臺灣博碩士論文加值系統

本研究使用二氧化鈦(TiO₂)以刮刀法製作光陽極薄膜，並使用不同溶液摻入銅葉綠素鈉粉末製備染料，再將醋酸(Glacial Acetic Acid, HOAc)、檸檬酸(Citric Acid, CA)這兩種有羧基的材料加入染料中，探討與原染料製備成染料敏化太陽能電池(Dye-Sensitized Solar Cells, DSSCs)後對光電轉換效率的影響。
研究結果表明，在銅葉綠素鈉染料中加入pH4+0.1ml的醋酸或檸檬酸，封裝成DSSCs後光電轉換效率相比於原染料分別提升10.5%與14.0%。在第七天的J-V curve量測顯示，相比於第一天，加入醋酸與檸檬酸的DSSCs短路電流密度分別提升7.14%與5.91%，填充因子分別下降9.03% 與1.32%。
以上的結果顯示在銅葉綠素鈉染料中加入檸檬酸能夠使DSSCs具有較好的光電轉換效率，此外在封裝完成七天後J-V特性的表現上有較高的穩定性，並且從填充因子觀察到其能量損耗較低，使得銅葉綠素鈉染料在實際應用中具有更高的可行性和穩定性。

In this study utilized titanium dioxide (TiO₂) to fabricate photoanode films using the doctor blade method and prepared dyes by incorporating sodium copper chlorophyllin powder into different solutions. Acetic acid ( Glacial Acetic Acid, HOAc) and citric acid ( Citric Acid, CA), both containing carboxyl groups, were added to the dye to investigate the impact on the photoelectric conversion efficiency of dye-sensitized solar cells ( DSSCs ) compared to the original dye.
The results indicate that adding pH4+0.1ml of acetic acid or citric acid to the sodium copper chlorophyllin dye and encapsulating it into DSSCs increased the photoelectric conversion efficiency by 10.5% and 14.0%, respectively, compared to the original dye. On the seventh day, J-V curve measurements showed that, compared to the first day, the short-circuit current of DSSCs with acetic acid and citric acid increased by 7.14% and 5.91%, respectively, while the fill factor decreased by 9.03% and 1.32%, respectively.
These results indicate that the addition of citric acid to the sodium copper chlorophyllin dye enhances the photoelectric conversion efficiency of DSSCs. Additionally, the J-V characteristics after seven days of encapsulation demonstrated higher stability and lower energy loss, as observed from the fill factor. This suggests that sodium copper chlorophyllin dye exhibits higher feasibility and stability for practical applications.

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 前言.................................................................1
1.2 研究動機與目的........................................................3
第二章 文獻回顧 .........................................................4
2.1 染料敏化太陽能電池(Dye-sensitized solar cells,DSSCs)..................4
2.1.1 太陽能電池發展歷史...................................................4
2.1.2 染料敏化太陽能電池介紹...............................................5
2.1.3 染料敏化太陽能電池的構成.............................................6
2.1.3.1 透明薄膜導電玻璃(Transparent conducting oxide, TCO)................6
2.1.3.2 半導體薄膜工作電極（Working electrode, WE）........................7
2.1.3.3 染料敏化劑（Dye-sensitized）.......................................7
2.1.3.4 電解液（Electrolyte）.............................................10
2.1.3.5 對電極（Counter electrode）.......................................11
2.1.4 染料敏化太陽能電池工作原理...........................................11
2.2 二氧化鈦(Titanium dioxide, TiO2)介紹..................................13
2.3 銅葉綠素鈉（Copper chlorophyllin sodium）.............................15
2.4 官能基(Functional group).............................................16
第三章 實驗方法 ........................................................17
3.1 實驗藥品與儀器.......................................................17
3.1.1 實驗材料...........................................................17
3.1.2 實驗儀器設備.......................................................18
3.2 實驗流程.............................................................19
3.2.1 導電玻璃基板清潔....................................................20
3.2.2 二氧化鈦漿料調配....................................................21
