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>.