本研究旨在開發高效能、穩定的單一片式染料敏化太陽能電池，主要聚焦於優化絕緣層結構、開發可印刷式電解質，以及探討添加二氧化鈦奈米粒子對電池性能的影響。研究結果顯示，採用二氧化鋯和二氧化鈦的雙層結構能夠有效提高光反射率並抑制電子再結合，在標準光照下達到8.34%的光電轉換效率，明顯優於單層結構。為提高電池穩定性，本研究以聚氧化乙烯（PEO）和聚甲基丙烯酸甲酯（PMMA）為增稠劑去形成可印刷式膠態電解質。通過優化高分子含量，在5 wt%添加量時達到最佳效能，電池效率達到7.10%，超越了傳統液態電解質電池的表現。研究結果也發現，在可印刷電解質中添加4 wt% 二氧化鈦奈米粒子能顯著提升電池性能。這種改善主要是因為二氧化鈦粒子增強了電解質的離子導電性和光散射效應，同時提高了光電極/電解質界面的電荷再結合阻力。在添加TiO2奈米粒子的可印刷電解質電池達到了7.29%的光電轉換效率，為本研究中最佳效率。電池穩定性測試顯示，採用可印刷電解質的電池在500小時後仍保持約90%的初始效率，優於液態電解質電池。此結果證實了開發的可印刷電解質不僅提高了電池效率，還顯著改善了其穩定性。

This research aims to develop high-efficiency and stable monolithic dye-sensitized solar cells, focusing mainly on optimizing the insulating layer structure, developing printable electrolytes, and exploring the impact of adding TiO2 nanoparticles on solar cell performance. Results show that the two-layer structure of ZrO2 and TiO2 can improve the light reflectivity, the efficiency reaches 8.34% under one sun illumination. In order to improve solar cells stability, We use polyethylene oxide and polymethyl methacrylate to form a printable electrolyte. By optimizing the polymer content, the best performance is achieved at adding 5 wt% polymer, and the solar cell efficiency reaches 7.10%, surpassing the performance of liquid electrolyte solar cells. We also found that adding 4 wt% TiO2 nanoparticles to the printable electrolyte can significantly improve solar cell performance. This improvement is due to the fact that TiO2 particles enhance the ionic conductivity and light scattering. The printable electrolyte cell adding TiO2 nanoparticles achieved 7.29%, which is the best efficiency in this study. Solar cell stability test shows that cells using printable electrolytes still maintain about 90% of their initial efficiency after 500 hours, which is better than liquid electrolyte solar cells.

[1] B. O'regan and M. Grätzel, "A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films," nature, vol. 353, no. 6346, pp. 737-740, 1991.
[2] M. S. Ahmad, A. K. Pandey, and N. Abd Rahim, "Advancements in the development of TiO2 photoanodes and its fabrication methods for dye sensitized solar cell (DSSC) applications. A review," Renewable and Sustainable Energy Reviews, vol. 77, pp. 89-108, 2017.
[3] 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.
[4] F. Santos, D. Ivanou, and A. Mendes, "The renaissance of monolithic dye-sensitized solar cells," Materials Today Communications, vol. 32, p. 104030, 2022.
[5] S. Ito, G. Rothenberger, P. Liska, P. Comte, S. M. Zakeeruddin, P. Péchy, "High-efficiency (7.2%) flexible dye-sensitized solar cells with Ti-metal substrate for nanocrystalline-TiO 2 photoanode," Chemical Communications, no. 38, pp. 4004-4006, 2006.
[6] H. Weerasinghe, P. Sirimanne, G. Franks, G. Simon, and Y. Cheng, "Low temperature chemically sintered nano-crystalline TiO2 electrodes for flexible dye-sensitized solar cells," Journal of Photochemistry and Photobiology A: Chemistry, vol. 213, no. 1, pp. 30-36, 2010.
[7] Y.-Y. Kuo and C.-H. Chien, "Sinter-free transferring of anodized TiO2 nanotube-array onto a flexible and transparent sheet for dye-sensitized solar cells," Electrochimica Acta, vol. 91, pp. 337-343, 2013.
[8] M. Grätzel, "Photoelectrochemical cells," nature, vol. 414, no. 6861, pp. 338-344, 2001.
