Crystallization process on amorphous GeTeSb samples near to eutectic point Ge15Te85

One of most important properties of some tellurium-based chalcogenide glasses is the optical and electrical switching between two states: the glass and the crystalline state. The understanding in these systems of the glass to crystal transition and its transformation kinetics is essential for their application in non-volatile memories. GeTeSb and GeTe amorphous samples of compositions close to the eutectic point Ge₁₅Te₈₅ were obtained by rapid solidification from the liquid state employing melt spinning technique. The glass forming ability of this system, for this cooling technique, is restricted to a small composition range nearby the binary eutectic. The crystallization kinetics of the samples was studied by means of differential scanning calorimetry (DSC) under both isothermal and continuous heating regimes. The quenched samples and the crystallization products have been characterized by X-ray diffraction with Cu(Kα) radiation. The crystallization temperature, activation energy, crystallization enthalpy and the dependence of these properties on concentration are reported. The crystallization study of Ge₁₅Te₈₅ glasses shows: a primary crystallization of Te superimposed with a secondary crystallization of GeTe. The addition of Sb (5 at.%) to the eutectic point Ge₁₅Te₈₅ modifies this behavior: the crystallization of Ge₁₃Sb₅Te₈₂ glasses consists on the crystallization of Te and Ge₂Sb₂Te_5. The crystallization of the ternary glasses was modeled.     

Electrical switching studies on Ge-Te-Tl chalcogenide glasses: Effect of thallium on the composition dependence of switching voltages

Bulk Ge₁₇Te_83−xTl_x glasses (0 ≤ x ≤ 13), have been found to exhibit memory type electrical switching. The switching voltages (also known as threshold voltage — V_th) of Ge₁₇Te_83−xTl_x glasses are found to decrease with increasing thallium content. The rate of decrease of V_th is greater at lower concentrations and V_th falls at a slower rate for higher thallium concentrations (x ≥ 6).The addition of thallium to the Ge-Te network fragments the covalent network and introduces ionic nature to it; the reduction in network connectivity leads to the decrease in switching voltages with thallium content. The decrease in the glass transition temperatures of Ge₁₇Te_83−xTl_x glasses with increasing thallium concentration supports the idea of decrease in network connectivity with Tl addition. The more metallic nature of Tl also contributes to the observed reduction in the switching voltages of Ge₁₇Te_83−xTl_x glasses with Tl content.Further, there is an interesting correlation seen between the threshold voltage V_th and the average bond energy, as a function of Tl content. In addition, the switching voltages of Ge₁₇Te_83−xTl_x glasses have been found to decrease with sample thickness almost linearly. The set-reset studies indicate that the Ge₁₇Te₈₁Tl₂ sample can be switched for more than 10 cycles, whereas other glasses could not be reset beyond two switching cycles.     

Evaluation of basic physical parameters of quaternary Ge–Sb-(S,Te) chalcogenide glasses

New quaternary chalcogenide Ge_xSb_40?xS₅₀Te₁₀ (x = 10, 20 and 27 at.%) and Ge_xSb_40?xS₅₅Te₅ (x = 20 and 27 at.%) glasses have been synthesized and the compositions have been characterized applying prompt gamma-ray activation analyses, neutron diffraction, and material density measurements. Using the experimental data, the basic physical parameters, such as average atomic volume, packing density, compactness, average coordination number, number of constrains, average heat of atomization and cohesive energy, of the synthesized glasses are evaluated and the results are discussed in a function of glass composition.     

Effects of Ge addition on the optical and electrical properties of eutectic Sb70Te30 films

The aim of this work is to study the influence of Ge addition on the optical and electrical properties in eutectic SbTe thin films (with the compositions: Sb₇₀Te₃₀, Ge₂Sb₇₀Te₂₈, Ge₅Sb₇₀Te₂₅ and Ge₁₀Sb₆₅Te₂₅) using visible optical reflectance, ellipsometry measurements, near infrared transmittance spectra, and four probe electrical resistivity measurements. From near infrared transmittance measurements the optical band gap was determined using Tauc’s expression for amorphous materials, a value of about 0.47 eV was obtained without any clear dependence on the Ge content. All amorphous films have approximately the same reflectance value, however the contrast ratio between the crystalline and amorphous phases decrease with increase of Ge. Using in situ four probe measurements versus temperature the dependence of the activation energy of conductance and the onset of the crystallization temperature have been determined for different materials. Four probe measurements have shown that the resistivity of amorphous films increases with increase of Ge. The results obtained have shown that optical and electrical properties of SbTe films with near eutectic composition change with the Ge content and depending on the application, in either optical or electrical memory devices, the most suitable composition needs to be determined.     

