Crystallization behavior of Ge-doped eutectic Sb70Te30 films in optical disks

We report laser-induced crystallization behavior of binary Sb-Te and ternary Ge-doped eutectic Sb70Te30 thin film samples in a typical quadrilayer stack as used in phase-change optical disk data storage. Several experiments have been conducted on a two-laser static tester in which one laser operating in pulse mode writes crystalline marks on amorphous film or amorphous marks on crystalline film, while the second laser operating at low-power cw mode simultaneously monitors the progress of the crystalline or amorphous mark formation in real time in terms of the reflectivity variation. The results of this study show that the crystallization kinetics of this class of film is strongly growth dominant, which is significantly different from the crystallization kinetics of stochiometric Ge-Sb-Te compositions. In Sb-Te and Ge-doped eutectic Sb70Te30 thin-film samples, the crystallization behavior of the two forms of amorphous states, namely, as-deposited amorphous state and melt-quenched amorphous state, remains approximately same. We have also presented experiments showing the effect of the variation of the Sb/Te ratio and Ge doping on the crystallization behavior of these films.     

Crystallization and amorphization studies of a Ge(2)Sb(2.3)Te(5) thin-film sample under pulsed laser irradiation

We present the results of crystallization and amorphization studies on a thin-film sample of Ge(2)Sb(2.3)Te(5), encapsulated in a quadrilayer stack as in the media of phase-change optical disk data storage. The study was conducted on a two-laser static tester in which one laser, operating in pulsed mode, writes either amorphous marks on a crystalline film or crystalline marks on an amorphous film. The second laser, operating at low power in the cw mode, simultaneously monitors the progress of mark formation in terms of the variations of reflectivity both during the write pulse and in the subsequent cooling period. In addition to investigating some of the expected features associated with crystallization and amorphization, we noted certain curious phenomena during the mark-formation process. For example, at low-power pulsed illumination, which is insufficient to trigger the phase transition, there is a slight change in the reflectivity of the sample. This is believed to be caused by a reversible change in the complex refractive index of the Ge(2)Sb(2.3)Te(5) film in the course of heating above the ambient temperature. We also observed that the mark-formation process may continue for as long as 1 mus beyond the end of the write laser pulse. This effect is especially pronounced during amorphous mark formation under high-power, long-pulse illumination.     

聚焦脉冲激光作用下Ge2Sb2Te5薄膜晶化过程及机理

采用聚焦脉冲激光研究了Ge2Sb2Te5薄膜在沉积和激光淬火两种非晶态下反射率与激光脉冲宽度变化的关系，发现沉积态的Ge2Sb2Te5薄膜在晶化触发阶段内的反射率随激光脉冲宽度增加而减小，经过激光淬火的非晶态Ge2Sb2Te5薄膜在晶化触发阶段内的反射率随激光脉冲宽度增加而变化平缓。本文借用气－液体系中过饱和度分析液滴形成的原理，从统计物理学角度详细研究了两种非晶态Ge2Sb2Te5薄膜在脉冲激光作用下的晶化过程及机理，结果表明，当Ge2Sb2Te5的非晶态程度处于未饱和或饱和状态时不形成晶核；当Ge2Sb2Te5的非晶态程度处于过饱和状态时，此时的Ge2Sb2Te5为亚稳态，可能形成大小不等的晶核，但只有半径大于临界晶核尺寸时才可能长大成晶粒，而应力降低晶化能垒，增加非晶态Ge2Sb2Te5的过饱和度是导致沉积态与激光淬火态的Ge2Sb2Te5薄膜在晶化触发阶段内反射率随激光脉冲宽度变化规律不一致的根本原因，并据此解释了Ge2Sb2Te5薄膜在这两种状态下的反射率随激光脉冲宽度的变化特点及规律。     

Study of Ge2Sb2Te5 Film for Nonvolatile Memory Medium

The amorphous Ge2Sb2Te5 film with stoichiometric compositions was deposited by co-sputtering of separate Ge, Sb, and Te targets on SiO2/Si (100) wafer in ultrahigh vacuum magnetron sputtering apparatus. The crystallization behavior of amorphous Ge2Sb2Te5 film was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and differential scanning calorimetry (DSC). With an increase of annealing temperature, the amorphous Ge2Sb2Te5 film undergoes a two-step crystallization process that it first crystallizes in face-centered-cubic (fcc) crystal structure and finally fcc structure changes to hexagonal (hex) structure. Activation energy values of 3.636±0.137 and 1.579±0.005 eV correspond to the crystallization and structural transformation processes, respectively. From annealing temperature dependence of the film resistivity, it is determined that the first steep decrease of the resistivity corresponds to crystallization while the second one is primarily caused by structural transformation from     

