Novel Blue Organic Dye for Dye-Sensitized Solar Cells Achieving High Efficiency in Cobalt-Based Electrolytes and by Co-Sensitization

Blue and green dyes as well as NIR-absorbing dyes have attracted great interest because of their excellent ability of absorbing the incident photons in the red and near-infrared range region. A novel blue D-pi-A dye (Dyenamo Blue), based on the diketopyrrolopyrrole (DPP)-core, has been designed and synthesized. Assembled with the cobalt bipyridine-based electrolytes, the device with Dyenamo Blue achieved a satisfying efficiency of 7.3% under one sun (AM1.5 G). The co-sensitization strategy was further applied on this blue organic dye together with a red D-pi-A dye (D35). The successful co-sensitization outperformed a panchromatic light absorption and improved the photocurrent density; this in addition to the open-circuit potential result in an efficiency of 8.7%. The extended absorption of the sensitization and the slower recombination reaction between the blue dye and TiO2 surface inhibited by the additional red sensitizer could be the two main reasons for the higher performance. In conclusion, from the results, the highly efficient cobalt-based DSSCs could be achieved with the co-sensitization between red and blue D-pi-A organic dyes with a proper design, which showed us the possibility of applying this strategy for future high-performance solar cells.

Dye-sensitized solar cells using cobalt electrolytes: the influence of porosity and pore size to achieve high-efficiency

Sadig Aghazada, Pascal Comte, Simon Mathew, Mohammad Khaja Nazeeruddin, Aswani Yella

Diffusion impediments in redox shuttles are a major limitation to realizing high power conversion efficiencies (PCEs) in dye sensitized solar cells (DSCs) using cobalt complexes. Mass transport limitations are strongly dependent on the pore size and the porosity of mesoporous TiO2 films. Herein, we examine the major factors responsible for mass transport limitations and identify ways to minimize them, achieving highly efficient cobalt based DSCs. Depending on the electrolyte and dye used, the pore size and the porosity of the TiO2 films must be modulated to facilitate diffusion of cobalt complexes through pores. The influence of porosity, pore size and viscosity of the electrolyte used on the performance of DSCs with different max. obtainable JSCs are studied in detail. These effects were studied using two dye solns., Y123 (0.2 mM) and a cocktail soln. of SM342/Y123 (0.2 mM each, 7 : 1). The JSC is affected primarily by lowered pore sizes as a result of the TiCl4 post-treatment. Transient photocurrent decay measurements were performed on devices featuring photoanodes fabricated with differing porosities and pore sizes. This study indicates that in cells featuring only Y123, recombination rates decreased with decreasing porosity of TiO2 films (i.e. higher TiCl4 concns. used in their post-treatment). Conversely, in DSCs fabricated with the SM342/Y123 dye cocktail, an intermediate TiCl4 post-treatment concn. (20 mM) afforded the lowest recombination rate, resulting in the preservation of a high open-circuit potential (VOC). It was found that this intermediate concn. regime is optimal in order to achieve an efficiency of over 12.7% at full sun intensity with the SM342/Y123 dye cocktail. Finally, it was concluded that the porosity and pore size must be modulated for different dyes and electrolytes to minimize diffusion limitations of the redox species.

Royal Soc Chemistry2017

Strategies to Optimizing Dye-Sensitized Solar Cells

Sophie Wenger

Dye-sensitized solar cells (DSCs) constitute a novel class of hybrid organic-inorganic solar cells. At the heart of the device is a mesoporous film of titanium dioxide (TiO2) nanoparticles, which are coated with a monolayer of dye sensitive to the visible region of the solar spectrum. The role of the dye is similar to the role of chlorophyll in plants; it harvests solar light and transfers the energy via electron transfer to a suitable material (here TiO2) to produce electricity — as opposed to chemical energy in plants. DSCs are fabricated of abundant and cheap materials using inexpensive processes (e.g. screen-printing) and are likely to be a significant contributor to the future commercial photovoltaic technology portfolio. The work conducted during this thesis aimed at optimizing the DSC using three different strategies: The use of versatile organic sensitizers for stable and efficient DSCs, the study of tandem device architectures in combination with other solar cells to harvest a larger fraction of the solar spectrum, and the development of a validated optoelectric model of the DSC. Organic donor-π-acceptor dyes are an interesting alternative to the standard metal-organic complexes used in DSCs. Efficient photovoltaic conversion and stable performance could be demonstrated with three classes of donor systems, namely diphenylamine, difluorenylaminophenyl, and π-extended tetrathiafulvalene. The highest conversion efficiencies were obtained with a difluorenylaminophenyl donor system (η = 8.3 % with a volatile electrolyte and η = 7.6 % with a solvent-free ionic liquid, which was a new record for organic dyes at the time of publication). Surprisingly, efficient regeneration of the oxidized dye by the I-/I3- redox mediator was found with the π-extended tetrathiafulvalene system, even though the thermodynamic driving force was as low as 150 mV. So far driving forces of 300-500 mV had been regarded as necessary for efficient regeneration of the dye cation. Also, important structure-property relationships pertaining to the recombination of electrons with the electrolyte and to the stability of the device could be identified (i.e. effect of linear vs. branched structure, linker length, and moieties used). The power conversion efficiency of solar cells can be extended beyond the limit for a single cell (∼ 30 %) by using multiple cells with different optical gaps in a tandem device. DSCs and chalcopyrite Cu(In,Ga)Se2 (CIGS) solar cells have complementary optical gaps and are thus suitable systems for integration in a tandem device. It was shown that a monolithic DSC/CIGS tandem device has the potential for increased efficiency over a mechanically stacked device due to increased light transmission to the bottom cell, and a monolithic DSC/CIGS device with an initial efficiency of η = 12.2 % was demonstrated. The degradation of the devices — induced by the corrosion of the CIGS cell in contact with the I-/I3- redox mediator — could be retarded with a protective thin conformal ZnO/TiO2 oxide layer coated on the CIGS cell by atomic layer deposition. Finally, an experimentally validated optical and electrical model of the DSC has been developed to assist the optimization process, which is predominantly conducted by empirical means in the DSC research community. The optical model allows to accurately calculate the internal quantum efficiency of devices, i.e. the ratio of extracted electrons to absorbed photons by the dye, a crucial and so far difficult to determine characteristic. Intrinsic parameters — like injection efficiency, electron diffusion length, or distribution of trap states in the TiO2 — can be extracted from experimental steady-state and time-dependent data with the electric model. The model allows to make a comprehensive and quantitative loss analysis of the different optical and electric loss channels in the DSC. The model has been implemented with a graphical user interface for straightforward usage. All three optimization strategies — organic dyes, tandem architecture, and device modeling — developed during this thesis make a valuable contribution to the development and commercialization of inexpensive and high efficiency DSCs. They enable a comprehensive view of the system and pave the way for a systematic analysis and reduction of losses, which has been the ultimate route to success for several established photovoltaic technologies.

