Temperature-dependent photoluminescence in La2/3Ca1/3MnO3

Visible photoluminescence and its temperature dependence of La_2/3Ca_1/3MnO₃ in the temperature range 138-293 K were measured. It was observed that the main broad band centered at ∼1.77 eV with the shoulders at ∼1.57 and ∼1.90 eV existed in the entire temperature range. It can be well fitted by three Gaussian curves B₁, B₂ and B₃ centered at ∼1.52, ∼1.75 and ∼1.92 eV, respectively. The intensities of the peak B₁ and B₂ vary as temperature increases. In the entire temperature range, the intensity of B₁ increases with increasing temperature, whereas that of B₂ decreases. The photoluminescence mechanisms for La_2/3Ca_1/3MnO₃ are presented based on the electronic structures formed by the interactions among spin, charge and lattice, in which B₁ was identified with the charge transfer excitation of an electron from the lower Jahn-Teller split e_g level of a Mn³⁺ ion to the e_g level of an adjacent Mn⁴⁺ ion, B₂ is assigned to the transition between the spin up and spin down e_g bands separated by Hund's coupling energy E_J and B₃ is attributed to the transition, determined by the crystal field energy E_C, between a t_2g core electron of Mn³⁺ to the spin up e_g bands of Mn⁴⁺ by a dipole allowed charge transfer process.     

TbMnO3 epitaxial thin films by pulsed-laser deposition

Epitaxial TbMnO₃ films have been fabricated on SrTiO₃(001) and LaAlO₃(001) substrates by pulsed laser deposition (PLD), the structure and surface morphology of the films were characterized by X-ray diffraction with Cu K_α radiation and atomic force microscopy. The electrical transport and magnetic properties of the TbMnO₃ films and bulk were examined, the resistivity and the forbidden band width E_g change with epitaxial orientation, semiconductor transport properties are found in the films and bulk, the average of the E_g of the films on SrTiO₃ and on LaAlO₃ is equal to the E_g of the bulk. The two TMO films have different magnetization mode, the magnetization of the film on SrTiO₃ have an analogy to that of TbMnO₃ single crystal.     

Crystal field investigation on the magnetic properties of Yb in Yb(CF3SO3)3·9H2O

Ytterbium tri-fluoromethanesulfonate (YbTFMS) single crystals are prepared from the slow evaporation of the aqueous solution of YbTFMS and the principal magnetic susceptibility perpendicular to the c-axis of the hexagonal crystal (χ_⊥) is measured from 300 K down to 13 K. Principal magnetic anisotropy Δχ(=χ_∥−χ_⊥) is measured from 300 K down to 80 K which provides principal magnetic susceptibility parallel to the c-axis (χ_∥) down to 80 K. Very good theoretical simulation of the observed magnetic properties of YbTFMS has been obtained using one electron crystal field (CF) analysis having C_3h site symmetry. No signature of ordering effect in the observed magnetic data is noticed down to the lowest temperature (13 K) attained, indicating the inter-ionic interaction to be of predominantly dipolar type. The calculated g-values are found to be g_∥=2.67 and g_⊥=2.51, respectively. CF analysis provides the electronic specific heat which gives two Schottky anomalies in its thermal variation down to ∼13 K. The temperature dependences of quadrupole splitting and hyperfine heat capacity are studied from the necessary information obtained from the CF analysis.     

Effect of heat treatment on the optical and electrical transport properties of Ge15Sb10Se75 and Ge25Sb10Se65 thin films

The effect of heat treatment on the optical and electrical properties of Ge₁₅Sb₁₀Se₇₅ and Ge₂₅Sb₁₀Se₆₅ thin films in the range of annealing temperature 373-723 K has been investigated. Analysis of the optical absorption data indicates that Tauc's relation for the allowed non-direct transition successfully describes the optical processes in these films. The optical band gap (E_g^opt.) as well as the activation energy for the electrical conduction (ΔE) increase with the increase of annealing temperature (T_a) up to the glass transition temperature (T_g). Then a remarkable decrease in both the E_g^opt. and ΔE values occurred with a further increase of the annealing temperature (T_a>T_g). The obtained results were explained in terms of the Mott and Davis model for amorphous materials and amorphous to crystalline structure transformations. Furthermore, the deduced value of E_g^opt. for the Ge₂₅Sb₁₀Se₆₅ thin film is higher than that observed for the Ge₁₅Sb₁₀Se₇₅ thin film. This behavior was discussed on the basis of the chemical ordered network model (CONM) and the average value for the overall mean bond energy 〈E〉 of the amorphous system Ge_xSb₁₀Se_90−x with x=15 and 25 at%. The annealing process at T_a>T_g results in the formation of some crystalline phases GeSe, GeSe₂ and Sb₂Se₃ as revealed in XRD patterns, which confirms our discussion of the obtained results.     

