Raman spectroscopic study on the structure of ZnCl2---ZnX2 and ZnCl2---KX (X = Br, I) glasses

Raman spectra have been measured for ZnCl₂---ZnX₂ and ZnCl₂---KX (X = Br, I) glasses to investigate the structure of the glasses with varying composition. The assignment of each band was made, and the change of the spectra with composition was explained in terms of the bridging and non-bridging states of halide ions and the change of the tetrahedral units, ZnX_nCl_4−n²⁻ (n = 0–4), formed in the glasses. As the content of ZnX₂ in ZnCl₂---ZnX₂ glasses increases (20 → 80 mol%), the peak frequency of the Zn---Cl stretching mode increases (238 → 248 cm⁻¹ in X = I glasses, 238 → 259 cm⁻¹ in X = Br glasses) while the Zn---I and Zn---Br stretching frequencies decrease (173 → 120 cm⁻¹ for Zn---I, 196 → 157 cm⁻¹ for Zn---Br). The decrease of the Zn---I and Zn---Br band frequencies was attributed to the increase of the number n of the ZnX_nCl_4−n²⁻ tetrahedra. The increase of the Zn---Cl frequency suggests the existence of the bonding state of Cl⁻ ions which is intermediate between the bridging and the non-bridging states. In ZnCl₂---KX glasses, the Zn---Cl_non-bridging band at about 300 cm⁻¹ was observed in addition to the bands observed in ZnCl₂---ZnX₂ glasses. The addition of KX produces non-bridging anions while the tetrahedral units, ZnX_nCl_4−n²⁻ are also formed.     

Phonons in TiO2---SiO2 glasses

We report the infrared and Raman studies of titanium doped vitreous silica glasses for a number of titanium concentrations. The vibrational modes associated with the randomly oriented chains of SiO₄ tetrahedra show broadenings and shifts. The LO-TO splitting of some Raman active modes decreases with increasing titanium concentration. This is attributed to the decrease in long-range coulomb fields associated with the chains of SiO₄ tetrahedra which are broken by the titanium atoms. The results are discussed in the context of random network models. An increase in the average intertetrahedral angle of the SiO₄ network is calculated from the data. This explains the anomalous decrease in the density of TiO₂---SiO₂ glasses with increasing titanium content. We identify two new modes associated with the distorted titanium tetrahedra. A polarized Raman mode at 1115 cm⁻¹ which is infrared inactive and an unpolarized Raman mode at 945 cm⁻¹ which is infrared active are observed.     

Studies of the optical properties of sodium copolyphosphate glasses

A number of samples of glassy sodium polyphosphate and copolyphosphates of sodium — cobalt, sodium — copper, sodium — nickel, sodium-manganese and sodium — calcium were prepared and their optical properties were investigated. The ultraviolet and visible spectra of these glasses were recorded at the room temperature. It was found that the fundamental absorption edge of these glasses usually occurs in the ultraviolet — visible region. The optical absorption edges (E₀) were calculated by using the relation h ν = B (hν − E₀)² where B is constant. The linear variation of (hν)^1/2 with hν where is the absorption coefficient and hν is the incident photon energy, is taken as evidence of non-direct interband transitions. The E₀ values obtained for copolyphosphate glasses appeared to depend on the size of the counter cation. The infrared spectra of all these glasses appeared to be almost the same, indicating the presence of characteristic P --- O --- P linkages of linear polyphosphate chains and two non bridging oxygen atoms bonded to phosphorus atoms O --- P --- O (PO₂) units in the polyphosphate tetrahedra.     

Ab initio study of NMR spectra of Li2S–SiS2 glass system

We obtained the chemical shielding constants of ²⁹Si in Li₂S–SiS₂ glass system on the basis of molecular orbital calculations. The relative chemical shieldings calculated at the HF/6-31G* level is −16.1 and −23.8 ppm for E(1) and E(0), respectively. These calculations are in good agreement with the previous NMR study: σ(E(2))>σ(E(1))>σ(E(0)). It is found theoretically that incorporation of Li₂S into SiS₂ does not influence the ²⁹Si chemical shift, while incorporation of Li₂O into SiO₂ does to a significant extent. It is also found that the existence of oxygen in Li₂S–SiS₂ glasses increases the chemical shielding of ²⁹Si by about 25 ppm, which is in good agreement with the experimental result.     

