Synthesis of Fe-doped ZnO particle/polymer hybrid from metalorganics
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Tomoko Nakafuku Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
Wataru Sakamoto Division of Nanomaterials Science, EcoTopia Science Institute, Nagoya University, Nagoya 464-8603, Japan
Shin-ichi Hirano Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan (Received 31 July 2004; accepted 2 March 2005)
An Fe-doped ZnO particle/polymer hybrid was synthesized from zinc acrylate (ZA) and iron allylacetylacetonate (IAA) using methylhydrazine. Nanocrystalline ZnO particles were formed in the organic matrix by hydrolysis and polymerization of ZA itself below 100 °C. The crystallinity of undoped ZnO particles in the hybrid was dependent upon the synthesis conditions. Similarly, the ZnO phase was observed for the product formed from ZA-IAA. Transmission electron microscopy and energy-dispersive x-ray analysis revealed that crystalline ZnO nanoparticles doped with Fe were dispersed in the organic matrix. The absorption edge of the undoped ZnO particle/polymer hybrid was blue-shifted with the decrease in size of the ZnO particles. On the other hand, the Fe-doped ZnO particle/polymer hybrid from ZA-IAA revealed a bathochromic shift of the absorption edge up to 600 nm.
I. INTRODUCTION
Recently, growing attention has been focused on inorganic/organic hybrid materials because of their applications in newly emerging composite materials.1–3 Inorganic particulate/organic hybrid materials attracted attention because nano-sized particles are known to possess interesting properties, such as superparamagnetism4 and quantum confinement effect.5 The blending of nanosized particles into polymers is very difficult and is always accompanied by the agglomeration of particles due to van der Waals force. Crystallization of such particles in situ in an organic matrix could be highly advantageous over the conventional mixing of metal oxide particles and polymers. The uniform formation of nano-sized crystalline particles results from controlled nucleation and growth, which is attributed to the reactivity of chemical bonds of metal-organic precursors. Thus, the chemical design of a)
Address all correspondence to this author. e-mail: [email protected] DOI: 10.1557/JMR.2005.0187 1470
http://journals.cambridge.org
J. Mater. Res., Vol. 20, No. 6, Jun 2005 Downloaded: 13 Mar 2015
the precursor is required for the synthesis of the hybrid materials. Earlier, the authors reported the synthesis of iron oxide/polymer hybrid6–8 and perovskite oxide/ oragnic hybrid materials9–12 from metalorganics. The iron oxide particle/organic hybrid showed superparamagnetism and quantum confinement effect based upon nano-sized iron oxide particles.7,8 Nanocrystalline BaTiO3, PbTiO3, and KNbO3 particles were dispersed in the organic matrices under the controlled hydrolysis and polymerization of corresponding double metalorganic precursors.9–12 Nano-sized ZnO particles are known to exhibit quantum confinement effects.13–16 ZnO particles less than 1
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