The structure of liquid As2Se3 and GeSe2 by neutron diffraction

The liquid structures of As₂Se₃ and GeSe₂ have been investigated using the neutron diffraction patterns. In both cases the structure factor showed a low first peak maximum which follows a weak but apparent pre-peak at very low momentum transfer. It was also observed that the radial distribution function of both materials are characterized by the well-defined first neighbor shell because of the deep minimum on its right-hand side although in the liquid state. These results indicate that strong covalent bondings between unlike atoms in the solid state still remain when melting. Both the structure factor and the distribution curves of these alloys are, on the whole, similar to those in the amorphous phase which have already been examined. A slight difference in the coordination number, however, is found between amorphous and liquid phases of these materials.     

Electron diffraction RDF analysis of amorphous As2Se3,AAs2Se2Te,As2SeTe2 and As2Te3 films

The local order in amorphous films of As₂Se₃, As₂Se₂Te, As₂SeTe₂, and As₂Te₃ has been examined by scanning electron diffraction with direct recording of the intensity of the elastically scattered electrons. The radial distribution functions indicate that there is a systematic increase in mean nearest neighbor distance as the Te concentration is increased, butthe mean coordination number increases slightly around 2.4. Pair function calculation of models shows that the 3-aand 2-fold coordinations of arsenic and chalcogens are retained in these glasses and the interatomic distances are close to those predicted from the Pauling covalent atomic radii of the constituent atomic species. The short range order appears to be similar in amorphous and crystalline As₂Se₃, but different in the case of As₂Te₃ as found by previous workers on bulk materials.     

Effect of hydrostatic pressure on the elastic moduli of As2S3 and As2Se3 glasses at 195 and 296 K

Velocities of 30 MHz longitudinal and shear ultrasonic waves have been measured in As₂S₃ and As₂Se₃ glasses as a function of hydrostatic pressure up to 1.5 kbar at 195 K and 3 kbar at 296 K. The elastic stiffness moduli are found to have relatively large, positive, pressure dependences which are about the same at both temperatures for both glasses. This behavior is attributed to the weakness of bonding between layers comprised of AsS₃ and AsS₃ pyramids.Inspection of data for a variety of glasses reveals a correlation between the value of C_L/3C_T and whether the elastic moduli are increased or decreased by pressure. (C_L is the longitudinal modulus and C_T the shear modulus.)Using the pressure dependences of the elastic moduli obtained in the present work, it is found that volume change is responsible for most of the temperature dependences of the moduli. In addition elastic gammas are obtained which are consistent with thermal Grüneisen gammas at 12 K. The pressure dependence of the volume of As₂S₃ glass at 296 K is calculated using the present results in the Murnagham equation. Agreement with volumetric data of Weir is obtained.     

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.     

On a chaotic potential field in vitreous As2Se3

Some experimental results of the vitreous As₂Se₃ investigation (the photoconductivity spectrum of volume examples, the temperature dependence of the thermoelectric E.M.F., the shift of the optical edge under the temperature and pressure) may be explained by the use of fluctuations of an internal potential field. A hypothesis about the nature of chaotic potential field is proposed, which is based on a negligible magnitude of the gap deformation potential D_g = D_c ? D_v, where D_c and D_v are deformation potentials of band edges. By this hypothesis the fluctuations of the substance density in glass generate the chaotic potential field of magnitude about a half of the gap E_g, while the gap magnitude fluctuates only slightly within some per cent of E_g. It is shown that the displacement of the optical edge at As₂Se₃ amorphization may be a demonstration of the deformation nature of the chaotic potential field in this material.     

Intrinsic and impurity infrared absorption in As2Se3 glass

A quantitative study of infrared absorption in the 250–4000 cm^?1 region of As₂Se₃ glasses doped with small amounts of As₂O₃ or purified by various procedures has been carried out with particular attention to absorption in the wavelength regions of the CO₂ and CO lasers. The dependence of the relative intensities of the oxide impurity bands in the 650–1340 cm^?1 region on the total amount of As₂O₃ added to the glass indicates the existence of three distinct oxide-impurity species. A number of higher-frequency impurity bands which are due to the presence of hydrogen in the glass and whose intensities are highly dependent on the glass-melting conditions have been observed and classified. Intrinsic multiphonon absorption in the 400–1100 cm^?1 region has been interpreted in terms of combination and overtone bands of the two highest-frequency fundamental vibrational modes. Absorption coefficients of As₂Se₃ glass in the 920–1090 cm^?1 CO₂ laser region are limited by intrinsic multiphonon absorption to values of around 10^?2 cm^?1. The lowest absorption coefficients measured in the 1700–2000 cm^?1 CO laser region were around 2 × 10^?3 cm^?1 and may contain contributions from hydrogen-impurity bands.     

