119Sn Mössbauer studies of glassy and crystalline compounds in the chalcogenide system SeSnAs

¹¹⁹Sn Mössbauer measurements have been carried out on 18 chalcogenide glasses of different composition in the system SeSnAs. In all cases tin is four-coordinated and appears to be tetrahedrally surrounded by selenium. Two of the glasses (Se₆₀Sn₃As₃₇ and Se₄₇Sn₃As₅₀) were crystallized by heat treatment, and their Mössbauer spectra have been measured as a function of crystallization temperature and annealing time. As a result of the heat treatment, crystalline SnSe and SnSe₂ are precipitated. The amount of each compound is determined by the composition of the original glass and the remaining glassy or crystalline phase (As₂Se₃ and As₄Se₄). The degree of the crystallization depends on the temperature and the annealing time, but not the mass ratio of the tin selenides formed.     

Preparation of mixed arsenic/antimony chalcogenide glasses and some optical and thermo-physical properties

The preparation of mixed glasses of As₂S_3−xSe_x (x = 0–3) and (1 − y) · As₂S₃y · Sb₂S₃ (y = 0–1) has been carried out by an in situ pouring technique. X-ray diffraction (XRD) was used to confirm the glassy nature of the materials and monitor devitrification. Visible-IR transmission, photoluminescence, refractive index and micro-Raman were measured as a function of composition. Microhardness (MH) and thermal expansion coefficient (TEC) were also measured. Raman peaks in As₂S₃ and As₂Se₃ were observed around 338 cm⁻¹ and 230 cm⁻¹, respectively in this first composition series in which S was replaced by Se. When As was replaced by Sb, in the case of second composition series, the As₂S₃ related Raman peak became broader and shifted to lower wave number, reflecting some structural change/devitrification. MH increased (1.31–1.50 GPa) with Se and Sb content while the TEC was found to decrease (2.5–1.4 × 10⁻⁵/K). The progressive increase in the content of either Se or Sb in As₂S₃ is anticipated to modify bond lengths and bond angles. The combined effect of these structural modifications would change the local structure of the glass forming a more rigid glass network thereby increasing the hardness and decreasing TEC.     

Characterization of new sulfur and selenium-based glasses containing lead iodide

The aim of this work is to investigate and qualify vitreous regions in new chalcogenide systems containing highly polarizable elements like S, Se, As, Sb, Bi, Pb and I. The sulfur based system, As₂S₃-Sb₂S₃-Bi₂S₃-PbI₂, as well as the selenium containing glasses As₂Se₃-Sb₂Se₃-PbI₂ have been studied. Large vitreous regions have been defined in the both systems: sulfur and selenium. Indeed, several glass compositions can accept in the vitreous network a molar concentration near 50% of PbI₂. Physical properties such as glass transition temperature, crystallization temperature, optical transmission, band-gap wavelength have been measured versus glassy compositions.     

Selective wet-etching and characterization of chalcogenide thin films in inorganic alkaline solutions

This paper deals with sensitivity of chalcogenide based photoresists in inorganic alkaline solutions. The thin films of As₃₃S₆₇, As₃₃S₅₀Se₁₇, As₃₃S_33.5Se_33.5, As₃₃S₁₇Se₅₀, and As₃₃Se₆₇ were studied. The selective wet-etching was carried out using NaOH, Na₂S and (NH₄)₂S alkaline solutions. The different sensitivity according to sample composition and used etching solution were found. Chalcogenide films as a potential photoresists could be classified either as ‘high-contrast’ or ‘low-contrast’ depending on the sample compositions, type of etchant and its concentration or on incident light energy.     

The structure of Hg-doped As2Se3 glasses

The structure of the semiconducting glassy As₂Se₃Hg_x system was investigated in a composition range x = 0.005?0.12. An explanation of the anomalous behaviour of the macroscopic density is proposed, based on the analysis of radial electron density distribution curves. A formula is given which correlates quantitatively the magnitude of coordination spheres with the experimental macroscopic density.     

