臺灣博碩士論文加值系統

本論文研究氧化銦錫對具氧化鉬電洞選擇性接觸層及鋁背表面電場之單晶矽太陽能電池光電特性研究，藉由導入透明導電材料氧化銦錫作為串接太陽能電池之介面電極，首先將氧化銦錫以濺鍍的方式沉積在具鋁背表面電場之太陽能電池之正面，其改變參數為濺鍍功率、時間及濺鍍工作壓力，接著透過霍爾效應分析儀、紫外光/可見光/近紅外光分光光譜儀、熱電子型場發射掃描式電子顯微鏡及紫外光光電子光譜儀探討氧化銦錫的薄膜特性，進一步，亦將氧化銦錫以濺鍍的方式沉積在具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池之正面，探討其對元件的光電特性之影響。
實驗結果顯示，在濺鍍功率固定時，光電轉換效率隨著濺鍍時間增加而下降，當濺鍍功率從50 W變動至60 W時，以55 W濺鍍功率其光電轉換效率衰減較小，接著在55 W的濺鍍功率下，探討濺鍍工作壓力的影響，實驗結果顯示，當工作壓力在 7 mTorr時，其光電轉換效率衰減最小，只有-2.44%。經由分光光譜儀檢測，ITO薄膜穿透率其結果為最高可達95%，且透過霍爾效應分析儀可以得知當濺鍍功率為55 W搭配30分鐘條件下，且工作壓力為7 mTorr時其移動率最高為88.2 cm2/Vs，電阻率為0.777 mΩ·cm，光電轉換效率衰減最小，經由熱場發射掃描式電子顯微鏡可得知氧化銦錫薄膜厚度變化為25-100 nm，從紫外光光電子光譜儀量測結果得知氧化銦錫功函數為3.99 eV。接續實驗為濺鍍氧化銦錫在具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池之正面，其實驗結果顯示，其特性變化趨勢與具Al背電極之網印式太陽能電池相同，綜合上述實驗可得知，當具氧化鉬電洞選擇性接觸層之單晶矽太陽能電池的表面濺鍍71 nm的氧化銦錫時，其開路電壓為639 mV、短路電流為39.35 mA/cm2、串聯電阻為1.65Ω·cm、填充因子為81.43%與光電轉換效率可達20.50%。

In this thesis, the effects of indium tin oxide (ITO) on photovoltaic characteristics of monocrystalline silicon solar cells (MSSCs) with molybdenum oxides as hole-selective contact layers (HSCLs) and Al back surface field (Al-BSF) were investigated. The ITO films as interfacial layers of the tandem solar cells were presented. Firstly, the ITO films were deposited on the front surfaces of the MSSCs with Al-BSF. The parameters, including sputtering power, time and working pressure, were investigated. Next, the material properties of the ITO thin films were analyzed by the Hall-effect analyzer, UV/VIS-IR spectroscopy, thermal field-emission scanning electron microscope (FE-SEM), and ultraviolet photoelectron spectroscopy (UPS). Furthermore, the ITO films were sputtered on the front surfaces of the MSSCs with molybdenum oxide HSCLs. The parameters, including sputtering power, time and working pressure, were investigated.
The experimental results show that photovoltaic conversion efficiency (PCE) decreases with increasing the sputtering time when fixed sputter power . The PCE is less degradation at 55 W sputtering power, when the sputtering power changes from 50 W to 60 W, Next, the effects of sputtering working pressure at sputtering power of 55 W were achieved. The experimental results show that when the working pressure is 7 mTorr, its PEC has the smallest degradation, which is only -2.44%. The transmittance of the ITO films is as high as 95% by UV/VIS-IR spectrometer. The ITO films with a mobility of 88.2 cm2/Vs and a resistivity of 0.777 mΩ·cm, as well as smallest PCE degradation were demonstrated by the sputter at 55 W power, 30 mins and 7 mTorr. The thicknesses of the ITO films varies from 25 to 100 nm were demonstrated by FE-SEM. The work function of the ITO is 3.99 eV by UPS. Furthermore, the ITO films were deposited on the surface of the MSSCs with molybdenum oxide as HSCLs. The results were same as the MSSCs with Al-BSF. According to optimum conditions, the MSSCs with molybdenum oxides as HSCLs, the open-circuit voltage of 639 mV, short-circuit current density of 39.35 mA/cm2, series resistance of 1.65 Ω-cm2, fill factor of 81.43 % and the PCE of 20.50 % were achieved at ITO thickness of 71 nm.

