Muhtar Ahart

Origin of morphotropic phase boundaries in ferroelectrics.

A piezoelectric material is one that generates a voltage in response to a mechanical strain (and vice versa). The most useful piezoelectric materials display a transition region in their composition phase diagrams, known as a morphotropic phase boundary, where the crystal structure changes abruptly and the electromechanical properties are maximal. As a result, modern piezoelectric materials for technological applications are usually complex, engineered, solid solutions, which complicates their manufacture as well as introducing complexity in the study of the microscopic origins of their properties. Here we show that even a pure compound, in this case lead titanate, can display a morphotropic phase boundary under pressure. The results are consistent with first-principles theoretical predictions, but show a richer phase diagram than anticipated; moreover, the predicted electromechanical coupling at the transition is larger than any known. Our results show that the high electromechanical coupling in solid solutions with lead titanate is due to tuning of the high-pressure morphotropic phase boundary in pure lead titanate to ambient pressure. We also find that complex microstructures or compositions are not necessary to obtain strong piezoelectricity. This opens the door to the possible discovery of high-performance, pure-compound electromechanical materials, which could greatly decrease costs and expand the utility of piezoelectric materials.

Pressure-induced metallization of silane

There is a great interest in electronic transitions in hydrogen-rich materials under extreme conditions. It has been recently suggested that the group IVa hydrides such as methane (CH4), silane (SiH4), and germane (GeH4) become metallic at far lower pressures than pure hydrogen at equivalent densities because the hydrogen is chemically compressed in group IVa hydride compounds. Here we report measurements of Raman and infrared spectra of silane under pressure. We find that SiH4 undergoes three phase transitions before becoming opaque at 27–30 GPa. The vibrational spectra indicate the material transforms to a polymeric (framework) structure in this higher pressure range. Room-temperature infrared reflectivity data reveal that the material exhibits Drude-like metallic behavior above 60 GPa, indicating the onset of pressure-induced metallization.

Brillouin scattering study in the GaN epitaxial layer

Abstract We have investigated the elastic properties of a GaN epitaxial layer on a sapphire substrate by Brillouin scattering in the backward and 90° scattering geometries. A sample of high optical quality grown by the two-flow MOCVD method with a complex structure of In 0.05 Ga 0.95 N(0.05 μm)/GaN(2 μm)/sapphire was used. The weak spectra were not simple due to the boundaries and the InGaN thin film. The elastic constants of GaN were estimated and compared with those obtained from X-ray diffraction.

Brillouin-scattering determination of the acoustic properties and their pressure dependence for three polymeric elastomers

The acoustic properties of three polymer elastomers, a cross-linked poly(dimethylsiloxane) (Sylgard 184), a cross-linked terpolymer poly(ethylene-vinyl acetate-vinyl alcohol), and a segmented thermoplastic poly(ester urethane) copolymer (Estane 5703), have been measured from ambient pressure to approximately 12 GPa by using Brillouin scattering in high-pressure diamond anvil cells. The Brillouin-scattering technique is a powerful tool for aiding in the determination of equations of state for a variety of materials, but to date has not been applied to polymers at pressures exceeding a few kilobars. For the three elastomers, both transverse and longitudinal acoustic modes were observed, though the transverse modes were observed only at elevated pressures (>0.7 GPa) in all cases. From the Brillouin frequency shifts, longitudinal and transverse sound speeds were calculated, as were the C(11) and C(12) elastic constants, bulk, shear, and Youngs moduli, and Poissons ratios, and their respective pressure dependencies. P-V isotherms were then constructed, and fit to several empirical/semiempirical equations of state to extract the isothermal bulk modulus and its pressure derivative for each material. Finally, the lack of shear waves observed for any polymer at ambient pressure, and the pressure dependency of their appearance is discussed with regard to instrumental and material considerations.

High-pressure Brillouin scattering of amorphous BeH2

High-pressure micro-Brillouin scattering is employed to investigate the pressure dependence of the sound velocity, refractive index, equation of state, and mechanical properties of amorphous BeH2. The refractive index n has been determined by using two scattering geometries (70 degrees and 180 degrees). The equation of state is deduced from the pressure dependences of the sound velocity. The bulk modulus is 14.2 (+/-3.0) GPa and its pressure derivative is 5.3 (+/-0.5). The polarizability is calculated from the refractive index and the density of the material. It increases with pressure while Poissons ratio decreases with pressure.

