The purpose of this work is to clarify the mechanism of piezoresistance in a class of ultra-sensitive strain gauges based on metallic films on 2D substrates (“2D/M” films).

Crosslinking is a ubiquitous strategy in polymer engineering to increase the thermomechanical robustness of solid polymers but has been relatively unexplored in the context of π‐conjugated (semiconducting) polymers. Notwithstanding, mechanical stability is key to many envisioned applications of organic electronic devices. For example, the wide‐scale distribution of photovoltaic devices incorporating conjugated polymers may depend on integration with substrates subject to mechanical insult—for example, road surfaces, flooring tiles, and vehicle paint. Here, a four‐armed azide‐based crosslinker (“4Bx”) is used to modify the mechanical properties of a library of semiconducting polymers. Three polymers used in bulk heterojunction solar cells (donors J51 and PTB7‐Th, and acceptor N2200) are selected for detailed investigation. In doing so, it is shown that low loadings of 4Bx can be used to increase the strength (up to 30%), toughness (up to 75%), hardness (up to 25%), and cohesion of crosslinked films. Likewise, crosslinked films show greater physical stability in comparison to non‐crosslinked counterparts (20% vs 90% volume lost after sonication). Finally, the locked‐in morphologies and increased mechanical robustness enable crosslinked solar cells to have greater survivability to four degradation tests: abrasion (using a sponge), direct exposure to chloroform, thermal aging, and accelerated degradation (heat, moisture, and oxygen).

Conventional processes for depositing thin films of conjugated polymers are restricted to those based on vapor, liquid, and solution‐phase precursors. Each of these methods bear some limitations. For example, low‐bandgap polymers with alternating donor–acceptor structures cannot be deposited from the vapor phase, and solution‐phase deposition is always subject to issues related to the incompatibility of the substrate with the solvent. Here, a technique to enable deposition of large‐area, ultra‐thin films (≈20 nm or more), which are transferred from the surface of water, is demonstrated. From the water, these pre‐solidified films can then be transferred to a desired substrate, circumventing limitations such as solvent orthogonality. The quality of these films is characterized by a variety of imaging and electrochemical measurements. Mechanical toughness is identified as a limiting property of polymer compatibility, along with some strategies to address this limitation. As a demonstration, the films are used as the hole‐transport layer in perovskite solar cells, in which their performance is shown to be comparable to controls formed by spin‐coating.