Molecular dynamics simulation of temperature-induced structural changes in cristobalite,coesite and amorphous silica

Structural changes in cristobalite, coesite, and amorphous silica have been investigated from 100 to 3000 K by molecular dynamics simulations. These have been made with ‘soft potentials’ that yield melting and glass transition temperatures in fair agreement with experimental data. The simulated density of cristobalite increases abruptly at the α–β transition, that of coesite increases gradually, whereas that of amorphous silica goes through a density maximum around 2000 K. In the three phases, the complex temperature-induced structural changes have been analyzed in terms of variations of the abundances of four ‘structons’ which represent different kinds of Si–O bond lengths and torsional angles between two SiO₄ units. These changes in cristobalite, coesite and amorphous silica can then be rationalized in terms of loosening of network and of dynamical rotation of SiO₄ units. The relation between structural changes and ring statistics is also discussed.     

Molecular dynamics simulation of polymorphic and polyamorphic transitions in tetrahedral network glasses: BeF2 and GeO2

It is well know that tetrahedral network glasses have anomalous properties such as a density maximum and bulk modulus minimum. The magnitudes of such anomalous properties are different among tetrahedral network glasses. The origin of this anomaly has not been explained yet. We had already analyzed the local structural changes in SiO₂ in terms of transformation of ‘structon’. The fragments of Si₂O₇ were categorized into four types named alpha-, beta-, gamma-, and delta-‘structons’. In this study we use molecular dynamics simulations to investigate the structural changes in crystalline and vitreous BeF₂ and GeO₂. First the simulated BeF₂ cristobalite and quartz clearly reproduce their alpha–beta transitions and the density in the vitreous BeF₂ shows a maximum around 2300 K. On the contrary, GeO₂ shows weak alpha–beta like transitions in cristobalite and quartz, and a density maximum is not observed in the vitreous phase. Next we perform the ‘structon’ analyses on BeF₂ and GeO₂. For the BeF₂ system the conversion between alpha- and beta-‘structons’ are almost complete, as previously observed in our study on the SiO₂ system. On the other hand, such transformation is incomplete in the GeO₂ system. We discuss similarities and dissimilarities between SiO₂, BeF₂, and GeO₂.     

Octahedral fluoride glasses: Raman spectra and structure of niobium pentafluoride

Raman spectroscopy is used to characterize the NbF₅ phases in the temperature range 80–500 K. A new clear glass is formed by quenching the melt to liquid nitrogen temperatures having a glass transition at ～206 K and crystallization at ～233 K. For all phases including the melt, the glass, the supercooled liquid, the crystalline solid and the gas, the Raman spectra show a rather common high frequency band at ～760 cm^?1 which is attributed to the Nb–F terminal frequency of partially bridged ‘NbF₆’ octahedra. Based on the systematics of the Raman spectra for all phases and the literature physicochemical data a model is proposed for the glass and the liquid phases where ‘NbF₆’ octahedral bridged in cis and/or trans configurations form a variety of cyclic and/or chain structures which intermix building up the overall structure. At exceptionally low energies (<11 cm^?1) a rather weak in intensity Boson peak is observed in the glass which shifts to even lower energies with increasing temperature. Librational and/or tortional motions of the bridged octahedra participating in the glass structure are possible candidates for the origin of this peak.     

Morphology of synthetic chrysoberyl and alexandrite crystals: Analysis of experimental data and theoretical modeling

A morphological analysis of chrysoberyl and alexandrite crystals obtained by flux crystallization has been performed. Seven morphological types of crystals are selected. The surface energies of the faces of chrysoberyl and alexandrite crystals and their isostructural analogs, BeCr₂O₄ and BeFe₂O₄, have been calculated by atomistic computer modeling using the Metadise program. A “combined” approach is proposed which takes into account both the structural geometry and the surface energy of the faces and thus provides better agreement between the theoretical and experimentally observed faceting of chrysoberyl and alexandrite crystals.     

The configurational entropy of glass

Configurational entropy is of fundamental importance to understanding the universal nature of the glassy state. According to the conventional view, the configurational entropy of a liquid is ‘frozen’ below the glass transition temperature (T_g) all the way to absolute zero. Contrary to this, we claim that: (i) there is an entropy loss associated with the liquid to glass transition, and (ii) the configurational entropy in the glassy state vanishes at absolute zero. This paper contrasts our arguments (called the ‘entropy loss’ view) and the conventional view.     

