Electronic structure and g factors of narrow-gap zinc-blende nanowires and nanorods

The Hamiltonian in the framework of eight-band effective-mass approximation of the zinc-blende nanowires and nanorods in the presence of external homogeneous magnetic field is given in the cylindrical coordinate. The electronic structure, optical properties, magnetic energy levels, and g factors of the nanowires and nanorods are calculated. It is found that the electron states consist of many hole-state components, due to the coupling of the conduction band and valence band. For the normal bands which are monotone functions of |k(z)|, long nanorods can be modeled by the nanowires, the energy levels of the nanorods approximately equal the values of the energy band E(k(z)) of the nanowires with the same radius at a special k(z), where k(z) is the wave vector in the wire direction. Due to the coupling of the states, some of the hole energy bands of the nanowires have their highest points at k(z)=0. Especially, the highest hole state of the InSb nanowires is not at the k(z)=0 point. It is an indirect band gap. For these abnormal bands, nanorods can not be modeled by the nanowires. The energy levels of the nanorods show an interesting plait-like pattern. The linear polarization factor is zero, when the aspect ratio L/2R is smaller than 1, and increases as the length increases. The g(z) and g(x) factors as functions of the k(z), radius R and length L are calculated for the wires and rods, respectively. For the wires, the g(z) of the electron ground state increases, and the g(z) of the hole ground state decreases first, then increases with the k(z) increasing. For the rods, the g(z) and g(x) of the electron ground state decrease as the R or the L increases. The g(x) of the hole ground state decreases, the g(z) of the hole ground state increases with the L increasing. The variation of the g(z) of the wires with the k(z) is in agreement with the variation of the g(z) of the rods with the L.

Electronic structure and electron g factors of HgTe quantum dots

The electronic structure and electron g factors of HgTe quantum dots are investigated, in the framework of the eight-band effective-mass approximation. It is found that the electron states of quantum spheres have aspheric properties due to the interaction between the conduction band and valence band. The highest hole states are S (l = 0) states, when the radius is smaller than 9.4 nm. the same as the lowest electron states. Thus strong luminescence from H-Te quantum dots with radius smaller than 9.4 nm has been observed (Rogach et al 2001 Phys. Statits Solidi b 224 153). The bandgap of H-Te quantum spheres is calculated and compared with earlier experimental results (Harrison et al 2000 Pure Appl. Chem. 72 295). Due to the quantum confinement effect, the bandgap of the small HgTe quantum spheres is positive. The electron g factors of HgTe quantum spheres decrease with increasing radius and are nearly 2 when the radius is very small. The electron g factors of HgTe quantum ellipsoids are also investigated. We found that as some of the three dimensions increase, the electron g factors decrease. The more the dimensions increase, the more the g factors decrease. The dimensions perpendicular to the direction of the magnetic field affect the g factors more than the other dimension.

Energy structure and fluorescence of Eu2+ in ZnS : Eu nanoparticles

Eu2+-doped ZnS nanoparticles with an average size of around 3 nm were prepared, and an emission band around 530 nm was observed. By heating in air at 150 degrees C, this emission decreased, while the typical sharp line emission of Eu3+ increased. This suggests that the emission around 530 nm is from intraion transition of Eu2+: In bulk ZnS:Eu2+, no intraion transition of Eu2+ was observed because the excited states of Eu2+ are degenerate with the continuum of the ZnS conduction band. We show that the band gap in ZnS:Eu2+ nanoparticles opens up due to quantum confinement, such that the conduction band of ZnS is higher than the first excited state of Eu2+, thus enabling the intraion transition of Eu2+ to occur.

The effects of electric field on the electronic structure of a semiconductor quantum dot

The effect of electric field on the electronic structure of a spherical quantum dot is studied in the framework of the effective-mass envelope-function theory. The dependence of the energy of electron states and hole states on the applied electric field and on the quantum dot size is investigated; the mixing of heavy holes and light holes is taken into account. The selection rule for the optical transition between the conduction band and valence band states is obtained. The exciton binding energies are calculated as functions of the quantum dot radius and the strength of the electric field. (C) 1998 American Institute of Physics.

