Excitations luminescent conjugated polymers

The lowest excited states in luminescent conjugated polymers are very similar to the dyes used in dye lasers (Chapter 3, section 3.5.3). Therefore the conjugated polymers can be used to achieve population inversion by optical pumping as with the laser dyes. 

Examples of the optical pumping of solutions of luminescent conjugated polymers include laser action at 596 nm of poly[2-methoxy-5-(2-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV) using excitation with 6 ns Nd YAG third harmonic pulses (354.7 nm). ° Tuning of hexane solutions of the co-polymer poly(2,2, 5,5 -tetraoctyl-p-terphenyl-4,4 -xylene-vinylene-p-phenylenevinylene) (TOP-PPV) was possible between 414 and 456 mn, similar to the classical coumarin laser dyes. ... 

Rriend, R.H., et al. 1997. Electronic excitations in luminescent conjugated polymers. Synth Met 84 463. 

We now turn to a discussion of the issue related to the nature of the emitting species in the lowest excited state of luminescent conjugated polymers, with the help of theoretical calculations including both electron-phonon and electron-electron interactions. Specifically, we address the following propositions that have been reported in the literature ... 

The role of disorder in the photophysics of conjugated polymers has been extensively described by the work carried out in Marburg by H. Bassler and coworkers. Based on ultrafast photoluminescence (PL) (15], field-induced luminescence quenching [16J and site-selective PL excitation [17], a model for excited state thermalizalion was proposed, which considers interchain exciton migration within the inhomogenously broadened density of states. We will base part of the interpretation of our results in m-LPPP on this model, which will be discussed in some detail in Sections 8.4 and 8.6. 

In another approach, a fluorescent conjugated polymer was used as the material for the preparation of a chemosensor to detect 2,4,6-trinitrotoluene (TNT) and its related nitroaromatic compounds. To this end, microparticles, made of three-dimensionally cross-linked poly(l,4-phenylene vinylene) (PPV) via emulsion polymerization, were synthesized [61]. This material was chosen due to its high fluorescence intensity and sensitivity to changes in its microenvironment. The chemosensor was exposed to vapour containing different amounts of TNT and quenching of the polymer luminescence at 560 nm was observed after excitation at 430 nm. The dependence of the fluorescence signal in response to the analyte was described by a modified Stem-Volmer equation that assumes the existence of two different cavity types. The authors proposed the modified Stem-Volmer equation as follows ... 

Long-lived photoluminescence, at 826 nm, is reported (t 15 (is) for thin films of the processable, -conjugated polymer, poly(3-hexylthio-phene) (93JA8447). Excitation of the n—n transition with 518 nm light (So >S ) yields only very weak luminescence of 826-nm light, even at 18 K. The emission is enhanced, to point where it can be observed at room temperature, when the excitation wavelength is 250 nm, but it is completely quenched by oxygen. Prompt fluorescence decays within... 

Hybridization between )r-conjugated polymers and metals at the nanoscale level has been used for luminescence enhancement and to realize biosensing through SPR coupling [6, 64,65,101,102]. The surface plasmon defines a coherent excitation of free electrons in metal nanostructures interacting with an incident electromagnetic... 

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