本研究聚焦於提升多孔對電極模板鈣鈦礦太陽能電池之鈣鈦礦滲孔率，系統性探討透多孔電極孔隙率、鈣鈦礦沉積方式與後續甲胺氣體處理對元件光伏參數的影響。首先，通過改變氧電漿蝕刻時間來調整多孔對電極尺寸，並經穿透率量測、電阻值量測、掃描式電子顯微鏡（Scanning Electron Microscope，簡稱 SEM）及電壓電流密度量測（J-V）後，選擇氧電漿蝕刻時間為 4.5 分鐘之多孔對電極模板之元件光伏表現為最佳模板，並作為後續實驗所使用之模板。
在此模板上製程出的元件效率可達 3.53%，但和目前常見的多孔碳對電極元件之元件相比仍有一段差距。因此我們首先通過接觸角量測，確認了本多孔對電極模板清水性並非元件表現不佳的原因。後續從 SEM 俯視圖上發現鈣鈦礦結晶後可能有封孔現象產生導致前驅液滲透不良，以及能量色散光譜儀（Energy Dispersive Spectroscope，簡稱 EDS）之線性掃描結果顯示鈣鈦礦組成中的主要元素 Pb 和 I 在進入多孔氧化層後元素比例下降，顯示鈣鈦礦於多孔層中分布不均且滲孔率不佳。綜合以上分析結果，我們認為封孔現象發生及鈣鈦礦滲孔率不佳可能是導致元件光伏表現不佳的原因。
在此基礎下，我們通過應用甲胺氣體處理，使鈣鈦礦能再次滲透進入多孔層中，提升滲孔率的同時，也提升元件短路電流密度及轉換效率。在 J-V 量測下得到最高 5.76% 的轉換效率，且於 EDS 區域分析及 X 射線光電子能譜儀（X-ray Photoelectron Spectrometer，簡稱 XPS）縱深分析中得到了元素 Pb 和 I 元素比例於多孔氧化層中提升的結果，證實甲胺氣體處理確實能些微改善鈣鈦礦滲孔率的問題。
總而言之，本研究於多孔對電極模板之鈣鈦礦太陽能電池元件上應用甲胺氣體處理，實現了提升鈣鈦礦於多孔氧化層中滲孔率的目標，並提升元件之短路電流密度及轉換效率。此結果亦能應用於後續元件重複利用後欲重新填充鈣鈦礦時，減少元件重複利用時的效率損失。

This study focuses on enhancing the perovskite infiltration rate in perovskite solar cells based on a porous counter electrode template, systematically investigating the effects of electrode porosity, deposition methods, and subsequent methylamine (MA) gas treatment on photovoltaic parameters. First, the dimensions of the porous electrode were tuned by varying the oxygen plasma etching time. Based on transmittance, sheet resistance, scanning electron microscope（SEM）, and voltage and current density（J-V）characterizations, the template etched for 4.5 minutes yielded the optimal photovoltaic performance and was selected for subsequent experiments.
Devices fabricated with this optimal template achieved a power conversion efficiency of 3.53%. To identify the performance bottleneck compared to conventional porous carbon electrodes, contact angle measurements were performed, confirming that the hydrophilicity of the template was not the limiting factor. However, top-view SEM revealed a pore-blocking phenomenon after crystallization, causing poor precursor infiltration. Furthermore, energy dispersive spectroscope（EDS）line scans indicated a drop in the ratio of lead and iodine inside the porous oxide layer, reflecting uneven perovskite distribution and insufficient infiltration.
To address these issues, MA gas treatment was introduced to liquefy and recrystallize the perovskite, facilitating its re-infiltration into the porous layer. This treatment successfully enhanced the infiltration rate, short-circuit current density, and overall efficiency, achieving a peak PCE of 5.76%. Both EDS elemental mapping and X-ray photoelectron spectrometer（XPS）depth profiling confirmed an increased proportion of Pb and I within the porous oxide layer, proving that MA gas treatment effectively mitigates poor infiltration. In conclusion, this work demonstrates that MA gas treatment significantly improves perovskite infiltration and device performance, offering a promising strategy to minimize efficiency loss when refilling perovskite into recycled templates for device reuse.

