Yoshitaka Ehara

Experimental evidence for orientation property of Pb(Zr0.35Ti0.65)O3 by manipulating polar axis angle using CaF2 substrate

Perfectly oriented (001), (101), and (111) Pb(Zr0.35Ti0.65)O3 (PZT) films were grown on identical (111)CaF2 substrates by metal-organic chemical vapor deposition. These films exclude domains parallel to the surface; therefore, all domains are actively switchable under the electric field between top and bottom electrodes. Saturation polarization values, Psat(001), Psat(101), and Psat(111), for these PZT films were 75, 50, and 43 μC/cm2, respectively. This orientation dependency was in a good agreement with the theoretical relationship for a tetragonal PZT single crystal, where Psat(001)=Psat(101)/2=Psat(111)/3.

Configuration and local elastic interaction of ferroelectric domains and misfit dislocation in PbTiO3/SrTiO3 epitaxial thin films

Abstract We have studied the strain field around the 90° domains and misfit dislocations in PbTiO3/SrTiO3 (001) epitaxial thin films, at the nanoscale, using the geometric phase analysis (GPA) combined with high-resolution transmission electron microscopy (HRTEM) and high-angle annular dark field––scanning transmission electron microscopy (HAADF-STEM). The films typically contain a combination of a/c-mixed domains and misfit dislocations. The PbTiO3 layer was composed from the two types of the a-domain (90° domain): a typical a/c-mixed domain configuration where a-domains are 20–30 nm wide and nano sized domains with a width of about 3 nm. In the latter case, the nano sized a-domain does not contact the film/substrate interface; it remains far from the interface and stems from the misfit dislocation. Strain maps obtained from the GPA of HRTEM images show the elastic interaction between the a-domain and the dislocations. The normal strain field and lattice rotation match each other between them. Strain maps reveal that the a-domain nucleation takes place at the misfit dislocation. The lattice rotation around the misfit dislocation triggers the nucleation of the a-domain; the normal strains around the misfit dislocation relax the residual strain in a-domain; then, the a-domain growth takes place, accompanying the introduction of the additional dislocation perpendicular to the misfit dislocation and the dissociation of the dislocations into two pairs of partial dislocations with an APB, which is the bottom boundary of the a-domain. The novel mechanism of the nucleation and growth of 90° domain in PbTiO3/SrTiO3 epitaxial system has been proposed based on above the results.

Dynamic piezoresponse force microscopy: Spatially resolved probing of polarization dynamics in time and voltage domains

An approach for probing dynamic phenomena during hysteresis loop measurements in piezoresponse force microscopy (PFM) is developed. Dynamic PFM (D-PFM) necessitates development of 5-dimensional (5D) data acquisition protocols and associated methods for analysis and visualization of multidimensional data. Using a combination of multivariate statistical analysis and phenomenological fitting, we explore dynamic behavior during polarization switching in model ferroelectric films with dense ferroelastic domain structures and in ferroelectric capacitors. In polydomain films, multivariate analysis of the switching data suggests that ferroelectric and ferroelastic components can be decoupled and time dynamics can be explored. In capacitors, a strong correlation between polarization dynamics and microstructure is observed. The future potential of D-PFM for probing time-dependent hysteretic phenomena in ferroelectrics and ionic systems is discussed.

Ultrafast switching of ferroelastic nanodomains in bilayered ferroelectric thin films

The dynamic switching of ferroelastic nanodomains in ferroelectric PbZr0.3Ti0.7O3/PbZr0.7Ti0.3O3 bilayers was investigated. Synchrotron microdiffraction using a high-speed pulse generator reveals that electric field pulses as short as 200 ns can switch the ferroelastic domain. Multiples of random distribution analysis of the field-induced changes in diffraction peak intensities finds a dynamic strain change from 0.2 to 1% with increasing the pulse width. Raman spectroscopy shows considerable decreases in A1(1TO) soft mode intensity after applications of short pulses, confirming the ferroelastic switching. The results demonstrate that ferroelastic domains can indeed move at time scales of the order of hundreds of nanoseconds.

Spontaneous polarization estimation from the soft mode in strain-free epitaxial polar axis-oriented Pb(Zr,Ti)O3 thick films with tetragonal symmetry

The ferroelectric property, crystal structure, and A1(1TO) soft mode of almost strain-free epitaxial polar axis-oriented tetragonal lead zirconate titanate thick films grown on CaF2 substrates were investigated by changing the Zr/(Zr+Ti) ratio and the temperature. The square of spontaneous polarization (Ps), Ps2, monotonically increased as tetragonal distortion, (c/a)−1, increased where a and c are the lattice parameters of the films and as the square of frequency in A1(1TO), ω2[A1(1TO)], increased. Additionally, the relationships of Ps2, (c/a−1), and ω2[A1(1TO)] were experimentally obtained, which confirmed the Ps value obtained from (c/a−1) and ω[A1(1TO)] without direct polarization measurements.

