Defect Dipole Thermal-stability to the Electro-mechanical Properties of Fe Doped PZT Ceramics

doi:10.15541/jim20240244

Abstract

Abstract:

The accepted doping ion in Ti⁴⁺-site of PbZr_yTi_1-_yO₃ (PZT)-based piezoelectric ceramics is a well-known method to increase mechanical quality factor (Q_m), since the acceptor coupled by oxygen vacancy becomes defect dipole, which prevents the domain rotation. In this field, a serious problem is that generally, Q_m decreases as the temperature (T) increases, since the oxygen vacancies are decoupled from the defect dipoles. In this work, Q_m of Pb_0.95Sr_0.05(Zr_0.53Ti_0.47)O₃ (PSZT) ceramics doped by 0.40% Fe₂O₃ (in mole) abnormally increases as T increases, of which the Q_m and piezoelectric coefficient (d₃₃) at room temperature and Curie temperature (T_C) are 507, 292 pC/N, and 345 ℃, respectively. The maximum Q_m of 824 was achieved in the range of 120-160 ℃, which is 62.52% higher than that at room temperature, while the dynamic piezoelectric constant (d₃₁) was just slightly decreased by 3.85%. X-ray diffraction (XRD) and piezoresponse force microscopy results show that the interplanar spacing and the fine domains form as temperature increases, and the thermally stimulated depolarization current shows that the defect dipoles are stable even the temperature up to 240 ℃. It can be deduced that the aggregation of oxygen vacancies near the fine domains and defect dipole can be stable up to 240 ℃, which pins domain rotation, resulting in the enhanced Q_m with the increasing temperature. These results give a potential path to design high Q_m at high temperature.

Key words: defect dipole, temperature characteristic, oxygen vacancy, electro-mechanical property, mechanical quality factor, hardening doping

CLC Number:

TQ174

SUN Yuxuan, WANG Zheng, SHI Xue, SHI Ying, DU Wentong, MAN Zhenyong, ZHENG Liaoying, LI Guorong. Defect Dipole Thermal-stability to the Electro-mechanical Properties of Fe Doped PZT Ceramics[J]. Journal of Inorganic Materials, 2025, 40(5): 545-551.

Figures/Tables 10

Fig. 1 Lattice, density and SEM image of PSZT-xFe ceramics (a) Lattice parameters of the T phase; (b) SEM image of PSZT-0.40Fe ceramics with inset showing the grain size distribution; (c) Relative density and average grain size

Fig. 2 Dielectric properties, P-E loops and I-E loops of PSZTs (a) ε and tanδ versus temperatures at 100 kHz of PSZT-xFe ceramics; (b) ε and tanδ versus temperatures at frequencies of 1, 10 and 100 kHz for PSZT-0.40Fe ceramic with inset showing tanδ versus temperatures in the range of 20-250 ℃; (c) P-E loops of PSZT-xFe ceramics; (d) I-E loops of PSZT-xFe ceramics. Colorful figures are available on website

Table 1 Electro-mechanical properties of PSZT-xFe ceramics

x	T_C/℃	T_θ/℃	C/(×10⁴)	E_C/(kV·cm^-1)	P_r/(μC·cm^-2)	d₃₃/(pC·N^-1)	Q_m	k_p	σ	ε(1 kHz)
0.36	343	336	7.0	31.3	1.95	300	409	0.67	0.31	1361
0.38	343	335	8.4	32.8	2.76	295	415	0.66	0.31	1253
0.40	345	333	11.3	34.5	1.65	292	507	0.64	0.32	1098
0.42	343	332	10.6	34.2	2.11	294	499	0.65	0.31	1109

Fig. 3 Electro-mechanical properties of PSZT-0.40Fe ceramic in the range of 20-240 ℃ (a) Impedance of 120-160 kHz; (b) Phase angle of 120-160 kHz; (c) Calculated Qm; (d) Calculated d31. Colorful figures are available on website

Fig. 4 Morphology and longitudinal piezoelectric response images of PSZT-0.40Fe ceramics in the same region (a) Morphology at room temperature; (b-f) Longitudinal piezoelectric response image in the range of 40-240 ℃. Colorful figures are available on website

Fig. 5 XRD patterns of PSZT-0.40Fe ceramics in the range of 20-240 ℃ (a) XRD patterns; (b) Color map. Colorful figures are available on website

Fig. 6 TSDC curve of poled PSZT-0.40Fe ceramic

Fig. S1 XRD patterns of PSZT-xFe ceramics (a) 2θ=17.5°-67.5°; (b) 2θ=42.7°-45.8°

Fig. S2 Rietveld refinement results of PSZT-xFe ceramics XRD patterns (a) x=0.36; (b) x=0.38; (c) x=0.40; (d) x=0.42

Fig. S3 SEM images of PSZT-xFe ceramics with insets showing corresponding grain size distribution (a) x=0.36; (b) x=0.38; (c) x=0.40; (d) x=0.42

