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.     

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.     

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 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.     

Optical constants of quaternary Ge–As–Te–In amorphous thin films evaluated from their reflectance spectra

Thin films of amorphous Ge₉As₂₀Te_{71? x} In _x with different compositions (x = 0, 3, 6 and 9 at. %) were obtained by deposition onto glass substrates by thermal evaporation. The reflection spectra, R(λ), of the films were obtained in the spectral region from 400 to 2500 nm. A straightforward analysis proposed by Ruiz-Perez et al., based on the use of the maxima and minima of the interference fringes, has been applied to derive the real and imaginary parts of the complex index of refraction, the thickness and the thickness variation of the studied films. Increasing In content is found to affect the refractive index and the extinction coefficient of the films. Optical absorption measurements were used to obtain the fundamental absorption edge as a function of composition. With increasing In content, the refractive index decreases, whereas the optical band gap, E_g , increases. The relationship between E_g and the chemical composition of the Ge₉As₂₀Te_{71? x} In _x system is discussed in terms of the cohesive energy, the average heat of atomization, H _s , and the average coordination number, N _r .     

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.     

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.     

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.     

Characterization of Fe–Nb sputtered thin films

Structure, composition and chemical behavior of co-sputtered Fe–Nb thin films are analyzed by different techniques, as conversion electron Mössbauer spectroscopy, x-ray photoelectron spectroscopy and x-ray diffraction. It is shown that oxygen is determinative in hindering the Fe–Nb alloy formation and, as a result, Fe_1−xO and Nb₂O₅ occur in significant amounts, even in vacuum. In spite of the oxygen role, a Fe–Nb alloy is formed in little amounts, which increase as the Nb content is increased. The increase of the Nb content is also related with the increase of Fe_1−xO and with a decreasing of the metallic Fe present. Mössbauer data indicate the Fe–Nb phase present is the Fe₂Nb Laves phase.     

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.     

Photoconductivity in amorphous thin films of Ge22Se78−xBix

Temperature and intensity dependence of photoconductivity is studied in amorphous thin films of Ge₂₂Se_78−x Bi_x with x = 0, 2 and 10. Transient photoconductivity measurements have also been made on the same samples. Our results show that photosensitivity decreases as Bi concentration is increased from x = 0 to x = 2. However, at high concentration of Bi(x = 10), photosensitivity again increases. Transient photoconductivity also show a different behaviour at low and high concentration of Bi. Results have been explained in terms of defect states produced due to Bi incorporation in GeSe system.     

Thermal and optical analysis of Te-substituted Sn–Sb–Se chalcogenide semiconductors

Bulk amorphous samples of Te-substituted Sn₁₀Sb₂₀Se_70−X Te _X (0≤X≤12) were prepared using a melt quenching technique. Calorimetric studies of the samples were performed using differential scanning calorimetry (DSC) and the glass transition temperature and crystallization temperature were evaluated from DSC scans. The glass transition temperature T _g exhibits a sharp decrease for small Te substitution of X=2, thereafter increases with increase in Te content up to X=10, and then decreases for further Te substitution. The apparent activation energy for glass transition and the activation energy for crystallization were calculated using Kissinger, modified Kissinger, and Matusita equations. The change in glass transition temperature T _g has been explained based on the bond formation energy of different heteropolar bonds. The optical band gap of thermally evaporated thin films of Sn₁₀Sb₂₀Se_70−X Te _X (0≤X≤12) was calculated from reflectance and transmittance data. The optical band gap variation with tellurium content exhibits a sharp decrease for an initial tellurium substitution of X=2 similar to that of the glass transition temperature and thereafter a peak is observed in optical band gap around X=4 composition.     

Some optical properties of Ge–S amorphous thin films

Amorphous Ge_xS_1−x films (x=0.27, 0.32, 0.36 and 0.4) were prepared by thermal evaporation. The values of the refractive index, the optical gap and the parameters of the Wemple–DiDomenico single oscillator model were determined. Using Miller's generalized rule the values of the third-order non-linear susceptibility were also estimated. Thermally induced bleaching was observed for films studied. Photobleaching was observed for sulfur rich and nearly stoichiometric films (x=0.27, 0.32) while for a germanium rich film (x=0.4) no response to the illumination was observed. The differences in photobleaching are attributed to the role of p-lone pair states and to an overall network rigidity of the films.     

Electrical and thermal properties of chalcogenide glass system Se75Ge25−x Sb x

The dc and thermal conductivities of five different compositions of the chalcogenide glass system Se₇₅Ge_25–x Sb _x have been studied in a temperature range below T _g. The dc conductivity results indicate that each composition has a single activation energy in the considered temperature range. The coefficient of thermal conductivity increased linearly with temperature below T _g for the compositions investigated. The increase of Sb content in the chalcogenide glass system leads to an increased coefficient of electrical conductivity , an increased coefficient of thermal conductivity , and to a decreased activation energy E and pre-exponential factor ₀. The observed compositional dependencies of and E have been correlated with the increase of weak bond density and the decrease of covalent bond density in the structure of the compositions investigated with increasing Sb content at the expense of Ge content. The decrease in ₀ and the increase in has been, respectively, correlated with the decrease in mobility and the increase in phonon velocity.