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Summary
Summary
This first comprehensive description of the most important material properties and device aspects closes the gap between general books on solar cells and journal articles on chalcogenide-based photovoltaics.
Written by two very renowned authors with years of practical experience in the field, the book covers II-VI and I-III-VI2 materials as well as energy conversion at heterojunctions. It also discusses the latest semiconductor heterojunction models and presents modern analysis concepts. Thin film technology is explained with an emphasis on current and future techniques for mass production, and the book closes with a compendium of failure analysis in photovoltaic thin film modules.
With its overview of the semiconductor physics and technology needed, this practical book is ideal for students, researchers, and manufacturers, as well as for the growing number of engineers and researchers working in companies and institutes on chalcogenide photovoltaics.
Author Notes
Roland Scheer received his diploma degree in electronic engineering from the University of Applied Sciences Berlin, Germany. He joined AEG Konstanz, Germany, in 1983 as electronic engineer. In parallel, he studied physics at the University of Konstanz and at the Technical University of Berlin where he received his physics diploma in 1990. In 1994, he finished his doctoral thesis in physics and joined the Helmholtz-Centre (former Hahn-Meitner Institute) in Berlin. His RD activities are focused on thin film solar ceils where he invented a new solar cell based on CulnS2. In 2002, Roland Scheer was visiting scientist at the Advanced institute for Science and Technology (AIST) in Tsukuba, Japan. He was lecturer at the University of Potsdam until in 2010 he became full professor holding the endowed chair for photovoltaics at the Martin-Luther-University in Halle-Wittenberg.
Hans-Werner Schock became head of the Institute of Technology at the Helmholtz Zentrum Berlin fr Materialien und Energie (former Hahn-Meitner Institute) in the division "Solar Energy Research" in late 2004. He received his diploma in electrical engineering in 1974 and obtained his PhD in electrical engineering from Stuttgart University, Germany, in 1986. Starting in the early 70s, he has taken the development of chalcogenide solar cells from basic investigations to the transfer to a pilot fabrication plant. From 1986 to 2003 he coordinated the research on chalcopyrite based solar cells in the framework of the European photovoltaic program. From 1982 to 2004 he was head of the compound semiconductor thin film group of the Institute of Physical Electronics at the University of Stuttgart. He is author or co-author of more than 300 contributions in books, scientific journals and published conference proceedings. For his achievements in the development of chalcopyrite based solar cells he received the prestigious "Becquerel Prize" in 2010.
Table of Contents
Preface | p. XI |
Symbols and Acronyms | p. XIII |
1 Introduction | p. 1 |
1.1 History of Cu(In,Ga)(S,Se) 2 Solar Cells | p. 1 |
1.1.1 Milestones of Cu(In,Ga)(S,Se) 2 Development | p. 3 |
1.2 History of CdTe Solar Cells | p. 5 |
1.2.1 Milestones of CdTe Development | p. 6 |
1.3 Prospects of Chalcogenide Photovoltaics | p. 7 |
2 Thin Film Heterostructures | p. 9 |
2.1 Energies and Potentials | p. 9 |
2.2 Charge Densities and Fluxes | p. 11 |
2.3 Energy Band Diagrams | p. 13 |
2.3.1 Rules and Conventions | p. 13 |
2.3.2 Absorber/Window | p. 17 |
2.3.3 Absorber/Buffer/Window | p. 20 |
2.3.4 Interface States | p. 24 |
2.3.5 Interface Dipoles | p. 29 |
