A theoretical study of light emission from nanoscale silicon

In comparing our calculated exciton energies with those obtained from pseudopotential calculations (Ref. 27) and from a previous tight binding calculation (Ref. 30), we stated that the differences between the three semi-empirical calculations arise because of different treatment of the nanocrystal surfaces. This appears not to be correct. Subsequent calculations with variable Si-H parameters have shown that the band gap is actually rather insensitive to the actual value of these. Instead, the important feature appears to be the overall quality of the bulk band structure parameterization. References 27 and 30 use more extensive and higher quality empirical parameterizations for bulk Si than the sp³s∗ model used by us. Repeating our time dependent calculations with an improved sp³d⁵ parameterization results in similar values to those of Refs. 27 and 30 for the exciton energies.¹ The agreement of the sp³s∗ values with experimental photoluminescence energies (Fig. 7) cannot, therefore, be regarded as well understood at this time.^1,2