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

Journal Article · Mon Dec 18 04:00:00 EST 2017 · Crystal Growth and Design

DOI:https://doi.org/10.1021/acs.cgd.7b01055· OSTI ID:1416674

Riechers, Shawn L. ^[1]; Kerisit, Sebastien N. ^[1]

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1. Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States

Elucidating how cation intermixing can affect the mechanisms of 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 (10-14) 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, intermixing, and substrate topography. The 3D islands not only grew preferentially along the [42-1] 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 stemmed from the significant Cd-Ca intermixing in the first layer, despite bulk thermodynamics predicting the formation of almost pure otavite. Composition effects were also responsible for the inability of 3D islands to grow on 2D layers in cases where both modes were observed to occur simultaneously. Overall, the AFM images highlighted the effects of intermixing on heteroepitaxial growth, particularly how it can induce thickness-dependent growth mechanisms at the nanoscale.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1416674
• Report Number(s): PNNL-SA-128035; 49839; 49689; KC0302060
• Journal Information: Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 1 Vol. 18; ISSN 1528-7483
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

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Environmental Molecular Sciences Laboratory