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。     

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。     

辉光放电质谱法在无机非金属材料分析中的应用

辉光放电质谱法(GDMS)作为一种固体样品直接分析技术,已广泛应用于金属、半导体等材料的痕量和超痕量杂质分析。近年来,随着制样方法和离子源装置的改进,GDMS同样也能很好地应用于玻璃、陶瓷、氧化物粉末等非导体材料的成分分析。简介了GDMS的基本原理和分析特点,概述了GDMS在无机非金属材料分析的方法以及应用情况。     

辉光放电质谱法研究高纯氧化铋中19种元素的相对灵敏度因子

采用标准溶液加入法,往高纯氧化铋中加入混合标液,烘干并研磨均匀,制备了5个高纯氧化铋的控制样品。在挑取适量的粉末样品压在高纯铟薄片上,建立了辉光放电质谱法(GDMS)研究高纯氧化铋中的Mg、Al、Ca等19个元素相对灵敏度因子的方法。实验考察了放电参数和制样面积对基体信号强度和稳定性的影响,优化后的辉光放电电流为1.8 mA,放电电压为950 V,压在铟薄片上的高纯氧化铋直径约为6~8 mm。通过选择合适的同位素,在4000的中分辨率下测定即可消除质谱干扰。为了验证加标的准确性,采用电感耦合等离子体质谱仪(ICP-MS)对控制样品进行测定,所有元素的回收率都在80%以上。采用GDMS法测定5个控制样品并结合ICP-MS的测定值建立工作曲线,大部分元素的线性均达到0.995以上;除Al、Ga、Sb外,大部分元素的校准相对灵敏度因子(calRSF)和仪器自带的标准相对灵敏度因子(stdRSF)的比值都在1/2~2之间,说明GDMS的半定量分析不会有数量级的差别。但对于某些需要准确测定纯度的定量分析,则必须采用基体相匹配的RSF值进行校正。     

辉光放电质谱法测定超高纯铝中痕量杂质元素EI北大核心CSCD

采用辉光放电质谱法(GDMS)分析超高纯铝样品(含铝量≥99.9995%)中B,Mg,Si,P,Cl,Ti等44种主要杂质元素,并且与电感耦合等离子体质谱法(ICPM S)进行对比,主要杂质元素含量检测结果一致。本工作对质谱干扰的排除和预溅射过程时间的确定进行了讨论,采用高纯铝标样对高纯铝中26种主要元素相对灵敏度因子(RSF)进行校正和验证,并考察了检测结果的准确性和精密度。结果表明,GDMS是超高纯铝样品直接测定的最有效手段之一。     

辉光放电质谱法测定超高纯铝中痕量杂质元素

采用辉光放电质谱法(GDMS)分析超高纯铝样品(含铝量≥99.9995%)中B,Mg,Si,P,Cl,Ti等44种主要杂质元素,并且与电感耦合等离子体质谱法(ICPM S)进行对比,主要杂质元素含量检测结果一致。本工作对质谱干扰的排除和预溅射过程时间的确定进行了讨论,采用高纯铝标样对高纯铝中26种主要元素相对灵敏度因子(RSF)进行校正和验证,并考察了检测结果的准确性和精密度。结果表明,GDMS是超高纯铝样品直接测定的最有效手段之一。     

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（GDMS）法校正高纯氧化铋中19种元素的相对灵敏度因子

采用标准溶液加入法往高纯氧化铋中加入混合标准溶液,烘干并研磨均匀,制备了5个高纯氧化铋的控制样品。再挑取适量的粉末样品压在高纯铟薄片上,建立了辉光放电质谱(GDMS)法校正高纯氧化铋中的Mg、Al、Ca等19种元素相对灵敏度因子的方法。实验考察了放电参数和制样面积对基体信号强度和稳定性的影响,优化后的辉光放电电流为1.8mA,放电电压为950V,压在铟薄片上的高纯氧化铋直径约为6～8mm。通过选择合适的同位素,在4000的中分辨率下测定即可消除质谱干扰。为了验证加标回收的准确性,采用电感耦合等离子体质谱(ICP-MS)法对控制样品进行测定,所有元素的加标回收率都在80%以上。采用GDMS法测定5个控制样品并结合ICP-MS法的测定值建立工作曲线,大部分元素的线性均达到0.995以上;除Al、Ga、Sb外,大部分元素的校准相对灵敏度因子(calRSF)和仪器自带的标准相对灵敏度因子(stdRSF)的比值都在1/2～2之间,说明GDMS的半定量分析不会有数量级的差别。但对于某些需要准确测定纯度的定量分析,则必须采用基体相匹配的RSF值进行校正。     

