Search

The crystal structure and bonding environment of K2Ca(CO3)2 bütschliite were probed under isothermal compression via Raman spectroscopy to 95 GPa and single crystal and powder X-ray diffraction to 12 and 68 GPa, respectively. A second order Birch-Murnaghan equation of state fit to the X-ray data yields a bulk modulus, K 0 = 46.9 GPa with an imposed value of K 0 ′ = 4 for the ambient pressure phase. Compression of bütschliite is highly anisotropic, with contraction along the c-axis accounting for most of the volume change. Bütschliite undergoes a phase transition to a monoclinic C2/m structure at around 6 GPa, mirroring polymorphism within isostructural borates. A fit to the compression data of the monoclinic phase yields V 0 = 322.2 Å3 , K 0 = 24.8 GPa and K 0 ′ = 4.0 using a third order fit; the ability to access different compression mechanisms gives rise to a more compressible material than the low-pressure phase. In particular, compression of the C2/m phase involves interlayer displacement and twisting of the [CO3] units, and an increase in coordination number of the K+ ion. Three more phase transitions, at ~ 28, 34, and 37 GPa occur based on the Raman spectra and powder diffraction data: these give rise to new [CO3] bonding environments within the structure. [ABSTRACT FROM AUTHOR]

Ga-Sb alloys with compositions ranging between ∼12 and 50 at. % Ga are promising materials for phase change random access memory applications. The short-range structures of two such alloys with compositions Ga14Sb86 and Ga46Sb54 are investigated, in their amorphous and crystalline states, using 71Ga and 121Sb nuclear magnetic resonance spectroscopy and synchrotron x-ray diffraction. The Ga and Sb atoms are fourfold coordinated in the as-deposited amorphous Ga46Sb54 with nearly 40% of the constituent atoms being involved in Ga-Ga and Sb-Sb homopolar bonding. This necessitates extensive bond switching and elimination of homopolar bonds during crystallization. On the other hand, Ga and Sb atoms are all threefold coordinated in the as-deposited amorphous Ga14Sb86. Crystallization of this material involves phase separation of GaSb domains in Sb matrix and a concomitant increase in the Ga coordination number from 3 to 4. Results from crystallization kinetics experiments suggest that the melt-quenching results in the elimination of structural 'defects' such as the homopolar bonds and threefold coordinated Ga atoms in the amorphous phases of these alloys, thereby rendering them structurally more similar to the corresponding crystalline states compared to the as-deposited amorphous phases. [ABSTRACT FROM AUTHOR]

Resistive heating of a sample in a diamond anvil cell (DAC) can generate a homogeneous temperature field across the sample chamber with reliable temperatures measured by a thermocouple. It is of importance in experiments aiming at exploring phase diagrams and quantifying thermoelastic properties of materials. Here, we present a ring-heater design developed for BX90 diamond anvil cells (DACs). It is made of a ring-shaped aluminum oxide holder hosting a tungsten wire coil inside and coupled with Ar + 2% H2 gas to prevent oxidation during experiment. This modular plug-and-play design enables in situ studies of samples via x-ray diffraction up to a temperature of 1700 K. Temperature in the BX90 sample volume as measured through a thermocouple was calibrated using the melting point of gold. As an application of this design, we report the thermal expansion coefficient of MgO at 9.5(1) GPa. [ABSTRACT FROM AUTHOR]

The structural, thermodynamic, and kinetic aspects of the transformations between the metastable amorphous and crystalline phases of GaSb are investigated as a function of pressure at ambient temperature using synchrotron x-ray diffraction experiments in a diamond anvil cell. The results are consistent with the hypothesis that the pressure induced crystallization of amorphous GaSb into the β-Sn crystal structure near ∼5 GPa is possibly a manifestation of an underlying polyamorphic phase transition between a semiconducting, low density and a metallic, high density amorphous (LDA and HDA, respectively) phases. In this scenario, the large differences in the thermal crystallization kinetics between amorphous GaSb deposited in thin film form by sputtering and that prepared by laser melt quenching may be related to the relative location of the glass transition temperature of the latter in the pressure-temperature (P-T) space with respect to the location of the critical point that terminate the LDA ↔ HDA transition. The amorphous → β-Sn phase transition is found to be hysteretically reversible as the β-Sn phase undergoes decompressive amorphization near ∼2 GPa due to the lattice instabilities that give rise to density fluctuations in the crystal upon decompression. [ABSTRACT FROM AUTHOR]

Pressure induced densification in a molecular arsenic sulfide glass is studied at ambient temperature using x-ray scattering, absorption and Raman spectroscopic techniques in situ in a diamond anvil cell. The relatively abrupt changes in the position of the first sharp diffraction peak, FSDP, and the pressure-volume equation of state near ∼2 GPa suggest a phase transition between low- and high-density amorphous phases characterized by different densification mechanisms and rates. Raman spectroscopic results provide clear evidence that the phase transition corresponds to a topological transformation between a low-density molecular structure and a high-density network structure via opening of the constituent As4S3 cage molecules and bond switching. Pressure induced mode softening of the high density phase suggests a low dimensional nature of the network. The phase transformation is hysteretically reversible, and therefore, reminiscent of a first-order phase transition. [ABSTRACT FROM AUTHOR]

The thermodynamic nature of phase stabilities and transformations are investigated in crystalline and amorphous Ge1Sb2Te4 (GST124) phase change materials as a function of pressure and temperature using high-resolution synchrotron x-ray diffraction in a diamond anvil cell. The phase transformation sequences upon compression, for cubic and hexagonal GST124 phases are found to be: cubic → amorphous → orthorhombic → bcc and hexagonal → orthorhombic → bcc. The Clapeyron slopes for melting of the hexagonal and bcc phases are negative and positive, respectively, resulting in a pressure dependent minimum in the liquidus. When taken together, the phase equilibria relations are consistent with the presence of polyamorphism in this system with the as-deposited amorphous GST phase being the low entropy low-density amorphous phase and the laser melt-quenched and high-pressure amorphized GST being the high entropy high-density amorphous phase. The metastable phase boundary between these two polyamorphic phases is expected to have a negative Clapeyron slope. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The Advanced Light Source (ALS) is a 1.9-GeV, third-generation synchrotron optimized for the production of VUV and soft X-rays from undulators. There is also a hard X-ray program at the ALS, which is based around three 6-T superconducting bending magnets [1] that shift the critical energy from 3 keV to 12 keV. The extreme conditions beamline at the ALS is situated on Beamline 12.2.2, which benefits from radiation produced by one of these superbend sources. The beamline is designed for X-ray diffraction, X-ray spectroscopy, and X-ray imaging of samples held in diamond-anvil high-pressure cells (DACs). In a DAC, samples are on the order of 10 to 50 μm in diameter and 10 to 30 μm thick and are contained in a metal gasket of typical inner diameters of 100 to 150 μm. For high-quality diffraction patterns with little or no contamination from diffraction from the gasket, the X-ray beam size needs to be on the order of 10 μm × 10 μm. [ABSTRACT FROM AUTHOR]

A high-pressure synchrotron x-ray diffraction study of the phase change alloy Ge1Sb2Te4 demonstrates the existence of a polyamorphic phase transition between the 'as deposited' low density amorphous (LDA) phase and a high density amorphous (HDA) phase at ∼10 GPa. The entropy of the HDA phase is expected to be higher than that of the LDA phase resulting in a negative Clapeyron slope for this transition. These phase relations may enable the polyamorphic transition to play a role in the memory and data storage applications. [ABSTRACT FROM AUTHOR]