Novel Hole Transporting Materials and Passivation Strategies for Efficient and Stable Perovskite Solar Cells

As the environment becomes increasingly worse since the industrial evolution, attention has been gradually attached on of green and renewable energy. Solar energy, as the energy source of earth, is abundant for humans. Perovskite solar cells (PSCs), as a novel and potential photovoltaic technique, has been overwhelmingly dazzling for more than a decade since it was first reported by Miyasaka in 2009. Its extraordinary optoelectronic properties immediately attract researchers’ tremendous attention and interests. The outstanding properties and simple manufacturing procedure facilitate the constant refreshing of power conversion efficiency (PCE) record, coming to 25.7% at present. However, there are still many obstacles and problems for PSCs on the way to commercialization and industrialization, such as poor stability, unsatisfying efficiency, toxicity, etc. Hole transport layer (HTL) plays an essential role in PSCs in p-i-n structure. Traditional hygroscopic and deliquescent spiro-OMeTAD suffers from poor stability and high cost, which impedes large-scale application. In this thesis, molecular engineering strategies were excused on HTL to get efficient and stable PSCs. Polymeric trithiophene-benzene (TTB) was designed based on previous reported dithiophene-benzene (DTB). One more thiophene was embedded into the main chain to further enhance the π-conjugation but not changed the edge-on orientation on perovskite layer. The device based on dopant-free TTB showed relatively high stability and comparable efficiency compared to that of spiroOMeTAD-based device. Later, we engaged structural engineering on dopant-free phthalocyanine (Pcs) which showed remarkable thermal and chemical stability. Three new Pcs molecules with different substitutions at peripheral sites are designed and are compared with one reported CuPc. Further, we found that pristine spiro could improve the Voc thus enhance the PCE. Pc-1 and CuPc-2 mixed with pristine spiro display higher Voc and PCE than only itself in solar cell. Finally, we achieved 16.0% and 17.1% based on dopant-free CuPc-2 and mixture of CuPc-2 and spiro. CuPc-2 based device preserve 98.5% of its CE after stored under atmosphere condition. Detrimental defect is another main factor affects the stability of PSCs. We proposed quaternary ammonium chloride to passivate the defects on perovskite surface. X-ray photoelectron spectroscopy (XPS) proved the interaction between tetramethylammonium chloride (TC) molecule and metallic lead atom, which could retard the effect of metallic Pb (Pb0) to the efficiency of PSCs. Our strategy showed satisfying results that passivated device showed improved voltage (1.06V) and efficiency (21.7%) compare to control one. Moreover, the passivated device also showed an enhanced stability, retaining 93.2% of its initial PCE after storage in drying cupboard for more than 30 days.
Those strategies will definitely give a guide way to further promote the performance of PSCs in terms of efficiency and stability problem.

(1) Chakhmouradian, A. R. Woodward, P. M. Physics and Chemistry of Minerals 2014, 41, 387. (2) Green, M. A., Ho-Baillie, A. Snaith, H. J. Nature Photonics 2014, 8, 506. (3) Goldschmidt, V. M. Die Naturwissenschaften 1926, 14, 477. (4) Saparov, B. Mitzi, D. B. Chemical Reviews 2016, 116, 4558. (5) Li, C., Lu, X., Ding, W., Feng, L., Gao, Y. Guo, Z. Acta Crystallographica Section B Structural Science 2008, 64, 702. (6) Xing, G., Mathews, N., Sun, S., Lim, S. S., Lam, Y. M., Gratzel, M., Mhaisalkar, S. Sum, T. C. Science 2013, 342, 344. (7) Stranks, S. D., Eperon, G. E., Grancini, G., Menelaou, C., Alcocer, M. J., Leijtens, T., Herz, L. M., Petrozza, A. Snaith, H. J. Science 2013, 342, 341. (8) Ponseca, C. S., Savenije, T. J., Abdellah, M., Zheng, K., Yartsev, A., Pascher, T., Harlang, T., Chabera, P., Pullerits, T., Stepanov, A. Journal of the American Chemical Society 2014, 136, 5189. (9) De Angelis, F. Petrozza, A. Nature Materials 2018, 17, 383. (10) Kojima, A., Teshima, K., Shirai, Y. Miyasaka, T. Journal of the American Chemical Society 2009, 131, 6050. (11) Im, J. H., Lee, C. R., Lee, J. W., Park, S. W. Park, N. G. Nanoscale 2011, 3, 4088. (12) Bach, U., Lupo, D., Comte, P., Moser, J. E., Weissörtel, F., Salbeck, J., Spreitzer, H. Grätzel, M. Nature 1998, 395, 583. (13) Kim, H.