A series of (ZnO)m(CoO)n digital alloys and superlattices grown by atomic layer deposition has been investigated by a range of experimental methods. The data provide evidences that the Co interdiffusion in the digital alloy structures is sufficient t
o produce truly random Zn1-xCoxO mixed crystals with x up to 40%. Conversely, in the superlattice structures the interdiffusion is not strong enough to homogenize the Co content along the growth direction results in the formation of (Zn,Co)O films with spatially modulated Co concentrations. All structures deposited at 160circC show magnetic properties specific to dilute magnetic semiconductors with localized spins S = 3/2 coupled by strong but short range antiferromagnetic interactions that lead to low temperature spin-glass freezing. It is demonstrated that ferromagnetic-like features, visible exclusively in layers grown at 200circC and above, are associated with an interfacial mesh of metallic Co granules residing between the substrate and the (Zn,Co)O layer. This explains why the magnitude of ferromagnetic signal is virtually independent of the film thickness as well as elucidates the origin of magnetic anisotropy. Our conclusions have been derived for layers in which the Co concentration, distribution, and aggregation have been determined by: secondary-ion mass spectroscopy, electron probe micro-analysis, high-resolution transmission electron microscopy with capabilities allowing for chemical analysis; x-ray absorption near-edge structure; extended x-ray absorption fine-structure; x-ray photoemission spectroscopy, and x-ray circular magnetic dichroism. Macroscopic properties of these layers have been investigated by superconducting quantum interference device magnetometery and microwave dielectric losses allowing to confirm the important role of metallic inclusions.
A theoretical model is presented which allows to reconcile findings of scanning tunnelling spectroscopy for (Ga,Mn)As [Richardella et al. Science 327, 66 (2010)] with results for tunneling across (Ga,Mn)As thin layers [Ohya et al. Nature Phys. 7, 342
(2011); Phys. Rev. Lett. 104, 167204 (2010)]. According to the proposed model, supported by a self-consistent solution of the Poisson and Schroedinger equations, a nonmonotonic behaviour of differential tunnel conductance as a function of bias is associated with the appearance of two-dimensional hole subbands rather in the GaAs:Be electrode than in the (Ga,Mn)As layer.
The sign, magnitude, and range of the exchange couplings between pairs of Mn ions is determined for (Ga,Mn)N and (Ga,Mn)N:Si with x < 3%. The samples have been grown by metalorganic vapor phase epitaxy and characterized by secondary-ion mass spectros
copy; high-resolution transmission electron microscopy with capabilities allowing for chemical analysis, including the annular dark-field mode and electron energy loss spectroscopy; high-resolution and synchrotron x-ray diffraction; synchrotron extended x-ray absorption fine-structure; synchrotron x-ray absorption near-edge structure; infra-red optics and electron spin resonance. The results of high resolution magnetic measurements and their quantitative interpretation have allowed to verify a series of ab initio predictions on the possibility of ferromagnetism in dilute magnetic insulators and to demonstrate that the interaction changes from ferromagnetic to antiferromagnetic when the charge state of the Mn ions is reduced from 3+ to 2+.
Systematic investigations of the structural and magnetic properties of single crystal (Ga,Mn)N films grown by metal organic vapor phase epitaxy are presented. High resolution transmission electron microscopy, synchrotron x-ray diffraction, and extend
ed x-ray absorption fine structure studies do not reveal any crystallographic phase separation and indicate that Mn occupies Ga-substitutional sites in the Mn concentration range up to 1%. The magnetic properties as a function of temperature, magnetic field and its orientation with respect to the c-axis of the wurtzite structure can be quantitatively described by the paramagnetic theory of an ensemble of non-interacting Mn$^{3+}$ ions in the relevant crystal field, a conclusion consistent with the x-ray absorption near edge structure analysis. A negligible contribution of Mn in the 2+ charge state points to a low concentration of residual donors in the studied films. Studies on modulation doped p-type (Ga,Mn)N/(Ga,Al)N:Mg heterostructures do not reproduce the high temperature robust ferromagnetism reported recently for this system.
