Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Pressure dependence of the optical-absorption edge of AlN and graphite-type BN

Effect of pressure on the band gaps on AlN and graphite-type BN (g-BN) has been studied up to 2.7 GPa at room temperature by measuring the optical-absorption edge of single crystals of each substance pressurized in a sapphire-anvil cell. The direct band gap of AlN shifted towards higher energy at a rate of 49±1 meV/GPa, whereas in g-BN the pressure dependence of the band gap was −36±1 meV/GPa. The results are compared with existing first-principles calculations.     

Phonon spectra of stoichiometric rare-earth compound of EuGa2S4

Investigations of EuGa₂S₄ have been done on the photoluminescence (PL) related to the transition between 4f⁶5d and 4f⁷ configuration of the Eu²⁺ ion and its excitation (PLE) spectra, Raman scattering and infrared absorption. The energies of phonons coupled to the ground and the excited states of the transition are analyzed to be 34 and 19 meV from the shapes of the PL and PLE bands, respectively. The former corresponds to the energy of the Raman line showing the highest intensity. The latter is close to the value obtained from analysis of the temperature dependence of the half width of the PL band. These correspondences indicate that the relevant emission of EuGa₂S₄ surely has phonon-terminated character.     

The effect of a large SWNT diameter distribution on cesium intercalation

Vapor-phase intercalation of a single-walled carbon nanotube sample with Cs was carried out and monitored in situ by Raman spectroscopy. Results indicate that the endpoint of the intercalation was limited by small interstitial gaps in the nanotube bundles. These small-diameter gaps are present because of the significant number of small-diameter nanotubes (0.9-1.0 nm, as calculated from Raman radial breathing mode frequencies) present in the sample. It is not possible to determine from our Raman spectra whether the early endpoint is the result of diffusion limitation or the equilibrium energetics at the endpoint, although some diffusion limitation is observed near the beginning of the reaction. A simple geometric model for expansion of the nanotube bundles under intercalation is presented; this model reproduces, reasonably well, measured expansions reported by others and explains both diffusion- and equilibrium-limited mechanisms in terms of the larger lattice expansion required for smaller-diameter nanotubes. Staging of the intercalation process, in analogy with the staged intercalation of graphite intercalation compounds, is not observed. Instead, the transverse mode peaks undergo a gradual decrease in intensity and a gradual charge transfer- and electronic coupling-induced downshift.     

Incident-angle dependence of the longitudinal optic mode and the Doppler effect in silica glass

The infrared reflection spectra of silica glass were monitored at different incident angles of the wave. The density of states (DOS) and frequency ω_LO of the longitudinal optic (LO) mode were found to be the functions of the incident angle. The DOS of the LO mode increases with increasing incident angle as a whole. However, two regions can be divided in which one is below ∼30° and the other is above 30°. The frequency ω_LO of the LO mode increases linearly with incident angle. The earlier proposed relationship between the shifted frequency produced by the Doppler effect and the source frequency of the main transverse optic (TO) mode was investigated by studying the infrared spectra of the annealed glass capillaries. The shifted frequency was found to be linearly proportional to the source frequency of the TO mode, as depicted by the Doppler effect.     

In situ Raman spectroscopy of cubic boron nitride to 90 GPa and 800 K

The temperature and pressure dependences of the Raman spectrum of the transverse-optical mode of cubic boron nitride were calibrated for applications to a Raman spectroscopy pressure sensor in optical cells to about 800 K and 90 GPa. A significant deviation from linearity of the pressure dependence is confirmed at pressures above 20 GPa. At ambient temperature, dv/dP slopes are 3.41(7) and 2.04(7) cm⁻¹/GPa at 0 and 90 GPa, respectively. A polynomial expression is used to fit the pressure–temperature dependence of the Raman line. The pressure dependence does not significantly change with temperature, as determined from experiments conducted up to 800 K. At 0 GPa, the dv/dP slope is 3.46(7) cm⁻¹/GPa at 800 K. At pressures above 90 GPa, the Raman spectrum of the transverse-optical mode cannot be observed because of an overlap of the signals of cubic boron nitride and diamond used as the anvils in the high-pressure cell.     

Zone center frequencies of the orthorhombic NdMnO3 perovskite

A short range force constant model has been applied for the first time to investigate the phonons in NdMnO₃ perovskite in the orthorhombic phase. The calculations with nine stretching and eight bending force constants provide good agreement for the observed Raman frequencies. The infrared frequencies have been assigned for the first time.     

