The microstructure of Y5V-1206 capacitor has been studied using X-ray diffractometry (XRD), scanning electron microscope (SEM), and transmission electron microscope (TEM). Twinning occurs when a crystal undergoes a shear stress which produces a crystal structure which is a mirror image of itself. In BaTiO3, twinning occurs in (111) plane and the orientation relationships of it between two grains have been analyzed. We can define it for transformation matrices. We supply high-voltage, low-current pulses to capacitor for breakdown of it. We confer on reason for breakdown. We suspect the discrepancy is due to the change in the field distribution above and below Curie Temperature in core-shell structure. It differentiates dielectric constant (

Des céramiques piézoélectriques sans-plomb de composition (CazBa1-z)(Ti1-x-wCoxNbw)O3- ont étésynthétisées e Li2O ou de Li2CO3des matériaux denses à une température de 1100 °C au lieu des 1300 °C usuellement requis pour fritter leBaTiO3.fonctionnelles : le coefficient piézoélectrique d33 et le coefficient de couplage kp atteignent respectivement255 pC/N et 43,5%. De plus, un recuit sous O2 des échantillons dopés au cobalt mène à un d33 = 265 pC/Net à un kp = 42,8%.En fonction de la nature des dopants, un caractère « doux » ou « dur » a été observé dans les céramiquespiézoélectriques. Le dopage par les ions Co/Li mène à un comportement « dur » et provoque desphénomènes de vieillissement. On observe ainsi pour un BT:Co,Li vieilli, un cycle P = f(E) àdouble boucle ou déformé pour des échantillons respectivement non-polarisés ou polarisés. Les cyclescours du temps. Ce champ inCes phénomènes particuliers sont dus à la formation de dipôle de défaut (MTi VO )x causée parin, les grandes valeurs ducoefficient de qualité mécanique (Qmsynthétisées vis-à-vis de fortes contraintes, mécanique ou électrique. Cela rend ces matériaux compétitifscomparés au PZT 4 pour des applications de type transduction acoustique. / (CazBa1-z)(Ti1-x-wCoxNbw)O3- lead-free piezoelectric ceramics were prepared using solid-state reaction. Theuse of a Li2O or Li2CO3 sintering aid enables one to obtain dense ceramics at a temperature of 1100 °Cinstead of the 1300°C used for BaTiO3 in conventional sintering. Insertion of Li/Ca/Co/Nb in the perovskitestructure improves functional properties: for micrograin-size ceramics, a piezoelectric charge constant andelectromechanical coupling factor of d33 = 255 pC/N and kp = 43,5% were reached, respectively.Furthermore, a thermal annealing of the cobalt doped sample under O2 atmosphere led to d33 = 265 pC/Nand kp = 42,8%.Soft/hard characteristics of the piezoelectric ceramics are observed depending on the dopant ions. The Co/Liacceptor dopants lead to hard piezoelectric ceramics and aging phenomena. The aged BT:Co,Li exhibitsdouble loops and a distorted hysteresis cycle for non-poled and poled ceramics, respectively. Distortedhysteresis loops for BT:Co,Li show an increased internal bias field with aging time. Insertion of donordopants such as niobium ions significantly reduces the internal field. These behaviors are related to thepresence of defect dipoles (MTi VO )x due to the insertion of acceptor dopants in the B sites following theoxygen vacancies to equilibrate charge compensation. The high mechanical quality factors (Qm > 1000)obtained for the doped BaTiO3 ceramics affords stability against mechanical stress and electrical stress of upto 400 VRMS/mm, which makes these materials competitive with PZT4 for acoustic transducer applications.

Various sizes of BaTiO3 and Cr3+-doped BaTiO3 nanocrystals were synthesized through hydrothermal and solvothermal methods. The applied solvents water, ethanol and benzyl alcohol lead to nanoparticles with average sizes of 200, 10 and 5 nm, respectively. The nanocrystals were treated with trioctylphosphine oxide to remove surface-bound dopant ions, and colloidal free-standing nanocrystals smaller than 10 nm were obtained by using oleic acid as a dispersant surfactant. The tetragonal-to-cubic phase transition at room temperature of undoped nanocrystalline BaTiO3 has been investigated by powder X-ray diffraction (XRD) and Raman spectroscopy. The size effect of nanoscale BaTiO3 is observed that the tetragonal phase becomes unstable with decreasing particle size. However, we found that ferroelectric tetragonal structure persists to some extent even for particles at 5 nm. The successful substitution of Ti4+ with Cr3+ in the host BaTiO3 lattice for all three sizes was achieved at different Cr3+/Ti4+ molar ratios. The dopant is found to significantly promote the phase transition, even dominate over the size effect. Ligand-field electronic absorption spectroscopy suggests a subtle change of the octahedral coordinated Cr3+ environments between particles at 5 and 10 nm, confirming the structural differences. Preliminary magnetic measurement indicates Cr3+ as isolated paramagnetic ions without any chromium clusters or oxides. The ability to rationally manipulate the ferroelectric properties of BaTiO3 by size and dopants, in combination with possible ferromagnetism induced by incorporating paramagnetic transition metal ions, opens up new opportunities for modern multiferroic materials in information storage technology.

