Structural and electronic properties of defects at grain boundaries in CuInSe2.

We report on a first-principles study of the structural and electronic properties of a Σ3 (112) grain boundary model in CuInSe2. The study focuses on a coherent, stoichiometry preserving, cation-Se terminated grain boundary, addressing the properties of the grain boundary as such, as well as the effect of well known defects in CuInSe2. We show that in spite of its apparent simplicity, such a grain boundary exhibits a very rich phenomenology, providing an explanation for several of the experimentally observed properties of grain boundaries in CuInSe2 thin films. In particular, we show that the combined effect of Cu vacancies and cation antisites can result in the observed Cu depletion with no In enrichment at the grain boundaries. Furthermore, Cu vacancies are unlikely to produce a hole barrier at the grain boundaries, but Na may indeed have such an effect. We find that Na-on-Cu defects will tend to form abundantly at the grain boundaries, and can provide a mechanism for the carrier depletion and/or type inversion experimentally reported.

A novel explanation for the increased conductivity in annealed Al-doped ZnO: an insight into migration of aluminum and displacement of zinc.

A combined experimental and first-principles study is performed to study the origin of conductivity in ZnO:Al nanoparticles synthesized under controlled conditions via a reflux route using benzylamine as a solvent. The experimental characterization of the samples by Raman, nuclear magnetic resonance (NMR) and conductivity measurements indicates that upon annealing in nitrogen, the Al atoms at interstitial positions migrate to the substitutional positions, creating at the same time Zn interstitials. We provide evidence for the fact that the formed complex of AlZn and Zni corresponds to the origin of the Knight shifted peak (KS) we observe in 27Al NMR. As far as we know, the role of this complex has not been discussed in the literature to date. However, our first-principles calculations show that such a complex is indeed energetically favoured over the isolated Al interstitial positions. In our calculations we also address the charge state of the Al interstitials. Further, Zn interstitials can migrate from AlZn and possibly also form Zn clusters, leading to the observed increased conductivity.

Extension of the basis set of linearized augmented plane wave (LAPW) method by using supplemented tight binding basis functions.

In order to increase the accuracy of the linearized augmented plane wave (LAPW) method, we present a new approach where the plane wave basis function is augmented by two different atomic radial components constructed at two different linearization energies corresponding to two different electron bands (or energy windows). We demonstrate that this case can be reduced to the standard treatment within the LAPW paradigm where the usual basis set is enriched by the basis functions of the tight binding type, which go to zero with zero derivative at the sphere boundary. We show that the task is closely related with the problem of extended core states which is currently solved by applying the LAPW method with local orbitals (LAPW+LO). In comparison with LAPW+LO, the number of supplemented basis functions in our approach is doubled, which opens up a new channel for the extension of the LAPW and LAPW+LO basis sets. The appearance of new supplemented basis functions absent in the LAPW+LO treatment is closely related with the existence of the u̇l-component in the canonical LAPW method. We discuss properties of additional tight binding basis functions and apply the extended basis set for computation of electron energy bands of lanthanum (face and body centered structures) and hexagonal close packed lattice of cadmium. We demonstrate that the new treatment gives lower total energies in comparison with both canonical LAPW and LAPW+LO, with the energy difference more pronounced for intermediate and poor LAPW basis sets.

The role of the VZn-NO-H complex in the p-type conductivity in ZnO.

Past research efforts aiming at obtaining stable p-type ZnO have been based on complexes involving nitrogen doping. A recent experiment by (J. G. Reynolds et al., Appl. Phys. Lett., 2013, 102, 152114) demonstrated a significant (∼10(18) cm(-3)) p-type behavior in N-doped ZnO films after appropriate annealing. The p-type conductivity was attributed to a VZn-NO-H shallow acceptor complex, formed by a Zn vacancy (VZn), N substituting O (NO), and H interstitial (Hi). We present here a first-principles hybrid functional study of this complex compared to the one without hydrogen. Our results confirm that the VZn-NO-H complex acts as an acceptor in ZnO. We find that H plays an important role, because it lowers the formation energy of the complex with respect to VZn-NO, a complex known to exhibit (unstable) p-type behavior. However, this additional H atom also occupies the hole level at the origin of the shallow behavior of VZn-NO, leaving only two states empty higher in the band gap and making the VZn-NO-H complex a deep acceptor. Therefore, we conclude that the cause of the observed p-type conductivity in experiment is not the presence of the VZn-NO-H complex, but probably the formation of the VZn-NO complex during the annealing process.

