B O L E T I N D E L A S O C I E DA D E S PA Ñ O L A D E

Cerámica y Vidrio
A R T I C U L O

Dielectric behavior of La1-xCaxMnO3 (0.4 ≤ x ≤ 0.5)

P.M. Botta, J. Mira, A. Fondado and J. Rivas

Departamento de Física Aplicada, Universidade de Santiago de Compostela Campus Universitario Sur, E-15782,
Santiago de Compostela, España.

In this work the dielectric behavior of semiconducting La-manganites in an intermediate Ca-doping regime is studied.
Ceramic samples were prepared by conventional solid-state reaction, using elemental oxides as starting reactants. A chemical,
structural and microstructural characterization of the prepared manganites was performed by iodometric titrations, X-ray
diffraction and scanning electron microscopy, respectively. The magnetic susceptibility and electrical resistivity as a function
of temperature were also measured. The complex dielectric permittivity of the samples was determined as a function
of frequency and temperature. Very high values of dielectric constant in a wide frequency and temperature range were
observed for all the synthesized samples. Moreover, an increase of the dielectric constant at temperatures close to charge-
order or metal-insulator transition is reported.

Keywords: dielectric constant, manganites, charge-order, perovskites.

Comportamiento dieléctrico de La1-xCaxMnO3 (0.4 ≤ x ≤ 0.5)

En este trabajo se estudia el comportamiento dieléctrico de manganitas de La dopadas con Ca en un rango de composición
cercano a 0.5. Se prepararon muestras cerámicas por el método de reacción en estado sólido, utilizando los óxidos elementales
como reactivos. Los materiales obtenidos fueron caracterizados química, estructural y microestructuralmente mediante
titulaciones iodométricas, difracción de rayos X y microscopía electrónica de barrido, respectivamente. Se hicieron medidas
de susceptibilidad magnética y resistividad eléctrica en función de la temperatura. Además se determinó la permitividad
dieléctrica compleja de las muestras sintetizadas en función de la frecuencia y la temperatura. Se observaron valores muy
elevados de la constante dieléctrica en un amplio rango de frecuencias y temperaturas para todos los materiales obtenidos.
También se encontró un aumento de la constante dieléctrica a temperaturas cercanas a las de las transiciones de orden de
carga o metal-aislante sufridas por estos materiales.

Palabras clave: constante dieléctrica, manganitas, orden de carga, perovskitas.

1. INTRODUCTION

The development of high dielectric permittivity materials material and contacts and/or grain boundaries (7). Studies
is nowadays one of the most important challenges of new on systems with charge condensation, such as Pr2/3Ca1/3MnO3
technologies. This is mainly owing to the role that they play in (8) and La3/2Sr1/2NiO4 (9) suggest the existence of a correlation
the design of high capacitance devices, which have a double between the dielectric properties and the electronic state in
interest: on one hand, as energy storage devices and on the this kind of compounds.
other hand, as capacitive elements in miniaturized circuits The system La1-xCaxMnO3 has a rich magnetic phase
(1). At present, in the industrial field, the standard solution diagram (10) where paramagnetism (PM), ferromagnetism
to obtain high dielectric constants has been searched in (FM), antiferromagnetism (AFM), and charge ordering (CO)
classical ferroelectric materials (2), in which exist spontaneous are determined by the temperature and the doping level x.
electric polarization due to charge separation. However, these Its ground state is ferromagnetic metallic for 0.15 < x < 0.5.
materials exhibit a steep variation of dielectric permittivity The phase boundary point x = 0.5 is a focus of great interest.
with small temperature changes, which constitutes a severe Upon lowering temperature this compound first undergoes
limitation for some applications. a PM to FM transition at T ≅ 225 K, and then to a COAFM
Recent reports of giant dielectric permittivity have directed phase at temperatures between 160 and 180 K, depending on
considerable attention to several new non-ferroelectric mixed the synthesis conditions (11,12). Compounds with 0.15 < x <
oxides and composites, such as CaCu3Ti4O12 (3), percolative 0.5 undergo transitions from a PM-insulating to a FM-metallic
BaTiO3-Ni (4) and (Li,Ti)-doped NiO (5). The enormous state at temperatures between 175 and 230 K, according to x.
dielectric constant of these materials seems to be a consequence In this context, we have focused on charge-ordered and
of an internal barrier-layer capacitor structure (IBLC) (6), close to metal-insulator transition manganites in order to
composed of insulating layers between semiconducting evaluate them as dielectric materials alternative to classical
grains. Other reports explain the apparent colossal dielectric ferroelectrics.
permittivity of these compounds by Maxwell-Wagner-type
contributions of depletion layers at the interfaces between

