固液界面温度的一种测量方法

固液界面处温度的精密测量是晶体生长动力学研究的一个重要实验数据。本实验设计了一种适合于偏光显微镜用的温度调节试样台,用直接动态观察法,借助于直径25微米的铜-康铜热电偶,测量了水杨酸苯酯晶体的固液界面附近的温度分布。在△T<3℃的低过冷度的生长条件下,铜制试样台的热量输运条件稳定。固液界面处的温度增加值约为熔液过冷度的1％。这种温度调节试样台适合于生长机理的高精度定量实验研究。 关键词：     

Structural and optical properties of metastable SiGe/Si films with a low germanium concentration

The properties of metastable Si_{1 ? x} Ge _x /Si (10% < x < 16%) layers grown by molecular beam epitaxy on Si(100) substrates have been investigated using atomic force microscopy, X-ray diffraction, and low-temperature luminescence spectroscopy. It has been shown that ring-like aggregates are formed on the surface of layers grown at temperatures of 500–700°C. The size and shape of these aggregates suggest that their formation is associated with the diffusion instability arising due to the existence of a relationship between the surface diffusion, stresses, and the wetting potential during the growth of the epitaxial film. The existence of deviations from the homogeneous germanium distribution in the layer plane has been confirmed by a detailed analysis of the X-ray rocking curves and two-dimensional diffraction patterns. The structures with severe surface disturbances are characterized by an abnormal change in the decay times of the emission lines of bulk silicon, which indicate the presence of local electric and/or strain fields in subsurface regions. The perturbations of the flat crystallization front are suppressed as the growth temperature of layers decreases to 350°C. Despite the absence of a coating layer of silicon, the photoluminescence spectra of the layers themselves depend weakly on their thickness and growth temperature and remain sensitive only to the technological concentration of germanium. A slowly decaying luminescence associated presumably with the localization of excitons near the SiGe-Si interface has been observed in one of the samples grown at a temperature of 700°C and containing a dense array of ring-like aggregates.     

Si-W/Si/SiO2/Si(100)的横截面电子显微镜研究

本文用横截面电子显微镜法分析了Si-W/Si/SiO₂/Si(100)在440—1000℃退火后的晶化过程,以及各个界面的变化情况.发现Si-W合金膜中,WSi₂并未优先在表面、界面处形成晶核.当退火温度不高于700℃时,反应在合金膜内发生,表面、界面起伏和缓.退火温度高达800—1000℃时,界面、表面出现原子扩散,造成剧烈的界面起伏;表面则出现小的热沟槽,Si/SiO₂界面也出现高分辨电子显微镜才能观察到的起伏.表面、界面的原子迁移的动力来源于晶界与表面、界面张力.由于SiO₂中Si—O键很稳定,不易发生Si和O在界面处的互扩散,所以Si/SiO₂界面起伏很小. 关键词：     

PEALD-deposited crystalline GaN films on Si(100) substrates with sharp interfaces

Polycrystalline gallium nitride(GaN) thin films were deposited on Si(100) substrates via plasma-enhanced atomic layer deposition(PEALD) under optimal deposition parameters. In this work, we focus on the research of the GaN/Si(100)interfacial properties. The x-ray reflectivity measurements show the clearly-resolved fringes for all the as-grown GaN films, which reveals a perfectly smooth interface between the GaN film and Si(100), and this feature of sharp interface is further confirmed by high resolution transmission electron microscopy(HRTEM). However, an amorphous interfacial layer(~ 2 nm) can be observed from the HRTEM images, and is determined to be mixture of Ga_xO_y and GaN by xray photoelectron spectroscopy. To investigate the effect of this interlayer on the GaN growth, an AlN buffer layer was employed for GaN deposition. No interlayer is observed between GaN and AlN, and GaN shows better crystallization and lower oxygen impurity during the initial growth stage than the GaN with an interlayer.     

