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Printed in the United States of America Vol. 2, 184–189, 2010

Effect of Mn Substitution for Fe in Multiferroic

BiFeO3: A First-Principles Study
Hai Wang1 , Haitao Huang1
∗ , and Biao Wang2
1
Department of Applied Physics and Materials Research Center, The Hong Kong Polytechnic University, Hong Kong, China
2
School of Physics and Engineering, Sun Yat-sen University, Guangzhou 510275, China

The effect of B-site Mn doping on the structural, electronic, and magnetic properties of multiferroic
BiFe1−x Mnx O3 (0 ≤ x ≤ 0
5) systems has been investigated based on the first-principles calculations
within the density functional theory using virtual crystal approximation (VCA). Our structural param-
eters of pure BiFeO3 agree well with experimental values and previous theoretical results. B-site Mn
doping has significant effect on the electronic by
Delivered andIngenta
magneticto:
properties of BiFeO3 , which are deter-
mined by Fe 3d−O 2p and Fe 3d−Fe 3d interactions. The induced magnetism may beascribed
SCD de l'Universit? d'Artois
to the superexchange interaction of Fe3+ –O2+ –Mn3+ . The total magnetization depends on the Mn
IP : 193.49.62.50
content rather than the volume effect of unit cell. The results may shed some light on the controlling
Tue, 22ofFeb
and tuning of the multiferroic properties 2011
BiFeO 3.
08:00:11
Keywords: First Principles, Multiferroic, BFO.

1. INTRODUCTION current. There have been extensive efforts to reduce the

leakage current through doping a small amount of other
RESEARCH ARTICLE

Recently, magnetoelectric or multiferroic materials have
attracted increasing attention1
2 owing to the rich physical
phenomena resulting from multi-order parameter interac-
tions and promising potential applications on the magnetic
control of ferroelectric polarization and vice versa.3 Indeed,
there are few magnetic ferroelectrics in nature, because
ferroelectricity seems to suppress magnetism.4 Although
some multiferroic composite materials show large mag-
netoelectric effect,5 single phase multiferroic materials
with strong coupling of ferroelectric and magnetic order-
ings are still attractive.6 Among them, BiFeO3 (BFO) is
an interesting multiferroic oxide at room temperature. It
exhibits both ferroelectricity with high Curie tempera-
ture (TC ≈ 830  C) and G-type antiferromagnetic proper-
ties below TN (≈370  C).7 The antiferromagnetic nature
of BFO results in weak magnetism and weak magneto-
electric coupling of BFO.8 Therefore, in order to induce
magnetism, the spiral magnetic structure of BFO should
be destroyed. For example, it can be done by doping of
other ions or by making low-dimensional structures9 in the
form of thin films10 or nanoparticles.11 First principles cal-
culation has predicted that the spontaneous polarization of
BFO single crystal is as high as 100 C/cm2 .12 However,
BFO films often show a polarization one order of magni-
tude lower than the theoretical value due to sizable leakage
∗
Author to whom correspondence should be addressed.
elements at A- (such as Ca, Sr, Ba, Pb,13 and La14 ) or
B-site (such as Cr,15 Sc,16 and Ti17 ).
Here, we focus on Mn-doped BFO, which exhibits a
magnetocapacitance effect18 at room temperature, better
properties in terms of leakage current,19 and better mul-
tiferroic properties.20 In fact, BiFeO3 and BiMnO3 were
found to form a solid solution in the entire composi-
tion range when prepared at a high pressure of several
GPa. BiFe1−x Mnx O3 (BFM) system has an orthorhom-
bic structure in the composition range of 02 ≤ x ≤ 06,
while BiMnO3 -type monoclinic structure appears when
x ≥ 06.21 In the BFM system only when x ≤ 02 was it
found to possess a polar BiFeO3 -type structure and weak
ferromagnetic moment at room temperature. By contrast,
it was reported that the BFO-type rhombohedral structure
can be preserved up to 30% of Mn in the BFM system by
using different preparation methods.18
22 Further increase
in the Mn content up to 50% while maintaining the rhom-
bohedral structure in BFM can be achieved by co-doping
of La at the A-site.23 As Mn content is increased, the lat-
tice constants (a and c and unit cell volume decrease,
while c/a ratio is basically unchanged, suggesting that the
crystal shape remains unchanged. It is well-known that Mn
doped BFO results in a magnetic ordering transition, e.g.,
from the long-range spiral spin antiferromagnetic ordering
to a collinear antiferromagnetic ordering with spins along
c axis. Both the structures before and after the transition

