Interaction range of P-dopants in Si[110] nanowires: determining the nondegenerate limit.

It is well known that the activation energy of dopants in semiconducting nanomaterials is higher than in bulk materials owing to dielectric mismatch and quantum confinement. This quenches the number of free charge carriers in nanomaterials. Though higher doping concentration can compensate for this effect, there is no clear criterion on what the doping concentration should be. Using P-doped Si[110] nanowires as the prototypical system, we address this issue by establishing a doping limit by first-principles electronic structure calculations. We examine how the doped nanowires respond to charging using an effective capacitance approach. As the nanowire gets thinner, the interaction range of the P dopants shortens and the doping concentration can increase concurrently. Hence, heavier doping can remain nondegenerate for thin nanowires.

Limits on passivating defects in semiconductors: the case of Si edge dislocations.

By minimizing the free energy while constraining dopant density, we derive a universal curve that relates the formation energy (E(form)) of doping and the efficiency of defect passivation in terms of segregation of dopants at defect sites. The universal curve takes the simple form of a Fermi-Dirac distribution. Our imposed constraint defines a chemical potential that assumes the role of "Fermi energy," which sets the thermodynamic limit on the E(form) required to overcome the effect of entropy such that dopant segregation at defects in semiconductors can occur. Using Si edge dislocation as an example, we show by first-principles calculations how to map the experimentally measurable passivation efficiency to our calculated E(form) by using the universal curve for typical n- and p-type substitutional dopants. We show that n-type dopants are ineffective. Among p-type dopants, B can satisfy the thermodynamic limit while improving electronic properties.

Controlling diffusion of lithium in silicon nanostructures.

The ability to control the diffusion of dopants or impurities is a controlling factor in the functionalization of materials used in devices both at the macro- and nanoscales. At the nanoscale, manipulating diffusion of dopants is complicated by a number of factors such as the role of quantum confinement and the large surface to volume ratio. Here we examine Li in Si nanostructures, as atoms with low atomic mass such as Li can be used as a carrier for energy storage with high specific energy capacity. Specifically, Li-ion batteries with specific energy capacity as high as 4200 mA h g(-1) using Si nanowires as anodes have been achieved. Using ab initio calculations, we determine how the factors of size and dimensionality can be used to achieve an optimal diffusion of Li atoms in Si nanostructures.

Role of confinement on diffusion barriers in semiconductor nanocrystals.

We find that quantum size effects not only play an important role in the electronic properties of defects in semiconductor nanocrystals, but also strongly affect the incorporation of defect atoms into the nanocrystals. In particular, using ab initio methods based on density functional theory, we predict that Mn defects will be energetically driven towards the surface of CdSe and ZnSe nanocrystals, and that the diffusion barrier of a Mn interstitial defect in a CdSe nanocrystal will be significantly lower than that in the bulk.

Magic structures of h-passivated 110 silicon nanowires.

We report a genetic algorithm approach combined with ab initio calculations to determine the structure of hydrogenated 110 Si nanowires. As the number of atoms per length increases, we find that the cross section of the nanowire evolves from chains of six-atom rings to fused pairs of such chains to hexagons bounded by {001} and {111} facets. Our calculations predict that hexagonal wires become stable starting at about 1.2 nm diameter, which is consistent with recent experimental reports of nanowires with diameters of about 3 nm.