Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS_{3}
Exploring the conduction mechanism in the chalcogenide perovskite BaZrS_{3} is of significant interest due to its potential suitability as a top absorber layer in silicon-based tandem solar cells and other optoelectronic applications. Theoretical and experimental studies anticipate native ambipolar...
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American Physical Society
2025-07-01
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| Series: | PRX Energy |
| Online Access: | http://doi.org/10.1103/t7ns-99dk |
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| author | Garima Aggarwal Adeem Saeed Mirza Stefania Riva Corrado Comparotto Robert J. W. Frost Soham Mukherjee Monica Morales-Masis Håkan Rensmo Jonathan Staaf Scragg |
| author_facet | Garima Aggarwal Adeem Saeed Mirza Stefania Riva Corrado Comparotto Robert J. W. Frost Soham Mukherjee Monica Morales-Masis Håkan Rensmo Jonathan Staaf Scragg |
| author_sort | Garima Aggarwal |
| collection | DOAJ |
| description | Exploring the conduction mechanism in the chalcogenide perovskite BaZrS_{3} is of significant interest due to its potential suitability as a top absorber layer in silicon-based tandem solar cells and other optoelectronic applications. Theoretical and experimental studies anticipate native ambipolar doping in BaZrS_{3}, although experimental validation remains limited. This study reveals a transition from highly insulating behavior to n-type conductivity (approximately 100 S/cm) in BaZrS_{3} thin films through annealing in an S-poor environment. BaZrS_{3} thin films are synthesized via a two-step process: co-sputtering of Ba-Zr followed by sulfurization at 600^{∘}C, and subsequent annealing in high vacuum. Ultraviolet-visible spectroscopy measurements reveal a red shift of approximately 100 meV in the band gap concurrent with sample-color darkening after vacuum annealing. The increase in defect density from the order of 10^{17} to 10^{21}cm^{−3} with vacuum annealing, coupled with the low activation energy (approximately 8 meV), and the n-type character of the defects, strongly suggests that sulfur vacancies (V_{S}) are responsible for the n-type doping, in agreement with theoretical predictions. Temperature-dependent Hall measurement shows that phonon scattering governs charge transport at room temperature in BaZrS_{3} films and that S vacancies are shallow donor defects acting as a weak impurity metal. The shift of the valence-band maximum (VBM) with respect to the Fermi level, quantified by hard x-ray photoelectron spectroscopy (Ga Kα, 9.25 keV), further corroborates the induced n type of conductivity in annealed samples. Our findings indicate that vacuum annealing induces V_{S} defects that dominate charge transport, resulting in n-type conductivity in BaZrS_{3} under S-poor conditions. These discoveries will inform important design choices, such as selecting appropriate contact materials, for integrating BaZrS_{3} into solar cell structures or other devices. |
| format | Article |
| id | doaj-art-9ea4d51448ef401c8361818ad968fd6c |
| institution | Kabale University |
| issn | 2768-5608 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | American Physical Society |
| record_format | Article |
| series | PRX Energy |
| spelling | doaj-art-9ea4d51448ef401c8361818ad968fd6c2025-08-20T03:50:16ZengAmerican Physical SocietyPRX Energy2768-56082025-07-014303300110.1103/t7ns-99dkCharge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS_{3}Garima AggarwalAdeem Saeed MirzaStefania RivaCorrado ComparottoRobert J. W. FrostSoham MukherjeeMonica Morales-MasisHåkan RensmoJonathan Staaf ScraggExploring the conduction mechanism in the chalcogenide perovskite BaZrS_{3} is of significant interest due to its potential suitability as a top absorber layer in silicon-based tandem solar cells and other optoelectronic applications. Theoretical and experimental studies anticipate native ambipolar doping in BaZrS_{3}, although experimental validation remains limited. This study reveals a transition from highly insulating behavior to n-type conductivity (approximately 100 S/cm) in BaZrS_{3} thin films through annealing in an S-poor environment. BaZrS_{3} thin films are synthesized via a two-step process: co-sputtering of Ba-Zr followed by sulfurization at 600^{∘}C, and subsequent annealing in high vacuum. Ultraviolet-visible spectroscopy measurements reveal a red shift of approximately 100 meV in the band gap concurrent with sample-color darkening after vacuum annealing. The increase in defect density from the order of 10^{17} to 10^{21}cm^{−3} with vacuum annealing, coupled with the low activation energy (approximately 8 meV), and the n-type character of the defects, strongly suggests that sulfur vacancies (V_{S}) are responsible for the n-type doping, in agreement with theoretical predictions. Temperature-dependent Hall measurement shows that phonon scattering governs charge transport at room temperature in BaZrS_{3} films and that S vacancies are shallow donor defects acting as a weak impurity metal. The shift of the valence-band maximum (VBM) with respect to the Fermi level, quantified by hard x-ray photoelectron spectroscopy (Ga Kα, 9.25 keV), further corroborates the induced n type of conductivity in annealed samples. Our findings indicate that vacuum annealing induces V_{S} defects that dominate charge transport, resulting in n-type conductivity in BaZrS_{3} under S-poor conditions. These discoveries will inform important design choices, such as selecting appropriate contact materials, for integrating BaZrS_{3} into solar cell structures or other devices.http://doi.org/10.1103/t7ns-99dk |
| spellingShingle | Garima Aggarwal Adeem Saeed Mirza Stefania Riva Corrado Comparotto Robert J. W. Frost Soham Mukherjee Monica Morales-Masis Håkan Rensmo Jonathan Staaf Scragg Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS_{3} PRX Energy |
| title | Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS_{3} |
| title_full | Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS_{3} |
| title_fullStr | Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS_{3} |
| title_full_unstemmed | Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS_{3} |
| title_short | Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS_{3} |
| title_sort | charge transport and defects in sulfur deficient chalcogenide perovskite bazrs 3 |
| url | http://doi.org/10.1103/t7ns-99dk |
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