Polynary silicon arsenic chalcogenide glasses with high softening temperatures

The introduction of Ag in SiAsTe glasses permits the incorporation of Se, otherwise volatile and/or degradable as a constituent in Si-containing chalcogenide glasses. SiAsAgTeSe glasses exhibit much higher softening ranges and glass transition temperatures than encountered in known chalgogenide systems. A glass Si₃₅As₁₅Ag₁₀Te₂₀Se₂₀ had the viscosity log ν = 13 at about 500°C, as compared to 370°C for the base glass Si₃₅As₂₅Te₄₀, the viscosity of log ν = 9.8 at about 560°C, as compared to 442°C for the base glass. Phase separation occurs in the system SiAsAgTeSe and becomes manifest in two glass transitions indicated by changes in the slopes of the expansion curves and breaks in the softening point-composition relations. The existence and behavior SiAsAgTeSe glasses suggests the possible development of higher T_g i.r. transparencies and higher T_g semiconductor glasses than described so far.     

On the compositional dependence of the optical gap in amorphous semiconducting alloys

It is found that the optical gap E_AB for amorphous A-B alloys can be determined by the energy gap E_A for element A and E_AB for the element B in the equation E_AB(Y) = YE_A + (1?Y) E_B where Y is the volume fraction of element A. Calculations based on a random bond network agree with experiments for SiGe, SbSe, and AsTe films (class A). Calculations based on a chemically ordered bond network which tends to form microscopic molecular species gree with experimental results for the AsSe, AsS, GeTe and Sb₂Se₃As₂Se₃ systems (class B). In contrast to the above systems, agreement with experiment is not obtained for the TeSe, As₂Te₃As₂Se₃ and GeTe₂GeSe₂ systems which contain atoms of both Te and Se (class C). The classification into three types (classes A, B and C) is consistent with the calculation based on effective medium percolation theory which interprets the compositional dependence of the conductivity of chalcogenide glasses.     

Studies of amorphous GeSeTe alloys (I): Preparation and calorimetric observations

We have used differential scanning calorimetry (DSC) to examine the thermally induced transformations of bulk and thin-film amorphous alloys within a large portion of the GeSeTe system. Most chalcogen-rich compositions showed a discontinuous increase of heat capacity when heated through the glass transition temperature T_G. The Ge-rich compositions, which could only be prepared as sputtered amorphous films, were invariably characterized by an irreversible exothermic crystallization process on heating, beginning at the crystallization temperature T_X. Values of T_g and T_X have been tabulated for all alloys investigated and the compositional dependence of T_g has been examined in the light of recent models for viscous flow in glass-forming chalcogenide systems. In addition, a region of liquid immiscibility has been observed in the vicinity of Ge₂₀Se₄₀Te₄₀ in which a GeSe₂-rich liquid phase segregates from a tellurium-rich liquid phase. The existence and limits of this immiscibility region have been rationalized on the basis of ionic perturbations to the covalent bonding. The segregation of a GeSe₂-rich liquid increases the concentration of GeSe bonds which are the strongest and most ionic of the six angle-bond types which can occur in this system.     

Thermally-induced structural and electrical effects in GeTe-based amorphous alloys

The thermal, structural electrical properties of bulk glasses based on GeTe compositions near the binary eutectic, Ge₁₅Te₈₅, are studied. Information regarding the non-crystalline state and the transformation from the non-crystalline to the crystalline state is reported. The particular alloys studied represent binary (Ge₁₇Te₈₃), ternary (Ge₁₅Te₈₀As₅) and quaternary (Ge₁₅Te₈₁Sb₂S₂) compositions. Structural information is obtained using X-ray diffraction techniques and density measurements. Thermal data are reported from differential scanning calorimetry (DSC), thermogravimetry (TGA) and mass spectrometry results. The electrical conductivity is measured as a function of temperature and, on the ‘as-prepared’ glasses, shows semi-conducting behavior with activation energies, E, of 0.43–0.48 eV. DSC, TGA and X-ray powder diffraction patterns indicate the samples crystallize as Te and GeTe in a two-step process, and melt at the binary eutectic temperature. The binary vaporizes as Te and GeTe in a two-step process. GeTeAs and GeTeSbS vaporize by essentially the same mechanism, with As evaporating (<300°C) before the Te, and Sb and S evaporating (420–480°C) after the Te but before GeTe. The results show that the properties of the bulk ‘as-prepared’ glasses are strikingly similar. Thermally-induced changes in the structural and electrical properties of bulk samples have been examined following a series of anneals (5 h, vacuum) at temperatures from 111°C to 190°C (glass transition temperature $\text{?125?133°}\text{C}$; crystallization temperature $\text{?206?228°}\text{C}$ as determined by DSC). DSC, TGA and mass spectrometry results have been correlated to electrical and structural changes. Results show that crystalline Te nucleates at the surface and forms a conductive surface layer. The conductivity of this surface layer is nearly temperature independent with E ≈ 10^?2 eV for all three alloys. Crystallization and the associated electrically conductive regions extend into the bulk material with further annealing. In these disordered alloys the additives As and Sb + S apparently do not act as electrical dopants in the sense of affecting the conductivity activation energy. The additives Sb + S however do retard crystallization of GeTe. The secondary crystallization product, GeTe, apparently changes the conduction mechanism to either a metallic or degenerate semiconductor type behavior.     

