During the past years there has been renewed interest in the wide-bandgap II-VI semiconductor ZnO, triggered by promising prospects for spintronic applications. First, ferromagnetism was predicted for dilute magnetic doping. In comprehensive investig
ation of ZnO:Co thin films based on the combined measurement of macroscopic and microscopic properties, we find no evidence for carrier-mediated itinerant ferromagnetism. Phase-pure, crystallographically excellent ZnO:Co is uniformly paramagnetic. Superparamagnetism arises when phase separation or defect formation occurs, due to nanometer-sized metallic precipitates. Other compounds like ZnO:(Li,Ni) and ZnO:Cu do not exhibit indication of ferromagnetism. Second, its small spin-orbit coupling and correspondingly large spin coherence length makes ZnO suitable for transporting or manipulating spins in spintronic devices. From optical pump/optical probe experiments, we find a spin dephasing time of the order of 15 ns at low temperatures which we attribute to electrons bound to Al donors. In all-electrical magnetotransport measurements, we successfully create and detect a spin-polarized ensemble of electrons and transport this spin information across several nanometers. We derive a spin lifetime of 2.6 ns for these itinerant spins at low temperatures, corresponding well to results from an electrical pump/optical probe experiment.
We report on the growth of epitaxial ZnO thin films and ZnO based heterostructures on sapphire substrates by laser molecular beam epitaxy (MBE). We first discuss some recent developments in laser-MBE such as flexible ultra-violet laser beam optics, i
nfrared laser heating systems or the use of atomic oxygen and nitrogen sources, and describe the technical realization of our advanced laser-MBE system. Then we describe the optimization of the deposition parameters for ZnO films such as laser fluence and substrate temperature and the use of buffer layers. The detailed structural characterization by x-ray analysis and transmission electron microscopy shows that epitaxial ZnO thin films with high structural quality can be achieved, as demonstrated by a small out-of-plane and in-plane mosaic spread as well as the absence of rotational domains. We also demonstrate the heteroepitaxial growth of ZnO based multilayers as a prerequisite for spin transport experiments and the realization of spintronic devices. As an example, we show that TiN/Co/ZnO/Ni/Au multilayer stacks can be grown on (0001)-oriented sapphire with good structural quality of all layers and well defined in-plane epitaxial relations.
The recent study of oxides led to the discovery of several new fascinating physical phenomena. High-temperature superconductivity, colossal magnetoresistance, dilute magnetic doping, or multiferroicity were discovered and investigated in transition-m
etal oxides, representing a prototype class of strongly correlated electronic systems. This development was accompanied by an enormous progress regarding thin film fabrication. Within the past two decades, epitaxial thin films with crystalline quality approaching semiconductor standards became available using laser molecular beam epitaxy. This evolution is reviewed, particularly with emphasis on transition-metal oxide thin films, their versatile physical properties, and their impact on the field of spintronics. First, the physics of ferromagnetic half-metallic oxides, such as the doped manganites, the double perovskites and magnetite is presented together with possible applications based on magnetic tunnel junctions. Second, the wide bandgap semiconductor zinc oxide is discussed particularly with regard to the controversy of dilute magnetic doping with transition-metal ions and the possibility of realizing p-type conductivity. Third, the field of oxide multiferroics is presented with the recent developments in single-phase multiferroic thin film perovskites as well as in composite multiferroic hybrids.
Transition metal oxides show fascinating physical properties such as high temperature superconductivity, ferro- and antiferromagnetism, ferroelectricity or even multiferroicity. The enormous progress in oxide thin film technology allows us to integra
te these materials with semiconducting, normal conducting, dielectric or non-linear optical oxides in complex oxide heterostructures, providing the basis for novel multi-functional materials and various device applications. Here, we report on the combination of ferromagnetic, semiconducting, metallic, and dielectric materials properties in thin films and artificial heterostructures using laser molecular beam epitaxy. We discuss the fabrication and characterization of oxide-based ferromagnetic tunnel junctions, transition metal-doped semiconductors, intrinsic multiferroics, and artificial ferroelectric/ferromagetic heterostructures - the latter allow for the detailed study of strain effects, forming the basis of spin-mechanics. For characterization we use X-ray diffraction, SQUID magnetometry, magnetotransport measurements, and advanced methods of transmission electron microscopy with the goal to correlate macroscopic physical properties with the microstructure of the thin films and heterostructures.
The existence of semiconductors exhibiting long-range ferromagnetic ordering at room temperature still is controversial. One particularly important issue is the presence of secondary magnetic phases such as clusters, segregations, etc... These are of
ten tedious to detect, leading to contradictory interpretations. We show that in our cobalt doped ZnO films grown homoepitaxially on single crystalline ZnO substrates the magnetism unambiguously stems from metallic cobalt nano-inclusions. The magnetic behavior was investigated by SQUID magnetometry, x-ray magnetic circular dichroism, and AC susceptibility measurements. The results were correlated to a detailed microstructural analysis based on high resolution x-ray diffraction, transmission electron microscopy, and electron-spectroscopic imaging. No evidence for carrier mediated ferromagnetic exchange between diluted cobalt moments was found. In contrast, the combined data provide clear evidence that the observed room temperature ferromagnetic-like behavior originates from nanometer sized superparamagnetic metallic cobalt precipitates.
