Te-rich Ge–Te–Se glass for the CO2 infrared detection at 15 μm

Te_80−xGe₂₀Se_x glasses have been prepared along the GeSe₄–GeTe₄ axis using the classical method in silica tube under vacuum. A phase separation domain appears for composition around Te₄₀Ge₂₀Se₄₀. Our attention was turned toward the Te-rich compositions corresponding to 1 < x < 5 at.%. These glasses are transparent from 4 to about 20 μm without any purification of the starting elements. Furthermore the difference ΔT between the crystallization temperature T_x and the vitreous transition temperature T_g lies at about 110 °C that is to say 30 °C higher than for the GeTe₄ reference glass. Finally the introduction of a few percentages of Se makes the glasses much easier to prepare and more stable against crystallization, making them drawable as optical fibers for example. Taking into account their transparency window, encompassing the CO₂ absorption band around 15 μm, the Te_80−xGe₂₀Se_x with 1 < x < 5 at.% could become matchless composition for the CO₂ infrared detection as planed by the Darwin mission of the European Space Agency.     

The selenium based chalcogenide glasses with low content of As and Sb: DSC, StepScan DSC and Raman spectroscopy study

Thermal properties and structure of As_xSe_100−x and Sb_xSe_100−x glass-forming systems (x = 0, 1, 2, 4, 8 and 16) were studied by conventional and StepScan DSCs and Raman spectroscopy. Compositional dependence of the glass transition temperature, T_g, was determined from reversible part of StepScan DSC records and discussed. The attention was also focused on the crystallization of undercooled melts of these systems. It was found that only selenium crystallizes from undercooled melts of As–Se system and its tendency to crystallize decreases markedly with increasing As content, for arsenic content higher than 4 at.% no crystallization was observed. In the case of Sb–Se system Sb₂Se₃ crystallizes in the first step followed by trigonal selenium crystallization from non-stoichiometric undercooled melt. Sb₂Se₃ crystallizes from incongruent melt with crystallization enthalpy ΔH_c(Sb₂Se₃) = −52 ± 2 J/(g of Sb₂Se₃), Johnson–Mehl–Avrami kinetics of crystallization and kinetic exponent close to 3 was found. Raman spectra were measured to obtain basic information on the structure of both glassy systems.     

On the glass transition temperature in covalent glasses

We give a simple demonstration of the formula relating the glass transition temperature, T_g, to the molar concentration x of a modifier in two types of glasses: binary glasses, whose composition can be denoted by X_nY_m+xM_pY_q, with X an element of 3rd or 4th group (e.g., B or Si, Ge), while M_pY_q is an alkali oxide or chalcogenide; next, the network glasses of the type A_xB_1−x, e.g., Ge_xSe_1−x, Si_xTe_1−x, etc. After comparison, this formula gives an exact expression of the parameter β of the modified Gibbs–Di Marzio equation.     

Optical and structural properties of Ge–Se bulk glasses and Ag–Ge–Se thin films

The optical and structural properties of Ge₂₀Se₈₀, Ge₂₅Se₇₅ and Ge₃₀Se₇₀ bulk glasses and Ag_x(Ge_0.20Se_0.80)_100−x thin films, where x = 0, 6, 11, 16, 20 and 23 at.% were studied. All samples were confirmed as amorphous according to XRD. The Raman spectra showed increase in 260 cm⁻¹ and 237 cm⁻¹ and decrease in 198 cm⁻¹ and 216 cm⁻¹ bands with different Se content in the bulk samples. The optical bandgap energy of bulk samples decreased (2.17–2.08 eV) and refractive index increased (2.389–2.426 at 1550 nm) with increasing Se content in bulk glasses. The Ge₂₀Se₈₀ thin films were prepared by vacuum thermal evaporation from Ge₃₀Se₇₀ bulk glasses. The Raman spectra of the films showed that peaks at 260 cm⁻¹ and 216 cm⁻¹ decreased their intensities with increasing Ag content in the thin films. The significant red shift of bandgap energy occurred upon different Ag content. The optically induced dissolution and diffusion resulted in graded refractive index profile along the film thickness caused by different Ag concentration. The refractive index increased from the substrate side to the top of thin films. The graded profile was getting more uniform with increasing content of silver in the thin film.     