Solid-phase crystallization of amorphous Si films on glass and Si wafer

When amorphous silicon films deposited on glass by physical or chemical vapor deposition are annealed, they undergo crystallization by nucleation and growth. The growth rate of Si crystallites is the highest in their 〈111〉 directions along or nearly along the film surface. The directed crystallization is likely to develop the 〈110〉//ND or 〈111〉//ND oriented Si crystallites. As the annealing temperature increases, the equiaxed crystallization increases, which in turn increases the random orientation. When amorphous Si is under a stress of the order of 0.1 GPa at about 540 °C, the tensile stress increases the growth rate of Si grains, whereas the compressive stress decreases the growth rate. However, the crystal growth rate increases with the increasing hydrostatic pressure, when the pressure is of the order of GPa at 530–540 °C. These phenomena have been discussed based on the directed crystallization model advanced before, which has been further elaborated.     

Origins of interdiffusion, crystallization and layer exchange in crystalline Al/amorphous Si layer systems

Aluminium-induced crystallization of amorphous silicon (a-Si) in Al/a-Si and a-Si/Al bilayers was studied upon annealing at low temperatures between 165 and 250 °C, by X-ray diffraction (XRD) and Auger electron spectroscopy (AES). Upon annealing the inward diffusion of Si along grain boundaries in Al takes place, followed by crystallization of this diffused Si. Continuous annealing leads to (more or less) layer exchange in both types of bilayers. The change in bulk energy of the Al phase (release of macrostress and microstrain, increase of grain size) promotes the occurrence of layer exchange, whereas changes in surface and interface energies counteract the layer exchange.     

Xenon-beam-induced atomic transport through Cr/Al and Cr2N/Al interfaces

Cr layers (60–75 nm) on Al substrates and Cr₂N layers (40–120 nm) on Al+3 wt.% Mg substrates were irradiated at 80 K and 300 K with 150–900 keV Xe-ions. The ion-beam-induced interface mixing was analyzed by means of Rutherford Backscattering Spectrometry (RBS). Both systems exhibit fairly small mixing rates, with those of Cr/Al being enhanced at 300 K target temperature, due to radiation-enhanced diffusion. The observed interface broadening is compared with predictions of ballistic and thermal spike mixing models. The low-temperature mixing rates in the system Cr/Al are underestimated by the ballistic model, but are rather well reproduced by local spike models. Mixing in the Cr₂N/Al system at both temperatures, on the other hand, seems to be rather well described by the ballistic model.     

Interface growth mechanism in ion beam sputtering-deposited Mo/Si multilayers

Despite the technological importance of metal/Si multilayer structures in microelectronics, the interface reactions occurring during their preparation are not yet fully understood. In this work, the interface intermixing in Mo/Si multilayer coatings has been studied with respect to their preparation conditions. Various samples, prepared at room temperature with different Mo deposition rates (0.06–0.43?Å?s^?1) and a constant Si rate, have been investigated by detailed TEM observations. Contrary to the Si-on-Mo interface where no evidence of chemical intermixing could be found, the Mo-on-Si interface presents a noticeable interface zone whose thickness was found to noticeably decrease (from 4.1 to 3.2?nm) when increasing the Mo deposition rate. Such intermixing phenomena correspond to diffusion mechanisms having coefficients ranging from 0.25?×?10^?15 to 1.2?×?10^?15?cm²?s^?1 at room temperature. By assuming a diffusion mechanism mainly driven by Mo–Si atomic exchanges to minimize the surface energy, the diffusion dependence with Mo deposition rate has been successfully simulated using a cellular automaton. A refined simulation including Mo cluster formation is also proposed to explain the scenario leading to the full crystallization of Mo layers.     

