Helicity-dependent resonant X-ray scattering in CuB2O4.

Exploitation of X-ray circular polarized beams to study forbidden Bragg reflections and new information that could be obtained in these experiments are discussed. It is shown that the intensities of such reflections can be different for the right- and left-circular polarizations (i.e. exhibiting circular dichroism) even for the dipole-dipole resonant transitions involved in the scattering process. This difference can be observed only in crystals having no center of inversion. Here, this approach is used to study helicity-dependent resonant diffraction in copper metaborate CuB2O4 single crystal, which is non-centrosymmetric but achiral. Nonetheless, a strong circular dichroism has been observed for hh0 forbidden reflections in the vicinity of the Cu K-edge. This effect is shown to originate from dipolar transitions in Cu atoms occupying the 8(d) Wyckoff position only.

Noncollinear Ordering of the Orbital Magnetic Moments in Magnetite.

The magnitude of the orbital magnetic moment and its role as a trigger of the Verwey transition in the prototypical Mott insulator, magnetite, remain contentious. Using 1s2p resonant inelastic x-ray scattering angle distribution (RIXS-AD), we prove the existence of noncollinear orbital magnetic ordering and infer the presence of dynamical distortion creating a polaronic precursor for the metal to insulator transition. These conclusions are based on a subtle angular shift of the RIXS-AD spectral intensity as a function of the magnetic field orientation. Theoretical simulations show that these results are only consistent with noncollinear magnetic orbital ordering. To further support these claims we perform Fe K-edge x-ray magnetic circular dichroism in order to quantify the Fe average orbital magnetic moment.

Paramagnetic gold in a highly disordered Au-Ni-O alloy.

Magnetic materials are usually classified into a distinct category such as diamagnets, paramagnets or ferromagnets. The enormous progress in materials science allows one nowadays, however, to change the magnetic nature of an element in a material. Gold, in bulk form, is traditionally a diamagnet. But in a ferromagnetic environment, it can adopt an induced ferromagnetic moment. Moreover, the growth of gold under certain conditions may lead to a spontaneous ferromagnetic or paramagnetic response. Here, we report on paramagnetic gold in a highly disordered Au-Ni-O alloy and focus on the unusual magnetic response. Such materials are mainly considered for plasmonic applications. Thin films containing Au, Ni and NiO are fabricated by co-deposition of Ni and Au in a medium vacuum of 2 × 10-2 mbar. As a result, Au is in a fully disordered state forming in some cases isolated nanocrystallites of up to 4 nm in diameter as revealed by high resolution transmission electron microscopy. The disorder and the environment, which is rich in oxygen, lead to remarkable magnetic properties of Au: an induced ferromagnetic and a paramagnetic state. This can be proven by measuring the x-ray magnetic circular dichroism. Our experiments show a way to establish and monitor Au paramagnetism in alloys.

Non-hysteretic first-order phase transition with large latent heat and giant low-field magnetocaloric effect.

First-order magnetic transitions (FOMTs) with a large discontinuity in magnetization are highly sought in the development of advanced functional magnetic materials. Isosymmetric magnetoelastic FOMTs that do not perturb crystal symmetry are especially rare, and only a handful of material families, almost exclusively transition metal-based, are known to exhibit them. Yet, here we report a surprising isosymmetric FOMT in a rare-earth intermetallic, Eu2In. What makes this transition in Eu2In even more remarkable is that it is associated with a large latent heat and an exceptionally high magnetocaloric effect in low magnetic fields, but with tiny lattice discontinuities and negligible hysteresis. An active role of the Eu-5d and In-4p states and a rather unique electronic structure borne by In to Eu charge transfer, altogether result in an unusual exchange mechanism that both sets the transition in motion and unveils an approach toward developing specific magnetic functionalities ad libitum.

Probing Magnetism in the Vortex Phase of PuCoGa_{5} by X-Ray Magnetic Circular Dichroism.

We measure x-ray magnetic circular dichroism (XMCD) spectra at the Pu M_{4,5} absorption edges from a newly prepared high-quality single crystal of the heavy-fermion superconductor ^{242}PuCoGa_{5}, exhibiting a critical temperature T_{c}=18.7 K. The experiment probes the vortex phase below T_{c} and shows that an external magnetic field induces a Pu 5f magnetic moment at 2 K equal to the temperature-independent moment measured in the normal phase up to 300 K by a superconducting quantum interference device. This observation is in agreement with theoretical models claiming that the Pu atoms in PuCoGa_{5} have a nonmagnetic singlet ground state resulting from the hybridization of the conduction electrons with the intermediate-valence 5f electronic shell. Unexpectedly, XMCD spectra show that the orbital component of the 5f magnetic moment increases significantly between 30 and 2 K; the antiparallel spin component increases as well, leaving the total moment practically constant. We suggest that this indicates a low-temperature breakdown of the complete Kondo-like screening of the local 5f moment.

