and long life. In order to further extend the a-Si:H market share, it is necessary to
accelerate cost reductions while further improving the device performance. That is, the
acceptance voltages and photosensitivity of the a-Si:H photoreceptor drums must be improved.
In addition, novel techniques for preventing image smearing under conditions which promote
surface adsorption, such as high temperature and high humidity, which do not require heating
the drum must be developed. Despite these problems, the a-Si:H photoreceptor drum offers
high stability, high quality copies and high durability, and the a-Si:H drums contain no
environmentally dangerous materials. These attributes will continue to fuel interest in further
developing a-Si:H based electrophotography.

REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]

W.E. Spear, P.G. LeComber [ Solid State Commun. (USA) vol.17 (1975) p.l 193 ]
I. Shimizu, T. Komatsu, E. Inoue [Photogr. Set Eng. (USA) vol.24 (1980) p.251 ]; I. Shimizu,
S. Shirai, E. Inoue [ J. Appl Phys. (USA) vol.52 (1981) p.2776 ]
N. Yamamoto, Y. Nakayama, K. Wakita, M. Nakano, T. Kwamura [ Jpn. J. Appl. Phys.
(Japan) vol.20 suppl.20-1 (1981) p.305 ]
I. Shimizu, S. Oda, K. Saito, H. Tomita, E. Inoue [ J. Phys. (France) vol.42 suppl.C-4 (1981)
p.1123]
E. Inoue, I. Shimizu [ Photogr. Sci. Eng. (USA) vol.26 (1982) p.148 ]
S. Oda, Y. Saito, I. Shimizu, E. Inoue [ Philos. Mag. B (UK) vol.43 (1981) p.1079 ]

7,5

Amorphous silicon alloy LEDs


D. Kruangam
July 1997

INTRODUCTION

At present, the needs for flat-panel and wide area displays are continually increasing. Examples
of flat-panel displays widely used are liquid crystal display (LCD), light emitting diode (LED)
and electroluminescence (EL). TABLE 1 shows a comparison of the characteristics of these
flat-panel displays. An advantage of the LCD is its low power consumption. However, the
LCD has some drawbacks: the viewing angle is limited, the contrast is poor, and it needs an
external light source. EL displays can be produced with a large area, but they need an
operational voltage higher than 100 V. LEDs seem to be suitable for a flat-panel display, since
the brightness is very high and they can be operated at a low voltage (less than 10 V). Some
disadvantages of LEDs are that they are made out of expensive and single crystalline
semiconductors, and they are packaged in a chip which has to be cut into a very small size
(e.g. 0.1 x 0.1 mm2). Therefore, a wide area LED display must be constructed by assembling a
large number of LED chips into arrays or a matrix.
TABLE 1 Comparisons of someflat-paneldisplays.
Descriptions

EL

LCD

c-LED

Principle

Intrinsic EL

Polarisation of light

Radiative
recombination
centres
Substrate

Colour centres

Glass

Glass

Possibility of
large area
Fabrication
temperature
Driving voltage
Current
consumption
Brightness
(cd/m2)
How to change
colour
Possibility of
full colour
Cost
Stability

Good

Good

Carrier injection
EL
Impurities,
band-to-band,
isoelectronic traps
Crystal
semiconductor
Fair

5000C
AC/DC 160 - 250 V
mA/cm2

DC<5V
nA/cm2

60 -1000

Amorphous
TFLED
Carrier injection EL
Localised states

Glass, metal,
ceramic, polymer
Very good

8000C

3000C

DC 2 - 10 V
A/cm2

DC 5 - 20 V
100 -1000 mA/cm2

>150

5-20

Rare earth

Filter

Crystal, impurity

Material contents

Yes

Yes

Yes

Yes

Middle
Fair

Cheap
Very good

Expensive
Very good

Cheap
Poor

Another approach to obtain a low cost and large area display is to develop an amorphous silicon
alloy LED. The first success of the fabrication of a visible-light amorphous silicon alloy based

LED can be traced back to 1985, when Kruangam et al [1] observed visible-light emission from
the p-i-n junctions of a-SiC:H deposited on a glass substrate. The details of their
electroluminescent properties have been described in Datareview 6.3. The device has been
particularly named cthin film light emitting diode9 (TFLED). The important motivation of the
development of the amorphous TFLED is to use the unique feature of amorphous
semiconductors that a lack of long range ordering in the atomic network relaxes the k-selection
rules for the optical transitions. This will give rise to a large optical absorption coefficient and
presumably a high luminescent efficiency, which can be used in the light emitting devices.
In this Datareview, information on the basic technologies, the properties and the applications of
amorphous Si alloy TFLEDs is described.

ADVANTAGES
DISPLAYS

OF AMORPHOUS

ALLOY

LEDs

FOR

FLAT-PANEL

Amorphous TFLEDs have several advantages over conventional crystalline LEDs as follows:
(1)

The optical energy gap of amorphous silicon based alloys (a-SiC:H, a-SiN:H, a-SiO:H)
can be varied widely from 1.7 eV to more than 4.0 eV by changing the composition of
Si/C, Si/N, Si/O in the films as shown in FIGURE 1 [2].
AlAs

GaP

SlC(/5) SIC(CO GaN ZnS

OPTICAL ENERGY GAP

eV
nra

x increase
FIGURE 1 Optical energy gaps of various amorphous silicon alloys [2].

