Characterization of crystal growth using a spiral nucleation model

Classical concepts of two-dimensional nucleation and spiral growth are used together with recent findings on the dynamics of dislocation spirals to derive a new crystal growth model. Initial growth nuclei result from the organization of adsorbed molecules in spirals around surface dislocations. The energetic barrier for the activation of the spiral nuclei is considerably lower than the admitted by classical two dimensional nucleation models. Stable nuclei evolve into bigger growth hillocks in supersaturated media through the incorporation of adsorbed units into their steps. The displacement velocity of steps during solution and vapour growth is calculated by different kinetic approaches, taking into consideration the distinct role of surface diffusion in each process, and avoiding known limitations of conventional theories. A generalized expression is obtained relating the crystal growth rate with main variables such as supersaturation, temperature, crystal size, surface topology and interfacial properties. At the end of the paper, the crystallization kinetics of sucrose measured at 40 °C is interpreted in the light of the new perspectives resulting from the proposed model. The application example illustrates how to estimate interfacial and topological properties from the experimental crystal growth results.     

Spirals on Si(1 1 1) at sublimation and growth: REM and LODREM observations

Using recently proposed improvements of reflection electron microsopy (REM) we study, in perfectly controlled thermodynamics conditions, spiral and spirals shapes on Si(1 1 1) surface. It is shown that the new method named low distortion reflection electron microscopy (LODREM) is a powerful instrument, resolving in much more details (compared with REM) growth or evaporation spirals at the crystal surface. More precisely, we examine the distance between two successive steps of a spiral at growth (or evaporation) with respect to the supersaturation (or undersaturation). It is found that this distance scales with an exponent close to −1/2. This result, which deviates from the BCF theory, originates from a non-local behavior with a slow kinetic of attachment of the adatoms at the steps.     

Stability of Crystal Growth Face and Dissolution Face in Crystallization from Solution under Microgravity

The stability of the shapes of crystal growth face and dissolution face in a two-dimensional mathematical model of crystal growth from solution under microgravity is studied.It is proved that the stable shapes of crystal growth face and dissolution face do exist,which are suitably shaped curves with their upper parts inclined backward properly.The stable shapes of crystal growth faces and dissolution faces are calculated for various values of parameters,Ra,Pr and Sc.It is shown that the stronger the convection relative to the diffusion in solution is,the more backward the upper parts of the stable crystal growth face and dissolution face are inclined.The orientation and the shape of dissolution face hardly affect the stable shape of crystal growth face and vice versa.     

微重力下溶液法晶体生长模型中晶体生长界面稳定性的研究

研究在微重力条件下溶液法晶体生长的一个二维数学模型中晶体生长界面的稳定性问题.对晶体生长界面为不同倾斜角度的平面的情况作了数值计算,计算结果表明有可能存在一个稳定的晶体生长界面,它应该是一个在Y=λ这一端向后倾的适当形状的曲面 关键词： 微重力 溶液法晶体生长 二维模型 生长界面的稳定性     

Effects of interface kinetics and anisotropy on the stability of the growing crystal face and dissolution face during crystallization from solution under microgravity

The stability of the shapes of the growing crystal face and dissolution face in a two-dimensional mathematical model of crystal growth from solution under microgravity is studied. Effects of the interface kinetics and anisotropy of crystallization and dissolution on the stability are also studied. It is proved that the stable shapes of crystal growth face and dissolution face do exist, which are of suitably shaped curves with their upper parts inclined backward properly no matter whether the interface kinetics and the anisotropy are taken into account or not. The stable shapes of the growing crystal faces and dissolution faces are calculated for various cases. The interface kinetics will make the inclination degree of stable crystal growth face reduce and that of stable dissolution face reduce slightly. The anisotropy of crystallization and dissolution may make the inclination degree of stable-growing crystal face smaller or larger, and that of the stable dissolution face varies very slightly.     

The mass transfer process and the growth rate of NaCl crystal growth by evaporation based on temporal phase evaluation

The mass transfer process and the crystal growth rate have been proved to be very important in the study of crystal growth kinetics, which influence the crystal quality and morphological stability. In this paper, a new method based on temporal phase evaluation was presented to characterize the mass transfer process in situ and determine the crystal growth rate. The crystallization process of NaCl crystal growth by evaporation was monitored in situ by a Mach-Zehnder interferometer, and the absolute concentration evolution, the evaporation rate and the real-time supersaturation of solution were obtained using temporal phase analysis, which acted as a novel technique to extract phase variation along time axis recently. Based on the evaporation rate and the absolution concentration, a new method to calculate mass transfer flux during the crystal growth without the knowledge of the mass transfer coefficient was proposed, and then the crystal growth rate could also be retrieved under the hypothesis of cubic crystals. The results show that the crystal growth rate increases with the supersaturation linearly. It is in agreement with the diffusion theories, which presume that matter is deposited continuously on a crystal face at a rate proportional to the difference in concentration between the points of deposition and the bulk of solution. The method is applicable to the research of crystallization process based on evaporation or vapor diffusion of which the precise conditions of nucleation and supersaturation are usually unknown because of the complexity of the evaporation rate and crystal growth rate.     

