Linear and nonlinear optical properties of KNbO3

Linear and nonlinear optical (NLO) properties of KNbO3 in various phases are calculated from their crystal structures. Nonlinear optical tensor coefficients are found to be very sensitive to the atomic geometry, changing as much as 85% between the ferroelectric tetragonal and rhombohedral phases. The predicted principal refractive indices are also found to be sensitive to their structural changes. In the tetragonal phase KNbO3 has the largest NLO responses, in the orthorhombic phase KNbO3 has the relative larger NLO coefficients, and in the rhombohedral structure KNbO3 has the large and homogeneous NLO properties. (C) 1998 Elsevier Science B.V. All rights reserved.

Comparison of non-linear optical susceptibilities of KNbO3 and LiNbO3

From the chemical bond viewpoint, second-order non-linear optical (NLO) tenser coefficients of KNbO3 and LiNbO3 crystals have been calculated. By using the bond-valence theory of complex crystals and the modified bond-charge model, we were able to determine contributions of each type of constituent chemical bond to the total second-order NLO susceptibility. The tenser values thus calculated are in good agreement with experimental data. From the comparison of NLO tenser coefficients of these two crystals, we found that the major NLO contributors are KO12 groups and LiO6 octahedra not the distorted NbO6 octahedra. The difference between their NLO properties arises from their different structural characters, and the high coordination number of constituent elements in KNbO3 makes its valence electrons become more delocalised compared with those of LiNbO3. (C) 1997 Elsevier Science Ltd. All rights reserved.

Synthesis of KNbO3 nanostructures by a microwave assisted hydrothermal method

One-dimensional nanostructures of KNbO3 have attracted a great interest in the scientific community, mainly because of their promising application as nanoelectromechanical systems (NEMS). However, the synthesis of KNbO3 structures becomes complex due to the natural tendency to form non-stoichiometric potassium niobates. In this context, we report on the crystallization of one-dimensional KNbO3 nanostructures through the reaction between Nb2O5 and KOH under microwave-assisted hydrothermal synthesis (M-H). The use of this synthesis method made possible a very fast synthesis of singlecrystalline powders. Based on SEM, TEM and XRD characterizations, the influence of the synthesis time and the reactants concentration in the structure and morphology of the resultant KNbO3 was established. The conditions that favor the crystallization of nanofingers were determined to be small amounts of Nb2O5 and short reaction times. (C) 2008 Elsevier B.V. All rights reserved.

Influence of the LiNbO3 and KNbO3 seeds on the sintering and electrical properties of PMN ceramic

The effect of LiNbO3 and KNbO3 seeds on the microstructure and dielectric characteristics of PMN ceramic prepared by columbite route have been investigated with the addition of 0, 1, and 2-wt% of seeds. X-ray diffraction, Scanning Electron Microscopy and an impedance analyzer were used to characterize the influence of seeds on physical characteristics and dielectric properties of PMN. LiNbO3 -seeded PMN samples present a significant increase in the amount of perovskite phase. The addition of LiNbO3 seeds in sintered PMN ceramics at 1100degreesC during 4 h causes a decrease in the porosity and the amount of pyrochlore phase. Weight losses during sintering of PMN ceramics are suppressed more significantly for LiNbO3 -seeded PMN. T-m of PMN ceramics changes with seeds concentration. KNbO3 seeds displace T-m to lower temperature whereas LiNbO3 causes its elevation. Dielectric constants of approximately 13,000 at 1 kHz was measured at -5degreesC in PMN ceramics with 1-wt% of LiNbO3 seeds.

