Study of the bandgap renormalization in Ga-doped ZnO films by means of optical absorption under high pressure and photoelectron spectroscopy

Abstract In this paper we investigate the band gap renormalization in heavily Ga-doped ZnO thin films deposited by pulsed laser deposition on C -plane sapphire and mica substrates. Thin films were studied by ultraviolet photoelectron spectroscopy and also by optical measurements under high pressure. The Fermi-level shift, as obtained from ultraviolet photoelectron experiments, exhibits a relatively small and positive shift (about 0.3 eV) with respect to the valence band for increasing electron concentrations up to 1021 cm−3. The optical gap exhibits a much larger increase (0.6 eV) for the same concentration range. Absorption measurements under pressure show that the pressure coefficient of …

Pressure-dependent modifications in the optical and electronic properties of Fe(IO3)3: the role of Fe 3d and I 5p lone–pair electrons

We have determined by means of optical-absorption experiments that Fe(IO3)3 is an indirect band-gap material with a band-gap energy of 2.1 eV. This makes this compound the iodate with the smallest band gap. We also found that under compression the band-gap energy has an unusual non-linear pressure dependence, which is followed by an abrupt and discontinuous decrease of the band gap at 24 GPa. The observed behavior is explained by means of density-functional calculations, which show that the behavior of the band gap is governed by the combined influence of Fe 4d and I 5p lone pair electrons. In addition, the abrupt decrease of the band-gap energy at 24 GPa is a consequence of a first-order s…

Investigation of acceptor levels and hole scattering mechanisms in p-gallium selenide by means of transport measurements under pressure

The effect of pressure on acceptor levels and hole scattering mechanisms in p-GaSe is investigated through Hall effect and resistivity measurements under quasi-hydrostatic conditions up to 4 GPa. The pressure dependence of the hole concentration is interpreted through a carrier statistics equation with a single (nitrogen) or double (tin) acceptor whose ionization energies decrease under pressure due to the dielectric constant increase. The pressure effect on the hole mobility is also accounted for by considering the pressure dependencies of both the phonon frequencies and the hole-phonon coupling constants involved in the scattering rates.

Compressibility and structural behavior of pure and Fe-doped SnO2 nanocrystals

We have performed high-pressure synchrotron X-ray diffraction experiments on nanoparticles of pure tin dioxide (particle size ~30nm) and 10 mol % Fe-doped tin dioxide (particle size ~18nm). The structural behavior of undoped tin dioxide nanoparticles has been studied up to 32 GPa, while the Fe-doped tin dioxide nanoparticles have been studied only up to 19 GPa. We have found that both samples present at ~13 GPa a second-order structural phase transition from the ambient pressure tetragonal rutile-type structure (P42/mnm) to an orthorhombic CaCl2-type structure (space group Pnnm). No phase coexistence was observed for this transition. Additionally, pure SnO2 presents a phase transition to a …

Lattice dynamics of CuAlO2 under high pressure fromab initio calculations

The density functional perturbation theory is employed to study the vibrational properties of CuAlO 2 under pressure. The calculations are preformed using the pseudopotential wave method and the local density approximation for the exchange-correlation (XC) potential. The d electrons of Cu are treated as valence states. We present the phonon dispersion curves. Our results are in good agreement with the available experimental Raman scattering experiments. Ab initio calculations show the presence of a dynamical instability, possibly related with the experimentally observed phase transition.

High-pressure electronic structure and phase transitions in monoclinic InSe: X-ray diffraction, Raman spectroscopy, and density functional theory

We have studied the crystal and electronic structure of monoclinic (MC) InSe under pressure finding a reversible phase transition to a ${\mathrm{Hg}}_{2}{\mathrm{Cl}}_{2}$-like tetragonal phase. The pressure evolution of the crystal structure was investigated by angle-dispersive x-ray diffraction and Raman spectroscopy in a diamond-anvil cell up to $30\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$. From the diffraction experiments, we deduced that MC InSe becomes gradually more symmetric under pressure, transforming the crystal structure into a tetragonal one at $19.4\ifmmode\pm\else\textpm\fi{}0.5\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$. This phase transition occurs without any volume change. Ra…

Photoconductivity and photovoltaic effect in indium selenide

Transport and phototransport properties of crystalline indium monoselenide (InSe) doped with a variety of elements are reported. Measured mobilities, lifetimes, and effective diffusion lengths of photoexcited carriers are used to interpret electrical and photovoltaic properties of several different structures. These include p‐n junctions, bismuth/p‐type InSe, platinum/n‐type InSe, and indium tin oxyde (ITO)/p‐type InSe. External solar efficiencies of the best devices are between 5% and 6%. The influence on the efficiency of the various parameters is evaluated, and ways of improvement are discussed.

Investigation of conduction-band structure, electron-scattering mechanisms, and phase transitions in indium selenide by means of transport measurements under pressure

In this work we report on Hall effect, resistivity and thermopower measurements in n-type indium selenide at room temperature under either hydrostatic and quasi-hydrostatic pressure. Up to 40 kbar (= 4 GPa), the decrease of carrier concentration as the pressure increases is explained through the existence of a subsidiary minimum in the conduction band. This minimum shifts towards lower energies under pressure, with a pressure coefficient of about -105 meV/GPa, and its related impurity level traps electrons as it reaches the band gap and approaches the Fermi level. The pressure value at which the electron trapping starts is shown to depend on the electron concentration at ambient pressure an…

High-pressure study of the behavior of mineral barite by x-ray diffraction

In this paper, we report the angle-dispersive x-ray diffraction data of barite, BaSO 4, measured in a diamond-anvil cell up to a pressure of 48 GPa, using three different fluid pressure-transmitting media (methanol-ethanol mixture, silicone oil, and He). Our results show that BaSO 4 exhibits a phase transition at pressures that range from 15 to 27 GPa, depending on the pressure media used. This indicates that nonhydrostatic stresses have a crucial role in the high-pressure behavior of this compound. The new high-pressure (HP) phase has been solved and refined from powder data, having an orthorhombic P2 12 12 1 structure. The pressure dependence of the structural parameters of both room- and…

Nonlinear pressure dependence of the direct band gap in adamantine ordered-vacancy compounds

A strong nonlinear pressure dependence of the optical absorption edge has been measured in defect chalcopyrites CdGa{sub 2}Se{sub 4} and HgGa{sub 2}Se{sub 4}. The behavior is due to the nonlinear pressure dependence of the direct band-gap energy in these compounds as confirmed by ab initio calculations. Our calculations for CdGa{sub 2}Se{sub 4}, HgGa{sub 2}Se{sub 4} and monoclinic {beta}-Ga{sub 2}Se{sub 3} provide evidence that the nonlinear pressure dependence of the direct band-gap energy is a general feature of adamantine ordered-vacancy compounds irrespective of their composition and crystalline structure. The nonlinear behavior is due to a conduction band anticrossing at the {Gamma} po…

Nanotexturing To Enhance Photoluminescent Response of Atomically Thin Indium Selenide with Highly Tunable Band Gap.

Brotons-Gisbert, Mauro et al.

Optical absorption of divalent metal tungstates: Correlation between the band-gap energy and the cation ionic radius

We have carried out optical-absorption and reflectance measurements at room temperature in single crystals of AWO4 tungstates (A = Ba, Ca, Cd, Cu, Pb, Sr, and Zn). From the experimental results their band-gap energy has been determined to be 5.26 eV (BaWO4), 5.08 eV (SrWO4), 4.94 eV (CaWO4), 4.15 eV (CdWO4), 3.9-4.4 eV (ZnWO4), 3.8-4.2 eV (PbWO4), and 2.3 eV (CuWO4). The results are discussed in terms of the electronic structure of the studied tungstates. It has been found that those compounds where only the s electron states of the A2+ cation hybridize with the O 2p and W 5d states (e.g BaWO4) have larger band-gap energies than those where also p, d, and f states of the A2+ cation contribu…

Dynamics of thermally induced optical nonlinearity in GaSe thin slabs

A study of the nonlinear effects shown by thin slabs of GaSe metaled with Au is presented.

Single crystal EXAFS at high pressure

Abstract We present a new technique for structure characterization under high pressure conditions. The use of an undulator beam of the third-generation ESRF source of synchrotron radiation has enabled the first single crystal EXAFS experiments at high pressure using a diamond anvil cell as pressure generator. Taking advantage of the linear polarization of X-rays the technique becomes an orientation-selective probe of the local structure of materials. We describe the principle of the technique and some applications.

Tuning the band gap of PbCrO4 through high-pressure: Evidence of wide-to-narrow semiconductor transitions

The electronic transport properties and optical properties of lead(II) chromate (PbCrO4) have been studied at high pressure by means of resistivity, Hall-effect, and optical-absorption measurements. Band-structure first-principle calculations have been also performed. We found that the low-pressure phase is a direct band-gap semiconductor (Eg = 2.3 eV) that shows a high resistivity. At 3.5 GPa, associated to a structural phase transition, a band-gap collapse takes place, becoming Eg = 1.8 eV. At the same pressure the resistivity suddenly decreases due to an increase of the carrier concentration. In the HP phase, PbCrO4 behaves as an n-type semiconductor, with a donor level probably associat…

Optical emission fromSiO2-embedded silicon nanocrystals: A high-pressure Raman and photoluminescence study

We investigate the optical properties of high-quality Si nanocrystals $(\mathrm{NCs})/\mathrm{Si}{\mathrm{O}}_{2}$ multilayers under high hydrostatic pressure with Raman scattering and photoluminescence (PL) measurements. The aim of our study is to shed light on the origin of the optical emission of the Si $\mathrm{NCs}/\mathrm{Si}{\mathrm{O}}_{2}$. The Si NCs were produced by chemical-vapor deposition of Si-rich oxynitride $(\mathrm{SRON})/\mathrm{Si}{\mathrm{O}}_{2}$ multilayers with 5- and 4-nm SRON layer thicknesses on fused silica substrates and subsequent annealing at 1150 \ifmmode^\circ\else\textdegree\fi{}C, which resulted in the precipitation of Si NCs with an average size of 4.1 a…

Fibre Bragg gratings tuned and chirped using magnetic fields

The authors report on the use of magnetic fields in conjunction with magnetostrictive materials for tuning and chirping optical fibre Bragg gratings. The Bragg wavelength shifts as a consequence of the strain induced in the fibre by a magnetostrictive rod when a magnetic field is applied. A tuning range of 1.1 nm has been achieved by a magnetic field of 103 mT and the grating has been chirped by applying non-uniform magnetic fields.

