Ti-site substitution using the higher-valent cation was performed on ferroelectric thin films of neodymium-substituted bismuth titanate, (Bi,Nd)4Ti3O12 (BNT), in order to improve its ferroelectric properties by compensating the space charge in BIT-based crystal. Ti-site-substituted BNT films, (Bi3.50Nd0.50)1-(x/12)(Ti3.00-xVx)O15 (x = 0 ∼ 0.09), were fabricated on (111)Pt/Ti/ SiO2/(100)Si substrates using a chemical solution deposition (CSD) technique. V5+-substitution enhanced the remanent polarization of BNT film without change in the coercive field. V5+-substitution also exhibited the possibilities for improving the endurance against leakage current and fatigue degradation.

To reveal the complete performance of intrinsic ferroelectriciy-related properties in single crystalline bismuth-layer-structured displacive ferroelectrics in film form on Si, the crucial roles of both orientation control technology by lattice matching from the atomic arrangement of substrate layer and configuration of the volume fraction of 90°-domain during cooling process were demonstrated. 1.2 μm-thick and Pr3+-substituted Bi4-xPrxTi3O12 (BPT, x =0.0, 0.3, 0.5, 0.7) films were grown on Ir(111)/Ti/SiO2/Si(001) substrates by chemical solution deposition (CSD) method with preferred orientation along the major component of Ps vector. BPT film of x =0.3 exhibited superb ferroelectric properties of remanent polarization 2Pr=92 μC/cm2, saturation polarization Psat=50 μC/cm2, and coercive field 2Ec=184 kV/cm. The film also showed uniform piezoelectric response with an effective piezoelectric coefficient of AFM-d33=36 pm/V. During the decomposition of precursor solutions, IrO2 layers were formed at the surface of Ir layers and promoted a/b-axes orientation. During the cooling process after grain growth, in addition, the differential thermal expansion and residual strain between film and substrate introduced bidirectional lateral stress into BPT film and might eliminate the 90°-domain walls dividing a-and b-domains through the relaxation by domain formation at the Curie temperature TC. Consequently the polar-axis orientation was distinctively grown along the film normal and the conjugate non-polar-axis was grown in-plane.

A combination of the preparation techniques for the ferroelectric films and the micro machining of Si is considered to be an effective way to fabricate microelectromechanical systems (MEMS), such as piezoelectric micro-transducer devices for the electrical and medical fields. In this study, 10-μm-thick disk shape lead zirconate titanate (PZT) thick films were successfully fabricated using a chemical solution deposition (CSD) process. Pt top electrode and PZT layer were etched by reactive ion etching (RIE) process, and 100 to 500-μm-diameter PZT micro disks were fabricated on Pt/SiO2/Si substrate. The relative dielectric constant, dissipation factor, remnant polarization and coercive field were εr = 1130, tanδ = 0.02, Pr = 14 μC/cm2 and Ec = 25 kV/cm, respectively. This means that the ferroelectric and dielectric properties of the PZT micro disks were comparable with that of the bulk PZT ceramics. The PZT micro disk showed the butterfly-shaped displacement curve, related with piezoelectric response, in the case of bipolar measurement. The piezoelectric constant of the PZT disks poled at 80Vfor 10 min was estimated to be AFM d33 = 221 pm/V. A resonance frequency of the radial oscillation was evaluated to apply for micro transducer devices.

Electric-field-induced displacements of PZT film capacitor Pt/PZT(5μm)/Pt/SiO2/Si(100) were calculated by finite element method with various parameters of sample geometry: the diameter of top electrode φ TE ranging from 0.2 μ m to 1000 μ m and whether PZT film was continuous or side-etched. If φ TE was larger than 40μ m, surface longitudinal displacement (corresponding to AFM-measured strain) was not equal to net longitudinal displacement of PZT film, including a contribution of the bending motion of substrate. In contrast, if φ TE was smaller than 4μ m and PZT film was continuous, effective d33 evaluated from net longitudinal displacement was smaller than intrinsic d33, because the side PZT film clamped the edge of the capacitor disk and prevented the whole disk from elongating longitudinally. It was also revealed that d33 value calculated from net longitudinal displacement of PZT film depended on the Poisson's ratio of PZT and was not equal to intrinsic d33, excluding the case that φ TE was smaller than 4μ m and PZT film was side-etched. In conclusion, it is suggested that smaller φ TE (< 4μ m, in our case) and side-etch treatment permit a precision measurement of d33; however this condition is difficult to be satisfied experimentally.