184 Sci. Adv. Mater. 2010, Vol. 2, No. 2 1947-2935/2010/2/184/006 doi:10.1166/sam.2010.1068

Wang et al. Effect of Mn Substitution for Fe in Multiferroic BiFeO3 : A First-Principles Study

are of G-type antiferromagnetic one.24
25 The experimen-
tal data on the effect of Mn-doping, however, seem to
be quite contradictory. On one hand, magnetization reduc-
tion was reported in 5% Mn-doped BFO system.26 On the
other hand, Mn doped BFO system gave rise to a spon-
taneous magnetization that increased with increasing Mn
content.20–22 The enhanced magnetization was attributed to
either the canting of antiferromagnetically ordered spins
by structural distortions27 or the breakdown of the balance
between antiparallel sublattice magnetization of Fe3+ due
to the substitution of metal ions with a different valence.28
Up to now, the optimum composition in the BFM sys-
tem is still unclear. Also unclear are the factors (e.g., vol-
ume effect or local structural distortion) that control the
multiferroic properties of BFM. A comprehensive under-
standing on the effect of Mn doping on structural, elec-
tronic, and magnetic properties of BFO is still lacking
although a dozen of theoretical papers on BFO has been
published.8
12
29
30
Delivered by Pure
SCD de l'Universit?
2. METHOD
Tue, 22 Feb 2011
In this work, a series of B-site Mn-doped hypotheti-
cal crystals BiFe1−x Mnx O3 (x = 0
01
02
03
and 0.5)
were selected for first principles study. The calculations
were performed using highly accurate full-potential lin-
earized augmented plane-wave method (FP-LAPW) as
implemented in WIEN2k code.31 Exchange and correlation
structural, electronic, and magnetic properties of BFM
with different Mn contents using the virtual crystal
approximation (VCA) method. Our calculations presented
here employed the experimental lattice parameters,7
24
where inner atomic coordinates were optimized. The opti-
mizations were performed using the MINI package of
WIEN2k. The rhombohedral structure with space group
R3 (No. 146) was used for VCA calculations. In the rhom-
bohedral structure set, Bi and Fe ions occupy the wyckoff
position 1a (x, x, x, with O ions at 3b (x, y, z. For
the composition of BiFe05 Mn05 O3 , apart from the VCA
method, we have also conducted the calculation based on
a supercell structure consisting of two BFO formula units
with one of the two Fe sites replaced by Mn.
3. RESULTS AND DISCUSSION
3.1. Structure
Ingenta to:
BiFeO3 has a rhombohedral structure with space
d'Artois
group R3c, where Bi atom sits at the origin.7 First of
IP : 193.49.62.50
all, we performed full structural optimization of the lat-
08:00:11
tice parameters and the atomic positions for pure BiFeO .
3
The structural parameters obtained are listed in Table I.
In our calculations, the homogeneous and collinear G-type
antiferromagnetic structure rather than the real spiral spin
structure were used. Similar approximation was also used
in pure BFO.12 Our results are in better agreement with
experimental values than others’ work because of the use

effects are treated within the generalized gradient approxi-
mation (GGA).32 The muffin-tin radii are 2.5, 2.0, 2.0, and
1.6 a.u. for Bi, Fe, Mn, and O, respectively. To control the
size of basis set for the wave functions, Rmt Kmax was set to
8.0. The well-converged basis sets consist of about 1023
LAPW functions and 86 local orbitals chosen for O 2s, Fe
3p, Fe 3d, and Bi 6p states. Integrations in the recipro-
cal space were performed by using improved tetrahedron
method33 and a 12 × 12 × 12 mesh was used to represent
292 k-points in the irreducible Brillouin zone (BZ).
To examine the effect of Mn substitution on the
multiferroic properties of BFO, we have calculated the
RESEARCH ARTICLE
of FP-LAPW method. It is clear that GGA is necessary for
the correct prediction of the equilibrium volume and inner
structural distortions. This is consistent with a conclusion
drawn from the first-principles calculations on BFO.29 In
addition, VASP-PAW-GGA method29 is found to give the
same accurate results.
Table II shows calculated structural parameters of pure
BFO and doped BFM systems with different Mn con-
tents. The results reveal that the addition of Mn ions
induces larger off-center displacements than those in pure
BFO system, suggesting observable structural distortion