Estudio de PMN cerámico dopado con KNbO3 y LiNbO 3 sintetizado por Pechini

PMN belongs to a special class of materials named relaxor ferroelectrics. It has high volumetric efficiency due to its high dielectric constant, which makes it in a perfect material for application in multilayer capacitors. When prepared the columbite route its preparation has many advantages. In this work, the preparations of columbite and PMN were done by Pechini and Partial Oxalate methods, respectively. The effects of the KNbO3 and LiNbO3 dopants added in various concentrations. The idea is founded on the correlations that they have with BaTiO3 y PbTiO3, respectively. The whole process was supervised by TG/DTA, XRD, SEM and determination of the specific surface area of the powders. LiNbO3 carries out the pre-sinterization of the particles, observed by a reduction in the surface area. There are not particle grow, but occur its lengthening. However, for KNbO3 these particle growth, but the agglomerates are softer. The effect produced by the doping during the synthesis of the PMN powder is different from the one produced in the columbite precursor. Pure precursor shows an average particle size of 0,2μm, but the addition of 5,0mol% of dopants carries out the formation of agglomerates close to 4μm. LiNbO 3 addition carries out spherical particles and pre-sinterization, while KNbO3 addition does not change the particles shape.

AM(1-x)Al(x)O(3-x) (A=Na or K; M=Nb or Ta): New anion-deficient Perovskite oxides exhibiting oxide ion conduction

Anion-deficient perovskite oxides of the formula AM(1-x)Al(x)O(3-x) (A = Na or K; M = Nb or Ta) have been prepared for 0 < x less than or equal to 0.5. Diffraction experiments reveal that while the potassium compounds adopt orthorhombic/cubic perovskite structures similar to the parent KNbO3/KTaO3, the sodium compound, NaNb0.5Al0.5O2.5, possesses a brownmillerite/LaSr-CuAlO5-like superstructure. Al-27 NMR spectra show an exclusive tetrahedral oxygen coordination for AI(III) in Na-Nb0.5Al0.5O2.5 (I) and both tetrahedral and octahedral coordination for Al(III) in KNb0.5Al0.5O2.5 (II). The results suggest a long-range and short-range ordering of oxide ion vacancies in I and II respectively. Electrical conductivity measurements show a significant oxide ion conduction for KNb1-xAlxO3-x, with the conductivity increasing with x up to x = 0.5. The differences in the Arrhenius plots of the ionic conductivity of I and II have been rationalized in terms of the long-range and short-range ordering of oxide ion vacancies in the anion-deficient perovskite oxides.

Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

Potassium niobate thin films prepared through polymeric precursor method

Thin films of potassium niobate were deposited on (100) Si substrates by the polymeric precursor method (Pechini method). Annealing in static air was performed at 600degrees C for 20 h. The obtained films were characterized by X-ray diffraction and atomic force microscopy (AFM). Electrical characterization of the films pointed to ferroelectricity via hysteresis loop. The dielectric constant, dissipation factor and resistance were measured in frequency region from 10 Hz to 10 MHz. At 1 MHz, the dielectric constant was 158 and the dissipation factor was 0.11. (C) 2004 Elsevier B.V. All rights reserved.

Study on the orientation degree of Pb1-xLaxTiO3 thin films by the rocking curve technique and its morphological aspects

Thin films of perovskite-type materials such as PbTiO3, BaTiO3, (Pb,La)TiO3, (Pb, La)(ZrTi)O-3, KNbO3, and Pb(Mg,Nb)03 have been attracting great interest for applications like non-volatile memories, ultrasonic sensors and optical devices. Thin film should be epitaxially grown or at least highly textured since the properties of this anisotropic material depend on the crystallographic orientation. For optical devices, in particular, an epitaxial thin film without defects are essential to reduce optical propagation losses. Pb1-xLaxTiO3 (PLT) where x=0, 13 and 27% thin films were prepared by a chemical method (polymeric precursors method), and deposited by the spin coating technique onto substrates of SrTiO3 (STO) and LaAlO3 (LAO). The films were then beat treated at 500 degrees C in a controlled atmosphere of 0,. The orientation degree of the thin films was obtained from rocking curve technique, by means of X-ray difftaction analysis. A microstructural study revealed that the films were crack-free, homogeneous and have low roughness. (c) 2006 Elsevier B.V. All rights reserved.

Síntese de templates para aplicação em piezocerâmicas livre de chumbo

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photochemical dynamics of laser-irradiated semiconductor nanostructures

Thesis (Ph.D.)--University of Washington, 2016-08

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.