臺灣博碩士論文加值系統

本研究論文探討藉由下轉換材料增強網印式單晶矽太陽能電池之光電特性研究，利用下轉換材料特性使短波長的光子轉換成長波長的光子增加矽基板內的電子電洞對，可進一步提升單晶矽太陽能電池的效率本研究分為兩大主題，首先使用具背鋁膠網印式單晶矽太陽能電池浸泡於下轉換材料(Eu摻雜Y2O3)水溶液，其參數為改變下轉換材料水溶液浸泡方式、下轉換材料重量百分比濃度與浸泡及烤乾的循環次數，接著使用具氧化鉬電洞選擇性接觸層網印式單晶矽太陽能電池搭配蒸鍍下轉換材料於元件的正表面，其參數為改變蒸鍍鍍率、不同遮蓋太陽能電池方式及蒸鍍電流
實驗結果顯示，隨著循環次數增加，其材料膜厚也會增加而導致光電轉換效率下降，因此具背鋁膠網印式單晶矽太陽能電池採用浸泡加烤乾的循環方式且其循環次數為15次，浸泡下轉換材料水溶液重量百分比濃度為3.5 wt%，其光電轉換效率為18.36 %，開路電壓為0.64 mV、短路電流為34.8 mA/cm2、填充因子為82 %與串聯電阻為1.62 Ω-cm接著採用具氧化鉬電洞選擇性接觸層網印式單晶矽太陽能電池元件探討蒸鍍轉換材料效應，實驗結果顯示，下轉換材料蒸鍍鍍率太低其可控性難，蒸鍍電流太高會使得氧化鉬與銀上有水氣而導致效率下降，因此在蒸鍍鍍率為0.6 nm/min、利用金屬盒遮蓋正面銀電極、蒸鍍電流為140安培，最佳光電轉換效率從20.3 %提升至20.6 %，開路電壓為0.65 V、短路電流為38.9 mA/cm2、填充因子為80.9 %、串聯電阻為1.57 Ω-cm2。

In this study, enhanced photovoltaic characteristics of screen-printed monocrystalline silicon solar cells (SMSSCs) were investigated by downconversion materials (DMs). Electron-hole paris of silicon substrate were increased by DMs that can transfer the photons from short wavelength to long wavelength. Thus, the conversion efficiency of SMSSCs can be enhanced. This study was divided into two topics. First, the front side of the SMSSCs with Al back-surface-field were dipped in the Eu-doped Y2O3 solution. The parameters, including various dipping methods, the concentrations of DMs solution, as well as cycling times of dip and dry, were investigated. Next, the DMs powders were thermally evaporated on the front side of the SMSSCs with molybdenum oxide hole-selective contact layers. The parameters, including various evaporate rates, currents, and shading method, were presented
The results show that the conversion efficiency (CE) decreases with increasing the thickness of DMs films due to the increase of the cycling times. Furthermore, a CE of 18.36%, an open-circuit voltage of 0.64 mV, a short-circuit current density of 34.8 mA/cm2, a fill factor of 82 %, and a series resistance of 1.62 Ω-cm were achieved at the number of fifteenth times of dip and dry as well as the concentration of 3.5 wt% for SMSSCs with Al back-surface-field. Next, the effects of evaporated DMs on the SMSSCs with molybdenum oxide hole-selective contact layers were demonstrated. The results suggested that the lower evaporate rate is difficultly to control. The CE degradation was presented by H2O ambient of the surface of the MoO2/Ag film due to large evaporated current. The CE of 20.6 %, an open-circuit voltage of 0.65 mV, a short-circuit current density of 38.9 mA/cm2, a fill factor of 80.9 %, and a series resistance of 1.57 Ω-cm were demonstrated at 0.6 nm/min of evaporate rate, metal shading box, and evaporate current of 140 A for SMSSCs with molybdenum oxide hole-selective contact layers.

