Improvement of crystal quality of AlN grown on sapphire substrate by MOCVD

The crystalline quality of aluminum nitride (AlN) epilayers grown on sapphire substrates by MOCVD was improved by increasing hydrogen flow rate during the high temperature growth process. The AlN epilayer exhibited a root mean square (rms) of roughness was 1.944 nm from the 2×2 µm² size atomic force microscopy (AFM) images. Full widths at half maximum (FWHMs) of (002) and (102) rocking curves of triple‐axis high resolution X‐ray diffraction (HRXRD) measurements were as narrow as 28.8 arc sec and 868 arc sec, respectively. The optical transmittance spectra showed a sharp absorption edge at a wavelength of 200 nm and strong Fabry‐Perot (FP) oscillations. It is proposed that the improvement in crystalline quality is due to the surface in the low‐temperature aluminum nitride (LT‐AlN) buffer layer is promoted to be stable Al‐polarity by the conditions of increasing hydrogen flow rate and ramping up the growth temperature. Addtionally, the parasitic reactions are effectively suppressed by increasing the hydrogen flow rate during the growth process of high temperature. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Stereo-selectivity in a cyclotriphosphazene derivative bearing an exocyclic P-O moiety

Nucleophilic substitution reactions of N(3)P(3)Cl(4)[O(CH(2))(2)NCH(3)], (1) with the sodium salts of mono- and di-functional alcohols [methanol (2), phenol (3), tetraethyleneglycol (4) and 1,3-propanediol (5)] were carried out in order to investigate a possible directing effect of the spiro O-moiety on the formation of mono-substituted (2a, 3a), non-geminal di-substituted (2c, 3c) and ansa (4a, 5a) derivatives. Compounds isolated from the reactions were characterized by elemental analysis, mass spectrometry, (1)H and (31)P NMR spectroscopy and X-ray crystallographic analysis showed that the substituent OR in compounds (2a, 3a and 2c, 3c) and the ansa-ring in compounds (4a, 5a) formed cis to the P-O moiety of the exocyclic [O(CH(2))(2)NCH(3)] spiro ring. The formation of products (2a-d, 3a-d, 4a, 5a and 5b) was quantified from the (31)P NMR spectra of the reaction mixtures, which showed an overwhelming preference for derivatives (2a, 3a, 2c, 3c, 4a, 5a) with the substituent cis to the P-O moiety of the exocyclic spiro ring (2a, 3a, 2c, 3c, 4a, 5a), except for reaction with 1,3-propanediol where the six-membered ring spiro derivative (5b) was about three times more abundant than the eight-membered ring ansa-derivative (5a). Overwhelming formation of products with the substituent cis to the exocyclic P-O moiety is proof that the cation-assisted mechanism is responsible for the stereo-selectivity in the reactions with alkoxides.     

电子回旋共振-射频双等离子体沉积氧化硅薄膜过程中的射频偏压效应

本文利用六甲基乙硅氧烷(HMDSO)和氧气(O2)为反应气体,利用微波电子回旋共振-射频双等离子体化学气相沉积法沉积氧化硅薄膜,并利用发射光谱对等离子体特性进行原位诊断.研究表明,RF偏压对氧化硅薄膜沉积速率和薄膜中的化学键结构产生有意义的影响.小的直流自偏压会略微提高沉积速率;但随着直流自偏压的增加,离子轰击效应及刻蚀作用加强,薄膜的沉积速率下降.在13.56MHz和400kHz两个不同射频频率条件下所沉积的薄膜中,O和Si的比例基本相同,均超过2∶1;但400kHz射频偏压下薄膜中的碳成分比例比13.56MHz条件下的要高得多.这可以归因为高的射频偏压的应用不仅可增强离子轰击效应,而且与体等离子体相互作用,使高活性的氧原子增多;而低频偏压的作用主要是增强离子轰击效应.     

Thermal annealing dependence of some optical properties of plasma-modified porous silicon

The photoluminescence and reflectance of porous silicon (PS) with and without hydrocarbon (CH_x) deposition fabricated by plasma enhanced chemical vapour deposition (PECVD) technique have been investigated. The PS samples were then, annealed at temperatures between 200 and 800 °C. The influence of thermal annealing on optical properties of the hydrocarbon layer/porous silicon/silicon structure (CH_x/PS/Si) was studied by means of photoluminescence (PL) measurements, reflectivity and ellipsometry spectroscopy. The composition of the PS surface was monitored by transmission Fourier transform infrared (FTIR) spectroscopy. Photoluminescence and reflectance measurements were carried out before and after annealing on the carbonized samples for wavelengths between 250 and 1200 nm. A reduction of the reflectance in the ultraviolet region of the spectrum was observed for the hydrocarbon deposited polished silicon samples but an opposite behaviour was found in the case of the CH_x/PS ones. From the comparison of the photoluminescence and reflectance spectra, it was found that most of the contribution of the PL in the porous silicon came from its upper interface. The PL and reflectance spectra were found to be opposite to one another. Increasing the annealing temperature reduced the PL intensity and an increase in the ultraviolet reflectance was observed. These observations, consistent with a surface dominated emission process, suggest that the surface state of the PS is the principal determinant of the PL spectrum and the PL efficiency.     

