Grain Boundary Engineering with Self-Assembled Porphyrin Supramolecules for Highly Efficient Large-Area Perovskite Photovoltaics

Zihan Fang; Luyao Wang; Xijiao Mu; Bin Chen; Qiu Xiong; Wei David Wang; Jiaxin Ding; Peng Gao; Yiying Wu; Jing Cao

doi:10.1021/jacs.1c07518

Grain Boundary Engineering with Self-Assembled Porphyrin Supramolecules for Highly Efficient Large-Area Perovskite Photovoltaics

J Am Chem Soc. 2021 Nov 17;143(45):18989-18996. doi: 10.1021/jacs.1c07518. Epub 2021 Oct 19.

Authors

Zihan Fang¹, Luyao Wang², Xijiao Mu¹, Bin Chen³, Qiu Xiong⁴, Wei David Wang¹, Jiaxin Ding⁵, Peng Gao⁴, Yiying Wu⁶, Jing Cao¹

Affiliations

¹ State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P.R. China.
² State School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, P.R. China.
³ Department of Electrical and Computer Engineering, University of Toronto, 35 St. George Street, Toronto, Ontario M5S 1A4, Canada.
⁴ State Key Laboratory of Design and Assembly of Functional Nanostructures and Fujian Provincial Key Laboratory of Nanomaterials Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P.R. China.
⁵ Instrumental Analysis Centre, Shanghai Jiao Tong University, Shanghai 200240, P.R. China.
⁶ Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.

PMID: 34665964
DOI: 10.1021/jacs.1c07518

Abstract

Grain boundary management is critical to the performance and stability of polycrystalline perovskite solar cells (PSCs), especially large-area devices. However, typical passivators are insulating in nature and limit carrier transport. Here, we design a supramolecular binder for grain boundaries to simultaneously passivate defects and promote hole transport across perovskite grain boundaries. By doping the monoamine porphyrins (MPs, M = Co, Ni, Cu, Zn, or H) into perovskite films, MPs self-assemble into supramolecules at grain boundaries. Organic cations in perovskites protonate MPs in supramolecules to form ammonium porphyrins bound on the perovskite grain surface, to passivate defects and extract holes from the perovskite lattice. Periodic polarons in supramolecules (especially NiP-supramolecule) promote the transport of extracted holes across boundaries, reducing nonradiative carrier recombination. The NiP-doped PSCs reveal a certified efficiency of 22.1% for an active area of 1.0 cm² with the remarkably improved open-circuit voltage and fill factor. The unencapsulated device retained over 80% initial performance under AM 1.5G solar light continuous illumination or heating at 85 °C over 3000 h.