Journal of Magnetism and Magnetic Materials 373 (2015) 8689

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Journal of Magnetism and Magnetic Materials

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

Ferromagnetism at room temperature in Co-doped KNbO3

bulk samples
A. Astudillo a,n, J.L. Izquierdo b, A. Gmez c, G. Bolaos a, O. Morn b
a

Low Temperature Laboratory, Department of Physics, University of Cauca, Calle 5 No. 4-70, Popayn, Colombia
Universidad Nacional de Colombia, Campus Medelln, Departamento de Fsica, Laboratorio de Materiales Cermicos y Vtreos, A.A. 568, Medelln, Colombia
c
Universidad Nacional de Colombia, Campus Medelln, Facultad de Minas, Laboratorio de Caracterizacin de Materiales, A.A. 568, Medelln, Colombia
b

art ic l e i nf o

a b s t r a c t

Article history:
Received 17 December 2013
Received in revised form
12 February 2014
Accepted 19 February 2014
Available online 27 February 2014

In this work, polycrystalline KNb1
xCoxO3 (x 0, 0.05 and 0.1) samples were synthesized through
standard solid-state reaction, and their structural and magnetic properties were carefully studied. The Xray powder diffraction (XRD) patterns show reections of a pure orthorhombic structure (space group
Bmm2) with lattice parameters being very close to those reported in the literature. The most important
point here is that all the samples ended up being single-phase with no affectation by impurities or
segregates. The XRD peaks of Co-doped samples are broadened and shifted to the right side as compared
to those of the pristine compound (x 0) suggesting effective substitution of Nb by Co ions. The Co-doped
samples exhibit ferromagnetic properties at room temperature, which contrasts starkly with the
paramagnetic behavior exhibited by the undoped sample. Interactions between bound magnetic
polarons are considered as a possible scenario to explain the appearance of the ferromagnetic signal
in the Co-doped samples.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
Multiferroics
Ferromagnetism
Solid-state reaction

1. Introduction
Multiferroic materials have attracted considerable interest
because of the coexistence of magnetic and ferroelectric ordering
[13]. However, there are very few multiferroic materials due to
the chemical incompatibility between materials showing magnetism and ferroelectricity separately [4]. The most interesting
characteristic of multiferroic materials is the possibility of controlling electrical polarization through a magnetic eld or magnetization through an electric eld. This property generates a great
potential for the fabrication of multifunctional devices such as
data storage elements, magnetic resonance devices controlled via
electric eld, transducers with electrically controlled piezoelectric
devices, etc. [510]. As stated above, there are only a few singlephase multiferroics, and most of them show multiferroic properties simultaneously at low temperatures. Therefore, how to combine room temperature (RT) multiferroics in a single phase
became an open question in materials science [11]. From the
preparation of dilute magnetic semiconductors (DMS), it is known
that the introduction of magnetic ions can alter the electronic and
magnetic properties of the semiconductors to a considerable
degree. By analogy with DMS, it is expected that room-

Corresponding author.
E-mail address: jaastudillo@unicauca.edu.co (A. Astudillo).

http://dx.doi.org/10.1016/j.jmmm.2014.02.071
0304-8853 & 2014 Elsevier B.V. All rights reserved.

temperature ferromagnetism to be introduced to ferroelectric

materials through doping with magnetic ions such as Co. Hence,
room-temperature single-phase multiferroics could be obtained.
Potassium niobate KNbO3 have perovskite-type structure and
shows a variety of properties such as ferroelecticity, piezoelectricity, nonlinear-optic response, photo-catalytic activity, etc.
[12,13]. Interestingly, KNbO3 exhibits several known phase transitions, namely from cubic to tetragonal at  710 K, tetragonal to
orthorhombic at  500 K (accompanied by a ferroelectric phase
transition) and nally from orthorhombic to rhombohedral at
260 K [14].
In this work, the careful preparation of polycrystalline
KNb1
xCoxO3 (x 0, 0.05 and 0.1) samples through standard
solid-state reaction is reported. The samples have been characterized after their structural, electrical and magnetic properties using
an X-ray diffraction and VSM magnetometry, respectively.

2. Experiment
Polycrystalline samples of KNb1
xCoxO3 System (x 0, 0.05,
and 0.1) were fabricated through standard solid-state reaction
using high-purity K2CO31.5 H2O, (99.998%), Nb2O5 (99.99%) and
Co3O4 (99.9%) as starting precursors. The precursors were mixed

