Anisotropic Epitaxial Behavior in the Amorphous Phase-Mediated Hydroxyapatite Crystallization Process: A New Understanding of Orientation Control

The precise control of crystallization is a key in the construction and engineering of crystalline materials, especially in biomineralization. Although it is generally accepted that biomineral crystals have evolved from their amorphous precursors, there are intense debates about crystallographic orientation control. By using in situ high-resolution transmission electron microscopy, we herein reveal that hydroxyapatite (HAP) is produced through its epitaxial growth from amorphous calcium phosphate with a preferential c-axis orientation. Abnormally but interestingly, this anisotropic epitaxial crystallization priority along the c-axis is not affected by the existing HAP crystalline substrate, which is exactly the same on either {002} or {100} facets. Molecular dynamics simulations suggest this preference is correlated with the interfacial energetic controls at the amorphous–crystalline transition frontier. The orientation control of biominerals here shows the key role of the interface energy, rather that the organic molecules or matrices, which provides a complementary understanding of the general c-axis orientation control of HAP in various biomineralization cases and aids in the development of an alternative strategy for crystallization control of functional materials.