Investigations on structural,elastic, thermodynamic and electronic properties of TiN,Ti2N and Ti3N2 under high pressure by first-principles

The lattice parameters, cell volume, elastic constants, bulk modulus, shear modulus, Young's modulus and Poisson's ratio are calculated at zero pressure, and their values are in excellent agreement with the available data, for TiN, Ti₂N and Ti₃N₂. By using the elastic stability criteria, it is shown that the three structures are all stable. The brittle/ductile behaviors are assessed in the pressures from 0 GPa to 50 GPa. Our calculations present that the performances for TiN, Ti₂N and Ti₃N₂ become from brittle to ductile with pressure rise. The Debye temperature rises as pressure increase. With increasing N content, the enhancement of covalent interactions and decline of metallicity lead to the increase of the micro-hardness. Their constant volume heat capacities increase rapidly in the lower temperature, at a given pressure. At higher temperature, the heat capacities are close to the Dulong–Petit limit, and the heat capacities of TiN and Ti₂N are larger than that of c-BN. The thermal expansion coefficients of titanium nitrides are slightly larger than that of c-BN. The band structure and the total Density of States (DOS) are calculated at 0 GPa and 50 GPa. The results show that TiN and Ti₂N present metallic character. Ti₃N₂ present semiconducting character. The band structures have some discrepancies between 0 GPa and 50 GPa. The extent of energy dispersion increases slightly at 50 GPa, which means that the itinerant character of electrons becomes stronger at 50 GPa. The main bonding peaks of TiN, Ti₂N and Ti₃N₂ locate in the range from −10 to 10 eV, which originate from the contribution of valance electron numbers of Ti s, Ti p, Ti d, N s and N p orbits. We can also find that the pressure makes that the total DOS decrease at the Fermi level for Ti₂N. The bonding behavior of N–Ti compounds is a combination of covalent and ionic nature. As N content increases, valence band broadens, valence electron concentration increases, and covalent interactions become stronger. This is reflected in shortening of Ti–N bonds.     

AlH3 between 65 and 110 GPa: Implications of electronic band and phonon structures

A first-principles density-functional-theory method has been used to reinvestigate the mechanical and dynamical stability of the metallic phase of AlH₃ between 65 and 110 GPa. The electronic properties and phonon dynamics as a function of pressure are also explored. We find electron–phonon superconductivity in the cubic Pm-3n structure with critical temperature T_c = 37 K at 70 GPa which decreases rapidly with the increase of pressure. Further unlike a previously calculated T_c-value of 24 K at 110 GPa, we do not find any superconductivity of significance at this pressure which is consistent with experimental observation.     

Effect of nitrogen partial pressure on Al–Ti–N films deposited by arc ion plating

AlTiN films with different nitrogen partial pressures were deposited using arc ion plating (AIP) technique. In this study, we systematically investigated the effect of the nitrogen partial pressure on composition, deposition efficiency, microstructure, macroparticles (MPs), hardness and adhesion strength of the AlTiN films. The results showed that with increasing the nitrogen partial pressure, the deposition rate exhibited a maximum at 1.2 Pa. Results of X-ray photoelectron spectroscopy (XPS) analysis revealed that AlTiN films were comprised of Ti–N and Al–N bonds. XRD results showed that the films exhibited a (1 1 1) preferred growth, and AlTi₃N and TiAl_x phases were observed in the film deposited at 1.7 Pa. Analysis of MPs statistics showed MPs decreased with the increase in the nitrogen partial pressure. In addition, the film deposited at 1.2 Pa possessed the maximum hardness of 38 GPa and the better adhesion strength.     

First-principles calculations on crystal structure and physical properties of rhenium dicarbide

Structural stability, elastic behavior, hardness, and chemical bonding of ideal stoichiometric rhenium dicarbide (ReC₂) in the ReB₂, ReSi₂, Hex-I, Hex-II, and Tet-I structures have been systematically studied using first-principles calculations. The results suggest that all these structures are mechanically stable and ultra-incompressible characterized by large bulk moduli. Formation enthalpy calculations demonstrated that they are metastable under ambient conditions, and the relative stability of the examined candidates decreases in the following sequence: Hex-I>Hex-II>ReB₂>Tet-I>ReSi₂. The hardness calculations showed that these structures are all hard materials, among which the Hex-I exhibits the largest Vickers hardness of 32.2 GPa, exceeding the hardness of α-SiO₂ (30.6 GPa) and β-Si₃N₄ (30.3 GPa). Density of states and electronic localization function analysis revealed that the strong C–C and C–Re covalent bonds are major driving forces for their high bulk and shear moduli as well as small Poisson's ratio.     

