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Ferroelectrics
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The Effect of PbO-Nonstoichiometry on Dielectric and Semiconducting Properties of PbFe0.5Nb0.5O3-Based Ceramics

I. P. Raevski , S. P. Kubrin , S. A. Kovrigina , S. I. Raevskaya
a a a a

, V. V. Titov , A. S. Emelyanov , M. A. Malitskaya & I. N.

a

Zakharchenko
a

Institute of Physics and Physical Department of Southern Federal University, Stachki Ave. 194, Rostov on Don, 344090, Russia Version of record first published: 23 Jun 2010.

To cite this article: I. P. Raevski , S. P. Kubrin , S. A. Kovrigina , S. I. Raevskaya , V. V. Titov , A. S. Emelyanov , M. A. Malitskaya & I. N. Zakharchenko (2010): The Effect of PbO-Nonstoichiometry on Dielectric and Semiconducting Properties of PbFe0.5Nb0.5O3-Based Ceramics, Ferroelectrics, 397:1, 96-101 To link to this article: http://dx.doi.org/10.1080/00150193.2010.484738

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Ferroelectrics, 397:96101, 2010 Copyright Taylor & Francis Group, LLC ISSN: 0015-0193 print / 1563-5112 online DOI: 10.1080/00150193.2010.484738

The Effect of PbO-Nonstoichiometry on Dielectric and Semiconducting Properties of PbFe0.5 Nb0.5 O3 -Based Ceramics
I. P. RAEVSKI, S. P. KUBRIN, S. A. KOVRIGINA, S. I. RAEVSKAYA, V. V. TITOV, A. S. EMELYANOV, M. A. MALITSKAYA, AND I. N. ZAKHARCHENKO
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Institute of Physics and Physical Department of Southern Federal University, Stachki Ave. 194, Rostov on Don, 344090, Russia
Dielectric, X-ray and electric resistivity studies of nonstoichiometric PbFe0.5 Nb0.5 O3 based ceramics obtained by solid-state reaction route with PbO/(Fe0.5 Nb0.5 O2 ) molar ratio differing from 0.6 to 1.2 have been carried out. Deviation from stoichiometric PbFe0.5 Nb0.5 O3 composition leads to formation of diphase mixtures containing ferroelectric perovskite PbFe0.5 Nb0.5 O3 phase and nonferroelectric PbO or pyrochlore Pb3 Nb4 O13 phases and to decreasing of the dielectric permittivity values. The electric resistivity of PbFe0.5 Nb0.5 O3 ceramics decreases dramatically when the sintering temperature increases. The formation of the pyrochlore phase decreases the room temperature resistivity values while the anomaly of the positive temperature coefcient of resistivity above the ferroelectric Curie temperature gradually diminishes with the increase of the pyrochlore content. Keywords Dielectric permittivities; ferroelectric ceramics; lead iron niobate; stoichiometry; positive temperature coefcient of resistivity.

Introduction
Ternary perovskite multiferroic PbFe0.5 Nb0.5 O3 (PFN) is a promising basic material for ceramic capacitors, piezoelectrics, electrostrictors and PTC resistors exhibiting positive temperature coefcient of resistivity (PTCR) [15]. Similar to other lead-containing complex perovskites, e. g. PbMg1/3 Nb2/3 O3 (PMN), the most common problem encountered during the synthesis of PFN is the appearance of stable pyrochlore phases [69]. These phases have a low dielectric permittivity values and it is commonly believed that even a minor content of pyrochlore phase (about few %) reduces sufciently of ceramics. The effect of the pyrochlore phase content on the dielectric properties of PMN has been thoroughly studied [8, 9], while the similar data for PFN are absent in literature. Besides, the effect of the pyrochlore phase on the semiconducting properties of PFN has not been studied yet. The scope of the present work is the study of dielectric and semiconducting properties of nonstoichiometric PFN-based ceramics with differing PbO/(Fe0.5 Nb0.5 O2 ) molar ratios.
Received September 22, 2009; in nal form January 20, 2010. Corresponding author. E-mail: igorraevsky@gmail.com

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The PbO-deciency is the most probable type of stoichiometry breaking in lead-containing oxides due to PbO evaporation during sintering. On the other hand, the opposite situation is also of practical interest as an addition of PbO excess is often used for lowering the sintering temperature and compensation of PbO losses in ceramics of complex lead-containing perovskites.

