E. Goering

Magnetic reflectometry of heterostructures

Measuring the magnetic configuration at complex buried layers and interfaces is an important task, which requires especially a non-destructive probing technique. X-ray resonant magnetic reflectometry (XRMR) combines the non-destructive depth profiling potential of x-ray reflectometry with the excellent sensitivity for magnetic phenomena, utilizing the x-ray magnetic circular dichroism effect. It provides the magnetic spatial distribution with a precision down to the angstrom scale, combined with element and symmetry specificity, sub-monolayer sensitivity, and the possible separation of spin and orbital magnetic moments. This review provides an overview to the XRMR technique in a tutorial way. We focus on the introduction to the theory, measurement types, and data simulation. We provide related experimental examples and show selected applications.

Ferromagnetic properties of the Mn-doped nanograined ZnO films

Dense nanograined pure and Mn-doped Zn1−xMnxO polycrystals with x ranging between 0.1–34 at. % were synthesized by the wet chemistry method from butanoate precursors. Pure and Mn-doped ZnO possesses ferromagnetic properties only if the ratio of grain boundary (GB) area to grain volume sGB exceeds a certain threshold value sth. The polycrystals in this work satisfy these conditions and, therefore, reveal ferromagnetic properties. The observed dependence of saturation magnetization on the Mn concentration shows an unexpected nonmonotonous behavior. The increase in saturation magnetization at low Mn concentration is explained by the injection of divalent Mn2+ ions and charge carriers into pure ZnO. The decrease in saturation magnetization between 0.1 and 5 at. % Mn can be explained by the increase in the portion of Mn3+ and Mn4+ ions. The second increase in saturation magnetization above 5 at. % Mn is explained by the formation of multilayer Mn segregation layer in ZnO GBs. The shape of the dependence of sat...

Induced magnetism of carbon atoms at the graphene/Ni(111) interface

We report an element-specific investigation of electronic and magnetic properties of the graphene/Ni(111) system. Using x-ray magnetic circular dichroism, the occurrence of an induced magnetism of the carbon atoms in the graphene layer is observed. We attribute this magnetic moment to the strong hybridization between C π and Ni 3d valence band states. The net magnetic moment of carbon in the graphene layer is estimated to be in the range of 0.05–0.1 μB per atom.

Orbital reflectometry of oxide heterostructures

The occupation of d orbitals controls the magnitude and anisotropy of the inter-atomic electron transfer in transition-metal oxides and hence exerts a key influence on their chemical bonding and physical properties. Atomic-scale modulations of the orbital occupation at surfaces and interfaces are believed to be responsible for massive variations of the magnetic and transport properties, but could not thus far be probed in a quantitative manner. Here we show that it is possible to derive quantitative, spatially resolved orbital polarization profiles from soft-X-ray reflectivity data, without resorting to model calculations. We demonstrate that the method is sensitive enough to resolve differences of ~3% in the occupation of Ni e(g) orbitals in adjacent atomic layers of a LaNiO(3)-LaAlO(3) superlattice, in good agreement with ab initio electronic-structure calculations. The possibility to quantitatively correlate theory and experiment on the atomic scale opens up many new perspectives for orbital physics in transition-metal oxides.

XMCD studies on Co and Li doped ZnO magnetic semiconductors

ZnO doped with a few per cent (<10%) of magnetic ions such as Co exhibit room temperature (RT) ferromagnetism, transforming it into a very promising candidate for future spin electronic applications. We present x-ray magnetic circular dichroism (XMCD) spectroscopy, which has been used in total electron yield, total fluorescence yield, and reflection mode to investigate the origin of ferromagnetism in such diluted magnetic semiconductor materials in a surface, bulk and interface sensitive way, respectively. We investigated three different types of samples: ZnO doped with 5% Co, artificially layered films, and layered films with additional co-doping of 10% Li. These films are prepared by pulsed laser deposition (PLD) and characterized by superconducting quantum interference device (SQUID) magnetometry. Extensive XMCD measurements at the Co L2,3 and the O K edges, done with a very good signal-to-noise ratio, have revealed only cobalt paramagnetism and non magnetic oxygen signatures at low and high temperatures. We do not see any element specific signature for ferromagnetism at all. By exclusion, our results suggest oxygen vacancies as the intrinsic origin for RT ferromagnetism in doped ZnO.

Ferromagnetism of Zinc Oxide Nanograined Films

The reasons for the appearance of ferromagnetic properties of zinc oxide have been reviewed. It has been shown that ferromagnetism appears only in polycrystals at a quite high density of grain boundaries. The critical size of grains is about 20 nm for pure ZnO and more than 40 μm for iron-doped zinc oxide. The solubility of manganese and cobalt in zinc oxide increases significantly with a decrease in the size of grains. The dependences of the saturation magnetization on the concentrations of cobalt, manganese, and ion are nonmonotonic. Even if the size of grains is below the critical value, the ferromagnetic properties of zinc oxide depend significantly on the texture of films and the structure of amorphous intercrystallite layers.

