Takashi Fujisawa

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.

Thick Epitaxial Pb(Zr0.35,Ti0.65)O3 Films Grown on (100)CaF2 Substrates with Polar-Axis-Orientation

(100)/(001)-oriented tetragonal Pb(Zr,Ti)O3 (PZT) films, which were thicker than 2 µm, were epitaxially grown on SrRuO3-covered (100)Si, (100)KTaO3, (100)SrTiO3, and (100)CaF2 substrates by metal organic chemical vapor deposition. The volume fraction of the (001)-orientation almost linearly increased as the thermal strain increased during the cooling process from the deposition temperature to the Curie temperature. Consequently, perfectly (001)-oriented, i.e., polar-axis-oriented, thick films were obtained on CaF2 substrates with a remanent polarization of 71 µC/cm2. This approach to grow polar-axis-oriented PZT thick films enabled the intrinsic piezoelectricity of PZT itself to be clarified, and has potential in novel applications.

Crystal structure and electrical property comparisons of epitaxial Pb(Zr,Ti)O3 thick films grown on (100)CaF2 and (100)SrTiO3 substrates

Epitaxial Pb(Zr,Ti)O3 (PZT) thick films of 2.0–3.0 μm thickness were grown at 600 °C on (100)cSrRuO3∥(100)SrTiO3 and (100)cSrRuO3∥(100)LaNiO3∥(100)CaF2 substrates by pulsed-metal organic chemical vapor deposition. All films showed (100) and/or (001) orientations with tetragonal symmetry. It was found that there is an almost linear relationship between the estimated thermal strain from the deposition temperature to the Curie temperature and the volume fraction of (001) orientation in the mixture of (100) and (001) orientations for the films on both substrates. Consequently, the perfectly (001)-oriented, i.e., polar-axis-oriented, PZT thick films were obtained on CaF2 with the Zr/(Zr+Ti) ratio from 0.20 to 0.40. Moreover, the lattice parameter of a- and c-axes and their ratio (c/a) of those polar-axis-oriented films were almost the same as the reported data for the powder, suggesting that the large strain is not remaining in those films. The relative dielectric constant (er) of the polar-axis-oriented Pb(Zr...

Domain structure of (100)/(001)-oriented epitaxial PbTiO3 thick films with various volume fraction of (001) orientation grown by metal organic chemical vapor deposition

(100)/(001)-oriented epitaxial PbTiO3 films thicker than 1 μm were grown on various types of substrates by chemical vapor deposition. The domain structures of these films with different volume fractions of (001) were investigated. Domain structures, consisting of (100)/(001)-oriented domains, were observed regardless of the type of substrate. However, the tilting angles of the a- and c-domains from the surface normal linearly changed with the volume fraction of the (001) orientation. These results suggest that the volume fraction of the (001) orientation is crucial in identifying the domain structure of PbTiO3 thick films.

Growth of Epitaxial KNbO3 Thick Films by Hydrothermal Method and Their Characterization

KNbO3 films were grown at 240 °C by the hydrothermal method using KOH and Nb2O5 as source materials. Film thickness increased with reaction time up to 3 h, however decreased for longer reaction times. A 16-µm-thick epitaxially grown KNbO3 film with {100}pc orientation were successfully grown on (100)cSrRuO3∥SrTiO3 substrate for 3 h. The relative dielectric constant and dielectric loss at 100 kHz were 415 and 8%, respectively. Clear hysteresis loops originating from ferroelectricity were observed and the remanent polarization was 20 µC/cm2 at the maximum applied electric field of 220 kV/cm. The effective longitudinal piezoelectric constant, d33eff, obtained using a laser Doppler velocimeter, was 86 pm/V.

Raman Spectroscopy Study of Oxygen Vacancies in PbTiO3 Thin Films Generated Heat-Treated in Hydrogen Atmosphere

Raman spectroscopy is utilized to study the evaluation of vacancies in PbTiO3 thin films subjected to hydrogen atmosphere heat treatment. The B1 mode consisted of only oxygen ion vibration was shifted to lower frequency with increasing heat treatment temperature. It was considered that the oxygen ions were lacking from PbTiO3, and that oxygen vacancies were generated. It was found that the frequency of the B1 mode is proportional to oxygen ion content. Pb ions were also lacking in the PbTiO3 thin films with oxygen ions and the number of oxygen vacancies was larger than that of Pb ions. We suggest that the Raman spectroscopy is a suitable tool for the evaluation of oxygen vacancies in PbTiO3 thin films.

