Mechanistic understanding of mechanochemical reactions is sparse and has been acquired mostly by stepwise ex situ analysis. We describe herein an unprecedented laboratory technique to monitor the ...course of mechanochemical transformations at the molecular level in situ and in real time by using Raman spectroscopy. The technique, in which translucent milling vessels are used that enable the collection of a Raman scattering signal from the sample as it is being milled, was validated on mechanochemical reactions to form coordination polymers and organic cocrystals. The technique enabled the assessment of the reaction dynamics and course under different reaction conditions as well as, for the first time, direct insight into the behavior of liquid additives during liquid‐assisted grinding.
Out of the dark: Mechanochemical reaction mechanisms were studied by a laboratory Raman spectroscopy technique developed for in situ and real‐time monitoring of milling reactions (see picture). The technique enabled the course of mechanochemical transformations of coordination polymers and organic materials to be followed as well as the study of liquid additives.
Monitoring of mechanochemical thiocarbamoylation by in situ Raman spectroscopy revealed the formation of aryl N‐thiocarbamoylbenzotriazoles, reactive intermediates deemed unisolable in solution. The ...first‐time isolation and structural characterization of these elusive molecules demonstrates the ability of mechanochemistry to access otherwise unobtainable intermediates and offers a new range of masked isothiocyanate reagents.
Saved from drowning in solvent: Switching from solution to mechanochemistry enabled the first‐time isolation and structural characterization of aromatic N‐thiocarbamoyl benzotriazoles, a family of reactive and previously thought unisolable intermediates of thiocarbamoylation reactions.
Friedel-Crafts (FC) acylation reactions were exploited in the preparation of ketone-functionalized aromatics. Environmentally more friendly, solvent-free mechanochemical reaction conditions of this ...industrially important reaction were developed. Reaction parameters such as FC catalyst, time, ratio of reagents and milling support were studied to establish the optimal reaction conditions. The scope of the reaction was explored by employment of different aromatic hydrocarbons in conjunction with anhydrides and acylation reagents. It was shown that certain FC-reactive aromatics could be effectively functionalized by FC acylations carried out under ball-milling conditions without the presence of a solvent. The reaction mechanism was studied by in situ Raman and ex situ IR spectroscopy.
Fluorine-doped tin oxide thin films (SnO2:F) are widely used as transparent conductive oxide electrodes in thin-film solar cells because of their appropriate electrical and optical properties. The ...surface morphology of these films influences their optical properties and therefore plays an important role in the overall efficiencies of the solar cells in which they are implemented. At rough surfaces light is diffusely scattered, extending the optical path of light inside the active layer of the solar cell, which in term improves light absorption and solar cell conversion efficiency. In this work, we investigated the surface morphology of undoped and doped SnO2 thin films and their influence on the optical properties of the films. We have compared and analysed the results obtained by several complementary methods for thin-film surface morphology investigation: atomic force microscopy (AFM), transmission electron microscopy (TEM), and grazing-incidence small-angle X-ray scattering (GISAXS). Based on the AFM and TEM results we propose a theoretical model that reproduces well the GISAXS scattering patterns.
In this paper, we studied the influence of polyvinylpyrrolidone (PVP) as a stabilization additive on optical and electrical properties of perovskite formamidinium lead iodide (FAPI) polycrystalline ...thin films on ZnO nanorods (ZNR). FAPI (as an active layer) was deposited from a single solution on ZNR (low temperature processed electron transport layer) using a one-step method with the inclusion of an anti-solvent. The role of PVP in the formation of the active layer was investigated by scanning electron microscopy and contact angle measurements to observe the effect on morphology, while X-ray diffraction was used as a method to study the stability of the film in an ambient environment. The effect of the PVP additive on the optical and electrical properties of the perovskite thin films was studied via photoluminescence, UV-Vis measurements, and electrical impedance spectroscopy. We have demonstrated that PVP inclusion in solution-processed perovskite FAPI thin films prevents the degradation of the film in an ambient atmosphere after aging for 2 months. The inclusion of the PVP also improves the infiltration of FAPI perovskite into ZnO nanostructures, increases electrical conductivity and radiative recombination of the photo-generated charge carriers. These results show promising information for promoting PVP stabilized FAPI perovskites for the new generation of photovoltaic devices.
