Zero-Dimensional Bismuth Halide Thin Films with High Orientation and Broadband Emission.
8 affiliations
- 1Istituto Italiano di Tecnologia , Center for Sustainable Future Technologies, Via Livorno 60, Torino10144, Italy.
- 2Politecnico di Torino , Department of Applied Science and Technology, Corso Duca degli Abruzzi 24, Torino10129, Italy.
- 3Department of Chemistry and INSTM, University of Pavia, Via Taramelli 16, Pavia27100, Italy.
- 4School of Mathematics and Physics, University of Science and Technology Beijing, Beijing100083, China.
- 5Istituto Italiano di Tecnologia, Materials Characterization Facility, Via Morego 30, Genova16163, Italy.
- 6Consiglio Nazionale Delle Ricerche, Institute for Photonics and Nanotechnology (CNR-IFN), Milano20133, Italy.
- 7Istituto Italiano di Tecnologia, Center for Nano Science and Technology, Via Rubattino 81, Milan20134, Italy.
- 8Consiglio Nazionale delle Ricerche, Institute for Superconducting and Innovative Materials and Devices (CNR-SPIN), c/o Department of Physical and Chemical Sciences, University of L'Aquila, Coppito, L'AquilaI-67100, Italy.
Abstract
Lead-free low-dimensional metal halides are emerging as highly tunable materials for optoelectronic applications. Here, we report a new class of zero-dimensional bismuth halides incorporating phenethylammonium (PEA) cations, namely PEA4BiI7 and PEA4BiBr7, and investigate their structural, thermal, and optoelectronic properties. Single-crystal X-ray diffraction reveals that both compounds consist of isolated [BiX6] octahedra separated by bulky organic cations, although they crystallize in different crystal systems and exhibit high stability under ambient conditions. In contrast, the chloride analogue adopts a distinct stoichiometry, PEA4Bi2Cl10, featuring edge-sharing octahedral dimers, highlighting the strong impact of halide substitution on the structural connectivity. Optical measurements show a systematic bandgap evolution following the trend Cl > Br > I, with pronounced excitonic absorption features in all compounds; density functional theory calculations indicate that the conduction band edge is dominated by the inorganic Bi-X framework, while the valence band edge progressively changes from the organic cation to the inorganic sublattice. Thin films were fabricated via a simple one-step spin-coating procedure. Particularly, PEA4BiI7 forms highly oriented, phase-pure thin films and exhibits broadband visible photoluminescence with excitation-dependent behavior. These results establish phenethylammonium bismuth halides as a versatile platform for stable, lead-free zero-dimensional semiconductors with promising potential for solution-processed optoelectronic devices.
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BibTeX
@article{neisius2026zerodimensional,
title = {{Zero-Dimensional Bismuth Halide Thin Films with High Orientation and Broadband Emission.}},
author = {Raphael Neisius and Marco Moroni and Yali Yang and Sergio Marras and Matteo Lorenzoni and Paola Ragonese and Cecilia Daniela Costa and Mengjiao Wang and Giuseppe Ferraro and Giulia Folpini and Alessandro Stroppa and Lorenzo Malavasi and Teresa Gatti and Isabella Poli},
journal = {Inorganic chemistry},
year = {2026},
month = sep,
doi = {10.1021/acs.inorgchem.6c03044},
url = {https://europepmc.org/article/MED/42916471},
note = {CC BY},
}
RIS
TY - JOUR
TI - Zero-Dimensional Bismuth Halide Thin Films with High Orientation and Broadband Emission.
AU - Raphael Neisius
AU - Marco Moroni
AU - Yali Yang
AU - Sergio Marras
AU - Matteo Lorenzoni
AU - Paola Ragonese
AU - Cecilia Daniela Costa
AU - Mengjiao Wang
AU - Giuseppe Ferraro
AU - Giulia Folpini
AU - Alessandro Stroppa
AU - Lorenzo Malavasi
AU - Teresa Gatti
AU - Isabella Poli
PY - 2026
DA - 2026/09/01
JO - Inorganic chemistry
DO - 10.1021/acs.inorgchem.6c03044
UR - https://europepmc.org/article/MED/42916471
AB - Lead-free low-dimensional metal halides are emerging as highly tunable materials for optoelectronic applications. Here, we report a new class of zero-dimensional bismuth halides incorporating phenethylammonium (PEA) cations, namely PEA4BiI7 and PEA4BiBr7, and investigate their structural, thermal, and optoelectronic properties. Single-crystal X-ray diffraction reveals that both compounds consist of isolated [BiX6] octahedra separated by bulky organic cations, although they crystallize in different crystal systems and exhibit high stability under ambient conditions. In contrast, the chloride analogue adopts a distinct stoichiometry, PEA4Bi2Cl10, featuring edge-sharing octahedral dimers, highlighting the strong impact of halide substitution on the structural connectivity. Optical measurements show a systematic bandgap evolution following the trend Cl > Br > I, with pronounced excitonic absorption features in all compounds; density functional theory calculations indicate that the conduction band edge is dominated by the inorganic Bi-X framework, while the valence band edge progressively changes from the organic cation to the inorganic sublattice. Thin films were fabricated via a simple one-step spin-coating procedure. Particularly, PEA4BiI7 forms highly oriented, phase-pure thin films and exhibits broadband visible photoluminescence with excitation-dependent behavior. These results establish phenethylammonium bismuth halides as a versatile platform for stable, lead-free zero-dimensional semiconductors with promising potential for solution-processed optoelectronic devices.
SN - 0020-1669
SN - 1520-510X
ER -