Band-edge problem in the theoretical determination of defect energy levels: the O vacancy in ZnO as a benchmark case

Calculations of formation energies and charge transition levels of defects routinely rely on density functional theory (DFT) for describing the electronic structure. Since bulk band gaps of semiconductors and insulators are not well described in semilocal approximations to DFT, band-gap correction schemes or advanced theoretical models which properly describe band gaps need to be employed. However, it has become apparent that different methods that reproduce the experimental band gap can yield substantially different results regarding charge transition levels of point defects. We investigate this problem in the case of the (+2/0) charge transition level of the O vacancy in ZnO, which has attracted considerable attention as a benchmark case. For this purpose, we first perform calculations based on non-screened hybrid density functionals, and then compare our results with those of other methods. While our results agree very well with those obtained with screened hybrid functionals, they are strikingly different compared to those obtained with other band-gap corrected schemes. Nevertheless, we show that all the different methods agree well with each other and with our calculations when a suitable alignment procedure is adopted. The proposed procedure consists in aligning the electron band structure through an external potential, such as the vacuum level. When the electron densities are well reproduced, this procedure is equivalent to an alignment through the average electrostatic potential in a calculation subject to periodic boundary conditions. We stress that, in order to give accurate defect levels, a theoretical scheme is required to yield not only band gaps in agreement with experiment, but also band edges correctly positioned with respect to such a reference potential

Optical response of ferromagnetic YTiO_3 studied by spectral ellipsometry

We have studied the temperature dependence of spectroscopic ellipsometry spectra of an electrically insulating, nearly stoichiometric YTiO_3 single crystal with ferromagnetic Curie temperature T_C = 30 K. The optical response exhibits a weak but noticeable anisotropy. Using a classical dispersion analysis, we identify three low-energy optical bands at 2.0, 2.9, and 3.7 eV. Although the optical conductivity spectra are only weakly temperature dependent below 300 K, we are able to distinguish high- and low-temperature regimes with a distinct crossover point around 100 K. The low-temperature regime in the optical response coincides with the temperature range in which significant deviations from Curie-Weiss mean field behavior are observed in the magnetization. Using an analysis based on a simple superexchange model, the spectral weight rearrangement can be attributed to intersite d_i^1d_j^1 \longrightarrow d_i^2d_j^0 optical transitions. In particular, Kramers-Kronig consistent changes in optical spectra around 2.9 eV can be associated with the high-spin-state (^3T_1) optical transition. This indicates that other mechanisms, such as weakly dipole-allowed p-d transitions and/or exciton-polaron excitations, can contribute significantly to the optical band at 2 eV. The recorded optical spectral weight gain of 2.9 eV optical band is significantly suppressed and anisotropic, which we associate with complex spin-orbit-lattice phenomena near ferromagnetic ordering temperature in YTiO_3

Effect of strain on hyperfine-induced hole-spin decoherence in quantum dots

We theoretically consider the effect of strain on the spin dynamics of a single heavy-hole (HH) confined to a self-assembled quantum dot and interacting with the surrounding nuclei via hyperfine interaction. Confinement and strain hybridize the HH states, which show an exponential decay for a narrowed nuclear spin bath. For different strain configurations within the dot, the dependence of the spin decoherence time $T_2$ on external parameters is shifted and the non-monotonic dependence of the peak is altered. Application of external strain yields considerable shifts in the dependence of $T_2$ on external parameters. We find that external strain affects mostly the effective hyperfine coupling strength of the conduction band (CB), indicating that the CB admixture of the hybridized HH states plays a crucial role in the sensitivity of $T_2$ on strain

Hybridization and spin decoherence in heavy-hole quantum dots

We theoretically investigate the spin dynamics of a heavy hole confined to an unstrained III-V semiconductor quantum dot and interacting with a narrowed nuclear-spin bath. We show that band hybridization leads to an exponential decay of hole-spin superpositions due to hyperfine-mediated nuclear pair flips, and that the accordant single-hole-spin decoherence time T2 can be tuned over many orders of magnitude by changing external parameters. In particular, we show that, under experimentally accessible conditions, it is possible to suppress hyperfine-mediated nuclear-pair-flip processes so strongly that hole-spin quantum dots may be operated beyond the `ultimate limitation' set by the hyperfine interaction which is present in other spin-qubit candidate systems.Comment: 7 pages, 3 figure

The volume change due to F centres in alkali halides

The change in volume due to F centres in alkali halides is calculated using the ion-size correction method of Bartram, Stoneham and Gash (1968). In all cases the volume change Delta V is positive (expansion of the crystal) and satisfactory agreement with experiment is found in the two cases where measurements are available. The fractional volume change ( Delta V/a 3 ) decreases systematically with increasing anion or cation size

Mesoscopic modelling of charge evolution in conducting polymers

We address here some of the issues relating to conducting polymer based devices. We examine the effects of polymer disorder on charge injection, transport, trapping and recombination in light-emitting diodes (LEDs) using a mesoscopic model which includes specific realizations of the electroluminescent polymer network. A key point of this model is to consider both the intermolecular and the interdomain charge carrier transport which are strongly influenced by structural polymer disorder. Simulations of bipolar charge evolution (electrons and holes) through a polydiacetylene (PDA) film, which are injected in the polymer layer from the appropriated electrodes, have been used to give some insights to the issue concerning the fraction of polymer molecules contributing to the conduction process as well as to light emission. The effect of charge traps, such as cross-links, on space charge and recombination is also discussed

Mesoscopic study of bipolar charge transport in polymer-based devices

We present generalised Monte-Carlo calculations of bipolar charge carrier transport in polydiacetylene to assess effects of some key factors on the properties of polymer-based light emitting diodes. Our mesoscopic model includes specific realisations of the polymer network and examines the effect of polymer structural order on current flow and charge recombination within the polymer layer. Specifically addressed are the issues concerning the fractions of polymer strands contributing to the charge injection processes at electrode interfaces and to electroluminescence. Our results suggest that radiative recombination increases as short chain concentration increases, whereas current efficiency shows an opposite behaviour. Radiative recombination decreases as charge injection efficiency decreases and its internal efficiency seems to saturate for a luminescent chain concentration greater than 30%. Our results also suggest that both current efficiency and space charge increases as charge injection efficiency decreases. Polymer disorder due to inclusions in the network does seem to contribute to reduce both current and recombination efficiencies

Singlet-triplet decoherence due to nuclear spins in a double quantum dot

We have evaluated hyperfine-induced electron spin dynamics for two electrons confined to a double quantum dot. Our quantum solution accounts for decay of a singlet-triplet correlator even in the presence of a fully static nuclear spin system, with no ensemble averaging over initial conditions. In contrast to an earlier semiclassical calculation, which neglects the exchange interaction, we find that the singlet-triplet correlator shows a long-time saturation value that differs from 1/2, even in the presence of a strong magnetic field. Furthermore, we find that the form of the long-time decay undergoes a transition from a rapid Gaussian to a slow power law ($\sim 1/t^{3/2}$) when the exchange interaction becomes nonzero and the singlet-triplet correlator acquires a phase shift given by a universal (parameter independent) value of $3\pi/4$ at long times. The oscillation frequency and time-dependent phase shift of the singlet-triplet correlator can be used to perform a precision measurement of the exchange interaction and Overhauser field fluctuations in an experimentally accessible system. We also address the effect of orbital dephasing on singlet-triplet decoherence, and find that there is an optimal operating point where orbital dephasing becomes negligible.Comment: 12 pages, 4 figure