Electrical Switching and Other Properties of Chalcogenide Glasses

Abstract | Electrical switching which has applications in areas such as information storage, power control, etc is a scientifically interesting and technologically important phenomenon exhibited by glassy chalcogenide semiconductors. The phase change memories based on electrical switching appear to be the most promising next generation non-volatile memories, due to many attributes which include high endurance in write/read operations, shorter write/read time, high scalability, multi-bit capability, lower cost and a compatibility with complementary metal oxide semiconductor technology.Studies on the electrical switching behavior of chalcogenide glasses help us in identifying newer glasses which could be used for phase change memory applications. In particular, studies on the composition dependence of electrical switching parameters and investigations on the correlation between switching behavior with other material properties are necessary for the selection of proper compositions which make good memory materials.In this review, an attempt has been made to summarize the dependence of the electrical switching behavior of chalcogenide glasses with other material properties such as network topological effects, glass transition & crystallization temperature, activation energy for crystallization, thermal diffusivity, electrical resistivity and others.

The electrical switching and thermal behavior of bulk Ge(15)Te(85-x)Sn(x) and Ge(17)Te(83-x)Sn(x) glasses

Bulk Ge(15)Te(85 - x)Sn(x) and Ge(17)Te(83 - x)Sn(x) glasses, are found to exhibit memory type electrical switching. The switching voltages (V(t)) and thermal stability of Ge(15)Te(85 - x)Sn(x) and Ge(17)Te(83 - x)Sn(x) glasses are found to decrease with Sn content. The composition dependence of v, 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 Ge(15)Te(85 - x)Sn(x) and Ge(17)Te(83 - x)Sn(x) glasses is found to be linear, in agreement with the memory switching behavior shown by these glasses. (C) 2011 Elsevier B.V. All rights reserved.

Effect of bismuth doping in GeSe and GeSeTe glasses by photoluminescence spectroscopy

Semiconducting chalcogenide glasses in the systems GeSe and GeSeTe with the addition of bismuth show unusual phenomena of p - to - n transition. Samples for characterization were prepared in bulk form by melt-quenching technique, with increasing Bi at. % to replace selenium. Photoluminescence (PL) spectroscopic studies on all the samples were carried out at 4.2K using an Ar-Ion laser for illuminating the samples. The laser power used was 200mw. Both the systems show a decrease in the intensity of PL signal with increasing Bi content. This interesting behavior is discussed on the basis of a charged defect model for chalcogenide glasses, proposed by Mott, Davis and Street (MDS). The effect of bismuth addition on these charged defects is also discussed to explain the carrier type reversal.

Structural and dielectric characteristics of Bi2O3-TiO2-SrB4O7 glasses

Glasses of the composition 0.20 Bi2O3 - 0.30 TiO2 - 0.50 SrB4O7 and 0.30 Bi2O3 - 0.45 TiO2 - 0.25 SrB4O7 have been fabricated by conventional glass processing technique. These glasses have been characterized using X-ray powder diffraction (XRD), differential thermal analysis (DTA) and high resolution transmission electron microscopy (HRTEM). The frequency response of the dielectric constant and the loss tangent of these glasses has been studied. The formation of the crystalline bismuth titanate, Bi4Ti3O12 (BiT) phase in the heat treated samples has been confirmed by XRD and HRTEM studies. The measured ET Of the glass-ceramics are found to be in good agreement with those predicted by the logarithmic mixture rule. Optical second harmonic generation (SHG) at 1064 nm has been observed in the heat treated samples and is attributed to the formation of crystalline Bi4Ti3O12 (BiT) phase in the SrB4O7 (SBO) matrix.

Non-linear electrical response of chalcogenide glasses: Memory state phenomena

Investigations on the switching behaviour of arsenic-tellurium glasses with Ge or Al additives, yield interesting information about the dependence of switching on network rigidity, co-ordination of the constituents, glass transition & ambient temperature and glass forming ability.

Photoluminescence study of mixed doped Ge-Se-In-Bi glasses

Photoluminescence studies, carried out using the Fourier Transform method rather than the conventional monochromator-dispersion method,are reported on glassy samples of indium-bismuth mixed doped Ge (10) Se(90-x-y) In (x) Bi (y) system (x,y = 5,10). The amorphous Bi2Se3 is found to be n-type like the crystalline counterpart. The possible contributions from microscopic cluster-level phase separation of Bi2Se3 and from the defects to the change in conductivity from p- to n- typein this system is discussed. The similar situation in related systems is also pointed out.

