ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 310 (2007) 21742176

www.elsevier.com/locate/jmmm

XPS study of ferrimagnetic double perovskite thin lms

H. Asano, N. Koduka, Y. Takahashi, M. Matsui
Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan
Available online 28 November 2006

Abstract
This paper reports X-ray photoelectron spectroscopy (XPS) study on thin lms of half-metallic materials with an ordered doubleperovskite structure. The XPS core-level spectra were measured for several Sr2FeMoO6 (SFMO) and Sr2CrReO6 (SCRO) lms with and
without in situ deposited thin overlayers of MgO and SrTiO3. For a fresh SFMO lm surface, the XPS spectrum of the Mo 3d region
showed a multiple feature, which reects the ferrimagnetic metallic nature. Whereas SFMO lms with overlayers of SrTiO3 showed
degraded interface properties, lms with overlayers of MgO showed the multiple feature similar to the fresh SFMO surface, indicating
that the electronic properties at the MgO interface were preserved. Very similar tendency was observed for the Re 4f core-level spectra of
the SCRO/overlayer systems.
r 2006 Elsevier B.V. All rights reserved.
PACS: 79.60; 75.70; 73.20-r
Keywords: X-ray photoelectron spectroscopy; Core-level spectrum; Binding energy; Half-metallic ferromagnet; Epitaxial thin lm

1. Introduction

2. Experiment

The double perovskites of the form A2BB0 O6 have

attracted extensive interest both due to their rich physics
and due to their technological importance. Several experimental and theoretical studies have demonstrated that
Sr2FeMoO6 (SFMO) and Sr2CrReO6 (SCRO) and other
related materials [1,2] exhibit a ferrimagnetic half-metallic
ground state with high Curie temperatures Tc (420 K for
SFMO and 635 K for SCRO), which makes them potential
candidates for spintronic applications. Since the electrical
and magnetic properties of this type of oxides are easily
modulated through surface/interface effects, it is important
to understand the electronic structure of the surface/
interface layers. In this paper, we report on the XPS
characterization of SFMO and SCRO thin lms with and
without thin overlayers of MgO and SrTiO3 in order to
investigate the modication of electronic structures at the
surface and interface.

Epitaxial thin lms of SFMO and SCRO were sputter

deposited on the lattice-matched substrates of Ba0.4Sr0.6TiO3-buffered and bare SrTiO3, respectively. Details of
deposition procedures and lm properties were previously
reported [3]. X-ray diffraction analysis conrmed that these
lms were in high phase purity and a high degree of the
B-site ordering (the long-range order parameter S40.9).
Surface characterization by atomic force microscopy
demonstrated that these lms had atomically at and
well-dened surfaces free from any surface precipitates.
Thin overlayers of MgO and SrTiO3 of 1 nm in thickness
were in situ deposited onto SFMO and SCRO lms. X-ray
photoelectron spectroscopy (XPS) spectra were acquired
with MgKa radiation (1254 eV).

Corresponding author. Tel.: +81 52 789 3568; fax: +81 52 789 3237.

E-mail address: asano@numse.nagoya-u.ac.jp (H. Asano).

0304-8853/$ - see front matter r 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2006.11.118

3. Results and discussion

At rst, the XPS investigations were undertaken on the
SFMO and SCRO lm surfaces in an as-grown state. It is
found that the spectra of the Sr 3d core-level region for
both lms show dominant contribution from those of the
Sr-containing perovskites with a small amount of surface

ARTICLE IN PRESS
H. Asano et al. / Journal of Magnetism and Magnetic Materials 310 (2007) 21742176

Normalized Intensity

Mo3d5/2

SFMO

Mo3d3/2

1 nm Cap/SFMO

1 nm Cap/SCRO
MgO

SrTiO3

50

45
Binding Energy (eV)

40

Fig. 2. XPS spectra of the Re 4f core level of SCRO lms (a) without an
overlayer and (b) with 1-nm-thick overlayers of MgO and SrTiO3.

Fig. 2, small contributions from O 2s and Cr 3p make the

quantitative analyses difcult. Even then, the shape and the
binding energy of the Re 4f peak for a SCRO surface are
quite different from those of simple Re oxides [5]. This
broad feature in the Re 4f peak is possibly due to the
unusual electronic state of Re in the metallic ferrimagnetic
SCRO, as in the case of Mo in the SFMO. As shown in
Fig. 2(b), the Re 4f spectrum for an SCRO lm with an
MgO overlayer of 1 nm showed the similar broad feature,
suggesting that the electronic structure of the interfacial
SCRO layer was preserved. Note that the component at
48.5 eV for SCRO lm with MgO is ascribed to the Mg 2p
core level. When the SCRO lm is capped with a SrTiO3
overlayer, the broad feature of the Re 4f spectra is strongly
modied. Very similar tendency between the SFMO and
SCRO cases may reect the intrinsic electronic and
chemical nature of the ferrimagnetic metallic doubleperovskite materials. Further studies are necessary to
elucidate the origin of the interfacial modication of the
double-perovskite lms with overlayer materials.

