The neutron diffraction study of liquid GeTe and As2Te3

The radial distribution analyses for GeTe and As₂Te₃ are made at temperatures above the melting point in the range of momentum transfer between 0.7 and 10.0 Å^?1 by the neutron diffraction technique. Furthermore, the local order in amorphous GeTe is determined by analyzing the intensity data of the electron diffraction of its thin film. The result for the amorphous film indicates that the local distribution of atoms in amorphous GeTe is not characteristic of the structure of its crystalline state. The shape of the peaks of the intensity curve for liquid GeTe differs from that for the amorphous and crystalline states. However, the short bond length and the small coordination number determined from liquid RDF suggest that the covalent-like bonding between nearest-neighbor atoms remains unbroken when melting. The general form of the structure factor for liquid As₂Te₃ is similar to that for the amorphous material reported previously. The position of the first peak of RDF in the liquid state is observed to be shifted to a shorter distance than the average of nearest-neighbor atoms in crystalline As₂Te₃. The structure of GeTe differs considerably between the crystalline, amorphous and liquid states, whereas the local order in the liquid As₂Te₃ is similar to that in the amorphous state but not in the crystalline state.     

Structural transformation on Se0.8Te0.2 chalcogenide glass

Using X-ray diffraction and differential scanning calorimetry (DSC), the structure and the crystallization mechanism of Se_0.8Te_0.2 chalcogenide glass has been studied. The structure of the crystalline phase has been refined using the Rietveld technique. The crystal structure is hexagonal with lattice parameter a = 0.443 nm and c = 0.511 nm. The average crystallite size obtained using Scherrer equation is equal 16.2 nm, so it lies in the nano-range. From the radial distribution function, the short range order (SRO) of the amorphous phase has been discussed. The structure unit of the SRO is regular tetrahedron with (r₂/r₁) = 1.61. The Se_0.8Te_0.2 glassy sample obeys the chemical order network model, CONM. Some amorphous structural parameters have been deduced. The crystallization mechanism of the amorphous phase is one-dimensional growth. The calculated value of the glass transition activation energy (E_g) and the crystallization activation energy (E_c) are 159.8 ± 0.3 and 104.3 ± 0.51 kJ/mol, respectively.     

Determination of partial pair distribution functions in amorphous Ge15Te85 by simultaneous RMC simulation of diffraction and EXAFS data

The atomic structure of amorphous Ge₁₅Te₈₅ has been studied by X-ray absorption spectroscopy (EXAFS) at Ge K-edge. EXAFS data were modeled simultaneously with existing X-ray and neutron diffraction measurements by the reverse Monte Carlo (RMC) simulation technique. Combination of the three independent measurements allowed separation of the partial pair correlation functions g_GeTe(r) and g_TeTe(r) and estimation of the corresponding coordination numbers.     

Production of amorphous iron-silicon powders via laser pyrolysis of gaseous precursors

Amorphous, submicron powders of FeSi_{(1 ? x)} were produced by laser augmented thermal decomposition of gaseous mixtures of Fe(CO)₅ and SiH₄. Production of metal and metalloid atoms is rapid enough at pyrolysis temperatures (about 350–600°C) to cause very large supersaturations. This leads to the nucleation and growth of nearly spherical amorphous FeSi_{(1 ? x)} particles 50–300 Å in diameter which form very fine chain-like agglomerations. The amorphous character of the particulate material was characterized by differential scanning calorimetry and electron diffraction. A glass to crystalline transition is observed near (610 ± 50). This technique may have potential uses for producing amorphous alloy powders where conventional techniques are impractical.     

The structure of nanovolumes of amorphous materials

In this paper we demonstrate reduced density function (G(r)) analysis from amorphous volumes as small as 2 nm in width. Obtaining the G(r) from a diffraction pattern is a common starting point in the characterisation of amorphous materials. The use of electrons to form the diffraction pattern allows very small volumes of amorphous material to be investigated.     

Conductivity and dielectric properties of polymer electrolytes PEO:LiN(CF3SO2)2 near glass transition

Results of measurements of PEO:LiN(CF₃SO₂)₂ polymer electrolytes of composition between 12:1 and 1.5:1 EO:Li, performed by impedance spectroscopy, impedance spectroscopy simultaneous with microscope observation, differential scanning calorimetry and X-ray diffraction were analyzed focusing on electrical properties of semicrystalline and rapidly cooled amorphous samples. In the loss spectra measured at low temperature, the occurrence of two dielectric relaxations was evidenced: local (β) and segmental (α). For each of the investigated electrolytes, the temperature dependence of the ionic conductivity and the frequency of α relaxation could be described by the VTF function with the same value of parameter T₀, which indicated close coupling of both phenomena. The local (β) relaxation exhibited an Arrhenius type temperature dependence. With increasing amount of salt, two effects were observed for amorphous samples: an increase of the glass transition temperature T_g affecting the α relaxation and changes of structure of PEO:LiN(CF₃SO₂)₂ complexes reflected in shift of the β relaxation frequency. Crystallization caused decrease of both the ionic conductivity and the strength of dielectric relaxations. The presence of crystalline phase was also reflected in a shift of the T_g of amorphous phase remaining in the system with respect to the T_g of amorphous electrolyte obtained by rapid cooling.     

