X-ray Magnetic Circular Dichroism Results Research Articles

Strong signature of uncompensated magnetization in frustrated cobalt manganites using x-ray magnetic circular dichroism study

The present study is focused on the investigation of the distorted tetragonal phase of mixed spinel oxides, due to their technological relevance in the field of electronics, spintronics, magnetism, catalysis, and electrochemical energy storage. Herein, we report on solgel synthesized multivalent cobalt manganites, CoMn2O4 (CMO), and subjected them to a comprehensive analysis to elucidate their physicochemical characteristics at room temperature. Analysis employing powder x-ray diffraction patterns and electron microscopy (including field-emission scanning electron microscopy and high-resolution transmission electron microscopy) results confirmed the formation of a pure and exceptionally crystalline, distorted tetragonal phase of mixed CMO. Synchrotron-based x-ray absorption spectroscopic (XAS) measurements in the total electron yield mode examined local electronic structures affirming the formation of CMO with uncompensated electronic states involving Co2+, Co3+, Mn2+, Mn3+, and Mn4+ cations. Concurrently, XAS and x-ray magnetic circular dichroism analyses revealed antiferromagnetic coupling within Co and Mn sublattices in CMO, indicating the presence of uncompensated electronic states. Vibrating sample magnetometry results demonstrated clear hysteresis behavior, explicitly indicating the coexistence of super-paramagnetic and canted antiferromagnetic characteristics in CMO, as validated through the Langevin function fitting and x-ray magnetic circular dichroism results. The noticeable absence of saturated magnetization confirmed the high degree of spin canting, primarily stemming from the presence of the Yafet–Kittel spin arrangement.

Synchrotron X-ray spectroscopic study of the antiferromagnetic-ferromagnetic transition in Ni-doped FeRh epitaxial thin films

We investigate the change of magnetism and electronic structure across the antiferromagnetic (AFM) -ferromagnetic (FM) transition of Ni-doped FeRh epitaxial thin films by x-ray magnetic circular dichroism (XMCD) and hard x-ray photoemission spectroscopy (HAXPES). The Rh L edge XMCD results indicate that the remnant FM phase at low temperature possesses smaller Rh moment than the normal FM phase which can undergo AFM-FM transition. The HAXPES results confirm an increase of Rh 4d density of state at the Fermi level and a possible “well-screened” state at the Ni 2p photoemission in the FM phase. FM fluctuation of the inter-site Fe-Fe exchange coupling within the AFM phase can be interpreted from the temperature dependence of the Fe 2p HAXPES results.

Quantifying Spin-Mixed States in Ferromagnets.

We quantify the presence of spin-mixed states in ferromagnetic 3D transition metals by precise measurement of the orbital moment. While central to phenomena such as Elliot-Yafet scattering, quantification of the spin-mixing parameter has hitherto been confined to theoretical calculations. We demonstrate that this information is also available by experimental means. Comparison of ferromagnetic resonance spectroscopy with x-ray magnetic circular dichroism results show that Kittel's original derivation of the spectroscopic g factor requires modification, to include spin mixing of valence band states. Our results are supported by abinitio relativistic electronic structure theory.

Magnetic anisotropic of thermally evaporated FeNi thin film: A soft X‐ray magnetic circular dichroism study

FeNi film was fabricated on Cu/MgO (001) substrates using thermal evaporation technique of a FeNi target to realize the formation of an L10‐FeNi phase. The magnetic anisotropy of FeNi film was systematically investigated by means of X‐ray absorption spectroscopy (XAS) and X‐ray magnetic circular dichroism (XMCD) techniques. Our L‐edge XAS and XMCD analysis is performed for 30‐nm FeNi film grown on Cu/MgO (001) substrate. The present experimental results of XAS and XMCD indicate that ~5% Fe atoms are oxidized. Our findings also showed that the orbital magnetic moment of Fe has a significant incident X‐ray angle dependence that exhibits a maximum value at the out‐of‐plane direction corresponding perpendicular to the plane. The origin of anisotropy is successfully explained by element‐specific XMCD technique. The enhancement in magnetic anisotropy energy (MAE) is due to orbital magnetic moments of Fe through spin–orbit interaction. The uniaxial anisotropy energy showed quantitatively good agreement with the volume MAE.

