Nitrogen-Containing Perylene Diimides: Molecular Design, Robust Aggregated Structures, and Advances in n-Type Organic Semiconductors

Organic semiconductors (OSCs) have attracted much attention because of their potential applications for flexible and printed electronic devices and thus have been extensively investigated in a variety of research fields, such as organic chemistry, solid-state physics, and device physics and engineering. Organic thin-film transistors (OTFTs), a class of OSC-based devices, have been expected to be an alternative of silicon-based metal oxide semiconductor field-effect transistors (MOS-FETs), which is the indispensable element for most of the current electronic devices. However, the noncovalently aggregated, van der Waals solid nature of the OSCs, by contrast to covalently bound silicon, conventionally exhibits lower carrier mobilities, limiting the practical applications of OTFTs. In particular, electron-transporting (i.e., n-type) OSCs lag behind their hole-transporting (p-type) counterparts in carrier mobility and ambient stability as OTFTs. This is primarily because of the difficulty in achieving compatibility between the aggregated structure exhibiting excellent carrier mobility and that with enough electron affinity. Recent understandings of carrier transport in OSCs explain that large and two-dimensionally isotropic transfer integrals coupled with small fluctuations are crucial for high carrier mobilities. In addition, from a practical point of view, the compatibility with practical device processes is highly required. Rational molecular design principles, therefore, are still demanded for developing OSCs and OTFTs toward high-end device applications. Herein, we will show our recent progress in the development of n-type OSCs with the key pi-electron core (pi-core) of benzo[de]isoquinolino[1,8-gh]quinolinetetracarboxylic diimide (BQQDI) on the basis of single-crystal OTFT technologies and the band-transport model enabled by two-dimensional molecular packing arrangements. The critical point is the introduction of electronegative nitrogen atoms into the pi-core: the nitrogen atoms in BQQDI not only deepen the molecular orbital energies but also allow hydrogen-bonding-like attractive intermolecular interactions to control the aggregated structures, unlike the conventional role of the nitrogen introduced into OSCs only for the former role. Hence, the BQQDI analogues exhibit air-stable OTFT behavior and two-dimensional brickwork packing structures. Specifically, phenethyl-substituted analogue (PhC2-BQQDI) has been shown as the first principal BQQDI-based material, demonstrating solution-processable thin-film single crystals, fewer anisotropic transfer integrals, and an effective suppression of molecular motions, leading to band-like electron-transport properties and stress-durable nchannel OTFT performances, in conjunction with the support of computational calculations. Insights into more fundamental points of view have been found by side-chain derivatization and OTFT studies on polycrystalline and single-crystal films. We hope that this Account provides readers with new strategies for designing high-performance OSCs by two-dimensional control of the aggregated structures.