High pressure effects on liquid viscosity and glass transition behaviour,polyamorphic phase transitions and structural properties of glasses and liquids

Since the pioneering work of Bridgman it has been known that pressure affects the glass transition of polymers and liquid state viscosities. Usually the T_g and viscosity both increase as a function of pressure as expected from ‘free volume’ theories. However, H₂O provided a notable exception in that the viscosity passes through a minimum at low temperature. It was thought that this might be linked to the anomalous thermal expansion behavior. However further research on geologically important aluminosilicate liquids revealed that they could show anomalous viscosity decreases with increasing pressure and this behavior is given a structural interpretation as five-fold coordinated Si⁴⁺ and Al³⁺ species are formed. Also the existence of polyamorphism or density-driven liquid–liquid phase transitions in certain systems can lead to anomalies in the T_g or η vs. P relations. This may be the case for H₂O, for example. Current research is focusing on investigating structural changes in liquids and glasses at high pressure as the rich variety of behavior is becoming recognized. Both experimental studies and computer simulations are important as the underlying phenomonology is linked to changes in the glass or liquid structure as a function of densification.     

Glass transition temperature dependence on heating rate and on ageing for amorphous selenium films

The study, by differential thermal analysis (DTA) of the glass transition of thermally evaporated amorphous selenium, allows the effect of ageing on structural properties to be observed. An enthalpic diagram is used to explain the shift of the glass transition region, with heating rate, and also with ageing. These shifts are directly dependent on structural relaxation in amorphous selenium. The model used, to express the change of the structural time relaxation with temperature, and with the departure of thermodynamic equilibrium leads to a slightly different expression for the dependence of T_g on heating rate than that previously published (by Moynihan et al.).The activation enthalpies of the studied phenomena compared with other results, seem to show that structural relaxation in a-Se principally involves bond breaking and reformation of chains.     

An electrospray technique for hyperquenched glass calorimetry studies: Propylene glycol and di-n-butyl phthalate

We describe an electrospray technique for in situ preparation, for differential scanning calorimetry study, of samples of molecular liquids quenched into the glassy state on extremely short time scales (hyperquenched). We study the cases of a hydrogen-bonded liquid, propylene glycol, PG and a Van der Waals liquid, di-n-butyl phthalate DBP. Using a fictive temperature method of obtaining the temperature dependence of enthalpy relaxation, we show that the electrospray method yields quenching rates of ∼10⁵ K/s, while the more common method, dropping a sealed pan of sample into liquid nitrogen, yields only 120 K/s. These hyperquenched samples start to relax, exothermically, far below the glass temperature, at a temperature (0.75T_g) where the thermal energy permits escape from the shallow traps in which the system becomes localized during hyperquenching. This permits estimation of the trap depths, which are then compared with the activation energy estimated from the fictive temperature of the glass and the relaxation time at the fictive temperature. The trap depth in molar energy units is compared with the ‘height of the landscape’ for PG, the quasi-lattice energy of the liquid based on the enthalpy of vaporization, and the single molecule activation energy for diffusion in crystals. The findings are consistent with the mechanism of relaxation invoked in a current model of relaxation in glassforming liquids. In the case of di-n-butyl phthalate we investigate the additional question of sub-T_g annealing effects. We find the ‘shadow’ glass transition, (an annealing prepeak) seen previously only in multicomponent mineral and metallic glasses. The phenomenon is important for understanding microheterogeneities in viscous liquid structures.     

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.     

Correlations between electronic structure of transition metal atoms and performance of high-k gate dielectrics in advanced Si devices

This paper develops a classification scheme for non-crystalline dielectrics that separates them into three groups with different amorphous morphologies, and identifies a linear scaling relationship between average bond ionicity and oxygen atom coordination. The classification scheme is applied to transition metal silicate and aluminate alloys and provides a structural model for molecular orbital, MO, calculations that are based on the coordination and symmetry of transition metal atoms and the orbital energies of their oxygen neighbors. The MO calculations show that conduction band offset energies with respect to Si scale inversely with the energy difference between transition metal atomic n+1 s- and n d-states providing an important insight into the choice of alternative gate dielectrics for advanced Si devices.     

