Influence of O2/Ar ratio on the properties of transparent conductive niobium-doped ZnO films

Niobium-doped ZnO transparent conductive films are deposited on glass substrates by radio frequency sputtering at 300℃. The influence of O2/Ar ratio on the structural, electrical and optical properties of the as-deposited films is investigated by X-ray diffraction, Hall measurement and optical transmission spectroscopy. The lowest resistivity of 4.0×10^-4Ω· cm is obtained from the film deposited at the O2/Ar ratio of 1/12. The average optical transmittance of the films is over 90%.     

Direct determination of trace silicon in lanthanum oxide by using a selective volatility and slurry sampling-FETV-ICP-AES

A new method for determination of trace sillicon in high purity lanthanum oxide by using electrothermal vaporization (ETV)-ICP-AES with polytetrafluoroethylene (PTFE) slurry as a fluorinating reagent has been proposed. Under the optimized experimental conditions, the fluorination reactions of analyte (Si) and matrix(La) with PTFE in the graphite furnace took place at high temperature, and the fractional volatilily between Si and La was observed. Based on this principle the matrix interference could be eliminated. The detection limit of Si was 4.0μg·L⁻¹, and the RSD was 3.4%(C=0.2mg·L⁻¹,n=10). The procedure proposed has been applied successfully to determine trace Si in La₂O₃ without any chemical pre-treatment. Supported by the National Natural Science Foundation of China Qin Yongchao: born in Dec. 1953, ph. D., Assciate Professor     

超声波下酸化碘酸钾和亚硫酸钠反应的反应速率研究

分别测定在有超声波作用和在无超声波作用条件下 ,酸化碘酸钾 (KIO3 )和亚硫酸钠 (Na2 SO3 )反应的反应速率方程式及活化能 ,从而研究该反应的机理以及超声波在该反应中的作用 ,并确定反应的最佳条件。实验得出 ,超声波对该反应有一定的促进作用 ,但是这种促进作用只提高反应的速率常数和降低反应的活化能 ,并没有改变反应机理。在超声波功率为 30 0W时 ,反应的速率方程表示式为 :v =k·c1 0 9(KIO3 ) ·c1 0 0 (Na2 SO3 )·c1 0 8(H+ ) ,其中 :k =95 0 (mol-1·L) 2 ·s-1,活化能为 17 35kJ·mol-1。实验还得出 ,在温度为2 98K时 ,当KIO3 与Na2 SO3 的初始浓度比为 2∶5 ,H+ 的初始浓度为 0 0 4 2 8mol·L-1,超声功率为 30 0W时 ,反应速率为最快 ,即v =4 31× 10 -4mol·L-1·s-1)。     

Correlation between structure and hardness of magnetron sputtering deposited CNx films

Carbon nitride films are deposited on Si (001) substrates by reactive dc magnetron sputtering graphite in a pure N2 discharge. The structure of carbon nitride films has been probed using Fourier transformation infrared, near edge X-ray absorption fine structure (NEXAFS) and high resolution electron microscopy (HREM), and the hardness has been evaluated in nanoin-dentation experiments. FTIR spectra show that N atoms are bound to sp1, sp2, and sp3 hybridized C atoms. C1s NEXAFS spectra show that the intensity of π* resonance is the lowest for the film grown at substrate temperature TS = 350℃, with a turbostratic-like structure and high hardness, while it is the highest for the film grown at TS = 100℃, with an amorphous structure and low hardness. The correlation between the structure and hardness of carbon nitride films has been discussed.     

