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Effect of alkaline earth metal doping on thermal, optical, magnetic and dielectric properties of

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2009 J. Phys. D: Appl. Phys. 42 065004

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IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 42 (2009) 065004 (8pp) doi:10.1088/0022-3727/42/6/065004

Effect of alkaline earth metal doping on

thermal, optical, magnetic and dielectric
properties of BiFeO3 nanoparticles
B Bhushan1 , A Basumallick2 , S K Bandopadhyay3 , N Y Vasanthacharya4
and D Das1,5
1
UGC-DAE Consortium for Scientific Research, Kolkata Centre III/LB-8, Bidhannagar,
Kolkata 700 098, India
2
Department of Metallurgy and Materials Engineering, BESU, Shibpur, Howrah 711103, India
3
Variable Energy Cyclotron Centre, 1/AF, Bidhannagar, Kolkata 700 064, India
4
Solid State and Structural Chemistry Unit, IISc, Bangalore-560 012, India
E-mail: [email protected]

Received 18 November 2008, in final form 6 January 2009

Published 3 March 2009
Online at stacks.iop.org/JPhysD/42/065004

Abstract
Substrate-free pure-phase BiFeO3 (BFO) nanoparticles doped with alkaline earth metals
(Ba, Sr and Ca) have been synthesized by a sol–gel route and their thermal, optical, dielectric
and magnetic properties are discussed. The characteristic structural phase transitions of BFO
nanoparticles are found to occur at much lower temperatures. A reduction of the Néel
temperature has been observed in the doped samples in comparison with the pristine one,
whereas the band gap shows a reverse trend. Iron was found to be only in the Fe3+ valence
state in all the doped samples. Magnetoelectric coupling is seen in our samples. Weak
ferromagnetism is observed at room temperature in all of the doped and undoped BFO
nanoparticles with the largest value of coercive field ∼1.78 kOe and saturation magnetization
∼2.38 emu g−1 for Ba and Ca doped BFO nanoparticles, respectively.

1. Introduction distorted perovskite structure with space group R3c. Besides

the robust multiferroic properties, BFO is also an environment-
Multiferroics may be classified as materials in which two friendly material. This has stimulated research on fabrication
or more of the primary ferroic properties are combined of BFO-based devices [9–11] to address the growing concern
in the same phase. For wider technological applicability about the toxicity of commercially available ferroelectric
these ferroic properties should have overlapping temperature devices, which are mostly made up of lead containing
windows [1, 2]. Multiferroics have immense application in materials [12].
data storage, spin valves, spintronics, quantum electromagnets, In spite of intense study, little effort has been made towards
microelectronic devices, etc [3, 4]. There has been a renewed the synthesis of substrate-free nanoparticles of single phase
interest in the research activities on multiferroics after recent BFO. Most of the published works on BFO have reported
theoretical breakthroughs in understanding the co-existence of the presence of impurity phases in the samples [13, 14]. Low
magnetic and electrical ordering in this class of materials [5, 6]. levels of impurities may not affect the structural and magnetic
BiFeO3 (BFO) is one of the most widely studied multiferroic properties; however, dielectric, optical or electrical properties
materials as it shows ferroelectricity with a high Curie can get altered by even a small amount of impurity. It stresses
temperature (TC = 830 ◦ C) and G-type antiferromagnetic the need to develop synthetic routes to obtain phase pure BFO
order below the Néel temperature, TN = 370 ◦ C with a compounds. Furthermore, a number of challenges remain to be
long-range cycloidal spin arrangement of wavelength 62 nm overcome for the technological applicability of BFO and they
incommensurate with the lattice [7, 8]. It has a rhombohedral include weak magnetic characteristics, lower magnetoelectric
coupling coefficients, wide differences in ferroic transition
5 Author to whom any correspondence should be addressed. temperatures (TC and TN ) and a high leakage current. In

