Nicolas Leclerc

High-Performance Solution-Processed Solar Cells and Ambipolar Behavior in Organic Field-Effect Transistors with Thienyl-BODIPY Scaffoldings

Green-absorbing dipyrromethene dyes engineered from bis-vinyl-thienyl modules are planar molecules, exhibiting strong absorption in the 713-724 nm range and displaying comparable electron and hole mobilities in thin films (maximum value 1 × 10(-3) cm(2)/(V·s)). Bulk heterojunction solar cells assembled with these dyes and a fullerene derivative (PC(61)BM) at a low ratio give a power conversion efficiency as high as 4.7%, with short-circuit current values of 14.2 mA/cm(2), open-circuit voltage of 0.7 V, and a broad external quantum efficiency ranging from 350 to 920 nm with a maximum value of 60%.

A New Supramolecular Route for Using Rod-Coil Block Copolymers in Photovoltaic Applications

A new polymer blend formed by poly(3-hexylthiophene)-poly(4-vinylpyridine) (P3HT-P4VP) block copolymers and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is reported. The P4VP and PCBM are mixed together by weak supramolecular interactions, and the resulting materials exhibit microphase separated morphologies of electron-donor and electron-acceptor rich domains. The properties of the blend, used in photovoltaic devices as active layers, are also discussed.

Absorption tuning of monosubstituted triazatruxenes for bulk heterojunction solar cells.

A series of triazatruxene (TAT)-functionalized Bodipy dyes were prepared by a sequence of reactions involving either cross-coupling reactions promoted by Pd complexes or a Knoevenagel reaction leading to a vinyl linker. The new dyes show large absorption coefficients and fluorescence quantum yields as well as interesting electrochemical properties. The blue dyes of this series exhibit interesting photovoltaic effects (V(OC) = 0.83 V, J(SC) = 3.6 mA/cm(2), efficiency 0.9%) in bulk heterojunction solar cells, due to the good hole mobility imported by the TAT entity.

Impact of Backbone Fluorination on π-Conjugated Polymers in Organic Photovoltaic Devices: A Review

Solution-processed bulk heterojunction solar cells have experienced a remarkable acceleration in performances in the last two decades, reaching power conversion efficiencies above 10%. This impressive progress is the outcome of a simultaneous development of more advanced device architectures and of optimized semiconducting polymers. Several chemical approaches have been developed to fine-tune the optoelectronics and structural polymer parameters required to reach high efficiencies. Fluorination of the conjugated polymer backbone has appeared recently to be an especially promising approach for the development of efficient semiconducting polymers. As a matter of fact, most currently best-performing semiconducting polymers are using fluorine atoms in their conjugated backbone. In this review, we attempt to give an up-to-date overview of the latest results achieved on fluorinated polymers for solar cells and to highlight general polymer properties’ evolution trends related to the fluorination of their conjugated backbone.

Perylenediimide-based donor-acceptor dyads and triads: impact of molecular architecture on self-assembling properties.

Perylenediimide-based donor-acceptor co-oligomers are particularly attractive in plastic electronics because of their unique electro-active properties that can be tuned by proper chemical engineering. Herein, a new class of co-oligomers has been synthesized with a dyad structure (AD) or a triad structure (DAD and ADA) in order to understand the correlations between the co-oligomer molecular architecture and the structures formed by self-assembly in thin films. The acceptor block A is a perylene tetracarboxyl diimide (PDI), whereas the donor block D is made of a combination of thiophene, fluorene, and 2,1,3-benzothiadiazole derivatives. D and A blocks are linked by a short and flexible ethylene spacer to ease self-assembling in thin films. Structural studies using small and wide X-ray diffraction and transmission electron microscopy demonstrate that AD and ADA lamellae are made of a double layer of co-oligomers with overlapping and strongly π-stacked PDI units because the sectional area of the PDI is about half that of the donor block. These structural models allow rationalizing the absence of organization for the DAD co-oligomer and therefore to draw general rules for the design of PDI-based dyads and triads with proper self-assembling properties of use in organic electronics.

Electronic Properties and Photovoltaic Performances of a Series of Oligothiophene Copolymers Incorporating Both Thieno[3,2-b]thiophene and 2,1,3-Benzothiadiazole Moieties.

