On the Complementarity of Absorption and MCD Spectroscopy

The use of magnetic circular dichroism(MCD) spectroscopy for probing the 4f n configuration of trivalent lanthanide ions is explored. The technique is compared with optical absorption spectroscopy. MCD is valuable for the detection of degenerate crystal field levels in uniaxial crystals and for observing transitions not resolved in the absorption sepctrum, for the study of the site symmetry and for checking the reliability of crystal field and intensity parameters. On the other hand, selection of the samples has to be done more carefully than for absorption spectroscopy, because an MCD spectrum can only be recorded in an isotropic direction.

Quantitative measurement of magnetic parameters by electron magnetic chiral dichroism

Electron magnetic circular dichroism opens a new door to explore magnetic properties by transmitted electrons in the transmission electron microscope. However, obtaining quantitative magnetic parameters, such as spin and orbital magnetic moment with element-specificity, goes a long way along with the development and improvement of this technique both in theoretical and experimental aspects. In this review, we will give a detailed description of the quantitative electron magnetic circular dichroism（EMCD） technique to measure magnetic parameters with spin-specificity, element-specificity,site-specificity, and orbital-spin-specificity. The discussion completely contains the procedures from raw experimental data acquisition to final magnetic parameters, together with the related custom code we have developed.

Spin chiral anisotropy of diamagnetic chiral mesostructured In_(2)O_(3)films

Spin chiral anisotropy(SChA)refers to the occurrence of different spin polarization in antipodal chiral structures.Herein,we report the SChA in diamagnetic chiral mesostructured In2O3 films(CMIFs)with manifestation of chirality-dependent magnetic circular dichroism(MCD)signals.CMIFs were grown on fluorine-doped tin dioxide conductive glass(FTO)substrates,which were synthesized via a hydrothermal route,with malic acid used as the symmetry-breaking agent.Two levels of chirality have been identified in CMIFs:primary nanoflakes with atomically twisted crystal lattices and secondary helical stacking of the nanoflakes.CMIFs exhibit chirality-dependent asymmetric MCD signals due to the different interactions of chirality-induced effective magnetic field and external magnetic field,which distinguish from the commonly observed external magnetic fielddependent symmetric MCD signals.These findings provide insights into spin manipulation of spin-paired diamagnets.

A new soft X-ray magnetic circular dichroism facility at the BSRF beamline 4B7B

X-ray magnetic circular dichroism （XMCD） has become an important and powerful tool because it allows the study of material properties in combination with elemental specificity, chemical state specificity, and magnetic specificity. A new soft X-ray magnetic circular dichroism apparatus has been developed at the Beijing Synchrotron Radiation Facility （BSRF）. The apparatus combines three experimental conditions： an ultra-high-vacuum environ- ment, moderate magnetic fields and in-situ sample preparation to measure the absorption signal. We designed a C-type dipole electromagnet that provides magnetic fields up to 0.5 T in parallel （or anti-parallel） direction rela- tive to the incoming X-ray beam. The performances of the electromagnet are measured and the results show good agreement with the simulation ones. Following film grown in situ by evaporation methods, XMCD measurements are performed. Combined polarization corrections, the magnetic moments of the Fe and Co films determined by sum rules are consistent with other theoretical predictions and experimental measurements.

Measurement of the polarization for soft X-ray magnetic circular dichroism at the BSRF beamline 4B7B

Three ultra-short-period W/B4C multilayers （1.244 nm, 1.235 nm and 1.034 nm） have been fabricated and used for polarization measurement at the 4BTB Beamline at the Beijing Synchrotron Radiation Facility （BSRF）. By using the rotating analyzer ellipsometry method, the linear polarization degree of light emerging from this beamline has been measured and the circular polarization evaluated for 700-860 eV. The first soft X-ray magnetic circular dichroism measurements are carried out at BSRF by positioning the beamline aperture out of the plane of the electron storage ring.