Electron-beam-initiated crystallization of iron-carbon films

A structure formed in nanocrystalline iron-carbon films exposed to an electron beam was studied. Explosive crystallization (EC) with the formation of dendrite and cellular-dendritic instabilities at a rate of up to 1 cm/s was observed. It was shown that the dependence between the growth rate of dendrite branches (or cells) during EC and the rounding radius of dendrite branch tips can be approximately described by equations used to calculate the crystal growth in supercooled melts. To explain the EC mechanism, a model of a liquid zone formed at the crystallization front was used. It was shown that the liquid zone arises due to energy accumulated in the film in the nanocrystalline state. It was assumed that this energy was accumulated due to the energy of elastic stresses.     

Growth of SrTiO3 on Si(001) by hybrid molecular beam epitaxy

We report the heteroepitaxial growth of SrTiO₃ thin films on Si(001) by hybrid molecular beam epitaxy (hMBE). Here, elemental strontium and the metal‐organic precursor titanium tetraisopropoxide (TTIP) were co‐supplied in the absence of additional oxygen. The carbonization of pristine Si surfaces during native oxide removal was avoided by freshly evaporating Sr into the hMBE reactor prior to loading samples. Nucleation, growth and crystallization behavior as well a structural properties and film surfaces were characterized for a series of 46‐nm‐thick SrTiO₃ films grown with varying Sr to TTIP fluxes to study the effect of non‐stoichiometric growth conditions on film lattice parameter and surface morphology. High quality SrTiO₃ thin films with epitaxial relationship (001)SrTiO₃ || (001)Si and [110]SrTiO₃ || [100]Si were demonstrated with an amorphous layer of around 4 nm thickness formed at the SrTiO₃/Si interface. The successful growth of high quality SrTiO₃ thin films with atomically smooth surfaces using a thin film technique with scalable growth rates provides a promising route towards heterogeneous integration of functional oxides on Si. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of composition modulation on the structural and optical properties of Si/Ge bilayers

We report structural as well as optical studies on Si/Ge bilayer structures having different individual layer thicknesses. The Raman spectrum of [Ge (5 nm)/Si (5 nm)] bilayer structure shows amorphous nature, while the [Si (5 nm)/Ge (5 nm)] bilayer structure shows a mixed nanocrystalline/amorphous behaviour of the layers. As the thickness of the individual layers increases to 10 nm, the introduction of large number of Si atoms at the interface results in reduction of Ge crystallization as well as higher intensity of interfacial SiGe alloy formation. This may be regarded as a consequence of the island growth induced surface roughening in the later case (i.e. in [Si (10 nm)/Ge (10 nm)] bilayer) as also revealed by corresponding atomic force microscopy (AFM) images. These results are also supported by Photoluminescence (PL) spectra recorded using two different photon energies of 300 and 488 nm along with the optical absorption measurements giving higher values of band gap as compared to their corresponding bulks, revealing the effect of quantum confinement in the deposited layers.     

The 4:5 Si-to-SiC atomic lattice matching interfaces in the system of Si(111) heteroepitaxially grown on 6H-SiC(001) substrates

Corresponding lattice planes of 4:5 Si-to-SiC atomic matching structures are observed at the Si(111)/6H-SiC(001) interface. The periodical Si/SiC interface structure is further illustrated and characterized by an atomic model derived from experiment results. It is discovered that there is a minor lattice mismatch of 0.26% in the structure. Moreover, the atomic structure of the interface and its stability are energetically investigated by molecular dynamics simulations. The results demonstrate that the atomic relaxations caused by lattice mismatch are slight to the growth of a perfect crystalline Si film and the interfaces are quite stable with the formation energy of ?22.452 eV.     

Identification of Ge/Si intermixing processes at the Bi/Ge/Si(111) surface

The chemical contrast between Si and Ge obtained by scanning tunneling microscopy on Bi-covered Si(111) surfaces is used as a tool to identify two vertical Ge/Si intermixing processes. During annealing of an initially pure Ge monolayer on Si, the intermixing is confined to the first two layers approaching a 50% Ge concentration in each layer. During epitaxial growth, a growth front induced intermixing process acting at step edges is observed. Because of the open atomic structure at the step edges, relative to the terraces, a lower activation barrier for intermixing at the step edge, compared to the terrace, is observed.     

