| 1. |
- 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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| 2. |
- Cappel, Ute B, et al.
(författare)
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Charge Generation Dynamics in CdS : P3HT Blends for Hybrid Solar Cells.
- 2013
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Ingår i: Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185 .- 1948-7185. ; 4:24, s. 4253-7
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Tidskriftsartikel (refereegranskat)abstract
- Development of design rules for hybrid inorganic-organic solar cells through understanding charge generation and recombination dynamics is an important pathway for the improvement of solar cell conversion efficiencies. In this Letter, we study the dynamics of charge generation in CdS:polymer blends by transient absorption spectroscopy. We show that charge generation following excitation of the inorganic component is highly efficient and can occur up to a few nanoseconds after excitation, allowing for diffusion of charges within the inorganic component to an interface. In contrast, charge generation following excitation of the organic component occurs on subpicosecond time scales but suffers from two loss processes, incomplete exciton dissociation and geminate recombination.
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| 3. |
- Cappel, Ute B, et al.
(författare)
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Oxygen-induced doping of spiro-MeOTAD in solid-state dye-sensitized solar cells and its impact on device performance.
- 2012
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Ingår i: Nano letters (Print). - : American Chemical Society (ACS). - 1530-6984 .- 1530-6992. ; 12:9, s. 4925-31
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Tidskriftsartikel (refereegranskat)abstract
- Solid state dye-sensitized solar cells (sDSCs) employing the hole conductor 2,2'7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-MeOTAD) require the presence of oxygen during fabrication and storage. In this paper, we determine the concentrations of oxidized spiro-MeOTAD within devices under different operating and storage conditions by UV-vis spectroscopy. Relative concentrations of spiro-MeOTAD(+) were found to be greater than 10% after illumination for standard sDSCs, where no chemical dopant had been used in the solar cell fabrication but oxygen and lithium ions were present. We suggest that oxidized spiro-MeOTAD is created as a byproduct of oxygen reduction at the TiO(2) surface during cell illumination. Furthermore, we studied the effect of light soaking under different conditions and associated changes in spiro-MeOTAD(+) concentration on the solar cell measurements. Our findings give insights to photochemical reactions occurring within sDSCs and provide guidelines for which doping levels should be used in device fabrication in absence of oxygen.
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| 4. |
- Cappel, Ute B, et al.
(författare)
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Removing cosmic ray features from Raman map data by a refined nearest neighbor comparison method as a precursor for chemometric analysis.
- 2010
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Ingår i: Applied Spectroscopy. - : Sage Publications. - 0003-7028 .- 1943-3530. ; 64:2, s. 195-200
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Tidskriftsartikel (refereegranskat)abstract
- An algorithm to remove cosmic ray (CR) features from Raman spectra collected in mapping experiments using a charge-coupled device (CCD) is presented. Each spectrum is compared to spectra collected from adjacent points in space using correlation values. The most similar neighbor (MSN) spectrum is selected, offset, and used for identification of CRs. The offset values are defined in terms of the noise level for data with a low signal-to-noise ratio and in terms of the peak height for data with a high signal-to-noise ratio. Scaled intensity values of the MSN spectra are used for replacement of contaminated pixels, allowing for full recovery of underlying spectral features. The algorithm is applicable for any Raman map where the particle sizes within the analyzed mixture are larger than the sampling size or to any other data where the sampling is more frequent than the variation, e.g., time series or temperature profiles. Its application to several maps of pharmaceutical samples is discussed here. With an appropriate offset value for the MSN spectra, no misdetections occur, and all CRs more intense than the offset are removed, which includes the CRs that would have hampered subsequent chemometric analysis by methods such as principal component analysis (PCA).
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| 5. |
- Cappel, Ute B., et al.
(författare)
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The influence of local electric fields on photoinduced absorption in dye-sensitized solar cells.
- 2010
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 132:26, s. 9096-9101
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Tidskriftsartikel (refereegranskat)abstract
- The dye-sensitized solar cell (DSC) challenges conventional photovoltaics with its potential for low-cost production and its flexibility in terms of color and design Transient absorption spectroscopy is widely used to unravel the working mechanism of DSCs A surprising, unexplained feature observed in these studies is an apparent bleach of the ground-state absorption of the dye, under conditions where the dye is in the ground state. Here, we demonstrate that this feature can be attributed to a change of the local electric field affecting the absorption spectrum of the dye, an effect related to the Stark effect first reported in 1913 We present a method for measuring the effect of an externally applied electric field on the absorption of dye monolayers adsorbed on flat TiO2 substrates. The measured signal has the shape of the first derivative of the absorption spectra of the dyes and reverses sign along with the reversion of the direction of the change in dipole moment upon excitation relative to the TiO2 surface A very similar signal is observed in photoinduced absorption spectra of dye-sensitized TiO2 electrodes under solar cell conditions, demonstrating that the electric field across the dye molecules changes upon illumination This result has important implications for the analysis of transient absorption spectra of DSCs and other molecular optoelectronic devices and challenges the interpretation of many previously published results.
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| 6. |
- Dowland, Simon A., et al.
