Experimental and theoretical study of band structure of InSe andIn1−xGaxSe(x<0.2)under high pressure: Direct to indirect crossovers
This paper reports on the pressure dependence of the absorption edge of indium selenide and ${\mathrm{In}}_{1\ensuremath{-}x}{\mathrm{Ga}}_{x}\mathrm{Se}$ alloys $(xl0.2)$ up to the pressure at which precursor effects of the phase transition prevent further transmission measurements. The absorption edge could be divided into three components exhibiting different pressure coefficients: one corresponding to a direct transition that could be analyzed through the Elliot-Toyozawa theory, and two supplementary edges with quadratic dependence on the photon energy. The first component is attributed to the direct transition at the Z point of the rhombohedral Brillouin zone. One of the quadratic abso…
Lattice dynamics of wurtzite and rocksalt AlN under high pressure: Effect of compression on the crystal anisotropy of wurtzite-type semiconductors
Raman spectra of aluminum nitride (AlN) under pressure have been measured up to $25\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$, i.e., beyond the onset of the wurtzite-to-rocksalt phase transition around $20\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$. The experimental pressure coefficients for all the Raman-active modes of the wurtzite phase are reported and compared to those obtained from ab initio lattice dynamical calculations, as well as to previous experimental and theoretical results. The pressure coefficients of all the Raman-active modes in wurtzite-type semiconductors (AlN, GaN, InN, ZnO, and BeO), as well as the relatively low bulk modulus and phase transition pressure in wurtzite AlN, a…
Anomální Ramanovy módy v teluridech
[EN] Two anomalous broad bands are usually found in the Raman spectrum of bulk and 2D Te-based chalcogenides, which include binary compounds, like ZnTe, CdTe, HgTe, GaTe, GeTe, SnTe, PbTe, GeTe2, As2Te3, Sb2Te3, Bi2Te3, NiTe2, IrTe2, and TiTe2, as well as ternary compounds, like GaGeTe, SnSb2Te4, SnBi2Te4, and GeSb2Te5. Many different explanations have been proposed in the literature for the origin of the anomalous broad bands in tellurides, usually located between 119 and 145 cm(-1). They have been attributed to the intrinsic Raman modes of the sample, to oxidation of the sample, to the folding of Brillouin-edge modes onto the zone center, to the existence of a double resonance, like that …
Crystal structure of sinhalite MgAlBO4 under high pressure
We report on high-pressure angle-dispersive X-ray diffraction data up to 27 GPa for natural MgAlBO4 sinhalite mineral and ab initio total energy calculations. The experimental bulk modulus of sinhalite is B-0 = 171(3) GPa with a first-pressure derivative of B-0' = 4.2(3). A comparison with other olivine-type compounds shows that the value for B0 is 27% larger than that of Mg2SiO4 forsterite and 29% smaller than that of Al2BeO4 chrysoberyl. These differences are interpreted, on the basis of our ab initio calculations, in terms of the relative incompressibility of Al-O bonds in AlO6 octahedra (with a calculated bulk modulus of 250(1) GPa) as compared to Mg-O bonds in MgO6 octahedra (with a ca…
Broadband, site selective and time resolved photoluminescence spectroscopic studies of finely size-modulated Y2O3:Eu3+ phosphors synthesized by a complex based precursor solution method
Undoped and Eu3+-doped cubic yttria (Y2O3) nanophosphors of good crystallinity, with selective particle sizes ranging between 6 and 37 nm and showing narrow size distributions, have been synthesized by a complex-based precursor solution method. The systematic size tuning has been evidenced by transmission electron microscopy, X-ray diffraction, and Raman scattering measurements. Furthermore, size-modulated properties of Eu3+ ions have been correlated with the local structure of Eu3+ ion in different sized Y2O3:Eu3+ nanophosphors by means of steady-state and time-resolved site-selective laser spectroscopies. Time-resolved site-selective excitation measurements performed in the 7F0 ¿ 5D0 peak…
Pressure effects on the vibrational properties of alpha-Bi2O3: an experimental and theoretical study
