Photophysics of carbazole-containing systems. 2. Fluorescence behaviour of poly(N-vinyl carbazole) and N-vinyl carbazole/methyl acrylate copolymer films

Abstract. The fluorescence behaviour of thin films of poly(N-vinyl carbazole), PNVCz, and a series of N-vinyl carbazole/methyl acrylate, NVCz/MA, copolymers has been investigated using both steady-state and time-resolved emission techniques. The fluorescence of PNVCz at 298 K is dominated by emission from two excimeric traps. Trap I has the conventional ‘sandwich’ structure formed from two fully overlapped aromatic rings. The other (trap II) is a species involving two partially overlapped carbazole substituents. The fluorescences of the NVCz/MA copolymers contain contributions from unassociated or monomeric carbazoyl excited states which increase in prominence as the aromatic content of the system is reduced. The influence of intermolecular interactions in creating excimer traps is apparent: even at a carbazole content of 8.3 mol%, excimer emission is evident. In PNVCz and copolymers of higher aromatic contents, the microtacticity of the macromolecule exerts a dominant influence upon the photophysical behaviour of the bulk polymer despite the moderating effects of intermolecular interactions between chromophores. As the temperature of the system is reduced, the contribution from trap II to the overall fluorescence from the polymer films increases relative to that made by emission from trap I. A