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We propose a set of design rules with a model Hamiltonian that allows electrons to form attracting pairs through the exploitation of a new combination of resonant band alignment and Coulombic repulsion. The pair bands and single particle bands in various lattices are calculated and compared in energy, and regions of net attraction are identified. This work provides guidelines for the construction of molecular systems, nanocrystals, and nanoparticle arrays with the potential for superconductivity. [ABSTRACT FROM AUTHOR]

We report here π-conjugated small molecules and polymers based on the new π-acceptor building block, bithiophenesulfonamide (BTSA). Molecular orbital computations and optical, electrochemical, and crystal structure analyses illuminate the architecture and electronic structure of the BTSA unit versus other acceptor building blocks. Field-effect transistors and photovoltaic cells demonstrate that BTSA is a promising unit for the construction of π-conjugated semiconducting materials. [ABSTRACT FROM AUTHOR]

A new series of metal-free organic chromophores (TPA-TTAR-A (l), TPA-T-TTAR-A (2), TPA-TTART- A (3), and TPA-T-TTAR-T-A (4)) are synthesized for application in dye-sensitized solar cells (DSSC) based on a donor-π-bridge-acceptor (D-π-A) design. Here a simple triphenylamine (TPA) moiety serves as the electron donor, a cyanoacrylic acid as the electron acceptor and anchoring group, and a novel tetrathienoacene (TTA) as the π-bridge unit. Because of the extensively conjugated TTA π-bridge, these dyes exhibit high extinction coefficients (4.5-5.2 X 104 M-1 cm-1). By strategically inserting a thiophene spacer on the donor or acceptor side of the molecules, the electronic structures of these TTA-based dyes can be readily tuned. Furthermore, addition of a thiophene spacer has a significant influence on the dye orientation and self-assembly modality on TiO2 surfaces. The insertion of a thiophene between the π-bridge and the cyanoacrylic acid anchoring group in TPA-TTAR-T-A (dye 3) promotes more vertical dye orientation and denser packing on TiO2 (molecular footprint = 79 Ų), thus enabling optimal dye loading. Using dye 3, a DSSC power conversion efficiency (PCE) of 10.1% with Voc = 0.833 V, JK = 16.5 mA/cm², and FF = 70.0% is achieved, among the highest reported to date for metal-free organic DSSC sensitizers using an I-/I3- redox shuttle. Photophysical measurements on dye-grafted TiO2 films reveal that the additional thiophene unit in dye 3 enhances the electron injection efficiency, in agreement with the high quantum efficiency. [ABSTRACT FROM AUTHOR]

Rational creation of polymeric semiconductors from novel building blocks is critical to polymer solar cell (PSC) development. We report a new series of bithiopheneimide-based donor-acceptor copolymers for bulk-heterojunction (BHJ) PSCs. The bithiopheneimide electron-deficiency compresses polymer bandgaps and lowers the HOMOs—essential to maximize power conversion efficiency (PCE). While the dithiophene bridge progression R2Si→R2Ge minimally impacts bandgaps, it substantially alters the HOMO energies. Furthermore, imide N-substituent variation has negligible impact on polymer opto-electrical properties, but greatly affects solubility and microstructure. Grazing incidence wide-angle X-ray scattering (GIWAXS) indicates that branched N-alkyl substituents increased polymer π-π spacings vs linear N-alkyl substituents, and the dithienosilole-based PBTISi series exhibits more ordered packing than the dithienogermole-based PBTIGe analogues. Further insights into structure-property-device performance correlations are provided by a thieno[3,4-c]pyrrole-4,6-dione (TPD)-dithienosilole copolymer PTPDSi. DFT computation and optical spectroscopy show that the TPD-based polymers achieve greater subunit-subunit coplanarity via intramolecular (thienyl)S···O(carbonyl) interactions, and GIWAXS indicates that PBTISi-C8 has lower lamellar ordering, but closer π-π spacing than does the TPD-based analogue. Inverted BHJ solar cells using bithiopheneimide-based polymer as donor and PC71BM as acceptor exhibit promising device performance with PCEs up to 6.41% and Voc > 0.80 V. In analogous cells, the TPD analogue exhibits 0.08 V higher Voc with an enhanced PCE of 6.83%, mainly attributable to the lower-lying HOMO induced by the higher imide group density. These results demonstrate the potential of BTI-based polymers for high-performance solar cells, and provide generalizable insights into structure-property relationships in TPD, BTI, and related polymer semiconductors. [ABSTRACT FROM AUTHOR]

The influence of solubilizing substituents on the photovoltaic performance and thin-film blend morphology of new benzo[1,2-b:6,5-b′]dithiophene (bBDT) based small molecule donor semiconductors is investigated. Solar cells based on bBDT(TDPP)2-PC71BM with two different types of side chains exhibit high power conversion efficiencies, up to 5.53%. [ABSTRACT FROM AUTHOR]