KDP晶体(100)面生长台阶聚并现象的AFM研究

采用激光偏振干涉手段实时测量了KDP晶体(100)面的生长速度与过饱和度之间的关系,用AFM技术观察了KDP晶体(100)面在不同过饱和度下的基本台阶和聚并台阶形貌,并据此分析了由基本台阶到聚并台阶的过程及其与过饱和度之间的关系.研究表明:过饱和度为1.8%时,(100)面上以基本台阶为主,基本台阶的高度为0.366 nm,约为半晶胞高度;增大过饱和度,基本台阶开始聚并,聚并初期,台阶高度增加,进而台阶宽度增加;随着过饱和度的增大,台阶聚并加剧,推移速度加快,但聚并台阶的斜率基本不变.     

ZTS晶体(100)面台阶聚并现象的AFM非实时研究

通过对301 K时,不同过饱和度以及掺杂2.5%(摩尔分数)尿素(σ=0.09)条件下生长的ZTS晶体进行AFM非实时扫描,对其(100)面的基本台阶以及聚并形成宏观台阶的形貌情况进行了研究。发现ZTS晶体(100)面在低过饱和度下(σ=0.03),以基本台阶推移为主,台阶高度约为0.553nm,近似为晶格参数a值的一半;在高过饱和度下(σ=0.09),以台阶聚并后的宏观台阶推移为主。而在同样的过饱和度下掺入尿素则会加剧台阶聚并的程度,该实验结果很好地符合了杂质诱导产生非对称台阶动力学系数理论模型。     

流动对ZTS晶体(100)面台阶生长动力学影响的研究

通过利用光学显微镜对ZTS晶体(100)面的台阶推移过程进行实时观察,对不同溶液供应速度及不同过饱和度下的台阶生长动力学进行了研究。结果表明,随着溶液供应速度S的增大,台阶平均推移速率先增大后减小。溶液供应速度S≈1.2mL/min时,台阶平均推移速率达到最大。而在静止的生长溶液中,台阶平均推移速率随着过饱和度σ的增大呈非线性增大,同时确定了生长死区σd和台阶平均推移速率急剧增大时的临界过饱和度值σ*,并计算了不同过饱和度阶段的台阶动力学系数和台阶活化能。     

硫脲硫酸锌晶体（100）面台阶生长动力学实时研究

运用光学显微镜实时观测了硫脲硫酸锌晶体（100）面台阶推移过程。获得了不同过饱和度、不同台阶高度、不同生长时间、不同台阶边缘扭折密度下的台阶推移速率;应用＂净流量＂模型解释了不同台阶推移速率的差异与过饱和度之间的依赖关系,计算了生长单元与台阶融合活化能及单台阶的动力学系数。通过分析发现台阶推移速率随过饱和度增加而线性增加,随台阶高度增加而下降;同一台阶推移速率随时间变化的现象与台阶重组过程有关;而台阶边缘扭折密度则从根本上决定了台阶推移速率的大小和变化趋势。     

pH值对ADP晶体(100)面生长的影响

通过对40℃、不同pH值和过饱和度下ADP晶体(100)面法向生长速度的研究,发现在同一过饱和度下,改变pH值后晶面的生长速度明显加快。实验数据显示,在过饱和度较低时,(100)面的生长以螺旋位错生长机制为主;过饱和度较高时,以二维成核生长机制为主,而且pH值的改变会促使ADP晶体在较低的过饱和度下就从位错生长机制向二维成核生长机制转变。利用实验数据计算出了不同pH值下、二维成核生长机制控制晶体生长时的台阶棱边能。最后,运用原子力显微镜(AFM)非实时观察了不同过饱和度、不同pH值下生长的ADP晶体(100)面的微观形貌,发现与正常pH值相比,在较低的过饱和度下,pH=2.5和5.0的晶面上就出现了二维核。     

