Efficient Green Emission from Wurtzite Al xIn1- xP Nanowires.

Direct band gap III-V semiconductors, emitting efficiently in the amber-green region of the visible spectrum, are still missing, causing loss in efficiency in light emitting diodes operating in this region, a phenomenon known as the "green gap". Novel geometries and crystal symmetries however show strong promise in overcoming this limit. Here we develop a novel material system, consisting of wurtzite Al xIn1- xP nanowires, which is predicted to have a direct band gap in the green region. The nanowires are grown with selective area metalorganic vapor phase epitaxy and show wurtzite crystal purity from transmission electron microscopy. We show strong light emission at room temperature between the near-infrared 875 nm (1.42 eV) and the "pure green" 555 nm (2.23 eV). We investigate the band structure of wurtzite Al xIn1- xP using time-resolved and temperature-dependent photoluminescence measurements and compare the experimental results with density functional theory simulations, obtaining excellent agreement. Our work paves the way for high-efficiency green light emitting diodes based on wurtzite III-phosphide nanowires.

Optical Properties of Strained Wurtzite Gallium Phosphide Nanowires.

Wurtzite gallium phosphide (WZ GaP) has been predicted to exhibit a direct bandgap in the green spectral range. Optical transitions, however, are only weakly allowed by the symmetry of the bands. While efficient luminescence has been experimentally shown, the nature of the transitions is not yet clear. Here we apply tensile strain up to 6% and investigate the evolution of the photoluminescence (PL) spectrum of WZ GaP nanowires (NWs). The pressure and polarization dependence of the emission together with a theoretical analysis of strain effects is employed to establish the nature and symmetry of the transitions. We identify the emission lines to be related to localized states with significant admixture of Γ7c symmetry and not exclusively related to the Γ8c conduction band minimum (CBM). The results emphasize the importance of strongly bound state-related emission in the pseudodirect semiconductor WZ GaP and contribute significantly to the understanding of the optoelectronic properties of this novel material.

Pseudodirect to Direct Compositional Crossover in Wurtzite GaP/InxGa1-xP Core-Shell Nanowires.

Thanks to their uniqueness, nanowires allow the realization of novel semiconductor crystal structures with yet unexplored properties, which can be key to overcome current technological limits. Here we develop the growth of wurtzite GaP/InxGa1-xP core-shell nanowires with tunable indium concentration and optical emission in the visible region from 590 nm (2.1 eV) to 760 nm (1.6 eV). We demonstrate a pseudodirect (Γ8c-Γ9v) to direct (Γ7c-Γ9v) transition crossover through experimental and theoretical approach. Time resolved and temperature dependent photoluminescence measurements were used, which led to the observation of a steep change in carrier lifetime and temperature dependence by respectively one and 3 orders of magnitude in the range 0.28 ± 0.04 ≤ x ≤ 0.41 ± 0.04. Our work reveals the electronic properties of wurtzite InxGa1-xP.

Hund's Rule-Driven Dzyaloshinskii-Moriya Interaction at 3d-5d Interfaces.

Using relativistic first-principles calculations, we show that the chemical trend of the Dzyaloshinskii-Moriya interaction (DMI) in 3d-5d ultrathin films follows Hund's first rule with a tendency similar to their magnetic moments in either the unsupported 3d monolayers or 3d-5d interfaces. We demonstrate that, besides the spin-orbit coupling (SOC) effect in inversion asymmetric noncollinear magnetic systems, the driving force is the 3d orbital occupations and their spin-flip mixing processes with the spin-orbit active 5d states control directly the sign and magnitude of the DMI. The magnetic chirality changes are discussed in the light of the interplay between SOC, Hund's first rule, and the crystal-field splitting of d orbitals.

Direct band gap wurtzite gallium phosphide nanowires.

The main challenge for light-emitting diodes is to increase the efficiency in the green part of the spectrum. Gallium phosphide (GaP) with the normal cubic crystal structure has an indirect band gap, which severely limits the green emission efficiency. Band structure calculations have predicted a direct band gap for wurtzite GaP. Here, we report the fabrication of GaP nanowires with pure hexagonal crystal structure and demonstrate the direct nature of the band gap. We observe strong photoluminescence at a wavelength of 594 nm with short lifetime, typical for a direct band gap. Furthermore, by incorporation of aluminum or arsenic in the GaP nanowires, the emitted wavelength is tuned across an important range of the visible light spectrum (555-690 nm). This approach of crystal structure engineering enables new pathways to tailor materials properties enhancing the functionality.

Influence of SiO2 matrix on electronic and optical properties of Si nanocrystals.

