Formation of a crosslinked POSS network by an unusual hydrosilylation: Thermo‐oxidative stabilization of the α‐cristobalite phase in its amorphous regions

A semicrystalline inorganic–organic hybrid crosslinked network containing polyhedral oligomeric silsesquioxane (POSS) cores was constructed by the unusual hydrosilylation of the terminal vinyl groups of an internal acetylene‐containing silane linker by a POSS monomer. Products from the thermal treatments of this network in either argon or air at 250, 550, and 1000 °C, respectively, were characterized by Fourier transform infrared, Solid‐state ¹³C and ²⁹Si magic angle spinning NMR, X‐ray diffraction and XPS analyses. The highly symmetrically functionalized POSS silica clusters, in the fluorite silica phase, in the network were found to remain unchanged on thermal treatment possibly due to the shielding of the silica core by the functionalities and a cancellation of thermal stresses on the silica core. Stabilization of the metastable α‐cristobalite phase, which is typically formed on cooling by a β‐ to α‐transition of the β‐cristobalite phase formed above 1400 °C, was observed in the amorphous regions in the network sample treated only to 1000 °C in air. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Liquid hydridosilane precursor prepared from cyclopentasilane via sonication at low temperatures without the action of light

We report on a liquid hydridosilane precursor ink prepared via the ultrasonically induced ring-opening polymerisation of cyclopentasilane (Si₅H₁₀) without irradiation by ultraviolet light. The sonication is carried out in N₂ atmosphere at temperatures between 20 and 75 °C. We use size exclusion chromatography (SEC) to show polymer growth and estimate molecular mass with increasing sonication time. In combination with UV–vis transmission measurements, further SEC analysis is used to compare solutions subjected to either purely thermal or ultrasonic treatment at the same process temperature and for the same duration. Our findings provide strong evidence showing that the initiation of the polymerisation is sonocatalytic in nature and not thermic due to the macroscopic temperature of the solution. The liquid precursor is used to produce homogeneous hydrogenated amorphous silicon (a-Si:H) thin films via spin coating and pyrolytic conversion. The optoelectronic properties of the films are subsequently improved by hydrogen radical treatment. Fourier transform infrared spectroscopy (FTIR) is used to determine a compact film morphology and electrical conductivity measurements show that the layers attain a light-to-dark photosensitivity ratio of 2 × 10³ making them suitable for application in optoelectronic devices.     

Fabrication and characterization of zinc oxide anti-reflective coating on flexible thin film microcrystalline silicon solar cell

This paper studies the fabrication and characterization of 80 nm zinc oxide anti-reflective coating (ARC) on flexible 1.3 μm thin film microcrystalline silicon (μc-Si) solar cell. High resolution X-ray diffraction (HR-XRD) shows a c-axis oriented ZnO (0 0 2) peak (hexagonal crystal structure) at 34.3° with full width at half maximum (FWHM) of 0.3936°. Atomic force microscope (AFM) measures high surface roughness root-mean-square (RMS) of the layer (50.76 nm) which suggests scattering of the incident light at the front surface of the solar cell. UV–vis spectrophotometer illustrates that ZnO ARC has optical transmittance of more than 80% in the visible and infra-red (IR) regions and corresponds to band gap (E_g) of 3.3 eV as derived from Tauc equation. Inclusion of ZnO ARC successfully suppresses surface reflectance from the cell to 2% (at 600 nm) due to refractive index grading between the Si and the ZnO besides quarter-wavelength (λ/4) destructive interference effect. The reduced reflectance and effective scattering effect of the incident light at the front side of the cell are believed to be the reasons why short-circuit current (I_sc) and efficiency (η) of the cell improve.     

Performance of a silicon monochromator under high heat load

The performance of a cryogenically cooled double‐crystal silicon monochromator was studied under high‐heat‐load conditions with total absorbed powers and power densities ranging from 8 to 780 W and from 8 to 240 W mm^?2, respectively. When the temperature of the first crystal is maintained close to the temperature of zero thermal expansion of silicon, the monochromator shows nearly ideal performance with a thermal slope error of 0.6 µrad. By tuning the size of the first slit, the regime of the ideal performance can be maintained over a wide range of heat loads, i.e. from power densities of 110 W mm^?2 (at total absorbed power of 510 W) to 240 W mm^?2 (at total absorbed power of 240 W).     

Directed Gas Phase Formation of Silene (H2SiCH2)

The silene molecule (H₂SiCH₂; X¹A₁) has been synthesized under single collision conditions via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with silane (SiH₄). Exploiting crossed molecular beams experiments augmented by high-level electronic structure calculations, the elementary reaction commenced on the doublet surface through a barrierless insertion of the methylidyne radical into a silicon-hydrogen bond forming the silylmethyl (CH₂SiH₃; X²A′) complex followed by hydrogen migration to the methylsilyl radical (SiH₂CH₃; X²A′). Both silylmethyl and methylsilyl intermediates undergo unimolecular hydrogen loss to silene (H₂SiCH₂; X¹A₁). The exploration of the elementary reaction of methylidyne with silane delivers a unique view at the widely uncharted reaction dynamics and isomerization processes of the carbon–silicon system in the gas phase, which are noticeably different from those of the isovalent carbon system thus contributing to our knowledge on carbon silicon bond couplings at the molecular level.     

Cover Feature: How Many O-Donor Groups in Enterobactin Does It Take to Bind a Metal Cation? (Chem. Eur. J. 28/2019)

The E. coli siderophore enterobactin, the strongest Fe^III chelator known to date, forms hexacoordinate complexes with Si^IV, Ge^IV, and Ti^IV. Synthetic protocols have been developed to prepare non-symmetric enterobactin analogues with varying denticities. Various benzoic acid residues were coupled to the macrocyclic lactone to afford a diverse library of ligands. These enterobactin analogues were bound to Si^IV, Ge^IV, and Ti^IV, and the complexes were investigated through experimental and computational techniques. The binding behavior of the synthesized chelators enabled assessment of the contribution of each of the phenolic hydroxy groups in enterobactin to metal-ion complexation. It was found that at least four O-donors are needed for enterobactin derivatives to act as metal binders. Density functional theory calculations indicate that the strong binding behavior of enterobactin can be ascribed to a diminished translational entropy penalty, a common feature of the chelate effect, coupled with the structural arrangement of the three catechol moieties, which allows the triseryl base to be installed without distorting the preferred local metal-binding geometry of the catecholate ligands.