Magnetic polarization of the americium J=0 ground state in AmFe(2).

Trivalent americium has a nonmagnetic (J=0) ground state arising from the cancellation of the orbital and spin moments. However, magnetism can be induced by a large molecular field if Am^{3+} is embedded in a ferromagnetic matrix. Using the technique of x-ray magnetic circular dichroism, we show that this is the case in AmFe_{2}. Since ⟨J_{z}⟩=0, the spin component is exactly twice as large as the orbital one, the total Am moment is opposite to that of Fe, and the magnetic dipole operator ⟨T_{z}⟩ can be determined directly; we discuss the progression of the latter across the actinide series.

Experimental evidence of Cr magnetic moments at low temperature in Cr2A(A=Al, Ge)C.

From x-ray magnetic circular dichroism experiments performed at low temperature on Cr2AlC and Cr2GeC thin films, it is evidenced that Cr atoms carry a net magnetic moment in these ternary phases. It is shown that the Cr magnetization of the Al-based compound nearly vanished at 100 K in agreement with what has been recently observed on bulk. X-ray linear dichroism measurements performed at various angles of incidence and temperatures clearly demonstrate the existence of a charge ordering along the c axis of the structure of Cr2AlC. All these experimental observations support, in part, theoretical calculations claiming that Cr dd correlations have to be considered to correctly describe the structure and properties of these Cr-based ternary phases.

Europium nitride: a novel diluted magnetic semiconductor.

Europium nitride is semiconducting and contains nonmagnetic Eu3+, but substoichiometric EuN has Eu in a mix of 2+ and 3+ charge states. We show that at Eu2+ concentrations near 15%-20% EuN is ferromagnetic with a Curie temperature as high as 120 K. The Eu3+ polarization follows that of the Eu2+, confirming that the ferromagnetism is intrinsic to the EuN which is, thus, a novel diluted magnetic semiconductor. Transport measurements shed light on the likely exchange mechanisms.

Direct evidence for significant spin-polarization of EuS in Co/EuS multilayers at room temperature.

The new era of spintronics promises the development of nanodevices, where the electron spin will be used to store information and charge currents will be replaced by spin currents. For this, ferromagnetic semiconductors at room temperature are needed. We report on significant room-temperature spin polarization of EuS in Co/EuS multilayers recorded by x-ray magnetic circular dichroism (XMCD). The films were found to contain a mixture of divalent and trivalent europium, but only Eu(++) is responsible for the ferromagnetic behavior of EuS. The magnetic XMCD signal of Eu at room temperature could unambiguously be assigned to magnetic ordering of EuS and was found to be only one order of magnitude smaller than that at 2.5 K. The room temperature magnetic moment of EuS is as large as the one of bulk ferromagnetic Ni. Our findings pave the path for fabrication of room-temperature spintronic devices using spin polarized EuS layers.

Spin fluctuations of paramagnetic Rh clusters revealed by x-ray magnetic circular dichroism.

The magnetic moment induced on Rh atoms, forming 1.6 nm average diameter clusters, embedded in an Al(2)O(3) matrix, has been determined using x-ray magnetic circular dichroism measurements. The magnetic moment varies linearly with the applied magnetic field. At 2.3 K and under 17 T, the spin magnetic moment amounts to 0.067(2) µ(B)/Rh atom. The orbital moment does not exceed 2% of the spin moment. The susceptibility is highly temperature dependent. This is in agreement with a prediction due to Moriya and Kawabata, that in itinerant electron systems, close to the onset of magnetism, the renormalization of the magnetic susceptibility by electron correlations, leads to a Curie-like behavior.

Above room temperature ferromagnetism in Si:Mn and TiO(2-delta)Co.

We present recent experimental results on the structural, electrical, magnetic, and magneto-optical properties of Mn-implanted Si and Co-doped TiO(2-delta) magnetic oxides. Si wafers, both n- and p-type, with high and low resistivity, were used as the starting materials for implantation with Mn ions at the fluencies up to 5 x 10(16) cm(-2). The saturation magnetization was found to show the lack of any regular dependence on the Si conductivity type, type of impurity and the short post-implantation annealing. According to XMCD Mn impurity in Si does not bear any appreciable magnetic moment at room temperature. The obtained results indicate that above room temperature ferromagnetism in Mn-implanted Si originates not from Mn impurity but rather from structural defects in Si. The TiO(2-delta):Co thin films were deposited on LaAlO3 (001) substrates by magnetron sputtering in the argon-oxygen atmosphere at oxygen partial pressure of 2 x 10(-6)-2 x 10(-4) Torr. The obtained transverse Kerr effect spectra at the visible and XMCD spectra indicate on intrinsic room temperature ferromagnetism in TiO(2-delta):Co thin films at low (< 1%) volume fraction of Co.