0022-3727/09/065004+08$30.00 1 © 2009 IOP Publishing Ltd Printed in the UK

J. Phys. D: Appl. Phys. 42 (2009) 065004 B Bhushan et al

order to overcome these problems, several researchers have

attempted to modify the Bi or Fe sites of BFO by substitution
with different transition metal ions or paramagnetic rare
earth metal ions to get enhanced magnetic, electric and
magnetoelectric properties [13–16]. However, there are only a
few reports on BFO substituted with non-magnetic alkaline
earth metal ions having ionic radius comparable with that
of Bi ions [17, 18]. In this work, we address these crucial
issues by synthesizing pure-phase BFO nanoparticles doped
with Ca, Sr and Ba metal ions and carrying out detailed
studies to comprehend the thermal, optical, magnetic and
dielectric properties of these systems. The motivation for
synthesis of alkali-earth doped BFO nanoparticles comes
from the interesting magnetic behaviour exhibited by BaFeO3 ,
SrFeO3 and CaFeO3 [19–21]. Clearly, iron is in 4+ states in
these perovskites. CaFeO3 exhibits metal to semiconductor
transition at a temperature close to room temperature. It
also shows charge disproportionation transitions for iron
at lower temperatures. SrFeO3 shows different types of
magnetoresistance effects for different oxygen stoichiometries
at different temperatures while BaFeO3 is itself a multiferroic.
A sol–gel method has been employed for the synthesis
of nanosized, phase pure, single crystalline BFO ceramics.
We have also prepared samples where 5% Bi3+ ions (ionic
radius = 1.03 Å) of BFO were substituted with Ba2+ ,
Sr2+ and Ca2+ ions having ionic radii 1.35 Å, 1.18 Å
and 1.00 Å, respectively, the chemical composition being
Figure 1. XRD patterns of (a) BFO, (b) BCFO, (c) BSFO and
Bi0.95 X0.05 FeO3 (X = Ba, Sr, Ca). These samples are
(d) BBFO. ∗ represents impurity phase.
designated as BBFO (Ba doped BFO), BSFO (Sr doped
BFO) and BCFO (Ca doped BFO). These prepared samples
in a Seiko EXSTAR model TG6000 and DSC6300 system,
were subsequently characterized by a number of techniques
respectively, while heating the sample in air. FTIR data of all
including x-ray diffraction (XRD), transmission electron
the samples were recorded with a Perkin Elmer spectrum GX
microscopy (TEM), selected area electron diffraction (SAED),
spectrometer in the mid-IR frequency range with a resolution of
energy dispersive spectroscopy (EDS), thermo gravimetric and
4 cm−1 . UV–vis absorption measurements were recorded on a
differential thermal analysis (TG-DTA), differential scanning
Shimadzu UV-1601PC spectrophotometer. Room temperature
calorimetry (DSC), UV–vis spectroscopy, dielectric constant
Mössbauer measurements were carried out in a standard PC
measurement, 57 Fe Mössbauer spectroscopy and vibrating
based set-up consisting of a 1024 channel MCA card, working
sample magnetometry (VSM).
in the constant acceleration mode. A 10 mCi 57 Co in Rh matrix
was used as the source. The system was calibrated with a high
2. Experimental details purity iron foil of thickness 12 µm. A least squares fitting
program LGFIT2 was used to fit the experimental data [23].
We employed a sol–gel technique, as reported by Park et al [22] All the magnetization data were taken using a Lakeshore
with some modifications to prepare BFO and doped BFO model 7400 series vibrating sample magnetometer in the field
samples. A 1 : 1 molar ratio of Bi(NO3 )3 ·5H2 O and Fe(NO3 )3 · range −10 to 10 kOe at room temperature. The dielectric
9H2 O were added successively to ethylene glycol. In the constant of all samples was measured on an LCR meter
case of the substituted samples a 0.95 : 1 : 0.05 molar ratio of (TEGAM USA, model 3550). An Ag–pellet–Ag capacitor
Bi(NO3 )3 · 5H2 O, Fe(NO3 )3 · 9H2 O and the corresponding salt was used for the dielectric constant measurements at room
(Ba(NO3 )2 for BBFO, Sr(NO3 )2 for BSFO and CaCl2 · 2H2 O temperature. To demonstrate the magnetoelectric coupling
for BCFO) were added to the solvent. The resulting mixture in our samples, the dielectric constant was also measured at
was stirred vigorously at 80 ◦ C for 1 h to obtain the sol. It different applied magnetic fields at a frequency of 100 Hz at
was then left to dry overnight at 80 ◦ C in an oven. The gel room temperature.
was preheated at 400 ◦ C and was finally annealed at 550 ◦ C
for 30 min. The structural analysis of the prepared samples
3. Results and discussions
was carried out by a Philips x-ray diffractometer with a cobalt
target (λ = 0.178 897 Å). The morphological characterization 3.1. Structural analysis
of the BFO nanoparticles was done with a JEOL 2010 model
high-resolution transmission electron microscope operating Figure 1 shows XRD patterns of all the samples
at 200 kV. All the TG-DTA and DSC data were recorded confirming clean phase formation of BFO, BBFO and BSFO

