This is the annual report of Okuyama Laboratory in Graduate School of Engineering Science, Osaka University, and attempts to give

a comprehensive view of our research activities in the field of semiconductor and ferroelectric physics. It includes a brief description on each research project conducted in our laboratory and publications in April 2004-March 2005. This report is issued with the hope that it will be useful for visitors to our laboratory.

II. Research Projects

Characterization of Fixed Charges in HfO2 Thin Films by Photoreflectance Spectroscopy and First Principle Calculation
M. Yoshida, J. Matsumoto, M. Sohgawa, T. Kanashima, A. Fujimoto and M. Okuyama Photoreflectance spectroscopy (PRS) is one of the modulation spectroscopy methods, which allows the contactless and non-destructive characterization of electric properties at the Si surface without the electrode formation, because it is full optical measurement. The density of states (DOS) and total energy of HfO2 monoclinic structure with the oxygen vacancy were calculated by using ABINIT, which is one of first principle calculation packages. It is found that the structure with positive charged vacancy is more stable that with not-charged vacancy. Fixed oxide charges in HfO2 thin films have been characterized by PRS. HfO2 films were deposited on Si by pulsed laser deposition (PLD) in N2, O2 and a mixture of these gases. PRS spectral intensity decreases with increasing positive charge in a film. HfO2 deposited in N2 has larger positive charges than that deposited in O2 because of smaller PRS spectral intensity of the former. It is confirmed by ArF laser irradiation that this positive charge is caused by oxygen vacancies in HfO2. Moreover, the effects of rapid thermal annealing (RTA) on HfO2/Si have been evaluated by PRS. The PRS spectral intensity becomes maximum by RTA at 600oC in N2 or O2. It is suggested that the suitable temperature for the RTA of the HfO2/Si structure prepared by PLD is 600oC.

Electrodeless Characterization of Memorized States of MFIS Structure by Photoreflectance Spectroscopy

M. Sohgawa, M. Yoshida, T. Kanashima, A. Fujimoto and M. Okuyama SrBi2Ta2O9 (SBT)/SiO2/Si structures have been characterized by photoreflectance spectroscopy (PRS) without electrode formation. SBT film was deposited on SiO2/n-Si by the metal-organic decomposition (MOD) method and annealed in O2 atmosphere at 600oC. The voltage was applied by attaching ITO transparent electrodes during PRS measurement. The PRS spectral intensity of SBT/SiO2/Si structure has hysteresis characteristics as well as a C-V curve. Additionally, the spectral intensity gradually decreases with time, in a similar way to reduction of the capacitance. These results mean

that the spectral intensity indicates the ferroelectricity of SBT film in SBT/SiO2/Si structure, so that it is considered that characterization of MFIS structure without electrode can be measured by PRS.

Characterizations of High-k Gate Thin Films and These Interfaces of MOS Structure
T. Tada, M. Tsumori, T. Kanashima and M. Okuyama Gate insulator films in ULSI devices become thinner and thinner, and the leakage current cannot be ignored. It is valid that the film thickness to be increased by using high-k materials instead of SiO2 to reduce the leakage. From this viewpoint, high-k materials such as HfO2, PrOx, etc. are studied. These films are deposited by sputtering, pulsed laser deposition, metal-organic chemical vapor deposition (MOCVD), etc. Especially, MOCVD has remarkable advantages, but the deposited films contain a large amount of organic contamination, because the source material such as Hf(O-t-C4H9)4 (HTB) contains carbon. In this paper, we have investigated the reduction of carbon impurities in the film by irradiation with vacuum ultraviolet (VUV) light during MOCVD (photoassisted MOCVD). Calculation results suggest that VUV irradiation is effective for decomposition of HTB. It is clearly seen from IR spectrum that the intensity of peak related to C-H is reduced by irradiation with VUV light during deposition. This suggests that photo-assisted MOCVD is effective for reduction of carbon contamination. Moreover, capacitance of photo-assisted MOCVD is larger than that of MOCVD, and the surface roughness is smaller than 0.1 nm.

Theoretical Study of Atomic Relaxation in 90 deg. Domain Walls of Ferroelectric Perovskite Films
D. Ricinschi, Y. Ishibashi and M. Okuyama In this project, we have studied the extent of atomic relaxation in a ferroelectric film assumed in the tetragonal phase, epitaxially grown on a cubic substrate. The problem has been solved within the framework of a Frenkel-Kontorova-type model, a chain of atoms harmonically coupled and subjected to the periodical action of the on-site substrate potential. The equilibrium profiles of the order parameter as a function of model parameters, including the film and substrate lattice constants, have been calculated by solving the Euler-Lagrange equations and minimizing the total energy. Subsequently we have applied the model for calculating atomic displacements in PbTiO3 and BaTiO3 thin films constrained onto typical substrates. Predictions have been made concerning the optimal substrate period assuring coherent matching of atoms in the ferroelectric layer with respect to substrate atoms.

