High pressure X-ray emission spectroscopy at the advanced photon source

ABSTRACT

The structural, electronic, and magnetic properties of materials under high pressure are of fundamental interest in physics, chemistry, materials science, and earth sciences. Among several hard X-ray-based techniques, X-ray emission spectroscopy (XES) provides a powerful tool to probe element-specific information for understanding the electronic and magnetic properties of materials under high pressure. Here, we discuss on the particular requirements and instrumentation used in high pressure XES experiments. We then present several examples to illustrate the recent progress in high pressure XES studies at the Advanced Photon Source, followed by an outlook toward future development in high pressure XES.     

High pressure raman studies of GaAs/A1As superlattices: folded-acoustic phonons and resonant second-order scattering

Abstract

Materials containing light elements and characterized by a dense structure present specific physico-chemical properties.

The carbonitrides C_xN_y, and in particular C₃N₄, have attracted the attention of the scientific community during these last ten years.

The main chemical problem in the synthesis of such materials is to introduce nitrogen into the lattice, due to the strong stability of N₂.

In order to prevent nitrogen loss, the use of high pressures and the selection of nitriding media can be developed.

The present contribution describes the main results obtained through two routes:

(i) the thermal decomposition of precursors containing carbon and nitrogen under high pressure conditions (2-6GPa) (without or with nitrogen solvent)

(ii) the high pressure condensation of “organic” precursors containing carbon and nitrogen.     

High pressure dynamic XAS studies using an energy-dispersive spectrometer

ABSTRACT

We present in this paper recent advances in the high pressure domain provided by the introduction of time-resolved energy-dispersive XAS (EDXAS) techniques at synchrotrons. We highlight technical aspects and describe two modes of acquisition: the ‘movie’ mode, where the time resolution is given by the detector acquisition speed and the ‘pump-and-probe’ mode, where the time resolution is given by the delay between the pump and the probe. These two modes define a frontier in the time resolution, respectively above and below the ～10?μs regime. In the former, examples of applications are chemical stability and reactions at high pressure and high temperature or probing the warm dense matter regime using rapid current ramps. In the latter, an example is given on studies of dynamically compressed matter, by coupling single-bunch EDXAS at high-brilliance synchrotron to a nanosecond high-power laser.     

Recent studies on pressure-induced chemical changes in food constituents

Abstract

The application of high hydrostatic pressure is one of the most promising novel minimal processing methods for food preservation. Under optimal process conditions the natural fresh properties of foods are retained. Pressure is an important thermodynamic factor as is temperature. Both pressure and temperature may influence the position of a chemical reaction equilibrium and the reaction rate. Examples of pressure effects on food quality related reactions are presented The effect of pressure on reactions resulting in flavour or colour defects or the formation of undesirable substances and the effect of pressure on the stability of valuable constituents like vitamin A or sulforaphane.     

High pressure effects on myofibrillar proteins

Abstract

Myofibrillar proteins were extracted from post rigor bovine meat with a potassium phosphate/potassium chloride buffer. Viscoelastic properties of myofibrillar properties were studied in a 0.6MKCl buffer, at pH = 6, used in an oscillating mode. Enthalpy patterns were determined with a differential scanning calorimeter. SDS PAGE was performed.

Results show that high pressure processing denatures myofibrillar proteins, which result in a decrease of myofibrillar protein extractability. Moreover, the viscoelastic properties of myofibrillar extracts are modified by a preliminary high-pressure treatment of meat. The storage modulus (G′) versus temperature graph presents an intermediate peak; the height of this peak and the final value (90°C) are dependant on the level of pressure.

Finally, enthalpy and electrophoresis patterns allow us to understand myofibrillar protein modifications induced by high hydrostatic pressure processing of meat.     

Peculiarities of phase transitions when synthesizing diamond in high pressure apparatus of various types

Abstract

The influence of P, T-parmeters and duration of heat when synthesizing diamond in high pressure apparatus both of recessed anvil-type and cylindrical type (belt-type) on properties of diamond powders was studied. The dependence of pressure in reaction cells on temperature of force elements of apparatus in initial state and on efficiency of high pressure production in a reaction cell before heating was shown.     

New packaging solutions for high pressure treatments of food

Abstract

High pressure is a promising technology for developing new processes in food treatment. In most cases, pre-packaged foods are used in high pressure treatments (HP). Consequently, the behavior of the package under treatment conditions is an important factor. The following work was devoted to the evaluation of different packages under high pressure conditions in the presence of different substances used as simulants. Three main characterizations were carried out after HP treatment: mechanical resistance, barrier properties and integrity.

The experimental results using multilayer plastic films (PA/PE) have led to the selection of several solutions which may be used as packages for high pressure treatments.     

