Magnetic Circular Dichroism (MCD) is a standard technique for the study of magnetic properties of materials in synchrotron beamlines. We present here a new scattering geometry in the Transmission Electron Microscope through which MCD can be observed with unprecedented spatial resolution. A convergent electron beam is used to scan a multilayer Fe/Au sample and record energy loss spectra. Differences in the spectra induced by the magnetic moments of the Fe atoms can be resolved with a resolution of 2 nm. This is a breakthrough achievement when compared both to the previous EMCD resolution (200 nm) or the best XMCD experiments (approx. 20 nm), with an improvement of two and one order of magnitude, respectively.
This paper discusses a theory of natural circular dichroism in the x-ray region. Integrated spectra are interpreted in terms of microscopic effective operators, which are derived in the framework of a localised (atomic) model. It is shown that the generators of a de Sitter group, such as that introduced by Goshen and Lipkin for nuclear structure, are suitable for describing electronic properties of non-centrosymmetric crystals.
The circular dichroism (CD) spectra of single-wall carbon nanotubes are calculated using a dipole approximation. The calculated CD spectra show features that allow us to distinguish between nanotubes with different angles of chirality, and diameters. These results provide theoretical support for the quantification of chirality and its measurement, using the CD lineshapes of chiral nanotubes. It is expected that this information would be useful to motivate further experimental studies.
Cobalt-doped ZnO (Co2+:ZnO) films were studied by magnetic circular dichroism (MCD) spectroscopy. A broad 300 K ferromagnetic MCD signal was observed between 1.4 and 4.0 eV after introducing shallow donor states by exposure of paramagnetic Co2+:ZnO films to zinc vapor. The new sub-bandgap ferromagnetic MCD intensity is attributed to low-energy photoionization transitions originating from a spin-split donor impurity band in ferromagnetic Co2+:ZnO.
Under symmetry breaking, a three-dimensional nodal-line semimetal can turn into a topological insulator or Weyl semimetal, accompanied by the generation of momentum-space Berry curvature. We develop a theory that unifies their circular dichroism and highlights the roles of Berry curvature distribution and light incident direction. Nontrivially, these phases exhibit distinct dichroic optical absorption and radial Hall effects, with characteristic scalings with photon energy and electric field. Our findings offer a new diagnosis tool for examining topological phases of matter.
Magnetic circular dichroism (MCD) of rutile Ti1-xCoxO2-d is systematically examined with various x and d to reveal a phase diagram for the appearance of ferromagnetism at higher carrier concentration and Co content. The phase diagram exactly matches with that determined from anomalous Hall effect (AHE). The magnetic field dependence of MCD also shows good coincidence with those of the magnetization and AHE. The coincidence of these independent measurements strongly suggests single and intrinsic ferromagnetic origin.
Magneto-optical properties of the ferromagnetic semiconductor GaMnAs are studied in a material specific multi-band tight-binding approach. Two realistic models are compared: one has no impurity band while the other shows an impurity band for low Mn concentrations. The calculated magnetic circular dichroism (MCD) is positive for both models proving that, unlike previously asserted, the observed positive MCD signal is inconclusive as to the presence or absence of an impurity band in GaMnAs. The positive MCD is due to the antiferromagnetic p-d coupling and the transitions into the conduction band…
X-ray magnetic circular dichroism (XMCD) signals are usually absent in antiferromagnets. In this letter, we report the observation of spontaneous XMCD spectra originating from the inverse triangular spin structure, or the polarization of the cluster magnetic octupole, in the chiral antiferromagnet Mn$_{3}$Sn thin film. The result is consistent with the recent theoretical predictions that the inverse triangular spin structure can give rise to finite XMCD signals in the absence of net magnetization [J. Phys. Soc. Jpn. 89, 083703 (2020) and Phys. Rev. Lett. 126, 157402 (2021)].
We present a unified interpretation of experimentally observed magnetic circular dichroism (MCD) in the ferromagnetic semiconductor (Ga,Mn)As, based on theoretical arguments, which demonstrates that MCD in this material arises primarily from a difference in the density of spin-up and spin-down states in the valence band brought about by the presence of the Mn impurity band, rather than being primarily due to the Zeeman splitting of electronic states.
