磁压缩系统中热脱附杂质粒子研究

磁压缩系统为俄罗斯实验物理研究院提出的核聚变方案。磁压缩系统腔室中杂质粒子可能来源于热脱附、等离子体刮削器壁等途径。利用ANSYS工具模拟5 MA脉冲电流流过腔室,并给出电极温度的二维分布图,结合研究小尺寸铜样品上杂质的解吸附来分析磁压缩系统腔室中热脱附过程产生的杂质粒子。通过测量3 keV的Ar+离子入射到Cu(110),Cu(111)样品表面的飞行时间谱,分析样品表面吸附的杂质种类,以及样品表面杂质含量随温度的变化关系。研究表明杂质粒子含量跟电极温度有关联性,且跟电极材料表面结构相关。     

Molecular view of copper deposition chemistry: (Hexafluoroacetylacetonate)Cu(vinyltrimethylsilane) on a Si(1 0 0)-2 × 1 surface

The chemistry of a common copper deposition precursor, (hexafluoroacetylacetonate)Cu(vinyltrimethylsilane), (hfac)Cu(VTMS), on a single crystal Si(1 0 0)-2 × 1 surface is described at the molecular level using a combination of experimental surface analytical techniques under ultra-high vacuum conditions with computational analysis. At a cryogenic temperature of 100 K, (hfac)Cu(VTMS) adsorbs on this surface molecularly, without noticeable decomposition. Upon surface annealing, VTMS is easily released into the gas phase below the room temperature, while the hfac ligand is bound to the surface through the copper atom. When (hfac)Cu(VTMS) is adsorbed at room temperature, VTMS is released into the gas phase immediately, leaving surface adsorbate analogous in structure to the one formed by adsorption at cryogenic temperature and a brief annealing to room temperature. Upon surface annealing, the hfac ligand decomposes and constitutes the main source of impurities in copper deposition process.     

Molecular engineered silica surfaces with an assembled anthracene monolayer as a fluorescent sensor for organic copper(II) salts

A novel fluorescence film has been fabricated by covalently coupling anthracene on a glass plate surface via a long flexible “Y” type spacer. Fluorescence measurement demonstrated that the emission of the film is dominated by anthracene monomer emission, and the emission can be selectively quenched by organic copper(II) salts including copper acetate, copper citrate, copper tartrate, etc. Addition of inorganic copper(II) salts like Cu(NO₃)₂, CuSO₄, CuCl₂, etc., however, has little effect upon the emission of the film. This observation was explained by considering the screening effect of the spacer layer, or spacer clusters, or even spacers adopting compact coiled conformation. Different from the reported fluorescence films with similar structures, immobilization of anthracene via a “Y” type spacer on a glass plate surface makes the fluorophore moieties exist in two different states, that is some of them were embedded within the spacer structures, and some of them might stay out of the structures. This hypothesis has been confirmed by model system, solvent effect and quenching mechanism studies. The emission of the film is sensitive to the presence of organic copper(II) salts like copper acetate. The response of the film to copper acetate is fully reversible. Presence of other inorganic salts, including Pb(Ac)₂, Cd(Ac)₂, Zn(Ac)₂, and inorganic copper(II) salts has little effect upon the sensing performance of the film to copper acetate.     

Influence of glyphosate on the copper dissolution in phosphate buffer

The electrochemical behavior of copper microelectrode in phosphate buffer in the presence of glyphosate was investigated by electrochemical techniques. It was observed that the additions of glyphosate in the phosphate buffer increased the anodic current of copper microelectrode and the electrochemical dissolution was observed. This phenomenon could be associated with the Cu(II) complexation by glyphosate forming a soluble complex. Physical characterization of the surface showed that, in absence of glyphosate, an insoluble layer covered the copper surface; on the other hand, in presence of glyphosate, it was observed a corroded copper surface with the formation of glyphosate complex in solution.     

Electrolytic metal deposition onto chemically modified electrodes

Some general features concerning electrochemical metal deposition onto electrodes modified with self-assembled monolayers (SAMs) of alkanethiols are discussed. Although thiols of various chain length are briefly addressed, special emphasis is placed on copper deposition onto an ethanethiol (C2)-modified Au(111) surface. The short alkanethiol blocks the surface to a great extent but does not completely suppress charge transfer. We have used in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) to characterize the structure and the electrochemical behavior of the C2 monolayer in sulfuric acid electrolyte before and after introducing copper ions to the system. The C2 adlayer consists of domains of two different ordered structures. It is shown that the adlayer undergoes a reversible order–disorder transition at potentials slightly negative of 0 V vs. SCE, which testifies to a surprisingly high mobility of the C2 molecules within the SAM. Copper deposition on C2-modified gold electrodes shows significant differences from the same process on the bare electrode. A sharp cathodic peak at -0.18 V vs. SCE is ascribed to the insertion of a Cu monolayer between Au and the organic adlayer. At low overpotentials the Cu deposit exhibits a ramified monatomic high morphology, if the ethanethiol adlayer is dense. Three-dimensional growth starts at large substrate defects. Received: 2 May 1999 / Accepted: 17 August 1999 / Published online: 6 October 1999     