-S., Lee, C.-R., Im, J.-H., Lee, K.-B., Moehl, T., Marchioro, A., Moon, S.-J., Humphry-Baker, R., Yum, J.-H., Moser, J. E. Scientific Reports 2012, 2, 591. (14) Jeon, N. J., Noh, J. H., Kim, Y. C., Yang, W. S., Ryu, S. Seok, S. I. Nature Materials 2014, 13, 897. (15) Ahn, N., Son, D. Y., Jang, I. H., Kang, S. M., Choi, M. Park, N. G. Journal of the American Chemical Society 2015, 137, 8696. (16) Xiao, M., Huang, F., Huang, W., Dkhissi, Y., Zhu, Y., Etheridge, J., Gray-Weale, A., Bach, U., Cheng, Y. B. Spiccia, L. Angewandte Chemie-International Edition 2014, 53, 9898. (17) Bi, D. Q., Yi, C. Y., Luo, J. S., Decoppet, J. D., Zhang, F., Zakeeruddin, S. M., Li, X., Hagfeldt, A. Gratzel, M. Nature Energy 2016, 1, 16142. (18) Zhao, P., Kim, B. J., Ren, X., Lee, D. G., Bang, G. J., Jeon, J. B., Kim, W. B. Jung, H. S. Advanced Materials 2018, 30, e1802763. (19) Yang, W. S., Noh, J. H., Jeon, N. J., Kim, Y. C., Ryu, S., Seo, J. Seok, S. I. Science 2015, 348, 1234. (20) Burschka, J., Pellet, N., Moon, S. J., Humphry-Baker, R., Gao, P., Nazeeruddin, M. K. Gratzel, M. Nature 2013, 499, 316. (21) Jiang, Q., Zhang, L., Wang, H., Yang, X., Meng, J., Liu, H., Yin, Z., Wu, J., Zhang, X. You, J. Nature Energy 2016, 2, 16177. (22) Jiang, Q., Zhao, Y., Zhang, X., Yang, X., Chen, Y., Chu, Z., Ye, Q., Li, X., Yin, Z. You, J. Nature Photonics 2019, 13, 460. (23) Noh, J. H., Im, S. H., Heo, J. H., Mandal, T. N. Seok, S. I. Nano Letters 2013, 13, 1764. (24) Jeon, N. J., Noh, J. H., Yang, W. S., Kim, Y. C., Ryu, S., Seo, J. Seok, S. I. Nature 2015, 517, 476. (25) Saliba, M., Matsui, T., Seo, J.-Y., Domanski, K., Correa-Baena, J.-P., Nazeeruddin, M. K., Zakeeruddin, S. M., Tress, W., Abate, A., Hagfeldt, A. Energy & Environmental Science 2016, 9, 1989. (26) Abdi-Jalebi, M., Andaji-Garmaroudi, Z., Cacovich, S., Stavrakas, C., Philippe, B., Richter, J. M., Alsari, M., Booker, E. P., Hutter, E. M., Pearson, A. J. Nature 2018, 555, 497. (27) Ran, C., Xu, J., Gao, W., Huang, C. Dou, S. Chemical Society Reviews 2018, 47, 4581. (28) Yang, S., Dai, J., Yu, Z., Shao, Y., Zhou, Y., Xiao, X., Zeng, X. C. Huang, J. Journal of the American Chemical Society 2019, 141, 5781. (29) Chen, B., Rudd, P. N., Yang, S., Yuan, Y. Huang, J. Chemical Society Reviews 2019, 48, 3842. (30) Meng, L., Sun, C., Wang, R., Huang, W., Zhao, Z., Sun, P., Huang, T., Xue, J., Lee, J.-W., Zhu, C. Journal of the American Chemical Society 2018, 140, 17255. (31) Wang, R., Xue, J., Wang, K. L., Wang, Z. K., Luo, Y., Fenning, D., Xu, G., Nuryyeva, S., Huang, T., Zhao, Y. Science 2019, 366, 1509. (32) Jiang, Q., Chu, Z., Wang, P., Yang, X., Liu, H., Wang, Y., Yin, Z., Wu, J., Zhang, X. You, J. Advanced Materials 2017, 29, 1703852. (33) Pang, S., Hu, H., Zhang, J., Lv, S., Yu, Y., Wei, F., Qin, T., Xu, H., Liu, Z. Cui, G. Chemistry of Materials 2014, 26, 1485. (34) National Renewable Energy Laboratory, https://www.nrel.gov/pv/cell. (35) Shockley, W. Queisser, H. J. Journal of Applied Physics 1961, 32, 510. (36) Heo, J. H., You, M. S., Chang, M. H., Yin, W., Ahn, T. K., Lee, S.-J., Sung, S.-J., Kim, D. H. Im, S. H. Nano Energy 2015, 15, 530. (37) Yoo, J. J., Seo, G., Chua, M. R., Park, T. G., Lu, Y., Rotermund, F., Kim, Y.-K., Moon, C. S., Jeon, N. J., Correa-Baena, J.-P. Nature 2021, 590, 587. (38) Jeong, M., Choi, I. W., Go, E. M., Cho, Y., Kim, M., Lee, B., Jeong, S., Jo, Y., Choi, H. W., Lee, J. Science 2020, 369, 1615. (39) Jeong, J., Kim, M., Seo, J., Lu, H., Ahlawat, P., Mishra, A., Yang, Y., Hope, M. A., Eickemeyer, F. T., Kim, M. Nature 2021, 592, 381. (40) Sun, Y. H., Wang, C. L., Zhao, D. W., Yu, J. S., Yin, X. X., Grice, C. R., Awni, R. A., Shrestha, N., Yu, Y., Guan, L. Solar RRL 2018, 2, 1700175. (41) Noh, J. H., Jeon, N. J., Choi, Y. C., Nazeeruddin, M. K., Grätzel, M. Seok, S. I. Journal of Materials Chemistry A 2013, 1, 11842. (42) Lee, M. M., Teuscher, J., Miyasaka, T., Murakami, T. N. Snaith, H. J. Science 2012, 338, 643. (43) Heo, J. H., Im, S. H., Noh, J. H., Mandal, T. N., Lim, C.