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Phys. Status Solidi B 248, No. 5, 12531257 (2011) / DOI 10.1002/pssb.201046420

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Localization and screening in GdNi alloy films


N. Wu* , D. LaGraffe , I. N. Yakovkin , and P. A. Dowben
1
,1

basic solid state physics

Department of Physics and Astronomy, Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln, Theodore Jorgenson Hall, 855 North 16th Street, Lincoln, Nebraska 68588-0299, USA 2 Ofce of Proliferation Detection NA-22, National Nuclear Security Administration, US Department of Energy, 1000 Independence Avenue SW, Washington, DC 20585, USA 3 National Academy of Science of Ukraine, Institute of Physics, Prospect Nauki 46, 03028 Kiev, Ukraine Received 2 August 2010, revised 1 October 2010, accepted 7 October 2010 Published online 9 November 2010 Keywords charge screening, GdNi, resonant photoemission, RKKY interaction
* Corresponding

author: e-mail ningwu@unlserve.unl.edu, Phone: 1 402 472 2797, Fax: 1 402 472 2879

Gd/Ni compounds with different Gd concentration have been investigated with constant initial state spectroscopy (CIS) of photoemission utilizing the light of synchrotron radiation. The photoemission cross-sections of Gd 5d and 4f states show a strong resonance in CIS spectra at the Gd 5p absorption edge. The screenings of Gd ions by Ni 3d conduction electrons results in a dramatic suppression of the 5p64f75d16s2 to 5p54f75d26s2

resonant enhancement of photoemission valence band intensities. This decrease in the super-CosterKronig photoemission resonant enhancement of the valence band can be related to the hybridized Gd 5d and Ni 3d bands near the Fermi level, consistent with performed rst-principles calculations of local densities of states.

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1 Introduction Alloys of gadolinium nickel have attracted much attention because of their magnetic [17] and extraordinary magneto-elastic properties [811]. In the ferromagnetic phase, strong 3d5d hybridization gives rise to a small Ni magnetic moment [11] and soft X-ray magnetic circular dichroism experiments indicate that this localized Ni moment is anti-parallel coupled to the Gd magnetic moment [12, 13]. The coupling of the Ni 3d electrons to the larger magnetic moment of the highly localized Gd 4f7 in Gd/Ni compounds argues for a more localized picture than occurs in the case of pure Ni [13]. Although Gd/Ni bilayer structures have been reported [14], these studies indicate that the Gd atoms easily diffuse into the Ni matrix and therefore a Gd/Ni alloy is more likely to exist at the interface [15, 16]. The charge distribution models [17] describe a picture where the 5d electrons of the rare earth elements transfer to the unlled 3d bands of transition metal in these rare earth transition metal alloys. In the other words, the 5d rare earth and 3d transition metal states are strongly hybridized in rst-principles calculations [11], consistent with experiment [11, 18, 19]. As Ni concentration increases, 3d electrons become more itinerant and therefore the screening effect on the Gd ions should be

more signicant. Indeed alloying gadolinium with transition metals does change the photoemission lifetimes [20], which should be indicative of changes of electron localization and screening in the photoemission nal state [2131]. While the changes in the resonant photoemission intensities have often been used to probe changes in metallicity, here we use the technique to explore screening effects on the Gd photoemission nal state in Gd/Ni alloys and ultimately further demonstrates the existence of a strong 3d5d hybridization in these alloys. 2 Experiment The resonant photoemission in this study was observed using a well-established spectroscopic tool: constant initial state spectroscopy (CIS) [2132]. CIS spectroscopy is basically a plot of the relative photoemission intensity of a valence band photoemission feature as a function of photon energy. As indicated by the name, such spectra can be obtained by measuring the photoemission intensities of a xed binding energy for various photon energies. There are some photoemission selection rule effects that will appear in the CIS spectra for Gd [32], but as with the photoemission experiments, the CIS spectra were taken with a light incidence angle of 328 with respect to the
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N. Wu et al.: Localization and screening in GdNi alloy films

surface normal, unless stated otherwise, and the photoelectrons were collected along the thin lm surface normal. For this geometry, matrix element effects [32] can be largely neglected. Here we provide the CIS spectra from the density of states (DOS) near the Fermi level (the position of the Gd surface state [33] just below the Fermi level, marked by an S in Fig. 1) and the shallow Gd 4f levels at roughly 8.6 eV, also as illustrated in Fig. 1. The angle-resolved photoemission and CIS experiments were performed using the 3 m toroidal grating monochromator (3 m TGM) beam line [32, 34, 35] at the synchrotron radiation center in Stoughton, Wisconsin, in an ultra high vacuum (UHV) chamber equipped with a hemispherical electron analyzer with an angular acceptance of 18, as described elsewhere [32, 34, 35]. The combined resolution of the electron energy analyzer and monochromator was 120 150 meV for photon energies in the range of 50120 eV. The photoelectrons were collected at the normal emission throughout this work both for the conventional photoemission and the CIS spectra shown here. For the different Gd/Ni alloys, resonant photoemission intensities have been normalized correcting for changes in the synchrotron ring current and photon uence. Photoemission spectra were taken at room temperature, or above the Curie temperature of 72 K for Gd50Ni50 [3638]. The alloy thin lms were fabricated by co-evaporation of Gd and Ni on a Cu(100) substrate at room temperature. The