From local structure to nanosecond recrystallization dynamics in AgInSbTe phase-change materials

Phase-change optical memories are based on the astonishingly rapid nanosecond-scale crystallization of nanosized amorphous 'marks' in a polycrystalline layer. Models of crystallization exist for the commercially used phase-change alloy Ge(2)Sb(2)Te(5) (GST), but not for the equally important class of Sb-Te-based alloys. We have combined X-ray diffraction, extended X-ray absorption fine structure and hard X-ray photoelectron spectroscopy experiments with density functional simulations to determine the crystalline and amorphous structures of Ag(3.5)In(3.8)Sb(75.0)Te(17.7) (AIST) and how they differ from GST. The structure of amorphous (a-) AIST shows a range of atomic ring sizes, whereas a-GST shows mainly small rings and cavities. The local environment of Sb in both forms of AIST is a distorted 3+3 octahedron. These structures suggest a bond-interchange model, where a sequence of small displacements of Sb atoms accompanied by interchanges of short and long bonds is the origin of the rapid crystallization of a-AIST. It differs profoundly from crystallization in a-GST.     

Dynamic theory of crystallization in Ge2Sb2.3Te5 phase-change optical recording media

We develop a theory of the crystallization dynamics of Ge(2)Sb(2.3)Te(5) thin films that shows good qualitative agreement with experimental reflectivity results from a two-laser static tester. The theory is adapted from the nucleation theory of liquid droplets from supersaturated vapor and elucidates the physics underlying the amorphous-to-crystalline phase transformation under short-pulse excitation. In particular, the theory provides a physical picture in which crystalline islands, or basic embryos, are thermally activated in the amorphous material and subsequently grow as stable nuclei are formed.     

Ge2Sb2Te5材料与非挥发相转变存储器单元器件特性

对Ge2Sb2Te5材料的结构、形貌和电学特性进行了表征,将材料应用于不挥发存储单元器件中并研究了器件性能。研究了退火温度对薄膜电阻率的影响,发现在从高阻向低阻状态转变的过程中,电阻率下降的趋势发生变化,形成拐点,分析表明这是由于在拐点处结构由面心立方向密排六方结构转变所致;对不同厚度Ge2Sb2Te5薄膜的电阻率进行了分析,结果表明当厚度薄于70nm时,电阻率随厚度显著上升而迁移率下降,材料晶态电学性能的测量显示,材料有正电阻温度系数并以空穴导电;测量了Ge2Sb2Fe5非挥发相转变存储器单元的I-V曲线,发现有阈值特性,在晶态时电学特性呈欧姆特性,非晶态时I-V低场为线性关系,电场较高时呈指数关系。     

Density functional calculations on the mechanical properties of nitrogen or oxygen doped crystalline Ge2Sb2Te5

The mechanical properties of pure and doped crystalline Ge2Sb2Te5 were investigated by using density functional calculations. Nitrogen or oxygen was added at either the interstitial or substitutional sites of cubic Ge2Sb2Te5. The lattice parameter, elastic stiffness and related moduli were investigated from the viewpoint of the doping concentration, dopant species, dopant states and film direction. The effect of the doping concentration was more dominant than those of the dopant species and their states on the non-directionality properties, such as the bulk modulus and lattice parameter. It turned out that Ge2Sb2Te5 became slightly more rigid as the doping concentration of nitrogen or oxygen increased. On the other hand, the effect of the film direction on the directional properties, such as the biaxial modulus of the Ge2Sb2Te5 film, was found to be more predominant than that of doping. The biaxial modulus of the (001) oriented film was calculated to be much higher than those of the other films, indicating that the (001) film is the most vulnerable to thermal stress.     

Metal organic chemical vapor deposition of phase change Ge1Sb2Te4 nanowires

The self-assembly of Ge(1)Sb(2)Te(4) nanowires (NWs) for phase change memories application was achieved by metal organic chemical vapor deposition, catalyzed by Au nanoislands in a narrow range of temperatures and deposition pressures. In the optimized conditions of 400 °C, 50 mbar, the NWs are Ge(1)Sb(2)Te(4) single hexagonal crystals. Phase change memory switching was reversibly induced by nanosecond current pulses through metal-contacted NWs with threshold voltage of about 1.35 V.     

