Microplasma Technology and Its Applications in Analytical Chemistry

Abstract

This review article describes some existing microplasma sources and their applications in analytical chemistry. These microplasmas mainly include direct current glow discharge (DC), microhollow-cathode discharge (MHCD) or microstructure electrode (MSE), dielectric barrier discharge (DBD), capacitively coupled microplasmas (CCμPs), miniature inductively coupled plasmas (mICPs), and microwave-induced plasmas (MIPs). The historical development and recent advances in these microplasma techniques are presented. Fundamental properties of the microplasmas, the unique features of the reduced size and volume, as well as the advantageous device structures for chemical analysis are discussed in detail, with the emphasis toward detection of gaseous samples. The analytical figures of merit obtained using these microplasmas as molecular/elemental-selective detectors for emission spectrometry and as ionization sources for mass spectrometry are also given in this review article.     

Inductively Coupled Plasma and Electron Cyclotron Resonance Plasma Etching of an InGaAlP Compound Semiconductor System

Current and future generations of sophisticated compound semiconductor devices require the ability for submicron scale patterning. The situation is being complicated because some of the new devices are based on a wider diversity of materials to be etched. Conventional RIE (reactive ion etching) has been prevalent across the industry so far, but has limitations for materials with high bond strengths or multiple elements. In this article, we suggest high-density plasmas such as ECR (electron cyclotron resonance) and ICP (inductively coupled plasma), for the etching of ternary compound semiconductors (InGaP, AlInP, AlGaP) that are employed for electronic devices such as heterojunction bipolar transistors (HBTs) or high electron mobility transistors (HEMTs), and photonic devices such as light-emitting diodes (LEDs) and lasers. Operating at lower pressure, high-density plasma sources are expected to meet target goals determined in terms of etch rate, surface morphology, surface stoichiometry, selectivity, etc. The etching mechanisms that are described in this article can also be applied to other III-V (GaAs-based, InP-based) as well as III-Nitride, because the InGaAlP system shares many of the same properties.     

Changes of the electron dynamics in hydrogen inductively coupled plasma

Changes of the electron dynamics in hydrogen （H2） radio-frequency （RF） inductively coupled plasmas are investigated using a hairpin probe and an intensified charged coupled device （ICCD）. The electron density, plasma emission intensity, and input current （voltage） are measured during the E to H mode transitions at different pressures. It is found that the electron density, plasma emission intensity, and input current jump up discontinuously, and the input voltage jumps down at the E to H mode transition points. And the threshold power of the E to H mode transition decreases with the increase of the pressure. Moreover, space and phase resolved optical emission spectroscopic measurements reveal that, in the E mode, the RF dynamics is characterized by one dominant excitation per RF cycle, while in the H mode, there are two excitation maxima within one cycle.     

电磁波在非磁化等离子体中衰减效应的实验研究

针对等离子体隐身技术在航空航天领域的良好应用前景, 开展垂直入射到具有金属衬底的非磁化等离子体中电磁波衰减特性的理论与实验研究. 利用WKB方法对电磁波衰减随等离子体参数的变化规律进行了理论分析. 利用射频电感耦合放电方式产生稳定的大面积等离子体层, 搭建了等离子体反射率弓形测试系统, 进行了电磁波在非磁化等离子体中衰减效应的实验研究. 利用微波相位法和光谱诊断法, 得到不同放电功率下的等离子体电子密度, 其范围为8.17×10⁹–7.61× 10¹⁰ cm^-3. 本实验获得的等离子体可以使2.7 GHz 和10.1 GHz电磁波分别得到一定的衰减, 且电磁波衰减的理论与实验结果符合较好. 结果表明, 提高等离子体电子密度和覆盖均匀性有利于增强等离子体对电磁波的衰减效果.     

The Darwin Direct Implicit Particle-in-Cell (DADIPIC) Method for Simulation of Low Frequency Plasma Phenomena

We describe a new algorithm for simulating low frequency, kinetic phenomena in plasmas. Darwin direct implicit particle-in-cell (DADIPIC), as its name implies, is a combination of the Darwin and direct implicit methods. Through the Darwin method the hyperbolic Maxwell's equations are reformulated into a set of elliptic equations. Propagating light waves do not exist in the formulation so the Courant constraint on the time step is eliminated. The direct implicit method is applied only to the electrostatic field with the result that electrostatic plasma oscillations do not have to be resolved for stability. With the elimination of these constraints spatial and temporal discretization can be much larger than that possible with explicit, electrodynamic PIC. We discuss the algorithms for pushing the particles and solving for the fields in 2D cartesian geometry. We also detail boundary conditions for conductors and dielectrics. Finally, we present two test cases, electron cyclotron waves and collisionless heating in inductively coupled plasmas. For these test cases DADIPIC shows agreement with analytic kinetic theory and good energy conservation characteristics.     