摘要......i
Abstract......ii
誌謝......iii
目錄......iv
表目錄......vii
圖目錄......viii
第一章 緒論......1
1.1背面射極鈍化應用於矽基太陽能電池之文獻回顧......1
1.2 電洞選擇性材料氧化鉬應用於太陽能電池之之文獻回顧......1
1.3氧化銦錫材料應用於光電元件之文獻回顧......3
1.4研究動機......4
1.5論文架構......5
第二章 實驗流程與特性測量......6
2.1 實驗前段製程......6
2.1.1 透過標準清洗法(Radio Corporation of America：RCA)清洗矽晶片將表面的微粒子以及自然氧化層(Native Oxide)......6
2.1.2藉由去離子水(DIW)、異丙醇(IPA)及氫氧化鉀(KOH)的鹼性混合液對矽晶片進行糙化(Textured)......7
2.1.3使用高溫爐管對矽晶片進行磷(Phosphorus)擴散(Diffusion)形成n+射極層......7
2.1.4使用快速熱退火(RTA)進行退火，藉著加熱來細化晶粒，釋放應力......8
2.1.5利用酸性混合液清洗矽晶片去除擴散時產生的磷玻璃(PSG)以及邊緣隔絕(Edge Isolation)......8
2.1.6透過電漿增強型化學氣相沉積法(Plasma Enhanced Chemical Vapor Deposition：PECVD)沉積氮化矽(SixNy)在n+射極層上作為抗反射層(ARC)......8
2.1.7藉由網印機將銀膠網印(Screen printing)至ARC上並烤乾......8
2.2 ITO對具鋁背表面電場之太陽能電池光電特性之影響......9
2.2.1藉由網印機將鋁膠網印(Screen printing)到矽晶片的背表面並將其烤乾......9
2.2.2通過燒結爐進行燒結(Fired)使銀膠刺穿氮化矽(SixNy)與射極接觸......9
2.2.3使用雷射切割機將矽晶片裁切成20×20 mm2......9
2.2.4太陽能電池電流-電壓特性量測(I-V measurement)......10
2.2.5正面濺鍍氧化銦錫......10
2.2.6 ITO濺鍍功率及時間對具鋁背表面電場之太陽能電池光電特性之影響......10
2.2.7 ITO濺鍍工作壓力對具鋁背表面電場之太陽能電池光電特性之影響......10
2.2.8 ITO濺鍍溫度對具鋁背表面電場之太陽能電池光電特性之影響......10
2.3 ITO薄膜特性分析......11
2.3.1紫外光∕可見光∕近紅外光分光光譜儀(UV/Visible/IR Spectrophotometer：UV/VIS/IR)......11
2.3.2熱電子型場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope：FE-SEM)......11
2.3.3霍爾效應分析儀 (Hall Effect Analyzer)......11
2.3.4外部量子效率(External Quantum Efficiency：EQE)......12
2.3.5紫外光光電子光譜儀(UV Photoelectorn Spectroscopy：UPS)......12
2.4 ITO對具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池光電特性影響......12
2.4.1通過燒結爐進行燒結(Fired)使銀膠刺穿氮化矽(SixNy)與射極接觸 12
2.4.2使用雷射切割機將矽晶片裁切成20×20 mm2......12
2.4.3在正面旋塗兩層抗蝕刻阻擋層(Polymer)並烤乾......13
2.4.4浸泡氫氟酸(DHF)混合液蝕刻背表面的自然氧化層......13
2.4.5背面熱蒸鍍氧化鉬顆粒......13
2.4.6背面熱蒸鍍銀金屬顆粒......13
2.4.7太陽能電池電流-電壓特性量測(I-V measurement)......14
2.4.8正面濺鍍氧化銦錫......14
2.4.9 ITO濺鍍功率及時間對具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池光電特性之影響......14
2.4.10 ITO濺鍍工作壓力對具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池光電特性之影響......14
2.4.11 ITO濺鍍溫度對具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池光電特性之影響......15
第三章 射頻濺鍍氧化銦錫對單晶矽太陽能電池之光電特性研究......35
3.1 ITO對具鋁背表面電場之太陽能電池光電特性之影響......35