Natural optical anisotropy of h-BN: Highest giant birefringence in a bulk crystal through the mid-infrared to ultraviolet range

The giant birefringence of layered h-BN was demonstrated by analyzing the interference patterns in reflectance and transmittance measurements in the mid-infrared to the deep ultraviolet energy range. The refractive index for polarization perpendicular to the c axis is much higher than the refractive index for polarization parallel to the c axis, and it displays a strong increase in the ultraviolet range that is attributed to the huge excitonic effects arising from the unique electronic structure of h-BN. Thus, h-BN is shown to exhibit a giant negative birefringence that ranges from -0.7 in the visible to -2 in the deep ultraviolet close to the band gap. The electronic dielectric constants f…

Electronic structure of CuAlO2 and CuScO2 delafossites under pressure

The electronic structure of CuAlO 2 and CuScO 2 delafossites is investigated by means of optical absorption measurements under pressure and ab initio band structure calculations. Measurements are carried out on CuAlO 2 monocrystals and pulsed laser deposited CuAlO 2 and CuScO 2 thin films up to 20 GPa. CuAlO 2 is an indirect semiconductor that is stable in the pressure range explored here. The pressure coefficients of the indirect and direct gaps are found to be 15 meV/GPa and 2 meV/GPa respectively. CuScO 2 is a direct semiconductor and the pressure coefficient of the excitonic peak energy is -5.5 meV/GPa. Two reversible phase transitions are observed in CuScO 2 . At 13 GPa the delafossite…

Monazite-type SrCrO4 under compression

We report a high-pressure study of monoclinic monazite-type SrCrO4 up to 26 GPa. Therein we combined x-ray diffraction, Raman and optical-absorption measurements with ab initio calculations, to find a pressure-induced structural phase transition of SrCrO4 near 8-9 GPa. Evidence of a second phase transition was observed at 10-13 GPa. The crystal structures of the high-pressure phases were assigned to the tetragonal scheelite-type and monoclinic AgMnO4-type structures. Both transitions produce drastic changes in the electronic band gap and phonon spectrum of SrCrO4. We determined the pressure evolution of the band gap for the low-pressure and high-pressure phases as well as the frequencies an…

Study of the Secondary Electron Yield in Dielectrics Using Equivalent Circuital Models

[EN] Secondary electron emission has an important role on the triggering of the multipactor effect; therefore, its study and characterization are essential in radio-frequency waveguide applications. In this paper, we propose a theoretical model, based on equivalent circuit models, to properly understand charging and discharging processes that occur in dielectric samples under electron irradiation for secondary electron emission characterization. Experimental results obtained for Pt, Si, GaS, and Teflon samples are presented to verify the accuracy of the proposed model. Good agreement between theory and experiments has been found.

High-pressure optical absorption in InN: Electron density dependence in the wurtzite phase and reevaluation of the indirect band gap of rocksalt InN

We report on high-pressure optical absorption measurements on InN epilayers with a range of free-electron concentrations (5×1017–1.6×1019 cm−3) to investigate the effect of free carriers on the pressure coefficient of the optical band gap of wurtzite InN. With increasing carrier concentration, we observe a decrease of the absolute value of the optical band gap pressure coefficient of wurtzite InN. An analysis of our data based on the k·p model allows us to obtain a pressure coefficient of 32 meV/GPa for the fundamental band gap of intrinsic wurtzite InN. Optical absorption measurements on a 5.7-μm-thick InN epilayer at pressures above the wurtzite-to-rocksalt transition have allowed us to o…

Investigation of lattice dynamical and dielectric properties of MgO under high pressure by means of mid- and far-infrared spectroscopy.

We investigate the lattice dynamical and dielectric properties of MgO single crystals and powders by measurements in the mid- and far-infrared frequency region under high pressures, ranging up to 21.7 GPa. The shift of the restrahlen region is used to determine the pressure dependence of the transverse and longitudinal optical modes. The analysis of the refractive index in the mid- and far-infrared region allowed us to obtain the pressure behavior of the static and electronic dielectric constants. The transverse effective charge slowly decreases under high pressure, reflecting the stability of MgO. As a consequence, the pressure dependence of the static and electronic dielectric constants i…

Photoluminescence in silicon-doped n-indium selenide

Photoluminescence results on silicon-doped indium selenide are reported. The effect of temperature and excitation intensity is studied. At low temperature, free and neutral donor bound exciton peaks are observed. Above 100 K only free exciton and band-to-band photoluminescence is detected. In order to give account of the full lineshape as a function of the absorption coefficient, the Urbach absorption tail of InSe is measured. Transmission and reflection photoluminescence spectra are also compared in order to study the effect of carrier diffusion. The shape of the photoluminescence spectrum can be accounted for through a direct gap model.

High-pressure x-ray diffraction andab initiostudy ofNi2Mo3N,Pd2Mo3N,Pt2Mo3N,Co3Mo3N, andFe3Mo3N: Two families of ultra-incompressible bimetallic interstitial nitrides

We have studied by means of high-pressure x-ray diffraction the structural stability of ${\text{Ni}}_{2}{\text{Mo}}_{3}\text{N}$, ${\text{Co}}_{3}{\text{Mo}}_{3}\text{N}$, and ${\text{Fe}}_{3}{\text{Mo}}_{3}\text{N}$. We also report ab initio computing modeling of the high-pressure properties of these compounds, ${\text{Pd}}_{2}{\text{Mo}}_{3}\text{N}$ and ${\text{Pt}}_{2}{\text{Mo}}_{3}\text{N}$. We have found that the nitrides remain stable in the ambient-pressure cubic structure at least up to 50 GPa and determined their equation of state. All of them have a bulk modulus larger than 300 GPa. Single-crystal elastic constants have been calculated in order to quantify the stiffness of the i…

Numerical analysis of thermally induced optical nonlinearity in GaSe layered crystal

A numerical approach to studying thermally induced optical nonlinearity in semiconductors is presented. A transient finite difference algorithm is applied to solve the thermal diffusion equation coupled with the nonlinear absorbance-transmittance of Au/GaSe/Au samples with an applied electric field. The presented analysis can deal with any arbitrary axisymmetric dependence of the input power over the sample and external electric field, and provides information about the steady state and transitory effects in the transmittance.

Crystal symmetry and pressure effects on the valence band structure ofγ-InSe andε-GaSe: Transport measurements and electronic structure calculations

This paper reports on Hall effect and resistivity measurements under high pressure up to 3--4 GPa in $p$-type $\ensuremath{\gamma}$-indium selenide (InSe) (doped with As, Cd, or Zn) and $\ensuremath{\epsilon}$-gallium selenide (GaSe) (doped with N or Sn). The pressure behavior of the hole concentration and mobility exhibits dramatic differences between the two layered compounds. While the hole concentration and mobility increase moderately and monotonously in $\ensuremath{\epsilon}$-GaSe, a large increase of the hole concentration near 0.8 GPa and a large continuous increase of the hole mobility, which doubled its ambient pressure value by 3.2 GPa, is observed in $\ensuremath{\gamma}$-InSe.…

Band gap of corundumlike α−Ga2O3 determined by absorption and ellipsometry

The electronic structure near the band gap of the corundumlike $\ensuremath{\alpha}$ phase of ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ has been investigated by means of optical absorption and spectroscopic ellipsometry measurements in the ultraviolet (UV) range (400--190 nm). The absorption coefficient in the UV region and the imaginary part of the dielectric function exhibit two prominent absorption thresholds with wide but well-defined structures at 5.6 and 6.3 eV which have been ascribed to allowed direct transitions from crystal-field split valence bands to the conduction band. Excitonic effects with large Gaussian broadening are taken into account through the Elliott-Toyozawa model, which y…

High-Pressure Softening of the Out-of-Plane A2u(Transverse-Optic) Mode of Hexagonal Boron Nitride Induced by Dynamical Buckling

We investigate the highly anisotropic behavior of the in-plane and out-of-plane infrared-active phonons of hexagonal boron nitride by means of infrared reflectivity and absorption measurements under high pressure. Infrared reflectivity spectra at normal incidence on high-quality single crystals show strict fulfillment of selection rules and an unusually long E1u[transverse-optic (TO)] phonon lifetime. Accurate values of the dielectric constants at ambient pressure ϵ0= 6.96, ϵ∞= 4.95, ϵ 0= 3.37, and ϵ∞ = 2.84 have been determined from fits to the reflectivity spectra. The out-of-plane A2u phonon reflectivity band is revealed in measurements on an inclined facet, and absorption measurements a…

Observation of the Cinnabar Phase in ZnSe at High Pressure

In this paper we describe the results of an energy dispersive X-ray diffraction experiment carried out in the ZnSe 1 m x Te x alloy and pure ZnSe under high pressure. In the downstroke the cinnabar phase is observed between the rocksalt and the zincblende phases. The analysis of the whole series of compositions ( x =0, 0.05, 0.1 and 0.2) enables us to establish its lattice parameters in ZnSe ( a =3.785 + and c =8.844 + at 10.5 GPa). The X-ray diffraction pattern simulation suggests that the internal parameters u and v are close to 0.5, indicating that the cinnabar phase in ZnSe is similar to that observed in GaAs and ZnTe. The cinnabar's stability range decreases as the Te content is reduce…

Infrared study of α–SiO2 single crystal under high pressure

We have measured high pressure α-quartz reflectance spectra in the mid infrared. We used single crystals, taking full profit of polarization. The quality of the spectra allows fitting the reflectance spectra. We have characterized the pressure evolution of E and A2 modes with increased precision, even in the spectral regions where they overlap. In addition, we have determined the TO-LO splitting of each mode. Some of the A2 modes show dramatic pressure variations of the LO-TO splitting, which cannot be explained only by changes in length and ionicity of individual bonds, requiring a new mechanism. We suggest that rotation of the SiO4 tetrahedra plays a fundamental role. We have also determi…

Shallow-donor impurities in indium selenide investigated by means of far-infrared spectroscopy.

Shallow impurities in n-type indium selenide (InSe) have been investigated by means of Fourier-transform spectroscopy in the far-infrared region. Three electric dipole transitions have been identified: 1s-2${\mathit{p}}_{\ifmmode\pm\else\textpm\fi{}}$, 1s-2${\mathit{p}}_{0}$, and 1s-3${\mathit{p}}_{\ifmmode\pm\else\textpm\fi{}}$, corresponding to electrons bound to native donors and tin-, silicon-, and chlorine-related donors, whose ionization energies (17.6, 18.1, 18.8, and 19 meV, respectively) have been determined through the Guerlach-Pollmann model. That model was also used to calculate the oscillator strengths of those dipole transitions, and then to estimate the shallow-donor concentr…

The application of the photoacoustic transmittance oscillations for determining elastic constants in gallium and indium selenides

Transmittance periodic oscillations are observed in GaSe and InSe on excitation with optical pulses. Such oscillations are explained in terms of photoacoustic generation of dilatational waves, which become resonant within the crystal. Spectral analysis of those oscillations in samples of different thickness has led to an accurate determination of the longitudinal acoustic‐wave velocity along the crystallographic axis c. Julio.Pellicer@uv.es ; Chantal.Ferrer@uv.es ; Vicente.Munoz@uv.es

Tetrahedral versus octahedral Mn site coordination in wurtzite and rocksalt Zn1−xMnxO investigated by means of XAS experiments under high pressure

Abstract We present the results of x-ray absorption measurements carried out in Zn 1− x Mn x O thin films under high pressure. The Mn environment remains essentially the same for nominal Mn concentrations given by x = 0.05 , 0.1, 0.15 and 0.25. Both the XANES (X-ray Absorption Near Edge Structure) and EXAFS (Extended X-ray Absorption Fine Structure) indicate that Mn occupies the Zn site, being surrounded by four oxygen atoms at 2.02±0.01 A. The substitutional hypothesis is reinforced by comparing the differences between the ambient (wurtzite) and high pressure (rocksalt) spectra, which correspond to tetrahedral and octahedral Mn environments.

