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.     

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     

Magnetoresistance in granular films formed by CoFe and phase change material

Magnetoresistance having a field and current dependence like that of GMR (but a rather small magnitude) has been observed in Co₇₀Fe₃₀/GeTe and Co₇₀Fe₃₀/Ge₂Sb₂Te₅ granular films. Film stacks were fabricated using tandem (multilayer) deposition and annealing was required for the films to develop the GMR-type response. This GMR-type behavior is distinct from AMR, which is observed before annealing. With films having the structure [CoFe 4 nm/GeTe 6 nm]₁₀, a magnetoresistance (MR) of 0.19 %, which has the GMR-type character can be observed after an optimal annealing temperature of 450 °C. TEM and X-ray reflectometry suggest that columnar granules with layered Fe form during deposition and with annealing. Magnetoresistive transport is believed to be between the discontinuous layers in each columnar grain. These discontinuous layers are observed to be superparamagnetic in SQUID ZFC-FC measurements measured from 5–300 K. Magnetoresistance can be fitted by the quadratic relation appropriate for GMR in granular films, especially at higher GeTe compositions. When Ge₂Sb₂Te₅ is used instead of GeTe, higher anneal temperatures are required before the MR with GMR character appears. This GMR type response does not appear when pure Fe is used instead of the CoFe alloy, with the samples showing only AMR in this case. This is due to the absence of Co which seems to cause a more granular growth.     

On the metal distribution in the system GeTe−Sb2Te3

The structures of GeSb₂Te₄, Ge₂Sb₂Te₅ and GeSb₄Te₇ are not determined completely by means of classical X-ray or electron diffraction studies. We have measured the Mössbauer parameters of¹²¹Sb in these compounds as well as in their binary constituent Sb₂Te₃ as an attempt to improve our knowledge on the question.     

Phase-change properties related to anharmonicity of local structure

Ge-Sb-Te pseudo-binary compounds are known to be phase-change materials (PCM). Most of these chalcogenide compounds are candidate for future phase-change random access memory (PCRAM) applications since they show abrupt change on crystalline-amorphous phase-change process. For the use in next-generation applications, increase of retention properties and decrease of power needed for phase-change process are required. These phase-change properties depend on various material characteristics, and thermal conductivity is one of them. In this study, to introduce an easier method for evaluating the local structural anharmonicity of phase-change materials, optical pump terahertz (THz) probe experiments were performed. By investigating the phonon behaviours in PCM by this method and comparing them with local structural information extracted from extended X-ray absorption fine structure (EXAFS) on Ge₁Sb₂Te₄ and Ge₂Sb₂Te₅ films, the effects of resonant bonding on lattice anharmonicity and thermal conductivity were determined. As resonant bonding in the local structure get enhanced, local distortion of the system decrease which cause the decrease in anharmonicity. The quantitatively-measured anharmonicity obtained from the optical pump THz probe experiments can be closely related to the structural and electrical properties, thus reflecting well the difference of phase-change properties between Ge₁Sb₂Te₄ and Ge₂Sb₂Te₅ 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.     

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.     

Raman scattering study of GeTe and Ge2Sb2Te5 phase-change materials

Structural details of the amorphous binary GeTe and ternary Ge₂Sb₂Te₅ (GST) phase-change materials are investigated with the aid of Raman scattering. In the case of the a-GeTe, a plethora of Raman bands have been recorded and assigned on the basis of a network structure consisting of corner- and edge-sharing tetrahedra of the type GeTe_4−nGe_n (n=0, 1, 2, 3, 4). Significant temperature-induced structural changes take place in this material even at temperatures well below the crystallization temperature. These changes tend to organize the local structure, in particular the coordination number of Ge atoms, so as to facilitate the amorphous-to-crystal transformation. The much simpler Raman spectrum of GST, characterized by one vibrational band, is accounted for by the dominance of the Sb₂T₃ component in Raman scattering; reasons about this explanation, as well as for the lack of any Te–Te bonds are briefly described.     

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.     

Effect of indium doping on Ge2Sb2Te5 thin films for phase-change optical storage

The influence of In doping on the crystallization kinetics of Ge₂Sb₂Te₅ has been investigated using four-point-probe electrical resistance measurements, grazing incidence X-ray diffraction (XRD), X-ray reflectometry (XRR), variable incident angle spectroscopic ellipsometry, a static tester, and atomic force microscopy. For a stoichiometric Ge₂Sb₂Te₅ alloy doped with 3% In, the amorphous-to-crystalline transition is observed at 150 °C in the sheet resistance measurements. XRD reveals the formation of a predominant NaCl-type Ge₂Sb₂Te₅ phase during the amorphous-to-crystalline transition together with small amounts of crystalline In₂Te₃. Density values of 5.88±0.05 g cm^-3 and 6.22±0.05 g cm^-3 are measured by XRR for the film in the amorphous and crystalline states, respectively. Perfect erasure can be achieved by laser pulses longer than 165 ns. The retarded crystallization, as compared with the undoped Ge₂Sb₂Te₅ alloy, is attributed to the observed phase segregation. Sufficient optical contrast is exhibited and can be correlated with the large density change upon crystallization. PACS 68.55.-a; 78.20.-e; 78.66.Jg     

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.     