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J. Phys. D: Appl. Phys. 42 (2009) 065004 B Bhushan et al

Figure 2. (a) TEM image of an individual BFO nanoparticle, (b) SAED pattern of BFO, (c) HRTEM image of a BFO nanoparticle and
(d) EDS of BFO nanoparticles.

nanoparticles. Some additional peaks were observed in the (figure 2(c)) lattice fringes can also be seen, which indicates
XRD pattern of BCFO that correspond to some impurity phase. the sample is free of defects and possesses a high degree of
Observed XRD patterns could be indexed to the rhombohedral crystallinity. The energy dispersive spectrum of the BFO
structure of BFO with space group R3c. The average crystallite nanocrystals is shown in figure 2(d) that confirms the presence
sizes of our samples, as calculated from the broadening of the of Bi, Fe and O in our prepared sample. Spectra taken at a
two most intense peaks ([1 0 4] and [1 1 0]) using the Scherrer number of selected positions of the sample show the presence
formula, were noted to be 77 nm, 34 nm, 29 nm and 28 nm of the same constituents. The Cu and C signals arise from the
for BFO, BBFO, BSFO and BCFO, respectively. The values TEM grid.
of the lattice strain (along [1 1 0]) were 0.003 24, 0.003 30,
0.005 84 and 0.005 05 for the BFO, BBFO, BSFO and BCFO 3.2. Thermal analysis
nanoparticles, respectively. It is also seen from figure 1(a) that
the twin peaks such as (1 0 4) and (1 1 0), (0 0 6) and (2 0 2), At room temperature BFO has a rhombohedral distorted
(1 1 6) and (1 2 2), etc merge together to form a single peak in perovskite structure (α-phase) but at higher temperatures it
the case of doped samples (figures 1(b)–(d)). The substantial shows changes in the crystal structure (orthorhombic β-phase
reduction of size in the doped samples could be due to restricted and cubic γ -phase) as reported by Speranskaya et al [24].
crystal growth as divalent cations (Ba, Sr and Ca) substitute Recent work by Palai et al also presented evidence of the
trivalent cations of Bi. existence of BFO in three different phases with a modified
A typical TEM image of the BFO sample prepared by the phase diagram of the above system [25]. They reported
present sol–gel method is shown in figure 2(a). The average that α to β phase transition occurs at 823 ◦ C, β to γ phase
particle size estimated from TEM images for the BFO sample transition takes place at 925 ◦ C, decomposition of the cubic
came out to be 95 nm. The SAED pattern is presented in phase into Bi2 Fe4 O9 occurs between 933 and 961 ◦ C and above
figure 2(b), showing the presence of sharp diffraction spots that that the compound decomposes into Bi2 O3 and Fe2 O3 . We
are a clear indication of well-developed, single crystalline BFO carried out DTA measurements to observe the changes, if any,
nanoparticles. It should be noted that the electron diffraction in the first-order structural transition temperatures of BFO
patterns obtained from different areas of the nanoparticles also nanoparticles with respect to bulk BFO and the subsequent
show similar sharp diffraction spots. In the HRTEM image effect after doping. The DTA graph of the samples that