[1] E. Becquerel, "Mémoire sur les effets électriques produits sous l’influence des rayons solaires," Comptes Rendus, 9, 561-567, 1839, doi: 10.4236/wjcmp.2015.54031.
[2] C. E. Fritts, "On a new form of selenium cell, and some electrical discoveries made by its use," American Journal of Science, vol. s3-26, no. 156, p. 465, 1883, doi: 10.2475/ajs.s3-26.156.465.
[3] F. C. Nix and A. W. Treptow, "A Thallous Sulphide Photo-e.m.f. Cell," J. Opt. Soc. Am., vol. 29, no. 11, pp. 457-462, 1939, doi: 10.1364/JOSA.29.000457.
[4] R. S. Ohl, "Light-sensitive electrical device," US Patent 2,402,662, 1946.
[5] D. M. Chapin, C. S. Fuller, and G. L. Pearson, "A New Silicon p‐n Junction Photocell for Converting Solar Radiation into Electrical Power," Journal of Applied Physics, vol. 25, no. 5, pp. 676-677, 2004, doi: 10.1063/1.1721711.
[6] M. A. Green, E. D. Dunlop, M. Yoshita, N. Kopidakis, K. Bothe, and G. Siefer, "Solar cell efficiency tables (version 67)," Prog. Photovolt. Res. Appl., vol. 34, no. 1, pp. 3-15, Jan. 2026, doi: 10.1002/pip.70068.
[7] NREL, "Best Research-Cell Efficiency Chart, " https://www.nrel.gov/pv/cell efficiency.html, (accessed 2026)
[8] L. SE, "Alta sets flexible solar record with 29.1% GaAs cell.," 2018.
[9] 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, 1991/10/01 1991, doi: 10.1038/353737a0.
[10] M. Grätzel, "Dye-sensitized solar cells," Journal of Photochemistry and Photobiology C: Photochemistry Reviews, vol. 4, no. 2, pp. 145-153, 2003/10/31/ 2003, doi: 10.1016/S1389-5567(03)00026-1.
[11] A. Kojima, K. Teshima, Y. Shirai, and T. Miyasaka, "Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells," Journal of the American Chemical Society, vol. 131, no. 17, pp. 6050-6051, 2009/05/06 2009, doi: 10.1021/ja809598r.
[12] N. Koide, A. Islam, Y. Chiba, and L. Han, "Improvement of efficiency of dye-sensitized solar cells based on analysis of equivalent circuit," Journal of Photochemistry and Photobiology A: Chemistry, vol. 182, no. 3, pp. 296-305, 2006/09/10, 2006, doi: 10.1016/j.jphotochem.
[13] G. Instruments, "DSSC: dye sensitized solar cells," https://www.gamry.com/application-notes/physechem/dssc-dye-sensitized-solar-cells/
[14] PVEDUCATION, "IV Curve," https://www.pveducation.org/pvcdrom/solar-cell-operation/iv-curve
[15] PVEDUCATION, "Quantum Efficiency," https://www.pveducation.org/pvcdrom/solar-cell-operation/quantum-efficiency
[16] J. C. Hulteen and R. P. Van Duyne, "Nanosphere lithography: A materials general fabrication process for periodic particle array surfaces," Journal of Vacuum Science & Technology A, vol. 13, no. 3, pp. 1553-1558, 1995, doi: 10.1116/1.579726.
[17] C. L. Haynes and R. P. Van Duyne, "Nanosphere Lithography: A Versatile Nanofabrication Tool for Studies of Size-Dependent Nanoparticle Optics," The Journal of Physical Chemistry B, vol. 105, no. 24, pp. 5599-5611, 2001/06/01 2001, doi: 10.1021/jp010657m.
[18] Xiaoguang Liang, Ruoting Dong, and Johnny C. Ho, "Self-Assembly of Colloidal Spheres toward Fabrication of Hierarchical and Periodic Nanostructures for Technological Applications," Advanced Materials Technologies, Volume4, Issue3, March 2019, 1800541, doi: 10.1002/admt.201800541.
