Fangping Zhuo

Coexistence of multiple positive and negative electrocaloric responses in (Pb, La)(Zr, Sn, Ti)O3 single crystal

The electrocaloric effect has been investigated in antiferroelectric (Pb, La)(Zr, Sn, Ti)O3 (PLZST) single crystals grown by the flux method. The measurements of polarization versus electric field loops on unpoled crystals revealed that at room temperature, a critical electric field of 1.8 kV/mm is needed to induce a ferroelectric phase from an antiferroelectric phase. The dielectric properties demonstrated that the induced ferroelectric phase recovers to antiferroelectric phase when temperature is above the depolarization temperature (70 °C–100 °C). Coexistence of the negative and positive electrocaloric effect has been achieved in ⟨001⟩-oriented PLZST single crystals. Multiple electrocaloric response values of −0.054 °C at room temperature, 0.17 °C near the depolarization temperature, −0.14 °C at 125 °C, and 0.75 °C around Curie temperature have been observed under an electric field of 3 kV/mm. The coexistence of multiple negative and positive electrocaloric effects in one material provides a possibilit...

Electric field induced metastable ferroelectric phase and its behavior in (Pb, La)(Zr, Sn, Ti)O3 antiferroelectric single crystal near morphotropic phase boundary

Antiferroelectric (AFE) (Pb, La)(Zr, Sn, Ti)O3 (PLZST) single crystal with composition near morphotropic phase boundary has been grown and studied. X-ray diffraction analysis and electrical properties reveal coexistence of antiferroelectric/ferroelectric (FE) phases, with the AFE phase dominated at room temperature. Temperature-dependent polarization and strain measurements indicate that the AFE phase can be induced into a metastable FE phase by electric field. The FE phase can be maintained in a wide temperature range above room temperature and recovers to AFE phase around a critical temperature of 90 °C, accompanied with remarkable change in field-induced strain. The strain at 90 °C (∼0.50%) is ten times larger than that at room temperature (∼0.04%), which makes the PLZST single crystal a promising candidate for thermal switch and actuator application.

Electric field induced phase transition and domain structure evolution in (Pb, La)(Zr, Sn, Ti)O3 single crystal

Antiferroelectric (Pb, La)(Zr, Sn, Ti)O3 (PLZST) single crystals with composition in the vicinity of morphotropic phase boundary have been grown and studied. From electric measurements, Raman study, and observation of domain structures, we found an electric field induced antiferroelectric to ferroelectric phase transition accompanied with fifteen times of strain difference. After this phase transition, the metastable ferroelectric phase (FEin) is preserved with soften of A1(TO1) mode and increase of long-range force. Coexistence of tetragonal (T) and rhombohedral (R) domains has been observed in virgin sample. Electric field induced T to R phase transition is verified by both extinction angle and domain morphology changes. Clamping “polar” structure formed by the embedded R phase would contribute to increase of long-range force. The remarkable strain difference accompany with induced phase transition makes the PLZST single crystal a promising candidate for electric switch and actuator applications.

Effect of A-site La3+ modified on dielectric and energy storage properties in lead zironate stannate titanate ceramics

(Pb1-1.5xLax)(Zr0.66Sn0.23Ti0.11)O3 (PLZST) ceramics with different lanthanum (La3+) content (x = 0–6%) were prepared by conventional solid state reaction process, and exhibited excellent electrical properties with high switching field from AFE to FE phase and electric breakdown strength. The maximum dielectric constant (em) and its corresponding temperature (Tm) decreased with La3+ doping and a phase transition from rhombohedral ferroelectric (FE) to tetragonal antiferroelectric (AFE) state was found at 2% La3+ doping. At room temperature, a maximum energy density of 1.47 J cm−3 was obtained for x = 4%. In addition, electric-field-dependent energy storage properties of PLZST (x = 4%) ceramics have been investigated, which could be ascribed to the AFE–FE phase transition associated with the increase of strain.

Field induced phase transitions and energy harvesting performance of (Pb,La)(Zr,Sn,Ti)O3 single crystal

(Pb,La)(Zr,Sn,Ti)O3 (PLZST) single crystals with composition close to the morphotropic phase boundary had been grown by the flux method. The antiferroelectric-ferroelectric phase switching electric field was 0.8 kV/mm. Temperature-dependent dielectric and polarization versus electric field hysteresis loops revealed that the electric field induced ferroelectric phase could transform back into the antiferroelectric phase at depolarization temperature (145 °C). An enhanced pyroelectric coefficient value of 1.46 μC/cm2/K was obtained at 145 °C, which is several times larger than that of conventional pyroelectric materials. Furthermore, multiple peak pyroelectric responses and an enhanced harvested energy density value of 0.4 J/cm3 were achieved in the PLZST crystal. The enhanced harvested energy density and multiple peak pyroelectric responses make the PLZST crystal a promising candidate for high sensitive temperature sensors and energy conversion technologies.

