The role of hydrogen in hydrogenated microcrystalline silicon film and in deposition process with VHF-PECVD technique

The role of hydrogen in hydrogenated microcrystalline silicon ($\mu $c-Si:H) thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition (VHF-PECVD) technique have been investigated in this paper. With \textit{in situ} optical emission spectroscopy (OES) diagnosis during the fabrication of $\mu $c-Si:H thin films under different plasma excitation frequency $\nu _{\rm e }$ (60MHz--90MHz), the characteristic peak intensities ($I_{{\rm SiH}^*}$, $I_{{\rm H}\alpha^*}$ and $I_{{\rm H}\beta ^*}$) in SiHVHF-PECVD技术 氢化微晶硅 光发射光谱 薄膜学VHF-PECVD technique, hydrogenated microcrystalline silicon, role of hydrogen, optical emission spectroscopyProject supported by the Natural Science Foundation of Guangdong Province, China (Grant No 05300378), the State Key Development Program for Basic Research of China (Grant Nos G2000028202 and G2000028203) and the Program on Natural Science of Jinan University, Guangzhou, China (Grant No 51204056).2005-11-252005-11-252006-01-05The role of hydrogen in hydrogenated microcrystalline silicon （μc-Si：H） thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition （VHF-PECVD） technique have been investigated in this paper. With in situ optical emission spectroscopy （OES） diagnosis during the fabrication of μc-Si：H thin films under different plasma excitation frequency Ve （60MHz-90MHz）, the characteristic peak intensities （IsiH＊, IHα＊ and IHβ＊ ） in SiH4＋H2 plasma and the ratio of （IHα＊ ＋ IHβ＊ ） to IsiH＊ were measured; all the characteristic peak intensities and the ratio （IHα＊ ＋ IHβ＊ ）/IsiH＊ are increased with plasma excitation frequency. It is identified that high plasma excitation frequency is favourable to promote the decomposition of SiH4＋H2 to produce atomic hydrogen and SiHx radicals. The influences of atomic hydrogen on structural properties and that of SiHx radicals on deposition rate of μc-Si：H thin films have been studied through Raman spectra and thickness measurements, respectively. It can be concluded that both the crystalline volume fraction and deposition rate are enhanced with the increase of plasma excitation frequency, which is in good accord with the OES results. By means of FTIR measurements, hydrogen contents of μc-Si：H thin films deposited at different plasma excitation frequency have been evaluated from the integrated intensity of wagging mode near 640 cm^-1. The hydrogen contents vary from 4% to 5%, which are much lower than those of μc-Si：H films deposited with RF-PECVD technique. This implies that μc-Si：H thin films deposited with VHF-PECVD technique usually have good stability under light-soaking.     

Photoluminescence characteristics of GaN：Si

Both the electrical and optical properties are studied of the GaN：Si films with carrier concentrations ranging from 10^17cm^-3 to 10^19cm^-3.rhe results indicate that the increase in slope of carrier concentration starts to slow down when the flow rate of SiH4 is larger than 6.38μmol/min, which is attributed to the amphoteric character of Si. At the same time, the photoluminescence results show that the FWHM of UV is widened,which can be interpreted quantitatively with a semi-classic model. Furthermore, the intensity ratio between the yellow and the UV luminescences reduces monotonically with Si dopants increasing.     

Theoretical analysis of ion kinetic energies and DLC film deposition by CH4＋ Ar （He） dielectric barrier discharge plasmas

The kinetic energy of ions in dielectric barrier discharge plasmas are analysed theoretically using the model of binary collisions between ions and gas molecules. Langevin equation for ions in other gases, Blanc law for ions in mixed gases, and the two-temperature model for ions at higher reduced field are used to determine the ion mobility. The kinetic energies of ions in CH4 ＋ Ar（He） dielectric barrier discharge plasma at a fixed total gas pressure and various Ar （He） concentrations are calculated. It is found that with increasing Ar （He） concentration in CH4 ＋ Ar （He） from 20% to 83%, the CH4＋ kinetic energy increases from 69.6 （43.9） to 92.1 （128.5）eV, while the Ar＋ （He＋） kinetic energy decreases from 97 （145.2） to 78.8 （75.5）eV. The increase of CH4＋ kinetic energy is responsible for the increase of hardness of diamond-like carbon films deposited by CH4 ＋ Ar （He） dielectric barrier discharge without bias voltage over substrates.     