[19] K. Burrows and V. Fthenakis, "Glass needs for a growing photovoltaics industry," Solar Energy Materials and Solar Cells, vol. 132, pp. 455-459, 2015/01/01/ 2015, doi: https://doi.org/10.1016/j.solmat.2014.09.028.
[20] H.-S. Kim, C.-R. Lee, J.-H. Im, K.-B. Lee, T. Moehl, A. Marchioro, S.-J. Moon, R. Humphry-Baker, J.-H. Yum, J. E. Moser, M. Grätzel, and N.-G. Park, "Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%," Scientific Reports, vol. 2, no. 1, pp. 591, 2012/08/21, 2012. doi: 10.1038/srep00591.
[21] M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami, and H. J. Snaith, "Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites," Science, vol. 338, no. 6107, pp. 643-647, 2012/11/02 2012, doi: 10.1126/science.1228604.
[22] J. Burschka et al., "Sequential deposition as a route to high-performance perovskite-sensitized solar cells," (in eng), Nature, vol. 499, no. 7458, pp. 316-9, Jul 18 2013, doi: 10.1038/nature12340.
[23] N. J. Jeon, J. H. Noh, Y. C. Kim, W. S. Yang, S. Ryu, and S. I. Seok, "Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells," Nature Materials, vol. 13, no. 9, pp. 897-903, 2014/09/01 2014, doi: 10.1038/nmat4014.
[24] M. Saliba et al., "Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency," Energy & Environmental Science, 10.1039/C5EE03874J vol. 9, no. 6, pp. 1989-1997, 2016, doi: 10.1039/C5EE03874J.
[25] 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, 1996/10/30/ 1996, doi: 10.1016/0927-0248(96)00063-3.
[26] J. M. Kroon et al., "Nanocrystalline dye-sensitized solar cells having maximum performance," Progress in Photovoltaics: Research and Applications, vol. 15, no. 1, pp. 1-18, 2007/01/01 2007, doi: 10.1002/pip.707.
[27] Y. Kashiwa, Y. Yoshida, and S. Hayase, "All-metal-electrode-type dye sensitized solar cells (transparent conductive oxide-less dye sensitized solar cell) consisting of thick and porous Ti electrode with straight pores," Applied Physics Letters, vol. 92, no. 3, p. 033308, 2008, doi: 10.1063/1.2837633.
[28] Z. Ku, Y. Rong, M. Xu, T. Liu, and H. Han, "Full Printable Processed Mesoscopic CH3NH3PbI3/TiO2 Heterojunction Solar Cells with Carbon Counter Electrode," Scientific Reports, vol. 3, no. 1, p. 3132, 2013/11/04 2013, doi: 10.1038/srep03132.
[29] A. Mei et al., "A hole-conductor–free, fully printable mesoscopic perovskite solar cell with high stability," Science, vol. 345, no. 6194, pp. 295-298, 2014/07/18 2014, doi: 10.1126/science.1254763.
[30] Z. Ku, X. Xia, H. Shen, N. H. Tiep, and H. J. Fan, "A mesoporous nickel counter electrode for printable and reusable perovskite solar cells," Nanoscale, vol. 7, no. 32, pp. 13363-13368, 2015, doi: 10.1039/C5NR03610K.
[31] M.-H. Li et al., "Robust and Recyclable Substrate Template with an Ultrathin Nanoporous Counter Electrode for Organic-Hole-Conductor-Free Monolithic Perovskite Solar Cells," ACS Applied Materials & Interfaces, vol. 9, no. 48, pp. 41845-41854, 2017/12/06 2017, doi: 10.1021/acsami.7b12367.
[32] P.-S. Shen et al., "A novel porous Ti/TiN/Ti thin film as a working electrode for back-contact, monolithic and non-TCO dye-sensitized solar cells," Sustainable Energy & Fuels, vol. 1, no. 4, pp. 851-858, 2017, doi: 10.1039/C6SE00118A.
[33] C.-M. Tsai et al., "Control of preferred orientation with slow crystallization for carbon-based mesoscopic perovskite solar cells attaining efficiency 15%," Journal of Materials Chemistry A, vol. 5, no. 2, pp. 739-747, 2017, doi: 10.1039/C6TA09036B.