Mn 2p soft X-ray absorption (XAS) spectroscopy excited with circularly polarized synchrotron radiation has been applied to a new class of material, c(2x2)CuMn/Cu(001) two-dimensional ordered surface alloy. A significant X-ray magnetic circular dichroism (XMCD) signal has been clearly observed at T=25K, indicating the existence of the ferromagnetic state under the external magnetic field of 1.4 Tesla. The lineshape analyses of the XAS and XMCD spectra clearly show that the Mn 3d state is rather localized and has a high spin magnetic moment due to its half-filled character.
Twisted bilayer graphene is a chiral system which has been recently shown to present circular dichroism. In this work we show that the origin of this optical activity is the rotation of the Dirac fermions' helicities in the top and bottom layer. Starting from the Kubo formula, we obtain a compact expression for the Hall conductivity that takes into account the dephasing of the electromagnetic field between the top and bottom layers and gathers all the symmetries of the system. Our results are based in both a continuum and a tight-binding model, and they can be generalized to any two-dimensiona…
We have measured Re 5d spin and orbital magnetic moments in the ferrimagnetic double perovskite Sr2CrReO6 by X-ray magnetic circular dichroism at the L_{2,3} edges. In fair agreement with recent band-structure calculations [Vaitheeswaran et. al., Ref 1], at the Re site a large 5d spin magnetic moment of -0.68 mu_B and a considerable orbital moment of +0.25 mu_B have been detected. We found that the Curie temperature of the double perovskites A2BB'O6 scales with the spin magnetic moment of the 'non-magnetic' B' ion.
We performed a soft x-ray magnetic circular dichroism (XMCD) study of a Zn$_{1-x}$V$_x$O thin film which showed small ferromagnetic moment. Field and temperature dependences of V 2$p$ XMCD signals indicated the coexistence of Curie-Weiss paramagnetic, antiferromagnetic, and possibly ferromagnetic V ions, quantitatively consistent with the magnetization measurements. We attribute the paramagnetic signal to V ions substituting Zn sites which are somewhat elongated along the c-axis.
Spin gapless semiconductors are known to be strongly affected by structural disorder when grown epitaxially as thin films. The magnetic properties of Mn2CoAl thin films grown on GaAs (001) substrates are investigated here as a function of annealing. This study investigates the atomic-specific magnetic moments of Mn and Co atoms measured through X-ray magnetic circular dichroism as a function of annealing and the consequent structural ordering. The results indicate that the structural distortion mainly affects the Mn atoms as seen by the reduction of the magnetic moment from its predicted value…
The results of fluorescence measurements of magnetic circular dichroism (MCD) in Mn L_2,L_3 X-ray emission and absorption for Heusler alloys NiMnSb and Co2MnSb are presented. Very intense resonance Mn L_3 emission is found at the Mn 2p_3/2 threshold and is attributed to a peculiarity of the threshold excitation in materials with the half-metallic character of the electronic structure. A theoretical model for the description of resonance scattering of polarized x-rays is suggested.
The electronic structure of a prototype dilute magnetic semiconductor (DMS), Ga1-xMnxAs, is studied by magnetic circular dichroism (MCD) spectroscopy. We prove that the optical transitions originated from impurity bands cause the strong positive MCD background. The MCD signal due to the E0 transition from the valence band to the conduction band is negative indicating that the p-d exchange interactions between the p-carriers and d-spin is antiferromagnetic. The negative E0 MCD signal also indicates that the hole-doping of the valence band is not so large as previously assumed. The impurity band…
We show, by way of tight-binding and first-principles calculations, that a one-to-one correspondence between electron's crystal momentum k and non-zero orbital angular momentum (OAM) is a generic feature of surface bands. The OAM forms a chiral structure in momentum space much as its spin counterpart in Rashba model does, as a consequence of the inherent inversion symmetry breaking at the surface but not of spin-orbit interaction. Circular dichroism (CD) angle-resolved photoemission (ARPES) experiment is an efficient way to detect this new order, and we derive formulas explicitly relating the …
Soft x-ray magnetic circular dichroism (XMCD) measurements at the Co L2,3 edges of Co doped rutile TiO2 at room temperature have revealed clear multiplet features characteristic of ferromagnetic Co2+ ions coordinated by O2- ions, being in sharp contrast to the featureless XMCD spectrum of Co metal or metallic clusters. The absorption and XMCD spectra agree well with a full atomic-multiplet calculation for the Co2+ high-spin state in the D2h-symmetry crystal field at the Ti site in rutile TiO2. The results indicate that the ferromagnetism arises from the Co2+ ions substituting the Ti4+ ions.