(2)

The colour of the light emission can be varied from red to white-blue by adjusting the
optical energy gap of the amorphous silicon alloys.

(3)

Because of the feature of amorphous networks, amorphous silicon alloys can be


deposited in large areas on various kinds of foreign substrates such as glass, stainless
steel [3], ceramic and polymer sheets.

(4)

The fabrication process of the amorphous TFLED does not require a high temperature
condition. This can lead to a low cost TFLED and the possibility that it can be mass
produced.

(5)

The amorphous TFLED can emit the light in a desired pattern by designing the pattern
of the internal conductive electrodes [2].

(6)

The amorphous TFLED can be operated at a low voltage (5 - 20 V). By utilising thin
film technology, the TFLED and its driving circuits might be fabricated on the same
substrate. This could lead to new and smart three-dimensional optoelectronic devices

BASIC STRUCTURE OF AMORPHOUS Si ALLOY TFLEDs

The basic structure of an amorphous TFLED is the p-i-n junction of amorphous silicon alloys.
It has been reported [5] that a-SiC:H is the best material for both the p-, n- injectors and
i-layers. FIGURE 2 shows the typical structure of an a-SiC.H TFLED (glassATO/p-a-SiC.H/
i-a-SiC:H/n-a-SiC:H/Al). The p- and n-layers act as injectors of holes and electrons,
respectively, into the luminescent active i-layer. Moreover, according to [5], the optimal
thicknesses of the p-i-n layers are 150 A, 500 A and 500 A, respectively, and the optical energy
gap of the i-layer necessary for visible light emission ranges from 2.5 to more than 3.0 eV. The
EL intensity strongly depends on the thickness and optical energy gap of the i-layer. FIGURE 3
shows schematic band diagrams of a-SiC:H p-i-n junctions in (a) thermal equilibrium and
(b) forward bias conditions. The injection electroluminescence is observed when the diode is
positively biased. In order to obtain a visible luminescence, the optical energy gap of the i-layer
has to be approximately the same as or larger than 2.3 eV, while the optical energy gaps of the
p- and n-layers should be chosen, at most, around 2.0 eV to ensure the effective valency
controllability to p- and n-type semiconductors. Therefore, holes and electrons are injected into
the i-layer by tunnelling effects through the notch barriers at the p/i and i/n interfaces,
respectively. TABLE 2 shows typical preparation conditions for an a-SiC.H TFLED.

Glass substrate

FIGURE 2 Typical structure of an a-SiC:H p-i-n TFLED [5].


TABLE 2 Preparation conditions for a-SiC:H p-i-n TFLED.
Power source
RF power
Substrate temperature
Total gas pressure
p-type a-SiC:H
i-type a-SiC:H
n-type a-SiC:H
Device area

C-coupling, 13.6 MHz


4W
1900C
l.Otorr
SiH4ZCH4ZB2H6= 1.5/3.5/0.03
SiHVC 2 H 4 =I^
SiHVCH4ZPH3 = 1.5/3.5/0.03
0.033 - 64 cm2

(a) zero bias

(b) forward bias


FIGURE 3 Schematic band diagrams of a-SiC:H p-i-n junctions in
(a) thermal equilibrium and (b) forward bias conditions [5].

BASIC PROPERTIES OF AMORPHOUS SILICON ALLOY TFLEDs

FIGURE 4 shows plots of I-V curves measured


at room temperature for a-SiC:H TFLEDs [6].
The parameter in FIGURE 4 is the optical
energy gap of the i-layer, i.e. 2.60, 2.85 and
3.0 eV. The optical energy gaps of the p- and
n-layers are kept constant at 2.0 eV. The
thickness of all the i-layer is set at 500 A. The
threshold of the voltage increases from about
7 V to 17 V as the optical energy gap of the
i-layer increases. The increase of the threshold
voltage with increasing optical energy gap of
the i-layer is due to the increase of the height of
the notch barriers at the p/i and i/n interfaces as
well as the series resistance of the i-layer. The
TFLED with the optical energy gap of the ilayer = 2.6 eV and 3.0 eV emits red and yellow
colour light, respectively. Examples of the EL
spectra and relationship between the EL
intensity and injection current have been shown
inDatareview6.3.

(raA/cm2) E
opt of i-layer

(V)

FIGURE 5 shows the dependence of the integral intensity of the light emission on the frequency
of the pulse current for a yellow a-SiC:H TFLED. It is found that the intensity of the light is
constant at frequencies below 100 kHz and starts to decrease at frequencies above 100 kHz.
The cut-off frequency at which the intensity of light is 70% of the value at low frequency is
about 500 kHz. This result implies that the a-SiC:H TFLED can respond fast enough to the
pulse current input with a frequency up to about 500 kHz. Therefore, the a-SiC:H TFLED can
be used in a pulse current scanning mode as a flat-panel display.

CD
QH
UJt-"
rvico
-JUJ

5
O
Zh
UD
-J

Amplitude of pulse current=16mA


Duty cycle=50%
glass/ITO/p-i-n a-SiC:H/Al TFLED
at 300 K

MODULATION FREQUENCY (Hz)

FIGURE 5 Dependence of the integral intensity of the light emission


on the frequency of the pulse current for a yellow a-SiC:H TFLED.

