Boris B. Straumal

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...

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.

Thermodynamic aspects of the grain boundary segregation in Cu(Bi) alloys

Abstract The grain boundary segregation of Bi in dilute polycrystalline Cu–Bi alloys was systematically studied as a function of temperature and composition. The temperature dependencies of the Gibbsian excess of Bi at the grain boundaries exhibited discontinuous changes at the temperatures close to, but different from the bulk solidus temperatures. The observed segregational phase transition was interpreted in terms of prewetting model.

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.

Ferromagnetism of nanostructured zinc oxide films

The paper presents a review of the causes of the occurrence of ferromagnetic properties in zinc oxide. It is shown that ferromagnetism only occurs in polycrystals at a fairly high density of grain boundaries. The critical grain size is about 20 nm for pure ZnO and over 1000 nm for zinc oxide doped with manganese. The solubility of manganese and cobalt in zinc oxide increases considerably with diminishing grain size. Even at the critical grain size, the ferromagnetic properties depend significantly on the film texture and the structure of intercrystalline amorphous layers.

Ferromagnetic behaviour of ZnO: the role of grain boundaries

The possibility to attain ferromagnetic properties in transparent semiconductor oxides such as ZnO is very promising for future spintronic applications. We demonstrate in this review that ferromagnetism is not an intrinsic property of the ZnO crystalline lattice but is that of ZnO/ZnO grain boundaries. If a ZnO polycrystal contains enough grain boundaries, it can transform into the ferromagnetic state even without doping with “magnetic atoms” such as Mn, Co, Fe or Ni. However, such doping facilitates the appearance of ferromagnetism in ZnO. It increases the saturation magnetisation and decreases the critical amount of grain boundaries needed for FM. A drastic increase of the total solubility of dopants in ZnO with decreasing grain size has been also observed. It is explained by the multilayer grain boundary segregation.

Penetration of Tin and zinc along tilt grain boundaries 43° [100] in Fe-5 at.% Si alloy : premelting phase transition ?

Abstract Tin and zinc penetration along the tilt grain boundary 43° [100] in b.c.c. Fe-5 at.% Si alloy is studied in the temperature range from 652 to 975°C. Wetting transition of grain boundary by the tin-rich melt at Tw = 810 ± 5°C is observed. About Tw there is a thin wetting film at grain boundary. With zinc penetration along the grain boundary a wetting film has been observed at all temperatures studied. Behind that film there is a region with an unusually high diffusivity of zinc, and below that region there is a region of “ordinary” grain boundary diffusivity. Such a phenomenon may be explained in terms of the phase transition “grain boundary-thin wetting film on the boundary”, which is commonly known as a premelting phase transition. A model is proposed which explains the form of the temperature dependence of the concentration cBt, at which such transition occurs, and, in particular, the influence of the “paramagnet-ferromagnet” transition in the bulk on the premelting transition. The influence of the temperature dependence of the volume solubility limit, c0, on the cBt(T) dependence is also discussed. In critical region below Curie point Tc critical exponents d of magnetic part of activation free energy of bulk and grain boundary diffusion are calculated. Critical index d for grain boundary diffusion by premelting layer, as well as activation energy in paramagnetic region, lies in the interval between bulk values of d and estimation of d for truly two-dimensional grain boundary diffusion.