Thermal diffusion near glass transition in Ge-Se glasses measured by photoacoustics

The glass transition in Ge _x Se_1−x ) (0·1 ⩽x ⩽ 0·25) glasses has been investigated using the photoacoustic (PA) technique. It is found that the PA amplitude and phase undergo anomalous changes at the glass transition temperatureT _g. The amplitude has critical minimum and phase has maximum values atT _g. The variation of the thermal diffusivity, determined by measuring the frequency dependence of the PA amplitude and phase, with temperature shows sharp decrease near the glass transition temperature. The temperature dependence of the optical energy gap also has been measured and it shows a decrease with temperature for all compositions, the rate of decrease being higher for temperatures greater thanT _g.     

Characteristics of photoconductivity in As-Sb-Se glasses

Characteristic features of photoconductivity in As _x Sb₁₅Se_85−x and As_xSb₁₀Se_90−x bulk glass systems have been measured and reported. Both a.c and d.c techniques have been employed for the measurements. The temperature dependence of photoconductivity has been analysed in terms of the ABFH model and both systems are found to exhibit type I photoconductivity. Photoconductivity shows a clear change in slope corresponding to the stoichiometric composition in both the systems. The composition dependence of photoconductivity is explained on the basis of chemically ordered covalent network (COCN) model. Photoconductivity response time of the two systems have been determined from frequency-resolved photocurrent (FRPC) measurements. Variation of response time with composition exhibits a clear change in slope at the stoichiometric composition in both the systems.     

Characterization of new quaternary chalcogenide As–Ge–Se–Sb thin films

This paper reports the effect of replacement of selenium by antimony on the optical gap and some other physical parameters of new quaternary chalcogenide As₁₄Ge₁₄Se_{72? x} Sb _x (where x = 3, 6, 9, 12 and 15 at%) thin films. Thin films with thickness 200–220 nm of As₁₄Ge₁₄Se_{72? x} Sb _x were prepared by thermal evaporation of the bulk samples. Increasing antimony content was found to affect the average heat of atomization, the average coordination number, number of constraints and cohesive energy of the As₁₄Ge₁₄Se_{72 ?x} Sb _x alloys. Optical absorption measurements showed that the fundamental absorption edge is a function of composition. Optical absorption is due to allowed, non-direct transition and the energy gap decreases with the increasing antimony content. The chemical bond approach has been applied successfully to interpret the decrease in the optical gap with increasing antimony content.     

Characterization of (As.Te)1-xSex thin films

1-x Se_x thin films (where x=0.20, 0.23, 0.27, 0.32 and 0.44) have been studied. Increasing the Se content was found to increase the optical energy gap and the activation energy for conduction of the investigated films. The optical energy gap of the As_0.40Te_0.40Se_0.20 films was increased up to 1.21 eV by increasing the film thickness to ∼120 nm, while thermal annealing at 480 K reduced it down to 0.83 eV. The decrease of the optical gap is discussed on the basis of amorphous–crystalline transformations. Received: 07 July 1997/Accepted: 30 July 1997     

Thermal conductivity of GexSb(As)ySe100‐x‐y glasses measured by Raman scattering spectra

We systematically measured thermal conductivity of Ge_xSb(As)₁₀Se_90−x, Ge_xSb₁₅Se_85−x, and Ge_xSb(As)₂₀Se_80−x chalcogenide glasses by measuring their Stokes and anti‐Stokes Raman scattering spectra and estimating the temperature raised by laser irradiation via the ratio of Stoke and anti‐Stokes scattering cross‐section. We aimed at demonstrating the viability of Raman scattering method for thermal conductivity measurements, and understanding the role of chemical composition in determining thermal conductivity of the chalcogenide glasses. We found that, while the values of the thermal conductivity measured in the paper are in a range from ~0.078 to 1.120 Wm^‐1K^‐1 that are in agreement with those reported data in the literatures, thermal conductivity increases before it reaches a maximum at the glass with chemically stoichiometric composition, and then decreases with increasing Ge content. We ascribed the threshold behavior of the thermal conductivity to the demixing of the structural units like GeSe₂, As₂Se₃ and Sb₂Se₃ from the main glass network. The present study demonstrated that Raman scattering method is simple and easy to measure thermal conductivity of the material. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of constant-energy surface anisotropy on the thermoelectric figure-of-merit of the n-Bi2 (Te,Se,S)3 solid solutions