3
J. Phys. D: Appl. Phys. 42 (2009) 065004 B Bhushan et al

Figure 3. DTA spectra of all samples. Inset shows the DSC curves
of BFO and BCFO samples.

shows various endothermic peaks is shown in figure 3. It

should be noted that no changes in weight are observed in
TG analysis (graph not shown) of all the samples in the
temperature range 700–1000 ◦ C. It is evident from figure 3
that for the pristine sample, the α to β phase transition occurs
at a relatively lower temperature of 795 ◦ C, while the β to
γ phase transition occurs at 831 ◦ C. Decomposition of the
cubic phase into Bi2 Fe4 O9 occurs between 927 and 975 ◦ C;
above that the compound decomposes into Bi2 O3 and Fe2 O3 .
However, none of the four endothermic peaks are visible in
the doped samples and the trends are also different. This may
happen in doped BFO nanoparticles as these transformations
may be influenced by the replacement of ions and the creation Figure 4. (a) FTIR spectra of BFO and doped BFO samples.
of oxygen vacancies. DSC data, as shown in the inset of (b) UV–vis absorption spectra of all samples.
figure 3, gives the second order phase change occurring in
the samples. As evident from the figure, the Néel temperature
in the case of BFO nanoparticles is 327 ◦ C, which is lower
in comparison with the BFO bulk sample (TN = 370 ◦ C). In
the case of doped nanoparticles, TN = 259 ◦ C, 315 ◦ C and
295 ◦ C for BCFO, BSFO and BBFO, respectively. It is quite
evident that TN has shifted towards room temperature in the
case of doped samples with the maximum shift in the Ca-doped
BFO nanoparticles, which is quite desirable for obtaining room
temperature magnetoelectric coupling [26].

3.3. Optical analysis

Figure 4(a) shows FTIR spectra at room temperature of all the
samples. It is clear that there are two fundamental vibration
bands at ∼552 and ∼443 cm−1 for the pristine and doped
samples. These bands are assigned to Fe–O stretching and
bending vibration, respectively, present in the FeO6 octahedral Figure 5. Mössbauer spectra of all samples taken at room
unit [27]. Also the BiO6 octahedral structure unit exhibits temperature.
absorption peaks at 525 cm−1 and 450 cm−1 [28]. The broad
nature of the observed vibration bands is due to the occurrence BFO nanoparticles exhibit an absorption peak at 530 nm that
of absorption peaks of both iron oxide and bismuth oxide at shifts to 405 nm, 401 nm and 410 nm in the case of BBFO,
nearly the same wavenumbers. Figure 4(b) shows the UV–vis BSFO and BCFO, respectively. The band gap was calculated
spectra of all the samples. As seen from the spectra, pristine from the point of inflection in the first derivative plot of

4
J. Phys. D: Appl. Phys. 42 (2009) 065004 B Bhushan et al

Table 1. Mössbauer parameters of all samples.

−1
a
IS (mm s ) QSb (mm s−1 ) c
Hint (T) Line width
Sample name (±0.01 mm s−1 ) (±0.01 mm s−1 ) (±0.3 T) (mm s−1 ) % Intensity
BFO Sd 0.38 0.33 49.05 0.56 86.42
De 0.18 0.75 — 0.44 13.58
BBFO S 0.30 0.23 48.7 0.69 83.25
D 0.16 0.66 — 0.70 16.75
BCFO S 0.32 0.19 48.7 0.69 96.28
D 0.17 0.44 — 0.53 3.72
BSFO S 0.30 0.24 48.9 0.80 100
a
IS = Isomer shift.
b
QS = Quadrupole splitting.
c
Hint = Internal magnetic field.
d
S = Sextet.
e
D = Doublet.

