High-symmetry Phase Research Articles

First-principles study of structural, elastic, electronic and vibrational properties of BiCoO3

We used density functional theory (DFT) to study the structural, elastic, electronic, and lattice dynamical properties of tetragonal BiCoO3 applying the “norm-conserving” pseudopotentials within the local spin density approximation (LSDA). The calculated equilibrium lattice parameters and atomic displacements are in agreement with the available experimental and theoretical results. Moreover, the structural stability of tetragonal BiCoO3 were confirmed by the calculated elastic constants. In addition, the elastic properties of polycrystalline aggregates including bulk, shear and Young's moduli, and Poisson's ratio are also determined. The electronic band structure, total and partial density of states (DOS and PDOS) with ferromagnetic spin configuration are obtained. The results show that tetragonal BiCoO3 has an indirect band gap with both up- and down-spin configurations and its bonding behavior is of covalent nature. We compute Born effective charge (BEC) which is found to be quite anisotropic of Bi, Co and O atoms. The infrared and Raman active phonon mode frequencies at the Г point are found. The phonon dispersion curves exhibit imaginary frequencies which lead from the high-symmetry tetragonal phase to low-symmetry rhombohedral phase in BiCoO3. The six independent elastic constants, including bulk, shear and Young's moduli, and Poisson's ratio, complete BEC tensor and phonon dispersion relations in tetragonal BiCoO3 are predicted for the first time. Results of the calculations are compared with the existing experimental and theoretical data.

Pro rol' fluktuatsiy koherentnykh zsuviv polozhennya rivnovahy atomiv pry fazovykh perekhodakh druhoho rodu

Second-order phase transitions in ferroics of the ferroelastic type have been studied theoretically. The temperature-induced phase transition in crystals with a wide forbidden gap caused by the interaction between electrons and a branch of acoustic vibrations in the crystal lattice is considered. The vertex part of this interaction with transverse lattice vibrations is calculated. The characteristic features of the thermodynamic potential at the transition point and the temperature dependence of the acoustic phonon dispersion at the transition over quasiequilibrium states are discussed. It is shown that the stabilization of structure fluctuations by the electron subsystem in the high-symmetry phase, and a reduction of soft mode frequencies makes those fluctuations metastable.

Unconventional magnetostructural transition in CoCr2O4 at high magnetic fields.

The magnetic-field and temperature dependencies of the ultrasound propagation and magnetization of single-crystalline CoCr(2)O(4) have been studied in static and pulsed magnetic fields up to 14 and 62 T, respectively. Distinct anomalies with significant changes in the sound velocity and attenuation are found in this spinel compound at the onset of long-range incommensurate-spiral-spin order at T(s)=27 K and at the transition from the incommensurate to the commensurate states at T(l)=14 K, evidencing strong spin-lattice coupling. While the magnetization evolves gradually with the field, steplike increments in the ultrasound clearly signal a transition into a new magnetostructural state between 6.2 and 16.5 K and at high magnetic fields. We argue that this is a high-symmetry phase with only the longitudinal component of the magnetization being ordered, while the transverse helical component remains disordered. This phase is metastable in an extended H-T phase space.

Zirconium and hafnium tert-butoxides and tert-butoxo-β-diketonate complexes – Isolation, structural characterization and application in the one-step synthesis of 3D metal oxide nanostructures

Long term storage of the pure commercial Zr(OtBu)4 in a sealed ampoule results in crystallization of a new high symmetry phase of Zr3O(OtBu)10 (1). Modification of Zr(OtBu)4 and Hf(OtBu)4 with 2,2,6,6,-tetramethyl-3,5-heptanedione (Hthd) produces dependent on the stoichiometry two types of derivatives, M(OtBu)2(thd)2 (2, 3) and M(OtBu)(thd)3 (4, 5) M=Zr(2, 4), Hf(3, 5), which have all been characterized by NMR and mass-spectral studies and for 4 and 5 also by complete X-ray single crystal studies. The latter failed for 2 and 3 in the view of their poor X-ray reflectivity. Addition of minor amounts of n-C5H11OH to 3 resulted in isolation of an unusual heteroleptic complex Hf2(OH)(OnC5H11)(OtBu)2(thd)4 (6). Thermal decomposition of compounds 1 and 3 in nitrogen atmosphere was studied for different thermal regimes by TGA-FTIR approach, revealing in all cases the formation of tetragonal ZrO2 and monoclinic HfO2 respectively, along with iso-butene, butanol and water for 1 and the same mixture including also Hthd for 3. Decomposition of 3 occurred always through intermediate melting, while higher heating rate for 1 permitted to achieve decomposition on in situ evaporation resulting in 3D hedgehog nanostructures according to SEM.