-S., Chang, J. A., Lee, Y. H., Kim, H.-j., Sarkar, A., Nazeeruddin, M. K. Nature Photonics 2013, 7, 486. (44) Eperon, G. E., Burlakov, V. M., Docampo, P., Goriely, A. Snaith, H. J. Advanced Functional Materials 2014, 24, 151. (45) Liu, M., Johnston, M. B. Snaith, H. J. Nature 2013, 501, 395. (46) Malinkiewicz, O., Yella, A., Lee, Y. H., Espallargas, G. M., Graetzel, M., Nazeeruddin, M. K. Bolink, H. J. Nature Photonics 2014, 8, 128. (47) Burschka, J., Pellet, N., Moon, S.-J., Humphry-Baker, R., Gao, P., Nazeeruddin, M. K. Grätzel, M. Nature 2013, 499, 316. (48) Kim, G., Min, H., Lee, K. S., Lee, D. Y., Yoon, S. M. Seok, S. I. Science 2020, 370, 108. (49) Ma, Y., Liu, N., Zai, H., Fan, R., Kang, J., Yang, X., Pei, F., Zhou, W., Wang, H., Chen, Y. Journal of Materials Chemistry A 2022, 10, 3506. (50) Chao, L., Xia, Y., Li, B., Xing, G., Chen, Y. Huang, W. Chem 2019, 5, 995. (51) Vak, D., Hwang, K., Faulks, A., Jung, Y. S., Clark, N., Kim, D. Y., Wilson, G. J. Watkins, S. E. Advanced Energy Materials 2015, 5, 1401539. (52) Schmidt, T. M., Larsen-Olsen, T. T., Carle, J. E., Angmo, D. Krebs, F. C. Advanced Energy Materials 2015, 5, 1500569. (53) Hwang, K., Jung, Y. S., Heo, Y. J., Scholes, F. H., Watkins, S. E., Subbiah, J., Jones, D. J., Kim, D. Y. Vak, D. Advanced Materials 2015, 27, 1241. (54) Tait, J. G., Manghooli, S., Qiu, W., Rakocevic, L., Kootstra, L., Jaysankar, M., Masse de la Huerta, C. A., Paetzold, U. W., Gehlhaar, R., Cheyns, D. Journal of Materials Chemistry A 2016, 4, 3792. (55) Huang, H., Shi, J., Zhu, L., Li, D., Luo, Y. Meng, Q. Nano Energy 2016, 27, 352. (56) Heo, J. H., Lee, M. H., Jang, M. H. Im, S. H. Journal of Materials Chemistry A 2016, 4, 17636. (57) Yang, Z. B., Chueh, C. C., Zuo, F., Kim, J. H., Liang, P. W. Jen, A. K. Y. Advanced Energy Materials 2015, 5, 1500328. (58) Deng, Y., Peng, E., Shao, Y., Xiao, Z., Dong, Q. Huang, J. Energy & Environmental Science 2015, 8, 1544. (59) Wu, W.-Q., Wang, Q., Fang, Y., Shao, Y., Tang, S., Deng, Y., Lu, H., Liu, Y., Li, T., Yang, Z. Nature Communications 2018, 9, 1625. (60) Lee, I., Yun, J. H., Son, H. J. Kim, T.-S. ACS Applied Materials & Interfaces 2017, 9, 7029. (61) Yue, Y., Salim, N., Wu, Y., Yang, X., Islam, A., Chen, W., Liu, J., Bi, E., Xie, F., Cai, M. Advanced Materials 2016, 28, 10738. (62) Yin, X., Guan, L., Yu, J., Zhao, D., Wang, C., Shrestha, N., Han, Y., An, Q., Zhou, J., Zhou, B. Nano Energy 2017, 40, 163. (63) Jung, E. H., Jeon, N. J., Park, E. Y., Moon, C. S., Shin, T. J., Yang, T.-Y., Noh, J. H. Seo, J. Nature 2019, 567, 511. (64) Ono, L. K., Liu, S. F. Qi, Y. Angewandte Chemie-International Edition 2020, 59, 6676. (65) Ball, J. M. Petrozza, A. Nature Energy 2016, 1, 16149. (66) Azpiroz, J. M., Mosconi, E., Bisquert, J. De Angelis, F. Energy & Environmental Science 2015, 8, 2118. (67) Snaith, H. J., Abate, A., Ball, J. M., Eperon, G. E., Leijtens, T., Noel, N. K., Stranks, S. D., Wang, J. T.-W., Wojciechowski, K. Zhang, W. The Journal of Physical Chemistry Letters 2014, 5, 1511. (68) Philippe, B., Park, B.-W., Lindblad, R., Oscarsson, J., Ahmadi, S., Johansson, E. M. J. Rensmo, H. Chemistry of Materials 2015, 27, 1720. (69) Christians, J. A., Miranda Herrera, P. A. Kamat, P. V. Journal of the American Chemical Society 2015, 137, 1530. (70) Niu, G., Guo, X. Wang, L. Journal of Materials Chemistry A 2015, 3, 8970. (71) Conings, B., Drijkoningen, J., Gauquelin, N., Babayigit, A., D'Haen, J., D'Olieslaeger, L., Ethirajan, A., Verbeeck, J., Manca, J., Mosconi, E. Advanced Energy Materials 2015, 5, 1500477. (72) Rong, Y. G., Liu, L. F., Mei, A. Y., Li, X. Han, H. W. Advanced Energy Materials 2015, 5, 1501066. (73) Lang, F., Shargaieva, O., Brus, V. V., Neitzert, H. C., Rappich, J. Nickel, N. H. Advanced Materials 2018, 30, 1702905. (74) Brus, V. V., Lang, F., Bundesmann, J., Seidel, S., Denker, A., Rech, B., Landi, G., Neitzert, H. C., Rappich, J. Nickel, N. H. Advanced Electronic Materials 2017, 3, 