Al-Induced Crystallization Growth of Si Films by Inductively Coupled Plasma Chemical Vapour Deposition

Polycrystalline Si （poly-Si） films are in situ grown on Al-coated glass substrates by inductively coupled plasma chemical vapour deposition at a temperature as low as 350℃. Compared to the traditional annealing crystalliza- tion of amorphous Si/Al-layer structures, no layer exchange is observed and the resultant poly-Si film is much thicker than Al layer. By analysing the depth profiles of the elemental composition, no remains of A1 atoms are detected in Si layer within the limit （〈0.01 at.%） of the used evaluations. It is indicated that the poly-Si material obtained by Al-induced crystallization growth has more potential applications than that prepared by annealing the amorphous Si/Al-layer structures.     

The crystallization kinetics of sodalites grown by the hydrothermal transformation of kaolinite studied by Si MAS NMR

The hydrothermal transformation of kaolinite to basic sodalite Na₈[AlSiO₄]₆ (OH · H₂O)₂ and hydroxoborate sodalite Na₈[AlSiO₄]₆ [B(OH)₄]₂ has been investigated at different temperatures (353 and 473 K). In the early stage of the reactions, the crystallization kinetics was studied by X-ray powder diffraction, thermogravimetry, IR spectroscopy and ²⁹Si MAS NMR spectroscopy. Besides the crystallization of the sodalites, no further intermediate phases were formed. MAS NMR of the ²⁹Si nucleus has been found to be a versatile tool to follow the progress of reactions from the signal ratio of the initial material and the crystallization product because the differences in chemical shifts result in well-separated signals. From these measurements, the growth rates of the sodalites could be determined quantitatively even for the very early stages of crystallization. It was found that sodium carbonate impurities in the NaOH solution used for the synthesis has an important influence on the reaction kinetics.     

Interfacial reaction barriers during thin-film solid-state reactions: The crystallographic origin of kinetic barriers at the NiS2/Si(111) interface

Epitaxial NiSi₂ islands have been grown on Si(111) substrates by the direct reaction of nickel vapour with the silicon substrate in ultra-high vacuum at 400° C. Growth kinetics was shown to depend on the orientation of the islands: A-oriented islands grow about ten times faster than B-oriented ones, with the ratio of the advance rates of the main growth fronts even reaching 30. Applying plan-view transmission electron microscopy and high-resolution electron microscopy of cross sections, a corresponding difference was found in the structure of the NiSi₂/Si(111) growth front: Steps at the B-oriented growth front were of three or six interplanar (111) spacings in height, whereas at the A-oriented growth front step-like defects of less than one interplanar (111) spacing in height were observed. These observations are explained by an atomic-scale model of the solid-state reaction, which involves the diffusion of nickel to the interfaces and the nucleation and subsequent lateral propagation of interfacial steps. The difference in the reaction kinetics originates from the presence of kinetic reaction barriers at the NiSi₂/Si(111) growth fronts, the barrier at the B-front being higher owing to the lower formation rate of steps of triple atomic height than that of steps of lower height at the A-NiSi₂/Si(111) growth front.     

Formation of the Si/Ti interface

The formation of the Si/Ti interface during the deposition of silicon on titanium polycrystalline substrates has been studied at room temperature (RT) using X-ray photoelectron spectroscopy (XPS), angle-resolved XPS (ARXPS), ultraviolet photoelectron spectroscopy (UPS) and ion scattering spectroscopy (ISS). The experimental results are consistent with a two-stage mechanism for Si growth: a first stage characterized by the simultaneous formation of a uniform titanium silicide layer, that reaches a limiting thickness of ∼3 monolayer (ML), and pure silicon islands 1 ML thick that grow on top of this layer up to coalescence, followed by a second stage in which pure silicon islands, with an average thickness of 9 ML, grow on top of the uniform titanium silicide layer + pure silicon ML structure formed during the first stage. As a whole, pure silicon species grows according to a Stranski-Krastanov mechanism, where the first ML is formed during the first stage and the islands during the second stage. The comparison of Ti/Si and Si/Ti interfaces shows that the structure and composition of the interface do not depend substantially on the deposition sequence, suggesting that the bulk chemistry of the compound formed at the interface dominates over the surface kinetics and the bulk substrate chemistry in determining the composition and structure of the interface.     