Table I. Experimental and calculated lattice constant a (Å), rhombohedral angel  (deg), unit cell volume V (Å3  and atomic fractional coordinates,
where a rhombohedral symmetry was assumed. Here, PAW represents projector augmented wave method. NCPP and USPP stand for norm-conserving
and ultrasoft pseudopotential, respectively.

a  V V /Vexp  Fe (x, x, x O (x, y, z

Exp.a 5.6343 59.348 12460 0.2208 0.5279, 0.3948, 0.9333

Exp.b 5.6301 59.343 12430 0.2207 0.523, 0.422, 0.939
Exp.c 5.6370 59.344 12477 0.2208 0.5244, 0.3972, 0.9344
Exp.d 5.6345 59.348 12461 0.2199 0.5267, 0.9367, 0.3961
Cal.e 5.4590 60.360 11598 −69% 0.2308 0.5423, 0.9428, 0.3980
Cal.f 5.5000 60.180 11500 −69% 0.2310 0.399, 0.541, 0.946
Cal.g 5.6970 59.235 12848 31% 0.2232 0.5342, 0.9357, 0.3865
Cal.h 5.6600 57.320 12043 −33% 0.2210 0.530, 0.936, 0.389
Cal.i 5.6720 59.240 12772 25% 0.2240 0.5353, 0.9367, 0.3882
a
Reference [11], b Reference [47], c Reference [31], d Reference [48]. e References [12, 18], VASP-PAW-LDA. f References [42, 43], ABINIT-NCPP-LDA. g Reference [41],
VASP-PAW-GGA. h Reference [49], PWSCF-USPP-LDA. i Present work, WIEN2k-FP-LAPW-GGA.

Sci. Adv. Mater. 2, 184–189, 2010 185

 Effect of Mn Substitution for Fe in Multiferroic BiFeO3 : A First-Principles Study Wang et al.

Table II. Calculated structure parameters of BFM with different is difficult, as suggested by Bi et al.34 We have also per-
Mn contents (0, 10, 20, 30, and 50%) using VCA method and the
formed the volume optimization on BFM with different Mn
experimental structure parameters of pure BFO.11 BFM50 stands for
BiFe05 Mn05 O3 supercell with one of the Fe sites substituted by Mn. The contents, and the results (not shown here) obtained con-
rhombohedral structure with space group R3 (No. 146) and the exper- firm what is experimentally observed,23 that is, as the Mn
imental structural parameters of BFO were adopted in the calculation. concentration increases, both the lattice constants a and c
Bi and Fe/Mn ions locate at 1a (x, x, x, while O ions at 3b (x, y, z. decrease as well as unit cell volume, while c/a ratio is
0% 10% 20% 30% 50% BFM50 basically unchanged.
Bi1x 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Bi2x 0.5000 0.4996 0.4996 0.4992 0.4990 0.4959 3.2. Electronic Properties
Fe1x 0.2254 0.2259 0.2247 0.2226 0.2216 0.2235
Fe2x 0.7254 0.7261 0.7256 0.7247 0.7263 For pure BFO, the major spin band structure equals to
0.7127
O1x 0.5405 0.5412 0.5391 0.5355 0.5324 the minor spin band structure, due to its antiferromagnetic
0.5315
O1y 0.9399 0.9415 0.9412 0.9431 0.9472 nature. The introduction of Mn into BFO has a significant
0.9257
O1z 0.3888 0.3882 0.3882 0.3878 0.3891 0.3825
effect on the majority spin band structure which brings
O2x 0.0406 0.0441 0.0432 0.0439 0.0474 0.0441
about a larger band-gap while its effect on the minor-
O2y 0.8888 0.8896 0.8903 0.8925 0.8973 0.8808
O2z 0.4399 0.4385 0.4382 0.4365 0.4338 ity spin band structure is negligible. Shown in Figure 1
0.4387
are the calculated band structures of pure BFO and 50%
Mn BFM systems along the high-symmetry directions in
within rhombohedral symmetry. This is consistent with the BZ (only majority spin states are shown). Here, the
Delivered
the experimental observations:24 atomic thermal displace-by Ingenta to: is located at the top of valence band, and is
Fermi level
SCD de l'Universit?
ments increase with increasing Mn content. As Mn content d'Artois
set to 0 eV. For pure BFO, in the valence band (VB), the
increases, the structural distortions decrease onlyIPslightly
: 193.49.62.50
energy band located at the lowest region of [−19
−17] eV
Tue, 22 Feb
without substantial variation. We have recalculated the2011
is 08:00:11
mainly occupied by O 2s states. The bands at about
structure parameters by using the experimental values of 24
−10 eV are Bi 6s states. The upper part of VB around
Mn-doped BFO and have found that the same conclusion [−7, 0] eV is dominated by Fe 3d states mixed with some
can be obtained. The total energy of O 2p and lesser Bi 6p states. The conduction band (CB)
BiFe05 Mn05 O3 calculated by VCA method is lower than region at about 1 to 3 eV is dominated by Fe 3d states. Bi
that of BFM50 supercell with one of the two Fe ions 6p states occupy the region of,3
6 eV. Above 8 eV, strong
replaced by Mn. This indicates that random arrangement mixing occurs among Bi 6p, Fe 3d and O 2p states. The
RESEARCH ARTICLE

