Mark D. Watson

High‐mobility Ambipolar Transistors and High‐gain Inverters from a Donor–Acceptor Copolymer Semiconductor

Ambipolar organic field-effect transistors (OFETs), which are capable of both p- and n-channel operations, are gaining attention as an alternative approach to mimicking complementary metal-oxide semiconductor (CMOS) digital integrated circuits for achieving high-performance and cost-effective circuits in organic electronics. [1‐13] Low power dissipation and high performance are some of the major advantages of CMOS technology over non-complementary ones. [14] Power consumption is minimized in CMOS circuits because the component transistors are selectively turned on only when the circuit is switching, otherwise they are off at the steady state. The better performance of a CMOS circuit in terms of sharp switching and high noise immunity arises because every elemental transistor actively contributes to the function of the circuit. [14] Most efforts towards CMOS-like circuits in organic electronics have focused on utilizing distinct p- and n-type semiconductors. [1,15] However, the necessity of lateral patterning of semiconductors in CMOS circuits makes device fabrication on a common substrate a very complex process. Ambipolar OFETs represent an approach to high-performance CMOS-like circuits that minimize patterning and complex fabrication processes. [1] Ambipolar transistors are also of interest in fundamental studies of charge transport in organic semiconductors [1,6,16] as well as the development of efficient light-emitting transistors. [8,17‐21]

Conjugated polymers from naphthalene bisimide.

Stille coupling of regioisomerically pure dibromonaphthalene bisimides (NBI) with various stannylated thiophene-based monomers yields (very) high molecular weight donor-acceptor conjugated polymers. Electrochemical and optical absorption measurements reveal that LUMO energies are essentially invariant and dictated by the NBI units, while HOMO energies are dictated by the thienyl comonomers. Optical energy gaps ranging from 1.7 to 1.1 eV are thus obtained. The polymers are also characterized by differential scanning calorimetry and fiber WAXD.

Phthalimide-Based Polymers for High Performance Organic Thin-Film Transistors

The synthesis and characterization of two new thiophene copolymers with backbone phthalimide units is reported. Thin-film optical and wide-angle X-ray diffraction measurements indicate extended electronic conjugation and close intermolecular pi-stacking for both polymers. Ambient carrier mobility of thin-film transistors prepared from these polymers is as high as 0.28 cm(2)/(V s) with an on/off ratio greater than 10(5).

Highly Fluorinated Benzobisbenzothiophenes

Expedient, facile syntheses of highly fluorinated benzobisbenzothiophenes (BBBT) are reported. Defined peripheral arrangements of sulfur and fluorine atoms lead to extensive crystalline networks of edge-to-edge S-F close contacts. The effects of various substitution patterns on self-assembly and electronic properties are described.

Efficient solar cells based on a new phthalimide-based donor–acceptor copolymer semiconductor: morphology, charge-transport, and photovoltaic properties

Bulk heterojunction solar cells based on blends of the new low band gap donor–acceptor copolymer, poly(N-(dodecyl)-3,6-bis(4-dodecyloxythiophen-2-yl)phthalimide) (PhBT12), and fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) or [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) were systematically investigated. The PhBT12/fullerene blend films were found to exhibit a crystalline nanoscale morphology with space-charge-limited mobility of holes as high as 4.0 × 10−4 cm2/Vs without thermal annealing, leading to moderately efficient devices. The performance of the solar cells varied significantly with PhBT12/fullerene composition, reaching a power conversion efficiency of 2.0% with a current density of 6.43 mA/cm2 and a fill factor of 0.55 for the 1:1 PhBT12/PC71BM blend devices. However, thermally annealed (120 °C) PhBT12/fullerene blend devices had negligible photovoltaic properties due to micrometer scale phase separation of the blends which is attributed to the long side chains. We expect that better photovoltaic performance can be achieved by modifying the polymer side chain length and the device processing as well. These results show that phthalimide-based donor–acceptor copolymer semiconductors, exemplified by PhBT12, are promising low band gap materials for developing efficient bulk heterojunction solar cells.

Conjugated polymers with large effective Stokes shift: benzobisdioxole-based poly(phenylene ethynylene)s.

Phenyleneethynylene-based conjugated copolymers using benzo[1,2-d:4,5-d]bis[1,3]dioxole (BDO) in the repeating unit are reported. The electronic structure of the BDO unit imparts a localized HOMO topology while the LUMO is delocalized over the polymer backbone, so that the lowest optical absorption band of the polymer has considerable intramolecular charge transfer character. This contrasts with published donor-acceptor polymers with localized LUMO and delocalized HOMO. The very large Stokes shifts of the monomers, which are due to the small oscillator strength of the lowest optical transition, are largely retained in the polymers as a result of covalently constrained dihedral angles in the substituents (not the backbone), as predicted/explained by calculations.

Benzodichalcogenophenes with perfluoroarene termini.

Benzodichalcogenophenes are functionalized at their termini via SN Ar reactions of their bismetalates with perfluoroarenes. The identities of X, Y, and W are varied to study the effects on LUMO energy levels and crystallization motif. X-ray crystallography reveals that nearly all new derivatives crystallize with coplanar ring systems within slipped 1D or 2D pi-stacks.