The Role of Oleic Acid: From Synthesis to Assembly of Perovskite Nanocuboid Two-Dimensional Arrays

Oleic acid, an 18-carbon chain fatty acid, has been widely used as a surfactant to fabricate colloidal nanocrystals. In previous work, we discovered a lamellar microemulsion strategy to fabricate sub-20 nm SrTiO3 nanocuboids using oleic acid and oleate species. Here, we demonstrate (i) the general synthesis with lamellar microemulsions of a family of compositionally varied BaxSr1-xTiO3 crystalline nanocuboids with uniform size, and (ii) subsequent assembly into two-dimensional arrays by nanoparticle-bound oleate in a nonpolar solvent. The measured interparticle distance (2.4 nm) of adjacent nanoparticles in an array is less than the length of a double oleate layer (similar to 4 nm). On the basis of calculations of the interfacial free energy, we propose the hydrophobic, hydrocarbon-terminated groups of oleate from adjacent nanocuboids are situated closely but do not overlap. Lower aspect ratio nanocuboids are bordered by four adjacent nanocuboids which results in a uniform direction self-assembly array, whereas higher aspect ratio nanocuboids are bordered by five or six adjacent nanocuboids and can develop an arced local coordination.