Most organic dyes synthesized for dye-sensitized solar cells (DSC) use a single linker group to bind to the metal oxide photo-anode. Here we describe the synthesis and testing of two new triphenylamine dyes containing either two carboxylic acids 5-[2-(4-diphenylamino-phenyl)-vinyl]-isophthalic acid (10) or two cyanoacrylic acids (2Z, 2′Z)-3, 3′-(5-((E)-4-(diphenylamino) styryl)-1, 3-phenylene) bis (2-cyanoacrylic acid) (8) as linker groups. Full characterization data are reported for these dyes and their synthetic intermediates. DSC devices have been prepared from these new dyes either by passive or fast dyeing and the dyes have also been tested in co-sensitized DSC devices leading to a PCE (η = 5.4%) for the double cyanoacrylate linker dye (8) co-sensitized with D149. The dye:TiO₂ surface interactions and dye excitations are interpreted using three modelling methods: density functional theory (at 0 K); molecular dynamics (at 298 K); time dependent density functional theory. The modelling results show the preferred orientation of both dyes on an anatase (1 0 1) TiO₂ surface to be horizontal, and both the simulated and experimental absorption spectra of the dye molecules indicate a red shifted band for (8) compared to (10). This is in line with broader light harvesting and J_sc for (8) compared to (10).

We report the synthesis of organometal halide perovskites by milling CH₃NH₃I and PbI₂ directly with an Al₂O₃ scaffold to create hybrid Al₂O₃-CH₃NH₃PbI₃ perovskites, without the use of organic capping ligands that otherwise limit the growth of the material in the three dimensions. Not only does this improve the ambient stability of perovskites in air (100 min versus 5 min for dimethylformamide (DMF)-processed material), the method also uses much fewer toxic solvents (terpineol versus dimethylformamide). This has been achieved by solid-state reaction of the perovskite precursors to produce larger perovskite nanoparticles. The resulting hybrid perovskite–alumina particles effectively improve the hydrophobicity of the perovskite phase whilst the increased thermal mass of the Al₂O₃ increases the thermal stability of the organic cation. Raman data show the incorporation of Al₂O₃ shifts the perovskite spectrum, suggesting the formation of a hybrid 3D mesoporous stack. Laser-induced current mapping (LBIC) and superoxide generation measurements, coupled to thermogravimetric analysis, show that these hybrid perovskites demonstrate slightly improved oxygen and thermal stability, whilst ultra-fast X-ray diffraction studies using synchrotron radiation show substantial (20×) increase in humidity stability. Overall, these data show considerably improved ambient stability of the hybrid perovskites compared to the solution-processed material.