Quantitative comparison of the magnetic proximity effect in Pt detected by XRMR and XMCD

X-ray resonant magnetic reflectivity (XRMR) allows for the simultaneous measurement of structural, optical, and magneto-optic properties and depth profiles of a variety of thin film samples. However, a same-beamtime same-sample systematic quantitative comparison of the magnetic properties observed using XRMR and x-ray magnetic circular dichroism (XMCD) is still pending. Here, the XRMR results (Pt L3 absorption edge) for the magnetic proximity effect in Pt deposited on the two different ferromagnetic materials Fe and Co33Fe67 are compared with quantitatively analyzed XMCD results. The obtained results are in very good quantitative agreement between the absorption-based (XMCD) and reflectivity-based (XRMR) techniques, taking into account an ab initio calculated magneto-optic conversion factor for the XRMR analysis. Thus, it is shown that XRMR provides quantitative reliable spin depth profiles important for spintronic and spin caloritronic transport phenomena at this type of magnetic interfaces.

The role of iron in magnetic damping of Mg(Al,Fe)2O4 spinel ferrite thin films

We have investigated magnesium aluminum ferrite thin films with a range of iron concentrations and identified the optimal iron content to obtain high crystalline quality thin films with the low magnetic damping required for spin current-based applications. Epitaxial MgAl2−x FexO4 films with 0.8 < x < 2.0 were grown by pulsed laser deposition on single crystal MgAl2O4 substrates and were characterized structurally and magnetically. We find that the x = 1.5 composition minimizes the room-temperature magnetic damping with a typical Gilbert damping parameter of αeff=1.8×10−3. This minimized damping is governed by a competition between the more robust magnetic ordering with increased iron content, x, and the more defective structure due to larger film-substrate lattice mismatch with increased iron content. The temperature-dependent magnetization curves indicate that Tc is suppressed below room temperature for iron content x≤1.2 and eventually suppressed entirely for x = 0.8. X-ray magnetic circular dichroism results indicate that for all x the magnetic moment is dominated by Fe3+ cations distributed in a 60:40 ratio on the octahedral and tetrahedral sites, with minimal contribution from Fe2+ cations. Films with x=1.4−1.6 exhibit very strong ferromagnetic resonance and low Gilbert damping with αeff=(1.8−6)×10−3, making them ideal candidates for microwave and spintronic applications.

Electronic structure investigation of GdNi using x-ray absorption, magnetic circular dichroism, and hard x-ray photoemission spectroscopy

GdNi is a ferrimagnetic material with a Curie temperature Tc = 69 K which exhibits a large magnetocaloric effect, making it useful for magnetic refrigerator applications. We investigate the electronic structure of GdNi by carrying out x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) at T = 25 K in the ferrimagnetic phase. We analyze the Gd M$_{4,5}$-edge ($3d$ - $4f$) and Ni L$_{2,3}$-edge ($2p$ - $3d$) spectra using atomic multiplet and cluster model calculations, respectively. The atomic multiplet calculation for Gd M$_{4,5}$-edge XAS indicates that Gd is trivalent in GdNi, consistent with localized $4f$ states. On the other hand, a model cluster calculation for Ni L$_{2,3}$-edge XAS shows that Ni is effectively divalent in GdNi and strongly hybridized with nearest neighbour Gd states, resulting in a $d$-electron count of 8.57. The Gd M$_{4,5}$-edge XMCD spectrum is consistent with a ground state configuration of S = 7/2 and L=0. The Ni L$_{2,3}$-edge XMCD results indicate that the antiferromagnetically aligned Ni moments exhibit a small but finite magnetic moment ( $m_{tot}$ $\sim$ 0.12 $\mu_B$ ) with the ratio $m_{o}/m_{s}$ $\sim$ 0.11. Valence band hard x-ray photoemission spectroscopy shows Ni $3d$ features at the Fermi level, confirming a partially filled $3d$ band, while the Gd $4f$ states are at high binding energies away from the Fermi level. The results indicate that the Ni $3d$ band is not fully occupied and contradicts the charge-transfer model for rare-earth based alloys. The obtained electronic parameters indicate that GdNi is a strongly correlated charge transfer metal with the Ni on-site Coulomb energy being much larger than the effective charge-transfer energy between the Ni $3d$ and Gd $4f$ states.

