缩胺基脲衍生物HeI PES和电子结构的研究

利用HeI紫外光电子能谱(PES)首次得到一组缩胺基脲衍生物的PES谱图。并利用RHF(6-31G^*^*)计算了它们的电子结构,解析了实验谱,分析和说明与实验电离能所对应的分子轨道的特征。论证了计算结果与实验值间很好的相符关系。并通过实验和计算结果,讨论了这类化合物取代基的影响和为何缺乏生物活性。     

醚基功能化离子液体[MOEMIm]Cl和[EOEMIm]Cl热力学性质

通过核磁共振氢谱,核磁共振碳谱,元素分析和热重分析对醚基功能化的离子液体[MOEMIm]Cl和[EOEMIm]Cl进行了表征。在温度范围T=288.15–328.15 K内,测定了离子液体[MOEMIm]Cl和[EOEMIm]Cl的密度(ρ)、表面张力(γ)和折光率(nD)。根据这些实验数据,讨论并计算了离子液体[MOEMIm]Cl和[EOEMIm]Cl的体积性质。计算出离子液体[MOEMIm]Cl和[EOEMIm]Cl的摩尔表面吉布斯自由能(gs)、摩尔表面熵(s)、摩尔表面焓(h)、摩尔极化度(Rm)和摩尔极化率(αp),h均近似为一个常数说明这两种离子液体从内部到表面的过程是一个等库仑过程,同时这两种离子液体的Rm和αp均与温度无关。本文还用摩尔表面Gibbs自由能改进Lorentz-Lorenz方程并预测离子液体表面张力,预测值与实验值高度相关。     

逐级电子转移过程的0.5次微分电分析法

卷积伏安法(新极谱法)是近十年发展起来的一种新电化学分析方法, 本文报导了逐级电子转移过程的0.51次微分电分析法的理论和实验结果, 用计算机模拟了理论极谱图, 讨论了标准分离电位和电子转移数对极谱的影响 。并选择0.1M的NH~4Cl-NH~4OH作为缓冲溶液中铜(II)的还原作为检验理论和实验之间的关系。     

碳原子和离子团簇奇偶性的研究

本文用Huckel-Hubbard方法,考虑多电子体系的组态相互作用,计算出线性碳原子和离子团簇(Gn,C_n~±)的π电子体系能量E_n。两相邻原子簇的能量差△E_N=|E_n-E_(n-1)|与n的关系显示出与实验相符合的奇偶性质。由于条件的限制,只计算到n为6的碳原子和离子团簇,然后利用电子结构图,外推出n为7和8的原子和离子团簇的π电子能量。所得结果也定性显示出团簇的奇偶性。此外,我们还利用D_v—X_α方法进行对比计算,并讨论了计算结果。     

非自由态Cu(Ⅱ)的径向波函数及其电子结构

本文利用非自由态离子的标度径向理论给出了非自由态Cu(Ⅱ)的3d径向波函数,讨论了Jahn-Teller效应对非自由度的影响。计算了一些Cu(Ⅱ)络合物的d-d电子光谱和g-因子,计算结果与实验值较为一致。     

异烟酸在银溶胶上的表面增强喇曼散射及影响因素

本文研究了异烟酸吸附在银溶胶表面的表面增强喇曼散射(SERS)光谱以及卤素离子、溶液pH值及溶液浓度对异烟酸SERS光谱的影响。文章提出了离子在银溶胶表面的吸附方式,即主要以—COO~-端吸附于银溶胶表面。最后,对所述实验现象作了定性讨论。     

定量AES分析中基体效应的迭代修正法

以Shimizu提出的定量AES分析关系为基础,作者提出一种可用于二元和多元合金定量AES分析的迭代方法。通过引入合金的原子序数和原子密度的概念,计算了合金中元素的基体效应修正因子。与其它方法不同的是,本法中基体效应修正因子是合金元素浓度的函数,受到整体组分的影响。通过对文献报道的五种典型单相多晶二元合金Ag-Pd,Ni-Pd,Cr-Fe,Mo-Fe和Ni-Mg的定量分析计算发现,本法的分析精密度优于F因子法、K因子法及改进K因子修正法。     