Low-temperature vibrational properties of KGd(WO4)2: (Er, Yb) single crystals studied by Raman spectroscopy

Temperature-dependent polarized Raman spectra of KGd(WO₄)₂: (Er, Yb) single crystals have been analyzed over the 77-292 K temperature range. The A_g and B_g spectra obtained are discussed in terms of factor group analysis. The spectra have been found to reveal the bands related to internal and external vibrations of WO₄²⁻, WOW and WOOW molecular groups. Strong depolarization of the majority of the Raman bands has been observed in the whole temperature range. Some anomalies in the spectral parameters of selected Raman bands below 175 K have been discussed in terms of the local distortion of WO₄²⁻ ions in KGd(WO₄)₂: (Er, Yb) crystals.     

Pressure induced lattice anomalies in pnictides

Hydrostatic pressure Raman and synchrotron XRD measurements at room temperature have been carried out on a series of NdFeAsO_1−xF_y (Nd1111) oxypnictides in order to investigate pressure-induced lattice modifications. The synchrotron XRD data indicate that there is an increased deviation of the lattice constants from smooth pressure dependence in the superconducting compound, in close agreement with the results from SmFeAsO_1−xF_x (Sm1111), although the effect is less pronounced in Nd1111. As in Sm1111 the hydrostatic pressure Raman measurements show that the A_1g mode of the rare earth atom deviates from the linear pressure dependence. Anomalous pressure dependence and a hysteresis is observed in the phonon width of the phonon modes. The calculated Grüneisen parameter for the Nd phonon is very similar to the corresponding value for SmFeAsO_1−xF_x compound and it does not vary with substitution. For the As mode it has a lower value indicating a stiffer phonon with the increased ion size. In connection with the XRD measurements the Raman data show a sudden increase of the pressure-induced lattice anomalies close to doping where the compounds become superconducting.     

Evaluation of stoichiometric rare-earth molybdate and tungstate compounds as laser materials

Photoluminescence spectra, photoluminescence decay curves and Raman scattering spectra have been investigated for stoichiometric rare-earth molybdate and tungstate compounds. NaNd(MoO₄)₂ and NaNd(WO₄)₂ show emissions due to the transition ⁴F_3/2→⁴I_9/2 in Nd³⁺. A possibility of laser oscillation in NaNd(MoO₄)₂ is pointed from comparisons of the emission intensity and the decay time constant with NaNd(WO₄)₂ where laser oscillations have been reported. In NaLa(MoO₄)₂ and NaLa(WO₄)₂, observed emissions which are not related to La³⁺ are probably due to the transitions in MoO₄^2- and WO₄^2- molecular ions, respectively, in scheelite crystal. Raman spectra of these compounds are similar, probably related to the same crystal structure. LiEr(MoO₄)₂ shows the emissions due to transitions ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 in Er³⁺, respectively, which are believed to be observed for the first time.     

Raman spectra of Ba6−3xSm8+2xTi18O54 solid solution

Raman spectra of Ba_6−3xSm_8+2xTi₁₈O₅₄ solid solution were investigated as the function of x and sintering time. Reasonable explanations were provided about the Raman shifts and their intensities at 1013, 590, 751, 280, 232 cm⁻¹. 1013 cm⁻¹ demonstrates the existence of BaCO₃ phase in solid solution, 590 cm⁻¹ is the symmetric stretching mode of the basal oxygens of the octahedral; 280 and 232 cm⁻¹ are the symmetric stretching modes resulted from the tilt of octahedral when large cation sites are Sm³⁺ and Ba²⁺. The shoulder peak appearing around 302 cm⁻¹ is related to the vacancy produced by the unequal valence of Sm³⁺ and Ba²⁺.     

Percolation picture for long wavelength phonons in zinc blende alloys: application to GaInAs

We propose a ‘one bond→two modes’ model for the long wavelength optical phonons in random zinc-blende A_xB_1−xC ternary alloys, based on the percolation site theory. Our model takes into account the ‘fractal→normal’ object transition, which goes with the ‘dispersion→continuum’ topology transition at the percolation thresholds of the A-C and B-C bonds. We first introduce the basics of our model in the case of Zn_1−xBe_x(Se,Te) mixed crystals, whose parent binaries display a high contrast in the bond stiffness, which enhances the percolation effects. We then focus our study on standard systems, which display a much weaker contrast in the bond stiffness. The multi-phonon behavior of GaInAs alloys is re-examined in the light of the percolation model, with much success.     

