Studies on n=2 Aurivillius phases: structure of the series Bi3-xLaxTiNbO9 (0 <= x <= 1)

The crystal structures of the solid solutions of Bi3-xLaxTiNbO9 (0 less than or equal to x less than or equal to 1) have been analyzed by powder X-ray diffraction with supporting evidence from selected area electron diffraction (SAD). The structure of the starting member (x = 0) is verified to be in the orthorhombic space group A2(1) am while the end member (x = 1) is determined to crystallize in the centrosymmetric orthorhombic space group Pmcb. The structure of x = 1 phase is solved by ab initio powder diffraction. The intermediate compositions belong to the space group A2(1) am as confirmed by Rietveld refinements. Rietveld refinements on all the compositions reveal that the La3+ ion is disordered only in the A site and not in the [Bi2O2](2+) layer. The tilt in the Ti/NbO6 octahedra decreases with increasing x. (C) 2003 Elsevier B.V. All rights reserved.

Synthesis, characterization, thermo- and photoluminescence properties of Bi3+ co-doped Gd2O3:Eu3+ nanophosphors

Gd2O3:Eu3+ (4 mol%) co-doped with Bi3+ (Bi = 0, 1, 3, 5, 7, 9 and 11 mol%) ions were synthesized by a low-temperature solution combustion method. The powders were calcined at 800A degrees C and were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared and UV-Vis spectroscopy. The PXRD profiles confirm that the calcined products were in monoclinic with little cubic phases. The particle sizes were estimated using Scherrer's method and Williamson-Hall plots and are found to be in the ranges 40-60 nm and 30-80 nm, respectively. The results are in good agreement with TEM results. The photoluminescence spectra of the synthesized phosphors excited with 230 nm show emission peaks at similar to 590, 612 and 625 nm, which are due to the transitions D-5(0)-> F-7(0), D-5(0)-> F-7(2) and D-5(0)-> F-7(3) of Eu3+, respectively. It is observed that a significant quenching of Eu3+ emission was observed under 230 nm excitation when Bi3+ was co-doped. On the other hand, upon 350 nm excitation, the luminescent intensity of Eu3+ ions was enhanced by incorporation of Bi3+ (5 mol%) ions. The introduction of Bi3+ ions broadened the excitation band of Eu3+ of which a new strong band occurred ranging from 320 to 380 nm. This has been attributed to the 6s(2)-> 6s6p transition of Bi3+ ions, implying a very efficient energy transfer from Bi3+ ions to Eu3+ ions. The gamma radiation response of Gd2O3:Eu3+ exhibited a dosimetrically useful glow peak at 380A degrees C. Using thermoluminescence glow peaks, the trap parameters have been evaluated and discussed. The observed emission characteristics and energy transfer indicate that Gd2O3:Eu3+, Bi3+ phosphors have promising applications in solid-state lighting.

GdAlO3:Eu3+:Bi3+ nanophosphor: Synthesis and enhancement of red emission for WLEDs

GdAlO3, GdAlO3:Eu3+ and GdAlO3:Eu3+:Bi3+ nanophosphors were synthesised by solution combustion technique. Pure orthorhombic phase was obtained from powder X-ray diffraction (PXRD) studies. Scanning electron microscopy (SEM) micrographs showed the porous, agglomerated and irregular shaped particles. The particle size obtained by transmission electron microscopy (TEM) measurement was in good agreement with the values obtained by Debye Scherrer's and W-H plots. The selected area electron diffraction (SAED) pattern show single crystalline nature of the sample. Photoluminescence (PL) measurements were carried out for GdAlO3:Eu3+ and GdAlO3:Eu3+:Bi3+ phosphors excited at a wavelength of 274 nm. The characteristic emission peaks of Eu3+ ions were recorded at 590, 614, 655 and 695 nm corresponding to D-5(0) -> F-7(J) (J = 1, 2, 3, 4) transitions respectively. However, with addition of Bi3+ ions in GdAlO3:Eu3+, PL intensity drastically enhanced. Orange red color was tuned to deep red color with the addition of Bi3+ ions in GdAlO3:Eu3+ phosphor. Therefore, the phosphor was highly useful as red component in WLEDs. A single well resoled glow peak at 225 degrees C was recorded in GdAlO3 and GdAlO3:Eu3+. Further, with addition of Bi3+ ions, an additional peak at 300 degrees C was recorded. TL glow curves of different UV-exposed GdAlO3:Eu3+:Bi3+ show two TL peaks at 207 and 300 degrees C respectively. The 207 degrees C peak show simple glow peak structure and its intensity increases linearly up to 25 mm and after that it decrease. (C) 2014 Elsevier B.V. All rights reserved.

