Emission characteristics of mixed gas plasmas in low-pressure glow discharges

Glow discharge optical emission spectrometry (GD-OES) with mixed plasma gases is reviewed. The major topic is the effect of type and content of gases added to an argon plasma on the emission characteristics as well as the excitation processes. Emphasis is placed on argon–helium, argon–oxygen, and argon–nitrogen mixed gas plasmas. Results for non-argon-matrix plasmas, such as neon–helium and nitrogen–helium mixtures, are also presented. Apart from the GD-OES, glow discharge mass spectrometry and furnace atomization plasma emission spectrometry with mixed plasma gases are also discussed.     

A study of the density of sputtered atoms in the plasma of the modified Grimm-type glow discharge source

The sputtering of atoms from the cathode of a modified Grimm-type glow discharge source was studied using hollow cathode lamps as primary sources. Absorption of copper atoms at a distance of 1.5 mm from the cathode was measured, using different discharge conditions, with helium, neon, argon, krypton and nitrogen as carrier gases. For conditions with voltages at and above 800 V, the greatest absorption (copper atom concentration) was obtained using argon as carrier gas. Absorption by copper and chromium, measured at varying distances from the cathode and at different discharge conditions, shows a maximum between 1 and 2 mm from the cathode. This phenomenon can only be explained by cluster sputtering or cluster formation in the plasma. By using the Doppler temperatures of the emission and absorption sources to calculate line profile halfwidths, measured absorbances can be converted to atom number densities.A diffusion model has been formulated to describe the diffusion of sputtered atoms through the plasma which is in a steady state. From the agreement obtained with experimental results, it is concluded that in principle this diffusion model can be used to predict the spatial distribution of sputtered atoms in the plasma.     

Design and construction of glow discharge-ion trap mass spectrometer (GD-ITMS) and its application for the analysis of volatile organic samples

In this study, we present a newly designed see-through type hollow cathode glow discharge (St-HCGD) cell developed for the analysis of volatile organic materials in an ion trap mass spectrometer. The cell was interfaced with a homemade ion trap mass spectrometer by adopting skimmer and sampler in an optimized dimensions based on the computer simulation done by SIMION software. The St-HCGD cell has a relatively small size (4×4×7 cm) with the diameter of the inner tube of 0.25′′. The anode and cathode were made of stainless steel-304 and helium was used as a buffer gas for discharge to enhance the Penning ionization process rather than sputtering process. Mass spectra of volatile organic samples such as benzene, toluene, cyclohexane were obtained by using the St-HCGD-ITMS.     

Laser optogalvanic spectroscopy of N2 from the AΣu metastable state in a corona excited supersonic expansion

A hollow cathode combined with a corona excited supersonic expansion has proven to be an efficient method of producing a stable discharge in a N₂/Ar gas mixture. A high-resolution and rotationally cold absorption spectrum of the well-known (2,0) and (8,7) bands of the B³Π_g ← A³Σ_u⁺ first positive system of N₂ was recorded. It illustrates the sensitivity of the laser optogalvanic detection technique coupled to such an apparatus. A significant reduction of the linewidth and an enhancement of the signal-to-noise ratio were obtained. A high variational excitation process has been observed and is discussed.     

The hollow cathode plume: A plasma emission source for solids

A hollow cathode discharge serves to form an energetic plasma plume which exhibits intense emission characteristics. The sample cathode is sputtered in the discharge to produce an atomic population which then flows into the plume through an exit orifice for subsequent excitation. Atomic absorption and emission profiles in the plume are shown. Emission spectra of major and minor elements show strong atomic and ionic lines of sputtered species, particularly from the inner core of the plume. A sample in the form of a small disc can serve as the base of the hollow cathode for more convenient sample preparation. The source is believed to have potential also in elemental analysis by mass spectrometry.     

