聚氧乙烯酸酯杂化物在平面硅/氧化硅上的共价接枝：氧化物上多酸酯层的研究
Covalent Grafting of Polyoxometalate Hybrids onto Flat Silicon/Silicon Oxide: Insights from POMs Layers on Oxides
摘要：
将聚氧乙烯酸酯（POMs）固定到氧化物上与催化、能量转换/存储或分子电子学领域中的许多应用相关。优化和理解分子/氧化物界面对于合理提高最终分子材料的性能至关重要。我们在此描述了POM杂化物的合成和共价接枝到平面Si/SiO2基板上的远程羧酸功能。特别注意已支付的分子层的表征和通过使用各种表征技术，包括椭圆偏振法，AFM，XPS和FTIR的氧化物界面处的POM锚定模式的描述。最后，探讨了垂直结结构中的电子输运性质，绘制了能级图，并结合循环伏安法、紫外-可见吸收光谱和理论计算对POM分子的电子特性进行了讨论。这些基于POM的分子结的电子性质由POM LUMO（d轨道）驱动，无论系链或锚定基团的性质如何。
英文摘要：
Immobilization of polyoxometalates (POMs) onto oxides is relevant to many applications in the fields of catalysis, energy conversion/storage or molecular electronics. Optimization and understanding the molecule/oxide interface is crucial to rationally improve the performance of the final molecular materials. We herein describe the synthesis and covalent grafting of POM hybrids with remote carboxylic acid functions onto flat Si/SiO2 substrates. Special attention has been paid to the characterization of the molecular layer and to the description of the POM anchoring mode at the oxide interface through the use of various characterization techniques, including ellipsometry, AFM, XPS and FTIR. Finally, electron transport properties were probed in a vertical junction configuration and energy level diagrams have been drawn and discussed in relation with the POM molecular electronic features inferred from cyclic-voltammetry, UV-visible absorption spectra and theoretical calculations. The electronic properties of these POM-based molecular junctions are driven by the POM LUMO (d-orbitals) whatever the nature of the tether or the anchoring group.
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