Dioxo鈥揊luoroalkoxide Tungsten(VI) Complexes for Growth of WOx Thin Films by Aerosol-Assisted Chemical Vapor Deposition

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• 作者：Richard O. Bonsu ; Hankook Kim ; Christopher O鈥橠onohue ; Roman Y. Korotkov ; Khalil A. Abboud ; Timothy J. Anderson ; Lisa McElwee-White
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：August 3, 2015
• 年：2015
• 卷：54
• 期：15
• 页码：7536-7547
• 全文大小：803K
• ISSN：1520-510X

文摘

The soluble bis(fluoroalkoxide) dioxo tungsten(VI) complexes WO₂(OR)₂(DME) [1, R = C(CF₃)₂CH₃; 2, R = C(CF₃)₃] have been synthesized by alkoxide鈥揷hloride metathesis and evaluated as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WO_x. The ¹H NMR and ¹⁹F NMR spectra of 1 and 2 are consistent with an equilibrium between the dimethoxyethane (DME) complexes 1 and 2 and the solvato complexes WO₂(OR)₂(CD₃CN)₂ [1b, R = C(CF₃)₂CH₃; 2b, R = C(CF₃)₃] in acetonitrile-d₃ solution. Studies of the fragmentation of 1 and 2 by mass spectrometry and thermolysis resulted in observation of DME and the corresponding alcohols, with hexafluoroisobutylene also generated from 1. DFT calculations on possible decomposition mechanisms for 1 located pathways for hydrogen abstraction by a terminal oxo to form hexafluoroisobutylene, followed by dimerization of the resulting terminal hydroxide complex and dissociation of the alcohol. AACVD using 1 occurred between 100 and 550 掳C and produced both substoichiometric amorphous WO_x and a polycrystalline W₁₈O₄₉ monoclinic phase, which exhibits 1-D preferred growth in the [010] direction. The work function (4.9鈥?.6 eV), mean optical transmittance (39.1鈥?1.1%), conductivity (0.4鈥?.3 S/cm), and surface roughness (3.4鈥?.9 nm) of the WO_x films are suitable for charge injection layers in organic electronics.