Magnetic tunnel junctions with a B2 -ordered CoFeCrAl equiatomic Heusler alloy

The equiatomic quaternary Heusler alloy CoFeCrAl is a candidate material for spin-gapless semiconductors (SGSs). However, to date, there have been no experimental attempts at fabricating a junction device. This paper reports a fully epitaxial (001)-oriented MgO barrier magnetic tunnel junction (MTJ) with CoFeCrAl electrodes grown on a Cr buffer. X-ray and electron diffraction measurements show that the (001) CoFeCrAl electrode films with atomically flat surfaces have a $B2$-ordered phase. The saturation magnetization is $380\phantom{\rule{0.16em}{0ex}}{\mathrm{emu}/\mathrm{cm}}^{3}$, almost the same as the value given by the Slater--Pauling--like rule, and the maximum tunnel magnetoresistance ratios at 300 K and 10 K are 87% and 165%, respectively. Cross-sectional electron diffraction analysis shows that the MTJs have MgO interfaces with fewer dislocations. The temperature- and bias-voltage-dependence of the transport measurements indicates magnon-induced inelastic electron tunneling overlapping with the coherent electron tunneling. X-ray magnetic circular dichroism (XMCD) measurements show a ferromagnetic arrangement of the Co and Fe magnetic moments of $B2$-ordered CoFeCrAl, in contrast to the ferrimagnetic arrangement predicted for the $Y$-ordered state possessing SGS characteristics. Ab initio calculations taking account of the Cr-Fe swap disorder qualitatively explain the XMCD results. Finally, the effect of the Cr-Fe swap disorder on the ability for electronic states to allow coherent electron tunneling is discussed.

Study of exchange bias in single-phase Dy0.2Nd0.8CrO3

We present a study of the magnetic properties of a single-phase Dy0.2Nd0.8CrO3 compound. Interestingly, a negative exchange bias (EB) effect is observed for a wide range of temperature and, below T = 5 K, a small positive EB is also noticed, which is accompanied by a crossing of the Zero Field Cooling and Field Cooling (ZFC-FC) curves. Moreover, in contrast to many results reported in the literature, we do not verify a magnetic reversal, not even at low magnetic fields. The X-ray magnetic circular dichroism results show clear evidences of a dichroic signal for Cr L2,3 edges at T = 30 K under a magnetic field of H = 4 T. Our results suggest that a ferromagnetic ordering of the Cr3+ and the long-range ordering for the Nd3+ can play an important role in the observation of the positive EB in this compound.

Spin and orbital moments of electrodeposited Fe28Co51Ni21 soft magnetic films determined by X-ray magnetic circular dichroism

Fe28Co51Ni21 ternary alloy thin films electrodeposited on GaAs wafers were investigated by scanning electron microscopy (SEM), magnetic force microscopy (MFM), X-ray absorption spectroscopy (XAS), and X-ray magnetic circular dichroism (XMCD). Experimental Magneto-optical Kerr effect (MOKE) data showed that the Fe28Co51Ni21 films present typical soft magnetic properties and no obvious in-plane magnetic anisotropy. The spin and orbital magnetic moments of Fe, Co, and Ni in the alloy were calculated by applying sum rules to the XMCD results. The spin moments of Fe atoms in the alloy decreased, which is attributed to the formation of an antiferromagnetic fcc phase. Increases in the orbital moments of Fe-group atoms were correlated with decreases in crystal field effects. The spin moments of Co and Ni atoms were enhanced by variations in the local environment after alloying.

Probing the magnetic moments of [MnIII6CrIII]3+ single-molecule magnets—A cross comparison of XMCD and spin-resolved electron spectroscopy

Single-molecule magnets (SMM) of the [MnIII6CrIII]3+ structural type prepared on Si and gold-coated glass substrates have been investigated by spin-resolved electron spectroscopy (SPES) and X-ray magnetic circular dichroism (XMCD) at the Mn L3,2 edge and in addition by XMCD at the Cr L3,2 edge using synchrotron radiation. Differences between the two methods are discussed. Despite its severe limitations for 3d transition metals, a spin sum rule evaluation is nevertheless performed for the MnIII centres in the [MnIII6CrIII]3+ SMM to provide a simple means of comparing XMCD and spin-resolved electron spectroscopy results.

