| 1. |
- Johansson, Erik M .J., et al.
(författare)
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Interfacial properties of photovoltaic TiO2/dye/PEDOT-PSS heterojunctions
- 2005
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Ingår i: Synthetic metals. - : Elsevier BV. - 0379-6779 .- 1879-3290. ; 149:03-feb, s. 157-167
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Tidskriftsartikel (refereegranskat)abstract
- Systems comprising a dense TiO2 film electrode, a ruthenium polypyridine dye and a PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(4-styrenesulphonate)) film were prepared. The heterojunctions were shown to have photovoltaic properties, with the dye absorbing the light, the TiO2 acting as an electron conducting material and PEDOT-PSS acting as a hole transport material. A series of dyes was used to investigate their influence on the photocurrent and the photovoltage characteristics of the heterojunction. These results were compared to a photoelectrochemical system in which the PEDOT-PSS was replaced by a liquid electrolyte containing triiodide/iodide redox-couple. Photoelectron spectroscopy (PES) was used to monitor the interfacial properties of the heterojunction and the investigation points out effects of importance when assembling the materials together to a functional unit. Specifically, it was concluded that the interaction with the dye clearly affects the structure of PEDOT-PSS, both with respect to the surface composition of PSS relative to PEDOT and with respect to the chemical state of the sulphur in the polymers. Moreover, a comparison of the Ru3d and the valence band spectra of the two different interfaces (dye/TiO2 and dye/PEDOT-PSS) indicates that the energy level structure of the dyes compared to the substrate is different for the two surfaces. Thus, in the combined energy level picture under dark conditions, the energy levels in TiO2 relative to the energy levels in PEDOT-PSS depend on the dye.
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| 2. |
- Agrios, Alexander G., et al.
(författare)
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Low-temperature TiO2 Films for Dye-sensitized Solar Cells : Factors Affecting Energy Conversion Efficiency
- 2008
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 112:27, s. 10021-10026
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Tidskriftsartikel (refereegranskat)abstract
- Semiconductor films prepd. by electrostatic layer-by-layer deposition can be used to fabricate dye-sensitized solar cells after low-temp. treatment (150 DegC). However, the resulting photocurrent is much less than when the film is sintered at 500 DegC. The difference in short-circuit current is a factor of 2.2 with the Ru-based dye N719 and is 3.5 with the org. dye D5. The photocurrent at a given wavelength is proportional to the light-harvesting efficiency, charge injection effciency, and charge collection efficiency. Sintered films take up more than 60% more of either dye than unsintered films and therefore absorb more photons. Electron injection is hindered in unsintered films due to a conduction band edge potential 100 mV more neg. than in a sintered electrode. Addnl. injection effects could be due to adsorption of the dye to polymer rather than to TiO2 in unsintered films, although our measurements were inconclusive on this point. Kinetic studies show electron transport times (ttr) an order of magnitude faster then electron lifetimes (te) in both sintered and unsintered electrodes. Furthermore, a Li+ insertion expt. shows that both films have good elec. connectivity between TiO2 nanoparticles. Unsintered films thus exhibit efficient charge transport despite the presence of polymer and the lack of heat treatment to induce necking.
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| 3. |
- Alarcon, H., et al.
(författare)
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Dye-sensitized solar cells based on nanocrystalline TiO2 films surface treated with Al3+ ions : Photovoltage and electron transport studies
- 2005
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 109:39, s. 18483-18490
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Tidskriftsartikel (refereegranskat)abstract
- Nanocrystalline TiO2 films, surface modified with Al3+, were manufactured by depositing a TiO2 suspension containing small amounts of aluminum nitrate or aluminum chloride onto conducting glass substrates, followed by drying, compression, and finally heating to 530 degrees C. Electrodes prepared with TiO2 nanoparticles coated with less than 0.3 wt % aluminum oxide with respect to TiO2 improved the efficiency of the dye sensitized solar cell. This amount corresponds to less than a monolayer of aluminum oxide. Thus, the Al ions terminate the TiO2 surface rather than form a distinct aluminum oxide layer. The aluminum ion surface treatment affects the solar cell in different ways: the potential of the conduction band is shifted, the electron lifetime is increased, and the electron transport is slower when aluminum ions are present between interconnected TiO2 particles.
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| 4. |
- Alarcon, Hugo, et al.
