Elucidating hydrogen assisting vacancy formation in metals: Mo and Nb as examples

Impurity H is inclined to be trapped by some defects with more space such as vacancy and grain boundary when it dissolves in a metal. Inversely, H can also enhance formation of large amount of vacancies even if there are few vacancies in intrinsic metals initially. Using first-principles simulation combined with statistical model, Mo and Nb as examples, we quantitatively calculate the concentration of vacancies including pure vacancy and H _n -vacancy (H _n V) complexes. The concentrations of vacancies in the form of H _n V notably increase due to the decrease of effective formation energy of vacancy from H stimulation. Our finding solves a long-standing puzzle on the atomistic mechanism underlying H assisting vacancy formation in some metals.     

Hydrogen behavior in Pd0.75Ag0.25H x studied by PAC and PAS

Hydrogen behavior in Pd_0.75Ag_0.25H _x has been investigated by both perturbed angular correlation (PAC) and positron annihilation lifetime spectroscopy (PAS) techniques. The PAC measurements with the ¹¹¹Ag/¹¹¹Cd probe nuclei were conducted at room temperature as a function of the hydrogen concentration x up to 0.35. At x = 0 the probe nuclei experienced no quadrupole perturbation, while a distinct perturbation was observed after hydrogen charging. The quadrupole interaction frequency ω ₁ and its distribution width σ ₁ and relative fraction f₁ all decrease with increasing hydrogen concentration, indicating size growth and concentration reduction of the hydrogen induced vacancy clusters. The measured frequency distribution width σ ₁ reveals hydrogen diffusion. The PAS measurements were also performed at room temperature. The obtained lifetimes and their variation with hydrogen concentration strongly support the PAC results. The experimental results can be explained by the appearance of the β-phase in the Pd_0.75Ag_0.25H _x samples. The α-phase is the major phase in the Pd_0.75Ag_0.25H _x samples. Charging of the hydrogen leads to the formation of the β-phase and the fraction of the β-phase increases with increasing hydrogen concentration. The present PAC and PAS results show that as the fraction of the β-phase increases, hydrogen induced vacancy clusters are formed and become larger and larger, while the cluster density reduces due to the combination of the vacancy clusters into larger size vacancy clusters.     

Divacancy complexes induced by Cu diffusion in Zn-doped GaAs

Positron annihilation spectroscopy was applied to investigate the nature and thermal behavior of defects induced by Cu diffusion in Zn-doped p-type GaAs crystals. Cu atoms were intentionally introduced in the GaAs lattice through thermally activated diffusion from a thin Cu capping layer at 1100 °C under defined arsenic vapor pressure. During isochronal annealing of the obtained Cu-diffused GaAs in the temperature range of 450?850 K, vacancy clusters were found to form, grow and finally disappear. We found that annealing at 650 K triggers the formation of divacancies, whereas further increasing in the annealing temperature up to 750 K leads to the formation of divacancy-copper complexes. The observations suggest that the formation of these vacancy-like defects in GaAs is related to the out-diffusion of Cu. Two kinds of acceptors are detected with a concentration of about 10¹⁶ ? 10¹⁷ cm^?3, negative ions and arsenic vacancy copper complexes. Transmission electron microscopy showed the presence of voids and Cu precipitates which are not observed by positron measurements. The positron binding energy to shallow traps is estimated using the positron trapping model. Coincidence Doppler broadening spectroscopy showed the presence of Cu in the immediate vicinity of the detected vacancies. Theoretical calculations suggested that the detected defect is V _Ga V _As-2Cu_Ga.     

Theoretical considerations regarding the defect structure of M1−xO cubic oxides for small departures from stoichiometry

This study examines the discrepancy between two models of defect structure proposed for M_1?xO cubic oxides with small departures from stoichiometry. One, involving vacancy aggregates such as 4:1 or 6:2 clusters is deduced by Callow et al. from the calculated defect formation energies. The other, involving free unassociated vacancies V″_M and V′_M is used by many authors to interpret their experimental results.In the particular case of M_1?xO, for which accurate thermodynamic data are available for 1273 K< T < 1423 K, it is shown that, between these two models, only the latter is consistent with the experimental ΔG(O₂) values and that the concentrations of clusters are negligible over the whole homogeneity range. Furthermore, the unassociated defect formation energies calculated by Catlow et al. [27] do not satisfactorily account for the experimental values of ΔH(O₂).     

Effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles

We explore the effects of hydrogen annealing on the room temperature ferromagnetism and optical properties of Cr-doped ZnO nanoparticles synthesized by the sol-gel method. X-ray diffraction and x-ray photoelectron spectroscopy data show evidence that Cr has been incorporated into the wurtzite ZnO lattice as Cr²⁺ ions substituting for Zn²⁺ ions without any detectable secondary phase in as-synthesized Zn_0.97Cr_0.03O nanopowders. The room temperature magnetization measurements reveal a large enhancement of saturation magnetization M_s as well as an increase of coercivity of H₂-annealed Zn_0.97Cr_0.03O:H samples. It is found that the field-cooled magnetization curves as a function of temperature from 40 to 400 K can be well fitted by a combination of a standard Bloch spin-wave model and Curie–Weiss law. The values of the fitted parameters of the ferromagnetic exchange interaction constant a and the Curie constant C of H₂-annealed Zn_0.97Cr_0.03O:H nanoparticles are almost doubled upon H₂-annealing. Photoluminescence measurements show evidence that the shallow donor defect or/and defect complexes such as hydrogen occupying an oxygen vacancy H_o may play an important role in the origin of H₂-annealing induced enhancement of ferromagnetism in Cr-H codoped ZnO nanoparticles.     

Palladium-vacancy pairs in p-type and n-type germanium

Time differential perturbed angular correlation spectroscopy was performed for n-type and p-type germanium samples that had been recoil-implanted with the probe ¹⁰⁰Pd/¹⁰⁰Rh. Two different measurements with the detectors aligned along <100> and <110> crystallographic directions of germanium confirm that the palladium probe pairs with the nearest neighbour vacancy and not a dopant. The pairs interact with a coupling constant of υ _Q = 10.7(2) MHz and this agrees with what has been observed in undoped Ge. This further suggests that the palladium pairs with a vacancy in germanium, doped or un-doped. It was also observed that there are more Pd-V pairs in Ga-doped than there are in Sb-doped Ge. DFT calculations of the binding energies of the Pd-defect complexes support the experimental observations.     

Defect studies in small CdTe clusters

We study Cd vacancy formation in prototype stoichiometric and non-stoichiometric CdTe clusters with and without passivation. For certain clusters like Cd₁₃Te₁₆, vacancy leads to severe distortion of the geometry due to propagation of defect. Annealing of the vacancy out of the cluster is observed in all unpassivated clusters. Passivated clusters retain their initial geometry and vacancy induced structural distortions are not seen in these clusters since the defect gets localized. Vacancy also induces intragap states. However, it was observed that the passivation of the dangling bonds created by the vacancy removes the intragap states. In an attempt to have CdTe clusters with extrinsic carriers, we substituted a Cd atom by its adjacent atoms Pd/Ag/In/Sn in these CdTe clusters. Substitutional doping of Cd by metal atoms increases the stability of unpassivated clusters. For certain clusters, metal atom doping leads to a half-metallic character. Pd/Ag-doped clusters are p-type semiconductors whereas In-doped clusters are n-type semiconductors. Sn doping in these clusters does not result in n-type semiconductors.     

Influence of the relative magnitude of the Jahn-Teller effect and level splitting in a cubic crystal field on the properties of the ground state of vacancy defects in semiconductors

The spatial structure of a vacancy and the properties of its electronic energy levels in a semiconductor with a lattice possessing point symmetry T _d are considered for an arbitrary relationship between the Jahn-Teller stabilization energy (associated with the F ₂ vibrational mode) and the t ₂-a ₁ splitting (Δ) caused by the cubic crystal field. The position of the minimum of the adiabatic potential and the distortion of the electronic density are calculated for the vacancy ground state for different relative values of Δ and coupling constants of the vacancy to the F ₂ vibrational mode. It is shown that, if the ground state of a carrier bound to a vacancy is a t ₂ state, the trigonal symmetry of the environment of the vacancy persists for any values of Δ, but the amount of displacements of atoms near the vacancy and the localization of the wave function of the bound carrier on the broken bond earmarked by the Jahn-Teller effect can depend heavily on Δ and are maximal at Δ → 0. This is also the case when the ground state of the vacancy is the a ₁ state, but the magnitude of Δ does not exceed a certain value, which is determined by the coupling constants and the elastic constant. The relation between Δ and the coupling constants is also shown to affect the properties of trigonal vacancy-shallow-donor complexes. For these complexes, calculations are performed of the dependence of the dipole direction determining the optical properties of the vacancy defect on the distortion of vacancy orbitals caused by the donor entering into the complex.     

