D. Martinez-Garcia

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 contribute to the top of the valence band and the bottom of the conduction band (e.g. PbWO4). The results are of importance in view of the large discrepancies existent in prevoiusly published data.

High conductivity of Ga-doped rock-salt ZnO under pressure: Hint on deep-ultraviolet-transparent conducting oxides

This letter reports on transport and optical experiments under pressure in thin films of Ga-doped ZnO in both the wurtzite and rock-salt phases. The conductivity of heavily Ga-doped ZnO thin films is shown to decrease by only a factor of 2 in the wurtzite-to-rock-salt phase transition, occurring at about 11.5 GPa, while the optical gap increases from 4 to more than 5 eV. Ga-doped rock-salt ZnO is shown to behave as a deep-ultraviolet-transparent conducting oxide, with resistivity values as low as 10−3Ωcm. The analysis of Burstein–Moss shift and free carrier absorption in rock-salt ZnO yield an estimation of the electron-hole reduced effective mass and electronic dielectric constant. Given the similarity between the electronic structures of rock-salt ZnO under pressure and rock-salt MgxZn1−xO at ambient pressure, this alloy could be a good deep-ultraviolet-transparent conducting oxide.

Density measurements of liquid under high pressure and high temperature

A new method for density measurements by means of X-ray absorption under high pressure and high temperature using synchrotron radiation has been developed. The method has been modified for a large-volume Paris-Edinburgh press and combined with intense high-energy X-rays at the ESRF. In order to overcome effects of deformation of sample shape under pressure, a ruby cylinder was used as a sample container. The density was determined from the intensity profile of transmitted X-rays. The densities of crystalline and liquid Bi were successfully measured up to 750 K at 1 GPa.

Hall-effect and resistivity measurements in CdTe and ZnTe at high pressure: Electronic structure of impurities in the zinc-blende phase and the semimetallic or metallic character of the high-pressure phases

We carried out high-pressure resistivity and Hall-effect measurements in single crystals of CdTe and ZnTe up to 12 GPa. Slight changes of transport parameters in the zincblende phase of CdTe are consitent with the shallow character of donor impurities. Drastic changes in all the transport parameters of CdTe were found around 4 GPa, i.e. close to the onset of the cinnabar to rock-salt transition. In particular, the carrier concentration increases by more than five orders of magnitude. Additionally, an abrupt decrease of the resistivity was detected around 10 GPa. These results are discussed in comparison with optical, thermoelectric, and x-ray diffraction experiments. The metallic character of the Cmcm phase of CdTe is confirmed and a semi-metallic character is determined for the rock-salt phase. In zincblende ZnTe, the increase of the hole concentration by more than two orders of magnitude is proposed to be due to a deep-to-shallow transformation of the acceptor levels. Between 9 and 11 GPa, transport parameters are consistent with the semiconducting character of cinnabar ZnTe. A two orders of magnitude decrease of the resistivity and a carrier-type inversion occurs at 11 GPa, in agreement with the onset of the transition to the Cmcm phase of ZnTe. A metallic character for this phase is deduced.

Thermoelastic behaviour of hexagonal graphite-like boron nitride

Abstract A synchrotron X-ray diffraction study on hexagonal graphite-like boron nitride (h-BN) was performed under high pressures and temperatures. From the measured P-V-Trelation for h-BN (with a three-dimensional ordering parameter P3 = 0.9) in the temperature range from 298 to 1273 K and up to 6.7 GPa, the thermoelastic parameters are derived by fitting a modified high temperature Birch-Murnaghan equation of state. The results are: bulk modulus B0[GPa] = 27.6-0.0081(T[K]-298) and its pressure derivative B1 = 10.5 + 0.0016(T [K] - 298). These values are for samples with P3 = 0.9 and are quite different for samples with different values of the order parameter. This parameter is shown to have a leading role in the determination of the thermoelastic properties of h-BN, which explains and reconciles the differences between previous results.

Compact multianvil device for in situ studies at high pressures and temperatures

We describe a recently developed device for in situ studies at pressures up to 25 GPa and temperatures up to 2300 K. The system consists of a 450 ton V7 Paris-Edinburgh press combined with a Stony Brook ‘T-cup’ multianvil stage. Such a compact large-volume set-up has a total mass of 100 kg only and can be readily used on most synchrotron radiation facilities. The optimization of the set-up by off-line tests is detailed, and we present some X-ray diffraction results which demonstrate the potential of the technique.

Pressure-induced phase transition and band-gap collapse in the wide-band-gap semiconductor InTaO4

This paper was partially supported by the Spanish Ministerio de Economia y Competitividad (MINECO) under Grants No. MAT2013-46649-C04-01/02/03 and No. MAT2015-71070-REDC (MALTA Consolider). The XRD experiments were performed at the MSPD-BL04 beamline at ALBA Synchrotron with the collaboration of ALBA staff. We thank S. Agouram from SC-SIE at Universitat de Valencia for technical support with the transmission electron microscope measurements.

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.

High-pressure and high-temperature X-ray diffraction studies of scheelite BaWO4

We carried out high-pressure (HP) and high-temperature (HT) in situ ADXRD synchrotron measurements in barium tungstate (BaWO4) up to 7.5 GPa and 800 K. Coexistence of the scheelite and fergusonite structures was found beyond 7 GPa, both at room temperature and HT, suggesting a polymorphism zone in the P–T phase diagram. The experiments are complemented by thermodynamic calculations within the quasi-harmonic approximation. At ambient pressure, a volume thermal expansivity of 9.5×10−6 K−1 was obtained for scheelite BaWO4. At HP, the thermal expansivity of the fergusonite doubles that of scheelite. Theoretical equation of state curves at HP and HT are also presented.

Nanocrystals of cdte formed by the pressure cycle method

Recently, it has been shown that CdTe has two sucessive phase transitions over a narrow pressure range at ≅3.5 GPa. In this work, the pressure cycle method using a Paris-Edinburgh cell up to 6 GPa has been applied to CdTe samples in order to obtain recovered CdTe nanocrystals which were characterized by high resolution transmission electron microscopy (HRTEM), electron diffraction and Raman scattering. Such retrieved nanocrystals are nearly spherical, with diameters ranging from 10 to 30 nm, and their structure is zinc-blende (ZB). Their Raman spectra is consistent with the CdTe phonon dispersion curves but reveal a phonon confinement effect.