Native point defects in CuIn(1-x)Ga(x)Se2: hybrid density functional calculations predict the origin of p- and n-type conductivity.

We have performed a first-principles study of the p- and n-type conductivity in CuIn(1-x)Ga(x)Se2 due to native point defects, based on the HSE06 hybrid functional. Band alignment shows that the band gap becomes larger with x due to the increasing conduction band minimum, rendering it hard to establish n-type conductivity in CuGaSe2. From the defect formation energies, we find that In/GaCu is a shallow donor, while V(Cu), V(In/Ga) and Cu(In/Ga) act as shallow acceptors. Using the total charge neutrality of ionized defects and intrinsic charge carriers to determine the Fermi level, we show that under In-rich growth conditions InCu causes strongly n-type conductivity in CuInSe2. Under increasingly In-poor growth conditions, the conductivity type in CuInSe2 alters to p-type and compensation of the acceptors by In(Cu) reduces, as also observed in photoluminescence experiments. In CuGaSe2, the native acceptors pin the Fermi level far away from the conduction band minimum, thus inhibiting n-type conductivity. On the other hand, CuGaSe2 shows strong p-type conductivity under a wide range of Ga-poor growth conditions. Maximal p-type conductivity in CuIn(1-x)Ga(x)Se2 is reached under In/Ga-poor growth conditions, in agreement with charge concentration measurements on samples with In/Ga-poor stoichiometry, and is primarily due to the dominant acceptor Cu(In/Ga).

The origin of p-type conductivity in ZnM2O4 (M = Co, Rh, Ir) spinels.

ZnM2O4 (M = Co, Rh, Ir) spinels are considered as a class of potential p-type transparent conducting oxides (TCOs). We report the formation energy of acceptor-like defects using first principles calculations with an advanced hybrid exchange-correlation functional (HSE06) within density functional theory (DFT). Due to the discrepancies between the theoretically obtained band gaps with this hybrid functional and the - scattered - experimental results, we also perform GW calculations to support the validity of the description of these spinels with the HSE06 functional. The considered defects are the cation vacancy and antisite defects, which are supposed to be the leading source of disorder in the spinel structures. We also discuss the band alignments in these spinels. The calculated formation energies indicate that the antisite defects ZnM (Zn replacing M, M = Co, Rh, Ir) and VZn act as shallow acceptors in ZnCo2O4, ZnRh2O4 and ZnIr2O4, which explains the experimentally observed p-type conductivity in those systems. Moreover, our systematic study indicates that the ZnIr antisite defect has the lowest formation energy in the group and it corroborates the highest p-type conductivity reported for ZnIr2O4 among the group of ZnM2O4 spinels. To gain further insight into factors affecting the p-type conductivity, we have also investigated the formation of localized small polarons by calculating the self-trapping energy of the holes.

Diffusion of interacting particles in discrete geometries.

We evaluate the self-diffusion and transport diffusion of interacting particles in a discrete geometry consisting of a linear chain of cavities, with interactions within a cavity described by a free-energy function. Exact analytical expressions are obtained in the absence of correlations, showing that the self-diffusion can exceed the transport diffusion if the free-energy function is concave. The effect of correlations is elucidated by comparison with numerical results. Quantitative agreement is obtained with recent experimental data for diffusion in a nanoporous zeolitic imidazolate framework material, ZIF-8.

Unveiling the Electronic Structure of Pseudotetragonal WO3 Thin Films.

WO3 is a 5d compound that undergoes several structural transitions in its bulk form. Its versatility is well-documented, with a wide range of applications, such as flexopiezoelectricity, electrochromism, gating-induced phase transitions, and its ability to improve the performance of Li-based batteries. The synthesis of WO3 thin films holds promise in stabilizing electronic phases for practical applications. However, despite its potential, the electronic structure of this material remains experimentally unexplored. Furthermore, its thermal instability limits its use in certain technological devices. Here, we employ tensile strain to stabilize WO3 thin films, which we call the pseudotetragonal phase, and investigate its electronic structure using a combination of photoelectron spectroscopy and density functional theory calculations. This study reveals the Fermiology of the system, notably identifying significant energy splittings between different orbital manifolds arising from atomic distortions. These splittings, along with the system's thermal stability, offer a potential avenue for controlling inter- and intraband scattering for electronic applications.

Spin-orbit-mediated manipulation of heavy-hole spin qubits in gated semiconductor nanodevices.

