A novel stable bisazide molecule that can freeze the bulk heterojunction morphology at its optimized layout by specifically bonding to fullerenes is reported. The concept is demonstrated with various polymers: fullerene derivatives systems enable highly thermally stable polymer solar cells.

The introduction of the urea function as structure directing agent of diacetylene organogels (DA-OGs) has been achieved. Despite the urea function being one of the most frequently used structure directing agents for the formation of organogels, it has never been exploited in the fabrication and photopolymerization of DA-OGs. The self-association of ureas involving two hydrogen bonds is much stronger than that of urethanes or amides, and the resulting supramolecular assemblies are completely insoluble. In this context, 1,1'-(hexa-2,4-diyne-1,6-diyl)bis(3-(10-(triethoxysilyl)decyl)urea) 2 was synthesized. Compound 2 was soluble owing to the triethoxysilane function that we recently used in the fabrication of a silylated bis-urea-stilbene organogel. It formed an organogel, and its photopolymerization was studied in cyclohexane. The loss of the gel state and the formation of a red solution resulting from the polymerization were found to be the result of the constraints introduced by the urea function in close vicinity to the polymerizable function. To obtain an ureido substituted diacetylenic organogelator affording a blue highly conjugated polydiacetylene (PDA) without a sol-gel transition, a propylene spacer was introduced to move the urea function away from the polymerizable function (derivative 3). The thermochromism exhibited by the latter in the solid state was studied. Using the same setup and the same sample, UV-vis and FTIR spectra were simultaneously recorded as a function of the temperature to highlight a relation between color changes and urea association mode changes. The data showed that the reversible thermochromic transition must be associated with a reversible supramolecular modification and, conversely, that irreversible chromic transitions are the result of irreversible structural modifications. The chromic effects of the acidic hydrolysis-polycondensation of the trialkoxysilyl groups to form a siloxane network were studied on a thin film of 3. In the same way, solvent effects on the color of the organogels of 3 were also investigated. Correlations could be established between the different stimuli. These results provide a deeper understanding of the precise molecular mechanism of the blue to red transition and of the reversibility of the purple to red transition generally encountered in PDA thermochromism.

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cited By 42International audienceReviewed are crosslinking strategies to stabilize the active-layer morphology of organic solar cells, namely donor-to-donor, donor-to-acceptor and acceptor-to-acceptor. The active layer of a polymer photovoltaic cell is mainly based on a blend of two components: a semiconducting polymer (electron donor) and a fullerene derivative (electron acceptor) to form the bulk heterojunction (BHJ). To offer optimum photovoltaic performances, the morphology of this layer has to be very carefully controlled at the nanoscale. The materials of the BHJ require specific phase segregation enabling the optimum photogenerated exciton diffusion and dissociation, and also to ensure pathways for charge carriers to electrodes. However, such a specific morphology is thermodynamically unstable over time and phase segregation occurs with thermal cycling under solar operating conditions inducing a decrease of solar cell efficiency. This review reports on the recent progress towards obtaining a stable optimized BHJ morphology and improved efficiency stability, using different chemical routes for crosslinking the organic semiconductors. © 2014 Society of Chemical Industry