Computational Materials Science 50 (2011) 1175–1178

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Computational Materials Science

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

A first principles study on the full-Heusler compound Mn2CuSb

Xiao-Ping Wei, Jian-Bo Deng, Shi-Bing Chu, Ge-Yong Mao, Lei-Bo Hu, Ming-Kun Yang, Xian-Ru Hu ⇑
Department of Physics, LanZhou University, Lanzhou 730000, 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: Electronic structure calculations from first-principles are employed to design half-metallic ferrimagnets
Received 14 October 2010 susceptible of finding applications in spintronics. The electronic structure and magnetism properties of a
Received in revised form 8 November 2010 new Mn-based Heusler alloy Mn2CuSb are studied and both possible L21 structures (CuHg2Ti and AlC-
Accepted 14 November 2010
u2Mn types) are taken into account. It is found that the CuHg2Ti-type structure is energetically more
Available online 8 December 2010
favorable than the AlCu2Mn-type structure and presents half-metallic character. Calculations show that
their total spin moment is 2.00lB for a wide range of equilibrium lattice constants and the total spin
Keywords:
magnetic moment is attributed mainly to the two Mn atoms. Simultaneously, the small spin magnetic
Heusler alloy
Half-metal
moments of Cu and Sb atoms are parallel and the compound is ferrimagnets. The total spin moment
Ferrimagnet mainly origins from the antiparallel configurations of the Mn partial moments. The CuHg2Ti-type
Electronic structure Mn2CuSb alloy keeps a 100% of spin polarization of states at the Fermi level. Our findings suggest that
Magnetic properties Mn2CuSb may be a promising material for future spintronic applications.
Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction d subshell. Different electronic configurations may have influence

on the site preference and electronic structure. Recently, Li et al.
During the past decade, increased interests in the field of [20] and Wei et al. [21] have studied the electronic structure of
magnetoelectronics or spintronics have intensified research on Mn2CuAl and Mn2CuGe theoretically. The spin moments of the
the so-called half-metallic materials, which are normal metals for Mn atoms in Mn2CuAl and Mn2CuGe being in antiparallel align-
one spin direction and semiconductors for the other and thus elec- ment have been reported.
trons near the Fermi level are of a unique spin character [1,2]. The half-metallic antiferromagnetism [22] and ferrimagnetism
Among these materials, the case of the Mn-based Heusler alloy [21] character is presented with a small contraction of the equilib-
with half-metallicity attracts much attention. Mn2VAl was the first rium lattice. Until now, the Full-Heusler alloy containing the sp
half-metallic material predicted from band theory calculations in element Sb has not been reported yet. The lack of experimental re-
Mn-based Heusler alloy [3,4]. In succession, Mn3Ge, Mn2FeZ ports are due to the difficulty of synthesizing the stoichiometric
(Z = Al, Sb) [5,6] and Mn2CoZ (Z = Al, Si, Ge, Sn, and Sb) [7–10] have compositions. Nonetheless, the theoretical investigations for the
also been predicted as half-metallic materials by theoretical and compound are still desirable and helpful for finding new functional
experimental studies. Meanwhile, a new ferromagnetic shape materials.
memory alloys (FSMAs) Mn2NiZ (Z = Ga, In, Sn, Sb, Al) [11–13] In this paper, site preference, the electronic structure and mag-
and MnNiIn [14–16] have been reported as newly discovered netic properties of the Full-Heusler Mn2CuSb alloy are studied by
FSMAs. All these make Mn2-based Heusler alloys a promising fam- first-principles calculations and the stable structure is determined.
ily for investigating new materials and phenomena such that peo-
ple take great efforts in searching for new functional materials in
this series of alloys. 2. Method of calculations
Until now, the site preference and electronic structure of Mn2YZ
(Y = V, Cr, Mn, Fe, Co, Ni) [17–19] have been thoroughly investi- The electronic density of states (DOS) and the magnetic proper-
gated. However, the properties of Mn2CuZ, which has Cu as the Y ties calculations are implemented using the full-potential local-
atom, are still unclear. It is well known that Cu atom has a filled orbital minimum-basis band structure scheme (FPLO) [23,24].
d subshell and leaves the 4s with one electron. This is different We use the scalar relativistic formulation and default initial spin
from some other 3d elements like Fe or Co, which has a unfilled splitting. The exchange-correlation potential by Perdew and Wang
is chosen in the local spin density approximation (LSDA) [25,26].
The self-consistent potential calculations are performed on a
⇑ Corresponding author. 30  30  30 k-mesh which corresponds to 1368 k-points in the
E-mail address: [email protected] (X.-R. Hu). irreducible Brillouin zone. The convergence of the self-consistent

0927-0256/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.commatsci.2010.11.017
1176 X.-P. Wei et al. / Computational Materials Science 50 (2011) 1175–1178

iterations is checked with respect to both the density (106 in code 0.5
specific units) and the total energy (108 Hartree). Mn2CuSb
AlCu2Mn-type
3. Results and discussions 0.4 CuHg2Ti-type