Diastereomeric β-cyclodextrin Complexes With Cizolirtine and Its Carbinol. A Molecular Dynamics Study

The enantiodifferentiation observed in the complexation of cizolirtine and its parent carbinol with g -cyclodextrin is due to differences in the average structure of each diastereomeric complex, as deduced from molecular dynamics simulations. Bimodal complexation is possible for all these molecules; both computations and experiments indicate the inclusion of the phenyl group. Two distinct inclusion orientations of this group were considered; although the preferred orientation was determined, the other one may contribute to the final average structure depending on the enantiomeric guest molecule.     

State of the art in catalytic oxidation of chlorinated volatile organic compounds

Chlorine-containing organic compounds (Cl-VOC) require special attention due to their distinct toxicity, high stability and persistence in the environment. Removal of Cl-VOC by catalytic oxidation over a wide variety of catalysts has been presented in literature. This paper reviews the state of the art in this subject, including different model compounds, nature of catalysts, and oxidation activity. Catalyst selectivity (CO₂ vs. CO and HCl vs. Cl₂), by-products formation and the causes of deactivation are also analyzed as the most important factors in the catalyst selection for practical applications.     

Synthesis,characterization, and antioxidant activity of heterocyclic Schiff bases

Schiff base derivatives have gained great importance due to revealing a great number of biological properties. Schiff bases were synthesized by treatment of 4-amino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one ( 1 ) with various aldehydes in methanol at reflux. In addition, diamine was reacted with an aldehyde to yield the corresponding Schiff bases. The structures of synthesized Schiff bases were elucidated by spectroscopic methods such as microanalysis, ¹H-NMR, ¹³C-NMR, and FTIR. Antioxidant activities of synthesized Schiff bases were carried out using different antioxidant assays such as 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH^•) scavenging, 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging, and reducing power activity. (E)-4-((1H-indol-3-yl)methyleneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one ( 3 ), (E)-1,5-dimethyl-4-((2-methyl-1H-indol-3-yl)methyleneamino)-2-phenyl-1H-pyrazol-3(2H)-one ( 5 ), (E)-1,5-dimethyl-2-phenyl-4-(thiophen-2-ylmethyleneamino)-1H-pyrazol-3(2H)-one ( 7 ), (E)-1,5-dimethyl-2-phenyl-4-(quinolin-2-ylmethyleneamino)-1H-pyrazol-3(2H)-one ( 9 ), (1S,2S,N1,N2)-N1,N2-bis((1H-indol-3-yl)methylene)cyclohexane-1,2-diamine ( 11 ), and (1S,2S,N1,N2)-N1,N2-bis((2-methyl-1H-indol-3-yl)methylene)cyclohexane-1,2-diamine ( 12 ) were synthesized in high yields. Compound 5 displayed a good ABTS^•+ activity. Compound 3 revealed the outstanding activity in all assays. Compound 7 has the best-reducing power ability in comparison to other synthesized compounds. Although compounds 5, 11, 12 are new, compounds 3, 7, 9 are known. Due to revealing a good antioxidant activity, the synthesized compounds ( 3, 5, 7 ) have the potential to be used as synthetic antioxidant agents.     

Synthesis and biological evaluation of 4,5,6,7-tetrahydrothieno[2,3-c]pyridine–based β-aminonitriles and their derivatives: β-amino carboxamides, (thio)ureas,and tetracycles

The preparation and cytotoxic characterization of 4,5,6,7-tetrahydrothieno[2,3-c]pyridine–based β-aminonitriles, β-amino carboxamides, and their (thio)urea and annulated derivatives were accomplished. Following a synthetic route involving Gewald three-component reactions (G-3CR) and a Lewis acid–catalyzed iso (thio)cyanate coupling, 30 compounds were prepared for antitumor evaluation. For derivatizations, a catalytic amount of CuOAc₂ (20 mol%) was essential for improving the reactivity of either the C-2 amino function of thiophene or isocyanates. The synthesized analogues demonstrated a weak to moderate antitumor activity in a low micromolar range against A549 and K562 cancer cell lines.     

4,5-Unsubstituted 2,3-dihydroisoxazoles in the synthesis of racemic 4-substituted isoxazolidine-5-carbonitriles

The synthesis of novel types of the 4-hydroxy- and 4-bromosubstituted isoxazolidines is described. Dihydroxylation reactions of 4,5-unsubstituted 2,3-dihydroisoxazoles proceed from the less hindered side and provide the major 3,4-trans-isoxazolidine-4,5-diols in good yields. On the other hand, the hydroxybromination reaction of the model 3-phenyl-2,3-dihydroisoxazole predominantly proceeds with 3,4-cis selectivity. Isoxazolidine-5-carbonitriles have been prepared from isoxazolidines possessing a good leaving group at C5 by treatment with TMSCN in the presence of TMSOTf.