Dependence of magnetic ordering temperature of doped and undoped EuFe2As2 on hydrostatic pressure to 0.8 GPa

The ac susceptibility of single crystalline tetragonal EuFe₂As₂, EuFe₂As_1.4P_0.6, and EuFe_1.715Co_0.285As₂ has been measured over the temperature and hydrostatic (He-gas) pressure ranges 10–60 K and 0–0.8 GPa, respectively. For all three samples the magnetic ordering temperature (17–19 K) from the Eu sublattice increases linearly with pressure, presumably due to the enhanced exchange coupling between Eu-layers. No evidence for a superconducting transition was observed in the susceptibility for any sample over the measured temperature/pressure range.     

First principles study of structural stability,electronic structure and mechanical properties of ReN and TcN

The crystal structure, structural stability, electronic and mechanical properties of ReN and TcN are investigated using first principles calculations. We have considered five different crystal structures: NaCl, zinc blende (ZB), NiAs, tungsten carbide (WC) and wurtzite (WZ). Among these ZB phase is found to be the lowest energy phase for ReN and TcN at normal pressure. Pressure induced structural phase transitions from ZB to WZ phase at 214 GPa in ReN and ZB to NiAs phase at 171 GPa in TcN are predicted. The electronic structure reveals that both ReN and TcN are metallic in nature. The computed elastic constants indicate that both the nitrides are mechanically stable. As ReN in NiAs phase has high bulk and shear moduli and low Poisson's ratio, it is found to be a potential ultra incompressible super hard material.     

High pressure transport characteristics of Bi2Te3, Sb2Te3, and BiSbTe3

This paper presents ambient and high pressure measurements of transport properties of the Bi₂Te₃–Sb₂Te₃ series of materials. The electrical resistivity, thermal conductivity, and Seebeck coefficient have been measured on both end compounds and the direct solid solution of the two at pressure up to 10 GPa. An additional discussion involving the high pressure structure will be presented. From this, it was determined that these materials undergo at least two structural phase transitions between 0 and 20 GPa and a discussion is presented regarding this and the changes in the transport properties.     

Effect of Ag addition on the third-order nonlinearity and physicochemical property of chalcohalide glass

In this work, the 70GeS₂–20In₂S₃–10CsI glass introduced with 0–10 mol% Ag₂S were prepared by the vacuumed melt-quenching technique. The physicochemical properties, such as glass transition temperature, density, refractive index, transmittance, hardness as well as third-order nonlinearity are investigated with the increasing Ag₂S contents. It was found that the refractive index (@632.8 nm), density, and hardness of glasses increase distinctly from 2.204 to 2.270, from 3.520 to 3.675 g cm⁻³ and from 180.9 to 227.9 kg mm⁻², respectively. Meanwhile, the nonlinear refractive index increases from 3.2 × 10⁻¹⁸ to 4.6 × 10⁻¹⁸ m²/W due to the increased refractive index. Finally, the Raman spectra are performed to structurally illustrate the role of Ag addition on the changes of the physicochemical properties. With the Ag₂S contents increasing, the vibration intensity of the [InS₄] and [InS₃I] tetrahedrons increases and the heavy Ag atoms result in the increased density and refractive index, as well as the nonlinear refractive index. The Ag-containing glass, which exhibited good thermal stability, excellent infrared transparency and ultrafast nonlinear optical properties, can be find applications for the IR window material or ultrafast infrared optics.     