3.1. Site preference and lattice constant

0.3
Full-Heusler alloys are represented in general by the generic for-

E-E0(eV)
mula X2YZ, where X and Y are transition metal elements and Z is an
s–p element, which has four unique crystal sites, i.e. A(0, 0, 0),



0.2
B 14 ; 14 ; 14 , C 12 ; 12 ; 12 and D 34 ; 34 ; 34 in Wyckoff coordinates as shown
in Fig. 1, Usually, the Full-Heusler compounds crystallize in L21
structure, which can be looked on as four interpenetrating face-
centered-cubic (fcc) lattices and have two possible structures: the 0.1
AlCu2Mn and CuHg2Ti-type structures. The AlCu2Mn-type Full-
Heusler compound has the structure whereby X atoms occupy
the (A, C) sites, while another Full-Heusler compound with the
0
CuHg2Ti-type structure has the (A, B) sites located by X atoms. The 5.7 5.8 5.9 6 6.1 6.2
site preference of the X and Y atoms is influenced by the number Lattice constant(Å)
of their valence electrons in the complicated crystallization process.
Fig. 2. Calculated total energy for Mn2CuSb compound as functions of lattice
Since there is always a degree of anti-site disorder in practical
parameters for both the AlCu2Mn and CuHg2Ti-type structures in the AFM state. The
applications, which may strongly affect the half-metallic properties zero of the energy has been chosen as the energy of the global equilibrium lattice
[27] the study on the site preference may be meaningful for syn- constant.
thesization of new half-metallic Heusler alloys.
In the process of studying the site preference of Cu atom in
Mn2CuSb alloy, it is found that, from neutron diffraction and 1.0 Mn2CuSb−band ↑
NMR studies [28,29] those elements with more valence electrons Mn2CuSb−band ↓

are favorable to occupy the (A, C) sites, with fewer ones occupying 0.0
B sites [30]. To verify this rule, some relevant calculations are per-
Energy εn(k) [eV]

formed. Firstly, we calculate the results of energy optimization for −1.0

both types of Full-Heusler structures. The optimized energy curves
and a graph of total energy corresponding to lattice constant for −2.0
the two types of Full-Heusler structures is plot (Fig. 2). The results
show that the equilibrium lattice constant for the CuHg2Ti and the −3.0
AlCu2Mn-type structures are 5.96 Å and 6.00 Å, respectively, and
the energy of the latter is higher than that of the former, which re- −4.0
veals that CuHg2Ti-type structure is energetically more favorable
for this specific lattice range. As a result, the two Mn sublattices −5.0
prefer to occupy A and B sites instead of the A and C sites. The rea- Γ X W K Γ L W U X
son is that the Cu atom has more valence electrons than the Mn
Fig. 3. Majority-spin and minority-spin band structure for CuHg2Ti-type Mn2CuSb
atom, and they tend to occupy the C site. The following calculations alloy under the equilibrium lattice constant 5.96 Å.
are based on the CuHg2Ti-type structure and calculated theoretical
equilibrium lattice constant is used.

metallic intersections at the Fermi level, indicating a strong

3.2. Electronic structure of Mn2CuSb
metallic nature of the spin-down electrons. However, the spin-up
band structure exhibits a band gap indicating semiconducting
The band structure of Mn2CuSb compound with CuHg2Ti-type
nature. Therefore, our results reveal that Mn2CuSb alloy exhibits
structure for the spin-up and the spin-down electrons is shown
half-metallic properties.
in Fig. 3. It is evident that the spin-down band structure has
The total and atom-resolved density of states per unit cell for
Mn2CuSb alloy and for a special lattice constant a = 5.96 Å is shown
in Fig. 4. We choose the spin-up states as positive value and
spin-down states as negative one for better comparison of spin
magnetic moments on spin-up and spin-down electrons. For the
investigation of Mn2CuSb alloy under the specific lattice constant,
there is a real gap in the spin-up states for the Full-Heusler alloy,
and the width of the band gap is 0.46 eV. The Fermi level just falls
within the gap in the spin-up band indicating semiconductor prop-
erties, which keeps a perfect 100% spin-polarization of the states at
the Fermi level, partially, because of the large value of the spin-
down density of state at the Fermi level.
The gap is created due to the large exchange splitting of both
the Mn and Cu atoms as can be seen in Fig. 4. The splitting for
the two spin channels is consistent compared to that of Mn atoms
Fig. 1. Schematic representation of the L21 structure. The unit cell has four crystal resolved density of state. In reality, this splitting upset in the two




sites as the basis: A(0,0,0), B 14 ; 14 ; 14 C 12 ; 12 ; 12 , and D 34 ; 34 ; 34 in Wyckoff coordinates. spin channels does not reveal physical difference. As is known,
 X.-P. Wei et al. / Computational Materials Science 50 (2011) 1175–1178 1177

