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

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:
Grant/Contract Number:
AC02-06CH11357
Type:
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)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1393545