0000000000048529
AUTHOR
Jani Kallioinen
Interligand Electron Transfer Determines Triplet Excited State Electron Injection in RuN3−Sensitized TiO2 Films
Electron injection from the transition metal complex Ru(dcbpy)(2)(NCS)(2) (dcbpy = 2,2'-bipyridine-4,4'-dicarboxylate) into a titanium dioxide nanoparticle film occurs along two pathways. The dominating part of the electron injection proceeds from the initially excited singlet state of the sensitizer into the conduction band of the semiconductor on the sub-hundred-femtosecond time scale. The slower part of the injection occurs from the thermalized triplet excited state on the picosecond time scale in a nonexponential fashion, as was shown in a previous study (Benko, G.; et al. J. Am. Chem. Soc. 2002, 124, 489). Here we show that the slower channel of injection is the result of the excited s…
Quaternary ammonium polyiodides as ionic liquid/soft solid electrolytes in dye-sensitized solar cells
Abstract Four new quaternary ammonium iodides, (Me 2 Pe 2 N)I, (Me 2 Hex 2 N)I, (Et 2 Pe 2 N)I and (Et 2 Hex 2 N)I, were synthesized and studied as electrolytes in dye-sensitized solar cells. All compounds were solids at room temperature. Influence of varying amounts of elemental iodine and the effect of tert -butylpyridine (TBP) on the performance of the cell was also studied. Addition of iodine lowered the melting points of the resulting polyiodides. From the ammonium iodides only (Me 2 Hex 2 N)I:I 2 (10:1) was liquid at the room temperature and the others were soft solids. Under illumination from a halogen lamp source at 10 mW cm −2 intensity, the highest power conversion efficiency of 2…
Dye-sensitized nanostructured TiO2 film based photoconductor
Grooves were etched in a conductive layer of a conductive, transparent glass, and a nanoporous TiO2 film was deposited on both the conductive and nonconductive area. The width of the grooves was 100 $\mu$m and 150 $\mu$m. A transparent TiO2 film was dye-sensitized, covered with an electrolyte, and sandwiched with a cover glass. The conductivity of the dye-sensitized TiO2 film permeated with electrolyte was studied in the dark and under illumination, and was observed to be dependent on light intensity, wavelength and applied voltage. This study shows that dye-sensitized nanoporous films can be used as a wavelength dependent photoconductor.
Electron Transfer from the Singlet and Triplet Excited States of Ru(dcbpy)2(NCS)2into Nanocrystalline TiO2Thin Films
Time-resolved absorption spectroscopy was used to study the femtosecond and picosecond time scale electron injection from the excited singlet and triplet states of Ru(dcbpY)(2)(NCS)(2) (RuN3) into titanium dioxide (TiO2) nanocrystalline particle film in acetonitrile. The fastest resolved time constant of similar to30 fs was shown to reflect a sum of two parallel ultrafast processes, nonergodic electron transfer (ET) from the initially excited singlet state of RuN3 to the conduction band of TiO2 and intersystem crossing (ISC). The branching ratio of 1.5 between the two competing processes gives rate constants of 1/50 fs(-1) for ET and 1/75 fs(-1) for ISC. Following the ultrafast processes, a…
Transient absorption studies of the Ru(dcbpy)2(NCS)2 excited state and the dye cation on nanocrystalline TiO2 film
We have measured dynamics of the Ru(dcbpy)2(NCS)2 [dcbpy = 4,4′-dicarboxy-2,2′-bipyridine] excited state and the dye cation on nanocrystalline TiO2 film in the wavelength region 700–900 nm. The dye in ethanol solution and Ru(dcbpy)2(NCS)2 sensitized nanocrystalline Al2O3 films were used as non-injecting reference samples for excited state identification. For TiO2/Ru(dcbpy)2(NCS)2 film the `reactant' decay and `product' formation kinetics observed at different probe wavelengths showed that the resolved transient absorption picosecond components (1.1±0.2), (12±2) and (100±5) ps are related to electron injection from the excited states of the dye to the semiconductor TiO2.
Photoinduced ultrafast dynamics of Ru(dcbpy)2(NCS)2-sensitized nanocrystalline TiO2 films:The influence of sample preparation and experimental conditions
In most of the previous ultrafast electron injection studies of Ru(dcbpy)2(NCS)2-sensitized nanocrystalline TiO2 films, experimental conditions and sample preparation have been different from study to study and no studies of how the differences affect the observed dynamics have been reported. In the present paper, we have investigated the influence of such modifications. Pump photon density, environment of the sensitized film (solvent and air), and parameters of the film preparation (crystallinity and quality of the film) were varied in a systematic way and the obtained dynamics were compared to that of a well-defined reference sample: Ru(dcbpy)2(NCS)2−TiO2 in acetonitrile. In some cases, …
Photoinduced ultrafast dye-to-semiconductor electron injection from nonthermalized and thermalized donor states.
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.
Towards roll-to-roll fabrication of electronics, optics and optoelectronics for smart and intelligent packaging
Embedding of optoelectrical, optical, and electrical functionalities into low-cost products like packages and printed matter can be used to increase their information content. These functionalities make also possible the realization of new type of entertaining, impressive or guiding effects on the product packages and printed matter. For these purposes, components like displays, photodetectors, light sources, solar cells, battery elements, diffractive optical elements, lightguides, electrical conductors, resistors, transistors, switching elements etc. and their integration to functional modules are required. Additionally, the price of the components for low-end products has to be in cent sc…
Dynamic preparation of TiO2 films for fabrication of dye-sensitized solar cells
Preparation of nanocrystalline porous titanium dioxide (TiO2) films with roll-to-roll compatible methods was studied. Gravure printing was used for spreading TiO2 paste and paper calendering for pressing TiO2 nanoparticle films. Influence of different preparation methods on performance of fabricated dye-sensitized solar cells (DSSCs) was investigated. The attained light into electricity conversion efficiency was compared with DSSCs fabricated on conductive plastic substrates by doctor-blading spreading with subsequent static pressing. The latter method achieved a light conversion efficiency as high as 5.1%. The efficiency of the cells with a gravure printed TiO2 film was found to be rather …
Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO)2I2 complex
Abstract Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [trans-I-Ru(dcbpy)(CO)2I2] (dcbpy= 4,4′-dicarboxy-2,2′-bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [cis-I-Ru(dcbpy)(CO)(Sol)I2] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K ind…