Growth and defect chemistry of amorphous hydrogenated silicon

Abstract

Magnetic resonance (NMR,EPR) and infrared studies are presented of amorphous hydrogenated silicon (a-Si:H) films prepared by homogeneous chemical vapor deposition (HOMOCVD) and rf plasma decomposition using silane and disilane. Hydrogen incorporation occurs with a small activation energy (∼0.06 eV) for all films, while the barrier for changes in spin defect density is almost an order of magnitude larger and comparable to that measured in defect annealing studies. Films deposited by rf(Si2H6) plasma exhibit the greatest hydrogen contents, followed by HOMOCVD and rf(SiH4) plasma material. NMR measurements suggest that HOMOCVD films are less disordered than plasma-deposited a-Si:H. Previous work and recent kinetic studies of plasma and thermal environments are extensively analyzed, along with thermodynamic and kinetic data, to determine a a-Si:H growth mechanisms most consistent with the experimental results. The model presented to explain compositional and defect changes with substrate temperature emphasizes plasma deposition by monoradical precursors and HOMOCVD growth by diradicals, resulting initially in a similar surface-bound intermediate in all cases. Plasma growth from Si2H6 involves the surface attachment of longer radical chains, compared to SiH4, while oligomeric diradicals could be present in HOMOCVD. The possibility that reactions at the hot reactor wall, as well as in the gas, create monoradicals in HOMOCVD is also explored in detail. Finally, film dehydrogenation and crosslinking reactions are examined, and experiments proposed to determine the channels most relevant for each deposition environment.