Experimental study of the structure of chalcogenide glassy semiconductors in three-component systems of Ge-As-Se and As-Sb-Se by means of NQR and EPR spectroscopy

The structure of chalcogenide glassy semiconductors in three-component systems of Ge-As-Se and As-Sb-Se has been studied by means of both NQR (nuclear quadrupole resonance) and EPR (electron paramagnetic resonance) spectroscopy. It is investigated that in the glasses of both systems the value of the electric field gradient at the resonating nuclei grows with increasing concentration of the clusters As₂Se₃ and Sb₂Se₃, thereby increasing the NQR resonance frequencies. It appears that for the Ge-As-Se system the structural transition from a two-dimensional to three-dimensional structure occurs at average coordination number $\bar r$ = 2.45. The EPR spectral parameters of glasses depend on the composition, the average coordination number and the temperature, and these are discussed. The effect of ”ageing” for CGS (chalcogenide glassy semiconductors) of As-Sb-Se system due to partial crystallization of the sample is observed from the EPR spectra.     

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.     

Structural investigation of Te-based chalcogenide glasses using Raman spectroscopy

Structural changes of metals (Zn, Sb, In, Ga) and metal halides (AgI, ZnI₂, CdI₂, PbI₂, BiI₃) modified GeTe₄ glasses were investigated with the aid of Raman spectroscopy. The Raman spectra of these glasses in the frequency region between 100 cm^?1 and 300 cm^?1 display four main bands at about 124, 140, 159 and 275 cm^?1 which are contributed by Ge–Te, Te–Te, Te–Te and Ge–Ge vibration modes. The intensity of 159 cm^?1 and 275 cm^?1 bands vary with the addition of different glass modifiers. While the relative intensity of the 124 cm^?1 and 140 cm^?1 bands are insensitive to composition changes. Glass modifiers like Zn, In and Sb act as glass network unstabilizer which will disorganize the glass network by opening up the chain structures of Ge–Te and Te–Te. In the case of Ga and metal halides, Ga can open up Ge–(Te–Te)_4/2 tetrahedra and form Ga–(Te–Te)_3/2 triangle. Iodine can form covalent bonds with tellurium and decrease the tendency of microcrystal formation. Thus both Ga and iodine ultimately act as glass network stabilizer.     

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.     

Pulse EPR spectroscopy of Cu2+-doped inorganic glasses

Two-frequency continuous-wave and pulse EPR (electron paramagnetic resonance) spectroscopical techniques are applied to determine static and dynamic EPR parameters of Cu²⁺ ions in oxide and fluoride glasses. The investigations are focussed on the analysis of strain effects in the glassy matrices, the identification of the magnetic nuclei in the vicinity of Cu²⁺ ions as well as the determination of the dependence of the phase memory timeT _M on temperature and resonance field. The results obtained by X-band continuous-wave EPR, X- and S-band echo-detected EPR, and X- and S-band electron spin echo envelope modulation studies of Cu²⁺-doped inorganic glasses yield information on the local symmetry of the Cu²⁺ coordination polyhedra, the chemical nature of the atoms in the second and higher coordination spheres, the distribution of the parameters of the static spin Hamiltonian and the low-temperature motions of the dopant-containing structural units. Special techniques like 2-D Mims ENDOR (electron nuclear double resonance) and hyperfine-correlated ENDOR are applied for the first time to doped inorganic glasses. From the spin relaxation measurements a stronger tendency of the Cu²⁺ ions to aggregate is found for fluoride glasses in comparison to aluminosilicate and phosphate glasses.     

Free-volume defects investigation of GeS2-Ga2S3-CsI chalcogenide glasses by positron annihilation spectroscopy

The transformation behavior of free-volume defect in (80GeS₂-20Ga₂S₃)_100-x (CsI)_x (x = 0, 5, 10, 15 mol%) chalcogenide glasses was studied by employing positron annihilation spectroscopic technique, which could reveal valuable information for in-depth understanding of nano-structural defects in glassy matrix. The results indicate that the structural changes caused by CsI additives can be adequately described by positron trapping modes determined with two-state model. The initial addition of CsI (x = 5 mol%) led to a void contraction, whereas, the void agglomeration occurred with the increase of CsI and the free-volume defects of the glasses were obviously reduced. The atomic density ρ is inversely proportional to the number of these defects. Meanwhile, the UV cut-off edge shifts toward short-wavelength with increasing of CsI. This study provides the valuable information of defects evolution in GeS₂-Ga₂S₃-CsI glasses.     

A study of hydroxyapatite nanocrystals by the multifrequency EPR and ENDOR spectroscopy methods

Specimens of powders of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) with average crystallite sizes in the range of 20–50 nm synthesized by the wet precipitation method have been investigated by the multifrequency (9 and 94 GHz) electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) methods. In specimens subjected to X-ray irradiation at room temperature, EPR signals that are caused by nitrogen compounds have been observed. Numerical calculations performed in terms of the density functional theory show that the observed EPR signal is caused by the occurrence of paramagnetic centers, the structure of which is NO ₃ ^2? and which replace the positions of PO ₄ ^3? in the hydroxyapatite structure.     