The p-electrons of carbon in the interstitial compound Fe3C hybridize with the Fe d-band and enhance the valence electron concentration of Fe from 8 to 8.67. At this concentration, substitutional 3d transition metals and alloys exhibit strong moment-volume coupling phenomena and associated magnetovolume instabilities, otherwise known as the Invar effect. For this reason, Fe3C is also expected to incorporate a strong magnetovolume instability, and therefore, we examine the pressure dependence of the of the K edge x-ray magnetic circular dichroism in Fe3C at ambient temperature and pressures up …
X-ray photoelectron emission microscopy in combination with x-ray magnetic circular dichroism is used to investigate the influence of an applied magnetic field on Néel caps (i.e., surface terminations of asymmetric Bloch walls). Self-assembled micron-sized Fe(110) dots displaying a moderate distribution of size and aspect ratios serve as model objects. Investigations of remanent states after application of an applied field along the direction of Néel-cap magnetization give clear evidence for the magnetization reversal of the Néel caps around 120 mT, with a $\pm$20 mT dispersion. No clear corre…
We have measured the X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD)at the Mn L3,2 edges in ferromagnetic Ga1-xMnxP for 0.018<x<0.042. Large XMCD asymmetries at the L3 edge indicate significant spin-polarization of the density of states at the Fermi energy. The temperature dependence of the XMCD and moment per Mn of 2.67 Bohr magnetons calculated using sum rules are consistent with magnetometry values. The spectral shapes of the XAS and XMCD are nearly identical with those for Ga1-xMnxAs indicating that the hybridization of Mn d and anion p states is similar in the two mate…
Femtosecond x-ray magnetic circular dichroism was used to study the time-dependent magnetic moment of 4 fs electrons in the ferromagnets Gd and Tb, which are known for their different spin-lattice coupling. We observe a two-step demagnetization with an ultrafast demagnetization time of 750 fs identical for both systems and slower times which differ sizeably with 40 ps for Gd and 8 ps for Tb. We conclude that spin-lattice coupling in the electronically excited state is enhanced up to orders of magnitude compared to equilibrium.
We report on the results of x-ray absorption (XAS), x-ray magnetic circular dichroism (XMCD), and photoemission experiments on {\it n}-type Zn$_{1-x}$Co$_x$O ($x=0.05$) thin film, which shows ferromagnetism at room temperature. The XMCD spectra show a multiplet structure, characteristic of the Co$^{2+}$ ion tetrahedrally coordinated by oxygen, suggesting that the ferromagnetism comes from Co ions substituting the Zn site in ZnO. The magnetic field and temperature dependences of the XMCD spectra imply that the non-ferromagnetic Co ions are strongly coupled antiferromagnetically with each other.
