Density Functional Theory (DFT) Study of Coumarin-based Dyes Adsorbed on TiO2 Nanoclusters—Applications to Dye-Sensitized Solar Cells

material

DFT Study of Binding and Electron Transfer from a Metal-Free Dye with Carboxyl, Hydroxyl, and Sulfonic Anchors to a Titanium Dioxide Nanocluster

We report results of density functional theory (DFT) calculations of a metal-free dye, 5-(4-sulfophenylazo)salicylic acid disodium salt, known as Mordant Yellow 10 (MY-10), used as sensitizer for TiO2 dye-sensitized solar cells (DSSCs). Given the need to better understand the behavior of the dyes adsorbed on the TiO2 nanoparticle, we studied various single and double deprotonated forms of the dye bound to a TiO2 cluster, taking advantage of the presence of the carboxyl, hydroxyl, and sulfonic groups as possible anchors. We discuss various binding configurations to the TiO2 substrate and the charge transfer from the pigment to the oxide by means of DFT calculations. In agreement with other reports, we find that the carboxyl group tends to bind in bidentate bridging configurations. The salicylate uses both the carboxyl and hydroxyl substituent groups for either a tridentate binding to adjacent Ti(IV) ions or a bidentate Ti-O binding together with an O-H-O binding, due to the rotation of the carboxyl group out of the plane of the dye. The sulfonic group prefers a tridentate binding. We analyze the propensity for electron transfer of the various dyes and find that for MY-10, as a function of the anchor group, the DSSC performance decreases in the order hydroxyl + carboxyl > carboxyl > sulfonate

A Combined Experimental and Computational Study of Chrysanthemin as a Pigment for Dye-Sensitized Solar Cells

The theoretical study of chrysanthemin (cyanidin 3-glucoside) as a pigment for TiO2-based dye-sensitized solar cells (DSSCs) was performed with the GAUSSSIAN 09 simulation. The electronic spectra of neutral and anionic chrysanthemin molecules were calculated by density functional theory with B3LYP functional and DGDZVP basis set. A better energy level alignment was found for partially deprotonated molecules of chrysanthemin, with the excited photoelectron having enough energy in order to be transferred to the conduction band of TiO2 semiconductor in DSSCs. In addition, we used the raw aqueous extracts of roselle (Hibiscus sabdariffa) calyces as the source of chrysanthemin and the extracts with various pH values were tested in DSSCs. The extracts and photosensitized semiconductor layers were characterized by UV-Vis spectroscopy, and DSSCs based on raw extracts were characterized by current density-voltage measurements

Pulsed Laser Fabrication of TiO₂ Buffer Layers for Dye Sensitized Solar Cells

We report on the fabrication of dye-sensitized solar cells with a TiO2 buffer layer between the transparent conductive oxide substrate and the mesoporous TiO2 film, in order to improve the photovoltaic conversion efficiency of the device. The buffer layer was fabricated by pulsed laser deposition whereas the mesoporous film by the doctor blade method, using TiO2 paste obtained by the sol–gel technique. The buffer layer was deposited in either oxygen (10 Pa and 50 Pa) or argon (10 Pa and 50 Pa) onto transparent conducting oxide glass kept at room temperature. The cross-section scanning electron microscopy image showed differences in layer morphology and thickness, depending on the deposition conditions. Transmission electron microscopy studies of the TiO2 buffer layers indicated that films consisted of grains with typical diameters of 10 nm to 30 nm. We found that the photovoltaic conversion efficiencies, determined under standard air mass 1.5 global (AM 1.5G) conditions, of the solar cells with a buffer layer are more than two times larger than those of the standard cells. The best performance was reached for buffer layers deposited at 10 Pa O2. We discuss the processes that take place in the device and emphasize the role of the brush-like buffer layer in the performance increase