Steering Solid–Solution Equilibria to Tame Phase Complexity and Instability in Dion-Jacobson Quasi-2D Halide Perovskites
7 affiliations
- 1Yonsei University
- 2Hanyang University
- 3University of Tennessee at Knoxville
- 4Graduate School of Carbon Neutrality
- 5Ulsan National Institute of Science and Technology
- 6Optigon Inc.
- 7School of Energy and Chemical Engineering
Abstract
Dion-Jacobson (DJ) quasi-two-dimensional (2D) halide perovskites (HPs) have emerged as a robust platform for optoelectronic applications, yet their crystallization pathways and subsequent phase evolution remain insufficiently understood. Herein, we integrate robotic high-throughput synthesis with automated spectral diagnosis and multimodal characterization to investigate 1,4-butanediammonium-based HPs containing methylammonium (MA) or formamidinium (FA) across composition and temperature. Tracking phase evolution and cation partitioning reveals competition between lattice stabilization, coarsening, and reconstruction within a coupled heterogeneous reaction system. Continued MA incorporation changes both the solids and surrounding solution, whereas greater initial FA capture does not ensure higher- n phase retention. Comparative extraction and spacer-treatment experiments support an additional pathway linking δ-containing FAPbI 3 structures to FA release and lower- n reconstruction. These findings provide experimental insight into the intricate solid–solution chemical equilibria underlying crystal maturation beyond nucleation. Exploiting this understanding, machine-learning-assisted multi-objective screening identifies synthesis conditions that sustain homogeneous, spectrally ‘frozen’ emission, guiding the formation of chemically stabilized, structurally robust HP frameworks. Applying the selected formulation to HP interfaces yields efficient solar cells with markedly improved thermal stability. Overall, this integrated experiment-analysis workflow translates solid–solution equilibrium chemistry into data-guided control of phase complexity, offering a strategy for durable HP optoelectronics.
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BibTeX
@misc{shin2026steering,
title = {{Steering Solid–Solution Equilibria to Tame Phase Complexity and Instability in Dion-Jacobson Quasi-2D Halide Perovskites}},
author = {Subeom Shin and Yifan Yu and Hochan Song and Jung Geon Son and Minhal Hasham and Seyeon Eom and Hyerin Kim and Minsub Um and Dong Suk Kim and Hyosung Choi and Mahshid Ahmadi and Jonghee Yang},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv-2025-m0l72/v2},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv-2025-m0l72/v2},
note = {CC BY},
}
RIS
TY - UNPB
TI - Steering Solid–Solution Equilibria to Tame Phase Complexity and Instability in Dion-Jacobson Quasi-2D Halide Perovskites
AU - Subeom Shin
AU - Yifan Yu
AU - Hochan Song
AU - Jung Geon Son
AU - Minhal Hasham
AU - Seyeon Eom
AU - Hyerin Kim
AU - Minsub Um
AU - Dong Suk Kim
AU - Hyosung Choi
AU - Mahshid Ahmadi
AU - Jonghee Yang
PY - 2026
DA - 2026/10/27
PB - ChemRxiv
DO - 10.26434/chemrxiv-2025-m0l72/v2
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv-2025-m0l72/v2
AB - Dion-Jacobson (DJ) quasi-two-dimensional (2D) halide perovskites (HPs) have emerged as a robust platform for optoelectronic applications, yet their crystallization pathways and subsequent phase evolution remain insufficiently understood. Herein, we integrate robotic high-throughput synthesis with automated spectral diagnosis and multimodal characterization to investigate 1,4-butanediammonium-based HPs containing methylammonium (MA) or formamidinium (FA) across composition and temperature. Tracking phase evolution and cation partitioning reveals competition between lattice stabilization, coarsening, and reconstruction within a coupled heterogeneous reaction system. Continued MA incorporation changes both the solids and surrounding solution, whereas greater initial FA capture does not ensure higher- n phase retention. Comparative extraction and spacer-treatment experiments support an additional pathway linking δ-containing FAPbI 3 structures to FA release and lower- n reconstruction. These findings provide experimental insight into the intricate solid–solution chemical equilibria underlying crystal maturation beyond nucleation. Exploiting this understanding, machine-learning-assisted multi-objective screening identifies synthesis conditions that sustain homogeneous, spectrally ‘frozen’ emission, guiding the formation of chemically stabilized, structurally robust HP frameworks. Applying the selected formulation to HP interfaces yields efficient solar cells with markedly improved thermal stability. Overall, this integrated experiment-analysis workflow translates solid–solution equilibrium chemistry into data-guided control of phase complexity, offering a strategy for durable HP optoelectronics.
ER -