3.1.1 固定濺鍍工作壓力，改變濺鍍功率及時間對具鋁背表面電場之太陽能電池光電特性之影響......35
3.1.2結論......36
3.1.3固定濺鍍功率及時間，改變濺鍍工作壓力對具鋁背表面電場之太陽能電池光電特性之影響......37
3.1.4結論......37
3.1.5固定濺鍍功率、時間和工作壓力，改變濺鍍溫度對具鋁背表面電場之太陽能電池光電特性之影響......37
3.1.6結論......38
3.2 ITO薄膜特性分析......38
3.2.1 ITO薄膜的電阻率、移動率、厚度、穿透率、能隙及功函數......38
3.2.2結論......39
3.3 ITO對具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池光電特性影響......39
3.3.1固定濺鍍工作壓力，改變濺鍍功率及時間對具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池光電特性之影響......39
3.3.2結論......40
3.3.3固定濺鍍功率及時間，改變濺鍍工作壓力對具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池光電特性之影響......40
3.3.4結論......41
3.3.5固定濺鍍功率、時間和工作壓力，改變濺鍍溫度對具蒸鍍氧化鉬電洞選擇性接觸層之太陽能電池光電特性之影響......41
3.3.6結論......41
第四章 總結論與未來展望......69
4.1總結論......69
4.2未來展望......69
參考文獻......70
Extended Abstract......74
Abstract......74
Introduction......75
Experimental......76
Results and Discussion......76
Conclusions......77
Results and Discussion......77

[1] C. Schmiga, M. Rauer, M. Rüdiger, K. Meyer, J. Lossen, H. J. Krokoszinski, M. Hermle, S. W. Glunz, “Aluminum Doped P+ Silicon for Back Emitter and Backside Field:
Results and Potential of Industrial N-Type and P-Type Solar Cells,” In Proceedings of the 25th European PV Solar Energy Conference and Exhibition, 2010, pp. 1163-1168.
[2] S. Gatza, K. Bothe, J. Müller, T. Dullweber, R. Brendel, “Analysis of Local Al-Doped Back Surface Fields for High Efficiency Screen-Printed Solar Cells,” Energy Procedia, vol. 8, 2011, pp. 318-323.
[3] A. Blakers, “Development of the PERC Solar Cell,” IEEE Journal of Photovoltaics, vol. 9, No. 3, 2019, pp. 629-635.
[4] M. Kim, D. Kim, D. Kim, Y. Kang, “Analysis of Laser-Induced Damage During Laser Ablation Process Using Picosecond Pulse Width Laser to Fabricate Highly Efficient PERC Cells,” Solar Energy, vol. 108, 2014, pp. 101-106.
[5] Y. Hwang, C. Park, J. Kim, J. Kim, J. Y. Lim, H. Choi, J. Jo, E. Lee, “Effect of Laser Damage Etching on I-PERC Solar Cells,” Renewable Energy, vol. 79, 2015, pp. 131-134.
[6] M. Kim, S. Park, D. K, “Highly Efficient PERC Cells Fabricated Using the Low Cost Laser Ablation Process,” Solar Energy Materials & Solar Cells, vol. 117, 2013, pp. 126-131.
