Potential of AMnO3 (A=Ca, Sr, Ba, La) as Active Layer in Inorganic Perovskite Solar Cells.

Inorganic perovskite CaMnO 3 ${{}_{3}}$ was proposed as a substitution for the TiO 2 ${{}_{2}}$ anatase in electron transport layers of solar cells containing the hybrid perovskite CH 3 ${{}_{3}}$ NH 3 ${{}_{3}}$ PbI 3 ${{}_{3}}$ based on increased mobility of electrons and better optical matching. Due to a suitable band gap concerning the absorption of sunlight, we investigate the potential of CaMnO 3 ${{}_{3}}$ and similar manganite perovskites, where Ca is replaced by either Sr, Ba or La, as an absorber layer in inorganic perovskite solar cells. In this study, we have used optical measurements on the synthesized AMnO 3 ${{}_{3}}$ (A=Ca, Sr, Ba, La) samples to aid density functional theory calculations (DFT) in order to accurately simulate the electronic and optical properties of AMnO 3 ${{}_{3}}$ compounds and gauge their potential for the role of absorber layer. Both experimental measurements and theoretical calculations show suitable band gap of 1.1-1.5 eV, depending on the compound, and absorption coefficients of the order of 10 5 ${{10}^{5}}$ cm - 1 ${{}^{-1}}$ in the visible part of the spectrum.

ZnO@TiO2 Core Shell Nanorod Arrays with Tailored Structural, Electrical, and Optical Properties for Photovoltaic Application.

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.

Mechanochemical Friedel-Crafts acylations.

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.

Trapping Reactive Intermediates by Mechanochemistry: Elusive Aryl N-Thiocarbamoylbenzotriazoles as Bench-Stable Reagents.

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.

Laboratory real-time and in situ monitoring of mechanochemical milling reactions by Raman spectroscopy.

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.

Surface Morphology of Textured Transparent Conductive Oxide Thin Film Seen by Various Probes: Visible Light, X-rays, Electron Scattering and Contact Probe.

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.

Formamidinium Lead Iodide Perovskite Films with Polyvinylpyrrolidone Additive for Active Layer in Perovskite Solar Cells, Enhanced Stability and Electrical Conductivity.

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.

Origin of Mangetotransport Properties in APCVD Deposited Tin Oxide Thin Films.

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).

Measurement method for the refractive index of thick solid and liquid layers.

A simple method is proposed for the refractive index measurement of thick solid and liquid layers. In contrast to interferometric methods, no mirrors are used, and the experimental setup is undemanding and simple. The method is based on the variation of transmission caused by optical interference within the layer as a function of incidence angle. A new equation is derived for the positions of the interference extrema versus incidence angle. Scattering at the surfaces and within the sample, as well as weak absorption, do not play important roles. The method is illustrated by the refractive index measurements of sapphire, window glass, and water.

Mechanochemical reactions studied by in situ Raman spectroscopy: base catalysis in liquid-assisted grinding.

In situ Raman spectroscopy was employed to study the course of a mechanochemical nucleophilic substitution on a carbonyl group. We describe evidence of base catalysis, akin to catalysis in solution, achieved by liquid-assisted grinding.

Mechanochemical C-H bond activation: rapid and regioselective double cyclopalladation monitored by in situ Raman spectroscopy.

The first direct mechanochemical transition-metal-mediated activation of strong phenyl C-H bonds is reported. The mechanochemical procedure, resulting in cyclopalladated complexes, is quantitative and significantly faster than solution synthesis and allows highly regioselective activation of two C-H bonds by palladium(II) acetate in asymmetrically substituted azobenzene. Milling is monitored by in situ solid-state Raman spectroscopy which in combination with quantum-chemical calculations enabled characterization of involved reaction species, direct insight into the dynamics and reaction pathways, as well as the optimization of a milling process.