Applied Surface Science 258 (2012) 4945–4951

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Thermodynamic stability, magnetism and half-metallicity of Heusler alloy

Co2 MnX(X = Si, Ge, Sn)(1 0 0) surface
Bo Wu a,b , Hongkuan Yuan a , Anlong Kuang a , Hong Chen a,∗ , Yu Feng a
a
School of Physical Science and Technology, Southwest University, Chongqing 400715, People’s Republic of China
b
Department of Physics, Zunyi Normal College, Zunyi 563002, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: The thermodynamic stability, magnetism and half-metallicity of Heusler alloy Co2 MnX(X = Si, Ge,
Received 23 November 2011 Sn)(1 0 0) surface are comprehensively investigated from the first-principles calculations. The calculated
Received in revised form 21 January 2012 phase diagram indicates that with increasing core electrons of X atoms in Co2 MnX(1 0 0) the CoCo ter-
Accepted 21 January 2012
mination will be faded out of the thermodynamic equilibrium region gradually. Due to the difference of
Available online 31 January 2012
Co X bonding the surface Co and Mn atoms prefer to move towards the slab and vacuum, respectively.
By comparing with the bulk, the surface Co and Mn atomic magnetic moments (AMMs) are enhanced
Keywords:
obviously because of the significant surface d-electronic localization. Further investigations of the par-
Heusler alloy
Structure stability
tial density of states (PDOS) show that the half-metallicity observed in bulk has been destroyed by
Magnetism the surface states in deficient-Mn atomic terminated surface, only the terminations capped pure Mn
Spin-polarization atoms in Co2 MnSi(1 0 0) and Co2 MnGe(1 0 0) surfaces preserve spin-polarization of 100% instead of the
Co2 MnSn(1 0 0) surface, which is a possible explanation for low experimental tunnel magnetoresistance
(TMR) value in Co2 MnSn(1 0 0)-based magnetic tunnel junctions (TMJs).
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
The half-metallic ferromagnets (HMFs) are characterized by a
semiconducting density of states (DOS) for the minority-spin band
and a metallic aspect for the majority-spin band, which brings 100%
spin polarization at the Fermi energy (εF ). As one of the potential
HMFs, Co-based Heusler alloy has attracted much research inter-
est due to its large magnetic moment and high Curie temperature.
It is, therefore, predicted to be a promising candidate for applica-
tions in spin-dependent devices. Previous studies showed that the
Co2 MnSi, Co2 MnGe and Co2 MnSn with L21 structure bear a Curie
temperature seperately above 900 K [1], 1000 K [2] and 800 K [3]
with magnetic moment of about 5 ␮B per unit cell. Experimental
investigations on their tunnel magnetoresistance (TMR) as elec-
trodes in Heusler compounds magnetic tunnel junctions (MTJs)
also revealed significant magnetoresistive effect. Relatively high
TMR ratios of 570% at 4.2 K measured in 2006 [4] has increased
to 630% in 2008 [5], and to 1135% in 2010 [6] for the Co2 MnSi-
based MTJs with MgO substrates. For the Co2 MnGe/MgO/Co2 MnGe
MTJs, the high TMR values of 185% in 2007 [7] and 650% in 2010
[6] at 4.2 K were also reported, which of the latter is already larger
than that of the promising Co2 Cr0.6 Fe0.4 Al- [8] and Co2 FeAl0.5 Si0.5
∗ Corresponding author. Tel.: +86 23 68367040.
E-mail address: chenh@swu.edu.cn (H. Chen).
-based [9] quarternary Heusler MTJs. However, the fact is that
the unexpected TMR steeply drops as temperature increases in
Co2 MnX series Heusler electrodes has been confirmed many times
[4,10–12], and the strong temperature dependence of the current-
perpendicular-to-the-plane (CPP) giant magnetoresistace (GMR) in
the Co2 MnGe-based spin-valve was also observed [13]. Ones have
considered many possible origins, such as nonquasiparticle state
[14], crystal defect [15], atomic disorder [16,17], etc., while up to
now it has not got a decisive result. Recently, the first-principles
calculations found that the half-metallicity observed in bulk can
be lost near the surface or interface because the surface or inter-
face states appeared in minority-spin gap [18], and the positions
of the surface states with respect to εF can be adjusted by doping
effects [19]. It is conceivable that the occurrence of surface states
is a strong probability for steep drop of TMR with the increase of
temperature. Hence, the surface properties of Heusler alloys are
every bit as important as the bulk properties, since they control the
interaction between the substance and the external environment,
and can help us understand the electronic and magnetic proper-
ties of Heusler alloys, which is the precondition for applications in
electrode devices.
