Solution-Processable Electrochemiluminescent Ion Gels for Flexible, Low-Voltage, Emissive Displays on Plastic

Ion gels comprising ABA triblock copolymers and ionic liquids have received much attention as functional materials in numerous applications, especially as gate dielectrics in organic transistors. Here we have expanded the functionality of ion gels by demonstrating low-voltage, flexible electrochemiluminescent (ECL) devices using patterned ion gels containing redox-active luminophores. The ECL devices consisted only of a 30 μm thick emissive gel and two electrodes and were fabricated on indium tin oxide-coated substrates (e.g., polyester) simply by solution-casting the ECL gel and brush-painting a top Ag electrode. The triblock copolymer employed in the gel was polystyrene-<i>block</i>-poly­(methyl methacrylate)-<i>block</i>-polystyrene, where the solvophobic polystyrene end blocks associate into micellar cross-links in the versatile ionic liquid 1-ethyl-3-methylimidazolium bis­(trifluoromethylsulfonyl)­imide ([EMI]­[TFSI]). An ECL gel containing ∼6.25 wt % Ru­(bpy)₃Cl₂ (relative to [EMI]­[TFSI]) as the luminophore turned on at an AC peak-to-peak voltage as low as 2.6 V (i.e., −1.3 to +1.3 V) and showed a relatively rapid response (sub-ms). The wavelength of maximum emission was 610 nm (red-orange). With the use of an iridium­(III) complex, Ir­(diFppy)₂(bpy)­PF₆ [diFppy = 2-(2′,4′-difluorophenyl)­pyridine; bpy = 2,2′-bipyridyl], the emitting color was tuned to a maximum wavelength of 540 nm (green). Moreover, when a blended luminophore system containing a 60:40 mixture of Ru­(bpy)₃²⁺ and Ir­(diFppy)₂(bpy)⁺ was used in the emissive layer, the luminance of red-orange-colored light was enhanced by a factor of 2, which is explained by the generation of the additional excited state Ru­(bpy)₃²⁺* by a coreactant pathway with Ir­(diFppy)₂(bpy)⁺* in addition to the usual annihilation pathway. This is the first time that enhanced ECL has been achieved in ion gels (or ionic liquids) using a coreactant. Overall, the results indicate that ECL ion gels are attractive multifunctional materials for printed electronics