时间相关离子散射谱（TDISS）用于研究气体覆盖度

本文介绍一种新的在超高真空装置内测量样品上气体覆盖度的方法:时间相关离子散射谱(TDISS).作者使用100 eV的He~+离子入射,测量了不同暴露量的氧、CO、丙烯和氢在Rh(111)表面上的覆盖度.使用前三种气体的实验取得了满意的结果,可以迅速地获得吸附等温线形式的气体暴露量和覆盖度间的关系曲线;氢覆盖度的测量效果不理想,原因在于入射离子对其强溅射作用.文中分析了这一方法的优缺点,并预示了下一步工作的方向,即将此法的应用推广到多晶、薄膜、粉末样品及多组元样品.     

Keggin杂多阴离子电子结构和物化性质与中心原子的 关系

使用密度泛函理论中的离散变分方法(DFT-DVM),以(XMo12O40)^n-(X=B,Al,Si,Ge,P,As,S)为例计算了七个Keggin杂多阴离子的电子结构,讨论了中心原子对Keggin阴离子的电子结构、稳定性、氧化还原性和酸性关系。根据计算结果,给出稳定性、氧化还原性强弱顺序,计算给出结果与实验一致。     

采用AlCl_3-EMIC-MgCl_2室温离子液体电沉积制备铝-镁合金（英文）

采用恒电流和恒电位技术,以及路易斯酸氯化铝(III)-1-乙基-3-甲基咪唑氯化物离子液体中添加氯化镁(II),室温下在铂和铜阴极表面电沉积制备了铝-镁合金.合金层中镁的含量随离子液体中氯化镁浓度和所施加的阴极电流密度的增加而增加.采用X-射线衍射谱(XRD)、扫描电子显微镜(SEM)和能量散射X-射线谱(EDAX)技术,研究了不同电沉积实验条件得到的电沉积层的晶体结构及表面形貌.增加沉积电流密度,可以制备出致密、光亮和结合力良好的电沉积层.铝-镁合金电沉积的阴极电流效率可达99%.应用电化学石英晶体微天平(EQCM)技术研究了电沉积合金的组成.根据重声阻抗分析得到的质量-电荷(m-Q)曲线斜率计算了金属共沉积层的化学成分.     

The role of the auxiliary atomic ion beam in C60(+)-Ar+ co-sputtering

Cluster ion sputtering has been proven to be an effective technique for depth profiling of organic materials. In particular, C(60)(+) ion beams are widely used to profile soft matter. The limitation of carbon deposition associated with C(60)(+) sputtering can be alleviated by concurrently using a low-energy Ar(+) beam. In this work, the role of this auxiliary atomic ion beam was examined by using an apparatus that could analyze the sputtered materials and the remaining target simultaneously using secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectrometry (XPS), respectively. It was found that the auxiliary 0.2 kV Ar(+) stream was capable of slowly removing the carbon deposition and suppresses the carbon from implantation. As a result, a more steady sputtering condition was achieved more quickly with co-sputtering than by using C(60)(+) alone. Additionally, the Ar(+) beam was found to interfere with the C(60)(+) beam and may lower the overall sputtering rate and secondary ion intensity in some cases. Therefore, the current of this auxiliary ion beam needs to be carefully optimized for successful depth profiling.     

A quantitative evaluation of inorganic boundary films formed in engine oils by TOF-SIMS depth profiling with low energy Cs sputtering

Quantitative evaluation of lubrication boundary films was investigated by time-of-flight secondary ion mass spectrometry depth profiling with low energy Cs sputtering. Relative sensitivity correction coefficient (RSC) for calcium phosphate, calcium carbonate, or calcium sulfate was determined by measuring the pellets of the mixture of these compounds. The RSCs for the three calcium salts varied with measurement conditions such as sputter energy and primary ion species. By using the RSC determined in this investigation, the depth profiles of the boundary films formed in real engine oil were corrected to quantitative profiles. The difference of structures between two lubrication boundary films on the different substrate materials formed in the same engine oil was clarified.     

Nanoscale imaging of hydrogen and sodium in alteration layers of corroded glass using ToF-SIMS: Is an auxiliary sputtering ion beam necessary?