Research Article Local structure and magnetic properties of a nanocrystalline Mnrich Cantor alloy thin film down to the atomic scale

The huge atomic heterogeneity of high-entropy materials along with a possibility to unravel the behavior of individual components at the atomic scale suggests a great promise in designing new compositionally complex systems with the desired multifunctionality.Herein,we apply multi-edge X-ray absorption spectroscopy(extended X-ray absorption fine structure(EXAFS),Xray absorption near edge structure(XANES),and X-ray magnetic circular dichroism(XMCD))to probe the structural,electronic,and magnetic properties of all individual constituents in the single-phase face-centered cubic(fcc)-structured nanocrystalline thin film of Cr_(20)Mn_(26)Fe_(18)Co_(19)Ni_(17)(at.%)high-entropy alloy on the local scale.The local crystallographic ordering and componentdependent lattice displacements were explored within the reverse Monte Carlo approach applied to EXAFS spectra collected at the K absorption edges of several constituents at room temperature.A homogeneous short-range fcc atomic environment around the absorbers of each type with very similar statistically averaged interatomic distances(2.54-2.55Å)to their nearest-neighbors and enlarged structural relaxations of Cr atoms were revealed.XANES and XMCD spectra collected at the L2,3 absorption edges of all principal components at low temperature from the oxidized and in situ cleaned surfaces were used to probe the oxidation states,the changes in the electronic structure,and magnetic behavior of all constituents at the surface and in the sub-surface volume of the film.The spin and orbital magnetic moments of Fe,Co,and Ni components were quantitatively evaluated.The presence of magnetic phase transitions and the co-existence of different magnetic phases were uncovered by conventional magnetometry in a broad temperature range.

Epitaxy growth of pure phase CeFeO_(3) thin films with high magneto-optical performance and strong vertical magnetic anisotropy

The magneto-optical effects of rare earth ferrite can be greatly improved by doping Ce^(3+)ions.CeFeO_(3)with high Ce^(3+)concentration has excellent magneto-optical properties in theory.And due to its perovskite structure it is more suitable to be deposited on the substrates of optical devices compared with the commercial garnet ferrite.In this paper,the pure phase Ce_(x)Fe_(2-x)O_(3)films were successfully obtained on the quartz glass and <100>-oriented SrTiO3crystal substrates by radio frequency magnetron sputtering.The effects of substrate and Ce:Fe ratio on the epitaxial orientation,magnetism and magnetooptical performance of films were systematically studied.For the Ce1.0Fe1.0O3/STO film,its MCD ellipticity(ψF) intensity can reach up to 4750(°)/cm in the visible band and 14090(°)/cm in near ultraviolet band.And it also shows a strong vertical magnetic anisotropy,which makes it maintain a good thermal stability when the device size is reduced.These mean that the Ce_(1.0)Fe_(1.0)O_(3)/STO film has a promising application in integrated optical communication devices.

Spin selectivity of chiral mesostructured diamagnetic BiOBr films

The chirality-induced spin selectivity(CISS)has been found in the antiferromagnetic and paramagnetic chiral inorganic materials with unpaired electrons,while rarely reported in the spin-paired diamagnetic inorganic materials with spin-pairing energy.Here,we report the CISS in the spin-paired diamagnetic BiOBr endowed with three levels of chiral mesostructures.Chiral mesostructured BiOBr films(CMBFs)were fabricated through a sugar alcohol-induced hydrothermal route.The antipodal CMBFs exhibited chirality-dependent,magnetic field-independent magnetic circular dichroism(MCD)signals,which indicates the existence of spin selectivity.The spin selectivity of CMBFs was speculated to be the result of the competing effect between the externally applied magnetic field and the effective magnetic field arisen from the spin electron motions in chiral potential.The chirality-induced effective magnetic field acts on the magnetic moment of electrons,potentially overcoming the spin-pairing energy and producing opposite energy changes for spin-down and spin-up electrons.

