You are on page 1of 7

Home

Search

Collections

Journals

About

Contact us

My IOPscience

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

Download details: IP Address: 14.139.82.99 The article was downloaded on 08/02/2012 at 16:46

Please note that terms and conditions apply.

98 O3 (PLBZT). India Solid State Physics Laboratory. 1. Microstructural analysis suggests that the shape of grains and intergranular residual pores are modified upon La doping.iop. Phys. Timarpur.com and klalyfph@iitr. Hence.65 Ti0.92 (Laz Bi1−z )0. Indian Institute of Technology. The dielectric constant and dielectric losses were measured as a function of frequency at room temperature for different frequencies starting from 0.org/JPhysD/37/3174 doi:10.9 and 0.6 and 0.9.3. La doping is one of the most widely used strategies to tailor the dielectric and optical properties of ferroelectric materials. Lucknow Road. It also enhances the breadth of diffuse phase transition (DPT) due to the promoted 3 Author to whom any correspondence should be addressed.92 (Laz Bi1−z )0. 13]. 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. a family of relaxor ferroelectrics. Much work has been done in the past to study the effects of substitution of single isovalent.00 © 2004 IOP Publishing Ltd Printed in the UK . 37 (2004) 3174–3179 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 . but not much work has been done to report the effect of double doping (of different radii) at the Pb site. There are several reports [8–11] concerning the synthesis and characterization of modified PZT synthesis by a solid-state reaction method with various Zr/Ti ratios. Introduction There has been continued interest in lead-based ABO3 type perovskites.9) were synthesized by the chemical co-precipitation method because of their better purity.65 Ti0. we conclude that the dielectric constant. Finally. with representative formula Pb0. in final form 2 September 2004 Published 28 October 2004 Online at stacks. powder samples of Pb0. 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. 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. particularly in Pb(Zr1−x Tix )O3 (PZT) based materials for a variety of applications such as transducers. better homogeneity and enhanced reactivity leading to the development of quality ceramics. 0. 3174 0022-3727/04/223174+06$30. The dielectric constant was found to be strongly influenced by frequency whereas the Curie temperature remained almost the same.35 )0. whereas the samples with z = 0. K L Yadav1.1 kHz to 1 MHz. thus enlarging the utilization temperature range of multi-layer ceramic capacitors (MLCCs) and holding promise for applications like precision displacement sensors [12.6 do not exhibit a pyrochlore phase.08 (Zr0.1088/0022-3727/37/22/019 Abstract Polycrystalline samples of the modified Pb(Zr1−x Tix )O3 (PZT) composition. India E-mail: klyadav35@yahoo. Depending upon the specific requirement for different applications.3. The XRD profile shows that the samples having z = 0.08 (Zr0 . supervalent or subvalent dopants with varying concentrations in the A and B sites of the PZT [14–24] for different device applications. have 3% of the pyrochlore phase. D: Appl. various compositions of the PZT system with various Zr/Ti ratios may be chosen. 0. respectively.in Received 5 April 2004. were prepared via the chemical route with z = 0. 0.3 and A R James2 1 2 Department of Physics. Delhi 110 054.98 O3 (PLBZT) (where z = 0.6.3.ernet. Phys.INSTITUTE OF PHYSICS PUBLISHING J. B-site compositional inhomogeneity. sensors and dielectric ceramics for capacitor applications particularly in the field of nonvolatile memories [1–7]. Roorkee 247 667.35 )0. XRD confirms the result obtained by differential scanning calorimetry.