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射極鈍化背接觸應用於太陽能電池之文獻回顧.....1
1-2過渡載子選擇性材料應用於太陽能電池之文獻回顧..... 1
1-3轉換材料應用於太陽能電池之文獻回顧 2
1-4研究動機..... 4
1.5論文架構.....4
2-1浸泡下轉換材料水溶液之前段實驗流程..... 5
2-1-1 清洗矽晶圓及去除自然氧化層（ Native oxide）..... 5
2-1-2 利用鹼式蝕刻液對矽晶片進行糙化（ Texture）..... 6
2-1-3藉由高溫爐管對矽基板進行磷擴散形成 n+射極層..... 6
2-1-4利用混合酸去除擴散完所形成的磷玻璃（ PSG）以及邊緣去除 Edge isolation）和背表面拋光（Polished）..... 6
2-1-5藉由電漿化學沉積系統（ Plasma Enhance Chemical Vapor Deposition
PECVD）沉積氮化矽 SiNx）於 n+射極層上 ......7
2-1-6利用網印機將鋁電極網印（ Screen-printing）至背表面並烤乾..... 7
2-1-7利用網印機將銀電極網印（ Screen-printing）至正表面並烤乾..... 7
2-1-8藉由燒結爐將銀電極刺穿氮化矽（ SiNx）並且於背面形成鋁背電場..... 7
2-1-9使用雷射切割機將試片切割成面積為 2 x 2 cm2 .....8
2-2改變下轉換材料浸泡方式及次數 .....8
2-2-1旋塗抗蝕刻阻擋層（ Polymer）於背表面 8
2-2-2以不同的方式及次數浸泡去離水及下轉換材料水溶液中..... 8
2-3改變下轉換材料重量百分比濃度及循環次數..... 9
2-4蒸鍍下轉換材料於正表面之前段實驗流程..... 9
2-4-1 清洗矽晶圓及去除自然氧化層（ Native oxide）..... 9
2-4-2 鹼式蝕刻液對矽晶片進行糙化（ Texture） .....10
2-4-3藉由高溫爐管對矽基板進行磷擴散形成 n+射極層..... 10
2-4-4利用混合酸去除擴散完所形成的磷玻璃（ PSG）以及邊緣去除 Edge isolation）和背表
面拋光 Polished..... 10
2-4-5藉由電漿化學沉積系統（ Plasma Enhance Chemical Vapor Deposition
PECVD）沉積氮化矽 SiNx）於 n+射極層上..... 11
2-4-6利用網印機將銀極網印（利用網印機將銀極網印（Screen-printing）至正表面並烤乾）
至正表面並烤乾 ...................................... 11
2-4-7藉由燒結爐將銀電極刺穿氮化矽（藉由燒結爐將銀電極刺穿氮化矽（SiNx）） ...... 11
2-4-8使用雷射切割機將試片切割成面積為使用雷射切割機將試片切割成面積為2 x 2 cm2 . 11
2-4-9旋塗兩層抗蝕刻阻擋層（旋塗兩層抗蝕刻阻擋層（Polymer）於正表面）於正表面 .. 12
2-4-10藉由氫氟酸（藉由氫氟酸（HF）將矽基板的自然氧化層（）將矽基板的自然氧化層
（Native oxide）去除）去除 ................ 12
2-5改變下轉換材料蒸鍍鍍率改變下轉換材料蒸鍍鍍率 ..... 12
2-5-1蒸鍍二氧化鉬（蒸鍍二氧化鉬（MoO2）於矽基板背面作為電洞傳輸層）於矽基板背面作為
電洞傳輸層 ..... 12
2-5-2蒸鍍銀（蒸鍍銀（AgAg）於二氧化鉬（）於二氧化鉬（MoOMoO22）上作為背表面電極）上
作為背表面電極 ............. 13
2-5-3將矽晶片黏貼至整面及正面銀電極（將矽晶片黏貼至整面及正面銀電極（BusbarBusbar）
上............. 13
2-5-4蒸鍍不同鍍率之下轉換材料於矽基板正表面蒸鍍不同鍍率之下轉換材料於矽基板正表面
........... 13
2-6改變太陽能改變太陽能電池遮蓋方式電池遮蓋方式 ............... 14
2-7改變下轉換材料蒸鍍電流及厚度改變下轉換材料蒸鍍電流及厚度 ........... 14
2-8光伏元件電性及物性量測光伏元件電性及物性量測 ..................... 14
2-8-1電流電流-電壓（電壓（I-V measurement）量測系統）量測系統 ........ 14
2-8-2外部量子效率（外部量子效率（External Quantum Efficiency；；EQE）系統量測）系
統量測 .......................... 14
2-8-3熱場發射電子顯微鏡（熱場發射電子顯微鏡（Thermal Field Emission Scanning
Electron Microscope；；TF-SEM）進行表面分析）進行表面分析 .... 15
