Ge/Sb2Te3 nanocomposite multilayer films for high data retention phase-change random access memory application

The amorphous-to-crystalline transition of Ge/Sb₂Te₃ nanocomposite multilayer films with various thickness ratios of Ge to Sb₂Te₃ were investigated by utilizing in situ temperature-dependent film resistance measurements. The crystallization temperature and activation energy for the crystallization of the multilayer films increased with the increase in thickness ratio of Ge to Sb₂Te₃. The difference in sheet resistance between amorphous and crystalline states could reach as high as 10⁴ Ω/□. The crystallization temperature and activation energy for the crystallization of Ge/Sb₂Te₃ nanocomposite multilayer films was proved to be larger than that of conventional Ge₂Sb₂Te₅ film, which ensures a better data retention for phase-change random access memory (PCRAM) use. A data retention temperature for 10 years of the amorphous state [Ge (2 nm)/Sb₂Te₃ (3 nm)]₄₀ film was estimated to be 165 °C. Transmission electron microscopy (TEM) images revealed that Ge/Sb₂Te₃ nanocomposite multilayer films had layered structures with clear interfaces.     

Characteristics of Si-doped Sb2Te3 thin films for phase-change random access memory

The characteristics of Si-doped Sb₂Te₃ thin films were investigated using differential scanning calorimetry (DSC), four-point probe technique, X-ray diffraction (XRD) analysis and high resolution transmission electron microscopy (HRTEM). It is found that the as-deposited Sb₂Te₃ film in our study is partly crystallized. Silicon doping increases the crystallization temperature and resistivity of Sb₂Te₃ film significantly. XRD and HRTEM analyses indicated that some of the doped Si atoms substitute for Sb or Te in the lattice, while others exists at the grain boundaries in the form of amorphous phase, which may be responsible for grain size reduction and high crystalline resistivity of Si-doped specimens. Compared with the conventional Ge₂Sb₂Te₅ film, Si-doped Sb₂Te₃ films exhibit lower melting temperature and higher crystalline resistivity, which is beneficial to RESET current reduction of phase-change random access memory (PRAM). These results show the feasibility of Si-doped Sb₂Te₃ films in PRAM application.     

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     

应用于相变存储器的Cu-Ge3Sb2Te5薄膜的结构及相变特性研究

采用磁控溅射法制备了不同Cu含量的Cu-Ge₃Sb₂Te₅薄膜, 原位测试了薄膜电阻与温度的关系, 并利用X射线衍射仪、透射电镜、透过和拉曼光谱仪分别研究了 Cu-Ge₃Sb₂Te₅薄膜的晶体结构、微结构、禁带宽度及成键情况. 结果表明, Cu-Ge₃Sb₂Te₅薄膜的结晶温度和结晶活化能随着Cu含量的增加而增大, Cu的加入有效改善Ge₃Sb₂Te₅薄膜的热稳定性和10年数据保持力. 随着Cu含量的增加, 非晶态Cu-Ge₃Sb₂Te₅薄膜的禁带宽度逐渐减小. 同时, 拉曼峰从129 cm^-1向127 cm^-1处移动, 这是由于Cu–Te极性键振动增强的缘故. Cu-Ge₃Sb₂Te₅结晶为均匀、相互嵌套的六方Cu₂Te和Ge₂Sb₂Te₅相.     

