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.     

Theoretical and experimental investigations of the properties of Ge2Sb2Te5 and indium-doped Ge2Sb2Te5 phase change material

We have carried out comprehensive computational and experimental study on the face-centered cubic Ge₂Sb₂Te₅ (GST) and indium (In)-doped GST phase change materials. Structural calculations, total density of states and crystal orbital Hamilton population have been calculated using first-principle calculation. 5 at.% doping of In weakens the Ge–Te, Sb–Te and Te–Te bond lengths. In element substitutes Sb to form In–Te-like structure in the GST system. In–Te has a weaker bond strength compared with the Sb–Te bond. However, both GST and doped alloy remain in rock salt structure. It is more favorable to replace Sb with In than with any other atomic position. X-ray diffraction (XRD) analysis has been carried out on thin film of In-doped GST phase change materials. XRD graph reveals that In-doped phase change materials have rock salt structure with the formation of In₂Te₃ crystallites in the material. Temperature dependence of impedance spectra has been calculated for thin films of GST and doped material. Thickness of the as-deposited films is calculated from Swanepoel method. Absorption coefficient (α) has been calculated for amorphous and crystalline thin films of the alloys. The optical gap (indirect band gap) energy of the amorphous and crystalline thin films has also been calculated by the equation \( \alpha h\nu = \beta (h\nu - E_{\text{g }} )^{2} \) . Optical contrast (C) of pure and doped phase change materials have also been calculated. Sufficient optical contrast has been found for pure and doped phase change materials.     

Scanning tunneling microscope light emission spectra of polycrystalline Ge2Sb2Te5 and Sb2Te3

We have observed scanning tunneling microscope light emission (STM-LE) spectra of Ge₂Sb₂Te₅ and Sb₂Te₃. Although these chalcogenide alloys exhibit band gaps less than 0.5 eV, the STM-LE was observed with a narrow spectral width at a photon energy of 1.5 eV for both materials. By analyzing its bias voltage, polarity, and temperature dependencies combined with recently reported theoretical electronic structures, we concluded that the STM-LE is excited by electronic transitions taking place in the local electronic structure having a direct gap-like shape with a band gap of 1.5 eV, commonly found in the electronic structures of both materials.     

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     

Dynamics of laser crystallization in amorphous Ge films

In situ time- and space-resolved transmission measurements have been used to investigate the crystal growth during laser irradiation of amorphous Ge films. For dwell times longer than 5 ms, microcrystallization processes comparable to conventional thermal annealing are observed, whereas for irradiation times shorter than 5 ms, shell like crystallites, 20 μm long, are obtained. The results from the pulsed measurements agree with corresponding experiments performed under cw-annealing conditions.     

New structural picture of the Ge2Sb2Te5 phase-change alloy

Using electron microscopy and diffraction techniques, as well as first-principles calculations, we demonstrate that as much as 35% of the total Ge atoms in the cubic phase of Ge2Sb2Te5 locate in tetrahedral environments. The Ge-vacancy interactions play a crucial stabilizing role, leading to Ge-vacancy pairs and the sharing of vacancies that clusters tetrahedral Ge into domains. The Ge2Sb2Te5 structure with coexisting octahedral and tetrahedral Ge produces optical and structural properties in good agreement with experimental data and explains the property contrast as well as the rapid transformation in this phase-change alloy.     

Optical Phonon Spectrum of the Ge2Sb2Te5 Single Crystal

JETP Letters - Raman scattering by optical phonons of the Ge2Sb2Te5 single crystal grown by the Bridgman method is studied for the first time. Another method for obtaining this compound based on...     

Switching phenomena in amorphous thin films of Ge,Cd x Te y and Sb x Se y

The threshold and memory switching effects in amorphous thin films of Ge, Cd _x Te _y and Sb _x Se _y , prepared by cathodic sputtering and vacuum evaporation are investigated. The switching is dependent on the polarity and the material of the contacts. The memory effect is typical for Ge and Cd _x Te _y films whilst the threshold effect sustaining a repeating frequency of about 0·1 Hz was found with Sb _x Se _y , films. The proper switching time was 0·2–0·4 s for the samples under consideration. A considerable variance of the critical intensity of the electric field when the switching set in was observed, as well as a variance of its dependence on the temperature and the surface properties of the substrate. With Ge samples the switching depended on the total amount of energy accumulated in them. A simple model is proposed on the ground of the achieved results assuming electronic processes in the first phase of the duration of the switching (i.e. injection from electrodes into the amorphous film) and bulk thermal processes leading to the creatin of a conduction channel in the second phase.     

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.     

Characteristics of Sn-Doped Ge2Sb2Te5 Films Used for Phase-Change Memory

Sn-doped Ge2Sb2Te5 thin films deposited on Si（100）/SiO2 substrates by rf magnetron sputtering are investigated by a differential scanning calorimeter, x-ray diffraction and sheet resistance measurement. The crystallization temperatures of the 3.58 at.%, 6.92 at.% and 10.04 at.% Sn-doped Ge2Sb2Te5 thin films have decreases of 5.3, 6.1 and 0.9℃, respectively, which is beneficial to reduce the switching current for the amorphous-to-crystalline phase transition. Due to Sn-doping, the sheet resistance of crystalline Ge2Sb2Te5 thin films increases about 2-10 times, which may be useful to reduce the switching current for the amorphous-to-crystalline phase change. In addition, an obvious decreasing dispersibility for the sheet resistance of Sn-doped Ge2Sb2Te5 thin films in the crystalline state has been observed, which can play an important role in minimizing resistance difference for the phase-change memory cell element arrays.     