Bol. Soc. Esp. Ceram. V., 45 [3] 163-168 (2006)

(c) Sociedad Española de Cerámica y Vidrio, 163
Consejo Superior de Investigaciones Científicas. [Link]
Licencia Creative Commons 3.0 España (by-nc)
 P.M. Botta, J. Mira, A. Fondado and J. Rivas

2. EXPERIMENTAL

2.1. Material synthesis

Polycrystalline samples were prepared by grinding

highly pure and dried La2O3, CaO, and Mn2O3 in an agate
ball-mortar. These oxides were mixed in three different
proportions according to the composition of La0.60Ca0.40MnO3
(LC40), La0.55Ca0.45MnO3 (LC45) and La0.50Ca0.50MnO3 (LC50).
The obtained powders were compacted using conventional
uniaxial pressing at 5 ton/cm2. Successive thermal treatments
at 1200 and 1300ºC in air with intermediate grindings of
the pellets were performed. The samples calcined at 1300ºC
were ground and part of the resulting powder was uniaxially
pressed at 10 ton/cm2 into pellets of 5 mm diameter and 1
mm height. The remaining powder was uniaxially pressed at 5
ton/cm2 into pellets of 10 mm diameter and 1 mm height. Both
types of pellets were sintered for 24 h at 1400ºC in air.

2.2. Structural and microstructural characterization

Fig. 1- XRD patterns for samples LC40, LC45 and LC50 calcined at
1400ºC.
Phase evolution of the samples was followed by X-ray
diffraction (XRD) using a Philips PW1710 diffractometer
equipped with a Cu anode, a proportional counter and a samples compacted at 5 and 10 ton/cm2. In the first case,
graphite monocromator. Micrographs of the samples were intergranular porosity with average size of 1-2 µm can
taken by scanning electron microscopy (SEM) using a LEO- be noticed. For the powders formed at higher pressure, a
435VP microscope. Oxygen content of each sample was very low porosity is observed, showing an almost complete
analyzed by iodometric titrations. sintering. The higher compaction degree obtained by pressing
at 10 ton/cm2 produces a more efficient mass transport during
2.3. Electrical and magnetic characterization the heating, leading to more homogeneous microstructures.
Magnetization between 5 and 300 K was measured in a Also, slightly larger grains are obtained for compositions with
commercial SQUID magnetometer. Measurements after both lower Ca content, which could suggest a correlation between
ZFC (zero-field cooling) and FC (field cooling) were carried the sintering rate and the La/Ca ratio for these manganites.
out applying a magnetic field of 100 Oe, under static heating. Since the better microstructures were obtained for the samples
In the case of ZFC the sample was cooled up to 5 K without
applying a magnetic field, while for FC curves a magnetic
field of 100 Oe was applied during the cooling.
Four-probe DC resistivity (ρ) measurements were taken
during dynamic heating between 80 and 350 K. The samples
were cut in uniform bars and contacts of silver were used in
order to attach Cu connections to them.
Complex dielectric permittivity was measured at
frequencies ranging from 20 to 1·106 Hz using a home-made
device coupled to an Agilent 4284A LCR-meter. A parallel-plate
capacitor was mounted in an aluminum box refrigerated with
liquid N2, coupled to a temperature controller able to measure
between 90 and 350 K. The measurements were taken during
static heating of the samples. Electrical contacts between the
electrodes and samples were assured by sputtering with gold
both material surfaces.

