10.1021/acs.chemmater.6b05084.s008
Matthew
S. Weimer
Matthew S.
Weimer
Robert F. McCarthy
Robert F.
McCarthy
Jonathan D. Emery
Jonathan D.
Emery
Michael J. Bedzyk
Michael J.
Bedzyk
Fatih G. Sen
Fatih G.
Sen
Alper Kinaci
Alper
Kinaci
Maria K. Y. Chan
Maria
K. Y. Chan
Adam S. Hock
Adam S.
Hock
Alex B. F. Martinson
Alex
B. F. Martinson
Template-Free Vapor-Phase Growth of Patrónite
by Atomic Layer Deposition
American Chemical Society
2017
Atomic Layer Deposition
VS 4 crystallinity
self-limiting growth rate
H 2 S half-cycle
vibrational
ALD
density
disulfide dimer moiety
quadrupole mass spectrometry
quartz crystal microbalance
transition metal sulfide
VS 4
DFT
V 2 S 3
film
Template-Free Vapor-Phase Growth
phase
vanadium
Self-limiting surface chemistry
2017-03-09 00:00:00
Media
https://acs.figshare.com/articles/media/Template-Free_Vapor-Phase_Growth_of_Patro_nite_by_Atomic_Layer_Deposition/4784497
Despite
challenges to control stoichiometry in the vanadium–sulfur
system, template-free growth of patrónite, VS<sub>4</sub>,
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 VS<sub>4</sub> is established via <i>in situ</i> quartz
crystal microbalance and quadrupole mass spectrometry between 150
and 200 °C. The V precursor, unconventionally, sheds all organic
components in the first half-cycle, while the H<sub>2</sub>S half-cycle
generates the disulfide dimer moiety, S<sub>2</sub><sup>–2</sup>, and oxidizes V<sup>3+</sup> to V<sup>4+</sup>. X-ray analysis establishes
VS<sub>4</sub> crystallinity and phase purity, as well as a self-limiting
growth rate of 0.33 Å/cy, modest roughness of 2.4 nm, and expected
density of 2.7 g/cm<sup>3</sup>. Phase pure films enable a new assignment
of vibrational modes and corresponding Raman activity of VS<sub>4</sub> that is corroborated by density functional theory (DFT) calculations.
Finally, at elevated growth temperatures, a change in the surface
mechanism provides a synthetic route to a second vanadium–sulfur
phase, V<sub>2</sub>S<sub>3</sub>.