Photoinduced effect in Ga-Ge-S based thin films

Glassy films of Ga₁₀Ge₂₅S₆₅ with 4 μm thickness were deposited on quartz substrates by electron beam evaporation. Photoexpansion (PE) (photoinduced increase in volume) and photobleaching (PB) (blue shift of the bandgap) effects have been examined. The exposed areas have been analyzed using perfilometer and an expansion of 1.7 μm (ΔV/V ≈ 30%) is observed for composition Ga₁₀Ge₂₅S₆₅ exposed during 180 min and 3 mW/cm² power density. The optical absorption edge measured for the film Ge₂₅Ga₁₀S₆₅ above and below the bandgap show that the blue shift of the gap by below bandgap photon illumination is considerable higher (ΔE_g = 440 meV) than ΔE_g induced by above bandgap illumination (ΔE_g = 190 meV). The distribution of the refraction index profile showed a negative change of the refraction index in the irradiated samples (Δn = −0.6). The morphology was examined using a scanning electron microscopy (SEM). The chemical compositions measured using an energy dispersive analyzer (EDX) indicate an increase of the oxygen atoms into the irradiated area. Using a Lloyd's mirror setup for continuous wave holography it was possible to record holographic gratings using the photoinduced effects that occur in them. Diffraction efficiency up to 25% was achieved for the recorded gratings and atomic force microscopy images are presented.     

Spectroscopic search for the free carrier screening of the excitonic binding

A spectroscopic determination of the energy gap E_g and the exciton energy E_x in highly excited Ge at T = 5–20K is presented. Within 0.05 meV we observe no shift of E_g and E_x up to electron-hole densities of 10¹⁴?10¹⁵ cm^?3. In this range all previous theories predict a sizeable band renormalization (ΔE_g ≈?0.3 meV to ? 2 meV).     

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.     

Calorimetric studies of the crystallization process in a-Se75S25−xAgx chalcogenide glasses

Calorimetric studies of amorphous Se₇₅S_25−xAg_x (x = 2, 4, 6 and 8) chalcogenide glasses are made at different heating rates (5, 10, 15 and 20 K/min) under non-isothermal condition using Differential scanning calorimetry. The values of glass transition temperature and crystallization temperature are observed to be composition and heating rate dependence. From the heating rate dependence of glass transition temperature and crystallization temperature, the activation energy for structural relaxation (ΔE_t), the activation energy of crystallization (ΔE_c) and the order parameter (n) have been calculated. It is observed that Se₇₅S₁₉Ag₆ has a minimum value of activation energy for structural relaxation (ΔE_t), which indicates that this particular glass has a larger probability to jump to a state of lower configurational energy and higher stability in the glassy region. On the basis of the obtained experimental data the temperature difference (T_c − T_g) is found to be maximum for Se₇₅S₁₉Ag₆, which further indicate that this glass is the thermally most stable in the entire composition range of investigation.     

Phenomenological thermodynamics of mixed valence phenomenon

The fluctuation of valence in some rare-earth (RE) compounds is described in terms of the effective potential seen by the RE ion. The nearly degenerate $\text{4?}{}^{\mathrm{n+1}}\text{(5d6s)}{}^2$ and $\text{4?}{}^{\mathrm{n}}\text{(5d6s)}{}^3$ levels of the RE ion split in energy in the presence of a repulsive potential. The energy separation (ΔE) between these levels is a function of external variables such as temperature, pressure or composition, which change the effective potential seen by the ion. The variation of ΔE with temperature is obtained for four Europium compounds from ¹⁵¹Eu Mössbauer isomer shift data. The temperature dependence of susceptibility is then obtained from the same (ΔE) variation and compared with experimental results. A characteristic temperature (T_υ) is found below and above which (ΔE) behave as ΔE = αT and ΔE = βT+γ respectively.     

The nature of temperature dependence of energy gaps in layer semiconductors

The temperature dependences of direct and indirect energy gaps in layer semiconductors GaS, GaSe and GaS_xSe_1?x are investigated in the temperature range 5–150 K. The nonmonotonous behaviour of E_g(T) dependences is observed in these crystals. It is shown that the effect of thermal expansion cannot in itself explain the observed anomalies. A new model of electron-phonon interaction explaining the E_g(T) behaviour in layer crystals is proposed.     

