Stoichiometric Vacancies Research Articles

Ti- and Ba-rich phlogopitic micas in alkaline basic and upper mantle igneous rocks; stoichiometry, stability, and Fe valence estimation reassessed and rationalised

Ti- and Ba-rich tri-octahedral micas occur in fractionated basic igneous rocks, metasomatized mantle peridotites, metamorphosed pelites/carbonates, and hydrothermally altered mineral deposits. Electron microprobe analyses (EMP), with all iron reported as FeO, were widely used in the 1970/80s to interpret Ti and Ba substitution mechanisms, based on 22 O2– unit cell calculations, implying that cation vacancies occur in octahedral and/or intersheet sites. In 1996 EMP with chemical and physical analyses for ferric and total Fe, H2O, (OH), and element-specific Fe X-ray Absorption Spectroscopy (both K and L-edges) established valence states for Fe and Ti and cation site occupancies, that ∼50 % O replaces (OH) molecules, and that 24 anion cell formulae show the absence of cation vacancies. Cell formula calculation protocol for phlogopitic micas is refined here and results tested against the stoichiometric formula for vacancy-free phlogopite, XIIK2VIMg6IV[Si6Al2]O20(OH)4. Hypothetical sheet silicate compositions, calculated with fixed contents of vacancies linked to particular mixed-valence element substitutions, confirm that reliable unit cell formulae for natural mica solids require that each stoichiometric vacancy must be accounted for. If reliable estimates for ‘excess O’ (denoted WO2−) are assigned to EMP analyses, the proportion of the oxy-mica component in a mica solid solution can be defined. This approach is tested using published analyses for Ti- and Ba-rich biotites from fractionated basic and ultramafic volcanic igneous rocks (oxymica range 2.5–45 %; TiO2 up to 14 %; BaO up to 23 %), upper mantle peridotites (equivalent values 7–18 %; 6 %; 0.7 %), and metasomatised upper mantle (2–37 %; 9 %; 23 %). Enrichments of Ti and Ba in micas are clearly linked to the extra oxygen charge required to neutralise the more highly charged Ba2+ and Ti4+ replacing K+ and Mg2+.Substitution mechanisms involving Ba, Ti, and Fe3+ in ideal phlogopite involve coupled inter-site / inter-valence interactions so both site-ordering and valence-balance between the different cation sites must be accounted for. The cation exchange 2XIIK+ + 4VI(Mg2+ + Fe2+) + 4IVSi4+ ↔ XIIBa2+ + 3VITi4+ + 4(Altotal + Fe3+ + Crtotal)3+ is used here so that valence and site order can be considered together. Compositional variations show well-defined trends towards high-oxymica content and vacancy-free Ti and Ba mica end-members, rather than to oxy-free end-members with essential vacancies. Average compositions for different source rock micas are used to assess compositional trends; molecular WO2− values are refined by relating initial estimates directly to the wt.% TiO2 contents; and refined WO2− and stoichiometrically calculated Fe3+/Fetotal ratios ranging ∼0.1–0.5) are correlated with possible primary magmatic values.

Effects of impurities on the cooling of photoexcited carriers in La1−xSrxCoO3−δ: A DFT and nonadiabatic molecular dynamics study

Photo-carrier relaxation in semiconductors determines their photon-conversion efficiency. Impurities have been proven to play an essential role in improving the efficiency and stability of perovskites. We studied the effects of Sr-doping and O-vacancies on the electronic band structure and photoexcited carrier cooling of perovskite-type LaCoO3 using density functional theory and nonadiabatic molecular dynamics methods. We found that the substitution of Sr2+ for La3+ in LaCoO3 leads to a semiconductor–metal transition, while a stoichiometric oxygen vacancy restores semiconductor properties in La1−xSrxCoO3−δ (δ = x/6). In addition, the oxygen vacancy basically changes the electronic band structures, and for visible light with low oxygen vacancy intensity, the photo-electron cooling can be reduced fourfold relative to that of pure LaCoO3. We clarify the functions of impurities, Sr-dopants, and O-vacancies in LaCoO3 and find that the average coupling strength between carriers (electrons/holes) and phonons can be used as a descriptor to characterize carrier relaxation, which is of great value for the further development of practical photo-conversion based on perovskites.