A series of donor-acceptor alternated conjugated copolymers, composed of thiophene, bithiophene, thieno[3,2-b]thiophene, and 2,1,3-benzothiadiazole units and differing from each other by the nature and the number of 3-alkylthiophene in the backbone, have been synthesized by Stille cross-coupling polymerization. The materials optical and electrochemical properties, in solution and in thin films, have been investigated using UV-Visible absorption and cyclic voltammetry. Bulk heterojunction solar cells using blends of the newly synthesized copolymers, as electron donor, and C60-PCBM or C70-PCBM, as electron transporting material, have been elaborated. A maximum power conversion efficiency of 1.8% is achieved with a 1:4 PPBzT(2) -C12:C70-PCBM weight ratio.

Efficiency enhancement of polymer photovoltaic devices using thieno-thiophene based copolymers as nucleating agents for polythiophene crystallization

A copolymer including thieno-thiophene units (DHPT3) has been synthesized and used as crystallization nucleating agent in the active layer of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) bulk heterojunction photovoltaic devices. We demonstrate in this work that the addition of DHPT3 in P3HT/PCBM thin films induces a marked structural ordering of the polythiophene phase. This structural order enhances the charge carrier transport properties and enlarges the active layer absorption spectrum. The photovoltaic devices power conversion efficiency prior to thermal annealing could be enhanced by a factor of 2 by adding 5% of DHPT3 into the blend.

Synthesis by Direct Arylation of Thiazole–Derivatives: Regioisomer Configurations–Optical Properties Relationship Investigation

The synthesis of thiazole(Tz)-based regioisomer materials using selective direct arylation to avoid any protection steps has been developed. A series of trimers in which the Tz groups sandwich either an electron-rich or an electron-deficient unit, with a regioselective orientation of the respective Tz unit, has therefore been synthesized. This chemical strategy has also been followed to synthesize a second series of pentamers in which the Tz group is used as a π-conjugated bridge between an electron-rich central unit and electron-deficient end-capping groups and vice versa. On both trimers and pentamers, the effect of Tz orientation on the conjugation properties of the synthesized materials was investigated by a combination of experimental measurements and density functional theory calculations. This study highlights that control of the orientation of the Tz unit leads to the synthesis of the most conjugated regioisomer derivative. The present work gives chemical synthesis tools for the synthesis of selectively oriented Tz-based materials as well as a general guideline for the design of Tz-based materials with the highest conjugation length, including the Tz-orientation effect.

Thiazole-based scaffolding for high performance solar cells

An interesting way of decreasing both HOMO and LUMO energy levels simultaneously while keeping the band-gap constant in soluble electron-donor small molecules for photovoltaic applications is presented. This consists in the replacement of thiophene rings by thiazole units in small molecules based on the alternation of electron-rich and electron-deficient moieties. A new diketopyrrolopyrrole-based dumbbell-shaped electron-donor soluble molecule for organic photovoltaic applications has been synthesized and characterized. It includes thiazole units as linkers between the bis-lactam core and the triazatruxene moieties used as π-stacking platforms. A power conversion efficiency of 6.3% has been attained with this thiazole derivative and in particular with an increase of the open-circuit voltage of 0.15 V with respect to the thiophene-based organic semiconducting counterpart. This open-circuit voltage increase is due to the lowering of the HOMO level of the thiazole derivative while its LUMO level has also been stabilized as highlighted by the similar band-gap measured for the thiazole and thiophene derivatives.

A deep-purple-grey thiophene–benzothiadiazole–thiophene BODIPY dye for solution-processed solar cells

In this work we explore the synthesis of an extended 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene dye (BODIPY) engineered from thiophene–benzothiadiazole–thiophene modules linked in the 3,5-substitution positions. We found that this highly soluble dye absorbs up to 800 nm in solution and up to 900 nm in thin films. An effective charge transfer absorption band was found at around 479 nm. The hybrid dye emits at 778 nm with a quantum yield of about 6%. Similar electrochemical and optical gaps were determined about 1.36 eV. When deposited in thin films the dye exhibits an ambipolar nature with well-balanced hole and electron mobilities. Bulk heterojunction solar cells based upon this dye blended with [6,6]phenylC61or71butyricacid methylester (PC61BM or PC71BM) provide a power conversion efficiency of about 1.26% upon a mild thermal annealing.