Elastic constant anomaly in Fe80−xMoxB20 metallic glasses

The extensional sound velocities V_E of Fe_80−xMo_xB₂₀(x = 6, 7, 8) metallic glasses have been measured between 100 and 600 K in a saturating magnetic field. Young's modulus (E = _E², = density) shows anomalous temperature dependence at and below the magnetic transition temperature of each glass studied. These anomalies are interpreted as arising from the change of long-range spin coupling energy at the Curie temperature in a molecular field approximation. Comparison is made with similar effects in other crystalline and non-crystalline magnetic materials.     

Mg掺杂调制铜铁矿结构CuAlO2多晶的微结构和电热传导

采用固相反应法制备铜铁矿结构的CuAl_1-xMg_xO₂ (x=0、0.005、0.01、0.02、0.03、0.04)多晶,研究了Mg掺杂对CuAlO₂多晶结构和性能的影响。Mg掺杂量x从0增加到0.02,样品均为菱方R3m单相,密度依次提高;所有样品呈半导体的热激活电输运行为,x=0.02样品在室温下的电阻率是未掺杂样品的1/19,热激活能显著下降(x=0时,ρ_{300 K}~5.54 Ω·m,E_a~0.328 eV;x=0.02时,ρ_{300 K}~0.29 Ω·m,E_a~0.218 eV),载流子浓度增加1个量级,主要因为Mg²⁺取代Al³⁺,引入新的受主能级。x>0.02时,MgAl₂O₄尖晶石杂相出现,使其电导率和热导率降低。CuAl_1-xMg_xO₂多晶的晶格热导率在总热导率中占绝对优势,且随温度升高(300~500 K)而下降,晶格热导Callaway模型模拟表明,所有样品的热阻主要源于点缺陷-声子散射。与x=0相比,x=0.02样品的室温热导率增大1倍(κ~13.065 0 W/(m·K)),声速增大,点缺陷-声子散射减弱,分析认为掺Mg形成强的Mg—O键,提高了晶体的弹性模量和声子频率,减弱了本征点缺陷、Mg掺杂引起的质量波动和应变场波动对声子的散射,同时Mg掺杂样品的密度提高也有利于增加热导率。     

Structural analysis of anodic alumina films

Structures of amorphous anodic alumina films have been investigated by the X-ray radial distrubution function and the correlation method. The amorphous anodic alumina films are considered to contain AlO₅ coordination polyhedra as well as AlO₄ tetrahedra and AlO₆ octahedra. Two types of conformation are taken into account by the correlation method; one (model A) is the conformation in which the above coordination polyhedra are arranged in a similar way to that found in the crystalline modifications of γ-Al₂O₃ within a short range of r < 4.5 Å and the other (model B) is the conformation in which coordination polyhedra are randomly arranged. The final model formed by mixing these two conformations (model A and B) in 1 : 1 ratio describes quantitatively the observed scattering intensity curves of the amorphous anodic alumina films.     

Thermal stability and crystallization kinetics of new As–Ge–Se–Sb glasses

Thermal stability and crystallization kinetics of As₁₄Ge₁₄Se_72−xSb_x (where x = 3, 6, 9, 12 and 15 at.%) glasses are studied by the differential scanning calorimetry. The values of the glass transition temperature (T_g) and the peak temperature of crystallization (T_p) are found to be dependent on heating rate and antimony content. From the heating rate dependence of T_g and T_p the values of the activation energy for glass transition (E_t) and the activation energy for crystallization (E_c) are evaluated and their composition dependence discussed. Crystallization studies have been made under non-isothermal conditions with the samples heated at several uniform rates. Using a recent analysis developed for non-isothermal crystallization studies, information on some aspects of the crystallization process has been obtained. The stability calculations emphasized that the thermal stability decreases with increasing the Sb content.     