the UV–vis absorption spectra of the nanoparticle systems

[29]. The band gap of BFO nanoparticle is ∼1.8 eV, which
is in agreement with the earlier reported values [25, 30, 31].
However, for all the doped samples the calculated band gap is
∼2.3 eV. A similar increase in the band gap was also observed
on doping of CdSe and ZnO nanocrystals with Mg2+ ions
[32, 33], which also belongs to the same class of alkaline earth
metals. The prominent shift in the absorption spectra of the
doped samples in comparison with pristine BFO is because of
rearrangement of the molecular orbitals due to the presence
of foreign elements that results in the change in the band
structure of the doped nanoparticles. As the band gap of
alkaline earth ferrates (∼3 eV) [21, 34, 35] is larger than BFO,
incorporation of these alkaline earth metals in BFO lattice
results in intermediate band gap values.

3.4. Hyperfine analysis

The hyperfine properties of BFO and doped BFO nanoparticles Figure 6. M–H curve of BFO and doped BFO nanoparticles
were studied by 57 Fe Mössbauer spectroscopy. Charge recorded at room temperature.
compensation due to the substitution of divalent ions in BFO
may cause either the formation of oxygen vacancies or the The isomer shift data of all samples confirm that Fe is present
conversion of Fe3+ ions into Fe4+ ions. Earlier, it was reported only in the Fe3+ state. No signature of Fe4+ or Fe2+ was found
that room temperature ferromagnetism in Ba doped BFO might in our samples by Mössbauer spectroscopy.
be due to the conversion of Fe3+ ions to Fe4+ ions [17].
The presence of Fe2+ ions was also proposed as one of the 3.5. Magnetization analysis
reasons for the weak ferromagnetic nature of the doped BFO
samples [36]. Using Mössbauer spectroscopic analysis we can In figure 6 hysteresis loops of BFO and doped BFO
precisely determine the oxidation state of Fe in the doped BFO nanoparticles at room temperature are shown. For all the
samples. Figure 5 shows the room temperature Mössbauer samples we can observe sizable hysteresis with a finite value
spectra of all the samples. Apart from BSFO all samples show of the coercive field, remanent magnetization and saturation
a combination of a sextet and a minor doublet. This minor magnetization that are tabulated in table 2. It should be
doublet may be due to superparamagnetic relaxation of finer noted that saturation in all M–H loops are easily achieved
particles as reported by Park et al [22]. Hyperfine parameters at an applied field of 10 kOe. The weakly ferromagnetic
of all the samples extracted from Mössbauer data are tabulated property in our substrate-free BFO nanoparticles as obtained at
in table 1. The obtained value of the hyperfine magnetic field is room temperature has originated for two main reasons: (1) the
consistent with previous reports [22, 37]. The large linewidths canting of spin arrangement and (2) the suppression of spiral
obtained in our samples were assigned to the presence of spin arrangement. The presence of spiral spin arrangement
different non-equivalent Fe sites in the crystal structure [38]. of wavelength 62 nm is responsible for the suppression of
However, later it was suggested that line broadening arose from magnetization in bulk BFO. But BFO nanoparticles having
the slight modulation of the hyperfine energies as the magnetic particle size of the order of this spiral spin structure
moments rotate with respect to the c-axis of the crystal [37]. exhibit room temperature ferromagnetism as observed in our

5
J. Phys. D: Appl. Phys. 42 (2009) 065004 B Bhushan et al

Table 2. Magnetic parameters at room temperature.