of Fe and Mn ions is more energetically favorable. In addi- top of VB is located between  –Z (only 0.015 eV higher
tion, the doping of Mn ions into BFO sharply increases its than the energy at Z), very close to Z, while the bottom
total energy, indicating that introduction of Mn into BFO of the conduction band sits at Z point. Hence an indirect

Fig. 1. Majority spin band structure of pure antiferromagnetic BFO (left panel) and BFM50 (right panel) along high-symmetry directions in BZ.

186 Sci. Adv. Mater. 2, 184–189, 2010

Wang et al. Effect of Mn Substitution for Fe in Multiferroic BiFeO3 : A First-Principles Study

(very close to direct) band gap of 1.06 eV is formed
between the top of the O 2p valence band and the bottom
of the Fe 3d conduction band. The calculated band gap
35
is very close to the experimental value of 1.3 eV and
previous theoretical results.12
36
The electrical properties
of BFO is determined by charge transfers from the occu-
pied O 2p to unoccupied Fe 3d states and d–d transition
between Fe 3d valence and conduction bands.35 Our calcu-
lated band structures agree quite well the results obtained
12
by VASP-PAW method, indicating the latter is as precise
as the FP-LAPW method used in this study. The electronic
band structures of Mn-doped BFO are found to be quite
similar to those of pure BFO.
Figure 2 shows the total density of states of pure and
Mn-doped BiFeO3 . Because Mn doping is hole doping,
the Fermi level of BFM systems should be shifted down-
ward as compared to pure BFO and electrons will fill
holes in the Mn 3d band. For 50% Mn-doped BFM sys-
tem, its spin-up band gap is about 1.0 eV greater than
that in pure BFO, while the spin-down band gap Delivered
remains by atoms.
SCD de
essentially unchanged. As found by Neaton et al.,12 the l'Universit? d'Artois
IP
Fe partial density of states in BFO is quite different for: 193.49.62.50
Tue, 22
the two spin states (spin up and spin down, Fe1 and Fe2, Feb 2011
respectively). From the partial density of states of Fe (not
shown here), one can draw the conclusion that Fe exists
in +3 oxidation state in pure BFO compound, indicating a
d 5 high-spin electronic configuration (detailed explanation
can be found in Ref. [37]). Likewise, Mn also exists in
the +3 oxidation state. Based on the ionic radii of Fe/Mn
contradictory to the experimental results,23 where no big
difference in unit cell volume was found. Since the aver-
age ionic radius of the Fe3+ /Mn3+ couple is closer to that
of Fe3+ ions in pure BFO, both Fe and Mn in BFM system
are likely to be in the +3 oxidation state. Mössbauer and
XPS measurements on La01 Bi09 Fe1−x Mnx O3 revealed that
all Fe ions exist in the +3 oxidation states, and hence Mn
substitution does not introduce any mixed valence into the
system.25 Recently, X-ray absorption spectroscopy39 shows
that mixed valence states of Fe2+ and Fe3+ exist in pure
BFO and Mn-doped BFO. However, since the content of
Fe2+ does not change with the introduction of Mn dopant,
the existence of Fe2+ can be ascribed to oxygen vacancies
rather than Mn doping.39
3.3. Magnetic Properties
Because Fe and Mn are magnetic ions, we first examined
the stability of magnetic ordering of B-site Fe and Mn
Ingenta to:found that the antiferromagnetic ordering is
It is
stable for BFO and it gives a ferrimagnetic structure for
the ground-state of BFM. The calculated total and local
08:00:11
magnetic moment (MM) of BFM with different Mn con-
tents are given in Table III. It is shown that pure BFO
has an antiferromagnetic nature and the total MM is zero,
although local MMs are not exactly equal. Local MM of
Bi is very small since Bi is strongly diamagnetic. Fe ion
has the largest local MM (3.69 B), which is very close
to the experimental value7 (3.75 B) and previous theoret-

