Structural phase transition (zincblende-rocksalt) and elastic properties in AlY (Y=N, P and As) compounds: Pressure-induced effects

The present paper addresses the pressure-induced structural aspects of ZnS-type (B3) to NaCl-type (B1) structure in AlY (Y=N, P, As). An effective-interionic interaction potential (EIoIP) with long-range Coulomb and three-body interactions and the Hafemeister-and-Flygare-type short-range overlap repulsion extended up to the second-neighbour ions and the van der Waals (vdW) interaction is developed. Emphasis has been given on evaluating the vdW coefficients by the Slater-Kirkwood variational method, as both the ions are polarizable. The lattice model calculations have revealed reasonably good agreement with the available experimental data on the phase-transition pressures (P_t=16, 14, 7.5 GPa) and the elastic properties of AlY (Y=N, P, As). The equation of state curves (plotted between V(P)/V(0) and pressure) for both the B3 and B1 structures obtained are in fairly good agreement with the experimental results. The calculated values of the volume collapses [ΔV(P)/V(0)] are also close to their observed data. Further, the variations of the second-order elastic constants with pressure follow a systematic trend that is almost identical to that exhibited by the observed data measured for other semiconducting compounds with B3→B1 structural phase transitions.     

High-pressure phases of CuI studied by129I-Mössbauer spectroscopy

The results of an¹²⁹I-Mössbauer study of the high-pressure phases of CuI at 4.2 K and for external pressures up to 71 kbar are reported. The isomer shiftS and the electric quadrupole interactionE _q are found to undergo larges discontinuities at the crystallographic phase-transition pressures of ?18 kbar from zinc-blence to rhombohedral structure and at ?46 kbar from rhombohedral to tetragonal. The pressure coefficients of these hyperfine parameters are significantly different for the three phases (zinc-blende; rhombohedral; tetragonal) dS/dP=?3.3; =+1.5; =2.5×10^?3 mm/s/kbar; dE _q/dP=0.0; =?0.92;=+0.31 Mc/s/kbar. These results cannot be explained in terms of a simple molecular-orbital picture; instead, they reflect pressure-induced variations of the halogen-p/metal-d hybridization in the valence bands of the various phases of CuI.     

The structure of n-alkane binary mixtures adsorbed on graphite

The thermodynamics and structure of the surface adsorbed phase in binary C15-C16 and C15-C17 n-alkane mixtures confined in graphite pores have been studied by differential scanning calorimetry and small-angle X-ray scattering. The previously observed selective adsorption of the longer alkane for chain length differences greater than five carbon atoms is verified but reduced for chain length differences less than or equal to two. With a difference in chain length of one carbon atom, Vegard's law is followed for the melting points of the adsorbed mixture and the (0 2) d-spacing is a continuous function of the mole fraction x. With a two-carbon atom difference, samples aged for 1 week have a lamellar structure for which the entities A_1−xB_x try to be commensurate with the substrate. The same samples aged for 1 month show a continuous parabolic x-dependence for both the melting points and the d-spacings. An explanation in terms of selective probability of adsorption is proposed based on crystallographic considerations.     

Irradiation-assisted photoelastic domain wall formation in X- and Y-cut lithium niobate

Irradiation-assisted photoelastic domain wall formation in single-crystalline X- and Y-cut lithium niobate (LNO) is studied at low displacement doses, namely, up to a maximum of 2.5×10⁻² dpa and annealed at 270 °C. The formation of surface ridges (or striations) is observed and quantified using atomic force and optical microscopy. In spite of the different crystallographic orientation of the two single-crystals a correlation between the density of surface defects and the displacement dose is established phenomenologically which means that the displacement damage and its consequent defect accumulation behavior prior to annealing (‘incubation phase’) defines to which extent the lattice undergoes an irreversible mechanical deformation immediately after annealing. This ridge formation mechanism assisted by irradiation and moderate annealing constitutes a fine tool to modify the near-surface structure and the local optical properties of LNO and hence it allows one to potentially micromachine new photonic devices.     