Titanium isopropoxide was added drop-wise to this solution. ( ) Pb(NO3 ).6 and 0. Nitrate salts (AR grade) of component atoms [Pb(NO3 )2 . A comparative analysis of both XRD and DTA shows that the reaction is completed at about 3175 . the XRD pattern of the as-prepared powder (calcined at 200˚C) has mixed peaks of the oxides of precursor compounds such as La2 O3 .08. The resulting solution was stirred on a magnetic stirrer for 2–3 h in order to get a clear transparent solution. this was also confirmed by XRD analysis. y = 0. Oven-dried powders of the three different compositions prepared were calcined at 800˚C for 4 h. and the weight becomes almost constant after 500˚C. The added titanium hydrolysed into an intermediate Ti(OH)4 and slowly redissolved. Pyris Diamond) at a heating rate of 5˚C min−1 . Before measuring the dielectric properties.3. The densities of sintered pellets were calculated by Archimedes’ method. As indicated. The DTA study reveals two endothermic peaks at 446˚C and 460˚C. (◦) Bi2 O3 .3. the sintered pellets were coated with high purity silver paste (to work as an electrode) and dried at 200˚C for 2 h. Microstructures of the samples were analysed by using scanning electron microscope (SEM) (LEO 435 VP). An onset of weight loss has been observed at 386˚C in TGA. A few drops of nitric acid were added to dissolve Ti(OH)4 completely and to get a clear solution. ( ) La2 O3 . A white precipitate was observed immediately after adding some amount of ammonia into the solution.9. DTA. thermogravimetric analysis (TGA) and differential thermogravimetry (DTG) of the oven-dried powder was carried out in a thermal analyser (Perkin Elmer. Thermal analysis. These powders were cold pressed into discs (pellets) at a pressure of 2 × 108 N m−2 using a uniaxial hydraulic press. the solution was vacuum filtered and washed several times with distilled water. The XRD patterns (figure 2) of the PLBZT (30/70) powders heat treated at temperatures ranging from 200˚C to 800˚C for 2 h. the first composition (30/70) was heated at different temperatures for 2 h starting from 200˚C up to 800˚C in steps of 100˚C and x-ray diffraction (XRD) was done. The pellets were sintered at 1100˚C for 6 h. 0. Experiment Powder samples of the PLBZT system were prepared according to the formula Pb1−x (Laz Bi1−z )x (Zry Ti1−y )(1−x/4) O3 via the chemical route for x = 0. DTG and TGA curves of as-prepared PLBZT powder for z = 0. To obtain the desired powder. Results and discussion TGA. Bi(NO3 )3 · 5H2 O. ZrO(NO3 )2 · 2H2 O] were dissolved in double distilled water. TiO2 . such as differential thermal analysis (DTA). Figure 2. La(NO3 )3 · 6H2 O. 60/40. ZrO2 . the pellets were placed in a covered alumina crucible with lead zirconate titanate powder during sintering. 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).3: (∗) TiO2 . DTG and DTA curves of the as-prepared PLBZT powder (oven dried at 150˚C) are shown in figure 1. XRD of PLBZT at different temperatures for z = 0. The rhombohedral phase of PLBZT is observed after calcinations at 400˚C.Structural and dielectric properties of PZT ceramics 2. Figure 1.154 18 nm) in a wide range of Bragg angles (20˚ 2θ 60˚) at room temperature. which gives information about the complete decomposition of complex oxyhydroxides at this temperature and also confirms that this temperature is sufficient to obtain the desired powder through this process. 90/10 according to the La and Bi ratio. 3. and Pb(NO3 )2 .65 and z = 0. The filtered powder cake was then kept in an oven (for 24 h) at 150˚C for drying. In order to prevent PbO loss and to maintain the stoichiometry of the compounds. were obtained to find the different phases during compound formation. using Cu Kα (λ = 0. which are due to the decomposition of Pb(NO3 )2 into PbO [25]. The dielectric constant (ε) and dielectric loss (tan δ) of the samples as a function of temperature (room temperature to 410˚C) were obtained using a capacitance measuring assembly (HP-4284A) with a three terminal sample holder. Compositions are denoted as 30/70. To find the temperature at which the pure phase was formed. (•) ZrO2 .