Generally, the Co2 MnX alloy with L21 structure cleaved along
Miller indices(1 0 0) crystal direction can create standard epi-
taxial terminated surfaces: CoCo and MnX terminations. These
surfaces are important for envisaged epitaxial growth of Co2 MnX
on MgO(1 0 0) or GaAs(1 0 0), materials to which it is very closely
lattice matched. Considering that a modified artificial termination

0169-4332/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2012.01.125
4946 B. Wu et al. / Applied Surface Science 258 (2012) 4945–4951
Fig. 1. The L21 structure of Heusler alloy.
consisting of pure Mn or Ge element can significantly change the
spin-polarization in Ga-doped Co2 MnGe film [19], the studies on
the modified artificial terminations caped the pure atoms, includ-
ing MnMn and XX terminations (SiSi, GeGe and SnSn termination),
are also focused for extensively searching possible films with the
high spin-polarization. Furthermore, the measured TMR values in
Co2 MnSn-based MTJs [20,21] are extremely small by compared
with that in Co2 MnSi- and Co2 MnGe-based MTJs, implying sig-
nificant surface and interface differences between them. Hence,
a comprehensive theoretical investigation on Co2 MnX[X = Si, Ge,
Sn](1 0 0) surface is crucial to help us understand the hyperfine sur-
face behaviors from the same materials group (the sp-elements of
alloys come from the same main group in periodic table).
2. Calculation methods
In general, the Co2 MnX (X is a sp-element) Heusler alloys bulk
with L21 crystal structure consists of four fcc sublattices. In Wyckoff
coordinates, Co at (1 0 0) and (0.5 0.5 0.5), Mn at (0.25 0.25 0.25),
and X at (0.75 0.75 0.75), see Fig. 1. In the bulk phase, each Mn or X
atoms sitting in an octahedral symmetry position, has 8 Co atoms as
the nearest neighbors, while each Co atom has 4 Mn and X atoms
as the nearest neighbors, formatting the FM-3M space group and
therefore building the novel minority-spin gap by hybridization
between the nearest d states of Co and Mn atoms [22–24].
For the present calculations, the Co2 MnX bulks are firstly
geometry optimized to find the minimal energy structures. Then,
those optimized bulk structures are cleaved along Miller indices
(1 0 0) crystal direction to create all cases of ‘ideal’ epitaxial ter-
minated surfaces: CoCo- and MnX-terminations (X = Si, Ge, Sn).
The modified MnMn and XX terminations are created by substi-
tuted surface atoms for Mn and X atoms in the MnX-terminations.
In our work, all the calculations are performed by Vienna ab
initio Simulation Package (VASP) within the density functional
theory (DFT), and exchange–correlation interaction is described
by Perdew–Burke–Ernzerhof (PBE) generalized gradient approx-
imation (GGA) [25,26]. For properly dealing with electron–ion
interaction, the projector-augmental wave (PAW) pseudopoten-
tial is applied [27]. In the optimizations of the bulks, we firstly
assume all the alloys are ferromagnetic, and the spin-polarization,
the 7 × 7 × 7 mesh of special k-points in the Brillouin zone as well as
the SCF convergence criterion of 10−6 eV are applied. In the case of
the surface calculations, a slab with 11 or 13 atom layers embedded
in the half-infinite vacuum from each side is entirely relaxed. The
thickness of vacuum is sufficiently large so that the middle layers
extremely approach bulk properties. When the positions of atoms
are relaxed, a convergence criterion of 0.02 eV/Å is set. To inves-
tigate the electronic density of states, a refined 0.3 Å grid space
between k-points in Brillouin zone is adopted.