Si-Sb-Te materials for phase change memory applications

Si-Sb-Te materials including Te-rich Si?Sb?Te? and Si(x)Sb?Te? with different Si contents have been systemically studied with the aim of finding the most suitable Si-Sb-Te composition for phase change random access memory (PCRAM) use. Si(x)Sb?Te? shows better thermal stability than Ge?Sb?Te? or Si?Sb?Te? in that Si(x)Sb?Te? does not have serious Te separation under high annealing temperature. As Si content increases, the data retention ability of Si(x)Sb?Te? improves. The 10 years retention temperature for Si?Sb?Te? film is ~393 K, which meets the long-term data storage requirements of automotive electronics. In addition, Si richer Si(x)Sb?Te? films also show improvement on thickness change upon annealing and adhesion on SiO? substrate compared to those of Ge?Sb?Te? or Si?Sb?Te? films. However, the electrical performance of PCRAM cells based on Si(x)Sb?Te? films with x > 3.5 becomes worse in terms of stable and long-term operations. Si(x)Sb?Te? materials with 3 < x < 3.5 are proved to be suitable for PCRAM use to ensure good overall performance.     

激光致溅射沉积Ge2Sb2Te5薄膜的结晶行为研究

利用XRD研究了激光致溅射沉积Ge2Sb2Te5薄膜的结晶行为，研究发现，与热致相变不同的是，激光致相变只发生从非晶态到FCC晶态结构的转变，从FCC与HCP的结构转变不再发生，这有利于提高相变光盘的信噪比。Ge2Sb2Te5薄膜的结晶程度受初始化功率和转速的影响。     

Simulation study on heat conduction of a nanoscale phase-change random access memory cell

We have investigated heat transfer characteristics of a nano-scale phase-change random access memory (PRAM) cell using finite element method (FEM) simulation. Our PRAM cell is based on ternary chalcogenide alloy, Ge2Sb2Te5 (GST), which is used as a recording layer. For contact area of 100 x 100 nm2, simulations of crystallization and amorphization processes were carried out. Physical quantities such as electric conductivity, thermal conductivity, and specific heat were treated as temperature-dependent parameters. Through many simulations, it is concluded that one can reduce set current by decreasing both electric conductivities of amorphous GST and crystalline GST, and in addition to these conditions by decreasing electric conductivity of molten GST one can also reduce reset current significantly.     

Effect of Initialization Technical Parameters on Optical Absorption of Ge2Sb2Te5 Thin Films

The optical absorption properties of phase-change optical recording thin films subjected to various initialization conditions were investigated. The effects of initialization power and velocity on optical constants of the Ge2Sb2Te5 thin films were also studied. The energy gap of Ge2Sb2Te5 thin films subjected to various initialization conditions was also obtained. It was found that the optical energy gap of the Ge2Sb2Te5 thin films increased with either increasing initialization laser power or decreasing initialization velocity, with peak of 0.908 eV at laser power of 1000 mW or initialization velocity of 4.0 m/s, but the continued increasing initialization laser power or decreasing initialization velocity resulted in the decrease of the optical energy gap. The change of the optical energy gap was discussed on the basis of amorphous crystalline transformation.     

Three distinct optical-switching states in phase-change materials containing impurities:From physical origin to material design

Ge2Sb2Tes is the most widely utilized chalcogenide phase-change material for non-volatile photonic applications,which undergoes amorphous-cubic and cubic-hexagonal phase transition under external excitations.However,the cubic-hexagonal optical contrast is negligible,only the amorphous-cubic phase transition of Ge2Sb2Te5 is available.This limits the optical switching states of traditional active dis-plays and absorbers to two.We find that increasing structural disorder difference of cubic-hexagonal can increase optical contrast close to the level of amorphous-cubic.Therefore,an amorphous-cubic-hexagonal phase transition with high optical contrast is realized.Using this phase transition,we have developed display and absorber with three distinct switching states,improving the switching perfor-mance by 50％.Through the combination of first-principle calculations and experiments,we reveal that the key to increasing structural disorder difference of amorphous,cubic and hexagonal phases is to intro-duce small interstitial impurities(like N)in Ge2Sb2Tes,rather than large substitutional impurities(like Ag)previously thought.This is explained by the formation energy and lattice distortion.Based on the impurity atomic radius,interstitial site radius and formation energy,C and B are also potential suit-able impurities.In addition,introducing interstitial impurities into phase-change materials with van der Waals gaps in stable phase such as GeSb4Te7,GeSb2Te4,Ge3Sb2Te6,Sb2Te3 will produce high optical con-trast amorphous-metastable-stable phase transition.This research not only reveals the important role of interstitial impurities in increasing the optical contrast between metastable-stable phases,but also proposes varieties of candidate matrices and impurities.This provides new phase-change materials and design methods for non-volatile optical devices with multi-switching states.     

