201133674 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種用以分析包含在基板之微量金屬等 分析對象物的基板分析裝置。並且，關於—種使用該基板 分析裝置之分析方法。 【先前技術】 就分析包含在半導體晶圓（W a f e r)等基板的金屬、有機 物質等分析對象物之分析裝置而言，一般係使用：用以餘 刻形成在基板之石夕氧化膜或氮化膜等氣相分解裝置、及用 以回收钮刻後之基板上所殘存之分析對象物的基板分析用 喷嘴。就使用該等裝置之分析手法而言，首先，將基板載 置在 VPD(Vap〇r Phase Deposition;氣相沉積）腔室 (比⑽以^等，_並導入氟化氫等蝕刻氣體，以蝕刻基板之形 成膜。然後’藉由基板分析用嘴嘴，將微量之分析液送出 至經過餘刻之基板，以所送出之分析液在基板上進行刮掃 (sweeping)。由於基板上之分杆對象物係移動於分析液 中’因此若以喷嘴抽吸經過刮掃之分析液，即能以微量之 分析液回收分析對象物，且可進行精確度佳之分析。 如此，在基板分析中，需要有以下二階段之步驟：藉 由氣相分解裝置银刻基板之步领、及藉由喷嘴回收分析對 象物之步驟。疋由於在半導體晶圓基板表面形成有自狹 氧化膜等時，其表面係成為親水性，送出分析液時分析液 即散漏，而造成回收困難之故。因此，在回收步驟中，由 於基板表面必須為疏水性，因此當親水性之氧化膜或氮化 322628 4 201133674 膜等形成在基板上時，必須要有預先去除該等氧化膜等蝕 刻步驟。 如此，以往在分析基板時，係使用氣相分解裝置與基 板分析用喷嘴之個別之裝置來進行蝕刻步驟及回收步驟之 二階段的步驟。特別是，氣相分解裝置為比較大型之裝置， 欲簡易地測量半導體製造生產線中之基板的分析等時，亦 需要有將欲測量之基板移送至VPD腔室等步驟等而有不 便。再者，當基板本身亦移送於氣相分解裝置與基板分析 用喷嘴之裝置間時，有產生污染之危險性。 因此，本發明人等係提供一種可藉由同一裝置全自動 地進行由氣相分解裝置所施行之#刻步驟、及由基板分析 用喷嘴所施行之回收步驟的全自動氣相分解裝置。依據該 裝置，可減少進行裝置間移送時基板被污染之風險。 再者，例如，藉由表面光伏電力（Surface Photo Vo 11age : SPV)法在基板上得知含有金屬等部位時，會有僅 將該特定部位局部地分析，而欲求出金屬等濃度的情形。 然而，如以往以氣相分解裝置與基板分析用喷嘴之個別裝 置分析基板時，會有無法正確地分析特定之局部部分之金 屬濃度等傾向。這是由於在由氣相分解裝置進行之蝕刻中 或#刻後，包含在基板之特定部位的分析對象物移動至其 他部位之故。在此背景之下，提案有一種局部地進行基板 之蝕刻的基板處理裝置（專利文獻1)。 再者，在以上之基板分析之回收步驟中，已知有一種 為了亦可短時間且有效率地刮掃大型化之基板，且增大喷 5 322628 201133674 嘴口徑，並使分析液與基板表面之接觸面積變大的方法。 然而，在使喷嘴口徑變大時，會有在刮掃時分析液容易從 喷嘴脫落之傾向，且會有分析液殘留在到掃後之基板的問 題產生。由此觀點來看，本發明人等係在專利文獻2中， 提案-種具有外緣朝前端方向突出之端面、及在前述端面 中偏心至外緣附近之開口的嘴嘴。再者，在專利文獻3中， 揭不有-種具有將喷嘴;I；内予以抽吸或減壓之機構的嘴 [先前技術文獻] [專利文獻] [專利文獻1]曰本特開2005-311140號公報 [專利文獻2]曰本特開2008-132401號公報 L專利文獻3]曰本特開平5-256749號公報 同樣地？為比二::相分解裝置係與習知之氣相分解裝j 進行基板之钱刻，者’專利文獻1雖局則 有在姓刻後分析對象物=㈣外進行回收步驟，因此售 進行正確分析之情形。至基板上之其他位置，而無沒 再者，即使在回 3記载之喷嘴巾，肖^財，於專利文獻2或專利文獻 膜的基板時，或分析疋在刀析具有多晶石夕或鶴石夕化物等 分析時，會有在^掃^晶圓等基材本身之所謂的主體（bulk) 【發明内容】 中產生分析液之脫落的傾向。 (發明所欲解決之課題） 322628 6 201133674 因此，本發明係提供一種可藉由同一裳置進行姓刻步 驟與回收步驟之兩步驟之小型且簡易的分析裝置，不論形 成在基板之臈的種類為何皆可進行分析 ，且亦適用在基板 上之局部分析的分析裝置。 (解決課題之手段） 用以解決前述課題之本發明的基板分析裝置係具備： 姓刻手段’藉由氣相分解法蝕刻包含分析對象物之基板； 及回收手I又’從噴嘴前端將分析液送出至基板上，以所送 出=刀析液刮掃基板表面後，由喷嘴前端抽吸分析液並回 刀析對象物；該基板分析裝置之特徵為：具備由將分析 液予=送出及抽吸之喷嘴本體、及配置在噴嘴本體之外周 的外官所構成之雙重管喷嘴；回收手段為雙重管喷嘴之喷 嘴本體；㈣手段係供給至喷嘴本體與外管之間的姓刻 體。 ’ 第1圖係顯不使用本發明之基板分析裝置進行基板分 析之示意圖。在第丨圖中，就錢而言，針對將在基板界 ，形成有氧化膜。X之基㈣时析之情形加以說明。本發 月之分析裝置係如第1圖所示，具備在噴嘴本體10之外周 ，置有外管20之雙重管構造的喷嘴者，如第丨圖之上圖的 箭頭所示，蝕刻手段為朝喷嘴前端方向供給至噴嘴本體1〇 與外官20之間15的蝕刻氣體。藉此，如第丨圖之下圖所 不，將送出分析液D之喷嘴本體之外周部分只的氧化膜〇又 予以蝕刻去除，而成為基板W本身露出之狀態。因此，即 使在例如於基板形成有氧化膜或氮化獏等親水性之膜時， 322628 7 201133674 送出分析液之部分的外周係成為疏水性之基板露出的狀 態，因此分析液不會濕散，可抑制回收率之降低。 依據本發明之基板分析裝置，如上述方式能以單一裝 置進行基板之形成膜的姓刻、及分析對象物之回收，因此 基板之污染風險會大幅減低，亦適用於局部性之分析。再 者，藉由以喷嘴刮掃基板表面，在基板上之任意位置，可 連續地進行蝕刻與回收。如此，由於只要使小型之喷嘴與 基板相對向，即可進行姓刻及回收，因此與使用習知之大 型氣相分解裝置等情形相比較，更適用於簡易的分析。 本發明之基板分析裝置的蝕刻手段只要可提供用以蝕 刻形成於基板之氧化膜等蝕刻氣體者即可。具體而言，亦 可為具備藉由氟酸等混酸溶液使屬於蝕刻氣體之蒸氣產生 之氣泡（bubb 1 ing)裝置者，亦可為具備使混酸溶液霧化之 喷霧器（nebu 1 i zer)者。喷霧器係可將濃度高之#刻氣體穩 定供給，因此在可縮短蝕刻時間之點具有功效。 喷嘴本體之尺寸係可為與以往回收步驟中使用之基板 分析用喷嘴相同程度之大小，可依欲分析之基板之尺寸 等，選擇任意之尺寸。相對於該喷嘴本體之喷嘴外管的大 小，較佳為直徑1. 5倍至2. 5倍，更佳為2倍左右。若為 此範圍内，則有以蝕刻手段施行之蝕刻將良好地進行，且 可確實地去除喷嘴本體之外周部分之形成膜的傾向。另一 方面，若相對於喷嘴本體之喷嘴外管之大小之直徑為未達 1. 5倍時，則在刮掃晶圓上時形成膜之蝕刻會有不充分之 情形，而在相對於喷嘴本體之喷嘴外管之大小之直徑為超 8 322628 201133674 過2. 5倍時，會有餘刻達至不需要之部分而對局部性分析 來說沒有效率之傾向。 而且，若採用本發明之雙重管構造之喷嘴，則在以從 • 喷嘴本體送出之分析液刮掃基板表面時，亦能在短時間内 - 有效率地對大型化之基板進行分析。藉由以圍繞進行刮掃 之分析液的方式配置外管，即可使圍繞分析液之管之口徑 增大，且能增加可保持之分析液的量，可使分析液與基板 表面之接觸面積增大，因此亦可縮短基板表面整體之刮掃 所需的時間。例如，比較以本發明之雙重管構造之喷嘴與 以習知之單重管構造之噴嘴所能保持之分析液的量時，雖 依喷嘴之口徑而不同，但在雙重管構造之喷嘴中約為500 至1000 //L左右，相對於此，在單重管構造之喷嘴中 約為100//L至150/zL左右。 如此，藉由採用雙重管喷嘴，可期待縮短基板表面之 刮掃時間的效果，然而若僅使外管之口徑增大時，有時會 有刮掃中分析液從喷嘴脱落之情形，且有在刮掃後之基板 殘留分析液之情形。因此，在本發明之基板分析裝置中， 除了蝕刻手段之外，較佳為具備將喷嘴本體與外管之間作 為排氣路徑之排氣手段，並且在外管前端具備外氣導入 孔。具備排氣手段與外氣導入孔時，刮掃基板表面之分析 液不容易從喷嘴脫落。詳細如後述，即使在分析具有多晶 矽或鎢矽化物等膜的基板時、或分析矽晶圓等基材本身之 所謂主體分析中，在不容易發生分析液之脫落之點特別有 效。 9 322628 201133674 藉由具有排氣手段及外氣導入孔之構成而可防止分析 液之脫落的原因，認為是由於藉由排氣將喷嘴本體與外管 之間作為減壓環境而維持容易保持分析液之狀態，且具有 外氣導入孔而藉此防止外氣不規則地流入之故。在此，就 「外氣不規則地流入排氣路徑内之情形」而言，考量難以 維持基板之水平狀態，且在分析時基板會傾斜之狀態的情 形，或分析表面狀態粗糙之基板的情形。例如，分析大型 之半導體基板等情形，或藉由前處理時之蝕刻而成為基板 表面狀態粗糙的情形。在上述情形下，是由於會有難以將 進行刮掃之喷嘴與基板之距離維持在一定之傾向之故。 具體而言，通常如第2圖（a)所示，刮掃中係將喷嘴與 基板之距離保持為大致均一，而在分析液充滿在外管前端 與基板之間的狀態下保持分析液。然而，如前所述，在成 為基板傾斜之狀態的情形等，在外管之圓周上之一部分， 容易產生與基板之距離變長的部分。因此，認為是在外管 前端與基板之間會產生未充滿分析液的間隙，由於此間隙 外氣會不規則地流入喷嘴内部之故。對此，依據本發明， 即使因該等基板之傾斜等而在外管前端與基板之間產生未 充滿分析液之隙間時，亦會促進沿著外氣導入孔的外氣之 流入，因此不容易發生分析液之脫落。此外，本發明之外 氣導入孔較佳為在外管前端之圓周上設置複數個，形狀係 可作成為缺口狀。 使用以上說明之本發明之基板分析裝置來分析基板 時，可一面以雙重管構造之喷嘴刮掃基板表面，一面進行 10 322628 201133674 蝕刻步驟及回收步驟。 以雙重管喷嘴進行之刮掃係能以與習知之回收步驟同 樣的方法進行。例如，可採用藉由一面使基板旋轉，一面 使喷嘴從内側移動至外側，而刮掃成旋渦狀之方法等。再 者，如前所述，本發明之喷嘴亦適用在局部地分析基板之 情形，在此情形下，只要以僅使欲分析之特定部位的基板 表面通過雙重管喷嘴之方式進行喷嘴操作即可。 此外，蝕刻步驟及回收步驟係可進行二次刮掃並使各 步驟分別進行，亦可以一次刮掃使蝕刻步驟與回收步驟同 時進行，而該進行二次刮掃並使各步驟分別進行的方式為 首先一面以雙重管喷嘴到掃基板表面整面（或局部）一面進 行蝕刻步驟後，再度對基板表面整面（或局部）進行回收步 驟。欲僅對基板上之一部分局部性進行分析時，較佳為使 蝕刻步驟與回收步驟同時進行。這是由於不會產生因蝕刻 導致分析對象物之擴散，而可良好地進行回收之故。 基板之形成膜為氧化膜或氮化膜等比較容易分解的膜 時，由於蝕刻所需之時間比較短，因此藉由以一次之刮掃 使蝕刻步驟與回收步驟同時進行，即可大幅地縮短分析時 間。另一方面，基板之形成膜為多晶矽、鎢矽化物、鈦、 氮化鈦等比較不容易分解的膜時，回收步驟係能在比較短 之時間進行，但蝕刻所需之時間比較長，因而有整體之分 析時間不容易縮短之傾向。因此，在分析形成有多晶矽等 膜的基板時，較佳為以在蝕刻步驟後進行回收步驟之方 式，分別進行各步驟。如此，與蝕刻步驟分開地進行回收 】1 322628 201133674 步驟時，在進行回收步驟時，於以分析液刮掃基板表面的 期間，藉由排氣手段對喷嘴本體與外管之間進行排氣，即 可防止分析液之脫落。 因此，特別是，具備排氣手段及外氣導入孔之基板分 析裝置係適用於具備多晶矽、鎢矽化物、鈦、氮化鈦之任 一者之膜的半導體基板、和半導體基板之晶圓基材的分 析。再者，亦適用於如形成電路圖案之晶圓在表面具有凹 凸之基板的分析。這是由於在基板表面為非疏水性之情形 時，亦可在不產生分析液之脫落的情形下進行刮掃。亦即， 由於多晶矽等膜或晶圓基材係比較不容易被分解，因此在 進行分解該等膜的蝕刻時，必須使用酸濃度高之混酸或強 酸等。因此，這是由於在分解多晶矽等膜後，因強酸等蝕 刻，基板表面會變粗糙而成為非疏水性，而有因表面張力 造成難以維持分析液之液滴狀態的傾向之故。 如本發明所示，在具備排氣手段與外氣導入孔之基板 分析裝置中，在基板表面變粗糙之情形時，亦可防止分析 液之脫落，因此以分析液而言，不僅是氟酸與過氧化氫之 混合溶液，亦可如亂酸與硝酸之混合溶液等，使用相較於 習知方法酸濃度更高之酸或強酸。因此，就分析對象物而 言，即使在包含有銅等不容易溶解於分析液的金屬之情形 時，亦可提升回收率。 在包含以上說明之蝕刻步驟及回收步驟的分析中，就 以喷嘴到掃基板表面之刮掃速度而言，特別是在考量以I虫 刻步驟進行蝕刻之基板之形成膜的種類之情形下，適當地 12 322628 201133674 選擇適合之速度。具體而言，如上所述，基板之形成膜為 多晶矽等情形時，由於蝕刻所需之時間比較長，因此蝕刻 及到掃速度係可設定為例如5mm/sec。另一方面，氧化膜 * 等由於#刻所需之時間比較短，因此可設定為例如3Omm/ • sec ° 就蝕刻步驟中所使用之蝕刻氣體而言，係可使用以往 所使用者，特別是以氟化氫氣體為佳。再者，亦可將臭氧 等氣體與氟酸一同導入而分析主體矽（bulk silicon)(基 板本身）。 在以上說明之本發明之分析方法中，可分析之基板的 種類雖無限定，但特別適用於晶圓等半導體基板之分析。 (發明之效果） 如以上之說明，本發明之基板分析裝置係可藉由同一 裝置進行蝕刻步驟與回收步驟之兩步驟的小型分析裝置。 依據本發明，可同時進行蝕刻步驟與回收步驟，且在分別 進行兩步驟之情形時，亦可在短時間進行回收步驟中之刮 掃，且不容易發生刮掃中之分析液之脫落。再者，本發明 之裝置亦適用於簡易的分析、或針對基板之特定部位的局 部性分析。 