Macromolecules, Vol.47, No.7, 2324-2332, 2014
Fullerene-Grafted Copolymers Exhibiting High Electron Mobility without Nanocrystal Formation
Well-soluble fullerene-grafted copolymers PPCBMs with high contents of pendant phenyl-C-61-butyric acid methyl ester (PCBM) between 30 and 64 wt % are reported. Herein, the tailor-made precursor copolymers poly(4-methoxystyrene-stat-4-tert-butoxystyrene) obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization are functionalized via an efficient polymer-analogous esterification. The synthesized acceptor copolymers retain the optical and electrochemical properties of the incorporated PCBM independent of their fullerene weight fraction. Their electron transport properties are studied by the space-charge limited current (SCLC) method. The maximum electron mobility mu(e) of 1 X 10(-4) cm(2) V-1 s(-1) is achieved for 37 wt % of incorporated PCBM. Below 50 wt % of PCBM, the acceptor polymers exhibit exceptional high charge carrier mobility compared to the corresponding blends of molecular PCBM and precursor copolymer. Detailed structural studies using AFM, TEM, and XRD are performed. We confirm amorphous morphology both in thin films and in bulk for the PPCBMs, which clearly indicates the absence of PCBM nanocrystals. Thus, an efficient charge carrier percolation is facilitated by the homogeneous distribution of PCBM in the copolymer. Additionally, the absence of nanocrystal formation was demonstrated during thermal annealing.