Dependence of dye regeneration and charge collection on the pore-filling fraction in solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cells rely on effective infiltration of a solid-state hole-transporting material into the pores of a nanoporous TiO 2 network to allow for dye regeneration and hole extraction. Using microsecond transient absorption spectroscopy and femtosecond photoluminescence upconversion spectroscopy, the hole-transfer yield from the dye to the hole-transporting material 2,2′,7,7′-tetrakis(N,N-di-p- methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) is shown to rise rapidly with higher pore-filling fractions as the dye-coated pore surface is increasingly covered with hole-transporting material. Once a pore-filling fraction of ≈30% is reached, further increases do not significantly change the hole-transfer yield. Using simple models of infiltration of spiro-OMeTAD into the TiO2 porous network, it is shown that this pore-filling fraction is less than the amount required to cover the dye surface with at least a single layer of hole-transporting material, suggesting that charge diffusion through the dye monolayer network precedes transfer to the hole-transporting material. Comparison of these results with device parameters shows that improvements of the power-conversion efficiency beyond ≈30% pore filling are not caused by a higher hole-transfer yield, but by a higher charge-collection efficiency, which is found to occur in steps. The observed sharp onsets in photocurrent and power-conversion efficiencies with increasing pore-filling fraction correlate well with percolation theory, predicting the points of cohesive pathway formation in successive spiro-OMeTAD layers adhered to the pore walls. From percolation theory it is predicted that, for standard mesoporous TiO2 with 20 nm pore size, the photocurrent should show no further improvement beyond an ≈83% pore-filling fraction. Solid-state dye-sensitized solar cells capable of complete hole transfer with pore-filling fractions as low as ∼30% are demonstrated. Improvements of device efficiencies beyond ∼30% are explained by a stepwise increase in charge-collection efficiency in agreement with percolation theory. Furthermore, it is predicted that, for a 20 nm pore size, the photocurrent reaches a maximum at ∼83% pore-filling fraction. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Absorbance kinetics of dye-doped systems with photochemical first order kinetics

Often it is assumed that absorbance decays in photochromic materials with the time dependence of the photochemical kinetics, i.e. exponentially for first order kinetics. Although this may hold in the limiting case of vanishing absorbance, deviations are to be expected for realistic samples, because the local photochemical kinetics slows down with increasing initial absorption and penetration depth of the radiation. We discuss the theory of the kinetics of initially homogeneous photochromic samples and derive analytical solutions. In extension of Tomlinson's theory we find an analytical solution that holds with good approximation even for samples that exhibit a small residual absorption in the saturation limit. The theoretical time dependence of the absorbance originating from photochemical first order kinetics of dye-doped systems is compared with experimental data published by Lafond et al. for fulgides doped in different polymer matrices. (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast dynamics of dye molecules in solution as a function of temperature

Femtosecond time-resolved studies using fluorescence depletion spectroscopy were performed on Rhodamine 700 in acetone solution and on Oxazine 750 in acetone and formamide solutions at different temperatures. The experimental curves that include both fast and slow processes have been fitted using a biexponential function. Time constants of the fast process, which corresponds to the intramolecular vibrational redistribution (IVR) of solute molecules, range from 300 to 420 fs and increase linearly as the temperature of the environment decreases. The difference of the average vibrational energy of solute molecules in the ground state at different temperatures is a possible reason that induces this IVR time-constant temperature dependence. However, the time constants of the slow process, which corresponds to the energy transfer from vibrational hot solute molecules to the surroundings occurred on a time scale of 1-50 ps, changed dramatically at lower temperature, nonlinearly increasing with the decrease of temperature. Because of the C-H...O hydrogen-bond between acetone molecules, it is more reasonable that acetone molecules start to be associated, which can influence the energy transfer between dye molecules and acetone molecules efficiently, even at temperatures far over the freezing point.