Wavelength selective materials modification of bulk As2S3 and As2Se3 by free electron laser irradiation

In this study we report first measurements of wavelength-selective infrared-induced materials modification of bulk As₂S₃ and As₂Se₃. These materials are currently being considered as candidate materials for infrared optical fiber transmission in the range of 1–10 μm. Our study is aimed at modifying oxygen, hydrogen and carbon impurities bound to chalcogenide constituent elements in the materials to reduce absorption. Tunable infrared radiation from the W.M. Keck Free Electron Laser (FEL) at Vanderbilt was used to excite specific vibrational modes, S–O–H and CH_x modes in bulk As₂S₃ and Se–H, CH_x and S–H₂ modes in bulk As₂Se₃. Changes in vibrational mode amplitudes are monitored by measuring the intensity of the Fourier transform infrared (FTIR) spectra before and after irradiation at appropriate wavelengths. By tuning wavelengths to hydrogen vibrational modes, we find evidence that hydrogen is released and/or redistributed athermally. In particular, following irradiation at specific resonant wavelengths, vibrational mode amplitudes as monitored by FTIR associated with CH_x are significantly reduced in bulk As₂S₃ and As₂Se₃ samples. In As₂S₃, the changes in CH_x modes are reversed by heat treatment at 115°C for 35 min in nitrogen atmosphere.     

Investigations of g-value correlations associated with the g = 4.3 ESR signal of Fe in glass

The g = 4.3 ESR signal of Fe³⁺ in glass is usually attributed to a “fully rhombic” distortion characterized by E = D/3, where E and D are the splitting constants belonging to the second-order rhombic and axial terms, respectively, of the crystal-field interaction. An alternate statistical approach to the origin of this signal has been given by Peterson et al. on the basis of axial symmetry and broad overlapping distribution of g_| and g that are correlated in opposition (negatively) resulting in spiking at g 4.3. The present paper reports detailed computer studies of the distribution of effective g value produced by large variations in both D and E to test whether negative g-value correlations leading to spiking at g 4.3 are generable from site dependent fluctuations in the second-order crystal-field terms. It is found that the ESR line arising from the middle Kramer's doublet in the fully rhombic limit (E → D/3, |D| > hν) uniquely generates the negative g-value correlation required for spiking at g 4.3.     

Disorder in GeSe2 small crystals and medium-range structure in amorphous GeSe2

The Raman scattering spectra of various forms of GeSe₂, such as amorphous films, single crystals, and small crystals prepared by a gas-evaporation deposition technique, are investigated with an excitation photon energy ranging from 2.1 to 2.8 eV. In the spectra of the crystals, there are two Raman bands, originating from two types of breathing vibrations of the GeSe_4/2 tetrahedra: one is spread over the corner-sharing tetrahedra and the other is quasi-localized on the edge-sharing tetrahedra. In addition to the resonant Raman scattering related to the edge-sharing tetrahedra through the exciton transition observed with 2.71 eV excitation in the single crystals, a new resonant spectrum is found only in the small crystals with 2.54 eV excitation. With increasing disorder in the crystals, the intensity ratio between the two breathing vibration bands increases in the off-resonant excitation region. The Raman spectra in the amorphous states are ascribed to the breathing vibrations of GeSe_4/2 tetrahedra which form a medium-range structure topologically similar to that of crystalline fragments.     

Compositional dependence of the optical gap in Ge1−xSx, Ge40−xSbxS60 and (As2S3)x(Sb2S3)1−x non-crystalline systems

An attempt is made to calculate the compositional dependence of the optical gap (E_g) in Ge_1−xS_x, Ge_40−xSb_xS₆₀ and (As₂S₃)_x(Sb₂S₃)_1−x non-crystalline systems in an alloy-like approach. From the comparison of both the experimental dependence of E_g and the calculated ones using the Shimakawa relation [E_{g AB} = YE_{g A} + (1−Y)E_{g B}] it is assumed that this equation is useful for such systems or parts of the systems which behave like almost ideal solutions.     

X-ray scattering studies of the short and medium range ordering in AsxTe1−x glasses

The structures of As_xTe_1−x(x = 0.2, 0.4, and 0.5) glasses are studied using the differential X-ray anomalous scattering technique. The partial distribution functions have also been obtained for the stoichiometric As₂Te₃ glass, giving information on the medium range ordering. All the glasses show chemical disorder to differing extents, the As₂Te₃ glass being the most disordered. The Te coordination number undergoes a change at x=0.4 where it is 2.5 compared with 2 for AsTe. This change indicates the existence of about 50% of threefold Te sites in the stoichiometric glass, as well as in the Te-rich glasses. Some of the physical properties of the glasses may be explained based on these results.     

