(1) 200416392 玖、發明說明 【發明所屬之技術領域】 本發明係關於藉離子移動率光譜測$法 與水之濃度的方法，與可進行此方法之系，統 【先前技術】 氫氣係廣泛地用於積體電路工業中$當 體。已知在製造此裝置時，所有使用材料之 要求，事貫上’可能存在於試劑或反應環境 入固態裝置而改變該固態裝置電氣性質，因 料。使用於製造之氣體的純度要求，可依製 體之特定方法而不同。通常，當氣體中雜 1 0 ppb (每十億份當中之份數，即，每1 〇9 一分子雜質）時認爲該氣體係適用於製造中 含量低於1 P P b。因此，能夠以精確和再現 體中極低雜質濃度係重要的。 可用於此目的之技術爲離子移動率光譜 界已知爲首字母縮略字IMS ;相同首字母縮 行此技術之儀器，在此例中意指「離子移動 此技術令人感到興趣的是其極高的靈敏度， 小及低成本；於適宜的條件下操作，氣體或 在兆分之一克（即，]〇_]2g )的量級，或濃 分之一（PPt，相當於每1 〇] 2樣品氣體分子 分析物質）的量級皆可在氣體介質中感測到 PCP Inc·爲名的美國專利案號5;4 5 7,3 1 6和 測量氫氣中氧 試劑氣體的氣 純度爲基本的 中的雜質會混 此造成生產廢 造商和使用氣 質含量不高於 總氣體分子對 ;較佳爲雜質 的方法測量氣 測定法，在業 略字也用於進 率光譜儀」。 附帶儀器尺寸 蒸氣物種的量 度在每百萬兆 對一分子之所 。以美國公司 5,955,886 ，以 (2) (2)200416392 及以申請人爲名的美國專利案號6,22 9, M3和PCT專利申 請案公告號 WO 02/40984，WO 02/052255 及 WO 02 / 0 5 4 0 5 8中已說明IMS儀器與使用這些儀器的分 析方法。 該技術之化學與物理原理，以及IM S儀器分析結果 說明，非常複雜。這些原理與結果的說明可參考書籍「離 子移動率光譜測定法」，由 G.A.Eiceman與Z.Karpas所 編纂，CRC出版社於1 994年出版。 簡言之，IMS儀器係由反應區、分離區和帶電顆粒收 集器構成。 包含輸送氣體中欲分析的氣體或蒸氣之樣品的離子化 通常藉63Ni發出之β射線於反應區中進行。離子化主要涉 及輸送氣體與所謂「試劑離子」形成之間的關係，接著該 試劑離子的電荷將依其電子或質子親合力的函數或離子電 位的函數分布於現有的物種上。 反應區藉由柵狀體與分離區分開，保持適當的電位時 ，該柵狀體能避免反應區產生的離子進入分離區。當柵狀 體電位消除的瞬間，使離子能進入分離區而提供分析的「 零時」。 分離區包含一組電極，由該組電極產生適於將離子輸 送至收集器之電場。在此區域中，提供與離子移動反方向 之氣流’以維持在大氣壓力。該逆向流動的氣體（在業界 定義爲「漂移氣體」）爲極純的氣體，該氣體可爲必須測 定雜質含量之氣體或不同的氣體。離子的移動速率依據電 場和氣體介質中之電場的截面而定，致使不同離子將以不 -6 - (3) (3)200416392 同時間越過分離區且到達顆粒收集器。在「零時」和到達 顆粒收集器之間的時間定義爲「飛行時間」。該收集器連 接到訊號製作系統，將以時間函數方式感測到的電流値轉 變爲最終圖形，其中顯示由波峰對應到不同離子的波峰之 「飛f了時間」函數，由此時間之測疋’得知可測定分析標 的之物質存在的試驗條件，然而，藉適當的運算系統可從 波峰區域估計所對應之物種的濃度。 然而，本發明者發現無法藉由上述所提及之原理以 I M S技術進行氫氣中氧與水的分析。 在實驗性硏究中，發明者首先發現爲了進行此分析， 必須使用選自氖、氬、氪和氙之稀有氣體充當漂移氣體， 因爲使用純的氫氣（亦即，該純的氣體相當於必須測定雜 質之氣體）時沒有波峰分離出來；在所引述的稀有氣體中 較佳者爲氬，因爲其在降低成本方面可提供最好的效果。 在這些條件下，由離子化構件形成之Η +與氬原子化合， 形成物種ArH+ (或與其他氬原子或其他中性分子結合而 形成其他更複雜的物種），爲此分析中之實際的反應物物 種。該ArH +物種以良好的效率將其電荷轉移到例如氮， N2，碳氧化物，CO和C02之分子，特別是以優異的效率 轉移到水分子，H20，致使這些存在氫氣中的雜質在IMS 分析中容易檢出。相反地，已注意到，電荷從ArH +轉移 到氧分子，〇 2，的反應效率幾乎爲零，致使由IM S氫氣 分析造成之光譜沒有相對於氧的波峰；結果’在此分析中 ，無法感測到氧的存在，甚至無法定性。 -7- (4) (4)200416392 【發明內容] 本發明之目的係提供藉離子化移動率光譜測定法測量 氨氣中氧與水之濃度的方法與系統。 此等_的係根據本發明而達成，本發明的第一目的在 於包含以下步驟的方法： a )對已去除氧與水之氫氣樣品進行第一次測量，以 測疋fe器之「背景」對水之測量的貢獻； b )對已去除水及視情況之其他雜質，但並非氧之相 同氫氣樣品進行第二次氧濃度之測量； c )對未經預先純化之氫氣樣品中的水濃度進行第三 次測量； d )比較步驟a、b、c三次測量的結果以單獨地測定 所分析之氫氣中的氧及水濃度； 其中，所有上述提及的測量係於IM S儀器的分離區 中使用選自氖、氬、氪和氙之中的漂移氣體進行，且至少 於b和c操作中，以所分析的氫氣樣品視情況需要在I M S 儀器的上游進行氧轉化成水的操作的方式操作，使得步驟 b中該轉化操作接著該去除水的步驟之後發生。 【實施方式】 在實驗過程中，發明者利用氫氣和已知量之氮、甲烷 '碳氧化物、水和氧等雜質所構成的樣品混合物進行許多 試驗。如先前提過的，儘管其他雜質在IMS光譜中會產 生波峰’但在氧的例子中並沒有觀察到波峰，即使當此雜 頁以較筒的濃度存在時也一樣。然而發明者注意到增加進 -8- (5) 200416392 入儀器之氫氣樣品的氧濃度，會增加水波峰的強度。 增加與進入氣體中之氧濃度並非呈線性的關係；此外 增加在不同IMS儀器，或甚至之後以相同的儀器測 不具再現性。 雖然尙未對該現象加以完整說明，但咸認爲依據 的運作條件、試驗溫度（於大約8 0至1 2 0 °C間）， 能由該儀器器壁之催化效應的結果，在儀器內側有一 氧會轉化成水。因爲轉化的程度無法預知，一部分氧 持分子物種的形式，因此在分析中無法感測到，然而 一部分係轉化成水且導致相關波峰強度的增加，因此 此物種濃度的讀數。 根據本發明的方法解決這些問題，能利用IMS 獲得氫氣中的氧與水之定量的及定性的測量。 因爲水在IM S測量中總以「背景」的形式存在 於水從儀器壁上緩慢脫附）’所以本方法的第一步馬: ，在於估計「背景」的量，而可於後續測量中加以考 藉由氫氣樣品之第一次IMS分析而進行，該第一次 分析已事先使此氫氣樣品進行氧與水去除步驟：以此 使第一次試驗中測得的水僅來自「背景」，而不含導 體的貢獻。氧與水的去除可以热體純化益元成，其貫 將說明於後。 根據本發明之方法的第二步驟中’ b，在相同氫 品中之水濃度的第二次1 M S測量係先對該氫氣樣品 部分純化步驟，其中將水和其他視情況需要之氧以外 質從氣體中去除，然後進行氧轉化成水的步驟。在此 但此 ，此 量並 儀器 也可 部分 仍保 ，另 改變 技術 (由 ^ 5 a 慮。 IMS 方法 入氣 施例 氣樣 進行 的雜 方法 (6) (6)200416392 中，第二次試驗中測得的的水量係由氧所形成的水和「背 景」的水構成。 本發明方法的第三步驟中’ c ’相同氫氣樣品之水濃 度的第三次測量係於相同氯氣樣品中進行’該氫氣樣品未 經事先純化，但在導入1MS儀器之前先經氧轉化成水的 步驟。在此試驗中，所測量的水量係由此三種貢獻構成， 即「背景」水，由氫氣中的雜質氧所形成的水，以及原本 存在氫氣中的雜質水。 φ 本方法的最後一步驟，d，在於比較步驟a、b、c三 次測量的結果以獨立地測定所分析之氫^氣中的氧與水之濃 度。特別是利用如下式之[H2〇]a，[H2〇]b和[H2〇]e表示三 試驗中獲得之水濃度測量結果： [H20]a係相當於儀‘器的水「背景」； 從減法[H20]b，[H2〇]。得到之値係從存在於初始氯氣 樣品中之氧衍生得到的水濃度；由此得到以下的反應化學 計量： φ Ο 2 + 2 Η 2 + 2 Η 2 〇 由此獲得原本存在於氫氣樣品中的氧濃度，該氧濃度 爲以上提供之減法所獲得之水濃度的一半； 最後，由減法[Η 2 〇 ] C - { [ Η 2 0 ] b + [ Η 2 0 ] a }算出的値爲原 本以雜質的形式存在氫氣樣品中的水濃度値。 顯然步驟a、b和C也能依不同於上述所指的時序進 行；同樣地，由步驟d的運算可於不同時間進行。例如’ 一系列步驟a、b和C結束時一起進行，或減法步驟（由 彼可得到從氧衍生得到之水濃度）能在試驗b之後進行’ -10- (7) (7)200416392 最後減法操作（由彼可得到實際上以雜質形式存在於最初 樣品中之水量）能於一系列試驗步驟結束時進行。運算步 驟較佳以自動化方法進行，例如，藉由微處理器同樣可以 適當的演算法從光譜波峰強度獲得[H20]a ’ [H2〇]b和 [H20]e 的値。 本發明的第二目的中，本發明係關於可進行上述方法 的系統。此系統包含： 一 IMS光譜儀； 一管線，用以將欲分析之氫氣樣品注入系統中； -至少一流體變向裝置構件，能使氣流沿著至少三次 要管線改道進入系統中； -第一次要管線，其上供有能去除存在於氫氣流中的 氧與水之第一氣體純化器； -第二次要管線，其上供有能去除水和其他視情況需 要之氧以外的雜質之第二氣體純化器； 一第三次要管線； 一流體選擇構件，試圖每次僅沿著該次要管線其中之 一直接將流體導入系統中； 一至少一該三次要管線之接合配件，位於IMS光譜 儀之上游或入口； -至少一轉化器，能將氧完全地轉化成水，在該第二 純化器的T游位置，使得該第三次要管線中的氫氣流在進 入光譜儀之前會先經過轉化器的位置。 