Solid-state diode-like chemiluminescence based on serial, immobilized concentration gradients in mixed-valent poly[Ru(vbpy){sub 3}](PF{sub 6}){sub 2} films
- Univ. of North Carolina, Chapel Hill, NC (United States)
The electronic conductivity and electrogenerated chemiluminescence (ECL) of thin, electropolymerized films of the fixed-site redox polymer poly[Ru(vbpy){sub 3}](PF{sub 6}){sub 2} (vbpy = 4-vinyl-4`-methyl-2,2`-bipyridine) on Pt interdigitated array electrodes were examined for both solvent-swollen and dry films. In both cases emission arose from {sup *}Ru{sup 2+} produced via the electron-transfer reaction between Ru{sup 3+} and Ru{sup 1+} states within the film (Ru = Ru-(vbpy){sub 3}). Dry films contained fixed concentration gradients of Ru{sup 3+}, Ru{sup 2+}, and Ru{sup 1+} states which were first introduced in an acetonitrile-swollen film via the constant potential oxidation and reduction of Ru{sup 2+} at opposing IDA fingers. The gradients were then immobilized by drying and cooling the film while retaining the inter-electrode bias (2.6V). The resulting dried and cooled films responded rapidly to changes in voltage bias and exhibited diode-like characteristics, conducting and emitting light at biases >2.6 V and undergoing a reverse bias breakdown current, unassociated with light emission, at ca. -5.5 V. At 0{degree}C the optimum quantum efficiency of solid-state ECL emission ({phi}{sub ECL}) was similar to that in solvent-swollen films: 0.0003 photon/electron. In contrast to the dry films, solvent-swollen films were slow to respond to changes in voltage bias and did not exhibit diode-like behavior. 18 refs., 7 figs.
- OSTI ID:
- 420724
- Journal Information:
- Journal of the American Chemical Society, Vol. 118, Issue 43; Other Information: PBD: 30 Oct 1996
- Country of Publication:
- United States
- Language:
- English
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