Glass formation in the GexTe100−x binary system: Synthesis by twin roller quenching and co-thermal evaporation techniques

The Ge–Te system exhibits one main composition domain where glasses can be easily prepared by melt quenching technique; this domain is centered on the eutectic composition Ge₁₅Te₈₅. In this work, bulk flakes and films of composition Ge_xTe_100−x with x  50 at.% were prepared by two different quenching techniques: (i) the twin roller quenching for bulk flakes and, (ii) the co-thermal evaporation for films (with thickness comprised between 2 and 14 μm). Electron Probe Micro-Analysis was used to check the composition of the materials while X-ray diffraction allowed identifying the amorphous state and/or the crystalline phases present in the Ge_xTe_100−x samples. Thermal properties for both types of materials were investigated by differential scanning calorimetry. The glass-forming regions were: 11.7–22.0 at.% Ge for bulk flakes and 10.2–35.9 at.% Ge for films. A similar thermal behavior of bulk flakes and thick films was highlighted by Differential Scanning Calorimetry.     

Optical and structural properties of Ge–Se bulk glasses and Ag–Ge–Se thin films

The optical and structural properties of Ge₂₀Se₈₀, Ge₂₅Se₇₅ and Ge₃₀Se₇₀ bulk glasses and Ag_x(Ge_0.20Se_0.80)_100−x thin films, where x = 0, 6, 11, 16, 20 and 23 at.% were studied. All samples were confirmed as amorphous according to XRD. The Raman spectra showed increase in 260 cm⁻¹ and 237 cm⁻¹ and decrease in 198 cm⁻¹ and 216 cm⁻¹ bands with different Se content in the bulk samples. The optical bandgap energy of bulk samples decreased (2.17–2.08 eV) and refractive index increased (2.389–2.426 at 1550 nm) with increasing Se content in bulk glasses. The Ge₂₀Se₈₀ thin films were prepared by vacuum thermal evaporation from Ge₃₀Se₇₀ bulk glasses. The Raman spectra of the films showed that peaks at 260 cm⁻¹ and 216 cm⁻¹ decreased their intensities with increasing Ag content in the thin films. The significant red shift of bandgap energy occurred upon different Ag content. The optically induced dissolution and diffusion resulted in graded refractive index profile along the film thickness caused by different Ag concentration. The refractive index increased from the substrate side to the top of thin films. The graded profile was getting more uniform with increasing content of silver in the thin film.     

Thermal dissolution of Ag(Cu) in amorphous Ge(Sx Se1 − x)2 system

Thermally induced solid state reaction of Ag(Cu) into thin Ge(S_x Se_1 − x)₂ films with x = 0, 0.1, 0.4 and 1.0 was investigated using a step by step technique in order to design films with exact Ag(Cu) concentrations for applications in integrated IR optical devices. A thin film of Ag(Cu) was deposited on top of the host Ge(S_x Se_1 − x)₂ films followed by annealing in vacuum at constant temperature, which resulted in homogeneous films of good optical quality. The variation in Ag(Cu) concentration in the films ranged between 5 and 35 at.%. The kinetics of the diffusion and dissolution of metal in the host films was measured by optically monitoring the change in thickness of doped chalcogenide during consecutive thermal annealing steps. The kinetics studies revealed that the thermal dissolution rate of the Cu is greater than that of Ag. Optical UV-VIS transmission spectra of chalcogenide glass layers, undoped and thermal doped by Ag(Cu), were measured to establish the optical properties of the films. The spectra were analyzed using the technique proposed by Swanepoel and the results show that the addition of metal increases the absorption coefficient in the power-law regime and consequently the optical gap decreases and the refractive index increases. The amorphous character of the films was checked by X-ray diffraction which confirmed the amorphous structure of all Ag(Cu)GeSSe thin films.     