Effect of composition and thermal annealing on the absorption and electrical conduction of Se85−xTe15Sbx glasses

The optical absorption of the as-prepared and thermally annealed Se_85−xTe₁₅Sb_x (0≤x≤9) thin films was measured. The mechanism of the optical absorption follows the rule of non-direct transition. The optical energy gap (E₀) decreased from 1.12 to 0.84 eV with increasing Sb content of the as-prepared films from 0 to 9 at.%. The as-prepared Se₇₆Te₁₅Sb₉ films showed an increase in (E₀) with increasing the temperature of annealing in the range above T_g (363 K). The electrical conductivity of the as-prepared and annealed films was found to be of Arrhenius type with temperature in the range 300-360 K. The activation energy for conduction was found to decrease with increasing both the Sb content and temperature of annealing. The results were discussed on the basis of the lone-pair electron effect and of amorphous crystalline transformation.     

Superparamagnetic behavior of La0.67Sr0.33MnO3 nanoparticles prepared via sol-gel method

Magnetic nanoparticles of La_0.67Sr_0.33MnO₃ (LSMO) manganite were prepared by sol-gel method. Phase formation and crystal structure of the synthesized powder were examined by the X-ray diffraction (XRD) using the Rietveld analysis. The mean particle size was determined by the transmission electron microscopy (TEM). Infrared transmission spectroscopy revealed that stretching and bending modes are influenced by calcinations temperature. The temperature dependence of the ac magnetic susceptibility was measured at different frequencies and ac magnetic fields in the selected ranges of 40-1000 Hz and 80-800 A/m, respectively. The temperature dependence of ac susceptibility shows a characteristic maxima corresponding to the blocking temperature near room temperature. The frequency dependence of the blocking temperature is well described by the Vogel-Fulcher law. By fitting the experimental data with this law, the relaxation time τ₀=1.7×10⁻¹² s, characteristic temperature T₀=262±3 K, anisotropy energy E_a/k=684±15 K and effective magnetic anisotropy constant k_eff=2.25×10⁴ erg/cm³ have been obtained. dc Magnetization measurement versus magnetic field shows that some of LSMO nanoparticles are blocked at 293 K. The role of magnetic interparticle interactions on the magnetic behavior is also investigated.     

Structure, band offsets and photochemistry at epitaxial α-Cr2O3/α-Fe2O3 heterojunctions

We test the hypothesis that electron-hole pair separation following light absorption enhances photochemistry at oxide/oxide heterojunctions which exhibit a type II or staggered band alignment. We have used hole-mediated photodecomposition of trimethyl acetic acid chemisorbed on surfaces of heterojunctions made from epitaxial α-Cr₂O₃ on α-Fe₂O₃(0001) to monitor the effect of UV light of wavelength 385 nm (3.2 eV) in promoting photodissociation. Absorption of photons of energies between the bandgaps of α-Cr₂O₃ (E_g = 4.8 eV) and α-Fe₂O₃ (E_g = 2.1 eV) is expected to be strong only in the α-Fe₂O₃ layer. The staggered band alignment should then promote the segregation of holes (electrons) to the α-Cr₂O₃ (α-Fe₂O₃) layer. Surprisingly, we find that the α-Cr₂O₃ surface alone promotes photodissociation of the molecule at hν = 3.2 eV, and that any effect of the staggered band alignment, if present, is masked. We propose that the inherent photoactivity of the α-Cr₂O₃(0001) surface results from the creation of bound excitons in the surface which destabilize the chemisorption bond in the molecule, resulting in photodecomposition.     

