Significant Improvement of Dye-Sensitized Solar Cell Performance by Small Structural Modification in π-Conjugated Donor-Acceptor Dyes

Two donor-π-acceptor (D-π-A) dyes are synthesized for application in dye- sensitized solar cells (DSSC). These D-π-A sensitizers use triphenylamine as donor, oligothiophene as both donor and π-bridge, and benzothiadiazole (BTDA)/cyanoacrylic acid as acceptor that can be anchored to the TiO2 sur- face. Tuning of the optical and electrochemical properties is observed by the insertion of a phenyl ring between the BTDA and cyanoacrylic acid acceptor units. Density functional theory (DFT) calculations of these sensitizers provide further insight into the molecular geometry and the impact of the additional phenyl group on the photophysical and photovoltaic performance. These dyes are investigated as sensitizers in liquid-electrolyte-based dye-sensitized solar cells. The insertion of an additional phenyl ring shows significant influence on the solar cells’ performance leading to an over 6.5 times higher efficiency (η = 8.21%) in DSSCs compared to the sensitizer without phenyl unit (η = 1.24%). Photophysical investigations reveal that the insertion of the phenyl ring blocks the back electron transfer of the charge separated state, thus slowing down recombination processes by over 5 times, while maintaining efficient electron injection from the excited dye into the TiO2-photoanode.

Electronic and structural modification of titanium dioxide/zinc oxide photoanode for dye-sensitized solar cells

Aravind Kumar Chandiran

Dye-sensitized solar cells (DSC) are a new class of molecular photovoltaics that mimics the natural photosynthesis, for the direct conversion of sunlight into electricity. A typical DSC is a sandwich of a dye sensitized nanoparticle TiO2 film and a catalyst coated counter electrode, with a redox electrolyte filling the space in between. The high internal surface area of the mesoporous TiO2 film ensures higher dye uptake for an efficient light harvesting. Following the light illumination, an electron from the highest occupied molecular orbitals (HOMO) of the dye is excited to its lowest unoccupied molecular orbitals (LUMO). Due to an effective electronic orbital coupling between dye and TiO2, the excited electrons are injected into TiO2. The oxidized dye is regenerated by the electron donor present in the electrolyte. The circuit is completed by the transfer of photogenerated electrons in TiO2 via an external load, to counter electrode regenerating the oxidized electrolyte species. In a conventional DSC, the transport rate of the photogenerated electrons in TiO2 competes with the parasitic electron recombination, as these two processes occur at a similar ms time domain. This thesis work is aimed at the fundamental understanding of these electron transfer processes at sensitized photoanodes that were subject to different bulk and surface electronic structural modifications. The implications were shown to be of profound interest for the fabrication of high efficiency and low cost dye-sensitized solar cells. In the first part of the thesis, the bulk electronic structure of the anatase TiO2 nanoparticles is modified by the incorporation of different concentrations of aliovalent cations (Nb5+, Ga3+, Y3+) in the crystal lattice. The cationic doping/substitution in the nanoparticles is achieved by hydrothermal process. The modified nanoparticles retained the parent anatase crystal structure of TiO2. The transparent dye-sensitized solar cells made with these modified films, using our standard heteroleptic metal complex sensitizers and iodide/triiodide redox electrolyte, displayed enhanced photovoltaic performances, at certain added concentrations. Charge extraction measurements in DSC, reveals a formation of deeper trap states below the conduction band of titanium dioxide when Nb ion is incorporated into the TiO2 lattice. On the other hand, Ga3+ and Y3+ did not significantly affect the trap states distribution compared to the reference device. The modification in the trap states and the oxygen stoichiometry due to these cation inclusions significantly influenced the electron recombination and transport rates. These properties are investigated in detail using transient decay techniques. Following the study on the electronic structure of the bulk TiO2, the influence of the surface modification of the TiO2 nanoparticles on the electron transfer dynamics is investigated. The kinetics of electron recombination from TiO2 to the single electron redox shuttles is fast, leading to a significant loss in the open-circuit potential (VOC) of devices. The emergence of cobalt complexes as a potential electrolyte motivated us to investigate the role of surface passivation of the titanium dioxide nanoparticles. Insulating sub-nanometer oxide tunneling layers deposited by atomic layer deposition (ALD) are known to block the electron recombination, thereby, leading to an increase in the VOC and the collection efficiency of the solar cell. A general perception in the DSC community is that any insulating oxide layer can block the recombination. However, in this work, it is unraveled that, just the insulating property of oxides is not sufficient. In addition, the properties such as the conduction band position and the oxidation state of the insulating oxide, the electronic structural modification induced to the underlying TiO2 mesoporous film, modification of surface charges (isoelectric point) and charge of the electrolyte species have to be considered. A complete photovoltaic study has been done by depositing different cycles (by ALD) of four insulating oxides (Ga2O3, ZrO2, Nb2O5 and Ta2O5) and their recombination characteristics, surface electronic properties, transport rate and injection dynamics are investigated with a standard organic dye and Co2+/Co3+ redox mediator. A comparison is made with the conventional iodide/triiodide electrolyte. The second part of the thesis is focused at the development of new type of photoanodes for effective electron transport to increase the charge collection efficiency. We present a way of utilizing thin and conformal overlayer of titanium dioxide or zinc oxide on an insulating mesoporous template as a photoanode for dye-sensitized solar cells. Different thicknesses of TiO2 ranging from 1 to 15 nm are deposited on the surface of the template by ALD. This systematic study helps unraveling the minimum critical thickness of the TiO2 overlayer required to transport the photogenerated electrons efficiently. A merely 6 nm thick TiO2 film on a 3 μm mesoporous insulating substrate is shown to transport 8 mA/cm2 of photocurrent density along with ≈900 mV of open-circuit potential, when using our standard donor-π-acceptor sensitizer and Co(bipyridine)3 redox mediator. The three dimensional conformal shell on the insulating core also exhibits one order of magnitude higher transport rate compared to the conventional TiO2 nanoparticles. Similar nanostructures were made by depositing ZnO on an insulating template and the electron transfer properties are compared with titania. We also developed ALD recipe for the deposition of crystalline TiO2 or ZnO at low temperatures (< 200 °C) on arbitrary mesoporous insulating templates, considering their prospects of making photoanodes on flexible plastic substrates. The experience gained about the deposition of conformal and pin-hole free TiO2 layer in the previous section is extended for the high efficiency solid-state mesoscopic solar cells based on CH3NH3PbI3 perovskite absorbers. We show that a 2 nm as-deposited ALD overlayer on a mesoporous TiO2 film, printed on a bare conducting glass, is sufficient to arrest the recombination process that lead to a power conversion efficiency of 11.5 %. A detailed investigation on the electron back reaction is presented using electrochemical impedance spectroscopy.

