Photoacoustic spectroscopy of thin films of As<Subscript>2</Subscript>S<Subscript>3</Subscript>, As<Subscript>2</Subscript>Se<Subscript>3</Subscript> and GeSe<Subscript>2</Subscript>

Photoacoustic spectroscopy (PAS) is one of the important branches of spectroscopy, which enables one to detect light-induced heat production following the absorption of pulsed radiation by the sample. As₂S₃, As₂Se₃ and GeSe₂ exhibit a wide variety of photo-induced phenomena that enable them to be used as optical imaging or storage medium and various electronic devices, including electro-optic information storage devices and optical mass memories. Therefore, accurate measurement of thermal properties of semiconducting films is necessary to study the memory density. The thermal conductivity of thin films of As₂S₃ (thickness 100 μm and 80 μm), As₂Se₃ (thickness 100 μm and 80 μm) and GeSe₂ (thickness 120 μm and 100 μm) has been measured using PAS technique. Our result shows that the thermal conductivity of thicker films is larger than the thinner films. This can be explained by the thermal resistance effect between the film and the surface of the substrate.      

High-pressure neutron diffraction study of BaFe<Subscript>2</Subscript>As<Subscript>2</Subscript>

The crystal structure of BaFe₂As₂ was studied by high-pressure neutron powder diffraction in the pressure range from ambient to 6.5 GPa as well as in the temperature range from 12 K to 293 K at 4.4 GPa and no pressure or temperature induced phase changes were observed. The compression mechanism of BaFe₂As₂ was found to be anisotropic as the a- and c-axes are reduced by 2.49 and 3.66%, respectively at 6.5 GPa. Within the FeAs layers the Fe-As and Fe-Fe bonds decrease by 2.49 and 3.66%, respectively. The Ba-As distance decreases by 3.70% while the As-As inter-atomic distance along the c-axis exhibits a complex pressure dependence. The bulk modulus B ₀ and its pressure derivative B ₀' were determined to be B ₀ = 59(2) GPa and B ₀' = 6.1(7) at ambient temperature.     

Band structure of new layered arsenides SrRu<Subscript>2</Subscript>As<Subscript>2</Subscript> and BaRu<Subscript>2</Subscript>As<Subscript>2</Subscript>

This paper reports on the results of the ab initio FLAPW-GGA band structure calculations for two new layered phases SrRu₂As₂ and BaRu₂As₂, which are isostructural and isoelectronic to the known tetragonal (Ca,Sr,Ba)Fe₂As₂ basis phases of the FeAs superconductor family. The energy bands, densities of states, topology of the Fermi surface, low-temperature electron specific heats, and molar Pauli paramagnetic susceptibilities of SrRu₂As₂ and BaRu₂As₂ are determined for the first time and discussed in comparison with those for BaFe₂As₂ and BaRh₂As₂.     

A nonlinear dynamic effect of formation of photo-induced periodic structures in waveguiding As<Subscript>2</Subscript>S<Subscript>3</Subscript>-Ag thin films

A nonlinear effect of spatiotemporal transformations of a focused linearly polarized Gaussian beam of a He-Ne laser obliquely incident (S and P polarizations) upon an As₂S₃-Ag film containing a small amount of chlorine and deposited onto a glass substrate is found and interpreted. The effect consists in the appearance, in the process of exposure, of beams diffracted and anisotropically scattered by periodic structures arising due to excitation of the waveguide TE₀ and TM₀ modes in the film. The diffraction measurements of the effective refractive indices for the TE₀ and TM₀ modes make it possible to calculate the refractive index and the thickness of the film from dispersion equations. Along with slow evolution of the diffraction and scattering patterns, we have found a persistent optical turbulence in the fringes of scattering from the structures related to excitation of the TE₀ modes. It is suggested that the turbulence is an indication of existence of reversible processes in the mechanism of photosensitivity.     

Filament-induced self-written waveguides in glassy As<Subscript>4</Subscript>Ge<Subscript>30</Subscript>S<Subscript>66</Subscript>

The filamentation of femtosecond laser pulses and filament-induced self-writing of a permanent waveguide are observed in As₄Ge₃₀S₆₆ chalcogenide glass. The radial profile of the self-written waveguide is extracted from the defocused transmission microscopic images via a two-step procedure: at first the phase image of the waveguide is computed using the transport-of-intensity equation and then the index profile is obtained from the phase image by applying the inversed Abel transform.     