第三章 藉由下轉換材料增強網印式單晶矽太陽能電池之光電特性研究藉由下轉換材料增強網印
式單晶矽太陽能電池之光電特性研究 ............................... 36
3-1探討下轉換材料水溶液對具背鋁膠網印式單晶矽太陽能電池光電特性之影響探討下轉換材料
水溶液對具背鋁膠網印式單晶矽太陽能電池光電特性之影響 ......... 36
3-1-1改變去離子水（改變去離子水（DIW）及下轉換材料（）及下轉換材料（Eu-doping
Y2O3）水溶液浸泡方）水溶液浸泡方式及次數之電流式及次數之電流-電壓（電壓（I-V
Measurement）及外部量子效率（）及外部量子效率（EQE）之）之量測結果分析量測結果
分析 ..... 36
3-1-2結論 ..... 37
3-1-3改變下轉換材料改變下轉換材料（（Eu-doping Y2O3））水溶液重量百分比濃度及循環次
數水溶液重量百分比濃度及循環次數電流電流-電壓電壓（（I-V Measurement））、外部
量子效率、外部量子效率（（EQE））及及熱場發射電子熱場發射電子顯微鏡（顯微鏡
（TF-SEM）之量測結果分析）之量測結果分析 ......... 38
3-1-4結論 ......................................................... 39
3-2探討蒸鍍下轉換材料粉末對具氧化鉬選擇性接觸層網印式單晶矽太陽能電池探討蒸鍍下轉換
材料粉末對具氧化鉬選擇性接觸層網印式單晶矽太陽能電池光電特性之影響光電特性之影響.
....40
3-2-1改變下轉換材料（改變下轉換材料（Eu-doping Y2O3）蒸鍍鍍率之電流）蒸鍍鍍率之電
流-電壓（電壓（I-V Measurement）、外部量子效率（）、外部量子效率（EQE）及熱場
發射電子顯微鏡（）及熱場發射電子顯微鏡（TF-SEM）之量測結果分析）之量測結果分析
..... 40
3-2-2結論 .... 41
3-2-3改變太陽能電池遮蓋方式之電流改變太陽能電池遮蓋方式之電流-電壓電壓 (I-V
Measurement)之量測結果分之量測結果分析析 .... 42
3-2-4結論 ...43
3-2-5改變下轉換材料（改變下轉換材料（Eu-doping Y2O3）蒸鍍電流及厚度之電流）蒸鍍電流
及厚度之電流-電壓（電壓（I-V Measurement）、外部量子效率（）、外部量子效率
（EQE）及熱場發射電子顯微鏡（）及熱場發射電子顯微鏡（TF-SEM）量測結果分析）量測
結果分析 ...................43
3-2-6結論...... 45
第四章 總結論與未來展望總結論與未來展望 ........................... 80
4.1 總結論 ..............80
4.2 未來展望..........................................................80
參考文獻................................................... 81
Extended Abstract .......... 85
Abstract ...... 85
Introduction ................ 86
Experiment ......... 86
Results and Discussion ....................... 87
Conclusion ................ 88
Results and Discussion ....................... 88

[1]S. Gatz, H. Hannebauer, R. Hesse1, F. Werner, A. Schmidt, T. Dullweber, J.
Schmidt, K. Bothe, and R. Brende, “19.4%-Efficient Large-Area Fully Screen-
Printed Silicon Solar Cells,” Physical Status Solidi, Vol. 5, pp. 147-149,
2011.
[2]J. H. Lai, A. Upadhyaya, S. Ramanathan, A. Das, K. Tate, V. Upadhyaya, A.
Kapoor, C. W. Chen, and A. Rohatgi, “High-Efficiency Large-Area Rear
Passivated Silicon Solar Cells With Local Al-BSF and Screen-Printed
Contacts,” IEEE Journal of Photovoltaics, Vol. 1, pp. 16-21, 2011.
[3]J. Schmidt, A. Merkle, R. Brendel, B. Hoex, M. C. M. van de Sanden and W.