Optical and spectroscopic characterization of germanium selenide glass films

A previews study of germanium selenide glass films by scanning electron microscopy and atomic force microscopy revealed a heterogeneous surface morphology consisting of granular regions 15–50 nm in size, which cause high optical losses. The present work was performed in order to further characterize such materials using spectroscopic ellipsometry, infrared (IR) and Raman spectroscopies. Chalcogenide glass films with GeSe₂, Ge₂₈Sb₁₂Se₆₀ and GeSe compositions have been deposited on single crystal silicon and silica glass substrates by vacuum thermal evaporation. The film thickness and the optical constants were obtained from spectroscopic ellipsometry using the Tauc-Lorenz dispersion formula. A model was derived for the film structure, which included a roughness layer at the surface. This top layer was found to have a thickness of 5–15 nm, of the order of the size of the granular regions previously reported. The optical bandgap of the samples increased with increasing selenium content, while the refractive index decreased. Despite a previous report of large scale phase separation in bulk Ge₂₆Sb₁₄Se₆₀ glass, the fundamental IR and Raman spectra obtained in the present work did not provide any clear evidence for such phase separation which could be associated with the heterogeneous nanostructure observed at the surface of the films.     

Vibrational modes and structure of (AgI)x (GeS1.5)100−x chalcohalide glasses

We report a structural investigation of bulk Ge-rich Ge–S–AgI chalcohalide glasses. A vibrational spectroscopic study of the quaternary system (AgI)_x (GeS_1.5)_100−x (0  x_AgI  20) has been undertaken using infrared spectroscopy and Fourier transform Raman scattering. It was found that the GeS_1.5 Raman spectrum is compatible with a glass structure composed of corner- and edge-sharing mixed GeS_nGe_4−n (n = 0–4) tetrahedra where units with n = 2–4 dominate, whilst the fraction of corner-sharing units are significantly lower than the corresponding fraction in the stoichiometric GeS₂ glass. The addition of AgI has revealed a subtle but systematic effect in the structure of the Ge-rich glass matrix, manifested by mild decrease of the ES units and the concomitant increase of complex GeS_nI_4−n or GeS_nGe_mI_4-n−m tetrahedra whose vibrational modes form a continuum at low frequencies. Although, AgI seems to cause subtle structural changes due to the formation of Ge–I bonds, it is also evident that AgI does not act as a real modifier that would depolymerize appreciably the Ge–S network structure.     

Evolution of chemical structure during silver photodiffusion into chalcogenide glass thin films

The change of chemical structure resulting after X-ray and photo-induced silver diffusion into chalcogenide glass (ChG) thin films is monitored by high resolution X-ray photoelectron spectroscopy (XPS). As₄₀S₆₀ and Ge₃₀Se₇₀ thin films, which are based on pyramids and tetrahedral structural units, are investigated as model materials. Survey, core level (As 3d, S 2p, Ge 3d, Ge 2p, Se 3d, Ag 3d_5/2, O 1s, C 1s) and valence band spectra have been recorded and analyzed. Reference point for the binding energy is established by the subsequent deposition of thin gold film on top of the measured samples. The chemical structure gradually changes during diffusion of silver in all the samples. The mechanism of change depends on the chemical composition, thickness of the diffused silver layer and conditions of irradiation. It is revealed that surface oxygen can play important role in the Ag photodiffusion process, leading to phase separation on the surface of the films. Photodiffusion of Ag into As₄₀S₆₀ film leads to the formation of a uniform ternary phase and arsenic oxides on the surface. The formation of ethane-like Ge₂(S_1/2)₆ units together with germanium oxidation are the main outcomes of X-ray induced Ag diffusion into Ge₃₀Se₇₀ film.     

Optical properties of thin films of system (As2Se3)80−x(As2Te3)x(SnTe)20 prepared by PLD

Thin amorphous films from system (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ were prepared by pulsed laser deposition (PLD) from their bulk glasses and their optical properties were studied by spectral ellipsometry. Spectral dependencies of refractive index, absorption and extinction coefficient and optical gap (1.41–1.66 eV for (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ with x = 20 resp. x = 0) were calculated from optical tansmittance, from ellipsometric data by Tauc method. High values of refractive index n₀ (2.49–2.60) and of non-linear χ⁽³⁾ coefficient of index of refraction (4.9–7.5 × 10⁻¹² esu for the glass (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ with x = 0 resp. x = 20) made studied thin films of system (As₂Se₃)_80−x(As₂Te₃)_x(SnTe)₂₀ promising candidates for application in optics and optoelectronics.     

