ABSTRACT
A diketopyrrolopyrrole (DPP) and perylene diimide (PDI)-based molecule, denoted as PDI-DPP-PDI, was investigated as an electron acceptor material in bulk heterojunction (BHJ) solar cells, with poly[[4,8-bis [5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl] [2-(2-ethyl-1-oxohexyl)thieno[3,4-b]thiophenediyl]] (PBDTTT-CT) as an electron donor. The donor polymer and the acceptor molecule have complementary absorption spectra, which is an essential feature for energy collection in organic solar cells. However, AFM images indicated the presence of isolated and microsized PDI-DPP-PDI domains along the surface of the films, which reduced the power conversion efficiency. Therefore, to improve the homogenization of the acceptor along the film, a post-deposition treatment, denoted as solvent vapor annealing (SVA), was performed in a saturated atmosphere containing the vapour of an organic solvent for 3-10 minutes. This procedure changed the optical and morphological properties of the PBDTTT-CT : PDI-DPP-PDI active layer, resulting in increased power conversion efficiency values by more than 2.5 times (reaching 5.1%). Theoretical simulation pointed out that the experimental absorbance band localized at 580 nm, which appeared after SVA treatment, is possibly related to an intense simulated band with a maximum at 572 nm, resulting from a pair of transitions starting in the copolymer and ending in PDI-DPP-PDI, in regions where both are stacked at about 3 Å. The most significant natural transition orbitals (NTOs) related to these transitions indicated charge transfer character. Moreover, analyses carried out by power spectrum density (PDS) of images acquired from the SVA-treated film indicated that in the region of larger frequencies, across the length scale at around 30-70 nm, an additional fractal region appeared with a Ds of 0.95, indicating a flattened region, possibly related to changes in the overall conformation after SVA treatment. This indicates an improvement in the molecular packing, a feature not observed in the as-cast film. The analyses by force curve spectroscopy pointed out increased adhesion forces and adhesion energy in the PBDTTT-CT : PDI-DPP-PDI film after SVA treatment; this feature enhanced the interfacial interaction with the top electrodes, reflecting improved charge extraction in the photovoltaic device.
ABSTRACT
Fluorene-based systems have shown great potential as components in organic electronics and optoelectronics (organic photovoltaics, OPVs, organic light emitting diodes, OLEDs, and organic transistors, OTFTs). These systems have drawn attention primarily because they exhibit strong blue emission associated with relatively good thermal stability. It is well-known that the electronic properties of polymers are directly related to the molecular conformations and chain packing of polymers. Here, we used three oligofluorenes (trimer, pentamer, and heptamer) as model systems to theoretically investigate the conformational properties of fluorene molecules, starting with the identification of preferred conformations. The hybrid exchange-correlation functional, OPBE, and ZINDO/S-CI showed that each oligomer exhibits a tendency to adopt a specific chain arrangement, which could be distinguished by comparing their UV/vis electronic absorption and (13)C NMR spectra. This feature was used to identify the preferred conformation of the oligomer chains in chloroform-cast films by comparing experimental and theoretical UV/vis and (13)C NMR spectra. Moreover, the oligomer chain packing and dynamics in the films were studied by DSC and several solid-state NMR techniques, which indicated that the phase behavior of the films may be influenced by the tendency that each oligomeric chain has to adopt a given conformation.