MATRIX TFLEDs

Kruangam et al [6] proposed a dot matrix array structure of a-SiC:H TFLEDs. By using this
matrix structure and scanning electronic circuits, movable emitting patterns of light can be
realised. The dot matrix TFLED display consists of a number of grid ITO electrodes deposited
perpendicularly to a number of grid Al electrodes, as shown in FIGURE 6. The emission is
observed at the crossing area of the front ITO and rear Al electrodes. Several versions of the
dot matrix yellow-orange displays with a screen size from 4 x 4 cm2 to 8 x 8 cm2 have been
demonstrated in [6]. The sizes of pixels are between 0.3 x 0.3 mm2 and 1 x 1 mm2. The results
from a simple analysis show that there is no cross talk in the display, and that the minimum
spacing distance between the adjacent two ITO or Al electrodes can be as small as the order of
a micrometre. The brightness of these TFLEDs is of the order of several cd/m2, so that the
emission has to be observed in a dim room. FIGURE 7 shows a photograph of an a-SiC:H
TFLED flat-panel display. TABLE 3 summarises basic parameters and properties of a-SiC:H
p-i-n thin film light emitting diodes.
Al bade
Electrode
p-i-n Layers of
or
or

ITO Front Electrode


Glass Substrate

LIGHT OUT PUT


FIGURE 6 Structure of a dot matrix TFLED display consisting of grid
ITO electrodes deposited perpendicularly to grid Al electrodes [6].

FIGURE 7 Photograph of a-SiC:H TFLED flat-panel display.


TABLE 3 Summary of basic parameters and properties
of a-SiC:H p-i-n thin film light emitting diodes.
Properties
Thickness of p-layer
Thickness of i-layer
Thickness of n-layer
Optical energy gaps of p- and n-layers
Optical energy gap of i-layer and colour of emission

Normal operation temperature


Threshold voltage
Rectification ratio of forward to reverse current
Current consumption
Brightness
Maximum frequency for pulse current operation

APPLICATIONS OF AMORPHOUS
FUNCTIONAL DEVICES

Typical values
150 A
500 A
500 A
2.OeV
2.5 eV (Red)
2.6 - 2.8 eV (Orange)
2.9-3.2 eV (Yellow)
>3.5eV (White blue)
Room temperature
7-17 V
~10 2 3 (at 8 V)
100 -1000 mA/cm2
5 - 20 cd/m2
~500kHz

TFLEDs

TO

OPTOELECTRONIC

Although the brightness of the a-SiC:H TFLED is still too low for a display application, it has
been reported [6] that an a-SiC:H TFLED has the possibility to be used as a light source for an
electronic application, for example, an amorphous photocoupler. The amorphous photocoupler
consists of an amorphous TFLED and an amorphous thin film photodiode (TFPD) sealed in a
single package, as shown in FIGURE 8. TABLE 4 summarises typical device parameters of an
amorphous photocoupler. The amorphous photocoupler is useful, for example, in providing

optical signal transmission, an interface between logic circuits, position and size detection of
moving objects, tape end detection, I/O interfaces from computers, etc. The advantages of the
amorphous photocouplers are as follows:
(1)

It is possible to fabricate an amorphous photocoupler either in a small or large area.

(2)

It is easy to fabricate arrays and matrix type photocouplers.

(3)

Both light emitting diode and photodiode are made from low cost amorphous silicon
alloys.

(4)

It is possible to deposit an amorphous TFLED and an amorphous TFPD on dual


surfaces of a common glass substrate and/or design multi-layer devices.

(5)

Both a photointerrupter and a photoisolator type can be realised by the amorphous


photocoupler.
PHOTO-INTERRUPTER
AiMORPHOUS
TFLED

AMORPHOUS
TFPD

glass substrate
TFLED

PHOTO-ISOLATOR

(a)

PHOTORESISTOR

glass substrate

(b)

TFPD

TFLED

glass substrate
TFLED

(C)

PHOTORESISTOR

glass substrate

(d)

FIGURE 8 Structures of amorphous photocouplers consisting of amorphous


TFLEDs and amorphous thin film photodiodes (TFPDs) [6].

TABLE 4 Device parameters of amorphous photocoupler consisting


of an amorphous TFLED and an amorphous TFPD.
Amorphous thin film LED
(TFLED)
P a-SiC:H E o p t =2.0eV
d=150A
a D = 10"7 S/cm
i a-SiC:H Eopt = 3.0eV
d = 500 A
n a-SiC:H E0Pt = 2.0 eV
d = 500 A
a D = 10"7 S/cm
External quantum
efficiency ~10'3%

Amorphous thin film


photodiode (TFPD)
a-SiC:H E o p t =2.0eV
d=150A
a D = 10"7 S/cm
E o p t =1.8eV
a-Si:H
d = 5000 A
E
MC-Si:H
opt = 2.0 eV
d = 500 A
a D = 10"1SZCm
Efficiency = 6% at AMI
(when measured
as a solar cell)

The current transfer ratio defined as the ratio of the output photocurrent of a TFPD to the input
current of a TFLED for the amorphous photocoupler obtained in the demonstration is of the
order of 10"5%. Here, the distance between the TFLED and TFPD is 1 mm2. It has been
reported [6] that the amorphous photocoupler can be operated up to a frequency of several
hundred kHz.
FIGURE 9 shows another novel structure of the
amorphous photocoupler where an a-SiC: H
TFLED and a TFPD are deposited on the same
side of a glass substrate [7]. The unique idea is
that some portion of the light from a TFLED
propagates in the glass substrate (waveguide) in the
lateral direction and the light is then reflected by
the textured-surface of the glass substrate so that
the light is turned up to the a-Si:H TFPD. The
textured surface of the glass substrate here acts as
a kind of a distributed Bragg reflector (DBR) and
is obtained by abrading the surface of a glass
substrate with SiC powder. By using this kind of
monolithic technology, a new kind of amorphous
optoelectronic integrated circuit (OEIC) might be
realised.

