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Effect of Ca and Ag doping on the functional properties

of BiFeO3 nanocrystalline powders and films

Article in Materials Research Society symposia proceedings. Materials Research Society · August 2014
DOI: 10.1557/opl.2014.778

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Mater. Res. Soc. Symp. Proc. Vol. 1675 © 2014 Materials Research Society
DOI: 10.1557/opl.2014.778

Effect of Ca and Ag doping on the functional properties of BiFeO3 nanocrystalline powders

and films
Gina Montes Albino1, Oscar Perales-Pérez3, Boris Renteria-Beleño3 and Yarilyn Cedeño-Mattei3
1
Department of Mechanical Engineering, University of Puerto Rico at Mayagüez P.O. Box
9045, Mayagüez, PR, 00681-9045 USA.
2
Department of Physics, University of Puerto Rico at Mayagüez, Mayagüez, PR, 00980, USA.
3
Department of Engineering Science and Materials, University of Puerto Rico at Mayagüez,
Mayagüez, PR, 00680-9044, USA.

ABSTRACT
The present work addresses the systematic evaluation of the influence of the incorporation of
dopant species (Ca+2, Ag+1) on the structural and functional properties of bismuth ferrite (BFO)
nanocrystalline powders and films. Pure and doped BFO powders and thin films were
synthesized by a modified sol-gel method. The concentration of the doping species varied from 0
up to 7 at %. The development of the host BFO structure was confirmed by XRD analyses of
samples annealed at 700°C for one hour in air and nitrogen atmosphere. Thicknesses of films
varied between 80 and 200 nm, depending on the concentration of Ca+2 species. Doped BFO
exhibited a magnetic behavior that turned from paramagnetic into ferrimagnetic with the increase
of Ca+2 concentrations.

INTRODUCTION
Proper-primary type BiFeO3 (BFO)-based multiferroics are rhombohedrally distorted acentric
structure (space group R3c) that exhibit G-type antiferromagnetic order with a long-periodicity
spiral below the Neel temperature of 643 K and ferroelectricity below 1103 K. The
ferroelectricity of BiFeO3 is due to Bi3+ 6s2 lone-pair distortions, whereas the residual moment of
the canted Fe3+spin structure results in weak ferromagnetism.Recently, perovskite-type transition
metal oxides ABO3 are of great interest because of their magnetic, dielectric, and transport
properties that emerge from the coupling of spin, charge, and orbital degrees of freedom. A-site
substitutions of trivalent (La3+, Nd3+, or Sm3+) 1-6 or divalent (Ba2+, Pb 2+,Sr2+, or Ca2+) 7-10
species for Bi3+and B-sublattice dopings with V5+, Nb5+, Mn4+, Ti4+, or Cr3+ ions, have recently
been investigated in order to improve the magnetoelectric coupling11-15. BFO perovskite type,
proper and lead-free multiferroic material can find potential and promising applications in the
development of multifunctional devices, solar energy devices, ferroelectric random access
memory and spintronics. These applications rely on the observed (anti)ferroelectricity,
(anti)ferromagnetism, and ferroelasticity behaviors in a single crystalline phase. On this basis,
the present work will attempt to find a suitable combination of deposition parameters, via a
modified sol-gel approach, for improving multifunctional BFO properties in powders and films.
If oxygen vacancies are generated during the material forming stage, structural, magnetic and
electric transitions could be tuned and hence, optimized. Therefore, the annealing stage of the
precursor solids will be carried out in a close-system in air or nitrogen atmospheres.
Furthermore, the expected variation in the structural and functional properties of BFO in
presence of different dopant species (A-site doping with Ca+2 and Ag+1 cations) will also be
evaluated; doping with a divalent cation would induce a p-type semiconductor behavior favoring
magnetic transition.

