Study of aluminium-modified Ge2Sb2Te5 thin films for the applicability as phase-change storage device material

Electrical and optical studies have been carried out on aluminium-modified Ge₂Sb₂Te₅ thin films to check its applicability as an active material in optical and electrical memory storage devices. Five polycrystalline bulk samples were prepared with compositions: Al_x(Ge₂Sb₂Te₅)_1?x; x = 0, 0.08, 0.14, 0.21, 0.25. Amorphous thin films were deposited from the polycrystalline bulk by thermal evaporation. Temperature-dependent resistance shows the increase in crystallization temperature of Ge–Sb–Te films on aluminium addition. Activation energy for conduction, conductivity, optical band gap, coefficient of refraction and extinction coefficient are studied with respect to Al content in both amorphous and crystalline phases of Ge–Sb–Te alloy films.     

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.     

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     

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     

Characteristics of Si-doped Sb2Te3 thin films for phase-change random access memory

The characteristics of Si-doped Sb₂Te₃ thin films were investigated using differential scanning calorimetry (DSC), four-point probe technique, X-ray diffraction (XRD) analysis and high resolution transmission electron microscopy (HRTEM). It is found that the as-deposited Sb₂Te₃ film in our study is partly crystallized. Silicon doping increases the crystallization temperature and resistivity of Sb₂Te₃ film significantly. XRD and HRTEM analyses indicated that some of the doped Si atoms substitute for Sb or Te in the lattice, while others exists at the grain boundaries in the form of amorphous phase, which may be responsible for grain size reduction and high crystalline resistivity of Si-doped specimens. Compared with the conventional Ge₂Sb₂Te₅ film, Si-doped Sb₂Te₃ films exhibit lower melting temperature and higher crystalline resistivity, which is beneficial to RESET current reduction of phase-change random access memory (PRAM). These results show the feasibility of Si-doped Sb₂Te₃ films in PRAM application.     

Ge/Sb2Te3 nanocomposite multilayer films for high data retention phase-change random access memory application

The amorphous-to-crystalline transition of Ge/Sb₂Te₃ nanocomposite multilayer films with various thickness ratios of Ge to Sb₂Te₃ were investigated by utilizing in situ temperature-dependent film resistance measurements. The crystallization temperature and activation energy for the crystallization of the multilayer films increased with the increase in thickness ratio of Ge to Sb₂Te₃. The difference in sheet resistance between amorphous and crystalline states could reach as high as 10⁴ Ω/□. The crystallization temperature and activation energy for the crystallization of Ge/Sb₂Te₃ nanocomposite multilayer films was proved to be larger than that of conventional Ge₂Sb₂Te₅ film, which ensures a better data retention for phase-change random access memory (PCRAM) use. A data retention temperature for 10 years of the amorphous state [Ge (2 nm)/Sb₂Te₃ (3 nm)]₄₀ film was estimated to be 165 °C. Transmission electron microscopy (TEM) images revealed that Ge/Sb₂Te₃ nanocomposite multilayer films had layered structures with clear interfaces.     

Studies on electrical switching behavior and optical band gap of amorphous Ge–Te–Sn thin films

Amorphous thin film Ge₁₅Te_85−x Sn _x (1≤x≤5) and Ge₁₇Te_83−x Sn _x (1≤x≤4) switching devices have been deposited in sandwich geometry using a flash evaporation technique, with aluminum as the top and bottom electrodes. Electrical switching studies indicate that these films exhibit memory type electrical switching behavior. The switching fields for both the series of samples have been found to decrease with increase in Sn concentration, which confirms that the metallicity effect on switching fields/voltages, commonly seen in bulk glassy chalcogenides, is valid in amorphous chalcogenide thin films also. In addition, there is no manifestation of rigidity percolation in the composition dependence of switching fields of Ge₁₅Te_85−x Sn _x and Ge₁₇Te_83−x Sn _x amorphous thin film samples. The observed composition dependence of switching fields of amorphous Ge₁₅Te_85−x Sn _x and Ge₁₇Te_83−x Sn _x thin films has been understood on the basis of Chemically Ordered Network model. The optical band gap for these samples, calculated from the absorption spectra, has been found to exhibit a decreasing trend with increasing Sn concentration, which is consistent with the composition dependence of switching fields.     

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.     

Influence of thickness on the optical properties of amorphous GeSe2 thin films: analysis using Raman spectra,Urbach energy and Tauc parameter

An analysis is reported of thickness-induced defects in amorphous GeSe₂ thin films deposited by the vacuum evaporation technique. X-ray diffraction studies confirmed the amorphous nature of the thin films. Optical absorption measurements revealed an indirect transition with an energy gap that increases with film thickness. A blue shift in optical transmittance edges was observed in annealed GeSe₂ thin films. The obtained lower values of Urbach energy (E _U) indicate that as thickness increases more ordered films can be produced. Raman spectra suggest that annealing promotes corner-sharing GeSe_4/2 tetrahedra and edge-sharing Ge₂Se_8/2 bi-tetrahedra bonding and leads to the reduction in disorder in bonding network, which is amply supported by the way of increase in band gap, increase in Tauc parameter (B ^1/2) and reduction in E _U from the analysis of transmittance spectra. Increasing the thickness promotes tetrahedral and bi-tetrahedral bonding through the reduction in bonding defects.     