We systematically investigated the heterointerfaces of

overlayer/SFMO (SCRO) using the Mo 3d (Re 4f) corelevel photoemission. The XPS observation reveals that the
quality of heterointerfaces of overlayer/SFMO(SCRO)
strongly depends on the overlayer materials. Such information about the surface/interface characteristics would be
useful for developing multilayer tunneling devices based on
these materials.

MgO

235

as-grown

4. Conclusions

SrTiO3
240

as-grown

SrMoO4

Re4f

SCRO

Normalized Intensity

impurity phase. The SFMO lms exhibited a single

spinorbit doublet with the Fe 2p3/2 peak at 710.5 eV,
which corresponds to the oxidized Fe. The SCRO lms
exhibited a single spinorbit doublet with the Cr 2p3/2 peak
at 575.5 eV, which can be assigned to Cr3+. As far as the Sr
3d core level and the 2p core level of the magnetic B
elements are concerned, the observed spectral behaviors are
consistent with those expected for these materials [1,2].
Since the electronic structures of nonmagnetic B0 ions
have been shown to play an important role in the magnetic
and electrical properties of these materials, the Mo 3d core
level of SFMO lms and the Re 4f core level of SCRO lms
were systematically examined. Fig. 1 shows XPS spectra of
the Mo 3d core level of SFMO lms (a) without an
overlayer and (b) with 1-nm-thick overlayers of MgO and
SrTiO3. For a fresh SFMO lm surface, the spectrum of
the Mo 3d main region showed a multiple feature, which
consisted of, in addition to the simple Mo 3d5/2 and 3d3/2
doublet peaks, the lling in the valley between the Mo 3d5/2
and 3d3/2 doublet peaks and the tail at the low binding
energy side. This multiple feature is an indication of the
unusual electronic state of Mo in the metallic ferrimagnetic
SFMO [4], and is in striking contrast with the sharp Mo
3d5/2 and 3d3/2 doublet peaks for insulating SrMoO4 phase,
as shown in the dashed line in Fig. 1(a). As shown in
Fig. 1(b), the Mo 3d spectrum for an SFMO lm with an
MgO overlayer of 1 nm showed the multiple feature,
indicating that the electronic structure of the interfacial
SFMO layer was preserved. Interestingly, the multiple
feature of the Mo 3d spectra is strongly modied when the
SFMO lm is capped with an SrTiO3 overlayer.
Fig. 2 shows XPS spectra of the Re 4f main region of
SCRO lms (a) without an overlayer and (b) with 1-nmthick overlayers of MgO and SrTiO3. Although the large
Re 4f component is mainly responsible for the spectra in

2175

230

225

Binding Energy (eV)

Fig. 1. XPS spectra of the Mo 3d core level of Sr2FeMoO6 lms
(a) without an overlayer and (b) with 1-nm-thick overlayers of MgO and
SrTiO3. The dashed line in (a) denotes the corresponding spectra of the
insulating SrMoO4.

Acknowledgment
This work was partially supported by a Grand-in-Aid
for Scientic Research from the Japan Society for the
Promotion of Science (No. 1736020).

ARTICLE IN PRESS
2176

H. Asano et al. / Journal of Magnetism and Magnetic Materials 310 (2007) 21742176

References
[1] K.I. Kobayashi, T. Kimura, H. Sawada, K. Terakura, Y. Tokura,
Nature 395 (1998) 677.
[2] H. Kato, T. Okuda, Y. Okimoto, Y. Tomioka, K. Oikawa,
T. Kamiyama, Y. Tokura, Phys. Rev. B 69 (2004) 184412.

[3] H. Asano, N. Koduka, K. Imaeda, M. Sugiyama, M. Matsui, IEEE

Trans. Magn. 41 (2005) 2811.
[4] D.D. Sarma, P. Mahadevan, T. Saha-Dasgupta, S. Ray, Phys. Rev.
Lett. 85 (2000) 2549.
[5] W.T. Tsyoe, F. Zaera, G.A. Somorjai, Surf. Sci. 200 (1988) 1.