# Magnetic circular dichroism in X-ray fluorescence of Heusler alloys at threshold excitation

## Abstract

The results of fluorescence measurements of magnetic circular dichroism (MCD) in Mn L<sub>2</sub>,<sub>3</sub> X-ray emission and absorption for Heusler alloys NiMnSb and Co<sub>2</sub>MnSb are presented. Very intense resonance Mn L<sub>3</sub> emission is found at the Mn 2p<sub>3/2</sub> 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.

Heusler alloys with chemical composition X<sub>2</sub>MnZ or XMnZ (X=Cu,Ni,Co,Fe,Pd,Pt; Z=Al,Ga,In,Si,Sn,Sb) and L2<sub>1</sub> or C1<sub>b</sub> crystal structure are of great interest since their discovery in 1903  because they are ternary intermetallic compounds with magnetic properties that can be altered by changing the degree or type of chemical order . First-principles spin-polarized calculations showed that the electronic structure of Heusler alloys has a metallic character for majority spin-electrons but an insulating character for minority spin-electrons which can induce the half-metallic ferromagnet state and band gap near the Fermi level.

It is supposed that X-ray fluorescence spectroscopy, performed with circularly polarized photons, could measure the spin polarization of the occupied density of states (DOS). This kind of dichroism in X-ray fluorescence closely related magnetic circular dichroism (MCD) in absorption  and is complementary to it. It is shown that a spin-polarized core hole may be used as a local site-specific spin detector for the valence states via appropriate valence-to-core dipole transitions. According to these expectations,the MCD effect can be observed without determining the polarization of emitted photons if the core holes are excited alternatively by the right- and left-handed circularly polarized radiation by using different sample magnetization directions. In this case the difference in the emitted radiation will closely reflect the spin-resolved local DOS.

MCD in X-ray emission is predicted theoretically in Ref.5, based on fully relativistic spin-polarized band structure calculations for iron. Experimentally, this effect is confirmed for pure Fe in Ref  and then is used for the study of the electronic structure of other magnetic systems as Co and Ni , Rh , Rh<sub>25</sub>Fe<sub>75</sub> and Ni<sub>45</sub>Fe<sub>55</sub>  and Fe-Co alloys . In this letter we present the results of study of magnetic dichroism in Mn 2p X-ray emission and absorption for Heusler alloys NiMnSb and Co<sub>2</sub>MnSb using energy-selective monochromatic excitation with circularly polarized X-rays.

The measurements were performed on beamline ID12B at the European Synchrotron Radiation Facility (ESRF). This beamline consists of a Dragon-like spherical grating monochromator producing some 83% circularly polarized x-rays. The extraordinarily low emittance of the 6 GeV stored electron beam allowed us to refocus the x-ray beam that passes the monochromator exit slit into a spot with dimensions of about 40 micron x 1 mm without excessive loss of intensity. The permanent magnet (NdFeB) devices were used to magnetize the sample for a fixed magnetization direction with H=0.2 T. The X-ray emission spectrometer consisted of an entrance 20 mkm slit, three spherical diffraction gratings, and a two-dimensional position-sensitive multichannel detector . It was oriented with its optical axis perpendicular to the incident X-rays, in a vertical dispersive geometry and was operated with a 1200 lines/mm grating in second order of diffraction at a spectral resolution of 1.1 eV. A single crystal of NiMnSb and a polycrystalline sample of Co<sub>2</sub>MnSb were taken for X-ray fluorescence measurements. The samples were scraped in vacuum of 10<sup>-6</sup> torr before the measurements. Fig. 1 shows the MCD effect in X-ray absorption and emission of NiMnSb excited by the right- and left-polarized radiation. The Mn 2p X-ray absorption spectrum (XAS) measured in a total electron yield (TEY) mode shows dichroism (Fig. 1a) at both L<sub>3</sub> (E<sub>exc</sub>=640.5 eV) and L<sub>2</sub> (E<sub>exc</sub>=652.0 eV) thresholds. The MCD effect is stronger at the L<sub>3</sub> threshold than that at L<sub>2</sub> threshold and a reason of this difference will be discussed later. The Mn 3d DOS is also presented.

