Comparison of Trichlorosilane and Trichlorogermane Decomposition on Silicon Surfaces Using FTIR Spectroscopy

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Abstract
Fourier transform infrared (FTIR) transmission spectroscopy was used to compare the decomposition of trichlorosilane (SiHCl3) and trichlorogermane (GeHCl3) on silicon surfaces. Chlorosilanes, such as SiHCl3 are employed in silicon chemical vapor deposition (CVD). Chlorosilanes and chlorogermanes are also possible molecular precursors for the controlled atomic layer growth of silicon and germanium. GeHCl3 may be useful for the deposition of germanium on silicon surfaces and the growth of Si1−xGex heterostructures. The FTIR studies were performed in-situ in an ultra-high vacuum chamber on high surface area, porous silicon samples. The FTIR spectra revealed that SiHCl3 dissociatively adsorbs at 200 K to form SiH, SiClx, ClSiH and Cl2SiH surface species. The presence of ClxSiH species is revealed by ClxSiH stretching (2196 cm−1) and bending (775, 744 cm−1) vibrations. The presence of these modes indicates that there is incomplete decomposition of SiHCl3 upon adsorption at 200 K. GeHCl3 also dissociatively adsorbs at 200 K to form SiH and SiClx species. An infrared absorption feature in the Ge-H stretching region (1970–1995 cm−1) was not detected in the FTIR spectrum. The absence of a Ge-H absorption feature argues that there is a complete transfer of hydrogen from germanium to surface silicon atoms at 200 K. The thermal stabilities of the surface species were studied with annealing experiments. The Clx SiH formed upon initial SiHCl3 exposures at 200 K were observed to decompose between 200–590 K and form additional surface SiH and SiCl species. For both GeHCl3 and SiHCl3 dissociative adsorption on porous silicon, the SiCL. (x = 2 or 3) surface species were converted to silicon monochloride surface species between 200–600 K. In addition, SiH surface species were lost upon annealing between 680–780 K as H2 desorbed from the surface. The adsorption kinetics of SiHCl3 and GeHCl3 were also monitored on porous silicon at various isothermal temperatures. These experiments provide insight into the surface chemistry of chlorosilanes and chlorogermanes during CVD and atomic layer controlled growth.