Proof of the elusive high-temperature incommensurate phase in CuO by spherical neutron polarimetry.

CuO is the only known binary multiferroic compound, and due to its high transition temperature into the multiferroic state, it has been extensively studied. In comparison to other prototype multiferroics, the nature and even the existence of the high-temperature incommensurate paraelectric phase (AF3) were strongly debated-both experimentally and theoretically-since it is stable for only a few tenths of a kelvin just below the Néel temperature. Until now, there is no proof by neutron diffraction techniques owing to its very small ordered Cu magnetic moment. Here, we demonstrate the potential of spherical neutron polarimetry, first, in detecting magnetic structure changes, which are not or weakly manifest in the peak intensity and, second, in deducing the spin arrangement of the so far hypothetic AF3 phase. Our findings suggest two coexisting spin density waves emerging from an accidental degeneracy of the respective states implying a delicate energy balance in the spin Hamiltonian.

Ensemble averaged structure-function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin.

Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure-function relationship for metallic NCs is to be quantified precisely. We address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction, respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Thus we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure-function relationship for the increasingly complex metallic NCs explored for practical applications.

Monolithic integration of room-temperature multifunctional BaTiO3-CoFe2O4 epitaxial heterostructures on Si(001).

The multifunctional (ferromagnetic and ferroelectric) response at room temperature that is elusive in single phase multiferroic materials can be achieved in a proper combination of ferroelectric perovskites and ferrimagnetic spinel oxides in horizontal heterostructures. In this work, lead-free CoFe2O4/BaTiO3 bilayers are integrated with Si(001) using LaNiO3/CeO2/YSZ as a tri-layer buffer. They present structural and functional properties close to those achieved on perovskite substrates: the bilayers are fully epitaxial with extremely flat surface, and exhibit robust ferromagnetism and ferroelectricity at room temperature.

Magnetoelectric effect and phase transitions in CuO in external magnetic fields.

Apart from being so far the only known binary multiferroic compound, CuO has a much higher transition temperature into the multiferroic state, 230 K, than any other known material in which the electric polarization is induced by spontaneous magnetic order, typically lower than 100 K. Although the magnetically induced ferroelectricity of CuO is firmly established, no magnetoelectric effect has been observed so far as direct crosstalk between bulk magnetization and electric polarization counterparts. Here we demonstrate that high magnetic fields of ≈ 50 T are able to suppress the helical modulation of the spins in the multiferroic phase and dramatically affect the electric polarization. Furthermore, just below the spontaneous transition from commensurate (paraelectric) to incommensurate (ferroelectric) structures at 213 K, even modest magnetic fields induce a transition into the incommensurate structure and then suppress it at higher field. Thus, remarkable hidden magnetoelectric features are uncovered, establishing CuO as prototype multiferroic with abundance of competitive magnetic interactions.

Polar domain walls trigger magnetoelectric coupling.

Interface physics in oxides heterostructures is pivotal in material's science. Domain walls (DWs) in ferroic systems are examples of naturally occurring interfaces, where order parameter of neighboring domains is modified and emerging properties may develop. Here we show that electric tuning of ferroelastic domain walls in SrTiO3 leads to dramatic changes of the magnetic domain structure of a neighboring magnetic layer (La1/2Sr1/2MnO3) epitaxially clamped on a SrTiO3 substrate. We show that the properties of the magnetic layer are intimately connected to the existence of polar regions at twin boundaries of SrTiO3, developing at , that can be electrically modulated. These findings illustrate that by exploiting the responsiveness of DWs nanoregions to external stimuli, even in absence of any domain contribution, prominent and adjustable macroscopic reactions of neighboring layers can be obtained. We conclude that polar DWs, known to exist in other materials, can be used to trigger tunable responses and may lead to new ways for the manipulation of interfacial emerging properties.

High Temperature Magnetic Stabilization of Cobalt Nanoparticles by an Antiferromagnetic Proximity Effect.