We report an experimental and theoretical high-pressure study of the vibrational properties of synthetic monoclinic bismuth oxide (alpha-Bi2O3), also known as mineral bismite. The comparison of Raman scattering measurements and theoretical lattice-dynamics ab initio calculations is key to understanding the complex vibrational properties of bismite. On one hand, calculations help in the symmetry assignment of phonons and to discover the phonon interactions taking place in this low-symmetry compound, which shows considerable phonon anticrossings; and, on the other hand, measurements help to validate the accuracy of first-principles calculations relating to this compound. We have also studied …
Unveiling the role of the lone electron pair in sesquioxides at high pressure: compressibility of β-Sb2O3
The structural, vibrational and electronic properties of the compressed beta-Sb2O3 polymorph, a.k.a. mineral valentinite, have been investigated in a joint experimental and theoretical study up to 23 GPa. The compressibility of the lattice parameters, unit-cell volume and polyhedral unit volume as well as the behaviour of its Raman- and IR-active modes under compression have been interpreted on the basis of ab initio theoretical simulations. Valentinite shows an unusual compressibility up to 15 GPa with four different pressure ranges, whose critical pressures are 2, 4, and 10 GPa. The pressure dependence of the main structural units, the lack of soft phonons, and the electronic density char…
Experimental and Theoretical Study of SbPO 4 under Compression
SbPO4 is a complex monoclinic layered material characterized by a strong activity of the non-bonding lone electron pair (LEP) of Sb. The strong cation LEP leads to the formation of layers piled up along the a-axis and linked by weak Sb-O electrostatic interactions. In fact, Sb is 4-fold coordination with O similar to what occurs with the P-O coordination, despite the large difference of ionic radii and electronegativity between both elements. Here we report a joint experimental and theoretical study of the structural and vibrational properties of SbPO4 at high pressure. We show that SbPO4 is not only one of the most compressible phosphates but also one of the most compressible compounds of …
Specific features of the electronic structure of III–VI layered semiconductors: recent results on structural and optical measurements under pressure and electronic structure calculations
In this paper we review some recent results on the electronic structure of III-VI layered semiconductors and its dependence under pressure, stressing the specific features that differentiate their behaviour from that of tetrahedrally coordinated semiconductors. We will focus on several unexpected results that have led to changes in the image that was currently accepted a few years ago. Intralayer bond angles change under pressure and the layer thickness remains virtually constant or increases. As a consequence, models based in intra- and inter-layer deformation potentials fail in explaining the low pressure nonlinearity of the band gap. Numerical-atomic-orbital/density-functional-theory ele…
On the ferroelastic nature of the scheelite-to-fergusonite phase transition in orthotungstates and orthomolybdates
Abstract New evidence supporting the ferroelastic nature of the pressure-induced scheelite-to-fergusonite phase transition in ABO 4 orthotungstates and orthomolybdates (A = Ca, Sr, Ba, Pb, Eu and B = W, Mo) has been obtained from the analysis of Raman spectroscopy data. In the studied scheelite-type compounds, one external translational mode of B g symmetry in the scheelite phase softens up to the transition pressure and then becomes a hard A g mode in the fergusonite high-pressure phase. However, other scheelite-type compounds not undergoing the scheelite-to-fergusonite transition do not show softening of the B g mode. The reported results have allowed us to establish a relationship betwee…
Structural and vibrational properties of CdAl2S4 under high pressure: Experimental and theoretical approach
The behavior of defect chalcopyrite CdAl2S4 at high pressures and ambient temperature has been investigated in a joint experimental and theoretical study. High-pressure X-ray diffraction and Raman scattering measurements were complemented with theoretical ab initio calculations. The equation of state and pressure dependences of the structural parameters of CdAl2S4 were determined and compared to those of other AB(2)X(4) ordered-vacancy compounds. The pressure dependence of the Raman-active mode frequencies is reported, as well as the theoretical phonon dispersion curves and phonon density of states at 1 atm. Our measurements suggest that defect chalcopyrite CdAl2S4 undergoes a phase transit…
