First-principles energetics of water clusters and ice: a many-body analysis.

Standard forms of density-functional theory (DFT) have good predictive power for many materials, but are not yet fully satisfactory for cluster, solid, and liquid forms of water. Recent work has stressed the importance of DFT errors in describing dispersion, but we note that errors in other parts of the energy may also contribute. We obtain information about the nature of DFT errors by using a many-body separation of the total energy into its 1-body, 2-body, and beyond-2-body components to analyze the deficiencies of the popular PBE and BLYP approximations for the energetics of water clusters and ice structures. The errors of these approximations are computed by using accurate benchmark energies from the coupled-cluster technique of molecular quantum chemistry and from quantum Monte Carlo calculations. The systems studied are isomers of the water hexamer cluster, the crystal structures Ih, II, XV, and VIII of ice, and two clusters extracted from ice VIII. For the binding energies of these systems, we use the machine-learning technique of Gaussian Approximation Potentials to correct successively for 1-body and 2-body errors of the DFT approximations. We find that even after correction for these errors, substantial beyond-2-body errors remain. The characteristics of the 2-body and beyond-2-body errors of PBE are completely different from those of BLYP, but the errors of both approximations disfavor the close approach of non-hydrogen-bonded monomers. We note the possible relevance of our findings to the understanding of liquid water.

Characterization and deformation response of orthotropic fibre networks with auxetic out-of-plane behaviour

In the present paper, highly porous fibre networks made of 316L fibres, with different fibre volume fractions, are characterized in terms of network architecture, elastic constants and fracture energies. Elastic constants are measured using quasi-static mechanical and modal vibration testing, yielding local and globally averaged properties, respectively. Differences between quasi-static and dynamic elastic constants are attributed to through-thickness shear effects. Regardless of the method employed, networks show signs of material inhomogeneity at high fibre densities, in agreement with X-ray nanotomography results. Strong auxetic (or negative Poisson's ratio) behaviour is observed in the through-thickness direction, which is attributed to fibre kinking induced during processing. Measured fracture energies are compared with model predictions incorporating information about in-plane fibre orientation distribution, fibre volume fraction and single fibre work of fracture. Experimental values are broadly consistent with model predictions, based on the assumption that this energy is primarily associated with plastic deformation of individual fibres within a process zone of the same order as the inter-joint spacing. © 2013 Published by Elsevier Ltd. on behalf of Acta Materialia Inc. All rights reserved.

Excitation energy dependent raman signatures of ABA- and ABC-stacked few-layer graphene

The dependence of the Raman spectrum on the excitation energy has been investigated for ABA-and ABC- stacked few-layer graphene in order to establish the fingerprint of the stacking order and the number of layers, which affect the transport and optical properties of few-layer graphene. Five different excitation sources with energies of 1.96, 2.33, 2.41, 2.54 and 2.81â €...eV were used. The position and the line shape of the Raman 2D, G*, N, M, and other combination modes show dependence on the excitation energy as well as the stacking order and the thickness. One can unambiguously determine the stacking order and the thickness by comparing the 2D band spectra measured with 2 different excitation energies or by carefully comparing weaker combination Raman modes such as N, M, or LOLA modes. The criteria for unambiguous determination of the stacking order and the number of layers up to 5 layers are established.

Amorphous oxide semiconductor TFTs for displays and imaging

© 2013 IEEE. This paper reviews the mechanisms underlying visible light detection based on phototransistors fabricated using amorphous oxide semiconductor technology. Although this family of materials is perceived to be optically transparent, the presence of oxygen deficiency defects, such as vacancies, located at subgap states, and their ionization under illumination, gives rise to absorption of blue and green photons. At higher energies, we have the usual band-to-band absorption. In particular, the oxygen defects remain ionized even after illumination ceases, leading to persistent photoconductivity, which can limit the frame-rate of active matrix imaging arrays. However, the persistence in photoconductivity can be overcome through deployment of a gate pulsing scheme enabling realistic frame rates for advanced applications such as sensor-embedded display for touch-free interaction.

A thermalization energy analysis of the threshold voltage shift in amorphous indium gallium zinc oxide thin film transistors under simultaneous negative gate bias and illumination