2.3.6 Deep Bulk States | p. 29 |
2.3.7 Bandgap Gradients | p. 32 |
2.4 Diode Currents | p. 36 |
2.4.1 Superposition Principle and Shifting Approximation | p. 36 |
2.4.2 Regions of Recombination | p. 37 |
2.4.3 Radiative Recombination | p. 40 |
2.4.4 Auger Recombination | p. 43 |
2.4.5 Defect Related Recombination | p. 44 |
2.4.5.1 SCR Recombination | p. 50 |
2.4.5.2 QNR Recombination | p. 60 |
2.4.5.3 Back Surface Recombination | p. 62 |
2.4.5.4 Interface Recombination | p. 63 |
2.4.6 Parallel Processes | p. 73 |
2.4.6.1 SCR and QNR Recombination | p. 73 |
2.4.6.2 SCR and IF Recombination | p. 75 |
2.4.7 Barriers for Diode Current | p. 76 |
2.4.8 Bias Dependence | p. 78 |
2.4.9 Non-Homogeneities | p. 79 |
2.5 Light Generated Currents | p. 80 |
2.5.1 Generation Currents | p. 81 |
2.5.2 Generation Function | p. 84 |
2.5.3 Photo Current | p. 86 |
2.5.4 Collection Function | p. 87 |
2.5.4.1 Absorber Quasi Neutral Region | p. 87 |
2.5.4.2 QNR with Graded Bandgap | p. 90 |
2.5.4.3 QNR with Back Surface Field | p. 91 |
2.5.4.4 Absorber Space Charge Region | p. 92 |
2.5.4.5 Buffer Layer | p. 94 |
2.5.4.6 Simulating the Collection Function | p. 95 |
2.5.5 Quantum Efficiency and Charge Collection Efficiency | p. 96 |
2.5.6 Barriers for Photo Current | p. 97 |
2.5.7 Voltage Dependence of Photo Current | p. 99 |
2.5.7.1 Width of SCR | p. 99 |
2.5.7.2 Interface Recombination | p. 100 |
2.5.7.3 Photo Current Barriers | p. 100 |
2.6 Device Analysis and Parameters | p. 101 |
2.6.1 Equivalent Circuits | p. 101 |
2.6.1.1 DC Equivalent Circuit | p. 101 |
2.6.1.2 AC Equivalent Circuit | p. 103 |
2.6.1.3 Module Equivalent Circuit | p. 105 |
2.6.2 Current-Voltage Analysis | p. 107 |
2.6.2.1 External Collection Efficiency | p. 107 |
2.6.2.2 Diode Parameters | p. 108 |
2.6.2.3 Open Circuit Voltage | p. 112 |
2.6.2.4 Fill Factor | p. 116 |
2.6.3 Capacitance-Voltage Analysis | p. 119 |
2.6.4 Admittance Spectroscopy | p. 122 |
3 Design Rules for Heterostructure Solar Cells and Modules | p. 129 |
3.1 Absorber Bandgap | p. 129 |
3.2 Band Alignment | p. 131 |
3.3 Emitter Doping and Doping Ratio | p. 137 |
3.4 Fermi Level Pinning | p. 140 |
3.5 Absorber Doping | p. 142 |
3.6 Absorber Thickness | p. 147 |
3.7 Grain Boundaries | p. 150 |
3.8 Back Contact Barrier | p. 156 |
3.9 Buffer Thickness | p. 159 |
3.10 Front Surface Gradient | p. 162 |
3.11 Back Surface Gradients | p. 165 |
3.12 Monolithic Series Interconnection | p. 171 |
4 Thin Film Material Properties | p. 175 |
4.1 A II -B VI Absorbers | p. 175 |
4.1.1 Physico-Chemical Properties | p. 175 |
4.1.2 Lattice Dynamics | p. 179 |
4.1.3 Electronic Properties | p. 180 |
4.1.3.1 Practical Doping Limits | p. 180 |
4.1.3.2 Defect Spectroscopy | p. 182 |
4.1.3.3 Minority Carrier Lifetime | p. 182 |
4.1.4 Optical Properties | p. 185 |
4.1.4.1 CdTe | p. 185 |
4.1.4.2 Multinary Phases | p. 187 |
4.1.5 Surface Properties | p. 188 |
4.1.6 Properties of Grain Boundaries | p. 189 |
4.2 A I -B III -C 2 VI Absorbers | p. 192 |
4.2.1 Physico-Chemical Properties | p. 193 |
4.2.1.1 Ternary Phase Diagrams | p. 193 |
4.2.1.2 Multinary Phases | p. 198 |
4.2.1.3 Diffusion Coefficients | p. 200 |
4.2.2 Lattice Dynamics | p. 201 |
4.2.3 Electronic Properties | p. 203 |
4.2.3.1 Single Point Defects | p. 204 |
4.2.3.2 Defect Complexes | p. 209 |
4.2.3.3 Defect Spectroscopy | p. 210 |
4.2.3.4 Practical Doping Limits | p. 214 |
4.2.3.5 Carrier Mobility | p. 215 |
4.2.3.6 Minority Carrier lifetime | p. 216 |
4.2.4 Optical Properties | p. 216 |
4.2.4.1 Ternary Semiconductors | p. 217 |
4.2.4.2 Multinary Semiconductors | p. 218 |
4.2.5 Surface Properties | p. 220 |
