Double perovskites are a promising family of lead-free materials that not only replace lead but also enable new optoelectronic applications beyond photovoltaics. Recently, a titanium (Ti)-based vacancy-ordered double perovskite, Cs₂TiBr₆, has been reported as an example of truly sustainable and earth-abundant perovskite with controversial results in terms of photoluminescence and environmental stability. Our work looks at this material from a new perspective, i.e., at the nanoscale. We demonstrate the first colloidal synthesis of Cs₂TiX₆ nanocrystals (X = Br, Cl) and observe tunable morphology and size of the nanocrystals according to the set reaction temperature. The Cs₂TiBr₆ nanocrystals synthesized at 185 °C show a bandgap of 1.9 eV and are relatively stable up to 8 weeks in suspensions. However, they do not display notable photoluminescence. The centrosymmetric crystal structure of Cs₂TiBr₆ suggests that this material could enable third-harmonic generation (THG) responses. Indeed, we provide a clear evidence of THG signals detected by the THG microscopy technique. As only a few THG-active halide perovskite materials are known to date and they are all lead-based, our findings promote future research on Cs₂TiBr₆ as well as on other lead-free double perovskites, with stronger focus on currently unexplored nonlinear optical applications.

Amorphous titania (am.-TiO₂) has gained wide interest in the field of photocatalysis, thanks to exceptional disorder-mediated optical and electrical properties compared to crystalline TiO₂. Here, we study the effects of intrinsic Ti³⁺ and nitrogen defects in am.-TiO₂ thin films via the atomic layer deposition (ALD) chemistry of tetrakis(dimethylamido)titanium(IV) (TDMAT) and H₂O precursors at growth temperatures of 100–200 °C. X-ray photoelectron spectroscopy (XPS) and computational analysis allow us to identify structural disorder-induced penta- and heptacoordinated Ti⁴⁺ ions (Ti_5/7c⁴⁺), which are related to the formation of Ti³⁺ defects in am.-TiO₂. The Ti³⁺-rich ALD-grown am.-TiO₂ has stoichiometric composition, which is explained by the formation of interstitial peroxo species with oxygen vacancies. The occupation of Ti³⁺ 3d in-gap states increases with the ALD growth temperature, inducing both visible-light absorption and electrical conductivity via the polaron hopping mechanism. At 200 °C, the in-gap states become fully occupied extending the lifetime of photoexcited charge carriers from the picosecond to the nanosecond time domain. Nitrogen traces from the TDMAT precursor had no effect on optical properties and only little on charge transfer properties. These results provide insights into the charge transfer properties of ALD-grown am.-TiO₂ that are essential to the performance of protective photoelectrode coatings in photoelectrochemical solar fuel reactors.

Visually black, electrically leaky, amorphous titania (am-TiO₂) thin films were grown by atomic layer deposition (ALD) for photocatalytic applications. Broad spectral absorbance in the visible range and exceptional conductivity are attributed to trapped Ti³⁺ in the film. Oxidation of Ti³⁺ upon heat treatment leads to a drop in conductivity, a color change from black to white and crystallization of am-TiO₂. ALD grown black TiO₂, without any heat treatment, is subject to dissolution in alkaline photoelectrochemical conditions. The best photocatalytic activity for solar water splitting is obtained for completely crystalline white TiO₂.