Direct observation of intrinsic piezoelectricity of Pb(Zr,Ti)O3 by time-resolved x-ray diffraction measurement using single-crystalline films

Lead zirconate titanate, Pb(Zr,Ti)O3 or PZT, is one of the most widely investigated ferroelectric and piezoelectric materials due to its superior properties. However, the intrinsic properties of PZT have not been directly measured due to the lack of fabrication of single crystals even though a basic understanding of intrinsic properties has been of interest developing lead-free piezoelectric materials. We demonstrated the direct observation of the intrinsic piezoelectric property by means of the detection of electric-field induced crystal lattice distortion of thick Pb(Zr0.35Ti0.65)O3 single-crystalline films with single polar-axis orientation and negligible residual strain using the time-resolved X-ray diffraction (XRD) together with the polarization response. Consequently, the effective converse piezoelectric response was experimentally revealed; hence, the electrostrictive coefficient, which is the conversion coefficient between the electrical and mechanical response, was determined. The obtained effec...

Epitaxially grown ferroelectric thin films for memory applications (ferroelectric random access memories)

Tetragonal Pb(Zr, Ti)O3 films were epitaxially grown on SrRuO3-coated SrTiO3 substrates by metal organic chemical vapor deposition. Perfect polar-axis-oriented 50 nm thick tetragonal films were successfully grown on (100)SrRuO3//(100)SrTiO3 substrates. The single phase of the tetragonal symmetry region was expanded to a Zr/(Zr + Ti) ratio of around 0.6 for these films but was reduced to around 0.4 when (100)/(001)-mixture oriented 250 nm thick films were obtained. The dependence of spontaneous polarization (Ps) on the lattice parameter of c-axis to a-axis (c/a ratio) was demonstrated using perfectly polar-axis-oriented films with various Zr/(Zr + Ti) ratios. The 250 nm thick (100)/(001), (110)/(101), and (111)-oriented tetragonal films were grown on (100), (110), and (111)-oriented substrates. The domain structure was analyzed in detail, and it was found that the observed saturation polarization (P sat) value can be explained by the Ps value and the 90° domain contribution. These data clearly demonstrate the importance of epitaxial film research for actual ferroelectric random access memories applications.

Single crystal-like selection rules for unipolar-axis oriented tetragonal Pb(Zr,Ti)O3 thick epitaxial films

We investigated the polarized Raman spectra of a strain-free, unipolar-axis oriented tetragonal Pb(Zr,Ti)O3 thick epitaxial film. We evaluated the single crystal-like selection rules of the A1- and E-symmetry components, and found an anomalous behavior in the angular dependence of the A1(1TO)-mode intensity similar to that observed in high-Tc superconductor single crystals. Raman tensor analyses of the A1(1TO) mode revealed complex phases may exist between two independent Raman-tensor components even in the single 180° domain state.

Polarized Raman study for epitaxial PZT thick film with the mixture orientation of (100)/(001)

(100)/(001)-oriented PZT thick films were grown on SrRuO3//(100) SrTiO3 and (100) MgO substrates by matel organic chemical vapor deposition (MOCVD) with different volume fraction of (001) orientation, and were compared with (001) single-oriented epitaxial PZT thick films grown on SrRuO3//LaNiO3//(100) CaF2 by polarized Raman spectroscopy. The spectra from (100)-oriented domain and (001)-oriented domain can be individually observed for the films with the mixture orientation of (100)/(001). Raman analysis revealed the different strain state of (100)-oriented and (001)-oriented domains. Moreover, the rotation dependence of A1(1TO) mode could be explained by the calculation using the volume fraction of (001)-oriented domains obtained from X-ray reciprocal space mapping analysis for the films with the mixture orientation of (100)/(001). These results suggest the local structure characterized by Raman spectroscopy almost agreed with the structure characterized by XRD analysis for the films with the mixture orientation of (100)/(001).