Compressibility and Structural Stability of Nanocrystalline TiO2 Anatase Synthesized from Freeze-Dried Precursors

The high-pressure structural behavior of 30 nm nanoparticles of anatase TiO2 was studied under hydrostatic and quasi-hydrostatic conditions up to 25 GPa. We found that the structural sequence is not sensitive to the use of different pressure transmitting media. Anatase-type nanoparticles exhibit a phase transition beyond 12 GPa toward a baddeleyite-type structure. Under decompression this phase transition is irreversible, and a metastable columbite-type structure is recovered at ambient conditions. The bulk modulus of anatase-type nanoparticles was determined confirming that nanoparticles of TiO2 are more compressible than bulk TiO2. Similar conclusions were obtained after the determination…

Pressure and temperature dependence of the band-gap in CdTe

In this paper we report on isothermal compression measurements (up to 5 GPa and 500 K) of the optical absorption edge of 1 μm epitaxial layers of CdTe growth by metalorganic chemical vapor deposition (MOCVD) on GaS substrates. The isothermal blue shift under pressure of the direct energy gap (Γ v 15 → Γ c 1 ) in the zinc-blende phase is about 7.1 × 10 -2 eV GPa -1 and is found to be independent of temperature within the experimental errors. The isobaric red shift in the stability range of the zinc-blende phase is about -3.76 × 10 -4 eV K -1 . Regarding the phase transitions, no discontinuity in the energy gap has been found in the narrow pressure range where the cinnabar phase can be presen…

High-pressure study of substrate material ScAlMgO4

We report on the structural properties of ScAlMgO4 studied under quasi-hydrostatic pressure using synchrotron high-pressure x-ray diffraction up to 40 GPa. We also report on single-crystal studies of ScAlMgO4 performed at 300 K and 100 K. We found that the low-pressure phase remains stable up to 24 GPa. At 28 GPa, we detected a reversible phase transformation. The high-pressure phase is assigned to a monoclinic distortion of the low-pressure phase. No additional phase transition is observed up to 40 GPa. In addition, the equation of state, compressibility tensor, and thermal expansion coefficients of ScAlMgO4 are determined. The bulk modulus of ScAlMgO4 is found to be 143(8) GPa, with a str…

Theoretical and experimental study of CaWO4 and SrWO4 under pressure

Abstract In this paper, we combine a theoretical study of the structural phases of CaWO 4 and SrWO 4 under high pressure along with the results of angle-dispersive X-ray diffraction (ADXRD) and X-ray absorption near-edge structure (XANES) measurements of both tungstates up to approximately 20 GPa. The theoretical study was performed within the ab initio framework of the density functional theory (DFT) using a plane-wave basis set and the pseudopotential scheme, with the generalized gradient approximation (GGA) for the exchange and correlation contribution to the energy. Under normal conditions, CaWO 4 and SrWO 4 crystallize in the scheelite structure. Our results show that in a hydrostatic …

Optical, X-ray absorption and photoelectron spectroscopy investigation of the Co site configuration in Zn1−xCoxO films prepared by pulsed laser deposition

Abstract In this paper, we investigate the Co site configuration in Zn1−xCoxO thin films by means of different spectroscopic techniques. Thin films were prepared by pulsed laser deposition with Co proportion from 1% to 30%. The Co 2p doublet observed in the X-ray photoelectron spectra exhibits the spin–orbit splitting and shake-up satellites typical of Co+2 ionization states. X-ray absorption spectra at the Co K-edge, taken in fluorescence mode, unambiguously show that Co atoms are in tetrahedral configuration substituting for Zn over the whole composition range. Optical absorption spectra provide further evidence of the tetrahedral coordination of Co cations, both through the internal tran…

Tuning And Chirping Fiber Bragg Gratings By A Magnetic Field

Variation of the optical absorption edge in AgGaS2 single crystals at high pressure

In this paper the optical absorption edge of AgGaS 2 is measured as a function of pressure up to 26 GPa in order to verify the effect of the three phases transitions occurring in that pressure domain. The direct energy gap increases linearly with pressure at the rate of about 4.0 x 10 -2 eV GPa -1 up to 10.2 GPa. The absence of any discontinuity in the energy gap in the pressure range of 4.2-10.2 GPa confirms that the volume change, in the chalcopirite to monoclinic second-order transition, if it exists, is very small. When the pressure is raised above 10.2 GPa, the energy gap drops suddenly by about 1.1 eV and the spectral form of the absorption coefficient is typical of semiconductors wit…

Direct to Indirect Crossover in III-VI Layered Compounds and Alloys under Pressure

The pressure dependence of the optical absorption edge of In1± xGaxSe (0 < x < 0.2) and GaTe has been investigated in order to determine the direct to indirect crossover pressure and the energy difference between the absolute and subsidiary minima of the conduction band at ambient pressure. In the In1± xGaxSe alloy, the crossover pressure decreases with increasing Ga proportion. For InSe, from the extrapolation to x = 0 the band crossover is found to occur at 4.3 GPa and the subsidiary minimum of the conduction band is located, at ambient pressure, (0.32 0.02) eV above the absolute minimum. In addition, the energy difference between the conduction band minima is shown to decrease linearly w…

Band-to-Band and Band-to-Acceptor Photoluminescence Studies in InSe under Pressure

We report on photoluminescence (PL) measurements under pressure on p-type N-doped InSe at 10 K and on n-type Si-doped InSe at room temperature. Low-temperature PL of N-doped InSe is dominated by a band-to-acceptor peak. From the pressure dependence of the ionization energy of the N related shallow acceptor, the pressure change of the hole effective mass is estimated through the Gerlach-Pollmann model for hydrogenic levels in uniaxial crystals and discussed in the framework of a k p model. Room temperature PL in Si-doped InSe is dominated by a band-to-band peak exhibiting a pressure shift in agreement with previous works. This PL peak has been measured up to 7 GPa and a steep reversible decr…

Formation of nanostructures in Eu3+ doped glass-ceramics: an XAS study.

We describe the results of x-ray absorption experiments carried out to deduce structural and chemical information in Eu(3+) doped, transparent, oxyfluoride glass and nanostructured glass-ceramic samples. The spectra were measured at the Pb and Eu-L(III) edges. The Eu environment in the glass samples is observed to be similar to that of EuF(3). Complementary x-ray diffraction experiments show that thermal annealing creates β-PbF(2) type nanocrystals. X-ray absorption indicates that Eu ions act as seeds in the nanocrystal formation. There is evidence of interstitial fluorine atoms around Eu ions as well as Eu dimers. X-ray absorption at the Pb-L(III) edge shows that after the thermal treatmen…

Effects of pressure and temperature on the dielectric constant of GaS, GaSe, and InSe:  Role of the electronic contribution

In this work we report on direct measurements of the temperature and pressure dependences of the low-frequency dielectric constant along c axis $({\ensuremath{\varepsilon}}_{\ensuremath{\parallel}})$ of GaS, GaSe, and InSe. The temperature dependence of both the ordinary and extraordinary refractive indexes is also presented. A large increase of ${\ensuremath{\varepsilon}}_{\ensuremath{\parallel}}$ under pressure has been observed. In the framework of a rigid ion model, the lattice contribution to ${\ensuremath{\varepsilon}}_{\ensuremath{\parallel}}$ is shown to increase slightly under pressure, due to the change of the angle between the anion-cation bond and the layer plane. Consequently, …

High-pressure x-ray-absorption study of GaSe

The III-VI layered semiconductor InSe has been studied by high-pressure single crystal x-ray absorption spectroscopy up to a maximum pressure of 14 GPa. The In-Se distance has been measured in both the low- pressure layered phase and the high-pressure NaCl phase. The bond compressibility in the layered phase is lower than the ``a'' crystallographic parameter compressibility, which implies an increase of the angle between the In-Se bond and the layer plane. Under plausible hypothesis, a description of the evolution of the whole structure with pressure is given. In particular, the intralayer distance is observed to increase with increasing pressure. A plausible precursor defect and a simple m…

Thin film growth and band lineup of In2O3 on the layered semiconductor InSe

Thin films of the transparent conducting oxide In2O3 have been prepared in ultrahigh vacuum by reactive evaporation of indium. X-ray diffraction, optical, and electrical measurements were used to characterize properties of films deposited on transparent insulating mica substrates under variation of the oxygen pressure. Photoelectron spectroscopy was used to investigate in situ the interface formation between In2O3 and the layered semiconductor InSe. For thick In2O3 films a work function of φ = 4.3 eV and a surface Fermi level position of EF−EV = 3.0 eV is determined, giving an ionization potential IP = 7.3 eV and an electron affinity χ = 3.7 eV. The interface exhibits a type I band alignmen…

Lattice and electronic contributions to the refractive index of CuWO4

We report an investigation of the refractive index dispersion and anisotropy in CuWO4 by means of interference measurements in two extinction directions from mid infrared to the visible region of the energy spectrum. The analysis of the refractive index dispersion yields ϵ(∞) = 4.5(1) for light polarization parallel to the c-axis and ϵ(∞) = 5.3(1) with respect to the other extinction axis. In addition, we report reflectance measurements carried out from the far infrared to the near ultraviolet to study the lattice and electronic contributions to the refractive index of CuWO4. We have determined the wavenumbers of nine infrared active lattice modes and compared them with previous ab initio c…

Experimental and Theoretical Study of Bi2O2Se Under Compression

[EN] We report a joint experimental and theoretical study of the structural, vibrational, elastic, optical, and electronic properties of the layered high-mobility semiconductor Bi2O2Se at high pressure. A good agreement between experiments and ab initio calculations is observed for the equation of state, the pressure coefficients of the Raman-active modes and the bandgap of the material. In particular, a detailed description of the vibrational properties is provided. Unlike other Sillen-type compounds which undergo a tetragonal to collapsed tetragonal pressure-induced phase transition at relatively low pressures, Bi2O2Se shows a remarkable structural stability up to 30 GPa; however, our res…

Cinnabar phase in ZnSe at high pressure

We have performed an energy-dispersive x-ray-diffraction experiment on ${\mathrm{ZnSe}}_{1\ensuremath{-}x}{\mathrm{Te}}_{x}$ alloys under high pressure with $x=0,$ 0.05, 0.1, and 0.2. In the downstroke a hexagonal phase appears. We suggest that this phase is cinnabar, whose stability range decreases as the Te content is reduced. The analysis of the whole series of compositions enables us to establish its lattice parameters in ZnSe $(a=3.785\AA{}$ and $c=8.844\AA{}$ at 10.5 GPa). The extinction of some diffraction peaks also suggests that the internal parameters u and $v$ are close to 0.5, indicating that the cinnabar phase in ZnSe is similar to that observed in GaAs and ZnTe.

Precursor effects of the Rhombohedral-to-Cubic Phase Transition in Indium Selenide

We report on the observation of precursor effects of the rhombohedral-to-cubic phase transition in Indium Selenide (InSe) with several experimental techniques. The pressure at which these precursor defects are first observed depends on the sensitivity of the experimental technique. In transport measurements, which are very sensitive to low defect concentrations, precursor effects are observed 5 to 6 GPa below the phase transition pressure whereas in X-ray diffraction measurements precursor effects are only observed 2 GPa below the phase transition pressure. We report optical absorption measurements, in which the precursor effects are shown by the growth and propagation of dark linear defect…

The effect of quantum size confinement on the optical properties of PbSe nanocrystals as a function of temperature and hydrostatic pressure

A study based on photoluminescence and absorption measurements as a function of temperature and pressure for PbSe nanocrystals with sizes in the range 3–13 nm reveals the influence of size quantum confinement on the observed variation. In the case of the temperature variation, the effective bandgap changes from showing a positive rate of change to showing a negative one (for a quantum dot 3 nm in diameter), which can be accounted for by incorporating a linear variation of the carrier effective masses into a simple calculation of the exciton ground state in the quantum dot. In the case of the pressure variation, we observe a clear inverse correlation between the absolute value of the pressur…

Pressure Dependence of the Bandgap Bowing in Zinc-Blende ZnTe 1− x Se x

We report on the pressure dependence of the bandgap bowing in the ZnTe 1 m x Se x alloy, in the whole composition range. The bandgap bowing parameter is shown to increase almost linearly with pressure from 1.23 at ambient pressure to 1.6 at 7 GPa. Saturation effects observed in the pressure dependence for x =0.1 and x =0.2 are shown to be related to the direct-to-indirect crossover. Results are discussed and interpreted in the framework of structural relaxation models for gap bowing. A prediction of these models (the negative bowing of the o 15 m ;X 1 transition) is shown to be compatible with the fact that the direct-to-indirect crossover pressure increases with the Se content.