Analysis of the Switching Characteristics of PZT Films by First Order Reversal Curve Diagrams
D. Ricinschi and M. Okuyama

We have previously proposed a new type of characterization of ferroelectric switching using First Order Reversal Curve (FORC) diagrams based on recording of minor hysteresis loops. This time we have applied this method to polycrystalline and epitaxial PZT thin films measured under various conditions and compared them to PZT ceramics. In each case we have been able to separate the reversible and irreversible contributions to switching and discuss the most dominant of them in relation to hysteresis loop shapes and ferroelectric switching mechanisms. The FORC diagrams of fatigued PZT exhibit features in agreement with its hysteresis probed at nanoscale and confirm a degradation mechanism based on local imprint. The asymmetrical tail present on measured FORC diagrams has been explained in terms of a nucleation-growth switching process triggered by latent nuclei. Although the FORC diagrams derived from such a model do not resemble the FORC diagrams derived by assuming a Preisach-type distribution of ferroelectric units, they show similar characteristics with the experimental ones. These findings attest the usefulness of the FORC diagrams for both characterizing various types of samples as well as the elucidation of ferroelectrics physics.

Elaboration of a nucleation-growth model for ferroelectric hysteresis loops with complete and partial switching
D. Ricinschi and M. Okuyama In this project we have proposed a two-dimensional lattice model based on a discrete Landau-Devonshire-type potential for calculating hysteresis loops of ferroelectric thin films in switching and sub-switching regimes, yielding good agreement with experimental data. Such a model is valuable for simulating the electric response of nonvolatile memory cells based on ferroelectric film capacitors. Setting the electric field below the nominal coercive field of Landau theory and placing nucleation seeds randomly in the lattice, switching proceeds with a nucleation-growth mechanism. Interactions with neighbors have also been taken into account. We have been able to qualitatively reproduce the shapes of experimental hysteresis loops measured on two types of PZT films in both switching and sub-switching regimes, as the negative susceptibility regions of minor loops are eliminated in our model. Snapshots of domain patterns associated to various points of hysteresis loops help understanding the nature of switching in time dependent electric field and may establish a link to modeling approaches based on ferroelectric property distributions.

First principles calculations on bismuth ferrite

D. Ricinschi, T. Kanashima, K-Y. Yun and M. Okuyama The application of ferroelectric thin films to nonvolatile memories require materials with large spontaneous polarization in order to increase the flexibility with respect to integration into high-density memory chips. The search of ferroelectrics with such improved properties needs theoretical predictions on the performance of novel materials. To achieve this task, first-principles calculations are shown recently to be a very valuable tool. During the last few years the new class of multiferroics has attracted a lot of

attention for their interesting physics and potential for novel applications making use of the magnetoelectric coupling. Among them, BiFeO3 has been known historically to have a rather small spontaneous polarization of only 6 mC/cm2 in single crystal form. However, recent measurements on epitaxial thin film samples have shown a 10 times larger polarization. It has been initially suggested that the origin of this large polarization is the epitaxial constraint imposed by the substrate onto which the film is grown. However our experimental data on polycrystalline films have revealed significant enhancement of polarization (including the world-largest ferroelectric polarization of 150 mC/cm2) even in absence of epitaxial matching. These findings are difficult to explain and therefore first-principles calculations are expected to play a major role. Indeed, our calculations have revealed that the spontaneous polarization in bulk BiFeO3 is indeed of order of 100 mC/cm2 and can be even larger, approaching the experimental giant value, in thin film form. This has the implication of proving that intrinsically BiFeO3 has a larger polarization and therefore a good potential to be used for nonvolatile memory applications.

Preparation of m=1-2 Series Bi2MoO6-Bi3TiNbO9 (BM-BTN) and Bi2WO6-Bi3TiNbO9 (BW-BTN) Natural-Superlattice-Structured Bismuth-Layer-Structured Ferroelectric Thin Films
Akira Shibuya, Minoru Noda, Masanori Okuyama and Keisuke Saito C-axis-oriented epitaxial natural-superlattice-structured Bi2MoO6-Bi3TiNbO9 (BMBTN) (m=1-2) and Bi2WO6-Bi3TiNbO9 (BW-BTN) (m=1-2) films are grown by pulsed-laser deposition (PLD) on SrTiO3 (001) substrates. The c-lattice constant (6.738 nm) of the BM-BTN film is very close to that (6.54 nm) of the superlattice structure of one BM unit cell and two BTN unit cells. The c-lattice constant (2.089 nm) of the BWBTN film is very close to that (2.07 nm) of the superlattice structure of one BW unit cell and one BTN unit cell. The long-range natural-superlattice-structure of BM and BTN films have been prepared on Pt(111)/TiO2/SiO2/Si substrates by PLD and oxygen postannealing at 650C. X-ray diffractions clearly show the formation of the long-range superlattice of the 15.5 nm iterative layer, which corresponds to 50 unit cells consisting of (113)-oriented BM and (115)-oriented BTN. These BM BTN thin films exhibit good ferroelectricity with a 2Pr of 40 mC/cm2.