Thermoactivated molecular motions in solids and determination of the energy of their activation by NQR spectroscopy methods

The activation energy of thermoactivated molecular motions in solids is determined by examining the influence of these motions on the temperature dependence of the nuclear quadrupole spin-lattice relaxation rate and quadrupole resonance (NQR) signal intensity for chlorine-35. In the latter case, the heating of the crystals is accompanied by the fading of resonance signals, which is analyzed using a linear correlation between the activation energy of this motion and the fade-out temperature. The correlation parameters are demonstrated to be dependant on the type of molecular motion. The relaxation method is shown to be more effective in studying molecular motion and evaluating its activation energy as compared to the NQR signal fading technique.     

Ionic conductivity of silver chalcogenide glasses

The dynamic response by electrical spectroscopy of ionically conducting chalcogenide glasses (Ag₂S)_x(GeS₂)_1–x has been studied. The activation energies E_d.c deduced from the Arrhenius plots are temperature dependent. Fitting the curves to log(σ_a.c)=f(log ω) leads to values of characteristic parameters that are dependent both on temperature and frequency. The obtained experimental results are compared with a theoretical model based on the concept of “free volume” fluctuations. A new approch is proposed leading to acceptable hopping distances. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994.     

Linear optical characterization of chalcogenide glasses

A simple experimental method is used to obtain the evolution of both the refractive index and the linear absorption coefficient as a function of the optical wavelength in the near infrared range (from 900 up to 1700 nm with 10 nm resolution). Several chalcogenide glasses (As₂S₃, As₂Se₃, GeSe₄) are tested and the corresponding Cauchy coefficients are determined. Comparison of our results shows a good agreement with values available in the literature at some wavelength. Application of this method is used to estimate Cauchy coefficients of Ge₁₀As₁₀Se₈₀ for the first time to our best knowledge.     

Urbach tails and the structure of chalcogenide glasses

A novel analysis of optical absorption tails of inorganic network glasses is shown to provide important information on the structure of the glass. The anomalous composition and temperature dependence of absorption tails in Ge_xSe_1?x and As_xSe_1?x systems indicate that these glasses retain locally layered structures at particular stoichiometries corresponding to GeSe₂ and As₂Se₃, and a reversible structural change is taking place well below the glass transition temperature. A phenomenological model for the absorption tail slope of glasses is proposed, analogous to the Urbach rule for crystalline materials.     

Low frequency Raman spectra of chalcogenide glasses

Low frequency (< 30 cm^-1) Raman scattering lineshapes for the chalcogenide glasses As₂S₃ and As₂Se₃ have been interpreted in terms of a model which explicitly includes acoustic (∼ ω2 density-of-states) and optic (rigid-layer like) vibrational modes.     

I – V characteristics of chalcogenide glasses

The mechanism is discussed for the switching of metal-chalcogenide-metal systems from the highly conducting to the poorly conducting state and vice versa. Experimental data illustrating these phenomena are presented. It is shown that it is possible in principle to produce high-speed film-type switches.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, Vol.12, No. 3, pp. 85–89, March, 1969.In conclusion the authors thank I. M. Anan'in and B. N. Sazhin for participating in the deposition, and S.A. Dembovskii for synthesizing the glasses.     

Study of divalent and trivalent chromium in forsterite by high-frequency EPR spectroscopy

Divalent and trivalent chromium ions Cr²⁺ and Cr³⁺ replacing magnesium ions at octahedral positions in Mg₂SiO₄: Cr and Mg₂SiO₄: Cr: Li crystals are investigated by submillimeter EPR spectroscopy in the frequency range 65–230 GHz. The crystals are grown from the melt by the Czochralski method. The content of mixed-valence chromium species in forsterite is analyzed. It is demonstrated that, in crystals grown in argon (the oxygen partial pressure is \(P_{O_2 } \) = 0.01 kPa), approximately half of the chromium ions are in the divalent form. The Cr²⁺ ions are distributed over the M1 and M2 positions in a ratio of approximately 2: 1. A change in the oxygen partial pressure \(P_{O_2 } \) and the chromium concentration, as well as an additional doping with lithium, does not lead to substantial changes in the distribution of divalent chromium ions over the positions. It is shown that an increase in the oxygen partial pressure \(P_{O_2 } \) from 0.01 to 2.00 kPa results in a decrease in the coefficient of divalent chromium distribution between the crystal and the melt. Doping with lithium also decreases the concentration of Cr²⁺ centers. In crystals grown without lithium, approximately half of the trivalent chromium ions are associated with magnesium vacancies. The addition of lithium leads to the destruction of these associates, an increase in the concentration of individual Cr³⁺ centers, and the formation of lithium associates with trivalent chromium ions. The conditions for the formation of associates of trivalent chromium ions with lithium ions are optimum when the crystal contains approximately identical amounts of Cr³⁺ and Li⁺ ions. Doping with lithium increases the concentration of Cr³⁺ ions and, thus, decreases the fraction of Cr²⁺ and Cr⁴⁺ ions in the total content of chromium centers.