Surface morphology and reaction at Cu/Si interface—Effect of native silicon suboxide

Copper thin films are deposited by thermal evaporation on unetched and etched monocrystalline silicon. The study by alpha particles backscattering (RBS) raises a strong diffusion of copper in silicon substrates with and without native suboxide layer. On the other hand, the X-rays diffraction shows the formation and the growth of Cu₃Si and Cu₄Si silicides. Whereas the scanning microscopy underlines large crystallites growth surrounded by black zones of silicon coming from the uncovered substrate, independently to the surface state of the substrate, after annealing at high temperature. The presence of native silicon suboxide at Cu/Si interface, influences in a drastic way the minimal temperature to which the interfacial reaction occurs. The oxygen impurities detected by microanalysis, after heat treatment under vacuum, are closely related to the growth of silicides crystallites.     

Photoluminescence of gold, copper and niobium as a function of temperature

A specially constructed instrument for measuring the low intensity photoluminescence emission spectra of metals is described. It uses low luminescence optical components and dedicated sample mounting techniques. Room temperature measurements agree closely with literature spectra for high-purity gold and are found to be sensitive to 100 ppm impurities. Detailed spectra are presented, which are weakly temperature dependent, for gold, copper and unpolished niobium between room temperature and 100 K. We conclude that this work provides accurate luminescence data for Au from 300 K down to 100 K. Although the (variable temperature) luminescence data for Cu are consistent both with the room temperature experimental data in the literature and theory, we conclude the role of surface adsorbates and/or oxides cannot be ruled out. Theory suggests that Nb has a factor ∼50 lower luminescence intensity than Au and Cu because the real part of the refractive index is a factor ∼5 higher and the density of states ∼2 eV below the Fermi energy is a factor of ∼4 lower than Au and Cu. Measurements are presented for unpolished Nb, but given the lack of signal detection for polished Nb and that theory predicts very weak signals, we conclude that the luminescence signals from pure Nb still remain below the sensitivity of our instrument.     

XPS studies of short pulse laser interaction with copper

The effect of laser ablation on copper foil irradiated by a short 30 ns laser pulse was investigated by X-ray photoelectron spectroscopy. The laser fluence was varied from 8 to 16.5 J/cm² and the velocity of the laser beam from 10 to 100 mm/s. This range of laser fluence is characterized by a different intensity of laser ablation. The experiments were done in two kinds of ambient atmosphere: air and argon jet gas.The chemical state and composition of the irradiated copper surface were determined using the modified Auger parameter (α′) and O/Cu intensity ratio. The ablation atmosphere was found to influence the size and chemical state of the copper particles deposited from the vapor plume. During irradiation in air atmosphere the copper nanoparticles react with oxygen and water vapor from the air and are deposited in the form of a CuO and Cu(OH)₂ thin film. In argon atmosphere the processed copper surface is oxidized after exposure to air.     

Improvement of Field Emission Characteristics of Copper Nitride Films with Increasing Copper Content

A copper nitride （Cu3N） thin film is deposited on a Si substrate by the reactive magnetron sputtering method. The XPS measurements of the composite film indicate that the Cu content in the film is increased to 80.82 at. % and the value of the Cu/N ratio to 4.2：1 by introducing 4% 112 into the reactive gas. X-ray diffraction measurements show that the film is composed of Cu3N crystallites with an anti-ReO3 structure. The effects of the increase of copper content on the field emission characteristics of the Cu3N thin film are investigated. Significant improvement in emission current density and emission repeatability could be attributed to the geometric field enhancement, caused by numerous surface nanotips, and the decrease of resistivity of the film.     

Phosphorous doped Ru film for advanced Cu diffusion barriers

Copper diffusion barrier properties of phosphorous doped Ru film are studied. Phosphorous out-diffusion to Ru from underneath phosphosilicate glass (PSG) layer results in P doped Ru film. The doped Ru film improves copper barrier properties and has excellent thermal stability. XRD graph indicates that there is no copper silicide and ruthenium silicide formations after annealing at 550 °C for 30 min in vacuum. This result is consistant with AES depth profiles which show no Cu, Ru, O and Si inter-diffusion. The phosphorous doped Ru barrier also blocks oxygen's diffusion to copper from the PSG layer. The phosphorous doped Ru film could be an alternative Cu diffusion barrier for advanced Cu interconnects.     