Pressure dependence of the optical properties of wurtzite and rock-salt Zn1–xCoxO thin films

In this paper we investigate the electronic structure of Zn 1-x Co x O by means of optical absorption measurements under pressure. Thin films of Zn 1-x Co x O with different Co content (from 1 to 30%) were prepared by pulsed laser deposition on mica substrates. Absorption spectra exhibit three main features that are clearly correlated to the Co content in the films: (i) absorption peaks in the infrared associated to crystal-field-split internal transitions in the Co 3d shell, with very small pressure coefficients due to their atomic character; (ii) a broad absorption band below the fundamental edge associated to charge transfer transitions, that exhibit relatively large pressure coefficient…

Structural and vibrational study of Bi2Se3under high pressure

The structural and vibrational properties of bismuth selenide (Bi${}_{2}$Se${}_{3}$) have been studied by means of x-ray diffraction and Raman scattering measurements up to 20 and 30 GPa, respectively. The measurements have been complemented with ab initio total-energy and lattice dynamics calculations. Our experimental results evidence a phase transition from the low-pressure rhombohedral ($R$-3$m$) phase (\ensuremath{\alpha}-Bi${}_{2}$Se${}_{3}$) with sixfold coordination for Bi to a monoclinic $C$2/$m$ structure (\ensuremath{\beta}-Bi${}_{2}$Se${}_{3}$) with sevenfold coordination for Bi above 10 GPa. The equation of state and the pressure dependence of the lattice parameters and volume …

Experimental and theoretical study of band structure of InSe andIn1−xGaxSe(x&lt;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…

High-pressure studies of topological insulators Bi2Se3, Bi2Te3, and Sb2Te3

Bi2Se3, Bi2Te3, and Sb2Te3 are narrow bandgap semiconductors with tetradymite crystal structure (R-3m) which have been extensively studied along with their alloys due to their promising operation as thermoelectric materials in the temperature range between 300 and 500¿K. Studies on these layered semiconductors have increased tremendously in the last years since they have been recently predicted and demonstrated to behave as 3D topological insulators. In particular, a number of high-pressure studies have been done in the recent years in these materials. In this work we summarize the main results of the high-pressure studies performed in this family of semiconductors to date. In particular, w…

High-pressure study of the infrared active modes in wurtzite and rocksalt ZnO

International audience; We present a high-pressure study of ZnO carried out in the mid- to far-infrared frequency domain with the aim of characterizing the optic modes of wurtzite and rocksalt ZnO. We obtained the pressure coefficients of the E1(TO), E1(LO), A1(TO), and A1(LO) modes of the low-pressure wurtzite phase and compare them with previous Raman measurements. The optical modes of the high-pressure rocksalt phase are infrared active, so we were able to determine their wave numbers and pressure dependencies. In the wurtzite phase, high pressure induces a slight decrease in both longitudinal and transverse effective charges. The decrease is more pronounced in the rocksalt phase.

Electrical and photovoltaic properties of indium‐tin‐oxide/p‐InSe/Au solar cells

Conditions for efficiency improvement and optimization in indium‐tin‐oxide/p‐indium‐selenide solar cells are discussed in this paper. This aim is achieved by using low‐resistivity p‐indium‐selenide and by incorporating a back‐surface‐field contact. This contact is insured by a p‐indium selenide/gold barrier whose rectifying behavior is explained through the complex impurity structure of p‐indium‐selenide. Electrical and photovoltaic properties of the cells are also reported. The efficiency parameters under AM1 simulated conditions have been improved up to 32 mA/cm2 for the short‐circuit current density, 0.58 V for the open‐circuit voltage, and 0.63 for the filling factor. As a result, solar…

Electron scattering mechanisms inn-type indium selenide

Electron scattering mechanisms in $n$-type indium selenide are investigated by means of the temperature dependence (4-500 K) of Hall mobility and the magnetic field dependence of Hall and magnetoresistance coefficients. The Schmid model for homopolar optical-phonon scattering can explain the temperature dependence of electron mobility above 40 K. The electron-phonon coupling constant is determined, ${g}^{2}=0.054$. The optical phonon involved in the process is identified as the ${A}_{1}^{\ensuremath{'}}$ phonon with energy 14.3 meV. The magnetic field dependence of Hall and magnetoresistance coefficients is discussed in terms of the Jones-Zener expansion.

Bandgap behavior and singularity of the domain-induced light scattering through the pressure-induced ferroelectric transition in relaxor ferroelectric A(x)Ba(1-x)Nb(2)O(6) (A: Sr,Ca)

[EN] In this letter, we have investigated the electronic structure of A(x)Ba(1-x)Nb(2)O(6) relaxor ferroelectrics on the basis of optical absorption spectroscopy in unpoled single crystals with A = Sr and Ca under high pressure. The direct character of the fundamental transition could be established by fitting Urbach's rule to the photon energy dependence of the absorption edge yielding bandgaps of 3.44(1) eV and 3.57(1) eV for A = Sr and Ca, respectively. The light scattering by ferroelectric domains in the pre-edge spectral range has been studied as a function of composition and pressure. After confirming with x-ray diffraction the occurrence of the previously observed ferroelectric to pa…

Pressure-induced phase transition in hydrothermally grown ZnO nanoflowers investigated by Raman and photoluminescence spectroscopy.

This paper reports the pressure-dependent photoluminescence and Raman spectral investigation of hydrothermally synthesized ZnO nanoflowers at room temperature. Intrinsic near-band-edge UV emission from ZnO nanoflowers is monotonously blue-shifted under pressures up to 13.8 GPa with a pressure coefficient of 26 meV GPa(-1), and this pressure value is nearly 5 GPa above the transition pressure from the wurtzite to the rock salt phase for bulk ZnO. The Raman band corresponds to the wurtzite phase, the [Formula: see text] and [Formula: see text] modes were observed up to about 11 GPa from the spectra. The apparent discrepancy in the transition pressures as determined from photoluminescence and …

High-pressure electrical transport measurements on p-type GaSe and InSe

We performed high-pressure Hall effect and resistivity measurements in p-type GaSe and InSe up to 12 GPa. The pressure behaviour of the transport parameters shows dramatic differences between both materials. In GaSe, the hole concentration and mobility increase moderately and continuously. In InSe, the hole mobility raises rapidly and the hole concentration increases abruptly near 0.8 GPa. The observed results are attributed to the different pressure evolution of the valence-band structure in each material. In InSe a carrier-type inversion is also detected near 4.5 GPa.

Optical Absorption of Zinc Selenide Doped with Cobalt (Zn1-xCoxSe) under Hydrostatic Pressure

Optical absorption of the diluted magnetic semiconductor Zn 1-x Co x Se (x = 0.02) has been measured at room temperature under hydrostatic pressure up to 14 GPa in a membrane diamond-anvil cell. We found two absorption features: (i) an absorption structure in the energy range 1.5 to 1.8 eV, with a negligible pressure shift (i.e. (0.45 ± 0.05) meV/GPa) which we have identified as the Co 2+ (3d 7 ) internal transition 4 A 2 (F) → 4 T 1 (P) and (ii) an onset in the energy range 2 to 2.7 eV which redshifts with pressure (dE/dP = (-8.1 ± 0.6) meV/GPa). We have attributed such absorption edge to charge transfer between the ZnSe valence band and the Co 2+ (3d 7 ) levels. On the assumption that tho…

Pressure Dependence of the Low-Frequency Dielectric Constant in III-VI Semiconductors

In this work we report on the pressure dependence of the low-frequency dielectric constant parallel to the c-axis (e∥) in GaS, GaSe, and InSe as obtained from direct capacitance measurements. A large increase of e∥ with pressure has been observed. The pressure change of the lattice polarizability along the c-axis is calculated in the framework of a rigid-ion model from the change of the angle of the anion–cation bond with respect to the layer plane, which results in a slight increase of the lattice contribution. Consequently, the pressure behaviour of e∥ is proposed to arise from the large increase of the electronic polarizability along the c-axis. This is explained through a decrease of th…

High-pressure structural phase transitions in CuWO4

We study the effects of pressure on the structural, vibrational, and magnetic behavior of cuproscheelite. We performed powder x-ray diffraction and Raman spectroscopy experiments up to 27 GPa as well as ab initio total-energy and lattice-dynamics calculations. Experiments provide evidence that a structural phase transition takes place at 10 GPa from the low-pressure triclinic phase (P-1) to a monoclinic wolframite-type structure (P2/c). Calculations confirmed this finding and indicate that the phase transformation involves a change in the magnetic order. In addition, the equation of state for the triclinic phase is determined: V0 = 132.8(2) A3, B0 = 139 (6) GPa and = 4. Furthermore, experim…

Optical absorption of zinc selenide doped with cobalt (Zn1−xCoxSe) under hydrostatic pressure

Abstract The optical absorption of the diluted magnetic semiconductor Zn1−xCOxSe (x = 0.02) has been measured at room temperature under hydrostatic pressure up to 14GPa in a membrane diamond-anvil cell. We found two absorption features: (i) an absorption structure in the energy range 1.6−1.8eV, with a negligible pressure shift (i.e., 0.45 ± 0.05 meV/GPa) which we have identified as the Co2+(3d7) internal transition 4A2(F)→+4T1(P) and (ii) an onset in the energy range 2−2.7eV which redshifts with pressure (−8.1±0.6meV/GPa). We have attributed such absorption edge to charge transfer between the ZnSe valence band and the Co2+(3d7) levels.

Optical properties of wurtzite and rock-salt ZnO under pressure

Abstract This paper reports on the pressure dependence of the optical absorption edge of ZnO in the wurtzite and rock-salt phase, up to 14 GPa. Both vapor-phase monocrystals and pulsed-laser-deposition thin films have been investigated. In both types of samples the wurtzite to rock-salt transition is observed at 9.7±0.2 GPa. The absorption tail of the fundamental gap, as measured in monocrystals, exhibits a pressure coefficient of 24.5±2 meV/GPa. The evolution under pressure of the full absorption edge of the wurtzite phase is studied with thin film samples, yielding a slightly lower pressure coefficient (23.0±0.5 meV/GPa for the A–B exciton). Rock-salt ZnO is shown to be an indirect semico…

Investigation of the local structure of As-related acceptor centres in InSe by means of fluorescence-detected XAS

In this paper we report on fluorescence-detected XAS measurements in arsenic-doped p-type indium selenide. Absorption spectra taken at the arsenic K-edge allow for an unambiguous determination of the bond length of the As atoms with their first neighbours that turns out to be 2.56 ± 0.02 A. The XANES spectrum and the bond length (as determined from EXAFS oscillations) exhibit weak anisotropy as the angle between the crystal c-axis and the x-ray polarization vector is changed. These results are fully compatible with the model of a single substitutional acceptor (As in Se site), with no bonds along the c-axis (that would give rise to strong linear dicroism in the XANES spectrum). The In–As bo…

High-pressure vibrational and optical study of Bi2Te3

We report an experimental and theoretical lattice dynamics study of bismuth telluride (Bi2Te 3 )u p to 23 GPa together with an experimental and theoretical study of the optical absorption and reflection up to 10 GPa. The indirect bandgap of the low-pressure rhombohedral (R-3m) phase (α-Bi2Te 3) was observed to decrease with pressure at a rate of − 6m eV/GPa. In regard to lattice dynamics, Raman-active modes of α-Bi2Te 3 were observed up to 7.4 GPa. The pressure dependence of their frequency and width provides evidence of the presence of an electronic-topological transition around 4.0 GPa. Above 7.4 GPa a phase transition is detected to the C2/m structure. On further increasing pressure two …