10 10
Total a=5.96(Å)
5 a=5.75(Å)
0 5
-5
-10 0
Mn(A)
3 3d
0 -5
-3
Mn(B) -10 Mn2CuSb
3 3d 10
0 a=6.10(Å) a=6.15(Å)
-3 5
Cu(C)
3 3d 0
0
-3 -5
1
Sb(D)
5p
-10
0 -8 -6 -4 -2 0 2 -8 -6 -4 -2 0 2
Energy EF(eV)
-1
-6 -4 -2 0 2
Fig. 5. Total DOS for the Mn2CuSb alloy as a function of the lattice constant. Black
Energy EF(eV) color corresponds to spin-up and red color line spin-down electrons. (For
interpretation of the references to color in this figure legend, the reader is referred
Fig. 4. The calculated total and atom resolved density of states for the Mn2CuSb to the web version of this article.)
Full-Heusler alloy. The arrows " and ; assign states of opposite spin that are spin-up
and spin-down states. The zero energy value corresponds to the Fermi level EF.
of four different lattice constants ranging between 5.75 Å and
the gap in Heusler alloys should be traced to the covalent hybrid- 6.15 Å. The total density of states present only marginal changes
ization between the lower-energy d states of the higher-valence with the lattice constant, and the Fermi level is shifted lower in en-
transition metal atom and the higher-energy d states of the ergy with respect to the gap, while the opposite occurs when we
lower-valence transition metal atom. The bonding hybrids are expand the lattice constant, which behaves as in a rigid-band mod-
localized mainly at the higher-valence atom site, while the anti- el. Thus, we can obtain the range of lattice constant for which they
bonding states are mainly located at the lower-valence atom site exhibit half-metal. Our findings show that the Mn2CuSb alloy is
[31,32]. Here, the unoccupied and occupied states consist mainly half-metallic between 5.76 and 6.14 Å, while the metallic behavior
of Mn characters, while for the occupied states the Cu and Sb atoms is found to be 6.15 Å. The width gap indicating half metallic is also
also have enough contributions. Thus, the large exchange splitting shown in Table 1. Thus, Mn2CuSb is probably the ideal case for
between the occupied states of one spin direction and the unoccu- experimentalists to try to synthesize.
pied states of the opposite spin direction for both Mn and Cu atoms
is added up to open the gap, because these peaks at the edge of the 3.3. Magnetic properties of Mn2CuSb
gap are exactly the same as that in Sb density of state. These peaks
(bonding and antibonding-peak) of total density of states at the The preceding discussion is concerned with the electronic struc-
Fermi level can be tracked back to the eg  t2g splitting in cubic ture and the formation of the band gap. We now turn to the mag-
crystal field, and it was assumed that the eg is doublet and t2g is netic properties. To discuss the behavior of the spin magnetic
triplet degenerate states. It is evident that the total electronic moments in Mn2CuSb alloy, we have given both the total and
states at the Fermi level mainly consist of 3d states of Mn(A) and atom-resolved spin moments for the alloy corresponding to lattice
Mn(B), which have a large overlap with the antibonding and bond- constants in Table 1, where half-metallicity is present within a cer-
ing states of Mn atoms in energy, indicating that a hybridization tain lattice constant range. This is also verified by the calculated to-
mainly occurs between Mn(A) and Mn(B). Thus, the gap mainly tal spin moments. Each Cu atom has a spin moment around 0.03
originates from the hybridization of the 3d states of the two Mn to 0.00lB, which only has little change. Mn atoms’ magnetic mo-
atoms. ments continuously increase when the lattice constant is expanded
Our results up to now concern only the specific lattice constant in the whole scale, and their magnetic moments show an opposite
5.96 Å. The question is whether Mn2CuSb alloy present half-metal- change behavior. While the Cu and Sb atoms magnetic moments
licity only for the specific lattice constant. It is well known that in a gradually increase as the lattice constant expands. Therefore, the
non-equilibrium process such as melt-spun and ball milling, the total magnetic moments keep the fixed value with half metallicity.
strain may be quite large, which makes the lattice parameter devi- Each Mn atom has four Cu atoms (and four Sb atoms) as first
ate from the ideal crystal structure. Moreover, the compound may
be synthesized as films by the molecular beam epitaxy (MBE) or
other methods and the strain induced by the substrate cannot be Table 1
escapable. Therefore, it is meaningful to study the relationship be- Calculated total and atom-resolved spin magnetic moments in lB and gap width for
CuHg2Ti-type structure as a function of the lattice parameter.
tween the magnetic property and the lattice constant for a given
material from both theoretical and technical standpoints. In order a (Å) A B C D Total Gap width (eV)
to see how the gap behaves and the differences of the position of Mn Mn Cu Sb
the Fermi level changing with the lattice parameters, we start from 5.70 0.36 2.35 0.00 0.00 1.99 –
the 5.96 Å lattice parameter and compress the lattice parameter in 5.80 0.62 2.61 0.01 0.00 2.00 0.18"
a uniform way. 5.90 0.91 2.88 0.02 0.01 2.00 0.36"
Here, we have implemented the calculations to investigate the 6.00 1.19 3.13 0.03 0.03 2.00 0.49"
6.10 1.44 3.35 0.05 0.04 2.00 0.39"
dependence of magnetic moments for lattice constant. In Fig. 5,
6.20 2.43 3.54 0.03 0.07 1.22 –
we present the total density of state for Mn2CuSb for an ensemble
1178 X.-P. Wei et al. / Computational Materials Science 50 (2011) 1175–1178

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