The electronic structure and magnetic ordering in La$_{1-x}$Pr$_x$Co$_2$P$_2$ ($x=$0, 0.25, and 1) phosphides have been studied theoretically using the fully relativistic spin-polarized Dirac linear muffin-tin orbital (LMTO) band-structure method. The X-ray absorption and X-ray magnetic circular dichroism spectra at the Co$L_{2,3}$ and Pr$M_{4,5}$ edges have been investigated theoretically within the framework of the LSDA+$U$ method. The core-hole effect in the final state as well as the effects of the electric quadrupole $E_2$ and magnetic dipole $M_1$ transitions have been investigated. Good…
We describe a new experimental setup for the detection of magnetic circular dichroism with fast electrons (EMCD). As compared to earlier findings the signal is an order of magnitude higher, while the probed area could be significantly reduced, allowing a spatial resolution of the order of 30 nm. A simplified analysis of the experimental results is based on the decomposition of the Mixed Dynamic Form Factor S(q,q',E) into a real part related to the scalar product and an imaginary part related to the vector product of the scattering vectors q and q'. Following the recent detection of chiral elec…
The magnetic properties of as-grown Ga$_{1-x}$Mn$_{x}$As have been investigated by the systematic measurements of temperature and magnetic field dependent soft x-ray magnetic circular dichroism (XMCD). The {\it intrinsic} XMCD intensity at high temperatures obeys the Curie-Weiss law, but residual spin magnetic moment appears already around 100 K, significantly above Curie temperature ($T_C$), suggesting that short-range ferromagnetic correlations are developed above $T_C$. The present results also suggest that antiferromagnetic interaction between the substitutional and interstitial Mn (Mn$_{i…
The growth of Fe nanoclusters on the Ge(001) surface has been studied using lowtemperature scanning tunnelling microscopy (STM) and density functional theory (DFT) calculations. STM results indicate that Fe nucleates on the Ge(001) surface, forming wellordered nanoclusters of uniform size. Depending on the preparation conditions, two types of nanoclusters were observed having either four or sixteen Fe atoms within a nanocluster. The results were confirmed by DFT calculations. Annealing the nanoclusters at 420 K leads to the formation of nanorow structures, due to cluster mobility at such tempe…
Element-specific orbital magnetic moments and their anisotropies in perpendicularly magnetised Co/Pd multilayers are investigated using Co L-edge and Pd M-edge angle-dependent x-ray magnetic circular dichroism. We show that the orbital magnetic moments in Co are anisotropic, whereas those in Pd are isotropic. The first-principles density-functional-theory calculations also suggest that the Co/Pd interfacial orbital magnetic moments in Co are anisotropic and contribute to the perpendicular magnetic anisotropy (PMA), and that the isotropic ones in Pd manipulates the Co orbitals at the interface …
The spin and orbital magnetic moments of the Fe3O4 epitaxial ultrathin film synthesized by plasma assisted simultaneous oxidization on MgO(100) have been studied with X-ray magnetic circular dichroism (XMCD). The ultrathin film retains a rather large total magnetic moment, i.e. (2.7+-0.15) uB/f.u., which is ~ 70% of that for the bulk-like Fe3O4. A significant unquenched orbital moment up to (0.54+-0.05) uB/f.u. was observed, which could come from the symmetry breaking at the Fe3O4/MgO interface. Such sizable orbital moment will add capacities to the Fe3O4-based spintronics devices in the magne…
We demonstrate sensitivity of the Mn 3d valence states to strain in the ferromagnetic semiconductors (Ga,Mn)As and (Al,Ga,Mn)As, using x-ray magnetic circular dichroism (XMCD). The spectral shape of the Mn $L_{2,3}$ XMCD is dependent on the orientation of the magnetization, and features with cubic and uniaxial dependence are distinguished. Reversing the strain reverses the sign of the uniaxial anisotropy of the Mn $L_3$ pre-peak which is ascribed to transitions from the Mn 2p core level to p-d hybridized valence band hole states. With increasing carrier localization, the $L_3$ pre-peak intensi…
The x-ray magnetic circular dichroism (XMCD) sum rule yields an extremely useful ground-state observable, which provides a quantitative measure of spontaneous time-reversal symmetry breaking (T-breaking) in a given material. I derive here its explicit expression within band-structure theory, in the general case: trivial insulators, topological insulators, and metals. Orbital magnetization provides a different measure of T-breaking in the electronic ground state. The two observables belong to the class of "geometrical" observables; both are local and admit a "density" in coordinate space. In bo…
Circular dichroism is a technologically important phenomenon contrasting the absorption and resultant emission properties between left- and right-handed circularly polarized light. While the chiral handedness of systems mainly determines the mechanism of the circular dichroism in linear optics, the counterpart in the nonlinear optical regime is nontrivial. Here, in contrast to traditional nonlinear circular dichroism responses from structured surfaces, we report on an unprecedented bulk-material-induced circular dichroism of second harmonic generation with a massive g-factor up to 1.8.