Influence of the nucleation time-lag on the activation energy in non-isothermal crystallization

In the present work, the influence of the nucleation time-lag on the non-isothermal glass crystallization is discussed. Differential thermal analysis (DTA) results of an iron-rich glass nucleated by Cr₂O₃ were obtained at different heating rates. The activation energy of crystallization, E_c, and the Avrami parameter, m, estimated by Kissinger's and Ozawa's equations were shown to be dependent on the heating rate. The value of E_c, obtained at 2.5, 5 and 7.5 K/min heating rates was calculated as 299 kJ/mol, while the value of E_c, obtained at 10, 15 and 20 K/min was as 499 kJ/mol. The value of m for ‘low' and ‘high' heating rates were 2.57 and 1.45, respectively. The results were interpreted on the basis of the non-steady state nature of the nucleation process. It was assumed that at high heating rates no nucleation takes place and the crystals grow on a existing fixed number of nuclei; the activation energy of crystal growth, E_g, can be estimated by applying the Kissinger equations. At low heating rates nucleation occurs and the number of nuclei formed is influenced by the heating rate; E_g can be estimated by the Matusita and Sakka equation.     

Structure and properties of the pure and Pr-doped Ge25Ga5Se70 and Ge30Ga5Se65 glasses

The Ge₂₅Ga₅Se₇₀ and Ge₃₀Ga₅Se₆₅ pure and Pr³⁺-doped glasses were prepared by direct synthesis from elements and PrCl₃. It was found that up to 1 mol% PrCl₃ can be introduced in the Ge₂₅Ga₅Se₇₀ and Ge₃₀Ga₅Se₆₅ glasses. Both types of glasses with overstoichiometric and substoichiometric content of Se were homogeneous and of black color. The optical energy gap is E^opt_g=2.10 eV, and the glass transition temperature is T_g=543 K for Ge₂₅Ga₅Se₇₀ and T_g=633 K for Ge₃₀Ga₅Se₆₅. The long-wavelength absorption edge is near 14 μm and it corresponds to multiphonon processes. Doping by Pr³⁺ ions creates absorption bands in transmission spectra, which can be assigned to the electron transitions from the ground ³H₄ level to the higher energy levels of Pr³⁺ ions ³H₅, ³H₆, ³F₂, ³F₃ and ³F₄, respectively. By excitation with YAG:Nd laser line (1064 nm), two intense luminescence bands (1343 and 1601 nm) were excited. The first band can be ascribed to electron transitions between ¹G₄ and ³H₅ energy levels of Pr³⁺ ions. Full width at half of maximum (FWHM) of the intensity of luminescence was found to be 70 nm for (Ge₂₅Ga₅Se₇₀)_1 − x(PrCl₃)_x and (Ge₃₀Ga₅Se₆₅)_1 − x(PrCl₃)_x glasses. The FWHM in selenide glasses is lower than in halide and sulphide glasses. The second luminescence band (1601 nm) can be probably ascribed to the transitions between ³F₃ and ³H₄ energy levels of Pr³⁺ ions. The absorption and luminescence spectra of Pr³⁺ ions in studied glasses are slightly influenced by stoichiometry of glassy matrix. The Raman spectra of studied glasses were deconvoluted and assignment of Raman bands to individual vibration modes of basic structural units was suggested. The structure of studied glasses is mainly formed by corner-sharing and edge-sharing GeSe₄ tetrahedra. The vibration modes of Ga-containing structural units were not found, they are apparently overlapping with Ge-containing structural units due to small difference between atomic weights of Ge and Ga. In the glasses with substoichiometry of Se, the Ge–Ge bonds of Ge₂Se₆ structural units were found. In Se-rich glasses the Se–Se vibration modes were found. In all studied glasses also ‘wrong' bonds between like atoms were found in small amounts. Maximum phonon energy of studied glasses is 320 cm⁻¹.     

A comparison of the medium-range order in glassy GeS2 and Sb2S3

In amorphous (a-) GeS₂ there is only one medium-range order (MRO) dependent X-ray scattering feature, i.e., the ‘first sharp diffraction peak’ (FSDP), whereas in a-Sb₂S₃ all scattering features in the interval 1–2.4 Å⁻¹ are in fact MRO-dependent. The basic element of MRO in a-GeS₂ is a part of a chain of corner bound tetrahedra extracted from the high temperature form of c-GeS₂; in a-Sb₂S₃ it is a part of a crystalline-like (Sb₂S₃)_n band. Ordering of parts of these bands is characterized by a greater interband separation than in the crystal. By contrast with a-GeS₂, the MRO-dependent medium-angle scattering features in a-Sb₂S₃ are less sensitive to fluctuations of the interband (intercluster) ordering distance.     