[9] M. Grätzel, "Conversion of sunlight to electric power by nanocrystalline dye-sensitized solar cells," Journal of Photochemistry and Photobiology A: Chemistry, vol. 164, no. 1-3, pp. 3-14, 2004.
[10] H. Rao, M. Zhou, Z. Pan, and X. Zhong, "Quantum dot materials engineering boosting the quantum dot sensitized solar cell efficiency over 13%," Journal of materials chemistry A, vol. 8, no. 20, pp. 10233-10241, 2020.
[11] A. Hagfeldt and M. Grätzel, "Molecular photovoltaics," Accounts of chemical research, vol. 33, no. 5, pp. 269-277, 2000.
[12] M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Müller, P. Liska, "Conversion of light to electricity by cis-X2bis (2, 2'-bipyridyl-4, 4'-dicarboxylate) ruthenium (II) charge-transfer sensitizers (X= Cl-, Br-, I-, CN-, and SCN-) on nanocrystalline titanium dioxide electrodes," Journal of the American Chemical Society, vol. 115, no. 14, pp. 6382-6390, 1993.
[13] M. K. Nazeeruddin, P. Pechy, and M. Grätzel, "Efficient panchromatic sensitization of nanocrystalline TiO 2 films by a black dye based on a trithiocyanato–ruthenium complex," Chemical Communications, no. 18, pp. 1705-1706, 1997.
[14] M. K. Nazeeruddin, P. Pechy, T. Renouard, S. M. Zakeeruddin, R. Humphry-Baker, "Engineering of efficient panchromatic sensitizers for nanocrystalline TiO2-based solar cells," Journal of the American Chemical Society, vol. 123, no. 8, pp. 1613-1624, 2001.
[15] M. K. Nazeeruddin, F. De Angelis, S. Fantacci, A. Selloni, G. Viscardi, P. Liska, "Combined experimental and DFT-TDDFT computational study of photoelectrochemical cell ruthenium sensitizers," Journal of the American Chemical Society, vol. 127, no. 48, pp. 16835-16847, 2005.
[16] P. Wang, S. M. Zakeeruddin, J. E. Moser, M. K. Nazeeruddin, T. Sekiguchi, and M. Grätzel, "A stable quasi-solid-state dye-sensitized solar cell with an amphiphilic ruthenium sensitizer and polymer gel electrolyte," Nature materials, vol. 2, no. 6, pp. 402-407, 2003.
[17] C.-Y. Chen, M. Wang, J.-Y. Li, N. Pootrakulchote, L. Alibabaei, C.-h. Ngoc-le, "Highly efficient light-harvesting ruthenium sensitizer for thin-film dye-sensitized solar cells," ACS nano, vol. 3, no. 10, pp. 3103-3109, 2009.
[18] Q. Yu, Y. Wang, Z. Yi, N. Zu, J. Zhang, M. Zhang, "High-efficiency dye-sensitized solar cells: the influence of lithium ions on exciton dissociation, charge recombination, and surface states," ACS nano, vol. 4, no. 10, pp. 6032-6038, 2010.
[19] T. Bessho, S. M. Zakeeruddin, C. Y. Yeh, E. W. G. Diau, and M. Grätzel, "Highly efficient mesoscopic dye‐sensitized solar cells based on donor–acceptor‐substituted porphyrins," Angewandte Chemie International Edition, vol. 49, no. 37, pp. 6646-6649, 2010.
[20] A. Yella, H.-W. Lee, H. N. Tsao, C. Yi, A. K. Chandiran, M. K. Nazeeruddin, "Porphyrin-sensitized solar cells with cobalt (II/III)–based redox electrolyte exceed 12 percent efficiency," science, vol. 334, no. 6056, pp. 629-634, 2011.
[21] S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B. F. Curchod, N. Ashari-Astani., "Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers," Nature chemistry, vol. 6, no. 3, pp. 242-247, 2014. [Online]. Available: https://core.ac.uk/download/30441718.pdf.
[22] T. Horiuchi, H. Miura, and S. Uchida, "Highly-efficient metal-free organic dyes for dye-sensitized solar cells," Chemical Communications, no. 24, pp. 3036-3037, 2003.