The composition dependence of electrical switching behavior of Ge7Se93−xSbx glasses

Bulk Ge₇Se_93?xSb_x (21 ? x ? 32) glasses are prepared by melt quenching method and electrical switching studies have been undertaken on these samples to elucidate the type of switching and the composition and thickness dependence of switching voltages. On the basis of the compressibility and atomic radii, it has been previously observed that Se-based glasses exhibit memory switching behavior. However, the present results indicate that Ge₇Se_93?xSb_x glasses exhibit threshold type electrical switching with high switching voltages. Further, these samples are found to show fluctuations in the current–voltage (I–V) characteristics. The observed threshold behavior of Ge₇Se_93?xSb_x glasses has been understood on the basis of larger atomic radii and lesser compressibilities of Sb and Ge. Further, the high switching voltages and fluctuations in the I–V characteristics of Ge–Se–Sb samples can be attributed to the high resistance of the samples and the difference in thermal conductivities of different structural units constituting the local structure of these glasses. The switching voltages of Ge₇Se_93?xSb_x glasses have been found to decrease with the increase in the Sb concentration. The observed composition dependence of switching voltages has been understood on the basis of higher metallicity of the Sb additive and also in the light of the Chemically Ordered Network (CON) model. Further, the thickness dependence of switching voltages has been studied to reassert the mechanism of switching.     

Bimolecular relaxation kinetics observed in radiation-optical properties of Ge–As(Sb)–S glasses

Numerical parameters of decaying bimolecular relaxation kinetics are analysed for radiation-optical properties of chalcogenide glasses within ternary stoichiometric As₂S₃–GeS₂ and Sb₂S₃–GeS₂ as well as non-stoichiometric As₂S₃–Ge₂S₃ systems in dependence on their composition. It is shown, that the observed compositional dependences of bimolecular relaxation parameters have a monotonic character in the glasses of both stoichiometric systems, while the anomalous extremum-like behavior is observed in the vicinity of average coordination number close to 2.7 in non-stoichiometric glasses.     

The electrical switching and thermal behavior of bulk Ge15Te85 − xSnx and Ge17Te83 − xSnx glasses

Bulk Ge₁₅Te_85 ? xSn_x and Ge₁₇Te_83 ? xSn_x glasses, are found to exhibit memory type electrical switching. The switching voltages (V_t) and thermal stability of Ge₁₅Te_85 ? xSn_x and Ge₁₇Te_83 ? xSn_x glasses are found to decrease with Sn content. The composition dependence of V_t has been understood on the basis of the decrease in the OFF state resistance and thermal stability of these glasses with tin addition. X-ray diffraction studies reveal that no elemental Sn or Sn compounds with Te or Ge are present in thermally crystallized Ge–Te–Sn samples. This indicates that Sn atoms do not interact with the host matrix and form a phase separated network of its own, which remains in the parent glass matrix as an inclusion. Consequently, there is no enhancement of network connectivity and rigidity. The thickness dependence of switching voltages of Ge₁₅Te_85 ? xSn_x and Ge₁₇Te_83 ? xSn_x glasses is found to be linear, in agreement with the memory switching behavior shown by these glasses.     

Structural study of GexSb40−xS60 (x = 10, 20 and 30) glasses

The atomic structures of Ge–Sb–S ternary glasses have been investigated by using the neutron diffraction method. The structure factor, S(q), for Ge_xSb_40−xS₆₀ (x = 10, 20 and 30) has a first sharp diffraction peak (FSDP) at around 1.1 Å⁻¹. The oscillation in S(q) persisted up over 25 Å⁻¹ indicates that the chemical short-range order is presented in these glasses. The aspect of S(q) for Ge₁₀Sb₃₀S₆₀ is different from those for Ge₂₀Sb₂₀S₆₀ and Ge₃₀Sb₁₀S₆₀. These results show that the atomic structure changes drastically between Ge₁₀Sb₃₀S₆₀ and Ge₂₀Sb₂₀S₆₀. The short-range order of tetrahedral GeS₄ and pyramidal SbS₃ units seems to exist in the Ge_xSb_40−xS₆₀ (x = 10, 20 and 30) glasses.     