相变光盘记录介质Sb-Se系和Ge-Sb-Te系合金组织及结构

按照配方熔炼制成Sb-Se系和Ge-Sb-Te系合金,对其组织结构进行了观察测试,研究结果表明,制备的合金组织比较均匀,X射线衍射结果表明,Sb-Se系合金1＃样品有Sb析出,2＃样品有Se析出,符合化学计量比的3＃样品全部形成Sb2Se3共晶体。Ge-Sb-Te系合金5＃样品有Sb析出,而符合化学计量比的4＃样品形成GeSb2Te4共晶体。     

Influence of the substrate temperature on the structure and surface roughness of Cd0.18Sb0.64Te0.18 films

Using a radiofrequency sputtering deposition technique, ternary Cd0.18Sb0.64Te0.18 thin films have been grown on glass substrates at several substrate temperatures (50–250°C). The samples have an Sb content of about 63 at %, as measured by Auger spectroscopy. The surface roughness, the structural and the electrical properties of the films were studied as a function of substrate temperature. X-ray diffraction (XRD) measurements showed that the structure of the films changes from an amorphous phase, when deposited at lower substrate temperatures, to a mixture of two crystalline phases (CdTe and Sb) for higher substrate temperatures. Atomic force microscopy shows an increase in the surface roughness with an increase in the substrate temperature, clearly showing the formation of crystalline phases with microcrystallite sizes in good agreement with those determined from XRD measurements. The amorphous-to crystalline transition is accompanied by an abrupt increase in the room temperature electrical conductivity of the films. This increase in the conductivity as well as its temperature dependence in the range of room temperature to 150°C can be understood in terms of an electrical percolation process through the conducting Sb crystallites.     

Surface nucleated crystallization in Ge15Te80As5 semiconducting glasses

The crystalline morphology of electrically conductive surface layers in thermally annealed bulk samples of Ge₁₅Te₈₀As₅ glass has been studied using a scanning electron microscope. Results confirm previous suggestions that crystallization is surface nucleated. Two regions of different crystalline morphology are observed and result from a two-stage crystallization process. Selected-area electron diffraction on extracted particles was used to identify the crystalline phases. The crystallites near the inner glassy material are Te, the first phase to segregate upon annealing. The crystalline material near the sample surface is more dense and contains two phases: GeTe (second-stage crystallization product) and crystalline Te. Energy Dispersive X-Ray Analysis with spacial resolution of 2–3 μm and accuracy of ±10% has shown that the “average” composition is the same for these crystalline regions and for the glassy material.     

Microscopic origin of the fast crystallization ability of Ge-Sb-Te phase-change memory materials

Ge-Sb-Te materials are used in optical DVDs and non-volatile electronic memories (phase-change random-access memory). In both, data storage is effected by fast, reversible phase changes between crystalline and amorphous states. Despite much experimental and theoretical effort to understand the phase-change mechanism, the detailed atomistic changes involved are still unknown. Here, we describe for the first time how the entire write/erase cycle for the Ge(2)Sb(2)Te(5) composition can be reproduced using ab initio molecular-dynamics simulations. Deep insight is gained into the phase-change process; very high densities of connected square rings, characteristic of the metastable rocksalt structure, form during melt cooling and are also quenched into the amorphous phase. Their presence strongly facilitates the homogeneous crystal nucleation of Ge(2)Sb(2)Te(5). As this simulation procedure is general, the microscopic insight provided on crystal nucleation should open up new ways to develop superior phase-change memory materials, for example, faster nucleation, different compositions, doping levels and so on.     

Interfacial phase-change memory

Phase-change memory technology relies on the electrical and optical properties of certain materials changing substantially when the atomic structure of the material is altered by heating or some other excitation process. For example, switching the composite Ge(2)Sb(2)Te(5) (GST) alloy from its covalently bonded amorphous phase to its resonantly bonded metastable cubic crystalline phase decreases the resistivity by three orders of magnitude, and also increases reflectivity across the visible spectrum. Moreover, phase-change memory based on GST is scalable, and is therefore a candidate to replace Flash memory for non-volatile data storage applications. The energy needed to switch between the two phases depends on the intrinsic properties of the phase-change material and the device architecture; this energy is usually supplied by laser or electrical pulses. The switching energy for GST can be reduced by limiting the movement of the atoms to a single dimension, thus substantially reducing the entropic losses associated with the phase-change process. In particular, aligning the c-axis of a hexagonal Sb(2)Te(3) layer and the 〈111〉 direction of a cubic GeTe layer in a superlattice structure creates a material in which Ge atoms can switch between octahedral sites and lower-coordination sites at the interface of the superlattice layers. Here we demonstrate GeTe/Sb(2)Te(3) interfacial phase-change memory (IPCM) data storage devices with reduced switching energies, improved write-erase cycle lifetimes and faster switching speeds.