ZnxMn1–xO Solid Solutions in the Rocksalt Structure: Optical, Charge Transport, and Photoelectrochemical Properties
Abstract
Theoretical predictions of ZnO:MnO solid solutions (abbreviated here as ZMO) with the rocksalt-type structure suggest improved visible light absorption and suitable band edge positions for the overall water splitting reaction, but experimental efforts to produce such phases are limited by the low solubility of Zn within this structure type. In this paper, we produce solid solutions of ZnxMn1–xO, with x = 0.5 and 0.3 in the metastable rocksalt phase, using high-pressure and high-temperature (HPHT) techniques. X-ray diffraction and electron microscopy methods were employed to determine the crystal structure, chemical composition, and homogeneity on the submicron scale. The solid solutions exhibit increased optical absorbance in the visible spectral range as compared to those of the parent oxides ZnO and MnO. Our theoretical calculations for ZnxMn1–xO with x = 0.5, 0.25 predict band gaps of 2.53 and 2.98 eV, respectively, with an unusually large band gap bowing. Our calculations also show small effective electron mass for these materials indicating their potential for solar energy applications. In conclusion, initial photoelectrochemical tests reveal that ZMO solid solutions are suitable for water oxidation and warrant further experimental optimization.
- Authors:
-
[1];
[2];
[1]
- Carnegie Inst. of Science, Washington, DC (United States)
- Arizona State Univ., Tempe, AZ (United States)
- Lehigh Univ., Bethlehem, PA (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1470231
- Grant/Contract Number:
- AC36-99GO10337; SC0001057
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Energy Materials
- Additional Journal Information:
- Journal Volume: 1; Journal Issue: 2; Related Information: CNGMD partners with National Renewable Energy Laboratory (lead); Colorado School of Mines; Harvard University; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; Oregon State University; SLAC National Accelerator Laboratory; Journal ID: ISSN 2574-0962
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; solar (photovoltaic); solar (fuels); solid state lighting; phonons; thermoelectric; hydrogen and fuel cells; defects; charge transport; optics; materials and chemistry by design; synthesis (novel materials); metastable oxides; high-pressure synthesis; band gap bowing; photoelectrochemical water-splitting
Citation Formats
Bhadram, Venkata S., Cheng, Qian, Chan, Candace K., Liu, Yiqun, Lany, Stephan, Landskron, Kai, and Strobel, Timothy A. ZnxMn1–xO Solid Solutions in the Rocksalt Structure: Optical, Charge Transport, and Photoelectrochemical Properties. United States: N. p., 2018.
Web. doi:10.1021/acsaem.7b00084.
Bhadram, Venkata S., Cheng, Qian, Chan, Candace K., Liu, Yiqun, Lany, Stephan, Landskron, Kai, & Strobel, Timothy A. ZnxMn1–xO Solid Solutions in the Rocksalt Structure: Optical, Charge Transport, and Photoelectrochemical Properties. United States. https://doi.org/10.1021/acsaem.7b00084
Bhadram, Venkata S., Cheng, Qian, Chan, Candace K., Liu, Yiqun, Lany, Stephan, Landskron, Kai, and Strobel, Timothy A. Thu .
"ZnxMn1–xO Solid Solutions in the Rocksalt Structure: Optical, Charge Transport, and Photoelectrochemical Properties". United States. https://doi.org/10.1021/acsaem.7b00084. https://www.osti.gov/servlets/purl/1470231.
@article{osti_1470231,
title = {ZnxMn1–xO Solid Solutions in the Rocksalt Structure: Optical, Charge Transport, and Photoelectrochemical Properties},
author = {Bhadram, Venkata S. and Cheng, Qian and Chan, Candace K. and Liu, Yiqun and Lany, Stephan and Landskron, Kai and Strobel, Timothy A.},
abstractNote = {Theoretical predictions of ZnO:MnO solid solutions (abbreviated here as ZMO) with the rocksalt-type structure suggest improved visible light absorption and suitable band edge positions for the overall water splitting reaction, but experimental efforts to produce such phases are limited by the low solubility of Zn within this structure type. In this paper, we produce solid solutions of ZnxMn1–xO, with x = 0.5 and 0.3 in the metastable rocksalt phase, using high-pressure and high-temperature (HPHT) techniques. X-ray diffraction and electron microscopy methods were employed to determine the crystal structure, chemical composition, and homogeneity on the submicron scale. The solid solutions exhibit increased optical absorbance in the visible spectral range as compared to those of the parent oxides ZnO and MnO. Our theoretical calculations for ZnxMn1–xO with x = 0.5, 0.25 predict band gaps of 2.53 and 2.98 eV, respectively, with an unusually large band gap bowing. Our calculations also show small effective electron mass for these materials indicating their potential for solar energy applications. In conclusion, initial photoelectrochemical tests reveal that ZMO solid solutions are suitable for water oxidation and warrant further experimental optimization.},
doi = {10.1021/acsaem.7b00084},
journal = {ACS Applied Energy Materials},
number = 2,
volume = 1,
place = {United States},
year = {Thu Feb 01 00:00:00 EST 2018},
month = {Thu Feb 01 00:00:00 EST 2018}
}
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