Solid-state NMR and XANES studies of lithium and silver silicate gels synthesized by the sol-gel route

The objective of this study is to understand the effect of low temperature sol-gel synthesis on the microstructural properties of lithium [xLi₂O-(1−x)SiO₂; x=0.1-0.8 in steps of 0.1] and silver [xAg₂O-(1−x)SiO₂; x=0.1-0.8 in steps of 0.1] silicate xerogels via solid state nuclear magnetic resonance (NMR) and X-ray absorption near edge structure (XANES) techniques. The Li silicate xerogels were analyzed with solid-state ⁷Li and ²⁹Si NMR and the Ag silicate xerogels were studied with Ag XANES. At high Li loading, ⁷Li NMR shows quadrupolar satellite transitions attributed to LiNO₃, a phase also found with X-ray diffraction (XRD). At low Li loading, both NMR and XRD results show an amorphous xerogel. The silicate network is monitored with ²⁹Si NMR and shows evidence of Li incorporation. For the Ag silicate xerogels, Ag-L-III XANES spectral studies show a local environment similar to AgNO₃ for low Ag loading levels, and an increased Ag oxidation for higher Ag loading levels. Si K edge spectra show only an amorphous phase, with no evidence of a crystalline quartz phase. The electrical conductivity of the lithium silicates was estimated from impedance data and the highest conductivity is exhibited by the 0.3Li₂O-0.7SiO₂ composition xerogel. The conductivity dependence on loading level strongly suggests that the observed conductivity is due to Li⁺ mobility. However, further experimental studies are needed to rule out the possibility that the conductivity is, at least in part, due to H⁺ mobility. Variation in conductivity is explained qualitatively using existing theoretical models.     

Effect of annealing temperature on the structural and optical properties of amorphous Sb2Te2Se thin films

Thin films of Sb₂Te₂Se were prepared by conventional thermal evaporation of the presynthesized material on Corning glass substrates. The chemical composition of the samples was determined by means of energy‐dispersive X‐ray spectrometry. X‐ray diffraction studies on the as‐deposited and annealed films revealed an amorphous‐to‐crystalline phase transition. The as‐deposited and annealed films at T _a = 323 and 373 K are amorphous, while those annealed at T _a= 423 and 473 K are crystalline with a single‐phase of a rhombohedral crystalline structure as that of the source material. The unit‐cell lattice parameters were determined and compared with the reported data. The optical constants (n , k ) of the investigated films were determined from the transmittance and reflectance data at normal incidence in the spectral range 400–2500 nm. The analysis of the absorption spectra revealed non‐direct energy gaps, characterizing the amorphous films, while the crystalline films exhibited direct energy gaps. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of fast ion conducting AgI–As2Se3 glasses

High-energy X-ray diffraction, neutron diffraction and extended X-ray absorption fine structure experiments have been carried out for (AgI)_x(As₂Se₃)_1−x glasses. The addition of a large amount of AgI does not significantly affect the short-range ordering of the host network matrix, that is, As(Se_1/2)₃ pyramidal units remain essentially intact on introducing AgI. The interatomic distance of Ag–I pairs is similar to the case of crystalline AgI. However, the coordination number of Ag–I pairs in the present glasses seems to be somewhat smaller than that in the crystalline AgI, suggesting a heavy distortion of tetrahedral coordinates of AgI units or structural disorder of the I–I sub cages in the glass state.     

Synthesis and characterization of germanium sulfide aerogels

The synthesis of germanium sulfide gels by thiolysis reactions of a non-aqueous solution of Ge(OEt)₄, followed by supercritical fluid extraction to create aerogels, is described. Analysis of the as-prepared GeS_x aerogels by powder X-ray diffraction (PXRD) and surface area analysis reveals an amorphous structure exhibiting very high surface areas, 755 m²/g, that rival those of the best SiO₂ aerogels when compared on a per mole basis. Transmission electron microscopy shows that the aerogel material is composed of a continuous network of GeS_x colloidal particles assembled in a three-dimensional architecture. A detailed comparison of GeS_x aerogels and their xerogel (bench-top dried) counterparts in terms of the influence of the synthetic methodology on morphology and surface area is reported. In the presence of adventitious moisture, the amorphous GeS_x is oxidized to a crystalline phase identified by X-ray photoelectron spectroscopy, Raman spectroscopy and PXRD cell refinement to be hexagonal GeO₂.     

