A study on surface symmetry and interfacial enhancement of SrTiO3 by second harmonic generation

The symmetry of the surfaces of SrTiO3and slightly Nb-doped SrTiO3crystals was investigated by the optical reflected second harmonic generation technique.The good agreement between experimental and theoretical results of the second harmonic intensity dependence on the azimuth angle indicates that the SrTiO3(001)surface is with 4mm symmetry and the Nb-doped SrTiO3(111)surface with 3m symmetry.The measurements of the polarization dependent second harmonic intensity confirm that conclusion.The enhancement of the surface polarization in the structure of SrTiO3capped La0.9Sr0.1MnO3films compared with that in the La0.9Sr0.1MnO3films has been obtained.     

Growth of SrTiO3 on Si(001) by hybrid molecular beam epitaxy

We report the heteroepitaxial growth of SrTiO₃ thin films on Si(001) by hybrid molecular beam epitaxy (hMBE). Here, elemental strontium and the metal‐organic precursor titanium tetraisopropoxide (TTIP) were co‐supplied in the absence of additional oxygen. The carbonization of pristine Si surfaces during native oxide removal was avoided by freshly evaporating Sr into the hMBE reactor prior to loading samples. Nucleation, growth and crystallization behavior as well a structural properties and film surfaces were characterized for a series of 46‐nm‐thick SrTiO₃ films grown with varying Sr to TTIP fluxes to study the effect of non‐stoichiometric growth conditions on film lattice parameter and surface morphology. High quality SrTiO₃ thin films with epitaxial relationship (001)SrTiO₃ || (001)Si and [110]SrTiO₃ || [100]Si were demonstrated with an amorphous layer of around 4 nm thickness formed at the SrTiO₃/Si interface. The successful growth of high quality SrTiO₃ thin films with atomically smooth surfaces using a thin film technique with scalable growth rates provides a promising route towards heterogeneous integration of functional oxides on Si. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Hall effect of tetragonal and orthorhombic SrRuO3 films

High quality orthorhombic and tetragonal SrRuO₃ thin films were grown by pulsed laser deposition on SrTiO₃(001) and Ba_0.75Sr_0.25TiO₃ buffered LaAlO₃(001) substrates. Resistivity vs. temperature curves showed a slope change at a Curie temperature of 147.5 ± 2 K for 40 nm thick films irrespective of crystalline symmetry. The Hall resistivity of both films contained an anomalous Hall contribution. The anomalous Hall coefficient was positive throughout the whole temperature range for the tetragonal film, whereas it showed a sign change at 143 K for the orthorhombic film. This is a strong indication that the Berry‐phase mechanism is the dominant anomalous Hall effect mechanism in SrRuO₃. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Correlation of structure and spin–phonon coupling in (La,Nd) doped BiFeO3 films

We studied the effect of structural change on the spin–phonon coupling in doped BiFeO₃ (BFO) films (Bi_0.8La_0.1Nd_0.1FeO₃) grown on SrTiO₃ (001) substrate. The temperature‐dependent Raman studies show phonon anomalies in the vicinity of magnetic ordering temperature T_N owing to the spin–phonon coupling. Doped films exhibit strong anomalies in the line widths of Raman bands around T_N revealing the presence of strong spin–lattice coupling. The modification in structure as a result of A‐site doping in BFO films plays an important role in controlling the nature of spin–phonon coupling. Copyright © 2014 John Wiley & Sons, Ltd.     

Temperature effects on the phonon spectrum in YBa2Cu3O7 single crystals and thin films

We have performed detailed investigations on the temperature dependence of the 335 cm^–1 phonon in single crystals and thin films of the YBa₂Cu₃O₇ superconductor. The frequency of this phonon exhibits a downshift of about 5 cm^–1 on passing the superconducting transition from above. The shift of the phonon in thin epitaxial films on MgO or SrTiO₃ substrates is only about 2.5 cm^–1. The width of the asymmetric phonon line displays a slight increase belowT _c due to the electron-phonon interaction in these systems.     

