Antoine Leliège

Triphenylamine/Tetracyanobutadiene-Based D-A-D π-Conjugated Systems as Molecular Donors for Organic Solar Cells

Thiophene-based D-A-D π-conjugated systems containing triphenylamine end groups connected to a 1,1,4,4-tetracyanobuta-1,3-diene acceptor by oligothiophene chains of variable length have been synthesized. These compounds show interesting light-harvesting properties and low-lying HOMO levels. Preliminary results on bilayer heterojunction solar cells with C(60) as acceptor show power conversion efficiency higher than 1.0%.

Small D-π-A systems with o-phenylene-bridged accepting units as active materials for organic photovoltaics.

Donor-acceptor (D-π-A) systems that combine triarylamine donor blocks and dicyanovinyl (DCV) acceptor groups have been synthesized. Starting from the triphenylamine (TPA)-thiophene-DCV compound (1) as a reference system, various synthetic approaches have been developed for controlling the light-harvesting properties and energy levels of the frontier orbitals in this molecule. Thus, the introduction of methoxy groups onto TPA, the replacement of one phenyl ring of TPA by a thiophene ring, or the extension of the π-conjugating spacer group lead to the modulation of the HOMO level. On the other hand, the fusion of the DCV group onto the vicinal thiophene ring by an ortho-phenylene bridge allows for a specific fine-tuning of the LUMO level. The electronic properties of the molecules were analyzed by using UV/Vis spectroscopy and cyclic voltammetry and the compounds were evaluated as donor materials in basic bilayer planar heterojunction solar cells by using C60 as acceptor material. The relationships between the electronic properties of the donors and the performance of the corresponding photovoltaic devices are discussed. Bilayer planar heterojunction solar cells that used reference compound 1 and C70 afforded power-conversion efficiencies of up to 3.7 %.

Exploiting the potential of 2-((5-(4-(diphenylamino)phenyl)thiophen-2-yl)methylene)malononitrile as an efficient donor molecule in vacuum-processed bulk-heterojunction organic solar cells

A comprehensive experimental study is reported on the optical and electrical characteristics of 2-((5-(4-(diphenylamino)phenyl)thiophen-2-yl)methylene)malononitrile (DPTMM) when used as molecular donor in an organic solar cell (OSC) device structure. A major property of this new donor-type material is an unusually deep highest-occupied molecular orbital (HOMO) level that leads to a high open-circuit voltage (Voc). A reasonably high hole-mobility was also observed in a hole-injection diode configuration. These are both promising factors for high-performance OSCs. In order to fully explore the potential of DPTMM in bulk-heterojunction-based OSCs, a step-wise experimental strategy was applied to optimize film composition and cell architecture. By co-evaporating the DPTMM with C60 to promote exciton dissociation by maximizing the heterojunction area power conversion efficiency (PCE) of 3.0% was achieved. Finally, inserting a buffer layer and a spatial gradient of the donor/acceptor ratio was found to provide better conduction paths for charge carriers. The maximum obtained PCE was 4.0%, which compares favorably with the state-of-the-art of high-performance OSCs. All optimized devices show quite unusual high Voc values up to 1 V.

Small molecular push–pull donors for organic photovoltaics: effect of the heterocyclic π-spacer

A series of (D–π–A) small push–pull molecules involving a triphenylamine electron-rich group (D) connected to a dicyanovinyl electron-deficient unit (A) through different chalcogenophene type π-connectors has been synthesized. Optical and electrochemical results reveal that the replacement of furan by thiophene and selenophene leads to a progressive decrease of the optical band gap of the material and to a parallel increase of hole mobility and power conversion efficiency (PCE). Thus, a PCE of 3.33% has been obtained for a simple air-processed solar cell involving the selenophene-based donor and the [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) as the acceptor.

A bridged low band gap A–D–A quaterthiophene as efficient donor for organic solar cells

α,ω-Bis(dicyanovinyl)quaterthiophene 1 with a median 4,4-diethyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene has been synthesized. UV-Vis absorption data show that the covalent bridging of the inner 2,2′-bithiophene leads to a significant reduction of the HOMO–LUMO gap essentially due to an increase of the HOMO level as confirmed by electrochemical and theoretical results. X-ray diffraction analysis of a single crystal of 1 shows that except for the out-of-plane ethyl groups, the conjugated system displays a quasi-planar geometry while the molecular packing exhibits strong π-stacking interactions and multiple short intermolecular contacts. Quaterthiophene 1 has been used as active donor material in organic solar cells of various architectures including bi-layer planar hetero-junctions and hybrid co-evaporated bulk hetero-junctions with C60 as electron acceptor material. A maximum conversion efficiency of 4.30% is obtained with a hybrid co-evaporated device. These results are discussed in terms of structure–properties relationships with reference to the open-chain parent α,ω-bis(dicyanovinyl)quaterthiophene 2.