Excitation energy transfer of porphyrin in polymer thin films by time-resolved scanning near-field optical microspectroscopy.
Thin films of water-soluble free-base porphyrin, 5,10,15,20-tetraphenyl-21H, 23H-porphinetetrasulphonic acid (TPPS) mixed with poly(diallyldimethyl ammonium chloride) (PDDA) have been prepared by a spin-coating method, in which the monomeric species were observed in the spin-coat film, whereas dimer was formed in the cast film prepared from TPPS/PDDA solution. Mesoscopic structures and dynamics of excitation energy migration and trapping of TPPS/PDDA spin-coat film have been analysed by time-resolved scanning near-field optical microspectroscopy (SNOM) and atomic force microscope. The observed film structure can be classified roughly into two parts: one is a large, flocculated polymer part, and the other is a smooth part widely spread around the flocculated polymers. In the smooth part, the observed spindle-like structure and circular hills and dips are essentially due to PDDA. The ellipsoidal small structures with approximately 2 microm length and < 1 microm width in the flocculated polymer part show non-exponential fluorescence decays. The non-exponential dynamics originates from the excitation energy migration among TPPS monomers and energy trapping to dimers. From the analysis of fluorescence decay curves based on the equation developed by Klafter and Blumen, the spectral dimension has been estimated to be approximately 1.46 for ellipsoidal structures. These results indicate that the distribution of the chromophore is inhomogeneous and a fractal-like structure exists even in the small domains determined by the resolution of the SNOM tip.
Miura
A
A
Department of Chemistry, School of Science, Kwansei Gakuin University, 1-1-155 Uegahara, Nishinomiya 662-8501, Japan. atu@kwansei.ac.jp
Yanagawa
Y
Y
Tamai
N
N