气相色谱-单光子电离飞行时间质谱的联用及在柴油组分表征中的应用

建立了一种气相色谱(GC)与单光子电离-飞行时间质谱(SPI-TOF MS)联用(GC/SPI-TOF MS)的分析方法。首先,设计了一种双层套管的传输管用于连接GC与SPI-TOF MS,实现了GC与单光子电离离子源的无缝连接。在此基础上,以n-十五烷标准品和苯/甲苯/二甲苯的标准气为对象,对电离源的重要电压参数进行了优化,得到了纯净的分子离子峰,实现了对各类有机物的快速和准确定性。最后,将该方法用于分析柴油中的挥发性与半挥发性有机物,获得了柴油组分的二维GC×SPI-TOF MS谱图。不需要复杂的谱图解析和数据处理,根据谱图中离子的质荷比(m/z)归纳了柴油的主要成分,包括脂肪烃、芳香烃和含量很低的苯并吡咯等含氮化合物;根据色谱的保留时间将柴油中的同分异构体区分开来。结果表明GC/SPI-TOF MS法是一种简单、有效的分析方法,非常适于柴油及复杂环境样品等的分析表征。     

Velocity and magnetic modulation methods applied to emission spectroscopy

Velocity modulation and magnetic modulation methods as a means of selective modulation of ionic species have been applied for the first time to emission spectroscopy using a grating spectrometer. Magnetic modulation can achieve concentration modulation effects of up to 100% for ionic species such as N₂⁺ at all spectrometer resolving powers. Both neutral and ionic species may be modulated but the depth of modulation depends in a non-trivial way on the discharge conditions and region being observed. Velocity modulation in contrast is highly ion specific but the modulation depth depends strongly on the resolving power being used. Ion selective spectra using both techniques have been observed for CO⁺ and N₂⁺ in the UV and far-UV regions.     

Comparative studies on excitation of nickel ionic lines between argon and krypton glow discharge plasmas

The emission characteristics of nickel ionic lines in a glow discharge plasma are investigated when argon or krypton was employed as the plasma gas. Large difference in the relative intensities of nickel ionic lines which are assigned to the 3d⁸4p–3d⁸4s transition is observed between the krypton plasma and the argon plasma. Different intense Ni II lines appear in the krypton spectrum and in the argon spectrum, such as the Ni II 231.601 nm for Kr and the Ni II 230.009 nm for Ar. The excitation energy of these Ni II emission lines can give a key in considering their excitation mechanisms. The explanation for these experimental results is that charge-transfer collisions between nickel atom and the plasma gas ion play a major role in exciting the 3d⁸4p excited levels of nickel ion. The conditions for energy resonance in the charge-transfer collision determine particular energy levels having much larger population; for example, the 3d⁸4p ⁴D_7/2 level (6.39 eV) for Kr and the 3d⁸4p ⁴P_5/2 level (8.25 eV) for Ar.     

N2O+离子B2П态的光谱与光解离动力学

用一束波长为360.55 nm的激光直接作用于超声射流的N₂O分子束, 通过(3+1)共振增强多光子电离(REMPI)过程制备纯净的N₂O⁺(X²П(0,0,0))母体离子, 再用另一束波长在243-278 nm范围的激光将母体离子激发至B²П态后解离. 扫描解离激光波长, 监测NO⁺离子碎片的强度, 从而获得N₂O⁺离子B²П态的光致碎片激发(PHOFEX)谱. 通过拟合转动分辨光谱, 得到了相应的转动常数和自旋分裂常数, 从而区分了A²Σ⁺态高振动能级和B²П态带源的贡献, 明确了N₂O⁺离子B²П态的光谱"带头"位置(37154 cm^-1), 并将获得的振动光谱初步归属为B²П(v₁,v₂,v₃)←X²П的振动跃迁序列. 通过对NO⁺碎片离子的飞行时间质谱峰形的分析, 还获得了解离过程中释放的平均平动能, 并结合电子激发态势能面, 讨论了N₂O⁺离子B²П态的解离机理.     

Construction of demountable hollow-cathode lamps for stimulating emission of organic compounds

A demountable hollow cathode has been constructed which provides emission spectra of organic compounds. The construction and operation of the hollow cathode is described. The emission spectra of organic and inorganic phosphates are illustrated and discussed.     