【實施方式】 以下，說明本發明之實施形態。 [第一實施形態] 實施例1 : 就實施例1而言，使用第3圖之喷嘴進行基板之分析。 13 322628 201133674 第3圖之噴嘴係由以喷嘴本體1〇及外管2〇所構成之雙重 s而構成。噴嘴本體1〇係與注射泵（syringe pu卯）相 連接，且可送出分析液D。再者，喷嘴係在喷嘴本體與 外管20之間連接有氟化氫（HF)蒸氣之產生裝置（未圖 示）’而可作為蝕刻手段朝箭頭方向供給蝕刻氣體。此外， 就HF蒸氣之產生裝置而言，可採用使氮氣在Η{Γ溶液中起 泡而產生HF蒸氣之裝置、或喷霧器等裝置等。 在本實施例中，使用噴嘴本體為1〇mm，外管為2〇mm， 且外管的直徑大小為噴嘴本體的直徑大小2倍的噴嘴。此 外，由於喷嘴本體之前端部變細，因此就前述噴嘴本體之 直徑而言，係以前端部以 準。 外之直徑相同之部分的大小為基 接著’說明使用前述噴嘴之具體的分析方法。就分析 對象之基板而言’係使用8 4(ineh)之㈣晶圓（_[Technical Field] The present invention relates to a substrate analysis device for analyzing an analysis object such as a trace amount of metal contained in a substrate. Further, an analysis method using the substrate analysis device is described. [Prior Art] For the analysis device for analyzing an object to be analyzed such as a metal or an organic substance on a substrate such as a semiconductor wafer, it is generally used to form a ruthenium oxide film or a nitrogen which is formed on the substrate. A gas phase decomposition device such as a chemical film, and a substrate analysis nozzle for recovering an analysis target remaining on the substrate after the button is engraved. In the analysis method using the devices, first, the substrate is placed in a VPD (Vap〇r Phase Deposition) chamber (by (10), etc., and an etching gas such as hydrogen fluoride is introduced to etch the substrate. The film is formed. Then, by using the nozzle for substrate analysis, a small amount of the analysis liquid is sent out to the substrate which has passed through the surface, and the sent analysis liquid is swept on the substrate. The system moves in the analysis liquid. Therefore, if the analysis liquid that has been swept by the nozzle is sucked, the analysis object can be recovered with a small amount of the analysis liquid, and the analysis can be performed with high precision. Thus, in the substrate analysis, it is necessary to have The following two steps are: a step of silver-etching a substrate by a gas phase decomposition device, and a step of recovering an object to be analyzed by a nozzle. When a self-dense oxide film or the like is formed on a surface of a semiconductor wafer substrate, the surface thereof is It becomes hydrophilic, and the analysis liquid is leaked when the analysis liquid is sent out, which causes difficulty in recovery. Therefore, in the recovery step, since the surface of the substrate must be hydrophobic, hydrophilic oxygen is required. Film or nitridation 322628 4 201133674 When a film or the like is formed on a substrate, an etching step such as removing the oxide film in advance is necessary. Thus, in the conventional analysis of the substrate, a gas phase decomposition device and a substrate analysis nozzle are used. The device performs the steps of the etching step and the second step of the recovery step. In particular, the gas phase decomposition device is a relatively large device, and when it is desired to easily measure the analysis of the substrate in the semiconductor manufacturing line, etc., the substrate to be measured is also required. It is inconvenient to transfer to the VPD chamber, etc. Further, when the substrate itself is transferred between the gas phase decomposition device and the device for the substrate analysis nozzle, there is a risk of contamination. Therefore, the present inventors have provided A fully automatic gas phase decomposition apparatus capable of fully performing the step of engraving by a gas phase decomposition apparatus and a recovery step performed by a nozzle for substrate analysis by the same apparatus. The risk of contamination of the substrate during transfer. Furthermore, for example, by Surface Photo Vo 11age (SPV) When it is known that a metal or the like is contained on the plate, the specific portion is only partially analyzed, and the concentration of the metal or the like is determined. However, when the substrate is analyzed by a separate device of the gas phase decomposition device and the substrate analysis nozzle, There is a tendency that the metal concentration of a specific partial portion cannot be correctly analyzed. This is because the analysis object included in a specific portion of the substrate moves to another portion during or after etching by the gas phase decomposition device. In view of this background, there is proposed a substrate processing apparatus for partially etching a substrate (Patent Document 1). Further, in the above-described substrate analysis recovery step, one is known to be short-time and Efficiently sweeping the enlarged substrate and increasing the nozzle diameter of the nozzle 5 532628 201133674 and increasing the contact area between the analysis solution and the substrate surface. However, when the nozzle diameter is increased, the analysis liquid tends to fall off from the nozzle during the wiping, and there is a problem that the analysis liquid remains on the substrate after the sweep. From this point of view, the inventors of the present invention have proposed a nozzle having an end surface in which the outer edge protrudes toward the distal end direction and an opening which is eccentric to the vicinity of the outer edge in the end surface. Further, in Patent Document 3, a nozzle having a mechanism for sucking or decompressing a nozzle; I; is disclosed [Patent Document] [Patent Document 1] 曰本特开2005 Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 5-256749. For the ratio of the second phase: phase decomposition device and the conventional gas phase decomposition device j, the patent document 1 has a recycling step after the last name analysis object = (4), so the sale is correct. Analysis of the situation. To the other position on the substrate, and no more, even in the case of the nozzle towel described in 3, Xiao Fuji, in the substrate of the patent document 2 or the patent document film, or the analysis