Ductility improvement of Zr-Cu-Ni-Al glassy alloy

We studied the relationship between the phase diagrams and formation of crystalline inclusions in cast samples in order to improve the ductility of Zr-Cu-Ni-Al bulk amorphous alloy. A Zr₅₀Cu₄₀Al₁₀ bulk amorphous alloy with a composition close to the ternary eutectic point has no crystalline inclusions and possesses superior mechanical properties of tensile strength σ_B=2000 MPa, Young’s modulus E=107 GPa and Vickers hardness HV=580. Oxygen embrittlement of Zr-Cu-Ni-Al bulk amorphous alloys can be avoided in the Zr₅₀Cu₃₀Ni₁₀Al₁₀ bulk amorphous alloy, which exhibits superior ductility and resistance to oxidation. Furthermore, we tried to improve ductility by cold rolling by making use of the apparent work-softening phenomenon of Zr-Cu-Ni-Al bulk amorphous alloys. Preliminary studies indicated that cold rolling to produce a fine slip-band structure, which enabled uniform deformation and superior deformability, is an important procedure for improving the ductility of Zr-Cu-Ni-Al bulk amorphous alloys.     

Time dependence of electrical resistance at high pressure in some tellurium based amorphous alloys

Electrical resistance measurements are reported for amorphous In₂₀Te₈₀ and Cu₂₅Au₅Te₇₀ alloys up to a pressure of 80 Kbar using a Bridgman anvil apparatus and a four lead arrangement to measure resistances. The amorphous samples are produced by liquisol quenching. The resistance shows time dependent changes which are analysed in detail. The contention that there is a pressure-induced transformation from the amorphous to the crystalline phase is confirmed by X-ray diffraction of samples recovered after they were pressurised to 35 Kbar in a hydrostatic environment.     

Calorimetric,diffraction and microscopic examination of evaporated amorphous germanium

Dynamic calorimetric and thermal gravimetric measurements revealed that evaporated, amorphous Ge adsorbed up to 3 wt % H₂O when exposed to the atmosphere. Desiccation removed one-half; however, the remainder was removed only by heating to 450°C which also completely recrystallized the material. The heat of crystallization was found to be, ΔH_c = 2.6 ± 0.4 kcal/mol.Electron microscopic examination revealed ≈100Å void network as found by others with heterogeneous crystallization as samples were annealed at ≈200°C. During the annealing and crystallization, the normally forbidden (222) electron diffraction reflection was frequently observed. We interpret this as being due to (111) twinning which is evidence of wurtzite-type bonding in the original evaporated, amorphous Ge material.     

Coordination structure of Li+ in concentrated aqueous lithium alaninate solutions

Time-of-Flight (TOF) neutron diffraction measurements with the ⁶Li/⁷Li isotopic substitution technique were carried out for aqueous 18 mol% lithium alaninate solutions in D₂O in order to obtain structural information on the interaction between Li⁺ and the amino acid molecule in the concentrated aqueous solution. The first-order difference function, Δ_Li(Q), was obtained from the difference between scattering cross sections observed for solutions involving dl-CH₃CH(ND₂)COO⁶Li and dl-CH₃CH(ND₂)COO⁷Li. The distribution function around Li⁺, G_Li(r), exhibits well resolved first and second peaks that are tentatively attributable to the nearest neighbor Li⁺ ⋯ O and Li⁺ ⋯ D interactions. However, the coordination number, n_LiD, estimated from the area under the second peak is found to be much larger than the value, 2n_LiO, evaluated from the first peak of the present G_Li(r). This implies that the nearest neighbor Li⁺ ⋯ alaninate ion interaction may contribute to the second peak. Structural parameters concerning the first coordination shell of the Li⁺ has been determined through the least squares fitting analysis of the observed Δ_Li(Q). It has been revealed that the Li⁺ is surrounded by 2.4(1) D₂O molecules and 2.3(2) alaninate ions with interatomic distances of r(Li⁺ ⋯ O_D2O) = 1.97(1) Å, r(Li⁺ ⋯ D_D2O) = 2.62(1) Å and r(Li⁺ ⋯ O_alaninate) = 2.38(1) Å, respectively.     