Fabrication of highly homogeneous As2Se3 glass under argon flow

The present study relates to a new method for the synthesis of As₂Se₃ glass in a controlled atmosphere. The advantage of this technique is that it does not require sealing of the silica reaction container and therefore makes it likely to substitute the current industrial batch by batch synthesis which actually needs very expensive single-use sealed silica vessels.An experimental device has been developed for these purposes. It is equipped with a stirring mechanism to homogenize the molten bath. In order to avoid contamination by oxygen and moisture, the synthesis is carried out under argon flow (pressure of 1 bar). Material losses during synthesis can be reduced to less than 2% when temperature is progressively increased up to 430 °C. Bulk glass ingots are finally obtained according to a two-step annealing process. Their chemical composition is analyzed by EDS and shows a variation range of less than 0.2%. The excellent reproducibility of the given method is also confirmed by the refractive indexes, that do not differ for more than 1 · 10⁻³ from one another.Adverse absorption bands due to oxygen do not occur in the 8-12 μm spectral region when 1000 ppm of Mg is added. As no distilling operation has been carried out until now, the magnesium oxide partially keeps staying in the glass and leads to scattering losses at short wavelengths.     

Bulk and impurity infrared absorption in 0.5 As2Se30.5 GeSe2 glass

A study of infrared absorption in the 250–4000 cm^?1 region has been carried out for 0.5 As₂Se₃0.5 GeSe₂ glasses quantitatively doped with oxide impurity. The frequencies of the intrinsic 2- and 3-phonon absorption bands at 490 and 690 cm^?1 correspond well to those predicted from combinations of the high frequency bands in the first order IR and Raman spectra of As₂Se₃ and GeSe₂ glasses.Glasses doped with As₂O₃ exhibit the same oxide impurity absorptionbands as those doped with GeO₂. Unlike As₂Se₃ glass, at impurity concentrations up to 1000 ppm As₂O₃, 0.5 As₂Se₃0.5 GeSe₂ glass exhibits only one major oxide impurity species, characterized by absorption bands at 780 and 1260 cm^?1 and due to oxygen bonded to network Ge. The observation of a much weaker network AsO vibration band at 670 cm^?1 confirms that oxygen bonds preferentially to Ge in this glass. The same minor oxide species appears to determine excess IR absorption at the CO₂ laser wavelength of 10.6 μm in both As₂Se₃ and 0.5 As₂Se₃ 0.5 GeSe₂ glasses. The frequencies and intensities of absorption bands due to hydrogen impurities are also quite comparable for these two materials.     

EXAFS measurements for liquid As2Se3 at high temperatures and pressures

Extended X-ray absorption fine structure (EXAFS) spectra from liquid As₂Se₃ around both the As and Se K-edges in the temperature-pressure range up to 1400°C and about 60 bar were measured. For the EXAFS measurements, a new type of high pressure vessel and a sample cell of own design made of polycrystalline sapphire were developed. Distinct EXAFS oscillations were obtained even at 1400°C. When the semiconductor-to-metal transition occurs at about 1000°C, the local environment around a central As atoms is substantially changes and a new As neighbor site is induced.     

Athermal photo-amorphization of As50Se50 films

A novel process for producing amorphous state, namely photo-induced transformation, is reported in a chalcogenide material, As₅₀Se₅₀, which in the crystalline phase is a molecular solid consisting of As₄Se₄ molecules. The crystalline-amorphous transition is athermal. Although the mechanism of photo-induced transformation to the amorphous state is not known, two possibilities are suggested: either photon-induced intramolecular bond-breaking leading to a cross-linked CRN-like network, or intermolecular bond-breaking resulting in an orientationally disordered molecular glass.     

Study of recombination of photocarriers in a-As2Se3 and As2Te3 by photoconductivity and photo-absorption measurements

Time-dependent photoconductivity and photo-absorption measurements, the latter using probe beams of 0.1 eV and 1.4 eV, were analyzed on the basis of a saturated band tail model. By a best fit procedure of theory to experiment band structure and recombination parameters for a-As₂Se₃ were obtained.     

Relief holograms in thin films of amorphous As2Se3 under high laser exposures

Hologram recording into thin films of amorphous As₂Se₃ was investigated experimentally. Apart from a hologram recorded at a relatively low exposure of several joules per square centimeter, a new hologram can be recorded at exposures of 10⁴–10⁵ J/cm². At these exposures a relief hologram is formed on the surface of the As₂Se₃ film. The holograms can be erased by heating or by illumination and new holograms can be recorded.     

