Bicyclo[3.2.0]hepta-1,4,6-triene: synthesis, thermal rearrangement, and anion formation

In order to determine the properties of the bicycloheptatrienyl anion (Ia) (predicted to be conjugatively stabilized by Hückel Molecular Orbital Theory) the neutral precursor, bicyclo[3. 2. 0] hepta-1, 4, 6-triene (I) was prepared by the following route.

Reaction of I with potassium-t-butoxide, potassium, or lithium dicyclohexylamide gave anion Ia in very low yield. Reprotonation of I was found to occur solely at the 1 or 5 position to give triene II, isolated as to its dimers.

A study of the acidity of I and of other conjugated hydrocarbons by means of ion cyclotron resonance spectroscopy resulted in determination of the following order of relative acidities:

H₂S ˃ C₅H₆ ˃ CH₃NO₂ ˃ 1, 4- C₅H₈ ˃ I ˃ C₂H₅OH ˃ H₂O; cyclo-C₇H₈ ˃ C₂ H₅OH; фCH₃ ˃ CH₃OH

In addition, limits for the proton affinities of the conjugate bases were determined:

350 kcal/mole ˂ PA(C₅ H₅^-) ˂ 360 kcal/mole

362 kcal/mole ˂ PA(C₅H₇^-, Ia, cyclo-C₇H₇^-) ˂ 377 kcal/mole PA(фCH₂^-) ˂ 385 kcal/mole

Gas phase kinetics of the trans-XVIII to I transformation gave the following activation parameters: E_a = 43.0 kcal/mole, log A = 15.53 and ∆S^ǂ (220°) = 9.6 cu. The results were interpreted as indicating initial 1,2 bond cleavage to give the 1,3-diradical which closed to I. Similar studies on cis-XVIII gave results consistent with a surface component to the reaction (E_a = 22.7 kcal/mole; log A = 9.23, ∆S^ǂ (119°) = -18.9 eu).

The low pressure (0.01 to 1 torr) pyrolysis of trans-XVIII gave in addition to I, fulvenallene (LV), ethynylcyclopentadiene (LVI) and heptafulvalene (LVII). The relative ratios of the C₇H₆ isomers were found to be dependent upon temperature and pressure, higher relative pressure and lower temperatures favoring formation of I. The results were found to be consistent with the intermediacy of vibrationally excited I and subsequent reaction to give LV and LVI.

Hydrogenated amorphous silicon and silicon nitride deposited at less than 100° C by ECR-PECVD for thin film transistors

A systematic study has been made of the growth of both hydrogenated amorphous silicon (a-Si:H) and silicon nitride (a-SiN) by electron cyclotron resonance plasma enhanced chemical vapour deposition (ECR-PECVD). In the case of a-SiN, helium and nitrogen gas is injected into the system such that it passes through the resonance zone. These highly ionised gases provide sufficient energy to ionise the silane gas, which is injected further downstream. It is demonstrated that a gas phase reaction occurs between the silane and nitrogen species. It is control of the ratio of silane to nitrogen in the plasma which is critical for the production of stoichiometric a-SiN. Material has been produced at 80°C with a Si:N ratio of 1:1.3 a breakdown strength of ∼6 MV cm-1 and resistivity of > 1014 Ω cm. In the case of a-Si:H, helium and hydrogen gas is injected into the ECR zone and silane is injected downstream. It is shown that control of the gas phase reactions is critical in this process also. a-Si:H has been deposited at 80 °C with a dark conductivity of 10-11 Ω-1 cm-1 and a photosensitivity of justbelowl 4×104. Such materials are suitable for use in thin film transistors on plastic substrates.

Microwave power effects on the properties of phosphorus-doped SiC:H films prepared using ECR-CVD

There has been a growing interest in hydrogenated silicon carbide films (SiC:H) prepared using the electron cyclotron resonance-chemical vapour deposition (ECR-CVD) technique. Using the ECR-CVD technique, SiC:H films have been prepared from a mixture of methane, silane and hydrogen, with phosphine as the doping gas. The effects of changes in the microwave power (from 150 to 900 W) on the film properties were investigated in a series of phosphorus-doped SiC:H films. In particular, the changes in the deposition rate, optical bandgap, activation energy and conductivity were investigated in conjunction with results from Raman scattering and Fourier transform infra-red (FTIR) analysis. It was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the amorphous matrix of the SiC:H films. This occurs in correspondence to a rapid increase in the conductivity and a reduction in the activation energy, both of which exhibit small variations in samples deposited at microwave powers exceeding 500 W. Analysis of IR absorption results suggests that hydrogen is bonded to silicon in the Si-H stretching mode and to carbon in the sp3 CHn rocking/wagging and bending mode in films deposited at higher microwave powers.