Characterization of natural-superlattice-structured Bi2MoO6-Bi4Ti3O12 (m=1-3) thin films

Akira Shibuya, Minoru Noda, Masanori Okuyama and Keisuke Saito Natural-superlattice-structured Bi2MoO6-Bi4Ti3O12 (BM-BIT) (m=1-3) thin films have been prepared on Pt/TiO2/SiO2/Si and SrTiO3 (001) single crystal substrates by pulsed laser deposition and show very good ferroelectric properties. The BM-BIT film seems to be almost single phase and its c-lattice constant is estimated to be 2.47 nm. This lattice constant is very close to that (2.45 nm) of the superlattice structure consisting of one BM unit cell and one BIT unit cell, namely 1-1 superlattice of BM-BIT. This natural-

superlattice structure consisting of non-sequential m number BLSF materials such as m=1-3 has never been reported so far. The reciprocal space mapping suggests that the BM-BIT film has not only BM-BIT superlattice but also BM because of clear BM (113) peak. The 2 of BM (002) peak is the same as BM-BIT (003) peak because c-lattice constant of BIT is almost the same as twice of c-lattice constant of BM. Theoretical curves of (001), (111) and (221) clearly indicate that the film consisting of BM-BIT and BM has an exact epitaxial BLSF structure along the c-axis. BM (m=1) is widely recognized not only as a ferroelectric material but also as a catalyst for use in selective oxidation. From this viewpoint, unusual BM-based natural-superlattice structures may be attributed to catalytic property of BM (m=1). Polycrystalline BM-BIT (m=1-3) thin film on Pt/TiO2/SiO2/Si substrate deposited at 450C and post-annealed at 650C is found to include both BIT (m=3), BM (m=1) and BM-BIT (m=1-3) phases from XRD pattern. The polycrystalline BM-BIT (m=1-3) film has much larger remanent polarization (2Pr = 54 mC/cm2). The Pr and coercive field (Ec) of the P-E hysteresis loops show good saturation behavior for the applied field. From SEM images of (a) BIT film and (b) BMBIT film deposited at 450C and annealed at 650C, the surface morphologies are quite different from each other, although both films are prepared by the same condition. The surface morphology of BIT film is very rough and the grain is plate-like. On the other hands, the surface of BM-BIT film is smooth in some locations and the grains are very large. Catalytic BM induces BM-BIT to enlarge the grain and domain structure during oxygen annealing. The large grain and domain structure may be also one reason why BM-BIT has good ferroelectricity.

Long-Range Natural-Superlattice of Bi2MoO6 and Bi3TiNbO9 Ferroelectric Thin Films

A. Shibuya, M. Noda and M. Okuyama Long-range natural-superlattice-structure of ferroelectric thin films consisting of Bi2MoO6 (BM) and Bi3TiNbO9 (BTN) have been prepared on Pt(111)/TiO2/SiO2/Si substrates by using a pulsed laser deposition (PLD) and an oxygen post-annealing at 650oC. X-ray diffraction clearly shows the formation of the long-range superlattice of 15.5 nm iterative layer which corresponds to 50 unit cells consisting of (113)-oriented BM and (115)-oriented BTN. The long-range superlattice structures are self-assembled from (222)-preferentially-oriented fluorite phase by oxygen post-annealing at 650oC. The long-range natural-superlattice-structured BM-BTN thin film shows good ferroelectricity reflected by the value of 2Pr, which is estimated to be 40 mC/cm2.

Polarization Hysteresis Control by La and Nd Substitutions in NaturalSuperlattice-Structured Bi3TiNbO9-Bi4Ti3O12 Thin Films

A. Shibuya, M. Noda and M. Okuyama La- and Nd- substitutions for A-site of Bi in natural-superlattice structure of Bi3TiNbO9Bi4Ti3O12 (BTN-BIT) films have been successfully carried out to reduce the coercive field (Ec) and enlarge the remanent polarization (Pr). These films have been grown on

Pt(100)/TiO2/SiO2/Si and Pt(111)/TiO2/SiO2/Si heated at 550oC by pulsed laser deposition. X-ray photoelectron spectroscopy analysis shows the chemical state and stability of the Bi ions in the films. The La substitution has increased Pr, but decrease Ec and their twice values are 52 mC/cm2 and 220 kV/cm, respectively. The 2Pr and 2Ec of the BTN-BIT:Nd0.5 film have been enhanced and are 70 mC/cm2 and 370 kV/cm, respectively. A-site substitutions of La and Nd are effective to control the hysteresis characteristics in natural-superlattice-structured BTN-BIT thin films.