Strongly (117)-oriented Bi4Ti3O12 (BIT) thin (300 nm in thickness) and thick (900 nm in thickness) films were successfully synthesized from chemical solution and the piezoelectric and ferrelectric properties were studied. The chemical solution of Bi-acetate and Ti-iso-propoxide dissolved in 2-methoxyethanol was spin-coated on Pt(111)/Ti/SiO2/Si(001) substrate, pyrolysed at 450–600 °C and annealed at 600 °C. On 300-nm-thick BIT thin film, Pt top electrodes were deposited through a metal mask by RF-sputtering. For longitudinal piezoelectric displacement measurement in partially unconstraint, 900-nm-thick BIT thick film, an array of disk-shape BIT capacitor cells with Pt top electrode layers standing on the Pt bottom electrode were fabricated by photolithography with the diameter of 80, 50, 30, 20 μm. To recover from plasma damage, post deposition annealing of 300-nm-thick BIT film and post lithograph annealing of 900-nm-thick BIT film were performed, respectively. Longitudinal piezoelectric displacement was measured directly from the Z-feedback and Z-error signals of an AFM piezoscanner head with application of ac electric field at 5 Hz and 1 kHz, respectively between the conductive cantilever tip contacted to the top Pt electrode and the bottom Pt electrode. By the removal of sidewalls of BIT, positive piezoelectric displacement response was measured. The maximum strain was about 0.1 % under bipolar drive (amplitude of 400 kV/cm or 4Ec). From the unipolar driven piezoelectric displacement, piezoelectric coefficient AFM-d33 was measured. The value of AFM-d33 increased to decreasing cell diameter and approached to a somewhat constant value of 12–13 pC/N. Considering the crystalline orientation, this value well corresponds to that of 20 pC/N which were reported previously in single crystal. The result of ferroelectric property measurement was rather contradictory. The values of remanent and saturated polarization Pr=20 and Psat=28 μC/cm2, respectively measured in 300-nm-thick BIT thin film were in good agreement with reported spontaneous polarization Ps=50 μC/cm2 along a-axis with the consideration of measured inclination angle of Ψ=58° between (200) and (117). In 900-nm-thick BIT thick film, on the other hand, measured values of Pr=6–7 μC/cm2 were much poorer than those of the thin film even with the consideration that measurement frequencies were 1 kHz in the thick film and 50 Hz in the thin film, although the films showed (117)-orientation. Measured piezoelectric response may reflect a specific single grain with favorable orientation in a cell, on the other hand, average value of ferroelectric property throughout a cell in the 900-nm-thick BIT thick film having mixed orientation of (117) and (020).

Bismuth titanate (Bi4Ti3O12; BIT) -based ferroelectric thin films fabricated from a view point of “the site-engineering technique” have been expected to improve the fatal disadvantage of a ferroelectric BIT film, i.e., its low spontaneous polarization; here, Bi- and Ti-site ions in the BIT crystal are cosubstituted by lanthanoid ions and cations with a higher charge valence, respectively, In the present study, we have mainly focused on Ti-site substitution of bismuth titanate (Bi4Ti3O12; BIT)-based thin films using some ions with higher charge valences (V5+, Nb5+, Ta 5+ and W6+; in this study) to enhance the ferroelectric properties of those materials. The BIT-based films with various chemical compositions were fabricated on a (111)Pt/Ti/SiO2/(100)Si substrate by a chemical solution deposition method.