Stable Cu2O nanocrystals grown on functionalized graphene sheets and room temperature H2S gas sensing with ultrahigh sensitivity

Stable Cu(2)O nanocrystals of around 3 nm were uniformly and densely grown on functionalized graphene sheets (FGS), which act as molecular templates instead of surfactants for controlled nucleation; the distribution density of nanocrystals can be easily controlled by FGS with different C/O ratios. The nanocomposite displays improved stability of the crystalline phase in wet air, which is attributed to finite-size effects that the high-symmetry crystalline phase is to be more stable at smaller size. Meanwhile, we conjecture that the oxygen adsorbed on the interfacial surface prefers to extract electrons from FGS, thus the interfacial bonding also makes a contribution in alleviating the process of corrosion to some extent. More importantly, the Cu(2)O-FGS nanocomposite based sensor realizes room temperature sensing to H(2)S with fantastic sensitivity (11%); even at the exposed concentration of 5 ppb, the relative resistance changes show good linearity with the logarithm of the concentration. The enhancement of sensitivity is attributed to the synergistic effect of Cu(2)O and FGS; on the one hand, surfactant-free capped Cu(2)O nanocrystals display higher surface activity to adsorb gas molecules, and on the other hand, FGS acting as conducting network presents greater electron transfer efficiency. These observations show that the Cu(2)O-FGS nanocomposite based sensors have potential applications for monitoring air pollution at room temperature with low cost and power consumption.

Pressure-driven Phase Transition in CaFeAsF at 40 and 300 K

We carried out systematic investigation of high pressure crystal structure and structural phase transition upto 46 GPa at 40 K and 25 GPa at 300 K in CaFeAsF using powder synchrotron x-ray diffraction experiments. Rietveld analysis of the diffraction data at 40 K reveals a structural phase transition from an orthorhombic to a monoclinic phase at Pc = 13.7 GPa, while increasing pressure. The transition to a lower symmetry phase (orthorhombic to monoclinic) in this 1111 compound under pressure is in contrast with the transition to a high symmetry phase (orthorhombic to tetragonal) as observed in the '122' type compounds. On heating from 40 K at high pressure, CaFeAsF undergoes a monoclinic to tetragonal phase transition around 25 GPa and 200 K. Further, it does not show any post-tetragonal phase transition, as observed in '122' compounds (CaFe2As2, BaFe2As2), and remains in the tetragonal phase upto 25 GPa at 300 K. The dPc/dT slope is found to be positive for CaFeAsF and CaFe2As2, unlike a negative gradient was found in case of BaFe2As2.

High-pressure behavior of dense hydrogen up to 3.5 TPa from density functional theory calculations

Structural behavior and equation of state (EOS) of atomic and molecular crystal phases of dense hydrogen at pressures up to 3.5 TPa are systematically investigated with density functional theory. The results indicate that the Vinet EOS model that fitted to low-pressure experimental data overestimates the compressibility of dense hydrogen drastically when beyond 500 GPa. Metastable multi-atomic molecular phases with weak covalent bonds are observed. When compressed beyond about 2.8 TPa, these exotic low-coordinated phases become competitive with the ground state and other high-symmetry atomic phases. Using nudged elastic band method, the transition path and the associated energy barrier between these high-pressure phases are evaluated. In particular for the case of dissociation of diatomic molecular phase into the atomic metallic Cs-IV phase, the existent barrier might raise the transition pressure about 200 GPa at low temperatures. Plenty of flat and broad basins on the energy surface of dense hydrogen have been discovered, which should take a major responsibility for the highly anharmonic zero point vibrations of the lattice, as well as the quantum structure fluctuations in some extreme cases. At zero pressure, our analysis demonstrates that all of these atomic phases of dense hydrogen known so far are unquenchable.