3.2.3 二氧化鈦光陽極製備....................................................22
3.2.4 調配銅葉綠素鈉染料....................................................23
3.2.5 調配電解液...........................................................24
3.2.6 製備對電極...........................................................24
3.2.7 染料敏化太陽能電池封裝................................................25
3.3 實驗設備量測儀器與特性分析..............................................26
3.3.1 複合薄膜之製備與特性分析..............................................26
3.3.1.1 油壓機............................................................26
3.3.1.2 場發射掃描式電子顯微鏡(Field emission scanning electron microscope, FE-SEM)................................26
3.3.2 染料敏化太陽能電池之特性分析 .........................................27
3.3.2.1 紫外光-可見光光譜儀(Ultraviolet-Visible spectroscopy, UV-Vis).......................................27
3.3.2.2 全波段入射光子-電子轉換效率測量系統(Incident photon to current conversion efficiency, IPCE)....................................................29
3.3.2.3 電壓-電流特性量測....................................................30
3.3.2.4 電化學阻抗頻譜分析量測（Electrochemical Impedance Spectroscopy, EIS） ....................................................33
3.3.2.5 傅立葉轉換紅外光譜 ( Fourier-transform infrared spectroscopy, FTIR) .................................................................38
第四章 結果與討論................................................39
4.1 二氧化鈦薄膜之場發射掃描式電子顯微鏡分析..........................39
4.2 染料敏化太陽能電池量測分析............................................40
4.2.1 在固定濃度下使用不同溶液結合銅葉綠素鈉製備染料之染料敏化太陽能電池特性分析 ............................................................40
4.2.1.1 使用不同溶液結合銅葉綠素鈉染料之UV-Vis量測分析..........................40
4.2.1.2 使用不同溶液結合銅葉綠素鈉染料之J-V curve量測分析..........................41
4.2.1.3 使用不同溶液結合銅葉綠素鈉染料之IPCE量測分析..........................42
4.2.2 使用無水乙醇調整銅葉綠素鈉粉末加入濃度製備染料之染料敏化太陽能電池特性分析..........................43
4.2.2.1調整銅葉綠素鈉粉末濃度製備染料之UV-Vis量測分析..........................43
4.2.2.2 調整銅葉綠素鈉粉末濃度製備染料之J-V curve量測分析..........................44
4.2.2.3調整銅葉綠素鈉粉末濃度製備染料之IPCE量測分析..........................45
4.2.3 使用含有羧基的材料以不同pH值加入銅葉綠素鈉染料中之染料敏化太陽能電池特性分析 ..........................46
4.2.3.1 二氧化鈦薄膜浸泡染料之UV-Vis量測分析..........................47
4.2.3.2 比較不同羧基材料pH值及加入量製備染料敏化太陽能電池之J-V curve量測分析 ..........................49
4.2.3.3 比較不同羧基材料pH值及加入量之IPCE量測分析 ..........................53
4.2.4 銅葉綠素鈉染料加入羧基溶液之染料敏化太陽能電池特性比較 ..........................57
4.2.4.1 比較有無加入羧基溶液之染料敏化太陽能電池之FTIR分析 ..........................57
4.2.4.2 比較有無加入羧基溶液之染料敏化太陽能電池之EIS分析 ..........................58
4.2.4.3 比較有無加入羧基溶液之染料敏化太陽能電池J-V curve量測分析 ..........................59
第五章 結論..........................61
參考文獻 ..........................62
Extended Abstract..........................68
Introduction..........................69
Experimental..........................69
Results and discussion..........................70
Conclusions..........................72
Reference..........................73

[1]J. Asafu-Adjaye, D. Byrne, and M. Alvarez, "Economic growth, fossil fuel and non-fossil consumption: A Pooled Mean Group analysis using proxies for capital," Energy Economics, vol. 60, pp. 345-356, Nov 2016, doi: 10.1016/j.eneco.2016.10.016.
[2]P. G. Taylor, O. L. d'Ortigue, M. Francoeur, and N. Trudeau, "Final energy use in IEA countries: The role of energy efficiency," Energy Policy, vol. 38, no. 11, pp. 6463-6474, Nov 2010, doi: 10.1016/j.enpol.2009.05.009.
[3]J. McCarthy, "A socioecological fix to capitalist crisis and climate change? The possibilities and limits of renewable energy," Environment and Planning A, vol. 47, no. 12, pp. 2485-2502, 2015.