Structural and Multiferroic Properties of BiFeO3 Thin Films

Kwi-Young Yun, Minoru Noda, Hiromasa Saeki, Hitoshi Tabata, Keisuke Saito and Masanori Okuyama BiFeO3 thin films have been prepared on Pt/TiO2/SiO2/Si substrates under various oxygen pressures of 0.15-0.005 Torr at a temperature of 450oC by pulsed-laser deposition. The effects of deposition pressure on their crystal structure and multiferroic properties have been investigated at room temperature. X-ray diffraction analysis (q-2q scans and 2-dimensional scans), shows that the BiFeO3 thin films consist of perovskite single-phase with tetragonal crystal structure and space group P4mm. The c-axis lattice constant decreases (4.062 to 4.006 and c/a ratio of the films decreases from 1.032 to 1.014 with decreasing the oxygen pressure. The surface roughness and grain size of the films depend dramatically on oxygen pressures. The dielectric constant of the films decreases with decreasing oxygen pressure. The film deposited at 0.05 Torr shows a stable current density and well-saturated hysteresis loop with twice the remanent polarization (2Pr) of 136 mC/cm2 and coercive field (2Ec) of 109 kV/cm. The BiFeO3 thin films also show the saturated weak ferromagnetic hysteresis loops with a small remanent magnetization.

Giant Ferroelectric Polarization in the Multiferroic BiFeO3 Thin Films

Kwi-Young YUN, Dan RICINSCHI, Takeshi KANASHIMA, Minoru NODA and Masanori OKUYAMA Ferroelectric BiFeO3 thin films have been deposited on Pt/TiO2/SiO2/Si substrate by pulsed-laser deposition. From the X-ray diffraction analysis, the BiFeO3 thin film consists of perovskite single-phase, and the crystal structure shows the tetragonal structure (c/a = 1.018) with a space group P4mm. It is obtained that the BiFeO3 thin film shows a well-saturated remarkably giant saturation polarization of 158 mC/cm2 and a remanent polarization of 146 mC/cm2 for a maximum applied voltage of 20 volt at 90 K. These values of polarization are largest ever-measured in ferroelectrics.

Bismuth Layer Structured Ferroelectric Thin Films Mixed with BiFeO3

S. Ikemori, A. Shibuya, M. Noda and M. Okuyama

Bismuth layer structured ferroelectrics (BLSFs) have good fatigue characteristics. BiFeO3 (BFO), on the other hand, have revealed to have giant remanent polarization (Pr). This time, we tried to incorporate the BFO perovskite structure into some BLSFs as one component of pseudo-perovskite block in the BLSF. This is a trial to build-up a superlattice structure within a pseudo-perovskite stacking blocks of a BLSF. Also, another trial is to make a ferromagnetic BLSF using Fe magnetic atoms in the BFO perovskite. So, we made two targets which compose both from BLSF and BFO, where Bi4TiNbO9 and Bi4Ti3O12 are used as BLSF, respectively. Those are Bi4TiNbFeO12 (BTNF) and Bi5Ti3FeO15 (BTFO15), thereafter, made those thin films on Pt(111)/TiO2/SiO2/Si substrates by using a pulsed laser deposition (PLD). For both cases, X-ray diffractions show the formations of new kind of BLSFs that contain BFO as one of pseudo-perovskite layer. BTFO15 thin film shows good ferroelectricity reflected by the value of 2Pr, which is estimated to be 56 mC/cm2.

Study on Metal-Ferroelectric-Insulator-Semiconductor (MFIS) Structure Using SiO2 Buffer Film with Nitrided Surface
Masakazu HIRAKAWA, Minoru NODA and Masanori OKUYAMA Surface of SiO2 film with 7.5 nm thickness has been nitrided by plasma treatment, aiming to make the SiO2-based buffer layer in Metal-Ferroelectric-InsulatorSemiconductor (MFIS) structure as thin as possible and simultaneously to maintain good barrier properties between the ferroelectric thin film and buffer layer. XPS spectra of N peak shows the concentration of N atoms into SiO2 layer nitrided by plasma treatment is distributed within depth of 1-2 nm from the surface and decreases gradually from the surface. Leakage current density of MIS structure at 3V is below 9x10-10 A/cm2, showing a good barrier property as an insulator. C-V curve of MIS structure shows steep transition region, indicating excellent Si/SiO2 interface properties. Memory window in C-V characteristic of MFIS structure using Sol-Gel-made SrBi2Ta2O9 (SBT) film is 0.7 V. Finally, a very long retention time of 5x105 sec (i.e. about 6 days) is obtained. Leakage current density of MFIS structure at hold voltage of 1.2 V is as low as about 5x10-9 A/cm2.