TFLED

TFPD

Textured-surface Glass Substrate

CONCLUSION

Amorphous silicon alloy thin film LEDs (TFLEDs) have some attractive points such as the
possibilities of low cost, light weight and large area. However, there are still several problems
that have to be overcome, e.g. low brightness and short lifetime. Apart from displays, the
TFLEDs have potential to be used as light sources in electronic applications, such as
photocouplers and OEICs.

REFERENCES
[1]
[2]
[3]
[4]
[5]
[6]
[7]

D. Kruangam, T. Endo, W. Guang-Pu, H. Okamoto, Y. Hamakawa [ Jpn. J. Appl Phys.


(Japan) vol.24 (1985) p.L806 ]
D. Kruangam, W. Boonkosum [Mater. Res. Soc. Symp. Proc. (USA) vol.345 (1994) p.305 ]
W. Boonkosum, D. Kruangam, B. DeLong, S. Panyakeow [ Mater. Res. Soc. Symp. Proc.
(USA) vol.336 (1994) p.849 ]
D. Kruangam, W. Boonkosum, B. Ratwises, T. Sujaridchai, S. Panyakeow [ 13th Australian
Microelectronics Conf. (Australia) (1995) p.259 ]
D. Kruangam [ a-SiC:H TFLED in Amorphous and Microcrystalline Semiconductor Devices
Ed. J. Kanicki (Artech House, USA, 1991) p.195 ]
D. Kruangam, W. Boonkosum, B. Ratwises, S. Panyakeow, B. DeLong [ Proc. 8th Int. School
on Cond. Matter Physics (Bulgaria) (1994) p.87 ]
D. Kruangam, T. Sujaridchai, K. Chirakawikul, B. Ratwises, S. Panyakeow [ Proc. 17th Int.
Conf. on Amorphous and Microcrystalline Semiconductors (Hungary) (1997) ]

CHAPTER 8

MACROSCOPIC DATA
8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9

Density of a-Si, a-SiNx, a-SiC and a-SiGe


Elastic constants of a-Si and a-Si:H
Hardness and wear of a-Si and a-Si:H
Intrinsic stress in a-Si and a-Si:H films
Thermal expansion coefficient of a-Si and a-Si.H
Specific heat of a-Si, a-Si:H and a-SiNx
Thermal conductivity of a-Si, a-SiNx and a-SiC
Melting point of a-Si and a-Si:H
Optical functions of amorphous silicon

8.1

Density of a-Si, a-SiNx, a-SiC and a-SiGe


H. Ohsaki and Y. Tatsumi
February 1997

INTRODUCTION

The density of amorphous materials depends strongly on their atomic structure (atomic
networks and dangling bond formation) and microscopic structure (void formation, boundarylike structure). The qualitative relationship between the density of the amorphous films and the
preparation conditions has been obtained by many researchers, but identical density values were
not obtained for each deposition condition, and the values vary with laboratories or machine
used.

AMORPHOUS SILICON

Bl

Crystalline Silicon

The density of single crystal silicon (c-Si) is a standard value for comparison with that of
amorphous silicon (a-Si) and hydrogenated amorphous silicon (a-Si:H). The density of c-Si has
been accurately measured by researchers from the US National Bureau of Standards (NBS)
[1-7], Physikalisch-Technische Bundesanstalt (PTB) [8-11], Istituto di Metrologia G.
Colonnetti (IMGC) [6,11-13] and Japanese National Research Laboratory of Metrology
(NRLM) [14], for the purpose of obtaining a solid density standard to take the place of water
which is the commonly adapted density standard. The density given lately is 2.32908350 +
0.00000036 g/cm3 at 200C and 101325 Pa by IMGC [13], which is slightly different from the
NBS value of 2.3290028 g/cm3 at 25C and 101325 Pa. NBS have measured the density of
several c-Si specimens of lightly doped transistor grades and have reported it to be 2.328993 2.329037 g/cm3 at 25C. Petley discusses a relation between the atomic weight and the density,
and points out that the total range of variation of the atomic weight for silicon is 0.001
(i.e. 36 ppm) [15]. Accordingly, we deduced that the density of c-Si is 2.3290 0.00008
g/cm 3 at25C.
The effects of the most common impurities, oxygen and carbon, on the density of c-Si have
been studied [16]. Because the interstitial oxygen impurities decrease the net density of c-Si by
0.09 x 10"8 and the substitutional carbon impurities increase the net density by 1.85 x 10"8, these
impurities, at not more than 10"5/cm3 concentration, do not affect the recommended value of the
density of c-Si.
Densities of c-Si at various temperatures can be evaluated from the thermal expansion
coefficients given both at low temperature ( 6 - 3 4 0 K) by Lyon [17] and at high temperature
(350 - 1500 K) by Okada [18]. It is then found that the density d (g/cm3) at T (K) has the
values given in TABLE 1.

TABLE 1 Densities of c-Si at various temperatures.