Experimental
The ceramic samples were prepared by conventional solid state reaction route. The calculated quantities of reagent grade PbO, Fe2 O3 and Nb2 O5 corresponding to the PbO/(Fe0.5 Nb0.5 O2 ) molar ratios from 0.6:1 to 1.2:1 (these compositions will be referred further as Pbx Fe0.5 Nb0.5 O3 where x varies from 0.6 to 1.2) were mixed thoroughly in agate mortar in the presence of ethyl alcohol. After drying this slurry, disks of 10 mm in diameter, were pressed at 100 MPa using polyvinyl alcohol as a binder. Sintering was carried out for 2 hours at 9601160 C in a closed alumina crucible. In some cases 1wt.% of Li2 CO3 was added before mixing. This addition promotes formation of the perovskite modication of PFN and reduces its conductivity [9, 10]. Several compositions were calcined at 850 C for 4 hours before sintering. The resultant slug was then ground and disc samples were pressed as described above. The density of ceramics was about 8595% of the theoretical one. For electrical measurements the samples were grinded and electroded by ring on silver paste or rubbing In-Ga alloy. Dielectric studies were carried out in the 0.1 kHz1 MHz frequency range with the aid of the computer-controlled E7-20 impedance analyzer in the course of continuous heating at a rate of 23 K/min. Resistivity values were measured under dc electric eld of 1 V/cm. X-ray studies were carried out at room temperature with the help of DRON-3 diffractometer using FeK radiation.

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Results and Discussion

X-ray studies of the ceramics obtained have shown that nominally stoichiometric PFN ceramics besides perovskite PFN phase usually contain small amounts of pyrochlore Pb3 Nb4 O13 phase. The volume percent of pyrochlore phase ,was estimated from the ratio of relative intensities of the (222) pyrochlore peak (I222 )PYRO and the (110) perovskite peak (I110 )PER [8]: = (I222 )PYRO 100% (I222 )PYRO + (I110 )PER (1)

For nominally stoichiometric PFN the coefcient is equal 35%. In stoichiometric PFN with addition of 1 wt.% of Li2 CO3 no pyrochlore phase was detected by X-ray studies. Decreasing of the PbO/(Fe0.5 Nb0.5 O2 ) molar ratio below stoichiometric 1:1 value leads to increasing of the pyrochlore phase content (see inset in Fig. 1). In compositions with x > 1 the PbO phase was detected besides the perovskite PFN phase. Dielectric studies have shown that the maximal value of permittivity m for the Pbx Fe0.5 Nb0.5 O3 ceramic compositions lowers greatly as x decreases (Fig. 1), however the diffusion of the (T) peak does not change substantially (Fig. 2a). The latter result implies that perovskite and pyrochlore phases seem to form a statistical mixture rather than a matrix system. Indeed reasonably good agreement of the experimental and calculated

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Figure 1. (T) dependences at 1 kHz measured on heating for some Pbx Fe0.5 Nb0.5 O3 ceramic compositions. Numbers at the curves correspond to x values. The inset shows compositional dependence of the pyrochlore Pb3 Nb4 O13 phase content for Pbx Fe0.5 Nb0.5 O3 +1wt.% Li2 CO3 compositions with x 1.

Figure 2. (a) Dependences of permittivity at 1 kHz related to its maximal value m on the reduced temperature T-Tm for some Pbx Fe0.5 Nb0.5 O3 ceramic compositions. (b) Experimental (points) and calculated using the Lichtenecker formula (solid lines) (T-Tm ) dependences for some Pbx Fe0.5 Nb0.5 O3 compositions. Numbers at the curves correspond to x values.

