Emergent Insulator–Metal Transition with Tunable Optical and Electrical Gap in Thin Films of a Molecular Conducting Composite

[Image: see text] Composites exhibit unique synergistic properties emerging when components with different properties are combined. The tuning of the energy bandgap in the electronic structure of the material allows designing tailor-made systems with desirable mechanical, electrical, optical, and/or thermal properties. Here, we study an emergent insulator–metal transition at room temperature in bilayered (BL) thin-films comprised of polycarbonate/molecular-metal composites. Temperature-dependent resistance measurements allow monitoring of the electrical bandgap, which is in agreement with the optical bandgap extracted by optical absorption spectroscopy. The semiconductor-like properties of BL films, made with bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF or ET) α-ET(2)I(3) (nano)microcrystals as two-dimensional molecular conductor on one side and insulator polycarbonate as a second ingredient, are attributed to an emergent phenomenon equivalent to the transition from an insulator to a metal. This made it possible to obtain semiconducting BL films with tunable electrical/optical bandgaps ranging from 0 to 2.9 eV. A remarkable aspect is the similarity close to room temperature of the thermal and mechanical properties of both composite components, making these materials ideal candidates to fabricate flexible and soft sensors for stress, pressure, and temperature aiming at applications in wearable human health care and bioelectronics.