Application of weakly ionized plasmas for materials sampling andanalysis

The use of weakly ionized plasmas as spectroscopic sources for materials sampling and analysis is reviewed. Plasma sources currently used for this purpose include direct-current and alternating-current plasmas, inductively coupled plasmas, microwave-induced plasmas, surface-wave plasmas, capacitively coupled plasmas, capacitive microwave plasmas, glow discharges, flowing afterglows, theta pinch discharges, exploding films and wires, and laser-produced plasmas. The authors give a summary of relevant characteristics of some of the plasma sources. Included are the source, common method of application, approximate detection limit for that method, applicability for solid sampling, susceptibility to matrix effects, approximate cost, and the most common usage for the method     

Nonmonotonic spatial decay and shield height effects in inductivelycoupled plasmas

Nonmonotonic spatial decay in electric field and space current distributions was recently observed in weakly collisional plasmas. The anomalous skin effect is found to be responsible for this phenomenon. Based on our proposed self-consistent analytic model, we successfully modeled the nonmonotonic spatial decay effect in inductively coupled plasma sources. The simulated spatial distribution of the induced E-field is compared to the measurements for different applied RF powers. Quantitative agreements for the electric field and qualitative agreement for the induced space current are achieved between the simulated and measured data. Also demonstrated is that the RF power and the reactor geometry such as the shield height has a direct impact upon the anomalous skin effect and its skin depth     

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对感应耦合氩气热等离子体的速度分布特性以及各操作参数对等离子体速度分布的影响进行了细致的研究。研究结果表明,与直流电弧热等离子体相比,感应耦合热等离子体速度小,弧流集中,速度峰值出现在等离子体炬下游,在线圈段上游出现明显的回流现象。此外,送气流量、感应电流等操作参数对等离子体速度分布有明显影响。研究结果可为等离子体球化粉末颗粒及其他应用提供理论指导。     

ICP光源的激光烧蚀固体样品引入方法进展

根据近几年来国内外的有关文献,叙述了ICP光源的激光烧蚀固体进样方法的研究进展及其在物质成分分析中的应用。着重阐述了激光输出特性(输出波长、脉冲宽度、重复频率、能量密度)和环境气氛(氦气、氩气)对样品烧蚀过程的影响,讨论了激光烧蚀室、气溶胶传输管道及样品引入改进装置在蒸发物质被传输到ICP光源过程中的作用。获得较小而均匀的气溶胶颗粒和稳定高效地将烧蚀物质输送到ICP是完善激光烧蚀固体进样技术的关键环节,元素分馏效应及蒸发物沉积是影响分析性能的重要因素。作为实际例子,也讨论了激光烧蚀固体进样电感耦合等离子体发射光谱法/质谱法在金属、玻璃、有机物及其他样品分析方面的应用,对分析方法的准确度、精密度、检出限和灵敏度进行了简要论述。     

Fundamental study towards a better understanding of low pressure radio-frequency plasmas for industrial applications

Two classic radio-frequency (RF) plasmas, i.e., the capacitively and the inductively coupled plasmas (CCP and ICP), are widely employed in material processing, e.g., etching and thin film deposition, etc. Since RF plasmas are usually operated in particular circumstances, e.g., low pressures (mTorr-Torr), high-frequency electric field (13.56 MHz-200 MHz), reactive feedstock gases, diverse reactor configurations, etc., a variety of physical phenomena, e.g., electron resonance heating, discharge mode transitions, striated structures, standing wave effects, etc., arise. These physical effects could significantly influence plasma-based material processing. Therefore, understanding the fundamental processes of RF plasma is not only of fundamental interest, but also of practical significance for the improvement of the performance of the plasma sources. In this article, we review the major progresses that have been achieved in the fundamental study on the RF plasmas, and the topics include 1) electron heating mechanism, 2) plasma operation mode, 3) pulse modulated plasma, and 4) electromagnetic effects. These topics cover the typical issues in RF plasma field, ranging from fundamental to application.     

