Ultrafast charge transfer in solid-state films of pristine cyanine borate and blends with fullerene

Photoinduced electron transfer in light-absorbing materials is the first step towards charge separation and extraction in small molecule-based organic solar cells. The excited state dynamics of the cyanine dye cation Cy3 paired with a tetraphenylborate counter-anion (Cy3-B) was studied in pristine solid-state films of the dye and in blends with the electron acceptor material PCBM. Here we show that photoexcited Cy3-B in pure films undergoes intra-ion pair reductive quenching on the picosecond time scale, while in blends with PCBM sub-picosecond formation of the Cy3 oxidized species is observed upon electron injection from the dye excited state into the fullerene. Kinetic competition between light-induced electron- and hole transfer processes strongly depends on the PCBM content in the blends. A high PCBM loading produces a fully intermixed phase, where the cyanine oxidized states appear on ultrashort (<160 fs) time scales. Lower PCBM contents, in contrast, lead to a Cy3-B segregated phase on top of the intermixed phase and slower excited state quenching. These findings show that the phase morphology indeed controls to a large extent the efficiency of primary photoinduced charge separation, on which small molecule-based organic photovoltaic cells rely

Dissociation of charge transfer states and carriers separation in bilayer organic solar cells - A time-resolved electroabsorption spectroscopy study

Ultrafast optical probing of the electric field by means of Stark effect in planar heterojunction cyanine dye / fullerene organic solar cells enables to directly monitor the dynamics of free electron formation during the dissociation of interfacial charge transfer (CT) states. Motions of electrons and holes is scrutinized separately by selectively probing the Stark shift dynamics at selected wavelengths. It is shown that only charge pairs with an effective electron-hole separation distance of less than 4 nm are created during the dissociation of Frenkel excitons. Dissociation of the Coulombically bound charge pairs is identified as the major rate-limiting step for charge carriers’ generation. Interfacial CT states split into free charges on the time-scale of tens to hundreds of picoseconds, mainly by electron escape from the Coulomb potential over a barrier that is lowered by the electric field. The motion of holes in the small molecule donor material during the charge separation time is found to be insignificant

Using the Stark effect to understand charge generation in organic solar cells

We have used a femtosecond-resolved spectroscopic technique based on the Stark effect (electromodulated differential absorption) in order to investigate free charge generation and charge drift in solar cell devices of neat conjugated polymer pBTTT and in its 1:1 (by weight) blend with PCBM. In the latter, the fullerene molecules intercalate between the polymer side-chains, yielding a co-crystal phase. Our results show that free charge generation in both materials is ultrafast and strongly dependent on the applied reverse bias. Charge drift to the electrodes (under strong reverse bias) occurs with comparable dynamics on the 1.2 ns time scale for neat pBTTT and the blend, and is probably dominated by hole transport within/between polymer chains

Chaotropic Agents Boosting the Performance of Photo-ionic Cells

Photo-ionic cells are a simple and scalable concept for direct solar energy storage, where the redox fuels produced by the photoreaction are separated in different phases to prevent recombination. The presence of chaotropic agents such as urea, that break the structure of water, was found to drastically enhance the quantum yield; a ten-fold increase of quantum yield to over 13 % was achieved by addition of chaotropes into a system based on the reductive quenching of Azure B by Co(II)-EDTA in water and the extraction of the leuco-dye in 1,2-dichloroethane

The Fate of Electron–Hole Pairs in Polymer:Fullerene Blends for Organic Photovoltaics

There has been long-standing debate on how free charges are generated in donor:acceptor blends that are used in organic solar cells, and which are generally comprised of a complex phase morphology, where intermixed and neat phases of the donor and acceptor material co-exist. Here we resolve this question, basing our conclusions on Stark effect spectroscopy data obtained in the absence and presence of externally applied electric fields. Reconciling opposing views found in literature, we unambiguously demonstrate that the fate of photo generated electron–hole pairs —whether they will dissociate to free charges or geminately recombine— is determined at ultrafast times, despite the fact that their actual spatial separation can be much slower. Our insights are important to further develop rational approaches towards material design and processing of organic solar cells, assisting to realize their purported promise as lead-free, third-generation energy technology that can reach efficiencies over 10%

Collision entre amateurs de cyclotourisme : les vertus de l'article 1384, alinéa 1 !

Note sous CA Metz, 1ère ch., 4 février 2010, RG n°06/01490. Sport ; cyclotourisme ; responsabilité civile ; accident ; article 1384 du code civil ; acceptation des risques ; garde de la chose

Chaotropic Agents Boosting the Performance of Photoionic Cells

Photoionic cells are a simple and scalable concept for direct solar energy storage, where the redox fuels produced by the photoreaction are separated in different phases to prevent recombination. The presence of chaotropic agents such as urea, that break the structure of water, was found to drastically enhance the quantum yield; a 10-fold increase of quantum yield to over 13% was achieved by addition of chaotropes into a system based on the reductive quenching of Azure B by Co­(II)­EDTA in water and the extraction of the leuco dye in 1,2-dichloroethane