ISSN 10637842, Technical Physics, 2011, Vol. 56, No. 11, pp. 1670–1674. © Pleiades Publishing, Ltd., 2011.

Original Russian Text © M.V. Gomoyunova, G.S. Grebenyuk, I.I. Pronin, 2011, published in Zhurnal Tekhnicheskoi Fiziki, 2011, Vol. 81, No. 11, pp. 130–134.

SURFACE, ELECTRON
AND ION EMISSION

Formation of Heusler Alloy Co2FeSi Thin Films

on the Surface of SingleCrystal Silicon
M. V. Gomoyunova*, G. S. Grebenyuk, and I. I. Pronin
Ioffe Physical Technical Institute, Russian Academy of Sciences, Politekhnicheskaya ul. 26, St. Petersburg, 194021 Russia
*email: Marina.Gomoyunova@mail.ioffe.ru
Received April 25, 2011

Abstract—The initial stages of Heusler alloy (Co2FeSi) thin film growth by reactive epitaxy on the Si(100)2 × 1
surface are studied, and formation conditions for this alloy are found. At a substrate temperature of lower
than, or equal to, 180°C, an island film of ternary Co–Fe–Si film grows on the surface. The silicon content
in this film is lower than in the compound to be synthesized. The film becomes continuous when its thickness
exceeds 1.2 nm. It is shown that postgrowth annealing at 240°C can raise the silicon content in the film and
be conducive to obtaining Heusler alloy of a desired composition. In situ measurements of the films show that
ferromagnetic ordering in them has a threshold and shows up at the coalescence growth stage of the Co–Fe–
Si island alloy.
DOI: 10.1134/S1063784211110107

INTRODUCTION tivity of 1 Ω cm) Si(100) wafers (misorientation rela

In recent years, halfmetallic ferromagnetic Heu
sler alloys have come into the spotlight of researchers
[1–8]. These materials are notable for 100% spin
polarization of electrons at the Fermi level [9] and are
therefore promising for creation of spintronic devices,
which are based on the injection of polarized electrons
into semiconductors. Cobaltbased Heusler alloys,
specifically, Co2FeSi compound offering the highest
Curie temperature (1100 K) and the highest magnetic
moment of atoms (6 μB), are especially attractive in
this respect [10, 11]. To date, this compound and other
Heusler alloys have been synthesized mostly on the
GaAs(100) and MgO(100) surfaces. At the same time,
attempts to synthesize the respective films on sili
con—the structure of particular interest for integra
tion of magnetic electron devices into chips by silicon
technology—have been made quite recently [12, 13].
It has been shown that good Co2FeSi films on the
Si(111) surface can be grown by molecular beam epitaxy.
In this article, we pioneer the synthesis of Co2FeSi
films on the Si(100)2 × 1 surface by means of a simpler
method—reactive epitaxy, in which only metal atoms
are applied on the heated silicon surface—and dem
onstrate the need for postgrowth annealing of the
films. The evolution of the elemental and phase compo
sitions, as well as the magnetic properties, of the films
during growth and subsequent annealing is studied.
1. EXPERIMENT
Films were deposited on atomically clean Si(100)2 ×
1 surfaces in ultrahigh vacuum (5 × 10–8 Pa). As sub
strates, we used KEF1 (phosphorusdoped to a resis
tive to the (100) surface was no more than 0.2°). The
surface was cleaned by the standard procedure: ex situ
processing by the Shiraki method with subsequent
heating in ultrahigh vacuum. The atomic structure of
the surface was examined with lowenergy electron
diffraction. During growth, Co and Fe layers as thin
as 2 and 1 Å, respectively, were alternately deposited
on the substrate surface. The deposition rate of both
metals was 0.3 Å/min, and the substrate temperature
was kept at 180°C (cobalt deposition) and 160°C (iron
deposition). After each deposition of Co and Fe, the
elemental composition and magnetic properties of the
growing film were studied.
Highresolution photoelectron spectroscopy using
synchrotron radiation was the main diagnostic
method. The photon energy was typically 135 eV, and
the energy resolution of the spectrometer (with regard
to that of the monochromator) was 100 meV. The ele
mental and phase compositions of the films were
determined from the core electron spectra. Emphasis
was on Si 2p electron spectra, which are highly sensi
tive to the chemical state of silicon atoms and their
local environment [14].
The magnetic properties of the films were studied
in situ by the elementspecific method of magnetic
linear dichroism in the photoemission of Co 3p and
Fe 3p electrons [15–18]. The essence of the magnetic
dichroism effect is that, when electrons are detected
within a narrow solid angle along the normal to the
sample surface, the energy position and the shape of
these spectral lines depend on the magnetization
direction in the plane of the film. The growing films
were magnetized with two Helmholtz coils placed in
the vacuum chamber. Current pulses passing through