EPFL2010

Novel organic dyes for enhanced red to near IR response in dye sensitised solar cells

The aim of this work was to develop new, organic dyes, capable of harvesting photons in the red to near-IR region of the spectrum. A series of squaraine and tricarbocyanine dyes were produced and characterised and their optical and redox properties studied. The results of initial photovoltaic tests, followed by optimisations of cell performance, have also been presented. These clearly demonstrate the effectiveness of these dyes in solar cells. A total of 12 new squaraine dyes were successfully synthesised, seven of which were tested in "dye-sensitised" solar cells. The efficiencies ranged from 1.2%-3.7%, for the best dye [B1]. It was concluded that enhanced performance could be achieved in the presence of chenodeoxycholic acid (CDCA) and tetrabutylpyridine (TBP). These additives both help to prevent aggregation and increase the cell potential, limiting charge collection losses and enhancing performance. Three new tricarbocyanine dyes were also synthesised, two of which were used in solar cells. Unfortunately, due to the interaction of [B12] with the electrolyte, the dye proved to be unstable, as both the absorption maxima in UV-vis and fluorescence emission wavelengths were shifted to higher energies. Thus, the red response of the dye was significantly reduced and photovoltaic performance hindered. A limited photo-response of [B14] was also seen, although this dye appeared to be very stable in the presence of the electrolyte. To deduce the possible reasons for the poor performance of these dyes, their optical and electrochemical properties were investigated. Thus, cyclic voltametry was employed to identify the redox potentials of the dyes and their charge injection and recombination dynamics were studied through nanosecond time-resolved transient laser spectroscopy. It was concluded that the dyes theoretically possess the ideal characteristics for solar cell function and that the problem of [B14] lay in the purity of the dye. [B14] proved to be very difficult to purify as the dye was unstable in solution and decomposed on the columns employed in chromatography. Fortunately the dye appeared to be stable in the presence of an electrolyte when adsorbed on TiO2. The dye gave an IPCE of 12% between 800 – 900nm, which is particularly impressive, especially if the purity of the dye is considered. A new method of purification must be found however, if photovoltaic performance is to be enhanced. Finally, the effects of a compact blocking layer on device performance were studied. It was clearly demonstrated that a compact layer was essential. This was investigated and a relationship between the structure of the dye and the necessity of the blocking layer was established.

EPFL2006

Strategies to Optimizing Dye-Sensitized Solar Cells

Sophie Wenger

EPFL2010

Dye-sensitized solar cells using cobalt electrolytes: the influence of porosity and pore size to achieve high-efficiency

Sadig Aghazada, Pascal Comte, Simon Mathew, Mohammad Khaja Nazeeruddin, Aswani Yella

Royal Soc Chemistry2017

Novel organic dyes for enhanced red to near IR response in dye sensitised solar cells

EPFL2006

Novel Blue Organic Dye for Dye-Sensitized Solar Cells Achieving High Efficiency in Cobalt-Based Electrolytes and by Co-Sensitization

Dye-​sensitized solar cells using cobalt electrolytes: the influence of porosity and pore size to achieve high-​efficiency

Strategies to Optimizing Dye-Sensitized Solar Cells

Novel organic dyes for enhanced red to near IR response in dye sensitised solar cells

Strategies to Optimizing Dye-Sensitized Solar Cells

Dye-​sensitized solar cells using cobalt electrolytes: the influence of porosity and pore size to achieve high-​efficiency

Novel organic dyes for enhanced red to near IR response in dye sensitised solar cells

Dye-sensitized solar cells using cobalt electrolytes: the influence of porosity and pore size to achieve high-efficiency

Dye-sensitized solar cells using cobalt electrolytes: the influence of porosity and pore size to achieve high-efficiency