Relation between elastic modulus and glass softening temperature in the delocalized atom model

The ratio of softening temperature (glass transition temperature) to elastic modulus (T _g /E) is mainly determined by the limiting elastic deformation of an interatomic bond, which characterizes the transition of a structural microregion from an elastic into a viscous-flow state. In silicate glasses, this transition is caused by the limiting deformation of directed ionic-covalent Si-O-Si bonds. In the case of amorphous hydrocarbons, it is related to the relatively weak intermolecular bonds between regions in chain macromolecules, and the T _g /E ratio is significantly higher than in inorganic glasses. In glassy systems of one class, this ratio turns out to be constant (T _g /E ?? const), and a linear correlation is detected between softening temperature and elastic modulus, which can be explained in terms of the delocalized atom model. The values of T _g /E can be used to classify glasses similarly to the well-known Angell classification according to so-called fragility.     

Temperature dependence of interband transitions and exchange splitting in nickel

Interband transitions of Ni have been studied as a function of temperature by observing energy losses of low energy electrons reflected from a Ni(100) surface. A threshold is found at E_g ～ 0.15 eV and interpreted as the onset of X^↑₅ → X^↓₂ transitions. The threshold remains unchanged for temperatures up to 900 K. The loss continuum below E_g exhibits an anomalous increase with temperature with a discontinuity in the slope at T ～ 1.2 T_c.     

Effective mass and energy-band parameters in InP by magnetophonon effect

We present measurements of the magnetophonon effect in InP from which we derive the effective mass of electrons at the conduction band edge in its temperature dependence. For the first time the measurements are extended well above room temperature up to T = 350 K in quasi-steady magnetic fields up to B = 15 T. The analysis of the measurements which corroborates the three-band interaction for InP allows us to determine the temperature dependence of the square E _p of the momentum matrix element, related to the effective mass, as E _p(T) = (16.6±0.2) eV-(4.8±1.0) [E _g(T)-E _go].     

Effects of different parameters on thermal and mechanical properties of aminated graphene/epoxy nanocomposites connected by covalent: A molecular dynamics study

This paper is devoted to studying the thermal and mechanical properties of aminated graphene (AG)/epoxy nanocomposites connected by covalent bond using molecular dynamics (MD) simulation. The effects of crosslinking degree, mass fraction and functionalized graphene (FG) type on AG/epoxy nanocomposites are considered. The elasticity modulus (E), the glass transition temperature (T_g), the coefficient of thermal expansion (CTE) and the interfacial energy (E_int) are also investigated. The MD simulation results indicate that, when the mass fraction of AG is between 1.2% and 3.1% and crosslinking degree reaches about 70%, the E, T_g, E_int and CTE of AG/epoxy nanocomposites are significantly improved compared with those of pure epoxy and graphene/epoxy nanocomposites. The reason is that AG not only possesses some excellent thermodynamic properties of graphene, but also has the function of curing agent to crosslink with epoxy monomer to form the carbon-nitrogen (C–N) covalent bond. A better interfacial interaction between nanoparticles and epoxy is essential in enhancing the thermal and mechanical properties of nanocomposite materials, which will provide a microscopic theoretical basis for the study of epoxy nanocomposites.     

Solvent and temperature dependence of the phosphorescence decay time of hexacyanochromate (III)

The temperature dependence of the ²E_g - ⁴A_2g phosphorescence of tetrabutylammonium hexacyanochromate (III) dissolved in various solvents has been measured within the liquid range of these solvents. In this limited temperature range, the reciprocal decay times obey Arrhenius relationship. From the absence of a solvent isotope effect, in ethanol and methanol and their monodeuterated analogues it is concluded that hydrogen bonds between the solvent and the complex ion do not provide promoting or accepting modes for the radiationless deactivation. The room temperature decay times have been found to correlate with the solvatochromic shift of the ⁴A_2g ? ⁴T_2g absorption bands and with Dimroth's E_T parameter. According to the selection rules for non-radiative decay a combination of CN stretching with either a Cr-C-N bending or a Cr-C stretching vibration is postulated as the promoting mode.     