A new global potential energy surface of the ground state of SiH2+ (X2A1) system and dynamics calculations of the Si+ + H2 (v0 = 2, j0 = 0) → SiH+ + H reaction

A global potential energy surface (PES) of the ground state of SiH$_{2}^{+}$ system is built by using neural network method based on 18223 ab initio points. The topographic properties of PES are presented and compared with previous theoretical and experimental studies. The results indicate that the spectroscopic parameters obtained from the new PES are in good agreement with the experimental data. In order to further verify the validity of the new PES, a test dynamics calculation of the Si$^{+} +$ H$_{2}$ ($v_0 = 2, j_{0} = 0$) $\to $ H $+$ SiH$^{+}$ reaction has been carried out by using the time-dependent wave packet method. The integral cross sections and rate constants are computed for the title reaction. The reasonable dynamical behavior indicates that the newly constructed PES is suitable for relevant dynamics investigations.     

Ground state for CH2 and symmetry for methane decomposition

Using the different level of methods B3P86, BLYP, B3PW91, HF, QCISD、 CASSCF （4,4） and MP2 with the various basis functions 6-311G^＊＊, D95, cc-pVTZ and DGDZVP, the calculations of this paper confirm that the ground state is X^-3B1 with C2v group for CH2. Furthermore, the three kinds of theoretical methods, i.e. B3P86、 CCSD（T, MP4） and G2 with the same basis set cc-pVTZ only are used to recalculate the zero-point energy revision which are modified by scaling factor 0.989 for the high level based on the virial theorem, and also with the correction for basis set superposition error. These results are also contrary to X^-3∑^-g for the ground state of CH2 in reference. Based on the atomic and molecular reaction statics, this paper proves that the decomposition type （1） i.e. CH4 →CH2＋H2, is forbidden and the decomposition type （2） i.e. CH4→CHa＋H is allowed for CH4. This is similar to the decomposition of SiH4.     

Steady-state and transient electronic transport properties of β-(AlxGa1-x)2O3/Ga2O3 heterostructures: An ensemble Monte Carlo simulation

The steady-state and transient electron transport properties of $\beta $-(Al$_{x}$Ga$_{1-x}$)$_{2}$O$_{3}$/Ga$_{2}$O$_{3}$ heterostructures were investigated by Monte Carlo simulation with the classic three-valley model. In particular, the electronic band structures were acquired by first-principles calculations, which could provide precise parameters for calculating the transport properties of the two-dimensional electron gas (2DEG), and the quantization effect was considered in the $\varGamma $ valley with the five lowest subbands. Wave functions and energy eigenvalues were obtained by iteration of the Schrödinger-Poisson equations to calculate the 2DEG scattering rates with five main scattering mechanisms considered. The simulated low-field electron mobilities agree well with the experimental results, thus confirming the effectiveness of our models. The results show that the room temperature electron mobility of the $\beta $-(Al$_{0.188}$Ga$_{0.812}$)$_{2}$O$_{3}$/Ga$_{2}$O$_{3}$ heterostructure at 10 kV$ \cdot$cm$^{-1}$ is approximately 153.669 cm$^{2}\cdot$V$^{-1}\cdot$s$^{-1}$, and polar optical phonon scattering would have a significant impact on the mobility properties at this time. The region of negative differential mobility, overshoot of the transient electron velocity and negative diffusion coefficients are also observed when the electric field increases to the corresponding threshold value or even exceeds it. This work offers significant parameters for the $\beta$-(Al$_{x}$Ga$_{1-x}$)$_{2}$O$_{3}$/Ga$_{2}$O$_{3}$ heterostructure that may benefit the design of high-performance $\beta$-(Al$_{x}$Ga$_{1-x}$)$_{2}$O$_{3}$/Ga$_{2}$O$_{3}$ heterostructure-based devices.     

在HT-7托卡马克上密度扫描实验中的边界湍流和输运

在HT-7托卡马克上密度扫描实验中使用一个快速扫描气动朗缪尔探针来研究边界湍流和输运。随着中心弦平均等离子体密度的增加，在等离子体边界观察到径向电场剪切增强，径向电场的增强能够解释边界输运的减小和全局粒子约束的改善。粒子约束时间的增加和垂直扩散系数的减小证明粒子输运降低了。在等离子体边界区域发现电离和辐射驱动湍流的特征，表明电离和辐射在湍流驱动过程中具有重要性。     