二维平移法小尺寸KDP单晶生长溶液流动与传质模拟

二维平移法是一种新型的晶体生长方法.在该方法中,晶体不再作正反转运动,而是沿着特定轨迹作周期性的平移运动.本工作对二维平移法小尺寸磷酸二氢钾(KDP)单晶生长过程进行了数值模拟研究,获得了不同平移速度、不同平移距离以及不同迎流角度下晶体附近溶液流动与晶面过饱和度分布.结果表明:增加平移速度,晶面过饱和度随之增加,但流场结构并无明显变化;增大平移距离,晶面的过饱和度反而降低,标准差则有逐渐增大的趋势,这不利于提高过饱和度均匀性;不同迎流角度下,柱面的过饱和度分布差异较大,对流的不对称性也更加明显,当迎流角度为45°时,对晶体生长更有利.此外,台阶推移结果表明,不均匀的过饱和度会造成台阶弯曲和聚并,二维平移法更利于台阶稳定推移,有望提高形貌稳定性和晶体质量.     

KDP晶体相变界面微观形貌及大台阶形成的AFM观察

采用原子力显微镜实时和非实时观察了不同过饱和度下KDP晶体(100)面相变界面微观形貌,观察到晶体从生长死区恢复生长的过程;首次得到大台阶形成过程的实时AFM图像,解释了大台阶的形成机理;分析了台阶失稳的原因。结果表明,不同实验条件下,KDP(100)面相变界面均呈现为台阶面。在低过饱和度下,生长台阶来源于螺位错;在较高过饱和度下,层状台阶列来源于二维核。     

ADP晶体{100}面族二维成核生长微观形貌的AFM研究

ADP晶体{100}面族微观形貌的非实时AFM(atomic force microscopy,AFM)成像表明,过饱和度σ=0.053时,晶面上出现二维成核生长;随σ增加至0.11,二维岛数量急剧增加,尺寸减小,分布渐趋均匀,二维成核生长逐渐增强,界面呈现出由光滑向粗糙转变的特征;各二维岛形状趋近于长条形,表现出各向异性,长轴平行于[001]晶向;二维岛上有单分子高度的台阶和台阶聚并后高度为2～3nm的大台阶;二维岛间融合时取向相同;σ=0.053时,融合后所形成的较大二维岛的生长呈现出周边快中心慢的情况,将可能导致产生晶体缺陷.     

L-丙氨酸掺杂下KDP晶体成核特性及生长实验研究

通过实验测定了L-丙氨酸掺杂下KDP溶液的亚稳区和诱导期,根据经典成核理论计算了晶体成核的热力学和动力学参数,分析了L-丙氨酸对KDP溶液成核特性的影响。结果表明,随着掺入的L-丙氨酸浓度的增大,KDP的溶解度减小,亚稳区变宽,诱导期变长,溶液更加稳定。采用吊晶法进行了KDP晶体生长实验,发现其(100)面法向生长速度随掺杂浓度增大而减小,在过饱和度σ>0.04时,晶体(100)面的生长以二维成核生长机制为主。     

磷酸二氢钾晶体薄表面层生长动力学实时显微研究

利用光学显微镜实时观测磷酸二氢钾(KDP)晶体柱面及锥面薄表面层的生长过程,测得不同过饱和度下薄表面层前端不同倾角的非正常棱边推移速度。结果表明:倾角越小,非正常棱边推移速度越慢,薄表面生长终止于其前端的正常棱边处;随着过饱和度的增大,非正常棱边推移速度线性增加。计算得到柱面及锥面薄表面层前端非正常棱边推移动力学系数,由于Eslice(010) Eslice(101),因而柱面薄表面层的生长动力学系数大于锥面。建立了基于非奇异面上台阶生长机制下的薄表面层生长体扩散模型。应用该模型解释了薄表面层生长速度随其厚度及前端非正常棱边倾角的变化关系,并讨论了溶液流动对薄表面层生长的影响。结果发现薄表面层生长存在一个使其以恒定厚度向前推移的临界厚度。     