The structure analysis liquid Sb2Se3 by neutron diffraction

The radial distribution analysis of liquid Sb₂Se₃ at 670, 720 and 770°C is carried out by the neutron diffraction method. A small but apparent maximum is found at $\text{K = 1.2}\text{A}\text{?}{}^{\mathrm{?1}}$ in the structure factor. The interatomic distance and the coordination number are 2.74 Å and 2.84 respectively, at 670°C. These results suggest that intramolecular bonds in the crystalline Sb₂Se₃ remain unbroken in the liquid state. The general feature of the structure factor and the distribution function for liquid Sb₂Se₃ is similar to that for the amorphous state. However, it is clear that the liquid phase tends to have a similar atomic arrangement to that of liquid tellurium.     

Crystallization of amorphous selenium and As0.005Se0.995

The effect of temperature on the crystallization kinetics of bulk amorphous selenium and the alloy As_0.005Se_0.995 has been studied using differential scanning calorimetry. A time-temperature-transformation (TTT) curve has been plotted from isothermal results over the temperature range 320 to 490 K, and shows the presence of two minima for both materials. Using the empirical Avrami expression for solid-state transformations, a number of kinetic parameters has been determined.     

X-ray diffraction measurements for liquid As2Se3 up to the semiconductor-metal transition region

X-ray diffraction measurements were performed for liquid (1-) As₂Se₃ at temperatures and pressures up to 1500°C and 70 bar. A high-pressure vessel and a sapphire sample cell were developed, according to the authors' own design, for measurements using the energy-dispersive method. The structure factor becomes broadened with increasing temperature and changes significantly at about 1000°C accompanied by the semiconductor-to-metal (SC-M) transition; the first sharp diffraction peak around 1.2Å⁻¹ disappears and the second and third maxima merge. The nearest-neighbor distance and the average coordination number start to increase when the SC-M transition occurs. The density of 1-As₂Se₃ in the temperature and pressure range up to 1600°C and 700 bar, respectively, were also measured by the X-ray absorption method. A volume contraction occurs in the SC-M transition region.     

Raman scattering of the mixed chalcogenide glass system As2SxSe3-x

Polarized room temperature Raman spectra of glassy As₂S_xSe_3-x for 0≦×≦3 have been measured. Spectra for crystalline As₂S₁Se₂ are reported. The polarization and intensity dependence upon composition are consistent with mixed pyramids of composition As₂S_nSe_3-n and preclude phase separation in the glassy system.     

Structure and bonding in the mixed chalcogenide system As2SxSe3−x

⁷⁵As Nuclear Quadrupole Resonance (NQR) lineshape measurements for the amorphous mixed chalcogenide system As₂S_xSe_3?x are reported. The line-shapes are asymmetric and approximately 8 MHz in width (full width at half maximum). The peak resonance frequency is observed to increase approximately linearly with x. The NQR results indicate the presence of mixed As₂(S, Se)₃ pyramidal structural units and are thus not consistent with models that predict the occurrence of anion subsite segregation. NQR measurements performed on crystalline As₂SSe₂ lend support to the structural model proposed for the glasses.     

Optical characterization of As2Se3-Ag4SSe-SnTe amorphous thin films

Amorphous thin films from the system As₂Se₃-Ag₄SSe-SnTe were prepared by thermal vacuum evaporation from the corresponding bulk glassy samples. The film structure and surface morphology were investigated by scanning electron microscopy and atomic force microscopy; the results revealed uniform, smooth and homogeneous coatings. The amorphous chalcogenide films are transparent in a wide spectral range as shown by transmission and reflection measurements in the VIS and NIR regions. The optical band gap was determined and its compositional dependence is discussed in terms of structural considerations and the formation of charged defect centers.     

X-ray photoelectron spectroscopic studies on Se/As2S3 and Sb/As2S3 nanomultilayered film

Photoinduced diffusion in Se/As₂S₃ and Sb/As₂S₃ nanomultilayered thin films are studied by X-ray photoelectron spectroscopy (XPS). The XPS measurements show the atomic movements during photoinduced diffusion in Se/As₂S₃ and Sb/As₂S₃ nanomultilayered film. The analysis of experimental data describes the nature of light induced changes in different structural units.     

Magnetic behaviour of 20Fe2O380[3B2O3(1−χ)PbOχAs2O3] glasses

The results of magnetic measurements performed on 20Fe₂O₃80[3B₂O₃(1?χ)PbOχAs₂O₃] glasses, in the temperature range 4.2 to 300 K are reported. By decreasing the temperature a downward curvature of reciprocal susceptibility is observed for T<50 K. The composition dependence of the paramagnetic Curie temperatures and Curie constants is discussed.