The Debye temperature and Grüneisen parameter of the CaLa<Subscript>2</Subscript>S<Subscript>4</Subscript>-La<Subscript>2</Subscript>S<Subscript>3</Subscript> system

The thermal expansion coefficient of solid solutions in the CaLa₂S₄-La₂S₃ system at a temperature of 300 K is investigated experimentally. The Debye temperature, the Grüneisen parameter, and the isothermal compressibility coefficient of solid solutions in the system under investigation are determined from the experimental thermal expansion coefficient. It is demonstrated that, upon substitution of calcium ions for cation vacancies in La₂S₃, the Debye temperature decreases, the isothermal compressibility coefficient increases, and the Grüneisen parameter remains constant for all compositions in the CaLa₂S₄-La₂S₃ system. A correlation between the ionic radii of Ca²⁺ and La³⁺, the concentration of cation vacancies, and the rigidity of the lattice, on the one hand, and the Debye temperature, the Grüneisen parameter, and the isothermal compressibility coefficient, on the other, is revealed for the studied samples.     

Photoluminescence of nanoparticles of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> solid solution

We have ground bulk samples to obtain nanoparticles of (Ga₂S₃)_1–x (Eu₂O₃) _x solid solutions, the sizes of which were determined using an atomic force microscope. The photoluminescence spectra of the nanoparticles were studied in the temperature interval 77–300 K. We have established the mechanisms for emission and transfer of energy from the matrix to the rare-earth ion, and we determined the Stokes shift (ΔS = 0.7 eV), the Huang–Rhys parameter (S = 16), and the optical phonon energy (ħ−ω = 23 meV).     

Effect of bismuth dopant on the dielectric properties of modified As<Subscript>2</Subscript>Se<Subscript>3</Subscript>

A comparative analysis has been performed for the specific features of the dispersion of the components of the complex permittivity for pure and bismuth-doped thin films of amorphous arsenic triselenide. A correlation between the experimental data and theoretical calculations of similar characteristics obtained in previous studies has been found. The mechanisms of the effects observed have been discussed.     

Electronic structure of novel multiple-band superconductor SrPt<Subscript>2</Subscript>As<Subscript>2</Subscript>

The electronic structure of the recently discovered superconductor SrPt₂As₂ with T _c = 5.2 K has been calculated in the local-density approximation. Despite its chemical composition and crystal structure are somehow similar to FeAs-based high-temperature superconductors, the electronic structure of SrPt₂As₂ is very much different. The crystal structure is orthorhombic (or tetragonal if idealized) and has layered nature with alternating PtAs₄ and AsPt₄ tetrahedra slabs sandwiched with Sr ions. The Fermi level is crossed by Pt-5d states with rather strong admixture of As-4p states. Fermi surface of SrPt₂As₂ is essentially three-dimensional, with complicated sheets corresponding to multiple bands. We compare SrPt₂As₂ with 1111 and 122 representatives of FeAs-class of superconductors, as well as with isovalent (Ba,Sr)Ni₂As₂ superconductors. Brief discussion of superconductivity in SrPt₂As₂ is also presented.     

Photoinduced gratings in a Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> ferroelectric crystal with the period depending on the optical pump power

The light scattering in the form of ring structures in Sn₂P₂S₆ crystals at the propagation of intense laser pump radiation along the b crystallographic axis is detected. Radiation passing through a crystal is completely scattered into a cone whose angle increases with the pump power and decreases reversibly with a decrease in this power. The observed effect can be attributed to a spontaneous increase in the amplitude of photoinduced bulk diffraction gratings and to the scattering of light on them in the directions where the phase increments of the photorefractive and diffraction natures compensate each other. A similar type of scattering was observed previously in other photorefractive crystals, but the appearance of gratings with the period easily varied by varying the pump power is demonstrated for the first time.     

Charge dynamics of the spin-density-wave state in BaFe<Subscript>2</Subscript>As<Subscript>2</Subscript>

We report on a thorough optical investigation of BaFe₂As₂ over a broad spectral range and as a function of temperature, focusing our attention on its spin-density-wave (SDW) phase transition at T_SDW = 135 K. While BaFe₂As₂ remains metallic at all temperatures, we observe a depletion in the far infrared energy interval of the optical conductivity below T_SDW, ascribed to the formation of a pseudogap-like feature in the excitation spectrum. This is accompanied by the narrowing of the Drude term consistent with the dc transport results and suggestive of suppression of scattering channels in the SDW state. About 20% of the spectral weight in the far infrared energy interval is affected by the SDW phase transition.     