Raman spectra and thermal analysis of a new lead–tellurium–germanate glass system

Differential scanning calorimetry (DSC) and Raman scattering studies of a new glass system, lead–tellurium–germanate glasses in the form of (90−x)GeO₂·xTeO₂·27PbO·10CaO with x=0, 10, 20, 30, and 40, are reported. The glass samples were fabricated using a conventional melt-quenching method. The Raman spectra and possible glass structures are discussed for different TeO₂ contents. The results indicate that increasing TeO₂ content up to 40 mol% in the glass system decreases the glass transition temperature and melting temperature, and suppresses the crystallization tendency in the fiber pulling temperature range. The lead–tellurium–germanate glass, GTPC, possesses a larger refractive index and a smaller maximum phonon energy than that of a lead–germanate glass, 63GeO₂·27PbO·10CaO, and shows a better thermal stability compared to a tellurite glass, 75TeO₂·20ZnO·5Na₂O (TZN). These improved properties could be beneficial for fabricating rare-earth doped fiber devices.     

Characterization of BGO glass–ceramic materials

Glass–ceramics of the compositions Bi₄Ge₃O₁₂ (BGO) and Bi₂O₃–GeO₂ have been obtained by pouring molten materials onto graphite plates heated below and above the glass transition temperatures. Glass transitions temperatures have been measured by DSC. T_g is lower in the case of BGO than with the Bi₂O₃–GeO₂ glass ceramics material. Crystallization is evaluated by X-ray diffraction and microscopic observations. The XRD measurements confirm the amorphous structure of the samples cast below T_g. The Hruby factor, which measures the stability of the glass–ceramics, is about 0.21 in the case of BGO glass ceramics suggesting a rather stable glass. The fluorescence under U.V. excitation is larger by one order of magnitude in the case of BGO glass–ceramics by comparison to the Bi₂O₃–GeO₂ glasses, suggesting it is a good candidate for scintillation materials. The images obtained under U.V. excitation shows structured luminescent centers in the case of BGO glass–ceramics.     

Properties and structure of binary tin phosphate glasses

The properties and structures of binary xSnO*(100 − x)P₂O₅ (50 ≤ x ≤ 70 mol%) glasses were evaluated. The glass transition temperatures (T_g), determined by differential thermal analysis (DTA), range from 246 to 264 °C, for glasses prepared under identical conditions. The refractive index (n_D) increases from 1.701 to 1.833 as x increases from 50 to 70, and the Abbe number (ν_D) decreases from 29.1 to 20.4 over the same range. Infrared spectroscopy was used to estimate water contents in the glasses, which decreased with an increase in SnO content, from about 1570 ppm OH for x = 50 to about 50 ppm OH for x = 70, for glasses quenched from melts held at 1000 °C for 15 min. Residual water affects thermal properties, like T_g, and variations in water contents due to differences in melt processing explain the wide variety of glass properties reported in the literature. Raman spectroscopy indicates that progressively shorter phosphate chains are present in the structures of the binary Sn-phosphate glasses with increasing SnO contents.     

Glass formation in the MoO3–Nd2O3–La2O3–B2O3 system

In MoO₃–Nd₂O₃–B₂O₃ and MoO₃–Nd₂O₃–La₂O₃–B₂O₃ systems, glasses were obtained in the region between 20 and 30 mol% Ln₂O₃. A liquid-phase separation region was observed near the MoO₃–B₂O₃ side up to 20 mol% Ln₂O₃ (La, Nd). The amorphous phases were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), UV–VIS and infrared spectroscopy (IR). According to DTA data B₂O₃-rich glasses are stable up to 630 °C while glasses rich in MoO₃ are stable up to 430 °C. The glasses are transparent in the visible region. Structural models for the glasses network were suggested on the basis of IR spectral investigations. It was established that BO₃ (1380 cm⁻¹), BO₄ (1100–950 cm⁻¹) and MoO₄ (860 cm⁻¹) groups build up the glass network. MoO₆ units (band at 880 cm⁻¹) together with BO₃ units participate in the formation of the glass network with a high MoO₃ content (80–90 mol%).     

