Title:
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Effective mass modelling of excitons in semiconductor nanocrystals
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This thesis investigates the properties of exciton states in semiconductor nanocrystals
using effective mass models. We focus on type-I core-shell nanocrystals in
which the staggered band alignments of the core and shell material mean the lowest
energy states for electrons and holes lie in different spatial regions, giving rise to
spatially indirect excitons.
The technological potential of type-I! nanocrystals provides motivation for understanding
single exciton states which determine many important optical properties.
In the first research chapter we study CdTe/CdSe and CdSe/CdTe nanocrystals
using a single-band and (2,6)-band effective mass model. The (2,6)-band model is
based on a multiband k·p theory previously developed for spherical quantum dot
heterostructures. We calculate exciton energies as a function of the core radius a
and shell width as of the heterostructure, and assign six exciton transitions in the
experimental absorption spectra of CdTe/CdSe nanocrystals.
The second research chapter is concerned with strained ZnTe/ZnSe nanocrystals.
The (2,6)-band model is modified to incorporate strain using a continuum elasticity
model. Exciton energies from absorption spectra are compared with the predictions
of the strained and unstrained nanocrystal models, showing that they only describe
the lowest exciton energy of one of the three size series. Improved agreement is found
for the change in exciton energy due to a particular shell width, with the strained
nanocrystal model giving much better fits to the as-dependence. The as-dependence
of nanocrystals with alloyed heterointerfaces is better described by the unstrained
nanocrystal model, indicating alloying relaxes the strain in this system.
In the final chapter we model spatial correlations between the electron and hole
in CdTe/CdSe and CdSe/CdTe nanocrystals using a configuration interaction approach
developed in the framework of the (2,6)-band k·p theory. We find that
the single-particle basis can, be restricted without changing t~e resulting exciton
energies significantly; using this decoupled configuration ihter~ction approach we
calculate exciton energy shifts due to correlation as a function of aand as. Dielectric
confinement increases correlation for many heterostructure designs by shifting
carrier wavefunctions away from the surface, and the interparticle Coulomb interaction
leads to large changes in radial probability density for the uniform dielectric
constant case. Dielectric confinement affects the correlated hole more than the electron
so that excitons in the CdSe/CdTe heterostructure are more affected by the
dielectric environment than those in the CdTe/CdSe heterostructure. The overall
behaviour of the correlated charge density is due to the net effect of the type-I!
spatial confinement, interparticle Coulomb attraction, dielectric confinement and
single-particle electronic structure.
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