Ti-site substitution of BIT films by the higher-valent ions, Bi3.99(Ti2.97V0.03)O12, Bi3.99(Ti2.97Nb0.03)O12, Bi3.99(Ti2.97Ta0.03)O12 and Bi3.98(Ti2.97W0.03)O12, reduced the leakage current density of BIT films from ∼ 10-6 down to ∼ 10-7 A/cm2 at an applied field of 50 kV/cm, while the substitution by the same-valent cation, e.g., Bi4.00(Ti2.97Zr0.03)O12, did not affect the behavior of leakage current. Whereas polarization (P) - electrical field (E) hysteresis loops of non-substituted and Zr-substituted BIT films were distorted due to the leakage current, non-distorted P-E loops were obtained at V5+-, Nb5+-, Ta5+- and W6+-substituted BIT films.

Also, Ti-site substitution was effective for improving the ferroelectric properties in lanthanoid-substituted BIT films. In the case of La3+-substituted BIT film (BLT), remanent polarization (Pr) of V5+- and W6+-substituted BLT films, (Bi3.24La0.75)(Ti2.97V0.03)O12 and (Bi3.23La0.75)(Ti2.97W0.03)O12 (13 and 12 μC/cm2, respectively), were larger than those of Zr4+- and non-substituted BLT films, (Bi3.25La0.75)(Ti2.97Zr0.03)O12 and (Bi3.25La0.75)(Ti3.00)O12 (8 and 9 μC/cm2, respectively), while those films had similar coercive field (Ec) of approximately 120 kV/cm. Also in the case of Nd3+-substituted BIT film (BNT), Pr and Ec values of V5+-substituted BNT film, (Bi3.24Nd0.75)(Ti2.98V0.02)O12, were 37 μC/cm2 and 119 kV/cm, respectively, which were comparable with those of conventional Pb-based ferroelectrics such as lead zirconate titanate, Pb(Zr,Ti)O3. We concluded that enhancement of the Pr value was achieved by the charge compensation of oxygen vacancies in BIT-based ferroelectrics using higher-valent cations than Ti4+ ion whereas no obvious differences were found in the crystal orientation and or microstructure of these films.

Oxygen-ionic and electronic conductive thin films with the composition of La0.6Sr0.4Co0.5Fe0.5O3-α (LSCF) were prepared on a porous alumina substrate by a chemical solution deposition (CSD) process and their oxygen permeating flux densities were measured. Thickness of the LSCF layer on the substrate was about 0.4 μm. Oxygen flux density of the LSCF sample was found to be 0.6 μmol·cm-2·s-1, however, time-dependent degradation of oxygen flux was observed. The CeO2 barrier layer between the LSCF layer and the substrate was effective in order to improve time-dependent degradation of oxygen flux.

Effects on ferroelectric and piezoelectric properties of top-electrode diameter variance from 80 to 8 μm were investigated using an AFM probing system connected with a ferroelectric test system with bipolar and unipolar signals at 5 Hz. The Pt and 1.2-μm-thick PZT layers were etched off to prepare Pt top electrode etched samples or Pt/PZT stack etched samples. In the case of bipolar measurement, the top electrode diameter did not affect ferroelectric properties, while the maximum displacement of the butterfly-shaped hysteresis curve, related with piezoelectric response, increased with decreasing top-electrode diameter. On the other hand, the longitudinal piezoelectric constant, AFM d33, calculated from the strain curve slope at 5 Hz, +5 V, increased with decreasing top-electrode diameter. The average value of the Pt/PZT stack-etched AFM d33 almost equals that of Pt-etched AFM d33. Average AFM d33 of the 8-μm-diameter Pt-etched and Pt/PZT stack-etched samples are 129 and 135 pm/V, respectively.

Ferroelectric Bi4Ti3O12 (BIT) thin films were modified by the substitution of Sr2+ ions for Bi3+ ions and of Nb5+ for Ti4+ (codoping) by spin-coating and decomposition of chemical solutions of metal-alkoxide materials (the nominal compositions of Bi4−xSrxTi3−xNbxO12 where x=0.0, 0.5, 1.0, 1.5). Single-phase thin films were crystallized above 550°C with BIT-type structure. The ferroelectric properties were found, though, with the values of Pr=10 μC/cm2 Ec=100 kV/cm, εr=300, and tanδ<5 % for Bi3.5Sr0.5Ti2.5Nb0.5O12 (x=0.5) annealed at 650 °C. Perhaps due to the lowering of the Curie temperature with increasing x, the maximum value of δr increased.