Phase transition characteristics of Ge–Sb–Te pseudobinary alloys in laser irradiation measurement

Optical switching and structural transformation of GeTe–Sb₂Te₃ pseudobinary alloys, Ge₂Sb₂Te₅, Ge₁Sb₂Te₄, and Ge₁Sb₄Te₇, were studied for data storage application. As-deposited Ge₂Sb₂Te₅, Ge₁Sb₂Te₄, and Ge₁Sb₄Te₇ thin films were amorphous and they crystallized to FCC and HCP upon heat treatment. Crystallization was accelerated by increasing the proportion of Sb₂Te₃ rather than GeTe in Ge–Sb–Te compounds; this was observed by reflectivity changes under nanosecond laser irradiation in static tester. The different crystallization kinetics according to composition might be affected by the structural incompatibility of GeTe under the ‘Umbrella Flip’ theory.     

Optical properties of Ge-As-Te thin films

Different compositions of Ge_xAs₁₀Te_90−x (x=5, 10, 15, 20, and 25 at%) chalcogenide glasses were prepared by the usual melt quench technique. Amorphous Ge_xAs₁₀Te_90−x thin films were deposited onto cleaned glass substrates using the thermal evaporation method. Transmission spectra, T(λ), of the films at normal incidence were measured in the wavelength range 400-2500 nm. A straightforward analysis proposed by Swanepoel based on the use of the maxima and minima of the interference fringes has been used to drive the film thickness, d, the complex index of refraction, n, and the extinction coefficient, k. It was found that, the addition of Ge content at the expense of Te atoms shifts the optical band gap to the short wavelength side (blue shift of the optical band gap) while the refractive index are found to decreases. The obtained results of the refractive index were discussed in terms of the electronic polarizability and the single-oscillator Wemple and DiDomenico model (WDD). The optical absorption is due to the allowed non-direct optical transitions. The observed increase in the optical band gap with the increase in Ge content was discussed in terms of the width of the tail states in the gap and the covalent bond approach.     

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.     

Ge2Sb2Te5薄膜光学性能和短波长静态记录特性的研究

利用直流磁控溅射制备了单层Ge₂Sb₂Te₅薄膜,研究了薄膜在400～800 nm区域的反射、透过光谱,计算了它的吸收系数,发现薄膜在400～800 nm波长范围内具有较强的吸收.随着薄膜厚度的增加,相应的禁带宽度Eg也随之增加.对Ge2Sb2Te5薄膜光存储记录特性的研究发现,在514.5 nm波长激光辐照样品时,薄膜具有良好的写入对比度,擦除前后的反射率对比度在6%~18%范围内.对实验结果进行了分析.     

Optical properties and crystallization of AgInTeSbGe phase-change optical disk media

AgInTeSbGe thin films were deposited by the dc sputtering method. Due to germanium doping in the AgInTeSb film, new Ag₂Te and Ge₂Sb₂Te₅ crystalline phases were formed. The crystallization temperature and the activation energy of the AgInTeSbGe thin film increased manifestly with the addition of Ge. The refractive index n and the extinction coefficient k of the AgInTeSbGe film in the amorphous and crystalline states were measured. The reflectivity contrast of the AgInTeSbGe phase-change optical disk was greater than %30 in almost the whole visible region. A minimum recording mark of about 220 nm in length was recorded using the AgInTeSbGe thin film as the recording medium. The reflectivity contrast of the minimum recording mark was about %25. PACS 42.70.Ln; 61.72.Ww; 78.66.Li; 81.30.Hd     

Ga30Sb70/Sb80Te20纳米复合多层薄膜的相变特性研究

采用磁控二靶(Ga₃₀Sb₇₀和Sb₈₀Te₂₀)交替溅射方法制备了新型Ga₃₀Sb₇₀/Sb₈₀Te₂₀纳米复合多层薄膜, 对多层薄膜周期中Ga₃₀Sb₇₀层厚度对相变特性的影响进行了研究. 结果表明, 多层薄膜的结晶温度可以通过周期中Ga₃₀Sb₇₀层厚度进行调节, 且随着Ga₃₀Sb₇₀层厚度的增加而升高. Ga₃₀Sb₇₀/Sb₈₀Te₂₀纳米复合多层薄膜的光学带隙随Ga₃₀Sb₇₀层厚度的增加而增大. 采用皮秒激光脉冲抽运光探测技术研究了多层薄膜的瞬态结晶动力学过程, 利用不同能量密度的皮秒激光脉冲可以实现Ga₃₀Sb₇₀/Sb₈₀Te₂₀多层薄膜非晶态和晶态的可逆转变.     

