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Title: Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides

Abstract

We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V 2O 3, VO 2, and V 2O 5 are realized via four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O 3, H 2O 2, H 2O/O 2, and H 2O 2/H 2. A clear distinction between non-oxidative protic ligand exchange and metal oxidation is demonstrated through sequential surface reactions with different non-metal precursors. This synergistic effect, provides greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H 2 gas. When H 2 is dosed after H 2O 2 during growth, amorphous films of VO 2 are deposited that are readily crystallized with a low temperature anneal. These VO 2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VOmore » 2.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [5]
  1. Illinois Inst. of Technology, Chicago, IL (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Div.
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Div.
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering and Dept. of Chemistry
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  5. Illinois Inst. of Technology, Chicago, IL (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.
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)
OSTI Identifier:
1393545
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 15; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Weimer, Matthew S., Kim, In Soo, Guo, Peijun, Schaller, Richard D., Martinson, Alex B. F., and Hock, Adam S. Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b01130.
Weimer, Matthew S., Kim, In Soo, Guo, Peijun, Schaller, Richard D., Martinson, Alex B. F., & Hock, Adam S. Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides. United States. doi:10.1021/acs.chemmater.7b01130.
Weimer, Matthew S., Kim, In Soo, Guo, Peijun, Schaller, Richard D., Martinson, Alex B. F., and Hock, Adam S. Fri . "Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides". United States. doi:10.1021/acs.chemmater.7b01130. https://www.osti.gov/servlets/purl/1393545.
@article{osti_1393545,
title = {Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides},
author = {Weimer, Matthew S. and Kim, In Soo and Guo, Peijun and Schaller, Richard D. and Martinson, Alex B. F. and Hock, Adam S.},
abstractNote = {We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V2O3, VO2, and V2O5 are realized via four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O3, H2O2, H2O/O2, and H2O2/H2. A clear distinction between non-oxidative protic ligand exchange and metal oxidation is demonstrated through sequential surface reactions with different non-metal precursors. This synergistic effect, provides greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H2 gas. When H2 is dosed after H2O2 during growth, amorphous films of VO2 are deposited that are readily crystallized with a low temperature anneal. These VO2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VO2.},
doi = {10.1021/acs.chemmater.7b01130},
journal = {Chemistry of Materials},
number = 15,
volume = 29,
place = {United States},
year = {Fri Jun 02 00:00:00 EDT 2017},
month = {Fri Jun 02 00:00:00 EDT 2017}
}

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