Ligand-induced self-assembly of twisted two-dimensional halide perovskites

Yang, Jonghee; Fuhr, Addis S.; Shin, Subeom; Roccapriore, Kevin M.; Dryzhakov, Bogdan; Hu, Bin; Kang, Byeongjoo; Ahn, Hyungju; Kim, Woojae; Sumpter, Bobby G.; Kalinin, Sergei V.; Ahmadi, Mahshid

doi:10.1038/s44160-025-00780-0

Ligand-induced self-assembly of twisted two-dimensional halide perovskites

Journal Article · Fri Mar 28 00:00:00 EDT 2025 · Nature Synthesis

DOI:https://doi.org/10.1038/s44160-025-00780-0· OSTI ID:2573612

^[1]; ^[2]; Shin, Subeom ^[1]; ^[2]; ^[3]; Hu, Bin ^[4]; Kang, Byeongjoo ^[1]; Ahn, Hyungju ^[5]; ^[1]; ^[2]; Kalinin, Sergei V. ^[6]; ^[4]

Yonsei Univ., Seoul (Korea, Republic of)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Univ. of Tennessee, Knoxville, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of)
Univ. of Tennessee, Knoxville, TN (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Two-dimensional (2D) halide perovskites (HPs) exhibit intriguing optoelectronic functionalities. Conventionally, 2D HPs have been synthesized with linear and planar molecular spacers, resulting in nominal modifications of their optoelectronic properties. In contrast, lower-dimensional HPs (0D and 1D) have proved accommodating to the incorporation of bulky molecular spacers. Fundamental insights into the incorporation of bulky molecular spacers in 2D HP structures remains elusive. Here, in this study, by implementing a high-throughput autonomous exploration workflow, the crystallization behaviours of 2D HPs based on a bulky 3,3-diphenylpropylammonium (DPA) spacer are comprehensively explored. Counterintuitive to conventional HP chemistry, synthesis of 2D DPA₂PbI₄ HPs is indeed feasible when the steric hindrance is mediated by minute incorporation of 3D HP precursors. Furthermore, a moiré superlattice is observed from the DPA₂PbI₄ flakes, indicating the spontaneous formation of twisted stacks of 2D HPs.We hypothesize that the unconventional van der Waals surface of DPA₂PbI₄ facilitates the self-assembly of the twisted stacks of 2D HPs. This work exemplifies how high-throughput experimentation can discover unconventional material systems in which the synthetic principle lies beyond conventional chemical intuition. Furthermore, these findings provide hints for how to chemically manipulate the twist stacking in 2D HPs, thus rendering a straightforward way for bespoke realization of functionalities in exotic materials systems via a bottom-up approach.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: Alfred P. Sloan Foundation; National Research Foundation of Korea (NRF); National Science Foundation (NSF); US Department of Homeland Security (DHS); US Department of the Navy, Office of Naval Research (ONR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); Yonsei University Research Fund

Grant/Contract Number:: AC05-00OR22725; SC0019288

OSTI ID:: 2573612

Journal Information:: Nature Synthesis, Journal Name: Nature Synthesis; ISSN 2731-0582

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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