Temperature‐dependent,micro‐Raman spectroscopic study of barium titanate nanoparticles

A comparative, temperature‐dependent (80–500 K at 5 K intervals), micro‐Raman spectroscopic study of 300 and 50 nm diameter ceramic BaTiO₃ nanoparticles was carried out with the purpose of elucidating the nanoparticle size effect on the temperature dependence of the polar and non‐polar phonons. A method for calibrating Raman intensities, along with an iterative spectral fitting algorithm, is proposed for concurrent Raman band position and intensity analysis, increasing the analytical abilities of single temperature point Raman spectroscopy. The 300 nm particles exhibit all three phase transitions, whereas the 50 nm particles do not show evidence of these phase transitions in the same temperature range. The Curie temperature appears to be a phonon converging point, irrespective of the phonon symmetry. An attempt was made to qualitatively relate the temperature‐dependent Raman spectra to complimentary non‐spectroscopic methods, such as heat capacity and X‐ray diffraction studies. The study proves that the temperature‐dependent behavior of the polar phonon, 265 cm⁻¹, can be utilized as a sensitive phase transition probe. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation of structural phase transition in polycrystalline SrTiO3 thin films by Raman spectroscopy

Polycrystalline SrTiO₃ thin films were prepared by pulsed laser deposition technique. The phonon properties and structural phase transition were studied by Raman spectroscopy. The first-order Raman scattering, which is forbidden in SrTiO₃ single crystal, has been observed in the films, due to the structural distortion caused by strain effect and oxygen vacancies. The Fano-type line shape of TO₂ phonon reveals the existence of polar microregions in the STO thin films. The evolution of TO₂ and TO₃ phonons with temperature shows the occurrence of a structural phase transition at 120 K related to the formation of polar macroregions in the films.     

Raman study of ultrathin Fe3O4 films on GaAs(001) substrate: stoichiometry,epitaxial orientation and strain

The growth and characterization of high‐quality ultrathin Fe₃O₄ films on semiconductor substrates is a key step for spintronic devices. A stable, single‐crystalline ultrathin Fe₃O₄ film on GaAs(001) substrate is obtained by post‐growth annealing of epitaxial Fe film with thicknesses of 5 and 12 nm in air. Raman spectroscopy shows a high ability to convincingly characterize the stoichiometry, epitaxial orientation and strain of such ultrathin Fe₃O₄ films. Polarized Raman spectroscopy confirms the unit cell of Fe₃O₄ films is rotated by 45° to match that of the Fe (001) layer on GaAs, which results in a built‐in strain of − 3.5% in Fe₃O₄ films. The phonon strain‐shift coefficient(−126 cm⁻¹) of the A_1g mode is proposed to probe strain effect and strain relaxation of thin Fe₃O₄ films on substrates. It can be used to identify whether the Fe layer is fully oxidized to Fe₃O₄ or not. Copyright © 2011 John Wiley & Sons, Ltd.     

Thickness dependence of the soft ferroelectric mode in SrTiO3 thin films deposited on MgO

We have measured the complex dielectric constants of SrTiO₃ thin films deposited on MgO substrate, by using the broadband terahertz time-domain spectroscopy. The dielectric dispersion of SrTiO₃ thin films with thickness of 1046, 460 and 55 nm has been observed in the frequency range from 0.1 to 8 THz. The dispersion mainly consists of the TO1 ferroelectric soft mode with a slight absorption of the TO2 phonon mode. From the analysis of the obtained dispersion, we found that the soft mode frequency hardens as the thickness of the film becomes thinner, and is extremely large compared with the bulk crystals. The damping of the soft mode is also larger than that of bulk SrTiO₃, which suggests the extrinsic nature of the broadening of the soft mode dispersion. In the thinnest film of 55 nm, even the shape of the dielectric dispersion changes, which may be related to integrated defects near the interface.     

Polarization-Dependent Light-Gated Phase Conjugation in Methyl-Orange Doped Polymer Film

We have investigated the polarization state of a gated phase conjugate beam using a methyl-orange doped poly-vinyl alcohol (MO/PVA) film in 16 different combinations of linear and circular polarization states of a probe beam and pump beams. The experimental results agree with the theoretical prediction based on the Jones matrix method. Of the third-order nonlinear susceptibility tensors X_ijkl of the MO/PVA film, the X₁₂₂₁ at the 647 nm wavelength in degenerate four-wave mixing under exposure of a gating 515 nm light takes a very small value compared with X₁₁₁₁ and X₁₁₂₂. On the other hand, in the configuration of a probe beam and pump beams having linearly crossed polarizations and without gating light, the MO/PVA film generates a strong linearly polarized PC beam, so that X₁₂₂₁ takes a large value at 515 nm.     