Thermally-induced structural and electrical effects in GeTe-based amorphous alloys

The thermal, structural electrical properties of bulk glasses based on GeTe compositions near the binary eutectic, Ge₁₅Te₈₅, are studied. Information regarding the non-crystalline state and the transformation from the non-crystalline to the crystalline state is reported. The particular alloys studied represent binary (Ge₁₇Te₈₃), ternary (Ge₁₅Te₈₀As₅) and quaternary (Ge₁₅Te₈₁Sb₂S₂) compositions. Structural information is obtained using X-ray diffraction techniques and density measurements. Thermal data are reported from differential scanning calorimetry (DSC), thermogravimetry (TGA) and mass spectrometry results. The electrical conductivity is measured as a function of temperature and, on the ‘as-prepared’ glasses, shows semi-conducting behavior with activation energies, E, of 0.43–0.48 eV. DSC, TGA and X-ray powder diffraction patterns indicate the samples crystallize as Te and GeTe in a two-step process, and melt at the binary eutectic temperature. The binary vaporizes as Te and GeTe in a two-step process. GeTeAs and GeTeSbS vaporize by essentially the same mechanism, with As evaporating (<300°C) before the Te, and Sb and S evaporating (420–480°C) after the Te but before GeTe. The results show that the properties of the bulk ‘as-prepared’ glasses are strikingly similar. Thermally-induced changes in the structural and electrical properties of bulk samples have been examined following a series of anneals (5 h, vacuum) at temperatures from 111°C to 190°C (glass transition temperature $\text{?125?133°}\text{C}$; crystallization temperature $\text{?206?228°}\text{C}$ as determined by DSC). DSC, TGA and mass spectrometry results have been correlated to electrical and structural changes. Results show that crystalline Te nucleates at the surface and forms a conductive surface layer. The conductivity of this surface layer is nearly temperature independent with E ≈ 10^?2 eV for all three alloys. Crystallization and the associated electrically conductive regions extend into the bulk material with further annealing. In these disordered alloys the additives As and Sb + S apparently do not act as electrical dopants in the sense of affecting the conductivity activation energy. The additives Sb + S however do retard crystallization of GeTe. The secondary crystallization product, GeTe, apparently changes the conduction mechanism to either a metallic or degenerate semiconductor type behavior.     

Capacitance-voltage characteristics of In0.3Ge2Sb2Te5 thin films

The influence of indium doping on the capacitance variation with temperature and applied bias voltage of Ge₂Sb₂Te₅ is investigated. The capacitance-voltage (C-V) measurements of In_0.3Ge₂Sb₂Te₅ and Ge₂Sb₂Te₅ thin films were performed for a sweep of voltages from −20 to +20 V at different temperatures. The results show different capacitance behavior of In_0.3Ge₂Sb₂Te₅ and Ge₂Sb₂Te₅ films. As the temperature increases the capacitance of the indium-doped sample decreases and becomes negative. The negative capacitance effect might be attributed to a significant increase of the film’s conductivity due to temperature and applied bias voltage. The nonlinearity in the capacitance and conductivity could be related to the nucleation mechanism as the temperature becomes close to the amorphous-crystalline transition temperature.     

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.     

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.     

Behavior of Ag photodoping in sulfide bulk glasses

The relationship between Ag photodoping behavior and glass structure has been studied using various sulfide bulk glasses. The transmission measurement revealed that the photodoping rate increased with an increase of S concentration in Ge–S glasses and GeS₂–SbS₂ glasses, while the disappearance of Ag film was not be observed in Ge₄₀S₆₀ and Ga₂S₃-based glasses, which contain modifier ions. The correlation between photodoping rate and S–S bond content in a host glass was confirmed. From the point of view of the behavior of Ag photodoping, sulfide glasses were classified into two groups: (1) a covalent glasses containing S–S bonds and (2) an ionic glasses containing modified ions.     

Ultrasonic wave velocities and attenuation in IVb-Vb-VIb chalcogenide glasses: 2–300 K

The velocities and attenuation of longitudinal and shear ultrasonic (12 MHz) waves have been measured for several chalcogenide glasses (Ge₁₀Si₁₂As₃₀Te₄₈, Ge₂₀As₃₀Se₅₀, Si₂₀As₃₂Te₄₈, Ge₁₀Si₁₂As₂₉Te₄₉, Ge₁₂S₁₄As₃₅Te₄₉). The bulk, shear and Young's moduli and the Poisson ratio are found to be insensitive to the glass composition. The temperature dependences of the longitudinal and shear-wave velocities are negative at higher temperatures and approach 0 K with a zero slope. The ultrasonic attenuation does not exhibit either the broad loss peak or the smaller low-temperature peak found in many other glasses: the elastic and anelastic behaviour is quite different from that of oxide glasses — no evidence for the existence of two-level systems has been obtained from the ultrasonic measurements.     

Reduced operating voltage in nanotube‐shaped Ge2Sb2Te5 unites by nanosphere lithography

Ge₂Sb₂Te₅ Units for Phase Change Memory are fabricated on 2‐dimesional polystyrene (PS) template in a magnetron sputtering system. SEM and TEM observations show the Ge₂Sb₂Te₅ nanotubes form on the 200 nm PS beads which are etched for 30 s. And the lengths of the nanotubes are tuned by the film deposition. HRTEM and the electron diffraction measurements confirm the phase transition between the amorphous and the crystallized state. Resistance–voltage measurements show the operating voltage of the Ge₂Sb₂Te₅ nanotube‐shaped unit is reduced due to the small contact area with the bottom electrode, which indicates its potential applications for phase change memory.     

