Microsecond dye regeneration kinetics in efficient solid state dye-sensitized solar cells using a photoelectrochemically deposited PEDOT hole conductor

Microsecond dye-regeneration kinetics was observed in efficient solid state dye-sensitized solar cells using photoelectrochemically deposited poly(3,4-ethylenedioxythiophene (PEDOT) hole conductors using transient absorption spectroscopy. The dye-regeneration rate is orders of magnitude slower than the case using the I-/I3- redox couple or commonly used small molecule hole conductor and is attributed to the low dye to PEDOT ratio within the films

Enhanced electron lifetime of CdSe/CdS quantum dot (QD) sensitized solar cells using ZnSe core-shell structure with efficient regeneration of quantum dots

Research on development of efficient passivation materials for high performance and stable quantum dot sensitized solar cells (QDSCs) is highly important. While ZnS is one of the most widely used passivation material in QDSCs, an alternative material based on ZnSe which was deposited on CdS/CdSe/TiO2 photoanode to form a semi-core/shell structure has been found to be more efficient in terms of reducing electron recombination in QDSCs in this work. It has been found that the solar cell efficiency was improved from 1.86% for ZnSe0 (without coating) to 3.99% using 2 layers of ZnSe coating (ZnSe2) deposited by successive ionic layer adsorption and reaction (SILAR) method. The short circuit current density (Jsc) increased nearly 1-fold (from 7.25 mA/cm2 to13.4 mA/cm2), and the open circuit voltage (Voc) was enhanced by 100 mV using ZnSe2 passivation layer compared to ZnSe0. Studies on the light harvesting efficiency (ηLHE) and the absorbed photon-to-current conversion efficiency (APCE) have revealed that the ZnSe coating layer caused the enhanced ηLHE at wavelength beyond 500 nm and a significant increase of the APCE over the spectrum 400-550 nm. A nearly 100% APCE was obtained with ZnSe2, indicating the excellent charge injection and collection process in the device. The investigation on charge transport and recombination of the device has indicated that the enhanced electron collection efficiency and reduced electron recombination should be responsible for the improved Jsc and Voc of the QDSCs. The effective electron lifetime of the device with ZnSe2 was nearly 6 times higher than ZnSe0 while the electron diffusion coefficient was largely unaffected by the coating. Study on the regeneration of QDs after photoinduced excitation has indicated that the hole transport from QDs to the reduced species (S2-) in electrolyte was very efficient even when the QDs were coated with a thick ZnSe shell (three layers). For comparison, ZnS coated CdS/CdSe sensitized solar cell with optimum shell thickness was also fabricated, which generated a lower energy conversion efficiency (η = 3.43%) than the ZnSe based QDSC counterpart due to a lower Voc and FF. This study suggests that ZnSe may be a more efficient passivation layer than ZnS, which is attributed to the type II energy band alignment of the core (CdS/CdSe quantum dots) and passivation shell (ZnSe) structure, leading to more efficient electron-hole separation and slower electron recombination

Exploiting Intermolecular Interactions between Alkyl-Functionalized Redox-Active Molecule Pairs to Enhance Interfacial Electron Transfer

The strategies to enhance electron transfer rates between redox-active, light-harvesting molecules attached to semiconductor surfaces and redox mediators in solution by modifying molecular structure are not fully investigated yet. Therefore, the design of molecules with controlled electron transfer rates remains a challenge. The aims of this work are to quantify the effect of long alkyl chain substitution on the electron transfer from cobalt(II/III) tris(2,2′-bipyridine) to organic molecules containing carbazole and thiophene and to demonstrate that alkyl chains can be used to enhance electron transfer between donor-acceptor pairs. To this end, we study the effect of using a combination of donor and acceptor molecules with and without alkyl chains on electron transfer kinetics. Using transient absorption spectroscopy, we show that when only the molecules or the mediators have long alkyl chains, electron transfer is slightly blocked as expected. Counterintuitively, electron transfer is up to 13 times faster when long alkyl chains are attached to both the redox-active molecules and the redox mediators. The faster electron transfer is explained by an alkyl-alkyl chain interaction between the donor/acceptor, leading to the proximity (trapping) of the redox mediators close to the π-conjugated backbone of the molecules. These results suggest that intermolecular interactions can be used to enhance the electron transfer rates significantly even with well-established insulating alkyl chains attached to molecules without changing the electrochemical driving force

Improved performance of porphyrin-based dye sensitised solar cells by phosphinic acid surface treatment

Chemical surface treatment of porphyrin-sensitised titania films using bis-(4-methoxyphenyl) phosphinic acid after dye adsorption, results in large improvements in DSSC efficiencies which originate primarily from higher short circuit currents. The result was attributed to a positive shift in the TiO2 quasi-Fermi level with simultaneous retardation of charge recombination. High device performances have been achieved even using simplified electrolyte matrices devoid of the common additives, LiI and t-butylpyridine

Dye regeneration and charge recombination in dye-sensitized solar cells with ferrocene derivatives as redox mediators

Ferrocene compounds are promising redox shuttles for application in dye-sensitized solar cells (DSCs). Chemical modification of the cyclopentadienyl rings is easily achievable affording almost unlimited variation of the redox properties. This allows fine-tuning of the driving force for dye-regeneration and optimization of the energy conversion efficiency of DSCs. Herein, six ferrocene derivatives have been chosen for investigation which cover the large redox potential range of 0.85 V, by virtue of simple alkylation and halogenation of the cyclopentadienyl ring, and enable improved matching of the energy levels of the sensitizer and the electrolyte. Although the focus of this work was to examine the effect of the redox potential on charge transfer processes, DSCs were fabricated which achieved high energy conversion efficiencies of over 5%. Charge transfer reactions were studied to reveal the dependence of the dye regeneration rate, recombination losses and recombination pathways on the reaction driving force. An increase in redox potential led to a higher efficiency due to higher open circuit potentials until a threshold is reached. At this threshold, the driving force for dye regeneration (18 kJ DE ¼ 0.19 V) becomes too small for efficient device operation, leading to rapid recombination between the oxidized dye and electrons in the TiO2 conduction band. As a result of this work guidelines can be formulated to aid the selection of redox couples for a particular sensitizer in order to maximize the utilization of incident solar energy

Enhancement of dye regeneration kinetics in dichromophoric porphyrin-carbazole triphenylamine dyes influenced by more exposed radical cation orbitals

Reduction kinetics of oxidized dyes absorbed on semiconductor surfaces and immersed in redox active electrolytes has been mainly modeled based on the free energy difference between the oxidation potential of the dye and the redox potential of the electrolyte. Only a few mechanisms have been demonstrated to enhance the kinetics by other means. In this work, the rate constant of the reduction of oxidized porphyrin dye is enhanced by attaching non-conjugated carbazole triphenylamine moiety using iodine/triiodide and tris(2,2′-bispyridinium)cobalt II/III electrolytes. These results are obtained using transient absorption spectroscopy by selectively probing the regeneration kinetics at the porphyrin radical cation and the carbazole triphenylamine radical cation absorption wavelengths. The enhancement in the reduction kinetics is not attributed to changes in the driving force, but to the more exposed dye cation radical orbitals of the dichromophoric dye. The results are important for the development of high efficiency photo-electrochemical devices with minimalized energy loss at electron transfer interfaces