Magnetic properties of textured CoPd nanocrystalline thin films.

CoPd is an important nanomaterial for magnetic and magneto-optic storage of information. In this work, CoPd alloyed thin films are grown via radio frequency magnetron sputtering on silicon, glass and polyimide substrates in a vacuum chamber with base pressure of 5 x 10(-8) mbar. The films are nanocrystalline with grain size between 4 and 80 nm. The magnetic properties of thoroughly textured CoPd alloyed thin films are compared to random polycrystalline ones. Magnetization hysteresis loops recorded under fields up to 12 kOe via a home-made magneto-optic Kerr-effect magnetometer reveal strong tendency for perpendicular magnetic anisotropy for the textured film. This anisotropy leads to the formation of well-defined stripe or labyrinthine ferromagnetic domains with the local spins oriented perpendicular to the film plane. The domain patterns and the hysteresis loops are simulated with micromagnetic calculations. Finally, an induced magnetic moment of 0.44 microB/atom is measured for Pd via X-ray magnetic circular dichroism and it is separated into spin and orbital magnetic moment contributions.

Strong paramagnetism of gold nanoparticles deposited on a Sulfolobus acidocaldarius S layer.

Magnetic properties of Au nanoparticles deposited on an archaeal S layer are reported. X-ray magnetic circular dichroism and superconducting quantum interference device magnetometries demonstrate that the particles are strongly paramagnetic, without any indication of magnetic blocking down to 16 mK. The average magnetic moment per particle is M(part)=2.36(7) µ(B). This contribution originates at the particle's Au 5d band, in which an increased number of holes with respect to the bulk value is observed. The magnetic moment per Au atom is 25 times larger than any measured in other Au nanoparticles or any other configurations up to date.

Co-doped ZnO epitaxial films: from a Brillouin-like paramagnet to a phase-separated superparamagnetic ensemble.

Co-doped ZnO films are epitaxially grown on sapphire by reactive magnetron sputtering. The preparation conditions such as temperature and the composition of the sputtering gas are systematically varied. For optimized growth conditions virtually all Co dopant atoms are located on substitutional Zn lattice sites as revealed by X-ray linear dichroism (XLD). The material behaves as a Brillouin-like paramagnet with S = 3/2 and L = 1 as revealed by integral and element specific magnetometry. Reducing the oxygen content during preparation leads to the onset of phase separation as revealed by X-ray diffraction, and more clearly by a strong reduction of the XLD signal. Such samples behave like a blocked superparamagnetic ensemble. In the entire range of preparation conditions no signs of intrinsic ferromagnetism are found.

Evidence for room-temperature multiferroicity in a compound with a giant axial ratio.

In the search for multiferroic materials magnetic compounds with a strongly elongated unit-cell (large axial ratio c/a) have been scrutinized intensely. However, none was hitherto proven to have a switchable polarization, an essential feature of ferroelectrics. Here, we provide evidence for the epitaxial stabilization of a monoclinic phase of BiFeO3 with a giant axial ratio (c/a=1.23) that is both ferroelectric and magnetic at room temperature. Surprisingly, and in contrast with previous theoretical predictions, the polarization does not increase dramatically with c/a. We discuss our results in terms of the competition between polar and antiferrodistortive instabilities and give perspectives for engineering multiferroic phases.

Using magnetic circular dichroism for the study of the magnetization and the magnetic moments of atoms in Nd(3)Fe(27.5)Ti(1.5).

An element-specific study of the Nd(3)Fe(27.5)Ti(1.5) compound using the hard x-ray magnetic circular dichroism (XMCD) technique is presented. The Nd L(2) and L(3) edge XMCD, as well as the Fe K edge XMCD, were measured in a magnetically oriented sample, parallel and perpendicular to its alignment direction. The XMCD spectra were recorded at three different temperatures, above, below and in between the characteristic peaks that the specific compound presents in AC susceptibility measurements. By probing the Nd L edges and the Fe K edge XMCD, we found that the dipolar R(5d)-Fe(3d) exchange interaction behaves differently with temperature change than the Fe-Fe magnetic interaction. Those differences appear to be in the vicinity of the AC susceptibility characteristic peaks. An XMCD signal was recorded at the Ti K edge, revealing a small orbital polarization due to the hybridization with Fe atomic states. This demonstrates the existence of a small finite magnetic moment in Ti atoms.

