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.     

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。     

Behavior of GeSbTeBi phase-change optical recording media under subnanosecond pulsed laser irradiation

We investigated the variations in reflectivity during the phase transition between amorphous and crystalline states of a Bi-doped GeTe-Sb2Te3 pseudobinary compound film with subnanosecond laser pulses, using a pump-and-probe technique. We also used a two-laser static tester to estimate the onset time of crystallization under 2.0-micros pulse excitation. Experimental results indicate that the formation of a melt-quenched amorphous mark is completed in approximately 1 ns, but that crystalline mark formation on an as-deposited amorphous region requires several hundred nanoseconds. Simple arguments based on heat diffusion are used to explain the time scale of amorphization and the threshold for creation of a burned-out hole in the phase-change film.     

Crystallization studies on phase-change optical recording media by use of a two-dimensional periodic mark array

We present the results of crystallization studies in thin-film samples of amorphous and crystalline Ge(x)Sb(y)Te(z). The experiments, conducted at moderately elevated temperatures, are based on measurements of the first-order diffraction efficiency from a two-dimensional periodic array of recorded marks. When the samples are slowly heated above room temperature, changes in the efficiencies of various diffracted orders give information about the on-going crystallization process within the sample. Two different compositions of the GeSbTe alloy are used in these experiments. Measurements on Ge(2)Sb(2.3)Te(5) films show crystallization dominated by nucleation. For the Sb-rich eutectic composition Ge-(SbTe), crystallization is found to be dominated by growth from crystalline boundaries. We also show that crystalline marks written by relatively high-power laser pulses are different in their optical properties from the regions crystallized by slow heating of the sample to moderate temperatures.     

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.     

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     

Investigation of crystallization and amorphization dynamics of phase-change thin films by subnanosecond laser pulses

We report experimental results on amorphization and crystallization dynamics of reversible phase-change (PC) thin-film samples, GeSbTe and GeBiTe, for optical disk data storage. The investigation was conducted with subnanosecond laser pulses using a pump-and-probe configuration. Amorphization of the crystalline films could be achieved with a single subnanosecond laser pulse; the amorphization dynamics follow closely the temperature kinetics induced in the irradiated spot. As for crystallization of the samples initially in the amorphous state, a single subnanosecond pulse was found to be insufficient to fully crystallize the irradiated spot, but we could crystallize the PC film (in the area under the focused spot) by applying multiple short pulses. Our multipulse studies reveal that the GeSbTe crystallization is dominated by the growth of nuclei whose initial formation is slow but, once formed, their subsequent growth (under a sequence of subnanosecond pulses) happens quickly. In the case of GeBiTe samples, the crystalline nuclei appear to be present in the material initially, as they grow immediately upon illumination with laser pulses. Whereas our amorphous GeSbTe samples required approximately 200 pulses for full crystallization, for the GeBiTe samples approximately 15 pulses sufficed.     

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。     

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.     

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。     

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.     

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.     

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.     

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.     

Microstructure and crystallization kinetics analysis of the (In15Sb85)(100-x)Zn(x) phase change recording thin films

The (In15Sb85)(100-x)Zn(x) films (x = 0 - 17.4) were deposited on nature oxidized Si wafer and glass substrate at room temperature by magnetron co-sputtering of Sb target and InZn composite target. The thermal property of the films was examined by a homemade reflectivity thermal analyzer. Microstructures of the films were analyzed by transmission electron microscope (TEM). We examined the effects of Zn addition on the thermal property, crystallization kinetics, and crystallization mechanism of the In15Sb85 recording film. As x = 0 - 17.4, thermal analysis shows that the (In15Sb85)(100-x)Zn(x) films have two phase transition temperature ranges which are 189 degrees C-215 degrees C and 300 degrees C-350 degrees C. It is found that the activation energy is increased with Zn content. This indicates that the thermal stability of amorphous state is improved by doping Zn. The optical contrasts of the films are all larger than 15%, as x = 0 - 6.2, indicating that the films have the potential in blue laser optical recording media application.     

Ultrafast switching in nanoscale phase-change random access memory with superlattice-like structures

Phase-change random access memory cells with superlattice-like (SLL) GeTe/Sb(2)Te(3) were demonstrated to have excellent scaling performance in terms of switching speed and operating voltage. In this study, the correlations between the cell size, switching speed and operating voltage of the SLL cells were identified and investigated. We found that small SLL cells can achieve faster switching speed and lower operating voltage compared to the large SLL cells. Fast amorphization and crystallization of 300 ps and 1 ns were achieved in the 40 nm SLL cells, respectively, both significantly faster than those observed in the Ge(2)Sb(2)Te(5) (GST) cells of the same cell size. 40 nm SLL cells were found to switch with low amorphization voltage of 0.9 V when pulse-widths of 5 ns were employed, which is much lower than the 1.6 V required by the GST cells of the same cell size. These effects can be attributed to the fast heterogeneous crystallization, low thermal conductivity and high resistivity of the SLL structures. Nanoscale PCRAM with SLL structure promises applications in high speed and low power memory devices.     

Ga doping induced structural and optical modification in $$\hbox {Ge}_{2}\hbox {Sb}_{2}\hbox {Te}_{5}$$ Ge 2 Sb 2 Te 5 thin films

\(\text {Ge}_2\text {Sb}_2\text {Te}_5\) (GST) is considered a promising candidate for next-generation data storage devices due to its unique property of non-volatility and low power consumption. In present work, the bulk alloys and thin films of (\(\text {Ge}_2\text {Sb}_2\text {Te}_5\))\(_{100-x}\text {Ga}_x\) (x = 0, 3, and 10) are prepared using melt quenching and thermal deposition method, respectively. The effect of Ga doping on host composition is investigated by analyzing X-ray diffraction patterns and field emission scanning electron microscope images. From obtained results, it is found that all doped thin films retained the amorphous nature and exhibited uniform and smooth morphology. In Raman spectra, the appearance of a new peak in 10% Ga-doped GST thin film indicated an alteration in the atomic arrangement of host lattice. Transmission spectra revealed the highly transparent nature of all deposited thin films in the near-infrared region. The optical band gap of Ga-doped GST thin film is lower than that of the pure GST thin film which can be correlated with an increase in band tailing, attributed to an increase in localized defect states in the band gap. Due to the pronounced electronegativity difference between the Ga and Te element, new Ga–Te bonds with a higher number of wrong bonds (Ge–Ge, Sb–Sb, and Ge–Sb) are expected to thermally stabilize the amorphous phase. Such results predict the better performance of Ga-doped GST composition for better performance of phase-change random access memory.