Multiphonon resonant Raman scattering in N‐doped ZnO

Multiphonon resonant Raman scattering in N‐doped ZnO films was studied, and an enhancement of the resonant Raman scattering process as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed at room temperature. The resonant Raman scattering intensity of the 1LO phonon in N‐doped ZnO appears three times as strong as that of undoped ZnO, which mainly arises from the defect‐induced Raman scattering caused by N‐doping. The nature of the 1LO phonon at 578 cm⁻¹ is interpreted as a quasimode with mixed A₁ and E₁ symmetry because of the defects formed in the ZnO lattice. In addition, the previously neglected impurity‐induced two‐LO‐phonon scattering process was clearly observed in N‐doped ZnO. Copyright © 2009 John Wiley & Sons, Ltd.     

Tensile strain induced changes in the optical spectra of SrTiO3 epitaxial thin films

Effect of biaxial tensile strains on optical function and band edge transitions of ultra thin epitaxial films was studied using as an example a 13 nm thick SrTiO₃ films deposited on KTaO₃ (100) single-crystal substrates. Optical functions in the 200–1200 nm spectral range were determined by spectroscopic ellipsometry technique. It was found that tensile strains result in a shift of the low energy band gap optical transitions to higher energies and decrease the refractive index in the visible region. Comparison of the optical spectra for strained SrTiO₃ films and for homoepitaxial strain-free SrTiO₃: Cr (0.01 at %) films deposited on SrTiO₃ (100) single crystalline substrates showed that this “blue” shift of the band gap could not be related to technological imperfections or to reduced thickness. The observed effect is connected with changes in the lowest conduction and in the top valence bands that are due to increase of the in-plane lattice constant and/or onset of the polar phase in the tensile strain-induced ultra-thin epitaxial SrTiO₃ films.     

外延PbZr0.4Ti0.6O3薄膜厚度对其铁电性能的影响

从Landau-Devonshire唯象理论出发，考虑到晶格失配导致的NFDA3位错应力场与极化场的耦合，研究了在SrTiO₃衬底上外延生长的PbZr_0.4Ti_0.6O₃薄膜厚度对其自发极化强度、电滞回线的影响. 结果表明，产生刃位错的PbZr_0.4Ti_0.6O₃薄膜临界厚度为～1.27nm，当薄膜厚度大于临界厚度时，在所形成的位错附近，极化强度出现急剧变化，形成自发极化强度明显减弱的“死层”；随着薄膜厚度的减小，位错间距增大，“死层”厚度与薄膜总厚度之比增加. 由薄膜电滞回线的变化情况可知，其剩余极化强度随着薄膜厚度的减小而逐渐减小. 关键词： 铁电薄膜 自发极化强度 电滞回线 位错     

Disorder‐induced Raman scattering effects in one‐dimensional ZnO nanostructures by incorporation and anisotropic distribution of Dy and Li codopants

In Dy³⁺ and Li⁺ codoped ZnO nanowires, the additives accumulate preferentially in {0001} planes, resulting in serious breakdown of the translational symmetry in ab plane and modification of the phonon oscillation field. Not only acoustic overtones, silent optical modes, surface optical (SO) phonon modes, and multi‐phonon processes can be effectively observed in the nonresonant Raman scattering (RS) and the Fourier‐transform infrared (FTIR) spectra, but the quasi‐LO and TO modes of mixed A₁ and E₁ symmetry also show a noticeable red shift from E₁ symmetry (in ab plane) to A₁ symmetry (along c axis). The presence of dislocations and internal strain at the surface layer rich in additives, coming from the segregation of additives, forms a quasi‐bilayer system, resulting in the appearance and enhancement of SO phonon modes in RS and FTIR spectra. The Fano interference, originating from the interaction between the discrete scattering from phonons and the continuum scattering from laser‐induced electrons in the doped nanostructures, leads to typical asymmetric lineshapes on the lower wavenumber sides. Copyright © 2010 John Wiley & Sons, Ltd.     

