ABSTRACT
We demonstrate the on-surface formation of homogeneous and uniform electrochromic films via ultrasonic spray coating. This fully automated process is capable of fabricating metallo-organic films on transparent conducting oxides (TCOs) on glass or flexible poly(ethylene terephthalate) (PET) with surface areas of up to 36 cm2 and film thicknesses of half a micron. The assembly process involves alternatingly spray-coating dilute solutions of structurally well-defined iron polypyridyl ([Fe(mbpy-py)3]2+) complexes and bis(benzonitrile)palladium dichloride (Pd(PhCN)2Cl2) onto conductive substrates, where the latter palladium salt was used as the inorganic cross-linker. The on-surface self-assembled three-dimensional networks are intensely colored and were subsequently integrated into laminated electrochromic devices (ECDs) containing a lithium-based gel electrolyte. The ECDs retain their intense color in the ground state, having a Δ Tmax of 40-49% at λmax ≈ 600 nm, and can be operated for up to 1500 redox cycles. The fluorine-doped tin oxide counter electrode coated with poly(3,4-ethylene-dioxythiophene)polystyrene sulfonate (PEDOT:PSS) as a charge-storage layer resulted in these stable devices. A significant decrease in the potential window of Δ E ≈ 2.5 V was achieved by using a metal grid on PET as the counter electrode. The operation of the electrochromic films is diffusion-controlled, and the diffusion coefficients ( Df) reflect their molecular densities. During these studies, we found that ClO4- is a suitable counterion of the lithium-based electrolytes for optimal ECD performance.
ABSTRACT
We demonstrate the mediation of charge transport and release in thin films and devices by shifting the redox properties of layers of metal complexes by light. The nanoscale surface arrangement of both photo- and electrochemically-active components is essential for the function of the thin films. Layers of well-defined ruthenium complexes on indium-tin-oxide electrodes provide electron-transport channels that allow the electrochemical addressing of layers of isostructural cobalt complexes. These cobalt complexes are electrochemically inactive when assembled directly on transparent metal-oxide electrodes. The interlayer of ruthenium complexes on such electrodes allows irreversible oxidation of the cobalt complexes. However, shifting the redox properties of the ruthenium complexes by excitation with light opens up an electron-transport channel to reduce the cobalt complexes; hence releasing the trapped positive charges.
ABSTRACT
In this study, we demonstrate a versatile approach for the formation of electrochromic nanoscale assemblies on transparent conductive oxides on both rigid and flexible substrates. Our method is based on the application of alternating spin-coated layers of well-defined metal polypyridyl complexes and a palladium(II) salt to form electrochemically addressable films with a high chromophore density. By varying the central metal ion of the polypyridyl complexes (Os, Ru, and Fe) and their ligands and by mixing these complexes, coatings with a wide range of colors can be achieved. These coatings cover a large area of RGB color space. The coloration intensities of these nanoscale films can be tuned by the number of deposition steps. The materials have very attractive ON/OFF ratios, electrochemical stabilities, and coloration efficiencies. Reversible color-to-colorless and color-to-color transitions were demonstrated, and the films were further integrated into sandwich cells.