Quantum dots of Cd0.5Mn0.5Te semimagnetic semiconductor formed by the cold isostatic pressure method

Cd_0.5Mn_0.5Te is a semimagnetic semiconductor, which crystallizes in the zinc-blende structure (ZB) and exhibits a magnetic spin glass like transition at 21 K. Under pressure it shows a first-order phase transition around 2.6 GPa to the NaCl like structure. In this work, the pressure cycled method using a Paris–Edinburgh cell up to 8 GPa has been applied to Cd_0.5Mn_0.5Te samples in order to obtain recovered nanocrystals. The nanoparticles have been characterized by EDX and electron microscopy. The X-ray and electron diffraction results confirmed the existence of nanocrystals in the ZB phase with an average size of 7 nm. Magnetization measurements made in the range of 2–300 K at low field show that the temperature of the magnetic transition decreases when the crystallites’ size is reduced.     

Structural phase stability,electronic structure and mechanical properties of alkali metal hydrides AMH4 (A=Li,Na; M=B,AL)

The structural stability of Alkali metal hydrides AMH₄ (A=Li, Na; M=B, Al) is analyzed among the various crystal structures, namely hexagonal (P6₃mc), tetragonal (P4₂/nmc), tetragonal (P-42₁c), tetragonal (I4₁/a), orthorhombic (Pnma) and monoclinic (P2₁/c). It is observed that, orthorhombic (Pnma) phase is the most stable structure for LiBH₄, monoclinic (P2₁/c) for LiAlH₄, tetragonal (P4₂/nmc) for NaBH₄ and tetragonal (I4₁/a) for NaAlH₄ at normal pressure. Pressure induced structural phase transitions are observed in LiBH₄, LiAlH₄, NaBH₄ and NaAlH₄ at the pressures of 4 GPa, 36.1 GPa, 26.5 GPa and 46 GPa respectively. The electronic structure reveals that these metal hydrides are wide band gap insulators. The calculated elastic constants indicate that these metal hydrides are mechanically stable at normal pressure.     

Structural,electronic and mechanical properties of alkaline earth metal oxides MO (M=Be,Mg, Ca,Sr, Ba)

The structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba) in the cubic (B1, B2 and B3) phases and in the wurtzite (B4) phase are investigated using density functional theory calculations as implemented in VASP code. The lattice constants, cohesive energy, bulk modulus, band structures and the density of states are computed. The calculated lattice parameters are in good agreement with the experimental and the other available theoretical results. Electronic structure reveals that all the five alkaline earth metal oxides exhibit semiconducting behavior at zero pressure. The estimated band gaps for the stable wurtzite phase of BeO is 7.2 eV and for the stable cubic NaCl phases of MgO, CaO, SrO and BaO are 4.436 eV, 4.166 eV, 4.013 eV, and 2.274 eV respectively. A pressure induced structural phase transition occurs from wurtzite (B4) to NaCl (B1) phase in BeO at 112.1 GPa and from NaCl (B1) to CsCl (B2) phase in MgO at 514.9 GPa, in CaO at 61.3 GPa, in SrO at 42 GPa and in BaO at 14.5 GPa. The elastic constants are computed at zero and elevated pressures for the B4 and B1 phases for BeO and for the B1 and B2 phases in the case of the other oxides in order to investigate their mechanical stability, anisotropy and hardness. The sound velocities and the Debye temperatures are calculated for all the oxides using the computed elastic constants.     

Mechanical properties of polycrystalline RuSr2GdCu2O8 superconductor

The main objective of this paper is to report the room temperature hardness and elastic modulus of the RuSr₂GdCu₂O₈ superconductor phase by instrumented indentation. Polycrystalline samples were produced by a solid state reaction technique. The samples were also characterized by scanning electron microscopy, X-ray diffraction and electrical resistivity measurements. The influence of porosity on the mechanical properties was avoided by considering only those indentations inside the grains. The hardness and elastic modulus were 8.6 GPa and 145 GPa, respectively. These values are comparable with those of Y-123. The indentation fracture toughness evaluated after conventional Vickers indentation was 1.9 MPa m^1/2.     