Study of microstructure in Agx(As0.33Se0.67)100−x chalcogenide glasses

Glasses with general formula Ag_x(As_0.33Se_0.67)_100−x were studied by means of modulated differential scanning calorimetry (MDSC), conductivity and permittivity measurements and atomic force acoustic microscopy (AFAM). In the whole range of doping (x = 2–12 at.% Ag) a phase separation was supposed. The proportional amount of the ion-conductive Ag rich phase increased with the Ag content. A rapid increase (almost four orders of magnitude) in the conductivity was observed in the Ag concentration range 4–8 at.%, which could be associated with the interconnection of this ion-conductive phase. The transition from a hole conductivity (at low Ag concentration) to a mixed ionic-hole conductivity at higher Ag concentration was studied by permittivity measurements.     

Te-rich Ge–Te–Se glass for the CO2 infrared detection at 15 μm

Te_80−xGe₂₀Se_x glasses have been prepared along the GeSe₄–GeTe₄ axis using the classical method in silica tube under vacuum. A phase separation domain appears for composition around Te₄₀Ge₂₀Se₄₀. Our attention was turned toward the Te-rich compositions corresponding to 1 < x < 5 at.%. These glasses are transparent from 4 to about 20 μm without any purification of the starting elements. Furthermore the difference ΔT between the crystallization temperature T_x and the vitreous transition temperature T_g lies at about 110 °C that is to say 30 °C higher than for the GeTe₄ reference glass. Finally the introduction of a few percentages of Se makes the glasses much easier to prepare and more stable against crystallization, making them drawable as optical fibers for example. Taking into account their transparency window, encompassing the CO₂ absorption band around 15 μm, the Te_80−xGe₂₀Se_x with 1 < x < 5 at.% could become matchless composition for the CO₂ infrared detection as planed by the Darwin mission of the European Space Agency.     

Structure and optical properties of chalcohalide glasses doped with Pr and Yb ions

Glasses of systems 100-y((GeS₂)₈₀(Sb₂S₃)_20−x(PbI₂)_x)yPr₂S₃, x = 0; 2; 5, 8; y = 0; 0.01; 0.1; 0.5 and 99.9-z((GeS₂)₈₀(Sb₂S₃)₁₈(PbI₂)₂)0.1Pr₂S₃zYb₂S₃, z = 0.05; 0.1; 0.15) were synthesized in high purity. Optically well transparent glasses were obtained for x  5 mol.% PbI₂, for y  0.1 mol.% Pr₂S₃ and for z  0.15 mol.% Yb₂S₃. The glasses were stable and homogeneous, as confirmed by X-ray diffraction and electron microscopy, with high optical transmittivity from visible (red) region up to infrared region (900 cm⁻¹). The density of the glasses was 3.26–3.33 gcm⁻³ for PbI₂ containing glasses. The glass transition temperature, T_g, was 320–336 °C. The optical absorption bands in rare-earth doped glasses corresponded to ³H₄–³F₄, ³H₄–³F₃, ³H₄–(³F₂ + ³H₆) f–f electron transitions of Pr³⁺ ions and to ²F_7/2–²F_5/2 f–f electron transitions of Yb³⁺ ions. Strong luminescence band with maximum near 1340 nm (electron transition ¹G₄–³H₅) was found in Pr₂S₃ doped glasses. The intensity of this band was rising with doping by Yb³⁺ ions. The possible mechanism of the luminescence enhancement is suggested.     