The hydrogen (H)/sodium (Na) interface is of great interest in glass corrosion research. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is one of the few techniques that can provide nanoscale H and Na imaging simultaneously. However, the optimized condition for ToF-SIMS imaging of H in glass is still unclear. In H depth profiling using ToF-SIMS, H background control is a key, in which an analysis ion beam and a sputtering ion beam work together in an interlaced mode to minimize it. Therefore, it is of great interest to determine if an auxiliary sputtering ion beam is also necessary to control H background in ToF-SIMS imaging of H. In this study, H imaging with and without auxiliary sputtering beams (Cs⁺, O₂⁺, and Ar_n⁺) was compared on a corroded international simple glass (ISG). It was surprising that the H/Na interface could be directly imaged using positive ion imaging without any auxiliary sputtering ion beam under a vacuum of 2 to 3 × 10⁻⁸ mbar. The H⁺ background was about 5% atomic percent on the pristine ISG glass, which was significantly lower than the H concentration in the alteration layer (~15%). Moreover, positive ion imaging could show distributions of other interesting species simultaneously, providing more comprehensive information of the glass corrosion. If an auxiliary O₂⁺ sputtering ion beam was used, the H⁺ background could be reduced but still higher than that in the depth profiling. Besides, this condition could cause significant loss of signal intensities due to strong surface charging.     

The influence of ion beam sputtering on the composition of the near-surface region of silicon carbide layers

The concentrations and the lattice structure of silicon carbide layers and single crystals are influenced by ion beam sputtering. The influence of ion beam sputtering and primary ion energy on preferential sputtering is investigated by Auger measurements and T-DYN simulations. In dependence on primary ion energy C is enriched. Preferential sputtering increases with decreasing ion energy. Sputtering has a strong influence on the Auger peak shapes of SiC. Except for low ion energy and glancing incidence the peak shapes are independent of the primary ion energy. T-DYN simulations help to explain and understand the near-surface processes during sputtering of SiC. For ion energy dependence of preferential sputtering there is a good agreement of the T-DYN simulation and the Auger measurement. Received: 10 October 1998 / Revised: 26 March 1999 / Accepted: 2 April 1999     

Plasma sputtering of water molecules from the liquid phase by low-energy ions: Molecular dynamics simulation

The ion bombardment-assisted transfer of the components of a solution to the plasma zone in an atmospheric-pressure glow discharge with a liquid cathode plays an important role. The dynamics of the impact of a 50–500 eV ion on the surface of liquid water was studied by molecular dynamics simulation. Data on the amount of water molecules transferred by ion impact to the gas phase are presented. It was shown that the sputtering yield of water can reach 450 molecules per ion at an energy consumption of 0.75 eV for sputtering. Structural changes occurring in the liquid phase under ion bombardment were analyzed on the basis of the dynamics of degradation of hydrogen bonds.     

Sputtering angle effects by Kr mixing in N+ ion beam on the lifetime of nitrided carbon stripper foils

Nitrided carbon stripper (NCS) foils with high nitrogen content were produced by ion beam sputtering of reactive nitrogen gas. Such foils seem to be very useful as strippers in high-intensity heavy ion accelerators. We have conducted comprehensive research, development, and production of such foils with high reproducibility. Krypton, a heavy noble gas, was mixed with the reaction nitrogen gas (IBSRN) in the ion beam sputtering process to produce stripper foils with short sputtering deposition time and long lifetimes in the high intensity ion beam irradiation. With the (N₂ + Kr) mixed gas ions we investigated the influence of different sputtering angles (α) on the lifetime of the NCS-foils in case of poly-graphite material. The lifetime measurement of these foils of 20 ± 5 μg/cm² was performed with a 3.2 MeV Ne⁺ ion beam as usual. The foils made at a sputtering angle of 15° showed a maximum of 11.0 and 7.5  C/cm² average charge density, respectively, which corresponded to about 275 and 187 times the lifetime of the best commercially available foils.     