in six-coordinate octahedral environment, the combination
2+ 4+
of Fe /Mn ions has an average ionic radius of 0.79 Å,
3+ 38
which is slightly larger than that of Fe . Therefore the
unit cell volume of BFM system with Fe2+ Mn4+ oxida-
tion state should be higher than that of pure BFO. This is
RESEARCH ARTICLE
ical one30 (3.65 B). It is greatly reduced from the formal
value of 5 B for high-spin Fe3+ ions. Similarly, the cal-
culated local MM value of Mn (about 3 B) is also much
smaller than the formal value of 4 B for high spin Mn3+
ions. The reduction of local MM is caused by the strong
Fe/Mn 3d–O 2p hybridization. In addition, O ions also
have a slight MM of 0.07 B, which is the result of the
hybridization between Fe 3d and O 2p states. The oxygen
MM values are about two orders of magnitude smaller than
those of Fe/Mn (see Table II) and hence Fe/Mn ions are
the main source of magnetism in BFM. Previous theoret-
ical calculations have shown that the canting of magnetic
moments was not significantly affected by the presence of

Table III. Calculated total and local magnetic moment (B/f.u.) of

BFM with different Mn contents (0, 10, 20, 30, and 50%) using VCA
method. BFM50 stands for the calculated results based on BiFe05 Mn05 O3
supercell with one of the Fe sites substituted by Mn. The experimental
structural parameters of BFO11 were used for all the calculations.

0% 10% 20% 30% 50% BFM50

Bi1 −0003 +0001 +0003 +0005 +0006 −0004

Bi2 +0003 +0003 +0006 +0008 +0010 −0006
Fe1 +3689 +3598 +3514 +3382 +3175 −3673
Fe2 −3690 −3748 −3812 −3861 −3907 +3142
Fig. 2. Total density of states in pure, 10% and 50% Mn-doped BFO
O1 +0069 +0044 +0035 +0021 +0012 +0112
systems (only the majority spin states are shown, while the minority spin
O2 −0068 −0058 −0062 −0054 −0053 +0033
states of doped BFO are similar to the majority spin states of pure BFO).
Total 0 −0200 −0400 −0600 −1000 −1000
The top of the valence band is set at 0 eV.

Sci. Adv. Mater. 2, 184–189, 2010 187

 Effect of Mn Substitution for Fe in Multiferroic BiFeO3 : A First-Principles Study Wang et al.