3. Results and discussion
3.1. Structure stability and atomic displacement
Due to the close relation to surface atomic epitaxial growth in
experiment, the thermodynamic stability, information of which is
little available in literature, is also emphasized in present work. In
order to study the relative stability of different atomic terminated
surfaces, the surface free energy as a function of atomic chemical
potentials within the framework of ab initio atomistic thermody-
namics is computed. Since the supercell model is symmetrically
built in our work, its surface free energy can be defined as
1 
= [G − (i Ni )]. (1)
2A slab
i
where  is the surface free energy, Gslab is Gibbs free energy of the
slab, A is the surface area of the supercell each side, and i and Ni
are the chemical potential and the corresponding number of the ith
atom in the slab. Note that each atomic chemical potential is not
independent and the slab is in thermodynamic equilibrium, the
following equilibrium condition would be satisfied with respect to
the Heusler alloy:
2Co + Mn + X = Gbulk , (2)
where Gbulk is the Gibbs free energy of the bulk. Hence, it is easy to
obtain the relation of the surface free energy with respect to Co
and Mn . In order to obtain the phase diagram, we have to confirm
the reasonable range of chemical potential firstly. It is clear that the
higher limits of Co and Mn are the average Gibbs free energy per
atom corresponding to Co and Mn bulk structures:
Co = GCo , Mn = GMn . (3)
Because the stoichiometric relation: 2Co(or Co2 X) + MnX(or
Mn) = Co2 MnX can be satisfied in bulk, the lower limits of Co and
Mn are, respectively, corresponding to:
1
Co = [G − GMnX ], (4)
2 bulk
Mn = [Gbulk − GCo2 X ], (5)
According to above relations, the phase diagram of the various
investigated surface are calculated, see Fig. 2. The label on each
region indicates the termination with the minimal free energy.
It is clearly seen that with increasing Co or Mn , the CoCo or
MnMn termination is more favorable. By comparing with different
Co2 MnX(1 0 0) surface terminations, we find that CoCo termina-
tion in the Co2 MnSn(1 0 0) surface has been excluded from the
thermodynamically stable region, and in the Co2 MnGe(1 0 0) sur-
face the thermodynamically stable region also include less region
of CoCo termination than that in the Co2 MnSi(1 0 0) surface. It
implies that the stable CoCo termination is hard to be accessible
within the limits set by the thermodynamic equilibrium in the
Heusler alloy system with richer core electrons of X atoms. With
increasing core electrons of X atoms, the valence electrons will lose
more itinerant properties, leading to enhancement of the formation
energy. Especially for CoCo-terminations, the contributions from
not only rich Co atoms but also the significant interface interac-
tions, such as dipolar interaction between the surface and interior
layers induced by the reduction of Co atomic coordination num-
ber, will sensitively decide the surface energy related to Co . As a
 B. Wu et al. / Applied Surface Science 258 (2012) 4945–4951
Fig. 2. The calculated phase diagram of the Co2 MnSi (a), Co2 MnGe (b) and Co2 MnSn
(c) (1 0 0) surface terminations. The different shadings show the stable region of
corresponding terminations. The thin dotted lines mark the low and high limits
of chemical potentials, and the thick dashed lines denote the thermodynamically
accessible region.
result, with the increase of core electrons of X atoms to obtain ther-
modynamically stable CoCo-terminations shall require the larger
Co value. This instability of CoCo terminations in similar Heusler
surfaces, such as the Co2 FeSi(1 0 0) [28], Co2 CrGa(1 0 0) [29] and
Co2 MnGe1−x Gax (1 0 0) surface [19], have been also confirmed.
To further understand the surface effects, the investigations
on relaxed atomic positions at the surfaces (S1), subsurface (S2)
and next subsurface (S3) are significative. In Fig. 3, the atomic
displacements with respect to the corresponding ideal posi-
tions (nonrelaxed atomic positions) for various terminations of
Co2 MnX(1 0 0) surface are listed, and the outermost 5 atomic layers
are also presented schematically. The positive and negative val-
ues indicate that the corresponding atoms (in parentheses) move
towards the vacuum and the slab, respectively, and zero implies
that the atom keep its position unmoved. It is evidently seen
4947
Table 1
The calculated atom-resolved magnetic moments and total magnetic moments
(TMM) per cell in Co2 MnX(X = Si, Ge, Sn) bulk.
Bulks Co (␮B ) Mn (␮B ) X (␮B ) TMM (␮B )
Co2 MnSi 0.994 3.072 −0.048 5.012
Co2 MnGe 0.947 3.141 −0.047 4.988
Co2 MnSn 0.923 3.301 −0.079 5.068
that these uppermost layer atoms undergo different displacements
with respect to the nonrelaxed positions. For the CoCo termina-
tions, the surface Co atoms have a larger displacement inward the
slab, while the subsurface Mn and X atoms are closer to the sur-
face layer. On the contrary, in the MnX terminations, the surface
Mn atoms tend to move towards the vacuum region while the X
atoms tend to shift into the slab, which leads to the roughness
of 0.3 Å for Co2 MnSi(1 0 0), 0.13 Å for Co2 MnGe(1 0 0) and 0.16 Å
for Co2 MnSn(1 0 0) surfaces. These behaviors indicate that Co X
bonding is more favorable than Co Mn bonding. It is just due to dis-
tinguishable Co Si, Co Ge and Co Sn bonding, the surface atomic
displacements in the modified MnMn terminations are different.
