We report on an ab initio study of the structural and electronic properties of B- and P-doped Si nanoclusters. The neutral impurities formation energies are calculated. We show that they are higher in smaller nanoclusters and that this is not related to the structural relaxation around the impurity. Their dependence on the impurity position within the nanocluster is also discussed. Finally, we have calculated the B and P activation energies showing the existence of a nearly linear scaling with the nanocluster inverse radius. Interestingly, no significant variation of the activation energy on the impurity species is found and the cluster relaxation gives a minor contribution to it.

We consider the classic Madelung problem of a lattice with N sites labeled i, each occupied by either an A or a B atom, and bearing a point charge ${\mathit{Q}}_{\mathit{i}}$ that depends on the environment of i. We find that, out of the $2^{\mathit{N}}$ possible lattice configurations of this binary ${\mathit{A}}_{1\mathrm{-}\mathit{x}}$ ${\mathit{B}}_{\mathit{x}}$ fcc alloy, the lowest-energy ‘‘ground-state structures’’ are the ${\mathit{A}}_3$B-, ${\mathit{A}}_2$ ${\mathit{B}}_2$- and ${\mathit{AB}}_3$-ordered superlattices with ordering vector (1,0,1/2). On the other hand, for the pseudobinary ${\mathit{A}}_{1\mathrm{-}\mathit{x}}$ ${\mathit{B}}_{\mathit{x}}$C zinc-blende alloy, the ground state corresponds to phase separation into AC+BC. Contrary to the accepted view, the Madelung energy of the random binary alloy is found to be nonvanishing.

Electronic and structural properties of small hydrogenated silicon nanoclusters as a function of dimension are calculated from ab initio technique. The effects induced by the creation of an electron-hole pair are discussed in detail, showing the strong interplay between the structural and optical properties of the system. The distortion induced on the structure after an electronic excitation of the cluster is analyzed together with the role of the symmetry constraint during the relaxation. We point out how the overall effect is that of significantly changing the electronic spectrum if no symmetry constraint is imposed to the system. Such distortion can account for the Stokes shift and provides a possible structural model to be linked to the four-level scheme invoked in the literature to explain recent results for the optical gain in silicon nanoclusters. Finally, formation energies for clusters with increasing dimension are calculated and their relative stability discussed.

Abrupt InAs/GaSb superlattices have In-Sb and Ga-As interfacial chemical bonds that are not present in the constituent materials InAs and GaSb. We study the effect of interfacial atomic mixing on the electronic structure of such superlattices, including electron and hole energies and wave function localization, interband transition energies, and dipole matrix elements. We combine an empirical pseudopotential method for describing the electronic structure with two different structural models of interfacial disorder. First, we use the “single-layer disorder” model and change in a continous way the composition of the interfacial bonds. Second, we study interfacial atomic segregation using a layer-by-layer kinetic model of molecular beam epitaxy growth, fit to the observed scanning tunneling microscopy segregation profiles. The growth model provides a detailed structural model of segregated InAs/GaSb superlattices with atomic resolution. The application of the empirical pseudopotential method to such structures reveals remarkable electronic consequences of segregation, among them a large blueshift of the band gap. This result explains the surprising gap increase with growth temperature observed for similar structures. In particular we find that (i) superlattices with only In-Sb interfacial bonds have lower band gaps (by 50 meV) than superlattices with only Ga-As interfacial bonds. (ii) Heavy-hole–to–electron transition energies increase with the number of Ga-As interfacial bonds more than light-hole–to–electron transition energies. (iii) The heavy-hole $\mathrm{hh}1\mathrm{}$ wave functions show a strong localization on the In-Sb interfacial bonds. The heavy-hole wave functions have very different amplitudes on the Ga-As interface and on the In-Sb interface. (iv) Sb segregates at InAs-on-GaSb growth, whereas As and In segregate at GaSb-on-InAs growth, but Ga does not segregate. (v) The segregation of Sb and In induces a blueshift in the band gap. (vi) There is an in-plane polarization anisotropy due to the low symmetry of the no-common-atom InAs/GaSb superlattice. This anisotropy is reduced by interfacial segregation.

The effects of B and P codoping on the impurity formation energies and electronic properties of Si nanocrystals (Si-nc) are calculated by a first-principles method. We show that, if carriers in the Si-nc are perfectly compensated by simultaneous doping with n- and p-type impurities, the Si-nc undergo a minor structural distortion around the impurities and that the formation energies are always smaller than those for the corresponding single-doped cases. The band gap of the codoped Si-nc is strongly reduced with respect to the gap of the pure ones showing the possibility of an impurity based engineering of the photoluminescence properties of Si-nc.

We show that the optical and electronic properties of nanocrystalline silicon can be efficiently tuned using impurity doping. In particular, we give evidence, by means of ab initio calculations, that by properly controlling the doping with either one or two atomic species, a significant modification of both the absorption and the emission of light can be achieved. We have considered impurities, either boron or phosphorous (doping) or both (codoping), located at different substitutional sites of silicon nanocrystals with size ranging from $1.1\text{to}1.8\mathrm{nm}$ in diameter. We have found that the codoped nanocrystals have the lowest impurity formation energies when the two impurities occupy nearest neighbor sites near the surface. In addition, such systems present band-edge states localized on the impurities, giving rise to a redshift of the absorption thresholds with respect to that of undoped nanocrystals. Our detailed theoretical analysis shows that the creation of an electron-hole pair due to light absorption determines a geometry distortion that, in turn, results in a Stokes shift between adsorption and emission spectra. In order to give a deeper insight into this effect, in one case we have calculated the absorption and emission spectra beyond the single-particle approach, showing the important role played by many-body effects. The entire set of results we have collected in this work give a strong indication that with the doping it is possible to tune the optical properties of silicon nanocrystals.