Mode softening in charge-density excitations of a two-dimensional electron gas driven by Rashba spin-orbit interaction

The electron density response of a uniform two-dimensional (2D) electron gas is investigated in the presence of a perpendicular magnetic field and Rashba spin-orbit interaction (SOI). It is found that, within the Hartree-Fock approximation, a charge density excitation mode below the cyclotron resonance frequency shows a mode softening behavior, when the spin-orbit coupling strength falls into a certain interval. This mode softening indicates that the ground state of an interacting uniform 2D electron gas may be driven by the Rashba SOI to undergo a phase transition to a nonuniform charge density wave state.

Charge-density and spin-density excitations in a two-dimensional electron gas with Rashba spin-orbit coupling

We study theoretically the charge-density and spin-density excitations in a two-dimensional electron gas in the presence of a perpendicular magnetic field and a Rashba type spin-orbit coupling. The dispersion and the corresponding intensity of excitations in the vicinity of cyclotron resonance frequency are calculated within the framework of random phase approximation. The dependence of excitation dispersion on various system parameters, i.e., the Rashba spin-orbit interaction strength, the electron density, the Zeeman spin splitting, and the Coulomb interaction strength is investigated.

Rashba spin-orbit coupling in InSb nanowires under transverse electric field

We investigate the Rashba spin-orbit coupling brought by transverse electric field in InSb nanowires. In small k(z) (k(z) is the wave vector along the wire direction) range, the Rashba spin-orbit splitting energy has a linear relationship with k(z), so we can define a Rashba coefficient similarly to the quantum well case. We deduce some empirical formulas of the spin-orbit splitting energy and Rashba coefficient, and compare them with the effective-mass calculating results. It is interesting to find that the Rashba spin-orbit splitting energy decreases as k(z) increases when k(z) is large due to the k(z)-quadratic term in the band energy. The Rashba coefficient increases with increasing electric field, and shows a saturating trend when the electric field is large. As the radius increases, the Rashba coefficient increases at first, then decreases. The effects of magnetic fields along different directions are discussed. The case where the magnetic field is along the wire direction or the electric field direction are similar. The spin state in an energy band changes smoothly as k(z) changes. The case where the magnetic field is perpendicular to the wire direction and the electric field direction is quite different from the above two cases, the k(z)-positive and negative parts of the energy bands are not symmetrical, and the energy bands with different spins cross at a k(z)-nonzero point, where the spin splitting energy and the effective g factor are zero.

ECR plasma in growth of cubic GaN by low pressure MOCVD

To heteroepitaxally grow the crystalline cubic-GaN (c-GaN) film on the substrates with large lattice mismatch is basically important for fabricating the blue or ultraviolet laser diodes based on cubic group III nitride materials. We have obtained the crystalline c-GaN film and the heteroepitaxial interface between c-Gan and GaAs (001) substrate by the ECR Plasma-Assisted Metal Organic Chemical Vapor Deposition (PA-MOCVD) under low-pressure and low-temperature (similar to600degreesC) on a homemade ECR-plasma Semiconductor Processing Device (ESPD). In order to decrease the growth temperature, the ECR plasma source was adopted as the activated nitrogen source, therefore the working pressure of MOCVD was decreased down to the region less than 1 Pa. To eliminate the damages from energetic ions of current plasma source, a Multi-cusp cavity,coupling ECR Plasma source (MEP) was selected to use in our experiment. To decrease the strain and dislocations induced from the large lattice mismatch between c-GaN and GaAs substrate, the plasma pretreatment procedure i.e., the initial growth technique was investigated The experiment arrangements, the characteristics of plasma and the growth procedure, the characteristics on-GaN film and interface between c-GaN and GaAs(001), and the roles of ECR plasma are described in this contribution.