1600438. (75) Zhao, J., Deng, Y., Wei, H., Zheng, X., Yu, Z., Shao, Y., Shield, J. E. Huang, J. Science Advance 2017, 3, eaao5616. (76) Yin, W. J., Shi, T. T. Yan, Y. F. Applied Physics Letters 2014, 104, 063903. (77) Kim, G. Y., Senocrate, A., Yang, T. Y., Gregori, G., Gratzel, M. Maier, J. Nat Mater 2018, 17, 445. (78) Aristidou, N., Sanchez-Molina, I., Chotchuangchutchaval, T., Brown, M., Martinez, L., Rath, T. Haque, S. A. Angew Chem Int Ed Engl 2015, 54, 8208. (79) O'Mahony, F. T. F., Lee, Y. H., Jellett, C., Dmitrov, S., Bryant, D. T. J., Durrant, J. R., O'Regan, B. C., Graetzel, M., Nazeeruddin, M. K. Haque, S. A. Journal of Materials Chemistry A 2015, 3, 7219. (80) Pang, S., Zhou, Y., Wang, Z., Yang, M., Krause, A. R., Zhou, Z., Zhu, K., Padture, N. P. Cui, G. J Am Chem Soc 2016, 138, 750. (81) Raga, S. R., Ono, L. K. Qi, Y. Journal of Materials Chemistry A 2016, 4, 2494. (82) Askar, A. M., Bernard, G. M., Wiltshire, B., Shankar, K. Michaelis, V. K. Journal of Physical Chemistry C 2017, 121, 1013. (83) Leguy, A. M. A., Hu, Y., Campoy-Quiles, M., Alonso, M. I., Weber, O. J., Azarhoosh, P., van Schilfgaarde, M., Weller, M. T., Bein, T., Nelson, J. Chemistry of Materials 2015, 27, 3397. (84) Motti, S. G., Meggiolaro, D., Barker, A. J., Mosconi, E., Perini, C. A. R., Ball, J. M., Gandini, M., Kim, M., De Angelis, F. Petrozza, A. Nature Photonics 2019, 13, 532. (85) Pellet, N., Gao, P., Gregori, G., Yang, T. Y., Nazeeruddin, M. K., Maier, J. Gratzel, M. Angewandte Chemie-International Edition 2014, 53, 3151. (86) Lee, J. W., Kim, D. H., Kim, H. S., Seo, S. W., Cho, S. M. Park, N. G. Advanced Energy Materials 2015, 5, 1501310. (87) Jeon, N. J., Noh, J. H., Yang, W. S., Kim, Y. C., Ryu, S., Seo, J. Seok, S. I. Nature 2015, 517, 476. (88) Jeong, J., Kim, H.-B., Kim, H., Walker, B., Song, S., Heo, J., Yoon, Y. J., Jo, Y., Choi, H., Kim, G.-H. ACS Energy Letters 2016, 1, 712. (89) Wang, L., McCleese, C., Kovalsky, A., Zhao, Y. Burda, C. Journal of the American Chemical Society 2014, 136, 12205. (90) Chen, Q., Zhou, H., Song, T.-B., Luo, S., Hong, Z., Duan, H.-S., Dou, L., Liu, Y. Yang, Y. Nano Letters 2014, 14, 4158. (91) Li, X., Dar, M. I., Yi, C., Luo, J., Tschumi, M., Zakeeruddin, S. M., Nazeeruddin, M. K., Han, H. Gratzel, M. Nature Chemistry 2015, 7, 703. (92) Wang, Z., Lin, Q., Chmiel, F. P., Sakai, N., Herz, L. M. Snaith, H. J. Nature Energy 2017, 2, 17135. (93) Bi, D., Li, X., Milić, J. V., Kubicki, D. J., Pellet, N., Luo, J., LaGrange, T., Mettraux, P., Emsley, L., Zakeeruddin, S. M. Nature Communications 2018, 9, 4482. (94) Tan, H., Jain, A., Voznyy, O., Lan, X., Garcia de Arquer, F. P., Fan, J. Z., Quintero-Bermudez, R., Yuan, M., Zhang, B., Zhao, Y. Science 2017, 355, 722. (95) Luo, D., Yang, W., Wang, Z., Sadhanala, A., Hu, Q., Su, R., Shivanna, R., Trindade, G. F., Watts, J. F., Xu, Z. Science 2018, 360, 1442. (96) Choi, K., Lee, J., Kim, H. I., Park, C. W., Kim, G.-W., Choi, H., Park, S., Park, S. A. Park, T. Energy & Environmental Science 2018, 11, 3238. (97) Yoo, J. J., Wieghold, S., Sponseller, M. C., Chua, M. R., Bertram, S. N., Hartono, N. T. P., Tresback, J. S., Hansen, E. C., Correa-Baena, J. P., Bulovic, V. Energy & Environmental Science 2019, 12, 2192. (98) Jo, Y., Oh, K. S., Kim, M., Kim, K. H., Lee, H., Lee, C. W. Kim, D. S. Advanced Materials Interfaces 2016, 3, 1500768. (99) Kim, M., Kim, G.-H., Lee, T. K., Choi, I. W., Choi, H. W., Jo, Y., Yoon, Y. J., Kim, J. W., Lee, J., Huh, D. Joule 2019, 3, 2179. (100) Min, H., Kim, M., Lee, S. U., Kim, H., Kim, G., Choi, K., Lee, J. H. Seok, S. I. Science 2019, 366, 749. (101) Zhang, C., Liang, S., Liu, W., Eickemeyer, F. T., Cai, X., Zhou, K., Bian, J., Zhu, H., Zhu, C., Wang, N. Nature Energy 2021, 6, 1154. (102) Zhang, F., Yi, C., Wei, P., Bi, X., Luo, J., Jacopin, G., Wang, S., Li, X., Xiao, Y., Zakeeruddin, S. M. Advanced Energy Materials 2016, 6, 1600401. (103) Huang, C., Fu, W., Li, C.-Z., Zhang, Z., Qiu, W., Shi, M., Heremans, P., Jen, A. K. Y. Chen, H. Journal of the American Chemical Society 2016, 138, 2528. (104) Li, Z. a., Zhu, Z., Chueh, C.-C., Jo, S. B., Luo, J., Jang, S.