Lattice Dynamics and Optoelectronic Properties of Vacancy-Ordered Double Perovskite Cs2TeX6 (X = Cl–, Br–, I–) Single Crystals
Abstract
The soft, dynamic lattice of inorganic lead halide perovskite CsPbX3 (X = Cl⁻, Br⁻, I⁻) leads to the emergence of many interesting photophysical and optoelectronic phenomena. However, probing their lattice dynamics with vibrational spectroscopy remains challenging. The influence of the fundamental octahedral building block in the perovskite lattice can be better resolved in zero-dimensional (0D) vacancy-ordered double perovskites of form A2BX6. Here we study Cs2TeX6 (X = Cl⁻, Br⁻, I⁻) single crystals to yield detailed insight into the fundamental octahedral building block and to explore the effect that its isolation in the crystal structure has on structural and electronic properties. The isolated [TeX6]2- octahedral units serve as the vibrational, absorbing, and emitting centers within the crystal. Serving as the vibrational centers, the isolated octahedra inform the likelihood of a random distribution of 10 octahedral symmetries within the mixed-halide spaces, as well as the presence of strong exciton-phonon coupling and anharmonic lattice dynamics. Serving as the absorbing and emitting centers, the isolated octahedra exhibit compositionally tunable absorption (1.50-3.15 eV) and emission (1.31-2.11 eV) energies. Due to greater molecular orbital overlap between neighboring octahedra with increasing halide anion size, there is a transition from a more molecule-like electronic structure in Cs2TeCl6 andmore »
- Authors:
-
[1];
[1];
[2];
[4];
[5];
[9]
- Univ. of California, Berkeley, CA (United States); California Research Alliance (CARA) and BASF Corporation, Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Katholieke Univ. Leuven, Heverlee (Belgium). cMACS, Department of Microbial and Molecular Systems
- Univ. of California, Berkeley, CA (United States)
- California Research Alliance (CARA) and BASF Corporation, Berkeley, CA (United States)
- BASF SE, Ludwigshafen am Rhein (Germany)
- California Research Alliance (CARA) and BASF Corporation, Berkeley, CA (United States); BASF SE, Ludwigshafen am Rhein (Germany)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience Institute, Berkeley, CA (United States); California Research Alliance (CARA) and BASF Corporation, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1833364
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 125; Journal Issue: 45; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Absorption; Crystal structure; Crystals; Lattices; Quantum mechanics
Citation Formats
Folgueras, Maria C., Jin, Jianbo, Gao, Mengyu, Quan, Li Na, Steele, Julian A., Srivastava, Shivani, Ross, Michael B., Zhang, Rui, Seeler, Fabian, Schierle-Arndt, Kerstin, Asta, Mark, and Yang, Peidong. Lattice Dynamics and Optoelectronic Properties of Vacancy-Ordered Double Perovskite Cs2TeX6 (X = Cl–, Br–, I–) Single Crystals. United States: N. p., 2021.
Web. doi:10.1021/acs.jpcc.1c08332.
Folgueras, Maria C., Jin, Jianbo, Gao, Mengyu, Quan, Li Na, Steele, Julian A., Srivastava, Shivani, Ross, Michael B., Zhang, Rui, Seeler, Fabian, Schierle-Arndt, Kerstin, Asta, Mark, & Yang, Peidong. Lattice Dynamics and Optoelectronic Properties of Vacancy-Ordered Double Perovskite Cs2TeX6 (X = Cl–, Br–, I–) Single Crystals. United States. https://doi.org/10.1021/acs.jpcc.1c08332
Folgueras, Maria C., Jin, Jianbo, Gao, Mengyu, Quan, Li Na, Steele, Julian A., Srivastava, Shivani, Ross, Michael B., Zhang, Rui, Seeler, Fabian, Schierle-Arndt, Kerstin, Asta, Mark, and Yang, Peidong. Tue .
"Lattice Dynamics and Optoelectronic Properties of Vacancy-Ordered Double Perovskite Cs2TeX6 (X = Cl–, Br–, I–) Single Crystals". United States. https://doi.org/10.1021/acs.jpcc.1c08332. https://www.osti.gov/servlets/purl/1833364.
@article{osti_1833364,
title = {Lattice Dynamics and Optoelectronic Properties of Vacancy-Ordered Double Perovskite Cs2TeX6 (X = Cl–, Br–, I–) Single Crystals},
author = {Folgueras, Maria C. and Jin, Jianbo and Gao, Mengyu and Quan, Li Na and Steele, Julian A. and Srivastava, Shivani and Ross, Michael B. and Zhang, Rui and Seeler, Fabian and Schierle-Arndt, Kerstin and Asta, Mark and Yang, Peidong},
abstractNote = {The soft, dynamic lattice of inorganic lead halide perovskite CsPbX3 (X = Cl⁻, Br⁻, I⁻) leads to the emergence of many interesting photophysical and optoelectronic phenomena. However, probing their lattice dynamics with vibrational spectroscopy remains challenging. The influence of the fundamental octahedral building block in the perovskite lattice can be better resolved in zero-dimensional (0D) vacancy-ordered double perovskites of form A2BX6. Here we study Cs2TeX6 (X = Cl⁻, Br⁻, I⁻) single crystals to yield detailed insight into the fundamental octahedral building block and to explore the effect that its isolation in the crystal structure has on structural and electronic properties. The isolated [TeX6]2- octahedral units serve as the vibrational, absorbing, and emitting centers within the crystal. Serving as the vibrational centers, the isolated octahedra inform the likelihood of a random distribution of 10 octahedral symmetries within the mixed-halide spaces, as well as the presence of strong exciton-phonon coupling and anharmonic lattice dynamics. Serving as the absorbing and emitting centers, the isolated octahedra exhibit compositionally tunable absorption (1.50-3.15 eV) and emission (1.31-2.11 eV) energies. Due to greater molecular orbital overlap between neighboring octahedra with increasing halide anion size, there is a transition from a more molecule-like electronic structure in Cs2TeCl6 and Cs2TeBr6-as expected from the effective 0D nature of these single crystals-to a dispersive electronic structure in Cs2TeI6, typical of three-dimensional (3D) bulk single crystals.},
doi = {10.1021/acs.jpcc.1c08332},
journal = {Journal of Physical Chemistry. C},
number = 45,
volume = 125,
place = {United States},
year = {Tue Nov 09 00:00:00 EST 2021},
month = {Tue Nov 09 00:00:00 EST 2021}
}
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