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.     

Determination of the thickness and optical constants of amorphous Ge–Se–Bi thin films

The effect of varying bismuth concentration on the optical constants of amorphous Ge₂₀Se_{80? x} Bi _x (where x = 0, 3, 6, 9 and 12 at%) thin films prepared by thermal evaporation has been investigated. The transmission spectra T(λ) of the films at normal incidence were obtained in the spectral region from 400 to 2500 nm. An analysis proposed by Swanepoel [J. Phys. E: Sci. Instrum. 16 (1983) p.1214], based on the use of the maxima and minima of the interference fringes, was applied to derive the real and imaginary parts of the complex index of refraction and also the film thickness. Increasing bismuth content was found to affect the refractive index and extinction coefficient of the Ge₂₀Se_{80? x} Bi _x films. Optical absorption measurements show that the fundamental absorption edge is a function of composition. With increasing bismuth content, the refractive index increases while the optical band gap decreases.     

On the properties and stability of thermally evaporated Ge–As–Se thin films

Thin films of Ge–As–Se chalcogenide glasses have been deposited by thermal evaporation from bulk material and submitted to thermal treatments. The linear refractive index and optical band-gap for as-deposited and annealed films have been analyzed as function of the deposition parameters, chemical composition and mean coordination number (MCN). The chemical composition of the films was found to be directly affected by deposition rate, with low rates producing films with elevated Ge and reduced As content, whilst at high rates the Ge content was generally reduced and As levels increased compared with the bulk starting material. As a result films with close to the same stoichiometry as the bulk glass could be obtained by choosing appropriate deposition conditions. As-deposited films with MCN in between 2.44 and 2.55 showed refractive indices and optical band-gaps very close to those of the bulk glass whereas outside this range the film indices were higher and the optical gaps lower than those of the bulk glass. Upon annealing at close to their glass transition temperature, high MCN films evolved such that their indices and band-gaps approached the bulk glass values whereas at low MCN films resulted in no changes to the film properties.     

Effect of composition and light intensity on the electrical properties of Sn–Sb–Se glassy films

Electrical and photoelectrical measurements have been performed on Sn_xSb₂₀Se_70-x (8≤x≤16) glassy films. The dc activation energy, optical gap and photoconduction parameters show a typical variation near x=10 composition indicating the occurrence of a rigidity percolation threshold in the present system. The photosensitivity increases with the increase in Sn content up to x=14 and an abrupt decrease for x=16 composition. Negative photoconductivity region have been observed in the higher temperature side for samples with x=10 and 16. This system belongs to the type II category of photoconductors. The results are explained on the basis of a change in the density of localized states present in the mobility gap with the change in the composition. PACS 71.20.Nr; 72.20.-I; 78.66.Jg; 81.05.Gc; 73.50.Pz     

Optical properties of polysiloxane hybrid thin films containing nano-sized Ag–As–Se chalcogenide clusters

Chalcogenide glasses are attractive for all-optical signal processing due to their outstanding optical properties, including large optical nonlinearity, a high refractive index and high photosensitivity. In device fabrication, a challenge lies in the difficulty of obtaining thin films with a high stability and good uniformity. In this paper, optical thin films containing nano-sized chalcogenide clusters in polysiloxane matrices are fabricated by a modified plasma deposition process. The optical absorption and luminescence emission properties of the hybrid thin films were characterized by UV-Vis-NIR and fluorescence spectroscopy. Luminescent emission from Ag–As–Se nano-sized clusters was observed for the first time in these nano-hybrid thin films, and the mechanism was discussed.     

Photoinduced effects on the optical constants of a-Ge–Se–Bi chalcogenide glassy thin films

In addition to the conversion from p-type to n-type conductivity that occurs in Ge–Se–Bi thin films when Bi is incorporated in a certain concentration. We found that, when these films were illuminated to UV light, after being annealed at glass transition temperature T _g, the photobleaching is dominant for Ge₂₀Se_80?x Bi _x (x=0, 2.5, and 5 at.%), while for Ge₂₀Se_72.5Bi_7.5 photodarkening is dominant. The photoinduced changes in the optical constants were studied. The refractive index (n) has been analysed according to the Wwmple–DiDominico single oscillator model and the values of E _o and E _d for exposed and unexposed films were determined, respectively. The photostructural effects were discussed in the light of single–double well model proposed by Tanaka and chemical bond approach.     

