PNNL

Abstract

We report the results of a detailed investigation of sol-gel synthesized nanoscale Zn1-xCoxO powders processed at 350 °C with 0 @ x @ 0.12 to understand how the structural, morphological, optical and magnetic properties of ZnO are modified by Co doping, in addition to searching for the theoretically predicated ferromagnetism. With x increasing to 0.03, both lattice parameters a and c of the hexagonal ZnO decreased suggesting substitutional doping of Co at the tetrahedral Zn2+ sites. For x > 0.03, these trends reversed and the lattice showed a gradual expansion as x approached 0.12, probably due to additional interstitial incorporation of Co. Raman spectroscopy measurements showed a rapid change in the ZnO peak positions for x > 0.03 suggesting significant disorder and changes in the ZnO structure, in support of additional interstitial Co doping possibility. Combined x-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance spectroscopy, photoluminescence spectroscopy and diffuse reflectance spectroscopy showed clear evidence for tetrahedrally coordinated high spin Co2+ ions occupying the lattice sites of ZnO host system, which became saturated for x > 0.03. Magnetic measurements showed a paramagnetic behavior in Zn1-xCoxO with increasing antiferromagnetic interactions as x increased to 0.10. Surprisingly, a weak ferromagnetic behavior was observed for the sample with x = 0.12 with a characteristic hysteresis loop showing a coercivity Hc ~ 350 Oe, 25% remanence Mr, a low saturation magnetization Ms ~ 0.04 emu/g and with a Curie temperature Tc ~ 540 K. The XPS data collected from Zn1-xCoxO samples showed a gradual increase in the oxygen concentration, changing the oxygen deficient undoped ZnO to an excess oxygen state for x = 0.12. This indicates that such high Co concentrations and appropriate oxygen stoichiometry may be needed to achieve adequate ferromagnetic exchange coupling between the incorporated Co2+ ions.