膦在硅（001）上解离的反应路径。

Reaction paths of phosphine dissociation on silicon (001).

作者信息

Warschkow O, Curson N J, Schofield S R, Marks N A, Wilson H F, Radny M W, Smith P V, Reusch T C G, McKenzie D R, Simmons M Y

机构信息

Centre for Quantum Computation and Communication Technology, School of Physics, The University of Sydney, Sydney, NSW 2006, Australia.

Centre for Quantum Computation and Communication Technology, School of Physics, The University of New South Wales, Sydney, NSW 2052, Australia.

出版信息

J Chem Phys. 2016 Jan 7;144(1):014705. doi: 10.1063/1.4939124.

DOI:10.1063/1.4939124

PMID:26747816

Abstract

Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH3) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH2+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH2 fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH3 stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.

摘要

利用密度泛函理论，并在大量扫描隧道显微镜（STM）图像数据的指导下，我们制定了磷化氢（PH₃）分子在室温下于Si(001)表面解离的详细机制。我们区分了主要解离序列，其中涉及可观察到的中间体PH₂+H、PH+2H和P+3H，以及产生PH+H、P+2H和孤立磷吸附原子的次要序列。后一序列的出现是因为PH₂片段在Si(001)上具有惊人的移动性，并且可以从构成PH₃化学计量的第三个氢原子处扩散开。我们计算出的活化能描述了扩散和解离途径之间的竞争，因此为STM实验中观察到的众多吸附质物种提供了一个全面的模型。