A new method to determine Si/SiO2 interface recombination parameters using a gate-controlled point-junction diode under illumination

A new method is presented to determine Si/SiO₂ interface recombination parameters. The device employed is constituted by a polysilicon-oxide-semiconductor capacitor with a microscale central junction (a gate-controlled point-junction diode). The excess minority carriers are photo-generated rather than being injected, which results in a one-dimensional current flow normal to the Si/SiO₂interface. The minority carrier quasi-Fermi level is probed at the Si/SiO₂ interface by means of the point junction. The one-dimensionality of the current flow and the exact knowledge of the minority carrier quasi-Fermi level permit an accurate measurement of the recombination rate. The method has been applied to characterize p-type 100 Si/SiO₂ interfaces with boron dopant concentrations ranging from 2.2×10¹⁵ to 2.0×10¹⁷ cm^-3. Data analysis has been performed using a numerical scheme to find a quasi-exact solution for the current recombining at the interface. It was found that the interface recombination parameters (trap density and capture cross-sections) depend only weakly on trap energy in a wide range around midgap. The cross-section for capturing electrons (σ_n) was found to greatly exceed (by a factor of 10² to 10³) the cross-section for capturing holes (σ_p).     

定向结晶条件下聚乙二醇6000的强动力学效应

在单向温度场条件下, 采用不同抽拉速度实现了聚乙二醇6000的定向生长、界面形貌的实时观测及界面温度的测量, 进而揭示了其生长机制. 实验结果表明, 随着抽拉速度的增大, 界面的温度逐渐减小, 过冷度逐渐增大. 运用高聚物结晶的次级形核理论模型, 对实验数据进行了计算, 得到在界面过冷度为13.5 K左右时, 生长机制发生了由区域Ⅱ向区域Ⅲ的转变. 实验数据与等温结晶数据的比较发现等温结晶方法中获得过冷度相对较大, 是因为其包含了热过冷. 聚乙二醇6000定向结晶过程中需要的最大动力学过冷度为20 K, 说明由于高聚物的二维形核, 其生长主要由界面动力学控制, 具有较强的动力学效应.     

爆轰加载下高纯铜界面Rayleigh-Taylor不稳定性实验研究

金属界面不稳定性是内爆物理压缩过程中关注的重要问题,与传统流体界面不稳定性具有显著区别.由于相关理论和实验诊断技术的限制,目前该问题的研究还明显不足.为加深对金属界面不稳定性扰动增长行为的认识,本文建立了爆轰加载下高纯铜界面Rayleigh-Taylor不稳定性研究的实验诊断技术和数据处理方法,得到了扰动发展早期不同时刻界面扰动增长的X光图像.实验结果分析表明:在爆轰产物的无冲击加载条件下扰动波长基本保持不变,而初始扰动幅值越大,界面扰动增长的趋势就越明显;同时随着样品前界面扰动的不断发展,在样品的后自由面也出现了与前界面初始相位相反的扰动特征,即样品前界面扰动为波谷的位置所对应的后界面先运动而逐渐演变为波峰,而前界面扰动为波峰的位置所对应的后界面则演变为波谷;在5.26μs时刻,界面扰动幅值增长为初始值的700%左右,应变率达到了约105/s.结合数值模拟研究表明:在此情况下常用的Steinberg-Cochran-Guinan模型在一定程度上低估了高纯铜材料强度的强化特性,无法准确地描述强度对界面扰动增长的制稳作用,从而导致数值模拟结果要大于实验测量结果.