Based on ab initio density functional theory we present electronic properties and the optical response for Si nanocrystals embedded in amorphous SiO(2) networks. Quasi-spherical dots with diameters from 0.8 to 1.6 nm are investigated. The results for Si nanocrystals embedded in SiO(2) are compared with corresponding results for hydrogenated Si nanocrystals of the same size. The calculations show the influence of the interface between nanocrystal and matrix on the electronic properties. The results are compared with recent experimental data and discussed in detail. As striking features, strong reductions of the gaps and their diameter variation are predicted due to the oxide presence. Electronic confinement mainly influences the absorption edge while at higher photon energies only broad peaks at almost fixed positions occur.

Guanine crystals: a first principles study.

We report first principles density functional theory studies on the basic ground state characteristics, dynamic properties, and the electronic structure of guanine crystals. The effect of water molecules within the crystal is studied in detail, and we discuss their influence on the structural, vibrational, and electronic properties. The geometries calculated for various crystal structures are compared with gas-phase calculations and available experimental data. Phonon frequencies and eigenvectors are predicted for intermolecular and intramolecular lattice vibrations. Vibrational and electronic density-of-states are presented and analyzed. The electronic band structure near the fundamental gap is calculated from the Kohn-Sham approach. We find that the former molecular HOMO states form a dispersive band in the pi-pi stacking direction upon condensation resulting in a large bandwidth of 0.83 eV. Consequences for the charge transport in layered van der Waals bonded organic molecular crystals are discussed.

Initial stage of Si(001) surface oxidation from first-principles calculations.

A comprehensive density-functional theory (DFT) study of the atomic structure, electronic properties, and optical response of the Si(001) surface at the initial stages of oxidation is presented. The most favored adsorption position of a single O atom on top of the (4 x 2)-reconstructed Si(001) surface is found at the back-bond of the "down" Si dimer atom. There is no energy barrier for oxygen insertion into this bond. The ionization energy of the surface reaches a maximum when the oxidation of the second Si monolayer starts. Oxidation leads to an increase of the energy gap between occupied and empty surface states. The calculated reflectance anisotropy spectroscopy (RAS) data in comparison with experiment suggest a considerable amount of surface disorder already after oxidation of the first monolayer.

Amorphous Ge quantum dots embedded in crystalline Si: ab initio results.

We study amorphous Ge quantum dots embedded in a crystalline Si matrix through structure modeling and simulation using ab initio density functional theory including spin-orbit interaction and quasiparticle effects. Three models are generated by replacing a spherical region within diamond Si by Ge atoms and creating a disordered bond network with appropriate density inside the Ge quantum dot. After total-energy optimisations of the atomic geometry we compute the electronic and optical properties. We find three major effects: (i) the resulting nanostructures adopt a type-I heterostructure character; (ii) the lowest optical transitions occur only within the Ge quantum dots, and do not involve or cross the Ge-Si interface. (iii) for larger amorphous Ge quantum dots, with diameters of about 2.0 and 2.7 nm, absorption peaks appear in the mid-infrared spectral region. These are promising candidates for intense luminescence at photon energies below the gap energy of bulk Ge.

Nonmetallic substrates for growth of silicene: an ab initio prediction.

By means of first-principles calculations we predict the stability of silicene layers as buckled honeycomb lattices on Cl-passivated Si(1 1 1) and clean CaF2(1 1 1) surfaces. The van der Waals interaction between silicene and the inert substrate stabilizes the adsorbate system while not destroying the Si pz-derived linear bands forming Dirac cones at the Brillouin zone corners. Only small gaps of about 3 and 52 meV are opened.

Influence of on-site Coulomb interaction U on properties of MnO(001)2 × 1 and NiO(001)2 × 1 surfaces.

We investigate the non-polar and antiferromagnetic (001) surfaces of MnO and NiO crystallizing in the antiferromagnetic type-II phase by means of spin-polarized density functional theory. Results are presented for surface energy, magnetization, and electronic structure. Besides the comparison of the two materials with differently filled minority-spin t(2g) shells we study the influence of exchange-correlation treatment within two schemes, the generalized gradient approximation GGA and the GGA + U scheme including an effective on-site d-d interaction U.

Influence of Strong Electron Correlation on Magnetism in Transition-Metal Doped Si Nanocrystals.

We studied the influence of strong electron correlation on magnetic properties of Si nanocrystals doped with the transition metal (TM) atoms Mn and Fe. Different approaches to describe exchange and correlation (XC) effects are compared within a density-functional framework. Beside a semilocal treatment, two different methods to include the influence of electron correlation on the localized TM 3d states are studied. They are based on XC functionals with the inclusion of on-site Coulomb repulsion or short-range screened exchange. We demonstrate a strong dependence of both electronic structure and magnetization on the used XC functional. The inclusion of strong correlation drastically changes position and occupation of the TM or TM-Si-bond-derived levels as well as the total magnetic moments.