M. M. Kessels, “Surface Passivation of High-efficiency Silicon Solar Cells
by Atomic layer deposited Al2O3,” Progress in Photovoltaics : Research and
Application, Vol. 16, pp. 461–466, 2018.
[4] Y. Hwang, C. S. Park, J. Kim, J. Y. Lim, H. Choi, J. Jo, and E. Lee,
“Effect of Laser Damage Etching on I-PERC Solar Cells,” Renewable Energy,
Vol. 79, pp. 131-134, 2015.
[5] L. G. Gerling, G. Masmitja, P. Ortega, C. Voz, R. Alcubilla, and J.
Puigdollers, “Transition Metal Oxides as Hole-Selective Contacts in Silicon
Heterojunctions Solar Cells,” Solar Energy Materials & Solar Cells, Vol.
145, pp. 109-115, 2016.
[6]K. Zilberberg, J. Meyerb, and T. Riedl, “Solution Processed Metal-Oxides
for Organic Electronic Devices,” Journal of Materials Chemistry C, Vol. 1,
pp. 4796-4815, 2013.
[7]X. Liu, C. Wangb, S. Yi, and Y. Gao, “Effect of Oxygen Plasma Treatment On
Air Exposed MoOx Thin Film,” Organic Electrons, Vol. 15, pp. 977-983, 2014.
[8]L. G. Gerling, G. Masmitja, P. Ortega, C. Voz, R. Alcubilla, and J.
Puigdollers, “Passivating/Hole-Selective Contact Based on V2O5/SiOx Stacks
Deposited at Ambient Temperature,” Energy Procedia, Vol. 124, pp. 584-592,
2017.
[9]M. Mews, A. Lemaire, and L. Korte, “Sputtered Tungsten Oxide as Hole
Contact for Silicon Heterojunction Solar Cells,” IEEE Journal of
Photovoltaics, Vol. 7 pp. 1209-1215, 2017.
[10]C. Battaglia, S. M. D. Nicolas, S. D. Wolf, X. Yin, M. Zheng, C. Ballif,
and A. Javey, “Silicon Heterojunction Solar Cell with Passivated Hole
Selective MoOx Contact,” Applied Physics Letters, Vol. 104, p. 113902,
2014.
[11] S. M. D. Nicolas, L. Barraud, S. Nicolay, A. Tomasi, B. Niesen, S. D.
Wolf, and C. Ballif, “22.5% Efficient Silicon Heterojunction Solar Cell
with Molybdenum Oxide Hole Collector,” Applied Physics Letters, Vol. 107,
p.081601, 2015.
[12] J. Shia, L. Shena, Y. Liua, J. Yua, J. Liua, L.Zhanga, Y. Liua, J. Biana,
Z. Liua, and F. Menga, “MoOx Modified ITO/a-Si:H(p) Contact for Silicon
Heterojunction Solar Cell Application,” Materials Research Bulletin, Vol.
120, pp. 176-181, 2018.
[13]L. Cattin, M. Morsli, F. Daho, S. Yapi, and A. Khelil, “Investigation of
Low Resistance Transparent MoO3/Ag/MoO3 Multilayer and Application as
Anode in Organic Solar Cells,” Thin Solid Films, Vol. 518 pp. 4560-4563,
2010.
[14] W. Wua, J. Baoa, Z. Liub, W. Lina, X. Yua, L. Caia, B. Liua, J. Songb, H.
Shena, “Multilayer MoOx/Ag/MoOx Emitters in Dopant-Free Silicon Solar
Cells,” Materials Letters, Vol. 189, pp. 86-88, 2017.
[15]H. D. Um, N. Kim, K. Lee, I. Hwang, J. H. Seo, and K. Seo, “Dopant-Free
All-Back-Contact Si Nanohole Solar Cells Using MoOx and LiF Films,” Nano
Letters, Vol. 16, pp. 981-987, 2016.
[16]U. Akın, and H. Safak, “Thickness Dependence of Dispersion Parameters of
The MoOx Thin Films Prepared Using The Vacuum Evaporation Technique,”
Journal of Alloys and Compounds, Vol. 647, pp. 146-151, 2015.
[17]A. L. F. Cauduro, Z. E. Fabrim, M. Ahmadpour, P. F. P. Fichtner, S.
