New Insights into the Mechanism of ZnO Formation from Aqueous Solutions of Zinc Acetate and Zinc Nitrate

The controlled synthesis of ZnO at the micro- and nanoscale has been the focus of significant research due to its importance in electrical and optoelectronic applications, and the potential of tuning its properties at the crystal formation stage. We present a detailed study of ZnO growth processes which supports and consolidates previous findings and gives a clearer understanding of the mechanism of ZnO formation. The influence of synthesis conditions on ZnO formation was investigated by comparison of two different growth routes (Zn(CH3COO)(2)-NH3 and Zn(NO3)(2)center dot 6H(2)O-HMTA) both known to result in the formation of wurtzite structured, twinned hexagonal rods of ZnO. The identities of the solid phases formed and supernatants were confirmed by data from SEM, XRD, FTIR, XPS, TGA, and ICP-OES analysis; giving insight into the involvement of multistep pathways. In both cases, reaction takes place via intermediates known as layered basic zinc salts (LBZs) which only later transform to the oxide phase. In the ZnAc2-NH3 system, crystal growth evolves as Zn(CH3COO)(2) -> LBZA (A: acetate) -> ZnO through a dissolution/reprecipitation process, with the formation of an additional product identified as LBZAC (C: carbonate). In contrast, in the Zn(NO3)(2)center dot 6H(2)O-HMTA system, solid-phase transformation occurs as Zn(NO3)(2)center dot 6H(2)O -> LBZN (N: nitrate) -> ZnO with no evidence of dissolution. Similar comprehensive studies can be applied to other solid-state processes to further advance functional materials design.