| 1. |
- Canton, Sophie, et al.
(författare)
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Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X-ray Absorption Spectroscopy
- 2014
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 118:8, s. 4536-4545
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Tidskriftsartikel (refereegranskat)abstract
- For numerous spin crossover complexes, the anisotropic distortion of the first coordination shell around the transition metal center governs the dynamics of the high-spin/low-spin interconversion. However, this structural parameter remains elusive for samples that cannot be investigated with crystallography. The present work demonstrates how picosecond X-ray absorption spectroscopy is able to capture this specific deformation in the photoinduced high-spin state of solvated [Fe(terpy)(2)](2+), a complex which belongs to the prominent family of spin crossover building blocks with nonequivalent metal-ligand bonds. The correlated changes in Fe-N-Axial, Fe-N-Distal, and bite angle N-Distal-Fe-N-Axial extracted from the measurements are in very good agreement with those predicted by DFT calculations in D-2d symmetry. The outlined methodology is generally applicable to the characterization of ultrafast nuclear rearrangements around metal centers in photoactive molecular complexes and nanomaterials, including those that do not display long-range order.
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| 2. |
- Cappel, Ute B., et al.
(författare)
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Characterization of the Interface Properties and Processes in Solid State Dye-Sensitized Solar Cells Employing a Perylene Sensitizer
- 2011
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 115:10, s. 4345-4358
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Tidskriftsartikel (refereegranskat)abstract
- We recently reported on a perylene sensitizer, ID176, which performs much better in solid state dye-sensitized solar cells than in those using liquid electrolytes with iodide/tri-iodide as the redox couple (J. Phys. Chem. C2009, 113, 14595-14597). Here, we present a characterization of the sensitizer and of the TiO2/dye interface by UV-visible absorption and fluorescence spectroscopy, spectroelectrochemistry, photoelectron spectroscopy, electroabsorption spectroscopy, photoinduced absorption spectroscopy, and femtosecond transient absorption measurements. We report that the absorption spectrum of the sensitizer is red-shifted by addition of lithium ions to the surface due to a downward shift of the excited state level of the sensitizer, which is of the same order of magnitude as the downward shift of the titanium dioxide conduction band edge. Results from photoelectron spectroscopy and electrochemistry suggest that the excited state is largely located below the conduction band edge of TiO2 but that there are states in the band gap of TiO2 which might be available for photoinduced electron injection. The sensitizer was able to efficiently inject into TiO2, when a lithium salt was present on the surface, while injection was much less effective in the absence of lithium ions or in the presence of solvent. In the presence of the hole conductor 2,2-,7,7-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9-spirobifluorene (spiro-MeOTAD) and LiTFSI, charge separation was monitored by the emergence of a Stark shift of the dye in transient absorption spectra, and both injection and regeneration appear to be completed within 1 ps. Regeneration by spiro-MeOTAD is therefore several orders of magnitude faster than regeneration by iodide, and ID176 can even be photoreduced by spiro-MeOTAD.
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| 3. |
- Chavillon, Benoit, et al.
(författare)
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P-Type Nitrogen-Doped ZnO Nanoparticles Stable under Ambient Conditions
- 2012
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 134:1, s. 464-470
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Tidskriftsartikel (refereegranskat)abstract
- Zinc oxide is considered as a very promising material for optoelectronics. However, to date, the difficulty in producing stable p-type ZnO is a bottleneck, which hinders the advent of ZnO-based devices. In that context, nitrogen-doped zinc oxide receives much attention. However, numerous reviews report the controversial character of p-type conductivity in N-doped ZnO, and recent theoretical contributions explain that N-doping alone cannot lead, to p-typeness in Zn-rich ZnO. We report here that the ammonolysis at low temperature or ZnO2 yields pure wurtzite-type N-doped ZnO nanoparticles with an extraordinarily large amount of Zn vacancies (up to 20%). Electrochemical and transient spectroscopy studies demonstrate that these Zn-poor nanoparticles exhibit a p-type conductivity that is stable over more than 2 years under ambient conditions.
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| 4. |
- Gibson, Elizabeth A., et al.
(författare)
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A p-Type NiO-Based Dye-Sensitized Solar Cell with an Open-Circuit Voltage of 0.35 V
- 2009
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 48:24, s. 4402-4405
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Tidskriftsartikel (refereegranskat)abstract
- In tandem: Employing a molecular dyad and a cobalt-based electrolyte gives a threefold-increase in open-circuit voltage (VOC) for a p-type NiO device (VOC=0.35 V), and a fourfold better energy conversion efficiency. Incorporating these improvements in a TiO2/NiO tandem dye-sensitized solar cell (TDSC), results in a TDSC with a VOC=0.91 V
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| 5. |
- Gibson, Elizabeth A., et al.
