Epitaxial thin films of an oxide-diluted magnetic semiconductor, Mn-doped ZnO, were fabricated by pulsed-laser deposition technique. Solubility of Mn into ZnO exceeds thermal equilibrium limit as a result of nonequilibrium film growth process. As Mn content is increased, the lattice constants of both a and c axes of wurtzite Zn1−xMnxO films (x<0.35) increase and the band gap expands although considerable in-gap absorption develops. Itinerant electrons over 1019 cm−3 can be doped into the Zn1−xMnxO films by Al doping, in contrast to low carrier density in the other II–VI diluted magnetic semiconductors. The temperature dependence of the resistivity is almost metallic and considerable magnetoresistance is observed at low temperatures.

We report on the magnetic properties of an oxide-diluted magnetic semiconductor (DMS), Zn0.64Mn0.36O. The temperature dependence of the magnetization shows a spin-glass behavior with the large magnitude of the Curie–Weiss temperature, corresponding to a stronger antiferromagnetic exchange coupling than other II–VI DMSs. The small effective Mn moment (x̄∼0.02) under high field also represents a strong antiferromagnetic exchange coupling in this compound.

Combinatorial laser molecular-beam epitaxy method was employed to fabricate epitaxial ZnO thin films doped with all the 3d transition metal (TM) ions in a high throughput fashion. The solubility behavior of TM ions was discussed from the viewpoints of the ionic radius and valence state. The magneto-optical responses coincident with absorption spectra were observed for Mn- and Co-doped samples. Cathodoluminescence spectra were studied for Cr-, Mn-, Fe-, and Co-doped samples, among which Cr-doped ZnO showed two sharp peaks at 2.97 eV and 3.71 eV, respectively, at the expense of the exciton emission peak of pure ZnO at 3.25 eV. Different magnetoresistance behavior was observed for the samples codoped with n-type carriers. Ferromagnetism was not observed for Cr- to Cu-doped samples down to 3 K.

Technology [Abstract] Magneto-optical properties of ZnO:Co and ZnO:Ni films were measured. Magnetization measurements show that some of the films are paramagnetic and others are ferromagnetic. Magnetic circular dichroism clarified that Zn 1-x Co x O and Zn 1-x Ni x O included in samples are paramagnetic diluted magnetic semiconductors. Ferromagnetic precipitations seem to be responsible for the observed ferromagnetic behaviors. Criteria to judge the ferromagnetic DMS are also discussed.

Strong magneto-optical effect of Zn1−xCoxO near the optical band gap is reported. Magnetic circular dichroism (MCD) and Faraday rotation of Zn1−xCoxO (x=0.012 and 0.016) at 5 K are as high as 2°/cm Oe at 3.4 eV, which are about two orders larger than those of ZnO. Absence of strong Co2+ d–d* transition near the optical band gap makes Zn1−xCoxO an useful material for short-wavelength magneto-optical applications. Large magneto-optical effects and paramagnetic temperature dependence of MCD show a strong mixing of the sp bands of the host ZnO with Co2+ d orbitals. The polarity of the MCD peak is negative indicating the antiferromagnetic p–d exchange interaction.