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Title: Role of Point Defects in Enhancing the Conductivity of BiVO4

Abstract

We report that bismuth vanadate is a promising photoanode for solar-to-fuel photocatalytic applications, and it has been extensively studied in recent years. However, the microscopic mechanism underlying the observed changes in electronic conductivity due to oxygen vacancies and nitrogen dopants remains unclear. Here, we combine electronic structure calculations at the hybrid density functional theory (DFT) level with constrained DFT, and we elucidate the role of defects in enhancing the transport properties of the material. We show that at low temperature, oxygen vacancies give rise to deep levels within the fundamental gap of BVO; however even as deep levels, oxygen vacancies can act as effective n-dopants and polaronic charge carriers, due to their favorable position in energy relative to polarons in the pristine bulk. In addition, we show that N atoms can be easily introduced in n-doped BiVO4 and that the presence of substitutional nitrogen affects the formation energy of polarons, effectively contributing to an increase of the carrier mobility in the material. Lastly, our results reconcile apparently conflicting experiments and they may be generalized to other transition metal oxides, thus providing a foundation for polaronic defect engineering in photoanodes for water photocatalysis.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]
  1. Ajou University, Suwon (Korea, Republic of); Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of California, Santa Cruz, CA (United States)
  3. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Research Foundation of Korea (NRF); National Science Foundation (NSF); University of Chicago - Materials Research Science & Engineering Center (MRSEC)
OSTI Identifier:
1616525
Grant/Contract Number:  
AC02-06CH11357; FG02-06ER46262; 2018R1C1B6008980; DMR-1760260
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 21; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Seo, Hosung, Ping, Yuan, and Galli, Giulia. Role of Point Defects in Enhancing the Conductivity of BiVO4. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.8b03201.
Seo, Hosung, Ping, Yuan, & Galli, Giulia. Role of Point Defects in Enhancing the Conductivity of BiVO4. United States. https://doi.org/10.1021/acs.chemmater.8b03201
Seo, Hosung, Ping, Yuan, and Galli, Giulia. Wed . "Role of Point Defects in Enhancing the Conductivity of BiVO4". United States. https://doi.org/10.1021/acs.chemmater.8b03201. https://www.osti.gov/servlets/purl/1616525.
@article{osti_1616525,
title = {Role of Point Defects in Enhancing the Conductivity of BiVO4},
author = {Seo, Hosung and Ping, Yuan and Galli, Giulia},
abstractNote = {We report that bismuth vanadate is a promising photoanode for solar-to-fuel photocatalytic applications, and it has been extensively studied in recent years. However, the microscopic mechanism underlying the observed changes in electronic conductivity due to oxygen vacancies and nitrogen dopants remains unclear. Here, we combine electronic structure calculations at the hybrid density functional theory (DFT) level with constrained DFT, and we elucidate the role of defects in enhancing the transport properties of the material. We show that at low temperature, oxygen vacancies give rise to deep levels within the fundamental gap of BVO; however even as deep levels, oxygen vacancies can act as effective n-dopants and polaronic charge carriers, due to their favorable position in energy relative to polarons in the pristine bulk. In addition, we show that N atoms can be easily introduced in n-doped BiVO4 and that the presence of substitutional nitrogen affects the formation energy of polarons, effectively contributing to an increase of the carrier mobility in the material. Lastly, our results reconcile apparently conflicting experiments and they may be generalized to other transition metal oxides, thus providing a foundation for polaronic defect engineering in photoanodes for water photocatalysis.},
doi = {10.1021/acs.chemmater.8b03201},
journal = {Chemistry of Materials},
number = 21,
volume = 30,
place = {United States},
year = {2018},
month = {9}
}

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