Reducing SAR in parallel excitation using variable-density spirals: a simulation-based study

Parallel excitation using multiple transmit channels has emerged as an effective method to shorten multidimensional spatially selective radiofrequency (RF) pulses, which have a number of important applications, including B1 field inhomogeneity correction in high-field MRI. The specific absorption rate (SAR) is a primary concern in high-field MRI, where wavelength effects can lead to local peaks in SAR. In parallel excitation, the subjects are exposed to RF pulses from multiple coils, which makes the SAR problem more complex to analyze, yet potentially enables greater freedom in designing RF pulses with lower SAR. Parallel-excitation techniques typically employ either Cartesian or constant-density (CD) spiral trajectories. In this article, variable-density (VD) spiral trajectories are explored as a means for SAR reduction in parallel-excitation pulse design. Numerical simulations were conducted to study the effects of CD and VD spirals on parallel excitation. Specifically, the electromagnetic fields of a four-channel transmit head coil with a three-dimensional head model at 4.7 T were simulated using a finite-difference time domain method. The parallel RF pulses were designed and the resulting excitation patterns were generated using a Bloch simulator. The SAR distributions due to CD and VD spirals were evaluated quantitatively. The simulation results show that, for the same pulse duration, parallel excitation with VD spirals can achieve a lower SAR compared to CD spirals for parallel excitation. VD spirals also resulted in reduced artifact power in the excitation patterns. This gain came with slight, but noticeable, degrading of the spatial resolution of the resulting excitation patterns.     

Ib型金刚石大单晶的限形生长

金刚石的限形生长有利于其后续加工.对于磨料级金刚石限形生长的研究已经比较透彻,但金刚石大单晶的限形生长尚缺乏全面系统的研究.本文以Fe Ni(64wt%:36wt%)合金为触媒,利用高温高压下的温度梯度法在5.6 GPa时对不同温度下分别沿(100)面和(111)面生长的Ib型金刚石大单晶的晶形进行了研究.研究表明:随着温度的升高,沿(100)晶面生长的金刚石大单晶的晶形分别为板状、塔状直至尖塔状,而沿(111)面生长的金刚石大单晶的晶形则分别为塔状和板状;分析了不同温度下分别沿(100)面和(111)面生长金刚石大单晶不同晶形高径比的变化情况.利用不同压力和温度下的金刚石大单晶合成实验绘制了沿(100)和(111)面生长金刚石大单晶的晶形在V形生长区域内的分布示意图,表明沿(111)面生长的金刚石大单晶V形区温度下限明显比以(100)面生长的高,而沿这两面生长金刚石大单晶的V形区温度上限差别并不明显.对不同生长面V形区温度上下限的差别进行了解释,据此实现了Ib型金刚石大单晶的限形生长.     

单晶金刚石边缘表面倾斜角度对同质外延生长的影响

利用微波等离子体化学气相沉积法,对单晶金刚石(100)晶面边缘进行精细切割抛光处理,形成偏离(100)晶面不同角度的倾斜面,在CH_4/H_2反应气体中进行同质外延生长,研究单晶金刚石边缘不同角度倾斜面对边缘金刚石外延生长的影响.实验结果表明,边缘倾斜面角度对边缘的单晶外延生长质量有影响,随着单晶金刚石边缘倾斜面角度的增大,边缘多晶金刚石数量先减少后增多,在倾斜角3.8°时边缘呈现完整的单晶外延生长特性.分析认为,边缘不同角度的倾斜面会改变周围电场强度和等离子体密度,导致到达衬底表面的含碳前驱物发生改变,倾斜面台阶表面的含碳前驱物浓度低于能形成层状台阶生长的临界浓度是减弱单晶金刚石生长过程中边缘效应的主要原因.     

