Laboratory of Laser Chemistry, Institute of Chemical Process Fundamentals, ASCR, 16502, Prague, Czech Republic.
Dalton Trans. 2012 Feb 14;41(6):1727-33. doi: 10.1039/c1dt11587a. Epub 2011 Dec 8.
IR laser-induced gas-phase photolysis of Fe(CO)(5)-SiH(4) mixtures occurs as SiH(4)-photosensitized decomposition of Fe(CO)(5) is accelerated by products of this decomposition and it results in deposition of amorphous Si/Fe nanocomposite films. Analyses of the deposited and subsequently annealed solid films were made by FTIR, Raman and X-ray photoelectron spectroscopy, X-ray diffraction and electron microscopy. The deposited films are amorphous, contain crystalline nanostructures of iron silicide FeSi(2) and undergo atmospheric oxidation in topmost layers to iron oxide and hydrogenated silicon oxide. Upon annealing they develop nanocrystalline structures of ferrisilicate, Fe(1.6)SiO(4), carbon-encaged iron disilicide, FeSi(2), and very rare hexagonal (high-pressure) Fe surviving at ambient conditions. The mechanism of formation of these nanostructures is discussed in terms of gas-phase and solid-phase reactions.
IR 激光诱导 Fe(CO)(5)-SiH(4)混合物的气相光解，是由于 Fe(CO)(5)的 SiH(4)-光解敏化分解被分解产物加速，从而导致非晶态 Si/Fe 纳米复合材料薄膜的沉积。通过傅里叶变换红外光谱、拉曼光谱和 X 射线光电子能谱、X 射线衍射和电子显微镜对沉积后的固体薄膜进行了分析。沉积的薄膜为非晶态，含有铁硅化物 FeSi(2)的结晶纳米结构，并在最顶层发生大气氧化，生成氧化铁和氢化硅氧化物。在退火过程中，它们会形成铁橄榄石、Fe(1.6)SiO(4)、碳笼封铁二硅化物、FeSi(2)的纳米晶结构，以及在环境条件下极为罕见的六方（高压）Fe 相。本文根据气相和固相反应，讨论了这些纳米结构的形成机制。