Anisotropy of the electron momentum distribution in Bi2Sr2CaCu2O8+δ superconductor studied by positron annihilation

The temperature dependent (30-300 K) Doppler broadening of the positron annihilated γ-radiation measurement has been investigated on single crystalline Bi₂Sr₂CaCu₂O_8+δ (Bi-2212) high T_c superconducting samples along two different crystallographic orientations. It has been observed that throughout the temperature range the electron momentum distribution has a larger value along the crystallographic c-axis than in the a-b plane. The temperature dependent Doppler broadened positron annihilation γ-radiation lineshape analysis shows a step like increase of S-parameter at the temperature region 92-116 K.     

Thickness-dependent magnetic order and phase-transition dynamics in epitaxial Fe-rich FeRh thin films

The control of magnetic order and phase-transition dynamics by various means is a key towards low-power spintronics. Here, we report a control on magnetic order and phase-transition dynamics by tuning film thickness in epitaxial FeRh films. Reduction of film thicknesses from 200 nm to 5 nm results in an anti-ferromagnetic to ferromagnetic phase change, accompanied by a 0.55% lattice expansion for c-axis. The phase-transition dynamics is highly dependent on the film thickness, and involves the release and recovery of lattice strain that results in a lower transition temperature and larger thermal hysteresis in thinner films. The findings help to understand the origin of thermal hysteresis and phase-transition dynamics in ultra-thin FeRh films. Possible approaches to narrow down thermal hysteresis are proposed.     

Studies of the electrical properties of nearly perfect K2ZnCl4 single crystals as measured during commensurate incommensurate-paraelectric phase transitions

Electrical conductivity and dielectric measurements were carried in the temperature range covering the commensurate ferroelectric-incommensurate-paraelectric normal phases (300-600 K) for the three main crystallographic axes of K₂ZnCl₄ single crystals. The values of activation energies in the three phases were calculated and discussed. A thermal hysteresis of about 12 K is observed which deduce the presence of first order transition for the lock-in ferroelectric transition at T_c=404 K. Conductivity anomalies were observed in both ferroelectric and paraelectric phases. The conduction mechanism was discussed. The suggested occurrence of discommensuration in K₂ZnCl₄ crystals upon the lock-in transition in contrast with conductivity and dielectric results explains the anomalous behavior for the b-axis measurements. The orientation of these discommensuration was discussed on a view of projection in the three standard crystallographic directions.     

Bilbao Crystallographic Server : Useful Databases and Tools for Phase-Transition Studies

Bilbao Crystallographic Server is a web site with crystallographic programs and databases available on-line. The programs give access to general information related to space groups (generators, general positions, Wyckoff positions, irreducible representations), group-subgroup or group-supergroup pairs of space groups, and/or results on specific crystal structures. The utility of the programs is illustrated by treating phase-transition problems related to structural pseudosymmetry.     

Critical behaviors of bond and crystal field dilution Blume–Emery–Griffiths model

The critical behavior of the spin-1 bond and crystal field dilution Blume–Emery–Griffiths model have been investigated on simple-cubic lattice within the framework of the effective field theory. In particular, both bond dilution and random crystal field are considered at the same time. The interplay between bond and crystal field dilution constructs rich and interesting phase diagrams. Significant distinctions are exhibited. When positive ratio α changes in a certain range, there exist double tricritical points in phase-transition lines in T–D plane. Moreover, this first-order phase transition is enlarged with increasing of ratio α at a fixed crystal field dilution concentration, while this first-order phase transition will shrink when bond dilution concentration is fixed. In addition, we observe that there exist two bond percolation thresholds for negative crystal field and α>0 in T–P plane.     

Structure refinements of cadmium substituted lead fluoroapatites by powder X-ray pattern fitting

Solid solutions of cadmium and lead fluoroapatite [Pb_(10−x)Cd_x(PO₄)₆F₂ (0?x?5)] were synthesized by a wet process in a basic medium. Replacement of lead by cadmium induces a linear variation of the crystallographic parameters “a” and “c” according to Végard's law. The cadmium content, as obtained from the refinement, is in agreement with the chemical analysis. The distribution of the lead and cadmium ions between two non-equivalent crystallographic sites, M(1) and M(2), was determined by the Rietveld method. The site-occupancy factors of atoms clearly indicate a preference of cadmium for site M(1) in the apatite structure in agreement with its smaller ionic radii. A progressive shift of the F⁻ ion toward the center of the triangles formed by the site M(2) metals has been observed with increasing cadmium content.     