Particle Ionic Coercive Remanant Saturation
sizea radius of field magnetization magnetization
Sample (nm) Dopant dopant (Å) (kOe) (emu g−1 ) (emu g−1 )
BFO 77 — — 0.22 0.09 0.41
BCFO 28 Ca2+ 1.00 0.14 0.46 2.38
BSFO 30 Sr2+ 1.18 0.09 0.073 0.64
BBFO 34 Ba2+ 1.35 1.78 0.33 0.91
a
As obtained from XRD data.

nanoparticle samples [39]. Also, numerous magnetization

studies of antiferromagnetic nanoparticles have shown that the
magnetization in large applied fields is considerably larger than
that in the corresponding bulk materials. It was suggested
by Néel [40–42] that this might be due to the finite number
of magnetic moments in nanoparticles, which may lead to
a difference in the numbers of spin in the two sublattices
because of random occupancy of lattice sites. This results
in an uncompensated magnetic moment that leads to enhanced
magnetic properties. The largest value of the coercive field,
HC , is obtained for the BBFO sample which is ∼1.78 kOe.
Such a high value of HC at room temperature is quite
significant. For the BCFO sample, saturation magnetization,
MS , at 10 kOe is ∼2.38 emu g−1 , which is substantially higher
as compared with our other samples. This value of MS for
Ca doped BFO is even larger when compared with some of
the ferro or paramagnetic metal ions doped BFO samples, as
reported earlier [14, 43, 44]. The obtained high values of HC
for BBFO and MS for BCFO are attributed to the presence of Figure 7. Dielectric constant of BFO and doped BFO nanoparticles
recorded at room temperature as a function of frequency. Inset:
dopant. As these divalent metal ions (Ca2+ , Sr2+ , Ba2+ ) get (a) variation of dielectric constant and (b) dielectric loss with
substituted at trivalent Bi sites in the BFO nanocrystal, a sort applied magnetic field for BCFO nanoparticles.
of charge imbalance could arise, which may destabilize the
system. To maintain the electroneutrality, one oxygen vacancy
would be created for every two alkali earth ions introduced frequency f = 1 MHz, εr was found to be 45.5, 31.4, 18.8
into the BFO lattice. Thus created oxygen vacancies may and 4.5 for BFO, BCFO, BSFO and BBFO, respectively.
contribute to the enhanced magnetic properties of the doped Some authors have reported very high values of εr in BFO
BFO samples as established by Rao and co-workers [45]. ceramics and thin films [14, 17, 44], but that might be due to
These vacancies also reduce the oxygen content to some extent
the Maxwell–Wagner contribution or by the substrate induced
and give rise to non-stoichiometry which may be expressed as
strain in the case of thin films [46]. As compared with the
Bi0.95 X0.05 FeO3-δ , where δ
0.025.
pristine BFO, all the doped samples show a lower value of
The effect of reduced particle size in the case of the doped
dielectric constant. This is consistent with the increase in
samples with respect to pristine is not so prominent as the
the band gap (section 3.3) as wide band gap materials are
values of HC and MS for BiFeO3 nanoparticles of similar
expected to have a lower dielectric constant following the
particle size are quite lower [22] as compared with that in our
inverse proportionality relation [47, 48]. Further, an interesting
doped nanoparticles. The observation of higher coercivity and
trend emerges if we look at the εr values of the doped BFO
saturation magnetization in some of the doped nanoparticles
samples. It can be noticed that the dielectric constant decreases
may help in finding a way for improving magnetization
in BiFeO3 that, in turn, will lead to many technological as the ionic radius of the dopant increases. This is in agreement
applications. with earlier studies where a similar correlation between the
ionic radii and the dielectric constant was obtained [49, 50].
One of the simplest and widely used methods to show
3.6. Dielectric analysis
multiferroic coupling is the examination of the dielectric
The dielectric constant (εr ) of all samples as a function constant with the applied magnetic field. In a multiferroic
of frequency at room temperature is illustrated in figure 7. material, the dielectric constant is perturbed by the onset
It can be seen that the dielectric constant decreases with of magnetic ordering that itself is affected by the applied
increasing frequency. However, all the samples show similar magnetic field. We have shown here the variation of the
behaviour. They all have a Debye-like relaxation. At dielectric constant as a function of the applied magnetic field,

6
J. Phys. D: Appl. Phys. 42 (2009) 065004 B Bhushan et al

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