High-temperature polymorphism and band-gap evolution in BaZrS3
Barium zirconium trisulfide (BZS) is a three-dimensional (3D) perovskite with optoelectronic properties suitable for photovoltaic (PV) and light-emitting diode (LED) applications that is conventionally reported in the orthorhombic Pnma (62) symmetry. Synchrotron X-ray diffraction, thermal analysis,...
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| Format: | Journal Article |
| Language: | English |
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2025
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| Online Access: | https://hdl.handle.net/10356/182599 |
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| author | Jaiswal, Ankit Sakharov, Konstantin A. Lekina, Yulia Kamonsuangkasem, Krongthong Tomm, Yvonne Wei, Fengxia White, Timothy John |
| author2 | School of Materials Science and Engineering |
| author_facet | School of Materials Science and Engineering Jaiswal, Ankit Sakharov, Konstantin A. Lekina, Yulia Kamonsuangkasem, Krongthong Tomm, Yvonne Wei, Fengxia White, Timothy John |
| author_sort | Jaiswal, Ankit |
| collection | NTU |
| description | Barium zirconium trisulfide (BZS) is a three-dimensional (3D) perovskite with optoelectronic properties suitable for photovoltaic (PV) and light-emitting diode (LED) applications that is conventionally reported in the orthorhombic Pnma (62) symmetry. Synchrotron X-ray diffraction, thermal analysis, and Raman and absorption spectroscopy revealed three high-temperature polymorphs that appear when BZS is heated in air prior to complete oxidation (BaZrS3 + 5O2 → BaSO4 + ZrO2 + 2SO2↑) at 700 °C with the approximate stability ranges: BaZrS3 IVPnma (62)T < 400 °CBaZrS3 IIICmcm (63)400 °C ≤ T ≤ 500 °CBaZrS3 II14/mcm (140)500 °C ≤ T ≤ 700 °CDifferential scanning calorimetry (DSC) revealed exothermic features accompanying the IV → III and III → II phase changes. Furthermore, the direct band gap varied inversely with temperature with distinct energies for each polymorph (1.84 eV ≤ IV ≤ 1.65 eV; 1.65 eV ≤ III ≤ 1.54 eV; 1.54 eV ≤ II ≤ 1.52 eV). Raman spectroscopy found that polymorphic changes up to 600 °C were reversible with bands characteristic of BaZrS3 IV entirely restored upon cooling to room temperature (RT). This more complete understanding of BSZ polymorphism provides a basis for producing crystallochemical variants with enhanced optoelectronic properties under ambient conditions. |
| first_indexed | 2025-03-09T14:38:30Z |
| format | Journal Article |
| id | ntu-10356/182599 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2025-03-09T14:38:30Z |
| publishDate | 2025 |
| record_format | dspace |
| spelling | ntu-10356/1825992025-02-11T06:38:54Z High-temperature polymorphism and band-gap evolution in BaZrS3 Jaiswal, Ankit Sakharov, Konstantin A. Lekina, Yulia Kamonsuangkasem, Krongthong Tomm, Yvonne Wei, Fengxia White, Timothy John School of Materials Science and Engineering School of Physical and Mathematical Sciences Institute of Materials Research and Engineering A*STAR Chemistry Barium alloys Differential thermal analysis Barium zirconium trisulfide (BZS) is a three-dimensional (3D) perovskite with optoelectronic properties suitable for photovoltaic (PV) and light-emitting diode (LED) applications that is conventionally reported in the orthorhombic Pnma (62) symmetry. Synchrotron X-ray diffraction, thermal analysis, and Raman and absorption spectroscopy revealed three high-temperature polymorphs that appear when BZS is heated in air prior to complete oxidation (BaZrS3 + 5O2 → BaSO4 + ZrO2 + 2SO2↑) at 700 °C with the approximate stability ranges: BaZrS3 IVPnma (62)T < 400 °CBaZrS3 IIICmcm (63)400 °C ≤ T ≤ 500 °CBaZrS3 II14/mcm (140)500 °C ≤ T ≤ 700 °CDifferential scanning calorimetry (DSC) revealed exothermic features accompanying the IV → III and III → II phase changes. Furthermore, the direct band gap varied inversely with temperature with distinct energies for each polymorph (1.84 eV ≤ IV ≤ 1.65 eV; 1.65 eV ≤ III ≤ 1.54 eV; 1.54 eV ≤ II ≤ 1.52 eV). Raman spectroscopy found that polymorphic changes up to 600 °C were reversible with bands characteristic of BaZrS3 IV entirely restored upon cooling to room temperature (RT). This more complete understanding of BSZ polymorphism provides a basis for producing crystallochemical variants with enhanced optoelectronic properties under ambient conditions. Ministry of Education (MOE) Nanyang Technological University The authors would like to thank the Monetary Academic Resources for Research (Grant No. 001561−00001) in Nanyang Technological University and Ministry of Education (MOE) for funding the research through the following grants: AcRF Tier 2 (Reference Nos: MOE-T2EP50220−0020 and MOE-T2EP50122−0005). 2025-02-11T06:38:53Z 2025-02-11T06:38:53Z 2024 Journal Article Jaiswal, A., Sakharov, K. A., Lekina, Y., Kamonsuangkasem, K., Tomm, Y., Wei, F. & White, T. J. (2024). High-temperature polymorphism and band-gap evolution in BaZrS3. Inorganic Chemistry, 63(51), 24157-24166. https://dx.doi.org/10.1021/acs.inorgchem.4c03895 0020-1669 https://hdl.handle.net/10356/182599 10.1021/acs.inorgchem.4c03895 39652717 2-s2.0-85211618618 51 63 24157 24166 en 001561−00001 MOE-T2EP50220−0020 MOE-T2EP50122−0005 Inorganic chemistry © 2024 American Chemical Society. All rights reserved. |
| spellingShingle | Chemistry Barium alloys Differential thermal analysis Jaiswal, Ankit Sakharov, Konstantin A. Lekina, Yulia Kamonsuangkasem, Krongthong Tomm, Yvonne Wei, Fengxia White, Timothy John High-temperature polymorphism and band-gap evolution in BaZrS3 |
| title | High-temperature polymorphism and band-gap evolution in BaZrS3 |
| title_full | High-temperature polymorphism and band-gap evolution in BaZrS3 |
| title_fullStr | High-temperature polymorphism and band-gap evolution in BaZrS3 |
| title_full_unstemmed | High-temperature polymorphism and band-gap evolution in BaZrS3 |
| title_short | High-temperature polymorphism and band-gap evolution in BaZrS3 |
| title_sort | high temperature polymorphism and band gap evolution in bazrs3 |
| topic | Chemistry Barium alloys Differential thermal analysis |
| url | https://hdl.handle.net/10356/182599 |
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