Mn 2p X-ray emission spectra (XES) measured at the L<sub>3</sub> threshold (E<sub>exc</sub>=640.5 eV), L<sub>2</sub> threshold (E<sub>exc</sub>=652 eV) and far above threshold (E<sub>exc</sub>=680 eV) show quite different fine structures. The Mn L<sub>3</sub> XES measured at E<sub>exc</sub>=640.5 eV (Fig. 1b), which corresponds to the 3d 4s$``$2p<sub>3/2</sub> transition, has two subbands A and B located at 637.0 and 640.5 eV, respectively. Both subbands show dichroism with the same sign as is found for the Mn L<sub>3</sub> XAS. The MCD effect reaches its maximum at emission energy E=640.5 eV which exactly corresponds to the Mn L<sub>3</sub> threshold. The double peak structure revealed in Mn 2p XES can be a result of superposition of spectra of normal emission (A) and elastic x-ray scattering, known as re-emission (B). The intensity of the B subband is found to be about 1.5 times higher than that of the A subband. The Fermi level (estimated from Mn2p<sub>3/2</sub> core level photoemission ), is at the intensity minimum between these two subbands which means that the B subband corresponds to re-emission from unoccupied 3d states which are populated during near-threshold excitation of the Mn 2p<sub>3/2</sub> electron to the conduction band. X-ray re-emission is usually observed in spectra of insulators (see, for example, reference ) but in the case of a Heusler alloy, it have been never seen with so high intensity.

In the Mn L<sub>3</sub> XES measured at the L<sub>2</sub> threshold excitation (E<sub>exc</sub>=652 eV), we found great changes in the intensity distribution. The intensity of the peak A with an emission energy E=637.5 eV is decreased with respect to the spectrum measured at E<sub>exc</sub>=640.5 eV and this peak is merged with the peak B forming a rather wide emission band centered at the emission energy E=638.3 eV. The main intensity is due to the Mn L<sub>2</sub> XES (3d4s$``$2p<sub>1/2</sub> transition) which again shows two peaks (A’ and B’) located at emission energies of 648.2 and 652.0 eV (with Fermi level in between these peaks) corresponding to normal emission and re-emission, respectively. The intensity ratio of relative intensity I(B)/I(A) in Mn L<sub>2</sub> XES is found to be opposite with respect to that of the Mn L<sub>3</sub> XES. Dichroism of the Mn L<sub>3</sub> XES (A) at the L<sub>2</sub> threshold is found to be higher than that of the Mn L<sub>3</sub> XES (A) at the L<sub>3</sub> threshold whereas dichroism of the Mn L<sub>3</sub> (B) at the L<sub>2</sub> threshold is absent. The Mn L<sub>2,3</sub> XES measured far above the thresholds at E<sub>exc</sub>=680 eV (Fig. 1d) shows dichroism with different sign for L<sub>3</sub> and L<sub>2</sub> and relatively high ratio of I(L<sub>2</sub>)/I((L<sub>3</sub>)=0.92 which is higher than that for pure Mn (0.27). We have found also anomalously high ratio I(L<sub>2</sub>)/I((L<sub>3</sub>)= 0.5-0.6 for that of Mn L<sub>2,3</sub> XES of Heusler alloys, measured with electron excitation . Fig. 2 shows MCD in Mn 2p X-ray emission for polycrystalline Co<sub>2</sub>MnSb excited by right- and left-polarized radiation at E<sub>exc</sub>=640.5, 644, 652 and 680 eV. As seen, the MCD behavior for Co<sub>2</sub>MnSb is found to be almost the same as that for NiMnSb. Therefore, one can conclude that experimentally observed MCD effects in near-threshold excited Mn 2p XES are the same for Heusler alloys with half-metallic character of electronic structure and can be discussed together.

To interpret obtained results we have developed a theory for the description of X-ray transitions under threshold excitation. Here we will discuss only the main aspects of this theory. The details are given in . The model is based on the calculated partial Mn 3d-density of states for NiMnSb  which has the following main features: (i) a strong exchange splitting (about 2 eV) which affects the valence states distribution, (ii) spin-down states have a strong peak above the Fermi level (spin-up states are absent in this region and located below the Fermi level). We will show that this peak can be used as a trap for an excited core electron with a spin selectivity and responsible for the high intense re-emission peak in XES. Let us discuss the MCD effects in XES of Heusler alloys. Core states are split by the spin-orbital interaction for 2p<sub>3/2</sub> and 2p<sub>1/2</sub> with mostly parallel and anti-parallel direction of the orbital moment with respect to the spin moment of an electron. The spin direction is fixed by the spin-polarization of unoccupied states in which core electron are excited under absorption of x-ray quanta. Therefore, in such a way the part of states with orbital moment projections parallel (or anti-parallel) to the spin moment of atom are selected. The photons with right (photon spin +1) and left (photon spin -1) polarizations interact differently with electrons having a fixed projection of the orbital moment.This leads to dichroism. X-ray emission is a reverse process with respect to x-ray absorption and therefore also reveals dichroism. Using theory of the second order on electron-phonon interaction we have given the quantitative description of emission, re-emission and absorption within the one-particle approach In the case of resonance 2p<sub>1/2</sub> and 2p<sub>3/2</sub> excitations with right-hand photons (q=+1), when the photon spin is parallel to the spin moment of the solid, the emission intensities are given by equations . This change of the dichroism sign can for differerent threshold excitations can be explained within framework of the two-step process for the X-ray emission. At first, the transition of core level electron to the conduction band takes place which is characterized by dichroism of absorption and then a normal emission occurs (with an X-ray transition from the valence band to the vacancy on the core level) which is characterized by dichroism of emission. In the case of the near-threshold excitation, these both constituents of dichroism have different signs because spin- polarizations of unoccupied and occupied states are different. In given case, dichroism of the first process (absorption) prevails. Under excitation far away from the threshold, the unoccupied states are unpolarized, $`P^e`$=0, and the result is determined by dichroism of the second step, i.e. emission.