根據本發明的系統容許不同的替代實施例。 例如’該三次要管線可保持平行直至進入IMS儀器 (8) (8)200416392 ’再以配件接合；在此實施例中，在第二和第三次要管線 上需要二獨立的氧轉化成水的轉化器。然而，該二轉化器 較佳以單一轉化器取代；在此例中，至少該第二和第三次 要管線必須藉由適當的配件接合，進入該唯一轉化器上游 的單一管線；第一次要管線可接合到該轉化器下游或該轉 化器上游的最後管線；在後面的範例中，三次要管線較佳 係藉由單一四通配件接合成單一管線，其爲類似一設置於 三次要管線上游之變向裝置的第二流體變向裝置構件。容 許流體選擇次要管線之一，使該流體沿著該管線導入系統 中的元件可爲各種類型：爲方便起見，使用於該次要管線 之各個上設置開關閥門的類型。 第1圖顯示本發明之較佳實施例，其使用單一氧轉化 成水之轉化器並將配件和熔接數目減至最小。系統1 〇包 含將系統連至所分析之氣體進入的管線所用的管線1 1， 以及用於選擇性地使氣流偏向，從管線1 1沿著次要管線 1 3，1 3 ’或]3 ”其中之一進入的構件1 2。然後使該三次要 管線藉由I M S儀器上游之單一管線]4中的構件1 2 5接在 一起。開關閥門1 6，1 6 ’和]6”係設置在該三次要管線之 各個上；藉由每次僅打開這些開關閥門的其中之一，使氣 流沿著所選擇之次要管線通往IMS儀器；該三個閥門係 示於圖中正好在構件1 2 ’上游，而且該閥門可設置在次要 管線的任何位置上。第一純化器1 7沿著第一次要管線， 1 3，設置，能從經過該管線之氫氣流中去除氧和水；第二 純化器1 8沿著第二次要管線設置，能從經過管線1 3，之 氫氣流中去除水和氧以外之其他視情況需要的任何雜質； -12- 200416392 Ο) 最後，在管線I 3 ”上沒有純化器。氧轉化成水的轉化器j 9 係沿管線1 4設置。 根據本發明的方法係以僅有其中之一次要管線的氣流 係選擇性地傳送至儀器1 5的方式，藉由適當的操作閥j 6 ，：1 6 ’和1 6 ”利用系統1 0進行；尤其，步驟&係藉來自管 線1 3之氣流傳送至儀器而進行，步驟b係藉來自管線 1 3 ’之氣流傳送至儀器而進行，及步驟c係藉來自管線1 3，’ 之氣流傳送至儀器而進行。 系統1 〇係以超純氣體管線領域的標準材料及技術生 產，例如使用氣體管線用的鋼製輸送管線、鋼製閥門以及 在系統運作之前，透過加熱對系統進行脫氣處理。 純化器1 7可爲鈀膜型，但基於經濟上的考量，最好 使用鎳系純化器，其可在室溫時運作。在這些純化器中， 金屬通常以具有高比表面積之支撐物，例如矽，上的沈積 物之形式存在；此種鎮系純化器係由例如美國S a n L U i s Obispo的SAES pure Gas公司所生產。 純化器]8必須能去除水和氧以外其他視情況需要的 任何雜質。例如，可能使用以沸石爲主的純化器，藉由在 約-5 0 °C至室溫之間的溫度時運作，能去除水和其他易於 濃縮的雜質，例如C02，但並非氧。較佳也可使用以化學 吸濕劑爲主之純化器，在室溫時運作；一些實施例係以氧 化硼爲主的純化器，該純化器可選擇性地去除水，或以鹼 土金屬氧化物爲主之純化器，可有效地去除水且，隨之也 可吸附C 0 2 ;基於經濟上的考量，較佳的鹼土金屬氧化物 係氧化鈣。此等純化器係由一般由鋼製的本體形成，該鋼 -13 - (10) (10)200416392 製本體裝備有用以連接（在入口和出口）到氣體管線之二 配件，且在本體內部中，吸濕材料通常呈分散形式（例如 ’粉末）並由網子或金屬過濾器保持，以免材料顆粒被氣 流輸送至純化器下游。使用於這些純化器之沸石在市面上 可由，例如美國公司 G 1· a c e D a v i s ο η，B a 11 i rn 〇 r e 5 Μ μ y 1 a n d ’或法國公司CEC A，Paris La Defence購得；驗土金屬和 氧化硼由化學產品零售商，例如A 1 d l. i c h，M e r c k等等販售 ;以氧化硼充當吸濕劑係以申請人之名說明於美國專利第 6,3 04,3 6 7 號中。 轉化器1 9必須能完全將氧轉化成水。此轉化器具有 與純化器1 8相似的構造，具有金屬本體，其中包含在轉 化過程中具有活性的材料，通常爲網狀，海綿狀或以分散 形式沉積在支撐物’例如用於催化應用之陶瓷或沸石支撐 物，上的過渡金屬。較佳係使用含鈀催化床的轉化器，或 基於經濟上的考量而使用鎳；在後面的例子中可以網狀或 海綿狀的方式使用鎳’且在高於1 〇 〇 °c的溫度時發生轉化 。可用於本發明之目的的海綿狀鎳，由英國，Wales， S w a n s e a的IN C 0公司所販售。 本發明更進一步藉由以下實施例說明。試驗結果顯示 在圖形中’其中顯示離子的飛行時間函數之波峰，以毫秒 (m s )爲單位；該波峰對應到不同離子濃度之面積。此等 離子大體上係視情況需要與更多輸送氣體分子結合之複雜 物種，可包含一、二或更多離子化氣體的分子，但爲求簡 化起見，圖式中的主要波峰以分子物種的簡式加以區分， 代替對應離子的實際化學式；例如，圖式上Η 2 Ο表示可 • 14- (11) (11)200416392 歸因於水的存在之離子’（H20)2表示對應到含水二聚體的 離子之離子，而RIΡ表示反應物離子，亦即A r Η +。波峰 強度以伏特（V )爲單位表示；藉由收集器直接測量轉換 成電流伏特數（時間單位內碰撞收集器之離子數目）係藉 由電子儀器進行。樣品離子化係藉由03Ni放射源而獲得 。儀器之分離區爲8 c m長；在所有試驗中，施加的電場 皆爲 1 2 8 V / c m。 實施例1 此例係根據本發明方法的操作a之進行的說明。 對已去除所有雜質之氫氣樣品進行IMS分析以測定 系統背景對水的測量之貢獻。該試驗用第1圖的系統進行 ，藉由通過其上装備純化益1 7之管線1 3 ’藉著將5 p p b 的水（藉由美國，德州，K1N-TEK of La Marque公司的校 正系統）添加至包含 5 ppb氧的氫氣（由義大利， B e r g a m 〇的S I A D公司提供）而製得氣體混合物；由系統 1 0之構造使純化步驟衍生得到之氣流經過將氧轉化成水 的轉化器，]9，即使此例中不需要最後的步驟也是一樣， 最後傳送至ί M S儀器1 5。該儀器之溫度保持恆定在1 〇 〇 °C，且使用純的氬充當漂移氣體，而樣品和漂移氣體間之 流動速率爲1 · 2 : 2 0。試驗結果示於第2圖之曲線a。 實施例2 此例係根據本發明方法的步驟b之進行的說明。 重複實施例〗的試驗，但傳送至IM S儀器時由起始 -15- (12) (12)200416392 混合物衍生得到之氣體已經先通過管線1 3 ’，因此只有水 被去除’然後再通過轉化器1 9。該S式驗結果不於弟2圖 之曲線b。 實施例3 此例係根據本發明方法的步驟c之進行的說明。 重複實施例1的試驗，但傳送至IMS儀器時起始混 合物已經先通過管線1 3 ”，因此無需任何純化步驟，然後 再通過轉化器1 9。該試驗結果示於第2圖之曲線c。 注意從第2圖之曲線圖的分析，經過條件a到c可歸 因於水和其二聚體的波峰強度呈規律地增加，然而反應物 離子之強度則降低。 在第一次試驗中，系統的運算系統測定冰濃度相當於 3 . ] p p b，代表系統的「背景」。 在第一次試驗中，由儀器測得的値爲1 1 . 6 p p b，減去 背景可獲得8 .5 ppb的値：將已傳送到儀器的5 ppb氧列 入考慮時，該5 p p b的氣轉化成1 0 p p b的水，在此例中 ，得到低於正確値1 5 %之「讀數」，在此雜質濃度値之下 ，該讀數爲可接受的數値。 最後’在第三次試驗中所有的貢獻皆存在，亦即「背 〃宁、」’仗氧衍生得到之水和原本存在樣品中的水；在此例 中儀器之「讀數」爲18.3 ppb，減去「背景」的3 l ppb 和從氧衍生得到之水】〇 ppb，獲得水之讀數爲5.2 ppb， 相對於正確値的誤差爲超過4 %，爲優異的結果。 因此根據本發明之方法和系統能以良好的可靠度、彼 -16- (13) (13)200416392 此獨立地測定氫氣樣品中的氧與水之濃度。 【圖式簡單說明】 以下本發明將參照圖式加以說明，其中： 第1圖槪略地顯示可將本發明的方法付諸實行之氣體 管線系統，該系統包含純化器和氧轉化成水的轉化器； 第2圖顯示對應於本發明方法的不同步驟之IM S氫 氣分析結果。 