An analytical model to represent crystallization kinetics in materials with metastable phase formation

The aim of this article is to propose a simple analytical model that can describe the isothermal crystallization process in materials when the formation of a stable crystalline phase is preceded by the formation of a metastable phase. This model explains deviations from the well-known Johnson-Mehl-Avrami-Kolmogorov kinetics theory and predicts the three slopes in Avrami’s plot. The model predictions were compared with experimental results obtained from X-ray measurements in the chalcogenide glasses with composition of Ge₂Sb₂Te₅ (thin films) and in aqueous solutions of methylhydrazine monohydrate during isothermal phase transformations. In order to validate the proposed model to represent experimental results, a computer program was developed. This program uses experimental data from measurements of the total volume fraction at different times during isothermal transformations and fits the model parameters that best represent the kinetic behavior of the system.     

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.     

Te NMR chemical shifts and tellurium coordination environments in crystals and glasses in the Ge-As-Sb-Te system

The local coordination environments of Te atoms have been investigated in crystalline and glassy binary and ternary tellurides in the system Ge-As-Sb-Te using ¹²⁵Te solid-state wideline nuclear magnetic resonance (NMR) spectroscopy. The average ¹²⁵Te NMR chemical shifts in these materials range from 300 to 1050, 90 to 700 and − 2000 to − 4100 ppm for 2, 3 and 6-coordinated environments, respectively. Te atoms are predominantly 2-coordinated in binary Ge-Te, As-Te and ternary Ge-As-Te glasses. The ¹²⁵Te NMR spectrum of the cubic Ge₁Sb₂Te₄ phase with rock salt structure is consistent with a random distribution of Ge/Sb vacancies in the lattice. Besides the coordination number, the ¹²⁵Te chemical shifts in these materials are also found to be sensitive to the chemical identity of the nearest neighbors. ¹²⁵Te NMR spectroscopy shows significant future promise in its application as a technique complementary to diffraction and EXAFS in understanding the short-range structure of amorphous Ge-As-Sb tellurides.     

Effect of antimony addition on the thermal and electrical-switching behavior of bulk Se-Te glasses

The thermal properties and electrical-switching behavior of semiconducting chalcogenide Sb_xSe_55−xTe₄₅ (2 ? x ? 9) glasses have been investigated by alternating differential scanning calorimetry and electrical-switching experiments, respectively. The addition of Sb is found to enhance the glass forming tendency and stability as revealed by the decrease in non-reversing enthalpy ΔH_nr, and an increase in the glass-transition width ΔT_g. Further, the glass-transition temperature of Sb_xSe_55−xTe₄₅ glasses, which is a measure of network connectivity, exhibits a subtle increase, suggesting a meager network growth with the addition of Sb. The crystallization temperature is also observed to increase with Sb content. The Sb_xSe_55−xTe₄₅ glasses (2 ? x ? 9) are found to exhibit memory type of electrical switching, which can be attributed to the polymeric nature of network and high devitrifying ability. The metallicity factor has been found to dominate over the network connectivity and rigidity in the compositional dependence of switching voltage, which shows a profound decrease with the addition of Sb.     

Electrical switching and thermal studies on bulk Ge-Te-Bi glasses

Bulk, melt quenched Ge₁₈Te_82-xBi_x glasses (1 ≤ x ≤ 4) have been found to exhibit memory type electrical switching behavior, which is in agreement with the lower thermal diffusivity values of Ge-Te-Bi samples. A linear variation in switching voltages (V_th) has been found in these samples with increase in thickness which is consistent with the memory type electrical switching. Also, the switching voltages have been found to decrease with an increase in temperature which happens due to the decrease in the activation energy for crystallization at higher temperatures. Further, V_th of Ge₁₈Te_82-xBi_x glasses have been found to decrease with the increase in Bi content, indicating that in the Ge-Te-Bi system, the resistivity of the additive has a stronger role to play in the composition dependence of V_th, in comparison with the network connectivity and rigidity factors. In addition, the composition dependence of crystallization activation energy has been found to show a decrease with an increase in Bi content, which is consistent with the observed decrease in the switching voltages. X-ray diffraction studies on thermally crystallized samples reveal the presence of hexagonal Te, GeTe, Bi₂Te₃ phases, suggesting that bismuth is not taking part in network formation to a greater extent, as reflected in the variation of switching voltages with the addition of Bi. SEM studies on switched and un-switched regions of Ge-Te-Bi samples indicate that there are morphological changes in the switched region, which can be attributed to the formation of the crystalline channel between two electrodes during switching.