辉光放电质谱法测定高纯材料中痕量硫杂质

准确测定并控制材料中杂质元素含量是发挥高纯材料性能不可或缺的环节。辉光放电质谱法(GDMS)是准确、快速、高灵敏分析高纯材料中痕量及超痕量硫的理想方法。对GDMS分析高纯铜和镍基高温合金中痕量硫的质谱干扰进行了讨论,优化了放电电流和放电电压,采用多种标准物质对硫的相对灵敏度因子(RSF)进行了校准和验证,并与二次离子质谱法(SIMS)进行分析结果比对,验证了GDMS定量分析结果的准确性和可靠性。     

辉光放电质谱法在高纯材料分析中的应用

高纯材料是现代高新技术发展的基础,在电子、光学和光电子等尖端科学领域发挥着重要作用。采用固体样品直接分析的辉光放电质谱法(GDMS),在高纯金属、高纯半导体材料的痕量和超痕量杂质分析中有着非常广泛的应用。综述了GDMS法对高纯金属、高纯半导体材料进行的元素分析,并对分析过程中工作参数、溅射时间、干扰峰等因素的影响进行了阐述。同时,也详述了应用GDMS法对高纯金属钛、镉,高纯半导体硅,分别进行的痕量杂质元素分析,结果显示放电稳定性良好,典型元素含量的相对标准偏差均在较为理想范围内。GDMS应用前景广泛,未来,GDMS将在除固体样品之外的其他样品类型的分析领域中发挥重要作用。     

高流速辉光放电质谱法测定镍基单晶高温合金中43种痕量元素北大核心CSCD

基于高流速辉光放电质谱法(GDMS)的质谱干扰消除技术,对镍基单晶高温合金中43种痕量元素的质谱干扰与同位素选择进行了研究,用于高性能镍基单晶高温合金的纯净化水平评价。固体样品采用直接进样,通过复杂基体质谱干扰计算判定、共存元素干扰消除等方式,确定了待测元素的同位素和分辨率模式,通过相应标准物质对待测元素的相对灵敏度因子进行校正,采用高流速GDMS测定镍基单晶高温合金中43种痕量元素。结果表明,痕量元素的检出限(3s)为1.04×10^(-7)%~6.60×10^(-3)%,大部分元素的检出限达到0.1μg·g^(-1)级别;对内控标准物质DD6-6#测定6次,测定值的相对标准偏差为0.59%~13%。方法分析结果与不同分析方法对照、标准物质比对,结果吻合度高。     

辉光放电质谱法测定高纯铟中痕量元素

采用辉光放电质谱法(GDMS)对高纯铟中铁、铜、铅、锌、铊、镉、锡等14种元素进行了测定,对仪器工作参数进行了优化,对预溅射过程时间的确定和质谱干扰的排除进行了讨论,结果表明,GDMS是目前具有足够灵敏度对高纯导电材料进行直接分析的有效手段。     

辉光放电质谱法测定氧化铟锡靶材中的元素含量

利用辉光放电质谱仪(GDMS)一次性直接测定ITO靶材中的主体元素和痕量元素。首先考察了ITO样品中的元素和Ar,H,O,N等气体元素形成的多原子离子干扰,利用X射线光电子能谱确定氧化铟锡靶材的主体元素In和Sn的组分,通过GDM S校正获得二者的相对灵敏度因子(RSF),从而对ITO中的In和Sn进行定量,并利用典型RSF对其他痕量元素进行半定量。测试的结果具有较好的准确度和精度。利用校正RSF和典型RSF相结合进行测试的方法同样适用于类似的掺杂的半导体材料。     

生物藻分离富集法在痕量元素分析中的应用及进展

生物藻分离富集痕量元素具有快速、简便、选择性好、富集效率高等特点，可望发展成为一种应用于痕量和超痕量元素分析的很有前途的特性分离富集方法。本文简述了这一领域的最新研究成果。     

MSPD-GC-ECD测定血液中甲氧基多溴联苯醚

以MSPD为萃取方法,GC-ECD为检测手段,建立了血液中痕量Me O-PBDEs的分析方法。通过对萃取材料、洗脱液、洗脱液体积和样品预处理的影响研究,确定了最佳分析条件:液氮研磨血液样品,ENVI-18为萃取材料,2 mL乙酸乙酯为洗脱液。在该条件下,应用于血液痕量MeO-PBDEs的测定,相对标准偏差小于10%,显示出良好的重复性;方法的检出限为0. 28～0. 62 ng/g,加标回收率在80. 2～117. 9%。结果表明,所建立的分析方法适合于血液中痕量MeO-PBDEs的检测。     