[23] S. Ito, S. M. Zakeeruddin, R. Humphry‐Baker, P. Liska, R. Charvet, P. Comte., "High‐efficiency organic‐dye‐sensitized solar cells controlled by nanocrystalline‐TiO2 electrode thickness," Advanced Materials, vol. 18, no. 9, pp. 1202-1205, 2006.
[24] S. Ito, H. Miura, S. Uchida, M. Takata, K. Sumioka, P. Liska., "High-conversion-efficiency organic dye-sensitized solar cells with a novel indoline dye," Chemical communications, no. 41, pp. 5194-5196, 2008.
[25] G. Zhang, H. Bala, Y. Cheng, D. Shi, X. Lv, Q. Yu, "High efficiency and stable dye-sensitized solar cells with an organic chromophore featuring a binary π-conjugated spacer," Chemical Communications, no. 16, pp. 2198-2200, 2009.
[26] W. Zeng, Y. Cao, Y. Bai, Y. Wang, Y. Shi, M. Zhang, "Efficient dye-sensitized solar cells with an organic photosensitizer featuring orderly conjugated ethylenedioxythiophene and dithienosilole blocks," Chemistry of Materials, vol. 22, no. 5, pp. 1915-1925, 2010.
[27] L. Kavan, J.-H. Yum, M. K. Nazeeruddin, and M. Grätzel, "Graphene nanoplatelet cathode for Co (III)/(II) mediated dye-sensitized solar cells," Acs Nano, vol. 5, no. 11, pp. 9171-9178, 2011.
[28] W. Xiang, W. Huang, U. Bach, and L. Spiccia, "Stable high efficiency dye-sensitized solar cells based on a cobalt polymer gel electrolyte," Chemical communications, vol. 49, no. 79, pp. 8997-8999, 2013.
[29] K. Kakiage, Y. Aoyama, T. Yano, K. Oya, J.-i. Fujisawa, and M. Hanaya, "Highly-efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes," Chemical communications, vol. 51, no. 88, pp. 15894-15897, 2015.
[30] G. Wolfbauer, A. M. Bond, J. C. Eklund, and D. R. MacFarlane, "A channel flow cell system specifically designed to test the efficiency of redox shuttles in dye sensitized solar cells," Solar energy materials and solar cells, vol. 70, no. 1, pp. 85-101, 2001.
[31] S. Nakade, T. Kanzaki, W. Kubo, T. Kitamura, Y. Wada, and S. Yanagida, "Role of electrolytes on charge recombination in dye-sensitized tio2 solar cell (1): the case of solar cells using the I-/I3-redox couple," The Journal of Physical Chemistry B, vol. 109, no. 8, pp. 3480-3487, 2005.
[32] C. Zhang, Y. Huang, Z. Huo, S. Chen, and S. Dai, "Photoelectrochemical effects of guanidinium thiocyanate on dye-sensitized solar cell performance and stability," The Journal of Physical Chemistry C, vol. 113, no. 52, pp. 21779-21783, 2009.
[33] T. W. Hamann, "The end of iodide? Cobalt complex redox shuttles in DSSCs," Dalton Transactions, vol. 41, no. 11, pp. 3111-3115, 2012.
[34] T. N. Murakami, S. Ito, Q. Wang, M. K. Nazeeruddin, T. Bessho, I. Cesar., "Highly efficient dye-sensitized solar cells based on carbon black counter electrodes," Journal of the Electrochemical Society, vol. 153, no. 12, p. A2255, 2006.
[35] K.-C. Huang, Y.-C. Wang, R.-X. Dong, W.-C. Tsai, K.-W. Tsai, C.-C. Wang, "A high performance dye-sensitized solar cell with a novel nanocomposite film of PtNP/MWCNT on the counter electrode," Journal of Materials Chemistry, vol. 20, no. 20, pp. 4067-4073, 2010.
[36] L. Kavan, J. H. Yum, and M. Grätzel, "Optically transparent cathode for dye-sensitized solar cells based on graphene nanoplatelets," Acs Nano, vol. 5, no. 1, pp. 165-172, 2011.
[37] J. M. Pringle, V. Armel, and D. R. MacFarlane, "Electrodeposited PEDOT-on-plastic cathodes for dye-sensitized solar cells," Chemical Communications, vol. 46, no. 29, pp. 5367-5369, 2010.