Circular dichroism in the angular distribution (CDAD) of photoelectrons from SrTiO3:Nb and CuxBi2Se3 is investigated by 7-eV laser ARPES. In addition to the well-known node that occurs in CDAD when the incidence plane matches the mirror plane of the crystal, we show that another type of node occurs when the mirror plane of the crystal is vertical to the incidence plane and the electronic state is two dimensional. The flower-shaped CDAD's occurring around the Fermi level of SrTiO3:Nb and around the Dirac point of CuxBi2Se3 are explained on equal footings. We point out that the penetration depth…
We have performed a theoretical study of the magnetic circular dichroism in the x-ray absorption spectra (XMCD) of the equiatomic CoPt and FePt ordered alloys as a function of the spin quantization axis. We found that the magnetization axis is along the [001] direction and the magneto-crystalline anisotropy energy (MCA) for the FePt compound is twice as large as that of the CoPt compound in agreement with experiment. The band structure and the total density of states confirm that all electronic states contribute to the MCA, and not just the states at the vicinity of the Fermi level. The orbita…
Recent quantitative measurements of the orbital to spin magnetic moment ratio $m_L/m_S$ in electron magnetic circular dichroism (EMCD) experiments have given a $m_L/m_S$ ratio that is larger than commonly accepted values. We demonstrate here that plural scattering may noticeably influence the $m_L/m_S$ ratio. An equation is derived which describes its influence as a function of the spectral integrals of the plasmon scattering region and zero-loss peak. The influence of the electron-plasmon scattering can be removed when electron energy-loss spectra of the ionization edge are deconvoluted by th…
Although the Ni_4 cluster includes more information regarding the Ni band structure with respect to the Anderson impurity model, it also favors very peculiar ground states which are incompatible with a coherent picture of all dichroism experiments.
The high brightness, broad spectral coverage and pulsed characteristics of infrared synchrotron radiation enable time-resolved spectroscopy under throughput-limited optical systems, as can occur with the high-field magnet cryostat systems used to study electron dynamics and cyclotron resonance by far-infrared techniques. A natural extension for magnetospectroscopy is to sense circular dichroism, i.e. the difference in a material's optical response for left and right circularly polarized light. A key component for spectroscopic circular dichroism is an achromatic 1/4 wave retarder functioning o…
The magnetic circular dichroism of III-V diluted magnetic semiconductors, calculated within a theoretical framework suitable for highly disordered materials, is shown to be dominated by optical transitions between the bulk bands and an impurity band formed from magnetic dopant states. The theoretical framework incorporates real-space Green's functions to properly incorporate spatial correlations in the disordered conduction band and valence band electronic structure, and includes extended and localized electronic states on an equal basis. Our findings reconcile unusual trends in the experiment…
Circular dichroism (CD) spectra of chiral bare and thiol-passivated gold nanoclusters have been calculated within the dipole approximation. The calculated CD spectra show features that allow us to distinguish between clusters with different indexes of chirality. The main factor responsible of the differences in the CD lineshapes is the distribution of interatomic distances that characterize the chiral cluster geometry. These results provide theoretical support for the quantification of chirality and its measurement, using the CD lineshapes of chiral metal nanoclusters.
