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Double doping effect on the structural and dielectric properties of PZT ceramics

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2004 J. Phys. D: Appl. Phys. 37 3174 (http://iopscience.iop.org/0022-3727/37/22/019) View the table of contents for this issue, or go to the journal homepage for more

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INSTITUTE OF PHYSICS PUBLISHING J. Phys. D: Appl. Phys. 37 (2004) 31743179

JOURNAL OF PHYSICS D: APPLIED PHYSICS PII: S0022-3727(04)78701-X

Double doping effect on the structural and dielectric properties of PZT ceramics
Puja Goel1 , K L Yadav1,3 and A R James2
1 2

Department of Physics, Indian Institute of Technology, Roorkee 247 667, India Solid State Physics Laboratory, Lucknow Road, Timarpur, Delhi 110 054, India

E-mail: klyadav35@yahoo.com and klalyfph@iitr.ernet.in

Received 5 April 2004, in nal form 2 September 2004 Published 28 October 2004 Online at stacks.iop.org/JPhysD/37/3174
doi:10.1088/0022-3727/37/22/019

Abstract Polycrystalline samples of the modied Pb(Zr1x Tix )O3 (PZT) composition, with representative formula Pb0.92 (Laz Bi1z )0.08 (Zr0.65 Ti0.35 )0.98 O3 (PLBZT), a family of relaxor ferroelectrics, were prepared via the chemical route with z = 0.3, 0.6 and 0.9. Crystalline phases of powders calcined at different temperatures and the microstructure of the sintered pellets were investigated by x-ray diffraction (XRD) analysis and scanning electron microscopy, respectively. XRD conrms the result obtained by differential scanning calorimetry. The XRD prole shows that the samples having z = 0.9 and 0.6 do not exhibit a pyrochlore phase, whereas the samples with z = 0.3, have 3% of the pyrochlore phase. Microstructural analysis suggests that the shape of grains and intergranular residual pores are modied upon La doping. The dielectric constant and dielectric losses were measured as a function of frequency at room temperature for different frequencies starting from 0.1 kHz to 1 MHz. The dielectric constant was found to be strongly inuenced by frequency whereas the Curie temperature remained almost the same. Finally, we conclude that the dielectric constant, loss and activation energy of PLBZT strongly suggest that these compounds are suitable for the preparation of high value capacitors and may be good candidates for device applications.

1. Introduction
There has been continued interest in lead-based ABO3 type perovskites, particularly in Pb(Zr1x Tix )O3 (PZT) based materials for a variety of applications such as transducers, sensors and dielectric ceramics for capacitor applications particularly in the eld of nonvolatile memories [17]. Depending upon the specic requirement for different applications, various compositions of the PZT system with various Zr/Ti ratios may be chosen. There are several reports [811] concerning the synthesis and characterization of modied PZT synthesis by a solid-state reaction method with various Zr/Ti ratios. La doping is one of the most widely used strategies to tailor the dielectric and optical properties of ferroelectric materials. It also enhances the breadth of diffuse phase transition (DPT) due to the promoted
3

Author to whom any correspondence should be addressed.

B-site compositional inhomogeneity, thus enlarging the utilization temperature range of multi-layer ceramic capacitors (MLCCs) and holding promise for applications like precision displacement sensors [12, 13]. Much work has been done in the past to study the effects of substitution of single isovalent, supervalent or subvalent dopants with varying concentrations in the A and B sites of the PZT [1424] for different device applications, but not much work has been done to report the effect of double doping (of different radii) at the Pb site. Hence, powder samples of Pb0.92 (Laz Bi1z )0.08 (Zr0 .65 Ti0.35 )0.98 O3 (PLBZT) (where z = 0.3, 0.6, 0.9) were synthesized by the chemical co-precipitation method because of their better purity, better homogeneity and enhanced reactivity leading to the development of quality ceramics. Our goal in the present work is to investigate the effect of supervalent double doping (La+3 and Bi+3 ) at the Pb site on the structural and dielectric properties and the nature of the ferroelectric phase transition in chemically synthesized PZT compounds. 3174