High-pressure elastic properties of a fluorinated copolymer: Poly(chlorotrifluoroethylene-co-vinylidene fluoride) (Kel-F 800)

The acoustic properties and their pressure dependence have been determined to 18.5 GPa for nearly amorphous poly(chlorotrifluoroethylene-co-vinylidene fluoride) (Kel-F 800) using high-pressureBrillouin scattering. At all measuredpressures, both longitudinal and transverse acoustic modes were observed allowing for calculation of the pressure-volume isotherm for this predominantly amorphous material. Analysis of the room temperature isotherm using semi-empirical equation of state fitting forms to 5.5 GPa yielded a zero-pressure bulk modulus,Ko , and pressure derivative, Ko ′, of 2.8 GPa and 30.6, respectively, which are consistent with the results from dilatometry measurements at very low pressures. Furthermore, the C11 and C12 elastic moduli for the isotropic polymer were determined at each pressure interval and, subsequently, examined to provide the pressure dependence of the bulk, shear, and Young’s moduli. These results are discussed in relation to polymer mechanics at pressures far exceeding those of previous, static compression experiments.

Pressure Dependence of Acoustic Properties of Liquid Ethanol by using High-pressure Brillouin Spectroscopy

Brillouin spectroscopy has been widely used for the investigation of acoustic properties of condensed matters in the hypersonic region. A high-pressure Brillouin spectrometer was set up by combining a diamond anvil cell and a tandem multi-pass Fabry-Perot interferometer. It was successfully applied to liquid ethanol, and the pressure dependence of the sound velocity, the refractive index and other acoustic properties were derived based on the measurements. The detailed optical setup and experimental procedure are described.

Cubic boron nitride as a primary calibrant for a high temperature pressure scale

We present results establishing a new high pressure scale at high temperature based on the thermal equation of state and elastic properties of cubic boron nitride (cBN). This scale is derived from simultaneous measurements of density and sound velocities at high pressure and temperature independent of any previous pressure scale. The present results obtained at room temperature to 27 GPa suggest the validity of the current ruby scale (within±4% at 100 GPa). At high temperature, data obtained at 16 GPa to 723 K are in fair agreement with the thermal equation of state of cBN reported in our previous work. We have also shown that cBN can serve as a convenient pressure gauge in X-ray and optical studies using the laser heated diamond anvil cell.

Pressure dependence of the monoclinic phase in (1–x)Pb(Mg1/3Nb2/3)O3-xPbTiO₃ solid solutions

We combine high-pressure x-ray diffraction, high-pressure Raman scattering, and optical microscopy to investigate a series of (1 - x)Pb(Mg1/3Nb2/3)O-3-xPbTiO(3) (PMN-xPT) solid solutions (x = 0.2, 0.3, 0.33, 0.35, 0.37, 0.4) in diamond anvil cells up to 20 GPa at 300 K. The Raman spectra show a peak centered at 380 cm(-1) starting above 6 GPa for all samples, in agreement with previous observations. X-ray diffraction measurements are consistent with this spectral change indicating a structural phase transition; we find that the triplet at the pseudocubic (220) Bragg peak merges into a doublet above 6 GPa. Our results indicate that the morphotropic phase boundary region (x = 0.33 - 0.37) with the presence of monoclinic symmetry persists up to 7 GPa. The pressure dependence of ferroelectric domains in PMN-0.32PT single crystals was observed using a polarizing optical microscope. The domain wall density decreases with pressure and the domains disappear at a modest pressure of 3 GPa. We propose a pressure-composition phase diagram for PMN-xPT solid solutions. DOI: 10.1103/PhysRevB.86.224111

Critical slowing down of relaxation dynamics near the Curie temperature in the relaxor Pb(Sc0.5Nb0.5)O3

Brillouin spectroscopy of Pb(Sc0.5Nb0.5)O3 single crystals reveals an order-disorder ferroelectric phase transition occurs at 110 °C upon cooling. A softening of the longitudinal acoustic (LA) mode is observed that can be attributed to the coupling between polar nanoregions and acoustic modes. A critical slowing down of the central peak, a feature of order-disorder ferroelectric phase transitions, is observed near Tc. The similarity in temperature dependences of the two kinds of relaxation times determined from the central peak and LA mode suggests that the changes in the central peak arise from local polarization fluctuations in the polar nanoregions.