Organic Single-Crystalline p–n Heterojunctions for High-Performance Ambipolar Field-Effect Transistors and Broadband Photodetectors

Organic semiconducting single crystals are ideal building blocks for organic field-effect transistors (OFETs) and organic photodetectors (OPDs) because they can potentially exhibit the best charge transport and photoelectric properties in organic materials. Nevertheless, it is usual for single-crystal OFETs to be built from one kind of organic material in which the dominant transport is either electron or hole; such OFETs show unipolar charge transport. Furthermore, single-crystal OPDs present high performance only in restricted regions because of the limited absorption of one-component single crystals. In an ideal situation, devices which comprise both electron- and hole-transporting single crystals with complementary absorptions, such as single-crystalline p-n heterojunctions (SCHJs), can permit broadband photoresponse and ambipolar charge transport. In this paper, a solution-processing crystallization strategy to prepare an SCHJ composed of C₆₀ and 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-PEN) was shown. These SCHJs demonstrated ambipolar charge-transport characteristics in OFETs with a balanced performance of 2.9 cm² V⁻¹ s⁻¹ for electron mobility and 2.7 cm² V⁻¹ s⁻¹ for hole mobility. This demonstration is the first of single-crystal OFETs in which both electron and hole mobilities were over 2.5 cm² V⁻¹ s⁻¹. OPDs fabricated upon as-prepared SCHJs exhibited highly sensitive photoconductive properties ranging from ultraviolet to visible and further to near-infrared regions as a result of complementary absorption between C₆₀ and TIPS-PEN, thereby attaining photoresponsivities that are among the highest reported values within the OPDs. This work would provide valuable references for developing novel SCHJ systems to achieve significant progress in high-performance ambipolar OFETs and broadband OPDs.