First-principles study of structural and vibrational properties of SrZrO3

Using first-principles calculations, we investigate the electronic, structural, and vibrational properties of SrZrO${}_{3}$. We start from the high-symmetry cubic perovskite phase, for which the phonon dispersion curves are reported. We point out the coexistence of structural antiferrodistortive instabilities at the R and M zone-boundary points and a ferroelectric instability at the zone center. We show that the strong antiferrodistortive motions suppress ferroelectricity and are responsible for the orthorhombic ground state as in CaTiO${}_{3}$. The structural properties of possible intermediate phases and of the orthorhombic $Pnma$ ground state are reported. For the latter, an assignment of IR and Raman zone-center phonon modes is proposed. The main features of the ferroelectric instability are also discussed, and we show that a ferroelectric ground state can even be induced in SrZrO${}_{3}$ by strain engineering.

Pressure dependence of the low-temperature crystal structure and phase transition behavior of CaFeAsF and SrFeAsF: A synchrotron x-ray diffraction study

We report systematic investigation of high pressure crystal structures and structural phase transition upto 46 GPa in CaFeAsF and 40 GPa in SrFeAsF at 40 K using powder synchrotron x-ray diffraction experiments and Rietveld analysis of the diffraction data. We find that CaFeAsF undergoes orthorhombic to monoclinic phase transition at Pc = 13.7 GPa while increasing pressure. SrFeAsF exhibits coexistence of orthorhombic and monoclinic phases over a large pressure range from 9 to 39 GPa. The coexistence of the two phases indicates that the transition is of first order in nature. Unlike in the 122 compounds (BaFe2As2 & CaFe2As2) we do not find any collapse tetragonal transition. The transition to a lower symmetry phase (orthorhombic to monoclinic) in 1111 compounds under pressure is in contrast with the transition to a high symmetry phase (orthorhombic to tetragonal) in 122 type compounds. On heating from 40 K at high pressure, CaFeAsF undergoes monoclinic to tetragonal phase transition around 25 GPa and 200 K. Further, it does not show any post-tetragonal phase transition and remains in the tetragonal phase upto 25 GPa at 300 K. The dPc/dT is found to be positive for the CaFeAsF & CaFe2As2, however the same was not found in case of BaFe2As2. We discuss observations of structural evolution in the context of superconductivity in these and other Fe-based compounds. It appears that the closeness of the Fe-As-Fe bond angle to its ideal tetrahedral value of 109.470 might be associated with occurrence of superconductivity at low temperature.

Phase transition behavior of mother phase of proton-conducting oxides, Sr 1− xBa xZrO 3

The phase diagram of Sr 1− x Ba x ZrO 3, which is the mother phase of highly proton-conducting oxides, has been established by differential scanning calorimetry (DSC), dilatometry and X-ray diffraction analysis at various temperatures. The phase boundaries and order of the transitions from the primitive orthorhombic phase to the body-centered orthorhombic, tetragonal and cubic phases have been determined. The temperatures of these three kinds of phase transition decreased with increasing Ba content. The jump in the specific heat of the second-order phase transitions from primitive orthorhombic to body-centered orthorhombic and from tetragonal to cubic also decreased with increasing Ba content. An increase in Ba content decreased the variation in the enthalpy of the first-order phase transition from body-centered orthorhombic to tetragonal. The temperature region where high symmetry phases, such as the cubic and tetragonal phases, were stable expanded with increasing Ba content, which was in agreement with the tolerance factor approaching unity.