Going back to the re-emission peaks at L<sub>3</sub> and L<sub>2</sub> thresholds we need to note that the relative intensity of a first one is higher than a second one. Though the calculations predict the decrease in the ratio $`I^r`$/$`I^e`$ from 1.0 to 0.45 on going from L<sub>3</sub> to the L<sub>2</sub> threshold, the observed re-emission peak at L<sub>2</sub> threshold is even lower than predicted. It can be due to a shorter lifetime of a L<sub>2</sub> core hole (compared to that of L<sub>3</sub> core hole) as a result of L<sub>3</sub> $``$ L<sub>2</sub> Auger transition. One can also expect that the field of a L<sub>2</sub> core hole with higher binding energy is screened stronger than that of a L<sub>3</sub> core hole. A value of the field directly determines the lifetime of the excited electron on the central atom and a probability of re-emission.

In conclusion we have found MCD effects in X-ray emission and absorption of Heusler alloys which evidence about strong exchange splitting of Mn 3d-states with different spin projections. The observed giant re-emission peak in the Mn XES at the L<sub>3</sub> threshold is due to the half-metallic character of the electronic structure of Heusler alloys. The long lifetime of the excited states (which is necessary for intense re-emission) is provided by the limitation of the radiation-less relaxation of excited electrons on the Fermi level and their delay on the atom by the field of the core hole. In Heusler alloys with large local magnetic moment there is a possibility of revealing of such a mechanism of suppression of the relaxation which is based on strong exchange splitting, typical for half-metallic systems. Both the existence of the energy gap in spin-down projection of Mn 3d-states and weak hybridization of Mn 3d electrons with nearest neighborhood conduce to the suppression of the excited electron relaxation. A theoretical model for the description of resonance scattering of polarized X-rays is suggested and the quantitative theory of X-ray emission MCD in terms of spin-polarized electron density of states and spin-orbital splitting of core levels is developed.

This work was supported by Russian Science Foundation for Fundamental Research (Project 96-15-96598 and 99-02-16266), NATO Linkage Grant (HTECH.LG 971222), Swedish Natural Science Research Council (NFR) and Goran Gustavsson Foundation in Natural Sciences and Medicine,Deutsche Forschungsgemeinschaft DFG project Br 1184/4 and Bundesministerium fur Bildung und Forshung (BMFB 05SB8MPB8). Technical assistance of ESRF staff is gratefully acknowledget. The single crystal of NiMnSb was supplied by Ch. Hordequien (CNRS) and polycrystaline Co<sub>2</sub>MnSb was supplied by Elena I. Shreder (Institute of Metal Physics, Russian Academy of Sciences-Ural Division)

Figures Caption:

Fig. 1 Excitation energy dependence of the Mn L<sub>2</sub>,<sub>3</sub> XES and Mn 2p XAS of NiMnSb. Mn 2p TEY spectrum (a) and XES spectra (b), (c), (d) ,excited with parallel aligment of photon spin and spin moment (filled squares) and antiparallel aligment (open circles). Mn 2p<sub>3/2</sub> and Mn2p<sub>1/2</sub> binding energies relative to Fermi level are indicated as E<sub>f</sub>(L<sub>3</sub>) and E<sub>f</sub>(L<sub>2</sub>),respectively Energy resolution is 1.1 eV The Mn 3d DOS  is shown at insertion at Fig 1.b

Fig. 2 Excitation energy dependence of Mn L<sub>2</sub>,<sub>3</sub> XES of Co<sub>2</sub>MnSb. Spectra (a), (b), (c), (d) excited with parallel aligment of photon spin and spin moment (filled squares), and antiparallel aligment (open circles). Corresponding excitation energies are shown right side of frame. Mn 2p<sub>3/2</sub> and Mn2p<sub>1/2</sub> binding energies relative to Fermi level indicated as E<sub>f</sub>(L<sub>3</sub>) and E<sub>f</sub>(L<sub>2</sub>), respectively.Energy resolution is 1.1 eV.