[4]A. Shrestha, A. A. Mustafa, M. M. Htike, V. You, and M. Kakinaka, "Evolution of energy mix in emerging countries: Modern renewable energy, traditional renewable energy, and non-renewable energy," Renewable Energy, vol. 199, pp. 419-432, Nov 2022, doi: 10.1016/j.renene.2022.09.018.
[5]J. Gong, J. Liang, and K. Sumathy, "Review on dye-sensitized solar cells (DSSCs): Fundamental concepts and novel materials," Renewable and Sustainable Energy Reviews, vol. 16, no. 8, pp. 5848-5860, 2012.
[6]E. Rodriguez, J. M. Cardemil, A. R. Starke, and R. Escobar, "Modelling the Exergy of Solar Radiation: A Review," Energies, vol. 15, no. 4, Feb 2022, Art no. 1477, doi: 10.3390/en15041477.
[7]C. Haddock and J. S. C. McKee, "Solar-energy collection, concentration,and thermal-conversion-a review," Energy Sources, vol. 13, no. 4, pp. 461-482, 1991, doi: 10.1080/00908319108909002.
[8]M. B. Hayat, D. Ali, K. C. Monyake, L. Alagha, and N. Ahmed, "Solar energy-A look into power generation, challenges, and a solar-powered future," International Journal of Energy Research, vol. 43, no. 3, pp. 1049-1067, Mar 2019, doi: 10.1002/er.4252.
[9]B. K. Ghosh, M. Hasanuzzman, I. Saad, K. A. Mohamad, and M. K. Hossain, "Photovoltaic technologies photo-thermal challenges: Thin active layer solar cells significance," Optik, vol. 274, Mar 2023, Art no. 170567, doi: 10.1016/j.ijleo.2023.170567.
[10]A. M. Bagher, M. M. A. Vahid, and M. Mohsen, "Types of solar cells and application," American Journal of optics and Photonics, vol. 3, no. 5, pp. 94-113, 2015.
[11]A. Carella, F. Borbone, and R. Centore, "Research Progress on Photosensitizers for DSSCs," Frontiers in Chemistry, vol. 6, Oct 2018, Art no. 481, doi: 10.3389/fchem.2018.00481.
[12]O. Berger, "Understanding the fundamentals of TiO₂ surfaces Part II. Reactivity and surface chemistry of TiO₂ single crystals," Surface Engineering, 2022 Dec 2022, doi: 10.1080/02670844.2023.2175505.
[13]S. Shalini, R. Balasundaraprabhu, T. S. Kumar, N. Prabavathy, S. Senthilarasu, and S. Prasanna, "Status and outlook of sensitizers/dyes used in dye sensitized solar cells (DSSCs): a review," International Journal of Energy Research, vol. 40, no. 10, pp. 1303-1320, Aug 2016, doi: 10.1002/er.3538.
[14]經濟部能源署. "台灣再生能源發電量統計."
[15]A. M. Ammar, H. S. Mohamed, M. M. Yousef, G. M. Abdel-Hafez, A. S. Hassanien, and A. S. Khalil, "Dye-sensitized solar cells (DSSCs) based on extracted natural dyes," Journal of Nanomaterials, vol. 2019, 2019.
[16]L. Zhang and J. M. Cole, "Anchoring groups for dye-sensitized solar cells," ACS applied materials & interfaces, vol. 7, no. 6, pp. 3427-3455, 2015.
[17]K. Sharma, V. Sharma, and S. Sharma, "Dye-sensitized solar cells: fundamentals and current status," Nanoscale research letters, vol. 13, pp. 1-46, 2018.
[18]S. K. Nag, T. K. Gangopadhyay, and J. Paserba, "Solar photovoltaics: A brief history of technologies [history]," IEEE Power and Energy Magazine, vol. 20, no. 3, pp. 77-85, 2022.
[19]K. Chopra, P. Paulson, and V. Dutta, "Thin‐film solar cells: an overview," Progress in Photovoltaics: Research and applications, vol. 12, no. 2‐3, pp. 69-92, 2004.