傅立叶变换离子回旋共振质谱在含糖小分子分析中的应用

傅立叶变换离子回旋共振质谱是一种近些年来逐渐发展起来的新型质谱仪器，由于该类质谱检测器的设计和检测原理与传统质谱有着根本的区别，通过它获取的数据具有高分辨和高质量测量精度的特点。通常，超过100000以上的分辨本领能够对质谱中非常临近的质谱峰进行区分，并结合串联质谱中的高质谱测量精度数据，可以给出明确的串联质谱碎裂途径。 本论文选择4对具有同分异构特点的二糖黄酮进行了系统研究，实验采取负离子模式的电喷雾傅立叶变换离子回旋共振质谱，结合持续非共振辐照碰撞诱导解离模式，对同分异构体的区分进行了研究。在实验过程中，建立了一种全新的质量校正方法，使得质谱测量平均误差小于1.00 ppm1。首次直接利用子离子的结构信息，确定了负离子模式下二糖黄酮的去质子化位点。实验中还发现，RDA解离途径仅仅当二糖黄酮的苷元是黄烷酮并且B环上没有过多的富电子基团的情况下才能发生，同时，具有α1→2糖连接的二糖黄酮在串联质谱中能够发生多键解离，并采用Gaussian 03 程序利用 B3LYP/6-31G方法对其进行了理论计算。为了进一步讨论α1→2糖连接二糖黄酮的串联质谱特点，在温和实验条件下，对上述化合物进行了氢氘交换实验。实验中首次发现温和条件下，黄酮的氢氘交换位点依赖于苷元结构，除了糖链上羟基和苷元上的酚羟基能够发生氢氘交换外，苷元为黄烷酮的二糖黄酮中，C（3）、C（6）和C（8）上的氢能够被直接交换掉，而苷元为黄酮骨架的二糖黄酮则在此位点不发生氢氘交换反应，并依据高质量测量精度数据对其子离子产生途径进行研究。 论文还系统研究了由葡萄糖缩合而成的二糖，4对二糖异构体负离子模式电喷雾傅立叶变换离子回旋共振质谱研究表明，其离子化过程中，生成的去质子化的二聚体是主要气相离子，依据单糖的实验和计算化学结果，论文中提出二糖化合物的离子化模型。计算化学的结果还证实，构成二聚体的单体直接具有强烈的相互作用，能够在串联质谱中产生共价键解离的子离子，而不是简单的单体解离。利用SORI CID还对二糖化合物的糖连接位点和糖苷键构型进行了区分研究。 论文的最后一部分研究了人工合成类肝素类化合物DHα、THα 和 THβ的结构表征，在极其温和的负离子模式电喷雾质谱条件下，类肝素化合物仍然容易发生多个SO3中性丢失。串联质谱中的子离子通过傅立叶变换离子回旋共振质谱高质量精度测量数据进行了确认。实验对研究类肝素类化合物的质谱表征提供了借鉴。

Resonant subband Landau level coupling in symmetric quantum well

Subband structure and depolarization shifts in an ultrahigh mobility GaAs/Al0.24Ga0.76As quantum well are studied using magnetoinfrared spectroscopy via resonant subband Landau level coupling. Resonant couplings between the first and up to the fourth subbands are identified by well-separated antilevel-crossing split resonance, while the hy-lying subbands were identified by the cyclotron resonance linewidth broadening in the literature. In addition, a forbidden intersubband transition (first to third) has been observed. With the precise determination of the subband structure, we find that the depolarization shift can be well described by the semiclassical slab plasma model and the possible origins for the forbidden transition are discussed.

Magnetospectroscopy of bound phonons in high purity GaAs

Far infrared magnetophotoconductivity performed on high purity GaAs reveals the existence of fine structures in the resonant magnetopolaron regions. The fine structures are attributed to the presence of bound phonons due to multiphonon processes. We demonstrate that the magnetopolaron energy spectrum consists of bound phonon branches and magnetopolaron branches. Our results also indicate that different phonons are bound to a single impurity, and that the bound phonon in Si-doped GaAs is a quasilocalized mode.