oxygen vacancies and no increase in macroscopic magne- Table V. Calculated local magnetic moment (B/f.u.) of BFM with
50% Mn under different unit cell volume. V0 stands for the theoretical
tization due to oxygen vacancies could be found.37 Hence,
equilibrium volume. The total MM equal to +1.00 B/f.u., which is
oxygen vacancies cannot be considered as the main reason independent of the unit cell volume.
40
for the suppression of spin modulation.
Experimentally, there are contradictory reports on the 0.96 V0 0.98 V0 1.0 V0 1.02 V0 1.04 V0
Mn-doping effect on magnetic properties of BFM. It is Bi1 −0009 −0010 −0010 −0011 −0012
reported that the average MM and the ordering tempera- Bi2 −0009 −0008 −0007 −0006 −0005
ture decrease with increasing Mn concentration in BFM Fe1 3535 3558 3577 3589 3600
system.18
24 Naganuma et al.26 reported that 5% Mn- Fe2 −2827 −2875 −2914 −2946 −2977
O1 0091 0097 0101 0106 0111
doping has negligible effect on the magnetization behavior. O2 0024 0026 0028 0029 0031
A general trend of increased magnetization with increasing
Mn content in BFM has also obtained a lot of experimental
supports.21
22 The calculated spontaneous magnetization 4. CONCLUSIONS
(e.g., total MM) of BFM, which increases linearly with
In summary, we have examined the effect of Mn doping on
increasing Mn content, is consistent with this trend.20
22
the structural, electronic, and magnetic properties of BFO
We believe that the total magnetization in BFM comes
system based on first-principles calculations. Our results
from the Fe–O–Mn antiferromagnetic superexchange inter-
confirm the multiferroic properties of Mn-doped BFO sys-
actions, rather than the antiferromagnetic superexchange
tem. DOS and local MM suggest that both Fe and Mn ions
interactions of Fe–O–Fe and Mn–O–Mn, which basically
Delivered by are in +3
Ingenta to:oxidation state. The spontaneous magnetization
cancel the magnetization of BFM system. Similar phe-
SCD
nomenon has been found in LaFeO3 –LaCrO3 systems.41 de l'Universit?
of d'Artois
the system is dependent on Mn content, while indepen-
IP
Recent study on Bi2 FeMnO6 epitaxial thin films also sup-: 193.49.62.50
dent of the unit cell volume and local structural distortions,
ported this mechanism.36 When Mn content Tue, 22 Feb
is 50%, the2011 08:00:11
suggesting the highly stable magnetism. Our results may
be effective for other B-site doped BFO systems.
induced magnetic moment is about 1.0 B per Fe–Mn
couple, which is expected for the antiferromagnetic order-
Acknowledgments: This work was supported by grants
ing between Fe3+ and Mn3+ ions.
from the Research Grants Council of the Hong Kong Spe-
Pure BFO shows a pressure-induced magnetic transi-
42 cial Administrative Region (Project: PolyU 5171/07E) and
tion from high-spin state to low-spin one. Here, we have
from the Hong Kong Polytechnic University (Projects No.:
studied the pressure effect by examining the volume depen-
RESEARCH ARTICLE

G-YF71 and G-YH07).

dence of the total and local MMs in BFM systems with 10
and 50% Mn and the results are given in Tables IV and V,
respectively. It is found that the total MM in BFM is inde- References and Notes
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while those on Bi sites show the opposite trend. In addi- M. Fiebig, Nature 430, 541 (2004).
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netization of BFM systems is very small since its local
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MM is one and three orders of magnitude smaller than Cruz, Y. H. Chu, C. Ederer, N. A. Spaldin, R. R. Das, D. M. Kim,
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11. T. J. Park, G. C. Papaefthymiou, A. J. Viescas, A. R. Moodenbaugh,
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10% Mn under different unit cell volumes. V0 stands for the theoretical 12. J. B. Neaton, C. Ederer, U. V. Waghmare, N. A. Spaldin, and K. M.
equilibrium volume. The total MM equals to −0200 B/f.u., which is Rabe, Phys. Rev. B 71, 014113 (2005).
independent of the unit cell volume. 13. V. A. Khomchenko, D. A. Kiselev, J. M. Vieira, A. L. Kholkin,
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Bi1 0002 0001 0001 0001 −0001
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Bi2 0001 0002 0002 0003 −0003
(2005).
Fe1 3492 +3519 3539 3560 3576
16. S. R. Shannigrahi, A. Huang, N. Chandrasekhar, D. Tripathy, and
Fe2 −3646 −3669 −3689 −3705 −3719
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O1 0041 +0043 0045 0047 0049
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Wang et al. Effect of Mn Substitution for Fe in Multiferroic BiFeO3 : A First-Principles Study

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Tue, 22 Feb 2011 08:00:11
Received: 7 July 2009. Accepted: 24 July 2009.

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