High-Throughput Experimental Study of Wurtzite Mn 1– x Zn x O Alloys for Water Splitting Applications

Ndione, Paul F.; Ratcliff, Erin L.; Dey, Suhash R.; Warren, Emily L.; Peng, Haowei; Holder, Aaron M.; Lany, Stephan; Gorman, Brian P.; Al-Jassim, Mowafak M.; Deutsch, Todd G.; Zakutayev, Andriy; Ginley, David S.

doi:10.1021/acsomega.8b03347

Title: High-Throughput Experimental Study of Wurtzite Mn _{1– x} Zn _x O Alloys for Water Splitting Applications

Abstract

We used high-throughput experimental screening methods to unveil the physical and chemical properties of Mn_1–xZn_xO wurtzite alloys and identify their appropriate composition for effective water splitting application. The Mn_1–xZn_xO thin films were synthesized using combinatorial pulsed laser deposition, permitting for characterization of a wide range of compositions with x varying from 0 to 1. The solubility limit of ZnO in MnO was determined using the disappearing phase method from X-ray diffraction and X-ray fluorescence data and found to increase with decreasing substrate temperature due to kinetic limitations of the thin-film growth at relatively low temperature. Optical measurements indicate the strong reduction of the optical band gap down to 2.1 eV at x = 0.5 associated with the rock salt-to-wurtzite structural transition in Mn_1–xZn_xO alloys. Transmission electron microscopy results show evidence of a homogeneous wurtzite alloy system for a broad range of Mn_1–xZn_xO compositions above x = 0.4. The wurtzite Mn_1–xZn_xO samples with the 0.4 < x < 0.6 range were studied as anodes for photoelectrochemical water splitting, with a maximum current density of 340 μA cm^–2 for 673 nm-thick films. These Mn_1–xZn_xO films were stable in pH = 10, showing no evidence of photocorrosion or degradation after 24 h undermore »« less

Authors:

^[1];

^[2]; Dey, Suhash R. ^[3];

^[1]; Peng, Haowei ^[1];

^[1]; Lany, Stephan ^[1]; Gorman, Brian P. ^[4]; Al-Jassim, Mowafak M. ^[1]; Deutsch, Todd G. ^[1];

^[1]; Ginley, David S. ^[1]

Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
Department of Materials Science and Engineering, The University of Arizona, Tucson, Arizona 85721, United States
Department of Materials Science and Metallurgical Engineering, Indian Institute of Technology Hyderabad, Kandi, Sangareddy, Hyderabad 502285, India
Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States, Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401, United States

Publication Date:: Wed Apr 24 00:00:00 EDT 2019

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1508685

Alternate Identifier(s):: OSTI ID: 1510035; OSTI ID: 1512675

Report Number(s):: NREL/JA-5900-73457
Journal ID: ISSN 2470-1343

Grant/Contract Number:: AC36-08GO28308

Resource Type:: Published Article

Journal Name:: ACS Omega

Additional Journal Information:: Journal Name: ACS Omega Journal Volume: 4 Journal Issue: 4; Journal ID: ISSN 2470-1343

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; analytical chemistry; catalysts; combinatorial chemistry; crystal structure; electric properties; energy level; phase; phase transition; semiconductors; solid state electrochemistry; solubility; spectra; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats


                    Ndione, Paul F., Ratcliff, Erin L., Dey, Suhash R., Warren, Emily L., Peng, Haowei, Holder, Aaron M., Lany, Stephan, Gorman, Brian P., Al-Jassim, Mowafak M., Deutsch, Todd G., Zakutayev, Andriy, and Ginley, David S. High-Throughput Experimental Study of Wurtzite Mn 1– x Zn x O Alloys for Water Splitting Applications.  United States: N. p., 2019. 
Web.  doi:10.1021/acsomega.8b03347.

