Evolution of thermal conductivity of In3Sbβ Teγ thin films up to 550 °C

The temperature dependent thermal conductivity of In–Sb–Te thin films has been measured by modulated photothermal radiometry in the 20–550 °C range for samples with different Te content. Significant changes with temperature are observed and ascribed to a sequence of structural transformations on the basis of in‐situ Raman spectra. The data suggest that the as‐deposited material consisting of a mixture of polycrystalline InSb_0.8Te_0.2and amorphous Te first undergoes a progressive crystallization of the amorphous part, mostly above 300 °C. Further increase in temperature above 460 °C leads, for higher Te content in the alloy, to the formation of crystalline In₃SbTe₂, intertwined with a less conductive compound, possibly InTe and/or InSb. Upon cooling to room temperature, the initial polycrystalline InSb_0.8Te_0.2phase is mostly recovered along with other compounds, with a slightly higher thermal conductivity than that of the as deposited material. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Characterization on electron beam evaporated α-MoO3 thin films by the influence of substrate temperature

Electrochromic molybdenum oxide (MoO₃) thin films were prepared by electron beam evaporation technique using the dry MoO₃ pellets. The films were deposited on glass and fluorine doped tin oxide (SnO₂:F or FTO) coated glass substrates at different substrate temperatures like room temperature (RT, 30 °C), 100 °C and 200 °C. The influence of substrate temperature on the structural, surface morphological and optical properties of the films has been studied. The X-ray diffraction analysis showed that the films are having orthorhombic phase MoO₃ (α-MoO₃) with 〈1 1 0〉 preferred orientation. The laser Raman scattering spectrum shows the polycrystalline nature of MoO₃ films deposited at 200 °C. The Raman-active band at 993 cm⁻¹ is corresponding to Mo–O stretching mode that is associated with the unique character of the layered structure of orthorhombic MoO₃. Needle—like morphology was observed from the SEM analysis. The energy band gap of MoO₃ films was evaluated which lies between 2.8 and 2.3 eV depending on the substrate temperature and substrates. The decrease in band gap value with increasing substrate temperature is owing to the oxygen-ion vacancies. The absorption edge shift shows the coloration effect on the films.     

Raman spectroscopy study of Na2MoO4·2H2O and Na2MoO4 under hydrostatic pressure

Raman spectroscopy measurements of polycrystalline Na₂MoO₄·2H₂O (NMHO) and Na₂MoO₄ (NM) under hydrostatic pressure (from 0 to 10 GPa) were performed. This study allowed us to monitor the stretching and bending vibrations of MoO₄ ions as well as the translational modes as a function of pressure. The pressure dependence of the wavenumbers of the modes indicates that the Na₂MoO₄·2H₂O undergoes two phase transitions at about ∼3 and ∼4 GPa. When releasing pressure, we have observed that the original spectrum is recovered, thereby pointing to a reversible process. The Na₂MoO₄ (NM) starting phase was found to be stable up to 10 GPa. The pressure‐dependent Raman data for NM did not reveal any structural modification. The influence of the pressure‐transmitting medium on the phase transitions is also discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Temperature‐induced phase transformations in Na2WO4 and Na2MoO4 crystals

Temperature‐dependent Raman studies on Na₂WO₄and Na₂MoO₄ crystals were performed in order to obtain information on structural changes induced by temperature evolution. The stability of the cubic phase of Na₂WO₄and Na₂MoO₄crystals was assessed and our results indicate that this phase is stable in the 8–823 K and 15–773 K ranges for Na₂WO₄ and Na₂MoO₄, respectively. The crystal of Na₂WO₄ shows a phase transition occurring at 833 K. Na₂MoO₄undergoes a sequence of three phase transitions, which were observed at 783–803, 823–913 and 943–950 K. In both crystals, a strong first‐order phase transition occurs as indicated by the behavior of the Raman modes: the Raman bands split and new bands appear below 100 cm⁻¹. These transitions are connected with tilting and/or rotations of the WO₄and MoO₄ tetrahedra, which leads to a disorder at the WO₄and MoO₄ sites. Copyright © 2010 John Wiley & Sons, Ltd.     

