Photoluminescence characterization of polythiophene films incorporated with highly functional molecules such as metallophthalocyanine.

The photoluminescence (PL) of conducting polymer polythiophene (PT) films incorporated with metallophthalocyanines (PcMs) such as CuPc, MgPc, FePc, Li2Pc, and CoPc was studied by PL and time-correlated single photon counting (TCSPC) measurements. Polymer films were prepared by electrochemical polymerization and PcMs migrated into the polymer films by a diffusion method using acetonitrile or toluene as a solvent to dissolve the PcMs. The wavelength of PL emission peaks changed significantly depending on the solvent used in the doping process. Using acetonitrile, the observed PL emission peaks originated from the Q band, whereas they were assigned to the Soret band in the case of toluene. TCSPC measurements showed that PL emission took place through a ligand-ligand transition process when using acetonitrile because the average lifetimes were comparable and independent of the central metal ions for CoPc-, Li2Pc-, and MgPc-doped polymer films. Conversely, using toluene, it was found that ligand-ligand emission occurred for Li2Pc-, MgPc-, and FePc-doped films. To identify the cause of the drastic change in PL emission pattern, x-ray photoelectron spectroscopy measurements were obtained. A lower binding energy component appeared in the C 1s core-level spectra of acetonitrile-processed PcM-doped PT films, whereas this component shifted to higher energy and overlapped with the main peak for toluene-processed PcM-doped PT films. The lower binding energy component corresponded to photoelectrons due to the C atoms in the benzene rings of the ligand. Lower binding energy components also appeared in the N 1s core-level spectra of acetonitrile-processed PcM-doped PT films, and this component shifted to higher energy for toluene-processed PcM-doped PT films. These lower energy components were assigned to the core-level peaks due to the N atoms at the meso position bridging between pyrrole rings. This suggests that the electron charge at the N sites of the meso positions in toluene-processed films was smaller than in acetonitrile-processed ones. The changes in energy at benzene C sites and meso N sites suggest that the electronic states of the phthalocyanine in the toluene-processed films were porphyrin-like, so the Soret band became dominant in the PL emission spectrum.