The surface Mn atom in Co2 MnSn(1 0 0) move toward the slab,
while in the Co2 MnSi(1 0 0) and Co2 MnGe(1 0 0) surface, the surface
Mn atoms have a larger displacement inward the vacuum region.
In the case of XX terminations, the surfaces X atomic displace-
ments gradually decrease from Co2 MnGe(1 0 0), Co2 MnSi(1 0 0) to
Co2 MnSn(1 0 0) surface, which may be attributed to the discrepan-
cies of Co X and Mn X bonding. Except for the CoCo-termination
of Co2 MnSi(1 0 0), the next subsurface atoms are almost limited
around their ideal positions owing to less influences of surface
effects, behaviors of which are extremely close to the corresponding
bulk.
3.2. Surface magnetic behaviors
In Fig. 3, the atom-resolved magnetic moments (AMMs) for
various terminations of Co2 MnX(1 0 0) surface are also gathered.
For convenience of comparisons with bulk values, the calculated
atom-resolved magnetic moments and total magnetic moments
(TMM) per cell in Co2 MnX(X = Si, Ge, Sn) bulk are also listed in
Table 1. We found that the next subsurface atomic moments are
extremely close to the corresponding bulk values, indicating imple-
mented GGA + PAW scheme is reliable to deal with the surface
system with d-electronic atoms. Due to the reduction of atomic
coordination numbers at surfaces, the crystal field is weakened and
the localization of d-electrons atoms are enhanced, resulting in a
rehybridization of the Mn and Co atoms. As a result, the surface
AMMs are obviously enhanced by comparing with the bulk values.
Previous experimental and theoretical investigations for surface
atomic magnetic properties of ternary Heusler alloy surface, such
as Co2 FeSi(1 0 0) [28], Co2 CrGa(1 0 0) [29] and Co2 MnSi(1 0 0) [30],
even the Heusler cluster [31], also reported the similar surface mag-
netic properties. However, for the CoCo-terminations, notice that
the AMM of subsurface Mn is extremely lower than that at the next
subsurface, it may be due to the fact that in CoCo terminations
the narrow average space between the uppermost two atomic lay-
ers enhances the hybridization between surface Co and subsurface
Mn atoms and therefore results in the reduction of subsurface Mn
magnetic moment. Owing to less relaxations of surface Co atoms
in Co2 MnSn(1 0 0) than in Co2 MnGe(1 0 0) and Co2 MnSi(1 0 0), see
Fig. 3(a), the surface Co atoms in Co2 MnSn(1 0 0) present a large
AMM values because of less hybridization. As for remnant MnX,
MnMn and XX terminations, the subsurface Co AMMs mostly
approach their bulk values in magnetism without the remarkable
dependence of various surface X atoms.
4948 B. Wu et al. / Applied Surface Science 258 (2012) 4945–4951
Fig. 3. The atomic displacements with respect to the corresponding nonrelaxed atomic positions and atom-resolved magnetic moments (AMMs) for (a) CoCo, (b) MnX,
(c) MnMn and (d) XX terminations of Co2 MnX(1 0 0) surface. Sj (j = 1, 2, 3) indicate the uppermost three atomic layers and following letters in parentheses denote the
corresponding atoms. See the text for details.
It is a novel phenomenon that in the XX-terminations the pos-
itive surface X AMM values are detected, which is contrary to the
negative surface X AMM in MnX terminations. The early works
by Watson et al. [32,33] indicated that the negative contribu-
tions of sp-electron atoms may originate from the RKKY indirect
exchange mechanism. In the RKKY exchange mechanism, the sp
conduction electrons works as a bridge in transferring magnetic
coupling between local d-electrons [34]. This sp–d mixing interac-
tion also always induces anti-ferromagnetic arrangement between
sp-electrons and d-electrons atoms, which will yield a negative
magnetic contribution. Hence, in MnX and MnMn terminated sur-
faces, the surface and subsurface X atoms are similar to their
behaviors in bulk and always present negative AMMs. While in
XX-terminations, the magnetic coupling between the uppermost
two atomic layers disappear because of the absence of surface Mn
atoms. As a result, we only observe positively localized surface X
AMMs.
