The effect of stoichiometry on the structural, thermal and electronic properties of thermally decomposed nickel oxide.

A thermal decomposition route with different sintering temperatures was employed to prepare non-stoichiometric nickel oxide (Ni1-δ O) from Ni(NO3)2·6H2O as a precursor. The non-stoichiometry of samples was then studied chemically by iodometric titration, wherein the concentration of Ni3+ determined by chemical analysis, which is increasing with increasing excess of oxygen or reducing the sintering temperature from the stoichiometric NiO; it decreases as sintering temperature increases. These results were corroborated by the excess oxygen obtained from the thermo-gravimetric analysis (TGA). X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) techniques indicate the crystalline nature, Ni-O bond vibrations and cubic structural phase of Ni1-δ O. The change in oxidation state of nickel from Ni3+ to Ni2+ were seen in the X-ray photoelectron spectroscopy (XPS) analysis and found to be completely saturated in Ni2+ as the sintering temperature reaches 700 °C. This analysis accounts for the implication of non-stoichiometric on the magnetization data, which indicate a shift in antiferromagnetic ordering temperature (T N) due to associated increased magnetic disorder. A sharp transition in the specific heat capacity at T N and a shift towards lower temperature are also evidenced with respect to the non-stoichiometry of the system.

Trioctylphosphine as self-assembly inducer.

Nickel nanoparticles (NPs) of different shapes and sizes in polydispersed as well as monodispersed forms were synthesized using trioctylphosphine (TOP), triphenylphosphine (TPP), oleylamine (OA) and their combinations as surfactants to study their self-assembly inducing capabilities. Randomly agglomerated polydispersed NPs were found for TPP and OA, and TPP or OA separately. However, in consolidation with the earlier report of Singh et al., J. Mater. Chem. C, 2014, 2, 8918, NPs formed using TOP only and a combination of TOP with OA naturally exhibited monodispersed NPs associated with natural nanolattice formation without any other external force or surfactants, demonstrating clearly the self-inducing capacity of TOP into monodispersed NPs and their self-assembled nanolattices. Fourier-transformed infra-red (FTIR) data clearly indicated the capping of these surfactants along with acetylacetonate ligands from nickel acetylacetonate precursor on the surface of the NPs. Remarkably, the narrowest zeta potential (ζ) base-widths were observed for samples possessing a self-assembled nanolattice, compared to the broader ones for randomly agglomerated particles.