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Figure 3. Dependences of room-temperature resistivity on sintering temperature TS for stoichiometric PbFe0.5 Nb0.5 O3 ceramics fabricated by: (1) One-step sintering of the mixture of oxides followed by slow cooling. (2) Sintering of the preliminary calcined mixture of oxides followed by slow cooling. (3) Sintering of the preliminary calcined mixture of oxides followed by quenching to room temperature.

(T) curves (Fig. 2b) was achieved by using the Lichtenecker formula [10]: ln = 1 ln 1 + 2 ln 2 + 3 ln 3 , (2)

where 1 , 2 , 3 and 1 , 2 , 3 are volume fractions and permittivities of the perovskite phase, pyrochlore phase and pores respectively. The values of 1 at different temperatures were taken from the experimental (T) curve for stoichiometric PbFe0.5 Nb0.5 O3 ceramics with addition of 1 wt.% of Li2 CO3 . These data were corrected for porosity using the Lichtenecker formula. The values of 2 = 100 for pyrochlore phase were taken for all temperatures [8, 9]. The step in the (T) curve at T 70 C, corresponding to the rhombohedral (monoclinic) -tetragonal phase transition [57] is well observed only in stoichiometric ceramic

Figure 4. Dependences of room-temperature resistivity on sintering temperature TS for nonstoichiometric Pbx Fe0.5 Nb0.5 O3 ceramic compositions fabricated by one-step sintering of the mixture of oxides followed by slow cooling. Numbers at the curves correspond to x values

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Figure 5. Temperature dependences of resistivity for nonstoichiometric Pbx Fe0.5 Nb0.5 O3 ceramic compositions. Numbers at the curves correspond to x values.

compositions. The temperature Tm of the (T) maximum varies only slightly on deviation from stoichiometric (x = 1) Pbx Fe0.5 Nb0.5 O3 composition, indicating that PFN phase maintain its stoichiometry across the whole 0.6 <x < 1.2 compositional range. The electrical resistivity of Pbx Fe0.5 Nb0.5 O3 ceramics depends dramatically on the sintering temperature TS for both stoichiometric and nonstoichiometric compositions (Figs. 3 and 4). Such behavior is believed to be due to the Fe ions valence changes from Fe3+ to Fe2+. This supposition is in line with the much lower resistivity values of stoichiometric PbFe0.5 Nb0.5 O3 ceramics quenched from TS to room temperature (curve 3 in Fig. 3). Lowering of PbO/(Fe0.5 Nb0.5 O2 ) ratio, leading to formation of the pyrochlore phase, decreases TS threshold above which low resistivity values are achieved (Fig. 4). On the other hand, Li-doping and addition of PbO excess, both eliminating the pyrochlore phase content, increase the ceramic resistivity. Thus, the presence of the pyrochlore phase seems to enhance the reduction of PbFe0.5 Nb0.5 O3 -based ceramics in the course of sintering. The similar situation is known for BaTiO3 ceramics with TiO2 excess where the reduction behavior is greatly governed by the amount of the Ba6 Ti17 O40 phase [1]. In accord with these considerations the PTCR anomaly above the ferroelectric Curie temperature gradually diminishes with the increase of the pyrochlore content (Fig. 5).

Summary
A deviation from stoichiometric PbFe0.5 Nb0.5 O3 composition by changing PbO/(Fe0.5 Nb0.5 O2 ) molar ratio leads to formation of diphase mixtures containing ferroelectric perovskite PbFe0.5 Nb0.5 O3 phase and nonferroelectric PbO or pyrochlore Pb3 Nb4 O13 phases. An increasing of non-perovskite phase content leads to decrease of the dielectric permittivity values, however the diffusion of the (T) maxima increases insufciently. Perovskite and pyrochlore phases seem to form a statistical mixture rather than a matrix system. The electrical resistivity of Pbx Fe0.5 Nb0.5 O3 ceramics depends dramatically on the sintering

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temperature TS . A lowering of PbO/(Fe0.5 Nb0.5 O2 ) ratio decreases TS threshold, above which low resistivity values are achieved.

Acknowledgment
This study is supported in part by the Russian Foundation for Basic Research (RFBR) grant 09-02-92672 IND a.

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