References 27

[1]	IZZAH T N, AHMAD Z A, MOHAMAD H. Influence of sintering parameters on structural, dielectric and piezoelectric properties of Ca, La and Sr doped PZT (PCLSZT) electroceramics. Mater. J. Sci.: Mater. Electron., 2021, 32: 18095.
[2]	JAFFE H. Piezoelectric ceramics. J. Am. Ceram., 1958, 41(11): 494.
[3]	FU H X, COHEN R E. Polarization rotation mechanism for ultrahigh electromechanical response in single-crystal piezoelectrics. Nature, 2000, 403(6767): 281.
[4]	REN X B. Large electric-field-induced strain in ferroelectric crystals by point-defect-mediated reversible domain switching. Nature, 2004, 3(2): 91.
[5]	JONES J L, SLAMOVICH E B, BOWMAN K J. Domain texture distributions in tetragonal lead zirconate titanate by X-ray and neutron diffraction. J. Appl. Phys., 2005, 97: 034113.
[6]	LI Z, THONG H, ZHANG Y, et al. Defect engineering in lead zirconate titanate ferroelectric ceramic for enhanced electromechanical transducer efficiency. Adv. Funct. Mater., 2021, 31: 2005012.
[7]	NGUYEN T N, THONG H, ZHU Z, et al. Hardening effect in lead-free piezoelectric ceramics. J. Mater. Res., 2021, 36: 996.
[8]	SANGAWAR S R, PRAVEENKUMAR B, KUMAR H H, et al. Effect of Fe and Fe-Ba substitution on the piezoelectric and dielectric properties of lead zirconate titanate ceramics. Mater. Sci. Eng. B, 2011, 176(3): 242.
[9]	CHEN C, WANG Y, LI Z Y, et al. Evolution of electromechanical properties in Fe-doped (Pb,Sr)(Zr,Ti)O₃ piezoceramics. J. Adv. Ceram., 2021, 10(3): 587.
[10]	LIU Y X, LI Z, THONG H C, et al. Grain size effect on piezoelectric performance in perovskite-based piezoceramics. Acta Phys. Sin., 2020, 69(21): 217704.
[11]	ZHANG D, ZENG J. The microstructure and electric properties of Bi³⁺ and Al³⁺ co-doped PZT ceramics. Ferroelectrics, 2018, 534(1): 212.
[12]	BRAJESH K, HIMANSHU A K, SHARMA H. Structural, dielectric relaxation and piezoelectric characterization of Sr²⁺ substituted modified PMS-PZT ceramic. Physica. B. Condens. Matter, 2012, 407(4): 635.
[13]	LIN J Y, CUI B H, CHENG J R, et al. Achieving both large transduction coefficient and high Curie temperature of Bi and Fe co-doped PZT piezoelectric ceramics. Ceram. Int., 2023, 49(1): 474.
[14]	LEE J K, YI J Y, HONG K S. The role of cation vacancies on micro-structure and piezoelectricity of lanthanum-substituted (Na_1/2Bi_1/2)TiO₃ ceramics. Jpn. J. Appl. Phys., 2004, 43: 6188.
[15]	DESU S B, PAYNE D A. Interfacial segregation in perovskites: III, micro-structure and electrical properties. J. Am. Ceram. Soc., 2010, 73(11): 3407.
[16]	KALEM V, ÇAM İ, TIMUÇIN M. Dielectric and piezoelectric properties of PZT ceramics doped with strontium and lanthanum. Ceram. Int., 2011, 37(4): 1265.
[17]	LANGMAN R A, RUNK R B, BUTLER S R. Isothermal grain growth of pressure-sintered PLZT ceramics. J. Am. Ceram. Soc., 1973, 56: 486.
[18]	YANG W W, ZENG H R, YAN F, et al. Microstructure-driven excellent energy storage NaNbO₃-based lead-free ceramics. Ceram. Int., 2022, 48(24): 37476.
[19]	UCHINO K, ZHENG J, CHEN Y, et al. Loss mechanisms and high power piezoelectrics. J. Mater. Sci., 2006, 41(1): 217.
[20]	PENG J, ZENG J, LI G, et al. Softening-hardening transition of electrical properties for Fe³⁺-doped (Pb_0.94Sr_0.05La_0.01)(Zr_0.53Ti_0.47)O₃ piezoelectric ceramics. Ceram. Int., 2017, 43(16): 13233.
[21]	KUMARI N, MONGA S, ARIF M, et al. Higher permittivity of Ni-doped lead zirconate titanate, Pb[(Zr_0.52Ti_0.48)_(1-_x₎Ni_x]O₃, ceramics. Ceram. Int., 2019, 45(4): 4398.
[22]	SUN X, DENG J, LIU L, et al. Dielectric properties of BiAlO₃-modified (Na, K, Li)NbO₃ lead-free ceramics. Mater. Res. Bull., 2016, 73: 437.
[23]	MCKINSTRY S T. Temperature dependence of the piezoelectric response in lead zirconate titanate films. J. Appl. Phys., 2004, 95(3): 1397.
[24]	LI C B W, THONG H C, LIU Y X, et al. Thermally induced domain reconfiguration in ferroelectric alkaline niobate. Adv. Funct. Mater., 2022, 32(38): 2204421.
[25]	HINTERSTEIN M, ROUQUETTE J, HAINES J, et al. Structural description of the macroscopic piezo- and ferroelectric properties of lead zirconate titanate. Phys. Rev. Lett., 2011, 107: 077602.
[26]	KITTEL C. Theory of the structure of ferromagnetic domains in films and small particles. Phys. Rev., 1946, 70(11): 965.
[27]	ANDRYUSHIN K, ANDRYUSHINA I, SADYKOV H, et al. The influence of thermodynamic history and external influences on the electrophysical properties of ferropiezoceramic materials based on a multicomposition system PZT-PMN- PZN+SiO₂. J. Adv. Dielectr., 2020, 10: 2060012.