Kanalisierungseffekte von Elektronen und Positronen in Silizium- und Anthrazenkristallen

Channeling of 148 keV electrons and 247 keV positrons in monocrystals of silicon and anthracene is found in transmission experiments. In anthracene the measurements are carried out atT=130 K. The number of transmitted electrons incident along the [110] axis of silicon and the [001] axis of anthracene is remarkably reduced. The number of transmitted positrons incident along these axes shows pronounced peaks. The theoretical critical angles for channeling are compared with the observed values.     

EPR of Mn2+ in Cd(COO)2· 3H2O single crystals

The electron paramagnetic resonance spectrum of Mn²⁺ has been investigated in cadmium oxalate trihydrate single crystals at room temperature. The spectrum, recorded in the X-band, consists of a set of lines all of which correspond to a single type of environment. None of the principal axes coincides with any crystallographic axis. The spectrum is satisfactorily described by a spin Hamiltonian with a rhombic crystalline electric field. The separations of the forbidden doublets (Δm = ± 1) in different electronic transitions have been calculated and compared with the observed doublet separations.     

On the tricritical point in MnSi under high pressures

The magnetic susceptibility of a MnSi single crystal is measured in the region of the ferromagnetic phase transition under pressures up to 0.8 GPa in compressed helium. It is found that the tricritical point on the phase-transition curve corresponds to a much lower pressure and a considerably higher temperature (P _tr ≈ 0.355 GPa and T _tr ≈ 25.2 K) than was reported earlier (P _tr ≈ 1.2 GPa and T _tr ≈ 12 K). New results impose certain limitations on theoretical analysis of tricritical phenomena in MnSi.     

Anisotropic and large low-field magnetic entropy change in a La4/3Sr5/3Mn2O7 single crystal

We have studied the magnetocaloric effect (MCE) in a bilayered La_4/3Sr_5/3Mn₂O₇ single crystal with applied field along both ab-plane and c-direction. Due to the quasi-two-dimensional structure, the crystal exhibits a strong anisotropy in the MCE. The difference of magnetic entropy change between two crystallographic directions depends on external magnetic fields and has a maximum of 2 J/kg K. A large low-field magnetic entropy change, reaching 3.2 J/kg K for a magnetic field change of 15 kOe, is observed when the applied field is along ab-plane. This large low-field magnetic entropy change is attributed to the rapid change of magnetization in response to external magnetic fields in the easy magnetizing plane.     

Thickness dependence on thermal stability of sputtered Ag nanolayer on Ti/Si(1 0 0)

Thermal stability of Ag layer on Ti coated Si substrate for different thicknesses of the Ag layer have been studied. To do this, after sputter-deposition of a 10 nm Ti buffer layer on the Si(1 0 0) substrate, an Ag layer with different thicknesses (150-5 nm) was sputtered on the buffer layer. Post annealing process of the samples was performed in an N₂ ambient at a flow rate of 200 ml/min in a temperature range from 500 to 700 °C for 30 min. The electrical property of the heat-treated multilayer with the different thicknesses of Ag layer was examined by four-point-probe sheet resistance measurement at the room temperature. Phase formation and crystallographic orientation of the silver layers were studied by θ-2θ X-ray diffraction analysis. The surface topography and morphology of the heat-treated films were determined by atomic force microscopy, and also, scanning electron microscopy. Four-point- probe electrical measurement showed no considerable variation of sheet resistance by reducing the thickness of the annealed Ag films down to 25 nm. Surface roughness of the Ag films with (1 1 1) preferred crystallographic orientation was much smaller than the film thickness, which is a necessary condition for nanometric contact layers. Therefore, we have shown that the Ag layers with suitable nano-thicknesses sputtered on 10 nm Ti buffer layer were thermally stable up to 700 °C.     