The influence of Nd dopants on spin and orbital moments in Nd-doped permalloy thin films

Magnetic properties of NdX-Ni80Fe20(1−X) thin films have been investigated using x-ray absorption spectroscopy and x-ray magnetic circular dichroism (XMCD) at room temperature. With the Nd concentration increasing, the ratio of orbital-to-spin moment of Ni and Fe increases significantly, indicating that the spin-orbit coupling in permalloy thin films is enhanced due to the Nd impurities. The spin and orbital moments have been obtained by the sum rules analysis, which shows that the Nd impurities lead to a strong dispersion of spin moments of Fe and Ni while have no effect on orbital moments in Nd-doped permalloy thin films. Element-specific XMCD hysteresis loops suggest an antiferromagnetic coupling between the magnetic moments of Nd and permalloy at room temperature. The static magnetic properties have been studied by vibrating sample magnetometer for comparison, which shows a nice agreement with the XMCD results.

Energy level alignment and interactive spin polarization at organic/ferromagnetic metal interfaces for organic spintronics

Energy level alignment and spin polarization at tetracyanoquinodimethane/Fe and acridine orange base/Fe interfaces are investigated by means of photoelectron spectroscopy and X-ray magnetic circular dichroism (XMCD), respectively, to explore their potential application in organic spintronics. Interface dipoles are observed at both hybrid interfaces, and the work function of Fe is increased by 0.7eV for the tetracyanoquinodimethane (TCNQ) case, while it is decreased by 1.2eV for the acridine orange base (AOB) case. According to XMCD results, TCNQ molecule has little influence on the spin polarization of Fe surface. In contrast, AOB molecule reduces the interfacial spin polarization of Fe significantly. Induced spin polarization of the two organic molecules at the interfaces is not observed. The results reveal the necessity of investigating the magnetic property changes of both the OSC and the FM during the process of energy level alignment engineering.

X-ray Magnetic Circular Dichroism Investigation of the Electron Transfer Phenomena Responsible for Magnetic Switching in a Cyanide-Bridged [CoFe] Chain

The cyanide-bridged [CoFe] one-dimensional chain, [Co(II)((R)-pabn)][Fe(III)(Tp)(CN)3](BF4)·MeOH·2H2O, where (R)-pabn = (R)-N2,N(2')-bis(pyridin-2-ylmethyl)-1,1'-binaphthyl-2,2'-diamine and Tp = hydrotris(pyrazolyl)borate, exhibits magnetic and electric bistabilities originating from an electron transfer coupled spin transition between Fe-CN-Co pairs. The use of L-edge X-ray absorption spectroscopy (XAS) in combination with L-edge X-ray magnetic circular dichroism (XMCD) is explored for the investigation of the electronic structure and magnetization of Co and Fe ions separately, in both diamagnetic and paramagnetic states. It has been established from susceptibility results that the switching between diamagnetic and paramagnetic phases emanates from electron transfer between low spin Fe(II) and Co(III), resulting in low spin Fe(III) (S = 1/2) and high spin Co(II) (S = 3/2). The XAS and XMCD results are consistent with the bulk susceptibility measurements, where greater detail regarding the charge transfer process is determined. The Fe-CN-Co electron transfer pathway is highlighted by a strongly XMCD dependent transition to a cyanide back bonding orbital, giving evidence for strong hybridization with Fe(III) t2g orbitals. In addition to thermally induced and photoinduced switching, [CoFe] is found to exhibit a switching by grinding induced dehydration. Analysis of XAS shows that on grinding diamagnetic [CoFe], 75% of metal ions lock into the magnetic Co(II)Fe(III) phase. Density functional theory calculations based on the [CoFe] crystal structure in the magnetic and nonmagnetic phases aid the spectroscopic results and provide a complementary insight into the electronic configuration of the [CoFe] 3d shells, quantifying the change in ligand field around Co and Fe centers on charge transfer.

Magnetic dead layer at the interface between a Co film and the topological insulator Bi2Se3

Co films were grown on top of a topological insulator Bi${}_{2}$Se${}_{3}$(111) substrate and studied using magneto-optic Kerr effect (MOKE) and x-ray magnetic circular dichroism (XMCD). Both MOKE and XMCD results show that there exists a \ensuremath{\sim}1.2-nm-thick magnetic dead layer of the Co film; i.e., an \ensuremath{\sim}1.2-nm Co film at the Co/Bi${}_{2}$Se${}_{3}$(111) interface loses its ferromagnetic order. The Co ferromagnetic order can be completely resumed by inserting a 3-nm Ag layer between the Co and Bi${}_{2}$Se${}_{3}$, indicating that the magnetic dead layer is due to the Co/Bi${}_{2}$Se${}_{3}$ interfacial mixing which is supported by the Co $L$-edge spectroscopy results.

