Influence of deposition temperature on amorphous structure of PECVD deposited a-Si:H thin films

The effect of deposition temperature on the structural and optical properties of amorphous hydrogenated silicon (a-Si:H) thin films deposited by plasma-enhanced chemical vapour deposition (PECVD) from silane diluted with hydrogen was under study. The series of thin films deposited at the deposition temperatures of 50–200°C were inspected by XRD, Raman spectroscopy and UV Vis spectrophotometry. All samples were found to be amorphous with no presence of the crystalline phase. Ordered silicon hydride regions were proved by XRD. Raman measurement analysis substantiated the results received from XRD showing that with increasing deposition temperature silicon-silicon bond-angle fluctuation decreases. The optical characterization based on transmittance spectra in the visible region presented that the refractive index exhibits upward trend with increasing deposition temperature, which can be caused by the densification of the amorphous network. We found out that the scale factor of the Tauc plot increases with the deposition temperature. This behaviour can be attributed to the increasing ordering of silicon hydride regions. The Tauc band gap energy, the iso-absorption value their difference were not particularly influenced by the deposition temperature. Improvements of the microstructure of the Si amorphous network have been deduced from the analysis.     

Logarithmic Finite-Size Correction in Non-neutral Two-Component Plasma on Sphere

We consider a general two-component plasma of classical pointlike charges \(+e\) (e is say the elementary charge) and \(-Z e\) (valency \(Z=1,2,\ldots \)), living on the surface of a sphere of radius R. The system is in thermal equilibrium at the inverse temperature \(\beta \), in the stability region against collapse of oppositely charged particle pairs \(\beta e^2 < 2/Z\). We study the effect of the system excess charge Qe on the finite-size expansion of the (dimensionless) grand potential \(\beta \varOmega \). By combining the stereographic projection of the sphere onto an infinite plane, the linear response theory and the planar results for the second moments of the species density correlation functions we show that for any \(\beta e^2 < 2/Z\) the large-R expansion of the grand potential is of the form \(\beta \varOmega \sim A_V R^2 + \left[ \chi /6 - \beta (Qe)^2/2\right] \ln R\), where \(A_V\) is the non-universal coefficient of the volume (bulk) part and the Euler number of the sphere \(\chi =2\). The same formula, containing also a non-universal surface term proportional to R, was obtained previously for the disc domain (\(\chi =1\)), in the case of the symmetric \((Z=1)\) two-component plasma at the collapse point \(\beta e^2=2\) and the jellium model \((Z\rightarrow 0)\) of identical e-charges in a fixed neutralizing background charge density at any coupling \(\beta e^2\) being an even integer. Our result thus indicates that the prefactor to the logarithmic finite-size expansion does not depend on the composition of the Coulomb fluid and its non-universal part \(-\beta (Qe)^2/2\) is independent of the geometry of the confining domain.     

Asymmetric Organocatalysis Under Mechanochemical Conditions

Asymmetric organocatalysis is a robust methodology providing access to numerous valuable compounds while having green chemistry principles in mind. The realization of organocatalytic transformation under solvent-free mechanochemical conditions brings additional benefits in terms of yields, selectivities, and, last but not least overall improved sustainability. This overview describes developments in the use of mechanochemistry as a vehicle for asymmetric organocatalytic transformations. The material is organized according to main catalytic activation modes, starting with covalent activation and proceeding to non-covalent activation modes. The advantages of mechanochemical organocatalytic reactions are particularly highlighted, but in some cases also, limitations are mentioned. Possibilities for target compound synthesis are also discussed.     

Crystal structure and theoretical investigation of the configurations of 1,3-dichloro-1,3-diazetidine-2,4-dione and 1,3-bis(trimethylsilyl)-1,3-diazetidine-2,4-dione

Crystal structures of 1,3-dichloro-1,3-diazetidine-2,4-dione ( 1 ) and the hitherto unknown compound 1,3-bis(trimethylsilyl)-1,3-diazetidine-2,4-dione ( 2 ) have been determined by X--ray crystallography: 1 : (CINCO)₂, M_r = 154.94, T = 295 K, orthorhombic, Pbca, a = 7.699(1), b = 6.706(1), c = 10.598(2) Å, V = 547.2(2) ų, Z = 4, d_x = 1.881 g/cm³, μ = 10.9 cm⁻¹, R = 3.14%, R_w = 2.82% (660 observations, 38 parameters). 2 : [(CH₃)₃SiNCO]₂, M_r = 230.41, T = 100 K, monoclinic, I2/a, a = 20.257(2), b = 6.416(1), c = 21.260(3) Å, β = 101.29(1)°, V = 2709.7(6) ų, Z = 8, d_x = 1.130 g/cm³, μ = 2.4 cm⁻¹, R = 4.86%, R_w = 4.39% (2375 observations, 151 parameters). In both compounds, the symmetry of the (XNCO)₂ framework (X = Cl, Si) was determined to be nearly C_2h with trans configuration of the exocyclic X atoms. Extreme values were observed for the angles between the ring plane and the exocyclic N–X bonds: 32.5(1)° in 1 and 2.5(2)° and 0.8(2)° in 2 , respectively. Quantum chemical procedures at various levels of theory (ab initio SCF and semi-empirical PM3) applied to 1 revealed the possible appearance of two isomers, a lower energy trans form and a higher energy cis form (approx. 2.4 kcal/mol above trans) differing mainly in the spatial arrangement of the chlorine atoms. The calculations excluded a planar heavy-atom configuration by missing a local energy minimum.     

Burning Graphite Faster than Carbon Black: A Case of Diffusion Control

External diffusion may be exploited as a tool to purify materials in a way thought to be inaccessible from a chemical reactivity point of view. A mixture of two carbonaceous materials, graphite and carbon black, are thermally oxidized in either i) outside total diffusion-limited regime or ii) total diffusion-limited regime. Depending on the treatment applied it is possible to purify either graphite, a trivial task, or carbon black, a task thought impossible. Introducing geometrical selectivity, controlled total diffusion-limited chemistry exceeds by far the field of carbon materials and can be used as an engineering tool for many materials purification, original synthesis, or to introduce asymmetry in a system. Several examples for direct applications of the findings are mentioned.