Organic solar cells now exceed 10% efficiency igniting interest not only in the fundamental molecular design of the photoactive semiconducting materials, but also in overlapping fields such as green chemistry, large-scale processing and thin film stability. For these devices to be commercially useful, they must have lifetimes in excess of 10 years. One source of potential instability, is that the two bicontinuous phases of electron donor and acceptor materials in the photoactive thin film bulk heterojunction, change in dimensions over time. Photocrosslinking of the π-conjugated semiconducting donor polymers allows the thin film morphology to be ‘locked’ affording patterned and stable blends with suppressed fullerene acceptor crystallization. This article reviews the performance of crosslinkable polymers, fullerenes and additives used to-date, identifying the most promising.

The performance of 6,13-(bis-triisopropylsilylethynyl)pentacene (TIPS-pentacene) and 1,1′-difluoro-5,11-(bis-triethylsilyl)acetylene-anthra[2,3-b:6,7-b′]dithiophene (TES-FADT) is highly dependent on the morphology enforced by their alkyl groups, with only triisopropylsilylethynyl and triethylsilylethynyl producing viable transistor devices, respectively. Asymmetric triisopropylsilylacetylene- and triethylsilylacetylene-functionalised pentacene and 2-fluoroanthradithiophene were synthesised to study the effects a small change to the solubilising groups has on the thin film morphology.

The prospect of using low cost, high throughput material deposition processes to fabricate organic circuitry and solar cells continues to drive research towards improving the performance of the semiconducting materials utilized in these devices. Conjugated aromatic polymers have emerged as a leading candidate semiconductor material class, due to their combination of their amenability to processing and reasonable electrical and optical performance. Challenges remain, however, to further improve the charge carrier mobility of the polymers for transistor applications and the power conversion efficiency for solar cells. This optimization requires a clear understanding of the relationship between molecular structure and both electronic properties and thin film morphology.In this Account, we describe an optimization process for a series of semiconducting polymers based on an electron rich indacenodithiophene aromatic backbone skeleton. We demonstrate the effect of bridging atoms, alkyl chain functionalization, and co-repeating units on the morphology, molecular orbital energy levels, charge carrier mobility, and solar cell efficiencies. This conjugated unit is extremely versatile with a coplanar aromatic ring structure, and the electron density can be manipulated by the choice of bridging group between the rings. The functionality of the bridging group also plays an important role in the polymer solubility, and out of plane aliphatic chains present in both the carbon and silicon bridge promote solubility. This particular polymer conformation, however, typically suppresses long range organization and crystallinity, which had been shown to strongly influence charge transport. In many cases, polymers exhibited both high solubility and excellent charge transport properties, even where there was no observable evidence of polymer crystallinity. The optical bandgap of the polymers can be tuned by the combination of the donating power of the bridging unit and the electron withdrawing nature of co-repeat units, alternating along the polymer backbone. Using strong donors and acceptors, we could shift the absorption into the near infrared.

We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm2 V–1 s–1, with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packing and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.