Thomas Tietze

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.

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.

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.

Structural and magnetic deconvolution of FePt/FeOx-nanoparticles using x-ray magnetic circular dichroism

Recently, magnetite nanoparticles have attracted much attention, due to their technological potential based on different optic, magnetic and catalytic sections. In particular, the magnetic properties of hybrid nanocrystals can be tailored by the combination of complementary magnetic materials like for example magnetite and FePt. In order to analyse the related magnetic and structural properties of the resulting bi-component systems, we present x-ray absorption and x-ray magnetic circular dichroism studies at the Fe L2,3 edges simultaneously performed in total electron yield and transmission mode, done at room and low temperatures. This provides in particular the separation of volume- and surface-related properties. The investigated system was made up of FePt/FeOx hybrid nanocrystals, which could be uniquely tuned in size and volume ratios. These measurements have been combined with magnetometry and high-resolution transmission electron microscopy studies. The separation between surface and bulk has been done by a deconvolution of the absorption spectra in terms of a linear superposition of reference spectra. With this universally applicable technique we are able to experimentally determine that the outer FeOx shell fraction at the surface has a strongly reduced magnetization and is of maghemite character, while the inner part is more magnetite like. So the technique shown here can be used to characterize nanoparticular systems and determine their structural and magnetic properties.

Unexpected room-temperature ferromagnetism in bulk ZnO

It is demonstrated that a transition from paramagnetic behavior to clear room-temperature ferromagnetism (RTFM) exists in pure bulk ZnO. A significant enhancement of RTFM has been observed in argon-annealed ZnO samples. Quantitative chemical analysis unambiguously indicates that oxygen-related vacancies at surface play a crucial role in this observed RTFM. We suppose that the surface magnetic states, paramagnetic in the pure nanoparticles, are converted to ferromagnetic phase after mechanical compaction. Additionally, it is found that weakly adsorbed carbon species could block the exchange coupling between isolated magnetic moments in the surface layers.

Perpendicular magnetisation from in-plane fields in nano-scaled antidot lattices

Investigations of geometric frustrations in magnetic antidot lattices have led to the observation of interesting phenomena like spin-ice and magnetic monopoles. By using highly focused magneto-optical Kerr effect measurements and x-ray microscopy with magnetic contrast we deduce that geometrical frustration in these nanostructured thin film systems also leads to an out-of-plane magnetization from a purely in-plane applied magnetic field. For certain orientations of the antidot lattice, formation of perpendicular magnetic domains has been found with a size of several μm that may be used for an in-plane/out-of-plane transducer.

Absence of element specific ferromagnetism in Co doped ZnO investigated by soft X-ray resonant reflectivity

On the quest for the intrinsic origin of ferromagnetism (FM) in ZnO doped with a few percent transition metal, we show detailed X-ray resonant magnetic reflectivity (XRMR) measurements, performed at the Co L2,3 and the O K edges of pulsed laser deposition (PLD) prepared samples. These samples show ferromagnetism at room temperature (RT) (QUID: about 2μB /Co). But in contrast to the QUID measurements, element specific reflection measurements as a function of angle (θ-2θ scans) and energy (const. qz) do not show any sign of ferromagnetism. Therefore, we can exclude without doubt Co as a possible origin for FM in this system. Our results are in perfect agreement with earlier published XMCD data and strongly support the new proposed grain boundary based model for oxygen vacancies related RT-FM.

Pinned orbital moments – A new contribution to magnetic anisotropy

Reduced dimensionality and symmetry breaking at interfaces lead to unusual local magnetic configurations, such as glassy behavior, frustration or increased anisotropy. The interface between a ferromagnet and an antiferromagnet is such an example for enhanced symmetry breaking. Here we present detailed X-ray magnetic circular dichroism and X-ray resonant magnetic reflectometry investigations on the spectroscopic nature of uncompensated pinned magnetic moments in the antiferromagnetic layer of a typical exchange bias system. Unexpectedly, the pinned moments exhibit nearly pure orbital moment character. This strong orbital pinning mechanism has not been observed so far and is not discussed in literature regarding any theory for local magnetocrystalline anisotropy energies in magnetic systems. To verify this new phenomenon we investigated the effect at different temperatures. We provide a simple model discussing the observed pure orbital moments, based on rotatable spin magnetic moments and pinned orbital moments on the same atom. This unexpected observation leads to a concept for a new type of anisotropy energy.

Corrigendum: 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.