Magnetooptics of non-Kramers Eu^(3+) ions in garnets:analysis complemented by crystal-field splitting modeling calculations

Spectra of absorption, luminescence, magnetic circular dichroism （MCD）, and magnetic circular polarization of lumines- cence （MCPL） in Gd3Ga5O12：Eu3＋ and Eu3Ga3O12 garnets were studied within the visible spectral range at 300 K. Analysis of the spectral and temperature dependences of the magnetooptical and optical spectra made it possible to identify the magneto-dipole （MD） and electro-dipole （ED） 4f→4f transitions occurring between Stark sublevels of the 7FJ （J=1, 2） and 5D0 multiplets in Eua＋-containing garnet structures. Quantum mechanical ＂mixing＂ had significant influence on quasi-degenerate states of the non-Kramers rare-earth Eu3＋ ion for Eu3GasOl2 in MCD due to forbidden MD transition 7F1→SD0 and for GdaGasOiE：EU3＋ in MCPL due to MD 4f→4f transition 5Do→7F1 and forced ED-transition 5Do→7F2. A parameterized Hamiltonian defined to operate within the entire 4f（6） ground electronic configuration of Eu3＋ ion was used to model the experimental Stark levels, including their irreducible rep- resentations and wavefunctions. The crystal-field parameters were determined through a Monte-Carlo method in which nine in- dependent crystal-field parameters, Bkq, were given random starting values and optimized using standard least-squares fitting between calculated and experimental levels. The final fitting standard deviation between 57 calculated-to-experimental levels was 0.73 meV.

Emerging 2D magnetic states in a graphene-based monolayer of EuC_(6)

Recent discoveries of intrinsic two-dimensional(2D)magnets open up vast opportunities to address fundamental problems in condensed matter physics,giving rise to applications from ultra-compact spintronics to quantum computing.The ever-growing material landscape of 2D magnets lacks,however,carbon-based systems,prominent in other areas of 2D research.Magnetization measurements of the Eu/graphene compound-a monolayer of the EuC_(6) stoichiometry-reveal the emergence of 2D ferromagnetism but detailed studies of competing magnetic states are still missing.Here,we employ element-selective X-ray absorption spectroscopy(XAS)and magnetic circular dichroism(XMCD)to establish the magnetic structure of monolayer EuC6.The system exhibits the anomalous Hall effect,negative magnetoresistance,and magnetization consistent with a ferromagnetic state but the saturation magnetic moment(about 2.5/%/Eu)is way too low for the half-filled f-shells of Eu^(2+)ions.Combined XAS/XMCD studies at the Eu L3 absorption edge probe the EuC6 magnetism in high fields and reveal the nature of the missing magnetic moments.The results are set against XMCD studies in Eu/silicene and Eu/germanene to establish monolayer EuC6 as a prominent member of the family of Eu-based 2D magnets combining the celebrated graphene properties with a strong magnetism of europium.

Al-driven peculiarities of local coordination and magnetic properties in single-phase Al_(x)-CrFeCoNi high-entropy alloys

Modern design of superior multi-functional alloys composed of several principal components requires in-depth studies of their local structure for developing desired macroscopic properties.Herein,peculiarities of atomic arrangements on the local scale and electronic states of constituent elements in the single-phase face-centered cubic(fcc)-and body-centered cubic(bcc)-structured high-entropy Alx-CrFeCoNi alloys(x=0.3 and 3,respectively)are explored by element-specific X-ray absorption spectroscopy in hard and soft X-ray energy ranges.Simulations based on the reverse Monte Carlo approach allow to perform a simultaneous fit of extended X-ray absorption fine structure spectra recorded at K absorption edges of each 3d constituent and to reconstruct the local environment within the first coordination shells of absorbers with high precision.The revealed unimodal and bimodal distributions of all five elements are in agreement with structure-dependent magnetic properties of studied alloys probed by magnetometry.A degree of surface atoms oxidation uncovered by soft X-rays suggests different kinetics of oxide formation for each type of constituents and has to be taken into account.X-ray magnetic circular dichroism technique employed at L2,3 absorption edges of transition metals demonstrates reduced magnetic moments of 3d metal constituents in the sub-surface region of in situ cleaned fcc-structured Al0.3-CrFeCoNi compared to their bulk values.Extended to nanostructured versions of multicomponent alloys,such studies would bring new insights related to effects of high entropy mixing on low dimensions.

