Tailoring precursors for deposition: synthesis, structure, and thermal studies of cyclopentadienylcopper(i) isocyanide complexes.
Tailoring precursors for deposition: synthesis, structure, and thermal studies of cyclopentadienylcopper(i) isocyanide complexes.
复制标题
DOI：
10.1021/acs.inorgchem.5b00448
复制
发表时间：
2015-05
影响因子：
4.6
通讯作者：
Alexander M Willcocks;Thomas Pugh;Samuel D. Cosham;J. A. Hamilton;S. Sung;Tobias Heil;P. Chalker;Paul A. Williams;G. Kociok‐Köhn;A. Johnson
中科院分区：
文献类型：
--
作者：
Alexander M Willcocks;Thomas Pugh;Samuel D. Cosham;J. A. Hamilton;S. Sung;Tobias Heil;P. Chalker;Paul A. Williams;G. Kociok‐Köhn;A. Johnson
在这里，我们报告的合成和表征的一个家庭的铜（I）金属前体周围的金属和异氰化物配体的基础。用单晶X-射线衍射分析确定了几种环戊二烯基异氰化铜配合物的分子结构。配合物的热重分析突出了异丙基异氰化物配合物[（η（5）-C5 H5）Cu（CN（i）Pr）]（2a）和叔丁基异氰化物配合物[（η（5）-C5 H5）Cu（CN（t）Bu）]（2b）作为可能的铜金属化学气相沉积（CVD）前体。前体的进一步修改与变化的取代基上的双金属配体系统（变化之间的H，Me，Et，和（i）Pr）已经允许的影响，这些变化将对功能，如稳定性，挥发性，和分解进行调查。作为该研究的一部分，已经测定了配合物2b、[（η（5）-MeC 5 H4）Cu（CN（t）Bu）]（3b）、[（η（5）-EtC 5 H4）Cu（CN（t）Bu）]（4 b）和[（η（5）-（i）PrC 5 H4）Cu（CN（t）Bu）]（5 b）在40-65 °C温度范围内的蒸气压。采用低压化学气相沉积（LP-CVD），使用前体2a和2b在H2气氛下在硅、金和铂衬底上合成金属铜的薄膜。通过扫描电子显微镜和原子力显微镜对在180 ° C和300 °C的衬底温度下沉积在硅和金衬底上的薄膜进行分析，揭示了温度依赖的生长特征：在300 °C下生长的薄膜是连续的，没有针孔，而在180 °C下生长的薄膜由高度结晶的纳米颗粒组成。相比之下，在180 °C下在铂衬底上的沉积显示出高度的表面覆盖，形成高密度、连续且无针孔的薄膜。粉末X射线衍射和X射线光电子能谱（XPS）都表明薄膜是高纯度的金属铜。
We report here the synthesis and characterization of a family of copper(I) metal precursors based around cyclopentadienyl and isocyanide ligands. The molecular structures of several cyclopentadienylcopper(I) isocyanide complexes have been unambiguously determined by single-crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl isocyanide complex [(η(5)-C5H5)Cu(CN(i)Pr)] (2a) and the tert-butyl isocyanide complex [(η(5)-C5H5)Cu(CN(t)Bu)] (2b) as possible copper metal chemical vapor deposition (CVD) precursors. Further modification of the precursors with variation of the substituents on the cyclopentadienyl ligand system (varying between H, Me, Et, and (i)Pr) has allowed the affect that these changes would have on features such as stability, volatility, and decomposition to be investigated. As part of this study, the vapor pressures of the complexes 2b, [(η(5)-MeC5H4)Cu(CN(t)Bu)] (3b), [(η(5)-EtC5H4)Cu(CN(t)Bu)] (4b), and [(η(5)-(i)PrC5H4)Cu(CN(t)Bu)] (5b) over a 40-65 °C temperature range have been determined. Low-pressure chemical vapor deposition (LP-CVD) was employed using precursors 2a and 2b to synthesize thin films of metallic copper on silicon, gold, and platinum substrates under a H2 atmosphere. Analysis of the thin films deposited onto both silicon and gold substrates at substrate temperatures of 180 and 300 °C by scanning electron microscopy and atomic force microscopy reveals temperature-dependent growth features: Films grown at 300 °C are continuous and pinhole-free, whereas films grown at 180 °C consist of highly crystalline nanoparticles. In contrast, deposition onto platinum substrates at 180 °C shows a high degree of surface coverage with the formation of high-density, continuous, and pinhole-free thin films. Powder X-ray diffraction and X-ray photoelectron spectroscopy (XPS) both show the films to be high-purity metallic copper.