Barclay 1985 the Electronic Transport Properties of Phd
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The Electronic Transport Properties of Undoped and Doped Arsenic Triselenide A thesis presented by Raymond Patrick Barclay (Sponsoring establishment Dundee College of Technology) to the CNAA in partial fulfilment of the requirements for the degree of Doctor of Philosophy March 1985 DECLARATION I declare that while registered as a candidate for the degree for which this thesis is presented I have not been a candidate for any other award. I further declare that except where stated the work contained in this thesis is original and was performed by the author. The author is grateful to Dr J T Edmond of Dundee University who helped with the preparation of the bulk glass, Dr. A. Long of Glasgow University who helped with the structural and chemical analysis of the arsenic triselenide films, and Mark Munro of Dundee College of Technology who assisted with the preparation of the computer programs. Signed Raymond Patrick Barclay. ADVANCED STUDIES In addition to the original research reported in this thesis the author followed a programme of postgraduate study. This program included attendance at the lectures and tutorials of the joint Scottish M. Sc course in the Physics and Technology of Amorphous Materials held at Dundee University during 1981-82. Also the author attended the Chelsea Meeting on Liquid and Amorphous Semiconductors in 1982, 1983 and 1984, presenting a paper at the 1984 meeting. ACKNOWLEDGMENTS The author is greatly indebted to and wishes to thank the following without whose help this work would not have been possible. Dr. Joseph M. Marshall and Dr. Charles Main for their supervision and encouragement throughout this investigation. Henry Fortuna, Charles Bullock and Anthony Hepburn for many -enlightening and critical discussions during both the theoretical and experimental aspects of this project. Dr. R.R. Gardner for extending to the author the use of the facilities of the Physics Department at Dundee College of Technology. Mr. J. Anderson and the technical staff of the Department of Physics for their help and advice during the course of this study. The Science and Engineering Research council and Dundee College of Technology for providing the financial assistance which made this work possible. THE ELECTRONIC TRANSPORT PROPERTIES OP UNDOPED AND DOPED ARSENIC TRISELENIDE RAYMOND P BARCLAY The electronic and transport properties of doped and undoped arsenic triselenide have been characterised in an extensive study. Measurement of optical absorption, d.c, conductivity, thermoelectric power and fast charge transient photoconductivity were made. In addition, an improved time of flight technique and a modulated steady state photocurrent experiment were developed. Results obtained from undoped, vitreous, evaporated and sputtered samples were explained on the basis of a multiple trapping transport model with trap levels E£ (0.62eV) and Eg (0.42eV) above the valence band edge. Variation of the dispersion parameter with temperature in vitreous material supports the presence of structure at E2 in the distribution of localised states N(E). Deviations from power law behaviour in the transient photodecay also suggest a structured N(E) and a computer simulation of the thermalisation process was developed in order to obtain N(E) from the data. For sputtered material a feature incorporated at Eg in a continuous tail of states gave the the best fit to the data. Determination of N(E) using two other recently developed spectroscopic techniques also gave excellent agreement in the energy position Eg. The spectroscopic analysis offered a new technique for obtaining values of the capture coefficient C and offers the possibility of obtaining the energy dependence of C (if any). In nickel doped specimens the Fermi-level was shifted by as much as 0.6eV, the conductivity increased by 11 orders of magnitude and n-type conduction, rarely seen in chalcogenides, observed. These unique findings were explained by inclusion of an acceptor level (E^ 0.22eV), introduced by nickel, into the intrinsic model density of states. Results obtained when incorporating indium infer a shift in the valence band edge by 0.03 eV rather than a shift of the Fermi-level. A decrease in the trap density at Eg with increasing indium content is also inferred. Table of Contents 1. INTRODUCTION TO AMORPHOUS SEMICONDUCTORS 1 1•1 General Review 1 1.2 Amorphous Solids and Glasses 2 1.3 Electronic Structure of Amorphous Solids 5 1.4 The Breakdown of Conventional Transport Theory 9 1.5 Extended State Conduction 12 1.6 Hopping Conduction 16 1.6.1 Hopping Conduction in Band Tails 16 1.6.2 Hopping Conduction at the Fermi-level 18 1.6.3 Small Polarons 19 1.7 