Critical Step Length as an Indicator of Surface Supersaturation during Crystal Growth from Solution

The surface processes that control crystal growth from solution can be probed in real-time by in situ 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 in situ microscopy by decoupling quantitative measurement from the influence of mass transport.