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Main Authors: Aggarwal, Garima, Mirza, Adeem Saeed, Riva, Stefania, Comparotto, Corrado, Frost, Robert J. W., Mukherjee, Soham, Morales-Masis, Monica, Rensmo, Håkan, Scragg, Jonathan Staaf
Format: Preprint
Published: 2024
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Online Access:https://arxiv.org/abs/2405.17327
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author Aggarwal, Garima
Mirza, Adeem Saeed
Riva, Stefania
Comparotto, Corrado
Frost, Robert J. W.
Mukherjee, Soham
Morales-Masis, Monica
Rensmo, Håkan
Scragg, Jonathan Staaf
author_facet Aggarwal, Garima
Mirza, Adeem Saeed
Riva, Stefania
Comparotto, Corrado
Frost, Robert J. W.
Mukherjee, Soham
Morales-Masis, Monica
Rensmo, Håkan
Scragg, Jonathan Staaf
contents 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 in BaZrS$_3$ through annealing in an S-poor environment. BaZrS$_3$ thin films are synthesized $\textit{via}$ a two step process: co-sputtering of Ba-Zr followed by sulfurization at 600 $^{\circ}$C, and subsequent annealing in high vacuum. UV-Vis measurement reveal a red-shift in the absorption edge concurrent with sample color darkening after annealing. The increase in defect density with vacuum annealing, coupled with low activation energy and n-type character of defects, strongly suggests that sulfur vacancies (V$_{\mathrm{S}}$) are responsible, in agreement with theoretical predictions. The shift of the Fermi level towards conduction band minimum, quantified by Hard X-ray Photoelectron Spectroscopy (Ga K$α$, 9.25 keV), further corroborates the induced n-type of conductivity in annealed samples. Our findings indicate that vacuum annealing induces V$_{\mathrm{S}}$ defects that dominate the charge transport, thereby making BaZrS$_3$ an n-type semiconductor under S-poor conditions. This study offers crucial insights into understanding the defect properties of BaZrS$_3$, facilitating further improvements for its use in solar cell applications.
format Preprint
id arxiv_https___arxiv_org_abs_2405_17327
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS$_3$
Aggarwal, Garima
Mirza, Adeem Saeed
Riva, Stefania
Comparotto, Corrado
Frost, Robert J. W.
Mukherjee, Soham
Morales-Masis, Monica
Rensmo, Håkan
Scragg, Jonathan Staaf
Materials Science
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 in BaZrS$_3$ through annealing in an S-poor environment. BaZrS$_3$ thin films are synthesized $\textit{via}$ a two step process: co-sputtering of Ba-Zr followed by sulfurization at 600 $^{\circ}$C, and subsequent annealing in high vacuum. UV-Vis measurement reveal a red-shift in the absorption edge concurrent with sample color darkening after annealing. The increase in defect density with vacuum annealing, coupled with low activation energy and n-type character of defects, strongly suggests that sulfur vacancies (V$_{\mathrm{S}}$) are responsible, in agreement with theoretical predictions. The shift of the Fermi level towards conduction band minimum, quantified by Hard X-ray Photoelectron Spectroscopy (Ga K$α$, 9.25 keV), further corroborates the induced n-type of conductivity in annealed samples. Our findings indicate that vacuum annealing induces V$_{\mathrm{S}}$ defects that dominate the charge transport, thereby making BaZrS$_3$ an n-type semiconductor under S-poor conditions. This study offers crucial insights into understanding the defect properties of BaZrS$_3$, facilitating further improvements for its use in solar cell applications.
title Charge Transport and Defects in Sulfur-Deficient Chalcogenide Perovskite BaZrS$_3$
topic Materials Science
url https://arxiv.org/abs/2405.17327