3.3. Surface electronic properties
In order to analyze the electronic properties of the surface layer
atoms, the partial densities of state (PDOS) of the outermost three
layer atoms are analyzed. In Fig. 4, the d-PDOS of Co and Mn atoms at
the surface, subsurface and next subsurface with respect to the dif-
ferent surface terminations are schematically graphed, and in the
terminations capped pure X atoms the p-PDOS of the surface X atom
is also plotted. Due to the reduction of surface atomic coordination
number and the interruption of the period crystal field of bulk, the
bulk negative electrostatic potential should rise at surface to match
to the vacuum zero potential level, resulting in lots of gathered
valence electrons at surface. Hence, in CoCo terminations, we can
see that the minority-spin bands of surface Co atoms are occupied
by these valence electrons and the minority-spin gaps observed in
bulk are also filled. Meanwhile, as a result of the enhancement of
hybridization between the surface Co and subsurface Mn, which
is induced by the sharply contracted average bond length of the
uppermost interlayer atoms, the majority-spin band of subsurface
Mn and next subsurface Co atom is pushed to high energy to serve
the reduction of exchange splitting. Unlike the CoCo terminations,
in the MnX terminations the surface Mn atoms shift towards vac-
uum and present large localicity to increase the exchange spitting
of d-electrons, inducing the movement of majority-spin peaks of
surface Mn atoms towards lower energy. While for the subsur-
face Co and next subsurface Mn atoms, because of less influence
from the surface effect, their electronic structures are very close to
corresponding bulk aspect.
As far as modified MnMn and XX terminations are concerned,
except for some similar surface behaviors to the MnX termination,
such as d-band shifts of surface Mn in MnMn terminations and
the small spin-polarizations of surface X atoms in pure X atoms
termination, a prominent distinction from the MnX terminations
is that the minority-spin peaks of surface Mn and subsurface Co
atoms observed in MnX terminations have been cleared away in
the MnMn terminations and suffer a remarkable enhancement in
XX-terminations, respectively. Further analyses reveal that these
small peaks pinned in minority-spin gap rapidly damp in the sub-
surface and finally disappear in the next subsurface or the deeper
layer. We deduce that these small peaks characterized by d-orbitals
are derived from surface states. In the terminations capped pure X
atoms, lots of sp-electrons are gathered at surface and intensely
polarized. According to RKKY indirect exchange mechanism, these
conduction sp-electrons can continually exchange with local d-
electrons of the nearest transition metal and works as a bridge in
hybridization between local d-electrons. As a result, in the XX ter-
minations the minority-spin gaps of the subsurface Co atoms are
filled entirely because of the larger exchange interaction, while in
 B. Wu et al. / Applied Surface Science 258 (2012) 4945–4951 4949

Fig. 4. The partial density of states (PDOS) of various atomic terminations for (a) Co2 MnSi(1 0 0), (b) Co2 MnGe(1 0 0) and (c) Co2 MnSn(1 0 0) surface. The lines and the shadow
region indicate atomic PDOS of the surface and bulk, respectively, and the subtitles mark atom terminations. Sj (j = 1, 2, 3) indicate the uppermost three atomic layers and
following letters denote the corresponding atoms.

the MnX terminations this effect should be decreased with seldom
surface X atoms, even disappear as surface X atoms are substituted
for Mn atoms entirely. In this sense, it seems that these small peaks
pinned the minority-spin gap are closely related to the rich surface
X atoms.
For further clarifying the origins of surface states, the Mn-void
and X-void terminations, which are created, respectively, by substi-
tuted surface Mn and X atoms for the vacancy in MnX terminations,
are investigated sequentially by using the same calculated param-
eters. As a representative case, in Fig. 5, the d-PDOS of surface Mn
4950 B. Wu et al. / Applied Surface Science 258 (2012) 4945–4951
Fig. 5. The d-PDOS of surface Mn and subsurface Co atoms, as well as p-PDOS of surface Sn atom in Mn-void and Sn-void atomic terminations of Co2 MnSn(1 0 0) by comparing
with that of the corresponding MnMn and SnSn terminations. Sj (j = 1, 2) indicate the uppermost two atomic layers and following letters denote the corresponding atoms.