Plasma-Pretreated Catalyst for Methanol Synthesis From Syngas

A new catalyst preparation method by combining the traditional coprecipitation method with an oxygen plasma pretreatment was developed in this paper. The ternary Cu/Zn/Al catalyst powders were first prepared by coprecipitation method, and then pretreated by the plasma in a fluidized-bed dielectric barrier discharge reactor with a carrier gas of a molar ratio of $hbox{O}_{2}/hbox{Ar} = 5/95$ . Then, the plasma-pretreated catalyst was conducted with the methanol synthesis test at the following conditions: $hbox{H}_{2}/hbox{CO}/hbox{N}_{2} = 64/32/4$, $Q = 900 hbox{sccm}$, $P = 4 hbox{MPa}$, and $T = 255 ^{circ}hbox{C}$. The plasma pretreatment could enhance the catalytic activity, e.g., the methanol selectivity increased from 28% to 72% and the methanol yield from 0.19 to 0.52 $hbox{g/g}_{rm cat.}cdothbox{h}$ , although the CO and $hbox{H}_{2}$ conversions were slightly decreased. On the other hand, the BET, inductively coupled plasma/optical emission spectroscopy, and X-ray diffraction analysis found that the catalytic properties did vary after plasma pretreatment. In short, this paper reveals that the plasma pretreatment is a viable process for preparation of Cu/Zn/Al catalyst in terms of methanol synthesis.      

Doubly Excited 1,3Fe States of Two-Electron Atoms under Weakly Coupled Plasma Environment *

Precise energy eigenvalues of metastable bound doubly excited $^{1,3}{\rm F}^{e}$ states originating from $2pnf$,($n=4$--6) configuration of helium-like ions $(Z=\text{2--4})$ under weakly coupled plasma (WCP) environment have been estimated within the framework of Ritz variational method. The wavefunction is expanded in explicitly correlated Hylleraas type basis set. The screened Coulomb potential is considered mimic the WCP environment. The atomic systems tend towards gradual instability and the number of excited metastable bound states reduces with increasing plasma strength. The wavelengths corresponding to $2pnf (^{1,3}{\rm F}^{e}) \rightarrow 2pn^\prime d (^{1,3}{\rm D}^{o})$ ($n=4$--6; $n^\prime=3$--6) transitions occurring between doubly excited states of plasma embedded two-electron ions are also reported.     

溶胶凝胶法制备参氟二氧化锡薄膜

利用溶胶凝胶方法，在硅碱玻璃底板上制备的透明低电阻SnO2:F薄膜，是一种低辐射导电薄膜。将SnCl4·5H2O 和 NH4F 溶解在50%乙醇和50%水的溶液中。制备条件为底板温度450℃，喷嘴与底板之间的距离60mm,载气流速8 L/min，制备时间5分钟。制成的SnO2:F薄膜面电阻为2Ω/□，可重复性好。并且文中还定性给出了SnO2:F薄膜其红外反射率与面电阻之间的关系。     

First-principles study on the electronic structure and optical properties of T12Cd2（SO4）3 and Rb2Cd2（SO4）3

With the help of ab initio full-potential linearized augmented plane wave （FPLAPW） method, calculating the electronic structure and linear optical properties is carried out for XCd2（SO4）3 （X =Tl, Rb）. The results show that Tl2Cd2（SO4）3 （TlCdS） has a larger band gap than Rb2Cd2（SO4）3 （RbCdS） and the energy bands for RbCdS are more dispersive than those of TlCdS. From their partial densities of states （PDOS）, we have observed that the hybridization between S ionic 2p and O atomic 2p orbitals forms SO4 ionic groups. The remarkable difference between RbCdS and TlCdS is, however, the degree of hybridization between cation （Tl and Rb） and its surrounding oxygen atoms. In the view of quantum chemistry, the strong p-d hybridization indicates the existence of their cation ionic bonds （Cd-O, Rb-O, and Tl-O）. The calculations of TlCdS and RbCdS show their optical properties to be less anisotropic. Their anisotropies in the optical properties mainly occur in a low photon energy region of 5-16 eV.     

Transition parameters of Li-like ions(Z = 7–11) in dense plasmas

The energy levels, transition energies, transition probabilities, weighted oscillator strengths, and line strengths of Lilike ions(Z = 7–11) in dense plasmas are investigated in this work. The relativistic effects and electron correlation effects are described by the MCDHF method. The ion sphere model is applied to include the dense plasma screening effect. The ground configuration 1 s~22 s and the excited 1 s~22 p, 1 s~23 l(l = 0–2) are considered. The configuration sets are enlarged until n = 7 where the calculated energy levels have converged. The critical free electron densities of 1 s~23 d states are estimated.Except for 1 s~23 s–1 s~23 p transitions, the transition energies for Δn = 0 increase, and for Δn ≠ 0 decrease with increasing free electron densities. For 1 s~23 s–1 s~23 p transitions, the spectra show blue-shift at lower free electron densities and red-shift at higher free electron densities, and the energy level crossing phenomens are observed at higher free electron densities.     