Removal of Ar+ beam‐induced damaged layers from polyimide surfaces with argon gas cluster ion beams

An Ar Gas Cluster Ion Beam (GCIB) has been shown to remove previous Ar⁺ ion beam‐induced surface damage to a bulk polyimide (PI) film. After removal of the damaged layer with a GCIB sputter source, XPS measurements show minor changes to the carbon, nitrogen and oxygen atomic concentrations relative to the original elemental bulk concentrations. The GCIB sputter depth profiles showed that there is a linear relationship between the Ar⁺ ion beam voltage within the range from 0.5 to 4.0 keV and the dose of argon cluster ions required to remove the damaged layer. The rate of recovery of the original PI atomic composition as a function of GCIB sputtering is similar for carbon, nitrogen and oxygen, indicating that there was no preferential sputtering for these elements. The XPS chemical state analysis of the N 1s spectra after GCIB sputtering revealed a 17% damage ratio of altered nitrogen chemical state species. Further optimization of the GCIB sputtering conditions should lead to lower nitrogen damage ratios with the elemental concentrations closer to those of bulk PI. Copyright © 2010 John Wiley & Sons, Ltd.     

Cluster ion beam profiling of organics by secondary ion mass spectrometry – does sodium affect the molecular ion intensity at interfaces?

The use of cluster ion beam sputtering for depth profiling organic materials is of growing technological importance and is a very active area of research. At the 44th IUVSTA Workshop on “Sputtering and Ion Emission by Cluster Ion Beams”, recent results were presented of a cluster ion beam depth profile of a thin organic molecular layer on a silicon wafer substrate. Those data showed that the intensity of molecular secondary ions is observed to increase at the interface and this was explained in terms of the higher stopping power in the substrate and a consequently higher sputtering yield and even higher secondary ion molecular sputtering yield. An alternative hypothesis was postulated in the workshop discussion which may be paraphrased as: “under primary ion bombardment of an organic layer, mobile ions such as sodium may migrate to the interface with the inorganic substrate and this enhancement of the sodium concentration increases the ionisation probability, so increasing the molecular ion yield observed at the interface”. It is important to understand if measurement artefacts occur at interfaces for quantification as these are of great technological relevance – for example, the concentration of drug in a drug delivery system. Here, we evaluate the above hypothesis using a sample that exhibits regions of high and low sodium concentration at both the organic surface and the interface with the silicon wafer substrate. There is no evidence to support the hypothesis that the probability of molecular secondary ion ionisation is related to the sodium concentration at these levels. © Crown copyright 2008. Reproduced with the permission of Her Majesty's Stationery Office. Published by John Wiley & Sons, Ltd.     

Development of B‐doped Si multiple delta‐layer reference materials for SIMS profiling

B‐doped Si multiple delta‐layers (MDL) were developed as certified reference materials (CRM) for secondary ion mass spectrometry (SIMS) depth profiling analysis. Two CRMs with different delta‐layer spacing were grown by ion beam sputter deposition (IBSD). The nominal spacing of the MDL for shallow junction analysis is 10 nm and that for high energy SIMS is 50 nm. The total thickness of the film was certified by high resolution transmission electron microscopy (HR‐TEM). The B‐doped Si MDLs can be used to evaluate SIMS depth resolution and to calibrate the depth scale. A consistency check of the calibration of stylus profilometers for measurement of sputter depth is another possible application. The crater depths measured by a stylus profilometer showed a good linear relationship with the thickness measured from SIMS profiling using the calibrated film thickness for depth scale calibration. The sputtering rate of the amorphous Si thin film grown by sputter deposition was found to be the same as that of the crystalline Si substrate, which means that the sputtering rate measured with these CRMs can be applied to a real analysis of crystalline Si. Copyright © 2005 John Wiley & Sons, Ltd.     

MgO Erosion Profile in the High Pressure Coplanar Discharge

The sputtering of the MgO protective layer by energetic ions is one of the factors limiting the lifetime of the plasma display panels (PDPs). The sputtering profile of the MgO layer in a coplanar PDP cell has been studied using two-dimensional particle-in-cell Monte-Carlo Collision (PIC–MCC) simulations. The sputtering profile of the MgO layer for various gas conditions is obtained accounting for the energy and angle distributions of different ion species and their respective sputtering yields. Based on the simulation results, the MgO layer is more aggressively sputtered in Ne-based discharges than in He-based discharges. As a result, it is expected that the addition of He to the Ne-Xe mixture in PDPs will reduce the sputtering of the MgO layer and extend the lifetime of the PDP cells.