Organic optoelectronics calls for materials combining bright luminescence and efficient charge transport. The former is readily achieved in isolated molecules, while the latter requires strong molecular aggregation, which usually quenches luminescence. This hurdle is generally resolved by doping the host material with highly luminescent molecules collecting the excitation energy from the host. Here, a novel concept of molecular self-doping is introduced in which a higher luminescent dopant emerges as a minute-amount byproduct during the host material synthesis. As a one-stage process, self-doping is more advantageous than widely used external doping. The concept is proved on thiophene-phenylene cooligomers (TPCO) consisting of four (host) and six (dopant) conjugated rings. It is shown that <1% self-doping doubles the photoluminescence in the TPCO single crystals, while not affecting much their charge transport properties. The Monte-Carlo modeling of photoluminescence dynamics reveals that host-dopant energy transfer is controlled by both excitonic transport in the host and host-dopant Förster resonant energy transfer. The self-doping concept is further broadened to a variety of conjugated oligomers synthesized via Suzuki, Kumada, and Stille crosscoupling reactions. It is concluded that self-doping combined with improved excitonic transport and host-dopant energy transfer is a promising route to highly luminescent semiconducting organic single crystals for optoelectronics.
In recent years, monolayer organic field-effect devices such as transistors and sensors have demonstrated their high potential. In contrast, monolayer electroluminescent organic field-effect devices are still in their infancy. One of the key challenges here is to create an organic material that self-organizes in a monolayer and combines efficient charge transport with luminescence. Herein, we report a novel organosilicon derivative of oligothiophene-phenylene dimer D2-Und-PTTP-TMS (D2, tetramethyldisiloxane; Und, undecylenic spacer; P, 1,4-phenylene; T, 2,5-thiophene; TMS, trimethylsilyl) that meets these requirements. The self-assembled Langmuir monolayers of the dimer were investigated by steady-state and time-resolved photoluminescence spectroscopy, atomic force microscopy, X-ray reflectometry, and grazing-incidence X-ray diffraction, and their semiconducting properties were evaluated in organic field-effect transistors. We found that the best uniform, fully covered, highly ordered monolayers were semiconducting. Thus, the ordered two-dimensional (2D) packing of conjugated organic molecules in the semiconducting Langmuir monolayer is compatible with its high-yield luminescence, so that 2D molecular aggregation per se does not preclude highly luminescent properties. Our findings pave the way to the rational design of functional materials for monolayer organic light-emitting transistors and other optoelectronic devices.
A series of novel highly soluble double-caged [60]fullerene derivatives were prepared by means of lithium-salt-assisted [2+3] cycloaddition. The bispheric molecules feature rigid linking of the fullerene spheres through a four-membered cycle and a pyrrolizidine bridge with an ester function CO R (R=n-decyl, n-octadecyl, benzyl, and n-butyl; compounds 1 a-d, respectively), as demonstrated by NMR spectroscopy and X-ray diffraction. Cyclic voltammetry studies revealed three closely overlapping pairs of reversible peaks owing to consecutive one-electron reductions of fullerene cages, as well as an irreversible oxidation peak attributed to abstraction of an electron from the nitrogen lone-electron pair. Owing to charge delocalization over both carbon cages, compounds 1 a-d are characterized by upshifted energies of frontier molecular orbitals, a narrowed bandgap, and reduced electron-transfer reorganization energy relative to pristine C . Neat thin films of the n-decyl compound 1 a demonstrated electron mobility of (1.3±0.4)×10 cm V s , which was comparable to phenyl-C -butyric acid methyl ester (PCBM) and thus potentially advantageous for organic solar cells (OSC). Application of 1 in OSC allowed a twofold increase in the power conversion efficiencies of as-cast poly(3-hexylthiophene-2,5-diyl) (P3HT)/1 devices relative to the as-cast P3HT/PCBM ones. This is attributed to the good solubility of 1 and their enhanced charge-transport properties - both intramolecular, owing to tightly linked fullerene cages, and intermolecular, owing to the large number of close contacts between the neighboring double-caged molecules. Test P3HT/1 OSCs demonstrated power-conversion efficiencies up to 2.6 % (1 a). Surprisingly low optimal content of double-caged fullerene acceptor 1 in the photoactive layer (≈30 wt %) favored better light harvesting and carrier transport owing to the greater content of P3HT and its higher degree of crystallinity.
State-of-the-art organic photovoltaic active layers typically undergo post-treatment such as thermal or solvent vapor annealing to increase their performance by tuning the bulk heterojunction morphology. The molecular crystallinity is one of the key factors that determine the morphology.Real-time tracking of the crystallinity during the post-treatment is strongly desired for understanding the physics of the crystallization process and for optimizing the post treatment 2 protocol. Here, we report on cold crystallization dynamics of the polymer in the temperature range of 50-150 °C in polymer:fullerene blends based on poly(3-hexylthiophene) with various fullerenebased acceptors (C60, PC61BM, PC71BM, bisPC61BM, HBIM, AIM8, and IrC60) in real-time by Raman microscopy. We also reveal how different solvents, fullerene acceptors, and temperatures affect cold crystallization during thermal annealing. We further demonstrate a correlation between the fullerene derivative weight and the polymer crystallinity for the as-cast films, and also a correlation of the polymer crystallinity before and after annealing. Our findings are essential for developing efficient strategies of morphology optimization in emerging organic photovoltaic devices with the real-time Raman microscopy tracking as a valuable tool.
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