Mass-spectrometric and optical study of products from laser-ablated PbTe(Ga)

The products of evaporation (p=10^–7 Torr) from the surface of a PbTe(Ga) target ablated by a focused Nd³⁺: YAl-laser (=1.08 m,=15 ns,w=0.47÷4.8 J cm^–2) have been studied using quadrupole mass spectrometry and optical spectrometry. Neutral Pb, Te, Ga, Te₂, and PbTe and singly charged ions of Pb, Te, and Ga were detected by mass spectrometry. The lines of Pb^I, Pb^II, Te^III, and Ga^I were observed in the 340÷760 nm region in the emission spectra; the lines of Pb^III and Te^III were absent. The time-current dependences of ions passed through a mass-filter for each vapor component at differentw and for the generation of the crater on the target surface were studied. The kinetic energy of the ions was estimated using an ion-optical decelerating lens. The temperature of the laser plasma was estimated from the intensities of the Pb^I lines.Submitted as a report at the VI All-Russian Conference on Laser Chemistry, Tuapse, September 18–23, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 223–226, February, 1994.     

Basic investigations for laser microanalysis: III. Application of different buffer gases for laser-produced sample plumes

We have measured the diameters and depths of craters in a copper sample and the amount of material ablated by the 1.06-m radiation of a pulsed Nd: YAG laser in the buffer gases argon, neon, helium, air and nitrogen as well as the emission intensities of analyte atoms in dependence on laser power and buffer gas pressure. The results are correlated with corresponding data of the plasma temperatures and the relative electron densities in the plasma. Criteria for the choice of the buffer gas, the buffer gas pressure and the laser power for optical emission spectrometry of microplasmas are given.     

Basic investigations for laser microanalysis: I. Optical emission spectrometry of laser-produced sample plumes

In order to find optimum conditions for laser ablation and atomization for analytical purposes, time resolved emission spectra of Nd:YAG laser-produced plasma plumes propagating into noble gas atmospheres of different pressures were measured with an optical multichannel analyzer. The time evolution of the plasma temperature was determined. Strong temperature changes were observed depending on the matrix composition. The analytical figures of merit of optical emission spectrometry (OES) of laser-produced sample plasmas were determined using, as examples, measurements of two analytes (silicon and chromium) in homogeneous and low-alloyed standard steel samples.     

Characterization of a laser‐nitrided titanium alloy by electron backscattered diffraction and electron probe microanalysis

After a laser gas nitriding treatment of the Ti‐7.5Al (atom %) titanium‐based alloy, we used a combination of electron backscattered diffraction (EBSD) in scanning electron microscope and electron probe microanalysis (EPMA) techniques in order to efficiently characterize the different phases in the resolidified layer. Representative measurements of chemical composition and reliable determination of crystal structure were possible for each phase of the complex microstructure. The reaction zone is formed by a mixture of isostructural TiN phases with dendritic and/or ‘coarse’ needles morphology, fixed into a α′‐Ti matrix (martensite) with a thin needle aspect. The nitrogen solubility was found to remain very low in the α′‐Ti matrix (up to 2–3 atom %), while in the TiN phase, an aluminum solubility as high as 4 atom % was measured, reducing drastically the nitrogen content into a Ti₇₉N₁₇Al₄ chemical composition. Copyright © 2005 John Wiley & Sons, Ltd.     

光电发射光谱法分析钛合金中的主要合金元素

依据光电发射光谱仪光源激发机理,结合钛合金的材料性能,选用火花放电激励光源和时间分解脉冲分布测光法,绘制钛合金中主要合金元素的工作曲线,对A l、V、Fe、S i、C、Mn、Cu、Mo、Sn、Zr、N i、Cr等元素进行光谱直接测定。测定结果与化学法测定结果基本一致,测定结果的相对标准偏差为0.72%~4.27%(n=11)。     

Chemical Bond Effects on Line Intensities in Arsenic X-Ray Emission Spectrum

This paper offers a critical analysis of chemical bond effects using X-ray fluorescent spectroscopy based on currently available equipment. Most chemical bond effects cannot be investigated with standard X-ray fluorescent spectrometers, primarily because of low spectral resolution. Therefore, we suggest an approach based on recording the intensity ratio of the last emission line (IR LEL) of the given X-ray series to the line of an electron transition between the core levels of the same atom. Using various chemical compounds of arsenic as an example, we investigated the dependence of the intensity ratio of the As K ₂ and As K ₁ lines (IR LEL of the arsenic K-series) on various structural parameters. An experimental study points to the existence of linear dependences of IR LEL on the radius of the first coordination sphere, the covalent radius of the nearest atom, and the concentration ratio between the elements of the corresponding phase, defining the deviation from stoichiometry. Using such dependences, one can determine, using X-ray data, the bond length of arsenic in various compounds on a low-resolution spectrometer.     