depositions were carried out under UHV conditions about 3 1010 Torr or less, as described elsewhere [15], and no evidence for impurities in the lms as-grown was found. 3 Suppression of photoemission resonance In this study, we have employed CIS to investigate how the resonant photoemission intensities and the Gd 5d/Ni 3d DOS in the region of the Fermi level evolve for thin lms of Gd80Ni20, Gd50Ni50, Gd30Ni70, and Gd20Ni80 alloys. The photoemission of the alloy valence band region in the vicinity of the Fermi level and in the region of the Gd 4f shallow core levels show a hint of the Gd surface state in the Gd80Ni20 alloy lms, seen in normal emission for pure Gd(0001) [33], although this assignment is compromised by the presence of nickel in the alloy thin lms. In the resonant photoemission process, a core exciton is formed, where an electron in a core level is excited to an unoccupied state near the Fermi level. However, this state is transient and unstable, and an electron on the valence band decays back to core level through an Auger-type process [39]. If an electron is emitted so that the nal state is identical with the direct photoemission process, then the excitation creating a core exciton opens another channel of photoemission with the same initial and nal energy states as the direct process. The initial gadolinium weighted states near the Fermi level will undergo the photoemission resonant enhancement [32]: 5p6 4f 7 5d1 6s2 ! 5p5 4f 7 5d2 6s2 ! 5p6 4f 7 5d0 6s2 e ; as the incident photon energy is swept through the Gd 5p shallow core level binding energies (roughly 21 eV for the 5p3/2 and 28 eV for the 5p1/2 [40]). We may split this Gd atomic super-CosterKronig process [32] into two parts: (i) excitation and (ii) Auger-like relaxation mechanism, as schematically illustrated in Fig. 2. This resonant enhancement is quite signicant at 25 and 32 eV, above the respective Gd 5p thresholds as seen in Fig. 3. Generally, the resonant photoemission intensities are greater for the excitations with large angular momentum states in gadolinium [32], the resonance involves the same principle quantum number (5), so the strong resonant enhancements observed are not surprising and indeed expected at the 5p shallow core threshold and consistent with prior observations [32]. These resonant enhancements of the photoemission intensities from the initial states near the Fermi level are quickly suppressed with increasing nickel content, however. Similarly, the initial 4f gadolinium weighted states at about 8.6 eV, also can undergo a photoemission resonant enhancement:

Figure 1 Photoemission spectra of Gd80Ni20, Gd50Ni50, Gd30Ni70, and Gd20Ni80 alloy thin lms, taken using a photon energy of 33 eV, with the photoelectrons collected along the thin lm normal. Note the intensity of the states near EF increases as the Ni concentration increases. S indicates the position of the Gd surface state [33] and B the Gd bulk 5d bands.
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5p6 4f 7 5d1 6s2 ! 5p5 4f 7 5d2 6s2 ! 5p6 4f 6 5d1 6s2 e ; which are quickly suppressed with increasing nickel content, as shown in Fig. 4. As Ni concentration increases, there is a dramatic suppression of the 5p64f75d16s2 to 5p54f75d26s2 resonant
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Phys. Status Solidi B 248, No. 5 (2011) 1255

Figure 2 A schematic general representation of the resonant photoemission process followed by an Auger-like decay for a 5p5d transition and direct photoemission from the top of the valence band.

enhancement of photoemission valence band intensities. One might attribute this loss in the photoemission resonant enhancement intensities to the decrease in Gd concentration. However, the decreases to the photoemission resonant enhancement intensity are so dramatic that other explanations must be sought. For example, the photoemission resonant enhancement for the Gd20Ni80 is not very signicant after normalization, in spite of the fact that there remains a considerable amount of Gd and the Gd 4f photoemission intensities (at roughly 8.6 eV binding energy), as seen in Fig. 1. The screening and lifetime effects must have a critical impact.

Figure 4 Constant initial state spectra of GdNi alloy at the normal emission with the Gd 4f state chosen as initial state. The arrow indicates increasing Ni concentration in the alloy thin lms: Gd80Ni20, Gd50Ni50, Gd30Ni70, and Gd20Ni80.