A. Astudillo et al. / Journal of Magnetism and Magnetic Materials 373 (2015) 8689

together in an appropriate stoichiometry. The powders were

grounded in an agate mortar with the help of polyvinyl alcohol.
The powders were then pelletized (1 cm in diameter and 2 mm
thickness) using a cylindrical press at a pressure of 4 t. Afterwards,
the pellets were preheated at 850 1C for 12 h and then sintered at
900 1C for 12 h in air atmosphere.
X-ray powder diffraction patterns of the compounds were registered with a Panalytical XPert Pro diffractometer, in a standard 2
conguration, using CuK radiation ( 0.15418 nm). The recorded
X-ray diffractograms were adjusted using a Rietveld renement which
allows one to obtain structural parameters such as the lattice
constants of the structure. For electrical characterization of the
samples, electrical polarization curves were measured using a Radiant
Technologies RT66A test system for ferroelectric materials. A standard
bipolar wave with period of 10 ms was applied to cylindrical pellets of
7 mm in diameter and thicknesses of about 1 mm. These pellets were
placed between copper electrodes simulating a parallel plate capacitor.
In turn, the magnetic response of the pellets was detected by sensible
measurements of the magnetization as a function of the eld using a
VSM magnetometer (Quantum Design).

3. Results and discussion

The XRD diffractograms of polycrystalline KNb1
xCoxO3 (x 0,
0.05, and 0.1) samples are presented in Fig. 1 (a). Diffractograms
demonstrate that all the compounds possess the polycrystalline
perovskite structure in KNbO3 phase. Moreover, the diffractograms
show no impurity peaks, which evidence that the synthesized
compounds are single-phase. This is very important result because

the synthesis of KNbO3 is very difcult due to the volatility of

potassium and the low melting point of KNbO3 [15]. Certainly, the
presence of impurity peaks, belonging to Nb2O5, has been reported
by other authors [14]. Fig. 1(b) shows the XRD diffractograms
plotted on an enlarged scale around the main peaks of the
structure. It is observed that the peaks of Co-doped samples are
shifted to higher angles as compared to the pattern of the pristine
compound (x 0). This suggests that Co ions are implanted into
KNbO3 lattice successfully. Because the radius of Co2 /Co3 ions is
comparable to that of Nb5 ions but is much smaller than that of
K ions, it is very probable that cobalt ions occupy the Nb sites of
KNbO3. In turn, the broadening of the peak with the addition of Co
implies reduction in the grain size concomitant with the increase
in the grain boundaries. The lattice parameters obtained by the
Rietveld renement ended up being a 5.696 , b3.975 , and
c 5.721 for KNbO3 samples. These values are very close to those
reported in the literature for the compound with orthorhombic
symmetry (space group Bmm2).
Fig. 2(a) shows the magnetic hysteresis loop of the KNb0.95Co0.05O3
sample recorded at room temperature. It is observed that the sample
is weakly ferromagnetised at room temperature. The remanent and
maximum magnetizations (at H1 T) are 1.6  10
3 and
6  10
2 emu/g, respectively. In Fig. 2(b), the M(H) dependence
measured on KNb0.9Co0.1O3 sample at room temperature is plotted.
Here, a paramagnetic contribution stemming, probably, from a
limited solubility of Co ions in KNbO3 lattice has been removed
leading to saturation (3.5  10
3 emu/g at H1 T). Although a weak
ferromagnetic signal is still observed at low elds, the signal is
considerably weakened as compared to that stemming from 5%
Co-doped sample. Hence, it is apparent that doping levels higher

x=0.1

x=0.05

Intensity [x103 c/s]

Intensity [x103 c/s]

6
4

x=0

0
20

40

60

87

x=0.1
x=0.05
x=0

6
4
2
0

80

31.0

2 []

31.5
2 []

32.0

Fig. 1. (a) X-ray powder diffraction patterns of polycrystalline KNb1
xCoxO3 (x 0, 0.05, and 0.1) samples synthesized by standard solid state reaction. (b) Enlarged XRD
patterns of KNb1
xCoxO3 samples around the mean peak of the structure.

-6

300 K
-0.5

0.0

0H [T]

0.5

emu/g]

-2

x=0.05

1 x=0.05
0
300 K
-1
-0.1 0.0 0.1
0H [T]

x=0.1

x=0.1
0

-3

0.5

M [x10

300 K
0.0

0H [T]

M [x10

-3

-0.5

M [x10-3 emu/g]

-1

KNb0.9Co0.1O3

1 x=0

emu/g]

-2

M [x10 emu/g]

M [x10-2 emu/g]

6 KNb Co O3
0.95
0.05

-2

300 K

-2

300 K

-0.2

0.0

0.2

H [T]
0

-1

0H [T]

Fig. 2. (a) Dependence of the magnetization as a function of magnetic eld, M(H), for KNb0.95Co0.05O3 sample at room temperature. Upper inset: M(H) dependence measured
on an undoped sample (x 0) at room temperature. Low inset: enlarged M(H) dependence for the KNb0.95Co0.05O3 sample. (b) M(H) dependence for KNb0.9Co0.1O3 sample
recorded at room temperature. Inset: M(H) dependence for KNb0.95Co0.05O3 sample at low elds.