-H. Jen, A. K. Y. Journal of the American Chemical Society 2016, 138, 11833. (105) Zhang, F., Wang, Z. Q., Zhu, H. W., Pellet, N., Luo, J. S., Yi, C. Y., Liu, X. C., Liu, H. L., Wang, S. R., Li, X. G. Nano Energy 2017, 41, 469. (106) Chen, S., Liu, P., Hua, Y., Li, Y., Kloo, L., Wang, X., Ong, B., Wong, W.-K. Zhu, X. ACS Applied Materials & Interfaces 2017, 9, 13231. (107) Arora, N., Wetzel, C., Dar, M. I., Mishra, A., Yadav, P., Steck, C., Zakeeruddin, S. M., Bäuerle, P. Grätzel, M. ACS Applied Materials & Interfaces 2017, 9, 44423. (108) Zhang, J., Xu, B., Yang, L., Mingorance, A., Ruan, C., Hua, Y., Wang, L., Vlachopoulos, N., Lira-Cantú, M., Boschloo, G. Advanced Energy Materials 2017, 7, 1602736. (109) Yang, L., Cai, F., Yan, Y., Li, J., Liu, D., Pearson, A. J. Wang, T. Advanced Functional Materials 2017, 27, 1702613. (110) Liu, X. Y., Zheng, X. L., Wang, Y. L., Chen, Z. L., Yao, F., Zhang, Q., Fang, G. J., Chen, Z. K., Huang, W. Xu, Z. X. Chemsuschem 2017, 10, 2833. (111) Rakstys, K., Paek, S., Gao, P., Gratia, P., Marszalek, T., Grancini, G., Cho, K. T., Genevicius, K., Jankauskas, V., Pisula, W. Journal of Materials Chemistry A 2017, 5, 7811. (112) Zheng, X. L., Wang, Y. L., Hu, J. H., Yang, G., Guo, Z., Xia, J. L., Xu, Z. X. Fang, G. J. Journal of Materials Chemistry A 2017, 5, 24416. (113) Guan, L., Yin, X., Zhao, D., Wang, C., An, Q., Yu, J., Shrestha, N., Grice, C. R., Awni, R. A., Yu, Y. Journal of Materials Chemistry A 2017, 5, 23319. (114) Xue, Y. Y., Wu, Y. Li, Y. Journal of Power Sources 2017, 344, 160. (115) Yang, G., Wang, Y. L., Xu, J. J., Lei, H. W., Chen, C., Shan, H. Q., Liu, X. Y., Xu, Z. X. Fang, G. J. Nano Energy 2017, 31, 322. (116) Pham, H. D., Do, T. T., Kim, J., Charbonneau, C., Manzhos, S., Feron, K., Tsoi, W. C., Durrant, J. R., Jain, S. M. Sonar, P. Advanced Energy Materials 2018, 8, 1703007. (117) Yin, C., Lu, J., Xu, Y., Yun, Y., Wang, K., Li, J., Jiang, L., Sun, J., Scully, A. D., Huang, F. Advanced Energy Materials 2018, 8, 1800538. (118) Guo, H., Zhang, H., Shen, C., Zhang, D., Liu, S., Wu, Y. Zhu, W.-H. Angewandte Chemie-International Edition 2020, 59, 1. (119) Jo, J. W., Bae, S., Liu, F., Russell, T. P. Jo, W. H. Advanced Functional Materials 2015, 25, 120. (120) Kim, G.-W., Kang, G., Kim, J., Lee, G.-Y., Kim, H. I., Pyeon, L., Lee, J. Park, T. Energy & Environmental Science 2016, 9, 2326. (121) Kim, G.-W., Lee, J., Kang, G., Kim, T. Park, T. Advanced Energy Materials 2018, 8, 1701935. (122) Bi, C., Wang, Q., Shao, Y., Yuan, Y., Xiao, Z. Huang, J. Nature Communications 2015, 6, 7747. (123) Liao, H.-C., Tam, T. L. D., Guo, P., Wu, Y., Manley, E. F., Huang, W., Zhou, N., Soe, C. M. M., Wang, B., Wasielewski, M. R. Advanced Energy Materials 2016, 6, 1600502. (124) Kranthiraja, K., Gunasekar, K., Kim, H., Cho, A.-N., Park, N.-G., Kim, S., Kim, B. J., Nishikubo, R., Saeki, A., Song, M. Advanced Materials 2017, 29, 1700183. (125) Xu, Y., Bu, T., Li, M., Qin, T., Yin, C., Wang, N., Li, R., Zhong, J., Li, H., Peng, Y. ChemSusChem 2017, 10, 2578. (126) Cai, F., Cai, J., Yang, L., Li, W., Gurney, R. S., Yi, H., Iraqi, A., Liu, D. Wang, T. Nano Energy 2018, 45, 28. (127) Liu, J., Ge, Q., Zhang, W., Ma, J., Ding, J., Yu, G. Hu, J. Nano Research 2018, 11, 185. (128) Kumar, C. V., Sfyri, G., Raptis, D., Stathatos, E. Lianos, P. Rsc Advances 2015, 5, 3786. (129) Cheng, M., Li, Y. Y., Safdari, M., Chen, C., Liu, P., Kloo, L. Sun, L. C. Advanced Energy Materials 2017, 7, 1602556. (130) Cao, J., Li, C., Lv, X., Feng, X., Meng, R., Wu, Y. Tang, Y. Journal of the American Chemical Society 2018, 140, 11577. (131) Yu, Z., Wang, L., Mu, X., Chen, C.-C., Wu, Y., Cao, J. Tang, Y. Angewandte Chemie International Edition 2021, 60, 6294. (132) Jeon, N. J., Lee, H. G., Kim, Y. C., Seo, J., Noh, J. H., Lee, J. Seok, S. I. Journal of the American Chemical Society 2014, 136, 7837. (133) Zhang, L. Z., Liu, C., Zhang, J., Li, X. N., Cheng, C., Tian, Y. Q., Jen, A. K. Y. Xu, B. M. Advanced Materials 2018, 30, 1804028. (134) Sun, X., Xue, Q., Zhu, Z., Xiao, Q., Jiang, K., Yip, H.