Extremely enhanced thermal stability of Y2/3Cu3Ti4O12 ceramics by a Pechini method

AbstractY2/3Cu3Ti4O12 ceramic is a novel semiconductor with potential applications in electronic devices. However, its resistance drift and surface structure defects limit the application for negative temperature coefficient thermistor devices. A comparative study of solid‐phase and a Pechini processing of Y2/3Cu3Ti4O12 is presented in this paper, in the particular comparative study of stability. The Pechini method is found to be effective in lowering sintering temperature and improving thermal stability (ΔR/R0 < 0.3％) in comparison with solid‐phase method. The origin of the stability deterioration is related to the oxidation state of Cu ions and the migration of sublattice. The Pechini method overcomes stoichiometric ratio deviations and cation vacancy diffusion, thus reducing metal ion segregation in a continuous high‐temperature environment and thereby showing unique insensitivity to oxygen. The important role of the Pechini method in improving thermal stability is revealed, which is expected to be used in the preparation of high stability electron devices.

Characterization of thin films of Ga 2 Se 3 on Si fabricated using electron beam evaporation technique

Many studies have been conducted in the past on compound semiconductor and wide-gap semiconductor for their possible usage in place of oxide in metal-oxide-semiconductor structures for high-speed metal-oxide-semiconductor field-effect transistors application. The best candidates for this purpose, however, are compounds with stoichiometric vacant A 2 III B 3 VI type sites. A 2 III B 3 VI type compounds are wide-gap semiconductors with stoichiometric vacancies and low concentration of free and localized charged carriers. It has that gate insulators can be constructed from wide-gap semiconductor layers with thicknesses smaller than the Debye Screening distance. These new MS'S (metal-Wide bandgap semiconductor-semiconductor) with a good lattice match have less of interface states thus giving better stability to the structure. The idea was to use these MS'S structures for photovoltaic applications with insignificant number of interface states. During literature survey, it was also found that Ga2Se3 is the most prospective candidate for forming a heterostructure with Silicon because of its various properties. Structurally, perfect and homogeneous in thickness Ga2Se3 layers have already been formed in quasi-closed volume by the Hot Wall technique by B. I. Sysoev in the Voronezh Technological Institute, Russia. However, this technology is not cost-efficient for photovoltaic applications, although it has the advantage of better control of Ga and Se components. Over the last few years, many attempts have been made using many other techniques such as Sol-gel technique, vapour phase epitaxy, molecular beam epitaxy, etc. for preparing the thin film of GaSe. The current work is an attempt to prepare the Ga2Se3 film using the electron beam evaporation technique as it appeared to be much simpler. Film of thicknesses varying from 70 to 1000 Å were grown. The films have been studied for their morphology and properties for future use in photovoltaics and other device fabrication like IR detectors, etc. Various techniques were used to study the behavior of the films like XRD, SEM, and TEM.

Energetics of intrinsic point defects and hydrogen in tungsten borides: a first-principles study

To understand the irradiation resistance and hydrogen (H) behavior in tungsten borides (W x B y ) in a burning plasma fusion environment, the energetics of intrinsic point defects and H in six stable ground state W borides, including W2B, WB, WB2, W2B5, WB3 and WB4, have been investigated using first-principles density functional theory calculations. The results show that the formation energies of interstitials and vacancies do not directly depend on the W and B content in W borides. However, the interaction between vacancies of a stoichiometric vacancy (SV) cluster in W x B y is related to the atomic ratio of B to W (y/x). The vacancies of a minimum-size SV cluster in W x B y are energetically repulsive for y/x ⩽ 1, while the vacancies energetically bind together for y/x larger than 1. The formation energy of B Frenkel pairs in each W boride is lower than that of W Frenkel pairs. Among the six evaluated W x B y compositions, WB has the highest and the lowest formation energy of H interstitials and H-vacancy complexes, respectively; however, these two energies in WB2 are in reverse order. The average H binding energies to single vacancies in WB and WB4 are comparable with that in W, while this binding energy in WB3 and WB2 is obviously higher or lower than in W, respectively. The diffusion activation energy of H in W borides is anisotropic. One dimensional (1D) diffusion of H in W2B, as well as 1D/2D diffusion in WB, W2B5, WB3 and WB4 are preferred at relatively low temperatures; however, three-dimensional diffusion of H is predicted in WB2. The diffusion activation energy of H generally increases with B content in W borides due to the increasing local charge deficit caused by strong B–B covalent bonds. This study is useful for evaluating the performance of W borides in a fusion environment.