A novel spintronic nanodevice is proposed that is able to manipulate the single heavy-hole spin state in a coherent manner. It can act as a single quantum logic gate. The heavy-hole spin transformations are realized by transporting the hole around closed loops defined by metal gates deposited on top of the nanodevice. The device exploits Dresselhaus spin-orbit interaction, which translates the spatial motion of the hole into a rotation of the spin. The proposed quantum gate operates on subnanosecond time scales and requires only the application of a weak static voltage which allows for addressing heavy-hole spin qubits individually. Our results are supported by quantum mechanical time-dependent calculations within the four-band Luttinger-Kohn model.

Ground state configurations and melting of two-dimensional non-uniformly charged classical clusters.

We consider classical two-dimensional (2D) Coulomb clusters consisting of two species containing five particles with charge q(1) and five with charge q(2), respectively. Using Monte Carlo and molecular dynamics (MD) simulations, we investigated the ground state configurations as well as radial and angular displacements of particles as a function of temperature and their dependence on the ratio q = q(2)/q(1). We found new configurations and a new multi-step melting behavior for q sufficiently different from the uniform charge limit q = 1.

Flow analyses in the lower airways: patient-specific model and boundary conditions.

Computational fluid dynamics (CFD) is increasingly applied in the respiratory domain. The ability to simulate the flow through a bifurcating tubular system has increased the insight into the internal flow dynamics and the particular characteristics of respiratory flows such as secondary motions and inertial effects. The next step in the evolution is to apply the technique to patient-specific cases, in order to provide more information about pathological airways. This study presents a patient-specific approach where both the geometry and the boundary conditions (BC) are based on individual imaging methods using computed tomography (CT). The internal flow distribution of a 73-year-old female suffering from chronic obstructive pulmonary disease (COPD) is assessed. The validation is performed through the comparison of lung ventilation with gamma scintigraphy. The results show that in order to obtain agreement within the accuracy limits of the gamma scintigraphy scan, both the patient-specific geometry and the BC (driving pressure) play a crucial role. A minimal invasive test (CT scan) supplied enough information to perform an accurate CFD analysis. In the end it was possible to capture the pathological features of the respiratory system using the imaging and computational fluid dynamics techniques. This brings the introduction of this new technique in the clinical practice one step closer.

Correlation between severity of sleep apnea and upper airway morphology based on advanced anatomical and functional imaging.

Determination of the apnea hypopnea index (AHI) as a measure of the severity of obstructive sleep apnea/hypopnea syndrome (OSAHS) is a widely accepted methodology. However, the outcome of such a determination depends on the method used, is time consuming and insufficient for prediction of the effect of all treatment modalities. For these reasons more methods for evaluating the severity of OSAHS, based on different imaging modalities, have been looked into and recent studies have shown that anatomical properties determined from three-dimensional (3D) computed tomography (CT) images are good markers for the severity of the OSAHS. Therefore, we correlated anatomical measurements of a 3D reconstruction of the upper airway together with flow simulation results with the severity of OSAHS in order to find a combination of variables to indicate the severity of OSAHS in patients. The AHI of 20 non-selected, consecutive patients has been determined during a polysomnography. All patients also underwent a CT scan from which a 3D model of the upper airway geometry was reconstructed. This 3D model was used to evaluate the anatomical properties of the upper airway in OSAHS patients as well as to perform computational fluid dynamics (CFD) computations to evaluate the airflow and resistance of this upper airway. It has been shown that a combination of the smallest cross-sectional area and the resistance together with the body mass index (BMI) form a set of markers that predict very well the severity of OSAHS in patients within this study. We believe that these markers can be used to evaluate the outcome of an OSAHS treatment.

Dynamics of scattering on a classical two-dimensional artificial atom.

A classical two-dimensional (2D) model for an artificial atom is used to make a numerical "exact" study of elastic and nonelastic scattering. Interesting differences in the scattering angle distribution between this model and the well-known Rutherford scattering are found in the small energy and/or small impact parameter scattering regime. For scattering off a classical 2D hydrogen atom different phenomena such as ionization, exchange of particles, and inelastic scattering can occur. A scattering regime diagram is constructed as function of the impact parameter (b) and the initial velocity (v) of the incoming particle. In a small regime of the (b,v) space the system exhibits chaos, which is studied in more detail. Analytic expressions for the scattering angle are given in the high impact parameter asymptotic limit.

The work function of few-layer graphene.

