RESUMEN
Double perovskites (DPs) with a generic formula A2 M'(I)MIII X6 (A and M are metal ions, and X=Cl, Br, I) are now being explored as potential alternatives to Pb-halide perovskites for solar cells and other optoelectronic applications. However, these DPs typically suffer from wide (≈3â eV) and/or indirect band gaps. In 2017, a new structural variety, namely layered halide DP Cs4 CuSb2 Cl12 (CCSC) with bivalent CuII ion in the place of M'(I) was reported, which exhibit a band gap of approximately 1â eV. Here, we report a mechanochemical synthesis of CCSC, its thermal and chemical stability, and magnetic response of CuII d9 electrons controlling the optoelectronic properties. A simple grinding of precursor salts at ambient conditions provides a stable and scalable product. CCSC is stable in water/acetone solvent mixtures (≈30 % water) and many other polar solvents unlike Pb-halide perovskites. It decomposes to Cs3 Sb2 Cl9 , Cs2 CuCl4 , and SbCl3 at 210 °C, but the reaction can be reversed back to produce CCSC at lower temperatures and high humidity. A long-range magnetic ordering is observed in CCSC even at room temperature. The role of such magnetic ordering in controlling the dispersion of the conduction band, and therefore, controlling the electronic and optoelectronic properties of CCSC has been discussed.
RESUMEN
The effect of annealing on the acidity and water uptake of Nafion films has been studied by using the acidity sensing fluorophore 2-(4'-pyridyl)benzimidazole (4PBI). The difference in acidity and the microenvironment of the fluorophore in annealed and nonannealed films is brought out in this study. The annealed film is found to have less water uptake than nonannealed films. The amount of water uptake increases upon acid treatment of the films, as all the steady-state and time-resolved behaviour of the molecule in nonannealed films is restored. These observations are rationalised by the formation of anhydrides upon annealing and their hydrolysis to sulfonic acid groups upon acid treatment. Interestingly, the acidity of annealed films is found to be even less than that of Na+ exchanged films, indicating that annealing removes more protons from the Nafion films than cation exchange can.
RESUMEN
The present work describes ultrafast thermalized and hot hole transfer processes from photo-excited CdSe quantum dots (QDs) and CdSe/ZnS core-shell QDs (CSQDs) to newly synthesized thiols. Three thiols namely 2-mercapto-N-phenylacetamide (AAT), 3-mercapto-N-phenylpropanamide (APT) and 3-mercapto-N-(4-methoxyphenyl) propanamide (ADPT) were synthesized and their interaction with both CdSe QDs and CdSe/ZnS CSQDs was monitored. Steady state absorption study suggests the exciton delocalization from CdSe QDs in the presence of the thiols. However similar features were not observed in the presence of a ZnS shell over a CdSe core, instead a broadening in the excitonic peak was observed with both APT and ADPT but not with AAT. This exciton delocalization and broadening in the excitonic peak was also confirmed by ultrafast transient absorption studies. Steady state and time resolved emission studies show hole transfer from photo-excited QDs and CSQDs to the thiols. A signature of hot hole extraction was observed in transient absorption studies which was confirmed by fluorescence upconversion studies. Both hot and thermalized hole transfer rates from CdSe QDs and CdSe/ZnS CSQDs to the thiols were determined using the fluorescence up-conversion technique. Experiments with different ZnS shell thicknesses have been carried out which suggest that hole transfer is possible till 2.5 monolayer of the ZnS shell. To the best of our knowledge we are reporting for the first time the extraction of hot holes from CdSe/ZnS type I CSQDs by a molecular adsorbate.
RESUMEN
Effects of annealing have been studied on the chemical structure, water uptake, and acidity of the cast Nafion thin film of thickness â¼ 6 µm using a fluorescent probe, 2-(3'-pyridyl)benzimidazole (3PBI), and attenuated total reflactance infrared (ATR-IR) spectroscopy. Nonannealed films and thick Nafion 117 membrane have been used as reference materials, in order to develop a complete understanding of the effect. Annealing has been found to cause a decrease in acidity of otherwise highly acidic ionomer, as sensed by the fluorescent probe and loss of water, as reflected in the ATR-IR spectrum. This observation is surprising and cannot be explained in the light of previous reports of physical changes. Our ATR-IR study has revealed changes in the chemical structure of the hydrophilic part of the ionomer, leading to the formation of sulfonic acid anhydrides. This phenomenon can rationalize the decreased acidity reported in our fluorescence study. Interestingly, acid treatment of the annealed film restores the acidity of the unannealed films. This cannot be rationalized simply by a greater proton uptake from the solution, as the film has to be electroneutral. It appears that the anhydrides formed during the annealing process undergo acid hydrolysis, leading to an increase in the number of SO3(-) groups and, consequently, an increase in the number of H3O(+) ions in the water channels. Besides, the films can be hydrated to an extent that is much greater than Nafion membranes, but the water uptake of acid treated annealed film is slightly less than that of nonannealed films. Hence, we conclude that, along with annealing, acid treatment, a procedure that is generally not performed on the cast films, is an important pretreatment procedure to improve the acidity and hence the transport properties of the cast film.
