C. Delerue

Ab initio calculation of the binding energy of impurities in semiconductors: Application to Si nanowires

We discuss the binding energy Eb of impurities in semiconductors within density functional theory (DFT) and the GW approximation, focusing on donors in nanowires as an example. We show that DFT succeeds in the calculation of Eb from the Kohn-Sham (KS) hamiltonian of the ionized impurity, but fails in the calculation of Eb from the KS hamiltonian of the neutral impurity, as it misses most of the interaction of the bound electron with the surface polarization charges of the donor. We trace this deficiency back to the lack of screened exchange in the present functionals.

Electron-phonon coupling and intervalley splitting determine the linewidth of single-electron transport through PbSe nanocrystals

The linewidth of the resonances in the single-electron tunneling spectra has been investigated for PbSe semiconductor nanocrystals (NCs) with scanning tunneling spectroscopy at low temperature. The linewidth of the resonances corresponding to tunneling through the first conduction and valence levels is found to increase with decreasing size of the NCs. Based on theoretical calculations, this broadening is mainly induced by the coupling between the tunneling electrons and the longitudinal optical phonon mode of the NC, and by the splitting of the degenerate electronic levels between the different L-valleys in the Brillouin zone. For the smallest sizes, it is shown that the intervalley splitting is the major source of broadening.

Transport properties of a two-dimensional PbSe square superstructure in an electrolyte-gated transistor

Self-assembled nanocrystal solids show promise as a versatile platform for novel optoelectronic materials. Superlattices composed of a single layer of lead–chalcogenide and cadmium–chalcogenide nanocrystals with epitaxial connections between the nanocrystals, present outstanding questions to the community regarding their predicted band structure and electronic transport properties. However, the as-prepared materials are intrinsic semiconductors; to occupy the bands in a controlled way, chemical doping or external gating is required. Here, we show that square superlattices of PbSe nanocrystals can be incorporated as a nanocrystal monolayer in a transistor setup with an electrolyte gate. The electron (and hole) density can be controlled by the gate potential, up to 8 electrons per nanocrystal site. The electron mobility at room temperature is 18 cm2/(V s). Our work forms a first step in the investigation of the band structure and electronic transport properties of two-dimensional nanocrystal superlattices with controlled geometry, chemical composition, and carrier density.

Preparation and study of 2-D semiconductors with Dirac type bands due to the honeycomb nanogeometry

The interest in 2-dimensional systems with a honeycomb lattice and related Dirac-type electronic bands has exceeded the prototype graphene1. Currently, 2-dimensional atomic2,3 and nanoscale4-8 systems are extensively investigated in the search for materials with novel electronic properties that can be tailored by geometry. The immediate question that arises is how to fabricate 2-D semiconductors that have a honeycomb nanogeometry, and as a consequence of that, display a Dirac-type band structure? Here, we show that atomically coherent honeycomb superlattices of rocksalt (PbSe, PbTe) and zincblende (CdSe, CdTe) semiconductors can be obtained by nanocrystal self-assembly and facet-to-facet atomic bonding, and subsequent cation exchange. We present a extended structural analysis of atomically coherent 2-D honeycomb structures that were recently obtained with self-assembly and facet-to-facet bonding9. We show that this process may in principle lead to three different types of honeycomb structures, one with a graphene type-, and two others with a silicene-type structure. Using TEM, electron diffraction, STM and GISAXS it is convincingly shown that the structures are from the silicene-type. In the second part of this work, we describe the electronic structure of graphene-type and silicene type honeycomb semiconductors. We present the results of advanced electronic structure calculations using the sp3d5s* atomistic tight-binding method10. For simplicity, we focus on semiconductors with a simple and single conduction band for the native bulk semiconductor. When the 3-D geometry is changed into 2-D honeycomb, a conduction band structure transformation to two types of Dirac cones, one for S- and one for P-orbitals, is observed. The width of the bands depends on the honeycomb period and the coupling between the nanocrystals. Furthermore, there is a dispersionless P-orbital band, which also forms a landmark of the honeycomb structure. The effects of considerable intrinsic spin-orbit coupling are briefly considered. For heavy-element compounds such as CdTe, strong intrinsic spin-‐orbit coupling opens a non-trivial gap at the P-orbital Dirac point, leading to a quantum Spin Hall effect10-12. Our work shows that well known semiconductor crystals, known for centuries, can lead to systems with entirely new electronic properties, by the simple action of nanogeometry. It can be foreseen that such structures will play a key role in future opto-electronic applications, provided that they can be fabricated in a straightforward way.