Infrared studies of Se-based polynary chalcogenide glasses (III): YxZxSxSe100−3x (Y = Ge,As; Z = As,Te)

The infrared (IR) absorption spectra for Y_xZ_xS_xSe_100?3x glasses (Y = Ge, As; Z = As, te), with x = 2.5 and 5.0, are measured in the wavenumber region 700-60 cm^?1 at room temperature. These IR spectra are qualitatively explained by comparing with the IR spectra of the binary and ternary glasses. In Ge_xAs_xS_xSe_100?3x glasses (x ? 5.0), the main spectral features are explained by both spectra of the two ternary glasses Ge_xS_xSe_100?2x and As_xS_xSe_100?2x. In Ge_xS_xTe_xSe_100?3x glasses (x ? 5.0), the main spectral features are well explained by both spectra of the two ternary glasses Ge_xS_xSe_100?2x and Ge_xTe_xSe_100?2x. On the other hand, main spectral features in As_xS_xTe_xSe_100?3x glasses (x ? 5.0) are well explained by both spectra of the ternary glasses As_xS_xSe_100?2x and the binary glasses Se_100?xTe_x. In these glasses with low concentrations (x ? 5.0) some chemical bonds are confirmed and some structural units estimated.     

The electronic properties of glasses in the Cux(As0.4Se0.6)100−x system with x between 5 and 30

Data are presented on the dc conductivity, thermopower and optical absorption of glasses in the CuAs₂Se₃ system. The electronic properties of the alloys differ markedly from those of As₂Se₃, but variations in composition do not introduce significant changes in properties, until the atomic percent of copper is greater than 25. The results are interpreted in terms of small polaron transport.     

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.     

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.     

Non-linear properties of chalcogenide glasses and fibers

High purity chalcogenide glasses were prepared in the series As₂S_(3?x)Se_x where x = 0 to 3. The measured third order non-linearities increase with the value of x, and are up to about 1000 times larger than silica for As₂Se₃ glass. We show that the anharmonic oscillator model, using the normalized photon energy, gives an excellent fit to the data over three orders of magnitude. Single mode optical fibers based on As₂S₃ and As₂Se₃ glasses have been fabricated using the double crucible technique and the Stimulated Brillouin Scattering (SBS) investigated. The threshold intensity for the SBS process was measured and used to estimate the Brillouin gain coefficient. Preliminary results indicate record high values for the figure of merit and theoretical gain, compared to silica, which bodes well for slow-light based applications in chalcogenide fibers.     

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.     

Glass formation and properties of chalcogenide systems XXVI: Permittivity and the structure of glasses AsxSe1−x and GexSe1−x

Correlation between the real part of the dielectric constant and the structure of glasses in the system As_xSe_1?x and Ge_xSe_1?x is reported. The mole polarization is calculated using the Sellmeyer approximation neglecting the Lorentz field. The vibrationally caused part of the permittivity which is obtained by subtraction of the mole refraction reflects ordered states in the investigated series. Besides the known crystalline compounds As₂Se₃ and As₄Se₄ the formation of the vitreous AsSe₃ and As₃Se₂ from the liquid state has to be supposed. In the system Ge_xSe_1?x the formation of the compounds GeSe₂ and Ge₂Se₃ is completed by GeSe₄ which as Ge₂Se₃ obviously only exists in the non-crystalline state. GeTe₄ has been reported as a metastable crystalline phase. The temperature dependence of ?_r of vitreous As₂Se₃ is tentatively interpreted in terms of the dipole orientation caused by conversion of the charge in valence alternation pairs.     