It has been previously observed that thin film transistors (TFTs) utilizing an amorphous indium gallium zinc oxide (a-IGZO) semiconducting channel suffer from a threshold voltage shift when subjected to a negative gate bias and light illumination simultaneously. In this work, a thermalization energy analysis has been applied to previously published data on negative bias under illumination stress (NBIS) in a-IGZO TFTs. A barrier to defect conversion of 0.65-0.75 eV is extracted, which is consistent with reported energies of oxygen vacancy migration. The attempt-to-escape frequency is extracted to be 10 6-107 s-1, which suggests a weak localization of carriers in band tail states over a 20-40 nm distance. Models for the NBIS mechanism based on charge trapping are reviewed and a defect pool model is proposed in which two distinct distributions of defect states exist in the a-IGZO band gap: these are associated with states that are formed as neutrally charged and 2+ charged oxygen vacancies at the time of film formation. In this model, threshold voltage shift is not due to a defect creation process, but to a change in the energy distribution of states in the band gap upon defect migration as this allows a state formed as a neutrally charged vacancy to be converted into one formed as a 2+ charged vacancy and vice versa. Carrier localization close to the defect migration site is necessary for the conversion process to take place, and such defect migration sites are associated with conduction and valence band tail states. Under negative gate bias stressing, the conduction band tail is depleted of carriers, but the bias is insufficient to accumulate holes in the valence band tail states, and so no threshold voltage shift results. It is only under illumination that the quasi Fermi level for holes is sufficiently lowered to allow occupation of valence band tail states. The resulting charge localization then allows a negative threshold voltage shift, but only under conditions of simultaneous negative gate bias and illumination, as observed experimentally as the NBIS effect. © 2014 AIP Publishing LLC.

Ni(Pt)-silicide contacts on CMOS devices: Impact of substrate nature and Pt concentration on the phase formation

Ni silicides used as contacts in source/drain and gate of advanced CMOS devices were analyzed by atom probe tomography (APT) at atomic scale. These measurements were performed on 45 nm nMOS after standard self-aligned silicide (salicide) process using Ni(5 at.% Pt) alloy. After the first annealing (RTA1), δ-Ni2Si was the only phase formed on gate and source/drain while, after the second annealing (RTA2), two different Ni silicides have been formed: NiSi on the gate and δ-Ni2Si on the source and drain. This difference between source/drain and gate regions in nMOS devices has been related to the Si substrate nature (poly or mono-crystalline) and to the size of the contact. In fact, NiSi seems to have difficulties to nucleate in the narrow source/drain contact on mono-crystalline Si. The results have been compared to analysis performed on 28 nm nMOS where the Pt concentration is higher (10 at.% Pt). In this case, θ-Ni2Si is the first phase to form after RTA1 and NiSi is then formed at the same time on source (or drain) and gate after RTA2. The absence of the formation of NiSi from δ-Ni 2Si/Si(1 0 0) interface compared to θ-Ni2Si/Si(1 0 0) interface could be related to the difference of the interface energies. The redistributions of As and Pt in different silicides and interfaces were measured and discussed. In particular, it has been evidenced that Pt redistributions obtained on both 45 and 28 nm MOS transistors correspond to respective Pt distributions measured on blanket wafers. © 2013 Elsevier B.V. All rights reserved.

Light induced instability mechanism in amorphous InGaZn oxide semiconductors

A model of the negative bias illumination stress instability in InGaZn oxide is presented, based on the photo-excitation of electrons from oxygen interstitials. The O interstitials are present to compensate hydrogen donors. The O interstitials are found to spontaneously form in O-rich conditions for Fermi energies at the conduction band edge, much more easily that in related oxides. The excited electrons give rise to a persistent photoconductivity due to an energy barrier to recombination. The formation energy of the O interstitials varies with their separation from the H donors, which leads to a voltage stress dependence on the compensation. © 2014 AIP Publishing LLC.

Quantitative structure-property relationships (QSPRs) on direct photolysis of PCDDs

By the use of partial least squares (PLS) method and 27 quantum chemical descriptors computed by PM3 Hamiltonian, a statistically significant QSPR were obtained for direct photolysis quantum yields (Y) of selected Polychlorinated dibenzo-p-dioxins (PCDDs). The QSPR can be used for prediction. The direct photolysis quantum yields of the PCDDs are dependent on the number of chlorine atoms bonded with the parent structures, the character of the carbon-oxygen bonds, and molecular polarity. Increasing bulkness and polarity of PCDDs lead to decrease of log Y values. Increasing the frontier molecular orbital energies (E-lumo and E-homo) and heat of formation (HOF) values leads to increase of log Y values. (C) 2001 Elsevier Science Ltd. All rights reserved.

Donor-donor binding in In2O3: Engineering shallow donor levels

Using first-principles band structure methods, we investigate the interactions between different donors in In2O3. Through the formation energy and transition energy level calculations, we find that an oxygen-vacancy creates a deep donor level, while an indium-interstitial or a tin-dopant induces a shallow donor level. The coupling between these donor levels gives rise to even shallower donor levels and leads to a significant reduction in their formation energies. Based on the analysis of the PBE0-corrected band structure and the molecular-orbital bonding diagram, we demonstrate these effects of donor-donor binding. In addition, total energy calculations show that these defect pairs tend to be more stable with respect to the isolated defects due to their negative binding energies. Thus, we may design shallow donor levels to enhance the electrical conductivity via the donor donor binding.

The effect of an electric field on the nonlinear response of InAs/GaAs quantum dots

The refractive nonlinearities of InAs/GaAs quantum dots under a dc electric field at photon energies above its band gap energy have been studied using the reflection Z-scan technique. The effect of the dc electric field on the nonlinear response of InAs/GaAs quantum dots showed similar linear and quadratic electro-optic effects as in the linear response regime at low fields. This implies that the electro-optic effect in the nonlinear regime is analogous to the response in the linear regime for semiconductor quantum dots. Our experimental results show the potential for voltage tunability in InAs quantum dot-based nonlinear electro-optic devices.