Thermodynamic, Raman and electrical switching studies on Si15Te85-xAgx (4 <= x <= 20) glasses

We have investigated thermal properties of bulk Si15Te85-xAgx (4 <= x <= 20) glasses in detail, through alternating differential scanning calorimetry experiments. The composition dependence of thermal parameters reveal the signatures of rigidity percolation and chemical threshold at compositions x = 12 and x = 19, respectively. The stability and glass forming ability of these glasses have also been determined using the data obtained from different thermodynamic quantities and it is found that the Si15Te85-xAgx glasses in the region 12 <= x <= 17 are more stable when compared to other glasses of the same series. Further, the blueshift observed in Raman spectroscopy investigations, in the composition range 12 <= x <= 13, support the occurrence of stiffness threshold in this composition range. All Si15Te85-xAgx (4 <= x <= 20) glasses are found to exhibit memory type switching (for sample thickness 0.25 mm) in the input current range 3-9 mA. The effect of rigidity percolation and chemical thresholds on switching voltages are observed at x = 12 and 19, respectively. (C) 2012 American Institute of Physics. [doi:10.1063/1.3682759]

Observation of high pressure o-GeTe phase at ambient pressure in Si-Te-Ge glasses

Te-rich Si15Te85-xGex (1 <= x <= 11) glasses are found to exhibit an anomalous phase separations with germanium composition. The structural transformation of o-GeTe crystalline phase from o-GeTe with a = 11.76 angstrom, b = 16.59 angstrom, c = 17.44 angstrom, to high pressure o-GeTe with a new reduced lattice parameters a = 10.95 angstrom, b = 4.03 angstrom, c = 4.45 angstrom, is observed at T-c3 in the composition range 6 <= x <= 11. Raman studies support the possible existence of high pressure o-GeTe phase which is observed in X-ray diffraction experiments. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. http://dx.doi.org/10.1063/1.3696862]

Thermo-physical and structural studies of sodium zinc borovanadate glasses in the region of high concentration of modifier oxides

This paper reports investigation of Na2O and ZnO modified borovanadate glasses in the highly modified regime of compositions. These glasses have been prepared by microwave route. Ultraviolet (UV) and visible, infrared (IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies have been used to characterize the speciation in the glasses. Together with the variation of properties such as molar volume and glass transition temperatures, spectroscopic data indicate that at high levels of modification, ZnO tends to behave like network former. It is proposed that the observed variation of all the properties can be reasonably well understood with a structural model. The model considers that the modification and speciation in glasses are strongly determined by the hierarchy of group electronegativities. Further, it is proposed that the width of the transitions of glasses obtained under same condition reflects the fragility of the glasses. An empirical expression has been suggested to quantify fragility on the basis of width of the transition regions. (C) 2012 Elsevier Ltd. All rights reserved.

Thermal diffusivity measurements on ternary Ge-Te-Tl glasses using Photo-thermal Deflection method: Effect of thallium addition

Photo-thermal Deflection (PTD) technique is used to investigate the thermal diffusivity (alpha) of Ge17Te83 - xTlx (0 <= x <= 13) glasses as a function of composition. The thermal diffusivity of these glasses is found to lie in the range 0.020 to 0.048 cm(2)/s, which is consistent with the memory type of electrical switching exhibited by these samples. Further, it is found that alpha shows an initial increase with Tl addition, followed by a decrease. The observed composition dependence of thermal diffusivity has been understood on the basis that the thallium atoms are incorporated as a covalent species for lower values of x, increasing the network rigidity; however, they enter as ionic species for higher x values, fragmenting the network. The initial increase in a is due to the increasing network rigidity and the subsequent decrease is because of the fragmentation of the network. Also, there is a strong correlation between the composition dependence of switching voltages observed earlier and the variation with composition of electrical resistivity and thermal diffusivity of Ge17Te83 - xTlx glasses obtained in the present study. (C) 2012 Elsevier B.V. All rights reserved.

Nonlinear Refraction and Two-Photon Absorption in Dense 2Bi(2)O(3)-B2O3 Glasses

High density transparent glasses (7.86 g/cc) were fabricated in the 2Bi(2)O(3)-B2O3 (BBO) system. Optical band gap of the obtained glasses was found to be 2.6eV. The refractive index measured for these glasses was 2.25 +/- 0.05 at lambda=543 nm. Nonlinear refraction and absorption studies were carried out on the BBO glasses using z-scan technique a lambda=532 nm of 10 ns pulse width. The nonlinear refractive index obtained was n(2)=12.1x10(-14) cm(2)/W and nonlinear absorption coefficient was beta=15.2 cm/GW. The n(2) and beta values of the BBO glasses were large compared to the other reported high index bismuth based oxide glass systems in the literature. These were attributed to the high density, high linear refractive index, low band gap and two photon absorption associated with these glasses. The electronic origin of large nonlinearities was discussed based on bond-orbital theory.