Characteristic mechanism for fast [formula omitted] conduction in [formula omitted

Solid hydrides are a new class of ionic conductors promising for future applications for hydrogen-carrier, catalysis, and energy conversion. The record-high H− conductivity reported for LaH2.5O0.25 is caused by extraordinarily large pre-exponential factor, which cannot be justified within any simple diffusion picture. To reveal H− dynamics in LaH2.5O0.25 on atomistic level, we developed DFT-based neural-network-potential for large-scale molecular dynamics (MD) simulation and discovered the H− diffusion mechanism: the stoichiometric vacancies are ordered and almost immobile, but they can be rarely kicked-out and become fast mobile vacancies that migrate in a coupled manner with 3H− ring-like rotations. The MD and DFT phonon analysis reveal that the mobile vacancy formation gives rise to an extremely large entropy leading to the anomalously large pre-exponential factor, and that the anharmonicity of H− vibrations causes the large pre-exponential factor. A design concept for faster H− conductor is proposed based on the present finding.

Probing the defect states of LuN1−δ: An experimental and computational study

We report electrical transport and optical spectroscopy measurements on LuN thin films variously doped with nitrogen vacancies along with the computed band structures of stoichiometric and nitrogen vacancy doped LuN. LuN has been the subject of several recent computational studies; however, the most recent experimental studies regarding its electronic properties are already over four decades old. Here, we bridge the void between computation and experiment with a combined study of LuN focusing on its electronic properties. We find that LuN is a semiconductor with an optical bandgap of ∼1.7 eV. Its conductivity can be controlled by nitrogen vacancy doping, which results in defect states at the conduction band minimum and valence band maximum. These results not only provide information on LuN but also help underpin understanding of the electronic properties of the entire rare-earth nitride series.

High-temperature spectrophotometry of indium chloride vapours as a method of study of the In – Se system

The goals of this work are as follows: (а) searching for a method of study of the In – Se system taking into account the specified problems and difficulties, (b) choosing a way for the instrumental implementation of this method, and (c) obtaining experimental evidence that this method and its implementation are promising. The choice of the In – Se system is related to the fact that indium selenides, layered structures and semiconductor phases with stoichiometric vacancies, are promising from the point of view of materials science. This choice is also related to the use of binary precursors for the synthesis of heterostructures based on CIS compounds.We studied the possibility of applying the auxiliary component method using the equilibrium with the participation of indium chloride vapours which were made to contact the condensed phases of the In – Se system. Equilibrium was achieved using high-temperature spectrophotometry of the vapour phase. The experiment had two stages. During the first stage we determined the absorption characteristics of the InCl3 vapour. During the second stage we studied the heterogeneous equilibrium of the unsaturated indium chloride vapour with several phases of the In – Se system. Over the course of the study, we determined the molar attenuation coefficients of the InCl3 vapour and plotted the temperature dependences of the value KP.It was found that the phase composition of the alloys significantly influences the position of the corresponding lines on the KP–T diagram, which proves the possibility of using the suggested auxiliary component method in its specific instrumental (spectrophotometric) implementation in order to study the In – Se system. We also showed the additional possibilities of using this method for plotting T-x diagrams of binary systems in such high-temperature areas where the binary solid phase is in equilibrium with the melt. This application of the method is related to the solubility of a vapour of an auxiliary component (chlorine in the form of indium chlorides) in the melts of binary phases (indium selenides).

Gold-Cage Perovskites: A Three-Dimensional AuIII-X Framework Encasing Isolated MX63- Octahedra (MIII = In, Sb, Bi; X = Cl-, Br-, I-).

