Size dependence of the bulk modulus of semiconductor nanocrystals from first-principles calculations

Abstract

The variation in the bulk modulus of semiconductor nanoparticles has been studied within first-principles electronic-structure calculations using the local density approximation (LDA) for the exchange correlation. Quantum Monte Carlo calculations carried out for a silicon nanocrystal Si₈₇H₇₆ provided reasonable agreement with the LDA results. An enhancement was observed in the bulk modulus as the size of the nanoparticle was decreased, with modest enhancements being predicted for the largest nanoparticles studied here, a size just accessible in experiments. To access larger sizes, we fit our calculated bulk moduli to the same empirical law for all materials, the asymptote of which is the bulk value of the modulus. This was found to be within 2–10 % of the independently calculated value. The origin of the enhancement has been discussed in terms of Cohen’s empirical law [M. L. Cohen, Phys. Rev. B 32, 7988 (1985)] as well as other possible scenarios.