Experimental and theoretical investigation of ligand effects on the synthesis of ZnO nanoparticles

ZnO nanoparticles with highly controllable particle sizes(less than 10 nm) were synthesized using organic capping ligands in Zn(Ac)2 ethanolic solution. The molecular structure of the ligands was found to have significant influence on the particle size. The multi-functional molecule tris(hydroxymethyl)-aminomethane (THMA) favoured smaller particle distributions compared with ligands possessing long hydrocarbon chains that are more frequently employed. The adsorption of capping ligands on ZnnOn crystal nuclei (where n = 4 or 18 molecular clusters of(0001) ZnO surfaces) was modelled by ab initio methods at the density functional theory (DFT) level. For the molecules examined, chemisorption proceeded via the formation of Zn...O, Zn...N, or Zn...S chemical bonds between the ligands and active Zn2+ sites on ZnO surfaces. The DFT results indicated that THMA binds more strongly to the ZnO surface than other ligands, suggesting that this molecule is very effective at stabilizing ZnO nanoparticle surfaces. This study, therefore, provides new insight into the correlation between the molecular structure of capping ligands and the morphology of metal oxide nanostructures formed in their presence

Origin of defect-related green emission from ZnO nanoparticles: effect of surface modification

We investigated the optical properties of colloidal-synthesized ZnO spherical nanoparticles prepared from 1-octadecene (OD), a mixture of trioctylamine (TOA) and OD (1:10), and a mixture of trioctylphosphine oxide (TOPO) and OD (1:12). It is found that the green photoluminescence (PL) of samples from the mixture of TOA/OD and TOPO/OD is largely suppressed compared with that from pure OD. Moreover, it is found that all spherical nanoparticles have positive zeta potential, and spherical nanoparticles from TOA/OD and TOPO/OD have a smaller zeta potential than those from OD. A plausible explanation is that oxygen vacancies, presumably located near the surface, contribute to the green PL, and the introduction of TOA and TOPO will reduce the density of oxygen vacancies near the surfaces. Assuming that the green emission arises due to radiative recombination between deep levels formed by oxygen vacancies and free holes, we estimate the size of optically active spherical nanoparticles from the spectral energy of the green luminescence. The results are in good agreement with results from TEM. Since this method is independent of the degree of confinement, it has a great advantage in providing a simple and practical way to estimate the size of spherical nanoparticles of any size. We would like to point out that this method is only applicable for samples with a small size distribution