of the enamel in the knife has a polycrystalline stone In the case of analysis such as the Heshixi compound, there is a tendency that the so-called bulk of the substrate itself such as the wafer is removed, and the analysis liquid is detached. (Problems to be Solved by the Invention) 322628 6 201133674 Therefore, the present invention provides a small and simple analysis device capable of performing two steps of a surname step and a recovery step by the same skirt, regardless of the type formed on the substrate Why it can be analyzed, and it is also applicable to the analysis device for local analysis on the substrate. (Means for Solving the Problem) The substrate analyzer according to the present invention for solving the above-mentioned problems includes: a method of surname etching "etching a substrate containing an analysis target by a gas phase decomposition method; and recycling the hand I and analyzing from the nozzle front end The liquid is sent to the substrate, and the surface of the substrate is scraped off by the sending of the knife-leaching liquid. Then, the analysis liquid is sucked from the tip end of the nozzle and the object is returned to the object. The substrate analysis device is characterized in that the analysis liquid is supplied and sent out. The suction nozzle body and the double tube nozzle formed by the outer officer disposed on the outer circumference of the nozzle body; the recovery means is a nozzle body of the double tube nozzle; and (4) the means is supplied to the first body between the nozzle body and the outer tube. Fig. 1 is a schematic view showing substrate analysis without using the substrate analysis apparatus of the present invention. In the figure, in terms of money, an oxide film is formed for the substrate boundary. The case of the basis of X (4) is explained. As shown in Fig. 1, the analysis device of the present month includes a nozzle having a double tube structure in which the outer tube 20 is disposed on the outer circumference of the nozzle body 10, as indicated by an arrow in the upper diagram of the first drawing, and the etching means is An etching gas supplied between the nozzle body 1A and the outer portion 20 is supplied toward the tip end direction of the nozzle. As a result, the oxide film 之外 of the outer peripheral portion of the nozzle body to which the analysis liquid D is sent is etched and removed as shown in the figure below, and the substrate W itself is exposed. Therefore, even when a hydrophilic film such as an oxide film or tantalum nitride is formed on the substrate, for example, the outer peripheral portion of the portion to which the analysis liquid is sent is exposed to a state in which the hydrophobic substrate is exposed, so that the analysis liquid is not wet. The reduction in recovery can be suppressed. According to the substrate analyzing apparatus of the present invention, as described above, the film formation of the substrate and the recovery of the analysis object can be performed in a single apparatus, so that the risk of contamination of the substrate is greatly reduced, and it is also suitable for local analysis. Further, etching and recovery can be continuously performed at any position on the substrate by scraping the surface of the substrate with a nozzle. As described above, since the small nozzle can be opposed to the substrate, the surname and the recovery can be performed. Therefore, it is more suitable for simple analysis than the conventional large-scale gas phase decomposition apparatus. The etching means of the substrate analyzing apparatus of the present invention may be provided as long as it can etch an etching gas such as an oxide film formed on the substrate. Specifically, it may be a bubble device that generates a vapor which is an etching gas by a mixed acid solution such as hydrofluoric acid, or may be a nebulizer equipped with a solution for atomizing a mixed acid solution (nebu 1 i zer) )By. The nebulizer is capable of stably supplying a high-concentration gas, and therefore has an effect at a point where the etching time can be shortened. The size of the nozzle body can be the same as that of the substrate analysis nozzle used in the conventional recovery step, and any size can be selected depending on the size of the substrate to be analyzed. 5倍优选优选左右左右左右。 The diameter of the outer nozzle of the nozzle body is preferably 1. 5 times to 2.5 times, more preferably about 2 times. If it is within this range, the etching by the etching means is performed satisfactorily, and the tendency of the film formation in the outer peripheral portion of the nozzle body can be surely removed. On the other hand, if the diameter of the outer tube of the nozzle body is less than 1.5 times, the etching of the film formed on the wafer may be insufficient, and the nozzle may be insufficient. The diameter of the outer tube of the nozzle of the main body is over 8 322628 201133674. When the time is 2.5 times, there is a tendency that the residual portion reaches the unnecessary portion and there is no efficiency for the local analysis. Further, according to the nozzle of the double pipe structure of the present invention, when the surface of the substrate is scraped by the analysis liquid sent from the nozzle body, the enlarged substrate can be efficiently analyzed in a short time. By arranging the outer tube around the analysis liquid for sweeping, the diameter of the tube surrounding the analysis liquid can be increased, and the amount of the analysis liquid that can be held can be increased, and the contact area between the analysis liquid and the surface of the substrate can be increased. The increase can also shorten the time required for the entire surface of the substrate to be scraped. For example, when comparing the amount of the analysis liquid which can be held