Electrical transport, magnetic properties of the half-metallic Fe3O4-based Schottky diode

Fe₃O₄ thin films were prepared successfully by using the rf-sputtering technique with Fe₂O₃ target. The inverse spinel structure of the film was determined by X-ray diffraction (XRD) and the single phase of the Fe₃O₄ was confirmed by the XPS measurements. The surface roughness increases with the increase of the partial pressure of hydrogen. A high saturated magnetic field, 5000 Oe, implies that there exist the antiphase boundaries (APBs) in the film. The higher coercive filed below T_V is ascribed to the lower symmetry of the monoclinic structure. The temperature dependence of resistance shows a very clear Verwey transition and it is implied that the electrical transport behavior follows the variable-range hopping (VRH) mechanism from 40 to 300 K. The current vs. voltage curves of Fe₃O₄/Si Schottky heterojunction exhibits good rectifying property. The ideality factor and Schottky barrier height were obtained from the fitting curves calculated by the standard thermionic emission/diffusion model.     

Fano line shape and anti-crossing of Raman active E2g peaks in the charge density wave state of NbSe2

Low energy Raman scattering from the ab-plane of the 2H polytype single crystal NbSe₂ has been investigated in the normal (N), incommensurate charge density wave (ICDW) and superconducting (SC) phases. The temperature dependence of the polarization resolved Raman response has been obtained for the excitation wavelength of 647 nm and fitted to phenomenological models for the E_2g and A_1g symmetry channels. The A_1g response can be fitted by a simple damped oscillator peak superimposed on continuous background. The E_2g response displays an anti-resonance interference pattern between the inter-layer phonon and the CDW-induced mode such that a hybridized configuration (Fano line shape [1]) is required for modelling. The polarization specific peak maxima positions and line widths as a function of temperature, deduced in this manner, are presented. Partial suppression of the electronic continuum scattering in the Raman shift range up to 110 cm⁻¹ in the A_1g symmetry channel and beyond 300 cm⁻¹ in the E_2g symmetry channel is indicative of high energy electronic states far away from the Fermi surface participating in the ICDW formation.     

Detailed infrared spectroscopic study of thermal transitions in new hybrid [(CH3)2CHNH3]4Cd3Cl10 crystal

Phase transitions of tetra(isopropylammonium)decachlorotricadmate(II) [(CH₃)₂CHNH₃]₄Cd₃Cl₁₀ crystal have been studied by infrared, far infrared and Raman measurements in wide temperature range, between 11 K and 388 K. The temperature changes of wavenumber, center of gravity, width and intensity of the bands were analyzed to clarify cationic and anionic contributions to the phase transitions mechanism. The results of investigation showed earlier by differential scanning calorimetry (DSC), thermal expansion and dielectric measurements clearly confirmed the sequence of phase transitions at T₁=353 K, T₂=294 K and T₃=260 K. The current results derived from DSC and infrared measurements revealed additional phase transition at T₄=120 K.     

Switching phenomenon and optical properties of Se85Te10Bi5 films

Se₈₅Te₁₀Bi₅ films of different thicknesses ranging from 126 to 512 nm have been prepared. Energy-dispersive X-ray (EDX) spectroscopy technique showed that films are nearly stoichiometric. X-ray diffraction (XRD) measurements have showed that the Se₈₅Te₁₀Bi₅ films were amorphous. Electrical conduction activation energy (ΔE_σ) for the obtained films is found to be 0.662 eV independent of thickness in the investigated range. Investigation of the current voltage (I-V) characteristics in amorphous Se₈₅Te₁₀Bi₅ films reveals that it is typical for a memory switch. The switching voltage V_th increases with the increase of the thickness and decreases exponentially with temperature in the range from 298 to 383 K. The switching voltage activation energy (ε) calculated from the temperature dependence of V_th is found to be 0.325 eV. The switching phenomenon in amorphous Se₈₅Te₁₀Bi₅ films is explained according to an electrothermal model for the switching process. The optical constants, the refractive index (n) and the absorption index (k) have been determined from transmittance (T) and reflectance (R) of Se₈₅Te₁₀Bi₅ films. Allowed non-direct transitions with an optical energy gap (E_g^opt) of 1.33 eV have been obtained. ΔE_σ is almost half the obtained value of E_g^opt, which suggested band to band conduction as indicated by Davis and Mott.     

