Electrochromic (EC) materials are able to change their optical properties, reversibly and persistently, by the application of an electrical voltage. These materials can be integrated in multilayer devices capable of modulating the optical transmittance between widely separated extrema. We first review the recent literature on inorganic EC materials and point out that today's research is focused on tungsten oxide (colouring under charge insertion) and nickel oxide (colouring under charge extraction). The properties of thin films of these materials are then discussed in detail with foci on recent results from two comprehensive investigations in the authors' laboratory. A logical exposition is obtained by covering, in sequence, structural features, thin film deposition (by sputtering), electronic band structure, and ion diffusion. A novel conceptual model is given for structural characteristics of amorphous W oxide films, based on notions of defects in the ideal amorphous state. It is also shown that the conduction band density of states is obtainable from simple electrochemical chronopotentiometry. Ion intercalation causes the charge-compensating electrons to enter localized states, implying that the optical absorption underlying the electrochromism can be described as ensuing from transitions between occupied and empty localized conduction band states. A fully quantitative theory of such transitions is not available, but the optical absorption can be modeled more phenomenologically as due to a superposition of transitions between different charge states of the W ions (6+, 5+, and 4+). The Ni oxide films were found to have a porous structure comprised of small grains. The data are consistent with EC coloration being a surface phenomenon, most likely confined to the outer parts of the grains. Initial electrochemical cycling was found to transform hydrated Ni oxide into hydroxide and oxy-hydroxide phases on the grain surfaces. Electrochromism in thus stabilized films is consistent with reversible changes between Ni hydroxide and oxy-hydroxide, in accordance with the Bode reaction scheme. An extension of this model is put forward to account for changes of NiO to Ni2O3. It was demonstrated that electrochromism is associated solely with proton transfer. Data on chemical diffusion coefficients are interpreted for polycrystalline W oxide and Ni oxide in terms of the lattice gas model with interaction. The later part of this review is of a more technological and applications oriented character and is based on the fact that EC devices with large optical modulation can be accomplished essentially by connecting W-oxide-based and Ni-oxide-based films through a layer serving as a pure ion conductor. Specifically, we treat methods to enhance the bleached-state transmittance by mixing the Ni oxide with other oxides characterized by wide band gaps, and we also discuss pre-assembly charge insertion and extraction by facile gas treatments of the films, as well as practical device manufacturing and device testing. Here the emphasis is on novel flexible polyester-foil-based devices. The final part deals with applications with emphasis on architectural “smart” windows capable of achieving improved indoor comfort jointly with significant energy savings due to lowered demands for space cooling. Eyewear applications are touched upon as well.

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Electrochromics for smart windows: thin films of tungsten oxide and nickel oxide, and devices based on these

Optical and electrochromic properties of oxygen sputtered tungsten oxide (WO3) thin films

The electron-selective layer (ESL) is an indispensable component of perovskite solar cells (PSCs) and is responsible for the collection of photogenerated electrons. Preparing ESL at a low temperature is significant for future fabrication of flexible PSCs. In this work, solution-processed amorphous WOx thin film was prepared facilely at low temperature and used as ESL in PSCs. Results indicated that a large quantity of nanocaves were observed in the WOx thin film. In comparison with the conventional TiO2 ESL, the WOx ESL exhibited comparable light transmittance but higher electrical conductivity. Compared with the TiO2-based PSCs, PSCs that use WOx ESL exhibited comparable photoelectric conversion efficiency, larger short-circuit current density, but lower open-circuit voltage. Electrochemical characterization indicated that the unsatisfied open-circuit voltage and fill factor were caused by the inherent charge recombination. This study demonstrated that this material is an excellent candidate for ESL.

Low-Temperature and Solution-Processed Amorphous WO(x) as Electron-Selective Layer for Perovskite Solar Cells.

The oxygen vacancy in WO3 has previously been implicated in the electrochromism mechanism in this material. Previous theoretical calculations on the oxygen vacancy in WO3 have not considered the full range of crystal structures adopted by the material. Here we report studies of the oxygen vacancy in seven crystal phases. The use of a very accurate tungsten plane-wave pseudopotential means that a byproduct of this study is a more detailed and complete picture of undefected WO3 than previously available. Electronic structures of the crystal phases in both undefected and defected systems have been calculated and are discussed. The band gap in WO3 is dependent upon bonding−antibonding interactions, these being dependent upon overlap in each direction. The effect of an oxygen vacancy is dependent upon the availability of both Op and Wd electrons, this being different for the various phases. A variety of behavior is predicted, which may be explained in terms of O2p−W5d mixing, including the formation of long W−...

The Oxygen Vacancy in Crystal Phases of WO3

Nanocrystalline tungsten oxide (WO3) films were grown by reactive magnetron sputter-deposition. The structure and optical properties of WO3 films were evaluated using grazing incidence x-ray diffraction and optical spectroscopic measurements. The effect of ultramicrostructure was significant on the optical characteristics of WO3 films. The band gap decreases from 3.25 to 2.92 eV with increasing grain-size from ∼9 to 50 nm while the films exhibit a transition from monoclinic to tetragonal phase. A direct microstructure-property relationship found suggests that tuning properties of WO3 films for desired applications can be achieved by tuning the conditions and controlling the phase.

K. Sasaki

Papers

Optical and electrochromic properties of RF reactively sputtered WO3 films