Phonons of hexagonal BN under pressure: Effects of isotopic composition

Raman scattering experiments on isotopically enriched hexagonal boron nitride have been performed under pressure up to 11 GPa at room temperature. The sublinear increase of the Raman-active E2g mode frequencies has been characterized. The pressure behavior has been analyzed by means of a bond-stiffness–bond-length scaling parameter γ which takes into consideration the vast differences in a- and c-axis compressibilities. The interlayer shear mode exhibits a γ parameter similar to that of graphite, and the mode frequency in isotopically pure samples separates faster at low pressures as a result of van der Waals interactions. Because of the extremely low a-axis compressibility, the intralayer …

Structural Metastability and Quantum Confinement in Zn1–xCoxO Nanoparticles

This paper investigates the electronic structure of wurtzite (W) and rock-salt (RS) Zn1-xCoxO nanoparticles (NPs) by means of optical measurements under pressure (up to 25 GPa), X-ray absorption, and transmission electron microscopy. W-NPs were chemically synthesized at ambient conditions and RS-NPs were obtained by pressure-induced transformation of W-NPs. In contrast to the abrupt phase transition in W-Zn1-xCoxO as thin film or single crystal, occurring sharply at about 9 GPa, spectroscopic signatures of tetrahedral Co(2+) are observed in NPs from ambient pressure to about 17 GPa. Above this pressure, several changes in the absorption spectrum reveal a gradual and irreversible W-to-RS pha…

High-pressure phase transitions and compressibility of wolframite-type tungstates

This paper reports an investigation on the phase diagram and compressibility of wolframite-type tungstates by means of x-ray powder diffraction and absorption in a diamond-anvil cell and ab initio calculations. The diffraction experiments show that monoclinic wolframite-type MgWO4 suffers at least two phase transitions, the first one being to a triclinic polymorph with a structure similar to that of CuWO4 and FeMoO4-II. The onset of each transition is detected at 17.1 and 31 GPa. In ZnWO4 the onset of the monoclinic-triclinic transition has been also found at 15.1 GPa. These findings are supported by density-functional theory calculations, which predict the occurrence of additional transiti…

Growth, characterization, and high-pressure optical studies of CuWO4

Copper tungstate (CuWO4) crystals grown by the top-seeded solution growth method were characterized by X-ray diffraction, Raman scattering, and optical measurements. CuWO4 has a triclinic structure (P 1¯) with a = 4.709 A, b = 5.845 A, c = 4.884 A, α = 88.3°, β = 92.5°, and γ = 97.2°. It consists of corner-linked CuO6 and WO6 octahedra, the former having a pseudo-tetragonally elongated geometry caused by the Cu2+ Jahn–Teller effect. Fifteen out of the eighteen Raman modes of CuWO4 are reported, discussed, and compared with those of other tungstates. We also determined the indirect band-gap energy of CuWO4 (2.3 eV) and its negative pressure coefficient up to 25 GPa. The pressure evolution of…

Anisotropy of the refractive index and absorption coefficient in the layer plane of gallium telluride single crystals

Refractive index and absorption coefficient of GaTe for light polarized in the optical axis directions in the layer plane are determined from transmission measurements. The refractive index is determined in the wavelength range from 0.7 to 25 μm and the absorption coefficient in the range of energies from 1.6 to 2 eV at room temperature and at 30 K. The optical constants are found to be anisotropic in the layer plane. The refractive index dispersion is interpreted through a Phillips-Van Vechten model and the Penn gaps for each direction are found to be E pg (⊥b) = 3.37 eV and E pg (∥b) = 3.58 eV. In the long-wavelength region a polar phonon contribution is also taken into account. The absor…

Investigation of nitrogen-related acceptor centers in indium selenide by means of photoluminescence: Determination of the hole effective mass

In this work we report on steady-state and time-resolved photoluminescence (PL) measurements in nitrogen-doped p-type indium selenide in the 33--210-K temperature range. In samples with low nitrogen concentration the photoluminescence spectrum consists of exciton-related peaks and a band-to-acceptor recombination peak (2.1-\ensuremath{\mu}s lifetime) with LO-phonon replica. An ionization energy of 65.5 meV is proposed for the nitrogen-related acceptor. A long-lived (18 \ensuremath{\mu}s) component, which consists of an asymmetric broadband centered around the acceptor peak, has been also detected by means of time-resolved PL. Samples with a higher nitrogen concentration show a PL spectrum t…

Optical and structural study of the pressure-induced phase transition of CdWO$_4$

Physical review / B 95(17), 174105 (2017). doi:10.1103/PhysRevB.95.174105

Refractive index of GaTe under high pressure

In this paper we describe two experiments, in the near- and mid-infrared, designed to investigate the evolution under pressure of the GaTe refractive index for polarization parallel and perpendicular to the crystallographic c-axis (in the layer plane). The refractive index dispersion for both light polarizations has been determined up to 5.5 GPa. It is found that the refractive index increases faster in the direction perpendicular to the c-axis than along the c-axis. To find out the origin of such a difference we used a Phillips-Van Vechten model and arrived at the conclusion that it is due to the different pressure behaviour of the Penn gap for each polarization.

High pressure EXAFS on GaTe single crystal including polarization

Electrical Resistivity Anisotropy of Silicon-Doped n-Indium Selenide

Trapping of three-dimensional electrons and transition to two-dimensional transport in the three-dimensional topological insulator Bi2Se3under high pressure

This paper reports an experimental and theoretical investigation on the electronic structure of bismuth selenide (Bi2Se3) up to 9 GPa. The optical gap of Bi2Se3 increases from 0.17 eV at ambient pressure to 0.45 eV at 8 GPa. The quenching of the Burstein-Moss effect in degenerate samples and the shift of the free-carrier plasma frequency to lower energies reveal a quick decrease of the bulk three-dimensional (3D) electron concentration under pressure. On increasing pressure the behavior of Hall electron concentration and mobility depends on the sample thickness, consistently with a gradual transition from mainly 3D transport at ambient pressure to mainly two-dimensional (2D) transport at hi…

Synthesis of a novel zeolite through a pressure-induced reconstructive phase transition process

et al.

Optical properties of thin films of ZnO prepared by pulsed laser deposition

In this paper we report on the structural features and optical properties of wurtzite ZnO films epitaxially grown on sapphire, fluorite and mica substrates by means of pulsed laser deposition (PLD). Post-deposition annealing results in a clear improvement of the film quality, reflected by the small width of the exciton-related lines in both the absorption and the photoluminescence spectra. Photoluminescence spectra revealed a multi-line structure which is identified in term of free excitons and excitons complexes with neutral donors and deep centers. The relative intensity of the PL lines mainly depends on the nature of the substrate used. Concerning optoelectronic applications it is especi…

Electronic structure of indium selenide probed by magnetoabsorption spectroscopy under high pressure

We report on an investigation of the peculiar electronic structure of the layered semiconductor InSe by magneto-optical experiments under high pressure up to 5 GPa. Magneto-absorption spectroscopy is performed under pulsed magnetic field up to 53 T using a specific setup. Excitonic magnetofingerprints and high-field oscillatory magnetoabsorption yield significant details on the band structure. In addition, the application of an external pressure unveils phenomena that confirm the specific $\mathbf{k}\ensuremath{\cdot}\mathbf{p}$ model proposed for this compound on the basis of earlier measurements.

Pressure-induced amorphization of YVO4:Eu3+ nanoboxes

A structural transformation from the zircon-type structure to an amorphous phase has been found in YVO4:Eu3+ nanoboxes at high pressures above 12.7 GPa by means of x-ray diffraction measurements. However, the pair distribution function of the high-pressure phase shows that the local structure of the amorphous phase is similar to the scheelite-type YVO4. These results are confirmed both by Raman spectroscopy and Eu3+ photoluminescence which detect the phase transition to a scheelite-type structure at 10.1 and 9.1 GPa, respectively. The irreversibility of the phase transition is observed with the three techniques after a maximum pressure in the upstroke of around 20 GPa. The existence of two …

Optical and photovoltaic properties of indium selenide thin films prepared by van der Waals epitaxy

Indium selenide thin films have been grown on p-type gallium selenide single crystal substrates by van der Waals epitaxy. The use of two crucibles in the growth process has resulted in indium selenide films with physical properties closer to these of bulk indium selenide than those prepared by other techniques. The optical properties of the films have been studied by electroabsorption measurements. The band gap and its temperature dependence are very close to those of indium selenide single crystals. The width of the fundamental transition, even if larger than that of the pure single crystal material, decreases monotonously with temperature. Exciton peaks are not observed even at low temper…

XRD and XAS structural study of CuAlO2under high pressure

International audience; We present the results of x-ray diffraction and x-ray absorption spectroscopy experiments in CuAlO2 under high pressure. We discuss the polarization dependence of the x-ray absorption near-edge structure at the Cu K-edge. XRD under high pressure evidences anisotropic compression, the a-axis being more compressible than the c-axis. EXAFS yields the copper-oxygen bond length, from which the only internal parameter of the delafossite structure is deduced. The combination of anisotropic compression and the internal parameter decrease results in a regularization of the AlO6 octahedra. The anisotropic compression is related to the chemical trends observed in the lattice pa…

HgGa2 Se4 under high pressure: An optical absorption study

High-pressure optical absorption measurements have been performed in defect chalcopyrite HgGa2Se4 to investigate the influence of pressure on the bandgap energy and its relation with the pressure-induced order–disorder processes that occur in this ordered-vacancy compound. Two different experiments have been carried out in which the sample undergoes either a partial or a total pressure-induced disorder process at 15.4 and 30.8 GPa, respectively. It has been found that the direct bandgap energies of the recovered samples at 1 GPa were around 0.15 and 0.23 eV smaller than that of the original sample, respectively, and that both recovered samples have different pressure coefficients of the dir…

Electronic structure of p-type ultraviolet-transparent conducting CuScO2 films

Abstract We investigate the electronic structure of CuScO 2 thin films grown on sapphire and mica substrates by pulsed laser deposition. X-ray diffraction and microanalysis confirm that the films have the expected delafossite crystal structure and stoichiometric proportions. The electronic structure is investigated by means of X-ray and ultraviolet photoelectron spectroscopy. Electronic states in the range 0–1350 eV are identified, making reference to theoretical density-of-states calculations up to 80 eV. Photoelectron spectra near the Fermi energy confirm the p-character of the films. Optical absorption spectroscopy shows that the films are transparent up to 3.7 eV and exhibit an intense …

Pressure dependence of the refractive index in wurtzite and rocksalt indium nitride

We have performed high-pressure Fourier transform infrared reflectance measurements on a freestanding InN thin film to determine the refractive index of wurtzite InN and its high-pressure rocksalt phase as a function of hydrostatic pressure. From a fit to the experimental refractive-index curves including the effect of the high-energy optical gaps, phonons, free carriers, and the direct (fundamental) band-gap in the case of wurtzite InN, we obtain pressure coefficients for the lowfrequency (electronic) dielectric constant e1 . Negative pressure coefficients of -8.8 × 10-2 GPa-1 and -14.8 × 10-2 GPa-1 are obtained for the wurtzite and rocksalt phases, respectively. The results are discussed …

Determination of the high-pressure crystal structure ofBaWO4andPbWO4

We report the results of both angle-dispersive x-ray diffraction and x-ray absorption near-edge structure studies in $\mathrm{Ba}\mathrm{W}{\mathrm{O}}_{4}$ and $\mathrm{Pb}\mathrm{W}{\mathrm{O}}_{4}$ at pressures of up to $56\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ and $24\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$, respectively. $\mathrm{Ba}\mathrm{W}{\mathrm{O}}_{4}$ is found to undergo a pressure-driven phase transition at $7.1\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ from the tetragonal scheelite structure (which is stable under normal conditions) to the monoclinic fergusonite structure whereas the same transition takes place in $\mathrm{Pb}\mathrm{W}{\mathrm{O}}_{4}$ at $9\phantom{\rule{0…

Optical absorption and Raman spectroscopy of CuWO4

Th e electronic absorption and Raman spectra of CuWO4 are studied as a function of pressure in the 0 - 20 GPa range. The below-gap absorption bands at 1.15, 1.38 and 1.56 eV correspond to Cu 2+ d-transitions split by the Jahn-Teller distortion of CuO6 (Req = 1.98 A; Rax = 2.39 A; Qθ = 0.47 A). Pressure induces a strong reduction of the JT distortion up to 10 GPa. Above this pressure we observe, by optical absorption and Raman spectroscopy, a first-order phase transition at 11 GPa with phase coexistence in the 10-12 GPa range, as it is confirmed by Raman spectroscopy. The absorption spectra suggest that two different Cu 2+ sites are formed in the high pressure phase, each having rather diffe…

Photoluminescence in ZnO:Co2+ (0.01%–5%) Nanoparticles, Nanowires, Thin Films, and Single Crystals as a Function of Pressure and Temperature: Exploring Electron–Phonon Interactions

This work investigates the electronic structure and photoluminescence properties of Co2+-doped ZnO and their pressure and temperature dependences through high-resolution absorption and emission spe...