Electronic structure and optical gain saturation of InAs1-xNx/GaAs quantum dots

The electronic band structures and optical gains of InAs1-xNx/GaAs pyramid quantum dots (QDs) are calculated using the ten-band k . p model and the valence force field method. The optical gains are calculated using the zero-dimensional optical gain formula with taking into consideration of both homogeneous and inhomogeneous broadenings due to the size fluctuation of quantum dots which follows a normal distribution. With the variation of QD sizes and nitrogen composition, it can be shown that the nitrogen composition and the strains can significantly affect the energy levels especially the conduction band which has repulsion interaction with nitrogen resonant state due to the band anticrossing interaction. It facilitates to achieve emission of longer wavelength (1.33 or 1.55 mu m) lasers for optical fiber communication system. For QD with higher nitrogen composition, it has longer emission wavelength and less detrimental effect of higher excited state transition, but nitrogen composition can affect the maximum gain depending on the factors of transition matrix element and the Fermi-Dirac distributions for electrons in the conduction bands and holes in the valence bands respectively. For larger QD, its maximum optical gain is greater at lower carrier density, but it is slowly surpassed by smaller QD as carrier concentration increases. Larger QD can reach its saturation gain faster, but this saturation gain is smaller than that of smaller QD. So the trade-off between longer wavelength, maximum optical, saturation gain, and differential gain must be considered to select the appropriate QD size according to the specific application requirement. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3143025]

Electronic structure and magnetic coupling properties of Gd-doped AlN: first-principles calculations

In this work, the electronic structure and magnetic coupling properties of Gd doped AlN have been investigated using first-principles method. We found that in the AlN:Gd system, due to the s-f coupling allowed by the symmetry, the exchange splitting of the conduction band is much larger than that of the valence band, which makes the electron-mediated ferromagnetism possible in this material. This property is also confirmed by the energy differences between anti-ferromagnetic and ferromagnetic phase for Al14Gd2N16 with different concentrations of electrons (holes), as well as by the calculated exchange constants. The result indicates that Gd-doped AlN is a promising candidate for the applications in future spintronic devices.

THEORY OF THE ELECTRONIC-STRUCTURE OF POROUS SI

A theoretical model for the electronic structure of porous Si is presented. Three geometries of porous Si (wire with square cross section, pore with square cross section, and pore with circular cross section) along both the [001] and [110] directions are considered. It is found that the confinement geometry affects decisively the ordering of conduction-band states. Due to the quantum confinement effect, there is a mixing between the bulk X and GAMMA states, resulting in finite optical transition matrix elements, but smaller than the usual direct transition matrix elements by a factor of 10(-3). We found that the strengths of optical transitions are sensitive to the geometry of the structure. For (001) porous Si the structure with circular pores has much stronger optical transitions compared to the other two structures and it may play an important role in the observed luminescence. For this structure the energy difference between the direct and the indirect conduction-band minima is very small. Thus it is possible to observe photoluminescence from the indirect minimum at room temperature. For (110) porous Si of similar size of cross section the energy gap is smaller than that of (001) porous Si. The optical transitions for all three structures of (110) porous Si tend to be much stronger along the axis than perpendicular to the axis.

A theoretical study of the effects of lithium intercalation on the electronic structure of TiS

The band structure of the intercalation complex of LiTiS has been computed using a semi-empirical tight-binding method and this is compared with the results of a revised TiS calculation. The results obtained confirm that changes in the basic electrical characteristics of TiS, which occur when it is intercalated with lithium, can be attributed to a rigid-band filling of its lowest unoccupied electron states as has previously been proposed. However, they also suggest that intercalation can act to alter the nature and the dispersion of some of the energy bands in the unintercalated crystal. The bands which are most affected by the process are those which derive from orbitals which have the same symmetry as the lithium 2s orbital, namely, the titanium 4s conduction level and the tightly bound sulphur 3s levels.

Electronic structure of a neutral oxygen vacancy in SrTiO3

The electronic structure of an isolated oxygen vacancy in SrTiO3 has been investigated with a variety of ab initio quantum mechanical approaches. In particular we compared pure density functional theory (DFT) approaches with the Hartree-Fock method, and with hybrid methods where the exchange term is treated in a mixed way. Both local cluster models and periodic calculations with large supercells containing up to 80 atoms have been performed. Both diamagnetic (singlet state) and paramagnetic (triplet state) solutions have been considered. We found that the formation of an O vacancy is accompanied by the transfer of two electrons to the 3d(z2) orbitals of the two Ti atoms along the Ti-Vac-Ti axis. The two electrons are spin coupled and the ground state is diamagnetic. New states associated with the defect center appear in the gap just below the conduction band edge. The formation energy computed with respect to an isolated oxygen atom in the triplet state is 9.4 eV.

Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

Engineering the electronic bandgaps and band edge positions in carbon-substituted 2D boron nitride: a first-principles investigation

Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C2xB1−xN1−x alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C (x < 0.25); and (b) the electronic structure of C2xB1−xN1−x can be further tuned not only with composition x, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C2xB1−xN1−x alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles.