Room temperature ferroelectricity of tetragonally strained SrTiO3 thin films on single crystal Rh substrates

Epitaxial SrTiO₃ thin films were deposited on single crystalline Rh substrates by pulsed laser deposition. The tetragonally stained structure of the SrTiO₃ thin films with a c/a ratio of 1.04 was confirmed by x-ray diffraction experiments. The SrTiO₃ thin films exhibited good ferroelectric properties with a high remanent polarization (2P_r) of 8 μC/cm² and a canonical ferroelectric piezoresponse hysteresis loop at room temperature. We estimated a high activation electric field of about 6.4 MV/cm for domain wall creeping. This activation electric field is higher than that of typical ferroelectric materials such as PbTiO₃.     

Experimental studies of the thermal properties of thin films by a probe technique with periodic heating

The thermal properties of SrTiO₃ thin films are investigated experimentally by recording the amplitude and phase of the temperature oscillations of a flat probe with the heat flux perpendicular to the plane of the film. Results are given from measurements of the specific heat and thermal conductivity of a leucosapphire substrate and the thermal conductivity of a SrTiO₃ film of thickness 2 μm. Fiz. Tverd. Tela (St. Petersburg) 39, 1299–1302 (July 1997)     

金属有机分解法制备的SrTiO3薄膜的光学特性

采用金属有机分解法（MOD）在石英衬底上沉积了SrTiO3薄膜。所制备的薄膜是晶格常数为a=b=c=3.90?的多晶结构。通过测量190—1100nm波段内的透射光谱，采用包络方法计算了薄膜的光学常数（折射率n和消光系数k）。结果表明，采用MOD方法制备的薄膜的折射率大于采用射频磁控溅射、溶胶—凝胶和化学气相沉积方法制备的薄膜的折射率；薄膜的折射率色散关系满足单振子模型，其中振子强度S0为0.88′1014m-2，振子能量E0为6.40eV；薄膜的禁带宽度为3.68eV。     

Production of high-quality metal-coated pyroelectric SrTiO3 films

A procedure for the production of metal-coated quasi-amorphous pyroelectric thin SrTiO₃ films is described. The films are grown in a modified 306 Edwards magnetron sputtering setup under controlled thermal conditions and stabilized high-accuracy vacuum and gas pressure conditions. Three-layer 200 nm metal-100 nm SrTiO₃-100 nm metal films are studied. The pyroelectric nature of the electric response of these films to heating is directly established, since metallic contacts made from the same material do not distort the measurement results, which excludes the effect of a contact potential difference on the measurement results.     

Vibrational Raman spectra of CdSx Se1‐x magic‐size nanocrystals

Resonant Raman scattering spectra of ultrasmall (<2 nm) magic‐size nanocrystals (NCs) are reported. The spectra of CdS and CdS_x Se_1‐x NCs, resonantly excited with 325 nm and 442 nm laser lines, correspondingly, reveal broad features in the range of bulk optical phonons. The relatively large width, ～50 cm^‐1, and downward shift, ～20 cm^‐1, of the Raman bands with respect to the longitudinal optical phonon in bulk crystals and large NCs are discussed based on the breaking of the translational symmetry and bond distortion in these ultrasmall NCs. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of (La,Ca)MnO3 ultrathin films deposited on SrTiO3 substrates

Epitaxial La_1?x Ca _x MnO₃ (x???0.33) ultrathin films with thickness between 3 and 6?nm have been grown on (001) SrTiO₃ substrates by sputter deposition. The films do not exhibit an insulator-metal transition as a function of temperature, which is normal in thicker films. High-resolution transmission electron microscopy and electron diffraction were used to investigate the crystal structure. It was found that the films grow coherently on the substrates and are perfectly crystalline. Their crystal structure was determined to be a body-centred orthorhombic structure with space group Imma, instead of the orthorhombic Pnma bulk structure. This structure change is probably responsible for the insulating property of the films.