Strong enhancement of molecular circular dichroism has the potential to enable efficient asymmetric photolysis, a method of chiral separation that has conventionally been impeded by insufficient yield and low enantiomeric excess. Here, we study experimentally how predicted enhancements in optical chirality density near resonant silicon nanodisks boost circular dichroism. We use fluorescence-detected circular dichroism spectroscopy to measure indirectly the differential absorption of circularly polarized light by a monolayer of optically active molecules functionalized to silicon nanodisk array…
The difference in the transmission for left and right circularly polarised light though thin films on substrates in a magnetic field is used to obtain the magnetic circular dichroism of the film. However there are reflections at all the interfaces and these are also different for the two polarisations and generate the polar Kerr signal. In this paper the contribution to the differences to the total transmission from the transmission across interfaces as well as the differences in absorption in the film and the substrate are calculated. This gives a guide to when it is necessary to evaluate the…
We show that the intensity of pumped states near Weyl point is different when pumped with left- and right-handed circular polarized light, which leads to a special circular dichroism (CD) in time-dependent angle resolved photoemission spectra (ARPES). We derive the expression for the CD of time-dependent ARPES, which is directly related to the chirality of Weyl fermions. Based on the above derivation, we further propose a method to determine the chirality for a given Weyl point from the CD of time-dependent ARPES. The corresponding CD spectra for TaAs has then been calculated from the first pr…
The expected features of diluted magnetic semiconductors still remain in controversial issue, concerning whether or not s, p-d (f) exchange interactions indeed modify the host semiconductor band structure. To solve this doubt, a new scheme for measuring magneto-optical (MO) effect is developed, called magnetic photoresistance circular dichroism (PR-MCD), which detects the differential photoresistance of materials between two circularly polarized excitations. That allows us to detect the MO effect induced only by interband transitions, and provide unambiguous evidence that the host semiconducto…
We theoretically investigate the origin of the x-ray magnetic circular dichroism (XMCD) spectra at the K edges of Mn and Ga in the ferromagnetic phase of Mn3GaC on the basis of an ab initio calculation. Taking account of the spin-orbit interaction in the LDA scheme, we obtain the XMCD spectra in excellent agreement with the recent experiment. We have analyzed the origin of each structure, and thus elucidated the mechanism of inducing the orbital polarization in the p symmetric states. We also discuss a simple sum rule connecting the XMCD spectra with the orbital moment in the p symmetric state…
To clarify whether or not (Ga,Cr)As is an intrinsic diluted magnetic semiconductor, a systematic study of the magnetic circular dichroism (MCD) was carried out for a series of (Ga,Cr)As epilayers grown by the low-temperature molecular-beam epitaxy technique. The present work provides unambiguous evidence for the intrinsic ferromagnetism of the (Ga,Cr)As epilayers with all the necessary properties in accordance with that of a diluted magnetic semiconductor, especially the hysteresis characteristics, which is opened up in the magnetic field dependence of MCD.
The helical Dirac fermions at the surface of topological insulators show a strong circular dichroism which has been explained as being due to either the initial-state spin angular momentum, the initial-state orbital angular momentum, or the handedness of the experimental setup. All of these interpretations conflict with our data from Bi2Te3 which depend on the photon energy and show several sign changes. Our one-step photoemission calculations coupled to ab initio theory confirm the sign change and assign the dichroism to a final-state effect. The spin polarization of the photoelectrons, inste…
Silicene (a monolayer of silicon atoms) is a topological insulator, which undergoes a topological phase transition to a band insulator under an external electric field. The spin polarization is unique and opposite at the K and K' points due to the spin-orbit coupling. Accordingly, silicene exhibits a strong circular dichroism with respect to optical absorption, obeying a certain spin-valley selection rule. It is remarkable that this selection rule is drastically different between these two types of insulators owing to a band inversion taking place at the phase transition point. Hence we can te…
Polarization-dependent photon spectroscopy (dichroism) using signal-enhancing superchiral beams is shown to be sensitive to magnetic properties of the sample, whereas previous investigations explored charge-like electronic properties of chiral samples. In the process of unveiling the potential to observe magnetic circular dichroism (MCD), we underline an affinity between spectroscopies using the Borrmann effect, twisted beams and superchiral beams. Use of an effective wavevector in a quantum-mechanical theory unites the aforementioned spectroscopies and vastly improves our understanding of the…
In the close vicinity of a chiral nanostructure, the circular dichroism of a biomolecule could be greatly enhanced, due to the interaction with the local superchiral fields. Modest enhancement of optical activity using a planar metamaterial, with some chiral properties, and achiral nanoparticles has been previously reported. A more substantial chirality enhancement can be achieved in the local filed of a chiral nanostructure with a three-dimensional arrangement. Using an embossed chiral nanostructure designed for chiroptical sensing, we measure the circular dichroism spectra of two biomolecule…
Time-resolved x-ray magnetic circular dichroism (XMCD) enables a unique spectroscopic view on complex spin and charge dynamics in multi-elemental magnetic materials. So far, its application in the soft-x-ray range has been limited to synchrotron-radiation sources and free-electron lasers. By combining a laser-driven plasma source with a magnetic thin-film polarizer, we generate circularly polarized photons in the soft x-ray regime, enabling the first XMCD spectroscopy at the Fe L edges in a laser laboratory. Our approach can be readily adapted to other transition metal L and rare earth M absor…
