On the optical properties of bismuth oxide thin films prepared by pulsed laser deposition

The optical properties of bismuth oxide films prepared by pulsed laser deposition (PLD), absorption in the photon energy range 2.50-4.30 eV and optical functions (n, k, epsilon(1), and epsilon(2)) in the domain 3.20-6.50 eV, have been investigated. As-prepared films (d = 0.05-1.50 mum) are characterized by a mixture of polycrystalline and amorphous phases. The fundamental absorption edge is described by direct optical band-to-band transitions with energies 2.90 and 3.83 eV The dispersion of the optical functions provided values of 4.40-6.25 eV for electron energies of respective direct transitions. In the spectral range 400-1000 nm, bismuth oxide films show a normal dispersion, which can be interpreted in the frame of a single oscillator model. (C) 2004 Elsevier B.V. All rights reserved.

Epitaxial Magnetic Oxide Nanocrystals Via Phase Decomposition of Bismuth Perovskite Precursors

The phase instability of bismuth perovskite (BiMO₃), where M is a ferromagnetic cation, is exploited to create self-assembled magnetic oxide nanocrystal arrays on oxide supports. Conditions during pulsed laser deposition are tuned so as to induce complete breakdown of the perovskite precursor into bismuth oxide (Bi₂ O₃ ) and metal oxide (M-O_x ) pockets. Subsequent cooling in vacuum volatizes the Bi₂ O₃ leaving behind an array of monodisperse nanocrystals. In situ reflective high energy electron diffraction beam is exploited to monitor the synthesis in real-time. Analysis of the patterns confi rms the phase separation and volatization process. Successful synthesis of M-O_x, where M = Mn, Fe, Co, and Cr, is shown using this template-free facile approach. Detailed magnetic characterization of nanocrystals is carried out to reveal the functionalities such as magnetic anisotropy as well as larger than bulk moments, as expected in these oxide nanostructures.

Development of the Oxide Ion Conductor Na0.5Bi0.5TiO3 (NBT) for Solid Oxide Cells

Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material with potential to replace lead zirconate titanate (PZT),1 however high leakage conductivity for the material has been widely reported.2 Through a combination of Impedance Spectroscopy (IS), O2- ion transference (EMF) number experiments and O18 tracer diffusion measurements, combined with Time-of-flight Secondary Ion Mass Spectrometry (TOFSIMS), it was identified that this leakage conductivity was due to oxygen ion conductivity. The volatilization of bismuth during synthesis, causing oxygen vacancies, is believed to be responsible for the leakage conductivity.3 The oxide-ion conductivity, when doped with magnesium, exceeds that of yttria-stabilized zirconia (YSZ) at ~500 °C,3 making it a potential electrolyte material for Intermediate Temperature Solid Oxide Cells (ITSOCs). Figure 1 shows the comparison of bulk oxide ion conductivity between 2 at.% Mg-doped NBT and other known oxide ion conductors.

As part of the UK wide £5.7m 4CU project, research has concentrated on trying to develop NBT for use in Intermediate Temperature Solid Oxide Cells (ITSOCS). With the aim of achieving mixed ionic and electronic conduction, transition metals were chemically doped on to the Ti-site. A range of experimental techniques was used to characterize the materials aimed at investigating both conductivity and material structure (Scanning Electron Microscopy (SEM), IS, X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS)). The potential for NBT as an ITSOC material, as well as the challenges of developing the material, will be discussed.

(1) Takenaka T. et al. Jpn. J. Appl. Phys 1999, 30, 2236.

(2) Hiruma Y. et al. J. Appl. Phys 2009, 105, 084112.

(3) Li. M. et al. Nature Materials 2013, 13, 31.