A study is reported of the thermoelectric and galvanomagnetic properties of n-Bi₂Te_3−x−y Se_xSe_y solid solutions for 0.12⩽x⩽0.36 and 0.12⩽y⩽0.21 within the 80–300 K temperature region. The thermoelectric figure-of-merit Z has been found to correlate with the parameters of the many-valley energy-band model including anisotropic carrier scattering. It is shown that a decrease in the constant-energy surface anisotropy and scattering anisotropy results in a growth of Z for optimum carrier concentrations in the solid solution. Fiz. Tverd. Tela (St. Petersburg) 41, 187–192 (February 1999)     

An evidence for a microscopic phase separation in AsSeAg glasses revealed by thermal and structural investigations

Alternating Differential Scanning Calorimetric (ADSC) studies show that Se rich As₂₀Se_80-xAg_x (0 ≤ x ≤ 15) glasses exhibit two endothermic glass transitions and two exothermic crystallization peaks; the observed thermal behavior has been understood on the basis that As₂₀Se_80-xAg_x glasses are microscopically phase separated, containing Ag₂Se phases embedded in an As-Se backbone. With increasing silver concentration, the Ag₂Se phase percolates in the As-Se matrix, with a well-defined percolation threshold at x = 8. A signature of this percolation transition is shown up in the thermal behavior, as sudden jumps in the composition dependence of non-reversing enthalpy, ΔH_nr obtained at the second glass transition reaction. Scanning Electron Microscopic (SEM) studies also confirm the microscopic phase separation in these glasses. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be associated with the silver phase percolation.     

Electronic structure,topological phase transitions and superconductivity in (K,Cs)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>2</Subscript>Se<Subscript>2</Subscript>

We present LDA band structure of novel hole doped high temperature superconductors (T _c ∼ 30 K) K _x Fe₂Se₂ and Cs _x Fe₂Se₂ and compare it with previously studied electronic structure of isostructural FeAs superconductor BaFe₂As₂ (Ba122). We show that stoichiometric KFe₂Se₂ and CsFe₂Se₂ have rather different Fermi surfaces as compared with Ba122. However at about 60% of hole doping Fermi surfaces of novel materials closely resemble those of Ba122. In between these dopings we observe a number of topological Fermi surface transitions near the Γ point in the Brillouin zone. Superconducting transition temperature T _c of new systems is apparently governed by the value of the total density of states (DOS) at the Fermi level.     

Optical absorption edge of As<Subscript>40–<Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>60</Subscript> glassy alloys

The fundamental absorption edge of glassy alloys of an As–Sb–S system was studied in the temperature range 77–300 K. The spectral and thermal behavior of the fundamental absorption edge of As_40–x Sb_xS₆₀ glasses was shown to be described by an exponential function of phonon energy. The temperature and concentration behavior of the optical band gap in the studied glasses was established. The well-known Varshni relationship was used to describe the temperature dependence of the optical band gap.     

Experimental study and configurational-coordinate model for photo-induced effects in amorphous As2Se3 films

The optical absorption of As₂Se₃ thin films is studied in the UV–VIS spectral range and the value of the optical energy gap is determined. The effect of photo-irradiation on the optical absorption and transmission of thin film samples is also investigated. The optical energy gap was found to decrease with photo-irradiation time. The results of photo-irradiation are discussed in correlation with the structural aspects of As₂Se₃. A model is proposed to account for the structural changes, resulting from photo-irradiation, causing the decrease of the energy gap. The effect of γ-radiation on the optical absorption of As₂Se₃ thin films was studied also and no detectable effect on the value of the optical energy gap was observed.     