Hassing, H. G. Rubahn, and M. Madsen, “Tunnel Oxide Passivated Carrier-
Selective Contacts Based on Ultra-Thin SiO2 Layers,” Applied Physics
Letters, Vol. 106, pp. 2020101, 2015.
[18]M. T. Greiner, L. Chai, M. G. Helander, W. M. Tang, and Z. H. Lu,
“Transition Metal Oxide Work Functions: The Influence of Cation Oxidation
State and Oxygen Vacancies,” Advanced Functional Materials, Vol. 22, pp.
1-12, 2012.
[19] J. Tonga, Y. Wanb, J. Cuib, S. Limc, N. Songa, and A. Lennona, “Solution-
Processed Molybdenum Oxide for Hole-Selective Contacts on Crystalline
Silicon Solar Cells,” Applied Surface Science, Vol. 4, pp. 139-146, 2017.
[20]M. Douvas, G. Georgiadou, C. Palilis, and M. Feckl, “Solution‐Processed
Hydrogen Molybdenum Bronzes as Highly Conductive Anode Interlayers in
Efficient Organic Photovoltaics,” Sol. Energy Mater. Sol. Cells, Vol. 188,
pp. 1-10, 2018.
[21] 楊忠諺, “一維稀土奈米發光材料的合成與鑑定,” Nano Communication, Vol. 19, pp.
24-31,2012
[22] 楊忠諺, “頻率轉換材料在能源元件的應用,” Nano Communication, Vol. 21, pp. 23-
26, 2014
[23]V. D. Rodrguez, V. K. Tikhomirov, J. M. Ramos, A. C. Yanes, and V. V.
Moshchalkov, “Towards Broad Range and Highly Efficient Down-Conversion of
Solar Spectrum by Er3+–Yb3+ Co-doped Nano-Structured Glass-Ceramics,”
Solar Energy Materials & Solar Cells, Vol. 94, pp. 1612-1617, 2010.
[24] P. Chung, H. H. Chung, and P. H. Hollowaya, “Phosphor Coatings to Enhance
Si Photovoltaic Cell Performance,” Journal of Vacuum Science & Technology
A, Vol. 25, pp. 60-66, 2007.
[25]J. Wu, G. Xie, J. Lin, Z. Lan, M. Huang, and Y. Huang, “Enhancing
Photoelectrical Performance of Dye-Sensitized Solar Cell by Doping with
Europium-doped Yttria Rare-Earth Oxide,” Journal of Power Sources, Vol.
195, pp.6937-6940, 2010.
[26]M .P. Campos-Arias , E. Zaleta-Alejandre, and C. Falcony, “Synthesis and
Fabrication of Y2O3:Tb3+ and Y2O3:Eu3+ Thin Films for Electroluminescent
Applications: Optical and Structural Characteristics,” Materials Chemistry
and Physics, Vol. 149-150, pp. 34-42, 2015.
[27]H. Miao, R. Ji, X. Hu, L. Han , Y. Hao, Q. Sun , D. Zhang, J. Fan , and J.
Bai, X. Hou, “Y2O3: Eu3+, Tb3+ Spherical Particles Based Anti-Reflection
and Wavelength Conversion Bi-Functional Films : Synthesis and Application
to Solar Cells,” Journal of Alloys and Compounds, Vol. 629 pp. 74-79,
2015.
[28]L. Jiang, W. Chen, J. Zheng, L. Zhu, L. Mo, Z. Li, L. Hu, T. Hayat, A.
Alsaedi, C. Zhang, and S. Dai, “Enhancing Photovoltaic Performance of
Perovskite Solar Cells by Down-Conversion Eu-complex,” ACS Applied
Materials & Interfaces, Vol. 9, pp. 1-42, 2017.
[29]J. Wang, Z. Zhang, X. Guo, J. Zgao, H. Chen, and X. Yang, “High Quality
Thin Film Phosphors of Y2O3:Eu3+ Deposited Via Chemical Bath Deposition,”
25th Eur. Journal of Rare Earths, Vol. 28, pp. 684-687, 2010.