Probing the ferroelectric phase transition in sol–gel‐derived polycrystalline bismuth ferrite thin films

Polycrystalline BiFeO₃ (BFO) thin films were successfully grown on Pt/Ti/SiO₂/Si(100) and SrTiO₃ (STO) (100) substrates using the chemical solution deposition (CSD) technique. X‐ray diffraction (XRD) patterns indicate the polycrystalline nature of the films with rhombohedrally distorted perovskite crystal structure. Differential thermal analysis (DTA) was performed on the sol–gel‐derived powder to countercheck the crystal structure, ferroelectric (FE) to paraelectric (PE) phase transition, and melting point of bismuth ferrite. We observed a significant exothermic peak at 840 °C in DTA graphs, which corresponds to an FE–PE phase transition. Raman spectroscopy studies were carried out on BFO thin films prepared on both the substrates over a wide range of temperature. The room‐temperature unpolarized Raman spectra of BFO thin films indicate the presence of 13 Raman active modes, of which five strong modes were in the low‐wavenumber region and eight weak Raman active modes above 250 cm⁻¹. We observed slight shifts in the lower wavenumbers towards lower values with increase in temperature. The temperature‐dependent Raman spectra indicate a complete disappearance of all Raman active modes at 840 °C corresponding to the FE–PE phase transitions. There is no evidence of soft mode phonons. Copyright © 2008 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman scattering studies on Na2Mo2O7 disodium dimolybdate

Temperature–dependent Raman studies of disodium dimolybdate (Na₂Mo₂O₇) crystal are reported. Lattice dynamical calculation was used to predict both wavenumbers and atomic displacements (eigenvectors) for the vibrational modes. These calculations were based on the classical rigid‐ion model. The high‐temperature Raman scattering study of the crystal showed that it remains in the orthorhombic structure in the 8–848 K range and undergoes a structural phase transition between 848 and 854 K. This phase transition is most likely connected with weak tiltings and/or rotations of both MoO₄ (tetrahedra) and MoO₆ (octahedra) units, which lead to a disorder in the oxygen sublattice. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and phonon properties of nanosized Aurivillius phase of Bi2MoO6

Nanosized crystallites Bi₂MoO₆ of a platelet shape were synthesized by a mild hydrothermal crystallization process. The effect of particle size on the structure and properties of Bi₂MoO₆ was studied by X‐ray diffraction, transmission electron microscopy, as well as Raman and infrared (IR) spectroscopies. Moreover, temperature‐dependent Raman spectra were collected for bulk and nanocrystalline Bi₂MoO₆. These studies showed that the thickness of the smallest crystallites is about 8–11 nm. Raman and IR studies have revealed that the damping and the intensity of Raman and IR bands are significantly modified with decreasing particle size and temperature. Moreover, some bands experience significant shifts both towards lower and higher wavenumbers. The obtained results indicate that, similar to the isostructural Bi₂WO₆, the orthorhombic distortion decreases with decreasing particle size. However, the structure of nanocrystalline Bi₂MoO₆ remains orthorhombic and noncentrosymmetric, and the structural changes are not the same as those observed in Bi₂WO₆. Copyright © 2010 John Wiley & Sons, Ltd.     

Ionic conductivity of double sodium-scandium and cesium-zirconium molybdates

The electrical properties of the Na₃Sc(MoO₄)₃ and Cs₂Zr(MoO₄)₃ compounds are investigated using impedance spectroscopy (1–10⁶ Hz) in the temperature range 100–650°C. Double molybdates in the form of a fine-crystalline powder are obtained by solid-phase synthesis in air at 450–600°C for 20–50 h. It is found that the temperature dependence of the ionic conductivity of ceramic samples exhibits anomalies at temperatures of 605 ± 5°C for Na₃Sc(MoO₄)₃ and 425 ± 15°C for Cs₂Zr(MoO₄)₃ due to the phase transitions, which are confirmed by the data of thermal analysis. Above the superionic transitions, the ionic conductivity reaches 0.084 S/cm (650°C) for Na₃Sc(MoO₄)₃ and 0.002 S/cm (462°C) for Cs₂Zr(MoO₄)₃.     

