Effect of fluorine substitution and position on phenylene spacer in carbazole based organic sensitizers for dye sensitized solar cells.

The preparation of a series of organic dyes having a carbazole donor, cyanoacrylic acid as an acceptor, and phenylene ring as a spacer with the difference in the positions of fluorine substitution is reported. Due to its unique properties of small size and high electronegativity, fluorine is now being extensively used to control the optoelectronic properties of organic conjugated materials. In this study, the results revealed that the specific position and number of fluorine substitution were very crucial to control the optical as well as the electrochemical properties of organic dyes. It was found that fluorine substitution led to a redshift in the absorption spectra of the dyes and reduced the band gap. The injection rate of photoexcited electrons was measured using time-resolved photoluminescence and the o-fluoro substituted dye MA1F-o showed the best electron injection dynamics. As a result of broad absorption and high electron injection rate, the dye MA1F-o outperformed other dyes with a power conversion efficiency of 4.02% (Jsc = 8.3 mA cm-2, Voc = 0.75 V and FF = 0.64). The non-fluorinated dye MA0F exhibited a power conversion efficiency of 3.23% (Jsc = 6.8, Voc = 0.72 and FF = 0.67). The dye MA1F-m exhibited the least molar absorption coefficient and a lower power conversion efficiency because of the meta inductive effect.

Design, synthesis and DSSC performance of o-fluorine substituted phenylene spacer sensitizers: effect of TiO2 thickness variation.

The influence of TiO2 film thickness on the performance of DSSCs with a new series of dyes having ortho-fluorine substituted phenyl spacers and different donor moieties is reported. Optical, electrochemical, molecular orbital and photovoltaic properties were studied by varying the TiO2 thickness (9 and 12 µm) using these dyes. The thickness variation of TiO2 films had a significant effect on the open circuit voltage (Voc), short circuit current (Jsc) and efficiency. The Jsc and Voc of dye 1b with a TiO2 film thickness of 12 µm (8.91 mA cm-2 and 0.63 V) were larger than those of the 9 µm film thickness device (8.40 mA cm-2 and 0.57 V). This could be due to the variation in the thickness of the TiO2 film. However, at an optimized thickness of the TiO2 film (12 µm), 1b exhibited the highest power conversion efficiency (η) of 4.0% (average 3.6%). This highest efficiency value for 1b from 3.3% to 4.0% without using any co-absorbents was solely based on changing the thickness of the TiO2 film. In addition 1b had a planar structure, whereas dyes 2b and 3b had three and two dimensional structures. The optimized geometry calculation of o-fluoro phenyl π-spacer dyes was ascertained by density functional theory (DFT) using the B3LYP/631G(d,p) basis set. These results reveal that dye 1b has higher efficiency due to the deeper HOMO level and it exhibited better charge transfer from donor to acceptor, compared to the other dyes.