溴代烷烃与活性氮的反应发光研究

在流动余辉装置上, 利用N₂空心阴极放电制备活性氮, 研究了活性氮与溴代烷烃(CHBr₃、CH₂Br₂、C₂H₅Br、C₄H₉Br) 反应的化学发光.上述所有反应中, 在550～750 nm波段均观察到了较强的NBr (b¹Σ+→X³Σ^-)跃迁发射谱. 同时在活性氮与CHBr₃和CH₂Br₂的反应中, 在流动管下游还观察到了CN (A²π, B²π→X²Σ⁺)的发射谱. 验证性的实验表明, 激发态NBr (b¹Σ⁺)是由二步过程形成: N(⁴S)与溴代烷烃反应生成NBr (X³Σ^-), 再通过N₂ (A ³Σ_u⁺)分子能量转移到激发态NBr (b¹Σ⁺); 而激发态的CN是通过N(⁴S) + CBr→CN(A, B) + Br过程形成的.     

Comparison of dielectric barrier discharge, atmospheric pressure radiofrequency-driven glow discharge and direct analysis in real time sources for ambient mass spectrometry of acetaminophen

Three plasma-based ambient pressure ion sources were investigated; laboratory constructed dielectric barrier and rf glow discharges, as well as a commercial corona discharge (DART source). All were used to desorb and ionize a model analyte, providing sampling techniques for ambient mass spectrometry (MS). Experimental parameters were optimized to achive highest signal for acetaminophen as the analyte. Insight into the mechanisms of analyte desorption and ionization was obtained by means of emission spectrometry and ion current measurements. Desorption and ionization mechanisms for this analyte appear to be identical for all three plasma sources. Emission spectra differ only in the intensities of various lines and bands. Desorption of solid analyte requires transfer of thermal energy from the plasma source to sample surface, in the absence of which complete loss of MS response occurs. For acetaminophen, helium was the best plasma gas, providing 100- to 1000-fold higher analyte response than with argon or nitrogen. The same trend was also evident with background ions (protonated water clusters). MS analyte signal intensity correlates with the ion density (expressed as ion current) in the plasma plume and with emission intensity from excited state species in the plasma. These observations support an ionization process which occurs via proton transfer from protonated water clusters to analyte molecules.     

Development of a laser ablation-hollow cathode glow discharge emission source and the application to the analysis of steel samples.

A novel atomic emission spectrometry comprising laser ablation as a sampling source and hollow cathode plasma for the excitation of ablated sample atoms is proposed. In this arrangement, a conventional Grimm-type discharge lamp is employed, but the polarity of the power supply is reversed so that the cylindrical hollow tube acts as a cathode and the glow discharge plasma is produced within this tube. A laser is irradiated to introduce sample atoms into the discharge plasma. Ablated atoms are excited by collisions with electrons and gas species, and emit characteristic radiation upon de-excitation. The experiments were conducted only in an atmosphere of helium gas so as to avoid a rapid erosion of the cathode hollow tube. Phase-sensitive detection with a lock-in amplifier was utilized to reject the continuous background emission of the plasma gas and emissions of sputtered atoms from the tube material. The unique feature of this technique is that the sampling and excitation processes can be controlled independently. The proposed technique was employed for the determination of Cr, Mn, and Ni in low-alloyed steel samples. The obtained concentrations are in good agreement with the reported values. The relative standard deviation (RSD), a measure of the analytical precision, was estimated to be 2-9% for Cr, 3-4% for Mn, and 4-11% for Ni determination.     

Investigation of a novel hollow cathode configuration for Grimm-type glow discharge emission

A hollow cathode configuration was designed for a Grimm-type glow discharge atomic emission spectrometer (GD-AES). The operating conditions including the hollow cathode dimension, applied pulsed voltage and argon pressure, were optimized. The 10-μs pulses at 1.8 kV in a 3-torr discharge worked best. A pulsed hollow cathode Grimm discharge (HCG) offers several advantages: efficient excitation and ionization; high sensitivity; temporal spectral resolution; and rapid sample interchange. The capability of this source for the determination of elemental composition in metals, alloys and in solution residues is investigated. Samples used in this study included copper and steel standards.     