A. Astudillo et al. / Journal of Magnetism and Magnetic Materials 373 (2015) 8689

x=0.1

0
-2
-4

-2

M [x10 emu/g]

x=0
x=0.05

M [x10-2 emu/g]

M [x10-2 emu/g]

88

-1

5K

-0.4

-0.2
0.0
0H [T]

0.2

0.4

5K
-0.2

-5
-0.1

0.0
0H [T]

0.0

0H[T]

0.1

0.2

Fig. 3. (a) Dependence of the magnetization as a function of magnetic eld, M(H), for samples with x 0, and x 0.05 at 5 K. (b) M(H) dependence for KNb0.9Co0.1O3 sample
recorded at 5 K.

6
3

-4

-2

x=0.1
x=0

0.1

0.0
4

-3

x=0.05

2
0

-0.1

-2

-6

-4

-6 -3

Polarization [x10-2C/cm2]

Polarization [x10-2C/cm2]

Electric Field [kV/cm]

Electric Field [kV/cm]

-0.2
0.0
0.2
Electric Field [kV/cm]
Fig. 4. Room-temperature ferroelectric hysteresis loop of samples with x 0,
x 0.05 (inset), and x 0.1. The solid line corresponds to the sample with x 0.1
recorded at a eld of  4 Kv/cm.

than 10% do not improve the ferromagnetism in the parent KNbO3

compound as observed in Fig. 2(b). Probably, the solubility limit of Co
ions in KNbO3 lattice is lower than 10%. More experimental work is
necessary to elucidate this effect. Here, it is important to signalize that
the parent KNbO3 is not magnetic. This is evidenced by the M(H)
dependence shown in the top inset of Fig. 2(a). A pure paramagnetic
signal is observed at 300 and 5 K [Fig. 3(a)]. The M(H) dependences of
5% and 10% Co-doped samples recorded at 5 K are shown in Fig. 3.
The evolution of the ferromagnetic signal stemming from 5% Codoped sample is clearly observed in Fig. 3(a). Indeed, a well-dened
hysteresis with stronger maximum magnetization and coercivity, as
compared with the curve recorded at 300 K, is evident from this plot.
This effect is not evident for 10% Co-doped sample [Fig. 3(b)]. As the
XRD patterns [Fig. 1(a)] show that no phases of Co elementary
substances and Co oxides are present in the fabricated samples, it is
probable that Co doping generate the magnetism into KNbO3
compound. Although the origin of the ferromagnetic signal observed
in the Co-doped compound should be carefully analyzed, a possible
scenario would consider the interactions between bound magnetic
polarons [12]. Certainly, as Co2 /Co3 ions substitute Nb5 , oxygen
vacancies are generated to obtain a charge balance, which leads to the
formation of bound magnetic polarons. The interaction between
these bound magnetic polarons would originate the weak ferromagnetism observed at room temperature in the doped KNbO3 compound [13].
Measurements of polarization as a function of the applied
electric eld (Fig. 4) on undoped and Co-doped samples evidence
a hysteretic feature, which is the characteristic of the ferroelectric

materials. The changes in the ferroelectric response with the

increasing of Co in the crystallographic sites of Nb are clearly
observed both in the main panel of Fig. 4 and inset of this plot. For
samples with x 0.05 and x 0.1, saturation polarization of
3  10
2 and 1.5  10
2 C/cm2 are found at applied elds of
3 and 2 kV/cm, respectively. The changes in the ferroelectric
response are, probably, due to the distortion of the perovskitelike structure that implies the tilting of the octahedrons in the
unit cell.

4. Conclusions
Single-phase, polycrystalline KNb1
xCoxO3 (x 0, 0.05, 0.1)
samples were fabricated the by solid-state reaction method. The
XRD patterns showed no affectation by foreign phases or impurities. The shift of the XRD patterns to higher angles with Co
doping suggested that Nb ions were replaced by the smaller Co
ions. KNb0.95Co0.05O3 samples displayed weak ferromagnetism at
room temperature which was reinforced at 5 K. The M(H) dependence of the KNb0.9Co0.1O3 sample showed a well dened hysteresis at low elds although without saturation. The diminished
ferromagnetism observed for samples with doping levels as high
as 10% would be associated with the solubility limit of Co ions in
the KNbCoO3 lattice. Polarization curves revealed the ferroelectric
behavior of both undoped and Co-doped samples although Codoped samples showed enhanced ferroelectricity which seems to
be linked to the distortion of KNbCoO3 lattice caused by the
smaller Co ions. Without doubt more experimental and theoretical
work is necessary to gain a closer insight into the fascinating
although complex behavior of the diluted KNbO3 compound.

Acknowledgments
Two of the authors (G. Bolaos and A. Astudillo) acknowledge
the nancial support from the Vicerrectora de investigaciones at
the Universidad del Cauca. O.M. acknowledges the support of the
Universidad Nacional de Colombia, Campus Medelln.

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