Role of Bi3+ ions for Er3+ ions efficient 1.54 mu m light emission in Er/Bi codoped SiO2 thin film prepared by sol-gel method

Er/Bi codoped SiO2 thin films were prepared by sol-gel method and spin-on technology with subsequent annealing process. The bismuth silicate crystal phase appeared at low annealing temperature while vanished as annealing temperature exceeded 1000 degrees C, characterized by X-ray diffraction, and Rutherford backscattering measurements well explained the structure change of the films, which was due to the decrease of bismuth concentration. Fine structures of the Er3+-related 1.54 mu m light emission (line width less than 7 nm) at room temperature was observed by photoluminescence (PL) measurement. The PL intensity at 1.54 gm reached maximum at 800 degrees C and decreased dramatically at 1000 degrees C. The PL dependent annealing temperature was studied and suggested a clear link with bismuth silicate phase. Excitation spectrum measurements further reveal the role of Bi3+ ions for Er3+ ions near infrared light emission. Through sol-gel method and thermal treatment, Bi3+ ions can provide a perfect environment for Er3+ ion light emission by forming Er-Bi-Si-O complex. Furthermore, energy transfer from Bi3+ ions to Er3+ ions is evidenced and found to be a more efficient way for Er3+ ions near infrared emission. This makes the Bi3+ ions doped material a promising application for future erbium-doped waveguide amplifier and infrared LED

V5+-doped Bi3.4Yb0.6Ti3O12 fatigue resistant ferroelectric thin films

In this paper, a serial of Bi3.4Yb0.6Ti3-xVxO12 (BYTV) thin film with different V5+ contents were deposited on Pt/Ti/SiO2/Si substrates by chemical solution deposition (CSD). The crystallized phase and electrical properties of the films were investigated using X-ray diffraction, polarization hysteresis loops, leakage current-voltage, and fatigue test. From our experimental results, it can be found that the ferroelectric properties can be improved greatly using V5+-doped in Bi3.4Yb0.6Ti3O12 (BYT) thin film, compared with the reported BYT thin film. The remanent polarization was enhanced and excellent leakage current characteristic with 10(-11)A at the bias voltage of 4V, which is much lower than the BYT thin film or some reported bismuth layer-structure ferroelectric films. Fatigue test shows that the fabricated films have good anti-fatigue characteristic after 10(10) switching cycles. (c) 2008 Published by Elsevier B.V.

Enhanced luminescence of gadolinium niobates by Bi3+ doping for field emission displays

Blue emitting GdNbO4: Bi3+ powder phosphors for field emission displays were prepared by a solid state reaction. Both photoluminescence and cathodoluminescence properties of the materials were investigated. GdNbO4 itself shows only a very weak luminescence in the blue spectral region. By doping Bi3+ in GdNbO4, the luminescence intensity was improved greatly. The emission spectrum of the GdNbO4: Bi3+ consists of a broad band with maximum at 445 nm (lifetime = 0.74 mu s; CIE chromaticity coordinates: x = 0.1519 and y = 0. 1196) for both UV and low voltage (1-7 kV) cathode ray excitation. In GdNbO4:Bi3+ phosphors, the energy transfer from NbO43- to activator Bi3+ occurred.