High pressure chemistry of molecular systems: Recent experimental results and developments

Abstract

It is widely recognized that relevant new chemistry is being discovered by applying high pressures. The study of the equation of state, pressure-induced phase transitions, reactivity, etc., of molecular systems are topics of increasing interest in high pressure science. This paper compiles recent studies performed by the author on molecular systems at high pressures. This includes, on the theoretical side, a reference to a universal model of EOS for both liquids and solids at high pressure. Several experiments performed by the author are also discussed; among others, a high pressure polymerization of carbon monoxide, the design of an anvil cell system developed in our laboratory, introducing an alternative Raman pressure scale when sapphires are mounted as anvils (SAC configuration) and, finally, several actual SAC experiments are presented, including examples of phase transitions and reactivity at high pressure on double and triple bonded molecular systems.     

RIXS in correlated electron systems under extreme conditions

ABSTRACT

We report here on the application of Resonant Inelastic X-ray Scattering (RIXS) in correlated electrons systems under pressure. Thanks to its bulk sensitivity and superior resolving power, RIXS appears as a powerful spectroscopic technique to unravel the local electronic and magnetic properties of materials at extreme conditions. The method is illustrated in vanadium-oxides- and Fe-based superconductors at high pressure.     

High oxygen pressures and the stabilization of six-coordinated Ir(VI) in an oxygen lattice

Abstract

During these last twenty five years a great efforts have been made in the Laboratoire de Chimie du Solide du CNRS in order to develop high oxygen pressure for the stabilization of unusual oxidation state of transition elements.

The aims of such research works was to correlate the increase of the Mⁿ⁺-O bond covalency versus the increase of the oxidation state n+ to the physicochemical properties of resulting oxides [1].

Iridium was an interesting element due to its position (5d) in the Periodic Table. In 1980 Ir(V) (d⁴) was stabilized in La₂LiIrO₆ in the perovskite structure [2]. Such a study had underlined the strong value of the spin-orbit coupling associated to Ir(V) [3].

The stabilization of Ir(VI) is interesting from two points of view : (i) its isotropic electronic configuration (d³), (ii) such a high oxidation state could lead to the strongest M-O bond in an oxygen lattice.

Selecting, through a specific methodology, the most appropriate local structural and chemical factors and with the help of high oxygen pressure, Ir(V1) was stabilized in the perovskite Ba₂CaIrO₆. Structural, magnetic and Mössbauer studies have been carried out in order to characterize the physicochemical properties induced by this unusual oxidation state.     

Hydrostatic pressure investigations of resonant tunnelling through X-minimum-related states in a single barrier GaAs/AlAs/GaAs heterostructure

Abstract

We have investigated the resonant tunnelling of electrons through X-valley related states in a single AlAs barrier with Si donor & doping. Under high hydrostatic pressure all the peaks observed in the differential conductance-voltage (σ-V) characteristics shift with a pressure rate of -lSmeV/kbar, which is expected for X-minima related electronic states.     

Pressure effect on structural,electronic optical and thermodynamic properties of cubic AlxIn1-xP: a first-principles study

ABSTRACT

First-principles total energy calculations have been performed using the full potential linearised augmented plane wave (FP-LAPW) method as implemented in the WIEN2k code based on the density functional theory (DFT) to investigate the Al-doping effects on the structural, electronic and optical properties of Al_xIn_1-xP ternary alloys in the zinc-blende (ZB) phase. Different approximations of exchange-correlations energy were used such as the local density approximation (LDA), the generalised gradient approximation within parameterisation of Perdew–Burke–Ernzerhof (PBE-GGA), and the Wu-Cohen (WC-GGA). In addition, we have calculated the band structures with high accuracy using the Tran-Blaha modified Becke–Johnson (TB-mBJ) approach. The pressure dependence of the electronic and optical properties of binary AlP, InP compounds and their related ternary alloys Al_xIn_1-xP were also investigated under hydrostatic pressure for (P?=?0.0, 5.0,10.0, 15.0, 20.0, 25.0?GPa), where it is found that InP compound change from direct to indirect band gap for P?≥?9.16?GPa. Furthermore, we have calculated the thermodynamic properties of InP and AlP binary compounds as well as the Al_xIn_1-xP solid solutions, where the quasi-harmonic Debye model has been employed to predict the pressure and temperature dependent Gibbs free energy, heat capacity, Debye temperature and entropy.     

Solvothermal synthesis of AlN

Abstract

Aluminum nitride is an important material due to its physical properties (electronic, thermal conductivity…). Different processes have been used for preparing such a material. The solvothermal synthesis is characterised by the use of a solvent in supercritical conditions in order to improve the reactivity of the precursors and to control the size of the crystalhtes. Using finely divided aluminum particles as precursor, a new process for the preparation of AlN has been optimised versus the thermodynamical parameters: pressure and temperature and the nature of the additive used for improving the kinetics of nitridation.     

A new route for the synthesis of nitrides: The solvothermal preparation of GaN

Abstract

A new solvothermal route for the synthesis of nitrides is proposed using liquid NH3 as solvent in supercritical conditions, Such a preparation method was applied to the synthesis of GaN using gallium metal as starting material.

GaN is a wide band-gap semi-conductor (3.4eV). It is a very attractive nitride due to its various applications in micro- and opto-electronics [1,2]. Consequently, many research groups are interested in synthesising GaN. Two methods have been principally developed:

(i) synthesis of thin films by epitaxy [3,4]

(ii) synthesis of bulk GaN by high pressure method [5,6].