Various sizes of BaTiO3 and Cr3+-doped BaTiO3 nanocrystals were synthesized through hydrothermal and solvothermal methods. The applied solvents water, ethanol and benzyl alcohol lead to nanoparticles with average sizes of 200, 10 and 5 nm, respectively. The nanocrystals were treated with trioctylphosphine oxide to remove surface-bound dopant ions, and colloidal free-standing nanocrystals smaller than 10 nm were obtained by using oleic acid as a dispersant surfactant. The tetragonal-to-cubic phase transition at room temperature of undoped nanocrystalline BaTiO3 has been investigated by powder X-ray diffraction (XRD) and Raman spectroscopy. The size effect of nanoscale BaTiO3 is observed that the tetragonal phase becomes unstable with decreasing particle size. However, we found that ferroelectric tetragonal structure persists to some extent even for particles at 5 nm. The successful substitution of Ti4+ with Cr3+ in the host BaTiO3 lattice for all three sizes was achieved at different Cr3+/Ti4+ molar ratios. The dopant is found to significantly promote the phase transition, even dominate over the size effect. Ligand-field electronic absorption spectroscopy suggests a subtle change of the octahedral coordinated Cr3+ environments between particles at 5 and 10 nm, confirming the structural differences. Preliminary magnetic measurement indicates Cr3+ as isolated paramagnetic ions without any chromium clusters or oxides. The ability to rationally manipulate the ferroelectric properties of BaTiO3 by size and dopants, in combination with possible ferromagnetism induced by incorporating paramagnetic transition metal ions, opens up new opportunities for modern multiferroic materials in information storage technology.

Hot-pressed BaTiO3 ceramics are prepared from commercial nano-size powder supplied by Cabot. Samples have been thoroughly analysed for the crystalline phases, microstructure, including stacking faults and dislocations, by X-ray diffractometry, scanning electron microscopy, and transmission electron microscopy. This research consists of three major endeavours: (a) the analysis of stacking faults, (b) the hexagonal

The BaTiO3 sample was made by dry pressure, it was artificial spread nickel paste on BaTiO3, and it was simulated multilayer ceramic capacitors (MLCC¡¦s) to make a sandwich structure with BaTiO3-Ni-BaTiO3 by sintered in YAGEO¡¦s laboratories. The samples have been thoroughly analysis for the interface between BaTiO3 dielectric and Ni electrode or NiO oxide, by X-ray diffractometry, scanning electron microscopy, and transmission electron microscopy. The interface between BaTiO3 and Ni has not orientation relationship as determined by selected area diffraction and it¡¦s not had dislocations in interface by two- beam image. The NiO oxide as determined by XRD and TEM, because of the thermodynamic potential of the Ni/NiO equilibrium was produced. The array of dislocations of Burgers vector is 1/2[ 10] in the interface, and Burgers vectors are 1/2[00 ], [ 1 ] as determined by high resolution images and Fast Fourier Transform simulation. Misfit dislocations along the interface occur to accommodate the lattice mismatch.

Recently, there has been increasing demands for high dielectric materials to replace SiO2 for high-density dynamic random access memories with ultralarge scale integration. TiO2 and BaTiO3 are very promising insulators for applications to DRAMs, as they exhibit higher dielectric constant.The growths of TiO2 and BaTiO3 thin films on (100) silicon are studied by MOCVD using Ti(i-OC3H7)4, Ba(DPM)2(tetraene)2 and N2O as precursors. The growth was performed in a cold wall horizontal system in the temperature range of 350~700¢J. The growth rates of TiO2 and BaTiO3 films are affected by the Ti flow rate, growth temperature and reactor pressure. The structures of TiO2 and BaTiO3 films are polycrystalline by X-ray diffraction examinations. The dielectric constant of as-grown TiO2 can reach 85 and BaTiO3 can reach 300 derived by C-V curves with the contact area 3.14¡Ñ10-4 cm2. In addition, the influences of postannealing treatment under an O2 and N2 ambient with different annealing temperature and time on the structural and electrical properties of as-grown TiO2 films will be also studied. However, TiO2 and BaTiO3 films have columnar structures acted the paths of leakage current. We use thermal annealing to reduce the leakage current. In the future, to enhance the dielectric constant and reduce the leakage current of the films is the goal in our study.