A combined theoretical and experimental study of electronic structure and optical properties of β-ZnMoO4 microcrystals

In this paper, a combined theoretical and experimental study on the electronic structure and photoluminescence (PL) properties of beta zinc molybdate (β-ZnMoO4) microcrystals synthesized by the hydrothermal method has been employed. These crystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, Fourier transform Raman (FT-Raman) and Fourier transform infrared (FT-IR) spectroscopies. Their optical properties were investigated by ultraviolet-visible (UV-Vis) absorption spectroscopy and PL measurements. First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level have been carried out. XRD patterns, Rietveld refinement, FT-Raman and FT-IR spectra showed that these crystals have a wolframite-type monoclinic structure. The Raman and IR frequencies experimental results are in reasonable agreement with theoretically calculated results. UV-Vis absorption measurements shows an optical band gap value of 3.17 eV, while the calculated band structure has a value of 3.22 eV. The density of states indicate that the main orbitals involved in the electronic structure of β-ZnMoO4 crystals are (O 2p-valence band and Mo 4d-conduction band). Finally, PL properties of β-ZnMoO4 crystals are explained by means of distortions effects in octahedral [ZnO6] and [MoO6] clusters and inhomogeneous electronic distribution into the lattice with the electron density map. © 2013 Elsevier Ltd. All rights reserved.

Local electronic structure, optical bandgap and photoluminescence (PL) properties of Ba(Zr0.75Ti0.25)O3 powders

Ba(Zr0.75Ti0.25)O3 (BZT-75/25) powders were synthesized by the polymeric precursor method. Samples were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques. Their electronic structures were evaluated by first-principle quantum mechanical calculations based on density functional theory at the B3LYP level. Their optical properties were investigated by ultraviolet-visible (UV-Vis) spectroscopy and photoluminescence (PL) measurements at room temperature. XRD patterns and Rietveld refinement data indicate that the samples have a cubic structure. XANES spectra confirm the presence of pyramidal [TiO5] clusters and octahedral [TiO6] clusters in the disordered BZT-75/25 powders. EXAFS spectra indicate distortion of Ti-O and Ti-O-Ti bonds the first and second coordination shells, respectively. UV-Vis absorption spectra confirm the presence of different optical bandgap values and the band structure indicates an indirect bandgap for this material. The density of states demonstrates that intermediate energy levels occur between the valence band (VB) and the conduction band (CB). These electronic levels are due to the predominance of 4d orbitals of Zr atoms in relation to 3d orbitals of Ti atoms in the CB, while the VB is dominated by 2p orbitals related to O atoms. There was good correlation between the experimental and theoretical optical bandgap values. When excited at 482 nm at room temperature, BZT-75/25 powder treated at 500 C for 2 h exhibited broad and intense PL emission with a maximum at 578 nm in the yellow region. © 2013 Elsevier Ltd. All rights reserved.

Electrical transport mechanisms and structure of hydrogenated and non-hydrogenated nanocrystalline Ga1-xMnxAs films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ab-initio determination of x-ray absorption near edge structure (xanes) spectra in an ultrasoft and norm conserving pseudopotentials scheme

X-ray absorption spectroscopy (XAS) is a powerful means of investigation of structural and electronic properties in condensed -matter physics. Analysis of the near edge part of the XAS spectrum, the so – called X-ray Absorption Near Edge Structure (XANES), can typically provide the following information on the photoexcited atom: - Oxidation state and coordination environment. - Speciation of transition metal compounds. - Conduction band DOS projected on the excited atomic species (PDOS). Analysis of XANES spectra is greatly aided by simulations; in the most common scheme the multiple scattering framework is used with the muffin tin approximation for the scattering potential and the spectral simulation is based on a hypothetical, reference structure. This approach has the advantage of requiring relatively little computing power but in many cases the assumed structure is quite different from the actual system measured and the muffin tin approximation is not adequate for low symmetry structures or highly directional bonds. It is therefore very interesting and justified to develop alternative methods. In one approach, the spectral simulation is based on atomic coordinates obtained from a DFT (Density Functional Theory) optimized structure. In another approach, which is the object of this thesis, the XANES spectrum is calculated directly based on an ab – initio DFT calculation of the atomic and electronic structure. This method takes full advantage of the real many-electron final wavefunction that can be computed with DFT algorithms that include a core-hole in the absorbing atom to compute the final cross section. To calculate the many-electron final wavefunction the Projector Augmented Wave method (PAW) is used. In this scheme, the absorption cross section is written in function of several contributions as the many-electrons function of the finale state; it is calculated starting from pseudo-wavefunction and performing a reconstruction of the real-wavefunction by using a transform operator which contains some parameters, called partial waves and projector waves. The aim of my thesis is to apply and test the PAW methodology to the calculation of the XANES cross section. I have focused on iron and silicon structures and on some biological molecules target (myoglobin and cytochrome c). Finally other inorganic and biological systems could be taken into account for future applications of this methodology, which could become an important improvement with respect to the multiscattering approach.