Behavioral response of pyrite structured Co0.2Fe0.8S2 nano-wires under high-pressure up to 8 GPa – Mössbauer spectroscopic and electrical resistivity studies

Pyrite-structured Co_0.2Fe_0.8S₂ nano wires with aspect ratio 45:1, synthesized using solution colloid method were studied under high pressure up to 8 GPa using ⁵⁷Fe Mössbauer spectroscopy (using diamond anvil cell) and electrical resistivity (using tungsten carbide cell) techniques. Room temperature S K-edge XANES studies at INFN-LNF synchrotron beam line signified the changes in the electronic structure owing to Co substitution. Magnetic measurements at 5 K demonstrated disordered ferromagnetic behavior similar to Griffith phase. The value of isomer shift identified Fe in divalent, low spin state corresponding to pyrite structure. Higher value of quadrupole splitting observed at ambient condition was due to large lattice strain and electric field gradient generated by large surface to volume ratio of the nano size of the system. With applied pressure, the value followed the expected trend of increase up to 4.3 GPa, then to decrease till 6.4 GPa. Such change in the trend suggested a phase transition. On decompression to ambient pressure, the system seemed to retain high pressure phase and nano structure. The pressure coefficient of electrical resistivity varying from −0.0454 to −0.166 Ω-cm/GPa across the transition pressure of ~4.5 GPa was sluggish suggesting second order phase transition. The pressure-dependent variations by Mössbauer parameters and electrical resistivity showed identical result. This is the first report of pressure effect on nano sized Co_0.2Fe_0.8S₂. Effect of particle size on transition pressure could not be evaluated due to lack of available reports on bulk system.     

In situ Raman spectroscopy of cubic boron nitride to 90 GPa and 800 K

The temperature and pressure dependences of the Raman spectrum of the transverse-optical mode of cubic boron nitride were calibrated for applications to a Raman spectroscopy pressure sensor in optical cells to about 800 K and 90 GPa. A significant deviation from linearity of the pressure dependence is confirmed at pressures above 20 GPa. At ambient temperature, dv/dP slopes are 3.41(7) and 2.04(7) cm⁻¹/GPa at 0 and 90 GPa, respectively. A polynomial expression is used to fit the pressure–temperature dependence of the Raman line. The pressure dependence does not significantly change with temperature, as determined from experiments conducted up to 800 K. At 0 GPa, the dv/dP slope is 3.46(7) cm⁻¹/GPa at 800 K. At pressures above 90 GPa, the Raman spectrum of the transverse-optical mode cannot be observed because of an overlap of the signals of cubic boron nitride and diamond used as the anvils in the high-pressure cell.     

Effects of morphology on photocatalytic performance of Zinc oxide nanostructures synthesized by rapid microwave irradiation methods

In this study, two different chemical solution methods were used to synthesize Zinc oxide nanostructures via a simple and fast microwave assisted method. Afterwards, the photocatalytic performances of the produced ZnO powders were investigated using methylene blue (MB) photodegradation with UV lamp irradiation. The obtained ZnO nanostructures showed spherical and flower-like morphologies. The average crystallite size of the flower-like and spherical nanostructures were determined to be about 55 nm and 28 nm, respectively. X-ray diffraction (XRD), scanning electronic microscopy (SEM), Brunauer–Emmett–Teller (BET), room temperature photoluminescence (RT-PL) and UV–vis analysis were used for characterization of the synthesized ZnO powders. Using BET N₂-adsorption technique, the specific surface area of the flower-like and spherical ZnO nanostructures were found to be 22.9 m²/gr and 98 m²/gr, respectively. Both morphologies show similar band gap values. Finally, our results depict that the efficiency of photocatalytic performance in the Zinc oxide nanostructures with spherical morphology is greater than that found in the flower-like Zinc oxide nanostructures as well as bulk ZnO.     

Influence of growth morphology on the Néel temperature of CrRu thin films and heterostructures

Dimensionality effects on epitaxial and polycrystalline Cr_1?xRu_x alloy thin films and in Cr/Cr–Ru heterostructures are reported. X-ray analysis on Cr_0.9965Ru_0.0035 epitaxial films indicates an increase in the coherence length in growth directions (1 0 0) and (1 1 0) with increasing thickness (d), in the range 20≤d≤300 nm. Atomic force microscopy studies on these films shows pronounced vertical growth for d>50 nm, resulting in the formation of columnar structures. The Néel temperatures (T_N) of the Cr_0.9965Ru_0.0035 films show anomalous behaviour as a function of d at thickness d≈50 nm. It is interesting to note that this thickness corresponds to that for which a change in film morphology occurs. Experiments on epitaxial Cr_1?xRu_x thin films, with 0≤x≤0.013 and d=50 nm, give T_N–x curves that correspond well with that of bulk Cr_1?xRu_x alloys. Studies on Cr/Cr_0.9965Ru_0.0035 superlattices prepared on MgO(1 0 0), with the Cr layer thickness varied between 10 and 50 nm, keeping the Cr_0.9965Ru_0.0035 thickness constant at 10 nm, indicate a sharp decrease in T_N as the Cr separation layers reaches a thickness of 30 nm; ascribed to spin density wave pinning in the Cr layers for d<30 nm by the adjacent CrRu layers.     