(författare)
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Cobalt Polypyridyl-Based Electrolytes for p-Type Dye-Sensitized Solar Cells
- 2011
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 115:19, s. 9772-9779
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Tidskriftsartikel (refereegranskat)abstract
- A series of polypyridyl cobalt complexes with different substituents was applied as redox mediators in p-type dye-sensitized solar cells (p-DSCs), consisting of mesoporous NiO sensitized with a perylenemonoimide naphthalenediimide (PMI-NDI) dyad. The photocurrent and photovoltages of the devices were found to depend on the steric bulk of the redox species rather than their electrochemical potential. Bulky substituents were found to slow the detrimental charge recombination reactions between holes in the NiO semiconductor and the reduced form of the redox couple. The open-circuit potential (V-OC) of each of the devices was superior to the equivalent PMI-NDIsensitized p-DSCs containing the triiodide/iodide redox couple.
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| 6. |
- Jäger, Michael, et al.
(författare)
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Cyclometalated Ru-II Complexes with Improved Octahedral Geometry : Synthesis and Photophysical Properties
- 2010
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 49:2, s. 374-376
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Tidskriftsartikel (refereegranskat)abstract
- Cyclometalated bis-tridentate ruthenium(II) complexes incorporating 2,6-diquinolin-8-ylpyridine ligands and exhibiting broad visible absorptions are described. A [Ru(N boolean AND N boolean AND N)(N boolean AND C boolean AND N)](+) complex based only on ligands with expanded bite angles has a metal-to-ligand charge-transfer excited-state lifetime of 16 ns, which is attributed to a strong ligand field and therefore reduced deactivation via metal-centered states.
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| 7. |
- Le Pleux, Loic, et al.
(författare)
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Synthesis, photophysical and photovoltaic investigations of acceptor-functionalized perylene monoimide dyes for nickel oxide p-type dye-sensitized solar cells
- 2011
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Ingår i: ENERGY & ENVIRONMENTAL SCIENCE. - : Royal Society of Chemistry (RSC). - 1754-5692 .- 1754-5706. ; 4:6, s. 2075-2084
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Tidskriftsartikel (refereegranskat)abstract
- We report on the synthesis, electrochemical, photophysical, and photovoltaic properties of a series of three organic dyads comprising a perylene monoimide (PMI) dye connected to a naphthalene diimide (NDI) or a fullerene (C-60) for application in dye-sensitized solar cells (DSCs) with nanocrystalline NiO electrodes. It was found that the secondary electron acceptor (NDI or C-60) in all the three dyads extends the charge separated state lifetime by about five orders of magnitude compared to the respective parent PMI dye. Nanosecond pump-probe experiments of the NiO/dyads in the presence of the electrolyte show that the reduction of triiodide by the secondary electron acceptor is slow in all the dyads, which we ascribe to a weak driving force for this reaction. This reaction is significantly faster with the cobalt electrolyte (tris(4,4'-di-tert-butyl-2,2'-bipyridine)cobalt(II/III)), whose driving force is larger; however, its reaction with the reduced dyads is still rather slow. We demonstrate that the larger photovoltage observed with the cobalt electrolyte (V-OC = 285 mV) relative to the iodide electrolyte (V-OC = 120 mV) is due to a decrease in the dark current for the former owing to slower interfacial electron transfer of the reduced mediator with the injected holes into the NiO electrode. In terms of photovoltaic performances, the most efficient dyad is the system in which the NDI is directly connected to the PMI (eta = 0.14% under AM 1.5 with the cobalt electrolyte), but the dyad containing the fullerene acceptor exhibits the highest IPCE and the highest short circuit current density (IPCE = 57%, J(SC) = 1.88 mA cm(-2)) with the iodide electrolyte. The latter performances are attributed to the slightly stronger reducing power of C-60 relative to NDI, which favours the reduction of the mediator in the electrolyte.
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| 8. |
- Odobel, Fabrice, et al.
(författare)
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Recent advances and future directions to optimize the performances of p-type dye-sensitized solar cells
- 2012
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Ingår i: Coordination chemistry reviews. - : Elsevier BV. - 0010-8545 .- 1873-3840. ; 256:21-22, s. 2414-2423
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Forskningsöversikt (refereegranskat)abstract
- This review provides a summary of the most important developments in the field of solar cells based on the sensitization of p-type semiconductors, such as NiO, and identifies the future challenges and opportunities to enhance their overall performance. In particular, the main factors responsible for the low open-circuit voltage, short circuit photocurrent and fill factor are discussed in detail.
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| 9. |
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