元件符號 10 系統 11 管線 12 構件 12， 接合配件 13 第一*次要管線 13’ 第二次要管線 13” 第三次要管線 14 單一管線 15 離子移動光譜儀 16 開關閥門 16’ 開關閥門 16” 開關閥門 1 7 第一純化器 18 第二純化器 19 轉化器 -17-(1) 200416392 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for measuring the $ method and the concentration of water by an ion mobility spectrum, and a system that can perform this method. [Prior technology] The hydrogen system is extensive Ground is used in the integrated circuit industry. It is known that in the manufacture of this device, all the requirements for the materials used may invariably exist in the reagent or the reaction environment into the solid-state device to change the electrical properties of the solid-state device. The purity requirements of the gases used in manufacturing may vary depending on the specific method of the system. Generally, when the gas is 10 ppb (parts per billion parts, that is, one molecule per 109 parts of impurities), the gas system is considered suitable for manufacturing with a content of less than 1 P P b. Therefore, it is important to be able to accurately and reproduce extremely low impurity concentrations in the volume. Techniques that can be used for this purpose are known in the ion mobility spectrum world as the acronym IMS; instruments with the same acronym for this technique, meaning in this case "Ion mobility is very interesting because it is extremely high The sensitivity, small and low cost; operating under appropriate conditions, the gas may be on the order of one trillionth of a gram (that is,] 〇] 2g), or one part of a concentration (PPt, equivalent to 1 〇] 2 sample gas molecular analysis substance) can be sensed in the gas medium in the name of PCP Inc. US Patent No. 5; 4 5 7, 3 1 6 and measuring the gas purity of oxygen reagent gas in hydrogen is basic Impurities in the mixture will cause production waste manufacturers and use gas content not higher than the total gas molecular pairs; the method of measuring impurities is preferred, which is also used in the rate spectrometer in the industry. Attached Instrument Size Vapor species are measured in one molecule per million trillion pairs. U.S. company 5,955,886, U.S. Patent No. 6,22 9, (2) (2) 200416392, and the applicant name, M3 and PCT Patent Application Publication Nos. WO 02/40984, WO 02/052255, and WO 02 / 0 5 4 0 5 8 IMS instruments and analytical methods using these instruments are described. The chemical and physical principles of this technology, as well as the analysis results of IMS instruments, are very complex. A description of these principles and results can be found in the book "Ion Mobility Spectroscopy", compiled by G.A. Eiceman and Z. Karpas, and published by CRC Press in 1994. In short, the IMS instrument consists of a reaction zone, a separation zone, and a charged particle collector. The ionization of the sample containing the gas or vapor to be analyzed in the transport gas is usually carried out in the reaction zone by beta rays emitted by 63Ni. Ionization mainly involves the relationship between the transport gas and the formation of the so-called "reagent ion", and then the charge of the reagent ion will be distributed to existing species as a function of its electron or proton affinity or as a function of ion potential. The reaction zone is separated from the separation zone by a grid. When the proper potential is maintained, the grid can prevent ions generated in the reaction zone from entering the separation zone. The moment the grid potential is eliminated, the ions can enter the separation zone and provide the "zero-hour" of analysis. The separation zone contains a set of electrodes from which an electric field suitable for transmitting ions to the collector is generated. In this region, a gas flow 'is provided in the direction opposite to the ion movement to maintain the atmospheric pressure. The gas flowing in the reverse direction (defined as "drift gas" in the industry) is an extremely pure gas, which can be a gas whose impurity content must be measured or a different gas. The moving speed of the ions depends on the electric field and the cross section of the electric field in the gas medium, so that different ions will pass through the separation zone and reach the particle collector at the same time at a time of -6-(3) (3) 200416392. The time between "zero hour" and arrival at the particle collector is defined as "time of flight". The collector is connected to a signal production system and converts the current sensed as a function of time into a final graph, which shows the "flying time" function corresponding to the peaks of different ions. 