Potts Stephen E, Carmalt Claire J, Blackman Christopher S, Leese Thomas, Davies Hywel O
Department of Chemistry, Materials Chemistry Centre, University College London, 20 Gordon Street, London, UK WC1H 0AJ.
Dalton Trans. 2008 Nov 14(42):5730-6. doi: 10.1039/b808650h. Epub 2008 Sep 9.
Thin films of tungsten carbonitride have been formed on glass by low-pressure chemical vapour deposition (LP)CVD at 550 degrees C from four closely related precursors: W(mu-N(t)Bu)(N(t)Bu)Cl(2)(H(2)N(t)Bu), [W(N(t)Bu)(2)Cl(2)(TMEDA)] (TMEDA = N,N,N',N'-tetramethylethylenediamine), [W(N(t)Bu)(2)Cl(2)(py)(2)] (py = pyridine) and [W(N(t)Bu)(2)Cl(N{SiMe(3)}(2))]. The grey mirror-like films were grown with a nitrogen or ammonia bleed gas. In all cases the chlorine content of the deposited films was less than 1 at% and the oxygen content of the films was lower for those grown using ammonia. Surprisingly, the use of ammonia did not significantly change the carbon content of the resulting films. Despite the coordination environment around the metal being essentially the same and the materials having a comparable volatility, some differences in film quality were observed. The films were uniform, adhesive, abrasion resistant, conformal and hard, being resistant to scratching with a steel scalpel. X-Ray powder diffraction patterns of all the films showed the formation of beta-WN(x)C(y). As a comparison the aerosol-assisted chemical vapour deposition (AA)CVD of W(mu-N(t)Bu)(N(t)Bu)Cl(2)(H(2)N(t)Bu) was investigated and amorphous tungsten carbonitride films were deposited.
通过低压化学气相沉积(LP)CVD,在550摄氏度下,由四种密切相关的前体在玻璃上形成了碳氮化钨薄膜:[W(μ-N(t)Bu)(N(t)Bu)Cl₂(H₂N(t)Bu)]₂、[W(N(t)Bu)₂Cl₂(TMEDA)](TMEDA = N,N,N',N'-四甲基乙二胺)、[W(N(t)Bu)₂Cl₂(py)₂](py = 吡啶)和[W(N(t)Bu)₂Cl(N{SiMe₃}₂)]。使用氮气或氨气作为载气生长出灰色镜面状薄膜。在所有情况下,沉积薄膜的氯含量小于1原子百分比,并且对于使用氨气生长的薄膜,其氧含量更低。令人惊讶的是,使用氨气并没有显著改变所得薄膜的碳含量。尽管金属周围的配位环境基本相同且这些材料具有相当的挥发性,但仍观察到薄膜质量存在一些差异。这些薄膜均匀、附着力强、耐磨、保形且坚硬,能用钢手术刀刮擦而不被划伤。所有薄膜的X射线粉末衍射图谱显示形成了β-WNₓCᵧ。作为对比,研究了[W(μ-N(t)Bu)(N(t)Bu)Cl₂(H₂N(t)Bu)]₂的气溶胶辅助化学气相沉积(AA)CVD,并沉积了非晶态碳氮化钨薄膜。