Micro‐Raman study of Zr‐substituted Bi4Ti3O12 ceramics

We have studied the lattice vibrational modes of Zr‐substituted Bi₄Ti₃O₁₂ ceramics using micro‐Raman spectroscopy. Replacement of Zr at the Ti site in the perovskite block is found from the increase in the lattice parameters as a function of Zr contents. Combined X‐ray diffraction patterns and Raman analysis suggested less than 40 mole% Zr solubility in Bi₄Ti₃O₁₂. At 40 mole% of Zr substitution or above, the unreacted monoclinic‐phase ZrO₂ is observed in the X‐ray diffraction patterns and the Raman spectra. The incorporation of Zr in Bi₄Ti₃O₁₂ reduces the soft mode wavenumber and the transition temperature. Moreover, temperature dependent studies confirmed the ferroelectric to paraelectric transition in Bi₄Ti₃O₁₂ at about 675 °C. On increasing the Zr content up to 40% on the Ti sites of Bi₄Ti₃O₁₂, a systematic decrease in the phase transition temperature from 675 to 630 °C was observed. Copyright © 2007 John Wiley & Sons, Ltd.     

Structural,spectroscopic and dielectric properties of KVO3

Polycrystalline samples of KVO₃, a member of the pyroxene structural family have been synthesised with high-temperature solid-state reaction technique. Preliminary structural and spectroscopic and detailed dielectric properties have been studied in different conditions. No dielectric anomaly or hysteresis loop has been observed in a wide temperature range (30°C to 450°C). Basic structural and spectroscopic (IR and Raman) studies suggest that at room temperature, KVO₃ is centrosymmetric as reported earlier. This and other observations do not support the recent report of ferroelectric phase transition in the compound.     

Pulsed laser deposition of molybdenum oxide thin films

Thin films of molybdenum oxide were deposited in vacuum by pulsed laser ablation using a xenon fluoride (351 nm) and a krypton fluoride (248 nm) excimer lasers. The films were deposited on unheated substrates and were post-annealed in air in the temperature range 300–500°C. The structural, morphological, chemical, and optical properties of the films were studied. As-deposited films were found to be dark. The transparency of the films was improved with annealing in air. The films were polycrystalline with diffraction peaks that belong to the orthorhombic phase of MoO₃. The surface morphology of the films showed a layered structure. Both the grain size and surface roughness increased with annealing temperature. The stoichiometry of the films improved upon annealing in air, with the best stoichiometry of MoO_2.95 obtained for films deposited by the XeF laser and annealed at 400°C. Similarly, the best transparency, with a transmittance exceeding 80%, was obtained with the films annealed in the temperature range 400–450°C.     

Surface optical Raman modes in GaN nanoribbons

Raman scattering studies were performed in GaN nanoribbons grown along [1 0 0]. These samples were prepared inside Na‐4 mica nanochannels by the ion‐exchange technique and subsequent annealing in NH₃ ambient. Detailed morphological and structural studies including the crystalline orientation were performed by analyzing the vibrational properties in these GaN nanoribbons. Pressure in the embedded structure was calculated from the blue shift of the E₂(high) phonon mode of GaN. Possible red shift of optical phonon modes due to the quantum confinement is also discussed. In addition to the optical phonons allowed by symmetry, two additional Raman peaks were also observed at ∼633 and 678 cm⁻¹ for these nanoribbons. Calculations for the wavenumbers of the surface optical (SO) phonon modes in GaN in Na‐4 mica yielded values close to those of the new Raman modes. The SO phonon modes were calculated in the slab (applicable to belt‐like nanoribbon) mode, as the wavenumber and intensity of these modes depend on the size and the shape of the nanostructures. The effect of surface‐modulation‐assisted electron–SO phonon scattering is suggested to be responsible for the pronounced appearance of SO phonon modes. A scaling factor is also estimated for the interacting surface potential influencing the observed SO Raman scattering intensities. Copyright © 2010 John Wiley & Sons, Ltd.     