Hall effect of FeTe and Fe(Se1–xTex) thin films

The Hall effect is investigated in thin-film samples of iron–chalcogenide superconductors in detail. The Hall coefficient (R_H) of FeTe and Fe(Se_1–xTe_x) exhibits a similar positive value around 300 K, indicating that the high-temperature normal state is dominated by hole-channel transport. FeTe exhibits a sign reversal from positive to negative across the transition to the low-temperature antiferromagnetic state, indicating the occurrence of drastic reconstruction in the band structure. The mobility analysis using the carrier density theoretically calculated reveals that the mobility of holes is strongly suppressed to zero, and hence the electric transport looks to be dominated by electrons. The Se substitution to Te suppresses the antiferromagnetic long-range order and induces superconductivity instead. The similar mobility analysis for Fe(Se_0.4Te_0.6) and Fe(Se_0.5Te_0.5) thin films shows that the mobility of electrons increases with decreasing temperature even in the paramagnetic state, and keeps sufficiently high values down to the superconducting transition temperature. From the comparison between FeTe and Fe(Se_1–xTe_x), it is suggested that the coexistence of ‘itinerant’ carriers both in electron and hole channels is indispensable for the occurrence of superconductivity.     

Structure and magnetic properties of co-sputtered Co–C thin films

We studied the structure and magnetic properties of co-sputtered Co_1−xC_x thin films using a transmission electron microscope (TEM) and a SQUID magnetometer. These properties were found to depend critically on deposition temperature, T_S, and composition, x. Generally, phase separation into metallic Co and graphite-like carbon phases proceeds with increasing T_S and decreasing x. Plan view and cross-sectional TEM images of the films prepared showed that Co grains about 10–20 nm in diameter and 30–50 nm in height are three-dimensionally separated by graphite-like carbon layers 1–2 nm thick. Optimum magnetic properties with saturation magnetization of 380 emu/cc and coercivity of 400 Oe were obtained for a film with x=0.5 and T_S=350°C.     

Evidence for insulator–metal transition in amorphous chalcogenide Se–Ge–Te films

The temperature dependence of the dc conductivity and thermoelectric power was determined for five different amorphous chalcogenide Se–Ge–Te films, with Ge?=?3.0–22?at.%, Se?=?0–97?at.% and Te?=?0–97?at.%. The films were prepared by thermal evaporation of GeSe₄, GeTe₄ and GeSe₂Te₂ quenched bulk materials. Values of the activation energy calculated from the temperature dependence of both electrical conductivity and thermoelectric power showed a decrease with increasing Ge content in the Se–Ge films as well as with replacement of Te for Se in the Se–Ge–Te films. The results showed an Anderson transition, with the conductivity showing insulating behaviour on the Ge–Se side to metallic behaviour at the binary composition Ge–Te. The radius of localization was obtained for the different compositions investigated. The wave function associated with the charge carriers at the composition Ge_3.3Te_96.7 is non-localized. A minimum metallic conductivity of 237?±?5?(Ω?cm)^?1 was found.     

ICEMS study of isothermal oxidation of Fe–Mn–Al–C–Cr–Si–Mo, Fe–Mn–Al–C–Cr–Si and Fe–9Cr–1Mo alloys

