Wide-area multilayered self-assembly of fluorapatite nanorods vertically oriented on a substrate as a non-classical crystal growth.

Oriented attachment of homogeneously shaped nanoblocks, such as nanocubes and nanorods, is attracting attention as a fundamental process of non-classical crystal growth to produce specific ordered architectures of functional materials. Although lateral alignments of horizontally oriented nanorod are commonly observed at the air-liquid and liquid-solid interfaces in dispersion systems, the accumulation of vertically oriented nanorods on a substrate has rarely been produced in a wide area over a millimeter-sized flat surface. Here, we achieved homogeneous stacking of vertical fluorapatite nanorods with a large aspect ratio (∼6) in a toluene-hexane mixture system through a gradual decrease in the dispersibility. Micrometer-thick flat films in which the c direction of fluorapatite nanorods was arranged perpendicularly to the surface were deposited on a substrate with a diameter of over 20 mm. The wide-area accumulation of vertical nanorods occurs through the self-assembly of laterally arranged clusters of nanorods covered with a stabilizing agent and subsequent gentle sedimentation on the substrate surface.