Stimulated interdiffusion and optical recording in Sb/As2S3 nanomultilayers

The role of the compositional modulation at nano-scale dimensions (2–10 nm) in the enhancement of optical recording parameters in nanomultilayers, which contain Sb as active, optical absorbing and diffusing layers and As₂S₃ as barrier (matrix) layers was investigated. Comparison was made with single homogeneous layers made of ternary (As₂S3)_xSb_1−x glasses and co-deposited from Sb and As₂S₃. It was shown that essential increase of the recording efficiency, sensitivity of the bleaching process, broadening of its spectral range occurs due to the stimulated interdiffusion of adjacent components in Sb/As₂S₃ nanomultilayers with optimized Sb layer thickness.     

High field electrical switching behavior of Ge10Se90−xTlx glasses

Electrical switching studies on bulk Ge₁₀Se_90−xTl_x (15 ? x ? 34) glasses have been undertaken to examine the type of switching, composition and thickness dependence of switching voltages. Unlike Ge-Se-Tl thin films which exhibit memory switching, the bulk Ge₁₀Se_90−xTl_x glasses are found to exhibit threshold type switching with fluctuations seen in their current-voltage (I-V) characteristics. Further, it is observed that the switching voltages (V_T) of Ge₁₀Se_90−xTl_x glasses decrease with the increase in the Tl concentration. An effort has been made to understand the observed composition dependence on the basis of nature of bonding of Tl atoms and a decrease in the chemical disorder with composition. In addition, the network connectivity and metallicity factors also contribute for the observed decrease in the switching voltages of Ge₁₀Se_90−xTl_x glasses with Tl addition. It is also interesting to note that the composition dependence of switching voltages of Ge₁₀Se_90−xTl_x glasses exhibit a small cusp around the composition x = 22, which is understood on the basis of a thermally reversing window in this system in the composition range 22 ? x ? 30. The thickness dependence of switching voltages has been found to provide an insight about the type of switching mechanism involved in these samples.     

Structure, electrical, optical and thermal properties of Ge4Sb4Tex (x = 8, 9 and 10) thin films

The crystalline samples of Ge₄Sb₄Te₁₀, Ge₄Sb₄Te₉, and Ge₄Sb₄Te₈ were prepared and their amorphous semiconducting thin films obtained by flash evaporation. Their sheet resistance decreased slowly with temperature up to 147–160 °C with activation energy of electrical conductivity ΔE = 0.40–0.44 eV. Above these temperatures, the sheet resistance drops abruptly by several orders due to crystallization. The drop of resistivity proceeds in two steps. Two steps of phase change were also found on curves of DSC and on the temperature dependence of index of refraction. It pays for slow heating rates, crystallization induced by short (≈30 ns) laser pulses proceeds probably in one step only for all studied samples (as it follows from X-ray diffraction), not only for Ge₂Sb₂Te₅ in which a single phase formation was confirmed. The crystallization temperatures are increasing slightly with decreasing Te content in the series Ge₄Sb₄Te₁₀–Ge₄Sb₄Te₉–Ge₄Sb₄Te₈ from 147 to 160 °C. The X-ray diffractograms revealed that in laser crystallized samples can be found only cubic modification of Ge₂Sb₂Te₅ type (a = 0.6 nm), while the samples annealed (230 °C, 2 h) or annealed after the crystallization with laser pulse, contain also small amounts of hexagonal phase.     