[20]A. Herez, H. Jaber, H. El Hage, T. Lemenand, M. Ramadan, and M. Khaled, "A review on the classifications and applications of solar photovoltaic technology," Aims Energy, vol. 11, no. 6, pp. 1102-1130, 2023, doi: 10.3934/energy.2023051.
[21]M. Gratzel and B. O’Regan, "A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO₂ films," Nature, vol. 353, no. 6346, pp. 737-740, 1991.
[22]S. Mozaffari, M. R. Nateghi, and M. B. Zarandi, "An overview of the Challenges in the commercialization of dye sensitized solar cells," Renewable and Sustainable Energy Reviews, vol. 71, pp. 675-686, 2017.
[23]A. Andualem and S. Demiss, "Review on dye-sensitized solar cells (DSSCs)," Edelweiss Appli Sci Tech, vol. 2, no. 2018, pp. 145-150, 2018.
[24]S. Lee et al., "Indium− Tin− Oxide-Based Transparent Conducting Layers for Highly Efficient Photovoltaic Devices," The Journal of Physical Chemistry C, vol. 113, no. 17, pp. 7443-7447, 2009.
[25]C. Sima, C. Grigoriu, and S. Antohe, "Comparison of the dye-sensitized solar cells performances based on transparent conductive ITO and FTO," Thin Solid Films, vol. 519, no. 2, pp. 595-597, Nov 2010, doi: 10.1016/j.tsf.2010.07.002.
[26]S. N. Sadikin, M. Y. A. Rahman, A. A. Umar, and M. M. Salleh, "Effect of Spin-Coating Cycle on the Properties of TiO₂ Thin Film and Performance of DSSC," International Journal of Electrochemical Science, vol. 12, no. 6, pp. 5529-5538, Jun 2017, doi: 10.20964/2017.06.57.
[27]T.-P. Huynh, T.-T. Hoang, P.-H. Nguyen, T.-N. Tran, and T.-V. Nguyen, "Preparation of TiO₂ thin film using modified doctor-blade method for improvement of dye-sensitized solar cell," in 2009 34th IEEE photovoltaic specialists conference (PVSC), 2009: IEEE, pp. 002168-002171.
[28]A. Agrawal, S. A. Siddiqui, A. Soni, K. Khandelwal, and G. D. Sharma, "Performance analysis of TiO₂/ based dye sensitized solar cell prepared by screen printing and doctor blade deposition techniques," Solar Energy, vol. 226, pp. 9-19, Sep 2021, doi: 10.1016/j.solener.2021.08.001.
[29]G. P. Smestad, "Education and solar conversion:: demonstrating electron transfer," Solar Energy Materials and Solar Cells, vol. 55, no. 1-2, pp. 157-178, 1998.
[30]T. Horiuchi, H. Miura, K. Sumioka, and S. Uchida, "High efficiency of dye-sensitized solar cells based on metal-free indoline dyes," Journal of the American Chemical Society, vol. 126, no. 39, pp. 12218-12219, 2004.
[31]S. Ito et al., "High-conversion-efficiency organic dye-sensitized solar cells with a novel indoline dye," Chemical communications, no. 41, pp. 5194-5196, 2008.
[32]M. K. Nazeeruddin, R. Splivallo, P. Liska, P. Comte, and M. Grätzel, "A swift dye uptake procedure for dye sensitized solar cells," Chemical Communications, no. 12, pp. 1456-1457, 2003.
[33]M. K. Nazeeruddin, R. Humphry-Baker, P. Liska, and M. Grätzel, "Investigation of sensitizer adsorption and the influence of protons on current and voltage of a dye-sensitized nanocrystalline TiO₂ solar cell," The Journal of Physical Chemistry B, vol. 107, no. 34, pp. 8981-8987, 2003.
[34]K. Portillo-Cortez, A. Martínez, A. Dutt, and G. Santana, "N719 Derivatives for application in a dye-sensitized solar cell (DSSCs): a theoretical study," The Journal of Physical Chemistry A, vol. 123, no. 51, pp. 10930-10939, 2019.
[35]N. Tomar, V. S. Dhaka, and P. K. Surolia, "A brief review on carbon nanomaterial counter electrodes for N719 based dye-sensitized solar cells," Materials Today: Proceedings, vol. 43, pp. 2975-2978, 2021.
