TY - DATA T1 - Template-Free Vapor-Phase Growth of Patrónite by Atomic Layer Deposition PY - 2017/03/09 AU - Matthew S. Weimer AU - Robert F. McCarthy AU - Jonathan D. Emery AU - Michael J. Bedzyk AU - Fatih G. Sen AU - Alper Kinaci AU - Maria K. Y. Chan AU - Adam S. Hock AU - Alex B. F. Martinson UR - https://acs.figshare.com/articles/media/Template-Free_Vapor-Phase_Growth_of_Patro_nite_by_Atomic_Layer_Deposition/4784497 DO - 10.1021/acs.chemmater.6b05084.s008 L4 - https://ndownloader.figshare.com/files/7860430 KW - Atomic Layer Deposition KW - VS 4 crystallinity KW - self-limiting growth rate KW - H 2 S half-cycle KW - vibrational KW - ALD KW - density KW - disulfide dimer moiety KW - quadrupole mass spectrometry KW - quartz crystal microbalance KW - transition metal sulfide KW - VS 4 KW - DFT KW - V 2 S 3 KW - film KW - Template-Free Vapor-Phase Growth KW - phase KW - vanadium KW - Self-limiting surface chemistry N2 - 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 and 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 of 2.4 nm, and expected density of 2.7 g/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. Finally, at elevated growth temperatures, a change in the surface mechanism provides a synthetic route to a second vanadium–sulfur phase, V2S3. ER -