Fluorescence Determination of Artemisinin Using Hemoglobin as Catalyst and Pyronine B as Substrate

0 IntroductionMaalnadria siusb atr ompajicosr .he aAltrthe pmrisoibnlienmi (n qtihneghtraoopsiucs,QHS,Fig.1) is a sesquiterpene endoperoxide isola-ted fromArtemisia annuaL., an ancient Chineseherbal medicine usedfor treatment of fever and ma-laria.Studies of the structure and activity relation-ship have shownthat endoperoxide groupis essentialfor anti malarial activity of QHS and absence of thismoiety lead to completely loss in activity of thedrug. Many techniques have been developed to de…     

Influence of modulation period for β-Cu2+xSe/SiC nano-multilayer films on their thermoelectric properties

In this study, β-Cu_2+xSe/SiC nano-multilayer films with different modulation period were successfully deposited on SiO₂/Si substrates by sputtering alternately using Cu–Se and SiC targets. The deposited films were observed on both surface and cross-section, and the thermoelectric properties were studied. The results show that both carrier concentration and mobility at room temperature decreased with the reducing modulation period for the nano-multilayer films. The conductivity slightly decreased and Seebeck coefficient greatly increased with the reducing modulation period. As a result of competition, the power factor of the nano multilayer films increased with the reducing modulation period because the positive effect of the Seebeck coefficient exceeded the negative effect of the conductivity. In the case of β-Cu_2+xSe/SiC nano multilayer film with the smallest modulation periods (210 ?nm), the power factor reached 0.39 ?mWm^?1K^?2 and 0.59 ?mWm^?1K^?2 at room temperature and 325 ?°C, respectively. The enhanced power factor for nano multilayer films is attributed to the scattering process at the β-Cu_2+xSe/SiC layer interface, which reduces the carrier concentration and the mobility. It is concluded that the thermoelectric properties of β-Cu_2+xSe films can be effectively improved by designing nano multilayer structure.     

Rate constants for the reaction of ozone with <Emphasis Type="Italic">n</Emphasis>-butyl, <Emphasis Type="Italic">s</Emphasis>-butyl and <Emphasis Type="Italic">t</Emphasis>-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide （n-BMS, CHaCH2CH2CH2SCH3）, sec-butyl methyl sulfide （s-BMS, CH3CH2（CH3）CHSCHa） and tert-butyl methyl sulfide （t-BMS, （CH3）3CSCH3） were measured using our smog chamber under supposedly pseudo-first-order conditions at 30002 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are （1.23 ± 0.06）×10-19, （5.08 ± 0.19）×10-20 and （2.26 ± 0.14）×10-20 cm3 molecule-1· s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.     

3,4-dichlorotoluene ammoxidation to 3,4-dichlorobenzonitrile over VPO/SiO<Subscript>2</Subscript> catalyst

Ammoxidation of 3,4-dichlorotoluene (DCT) to prepare 3,4-dichlorobenzonitrile (DCBN) over silica supported vanadium phosphorus oxide catalysts has been studied. On the VPO/SiO₂ catalyst, the influence of the reaction temperature, the molar ratio of air/DCT, the molar ratio of NH₃/DCT in the feed gas and the space velocity (v ₁) on the conversion, yield and selectivity was observed. The most appropriate reaction condition is: reactionT=673 K,n(DCT):n(NH₃):n(air)=1:7:30 andv ₁=250 h⁻¹. At this optimum reaction condition, the conversion of DCT is 97.8%; the molar yield of DCBN is 67.4%. It was found that the addition of element phosphorus can improve the yield of DCBN compared with VO/SiO₂ catalyst. Foundation item: Supported by Youth Chen-Guang Project of the Committee of Science and Technology of Wuhan (20015005042) Biography: Huang Chi(1972-), male, Ph D, Lecture, research direction: ammoxidation.     

Studies on reduced extent method for inhibited thermokinetics of enzyme-catalyzed reaction

The thermokinetic reduced extent equations of reversible inhibitions for Michaiels-Menten enzymatic reaction were deduced, and then the criteria for distinguishing inhibition type was given and the methods for calculating kinetic parameters,K _M,K _i andv _m were suggested. This theory was applied to inverstigate the inhibited thermokinetics of laccase-catalyzed oxidation ofo-dihydroxybenzene bym-dihydroxybenzene. The experimental results show the inhibition belongs to reversible competitive type,K _M=6.224×10⁻³ mol·L⁻¹,K _i=2.363×10⁻² mol·L⁻¹. Xiong Ya: born Sep. 1961, Ph. D. graduate student. Curent research interest is in biothermochemistry research Supported by the National Natural Science Foundation of China     