Structure and optical properties of chalcohalide glasses doped with Pr and Yb ions

Glasses of systems 100-y((GeS₂)₈₀(Sb₂S₃)_20−x(PbI₂)_x)yPr₂S₃, x = 0; 2; 5, 8; y = 0; 0.01; 0.1; 0.5 and 99.9-z((GeS₂)₈₀(Sb₂S₃)₁₈(PbI₂)₂)0.1Pr₂S₃zYb₂S₃, z = 0.05; 0.1; 0.15) were synthesized in high purity. Optically well transparent glasses were obtained for x  5 mol.% PbI₂, for y  0.1 mol.% Pr₂S₃ and for z  0.15 mol.% Yb₂S₃. The glasses were stable and homogeneous, as confirmed by X-ray diffraction and electron microscopy, with high optical transmittivity from visible (red) region up to infrared region (900 cm⁻¹). The density of the glasses was 3.26–3.33 gcm⁻³ for PbI₂ containing glasses. The glass transition temperature, T_g, was 320–336 °C. The optical absorption bands in rare-earth doped glasses corresponded to ³H₄–³F₄, ³H₄–³F₃, ³H₄–(³F₂ + ³H₆) f–f electron transitions of Pr³⁺ ions and to ²F_7/2–²F_5/2 f–f electron transitions of Yb³⁺ ions. Strong luminescence band with maximum near 1340 nm (electron transition ¹G₄–³H₅) was found in Pr₂S₃ doped glasses. The intensity of this band was rising with doping by Yb³⁺ ions. The possible mechanism of the luminescence enhancement is suggested.     

Influence of alkali and alkali-earth metal oxide substitutions on the properties of lithium-iron-phosphate glasses

The influences of different alkali and alkali-earth oxide substitutions on the properties of lithium-iron-phosphate (LIP) glasses have been studied. Na₂O, K₂O, MgO, CaO and BaO were used to substitute Li₂O to prepare LIP glasses with molar compositions of (20 − x)Li₂O − xR₂O(RO) − 30Fe₂O₃ − 50P₂O₅ (x = 2.4, 4, 5.6 and 7.2). The glass transition temperature (T_g) was determined by the differential thermal analysis technique. The density and chemical durability of the prepared glasses were measured based on the Archimedes principle and the weight losses after the glasses were boiled in water. The results show that T_g decreases with the initial substitutions, whereas the density and chemical durability increase. The diminution of the aggregation effect of Li⁺ ions on the glass structure due to the decrease in Li⁺ concentration, the larger molecule weights of the substitutes, the mixed-alkali and depressing effects as well the slower mobility of substitute ions mainly contribute to the initial changes in T_g, density and chemical durability of the LIP glasses, respectively. Further increasing the amounts of substitutes brings about increasing diminution of the aggregation effect of Li⁺ ions and breakage of the glass network on the one hand and increasing amounts of substitutes with larger molecule weights and ion radii on the other hand. Both aspects influence the glass properties oppositely and consequently non-monotonic variations in the properties of LIP glasses with the substitutions are observed.     

Network topological thresholds in gallium doped As–Te glasses – Electrical and thermal investigations

Electrical switching and differential scanning calorimetric studies are undertaken on bulk As₂₀Te_80−xGa_x glasses, to elucidate the network topological thresholds. It is found that these glasses exhibit a single glass transition (T_g) and two crystallization reactions (T_c1 & T_c2) upon heating. It is also found that there is only a marginal change in T_g with the addition of up to about 10% of Ga; around this composition an increase is seen in T_g which culminates in a local maximum around x = 15. The decrease exhibited in T_g beyond this composition, leads to a local minimum at x = 17.5. Further, the As₂₀Te_80−xGa_x glasses are found to exhibit memory type electrical switching. The switching voltages (V_T) increase with the increase in gallium content and a local maximum is seen in V_T around x = 15. V_T is found to decrease with x thereafter, exhibiting a local minimum around x = 17.5. The composition dependence of T_c1 is found to be very similar to that of V_T of As₂₀Te_80−xGa_x glasses. Based on the present results, it is proposed that the composition x = 15 and x = 17.5 correspond to the rigidity percolation and chemical thresholds, respectively, of As₂₀Te_80−xGa_x glasses.     