-L., Yan, H. Li, Z. a. Chemical Science 2018, 9, 2698. (135) Leijtens, T., Giovenzana, T., Habisreutinger, S. N., Tinkham, J. S., Noel, N. K., Kamino, B. A., Sadoughi, G., Sellinger, A. Snaith, H. J. ACS Applied Materials & Interfaces 2016, 8, 5981. (136) Zhang, L. Z., Liu, C., Wang, X. Z., Tian, Y. N., Jen, A. K. Y. Xu, B. M. Advanced Functional Materials 2019, 29, 1904856. (137) Barranco, A., Lopez‐Santos, M. C., Idigoras, J., Aparicio, F. J., Obrero‐Perez, J., Lopez‐Flores, V., Contreras‐Bernal, L., Rico, V., Ferrer, J., Espinos, J. P. Advanced Energy Materials 2019, 10, 1901524. (138) Tan, B., Raga, S. R., Chesman, A. S. R., Furer, S. O., Zheng, F., McMeekin, D. P., Jiang, L. C., Mao, W. X., Lin, X. F., Wen, X. M. Advanced Energy Materials 2019, 9, 1901519. (139) Saliba, M., Orlandi, S., Matsui, T., Aghazada, S., Cavazzini, M., Correa-Baena, J. P., Gao, P., Scopelliti, R., Mosconi, E., Dahmen, K. H. Nature Energy 2016, 1, 15017. (140) Xu, B., Zhang, J., Hua, Y., Liu, P., Wang, L., Ruan, C., Li, Y., Boschloo, G., Johansson, E. M. J., Kloo, L. Chem 2017, 2, 676. (141) Jeon, N. J., Na, H., Jung, E. H., Yang, T. Y., Lee, Y. G., Kim, G., Shin, H. W., Seok, S. I., Lee, J. Seo, J. Nature Energy 2018, 3, 682. (142) Cai, B., Xing, Y. D., Yang, Z., Zhang, W. H. Qiu, J. S. Energy & Environmental Science 2013, 6, 1480. (143) Liu, J., Wu, Y. Z., Qin, C. J., Yang, X. D., Yasuda, T., Islam, A., Zhang, K., Peng, W. Q., Chen, W. Han, L. Y. Energy & Environmental Science 2014, 7, 2963. (144) Guo, H., Zhang, H., Shen, C., Zhang, D., Liu, S., Wu, Y. Zhu, W.-H. Angewandte Chemie International Edition 2021, 60, 2674. (145) Bi, D., Yang, L., Boschloo, G., Hagfeldt, A. Johansson, E. M. J. The Journal of Physical Chemistry Letters 2013, 4, 1532. (146) Jung, E. H., Jeon, N. J., Park, E. Y., Moon, C. S., Shin, T. J., Yang, T. Y., Noh, J. H. Seo, J. Nature 2019, 567, 511. (147) Jeong, M. J., Yeom, K. M., Kim, S. J., Jung, E. H. Noh, J. H. Energy & Environmental Science 2021, 14, 2419. (148) Pham, H. D., Yang, T. C.-J., Jain, S. M., Wilson, G. J. Sonar, P. 2020, 10, 1903326. (149) Gao, K., Xu, B., Hong, C. S., Shi, X. L., Liu, H. B., Li, X. S., Xie, L. H. Jen, A. K. Y. Advanced Energy Materials 2018, 8, 1800809. (150) Wu, J. C., Liu, C., Deng, X., Zhang, L. Z., Hu, M. M., Tang, J., Tan, W. C., Tian, Y. Q. Xu, B. M. Rsc Advances 2017, 7, 45478. (151) Kim, G.-W., Lee, J., Kang, G., Kim, T. Park, T. Advanced Energy Materials 2018, 8, 1701935. (152) Urbani, M., Ragoussi, M.-E., Nazeeruddin, M. K. Torres, T. Coordination Chemistry Reviews 2019, 381, 1. (153) Van Nostrum, C. F. Nolte, R. J. M. Chemical Communications 1996, 2385. (154) Wasielewski, M. R. Accounts of Chemical Research 2009, 42, 1910. (155) Imahori, H., Umeyama, T., Kurotobi, K. Takano, Y. Chemical Communications 2012, 48, 4032. (156) Rawling, T. McDonagh, A. Coordination Chemistry Reviews 2007, 251, 1128. (157) Guillaud, G., Simon, J. Germain, J. P. Coordination Chemistry Reviews 1998, 178-180, 1433. (158) Martínez-Díaz, M. V., de la Torre, G. Torres, T. Chemical Communications 2010, 46, 7090. (159) Martín-Gomis, L., Fernández-Lázaro, F. Sastre-Santos, Á. Journal of Materials Chemistry A 2014, 2, 15672. (160) Brogdon, P., Cheema, H. Delcamp, J. H. ChemSusChem 2018, 11, 86. (161) Wu, S., Liu, Q., Zheng, Y., Li, R. Peng, T. Journal of Power Sources 2017, 359, 303. (162) Jin, S., Wei, Y., Huang, F., Yang, X., Luo, D., Fang, Y., Zhao, Y., Guo, Q., Huang, Y. Wu, J. Journal of Power Sources 2018, 404, 64. (163) Mozaffari, M., Behjat, A. Torabi, N. Journal of Materials Science: Materials in Electronics 2018, 29, 18187. (164) Wang, J.-M., Wang, Z.-K., Li, M., Hu, K.-H., Yang, Y.-G., Hu, Y., Gao, X.-Y. Liao, L.-S. ACS Applied Materials & Interfaces 2017, 9, 13240. (165) Zhang, X.-F., Zhou, X., Zhang, L. Xu, B. Journal of Materials Chemistry A 2018, 6, 12515. (166) Seo, J., Jeon, N. J., Yang, W. S., Shin, H.-W., Ahn, T. K., Lee, J., Noh, J. H. Seok, S. I. Advanced Energy Materials 2015, 5, 1501320. (167) Nouri, E., Wang, Y.-L., Chen, Q., Xu, J.-J., Dracopoulos, V., Sygellou, L., Xu, Z.