105
EXPERIMENTAL

Materials
Pure and doped bismuth ferrite thin films were synthesized in acetic acid medium. Bismuth
Nitrate [Bi(NO3)3.5H2O, purity 99.9%], Iron Nitrate [Fe(NO3)3.9H2O, purity 99.9 %], Calcium
Nitrate [Ca(NO3)2.4H2O purity 99%] and Silver Nitrate [AgNO3, purity 99.99 %], salts. Suitable
weights of Bi1-xMxFeO3 (M= Ca or Ag ) salts are used to achieve the desired atomic percentages,
‘x’, according to the stoichiometry.

Synthesis of powders and thin films

Powders synthesis started with the dissolution of precursor salts in acetic acid for 1 hour
followed by the dropwise addition of the resulting solution on petri dish, and finally dried in air
for 12 hours at 80°C. Thin films were synthesized by first dissolving the precursor salts in acetic
acid and contacted with glycol (1mL of glycol added to 4mL of the precursor solution) in order
to control the viscosity. The homogeneous solution was added dropwise onto a clean Si (100)
substrate and spin-coated at 3000 rpm for 20 s. After each coating cycle, produced films are pre-
dried for 5 minutes at two different temperatures (150ºC and 250ºC) in order to remove organic
residuals. These spin-coating/drying cycles were repeated for twenty times to thick the films.
Powders and spin-coated films were then thermally treated in air or nitrogen for one hour at
700ºC. The heating rate was 5 ºC/min in all experiments.

Materials characterization
The structure of the synthesized powders and films was determined using a Siemens D5000 X-
Ray Diffractometer (XRD) with Cu-Kα radiation. The room-temperature magnetic hysteresis
(M-H) loops were measured using a Lake Shore 7410 Vibrating Sample Magnetometer (VSM).

DISCUSSION
X-ray diffraction analyses
Pure and Ca doped BFO powders and films
XRD spectra for Ca-BFO samples produced after the thermal treatment stage are shown in
figures 1 through 3. Figures 1 and 2 show the Ca-BFO(0 - 7 at % Ca) powders annealed in air
and nitrogen atmosphere, respectively. As observed in figures 1a and 2a, main XRD peaks
corresponding to BFO phase coexisted with low intensity peaks in the 25° - 30° 2θ range, which
are attributed to small amount of impurity phases (Bi2Fe4O9 or Bi25FeO39 intermediate oxides).
The same XRD patterns suggest that a suitable Ca doping could be conducive to the inhibition of
the formation of the impurity phases (7 at.% and 2 at.% of Ca in air and nitrogen atmosphere,
respectively). Average crystallite sizes for varied from 42 to 26nm and 42 to 33nm, in powders
annealed in air or nitrogen, respectively. Figures 1b and 2b show the magnification of the peak
corresponding to the (204) plane; a slight but evident shift towards lower 2T values was observed
and suggested the actual dopant incorporation in the BFO host structure. The ionic radii of Ca +2
is larger (1.26Å) than Bi+3 (1.17Å); this difference would explain the corresponding expansion in
the unit cell as suggested by the shift of the XRD peaks16-17. Figure 3 shows the XRD pattern
corresponding to the Ca-doped BiFeO3 thin film deposited onto Si (100) by spin coating process.
The film thickness was 200 nm. Only the main characteristic peaks corresponding to the BFO
structure were observed. Thee inhibition on the formation of the impurities could be attributed to
substrate effects as well as the suitable calcium content.

106
 b) Air
a) Air

(110)
(104)
(204)
Intensity (A.U.)

(204)
(108)

Intensity (A.U.)
(102)

(204)

(116)
(112)
(202)
(006)
Ca=7%

Ca=7% Ca=5%
Ca=5%
Ca=2%
Ca=2%
Pure Pure

20 25 30 35 40 45 50 55 60 45.0 45.5 46.0 46.5 47.0

2 Theta degree 2 Theta degree

Fig 1. XRD patterns of: (a) pure and Ca- BFO powders annealed in air. (b) magnification of the
angular region around the (204) peak; a slight shift to as Ca- dopant content
increased from 0 to 7 at.% was observed.
a) Nitrogen b) Nitrogen
(104)
(110)

(204)
(204)
(108)
Intensity (A.U.)