[7] J. Schmidt, Y. A. Merkle, R. Brendel, B. Hoex, M. C. M. Sanden, W. M .M. Kessels, “Surface Passivation of High-Efficiency Silicon Solar Cells by Atomic-Layer-Deposited Al2O3,” Progress in Photovoltaics, vol. 16, 2008, pp. 461-466.
[8] P. S. Cast, J. Benick, D. Kania, L. Weiss, M. Hofmann, J. Rentsch, R. Preu, S. W. Glunz, “High-Efficiency C-Si Solar Cells Passivated with ALD and PECVD Aluminum Oxide,” IEEE Electronic Device Letters, vol. 31,No. 7, 2010, pp. 695-697.
[9] S. Mack, A. Wolf, C. Brosinsky, S. Schmeisser, A. Kimmerle, P. S. Cast, M. Hofmann, D. Biro, “Silicon Surface Passivation by Thin Thermal Oxide/PECVD Layer Stack Systems,” IEEE Journal of Photovoltaic, vol. 1, No. 2, 2011, pp. 135-145.
[10] M. Hofmann, C. Schmidt, N. Kohn, J. Rentsch, S. W. Glunz, R. Preu, “Stack System of PECVD Amorphous Silicon and PECVD Silicon Oxide for Silicon Solar Cell Rear Side Passivation,” Progress in Photovoltaics, vol. 16, 2008, pp. 509-518.
[11] C. Yu, S. Xu, J. Yao, S. Han, “Recent Advances in and New Perspectives on Crystalline Silicon Solar Cells with Carrier-Selective Passivation Contacts,” Crystals, vol. 8, No. 430, 2018, pp. 1-18.
[12] L. G. Gerling, C. Voz, R. Alcubilla, J. Puigdollers, “Origin of Passivation in Hole-Selective Transition Metal Oxides for Crystalline Silicon Heterojunction Solar Cells,” Journal of Materials Research, vol. 32, 2017, pp. 260-268.
[13] L. Fang, S. J. Baik, K. S. Lim, “Transition Metal Oxide Window Layer in Thin Film Amorphous Silicon Solar Cells,” Thin Solid Films, vol. 556, 2014, pp. 515-519.
[14] M. T. Greiner, L. Chai, M. G. Helander, W. M. Tang, Z. H. Lu, “Transition Metal Oxide Work Functions: The Influence of Cation Oxidation State and Oxygen Vacancies,” Advanced Functional Materials, vol. 22, No. 7, 2012, pp. 4557-4568.
[15] J. Griffin, D. C. Watters, H. Yi, A. Iraqi, D. Lidzey, A. R. Buckley, “The Influence of MoOx Anode Stoicheometry on the Performance of Bulk Heterojunction Polymer Solar Cells,” Advanced Energy Materials, vol. 3, 2013, pp. 1-6.
[16] J. Sun, Q. Zheng, S. Cheng, H. Zhou, Y. Lai, J. Yu, “Comparing Molybdenum Oxide Thin Films Prepared by Magnetron Sputtering and Thermal Evaporation Applied in Organic Solar Cells,” Mater Electron, vol. 27, 2016, pp. 3245-3249.
[17] R. Sagar, A. Rao, “Increasing the Silicon Solar Cell Efficiency with Transition Metal Oxide Nano-Thin Films as Anti-Reflection Coatings,” Materials Research Express, vol. 7, 2020, p. 016433.
[18] Y. Yin, X. Pan, M. R. Andersson, D. A. Lewis, G. G. Andersson, “Mechanism of Organic Solar Cell Performance Degradation upon Thermal Annealing of MoOx,” ACS Appl. Energy Mater, vol. 3, 2020, pp. 366-376.
[19] S. Chambon, L. Derue, M. Lahaye, B. Pavageau, L. Hirsch, G. Wantz, “MoO3 Thickness, Thermal Annealing and Solvent Annealing Effects on Inverted and Direct Polymer Photovoltaic Solar Cells,” Materials, vol. 5, 2012, pp. 2521-2536.
