Single-molecule microscopy studies of electric-field poling in chromophore-polymer composite materials

One strategy for increasing the efficiency of organic electrooptic devices based on chromophore-polymer composite materials is to improve chromophore ordering. In these materials, ordering is induced through the interaction of the chromophore dipole moment with an external electric field, applied at temperatures near the Tg of the polymer host, a process referred to as "poling". To provide insight into the molecular details of the poling process under conditions representative of device construction, the rotational dynamics of single 4-dicyano-methylene-2-methyl-6-(p-(dimethylamino)styryl)-4H-pyran (DCM) molecules in poly(methyl acrylate) at T = Tg + 11 degrees C in the presence and absence of an electric field are investigated using single-molecule confocal fluorescence microscopy. Single-molecule rotational dynamics are monitored through the time evolution of the fluorescence anisotropy. The anisotropy correlation function demonstrates nonexponential decay, with beta values derived from fits using the Kohlrausch-Williams-Watts law ranging from 0.7 to 1 with beta(KWW) = 0.83. This observation is consistent with previous studies of molecular rotation dynamics in polymer melts and reflects the dynamical heterogeneity provided by the polymer host. The rotational dynamics of DCM are weakly perturbed in the presence of a 50 V/microm electric field, typical of the field strength employed in device construction. The expected perturbation of the rotational dynamics is determined and found to be consistent with the alignment potential created by the electric field relative to the amount of thermal energy available. The relevance of these findings with respect to current models of the poling process is discussed. This work demonstrates the utility of polarization-sensitive single-molecule microscopy in elucidating the details of molecular reorientation during poling.