The Distribution of a CP-asymmetric quantity in the decay channel J / Ψ → π + π ? π 0

The distribution of a CP-asymmetric quantityA in the decay channelJ/ψ→π ⁺ π ⁻ π ⁰ is investigated. This dimensionless quantityA is constructed from the momenta of the π-meson final states, namely A=P _x ^{π +} P _y ^{π −} -P _x ^{π −} P _y ^{π −}, whereP _h,P _x ^h andP _y ^h are the module of the momentum of a hadron h, the x- and y-components of that momentum respectively, theJ/ψ particle is produced by e⁺ e⁻ collision, and the direction of the momentum of e⁺ is taken to be the positive direction ofz axis. There would exists the violation under the combined transformation of charge conjugation and space reflection (CP violation) when the average ofA among a lot of events, 〈A〉, be examined to be nonzero clearly from data. In this way, 748 events are selected from the BES experimental data, and analyzed. The corresponding averageA-value is measured to be 〈A〉 = 0.010 39 ± 0.014 61 ± 0.015 2. Further, some discussion of our result, the size of the data sample being need for further attempt and a possible perspective are given.     

A novel Pd/silicalite-1 composite membrane for hydrogen separation

A novel Pd/silicalite-1 composite membrane supported on the macroporous tubular stainless steel substrate was successfully fabricated by electroless plating at 303 K. The structure, morphology and gaseous permeability of the membrane were detected by X-ray diffractiometry （XRD）, scanning electron microscopy （SEM） and single-gas permeation test, respectively. Results confirm the formation of a thin, smooth, and continuous Pd/silicalite-1 composite membrane. The obtained composite membrane shows a high H2 permeance of 1.15×10^-6 mol. m^-2. s^-1. Pa^-1 with moderate H2 selectivity of 250 for H2/N2 at 773 K, at 0.1 MPa pressure drop, suggesting the potential application for H2 separation.     

Crystal structure and negative thermal expansion of solid solution Lu<Subscript>2</Subscript>W<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>12</Subscript>

A new series of solid solutions Lu₂W_3−x Mo _x O₁₂ (0.5≤x≤2.5) were successfully synthesized by the solid-state method. Their crystal structure and negative thermal expansion properties were studied using high-temperature X-ray powder diffraction and the Rietveld method. All samples of rare-earth tungstates and molybdates are found to crystallize in the same orthorhombic structure with space group Pnca and show the negative thermal expansion phenomena related to transverse vibration of bridging oxygen atoms in the structure. Thermal expansion coefficients (TEC) of Lu₂W_3−x Mo _x O₁₂ are determined as −20.0×10⁻⁶ K⁻¹ for x=0.5 and −16.1×10⁻⁶ K⁻¹ for x=2.5 but -18.6×10⁻⁶ and −16.9×10⁻⁶ K⁻¹ for unsubstituted Lu₂W₃O₁₂ and Lu₂Mo₃O₁₂ in the identical temperature range of 200 to 800°C. High-temperature X-ray diffraction (XRD) data and bond length analysis suggest that the difference between W-O and Mo-O bond is responsible for the change of TECs after the element substitution in this series of solid solutions.     

Molecule modification and mass deposition induced by the implantation of low energy Fe+ ion beams into amino acids

Fe⁺ ion beams with the energy of 110 keV were implanted into films of L(+)-cysteine (HSCH₂CH(NH₂)COOH). One of the single crystals grown in hydrochloric acid solution with the implanted samples through slow evaporation was structurally characterized by the X-ray crystallography. The crystal is monoclinic, space group C2, with a = 1.8534(4) nm, b = 0.5234(1) nm, c = 0.7212(1) nm, β= 103.72°, V = 0.67965(3) nm³, Z = 4, F(000) = 144.0, D{clac} = 1.763 g · cm⁻³, μ(MoK _a = 1.06 mm⁻¹, T = 293(2) K. R = 0.0379, wR = 0.0835 for 660 observed reflections (I > 2σ(I)). The structural formula of the crystal compound is (CH₂CH(NH₂)NO₂)ClFe (M _r = 180.38 u). Products of heavy ion beam irradiation were purified and it was directly confirmed that the implanted Fe⁺ ions had been deposited in the novel molecules. The same doses of Fe⁺ ion beams of the same energy were implanted into films of L(+)-cysteine hydrochloride monohydrate. FTIR spectroscopy of the implanted samples proved that some of the original molecules were seriously damaged and significant modifications were induced.     