Features in the photoluminescence line-shape of heavily Er-doped Ge–S–Ga glasses

Erbium doped chalcogenide glasses are of great interest in the integrated optoelectronic technology due to their Er³⁺ intra-4f emission at the standard telecommunication wavelength of 1.54 μm. In this paper, the photoluminescence (PL) of a series of (GeS₂)_x(Ga₂S₃)_100−x (x = 75 and 67) glasses doped with high amounts of Er₂S₃ (1.8, 2.1, 2.4 and 2.7 mol%) under excitation with 1064 nm light has been studied. A quenching PL effect at 1.22 аt.% Er-doped (GeS₂)₇₅(Ga₂S₃)₂₅ and 1.39 аt.% Er-doped (GeS₂)₆₇(Ga₂S₃)₃₃ glasses has been established. The relative changes in PL line-shape at around 1540 nm have been estimated by deconvoluting the spectra to Gaussian sub-bands centered at 1519 ± 1, 1537 ± 1, 1546 ± 1, 1555 ± 1 and 1566 ± 4 nm, which correspond to F₂₁, F₁₁, F₂₂, F₁₂ and F₁₃ transitions in the ⁴I_13/2 and ⁴I_15/2 energy levels and have intensity and manifestation that are strongly depend on the Er-doping level. The influence of gallium on the PL efficiency has been evaluated with a view to enhanced emission cross-section.     

Electro-optical characterization of Ge–Se–Te glasses

Chalcogenide bulk glasses Ge₂₀Se_80−xTe_x for x(0,15) have been prepared by systematic replacement of Se by Te. Selected glasses have been doped with Ho, Er and Pr, and samples have been characterized by transmission spectroscopy, measurements of dc electrical conductivity and low-temperature photoluminescence. Absorption coefficients have been derived from measured transmittance and estimated reflectance. Arrhenius plots of dc electrical conductivity, in the measured temperature range 300–460 K, are characterized by single activation energies roughly equal to the half of the optical gap. Activation energies deduced from Arrhenius plots reveal a systematic decrease with increasing Te content. Similarly, both absorption and low-temperature photoluminescence spectra reveal shifts of absorption edge and/or dominant luminescence band to longer wavelength due to Te → Se substitution. Samples doped with Ho and Er exhibit a strong luminescence at 1200 and 1540 nm due to ⁵I₆ → ⁵I₈ and ⁴I_13/2 → ⁴I_15/2 transitions of Ho³⁺ and Er³⁺ ions, respectively. Pr doped samples exhibit only a relatively weak luminescence peak at 1590 nm, which we tentatively assign to ³F₃ → ³H₄ transition of Pr³⁺ ions. Absorption of the base glass luminescence at 1460 and 1520 nm has been observed at low temperature on samples doped with Pr and Er, respectively.     

Vibrational modes and structure of (AgI)x (GeS1.5)100−x chalcohalide glasses

We report a structural investigation of bulk Ge-rich Ge–S–AgI chalcohalide glasses. A vibrational spectroscopic study of the quaternary system (AgI)_x (GeS_1.5)_100−x (0  x_AgI  20) has been undertaken using infrared spectroscopy and Fourier transform Raman scattering. It was found that the GeS_1.5 Raman spectrum is compatible with a glass structure composed of corner- and edge-sharing mixed GeS_nGe_4−n (n = 0–4) tetrahedra where units with n = 2–4 dominate, whilst the fraction of corner-sharing units are significantly lower than the corresponding fraction in the stoichiometric GeS₂ glass. The addition of AgI has revealed a subtle but systematic effect in the structure of the Ge-rich glass matrix, manifested by mild decrease of the ES units and the concomitant increase of complex GeS_nI_4−n or GeS_nGe_mI_4-n−m tetrahedra whose vibrational modes form a continuum at low frequencies. Although, AgI seems to cause subtle structural changes due to the formation of Ge–I bonds, it is also evident that AgI does not act as a real modifier that would depolymerize appreciably the Ge–S network structure.     

Influence of Ga incorporation on photoinduced phenomena in Ge–S based glasses

To study the influence of Ga addition on photoinduced effect, GaGeS glasses with constant atomic ratio S/Ge = 2.6 have been prepared. Using Raman spectroscopy, we have reported the effect of Ga on the structural behavior of these glasses. An increase of the glass transition temperature T_g, the linear refractive index and the density have been observed with increasing gallium content. The photoinduced phenomena have been examined through the influence of time exposure and power density, when exposed to above light bandgap (3.53 eV). The correlation between photoinduced phenomena and Ga content in such glasses are shown hereby.     