The kinetics of vacancy annihilation and short range order formation in Ni 11.4 at % Cr

In Ni-Cr alloys annealing after quenching from high temperatures leads to an increase of electrical resistivity which is attributed to a short range order state often denoted as K-state. Here the kinetics of the formation of the K-state in a Ni 10% Cr alloy is investigated by resistivity measurements for different quenching and annealing temperatures. The measurements are analyzed by an extended Schulze-Lücke method [22] which assumes that the rate of resistivity change is proportional to the vacancy concentration and that this rate as well as the rate of vacancy annihilation is described by a chemical rate equation.This analysis allowed a quantitative determination of the parameters determining the kinetics of short range order formation under different vacancy concentrations as well as the kinetics of annealing out of the quenched-in surplus vacancies. Among other quantities this treatment yielded the activation energies for vacancy formation H_F = 1.16 eV, for vacancy migration H_M = 1.56 eV and, as an independent cross check, for self diffusion H_D = 2.73 eV in good agreement with H_F + H_M = 2.72 eV.     

A molecular cluster model of the Vo. center in paratellurite

A RHF-SCF electronic structure calculation has been performed by means of the MELD program package for a cluster model of the V_o^.-center, a basic radiation-induced defect in paratellurite identified recently by ESR as an oxygen vacancy defect with a net positive charge. A “perfect” Te₂O₇H₆ cluster has been constructed with an effective core potential and an STO-3G valence basis set complemented by a single Gaussian d-function on Te. The charge distribution inside this cluster has been optimized by adjusting positions and nuclear charges of the peripheral “hydrogens”. A Mulliken analysis of a Te₂O₆H₆ defect cluster derived from the perfect one by removing an O⁻ ion and relaxing both Te's showed that the unpaired spin is primarily concentrated on the Te nearest to the oxygen vacancy with appreciable spin densities on nearby atoms and a substantially modified distribution of the surplus charge. The open-shell wave function has also been employed to derive hyperfine constants, taking into account relativistic corrections in independently calculated values of |;ψ_5s(0)|² and 〈r⁻³〉_5p for the Te atom, but neglecting core polarization. The calculated spin populations and hyperfine parameters account for all major features of the ESR spectra.     

Quantum-Size Dependence of the Energy for Vacancy Formation in Charged Small Metal Clusters. Drop Model

Self-consistent computations of the monovacancy formation energy are performed for Na _N , Mg _N , and Al _N (12 < N ≤ 168) spherical clusters in the drop model for stable jelly. Scenarios of the Schottky vacancy formation and “bubble vacancy blowing” are considered. It is shown that the asymptotic behavior of the size dependences of the energy for the vacancy formation by these two mechanisms is different and the difference between the characteristics of a charged and neutral cluster is entirely determined by the difference between the ionization potentials of clusters and the energies of electron attachment to them.     

Hydrogen passivation of oxygen vacancies in LaAlO3

Through first-principles calculation using the screened hybrid functional, we investigate the energetics and electronic structure of substitutional hydrogen (H_O) in which one hydrogen replaces an oxygen atom in LaAlO₃. The calculated binding energy between the hydrogen and the oxygen vacancy (V_O) indicates that H_O is energetically likely to form in the oxide. H_O releases one electron to the conduction band, so it is a shallow donor. Most importantly, H_O completely eliminates the in-gap defect states associated with V_O, suggesting that hydrogen can be used as passivating agent for V_O acting as a carrier trap or fixed charge in the oxide and near the oxide/semiconductor interface in LaAlO₃-based devices.     

Energetics of defect formation and interaction in pyrrhotite Fe1−xS and its homogeneity range

Sulphur fugacities in equilibrium with Fe_1?xS (pyrrhotite) were measured at different temperatures in the range 820–1374 K by direct (silica gauges) and indirect (H₂S/H₂) methods. The results give direct evidence of the boundaries of the homogeneity range and can be interpreted in terms of iron vacancy formation and interaction and of an additional defect, e.g. iron on sulphur sites. The homogeneity range of Fe_1?xS is calculated as a function of temperature from the energetic parameters of the defects and the sulphur fugacities limiting the existence region of this phase.Fe_1?xS exists with positive values of x except at the eutectic with iron (1261 K) where x is 0±0.0001.     

Ab initio study of formation, migration and binding properties of helium-vacancy clusters in aluminum

Ab initio calculations based on density functional theory have been performed to study the dissolution and migration of helium, and the stability of small helium-vacancy clusters He_nV_m (n, m=0-4) in aluminum. The results indicate that the octahedral configuration is more stable than the tetrahedral. Interstitial helium atoms are predicted to have attractive interactions and jump between two octahedral sites via an intermediate tetrahedral site with low migration energy. The binding energies of an interstitial He atom and an isolated vacancy to a He_nV_m cluster are also obtained from the calculated formation energies of the clusters. We find that the di- and tri-vacancy clusters are not stable, but He atoms can increase the stability of vacancy clusters.     