Growth of 4-(dimethylamino) benzaldehyde doped triglycine sulphate single crystals and its characterization

Single crystals of triglycine sulphate (TGS) doped with 1 mol% of 4-(dimethylamino) benzaldehyde (DB) have been grown from aqueous solution at ambient temperature by slow evaporation technique. The effect of dopant on the crystal growth and dielectric, pyroelectric and mechanical properties of TGS crystal have been investigated. X-ray powder diffraction pattern for pure and doped TGS was collected to determine the lattice parameters. FTIR spectra were employed to confirm the presence of 4-(dimethylamino) benzaldehyde in TGS crystal, qualitatively. The dielectric permittivity has been studied as a function of temperature by cooling the sample at a rate of 1 °C/min. An increase in the Curie temperature T_c=51 °C (for pure TGS, T_c=48.5 °C) and decrease in maximum permittivity has been observed for doped TGS when compared to pure TGS crystal. Pyroelectric studies on doped TGS were carried out to determine pyroelectric coefficient. The Vickers's hardness of the doped TGS crystals along (0 1 0) face is higher than that of pure TGS crystal for the same face. Domain patterns on b-cut plates were observed using scanning electron microscope. The low dielectric constant, higher pyroelectric coefficient and higher value of hardness suggest that doped TGS crystals could be a potential material for IR detectors.     

溶液中晶体生长动力学的MC计算机模拟研究

用蒙特卡罗计算机模拟方法研究了溶液中晶体表面的生长台阶和生长动力学,着重讨论了表面尺寸、表面粗糙度以及溶液过饱和度对晶体生长速率的影响以及相应的生长机制.     

Quantitative analysis of electron diffraction data from epitaxially grown crystals

Epitaxial growth produces oriented crystal projections where a long unit cell axis is parallel to the major crystal face rather than perpendicular to it and thus provides a favorable condition for electron diffraction data collection which minimizes perturbations due to elastic crystal bending. Even though the crystals are not so perfect as those produced by solution growth, the intensity data from them have been useful for the quantitative crystal structure analysis of several molecular organic compounds and linear polymers as discussed in this review.     

Multiscale simulations of damage of perfect crystal Cu at high strain rates

We use the molecular dynamics code, large-scale atomic/molecular massively parallel simulator (LAMMPS), to simulate high strain rate triaxial deformation of crystal copper to understand void nucleation and growth (NAG) within the framework of an experimentally fitted macroscopic NAG model for polycrystals (also known as DFRACT model). It is seen that void NAG at the atomistic scales for crystal copper (Cu) has the same qualitative behaviour as the DFRACT model, albeit with a different set of parameters. The effect of material temperature on the nucleation and growth of voids is studied. As the temperature increases, there is a steady decrease in the void NAG thresholds and close to the melting point of Cu, a double-dip in the pressure–time profile is observed. Analysis of this double-dip shows disappearance of the long-range order due to the creation of stacking faults and the system no longer has a face centred cubic (fcc) structure. Molecular dynamics simulation of shock in crystal Cu at strain rates high enough to cause spallation of crystal Cu are then carried out to validate the void NAG parameters. We show that the pre-history of the material affects the void nucleation threshold of the material. We also simulate high-strain-rate triaxial deformation of crystal Cu with defects and obtain void NAG parameters. The parameters are then used in a macroscale hydrodynamic simulation to obtain spallation threshold of realistic crystal Cu. It is seen that our results match experimental results within the limit of 20% error.     

Adsorption and electron properties of thin nickel films on W(110) surface

The evolution of the properties of ordered nickel films with thicknesses increasing from one to three atomic monolayers (ML) adsorbed on the W(110) single crystal surface is studied under ultrahigh vacuum conditions by the methods of reflection-absorption infrared spectroscopy (RAIRS) and ultraviolet photoelectron spectroscopy (UPS). The film structure corresponds to that of the Ni(111) single crystal face. The RAIRS technique is used to study the vibrational properties of the probing NO molecules adsorbed on the nickel films studied. In the course of the nickel film growth, whereby its thickness increases from 1 to 3 ML, both the vibrational and photoelectron spectra exhibit significant variation, which is indicative of a change in the adsorption and electron properties of the film. Stabilization of the IR and photoelectron spectra at a film thickness of 3 ML indicates that this thickness corresponds to the formation of the main adsorption and electron properties of the deposit. At the same time, the vibrational spectra of NO molecules adsorbed on a monoatomic nickel film exhibit features typical of adsorption on the W[110] surface of a massive tungsten crystal.     

The formation of a dislocation spiral on the (101) face of a monoclinic lysozyme crystal: High-resolution experiments

The elementary processes of crystal growth in the case of a low kink density on step edges have been studied by in situ atomic force microscopy. High-resolution images of the first turn of the polygonal dislocation spiral on the (101) face of monoclinic lysozyme crystals, which allow one to discern separate crystal cells, have been obtained. It has been shown that the dependence of the spiral segment velocity on its length is inconsistent with the Gibbs-Thomson law and is represented by several rectilinear sections. The results were explained by taking into account the features of the growth of crystals with a low kink density at low supersaturation.     