-X., Mohammadi, M. R. Lianos, P. Electrochimica Acta 2016, 222, 1417. (168) Zhao, J. H., Mu, X., Wang, L., Fang, Z., Zou, X. Cao, J. Angewandte Chemie-International Edition 2022, 61, e202116308. (169) Fang, Z., Wang, L., Mu, X., Chen, B., Xiong, Q., Wang, W. D., Ding, J., Gao, P., Wu, Y. Cao, J. Journal of the American Chemical Society 2021, 143, 18989. (170) Habisreutinger, S. N., Leijtens, T., Eperon, G. E., Stranks, S. D., Nicholas, R. J. Snaith, H. J. Nano Letters 2014, 14, 5561. (171) Kim, Y. C., Yang, T. Y., Jeon, N. J., Im, J., Jang, S., Shin, T. J., Shin, H. W., Kim, S., Lee, E., Kim, S. Energy & Environmental Science 2017, 10, 2109. (172) Jiang, X., Yu, Z., Lai, J., Zhang, Y., Lei, N., Wang, D. Sun, L. Science China Chemistry 2017, 60, 423. (173) Duong, T., Peng, J., Walter, D., Xiang, J., Shen, H., Chugh, D., Lockrey, M., Zhong, D., Li, J., Weber, K. ACS Energy Letters 2018, 3, 2441. (174) Zheng, X., Wang, Y., Hu, J., Yang, G., Guo, Z., Xia, J., Xu, Z. Fang, G. Journal of Materials Chemistry A 2017, 5, 24416. (175) Hu, Q., Rezaee, E., Li, M., Chen, Q., Cao, Y., Mayukh, M., McGrath, D. V. Xu, Z.-X. ACS Applied Materials & Interfaces 2019, 11, 36535. (176) Yu, Z., Wang, L., Mu, X., Chen, C. C., Wu, Y., Cao, J. Tang, Y. Angewandte Chemie-International Edition 2021, 60, 6294. (177) Pazos-Outón, L. M., Xiao, T. P. Yablonovitch, E. The Journal of Physical Chemistry Letters 2018, 9, 1703. (178) Saliba, M., Matsui, T., Seo, J. Y., Domanski, K., Correa-Baena, J. P., Nazeeruddin, M. K., Zakeeruddin, S. M., Tress, W., Abate, A., Hagfeldt, A. Energy Environ Sci 2016, 9, 1989. (179) Quan, L. N., Yuan, M., Comin, R., Voznyy, O., Beauregard, E. M., Hoogland, S., Buin, A., Kirmani, A. R., Zhao, K., Amassian, A. Journal of the American Chemical Society 2016, 138, 2649. (180) Grancini, G., Roldán-Carmona, C., Zimmermann, I., Mosconi, E., Lee, X., Martineau, D., Narbey, S., Oswald, F., De Angelis, F., Graetzel, M. Nature Communications 2017, 8, 15684. (181) deQuilettes, D. W., Koch, S., Burke, S., Paranji, R. K., Shropshire, A. J., Ziffer, M. E. Ginger, D. S. ACS Energy Letters 2016, 1, 438. (182) Zhang, Y., Li, Y., Zhang, L., Hu, H., Tang, Z., Xu, B. Park, N. G. Advanced Energy Materials 2021, 11, 2102538. (183) Ke, W., Xiao, C., Wang, C., Saparov, B., Duan, H. S., Zhao, D., Xiao, Z., Schulz, P., Harvey, S. P., Liao, W. Advanced Materials 2016, 28, 5214. (184) Wen, T. Y., Yang, S., Liu, P. F., Tang, L. J., Qiao, H. W., Chen, X., Yang, X. H., Hou, Y. Yang, H. G. Advanced Energy Materials 2018, 8, 1703143. (185) Peng, J., Khan, J. I., Liu, W. Z., Ugur, E., Duong, T., Wu, Y. L., Shen, H. P., Wang, K., Dang, H., Aydin, E. Advanced Energy Materials 2018, 8, 1801208. (186) Zheng, X., Chen, B., Dai, J., Fang, Y., Bai, Y., Lin, Y., Wei, H., Zeng, Xiao C. Huang, J. Nature Energy 2017, 2, 17102. (187) Bu, T., Li, J., Zheng, F., Chen, W., Wen, X., Ku, Z., Peng, Y., Zhong, J., Cheng, Y.-B. Huang, F. Nature Communications 2018, 9, 4609. (188) Son, D.-Y., Kim, S.-G., Seo, J.-Y., Lee, S.-H., Shin, H., Lee, D. Park, N.-G. Journal of the American Chemical Society 2018, 140, 1358. (189) Kubicki, D. J., Prochowicz, D., Hofstetter, A., Zakeeruddin, S. M., Grätzel, M. Emsley, L. Journal of the American Chemical Society 2017, 139, 14173. (190) Abdi-Jalebi, M., Dar, M. I., Sadhanala, A., Senanayak, S. P., Franckevicius, M., Arora, N., Hu, Y. Y., Nazeeruddin, M. K., Zakeeruddin, S. M., Gratzel, M. Advanced Energy Materials 2016, 6, 1502472. (191) Saliba, M., Matsui, T., Domanski, K., Seo, J. Y., Ummadisingu, A., Zakeeruddin, S. M., Correa-Baena, J. P., Tress, W. R., Abate, A., Hagfeldt, A. Science 2016, 354, 206. (192) Zhao, P., Yin, W., Kim, M., Han, M., Song, Y. J., Ahn, T. K. Jung, H. S. Journal of Materials Chemistry A 2017, 5, 7905. (193) Abdi-Jalebi, M., Pazoki, M., Philippe, B., Dar, M. I., Alsari, M., Sadhanala, A., Divitini, G., Imani, R., Lilliu, S., Kullgren, J. ACS Nano 2018, 12, 7301. (194) Pool, V. L., Gold-Parker, A., McGehee, M. D. Toney, M. F. Chemistry of Materials 2015, 27, 7240. (195) Li, X., Chen, C. C., Cai, M. L., Hua, X., Xie, F. X., Liu, X., Hua, J. L., Long, Y. T., Tian, H. Han, L. Y. Advanced Energy Materials 2018, 8, 1800715. (196) Lee, D. S., Yun, J. S., Kim, J., Soufiani, A. M., Chen, S., Cho, Y., Deng, X., Seidel, J., Lim, S., Huang, S. ACS Energy Letters 2018, 3, 647. (197) Wang, Z. P., Lin, Q. Q., Chmiel, F. P., Sakai, N., Herz, L. M. Snaith, H. J. Nature Energy 2017, 2, 17135. (198) Lin, Y., Bai, Y., Fang, Y., Chen, Z., Yang, S., Zheng, X., Tang, S., Liu, Y., Zhao, J. Huang, J. The Journal of Physical Chemistry Letters 2018, 9, 654. (199) Zhao, T., Chueh, C.