Fabrication and Characterization of Ferroelectric Gate Field Effect Transistor Memory based on Ferroelectric-Insulator Interface Conduction
B. Y. Lee, S. Ikemori, M. Noda and M. Okuyama A new type of ferroelectric gate field effect transistor (FET) using ferroelectric-insulator interface conduction has been proposed. Drain current flows along the interface between the ferroelectric and insulator layers and needs no semiconductor although the conventional FET has conduction channel in semiconductor underneath the gate region. It is found that holes are produced at the interface corresponding to large polarization of the ferroelectric film. The memory retention time is considered to be larger than that in MFIS-FET because of little depolarization field in the ferroelectric film. The FET has

been fabricated by forming drain and source electrodes on the deposited ferroelectric film (PZT) on Pt substrate, before stacking insulation film, then forming the gate electrode. The Id-Vd characteristic looks like the conventional curves of usual p-channel FET and the drain current is controlled by gate voltage. The Id-Vg characteristics show counterclockwise hysteresis loop due to polarization hysteresis of the PZT film. The FET shows that (1) On/Off ratio of the drain current is in order of about 5, (2) the maximum drain current is as large as ~110-5A and subthreshold leakage current is ~310-11A at gate width of 500mm, (3) On/Off current ratio due to polarization reversal is in order of about 3, (4) the drain current increases proportionally to increase in gate width.

Preparation of (Pb,Ba)TiO3 thin films by sol-gel method followed by hydrothermal treatment using Ba(OH)2 at 200oC or less
Y. Sakioka , T. Naoyama, D. Ricinschi, M. Noda and M. Okuyama Recently low temperature preparation of ferroelectric thin films has been required for the development of highly integrated ferroelectric memory. It is reported that PZT thin films were prepared at low temperature so far by sol-gel method followed by hydrothermal treatment with KOH solution, and confirmed to have good electrical properties. However, the KOH is impossible to be applied to a conventional Si ULSI process since potassium ion in the KOH is well known as a notorious mobile-impurity ion and also the KOH etches off the Si substrate seriously. Therefore, in this work we have newly prepared (Pb,Ba)TiO3 (PBT) thin films by hydrothermal treatment using Ba(OH)2 alkaline solution other than KOH. The sol-gel solution of TiO2 obtained from Mitsubishi Material Corp. was spin-coated on Pt/Ti/SiO2/Si wafer at 500 rpm for 5 sec and then at 4000 rpm for 30 sec. The gel films were pre-baked in air at 200oC for 20 min. TiO2 gel films of about 200-300 nm were prepared by repeating this process by 3 times. And then TiO2 gel films were treated in alkaline solution in an autoclave. Hydrothermal treatment was carried out in an autoclave by submerging the TiO2 gel films in 35 ml Ba(OH)2 + Pb(OH)2 mixed solution. For the treatment, the autoclave was sealed and heated to the working temperature of 200oC and maintained for 3 hours. After the treatment, the PBT thin films were rinsed in boiling deionized water and then dried at 150oC in air. PBT thin films were successfully prepared at 200oC or less by sol-gel-hydrothermal treatment method using Ba(OH)2. The PBT thin film of the best property was prepared by hydrothermal treatment at 200oC in 0.3M Ba(OH)2+0.2M Pb(OH)2 solutions using a TiO2 gel film which had been baked at 200oC. According to XRF analysis, a ratio of Pb/Ba of this PBT thin film was about 1.10. The PBT thin film has good hysteresis loop of Pr = 21 mC/cm2 and good piezo-electric property. This process can be applied to Si ULSI back-end process because this process does not require high temperature and KOH solutions.

A low temperature preparation of BaTiO3 thin film by sol-gelhydrothermal treatment below 210oC
T. Naoyama, Y. Sakioka, K.Harada, M. Noda and M. Okuyama