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                    Ndione, Paul F., Ratcliff, Erin L., Dey, Suhash R., Warren, Emily L., Peng, Haowei, Holder, Aaron M., Lany, Stephan, Gorman, Brian P., Al-Jassim, Mowafak M., Deutsch, Todd G., Zakutayev, Andriy, & Ginley, David S. High-Throughput Experimental Study of Wurtzite Mn 1– x Zn x O Alloys for Water Splitting Applications.  United States.  https://doi.org/10.1021/acsomega.8b03347

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                    Ndione, Paul F., Ratcliff, Erin L., Dey, Suhash R., Warren, Emily L., Peng, Haowei, Holder, Aaron M., Lany, Stephan, Gorman, Brian P., Al-Jassim, Mowafak M., Deutsch, Todd G., Zakutayev, Andriy, and Ginley, David S. Wed .  
"High-Throughput Experimental Study of Wurtzite Mn 1– x Zn x O Alloys for Water Splitting Applications".  United States.  https://doi.org/10.1021/acsomega.8b03347.

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@article{osti_1508685,

  title        = {High-Throughput Experimental Study of Wurtzite Mn 1– x Zn x O Alloys for Water Splitting Applications},

  author       = {Ndione, Paul F. and Ratcliff, Erin L. and Dey, Suhash R. and Warren, Emily L. and Peng, Haowei and Holder, Aaron M. and Lany, Stephan and Gorman, Brian P. and Al-Jassim, Mowafak M. and Deutsch, Todd G. and Zakutayev, Andriy and Ginley, David S.},

  abstractNote = {We used high-throughput experimental screening methods to unveil the physical and chemical properties of Mn1–xZnxO wurtzite alloys and identify their appropriate composition for effective water splitting application. The Mn1–xZnxO thin films were synthesized using combinatorial pulsed laser deposition, permitting for characterization of a wide range of compositions with x varying from 0 to 1. The solubility limit of ZnO in MnO was determined using the disappearing phase method from X-ray diffraction and X-ray fluorescence data and found to increase with decreasing substrate temperature due to kinetic limitations of the thin-film growth at relatively low temperature. Optical measurements indicate the strong reduction of the optical band gap down to 2.1 eV at x = 0.5 associated with the rock salt-to-wurtzite structural transition in Mn1–xZnxO alloys. Transmission electron microscopy results show evidence of a homogeneous wurtzite alloy system for a broad range of Mn1–xZnxO compositions above x = 0.4. The wurtzite Mn1–xZnxO samples with the 0.4 < x < 0.6 range were studied as anodes for photoelectrochemical water splitting, with a maximum current density of 340 μA cm–2 for 673 nm-thick films. These Mn1–xZnxO films were stable in pH = 10, showing no evidence of photocorrosion or degradation after 24 h under water oxidation conditions. Doping Mn1–xZnxO materials with Ga dramatically increases the electrical conductivity of Mn1–xZnxO up to ~1.9 S/cm for x = 0.48, but these doped samples are not active in water splitting. Mott–Schottky and UPS/XPS measurements show that the presence of dopant atoms reduces the space charge region and increases the number of mid-gap surface states. Overall, this study demonstrates that Mn1–xZnxO alloys hold promise for photoelectrochemical water splitting, which could be enhanced with further tailoring of their electronic properties.},

  doi          = {10.1021/acsomega.8b03347},

  journal      = {ACS Omega},

  number       = 4,

  volume       = 4,

  place        = {United States},

  year         = {Wed Apr 24 00:00:00 EDT 2019},

  month        = {Wed Apr 24 00:00:00 EDT 2019}

}

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Figure 1: (a, b) Oxidation state maps obtained by XRD of the Mn−O system at (a) different total pressures as a function of substrate temperature and (b) different oxygen pressures as a function of substrate temperature. (c) Representative XRD patterns of the different phases, with the same color code asmore »

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Title: High-Throughput Experimental Study of Wurtzite Mn 1– x Zn x O Alloys for Water Splitting Applications

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Title: High-Throughput Experimental Study of Wurtzite Mn _{1– x} Zn _x O Alloys for Water Splitting Applications