The behavior of electron and hole transport in semiconductor materials is influenced by lattice-mismatch at the interface. It is well known that carrier scattering in a confined region is dramatically reduced. In this work, we studied the effects of coupling both the strain and confinement simultaneously. We report on the fabrication and characterization of nanoscale planar, wall-like, and wire-like Si/SiO2 structures. As the Si nanostructure dimensions were scaled down to the quantum regime by thermal oxidation of the Si, changes to the band structure and carrier effective mass were observed by both optical and electrical techniques. Transient-time response measurements were performed to examine the carrier generation and recombination behavior as a function of scaling. Signal rise times decreased for both carrier types by an order of magnitude as Si dimensions were reduced from 200 to 10 nm, meaning that the carrier velocity is increasing with smaller scale structures. This result is indicative of decreased Si bandgap energy and carrier effective mass. Photoluminescence measurements taken at 50K showed changes in the PL response peak energies, which illustrates changes in the band structure, as the Si/SiO2 dimensions are scaled.