Effective Mass Enhancement and Thermal Conductivity Reduction for Improving the Thermoelectric Properties of Pseudo-Binary Ge2Sb2Te5

Ge₂Sb₂Te₅ is a famous phase-change memory material for rewriteable optical storage, which is widely applied in the information storage field. The stable trigonal phase of Ge₂Sb₂Te₅ shows potential as a thermoelectric material as well, due to its tunable electrical transport properties and low lattice thermal conductivity. In this work, the carrier concentration and effective mass of Ge₂Sb₂Te₅ are modulated by substituting Te with Se. Meanwhile, the thermal conductivity reduces from 2.48 W m⁻¹ K⁻¹ for Ge₂Sb₂Te₅ to 1.37 W m⁻¹ K⁻¹ for Ge₂Sb₂Te_3.5Se_1.5 at 703 K. Therefore, the thermoelectric figure of merit zT increases from 0.24 for Ge₂Sb₂Te₅ to 0.41 for Ge₂Sb₂Te_3.5Se_1.5 at 703 K. This study reveals that Se alloying is an effective way to enhance the thermoelectric properties of Ge₂Sb₂Te₅.     

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.     

Temperature dependence of thermal properties of Ag<Subscript>8</Subscript>In<Subscript>14</Subscript>Sb<Subscript>55</Subscript>Te<Subscript>23</Subscript> phase-change memory materials

The dependence of thermal properties of Ag₈In₁₄Sb₅₅Te₂₃ phase-change memory materials in crystalline and amorphous states on temperature was measured and analyzed. The results show that in the crystalline state, the thermal properties monotonically decrease with the temperature and present obvious crystalline semiconductor characteristics. The heat capacity, thermal diffusivity, and thermal conductivity decrease from 0.35 J/g K, 1.85 mm²/s, and 4.0 W/m K at 300 K to 0.025 J/g K, 1.475 mm²/s, and 0.25 W/m K at 600 K, respectively. In the amorphous state, while the dependence of thermal properties on temperature does not present significant changes, the materials retain the glass-like thermal characteristics. Within the temperature range from 320 K to 440 K, the heat capacity fluctuates between 0.27 J/g K and 0.075 J/g K, the thermal diffusivity basically maintains at 0.525 mm²/s, and the thermal conductivity decreases from 1.02 W/m K at 320 K to 0.2 W/m K at 440 K. Whether in the crystalline or amorphous state, Ag₈In₁₄Sb₅₅Te₂₃ are more thermally active than Ge₂Sb₂Te₅, that is, the Ag₈In₁₄Sb₅₅Te₂₃ composites bear stronger thermal conduction and diffusion than the Ge₂Sb₂Te₅ phase-change memory materials.     

相变存储材料Ge1Sb2Te4和Ge2Sb2Te5薄膜的结构和电学特性研究

采用射频磁控溅射方法制备了两种用于相变存储器的Ge₁Sb₂Te₄和Ge₂Sb₂Te₅相变薄膜材料,对其结构、电学输运性质和恒温下电阻随时间的变化关系进行了比较和分析.X射线衍射(XRD)和原子力显微镜(AFM)的结果表明:随着退火温度的升高,Ge₁Sb₂Te₄薄膜逐步晶化,由非晶态转变为多晶态,表面出现均匀的、 关键词： 硫系相变材料 1Sb₂Te₄')" href="#">Ge₁Sb₂Te₄ 2Sb₂Te₅')" href="#">Ge₂Sb₂Te₅     

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.     

Phase transition characteristics of Ge–Sb–Te pseudobinary alloys in laser irradiation measurement

Optical switching and structural transformation of GeTe–Sb₂Te₃ pseudobinary alloys, Ge₂Sb₂Te₅, Ge₁Sb₂Te₄, and Ge₁Sb₄Te₇, were studied for data storage application. As-deposited Ge₂Sb₂Te₅, Ge₁Sb₂Te₄, and Ge₁Sb₄Te₇ thin films were amorphous and they crystallized to FCC and HCP upon heat treatment. Crystallization was accelerated by increasing the proportion of Sb₂Te₃ rather than GeTe in Ge–Sb–Te compounds; this was observed by reflectivity changes under nanosecond laser irradiation in static tester. The different crystallization kinetics according to composition might be affected by the structural incompatibility of GeTe under the ‘Umbrella Flip’ theory.     

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.     