4 Enhancement of density of states near Fermi level An electron in a lattice composed of simple metal atoms sees a potential: Ur e2 expls r; r (1)

where ls is the screening parameter. When ls is large enough the core exciton unbinds for this small potential. On the other hand, ls can decrease, at some critical point, until a bound state is possible. Usually, the intensity of the resonant photoemission process is inversely proportional to the screening parameter ls as [21, 2331]: 1 I : ls I0 (2)

Figure 3 Constant initial state spectra of GdNi alloys with the initial state chosen as Gd 5d states near the Fermi level. The arrow indicates increasing Ni concentration in the alloy thin lms: Gd80Ni20, Gd50Ni50, Gd30Ni70, and Gd20Ni80.
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Thus there must be a huge increase in the screening parameter with increasing nickel content in Gd/Ni alloys, far greater than represented by the nickel content alone. This increasing screening not only diminishes peak intensity but also shifts the cross-section maximum to higher photon energies [21]. For a system with strong hybridization between Gd and Ni (as suggested by prior photoemission studies [19]), the screening parameter can be then roughly related to the DOS at the Fermi level. For a purely twodimensional system, ThomasFermi screening theory indicates that ls is proportional to the DOS in the vicinity
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N. Wu et al.: Localization and screening in GdNi alloy films

of the Fermi level [21, 23, 41]: ls 2pe ns ; kkB T


2

(3)

where k is the average dielectric constant. The screening parameter, therefore, increases with increasing DOS at the Fermi energy, i.e., the increasing numbers of conduction electrons. The Gd/Ni alloys are expected to show an increase in the DOS at the Fermi level due to the signicant Ni 3d occupation. To evaluate the changes in DOS induced by alloying Ni in Gd, we have performed spin-polarized DFT calculations for a model fcc structure, in which a Ni atom substitutes one Gd atom in the cubic unit cell containing four atoms. (As it has been shown earlier [4244], DOS calculated for hcp and fcc Gd are very similar.) The calculations were performed with ABINIT [45] program, using norm-conserving pseudopotentials and generalized gradient approximation (GGA-PBE) [46] for exchange correlation. The energy cutoff was 30 Hartrees and a 6 6 6 k-point lattice provided the convergence of total energies about 104 Hartrees. Due to the same number of atoms in the cell, a comparison of DOS for Gd and Gd3Ni

alloy is straightforward (Fig. 5). Thus, it is found that with adding Ni the DOS near the Fermi level increases, as it could be expected from a high density of d states of Ni. This is seen in the photoemission intensities near the Fermi level (see Fig. 1), which allows us to suggest that both experiment and calculations conrm that more Ni concentration results in more effective screening (larger ls), which is the result of rise in the itinerant electron DOS near the Fermi level. These DOS calculations are, of course, idealized approximations and do not include lattice imperfections nor the possibility of occupancy of interstitial sites. The results suggest that the Gd atoms tend to be surrounded by Ni atoms to enhance the efciency by which the 3d Ni conduction electrons contribute to the quenching of the Gd core exciton created in the resonant photoemission process. Of course this in turn would result in an increased localization of otherwise more itinerant Ni 3d electrons. Yano et al. [13] have pointed out that Ni 3d electrons in Gd/Ni alloys are expected to be more localized than those of pure Ni metal. Talik and Neumann [19] found evidence for strong hybridization of the Ni 3d states with 5d states of Gd in X-ray photoelectron spectroscopy. This strong hybridization between Ni and Gd will cause an effective increase in the unoccupied Gd 5d band width and that is fundamental origin of the shift in the CIS resonance peak from 33 to 35 eV at the 4f initial state, seen in Fig. 4 as nickel concentration increases. The fact that each Gd atom tends to be adjacent to a Ni atom suggests that the alloying process favors an ordered or weakly ordered alloy, even when formed at room temperature. Such local ordering and strong GdNi hybridization would tend to suppress the reactivity of gadolinium to a metal thin lm less susceptible to oxidation, as is the case for nickel. The suppression of Gd oxidation makes such Gd/Ni lms worth considering as a neutron conversion layer for solid state neutron detector devices [4751]. 5 Conclusion In conclusion, we have observed strong resonant photoemission of Gd 5d and 4f states that are quickly and strongly suppressed by increases in the nickel content of Gd/Ni alloy thin lms. It is likely that these alloys adopt short range order in the vicinity of each Gd atom and that the Gd 5dNi 3d and 6s4s states of GdNi nearest neighbor atoms are strongly hybridized.
Acknowledgements This work was supported by the Defence Threat Reduction Agency (grant no. HDTRA1-07-10008), and the Nebraska Research Initiative. The authors are particularly grateful to Wlad Borgiel for a number of very helpful discussions. The views expressed in this article are those of the authors and do not reect the ofcial policy or position of the National Nuclear Security Administration, Department of Defence or the US Government.

Figure 5 (online color at: www.pss-b.com) DOS of bulk Gd (a) and the Gd3Ni compound (b). Both (a) and (b) plots have been obtained for the same fcc structure with a cubic unit cell containing four atoms. Spin-up and spin-down DOS are shown by solid and dashed lines, respectively. As Ni is alloyed with Gd, the DOS near the Fermi level increases due to high density of d states of Ni.
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