The surface chemistry of CH_3–, CD_3–, and C_(10)H_(21)–Ge(111) surfaces prepared through a bromination/alkylation method have been investigated by infrared spectroscopy. Well-ordered CH_3–Ge(111) surfaces could be prepared only if, prior to bromination, the surface was etched with 6.0 M HCl or with a two-step etch of H_2O_2 (1.5 M)/HF (5.1 M) followed by a short HF (6.0 M) etch. The etching method used to make the Ge precursor surface, and the formation of a bromine-terminated intermediate Ge surface, were of critical importance to obtain clear, unambiguous infrared absorption peaks on the methyl-terminated Ge surfaces. Polarization-dependent absorption peaks observed at 1232 cm^(–1) for CH_3–Ge(111) surfaces and at 951 cm^(–1) for CD_3–Ge(111) surfaces were assigned to the methyl “umbrella” vibrational mode. A polarization-dependent peak at 2121 cm^(–1) for CD_3–Ge(111) surfaces was assigned to the symmetric methyl stretching mode. Polarization-independent absorption peaks at 755 cm^(–1) for CH_3–Ge(111) and at 577 cm^(–1) for CD_3–Ge(111) were assigned to the methyl rocking mode. These findings provide spectroscopic evidence that the methyl monolayer structure on the alkylated Ge is well-ordered and similar to that on analogous Si(111) surfaces, despite differences in the composition of the precursor surfaces. The X-ray photoelectron spectra of CH_3–Ge(111) surfaces, however, were not highly dependent upon the etching method and showed a constant C 1s:Ge 3d ratio, independent of the etching method. The infrared spectra of C_(10)H_(21)–Ge(111) surfaces were also not sensitive to the initial etching method. Hence, while the final packing density of the alkyl groups on the surface was similar for all etch methods studied, not all methods yielded a well-ordered Ge(111)/overlayer interface