Magnetoelectric and converse magnetoelectric res ponses in TbxDy1-xFe2-y alloy ＆ Pb（Mg1/3Nb2/3）（1-x）TixO3 crystal laminated composites

Measured results of magnetoelectric （ME） and converse magnetoelectric （CME） effects of TbxDy1-xFe2-y/ Pb（Mg1/3Nb2/3）（1-x）TixO3/TbxDy1-xFe2-y （TD/PMNT/TD） and PMNT/TD/PMNT laminated composites are presented. ME effect was determined by measuring laminate voltage output under a Helmholtz-generated AC field biased by a DC field （0-1 kOe） （1Oe = 79.58 A/m）. The CME effect was measured by recording the voltage induced in a solenoid encompassing the ME sample while exposed to a DC bias field and PMNT layer driven by a 10 V AC source. The ME and CME responses in the two laminated structure are linear. The highest values of ME coefficients in TD/PMNT/TD and PMNT/TD/PMNT composites are 384 mV/Oe and 158 mV/Oe, respectively, while the highest values of CME coefficients in the two composites are 118 mG/V and 162 mG/V （1 G=10^-4 T）, respectively.     

I-V andC-V properties of TiO2 thin film by pulsed-laser reactive deposition

TiO-2 thin films have bee deposited on p-Si(111) substrates by pulsed-laser ablation of metallic Ti target in the O-3 ambient. The current-voltage and capacitance-voltage of the Al/TiO-2/Si capacitors are measured. The results show that the dielectric constant of thin film after being annealed at 700℃ is found to be 46, and the border trap density and the interface state density at the TiO-2/p-Si interface are 1.8×10 12 cm -2 and 2×10 12 eV -1·cm -2, respectively. The conduction mechanisms of as-deposited films are also discussed.     

The comparative investigation on redox property and second-order nonlinear response of Keggin-type α-[PM12O39NPh]3− (M = W and Mo) and Mo6NPh

Keggin-type phenylimido-polyoxometalates α-[PM₁₂O₃₉NPh]³⁻ (M = W and Mo) have been systematically investigated on the electronic structures, redox as well as nonlinear optical (NLO) properties by density functional theory (DFT). The strong M≡N bond confirmed by natural bond orbital (NBO) analysis comprises one s bond and two π bonds, the same as Mo≡N in [Mo₆O₁₈NPh]²⁻. Furthermore, phenylimido segment effectively modifies the electronic properties of α-[PM₁₂O₃₉NPh]³⁻. On one hand, when enlarging the inorganic cluster from {Mo₆O₁₈} to {PMo₁₂O₃₉}, the energy gap between HOMO and LUMO in α-[PMo₁₂O₃₉NPh]³⁻ decreased, resulting in enormously anodic shift for the reduction potential, while the excitation energy is less and the total second-order polarizability β ₀ is up to 438-3×10⁻³⁰ esu, which is nearly 10 times larger than that of [Mo₆O₁₈NPh]²⁻. On the other hand, when metal W in α-[PM₁₂O₃₉NPh]³⁻ is substituted by Mo, the interaction between Mo and N is enhanced and the redox ability becomes stronger. The β ₀ value for α-[PMo₁₂O₃₉NPh]³⁻ is more than 5 times higher than that of α-[PW₁₂O₃₉NPh]³⁻. It indicates that changing appropriate metal or enlarging the inorganic cluster will improve the redox properties and second-order nonlinear response. Moreover, the electron transition for three compounds mentioned above occurred mainly from organoimido segment (as the electron donor) to polyanion cluster (as the acceptor). As a result, α-[PMo₁₂O₃₉NPh]³⁻ may be a promising candidate for oxidant and nonlinear optical material. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. Supported by National Natural Science Foundation of China (Grant No. 20573016), Training Fund of NENU’s Scientific Innovation Project (Grant No. NENUSTC07017), Science Foundation for Young Teachers of Northeast Normal University (Grant No. 20070304) and Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT)     

