| 1. |
- Benko, Gabor, et al.
(författare)
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Photoinduced Electron Injection from Ru(dcbPY)2(NCS)2 to SnO2 and TiO2 Nanocrystalline Films.
- 2003
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 125:5, s. 1118-1119
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Tidskriftsartikel (refereegranskat)abstract
- Photoinduced electron injection from the sensitizer Ru(dcbpy)2(NCS)2 (RuN3) into SnO2 and TiO2 nanocrystalline films occurs by two distinct channels on the femto- and picosecond time scales. The faster electron injection into the conduction band of the different semiconductors originates from the initially excited singlet state of RuN3, and occurs in competition with intersystem crossing. The rate of singlet electron injection is faster to TiO2 (1/55 fs-1) than to SnO2 (1/145 fs-1), in agreement with higher density of conduction band acceptor states in the former semiconductor. As a result of competition between the ultrafast processes, for TiO2 singlet, whereas for SnO2 triplet electron injection is dominant. Electron injection from the triplet state is nonexponential and can be fitted with time constants ranging from ~1 ps (2.5 ps for SnO2) to ~50 ps for both semiconductors. The major part of triplet injection is independent of the semiconductor and is most likely controlled by intramolecular dynamics in RuN3. The overall time scale and the yield of electron injection to the two semiconductors are very similar, suggesting that processes other than electron injection are responsible for the difference in efficiencies of solar cells made of these materials.
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| 2. |
- Benko, Gabor, et al.
(författare)
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Photoinduced Ultrafast Dye-to-Semiconductor Electron Injection from Nonthermalized and Thermalized Donor States.
- 2002
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 124:3, s. 489-493
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Tidskriftsartikel (refereegranskat)abstract
- Electron injection from the transition metal complex Ru(dcbpy)(2)(NCS)(2) (dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) into a titanium dioxide nanocrystalline film occurs on the femto- and picosecond time scales. Here we show that the dominating part of the electron transfer proceeds extremely rapidly from the initially populated, vibronically nonthermalized, singlet excited state, prior to electronic and nuclear relaxation of the molecule. The results are especially relevant to the understanding and design of molecular-based photovoltaic devices and artificial photosynthetic assemblies.
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| 3. |
- Corani, Alice, et al.
(författare)
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Superior photoprotective motifs and mechanisms in eumelanins uncovered.
- 2014
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 136:33, s. 11626-11635
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Tidskriftsartikel (refereegranskat)abstract
- Human pigmentation is a complex phenomenon commonly believed to serve a photoprotective function through the generation and strategic localization of black insoluble eumelanin biopolymers in sun exposed areas of the body. Despite compelling biomedical relevance to skin cancer and melanoma, eumelanin photoprotection is still an enigma: What makes this pigment so efficient in dissipating the excess energy brought by harmful UV-light as heat? Why has Nature selected 5,6-dihydroxyindole-2-carboxylic acid (DHICA) as the major building block of the pigment instead of the decarboxylated derivative (DHI)? By using pico- and femtosecond fluorescence spectroscopy we demonstrate herein that the excited state deactivation in DHICA oligomers is 3 orders of magnitude faster compared to DHI oligomers. This drastic effect is attributed to their specific structural patterns enabling multiple pathways of intra- and interunit proton transfer. The discovery that DHICA-based scaffolds specifically confer uniquely robust photoprotective properties to natural eumelanins settles a fundamental gap in the biology of human pigmentation and opens the doorway to attractive advances and applications.
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| 4. |
- De, Swati, et al.
(författare)
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Geminate charge recombination in alternating polyfluorene copolymer/fullerene blends
- 2007
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 129:27, s. 8466-8472
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Tidskriftsartikel (refereegranskat)abstract
- By measuring excited state and charge dynamics in blends of an alternating polyfluorene copolymer and fullerene derivative over nine orders in time and two orders in light intensity, we have monitored the light-induced processes from ultrafast charge photogeneration to much slower decay of charges by recombination. We find that at low light intensities relevant to solar cell operation relatively fast (∼30 ns) geminate recombination is the dominating charge decay process, while nongeminate recombination has a negligible contribution. The conclusion of our work is that under solar illumination conditions geminate recombination of charges may be directly competing with efficient charge collection in polymer/fullerene solar cells. © 2007 American Chemical Society.
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| 5. |
- Gauden, Magdalena, et al.
(författare)
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Role of Solvent, pH, and Molecular Size in Excited-State Deactivation of Key Eumelanin Building Blocks: Implications for Melanin Pigment Photostability.
- 2008
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 130:50, s. 17038-17043
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Tidskriftsartikel (refereegranskat)abstract
- Ultrafast time-resolved fluorescence spectroscopy has been used to investigate the excited-state dynamics of the basic eumelanin building block 5,6-dihydroxyindole-2-carboxylic acid (DHICA), its acetylated, methylated, and carboxylic ester derivatives, and two oligomers, a dimer and a trimer in the O-acetylated forms. The results show that (1) excited-state decays are faster for the trimer relative to the monomer; (2) for parent DHICA, excited-state lifetimes are much shorter in aqueous acidic medium (380 ps) as compared to organic solvent (acetonitrile, 2.6 ns); and (3) variation of fluorescence spectra and excited-state dynamics can be understood as a result of excited-state intramolecular proton transfer (ESIPT). The dependence on the DHICA oligomer size of the excited-state deactivation and its ESIPT mechanism provides important insight into the photostability and the photoprotective function of eumelanin. Mechanistic analogies with the corresponding processes in DNA and other biomolecules are recognized.
