Effect of Fullerene Intercalation on the Conformation and Packing of Poly-(2-methoxy-5-(3′-7′-dimethyloctyloxy)-1,4-phenylenevinylene)

Abstract

Photoluminescence (PL) and resonance Raman spectroscopy are used to track changes in the conformations and packing of poly-(2-methoxy-5-(3'-7'-dimethyloctyloxy)-1,4-phenylenevinylene) (MDMO-PPV) chains with the addition of [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) molecules. PL lineshapes of MDMO-PPV thin films as a function of annealing time were first measured to determine the spectroscopic signatures of chain conformations and packing in the absence of PCBM. Annealing results in enhanced interchain interactions leading to red-shifts of PL 0-0 transitions by up to ∼300 cm(-1) and apparent increases of the line shape Huang-Rhys factors. Wavelength-dependent PL lifetimes of as-cast and films annealed for short times (∼30 s) are nonexponential with an instrument-limited component of ∼100 ps and a ∼350 ps component. With longer annealing times, decays become single exponential with an average lifetime of ∼1 ns indicating that all excitations efficiently funnel to strongly coupled interchain sites. Addition of PCBM disrupts MDMO-PPV interchain interactions causing PL 0-0 transitions to blue-shift, increases in line width, and decreases in apparent Huang-Rhys factors. Resonance Raman spectra of MDMO-PPV/PCBM thin films with variable PCBM weight fractions (∼50:1 up to 1:8 w/w) were then measured using short (488 nm) and long (568 nm) excitation wavelengths. The out-of-plane vinylene C-H wag mode of MDMO-PPV (∼964 cm(-1)) showed pronounced increases in intensity of up to ∼30% and red-shifts of up to 5 cm(-1) with increasing PCBM content. These changes result from a decrease of planarity between chain segments that suppresses interchain interactions. Furthermore, red-shifts of up to ∼4 cm(-1) were observed for the C═C symmetric stretch of the MDMO-PPV vinylene group (∼1625 cm(-1)) with 488 nm excitation. The sensitivity of the MDMO-PPV vinylene group vibrations with PCBM indicates preferential interactions between these two molecules and is consistent with intercalation of PCBM into the polymer structure. This assignment was confirmed by thermally annealing of MDMO-PPV/PCBM films to remove intercalated PCBM molecules, which partially restores interchain interactions as seen from smaller intensity increases (∼15%) and red-shifts (∼2 cm(-1)) of the ∼964 cm(-1) mode. Overall, the spectroscopic results show that MDMO-PPV chains adopt distorted conformations (i.e., less intrachain order and shorter conjugation lengths) that have important implications for explaining the structural origins for large improvements in charge mobilities in MDMO-PPV/PCBM blends.