This report will try to review briefly the work achieved from 1982 to 1984 in different “subjects to be considered by Commission 31 Time” as adopted in Grenoble 1976. It contains also information provided by Commission members, for which hearty thanks are to be given. The limitation of space required the abbrevation of some institution reports.

Single-walled carbon nanotube (SWCNT) growth were carried out on SiO2/Si substrates using Pt catalysts at different temperatures, from 400°C to 700°C, under various ethanol pressures by an alcohol gas source method, a type of cold-wall chemical vapor deposition (CVD). Raman measurements showed that the optimal ethanol pressure decreased as the growth temperature was reduced, and that SWCNTs grew even at 400°C by optimizing the ethanol pressure to 1×10-5 Pa in a high vacuum system. Compared to the SWCNTs grown from Co catalysts, the diameters of SWCNTs grown from Pt were smaller, irrespective of the growth temperature. In addition, both the SWCNT diameter and the distribution became narrower by reducing the growth temperature and we obtained small-diameter SWCNTs of which the diameters were less than 1 nm using Pt catalysts.

Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.

Bismuth titanate (Bi4Ti3O12; BIT) -based ferroelectric materials are proposed from the view of the “Site-engineering”, where the Bi-site ions are substituted by lanthanoid ions (La3+ and Nd3+) and Ti-site ions by other ions with higher charge valence (V5+). In the present study, influences of vanadium (V) - substitution for (Bi,M)4Ti3O12 thin films [M = lanthanoid] on the ferroelectric properties are evaluated. V-substituted (Bi,M)4Ti3O12 films have been fabricated using a chemical solution deposition (CSD) technique on the (111)Pt/Ti/SiO2/(100)Si substrate. Remnant polarization of (Bi,La)4Ti3O12 and (Bi,Nd)4Ti3O12 films has been improved by the V-substitution independent of the coercive field. The processing temperature of BLT and BNT films could also be lowered by the V-substitution.

In this study, thick sol-gel PZT(Pb(Zr1−xTix)O3) films were fabricated and their characteristics were investigated for angular rate sensor applications. The crack-free thick sol-gel PZT films were successfully deposited on silicon substrates by multiple spin-coating technique combined with rapid thermal annealing(RTA). The thickness of the PZT films is 1.5 νm, which is required by a vibration angular rate sensor for a good actuation and sensing. The remnant polarization of the PZT films is 12.0νC/cm2. The PZT films were applied to the vibration angular rate sensor structure, and the vibration of 1.78νm in amplitude at the resonant frequency of 35.8kHz was obtained. In this case, the driving voltage of 5Vp-p by bulk piezoelectric materials was applied to the driving electrode with out of phase signal through voltage and inverting amplifier.

The oscillating output voltage obtained by external actuation using a stacked piezo-actuator showed the values of 0.76V and 0.87V in outer/inner driving electrode at driving voltage of 5Vp-p.

Y1Ba2Cu3O7-x superconducting composites have been prepared on metallic substrate by rf magnetron sputtering method. Buffer layer of thin SrTiO3 layer between superconducting film and the substrate was found to be effective to realize superconductivity. Preferable grain alignment of c-axis was also obtained. The critical current density at 77K was 2.2x103 A/cm2 with Tc at 83K, and it was found that the thicker films had the higher Jc values.

The C60/C70 thin film crystals have been fabricated on the (001) surface of alkali halide substrates, KC1, KBr, and NaCl, and their structures have been studied. The crystal structure analyses by TEM show that the hexagonal closed packing (hep) with lattice parameters of a=10.0 Å and c=16.3 Å and the face-centered cubic (fee) with a=14.2 Å coexist in the C60 thin film crystals. The C70 thin film crystals show an expanded lattice constant of a=10.5 Å from the view perpendicular to the stacking plane. The ratio of hep to fee is dependent on the kind of the substrates and on the substrate temperatures during the crystal growth. The observed reversible change in the Raman spectrum of the C60 thin films implies a rotational molecular motion in the thin film crystals.

Al substitution for Zr/Ti site of PZT was attempted using a sol-gel method, and the ferroelectric properties of 200nm-thick Al doped PZT thin films were compared with those of non- doped PZT film. The leakage current of the thin films decreased with increasing Al content. Ps and Pr also decreased with increasing Al content, whereas Ec did not show a significant change. Furthermore, a simple capacitor cell structure like FeRAM was prepared using a seed layer process. The capacitor structure was Pb(Ti0.975Al0.025)O3/ Pb1.1((Zr0.52Ti0.48)0. 975Al0.025)O3/ Pb(Ti0.975Al0.025)O3, and 2Pr was 26μC/cm2. The fatigue properties of the A1 doped PZT capacitor cell showed a little improvement, because the reduction rate of the fatigue was smaller than that of non-doped PZT thin film.

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 P s vector. BPT film of x =0.3 exhibited superb ferroelectric properties of remanent polarization 2P r =92 μC/cm2, saturation polarization P sat=50 μC/cm2, and coercive field 2E c =184 kV/cm. The film also showed uniform piezoelectric response with an effective piezoelectric coefficient of AFM-d 33=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 T C . Consequently the polar-axis orientation was distinctively grown along the film normal and the conjugate non-polar-axis was grown in-plane.

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-x V x )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.

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 d 33 evaluated from net longitudinal displacement was smaller than intrinsic d 33, 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 d 33 value calculated from net longitudinal displacement of PZT film depended on the Poisson's ratio of PZT and was not equal to intrinsic d 33, 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 d 33; however this condition is difficult to be satisfied experimentally.

Extended abstract of a paper presented at Microscopy and Microanalysis 2005 in Honolulu, Hawaii, USA, July 31--August 4, 2005

This work presents the preliminary experimental results of Pb(ZrxTi1−x)O3 (PZT) thin films preparation to develop a new combinatorial process by chemical solution deposition (CSD) method. PZT thin films were fabricated from the PbZrO3 (PZ) and PbTiO3 (PT) multilayers on a substrate of Si/SiO2/Ti/Pt. The precursor PT and PZ solutions were coated in different sequences, (i) in the PT start sequence and (ii) in the PZ start sequence, and with different PT and PZ concentrations. It was found that the deposition sequence of PT and PZ led to the differences in composition, microstructure, texture, and ferroelectric property of the resultant thin films. The PT start deposition was suitable for preparation of the PZT thin films, while the PZ start deposition caused composition deviation and bad ferroelectric property. The postannealing had little effect for the formation of the PZT thin films from the multi-PT and PZ layers. A single perovskite phase of PZT can be obtained from the deposited multi-PT and PZ layers even without any postannealing when concentrations of the precursor PT and PZ solution are smaller than 0.025 M and the deposition sequence is in the PT start sequence. This method would be a constructive way to develop and study other thin film materials systems.