H2_Mankelevich_Ashfold_Umemoto_11_9_13_MNRA.doc

Molecular dissociation and vibrational excitation on a metal hot filament surface. Yuri A. Mankelevicha, Michael N.R. Ashfoldb and Hironobu Umemotoc,d a Skobel’tsyn Institute of Nuclear Physics, Moscow State University, Leninskie Gory, Moscow, 119991 Russia b School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom c Graduate School of Engineering, Shizuoka University, Johoku, Naka, Hamamatsu, Shizuoka 432-8561, Japan d Japan Science and Technology Agency, CREST, Sanbancho, Chiyoda, Tokyo 102-0075, Japan Abstract The dissociation of diatomic molecules (H2, N2, O2) on the surface of a metal hot filament (HF) has been studied theoretically, within the framework of a unified two-step reaction mechanism, and via joint experimental-modeling studies of the gas temperature and selected species concentration distributions in the vicinity of the HF. This approach allows description of the variations in atomic concentrations with distance (d, measured from the HF) as functions of HF temperature and gas pressure. Complications associated with the extension of such analyses to interpretations of prior experimental measurements for larger, heteronuclear molecules (CH4, nitrogen oxides) are discussed. The present analysis also provides a rationale for the d-dependent non-equilibrium [N2(v=1)]/[N2(v=0)] vibrational population ratios measured in tungsten HF-activated N2 gas samples. I. Introduction The dissociation of molecular species (e.g. H2, N2, O2, hydrocarbons, nitrogen oxides) on metal hot filaments (HFs) constitutes a scalable, three-dimensional (3-D), large-area radical source with application in the chemical vapor deposition (CVD) of diamond films [1-3] and Si-containing layers for solar cells [4], in the deposition of materials like GaN [5], SiO2 [6], and Al2O3[7], in etching [8], in boron and nitrogen doping [9-11], and in surface treatments (e.g. cleaning [12], modification [13] and nitridation [14]). HF sources have also limitations, including lim