Structural study of AsS2–Ag glasses over a wide concentration range

(As_0.33S_0.67)_100-xAg_x (0 ≤ x ≤ 28) bulk glasses showing micro-phase separation in a wide concentration range have been studied by X-ray diffraction, neutron diffraction and extended X-ray absorption fine structure measurements. The AsAgS₂ composition, which forms a homogeneous glass, is modeled with the reverse Monte-Carlo simulation technique. It is established that Ag prefers the environment of S; Ag―As bonding cannot be observed. Similarly to the AsAgS₂ crystalline modifications smithite and trechmannite, the main structural units of the glass are AsS₃ pyramids. The covalent network of As and S atoms becomes fragmented in the glassy AsAgS₂ unlike in the glassy AsS₂. The environment of Ag atoms in the AsAgS₂ glass differs from that in the crystalline state. In average, each Ag atom has four nearest neighbors, three of them being S and one being Ag.     

Properties and structure of AsTe glasses: (I). Glass-forming ability and related properties

AsTe glasses have been investigated for determining the molecular mechanisms of glass formation and of crystallization. Stable and homogeneous bulk glasses are prepared throughout the range of concentration from 20 to 65 at % As, by using an improved quenching method. GFA (glass-forming ability) is determined with respect to the rate of cooling. Density, microhardness, T_g and ΔC_p at T_g are measured in the whole range of glass formation. Finally a quantitative analysis of the kinetics of crystallization is carried out. It appears that most properties which involve molecular motions exhibit anomalies for As₄₀ Te₆₀ composition (As₂Te₃ is the unique definite compound of the system). So GFA shows a sharp depression for this critical composition; similarly enthalpy and kinetics of crystallization are drastically modified at As₄₀Te₆₀. For Te-rich glasses, crystallization occurs at low temperature by homogeneous nucleation with a small energy of activation. For As-rich glasses, crystallization occurs at much higher temperatures. Above 200°C it is controlled by growth with an high activation energy which indicates deep rearrangements of the relative positions of the atoms by chemical diffusion. A coherent analysis of all the data is developed which shows that important differences of local order exist between amorphous and crystalline states and also between the two well-distinct types of glasses we are dealing with. The aim of paper II is to determine these differences from diffraction data.     

X-Ray diffraction study of the evolution of phase and structural state and macroscopic stress during annealing of soft magnetic Fe95 − x Zr5N x films prepared by ion-plasma deposition

The evolution of the phase composition, nanostructure parameters, and macroscopic stress in soft magnetic Fe_{95 ? x} Zr₅N _x films (prepared by ion-plasma deposition onto quartz substrates) during their annealing has been investigated by X-ray diffraction. During deposition, depending on the N content, either a mixed structure composed of an X-ray amorphous phase enriched in Zr and N and a crystalline phase (α-Fe(N) solid solution) or an X-ray amorphous phase enriched in Fe, Zr, and N is formed in the films. During annealing, depending on the temperature and nitrogen content, different combinations of crystalline phases (α-Fe(N) and Zr(N) solid solutions, α-Fe, Fe₄N, Fe₂N, ZrO₂) are formed in the films. The large compressive stress formed in the films during deposition changes to a lower tensile stress during annealing.     

Recombination processes in amorphous selenium

In order to determine the recombination lifetime τ_r we have studied the photoconduction under pulsed light in amorphous selenium. Experimental results, relative to the variation of τ_r with temperature, enable us to calculate the parameters which characterized the recombination centers: capture cross sections S_n and S_p (and their variations with T), localization of the level E_r, density of states N_r.     

Crystallization kinetics of Fe73.5−xMnxCu1Nb3Si13.5B9 (x = 0, 1, 3, 5, 7) amorphous alloys

In this study, we have investigated the effect of substituting Mn for Fe on the crystallization kinetics of amorphous Fe_73.5−xMn_xCu₁Nb₃Si_13.5B₉ (x = 1, 3, 5, 7) alloys. The samples were annealed at 550 °C and 600 °C for 1 h under an argon atmosphere. The X-ray diffraction analyses showed only a crystalline peak belonging to the α-Fe(Si) phase, with the grain size ranging from 12.2 nm for x = 0 to 16.7 nm for x = 7. The activation energies of the alloys were calculated using Kissinger, Ozawa and Augis-Bennett models based on differential thermal analysis data. The Avrami exponent n was calculated from the Johnson-Mehl-Avrami equation. The activation energy increased up to x = 3, then decreased with increasing Mn content. The values of the Avrami exponent showed that the crystallization is typical diffusion-controlled three-dimensional growth at a constant nucleation rate.