Chemistry with a tiny hammer - cleaving the C-H bonds of adsorbed organic molecules with hyperthermal protons

这个建议旨在探索我的概念，用一个小锤子-一个超热质子，合成新的聚合物薄膜。 最近我的研究小组发现，当吸附的碳氢分子被10 eV的质子轰击时，能量转移在H-H碰撞中是有效的，而在H-C碰撞中是无效的。 运动学上的这种差异导致C-H键的裂解而没有C-C键断裂。 吸附的烃分子由此交联成可交联聚合物膜。 在接下来的五年里，我们将进一步阐明这种方法的性质和反应机理，以及它对生产具有定制物理和化学性能的新型聚合物薄膜的适用范围。 为了研究反应机制，我们将分析在离子轰击过程中从吸附的前体分子发射的物质作为离子能量和离子类型（H+，D+和He+）的函数。 我们将把这些数据与从轰击样品的表面分析中收集的数据进行比较。 为了探索所提出的超热质子方法的应用，我们将使用它来裂解共轭半导体聚合物膜的C-H键，从而增加平均共轭链长度与诱导交联。 通常将沉积的共轭聚合物膜热固化以增加交联和导电性。拟议的质子处理提供了一种有吸引力的替代方案，因为它是一种无需加热的干式工艺。 除了这个应用程序，我们将使用该方法来交联不饱和和芳香族有机硅烷自组装单分子膜的导电基板，如n-TiO 2，分子电子学的发展。 我们已作好准备，并确定我们建议的方法是可行的。因此，我们有信心，如果拟议的项目获得批准，我们将产生具有科学和技术影响的原创成果，并在这一市场驱动的领域培养高素质的人才。

This proposal aims at exploring my concept of performing chemistry with a tiny hammer - a hyperthermal proton, for the synthesis of novel polymer films.  Recently my research team showed that when adsorbed hydrocarbon molecules are bombarded by 10eV protons, the energy transfer is effective in H-H collisions but ineffective in H-C collisions.  Such a difference in kinematics leads to the cleavage of C-H bonds with no C-C bond breakage.  The adsorbed hydrocarbon molecules are thereby cross-linked into an ultrathin polymer film.  In the next five years, we will further clarify the nature and reaction mechanisms of this method and its scope of applicability towards the production of novel polymer films having tailor-made physical and chemical properties.  To study the reaction mechanisms, we will analyze species emitted from adsorbed precursor molecules during ion bombardment as a function of ion energy and ion type (H+, D+, and He+).  We will compare these data with those collected from surface analysis of the bombarded samples.  To explore the applications of the proposed hyperthermal proton method, we will use it to cleave C-H bonds of conjugated semiconducting polymer films and thereby to increase the average conjugated chain length with the induced cross-linking.  Normally as-deposited conjugated polymer films are thermally cured to increase cross-linking and electrical conductivity. The proposed proton treatment provides an attractive alternative as it is a dry process with no heating requirement.  In addition to this application, we will use the method to cross-link unsaturated and aromatic organosilane self-assembly monolayers on conductive substrates such as n-TiO2, for the development of molecular electronics.   We have already paved the ground work and confirmed the feasibility of our proposed approaches. Therefore, we are confident that if the proposed project is approved, we will produce original results bearing both scientific and technological impacts, and train highly qualified personnel in this market-driven field.