High-pressure, high-temperature phase diagram of InSe: A comprehensive study of the electronic and structural properties of the monoclinic phase of InSe under high pressure

We report on an investigation of the high-pressure, high-temperature phase diagram of InSe. We optically observed the phase transition from the rhombohedral polytype (InSe-I) to the monoclinic phase (InSe-II) and determined the phase boundary up to $10\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$. High-pressure resistivity measurements were performed to complement the optical measurements. Monoclinic and cubic InSe (InSe-III) were observed to be metastable around $14.5\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ and $420\phantom{\rule{0.3em}{0ex}}\mathrm{K}$, and evidence suggesting the existence of an as yet unidentified new high-pressure and high-temperature phase was found. By means of optical ab…

Structural evolution of theCuGaO2delafossite under high pressure

We have performed pseudopotential calculations and x-ray-diffraction and x-ray-absorption measurements on the ${\mathrm{CuGaO}}_{2}$ delafossite under high pressure. We have completely characterized the structural behavior of the low pressure phase. We have found out that the a axis is more compressible than the c axis, and as a consequence the oxygen octahedra defined by the gallium environment tend to become more regular under high pressure. We have determined the internal parameter describing the oxygen position inside the unit cell, and seen that it is nearly constant when pressure is applied. We have observed an irreversible phase transition affecting the copper environment but not the…

High-pressure lattice dynamics in wurtzite and rocksalt indium nitride investigated by means of Raman spectroscopy

We present an experimental and theoretical lattice-dynamical study of InN at high hydrostatic pressures. We perform Raman scattering measurements on five InN epilayers, with different residual strain and free electron concentrations. The experimental results are analyzed in terms of ab initio lattice-dynamical calculations on both wurtzite InN (w-InN) and rocksalt InN (rs-InN) as a function of pressure. Experimental and theoretical pressure coefficients of the optical modes in w-InN are compared, and the role of residual strain on the measured pressure coefficients is analyzed. In the case of the LO band, we analyze and discuss its pressure behavior considering the double-resonance mechanis…

High pressure and high magnetic field behaviour of free and donor-bound-exciton photoluminescence in InSe

We report here first magneto-photoluminescence investigations under high pressure up to 6 GPa on III-VI layered semiconductor InSe. Both diamagnetism and magnetic field induced gap opening driven by Landau quantization became observable by using a 60 T pulsed magnet. The pressure-induced enhancement of the diamagnetic coefficient is consistent with the increase of the dielectric constant under pressure while the evolution of the linear coefficient is consistent with a slight increase of the electron effective mass up to 4 GPa and a direct-to-indirect conduction-band crossover around that pressure.

Peptide metal-organic frameworks under pressure: flexible linkers for cooperative compression

We investigate the structural response of a dense peptide metal-organic framework using in situ powder and single-crystal X-ray diffraction under high-pressures. Crystals of Zn(GlyTyr)2 show a reversible compression by 13% in volume at 4 GPa that is facilitated by the ability of the peptidic linker to act as a flexible string for a cooperative response of the structure to strain. This structural transformation is controlled by changes to the conformation of the peptide, which enables a bond rearrangement in the coordination sphere of the metal and changes to the strength and directionality of the supramolecular interactions specific to the side chain groups in the dipeptide sequence. Compar…

Three-dimensional electrons and two-dimensional electric subbands in the transport properties of tin-dopedn-type indium selenide: Polar and homopolar phonon scattering

Electron-scattering mechanisms in n-type indium selenide doped with different amounts of tin are studied by means of the Hall effect (30--300 K) and photo-Hall effect (300 K). The electron mobility at room temperature is found to increase with the free-electron concentration in samples with low tin content. The same behavior is observed when the electron concentration increases due to thermal annealing or photogeneration. That is explained through the presence of two kinds of free electrons contributing to the charge transport along the layers: high-mobility three-dimensional (3D) electrons in the conduction band, and low-mobility two-dimensional electrons in the electric subbands. These 2D…

Role ofp-dands-dinteractions in the electronic structure and band gap of Zn1−xMxO (M=Cr, Mn, Fe, Co, Ni, and Cu): Photoelectron and optical spectroscopy and first-principles band structure calculations

We report an investigation on the effect of $p$-$d$ and $s$-$d$ interactions in the electronic structure, and especially in the band-gap value, of wurtzite wide-gap diluted magnetic semiconductors Zn${}_{1\ensuremath{-}x}$${M}_{x}$O ($M=\mathrm{Cr}$, Mn, Fe, Co, Ni, Cu). Thin films prepared by pulsed laser deposition are investigated by means of optical absorption at low-temperature and photoelectron spectroscopy. Pure wurzite phase is shown to be maintained for Co and Mn concentrations up to 25$%$ and for Cr up to 10$%$, while in the case of Fe, Ni, and Cu, other phases are present for concentrations higher than 5, 2, and 1$%$, respectively. The band gap of the Zn${}_{1\ensuremath{-}x}$${M…

GaS and InSe equations of state from single crystal diffraction

We have performed single crystal angle dispersive X-ray diffraction at high pressure in order to investigate the GaS and InSe equations of state. We situate the transition from β-GaS to GaS-II at 2 7 0 3. ± . GPa. In the InSe experiment we locate the beginning of the phase transition at 7.6 ± 0.6 GPa. The equations of state of β-GaS ( 0 43 27 0 06V = . ± . Å 3 , 37 2 GPaB = ± , 5 2B = .¢ ), GaS-II ( 0 42 4 0 2V = . ± . Å 3 , 50 3 GPaB = ± and 4 3 0 3B = . ± .¢ ) and γ-InSe ( 0 58 4 0 2V = . ± . Å 3 , 24 3 GPaB = ± and 8 6 0 8B = . ± .¢ ) are discussed and compared with the results of an ab-initio calculation.

Low-cost set-up for Fourier-transform infrared spectroscopy in diamond anvil cell from 4000 to 400 cm−1

An experimental set-up for Fourier-transform infrared (FTIR) studies at high pressure in the mid-IR region (400–4000 cm−1) is constructed using a compact TEO-400 FTIR interferometer module and an external microscopic optical bench with cassegrain focusing objectives. Cassegrain-type reflective objectives act as an excellent beam condenser that facilitates the interfacing between FTIR spectrometer and diamond anvil cell. This set-up is capable of recording transmission and reflection infrared spectra at high pressure. Preliminary results are reported both in the reflection (pressure dependence of polar phonons in CuWO4) and transmission configuration (polarized light absorption of polar phon…

High-pressure x-ray absorption study of GaTe including polarization

The evolution of the local structure in GaTe under pressure is studied by x-ray absorption spectroscopy experiments at the Ga K-edge (10.368 keV) on oriented single crystals. Taking advantage of the linearly polarized character of synchrotron radiation, the pressure evolution of both the Ga-Te and the in-plane Ga-Ga bond lengths could be determined, in spite of the small amplitude of the latter. Our measurements show that both distances are much less compressible than what could be inferred from the bulk compressibility, which evidences a strong variation of Ga-Ga-Te and Te-Ga-Te angles under pressure. The Te-Te intralayer distance perpendicular to the layers is observed to increase with in…

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…

Refractive index of the CuAlO2delafossite

The refractive index of the CuAlO2 delafossite has been determined from interference measurements in single crystals performed in the visible, near and mid infrared regions of the spectrum. The analysis of the refractive index dispersion corresponding to light polarization perpendicular to the c-axis (P ⊥ c) yields a static dielectric constant of 0 = 7.7 ± 0.8 and a low frequency electronic constant ∞ = 5.1 ± 0.1. The relevant infrared active mode is found to be at 550 ± 25 cm−1. The electronic contribution can be well described by a Penn gap at 39 000 ± 1000 cm−1. Both the refractive index and its dispersion are found to be smaller for P||c than for P ⊥ c.

The electronic structure of zircon-type orthovanadates: Effects of high-pressure and cation substitution

The electronic structure of four ternary-metal oxides containing isolated vanadate ions is studied. Zircon-type YVO4, YbVO4, LuVO4, and NdVO4 are investigated by high-pressure optical-absorption measurements up to 20 GPa. First-principles calculations based on density-functional theory were also performed to analyze the electronic band structure as a function of pressure. The electronic structure near the Fermi level originates largely from molecular orbitals of the vanadate ion, but cation substitution influence these electronic states. The studied ortovanadates, with the exception of NdVO4, undergo a zircon-scheelite structural phase transition that causes a collapse of the band-gap energ…

Tin-related double acceptors in gallium selenide single crystals

Gallium selenide single crystals doped with different amounts of tin are studied through resistivity and Hall effect measurements in the temperature range from 30 to 700 K. At low doping concentration tin is shown to behave as a double acceptor impurity in gallium selenide with ionization energies of 155 and 310 meV. At higher doping concentration tin also introduces deep donor levels, but the material remains p-type in the whole studied range of tin doping concentrations. The deep character of donors in gallium selenide is discussed by comparison of its conduction band structure to that of indium selenide under pressure. The double acceptor center is proposed to be a tin atom in interlayer…

Growth of manganese sulfide (α-MnS) thin films by thermal vacuum evaporation: Structural, morphological and optical properties

Abstract MnS thin films have been successfully prepared by thermal evaporation method at different substrate temperatures using different masses of MnS powder. The prepared films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and UV–visible spectrophotometry. The XRD measurements show that the films crystallized in the pure α-MnS for substrate temperatures above 100 °C. The optical bandgap of thin films is found to be in the range of 3.2–3.3 eV. A factorial experimental design was used for determining the influence of the two experimental parameters on the films growth.