[38] A. Kay and M. Grätzel, "Low cost photovoltaic modules based on dye sensitized nanocrystalline titanium dioxide and carbon powder," Solar Energy Materials and Solar Cells, vol. 44, no. 1, pp. 99-117, 1996.
[39] A. Hinsch, R. Kinderman, M. Späth, E. Rijnberg, and J. van Roosmalen, "THE PERFORMANCE OF DYE-SENSITISED SOLAR CELLS WITH A ONE-FACIAL, MONOLITHIC LAYER BUILT-UP PREPARED BY SCREEN PRINTING," in 2nd World Conference and Exhibition on Photovoltaic Solar Energy Conversion, 1998, pp. 6-10.
[40] H. Pettersson et al., "The monolithic multicell: a tool for testing material components in dye‐sensitized solar cells," Progress in Photovoltaics: Research and Applications, vol. 15, no. 2, pp. 113-121, 2007.
[41] M. Gorlov, H. Pettersson, A. Hagfeldt, and L. Kloo, "Electrolytes for dye-sensitized solar cells based on interhalogen ionic salts and liquids," Inorganic chemistry, vol. 46, no. 9, pp. 3566-3575, 2007.
[42] A. Hinsch, S. Behrens, M. Berginc, H. Bönnemann, H. Brandt, A. Drewitz, "Material development for dye solar modules: results from an integrated approach," Progress in Photovoltaics: Research and Applications, vol. 16, no. 6, pp. 489-501, 2008.
[43] S. J. Thompson, N. W. Duffy, U. Bach, and Y.-B. Cheng, "On the role of the spacer layer in monolithic dye-sensitized solar cells," The Journal of Physical Chemistry C, vol. 114, no. 5, pp. 2365-2369, 2010.
[44] S. J. Thompson, J. M. Pringle, X. L. Zhang, and Y.-B. Cheng, "A novel carbon–PEDOT composite counter electrode for monolithic dye-Sensitized solar cells," Journal of Physics D: Applied Physics, vol. 46, no. 2, p. 024007, 2012.
[45] G. Liu, H. Wang, X. Li, Y. Rong, Z. Ku, M. Xu, "A mesoscopic platinized graphite/carbon black counter electrode for a highly efficient monolithic dye-sensitized solar cell," Electrochimica Acta, vol. 69, pp. 334-339, 2012.
[46] D. Fu, P. Lay, and U. Bach, "TCO-free flexible monolithic back-contact dye-sensitized solar cells," Energy & Environmental Science, vol. 6, no. 3, pp. 824-829, 2013.
[47] J. Kwon, N.-G. Park, J. Y. Lee, M. J. Ko, and J. H. Park, "Highly efficient monolithic dye-sensitized solar cells," ACS Applied Materials & Interfaces, vol. 5, no. 6, pp. 2070-2074, 2013.
[48] F. Behrouznejad, N. Taghavinia, and N. Ghazyani, "Monolithic dye sensitized solar cell with metal foil counter electrode," Organic Electronics, vol. 57, pp. 194-200, 2018.
[49] F. Santos, C. Hora, G. Bernardo, D. Ivanou, and A. Mendes, "Efficient monolithic dye sensitized solar cells with eco-friendly silica-titania spacer layers," Solar Energy, vol. 183, pp. 419-424, 2019.
[50] F. Santos, C. Hora, D. Ivanou, and A. M. Mendes, "Efficient liquid-junction monolithic cobalt-Mediated dye-sensitized solar cells for solar and artificial light conversion," ACS Applied Energy Materials, vol. 4, no. 5, pp. 5050-5058, 2021.
[51] S. Venkatesan, C.-Y. Chiang, H. Teng, and Y.-L. Lee, "Monolithic quasi-solid-state dye sensitized solar cells prepared entirely by printing processes," ACS Sustainable Chemistry & Engineering, vol. 11, no. 13, pp. 5293-5302, 2023.
[52] M.-S. Kang, K.-S. Ahn, and J.-W. Lee, "Quasi-solid-state dye-sensitized solar cells employing ternary component polymer-gel electrolytes," Journal of power sources, vol. 180, no. 2, pp. 896-901, 2008.