Temperature induced phase transformations and negative electrocaloric effect in (Pb,La)(Zr,Sn,Ti)O3 antiferroelectric single crystal

Temperature induced phase transitions and electrocaloric effect (ECE) of (Pb,La)(Zr,Sn,Ti)O3 (PLZST) single crystals have been comprehensively studied. Based on the in situ evolution of domain structures and dielectric properties of the PLZST crystals, the phase transitions during heating are in the sequence of orthorhombic antiferroelectric → rhombohedral ferroelectric → cubic paraelectric. Coexistence of the negative and positive ECEs has been achieved in the PLZST single crystals. A negative ECE value of −1.26 °C and enhanced electrocaloric strength of −0.21 K mm/kV near the Curie temperature have been obtained. A modified Landau model gives a satisfactory description of the experimentally observed unusual ECE. Moreover, a temperature–electric field phase diagram is also established based on theoretical analysis. Our results will help people understand better the electrocaloric family, particularly on the negative and/or positive effect in antiferroelectrics and ferroelectrics.

Structural phase transition, depolarization and enhanced pyroelectric properties of (Pb1−1.5xLax)(Zr0.66Sn0.23Ti0.11)O3 solid solution

(Pb1−1.5xLax)(Zr0.66Sn0.23Ti0.11)O3 (PLZST) (x = 0–0.024) ceramics were designed based on chemical composition modification and fabricated using the conventional solid-state method. Structural phase transition, thermal depolarization and pyroelectric properties of the PLZST system were investigated systematically. Phase structures of various chemical compositions in the PLZST system were discussed based on the electronegativity difference versus tolerance factor relationship phase diagram. Enhanced pyroelectric response with a value of 14.01 μC cm−2 K−1 was realized for the ceramics with x = 0.018, which is far larger than the previously reported values. The results indicated that there was a quadratic function relationship between the pyroelectric peak temperature (Tpeak) and composition (x): Tpeak = 182 + 404x − 3.0 × 105x2. The composition dependence of the wide range pyroelectric response over 19–185 °C was obtained by changing x from 0 to 0.024. Our results also reveal that the enhanced and wide temperature range pyroelectric properties of the composition-optimized PLZST system are of great significance to pyroelectric technology.

Phase transition and domain configuration of poled rhombohedral PIN–PZ–PMN–PT single crystals

A perovskite single crystal of the quaternary system PIN–PZ–PMN–PT, with rhombohedral (R) symmetry (3m) and a size of 10 × 10 × 6 mm3, was successfully grown by a slow cooling method, which had a high rhombohedral-to-tetragonal (T) ferroelectric (FE) phase transition temperature (TR–T = 129 °C). The introduction of In3+ and Zr4+ enhanced the repulsion intensity between Pb2+ and B-site cations in the ABO3 lattice and increased the energy difference ΔET–R, resulting in an improved FE phase transition temperature compared to the PMN–PT binary system single crystals. The evolution of domain configuration induced by both electric field and temperature was studied for the [001]C PIN–PZ–PMN–PT single crystal by using a polarized light microscope. Star porphyritic domains with short-range order before poling and stripe domains with long-range order after poling were observed, respectively, confirming the typical relaxor domain configurations of the R phase. Fine domain walls induced by temperature for the poled [001]C sample were responsible for the high piezoelectric property. Furthermore, minor ferroelectric property variations (ΔPmax < 6%, ΔPr < 10%) were observed at the temperature range from 20 °C to 140 °C, indicating the good thermal stability of the quaternary system PIN–PZ–PMN–PT single crystal.

Field-induced phase transitions and enhanced double negative electrocaloric effects in (Pb,La)(Zr,Sn,Ti)O3 antiferroelectric single crystal

Field-induced phase transitions and electrocaloric effect have been studied in (Pb,La)(Zr,Sn,Ti)O3 (PLZST) antiferroelectric single crystal. Temperature dependent dielectric, Raman spectra, as well as in situ domain evolution demonstrated that the order of phase transitions during heating is in the sequence of orthorhombic antiferroelectric → tetragonal antiferroelectric → cubic paraelectric. Enhanced negative electrocaloric effect value of −3.6 °C and electrocaloric strength of 0.3 K mm/kV at 125 °C have been achieved. Double negative effects (−0.7 °C at 45 °C and −3.6 °C at 125 °C) and a relatively large positive effect (1 °C) near Curie temperature (190 °C) have been found in the PLZST single crystal. Moreover, microscopic dipoles and a phenomenological Landau-type model were employed to understand these unusual electrocaloric effects. Enhanced negative effect and the coexistence of both negative and positive effects in one material are promising for us to develop practical solid-state cooling devices ...

Giant Negative Electrocaloric Effect in (Pb,La)(Zr,Sn,Ti)O3 Antiferroelectrics Near Room Temperature

(Pb0.97La0.02)(Zr xSn0.94- xTi0.06)O3 (PLZST) antiferroelectric ceramics with x = 0.75-0.90 have been fabricated and found to be a novel electrocaloric material system with a giant negative electrocaloric effect (Δ T = -11.5 K) and a large electrocaloric strength (|Δ T/Δ E| = 0.105 K cm kV-1) near room temperature. Additionally, the PLZST antiferroelectric ceramic also exhibits a large positive electrocaloric effect around the Curie temperature. The giant negative effect and the coexistence of both positive and negative electrocaloric effects in one material indicate a promising possibility to develop mid- to large-scale solid-state cooling devices with high efficiency.