Methane sensor based on SnO<Subscript>2</Subscript>/In<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanostructure

Two sets of samples of SnO₂/In₂O₃/TiO₂ system have been fabricated with different concentrations of component materials. In the first set TiO₂ with rutile structure was used, while in the second set it has the structure of anatase. Thin films (up to 50 nm) of obtained mixtures were deposited. Their sensitivity and selectivity with respect to methane (CH4) were studied. Nanostructure on the basis of 70%SnO₂ — 10%In₂O₃ — 20%TiO₂(anatase) exhibits sufficient sensitivity to methane.     

Fabrication and characterization of visible light-driven In<Subscript>2.77</Subscript>S<Subscript>4</Subscript>/In(OH)<Subscript>3</Subscript> composite photocatalysts with excellent redox performance

The In_2.77S₄ microspheres had been firstly fabricated by using polyethylene glycol (PEG) as the morphological modifier and then used to hybridize with In(OH)₃ nanocubes by a simply depositional method. The structure, optical properties, morphology, chemical compositions, and charge carrier behaviors of the as-prepared In_2.77S₄/In(OH)₃ composites were characterized, respectively. The methyl orange, tetracycline, rhodamine B, and Cr(VI) dilute solution were selected to evaluate their photocatalytic activities. Experimental results showed that In(OH)₃ nanocubes could improve the photocatalytic activity and recyclability of the In_2.77S₄ microspheres under the visible light irradiation. With the usage of In(OH)₃ increased, the photocatalytic efficiency of the hybrids was firstly increased and then decreased. When the mass ratios of In_2.77S₄ to In(OH)₃ were 6:2, it reached the maximum of 100% in 15 min for methyl orange, obviously higher than 67.4% of In_2.77S₄ and 1.1% of In(OH)₃. Meanwhile, it could also oxidize 85.6% of tetracycline in 20 min, 97.8% of rhodamine B in 7.5 min, and reduce 92.9% of Cr(VI) in 30 min under the visible light irradiation. Moreover, it could still degrade 91.7% of methyl orange solution after 3 cycles, which was much higher than 40.7% of In_2.77S₄ microspheres. In addition, the possible mechanism of enhancing photocatalytic properties was proposed.     

Band structure of (Sr<Subscript>3</Subscript>Sc<Subscript>2</Subscript>O<Subscript>5</Subscript>)Fe<Subscript>2</Subscript>As<Subscript>2</Subscript> as a possible basis phase of new FeAs superconductors

The results of the ab initio FLAPW-GGA computations of the band structure of the recently synthesized layered tetragonal (space group I4/mmm) arsenide (Sr₃Sc₂O₅)Fe₂As₂ as a possible basis phase of a new group of FeAs superconductors are presented. For (Sr₃Sc₂O₅)Fe₂As₂, the energy bands, electron state density distributions, Fermi surface topology, low-temperature electron specific heat, molar Pauli paramagnetic susceptibility, and effective atomic charges have been determined. These results are discussed compared to similar data for the layered tetragonal crystals LaFeAsO, SrFeAsF, SrFe₂As₂, and LiFeAs that are the basis phases of the recently discovered high-temperature (T _C ～ 26–56 K) 《1111》, 《122》, and 《111》 FeAs superconductors.     

Photoaccumulating film systems based on TiO<Subscript>2</Subscript>/MoO<Subscript>3</Subscript> and TiO<Subscript>2</Subscript>/MoO<Subscript>3</Subscript>:V<Subscript>2</Subscript>O<Subscript>5</Subscript> nanoheterostructures

The thin-film photocatalysts TiO₂/MoO₃ and TiO₂/MoO₃:V₂O₅ obtained by a combination of sol–gel and sintering techniques were studied using the photooxidation of probing dyes, EPR spectroscopy, X-ray diffraction analysis, and electron microscopy. It was shown that due to charge accumulation caused by UV irradiation, these photocatalysts retain their oxidative activity and ability for self-sterilization in the dark for a long time after irradiation was terminated (up to 5 h for TiO₂/MoO₃:V₂O₅).     