4.2.5.1 Surface Composition | p. 220 |
4.2.5.2 Surface Electronics | p. 222 |
4.2.6 Properties of Grain Boundaries | p. 224 |
4.3 Buffer Layers | p. 226 |
4.4 Window Layers | p. 226 |
4.4.1 Low Resistance Windows | p. 226 |
4.4.2 High Resistance Windows | p. 230 |
4.5 Interfaces | p. 230 |
5 Thin Film Technology | p. 235 |
5.1 CdTe Cells and Modules | p. 235 |
5.1.1 Substrates | p. 235 |
5.1.2 Window Layers for CdTe Cells | p. 236 |
5.1.3 Buffer Layers for CdTe Cells | p. 237 |
5.1.4 CdTe Absorber Layer | p. 240 |
5.1.5 Activation by Chlorine Treatment | p. 243 |
5.1.6 Influence of Oxygen | p. 245 |
5.1.7 Influence of Copper | p. 246 |
5.1.8 Back Contact | p. 249 |
5.1.8.1 Surface Modification | p. 249 |
5.1.8.2 Primary and Secondary Contacts | p. 250 |
5.1.9 Module Fabrication and Life Cycle Analysis | p. 251 |
5.2 Cu(In,Ga)(S,Se) 2 Cells and Modules | p. 252 |
5.2.1 Substrates | p. 253 |
5.2.2 Back Contacts | p. 253 |
5.2.3 Cu(In,Ga)(S,Se) 2 Absorber Layers | p. 255 |
5.2.3.1 Co-evaporation | p. 257 |
5.2.3.2 Deposition Reaction | p. 260 |
5.2.3.3 Sputtering | p. 262 |
5.2.3.4 Epitaxy, Chemical Vapor Deposition, and Vapor Transport Processes | p. 262 |
5.2.4 Influence of Sodium | p. 262 |
5.2.5 Influence of Gallium | p. 265 |
5.2.6 Influence of Sulfur | p. 265 |
5.2.7 Influence of Oxygen | p. 266 |
5.2.8 Buffer Layers of CIGS | p. 268 |
5.2.8.1 Chemical Bath Deposited CdS | p. 268 |
5.2.8.2 Alternative Buffer Layers | p. 270 |
5.2.9 Window Layers of CIGS | p. 272 |
5.2.10 Module Fabrication | p. 273 |
6 Photovoltaic Properties of Standard Devices | p. 277 |
6.1 CdTe Device Properties | p. 277 |
6.1.1 Solar Cell Parameters | p. 277 |
6.1.2 Diode Currents | p. 277 |
6.1.3 Collection Functions | p. 279 |
6.1.4 Device Anomalies | p. 280 |
6.1.5 Transient Effects and Metastability | p. 281 |
6.1.6 Device Model | p. 282 |
6.1.7 Stability | p. 285 |
6.2 A I -B III -C 2 VI Device Properties | p. 286 |
6.2.1 Solar Cell Parameters | p. 286 |
6.2.2 Diode Currents | p. 288 |
6.2.3 Collection Function | p. 290 |
6.2.4 Transient Effects and Metastability | p. 292 |
6.2.4.1 Relaxed State | p. 292 |
6.2.4.2 Models for Relaxed State | p. 293 |
6.2.4.3 Red light Effect | p. 294 |
6.2.4.4 Forward Bias Effect | p. 295 |
6.2.4.5 Blue Light Effect | p. 295 |
6.2.4.6 White Light Effect | p. 296 |
6.2.4.7 Reverse Bias Effect | p. 296 |
6.2.4.8 Models for Metastability | p. 297 |
6.2.4.9 Implications for Module Testing | p. 298 |
6.2.5 Device Model | p. 299 |
6.2.6 Stability | p. 302 |
7 Appendix A: Frequently Observed Anomalies | p. 305 |
7.1 JV Curves | p. 305 |
7.1.1 Roll Over Effect | p. 305 |
7.1.2 Crossover | p. 306 |
7.1.3 Kink in Light JV Curve | p. 306 |
7.1.4 Violation of Shifting Approximation | p. 307 |
7.2 Solar Cell Parameters | p. 308 |
7.2.1 Reduced J sc but High V oc | p. 308 |
7.2.2 Reduced V oc but High J sc | p. 308 |
7.2.3 High J sc but Low FF | p. 309 |
7.3 Diode Parameters | p. 309 |
7.3.1 Diode Parameter A > 2 | p. 309 |
7.3.2 Activation Energy E a | p. 309 |
7.3.3 Diode Quality Factor Illumination Dependent | p. 310 |
7.3.4 Diode Quality Factor Temperature-Dependent | p. 310 |
7.4 Quantum Efficiency | p. 311 |
7.4.1 High J sc but Low EQE | p. 311 |
7.4.2 Low J sc but High EQE | p. 311 |
7.4.3 Low Blue Response in IQE | p. 311 |
7.4.4 Low Red Response in IQE | p. 312 |
7.4.5 Quantum Efficiency Low at All Wavelengths | p. 312 |
7.4.6 Apparent Quantum Efficiency | p. 313 |
7.5 Transient Effects | p. 313 |
7.5.1 V oc Time-Dependent with dV oc /dt > 0 | p. 313 |
7.5.2 V oc Time-Dependent with dV oc /dt | p. 314 |
8 Appendix B: Tables | p. 315 |
References | p. 321 |
Index | p. 361 |