Cu2O crystals are synthesised hydrothermally with an 8-branched morphology, which can undergo a transition to a cubic shape by increasing the reaction time. The rapid branch formation of these structures is studied over time using SEM, TEM, SAED, PXRD and TGA. The formation of Cu 2+ /PVP soft matter clusters is shown to play a key role in the reduction of Cu 2+ , the nucleation of Cu2O crystals and the rapid growth of branches along all eight equivalent <111> directions of the cubic Cu2O structure, due to the presence of negatively charged hydroxyl sites on the {111} surfaces. This non-classical crystal growth mechanism, which relies on aggregation of the precursor on the crystal surface, may help us to understand the formation of many abnormal crystal morphologies.
INTRODUCTIONCuprous oxide, Cu2O, is a semiconductor material which has a cubic structure, a direct band gap of 2.137 eV 1,2 and which typically exhibits p-type semiconductor characteristics due to the presence of Cu vacancies. [3][4][5] Due to its unique and interesting magnetic and optical properties, Cu2O has been widely studied due to its potential applications in a huge range of fields such as catalysis, 6,7 gas sensing 8 and the conversion of solar energy into chemical or electrical energy 9-11 as well as having been at the centre of research into the Bose-Einstein condensation of excitons. 12 Cu2O has been shown to exhibit a wide variety of morphologies such as thin films, 13,14 nanorod arrays, 15 nanospheres or nanocubes [16][17][18] and even hollow crystals. 19,20 Since the suitability of Cu2O for its various applications is so highly dependent on its morphology and microstructure, 21 an array of different and often complicated techniques have been utilised to attempt to control the shapes and sizes of Cu2O crystals. These have included electrochemical deposition, 22-25 high pressure sputtering, 26 sonochemical methods 27 and many other techniques 28,29 but the control of Cu2O morphologies synthesized via more facile, hydrothermal routes has rarely been reported.More recently, there has been interest in dendritic or branched morphologies and, in particular, the highly symmetric "8-pod branching growth" 30-32 of Cu2O crystals as the high degree of branching in such structures results in a much higher surface area than that of the more typical cubic or octahedral Cu2O crystals and may, therefore, increase the efficiencies of Cu2O crystals for their various applications. Little is understood about the mechanism by which these structures form, however, as many highly symmetric metal oxide crystals are thought to be single crystals so their growth goes unstudied as they are assumed to follow the classical growth route, first established over 100 years ago. This so-called "bottom-up" theory of crystal growth is described by the Bravais-Friedel-Donnay-Harker (BFDH) law [33][34][35] and Hartman-Perdok theory 36 and explains how single crystals are formed from a single nucleus via layer-by-layer deposition of the building units on the crys...