Photocontrol of magnetization in Al-substituted Fe3O4 thin films

Thin films of (111)-oriented spinel ferrite Al_0.5Fe_2.5O₄ have been prepared by a pulsed-laser deposition (PLD) technique on α-Al₂O₃ (0001) substrates. The films exhibit cluster-glass behaviors with a spin-freezing temperature, T_g, near or above room temperature. The magnetization was found to increase following light irradiation below T_g, which indicates the photoinduced melting of cluster-glass states. An analysis comparing the dynamic behavior of magnetic response to light irradiation between zero-field-cooled (ZFC) states and field-cooled (FC) states at 10 K under various light intensities, I, revealed that the direct photoexcitation of spins occurs when I≤0.78 mW/mm², while the thermal heating effect following the light absorption of the samples also contributes to the enhancement of magnetization when I≥1.22 mW/mm². The magnetization of the films could be controlled by light irradiation even at room temperature. This suggests the possibility of utilizing these films in the development of novel magneto-optical memory devices.     

Combinatorial synthesis and optical characterization of alloy and superlattice films based on SrTiO3 and LaAlO3

We have grown alloy and superlattice films consisting of SrTiO₃ (STO) and LaAlO₃ (LAO) by pulsed laser deposition using composition-spread technique. All the (STO)_x(LAO)_1−x (0 ≤ x ≤ 1) alloy and superlattice films exhibited a single-phase perovskite structure. The optical properties of these films were characterized by absorption spectroscopy at room temperature. The spectra show a broad absorption due to O 2p-Ti 3d(t_2g) transition in an ultraviolet region. We found that absorption edges of both alloy and superlattice films systematically shifted to higher energy with increasing LAO composition. Clear difference was observed in the composition dependence of the indirect and a direct band edges.     

Refractive index, oscillator parameters and temperature-tuned energy band gap of Tl4In3GaS8-layered single crystals

Transmission and reflection measurements in the wavelength region 450-1100 nm were carried out on Tl₄In₃GaS₈-layered single crystals. The analysis of the room temperature absorption data revealed the presence of both optical indirect and direct transitions with band gap energies of 2.32 and 2.52 eV, respectively. The rate of change of the indirect band gap with temperature dE_gi/dT=-6.0×10⁻⁴ eV/K was determined from transmission measurements in the temperature range of 10-300 K. The absolute zero value of the band gap energy was obtained as E_gi(0)=2.44 eV. The dispersion of the refractive index is discussed in terms of the Wemple-DiDomenico single-effective-oscillator model. The refractive index dispersion parameters: oscillator energy, dispersion energy, oscillator strength and zero-frequency refractive index were found to be 4.87 eV, 26.77 eV, 8.48×10¹³ m⁻² and 2.55, respectively.     

Structural and electrical transport properties of Nb-doped TiO2 films deposited on LaAlO3 by rf sputtering

We have investigated the structural and electrical transport properties of Nb-doped TiO₂ films deposited on (1 0 0) LaAlO₃ substrates by rf magnetron sputtering at temperatures ranging from 873 K to 1073 K. Films deposited below 998 K are anatase, and mixed phases between anatase and rutile exist in the film grown at higher temperatures. We find that films deposited at low temperatures exhibit semiconductor behavior, while metallic conductivity is observed in the most conducting film deposited at 998 K. For this sample, compared to electron-phonon scattering mechanism, electron-phonon-impurity interference effect plays an important role in its electron transport process. Moreover, the temperature coefficient of the resistivity for the film deposited at 1073 K is negative from 2 K to 300 K. The temperature dependence of resistivity for the film is described by ∼exp(b/T)^1/2 at temperatures from 80 K down to 30 K, and by the fluctuation induced tunneling model from 80 K to 300 K.     

Fluoride glasses in the InF3-GaF3-YF3-PbF2-CaF2-ZnF2 system

New glasses have been synthesized in a multicomponent system based on indium fluoride. Samples of a few mm in thickness were obtained. They are transparent and homogeneous. Main physical properties such as density, characteristic temperatures, density, thermal expansion and refractive index have been measured. The evolution versus composition is reported for samples with the formula: (35−x) InF₃-xGaF₃-10YF₃-25PbF₂-15CaF₂-15ZnF₂. T_g lies between 260 and 296 °C while melting starts around 480 °C. Glass samples are stable at room temperature. By comparison with other standard fluoride glasses, they exhibit higher refractive index and density.     

The role of As2O3 on the stability and some physical properties of PbO-Sb2O3 glasses

PbO-Sb₂O₃ glasses added with different concentrations of As₂O₃ (10-55 mol%) were prepared to understand their IR spectra, elastic properties (Young's modulus E, Shear modulus G, microhardness H), optical absorption and dielectric properties (constant ε, loss tan δ, ac conductivity σ_ac over a moderately wide range of frequency and temperature and breakdown strength in air medium at room temperature). Results have indicated that the structure of the PbO-Sb₂O₃-As₂O₃ glass is more rigid when the concentration of As₂O₃ is around 40 mol%.     