辉光放电质谱法测定超高纯铜溅射靶材中痕量杂质元素及其相对灵敏度因子的求取北大核心CSCD

通过选择合适的同位素及分辨率,提出了辉光放电质谱法(GDMS)测定超高纯铜溅射靶材中39种痕量杂质元素的分析方法。对辉光放电过程中的参数进行了优化,条件如下:放电气体流量为450 mL·min^(-1),放电电流为2.00 mA,预溅射时间为20 min。由于高纯铜的GDMS标准样品极难获得,为提高痕量杂质元素的检测准确度,在现有的标准样品条件下,利用高纯铜标准样品只获得了与基体匹配的21种杂质元素的相对灵敏度因子(RSF),其余18种杂质元素的RSF只能按照仪器自带的标准RSF进行计算。参照美国材料与试验协会的标准ASTM F1593-08(2016)的TypeⅢ中的第2种方法计算33种杂质元素的检出限,而其他6种主要杂质元素因其含量高于仪器噪声水平而无法用此法得到检出限。用GDMS对超高纯铜溅射靶材样品进行了检测,主要杂质元素为硅、磷、硫、氯、铁、银,检出量为0.015~0.082μg·g^(-1),杂质总量小于1μg·g^(-1)。除锌、碲、金的检出限在10 ng·g^(-1)级外,其余元素的检出限能够达到ng·g^(-1)级,其中钍、铀的检出限甚至达到了0.1 ng·g^(-1)级,说明方法能够满足GB/T 26017-2010中的6N(99.9999%)超高纯铜溅射靶材的检测要求。     

复杂样品痕量极性小分子化合物的样品前处理及分析方法研究进展

核苷、胺、氨基酸等极性小分子化合物是生物、食品、环境等领域重要的研究对象,但各种复杂基体中痕量极性小分子的分离分析需要高效的前处理介质和技术以及快速灵敏的分析方法。本文综述了硅胶材料、有机聚合物、炭材料和硼酸材料等样品前处理分离介质及反相液相色谱、亲水作用色谱等分析方法在复杂样品痕量极性小分子化合物分析中的应用,并展望了其发展趋势。     

辉光放电质谱测量中的相对灵敏度因子研究

辉光放电质谱(GDMS)作为高纯金属和半导体材料分析的强有力工具在国内已得到了大量应用,该文简要介绍了GDMS的基本原理和国内外应用现状,对仪器测量条件的选择、测量重复性进行了详细研究,对于含量在1 mg/kg左右的杂质,测量的重复性将产生约1%～5%的不确定度;对不同金属基体的系列标准物质进行对比研究,发现对于基体相同的样品,杂质元素在较宽的浓度范围内可以使用同样的校正系数进行校正,大部分元素的线性相关系数达到0.999以上,但对于不同基体的样品,测量中仍存在明显的基体效应,一些元素,尤其是轻质量数元素的相对灵敏度因子(RSF)设定值存在较大的偏差,并不适合定量分析,但绝大部分不超过2倍误差,可以满足半定量分析的要求。通过对GDMS定量分析中关键因素的研究,认为相对灵敏度因子的校正是GDMS测量结果可溯源性的关键。     

辉光放电质谱技术应用进展

对辉光放电质谱(GDMS)在金属与半导体、非导体、薄层与深度分析、分子信息分析方面的应用和一些新装置、新方法进行了综述.着重介绍了近20年来我国学者在辉光放电质谱方面的成就,并结合国际上的报道对该领域的发展现状进行了总结.     

On-line coupling of ion chromatography and atomic spectrometry and use of direct graphite furnace atomic absorption spectrometry as new tools for ultra trace determinations in refractory metals

On-line coupling of inductively coupled plasma (ICP) techniques such as ICP-AES and ICP-MS with ion chromatography (IC) offers unique features for ultra-trace analysis. An on-line preconcentration procedure based on cation exchange enables sub-ng/g analysis in complex matrices like molybdenum and tungsten. The best dissolution reagent for these matrices is hydrogen peroxide, which can be cleaned to ultra high purity with the same metal free chromatography equipment used for the preconcentration. Preconcentration is possible for elements that show cationic reactions within acidic peroxide containing solutions. In this study 28 elements detrimental for microelectronics applications are observed. A comparison of the combinations IC-ICP-AES and IC-ICP-MS with glow discharge mass spectrometry (GDMS) for the analysis of today's purest tungsten samples shows the analytical power and accuracy of the coupled devices. Graphite furnace atomic absorption spectrometry (GFAAS) as an extremely sensitive analytical technique is applied with and without the same sample pretreatment as used for the on-line coupling. Direct GFAAS measurements of alkali metals are complementary to IC-ICP techniques. The data evaluated with these wet chemical techniques are compared to the usual manufacturers characterisation technique GDMS. With respect to the low concentrations present in these high purity materials (ng/g level in the solid) the discrepancies between all methods are acceptable. The sensitivity of IC-ICP-MS is in most cases far superior to IC-ICP-AES and for some elements also to GDMS. Furthermore the specific advantages of on-line coupling such as the elimination of isobaric interferences in ICP-MS or spectral interferences in ICP-AES are shown for ICP-AES and ICP-MS determinations.     

