Thermal effect of Ge_2Sb_2Te_5 in phase change memory device

The properties of Raman phonons are very important due to the fact that they can availably reflect some important physical information. An abnormal Raman peak is observed at about 558 cm-1in In film composed of In/InOx core–shell structured nanoparticles, and the phonon mode stays very stable when the temperature changes. Our results indicate that this Raman scattering is attributed to the existence of incomplete indium oxide in the oxide shell.     

Characterization of Cr‐doped Sb2Te3 films and their application to phase‐change memory

Phase‐change memory (PCM) is regarded as one of the most promising candidates for the next‐generation nonvolatile memory. Its storage medium, phase‐change material, has attracted continuous exploration. Along the traditional GeTe–Sb₂Te₃ tie line, the binary compound Sb₂Te₃ is a high‐speed phase‐change material matrix. However, the low crystallization temperature prevents its practical application in PCM. Here, Cr is doped into Sb₂Te₃, called Cr–Sb₂Te₃ (CST), to improve the thermal stability. We find that, with increase of the Cr concentration, grains are obviously refined. However, all the CST films exhibit a single hexagonal phase as Sb₂Te₃ without phase separation. Also, the Cr helps to inhibit oxidation of Sb atoms. For the selected film CST_10.5, the resistance ratio between amorphous and crystalline states is more than two orders of magnitude; the temperature for 10‐year data retention is 120.8 °C, which indicates better thermal stability than GST and pure Sb₂Te₃. PCM cells based on CST_10.5 present small threshold current/voltage (4 μA/0.67 V). In addition, the cell can be operated by a low SET/RESET voltage pulse (1.1 V/2.4 V) with 50 ns width. Thus, Cr–Sb₂Te₃ with suitable composition is a promising novel phase‐change material used for PCM with high speed and good thermal stability performances. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

ZnSb掺杂的Ge2Sb2Te5薄膜的相变性能研究

本文采用双靶(ZnSb靶和Ge₂Sb₂Te₅靶)共溅射制备了系列ZnSb掺杂的Ge₂Sb₂Te₅(GST)薄膜. 利用X射线衍射、透射电子显微镜、原位等温/变温电阻测量、X射线光电子能谱等测试研究了薄膜样品的非晶形态、电学及原子成键特性. 利用等温原位电阻测试表明ZnSb掺杂的Ge₂Sb₂Te₅薄膜具有更高的结晶温度. 采用Arrhenius 公式计算发现ZnSb掺杂的Ge₂Sb₂Te₅薄膜的十年数据保持温度均高于传统的Ge₂Sb₂Te₅薄膜的88.9℃. 薄膜在200, 250, 300和350℃ 下退火后的X射线衍射图谱表明ZnSb的掺杂抑制了Ge₂Sb₂Te₅薄膜从fcc态到hex态的转变. 通过对薄膜的光电子能谱和透射电镜分析可知Zn, Sb, Te原子之间键进行重组, 形成Zn–Sb 和Zn–Te 键, 且构成非晶物质存在于晶体周围. 采用相变静态检测仪测试样品的相变行为发现ZnSb掺杂的Ge₂Sb₂Te₅薄膜具有更快的结晶速度. 特别是(ZnSb)_24.3(Ge₂Sb₂Te₅)_75.7薄膜, 其结晶温度达到250℃, 十年数据保持温度达到130.1℃, 并且在70 mW激光脉冲功率下晶化时间仅～64 ns, 远快于传统Ge₂Sb₂Te₅薄膜的晶化时间～280 ns. 以上结果表明(ZnSb)_24.3(Ge₂Sb₂Te₅)_75.7薄膜是一种热稳定性好且结晶速度快的相变存储材料.     

Phase transformation mechanism of In–Sb–Te through the boundary reaction between InSb and InTe

The boundary reaction between InSb and InTe bilayers shows that In₃Sb₁Te₂ (IST) is formed at the InTe side first due to the diffusion of Sb atoms from InSb to InTe rather than the diffusion of Te atoms from InTe to InSb at the crystallization temperature of IST. The diffusion of Sb atoms into InTe changes the atomic configuration of InTe, which leads to small lattice distortion and a coherent boundary region for the formation of IST crystalline thin films. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Low-temperature phase transformation of CZTS thin films

The low temperature phase transformation in the Cu_2ZnSnS_4(CZTS) films was investigated by laser annealing and low temperature thermal annealing.The Raman measurements show that a-high-power laser annealing could cause a red shift of the Raman scattering peaks of the kesterite(KS) structure and promotes the formation of the partially disordered kesterite(PD-KS) structure in the CZTS films,and the low-temperature thermal annealing only shifts the Raman scattering peak of KS phase by several wavenumber to low frequency and the broads Raman peaks in the low frequency region.Moreover,the above two processes were reversible.The Raman analyses of the CZTS samples prepared under different process show that the PD-KS structure tends to be found at low temperatures and low sulfur vapor pressures.Our results reveal that the control of the phase structure in CZTS films is feasible by adjusting the preparation process of the films.     