Correcting the systematic error of the density functional theory calculation: the alternate combination approach of genetic algorithm and neural network

The alternate combinational approach of genetic algorithm and neural network (AGANN) has been presented to correct the systematic error of the density functional theory (DFT) calculation. It treats the DFT as a black box and models the error through external statistical information. As a demonstration, the AGANN method has been applied in the correction of the lattice energies from the DFT calculation for 72 metal halides and hydrides. Through the AGANN correction, the mean absolute value of the relative errors of the calculated lattice energies to the experimental values decreases from 4.93% to 1.20% in the testing set. For comparison, the neural network approach reduces the mean value to 2.56%. And for the common combinational approach of genetic algorithm and neural network, the value drops to 2.15%. The multiple linear regression method almost has no correction effect here.

Structural and optical properties of Al1-xInxN epilayers on GaN template grown by metalorganic chemical vapor deposition

This paper reports that Al1-xInxN epilayers were grown on GaN template by metalorganic chemical vapor deposition with an In content of 7%-20%. X-ray diffraction results indicate that all these Al1-xInxN epilayers have a relatively low density of threading dislocations. Rutherford backscattering/channeling measurements provide the exact compositional information and show that a gradual variation in composition of the Al1-xInxN epilayer happens along the growth direction. The experimental results of optical reflection clearly show the bandgap energies of Al1-xInxN epilayers. A bowing parameter of 6.5 eV is obtained from the compositional dependence of the energy gap. The cathodoluminescence peak energy of the Al1-xInxN epilayer is much lower than its bandgap, indicating a relatively large Stokes shift in the Al1-xInxN sample.

Defects in gallium nitride nanowires: First principles calculations

Atomic configurations and formation energies of native defects in an unsaturated GaN nanowire grown along the [001] direction and with (100) lateral facets are studied using large-scale ab initio calculation. Cation and anion vacancies, antisites, and interstitials in the neutral charge state are all considered. The configurations of these defects in the core region and outermost surface region of the nanowire are different. The atomic configurations of the defects in the core region are same as those in the bulk GaN, and the formation energy is large. The defects at the surface show different atomic configurations with low formation energy. Starting from a Ga vacancy at the edge of the side plane of the nanowire, a N-N split interstitial is formed after relaxation. As a N site is replaced by a Ga atom in the suboutermost layer, the Ga atom will be expelled out of the outermost layers and leaves a vacancy at the original N site. The Ga interstitial at the outmost surface will diffuse out by interstitialcy mechanism. For all the tested cases N-N split interstitials are easily formed with low formation energy in the nanowires, indicating N-2 molecular will appear in the GaN nanowire, which agrees well with experimental findings.

Investigation of gain recovery for InAs/GaAs quantum dot semiconductor optical amplifiers by rate equation simulation

The gain recoveries in quantum dot semiconductor optical amplifiers (QD SOAs) are numerically studied by rate equation simulation. Similar to the optical pump-probe experiment, the injection of double 150 fs optical pulses is used to simulate the gain recovery of a weak continuous signal under different injection levels, inhomogeneous broadenings, detuning wavelengths, and pulse signal energies for the QD SOAs. The obtained gain recoveries are then fitted by a response function with multiple exponential terms to determine the response times. The gain recovery can be described by three exponential terms with the time constants, which can be explained as carrier relaxation from the excited state to the ground state, carrier captured by the excited state from the wetting layer, and the supply of the wetting layer carriers. The fitted lifetimes decrease with the increase of the injection currents under gain unsaturation, slightly decrease with the decrease of inhomogeneous broadening of QDs, and increase with the increase of detuning wavelength between continuous signal and pulse signal and the increase of the pulse energy.

The formation and electronic structures of 3d transition-metal atoms doped in silicon nanowires

Using first-principles methods, we systematically study the mechanism of defect formation and electronic structures for 3d transition-metal impurities (V, Cr, Mn, Fe, and Co) doped in silicon nanowires. We find that the formation energies of 3d transition-metal impurities with electrons or holes at the defect levels always increase as the diameters of silicon nanowires decrease, which suggests that self-purification, i.e., the difficulty of doping in silicon nanowires, should be an intrinsic effect. The calculated results show that the defect formation energies of Mn and Fe impurities are lower than those of V, Cr, and Co impurities in silicon nanowires. It indicates that Mn and Fe can easily occupy substitutional site in the interior of silicon nanowires. Moreover, they have larger localized moments, which means that they are good candidates for Si-based dilute magnetic semiconductor nanowires. The doping of Mn and Fe atom in silicon nanowires introduces a pair of energy levels with t(2) symmetry. One of which is dominated by 3d electrons of Mn or Fe, and the other by neighboring dangling bonds of Si vacancies. In addition, a set of nonbonding states localized on the transition-metal atom with e symmetry is also introduced. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.3000445]