(författare)
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Photoinduced electron and hole transfer in CdS:P3HT nanocomposite films : effect of nanomorphology on charge separation yield and solar cell performance
- 2013
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Ingår i: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 1:44, s. 13896-13901
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Tidskriftsartikel (refereegranskat)abstract
- The influence of morphology on the photophysical properties of blend films containing in situ grown CdS and poly(3-hexylthiophene-2,5-diyl) (P3HT), fabricated utilising a metal xanthate single source precursor, is reported. A combination of transient absorption spectroscopy (TAS), transmission electron microscopy (TEM) and photovoltaic device measurements are employed to study the relationship between the efficiency of charge separation, photocurrent generation and thin film morphology. We identify that a significant proportion of the extractable charge originates from the direct excitation of CdS followed by hole-transfer to the P3HT polymer. The yield of this hole-transfer step from the inorganic CdS to the organic polymer is largely unaffected by the film’s nanomorphology, while the dissociation of P3HT excitons into free charges at the CdS:P3HT interface is found to be strongly dependent on this parameter with high yields of charge transfer only being achieved at high CdS loadings. The present study elucidates design rules for the optimization of hybrid inorganic-organic solar energy conversion devices.
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| 7. |
- Feldt, Sandra M., et al.
(författare)
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Characterization of surface passivation by poly(methylsiloxane) for dye-sensitized solar cells employing the ferrocene redox couple.
- 2010
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 114:23, s. 10551-10558
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Tidskriftsartikel (refereegranskat)abstract
- One-electron outer-sphere redox couples, such as ferrocene/ferrocenium, are an interesting alternative to the iodide/triiodide redox couple that is normally employed in dye-sensitized solar cells (DSCs) because they should reduce the driving force needed to regenerate the dye. Unfortunately, one-electron redox couples also show enhanced recombination with photoinjected electrons, and methods to inhibit this recombination are needed for functioning DSCs. In this study, dye-sensitized titanium dioxide surfaces were passivated by a trichloromethylsilane reaction in order to decrease the fast recombination rates when using the ferrocene redox couple. The formation and binding of poly(methylsiloxane) on the dye-sensitized TiO2 surface was verified with infrared spectroscopy and photoelectron spectroscopy. Photoelectrochemical characterization of the silanization method showed that the treatment decreased the recombination rate of photoinjected electrons with ferrocenium and thereby improved the efficiency of the DSC. Transient absorption spectroscopy revealed, however, that the poly(methylsiloxane) coatings slowed down the regeneration of the oxidized dye by the ferrocene and prevented the regeneration of some of the dye molecules.
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| 8. |
- Lee, George P, et al.
(författare)
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Light-driven transformation processes of anisotropic silver nanoparticles.
- 2013
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 7:7, s. 5911-21
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Tidskriftsartikel (refereegranskat)abstract
- The photoinduced formation of silver nanoprisms from smaller silver seed particles in the presence of citrate anions is a classic example of a photomorphic reaction. In this case, light is used as a convenient tool to dynamically manipulate the shape of metal nanoparticles. To date, very little is known about the prevailing reaction mechanism of this type of photoreaction. Here we provide a detailed study of the shape transformation dynamics as a function of a range of different process parameters, such as photon energy and photon flux. For the first time, we provide direct evidence that the photochemical synthesis of silver nanoprisms from spherical seed nanoparticles proceeds via a light-activated two-dimensional coalescence mechanism. On the other hand, we could show that Ostwald ripening becomes the dominant reaction mechanism when larger silver nanoprisms are grown from photochemically synthesized smaller nanoprisms. This two-step reaction proceeds significantly faster and yields more uniform, sharper nanoprisms than the classical one-step photodevelopment process from seeds. The ability to dynamically control nanoparticle shapes and properties with light opens up novel synthesis avenues but also, more importantly, allows one to conceive new applications that exploit the nonstatic character of these nanoparticles and the ability to control and adjust their properties at will in a highly dynamic fashion.
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| 9. |
- Lindblad, Rebecka, et al.
(författare)
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Energy level alignment in TiO2/metal sulfide/polymer interfaces for solar cell applications.
- 2014
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 16:32, s. 17099-107
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Tidskriftsartikel (refereegranskat)abstract
- Semiconductor sensitized solar cell interfaces have been studied with photoelectron spectroscopy to understand the interfacial electronic structures. In particular, the experimental energy level alignment has been determined for complete TiO2/metal sulfide/polymer interfaces. For the metal sulfides CdS, Sb2S3 and Bi2S3 deposited from single source metal xanthate precursors, it was shown that both driving forces for electron injection into TiO2 and hole transfer to the polymer decrease for narrower bandgaps. The energy level alignment results were used in the discussion of the function of solar cells with the same metal sulfides as light absorbers. For example Sb2S3 showed the most favourable energy level alignment with 0.3 eV driving force for electron injection and 0.4 eV driving force for hole transfer and also the most efficient solar cells due to high photocurrent generation. The energy level alignment of the TiO2/Bi2S3 interface on the other hand showed no driving force for electron injection to TiO2, and the performance of the corresponding solar cell was very low.
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| 10. |
- O'Mahony, Flannan T. F., et al.
(författare)
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Low-temperature solution processing of mesoporous metal-sulfide semiconductors as light-harvesting photoanodes.
- 2013
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Ingår i: Angewandte Chemie International Edition. - : Wiley-VCH Verlagsgesellschaft. - 1433-7851 .- 1521-3773. ; 52:46, s. 12047-51
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Tidskriftsartikel (refereegranskat)abstract
- Structured absorbers: Mesoporous films of highly crystalline Sb 2S3 are prepared from a doctor-bladed precursor paste that is thermally annealed. This facile and versatile processing route allows for control of the pore size through variation of the annealing temperature. The resulting high surface area allows for efficient charge transfer to a polymeric hole acceptor; hence, such films could form the basis of a novel hybrid organic-inorganic photovoltaic device.
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