3. RESULTS AND DISCUSSION

Figure 1 shows the XRD patterns of the synthesized

materials. In each case, all the diffraction peaks belong to
the desired phases, confirming the completion of the solid-
sate reaction and the absence of spurious phases. Structural
parameters of the formed phases are in good agreement with
those reported by crystallographic databases (13). Iodometric
titrations resulted in oxygen contents very close to the
stoichiometric value (3.00) for all the studied compositions.
Micrographs of the sintered materials are observed in Fig. 2- SEM micrographs of samples LC40, LC45 and LC50 uniaxially
Figure 2. Differences in microstructure are observed between pressed at 5 (a) and 10 (b) ton/cm2. All the pellets were sintered at
1400ºC. Bar: 20mm.

164 (c) Sociedad Española de Cerámica y Vidrio,

Bol. Soc. Esp. Ceram. V., 45 [3] 163-168 (2006)

Consejo Superior de Investigaciones Científicas. [Link]

Licencia Creative Commons 3.0 España (by-nc)
Dielectric behavior of La1-xCaxMnO3 (0.4 ≤ x ≤ 0.5)

pelletized at higher pressures, only the magnetic and dielectric

properties of these materials were measured.
Figure 3 shows the magnetic susceptibility (χ) as a function
of temperature. Samples LC40 and LC45 show a typical
FM-PM transition at Curie temperatures (TC) of 265 and 250
K, respectively. For sample LC50 an AFM-FM transition at
about 185 K and a FM-PM transition at 220 K are observed.
All these temperatures coincide with those obtained from the
magnetic phase diagram (10), confirming the good quality
of the synthesized materials. The large hysteresis exhibited
between ZFC and FC curves can be explained taking into

Fig. 4- DC resistivity (ρ) vs. temperature for samples LC40 y LC45 (a)
and LC50 (b).

account the nature of these magnetic transitions, in which the

transformation from PM to FM state involves a progressive
appearance of FM domains. Upon cooling, the application
of a magnetic field (FC curves) can enlarge the size of these
domains, provoking higher magnetic susceptibilities than
those displayed for ZFC curves at temperatures below Tc.
DC resistivity as a function of temperature is shown in
Figure 4. The resistivity values represented in this figure are
relative to those measured at 300 K for LC40, LC45 and LC50
(which are 2.8·10-2, 6.3·10-3 and 4.8·10-3 Ω.cm, respectively).
For samples LC40 and LC45 metal-insulator transitions are
observed at 264 and 251 K, respectively. Taking into account the
magnetic behavior (Fig. 3) we can conclude that upon heating
these systems are changing from a ferromagnetic-metallic
to a paramagnetic-insulating (or semiconducting) state. In
contrast, sample LC50 always shows values of δρ/δT < 0,
which indicates an insulating (or semiconducting) response in
the entire temperature range. However, a wide and small band
centered at T ∼ 180 K can be noticed, as a consequence of a
charge-order transition, according to previous reports (10-12).
Figure 5 shows the real part of the relative permittivity
(dielectric constant, ε’r) of the samples as a function of
frequency at several temperatures. For the three compositions,
a plateau of ε’r between 1·105 and 1·106 can be observed at
frequencies from 300 to 3·105 Hz. These abnormally high
Fig. 3- Magnetic susceptibility (χ) as a function of temperature for sin- dielectric constant values are the result of the combination of
tered samples LC40 (a), LC45 (b) and LC50 (c). intrinsic and extrinsic effects. The first ones are related to the

Bol. Soc. Esp. Ceram. V., 45 [3] 163-168 (2006)

(c) Sociedad Española de Cerámica y Vidrio, 165
Consejo Superior de Investigaciones Científicas. [Link]
Licencia Creative Commons 3.0 España (by-nc)
 P.M. Botta, J. Mira, A. Fondado and J. Rivas

Fig. 5- Real part of the complex relative dielectric permittivity ( ε’r )

vs frequency at selected temperatures for LC40 (a), LC45(b) and LC50 Fig. 6- Loss tangent (tanδ) vs. frequency at several temperatures for
(c). LC40 (a), LC45 (b) and LC50 (c).

