No abstract

Highly effi cient light absorption and charge separation within the photosystem and reaction center (RC) complexes of photosynthetic plants and bacteria are of great interest for solar cell and photo detector applications, since they offer almost unity quantum yield and expected ultimate power conversion effi ciencies of more than 18% and 12%, respectively. In addition, the charge separated states created by these protein complexes are very long lived compared to conventional semiconductor solar cells. In this work, a novel technique is presented for the deposition of photosynthetic protein complexes, by electrospraying RCs of Rhodobacter sphaeroides onto highly ordered pyrolytic graphite (HOPG) electrodes. Remarkably, it is shown that the RCs not only survive exposure to the high electric fi elds but also yield peak photocurrent densities of up to 7 µA cm −2 , which is equal to the highest value reported to date.

Bacterial photosynthetic reaction centers (RCs) are promising materials for solar energy harvesting, due to their high quantum efficiency. A simple approach for making a photovoltaic device is to apply solubilized RCs and charge carrier mediators to the electrolyte of an electrochemical cell. However, the adsorption of analytes on the electrodes can affect the charge transfer from RCs to the electrodes. In this work, photovoltaic devices were fabricated incorporating RCs from purple bacteria, ubiquinone-10 (Q2), and cytochrome c (Cyt c) (the latter two species acting as redox mediators). The adsorption of each of these three species on the gold working electrode was investigated, and the roles of adsorbed species in the photocurrent generation and the cycle of charge transfer were studied by a series of photochronoamperometric, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and cyclic voltammetry (CV) tests. It was shown that both redox mediators were required for photocurrent generation; hence, the RC itself is likely unable to inject electrons into the gold electrode directly. The reverse redox reactions of mediators at the electrodes generates electrical current. Cyclic voltammograms for the RC-exposed gold electrode revealed a redox couple due to the adsorbed RC at ∼ +0.5 V (vs NHE), which confirmed that the RC was still redox active, upon adsorption to the gold. Photochronoamperometric studies also indicated that RCs adsorb, and are strongly bound to the surface of the gold, retaining functionality and contributing significantly to the process of photocurrent generation. Similar experiments showed the adsorption of Q2 and Cyt c on unmodified gold surfaces. It was indicated by the photochronoamperometric tests that the photocurrent derives from Q2-mediated charge transfer between the RCs and the gold electrode, while solubilized Cyt c mediates charge transfer between the P-side of adsorbed RC and the Pt counter electrode. Also, the stability of the adsorbed RCs and mediators was evaluated by measuring the photocurrent response over a period of 1 week. It is found that ∼46% of the adsorbed RCs remain active after a week under aerobic conditions. A significantly extended lifetime is expected by removing oxygen from the electrolyte and sealing the device.

Control over phase separation and morphology is critical to optimal function in polymer optoelectronic devices. Here, two fully conjugated oligomeric compatibilizers are introduced, and their effect on the phase separation of blends of poly(9,9′-dioctylfluorene-co-benzothiadiazole) (F8BT) with poly(9,9′-dioctylfluorene-co-bis-N,N′-(4,butylphenyl)bis-N,N′-phenyl-1,4-phenylenediamine) (PFB) are reported. AFM and STXM analysis demonstrate that the addition of compatibilizer altered the size and relative composition of phaseseparated domains formed during spin-casting. Small structural differences between the two compatibilizers brought about significantly different morphological changes to the blends, suggesting that further development of compatibilizer structure could enable enhanced control toward desired blend film morphologies.