Metal oxides are the key ingredients for the development of many advanced functional materials and smart devices. Nanostructuring has emerged as one of the best tools to unlock their full potential. Tungsten oxides (WOx) are unique materials that have been rigorously studied for their chromism, photocatalysis, and sensing capabilities. However, they exhibit further important properties and functionalities that have received relatively little attention in the past. This Feature Article presents a general review of nanostructured WOx, their properties, methods of synthesis, and a description of how they can be used in unique ways for different applications. Tungsten oxides (WOx) are unique functional materials that can be obtained in a vast variety of nanostructured forms. This Feature Article presents a comprehensive review on the properties of WOx that goes beyond chromism and photocatalysis, for which they are usually investigated for. This is followed by a survey of their synthesis methods and implementations for different applications.

Nanostructured Tungsten Oxide – Properties, Synthesis, and Applications

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.

/pdf/electrochromics-for-smart-windows-thin-films-of-tungsten-aw0rai8h60.pdf

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

Many transition metal-oxide films exhibit an electrochromic (EC) effect as they change their optical transmittance upon charge insertion or extraction. These materials may be integrated into multilayer devices, and the optical modulation is then produced by application of a small electrical voltage. Electrochromic films are therefore being developed for application in dynamic or “smart” windows that are at the forefront of emerging energy-saving advances in building technologies. Here we will describe the state-of-the-art technology that is being implemented in commercial applications. It predominantly relies on the use of tungsten oxide-based films (coloring with ion insertion) and nickel oxide-based films (coloring with ion extraction). We also suggest future research directions that are motivated by the need to reduce the production costs of large-area EC windows. Specifically, we describe the possibility of alternative less expensive manufacturing processes, as well as the development of flexible EC devices that allow for an inexpensive “retrofit” installation to existing structures.

Metal-oxide films for electrochromic applications: present technology and future directions

WO3 thin layers with nanometer-scale periodicity were prepared by evaporation-induced self-assembly (EISA) using a novel amphiphilic block-copolymer template (poly(ethylene-co-butylene)-block-poly(ethylene oxide)). The evolution of the mesoporous ordered network and the crystallinity of the framework were monitored by 2D-SAXS, WAXS, SEM, XPS, and porosimetry. By annealing the films, the pore-wall crystallinity is adjusted between fully amorphous and highly crystalline without mesostructural degradation. Thus, the crystalline-film framework is composed of phase-pure monoclinic WO3 nanoparticles (12-14 nm in size). Furthermore, heat treatment transforms the originally spherical mesopores into ellipsoids, resulting in a unidirectionally shrunken, but still well-defined and fully accessible bcc mesopore architecture. The influence of mesoporosity and crystallinity on electrochemical/electrochromic characteristics was addressed by monitoring electrochemical features and the absorption changes during Li insertion/extraction (repetitive potentiostatic cycling). Both the amorphous and crystalline mesoporous films possess electrochromic response times on the order of only seconds, which are attributable to the facilitated insertion of guest ions due to shortening of the diffusion path lengths. Also, the insertion/extraction reversibility of crystalline WO3 layers with 3D mesoporosity is improved compared to amorphous ones and reaches values close to 100%.

Elb. El Idrissi

Papers

Preparation and characterization of pyrolytic spray deposited electrochromic tungsten trioxide films

Electrochromic effect in WO3 thin films prepared by spray pyrolysis