Dye-sensitized sputtered titanium oxide films for photovoltaic applications: influence of the O2/Ar gas flow ratio during the deposition

À propos de ce résultat

Cette page est générée automatiquement et peut contenir des informations qui ne sont pas correctes, complètes, à jour ou pertinentes par rapport à votre recherche. Il en va de même pour toutes les autres pages de ce site. Veillez à vérifier les informations auprès des sources officielles de l'EPFL.

Interface engineering in solid-state dye-sensitized solar cells

Jessica Krüger

Dye-sensitised nanocrystalline solar cells are currently subject of intense research in the framework of renewable energies as a low-cost photovoltaic device. In particular dye-sensitised cells based on spiro-MeOTAD have gained attention as promising approach towards an organic solid-state solar cell. However, the efficiency in such dye-sensitised solid-state solar devices (SSD) was so far only ca. 10 % of the values reported at AM1.5 for the classical dye-sensitised solar cell with an electrolyte hole transporting medium (DSSC). The objective of the present work is to study the limitations that emerge from the exchange of the electrolyte by the solid-state system and that oppose photovoltaic photon-to-electron conversion as high as for the DSSC. Interfacial charge recombination is an important loss mechanism in dye-sensitised solar cells. This is particularly true for SSD, as the solid hole-transporting medium is less efficient in screening of internal fields which assist recombination. A variety of strategies were tested in the SSD to minimise interfacial charge recombination. The most promising approach was the blending of the hole-transporting medium with tert.-butylpyridine (tBP) and lithium ions. Optical and electrochemical techniques, such as nanosecond laser spectroscopy, impedance spectroscopy and photovoltaic characterisation measurements, were used to study the impact of the additives on the SSD. Both lithium ions as well as tBP were found to increase the open circuit potential of the SSD. At the same time tBP was found to considerably lower the current output. The interaction of the additives was studied and their concentration in the spiro-MeOTAD medium optimised. The doping of the spiro-MeOTAD film, which was intended to support the hole transport, was found to enhance interfacial recombination significantly. The morphological properties of the TiO2, in particular layer thickness, particle size and film porosity, play a more important role in the SSD than in the DSSC. Penetration of the hole conductor into the TiO2 pores and electron diffusion length are coupled to these properties. As a result the light harvesting cannot be controlled at will via the TiO2 film thickness and the active surface area for dye adsorption. An enhanced light harvesting for thin TiO2 layers offers advantages for the charge transport and the formation of the interpenetrating network. The dye uptake in presence of silver ions was found to increase the dye loading and to significantly improve the device performance of thin TiO2 layer devices. The mechanism of this simple dye modification technique was studied by a variety of spectroscopic techniques. From spectroscopic evidence it is inferred that the silver is binding to the sensitiser via the ambidentate thiocyanate, allowing the formation of ligand-bridged dye complexes. The beneficial influence of the silver ions on the photovoltaic performance was not limited to the application of the standard N3 dye nor to the spiro-MeOTAD. SSDs were furthermore studied by frequency resolved techniques. Intensity modulated photocurrent spectroscopy (IMPS) and intensity modulated photovoltage spectroscopy (IMVS) were performed over a wide range of illumination intensities. The IMPS and IMVS responses provide information about charge transport and electron-hole recombination processes respectively. For the range of light intensities investigated, the dynamic photocurrent response appears to be limited by the transport of electrons in the nanocrystalline TiO2 film rather than by the transport of holes in the spiro-MeOTAD. The diffusion length of electrons in the TiO2 was found to be 4.4 μm. This value was almost independent of the light intensity as a consequence of the fact that the electron diffusion coefficient and the rate constant for electron-hole recombination both increase in the same way with light intensity but with opposite sign. The results of this work provide for a substantial improvement of the overall photovoltaic performance compared to earlier results for this type of SSD. However, this study reveals also that high conversion efficiencies as are measured for DSSC are not likely to be reachable with the spiro-MeOTAD system due to the significantly slower charge transport in the spiro-MeOTAD compared to the electrolyte redox mediator.