ε-(AlxGa1-x)2O3/ε-Ga2O3异质结电子输运性质研究

Ga₂O₃是一种新兴的宽带隙半导体,在电力和射频电子系统中具有潜在的应用前景。前期研究以β-Ga₂O₃为主,并且已经对β-(Al_xGa_1-x)₂O₃/Ga₂O₃异质结构中的二维电子气(2DEG)进行了理论计算,本文主要研究ε-(Al_xGa_1-x)₂O₃作为势垒层对ε-(Al_xGa_1-x)₂O₃/ε-Ga₂O₃异质结电子输运性质的影响,首先介绍了ε-(Al_xGa_1-x)₂O₃/ε-Ga₂O₃异质结的结构和性质,分析计算了由于ε-(Al_xGa_1-x)₂O₃/ε-Ga₂O₃异质结的自发极化和压电极化所产生的极化面电荷密度,以及极化对2DEG浓度产生的影响,接着分析了在不同Al摩尔组分下,ε-(Al_xGa_1-x)₂O₃势垒层厚度与合金无序散射、界面粗糙度散射和极性光学声子散射之间的关系。最后通过计算得出结论:界面粗糙度散射和极性光学声子散射对ε-(Al_xGa_1-x)₂O₃/ε-Ga₂O₃异质结的电子输运性质有重要影响,合金无序散射对异质结的输运性质影响较小;2DEG浓度、合金无序散射、界面粗糙度散射和极性光学声子散射的电子迁移率强弱由ε-(Al_xGa_1-x)₂O₃势垒层的厚度和Al摩尔组分共同决定。     

Electronic properties and atomic structure of (Ti, Zr, Hf)---(Ni, Cu) metallic glasses

The available experimental and theoretical data on the electronic density of states at the Fermi level, n(E_F), of non-magnetic melt-quenched TE_100-xTL_x amorphous alloys (Te = Ti, Zr or Hf; TL = Ni or Cu) and for the corresponding crystalline counterparts is reviewed. First, the low-temperature specific heat and superconductive data are summarized, in order to derive experimental n(E_F) values. A comparison with n(E_F) data from theoretical band structure calculations shows good overall agreement, both qualitative and quantitative. By taking into account recent results on the different structural modifications of Ti, Zr and Hf metals, an extrapolation of the composition dependence of n(E_F) in TE-TL glasses to pure amorphous TE metals suggests that the local structure of these TE-TL amorphous alloys may be described by an fcc-like atomic arrangement. Some other reported results, which supply further evidence for the proposed fcc-like local structure in this type of metallic glass, are also discussed.     

The polycarbosilane-to-SixC1−x conversion studied by inelastic neutron scattering and infrared absorption

Polycarbosilane (PC) is a precursor which is converted to Si_xC_1−x fibers by pyrolysis in an inert gas atmosphere. The changes in the atomic vibrational spectrum during the conversion process from PC to Si_xC_1−x have been examined by means of inelastic neutron scattering (INS) and infrared absorption (IR). The existence of transverse-optical(TO)- and longitudinal-optical(LO)-like phonon modes due to amorphous SiC clusters was established in the original and pyrolyzed PC by INS measurements. After pyrolyzing at 700–800°C, these modes appear distinctly around 730 and 930 cm⁻¹, respectively, in the INS spectra. Pyrolysis at 1000°C makes these TO- and LO-like phonon modes sharper.     

A SAXS study of V2O5·nH2O sols and gels

Small-angle X-ray scattering (SAXS) measurements on V₂O₅·nH₂O sols and gels, prepared by dissolving V₂O₅ glass into water at room temperature, show that there are V₂O₅ polymeric fibers entangled like random coils in the sol of n 5000, while the deviation from the random coil behavior occurs in the dilute sol of n 6000.

A Bragg peak appears at the scattering vector h 0.02 Å⁻¹ to be superimposed on an asymptotic h⁻²-course in the SAXS curve of the concentrated sol of n 680. This means that the spatial correlation between V₂O₅ polymeric fibers takes place even in the fluid state.

V₂O₅·nH₂O sols completely lose fluidity at n 250 to transfer to the gel state, where V₂O₅ polymeric fibers begin to pile up in the parallel with a substrate surface. Such a layer structure is preserved up to the gel of n 4. However, V₂O₅ polymeric fibers are randomly oriented within each layer.