charge condensation that takes place in some systems with the curves up to 1·109 Hz (a enough high frequency to consider
cations of variable valence, such as Ni2+-Ni3+ and Mn3+-Mn4+ a complete relaxation) may be a good approximation to
(8,9). The extrinsic factors are associated to the interfacial intrinsic ε’r values (14). This gives dielectric constants of about
polarization produced in grain boundaries and contacts 50 for these manganites. Therefore, the extrinsic effects play an
sample-electrode (7). At the highest frequencies a drop of extremely significant role in the dielectric response of this kind
dielectric constant is observed for all the temperatures, of materials, specially at low frequencies.
suggesting the relaxation of these interfacial phenomena. In Figure 6 dielectric loss tangent vs frequency is plotted.
In this way, in order to evaluate both contributions, the Very high values are observed at low frequencies for all the
realization of dielectric measurements at higher frequencies prepared manganites. In fact, values as high as 1·104 are reached
would be necessary. In spite of this, a linear extrapolation of for LC50. At higher frequencies tanδ exponentially decreases up
to reach values ranged between 2 and 10. These high dielectric

166 (c) Sociedad Española de Cerámica y Vidrio,

Bol. Soc. Esp. Ceram. V., 45 [3] 163-168 (2006)

Consejo Superior de Investigaciones Científicas. [Link]

Licencia Creative Commons 3.0 España (by-nc)
Dielectric behavior of La1-xCaxMnO3 (0.4 ≤ x ≤ 0.5)

losses are a direct consequence of the semiconducting nature of is shown in Figure 7. A clear maximum (of increasing intensity
these materials, which have relatively high DC conductivities. for lower frequencies) is observed for all the samples. For
The high tanδ values are a serious obstacle for the application LC50 this maximum is centered on 185 K, which is the charge
of these manganites as dielectric materials. However, this ordering temperature, according to Fig. 4b. A similar behavior
limitation could be overcome using these compounds in was recently observed in La1.5Sr0.5NiO4, which was attributed
composite materials together with insulating oxides, such as to a rearrangement from the checkerboard-type charge
Al2O3 or SiO2. A comparison between tanδ curves of LC40, ordering to the stripe-type one (15). However, for LC40 and
LC45 and LC50 reveals that the higher Ca2+ content the higher LC45 these peaks are observed too, in spite of these samples
dielectric loss. This could be explained considering that the does not show charge ordering. In these cases the ε’r peaks
Ca2+ content is proportional to the hole concentration, since appear at temperatures very close to their corresponding
each Ca2+ ion produces the lost of an electron from a Mn3+ ion, metal-insulator transitions, as shown in Fig. 4a. All this
leading to an increase of the free carrier conduction. evidence seems to indicate the existence of a link between
The dependence of the dielectric constant with temperature the electronic state of the material and its dielectric function.
This experimental observation could motivate further studies
about similar systems that exhibit high dielectric constants by
non-ferroelectric mechanisms.

4. SUMMARY

The synthesized materials (La0.60Ca0.40MnO3, La0.55Ca0.45MnO3

and La0.50Ca0.50MnO3) show huge dielectric constants (105-106)
in a wide range of frequencies and temperatures. These
values are mainly the result of a strong extrinsic contribution
(interfacial polarization), besides an intrinsic effect due to
charge condensation.
The dielectric constant of these manganites exhibits
a maximum in temperature. For La0.60Ca0.40MnO3 and
La0.55Ca0.45MnO3 this is associated to their respective metal-
insulator transitions, while for La0.50Ca0.50MnO3 the peak is
related to a charge-order rearrangement.
Although the high dielectric losses observed for these
manganites make difficult its application as dielectric materials,
they could be used for the synthesis of composite materials
together with insulating matrixes.

ACKNOWLEDGEMENTS

This work was financed by MAT2004-05130 from MEC

(Spain). PMB thanks CONICET and Fundación Antorchas
(Argentina) for grants.

