Evolution of the Electronic and Excitonic Properties in 2D Ruddlesden–Popper Perovskites Induced by Bifunctional Ligands

Zhong, Xinjue; Ni, Xiaojuan; Kaplan, Alan; Zhao, Xiaoming; Ivancevic, Marko; Ball, Melissa L.; Xu, Zhaojian; Li, Hong; Rand, Barry P; Loo, Yueh‐Lin; Brédas, Jean‐Luc; Kahn, Antoine

doi:10.1002/aenm.202304345

Evolution of the Electronic and Excitonic Properties in 2D Ruddlesden–Popper Perovskites Induced by Bifunctional Ligands (in EN)

Journal Article · Wed Jan 10 23:00:00 EST 2024 · Advanced Energy Materials

DOI:https://doi.org/10.1002/aenm.202304345· OSTI ID:2575809

^[1]; Ni, Xiaojuan ^[2]; Kaplan, Alan ^[1]; Zhao, Xiaoming ^[1]; Ivancevic, Marko ^[1]; Ball, Melissa L. ^[1]; Xu, Zhaojian ^[1]; Li, Hong ^[2]; Rand, Barry P ^[1]; Loo, Yueh‐Lin ^[1]; Brédas, Jean‐Luc ^[2]; ^[1]

Princeton Univ., NJ (United States)
Univ. of Arizona, Tucson, AZ (United States)

2D Ruddlesden–Popper metal‐halide perovskites exhibit structural diversity due to a variety of choices of organic ligands. Incorporating bifunctional ligands in such materials is particularly intriguing since it can result in novel electronic properties and functions. However, an in‐depth understanding of the effects of bifunctional ligands on perovskite structures and, consequently, their electronic and excitonic properties, is still lacking. Here, in this work, n = 1 2D perovskites built with organic ligands containing ─CN, ─OH, ─COOH, ─phenyl (Ph), and ─CH₃ functional groups are investigated using ultraviolet and inverse photoemission spectroscopies, density functional theory calculations, and tight‐binding model analyses. The experimentally determined electronic gaps of the ─CN, ─COOH, ─Ph, and ─CH₃ based perovskites exhibit a strong correlation with the in‐plane Pb─I─Pb bond angle, while the ─OH based perovskite deviates from the linear trend. Based on the band structure calculations, this anomaly is attributed to the out‐of‐plane dispersion, caused predominantly by significant interlayer electronic coupling that is present in ─OH based perovskites. These results highlight the complex and diverse impacts of organic ligands on electronic properties, especially in terms of the involvement of strong interlayer electronic coupling. The impact of the bifunctional ligands on the evolution of the exciton binding energy is also addressed.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office; Office of Naval Research (ONR); National Science Foundation (NSF)

Grant/Contract Number:: EE0008560

OSTI ID:: 2575809

Alternate ID(s):: OSTI ID: 2281035

Journal Information:: Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 18 Vol. 14; ISSN 1614-6840; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: EN

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