In this work we have newly prepared BaTiO3 (BTO) thin films by hydrothermal treatment using Ba(OH)2 alkaline solution other than KOH, aiming also to apply for a low temperature ferroelectric capacitor fabrication of Si ULSI back-end process. The solgel solution of TiO2 was spin-coated on Pt/Ti/SiO2/Si wafer at 500 rpm for 5 sec and then at 4000 rpm for 30 sec. The gel films were pre-baked in air at 200oC for 20 min. TiO2 gel films of about 350 nm were prepared by repeating this process by 4 times. And then TiO2 gel films were treated in alkaline solution in an autoclave. Ba(OH)2 which dissolves easily was used as alkaline solution. Hydrothermal treatment was carried out in an autoclave by submerging the TiO2 gel films in 500 ml Ba(OH)2 solution. The temperature of the solution is 140-210oC, hold time is 0-3 h, and Ba(OH)2 concentration is 0.03-1.0M, respectively. For the treatment, the autoclave was sealed and heated. After the treatment, the BTO thin films were rinsed in boiling deionized water and then dried at 120oC in air for 10 min. The crystalline of the BTO thin film treated hydrothermally was improved greatly by lowering the pre-baking temperature of TiO2 gel film from 350oC to 200oC. The grain structure of the BTO thin film depends on the Ba(OH)2 concentration. The BTO thin film of the best property was prepared by hydrothermal treatment at 210oC for 3 h in 0.2M Ba(OH)2 solution using a TiO2 gel film which had been baked at 200oC for 20 min in air. According to ICP analysis, a ratio of Ti/Ba of the BTO thin film was about 1.2. The BTO thin film has hysteresis loop of Pr = 5 mC/cm2.

A Highly Sensitive Ba(Ti1-xSnx)O3 Thin Film Ferroelectric Bolometer For Uncooled Infrared Sensor
D. Popovici, S. Murakami, M. Matsumoto, M. Noda and M. Okuyama Polycrystalline Ba(Ti0.85Sn0.15)O3 (BTS15) thin films have been prepared on Pt/Ti/SiO2/Si wafers by Metal-Organic Decomposition (MOD) process. Spin-coating was performed in rich N2 atmosphere using different N2 gas flow rates from 0 to 5 l/min while keeping the other fabrication steps the same. The influence of N2 gas during the spin-coating was investigated. SEM images revealed that the N2 gas flow has no influence on the thickness of the films however further investigations using AFM and XRD revealed that nitrogen gas flow plays an important role in obtaining films with a good crystallinity and a good grain size/RMS roughness ratio. Also, XPS investigations revealed that, for the samples obtained while using 4 l/min N2 flow during spinning, the concentration of oxygen vacancies has the smallest value among the investigated samples. Investigations on the electrical properties of the BTS15 thin films revealed that N2 flow rate plays an important role in obtaining good electrical properties. Analysis of the hysteresis loops obtained for BST15 thin films showed that the polarization decreases with increasing in nitrogen flow from 0 to 3 l/min and increases when the nitrogen flow is increased up to 4 l/min then decreases again when the nitrogen flow is further increased. On the other hand, the leakage current density decreases for the BST15 samples that were obtained when the nitrogen flow was increased from 0 to 4 l/min and increases when the nitrogen flow is further increased. These behaviors can be explained considering the fact that the grain size and the roughness of the sample are affected by the different nitrogen flow rate as revealed by AFM and XRD investigations and that the O vacancy

concentration is also influenced by the N2 gas flow as revealed by XPS investigations. What is more important, Temperature Coefficient of Dielectric constant (TCD), which is a very important parameter for a dielectric bolometer, is also affected by the different nitrogen flow rate having very good values of more than 1 %/K for a wide temperature range when the N2 flow rate was 4l/min, making this film suitable for infrared sensing applications.

Fabrication of Dielectric Bolometer Mode IR Sensor Using Surface Bulk Micromachine Structure
M. Matsumoto, M. Uno, S. Murakami, D. Popovici, M. Noda and M. Okuyama We have developed new thermal isolation structure by surface bulk micromachining for dielectric bolometer (DB) mode infrared sensor in order to improve thermal isolation, infrared absorption and pixel density. In the structure, detector pixel is on bridgesupported membrane that consists of three layers of SiO2/Si3N4/SiO2, and is covered at the top with another SiO2. The structure of SiO2/Si3N4/SiO2 improves adhesion with lower electrode of Pt/Ti of ferroelectric (Ba,Sr)TiO3 or Ba(Ti,Sn)O3 infrared detector capacitor, compared with Si3N4/SiO2. Moreover, the structure overcoated by SiO2 at the top contributes to increase infrared absorption and improve DB sensor performance, and enables to increase pixel density as the anisotropic etching occurs at surface region of Si beneath the detector pixel. Since the DB pixel is buried in the membrane, it also becomes possible to use various materials as ferroelectric and infrared absorption films even the anisotropic etchant tolerance is insufficient. The new DB pixel has twice or more larger output voltage than the conventional one, even the capacitor area of the new DB is one forth of the previous. Thus, the new DB pixel structure is considered to be promising for higher-density infrared Uncooled Focal Plane Arrays (UFPAs).