T
d

<55
2.3306

60-85
2.3307

90-150
2.3308

160-170
2.3307

200
2.3304

250
2.3298

300
2.3290

T
d

350
2.3280

400
2.3269

500
2.3245

600
2.3220

700
2.3192

800
2.3164

900
2.3136

T
d

1000
2.3106

1100
2.3077

1200
2.3047

1300
2.3016

1400
2.2986

1500
2.2955

The apparent uncertainties are less than 0.0001 g/cm3.


B2

Amorphous Silicon

a-Si is prepared by self-implantation [19-21], vacuum evaporation [22-26] or sputtering


[27,28]. The physical properties depend on preparation conditions. The densities spread in the
region of 73 - 99% of that of c-Si [19-28]. The densities are given separately according to the
preparation method (TABLES 2-4).

Density
Density ratio
Ref
(g/cm3)
ofa-Sitoc-Si
2.29
0.982 + 0.001
[19]
TABLE 2 Densities of a-Si films prepared by the self-implantation method.
2.28
0.98
[20]
2.05
0.95 + 0.01
[211

Density
(g/cm3)
1.71+0.09
1.75 - 1.85
>2.1
2.07 - 2.25
2.24
2.16 + 0.10

Pressure
Density ratio Substrate temp. Deposition rate
(nm/s)
(0C)
(Pa)
ofa-Sitoc-Si
0.012-0.186
RT
0.73
5.6 x IO"6 - 5.6 x 10 4
TABLE 3 Densities of a-Si deposited by vacuum evaporation. 4
0.2-1
RT
0.75 - 0.80
io0.2-1
>270
>0.90
IO4
0.1 - 1.6
25 - 400
0.89 - 0.97
7 x 10 5
0.5
RT
0.96
1.63-3.33
RT
0.93 + 0.04

Ref
[22]
[23]
[23]
[24]
[25]
[261

TABLE 4 Densities of a-Si deposited by sputtering.


Density
(g/cm3)
2.30
2.29

Density ratio
of a-Si to c-Si
0.988
0.98

Deposition rate
(nm/s)
0.1

Ref
[27]
[28]

High energy Si implantation into c-Si makes an a-Si thin layer. Spitzer shows that selfimplanted a-Si is void free [20] and that relaxation by thermal annealing does not change the
density [19-21].
Densities of a-Si deposited by vacuum evaporation vary widely between researchers. Tatsumi
shows that the density of a-Si deposited on a room temperature substrate is independent of its

thickness (102 - 514 nm), deposition rate (0.012 - 0.186 nm/s) and of the environmental
pressure during the deposition (5.6 x IO"6 - 5.6 x 10"4 Pa) [22]; other researchers obtained
denser a-Si with higher deposition rates. Brodsky shows that the density increases (2.07 - 2.25
g/cm3) with the substrate temperature (25 - 4000C) [24].
Densities of a-Si deposited by sputtering have been published in two papers [27,28]. The
densities obtained are quite similar and given in TABLE 4.
B3

Hydrogenated Amorphous Silicon

a-Si:H is prepared by glow-discharge decomposition [29-42], sputtering [27,28,43] or thermal


decomposition (CVD: chemical vapour deposition) [44,45], and the densities are tabulated
separately (TABLES 5, 9, 10).
Glow-discharge decomposition is the most widely used method but the densities of a-Si:H
change with preparation conditions.
TABLE 5 Densities of a-Si :H deposited by glow-discharge decomposition.
Density
(g/cm3)
2.09 - 2.30
2.16-2.25
2.14-2.25
1.58-1.79
2.14
2.18-2.25
2.0-2.3
2.02
1.98-2.10
2.24
1.92-2.27
1.47, 1.70
2.00, 2.28
1.92-2.27
2.13
1.9 + 0.15

Density ratio
ofa-Si:Htoc-Si
0.90 - 0.99
0.93 - 0.97
0.92 - 0.97
0.68 - 0.77
0.92
0.94 - 0.97
0.86 - 0.99
0.87
0.85 - 0.90
0.96
0.82 - 0.97
0.63, 0.73
0.86, 0.98
0.82 - 0.97
0.91
0.82

Substrate temp.
(0C)
150 - 370
150 - 370
50 - 320
23 4
200
25 - 320
70 - 300
60-80
RT
High temp
25 - 450
25
250
25 - 450
RT

Deposition rate
(nm/s)

H content
(at.%)
7.3 - 15.4
5-15

0.05 -1.5
0.72 -1.720
0.879

0.3

332

7-26
35,25
14, 18
7-26

Ref
[29,30]
[31]
[32]
[33]
[33]
[34]
[35]
[36]
[37]
[37]
[38]
[39]
[39]
[40]
[41]
[42]

Most operating parameters (applied power, total pressure and gas flow rate) do not affect the
obtained density [33]. Ozawa [34] and Weitzel [35] show that the density increases with
substrate temperature but Jones indicates no clear relationship between the density and the
substrate temperature [32].

