Organic solar cells (OSCs) are lightweight, have adaptable colors, and can be produced in low‐cost procedures on transparent and flexible surfaces. This makes them attractive for markets in which other technologies cannot compete, for example in architectural and consumer product integration. However, both efficiencies and long term operational stability of OSCs do not yet meet the standards set by their inorganic counterparts. This review compiles the growing knowledge about how nanostructured carbon materials, such as fullerenes and carbon nanotubes, decisively influence the operational stability of organic photovoltaics. Firstly, important degradation pathways are introduced and a differential detection scheme is set up to find the dominant loss channel by means of state‐of‐the‐art characterization methods. Then, fullerenes ability to both stabilize and destabilize the donor polymer against photooxidation via different mechanisms (e.g., inner filter effect or radical scavenging) is examined in detail. The “burn‐in” problem, an initial rapid efficiency loss in PC60BM‐based OSCs, is shown to derive from light‐induced PC60BM dimerization, an effect that can also be positively exploited to reduce thermal degradation. Finally, thermal stabilization via additional approaches involving the fullerene derivative, such as crosslinking or incorporation into block copolymers, is presented.

In the printing industry, the exploitation of triggerable materials that can have their surface properties altered on application of a post-deposition external stimulus has been crucial for the production of robust layers and patterns. To this end, herein, a series of clickable poly(R-alkyl p-styrene sulfonate) homopolymers, with systematically varied thermally-labile protecting groups, has been synthesised via reversible addition-fragmentation chain transfer (RAFT) polymerisation. The polymer range has been designed to offer varied post-deposition thermal treatment to switch them from hydrophobic to hydrophilic. Suitable RAFT conditions have been identified to produce well-defined homopolymers (Đ, M w /M n < 1.11 in all cases) at high monomer conversions (>80% for all but one monomer) with controllable molar mass. Poly(p-styrene sulfonate) with an isobutyl protecting group has been shown to be the most readily thermolysed polymer that remains stable at room temperature, and was thus investigated further by incorporation into a diblock copolymer, P3HT-b-PiBSS, by click chemistry. The strategy for preparation of thermal modifiable block copolymers exploiting R-protected p-styrene sulfonates and azide-alkyne click chemistry presented herein allows the design of new, roll-to-roll processable materials for potential application in the printing industry, particularly organic electronics.

Large-scale introduction of Organic Solar Cells (OSCs) onto the market is currently limited by their poor stability in light and air, factors present in normal working conditions for these devices. Thus, great efforts have to be undertaken to understand the photodegradation mechanisms of their organic materials in order to find solutions that mitigate these effects. This study reports on the elucidation of the photodegradation mechanisms occurring in a low bandgap polymer, namely, Si-PCPDTBT (poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl]). Complementary analytical techniques (AFM, HS-SPME-GC-MS, UV–vis and IR spectroscopy) have been employed to monitor the modification of the chemical structure of the polymer upon photooxidative aging and the subsequent consequences on its architecture and nanomechanical properties. Furthermore, these different characterization techniques have been combined with a theoretical approach based on quantum chemistry to elucidate the evolution of the polymer alkyl side chains and backbone throughout exposure. Si-PCPDTBT is shown to be more stable against photooxidation than the commonly studied p-type polymers P3HT and PCDTBT, while modeling demonstrated the benefits of using silicon as a bridging atom in terms of photostability.