Twinning hierarchy, shape memory, and superelasticity demonstrated by molecular dynamics

A martensitic phase transition exhibiting shape memory, transformation-induced plasticity, or superelasticity typically involves a transformation between a high temperature, high symmetry phase and a low temperature, low symmetry phase. There have been numerous attempts using molecular dynamics to simulate the shape memory behavior, where the memory is stored in a twinned martensite and deformation occurs by motion of twin boundaries. However, the 3D case has always proved elusive, because suitable interatomic potentials to produce a unique low temperature phase are difficult to obtain. Here we present a study in which the binary Morse potential is tuned specifically to maximize the difference between L1${}_{0}$ and B19 (Strukturbericht notation, spacegroups P4/mmm and Pmma) structures. The twinned structure of martensite has been induced by gradually cooling the sample below the transition temperature. A bar-shaped sample was plastically deformed in the martensite phase, and on reheating above the transition temperature the initial shape was recovered. The effect of the shear-induced phase transition on the nanostructure of resulting martensite has also been investigated. An unusual discovery is that of a hierarchy of twins: nanotwins accommodate the mismatch between austenite and martensite at the habit plane, while dynamically created macrotwins are responsible for the deformation behavior and shape memory.

Molecular dynamics simulation study of microstructure evolution during cyclic martensitic transformations

Shape memory alloys (SMA) exhibit a number of features which are not easily explained by equilibrium thermodynamics, including hysteresis in the phase transformation and “reverse” shape memory in the high symmetry phase. Processing can change these features: repeated cycling can “train” the reverse shape memory effect, while changing the amount of hysteresis and other functional properties. These effects are likely to be due to formations of localised defects and these can be studied by atomistic methods. Here we present a molecular dynamics simulation study of such behaviour employing a two-dimensional, binary Lennard–Jones model. Our atomistic model exhibits a symmetry breaking, displacive phase transition from a high temperature, entropically stabilised, austenite-like phase to a low temperature martensite-like phase. The simulations show transformations in this model material proceed by non-diffusive nucleation and growth processes and produce distinct microstructures. We observe the generation of persistent lattice defects during forward-and-reverse transformations which serve as nucleation centres in subsequent transformation processes. These defects interfere the temporal and spatial progression of transformations and thereby affect subsequent product morphologies. During cyclic transformations we observe accumulations of lattice defects so as to establish new microstructural elements which represent a memory of the previous morphologies. These new elements are self-organised and they provide a basis of the reversible shape memory effect in the model material.

Reorientation transitions in rhombohedral magnets

Reorientation transitions in a rhombohedral magnet have been studied taking into account invariants up to the sixth order inclusive. Unlike the hexagonal, tetragonal, and orthorhombic magnets, in rhombohedral magnets transitions into the high-symmetry phase are possible only through a first-order phase transition. It has been shown that critical, triple, and quadruple points can exist in the phase diagram.

Mechanical Behavior of Alpha, Beta, and Gamma Plutonium

Plutonium is a highly unusual metal displaying six allotropic phases between room temperature and 550 Centigrade. The crystal structures present vary from low-density high-symmetry cubic phases to high-density low-symmetry monoclinic phases, presenting unique challenges and opportunities for the researcher. In addition, the properties of plutonium may change over time due to radioactive decay, introducing radiation damage and causing changes in chemistry.Castings of high-density Plutonium were created as part of a research and development effort at Los Alamos National Laboratory. The as-cast material was characterized using a variety of techniques, including resonant ultrasound spectroscopy (RUS), dilatometry, and quasi-static mechanical testing. A brief overview of the experimental technique of RUS as it applies to plutonium will be presented, along with discussion of the elastic moduli of alpha plutonium measured in the newly as-cast state. Compression tests of alpha plutonium and tensile tests of beta and gamma phase plutonium will be presented and compared with previous literature and experiments including older alpha plutonium specimens by previous authors.

Raman Scattering Study Temperature Phase Transitions of Rb2KInF6 Crystal

Raman scattering spectra of Rb2KInF6 crystal have been studied in a wide temperature range, including two phase transitions: from cubic to tetragonal, and then – to the monoclinic phase. Hardening of soft phonon modes was observed that attributes them to the transitions of displacive type. Parameters of Raman lines have been quantitatively analyzed and found in good agreement with known thermodynamic characteristics of these transitions. No evidences of order – disorder processes were observed in the Raman spectra of the high-symmetry phase.