(204)

Intensity (A.U.)
(102)

(116)
(006)

(112)
(202)

Ca=7% Ca=7%

Ca=5% Ca=5%
Ca=2% Ca=2%
Pure Pure

20 25 30 35 40 45 50 55 60 44 45 46 47 48

2 Theta degree 2 Theta degree

Fig 2. XRD patterns of: (a) pure and Ca-BFO powders annealed in nitrogen atmosphere and, (b)
magnification of the angular region around the (204) peak.
Bi Ca FeO
0.93 0.07 3
Nitrogen
Intensity ( A.U.)

(104)
(102)

(202)

(204)

(116)

(204)

20 25 30 35 40 45 50 55 60

2 Theta (degree)
Fig 3. XRD pattern corresponding to 20-layers Ca-BFO/Si (100) thin film. The Ca content was
set at 7 at %.

107
 Pure and Ag-doped BFO powders
XRD spectra for Ag-BFO powders formed under air and nitrogen atmospheres are shown in
figures 4 and 5. The main peaks corresponding to the BFO host structure that co-existed with
impurity Bi-oxide phases were detected. The electronic decompensation due to the substitution
of trivalent Bi+3 by monovalent Ag+ would have altered oxygen diffusion promoting the formation
of other oxide phases. Despite of the presence of these impurities, a remarkable shift towards
lower diffraction angles was observed for the BFO peaks (Figure 4b and 5b) in presence of 2 at.
% of Sag; it was interesting to observe that the (204) peak was slightly shifted towards higher 2θ
values when the Ag content was increased up to 7 at.%. The expansion of the unit BFO unit cell
due to the incorporation of large Ag ions (1.42 Å) could be related to this displacement of the
diffraction peaks of the host BFO structure. In turn, the average crystallite sizes for Ag-BFO
powders treated in air and nitrogen decreased 40 to 26 nm (annealed in air) and 40 to 37 nm
(annealed in nitrogen), when the dopant content increases from 0 up to 7%.

a) Air b) Air
(104)
(110)

(204)
Intensity (A.U.)

Intensity (A.U.)
(116)
(204)

(204)
(108)
(202)
(102)

(112)
(006)

Ag=7% Ag=7%
Ag=5% Ag=5%
Ag=2%
Ag=2%
Pure
Pure
20 23 25 28 30 33 35 38 40 43 45 48 50 53 55 58 60
45.0 45.3 45.5 45.8 46.0 46.3 46.5 46.8 47.0
 Theta degree
 Theta degree
Fig 4. XRD patterns of: (a) pure and Ag-BFO powders annealed in air atmosphere, and (b)
magnification of the angular region around the (204) peak.
a) Nitrogen b) Nitrogen
(104)
(110)
(102)

(204)
(204)

(204)
(116)
(202)

(112)

Intensity (A.U)
Intensity (A.U)

(108)
(006)

Ag=7% Ag=7%
Ag=5%
Ag=5%
Ag=2% Ag=2%
Pure Pure

20 25 30 35 40 45 50 55 60 45.0 45.5 46.0 46.5 47.0

2 Theta(degree) 2 Theta degree
Fig 5. XRD patterns of: (a) pure and Ag-BFO powders annealed in nitrogen atmosphere, and (b)
magnification of the angular region around the (204) peak.