'I know the test conditions that can determine the existence of the target substance for analysis, but the concentration of the corresponding species can be estimated from the peak region by an appropriate computing system. However, the present inventors have found that the analysis of oxygen and water in hydrogen cannot be performed by the IMS technique by the above-mentioned principle. In an experimental investigation, the inventors first discovered that in order to perform this analysis, a rare gas selected from neon, argon, krypton, and xenon must be used as the drift gas, because pure hydrogen (that is, the pure gas is equivalent to the necessary There is no peak separation when measuring the gas of impurities); among the rare gases cited, argon is preferred because it provides the best effect in terms of cost reduction. Under these conditions, the Η + formed by the ionized member is combined with the argon atom to form the species ArH + (or combined with other argon atoms or other neutral molecules to form other more complex species), which is the actual reaction in this analysis Species. The ArH + species transfers its charge to molecules such as nitrogen, N2, carbon oxides, CO, and CO2 with good efficiency, especially to water molecules, H20 with excellent efficiency, causing these impurities in hydrogen to be present in the IMS Easy to detect during analysis. On the contrary, it has been noticed that the charge transfer efficiency from ArH + to the oxygen molecule, 〇2, is almost zero, so that the spectrum caused by the hydrogen analysis of IM S does not have a peak relative to oxygen; the result 'In this analysis, it was not possible The presence of oxygen is sensed and cannot even be characterized. -7- (4) (4) 200416392 [Summary of the Invention] The object of the present invention is to provide a method and system for measuring the concentration of oxygen and water in ammonia by ionization mobility spectrometry. These systems are achieved according to the present invention. The first object of the present invention is a method including the following steps: a) The first measurement is performed on a hydrogen sample from which oxygen and water have been removed to measure the "background" of the device. Contribution to the measurement of water; b) the second measurement of the oxygen concentration of the same hydrogen sample from which water and other impurities have been removed but not oxygen; c) the water concentration of the hydrogen sample without prior purification Perform the third measurement; d) Compare the results of the three measurements in steps a, b, and c to individually determine the oxygen and water concentrations in the analyzed hydrogen; where all the above-mentioned measurements are in the separation zone of the IM S instrument Using a drift gas selected from neon, argon, krypton, and xenon, and at least in operations b and c, with the hydrogen sample being analyzed as required, the operation of converting oxygen to water upstream of the IMS instrument as appropriate Operate such that the conversion operation in step b occurs after the step of removing water. [Embodiment] During the experiment, the inventor conducted many experiments using a sample mixture composed of hydrogen and known amounts of impurities such as nitrogen, methane, carbon oxides, water, and oxygen. As mentioned earlier, although other impurities may generate peaks' in the IMS spectrum, no peaks were observed in the oxygen example, even when this impurity is present at a more concentrated concentration. However, the inventors noticed that increasing the oxygen concentration of the hydrogen sample into the instrument would increase the intensity of the water peaks. The increase is not linearly related to the oxygen concentration in the incoming gas; furthermore, the increase is not reproducible when measured on different IMS instruments, or even with the same instrument. Although this phenomenon has not been fully explained, Xian believes that the operating conditions and test temperatures (between about 80 and 120 ° C) can be determined by the catalytic effect of the wall of the instrument on the inside of the instrument. One