Thermal activation tends to destroy the magnetic stability of small magnetic nanoparticles, with crucial implications for ultrahigh density recording among other applications. Here we demonstrate that low-blocking-temperature ferromagnetic (FM) Co nanoparticles (T(B)<70 K) become magnetically stable above 400 K when embedded in a high-Néel-temperature antiferromagnetic (AFM) NiO matrix. The origin of this remarkable T(B) enhancement is due to a magnetic proximity effect between a thin CoO shell (with low Néel temperature, T(N), and high anisotropy, K(AFM)) surrounding the Co nanoparticles and the NiO matrix (with high T(N) but low K(AFM)). This proximity effect yields an effective antiferromagnet with an apparent T(N) beyond that of bulk CoO, and an enhanced anisotropy compared to NiO. In turn, the Co core FM moment is stabilized against thermal fluctuations via core-shell exchange-bias coupling, leading to the observed T(B) increase. Mean-field calculations provide a semiquantitative understanding of this magnetic-proximity stabilization mechanism.

Synthesis, structure and in vitro cytotoxic studies of novel paramagnetic palladium(III) complexes with hematoporphyrin IX.

Two coordination compounds of Pd(III) with hematoporphyrin IX ((7,12-bis(1-hydroxyethyl)-3,8,13,17-tetramethyl-21H-23H-porphyn-2,18-dipropionic acid), Hp), dinuclear [Pd(III)2(Hp-3H)Cl3(H2O)5]·2PdCl2, 1 and mononuclear [Pd(III)(Hp-2H)Cl(H2O)]·H2O, 2 were obtained and structurally characterized in solid state and solution using spectroscopic, thermal and magnetic methods. In the dinuclear complex, 1 one of the Pd(III) ions is coordinated to the deprotanated COO(-) groups from the side chains of the porphyrin ligand and the second Pd(III) ion - to two adjacent pyrrole N-atoms on the top of the porphyrin ring and a Pd(III)-Hp-Pd(III) system was formed. The Pd(III) ion in the mononuclear complex, 2 is incorporated in the porphyrin core. The Pd(III) centers in both complexes have a distorted octahedral coordination filled with additional donor species such as Cl(-) and H2O. The studied compounds showed in vitro cell growth inhibitory effects at micromolar concentration against a panel of human tumor cell lines. A DNA fragmentation assay indicated that the growth inhibitory effects are at least partly mediated by induction of apoptosis.

Dipolar driven spontaneous self assembly of superparamagnetic Co nanoparticles into micrometric rice-grain like structures.

Superparamagnetic single crystal single domain Co nanoparticles of 6 nm in diameter evaporated onto highly pyrolytic oriented graphite spontaneously self-assemble into super structures with an elongated shape. These structures have been studied by optical and scanning electron microscopies, atomic and magnetic force microscopy, electron dispersive X-ray analysis, and SQUID magnetometry. We propose that the weak dipolar interactions between superparamagnetic dipoles of the cobalt nanoparticles are responsible for the formation of these structures when the dipolar magnetic interactions are strong enough to influence the general process of self-assembly dominated by van der Waals forces between neighboring nanoparticles and between nanoparticles and the substrate during evaporation of the solvent.

Beating the superparamagnetic limit with exchange bias.

Interest in magnetic nanoparticles has increased in the past few years by virtue of their potential for applications in fields such as ultrahigh-density recording and medicine. Most applications rely on the magnetic order of the nanoparticles being stable with time. However, with decreasing particle size the magnetic anisotropy energy per particle responsible for holding the magnetic moment along certain directions becomes comparable to the thermal energy. When this happens, the thermal fluctuations induce random flipping of the magnetic moment with time, and the nanoparticles lose their stable magnetic order and become superparamagnetic. Thus, the demand for further miniaturization comes into conflict with the superparamagnetism caused by the reduction of the anisotropy energy per particle: this constitutes the so-called 'superparamagnetic limit' in recording media. Here we show that magnetic exchange coupling induced at the interface between ferromagnetic and antiferromagnetic systems can provide an extra source of anisotropy, leading to magnetization stability. We demonstrate this principle for ferromagnetic cobalt nanoparticles of about 4 nm in diameter that are embedded in either a paramagnetic or an antiferromagnetic matrix. Whereas the cobalt cores lose their magnetic moment at 10 K in the first system, they remain ferromagnetic up to about 290 K in the second. This behaviour is ascribed to the specific way ferromagnetic nanoparticles couple to an antiferromagnetic matrix.