Superconductivity in Ti-doped iron-arsenide compound Sr<Subscript>4</Subscript>Cr<Subscript>0.8</Subscript>Ti<Subscript>1.2</Subscript>O<Subscript>6</Subscript>Fe<Subscript>2</Subscript>As<Subscript>2</Subscript>

Superconductivity was achieved in Ti-doped iron-arsenide compound Sr₄Cr_0.8Ti_1.2O₆Fe₂As₂ (abbreviated as Cr-FeAs-42622). The X-ray diffraction measurement shows that this material has a layered structure with the space group of P4/nmm, and with the lattice constants a = b = 3.9003 Å and c = 15.8376 Å. Clear diamagnetic signals in ac susceptibility data and zero-resistance in resistivity data were detected at about 6 K, confirming the occurrence of bulk superconductivity. Meanwhile we observed a superconducting transition in the resistive data with the onset transition temperature at 29.2 K, which may be induced by the nonuniform distribution of the Cr/Ti content in the FeAs-42622 phase.     

Multiple magnetic transitions in single crystals of Ce<Subscript>12</Subscript>Fe<Subscript>57.5</Subscript>As<Subscript>41</Subscript> and La<Subscript>12</Subscript>Fe<Subscript>57.5</Subscript>As<Subscript>41</Subscript>

Measurements of magnetic and transport properties were performed on needle-shaped single crystals of Ce₁₂Fe_57.5As₄₁ and La₁₂Fe_57.5As₄₁. The availability of a complete set of data enabled a side-by-side comparison between these two rare earth compounds. Both compounds exhibited multiple magnetic orders within 2–300 K and metamagnetic transitions at various fields. Ferromagnetic transitions with Curie temperatures of 100 and 125 K were found for Ce₁₂Fe_57.5As₄₁ and La₁₂Fe_57.5As₄₁, respectively, followed by antiferromagnetic type spin reorientations near Curie temperatures. The magnetic properties underwent complex evolution in the magnetic field for both compounds. An antiferromagnetic phase transition at about 60 K and 0.2 T was observed merely for Ce₁₂Fe_57.5As₄₁. The field-induced magnetic phase transition occurred from antiferromagnetic to ferromagnetic structure. A strong magnetocrystalline anisotropy was evident from magnetization measurements of Ce₁₂Fe_57.5As₄₁. A temperature-field phase diagram was present for these two rare earth systems. In addition, a logarithmic temperature dependence of electrical resistivity was observed in the two compounds within a large temperature range of 150–300 K, which is rarely found in 3D-based compounds. It may be related to Kondo scattering described by independent localized Fe 3d moments interacting with conduction electrons.     

Acoustic attenuation in ferroelectric Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> crystals

The temperature and frequency dependencies of sound attenuation for the proper uniaxial ferroelectric Sn₂P₂S₆, which has a strong nonlinear interaction of the polar soft optic and fully symmetrical optic modes that is related to the triple well potential, were studied by Brillouin spectroscopy. It was found that the sound velocity anomaly is described in the Landau-Khalatnikov approximation with one relaxation time. For explanation of the observed temperature and frequency dependencies of the sound attenuation in the ferroelectrric phase, the accounting of several relaxation times is needed and, for quantitative calculations, the mode Gruneisen coefficients are more appropriate as interacting parameters than are the electrostrictive coefficients. Relaxational sound attenuation by domain walls also appears in the ferroelectric phase of Sn₂P₂S₆ crystals.     

Photoluminescence of CaGa<Subscript>2</Subscript>S<Subscript>4</Subscript>:Pr Polycrystals

The photoluminescence (PL) and PL excitation spectra of CaGa₂S₄ polycrystals doped with praseodymium are studied in the regions of the activator absorption and the fundamental absorption of the host. It is found that the PL excitation spectrum consists of two regions: broadband absorption in the range of 200-380 nm corresponding to the fundamental absorption of the host and the narrow-band absorption of the dopant in the range of 430–515 nm. The luminescence spectra are different for different excitation wave-lengths, which occurs because Pr³⁺ ions substitute divalent cations occupying different crystallographic positions in the host crystal lattice.     

Optimized second-order optical nonlinearity in thermally poled GeS<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>-KI chalcohalide glass

0.56GeS₂-0.24Ga₂S₃-0.2KI (mol%) chalcohalide glass was prepared and second-harmonic generation was observed by the thermal poling process. Second-order optical nonlinearity in the glass was also investigated by different poling temperature, voltage and time to optimize the poling parameters to improve χ ⁽²⁾. The maximum χ ⁽²⁾ in our study as large as 3.74 pm/V was obtained under the optimized poling condition with 5.2 kV, 260°C and 120 minutes.