Leakage current behavior of Bi3.25La0.75Ti3O12 ferroelectric thin films deposited on different bottom electrodes

Bi3.25La0.75Ti3O12 (BLT) thin films were grown on LaNiO3 (LNO), RuO2 (RuO2) and La0.5Sr0.5CoO3 (LSCO) bottom electrodes by using the polymeric precursor method and microwave furnace. The bottom electrode is found to be an important parameter which affects the crystallization, morphology and leakage current behaviors. The XRD results clearly show that film deposited on LSCO electrode favours the growth of (117) oriented grains whereas in films deposited on LNO and RuO2 the growth of (001) oriented grains dominated. The film deposited on LSCO has a plate-like grain structure, and its leakage current behavior is in agreement with the prediction of the space-charge-limited conduction model. on the other hand, the films deposited on RuO2 and LNO electrodes present a rounded grain shape with some porosity, and its high field conduction is well explained by the Schottky and Poole-Frenkel emission models. The remanent polarization (P-r) and the drive voltage (V-c) were in the range of 11-23 mu C cm(-2) and 0.86-1.56 V, respectively, and are better than the values found in the literature. (c) 2007 Published by Elsevier B.V.

Influence of the solution pH on the morphological, structural and electrical properties of Bi3.50La0.50Ti3O12 thin films obtained by the polymeric precursor method

Lanthanum-doped Bi4Ti3O12 thin films (BLT) were deposited on Pt/Ti/SiO2/Si substrates using a polymeric precursor solution. The spin-coated films were specular, crack-free and crystalline after annealing at 700 degrees C for 2 h. Crystallinity and morphological evaluation were examined by X ray diffraction (YRD) and atomic force microscopy (AFM). The stability of the formed complex is of extreme importance for the formation of the perovskite phase. Films obtained from acid pH solution present elongated grains around 200 ran in size, whereas films obtained from basic solution present a dense microstructure with spherical grains (100 nm). The dielectric and ferroelectric properties of the BLT films are strongly affected by the solution pH. The hysteresis loops are fully saturated with a remnant polarization and coercive voltage of P-r=20.2 mu C/cm(2) and V-c = 1.35 V and P-r= 15 mu C/cm(2) and V-c = 1.69 V for the films obtained from basic and acid solutions, respectively. (C) 2005 Elsevier B.V. All rights reserved.

Oriented growth of Bi3.25La0.75Ti3O12 thin films on RuO2/SiO2/Si substrates by using the polymeric precursor method: Structural, microstructural and electrical properties

c-axis oriented Bi3.25La0.75Ti3O12 (BLT) thin films were grown on a RuO2 top electrode deposited on a (100) SiO2/Si substrate by the polymeric precursor method. X-ray diffraction and atomic force microscope investigations indicate that the films exhibit a dense, well crystallized microstructure having random orientations with a rather smooth surface morphology. The electrical properties of preferred oriented Bi3.25La0.75Ti3O12 (BLT) thin films deposited on RuO2 bottom electrode leaded to a large remnant polarization (P-r ) of 17.2 mu C/cm(2) and (V-c ) of 1.8 V, fatigue free characteristics up to 10(10) switching cycles and a current density of 2.2 mu A/cm(2) at 5 V. We found that the polarization loss is insignificant with nine write/read voltages at a waiting time of 10,000 s. Independently of the applied electric field the retained switchable polarization approached a nearly steady-state value after a retention time of 10 s.

Retention characteristics in Bi3.25La0.75Ti3O12 thin films prepared by the polymeric precursor method

Ferroelectric Bi3.25La0.75Ti3O12 (BLT) thin films were deposited on Pt/Ti/SiO2/Si substrates by the polymeric precursor method. The films present c-axis preferred orientation after annealing at 700 degrees C for 2 h in conventional furnace. All the capacitors showed good polarization fatigue characteristics at least up to 1x10(10) bipolar pulse cycles and excellent retention properties up to 1x10(4) s. We found that the polarization loss is insignificant with five write/read voltages at a waiting time of 10 000 S. Independently of the applied electric field the retained switchable polarization approached a nearly steady-state value after a retention time of 10 s. (C) 2005 American Institute of Physics.