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.     

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     

EXAFS study of local order in the amorphous chalcogenide semiconductor Ge2Sb2Te5

Studies of amorphous (a-) semiconductors have been driven by technological advances as well as fundamental theories. Observation of electrical switching, for example, fueled early interest in a-chalcogenides. More recently switching of the a-chalcogenide Ge₂Sb₂Te₅ has been applied quite successfully to DVD technology where the quest for the discovery of better-suited materials continues. Thus, switching provides researchers today with an active arena of technological as well as fundamental study. On the theoretical front, bond constraint theory — or BCT — provides a powerful framework for understanding the structure and properties of a-materials. Applications of BCT to switching in Ge₂Sb₂Te₅ holds the promise of finding the best composition suited for switching applications. This work presents EXAFS data that describe local bonding configurations in as-deposited Ge₂Sb₂Te₅. The data show that Ge₂Sb₂Te₅ may best be viewed as a random array of Ge₂Te₃ and Sb₂Te₃ structural units imbedded in a tissue of a-Te, 17% of which is over coordinated. In addition, a valence alternation pair defect is introduced to the model to satisfy charge conservation constraints.     

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     

Investigation of phase changes in Ge1Sb4Te7 films by single ultra-fast laser pulses

The phase transformations induced in a Ge₁Sb₄Te₇ system by a femtosecond (fs) laser exposure were investigated. The system has a multilayer structure of 15 nm ZnS–SiO₂/80 nm Ge₁Sb₄Te₇/100 nm ZnS–SiO₂/0.6 mm polycarbonate substrate. The morphology and contrast of marks formed in both amorphous and crystalline backgrounds by single fs pulses were characterized using an optical microscope. X-ray diffraction was applied to identify the crystal structures formed by single fs shots. Phase-reversible transformations in the system have been achieved through careful adjustment of the laser fluence. The mechanism of reversibility triggered by fs laser pulses is discussed. The feasibility of phase-change reversible optical recording with the active Ge₁Sb₄Te₇ layer using single fs pulses with a duration of 400 fs within well-defined fluence and pulse energy windows is therefore demonstrated. Our work also demonstrates that it is possible to record and retrieve data rapidly in the Ge₁Sb₄Te₇ film within a conventional optical disk structure using non-amplified laser systems as laser sources. PACS 78.47.+p; 61.80.Ba; 47.20.Hw; 81.40.Ef     

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.     

Characterization of Cr‐doped Sb2Te3 films and their application to phase‐change memory

Phase‐change memory (PCM) is regarded as one of the most promising candidates for the next‐generation nonvolatile memory. Its storage medium, phase‐change material, has attracted continuous exploration. Along the traditional GeTe–Sb₂Te₃ tie line, the binary compound Sb₂Te₃ is a high‐speed phase‐change material matrix. However, the low crystallization temperature prevents its practical application in PCM. Here, Cr is doped into Sb₂Te₃, called Cr–Sb₂Te₃ (CST), to improve the thermal stability. We find that, with increase of the Cr concentration, grains are obviously refined. However, all the CST films exhibit a single hexagonal phase as Sb₂Te₃ without phase separation. Also, the Cr helps to inhibit oxidation of Sb atoms. For the selected film CST_10.5, the resistance ratio between amorphous and crystalline states is more than two orders of magnitude; the temperature for 10‐year data retention is 120.8 °C, which indicates better thermal stability than GST and pure Sb₂Te₃. PCM cells based on CST_10.5 present small threshold current/voltage (4 μA/0.67 V). In addition, the cell can be operated by a low SET/RESET voltage pulse (1.1 V/2.4 V) with 50 ns width. Thus, Cr–Sb₂Te₃ with suitable composition is a promising novel phase‐change material used for PCM with high speed and good thermal stability performances. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Migration of nitrogen in hexagonal Ge2Sb2Te5: An ab‐initio study

The migration barrier energies of the nitrogen atom and N₂ molecule, and the activation barriers for the dissociation and formation of N₂ in Ge₂Sb₂Te₅ were calculated by ab‐initio methods. Various transition and metastable states were found along the migration pathway. Migration barrier energies up to 1.19 eV for the nitrogen atom suggest that it is difficult for it to move from one site to any other site or diffuse out from Ge₂Sb₂Te₅ although doped nitrogen is energetically less stable with respect to N₂ in vacuum. N₂ in Ge₂Sb₂Te₅ was hardly expected to dissociate into nitrogen atoms and vice versa. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)