and subsurface Co atoms, as well as p-PDOS of surface Sn atom
in Mn-void and Sn-void termination of the Co2 MnSn(1 0 0) surface
are plotted. The expected shifts of spin-majority bands of surface
Mn atoms towards the lower energy orientation and extremely
small spin-polarizations of surface Sn atoms are observed due to
increasing surface atomic localization. For the subsurface Co atom,
the focused spin-minority gaps in MnMn-termination has been fill
by surface states in Mn-void terminations, and the peaks pinned
the spin-minority gap of the bulk are also significantly enhanced
in Sn-void termination. The absence of half of surface Mn or Sn
atoms shall expose partial subsurface Co atoms to the vacuum and
enforce them to behave like surface Co atoms, of which the spin-
minority band is occupied by lots of surface valence electrons and
the spin-minority gap is destroyed as mentioned before. Hence, the
surface states are mainly derived from the d-orbitals of the subsur-
face transition metal atoms displace of the surface atoms, and to
be significant when the nearest magnetism-coupled atoms of the
subsurface atom are lessen. In such mechanism, the sp-electrons of
surface X atoms mainly play a ‘bridge’ role in magnetic exchange
between transition metal atoms. The deficient-Mn terminated sur-
face rather than the deficient-X terminated surface tend to yield
the surface states in the spin-minority gap.
High spin-polarization plays an important role in HMFs for
applications in the spindependent devices. The HMF film with a
Fermi level situated in minority-spin gap can present ideal spin
polarization rate of 100% and be promising materials for appli-
cations. Due to the evident differences in atomic radii and core
electrons of X atoms in the Co2 MnX bulks and surfaces, with the
increase of the inner-shell electrons of X atoms, we can be seen that
the Fermi level is posited near, even under the bottom of minority-
spin gap. Especially, in the MnMn-termination of Co2 MnX(1 0 0)
surface, without the influences of surface states, the Fermi level
always stands in the middle of minority-spin gap of the surface
and next subsurface Mn atoms. However, considering the subsur-
face Co atom, the Fermi level is just above, near and under the
hemline of the corresponding minority-spin gap for Co2 MnSi(1 0 0),
Co2 MnGe(1 0 0) and Co2 MnSn(1 0 0), respectively. In this sense, the
MnMn-terminations of Co2 MnSi(1 0 0) and Co2 MnGe(1 0 0) present
more superiorities than that of Co2 MnSn(1 0 0) for applications in
ferromagnetic electrodes because of ideal spin-polarization. In fact,
Co2 MnSn(1 0 0) film deposited on MgO(1 0 0) substrates presented
very small TMR value (less than 5% at 5 and 300 ◦ C), and its cell
magnetic moment which mainly derives from interface local mag-
netism was less than 5 ␮B [21]. A possible comprehension is the
poor half-metallic stability in bulk and surface phase of Co2 MnSn.
Because its εF locates at the edge of the minority-spin gap, the
effects related to temperature, such as depositing conditions, crys-
tal defect and atomic disorder, easily lead to significant changes in
electronic and magnetic properties, even the sharp reduction of the
spin-polarization ratios.
4. Conclusion
By using the first-principles calculations within density func-
tional theory (DFT), the thermodynamic stability, atom-resolved
magnetism and electronic structure of various atomic termina-
tions in Co2 MnX(X = Si, Ge, Sn)(1 0 0) surfaces are systematically
studied. The calculated equilibrium phase diagram indicates that
with increasing the core electrons of X atoms of Co2 MnX(1 0 0),
the CoCo-termination will be gradually faded out of the thermo-
dynamic equilibrium region. Due to the discrepancies between the
nearest Co X bonding and Co Mn bonding, we can evidently see
that the surface Co and Mn atoms, respectively, move towards the
slab and vacuum. By comparing with the bulk, the surface Co and
Mn AMMs are enhanced obviously owing to the rigorous local-
ization of surface d-electronic atoms, while the subsurface AMMs
are very close to the bulk values except for the CoCo-terminations.
With the increase of core-electrons of X atom in Co2 MnX(1 0 0), the
Fermi level will gradually shift towards low-energy orientation. The
half-metallicity observed in bulk has been destroyed by the surface
states in deficient-Mn atomic terminated surface, only the termi-
nations capped Mn atoms in Co2 MnSi(1 0 0) and Co2 MnGe(1 0 0)
 B. Wu et al. / Applied Surface Science 258 (2012) 4945–4951
preserve the half-metallicity instead of the Co2 MnSn(1 0 0) surface,
which is a possible explanation for low experimental TMR value in
Co2 MnSn(1 0 0)-based TMJs.
Acknowledgements
This work was supported by the National Natural Sci-
ence Foundation of China (11175146 and 10904125), Natural
Science Foundation of Chongqing (CSTC-2008BB4253 and CSTC-
2011BA6004) and Science and Technology Research Foundation of
Zunyi (ZSKHSZ-201008).
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