Electrical transport in n-type semiconducting Ge120BixSe70−xTe10 glasses

Resistivity and thermoelectric power were measured as a function of temperature and composition for Ge₂₀Bi_xSe_70?xTe₁₀ glasses (x = 0–11). The results were compared with the case of of Ge₂₀Bi_xSe_80?x glasses to see on the electrical properties the influence of the substitution of Te for a part of Se. The glasses show n-type conduction for x ? 9, which was not affected by the substitution of Te. The resistivity was about three orders of magnitude lower for the glasses with x < 10, and remained almost the same for x ? 10, compared with the glasses not containing Te. From the composition dependence of the calculated concentration of covalent bonds in the glasses, it was proposed that the appearance of n-type conduction was closely related to the formation of a sufficient number of BiSe bonds and the disappearance of the bonds between two chalcogen atoms such as TeSe or SeSe bonds, and that the remarkably low resistivity in the present glasses with x < 10 was likely to be attributed to the formation of TeSe bonds.     

Dielectric Properties of Beta Barium Borate and Potassium Pentaborate Single Crystals

Single crystals of beta barium borate and potassium pentaborate (commonly known as β-BaB₂O₄ or BBO and KB₅O₈. 4 H₂O or KB5) were grown by high and low temperature solution growth methods, respectively. The dielectric constant and loss tangent were determined as a function of temperature. Frequency response of the dielectric constant and tan δ have been studied over a frequency range of 0.1 −100 kHz; it is found that both the dielectric constant and tan δ decrease with increase in frequency for both crystals. The dielectric constant and tan δ are found to increase with increase in temperature for both the crystals. Further, the dielectric constant and tan δ measured on different orientations of the grown crystals reveal the anisotropic nature of the crystals.     

Glass formation and properties of chalcogenide systems XVIII. On glass formation in the system GePbSeTe

The glass formation range of the system GePbSeTe has been investigated. For selected series properties such as the mole volume, glass transition temperature and the electrical direct current conductivity are discussed with respect to their dependence on composition. For some series the results can be compared with the properties of glasses containing Sn instead of Pb. The change in the energy gap for the crystalline compounds SnSe, SnTe, PbSe and PbTe is reflected by the data of the Sn or Pb containing glasses.     

On the anomalies in density,Young's modulus and glass temperature of PdSi glasses

The densities, Young's moduli and glass transition temperatures have been measured for binary PdSi glassy alloys. These glassy alloys exhibit a negative deviation from Vegard's law an enhancement in Young's modulus and a tendency to lower the glass transition temperature in the region of the eutectic composition. The observed nonlinearity in these physical properties is shown to be better agreement with an alloy mixing effect rather than the structural ordering model.     

On possible binary molecular structure in the AsTeSe amorphous system

We present here experimental results on sixty different compositions of the ternary arsenic-tellurium-selenium system. The parameters considered here are: electrical conductivity and its thermal dependence, and transformation temperatures deduced from differential thermal analysis measurements. The synthesis of results leads to the vitrification area for glasses obtained by air quenching and gives rise to an analysis of the influence of the relative concentration of two elements with respect to the third considered as a parameter.DTA studies permit the separation of two different areas in the vitrification surface, corresponding to materials involving or not involving crystallization processes. We have investigated the possible existence of binary or ternary molecular structures in the vitrification region. The results presented here lead to the conclusion that no ternary molecular structure occurs in the AsTeSe system. Nevertheless it seems possible to conclude that one binary molecular structure can be built around As₂Se₃.     

Dielectric relaxation in iron-containing borate glasses

The ac and dc conductivities, dielectric constant and dielectric loss of a series of calcium borate glasses containing Fe₂O₃ up to 10 mol% were measured as a function of temperature (300–700 K) and frequency (10²–10⁵ c/s). Glasses melted in platinum crucibles were found to show slightly higher dielectric constants and conductivities than glasses melted in zirconia crucibles under the same melting conditions. Relaxation effects with a distribution of relaxation times were observed for all the glasses of this system. The data show that the pre-exponential factor τ₀ is about 10^?11 s. Peaks in tan δ were found to shift to higher temperatures when the frequency of measurements was increased. Activation energy for dc conduction was found to be equal to that of ac conduction. No polarization effects were observed in these glasses, indicating that conduction is predominantly electronic.     

