A. Fink et al., Ethylene adsorption on Ge(100)-(2x1): A combined angle-resolved photoemission and thermal desorption spectroscopy study, J CHEM PHYS, 115(6), 2001, pp. 2768-2775
Ethylene adsorption on vicinal, single-domain Ge(100)-(2x1) has been invest
igated by thermal desorption spectroscopy (TPD) and angle-resolved photoemi
ssion (ARUPS) using linearly polarized synchrotron radiation. Thermal desor
ption experiments show that chemisorbed C2H4 desorbs from Ge(100) nondissoc
iatively around 393 K with a high temperature shoulder which is tentatively
assigned to step site desorption. The ethylene saturation coverage is stro
ngly temperature dependent. Adsorption at 90 K saturates at 0.38 monolayer
(ML), whereas adsorption at 170 K leads to a saturation coverage of approxi
mately 1 ML. This behavior is explained by an adsorption barrier for covera
ges exceeding 0.38 ML. ARUP spectra for a dilute and the saturated ethylene
monolayer reveal clear differences. Using photoemission selection rules a
highly (C-2v) symmetric adsorption geometry with a C-C bond axis parallel t
o the Ge-Ge dimer axis is found for the dilute layer; whereas a reduced C-2
adsorption symmetry is found for the saturated ethylene layer. The compari
son of photoemission spectra for C2H4 on Ge(100) and Si(100) shows that C2H
4 is di-sigma bound to the dangling bonds of a single Ge-Ge dimer. For two
molecular orbitals, 1b(3u) and 1b(2g), one-dimensional band structures with
dispersion widths of 0.5 and 0.39 eV, respectively, along the Ge-Ge dimer
rows are found which present a straightforward explanation for the observed
symmetry reduction and adsorption behavior. (C) 2001 American Institute of
Physics.