ZnO has prominent electron transport and optical properties, beneficial for photovoltaic application, but its surface is prone to the formation of defects. To overcome this problem, we deposited ...nanostructured TiO2 thin film on ZnO nanorods to form a stable shell. ZnO nanorods synthesized by wet-chemistry are single crystals. Three different procedures for deposition of TiO2 were applied. The influence of preparation methods and parameters on the structure, morphology, electrical and optical properties were studied. Nanostructured TiO2 shells show different morphologies dependent on deposition methods: (1) separated nanoparticles (by pulsed laser deposition (PLD) in Ar), (2) a layer with nonhomogeneous thickness (by PLD in vacuum or DC reactive magnetron sputtering), and (3) a homogenous thin layer along the nanorods (by chemical deposition). Based on the structural study, we chose the preparation parameters to obtain an anatase structure of the TiO2 shell. Impedance spectroscopy shows pure electron conductivity that was considerably better in all the ZnO@TiO2 than in bare ZnO nanorods or TiO2 layers. The best conductivity among the studied samples and the lowest activation energy was observed for the sample with a chemically deposited TiO2 shell. Higher transparency in the visible part of spectrum was achieved for the sample with a homogenous TiO2 layer along the nanorods, then in the samples with a layer of varying thickness.
Transparent conducting oxides (TCO) with high electrical conductivity and at the same time high transparency in the visible spectrum are an important class of materials widely used in many devices ...requiring a transparent contact such as light-emitting diodes, solar cells and display screens. Since the improvement of electrical conductivity usually leads to degradation of optical transparency, a fine-tuning sample preparation process and a better understanding of the correlation between structural and transport properties is necessary for optimizing the properties of TCO for use in such devices. Here we report a structural and magnetotransport study of tin oxide (SnO2), a well-known and commonly used TCO, prepared by a simple and relatively cheap Atmospheric Pressure Chemical Vapour Deposition (APCVD) method in the form of thin films deposited on soda-lime glass substrates. The thin films were deposited at two different temperatures (which were previously found to be close to optimum for our setup), 590 °C and 610 °C, and with (doped) or without (undoped) the addition of fluorine dopants. Scanning Electron Microscopy (SEM) and Grazing Incidence X-ray Diffraction (GIXRD) revealed the presence of inhomogeneity in the samples, on a bigger scale in form of grains (80–200 nm), and on a smaller scale in form of crystallites (10–25 nm). Charge carrier density and mobility extracted from DC resistivity and Hall effect measurements were in the ranges 1–3 × 1020 cm−3 and 10–20 cm2/Vs, which are typical values for SnO2 films, and show a negligible temperature dependence from room temperature down to −269 °C. Such behaviour is ascribed to grain boundary scattering, with the interior of the grains degenerately doped (i.e., the Fermi level is situated well above the conduction band minimum) and with negligible electrostatic barriers at the grain boundaries (due to high dopant concentration). The observed difference for factor 2 in mobility among the thin-film SnO2 samples most likely arises due to the difference in the preferred orientation of crystallites (texture coefficient).
A series of thin silicon films with different degrees of crystallinity were prepared by decomposition of silane gas highly diluted with hydrogen, in radiofrequency glow discharge. The crystallite ...size, shape, and the portion of crystalline phase were investigated by high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), Raman spectroscopy (RS), and X-ray powder diffraction (XRD). The absorption coefficient (
α) was calculated from the measurement of UV–vis-transmittance. By using RS, the volume fractions of the crystalline phase were estimated from the ratio of the integrated intensities of transversal optical (TO)-related crystalline and amorphous bands. These results were in excellent agreement with the mean crystallite sizes measured in HRTEM images and crystallite sizes refined from XRD measurements. The red shift of absorption, appearing as a result of the increase of the crystal fraction, depends on the size and distribution of nanocrystals.
A new simple Monte Carlo method is introduced for the study of electrostatic screening by surrounding ions. The proposed method is not based on the generally used Markov chain method for sample ...generation. Each sample is pristine and there is no correlation with other samples. As the main novelty, the pairs of ions are gradually added to a sample provided that the energy of each ion is within the boundaries determined by the temperature and the size of ions. The proposed method provides reliable results, as demonstrated by the screening of ion in plasma and in water.
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