ICP等离子体鞘层附近区域发光光谱特性分析

为了独立控制鞘层附近区域离子密度和离子能最分布,采用光发射谱(OES)测量技术,对不同射频功率、放电气压和基底偏压下感应耦合等离子体鞘层附近区域辉光特性进行了研究.原子谱线和离子谱线特性分析表明,在鞘层附近区域感应耦合等离子体具有较高的离子密度和较低的电子温度.改变放电气压和射频功率,对得到的光谱特性分析表明,鞘层附近区域离子密度随射频功率的增大而线性增大,在低压下随气压的升高而增大.低激发电位原子谱线强度增加迅速,高激发电位原子谱线强度增加缓慢,而离子谱线强度增加很不明显.改变基底直流偏压,对得到的发射光谱强度变化分析表明,谱线强度随基底正偏压的增加而增大.随着基底负偏压的加入,谱线强度先减小而后增大;直流偏压为-30 V时,光谱强度最弱.快速离子和电子是引起Ar激发和电离过程的主要能量来源.     

RF electric field penetration and power deposition into nonequilibrium planar-type inductively coupled plasmas

The RF electric field penetration and the power deposition into planar-type inductively coupled plasmas in low-pressure discharges have been studied by means of a self-consistent model which consists of Maxwell equations combined with the kinetic equation of electrons. The Maxwell equations are solved based on the expansion of the Fourier--Bessel series for determining the RF electric field. Numerical results show the influence of a non-Maxwellian electron energy distribution on the RF electric field penetration and the power deposition for different coil currents. Moreover, the two-dimensional spatial profiles of RF electric field and power density are also shown for different numbers of RF coil turns.     

Comparison of excessive Balmer /spl alpha/ line broadening of inductively and capacitively coupled RF, microwave, and glow-discharge hydrogen plasmas with certain catalysts

From the width of the 656.3-nm Balmer /spl alpha/ line emitted from inductively and capacitively coupled radio frequency (RF), microwave, and glow-discharge plasmas, it was found that inductively coupled RF helium-hydrogen and argon-hydrogen plasmas showed extraordinary broadening corresponding to an average hydrogen atom energy of 250-310 and 180-230 eV, respectively, compared to 30-40 and 50-60 eV, respectively, for the corresponding capacitively coupled plasmas. Microwave helium-hydrogen and argon-hydrogen plasmas showed significant broadening corresponding to an average hydrogen atom energy of 180-210 and 110-130 eV, respectively. The corresponding results from the glow-discharge plasmas were 33-38 and 30-35 eV, respectively, compared to /spl ap/ 4 eV for plasmas of pure hydrogen, neon-hydrogen, and xenon-hydrogen maintained in any of the sources. Similarly, the average electron temperatures T/sub e/ for helium-hydrogen and argon-hydrogen inductively coupled RF and microwave plasmas were high (43 200 /spl plusmn/ 5% K, 18 600 /spl plusmn/ 5% K, 30 500 /spl plusmn/ 5% K, and 13 700 /spl plusmn/ 5% K, respectively); compared to 9300 /spl plusmn/ 5% K, 7300 /spl plusmn/ 5% K, 8000 /spl plusmn/ 5% K, and 6700 /spl plusmn/ 5% K for the corresponding plasmas of xenon-hydrogen and hydrogen alone, respectively. Stark broadening or acceleration of charged species due to high electric fields cannot explain the inductively coupled RF and microwave results since the electron density was low and no high field was present. Rather, a resonant energy transfer mechanism is proposed.     

A Comparative Study of Single and Double Langmuir Probe Techniques for RF Plasma Characterization

In this study, the plasma density and electron temperature of Radio Frequency (RF) plasmas were determined by three types of Langmuir probes, namely a conventional double probe, a single probe with RF choke and a single probe with RF choke and compensating electrode. The same plasmas were characterized by the three probes, each performing three measurements per plasma condition, in order to determine the precision of the measurement results. After performing a comparative analysis, which looked at the precision and the accuracy of these results, the conclusion is that the double probe, which has already the advantage of the simplest construction, yields the most reliable results for both capacitively and inductively coupled RF plasmas. The single probe with RF choke and compensating electrode has a similar precision as the single probe without compensating electrode, but its accuracy is better.     