REFERENCES
1. R.J. Cava, Dielectric materials for applications in microwave communications,
J. Mater. Chem. 11 54-62 (2001).
2. B.G. Kim, S.M. Cho, T-Y. Kim and H.M. Jang, Giant dielectric permittivity
observed in Pb-based perovskite ferroelectrics, Phys. Rev. Lett. 86 3404-3406
(2001).
3. C.C. Homes, T. Vogt, M. Shapiro and A.P. Ramírez, Optical response of high-
dielectric-constant perovskite-related oxide, Science 293 673-676 (2001).
4. C. Pecharromán, F. Esteban-Betegón, J.F. Bartolomé, S. López-Esteban
and J.S. Moya, New percolative BaTiO3-Ni composites with a high and
frequency-independent dielectric constant (εr = 80 000), Adv. Mater. 13
1541-1544 (2001).
5. J. Wu, C.-W. Nan, Y. Lin and Y. Deng, Giant dielectric permittivity observed
in Li and Ti doped NiO, Phys. Rev. Lett. 89 217601 (2002).
6. D.C. Sinclair, T.B. Adams, F.D: Morrison and A.R. West, CaCu3Ti4O12: one-
step internal barrier layer capacitor, Appl. Phys. Lett. 80 2153-2155 (2002).
7. P. Lunkenheimer, V. Bobnar, A.V. Pronin, A.I. Ritus, A.A. Volkov and A.
Loidl, Origin of apparent colossal dielectric constants, Phys. Rev. B 66
052105 (2002).
8. C. Jardón, F. Rivadulla, L.E. Hueso, A. Fondado, J. Rivas, M.A. López
Quintela, R. Zysler, M. T. Causa and P. Sande, Experimental study of charge
ordering transition in Pr0.67Ca0.33MnO3, J. Magn Magn. Mater. 195-197 475-
Fig. 7- ε’r as a function of temperature at selected frequencies for LC40 476 (1999).
(a), LC45 (b) and LC50 (c). The frequency values are given in kHz.

Bol. Soc. Esp. Ceram. V., 45 [3] 163-168 (2006)

(c) Sociedad Española de Cerámica y Vidrio, 167
Consejo Superior de Investigaciones Científicas. [Link]
Licencia Creative Commons 3.0 España (by-nc)
 P.M. Botta, J. Mira, A. Fondado and J. Rivas

9. J. Rivas, B. Rivas-Murias, A. Fondado, J. Mira and M.A. Señarís-Rodríguez, 12. M. Roy, F.J. Mitchell, A.P. Ramírez and P.E. Schiffer, A study of the magnetic
Dielectric response of the charge-ordered two-dimensional nickelate and electrical crossover region of La0.5±δCa0.5±δMnO3, J. Phys.: Condens.
La1.5Sr0.5NiO4, Appl. Phys. Lett. 85 6224-6226 (2004). Matter. 11 4834-4859 (1999).
10. S.-W. Cheong and C.H. Chen, Colossal magnetoresistance, charge ordering 13. ICSD, Inorganic Crystal Structure Database 2004.
and related properties of manganese oxides, 241-266, C.N.R. Rao and B. 14. A. von Hippel, Dielectrics and Waves, Artech House, London, 1954.
Raveau Ed., World Scientific, Singapore, 1998. 15. R. Kajimoto, K. Ishizaka, H. Yoshizawa,Y. Tokura, Spontaneous
11. P. Levy, F. Parisi, G. Polla, D. Vega, G. Leyva and H. Lanza, Controlled rearrangement of the checkerboard charge order to stripe order in
phase separation in La0.50Ca0.50MnO3, Phys. Rev. B 62 6437-6441 (2000). La1.5Sr0.5NiO4, Phys Rev. B 67 014511 (2003).

Recibido: 15.07.05
Aceptado: 09.02.06

168 (c) Sociedad Española de Cerámica y Vidrio,

Bol. Soc. Esp. Ceram. V., 45 [3] 163-168 (2006)

Consejo Superior de Investigaciones Científicas. [Link]

Licencia Creative Commons 3.0 España (by-nc)