温度对Ib型和IIa型金刚石大单晶(100)表面特征的影响

本文在5.6 GPa, 1250–1340 ℃的条件下, 利用温度梯度法, 以FeNiMnCo 合金为触媒, 沿籽晶的(100)晶面成功合成了不同晶形的优质Ib型和IIa型金刚石大单晶. 利用激光拉曼附件显微镜, 分别对上述不同温度下合成的两类金刚石样品上表面(100)面的中心区域及棱角区域进行观察分析. 研究发现, Ib型和IIa型金刚石大单晶(100)晶面上从中心到棱角处黑色纹路的分布逐渐变黑变密集; 另外, 随着金刚石合成温度的升高, Ib型金刚石大单晶(100)面上黑色纹路由稀疏逐渐变稠密, 而IIa型金刚石大单晶的黑色纹路较为稀疏; Ib型金刚石大单晶的形貌特征表现为从低温晶体的不规则分布过渡到中温、高温晶体的典型树枝状分布. IIa型金刚石大单晶(100)面特征随温度变化规律与Ib型的类似. 这两类金刚石大单晶表面特征的差异可能是由于IIa 型金刚石具有比Ib型更小的生长速度和更少的氮含量. 最后, 对两类塔状金刚石大单晶进行拉曼光谱测试分析, 结果表明IIa型金刚石大单晶的品质较Ib型金刚石大单晶好.     

The instability of the surface of helium crystal in a superfluid flow

The problem on crystal growth under conditions of normal incidence of fluid on the boundary is investigated for stability. The threshold velocity of the emergence of instability is found; at low temperatures, this velocity proves to be much lower than the sound velocity. The stability is examined of the shape of cylindrical crystal in a fluid flow parallel to the crystal axis. The behavior of the atomically rough surface of crystal helium is experimentally investigated in a jet of fluid in the temperature range from 1 to 1.4 K, where the emergence is observed of an instability of the type previously predicted by Kagan, as well as by Nozieres and Uwaha. Observations reveal that, below the roughening transition, the (0001) basal face is stable in a jet of fluid.     

Dislocation structure and microhardness of L-arginine perchlorate single crystal

This paper presents the chemical etching and microhardness studies carried out on L-arginine perchlorate (LAPCl), a non-linear optical crystal (NLO) with a view to characterize the dislocation structure and mechanical strength of the grown crystals. LAPCl crystals employed in this investigation were grown from aqueous solution by solvent evaporation method. Optical microscopic studies of as grown habit faces revealed formation of macrosteps and valley on (100) habit face. Chemical etching of (100) face with impurity added organic solvents played an important role in the formation of etch pits. Selective etching of matched pairs on opposite faces of the same plane confirms that the pits are formed at the dislocation sites. Microhardness measurement by indentation method shows decrease of microhardness with increasing load. Nature of hardness profile is explained with the help of Meyer’s law. The work hardening index value indicates that LAPCl belongs to hard crystal category.     

LD端面泵浦不同掺杂离子YAG晶体的热效应研究

通过建立激光晶体热传导模型,针对相同基质YAG晶体不同掺杂离子,求解泊松方程,得到不同Nd3+和Yb3+掺杂浓度的YAG晶体内温度场分布,并进行了对比分析。研究结果表明:在相同条件下,随着Nd3+和Yb3+掺杂浓度的增加,YAG晶体端面中心温度升高,晶体中心轴温度衰减越快,热焦距越小;当Yb3+掺杂浓度达到Nd3+掺杂浓度的近10倍时,热效应基本相同。这一结论为降低同基质晶体的热效应提供了理论依据。     

Correlation between growth of high-index faces, relative growth rates and crystallographic structure of crystal

According to contemporary crystal growth theories, crystals are bound by low-index faces which are the most slowly growing. However, high-index faces are observed in crystal habits more and more often. In this paper the growth of high-index faces is analysed from a crystallographic perspective. It is shown that the crystallographic structure of a given crystal, expressed by the trigonometric function of appropriate interfacial angles, influences to great degree the crystallisation process and the morphology of crystals, in particular the behaviour of high-index faces. Additionally, it is concluded that at particular crystallographic structure of a crystal, a given high-index face may exist in the habit and develop its size, although it grows much faster than the neighbouring faces. Received 31 July 2001