辉光放电质谱法测定纯锡中24种杂质元素和锡记忆效应的消除

采用辉光放电质谱法(GDMS)测定了纯锡中24种杂质元素,分析方法为无标定量分析。分析前纯锡样品须依次用乙醇、水及乙醇冲洗以除去表面的灰尘颗粒,凉干后用于分析。本工作对辉光放电过程中的三项关键因素,即辉光放电电压、放电电流及放电气流三者在辉光放电溅射/电离时的相互关系及其对总离子流强度的影响进行了试验和讨论,并确定了仪器在最佳状态时辉光放电的优化条件为:放电电压590V,放电电流30mA,放电气流450mL·min~(-1)。为排除各元素测定中质谱(MS)干扰的影响,选择了在不同的分辨模式(中/高)下用相对丰度较高、干扰较少的质量数进行分析。所测定元素测定结果的相对标准偏差(n=5)均小于15%。各元素的检出限(3s)为0.003～0.174μg·g~(-1)之间。本方法所得测定结果与电感耦合等离子体原子发射光谱法(ICP-AES)或电感耦合等离子体质谱法(ICP-MS)的测定结果基本一致。经试验,通过更换GDMS的阳极帽、导流管、采样锥和透镜等4种耗材,可完全消除锡的记忆效应。     

GD-MS法和ICP-MS法测定高纯铌中痕量元素

采用辉光放电质谱法(GD-MS)对高纯铌中Ta,Mo,W等痕量杂质元素进行了测试,并对GD-MS工作参数进行了优化,部分元素与采用电感耦合等离子体质谱法(ICP-MS)定量分析的结果进行比较,对某些元素含量差别较大的原因进行了分析,论述了Element GD辉光放电质谱仪的特点及其在痕量杂质分析上的优势。     

Inorganic trace analysis by mass spectrometry

Mass spectrometric methods for the trace analysis of inorganic materials with their ability to provide a very sensitive multielemental analysis have been established for the determination of trace and ultratrace elements in high-purity materials (metals, semiconductors and insulators), in different technical samples (e.g. alloys, pure chemicals, ceramics, thin films, ion-implanted semiconductors), in environmental samples (waters, soils, biological and medical materials) and geological samples. Whereas such techniques as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS) have multielemental capability, other methods such as thermal ionization mass spectrometry (TIMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS) have been used for sensitive mono- or oligoelemental ultratrace analysis (and precise determination of isotopic ratios) in solid samples. The limits of detection for chemical elements using these mass spectrometric techniques are in the low ng g⁻¹ concentration range. The quantification of the analytical results of mass spectrometric methods is sometimes difficult due to a lack of matrix-fitted multielement standard reference materials (SRMs) for many solid samples. Therefore, owing to the simple quantification procedure of the aqueous solution, inductively coupled plasma mass spectrometry (ICP-MS) is being increasingly used for the characterization of solid samples after sample dissolution. ICP-MS is often combined with special sample introduction equipment (e.g. flow injection, hydride generation, high performance liquid chromatography (HPLC) or electrothermal vaporization) or an off-line matrix separation and enrichment of trace impurities (especially for characterization of high-purity materials and environmental samples) is used in order to improve the detection limits of trace elements. Furthermore, the determination of chemical elements in the trace and ultratrace concentration range is often difficult and can be disturbed through mass interferences of analyte ions by molecular ions at the same nominal mass. By applying double-focusing sector field mass spectrometry at the required mass resolution—by the mass spectrometric separation of molecular ions from the analyte ions—it is often possible to overcome these interference problems. Commercial instrumental equipment, the capability (detection limits, accuracy, precision) and the analytical application fields of mass spectrometric methods for the determination of trace and ultratrace elements and for surface analysis are discussed.     