Hardness and microstructural variation of Al–Mg–Mn–Sc–Zr alloy

Variations of Vickers hardness were observed in Al–Mg–Mn alloy and Al–Mg–Mn–Sc–Zr alloy at different ageing times, ranging from a peak value of 81.2 HV at 54 ks down to 67.4 HV at 360 ks, below the initial hardness value, 71.8 HV at 0 ks for the case of Al–Mg–Mn–Sc–Zr alloy. Microstructures of samples at each ageing stage were examined carefully by transmission electron microscopes (TEMs) both in two-dimensions and three-dimensions. The presence of different types, densities, and sizes of particles were observed dispersed spherical Al₃Sc_1−xZr_x and also block-shaped Al₃Sc precipitates growing along <1 0 0>_Al with facets {1 0 0} and {1 1 0} of the precipitates. TEM analysis both in two-dimensions and three-dimensions, performed on various samples, confirmed the direct correlation between the hardness and the density of Al₃Sc.     

Pressure-induced coordination crossover in magnetite; the breakdown of the Verwey–Mott localization hypothesis

Temperature-dependent ⁵⁷Fe Mössbauer spectroscopy to 40 GPa shows that Fe₃O₄ magnetite undergoes a coordination crossover (CC), whereby charge density is shifted from octahedral to tetrahedral sites and the spinel structure thus changes from inverse to normal with increasing pressure and decreasing temperature. A precursor to the CC is a d-charge decoupling within the octahedral sites at the inverse-spinel phase. The CC transition takes place almost exactly at the Verwey transition temperature (T_V=122 K) at ambient pressure. While T_V decreases with pressure the CC-transition temperature increases with pressure, reaching 300 K at 10 GPa. The d electron localization mechanism proposed by Verwey and later by Mott for T<T_V is shown to be unrelated to the actual mechanism of the metal–insulator transition attributed to the Verwey transition. It is proposed that a first-order phase transition taking place at ∼T_V at ambient pressure opens a small gap within the oxygen p-band, resulting in the observed insulating state at T>T_V.     

Time-resolved spectroscopy in LiCaAlF6 doped with Cr3+ as a function of pressure and temperature: Excited-state crossover and phase-transition effects

This work investigates phase transition (PT) and excited-state-crossover (ESCO) effects on the photoluminescence (PL) properties of LiCaAlF₆: Cr³⁺. The structural requirements for changing the Cr³⁺ PL behavior from a broad-band emission at 1.59 eV (781 nm) at ambient conditions, to ruby-like narrow-line emission at 1.87 eV (663 nm) are analyzed in the 0–35 GPa range. We report a PL study on LiCaAlF₆: Cr³⁺ by means of time-resolved emission as a function of pressure and temperature. In particular we focus on the PL variations occurring around the pressure-induced trigonal-to-monoclinic first-order PT in LiCaAlF₆ at 7 GPa.     

Addendum to “Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)” by K.-S. Lee et al. [J. Phys. Chem. Solids 73 (2012) 890]

While a paper mentioned above being published on line, we have become aware of the high-pressure neutron diffraction study of squaric acid (H₂C₄O₄) by C.L. Bull et al. They developed that neutron diffraction experiments could be performed under quasi-hydrostatic conditions to pressures of up to 18 GPa and showed that the tetragonal phase of H₂C₄O₄ was still observed at 14.5 GPa (above the critical pressure of P_c=0.75 GPa at room temperature) beyond the previous pressure limits of 7 GPa. Taking the high-pressure neutron diffraction results into consideration, modified temperature-pressure phase diagram in the paper stated above is reported.