Infrared and Raman spectra of the silicon-hydrogen bonds in amorphous silicon prepared by glow discharge and sputtering

We have studied the number and nature of the silicon-hydrogen bonds in amorphous silicon films prepared in plasmas either of silane or of hydrogen and argon. The films from silane glow discharges have qualitatively different Raman and infrared spectra which depend on deposition parameters such as substrate temperature and silane gas pressure. Three main groups of spectral bands are seen associated with the Si-H bonds: the Si-H bond stretch bands, the bands due to relative bending of two or three Si-H bonds with a common silicon atom, and the "wagging" bands of Si-H bonds with respect to the Si matrix. These bands are split in a way suggestive of the presence of SiH, Si${\mathrm{H}}_2$, and Si${\mathrm{H}}_3$ complexes: the bond-bending bands are absent when only SiH bonds are present. All three types of complexes are identified in films deposited from glow discharges of silane at pressures ∼ 1 Torr and room temperature. Higher substrate temperatures and/or lower pressures reduce the Si${\mathrm{H}}_2$ and Si${\mathrm{H}}_3$ concentrations: films deposited at 250°C and 0.1 Torr contain only SiH groups. From the strength of the corresponding absorption bands, H concentrations as high as 35 to 52 atomic percent are estimated. Films sputtered at 200°C in a 10% ${\mathrm{H}}_2$-90% Ar mixture contain all three groupings observed in the silane-derived samples. Deuterated sputtered films are used to confirm the analysis. The first- and second-order Raman scattering spectra of the Si-Si bonds in pure and hydrogenated $a-\mathrm{S}\mathrm{i}$ are also discussed. The scattering efficiency of $a-\mathrm{S}\mathrm{i}$ is found to be as much as 10 times that of crystal Si. The depolarization ratio of the $a-\mathrm{S}\mathrm{i}$ Raman spectrum has been remeasured. Finally, a picture is presented of when it is appropriate to refer to heavily hydrogenated $a-\mathrm{S}\mathrm{i}$ as still being a material describable by $a-\mathrm{S}\mathrm{i}$ network models.