The purpose of this paper is to investigate the isothermal behavior of Fe–27.3Mn–7.6Al–C–6.5Cr–0.25Si–0.88Mo (Mo(0)) and Fe–27.3Mn–7.6Al–1.0C–6.5Cr–0.25Si (Mo(1)) alloys and compare it against Fe–9Cr–1Mo (FCR) commercial alloy. The experiments were carried out at 600°C, 700°C, 750°C and 850°C, each one during 72 h in static air. The oxidation kinetics was measured as a function of time using a Thermogravimetry analyzer (TGA). The structure and composition of the oxide scale were characterized by X-ray diffraction (XRD) and Integral Conversion Electron Mössbauer Spectroscopy (CEMS). The TGA results show that at all oxidation temperatures the sample FCR exhibit the lowest kinetic corrosion and the lowest weight gain, whereas Mo(0) the highest. By CEMS technique it were found a broad magnetic sextet, which has been fit by one hyperfine field distribution with mean hyperfine field characteristic to ferritic/martensite phase, one Fe^3?+? doublet and one singlet for the Mo(0) and Mo(1) alloys. Samples oxidized at highest temperatures exhibit a strong paramagnetic line, probably due that the Cr or Mn oxides may be enriched on the surface. Then, the magnetic phase can be converted partially into austenite phase at highest temperatures.     

The dependence of photosensitivity on composition for thin films of Ge x As y Se1–x–y chalcogenide glasses

We have prepared twelve Ge–As–Se chalcogenide glass films with different chemical compositions and investigated their stability to exposure with near bandedge light. The evolution of two key parameters, the refractive index at 1550 nm and the bandgap with increasing fluence were fitted with stretched-exponential functions. While most of the films showed photo-bleaching (or photodarkening) behavior, we found that for films with a mean coordination number (MCN) around ≈2.45–2.50, neither the bandgap nor the refractive index changed upon irradiation, demonstrating that photostable glasses exist with a particular chemical composition corresponding to the strongest glass formers. Such photostable glasses are the best choice for applications in photonics.     

Structural,optical and electrical properties of laser irradiated Pb doped Ga–Se chalcogenide thin films

Using the Transverse Electrical Excitation at Atmospheric Pressure (TEA) nitrogen laser, we had irradiated the amorphous thin films of Ga₁₀Se₈₁Pb₉ chalcogenide glass and the results have been discussed in terms of the structural aspects of Ga₁₀Se₈₁Pb₉ glass. The observed changes are associated with the interaction of the incident photon and the lone-pairs electrons which affects the band gap. The X-ray structural characterization revealed the amorphous nature of as prepared films and polycrystalline nature of the laser irradiated films. The optical band gap of these thin films is measured by using the absorption spectra as a function of photon energy in the wavelength region 400–1200 nm. It is found that the optical band gap decreases while the absorption coefficient increases with increasing the irradiation time. The decrease in the optical band gap has been explained on the basis of change in nature of films, from amorphous to polycrystalline state, with the increase in exposure time. The dc conductivities and activation energies of these thin films are measured in temperature range 303–403 K. It has been found that the activation energy in Ga₁₀Se₈₁Pb₉ chalcogenide thin films decreases whereas the dc conductivity increases at each temperature by increasing the irradiation time.     

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.     

Mössbauer effect studies of Fe–C combinatorially sputtered thin films

Alloys of Fe_{1? x} C _x were produced using combinatorial sputtering methods. The composition of the films as a function of position was determined using electron microprobe techniques and the results have shown that a composition range of about 0.35?<?x?<?0.75 was obtained. X-ray diffraction methods were employed to study the structure of the thin films and showed that all portions of the films were amorphous or nanostructured. Room temperature ⁵⁷Fe Mössbauer spectroscopy was utilized to study the atomic environment around the Fe atoms. Hyperfine field distributions of ferromagnetic alloys, as extracted from the Mössbauer analysis, suggested the existence of two classes of Fe sites: (1) classes of Fe sites that have primarily Fe neighbours corresponding to a high-field component in the distribution and (2) classes of Fe sites that have a greater number of C neighbours, corresponding to a low-field component. The magnetic splitting decreased as a function of increasing carbon concentration and alloys with x greater than about 0.68 were primarily paramagnetic in nature. These spectra exhibited distributions of quadrupole splitting with mean splitting in excess of 1.0?mm/s. This indicates a higher degree of local asymmetry around the Fe sites than typically seen in other Fe-metalloid systems.