Synthesis, Self-Assembly, Disassembly, and Reassembly of Two Types of Cu2O Nanocrystals Unifaceted with {001} or {110} Planes

Abstract

In this work, we describe a solution-based synthesis of monodisperse Cu(2)O nanocrystals with controllable sizes in the nanoscale regime. Two types of nanocrystals, cubes and rhombic dodecahedra unifaceted with either {001} or {110} crystal planes, have been prepared at a 100% morphological yield. In particular, synthetic parameters and formation processes of the Cu(2)O nanocrystals have been investigated in detail, and a range of well-oriented supercrystals/superlattices built from the two types of nanobuilding blocks have been attained for the first time. It has been revealed that n-hexadecylamine used in the present work plays multiple roles: it serves as a chelating ligand to form [Cu(NH(2)C(16)H(33))(4)](2+) complex precursor, as a phase-transferring agent to transfer divalent Cu(2+) ions into the organic phase, as a reducing agent to generate monovalent Cu(+) (i.e., Cu(2)O), as a passivating adsorbate to control crystal morphology, and as a surface capping agent to generate self-assemblies of nanocrystals via van der Waals interaction. Apart from synthesis and self-assembly, disassembly and reassembly of Cu(2)O nanocrystals have also been investigated. The disassembly processes are accompanied with aggregative growths of nanocrystals, which can be attributed to a combined process of "oriented attachment" and Ostwald ripening, leading to permanent engagement and enlargement of nanocrystals. Finally, our self-assembled nanocrystals of Cu(2)O show a lower detection limit, lower operating temperature, and higher sensitivity in ethanol vapor detection, compared with other Cu(2)O-based alcohol sensors reported in the recent literature. A greater depletion layer of carrier and a relatively small contact potential may account for the observed sensing enhancement in the sensors made from the organized Cu(2)O nanocrystals.