全永磁ECR离子源研究进展

Electron Cyclotron Resonance (ECR) ion source is regarded as the most efficient machine to produce stable multiple charge state ion beams. Because of the special characteristics, all-permanent magnet ECR ion sources have been widely adopted around the world to produce stable ion beams of multiple charge state with good repetition have been widely adopted around the world to produce stable ion beams of multiple charge state with good repetition and high duty factor for compact research platforms and ion beam implanters. In this paper, all-permanent magnet ECR ion sources developed at IMP are presented, and typical parameters and performances are discussed. The high charge state source, LAPECR2, is mainly used to produce intense high charge state ion beams, and the LAPECR1 source is designed to produce intense ion beams of medium and low charge state. An improved LAPECR1-M is specially designed to produce heavy metal ion beams of low charge state. These ECR ion sources have been adopted by different experimental terminals at IMP and, with their nice performance, many experimental studies could be possible. 中文文摘：ECR(电子回旋共振)离子源是产生稳定的强流多电荷态离子束流最有效装置。全永磁ECR 离子源因其独特的特点为很多中小型多电荷态离子束流实验平台与离子注入机等系统所采用，为后者产生重复性好、稳定性强的多电荷态离子束流。本文着重论述了中国科学院近代物理研究所研制的几台全永磁多电荷态ECR 离子源及其特性与典型性能，如能产生强流高电荷态离子束流的高性能全永磁离子源LAPECR2，能产生强流中 低电荷态离子束流的LAPECR1，能产生多电荷态重金属离子束流的LAPECR1-M 等。这些性能稳定的离子源为提高近代物理研究所相关试验平台的性能提供了关键的束流品质保障。

Effects of magnetic configuration on hot electrons in highly charged ECR plasma

To investigate the hot electrons in highly charged electron cyclotron resonance (ECR) plasma, Bremsstrahlung radiations were measured on two ECR ion sources at the Institute of Modern Physics. Used as a comparative index of the mean energy of the hot electrons, a spectral temperature, Tspe, is derived through a linear fitting of the spectra in a semi-logarithmic representation. The influences of the external source parameters, especially the magnetic configuration, on the hot electrons are studied systematically. This study has experimentally demonstrated the importance of high microwave frequency and high magnetic field in the electron resonance heating to produce a high density of hot electrons, which is consistent with the empirical ECR scaling laws. The experimental results have again shown that a good compromise is needed between the ion extraction and the plasma confinement for an efficient production of highly charged ion beams. In addition, this investigation has shown that the correlation between the mean energy of the hot electrons and the magnetic field gradient at the ECR is well in agreement with the theoretical models.中文摘要：ECR(电子回旋共振)离子源是产生稳定的强流多电荷态离子束流最有效装置。全永磁 ECR 离子源因其独特的特点为很多中小型多电荷态离子束流实验平台与离子注入机等系统所采用，为后者产生重复性好、稳定性强的多电荷态离子束流。本文着重论述了中国科学院近代物理研究所研制的几台全永磁多电荷态ECR离子源及其特性与典型性能，如能产生强流高电荷态离子束流的高性能全永磁离子源LAPECR2，能产生强流中低电荷态离子束流的LAPECR1，能产生多电荷态重金属离子束流的LAPECR1-M等。这些性能稳定的离子源为提高近代物理研究所相关试验平台的性能提供了关键的束流品质保障。

强流高电荷态全永磁ECR离子源LAPECR2的初步调试

研制成功了一台强流高电荷态全永磁ECR(Electron Cyclotron Resonance)离子源LAPECR2(Lanzhou All Permanent Magnet ECR Ion Source No.2)。该离子源在完成磁体装配后已成功在近代物理研究所320 kV高压平台上安装就位,与后束运线完成对接组装。离子源于2005年7月在14.5 GHz实现了第一次成功起弧,并引出较强的混合束流。目前离子源已与后束线以及部分实验终端完成了联调,在实验终端能够获得强流较高电荷态的离子束流。本文将着重论述该全永磁源的结构技术特点和主要参数指标。本文还着重论述了LAPECR2离子源在14.5 GHz微波功率馈入条件下的初步调试结果,在此基础上对束流向实验终端联调的实验结果进行了讨论,着重分析了影响束流引出与传输效率的主要因素。

超导ECR源SECRAL轫致辐射谱的测量

热电子在ECR(Electron Cyclotron Resonance)源中有着非常重要的作用,为了研究ECR源的工作参数(微波功率、磁场等)对热电子的影响,我们对SECRAL(Superconducting ECR ion source with Advanced design in Lanzhou)等离子体在轴向发出的轫致辐射谱进行了系统的测量。从测得的轫致辐射谱中我们得到用来衡量热电子能量的参考量——光谱温度Tspe,并且对ECR源的几个工作参数与Tspe的关系进行了讨论。