Blend thin films, prepared by dip-coating, of polyfluorene (F8 or PFO), acting as an electron donor, and [6,6]-phenyl-C61- butyric acid methyl ester (PC60BM), acting as the electron acceptor, have been characterized by UV/VIS absorption spectroscopy, static and dynamic fluorescence, and atomic force microscopy. Four different solvents were used for the film preparation; the monohalogenated fluorobenzene and chlorobenzene and their dihalogenated counterparts odifluorobenzene and o-dichlorobenzene, respectively. Fluid mechanics calculations were used to determine the withdrawal speed for each solvent, in order to prepare wet films of comparable thicknesses. The resulting dry films were also of similar thicknesses. It was found that the choice of solvent influences the ability for F8 to form its β-phase.
When preparing the active layer film for organic optoelectronic devices, e.g., solar cells, spin-coating is often used for the deposition of the solution of electron donor and acceptor molecules. An alternative, among others, is to use dipcoating, where the substrate is dipped into the solution and subsequently withdrawn, all at coordinated speeds and times. In order to develop knowledge on how the final active layer morphology is influenced by preparation parameters, different coating methods are compared. In this contribution, we report on a comparative study of thin deposited films from a model system. The investigated model system is poly(9,9-dioctylfluorene) (F8, also referred to as PFO) as donor and [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) as acceptor. Combining fluorescence and absorption spectroscopy with atomic force microscopy allows us to conclude that dipcoating offers increased possibilities to manipulate the film morphology, that the transition of the glassy F8 α-phase to the more ordered β-phase is influenced by the dipping speed as well as by the blend ratio, and that the long-wavelength emission of F8 cannot stem from the oxidized keto-F8 only.
The quinoxaline-based polymer TQ1 (poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5- diyl]) is a promising candidate as electron donor in organic solar cells. In combination with the electron acceptor [6,6]- phenyl-C71- butyric acid methyl ester (PC70BM), TQ1 has resulted in solar cells with power conversion efficiencies of 7 %.
We have studied TQ1 films, with and without PC70BM, spin-casted from different solvents, by fluorescence spectroscopy and UV/VIS absorption spectroscopy. We used chloroform (CF), chlorobenzene (CB), and odichlorobenzene (o-DCB) as solvents for the coating solutions and 1-chloronaphthalene (CN) as solvent additive. CN addition has been shown to enhance photo-conversion efficiency of these solar cells. Phase-separation causes lateral domain formation in the films and the domain size depends on the solvent . These morphological differences coincide with changes in the spectroscopic patterns of the films.
From a spectroscopic point of view, TQ1 acts as fluorescent probe and PC70BM as quencher. The degree of fluorescence quenching is coupled to the morphology through the distance between TQ1 and PC70BM. Furthermore, if using a bad solvent for PC70BM, morphological regions rich in the fullerene yield emission characteristic for aggregated PC70BM. Clear differences were found, comparing the TQ1:PC70BM blend films casted from different solvents and at different ratios between the donor and acceptor. The morphology also influences the UV/VIS absorption spectra, yielding further information on the composition.
The results show that fluorescence and UV/VIS absorption spectroscopy can be used to detect aggregation in blended films and that these methods extend the morphological information beyond the scale accessible with microscopy.
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