Characterization of high-purity aluminium

Summary The state of the art in characterization of high-purity aluminium, including activation analysis, glow discharge mass spectrometry (GDMS) and wet chemical multistep procedures has been described. It has been shown on the basis of comparative tests, in which laboratories in Europe, Japan and USA have participated, that with regard to power of detection as well as reproducibility even at levels below 500 ng/g neutron activation analysis (INAA, RNAA), wet chemical multistep procedures and GDMS can contribute to the characterization of high-purity aluminium. The measurement of the resistivity ratio have proved as a suitable test for the integral content of dissolved impurities. H at levels of 0.3 g/g can be measured by vacuum solid extraction or carrier gas fusion. For a complete and optimal characterization of high-purity aluminium all these methods are needed and should periodically be checked against each other.

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Charakterisierung von hochreinem Aluminium

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Thanks are expressed to VAW High-Purity Metal Division for allowing of publishing the foregoing results and financial support.     

无机质谱法在固体直接分析中的应用

本文归纳了无机质谱法在固体直接分析中的应用,并详细阐述了辉光放电质谱法(GDMS)、二次离子质谱法(SIMS)、激光溅射电感耦合等离子体质谱法(LA-ICPMS)和激光电离质谱法(LIMS)四种可用于固体样品直接检测的无机质谱法的检测原理、应用以及各自的优缺点.     

Investigations on cluster and molecular ion formation by plasma mass spectrometry

The formation of molecular and cluster ions of different inorganic materials in plasma mass spectrometry – spark source mass spectrometry (SSMS), radiofrequency glow discharge mass spectrometry (rf GDMS), laser ionization mass spectrometry (LIMS), inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) – was investigated and compared. Similar abundance distributions of cluster ions were observed for a graphite sample, for boron nitride/ graphite and for metal oxide/graphite mixtures using different plasma mass spectrometric methods. A correlation of intensities of metal argide ions in ICP-MS with their bond dissociation energies was used to estimate unknown dissociation energies of molecular ionic species. For the elements of the 2nd or 3rd period in the periodic table, the intensities of most argon molecular ions (ArX⁺) measured by ICP-MS rise with increasing atomic number in a similar manner to the theoretically calculated bond dissociation energies of argon molecular ions.     

Relative ion yields measured with a high-resolution glow discharge mass spectrometer operated with an argon/hydrogen mixture

Quantitative elemental analysis by glow discharge mass spectrometry (GDMS) requires a calibration factor for each element. The calibration factors used in the present work are called relative ion yields (RIYs). The RIYs of each of 19 elements within samples of four National Institute of Standards and Technology steel reference materials (nos. 661-664) were measured using pure argon and an argon mixture containing 1.0% hydrogen by volume. The RIYs measured using pure argon correlated within a factor of approximately 2–3 to the RIYs calculated by a theoretical model. The RlYs measured for these 19 elements using the argon mixture containing 1.0% hydrogen correlated within a factor of approximately 1.3 to the calculated RIYs. These results may have significant analytical potential with respect to GDMS and may have application to other plasma techniques.     

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.     

Characterization of high purity gallium

Multi-step wet analytical procedures were tested on gallium samples of different purity grades. Results obtained were compared with those of spark source mass spectrometry (SSMS) and glow discharge mass spectrometry (GDMS). It was found that multi-step procedures, as applied, with preconcentration factors of 200 are suitable to determine most of the detectable elements in high purity gallium in the ng/g-range. The results thus obtained agree well with those obtained by mass spectrometry. The sensitivity of the multi-step and mass spectrometry methods is not sufficient to detect traces of the investigated elements in super purity gallium, i.e. better than 6 N. These qualities can be differentiated, however, by single crystal resistivity measurement.     

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.