The non-isotropic character of electric and dielectric properties of ammonium zinc chloride crystal

The dielectric constant, ε, and the d.c. conductivity, σ, were measured along the a-, b- and c-axes of (NH₄)₂ZnCl₄ (AZC) crystal in the 300-450 K temperature range. Crystals of AZC grown from aqueous solutions containing excess of ZnCl₂ were used. The value of the dielectric permittivity of AZC is extremely small compared to other ferroelectric crystals. Pronounced broad or step-like peaks at the phase transition temperatures were detected along the a- and b-axes, while ε along the c-axis is temperature independent up to the end of the measuring range. Reciprocal of the dielectric permittivity in the range of the commensurate to incommensurate phase transition obeys a relation similar to the Curie-Weiss law that is valid for second order ferroelectric/paraelectric phase transitions. The constants of the proposed relationship applied to the cooling run are given. The J-E characteristics along the three crystallographic axes were measured in the normal, incommensurate, commensurate and antiferroelectric phases. Hence, the type of conduction mechanism has been estimated. Parameters of Poole-Frenkel and Richardson-Schottky types of conduction mechanism have been determined. The effect of applied electric field on the conductivity measurement was also tested. Conductivity anomalies with different character were observed at the phase transition temperatures. The lnσ−1000/T dependence revealed thermal activation energy of conduction along the a-, b- and c-axes with different values in different phases of AZC.     

Displacive phase-transition of cuprite Ag2O revealed by extended x-ray absorption fine structure

The low-temperature phase-transition of silver oxide (Ag₂O) has been investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy as a function of temperature. The thermal evolution of the local structure around Ag atoms has been determined. In particular, below the phase-transition temperature at ∼35 K, a progressive splitting of the Ag–Ag next-nearest-neighbor distances is observed. This definitely supports the idea that the phase-transition of Ag₂O is due to displacive disorder of the Ag atoms.     

Pressure-induced phase transitions of lanthanide monoarsenides LaAs and LuAs with a NaCl-type structure

By use of synchrotron radiation the powder X-ray diffraction of lanthanide monoarsenides LaAs and LuAs with a NaCl-type structure has been studied up to 60 GPa at room temperature. First-order phase transitions with the crystallographic change were found at around 20 GPa for LaAs, and 57 GPa for LuAs. The high-pressure form of LaAs is a tetragonal structure and can be viewed as a distorted CsCl-type structure. The atoms in the tetragonal structure are located at La: 0, 0, 0; As: 1/2, 1/2, 1/2. The space group is P4/mmm. The structural change to the tetragonal structure occurs with the volume collapse of about 10%. The structure of these high-pressure phases of LuAs is unknown. The volume vs. pressure curves for LaAs and LuAs are fitted by a Birch equation of state. The bulk moduli of both arsenides are 92±6 GPa for LaAs and 85±3 GPa for LuAs. The high-pressure structural behavior of LaX (X=P, As and Sb) and LnAs (Ln=lanthanide) with the NaCl-type structure is discussed.     

Channelingeffekte bei der Lichtausbeute von Anthrazen-, Naphthalin- undp-Terphenylkristallen bei Anregung mit α-Teilchen

The scintillation light yield of anthracene atT=300 °K andT=80 °K and of naphthalene andp-terphenyl atT=80 °K was investigated for impact directions in the (a, c)-plane. The light yield was measured for welldefined integration times. The relative depth of the channeling-minimum observed for impact directions parallel to thec-axis of anthracene is found to increase with increasing integration times. For the first time channeling-minima of the light yield were observed at impact directions parallel to thec- and the [102]-axis of naphthalene and thec- and [¯102]-axis ofp-terphenyl. The [¯102]-axis ofp-terphenyl shows a more pronounced effect than thec-axis.     

Spontaneous emission rates of a single-impurity molecule in birefringent host crystals for electric quadrupole transitions

In a birefringent host crystal, the spontaneous emission rate of zero-phonon line of a single-impurity molecule depends on the angles between the transition dipole moment and the principal axes of the dielectric (permittivity) tensor and also on the main dielectric constants of a host crystal. In this paper, the spontaneous emission rate of the electric quadrupole transition of a single-impurity molecule is calculated for uniaxial host crystals with the ordinary reflective indices n_o=1.5, 2, 3 and a variable extraordinary reflective index, and for seven biaxial host crystals (anthracene, chrysene, diphenyl, fluorine, naphthalene, phenanthrene, terphenyl). For the above-mentioned biaxial crystals, differences in the values of spontaneous emission rate of the quadrupole transition in the same host crystal are up to 11%.