Ordered helium trapping and bonding in compressed arsenolite: Synthesis ofAs4O6·2He
Compression of arsenolite has been studied from a joint experimental and theoretical point of view. Experiments on this molecular solid at high pressures with different pressure-transmitting media have been interpreted thanks to state-of-the-art ab initio calculations. Our results confirm arsenolite as one of the most compressible minerals and provide evidence for ordered helium trapping above 3 GPa between adamantane-type $\mathrm{A}{\mathrm{s}}_{4}{\mathrm{O}}_{6}$ cages. Our calculations indicate that, at relatively small pressures, helium establishes rather localized structural bonds with arsenic forming a compound with stoichiometry $\mathrm{A}{\mathrm{s}}_{4}{\mathrm{O}}_{6}\ifmmode\c…
Compressibility Systematics of Calcite-Type Borates: An Experimental and Theoretical Structural Study on ABO(3) (A = Al, Sc, Fe, and In)
The structural properties of calcite-type orthoborates ABO(3) (A = Al, Fe, Sc, and In) have been investigated at high pressures up to 32 GPa. They were studied experimentally using synchrotron powder X-ray diffraction and theoretically by means of ab initio total-energy calculations. We found that the calcite-type structure remains stable up to the highest pressure explored in the four studied compounds. Experimental and calculated static geometries (unit-cell parameters and internal coordinates), bulk moduli, and their pressure derivatives are in good agreement. The compressibility along the c axis is roughly three times that along the a axis. Our data clearly indicate that the compressibi…
Band structure of indium selenide investigated by intrinsic photoluminescence under high pressure
This paper reports on photoluminescence experiments in $n$-type indium selenide $(T=300\phantom{\rule{0.3em}{0ex}}\mathrm{K})$ under hydrostatic pressure up to 7 GPa at low and high excitation densities. Photoluminescence measurements at low excitation density exhibit a broad band around the energy of the direct band gap of $\mathrm{InSe}$ and with the same pressure dependence. The reversible increase of its linewidth above $1\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ is associated to a direct-to-indirect band-gap crossover between valence band maxima. The reversible decrease of its intensity above $4\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ is interpreted as evidence of a direct-to-indirect b…
Crystal structure of HgGa2Se4 under compression
We report on high-pressure x-ray diffraction measurements up to 17.2 GPa in mercury digallium selenide (HgGa2Se4). The equation of state and the axial compressibilities for the low-pressure tetragonal phase have been determined and compared to related compounds. HgGa2Se4 exhibits a phase transition on upstroke toward a disordered rock-salt structure beyond 17 GPa, while on downstroke it undergoes a phase transition below 2.1 GPa to a phase that could be assigned to a metastable zinc-blende structure with a total cation-vacancy disorder. Thermal annealing at low- and high-pressure shows that kinetics plays an important role on pressure-driven transitions.
Negative pressures in CaWO4 nanocrystals
Tetragonal scheelite-type CaWO4 nanocrystals recently prepared by a hydrothermal method show an enhancement of its structural symmetry with the decrease in nanocrystal size. The analysis of the volume dependence of the structural parameters in CaWO4 nanocrystals with the help of ab initio total-energy calculations shows that the enhancement of the symmetry in the scheelite-type nanocrystals is a consequence of the negative pressure exerted on the nanocrystals; i.e., the nanocrystals are under tension. Besides, the behavior of the structural parameters in CaWO4 nanocrystals for sizes below 10 nm suggests an onset of a scheelite-to-zircon phase transformation in good agreement with the predic…
Experimental and Theoretical Investigations on Structural and Vibrational Properties of Melilite-Type Sr2ZnGe2O7 at High Pressure and Delineation of a High-Pressure Monoclinic Phase.