Evaluation of a hollow cathode atomic emission source designed for continuous solution sample introduction

A hollow cathode discharge capable of continuous operation with solution sample introduction is described. Discharge current densities up to 0.64 are maintained in a helium plasma. Analyte emission intensities are optimized in terms of anode placement in relation to the hollow cathode, carrier gas flow rate, discharge current and sample solution flow rate. Detection limits for selected elements are reported and range from 0.03 for Li to 200 for Zn. Temporal stability of the discharge is examined and a calibration curve for Li is presented.     

The design and characteristics of direct current glow discharge atomic emission source operated with plain and hollow cathodes

A compact direct current glow discharge atomic emission source has been designed and constructed for analytical applications. This atomic emission source works very efficiently at a low-input electrical power. The design has some features that make it distinct from that of the conventional Grimm glow discharge source. The peculiar cathode design offered greater flexibility on size and shape of the sample. As a result the source can be easily adopted to operate in Plain or Hollow Cathode configuration. I-V and spectroscopic characteristics of the source were compared while operating it with plain and hollow copper cathodes. It was observed that with hollow cathode, the source can be operated at a less input power and generates greater Cu I and Cu II line intensities. Also, the intensity of Cu II line rise faster than Cu I line with argon pressure for both cathodes. But the influence of pressure on Cu II lines was more significant when the source is operated with hollow cathode.     

Study of some excitation characteristics of the discharge in a hot hollow cathode

Some excitation characteristics of the discharge in a hot hollow cathode were investigated. A graphite cathode coated with evaporated films of copper, iron, manganese or titanium, and argon or helium fill gas were applied. The dependence of spectral-line intensities on fill gas pressure and discharge current were studied. At 0.4 A discharge current and various fill gas pressures, the excitation temperatures for iron, manganese and titanium were determined.     

The laser as an analytical probe in glow discharge mass spectrometry

A pulsed dye laser was used alone and in combination with an auxiliary glow discharge for diagnostic studies. We have compared the mass ablation rate and ion signal in high vacuum and in the presence of an ambient buffer gas. Laser pulse energy and repetition rate were studied over the analytical range of the system. The effect of ambient gas pressure on redeposition was determined for three different gases: helium, neon, and argon. The laser/auxiliary discharge system was also shown to have analytical utility for the analysis of nonconducting samples. Spectra are included to illustrate the enhancement of the laser atomization/discharge ionization scheme over laser atomization/ionization.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Investigation of different crude oils applying thermal analysis/mass spectrometry with soft photoionisation

A variety of crude oil samples have been investigated by the combined methods of thermal analysis and mass spectrometry by means of a newly developed prototype of a thermogravimetry—single photon ionisation time-of-flight mass spectrometer coupling (TG-SPI-TOFMS). Single photon ionisation (SPI) was conducted utilising a novel electron beam pumped argon excimer lamp (EBEL) as photon source, and a TOFMS with orthogonal acceleration has been applied for the detection of the mass to charge signals. The advantage of the soft SPI technique over EI for the analysis of such complex samples could be clearly demonstrated, as the aliphatic hydrocarbons present in crude oil may be detected via their respective molecular ion signals, not showing the intense fragmentation typical for EI spectra of this substance class. The application of SPI revealed furthermore two distinct decomposition regions, dominated by evaporation and pyrolysis processes, respectively. Moreover, different crude oils could be distinguished by TA/SPI mass spectra due to their unique molecular signatures.     

A comparison of argon and mixed gas plasmas for inductively coupled plasma-mass spectrometry

The effects of adding N₂ to the outer gas flow of an Ar plasma in inductively coupled plasma mass spectrometry (ICP-MS) are illustrated. With 5% N₂ added to the outer gas flow and provided the central (nebulizer) gas flow is increased, modest signal enhancements (up to a factor of 4) are observed. The degree of enhancement depends on the extent to which an element forms a strong metal oxide bond and also, to some extent, on ionization potential. An important feature of N₂ mixed gas plasmas for ICP-MS is that the signals for analyte oxide species (MO⁺) and certain background species (ArO⁺, ArOH⁺, Ar₂⁺, ClO⁺, and ArCl⁺) are significantly reduced (an order of magnitude) by the addition of N₂ to the outer gas flow. In addition to these observations, some results are also presented for O₂ and air (outer gas) mixed gas plasmas and N₂ (central gas) mixed gas plasmas.