Preparation of Ferroelectric Ba(Ti,Zr)O3 Thin Films by Pulsed Laser Deposition

S. Murakami, D. Popovici, M. Uno, K. Satoh, M. Noda and M. Okuyama Pulsed laser deposition method has been used to prepare Ba(Ti0.8,Zr0.2)O3 (BTZ20) thin films on Pt/Ti/SiO2/Si substrate. From the deposition temperature dependence of the XRD patterns of the BTZ20 films, it found that the film deposited at 500oC have a perovskite phase and a preferred orientation with (110) dominant. However, the dissipation factor of the as-deposited film was around 0.2, meaning that it is too high to use the film as sensing material of the infrared sensor of dielectric bolometer (DB) mode. Therefore, we have investigated the post-annealing effect in order to decrease the dissipation factor. When the deposited films were post-annealed for 30 min at temperature of 600 or 700oC in oxygen rich atmosphere, the dissipation factor of the films becomes less than 0.05, which is low enough to use in the infrared sensor of DB mode. From the temperature dependence of the dielectric constant, the temperature coefficient

of dielectric constant (TCD) of the 600oC-post-annealed BTZ20 film is determined to be -0.16 %/K at 25oC, and Tc is considered to be below 15oC. By optimizing Ti/Zr composition ratio of the BTZ film, Tc shall be close to the room temperature. This means the improvement of TCD, and makes it more promising for realizing the highly sensitive IR sensor of DB mode.

A Low-Loss (Ba0.6Sr0.4)TiO3 Thin Film for RF Tunable Device by Using Initial Nucleation Layer
D. Popovici, M. Noda, Y. Sasaki, M. Komaru, and M. Okuyama Barium Strontium Titanate (BST) thin films have been deposited on (100)-oriented MgO substrate by combining preparation of initial layer by Pulsed Laser Deposition and main layer by Metal-Organic-Decomposition method. Films with an initial layer of 20, 30 and 40 nm thickness and final thickness of 400, 650 and 800 nm have been obtained. Physical and dielectric properties of the BST thin films have been characterized from the viewpoint of frequency-agile micro and millimeter circuit applications. The results reveal that Ba0.6Sr0.4TiO3 thin films have a good crystallinity with characteristic orientation that is affected by the deposition conditions of the initial layer. Measured tunability and dielectric loss at 1 MHz with a maximum applied voltage of 40 V are obtained for the two kinds of interlayer. For interdigital (ID) capacitors with a finger spacing of 10 mm, formed on a 400 nm thick BST film, the tunability is increased in the films with the interlayer deposited at room temperature, while the dielectric loss keeps nearly the same and very low value less than 0.004. Increase in the thickness of the interlayer from 20 nm to 30 or 40 nm seems to have a negative effect on tunability. As the value of tunability is related mainly to the part of MOD-made BST layer because the PLD-made interlayer is thin, the reason for the behavior is considered to be attributed to the relaxation of strain in the MOD-made layer. The strain is caused by the lattice mismatch between MgO and BST interlayer film. It is already reported that the highest tunability is obtained for BST thin films in which the strain presents and has an optimum value. According to the result, films without optimum strain have smaller tunabilities. Because we observed a separation of the interlayer into small islands when the thickness is less than 20 nm, the optimum interlayer thickness was set to be 20 nm. Increase in the total BST film thickness induces an increment in tunability as expected, with the dielectric loss remaining at small values of 0.002-0.004. As for stacked capacitor case, the electric field inside the BST film with thickness less than 1 mm is larger than that in the ID capacitor with wider gap of 10 mm, therefore, it is expected to show a larger tunability and larger loss. We found that the tunability increases up to about 40 % in a Pt/BST/Pt stacked capacitor structure when the applied electric field was from -/+170 to +/-170 kV/cm and also that the loss increases up to 0.04 at the same frequency. At microwave frequencies, classic-shaped coplanar waveguide (CPW) lines formed on BST/(100)MgO were investigated. A differential phase shift of 18 degree was obtained at 20 GHz with insertion loss of about -2 dB at 60 V for Au/Cr interconnection. Finally, a 3stage LC-ladder-type phase shifter with the CPW structure has been fabricated

considering the experimental results obtained for the CPW lines and a maximum phase shift of 40 degrees is obtained at 20 GHz and 60 V.

