School of Earth, Atmospheric and Environmental Sciences, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Rapid Commun Mass Spectrom. 2009 Nov;23(21):3355-60. doi: 10.1002/rcm.4257.
Time-of-flight secondary ion mass spectrometry is a very useful tool for the comprehensive characterization of samples by in situ measurements. A pulsed primary ion beam is used to sputter secondary ions from the surface of a sample and these are then recorded by a time-of-flight mass spectrometer. The parallel detection of all elements leads to very efficient sample usage allowing the comprehensive analysis of sub-micrometre sized samples. An inherent problem is accurate quantification of elemental abundances which mainly stems from the so-called matrix effect. This effect consists of changes in the sputtering and ionization efficiencies of the secondary neutrals and ions due to different sample compositions, different crystal structure or even different crystallographic orientations. Here we present results obtained using C60 molecules as a new primary ion species for inorganic analyses. The results show an improvement in quantification accuracy of elemental abundances, achieving relative errors as small as the certified uncertainties for the analyzed silicate standards. This improvement is probably due to the different sputter mechanism for C60+ primary ions from that for single atomic primary ions such as Ga+, Cs+ or Ar+. The C60+ cluster breaks up on impact, distributing the energy between its constituent carbon atoms. In this way it excavates nano-craters, rather than knocking out single atoms or molecules from the surface via a collision cascade, leading to a more reproducible sputter process and much improved quantification.
飞行时间二次离子质谱是一种非常有用的工具,可通过原位测量对样品进行综合表征。脉冲式初级离子束用于从样品表面溅射次级离子,然后通过飞行时间质谱仪对其进行记录。所有元素的平行检测可实现非常高效的样品使用,从而允许对亚微米大小的样品进行综合分析。一个固有的问题是元素丰度的准确定量,这主要源于所谓的基质效应。这种效应包括由于不同的样品组成、不同的晶体结构甚至不同的晶体取向,导致次级中性粒子和离子的溅射和电离效率发生变化。在这里,我们展示了使用 C60 分子作为无机分析的新初级离子种类所获得的结果。结果表明,元素丰度的定量准确性得到了提高,对于分析的硅酸盐标准,相对误差可以小到分析证书中给出的不确定度。这种改进可能归因于 C60+初级离子与 Ga+、Cs+或 Ar+等单个原子初级离子的溅射机制不同。C60+团簇在撞击时会分解,将能量分配给其组成的碳原子。这样它就会挖掘出纳米级的陨石坑,而不是通过碰撞级联从表面敲出单个原子或分子,从而导致更可重复的溅射过程和大大提高的定量精度。