Former studies have demonstrated a strong interest toward the crystallization of CaCO3 polymorphs in solution. Nowadays, CaCO3 crystallization on solid surfaces is extensively being studied using biomolecules as substrates for the control of the growth aiming at various applications of CaCO3. Calcium carbonate exists in an amorphous state, as three anhydrous polymorphs (aragonite, calcite and vaterite), and as two hydrated polymorphs (monohydrocalcite and ikaite). The vaterite polymorph is considered as one of the most attractive forms due to its large surface area, biocompatibility, mesoporous nature, and other features. Based on physical or chemical immobilization approaches, vaterite can be grown directly on solid surfaces using various (bio)molecules, including synthetic polymers, biomacromolecules such as proteins and peptides, carbohydrates, fibers, extracellular matrix components, and even biological cells such as bacteria. Herein, the progress on the modification of solid surfaces by vaterite CaCO3 crystals is reviewed, focusing on main findings and the mechanism of vaterite growth initiated by various substances mentioned above, as well as the discussion of the applications of such modified surfaces.

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