Microwave-Assisted Non-aqueous and Low-Temperature Synthesis of Titania and Niobium-Doped Titania Nanocrystals and Their Application in Halide Perovskite Solar Cells as Electron Transport Layers.

Undoped and Nb-doped TiO2 nanocrystals are prepared by a microwave-assisted non-aqueous sol-gel method based on a slow alkyl chloride elimination reaction between metal chlorides and benzyl alcohol. Sub-4 nm nanoparticles are grown under microwave irradiation at 80 °C in only 3 h with precise control of growth parameters and yield. The obtained nanocrystals could be conveniently used to cast compact TiO2 or Nb-doped TiO2 electron transport layers for application in formamidinium lead iodide-based photovoltaic devices. Niobium doping is found to improve the cell performance by increasing the conductivity and mobility of the electron transport layer. At the same time, a measurable decrease in parasitic light absorption in the low wavelength portion of the spectrum was observed.

Mixed-Metal Cu-Zn Thiocyanate Coordination Polymers with Melting Behavior, Glass Transition, and Tunable Electronic Properties.

The solid-state mechanochemical reactions under ambient conditions of CuSCN and Zn(SCN)2 resulted in two novel materials: partially Zn-substituted α-CuSCN and a new phase CuxZny(SCN)x+2y. The reactions take place at the labile S-terminal, and both products show melting and glass transition behaviors. The optical band gap and solid-state ionization potential can be adjusted systematically by adjusting the Cu/Zn ratio. Density functional theory calculations also reveal that the Zn-substituted CuSCN structure features a complementary electronic structure of Cu 3d states at the valence band maximum and Zn 4s states at the conduction band minimum. This work shows a new route to develop semiconductors based on coordination polymers, which are becoming technologically relevant for electronic and optoelectronic applications.

Processable UiO-66 Metal-Organic Framework Fluid Gel and Electrical Conductivity of Its Nanofilm with Sub-100 nm Thickness.

Zr-based UiO-66 metal-organic framework (MOF) is one of the most studied MOFs with a wide range of potential applications. While UiO-66 is typically synthesized as a microcrystalline solid, we employ a particle downsizing strategy to synthesize UiO-66 as fluid gel with unique rheological properties, which allows the solution-based processing as sub-100 nm films and enhances the electrical conductivity of its pristine structure. Film thicknesses ranging from 40 to 150 nm could be achieved by controlling the spin-coating parameters. The generality of the method is also demonstrated for other Zr-based MOFs including MOF-801 and MOF-808. The impact of particle size and film thickness at the nanoscale on electrical properties of UiO-66 is shown to realize new features that are distinct from those of the bulk powder phase. An electrical insulator UiO-66 shows a significant increase in the electrical conductivity (10-5 S cm-1 compared to 10-7 S cm-1 in the bulk powder phase) when the 10 nm particles are distributed on the substrate with a thickness less than 100 nm. The findings establish a new route for processing of MOF materials as thin films with fine-tuned thickness and offer a new perspective for transport properties of Zr-based MOFs without structural modification.