Critical Step Length as an Indicator of Surface Supersaturation during Crystal Growth from Solution.
Crystal growth & design(2022)
Abstract
The surface processes that control crystal growth from solution can be probed in real-time by microscopy. However, when mass transport (partly) limits growth, the interfacial solution conditions are difficult to determine, precluding quantitative measurement. Here, we demonstrate the use of a thermodynamic feature of crystal surfaces-the critical step length-to convey the local supersaturation, allowing the surface-controlled kinetics to be obtained. Applying this method to atomic force microscopy measurements of calcite, which are shown to fall within the regime of mixed surface/transport control, unites calcite step velocities with the Kossel-Stranski model, resolves disparities between growth rates measured under different mass transport conditions, and reveals why the Gibbs-Thomson effect in calcite departs from classical theory. Our approach expands the scope of microscopy by decoupling quantitative measurement from the influence of mass transport.
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Key words
surface supersaturation,crystal growth,critical step length
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