0022-3727/04/223174+06$30.00

2004 IOP Publishing Ltd

Printed in the UK

Structural and dielectric properties of PZT ceramics

2. Experiment
Powder samples of the PLBZT system were prepared according to the formula Pb1x (Laz Bi1z )x (Zry Ti1y )(1x/4) O3 via the chemical route for x = 0.08, y = 0.65 and z = 0.3, 0.6 and 0.9. Compositions are denoted as 30/70, 60/40, 90/10 according to the La and Bi ratio. Nitrate salts (AR grade) of component atoms [Pb(NO3 )2 , La(NO3 )3 6H2 O, Bi(NO3 )3 5H2 O, ZrO(NO3 )2 2H2 O] were dissolved in double distilled water. The resulting solution was stirred on a magnetic stirrer for 23 h in order to get a clear transparent solution. Titanium isopropoxide was added drop-wise to this solution. The added titanium hydrolysed into an intermediate Ti(OH)4 and slowly redissolved. A few drops of nitric acid were added to dissolve Ti(OH)4 completely and to get a clear solution. A white precipitate was observed immediately after adding some amount of ammonia into the solution. To obtain the desired powder, the solution was vacuum ltered and washed several times with distilled water. The ltered powder cake was then kept in an oven (for 24 h) at 150C for drying. Thermal analysis, such as differential thermal analysis (DTA), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG) of the oven-dried powder was carried out in a thermal analyser (Perkin Elmer, Pyris Diamond) at a heating rate of 5C min1 . Oven-dried powders of the three different compositions prepared were calcined at 800C for 4 h. These powders were cold pressed into discs (pellets) at a pressure of 2 108 N m2 using a uniaxial hydraulic press. The pellets were sintered at 1100C for 6 h. In order to prevent PbO loss and to maintain the stoichiometry of the compounds, the pellets were placed in a covered alumina crucible with lead zirconate titanate powder during sintering. The densities of sintered pellets were calculated by Archimedes method. The formation and quality of the PLBZT compound in calcined powder as well as in sintered pellets were studied using an x-ray diffractometer (PW 1140/90), using Cu K ( = 0.154 18 nm) in a wide range of Bragg angles (20 2 60) at room temperature. To nd the temperature at which the pure phase was formed, the rst composition (30/70) was heated at different temperatures for 2 h starting from 200C up to 800C in steps of 100C and x-ray diffraction (XRD) was done. Before measuring the dielectric properties, the sintered pellets were coated with high purity silver paste (to work as an electrode) and dried at 200C for 2 h. The dielectric constant () and dielectric loss (tan ) of the samples as a function of temperature (room temperature to 410C) were obtained using a capacitance measuring assembly (HP-4284A) with a three terminal sample holder. Microstructures of the samples were analysed by using scanning electron microscope (SEM) (LEO 435 VP).

Figure 1. DTA, DTG and TGA curves of as-prepared PLBZT powder for z = 0.3.

Figure 2. XRD of PLBZT at different temperatures for z = 0.3: () TiO2 , ( ) Pb(NO3 ), ( ) La2 O3 , () Bi2 O3 , () ZrO2 .

3. Results and discussion

TGA, DTG and DTA curves of the as-prepared PLBZT powder (oven dried at 150C) are shown in gure 1. The DTA study reveals two endothermic peaks at 446C and 460C, which are due to the decomposition of Pb(NO3 )2 into PbO [25]. An onset of weight loss has been observed at 386C in TGA, and

the weight becomes almost constant after 500C, which gives information about the complete decomposition of complex oxyhydroxides at this temperature and also conrms that this temperature is sufcient to obtain the desired powder through this process; this was also conrmed by XRD analysis. The XRD patterns (gure 2) of the PLBZT (30/70) powders heat treated at temperatures ranging from 200C to 800C for 2 h, were obtained to nd the different phases during compound formation. As indicated, the XRD pattern of the as-prepared powder (calcined at 200C) has mixed peaks of the oxides of precursor compounds such as La2 O3 , ZrO2 , TiO2 , and Pb(NO3 )2 . The rhombohedral phase of PLBZT is observed after calcinations at 400C. A comparative analysis of both XRD and DTA shows that the reaction is completed at about 3175

P Goel et al

Table 1. Structural and electrical parameters of PLBZT ceramics. Lattice constant Composition (z) 0.3 0.6 0.9 a (nm) 0.402 0.404 0.404 89.72 86.99 89.80 Electrical properties at 1 kHz max 3980 4982 9440 Tc (C) 360 286 214 1.88 1.77 2.08 Ea (eV) 5.96 2.02 0.88 Density (gm cm3 ) 7.35 7.55 7.68

