J Mater Sci: Mater Electron DOI 10.

1007/s10854-009-0035-9

Inuence of low trivalent iron doping on the electrical characteristics of PZT

K. P. Rema Vinod K. Etacheri V. Kumar

Received: 12 October 2009 / Accepted: 25 November 2009 Springer Science+Business Media, LLC 2009

Abstract Piezoelectric materials based on lead zirconium titanium oxide with a composition near the morphotropic phase boundary, (Pb0.94Sr0.06)(Zr0.53Ti0.47)O3[PSZT] have been synthesized by solgel method. The inuence of B-site aliovalent dopant Fe3? on the structure, ferroelectric, dielectric, piezoelectric characteristics and microstructure have been investigated. The inuence of the transition metaloxygen vacancy defect-dipoles on the electrical characteristics have also been investigated.

1 Introduction The Pb(ZrxTi1-x)O3[PZT] is a typical perovskite represented by the formula ABO3 wherein A and B are divalent and tetravalent cations respectively. PZT with a composition near the morphotropic phase boundary (MPB) where the Zr/Ti ratio is *(53/47) exhibit optimum piezoelectric properties [1, 2]. Lower-valent substituents at the A or B sites of ABO3 render the PZT hard [37]. Hard PZT is characterized by lower values of dielectric constant, dielectric loss and higher values of mechanical quality factor. Typical lower-valent substituents in PZT include K?-cation at the A-site and Fe3?, Mn3?-cations at the B-site. There are several studies reported [312] on the B-site trivalent ion (Fe3?, Mn3?) substituted PZT. The inuence of polarized defects on polarization switching in A-site K?-substituted PKZT(4/65/35) have been studied in
K. P. Rema V. K. Etacheri V. Kumar (&) Center for Materials for Electronics Technology [Scientic Society, Department of Information Technology, Ministry of Communications and Information Technology, Government of India], Shornur Road, M.G.Kavu, Athani P.O., Trissur 680771, Kerala, India e-mail: vkumar10@yahoo.com

detail and reported [13]. In B-site acceptor-doped PZT, the exact nature of the domain-wall pinning mechanism, especially the role of transition metal ion-oxygen vacancy defect-dipoles, have not been studied in detail. Also there is considerable scatter in data in the literature with regard to the site substitution by the dopant. We have recently reported that Mn3?-dopant at the B-site imparts certain soft characteristics to PZT [8]. Therefore we have investigated in detail the inuence of small amounts of an ideal acceptor dopant, Fe3?, 0.001 B y B 0.01, on the electrical properties of (Pb0.94Sr0.06)(Zr0.53Ti0.47)FeyO3 [PSZT]. The composition PSZT assumes signicance as it is near the MPB which is widely used in transducer applications.

2 Experimental The solid-solution with the MPB composition was chosen as the basis for doping with different amounts (0.001 B y B 0.01) of Fe3? to yield the compositions with the general formula, Pb0:94 Sr0:06 Zr0:53 Ti0:47 z Fe3 O3 PSZTF where y z = 1-3/4y. PSZTF were synthesized by solgel method as per the procedure adapted from our earlier work [8]. For the preparation of the precursor solution, basic lead acetate (Merck, India), Strontium acetate (Aldrich, Germany), Zirconium(IV)acetylacetonate(Merck, Germany), Manganese (III) acetylacetonate and Iron(III) acetyl acetonate (Aldrich, Germany) were dissolved in acetic acid, [CH3COOH]/ [Zr ? Ti ? Mn] = 25, and was mixed with Titanium tetraisopropoxide, Ti(OiC3H7)4 (Aldrich, Germany) in iso-propyl alcohol under constant stirring condition. To induce hydrolysis, water, [H2O]/[Ti] = 2, was added drop wise to this solution and stirring continued for another hour. The clear homogeneous precursor solution was then allowed to gel at room temperature The gel derived powders, obtained after

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calcination at 600 C for 2 h, were isostatically pressed at 200 MPa into pellets of diameter 10 mm and thickness 1.0 mm. The PSZTF specimens were sintered, at a temperature of 1,200 C for 3 h under constant PbO atmospheres maintained using a mixture, PbZrO3 ? 10% ZrO2, as reported [14]. The sintered PSZT specimens were polished and electroded with silver paste and subsequently cured at 700 C for 30 min. Two sets of samples were prepared. One set of samples were not poled. The other set was poled by applying a DC electric eld of 2.5 kV/mm at elevated temperatures for 60 min in a silicone oil bath and then slowly cooled down to ambient temperature. The piezoelectric characteristics were measured 24 h after poling. Electromechanical characteristics were calculated from the resonance measurements. The d33 constant was measured by applying a known force to the electroded surfaces of the piezoelectric specimen and measuring the electrical charges generated in the same direction using a d33 meter (Model Pennebaker 8000, APC Inc., PA, USA). Dielectric properties of the sintered compacts were determined at 1 kHz using an impedance analyzer (Model 4192A, Agilent Technologies, CA, USA). Microstructure of the sintered pellets were recorded using a SEM (Model JSM840A, JEOL, Tokyo, Japan). Electron Paramagnetic Resonance spectrum of the specimens were recorded at liquid nitrogen temperature using X band EPR spectrometer (Model E-112, Varian, USA). Ferroelectric hysteresis (P-E) of the sintered compacts were measured using a TF Analyser (Model 2000, aixACCT, Germany). The Curie temperature, Tc was determined on sintered and powdered samples using a differential scanning calorimeter (Model DSC 822E, Mettler Toledo, Schwerzenbach, Switzerland) in Nitrogen atmosphere, at a constant heating rate of 10 C/min.

