Phase stability and electronic structure of Si2Sb2Te5 phase-change material

On the basis of an ab initio computational study, the present work provide a full understanding on the atomic arrangements, phase stability as well as electronic structure of Si₂Sb₂Te₅, a newly synthesized phase-change material. The results show that Si₂Sb₂Te₅ tends to decompose into Si₁Sb₂Te₄ or Si₁Sb₄Te₇ or Sb₂Te₃, therefore, a nano-composite containing Si₁Sb₂Te₄, Si₁Sb₄Te₇ and Sb₂Te₃ may be self-generated from Si₂Sb₂Te₅. Hence Si₂Sb₂Te₅ based nano-composite is the real structure when Si₂Sb₂Te₅ is used in electronic memory applications. The present results agree well with the recent experimental work.     

Electrochemical deposition of Bi2Te3-based thin films

The electrochemical reduction processes on stainless-steel substrates from an aqueous electrolyte composed of nitric acid, Bi³⁺, HTeO₂⁺, SbO⁺ and H₂SeO₃ systems were investigated using cyclic voltammetry. The thin films with a stoichiometry of Bi₂Te₃, Bi_0.5Sb_1.5Te₃ and Bi₂Te_2.7Se_0.3 have been prepared by electrochemical deposition at selected potentials. The structure, composition, and morphology of the films were studied by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM) and electron microprobe analysis (EMPA). The results showed that the films were single phase with the rhombohedral Bi₂Te₃ structure. The morphology and growth orientation of the films were dependent on the deposition potentials.     

Crystallization of Ge2Sb2Te5 phase—change optical disk media

In this paper, the crystallization behaviour of amorphous Ge₂Sb₂Te₅ thin films is investigated using differential scanning calorimetry), x-ray diffraction and optical transmissivity measurements. It is indicated that only the amorphous phase to face-centred-cubic phase transformation occurs during laser annealing of the normal phase-change structure, which is a benefit for raising the phase-change optical disk's carrier-to-noise ratio (CNR). For amorphous Ge₂Sb₂Te₅ thin films, the crystallization temperature is about 200℃ and the melting temperature is 546.87℃. The activation energy for the crystallization, E_a, is 2.25eV. The crystallization dynamics for Ge₂Sb₂Te₅ thin films obeys the law of nucleation and growth reaction. The sputtered Ge₂Sb₂Te₅ films were initialized by an initializer unit. The initialization conditions have a great effect on the reflectivity contrast of the Ge₂Sb₂Te₅ phase-change optical disk.     

Switching phenomenon and optical properties of Se85Te10Bi5 films

Se₈₅Te₁₀Bi₅ films of different thicknesses ranging from 126 to 512 nm have been prepared. Energy-dispersive X-ray (EDX) spectroscopy technique showed that films are nearly stoichiometric. X-ray diffraction (XRD) measurements have showed that the Se₈₅Te₁₀Bi₅ films were amorphous. Electrical conduction activation energy (ΔE_σ) for the obtained films is found to be 0.662 eV independent of thickness in the investigated range. Investigation of the current voltage (I-V) characteristics in amorphous Se₈₅Te₁₀Bi₅ films reveals that it is typical for a memory switch. The switching voltage V_th increases with the increase of the thickness and decreases exponentially with temperature in the range from 298 to 383 K. The switching voltage activation energy (ε) calculated from the temperature dependence of V_th is found to be 0.325 eV. The switching phenomenon in amorphous Se₈₅Te₁₀Bi₅ films is explained according to an electrothermal model for the switching process. The optical constants, the refractive index (n) and the absorption index (k) have been determined from transmittance (T) and reflectance (R) of Se₈₅Te₁₀Bi₅ films. Allowed non-direct transitions with an optical energy gap (E_g^opt) of 1.33 eV have been obtained. ΔE_σ is almost half the obtained value of E_g^opt, which suggested band to band conduction as indicated by Davis and Mott.     

Effects of double filling of Pb and Ba on thermoelectric properties of PbxBayCo4Sb11.5Te0.5 compounds by HPHT

Skutterudite compounds Pb_xBa_yCo₄Sb_11.5Te_0.5 (x≤0.23,y≤0.27) with bcc crystal structure have been prepared by the high pressure and high temperature (HPHT) method. The study explored a chemical method for filling Pb and Ba atoms into the voids of CoSb₃ to optimize the thermoelectric figure of merit ZT in the system of Pb_yBa_xCo₄Sb_11.5Te_0.5. The structure of Pb_xBa_yCo₄Sb_11.5Te_0.5 skutterudites was evaluated by means of X-ray diffraction. The Seebeck coefficient, electrical resistivity and power factor were performed from room temperature to 710 K. Compared with Co₄Sb_11.5Te_0.5, the thermal conductivity of Pb and Ba double-filled samples was reduced evidently. Among all filled samples, Pb_0.03Ba_0.27Co₄Sb_11.5Te_0.5 showed the highest power factor of 31.64 μW cm⁻¹ K⁻² at 663 K. Pb_0.05Ba_0.25Co₄Sb_11.5Te_0.5 showed the lowest thermal conductivity of 2.73 W m⁻¹ K⁻¹ at 663 K, and its maximum ZT value reached 0.63 at 673 K.     