低能CU6团簇在CU(001)表面和AU(001)表面沉积的分子动力学模拟研究

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Adsorption of L-Alanine on Cu（111） Studied by Scanning Tunnelling Microscopy

The adsorption of L-alanine on Cu（111） surface is studied by means of scanning tunnelling microscopy under ultra-high vacuum conditions. The results show that the adsorbates are chemisorbed on the surface, and can form a two-dimensional gas phase, chain phase and solid phase, depending on deposition rate and amount. The adsorbed molecules can be imaged as individual protrusions and parallel chains in gas and chain phases respectively. It is also found that alanine can form （2 × 2） superstructure on Cu（111） and copper step facet to （110） directions in solid phase. On the basis of our scanning tunnelling microscopic images, a model is proposed for the Cu（111）（2 ×2）-alanine superstructure. In the model, we point out the close link between （110）-direction hydrogen bond chains with the same direction copper step faceting.     

Mechanism of Cu transport along clean Si surfaces

Cu diffusion along clean Si(111), (110) and (100) surfaces are investigated by Auger electron spectroscopy and low energy electron diffraction. The effective diffusion coefficients of copper are measured in the temperature range from 500 to 650°C. It is shown that the Cu transport along silicon surface occurs by the diffusion of Cu atoms through Si bulk and the segregation of Cu atoms to the surface during the diffusion process. It is found that the segregation coefficients of Cu to silicon surface during the diffusion process depend on surface orientation.     

Influence of copper crystal surface on the CVD growth of large area monolayer graphene

We study the influence of the surface structure of copper single crystals on the growth of large area monolayer graphene by chemical vapor deposition (CVD) in ultra-high vacuum (UHV). Using atomic-resolution scanning tunneling microscopy (STM), we find that graphene grows primarily in registry with the underlying copper lattice for both Cu(111) and Cu(100). The graphene has a hexagonal superstructure on Cu(111) with a significant electronic component,whereas it has a linear superstructure on Cu(100). Graphene on Cu(111) forms a microscopically uniform sheet, the quality of which is determined by the presence of grain boundaries where graphene grains with different orientations meet. Graphene grown on Cu(100) under similar conditions does not form a uniform sheet and instead displays exposed nanoscale edges. Our results indicate the importance of the copper crystal structure on the microstructure of graphene films produced by CVD.     

Scanning tunneling microscopy investigation of leucine and asparagine adsorbed on Cu(1 1 1)

Adsorption of leucine and asparagine on Cu(1 1 1) surface has been studied by means of scanning tunneling microscopy (STM) in ultra-high vacuum (UHV) conditions. It has been found that leucine can form (3 × 2) superstructure on Cu(1 1 1) and copper steps facet to 〈1 1 0〉 directions. On the basis of our STM images, model has been proposed for the Cu(1 1 1)(3 × 2)-leucine superstructure. The model explains quite naturally the motivation behind the step faceting process. On the other hand, asparagine cannot form any ordered superstructure on Cu(1 1 1) and no copper step faceting can be observed either. The role of amino group in the side chain played in asparagine adsorption geometry is discussed in this paper.     

Enhancement in hydrophobicity of silica films using metal acetylacetonate and heat treatment

Water is one of the most affecting chemicals that can cause damage to the solid surface. To protect the surface due to the action of water, the surface should be made hydrophobic. In the present study, the improvement in hydrophobicity of silica films using metal acetylacetonate (M-acac) by employing heat treatment to methyltrimethoxy silane (MTMS) based silica coatings is reported as a novel attempt. Instead of following the established trends of the surface derivatization or co-precursor method, iron acetylacetonate Fe(acac)₃, copper acetylacetonate Cu(acac)₂ and heat treatment were used to incorporate hydrophobicity with silica coatings. As M-acac is readily soluble in organic solvents, Fe(acac)₃ and Cu(acac)₂ were dissolved in methanol (MeOH) and their concentration was varied from 0 to 0.025 M. The coating solution was prepared by optimizing molar ratio of MTMS:MeOH:basic H₂O to 1:7.15:6.34, respectively. Gelation time (t_g) for Cu(acac)₂ containing silica sol and that containing Fe(acac)₃ were noted to be 30 and 55 min, respectively. The substrates were taken out after gelation and heat treated at 150 °C for 2 h. The heat treated films showed a dramatic increase in the static water contact angle from 82° to as high as 142°.     

