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- Avendaño Soto, Esteban Damián, 1975-
(författare)
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Electrochromism in Nickel-based Oxides : Coloration Mechanisms and Optimization of Sputter-deposited Thin Films
- 2004
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Electrochromic properties of sputter-deposited nickel-based oxide films have been studied with a two-fold goal. From a practical point of view, the optical switching performance has been improved by optimizing the deposition conditions and film stoichiometry with respect to oxygen and hydrogen, and further by adding Mg, Al, Si, Zr, Nb or Ta to the films. From a theoretical point of view, details of the coloration mechanism have been studied by means of electrochemical intercalation (CV, GITT), optical measurements (UV, VIS, NIR and MIR), RBS, XRD, XPS and EXAFS. Optimization of deposition conditions has been illustrated by the example of films made by sputtering of a non-magnetic Ni(93)V(7) % wt. target in an atmosphere of Ar/O2/H2. The optimized films exhibit transmittance modulation between 20% and 75 % at 18 mC/cm2 charge intercalation. The remaining problem with nickel oxide and nickel vanadium oxide films is their residual yellow-brown color tint in the bleached state, which disappears as the short-wavelength transmittance increases upon addition of Mg, Al, Zr or Ta. Optimization of deposition conditions by co-sputtering from two targets and the film composition for mixed oxide films has been illustrated by the example of nickel aluminium oxide. The mechanisms of coloration upon electrochemical charge insertion and ozone exposure have been investigated. In the beginning of the electrochemical cycling, first, a reconstruction and crystallization is observed with the outer most part of the grain surface being transformed from oxygen rich nickel oxide into nickel oxy-hydroxide and hydroxide by transfer of H+ and OH- groups. After the charge capacity has been stabilized, only a transfer of H+ occurs with two reversible reactions involved: the first one from Ni(OH)2 to NiOOH and the second one from NiO and Ni(OH)2 to Ni2O3. Ozone coloration is described by a similar reaction scheme. The ozone molecule is split on the surface and dehydrogenates Ni(OH)2 into NiOOH. Further dehydrogenation produces Ni2O3 as in the electrochemical coloration.
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- Backholm, Jonas, 1977-
(författare)
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Electrochromic Properties of Iridium Oxide Based Thin Films
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Electrochromic iridium oxide (IrOx) and iridium-tantalum oxide (IrTaOx) thin films were prepared by reactive magnetron sputtering. Composition, density, and structure were determined using Rutherford backscattering spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and electron energy loss spectroscopy. The electronic density of states (DOS) and the solid phase chemical diffusion coefficient (D) were determined for hydrogen in IrOx and IrTaOx by potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS). The complex refractive indices were determined for colored and bleached IrOx and IrTaOx by inverting transmission and reflectance, measured using spectrophotometry in the 300-2500 nm wavelength range. A very porous structure, with a stoichiometry of IrO2.2, was found for IrOx. It contained ~4 nm sized grains. The IrTaOx had a denser structure built up by ~4 nm sized grains. The composition of IrTaOx was found to vary on a nanometer scale, with an average composition of IrTa1.4O5.6. It was found that DOS can be measured using PITT and EIS in the presence of spontaneous side reactions, even for systems influenced by non-negligible charge transfer kinetics and Ohmic drops. It was found that the measured DOS is 30-50% of the theoretically calculated DOS and that D is in the 10-10 – 10-11 cm2/s range for both materials. The hydrogen diffusion mechanism was described by an anomalous diffusion model, possibly indicating percolation or diffusion paths described by a fractal network. The refractive indices were found to be ~1.3 and ~2 for IrOx and IrTaOx, respectively, and independent of coloration state, whereas the extinction coefficients were found to modulate by ~30% for IrOx and ~50% for IrTaOx, making IrTaOx more favorable for electrochromic applications. A modulation peak was found at ~660 nm for both IrOx and IrTaOx associated with the removal of intraband transitions within the Ir t2g band.
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