404 α 89. Hence. the variation of ε and tan δ of the samples with temperature was studied.89 and β1/2 is the full width at half maximum intensity. It is apparent from figures 5(a)–(c) that 3176 Figure 3.99˚ 89. Lattice parameters (table 1) were calculated using the dhkl values calculated from XRD patterns of pellets sintered at 1000˚C.9 a (nm) 0.9 sintered at 1100˚C.80˚ Electrical properties at 1 kHz εmax 3980 4982 9440 Tc (˚C) 360 286 214 γ 1. (b) z = 0. Structural and electrical parameters of PLBZT ceramics.08 Ea (eV) 5.3.55 7.68 450˚C. the variation of ε with temperature (40–410˚C) at different frequencies (0.96 2. Lattice constant Composition (z) 0.6 and (c) z = 0. Bi) doping (for z = 0.3. no change could be observed in the basic crystal structure of PZT after (La.3.77 2. calculated from XRD patterns by making use of Scherrer’s equation [29] P = Kλ/(β1/2 cos θ) where K = 0.02 0. except that a pyrochlore peak is observed near the perovskite (110) peak for z = 0. as can be seen from table 1.35 7. Diffraction peaks become sharper upon calcinations at temperatures higher than 500˚C due to better crystallization of the material.P Goel et al Table 1.3 0. This broadening is believed to be due to the compositional . respectively. which is small and in agreement with the value reported [28] for doped PZT. SEM micrographs of PLBZT pellets (a) z = 0. This increase can be explained on the basis of the dipole mechanism [30] of losses given by ωτ = 1. which is the condition for the maximum of dielectric losses in a polar dielectric at a given temperature. The XRD profile reveals that complete crystallization of PLBZT could be achieved at calcinations around 500˚C and this is confirmed from the TGA (figure 2) as no weight loss is observed after 500˚C. From the diffraction pattern of the PLBZT and calculated lattice parameters (a and α values).404 0. These values are found to be consistent with the reported values [26].9 at the A site). which is in accordance with the high-density value.72˚ 86.6 0. The frequency variation of the dielectric constant (ε) and the dielectric loss (tan δ) of the sample are plotted in figures 4(a) and (b). The pattern of dielectric losses is irregular up to a frequency of 100 kHz for all the compositions and then starts increasing continuously. The frequency variation of ε is like that of normal ferroelectric materials. The sintered pellets have been found to have a grain size of the order of (∼1. To determine the nature of the ferroelectric phase transition. SEM micrographs of the pellets prepared from PLBZT powder and sintered at 1100˚C are shown in figures 3(a)–(c). 0. the frequency (ω) corresponds to such a ratio between the period of an external field and the time τ 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.2 µm) and uniform grain distribution.6.88 1. this composition can also be considered as a single phase. Here. The relative amount of the pyrochlore phase to the perovskite phase was estimated using the following peak area ratio equation [27]: %Pyrochlore = Apyrochlore × 100.88 Density (gm cm−3 ) 7.1 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. Apyrochlore + A(110) where Apyrochlore and A(110) are the areas under the pyrochlore peak and the (110) perovskite phase. 0.402 0. The pyrochlore value is 3%. The measured linear particle size ranged from 20 to 27 nm. of the powders calcined at different temperatures (400–800˚C).