TABLE 6 Densities of a-Si:H deposited by glow-discharge decomposition at various substrate temperatures


(upper table [34] and lower one [35]).
Substrate
temp. (0C)
Density
(g/cm3)
Substrate
temp. (0C)
Density
(g/cm3)

65

130

200

250

320

1.72

1.97

2.12

2.19

2.25

100

150

200

250

300

350

2.07

2.10

2.18

2.28

2.35

2.38

Schmidt shows that the density increases with decrease of hydrogen content in the a-Si:H, and
Kuschnereit indicates that the maximum densities are obtained with hydrogen content around
8 - 10 at.%.
TABLE 7 Densities of a-Si:H deposited by glow-discharge decomposition with various hydrogen contents
(upper half [29] and lower half [31]).
Density
(g/cm3)
2.09
2.28
2.30
2.16 + 0.02
2.30 0.02
2.25 + 0.05

Density ratio
ofa-Si:Htoc-Si
0.897
0.979
0.988
0.93
0.99
0.97

Substrate temp.
(C)
150
250
370
150
250
370

H content
(at.%)
15.4
10.6
7.3
15
9
5

Tsai and Fritzsche measured the densities of a-Si:H deposited at cathode and anode. The
results show that the deposition position is not important but hydrogen content is related to the
density [38,40].
TABLE 8 Densities of a-Si:H deposited by glow-discharge decomposition at cathode and anode [38].
Density
(g/cm3)
2.10
2.15
2.27
1.92
2.17
2.21

Density ratio
ofa-Si:Htoc-Si
0.90
0.92
0.97
0.82
0.93
0.95

Substrate temp.
(0C)
25
270
450
25
270
450

H content
(at.%)
20
14
7
26
12
11

DC bias
Cathode
Cathode
Cathode
Anode
Anode
Anode

The density of a-Si:H deposited by sputtering has been published in three papers [27,28,43]
summarised in TABLE 9.

TABLE 9 Densities of a-Si:H deposited by sputtering.


Density
(g/cm3)
2.20
1.30 -1.79
1.73-2.07
1.90-2.24

Density ratio
ofa-Si:Htoc-Si
0.95
0.56 - 0.77
0.74 - 0.89
0.82 - 0.96

Substrate temp.
(0C)

H content
(at.%)
10

-196
27

Ref
[27]
[43]
[43]
[28]

The density of CVD a-Si:H has been published in two papers [31,44]. From the results, denser
a-Si:H is obtained at higher substrate temperatures.
TABLE 10 Densities of a-Si:H deposited by thermal decomposition (CVD).
Density
(g/cm3)
1.625 + 0.08
2.114 + 0.02
2.20 + 0.05
2.20 + 0.05
2.24 + 0.05
2.26

Density ratio
ofa-Si:Htoc-Si
0.70
0.91
0.95
0.95
0.96
0.97

SILICON NITRIDE

Cl

Crystalline Silicon Nitride

Substrate temp.
(0C)
150
200
250
270
300
550 - 650

H content
(at.%)
18
15
7
8
10

Ref
[31]
[31]
[31]
[31]
[31]
[44]

The densities of c-SisN4 are evaluated from X-ray data [45,46]. The evaluated densities are
presented in TABLE 11.
TABLE 11 Densities of C-Si3N4 evaluated from X-ray data.
Polytype

Density
(gfcm3)
3.183

(X-Si3N4

P-Si3N4
C2

3.200

Ref
[45]

I [46]

Amorphous Silicon Nitride

Amorphous silicon nitride (a-SiNx) and hydrogenated amorphous silicon nitride (a-SiNx:H) may
be prepared by sputtering, thermal decomposition (CVD) [47-49] or glow-discharge
decomposition (PECVD: plasma enhanced chemical vapour deposition) [50-54]. The
composition of a-SiNx and a-SiNx:H changes with deposition conditions and the properties also
change.
For example, the oxidation mechanism changes with the composition and
stoichiometric SiNx (namely Si3N4) has the lowest oxidation rate [55]. However, the relation
between the density and the composition is not clear.

TABLE 12 Densities of a-SiNx:H deposited by CVD.


Composition

Sio.48No.52

Density
(g/cm3)
2.68 - 3.44
2.79
3.00.1

Substrate temp.
(0C)
752 - 812
760
835

Ref
[47]
[48]
[49]

TABLE 13 Densities of a-SiNx:H deposited by PECVD.


Composition
Sio.4oNo.48Ho. 12
si0.37N0.37H0.25
si0.44N0.56
si0.33N0.35o0.17H
0.15

si0.42N0.37H0.21
si0.27N0.39H0.34
si0.22N0.42H0.36
Sio.2lNo.4lHo.38
Sio.58No.42-H
Sio.4lNo.54-H

Density
(g/cm3)
2.44
2.0
2.6
2.37
2.65 - 3.00*1
2.43 -2.87*2
2.49
2.24
2.08
2.18
2.74 - 3.05
1.65
2.25
2.1

Substrate temp.
(0C)
370 - 400
300
800
300
350
350
300
300
300
300
300 - 600
330 - 350
330 - 350
330 - 350

Deposition rate
(nm/s)
33.3-66.7
12.5

H content
(at.%)
12
25
0
15

21
34
36
38

Ref
[50]
[50]
[50]
[50]
[51]
[51]
[52]
[52]
[52]
[52]
[53]
[54]
[54]
[54]

si0.39N0.36H0.25

* 1 and *2 were measured on the same samples by X-ray reflectometry


and IR chemical bond analysis, respectively.