by the nozzle of the double tube structure of the present invention and the nozzle of the conventional single tube structure, although it varies depending on the diameter of the nozzle, it is approximately in the nozzle of the double tube structure. It is about 500 to 1000 //L, and in this case, it is about 100//L to 150/zL in the nozzle of the single pipe structure. As described above, the effect of shortening the wiping time of the substrate surface can be expected by using the double tube nozzle. However, if only the diameter of the outer tube is increased, the analysis liquid may be detached from the nozzle during the scuffing, and The case where the analysis liquid remains on the substrate after the squeegee. Therefore, in the substrate analysis device of the present invention, in addition to the etching means, it is preferable to provide an exhaust means for making an exhaust path between the nozzle main body and the outer tube, and an outer air introduction hole is provided at the outer end of the outer tube. When the exhaust means and the external air introduction hole are provided, the analysis liquid scraping the surface of the substrate does not easily fall off from the nozzle. As will be described in detail later, even in the so-called main body analysis for analyzing a substrate having a film such as polycrystalline germanium or tungsten germanide, or analyzing the substrate itself such as a germanium wafer, it is particularly effective in that the analysis liquid is not easily peeled off. 9 322628 201133674 The reason why the analysis liquid can be prevented from falling off by the configuration of the exhaust means and the external air introduction hole is considered to be that the pressure between the nozzle body and the outer tube is maintained as a decompression environment by the exhaust gas. The state of the liquid has an external air introduction hole to prevent the outside air from flowing irregularly. Here, in the case of "the situation in which the outside air flows into the exhaust path irregularly", it is considered that it is difficult to maintain the horizontal state of the substrate, and the state in which the substrate is inclined during analysis, or the case where the substrate having a rough surface state is analyzed . For example, in the case of analyzing a large-sized semiconductor substrate or the like, or by etching at the time of pre-processing, the surface condition of the substrate is rough. In the above case, it is difficult to maintain the distance between the nozzle for cleaning and the substrate to be constant. Specifically, as shown in Fig. 2(a), the distance between the nozzle and the substrate is kept substantially uniform during the wiping, and the analysis liquid is held while the analysis liquid is filled between the tip end of the outer tube and the substrate. However, as described above, in a state where the substrate is inclined, a portion which is long on the circumference of the outer tube is likely to be generated in a portion on the circumference of the outer tube. Therefore, it is considered that a gap which is not filled with the analysis liquid is generated between the front end of the outer tube and the substrate, and the outside air may flow irregularly into the inside of the nozzle due to the gap. On the other hand, according to the present invention, even when a gap between the outer tube front end and the substrate is not filled with the analysis liquid due to the inclination of the substrate or the like, the inflow of the outside air along the external air introduction hole is promoted, so that it is not easy. The shedding of the analytical solution occurred. Further, in the outside air introducing hole of the present invention, it is preferable that a plurality of holes are provided on the circumference of the front end of the outer tube, and the shape can be formed into a notch shape. When the substrate is analyzed using the substrate analysis apparatus of the present invention described above, the substrate surface can be scraped with a double tube structure to perform an etching step and a recovery step of 10 322628 201133674. The sweeping with a double tube nozzle can be carried out in the same manner as the conventional recycling step. For example, a method in which the nozzle is swung from the inside to the outside while the substrate is rotated while rotating the substrate can be used. Furthermore, as described above, the nozzle of the present invention is also suitable for the case where the substrate is partially analyzed. In this case, the nozzle operation can be performed by simply passing the surface of the substrate of the specific portion to be analyzed through the double tube nozzle. . In addition, the etching step and the recycling step may be performed by two times of sweeping and each step may be performed separately, or the etching step and the recycling step may be performed simultaneously, and the second sweeping is performed and the steps are separately performed. In order to perform the etching step on the entire surface (or part) of the surface of the substrate after the double tube nozzle is first applied, the entire surface (or part) of the substrate surface is again subjected to a recovery step. In order to analyze only a part of the substrate on the substrate, it is preferred to carry out the etching step and the recovery step simultaneously. This is because the diffusion of the analyte due to etching does not occur, and the recovery can be performed satisfactorily. When the formation film of the substrate is a film which is relatively easily decomposed such as an oxide film or a nitride film, since the time required for etching is relatively short, the etching step and the recovery step can be simultaneously performed by one-time wiping, which can be greatly shortened. Analysis time. On the other hand, when the formation film of the substrate is a film which is relatively difficult to decompose, such as polycrystalline germanium, tungsten germanide, titanium, or titanium nitride, the recovery step can be performed in a relatively short period of time, but the time required for etching is relatively long, and thus There is a tendency that the overall analysis time is not easy to shorten. Therefore, in the case of analyzing a substrate on which a film such as polycrystalline germanium is formed, it is preferred to carry out each step by performing a recovery step after the etching step. In this way, in the step of recovering separately from the etching step, in the step of performing the recovery step, during the recovery step, the nozzle body and the outer tube are vented by the exhaust means while the surface of the substrate is being scraped by the analysis liquid. It can prevent the falling of the analytical solution. Therefore, in particular, the substrate analysis apparatus including the exhaust means and the external air introduction hole is applied to a semiconductor substrate including a film of any of polycrystalline germanium, tungsten germanide, titanium, or titanium nitride, and a wafer base of the semiconductor substrate. Analysis of materials. Furthermore, it is also applicable to the analysis of a substrate having a concave surface on a surface of a wafer in which a circuit pattern is formed. This is because when the surface of the substrate is not hydrophobic, it can be scraped without causing the falling of the analysis liquid. That is, since a film such as polysilicon or a wafer substrate is less likely to be decomposed, it is necessary to use a mixed acid or a strong acid having a high acid concentration when performing etching for decomposing the films. Therefore, this is because after the film such as polycrystalline germanium is decomposed, the surface of the substrate becomes rough due to etching with a strong acid or the like, and it becomes non-hydrophobic, and there is a tendency that it is difficult to maintain the state of the droplet of the analysis liquid due to the surface tension. According to the present invention, in the substrate analysis device including the exhaust means and the external air introduction hole, when the surface of the substrate becomes rough, the separation of the analysis liquid can be prevented, so that the analysis liquid is not only the hydrofluoric acid. The mixed solution with hydrogen peroxide may be a mixed solution of a chaotic acid and nitric acid, or the like, or an acid or a strong acid having a higher acid concentration than a conventional method. Therefore, in the case of analyzing the object, the recovery rate can be improved even when a metal such as copper which is not easily dissolved in the analysis liquid is contained. In the analysis including the etching step and the recovery step described above, in terms of the sweep speed of the nozzle to the surface of the substrate, in particular, in consideration of the type of film formed by the substrate which is etched by the insect cutting step, Properly 12 322628 201133674 Choose the right speed. Specifically, as described above, when the formation film of the substrate is polycrystalline germanium or the like, since the time required for etching is relatively long, the etching and the sweep speed can be set to, for example, 5 mm/sec. On the other hand, since the time required for the etching of the oxide film* or the like is relatively short, it can be set to, for example, 3Omm/ • sec °. For the etching gas used in the etching step, it is possible to use a conventional user, in particular, It is preferred to use hydrogen fluoride gas. Further, a bulk gas such as ozone may be introduced together with the hydrofluoric acid to analyze the bulk silicon (the substrate itself). In the analysis method of the present invention described above, the type of the substrate that can be analyzed is not limited, but is particularly suitable for analysis of a semiconductor substrate such as a wafer. (Effects of the Invention) As described above, the substrate analyzing apparatus of the present invention is a small-sized analyzing apparatus which can perform two steps of an etching step and a recovery step by the same apparatus. According to the present invention, the etching step and the recovery step can be simultaneously performed, and in the case where the two steps are respectively performed, the wiping in the recovery step can be performed in a short time, and the falling of the analysis liquid in the wiping is less likely to occur. Furthermore, the apparatus of the present invention is also suitable for simple analysis or for local analysis of specific parts of the substrate. [Embodiment] Hereinafter, embodiments of the present invention will be described. [First Embodiment] Example 1: In the first embodiment, the analysis of the substrate was carried out using the nozzle of Fig. 3. 13 322628 201133674 The nozzle of Fig. 3 is composed of a double s composed of a nozzle body 1 〇 and an outer tube 2 。. The nozzle body 1 is connected to a syringe pump and can send the analysis solution D. Further, the nozzle is connected to a hydrogen fluoride (HF) vapor generating device (not shown) between the nozzle body and the outer tube 20, and the etching gas can be supplied as an etching means in the direction of the arrow. Further, as the HF vapor generating device, a device for generating HF vapor by bubbling nitrogen gas in a ruthenium solution, a device such as a sprayer, or the like can be used. In the present embodiment, the nozzle body is 1 mm, the outer tube is 2 mm, and the diameter of the outer tube is twice the diameter of the nozzle body. Further, since the front end portion of the nozzle body is tapered, the diameter of the nozzle body is referred to as the front end portion. The size of the portion having the same outer diameter is based on the specific analytical method using the aforementioned nozzle. For the substrate of the analysis object, the system uses 8 (inh) (four) wafers (_
SiHc〇nWafer)基材。針_此基材，以使Na、Mg、A1等分 析對象物之各金屬濃度成為5xir at〇ms/cm2左右之、農产 的方式，肢鮮溶_下在晶圓上並使其賴而強制= 變污染者肢分析。此外，針躲此晶®純，在不進行 餘刻之情形下直接送出分析液時，分析㈣濕散在基板 上。因此，認為S在此晶圓基材形成有自絲化膜。 針對此半導體基板，使用第3圖之雙重管噴嘴，以 :欠之到掃同時娜刻步驟與回收步驟而進行:析:; 先’將雙重官喷嘴浸潰在包含3%HF、雛⑺之分析液，並 以注射泵3G進行抽吸，冑5叫L之分析液填充在喷嘴本 322628 201133674 體10之液槽内。接著，將喷嘴移動至晶圓基板上，以lL/min 將氮氣供給至喷霧器，並使用以200 //L/min供給HF濃度 49wt%之HF溶液而產生的蒸氣供給在喷嘴本體與外管之 間。在進行此蒸氣供給之同時，將約150//L之分析液送出 至基板上，利用喷嘴以3Omm/mi η之速度對基板上進行刮 掃，以進行分析對象物之回收。 實施例2 : 在本實施例中，針對與實施例1同樣之基板，使用第 3圖之雙重管噴嘴進行蝕刻步驟後，另外進行回收步驟。 首先，以lL/min將氮氣供給至喷霧器，並使用以200 //L/ min供給HF濃度49wt%之HF溶液而產生的蒸氣供給在喷嘴 本體與外管之間。此時，基板上之刮掃係以30mm/min之速 度進行。接著，將雙重管喷嘴浸潰在包含3%HF、4%札〇2之 分析液，並以注射泵30進行抽吸，將500 # L之分析液填 充在喷嘴本體10之液槽内。將約150//L之該分析液送出 至基板上，利用喷嘴以30mm/min之速度對基板上進行刮 掃，以進行分析對象物之回收。 由以上之結果得知，在實施例1、2之分析中，分析液 不會濕散在基板上，可良好地進行回收。再者，分析所需 之時間亦為比較短之時間。具體而言，在實施例1中，能 以5分鐘同時進行蝕刻與回收。再者，實施例2之分析時 間係#刻5分鐘、回收5分鐘，合計10分鐘。 另一方面，相對於此，如習知之分析方法所示，在進 行以具備VPD腔室等氣相分解裝置所施行之蝕刻、及以噴 15 322628 201133674 嘴施行之回收時，就分析時間而言，蝕刻需要約3分鐘、 分析對象物之回收需要約5分鐘，且亦必須要有使基板移 送至裝置間之步驟。因此，在習知之分析方法中，若亦考 慮到基板之移送時間時，則需要比實施例1、2更多之分析 時間。 接著，針對包含藉由實施例1所回收之分析對象物的 分析液，利用感應耦合電漿（plasma)質量分析裝置（ICP-MS) 測量下述表1所示之元素之晶圓中的濃度。並且，針對同 一基板反覆進行合計3次上述之回收步驟及元素濃度之分 析，以求出回收率。回收率係由相對於以3次之分析檢測 出的元素濃度之合計値的比例（回收率）計算出第1次之分 析所檢測出的元素濃度。分析方法一般較佳為能以1次之 分析檢測出全部之對象物，因此前述回收率越高，越顯現 能以第1次之分析檢測出許多元素的良好結果。 16 322628 201133674 [表1] 元素名稱 晶圓中濃度（atoms/cm2) 第1次 第2次 第3次 回收率（％) Na 7. 25xl〇10 9. 30xl08 2. 17xl〇8 卜， 98% Mg 5.52xl〇10 6. 44xl08 2.48xl〇8 98% A1 1.05xl〇n 5. 67xl09 1. 13xl〇9 94% Ca 3. 67xl010 1.05xl09 2.87x1〇8 96% Cr 4. 44x10】。 3. llxlO8 1. 〇lxl〇8 --- 1— 99% Μη j 4. 24xl〇10 3. 35xl08 8. 49xl〇7 99% Fe 6· 14xl〇〗° 6.77xl〇8 2.57x1〇8 98% Co 4. 63xl〇10 3. 13xl08 3.2lxl〇7 99% ___ 3. 92xl〇10 1.98x10® 7.83x1〇7 99% Cu —------ 2. 44xl〇10 1. 18xl09 3. 97xl〇8 94% Zn 3. 35xl〇10 6. 05xl〇8 1.〇8xl〇8 98% K -----— 6. 24xl〇10 7. 68xl〇8 2. 39xl〇8 98% Li 4.41xl〇10 8.28xl〇8 6.53x10s 97% Cd ------- 4. 92xl〇10 1.27xl〇8 8. 7〇xl〇7 100% W ----- 3. 23xl〇10 7. 76xl〇8 l.〇3xl〇8 — 97% Pb ^—~~~__ 4. 97xl〇10 3. 28xl〇8 1_1. 12xl07 --- 99% Ba —、 4. 63xl〇10 8.92xl〇8 2. 18xl〇8 98% ’針對半導體基板所含之 高的分析。 由表1得知’依據實施例 微里之分析對象物，可進行回收率 [第二實施形態] 在本實施形態中’針對形成有多晶㈣之半導體基 322628 17 201133674 板，除了與實施例丨同樣地具備蝕刻手段之外，復利用亦 具備排氣手段及外氣導入孔之噴嘴進行分析。 實施例3 : 利用第2圖之喷嘴進行基板之分析。第2圖（a)係喷嘴 之縱剖面圖，第2圖（b)係噴嘴前端之橫剖面圖。第2圖之 喷嘴係由以喷嘴本體10及外管2〇所構成之雙重管而構 成。喷嘴本體1〇係與注射泵3〇相連接，而可送出分析液 D。再者，與實施例1同樣地，在喷嘴本體1〇與外管2〇之 間連接有作為蝕刻手段之HF產生裝置（未圖示），並且連接 有排氣泵（未圖示）以作為可朝箭頭方向排氣至噴嘴本體1〇 與外管20之間的排氣手段。此外，邢產生裝置及排氣泵 係可藉由閥進行切換。外管2〇係在前端部具備外氣導入孔 21，在本實施形態中，如第2圖化）所示，在外管之圓周上 設置有由4個部位之缺口所構成的外氣導入孔21。在本實 %例中，使用噴嘴本體為1〇mm，外管為2〇mm，且外管的直 徑大小為噴嘴本體的直徑大小2倍的喷嘴。此外，由於如 第2圖（a)所示喷嘴本體之前端部會變細，.因此就前述喷嘴 本體之直徑而言’係以前端部以外之直徑相同之部分的大 小為基準。 接著’針對使用前述噴嘴之具體的分析方法進行說 明。就分析對象之基板而言，係使用在由8吋之矽所構成 的晶圓基材形成有l〇〇〇A(i〇〇nm)之矽氧化膜、且在該氧化 膜之上形成有l〇〇〇A(i〇〇nm)之多晶矽膜的半導體基板。 針對此半導體基板，首先在進行蝕刻步驟後，進行回 322628 18 201133674 收步驟。首先，以lL/min對喷霧器供給氮氣，並將以200 // L/min供給HF濃度49wt%之HF溶液而產生的蒸氣及臭氧 含有氣體（以輸出200kW之氣體放電器對由氧20%與氮80% - 所構成之氣體進行氣體放電所產生）供給至噴嘴本體與外 . 管之間。此時，基板上之刮掃係以5mm/min之速度進行。 接著，將第2圖之喷嘴浸潰在包含1%HF、4%H2〇2之分 析液’以注射果3 0進行抽吸並將10 0 0 // L之分析液填充在 喷嘴本體10之液槽内。之後，使600//L之分析液D送出 至半導體基板W上，以在外管20之前端圍繞分析液D之方 式保持，並且以使分析液D通過基板W之表面整體的方式 操作喷嘴。喷嘴操作係能以例如一面使基板W旋轉一面使 喷嘴10從内側移動至外側等方法對基板W之表面整體進 行。 在前述喷嘴操作中，藉由排氣泵以排氣速度0.3L/min 至1. OL/miη進行朝第2圖（a)之箭頭方向的排氣。在本實 施例中，於以上之喷嘴操作中，能不會殘留分析液而對基 板W之表面整體進行喷嘴操作。 就對以上之實施例3的比較而言，係使用僅由未具有 外管20之喷嘴本體10(單重管構造）所構成的習知喷嘴進 行基板之分析。就進行分析之基板而言，係使用與實施例 3同樣之半導體基板，蝕刻步驟係在VPD腔室内設置半導 體基板之後，供給以喷霧器使HF濃度49wt%之HF溶液霧 化之蒸氣、及以輸出200kW之氣體放電器對由氧20%與氮 80%所構成之氣體進行氣體放電而產生之臭氧含有氣體。此 19 322628 201133674 外’HF溶液4及氧含有氣體之供給量係調整成使氟化氫（HF) 之崧氣成為0. 5L/min至1.5L/min，使臭氧含有氣體成為 〇. 5L/min至2. OL/min。之後，使用前述單重管構造之噴 鳴，並使用1%HF、4%H2〇2作為分析液而回收分析對象物。 此時，送出至半導體基板w上之分析液D係設為至 1504。 再者，就相對於實施例3之另一比較例而言，係使用 未具有第2圖（a)中之外氣導入孔21的噴嘴進行分析。在 該比較例中，除了使用未具有外氣導入孔之喷嘴以外的分 析條件係設定為與實施例3同樣之方法。 ，述之結果，如實施例3所示，以具備外氣導入孔之 -重官噴嘴進行分析之情形’相對於在刮掃㈣完全沒有 刀析液從喷鳴脫落之情形，在使用單重管之喷嘴或未具有 ^氣導=孔之噴嘴時，會有分析液會在刮掃中從喷嘴脫 洛’且谷易殘留在基板上之傾向。之所以會造成該傾向的 原因’可能是當外氣流人喷嘴内料，難以藉由喷嘴保 分析液之故。 接著 八、 針對糟由實施例3所回收之包含分析對象物的 分析液，利用感應輕合電f f f分析裝置⑽,測量下 述表2所示之元素之晶圓中的濃度。並^，針對同一基板 反覆進行合計3次上述回收步驟及元素毅之分析，二求 二：收率。回收率係由相對於以3次之分析所檢測出之元 素:辰度之合計値的比例(回收率)來計算出第1次之分析所 檢測出的元讀度。分析方法較佳為-般能以1次之分析 322628 20 201133674 第1次之分析於物’因此前述回收率越高，越顯現能以 [表2] 出許多元素的良好結果。SiHc〇nWafer) substrate. Needle_This substrate is such that the concentration of each metal of the analytes such as Na, Mg, and A1 is about 5xir at 〇ms/cm2, and the method of agricultural production is to dissolve the oxalate on the wafer. Forced = variable polluted limb analysis. In addition, the needle is immersed in this crystal pure, and when the analysis liquid is directly sent out without the residual engraving, the analysis (4) is wet on the substrate. Therefore, it is considered that S forms a self-filing film on the wafer substrate. For the semiconductor substrate, the double tube nozzle of Fig. 3 is used to: immerse the sweeping step and the recovery step: analysis: first, the double official nozzle is immersed in the 3% HF, the young (7) Analyze the solution and pump it with the syringe pump 3G. The analytical solution of 胄5, L is filled in the tank of the nozzle 322628 201133674 body 10. Next, the nozzle was moved onto the wafer substrate, nitrogen gas was supplied to the atomizer at 1 L/min, and steam generated by supplying an HF solution having an HF concentration of 49 wt% at 200 //L/min was supplied to the nozzle body and the outside. Between the tubes. While the vapor supply was being performed, about 150//L of the analysis liquid was sent to the substrate, and the substrate was scraped at a speed of 3Omm/mi η by the nozzle to recover the analyte. [Embodiment 2] In the present embodiment, the same procedure as in the first embodiment was carried out, and after the etching step was carried out using the double tube nozzle of Fig. 3, a recovery step was additionally performed. First, nitrogen gas was supplied to the atomizer at 1 L/min, and steam generated by supplying an HF solution having an HF concentration of 49 wt% at 200 // L/min was supplied between the nozzle body and the outer tube. At this time, the wiping on the substrate was carried out at a speed of 30 mm/min. Next, the double tube nozzle was immersed in an analysis liquid containing 3% HF and 4% Sapporo 2, and suctioned by a syringe pump 30, and 500 #L of the analysis liquid was filled in the liquid tank of the nozzle body 10. About 150 / / L of the analysis liquid was sent to the substrate, and the substrate was scraped at a speed of 30 mm / min by a nozzle to recover the analyte. From the above results, in the analysis of Examples 1 and 2, the analysis liquid was not wetly scattered on the substrate, and the recovery was well performed. Furthermore, the time required for the analysis is also relatively short. Specifically, in Example 1, etching and recovery can be simultaneously performed in 5 minutes. Further, the analysis time of Example 2 was carried out for 5 minutes and recovered for 5 minutes for a total of 10 minutes. On the other hand, as shown in the conventional analysis method, when performing etching by a gas phase decomposing apparatus such as a VPD chamber and recycling by a nozzle of 15 322628 201133674, the analysis time is The etching takes about 3 minutes, the recovery of the analyte is about 5 minutes, and there is also a need to transfer the substrate to the device. Therefore, in the conventional analysis method, if the transfer time of the substrate is also considered, more analysis time than Embodiments 1 and 2 is required. Next, the concentration in the wafer of the elements shown in the following Table 1 was measured by an inductively coupled plasma mass spectrometer (ICP-MS) for the analysis liquid containing the analyte to be recovered by the first embodiment. . Then, the above-mentioned recovery step and element concentration analysis were carried out three times in total for the same substrate to determine the recovery rate. The recovery rate was calculated from the ratio (recovery rate) of the total enthalpy of the element concentration detected by the analysis of three times, and the element concentration detected by the first analysis was calculated. In the analysis method, it is generally preferred to detect all the objects by one analysis. Therefore, the higher the recovery rate, the better the results of the detection of many elements by the first analysis. 16 322628 201133674 [Table 1] Element name Wafer concentration (atoms/cm2) 1st 2nd 3rd recovery rate (%) Na 7. 25xl〇10 9. 30xl08 2. 17xl〇8 Bu, 98% Mg 5.52 Xl〇10 6. 44xl08 2.48xl〇8 98% A1 1.05xl〇n 5. 67xl09 1. 13xl〇9 94% Ca 3. 67xl010 1.05xl09 2.87x1〇8 96% Cr 4. 44x10]. 3. llxlO8 1. 〇lxl〇8 --- 1— 99% Μη j 4. 24xl〇10 3. 35xl08 8. 49xl〇7 99% Fe 6· 14xl〇〗 6.77xl〇8 2.57x1〇8 98% Co 4. 63xl〇10 3. 13xl08 3.2lxl〇7 99% ___ 3. 92xl〇10 1.98x10® 7.83x1〇7 99% Cu —------ 2. 44xl〇10 1. 18xl09 3. 97xl〇 8 94% Zn 3. 35xl〇10 6. 05xl〇8 1.〇8xl〇8 98% K ------ 6. 24xl〇10 7. 68xl〇8 2. 39xl〇8 98% Li 4.41xl〇 10 8.28xl〇8 6.53x10s 97% Cd ------- 4. 92xl〇10 1.27xl〇8 8. 7〇xl〇7 100% W ----- 3. 23xl〇10 7. 76xl〇 8 l.〇3xl〇8 — 97% Pb ^—~~~__ 4. 97xl〇10 3. 28xl〇8 1_1. 12xl07 --- 99% Ba —, 4. 63xl〇10 8.92xl〇8 2. 18xl 〇8 98% 'High analysis for semiconductor substrates. It is understood from Table 1 that the recovery rate can be obtained according to the analysis object of the embodiment [Second embodiment] In the present embodiment, the semiconductor substrate 322628 17 201133674 formed with polycrystalline (tetra) is provided, except for the embodiment. In addition to the etching means, the same means of the exhaust means and the nozzle of the external air introduction hole are also used for analysis. Example 3: The analysis of the substrate was carried out using the nozzle of Fig. 2. Fig. 2(a) is a longitudinal sectional view of the nozzle, and Fig. 2(b) is a transverse sectional view of the tip end of the nozzle. The nozzle of Fig. 2 is constituted by a double tube composed of a nozzle body 10 and an outer tube 2''''''' The nozzle body 1 is connected to the syringe pump 3, and the analysis liquid D can be sent. Further, in the same manner as in the first embodiment, an HF generating device (not shown) as an etching means is connected between the nozzle body 1A and the outer tube 2A, and an exhaust pump (not shown) is connected as The exhaust means can be exhausted in the direction of the arrow to between the nozzle body 1 and the outer tube 20. In addition, the Xing generator and the exhaust pump can be switched by valves. The outer tube 2 is provided with an outer air introduction hole 21 at the distal end portion. In the present embodiment, as shown in FIG. 2, an outer air introduction hole formed by a notch of four portions is provided on the circumference of the outer tube. twenty one. In the present example, the nozzle body is 1 mm, the outer tube is 2 mm, and the diameter of the outer tube is 2 times the diameter of the nozzle body. Further, since the front end portion of the nozzle body is tapered as shown in Fig. 2(a), the diameter of the nozzle body is based on the size of the portion having the same diameter other than the tip end portion. Next, a description will be made on a specific analysis method using the aforementioned nozzle. For the substrate to be analyzed, a tantalum oxide film of 10 A (i〇〇nm) is formed on a wafer substrate composed of 8 Å, and a film is formed on the oxide film. A semiconductor substrate of a polysilicon film of 〇〇〇A (i〇〇nm). For this semiconductor substrate, first, after the etching step, the step of returning to 322628 18 201133674 is performed. First, nitrogen is supplied to the atomizer at 1 L/min, and steam and ozone-containing gas are generated by supplying HF solution having an HF concentration of 49 wt% at 200 // L/min (to output a gas damper pair of 200 kW by oxygen 20 % is supplied between the nozzle body and the outer tube by a gas discharge of 80% of the nitrogen gas. At this time, the wiping on the substrate was performed at a speed of 5 mm/min. Next, the nozzle of FIG. 2 is immersed in the analysis liquid containing 1% HF, 4% H 2 〇 2, and the injection liquid is sucked by the injection fruit 30 and the analysis liquid of 100 Ω / L is filled in the nozzle body 10 Inside the tank. Thereafter, 600 / / L of the analysis liquid D is sent out onto the semiconductor substrate W to be held around the analysis liquid D at the front end of the outer tube 20, and the nozzle is operated in such a manner that the analysis liquid D passes through the entire surface of the substrate W. The nozzle operation system can perform the entire surface of the substrate W by, for example, rotating the substrate W while moving the nozzle 10 from the inside to the outside. In the above nozzle operation, the exhaust gas is directed toward the arrow direction of Fig. 2(a) by an exhaust pump at an exhaust speed of 0.3 L/min to 1. OL/miη. In the present embodiment, in the above nozzle operation, the entire surface of the substrate W can be subjected to nozzle operation without leaving the analysis liquid. For the comparison of the above embodiment 3, the analysis of the substrate was carried out using a conventional nozzle composed only of the nozzle body 10 (single pipe structure) having no outer tube 20. For the substrate to be analyzed, the same semiconductor substrate as in Example 3 was used, and after the semiconductor substrate was placed in the VPD chamber, the vapor was irradiated with a sprayer to atomize the HF solution having an HF concentration of 49% by weight, and The ozone-containing gas generated by gas discharge of a gas composed of 20% of oxygen and 80% of nitrogen is outputted by a gas discharger of 200 kW. 5L/分钟到到。 5 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 2. OL/min. Thereafter, the above-mentioned single tube structure was used for the squirting, and 1% HF and 4% H 2 〇 2 were used as the analysis liquid to collect the analyte. At this time, the analysis liquid D sent to the semiconductor substrate w was set to 1504. Further, with respect to another comparative example of the third embodiment, the analysis was carried out using a nozzle which did not have the outside air introduction hole 21 in Fig. 2(a). In the comparative example, the analysis conditions other than the use of the nozzle having no external air introduction hole were set in the same manner as in the third embodiment. As a result, as shown in the third embodiment, the case where the analysis is performed with the heavy-duty nozzle having the external air introduction hole is the case where the single-weight is used in the case where the knife-out liquid is completely detached from the squealing in the wiping (four). When the nozzle of the tube or the nozzle that does not have the gas guide = hole, there is a tendency that the analysis liquid will be detached from the nozzle during the sweeping and the valley tends to remain on the substrate. The reason why this tendency is caused may be that when the external airflow nozzle is filled, it is difficult to protect the liquid by the nozzle. Next, the concentration in the wafer of the elements shown in Table 2 below was measured by the induction light-weight f f f analyzing device (10) for the analysis liquid containing the analyte to be recovered by the third embodiment. And ^, for the same substrate, the total of the above-mentioned recovery steps and the analysis of the elements are repeated three times, and the second is two: the yield. The recovery rate was calculated from the ratio (recovery rate) of the total enthalpy of the elements detected by the analysis of the three times (recovery rate) to the first reading. The analysis method is preferably one-time analysis. 322628 20 201133674 The first analysis is on the object. Therefore, the higher the recovery rate described above, the better the results of many elements can be exhibited in [Table 2].
由表2得知 檢測出全部之磐 ^ . ，在實施例3中，亦可對於包含在半導@ 基板之微量之分析料物進行时率高之分析。導體 (產業上之可利用性） 可進 本發明係在評價包含在基板之金屬等污毕 在進行以高感度檢測出微量之污染物的基板分㈣ 322628 21 201133674 行簡易分析、或對基板之特定部位進行局部分析的分析裝 置。 【圖式簡單說明】 第1圖係使用本發明之基板分析裝置的基板分析之示 意圖。 第2圖係具備排氣手段及外氣導入孔之基板分析裝置 的縱剖面圖（a)及該裝置之實施例3之喷嘴前端的橫剖面 圖（b)。 第3圖係實施例1中之基板分析裝置的縱剖面圖。 【主要元件符號說明】 10 噴嘴本體 20 外管 21 外氣導入孔 30 注射泉 D 分析液 Ox 氧化膜 T 喷嘴 W 晶圓 22 322628It is known from Table 2 that all of the defects are detected. In Example 3, the analysis of the trace amount of the analyte contained in the semiconducting @ substrate can also be performed. Conductor (Industrial Applicability) The present invention can be used to evaluate a substrate containing a metal such as a substrate, and to perform a high-sensitivity detection of a trace amount of a contaminant. (4) 322628 21 201133674 Simple analysis, or on a substrate An analytical device for performing local analysis at a specific site. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the substrate analysis using the substrate analyzing apparatus of the present invention. Fig. 2 is a longitudinal sectional view (a) of a substrate analyzing apparatus including an exhausting means and an external air introducing hole, and a cross-sectional view (b) of the nozzle tip of the third embodiment of the apparatus. Fig. 3 is a longitudinal sectional view showing a substrate analyzing apparatus in the first embodiment. [Main component symbol description] 10 nozzle body 20 outer tube 21 external air introduction hole 30 injection spring D analysis liquid Ox oxide film T nozzle W wafer 22 322628