Optical properties and structure of amorphous films Agx(As0.33S0.67−ySey)100−x

As₃₃S_67−ySe_y, where y = 0, 16.75, 33.5, 50.25 and 67, amorphous thin films were prepared by a vacuum thermal evaporation technique. The films with known silver concentrations and good optical quality were prepared by thermal vacuum evaporation of a silver film on the top of As₃₃S_100−ySe_y films with sequential step-by-step optically- and thermally-induced diffusion and dissolution (OIDD) of silver. The range of silver content was x = 0–25 at.%. The kinetics of OIDD of silver were measured optically by monitoring the change of thickness of the undoped part of the chalcogenide during broadband illumination. Compositions of the reaction products have been determined by scanning electron microscope with energy-dispersive X-ray microanalyser EDS. Optical properties $(T\text{,}n\text{,}{E}_{\text{g}}^{\text{opt}})$ of thin films were measured and/or calculated by the Swanepoel method [R. Swanepoel, J. Phys. E: Sci. Instrum. 16 (1983) 1214]. The refractive index increase with increasing silver and selenium concentration has been shown. The difference of the refractive index (Δn) between undoped and silver doped films was ∼0.4 and between As₃₃S₆₇ and As₃₃Se₆₇ was films ∼0.42. Non-linear indices of refraction were estimated according to Tichy’s formula [H. Ticha, L. Tichy, J. Optoel, Adv. Mat. 4 (2002) 381]. The values of non-linear refractive index grew with increasing silver and selenium content. The difference of optical bandgap, $\mathrm{\Delta }{E}_{\text{g}}^{\text{opt}}$, between undoped As₃₃S₆₇ and fully doped films with Ag and Se was ∼1 eV. Raman spectroscopy showed a decrease in S–S or Se–Se bonds with increasing silver content.     

Electrical and optical properties of Sn10Sb20−xBixSe70 (0 x 8) glassy films

Chalcogenide glasses are interesting materials due to their infrared transmitting properties and photo-induced effects exhibited by them. Thin films of the glasses Sn₁₀Sb_20−xBi_xSe₇₀ (0 x 8) prepared by melt quenching technique were evaporated in a vacuum better than 10⁻⁵ mbar. Optical transmission spectra of all the deposited films were obtained in a range 400–2500 nm. The optical band gap and the absorption coefficient were calculated from the transmission data and refractive index was calculated using the swanepoel method. The optical band gap initially increases with increase in Bi content (for x = 2) and then decreases sharply for higher Bi concentrations. The refractive index as well as absorption coefficient decrease with increase in wavelength. The dark activation energy initially increases with increase in Bi content and then decreases with further addition.     

A composition dependent thermal behavior of GexSe35−xTe65 glasses

Alternating differential scanning calorimetric (ADSC) studies have been performed to understand the thermal behavior of bulk Ge_xSe_35?xTe₆₅ glasses (17 ? x ? 25); it is found that the glasses with x ? 20 exhibit two crystallization exotherms (T_c1 & T_c2). On the other hand, those with x ? 20.5, show a single crystallization reaction upon heating. The exothermic reaction at T_c1 has been found to correspond to the partial crystallization of the glass into hexagonal Te and the reaction at T_c2 is associated with the additional crystallization of rhombohedral GeTe phase. The glass transition temperature of Ge_xSe_35?xTe₆₅ glasses is found to show a linear but not-steep increase, indicating a progressive, but a gradual increase in network connectivity with Ge addition. It is also found that T_c1 of Ge_xSe_35?xTe₆₅ glasses with x ? 20, increases progressively with Ge content and eventually merges with T_c2 at x ≈ 20.5 (〈r〉 = 2.41); this behavior has been understood on the basis of the reduction in TeTe bonds of lower energy and increase in GeTe bonds of higher energy, with increasing Ge content. Apart from the interesting composition dependent crystallization, an anomalous melting behavior is also exhibited by the Ge_xSe_35?xTe₆₅ glasses.     

Surface morphology of as-deposited and illuminated As–Se chalcogenide thin films

The role of the composition and of the related changes of the structure in the formation of the surface of amorphous As_xSe_1−x (0 < x < 0.5) layers before and after light treatment was investigated by direct measurements of the surface roughness at nanometer-scale and surface deformations at micrometer-scale under influence of illumination. It was established that the surface roughness of the films, deposited by vacuum thermal evaporation, decreased with increasing As content, especially in compositions 0.1  x  0.3, where the maximum light stimulated surface deformations (localized expansion) occurs. Both relate to the rigidity percolation range and the maximum photoplastic effects, which are not directly connected to the known photodarkening effect, since it is minimal for these compositions.     