Entropically Stabilized Local Dipole Formation in Lead Chalcogenides

We report the observation of local structural dipoles that emerge from an undistorted ground state on warming, in contrast to conventional structural phase transitions in which distortions emerge on cooling. Using experimental and theoretical probes of the local structure, we demonstrate this behavior in binary lead chalcogenides, which were believed to adopt the ideal, undistorted rock-salt structure at all temperatures. The behavior is consistent with a simple thermodynamic model in which the emerging dipoles are stabilized in the disordered state at high temperature due to the extra configurational entropy despite the fact that the undistorted structure has lower internal energy. Our findings shed light on the anomalous electronic and thermoelectric properties of the lead chalcogenides. Similar searches may show that the phenomenon is more widespread.

Size-Dependent Infrared Phonon Modes and Ferroelectric Phase Transition in BiFeO3 Nanoparticles

One emergent property of ferroelectric nanoparticles is the sized-induced structural distortion to a high-symmetry paraelectric phase at small particle sizes. Finite length scale effects can thus be advantageously employed to elucidate ferroelectric transition mechanisms. In this work, we combine infrared spectroscopy with group theory and lattice dynamics calculations to reveal the displacive nature of the ferroelectric transition in BiFeO3, a room temperature multiferroic. Systematic intensity and frequency trends in selected vibrational modes show that the paraelectric phase is Pm3m and the lowest frequency A1 feature is the soft mode that drives the first order transition. Finite length scale effects are also evident in the electronic structure with a red-shifted band gap in nanoscale BiFeO3 compared with that of the rhombohedral film, a result that can impact the development of ferroelectric photovoltaics and oxide-based electronics. Taken together, these findings demonstrate the foundational importance of size effects for enhancing the rich functionality and broad utility of transition metal oxides.

Superconductivity forCaC6to 32 GPa hydrostatic pressure

The dependence of the superconducting transition temperature Tc of CaC6 has been determined as a function of hydrostatic pressure in both helium-loaded gas and diamond-anvil cells to 0.6 and 32 GPa, respectively. Following an initial increase at the rate +0.39(1) K/GPa, Tc drops abruptly from 15 K to 4 K at 10 GPa. Synchrotron x-ray measurements to 15 GPa point to a structural transition near 10 GPa from a rhombohedral to a higher symmetry phase.

(Invited) Dielectric Properties and Flat-Band Voltages of Doped- HfO2 Thin Films

The control of high-symmetry phases of HfO2 can be achieved by cationic substitution for Hf. The electrical properties of the cubic HfO2 phase stabilized by addition of yttrium or magnesium were investigated. The introduction of moderate Y or Mg doping content (~10-15%) in HfO2 results in an enhancement of the dielectric constant. No degradation of the interface state density and of the leakage current was noticed. The flat-band voltage is shifted to positive voltages, similarly as it was observed for monoclinic and cubic pure HfO2 thin films. This result confirms that the contribution of the SiO2/high-k interface to the flat-band voltage depends on the structural interface properties.

Antiferromagnetic and structural transitions in the superoxideKO2from first principles: A2p-electron system with spin-orbital-lattice coupling

KO2 exhibits concomitant antiferromagnetic (AFM) and structural transitions, both of which originate from the open-shell 2p electrons of O$_{2}^{-}$ molecules. The structural transition is accompanied by the coherent tilting of O$_{2}^{-}$ molecular axes. The interplay among the spin-orbital-lattice degrees of freedom in KO2 is investigated by employing the first-principles electronic structure theory and the kinetic-exchange interaction scheme. We have shown that the insulating nature of the high symmetry phase of KO2 at high temperature (T) arises from the combined effect of the spin-orbit coupling and the strong Coulomb correlation of O 2p electrons. In contrast, for the low symmetry phase of KO2 at low T with the tilted O$_{2}^{-}$ molecular axes, the band gap and the orbital ordering are driven by the combined effects of the crystal-field and the strong Coulomb correlation. We have verified that the emergence of the O 2p ferro-orbital ordering is essential to achieve the observed AFM structure for KO2.