Matrix effects in the analysis of biological matrices by axial view inductively coupled plasma optical emission spectrometry

We are reporting observations of positive and negative variations of emission line intensities during the determination of boron and titanium in biological matrices by axial view inductively coupled plasma optical emission spectrometry with segmented charge-coupled device detection. The study included the testing of several elements (yttrium, palladium and platinum) and analytical wavelengths for internal standardization, aiming to compensate for variations in signal recovery due to matrix interferences. Human albumin was chosen as principal matrix component to assess the effect of variable chemical and instrumental operating conditions on boron response. A parametric study was performed by considering the application of two different nebulizer–aerosol chamber systems, the effect of plasma operating conditions on analyte and internal standard signals and the influence of common blood plasma electrolytes, added as salts of alkaline or alkaline earth elements. The pneumatic injection systems tested were a standard cross-flow nebulizer with a Scott type spray chamber and a concentric Meinhard type device coupled to a glass cyclonic spray chamber. The change from standard (i.e. medium RF power and relatively high aerosol carrier gas flow rate) to robust (i.e. higher RF power and lower carrier gas flow rate) conditions contributed to large, non-correlated variations in boron intensities and in some of the analyte/internal standard ratios. Significant memory effects were observed for injection of boron solutions prepared with boric acid and containing small amounts of acid, but those effects were negligible when the boron carrier compound was boronophenylalanyne. The injection of titanium solutions did not produce analyte carry-over effects. When internal standards were employed, a less effective signal compensation was consistently observed for boron at higher albumin concentrations when the difference in energies of the lines was between 4.5 and 6 eV. This effect was enhanced for some line pairs when robust conditions are employed. Differences in the response between nebulizers were minor, with a slight advantage in sensitivity for the cross-flow/Scott system. Yttrium was found to be useful for signal compensation in the determination of boron and titanium in blood and human plasma provided that the equivalent concentration of albumin in the nebulized sample dilutions was kept below 0.2% w/v. Simultaneous measurement of a reference strontium line was found to be useful as an additional verification of the response of yttrium as internal standard.     

Structural research on non transition metal double nitrites: Crystal structure, optical absorption and emission of TlBa2(NO2)5

The thallium-barium double nitrite, TlBa₂(NO₂)5, is pyroelectric in the 77-600 K range and crystallizes in thePca2 ₁ space group. The lattice constants at 293 K are: a = 17.868(12),b = 4.934(3),c = 13-426(11) A (MoKa, λ = 0.71069 A). There are four stoichiometric units in the unit cell of volume V= 1184(1) A³ (D _o = 3.98,D _x = 3.979 Mgm⁻³),F (000) = 1232, μ = 20.36mm⁻¹. The crystal structure was solved by Patterson and Fourier methods and refined by least-squares to a final conventional agreement indexR = 0.053 for 1371 independent reflections collected in a θ range of 3–30°, using MoKα radiation. There are two independent barium atoms surrounded by NO ₂ ⁻ groups, both with coordination number 10 and distances in the ranges Ba-O = 2.69(4)-3.18(4) A and Ba-N = 3.01(4)-3.18(4) A. The environment of thallium is clearly affected by the lone-pair stereoactivity and involves 12 Tl-O and Tl-N contacts less than 3.5A, but only four Tl-O distances are shorter than 3 A (min. 2.76(2), max. 2.85(3) A), with a pyramidal coordination and thallium at the apex of the pyramid. All these coordination polyhedra are joined in chains running along the shortest lattice vector [010]. The single crystal electronic spectra, studied in absorption with polarized light and in photostimulated emission, are interpreted as due to transitions involving NO ₂ ⁻ electronic levels perturbed by Tl⁺, whose spin-orbit interaction makes probable also the forbidden singlet-triplet transitions, in agreement with the interpretative picture given for post-transition metal nitrites.     