A theoretical and experimental study of the work function of few-layer graphene is reported. The influence of the number of layers on the work function is investigated in the presence of a substrate, a molecular dipole layer, and combinations of the two. The work function of few-layer graphene is almost independent of the number of layers with only a difference between monolayer and multilayer graphene of about 60 meV. In the presence of a charge-donating substrate the charge distribution is found to decay exponentially away from the substrate and this is directly reflected in the work function of few-layer graphene. A dipole layer changes the work function only when placed in between the substrate and few-layer graphene through a change of the charge transfer between the two.

Ab initio study of hydrogenic effective mass impurities in Si nanowires.

The effect of B and P dopants on the band structure of Si nanowires is studied using electronic structure calculations based on density functional theory. At low concentrations a dispersionless band is formed, clearly distinguishable from the valence and conduction bands. Although this band is evidently induced by the dopant impurity, it turns out to have purely Si character. These results can be rigorously analyzed in the framework of effective mass theory. In the process we resolve some common misconceptions about the physics of hydrogenic shallow impurities, which can be more clearly elucidated in the case of nanowires than would be possible for bulk Si. We also show the importance of correctly describing the effect of dielectric confinement, which is not included in traditional electronic structure calculations, by comparing the obtained results with those of G0W0 calculations.

Auger electron emission initiated by the creation of valence-band holes in graphene by positron annihilation.

Auger processes involving the filling of holes in the valence band are thought to make important contributions to the low-energy photoelectron and secondary electron spectrum from many solids. However, measurements of the energy spectrum and the efficiency with which electrons are emitted in this process remain elusive due to a large unrelated background resulting from primary beam-induced secondary electrons. Here, we report the direct measurement of the energy spectra of electrons emitted from single layer graphene as a result of the decay of deep holes in the valence band. These measurements were made possible by eliminating competing backgrounds by employing low-energy positrons (<1.25 eV) to create valence-band holes by annihilation. Our experimental results, supported by theoretical calculations, indicate that between 80 and 100% of the deep valence-band holes in graphene are filled via an Auger transition.

Free surfaces recast superconductivity in few-monolayer MgB2: Combined first-principles and ARPES demonstration.

Two-dimensional materials are known to harbour properties very different from those of their bulk counterparts. Recent years have seen the rise of atomically thin superconductors, with a caveat that superconductivity is strongly depleted unless enhanced by specific substrates, intercalants or adatoms. Surprisingly, the role in superconductivity of electronic states originating from simple free surfaces of two-dimensional materials has remained elusive to date. Here, based on first-principles calculations, anisotropic Eliashberg theory, and angle-resolved photoemission spectroscopy (ARPES), we show that surface states in few-monolayer MgB2 make a major contribution to the superconducting gap spectrum and density of states, clearly distinct from the widely known, bulk-like σ- and π-gaps. As a proof of principle, we predict and measure the gap opening on the magnesium-based surface band up to a critical temperature as high as ~30 K for merely six monolayers thick MgB2. These findings establish free surfaces as an unavoidable ingredient in understanding and further tailoring of superconductivity in atomically thin materials.

Inhomogeneous melting in anisotropically confined two-dimensional clusters.

Molecular dynamic simulations are performed to investigate the melting process of two-dimensional clusters of classical charged particles trapped in an anisotropic parabolic potential. The confined particles interact through a repulsive potential. We find that the eccentricity of the confinement potential strongly affects the melting pattern of such clusters. Increasing the eccentricity of the confinement potential drives the system through three different melting regimes. Inhomogeneous melting is the typical melting process for anisotropically confined clusters and its appearance in small systems occurs in a distinct form called here internal intershell melting. The latter involves only particles in the center of the cluster while particles on the far left and right of the cluster are still ordered having a much higher melting temperature. Using the Lindemann's criterion the melting temperatures are determined as a function of the different parameters. The internal intershell melting process is found for both long-range (i.e., logarithmic) and short-range (i.e., screened Coulomb) interparticle interaction. Decreasing the range of the interparticle interaction increases the eccentricity of the confinement potential for which internal intershell melting can occur.

Spectrum of classical two-dimensional Coulomb clusters.

The frequency spectrum of a system of classical charged particles interacting through a Coulomb repulsive potential and which are confined in a two-dimensional parabolic trap is studied. It is shown that, apart from the well-known center-of-mass and breathing modes, which are independent of the number of particles in the cluster, there are more "universal" modes whose frequencies depend only slightly on the number of particles. To understand these modes the spectrum of excitations as a function of the number of particles is compared with the spectrum obtained in the hydrodynamic approach. The modes are classified according to their averaged vorticity and it is shown that these "universal" modes have the smallest vorticity and follow the hydrodynamic behavior.