Thermoelectric power and phase transition of polycrystalline As2Te3 under pressure

The pressure dependence of the thermoelectric power of monoclinic As₂Te₃ is measured up to 10 GPa using a Mao-Bell diamond anvil cell. The thermoelectric power never reaches an absolute value greater than the ambient pressure value of 242 μV/K. Evidence of a phase transition is present between 6 and 8 GPa where the thermoelectric power reaches an absolute value of 225 μV/K after passing through a minimum of S≈75 μV/K. X-ray diffraction experiments confirm that the resulting structure is β-As₂Te₃, which is isostructural with Bi₂Te₃ and Sb₂Te₃.     

Superconductivity and non-metallicity induced by doping the topological insulators Bi2Se3 and Bi2Te3

We show that by Ca doping the Bi₂Se₃ topological insulator, the Fermi level can be fine tuned to fall inside the band gap and therefore suppresses the bulk conductivity. Non-metallic Bi₂Se₃ crystals are obtained. On the other hand, the Bi₂Se₃ topological insulator can also be induced to become a bulk superconductor, with T_c∼3.8 K, by copper intercalation in the van der Waals gaps between the Bi₂Se₃ layers. Likewise, an as-grown crystal of metallic Bi₂Te₃ can be turned into a non-metallic crystal by slight variation in the Te content. The Bi₂Te₃ topological insulator shows small amounts of superconductivity with T_c∼5.5 K when reacted with Pd to form materials of the type Pd_zBi₂Te₃.     

On the origin of two-dimensional electron gas states at the surface of topological insulators

The ab initio calculations of the electronic structure in the bulk and at the (0001) surface of narrow-band Bi₂Se₃, Sb₂Te₃, Sb₂STe₃, and Sb₂SeTe₂ semiconductors have been performed. It has been shown that ternary compounds Sb₂STe₂ and Sb₂SeTe₂, as well as the previously known compounds Bi₂Se₃ and Sb₂Te₃, are three-dimensional topological insulators. The influence of the subsurface van der Waals gap expansion on the surface electronic structure of these compounds has been analyzed. It has been shown that this expansion leads to the formation of new (trivial) surface states, namely a parabolic state in the conduction band and an M-shaped state in the valence band. These results explain the phenomena discovered recently in photoemission experiments and reveal the nature of new states that are caused by the adsorption of atoms on the surfaces of the layered topological insulators.     

Electrical transport and high thermoelectric properties of PbTe doped with Bi2Te3 prepared by HPHT

In this paper, n-type lead telluride (PbTe) compounds doped with Bi₂Te₃ have been successfully prepared by high pressure and high temperature (HPHT) technique. The composition-dependent thermoelectric properties of PbTe doped with Bi₂Te₃ have been studied at room temperature. The figure-of-merit, Z, for PbTe is very sentivite to the dopants, which could be improved largely although the doped content of Bi₂Te₃ is very small (<0.08 mol%). In addition, the maximum value reaches to 9.3×10⁻⁴ K⁻¹, which is about 20% higher than that of PbTe alloyed with Bi₂Te₃ sintered at ambient pressure (7.6×10⁻⁴ K⁻¹) and several times higher than that of small grain size PbTe containing other dopants. The improved thermoelectric performance in this study may be due to the effect of high pressure and the low lattice thermal conductivity resulting from Bi₂Te₃ as source of dopants.     

A transmission electron microscopy study on the atomic arrangement and grain growth of hexagonal structured Ge2Sb2Te5

The atomic arrangement and grain growth of the hexagonal structured Ge₂Sb₂Te₅ were investigated by a transmission electron microscopy study. Unlike the isotropic crystallization of face-centered-cubic (fcc) structured Ge₂Sb₂Te₅, the hexagonal structured Ge₂Sb₂Te₅ grain was preferably grown to a large degree with a specific direction. As a result, we have revealed that the grain growth occurred parallel to the (0 0 0 1) plane, and identified the atomic arrangement of the hexagonal structured Ge₂Sb₂Te₅ having nine cyclic layers by analyzing the high-resolution transmission electron microscopy images and simulated images obtained in the direction of zone axis.     