Local structure in Ga1−xInxSe alloys

Abstract In this work we study the local structure of layered G a 1 − x I n x S e alloys by means of X-ray Absorption. We complement our research with a Raman study. The available alloys have compositions close to the host binaries. The dependence of XANES (X-ray Near Edge Structure) features with synchrotron polarization clearly establishes the substitutional character of the alloying cations. Interstitial atoms, if present, remain under the detection limit of the technique. EXAFS (Extended X-ray Absorption Fine Structure) demonstrates the existence of G a − I n bonds in the alloys. The cation-anion bond-lengths in the alloys remain similar to that of the pure compounds. There is no signif…

Optical and electronic properties of 2H−MoS2 under pressure: Revealing the spin-polarized nature of bulk electronic bands

Monolayers of transition-metal dichalcogenide semiconductors present spin-valley locked electronic bands, a property with applications in valleytronics and spintronics that is usually believed to be absent in their centrosymmetric (as the bilayer or bulk) counterparts. Here we show that bulk $2\mathrm{H}\text{\ensuremath{-}}\mathrm{Mo}{\mathrm{S}}_{2}$ hides a spin-polarized nature of states determining its direct band gap, with the spin sequence of valence and conduction bands expected for its single layer. This relevant finding is attained by investigating the behavior of the binding energy of $A$ and $B$ excitons under high pressure, by means of absorption measurements and density-functi…

Deep Levels in Silicon Doped n-Indium Selenide

Vibrational properties of delafossiteCuGaO2at ambient and high pressures

In this paper we investigate the vibrational properties of $\mathrm{Cu}\mathrm{Ga}{\mathrm{O}}_{2}$ delafossite by means of Raman experiments and ab initio calculations. Both investigations have been performed at ambient pressure and also at high pressure. The two Raman-active modes have frequencies ${w}_{{E}_{g}}=368\ifmmode\pm\else\textpm\fi{}1\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ and ${w}_{{A}_{1g}}=729\ifmmode\pm\else\textpm\fi{}1\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$, and pressure coefficients $2.78\ifmmode\pm\else\textpm\fi{}0.03\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}∕\mathrm{GPa}$ $({E}_{g})$ and $4.64\ifmmode\pm\else\text…

Crystalline-Size Dependence of Dual Emission Peak on Hybrid Organic Lead-Iodide Perovskite Films at Low Temperatures

In this work, we have investigated the crystalline-size dependence of optical absorption and photoluminescence emission of CH3NH3PbI3 films, which is necessary to identify the potential practical applications of the gadgets based on perovskite films. This study was carried out at low temperatures to minimize the extra complexity induced by thermal effects. The purpose was to clarify the origin of the dual emission peak previously reported in the literature. We found that the grain size is responsible for the appearance or disappearance of this dual emission on CH3NH3PbI3 at low temperatures, whereas we have inferred that the thickness of the perovskite layer is a much more important factor …

Anomalous High-Pressure Jahn-Teller Behavior inCuWO4

High-pressure optical-absorption measurements performed in CuWO4 up to 20 GPa provide experimental evidence of the persistence of the Jahn-Teller (JT) distortion in the whole pressure range both in the low-pressure triclinic and in the highpressure monoclinic phase. The electron-lattice coupling associated with the eg(Exe) and t2g(Txe) orbitals of Cu2+ in CuWO4 are obtained from correlations between the JT distortion of the CuO6 octahedron and the associated structure of Cu2+ d-electronic levels. This distortion and its associated JT energy (EJT) decrease upon compression in both phases. However, both the distortion and associated EJT increase sharply at the phase transition pressure (PT = …

Pressure and temperature dependence of the lattice dynamics ofCuAlO2investigated by Raman scattering experiments andab initiocalculations

We have studied the vibrational properties of $\mathrm{Cu}\mathrm{Al}{\mathrm{O}}_{2}$ by means of Raman scattering in ambient conditions, at low temperature, and also at high pressure. Results are discussed in the framework of an ab initio calculation. Raman active modes have wave numbers ${\ensuremath{\sigma}}_{{E}_{g}}=418.1\ifmmode\pm\else\textpm\fi{}0.2\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ and ${\ensuremath{\sigma}}_{{A}_{1g}}=767.2\ifmmode\pm\else\textpm\fi{}0.3\phantom{\rule{0.3em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$. Polarized measurements with single crystals have confirmed their symmetry. We present and discuss the phonon-dispersion curves. Below $200\phant…

First-principles study of the electronic structure of cubicGaS: Metallic versus insulating polymorphs

The electronic structure of different polymorphs of gallium sulphide $(\mathrm{GaS})$ with cubic structure is investigated by means of first-principles band structure calculations in connection with experimental reports on a metastable semiconducting cubic form of this material. The expected metallic character of simple cubic phases containing one $\mathrm{GaS}$ group per unit cell (rocksalt or zinc-blende) is confirmed by the calculations. A cubane-based zinc-blende structure is found to exhibit a band gap which is compatible with experimental results but the unit cell parameter is much larger than the reported ones. We have also studied cubic phases containing hydrogen. It is found that t…

Tuning the Direct and Indirect Excitonic Transitions of h-BN by Hydrostatic Pressure

The pressure dependence of the direct and indirect bandgap transitions of hexagonal boron nitride is investigated using optical reflectance under hydrostatic pressure in an anvil cell with sapphire windows up to 2.5 GPa. Features in the reflectance spectra associated with the absorption at the direct and indirect bandgap transitions are found to downshift with increasing pressure, with pressure coefficients of −26 ± 2 and −36 ± 2 meV GPa–1, respectively. The GW calculations yield a faster decrease of the direct bandgap with pressure compared to the indirect bandgap. Including the strong excitonic effects through the Bethe–Salpeter equation, the direct excitonic transition is found to have a…

Structural, vibrational and electrical study of compressed BiTeBr

Compresed BiTeBr has been studied from a joint experimental and theoretical perspective. Room-temperature x-ray diffraction, Raman scattering, and transport measurements at high pressures have been performed in this layered semiconductor and interpreted with the help of ab initio calculations. A reversible first-order phase transition has been observed above 6–7 GPa, but changes in structural, vibrational, and electrical properties have also been noted near 2 GPa. Structural and vibrational changes are likely due to the hardening of interlayer forces rather than to a second-order isostructural phase transition while electrical changes are mainly attributed to changes in the electron mobilit…

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…

Temperature and pressure dependence of the optical absorption in hexagonal MnTe

The absorption edge of hexagonal (NiAs structure) antiferromagnetic MnTe has been measured by means of light transmission experiments carried out at different temperatures in the range 16--420 K $(P=1\mathrm{bar})$ and hydrostatic pressures up to 9 GPa $(T=295\mathrm{K}).$ An indirect band gap has been found, in agreement with previous band-structure calculations, with an energy of ${E}_{\mathrm{ig}}=1.272\ifmmode\pm\else\textpm\fi{}0.013\mathrm{eV}$ at room temperature and pressure. The temperature dependence of the absorption edge is linear above the N\'eel temperature ${T}_{N}=310\mathrm{K},$ with a temperature coefficient $dE/dT=\ensuremath{-}(3.5\ifmmode\pm\else\textpm\fi{}0.1)\ifmmode…

High-pressure structural investigation of several zircon-type orthovanadates

Room temperature angle-dispersive x-ray diffraction measurements on zircon-type EuVO4, LuVO4, and ScVO4 were performed up to 27 GPa. In the three compounds we found evidence of a pressure-induced structural phase transformation from zircon to a scheelite-type structure. The onset of the transition is near 8 GPa, but the transition is sluggish and the low- and high-pressure phases coexist in a pressure range of about 10 GPa. In EuVO4 and LuVO4 a second transition to a M-fergusonite-type phase was found near 21 GPa. The equations of state for the zircon and scheelite phases are also determined. Among the three studied compounds, we found that ScVO4 is less compressible than EuVO4 and LuVO4, b…

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…

Characterization and Decomposition of the Natural van der Waals SnSb2Te4 under Compression

[EN] High pressure X-ray diffraction, Raman scattering, and electrical measurements, together with theoretical calculations, which include the analysis of the topological electron density and electronic localization function, evidence the presence of an isostructural phase transition around 2 GPa, a Fermi resonance around 3.5 GPa, and a pressure-induced decomposition of SnSb2Te4 into the high-pressure phases of its parent binary compounds (alpha-Sb2Te3 and SnTe) above 7 GPa. The internal polyhedral compressibility, the behavior of the Raman-active modes, the electrical behavior, and the nature of its different bonds under compression have been discussed and compared with their parent binary…

Low temperature mobilities of 2-D electrons in indium selenide: Neutral and ionized impurity scattering

Abstract Low temperature mobility of 2-D electrons in indium selenide is calculated, taking into account neutral and ionized impurity scattering. Two-dimensional electric subbands are originated due to quantum size effects, at both sides of thin ϵ-polytype layers, separated by two stacking faults from the bulk γ-InSe. Ionized impurities are in the ϵ-layer and then, spatially separated from 2-D electrons. Neutral impurities are adsorbed to stacking faults in the ϵ-γ interface. A relaxation time for dipole-like neutral impurity scattering is deduced. Calculated mobilities are compared to previous experimental results and the areal concentration of the neutral impurities is so estimated. The i…

Effects of high pressure on the optical absorption spectrum of scintillating PbWO4 crystals

The pressure behavior of the absorption edge of PbWO4 was studied up to 15.3 GPa. It red-shifts at -71 meV/GPa below 6.1 GPa, but at 6.3 GPa the band-gap collapses from 3.5 eV to 2.75 eV. From 6.3 GPa to 11.1 GPa, the absorption edge moves with a pressure coefficient of -98 meV/GPa, undergoing additional changes at 12.2 GPa. The results are discussed in terms of the electronic structure of PbWO4 which attribute the behavior of the band-gap to changes in the local atomic structure. The changes observed at 6.3 GPa and 12.2 GPa are attributed to phase transitions.

Electronic structure and optical properties of CdTe rock-salt high pressure phase

This paper reports on optical absorption and reflectance measurements in thin CdTe samples up to 15 GPa. All studied samples become virtually opaque at the pressure transition between the zinc-blende and rock-salt phases (3.9 GPa). As pressure increases up to 10 GPa, a relative transparency region is observed between 1.2 eV and 2.4 eV, whose high energy edge shifts to higher photon energies. Above 10 GPa the transparency region gradually shrinks and disappears at about 11 GPa. The low energy side of the absorption spectrum is attributed to free carrier absorption, as electronic structure calculations show that rock-salt CdTe is a semimetal or a low gap semiconductor. Band filling effects lo…

Bond length compressibility in hard ReB2 investigated by x-ray absorption under high pressure

International audience; This work describes x-ray absorption measurements under high pressure in ReB2 , complemented by ab initio calculations. The EXAFS analysis yields the average Re–B bond compressibility, which turns out to be χReB = 5.6(9) × 10− 4 GPa−1 . Combining this information with previous x-ray diffraction experiments we have characterized the network of covalent bonds responsible for the rigidity of the structure. The main conclusion is that the compression is anisotropic and nonhomogeneous, reflecting bonding differences between Re–B and B–B bonds and also between nonequivalent Re–B bonds. The layer defined by boron atoms tends to become flatter under high pressure. As a conse…

Long lifetime of the E1u in-plane infrared-active modes of h -BN

We present an infrared reflectivity study of the ${E}_{1u}$ in-plane phonons of hexagonal BN as a function of temperature in the 40--680 K range. The infrared reflectance spectra of high-quality lamellar single crystals are accurately fitted using Lowndes' factorized form of the dielectric response, where the longitudinal-optic (LO) frequency is an independent adjustable parameter. From this analysis we obtain reliable values for the phonon damping of the IR-active ${E}_{1u}$ phonons which couple to light and give rise to the phonon-polariton excitations in this hyperbolic material. Anharmonic coupling potentials are estimated from the temperature dependence of the damping parameters. The $…

Transport measurements in InSe under high pressure and high temperature: shallow-to-deep donor transformation of Sn related donor impurities

We have investigated the temperature dependence of the transport parameters of Sn-doped InSe at different pressures, up to 2.5 GPa. A noticeable change in the temperature dependence of all the transport parameters has been observed above 1.2 GPa. This fact is explained by assuming the transformation of Sn shallow donors into deep donors at a hydrostatic pressure of 1.1 GPa, and by taking into account the transfer of electrons from the absolute minimum to higher energy minima in the conduction band. At ambient pressure, the position of the Sn deep level is estimated to lie 75 ± 20 meV above the absolute conduction-band minimum.

