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Growth and characterization of single crystals across the BaTiO3-CaTiO3-BaZrO3 phase diagram for lead-free piezoelectrics

Abstract : Solid solutions belonging to BaZrO3–BaTiO3–CaTiO3 (BCTZ) pseudo-ternary system are promising candidates for lead-free piezoelectrics. This thesis aims at growing and characterizing various single crystals of the BCTZ system: the end members BaZrO3 and CaTiO3 as well as Ba1-xCaxTi1-yZryO3 solid solution compounds with zirconium (Zr) and calcium (Ca) contents close to Ba(Zr0.2Ti0.8)O3-50(Ba0.7Ca0.3)TiO3 composition (BZT-50BCT) where high piezoelectric performances are expected.CaTiO3 and BaZrO3 single crystals were both grown from high temperature solution by the flux method and from the melt by the optical floating zone technique. In the case of CaTiO3 grown with a mirror furnace at 1975°C, aluminum (Al), magnesium (Mg) and barium (Ba) as main impurities were detected. The Raman spectra of CaTiO3 are in good agreement with the spectra referenced in the literature. The growth of BaZrO3 was more challenging because of its very high melting point (2700°C). BaB2O4 flux was successfully used to produce 150-200 μm-sized BaZrO3 crystals at half its melting point (1350°C) and bulk centimeter-sized BaZrO3 boules were grown from the melt. Sr, Hf, Ca and Ti were detected by GDMS and SIMS as main impurities in the range of 0.3-0.5 at.%. The optical band gap is found to be ~4.8 eV and indicates the high quality of the BaZrO3 crystals grown with mirror furnace. Low temperature dielectric properties of BaZrO3 are displayed and confirmed the absence of structural phase transition. Raman investigations reveal that even though BaZrO3 does not have any phase transition at low temperatures, it exhibits a high-pressure phase transition from cubic to tetragonal at 11GPa at room temperature.In the second part, BCTZ centimeter-sized single crystals have been successfully grown by the top seeded solution growth technique. Ca and Zr content profiles throughout the as-grown boules indicate that their effective segregation coefficients are highly dependent on their initial concentration in the liquid solution. Concentrations evolve substantially during the crystal growth, making the BCTZ crystal growth a tricky issue when a narrow compositions range is targeted, as in the vicinity of the phase convergence region. Furthermore, spinodal decomposition was observed, indicating the coexistence of two solid solutions with close compositions in BCTZ crystals. Dielectric and piezoelectric properties were measured for some crystals, which were found to display a variety of behavior form relaxor to pure ferroelectric. In addition, an abnormal double-like PE hysteresis loop was observed, that was associated to an irreversible effect disappearing upon poling.
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Submitted on : Friday, November 30, 2018 - 4:43:49 PM
Last modification on : Tuesday, December 11, 2018 - 3:11:54 PM
Long-term archiving on: : Friday, March 1, 2019 - 3:36:43 PM


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  • HAL Id : tel-01941079, version 1



Cong Xin. Growth and characterization of single crystals across the BaTiO3-CaTiO3-BaZrO3 phase diagram for lead-free piezoelectrics. Material chemistry. Université de Bordeaux, 2018. English. ⟨NNT : 2018BORD0211⟩. ⟨tel-01941079⟩



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