The new proposed process leads to fine microcrystallites of GaN with the wurtzite-type structure. The chemical purity can be optimised versus the synthesis mechanism. The size and shape of the crystallites would be influenced by the nature of the nitriding additive and the thermodynamical conditions (pressure and temperature) used for the synthesis.     

Demixing in binary systems at high pressure

Abstract

It is a well-recognized fact that the application of pressure has a large influence on the properties of pure substances. It will be shown here that this is even more true in the case of mixtures. Under high pressure, several new and interesting phenomena are observed. Some recent results will be presented and discussed.     

Structural and electronic properties of wurtzite,zincblende and rocksalt Al1 − xInxN ternary alloys at ambient and high pressure

ABSTRACT

Although AlInN is originally a wurtzite structure, zincblende and rocksalt are other potential phases. It will be interesting to have a comparative study of the physical properties of this compound in various phases. A DFT-based study of wurtzite, zincblende and rocksalt phases of AlInN alloys is carried out. Structural (lattice parameter, bulk modulus) and electronic properties (energy band gap, and electron effective mass) of the Al_{1??? x}In_xN alloys are investigated, at ambient pressure, throughout the whole range of indium contents for all considered phases. High pressure effects on the studied parameters are also examined, with the phase transition pressures computed for different values of In concentrations, and compared with available data. Structural density functional calculations are performed with Perdew–Burke–Ernzerhof gradient-corrected functional for solids (PBEsol), while electronic structure is computed with the modified Becke–Johnson (TB-mBJ) potential exchange to ensure a better accuracy of calculated the band gaps. Alloy randomness is taken into account using a special quasi-random structure.     

Metalinsulator transition induced by pressure in chemically bonded solids

Abstract

A review is given of metal-insulator transitions induced by pressure in chemically bonded solids.

After an introduction to energy band overlap mechanisms, which appear very useful to characterize the insulator-metal transitions in some solids (the rare gases He and Xe, the iso-electronic sequence of Xe, H₂ and I₂), some discussion is given of electron correlation in relation to molecular dissociation. However, it is to be emphasized that such dissociation is a sufficient, but not a necessary, condition for metallization in H. and I₂. For N₂, the above considerations, which focussed dominantly on ground-state properties as a function of pressure, need transcending because the observation of metallization in this system plainly involves thermal effects in an important way.

The final part of the review considers the way various low-dimensional solids (polyacetylene, TTF-TCNQ, and appropriate phases of H₂ and I₂) are altered by application of high pressures. Present understanding leads to the conclusion that there should be an interesting interplay between Hubbard on-site electron correlation, bond-charge repulsion and near-neighbour interaction, as a function of thermodynamic state.     

High pressure transormations of pyrope (garnet) and pyrope (pyroxene)

Abstract

Clinopyroxenes with higher contents of calcium and alumina in pyroxenites from inclusions in serpentinites of the central part of the granulite complex near Waldheim/Saxony contains several different exsolutions as producte of diffusive transformations under high pressures. The interpretation of the chemical composition of the exsolutions and the pyroxene host in application to the Published thermobarometers in the CMAS-system shows very different values between 685–1400°C temperature and 8 to above 30 kbar pressure, indicating a polymetamorphic high pressure history of the pyroxenites. The partial transformation of the pyrope (garnet) to pyrope (pyroxene) is strong kinetic influenced.     

Bridge Effect in Charge Transfer Absorption Bands. Para-substituted Benzylideneacetones

Abstract

The electronic absorption charge transfer bands in a series of para - substituted benzalketones are analyzed in order to stablish the role of the electron-donor substkuent as well as the electronic properties of the molecular structure of the π-conduction channel.

Absorption bands assignment of the π-π^? electronic transitions in the near ultraviolet spectral region is carry out from an experimental and theoretical point of view. The photo-induced charge transfer spectral bands in these aromatic compounds follow the same spectral pattern than the para-substituted benzaldehydes and acetophenones and the electronic transition takes place in the π,π^?(¹L_a) excited state. However, our semiempirical M.O. calculations show that this charge transfer process involve the electron-acceptor carbonyl group and the olefinic bond bridge as a second electron-acceptor group.     

Pressure Effects on Anisotropic Low-Dimensional Superconductors Close to an Electronic Topological Transition

Hydrostatic pressure or anisotropic stress can modify the electronic properties of a metal, thus inducing a change in the topology of its Fermi surface. In the case of low-dimensional anisotropic superconductors (such as high- T c cuprates, some organic salts, or heavy Fermion compounds), such changes result in a nonmonotonic dependence of several properties on the critical parameter z , measuring the distance of the chemical potential from the electronic topological transition (ETT). This has to be contrasted with the monotonic, nearly step-like z -dependence of the same quantities in the 3D case. Such a non-monotonic behavior is in agreement with the trend observed for T c as a function of pressure and other material specific quantities in several high- T c cuprate compounds. On the other hand, higher pressures than those reported in the literature (～ 10 kbar) should be investigated, in order to find evidence for ETT effects in the BEDT-TTF-based salts.