Neutron studies of an inorganic plastic glass

A neutron diffraction investigation has been performed of the structure of four chalcogenide glasses, using the D4c diffractometer on the high-flux reactor at the Institut Laue-Langevin (ILL). Vitreous Ge₃As₅₂S₄₅ is shown to have a structure based on As₄S₃ molecules, whereas that of its selenide analogue, vitreous Ge₃As₅₂Se₄₅, involves far fewer As₄Se₃ molecules. Two As₂X₃ reference glasses (X = S or Se) have purely network structures. As-X, and As-As bond lengths have been extracted, together with their associated co-ordination numbers, from peak fits to the real space correlation functions, T(r), and suggest that all four glasses are chemically ordered; i.e. that they contain the maximum possible number of As-X (and Ge-X) bonds. The molecular nature of vitreous Ge₃As₅₂S₄₅ is evident from the enhanced first diffraction peak relative to the As₂S₃ reference glass, and has been further investigated by comparing its interference function, Qi(Q), with that expected for an isolated As₄S₃ molecule. On the other hand, the second diffraction peak for vitreous Ge₃As₅₂S₄₅ is not reproduced by a random orientation molecular model, indicating that there is orientational correlation between adjacent molecules, and this is discussed with respect to the structure of the corresponding As₄S₃ crystalline phases. The neutron-weighted vibrational density of states (VDOS) for vitreous Ge₃As₅₂S₄₅, obtained with the ISIS MARI spectrometer, unambiguously confirms the existence of As₄S₃ molecules, as revealed by a peak at ~ 34 meV arising from the triangle of As atoms that form the base of the molecule. MARI data recorded at ambient temperature also reveal a strong quasi-elastic component in the scattered intensity, which has been further investigated using the IN5 quasi-elastic scattering spectrometer (ILL) and indicates the presence of rotational diffusion of the As₄S₃ molecules; i.e. that, at ambient temperature, vitreous Ge₃As₅₂S₄₅ behaves as a plastic glass. A possible structural model for vitreous Ge₃As₅₂S₄₅ comprises a two-dimensional tangled GeS₂ net with As₄S₃ molecules trapped in its folds whereas, for vitreous Ge₃As₅₂Se₄₅, a clathrate model appears more appropriate.     

Local atomic arrangement and bonding studies in amorphous As2Se3As4Se4

The local atomic arrangement in amorphous As₂Se₃As₄Se₄ glasses was investigated with ESCA (electron spectroscopy for chemical analysis) and RDF (radial-distribution function) analysis. Measured changes of RDF peak areas and ESCA chemical shifts give direct evidence for the preservation of the local bonding schemes of both crystalline As₂Se₃ and As₄Se₄ in their amorphous states. The valence-band structures of amorphous As, Se, As₂Se₃ and As₄Se₄ are also measured with ESCA and discussed in conjunction with the bonding schemes of these glasses.     

DC electronic transport in binary arsenic chalcogenide glasses

dc conductivity and Seebeck measurements have been carried out at temperatures below T_g on well characterized bulk samples of amorphous As₂Te₃, As₂Se₃, and As₂S₃. Several models for conduction in these materials have been compared to the data. It is concluded that the models involving polaron hopping conduction are in better agreement with available data than are models involving hopping in the tails of localized band-tail states.     

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.     

Infrared laser ablation of glassy As2Se3

In this study, we report the first measurements of wavelength and pulse length dependence of ablation thresholds in glassy As₂Se₃. Ablation yields, obtained from time-of-flight spectra were compared to laser intensity curves to obtain laser ablation thresholds. The wavelength dependence of the ablation thresholds were obtained by tuning the Vanderbilt–Keck free electron laser in the range of 3.2–5 μm. Pulse dependence of the ablation thresholds were obtained with a 5 μs macropulse in the wavelength range 3.2–5 μm and with macropulses ranging from 200 to 1000 ns at the wavelength of 3.5 μm. The wavelength dependence of the ablation threshold did not indicate that impurity absorption was a major factor in the ablation process in glassy As₂Se₃. The ablation threshold decreased with wavelengths corresponding to higher photon energies. In addition, a sharp increase in ablation threshold was observed with decrease in the macropulse length. Optical images of ablation craters at intensities above the threshold reveal significant melting on the sample surface. We will discuss the wavelength and pulse length dependence of the laser ablation threshold in glassy As₂Se₃ in terms of a multi-photon process and a cumulative heating process.     

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.     

High-field behaviour of amorphous AsSe films

Thin films of composition AsSe_χ where 0.8 ≤ χ ≤ 1.0 obtained by the evaporation of both crystalline and glassy As₂Se₃ have been examined for their high-field behaviour. The films exhibit two essentially linear I–V regions with a smooth nonlinear change over. While the initial linear region may perhaps correspond to a Poole-Frenkel emission, the very high-field linear region is likely to arise from a distortion of the band shapes and lowering of the mobility gap.     

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.