Enhanced ferroelectric property of (Pb0.95Ca0.05)(Nb0.02Zr0.80Ti0.20)O3 thin films prepared by RF magnetron sputtering

(Pb_0.95Ca_0.05)(Nb_0.02Zr_0.80Ti_0.20)O₃ [PCNZT] thin films were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering with and without a LaNiO₃ [LNO] buffer layer. Ca and Nb elements in PZT films enhance the ferroelectric property, LaNiO₃ buffer layer improves the crystal quality of the PCNZT thin films. PCNZT thin films possess better ferroelectric property than that of PZT films for Ca and Nb ion substitution, moreover, PCNZT thin films with a LNO buffer layer possess (1 0 0) orientation and good ferroelectric properties with high remnant polarization (P_r = 38.1 μC/cm²), and low coercive field (E_c = 65 kV/cm), which is also better than that of PCNZT thin films without a LNO buffer layer (P_r = 27.9 μC/cm², E_c = 74 kV/cm). The result shows that enhanced ferroelectric property of PZT films can be obtained by ion substitution and buffer layer.     

The structure and magnetotransport properties of La2/3Sr1/3MnO3/Ba(La)TiO3 composites

The effect of Ba(La)TiO₃ doping on the structure and magnetotransport properties of La_2/3Sr_1/3MnO₃(LSMO)/xBa(La)TiO₃ (x=0.0, 1.0, 5.0 mol%) have been investigated. The X-ray diffraction patterns and microstructural analysis show that BaTiO₃ and LSMO phases exist independently in BaTiO₃-doped composites. The metal-insulator transition temperature (T_MI) decreases whereas the maximum resistivity increases very quickly by the increase of BaTiO₃ doping level. The partial substitution of Ba by La(0.35 mol%) results in a decrease in resistivity of LSMO/xBa(La)TiO₃ composites. Magnetoresistance of BaTiO₃-doped composites decreases monotonously in the temperature range 200-400 K in a magnetic field of 5 T, which is completely different from that of LSMO compound. The value of MR decreases at low field (H<1 T) and increases at high fields (H>1 T) with increasing the BaTiO₃ doping level at low temperatures below 280 K. These investigations reveal that the magnetotransport properties of LSMO/xBa(La)TiO₃ composites are dominated by spin-dependent scattering and tunneling effect at the LSMO/BaTiO₃/LSMO magnetic tunnel junction.     

Magnetic properties and EPR spectra of [Cu(L-arginine)2](NO3)2·3H2O

Magnetic and EPR data have been collected for complex [Cu(L-Arg)₂](NO₃)₂·3H₂O (Arg=arginine). Magnetic susceptibility χ in the temperature range 2-160 K, and a magnetization isotherm at T=2.29(1) K with magnetic fields between 0 and 9 T were measured. The observed variation of χT with T indicates predominant antiferromagnetic interactions between Cu(II) ions coupled in 1D chains along the b axis. Fitting a molecular field model to the susceptibility data allows to evaluate g=2.10(1) for the average g-factor and J=−0.42(6) cm⁻¹ for the nearest neighbor exchange coupling (defined as H_ex=-∑J_ijS_i·S_j). This coupling is assigned to syn-anti equatorial-apical carboxylate bridges connecting Cu(II) ion neighbors at 5.682 Å, with a total bond length of 6.989 Å and is consistent with the magnetization isotherm results. It is discussed and compared with couplings observed in other compounds with similar exchange bridges. EPR spectra at 9.77 were obtained in powder samples and at 9.77 and at 34.1 GHz in the three orthogonal planes of single crystals. At both microwave frequencies, and for all magnetic field orientations a single signal arising from the collapse due to exchange interaction of resonances corresponding to two rotated Cu(II) sites is observed. From the EPR results the molecular g-tensors corresponding to the two copper sites in the unit cell were evaluated, allowing an estimated lower limit |J |>0.1 cm⁻¹ for the exchange interaction between Cu(II) neighbors, consistent with the magnetic measurements. The observed angular variation of the line width is attributed to dipolar coupling between Cu(II) ions in the lattice.