Direct comparison between perovskite-structured hybrid organic-inorganic methylammonium lead bromide (MAPbBr3) and all-inorganic cesium lead bromide (CsPbBr3), allows identifying possible fundamental differences in their structural, thermal and electronic characteristics. Both materials possess a similar direct optical band gap, but CsPbBr3 demonstrates a higher thermal stability than MAPbBr3. In order to compare device properties, we fabricated solar cells, with similarly synthesized MAPbBr3 or CsPbBr3, over mesoporous titania scaffolds. Both cell types demonstrated comparable photovoltaic performances under AM1.5 illumination, reaching power conversion efficiencies of ∼6% with a poly aryl amine-based derivative as hole transport material. Further analysis shows that Cs-based devices are as efficient as, and more stable than methylammonium-based ones, after aging (storing the cells for 2 weeks in a dry (relative humidity 15-20%) air atmosphere in the dark) for 2 weeks, under constant illumination (at maximum power), and under electron beam irradiation.
Solar cells based on “halide perovskites” (HaPs) have demonstrated unprecedented high power conversion efficiencies in recent years. However, the well-known toxicity of lead (Pb), which is used in the most studied cells, may affect its widespread use. We explored an all-inorganic lead-free perovskite option, cesium tin bromide (CsSnBr3), for optoelectronic applications. CsSnBr3-based solar cells exhibited photoconversion efficiencies (PCEs) of 2.1%, with a short-circuit current (J SC) of ∼9 mA cm–2, an open circuit potential (V OC) of 0.41 V, and a fill factor (FF) of 58% under 1 sun (100 mW cm–2) illumination, which, even though meager compared to the Pb analogue-based cells, are among the best reported until now. As reported earlier, addition of tin fluoride (SnF2) was found to be beneficial for obtaining good device performance, possibly due to reduction of the background carrier density by neutralizing traps, possibly via filling of cation vacancies. The roles of SnF2 on the properties of the CsSnBr3 were investigated using ultraviolet photoemission spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) analysis.
Strongly bound and highly stable gold island films on glass are obtained by a simple, one‐step preparation procedure (see figure) based on high‐temperature annealing and partial embedding of gold nanostructures evaporated on glass, providing stable and effective localized plasmon transducers.
Gold island films displaying localized plasmon properties were prepared by evaporation of just-percolated Au films onto glass substrates followed by annealing at g550 °C. Annealing induces depercolation and formation of large, singlecrystalline, well-separated islands, partially embedded in the glass. Two dewetting mechanisms were identified, depending on the initial film morphology. The variability of island sizes and shapes provides effective means of tuning the position of the localized surface plasmon resonance (LSPR) band in a wide wavelength range. With an increase in the Au nominal thickness a transition occurs from transducers dominated by absorbance to ones dominated by scattering. Numerical simulations taking into account the shape and size distribution in actual island samples are in agreement with the experimental spectra. Refractive index sensitivity (RIS) measurements at a constant wavelength or at a constant extinction, tailored to the specific transducer, provide superior sensitivity to refractive index change, up to ca. 600 nm RIU À1 in wavelength shift.
Ultrathin gold films prepared by evaporation of sub-percolation layers (typically up to 10 nm nominal thickness) onto transparent substrates form arrays of well-defined metal islands. Such films display a characteristic surface plasmon (SP) absorption band, conveniently measured by transmission spectroscopy. The SP band intensity and position are sensitive to the film morphology (island shape and inter-island separation) and the effective dielectric constant of the surrounding medium. The latter has been exploited for chemical and biological sensing in the transmission localized surface plasmon resonance (T-LSPR) mode. A major concern in the development of T-LSPR sensors based on Au island films is instability, manifested as change in the SP absorbance following immersion in organic solvents and aqueous solutions. The latter may present a problem in the use of Au island-based transducers for biological sensing, usually carried out in aqueous media. Here, we describe a facile method for stabilizing Au island films while maintaining a high sensitivity of the SP absorbance to analyte binding. Stabilization is achieved by coating the Au islands with an ultrathin silica layer, ca. 1.5 nm thick, deposited by a sol-gel procedure on an intermediate mercaptosilane monolayer. The silica coating is prepared using a modified literature procedure, where a change in the reaction conditions from room temperature to 90 degrees C shortened the deposition time from days to hours. The system was characterized by UV-vis spectroscopy, ellipsometry, XPS, HRSEM, AFM, and cyclic voltammetry. The ultrathin silica coating stabilizes the optical properties of the Au island films toward immersion in water, phosphate buffer saline (PBS), and various organic solvents, thus providing proper conditions where the optical response is sensitive only to changes in the effective dielectric constant of the immediate environment. The silica layer is thin enough to afford high T-LSPR sensitivity, while the hydroxyl groups on its surface enable chemical modification for binding of receptor molecules. The use of silica-encapsulated Au island films as a stable and effective platform for T-LSPR sensing is demonstrated.
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