Wook Jo

Lanthanum-substituted bismuth titanate for use in non-volatile memories

Non-volatile memory devices are so named because they retain information when power is interrupted; thus they are important computer components. In this context, there has been considerable recent interest in developing non-volatile memories that use ferroelectric thin films—‘ferroelectric random access memories’, or FRAMs—in which information is stored in the polarization state of the ferroelectric material. To realize a practical FRAM, the thin films should satisfy the following criteria: compatibility with existing dynamic random access memory technologies, large remnant polarization (Pr) and reliable polarization-cycling characteristics. Early work focused on lead zirconate titanate (PZT) but, when films of this material were grown on metal electrodes, they generally suffered from a reduction of Pr (‘fatigue’) with polarity switching. Strontium bismuth tantalate (SBT) and related oxides have been proposed to overcome the fatigue problem, but such materials have other shortcomings, such as a high deposition temperature. Here we show that lanthanum-substituted bismuth titanate thin films provide a promising alternative for FRAM applications. The films are fatigue-free on metal electrodes, they can be deposited at temperatures of ∼650 °C and their values of Pr are larger than those of the SBT films.

Giant electric-field-induced strains in lead-free ceramics for actuator applications – status and perspective

In response to the current environmental regulations against the use of lead in daily electronic devices, a number of investigations have been performed worldwide in search for alternative piezoelectric ceramics that can replace the market-dominating lead-based ones, representatively Pb(ZrxTi1-x)O3 (PZT)-based solid solutions. Selected systems of potential importance such as chemically modified and/or crystallographically textured (K, Na)NbO3 and (Bi1/2Na1/2)TiO3-based solid solutions have been developed. Nevertheless, only few achievements have so far been introduced to the marketplace. A recent discovery has greatly extended our tool box for material design by furnishing (Bi1/2Na1/2)TiO3-based ceramics with a reversible phase transition between an ergodic relaxor state and a ferroelectric with the application of electric field. This paired the piezoelectric effect with a strain-generating phase transition and extended opportunities for actuator applications in a completely new manner. In this contribution, we will present the status and perspectives of this new class of actuator ceramics, aiming at covering a wide spectrum of topics, i.e., from fundamentals to practice.

On the phase identity and its thermal evolution of lead free (Bi1/2Na1/2)TiO3-6 mol% BaTiO3

Temperature-dependent dielectric permittivity of 0.94(Bi1/2Na1/2)TiO3-0.06BaTiO3 (BNT-6BT) lead-free piezoceramics was studied to disentangle the existing unclear issues over the crystallographic aspects and phase stability of the system. Application of existing phenomenological relaxor models enabled the relaxor contribution to the entire dielectric permittivity spectra to be deconvoluted. The deconvoluted data in comparison with the temperature-dependent dielectric permittivity of a classical perovskite relaxor, La-modified lead zirconate titanate, clearly suggest that BNT-6BT belongs to the same relaxor category, which was also confirmed by a comparative study on the temperature- dependent polarization hysteresis loops of both materials. Based on these results, we propose that the low-temperature dielectric anomaly does not involve any phase transition such as ferroelectric- to-antiferroelectric. Supported by transmission electron microscopy and X-ray diffraction experiments at ambient temperature, we ...

Origin of the large strain response in (K0.5Na0.5)NbO3-modified (Bi0.5Na0.5)TiO3-BaTiO3 lead-free piezoceramics

The mechanism of the giant unipolar strain recently observed in a lead-free piezoceramic, 0.92(Bi0.5Na0.5)TiO3−0.06BaTiO3−0.02(K0.5Na0.5)NbO3 [S.-T. Zhang, A. B. Kounga, E. Aulbach, H. Ehrenberg, and J. Rodel, Appl. Phys. Lett. 91, 112906 (2007) was investigated. The validity of the previously proposed mechanism that the high strain comes both from a significant volume change during the field-induced phase transition, from an antiferroelectric to a ferroelectric phase and the domain contribution from the induced ferroelectric phase was examined. Monitoring the volume changes from the simultaneously measured longitudinal and transverse strains on disk-shaped samples showed that the phase transition in this specific material does not involve any notable volume change, which indicates that there is little contribution from a volume change due to the phase transition to the total strain response. Temperature dependent hysteresis measurements on unpoled samples of a nearby ferroelectric composition, 0.93(Bi0.5...

Evolving morphotropic phase boundary in lead-free (Bi1/2Na1/2)TiO3–BaTiO3 piezoceramics

The correlation between structure and electrical properties of lead-free (1−x)(Bi1/2Na1/2)TiO3–xBaTiO3 (BNT-100xBT) polycrystalline piezoceramics was investigated systematically by in situ synchrotron diffraction technique, combined with electrical property characterization. It was found that the morphotropic phase boundary (MPB) between a rhombohedral and a tetragonal phase evolved into a morphotropic phase region with electric field. In the unpoled material, the MPB was positioned at the transition from space group R3m to P4mm (BNT-11BT) with optimized permittivity throughout a broad single-phase R3m composition regime. Upon poling, a range of compositions from BNT-6BT to BNT-11BT became two-phase mixture, and maximum piezoelectric coefficient was observed in BNT-7BT. It was shown that optimized electrical properties are related primarily to the capacity for domain texturing and not to phase coexistence.