Analysis of solution residues by glow discharge mass spectrometry

A technique for the analysis of microliter volumes of solution by glow discharge mass spectrometry (GDMS) has been successfully demonstrated. Cathode preparation involves mixing an aliquot of the sample solution with a pure conducting powder, followed by drying and pressing before conventional GDMS analysis. The analyte signal at the 100-ppm level was observed to be stable to better than 5% for the duration of the analysis (30–45 min). Internal and external reproducibilities were better than 5%, and the ion signal intensity was linear with concentration over at least four orders of magnitude. Quantification was demonstrated by means of user-defined relative sensitivity factors. Relative standard deviations were better than 15% for the elements investigated, with no preconcentration of the analyte.     

Application of the glow discharge mass spectrometry (GDMS) for the multi-element trace and ultratrace analysis of sputtering targets

Glow discharge mass spectrometry using a VG9000 high resolution mass spectrometer has been applied to both the multi-element trace and ultra trace analyses of sputtering target materials, i.e. aluminium-based alloys, cobalt-based alloys, titanium and platinum. Element dependent relative sensitivity factors (RSF) have been determined using reference materials in order to provide the possibility for quantitative analyses. Aluminium-based and cobalt-based alloys have been extensively analysed to demonstrate precision of GDMS analyses. Detection limits in the ng/g and sub-ng/g ranges, i.e. 0.2 ng/g for U and Th have been determined in aluminium-based alloys. Comparative analyses for alloy components in cobalt-based alloys as well as trace concentrations in titanium have been performed. GDMS has been also applied to multi-element depth profile analyses in contaminated and noncontaminated platinum targets.     

Detection of trace radioisotopes in soil, sediment and vegetation by glow discharge mass spectrometry

The possibility for the determination of some radioisotopes of cesium, strontium, plutonium, uranium and thorium by glow discharge mass spectrometry (GDMS) in soils, sediments and vegetations is investigated. The preparation of samples is described as a combination of the use of a conductive host matrix and a secondary cathode in order to decrease the dilution effect of the blending material for the trace level determination and to gain a stable discharge. Effects of interferences arising from the nature of the conductive host matrix and of the secondary cathode on the sensitivity of the method are discussed. The determination of ¹³⁷Cs and ⁹⁰Sr has been attempted and the results obtained were in agreement with those from other analytical techniques. Accuracy, internal and external precisions have been also evaluated. GDMS is shown to be a helpful technique for the determination of radioisotopes in environmental samples. Radioisotopes can be determined according to the matrix of the sample (e.g. grass), also in presence of isobaric interferences. However, limitations still exist on the application of GDMS.     

Element speciation analysis by capillary electrophoresis

An overview of recent developments in the application of capillary electrophoresis to simultaneous separation and determination of different chemical forms of an inorganic element is presented, with particular emphasis placed on metal speciation analysis. Examples of species analysis are addressed, covering metal ions in different oxidation states, metal complexes with inorganic and organic ligands, metalloid oxoanions, organometallic compounds, ionic non-metal species, etc. The speciation performance of capillary electrophoresis is illustrated by a number of practically relevant applications. The method's strengths and current limitations with regard to chemical speciation studies are critically discussed.     

New developments and applications in GDMS

An overview is given about the new developments in GDMS, both with respect to the glow discharge source as to the coupling with various kinds of mass spectrometers. Moreover, as for every analytical technique, methodological and fundamental research is being carried out to improve the analytical results of GDMS, and some of the new developments in these fields will be discussed as well. Finally, the various analytical applications of GDMS will be presented. Received: 11 November 1998 / Revised: 29 January 1999 / Accepted: 6 February 1999     

Detection of trace radioisotopes in soil,sediment and vegetation by glow discharge mass spectrometry

The possibility for the determination of some radioisotopes of cesium, strontium, plutonium, uranium and thorium by glow discharge mass spectrometry (GDMS) in soils, sediments and vegetations is investigated. The preparation of samples is described as a combination of the use of a conductive host matrix and a secondary cathode in order to decrease the dilution effect of the blending material for the trace level determination and to gain a stable discharge. Effects of interferences arising from the nature of the conductive host matrix and of the secondary cathode on the sensitivity of the method are discussed. The determination of (137)Cs and (90)Sr has been attempted and the results obtained were in agreement with those from other analytical techniques. Accuracy, internal and external precisions have been also evaluated. GDMS is shown to be a helpful technique for the determination of radioisotopes in environmental samples. Radioisotopes can be determined according to the matrix of the sample (e.g. grass), also in presence of isobaric interferences. However, limitations still exist on the application of GDMS.