Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
J Am Chem Soc. 2011 Dec 28;133(51):20769-77. doi: 10.1021/ja205140h. Epub 2011 Dec 1.
For over a quarter of a century the hydrogen-terminated Si(111) single-crystalline surface has been the gold standard as a starting point for silicon surface modification chemistry. However, creating a well-defined and stable interface based on Si-N bonds has remained elusive. Despite the fact that azides, nitro compounds, and amines do lead to the formation of surface Si-N, each of these modification schemes produces additional carbon- or oxygen-containing functional groups that in turn react with the surface itself, leaving contaminants that affect the interface properties for any further modification protocols. We describe the preparation of a Si(111) surface functionalized predominantly with Si-NH-Si species based on chlorination followed by the room temperature ammonia treatment utilizing NH(3)-saturated tetrahydrofuran (THF). The obtained surface has been characterized by infrared spectroscopy and X-ray photoelectron spectroscopy. This analysis was supplemented with DFT calculations. This newly characterized surface will join the previously established H-Si(111) and Cl-Si(111) surfaces as a general starting point for the preparation of oxygen- and carbon-free interfaces, with numerous potential applications.
在过去的四分之一个世纪里,氢终止的 Si(111) 单晶表面一直是硅表面改性化学的起点,是黄金标准。然而,基于 Si-N 键创建一个定义明确且稳定的界面仍然难以实现。尽管叠氮化物、硝基化合物和胺确实会导致表面 Si-N 的形成,但这些修饰方案中的每一种都会产生额外的含碳或含氧官能团,这些官能团反过来又会与表面本身反应,留下污染物,影响任何进一步修饰方案的界面特性。我们描述了一种基于氯化,然后在室温下用氨处理,利用氨饱和的四氢呋喃(THF)来制备主要含有 Si-NH-Si 物种的 Si(111) 表面的方法。所得到的表面已经通过红外光谱和 X 射线光电子能谱进行了表征。该分析得到了密度泛函理论(DFT)计算的补充。这个新的表面将与之前建立的 H-Si(111) 和 Cl-Si(111) 表面一起作为制备无碳和无氧界面的通用起点,具有许多潜在的应用。