Chemical composition of matrix-embedded ternary II–VI nanocrystals derived from first- and second-order Raman spectra

A one- and multiphonon Raman scattering study is performed for an extensive set of CdS_1–xSe_x, Cd_1–yZn_yS, Cd_1–yZn_ySe, and CdSe_1–xTe_x nanocrystals to investigate the applicability of first- and second-order Raman spectra for the determination of the matrix-embedded ternary nanocrystal composition. For one-mode ternary systems both the LO and 2LO phonon frequencies in the Raman spectra are shown to be a good measure of the nanocrystal composition. For two-mode systems, the approaches based on the difference of the LO phonon frequencies (first-order Raman spectra) or double LO overtone and combination tone frequencies (second-order Raman spectra) as well as on the LO phonon band intensity ratios are analysed. The weak electron–phonon coupling in the II–VI nanocrystals and the polaron constant values for the nanocrystal sublattices are discussed.     

High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

Collective dynamics of supercritical water

Inelastic X-ray scattering experiments on sub- and supercritical water were performed to investigate collective dynamics of this unique solvent. Analysis within a generalized Langevin formalism shows that the positive dispersion of the sound velocity, as compared to the hydrodynamic value, first decreases (1.0<ρ<0.8 g cm⁻³) at all measured momentum transfers (1.3-10.7 nm⁻¹), and then increases (0.7<ρ<0.26 g cm⁻³) again only at higher momentum transfers. We suggest the initial decrease is due to approaching the percolation limit in the number of hydrogen bonds, and the subsequent increase is due to the formation of rigid dimers in sub- and supercritical water.     

Doping dependence of the electronic Raman spectra in cuprates

We report electronic Raman scattering measurements on Bi₂Sr₂(Y_1−xCa_x)Cu₂O_8+δ single crystals at different doping levels. The dependence of the spectra on doping and on incoming photon energy is analyzed for different polarization geometries, in the superconducting and in the normal state. We find the scaling behavior of the superconductivity pair-breaking peak with the carrier concentration to be very different in B_1g and B_2g geometries. Also, we do not find evidence of any significant variation in the lineshape of the spectra in the overdoped region in both symmetries, while we observe a reduction of the intensity in B_2g upon decreasing photon energies. The normal state data are analyzed in terms of the memory-function approach. The quasiparticle relaxation rates in the two symmetries display a dependence on energy and temperature which varies with the doping level.     

The effects of plastic deformation on band gap, electronic defect states and lattice vibrations of rutile

The extensive polygonization of 200 nm rutile crystals in high-energy dry milling allowed to study the spectral properties of grain boundaries and adjacent microstrained crystalline matter. Changes in UV, VIS, NIR, IR and FIR spectra during milling were followed. For the UV absorption edge the value of unstrained rutile was retained while residual traces of anatase, intergrown with the rutile phase, continued to act as traps for photoinduced charges. The evolving broad absorption in VIS and NIR could be attributed to electrons weakly bound to defects in the packing of oxygen anions at the grain boundaries, which may relax to face-sharing Ti³⁺-O octahedra. Among the IR-active lattice vibrations, the narrow E_u⁽²⁾ band showed a shift to higher frequencies by 15 cm⁻¹ which is definitively not due to phonon confinement or Fröhlich surface modes but probably to coupling of the bulk phonon to a plasmon at the grain boundary. At the external surface of the polygonized primary particle, the regular atomic order is destroyed by milling so that hydroxylation is replaced by physisorption of H₂O, as shown by IR and TG.     

Pressure and volume dependence of Grüneisen parameter of solids

Using the assumption δ_T=δ_T0(V/V₀)^k and the Grüneisen parameter γ macroscopic definition expression, we obtained a relationship for the volume dependence of the Grüneisen parameter γ. We have calculated the Grüneisen parameter γ with this relationship for NaCl and ε-Fe at high pressure under study. The calculated values of γ are found to show fairly in good agreement with available experimental data.     

Raman spectra of samarium-fullerene intercalation compounds

Samarium-fullerene intercalation compounds of nominal composition Sm_xC₆₀ (x=1,2,…,6) have been synthesized by a solid-state reaction method. We obtain a Sm_2.75C₆₀ superconducting phase with orthogonal structure and a Sm₆C₆₀ phase with body-centered cubic structure. The broadening and weakening of Raman peaks of the Sm_xC₆₀ compounds are due to the distortion of C₆₀ and electron-phonon interaction. The Raman measurements reveal that the distortion of C₆₀ decrease in Sm_xC₆₀ (x=3,4,5) exposed to air, although the fulleride solids have transformed into an amorphous state. The Raman results also show that the distortion of C₆₀ is still very large in the Sm₆C₆₀ exposed to air, or the C₆₀ molecules have been destroyed and become some amorphous carbide.