Manifestation of intermediate phase in mechanical properties: Nano-indentation studies on Ge-Te-Si bulk chalcogenide glasses

Nano-indentation studies have been undertaken on bulk Ge15Te85-xSix glasses (0 <= x <= 9), to estimate hardness, H and elastic modulus, E. It is found that E and H increase initially with the increase in the atomic percent of Si. Further, a plateau is seen in the composition dependence of E and H in the composition range 2 <= x <= 6. It is also seen that the addition of up to 2 at% Si increases the density rho of the glass considerably; however, further additions of Si lead to a near linear reduction in rho, in the range 2 <= x <= 6. Beyond x=6, rho increases again with Si content. The variation of molar volume V-m brings out a more fascinating picture. A plateau is seen in the intermediate phase suggesting that the molecular structure of the glasses is adapting to keep the count of constraints fixed in this particular phase. The observed variations in mechanical properties are associated with the Boolchand's intermediate phase in the present glassy system, in the composition range 2 <= x <= 6, suggested earlier from calorimetric and electrical switching studies. The present results reveal rather directly the existence of the intermediate phase in elastic and plastic properties of chalcogenide glasses. (C) 2012 Elsevier Ltd. All rights reserved.

Thermally reversing window in Ge15Te85-xInx glasses: Nanoindentation and micro-Raman studies

Nanoindentation studies on Ge15Te85-xInx glasses indicate that the hardness and elastic modulus of these glasses increase with indium concentration. While a pronounced plateau is seen in the elastic modulus in the composition range 3 <= x <= 7, the hardness exhibits a change in slope at compositions x = 3 and x = 7. Also, the density exhibits a broad maximum in this composition range. The observed changes in the mechanical properties and density are clearly associated with the thermally reversing window in Ge15Te85-xInx glasses in the composition range 3 <= x <= 7. In addition, a local minimum is seen in density and hardness around x = 9, the chemical threshold of the system. Further, micro-Raman studies reveal that as-quenched Ge15Te85-xInx samples exhibit two prominent peaks, at 123 cm(-1) and 155 cm(-1). In thermally annealed samples, the peaks at 120 cm(-1) and 140 cm(-1), which are due to crystalline Te, emerge as the strongest peaks. The Raman spectra of polished samples are similar to those of annealed samples, with strong peaks at 123 cm(-1) and 141 cm(-1). The spectra of lightly polished samples outside the thermally reversing window resemble those of thermally annealed samples; however, the spectra of glasses with compositions in the thermally reversing window resemble those of as-quenched samples. This observation confirms the earlier idea that compositions in the thermally reversing window are non-aging and are more stable. (C) 2012 Elsevier B.V. All rights reserved.

Electrical transport characteristics of ZnO-Bi2O3-B2O3 glasses

Optically clear glasses in the ZnO-Bi2O3-B2O3 (ZBBO) system were fabricated via the conventional melt-quenching technique. Dielectric constant and loss measurements carried out on ZBBO glasses unraveled nearly frequency (1 kHz-10 MHz)-independent dielectric characteristics associated with significantly low loss (D = 0.004). However, weak temperature response was found with temperature coefficient of dielectric constant 18 +/- 4 ppm A degrees C-1 in the 35-250 A degrees C temperature range. The conduction and relaxation phenomena were rationalized using universal AC conductivity power law and modulus formalism respectively. The activation energy for relaxation determined using imaginary parts of modulus peaks was 2.54 eV which was close to that of the DC conduction implying the involvement of similar energy barriers in both the processes. Stretched and power exponents were temperature dependent. The relaxation and conduction in these glasses were attributed to the hoping and migration of Bi3+ cations in their own and different local environment.

Shear bands mediate cavitation in brittle metallic glasses

Recent experimental studies have revealed nanoscale cavities and periodic corrugations on the fracture surfaces of brittle metallic glasses. How such cavitation in these materials leads to brittle failure remains unclear. Here we show, using atomistic and continuum finite element simulations, that a shear band can mediate cavity nucleation and coalescence owing to plastic flow confinement caused by material softening. This leads to brittle fracture as cavities nucleate and coalesce within a shear band, causing the crack to extend along it. (c) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.