Ultrafast vibrational and thermal relaxation of dye molecules in solutions

Intra- and intermolecular relaxations of dye molecules are studied after the excitation to the high-lying excited states by a femtosecond laser pulse, using femtosecond time-resolved stimulated emission pumping fluorescence depletion spectroscopy (FS TR SEP FD). The biexponential decays indicate a rapid intramolecular vibrational redistribution (IVR) depopulation followed by a slower process, which was contributed by the energy transfer to the solvents and the solvation of the excited solutes. The time constants of IVR in both oxazine 750 and rhodamine 700 are at the 290-360 fs range, which are insensitive to the characters of solvents. The solvation of the excited solutes and the cooling of the hot solute molecules by collisional energy transfer to the surrounding takes place in the several picoseconds that strongly depend on the properties of solvents. The difference of Lewis basicity and states density of solvents is a possible reason to explain this solvent dependence. The more basic the solvent is, which means the more interaction between the solute and the neighboring solvent shell, the more rapid the intermolecular vibrational excess energy transfer from the solute to the surroundings and the solvation of the solutes are. The higher the states density of the solvent is, the more favorable the energy transfer between the solute and solvent molecules is.

zero point of charge of cupric hydroxide and surface area determination by dye adsorption

zero point of charge of freshly precipitated cu(oh)2 has been determined to lie at pH 7.7 by means of microclectrophoresis technique. Day aged hydroxide shows an acid zpc shift to pH 7.3. these experimental values approximate the equivalence points of cu+ and oh_ ,which can be estimated from the solubility diagram constructed fo gu(oh)2 and cuo.

A solid-state dye-sensitized solar cell based on a novel ionic liquid gel and ZnO nanoparticles on a flexible polymer substrate

This paper describes a new strategy to make a full solid-state, flexible, dye-sensitized solar cell (DSSC) based on novel ionic liquid gel, organic dye, ZnO nanoparticles and carbon nanotube (CNT) thin film stamped onto a polyethylene terephthalate (PET) substrate. The CNTs serve both as the charge collector and as scaffolds for the growth of ZnO nanoparticles, where the black dye molecules are anchored.

High-performance dye-sensitized solar cells based on solvent-free electrolytes produced from eutectic melts

Low-cost excitonic solar cells based on organic optoelectronic materials are receiving an ever-increasing amount of attention as potential alternatives to traditional inorganic photovoltaic devices. In this rapidly developing field, the dye-sensitized solar cell(1) (DSC) has achieved so far the highest validated efficiency of 11.1% (ref. 2) and remarkable stability(3).

An organic sensitizer with a fused dithienothiophene unit for efficient and stable dye-sensitized solar cells

We report a high molar extinction coefficient organic sensitizer for high efficiency dye-sensitized solar cells. In combination with a solvent-free ionic liquid electrolyte, we have demonstrated a similar to 7% cell showing an excellent stability measured under the thermal and light soaking dual stress. This is expected to have an important practical consequence on the production of flexible, low-cost, and lightweight DSC based on plastic matrix.

Enhance the optical absorptivity of nanocrystalline TiO2 film with high molar extinction coefficient ruthenium sensitizers for high performance dye-sensitized solar cells

We report two new heteroleptic polypyridyl ruthenium complexes, coded C101 and C102, with high molar extinction coefficients by extending the pi-conjugation of spectator ligands, with a motivation to enhance the optical absorptivity of mesoporous titania film and charge collection yield in a dye-sensitized solar cell. On the basis of this C101 sensitizer, several DSC benchmarks measured under the air mass 1.5 global sunlight have been reached.

A new heteroleptic ruthenium sensitizer enhances the absorptivity of mesoporous titania film for a high efficiency dye-sensitized solar cell

A heteroleptic polypyridyl ruthenium complex, cis-Ru(4,4'-bis(5-octylthieno[3,2-b]thiophen-2-yl)-2,2'-bipyridine)(4,4'-dicarboxyl-2,2'-bipyridine)(NCS) 2, with a high molar extinction coefficient of 20.5 x 10(3) M-1 cm(-1) at 553 nm has been synthesized and demonstrated as a highly efficient sensitizer for a dye-sensitized solar cell, giving a power conversion efficiency of 10.53% measured under an irradiation of air mass 1.5 global ( AM 1.5G) full sunlight.

Tetrahydrothiophenium-based ionic liquids for high efficiency dye-sensitized solar cells

Binary melts of S-ethyltetrahydrothiophenium iodide and dicyanoamide (or tricyanomethide) have been employed for dye-sensitized solar cells with high power conversion efficiencies up to 6.9% under the illumination of AM 1.5G full sunlight. We have further shown that the transport of triiodide in ionic liquids with high iodide concentration is viscosity-dependent in terms of a physical diffusion coupled bond exchange mechanism apart from the simple physical diffusion.