Thermodynamic and thermokinetic characteristics of the glass transition in a GeSe2GeTeSb2Te3 alloy

Glassy alloys of (GeSe₂)₇₀ (GeTe)₁₅ (Sb₂Te₃)₁₅ were prepared by water-quenching and subjected to several thermal treatments through the glass transition region. The thermodynamic and thermokinetic characteristics of the glass were inferred from heat capacity measurements by differential scanning calorimetry. It was demonstrated that the undercooled liquid obtained by heating the glass is in equilibrium, and what is more, that not only each particular cooling process through the glass transition produces a given glass, but also that any trance of the glass may be suppressed by reheating above glass transition. The enthalpy and entropy differences between each glass and the undercooled liquid used to obtain that particular glass were taken as properties sensitive to the relaxation inherent to the formation of the glass. The activation energy spectrum characterizing the relaxation processes on cooling through the glass transition has been obtained. It has a peak energy of 1.43 eV which may be related to the bonds between the constituent atoms of the sample with weaker interaction energy. Therefore, the relaxation may be due to a breaking and rearrangement of these bonds in the glassy structure.     

Structural evolution of metallic glasses during annealing through in situ synchrotron X-ray diffraction

In this work we study the structural evolution of Al and Fe based metallic glass compositions. The samples were obtained as ribbons by melt-spinning, their glass stability and crystallization were analyzed by differential scanning calorimetry and dilatometry, structural changes were followed by in situ synchrotron X-ray diffraction during annealing throughout glass transition and crystallization. The synchrotron results are compared with the calorimetric and dilatometric measurements and the structural changes occurred during annealing are determined and described for each alloy.     

Effects of mixed alkaline earth oxides additive on crystallization and structural changes in borosilicate glasses

The effects of mixed alkaline earth oxides on crystallization and structural changes in a multi-component borosilicate glass system are studied by using X-ray diffraction (XRD) and transmission electron microscope (TEM). It is found that the crystallization is decreased with increasing alkaline earth oxide content and there are also a series changes occurred in TEM images. This paper introduces the conception that alkaline earth ions tend to occupy their preferred sites regardless of glass systems. This conception is assisted to explain the TEM images to some extent by suggesting a simple structural model about non-bridging oxygen in glass network. The conception also indicates a ‘blocking effect’ existing in such a multi-component borosilicate glass system, which may be responsible for XRD results in chief. In addition, the structural model suggested by TEM results refers a new unit of Si–O–M²⁺–O–B, which helps in understanding the minimum exhibits in XRD results. Moreover, a dielectric test is taken to study glass properties in detail.     

Viscous behaviour of undercooled metallic melts

Viscosity data for non-crystalline Au_0.77Ge_0.136Si_0.094 alloys in the region of the glass transition temperature and above the melting point, are fitted to a single expression of the type proposed by Doolittle. This expression also leads to reasonable values for the activation energy for hole formation in the liquid and for the liquid free volume at the glass transition temperature. A similar procedure was applied to the viscosity data of a Pd_0.775Cu_0.06Si_0.165 non-crystalline alloy. By assuming values for the liquid free volume at both the glass transition temperature and the melting point, the analysis is also extended to Pd_0.82Si_0.18 alloys for which no viscosity data are available. Here, time-temperature-transformation (T-T-T) curves for crystallization are calculated for each of the three alloys, and used to determine the critical cooling rates for the formation of an amorphous solid.     

Crystallization kinetics and optical band gap studies of Se96In4 glass before and after slow neutron irradiation

Results of differential scanning calorimetry (DSC) under non-isothermal condition on Se₉₆In₄ semiconducting chalcogenide glass before and after slow neutron irradiation, for different exposure times, have been reported and discussed. Some of Sn atoms have been injected into the glass by nuclear transmutation processes and the binary glass is converted into a ternary. This is accompanied by an increase in the activation energy of crystallization, E_c, and in the glass transition temperature, T_g and a decrease in the glass transition activation energy, E_t, in the onset crystallization temperature, T_c and in the peak temperature of crystallization T_p. Optical band gap measurements have also been carried out, before and after irradiation, on identical thin pellets of Se₉₆In₄ glass. The energy band gap, E_g, is found to decrease upon irradiation. These effects have been attributed to a structural change upon doping and to irradiation induced defects.     