Specific features of Eu^(3+) and Tb^(3+) magnetooptics in gadolinium-gallium garnet (Gd_3Ga_5O_(12))

We reported magnetooptical properties of Eu3＋（4f（6）） and Tb3＋（4f（8）） in single crystals of Gd3Ga5O12 （GGG）, Y3Ga5O12 （YGG）, and Eu3＋（4f（6）） in Eu3Ga5O12 （EuGG） for both ions occupying sites of D2 symmetry in the garnet structure. Absorption, luminescence, and magnetic circular polarization of luminescence （MCPL） spectra of Tb3＋ in GGG and YGG and absorption and magnetic circular dichroism （MCD） of Eu3＋ in EuGG were studied. The data were obtained at 85 K and room temperature （RT）. Magnetic susceptibility of Eu3＋ in EuGG was also measured between 85 K and RT. The magnetooptical and magnetic susceptibility data were modeled using the wavefunctions of the crystal-field split energy （Stark） levels of Eu3＋ and Tb3＋ occupying D2 sites in the same garnets. The results reported gave a precise determination of these Stark level assignments and confirmed the symmetry labels （irreducible representations） of the closely-spaced Stark levels （quasi-doublets） found in the 5D1 （Eu3＋） and 5D4 （Tb3＋） multiplets. Ultraviolet （UV） excitation （300 nm） of the 6PJ and 6IJ states of Gd3＋ in the doped GGG crystals led to emission from 5D4 （Tb3＋） and 5D1 and 5D0 （Eu3＋） through radiationless energy transfer to the 4f（n–1）5d band of Tb3＋ and to UV quintet states of Eu3＋. The temperature-dependent emission line shapes and line shifts of the magnetooptical transitions excited by UV radiation suggested a novel way to explore energy transfer mechanisms in this rare-earth doped garnet system.

Iridium complex of porphycene:a new member of metalloporphycene

Iridium(Ⅲ)porphycene complex was synthesized and structurally characterized for the first time.The introduction of the posttransition iridium(Ⅲ)ion not only significantly enhances the absorption intensity at the end of visible region,but also displays efficient singlet oxygen quantum yield(76%),which is applicable for photodynamic therapy in living cells.

Competing magnetic states in silicene and germanene 2D ferromagnets

Two-dimension(2D)magnets have recently developed into a class of stoichiometric materials with prospective applications in ultra-compact spintronics and quantum computing.Their functionality is particularly rich when different magnetic orders are competing in the same material.Metalloxenes REX2(RE=Eu,Gd;X=Si,Ge),silicene or germanene—heavy counterparts of graphene—coupled with a layer of rare-earth metals,evolve from three-dimension(3D)antiferromagnets in multilayer structures to 2D ferromagnets in a few monolayers.This evolution,however,does not lead to fully saturated 2D ferromagnetism,pointing at a possibility of coexisting/competing magnetic states.Here,REX2 magnetism is explored with element-selective X-ray magnetic circular dichroism(XMCD).The measurements are carried out for GdSi2,EuSi2,GdGe2,and EuGe2 of different thicknesses down to 1 monolayer employing K absorption edges of Si and Ge as well as M and L edges of the rare-earths.They access the magnetic state in REX2 and determine the seat of magnetism,orbital,and spin contributions to the magnetic moment.High-field measurements probe remnants of the bulk antiferromagnetism in 2D REX2.The results provide a new platform for studies of complex magnetic structures in 2D materials.

Influence of the photon beam position on incident SR intensity at the SXMCD endstation

A small fluctuation of the photon beam position will affect the intensity and polarization characteristics of synchrotron radiation （SR） when it enters an endstation through the related beamline. In this paper, by changing the electron orbit equilibrium position in the vertical direction, we have measured the corresponding changes in the absorption strength of the SR with a gold mesh in different chopper aperture positions. It is found that for three aperture positions, the absorption intensity of the gold mesh shows a good Gaussian distribution as the photon beam position moves, while the ratio of the SR intensity passing through the upper and lower apertures shows a monotonous variation. This suggests a new method for estimating the circular polarization degree of SR originating from the bending magnet based on our current measurement.