The effect of fast neutron irradiation on the optical modulation spectra of GaAs

The electroreflectance and wavelength-modulated reflectance spectra of GaAs were measured before and after several reactor irradiation periods. High resistivity n type GaAs crystals were irradiated at a temperature between 300 and 310 K up to a fast neutron fluence of 3.3 × 10¹⁷n/cm². The E₀ and E₀+Δ_o peaks shift nonlinearly toward lower energy, the change reaching a maximum value of about ? 50 meV at 10¹⁷n/cm². At this fluence an additional peak appears at 1.33 eV. The E₁ and E₁+Δ₁ peaks move almost linearly toward higher energy with increasing fast neutron fluence, the shift being about + 25 meV at 2 × 10¹⁷n/cm². The results are discussed taking into account infrared absorption measurements and the calculations made by McNichols, Hayes and Ginell concerning the metallic GaAs precipitates. The effect of possible internal stress produced by the fast neutron bombardment on the modulation spectra is also discussed.     

Effect of Alkyl Side Chain Length on Relaxation Behaviors in Poly(n-alkyl Acrylates) and Poly(n-alkyl Methacrylates)

Dynamic mechanical analysis (DMA) is used to investigate the effect of alkyl side chain length on the relaxation behavior of poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) above the glass transition temperature (T_g). Master curves and shift factors (log a_T) were obtained using the time–temperature superposition (TTS) principle. The log a_T curves of PnAA and PnAMA exhibit a dynamic crossover from one Vogel–Fulcher–Tammann–Hesse (VFTH) equation to another above T_g. The corresponding temperature was designated as the dynamic crossover temperature (T_c). It is found that T_c/T_g and the apparent activation energy (E_g) increases, e whereas the fragility index (m) decreases with increasing alkyl side chain length. Further analysis shows that m ∝ T_g, E_g∝ , and E_g∝ m² for both PnAA and PnAMA.     

Infrared laser modulation spectroscopy

The lack of sensitivity in far infrared of conventional modulation techniques can be overcome by the use of a laser beam as a powerful high resolution infrared source. As an illustration of these features we describe a thermoreflectance experiment performed on mercury telluride using a frequency stabilised CO₂ laser. In this experiment a thin slab of HgTe was illuminated by the beam of the laser. A continuous shift of the Γ_6v?Γ_8c energy interval was produced by a slow temperature variation while the sample was submitted to a slight temperature modulation obtained by low frequency Joule heating. Synchronous and direct detection of the reflected beam gave the relative variation of reflectivity as a function of the sample temperature. Several spectra obtained at different emission lines enable us to determine the energy difference (E_g) between Γ_6v and Γ_8c inverted states. As a first approach a qualificative fit has been obtained with a simple model of dielectric constant and its temperature derivative. These results give the first direct determination of E_g near room temperature E_g = ? 117.04 meV at T = 286 ± 2 K.     

Anomaly in the lattice partition function

The lattice partition function Z(T)=σ_(Si) exp(−H/k_BT), where H, k_B and T are the Hamiltonian of the system, the Boltzmann constant and the absolute temperature, respectively, leads to a vanishing spontaneous magnetisation for all temperatures, independently of the lattice considered. This feature is related to the symmetry breaking in these systems. In comparing this relation to the well-known partition function Z(T)=σ_n exp(−E_n/k_BT) where E_n is energy, we observe an incompatibility which could be the reason that this partition function leads to a vanishing spontaneous magnetisation.     

Influence of temperature on raman spectra of the FeS2 single crystal with pyrite structure

Raman scattering in a natural FeS₂ single crystal with the pyrite structure was investigated in the temperature range of 80–300 K. All five Raman-active modes E _g , T _g (1), T _g (2), A _g , and T _g (3) were observed under normal conditions (T = 23°C). The influence of temperature on the Raman spectra was studied in the HH configurations (polarizations of the incident and scattered radiations are parallel), which made it possible to detect the strongest spectral lines A _g and E _g . Widths of modes E _g and A _g were substantially smaller than those given in previous publications. It was found that the temperature dependences of frequencies and widths (FWHM) of modes A _g and E _g are approximated well by the Klemens model, which describes the three-phonon scattering mechanism.     