[34] G. Grancini et al., "One-Year stable perovskite solar cells by 2D/3D interface engineering," Nature Communications, vol. 8, no. 1, p. 15684, 2017/06/01 2017, doi: 10.1038/ncomms15684.
[35] P. Zhang, G. Kapil, K. Hamada, S. S. Pandey, T. Ma, and S. Hayase, "Study To Observe the Effect of PbI2 Passivation on Carbon Electrode for Perovskite Solar Cells by Quartz Crystal Microbalance System," ACS Sustainable Chemistry & Engineering, vol. 6, no. 8, pp. 10221-10228, 2018/08/06 2018, doi: 10.1021/acssuschemeng.8b01550.
[36] A. Schneider, A. Efrati, S. Alon, M. Sohmer, and L. Etgar, "Green energy by recoverable triple-oxide mesostructured perovskite photovoltaics," Proceedings of the National Academy of Sciences, vol. 117, no. 49, pp. 31010-31017, 2020/12/08 2020, doi: 10.1073/pnas.2013242117.
[37] J. Barichello, L. Vesce, F. Matteocci, E. Lamanna, and A. Di Carlo, "The effect of water in Carbon-Perovskite Solar Cells with optimized alumina spacer," Solar Energy Materials and Solar Cells, vol. 197, pp. 76-83, 2019/08/01/ 2019, doi: 10.1016/j.solmat. 2019.03.029.
[38] Q. Wang et al., "Crystallization Control of Ternary-Cation Perovskite Absorber in Triple-Mesoscopic Layer for Efficient Solar Cells," Advanced Energy Materials, vol. 10, no. 5, p. 1903092, 2020/02/01 2020, doi: 10.1002/aenm.201903092.
[39] K. Cao et al., "Efficient screen printed perovskite solar cells based on mesoscopic TiO2/Al2O3/NiO/carbon architecture," Nano Energy, vol. 17, pp. 171-179, 2015/10/01/ 2015, doi: 10.1016/j.2015.08.009.
[40] G. Mathiazhagan et al., "Double-Mesoscopic Hole-Transport-Material-Free Perovskite Solar Cells: Overcoming Charge-Transport Limitation by Sputtered Ultrathin Al2O3 Isolating Layer," ACS Applied Nano Materials, vol. 3, no. 3, pp. 2463-2471, 2020/03/27 2020, doi: 10.1021/acsanm.9b02563.
[41] N. Posthuma et al., "Development and Analysis of Small Area High Efficiency Interdigitated Back Contact Silicon Solar Cells. 2012, doi: 10.4229/27thEUPVSEC2012-2AO.2.2.
[42] Chen-Fu Lin et al., "Back-contact perovskite solar cells" Semiconductor Science and Technology, Volume 36, Number 8, doi: 10.1088/1361-6641/ac0577.
[43] T. Ma, Q. Song, D. Tadaki, M. Niwano, and A. Hirano-Iwata, "Unveil the Full Potential of Integrated-Back-Contact Perovskite Solar Cells Using Numerical Simulation," ACS Applied Energy Materials, vol. 1, no. 3, pp. 970-975, 2018/03/26 2018, doi: 10.1021/acsaem.8b00044.
[44] X. Lin et al., "Dipole-field-assisted charge extraction in metal-perovskite-metal back-contact solar cells," Nature Communications, vol. 8, no. 1, p. 613, 2017/09/20 2017, doi: 10.1038/s41467-017-00588-3.
[45] C. Goh, S. R. Scully, and M. D. McGehee, "Effects of molecular interface modification in hybrid organic-inorganic photovoltaic cells," Journal of Applied Physics, vol. 101, no. 11, p. 114503, 2007, doi: 10.1063/1.2737977.
[46] S. Kobayashi et al., "Control of carrier density by self-assembled monolayers in organic field-effect transistors," (in eng), Nat Mater, vol. 3, no. 5, pp. 317-22, May 2004, doi: 10.1038/nmat1105.
[47] X. Lin et al., "Effect of Grain Cluster Size on Back-Contact Perovskite Solar Cells," Advanced Functional Materials, vol. 28, no. 45, p. 1805098, 2018/11/01 2018, doi: 10.1002/adfm.201805098
[48] M. Wong-Stringer et al., "A flexible back-contact perovskite solar micro-module," Energy & Environmental Science, vol. 12, no. 6, pp. 1928-1937, 2019, doi: 10.1039/C8EE03517B.
