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.     

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     

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。     

Low-consumption phase change material with good data retention selected from SbxTe

Various compositions of SbxTe phase-change films have been investigated by means of in situ temperature-dependent resistance measurement. Although crystallization temperature of Sb3Te is about 536 K, a little lower than those of Sb2Te and Sb4Te, it has a better data retention performance than the other two compositions. X-ray diffraction patterns imply that poly-crystalline structures of Sb-Te alloys are all hexagonal, and phase separation appears in SbTe3, Sb2Te, Sb3Te and Sb4Te alloys. Sb2Te and Sb3Te have been selected for phase-change random access memory devices. RESET voltage for Sb3Te is 1.2 V when the voltage pulse width is 50 ns, 0.3 V lower than that for Sb2Te. By using the voltage pulse width of 200 ns, Sb3Te needs 1.8 V and 4 V to complete SET-RESET performance, 0.4 V and 0.5 V lower than Sb2Te respectively. It indicates that Sb3Te is more suitable for the application of phase-change random access memory.     

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。     

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.     

The order and annealing of quench-condensed lead-based alloys studied by the phonon spectrum from electron tunnelling and by resistance measurements

Metal films consisting of Pb plus 10 at. % of one of eleven different impurities were quench-condensed on substrates at temperatures below 2 K. Ag, Cd, Ga, Ge, In, Mg, Na, Sb, Sn, Te and Zn were used as impurity elements. For these disordered films, the temperature for the transformation from an amorphous to a crystalline state varied qualitatively in accordance with the melting temperature of the impurity element. The degree of order in the disordered films was estimated from the phonon structure in superconductive tunnelling experiments. Structural changes after annealing at 30, 100 and 300 K were studied via altered phonon distributions. During the annealing the resistance as a function of temperature was also monitored. Three different transformations of the lattice order were registered. The most striking of these transformations was the one that took the film from an amorphous into a crystalline state. If the melting temperature of the impurity was greater than twice the value for pure lead, the film transformed directly from an amorphous to a long-range ordered crystalline film at a relatively high annealing temperature. A transformation within the amorphous state was also observed. In contrast to previously reported results, an atomic size difference of 10% between the constituents was not required in order to form an amorphous state in quench-condensed films for this type of alloy.     

Crystallization kinetics of amorphous Ga-Sb films extended for phase-change memory

Performance of phase-change materials based on Ga-Te-Sb was found getting better with decreasing Te content in our earlier studies. We concerned much properties of Te-free, Sb-rich binary Ga-Sb, which has been known to possess extremely fast crystallization behavior. Non-isothermal and isothermal crystallization kinetics of amorphous Sb-rich Ga-Sb films were explored by temperature dependent electrical resistance measurements. The crystallization temperature (183 to 261 degrees C) increases with decreasing Sb content (91 to 77 at%). The activation energy and rate-factor vary with Sb contents and reach the maximum at Ga19Sb81. The kinetic exponent is smaller than 1.5 at Sb < 85 at% denoting that the mechanism is one-dimensional crystal-growth from nuclei. The temperature corresponding to 10-year data-retention, evaluated from films, is 180 degrees C (Ga19Sb81) and 137 degrees C (Ga13Sb87), respectively. We verified memory performance using test-devices made of Ga16Sb84 working at voltages with 100 ns pulse-width.     

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.     

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.     

Magnetic properties and phase change features in Fe-doped Ge-Sb-Te

The relationship between magnetic property and phase change features in Fe-doped Ge-Sb-Te has been studied. Fe-doped Ge-Sb-Te is a phase change magnetic material, which exhibits a fast phase change feature and different magnetic, optical and electrical properties between amorphous and crystalline states. However, the crystallization temperature increases and crystallization rate drops with an increase of Fe doping content. Fe doping content should be less than the solid solubility limit so that Fe-doped Ge-Sb-Te has both magnetic property and phase change features. Fe-doped Ge-Sb-Te at crystalline state shows p-type conduction and has a high hole concentration. The Ruderman-Kittel-Kasuya-Yosida indirect interaction via carriers is the origin of the ferromagnetism in Fe-doped Ge-Sb-Te.     

基于Ga-SbTe的高性能相变存储单元的设计和仿真

相变存储器(PCM)因依靠电阻率的变化来存储的模式,成为65nm以下非易失存储器应用的研究热点.然而,相变存储器的擦写功耗、复位电压、热稳定性和擦写寿命一直是相变存储器发展的几个瓶颈.对此,设计了一种基于相变合金Ga3Sb8Te1的新型嵌入式相变存储器,并建立有限元(FEA)热学,结晶动力学和SPICE宏模型.通过瞬态热学和结晶动力学仿真表明,基于Ga3sb8Te1的相变存储器具有更高的热稳定性和可循环擦写次数、更低的复位功耗,更快的置位频率,是一种较为理想的高性能相变存储器.     

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.     

Rapid solidification of zirconium-based alloys

Zr based metal-metal binary and ternary alloys can be obtained in the amorphous state in very wide composition ranges. Several eutectic reactions and intermetallic compounds are present in these alloy systems which provide opportunities for examining the validity of different theories on glass formation. The amorphous phases in these alloys decompose by a variety of crystallization mechanisms. Instances of polymorphic, primary and eutectic crystallization have been encountered in these glasses. Zr-based metallic glasses possess excellent corrosion resistance and mechanical properties. In several studies their properties have been compared with that of their crystalline counterparts and interesting differences have emerged. In the solute lean Zr-based alloys very large freezing ranges are available for studying the liquid to solid transformation. It has been possible to study the formation of some of the low temperature phases directly from the liquid. This paper describes some of the aforementationed studies carried out on Zr-based amorphous and crystalline alloys.     

Thin film deposition on plastic substrates using silicon nanoparticles and laser nanoforming

Reduced melting temperature of nanoparticles is utilized to deposit thin polycrystalline silicon (c-Si) films on plastic substrates by using a laser beam without damaging the substrate. An aqueous dispersion of 5 nm silicon nanoparticles was used as precursor. A Nd:YAG (1064 nm wavelength) laser operating in continuous wave (CW) mode was used for thin film formation. Polycrystalline Si films were deposited on flexible as well as rigid plastic substrates in both air and argon ambients. The films were analyzed by optical microscopy for film formation, scanning electron microscopy (SEM) for microstructural features, energy dispersive spectroscopy (EDS) for impurities, X-ray photoelectron spectroscopy (XPS) for composition and bond information of the recrystallized film and Raman spectroscopy for estimating shift from amorphous to more crystalline phase. Raman spectroscopy showed a shift from amorphous to more crystalline phases with increasing both the laser power and irradiation time during laser recrystallization step.     

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.