Thermal phase change and activation energy of crystallization of Ge-Sb-Te-Sn thin films

To improve the optical storage performance, Sn was doped into Ge2Sb2Te5 phase change thin films. The optical and thermal properties of Sn-doped Ge2Sb2Te5 film were investigated. The crystal structures of the as-sputtered and the annealed films were identified by the X-ray diffraction (XRD) method. The differential scanning calorimeter (DSC) method is used to get the crystallization temperature and crystallization energy (Ea). It was found that proper Sn-doping could highly improve storage performance of the Ge2Sb2Te5 media.     

Ab Initio computer simulation of the early stages of crystallization: application to Ge(2)Sb(2)Te(5) phase-change materials

By virtue of the ultrashort phase-transition time of phase-change memory materials, e.g., Ge(2)Sb(2)Te(5), we successfully reproduce the early stages of crystallization in such a material using ab initio molecular-dynamics simulations. A stochastic distribution in the crystallization onset time is found, as generally assumed in classical nucleation theory. The critical crystal nucleus is estimated to comprise 5-10 (Ge,Sb)(4)Te(4) cubes. Simulated growth rates of crystalline clusters in amorphous Ge(2)Sb(2)Te(5) are consistent with extrapolated experimental measurements. The formation of ordered planar structures in the amorphous phase plays a critical role in lowering the interfacial energy between crystalline clusters and the amorphous phase, which explains why Ge-Sb-Te materials exhibit ultrafast crystallization.     

短波长相变光盘记录介质Ge2Sb2Te5薄膜的制备及静态性能研究

研究了６３２．８ｎｍ波长下适用的相变光盘介质Ｇｅ２Ｓｂ２Ｔｅ５薄膜的制备方法和静态光存诸记录特性，发现该薄膜可在１００ｎｓ条件下实现直接重写，在优化膜层结构后，写擦循环次数高达１０＾６，反射率对比度在１５％以上。     

Density functional simulations of Sb-rich GeSbTe phase change alloys

We generated models of the amorphous phase of Sb-rich GeSbTe phase change alloys by quenching from the melt within density functional molecular dynamics. We considered the two compositions Ge(1)Sb(1)Te(1) and Ge(2)Sb(4)Te(5). Comparison with previous results on the most studied Ge(2)Sb(2)Te(5) allowed us to draw some conclusions on the dependence of the structural properties of the amorphous phase on the alloy composition. Vibrational and electronic properties were also scrutinized. Phonons at high frequencies above 200?cm(-1) are localized in tetrahedra around Ge atoms in Sb-rich compounds as well as in Ge(2)Sb(2)Te(5). All compounds are semiconducting in the amorphous phase, with a band gap in the range 0.7-1.0?eV.     

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.     

Structural and electrical analysis of In–Sb–Te‐based PCM cells

Two In–Sb–Te compounds with low Te content (12 at.% and 17 at.%), deposited by metalorganic chemical vapour deposition, were implemented into prototype phase‐change memory devices of size 50 × 50 nm² and 93 × 93 nm². These chalcogenides yielded devices with higher threshold voltage than those based on Ge–Sb–Te alloys. The endurance and programming window were markedly improved (from 10³ to 10⁶ cycles and from 1 to 2 orders of magnitude, respectively) when employing the Te‐richer alloy. Moreover, in situ structural and electrical analysis on TiN/In–Sb–Te/dielectric stacks provided additional insight on the thermal stability of the two ternary phases In₃SbTe₂ and InSb_0.8Te_0.2, which were found to coexist in these compounds. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

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.     

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.     

高压下稳态六方Ge2Sb2Te5结构、电子和光学性质的第一性原理研究

采用基于密度泛函理论的广义梯度近似方法研究了稳态六方petrov原子序列结构Ge2Sb2Te5的结构、电子和光学性质。计算所得的平衡态晶格参数与实验数据和先前的理论结果吻合很好。基态的能带结构和态密度表明了稳态六方petrov原子序列结构的Ge2Sb2Te5持有金属性。从压强影响下体积的变化趋势发现稳态六方Ge2Sb2Te5在17 GPa和34 GPa 出现不稳定,暗示在此压强下的相变发生,这与2009年Krbal等人的实验结果相吻合。同时,还系统地研究了稳态六方petrov原子序列结构的Ge2Sb2Te5高压下的光学性质,得到了高压下介电函数、吸收率、光反射率、折射率、消光系数和电子能量损失谱在20 eV内的变化情况。     

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.     