Growth and characterisation of MnTe crystals

We report on the low temperature growth of MnTe crystals by means of travelling solution methods. Two different processes are considered; a classical THM process using a low temperature presynthesised MnTe ingot, and a modified THM process, in which an increasing length of solvent zone collects the tellurium that was added to the stoichiometric charge to decrease the reaction temperature. Ingots from the two methods are analysed by means of scanning electron microscopy, X-ray diffractometry, resistivity, susceptibility and optical absorption measurements.

Front Cover: High-pressure studies of topological insulators Bi2 Se3 , Bi2 Te3 , and Sb2 Te3 (Phys. Status Solidi B 4/2013)

High‐temperature behavior of impurities and dimensionality of the charge transport in unintentionally and tin‐doped indium selenide

A systematic study of the electron transport and shallow impurity distribution in indium selenide above room temperature or after an annealing process is reported by means of far‐infrared‐absorption and Hall‐effect measurements. Evidences are found for the existence of a large concentration of deep levels (1012–1013 cm−2), related to impurities adsorbed to stacking faults in this material. Above room temperature impurities can migrate from those defect zones and then become shallow in the bulk. The subsequent large increase of 3D electrons can change the dimensionality of the electron transport, which in most cases was 2D. The temperature dependence of the resistivity parallel to the c axis…

Temperature dependence of refractive index and absorption coefficient of GaSe at 633 nm

Abstract Measurements of the ordinary refractive index and the absorption coefficient ( E /t] to c axis ) of gallium selenide at 633 nm, in the temperature range [20,100] °C, are reported. Useful analytical approximations obtained after a least squares fitting process are provided, as well. These results are basic for any theoretical model of nonlinear and bistable optical devices based on GaSe.

Pressure effects on the electronic and optical properties ofAWO4wolframites (A =Cd, Mg, Mn, and Zn): The distinctive behavior of multiferroic MnWO4

The electronic band-structure and band-gap dependence on the $d$ character of ${A}^{2+}$ cation in $A$WO${}_{4}$ wolframite-type oxides is investigated for different compounds ($A$ $=$ Mg, Zn, Cd, and Mn) by means of optical-absorption spectroscopy and first-principles density-functional calculations. High pressure is used to tune their properties up to 10 GPa by changing the bonding distances establishing electronic to structural correlations. The effect of unfilled $d$ levels is found to produce changes in the nature of the band gap as well as its pressure dependence without structural changes. Thus, whereas Mg, Zn, and Cd, with empty or filled $d$ electron shells, give rise to direct and…

Pressure dependence of photoluminescence of InAs/InP self-assembled quantum wires

6 páginas, 4 figuras, 1 tabla.-- PACS 62.50.+ p, 73.21.Hb, 78.55.Cr, 78.67.Lt, 81.15.Hi, 81.16.Dn

Structure Solution of the High-Pressure Phase of CuWO4 and Evolution of the Jahn–Teller Distortion

In this work, we have investigated the structural behavior of cuproscheelite up to 33.9 GPa by means of high-pressure single-crystal X-ray diffraction (SXRD) and extended X-ray absorption fine structure (EXAFS). According to EXAFS, beyond 9 GPa a phase transition takes place. On the basis of SXRD, the transition is from the triclinic (P1) structure to a monoclinic (P2/c) structure isotypic to wolframite. The transition implies abrupt changes of CuO6 and WO6 octahedra, but no coordination change. Further, we report the role played by the Jahn–Teller distortion of the CuO6 octahedra on the mechanism of the phase transition as well as the changes in the behavior of the Cu–O bonds for the tricl…

Light-induced transmission nonlinearities in gallium selenide

The intensity of a He–Ne laser (633 nm, 5 mW) transmitted by different GaSe samples is observed to change in correlation with a Nd-yttrium–aluminum–garnet laser pulse (532 nm, 7.8 ns, 3 mJ) which excites them. Such time response has been attributed to a nonlinear optical effect, i.e., a decrease in the refractive index due to the exciton screening by the photogenerated carriers. A calculation of the absorption coefficient and refractive index at different carrier concentrations has led to a reconstruction of transmittance transients which fully agree with the experimental data at different incident intensities and temperatures. Chantal.Ferrer@uv.es ; Jaqueline.Bouvier@uv.es ; Miguel.Andres@…

High-pressure structural study of the scheelite tungstatesCaWO4andSrWO4

Angle-dispersive x-ray-diffraction and x-ray-absorption near-edge structure measurements have been performed on ${\mathrm{CaWO}}_{4}$ and ${\mathrm{SrWO}}_{4}$ up to pressures of approximately 20 GPa. Both materials display similar behavior in the range of pressures investigated in our experiments. As in the previously reported case of ${\mathrm{CaWO}}_{4}$, under hydrostatic conditions ${\mathrm{SrWO}}_{4}$ undergoes a pressure-induced scheelite-to-fergusonite transition around 10 GPa. Our experimental results are compared to those found in the literature and are further supported by ab initio total-energy calculations, from which we also predict the instability at larger pressures of the …

Phase segregation in Mg$_{x}$Zn$_{1-x}$O probed by optical absorption and photoluminescence at high pressure

The appearance of segregated wurtzite Mg$_x$Zn$_{1-x}$O with low Mg content in thin films with $x&gt;0.3$ affected by phase separation, cannot be reliably probed with crystallographic techniques owing to its embedded nanocrystalline configuration. Here we show a high-pressure approach which exploits the distinctive behaviors under pressure of wurtzite Mg$_x$Zn$_{1-x}$O thin films with different Mg contents to unveil phase segregation for $x&gt;0.3$. By using ambient conditions photoluminescence (PL), and with optical absorption and PL under high pressure for $x=0.3$ we show that the appearance of a segregated wurtzite phase with a magnesium content of x $\sim$ 0.1 is inherent to the wurtzit…

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…

Effects of Conduction Band Structure and Dimensionality of the Electron Gas on Transport Properties of InSe under Pressure

We report Hall effect and resistivity measurements in InSe under pressure. The electron concentration strongly decreases under pressure in samples exhibiting 3D transport behaviour. This is explained by the existence of an excited minimum in the conduction band moving to lower energies under pressure. The related impurity level traps electrons as it reaches the band gap and approaches the Fermi level. In samples exhibiting 2D behaviour the electron concentration remains constant. This behaviour, together with the pressure dependence of the Hall mobility, is consistent with a previous model which considers high mobility 3D electrons and low mobility 2D electrons to contribute to charge trans…

Strong optical nonlinearities in gallium and indium selenides related to inter-valence-band transitions induced by light pulses

A nonlinear optical effect is shown to occur in gallium and indium selenides at photon energies of the order of 1.5 eV. It corresponds to transitions from a lower-energy valence band to the uppermost one when a nonequilibrium degenerate hole gas is created in the latter by a laser pulse. This inter-valence-band transition is allowed by crystal symmetry. Its oscillator strength is estimated through the $f$-sum rule and turns out to be about two orders of magnitude higher than that of the fundamental transition. The intensity of this effect is stronger when the pump pulse photon energy is close to that of the inter-valence-band transition; a condition that can be fulfilled only in indium sele…

Correlation between optical and transport properties of Ga-doped ZnO thin films prepared by pulsed laser deposition

Abstract In this paper we report on the correlation between the transport and optical properties of Ga-doped ZnO films epitaxially grown on C-oriented sapphire substrates by means of pulsed laser deposition. Thin films with electron concentrations ranging between 10 20 and 10 21  cm −3 were prepared from targets containing 0.25–5 at.% Ga. The Ga content in the thin films was estimated by XPS, from the ratio between the intensities of the 2p peaks of Ga and Zn. The electron concentration in the films is very close to the Ga content for films prepared from low Ga content targets even at high deposition temperature. For Ga contents in the target larger than 1%, the Ga content in the films incr…

Pressure dependence of the interlayer and intralayer E2g Raman-active modes of hexagonal BN up to the wurtzite phase transition

We present a Raman-scattering study of the interlayer and intralayer ${E}_{2g}$ Raman-active modes of hexagonal boron nitride $(h\ensuremath{-}\mathrm{BN})$ under hydrostatic pressure for pressures up to the transition to the wurtzite phase (10.5 GPa). Pressure coefficients and Gr\"uneisen parameters are determined for both modes, and are compared to ab initio calculations based on density functional perturbation theory. The pressure coefficient of the low-energy interlayer mode is higher than that of the high-energy intralayer mode owing to the large compressibility of the $h\ensuremath{-}\mathrm{BN}$ crystal along the $c$ direction. Both modes exhibit a sublinear phonon frequency increase…

X-ray-absorption fine-structure study of ZnSexTe1−x alloys

X-ray-absorption fine-structure experiments at different temperatures in ZnSexTe1−x (x=0, 0.1, 0.2, 0.55, 0.81, 0.93, 0.99, and 1.0) have been performed in order to obtain information about the structural relaxation and disorder effects occurring in the alloys. First and second neighbor distance distributions have been characterized at the Se and Zn K edges, using multiple-edge and multiple-scattering data analysis. The first neighbor distance distribution was found to be bimodal. The static disorder associated with the Zn–Te distance variance did not depend appreciably on composition. On the other hand, the static disorder associated with the Zn–Se distance increased as the Se content dimi…

ChemInform Abstract: Tuning the Band Gap of PbCrO4Through High-Pressure: Evidence of Wide-to-Narrow Semiconductor Transitions.

Commercial polycrystalline and cleaved platelets from natural PbCrO4 are studied in a diamond anvil cell at ≤ 21 GPa.

Buildup and structure of theInSe∕Ptinterface studied by angle-resolved photoemission and x-ray absorption spectroscopy

The atomic structure and the electronic nature of the $\mathrm{In}\mathrm{Se}∕\mathrm{Pt}$ interface have been studied by x-ray absorption spectroscopy and angle-resolved photoemission, respectively. By these measurements, it has been found that Pt atoms equally incorporate into two trigonal-prismatic intralayer positions existing within the InSe layer, although, at low Pt coverage, Pt atoms seem to prefer one of these sites, where they have a lower interaction with Se atoms. The atomic structure of the $\mathrm{In}\mathrm{Se}∕\mathrm{Pt}$ interface appears to determine its electronic behavior as Pt deposition increases. At initial stages of Pt diffusion, isolated Pt atoms act as a surface …

CCDC 1427507: Experimental Crystal Structure Determination

Related Article: Eugenio Coronado, M. Carmen Giménez-López, Tomasz Korzeniak, Georgiy Levchenko, Francisco M. Romero, Alfredo Segura, Valentín García-Baonza, Julio C. Cezar, Frank M. F. de Groot, Alla Milner, Moshe Paz-Pasternak|2008|J.Am.Chem.Soc.|130|15519|doi:10.1021/ja8047046

CCDC 1588161: Experimental Crystal Structure Determination

Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D

CCDC 1588164: Experimental Crystal Structure Determination

Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D

CCDC 1588162: Experimental Crystal Structure Determination

Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D

CCDC 1588165: Experimental Crystal Structure Determination

Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D

CCDC 1588166: Experimental Crystal Structure Determination

Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D

CCDC 1427488: Experimental Crystal Structure Determination

Related Article: Eugenio Coronado, M. Carmen Giménez-López, Tomasz Korzeniak, Georgiy Levchenko, Francisco M. Romero, Alfredo Segura, Valentín García-Baonza, Julio C. Cezar, Frank M. F. de Groot, Alla Milner, Moshe Paz-Pasternak|2008|J.Am.Chem.Soc.|130|15519|doi:10.1021/ja8047046

CCDC 1588163: Experimental Crystal Structure Determination

Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D

CCDC 1588160: Experimental Crystal Structure Determination

Related Article: José Navarro-Sánchez, Ismael Mullor-Ruíz, Catalin Popescu, David Santamaría-Pérez, Alfredo Segura, Daniel Errandonea, Javier González-Platas, Carlos Martí-Gastaldo|2018|Dalton Trans.|47|10654|doi:10.1039/C8DT01765D