Substitution and proton doping effect on SrZrO3 behaviour: high‐pressure Raman study

The high‐pressure Raman studies of pure, Yb‐modified, protonated and non‐protonated SrZrO₃ dense ceramics were performed between 0.1 and 40 GPa using a diamond anvil cell. Lanthanide‐modified, protonated SrZrO₃ perovskites are potential materials for electrolytic membrane in fuel cells and electrolysers working at medium temperature. The comparison of the Raman spectra shows important differences in the pressure behaviour between the pure and Yb‐modified SrZrO₃ ceramics. SrZrO₃ exhibits a rigid structure without any structural modification, whereas for both SrZr_0.93 Yb_0.07 O_2.965 and SrZr_0.93 Yb_0.07 O_2.962 H_0.003 a sequence of structural modifications at 10, 20 and 35 GPa is revealed. The character of these structural modifications is very similar to that observed as a function of the temperature (orthorhombic Pnma 750 °C → pseudo‐tetragonal Imma 840 °C → tetragonal I4/mcm 1070 °C → cubic Pm3m), which suggests that they can be considered as the phase transitions. Despite the low level of proton content (0.3% mole/mole), significant difference between protonated and non‐protonated compounds is observed for the 700–750 cm⁻¹ doublet assigned to the Zr O octahedron stretching mode, perturbed by an oxygen atom vacancy and/or neighbouring Yb ion. The location of proton is discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Temperature‐dependent Raman scattering studies of Na2MoO4

The mode assignment of the cubic phase of anhydrous Na₂MoO₄ was carried out on the basis of lattice dynamic calculation using the classical rigid‐ion model. Temperature‐dependent studies indicate that this crystal remains in the cubic structure in the 15–773 K range and undergoes a phase transition at around 783 K. The behavior of the Raman modes indicates that this transition is strongly first‐order in nature and the phase above 773 K may have an orthorhombic symmetry. This transition is connected with tilting and/or rotations of the MoO₄ tetrahedra, which lead to a disorder at the MoO₄ sites. Our results give also evidence that the Mo O bond lengths decrease in the high‐temperature phase. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman and IR studies of BaBi2Ta2O9 prepared by a sol–gel process

The formation of ferroelectric BaBi₂Ta₂O₉ (BBT) by a sol–gel process was studied by X‐ray, Raman and infrared (IR) spectroscopy. Our results show that the formation of a Bi‐layered phase proceeds via an intermediate fluorite‐type phase. This method allows obtaining a BBT phase already at 750 °C. This temperature is about 150–200 °C lower than that required in the conventional solid‐state reaction. Therefore, a material with smaller particle size can be obtained. Raman and IR studies of the obtained Bi‐layered phase show that phonon properties of the synthesized particles are slightly different from those of the bulk material due to the size effect, defects and weak changes in local order. Temperature dependence of Raman and IR wavenumbers is consistent with the orthorhombic distortion of the BBT structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Investigation of thermostability and phonon–phonon interactions in Mo6S3I6 nanowires by Raman scattering spectroscopy