[36]G. V. Belessiotis, M. Antoniadou, I. Ibrahim, C. S. Karagianni, and P. Falaras, "Universal electrolyte for DSSCs οperation under both simulated solar and indoor fluorescent lighting," Materials Chemistry and Physics, vol. 277, p. 125543, 2022.
[37]J. Wu et al., "Electrolytes in dye-sensitized solar cells," Chemical reviews, vol. 115, no. 5, pp. 2136-2173, 2015.
[38]A. Hauch and A. Georg, "Diffusion in the electrolyte and charge-transfer reaction at the platinum electrode in dye-sensitized solar cells," Electrochimica acta, vol. 46, no. 22, pp. 3457-3466, 2001.
[39]Y.-L. Lee, C.-L. Chen, L.-W. Chong, C.-H. Chen, Y.-F. Liu, and C.-F. Chi, "A platinum counter electrode with high electrochemical activity and high transparency for dye-sensitized solar cells," Electrochemistry Communications, vol. 12, no. 11, pp. 1662-1665, 2010.
[40]J. W. Gong, J. Liang, and K. Sumathy, "Review on dye-sensitized solar cells (DSSCs): Fundamental concepts and novel materials," Renewable & Sustainable Energy Reviews, vol. 16, no. 8, pp. 5848-5860, Oct 2012, doi: 10.1016/j.rser.2012.04.044.
[41]A. L. Linsebigler, G. Lu, and J. T. Yates Jr, "Photocatalysis on TiO₂ surfaces: principles, mechanisms, and selected results," Chemical reviews, vol. 95, no. 3, pp. 735-758, 1995.
[42]F. Parrino and L. Palmisano, Titanium dioxide (TiO₂) and its applications. elsevier, 2020.
[43]D. A. Hanaor and C. C. Sorrell, "Review of the anatase to rutile phase transformation," Journal of Materials science, vol. 46, pp. 855-874, 2011.
[44]U. Diebold, "The surface science of titanium dioxide," Surface Science Reports, vol. 48, no. 5-8, pp. 53-229, 2003, Art no. Pii s0167-5729(02)00100-0, doi: 10.1016/s0167-5729(02)00100-0.
[45]X. Chen and S. S. Mao, "Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications," Chemical reviews, vol. 107, no. 7, pp. 2891-2959, 2007.
[46]P. Bobbio and M. Guedes, "Stability of copper and magnesium chlorophylls," Food chemistry, vol. 36, no. 3, pp. 165-168, 1990.
[47]T. S. Chemicals. "Chlorophyllin, coppered trisodium salt, Thermo Scientific Chemicals."
[48]C. O'Rourke and D. R. Bowler, "DSSCs anchoring groups: a surface dependent decision," Journal of Physics: Condensed Matter, vol. 26, no. 19, p. 195302, 2014.
[49]A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, and H. Pettersson, "Dye-sensitized solar cells," Chemical reviews, vol. 110, no. 11, pp. 6595-6663, 2010.
[50]E. Galoppini, "Linkers for anchoring sensitizers to semiconductor nanoparticles," Coordination Chemistry Reviews, vol. 248, no. 13-14, pp. 1283-1297, 2004.
[51]H. Lindström, A. Holmberg, E. Magnusson, L. Malmqvist, and A. Hagfeldt, "A new method to make dye-sensitized nanocrystalline solar cells at room temperature," Journal of Photochemistry and Photobiology A: chemistry, vol. 145, no. 1-2, pp. 107-112, 2001.
[52]羅聖全 and 羅聖全, "科學基礎之重要利器-掃描式電子顯微鏡 (SEM)," 科學研習,國立中央大學, p. 52, 2013.
[53]F. S. Rocha, A. J. Gomes, C. N. Lunardi, S. Kaliaguine, and G. S. Patience, "Experimental methods in chemical engineering: Ultraviolet visible spectroscopy—UV‐Vis," The Canadian Journal of Chemical Engineering, vol. 96, no. 12, pp. 2512-2517, 2018.
[54]J. Ashenhurst. "Introduction To UV-Vis Spectroscopy.".