The changes are ascribed to the lead vacancies and the resulting increase in domain wall mobility [33]. (a) Frequency dependence of dielectric constant at room temperature for (a) z = 0.3. which enhances the peak dielectric constant (figure 7). (b) Frequency dependence of dielectric losses at room temperature for (a) z = 0. These fluctuations occur when Pb+2 . TCε = 100 εRT where εT is the permittivity at any temperature T and εRT is its room temperature value. (b) z = 0.6 and (c) z = 0. 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]. The relative variation of the dielectric permittivity with temperature between room temperature and 400˚C for all the compositions are shown in figures 6(a)–(c). . (b) z = 0. The degree of diffuseness (γ ) in the dielectric peak of the material was estimated by using the expression 1 1 − ε εmax − ∝ (T − Tc )γ .9 compositions. and/or substitutional disordering in the arrangement of cations in one or more crystallographic sites of the structure.9 compositions of PLBZT.9 compositions of PLBZT. 28]. From the above dielectric analysis we have found that the peak dielectric constant increased with an increase in La+3 concentration.3.6 and (c) z = 0. whereas only a small shift in Curie temperature could be observed. respectively.3. fluctuations. Curve (c) is significantly broader than curve (a).9 as a function of temperature. The variation of dielectric loss with temperature (40–410˚C) at frequencies starting from 0. Figure 4.3.Structural and dielectric properties of PZT ceramics (a) (b) Figure 5. Variation of dielectric constant with temperature (at different frequencies) for (a) z = 0. This large value of γ (table 1) confirms the second-order phase transition and the high degree of disorderliness in the material [18. with different local Curie points [31. at 1 kHz frequency. which leads to microscopic or nanoscopic heterogeneity in the compounds.6 and (c) z = 0. Ti+4 and Zr+4 are replaced by soft dopants La+3 and Bi+3 . Variation of % TCε for (a) z = 0. The temperature coefficient of permittivity (TCε ) is defined as εT − εRT .1 kHz to 1 MHz is 3177 where ε and εmax are the dielectric constants at temperature T (T > Tc ) and εmax (maximum value of ε at the transition temperature Tc ). (b) z = 0. Figure 6. It is also clear that an increase in frequency causes a decrease in the maximum value of the dielectric constant. (b) z = 0. 32].6 and (c) z = 0. This indicates that PLBZT (90/10) possesses a more diffuse phase transition than the rest of the compositions.

are present [30].03PbO↑ taking place during sintering.01La2 O3 + Pb(ZrTi)O3 → (Pb0. shown in figures 8(a)–(c). on the other hand. This growth in tan δ is brought about by an increase both in the conduction of residual current and the conduction of absorption current. where ε0 is the vacuum dielectric constant. Variation of dielectric constant (at room temperature (εRT ) and at Tc (εmax ) and Tc as a function of composition (z).97 La0. tan δ increases appreciably when the temperature rises. The dielectric loss was found to be very small and nearly the same at all the frequencies in the temperature range 40–125˚C. there is a reduction in energy required to overcome the resistance of the viscous medium.9 compositions at different frequencies. .01 )(ZrTi)O3 +0. Above 125˚C. In a polar substance.3. with La doping) as in the reaction 0.P Goel et al Figure 7. vacancies (here. (b) z = 0.6 and (c) z = 0.6 and (c) z = 0. Figure 8. The activation energy Ea can be calculated by making use of this plot and the relation given below: σ = σ0 exp − Ea KB T . on the one hand. a continuous increase in tan δ was observed. The calculated values of activation energy at 1 kHz frequency for all the compositions are given in table 1. 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 type of conductivity has been confirmed as p-type [35]. Conductivity vs temperature characteristics of PLBZT (a) z = 0. Figure 9 is the plot of log(σ ) with respect to the inverse temperature (T −1 ). 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.02–0.3. The conductivity is given by σ = ωε0 ε tan δ. losses due to electrical conduction. (b) z = 0. This is believed to be due to the formation of Pb site 3178 Figure 9.9 compositions at 1 kHz frequency. As a general rule. ω is the angular frequency and KB is the Boltzmann constant. which increase with an increase in temperature. Dielectric loss variation as a function of temperature of PLBZT (a) z = 0. The observed tan δ of our samples were nearly the same for all the compositions at lower temperatures but started rising on raising the temperature. and the increase in the degree of dipole orientation. and was greater at lower frequencies. The value of Ea decreases with increasing La+3 as can be seen from figure 9. In actual fact. apart from dipole losses.