Co/Ni(111) superlattices studied by microscopy, x-ray absorption, andab initiocalculations

We explore the origins of perpendicular magnetic anisotropy in epitaxial and textured Co/Ni(111) superlattices using a combination of thin-film growth, structural characterization, x-ray magnetic circular dichroism (XMCD), and ab initio calculations. Transmission electron microscopy and x-ray diffraction experiments allow us to show that the bulk magnetoelastic contribution to the total magnetic energy is small compared to the interface anisotropy. The magnetic properties are studied by using XMCD at the Co and Ni L 2,3 edges. Hysteresis loops performed at the Co L 3 edge confirm the perpendicular magnetization for Co thicknesses up to four monolayers. The spin and orbital moments were deduced using the XMCD sum rules. The results are explained by considering two kinds of magnetic moments for Co, distinguishing the interfaces from the rest of the layers. Both effective spin and orbital moments of Co atoms are found to be enhanced at the Co-Ni interfaces, whereas the magnetic moment of Co surrounded by Co is similar to the bulk value. Ab initio calculations allow us to show a strong enhancement of the dipole operator contribution on Co atoms at the interface that is partly responsible for this high effective spin moment at the interface. Such a moment enhancement is not observed for Ni, with the dipole operator contribution being close to zero. Finally, we observed a very surprising proportionality between the effective spin and orbital moments, independent of the absorption edge or deposition technique used. We assign this peculiar behavior to the fact that the magnetic dipole operator involved in the sum rules is closely linked to the increase of the Co orbital moment at the interface. Based on XMCD results obtained on both molecular beam epitaxy and sputter-deposited samples, this link allows us to show the extreme sensitivity of the perpendicular anisotropy with the chemical ordering at the interface.

Performance upgrade in the JAEA actinide sciencebeamline BL23SU at SPring-8 with anewtwin-helical undulator.

The soft X-ray beamline BL23SU at SPring-8 has undergone an upgrade with a twin-helical undulator of in-vacuum type to enhance the experimental capabilities of the endstations. The new light source with a fast helicity-switching operation allows not only the data throughput but also the sensitivity in X-ray magnetic circular dichroism (XMCD) to be improved. The operational performance and potential are described by presenting XMCD results of paramagnetic β-US(2) measured with a 10 T superconducting magnet.

Ferromagnetism in ZnO co-doped with Mn and N studied by soft x-ray magnetic circular dichroism

We have investigated the electronic structure of ZnO:Mn and ZnO:Mn,N thin films using x-ray magnetic circular dichroism (XMCD) and resonance-photoemission spectroscopy. From the Mn 2p → 3d XMCD results, it is shown that, while XMCD signals only due to paramagnetic Mn2+ ions were observed in ZnO:Mn, nonmagnetic, paramagnetic, and ferromagnetic Mn2+ ions coexist in ZnO:Mn,N. XMCD signals of ZnO:Mn,N revealed that the localized Mn2+ ground state and Mn2+ state hybridized with ligand hole coexisted, implying p-d exchange coupling. In the valence-band spectra, spectral weight near the Fermi level was suppressed, suggesting that interaction between magnetic moments in ZnO:Mn,N has localized nature.

ODE: a new beam line for high-pressure XAS and XMCD studies at SOLEIL

X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) under pressure are probes of local order and microscopic magnetic properties. XMCD is a selective probe that has access to a large variety of elements. The dispersive extended X-ray absorption fine structure (EXAFS) station at SOLEIL (ODE beam line) provides the possibility to perform numerous pressure XAS and XMCD experiments with an excellent statistic. The main advantages of dispersive XAFS are the focusing optics, the short acquisition time (few μs) and great stability during the measurements due to the absence of any mechanical movement. These advantages allow the study of small samples, 70 μm at SOLEIL, which is mandatory in the case of high-pressure studies. We present the new ODE beam line at SOLEIL and its first high-pressure XMCD results.

The Effect of Disordering on Magnetic Properties of Fe-Al Alloys

The results of magnetometric, Mössbauer and XMCD (X-ray Magnetic Circular Dichroism) studies of B2 or DO3–type ordered (25 to 35 at.%Al) and disordered by mechanical activation (35 to 60 at.% Al) Fe-Al alloys are considered. For the description of magnetic characteristics of the studied alloys the validity of local magnetic moments models is discussed. The models suppose that Fe atom local magnetic moments are collinear with magnitude and direction depending on the number of Al atoms in the Fe nearest neighbourhood.