Solution processed polymer/fullerene blend films are receiving extensive attention as the photoactive layer of organic solar cells. In this paper we report a range of photophysical, electrochemical, physicochemical and structural data which provide evidence that formation of a relatively pure, molecularly ordered phase of the fullerene component, phenyl-C 61 -butyric acid methyl ester (PCBM), may be the key factor driving the spatial separation of photogenerated electrons and holes in many of these devices. PCBM crystallisation is shown to result in an increase in its electron affinity, providing an energetic driving force for spatial separation of electrons and holes. Based upon our observations, we propose a functional model applicable to many organic bulk heterojunction devices based upon charge generation in a finely intermixed polymer/fullerene phase followed by spatial separation of electrons and holes at the interface of this mixed phase with crystalline PCBM domains. This model has significant implications for the design of alternative acceptor materials to PCBM for organic solar cells.
We report the synthesis of a selenophene -diketopyrrolopyrrole monomer and its co-polymerisation with selenophene and thieno [3,2-b]thiophene monomers by Stille coupling. The resulting low band gap polymers exhibit ambipolar charge transport in organic field effect transistors. High and balanced electron and hole mobilities in excess of 0.1 cm 2 V -1 s -1 were observed in bottom gate, bottom contact devices, 10 suggesting that selenophene inclusion is a promising strategy for the development of ambipolar organic semiconductors.
The synthesis and characterization of a series of poly(3-alkyltellurophene)s are described. Polymers are prepared by both electrochemical and Kumada catalyst transfer polymerization methods. These polymers have reasonably high molecular weights (M(n) = 5.4-11.3 kDa) and can be processed in a manner analogous to that of their lighter atom analogues. All examples exhibit red-shifted optical absorption, as well as solid-state organization, as evidenced by absorption spectroscopy and atomic force microscopy. Overall, the synthesis and characterization of these materials open up a wide range of future studies involving tellurium-based polyheterocycles.
We study the molecular order and morphology in poly(3-hexylthiophene) (P3HT) and poly(3-hexylselenophene) (P3HS) thin films and their blends with [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM). We find that substitution of the sulfur atoms in the thiophene rings of P3HT by heavy selenium atoms increases the tendency of the molecules to form better ordered phase; interestingly, their overall fraction of ordered phase is much lower than that of P3HT-based films. The higher tendency of P3HS molecules to order (aggregate) is consistent with more planar chain conformation simulated. The lower fraction of ordered phase (or the higher fraction of disordered phase) in P3HS-based films is clearly identified by in-plane skeleton Raman modes under resonant excitation conditions, such as a smaller ratio of the C═C modes associated with the ordered (∼1422 cm(-1)) and disordered (∼1446 cm(-1)) phases (I(1422 cm(-1))/I(1446 cm(-1)) = 1.4 for P3HS and 0.6 for P3HS:PCBM), compared with P3HT-based films (I(1449 cm(-1))/I(1470 cm(-1)) = 2.5 for P3HT and 1.0 for P3HT:PCBM) and a larger Raman dispersion of the C═C mode: P3HS (17 cm(-1)) versus P3HT (6 cm(-1)) and P3HS:PCBM (36 cm(-1)) versus P3HT:PCBM films (23 cm(-1)). The higher fraction of disordered phase in P3HS prevents the formation of micrometer-sized PCBM aggregates in blend films during thermal annealing. Importantly, this lower fraction but better quality of ordered phase in P3HS molecules strongly influences P3HS:PCBM photovoltaic performance, producing smaller short-circuit current (J(sc)) in pristine devices, but significantly larger increase in J(sc) after annealing compared to P3HT:PCBM devices. Our results clarify the effects of heavy atom substitution in low band gap polymers and their impact on blend morphology and device performance. Furthermore, our study clearly demonstrates resonant Raman spectroscopy as a simple, but powerful, structural probe which provides important information about "fraction/quantity of ordered phase" of molecules, not easily accessible using traditional X-ray-based techniques.
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