Molecular Engineering of Push-Pull Porphyrin Dyes for Highly Efficient Dye-Sensitized Solar Cells: The Role of Benzene Spacers

Porphyrins have drawn much attention as sensitizers owing to the large absorption coefficients of their Soret and Q bands in the visible region. In a donor and acceptor zinc porphyrin we applied a new strategy of introducing 2,1,3-benzothiadiazole (BTD) as a pi-conjugated linker between the anchoring group and the porphyrin chromophore to broaden the absorption spectra to fill the valley between the Soret and Q bands. With this novel approach, we observed 12.75% power-conversion efficiency under simulated one-sun illumination (AM1.5G, 100 mW cm(-2)). In this study, we showed the importance of introducing the phenyl group as a spacer between the BTD and the zinc porphyrin in achieving high power-conversion efficiencies. Time-resolved fluorescence, transient-photocurrent-decay, and transient-photovoltage-decay measurements were employed to determine the electron-injection dynamics and the lifetime of the photogenerated charge carriers.

Synthesis, Characterization, and DFT-TDDFT Computational Study of a Ruthenium Complex Containing a Functionalized Tetradentate Ligand

Pascal Comte, Filippo de Angelis, Davide Di Censo, Paul Liska, Mohammad Khaja Nazeeruddin, Guido Viscardi

A ruthenium complex trans-[Ru(L)(NCS)2], L ) 4,4¢¢¢-di- tert-butyl-4¢,4¢¢-bis(carboxylic acid)-2,2¢:6¢,2¢¢:6¢¢,2¢¢¢- quaterpyridine (N886), was synthesized and characterized by spectroscopic and electrochemical methods. The absorption spectrum of the N886 complex shows metal-to-ligand charge-transfer transitions in the entire visible region and quasi-reversible oxidation and reduction potentials at E1/2 ) +0.38 and -1.92 V vs ferrocene, respectively. The electronic spectra of the N886 complex were calculated by density functional theory (DFT)-time-dependent DFT, which qualitatively reproduces the experimental absorption spectra for both the protonated and deprotonated species. From the analysis of the computed optical transitions of N886, we assign its absorption bands as mixed Ru/SCN-to-quaterpyridine charge-transfer transitions, which extend from the near-IR to the UV regions. The panchromatic response of the N886 complex renders it as a suitable sensitizer for solar energy conversion applications based on titanium dioxide mesoporous electrodes. The preliminary results using the N886 complex as a sensitizer in a dye-sensitized solar cell, with an electrolyte containing 0.60 M butylmethylimidazolium iodide, 0.03 M I2, and 0.50 M tert-butylpyridine in a mixture of acetonitrile and valeronitrile (volume ratio 1:1), show 40% incident photonto- current efficiencies, yielding under standard AM 1.5 sunlight a short-circuit photocurrent density of 11.8 ± 0.2 mA/cm2, an open-circuit voltage of 680 ± 30 mV, and a fill factor of 0.73 ± 0.03, corresponding to an overall conversion efficiency of 5.85%.

2006

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

High-voltage (1.8 V) tandem solar cell system using a GaAs/AlXGa(1-X)As graded solar cell and dye-sensitised solar cells with organic dyes having different absorption spectra

Pascal Comte, Michael Graetzel, Paul Liska, Péter Péchy, Jun Ho Yum

Stacked multijunction (tandem) solar cells have been prepared by mechanically stacking dye-sensitised solar cells (DSCs) and a GaAs/AlXGa(1-X)As graded solar cell (GGC) as the top and bottom cells, respectively. Three organic dyes with different absorption spectra (D131, D102 and D205) were used in the DSCs, in order to match the photocurrent density between the DSC and the GGC. Tuning the absorption range of the DSC by choosing an appropriate dye, increased the overall photovoltaic conversion efficiency due to the optimal utilisation of the solar spectrum in the individual cells. The open circuit photovoltages (V-OC) of the GGC and the DSC with D131 were 1.11 V and 0.76 V, respectively, resulting in a V-OC of 1.85 V and a photovoltaic conversion efficiency of 7.63% for the tandem cell. Although the overall conversion efficiency has not exceeded that of the GGC (7.66%), these tandem cells provide adequate V-OC values for water splitting applications. (C) 2011 Elsevier Ltd. All rights reserved.

2011

Solid-State Sensitized Heterojunction Solar Cells

Soo-Jin Moon

EPFL2011