Deposition behavior in a low‐temperature cascade arc torch (CAT) polymerization process

Two kinds of hydrocarbon type monomers and three kinds of organosilicons were polymerized by a low‐temperature cascade arc argon plasma torch. Their deposition behaviors were studied as a function of experimental parameters and monomer elemental compositions. It was found that the normalized deposition rate (DR), expressed as deposition yield of DR/(FM)_m, was determined by a composite operational parameter, W*(FM)_c/(FM)_m, where W is the power input, and (FM)_c and (FM)_m are the mass flow rates of carrier gases and monomers, respectively. Experimental results indicated that the deposition yield is highly dependent on the elementary compositions of monomers. Optical emission spectroscopy study on the argon plasma torch showed that the emission intensity of excited argon neutrals was proportional to the value of the parameter W*(FM)_c. These results further certified that excited argon neutrals are the main energy carriers from the cascade arc column to activate monomers in the argon plasma torch. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 967–982, 1999     

Interpretation of soft X-ray emission spectra in terms of relativistic electric dipole transition probabilities

The emission process for eigenstates of a model Dirac Hamiltonian of “muffintin” type is described in terms of relativistic electric dipole (E1) transitions with the assumption that the final state is a localized core eigenstate of the system. The proposed method is applied to theL-emission spectrum of V in VC and to theL- andM-emission spectrum of Nb in NbC. Resulting theoretical spectra are compared with experimental data.     

Mechanism of silicon film deposition in the RF plasma reduction of silicon tetrachloride

Plasma-chemical reduction of SiCl₄ in mixtures with H₂ and Ar has been studied by optical emission spectroscopy (OES) and laser interferometry techniques. It has been found that the Ar:H₂ ratio strongly affects the plasma composition as well as the deposition (r _D) and etch (r _E) rates of Si: H, Cl films and that the electron impact dissociation is the most important channel for the production of SiCl_x species, which are the precursors of the film growth. Chemisorption of SiCl_x and the reactive surface reaction SiCl_x+H–SiCl_(x–1)0+HCl are important steps in the deposition process. The suggested deposition model givesr _D [SiCl_x][H], in agreement with the experimental data. Etching of Si: H, Cl films occurs at high Ar: H₂ ratio when Cl atoms in the gas phase become appreciable and increases with increasing Cl concentration. The etch rate is controlled by the Cl atom chemisorption step.     

ADP晶体晶格振动模式的拉曼光谱分析

在100~4 000 cm-1波数范围内,发现了由LabRAM HR800和Renishaw 2000 micro-Raman spectroscopy两种仪器获得的磷酸二氢铵(ADP)晶体拉曼峰不同。为探究其原因,对ADP晶体进行了空间群分析和晶格振动模式指认。分析结果表明,其原因在于非线性光学晶体中PO4、OH、P-OH和NH4基团的极化变形。     

PECVD of amorphous hydrogenated oxygenated nitrogenated carbon films

An actinometric optical emission spectroscopy (AOES) study of the trends in the concentrations of the plasma species H, CH, CO, OH, and CN in film-producing glow discharges of mixtures of isopropanol and nitrogen was undertaken. Conventional AOES was used to obtain the trends in the plasma concentrations of these species as a function of the proportion of nitrogen in the feed, R_n. A dynamic variant of actinometry in which trends in the concentrations of plasma species are measured as a function of time following the cutting of one of the principal gas flows was also employed to investigate the relative importance of gas phase and plasma/polymer–surface interactions in the production of the species of interest. Each of the above-mentioned species is produced, to some degree, by plasma/polymer–surface reactions. As revealed by transmission infrared spectroscopy, the films deposited contain C H, CO, and O H groups. For R_n > 0, the films become nitrogenated, with both N H and CN groups being present. As revealed by transmission ultraviolet-visible spectroscopy, both the optical gap and the refractive index of the deposited films decrease as R_n is increased. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1881–1888, 1998     

Ein- und zweikernige MoII-Phthalocyaninate(2–): Darstellung und Eigenschaften von Bis(cyano)phthalocyaninato(2–)molybdat(II) und Bis(phthalocyaninato(2–)molybdän(II))