450C. The XRD prole reveals that complete crystallization of PLBZT could be achieved at calcinations around 500C and this is conrmed from the TGA (gure 2) as no weight loss is observed after 500C. Diffraction peaks become sharper upon calcinations at temperatures higher than 500C due to better crystallization of the material. Lattice parameters (table 1) were calculated using the dhkl values calculated from XRD patterns of pellets sintered at 1000C. These values are found to be consistent with the reported values [26]. From the diffraction pattern of the PLBZT and calculated lattice parameters (a and values), no change could be observed in the basic crystal structure of PZT after (La, Bi) doping (for z = 0.3, 0.6, 0.9 at the A site), except that a pyrochlore peak is observed near the perovskite (110) peak for z = 0.3. The relative amount of the pyrochlore phase to the perovskite phase was estimated using the following peak area ratio equation [27]: %Pyrochlore = Apyrochlore 100, Apyrochlore + A(110)

where Apyrochlore and A(110) are the areas under the pyrochlore peak and the (110) perovskite phase. The pyrochlore value is 3%, which is small and in agreement with the value reported [28] for doped PZT. Hence, this composition can also be considered as a single phase. The measured linear particle size ranged from 20 to 27 nm, of the powders calcined at different temperatures (400800C), calculated from XRD patterns by making use of Scherrers equation [29] P = K/(1/2 cos ) where K = 0.89 and 1/2 is the full width at half maximum intensity. SEM micrographs of the pellets prepared from PLBZT powder and sintered at 1100C are shown in gures 3(a)(c). The sintered pellets have been found to have a grain size of the order of (1.2 m) and uniform grain distribution, which is in accordance with the high-density value, as can be seen from table 1. The frequency variation of the dielectric constant () and the dielectric loss (tan ) of the sample are plotted in gures 4(a) and (b), respectively. The frequency variation of is like that of normal ferroelectric materials. The pattern of dielectric losses is irregular up to a frequency of 100 kHz for all the compositions and then starts increasing continuously. This increase can be explained on the basis of the dipole mechanism [30] of losses given by = 1, which is the condition for the maximum of dielectric losses in a polar dielectric at a given temperature. Here, the frequency () corresponds to such a ratio between the period of an external eld and the time of the relaxation of the dipole as is needed to observe the greatest loss of energy to overcome the resistance of the viscous medium by the dipoles. To determine the nature of the ferroelectric phase transition, the variation of and tan of the samples with temperature was studied. It is apparent from gures 5(a)(c) that 3176

Figure 3. SEM micrographs of PLBZT pellets (a) z = 0.3, (b) z = 0.6 and (c) z = 0.9 sintered at 1100C.

the variation of with temperature (40410C) at different frequencies (0.1 kHz to 1 MHz) is a broadened curve rather than a sharp peak (as in normal ferroelectrics) around Tc , which is one of the most important characteristics of a disordered perovskite structure with a diffuse phase transition. This broadening is believed to be due to the compositional

Structural and dielectric properties of PZT ceramics

(a)

(b)

Figure 5. Variation of dielectric constant with temperature (at different frequencies) for (a) z = 0.3, (b) z = 0.6 and (c) z = 0.9 compositions.

Figure 4. (a) Frequency dependence of dielectric constant at room temperature for (a) z = 0.3, (b) z = 0.6 and (c) z = 0.9 compositions of PLBZT. (b) Frequency dependence of dielectric losses at room temperature for (a) z = 0.3, (b) z = 0.6 and (c) z = 0.9 compositions of PLBZT.

uctuations, and/or substitutional disordering in the arrangement of cations in one or more crystallographic sites of the structure, which leads to microscopic or nanoscopic heterogeneity in the compounds, with different local Curie points [31, 32]. These uctuations occur when Pb+2 , Ti+4 and Zr+4 are replaced by soft dopants La+3 and Bi+3 . The changes are ascribed to the lead vacancies and the resulting increase in domain wall mobility [33]. It is also clear that an increase in frequency causes a decrease in the maximum value of the dielectric constant, whereas only a small shift in Curie temperature could be observed. The degree of diffuseness ( ) in the dielectric peak of the material was estimated by using the expression 1 1 max (T Tc ) ,

Figure 6. Variation of % TC for (a) z = 0.3, (b) z = 0.6 and (c) z = 0.9 as a function of temperature, at 1 kHz frequency.

