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However, the performance of inverted PSCs remains limited by intrinsic defects in perovskite thin films, primarily due to inadequate control over crystallization on the poor\u2010quality SAM substrates. Here, we reported a proton transfer\u2010hydrogen bond network using a multifunctional additive phenylguanidine carbonate over a co\u2010adsorbed SAM (Co\u2010SAM) system. This strategy promoted the formation of guanidinium\u2010formamidinium hydrogen\u2010bonded complexes, which stabilize intermediate phases, suppress the generation of impurity phases during nucleation and accelerate the transition from \u03b4\u2010phase to \u03b1\u2010phase. The significantly delayed crystallization process successfully induced large perovskite grains with suppressed intrinsic defects. Moreover, a high coverage, uniformity, and dense molecular packing was achieved for the Co\u2010SAM, ensuring an excellent growth substrate for subsequent perovskite deposition. PSCs ultimately achieved a power conversion efficiency (PCE) of 26.65%, with enhanced operational stability\u2010retaining 92.5% of initial PCE after\u00a0&gt;1200 h of maximum power point tracking.<\/jats:p>","DOI":"10.1002\/anie.202522939","type":"journal-article","created":{"date-parts":[[2025,11,17]],"date-time":"2025-11-17T09:14:42Z","timestamp":1763370882000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Proton Transfer\u2010Hydrogen Bonds Network for Highly Efficient and Stable Inverted Perovskite Solar Cells"],"prefix":"10.1002","volume":"65","author":[{"given":"Yiting","family":"Zheng","sequence":"first","affiliation":[{"name":"State Key Laboratory of Flexible Electronics (LoFE) and Institute of Advanced Materials (IAM) School of Flexible Electronics (Future Technologies) Nanjing Tech University (Nanjing Tech)  30 South Puzhu Road Nanjing Jiangsu 211816 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pingping","family":"Ma","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Flexible Electronics (LoFE) and Institute of Advanced Materials (IAM) School of Flexible Electronics (Future Technologies) Nanjing Tech University (Nanjing Tech)  30 South Puzhu Road Nanjing Jiangsu 211816 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tingting","family":"Niu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Flexible Electronics (LoFE) and Institute of Advanced Materials (IAM) School of Flexible Electronics (Future Technologies) Nanjing Tech University (Nanjing Tech)  30 South Puzhu Road Nanjing Jiangsu 211816 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lingfeng","family":"Chao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Flexible Electronics (LoFE) and Institute of Advanced Materials (IAM) School of Flexible Electronics (Future Technologies) Nanjing Tech University (Nanjing Tech)  30 South Puzhu Road Nanjing Jiangsu 211816 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shijing","family":"Qian","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Flexible Electronics (LoFE) and Institute of Advanced Materials (IAM) School of Flexible Electronics (Future Technologies) Nanjing Tech University (Nanjing Tech)  30 South Puzhu Road Nanjing Jiangsu 211816 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yingdong","family":"Xia","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Flexible Electronics (LoFE) and Institute of Advanced Materials (IAM) School of Flexible Electronics (Future Technologies) Nanjing Tech University (Nanjing Tech)  30 South Puzhu Road Nanjing Jiangsu 211816 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9694-4246","authenticated-orcid":false,"given":"Yonghua","family":"Chen","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Flexible Electronics (LoFE) and Institute of Advanced Materials (IAM) School of Flexible Electronics (Future Technologies) Nanjing Tech University (Nanjing Tech)  30 South Puzhu Road Nanjing Jiangsu 211816 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,11,17]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41560\u2010017\u20100067\u2010y"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.joule.2021.11.003"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41560\u2010020\u201000687\u20104"},{"key":"e_1_2_7_4_1","unstructured":"National Renewable Energy Laboratory (NREL). 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