Heteroepitaxial growth of Cu2O thin film on ZnO by metal organic chemical vapor deposition

Cuprous oxide (Cu₂O) thin films were grown epitaxially on c-axis-oriented polycrystalline zinc oxide (ZnO) thin films by low-pressure metal organic chemical vapor deposition (MOCVD) from Copper(II) hexafluoroacetylacetonate [Cu(C₅HF₆O₂)₂] at various substrate temperatures, between 250 and 400 °C, and pressures, between 0.6 and 2.1 Torr. Polycrystalline thin films of Cu₂O grow as single phase with [1 1 0] axis aligned perpendicular to the ZnO surface and with in-plane rotational alignment due to (2 2 0)_Cu2O(0 0 0 2)_ZnO; [0 0 1]_Cu2O[1 2¯ 1 0]_ZnO epitaxy. The resulting interface is rectifying and may be suitable for oxide-based p–n junction solar cells or diodes.     

Peculiarities of photoluminescence excited by 157 nm wavelength F2 excimer laser in fused and unfused silicon dioxide

Photoluminescence (PL) spectra and kinetics of high purity amorphous silicon dioxide with ultra low hydroxyl content is studied under the excitation by F₂ excimer laser (157 nm wavelength) pulses. Materials synthesized in the SPCVD plasma chemical process are studied before and after fusion. Two bands are found in the PL spectra: one centered at 2.6–2.9 eV (a blue band) and the other at 4.4 eV (a UV band). Luminescence intensity of unfused material is found to increase significantly with exposure time starting from a very small level, whereas in fused counterpart it does not depend on irradiation time. Both bands show complicated decay kinetics, to which add exponential and hyperbolic functions. The UV band of the unfused material is characterized by decay with exponential time constant τ  4.5 ns and hyperbolic function t⁻ⁿ, where n = 1.5 ± 0.4. For the blue band the hyperbolic decay kinetics with n  1.5 extends to several milliseconds, gradually transforming to the exponential one with τ = 11 ± 0.5 ms. In fused glass relative contribution of the fast component to the UV band is small whereas for the blue one it is great, that allows one to more accurately determine the hyperbolic law factor n = 1.1 ± 0.1 typical for tunneling recombination. Simultaneous intracenter and recombination luminescence, the later occurring with the participation of laser radiation induced defects, add particular features to the decay kinetics. Spectra of the above luminescence processes are different. A less sharp position of bands is associated with the recombination luminescence. The origin of the observed PL features we attribute to the presence of oxygen deficient centers in glass network in the form of twofold coordinated silicon. Such centers being affected by network irregularities can be responsible for the recombination PL component. A great variety of network irregularities is responsible for centers’ structural inequivalence, which causes a non-uniform broadening of PL spectral and kinetic parameters.     

Growth and characterization of pendeo-epitaxial GaN on 4H–SiC substrates

Growth on AlN/4H–SiC substrates of coalesced, non-polar GaN films having volumes of material with reduced densities of dislocations and stacking faults has been achieved from etched stripes via the statistical and experimental determination of the effect of temperature and V/III ratio on the lateral and vertical growth rates of the GaN{0 0 0 1} faces combined with pendeo-epitaxy. AFM of the uncoalesced GaN(0 0 0 1) and GaN vertical faces revealed growth steps with some steps terminating at dislocations on the former and a pitted surface without growth steps, indicative of decomposition, on the latter. Coalescence was achieved via (a) a two-step route and the parameters of (1) and V/III=1323 for 40 min and (2) 1020 °C and V/III=660 for 40 min and (b) a one-step route that employed and a V/III ratio=660 for 6 h. The densities of dislocations in the GaN grown vertically over and laterally from the stripes were 4×10¹⁰ cm⁻² and 2×10⁸ cm⁻², respectively; the densities of stacking fault in these volumes were 1×10⁶ cm⁻¹ and 2×10⁴ cm⁻¹, respectively. The defects in the wing material were observed primarily at the bottom of the film where lateral growth of the GaN occurred from the AlN and the SiC. Plan view AFM also revealed different microstructures and a reduction in the RMS roughness values from 1.2 to 0.95 nm in these respective regions.