McMillan L D and Zuleeg R 1991 J. Lett. 66 790 [4] Scott J F. Lett. Prasad C D and Lal Ramji 1990 Mater. Ceram. In dielectric studies. which is also confirmed by the SEM analysis. Sci. Soc. Eng. 82 94 [23] Shannigrahi S R. Fulrath R M and Pask J A 1981 J. Rev. Am. Sci. Am. India [27] Garg A and Agarwal D C 2001 Mater. Tay F E H. 24 163 [29] Scherrer P 1918 Nachr. Sci. Solids 24 979 3179 . Phys. B 25 29 [20] Sharma H D. 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. Goel T C. Appl. 79 530 [8] Takahashi M 1971 Japan. Bull. 82 797 [11] Wei Hng Q and Hoon H 2002 Mater. Lett. The chemical route allows a low temperature synthesis (450˚C) and ensures a molecular level of homogeneity. Pure Appl. 64 422 [3] Hiramath B V. Soc. Appl. Pillai P K C and Pramila C 1996 J. Hong Y S. Kor. 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 fixed Zr/Ti (65/35) ratio prepared by the co-precipitation method. Kharagpur. Lett. Tagantsev A K. Cook W R and Jaffe H 1971 Piezoelectric Ceramics (New York: Academic) [2] Chandatreya S S. 31 155 [19] Sharma H D. Soc. The results can be summarized as follows: XRD studies confirm the formation of a rhombohedral phase of all the studied samples at 450˚C. Lett. Phys. Appl. Soc. 76 109 [7] Paruch P. the transition temperature is found to decrease whereas ε is found to increase with the increasing concentration of lanthanum. Chem. 51 434 [25] Dayal Rajiv. Park C Y. Ceram. Sci. 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. Tybell T and Triscone J M 2001 Appl. B 50 698 [6] Bell A J 2000 Appl. Phys. Am. 12 1603 [14] Yadav K L and Choudhary R N P 1992 Solid State Ionics: Materials and Applications ed B W R Chowdari et al (Singapore: World Scientific Publishing Company) p 735 [15] Pramila P. 75 151 [12] Tan Q and Viehland D 1987 J. Eng. Zhang P L and Qu B D 1994 Phys. Goel T C and Pillai P K C 1993 J. Brooks K G and Setter N 1997 J. Kim K and Kim S J 1994 J. Soc. Gott. Mater. Phys. Acknowledgments The authors thank Professor M R Maurya (Department of Chemistry. Phys. Am. 80 336 [22] Park H B. Res. The density increases with the increasing concentration of La+3 . Kingon A I and Biggers J V 1983 J. Mater. B 86 134 [28] Shannigrahi S R. Hing P and Choudhary R N P 2001 Mater. Phys. dielectric and piezoelectric properties of modified PLZT ceramics PhD Thesis Indian Institute of Technology. Ceram. Syh-Yuh-cheug and Chung-Churag Wei 1986 Ferroelectrics 67 93 [34] Smyth C P 1955 Dielectric Behaviours and Structure (GB: McGraw Hill) [35] Gerson R and Jaffe H 1963 J. 25 1935 [26] Yadav K L 1994 Structural. There is a variation in the grain size with different concentrations of La+3 and Bi+3 . Tripathi A K. Phys. Phys. 12 561 [18] Jung S C. Ceram. Govindan A. 12 1657 [16] Yadav K L and Choudhary R N P 1993 J. Lett. Charier V. 81 361 [13] Lee K M. Ceram. Jang H M and Park W J 1997 J. Mater. Res. Chem. D 14 23 [33] Sheu-Li-Fu. Mater. Sci. Appl. Mater. 15 1424 [21] Klissurska R D. Park H B. PG thanks MHRD for providing a research fellowship. Kim J. Goel T C and Pillai P K C 1994 J. Kim K and Kim S J 1999 J. 28 769 [17] Yadav K L and Choudhary R N P 1993 J. Am. It is finally concluded that the dielectric constant. Soc. Ceram. Eur. 10 643 [9] Heartling G H 1987 Ferroelectrics 75 25 [10] Heartling G H 1999 J. References [1] Jaffe B. Ceram. Sci. Arujo C A.Structural and dielectric properties of PZT ceramics 4. Choudhary R N P and Acharya H N 1999 J. J. Wong Y G. Melnick B M. 70 382 [5] Zhong W L. Mater. Sci. Soc. Yao K and Choudhary R N P 2004 J. 85 1713 [24] Ray J. 2 98 [30] Tareev B 1979 Physics of Dielectric Materials (Moscow: Mir) chapter 3 [31] Lines M E and Glass A M 1977 Principles and Applications of Ferroelectrics and Related Materials (Oxford: Oxford University Press) [32] Yadav K L and Choudhary R N P 1995 Bull.