EPFL2013

Harvesting UV Photons for Solar Energy Conversion Applications

Magdalena Anna Marszalek, Jacques-Edouard Moser

We report the synthesis and characterization of five new donor–π–spacer–acceptor dye molecules with a diphenylamine donor, fluorene–1,2,5-oxadiazole spacers and a range of acceptor/anchor groups (carboxylic acid 1, cyanoacrylic acid 2 and 3, alcohol 4 and cyano 5) to facilitate electron injection from the excited dye into the TiO2 photoanode in dye-sensitized solar cells (DSSCs). Detailed photophysical studies have probed the dyes' excited state properties and revealed structure–property relationships within the series. Density functional theory (DFT) and time dependent DFT (TDDFT) calculations provide further insights into how the molecular geometry and electronic properties impact on the photovoltaic performance. A special feature of these dyes is that their absorption features are located predominantly in the UV region, which means the dye-sensitized TiO2 is essentially colorless. Nevertheless, DSSCs assembled from 1 and 2 exhibit photovoltaic power conversion efficiencies of η = 1.3 and 2.2%, respectively, which makes the dyes viable candidates for low-power solar cells that need to be transparent and colorless and for applications that require enhanced harvesting of UV photons.

Royal Soc Chemistry2014

High-conversion-efficiency organic dye-sensitized solar cells: molecular engineering on D-A-pi-A featured organic indoline dyes

Michael Graetzel, Magdalena Anna Marszalek, Yinghui Wu, Shaik Mohammed Zakeeruddin, Qixing Zhang

This paper reports a new D-A-pi-A organic dye WS-9, which is derived from the known dye WS-2 by incorporating an n-hexylthiophene unit into the pi-conjugation. Due to the presence of a strong electron-withdrawing benzothiadiazole unit in the pi-bridge, the specific D-A-pi-A organic dyes show more complicated electronic transition absorption bands than traditional D-pi-A dyes. The origins of the absorption bands in D-A-pi-A organic dyes are analysed by density functional theory (DFT). The calculated results in combination with the deprotonation experiments suggest that the spectral response range of D-A-pi-A organic dyes is superior to that of D-pi-A ones. When employed in dye-sensitized solar cells (DSSCs), the two dyes show a large difference in aggregation behaviour. It was found that WS-2 forms the unfavourable aggregates more easily. High performance of WS-2 strongly depends on the coadsorbent and suitable dye bath solvent. In contrast, WS-9 shows strong anti-aggregation ability, and always exhibits high performance regardless of the coadsorbent and dye bath solvent. Transient photovoltage and photocurrent decay experiments as well as electrochemical impedance spectroscopy indicate that the injected electron lifetime and charge recombination resistance are largely increased due to the introduction of a hexylthiophene unit, resulting in the high photovoltage based on WS-9. The optimized power conversion efficiency of WS-9 reaches 9.04% with high photocurrent (18.00 mA cm(-2)) and photovoltage (696 mV). The accelerating dye photo-stability was tested upon light irradiation of a dye-adsorbed TiO2 film in the absence of redox electrolyte, and a WS-9-based DSSC device with ionic liquid redox electrolyte. These results suggest that the structural engineering of organic dyes is important for highly efficient photovoltaic performance of solar cells, and our research will pave a novel way to design new efficient D-A-pi-A organic dye sensitizers.