Search

We report the synthesis of 9 new half squaraine (HfSQ) dyes; 5 containing a benzothiazole moiety and 4 containing an indolenine moiety. X-ray single crystal structural and characterisation data have been correlated with device data to understand the widely reported but poorly understood influence of S heteroatoms on DSC device performance. The S heteroatom in these new dyes has also been used as an atomic probe of the dye–TiO2 interface to dye binding and orientation. Thus, for the first time, using the S heteroatom probe, angle-resolved X-ray photoelectron (AR-XPS) data have shown these dyes sit horizontally at the dye–TiO2 interface confirmed by DFT computer modelling of novel and analogous HfSQ dyes with a benzoindole backbone. [ABSTRACT FROM AUTHOR]

Thermal analysis (TGA and DSC), coupled with evolved gas FTIR spectroscopy, has been used to study the changes occurring during, and differences between materials after, the annealing step of mixed-halide methylammonium lead halide perovskites. This is important because, to date, the material is the most efficient light harvester in highly efficient, 3rd generation perovskite photovoltaic devices, and processing plays a significant role in device performance. TGA-FTIR data show only solvent evolution during the annealing step, whilst post-annealing analysis shows that the resulting material still contains a significant amount of residual solvent; however, efficient DMF removal was possible using a silica gel desiccant for a period of 3 days. The data also show that methylammonium halide decomposition does not occur until temperatures well above those used for perovskite processing, suggesting that this is not a significant issue for device manufacture. The absence of a well-defined, reversible tetragonal – cubic phase change around 55 °C in the DSC data of the annealed material, and the presence of HCl in evolved gas analysed following thermal decomposition, demonstrates that CH3NH3I3−xClx does retain some Cl after annealing and does not simply form stoichiometric CH3NH3PbI3 as has been suggested by some workers. [ABSTRACT FROM AUTHOR]

Nano-structured metal oxide films are key components of dye-sensitized (DSC) solar cells. Scaling such devices requires lower temperature processing to enable cheaper substrates to be used. In this context, we report a new and scalable method to sinter binder-containing metal oxide pastes to make DSC photo-electrodes at lower temperatures. Metal peroxide powders (CaO2, MgO2, or ZnO2) were added to terpineol-based P25 pastes containing ethyl cellulose binder or to commercial TiO2 paste (DSL18NR-T). Thermal analysis shows that binder decomposition occurs at 300 °C instead of the standard 450 °C for a TiO2-only paste and suggests that the metal peroxides act as combustion promoters releasing heat and oxygen within the film while heating. The data show that this heat and oxygen release coincide best with binder combustion for ZnO2 and DSC device tests show that adding ZnO2 to TiO2 pastes produces the best performances affording ç = 7.5% for small devices (0.26 cm2) and ç = 5.7% at 300 °C or 450 °C for DSL18NR-T/ZnO2 for larger (1 cm2) devices. To the best of our knowledge, the performance of the (0.26 cm2) cells is comparable to the highest efficiency devices reported for DSCs fabricated using low temperature methods. The device efficiency is most strongly linked with Jsc; BET and dye sorption measurements suggest that Jsc is linked with the metal oxide surface area and dye loading. The latter is linked to the availability of surface sorption sites for dye molecules which is strongly negatively affected by any residual organic binder which resulted from incomplete combustion. [ABSTRACT FROM AUTHOR]

This paper reports the synthesis of a series of new half-squaraine dyes (Hf-SQ) based around a common chromophoric unit consisting of linked indoline and squaric acid moieties. Carboxylate groups have been incorporated onto this core structure at four different points to study the influence of the anchoring group position on dye-sensitized solar cell (DSC) device performance. Dyes have been linked to TiO2 directly through the squaric acid moiety, through a modified squaric acid unit where a vinyl dicyano group has replaced one carbonyl, via an alkyl carboxylate attached to the indole N or through a carboxylate attached to the 4 position of a benzyl indole. Contact angle measurements have been studied to investigate the hydrophobic/hydrophilic properties of the dyes and the results have been compared to N719 and Z907. Full characterization data of all the dyes and synthetic intermediates are reported including single-crystal X-ray structural analysis for dye precursors; the indole (2a) and the half-squarylium esters (3a) and (6b), as well as the dyes (4c), (8) and (12). Dye colours range from yellow to red/brown in solution (λmax range from 430 to 476 nm) with ε ranging from 38 000 to 133 100 M−1 cm−1. The performance of the dyes in DSCs shows the highest efficiency yet reported for a Hf-SQ dye (η = 5.0%) for 1 cm2 devices with a spectral response ranging from 400 to 700 nm depending on the dye substituents. Co-sensitization of half-squarylium dye (7b) with squaraine dye (SQ2) resulted in a broader spectral response and an improved device efficiency (η = 6.1%). Density functional theory (DFT) calculations and cyclic voltammetry have been used to study the influence of linker position on dye HOMO–LUMO levels and the data has been correlated with I–V and EQE data. [ABSTRACT FROM AUTHOR]