[55]X.-Z. Guo, Y.-H. Luo, Y.-D. Zhang, X.-C. Huang, D.-M. Li, and Q.-B. Meng, "Study on the effect of measuring methods on incident photon-to-electron conversion efficiency of dye-sensitized solar cells by home-made setup," Review of scientific instruments, vol. 81, no. 10, 2010.
[56]I. Intergovernmental Panel on Climate Change. "Working Group I: The Physical Science Basis.".
[57]光焱科技股份有限公司. "Solar Simulator- Basic Knowledge and Working Principles.".
[58]M. Diantoro, T. Suprayogi, A. Hidayat, A. Taufiq, A. Fuad, and R. Suryana, "Shockley’s equation fit analyses for solar cell parameters from IV curves," International Journal of Photoenergy, vol. 2018, 2018.
[59]S. Sarker, A. Ahammad, H. W. Seo, and D. M. Kim, "Electrochemical impedance spectra of dye-sensitized solar cells: fundamentals and spreadsheet calculation," International Journal of Photoenergy, vol. 2014, 2014.
[60]J.-P. Diard, N. Glandut, C. Montella, and J.-Y. Sanchez, "One layer, two layers, etc. An introduction to the EIS study of multilayer electrodes. Part 1: Theory," Journal of Electroanalytical Chemistry, vol. 578, no. 2, pp. 247-257, 2005.
[61]L. Han, N. Koide, Y. Chiba, and T. Mitate, "Modeling of an equivalent circuit for dye-sensitized solar cells," Applied Physics Letters, vol. 84, no. 13, pp. 2433-2435, 2004.
[62]A. Subramanian, C.-Y. Ho, and H. Wang, "Investigation of various photoanode structures on dye-sensitized solar cell performance using mixed-phase TiO₂," Journal of alloys and compounds, vol. 572, pp. 11-16, 2013.
[63]scinco. "傅立葉轉換紅外光譜(FTIR)分析原理." https://www.scincotaiwan.tw/zh-cht/TechnicalSupport_Detail-21.html (July 4, 2024).
[64]Renishaw. "Interferometry explained." https://www.renishaw.com/tw/interferometry-explained--7854 (July 4, 2024).
[65]M. Rahman, A. Umar, R. Taslim, and M. Salleh, "Effect of organic dye, the concentration and dipping time of the organic dye N719 on the photovoltaic performance of dye-sensitized ZnO solar cell prepared by ammonia-assisted hydrolysis technique," Electrochimica acta, vol. 88, pp. 639-643, 2013.
[66]A. K. Kolah, N. S. Asthana, D. T. Vu, C. T. Lira, and D. J. Miller, "Reaction kinetics of the catalytic esterification of citric acid with ethanol," Industrial & engineering chemistry research, vol. 46, no. 10, pp. 3180-3187, 2007.
[67]A. Pirashanthan, M. Thanihaichelvan, K. Mariappan, D. Velauthapillai, P. Ravirajan, and Y. Shivatharsiny, "Synthesis of a carboxylic acid-based ruthenium sensitizer and its applicability towards Dye-Sensitized Solar Cells," Solar Energy, vol. 225, pp. 399-406, 2021.
[68]H.-K. Song, Y. H. Park, C.-H. Han, and J.-G. Jee, "Synthesis of ruthenium complex and its application in dye-sensitized solar cells," Journal of Industrial and Engineering Chemistry, vol. 15, no. 1, pp. 62-65, 2009.
[69]A. Omar, M. S. Ali, and N. Abd Rahim, "Electron transport properties analysis of titanium dioxide dye-sensitized solar cells (TiO₂-DSSCs) based natural dyes using electrochemical impedance spectroscopy concept: A review," Solar Energy, vol. 207, pp. 1088-1121, 2020.
[70]A. R. Bredar, A. L. Chown, A. R. Burton, and B. H. Farnum, "Electrochemical impedance spectroscopy of metal oxide electrodes for energy applications," ACS Applied Energy Materials, vol. 3, no. 1, pp. 66-98, 2020.
[71]G. T. Tractz et al., "Recombination study of dye sensitized solar cells with natural extracts," Journal of the Brazilian Chemical Society, vol. 30, no. 2, pp. 371-378, 2019.