Changes in crystal structure and ferroelectric properties are investigated for (100)/(001)-oriented epitaxial PbTiO3 thin films grown on CaF2 substrates by metal organic chemical vapor deposition. In this work, PbTiO3 films, with thickness ranging from 60 to 2000 nm, presented volume fraction of (001)-oriented c-domain higher than 90%. Hence, the residual strain is smaller compared to films deposited on widely investigated SrTiO3 substrates. Additionally, more than 60 μC/cm2 remnant polarization is obtained for all film thickness ranges, and the estimated spontaneous polarization taking into account c-domain volume fraction is about 80 μC/cm2 regardless of film thickness, in good agreement with reported values for the single crystal.

Epitaxial rhombohedral Pb(Zr0.65Ti0.35)O3films with (100) and (110)/(10-1) and (111)/(11-1) orientations were grown on various kinds of singlecrystal substrates having different thermal expansion coefficient. Volume fractions of (110) and (111) orientations in respective (110)/(10-1) and (111)/(11-1)-oriented films were almost linearly increased with increasing thermal strain, εthermal, applied to the films that wasgenerated under the cooling process after the deposition from the growth temperature to the Curie temperature.Observed saturationpolarization (Psat)was changed linearly with the volume fractions of (110) and (111) orientations, in the same manner asthe volume fractions of (001) and (101) orientations in (001)/(100) and (101)/(110) oriented tetragonal Pb(Zr,Ti)O3 filmsreported previously. These results showed that the volume fraction of the non-180o domains Pb(Zr,Ti)O3films of both tetragonal and rhombohedral symmetriescan be manipulated by εthermal, which brings possibly to control the Psat value.

The growth mechanism of large-size domains in PbTiO3/SrTiO3 heteroepitaxial thin films was examined using annular bright field (ABF) – scanning transmission electron microscopy and geometric phase analysis (GPA). {101} domain walls surrounded 90° domains. The large 90° domain grows by the coalescence of the nano-size domains of less than 5 nm width. A strain map obtained from the GPA of ABF-STEM image showed that 90° domains interacted elastically and attractively with edge dislocations at PbTiO3/SrTiO3 interface through simple shear strain.

Crystal structure change with an applied electric field was investigated by Raman spectroscopy and X-ray diffraction (XRD) for the 1 μm-thick (100)/(001) one-axis oriented tetragonal Pb(Zr0.3Ti0.7)O3 films prepared on Pt-covered (100) Si substrates by chemical solution deposition technique. As-deposited films were under the strained condition in good agreement with the estimation from the thermal strain applied under the cooling process after the deposition from the Curie temperature to the room temperature. This strain was ascertained to be relaxed by an applied electric field in accompanying with the dramatic increase of the volume fraction of (001) orientation. These results demonstrate the importance of the crystal structure measurement not only as-deposited films, but also after applied electric field, such as after poling.

Raman scattering spectra and ferroelectric properties of epitaxial tetragonal Pb(Zr, Ti)O3 were investigated for polar axis-oriented thin films with various Zr/(Zr + Ti) ratios and by changing the ratios from 0 to 0.50 at different measurement temperatures. The chosen films in the thickness range of 1–2 μm present the advantage of showing small residual strain. The E (TO) modes were successfully isolated using cross-polarization configurations, while A1 (TO) and B1 modes were activated using parallel polarization configurations. Systematic changes in Raman peak positions were observed with changes in the Zr/(Zr + Ti) ratios at different measurement temperatures. It was found in both cases that the tetragonal distortion (c/a-1) and the value of square of spontaneous polarization (Ps2) linearly increased with increasing ω2[A1(1TO)], where a and c are the lattice parameters of a and c-axes. This indicates that monitoring A1(1TO) mode is efficient as a characterization method of ferroelectricity. It can also be used as a novel nondestructive process check or reliability assessment technique during fabrication of microelectromechanical systems (MEMS) using piezoelectric materials.

Perfectly (111)-oriented rhombohedral Pb(Zr, Ti)O3 [PZT] films were successfully grown on (111) CaF2 substrates. These films have the polar-axis perpendicular to the substrate surface without non-180o domains. Well saturated polarization (P) –electric field (E) hysteresis loops were observed at various frequencies and temperatures. Temperature dependence of the saturation polarization (Psat.) was in good agreement with the estimated one by Haun et al. using phenomenological approach but did not strongly depend on the measured frequencies. On the other hand, the coercive field (Ec) increased with decreasing temperature and with increasing the measurement frequency.

Crystal structure change with the temperature was investigated for 3 m-thick (100)/(001)-oriented epitaxial PbTiO3 films grown on SrTiO3 substrates. Complex strain-relaxed domain structure labeled as Type III was observed and directly transformed to the cubic phase at about 490°C. This transition temperature and the lattice parameter (a and c- axes) change with the temperature well agreed with the reported data for the PbTiO3 powders. The volume fraction of the (001) orientations, Vc, was almost independent of the temperature up to the phase transition temperature. The tilting angles of the spots in XRD plan view were almost the same with the estimated ones from the lattice parameters and the Vc. This suggests that the angle of the domains identified by the domain structure in Type III. This structure is mainly determined by the tetragonality, (c/a ratio) and the Vc.