Chemical aspects of glass formation in telluride systems

The compositional dependence of the electrical activation energy, the optical absorption and the glass transition temperature in typical binary, pseudo-binary and ternary glass forming telluride systems has been measured in an effort to correlate chemical binding with physical properties. A modification of the valency satisfaction model to include chemical ordering effects is required to account for the property singularities observed in the GeTe system at the composition GeTe₂. The ordering effects in Te-based alloys containing Ge are further verified by an endothermic disordering reaction in these liquids peaking between 400–475°C depending on composition.     

Experimental studies of phase equilibria in high-temperature ternary immiscible metallic melts

Shear viscosity measurements were carried out for a liquid immiscible ternary system In–Se–Te in a temperature range from the monotectic to about 1200 K using an oscillating-cup viscometer. It was revealed that the ternary In₈₀Se_xTe_20−x (0 ⩽ x ⩽ 20 at.%) system may be considered as a set of quasibinary In–(Se/Te) alloys of almost critical concentrations. A variation of the Se to Te ratio at constant content of In changes the properties of coexisting liquids and affects the binodal temperature. The critical parameters describing the peculiarities of viscosity behavior in the vicinity of the critical point are evaluated. The analysis based on the dynamic theory of phase transitions for viscosity in the phase separation region is proposed. The results are compared with available data for immiscible dielectric solutions and metallic melts.     

Photo-acoustic spectroscopy of SixSe1−x glasses

The optical properties near the fundamental absorption edge has been studied for a series of Si_xSe_1−x glasses using photoacoustic spectroscopy. The compositional dependence of the bandgap E_O, derived from these measurements, is presented and contrasted with the GeSe and the SiS systems. This data is qualitatively explained with a model which accounts for differing numbers of homopolar and heteropolar and heteropolar bonds as the composition is varied. Additional support for this interpretation is found in the compositional behavior of the glass transitions of these alloys.     

Refractive index of chalcogenide glasses over a wide range of compositions

The refractive index frequency dependence in the 1–11 μm range for AsSe, GeSe and AsGeSe glassforming systems and for three- and four-component systems obtained by substitution of antimony, bismuth, tin, lead, sulphur and tellurium for arsenic, germanium and selenium, being their periodic system counterparts, is investigated. A comparison of optical constants of chalcogenide glasses with those for other optical materials by means of constructing of an Abbe-type diagram in n_2.0 ? v_2.0 coordinates is considered. The possibility of chalcogenide glass refraction calculation by means of additive formulas is discussed. It is shown that critical points on the property-composition curves coincide with structural region boundaries in all of the investigated systems. These data are considered as further experimental support for the polymer nature of chalcogenide glasses.     

Electronic and thermodynamic properties of liquid chalcogenides

Recent measurements of various physical properties such as compressibility, electrical conductivity, optical reflectivity and nuclear magnetic resonance shift over wide temperature and pressure range are reported for liquid Se and SeTe mixtures. The observed semiconductor to metal transition for liquid Se and SeTe mixtures is accompanied by a substantial modification of the chain structure. A simple model of the transition to metallic state is proposed. The effect of charged additives on the transport properties of liquid Se is also discussed in connection with the change of the bonding configuration.     

Self-diffusion in the chalcogenide glass system SeGeAs

Se, As and Ge self-diffusion were investigated in three different glasses of the chalcogenide system SeGeAs by means of the radioactive tracers ⁷⁵Se, ⁷³As and ⁷¹Ge. All D values (Se between 200 and 290°C, As between 240 and 290°C and Ge between 280 and 295°C) lay between 10^?14 and 5 × 10^?16 cm² s^?1. The diffusion profiles were analyzed using a chemical micro-etching technique. Roles of glass structure and possible diffusion mechanism are discussed.     

On the structure of amorphous GexTe1−x systems

Calculations have been made for the quadrupole splitting of a $\text{3}\text{2}$ spin state of Te¹²⁵ in an amorphous Ge_xTe_1?x system. The results favour the existence of a threefold coordinated black phosphorus structure with an excess of TeTe chains for x-values between o and 0.5; beyond 0.5, threefold coordinated GeTe and an excess of amorphous Ge coexist.     