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| 6. |
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| 7. |
- He, Jianjun, et al.
(författare)
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Modified phthalocyanines for efficient near-IR sensitization of nanostructured TiO2 electrode
- 2002
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 124:17, s. 4922-4932
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Tidskriftsartikel (refereegranskat)abstract
- A zinc phthalocyanine with tyrosine substituents (ZnPcTyr), modified for efficient far-red/near-IR performance in dye-sensitized nanostructured TiO2 solar cells, and its reference, glycine-substituted zinc phthalocyanine, (ZnPcGly), were synthesized and characterized. The compounds were studied spectroscopically, electrochemically, and photoelectrochemically. Incorporating tyrosine groups into phthalocyanine makes the dye ethanol-soluble and reduces surface aggregation as a result of steric effects. The performance of a solar cell based on ZnPcTyr is much better than that based on ZnPcGly. Addition of 3alpha,7alpha-dihydroxy-5beta-cholic acid (cheno) and 4-tert-butylpyridine (TBP) to the dye solution when preparing a dye-sensitized TiO2 electrode diminishes significantly the surface aggregation and, therefore, improves the performance of solar cells based on these phthalocyanines. The highest monochromatic incident photo-to-current conversion efficiency (IPCE) of similar to24% at 690 nm and an overall conversion efficiency (eta) of 0.54% were achieved for a cell based on a ZnPcTyr-sensitized TiO2 electrode. Addition of TBP in the electrolyte decreases the IPCE and eta considerably, although it increases the open-circuit photovoltage. Time-resolved transient absorption measurements of interfacial electron-transfer kinetics in a ZnPoTyr-sensitized nanostructured 702 thin film show that electron injection from the excited state of the dye into the conduction band of TiO2 is completed in similar to500 fs and that more than half of the injected electrons recombines with the oxidized dye molecules in similar to300 ps. In addition to surface aggregation, the very fast electron recombination is most likely responsible for the low performance of the solar cell based on ZnPcTyr.
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| 8. |
- Pal, S. K., et al.
(författare)
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Geminate Charge Recombination in Polymer/Fullerene Bulk Heterojunction Films and Implications for Solar Cell Function
- 2010
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 1520-5126 .- 0002-7863. ; 132:35, s. 12440-12451
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the influence of three different fullerene derivatives on the charge generation and recombination dynamics of polymer/fullerene bulk heterojunction (BHJ) solar cell blends. Charge generation in APFO3/[70]PCBM and APFO3/[60]PCBM is very similar and somewhat slower than charge generation in APFO3/[70]BTPF. This difference qualitatively matches the trend in free energy change of electron transfer estimated from the LUMO energies of the polymer and fullerene derivatives. The first order (geminate) charge recombination rate is significantly different for the three fullerene derivatives studied and increases in the order APFO3/[70]PCBM
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| 9. |
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| 10. |
- Pan, Jie, et al.
(författare)
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Photoinduced electron transfer between a carotenoid and TiO2 nanoparticle
- 2002
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 124:46, s. 13949-13957
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Tidskriftsartikel (refereegranskat)abstract
- The dynamics of photoinduced electron injection and recombination between all-trans-8'-apo-beta-caroten-8'-oic acid (ACOA) and a TiO2 Colloidal nanoparticle have been studied by means of transient absorption spectroscopy. We observed an ultrafast (similar to360 fs) electron injection from the initially excited S-2 state of ACOA into the TiO2 conduction band with a quantum yield of similar to40%. As a result, the ACOA(.+) radical cation was formed, as demonstrated by its intense absorption band centered at 840 nm. Because of the competing S-2-S-1 internal conversion, similar to60% of the S-2-state population relaxes to the S-1 state. Although the S-1 state is thermodynamically favorable to donate electrons to the TiO2, no evidence was found for electron injection from the ACOA S, state, most likely as a result of a complicated electronic nature of the S, state, which decays with a similar to18 ps time constant to the ground state. The charge recombination between the injected electrons and the ACOA(.+) was found to be a highly nonexponential process extending from picoseconds to microseconds. Besides the usual pathway of charge recombination forming the ACOA ground state, about half of the ACOA(.+) recombines via the ACOA triplet state, which was monitored by its absorption band at 530 nm. This second channel of recombination proceeds on the nanosecond time scale, and the formed triplet state decays to the ground state with a lifetime of similar to7.3 mus. By examination of the process of photoinduced electron transfer in a carotenoid-semiconductor system, the results provide an insight into the photophysical properties of carotenoids, as well as evidence that the interfacial electron injection occurs from the initially populated excited state prior to electronic and nuclear relaxation of the carotenoid molecule.
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