Synthesis and high temperature thermoelectric transport properties of Si-based type-I clathrates

N-type Si-based type-I clathrates with different Ga content were synthesized by combining the solid-state reaction method, melting method and spark plasma sintering (SPS) method. The effects of Ga composition on high temperature thermoelectric transport properties were investigated. The results show that at room temperature, the carrier concentration decreases, while the carrier mobility increases slightly with increasing Ga content. The Seebeck coefficient increases with increasing Ga content. Among all the samples, Ba_7.93Ga_17.13Si_28.72 exhibits higher Seebeck coefficient than the others and reaches -135~μ V.K^-1 at 1000 K. The sample prepared by this method exhibits very high electrical conductivity, and reaches 1.95× 10⁵S.m^-1 for Ba_8.01Ga_16.61Si_28.93 at room temperature. The thermal conductivity of all samples is almost temperature independent in the temperature range of 300--1000~K, indicating the behaviour of a typical metal. The maximum {ZT} value of 0.75 is obtained at 1000~K for the compound Ba_7.93Ga_17.13Si_28.72.     

SF_6分子最高占据轨道对称性的判断

量化计算是理论研究分子的重要手段,对于具有高对称群的分子,采用子群计算是常用的方法.分子的电子态或分子轨道等的对称性在子群的表示中会出现重迭,从而不能从子群的结果直接给出电子态或分子轨道对称性的归属.本文以如何判断SF6基态1 A_(1g)的电子组态中最高占据轨道的对称性为例来解决这个问题.针对某些文献中的SF6基态1 A1g的电子组态中,最高占据轨道对称性是T_(1g)却写成T_(2g)的问题,采用Molpro量化计算软件,对SF6基态的平衡结构,进行了HF/6-311G*计算,得到了能量三重简并的最高占据轨道的函数表达式,进而运用O_h群的对称操作作用在三个轨道函数上,得到各操作的矩阵表示,于是得到特征标,最后确定了最高占据轨道为T_(1g)对称性.     

Research of the behaviour of O chemisorption on the (110) surface of Rhx--Pt1－x alloy

An atomic group model of the disordered binary alloy Rhx-Pt1-x has been constructed to investigate surface segregation. According to the model, we have calculated the electronic structure of the Rhx-Pt1-x alloy surface by using the recursion method when O atoms are adsorbed on the Rhx-Pt1-x （110） surface under the condition of coverage 0.5. The calculation results indicate that the chemical adsorption of O changes greatly the density of states near the Fermi level, and the surface segregation exhibits a reversal behaviour. In addition, when x 〈 0.3, the surface on which O is adsorbed displays the property of Pt; whereas when x 〉 0.3 it displays the property of Rh.     

30-5000eV的电子被若干分子散射的总截面计算的一种修正势方法

利用可加性规则，使用Hartree-Fock波函数，采用由束缚原子概念修正过的复光学势，在30~5000eV这一较大的能域内对电子被N2、NO、NO2、CH4、CF4、CF3H、C2H2及C2H4散射的总截面进行了计算。束缚原子不同于自由原子之处，是束缚原子概念考虑了不同分子中的不同的电子云重叠情况，并根据电子云的重叠情况对复光学势进行修正。文中，将定量的计算结果与实验结果及其它理论计算结果进行了比较，结果显示出在30~5000eV内，计算结果与实验结果及其它理论计算结果间有较好的一致性。同时结果也表明，在较低的能量下，尤其是当入射电子的能量低于500eV时，利用被束缚原子概念修正过的复光学势进行计算得到的结果，要比利用未被束缚原子概念修正的复光学势计算得到的结果更接近于实验值。因此，在复光学势中考虑电子云的重叠效应可改善电子被分子散射的总截面的计算精度。     

Finite element simulation of Love wave sensor for the detection of volatile organic gases