Low temperature exchange bias in [DyFe(2)/YFe(2)] superlattices: effect of the thermo-magnetic preparation.

The effect of the thermo-magnetic preparation on exchange bias is investigated in an exchange-coupled [3 nm DyFe(2)/12 nmYFe(2)](22) superlattice. X-ray magnetic circular dichroism (XMCD) experiments at low temperature reveal that exchange bias originates from the quenched DyFe(2) magnetization, biasing the unpinned YFe(2) reversal. This quenched configuration can be tailored by changing the cooling field or the magnetic preparation at 300 K before zero-field cooling. Changing the amplitude of the cooling field induces interface domain walls and tends to modify the orientation of the pinning moments at the interfaces. This results in the observation of single loops and in the continuous variation of the bias field as a function of the cooling field. A specific magnetic preparation (field cycling) at 300 K induces different remanent states with lateral domains in the pinning layer, which remain unchanged at low temperature after zero-field cooling and behave independently. This gives rise to combined loops, whose shape reflects the domain populations.

Inhomogeneous alloying in FePt nanoparticles as a reason for reduced magnetic moments.

The reduced magnetic moments of oxide-free FePt nanoparticles are discussed in terms of lattice expansion and local deviation from the averaged composition. By analyses of the extended x-ray absorption fine structure of FePt nanoparticles and bulk material measured both at the Fe K and Pt L(3) absorption edge, the composition within the single nanoparticles is found to be inhomogeneous, i.e. Pt is in a Pt-rich environment and, consequently, Fe is in an Fe-rich environment. The standard Fourier transformation-based analysis is complemented by a wavelet transformation method clearly visualizing the difference in the local composition. The dependence of the magnetic properties, i.e. the element-specific magnetic moments on the composition in chemically disordered Fe(x)Pt(1-x) alloys, is studied by fully relativistic SPR-KKR band structure calculations supported by experimental results determined from the x-ray magnetic circular dichroism of 50 nm thick films and bulk material.

Absence of intrinsic ferromagnetic interactions of isolated and paired Co dopant atoms in Zn1-xCoxO with high structural perfection.

We report element specific structural and magnetic investigations on Zn(1-x)Co(x)O epitaxial films using synchrotron radiation. Co dopants exclusively occupy Zn sites as revealed by x-ray linear dichroism having an unprecedented degree of structural perfection. Comparative magnetic field dependent measurements by x-ray magnetic circular dichroism and conventional magnetometry consistently show purely paramagnetic behavior for isolated Co dopant atoms with a magnetic moment of 4.8 (mu B). However, the total magnetization is reduced by approximately 30%, demonstrating that Co-O-Co pairs are antiferromagnetically coupled. We find no sign of intrinsic ferromagnetic interactions for isolated or paired Co dopant atoms in Co:ZnO films.

Magnetic properties of Co(N)RhM nanoparticles: experiment and theory?

The magnetism of Co-Rh nanoparticles is investigated experimentally and theoretically. The particles (approximately 2 nm) have been synthesized by decomposition of organometallic precursors in mild conditions of pressure and temperature, under hydrogen atmosphere and in the presence of a polymer matrix. The magnetic properties are determined by SQUID, Mössbauer spectroscopy, and X-ray magnetic circular dichroism (XMCD). The structural and chemical properties are characterized by wide angle X-ray scattering, transmission electronic microscopy and X-ray absorption near edge spectroscopy. All the studied Co-Rh clusters are magnetic with an average spin moment per atom mu that is larger than the one of macroscopic crystals or alloys with similar concentrations. The experimental results and comparison with theory suggest that the most likely chemical arrangement is a Rh core, with a Co-rich outer shell showing significant Co-Rh mixing at the interface. Measured and calculated magnetic anisotropy energies (MAEs) are found to be higher than in pure Co clusters. Moreover, one observes that the MAEs can be tuned to some extent by varying the Rh concentration. These trends are well accounted for by theory, which in addition reveals important spin and orbital moments induced at the Rh atoms as well as significant orbital moments at the Co atoms. These play a central role in the interpretation of experimental data as a function of Co-Rh content. A more detailed analysis from a local perspective shows that the orbital and spin moments at the Co-Rh interface are largely responsible for the enhancement of the magnetic moments and magnetic anisotropy.