Liquid State and Zombie Dye Sensitized Solar Cells with Copper Bipyridine Complexes Functionalized with Alkoxy Groups

Copper redox mediators can be employed in dye sensitized solar cells (DSCs) both as liquid electrolytes or as solid state hole transport materials (HTMs). The solid state devices that employ copper complex HTMs can be simply obtained by solvent evaporation in liquid state devices. During this evolution, the copper complex molecules present in the electrolyte solvent slowly aggregate in the pores of the TiO2 film and also close the gap between the TiO2 film and counter electrode. However, the crystallization of the HTM that infiltrated in the mesoscopic TiO2 pores can lead to low photovoltaic performance. In order to prevent this problem, we designed two copper redox mediators [Cu(beto)2]1+ (beto = 4,4′-diethoxy-6,6′-dimethyl-2,2′-bipyridine) and [Cu(beto2Ox)2]1+ (beto2Ox = 4,4′-bis(2- methoxyethoxy)-6,6′-dimethyl-2,2′-bipyridine) with extended side chains. First, we studied these complexes in liquid state devices in reference to the [Cu(tmby)2]2+/1+ complex (tmby = 4,4′,6,6′- tetramethyl-2,2′ bipyridine). The solar-to- electrical power conversion efficiencies for liquid state devices were over 10% for all of the complexes by using the organic Y123 dye under 1000 Wm−2 AM1.5G illumination. However, solid state devices showed significantly diminished charge transport properties and short circuit current density values even though the crystallization was reduced.

Molecular gelation of ionic liquid-sulfolane mixtures, a solid electrolyte for high performance dye-sensitized solar cells

Jean-David Décoppet, Michael Graetzel, Thomas Moehl, Shaik Mohammed Zakeeruddin

Cyclohexanecarboxylic acid-[4-(3-tetradecylureido)phenyl]amide is an efficient gelator to solidify ionic liquid electrolytes. In this paper we apply this low molecular weight gelator to solidify the newly prepared sulfolane based ionic liquid electrolyte. This solid electrolyte is successfully applied as an electrolyte for dye sensitized solar cells. This solid electrolyte is thermo-reversible, upon heating it will become a liquid and at room temperature it will solidify, facilitating the cell filling by the electrolyte. Applying this solid electrolyte we obtained 7.8% power conversion efficiency under simulated AM 1.5 full sunlight intensity. The devices with liquid and solid electrolytes were analysed by electrochemical impedance spectroscopy to explain the differences in the photovoltaic performance. These cells were also measured under outdoor conditions at Jeddah, Saudi Arabia to explore the feasibility of practical applications of this electrolyte.

Royal Society of Chemistry2014

Solid state nanocrystalline titanium oxide photovoltaic cells

The dye solar cell, is a novel photoelectrochemical solar cell presenting unique advantages, as the use of low cost materials and the potential simplicity of manufacturing. However, a liquid electrolyte is actually required for the transport of the photogenerated positive charges. A major breakthrough is the replacing of the liquid electrolyte by a solid-state hole conducting material – the aim of this work. First, the metal/TiO2 junction was investigated, with either silver or gold as rectifying contact. Sensitization was demonstrated, as action spectra were measured using different dyes. The evaporated metal could not enter the pores of the nanocrystalline TiO2 to contact all the dye molecules, hence only low photovoltaic performances were obtained. Furthermore, these metal/TiO2 junctions showed a high sensitivity to humidity and to forward bias polarization. The use of an electrically conducting polymer, poly(bithiophene), was studied in a metal/polymer junction and in TiO2/polymer devices with flat and nanocrystalline TiO2 electrodes. The photoelectric characterizations indicated that electrochemically reduced poly(bithiophene) was able to inject electrons into TiO2, i.e. sensitizing TiO2, and it acted as a hole conducting layer. Short-circuit current densities of 2-3 mA/cm2 were measured at an irradiation of 1.2 W/cm2. The open-circuit voltages were in the 250-350 mV range, depending on the light intensity and temperature. The use of a transparent hole conducting material, CuI, which is a wide bandgap p-type semiconductor, was demonstrated in a nanocrystalline junction made of highly porous sensitized TiO2 and solution-cast CuI. A short-circuit current of 1 mA/cm2 was achieved under one sun simulated light; the open-circuit voltage was 600 mV and the light-to-power conversion efficiency was 0.3 %. The peak quantum efficiencies of 8 % in the UV, and 3 % in the visible, showed that the nanocrystalline junction was working inefficiently, probably due to the poor electrical contact between the TiO2 nanocrystallites and the CuI crystals. Furthermore, the sensitizer was not tuned to inject holes into the valence band of CuI. As conclusion, a controlled-capillary pore based sensitized device is suggested. In this concept, all the internal surface of the TiO2 electrode coated with sensitizer is contacted with the transparent hole conducting layer, hence improving the photovoltaic properties of the device.

EPFL1996

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

Interface engineering in solid-state dye-sensitized solar cells

Jessica Krüger

EPFL2003

Solid state nanocrystalline titanium oxide photovoltaic cells

EPFL1996