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Microwave Induced Remote Hydrogen Plasma (Mirhp) Passivation of Multicrystalline Silicon Solar Cells

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Microwave Induced Remote Hydrogen Plasma (Mirhp) Passivation of Multicrystalline Silicon Solar Cells MICROWAVE INDUCED REMOTE HYDROGEN PLASMA (MIRHP) PASSIVATION OF MULTICRYSTALLINE SILICON SOLAR CELLS Dissertation zur Erlangung des akademischen Grades des Doktors der Naturwissenschaften (Dr. rer. nat.) an der Universität Konstanz Fakultät für Physik vorgelegt von Markus Spiegel Konstanz, Oktober 1998 Contents 1 Introduction 1 1.1 The energy problem - need for photovoltaics 1 1.2 The importance of multicrystalline silicon for the PV industry 1 1.3 Organization of this work 3 2 Multicrystalline silicon materials and laboratory cell processing 5 2.1 Introduction 5 2.2 Production of multicrystalline silicon 5 2.2.1 Block cast mc-Si 5 2.2.2 Ribbon cast mc-Si 6 2.3 Structural and electrical properties 6 2.4 Processing of laboratory solar cells 7 2.4.1 Cells with homogeneous emitter 7 2.4.2 Cells with selective emitter 8 2.4.3 Cell processing using RGS and EFG base material 8 3 Characterization of silicon wafers and cells 10 3.1 Introduction 10 3.2 Contactless measurement methods 10 3.2.1 Surface photovoltage method 10 3.2.2 Microwave-detected photoconductance decay technique (MW-PCD) 12 3.3 Measurements on solar cells 13 3.3.1 Dark I-V characteristics - the two-diode model 13 3.3.2 Illuminated I-V characteristics 13 3.3.3 LBIC 14 3.3.4 Spectral response 15 3.3.4.1 Measurement and determination of the internal quantum efficiency (IQE) 15 3.3.4.2 Influence of the bias light on the IQE 16 3.3.4.3 Influence of a high temperature step on the IQE of EFG solar cells 17 3.4 Theory on the internal quantum efficiency (IQE) 17 3.4.1 Introduction 17 3.4.2 Literature work 18 3.4.2.1 Contributions of emitter, space charge region and base to the IQE 18 3.4.2.2 Additional approximations for the base IQE 20 3.4.2.2.1 wb >> Lb 20 3.4.2.2.2 wb << Lb 20 3.4.3 The general problem with the approximated base IQEs 21 3.4.4 Own work 22 3.4.4.1 Approximations on the emitter and space charge region 22 II Contents 3.4.4.2 Direct way of deducing approximated IQEe+scr 23 3.4.4.3 Proof for 1/IQEtotal 1+1/(Lbα) ´near´ the space charge region 24 3.4.4.4 Comparison of the different approximated total IQEs 25 3.4.4.5 Validity region of eq. (3.23) 25 3.4.4.6 Theoretical and experimental accuracy 27 3.4.4.7 Consequences of eq. (3.23) 29 3.4.4.8 Influence of a weak surface texturization 30 4 Microwave induced remote hydrogen plasma (MIRHP) passivation 33 4.1 Introduction 33 4.2 The MIRHP device 34 4.3 Optimization of the MIRHP process 35 4.3.1 Procedure of the optimization 35 4.3.2 Optimization of the microwave power, gas flow and gas pressure 35 4.3.2.1 EMC base material 36 4.3.2.2 SOLAREX base material 37 4.3.3 Optimization of the diffusion temperature and process time 38 4.3.3.1 Cast silicon 38 4.3.3.2 Ribbon silicon 40 4.3.4 LBIC measurements 41 4.3.5 Summary of the optimal process parameters for the investigated materials 42 4.4 MIRHP of RGS solar cells 44 4.4.1 Introduction 44 4.4.2 Flat cells 44 4.4.2.1 Cell processing 44 4.4.2.2 IQE before H-passivation 45 4.4.2.3 Improvement of RGS cell performance due to MIRHP 46 4.4.3 V-grooved cells 47 4.4.3.1 Cell processing 47 4.4.3.2 Homogeneity of the RGS material, benefit from forming gas annealing 47 4.4.3.3 Benefit from the MIRHP applied before the DARC 49 4.4.3.3.1 I-V characteristics 49 4.4.3.3.2 IQE-measurements 50 4.4.3.4 The MIRHP applied after the DARC 51 4.4.4 Results on RGS cells 52 4.5 Results on multicrystalline PERL-cells 52 4.5.1 Introduction 52 4.5.2 Combining the MIRHP passivation with the PERL cell process 53 4.5.3 Influence of MIRHP and thermal annealing on PERL cells 53 4.5.4 Improvement of the IQE by the MIRHP 54 4.5.5 Illuminated I-V results 55 4.5.6 Conclusions 56 4.6 MIRHP of cells with homogeneous emitter 56 4.7 Summary of results 58 5 Diffusion and effusion of hydrogen in silicon 60 5.1 Introduction 60 5.2 Theoretical work on hydrogen diffusion 60 5.2.1 Free diffusion of hydrogen 60 5.2.2 Multiple trapping of hydrogen 61 Contents III 