Zinc Phthalocyanine−Graphene Hybrid Material for Energy Conversion: Synthesis, Characterization, Photophysics and Photoelectrochemical Cell Preparation

Graphene exfoliation upon tip sonication in o-­‐DCB was accomplished. Then, covalent grafting of (2-­‐ aminoethoxy)(tri-­‐tert-­‐butyl) zinc phthalocyanine (ZnPc), to exfoliated graphene sheets was achieved. The newly formed ZnPc-­‐graphene hybrid material was found soluble in common organic solvents without any precipitation for several weeks. Application of diverse spectroscopic techniques verified the successful formation of ZnPc-­‐graphene hybrid materi-­‐ al, while thermogravimetric analysis revealed the amount of ZnPc loading onto graphene. Microscopy analysis based on AFM and TEM was applied to probe the morphological characteristics and to investigate the exfoliation of graphene sheets. Efficient fluorescence quenching of ZnPc in the ZnPc-­‐graphene hybrid material suggested that photoinduced events occur from the photoexcited ZnPc to exfoliated graphene. The dynamics of the photoinduced electron transfer was evaluated by femtosecond transient absorption spectroscopy, thus, revealing the formation of transient species such as ZnPc+ yielding the charge-­‐separated state ZnPc•+–graphene•–. Finally, the ZnPc-­‐graphene hybrid material was integrated into a photoactive electrode of an optical transparent electrode (OTE) cast with nanostructured SnO2 films (OTE/SnO2), which exhibited sta le and reproducible photocurrent responses and the incident photon-­‐to-­‐current conversion efficien-­‐ cy was determine

ミナミ タイヘイヨウ ヒカク チタイ ジョウヤク ケイセイ カテイ ニ オケル オーストタリア ノ カクグンシュク ガイコウ セイサク

Alternate bilayer structures of N,N'-bis(2,5-di-tert-butylphenyl)-3,4,9,10- perylene dicarboximide (PDI), freebase phthalocyanines (Pc), and double-linked free-base phthalocyanine-fullerene dyad (Pc-C 60) were prepared by the Langmuir-Schäfer method and studied using a range of optical spectroscopy methods including femtosecond pump-probe and up-conversion. An efficient quenching of the PDI fluorescence by Pc and Pc-C 60 dyad was observed in both steady-state and time-resolved fluorescence measurements. The quenching takes place in less than a few picoseconds, and is due to energy transfer from perylene dicarboximide to phthalocyanine chromophore in PDI|Pc and PDI|Pc-C 60 films. In the PDI|Pc-C 60 bilayer structure the energy transfer is followed by a charge separation in the Pc-C 60 layer, yielding a long-lived (a few microseconds) intermolecular charge separated state similar to that reported recently for Pc-C 60 Langmuir-Blodgett films (Lehtivuori, H.; et al. J. Phys. Chem. C 2008, 112, 9896-9902)

Impact of concentration self-quenching on the charge generation yield of fullerene based donor-bridge-acceptor compounds in the solid state

A fullerene based Donor-Bridge-Acceptor (DBA) compound, incorporating a pi-extended tetrathiafulvalene electron donor, is investigated with respect to its photophysics in solution versus solid state. Solid films of neat DBA are compared with blend films where the DBA compound is diluted in the inert, low dielectric, polymer poly(styrene). It is found that the moderate intermolecular electronic coupling and donor-acceptor separation (22 angstrom) in this case leads to the generation of more dissociated, intermolecular charges than a mixture of the donor and acceptor reference compounds. However, the increased intermolecular interactions in the solid state lead to the excited state of the fullerene suffering from concentration self-quenching. This is found to severely affect the charge generation yield in solid films. The impact of competing intra and intermolecular interactions in the solid state upon the film photophysics is analysed in terms of a kinetic model which includes both the effects of concentration self-quenching and the impact of film composition upon the dielectric stabilisation of charge separated states. We conclude that both concentration self-quenching and dielectric stabilisation are critical in determining the photophysics of the blend films, and discuss strategies based upon our observations to enhance the charge photogeneration properties of organic films and photovoltaic devices based upon DBA compounds