In recent years, there has been increasing demands for high dielectric materials to replace SiO2 for high-density dynamic random access memories with ultra large scale integration (ULSI). As the dimensions of the charge storage node decrease in high-density dynamic random access memories (DRAMs), TiO2 and BaTiO3 are very promising candidates for applications with exhibiting higher dielectric constant, high refractive index and high chemical stability. The growth of TiO2 and BaTiO3 thin films on various substrates i.e. (100) silicon¡B(100) GaAs¡B(100) InP and (100) MgO are studied by MOCVD using Ti(i-OC3H7)4, Ba(DPM)2, N2O and O2 as precursors. The growth was performed in a cold wall horizontal system in the temperature range of 280~750¢J. The growth rates and structure of TiO2 and BaTiO3 films are affected by the substrate temperature and reactor pressure, etc. The phase transition properties of TiO2 were studied via X-ray diffraction measurements. X-ray diffraction examination shows that phase transition of TiO2 films are at the same temperature of 450 oC on different substrates. Phase-pure rutile is obtained down to 450¢J on InP (100) and GaAs (100), while phase-pure anatase is obtained up to 450¢Jon MgO (100). The optical and electrical properties are associated with the film structures. TiO2 single phase films with rutile (110) orientation were successfully grown on InP (100) at 500¢J. In-plane epitaxial relationship of anatase TiO2 (100) // MgO (100) is present between 300¢J and 375¢J. In addition, the influences of substrate temperature and oxidizer on the structural and electrical properties of BaTiO3 films will be also studied. However, TiO2 and BaTiO3 films have columnar structures acted the paths of leakage current resulting low dielectric constant. We use thermal annealing to improve the quality of TiO2 with respect to leakage current density and dielectric constant. Dielectric constants of annealed TiO2 films were as high as 110.08. Leakage current density reduced to 5 ¡Ñ 10-5 A/cm2. In the future, to improve the crystal structure of the films is the goal in our study.

Commericially available BaTiO3 powder was die-pressed to discs, and sintered by a two-stage firing consisting of reducing in low oxygen partial pressures (pO2) and re-oxidizing in a higher pO2 to simulate the industrial process of manufacturing the multi-layer ceramic capacitors(MLCC). Both undoped and MgO-doped discs as well as commercial MLCC chips, provided by Ferro Electronic Material Systems, have been investigated for sintered microstructures using the scanning electron microscopy (SEM) and transmission electron microscopy (TEM), crystalline phases using the X-ray diffractometry (XRD), and dielectric properties using the frequency response analysis. A comparison between the microstructures is made in order to look for the microstructure origin of the macroscopic behaviour, e.g. dielectric properties.It is found that the crystalline phases have changed frompredominantly tetragonal to pseudo-cubic with MgO > 0.5 mol.%. Apart from grain growth being effectively suppressed in MgO-doped compositions, grains containing the characteristic ferroelectric domains in undoped samples have decreased significantly in number. The indication is that Mg2+ dissolving into the BaTiO3 lattice, substituting for the Ti4+ site reduces the c/a ratio. However, unlike what was reported before, no direct experimental evidence is found to support that grain growth inhibition is effected by Mg2+ segregation to grain boundaries.Dislocation loops are observed ubiquitously in all samples, although bothMgO doping and low pO2 have decisive effect on their density in sintered grains. In MLCC chips, the microstructure is characterised by core-shell grains representing the dissolution of solutes, and modulated grains representing the ordering of chemical defects, e.g. substitutional defects and oxygen vacancies forming defect clusters.Residual pores located intragranularly in the MLCC chips are also observed, and its origin discussed. The formation of such pores is attributed to vacancy condensation which is enhanced by the increased oxygen vacancies due to MgO doping, as an acceptor, and by low pO2 firing.

ABSTRACT In recent years, there has been increasing demands for high dielectric materials to replace SiO2 for high-density dynamic random access memories with ultra large scale integration (ULSI). As the dimensions of the charge storage node decrease in high-density dynamic random access memories (DRAMs), TiO2 and BaTiO3 are very promising candidates for applications with exhibiting higher dielectric constant, high refractive index and high chemical stability. The physical and chemical properties of LPD thin film by means of several measuring instruments, including Fourier Transform Infrared Spectrometer (FTIR), Auger Electron Spectroscopy (AES), Secondary Ion Spectrometer (SIMS), and X-Ray Diffractometer (XRD). As for the category in the electrical properties, such as C-V curve and I-V curve, of LPD-BTO thin film is comprehended in the most important part of this chapter. Further, we try to improve these electrical properties of LPD-TiO2 and LPD-BTO thin film by post-annealing in oxygen atmosphere at several high temperatures. From leakage current density-electric field intensity voltage (J-E) and capacitance-voltage (C-V) measurements, the leakage current densities are about (LPD-TiO2: 1 ¡Ñ 10-5 A/cm2 and LPD-BTO: 5 ¡Ñ 10-9 A/cm2). And the individual dielectric constants of both films (TiO2 and BTO) are calculated about 40 and 60. This value is larger than thermal oxide, PECVD oxide, and LPD-SiO2. We also can obtain the flat band voltage shifts of LPD-TiO2 and LPD-BTO films which are about ¡V0.5V and 0V; the effective oxide charges which are calculated about ¡V4.52¡Ñ1011 cm-2 and ¡V2.27¡Ñ1012 cm-2 The future goals: (1) Raising the atomic concentration of oxygen within both films and of barium within LPD-BTO film. (2) Shortening the process in preparation of both deposition solutions. (3) Re-checking both models.