Thermal expansion of a YBa2Cu3O7 superconducting ceramic

The thermal expansion of the High T_c superconducting ceramic YBa₂Cu₃O_7-δ has been measured from 50 K up to room temperature by means of a capacitance dilatometer. No detectable anomalous change in lenght is observed at the critical temperature T_c, within the resolution of our experimental set up: Δl/l = 5 10⁻⁸. This indicates a weak dependence of T_c on pressure, contrarily to the one measured on (LaBa)CuO lower T_c superconducting ceramics. The Debye temperature is also estimated.     

Dielectric Spectroscopy of Strongly Correlated Electronic States of Vanadium Dioxide

The thermal evolution of the conductivity of a VO₂ film and database-obtained band gap E_g of film nanocrystallites is traced in the temperature range of –196°C < T < 100°C (77 K < T < 273 K); the level position of donor impurity centers is determined to be E_d = 0.04 eV. It is shown that energy E_g decreases from 0.8 to ～0 eV with an increase in temperature in the range of 273 K < T < 300 K, which is caused by the narrowing of the energy gap due to correlation effects and considered as the temperature-extended Mott “insulator–metal” electron phase transition with the monoclinic lattice symmetry retained. The subsequent jump in the symmetry from monoclinic to tetragonal with a further increase in temperature is considered as the Peierls structural phase transition, the temperature of which is in the vicinity of 340 K and determined by the size effects, nonstoichiometry of VO₂ film nanocrystallites, and degree of their adhesion to the substrate.     

Lattice thermal conductivity of compounds with inhomogeneous intermediate rare-earth ion valence

The thermal conductivity κ (within the range 4–300 K) and electrical conductivity σ (from 80 to 300 K) of polycrystalline Sm₃S₄ with the lattice parameter a=8.505 Å (with a slight off-stoichiometry toward Sm₂S₃) are measured. For T>95 K, charge transfer is shown to occur, as in stoichiometric Sm₃S₄ samples, by the hopping mechanism (σ ～ exp(?ΔE/kT) with ΔE ～ 0.13 eV). At low temperatures [up to the maximum in the lattice thermal conductivity κ_ph(T)], κ_ph ～ T ^2.6; in the range 20–50 K, κ_ph ～ T ^?1.2; and for T>95 K, where the hopping charge-transfer mechanism sets in, κ_ph ～ T ^?0.3 and a noticeable residual thermal resistivity is observed. It is concluded that in compounds with inhomogeneous intermediate rare-earthion valence, to which Sm₃S₄ belongs, electron hopping from Sm²⁺ (ion with a larger radius) to Sm³⁺ (ion with a smaller radius) and back generates local stresses in the crystal lattice which bring about a change in the thermal conductivity scaling of κ_ph from T ^?1.2 to T ^?0.3 and the formation of an appreciable residual thermal resistivity.     

Calorimetric study of Te15(Se100− x Bi x )85 glassy alloys using differential thermal analysis

A calorimetric study of Te₁₅(Se_{100? x} Bi _x )₈₅ glassy alloys (x = 0, 1, 2, 3 and 4 at. %) is reported. Differential thermal analysis (DTA) was performed at heating rates of 10, 15, 20 and 25 K/min. The spectra were used to determine the glass transition temperature, T_g , the crystallisation temperature, T_c and the melting temperature, T_m . All these parameters shift to higher values with increasing heating rate, β. The glass transition temperature and the melting temperature increase, and the crystallisation temperature decreases, with increase in the Bi content, x. The activation energy of the glass transition, E_g , was evaluated using the Moynihan and Kissinger methods. The activation energy of crystallisation, E_c , was calculated using modified Kissinger and Matusita approaches. The thermal stability of these glasses has been studied and found to decrease with increase in Bi content. The results obtained are explained on the basis of a chemically ordered network model and an average coordination number.