The three-dimensional (3D) finite element (FE) simulation and analysis of Love wave sensors based on polyisobutylene (PIB) layers/SiO$_{2}$/ST-90$^\circ$X quartz structure are presented in this paper, as well as the investigation of coupled resonance effect on the acoustic properties of the devices. The mass sensitivity of the basic Love wave device with SiO$_{2}$ guiding layers is solved analytically. And the highest mass sensitivity of 128 m$^{2}$/kg is obtained as $h_{\rm s}/\lambda =0.175$. The sensitivity of the Love wave sensors for sensing volatile organic compounds (VOCs) is greatly improved due to the presence of coupled resonance induced by the PIB nanorods on the device surface. The frequency shifts of the sensor corresponding to CH$_{2}$Cl$_{2}$, CHCl$_{3}$, CCl$_{4}$, C$_{2}$Cl$_{4}$, CH$_{3}$Cl and C$_{2}$HCl$_{3}$ with the concentration of 100 ppm are 1.431 kHz, 5.507 kHz, 13.437 kHz, 85.948 kHz, 0.127 kHz and 17.879 kHz, respectively. The viscoelasticity influence of the sensitive material on the characteristics of SAW sensors is also studied. By taking account of the viscoelasticity of the PIB layers, the sensitivities of the SAW sensors with the PIB film and PIB nanorods decay in different degree. The gas sensing property of the Love wave sensor with PIB nanorods is superior to that of the PIB films. Meanwhile, the Love wave sensors with PIB sensitive layers show good selectivity to C$_{2}$Cl$_{4}$, making it an ideal selection for gas sensing applications.     

等离子体对含硼两相流扩散燃烧特性的影响

为排除来流空气对含硼燃气的掺混效应, 研究等离子体对含硼富燃料推进剂在补燃室二次燃烧过程的影响, 建立了含硼两相流平行进气扩散燃烧物理模型. 利用高速摄影仪拍摄了含硼燃气在补燃室二次燃烧的火焰图像, 分析了该物理模型的扩散燃烧特性和硼颗粒的二次点火距离. 采用硼颗粒的King点火模型、有限速度/涡耗散模型、颗粒轨道模型和RNG k-ε模型以及等离子体模型, 模拟了一定条件下等离子体对含硼两相流扩散燃烧过程的影响. 结果表明, 依据含硼燃气二次燃烧图像得到的硼颗粒二次点火距离, 与数值模拟结果基本一致, 保证了该物理模型和计算方法的可靠性. 含硼两相流经过等离子体区域后, 硼颗粒在运动轨迹上颗粒温度明显增加, 颗粒直径明显减小, B₂O₃的质量分数分布区域明显扩增, 70%的硼颗粒在到达补燃室2/3尺寸前燃烧效率已达到100%, 硼颗粒充分燃烧释放出更多热量导致中心流线区域温度增加近1/2, 可见等离子体可以明显强化含硼两相流的燃烧过程, 提高硼颗粒的燃烧效率.     

The evaluation of bond dissociation energies for NO2 scission in nitro compounds using density functional and complete basis set methods

By using the density functional theory （B3LYP） and four highly accurate complete basis set （CBS-Q, CBS-QB3, CBS-Lq, and CBS-4M）ab initio methods, the X（C, N, O）-NO2 bond dissociation energies （BDEs） for CH3NO2, C2H3NO2, C2H5NO2, HONO2, CH3ONO2, C2H5ONO2, NH2NO2 （CH3）2NNO2 are computed. By comparing the computed BDEs and experimental results, it is found that the B3LYP method is unable to predict satisfactorily the results of bond dissociation energy （BDE）; however, all four CBS models are generally able to give reliable predication of the X（C, N, O）-NO2 BDEs for these nitro compounds. Moreover, the CBS-4M calculation is the least computationally demanding among the four CBS methods considered, Therefore, we recommend CBS-4M method as a reliable method of computing the BDEs for this nitro compound system.     

Synthesis and characterization of Ca2Sn1-xCexO4 with blue luminescence originating from Ce^4＋ charge transfer transition

Ce^4＋-doped Ca2SnO4 with a one-dimensional structure, which emits bright blue light, is prepared by using a solid-state reaction method. The x-ray diffraction results show that the Ce^4＋ ions doped in Ca2SnO4 occupy the Sn^4＋ sites. The excitation and emission spectra of Ca2Sn1-xCexO4 appear to have broad bands with peaks at - 268nm and -442nm, respectively. A long excited-state lifetime （-83μs） for the emission from Ca2Sn1-xCexO4 suggests that the luminescence originates from a ligand-to-metal Ce^4＋ charge transfer （CT）. The luminescent properties of Ca2Snl_xCexO4 have been compared with those of Sr2CeO4, which is the only material reported so far to show Ce^4＋ CT luminescence. More interestingly, it is observed that the emission intensity of Ca2Sn1-xCexO4 with a small doping concentration （x - 0.03） is comparable to that of Sr2CeO4 in which the concentration of active centre is 100%.