Kinetic study of the reaction of chlorine atoms with 3-methyl-3-buten-1-ol

The reaction of a typical unsaturated alcohol, 3-methyl-3-buten-1-ol （MBO331）, with Cl atoms, was investigated for the first time. The reaction was investigated using discharged flow-tube coupled with electron impact mass spectrometer. The experiments were performed over the temperature range of 248 K-298 K and at pressure of 1 torr in He as the bath gas. The obtained kinetic data were used to derive the Arrhenius expression： k1 = （3.47 ± 1.21） × 10^-11 exp[（ 599 ±69）/7] cm^3 molecule^-1 s^-1. Finally, atmospheric lifetimes of the MBO331 with respect to OH radicals, NO3 radicals and CI atoms have been calculated and the atmospheric implications are considered briefly.     

CaCl2的水解反应对固态SiO2显微特征的影响

利用扫描电镜(SEM)和能谱仪(EDS)等手段,并结合热力学理论计算,研究了浸泡在1173 K温度下脱水不完全的CaCl2熔盐中的固态SiO2圆柱样显微特征变化及其原因,初步分析了CaCl2盐的水解反应对固态SiO2电解特性的影响.结果表明,未严格脱水操作的CaCl2盐很容易高温水解,生成的CaO在熔体中的活度只要不低于0.001,即可与SiO2逐级形成CaO·SiO2(CS)、3CaO·2SiO2(C3 S2)和2CaO·SiO2(C2 S)等多种硅酸盐,导致圆柱体外表面的形貌、结构发生较大变化;圆柱体内部渗透进入的熔盐中CaO含量低,形貌变化较小.外表面硅酸盐层的存在使仅内置阴极集流体的固态Si O 2圆柱体电解还原速度减慢和难度增加.     

Density functional theory study on the insertion reaction mechanism of dibromocarbene with formaldehyde

The insertion reaction mechanism of CBr2 with CH3CH2O has been studied by using the B3LYP/6-311G(d) and CCSD(T)/6-311G(d) at single point. The geometries of reactions,transition state and products were completely optimized. All the transition state is verified by the vibrational analysis and the internal re-action coordinate (IRC) calculations. The results show that reaction (1) is the dominant reaction path,which proceeds via two steps: i) two reactants form an intermediate (IM1),which is an exothermal re-action of 8.62 kJ·mol?1 without energy barrier; ii) P1 is obtained via the TS1 and the H-shift,in which the energy barrier is 44.53 kJ·mol?1. The statistical thermodynamics and Eyring transition state theory with Wigner correction are used to study the thermodynamic and kinetic characters of this reaction in temperature range from 100 to 2200 K. The results show that the appropriate reaction temperature ranges from 200 to 1900 K at 1.0 atm,in which the reaction has a bigger spontaneity capability,equi-librium constant (K) and higher rate constant (k).     

Influence of post-annealing on the properties of Ta-doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> transparent conductive films

Ta-doped In₂O₃ transparent conductive oxide films were deposited on glass substrates using radio-frequency (RF) sputtering at 300°C. The influence of post-annealing on the structural, morphologic, electrical and optical properties of the films was investigated using X-ray diffraction, field emission scanning electron microscopy, Hall measurements and optical transmission spectroscopy. The obtained films were polycrystalline with a cubic structure and were preferentially oriented in the (222) crystallographic direction. The lowest resistivity, 5.1×10⁻⁴ Ω cm, was obtained in the film annealed at 500°C, which is half of that of the un-annealed film (9.9×10⁻⁴ Ω cm). The average optical transmittance of the films was over 90%. The optical bandgap was found to decrease with increasing annealing temperature.