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Anisotropic Growth of Otavite on Calcite: Implications for Heteroepitaxial Growth Mechanisms

机译：方解石上奥塔维特的各向异性生长：杂志生长机制的影响

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src="http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/cgdefu/2018/cgdefu.2018.18.issue-1/acs.cgd.7b01055/20171227/images/medium/cg-2017-010559_0008.gif">Elucidating the molecular-scale mechanisms driving complex growth behaviors during heteroepitaxial growth in aqueous media has remained a challenging endeavor. Toward this goal, in situ atomic force microscopy was employed to image the heteroepitaxial growth of otavite (CdCO3) at the (101?4) surface of calcite (CaCO3) single crystals in static aqueous conditions. Heteroepitaxial growth proceeded via spreading of three-dimensional (3D) islands and two-dimensional (2D) atomic layers at low and high initial saturation levels, respectively. Experiments were carried out as a function of applied force and imaging mode thus enabling determination of growth mechanisms unaltered by imaging artifacts. This approach revealed the significant anisotropic nature of heteroepitaxial growth on calcite in both growth modes and its dependence on supersaturation, film thickness, and substrate topography. The 3D islands not only grew preferentially along the [421?] direction relative to the [010] direction, resulting in rod-like surface precipitates, but also showed clear preference for growth from the island end rich in obtuse/obtuse kink sites. Pinning to step edges was observed to often reverse this tendency. In the 2D growth mode, the relative velocities of acute and obtuse steps were observed to switch between the first and second atomic layers. This phenomenon likely stems from significant Cd–Ca intermixing in the first layer, despite bulk thermodynamics predicting the formation of almost pure otavite. Composition effects may also be responsible for the inability of 3D islands to grow on 2D layers in cases where both modes were observed to occur simultaneously. Overall, the complex heteroepitaxial growth in general and thickness-dependent growth mechanisms in particular provide insight
机译：src =“http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/cgdefu/2018/cgdefu.2018.18.issue-1/acs.cgd.7b01055/20171227/images/medium /cg-2017-010559_0008.gif“选出在含水培养基中杂交生长期间推动络合生长行为的分子级机制仍然存在挑战性的努力。朝向这种目标，在原位原子力显微镜中用于在方解石的（101'4）表面（Caco 3 ）处的奥塔维矿石（CdCo 3 ）的异质生长静态水性条件下的单晶。通过在低且高初始饱和水平下分别通过三维（3D）岛和二维（2D）原子层的三维（3D）岛和二维（2D）原子层进行的异质轴生长。作为施加力和成像模式的函数进行实验，从而能够确定通过成像伪影未置换的生长机制。这种方法揭示了生长模式中方解石对方解石对方解石的显着各向异性性质及其对超饱和，膜厚度和衬底地形的依赖性。相对于[010]方向，3D岛不仅沿[421〜]方向优先增长，导致棒状表面沉淀，但还显示出透明偏好于富含岛状的岛状的生长溶胀/钝的扭结扭结。观察到循环边缘通常逆转这种趋势。在2D生长模式中，观察到急性和钝的步骤的相对速度在第一和第二原子层之间切换。这种现象可能源于第一层中的显着的CD-CA混合，尽管散装热力学预测几乎纯耳磨机的形成。在观察到两种模式的情况下，组成效应也可能负责3D岛在2D层上生长2D层。总体而言，综合性杂志生长在一般和厚度依赖性的生长机制中特别提供见解

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  • 来源
    《Crystal growth & design》 |2018年第1期|共12页
  • 作者

    Shawn L. Riechers; Sebastien N. Kerisit;

  • 作者单位

    Physical Sciences Division Pacific Northwest National Laboratory Richland Washington 99352 United States;

    Physical Sciences Division Pacific Northwest National Laboratory Richland Washington 99352 United States;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 晶体学;
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