Nano-scale gap filling and mechanism of deposit-etch-deposit process for phase-change material

Ge2Sb2Te5 gap filling is one of the key processes for phase-change random access memory manufacture.Physical vapor deposition is the mainstream method of Ge2Sb2Te5 film deposition due to its advantages of film quality,purity,and accurate composition control.However,the conventional physical vapor deposition process cannot meet the gapfilling requirement with the critical device dimension scaling down to 90 nm or below.In this study,we find that the deposit-etch-deposit process shows better gap-filling capability and scalability than the single-step deposition process,especially at the nano-scale critical dimension.The gap-filling mechanism of the deposit-etch-deposit process was briefly discussed.We also find that re-deposition of phase-change material from via the sidewall to via the bottom by argon ion bombardment during the etch step was a key ingredient for the final good gap filling.We achieve void-free gap filling of phase-change material on the 45-nm via the two-cycle deposit-etch-deposit process.We gain a rather comprehensive insight into the mechanism of deposit-etch-deposit process and propose a potential gap-filling solution for over 45-nm technology nodes for phase-change random access memory.     

Polarization readout analysis for multilevel phase change recording by crystallization degree modulation

Four different states of Si15Sb85 and Ge2Sb2Te5 phase change memory thin films are obtained by crystallization degree modulation through laser initialization at different powers or annealing at different temperatures. The polarization characteristics of these two four-level phase change recording media are analyzed systematically. A simple and effective readout scheme is then proposed, and the readout signal is numerically simulated. The results show that a high-contrast polarization readout can be obtained in an extensive wavelength range for the four-level phase change recording media using common phase change materials. This study will help in-depth understanding of the physical mechanisms and provide technical approaches to multilevel phase change recording.     

Raman spectra and XPS studies of phase changes in Ge2Sb2Te5 films

Ge_2Sb_2Te_5 film was deposited by RF magnetron sputtering on Si (100) substrate. The structure of amorphous and crystalline Ge_2Sb_2Te_5 thin films was investigated using XRD, Raman spectra and XPS. XRD measurements revealed the existence of two different crystalline phases, which has a FCC structure and a hexagonal structure, respectively. The broad peak in the Raman spectra of amorphous Ge_2Sb_2Te_5 film is due to the amorphous －Te－-Te－ stretching. As the annealing temperature increases, the broad peak separates into two peaks, which indicates that the heteropolar bond in GeTe_4 and the Sb－Sb bond are connected with four Te atoms, and other units such as (TeSb) Sb－Sb (Te_2) and (Sb_2) Sb－Sb (Te_2), where some of the four Te atoms in the above formula are replaced by Sb atoms, remain in crystalline Ge_2Sb_2Te_5 thin film. And from the results of Raman spectra and XPS, higher the annealing temperature, more Te atoms bond to Ge atoms and more Sb atoms substitute Te in (Te_2) Sb－Sb (Te_2).     

Synthesis and thermoelectric properties of Mn-doped AgSbTe₂ compounds

Polycrystalline p-type Ag 0.9 Sb 1.1 x Mn x Te 2.05(x = 0.05,0.10,and 0.20) compounds have been prepared by a combined process of melt-quenching and spark plasma sintering.The sample composition of Ag 0.9 Sb 1.1 x Mn x Te 2.05 has been specially designed in order to achieve the doping effect by replacing part of Sb with Mn and to present the uniformly dispersed Ag 2 Te phase in the matrix by adding insufficient Te,which is beneficial for optimizing the electrical transport properties and enhancing the phonon scattering effect.All the samples have the NaCl-type structure according to our X-ray powder diffraction analysis.After the treatment of spark plasma sintering,only the sample with x = 0.20 has a small amount of MnTe 2 impurities.The thermal analysis indicates that a tiny amount of Ag 2 Te phase exists in all these samples.The presence of the MnTe 2 impurity with high resistance and high thermal conductivity leads to the deteriorative thermoelectric performance of the sample with x = 0.20 due to the decreased electrical transport properties and the increased thermal conductivity.In contrast,the sample with x = 0.10 exhibits enhanced thermoeletric properties due to the Mn-doping effect.A dimensionless thermoelectric figure of merit of 1.2 is attained for the sample with x = 0.10 at 573 K,showing promising thermoelectric properties in the medium temperature range.     

