Synthesis, characterisation and in situ colorimetry of electrochromic Ruthenium purple thin films

Ruthenium purple (RP) films on transmissive tin-doped indium oxide (ITO)/glass substrates have been synthesised by an electrochemical coagulation technique using an aqueous RP colloidal suspension prepared from separate very dilute aqueous solutions of iron(III) chloride and potassium hexacyanoruthenate(II), with dilute potassium chloride as supporting electrolyte solution. To aid stability of the RP films, ruthenium(III) chloride was added to the RP colloidal suspension. Using the CIE (Commission Internationale de l’Eclairage) system of colorimetry, the colour stimulus of the electrochromic RP films and the changes that take place on reversibly switching to the colourless form have been calculated from in situ visible spectra recorded under electrochemical control. On electrochemical reduction, the intensely absorbing bright purple mixed-valence iron(III) hexacyanoruthenate(II) chromophore is reduced to the colourless iron(II) hexacyanoruthenate(II) form. Sharp and reversible changes in the hue and saturation occur, as shown by the track of the CIE 1931 xy chromaticity coordinates. Concurrently, as the purple chromophore is bleached, a large increase in the relative luminance of the electrochromic film is observed. For the purple state, the CIELAB 1976 colour space coordinates were L* = 64, a* = 27 and b* = −36, with a complementary wavelength (λc) calculated as 555 nm, in excellent agreement with the absorption maximum (λmax) of 550 nm for the intervalence charge-transfer (IVCT) band.