Hydrogen adsorption and storage of Ca-decorated graphene with topological defects: A first-principles study

As a candidate for hydrogen storage medium, geometric stability and hydrogen capacity of Ca-decorated graphene with topological defects are investigated using the first-principle based on density functional theory (DFT), specifically for the experimentally realizable single carbon vacancy (SV), 585 double carbon vacancy (585 DCV) and 555–777 double carbon vacancy (555–777 DCV) defects. It is found that Ca atom can be stabilized on above defective graphenes since Ca׳s binding energy on vacancy defect is much larger than its cohesive energy. Up to six H₂ molecules can stably bind to a Ca atom on defective graphene with the average adsorption energies of 0.17–0.39 eV/H₂. The hybridization of the Ca-3d orbitals with H₂-σorbitals and the electrostatic interaction between the Ca cation and the induced H₂ dipole both contribute to the H₂ molecules binding. Double-side Ca-decorated graphene with 585 DCV and 555–777 DCV defects can theoretically reach a gravimetric capacity of 5.2 wt% hydrogen, indicating that Ca-decorated defective graphene can be used as a promising material for high density hydrogen storage.     

Properties suggesting H3+-type clusters in some metallic hydrides

The p-c-T relationships for the hydrogen-rich phase of some metallic hydrides are calculated supposing the formation of H₃⁺ -type clusters in the metal lattice in equilibrium with the hydrogen gas. The experimental data for the hydride phase of LaNi₅, Pd, Nb (H?Nb? 0.75) and U are consistent with this model. Other properties reported in literature which seem to support this model are discussed.     

Investigation of PdZn nanoparticle formation upon the thermal decomposition of acetate precursors by in situ XRD and XAFS

The formation of metal or metal-oxide nanoparticles from four different precursor systems, including palladium(II) acetate, zinc(II) acetate, their 1: 1 mechanical mixture and the palladium-zinc bimetallic acetate complex PdZn(OCOMe)₄(H₂O), upon heating in a He + 5% H₂ atmosphere is studied using the X-ray diffraction and EXAFS (Extended X-ray absorption fine structure) techniques in the in situ mode. X-ray diffraction is primarily used to monitor changes in the phase composition of the samples. At specific moments when qualitative changes in the composition occur, EXAFS spectra at the K-edges of Pd and Zn are also measured. Using a combination of these two techniques, a detailed sequence of the phase transformations in each of the four precursor systems is revealed. It is found that the bimetallic acetate complex and the mixture of two monometallic acetates undergo chemical reduction to form zerovalent palladium under milder conditions than zinc acetate. However, the formation of a PdZn alloy from the mixture of metal acetates proceeds with a significant diffusion barrier.     

Electronic structures and optical properties of rutile TiO2 with different point defects from DFT + U calculations

The electronic states and formation energies of four types of lattice point defects in rutile TiO₂ are studied using the first-principles calculations. The existence of oxygen vacancy leads to a deep donor defect level in the forbidden band, while the Ti interstitial forms two local states. It is predicted that oxygen vacancy prefers to combine with Ti-interstitial to form V_O–Ti_i dimer by a partial 3d electron transfer from the Ti_i to its neighboring V_O. The charge distribution between a Ti interstitial and its neighboring Ti ions partially shields the Coulomb interactions. Lastly, optical properties of these defective lattices are discussed.     

The kinetics of formation and the parameters of radiation defect clusters in silicon

An approximate analytic solution of the system of equations describing the kinetics of formation and the parameters of radiation defect clusters in crystals is obtained. A model corresponding to the real parameters of Si is assumed as a basis for calculation and it is shown that two types of secondary radiation defect clusters may be realized corresponding to the congealing and spreading of the initial vacancy clusters. The cluster type depends on the incident energy of the particle which creates the effects and on the physical parameters of the crystal under irradiation. For a congealing cluster most of the initial vacancies react within the original volume of the damage cascade and for a spreading cluster the final concentration of divacancies and A-centres within the original cascade volume is much less than the initial vacancy concentration, i.e. most of the vacancies form divacancies and A-centres dispersed throughout the crystal volume.

The definition of the concept “threshold energy of cluster formation” as the minimum primarily displaced atom energy for the creation of a “congealing” vacancy cluster is proposed.

It is shown that A-centres form a belt surrounding a central divacancy cluster.