Structure and properties of lanthanum galliogermanate glasses

Lanthanum galliogermanate glasses were prepared. Raman spectra, molar volumes, glass transition temperatures and activation energies for glass transition and crystallization were obtained. For glasses having the same La₂O₃/GeO₂ ratio, the molar volumes increase with the Ga₂O₃ content, and the glass transition temperatures, activation energies for glass transition and crystallization, increase initially then decrease as the ratio of Ga₂O₃/GeO₂ increases. For glasses having the same Ga₂O₃/GeO₂ ratio, the molar volumes increase with La₂O₃ content, and the glass transition temperatures increase as the ratio of La₂O₃/GeO₂ increases. The change of glass structure and its properties with composition is correlated with the concentration of lanthanum ion.     

The influence of Ta2O5 additions on the thermal properties and crystallization kinetics of a lithium zinc silicate glass

The lithium zinc silicate glass exhibits two crystallization exotherms corresponding to the formation of Li₂ZnSiO₄ and silica phases, respectively. The silica phases include tridymite and cristobalite. The influence of Ta₂O₅ additions on the thermal properties and non-isothermal crystallization kinetics of this glass, including nucleation rate maxima and activation energies for crystallization, has been determined by differential scanning calorimetry and X-ray diffraction. It has been found that Ta₂O₅ affects the crystallization behavior markedly, inhibiting the crystallization of high thermal expansion silica phases at lower concentrations, whilst at higher concentrations also suppressing crystallization of the Li₂ZnSiO₄ phase. At the higher concentrations, these phases are replaced by small amounts of LiTaO₃ and LiTaSiO₅.     

Electrical conductivity and 11B NMR studies of sodium borosilicate glasses

A large number of compositions within the SiO₂–NaO₂–B₂O₃ (SNB) ternary glass system were investigated by various complementary techniques. Impedance spectroscopy was used to determine the parameters related to sodium ion diffusion in the glass structure; high-field boron NMR measurements on a series of samples identified and quantified the boron coordination as a function of the composition; exhaustive DTA measurements gave the glass transition temperature for all the compositions studied. Based on these results we demonstrate that the activation energy of sodium ion diffusion is closely related to the boron coordination number and involves two types of structural motifs: one corresponding to the sodium associated to non-bridging oxygen atoms, and the other to sodium compensating B^IV motif. We also show that simple DTA measurements of the glass transition temperature can be used to define structural domains within this ternary composition range.     

Structural and physical properties of a novel TeO2-BaO-SrO-Ta2O5 glass system for photonic device applications

A detailed study on a novel TeO₂-BaO-SrO-Ta₂O₅ glass system developed for photonic device applications is reported in this paper. The glass transition and crystallization temperatures could be selected by varying the Ta₂O₅ content in this glass system. This glass system is found to have good thermal stability among tellurite glasses. Raman spectroscopy has been used as a tool to analyze the structural details of this technologically important glass system. In addition to the TeO₄ trigonal bipyramid and TeO₃ trigonal pyramid structural units, glasses in this system revealed the presence of an additional Raman band attributed to TaO₆ octahedra. The Raman bandwidth of the present glasses are broader compared to the conventional tellurite glasses by 35%. The influence of a gradual addition of the modifier oxides on the coordination geometry of tellurium atoms has been elucidated. Unlike the other tellurite glasses, even at higher modifier concentrations the TeO₄ structural units dominate in the glass network compared to TeO₃ trigonal pyramids. The ratio of TeO₄/TeO₃ structural units was discussed for different series of glass compositions.     

Surface structure and properties of NiZr model metallic glasses: A molecular dynamics simulation

A systematic study of the surface structure and properties of NiZr model metallic glasses is reported using atomistic simulations. It is found that at low temperatures below the glass transition temperatures, the surface retains the amorphous structure and the surface energy γ is significantly lower (∼50%) than that of the corresponding crystalline alloy constituents. The variation of alloy concentration has little effect on γ; but increase in cooling rate and annealing temperature can lead to large decrease in γ. At elevated temperatures, γ increases with temperature and surface melting occurs at a temperature about 30% below T_g. At all temperatures up to T_g, the surface remains atomically smooth.