A 20 GHz MOD-made BST Thin Film Tunable Phase Shifter for Phase Adjustment of Digital 360-degree PHEMT Phase Shifter
M. Noda, Y. Sasaki, D. Popovici, M. Okuyama, Makio Komaru We have newly designed and fabricated both BaxSr1-xTiO3 (BST) ferroelectric thin film tunable phase shifter and pseudomorphic HEMT MMIC digital 360-degree phase shifter. The HEMT MMIC also shows a digital 360-degree phase shift with 11.25 degree interval, thus the BST phase shifter can be usable for phase adjustment of the MMIC. Generally a phase shifter is used to adjust arbitrary pass phase, then it is necessary to control all the phase of 360 degree. For a realistic situation, it is required to compensate precise phase between two adjacent phases in digital phase shifter. In this work, for a real and useful application, we used the BST tunable phase shifter to compensate the phase in a pseudo-morphic HEMT MMIC digital 360-degree phase shifter. The phase shifter circuit is constructed as a switch type of low-pass and high-pass filters. The IC is composed of PHEMT, inductor, MIM capacitor and resistor on GaAs substrate. The circuit is correctly operated as a digital phase shifter. A phase error of 3.9 degrees rms and the maximum phase error of 7.9 dB are obtained for the phase shifter IC at 20 GHz. As the developed BST tunable phase shifter can shift phase up to 40 degree, it can be combined with the digital phase shifter and can perform a precise phase compensation. Finally it is found that the new BST film process is very promising for realizing a micro and millimeter-wave tunable device.

Sensitivity Improvement on Piezoelectric Ultrasonic Micro Sensors by Diaphragm Deflection Control

H. Nishimoto, K. Yamashita, and M. Okuyama Ultrasonic microsensors with piezoelectric thin films on silicon-micromachined thin diaphragm structure have been developed. The diaphragm tends to show static deflection due to the residual stress of each layer. The effect of the static deflection to sensitivity has been revealed as that the deflection which make the piezoelectric layer convex improves the sensitivity. Since the static defection is caused by buckling of the diaphragm which has compressive stress, one can control the buckling direction by applying a pressure onto a proper side of the diaphragm so that it deflects to the desired direction. In order to find the adequate condition of the pressure application, diaphragms in each stage of fabrication process have been used to buckle it by vacuum aspiration. In the cases of an SiO2/Si/SiO2 structure and a structure of lower electrode (Pt/Ti) on it, the diaphragms have broken before they buckle. In the case of a complete sensor structure, the diaphragms have re-buckled back after stopped aspiration. In the case of a structure during preparing sol-gel PZT layer, the diaphragms have buckled, and maintained the desired deflection through the total fabrication process. Forty-nine diaphragms have been applied the vacuum aspiration treatment and 88% of them have been deflected to the

desired direction, and improved in their sensitivity. The improved sensitivity is over 20 30 mV/Pa, which is high enough for measurement of 1 m distance.

Deflection Control by Residual Stress and Bending Moment on Micromachined Multilayer Diaphragms
K. Matano, H. Nishimoto, K. Yamashita and M. Okuyama Static deflection of diaphragms having silicon-micromachined multilayer structure can be controlled by residual stress of each layer and bending moment. Firstly, the residual stress of each layer have been investigated. Three structures of (1) SiO2/Si/SiO2, (2) Pt/Ti on (1) and (3) PZT on (2) are fabricated and measured their static deflection. Using the analytical method by I. Demier et al., the residual stress of the structures are calculated and it is found that Pt/Ti layer causes large compressive stress (equivalent stress of -303 MPa) and PZT layer causes tensile stress (equivalent stress of +137 MPa). Therefore, thick Pt/Ti layer make more deflection upward. Next, the bending moment of structures at the moment that the bulk support layer is etched out and the thin structure is released. In the case of conventional structure (1), bending moment tends to make the diaphragm deflect downward, while the structure (2) tends to make it upward. Thereby, fabrication process has been modified that Pt/Ti layer is prepared before the thin diaphragm structure is released. Finally, new diaphragm chip of forty-nine element array with the modified layer structure and/or the modified process is fabricated. A diaphragm array with the modified layer structure has been improved in its upward deflected elements of 35% compared with the conventional ones of 10%. Moreover, A diaphragm array with both the modified layer structure and the modified process has been improved up to 75%.

Accuracy Improvement of Real-Time and Three-Dimensional Position Measurement System Using Ultrasonic Micro Array Sensor
Y. Kaneko, K. Yamashita and M. Okuyama A real-time and portable three-dimensional position measurement system has been developed using silicon-micromachined ultrasonic array sensor and digital signal processing unit using an FPGA and A/D converter ICs instead of a conventional digital oscilloscope. The prototype system used an array sensor as two linear arrays for horizontal and vertical direction measurement. Object position was determined as its direction, horizontal angle (direction) and vertical angle (elevation) by using delay and summation method. The prototype system could not measure positions of plural objects because combinations of plural peaks of direction and elevation have ambiguity and the system can not assign each peak to each object. This ambiguity is resolved using two dimensional direction-elevation peak assignment. However, two-dimensional angular measurement using two linear arrays has lower position accuracy than one-dimensional angular measurement using one linear array. In order to realize precise position of plural object, the one-dimensional and two-dimensional angular measurements has been combined. Firstly, angular peaks are assigned using two-dimensional measurement, and

then the precise position of each peaks is adjusted using one-dimensional measurement. The measurement system has been improved using this method and successfully realized precise position measurement of plural objects.