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首页> 外文会议>State-of-the-art program on compound semiconductors 50 (SOTAPOCS 50)-and-processes at the semiconductor solution interface 3 >In-situ infrared kinetic study of multistep chemical modifications of organic monolayers at silicon surfaces
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In-situ infrared kinetic study of multistep chemical modifications of organic monolayers at silicon surfaces

机译：硅表面有机单层多步化学修饰的原位红外动力学研究

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摘要

The reaction of activation of acid-terminated organic monolayers grafted on (111)Si surfaces into succinimidyl-ester terminated monolayers by treatment in N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS) has been studied by infrared spectroscopy and its kinetics have been followed in situ. The reaction exhibits non exponential kinetics, with an initial fast rise in the appearance of succinimidyl ester followed by a long reaction tail. The origin of this behavior can be ascribed either to the existence of a fast reaction pathway involving anhydride formation, or to the rate limitation by steric hindrance effects. The subsequent amidation of the succinimidyl ester layers by a primary amine has been studied similarly. Here, the kinetics are found to be exponential, but the reaction rate exhibits a sublinear dependence on the amine concentration. This behavior is ascribed to the effects of electrostatic interactions on the adsorption of the protonated amine onto the Si surface prior to reaction.
机译：通过在N-乙基-N'-（3-二甲基氨基丙基）-碳二亚胺（EDC）和N-羟基琥珀酰亚胺（NHS）中进行处理，将接枝在（111）Si表面上的酸封端的有机单层活化为琥珀酰亚胺基酯封端的单层的反应已经通过红外光谱法对其进行了研究，并且对其动力学进行了原位跟踪。该反应表现出非指数动力学，琥珀酰亚胺酯的外观最初快速上升，随后是长反应尾。这种行为的起因可以归因于存在涉及酸酐形成的快速反应路径，或者归因于空间位阻效应的速率限制。类似地研究了随后由伯胺酰胺化琥珀酰亚胺基酯层。在此，发现动力学是指数的，但是反应速率显示出对胺浓度的亚线性依赖性。该行为归因于静电相互作用对反应之前质子化胺在Si表面上的吸附的影响。

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