EPFL2003

Alternative redox systems for the dye-sensitized solar cell

Hervé Nusbaumer

Due to their high efficiencies and their potentially low production costs, dye-sensitized solar cells (DSSC) have attracted much attention during the last few years. The technology is based on a layer made of mesoscopic TiO2 film which significantly increases the optical path for light harvesting by the surface-anchored sensitizer molecules, whilst keeping an efficient contact with the electrolytic solution. These sensitizer molecules are often based on ruthenium polypyridyl complexes because of their high absorption coefficients in the visible, but any dye could be used to sensitize the semiconducting TiO2. The standard DSSC usually contain organic electrolytes with dissolved triiodide/iodide as the redox couple. Cells based on alternative electrolytes have been developed and were used in early DSSC designs, but showed somehow deceiving photovoltaic performances. Until now, endeavors to increase the photovoltage of dye-sensitized nanocrystalline cells by replacing iodide by a one-electron, outer-sphere redox couple with a more positive oxidation potential have not succeeded. This has been largely due to limitations imposed by the dark current and the slow diffusion of the alternate mediator. The work presented here focused on finding efficient alternative redox couples for the DSSC, able to rival the classical triiodide/iodide couple. The tested compounds were triarylamines, platinum complexes and cobalt complexes. Triarylamines and platinum complexes proved considerably less effective than the classical couple in term of photoelectrochemical efficiencies. Cobalt complexes however displayed far more interesting behavior. The experiments carried out demonstrated that the [Co(bip)2]3+/2+ complexes were the most suitable candidates to be used as redox mediators as their photoelectrochemical and kinetic behavior rivaled those of the triiodide/iodide redox couple. The system however had to be optimized to reach high efficiencies. Heteroleptic dyes incorporating long alkyl chains were found to be the most appropriate category of dye, boosting further the DSSC efficiency by reducing the dark current within the cells. Co-grafting the sensitizer and co-adsorbent led to an improved photovoltaic efficiency through the increased photocurrent. Silver addition in the dye solution also leads to a global improvement of the photovoltaic parameters. To avoid diffusion problems with the large molecules in the electrolyte, very thin nanocrystalline TiO2 layers had to be employed. A 3 μm thick nanoporous layer with a 3 μm scattering layer was found to be optimal. As cobalt complexes may undergo electrochemical processes on the SnO2 layer of the photoelectrode, a blocking layer of compact TiO2 was used to reduce the dark current. The electrochemical regeneration of the cobalt complexes with the SnO2 is not fast enough to support cell function and the counter electrode must be covered either with platinum or gold layer to ensure a good fill factor. The optimization of the electrolyte itself mainly concerned the choice of the solvent, the redox mediator concentration, the best degree of oxidation, the additives that can be used to improve the photovoltaic parameters and finally how to increase the redox couple solubility. The best efficiencies were achieved with an acetonitrile/ethylene carbonate (2:3) solvent mixture, with a total redox mediator concentration between 0.10 to 0.15 M. If 10% of this total concentration is oxidized, the current density reaches its maximum whilst having a negligible effect on the photovoltage. 4-tert-butylpyridine (TBP) and lithium perchlorate were tried as additives in the electrolyte, as TBP increases the photovoltage and Li+ the photocurrent. The optimal concentrations of these two additives was found to be around 0.05 M TBP and 0.1 M LiClO4 for an electrolyte having a total cobalt complex concentration of 0.1 M. Mass-transport within the cell is the limiting factor for high currents when using cobalt complexes as redox mediators. Attempts to reduce the solvent viscosity by using alternative solvents to the acetonitrile/ethylene carbonate mixture were not successful. One way to solve the diffusion problem was to irradiate the cell from the counter electrode side. This method works well at high irradiation intensities. Finally, reduction of the distance between the electrodes also enhances diffusion. The use of [Co(bip)2]3+/2+ complexes, with appropriate dyes and taking into account the optimizations already described above, allowed efficiencies of 8% under an irradiance of 95 W · m-2, as well as IPCEs over 80% at 540 nm to be obtained. At full sun, efficiencies of over 4% were reached, with short circuit current densities of 9.5 mA · cm-2 and open circuit voltages of the order of 860 mV.