Carrier mobility in nonstoichiometric n-Bi2Te3−x Sex solid solutions

A study has been made of the thermoelectric and galvanomagnetic properties of n-Bi₂Te_3−x Se_x solid solutions (x=0.3 and 0.36) in the temperature range 80–300 K. The lowest carrier concentrations, (0.8–1)×10¹⁸ cm⁻³, were obtained by displacing the solid solution from the stoichiometric to a Te-rich composition. At such carrier concentrations, the second subband in the conduction band of n-Bi₂Te_3−x Se_x is not filled, which results in a growth of mobility because of the absence of interband scattering, and brings about an increase of thermoelectric efficiency in the 80–120-K range. Fiz. Tverd. Tela (St. Petersburg) 39, 483–487 (March 1997)     

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.      

X-ray,electrical conductivity,magnetic and infrared studies of the system Co2−x Ge1−x Fe2x O4

X-ray, electrical conductivity, magnetic hysteresis and IR studies for the system Co_2−x Ge_1−x Fe_2x O₄ were carried out. All the compounds, 0⩽x⩽1, showed cubic symmetry. X-ray intensity calculations, magnetic hysteresis measurements and IR studies indicated the presence of Ge⁴⁺ at tetrahedral, Co²⁺ at octahedral and Fe³⁺ at both the sites. The activation energy and threshold frequency decreased with increasing value ofx. The compounds withx⩽0.5 arep-type and those withx⩾0.75 aren-type semiconductors. Magnetic hysteresis indicated that all the compounds are ferrimagnetic except forx=0 which is antiferromagnetic. The shapes of χ/χ _i vsT plots, highH _c values andJ _R/J_s ratios showed that all the compounds exceptx=0 exhibit single-domain behaviour. Curie temperature,T _c increased with increasing Fe³⁺ ions. The probable ionic configuration for the system is suggested as Ge _1−x ⁴⁺ Fe _x ³⁺ [co _2−x ²⁺ Fe _x ³⁺ ]O ₄ ²⁻ .     

Effect of replacement of Se by S on structural and physical properties of Ge–Sb–As–Se–S chalcogenide glasses

In the present study, the structural and opto-mechanical properties of Ge–Sb–As–Se–S chalcogenide glasses have been investigated. For this purpose, different bulk glasses of Ge₂₀Sb₅As₁₅Se_60?xS_x (0 ≤ x≤50) were prepared by conventional melt quenching technique in quartz ampoule and different characteristics of prepared glasses such as glass transition temperature, density, hardness, transmittance, optical band gap energy and refractive index were determined. The value of hardness and glass transition temperature of prepared glasses were found to increase with increasing the sulfur content as a result of formation of GeS₄ tetrahedral units and increasing the network connectivity and average bonding energy. The optical energy gap (according to Tauc’s relation), transmittance and refractive index of prepared glasses are in direct relation with sulfur content. In this study, the highest value of transmittance (about 70%) and lowest value of refractive index (2–2.3) was achieved in Ge₂₀Sb₅As₁₅Se₄₀S₂₀ and Ge₂₀Sb₅As₁₅Se₁₀S₅₀ glasses, respectively.     

Low temperature elastic behaviour of As-Sb-Se and Ge-Sb-Se glasses

The ternary glasses of arsenic and germanium with antimony and selenium can be prepared in large sizes for optical purposes. The elastic behaviour of eight compositions of each glass has been studied down to 4.2 K using a 10 MHz ultrasonic pulse echo interferometer. The glasses have a normal elastic behaviour, with the velocities gradually increasing as the temperature is lowered. An anharmonic solid model of Lakkad satisfactorily explains the temperature variations. The elastic moduli of Ge _x Sb₁₀Se_90?x glasses increase linearly as the Ge content is increased up to 25 at. % and beyond this the increase is nonlinear. (AsSb)₄₀Se₆₀ glasses show a linear increase in elastic moduli with increasing Sb content. The elastic moduli of As _x Sb₁₅Se_85?x glasses exhibit a drastic change near the stoichiometric composition As₂₅Sb₁₅Se₆₀. These behaviours have been qualitatively explained on the basis of the structural changes in glasses.     