oxygen will turn into water. Because the degree of transformation is unpredictable, part of the oxygen is in the form of a molecular species and therefore cannot be sensed in the analysis. However, part of it is converted to water and results in an increase in the intensity of the relevant peaks, so the concentration of this species is read. The method according to the present invention solves these problems, and can use IMS to obtain quantitative and qualitative measurements of oxygen and water in hydrogen. Because water always exists in the form of "background" in the measurement of IMs, the water is slowly desorbed from the wall of the instrument.) Therefore, the first step of this method is to estimate the amount of "background", which can be used in subsequent measurements. This is done by the first IMS analysis of the hydrogen sample, which has been subjected to the oxygen and water removal steps in advance: this way the water measured in the first test comes only from the "background" Without the contribution of a conductor. Removal of oxygen and water can be purified by hot body, which will be described later. In the second step of the method according to the present invention, 'b, the second 1 MS measurement of the water concentration in the same hydrogen product is a partial purification step of the hydrogen sample, in which water and other oxygen as needed It is removed from the gas and then the step of converting oxygen to water is performed. Here, however, the quantity and equipment may be partially guaranteed, and the technology is changed (considered by ^ 5a. IMS method, gas sample, gas sample, and other methods (6) (6) 200416392, the second test The amount of water measured in the experiment is composed of water formed by oxygen and "background" water. In the third step of the method of the present invention, the third measurement of the water concentration of the same hydrogen sample in 'c' was performed in the same chlorine gas sample. 'The hydrogen sample was not purified in advance, but was first converted to water by oxygen before being introduced into the 1MS instrument. In this experiment, the measured water volume was composed of three contributions, namely "background" water, which The water formed by the impurity oxygen, and the impurity water originally existing in hydrogen. Φ The last step of the method, d, is to compare the results of the three measurements of steps a, b, and c to independently determine the hydrogen in the analyzed gas. The concentration of oxygen and water. In particular, the following formulas [H2〇] a, [H2〇] b and [H2〇] e are used to represent the water concentration measurement results obtained in the three tests: [H20] a is equivalent to the instrument Water "background"; from subtraction [H20] b, [H2〇]. The obtained hydrazone is the water concentration derived from the oxygen present in the initial chlorine gas sample; thus the following reaction stoichiometry is obtained: φ Ο 2 + 2 Η 2 + 2 Η 2 〇 Thus, the original Oxygen concentration, which is half of the water concentration obtained by the subtraction provided above; finally, 値 calculated from the subtraction [Η 2 〇] C-{[Η 2 0] b + [Η 2 0] a} is the original The water concentration 値 in the hydrogen sample exists as an impurity. Obviously, steps a, b, and C can also be performed at a different time sequence than the above; similarly, the operation of step d can be performed at different times. For example, 'a series Steps a, b, and C are performed together, or the subtraction step (from which the water concentration derived from oxygen can be obtained) can be performed after test b '-10- (7) (7) 200416392 The final subtraction operation (by another The amount of water that can actually be present in the original sample as impurities can be obtained at the end of a series of experimental steps. The calculation steps are preferably performed automatically, for example, the microprocessor can also perform appropriate algorithms from the spectral peaks strength Obtain [H20] a '[H2O] b and [H20] e. In a second object of the present invention, the