5.2.3 Methods for extracting diffusion parameters from H-depth data 62 5.2.3.1 The topt-method 63 5.2.3.2 The tconst-method 64 5.2.3.3 The Tconst-method 64 5.3 Experimental determination of hydrogen/deuterium in silicon 65 5.3.1 Introduction 65 5.3.2 Thermal effusion (TE) 65 5.3.3 Secondary ion mass spectroscopy (SIMS) 66 5.3.4 Discussion 67 5.4 A new approach to determine the passivation depth of hydrogen in solar cells 67 5.4.1 Introduction 67 5.4.2 Two-layer model of the IQE 68 5.4.2.1 Exact calculation of the base IQE 68 5.4.2.2 Approximations of the base region 71 5.4.2.2.1 Thick second base region 71 5.4.2.2.2 High back side recombination velocity 72 5.4.2.3 The total IQE 73 5.4.2.4 Comparison of the approximated total IQEs 74 5.4.2.5 Theoretical and experimental accuracy 75 5.4.2.6 Summary of this section 76 5.4.3 Experiment 78 5.4.3.1 Fit of the two-layer model to experiment 78 5.4.3.2 Comparison of the two-layer model with PC-1D 79 5.4.3.3 Extraction of diffusion parameters for SOLAREX base material 80 5.4.3.4 Comparison of the diffusion constants of different mc-Si materials 81 5.5 Effusion experiments on solar cells 81 5.5.1 Introduction 81 5.5.2 Influence of H-effusion on the IQE 82 5.5.3 Influence of H-effusion on the illuminated and dark I-V parameters 83 5.6 Conclusions 85 6 The MIRHP process within an industrial cell production line 87 6.1 Introduction 87 6.2 Industrial solar cell production at Eurosolare and Solarex 87 6.3 MIRHP of screen-printed cells. 89 6.3.1 MIRHP after cell processing 89 6.3.2 MIRHP in industrial cell processes 90 6.3.2.1 MIRHP within the production line at Eurosolare 91 6.3.2.2 MIRHP within the production line at Solarex 92 6.3.3 Industrial importance of the MIRHP processes 93 6.4 PECVD SiN 94 6.5 Combination of PECVD SiN and MIRHP 95 6.6 Conclusions 96 7 Summary 97 8 References 99 9 Appendixes 105 9.1 Single-layer IQE 105 9.2 Single-layer IQE at α = 1/Lb 106 IV Contents 9.3 Single-layer IQE and weak surface texturization 107 9.4 Double-layer IQE 110 9.5 Double-layer IQE at α = 1/L1 and α = 1/L2 111 9.6 From the double-layer IQE back to the single-layer IQE 114 9.7 Double-layer IQE and weak surface texturization 115 10 List of abbreviations, symbols, figures and tables 117 10.1 List of abbreviations 117 10.2 List of symbols 118 10.3 List of figures 120 10.4 List of tables 121 11 List of Publications 123 12 Zusammenfassung 126 13 Danksagung 128 1 Introduction 1.1 The energy problem - need for photovoltaics Today, the main contribution to the world-wide used energy comes from fossil and nuclear resources. Because of the limitations of the oil, gas, coal and uranium resources and environmental problems such as the green house effect, acid rain and nuclear by-products most energy scenario studies predict a fundamental change in the world energy supply during the coming century [1, 2]. In these studies it is supposed that renewable energy systems, such as wind energy, photovoltaics, solar heating and biomass will become more important. These energy systems do not depend on resources, which are limited to our earth, but on the constant radiation - at least for the human horizon - of the sun. Among these renewable energies, the photovoltaic conversion of light energy into electricity is very promising. Photovoltaic (PV) systems are reliable, almost maintenance-free and do not cause polluting by-products. Additionally, photovoltaics is modular in the range from milliwatt to megawatt. Because of these advantages photovoltaics is one of the fastest growing markets during the last years as can be seen in the world photovoltaic cell and module shipments from 1980 to 1997 shown in Fig. 1.1. Despite these advantages, the installed world total PV power is still below the power output of one single nuclear power station. The relatively high costs of PV modules in the range of $3.5-4.5/Wp [3] are the reason for the small contribution of PV energy compared to the total electric energy consumption. Fig. 1.1: Total world photovoltaic cell and 120 world photovoltaic cell 120 module shipment. The contribution of thin and module shipments film cells and modules is also shown for 100 100 comparison [4].
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