Template-free vapor-phase growth of patrónite by atomic layer deposition
Abstract
Despite challenges to control stoichiometry in the vanadium-sulfur system, template-free growth of patrónite, VS4, 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 H2S half-cycle generates the disulfide dimer moiety, S2-2, and oxidizes V3+ to V4+. X-ray analysis establishes VS4 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/cm3 ). 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, V2S3.
- Authors:
-
- Illinois Institute of Technology, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); Microlink Devices, Inc., Niles, IL (United States)
- Northwestern Univ., Evanston, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1352533
- Grant/Contract Number:
- AC02-06CH11357; SC0001059
- Resource 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)
- 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
Citation Formats
Weimer, Matthew S., McCarthy, Robert F., Emery, Jonathan D., Bedzyk, Michael J., Sen, Fatih G., Kinaci, Alper, Chan, Maria K. Y., Hock, Adam S., and Martinson, Alex B. F. Template-free vapor-phase growth of patrónite by atomic layer deposition. United States: N. p., 2017.
Web. doi:10.1021/acs.chemmater.6b05084.
Weimer, Matthew S., McCarthy, Robert F., Emery, Jonathan D., Bedzyk, Michael J., Sen, Fatih G., Kinaci, Alper, Chan, Maria K. Y., Hock, Adam S., & Martinson, Alex B. F. Template-free vapor-phase growth of patrónite by atomic layer deposition. United States. https://doi.org/10.1021/acs.chemmater.6b05084
Weimer, Matthew S., McCarthy, Robert F., Emery, Jonathan D., Bedzyk, Michael J., Sen, Fatih G., Kinaci, Alper, Chan, Maria K. Y., Hock, Adam S., and Martinson, Alex B. F. Thu .
"Template-free vapor-phase growth of patrónite by atomic layer deposition". United States. https://doi.org/10.1021/acs.chemmater.6b05084. https://www.osti.gov/servlets/purl/1352533.
@article{osti_1352533,
title = {Template-free vapor-phase growth of patrónite by atomic layer deposition},
author = {Weimer, Matthew S. and McCarthy, Robert F. and Emery, Jonathan D. and Bedzyk, Michael J. and Sen, Fatih G. and Kinaci, Alper and Chan, Maria K. Y. and Hock, Adam S. and Martinson, Alex B. F.},
abstractNote = {Despite challenges to control stoichiometry in the vanadium-sulfur system, template-free growth of patrónite, VS4, 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 H2S half-cycle generates the disulfide dimer moiety, S2-2, and oxidizes V3+ to V4+. X-ray analysis establishes VS4 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/cm3 ). 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, V2S3.},
doi = {10.1021/acs.chemmater.6b05084},
journal = {Chemistry of Materials},
number = 7,
volume = 29,
place = {United States},
year = {Thu Mar 09 00:00:00 EST 2017},
month = {Thu Mar 09 00:00:00 EST 2017}
}
Web of Science
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