present invention relates to a system capable of performing the above method. The system includes: an IMS spectrometer; a pipeline, To inject the hydrogen sample to be analyzed into the system;-at least one fluid redirecting device component, which can redirect the gas flow into the system along at least three major pipelines;-the first major pipeline, on which the hydrogen present can be removed A first gas purifier for oxygen and water in the stream; a second secondary line on which a second gas purifier capable of removing impurities other than oxygen as needed from the oxygen is provided; a third secondary line A fluid selection member that attempts to direct the fluid directly into the system along only one of the secondary pipelines at a time; a joint fitting for at least one of the three secondary pipelines located upstream or at the inlet of the IMS spectrometer;-at least one converter It can completely convert oxygen into water. At the position T of the second purifier, the hydrogen flow in the third secondary pipeline will pass through the position of the converter before entering the spectrometer. The system according to the invention allows different alternative embodiments. For example, 'The three minor pipelines can remain parallel until entering the IMS instrument (8) (8) 200416392' and then joined with fittings; in this embodiment, two separate oxygens are required to be converted into water on the second and third minor pipelines. Converter. However, the two converters are preferably replaced by a single converter; in this example, at least the second and third secondary lines must be joined by suitable fittings to enter a single line upstream of the single converter; the first time The main pipeline can be connected to the downstream of the converter or the last pipeline upstream of the converter; in the following example, the third pipeline is preferably connected to a single pipeline by a single four-way fitting, which is similar to the one provided in the third pipeline. The second fluid redirecting device component of the redirecting device upstream of the pipeline. The fluid is allowed to select one of the secondary lines so that the components along which the fluid is introduced into the system can be of various types: for convenience, the type of on-off valve used on each of the secondary lines. Figure 1 shows a preferred embodiment of the present invention which uses a single oxygen to water converter and minimizes the number of fittings and welds. System 10 includes line 11 for connecting the system to the line where the gas being analyzed enters, and for selectively biasing the gas flow from line 11 along the secondary line 1 3, 1 3 'or] 3 " One of them enters the component 1 2. Then the three main pipelines are connected together through the components 1 2 5 in the single pipeline upstream of the IMS instrument. The on-off valves 16, 16 'and] 6 ”are arranged at Each of the three major pipelines; by opening only one of these switching valves at a time, the air flow is routed along the selected minor pipeline to the IMS instrument; the three valves are shown in the figure exactly at component 1 2 'upstream, and the valve can be placed anywhere on the secondary line. The first purifier 17 is installed along the first main line, 1 3, and can remove oxygen and water from the hydrogen stream passing through the line; the second purifier 18 is installed along the second main line, and can be removed from After the line 1 3, the hydrogen stream removes any impurities other than water and oxygen as needed; -12-200416392 〇) Finally, there is no purifier on line I 3 ”. Converter for converting oxygen to water j 9 It is arranged along the pipeline 14. The method according to the invention is such that only one of the secondary pipelines is selectively delivered to the instrument 15 by means of an airflow system, by appropriately operating the valve j 6: 1 6 ′ and 1 6 "is performed using system 10; in particular, step & is performed by transmitting air flow from line 13 to the instrument, step b is performed by transmitting