[20] K. Mallem, S. Kim, S. Chowdary, S. Kim, J. Park, J. Kim, S. Dutta, M. Ju, Y. Kim, Y. H. Cho, E. C. Cho, J. Yi, “Influence of Molybdenum Oxide Thickness, Electronic Structure, and Work Function on the Performance of Hole Selective Silicon Heterojunction Solar Cells,” IEEE, 2019.
[21] S. Cao, J. Li, Y. Lin, T. Pan, G. Du, J. Zhang, L. Yang, X. Chen, L. Lu, N. Min, M. Yin, D. Li, “Interfacial Behavior and Stability Analysis of P-Type Crystalline Silicon Solar Cells Based on Hole-Selective MoOx/Metal Contacts,” RRL Solar, vol. 3, 2019, p. 1900274.
[22] L. Cattin, Y. Lare, M. Makha, M. Fleury, F. Chandezon, T. Abachi, M. Morsli, K. Napo, M. ddou, J. C. Bernède, “Effect of the Agdeposition Rate on the Properties of Conductive Transparent MoO3/Ag/MoO3 Multilayers,” Solar Energy Materials & Solar Cells, vol. 117, 2017, pp. 103-109.
[23] D. Yang, X. Zhang, Y. Hou, K. Wang, T. Ye, J. Yoon, C. Wu, M. Sanghadasa, S. Liu, S. Priya, “28.3%-Efficiency Perovskite/Silicon Tandem Solar Cell by Optimal Transparent Electrode for High Efficient Semitransparent Top Cell,” Nano Energy, vol. 84, 2021, p. 105934.
[24] E. Lamanna, F. Matteocci, E. Calabro, L. Serenelli, E. Salza, L. Martini, F. Menchini, M. Izzi, A. Agresti, S. Pescetelli, S. Bellani, A. E. D. R. Castillo, F. Bonaccorso, M. Tucci, A. D. Carlo, “Mechanically Stacked, Two-Terminal Graphene-Based Perovskite/Silicon Tandem Solar Cell with Efficiency over 26%,” Joule, vol. 4, 2020, pp. 865-881.
[25] Z. Qiua, Z. Xua, N. Lia, N. Zhoua, Y. Chena, X. Wanb, J. Liub, N. Lib, X. Haoe, P. Bie, Q. Chend, B. Caoc, H. Zhoua, “Monolithic Perovskite/Si Tandem Solar Cells Exceeding 22% Efficiency Via Optimizing Top Cell Absorber,” Nano Energy, vol. 53, 2018, pp. 798-807.
[26] Y. Wu, D. Yan, J. Peng, T. Duong, Y. Wan, S. P. Phang, H. Shen, N. Wu, C. Barugkin, X. Fu, S. Surve, D. Grant, D. Walter, T. P. White, K. R, Catchpole, K. J. Weber, “Monolithic Perovskite/Silicon-Homojunction Tandem Solar Cell with Over 22% Efficiency,” Energy & Environmental Science, vol. 10, 2017, pp. 2472-2479.
[27] C. U. Kima, J. C. Yua, E. D. Junga, I. Y. Choia, W. Parka, H. Leea, I. Kimb, D. K. Leec, K. K. Hongd, M. H. Songa, K. J. Choia, “Optimization of Device Design for Low Cost and High Efficiency Planar Monolithic Perovskite/Silicon Tandem Solar Cells,” Nano Energy, vol. 60, 2019, pp. 213-221.
[28] J. Kwon, M. J. Im, C. U. Kim, S. H. Won, S. B. Kang, S. H. Kang, I. T. Choi, H. K. Kim, I. H. Kim, J. H. Park, K. J. Choi, “Two-Terminal DSSC/Silicon Tandem Solar Cells Exceeding 18% Efficiency,” Energy & Environmental Science, vol. 9, 2016, pp. 3657-3665.
