Silicon-germanium (Si1−xGex:H) thin films have been prepared by plasma enhanced chemical vapor deposition of SiH4 and GeH4 and measured during growth using real time spectroscopic ellipsometry. A two-layer virtual interface analysis has been applied to study the structural evolution of Si:H films prepared in multistep processes utilizing alternating intermediate and low H2-dilution material layers, which have been designed to produce predominately amorphous films with a controlled distribution of microcrystalline particles. The compositional evolution of alloy-graded a-Si1−xGex:H has been studied as well using similar methods. In each case, depth profiles of microcrystalline content, fμc, or Ge content, x, have been extracted. Additionally, real time spectroscopic ellipsometry has been used to monitor post-deposition exposure of a-Si:H, a-Si1−xGex:H, and a-Ge:H films to a hydrogen plasma in situ in order to determine sub-surface amorphous film modification similar to that which would occur when a highly H2-diluted layer is deposited on a layer prepared with lower dilution. These analyses provide guidance for enhanced performance of Si:H based solar cells, through controlled bandgap grading using compositionally graded amorphous binary alloys (a-Si1−xGex:H) or the incorporation of controlled fractions of microcrystallites into bulk amorphous i-layer materials, and by providing a fundamental understanding of the modification of component layers during the deposition of subsequent layers in multilayer stacks.