Phase changeable silver selenide thin films fabricated by pulse electrodeposition

We have used a simple and direct method to successfully prepare Ag₂Se thin films by pulse electrodeposition from a single aqueous solution of Ag and Se ions. The composition analysis confirms the stoichiometry and the morphological characterization shows that the thin films are dense and smooth. The films have the orthorhombic structure of regular Ag₂Se materials at room temperature, while the electrical measurements reveal an interesting electrical behavior, similar to that of the Ag₂Se nanowire arrays. The Ag₂Se thin films were successfully deposited into polymer templates to form well-defined Ag₂Se nanostructure, which provides a possibility to apply the method to high density, non-volatile memories based on phase change materials.     

Phase transformation and quantum confinement effect in CdSe/Se multilayer thin films prepared by physical vapour deposition

CdSe/Se multilayer (ML) thin films with different thickness ratios of Se and CdSe sublayers were prepared by using a thermal evaporation method. Prepared samples were annealed at temperature 300 K. From X-ray diffraction (XRD) studies, samples prepared at room temperature showed a (100) plane of CdSe with wurtzite structure, whereas the annealed samples confirmed the cubic structure. Stress created in ML systems was calculated from XRD data and found that it increases with decreasing particle size. The energy band gap value of a CdSe/Se ML thin film is shifted to a value higher than that of the bulk CdSe (1.74 eV) semiconductor. This is due to decrease in the crystallite size smaller than the Bohr exciton diameter of CdSe (11.2 nm). Crystallite sizes (≈5 nm) were calculated from UV–VIS data with the predictions of an effective mass approximation model. The photoluminescence peak of the ML samples is split into two bands having nearest values due to the emissions from spin–orbit split-up of the excited energy state.     

Phase transitions and domain structures in thin ferroelectric films

Recent advances in technology made available high quality thin ferroelectric films and ferroelectric–paraelectric multilayers. But understanding of the properties of these systems is far from being complete. In particular, it is not clear why various anomalies observed at phase transitions here are different from those in high quality bulk systems. The aim of the paper is to discuss some specific features of ferroelectric phase transitions in thin films and multilayers which are taken into account only partially by the theory. The discussion is limited to revealing the character of ferroelectric state forming just after the transition, i.e. if it is single-domain or multi-domain, if it is single-phase or two-phase. First, thin films with electrodes and on a substrate are discussed. The role of non-ideality of electrodes in realization of one of the first pairs of possibilities is emphasized. A more recent idea is that even for ideal electrodes a domain formation is possible when some conditions on the electrode–ferroelectric interface and the material constants of the material are met. This seems to be quite possible for the considered systems. Clamping by the substrate may lead to formation of a two-phase state which is practically unexplored for very thin films on substrates. Second, ferroelectric–paraelectric multilayers are considered which are more challenging for theoretical study than the thin films. Indeed, despite periodicity in the composition the domain structures are almost never periodic along the multilayer. The non-ideality of electrodes seems to lead to practical impossibility of single-domain ferroelectric phase transition in the multilayers of the considered type.     

立方氮化硼薄膜沉积过程的相变研究

从能量和结构两个角度分析了BN四种相的转变过程，以及杂质和缺陷对立方氮化硼(c-BN)薄膜制备的影响.研究了从六角氮化硼(h-BN)到c-BN转变的一个可能的过程，即h-BN→菱形氮化硼(r-BN)→c-BN过程.对纯的h-BN到r-BN的转变需要克服一个很高的能量势垒，在实验室条件下很难能够提供能量来越过这个势垒.而从r-BN到c-BN的转变只需要克服一个很低的能量势垒.这个能量势垒要低于从h-BN到纤锌矿氮化硼(w-BN)转变所需要克服的能量势垒.c-BN薄膜的制备过程中，薄膜在高能粒子轰击下，会产生大量的缺陷，这些缺陷对立方相的形成起到了重要的作用，缺陷和杂质的存在大大降低了从h-BN到r-BN转变的能量势垒.根据这个理论模型，在两步法制备c-BN薄膜的基础上，调整实验参数，形成三步法制备高质量c-BN薄膜.主要研究了三步法中第一步的时间和衬底负偏压对c-BN薄膜制备的影响，找到合适的沉积时间和衬底负偏压分别为5min和-180V.采用三步法制备薄膜，可以重复得到高立方相体积分数(立方相体积分数超过80%)的BN薄膜，并且实验重复性达到70%以上. 关键词： 立方氮化硼 能量势垒 缺陷 衬底偏压     

Phase transformation kinetics induced in thin sol-gel PZT films under thermal annealing

The surface morphology evolution and phase transformation kinetics in thin lead zirconate-titanate (PZT) sol-gel films during rapid thermal annealing were studied by in situ measurement of scattered light intensity and by recording successive instantaneous optical microscope images. We also studied the variation of the texture perfection, the fraction of the growing phase, and the angular dependence of the scattered intensity in partially annealed samples. The parameters characterizing the kinetics of the pyrochlore-perovskite phase transformation were derived by a mathematical treatment of the experimental data. The phase transformation kinetics and the film crystalline texture are shown to depend substantially on the pyrolysis temperature. The texture formation mechanism is considered.     