Fig. 1 X-ray diffraction patterns of Pb0:94 Sr0:06 Zr0:53 Ti0:47 z Fe3 O3 ; z = 1-3/4y (a) y = 0 (b) .001 (c) .002 (d) .003 (e) .004 y (f) .005 and (g) .01 Table 1 c/a ratio of (Pb0.94 Sr0.06)(Zr0.53Ti0.47)zFeyO3 (PS)(ZT)zFeyO3 y (atom%) 0 0.001 0.002 0.003 0.004 0.005 0.010 c/a Ratio 1.022 1.021 1.021 1.021 1.020 1.017 1.016 Structure Tetragonal Tetragonal Tetragonal Tetragonal Tetragonal Tetragonal Tetragonal

3 Results and discussion Figure 1 shows the XRD patterns of the Fe-doped system conrming the presence of only the perovskite phase. In comparison with the undoped composition, c/a ratio decreases for the Fe-doped composition (Table 1) along with a decrease in Tc (Fig. 2). These are due to the decrease in BOB coupling as a result of incorporation of Fe3?-cations at the B-site. Incorporation of Fe3? at the B-site is also conrmed by the continuous decrease in the Curie temperature, Tc (Fig. 2). Figure 3a shows the P-E characteristics of the PSZTFe virgin specimens at room temperature revealing doubleloop nature. The P-E characteristics are similar to those reported for ferroelectrics containing randomly oriented polarisable defects [13, 15]. The degree of double-loop characteristics is quite pronounced. The magnitude of the remanent polarization (Pr) decreases as the double-loop characteristic increases and

Fig. 2 Tc of PSZTFe as a function of Fe-content

the switchable polarization is considerably less than that of the undoped system. The mechanism by which the B-site dopant inuences the polarization switching characteristics

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J Mater Sci: Mater Electron Fig. 3 P-E hysteresis characteristics of Fe-doped (A) virgin and (B) poledPSZTFey specimens at room temperature. a y = 0 b 0.001 c 0.002 d 0.003 and e 0.005

of PSZT can be explained as follows. For the trivalent acceptor dopant M at the B-site of the perovskite, charge compensation is achieved by creating oxygen vacancy as represented in Eq. 1; 2BO2 M2 O3 2M0B 3Oo V ! o 1

Fig. 4 EPR spectra of (Fe0Ti V ) defectdipole in PSZTFe o

Fig. 5 Internal electric eld (Ei) as a function of the dopant concentration in poled specimens of PSZTFe

where M0B indicates a singly negatively charged acceptor at the B-site and V a doubly positively charged oxygen o vacancy with respect to the neutral lattice according to Kroger and Vink. The negatively charged trivalent dopant at the B-site forms a defect-dipole with the positively charged V , o M0B V . In the EPR spectrum (Fig. 4) the signals at o 0 g & 5.7 and g & 4.3 are characteristic of (FeTi V ) o defect-dipole in PZT of MPB composition [16]. Such defect-dipoles, if they are mobile, have been reported to pin domain walls suppressing nucleation and growth of domains in the direction of the applied electric eld [4, 17, 18]. In the case of the poled samples, the P-E curves (Fig. 3b) reveal strong asymmetry with only a single loop. The polarization is switchable only to the reverse-biased state. Also the magnitude of this switchable polarization decreases with increasing Fe-content. For [Fe3?] C 0.005, the P-E curve is considerably constricted (Fig. 3b(e)). The P-E curves are similar to those reported for A-site K?-substituted PZT (65/35) [13]. In poled specimens, as a result of the applied electric eld, the defect-dipoles undergo a preferred alignment leading to the development of an internal electric eld (Ei). This internal electric eld (Ei) was estimated from the current curves obtained by differentiating the polarization curves as described previously [18] and are plotted in Fig. 5. With increasing Fe3? concentration, Ei increases up to a maximum value of -10 kV/cm for an Fe concentration as low as 0.4 at%. This shows that very high internal electric elds are developed with Fe-doping as a result of the preferred alignment of the (Fe0Ti V ) defect-dipole. These results also correlate well o

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Fig. 6 Effect of dopant concentration on a piezoelectric and b dielectric characteristics of PSZTFe

Fig. 7 SEM micrographs of sintered specimens of PSZTFeyO3; y(at%) = a 0; b 0.001;c 0.002; d 0.005; and e 0.01

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with their piezoelectric and dielectric characteristics (Fig. 6a, b). The micrographs shown in Fig. 7ae reveal well dened microstructures with crystal-like faces up to a Fe-dopant concentration, y B 0.005. It is seen that the grain size is strongly inuenced by the Fe content. The undoped composition (Fig. 7a) has an average grain size of 8.0 lm. As the Fe content increases, the grain size decreases to 3.0 lm for the composition with a Fe-dopant concentration, y = 0.01 (Fig. 7e). This reduction in grain size is due to the inhibition of grain growth by the oxygen vacancies as a result of Fe doping. There is good correlation between the microstructures and the electrical characteristics.

Principal, SN College, Nattika for the leave granted which enabled her to pursue this research at C-MET, Trissur.

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4 Conclusion A detailed investigation of the Polarization Switching characteristics of Fe3?-doped PSZT has revealed the inuence of the (Fe0Ti V ) defect-dipole on the polario zation switching characteristics. These dipoles are found to have high mobilities in virgin specimens whereas they are preferentially oriented in poled specimens leading to the development of signicant internal electric elds. These results are also found to correlate well with the observed dielectric and piezoelectric characteristics.
Acknowledgments One of the authors KPR is grateful to University Grants Commission (UGC) for the FIP fellowship and to the

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