SILICON CARBIDE

Dl

Crystalline Silicon Carbide

The densities of silicon carbide (c-SiC) were reviewed by Harris [56] and are presented in
TABLE 14 from [56].
TABLE 14 Densities of c-SiC.
Polytype
2H
3C
3C
6H
6H

D2

Density
(g/cm3)
3.214
3.166
3.21427
3.210
3.24878

Temperature
(K)
293
300
300
300
1
300

Amorphous Silicon Carbide

Amorphous silicon carbide (a-SiC) and hydrogenated amorphous silicon carbide (a-SiC:H) have
been prepared by glow-discharge decomposition (PECVD: plasma enhanced chemical vapour

deposition) [57,58] and sputtering [59]. The density values have been published less than those
of other silicon-related amorphous alloys and are presented in TABLE 15. There is a rough
tendency for higher density a-SiC with higher Si contents and Jean shows that the maximum
density was obtained for a-SiC with a Si/C ratio of unity [57].
TABLE 15 Densities of a-SiC deposited by PECVD and sputtering.
Method

Composition

PECVD
PECVD
PECVD
PECVD
PECVD
Sputter
Sputter

Sio.3Co.7-H
Sio.5Co.5-H
Sio.8Co.2-H
Sio.2Co.8-H
Sio.8Co.2-H
Sio.2Co.8*H
Sio.7Co.3-H

Density
(g/cm3)
2.2
2.5
2.4
2.0
2.5
2.2
3.0

AMORPHOUS SiGe ALLOY

El

Crystalline SiGe Alloy

Substrate temp.
(0C)
250
250
250

H content
(at.%)
27
27
27

Ref
[57]
[57]
[57]
[58]
[58]
[59]
[59]

The densities of SiGe alloy have been measured throughout the entire alloy system [60] and are
presented in TABLE 16.
TABLE 16 Densities of crystalline SiGe alloys with various compositions [60].
Content of
Ge (at.%)
Density
(g/cm3)
Content of
Ge (at.%)
Density
(g/cm3)

E2

10

20

30

40

50

2.3277

2.6825

3.0075

3.3265

3.6405

3.9470

60

70

80

90

100

4.2465

4.5335

4.8115

5.0740

5.3256

Amorphous SiGe

Some measurements of the density of a-SiGe have been published [61,62] and are presented in
TABLE 17.
TABLE 17 Density of a-SiGe and C-SiGe prepared by Si and Ge high energy ion-implantation [61,62].
Composition
Si
Sio.85Geo.15
Sio.66Geo.34
Sio.48Geo.52
Sio.24Geo.76

Ge

Density of amorphous SiGe


(g/cm3)
2.289
2.802
3.389
3.947
4.617
5.244

Density of crystalline SiGe


(g/cm3)
2.327
2.861
3.457
4.009
4.694
5.326

Density ratio of
crystalline to amorphous
1.0164 + 0.0010
1.021+0.002
1.020 0.002
1.015 + 0.0010
1.0168 + 0.0017
1.0155 + 0.0019

CONCLUSION

Densities of amorphous silicon-related materials change with preparation conditions. So far no


definite relation between the density and the preparation conditions has been established.
Therefore, on referring to the density of the amorphous materials, it is necessary to study the
full preparation conditions in the original paper.

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8.2

Elastic constants of a-Si and a-Si:H


T.A. Hayes and M.E. Kassner
February 1997

INTRODUCTION

The quantitative description of any phenomenon involving the elastic deformation of a solid is
based on the knowledge of its elastic constants. For an isotropic material, two constants have
to be known for a full description of its response to mechanical deformation. Commonly,
Young's modulus and Poisson's ratio are chosen for this parametrisation and others, such as the
bulk modulus and the shear modulus, may be derived from these. Of the elastic constants,
Young's modulus, the bulk modulus and the shear modulus have all been measured for
amorphous silicon or hydrogenated amorphous silicon. These constants are often calculated
from indirect measurements such as sound velocity or mechanical deformation experiments.
Sound velocity measurements require the knowledge of the density of the film to calculate the
elastic constants. Mechanical deformation experiments on specimens in thin film form require
the knowledge of a second elastic constant, e.g. Poisson's ratio, the value of which is often
assumed to be the average crystalline value. Experimentally determined elastic moduli should
therefore be viewed conservatively with respect to their accuracy.

HYDROGENATED AMORPHOUS SILICON: ELASTIC MODULUS

The measurement of the longitudinal acoustic wave velocity, Vi, yields the elastic constant Cn
through the relation
(i)
[1] where p is the film density. Measurements as a function of hydrogen concentration have
been undertaken by Grimsditch et al [2]. In order to calculate the Young's modulus, E, the
relation
(2)
was utilised [1] assuming a Poisson's ratio, v, of 0.22 (average crystalline silicon property).
The hydrogen concentration was varied by changing the plasma deposition conditions and the
film densities were independently measured. Sound velocities were indirectly measured from
the Brillouin shift. It was observed that Young's modulus systematically decreases with
increasing hydrogen content from 15 x 1011 dyn/cm2 at 15 at.% H to 7 x 1011 dyn/cm2 at 35
at.% H. Crystalline silicon has a directionally averaged Young's modulus of approximately
16.6 x 1011 dyn/cm2 [3]. These data appear in FIGURE 1 below plotted with other Young's
modulus determinations.

Average Crystaline Vau


l e [3]

Elastic Modulus (101' dynes/cm2)

Grimsditch et al. [2]


Jansen et al. [4]
Tanaka [6]
Witvrouw et al. (13]
Jiang et ai. [7]
Cox-Smith et al. f 12]

Atomic % H

FIGURE 1 Elastic (Young's) modulus as a function of hydrogen concentration.

