A process for chemically synthesizing size-controllable nickel oxide (NiO) nanoparticles (NPs) within the interior of mesoporous silicon (PSi) thin films is presented. The method is demonstrated to provide control of the average NP size over an order of magnitude, from 9 nm to 128 nm diameter, by fabricating PSi films with mean pore diameters ranging from 32 to 140 nm and annealing at temperatures between 300 and 1100 °C. NiO NPs are readily detached from the PSi films through electrolytic dissolution of the PSi host matrix. Nanocomposite films and NPs are characterized through x-ray diffraction, scanning electron microscopy, transmission electron microscopy, and energy-dispersive x-ray spectroscopy. Optical absorbance measurements of free NiO NPs in aqueous suspension indicate that the optical bandgap is tuned from 3.65 to 3.9 eV, as expected from the effects of quantum confinement. This synthesis process is amenable to the batch fabrication of a wide variety of metal oxide NPs at temperatures up to 1000 °C with sizes below 100 nm. The method is advantageous over conventional chemical synthesis techniques as it facilitates control of the resulting NP size across a wide range and also permits high-temperature annealing while precluding extended crystallite formation. Furthermore, the use of a PSi template enables direct integration of nanoparticulate metal oxide into Si-based, on-chip applications. NiO was selected here as the model system to demonstrate this technique due to its numerous applications including energy storage and memristor technologies.
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This work was supported in part by the National Science Foundation (DMR-1207019). The authors thank J. Keum for assistance with x-ray diffraction measurements and J. R. McBride for assistance with EDX mapping. X-ray diffraction was performed at the Center for Nanophase Materials Sciences, which is a DOE Office of User Science Facility. All other material characterization, including TEM (NSF EPS 1004083), was performed at the Vanderbilt Institute of Nanoscale Science and Engineering. J. S. Fain acknowledges support from a National Science Foundation Graduate Fellowship.
Ai L, Guojia F et al (2008) Influence of substrate temperature on electrical and optical properties of p-type semitransparent conductive nickel oxide thin films deposited by radio frequency sputtering. Appl Surf Sci 254:2401–2405. doi:10.1016/j.apsusc.2007.09.051CrossRefGoogle Scholar
Arico AS, Bruce P, Scrosati B, Tarascon J-M, Van Schalkwijk W (2005) Nanostructured materials for advanced energy conversion and storage devices. Nat Mater 4:366–377. doi:10.1038/nmat1368CrossRefGoogle Scholar
Banerjee N, Krupanidhi SB (2010) Synthesis, structural characterization and formation mechanism of giant-dielectric CaCu3Ti4O12 nanotubes. Nat Sci 2:688–693. doi:10.4236/ns.2010.27085Google Scholar
Dharmaraj N, Prabu P, Nagarajan S, Kim CH, Park JH, Kim HY (2006) Synthesis of nickel oxide nanoparticles using nickel acetate and poly(vinyl acetate) precursor. Mater Sci Eng B 128:111–114. doi:10.1016/j.mseb.2005.11.021CrossRefGoogle Scholar
Fox M (2001) Optical properties of solids. Oxford University Press, OxfordGoogle Scholar
Hooker PD, Klabunde KJ (1993) Reaction of nickel atoms with molton salts. A new approach to the synthesis of nanoscale metal, metal oxide, and metal carbide particles. Chem Mater 5:1089–1093. doi:10.1021/cm00032a011CrossRefGoogle Scholar
Jones CF, Segall RL, Smart RSC, Turner PS (1977) Semiconducting oxides: the effect of prior annealing temperature on dissolution kinetics of nickel oxide. J Chem Soc Faraday Trans 1(73):1710–1720. doi:10.1039/F19777301710CrossRefGoogle Scholar
Lee M-J, Han S et al (2009) Electrical manipulation of nanofilaments in transition-metal oxides for resistance-based memory. Nano Lett 9:1476–1481. doi:10.1021/n1803387CrossRefGoogle Scholar
Mendoza-Galvan A, Vidales-Hurtado MA, Lopez-Beltran AM (2009) Comparison of the optical and structural properties of nickel oxide-based thin films obtained by chemical bath and sputtering. Thin Solid Films 517:3115–3120. doi:10.1016/j.tsf.2008.11.094CrossRefGoogle Scholar
Ortega D, Hernandez-Garrido JC, Blanco-Andujar C, Garitaonandia JS (2013) Suppression and enhancement of the ferromagnetic response in Fe-doped ZnO nanoparticles by calcination of organic nitrogen, phosphorus, and sulfur compounds. J Nanopart Res 15:2120. doi:10.1007/s11051-013-2120-5CrossRefGoogle Scholar
Srinivasan V, Weidner JW (2000) Studies on the capacitance of nickel oxide films: effect of heating temperature and electrolyte concentration. J Electrochem Soc 147:880–885. doi:10.1149/1.1393286CrossRefGoogle Scholar
Wakefield G, Dobson PJ, Foo YY, Loni A, Simons A, Hutchison JL (1997) The fabrication and characterization of nickel oxide films and their application as contacts to polymer/porous silicon electroluminescent devices. Semicond Sci Technol 12:1304–1309. doi:10.1088/0268-1242/12/10/019CrossRefGoogle Scholar
Wang J, Wei L et al (2012) Preparation of high aspect ratio nickel oxide nanowires and their gas sensing devices with fast response and high sensitivity. J Mater Chem 22:8327–8335. doi:10.1039/c2jm16934gCrossRefGoogle Scholar
Yuan C, Zhang X, Su L, Gao B, Shen L (2009) Facile synthesis and self-assembly of hierarchical porous NiO nano/micro spherical superstructures for high performance supercapacitors. J Mater Chem 19:5772–5777. doi:10.1039/b902221jCrossRefGoogle Scholar
Yuan L, Meng S, Zhou Y, Yue Z (2013) Controlled synthesis of anatase TiO2 nanotube and nanowire arrays via AAO template-based hydrolysis. J Mater Chem A 1:2552–2557. doi:10.1039/c2ta00709fCrossRefGoogle Scholar
Zheng MJ, Zhang LD, Li GH, Shen WZ (2002) Fabrication and optical properties of large-scale uniform zinc oxide nanowire arrays by one-step electrochemical deposition technique. Chem Phys Lett 363:123–128. doi:10.1016/S0009-2614(02)01106-5CrossRefGoogle Scholar