Ferroelectric and pyroelectric properties of Mn-doped lead zirconate titanate ceramics

doi:10.1016/j.ceramint.2014.02.113

Ceramics International

Volume 41, Issue 5, Part A, June 2015, Pages 6158-6163

https://doi.org/10.1016/j.ceramint.2014.02.113 Get rights and content

Abstract

PbNb_0.02(Zr_0.95Ti_0.05)_0.98O₃ (PNZT95/5) ceramics with Mn doping were prepared and the effects of Mn doping on the phase structure and electrical properties were investigated. It was found that Mn addition did not cause a remarkable change in rhombohedral perovskite structure, but significantly altered ferroelectric and pyroelectric properties of the PNZT95/5 ceramics. PNZT95/5 ceramics usually possessed a normal single hysteresis loop character when no aging process was employed, whereas Mn doped PNZT95/5 (PNMZT95/5) ceramics exhibited a double-hysteresis-like loop character because of the defect dipoles formed by Mn²⁺ and O²⁻ vacancies. Meanwhile, ferroelectric features such as the polarization and coercive field showed a strong frequency and temperature dependence. Furthermore, Mn substitution resulted in the weakened dielectric property and enhanced pyroelectric property of the ceramics. The relevant pyroelectric coefficient (p) and detectivity figure of merit (F_D) increased from 7.90×10⁻⁸ to 9.15×10⁻⁸ C cm⁻² K⁻¹ and 8.69×10⁻⁵ to 16.74×10⁻⁵ Pa^−1/2, respectively, which make the PNMZT95/5 ceramics potential application in commercial infrared detectors.

Introduction

The Zr-rich Pb(Zr_0.95Ti_0.05)O₃ (PZT95/5) ceramics are important ferroelectric materials with excellent dielectric, pyroelectric properties and fast response of infrared radiation. However, PZT95/5 ceramics exhibit poor spontaneous polarization ability and hence the polarization reversal becomes difficult due to the neighboring boundary of ferroelectrics (FE)/antiferroelectric (AFE). Moreover, the sintering temperature of pure PZT95/5 ceramics is usually higher than 1200 °C, which gives rise to the compositional variation and the creation of cation vacancies in ceramics because of the volatility of PbO during annealing process. Therefore, much attention has been focused on the modification of PZT by substitution method [1], [2]. Compositional modifications using dopants have attracted more and more interest due to their remarkable effects even only small amounts of dopant are used. Nb₂O₅ additives are most often used for this purpose and an amount of about 1 mol% is the most favorable [3], [4], [5], [6]. PbNb_0.02(Zr_0.95Ti_0.05)_0.98O₃ with Mn doping (PNMZT95/5) ceramics exhibit double-hysteresis-like loops when no aging process is employed, which is often observed in the conventional ferroelectrics (e.g., BaTiO₃) [7], [8], [9]. However, to date, little work about this phenomenon in PZT ceramics is reported.

As a matter of fact, the main parameters for judging the quality of pyroelectric materials are the pyroelectric coefficient and figure of merit (FOM). A good pyroelectric material should possess a large pyroelectric coefficient, small dielectric constant and dielectric loss. In this work, Nb₂O₅ and MnCO₃ are selected to stabilize FE phase and reduce dielectric loss [10], [11]. The pyroelectric and ferroelectric properties, especially the frequency and temperature dependence of P–E loops in PNMZT95/5 ceramics are investigated. A double-hysteresis like loop in PNMZT95/5 ceramics is observed for the first time. The formation mechanism of this abnormal hysteresis loop and the influence of Mn on pyroelectric property are also discussed.

Section snippets

Experimental procedure

The PNZT95/5 and PNMZT95/5 ceramics were synthesized by a solid-state reaction method. The reagent-grade materials, Pb₃O₄ (98% purity), ZrO₂ (99% purity), Nb₂O₅ (99.5% purity), TiO₂ (99% purity) and MnCO₃ (98% purity) were mixed as starting materials according to the stoichiometric ratio and then milled in distilled water for 16 h. After drying, the powders were calcined at 850 °C for 2 h. Then the calcined powders were ground in distilled water for 6 h and dried. The powders were finally

Results and discussion

Fig. 1a shows the XRD patterns of the synthesized PNZT95/5 and PNMZT95/5 ceramics. Both ceramics possess a typical Zr-rich rhombohedral perovskite structure, no pyrochlore or other phase is observed. From the enlarged XRD patterns in the 2 $θ$ angle of 30–32° (Fig. 1b), 43–45° (Fig. 1c) and 54–55° (Fig. 1d), it can be seen that the diffraction peaks shift to a large angle direction, which indicate the distortion of the crystal lattice of the ceramics due to the ionic size effect. It is reported

Conclusion

Mn-doped PNZT95/5 (PNMZT95/5) ceramics are synthesized and double-hysteresis-like loop is observed. No obvious change occurs in the rhombohedral phase structure in the case of Mn doping. Based on the symmetry-conforming principle of point defects, the acceptor dopant Mn ions and O vacancies form Mn"_Zr/Ti-V_O defect dipoles along the polarization direction, which remain in the original orientation and provide a restoring force to reverse the switched polarization. Meanwhile, PNMZT95/5 ceramics

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Ferroelectric and pyroelectric properties of Mn-doped lead zirconate titanate ceramics

Abstract

Introduction

Section snippets

Experimental procedure

Results and discussion

Conclusion

J. Eur. Ceram. Soc.

J. Alloys Compd.

J. Alloys Compd.

J. Alloys Compd.

Solid State Commun.

J. Alloys Compd.

Ceram. Int.

Ceram. Int.

J. Alloys Compd.

Ceram. Int.

Multistage heat-electric energy convertion working on FR(LT) –FR(HT) phase transition in Nb-doped PZT-97/3 ceramics

Ferroelectrics

Effects of niobium doping on the microstructure and electrical properties of 0.36BiScO3–0.64PbTiO3 ceramics

J. Am. Ceram. Soc.

Study of ferroelectric hysteresis scaling exponents in aged polycrystalline BaTiO3

Ferroelectrics

Large recoverable electrostrain in Mn-doped (Ba,Sr)TiO3 ceramics

Appl. Phys. Lett.

Multistage heat-electric energy convertion working on F_R(LT) –F_R(HT) phase transition in Nb-doped PZT-97/3 ceramics

Effects of niobium doping on the microstructure and electrical properties of 0.36BiScO₃–0.64PbTiO₃ ceramics

Study of ferroelectric hysteresis scaling exponents in aged polycrystalline BaTiO₃

Large recoverable electrostrain in Mn-doped (Ba,Sr)TiO₃ ceramics