Grain boundaries as the controlling factor for the ferromagnetic behaviour of Co-doped ZnO

The influence of the grain boundary (GB) specific area s GB on the appearance of ferromagnetism in Co-doped ZnO has been analysed based on a review of numerous research contributions from the literature on the origin of the ferromagnetic behaviour of Co-doped ZnO. An empirical correlation has been found that the value of the specific grain boundary area s GB is the main factor controlling such behaviour. The Co-doped ZnO becomes ferromagnetic only if it contains enough GBs, i.e., if s GB is higher than a certain threshold value s th = 1.5 × 106 m2/m3. It corresponds to the effective grain size of about 1 µm assuming a full dense material and equiaxial grains. The magnetic properties of Co-doped (0 to 42 at. %) ZnO dense nanograined thin films have been investigated. The films were deposited using the wet chemistry “liquid ceramics” method. The samples demonstrate ferromagnetic behaviour with J s up to 0.12 emu/g and coercivity H c ∼ 0.01 T. Saturation magnetization non-monotonically depends on the Co concentration. The dependence on Co content can be explained by the changes in the structure of a ferromagnetic “grain boundary foam” responsible for the magnetic properties of pure and doped ZnO.

Interfacial dominated ferromagnetism in nanograined ZnO: a μSR and DFT study

Diamagnetic oxides can, under certain conditions, become ferromagnetic at room temperature and therefore are promising candidates for future material in spintronic devices. Contrary to early predictions, doping ZnO with uniformly distributed magnetic ions is not essential to obtain ferromagnetic samples. Instead, the nanostructure seems to play the key role, as room temperature ferromagnetism was also found in nanograined, undoped ZnO. However, the origin of room temperature ferromagnetism in primarily non–magnetic oxides like ZnO is still unexplained and a controversial subject within the scientific community. Using low energy muon spin relaxation in combination with SQUID and TEM techniques, we demonstrate that the magnetic volume fraction is strongly related to the sample volume fraction occupied by grain boundaries. With molecular dynamics and density functional theory we find ferromagnetic coupled electron states in ZnO grain boundaries. Our results provide evidence and a microscopic model for room temperature ferromagnetism in oxides.

Grain Boundary Layers in Nanocrystalline Ferromagnetic Zinc Oxide

The complete solubility of an impurity in a polycrystal increases with decreasing grain size, because the impurity dissolves not only in the crystallite bulk but also on the grain boundaries. This effect is especially strong when the adsorption layers (or the grain boundary phases) are multilayer. For example, the Mn solubility in the nanocrystalline films (where the size of grains is ∼20 nm) is more than three times greater than that in the ZnO single crystals. The thin nanocrystalline Mn-doped ZnO films in the Mn concentration range 0.1–47 at % have been obtained from organic precursors (butanoates) by the “liquid ceramic” method. They have ferromagnetic properties, because the specific area of the grain boundaries in them is greater than the critical value [B.B. Straumal et al., Phys. Rev. B 79, 205206 (2009)]. The high-resolution electron transmission microscopy studies show that the ZnO nanocrystalline grains with the wurtzite lattice are separated by amorphous layers whose thickness increases with the Mn concentration. The morphology of these layers differs greatly from the structure of the amorphous prewetting films on the grain boundaries in the ZnO:Bi2O3 system.

Ferromagnetic behaviour of Fe-doped ZnO nanograined films

Summary The influence of the grain boundary (GB) specific area s GB on the appearance of ferromagnetism in Fe-doped ZnO has been analysed. A review of numerous research contributions from the literature on the origin of the ferromagnetic behaviour of Fe-doped ZnO is given. An empirical correlation has been found that the value of the specific grain boundary area s GB is the main factor controlling such behaviour. The Fe-doped ZnO becomes ferromagnetic only if it contains enough GBs, i.e., if s GB is higher than a certain threshold value s th = 5 × 104 m2/m3. It corresponds to the effective grain size of about 40 μm assuming a full, dense material and equiaxial grains. Magnetic properties of ZnO dense nanograined thin films doped with iron (0 to 40 atom %) have been investigated. The films were deposited by using the wet chemistry “liquid ceramics” method. The samples demonstrate ferromagnetic behaviour with J s up to 0.10 emu/g (0.025 μB/f.u.ZnO) and coercivity H c ≈ 0.03 T. Saturation magnetisation depends nonmonotonically on the Fe concentration. The dependence on Fe content can be explained by the changes in the structure and contiguity of a ferromagnetic “grain boundary foam” responsible for the magnetic properties of pure and doped ZnO.