Transport properties of antiferromagnetic fcc-iron alloys

A study is reported of the electrical resistance and thermopower of Fe_xNi_80−x Cr₂₀ fcc alloys within the 44⩽x⩽70 at. % range. It is shown that, at low temperatures, they typically exhibit minima in the temperature dependences of electrical resistance. The appearance of these anomalies is attributed to the formation of a gap in the conduction electron spectrum due to the onset of long-or short-range antiferromagnetic order in the alloys. The effect of magnetic field on the magnetic states appearing in frustrated antiferromagnetic alloys has been studied, and an H-T magnetic phase diagram constructed. Fiz. Tverd. Tela (St. Petersburg) 40, 101–105 (January 1998)     

Structural and electronic properties of GaN x As1−x alloys

The structural and electronic properties of cubic GaN _x As_1−x with N-concentration varying between 0.0 and 1.0 with step of 0.25 were investigated using the full potential–linearized augmented plane wave (FP-LAPW) method. We have used the local density approximation (LDA) and the generalized gradient approximation (GGA) for the exchange and correlation potential. In addition the Engel-Vosko generalized gradient approximation (EVGGA) was used for the band-structure calculations. The structural properties of the binary and ternary alloys were investigated. The electronic band structure, total and partial density of states as well as the electron charge density were determined for both the binary and their related ternary alloys. The energy gap of the alloys decreases when we move from x=0.0 to 0.25; then it increases by a factor of about 1.8 when we move from 0.25 to 0.5, 0.75 and 1.0 using EVGGA. For both LDA and GGA moving from x=0.0 to 0.25 causes the band gap to close, showing the metallic nature of the GaN_0.25As_0.75 alloy. When the composition of N moves through x=0.25, 0.5, 0.75 and 1, the band gap increases.     

Threshold electrical switching in As45Te55-xInx and As50Te50-xInx glasses

The electrical switching behaviour of As₄₅Te_55-xIn_x (5≤x≤15) and As₅₀Te_50-xIn_x (2.5≤x≤11.5) has been studied over a wide range of compositions. These glasses are found to exhibit threshold switching. The composition dependence of switching voltage (V_t) has been found to exhibit a change in slope and a local minimum at compositions x=10 and 12.5 for As₄₅Te_55-xIn_x and x=7.5 and 10.8 for As₅₀Te_50-xIn_x, respectively. The slope change in V_t verses x and the local minimum have been identified using two network topological effects, namely the rigidity percolation threshold and the chemical threshold. Received: 23 August 2001 / Accepted: 27 August 2001 / Published online: 11 February 2002     

Amorphous-to-crystalline transition in Ge22Se78−x Bi x system

Summary Crystallization kinetics is studied in glassy Ge₂₂Se_78−x Bi _x (0≤x≤10) using isothermal annealing at various temperatures between the glass transition and melting. D.c. conductivity is taken as a parameter to estimate the extent of crystallization (α). The activation energy of crystallization (ΔE) and the order parameter (n) are calculated by fitting the values of α in Avrami’s equations of isothermal transformation. The results indicate that ΔE is highly composition dependent and decreases as the Bi concentration increases.     

Electrical switching studies on As<Subscript>40</Subscript>Te<Subscript>60-x</Subscript>Se<Subscript>x</Subscript> and As<Subscript>35</Subscript>Te<Subscript>65-x</Subscript>Se<Subscript>x</Subscript> glasses

The I–V characteristics of bulk As₄₀Te_60-xSe_x and As₃₅Te_65-xSe_x glasses have been studied with a current sweep of 0–18 mA-0, over a wide range of compositions (4≤x≤22). All the glasses studied showed a threshold electrical switching behaviour. The number of switching cycles withstood by the samples has been found to depend on the ON-state current. It is seen that the switching voltages increase with increase in selenium content. Further, the switching voltages are found to be almost independent of the thickness of the sample (d), in the range 0.18–0.3 mm. Also, the switching voltages and the number of switching cycles withstood by the samples are found to decrease with temperature. Received: 6 November 2002 / Accepted: 8 November 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +91-80/360-0135, E-mail: sasokan@isu.iisc.ernet.in