(författare)
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Modification of nanostructured TiO2 electrodes by electrochemical Al3+ insertion : Effects on dye-sensitized solar cell performance
- 2007
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 111:35, s. 13267-13274
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Tidskriftsartikel (refereegranskat)abstract
- Nanostructured TiO2 films were modified by insertion with aluminum ions using an electrochemical process. After heat treatment these films were found suitable as electrodes in dye-sensitized solar cells. By means of a catechol adsorption test, as well as photoelectron spectroscopy (PES), it was demonstrated that the density of Ti atoms at the metal oxide/electrolyte interface is reduced after Al modification. There is, however, not a complete coverage of aluminum oxide onto the TiO2, but the results rather suggest either the formation of a mixed Al-Ti oxide surface layer or formation of a partial aluminum oxide coating. No new phase could, however, be detected. In solar cells incorporating Al-modified TiO2 electrodes, both electron lifetimes and electron transport times were increased. At high concentrations of inserted aluminum ions, the quantum efficiency for electron injection was significantly decreased. Results are discussed at the hand of different models: A multiple trapping model, which can explain slower kinetics by the creation of additional traps during Al insertion, and a surface layer model, which can explain the reduced recombination rate, as well as the reduced injection efficiency, by the formation of a blocking layer.
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| 5. |
- Bernhardt, Paul V., et al.
(författare)
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Tailoring mixed-valence Co-III/Fe-II complexes for their potential use as sensitizers in dye sensitized solar cells
- 2008
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Ingår i: New Journal of Chemistry. - : Royal Society of Chemistry (RSC). - 1144-0546 .- 1369-9261. ; 32:4, s. 705-711
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Tidskriftsartikel (refereegranskat)abstract
- Dinuclear class II Co-III/Fe-II mixed-valence complexes of type [LnCo (III)(mu-NC) Fe-II(CN)(3)L-2](m-) (where L-n represents a pentadentate macrocycle and L-2 a bpy ligand or two cyanides) have electronic properties that make them possible sensitizers in DSSC ( dye sensitized solar cells). For this purpose the new complex Na-2[{trans-L14COOCo III( m-NC)} Fe II( CN) 5] has been prepared and characterized by the usual methods and its sensitizer properties compared with those of the already known [{trans-L14COOCo (III)(mu-NC)}Fe-II(CN)(5)](2-)(CN)(3)(bipy)(eq,ax)](ClO4). The complex [{trans-L14COOCo (III)(mu-NC)}Fe-II(CN)(5)](2-) has been designed for the actuation of an electron injection from the cobalt centre on MMCT, while the [{trans-L14COOCo (III)(mu-NC)}Fe-II(CN)(3)(bipy)](+) structure can produce a tuned injection from the iron centre via an MLCT electronic state, as described for similar systems. The characterization on solid oxide semiconductor supports has been carried out for these two complexes and the results have been compared with the behaviour observed in aqueous solution and in solvents of varying polarities. Their use in DSSC has been checked and, while a sensitizer response is observed for [{trans-L14COOCo (III)(mu-NC)}Fe-II(CN)(5)](2-), complex [{trans-L14COOCoIII(mu-NC)}Fe-II(CN)(3)(bipy)(eq,ax)](+) does not produce any electrical current on illumination. The low efficiency of the built DSSC can be easily related both with the very low value of the extinction coefficient of the MMCT band responsible for the electron injection, and with the small driving force for the reduction of the complex with the standard I-2/I-3 (-) system used after electron injection.
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| 6. |
- Borgström, Magnus, et al.
(författare)
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Sensitized hole injection of phosphorus porphyrin into NiO : Toward new photovoltaic devices
- 2005
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 109:48, s. 22928-22934
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Tidskriftsartikel (refereegranskat)abstract
- This paper describes the preparation and the characterization of a photovoltaic cell based on the sensitization of a wide band gap p-type semiconductor (NiO) with a phosphorus porphyrin. A photophysical study with femtosecond transient absorption spectroscopy showed that light excitation of the phosphorus porphyrin chemisorbed on NiO particles induces a very rapid interfacial hole injection into the valence band of NiO, occurring mainly on the 2-20 ps time scale. This is followed by a recombination in which ca. 80% of the ground-state reactants are regenerated within 1 ns. A photoelectrochernical device, prepared with a nanocrystalline NiO electrode coated with the phosphorus porphyrin, yields a cathodic photocurrent indicating that electrons indeed flow from the NiO electrode toward the solution. The low incident-to-photocurrent efficiency (IPCE) can be rationalized by the rapid back recombination reaction between the reduced sensitizer and the injected hole which prevents an efficient regeneration of the sensitizer ground state from the iodide/triiodide redox mediator. To the best of our knowledge, this work represents the first example of a photovoltaic cell in which a mechanism of hole photoinjection has been characterized.
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| 7. |
- Boschloo, G., et al.
