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.

     

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     

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。     

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。     

Sn和Te掺杂对CrSb2热电性能的不同影响

研究了Sn、Te掺杂对CrSb_2热电性能的不同影响。结果表明,Sn、Te掺杂引起的晶格畸变使电子浓度提高,Te替代Sb是n-型掺杂,而Sn替代Sb是p-型掺杂。由于补偿效应,CrSb_(1.99)Sn_(0.01)的电子浓度小于CrSb_(1.99)Te_(0.01)的电子浓度,导致Sn掺杂使CrSb_2的电阻率和热电势|S|降低的幅度较小。掺杂后声子杂质(Sn、Te)散射增强,CrSb_(1.99)Sn_(0.01)和CrSb_(1.99)Te_(0.01)的热导率都明显减小,而Te的原子量比Sn的大,散射作用更强,热导率减小的幅度更加明显。因此,Te掺杂改善了CrSb_2的热电性能,而Sn掺杂没有改善其性能。此外,由于Sn和Te的d轨道填满了电子而没有磁性,掺杂后样品的Neel温度没有明显改变.     

MOCVD of Bi2Te3 and Sb2Te3 on GaAs substrates for thin-film thermoelectric applications

Metal organic chemical vapour deposition (MOCVD) has been investigated for growth of Bi2Te3 and Sb2Te3 films on (001) GaAs substrates using trimethylbismuth, triethylantimony and diisopropyltelluride as metal organic sources. The surface morphologies of Bi2Te3 and Sb2Te3 films were strongly dependent on the deposition temperatures as it varies from a step-flow growth mode to island coalescence structures depending on deposition temperature. In-plane carrier concentration and electrical Hall mobility were highly dependent on precursor ratio of VI/V and deposition temperature. By optimizing growth parameters, we could clearly observe an electrically intrinsic region of the carrier concentration over the 240 K in Bi2Te3 films. The high Seebeck coefficient (of -160 microVK(-1) for Bi2Te3 and +110 microVK(-1) for Sb2Te3 films, respectively) and good surface morphologies of these materials are promising for the fabrication of a few nm thick periodic Bi2Te3/Sb2Te3 super lattice structures for thin film thermoelectric device applications.     

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.     

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.     

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.     

Preparation of Sb:SnO2 thin films and its effect on opto-electrical properties

The present study focuses on pure and antimony (Sb)-doped tin oxide thin film and its influence on their structural, optical, and electrical properties. Both undoped and Sb-doped SnO₂ thin films have been grown by using simple, inexpensive pyrolysis spray technique. The deposition temperature was optimized to 450 °C. X-ray diffractions pattern have revealed that the films are polycrystalline and have tetragonal rutile-type crystal structure. Undoped SnO₂ films grow along (110) preferred orientation, while the Sb-doped SnO₂ films grow along (200) direction. The size of Sb-doped tin oxide crystals changes from 26.3 to 58.0 nm when dopant concentration is changed from 5 to 25 wt%. The transmission spectra revealed that all the samples are transparent in the visible region, and the optical bandgap varies between 3.92 and 3.98 eV. SEM analysis shows that the surface morphology and grain size are affected by the doping rate. All the films exhibit a high transmittance in the visible region and show a sharp fundamental absorption edge at about 0.38–0.40 nm. The maximum electrical conductivity of 362.5 S/cm was obtained for the film doped with 5 wt% Sb. However, the carrier concentration is increased from 0.708?×?10¹⁸ to 4.058?×?10²⁰ cm³. The electrical study reveals that the films have n-type electrical conductivity and depend on Sb concentration. We observed a decrease in sheet resistance and resistivity with the increase in Sb dopant concentration. For the dopant concentration of 5 wt% of Sb in SnO₂, the Rs and ρ were found minimum with the values of 88.55 (Ω cm^?2) and 2.75 (Ω cm), respectively. We observed an increase in carrier concentration and a decrease in mobility with the addition of Sb up to 25 wt%. The highest figure of merit values 2.5?×?10^–3 Ω^?1 is obtained for the 5wt% Sb, which may be considered potential materials for solar cells' transparent windows.

     

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.     

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。     

不同浓度Cu掺杂SnO2材料电学和力学性质的研究

为研究Cu掺入对SnO_2性能的影响,本文采用密度泛函理论和平面波赝势法,建立了未掺杂SnO_2和不同比例Cu掺杂的SnO_2晶胞模型,对Sn_(1-x)Cu_xO_2(x=0、0.083、0.125、0.167、0.25、0.5)超晶胞体系进行优化计算、能量计算和弹性模量计算,得到晶格常数、弹性模量、电荷分布、能带结构和态密度图.研究表明:掺杂能够使得材料的弹性模量大幅减小,对应的硬化函数值降低,易于材料加工;在电性质方面,掺杂后,材料均属于直接带隙半导体材料.当x0.25时,由于掺杂浓度过高使得晶格发生畸变,电性质与未掺杂情况类似;当x0.25时,随着掺杂浓度的降低,导带收缩加剧,局域性增强,禁带宽度变窄,使得电子从价带受激跃迁所需能量降低,故掺杂后材料表现出半金属性,导电性增强.     