Study of aluminium-modified Ge2Sb2Te5 thin films for the applicability as phase-change storage device material

Electrical and optical studies have been carried out on aluminium-modified Ge₂Sb₂Te₅ thin films to check its applicability as an active material in optical and electrical memory storage devices. Five polycrystalline bulk samples were prepared with compositions: Al_x(Ge₂Sb₂Te₅)_1?x; x = 0, 0.08, 0.14, 0.21, 0.25. Amorphous thin films were deposited from the polycrystalline bulk by thermal evaporation. Temperature-dependent resistance shows the increase in crystallization temperature of Ge–Sb–Te films on aluminium addition. Activation energy for conduction, conductivity, optical band gap, coefficient of refraction and extinction coefficient are studied with respect to Al content in both amorphous and crystalline phases of Ge–Sb–Te alloy films.     

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.     

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.     

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.     

Investigation on Ge5−x Sb x Te5 phase-change materials by first-principles method

The structure stability and chemical bonding of Ge_5?x Sb _x Te₅ (x=0,1,2) phase-change alloys were studied by ab initio calculations. By analyzing formation energies, density of states and electron localization function, we have shown that the chemical bonding character of Ge₄Sb₁Te₅ is quite similar to that of GeTe and hence a NaCl crystalline state is expected. The introduction of extra electrons by Sb in Ge₄Sb₁Te₅ and Ge₃Sb₂Te₅ results in states at the Fermi Level. With increasing Sb contents as in Ge₃Sb₂Te₅, the chemical bonding becomes rather inhomogeneous.     

Morphological characteristics of amorphous Ge2Sb2Te5 films after a single femtosecond laser pulse irradiation

The morphology of materials resulting from laser irradiation of the single-layer and the multilayer amorphous Ge₂Sb₂Te₅ films using 120 fs pulses at 800 nm was observed using scanning electron microscopy and atomic force microscopy. For the single-layer film, the center of the irradiated spot is depression and the border is protrusion, however, for the multilayer film, the center morphology changes from a depression to a protrusion as the increase of the energy. The crystallization threshold fluence of the single-layer and the multilayer film is 22 and 23 mJ/cm², respectively.     

Microstructures and thermoelectric properties of GeSbTe based layered compounds

Microstructures and thermoelectric properties of Ge₁Sb₂Te₄ and Ge₂Sb₂Te₅ chalcogenide semiconductors have been investigated to explore the possibility of their thermoelectric applications. The phase transformation from the face-centered cubic to hexagonal structure was observed in Ge₂Sb₂Te₅ compounds prepared by the melt spinning technique. The Seebeck coefficient and electrical resistivity of the alloys were increased due to the enhanced scattering of charge carriers at grain boundaries. The maximum power factors of the rapidly solidified Ge₁Sb₂Te₄ and Ge₂Sb₂Te₅ attained 0.975×10^-3 W m^-1K^-2 at 750 K and 0.767×10^-3 W m^-1K^-2 at 643 K respectively, higher than those of water quenched counterparts, implying that thermoelectric properties of GeSbTe based layered compounds can be improved by grain refinement. The present results show this class of chalcogenide semiconductors is promising for thermoelectric applications. PACS  84.60.Rb; 81.05.Hd; 72.20.Pa; 64.70.Kb; 61.66.Fn     

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.     

Investigation of electrical characteristics of the In3Sb1Te2 ternary alloy for application in phase‐change memory

A simple layered phase‐change random access memory (PRAM) cell was fabricated using the In₃Sb₁Te₂ alloy. The overall resistance value of the reset state was about 70 times larger than that of the set state. The resistance difference between the amorphous and crystalline state was fairly well maintained after 10² cycles. Interestingly, the measured current–voltage (I –V) curve showed three obvious steps in the crystalline state. By means of high temperature X‐ray diffractometry (HTXRD) and differential scanning calorimetry (DSC) experiments, we confirmed that the current steps originate from successive structural transformations of the In₃Sb₁Te₂ ternary alloy. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)