-C., Chen, Q., Rajagopal, A. Jen, A. K. Y. ACS Energy Letters 2016, 1, 757. (200) Jung, M., Shin, T. J., Seo, J., Kim, G. Seok, S. I. Energy & Environmental Science 2018, 11, 2188. (201) Zheng, X., Deng, Y., Chen, B., Wei, H., Xiao, X., Fang, Y., Lin, Y., Yu, Z., Liu, Y., Wang, Q. Advanced Materials 2018, 30, e1803428. (202) Yin, X., Song, Z., Li, Z. Tang, W. Energy & Environmental Science 2020, 13, 4057. (203) Claessens, C. G., Hahn, U. Torres, T. The Chemical Record 2008, 8, 75. (204) Zhu, H., Shen, Z., Pan, L., Han, J., Eickemeyer, F. T., Ren, Y., Li, X., Wang, S., Liu, H., Dong, X. ACS Energy Letters 2021, 6, 208. (205) Schulz, P., Edri, E., Kirmayer, S., Hodes, G., Cahen, D. Kahn, A. Energy & Environmental Science 2014, 7, 1377. (206) Guo, H., Zhang, H., Shen, C., Zhang, D., Liu, S., Wu, Y. Zhu, W. H. Angewandte Chemie-International Edition 2021, 60, 2674. (207) Wang, S. H., Sakurai, T., Wen, W. J. Qi, Y. B. Advanced Materials Interfaces 2018, 5, 1800260. (208) Li, Y., Zhang, Y., Zhang, L. Z., Liu, C., Zhou, X. Y., Wang, D., Niu, B. B., Lu, C. L., Chang, J. H., Jiang, X. N. Solar RRL 2022, 6, 2101107. (209) Zhang, T., Yang, M., Zhao, Y. Zhu, K. Nano Letters 2015, 15, 3959. (210) Cho, H., Jeong, S. H., Park, M. H., Kim, Y. H., Wolf, C., Lee, C. L., Heo, J. H., Sadhanala, A., Myoung, N., Yoo, S. Science 2015, 350, 1222. (211) Son, D.-Y., Lee, J.-W., Choi, Y. J., Jang, I.-H., Lee, S., Yoo, P. J., Shin, H., Ahn, N., Choi, M., Kim, D. Nature Energy 2016, 1, 16081. (212) Jiang, J., Jin, Z., Lei, J., Wang, Q., Zhang, X., Zhang, J., Gao, F. Liu, S. Journal of Materials Chemistry A 2017, 5, 9514. (213) Tress, W., Marinova, N., Inganas, O., Nazeeruddin, M. K., Zakeeruddin, S. M. Graetzel, M. Advanced Energy Materials 2015, 5, 1400812. (214) Shao, Y., Yuan, Y. Huang, J. Nature Energy 2016, 1, 15001. (215) De Marco, N., Zhou, H., Chen, Q., Sun, P., Liu, Z., Meng, L., Yao, E.-P., Liu, Y., Schiffer, A. Yang, Y. Nano Letters 2016, 16, 1009. (216) Tress, W., Marinova, N., Moehl, T., Zakeeruddin, S. M., Nazeeruddin, M. K. Grätzel, M. Energy & Environmental Science 2015, 8, 995. (217) Domanski, K., Roose, B., Matsui, T., Saliba, M., Turren-Cruz, S.-H., Correa-Baena, J.-P., Carmona, C. R., Richardson, G., Foster, J. M., De Angelis, F. Energy & Environmental Science 2017, 10, 604. (218) Zheng, D., Peng, R., Wang, G., Logsdon, J. L., Wang, B., Hu, X., Chen, Y., Dravid, V. P., Wasielewski, M. R., Yu, J. Advanced Materials 2019, 31, e1903239. (219) Luo, J., Xia, J., Yang, H., Chen, L., Wan, Z., Han, F., Malik, H. A., Zhu, X. Jia, C. Energy & Environmental Science 2018, 11, 2035. (220) Tauc, J., Grigorovici, R. Vancu, A. physica status solidi (b) 1966, 15, 627. (221) Niu, T., Lu, J., Munir, R., Li, J., Barrit, D., Zhang, X., Hu, H., Yang, Z., Amassian, A., Zhao, K. Advanced Materials 2018, 30, e1706576. (222) Ravishankar, S., Gharibzadeh, S., Roldán-Carmona, C., Grancini, G., Lee, Y., Ralaiarisoa, M., Asiri, A. M., Koch, N., Bisquert, J. Nazeeruddin, M. K. Joule 2018, 2, 788. (223) Li, Z., Zhang, C., Shao, Z., Fan, Y., Liu, R., Wang, L. Pang, S. Journal of Materials Chemistry A 2018, 6, 9397. (224) Nie, W., Tsai, H., Asadpour, R., Blancon, J. C., Neukirch, A. J., Gupta, G., Crochet, J. J., Chhowalla, M., Tretiak, S., Alam, M. A. Science 2015, 347, 522. (225) Dar, M. I., Franckevičius, M., Arora, N., Redeckas, K., Vengris, M., Gulbinas, V., Zakeeruddin, S. M. Grätzel, M. Chemical Physics Letters 2017, 683, 211. (226) Piatkowski, P., Cohen, B., Javier Ramos, F., Di Nunzio, M., Nazeeruddin, M. K., Grätzel, M., Ahmad, S. Douhal, A. Physical Chemistry Chemical Physics 2015, 17, 14674. (227) Xiao, M., Joglekar, S., Zhang, X., Jasensky, J., Ma, J., Cui, Q., Guo, L. J. Chen, Z. Journal of the American Chemical Society 2017, 139, 3378.