EPFL2004

Solid-State Sensitized Heterojunction Solar Cells

Soo-Jin Moon

Dye-sensitized solar cells (DSCs) are considered as an emerging technology in order to replace conventional silicon solar cells or thin film solar cells such as amorphous silicon, CIGS, and CdTe. Liquid electrolytes containing iodide/triiodide redox couple have a durability problem due to the corrosion of metal contacts. In order to improve the long-term stability of DSC device it is important to find an alternate efficient redox couple. In search of this we are using 2,2',7,7'-tetrakis-(N,N-di-methoxyphenylamine)- 9,9'-spirobifluorene (spiro-OMeTAD) as a hole transport material for solid-state dye-sensitized solar cells (SSDSCs). In comparison to the liquid electrolytes the efficiencies of SSDSCs are inferior, they are around only 30% of the efficiencies obtained with the liquid electrolytes. In optimizing the device performance and stability of SSDSCs, various light harvesting systems are employed to enhance a photovoltaic performance and investigated their properties in SSDSCs. In SSDSCs we use thin TiO2 films to avoid the pore-filling problem of HTM. Hence it is critical to use high molar extinction coefficient dyes with an efficient light harvesting capability for SSDSCs. Representative ruthenium sensitizers such as N719 or Z907 have shown good and stable performances in liquid electrolyte-based DSCs. However, their performances are low in SSDSCs due to insufficient light harvesting in thin mesoporous TiO2 films. A new family of heteroleptic polypyridyl ruthenium sensitizers having thiophene units was employed to increase the light harvesting capabilities and their applicability in SSDSCs. These new dyes could improve the absorbed photon-to-current conversion efficiencies as well as power conversion efficiencies due to their high molar extinction coefficients. The thiophene units of the ancillary ligands not only enhanced molar extinction coefficients but also augmented electron lifetime in the devices. In general, ruthenium sensitizers possess lower molar extinction coefficients compared to organic dyes. In order to increase the molar extinction coefficients and bathochromic shift in the absorption spectra of organic dyes, we applied donor-acceptor concept in organic dyes with different π-conjugation bridges. Consequently, we achieved 6 % power conversion efficiency at AM 1.5G solar irradiation (100 mW/cm2) in a solid-state dye-sensitized solar cell. Transient photovoltage and photocurrent decay measurements showed that the enhanced performance of this device was ascribe to higher charge collection efficiency over a wider potential range. We also examined near infrared absorbing dyes and they could be employed to different device architectures such as tandem cells, Förster Resonance Energy Transfer, or co-sensitization to substantiate panchromatic response. Another interesting type of sensitizers is semiconductor or quantum dots due to their unique properties. However, the efficiency of the semiconductor-sensitized solar cells was only 1-2 % range. Recently, much improved efficiencies were reported with Sb2S3-sensitized cells using different hole conductors. The Sb2S3-sensitized cells with spiro-OMeTAD demonstrated a very high incident photon-to-conversion efficiency (IPCE) of 90 %. This excellent result shows that the semiconductor sensitizers are promising candidate as light absorbers for SSDSCs. Most of the standard ruthenium and organic dyes have the limited absorption in near infrared region of the solar spectrum. Porphyrin sensitizers possess strong absorptions in the visible and near infrared region and they have good chemical, photochemical and thermal stability. However, the power conversion efficiency of SSDSCs devices using a novel D-π-A porphyrin we reached only 1.6 %. In order to improve a cell performance, porphyrin was co-sensitized with an organic dye to increase light harvesting capability in the green wavelength region as well as to reduce the dye aggregation. Instead of spiro-OMeTAD a polymer hole conductor was applied, which had intense spectral response in the visible region. Interestingly, in this system the polymer hole conductor showed dual functions, as a light absorber and a hole transporter. This hybrid solar cell exhibited a clear panchromatic response and improved the power conversion efficiency of device compared to the cell with spiro-OMeTAD.

EPFL2011