氮掺杂对SnO2薄膜光电性能的影响

SnO2薄膜具有透明导电的特性,因而被制成透明电极而广泛应用于平板显示器和太阳能电池中。研究表明,经掺杂的薄膜具有更优异的光电性能,然而传统的掺杂元素Sb,Te或F较为昂贵且有毒性,因此,掺氮将有望解决上述问题。本文利用反应射频磁控溅射法制备出不同氧含量的SnO2以及氮掺杂SnO2薄膜,并分析了薄膜的形貌结构及光电性能。结果表明:薄膜沉积过程中氧分压和氮掺杂对薄膜性能影响较大。在SnO2薄膜中,晶粒呈包状形态,随着氧分压的增加,晶粒取向从(101)转向(110)方向,晶粒尺寸逐渐变小,可见光透光率提升到80%以上,光学带隙增加到4.05 eV;在氮掺杂SnO2薄膜中,晶粒呈四棱锥形态,晶粒取向为(101)方向,随着氧分压的增加,可见光的透过率同样提升到80%以上,光学带隙增加到3.99 eV。SnO2薄膜和氮掺杂SnO2薄膜的电阻率最低分别达到1.5×10-1和4.8×10-3Ω.cm。     

Structure and topological transport in Pb-doping topological crystalline insulator SnTe(001) film

Topological crystalline insulator(TCI) as a new type of topological materials has attracted extensive research interests for its tunable topological properties. Due its symmetry topological protection essence,the structure investigation provides a solid basement for tuning its topological transport properties.On Sr TiO_3(111) substrate, the Sn Te film was found to be epitaxial growth only along [001] while not[111] direction. The detailed structural study was performed and a structural model was proposed to elucidate epitaxial growth of the Sn Te(001) film. The transport properties of Sn Te(001) film were further investigated and a typical weak anti-localization effect was observed. By Pb-doping into Sn Te, the bulk carriers were inhibited and its topological surface states were strengthened to induce the enhanced surface transport contribution. With tunable multiple transport channels from the even Dirac cones, the TCI Sn Te film systems will have the potential application in future spintronics devices.     

High-resolution transmission electron microscopy study of electrically-driven reversible phase change in ge2sb2te5 nanowires

By combining high-resolution transmission electron microscopy (HRTEM) characterization and electrical measurements on a unique device platform, we study the reversible electrically-driven phase-change characteristics of self-assembled Ge(2)Sb(2)Te(5) nanowires. Detailed HRTEM analyses are used to correlate and understand the effect of full and intermediate structural transformations on the measured electrical properties of the nanowire devices. The study demonstrates that our unique approach has the potential to provide new information regarding the dynamic structural and electrical states of phase-change materials at the nanoscale, which will aid the design of future phase-change memory devices.     

Phosphorus atomic layer doping of germanium by the stacking of multiple δ layers

In this paper we demonstrate the fabrication of multiple, narrow, and closely spaced δ-doped P layers in Ge. The P profiles are obtained by repeated phosphine adsorption onto atomically flat Ge(001) surfaces and subsequent thermal incorporation of P into the lattice. A dual-temperature epitaxial Ge overgrowth separates the layers, minimizing dopant redistribution and guaranteeing an atomically flat starting surface for each doping cycle. This technique allows P atomic layer doping in Ge and can be scaled up to an arbitrary number of doped layers maintaining atomic level control of the interface. Low sheet resistivities (280 Ω/ [symbol see text ) and high carrier densities (2 × 10(14) cm( - 2), corresponding to 7.4 × 10(19) cm( - 3)) are demonstrated at 4.2 K.     

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.     

Sb掺杂对ZnO-V2O5多元系压敏电阻的影响

本文研究了V/Sb预合成粉、SbVO4和Sb2O3等三种不同形式的Sb掺杂对ZnO-V2O5基压敏陶瓷结构和性能的影响.化学计量比不变情况下,上述Sb掺杂方式的改变,使烧结过程中Sb3 离子在陶瓷样品中的浓度上升,促进Zn7Sb2O12型尖晶石相形成,材料晶粒随之细化.同时材料的压敏电压出现大幅上升,而非线性系数和漏电流密度受Sb掺杂形式的变化影响不大.Sb以V/Sb预合成粉进行掺杂可以获得较大尺寸的晶粒,有利于材料在低压方面的应用.     

Nano composite Si2Sb2Te film for phase change memory

Growth-dominant Sb₂Te material with large crystal grain is converted to the nano composite material after Si doping. The increase of Si content in Si_xSb₂Te material helps to further diminish the grain size, form more uniform grain distribution, and enhance the thermal stability of the amorphous phase. Si₂Sb₂Te crystallizes into a nano composite structure [amorphous Si + crystalline Sb₂Te (< 20 nm grain size)] without any Te or Sb phase segregation, which ensures better operation stability for the application in T-shaped phase change memory device. Comparing to Ge₂Sb₂Te₅ film, Si₂Sb₂Te film shows better data retention ability (10 years at 397 K). Meanwhile, electrical measurements prove that phase change memory cell based on Si₂Sb₂Te film also has low power consumption than that of the Ge₂Sb₂Te₅ film based cell.