In situ AFM and Raman spectroscopy study of the crystallization behavior of Ge2Sb2Te5 films at different temperature

Using in situ atomic force microscope (AFM) and Raman spectroscopy, the real-time crystallization properties of Ge₂Sb₂Te₅ films at different temperature were characterized. The given AFM topograph and phase images revealed that the structure of amorphous Ge₂Sb₂Te₅ films began to change at a temperature of as low as 100 °C. When the temperature reached 130 °C, some crystal fragments had formed at the film surface. Heating up to 160 °C, the size of the visible crystal fragments increased, but decreased at a higher temperature of 200 °C. When the Ge₂Sb₂Te₅ film was cooled down to room temperature (RT) from 200 °C, the crystal fragments divided into crystal grains due to the absence of heating energy. The Raman spectra at different temperature further verified the structure evolution of the Ge₂Sb₂Te₅ film with temperature. This work is of significance for the preparation of Ge₂Sb₂Te₅ films and the erasing of data.     

基于Si掺杂Sb2Te3薄膜的相变存储器研究

采用磁控三靶(Si，Sb及Te)共溅射法制备了Si掺杂Sb₂Te₃薄膜，作为对比，制备了Ge₂Sb₂Te₅和Sb₂Te₃薄膜，并且采用微加工工艺制备了单元尺寸为10μm×10μm的存储器件原型来研究器件性能.研究表明，Si掺杂提高了Sb₂Te₃薄膜的晶化温度以及薄膜的晶态和非晶态电阻率，使得其非晶态与晶态电阻率之比达到10⁶，提高了器件的电阻开/关比；同Ge₂Sb₂Te₅薄膜相比，16at% Si掺杂Sb₂Te₃薄膜具有较低的熔点和更高的晶态电阻率，这有利于降低器件的RESET电流.研究还表明，采用16at% Si掺杂Sb₂Te₃薄膜作为存储介质的存储器器件原型具有记忆开关特性，可以在脉高3V、脉宽500ns的电脉冲下实现SET操作，在脉高4V、脉宽20ns的电脉冲下实现RESET操作，并能实现反复写/擦，而采用Ge₂Sb₂Te₅薄膜的相同结构的器件不能实现RESET操作. 关键词： 相变存储器 硫系化合物 2Te₃薄膜')" href="#">Si掺杂Sb₂Te₃薄膜 SET/RESET转变     

Effect of thermal annealing on microstructural properties of Ti/Ge2Sb2Te5/Ti thin films deposited on SiO2/Si substrates by a sputtering method

Ti/Ge₂Sb₂Te₅/Ti thin films deposited by a sputtering method on SiO₂/Si substrates were annealed at 400 °C in N₂ atmosphere and characterized by using transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) in order to investigate the inter-diffusion of the Ti/Ge₂Sb₂Te₅/Ti system due to annealing. The TEM and AES results showed that the interface between the Ti and the Ge₂Sb₂Te₅ layers was unstable and Ti atoms were incorporated into the Ge₂Sb₂Te₅ thin film upon annealing. The Te and Sb atoms of the Ge₂Sb₂Te₅ layer diffused into the Ti layer. The intermixing layers between the Ge₂Sb₂Te₅ layer and two Ti layers were formed. These results indicate that the microstructural properties of the Ti/Ge₂Sb₂Te₅/Ti systems can be degraded by the postgrowth thermal annealing.     

Effective method for preparation of oxide-free Ge2Sb2Te5 surface: An X-ray photoelectron spectroscopy study

Cleaning the surfaces of the as-deposited Ge₂Sb₂Te₅ was studied by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and X-ray diffraction (XRD). The mixed native oxides on the as-deposited Ge₂Sb₂Te₅ surface can be easily removed by dipping Ge₂Sb₂Te₅ in de-ionized water for 1 min, while the surface morphology remains unchanged after cleaning. Native oxides only re-grow after exposure to air for more than 4 min. Although dipping in water leads to a surface layer deficient in Ge and Sb, the surface composition of Ge₂Sb₂Te₅ can recover to its stoichiometric value after annealing at 200 °C in vacuum. The phase remains amorphous at room temperature after dipping in water, and changes to fcc and hcp after annealing at 100 and 220 °C, respectively.     