Iron trichloride as oxidizer in acid slurry for chemical mechanical polishing of Ge2Sb2Te5

The effect of iron trichloride （FeC13） on chemical mechanical polishing （CMP） of Ge2Sb2Te5 （GST） film is inves- tigated in this paper. The polishing rate of GST increases from 38 nm/min to 144 nm/min when the FeC13 concentration changes from 0.01 wt% to 0.15 wt%, which is much faster than 20 nm/min for the 1 wt% H2O2-based slurry. This polish- ing rate trends are inversely correlated with the contact angle data of FeCl3-based slurry on the GST film surface. Thus, it is hypothesized that the hydrophilicity of the GST film surface is associated with the polishing rate during CMP. Atomic force microscope （AFM） and optical microscope （OM） are used to characterize the surface quality after CMP. The chemical mechanism is studied by potentiodynamic measurements such as Ecorr and Icorr to analyze chemical reaction between FeCl3 and GST surface. Finally, it is verified that slurry with FeCl3 has no influence on the electrical property of the post-CMP GST film by the resistivity-temperature （RT） tests.     

Land/groove optical recording with GeTe/Sb2Te3 superlattice-like structure

A superlattice-like (SLL) structure was applied to phase-change optical recording. The recording layer consisting of alternating thin layers of two different phase-change materials, GeTe and Sb2Tes, were grown by magnetron sputtering on polycarbonate substrates. Land/groove optical recording was adopted to suppress crosstalk and obtain a large track density. Dynamic properties of the SLL disc were investigated with the shortest 1T pulse duration of 8 ns. Clear eye pattern was observed after 10000 direct overwrite cycles. Erasability above 20 dB was achieved at a constant linear velocity of 19 m/s. Carrier-noise ratio (CNR) kept above 46 dB when the recording frequency reaches 21 MHz. The SLL phase change optical disc demonstrates a better recording performance than the Ge1Sb2Te4 and Ge1Sb4Te7 discs in terms of CNR, erasability, and overwrite jitter.     

Effects of Ge doping on the properties of Sb2Te3 phase-change thin films

Ge-doped Sb₂Te₃ films were prepared by magnetron sputtering of Ge and Sb₂Te₃ targets on SiO₂/Si (1 0 0) substrates. The effect of Ge doping on the structure was studied in details by X-ray diffraction, differential scanning calorimetry, and X-ray photoelectron spectroscopy measurements. It is indicated that Ge atoms substitute for Sb/Te in lattice sites and form Ge-Te bonds, moreover, a metastable phase was observed in Ge-doped specimens. Both crystallization temperature and resistivity of amorphous Sb₂Te₃ increase after Ge doping, which are beneficial for improving room temperature stability of the amorphous state and reducing the SET current of chalcogenide random access memory.     

GeSbTe deposition for the PRAM application

GeSbTe (GST) chalcogenide thin films for the phase-change random access memory (PRAM) were deposited by an atomic layer deposition (ALD) process. New precursors for GST thin films made with an ALD process were synthesized. Among the synthesized precursors, Ge(N(CH₃)₂)₄, Sb(N(CH₃)₂)₄, and Te(i-Pr)₂ (i-Pr = iso-propyl) were selected. Using the above precursors, GST thin films were deposited using an H₂ plasma-assisted ALD process. Film resistivity abruptly changed after an N₂ annealing process above a temperature of 350 °C. Cross-sectional scanning electron microscope (SEM) photographs of the GST films on the patterned substrate with aspect ratio of 7 shows that the step coverage is about 90%.     

Pressure enhancement of the giant magnetocaloric effect in Tb5Si2Ge2

Effects of temperature and pressure on magnetic, elastic, structural, and thermal properties of Tb5Si2Ge2 have been studied by means of macroscopic (thermal expansion and magnetization) and microscopic (neutron powder diffraction) techniques. We present evidence that the high-temperature second-order ferromagnetic transition can be coupled with the low-temperature first-order structural phase change into a single first-order magnetic-crystallographic transformation at and above a tricritical point in the vicinity of 8.6 kbar. This pressure-induced coupling has a remarkable effect on the magnetocaloric effect, transforming Tb5Si2Ge2 from an ordinary into a giant magnetocaloric effect material.