(författare)
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A comparative study of a polyene-diphenylaniline dye and Ru(dcbpy)(2)(NCS)(2) in electrolyte-based and solid-state dye-sensitized solar cells
- 2008
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Ingår i: Thin Solid Films. - : Elsevier BV. - 0040-6090 .- 1879-2731. ; 516:20, s. 7214-7217
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Tidskriftsartikel (refereegranskat)abstract
- A small organic sensitizer, the polyene-diphenylaniline dye D5, was compared with the standard sensitizer N719 (Ru(dcbPY)(2)(NCS)(2)) in a dyesensitized solar cell investigation. In solar cells with relatively thin layers of mesoporous TiO2 (< 3 mu m) D5 outperformed N719 because of its high extinction coefficient. D5 showed also better performance than N719 in the case of sensitization of mesoporous ZnO. In solid-state solar cells, where the iodide/triiodide electrolyte was replaced by an amorphous hole conductor (spiro-OMeTAD), D5 gave promising preliminary results. The hole conductivity, observed in monolayers of D5 adsorbed at TiO2, may possibly lead to improved performance in such cells.
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| 8. |
- Boschloo, Gerrit, et al.
(författare)
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Activation energy of electron transport in dye-sensitized TiO2 solar cells
- 2005
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 109:24, s. 12093-12098
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Tidskriftsartikel (refereegranskat)abstract
- Various characteristics of dye-sensitized nanostructured TiO2 solar cells, such as electron transport and electron lifetime, were studied in detail using monochromatic illumination conditions. The electron transport was found to be a thermally activated process with activation energies in the range of 0.10-0.15 eV for light intensities that varied 2 orders of magnitude. Electron lifetimes were determined using a new method and found to be significantly larger (> 1 s) than previously determined. An average potential was determined for electrons in the nanostructured TiO2 under illumination in short-circuit conditions. This potential is about 0.2 V lower than the open-circuit potential at the same light intensity. The electron transport time varies exponentially with the internal potential at short-circuit conditions, indicating that the gradient in the electrochemical potential is the driving force for electron transport in the nanostructured TiO2 film. The applicability of the conventionally used trapping/detrapping model is critically analyzed. Although experimental results can be fitted using a trapping/detrapping model with an exponential distribution of traps, the distribution parameters differ significantly between different types of experiment. Furthermore, the experimental activation energies for electron transport are smaller than those expected in a trapping/detrapping model.
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| 9. |
- Boschloo, Gerrit, et al.
(författare)
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Characteristics of the Iodide/Triiodide Redox Mediator in Dye-Sensitized Solar Cells
- 2009
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Ingår i: Accounts of Chemical Research. - : American Chemical Society (ACS). - 0001-4842 .- 1520-4898. ; 42:11, s. 1819-1826
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Forskningsöversikt (refereegranskat)abstract
- Dye-sensitized solar cells (DSCs) have gained widespread interest because of their potential for low-cost solar energy conversion. Currently, the certified record efficiency of these solar cells is 11.1%, and measurements of their durability and stability suggest lifetimes exceeding 10 years under operational conditions, The DSC is a photoelectrochemical system: a monolayer of sensitizing dye is adsorbed onto a mesoporous TiO2 electrode, and the electrode is sandwiched together with a counter electrode. An electrolyte containing a redox couple fills the gap between the electrodes. The redox couple is a key component of the DSC. The reduced part of the couple regenerates the photo-oxidized dye. The formed oxidized species diffuses to the counter electrode, where it is reduced. The photovoltage of the device depends on the redox couple because it sets the electrochemical potential at the counter electrode. The redox couple also affects the electrochemical potential of the TiO2 electrode through the recombination kinetics between electrons in TiO2 and oxidized redox species. This Account focuses on the special properties of the iodide/triiodide (I-/I-3(-)) redox couple in dye-sensitized solar cells. It has been the preferred redox couple since the beginning of DSC development and still yields the most stable and efficient DSCs. Overall, the iodide/triiodide couple has good solubility, does not absorb too much light, has a suitable redox potential, and provides rapid dye regeneration. But what distinguishes I-/I-3(-) from most redox mediators is the very slow recombination kinetics between electrons in TiO2 and the oxidized part of the redox couple, triiodide. Certain dyes adsorbed at TiO2 catalyze this recombination reaction, presumably by binding iodine or triiodide. The standard potential of the iodide/triiodide redox couple is 0.35 V (versus the normal hydrogen electrode, NHE), and the oxidation potential of the standard DSC-sensitizer (Ru(dcbpy)(2)(NCS)(2)) is 1.1 V. The driving force for reduction of oxidized dye is therefore as large as 0.75 V. This process leads to the largest internal potential loss in DSC devices. We expect that overall efficiencies above 15% might be achieved if half of this internal potential loss could be gained. The regeneration of oxidized dye with iodide leads to the formation of the diiodide radical (I-2(-center dot)). The redox potential of the I-2(-center dot)/I- couple must therefore be considered when determining the actual driving force for dye regeneration. The formed I-2(-center dot) disproportionates to I-3(-) and I-, which leads to a large loss in potential energy.
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| 10. |
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