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Title: Template-free vapor-phase growth of patrónite by atomic layer deposition

Despite challenges to control stoichiometry in the vanadium-sulfur system, template-free growth of patrónite, VS 4, thin films is demonstrated for the first time. A novel atomic layer deposition (ALD) process enables the growth of phase pure films and the study of electrical and vibrational properties of the quasi-one-dimensional (1D) transition metal sulfide. Self-limiting surface chemistry during ALD of VS4 is established via in situ quartz crystal microbalance and quadrupole mass spectrometry between 150 to 200 °C. The V precursor, unconventionally, sheds all organic components in the first half-cycle, while the H 2S half-cycle generates the disulfide dimer moiety, S 2 -2, and oxidizes V 3+ to V 4+. X-ray analysis establishes VS 4 crystallinity and phase purity, as well as a self-limiting growth rate of 0.33 Å/cy, modest roughness (2.4 nm) and expected density (2.7g/cm 3 ). Phase pure films enable a new assignment of vibrational modes and corresponding Raman activity of VS4 that is corroborated by density functional theory (DFT) calculations. Lastly, at elevated growth temperatures, a change in the surface mechanism provides a synthetic route to a second vanadium-sulfur phase, V 2S 3.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [3] ;  [4] ;  [4] ; ORCiD logo [4] ; ORCiD logo [1] ; ORCiD logo [4]
  1. Illinois Institute of Technology, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Microlink Devices, Inc., Niles, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 7; 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:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Atomic Layer Deposition; Density Functional Theory; In Situ Quartz Crystal Microbalance; Patrónite; Raman Spectroscopy; V(V2 -2)2; VS4
OSTI Identifier:
1352533