The temperature coefcient of permittivity (TC ) is dened as T RT , TC = 100 RT where T is the permittivity at any temperature T and RT is its room temperature value. The relative variation of the dielectric permittivity with temperature between room temperature and 400C for all the compositions are shown in gures 6(a)(c). Curve (c) is signicantly broader than curve (a). This indicates that PLBZT (90/10) possesses a more diffuse phase transition than the rest of the compositions. From the above dielectric analysis we have found that the peak dielectric constant increased with an increase in La+3 concentration, which implies that the substitution of La+3 ions at the A site is more effective in increasing the dipole moment of the lattice [34], which enhances the peak dielectric constant (gure 7). The variation of dielectric loss with temperature (40410C) at frequencies starting from 0.1 kHz to 1 MHz is 3177

where and max are the dielectric constants at temperature T (T > Tc ) and max (maximum value of at the transition temperature Tc ), respectively. This large value of (table 1) conrms the second-order phase transition and the high degree of disorderliness in the material [18, 28].

P Goel et al

Figure 7. Variation of dielectric constant (at room temperature (RT ) and at Tc (max ) and Tc as a function of composition (z).

shown in gures 8(a)(c). The dielectric loss was found to be very small and nearly the same at all the frequencies in the temperature range 40125C. Above 125C, a continuous increase in tan was observed, and was greater at lower frequencies. As a general rule, tan increases appreciably when the temperature rises. This growth in tan is brought about by an increase both in the conduction of residual current and the conduction of absorption current. In actual fact, the rise in temperature and the resulting drop in viscosity exert a double effect on the amount of losses due to the friction of the rotating dipoles, on the one hand, and the increase in the degree of dipole orientation, on the other hand; there is a reduction in energy required to overcome the resistance of the viscous medium. In a polar substance, apart from dipole losses, losses due to electrical conduction, which increase with an increase in temperature, are present [30]. The observed tan of our samples were nearly the same for all the compositions at lower temperatures but started rising on raising the temperature. Figure 9 is the plot of log( ) with respect to the inverse temperature (T 1 ). The activation energy Ea can be calculated by making use of this plot and the relation given below: = 0 exp Ea KB T .

Figure 8. Dielectric loss variation as a function of temperature of PLBZT (a) z = 0.3, (b) z = 0.6 and (c) z = 0.9 compositions at different frequencies.

The conductivity is given by = 0 tan , where 0 is the vacuum dielectric constant, is the angular frequency and KB is the Boltzmann constant. The calculated values of activation energy at 1 kHz frequency for all the compositions are given in table 1. The value of Ea decreases with increasing La+3 as can be seen from gure 9. This type of conductivity has been conrmed as p-type [35]. Substitution of supervalent cations such as La+3 or Bi+3 for Pb+2 contributes electrons and thus reduces the hole conductivity according to the law of mass action. This is believed to be due to the formation of Pb site 3178

Figure 9. Conductivity vs temperature characteristics of PLBZT (a) z = 0.3, (b) z = 0.6 and (c) z = 0.9 compositions at 1 kHz frequency.

vacancies (here, with La doping) as in the reaction 0.01La2 O3 + Pb(ZrTi)O3 (Pb0.97 La0.020.01 )(ZrTi)O3 +0.03PbO taking place during sintering.

Structural and dielectric properties of PZT ceramics

4. Conclusions
In this work we have reported the effect of supervalent double doping (donor type) on the structural and dielectric properties of a composition of PZT near the morphotropic phase boundary (MPB) with xed Zr/Ti (65/35) ratio prepared by the co-precipitation method. The chemical route allows a low temperature synthesis (450C) and ensures a molecular level of homogeneity. The results can be summarized as follows: XRD studies conrm the formation of a rhombohedral phase of all the studied samples at 450C. The density increases with the increasing concentration of La+3 , which is also conrmed by the SEM analysis. There is a variation in the grain size with different concentrations of La+3 and Bi+3 . In dielectric studies, the transition temperature is found to decrease whereas is found to increase with the increasing concentration of lanthanum. It is nally concluded that the dielectric constant, loss and activation energy of PLBZT strongly suggest that these compounds are suitable for the preparation of high value capacitors and may be good candidates for device applications.

Acknowledgments
The authors thank Professor M R Maurya (Department of Chemistry, IIT Roorkee) for his help in material preparation and the Head of the Physics Department and Head of Metallurgy and Materials Engineering for their kind help and encouragement. PG thanks MHRD for providing a research fellowship.

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