[29] A. A. Ashouri, E. Köhnen, B. Li, A. Magomedov, H. Hempel, P. Caprioglio, J. A. Márquez, A. B. M. Vilches, E. Kasparavicius, J. A. Smith, N. Phung, D. Menzel, M. Grischek, L. Kegelmann, D. Skroblin, C. Gollwitzer, T. Malinauskas, M. Jošt, G. Matic, B. Rech, R. Schlatmann, M. Topic, L. Korte, A. Abate, B. Stannowski, D. Neher, M. Stolterfoht, T. Unold, V. Getautis, S. Albrecht, “Monolithic Perovskite/Silicon Tandem Solar Cell with >29% Efficiency by Enhanced Hole Extraction,” Science, vol. 370, 2020, pp. 1300-1309.
[30] H. Kanda, N. Shibayama, A. Uzum, T. Umeyama, H. Imahori, Y. H. Chiang, P. Chen, M. K. Nazeeruddin, S. Ito, “Facile Fabrication Method of Small-Sized Crystal Silicon Solar Cells for Ubiquitous Applications and Tandem Device with Perovskite Solar Cells,” Materials Today Energy, vol. 7, 2018, pp. 190-198.
[31] S. I. Kim, T. D. Jung, P. K. Song, “Enhanced Characterization of ITO Films Deposited on PET by RF Superimposed DC Magnetron Sputtering,” Thin Solid Films, vol. 518, 2010, pp. 3085-3088.
[32] K. Utsumiu, O. Matsunaga, T. Takahata, “Low Resistivity ITO Film Prepared Using the Ultra High Density ITO Target,” Thin Solid Films, vol. 334, 1998, pp. 30-34.
[33] J. Txintxurreta, E. G. Berasategui, R. Ortiz, O. Hernández, L. Mendizábal, J. Barriga, “Indium Tin Oxide Thin Film Deposition by Magnetron Sputtering at Room Temperature for the Manufacturing of Efficient Transparent Heaters,” Coatings, vol. 11, 2021, p. 11010092.
[34] H. Ma, J. S. Cho, C. H. Park, “A Study of Indiumtin Oxide Thin Filmdeposited at Low Temperature Using Facing Target Sputtering System,” Surface and Coatings Technology, vol. 153, 2002, pp. 131-137.
[35] T. J. Vink, W. Walrave, J. L. C. Daams, P. C. Baarslag, J. E. A. M. Meerakker, “On the Homogeneity of Sputter-Deposited ITO Films Part I. Stress and Microstructure,” Thin Solid Films, vol. 266, 1995, pp. 145-151.
[36] H. Kanda, A. Uzum, H. Nishino, T. Umeyama, H. Imahori, Y. Ishikawa, Y. Uraoka, S. Ito, “Interface Optoelectronics Engineering for Mechanically Stacked Tandem Solar Cells Based on Perovskite and Silicon,” ACS Applied Materials & Interfaces, vol. 8, 2016, pp. 33553-33561.
[37] J. Lee, H. Jung, J. Lee, D. Lim, K. Yang, J. Yi, W. C. Song, “Growth and Characterization of Indium Tin Oxide Thin Films Deposited on PET Substrates,” Thin Solid Films, vol. 516, 2008, pp. 1634-1639.
[38] S. Zhu, X. Yao, Q. Ren, C. Zheng, S. Li, Y. Tong, B. Shi, S. Guo, L. Fan, H. Ren, C. Wei, B. Li, Y. Ding, Q. Huang, Y. Li, Y. Zhao, X. Zhang, “Transparent Electrode for Monolithic Perovskite/Silicon-Heterojunction Two Terminal Tandem Solar Cells,” Nano Energy, vol. 45, 2018, pp. 280-286.
[39] A. M. Gheidari, F. Behafarid, G. Kavei, M. Kazemzad, “Effect of Sputtering Pressure and Annealing Temperature on the Properties of Indium Tin Oxide Thin Films,” Materials Science and Engineering B, vol. 136, 2007, pp. 37-40.