掺Sn的Ge2Sb2Te5相变存储薄膜的光学性质

提高存储密度和存取速率一直是光存储发展的方向。这对目前用于可擦重写存储的相变材料提出了越来越多的要求：它们既要对短波长有足够的响应,同时其相变速度也越快越好。因此,相变材料性能的改进十分重要,掺杂是提高相变材料性能的重要手段之一。用直流溅射法制备了掺杂不同量Sn的Ge2Sb2Te5相变薄膜,由热处理前后薄膜的X射线衍射（XRD）发现：薄膜发生了从非晶态到晶态的相变。研究了薄膜在250—900nm区域的反射光谱和透射光谱。结果表明：适当的Sn掺杂能大大增加热处理前后材料在短波长（300—405nm）的反射率衬比度,可见,通过Sn掺杂改良相变材料的短波长光存储性能是一种有效的途径。     

Current-voltage characteristics of thin Ge2Sb2Te5 films taken using a measuring circuit with a current source

The measuring circuit with a voltage generator, which is traditionally used for studying electric properties of glasslike semiconductors, is compared with an alternative version using a current generator. The results obtained in the latter case reflect the interrelation between the memory formation effect and changes in the electrical parameters more comprehensively. A new electric parameter, viz. hold voltage U _hold, which has not been described earlier, is introduced. The relation between U _hold and the memory formation process during the phase transition is established. The effect of emergence of oscillations in the current-limiting regime in the conduction channel in the film is detected.     

氮掺杂Ge2Sb2Te5相变存储器的多态存储功能

通过反应溅射的方法,制备了N掺杂的Ge2Sb2Te5(N-GST)薄膜,用作相变存储器的存储介质.研究表明,掺杂的N以GeN的形式存在,不仅束缚了Ge2Sb2Te5 (GST)晶粒的长大也提高了GST的晶化温度和相变温度.利用N-GST薄膜的非晶态、晶态面心立方相和晶态六方相的电阻率差异,能够在同一存储单元中存储三个状态,实现相变存储器的多态存储功能.     

Application of bond constraint theory to the switchable optical memory material Ge2Sb2Te5

A new extended x-ray-absorption fine structure spectroscopy study of local bonding identifies for the first time significant concentrations of Ge-Ge bonds in amorphous Ge2Sb2Te5. The study provides a new understanding of the local molecular structure of this phase-change material. Application of bond constraint theory indicates that the amorphous phase is an ideal network structure in which the average number of constraints per atom equals the network dimensionality. Analysis within this framework imparts new and significant insights concerning the nature of the reversible optically driven amorphous-crystalline phase transition of Ge2Sb2Te5.     

Nickel induced lateral crystallization behavior of amorphous silicon films

Nickel induced lateral crystallization of amorphous silicon with and without electric field has been studied. Dendritic silicon growth behavior is observed, with crystallites of a few hundred nanometers in width and up to a few microns in length. The behavior can be understood from the preferential epitaxial growth of silicon from the (1 1 1) facets of the NiSi₂ precipitate, which forms during the early stage of the annealing process. The dendritic growth fronts are different with and without electric field in the nickel induced lateral crystallization process. Electric field is found to be beneficial in increasing the lateral crystallization rate and improving the film crystallinity. Joule heating plays an important role as well to enhance the lateral crystallization.     

溅射气压对Ge2Sb2Te5薄膜光学常数的影响

实验研究了氩气气压对溅射制备的Ge2 Sb2 Te5 薄膜的光学常数随波长变化的影响 ,结果表明 :随薄膜制备时氩气气压的增加 ,Ge2 Sb2 Te5 薄膜的折射率n先增大后减小 ,而消光系数k先减小后增大。二者都随波长的变化而变化 ,且在长波长范围变化较大 ,短波长范围变化较小 ,解释了溅射气压对Ge2 Sb2 Te5 薄膜的光学常数影响的机理     

Pressure-induced site-selective disordering of Ge2Sb2Te5: a new insight into phase-change optical recording

We demonstrate that , the material of choice in phase-change optical recording (such as DVD-RAM), can be rendered amorphous by the application of hydrostatic pressure. It is argued that this structural change is due to a very strong second-nearest-neighbor Te-Te interaction that determines the long-range order in the metastable cubic phase of and also to the presence of vacancies. This newly discovered phenomenon suggests that pressure is an important factor for the formation of the amorphous phase which opens new insight into the mechanism of phase-change optical recording.     

Different crystallization processes of as-deposited amorphous Ge2Sb2Te5 films on nano- and picosecond single laser pulse irradiation

The crystallization dynamics of as-deposited amorphous Ge₂Sb₂Te₅ films induced by nano- and picosecond single laser pulse irradiation is studied using in situ reflectivity measurements. Compared with nanosecond laser pulse, the typical recalescence phenomenon did not appear during the picosecond laser pulse-induced crystallization processes when the pulse fluence gradually increased from crystallization to ablation threshold. The absence of melting and recalescence phenomenon significantly decreased the crystallization time from hundreds to a few tens of nanoseconds. The role of pulse duration time scale on the crystallization process is qualitatively analyzed.