108
Room-temperature M-H measurements
Pure and Ca doped BFO powders and films
Room-temperature M-H loops of pure and Ca-BFO powders annealed for one hour at 700°C in
air and nitrogen are shown in figures 6 a and b, respectively. As evident, doping of BFO with Ca
drastically changed the magnetic behavior from paramagnetic to ferrimagnetic18. A rising trend
in coercivity was also observed when the Ca concentration was increased up to 7%. The
corresponding coercivity values varied from 10 to 16 Oe when annealed in air (figure 6a) and
from 5 to 35 Oe when the annealing was performed in nitrogen (figure 6b) atmosphere. In turn,
figure 7 shows the M-H loops for thin films of Ca (7 at. %)-BFO/ Si(100) annealed at 700°C in
nitrogen atmosphere. Maximum magnetization values was dependent on the thickness vary from
80 to 200nm depending of different coatings in the film. Coercivity values are 40, 33, and 23 Oe
for 20, 15, and 10 layers, respectively.
0.10
a) 0.10
b) X=7%
X=2%

X=2%
0.05
0.05
X=5%
Magnetization (emu/g)
Magnetization (emu/g)

X=5%

0.00
X=0%
0.00

-0.05 -0.05
X=0%

X=7% Nitrogen
Air
-0.10 -0.10
-3600 -2400 -1200 0 1200 2400 3600 -3600 -2400 -1200 0 1200 2400 3600

Field (Oe) Field (Oe)

Fig 6. Room-temperature M-H loops corresponding to Ca-doped bismuth ferrite powders
synthesized at different calcium atomic percentages, ‘x’, annealed at 700°C for 1hour in: ( a) air
and (b) nitrogen.
t=20
0.0008
t=15 Fig 7. Room-temperature M-H loops for Ca (7
t=10
at.%)-BFO/Si(100) films with different
thicknesses (‘t’’ is the numbers of layers used
Magnetization (emu)

0.0004

in the precursor film preparartion. The

0.0000 magnetic field was applied perpendicular to the
film plane. The coercivity was as high as 40
-0.0004
Oe for 20 layer thick film (thickness = 200nm)
doped at 7 at % Ca.
-0.0008 Nitrogen
-10000 -5000 0 5000 10000

Field (Oe)

109
Pure and Ag doped BFO powders
Figure 8 shows the M-H loops of Ag-BFO powders annealed in air. The hysteresis loops exhibit
the same tendency as in Ca-BFO powders, i.e., the material changed from paramagnetic into
ferri/ferromagnetic after doping with Ag species. Coercivity was as high as 97 Oe for the BFO
doped with 7 at. % of Ag. The observed effect of the Ca and Ag dopants on the magnetic nature
of the BFO host could be attributed to apparent incorporation of Ca and Ag cations into the BFO
lattice as well as to the probable p-type semiconductor behavior19, 20.
0.05
X=0%
0.04

0.03
X=7%
Fig 8. Room-temperature M-H
loops for Ag- doped bismuth ferrite
Magnetization (emu/g)

0.02
X=5%
0.01 powders synthesized at different
0.00 silver atomic percentages, ‘x’,
-0.01 annealed at 700°C by 1h in air
X=2%
-0.02 atmosphere.
-0.03

-0.04
Air
-0.05
-3600 -2400 -1200 0 1200 2400 3600

Field (Oe)

CONCLUSIONS
Pure and Ca- and Ag-BFO nanocrystalline powders and thin films were synthesized using a
modified sol-gel technique. X-ray diffraction analyses confirmed the formation of well
crystallized cubic rhombohedral BFO phase. BFO single phase formations were obtained for 7
and 2 at % of Ca- doped BFO powders in air and nitrogen atmosphere, respectively. M-H
measurements of the Ca-BFO powders and films and the Ag-BFO powders evidenced the strong
influence of the type and amount of dopants on the magnetic characteristics of the host BFO
structure; depending on the dopant amount, the material drastically changed from a paramagnetic
into a ferromagnetic ones.

ACKNOWLEDGMENTS
This material is based upon work supported by the DOE-Grant No FG02-08ER46526. Special
thanks to Brian Ferrer and Walter Guzman who helped with the synthesis process. Particular
acknowledgemt to the support from Dr. Ram Katiyar’s group from the Speclab Laboratory at
UPR-Rio Piedras Campus.

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