air flow from line 13 'to the instrument, and step c is performed by The flow of lines 1 3, 'is transmitted to the instrument. System 10 is produced with standard materials and technologies in the field of ultra-pure gas pipelines, such as the use of steel pipelines for gas pipelines, steel valves, and degassing of the system by heating before the system operates. The purifier 17 may be a palladium membrane type, but for economic reasons, it is preferable to use a nickel-based purifier, which can be operated at room temperature. In these purifiers, the metal is usually in the form of a deposit with a high specific surface area, such as silicon; such town-type purifiers are produced by, for example, SAES pure Gas Company of San Lu is Obispo, USA . The purifier] 8 must be able to remove any impurities other than water and oxygen, as needed. For example, it is possible to use a zeolite-based purifier that can remove water and other easily-concentrated impurities, such as CO2, but not oxygen, by operating at temperatures between about -50 ° C and room temperature. A purifier based on a chemical hygroscopic agent is also preferred, and operates at room temperature; some embodiments are purifiers based on boron oxide, which can selectively remove water or oxidize with alkaline earth metals The material-based purifier can effectively remove water and can also adsorb C 0 2; based on economic considerations, the preferred alkaline earth metal oxide is calcium oxide. These purifiers are generally formed of a steel body. The steel -13-(10) (10) 200416392 body is equipped with two fittings to connect (at the inlet and outlet) to the gas line and is inside the body. In general, hygroscopic materials are usually in a dispersed form (such as 'powder') and held by a mesh or metal filter to prevent material particles from being transported downstream of the purifier by the air stream. The zeolites used in these purifiers are commercially available from, for example, the American company G 1 · ace D avis ο η, B a 11 i rn 〇re 5 μ y 1 and 'or the French company CEC A, Paris La Defence; Soil testing metals and boron oxide are sold by chemical product retailers such as A 1 d l. Ich, Merck, etc .; the use of boron oxide as a hygroscopic agent is described in the name of the applicant in US Patent No. 6,3 04, 3 6 7 in. The converter 19 must be able to completely convert oxygen into water. This converter has a similar structure to the purifier 18, with a metal body containing materials that are active during the conversion process, usually in the form of a net, sponge or deposited on a support 'for example for catalytic applications Ceramic or zeolite support, transition metal on. It is preferred to use a palladium-containing catalyst bed, or use nickel based on economic considerations; in the following examples, nickel can be used in a mesh or sponge-like manner and at temperatures above 1000 ° C. Conversion takes place. Spongy nickel which can be used for the purpose of the present invention is sold by the company IN C 0, Wales, Swaan sea, UK. The invention is further illustrated by the following examples. The test results are shown in the graph, where the peaks of the time-of-flight function of the ions are shown in milliseconds (m s); the peaks correspond to areas with different ion concentrations. This plasma is generally a complex species that needs to be combined with more transported gas molecules, depending on the situation. It can contain one, two or more molecules of ionized gas, but for simplicity, the main peaks in the diagram are based on the molecular species. Distinguish the short form, instead of the actual chemical formula of the corresponding ion; for example, Η 2 〇 on the figure indicates that it can be • 14- (11) (11) 200416392 The ion attributed to the presence of water '(H20) 2 means that it corresponds to water Polymer ion, and RIP stands for reactant ion, that is, A r Η +. The peak intensity is expressed in units of volts (V); the direct measurement by the collector into the current volts (the number of ions that hit the collector in time units) is