The Study of One-dimensional, Two-dimensional and Three-dimensional Elemental Distribution in Solids Using High Irradiance Laser Ionization Time-of-Flight Mass Spectrometry

随着材料科学的快速发展，传统的基于溶液的分析方法因为其繁琐的样品前处理、易引入污染以及只能提供样品整体的组成信息等不足已经远远满足不了现代科学的需求，因此发展固体直接分析法一直备受关注。 本课题组自行研制的低压氦气辅助高功率密度激光电离飞行时间质谱（LI-TOFMS）被证实是一项非常优越的固体直接分析技术，应用范围涵盖了导体，半导体和非导体领域，可以同时进行包括非金属元素在内的多元素快速分析；此外，该项技术还可以实现无标准样品校准的半定量分析，这在固体直接分析中是非常关键的，因为基质匹配的固体标准样品一般难以获得。本论文主要是基于该项技术发展其对实际固体样品组成的空间分布分析方法，其中包括有...With the rapid development of material science, the traditional solution-based analytical strategy is difficult to satisfy the requirement of modern science, which is attributed to its shortcomings, such as tedious pretreatment for sample, ease to be contaminated, limited capability to get rough composition information etc. Considering these, developing a method with the capacity to directly analy...学位：理学博士院系专业：化学化工学院_分析化学学号：2052012015348

The Technique of High Irradiance Laser Ionization Time-of-Flight Mass Spectrometry

对于传统的高功率激光质谱存在的关键问题,如离子动能分散、多价离子和多原子离子干扰、基体效应和分馏效应等,高功率激光电离飞行时间质谱(lI-TOf MS)通过仪器结构设计及实验条件的优化等可以很好地解决。目前,lI-TOf MS的应用包括地质和金属样品中元素的定性和无标样半定量分析、非金属元素的测定、元素表面成像分析和薄层的深度剖析、液体残渣分析、复杂生物材料中元素组成的确定,甚至对于有机金属化合物也可以同时获得分子、碎片和元素信息。本工作综述了lI-TOf MS技术的发展历程,分析了其在不同领域中的优势,并对其应用领域拓展的新方向和仪器的改进目标进行了展望。This article reviews the development and the applications of high irradiance laser ionization time-of-flight mass spectrometry(LI-Tof MS).The critical problems in traditional high irradiance laser mass spectrometry,such as the large kinetic energy distribution of ions,multiply charged ions,polyatomic ions,matrix effect as well as fractionation effect,have been successfully solved via the new design of instrumental structure as well as the optimization of the experiment conditions.Recent applications include qualitative and semiquantitative analysis of geological and metal solids without standards,determination of nonmetallic elements,elemental imaging and depth profiling of coatings,solution residue analysis,elemental analysis of complicated biomaterial,and simultaneous acquisition of elemental,fragmental,and molecular information on organometallic compounds,which demonstrates the high irradiance laser ionization time-of-flight mass spectrometry as a versatile technique in analysis.国家自然科学基金(21027011); 教育部创新团队基金(IRT13036)资

Mass Spectrometric Methods for Colorative Mechanism Analysis of Yaozhou Porcelain Glaze

采用实验室自制飞秒激光电离飞行时间质谱(fS-lI-TOfMS)对唐代、五代、宋代、金代以及明代等五个朝代的耀州窑古瓷片釉层进行多元素同时分析,研究其呈色机理,以过渡元素为重点考察陶瓷釉层中所有可能着色元素的着色效果。推测耀州黑瓷烧制采用的很可能是CO-Cr-fE-Mn系黑色釉料;明代白釉形成的主要原因是fE元素含量低,还有可能与nI元素有关;釉层中P元素含量增多会导致釉色偏黄。毫无疑问,这一系列发现是对整个耀州瓷体系釉层呈色机理的重要补充。An in-house-built femtosecond laser ionization time-of-flight mass spectrometry(fs-LI-TofMS)has been applied to the multi-elemental analysis of porcelain glaze from Yaozhou kiln.The samples are selected representing products of different dynasties,including Tang,Five,Song,Jin,and Ming Dynasty.For exploring the colorative mechanism of Yaozhou porcelain through the elemental analysis of the glaze,the effects of all potential coloring elements,especially transition elements,were considered.There was a speculation that the typical Co-Cr-Fe-Mn recipe was used in the fabrication of Yaozhou black glaze;the low content of Fe and high content of Ni resulted in the porcelain of white glaze;an increase content of P could lead the porcelain to be yellow-glazed.Undoubtedly,this research is an important supplement to the study of the colorative mechanism of the Yaozhou porcelain system.国家自然科学基金项目(21427813); 中央高校基本科研业务费项目(20720140539)资

Rapid Depth Profiling via High Irradiance Laser Ionization Orthogonal Time-of-Flight Mass Spectrometry

高功率激光电离垂直飞行时间质谱(lI-O-TOfMS)应用于薄层的深度分析是目前一项相对新颖的分析技术,不仅可以分析薄层的厚度,而且可以同时确定其中的元素组成及其随深度的分布情况。激光参数:波长532 nM,脉宽4.5 nS,功率密度9x109W/CM2。该项分析技术可以分析单镀层和多镀层的薄层样品。薄层的分辨厚度范围达到微米水平。相比其它薄层分析技术,lI-O-TOfMS是一项多功能的深度分析工具。As a relatively new technique,high irradiance laser( 4.5 ns,532 nm,9×109W / cm2) ionization orthogonal time-of-flight mass spectrometry( LI-O-TofMS) has been applied for depth profile analysis of various coated samples as well as element determination with respect to depth in solid samples.This technique is capable of performing depth profiling of coated layer with a thicknesses from sub-micrometer to tens micrometer scale; and can examine samples with monolayer and multilayer coated.Compared with other analytical techniques,LI-O-TofMS is a versatile analytical tool in rapid depth profiling of coated samples.国家质检总局科技计划项目(No.2013IK018); 国家自然科学基金项目(No.21027011)资助~