Thermoelectric Power 20 1.7.1 Conduction in Localised States Near the 22 Mobility Edge 1.7.2 Conduction at the Fermi Level 22 1.8 Optical Absorption in Amorphous Semiconductors 23 1.8.1 Absorption Edge 25 2. REVIEW OF PREVIOUS WORK ON ARSENIC TRISELENIDE 31 2.1 The Chalcogenide Glasses 31 2.1.1 The Structure of Arsenic Triselenide 32 2.2 Band Models 34 2.2.1 The Cohen-Fritzsche-Ovshinsky Model 35 2.2.2 The Davis-Mott Model 35 2.3 The Conductivity and Thermopower 36 2.4 Drift Mobility 42 2.5 Transient Photoconductivity Measurements 46 2.6 Defects in Chalcogenides 47 2.7 Photoluminescence and Photo-Induced ESR 51 2.8 Modification of Arsenic Triselenide 56 2.8.1 Mobility Measurements in Doped Arsenic 59 Triselenide 3. PHOTOCONDUCTIVITY AND DISPERSIVE TRANSPORT 59 i 3.1 Photoconductivity 59 3.1.1 Lifetimes 59 3.1.2 Trapping and Recombination 60 3.1.3 Capture Cross Sections 61 3.1.4 Quantum Efficiency 62 3.1.5 Simple Rate Equations 64 3.1.6 Quasi Fermi Levels 65 3.1.7 Demarcation Levels 66 3.1.8 Analysis of Photoconductivity Data 66 3.1.9 Distributed Trapping Centres 69 3.1.10 Exponential Tail Model 71 3.1.11 Photomobility 75 3.1.12 Photocurrent Decay 76 3.2 Anomalously Dispersive Transport 79 3.2.1 The Scher-Montroll Model of Anomalous 81 Dispersion 3.2.2 Trap Limited Band Transport and Anomalous 83 Dispersion 4. COMPUTER SIMULATION STUDY OF AMORPHOUS 94 SEMICONDUCTORS 4.1 Multilevel Analogue Solution 94 4.1.1 R.C. Analogue for an Exponential Tail 95 4.1.2 Discrete Levels 96 4.1.3 Other Distributions of Localised States 98 4.1.4 Methods Used To Solve the Differential 100 Equations 4.2 Computer Simulations:-Results and Discussion 103 5. EXPERIMENTAL TECHNIQUES 111 5.1 Introduction H I 5.2 Preparation of Samples 111 5.2.1 Preparation of the Bulk Glass 111 5.2.2 The Preparation of Vitreous Specimens 113 5.2.3 Evaporated Films 113 5.3 Introduction to the Sputtering Process 114 5.3.1 The Nordiko Sputtering System 115 5.3.2 Thickness Measurements 118 5.4 Deposition of Electrodes and Their Geometry 119 5.5 Electrical Measurements 121 5.5.1 Sample Holder for D.C. Conductivity and 121 Photoconductivity Measurements 5.5.2 d.c. Conductivity 123 5.5.3 The Time of Flight Technique 123 5.5.3.1 Minimization of Space-charge 128 i i 5.6 Transient Photoconductivity 130 5.7 Steady State Photoconductivity Techniques 132 5.7.1 High Power Light Emitting Diodes 132 5.7.2 Modulation of Steady State Photoconductivity 132 5.8 Thermoelectric Power 133 5.9 Optical Absorption 134 6. EXPERIMENTAL RESULTS AND DISCUSSION 136 6.1 Optical Absorption 136 6.2 Dark d.c. Conductivity 137 6.2.1 Analysis Of Conductivity Data 139 6.3 Drift Mobility Data 140 6.3.1 Vitreous Specimens 140 6.3.2 Annealed Evaporated Specimens 141 6.3.3 Sputtered Specimens 142 6.4 Transient Photocurrent 143 6.4.1 Vitreous Specimens 143 6.4.2 Evaporated Specimens 144 6.4.3 Sputtered Specimens 145 6.5 Photomobilities, Decaytimes and Steady State 145 Photoconductivity 6.5.1 Sputtered Specimens 146 6.5.2 Vitreous Specimens 147 7. DISCUSSION OF RESULTS 148 7.1 Optical Absorption 148 7.2 Conductivity and Drift Mobility 148 7.3 Dispersive Transport 152 7.4 Computer Simulations and SpectroscopicAnalysis of 156 The Transient Decay Results 7.5 Steady State Photoconductivity 163 7.5.1 Sputtered Samples 166 7.6 The Origin of the Fast Transit Pulse in Sputtered 167 Material 8. THE EFFECTS OF DOPING ARSENIC TRISELENIDE WITH 169 NICKEL i i i 8.1 d.c Conductivity 170 8.1.1 Thermoelectric Power Results 172 8.2 Optical Absorption 172 8.3 Photoconductivity Results 173 8.4 Discussion and Analysis 174 8.5 Discontinuities in the Conductivity Curves 181 8.6 Photoconductivity Analysis 183 8.6.1 Optical Absorption 186 9. INDIUM DOPED SAMPLE-RESULTS AND DISCUSSION 189 9.1 Photoconductivity results 190 9.2 Transient Photoconductivity-Fast Charge 192 9.3 Discussion and Analysis 192 10. SUMMARY OF DISCUSSION 198 10.1 Undoped Arsenic triselenide 198 10.2 Doped Arsenic Triselenide 200 10.3 Publications 201 REFERENCES 203 ABSTRACT 211 iv Chapter 1 INTRODUCTION TO AMORPHOUS SEMICONDUCTORS 1.1 General Review The study of the physical properties of amorphous semiconductors has become a very active and important field in solid state physics. The pioneering work was begun, by the Leningrad school 1> 2 neariy three decades ago, but only in the last fifteen years or so has the interest been widespread. The interest arose from two sides. The realization in 1968, by Ovshinsky ^ , that films of chalcogenide alloys show fast and reversible switching from a high to a low resistance state was one long reason for the rapid growth of interest. This initiated the discussions about the physical interpretation of switching, fundamental question being whether the switching is either of thermal nature or of electronic nature.