雷射剝蝕感應耦合電漿質譜儀（LA-ICPMS）具有總體（bulk）、微區（micro area）、直接（direct）、空間解析（spatially-resolved）及同位素（isotopic）分析等的功能，在環境、生物、地球化學及半導體材料等領域的研究中，扮演著舉足輕重的角色。分析化學家責無旁貸的解決LA-ICP-MS所面對的定量問題外，尋求LA-ICP-MS直測技術的跨領域合作，提供技術瓶頸之解決之道。
本論文分為兩部分。第一部份係利用LA-ICPMS建立單根毛髮空間解析分析技術，提供與一般血液及尿液樣本不同之生理訊息。本研究以鉈中毒患者之頭髮為樣本，利用具微區微量分析（micro trace analysis）能力之LA-ICPMS，對內含鉈元素之毛髮進行空間解析之定性及定量分析，時間解析度可達單日。本研究利用LA-ICPMS所建立的快速及簡單的毛髮截面元素分析技術，避免傳統毛髮截面前處理的繁瑣過程。利用具微區微量分析特性的LA-ICPMS，採用縱深解析（Depth resolved）的概念來執行線性直徑掃描分析，完全免除具高度經驗及技術性之包埋、切片等前處理過程。
第二部份探討固態樣品分析之定量方法。長久以來固體直測技術在進行定量分析時，總是需要面對基質匹配之固態標準品難求的問題。多年來陸續有液態標準品較正LA-ICPMS之定量方法發表，其成果雖有一定程度之績效，惟多數方法仍無法避免使用固態標準品的需求。因此本研究嘗試結合同位素稀釋法（Isotope dilution method）與雷射剝蝕感應耦合電漿質譜儀，不需藉由任何固態及內標準元素的使用，直接以液態標準品來做固態樣品的定量分析。本研究將此技術應用於矽晶圓中硼元素的量測，所得之偵測極限相當於2.8E15 atom/cm，藉由三個重複樣品的分析，精密度達到8％。至於準確度之評估，則利用本方法與濕式化學方法及四點探針法（four-point probe）進行方法間比對。由所得結果，發現本法之量測結果與濕式化學方法頗為ㄧ致，而四點探針法測值則偏低。整體而言on-line-LA-ICP-IDMS連線系統非常適合量測矽晶圓中微量硼元素。

Laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) is capable of direct analysis, bulk analysis, multi-elemental analysis, isotopic analysis, micro analysis, and spatially analysis. Therefore, applications of LA-ICPMS now span a great range of academic and industrial fields that include geological, archaeological, forensic, biological and material research. However, for quantification analysis, calibration remains a challenge for analysis of a wide variety of samples. In addition, upgrading the instrumentation, analyst should pay more attention to find the cooperation of different scientific field
There are two topics included in this work. Firstly, the aim of the present study was to utilize LA-ICPMS to establish a high spatially-resolved single hair analysis, including elemental retrospect analysis and cross-sectional analysis. Hair, one of the metabolic end products, can continuously record the physical status among its lifecycle. In particularly, metals can accumulated into the hair structure along a single strand during growth. In this study, a thallium-poisoned hair was investigated. The time resolution of the retrospect analysis can be down to one day. In this study, we established a ease and rapid cross-section elemental analysis method by utilizing the capability of depth profile and micro trace analysis of LA-ICP-MS to execute linear scan analysis across hair diameter without laborious pretreatment of hair embedding and cutting . Furthermore, the spatial resolution can be achieved down to 0.3~0.5 μm.
Secondly, we have developed a direct solid analysis method, based on the on-line isotope dilution technique coupled with laser ablation/inductively coupled plasma mass spectrometry (LA-ICP-MS), for the determination of boron in p-type silicon wafers. The laser-ablated sample aerosol was on-line mixed with an enriched boron aerosol supplied continuously using a conventional nebulization system. Upon mixing the two aerosol streams, the isotope ratio of boron changed rapidly and was then recorded by the ICP-MS system for subsequent quantification based on the isotope dilution principle. As an on-line solid analysis method, this system accurately quantifies boron concentrations in silicon wafers without the need for an internal or external solid reference standard material. Using this on-line isotope dilution technique, the limit of detection for boron in silicon wafers is 2.8 □ 1015 atoms cm–3. The analytical results obtained using this on-line methodology agree well with those obtained using wet chemical digestion methods for the analysis of p-type silicon wafers containing boron concentrations ranging from 1.0 □ 1016 to 9.6 □ 1018 atoms cm–3.

第一章 前言 1
1.1雷射剝蝕感應耦合電漿質譜儀在固體直測技術扮演的角色 1
1.1.1固體直測技術的重要性 1
1.1.2雙激發源固體直測技術的發展歷程 2
1.1.3雷射剝蝕感應耦合電漿質譜儀的發展歷程 3
1.1.4研究方向與目標 7
第二章 利用雷射剝蝕感應耦合電漿質譜儀進行單根頭髮中微量元素空間分佈之定性及定量分析 8
2.1前言 8
2.1.1雷射剝蝕感應耦合電漿質譜儀在生物監控上的應用 8
2.1.2元素在人體的組成及功能 10
2.1.3微量元素的監控模式 11
2.1.4生物監控的特性 11
2.1.5頭髮在生物監控所扮演的角色 12
2.1.6單根毛髮回溯分析及橫截面分析技術之回顧 14
2.1.7研究方向與目標 18
2.2實驗設計 18
2.2.1試劑來源 18
2.2.2樣品製備 19
2.2.3儀器裝置 19
2.3結果與討論 21
2.3.1單根頭髮之定性空間分析 21
2.3.2單根頭髮的定量空間分析 26
2.4結論 33
第三章 開發同位素稀釋法配合雷射剝蝕感應耦合電漿質譜儀進行矽晶圓中硼的定量分析 35
3.1前言 35
3.1.1固體直測技術的發展 35
3.1.2雷射剝蝕感應耦合電漿質譜儀定量方法回顧 36
3.1.3同位素稀釋法在定量分析上的演進 37
3.1.4研究方向與目標 37
3.2實驗設計 38
3.2.1試劑來源 38
3.2.2儀器裝置 38
3.2.3儀器參數及同位素稀釋法操作條件 39
3.3結果與討論 40
3.3.1同位素稀釋法訊號校正及數據處理 40
3.3.2雙導入系統之最佳化 43
3.3.3分析特色及應用 44
3.4結論 46
參考文獻 47

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