This review summarizes Raman scattering data for different stable and metastable phases of vanadium oxides. We analyze literature data on crystal structures existing in the binary vanadium‐oxygen system. If available, we combine these data with experimental Raman spectra and relations of vibrational modes with the atomic arrangements and motions in crystals. Further, we employ arc sputtering to produce vanadium oxide films, including α and β‐vanadium, V14O6, VO, V2O3, V3O5, several phases of VO2, V6O13, V3O7, and V2O5, as confirmed by X‐ray diffraction analysis. All the films are studied using Raman spectroscopy: low‐ and high‐temperature V3O5 and VOx (1.67 < x < 2) are investigated for the first time. We demonstrate that a significant change in the V3O5 spectrum takes place along the phase transition occurring at approximately 140 °C. Moreover, we describe differences between the spectra of VO2 polymorphs produced without doping impurities, VO2 (M1), VO2 (M2), and VO2 (T). Finally, we analyze conflicting data on V7O16 and V3O7 and provide an explanation of the observed spectra. Overall, 21 spectra are identified for 53 known phases. Our work is aimed at laying the groundwork for easy identification of vanadium oxide phases in thin films, using Raman spectroscopy.
The voltage generated in a noncentrosymmetric crystal due to the bulk photovoltaic effect (BPE) can greatly exceed the energy gap, however, the light energy conversion efficiency is extremely low. Here we show that the BPE is remarkably enhanced in the case of thin films. The measurements of the BPE in heteroepitaxial single domain ferroelectric BaTiO 3 thin films reveal the enhancement of both photoinduced electric field and conversion efficiencies of the BPE by more than 4 orders of magnitude. Besides the fundamental aspect, our results indicate the potential for the use of the BPE in photovoltaic applications.
Electroresistance in ferroelectric tunnel junctions is controlled by changes in the electrostatic potential profile across the junction upon polarization reversal of the ultrathin ferroelectric barrier layer. Here, hard X-ray photoemission spectroscopy is used to reconstruct the electric potential barrier profile in as-grown Cr/BaTiO3(001)/Pt(001) heterostructures. Transport properties of Cr/BaTiO3/Pt junctions with a sub-μm Cr top electrode are interpreted in terms of tunneling electroresistance with resistance changes of a factor of ∼30 upon polarization reversal. By fitting the I-V characteristics with the model employing an experimentally determined electric potential barrier we derive the step height changes at the BaTiO3/Pt (Cr/BaTiO3) interface +0.42(−0.03) eV following downward to upward polarization reversal.
Pulsed laser deposition has been used to grow thin (10–84 nm) epitaxial layers of Yttrium Iron Garnet Y3Fe5O12 (YIG) on (111)–oriented Gadolinium Gallium Garnet substrates at different growth conditions. Atomic force microscopy showed flat surface morphology both on micrometer and nanometer scales. X-ray diffraction measurements revealed that the films are coherent with the substrate in the interface plane. The interplane distance in the [111] direction was found to be by 1.2% larger than expected for YIG stoichiometric pseudomorphic film indicating presence of rhombohedral distortion in this direction. Polar Kerr effect and ferromagnetic resonance measurements showed existence of additional magnetic anisotropy, which adds to the demagnetizing field to keep magnetization vector in the film plane. The origin of the magnetic anisotropy is related to the strain in YIG films observed by XRD. Magneto-optical Kerr effect measurements revealed important role of magnetization rotation during magnetization reversal. An unusual fine structure of microwave magnetic resonance spectra has been observed in the film grown at reduced (0.5 mTorr) oxygen pressure. Surface spin wave propagation has been demonstrated in the in-plane magnetized films.
Systematic and in-depth studies of the structure, composition, and efficiency of hydrogen evolution reactions (HERs) in MoSx films, obtained by means of on- and off-axis pulsed laser deposition (PLD) from a MoS2 target, have been performed. The use of on-axis PLD (a standard configuration of PLD) in a buffer of Ar gas, with an optimal pressure, has allowed for the formation of porous hybrid films that consist of Mo particles which support a thin MoSx~2+δ (δ of ~0.7) film. The HER performance of MoSx~2+δ/Mo films increases with increased loading and reaches the highest value at a loading of ~240 μg/cm2. For off-axis PLD, the substrate was located along the axis of expansion of the laser plume and the film was formed via the deposition of the atomic component of the plume, which was scattered in Ar molecules. This made it possible to obtain homogeneous MoSx~3+δ (δ~0.8–1.1) films. The HER performances of these films reached saturation at a loading value of ~163 μg/cm2. The MoSx~3+δ films possessed higher catalytic activities in terms of the turnover frequency of their HERs. However, to achieve the current density of 10 mA/cm2, the lowest over voltages were −162 mV and −150 mV for the films obtained by off- and on-axis PLD, respectively. Measurements of electrochemical characteristics indicated that the differences in the achievable HER performances of these films could be caused by their unique morphological properties.
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