Impact of backbone fluorination on nanoscale morphology and excitonic coupling in polythiophenes.

Fluorination represents an important strategy in developing high-performance conjugated polymers for photovoltaic applications. Here, we use regioregular poly(3-ethylhexylthiophene) (P3EHT) and poly(3-ethylhexyl-4-fluorothiophene) (F-P3EHT) as simplified model materials, using single-molecule/aggregate spectroscopy and molecular dynamic simulations, to elucidate the impacts of backbone fluorination on morphology and excitonic coupling on the molecular scale. Despite its high regioregularity, regioregular P3EHT exhibits a rather broad distribution in polymer chain conformation due to the strong steric hindrance of bulky ethylhexyl side chains. This conformational variability results in disordered interchain morphology even between a few chains, prohibiting long-range effective interchain coupling. In stark contrast, the experimental and molecular dynamic calculations reveal that backbone fluorination of F-P3EHT leads to an extended rod-like single-chain conformation and hence highly ordered interchain packing in aggregates. Surprisingly, the ordered and close interchain packing in F-P3EHT does not lead to strong excitonic coupling between the chains but rather to dominant intrachain excitonic coupling that greatly reduces the molecular energetic heterogeneity.

Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties.

The microstructure of the active blend layer has been shown to be a critically important factor in the performance of organic solar devices. Block copolymers provide a potentially interesting avenue for controlling this active layer microstructure in solar cell blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation (KCTP) conditions. We compare the behavior of the block copolymer to that of the corresponding homopolymer blends. In both types of system, we find the fluorinated segments tend to dominate the UV-visible absorption and molecular vibrational spectral features, as well as the thermal behavior. In the block copolymer case, non-fluorinated segments appear to slightly frustrate the aggregation of the more fluorinated block. However, in situ temperature dependent Raman spectroscopy shows that the intramolecular order is more thermally stable in the block copolymer than in the corresponding blend, suggesting that such materials may be interesting for enhanced thermal stability of organic photovoltaic active layers based on similar systems.

Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes.

We report two strategies toward the synthesis of 3-alkyl-4-fluorothiophenes containing straight (hexyl and octyl) and branched (2-ethylhexyl) alkyl groups. We demonstrate that treatment of the dibrominated monomer with 1 equiv of alkyl Grignard reagent leads to the formation of a single regioisomer as a result of the pronounced directing effect of the fluorine group. Polymerization of the resulting species affords highly regioregular poly(3-alkyl-4-fluoro)thiophenes. Comparison of their properties to those of the analogous non-fluorinated polymers shows that backbone fluorination leads to an increase in the polymer ionization potential without a significant change in optical band gap. Fluorination also results in an enhanced tendency to aggregate in solution, which is ascribed to a more co-planar backbone on the basis of Raman and DFT calculations. Average charge carrier mobilities in field-effect transistors are found to increase by up to a factor of 5 for the fluorinated polymers.

Measurement of Cohesion and Adhesion of Semiconducting Polymers by Scratch Testing: Effect of Side-Chain Length and Degree of Polymerization.

Most advantages of organic electronic materials are enabled by mechanical deformability, as flexible (and stretchable) devices made from these materials must be able to withstand roll-to-roll printing and survive mechanical insults from the external environment. Cohesion and adhesion are two properties that dictate the mechanical reliability of a flexible organic electronic device. In this paper, progressive-load scratch tests are used for the first time to correlate the cohesive and adhesive behavior of poly(3-alkylthiophenes) (P3ATs) with respect to two molecular parameters: length of the alkyl side chain and molecular weight. In contrast to metrological techniques based on buckling or pull testing of pseudofreestanding films, scratch tests reveal information about both the cohesive and adhesive properties of thin polymeric films from a single procedure. Our data show a decrease in cohesion and adhesion, that is, a decrease in overall mechanical robustness, with increasing length of the side chain. This behavior is likely due to increases in free volume and concomitant decreases in the glass transition temperature. In contrast, we observe increases in both the cohesion and adhesion with increasing molecular weight. This behavior is attributed to an increased density of entanglements with high molecular weight, which manifests as increased extensibility. These observations are consistent with the results of molecular dynamics simulations. Interestingly, the normal (applied) forces associated with cohesive and adhesive failure are directly proportional to the average degree of polymerization, as opposed to simply the molecular weight, as the length of the alkyl side chain increases the molecular weight without increasing the degree of polymerization.

Pentafluorobenzene end-group as a versatile handle for para fluoro "click" functionalization of polythiophenes.

A convenient method of introducing pentafluorobenzene (PFB) as a single end-group in polythiophene derivatives is reported via in situ quenching of the polymerization. We demonstrate that the PFB-group is a particularly useful end-group due to its ability to undergo fast nucleophilic aromatic substitutions. Using this molecular handle, we are able to quantitatively tether a variety of common nucleophiles to the polythiophene backbone. The mild conditions required for the reaction allows sensitive functional moieties, such as biotin or a cross-linkable trimethoxysilane, to be introduced as end-groups. The high yield enabled the formation of a diblock rod-coil polymer from equimolar reactants under transition metal-free conditions at room temperature. We further demonstrate that water soluble polythiophenes end-capped with PFB can be prepared via the hydrolysis of an ester precursor, and that such polymers are amenable to functionalization under aqueous conditions.

Comparison of Methods for Determining the Mechanical Properties of Semiconducting Polymer Films for Stretchable Electronics.

This paper describes a comparison of two characterization techniques for determining the mechanical properties of thin-film organic semiconductors for applications in soft electronics. In the first method, the film is supported by water (film-on-water, FOW), and a stress-strain curve is obtained using a direct tensile test. In the second method, the film is supported by an elastomer (film-on-elastomer, FOE), and is subjected to three tests to reconstruct the key features of the stress-strain curve: the buckling test (tensile modulus), the onset of buckling (yield point), and the crack-onset strain (strain at fracture). The specimens used for the comparison are four poly(3-hexylthiophene) (P3HT) samples of increasing molecular weight (Mn = 15, 40, 63, and 80 kDa). The methods produced qualitatively similar results for mechanical properties including the tensile modulus, the yield point, and the strain at fracture. The agreement was not quantitative because of differences in mode of loading (tension vs compression), strain rate, and processing between the two methods. Experimental results are corroborated by coarse-grained molecular dynamics simulations, which lead to the conclusion that in low molecular weight samples (Mn = 15 kDa), fracture occurs by chain pullout. Conversely, in high molecular weight samples (Mn > 25 kDa), entanglements concentrate the stress to few chains; this concentration is consistent with chain scission as the dominant mode of fracture. Our results provide a basis for comparing mechanical properties that have been measured by these two techniques, and provide mechanistic insight into fracture modes in this class of materials.