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Adsorption and thermal decomposition of SiH4 on Cu( 1 1 1 ) at 1 1 0 K has been studied by the calculation of silicon K-edge near edge x-ray absorption fine structure spectra using multiple-scattering cluster method. It is found that the cleavage of Si-H bond yields SiH3 species adsorbed on the fcc 3-fold hollow sites on Cu (111) surface at 110K.