Growth of (111)-oriented BaTiO3–Bi(Mg0.5Ti0.5)O3 epitaxial films and their crystal structure and electrical property characterizations

Epitaxial (1−x)BaTiO3−xBi(Mg0.5Ti0.5)O3 films with x = 0 − 0.9 were grown on (111)cSrRuO3//(111)SrTiO3 substrates by pulsed laser deposition (PLD). Plotting the temperature where dielectric constant reaches a maximum {T[ɛr(max.)]} versus Bi(Mg0.5,Ti0.5)O3 content present minimum at x = 0.1. On the other hand, the remanent polarization (Pr) and the effective transverse piezoelectric constant [d33(eff.)] showed minimum at 0.1 and 0.2, respectively, but increased with the increase of x in (1−x)BaTiO3−xBi(Mg0.5Ti0.5)O3 above these values. These results show the simultaneous increase of T[ɛr(max.)] and d33(eff.) for the films above x = 0.2 that normally showed treads off characteristics.

In situ Raman spectroscopy for characterization of the domain contributions to electrical and piezoelectric responses in Pb(Zr,Ti)O3 films

We employed in situ Raman spectroscopy under electric field for (100)/(001)-oriented tetragonal Pb(Ti0.61Zr0.39)O3 films with (001)-volume fraction (VC) of 35%. The increase in VC was revealed above 200 kV/cm, which resulted in the larger remanent polarization. In addition, the application of high enough field also brings a feature, i.e., large reversible change in VC with/without electric field that can quantitatively explain the enhanced piezoelectric response. These demonstrate the usefulness of in situ Raman observation to probe the domain contributions to the electrical and piezoelectric responses.

Dependence of e31,f on polar axis texture for tetragonal Pb(Zrx,Ti1−x)O3 thin films

It was shown by Ouyang et al. [Appl. Phys. Lett. 86, 152901 (2005)] that the piezoelectric e31,f coefficient is largest parallel to the spontaneous polarization in tetragonal PbZrxTi1−xO3 (PZT) films. However, the expected piezoelectric data are typically calculated from phenomenological constants derived from data on ceramic PZT. In this work, the dependence of e31,f on c-axis texture fraction, f001, for {001}PZT thin films was measured by growing films with systematically changed f001 using CaF2, MgO, SrTiO3, and Si substrates. An approximately linear increase in e31,f with f001 was observed for compositions up to 43 mol. % Zr, and 100% c-domain properties were extrapolated. It was demonstrated that c-axis PZT films can achieve e31,f exceeding −12 C/m2 for many tetragonal compositions. The energy harvesting figure of merit, e31,f2/er, for c-axis PZT films surpassed 0.8 C2/m4. This is larger than the figure of merit of gradient-free PZT films grown on Si substrates by a factor of four.

Film Thickness Dependence of Ferroelectric Properties of (111)-Oriented Epitaxial Bi(Mg1/2Ti1/2)O3 Films

The origin of the ferroelectricity of Bi(Mg1/2Ti1/2)O3 films was investigated. Epitaxial Bi(Mg1/2Ti1/2)O3 films with film thicknesses of 50 to 800 nm were grown on (111)cSrRuO3/(111)SrTiO3 substrates by pulsed laser deposition. A Bi(Mg1/2Ti1/2)O3 film was not strongly clamped from the substrate and identified to have rhombohedral symmetry with a = 0.398 nm and α= 89.8°, which was independent of film thickness within 100 to 800 nm. The relative dielectric constant, remanent polarization, and coercive field of the Bi(Mg1/2Ti1/2)O3 films at room temperature were almost constant at about 250, 60 µC/cm2, and 240 kV/cm, respectively, for film thicknesses above 200 nm. These data suggest that Bi(Mg1/2Ti1/2)O3 films are ferroelectric.

Impact of pulse poling on static and dynamic ferroelastic-domain contributions in tetragonal Pb(Ti, Zr)O3 films determined by in-situ x–ray diffraction analysis

The effects of bipolar pulse poling on the ferroelastic domain structure and their contribution to the electrical and piezoelectric properties of Pb(Ti0.7Zr0.3)O3 films are investigated. Micro x-ray diffraction measurements clearly show that the volume fraction of the c-domain increases irreversibly as the poling field is increased, leading to changes in the remanent polarization, dielectric constant, and piezoelectric coefficient. Theoretical estimations well explain the changes of remanent polarization and dielectric constant, but the increase in piezoelectric coefficient is much larger than the theoretical estimation. In-situ x-ray diffraction analysis under an electric field reveals that this disagreement is due to the unexpected activation of the ferroelastic domain wall motion. Our results provide new insight into the poling effect on the electric and piezoelectric properties of ferroelectric films.