performed by electronic instruments. Sample ionization was obtained with a 03Ni radiation source. The separation zone of the instrument is 8 cm long; in all tests, the applied electric field was 128 V / cm. Example 1 This example is a description of operation a according to the method of the present invention. IMS analysis was performed on a hydrogen sample with all impurities removed to determine the contribution of the system background to the measurement of water. The test was performed using the system of Figure 1 by equipping Purification 17 with a pipeline 13 'through 5 ppb of water (by the K1N-TEK of La Marque, Texas, USA calibration system). A gas mixture was prepared by adding 5 ppb of oxygen to hydrogen gas (supplied by SIAD, Bergamo, Italy); the structure of system 10 allowed the gas stream derived from the purification step to pass through a converter that converts oxygen to water, ] 9, even if the last step is not needed in this example, it is finally transferred to the MS instrument 1 5. The temperature of the instrument was kept constant at 1000 ° C, and pure argon was used as the drift gas, and the flow rate between the sample and the drift gas was 1 · 2: 2 0. The test results are shown in curve a in FIG. 2. Example 2 This example is a description of step b according to the method of the present invention. The test of the example was repeated, but the gas derived from the starting -15- (12) (12) 200416392 mixture had been passed through the line 1 3 'when transferring to the IMS instrument, so only water was removed' and then passed through the conversion器 1 9. The result of the S-type test is not the same as the curve b in Figure 2. Example 3 This example is a description of step c of the method of the present invention. The test of Example 1 was repeated, but the starting mixture had already passed through the line 13 "when transferred to the IMS instrument, so no purification step was required before passing through the converter 19. The results of this test are shown in curve c in Figure 2. Note that from the analysis of the graph in Figure 2, after conditions a to c, the peak intensities attributable to water and its dimers increase regularly, but the intensity of the reactant ions decreases. In the first test, The system's computing system measures the ice concentration to be equivalent to 3] ppb, which represents the "background" of the system. In the first test, the radon measured by the instrument was 11.6 ppb, and the background was subtracted to obtain 8.5 ppb of radon: When 5 ppb oxygen transferred to the instrument was taken into account, the 5 ppb The gas is converted to 10 ppb of water. In this example, a "reading" below 15% of the correct value is obtained. Below this impurity concentration, the reading is an acceptable number. Finally, in the third test, all the contributions existed, that is, "Bei Ning," "water derived from oxygen and water originally present in the sample; in this example, the" reading "of the instrument is 18.3 ppb, Subtracting 3 l ppb of "background" and water derived from oxygen] 0 ppb, the water reading obtained was 5.2 ppb, and the error relative to the correct value was more than 4%, which is an excellent result. Therefore, the method and system according to the present invention can independently determine the concentration of oxygen and water in a hydrogen sample with good reliability. [Brief description of the drawings] The present invention will be described below with reference to the drawings, in which: FIG. 1 schematically shows a gas pipeline system capable of putting the method of the present invention into practice. The system includes a purifier and Converter; Figure 2 shows the results of the IM S hydrogen analysis corresponding to the different steps of the method of the present invention. Component symbol 10 System 11 Line 12 Component 12, Mating fitting 13 First * secondary line 13 'Second secondary line 13 "Third primary line 14 Single line 15 Ion mobile spectrometer 16 On-off valve 16' On-off valve 16" Switch Valve 1 7 First Purifier 18 Second Purifier 19 Converter-17-