Sub-target effect in film analysis using TEA CO2 laser-induced plasma

A TEA CO₂ laser beam (500 mJ, 200 ns) was focused on film samples, under low pressure surrounding gas at around 1 Torr. It has been found that to generate the laser plasma for the sample of oil or powder, the sample should be attached in the form of thin film on the surface of a metal, such as copper plate, which acts as a sub-target. The plasma has favorable characteristics for spectrochemical analysis due to its low background and sharp line spectrum, and hence an optical multichannel analyzer (OMA) without gated function can be used for spectrum acquisition. Using the sub-target effect we have performed for analyses on water molecular layer and water impurities, where the water was condensed by heating process or electrolysis process on the sub-target so that impurities in the water were attached to the metal surface. It should be emphasized that in this case the sub-target itself has never been ablated and no any damaged on its surface. Another application of the sub-target effect is used for the analysis of oil contamination in soils. We have succeeded to detect clearly the emission line of C I 247.9 nm from the carbon as a major constituent of the oil. To derive the carbon emission intensity coming only from oil, compensation was made to cancel the contribution from other organic species using the emission of Ca, which inherently contains in other organic species in soil. As result, a good linear relationship between carbon emission intensity and oil concentration was obtained.     

Si cleaning method without surface morphology change by cyanide solutions

Hydrogen cyanide (HCN) aqueous solutions can remove copper contaminants from Si surfaces more effectively than hydrochloric acid/hydrogen peroxide mixture (HPM) and sulfuric acid/hydrogen peroxide mixture (SPM). When pH of the HCN solutions is adjusted at 9, Si surface morphology is not changed, while when pH exceeds 10, the Si surfaces are considerably roughed. AFM measurements show that Cu contaminants are present in the form of particles on the bare Si surfaces. XPS measurements show that the particles consist of metallic Cu. The Cu particle height decreases almost linearly with the cleaning time, and the Cu surface concentration decreases exponentially with it. It is concluded that Cu particles gradually dissolve into the HCN aqueous solutions by the direct reaction with cyanide ions at the surface of the Cu particles.     

Growth, EPR and optical absorption spectra of l-threonine single crystals doped with Cu ions

We investigated the crystal growth, electron paramagnetic resonance (EPR) and optical absorption spectra of l-threonine doped with Cu²⁺. The quality, size and habit of the single crystals grown from aqueous solution by the slow solvent evaporation and by the cooling methods vary when the impurities are introduced during the growth process. The variations with the magnetic field orientation of the EPR spectra of single-crystal samples at room temperature and 9.77 GHz in three crystal planes (ab, bc and ac) show the presence of copper impurities in four symmetry-related sites of the unit cell. These spectra display well resolved hyperfine couplings of the of Cu²⁺ with the I_Cu= of the copper nuclei. Additional hyperfine splittings, well-resolved only for specific orientations of the magnetic field, indicate that the copper impurity ions in the interstitial sites have two N ligands with similar hyperfine couplings. The principal values of the g and A_Cu tensors calculated from the EPR data are g₁=2.051(1), g₂=2.062(2), g₃=2.260(2), A_Cu,1=16.9(5)×10⁻⁴ cm⁻¹, A_Cu,2=21.8(6)×10⁻⁴ cm⁻¹, A_Cu,3=180.0(5)×10⁻⁴ cm⁻¹. The principal directions corresponding to g₃ and to A_Cu,3 are coincident within the experimental errors, reflecting the orientation of the bonding planes of the copper ions in the crystal. The values of the crystal field energies are evaluated from the optical absorption spectrum, and the crystal field and bonding parameters of the Cu impurities in the crystal are calculated and analyzed. The EPR and optical absorption results are discussed in terms of the crystal structure of l-threonine and the electronic structure of the Cu²⁺ ions, and compared with data reported for other systems. The effects of the impurities in the growth and habit of the crystals are also discussed.     

热镀铜层冷凝过程的分子动力学模拟

采用常温、常压分子动力学模拟方法和FS(Finnis Sinclair)势 ,研究了在周期性边界条件下由 5 0 0个原子构成的液态Cu模型系统的凝固过程 ,考察了不同降温速率下Cu的凝固行为 ,得到了不同温度、不同冷却速率下Cu的双体分布函数 ;采用HA键型指数法统计了各种小原子团在不同温度下所占比例 ,采用键取向序分析了体系降温全过程的局域取向对称性 ,得到原子体系微观结构组态变化的重要信息 ;最后 ,利用能量分析的方法对体系微观结构的变化进行了说明 ,给出了液态Cu冷凝过程中微观结构转变的重要信息 .