Fatigue-free behavior of Bi3.25La0.75Ti3O12 thin films grown on several bottom eletrodes by the polymeric precursor method

Fatigue-free Bi3.25La0.75Ti3O12 (BLT) thin films were grown on LaNiO3,RuO2, and La0.5Sr0.5CoO3 bottom electrodes in a microwave furnace at 700 degreesC for 10 min. The remanent polarization (P-r) and the drive voltage (V-c) were in the range of 11-23 muC/cm(2) and 0.86-1.56 V, respectively, and are better than the values found in the literature. The BLT capacitors did not show any significant fatigue up to 10(10) read/write switching cycles. (C) 2004 American Institute of Physics.

Ferroelectric properties and leakage current characteristics of Bi3.25La0.75Ti3O12 thin films prepared by the polymeric precursor method

The ferroelectric properties and leakage current mechanisms of preferred oriented Bi3.25La0.75Ti3O12 (BLT) thin films deposited on La0.5Sr0.5CoO3 by the polymeric precursor method were investigated. These films showed excellent ferroelectric properties in terms of large remnant polarization (2P(r)) of 47.6 mu C/cm(2) and (2E(c)) of 55 kV/cm, fatigue-free characteristics up to 10(10) switching cycles, and a current density of 0.7 mu A/cm(2) at 10 kV/cm. X-ray diffraction and scanning electron microscope investigations indicate that the deposited films exhibit a dense, well-crystallized microstructure having random orientations and with a rather smooth surface morphology. The improved ferroelectric and leakage current characteristics can be ascribed to the platelike grains of the BLT films, which make the domain walls easier to be switched under external field.

Fatigue and retention properties of Bi3.25La0.75Ti3O12 films using LaNiO3 bottom electrodes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ferroelectric and dielectric characteristics of Bi3.25La0.75Ti3O12 thin films prepared by the polymeric precursor method

The ferroelectric properties and leakage current mechanisms of preferred oriented Bi3.25La0.75 Ti3O12 (BLT) thin films deposited on La0.5Sr0.5CoO3 (LSCO) by the polymeric precursor method were investigated. Atomic force microscopy indicates that the deposited films exhibit a dense microstructure with a rather smooth surface morphology. The improved ferroelectric and leakage current characteristics can be ascribed to the plate-like grains of the BLT films. © 2006 Trans Tech Publications, Switzerland.

Phase conversions in calcium manganites with changing Ca/Mn ratios and their influence on the electrical transport properties

The phase-interconversions between the spinel-, brownmillerite-, defect rocksalt and perovskite-type structures have been investigated by way of (i) introducing deficiency in A-sites in CaxMn2-xO3 (0.05 <= x <= 1) i.e., by varying Ca/Mn ratio from 0.025 to 1 and (ii) nonstoichiometric CaMnO3-delta (CMO) with 0.02 <= delta <= 1. The temperature dependence of resistivity (rho-T) have been investigated on nonstoichiometric CaMnO3-delta (undoped) as well as the CMO substituted with donor impurities such as La3+, Y3+, Bi3+ or acceptor such as Na1+ ion at the Ca-site. The rho-T characteristics of nonstoichiometric CaMnO3-delta is strongly influenced by oxygen deficiency, which controls the concentration of Mn3+ ions and, in turn, affects the resistivity, rho. The results indicated that the substitution of aliovalent impurities at Ca-site in CaMnO3 has similar effects as of CaMnO3-delta ( undoped) annealed in atmospheres of varying partial pressures whereby electron or hole concentration can be altered, yet the doped samples can be processed in air or atmospheres of higher P-O2. The charge transport mechanisms of nonstoichiometric CaMnO3-delta as against the donor or acceptor doped CaMnO3 (sintered in air, P-O2 similar to 0.2 atm) have been predicted. The rho (T) curves of both donor doped CaMnO3 as well as non-stoichiometric CaMnO3-delta, is predictable by the small polaron hopping (SPH) model, which changes to the variable range hopping (VRH) at low temperatures whereas the acceptor doped CaMnO3 exhibited an activated semiconducting hopping ( ASH) throughout the measured range of temperature (10-500 K).