We report a combined experimental and theoretical study of melilite-type germanate, Sr2ZnGe2O7, under compression. In situ high-pressure X-ray diffraction and Raman scattering measurements up to 22 GPa were complemented with first-principles theoretical calculations of structural and lattice dynamics properties. Our experiments show that the tetragonal structure of Sr2ZnGe2O7 at ambient conditions transforms reversibly to a monoclinic phase above 12.2 Gpa with similar to 1% volume drop at the phase transition pressure. Density functional calculations indicate the transition pressure at, similar to 13 GPa, which agrees well with the experimental value. The structure of the high-pressure mono…
Effects of high-pressure on the structural, vibrational, and electronic properties of monazite-type PbCrO4
We have performed an experimental study of the crystal structure, lattice dynamics, and optical properties of PbCrO 4 (the mineral crocoite) at ambient and high pressures. In particular, the crystal structure, Raman-active phonons, and electronic band gap have been accurately determined. X-ray-diffraction, Raman, and optical absorption experiments have allowed us also to completely characterize two pressure-induced structural phase transitions. The first transition is from a monoclinic structure to another monoclinic structure. It maintains the symmetry of the crystal but has important consequences in the physical properties; among others, a band-gap collapse is induced. The second one invo…
Pressure-induced structural phase transitions in materials and earth sciences
Pressure is an important thermodynamic parameter since it allows an increase of matter density by reducing volume. The reduction of volume by applying high pressures leads to an overall decrease of interatomic and intermolecular distances that allows exploring in detail atomic and molecular interactions. Therefore, high-pressure research has improved our fundamental understanding of these interactions in solids, liquids and gasses. The study of the structure of matter under compression is a rapid developing field that is receiving increasing attention especially due to continuous experimental and theoretical developments. In this article, we give a brief description of the experimental and …
Structural and vibrational study of pseudocubic CdIn2Se4 under compression
We report a comprehensive experimental and theoretical study of the structural and vibrational properties of a-CdIn2Se4 under compression. Angle-dispersive synchrotron X-ray diffraction and Raman spectroscopy evidence that this ordered-vacancy compound with pseudocubic structure undergoes a phase transition (7 GPa) toward a disordered rocksalt structure as observed in many other ordered-vacancy compounds. The equation of state and the pressure dependence of the Raman-active modes of this semiconductor have been determined and compared both to ab initio total energy and lattice dynamics calculations and to related compounds. Interestingly, on decreasing pressure, at similar to 2 GPa, CdIn2Se…
Experimental and Theoretical Studies on alfa-In2Se3 at High Pressure
[EN] alpha(R)-In2Se3 has been experimentally and theoretically studied under compression at room temperature by means of X-ray diffraction and Raman scattering measurements as well as by ab initio total-energy and lattice-dynamics calculations. Our study has confirmed the alpha (R3m) -> beta' (C2/m) ? beta (R (3) over barm) sequence of pressure-induced phase transitions and has allowed us to understand the mechanism of the monoclinic C2/m to rhombohedral R (3) over barm phase transition. The monoclinic C2/m phase enhances its symmetry gradually until a complete transformation to the rhombohedral R (3) over barm structure is attained above 10-12 GPa. The second-order character of this transi…
Neutron irradiation defects in gallium sulfide: Optical absorption measurements
Gallium sulfide single crystals have been irradiated with different thermal neutron doses. Defects introduced by neutron irradiation turn out to be optically active, giving rise to absorption bands with energies ranging from 1.2 to 3.2 eV. Bands lying in the band-gap exhibit Gaussian shape. Their energies and widths are independent of the irradiation dose, but their intensities are proportional to it. Thermal annealing is completed in two stages, ending at around 500 and 720 K, respectively. Centers responsible for the absorption bands are proposed to be gallium-vacancy-galliuminterstitial complexes in which the distance between the vacancy (acceptor) and the interstitial (donor) determines…