1670
 FORMATION OF HEUSLER ALLOY CO2FeSi THIN FILMS
the coils generated a magnetic field of 1000 Oe, which
sufficed to saturate the film. In experiments, the elec
tron spectra were taken in the remanent magnetization
mode for two oppositely directed magnetic fields.
Experiments were conducted in vacuum (10–8 Pa) at
room temperature.
2. RESULTS AND DISCUSSION
From the variation of the Si, Co, and Fe line inten
sities with the film thickness, it follows that the con
tent of the metals in the forming film monotonically
increases, while that of silicon drops. For example, at
a deposition dose of 9 Å, the Si concentration
decreases by 50%. Although the Co dose exceeded the
Fe dose only twice, the Co content in the subsurface
layer was four times higher than the Fe content. This
finding is explained by different reactivities of these
metals [19–21]. Fe atoms penetrate into the surface
layers of silicon more extensively than Co atoms;
therefore, the Co/Fe concentration ratio in the grow
ing film does not equal the ratio of the deposition
doses for these metals. As the film grows and the inter
diffusion of silicon and metal atoms weakens, the
Co/Fe concentration ratio approaches 2. The Si con
centration continues decreasing, reaching 15% in the
films more than 20 Å thick.
The phase composition of the film derived from the
Si 2p spectra is illustrated in Fig. 1, which shows the
spectrum for the initial reconstructed Si(100)2 × 1 sur
face and also spectra taken at different growth stages of
the Heusler alloy film. In addition, Fig. 1 shows the
results of decomposition of the spectra into compo
nents corresponding to different phases. Decomposi
tion was made according to the standard technique
(see, e.g., [22]). All modes of the spectra are the dou
blets of the Si 2p3/2 and Si 2p1/2 sublevels described by
Voigt functions with different parameters. Having ana
lyzed the whole body of experimental data, we deter
mined the number of spectral modes and their charac
teristic binding energies and FWHM values.
The experimental spectrum taken of the Si(100)2 × 1
surface agrees well with published data [23–25]. It
includes the modes of the upper (Su) and lower (Sl)
atoms of dimers, modes of atoms of the second layer
(S1), and two modes of atoms of the third layer (S2, S '2 ).
After the first cobalt layer (2 Å) had been deposited,
the surface modes of the substrate disappeared, indi
cating that the surface is no longer reconstructed. Vol
ume mode B of silicon monotonically declines with
increasing thickness of the film. At the same time, new
modes arise in the spectrum that are similar to those
observed earlier in the spectra of Co/Si(100)2 × 1 and
Fe/Si(100)2 × 1 twocomponent systems [19–21]. For
example, mode I with a binding energy of 99.61 eV, the
intensity of which slightly rises as the film grows,
belongs to interfacial CoSi silicide covering the silicon
substrate. This mode arises almost simultaneously
TECHNICAL PHYSICS Vol. 56 No. 11 2011
1671
with mode C having a binding energy of 99.01 eV.
Mode C is an analogue of modes in the spectra of Si–
Co and Si–Fe solid solutions and represents Co–Fe–
Si ternary alloy. As has been noted above, the Co/Fe
concentration ratio in this alloy increases with the
thickness of the film, approaching 2 at a thickness of
21 Å, and the concentration of the dissolved silicon,
conversely, decreases. As a result, the intensity
of mode C drops when the thickness exceeds 15 Å. It
should also be noted that volume mode B of silicon
decays much more slowly than in the case of the binary
systems. This means that the film of the Co–Fe–Si
alloy grows according to the island mechanism.
Islands coalesce when Co and Fe layers become about
12 Å thick.
Mode S in these spectra is also of interest. It origi
nates at a film thickness of 6 Å and becomes dominat
ing at a thickness of 21 Å. Its binding energy, 98.74 eV,
corresponds to a monolayer film of silicon having seg
regated on the sample surface. Segregation of silicon
on the surface of the Co–Fe–Si film, as well as on the
surface of the binary systems, is explained by a lower
free energy of the Si surface compared with the free
energy of the alloy [19–21].
Thus, one cannot directly synthesize a film of
Co2FeSi Heusler alloy using reactive epitaxy at a tem
perature equal to, or lower than, 180°C. While the
Co/Fe concentration ratio in the film is close to 2, the
silicon content in it is far below the required value
(25%). Growth at higher temperatures is inadvisable,
since the enhanced island growth deteriorates the film
morphology in this case. Postgrowth annealing of the
resulting continuous film seems to be more promising.
During annealing, the temperature stepwise rose to
300°C. It was found that the postgrowth annealing at
240°C has a considerable influence on the elemental
and phase compositions of the film. The silicon con
tent in it becomes nearly equal to the iron content, and
the Co/Fe concentration ratio remains equal to 2.
Thus, the elemental composition of the film after
annealing totally coincides with the stoichiometric
composition of Co2FeSi compound.
The spectrum of Si 2p electrons, which illustrates
the influence of postgrowth annealing on the phase
composition of the film, is shown at the bottom of the
righthand column in Fig. 1. It is seen that annealing
transforms mode C into mode F of Co2FeSi com
pound, which has a much shorter FWHM (0.29 eV)
and becomes dominant in the spectrum. It should also
be noted that such an FWHM value is nearly coinci
dent with the value of this parameter for volume mode
B of singlecrystal silicon (0.28 eV). This indicates a
high degree of ordering in the structure of the Heusler
alloy film grown.
Let us now turn to the magnetic properties of the
films. The typical spectra of Co 3p and Fe 3p electrons
taken after magnetization in two opposite directions
(↑, ↓) parallel to the surface are presented on the left
of Fig. 2. When the thickness of both Co and Fe layers
1672 GOMOYUNOVA et al.