Optical investigation of vacuum evaporated Se80−xTe20Sbx (x = 0, 6, 12) amorphous thin films

Amorphous thin films of Se_80−xTe₂₀Sb_x (x = 0, 6, 12) chalcogenide glasses has been deposited onto pre-cleaned glass substrate using thermal evaporation technique under a vacuum of 10⁻⁵ Torr. The absorption and transmission spectra of these thin films have been recorded using UV spectrophotometer in the spectral range 400–2500 nm at room temperature. Swanepoel envelope method has been employed to obtain film thickness and optical constants such as refractive index, extinction coefficient and dielectric constant. The optical band gap of the samples has been calculated using Tauc relation. The study reveals that optical band gap decreases on increase in Sb content. This is due to decrease in average single bond energy calculated using chemical bond approach. The values of urbach energy has also been computed to support the above observation. Variation of refractive index has also been studies in terms of wavelength and energy using WDD model and values of single oscillator energy and dispersion energy has been obtained.     

The thickness dependence of the crystallization behavior in sandwiched amorphous Ge2Sb2Te5 thin films

The thickness dependent crystallization behavior of thin amorphous Ge₂Sb₂Te₅(GST) films sandwiched between different cladding materials has been investigated based on a thermodynamic model. It is revealed that there is a critical thickness below which the crystallization cannot occur. The critical thickness is determined by the energy difference Δγ between the crystalline GST/substrate interface energy and the amorphous GST/substrate interface energy, the melting enthalpy, and the mole volume. The calculated result is in good agreement with the experiments. Furthermore, the crystallization temperature is also affected by interface energy difference Δγ. Larger Δγ gives rise to a higher crystallization temperature, and vice versa. This impact becomes stronger as the film thickness is decreased.     

Compositional dependence of the optical properties of the amorphous GexTe1−x system

Optical absorption at room temperature of vacuum evaporated Ge_xTe_1−x (0.125?x?0.225) amorphous thin films has been studied as a function of composition. It was found that the optical absorption is due to a direct transition. The real and imaginary parts of the dielectric constant were determined. The single-oscillator energy (E_o) and the energy dispersion parameter (E_d) have been calculated and discussed in terms of the Wemple and Di-Domenico model. The relationship between the optical gap, the average heat of atomization and the coordination numbers has been determined. The optical properties of the amorphous thin films do not change monotonically with increasing Ge content. The observed behavior of the optical properties in the range of compositions studied are explained on the basis of the Bond Constraint Theory (BCT) and rigidity theory, which provide a powerful framework for understanding the structure and properties of amorphous materials. The non-monotonic variation of the optical properties indicates that a transition from floppy to rigid occurs in the Ge_xTe_1−x films.     

应用于相变存储器的Cu-Ge3Sb2Te5薄膜的结构及相变特性研究

采用磁控溅射法制备了不同Cu含量的Cu-Ge₃Sb₂Te₅薄膜, 原位测试了薄膜电阻与温度的关系, 并利用X射线衍射仪、透射电镜、透过和拉曼光谱仪分别研究了 Cu-Ge₃Sb₂Te₅薄膜的晶体结构、微结构、禁带宽度及成键情况. 结果表明, Cu-Ge₃Sb₂Te₅薄膜的结晶温度和结晶活化能随着Cu含量的增加而增大, Cu的加入有效改善Ge₃Sb₂Te₅薄膜的热稳定性和10年数据保持力. 随着Cu含量的增加, 非晶态Cu-Ge₃Sb₂Te₅薄膜的禁带宽度逐渐减小. 同时, 拉曼峰从129 cm^-1向127 cm^-1处移动, 这是由于Cu–Te极性键振动增强的缘故. Cu-Ge₃Sb₂Te₅结晶为均匀、相互嵌套的六方Cu₂Te和Ge₂Sb₂Te₅相.     

Optical characterization of tin containing novel chalcogen rich glassy semiconductors

Amorphous thin film materials with different compositions of Se_80?xTe₂₀Sn_x (0 ≤ x ≤ 10) system have been deposited on glass substrates by a well known thermal evaporation technique. Structural characterization of different compositions of aforementioned system has been done by Raman spectroscopy. The optical properties of thin films have been studied in the wavelength range 200–1100 nm by the utilization of the optical absorbance spectra of deposited thin films. To calculate the optical band gap from the optical absorption spectra, we have used Tauc model that follows the mechanism of allowed ‘non-direct electronic transition’. Subsequently, we have determined the energy band gap, metallization criterion and refractive index of thin films of aforesaid system. The variation in optical properties with composition has been interpreted in terms of density of defect states.