The Cs8AuIII4MIIIX23 (M = In3+, Sb3+, Bi3+; X = Cl-, Br-, I-) perovskites are composed of corner-sharing Au-X octahedra that trace the edges of a cube containing an isolated M-X octahedron at its body center. This structure, unique within the halide perovskite family, may be derived from the doubled cubic perovskite unit cell by removing the metals at the cube faces. To our knowledge, these are the only halide perovskites where the octahedral sites do not bear an average 2+ charge. Charge compensation in these materials requires a stoichiometric halide vacancy, which is disordered around the Au atom at the unit-cell corner and orders when the crystallization is slowed. Using X-ray crystallography, X-ray absorption spectroscopy, and pair distribution function analysis, we elucidate the structure of this unusual perovskite. Metal-site alloying produces further intricacies in this structure, which our model explains. Compared to other halide perovskites, this class of materials shows unusually low absorption onset energies ranging between ca. 1.0 and 2.4 eV. Partial reduction of Au3+ to Au+ affords an intervalence charge-transfer band, which redshifts the absorption onset of Cs8Au4InCl23 from 2.4 to 1.5 eV. With connected Au-X octahedra and isolated M-X octahedra, this structure type combines zero- and three-dimensional metal-halide sublattices in a single material and stands out among halide perovskites for its ordering of homovalent metals, ordering of halide vacancies, and incorporation of purely trivalent metals at the octahedral sites.

A novel titanium oxycarbide phase with metal-vacancy (Ti1-yCxO1-x): Structural and thermodynamic basis

A unique phenomenon of TiC–TiO2 reaction at 900 °C is established, forming a quasi-pure phase of abnormal titanium oxycarbide, since it is commonly synthesized at temperatures above 1500 °C. Impurity of Magnéli phase (TinO2n-1, 4≤n≤9) is also detected in the product. Thermodynamics analysis indicates that the critical C/O concentration of titanium oxycarbide (x in TiCxO1-x) equilibrated with Magnéli phase at 900 °C is around 0.66, typically 0.651 for Ti4O7. The obtained titanium oxycarbide phase contains metal-vacancy in Ti site, as Ti1-yCxO1-x which is reported the first time, differing from stoichiometric vacancy of both Ti site and C/O site in conventional TiCxO1-x. The dominating part of TiC–TiO2 reaction at 900 °C is reaction via solid solution as directly introducing the Ti and O atoms of TiO2 into the FCC structure of TiC, which leads to the formation of metal-vacancy without altering the original lattice size, instead maintaining at the same level of TiC regardless of the variation of corresponding C/O concentration. The obtained maximum concentration of metal-vacancy in Ti1-yCxO1-x is 18%, close to the theoretical capacity of 18.9% which exists when the starting molar ratio of TiC and TiO2 is aiming to the formation of TiC0.651O0.349, as the critical composition equilibrated with Ti4O7. The stability of metal-vacancy in titanium oxycarbide is verified by first-principles calculation in the perspective of energy.

Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy.

Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L2,3-edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine FeI dopant ions to be linearly coordinated, occupying a D6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L2,3-edge XAS from which the energy reduction of 3dz2 due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L3-edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (∼280 cm−1), that corresponds with Orbach relaxation via the first excited, MJ = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.

Computational study of HCl adsorption on stoichiometric and oxygen vacancy PuO2 {111}, {110} and {100} surfaces

The interactions between HCl and both the pristine and defect {111}, {110} and {100} surfaces of PuO2 are modelled using hybrid density functional theory, within the periodic electrostatic embedded cluster method. In the case of the pristine surfaces, adsorptions onto the {110} surface are the most stable, likely due in part to the presence of surface hydrogen bonds. In addition, results suggest that even when dissociatively adsorbed onto the surface, the proximity of the hydrogen and chlorine atoms has a significant impact on the stability of the system. The electronic structure of both the pristine and reduced surfaces of PuO2 and UO2 is also probed, with unpaired electrons left behind in a neutral oxygen vacancy defect site having a greater tendency to delocalise on the surface of UO2 than PuO2. HCl adsorptions on the reduced surfaces reveal that configurations in which the chlorine atom attempts to “heal” the gap left by the oxygen vacancy in the {111} surface are by far the most stable of all considered. Finally, molecular thermodynamics is employed to translate adsorption energies to HCl thermal desorption temperatures, for each geometry considered. Particularly when a chlorine atom is embedded in the surface of PuO2, the temperatures required for thermal desorption to occur are high, implying that although thermal treatment is likely to remove some chlorine contamination from PuO2 samples, some will likely remain bound to defect sites within the material.

