基于碳化硅衬底的宽禁带半导体外延

宽禁带半导体具备禁带宽度大、电子饱和飘移速度高、击穿场强大等优势,是制备高功率密度、高频率、低损耗电子器件的理想材料。碳化硅(SiC)材料具有热导率高、化学稳定性好、耐高温等优点,在SiC衬底上外延宽禁带半导体材料,对充分发挥宽禁带半导体材料的优势,并提升宽禁带半导体电子器件的性能具有重要意义。得益于SiC衬底质量持续提升及成本不断降低,基于SiC衬底的宽禁带半导体电子市场占比呈现逐年增加的态势。在SiC衬底上外延生长高质量的宽禁带半导体材料是提高宽禁带半导体电子器件性能及可靠性的关键瓶颈。本文综述了近年来国内外研究者们在SiC衬底上外延SiC、氮化镓(GaN)、氧化镓(Ga₂O₃)所取得的研究进展,并展望了SiC衬底上宽禁带半导体外延的发展及应用前景。     

Mechanism and Stereoselectivity of the Elementometalation Process of Activated Alkyne RCCR(RCO2Me) by Cp2TaH3

The elementometalation process is a fundamental chemical step in several catalytic cycles. In this work, density functional theory computations have elucidated the detailed elementometalation mechanism of activated alkyne RCCR(RCO₂Me) by Cp₂TaH₃ and rationalized the selectivity in experimental findings. The calculated results show that in the formation process of (E)-olefin monohydride((E)-Pro), the Gibbs free energy barrier is low and the entire reaction is spontaneous and exothermic; thus, (E)-Pro can be formed easily. The formation of (Z)-η²-olefin monohydride complex ((Z)-Pro) is difficult due to its high Gibbs free energy barrier. The formation process (E)-Pro consists of the following five steps: hydride H1-shift, conformational isomerism 1, hydride H2-shift, conformational isomerism 2, and olefin coordination process. Topological analysis shows that there is a five-membered ring plane structure in the reaction pathway and that the final product (E)-Pro belongs to a typical η²-olefin monohydride complex. Our calculated results provide an explanation for experimental observations and useful insights for further development of olefin functionalization. © 2019 Wiley Periodicals, Inc.     

Influence of counter-anion on the coordination geometry of manganese(II) complexes with methyl-2-pyrazinecarboximidate ligand

Two new complexes of [Mn(2-MPyzCI)₂Cl₂].H²O (1) and [Mn(2-MPyzCI)₂(H₂O)₂](NO₃)₂ (2) were synthesized from the reaction of MnX₂.4H₂O (X=Cl^? and NO₃^?) with 2-cyanopyrazine in methanolic solution. The chelating methyl pyrazine-2-carboximidate (2-MPyzCI) ligand is formed via the methanolysis of 2-cyanopyrazine. Although coordination environment around manganes(II) ions is similar, but these complexes are different in geometrical position of 2-MPyzCI ligands. As both compounds are synthesized under the same reaction conditions, the only difference between these two complexes are counter ions and changing of geometrical position of ligands can be considered as a result of influence of the counter-anions on the molecular structures.     

Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λ_max = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k₁ versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k₁) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = s_N (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .     

Synthesis,crystal structure and conformational analysis of an unexpected [1,5]dithiocine product of aminopyridine and thiovanillin

The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C₂₁H₁₈N₂O₂S₂·0.463CH₃OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol^?1 between the two conformers.     

Lump and interaction solutions to the (3+1)-dimensional Burgers equation

The(3+1)-dimensional Burgers equation, which describes nonlinear waves in turbulence and the interface dynamics,is considered. Two types of semi-rational solutions, namely, the lump–kink solution and the lump–two kinks solution, are constructed from the quadratic function ansatz. Some interesting features of interactions between lumps and other solitons are revealed analytically and shown graphically, such as fusion and fission processes.     

An investigation of paddle wheel Cu2(μ2-O2CCH3)4 for gas molecule adsorptions

Metal organic frameworks (MOFs) have been well-known and extensively researched due to the high storage /good selectivity for gas molecules. Herein, the structures and electron paramagnetic resonance (EPR) spectra for dicopper paddle wheel MOF compound (Cu₂(µ₂-O₂CCH₃)₄ with various gas molecule are theoretically investigated by density functional theory (DFT) calculations. The adsorption energies and isotherms (including pure gas molecules and the mixed ones) are calculated for the gas molecules interacting with the unsaturated Cu₂(µ₂-O₂CCH₃)₄. Both quantities exhibit the roughly consistent orders (e.g. H₂S?>?NH₃?>?CO₂?>?CO?>?H₂O?>?N₂?>?NO?>?H₂ for isotherms and H₂S?>?NH₃?>?N₂?>?CO₂?>?NO?>?H₂O?>?H₂?>?CO for adsorption energies), possibly suggesting that this material may act as a potential adsorbent of these gas molecules. The catalytic property of Cu₂(µ₂-O₂CCH₃)₄ for oxidation of CO and NO into non-toxic molecules and splitting of H₂O into H₂ and O₂ in the solvent condition are uniformly discussed. Simulation of Grand Canonical Monte Carlo (GCMC) in MS 8.0 and calculations in Langmuir model reveal that Cu₂(µ₂-O₂CCH₃)₄ has good selectivity for CH₄ in natural gas (CH₄/CO₂/N₂) and SO₂ in fog (SO₂/NO/NO₂/H₂O/O₂), which would exhibit potential environmentally friendly applications.     

Interaction of 1-acylamino-2,2-dichloroethenyl(triphenyl)phosphonium chlorides with alkanolamines

Abstract

It is shown that the interaction of 1-acylamino-2,2-dichloroethenyl(triphenyl)-phosphonium chlorides with alkanolamines having a primary amino group results in the formation of 4-oxazolylphosphonium salts containing hydroxyalkylamine substituents at position 5 of the oxazole cycle. Under similar conditions the reaction of N-substituted alkanolamines with 1-acylamino-2,2-dichloroethenyl-(triphenyl)phosphonium chlorides leads to the formation of 1,3-oxazolidin-2-ylidene derivatives, in which the triphenylphosphonium group is located in the side chain. The structure of the new synthesized compounds has been reliably proven by elemental analysis, IR, ¹Н, ¹³С, ³¹Р NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction.