200938826 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種揮發性有機污染物分析之前處 理方法，且特別是有關於一種適用於以氣相層析質譜儀分 析的揮發性有機污染物分析之前處理方法。 【先前技術】 由於半導體元件體積微小化的趨勢’晶圓表面殘留 Ο 之奈米污染物極易對元件效能產生影響，因此如何將晶圓 表面之污染物完全去除則顯得格外重要。 在半導體製造過程中，經常使用各種不同的化學藥 劑或物質來進行晶圓的製作’如光阻剝除、姓刻及濕式清 洗技術等步驟，之後又須利用水把晶片表面殘留的化學藥 劑清除，故需使用大量超純水（去離子水）。因此’去離子 水的水質也會對製程產生影響。 去離子水的水質檢驗方法一般可使用液相層析質譜 ❹ 儀（Liquid chromatography-mass spectrometry, LC-MS)或氣 相層析質譜儀（Gas chromatography-mass spectrometry, GC-MS)來檢測水中的有機物殘餘量。其中，非揮發性有機 污染物可以液相層析質譜儀檢測，揮發性的有機污染物則 以氣相層析質譜儀檢測。 然而，進行氣相層析時所使用的分析瓶内所含的空氣 中，揮發性有機物的含量往往比樣品本身所含的揮發性有 機物濃度還高，導致在進行氣相層析質譜分析時，會產生 200938826 干擾訊號 ，從而影響了檢測的準確度 【發明内容】 因此本發明的目的之_就是在提供 污染物分析之前處理方法， 用乂解決傳統以氣相層析質譜 =::r物時’分析瓶一_干 ❹ 八被t發月之上述目的’提出"'種揮發性有機污染物 刀之刖理方法’包含提供—分析瓶，其中分析瓶内部 無法直接接觸外界空氣；設置—管路，管路之-端與分析 瓶連通；經由分析瓶管路導人_聽氣體進人分析瓶；再 導出氣滌氣體’並重複進行上述導人氣體及導出氣體步 驟，直到該分析瓶内達到—預定潔淨度為止，最後再將欲 分析的液體樣品導入分析瓶中。 ❹ 本發明實施例利用管路將—氣滌氣體通人處與密閉 狀態的分析瓶中’再將分析瓶中所含的空氣導出，以重複 進打導入氣體及導出氣體之步驟，或連續氣蘇之方式帶出 污染物直到分析瓶内達到預定潔淨度為止，藉此可去除分 析瓶中所含的空氣雜質，而避免干擾氣相層析質譜儀的分 析結果。 【實施方式】 請參照第1圖，其繪示依照本發明一實施例的一種微 污染分析之前處理的方法流程圖。 200938826200938826 IX. Description of the invention: [Technical field of invention] The present invention relates to a method for treating volatile organic pollutants prior to analysis, and in particular to a volatile organic pollution suitable for analysis by gas chromatography mass spectrometry The method of analysis before the object analysis. [Prior Art] Due to the trend of miniaturization of semiconductor components 'Residual surface defects Ο Nano-contaminants are highly susceptible to component performance, so how to completely remove contaminants on the wafer surface is particularly important. In the semiconductor manufacturing process, a variety of different chemicals or substances are often used for wafer fabrication, such as photoresist stripping, surname etching, and wet cleaning techniques, and then the chemical residues that must be left on the wafer surface by using water. Clear, so use a lot of ultrapure water (deionized water). Therefore, the quality of deionized water will also have an impact on the process. The water quality test method for deionized water can generally be detected by liquid chromatography-mass spectrometry (LC-MS) or gas chromatography-mass spectrometry (GC-MS). Residual amount of organic matter. Among them, non-volatile organic pollutants can be detected by liquid chromatography mass spectrometry, and volatile organic pollutants are detected by gas chromatography mass spectrometry. However, in the air contained in the analytical flask used for gas chromatography, the content of volatile organic compounds tends to be higher than the concentration of volatile organic compounds contained in the sample itself, resulting in gas chromatography mass spectrometry. Will generate 200938826 interference signal, thus affecting the accuracy of detection. [Inventive content] Therefore, the object of the present invention is to provide a method for treating pollutants before the conventional gas chromatography mass spectrometry =::r 'Analyze the bottle one _ dry ❹ eight by the t-month of the above purpose 'propose' 'a kind of VOC knife treatment method' contains the provision - analysis bottle, in which the analysis bottle can not directly contact the outside air; The pipeline, the end of the pipeline is connected to the analysis bottle; the pipeline is guided through the analysis bottle, the gas is introduced into the analysis bottle, the gas scrubbing gas is further extracted, and the above-mentioned gas introduction and gas extraction steps are repeated until the analysis bottle is The inside reaches - the predetermined cleanliness, and finally the liquid sample to be analyzed is introduced into the analysis bottle. ❹ In the embodiment of the present invention, the air contained in the analysis bottle is taken out by the pipeline, and the air contained in the analysis bottle is further extracted, and the step of introducing the gas and the gas is repeated, or the continuous gas is used. The method of Su brings out the contaminants until the predetermined cleanliness is reached in the analysis bottle, thereby removing the air impurities contained in the analysis bottle and avoiding interference with the analysis results of the gas chromatography mass spectrometer. [Embodiment] Please refer to FIG. 1 , which is a flow chart of a method for processing before micro-polluting analysis according to an embodiment of the invention. 200938826
本發明之微污染分析之前處理包含下列步驟：（a)提供 一分析瓶’並使分析瓶内部無法直接接觸外界空氣；（b) 設置一管路，瓶管路之一端與分析瓶連通；（c)導入一氣滌 氣體進入分析瓶；（d)導出氣滌氣體；（e)重複進行上述導入 氣體及導出氣體步驟，直到該分析瓶内達到一預定潔淨度 為止（例如揮發性有機化合物含量為5 ppb以下）；⑴將欲 分析的液體樣品導入分析瓶中D 依照本發明之一實施例，步驟包含導入一氣滌氣體 進入刀析瓶，至分析瓶中形成一正壓環境；步驟（d)包含導 出氣滌氣體，解除分析瓶_之正壓環境並帶出污染物。 依照本發明之另一實施例’步驟（C)及步驟（d)係同時進 行，包含導入一氣務氣體進入分析瓶，並以連續氣滌之方 式’直接導出氣蘇氣體帶出污染物’以達到預定潔淨度為 止（例如揮發性有機化合物含量為5 ppb以下卜其中，連 續氣滌係指經由瓶口或一管路將一氣滌氣體持續吹入分 析瓶中，再將通過分析瓶後帶有污染物的氣滌氣體經由瓶 口或另一管路持續導出’以帶出污染物。 S —實施存I丨 請參照第2A〜2C目，其緣示依照本發明一實施例的 微污染分析之前處理的操作示意圖。 首先提供-微污染分析前處理設傷，微污染分析前處 理之設備_可分為兩部分，第一部份包含—樣品槽11〇、 —汲取裝置12〇、一切換閥130及-輸送管路U2。樣品槽 200938826The prior treatment of the micro-contamination analysis of the present invention comprises the steps of: (a) providing an analytical bottle 'and making the inside of the analytical bottle incapable of direct contact with the outside air; (b) providing a conduit through which one end of the vial is in communication with the analytical vial; c) introducing a gas scrubbing gas into the analytical flask; (d) deriving the gas scrubbing gas; (e) repeating the introducing gas and deriving the gas step until a predetermined cleanliness is reached in the analytical flask (eg, the volatile organic compound content is 5 ppb or less); (1) introducing the liquid sample to be analyzed into the analysis bottle D. According to an embodiment of the invention, the step comprises introducing a gas-purifying gas into the knife-resolving bottle to form a positive pressure environment in the analysis bottle; step (d) It includes the extraction of gas scrubbing gas, which removes the positive pressure environment of the analytical flask and brings out pollutants. According to another embodiment of the present invention, the steps (C) and (d) are carried out simultaneously, including introducing a gas into the analysis bottle, and directly extracting the gas from the gas to the contaminant in a continuous gas scrubbing manner. Until the predetermined cleanliness is reached (for example, the content of volatile organic compounds is 5 ppb or less). Continuous gas-purifying means that a gas-gas scrubbing gas is continuously blown into the analytical vial via a bottle mouth or a pipe, and then passed through the analytical bottle. The gas-purifying gas of the contaminant is continuously exported through the bottle mouth or another pipe to carry out the pollutants. S - Implementation of the solution I refer to the 2A to 2C, and the micro-contamination analysis according to an embodiment of the present invention is shown. Schematic diagram of the previous processing. Firstly provided - micro-contamination analysis pre-treatment, micro-contamination analysis pre-processing equipment _ can be divided into two parts, the first part contains - sample tank 11 〇, - extraction device 12 〇, a switch Valve 130 and - delivery line U2. Sample tank 200938826
不同閥位來轉換不同的流道與輸送管路112之不同區段連 140、一切換閥150、一分析 其中氣體源140連接一氣體輸 ’分析瓶160具有一上蓋162 第二部分包含一氣體源14〇、 瓶160及一加熱裝置17〇;其中氣 送管路142及一吸附管144， 密封於分析瓶160, 一分析瓶管路164之一端穿過上蓋162 延伸插入分析瓶160中，另端可用以與切換閥15〇之流道 的連接端連接。此外，切換閥13〇與切換閥15〇之間連接 一管路146。 請參照第2A圖，為本發明實施例之樣品循環步驟的 操作示意圖。 樣品循環步驟之操作包含將切換閥13〇切換（如以旋 轉方式）至一第一閥位，可利用人力、機械、氣壓或電磁等 方式旋轉，切換閥130於一第一閥位時可使第一流道！32 之連接端133a與輸送管路Π2的區段114相連通，另一連 接端133b與區段115相連通；第二流道134之連接端135a 與區段115相連通，另一連接端135b與區段116相連通。 因此’樣品槽110中之樣品經由連接樣品槽11〇及第 一流道132的區段114進入第一流道丨32，再經由連接第 一流道132與第二流道134之間的區段115送入第二流道 200938826 134中，再由連接第二流道134與汲取裝置12〇之間的區 段116通過汲取裝置120，使樣品於樣品槽11〇與汲取裝 置120之間流動’直至樣品充滿整個輸送管路I〗]及第一 流道132與第二流道134之間。依照本發明之實施例，汲 取裝置120為一蠕動泵浦。 分析瓶清潔步驟的操作包含將切換閥15〇切換（如以 旋轉方式）至一第一閥位，可利用人力、機械、氣壓或電磁 等方式旋轉，切換閥150旋轉至一第一閥位可使切換閥15〇 上之流道152的連接端153 b與分析瓶管路丨64連通，連 接端153a與管路146連通’管路146可與切換閥130之第 二流道136的連接端137a相接，另一連接端uyb則與氣 體輸送管路142相接。 如此，可使氣體源140所供應之氣體（例如氮氣）通過 吸附管144,吸附氣體中所含的碳氫化合物等有機物雜質 後’經切換閥130的第三流道136、連接切換閥13〇與切 換閥150之間的管路146、切換閥150的流道152及分析 瓶管路164送入分析瓶160中。 凊參照第2B圖，為本發明實施例之分析瓶清潔步驟 的操作示意圖。當氣體持續吹入分析瓶16〇中，形成一正 遷環境時，可將切換閥150切換至一第二閥位，使切換閥 BO上之流道152的連接端153a與分析瓶管路164相連 通，另一連接端153b則與一外部管路154連通，將氣體 排出分析瓶160外’以解除分析瓶16〇中之正壓狀態。 依照本發明之實施例’可藉由重複切換切換閥15〇之 200938826 第-閥位與第二閥&，進;^充入氣體及排&氣體的動作， 以將分析瓶160中原本所含的空氣完全趕出，達到一預定 之潔淨度（例如揮發性有機化合物含量為5 ppb以下），以 避免空氣中雜質對於後續分析所造成的干擾。 請參照f 2C ®，為本發明實施例之樣品注入步驟的 操作示意圖。樣品注入步驟包含將切換閥13〇切換至該第 一閥位，區段115之兩端分別與第三流道136之連結端Different valve positions are used to switch between different flow passages and different sections of the delivery line 112, a switching valve 150, an analysis in which the gas source 140 is connected to a gas supply. The analysis bottle 160 has an upper cover 162 and the second portion contains a gas. The source 14A, the bottle 160 and a heating device 17〇; wherein the gas delivery line 142 and a adsorption tube 144 are sealed in the analysis bottle 160, and one end of the analysis bottle line 164 is inserted into the analysis bottle 160 through the upper cover 162, The other end can be used to connect to the connection end of the flow path of the switching valve 15〇. Further, a line 146 is connected between the switching valve 13A and the switching valve 15A. Referring to Figure 2A, there is shown a schematic diagram of the operation of the sample recycling step of the embodiment of the present invention. The operation of the sample circulation step includes switching (eg, rotating) the switching valve 13 to a first valve position, which can be rotated by human, mechanical, pneumatic or electromagnetic means, and the switching valve 130 can be used in a first valve position. The first flow! The connection end 133a of 32 is in communication with the section 114 of the delivery line Π2, the other connection end 133b is in communication with the section 115; the connection end 135a of the second flow path 134 is in communication with the section 115, and the other connection end 135b Connected to section 116. Therefore, the sample in the sample tank 110 enters the first flow channel 32 via the segment 114 connecting the sample cell 11 and the first flow channel 132, and is then sent via the segment 115 between the first flow channel 132 and the second flow channel 134. In the second flow channel 200938826 134, the section 116 between the second flow channel 134 and the scooping device 12A is passed through the scooping device 120 to cause the sample to flow between the sample cell 11 and the scooping device 120 until the sample It fills the entire conveying line I] and between the first flow path 132 and the second flow path 134. In accordance with an embodiment of the invention, the extraction device 120 is a peristaltic pump. The operation of the analysis bottle cleaning step comprises switching (eg, in a rotating manner) the switching valve 15 to a first valve position, which can be rotated by human, mechanical, pneumatic or electromagnetic means, and the switching valve 150 is rotated to a first valve position. The connection end 153b of the flow path 152 of the switching valve 15 is connected to the analysis bottle line 丨64, and the connection end 153a is in communication with the line 146. The connection of the line 146 to the second flow path 136 of the switching valve 130 137a is connected, and the other connection end uyb is connected to the gas delivery line 142. In this way, the gas (for example, nitrogen) supplied from the gas source 140 can be passed through the adsorption tube 144, and the organic impurities such as hydrocarbons contained in the gas can be adsorbed, and then the third flow path 136 of the switching valve 130 is connected to the switching valve 13〇. The line 146 between the switching valve 150, the flow path 152 of the switching valve 150, and the vial line 164 are fed into the analysis bottle 160. Referring to Figure 2B, there is shown a schematic view of the operation of the analytical bottle cleaning step of the embodiment of the present invention. When the gas is continuously blown into the analysis bottle 16 , to form a positive environment, the switching valve 150 can be switched to a second valve position, so that the connection end 153a of the flow path 152 on the switching valve BO and the analysis bottle line 164 In communication, the other connection end 153b is in communication with an external line 154 to discharge the gas out of the analysis bottle 160 to relieve the positive pressure state in the analysis bottle 16〇. According to an embodiment of the present invention, the operation of the gas and the & gas can be performed by repeatedly switching the switching valve 15〇200938826 first-valve position and the second valve& The contained air is completely ejected to a predetermined degree of cleanliness (eg, VOC content below 5 ppb) to avoid interference with impurities in the air for subsequent analysis. Please refer to f 2C ® , which is a schematic diagram of the operation of the sample injection step of the embodiment of the present invention. The sample injection step includes switching the switching valve 13A to the first valve position, and the two ends of the segment 115 are respectively coupled to the third flow path 136.
Ο 137a及第二流道134之連接端135b相連，此時輸送管路 112的區段115中充滿樣品。 而第二流道134連接端135a可與氣體輸送管路142 連接以通入氣體，第三流道136之連結端137b則與管路 146之一端相連接，樣品藉由氣體源14〇產生的推力可流 至管路146中，切換閥150切換回第一閥位，管路146二 另端可與流道152之連結端153a連通，連結端15讣可與 分析瓶管路164連通，因此可將樣品隨著氣體之推送進、 分析瓶160中，以進行後續之分析。 J二實施你丨 請參照第3A〜3B圖，其繪示依照本發明另—實施你 的微污染分析之前處理的操作示意圖。 $ 前處 首先提供一微污染分析前處理設備，微污染分析 理設備200包含一容室210、一分析瓶23〇、—樣品輪、 裝置240及一氣體源250。 〇 送 其中’容室21〇包含-閥件211、—管路212、—間件 200938826 213、一官路214及一封蓋裝置216、推移件215及推移件 217。分析瓶230之開口部分231設置於容室21〇中，推 移件215可用以上下移動分析瓶23〇之位置，分析瓶咖 具有一分離之上蓋232,夾持於封蓋裝置216之失持部 218，當欲蓋合分析瓶23〇之上蓋時，可利用推移件出 將分析瓶230向上推移使上蓋232與分析瓶23〇結合。 閥件211活設於容室21〇之側壁，用以連通容室内與 容室外；閥件211之一端延伸入容室21〇中，並與管路 之一端相連，閥件211之另端設於容室21〇外，具有—第 一閥位219可與樣品輸送裝置24〇組裝以輸入樣品。推移 件217設置於側壁與閥件211之接觸點，用以前後移動閥 件211以調整管路212之位置。 依照本發明之另一實施例，容室21〇可不需具有推移 件215及推移件217之功能，管路212可為一軟質管體， 當欲蓋合分析瓶230之上蓋時，可直接將分析瓶23〇向上 推移使上蓋232與分析瓶230結合。 如前所述，管路212之一端與閥件211相連，另端則 延伸對準分析瓶230之開口部分231，藉此將樣品輸送裝 置240中之樣品送至分析瓶230。 氣體源250連設有一管路252，管路252與閥件211 之一第二閥位220相連通，用以將乾淨的氣體通入容室21〇 中。 請參照第3A圖，為本發明實施例之分析瓶清潔步驟 的操作示意圖。將分析瓶230之上蓋232以蓋口朝下方式 11 200938826 活夾於封蓋裝置216之夾持部218，夾持部218安置於容 室210之上方連接部，分析瓶230設於容室21〇中對應於 上蓋232之正下方的位置。 依照本發明之一實施例，分析瓶清潔步驟包含開啟閥 件211之第二閥位22〇，將氣體源25〇提供之氣體經由管 路212通入容室21〇及分析瓶23〇中，直到氣體與空氣之 混合物完全充滿容室210及分析瓶230中，漸漸形成一正 壓環境時’再開啟閥件213將分析瓶230及容室210之氣 體與空氣之混合物經由管路214排出，並重複上述動作， 藉由切換閥件211及闊件213來趕出分析瓶23〇及容室21〇 原本所含具有雜質的空氣’直至分析瓶23〇及21〇容室中 達到一預定潔淨度（例如揮發性有機化合物含量為5 ppb以 下）為止。 依照本發明之另一實施例，分析瓶清潔步驟包含同時 ，啟闕件211及閥件213，將氣體源250提供之氣體經由 S路212通入容室210及分析瓶230中，並將分析瓶23〇 ❹ 及容室210之氣體與空氣之混合物經由管路214排出，並 以連續驗之方式帶出污染物，持續—段時間直至分析瓶 =0及容室21G中所含的空氣完全被氣體源，所提供之 氣體所取代’直至分析瓶23〇及⑽容室中一 明 > "、、第3B圖，為本發明實施例之樣品注入步驟的 操作示意圖。關閉BA & 1& 蝎件211之第二閥位220，將樣品輸送 裝置240之針頭插人 入閥件211之第一閥位219，使欲分析 12 ❹ ❹ 200938826 5液241經由管路212導入清潔後的分析瓶230 中。樣4送裝置24G可為乾淨的針筒、泵浦等。 作照第冗圖，為本發明一實施例之封蓋步驟的操 不、。利用推移件217將閥件211向容室21〇外之方 1推移’使管路212離開分析瓶23〇上方，再利用推移件 將分析瓶向上推移，使分析瓶23〇與上蓋加結合， 3=及推移件217的操作可以人力、機械或氣•等 依知本發明之另一實施例，管路212可為一軟質管 當欲蓋合分析瓶230之上蓋時’可直接將分析瓶23〇 向上移使上蓋232與分析瓶23〇結合。 雖然本發明已以數實施例揭露如上，然其並非用以限 =發明’任何熟習此技藝者’在不脫離本發明之精神和 =内自可作各種之更動與潤飾，因此本發明之保護範 圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 ▲為讓本發明之上述和其他目的、特徵、優點與實施例 能更明顯易懂，所附圖式之詳細說明如下： 第1圖係緣示依照本發明一實施例的—種微污染分析 之前處理的方法流程圖。 x、 第2A圖為本發明實施例之樣品循環步驟的操作示意 圖0 * 13 200938826 第2B圖為本發明實施例之分析瓶清潔步驟的操作示 意圖6 第2C圖，為本發明實施例之樣品注入步驟的操作示 意圖。 第3A圖為本發明實施例之分析瓶清潔步驟的操作示 意圖。 第3 B圖，為本發明實施例之樣品注入步驟的操作干 意圖。 第3C圖，為本發明實施例之封蓋步驟的操作示意圖。 【主要元件符號說明】 100 :設備 110 .樣品槽 112 :輸送管路 114 :區段 115 :區段 116 :區段 120 :汲取裝置 130 :切換閥 132 :第一流道 133a :連接端 133b :連接端 134 :連接端 135a :連接端 136 :第三流道 137b :連接端 142 :氣體輸送管絡 135b :連接端 137a :連接端 140 :氣體源 144 :吸附管 146 :管路 152 :流道 153b :連接端 150 :切換閥 153a :連接端 160 :分析瓶 14 200938826 162 ： 上蓋 164 ： 分析瓶管路 170 ： 加熱裝置 200 ： 設備 210 : 容室 211 ： 閥件 212 : 管路 213 ： 閥件 214 ： 管路 215 ： 推移件 216 ： 封蓋裝置 217 ： 推移件 218 ： 夾持部 219 ： 第一閥位 220 : 第二閥位 230 ： 分析瓶 231 ： 開口部分 232 ： 上蓋 240 ： 樣品輸送裝置 241 ： 液體樣品 250 ： 氣體源 252 ： 管路The connection end 135b of the 137137a and the second flow path 134 is connected, and the section 115 of the delivery line 112 is filled with the sample. The connecting end 135a of the second flow path 134 can be connected to the gas delivery line 142 to pass the gas, and the connecting end 137b of the third flow path 136 is connected to one end of the line 146, and the sample is generated by the gas source 14 The thrust can flow into the line 146, the switching valve 150 is switched back to the first valve position, the other end of the line 146 can communicate with the connecting end 153a of the flow path 152, and the connecting end 15 can be connected to the analytical bottle line 164, so The sample can be pushed into the analysis bottle 160 with the gas for subsequent analysis. J II Implementation You Please refer to Figures 3A to 3B for a schematic diagram of the operation of the process prior to implementing your micro-contamination analysis in accordance with the present invention. $ Front Front A micro-contamination analysis pre-treatment device is provided. The micro-polluting analytical device 200 includes a chamber 210, an analytical vial 23, a sample wheel, a device 240, and a gas source 250.其中 The container 21 includes a valve member 211, a pipe 212, a partition member 200938826 213, an official road 214 and a cover device 216, a pusher member 215, and a pusher member 217. The opening portion 231 of the analysis bottle 230 is disposed in the chamber 21〇, and the pushing member 215 can move the position of the analysis bottle 23〇 from above, and the analysis bottle has a separate upper cover 232 and is clamped to the missing portion of the capping device 216. 218, when it is desired to cover the upper cover of the analysis bottle 23 ,, the analysis bottle 230 can be pushed up by the pusher to bring the upper cover 232 into the analysis bottle 23 。. The valve member 211 is disposed on the side wall of the chamber 21 to communicate with the chamber and the chamber; one end of the valve member 211 extends into the chamber 21 and is connected to one end of the tube, and the other end of the valve member 211 is disposed. Outside the chamber 21, there is a first valve position 219 that can be assembled with the sample delivery device 24 to input a sample. The pushing member 217 is disposed at a contact point of the side wall with the valve member 211 for moving the valve member 211 back and forth to adjust the position of the pipe 212. According to another embodiment of the present invention, the chamber 21〇 does not need to have the function of the pushing member 215 and the pushing member 217, and the tube 212 can be a soft tube body. When the lid of the analysis bottle 230 is to be covered, the tube can be directly The analysis bottle 23 is pushed upward to bond the upper cover 232 with the analysis bottle 230. As previously mentioned, one end of the line 212 is connected to the valve member 211 and the other end is extended to the open portion 231 of the analysis bottle 230, whereby the sample in the sample delivery unit 240 is sent to the analysis bottle 230. The gas source 250 is connected to a line 252 which communicates with a second valve position 220 of the valve member 211 for introducing clean gas into the chamber 21A. Please refer to FIG. 3A, which is a schematic diagram of the operation of the cleaning step of the analytical bottle according to an embodiment of the present invention. The upper cover 232 of the analysis bottle 230 is clamped to the clamping portion 218 of the capping device 216 with the cap opening downward 11 200938826. The clamping portion 218 is disposed at the upper connecting portion of the chamber 210, and the analysis bottle 230 is disposed in the chamber 21 The middle corresponds to the position directly below the upper cover 232. According to an embodiment of the present invention, the analysis bottle cleaning step includes opening the second valve position 22 of the valve member 211, and passing the gas supplied from the gas source 25 to the chamber 21 and the analysis bottle 23 through the line 212. Until the mixture of gas and air completely fills the chamber 210 and the analysis bottle 230, gradually forming a positive pressure environment, the valve 213 is reopened to discharge the mixture of gas and air of the analysis bottle 230 and the chamber 210 via the line 214. And repeating the above operation, by switching the valve member 211 and the wide member 213 to drive out the analysis bottle 23 〇 and the chamber 21 〇 originally containing air with impurities ' until the analysis bottles 23 〇 and 21 〇 room to achieve a predetermined clean The degree (for example, the volatile organic compound content is 5 ppb or less). According to another embodiment of the present invention, the analysis bottle cleaning step includes simultaneously, the opening member 211 and the valve member 213, and the gas supplied from the gas source 250 is introduced into the chamber 210 and the analysis bottle 230 via the S-way 212, and the analysis is performed. The gas and air mixture of the bottle 23 〇❹ and the chamber 210 is discharged through the line 214, and the contaminants are taken out in a continuous test for a period of time until the analysis bottle = 0 and the air contained in the chamber 21G is completely It is replaced by the gas source and the supplied gas 'up to the analysis bottle 23 〇 and (10) the chamber <""<3>, FIG. 3B, which is a schematic view of the operation of the sample injection step of the embodiment of the present invention. The second valve position 220 of the BA &1& 蝎 member 211 is closed, and the needle of the sample delivery device 240 is inserted into the first valve position 219 of the valve member 211, so that the liquid 241 to be analyzed 12 ❹ ❹ 200938826 is passed through the pipeline 212. Import into the cleaned analytical flask 230. The sample delivery device 24G can be a clean syringe, a pump, or the like. The photographing redundancy diagram is an operation of the capping step of an embodiment of the present invention. The valve member 211 is moved to the outside of the chamber 21 by the pusher 217. The pipe 212 is moved away from the analysis bottle 23, and the analysis bottle is pushed up by the pusher to combine the analysis bottle 23〇 with the upper cover. 3 = and the operation of the pushing member 217 can be human, mechanical or gas, etc. According to another embodiment of the present invention, the pipe 212 can be a soft pipe. When the cover of the analysis bottle 230 is to be covered, the analysis bottle can be directly 23〇 is moved upward to bond the upper cover 232 with the analysis bottle 23〇. The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention to the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope is subject to the definition of the scope of the patent application attached. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; A method flow chart for processing before micro-pollution analysis. x, FIG. 2A is a schematic diagram of the operation of the sample circulation step according to the embodiment of the present invention. 0 * 13 200938826 FIG. 2B is a schematic diagram of the operation of the analysis bottle cleaning step according to the embodiment of the present invention. FIG. 2C is a sample injection of an embodiment of the present invention. A schematic diagram of the operation of the steps. Fig. 3A is a schematic illustration of the operation of the analytical bottle cleaning step of the embodiment of the present invention. Fig. 3B is a schematic view of the operation of the sample injecting step of the embodiment of the present invention. FIG. 3C is a schematic view showing the operation of the capping step of the embodiment of the present invention. [Main component symbol description] 100: Apparatus 110. Sample tank 112: Delivery line 114: Section 115: Section 116: Section 120: Extraction device 130: Switching valve 132: First flow path 133a: Connection end 133b: Connection Terminal 134: connection end 135a: connection end 136: third flow path 137b: connection end 142: gas delivery pipe network 135b: connection end 137a: connection end 140: gas source 144: adsorption tube 146: line 152: flow path 153b : connection end 150 : switching valve 153a : connection end 160 : analysis bottle 14 200938826 162 : upper cover 164 : analysis bottle line 170 : heating device 200 : device 210 : chamber 211 : valve member 212 : line 213 : valve member 214 : Line 215 : Pusher 216 : Covering device 217 : Pushing member 218 : Holding portion 219 : First valve position 220 : Second valve position 230 : Analysis bottle 231 : Opening portion 232 : Upper cover 240 : Sample conveying device 241 : Liquid Sample 250 : Gas Source 252 : Piping
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