Nucleation of solid solutions crystallizing from aqueous solutions

The study of nucleation and growth mechanisms of salts from aqueous solutions, as a function of supersaturation, is described using both macroscopic and microscopic experiments. In situ observations in a fluid cell in an atomic force microscope (AFM) reveal phenomena not accounted for in standard crystal-growth theories, specifically on the role of the crystal structure of the substrate in controlling spiral growth and two-dimensional nucleation. As a model example, the crystallization of two isostructural salts, BaSO(4) and SrSO(4), is described. The growth of solid-solution crystals is considerably more complex. The supersaturation of a given aqueous solution relative to a solid solution is different with respect to each solid composition, and it leads to the possibility that different compositions can simultaneously grow by different mechanisms on the same crystal face. Oscillatory compositional zoning is another consequence of the interplay between the thermodynamics and the kinetics of nucleation. The factors which control nucleation and growth of the solid solution (Ba,Sr)SO(4) from an aqueous solution are described. The predictions made from the theory are compared with direct observations of crystal growth in an AFM.     

ADP晶体的生长丘、台阶微观形貌及台阶棱边能

ADP晶体{100}面族生长的实时与非实时AFM(atomic force microscopy,AFM)研究表明,过饱和度σ处于0.005～0.04,生长温度介于293～313K之间时,晶面上观察到位错生长丘和其它晶体缺陷所形成的生长丘,晶面主要为台阶推进方式生长;位错生长丘上空洞的出现与位错弹性理论相符;随过饱和度σ降低,台阶形貌会发生相应变化;生长温度为298K时,台阶棱边能不小于6.2×10-7J/cm2.     

Preferential Interface Nucleation: An Expansion of the VLS Growth Mechanism for Nanowires

A review and expansion of the fundamental processes of the vapor–liquid–solid (VLS) growth mechanism for nanowires is presented. Although the focus is on nanowires, most of the concepts may be applicable to whiskers, nanotubes, and other unidirectional growth. Important concepts in the VLS mechanism such as preferred deposition, supersaturation, and nucleation are examined. Nanowire growth is feasible using a wide range of apparatuses, material systems, and growth conditions. For nanowire growth the unidirectional growth rate must be much higher than growth rates of other surfaces and interfaces. It is concluded that a general, system independent mechanism should describe why nanowires grow faster than the surrounding surfaces. This mechanism is based on preferential nucleation at the interface between a mediating material called the collector and a crystalline solid. The growth conditions used mean the probability of nucleation is low on most of the surfaces and interfaces. Nucleation at the collector‐crystal interface is however different and of special significance is the edge of the collector‐crystal interface where all three phases meet. Differences in nucleation due to different crystallographic interfaces can occur even in two phase systems. We briefly describe how these differences in nucleation may account for nanowire growth without a collector. Identifying the mechanism of nanowire growth by naming the three phases involved began with the naming of the VLS mechanism. Unfortunately this trend does not emphasize the important concepts of the mechanism and is only relevant to one three phase system. We therefore suggest the generally applicable term preferential interface nucleation as a replacement for these different names focusing on a unifying mechanism in nanowire growth.     

Kinetically controlled fabrication of C60 1-dimensional crystals

Considering the current application of fullerenes in the field of organic semiconductor devices, the highly crystalline or single crystal fullerene nanostructures with controlled shape and size contains some breakthrough for improved efficiency. Recently, fullerene 1-dimensional nanostructures, including nanowhiskers and nanotubes, become attractive kind of materials since the development of liquid-liquid interface precipitation (LLIP) process. The LLIP process has critical advantage; the fabrication of highly crystalline, even single crystal, fullerene 1-dimensional nanostructures with simple apparatus. However, the fabrication fullerene 1-dimensional structures by LLIP process requires long process time from one day to several days. In order to overcome this drawback, a modified process from conventional LLIP process is suggested. In the modified LLIP process, the nucleation step and growth step were divided. For the nucleation step, saturated fullerene solution is mixed with small amount of alcohols such as 2-propanol or ethanol. For the controlled growth step, the fullerenes in the nucleated solution are precipitated by addition of alcohol, which is injected to the bottom of the solution with controlled flow rate. In this modified process, the shape of the precipitated fullerene crystals is critically dependent on the nucleation steps and the size is dependent on the precipitation rate. By combination of proper nucleation step and growth rate, a well defined fullerene 1-dimensional structures, of 200-500 nm width and of hundreds microm length can be fabricated within two hours. In addition, by controlling injection rate and degree of supersaturation, several types of 1-dimensional structures including micro-tubes can be prepared and, by changing solvent and alcohol, several shape of C60 crystals including polyhedral particles and plates can be prepared.     