Other data for the Young's modulus of hydrogenated amorphous silicon films can be derived
from experiments where bending is thermally induced in bi-metallic samples. This class of
experiments yields the bi-elastic modulus
(3)
and in order to arrive at Young's modulus, a value for Poisson's ratio v must again be assumed.
With a value of 15 x 1011 dyn/cm2 for the bi-elastic modulus [4] and assuming the average
crystalline value of 0.22 for the Poisson's ratio of the amorphous material, a value of 12 x 1011
dyn/cm2 is calculated for amorphous silicon films with 20 at.% H. This value, as can be
observed in FIGURE 1, is in good agreement with Young's modulus data for a comparable
specimen calculated from sound velocity data [2]. Data from another author [5] yields a higher
Young's modulus of 25 x 1011 dyn/cm2; however the hydrogen concentration of the material
was not reported.
Another determination of the Young's modulus is obtained from the determination of the bulk
modulus B by hydrostatic compression [6]. The consistent bulk modulus was measured to be
approximately 6 x 1011 dyn/cm2 at atmospheric and 50 kbar pressures. Using the relation
(4)
with v = 0.22, a Young's modulus of 10 x 1011 dyn/cm2 is derived for a film with 10 at.% H,
somewhat lower than other determinations for hydrogenated amorphous silicon films [2,4] but
close to those determined by Jiang et al [7].

Jiang and his coworkers [7] examined the effect of changes in hydrogen concentration on the
Young's modulus using nanoindentation to determine the Young's modulus. The Young's
modulus was calculated based on stiffness data obtained from an indentation-loading curve.
Although these data are significantly lower than those reported by Grimsditch et al, they still
illustrated a steady drop in the Young's modulus with increasing hydrogen concentration. The
Young's modulus decreased from 10 x 1011 dyn/cm2 at approximately 2 at.% H to 6 x 1011
dyn/cm2 at approximately 17 at.% H.

HYDROGENATED AMORPHOUS SBLICON: SHEAR MODULUS

In an isotropic solid, the shear modulus, \i, is related to the Young's modulus using EQN (5):
(5)
This relation appears generally to be obeyed for amorphous and hydrogenated amorphous
silicon.
The elastic constant, c44, which for an isotropic material is equivalent to the shear modulus, |a,
has been calculated independently of the Young's modulus from the transverse acoustic wave
velocity Vt through EQN (6) [I]:
(6)
Senn et al [8] reported values for glow discharge deposited films with 15 and 35 at.% hydrogen
to be 4.7 and 2.4 x 1011 dyn/cm2 respectively. This decrease, as might be expected, is in
relative agreement with the decrease in Young's modulus with increasing hydrogen reported
above. An almost identical value of the shear modulus (4.5 x 1011 dyn/cm2) was measured for a
sputtered amorphous film containing nominally no hydrogen. Another author [9] measured a
value of 5.64 x 1011 dyn/cm2 for a glow discharge deposited unhydrogenated amorphous silicon
film which is close to the average crystalline value of 6.4 x 1011 dyn/cm2. Young's moduli
calculated from these values, using EQN (5) and a Poisson's ratio of 0.22, fall in the range of
Young's moduli reported above. Although data are few, these experimental data are in fair
agreement with theoretical determinations [10,11].

UNHYDROGENATED AMORPHOUS SILICON

For amorphous silicon films which nominally contain no hydrogen, the Young's modulus has
been determined by sound velocity measurements [12], thermally induced bending of identical
films deposited on two different substrates [13], and by bending tests on whiskers [14]. The
sound velocity in films prepared by evaporation [12] yielded a value of approximately 9 x 1011
dyn/cm2 for Young's modulus (assuming an amorphous film density equal to the crystalline
density). Thermally induced bending experiments [13] resulted in a value for the bi-elastic
modulus of 14 x 1011 dyn/cm2, or, assuming a Poisson's ratio of 0.22, a Young's modulus of
11 x 1011 dyn/cm2. These values are in the range of values reported for hydrogenated
amorphous silicon with low hydrogen concentrations and are in good agreement with
theoretical determinations of the Young's modulus by Feldman et al [10] who used structural

and interatomic potential models to calculate a Young's modulus for amorphous silicon of 10.5
to 13.1 x 1011 dyn/cm2. Results from other measurements have yielded somewhat lower values.
As an example, the direct measurement of Young's modulus from the bending of amorphous
silicon whiskers has yielded an average value of (6 3) x 1011 dyn/cm2.

CONCLUSION

It is apparent from the large variation in reported data that the elastic modulus and shear
modulus for amorphous and hydrogenated amorphous silicon are still somewhat unclear.
Although it is consistently reported that the elastic constants decrease with increasing hydrogen,
the numerical values associated with these reports should be viewed with caution. It would be
desirable to complement the existing database with further measurements, specifically aimed at
the understanding of the effects of the amorphous nature of the films and the role that hydrogen
plays in the elastic properties of the film. These measurements should preferably be direct
determinations of the elastic film properties, using micromechanical techniques [15] or
nanotensilometry.

ACKNOWLEDGEMENT The authors would like to acknowledge Dr. Frank Jansen for making his files on
amorphous silicon available and for developing the groundwork and structure of the current Datareview as it is
based on the Datareview that he authored in 1988.

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