[49] A. N. Jumabekov, J. A. Lloyd, D. M. Bacal, U. Bach, and A. S. R. Chesman, "Fabrication of Back-Contact Electrodes Using Modified Natural Lithography," ACS Applied Energy Materials, vol. 1, no. 3, pp. 1077-1082, 2018/03/26 2018, doi: 10.1021/acsaem.7b00213.
[50] Q. Hou et al., "Back-contact perovskite solar cells with honeycomb-like charge collecting electrodes," Nano Energy, vol. 50, pp. 710-716, 2018/08/01/ 2018, doi: 10.1016/j.nanoen.2018.06.006.
[51] S. Deng et al., "Back-contact perovskite solar cell fabrication via microsphere lithography," Nano Energy, vol. 102, p. 107695, 2022/11/01/ 2022, doi: 10.1016/j.nanoen.2022.107695.
[52] K. J. Prince et al., "Complementary interface formation toward high-efficiency all- back-contact perovskite solar cells," Cell Reports Physical Science, vol. 2, no. 3, p. 100363, 2021/03/24/ 2021, doi: 10.1016/j.xcrp.2021.100363.
[53] K. J. Prince, C. P. Muzzillo, M. Mirzokarimov, C. A. Wolden, and L. M. Wheeler, "All-Back-Contact Perovskite Solar Cells Using Cracked Film Lithography," ACS Applied Energy Materials, vol. 5, no. 8, pp. 9273-9279, 2022/08/22 2022, doi: 10.1021/acsaem.2c01298.
[54] L. Huang et al., "New Films on Old Substrates: Toward Green and Sustainable Energy Production via Recycling of Functional Components from Degraded Perovskite Solar Cells," ACS Sustainable Chemistry & Engineering, vol. 5, no. 4, pp. 3261-3269, 2017/04/03 2017, doi: 10.1021/acssuschemeng.6b03089.
[55] J. M. Kadro et al., "Proof-of-concept for facile perovskite solar cell recycling," Energy & Environmental Science, 10.1039/C6EE02013E vol. 9, no. 10, pp. 3172-3179, 2016, doi: 10.1039/C6EE02013E.
[56] L. Huang et al., "Efficient electron-transport layer-free planar perovskite solar cells via recycling the FTO/glass substrates from degraded devices," Solar Energy Materials and Solar Cells, vol. 152, pp. 118-124, 2016/08/01/ 2016, doi: 10.1016/j.solmat.2016.03.035.
[57] A. Binek et al., "Recycling Perovskite Solar Cells To Avoid Lead Waste," ACS Applied Materials & Interfaces, vol. 8, no. 20, pp. 12881-12886, 2016/05/25 2016, doi: 10.1021/acsami.6b03767.
[58] L. Hong et al., "Improvement and Regeneration of Perovskite Solar Cells via Methylamine Gas Post-Treatment," Advanced Functional Materials, vol. 27, no. 43, p. 1703060, 2017/11/01 2017, doi: 10.1002/adfm.201703060.
[59] R. G. Charles, A. Doolin, R. García-Rodríguez, K. V. Villalobos, and M. L. Davies, "Circular economy for perovskite solar cells – drivers, progress and challenges," Energy & Environmental Science, 10.1039/D3EE00841J vol. 16, no. 9, pp. 3711-3733, 2023, doi: 10.1039/D3EE00841J.
[60] S. Ito et al., "Fabrication of screen-printing pastes from TiO2 powders for dye-sensitised solar cells," Progress in Photovoltaics: Research and Applications, vol. 15, no. 7, pp. 603-612, 2007/11/01 2007, doi: 10.1002/pip.768.
[61] Schütz ER, Majewski M, Ronsin OJJ, Harting J, Schmidt-Mende L. "Controlling Parasitic Nucleation in Methylamine-Treated Perovskite Films via Artificial Seeding and Phase-Field Simulations. " Small Sci. 2026 May 15;6(5):e70301. doi: 10.1002/smsc.70301.