Elastic constants,hardness and their implications to flow properties of metallic glasses

The longitudinal and transverse sound velocities and Vickers hardness of metallic glasses (Pd_{1 ? x}Ni_x)_0.80P_0.20, (Pd_{1 ? x}Fe_x)_0.80P_0.20 and (Pt_{1 ? x}Ni_x)_0.75P_0.25 have been measured. The elastic constants at room temperature exhibit a positive deviation with composition χ from linearity whereas the hardness shows a negative deviation. The increase in elastic constants has been attributed to a denser packing of the alloys on mixing. The reduced hardness H_rH/μ versus χ exhibits a remarkable similarity to a T_g versus χ relationship. This seems to indicate that flow mechanisms involved in metallic glasses above and below the glass-transition temperature are of similar origins. It is the excess entropy of disorder associated with alloying which lowers the hardness as well as the viscosity of metallic glasses. The metallic glasses possess in general a relatively high Poisson's ratio ν ≈ 0.40 and a shear modulus approaching that of the noble metals Cu, Ag and Au. Among the metallic glasses observed, the PtP glasses exhibit the highest ν = 0.42, whereas the glasses containing Fe tend to have lower values. The phenomenon that the conduction electrons in the glassy alloys behave as in the noble metals may be partly attributed to the filling of d shell orbitals of the transition metals in the PtP, PdP and NiP alloys. The high ν of metallic glasses is believed to be responsible for the ductile behavior of these glasses. Poisson's ratio ν of metallic glasses was observed to decrease with decreasing temperature. It is suggested that the decreasing ν with falling temperature causes the rapid increase in the fracture strength of Fe-based glasses.     

Electrical properties of GeSbSe glasses

The dc and ac conductivities of glasses of the system GeSbSe (with the general formula Ge_xSb₁₀Se_90?x have been studied. The dc conductivity results indicate a maximum in the glass transition temperature and activation energy and a minimum in conductivity for the composition Ge₂₅Sb₁₀Se₆₅. These results have been explained on the basis of the prevalent structural arrangement wherein structural units of GeSe₂ and Sb₂Se₃ are dispersed among excess Se or Ge. Based on this picture, a model has been developed which accounts for the observed dependence of conductivity on composition at any temperature. The ac results have been utilized to find the hopping conductivity as a function of composition; the characteristics of lone pair amorphous semiconductors seem to account for the observed features.     

Compositional dependence of the thermal,structural, and electrical properties of AsTeI glasses

Thermal, structural, and electrical properties of semiconducting AsTeI (and AsTe) glasses have been examined as a function of concentration. Analytical techniques have been developed for quantitative chemical analysis of all three components. Differential scanning calorimetry data indicate a broad endothermic reaction, T_min ∼ 145 °C, above the glass transition (T_g = 120 ± 8 °C) for iodine compositions of 0 to ∼ 20 at%. Above this reaction temperature the thermal data are composition dependent. For glasses with I ? 35 at %, T_g is much lower (65–70 °C) and the endothermic reaction is much sharper with a minimum at ∼ 133 °C. The wide variation in thermal properties with composition suggests that electrical effects associated with high temperatures (e.g. switching and memory phenomena) may also be composition dependent, as well as being dependent upon kinetics. Structural studies show that phase segregation above T_g is dependent upon kinetics as well as upon temperature. Thermal, structural, and electrical data give evidence that As₂Te₃ exists as a unit in the non-crystalline state. This structural unit, stable at high temperatures, is present in the molten material and is thought to be present as the supercooled liquid is quenched. The short-range order extends to long-range order upon devitrification and the first crystalline phase detected is monoclinic As₂Te₃. Apparently metastable under the conditions of formation, this phase converts to a previously unreported fcc phase upon further heat treatment. Similar crystalline structures are known to be associated with thermally- and electrically-induced memory phenomena in AsTeGe and AsTeI glasses. Density measurements at room temperature show that (1) there are no phase miscibility gaps in the glass substructure or different crystalline phases segregating as the I content is varied, and (2) there is a large change in molar volume with increasing I concentration, whereas the molar weight does not change significantly. Electrical conductivity, σ, data in the region around room temperature, show that the σ₀ values, determined from σ = σ₀e^−E/kt, range from 10² to 10³ (Ω-cm)⁻¹. A possible dependence of σ₀ on I content may be due to changes in molar volume. The more homogeneous glasses appear to show breakpoints in the σ versus 1/T data; the corresponding changes in E are only 0.02–0.06 eV, with E = 0.04 eV being most frequently observed. For As₅₀Te_50−xI_x glasses, σ at a given temperature increases as the iodine concentration is increased to about 5 at % and then decreases with further increase in I content. Correspondingly there is a minimum in the E versus I concentration data at I ∼ 5 at %. Results suggest that dependence of the σ breakpoints on glass homogeneity and the variation of E with I concentration may be due to trapping effects.