Sb_2Te_3热电薄膜的离子束溅射制备与表征

采用离子束溅射技术交替沉积Sb-Te-Sb多层薄膜后进行高真空热处理,直接制备Sb2Te3薄膜.利用X射线衍射(XRD)仪、霍尔系数测试仪、薄膜Seebeck系数测量系统对所制备的薄膜特性进行表征.XRD测量结果显示,薄膜的主要衍射峰与Sb2Te3标准衍射峰相同,在[101]/[012]晶向取向明显,存在较多的Te杂质峰;霍尔系数测试结果表明,薄膜为p型半导体薄膜,薄膜电阻率较低,其电导率接近于金属电导率,载流子浓度量级为1023cm-3,具有良好的电学性能;Seebeck系数测量结果显示,薄膜具有良好的热电性能,在不同条件下制备的薄膜的Seebeck系数在7.8—62μV/K范围;在所制备的薄膜中,退火时间为6h、退火温度为200℃的薄膜其Seebeck系数达到最大,约为62μV/K,且电阻率最小.     

Temperature dependence of the Raman spectra of Bi2Te3 and Bi0.5Sb1.5Te3 thermoelectric films

The temperature dependence of the Raman spectra of Bi₂Te₃ and Bi_0.5Sb_1.5Te₃ thermoelectric films was investigated. The temperature coefficients of the E_g(2) peak positions were determined as –0.0137 cm^–1/°C and –0.0156 cm^–1/°C, respectively. The thermal expansion of the crystal caused a linear shift of the Raman peak induced by the temperature change. Based on the linear relation, a reliable and noninvasive micro‐Raman scattering method was shown to measure the thermal conductivity of the thermoelectric films. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

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.     

Thermal stability and data retention of resistive random access memory with HfO_x/ZnO double layers

As an industry accepted storage scheme, hafnium oxide(HfO_x) based resistive random access memory(RRAM)should further improve its thermal stability and data retention for practical applications. We therefore fabricated RRAMs with HfO_x/ZnO double-layer as the storage medium to study their thermal stability as well as data retention. The HfO_x/ZnO double-layer is capable of reversible bipolar switching under ultralow switching current( 3 μA) with a Schottky emission dominant conduction for the high resistance state and a Poole–Frenkel emission governed conduction for the low resistance state. Compared with a drastically increased switching current at 120℃ for the single HfO_x layer RRAM, the HfO_x/ZnO double-layer exhibits excellent thermal stability and maintains neglectful fluctuations in switching current at high temperatures(up to 180℃), which might be attributed to the increased Schottky barrier height to suppress current at high temperatures. Additionally, the HfO_x/ZnO double-layer exhibits 10-year data retention @85℃ that is helpful for the practical applications in RRAMs.     

Electrodeposition of thermoelectric Bi2Te3 thin films with added surfactant

Bismuth telluride (Bi₂Te₃) thin films were electrodeposited at room temperature from nitric baths in the presence of a surfactant, cetyltrimethylammonium bromide (CTAB). Nearly stoichiometric Bi₂Te₃ thin films were obtained from electrolytes containing 7.5 mM Bi(NO₃)₃. The surface morphology and mechanical properties of the electrodeposited thin film were improved by the addition of CTAB to the electrolyte, while the electrical and thermoelectric properties were preserved. Post-deposition annealing in a reducing environment did not improve the electrical and thermoelectric properties, possibly because the change in the microstructure of the Bi₂Te₃ thin film was too small.     

Thickness-dependent electrical and optical properties of Ge8Sb2Te11 thin films

The amorphous Ge₈Sb₂Te₁₁thin films with varying thickness are thermally deposited on well-cleaned glass substrate from its polycrystalline bulk. Absence of any sharp peak confirms the amorphous nature of deposited films. Thickness-dependent electrical and optical properties including dc-activation energy, sheet resistivity, optical band gap, band tailing parameter, etc. of Ge₈Sb₂Te₁₁thin films have been studied. The optical parameters have been calculated from transmission, reflection and absorbance data in the spectral range of 200–1100 nm. It has been found that optical band gap and band tailing parameter decreases with the increase in Ge₈Sb₂Te₁₁thin films thickness. The dc-activation energy and sheet resistivity decreases while the crystallization temperature of the amorphous Ge₈Sb₂Te₁₁ films increases with the increase in thickness of the films. The decrease of the sheet resistivity has been substantiated quantitatively using the classical size-effect theory. These results have been explained on the basis of rearrangements of defects and disorders in the amorphous chalcogenide system.