Mono- and Dinuclear Mo^II Phthalocyaninates(2–): Syntheses and Properties of Bis(cyano)phthalocyaninato(2–)molybdate(II) and Bis(phthalocyaninato(2–)molybdenum(II)) Blue diamagnetic bis(phthalocyaninato(2–)molybdenum(II)) is synthezied by reduction of oxophthalocyaninato(2–)molybdenum(IV) with boiling triphenylphosphine. The Mo–Mo stretching vibration ist observed in the resonance Raman spectrum at 374 cm^–1. It is chemically inert and dissolves in conc. sulfuric acid without decomposition. It reacts with molten tetra(n-butyl)ammonium cyanide to yield redbrown paramagnetic bis[tetra(n-butyl)ammonium] biscyanophthalocyaninato(2–)molybdate(II) (μ_eff = 3.15 μ_B; S = 1). The complex salt is very instable and demetallizes in solution. In the extraordinary UV-VIS-NIR spectrum an intense trip-triplet transition at 7780 cm^–1 together with a very structured B region between 14000 and 21000 cm^–1 of comparable absorbance is observed.     

Defining and measuring optical frequencies: the optical clock opportunity--and more (Nobel lecture).

Four long-running currents in laser technology met and merged in 1999-2000. Two of these were the quest toward a stable repetitive sequence of ever-shorter optical pulses and, on the other hand, the quest for the most time-stable, unvarying optical frequency possible. The marriage of ultrafast- and ultrastable lasers was brokered mainly by two international teams and became exciting when a special "designer" microstructure optical fiber was shown to be nonlinear enough to produce "white light" from the femtosecond laser pulses, such that the output spectrum embraced a full optical octave. Then, for the first time, one could realize an optical frequency interval equal to the comb's lowest frequency, and count out this interval as a multiple of the repetition rate of the femtosecond pulse laser. This "gear-box" connection between the radiofrequency standard and any/all optical frequency standards came just as sensitivity-enhancing ideas were maturing. The four-way union empowered an explosion of accurate frequency measurement results in the standards field and prepared the way for refined tests of some of our cherished physical principles, such as the time-stability of some of the basic numbers in physics (e.g. the "fine-structure" constant, the speed of light, certain atomic mass ratios), and the equivalence of time-keeping by clocks based on different physics. The stable laser technology also allows time-synchronization between two independent femtosecond lasers so exact they can be made to appear as if the source were a single laser. By improving pump-probe experiments, one important application will be in bond-specific spatial scanning of biological samples. This next decade in optical physics should be a blast!     

Passion for precision.

Optical frequency combs from mode-locked femtosecond lasers have revolutionized the art of counting the frequency of light. They can link optical and microwave frequencies in a single step, and they provide the long missing clockwork for optical atomic clocks. By extending the limits of time and frequency metrology, they enable new tests of fundamental physics laws. Precise comparisons of optical resonance frequencies of atomic hydrogen and other atoms with the microwave frequency of a cesium atomic clock are establishing sensitive limits for possible slow variations of fundamental constants. Optical high harmonic generation is extending frequency comb techniques into the extreme ultraviolet, opening a new spectral territory to precision laser spectroscopy. Frequency comb techniques are also providing a key to attosecond science by offering control of the electric field of ultrafast laser pulses. In our laboratories at Stanford and Garching, the development of new instruments and techniques for precision laser spectroscopy has long been motivated by the goal of ever higher resolution and measurement accuracy in optical spectroscopy of the simple hydrogen atom which permits unique confrontations between experiment and fundamental theory. This lecture recounts these adventures and the evolution of laser frequency comb techniques from my personal perspective.     

等离子体基低能离子注入的光谱诊断

采用发射光谱（ＯＥＳ）技术系统地研究了电子回旋共振（ＥＣＲ）微波等离子体基低能离子注入的等离子体特性。结果表明：纯氮气形成的等离子体中的活性粒子主要是Ｎ２和Ｎ＋２，等离子体中电子与气体分子碰撞使Ｎ２产生激发和电离，而使Ｎ２离解的作用很小；氮氩混合气形成的等离子体中，随着氩气分压的增加，Ｎ２和Ｎ＋２的浓度降低，同时氩气对氮分子离解的贡献很小；直接施加于试样的脉冲负偏压对等离子体特性没有明显影响，但存在着一定的溅射作用。