hν = 135 eV Si 2p
15 Å
C
B
B S
S1
I
Sd
S'2 S2
Su

S
B 21 Å
6Å
Intensity, arb. units

C
C
I
I
S
B

12 Å 240 °C F
B
C
S S
D
I
I

102 101 100 99 98 102 101 100 99 98

Binding energy, eV

Fig. 1. Spectra of photoexcited Si 2p electrons that characterize the growth stages of Heusler alloy Co2FeSi films on the Si(100)2 × 1
surface and the results of decomposition of the spectra.

reaches 9 Å, the spectra I↑(E) and I↓(E) are nearly
coincident. The same is also observed at smaller thick
nesses, which suggests the absence of the remanent
magnetization in the films along the surface. The lin
ear magnetic dichroism in the photoemission of Co 3p
and Fe 3p electrons arises and grows strong at thick
nesses above 13 Å, when systematic distinctions
between the I↑(E) and I↓(E) spectra appear. As is seen
in Fig. 2 for a thickness of 15 Å, the maxima of the
I↓(E) spectra become sharper and shift toward lower
binding energies. The distinctions are highlighted in
the difference curves I↑(E) – I↓(E) shown on the right
of Fig. 2. Thus, in this range of thicknesses, the films
become ferromagnetic and ferromagnetic ordering has
a threshold. Note that the thickness corresponding to
this threshold almost coincides with the thickness at
which islands of Co–Fe–Si alloy coalesce (see above).
The amount of the linear magnetic dichroism can
be characterized by magnetic asymmetry S(E), which
is usually defined as S(E) = [I↑(E) – I↓(E)]/[I↑(E) +
I↓(E)]. The ferromagnetic ordering is usually quanti
tatively estimated through the magnetic asymmetry
amplitude, A = [S(E)max – S(E)min] × 100. In the case
of multicomponent systems, quantity A can be deter

TECHNICAL PHYSICS Vol. 56 No. 11 2011

 FORMATION OF HEUSLER ALLOY CO2FeSi THIN FILMS 1673

(a) (b)
I↑
I↓
Co 3p

Co 3p Fe 3p
Intensity, arb. units

Difference (I↑ − I↓)

Fe 3p 15 Å

15 Å

9Å
9Å

64 60 56 52 48 64 60 56 52 48
Binding energy, eV
Fig. 2. (a) Spectra of Co 3p and Fe 3p electrons taken at two opposite magnetization directions for the films with different thick
nesses and (b) their corresponding difference spectra.

mined for an atom of each element and its value is pro
portional to the mean magnetic moment of respective
atoms [17, 18]. In our case, amplitude A beyond the
threshold monotonically grows, saturating at 18–20 Å,
for both cobalt and iron. Remarkably, the maximal
value of A for iron atoms (21.5%) is noticeably higher
than for the Fe film on the Si(100)2 × 1 surface (16%).
For cobalt atoms, conversely, the magnetic symmetry
amplitude is lower (12%) than for the binary Co/Si
system (18%) [20]. Finally, in the case of the synthesized
Heusler alloy, the value of A for iron atoms is twice as high
as for cobalt atoms. Hence, the magnetic moment of iron
atoms is twice as high as that of cobalt atoms. This finding
is consistent with data obtained in [20].
CONCLUSIONS
Thus, we demonstrated the feasibility of synthesiz
ing Heusler alloy Co2FeSi thin films on the Si(100)2 × 1
surface using reactive epitaxy and subsequent post
growth annealing.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda
tion for Basic Research (project no. 100200632) and
the Russian–German laboratory at the HZB BESSY
storage ring.
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