Electric-field-induced phase transformation at a lead-free morphotropic phase boundary: Case study in a 93%(Bi0.5Na0.5)TiO3–7% BaTiO3 piezoelectric ceramic

The electric-field-induced strain in 93%(Bi0.5Na0.5)TiO3–7%BaTiO3 polycrystalline ceramic is shown to be the result of an electric-field-induced phase transformation from a pseudocubic to tetragonal symmetry. High-energy x-ray diffraction is used to illustrate the microstructural nature of the transformation. A combination of induced unit cell volumetric changes, domain texture, and anisotropic lattice strains are responsible for the observed macroscopic strain. This strain mechanism is not analogous to the high electric-field-induced strains observed in lead-based morphotropic phase boundary systems. Thus, systems which appear cubic under zero field should not be excluded from the search for lead-free piezoelectric compositions.

Lead-free piezoceramics with giant strain in the system Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5NbO3. I. Structure and room temperature properties

Lead-free piezoelectric ceramics, 1� xyBi 0.5 Na 0.5 TiO 3 -xBaTiO 3 -yK 0.5 Na 0.5 NbO 3 0.05x 0.07 and 0.01y 0.03, have been synthesized by a conventional solid state sintering method. The room temperature ferroelectric and piezoelectric properties of these ceramics were studied. Based on the measured properties, the ceramics were categorized into two groups: group I compositions having dominant ferroelectric order and group II compositions displaying mixed ferroelectric and antiferroelectric properties at room temperature. A composition from group II near the boundary between these two groups exhibited a strain as large as 0.45% at an electric field of 8k V/ mm. Polarization in this composition was not stable in that the piezoelectric coefficient d33 at zero electric field was only about 30 pm/ V. The converse piezoelectric response becomes weaker when the composition deviated from the boundary between the groups toward either the ferroelectric or antiferroelectric compositions. These results were rationalized based on a field induced antiferroelectric-ferroelectric phase transition.

DIFFERENCES IN NATURE OF DEFECTS BETWEEN SRBI2TA2O9 AND BI4TI3O12

X-ray photoemission spectroscopy measurements were executed to compare the nature of defects in SrBi2Ta2O9 (SBT) and Bi4Ti3O12 (BTO) films. In the SBT film, it was found that the oxygen ions at the metal–oxygen octahedra were much more stable than those at the Bi2O2 layers. On the other hand, for the BTO film, oxygen vacancies could be induced both at the titanium–oxygen octahedra and at the Bi2O2 layers. We suggested that the difference in stability of the metal–oxygen octahedra should be related to different fatigue behaviors of the SBT and the BTO films.

Morphotropic phase boundary in (1−x)Bi0.5Na0.5TiO3–xK0.5Na0.5NbO3 lead-free piezoceramics

The electromechanical behavior of (1−x)Bi0.5Na0.5TiO3–xK0.5Na0.5NbO3 (BNT-KNN) lead free piezoelectric ceramics is investigated for 0⩽x⩽0.12 to gain insight into the antiferroelectric-ferroelectric (AFE-FE) phase transition on the basis of the giant strain recently observed in BNT-based systems. At x≈0.07, a morphotropic phase boundary (MPB) between a rhombohedral FE phase and a tetragonal AFE phase is found. While the piezoelectric coefficient is largest at this MPB, the total strain further increases with increasing KNN content, indicating the field-induced AFE-FE transition as the main reason for the large strain.

Lead-free piezoceramics with giant strain in the system Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5NbO3. II. Temperature dependent properties

The temperature dependence of the dielectric and ferroelectric properties of lead-free piezoceramics of the composition (1−x−y)Bi0.5Na0.5TiO3–xBaTiO3–yK0.5Na0.5NbO3 (0.05⩽x⩽0.07, 0.01⩽y⩽0.03) was investigated. Measurements of the polarization and strain hystereses indicate a transition to predominantly antiferroelectric order when heating from room temperature to 150°C, while for 150<T<200°C both remnant polarization and coercive field increase. Frequency-dependent susceptibility measurements show that the transition is relaxorlike. For some samples, the transition temperature Td is high enough to allow mostly ferroelectric ordering at room temperature. These samples show a drastic increase of the usable strain under an external electric field just after the transition into the antiferroelectric state at high temperatures. For the other samples, Td is so low that they display significant antiferroelectric ordering already at room temperature. In these samples, the usable strain is relatively stable over a...