不同运动方式KDP单晶生长流动与物质输运数值分析

针对两种不同运动方式下的KDP单晶生长,进行了流动与物质输运模拟.分析和比较了不同运动方式下,晶面附近溶液流动及晶面过饱和度分布特征.研究了晶体尺寸对晶面过饱和度场的影响.结果表明:二维运动法中,晶面遭受的水动力学条件较为复杂,使得其过饱和度分布不如转晶法规则;二维运动法锥面过饱和度明显高于转晶法;单位周期内,转晶法晶面平均过饱和度存在较大波动,而二维运动法过饱和度随时间变化较小;总体上看,小尺寸晶体时,二维运动法晶面过饱和度梯度小于转晶法;大尺寸晶体时,二维运动法晶面过饱和度梯度大于转晶法.     

Kinetic Monte Carlo simulation of an atomistic model for oxide island formation and step pinning during etching by oxygen of vicinal Si(100)

A lattice-gas model is developed to describe the simultaneous oxidation and etching of Si(100) surfaces exposed oxygen. The model incorporates nucleation of oxide islands via conversion of on-surface to back-bonded oxygen, together with an observed transformation in the shapes of just-formed islands from linear to two-dimensional. Model analysis via Kinetic Monte Carlo simulation quanti?es oxygen uptake and oxide island nucleation kinetics, including possible enhanced nucleation at step edges. Simulated etching of vicinal Si(100) surfaces reveals that receding steps are pinned by oxide islands and transform into ?nger-like structures even at higher temperatures where oxide island growth is inhibited.     

InAs自组织量子点(线)的制备和表征

在InP(001)基衬底上用分子束外延方法生长了InAs纳米结构材料，通过改变生长方式，得到了InAs量子点和量子线。根据扫描电镜和透射电镜观测结果的分析，认为衬底旋转时浸润层三角形状的台阶为InAs量子线的成核提供了优先条件，停止衬底旋转时InAlAs缓冲层沿[11^-0]方向分布的台阶促使InAs优先形成量子点。讨论了量子点和量子线的形成机理。     

化学气相沉积碳化钛的热力学和动力学研究

对采用ＴｉＣｌ４－ＣＨ４－Ｈ２反应体系化学气相沉积碳化钛的反应热力学和成核热力学因素进行了分析，并在实验的基础上研究了不同沉积温度下化学气相沉积ＴｉＣ过程的动力学特征，以及在不同的动力学控制机制下气相过饱和度的成核过程对ＴｉＣ涂层的析出形态的影响。在沉积过程中，气相过饱和度和动力学控制机制是控制沉积物的成核过程和析出形态的决定因素。     

Growth mechanism of NaBrO3 crystals from aqueous solutions

To study the growth mechanism of {111} faces of NaBrO₃, crystals were grown at different supersaturations ranging from 2% to 8%. The growth mechanisms were investigated based on the growth rate versus supersaturation relation and from the surface features observed on {111} faces. The growth mechanism of these crystals appear to be due to 2D nucleation. The growth rate curve has been further investigated using Ohara and Reid equations. Polynucleation model in two-dimensional nucleation growth theory is suggested as the most possible growth mechanism for these crystals in the present supersaturation range.