Experimental and theoretical study of silicon-doped Sb2Te3 thin films: Structure and phase stability

The influence of Si in Sb₂Te₃ on structure and phase stability was studied by experiments and ab initio calculations. With the increase of Si content in Sb₂Te₃ samples, the crystallization temperature increases and the crystalline grain size decreases. The incorporation of Si atoms into Sb₂Te₃ lattice is energetically unfavorable and hence Si atoms most probably accumulated in the boundaries of Sb₂Te₃ grains.     

Electro- and thermoreflectance of Bi2Te3 and Bi2Se3

Electroreflectance measurements in Bi₂Te₃ and Bi₂Se₃ with the electric field vector of the incident light both inclined and perpendicular to the C-axis have been made at room temperature. The structures found by other workers in the reflection measurements are observed in the present experiment, together with new structures at 0.91 eV, 1.18 eV, 1.78 eV, and 2.61 eV in Bi₂Se₃ which are not related to formerly observed transitions. From these measurements, the selection rules for direct optical transitions in Bi₂Te₃ and Bi₂Se₃ are studied. Thermoreflectance measurements are also made at both room and liquid-nitrogen temperatures. The positions of the peaks obtained in the present work are compared with the electroreflectance and reflection data.     

High thermal stability and low thermal conductivity in Ga30Sb70/Sb80Te20 nanocomposite multilayer films

The reliability characteristics and thermal conductivity of Ga₃₀Sb₇₀/Sb₈₀Te₂₀ nanocomposite multilayer films were investigated by isothermal resistance and transient thermoreflectance (TTR) measurements, respectively. The crystallization temperature and activation energy for the crystallization can be modulated by varying the layer thickness of Ga₃₀Sb₇₀. A data retention time of ten years of the amorphous state [Ga₃₀Sb₇₀ (3 nm)/Sb₈₀Te₂₀ (5 nm)]₁₃, [Ga₃₀Sb₇₀ (5 nm)/Sb₈₀Te₂₀ (5 nm)]₁₀, and [Ga₃₀Sb₇₀ (10 nm)/Sb₈₀Te₂₀ (5 nm)]₇ was estimated when ambient temperature is 137, 163, and 178 °C, respectively. Ga₃₀Sb₇₀/Sb₈₀Te₂₀ nanocomposite multilayer films were found to have lower thermal conductivity in both the amorphous and crystalline state compared to Ge₂Sb₂Te₅ film, which will promise lower programming power in the phase-change random access memory.     

Hall mobility of amorphous Ge2Sb2Te5

The electrical conductivity, Seebeck coefficient, and Hall coefficient of three-micron-thick films of amorphous Ge₂Sb₂Te₅ have been measured as functions of temperature from room temperature down to as low as 200 K. The electrical conductivity manifests an Arrhenius behavior. The Seebeck coefficient is p-type with behavior indicative of multi-band transport. The Hall mobility is n-type and low (near 0.07 cm²/V s at room temperature).     

Performance improvement of Sb2Te3 phase change material by Al doping

Al doped Sb₂Te₃ material was proposed to improve the performance of phase-change memory. Crystallization temperature, activation energy, and electrical resistance of the Al doped Sb₂Te₃ films increase markedly with the increasing of Al concentration. The additional Al-Sb and Al-Te bonds enhance the amorphous thermal stability of the material. Al_0.69Sb₂Te₃ material has a better data retention (10 years at 110 °C) than that of Ge₂Sb₂Te₅ material (10 years at 87 °C). With a 100 ns width voltage pulse, SET and RESET voltages of 1.3 and 3.3 V are achieved for the Al_0.69Sb₂Te₃ based device.     

Effects of Si doping on the structural and electrical properties of Ge2Sb2Te5 films for phase change random access memory

The effects of Si doping on the structural and electrical properties of Ge₂Sb₂Te₅ film are studied in detail. Electrical properties and thermal stability can be improved by doping small amount of Si in the Ge₂Sb₂Te₅ film. The addition of Si in the Ge₂Sb₂Te₅ film results in the increase of both crystallization temperature and phase-transition temperature from face-centered cubic (fcc) phase to hexagonal (hex) phase, however, decreases the melting point slightly. The crystallization activation energy reaches a maximum at 4.1 at.% and then decreases with increasing dopant concentration. The electrical conduction activation energy increases with the dopant concentration, which may be attributed to the increase of strong covalent bonds in the film. The resistivity of Ge₂Sb₂Te₅ film shows a significant increase with Si doping. When doping 11.8 at.% of Si in the film, the resistivity after 460 °C annealing increases from 1 to 11 mΩ cm compared to the undoped Ge₂Sb₂Te₅ film. Current-voltage (I-V) characteristics show Si doping may increase the dynamic resistance, which is helpful to writing current reduction of phase-change random access memory.