Elucidating the effect of precursor decomposition time on the structural and optical properties of copper(i) nitride nanocubes

To study the effect of time on the colloidal synthesis of Cu(3)N nanoparticles, copper(ii) nitrate was thermally decomposed at 260 °C for up to 60 min in octadecylamine as a stabilizing ligand. Thermolysis of the nitrate followed four steps which included; nucleation, growth, ripening and decomposition. At 5 min, partially developed nanocubes were found in a dense population of Cu(3)N nuclei. Well-defined Cu(3)N nanocubes were obtained at 15 min with no presence of the nuclei. TEM images showed disintegration of the cubes at 20 min and as time progressed, all the Cu(3)N decomposed to Cu by 60 min. The formation of the Cu(3)N nanocubes was confirmed by XRD and XPS. FTIR suggested the formation of a nitrile (RCN) as a result of the thermal decomposition in octadecylamine (ODA) and this was confirmed using NMR and hence, a reaction mechanism was then proposed. The optical properties of the as-synthesized Cu(3)N were studied using UV-vis and photoluminescence spectroscopies. The absorption spectra for particles synthesized from 5 min to 15 min showed a singular exciton peak while from 20 min to 60 min two peaks were observed. The two peaks may both be associated with the two direct transitions observed in Cu(3)N or the more red-shifted peak could be a result of localized surface plasmon resonance due to the Cu nanoparticles. Nevertheless, similar to other studies, it is clear that the optical properties of Cu(3)N are complex.