Transition metals in ZnO nanocrystals: Magnetic and structural properties

Abstract

Currently, wide-gap ZnO nanoparticles bear important potential application in electro-optical devices, transparent ultraviolet protection films, and spintronic devices. We have studied the magnetic properties of nanocrystals of ZnO(Fe, Co, Mn) prepared by two methods of synthesis. We have used the microwave assisted hydrothermal synthesis and traditional wet chemistry method followed by calcination. The detailed structural characterization was performed by means of X-ray diffraction and micro-Raman spectroscopy measurements. The morphology of the samples was studied by means of SEM and TEM microscopy. The results of systematic measurements of AC magnetic susceptibility as a function of temperature and frequency as well as SQUID magnetization are presented. The SQUID magnetization measurements revealed a clear bifurcation of the FC and ZFC plots. Such behavior suggested superparamagnetic behavior above the blocking temperature. The dynamic magnetic measurements were performed at small AC magnetic field with amplitude not exceeding 5 Oe and different frequency values (from 7 Hz to 9970 Hz). For ZnO(Fe) and ZnO(Mn), the AC susceptibility maxima has been found for in-phase susceptibility Re(?) and for out of phase susceptibility Im(?). We analyzed the observed frequency dependence of the peak temperature in the AC susceptibility curve using the empirical parameter ? that is a quantitative measure of the frequency shift and is given by the relative shift of the peak temperature per decade shift in frequency, as well as Vogel- Fulcher law. We observed two different types of magnetic behavior, spin-glasslike behavior or superparamagnetic behavior, depending on the synthesis process. For ZnO(Co) nanocrystalline samples high temperature Curie-Weiss behavior in AC magnetic susceptibility was observed. We observed that the determined negative values of the Curie- Weiss temperature ? depend strongly on the nominal content of cobalt oxide. It was shown that for calcination method the values of ? increase with the increase of magnetic ion content indicating enhancement of predominance of antiferromagnetic interactions. For hydrothermal method the opposite effect was observed indicating the breakdown of predominance of aniferromagnetic coupling with the increase of nominal magnetic ion content. This paper gives an in-depth discussion of the structural and magnetic properties of ZnO nanocrystals in addition to the technological issues such as different methods of wet chemical synthesis.