Effect of silver doping on the structure and phase separation of sulfur-rich As–S glasses: Raman and SEM studies

We report on the structural details and microphase separation of the bulk glasses Ag_x·(As₃₃S₆₇)_100-x for 0x25. Glass–glass phase separation occurs over a wide range of Ag content, i.e. 4x20. An off-resonant polarized Raman spectroscopic study has been carried out to elucidate structural aspects at the short- and medium-range structural order of the glasses. Analysis of Raman spectra revealed quantitative changes of the sulfur-rich microenvironments that reduce upon adding Ag. Scanning electron microscopy combined with X-rays microanalysis have been utilized to examine the type and extent of phase separation, and to provide quantitative details on the atomic concentrations in the Ag-poor and Ag-rich phases. It has been shown that at 7 at.% Ag the Ag-rich phase percolates through the structure; this effect can be associated with an ionic-to-superionic behavior of these glasses in accordance with similar studies on the stoichiometric arsenic sulfide glass; although the phase separation observed in the present glasses is qualitatively different.     

Glass formation in the GexTe100−x binary system: Synthesis by twin roller quenching and co-thermal evaporation techniques

The Ge–Te system exhibits one main composition domain where glasses can be easily prepared by melt quenching technique; this domain is centered on the eutectic composition Ge₁₅Te₈₅. In this work, bulk flakes and films of composition Ge_xTe_100−x with x  50 at.% were prepared by two different quenching techniques: (i) the twin roller quenching for bulk flakes and, (ii) the co-thermal evaporation for films (with thickness comprised between 2 and 14 μm). Electron Probe Micro-Analysis was used to check the composition of the materials while X-ray diffraction allowed identifying the amorphous state and/or the crystalline phases present in the Ge_xTe_100−x samples. Thermal properties for both types of materials were investigated by differential scanning calorimetry. The glass-forming regions were: 11.7–22.0 at.% Ge for bulk flakes and 10.2–35.9 at.% Ge for films. A similar thermal behavior of bulk flakes and thick films was highlighted by Differential Scanning Calorimetry.     

The correlation between the pressure sensitivity and the fragility/glass transition temperature in bulk metallic glasses

The correlations between the pressure sensitivity and the fragility/glass transition temperature have been addressed in various bulk metallic glasses in the present work. The results demonstrate that the pressure sensitivity of bulk metallic glasses is closely related to both the fragility index (m) and the glass transition temperature (T_g). The physical origin of the correlations has been discussed from their disordered structure, which is determined by the glass transition behavior and the glass transition temperature.     

Optical properties of thin films of system (As2Se3)80−x(As2Te3)x(SnTe)20 prepared by PLD

Thin amorphous films from system (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ were prepared by pulsed laser deposition (PLD) from their bulk glasses and their optical properties were studied by spectral ellipsometry. Spectral dependencies of refractive index, absorption and extinction coefficient and optical gap (1.41–1.66 eV for (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ with x = 20 resp. x = 0) were calculated from optical tansmittance, from ellipsometric data by Tauc method. High values of refractive index n₀ (2.49–2.60) and of non-linear χ⁽³⁾ coefficient of index of refraction (4.9–7.5 × 10⁻¹² esu for the glass (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ with x = 0 resp. x = 20) made studied thin films of system (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ promising candidates for application in optics and optoelectronics.     

Mg based bulk metallic glasses: Glass transition temperature and elastic properties versus toughness

In this work, optimal compositions for bulk metallic glasses (BMGs) formation in the ternary Mg-Cu-Nd and Mg-Ni-Nd systems are located at the Mg₅₇Cu₃₄Nd₉ and Mg₆₄Ni₂₁Nd₁₅, respectively, with the critical diameter of 4 mm for the rods fabricated by copper mold casting. As indicated by notch toughness testing, Mg₆₄Ni₂₁Nd₁₅ BMG (K_Q = 5.1 MPa√m) manifests higher toughness with respect to the Mg₅₇Cu₃₄Nd₉ (K_Q = 3.6 MPa√m), even though both BMGs have similar compressive fracture strength of 870-880 MPa. Such an improvement in toughness for Mg BMGs correlates with the reduction of shear modulus and the enhancement of thermal stability to resist to the structural relaxation at room temperature, which is indicated by the elevated glass transition temperature T_g. Under the Mode I loading condition, morphology in fracture surface of the Mg₆₄Ni₂₁Nd₁₅ BMG varies along the crack propagation path. Fractographic evolution of the fracture surface follows the Taylor's meniscus instability criterion. For the Mg-based BMGs, shear modulus scales with the glass transition temperature, and can be expressed as μ = 4.7 + 625T_g/V_m[1-4/9(T/T_g)^2/3]. Meanwhile, correlation between the calorimetric T_g and elastic properties at T_g can be rationalized with Egami's model.