Radiation Resistance of (HgSe)3(In2Se3)<Mn>

We present the results of studies of the effect of electron irradiation on the electrophysical parameters of (HgSe)3(In2Se3) crystals, which are semimagnetic semiconductors with stoichiometric vacancies. It is shown that irradiation of (HgSe)3(In2Se3) with high-energy electrons (Ee = 10 MeV, dose D = 1016 cm–2) has little effect on the electrophysical and magnetic properties, which indicates their high radiation resistance.

Gallium vacancy ordering in Ga2Se3 thin layers on Si(100), Si(111), and Si(123) substrates

Thin Ga2Se3 layers deposited on silicon substrates with the (100), (111), and (123) orientations are studied by transmission electron microscopy and X-ray microanalysis. Some features and regularities of the stoichiometric gallium vacancy ordering at different substrate orientations are discussed. The Ga3Se4(100)с(2 × 2) and Ga2Se3(111)(√3 × √3)-R30° ordered structures are formed on the Si(100) and Si(111) surfaces, respectively.

Stoichiometric partially-protonated states in hydroxide perovskites: the jeanbandyite enigma revisited

AbstractThe original description of the hydroxide perovskite jeanbandyite gives a formula (Fe1–x3+,□x)(Sn1–y,□y) (OH)6 (□= vacancy), which implies the possibility of stoichiometric vacancies at B and B' sites. The validity of this formula has been questioned subsequently. Furthermore, jeanbandyite has metrically a cubic unit cell, but it is optically uniaxial. It is clear that a structure determination is needed to clarify the nature of this enigmatic mineral. Previous studies could find no crystals of sufficient quality for structure determination using X-ray diffractometers available at the time. Crystals of jeanbandyite from Hingston Down, Cornwall, UK and the type locality Llallagua, Bolivia, have been found that are of a quality that allows structure refinement by single-crystal X-ray diffraction. Structural data for crystals from each locality are presented that clarify the nature of jeanbandyite and raise some interesting questions concerning the significance of partially deprotonated states in perovskite-type structures. The structures of both jeanbandyite crystals are cubic with space group Pn3 and unit-cell parameters a = 7.658(2) Å (Llallagua) and 7.6427(2) Å (Hingston). The octahedral tilt system is a+a+a+ and corresponds to that of the aristotype of BB'(OH)6 hydroxide double perovskites. Structure determination demonstrates that B is very Fe3+-rich and B' is filled by Sn, thereby requiring revision of the general jeanbandyite formula to Fex3+Fe(1–x)2+Sn(OH)(6–x)Oxfor 1≥ × > 0.5, with an ideal end-member formula Fe3+Sn(OH)5O. As such, jeanbandyite corresponds to oxidized natanite with partially deprotonated oxygen sites. This stoichiometry cannot be represented in space group Pn3̄ for the observed unit cell as it implies more than one non-equivalent oxygen atom. Consequently, it is inferred that there is no long-range ordering of deprotonated oxygen sites. It is, however, conceivable that the uniaxial optical character of jeanbandyite is linked to the local short-range order of deprotonated domains.

Effects of stoichiometry on the transport properties of crystalline phase-change materials

It has recently been shown that a metal-insulator transition due to disorder occurs in the crystalline state of the GeSb2Te4 phase-change compound. The transition is triggered by the ordering of the vacancies upon thermal annealing. In this work, we investigate the localization properties of the electronic states in selected crystalline (GeTe)x-(Sb2Te3)y compounds with varying GeTe content by large-scale density functional theory simulations. In our models, we also include excess vacancies, which are needed to account for the large carrier concentrations determined experimentally. We show that the models containing a high concentration of stoichiometric vacancies possess states at the Fermi energy localized inside vacancy clusters, as occurs for GeSb2Te4. On the other hand, the GeTe-rich models display metallic behavior, which stems from two facts: a) the tail of localized states shrinks due to the low probability of having sizable vacancy clusters, b) the excess vacancies shift the Fermi energy to the region of extended states. Hence, a stoichiometry-controlled metal-insulator transition occurs. In addition, we show that the localization properties obtained by scalar-relativistic calculations with gradient-corrected functionals are unaffected by the inclusion of spin-orbit coupling or the use of hybrid functionals.