[30]C. L. Cheng, and J. Y. Yang, “Hydrothermal Synthesis of Eu3+-Doped Y(OH)3
Nanotubes as Downconversion Materials for Efficiency Enhancement of
Screen-Printed Monocrystalline Silicon Solar Cells,” IEEE Electron Device
Letters, Vol. 33, pp. 697-699, 2010.
[31]J. Wang, J. Wu, J. Lin, M. Huang, Y. Huang, Z. Lan, Y. Xiao, G. Yue, S.
Yin, and T. Sato, “Application of Y2O3:Er3+ Nanorods in Dye-Sensitized
Solar Cells,” Chemistry Sustainability Energy Materials, Vol. 5, pp. 1307-
1312, 2012.
[32]H. S. Min, Y. C. Joo, and O. S. Song, “Effects of Wafer Cleaning and
Annealing on Glass/Silicon Wafer Direct Bonding,” Journal of Electronic
Packaging, Vol. 126, pp. 120-123, 2004.
[33] S. Y. Liena, C. H. Yanga, C. H. Hsua, Y. S. Linb, C. C. Wang, and D. S.
Wuub, “Black Silicon Layer Formation for Application in Solar Cells,”
Materials Chemistry and Physics, Vol. 133, pp. 63-68, 2012.
[34]J. S. Yoo, I. O. Parm, U. Gangopadhyay, K. Kim, S. K. Dhungel, D.
Mangalaraj, J. Yi, “Solar Energy Materials & Solar Cells, Vol. 90, pp.
3085-3093, 2006.
[35]E. Cornagliottia, M. Ngamob, L. Tousa, R. Russella, J. Horzela, D.
Hendrickxa, B. Douharda, V. Prajapatia, T. Janssensa, and J. Poortmansa,
“Integration of Inline Single-Side Wet Emitter Etch In PERC Cell
Manufacturing,” Energy Procedia, Vol. 27, pp. 684-687, 2012.
[36] Y. Wan, K. R. McIntosh, and A. F. Thomson, “Characterization and
Optimization of PECVD SiNx as An Antireflection Coating and Passivation
Layer for Silicon Solar Cells,” AIP Advances, Vol. 3, p. 032113, 2013.
[37] A. Rohatgi, and J. W. Jeong, “High-Efficiency Screen-Printed Silicon
Ribbon Solar Cells by Effective Defect Passivation and Rapid Thermal
Processing,” Applied Physics Letters, Vol. 82, pp. 1-4, 2003.
[38]F. Huster, “Investigation of The Alloying Process of Screen Printed
Aluminum Pastes for The BSF Formation on Silicon Solar Cells,” 20th
European Photovoltaic Solar Energy Conference and Exhibition, Barcelona,
Vol. 6-10, pp. 684-687, 2005.
[39]D. Meier, H. Preston Davis, and A. Shibata, “Self-Doping Contacts and
Associated Silicon Solar Cell Structures,” 2nd Word Conference and
Exhibition on Photovoltaic Solar Energy Conversion, Vol. 6-8, pp. 1491-
1494, 1998.
[40] S. S. Liao, C. L. Chuang, Y. C. Lin, C. F. Dee, B. Y. Majlis, and E. Y.
Chang, “Effect of Surface Passivation by A Low Pressure and Temperature
Environment-Grown Thermal Oxide Layer for Multi-Crystalline Silicon Solar
Cells,” Thin Solid Films, Vol. 660, pp. 1-9, 2018.
[41] T. Longjuan, Z. Yinfang, Y. Jinling, L. Yan, Z. Wei, X. Jing, L. Yunfei,
and Y. Fuhua, “Dependence of Wet Etch Rate on Deposition, Annealing
Conditions and Etchants for PECVD Silicon Nitride film,” Journal of
Semiconductors, Vol. 30, p.096005, 2009.
[42] S. Watanabe, N. Nakayama, and T. Ito, “Homogeneous Hydrogen-terminated Si
(111) Surface Formed Using Aqueous HF Solution and Water,” Applied Physics
Letters, Vol. 59, pp. 1457-1460, 1991.
[43] H. Guoa, W. Zhanga, L. Loub, A. Brioudec, and J. Mugnierc, “Structure and
Optical Properties of Rare Earth Doped Y2O3 Waveguide Films Derived by Sol
–Gel Process,” Thin Solid Films, Vol. 458, pp. 274-280, 2018.