Orientation phenomena for direct s-p electron-ion collisional excitations in weakly coupled plasmas using the screened hyperbolic-orbit trajectory method

Orientation phenomena for direct electron-ion collisional excitations in weakly coupled plasmas () are investigated using the semiclassical curved trajectory method including the close-encounter effects. The results show that the orientation parameters including the close-encounter effects obtained by the hyperbolic-orbit trajectory method have maxima and minima for small impact parameter regions. Received 18 August 1999 and Received in final form 6 December 1999     

电感耦合等离子体质谱法测定硅藻土助滤剂中的重金属元素

建立了硅藻土助滤剂中多个重金属元素的分析方法。以氢氟酸、硝酸和磷酸为混合试剂采用微波消解法对硅藻土助滤剂进行密闭消解,应用电感耦合等离子体质谱(ICP-MS)法对消解液中的Be,Cr,Ni,As,Cd,Sb,Sn,Tl,Hg,Pb等10个元素进行测定。研究了高硅基体存在时所产的质谱干扰,首先通过优化仪器工作参数以及待测元素同位素的选择,最大程度地避免了质谱分析过程中的多种干扰,然后选择动态反应（DRC）技术消除了其它质谱干扰,多元素（Li,Sc,Y,In,Bi）内标溶液的使用消除了基体效应,维持了分析信号的稳定。分析结果显示,10个待测元素的检出限在3.29～15.68 ng·L-1之间,相对标准偏差（RSD）≤4.62%,加标回收率为90.71%～107.22%。方法的灵敏度高,准确度和精密度好,可用于硅藻土助滤剂的质量控制和安全评价。     

激光熔蚀-电感耦合等离子体质谱法测定底泥沉积物中的总汞

采用激光熔蚀-电感耦合等离子体质谱法(LA-ICP-MS)测定了底泥沉积物中的总汞,沉积物样品经高压压坯后直接进行激光熔蚀测定,并对内标选定、样品粒度以及汞的形态等影响因素进行了研究,以2个底泥标准样和1个土壤标准样的测定结果来绘制标准曲线,并用于实际样品的测定,方法简便实用,测定结果与同位素稀释冷蒸气发生ICP-MS法十分吻合,方法检出限为0.02 mg·kg-1,测定速度可达每小时10样。     

温度、密度对磁化等离子体光子晶体缺陷模的影响

采用等温近似,用磁化等离子体的分段线形电流密度卷积(Piecewise Linear Current Density Recursive Convolution,PLCDRC)时域有限差分(Finite-differentce Time-domain,FDTD)算法研究了具有单一缺陷层的一维磁化等离子体光子晶体的缺陷模特性;以高斯脉冲为激励源,用算法公式计算所得的电磁波透射系数,讨论了温度和等离子体层密度对其缺陷模的影响。结果表明:改变温度和等离子体层密度可以获得不同的缺陷模。     

大气颗粒物重金属元素分析技术研究进展

大气颗粒物已经成为当前大气环境首要污染物,而其中重金属由于具有非降解性和滞后性,严重威胁人类生命和自然环境,已成为当前研究热点。对分析大气颗粒物中重金属元素所用原子吸收光谱法、电感耦合等离子体原子发射光谱法、电感耦合等离子体质谱法、荧光光谱法、中子活化法、辉光放电原子发射光谱法、微波等离子体原子发射光谱法和激光诱导击穿光谱法进行了综述,并尝试对这些技术的不足之处提出一些改进建议：连续光源原子吸收光谱法同时测定多种元素,原子发射光谱法直接测定颗粒物,高分辨率激光剥蚀电感耦合等离子质谱法测定固体样品,低散射同步加速荧光法测定大气颗粒物和k₀中子活化法测定对流层发射性元素。大气颗粒物重金属元素的时空分布差异和人类对环境空气质量要求的提高以及现代仪器科学技术的高速发展促使大气颗粒物重金属元素分析技术朝着实时、快速、检出限低、直接测定和操作简便的方向发展。     

Composition and Thermodynamic Properties of Dense Alkali Metal Plasmas

In this work composition and thermodynamic properties of dense alkali metal plasmas (Li, Na) were investigated. Composition was derived by solving the Saha equations with corrections due to nonideality. The lowering of the ionization potentials was calculated on the basis of pseudopotentials by taking screening and quantum effects into account (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)