Effect of vacancies on the structure and properties of Ga2(Se0.33Te0.67)3

Ga2(Se0.33Te0.67)3 belongs to a family of materials with large intrinsic vacancy concentrations that are being actively studied due to their potential for diverse applications that include thermoelectrics and phase-change memory. In this article, the Ga2(Se0.33Te0.67)3 structure is investigated via synchrotron x-ray diffraction, electron microscopy, and x-ray absorption experiments. Diffraction and microscopy measurements showed that the extent of vacancy ordering in Ga2(Se0.33Te0.67)3 is highly dependent on thermal annealing. It is posited that stoichiometric vacancies play a role in local atomic distortions in Ga2(Se0.33Te0.67)3 (based on the fine structure signals in the collected x-ray absorption spectra). The effect of vacancy ordering on Ga2(Se0.33Te0.67)3 material properties is also examined through band gap and Hall effect measurements, which reveal that the Ga2(Se0.33Te0.67)3 band gap redshifts by ≈0.05 eV as the vacancies order and accompanied by gains in charge carrier mobility. The results serve as an encouraging example of altering material properties via intrinsic structural rearrangement as opposed to extrinsic means, such as doping.

Structure and Phase Changes in Natural and Synthetic Magnesium Aluminum Spinel

Natural spinel crystals from Ural and Pamir deposits and synthetic magnesium aluminium spinel single crystals with different stoichiometry (MgO.nAl2O3 ) grown by Verneuil method were used. The photoluminescence (PL), its excitation (PLE) and optical absorption of stoichiometric and nonstoichiometric magnesium aluminium spinel crystals containing the chromium and manganese ions and defects produced by fast neutron irradiation( fluence up to 1020cm-2, E>0.1 MeV) are investigated. The broadening of R- and N-lines takes place in synthetic stoichiometric spinel. Structure of synthetic nonstoichiometric spinels (n>1) has to be more disordered, since in addition to the site exchange the so called stoichiometric vacancies are present in the structure. The R- and N-lines broadening takes place after spinel crystals irradiation by fast neutron too. The neutron irradiation causes increasing of the spinel inversion. Furthermore the great deviation from stoichiometry leads to the local structure of α-Al2O3 formation around Cr3+ ions. The orange emission band at 570 nm is belonging to complex center “Mn2+-F+ (or F centre)”.

Materials and Photosensor Devices with High Radiation Stability

Semiconductor Hg3In2Te6 crystals and their analogous are solid solutions of In2Te3 and HgTe. Hg3In2Te6 crystals are congruently melted as chemical compound. Like In2Te3 the Hg3In2Te6 crystal has cubic crystal lattice with stoichiometric vacancies in their crystal structure. The electroconductivity, photoconductivity, mechanical, chemical properties of the crystals do not deteriorate after their irradiation by γ-photons with energies up to 1 MeV and doses up to 1018 cm-2 , by electrons with energies up to 300 MeV and doses up to 1019 cm-2 and by mixed reactor irradiation (filtered slow neutrons) with doses up to 1019 cm-2 [1,2]. This feature is determined by high concentration (~1021 cm-3) of stoihiometric vacancies (Vs) in crystal structure, where every third In-cation node is empty. These Vs are electroneutral, they capture all impurity atoms in these crystals and kept them in electroneutral state too. On the other hand this feature doesn't allow to form direct p-n junctions in these crystals by introducing the impurities. However, we have developed p-n junction analogues in form of Schottki diodes and corresponding photodiodes with semitransparent metal layer on single crystal Hg3In2Te6 substrate that allows irradiation to get into active region preserving this way all the advantages compared to p-n junction.

The role of stoichiometric vacancy periodicity in pressure-induced amorphization of the Ga2SeTe2 semiconductor alloy

We observe that pressure-induced amorphization of Ga2SeTe2 (a III-VI semiconductor) is directly influenced by the periodicity of its intrinsic defect structures. Specimens with periodic and semi-periodic two-dimensional vacancy structures become amorphous around 10–11 GPa in contrast to those with aperiodic structures, which amorphize around 7–8 GPa. The result is an instance of altering material phase-change properties via rearrangement of stoichiometric vacancies as opposed to adjusting their concentrations. Based on our experimental findings, we posit that periodic two-dimensional vacancy structures in Ga2SeTe2 provide an energetically preferred crystal lattice that is less prone to collapse under applied pressure. This is corroborated through first-principles electronic structure calculations, which demonstrate that the energy stability of III-VI structures under hydrostatic pressure is highly dependent on the configuration of intrinsic vacancies.