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Title: Template-Free Vapor-Phase Growth of Patrónite by Atomic Layer Deposition

Authors:
ORCiD logo [1]; ; ORCiD logo [2]; ORCiD logo [2]; ; ; ORCiD logo; ORCiD logo [1]; ORCiD logo
  1. Department of Chemistry, Illinois Institute of Technology, 3101 South Dearborn Street, Chicago, Illinois 60616, United States
  2. Department of Materials Science and Engineering, Northwestern University, 2220 Campus Drive, Evanston, Illinois 60208, United States
Publication Date:
Research Org.:
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) (SC-22)
OSTI Identifier:
1388121
DOE Contract Number:
SC0001059
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 29; Journal Issue: 7; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), solar (photovoltaic), solar (fuels), photosynthesis (natural and artificial), bio-inspired, hydrogen and fuel cells, electrodes - solar, defects, charge transport, spin dynamics, membrane, materials and chemistry by design, optics, synthesis (novel materials), synthesis (self-assembly)

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. 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., and Martinson, Alex B. F. Fri . "Template-Free Vapor-Phase Growth of Patrónite by Atomic Layer Deposition". United States. doi:10.1021/acs.chemmater.6b05084.
@article{osti_1388121,
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 = {},
doi = {10.1021/acs.chemmater.6b05084},
journal = {Chemistry of Materials},
number = 7,
volume = 29,
place = {United States},
year = {Fri Mar 24 00:00:00 EDT 2017},
month = {Fri Mar 24 00:00:00 EDT 2017}
}
  • 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 2more » -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.« less
  • Abstract not provided.
  • Examinations of enzymatic catalysts suggest one key to efficient catalytic activity is discrete size metallo clusters. Mimicking enzymatic cluster systems is synthetically challenging because conventional solution methods are prone to aggregation or require capping of the cluster, thereby limiting its catalytic activity. We introduce site-selective atomic layer deposition (ALD) on porphyrins as an alternative approach to grow isolated metal oxide islands that are spatially separated. Surface-bound tetra-acid free base porphyrins (H2TCPP) may be metalated with Mn using conventional ALD precursor exposure to induce homogeneous hydroxide synthetic handles which acts as a nucleation point for subsequent ALD MnO island growth. Analyticalmore » fitting of in situ QCM mass uptake reveals island growth to be hemispherical with a convergence radius of 1.74 nm. This growth mode is confirmed with synchrotron grazing-incidence small-angle X-ray scattering (GISAXS) measurements. Finally, we extend this approach to other ALD chemistries to demonstrate the generality of this route to discrete metallo island materials.« less
  • Titanium dioxide atomic layer deposition (ALD) is shown to proceed selectively on oxidized surfaces with minimal deposition on hydrogen-terminated silicon using titanium tetrachloride (TiCl{sub 4}) and titanium tetra-isopropoxide [Ti(OCH(CH{sub 3}){sub 2}){sub 4}, TTIP] precursors. Ex situ x-ray photoelectron spectroscopy shows a more rapid ALD nucleation rate on both Si–OH and Si–H surfaces when water is the oxygen source. Eliminating water delays the oxidation of the hydrogen-terminated silicon, thereby impeding TiO{sub 2} film growth. For deposition at 170 °C, the authors achieve ∼2 nm of TiO{sub 2} on SiO{sub 2} before substantial growth takes place on Si–H. On both Si–H and Si–OH, themore » surface reactions proceed during the first few TiCl{sub 4}/TTIP ALD exposure steps where the resulting products act to impede subsequent growth, especially on Si–H surfaces. Insight from this work helps expand understanding of “inherent” substrate selective ALD, where native differences in substrate surface reaction chemistry are used to promote desired selective-area growth.« less