Quantum confinement in nanoscale silicon: The correlation of size with bandgap and luminescence

The optical properties of silicon nanocrystallites of known sizes, present in supercritically dried porous silicon films of porosities as high as 92%, have been measured by a variety of techniques. The bandgap and luminescence energies have been measured as a function of size for the first time. The bandgap increases by more than 1 eV due to quantum confinement. The peak luminescence energy which also shifts to the blue is increasingly Stokes shifted with respect to the bandgap, as the size decreases. The measured bandgap is in agreement with realistic theories and the Stokes-shift between bandgap and luminescence energies coincides with the exciton binding energy predicted by these theories. These results demonstrate unambiguously and quantitatively the role of quantum confinement in the optical properties of this indirect gap semiconductor. (C) 1998 Elsevier Science Ltd.