Detailed Raman scattering measurements were performed on molybdenum–sulfur–iodine nanowires (Mo₆S₃I₆). At room temperature, 21 well‐resolved Raman modes were experimentally observed for the first time in this new compound. The phase stability and vibrational properties of the nanowires were investigated by different temperature treatments. High‐temperature Raman spectra showed that the phase separation of Mo₆S₃I₆ nanowires took place between 573 and 673 K, followed by appearance of a new mode at 819 cm⁻¹ characteristic of the MoO₃ phase. Low‐temperature Raman scattering spectra showed a significant difference in phonon–phonon interactions between internal and external Raman modes of Mo₆S₃I₆ nanowires. These interesting vibrational properties can give new insights for improved material preparation and achievement of higher conductivity and other functional properties of these otherwise interesting materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman scattering from three phases in LiIO3

We studied the temperature dependence of the Raman spectrum of LiIO₃, from room temperature up to t ～ 350°C. Two discontinuous changes in the spectrum are observed as temperature increases. The first one is reversible and occurs in a temperature range between 215°C and 260°C, depending upon sample origin (single crystal or powder) and thermal history. The second occurs at t ? 290°C and becomes irreversible once the samples are heated above 340°C. Each phase has a characteristic spectrum, distinct from that of the other two. Although the occurence of these phase changes are in complete agreement with studies made with X-ray diffraction and differential thermal analysis (DTA), it is at variance with previous Raman and infrared work which report no qualitative change in spectrum at the α ? γ phase transition. We believe this disagreement comes about because our measurements are the first ones so far to have actually passed through the transition.     

Electrocaloric effect in antiferroelectric PbZrO3 thin films

Antiferroelectric PbZrO₃ thin films have been deposited on Pt(111)/Ti/SiO₂/Si substrate by polymer modified sol–gel route. Temperature dependent P –E hysteresis loops have been measured at 51 MV/m within a temperature range of 40 °C to 330 °C. The maximum electrocaloric effect ～0.224 × 10^–6 K mV^–1 has been observed near the dielectric phase transition temperature (235 °C) of the thin films. The electrocaloric effect and its strong temperature dependence have been attributed to nearly first‐order phase transition. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High-temperature X-ray diffraction and Raman scattering studies of Ba-doped (Na0.5Bi0.5)TiO3 Pb-free piezoceramics

The structural changes in (100 ? x)Na_0.5Bi_0.5TiO₃–xBaTiO₃ (0 ≤ x ≤ 10) ceramics were investigated as a function of composition and temperature by X-ray diffraction and Raman spectroscopy. As Ba concentration increases, the structure changed from rhombohedral to tetragonal (x ≥ 6.5) across a morphotropic phase boundary like phase coexistence at x ～ 5.5, which is further evidenced by phonon anomalies observed in composition-dependent Raman spectra. On heating, the disappearance of peak splits in {111} (x ≤ 5) and {200} (x ≥ 6.5) Bragg peaks and the changes in their 2θ-positions indicated temperature-driven structural changes: ferroelectric to antiferroelectric (≈T_d, depolarization temperature) at 220 °C and antiferroelectric to paraelectric (rhombohedral to tetragonal) at 320 °C. In addition, Raman spectral analysis suggested that at elevated temperatures, two tetragonal phases with slightly different space groups coexisted at x ≥ 6.5 and most of the phase transition temperatures shifted towards left with increasing x.     

Raman studies on nanocomposite silicon carbonitride thin film deposited by r.f. magnetron sputtering at different substrate temperatures

Raman studies of nanocomposite SiCN thin film by sputtering showed that with increase of substrate temperature from room temperature to 500 °C, a transition from mostly sp² graphitic phase to sp³ carbon took place, which was observed from the variation of I_D/I_G ratio and the peak shifts. This process resulted in the growth of C₃N₄ and Si₃N₄ crystallites in the amorphous matrix, which led to increase in hardness (H) and modulus (E) obtained through nanoindentation. However, at a higher temperature of 600 °C, again an increase of sp² C concentration in the film was observed but the H and E values showed a decrease due to increased growth of the graphitic carbon phase. The whole process got reflected in a modified four‐stage Ferrari–Robertson model of Raman spectroscopy. Copyright © 2010 John Wiley & Sons, Ltd.