Double perovskites are promising candidates for less toxic and highly stable metal halide perovskites, but their optoelectronic performances still lag behind those of the lead halide counterpart, due to the indirect nature of the bandgap and the strong electron–phonon coupling. Reducing the dimensionality of Cs2AgBiBr6 down to a 2D layered form is strategic in order to tune the band gap from indirect to direct and provides new insights into the structure–property relationships of double perovskites. Herein, we report on a series of monolayer 2D hybrid double perovskites of formula (RA)4AgBiBr8, where RA represents different primary ammonium large cations with alkyl- and aryl-based functionalities. An in-depth experimental characterization of structure, film morphology, and optical properties of these perovskites is carried out. Interestingly, the variation of the ammonium cation and the interplanar distance between adjacent inorganic monolayers has peculiar effects on the film-forming ability and light emission properties of the perovskites. Experiments have been combined with DFT calculations in order to understand the possible origin of the different emissive features. Our study provides a toolbox for future rational developments of 2D double perovskites, with the aim of narrowing the gap with lead halide perovskite optoelectronic properties.
Commercialization of lead halide perovskite-based devices is hindered by their instability towards environmental conditions. In particular, water promotes fast decomposition, leading to a drastic decrease in device performance. Integrating water-splitting active species within ancillary layers to the perovskite absorber might be a solution to this, as they could convert incoming water into oxygen and hydrogen, preserving device performance. Here, we suggest that a CuSCN nanoplatelete/p-type semiconducting polymer composite, combining hole extraction and transport properties with water oxidation activity, transforms incoming water molecules and triggers the in situ p-doping of the conjugated polymer, improving transport of photocharges. Insertion of the nanocomposite into a lead perovskite solar cell with a direct photovoltaic architecture causes stable device performance for 28 days in high-moisture conditions. Our findings demonstrate that the engineering of a hole extraction layer with possible water-splitting additives could be a viable strategy to reduce the impact of moisture in perovskite devices.
ZnS nanosystems are being extensively studied for their possible use in a wide range of technological applications. Recently, the gradual oxidation of ZnS to ZnO was exploited to tune their structural, electronic, and functional properties. However, the inherent complexity and size dependence of the ZnS oxidation phenomena resulted in a very fragmented description of the process. In this work, different-sized nanosystems were obtained through two different low temperature wet chemistry routes, namely, hydrothermal and inverse miniemulsion approaches. These protocols were used to obtain ZnS samples consisting of 21 and 7 nm crystallites, respectively, to be used as reference material. The obtained samples were then calcinated at different temperatures, ranging from 400 to 800 °C toward the complete oxidation of ZnO, passing through the coexistence of the two phases (ZnS/ZnO). A thorough comparison of the effects of thermal handling on ZnS structural, chemical, and functional evolution was carried out by TEM, XRD, XAS, XPS, Raman, FT-IR, and UV–Vis. Finally, the photocatalytic activity in the H2 evolution reaction was also compared for selected ZnS and ZnS/ZnO samples. A correlation between size and the oxidation process was observed, as the smaller nanosystems showed the formation of ZnO at lower temperature, or in a larger amount in the case of the ZnS and ZnO co-presence. A difference in the underlying mechanism of the reaction was also evidenced. Despite the ZnS/ZnO mixed samples being characterized by an increased light absorption in the visible range, their photocatalytic activity was found to be much lower.
ZnS nanoparticles (NPs) were synthesized using a simple, green, and reproducible hydrothermal method. Transmission electron micrographs show polyhedral NPs having an average diameter of 21 nm; whereas the X-ray diffraction analysis is consistent with the exclusive presence of cubic ZnS; however no oxide could be detected. A comprehensive characterization of the NPs’ surface was accomplished through X-ray photoelectron spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), Raman, and thermogravimetric analysis–differential scanning calorimetry, showing a fairly pure ZnS composition and a remarkable amount of adsorbed water molecules. The interaction capabilities of the surface were probed in situ by DRIFT using small molecules (CO, CO2, methanol, pyridine) as molecular probes. The same interactions were also theoretically studied with density functional calculations using a slab model based on the sphalerite ZnS (110) surface. By comparing theoretical and experimental vibrational shifts, insights on the nature of the interaction between molecular probes and surfaces were obtained. Water was found to alter both the structure as well as the reactivity of the surface, mediating the interaction of methanol with the surface, and allowing the conversion of CO2 into surface carbonates. Pyridine was instead evidenced to be able to replace water molecules because of its high adsorption energy (1 eV) which is in tune with the known pyridine-detection capabilities of ZnS. No −SH moieties or Lewis acid behavior of the exposed S atoms were observed.
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