200908133 九、發明說明 【發明所屬之技術領域】 本發明，係爲有關於用以將基板表面上之以光阻劑作 爲例不的有機物除去之技術。 【先前技術】 在將基板上之以光阻劑來作例示的有機物除去之方法 中，例如係有在專利文獻1中所揭示之乾式法與濕式法。 作爲乾式法，係例示有氧電漿灰化法。此方法，雖然 不會產生公害，但是，係有會對基板造成損傷之問題、以 及用以使氧氣體電漿產生之裝置係爲高價的問題。 濕式法，係將有機系或無機系之溶劑作爲剝離溶劑。 有機系之溶劑，例如係可列舉有以酚與鹵素溶劑爲主成分 者。作爲無機系之溶劑，係可列舉有：包含硫酸與過氧化 氫者、包含氨與過氧化氫者、包含氟酸者、包含鹽酸與過 氧化氫者。此些之溶離液，由於係爲有害，因此係成爲需 要用以將光阻劑除去之廢液無害化的設備。 爲了解決前述乾式法以及濕式法之問題’在專利文獻 1中所揭示之光阻劑除去方法中，係經由包含有水或是乙 醇又或是由此些所成之溶媒分子之濕潤臭氧，來進行基板 之光阻劑的除去與前述基板之洗淨。但是，當蒸氣在基板 上結露的情況時，由於會有臭氧所致之對光阻劑分解的妨 害，因此，係以在不會使其結露於基板上的條件下來進行 爲理想。 -4- 200908133 又，雖然並非光阻劑之 利文獻2之半導體蝕刻方法 則係在超純水中使臭氧氣體 含有水蒸氣之臭氧氣體，並 —同供給至基板處。此時， 槽的溫度設定爲較基板以及 高，而使基板之表面結露， 氧以及鹼性成分之作用，而 且高速地作蝕刻。 臭氧水中之臭氧濃度， 的溶解度、和與水相接觸之 )，因此，就算是在大氣壓 觸，其濃度亦係僅爲百數十 是爲了提昇臭氧濃度，而對 含有氣體（絕大部分之成分 ，臭氧水之臭氧濃度係亦仍 進而，在被使用於產業 使用有無聲放電式者，但是 要添加氮，而在由此所產生 Ν Ο X，並藉由溶解於水中， 不被期望之效果的情況。 [專利文獻1 ]日本特開 [專利文獻2]日本特開 除去技術，但是，若是藉由專 以及半導體裝置之製造方法， 起泡（b u b b 1 i n g )，而得到包 將此與酸性又或是鹼性之氣體 係藉由將用以進行前述起泡之 將基板作保持之台的溫度爲更 並藉由此結露後之水蒸氣與臭 成爲目旨夠將G a A s系材料確貫 由於係依存於臭氧之相對於水 氣體中的臭氧分壓（亨利定律 下使100%之臭氧氣體與水接 ppm左右。一般而言，就算 臭氧濃度lOvol%左右之臭氧 係爲氧）加壓以提昇臭氧分壓 停留在百數十ppm左右。 用之臭氧產生器中，雖係廣泛 ，爲了提昇臭氧濃度，係有必 之臭氧含有氣體中，係包含有 而成爲硝酸，而有導致產生並 2001-290287 號公報 2004-235316 號公報 200908133 【發明內容】 於此，申請專利範圍第1項所記載之高濃度臭氧水製 造方法，係在較大氣壓爲更低壓的狀態下，使臭氧氣體與 水蒸氣混合，而後，將包含有此臭氧之水蒸氣冷卻並使其 結露，而製造高濃度臭氧水。由於係在較大氣壓爲更低壓 的狀態下，而將臭氧氣體與水蒸氣混合，因此，混合比係 被最適化，藉由此，能夠產生臭氧濃度爲較在大氣壓下所 產生之臭氧水更高的高濃度臭氧水。又，藉由對臭氧氣體 與水蒸氣間之混合比作改變，能夠對其濃度自由地作變化 。前述臭氧氣體，係只要使用臭氧濃度爲數十％以上者即 可。在本發明中，由於係在較大氣壓爲更低壓的狀態下而 將臭氧氣體與水蒸氣作混合，因此，係能夠避免爆炸的危 險性。 申請專利範圍第2項之高濃度臭氧水製造方法，係在 申請專利範圍第1項之高濃度臭氧水製造方法中，具備以 下特徵：前述臭氧氣體，係爲基於蒸氣壓之差異而對臭氧 含有氣體僅將臭氧作液化分離，而後再使其氣化所得到的 超高濃度臭氧氣體。藉由利用此超高濃度臭氧氣體，能夠 有效率的製造高濃度臭氧水。 申請專利範圍第3項所記載之高濃度臭氧水製造裝置 ，其特徵爲，具備有：被供給有臭氧氣體與水蒸氣之處理 室；和將此處理室之內壓控制在較大氣壓爲更低壓之幫浦 ;和將前述處理室之內側面與天花板面作加熱之加熱手段 ;和將前述處理室之底面部作冷卻之冷卻機構，經由前述 -6- 200908133 加熱手段， 度的溫度， 控制在較大 與前述水蒸 前述冷卻機 大氣壓爲更 因此，能夠 更高的高濃 混合比作改 體，係只要 中，由於係 水蒸氣作混 申請專 申請專利範 下特徵前 異而對臭氧 化，以產生 由從此臭氧 述處理室處 申請專 如申請專利 水製造裝置 前述處理室 之底部係經 而將前述處 同時，經由 氣壓爲更低 氣混合，而 構來冷卻， 低壓的狀態 產生臭氧濃 度臭氧水。 變，能夠對 使用臭氧濃 在較大氣壓 合，因此， 利範圍第4 圍第3項之 述臭氧氣體 含有氣體僅 超高濃度臭 產生裝置而 ，能夠有效 利範圍第5 範圍第3項 中，具備有 之底部埋設 由在流通路 理室加熱至 前述幫浦， 壓，在此狀 後，將此包 而在底面部 下，而將臭 度爲較在大 又，藉由對 其濃度自由 度爲數十％ 爲更低壓的 係能夠避免 項之高濃度 高濃度臭氧 之供給，係 將臭氧作液 氧氣體之臭 將目U述超筒 率的製造高 項之高濃度 又或是第4 以下特徵： 冷媒之流通 中所流通之 不會使水蒸 而將前述處 態下，將前 含有臭氧之 使其結露。 氧氣體與水 氣壓下所產 臭氧氣體與 地作變化。 以上者即可 狀態下而將 爆炸的危險 臭氧水製造 水製造裝置 爲藉由基於 化分離，而 氧產生裝置 濃度臭氧氣 濃度臭氧水 臭氧水製造 項所記載之 前述冷卻機 路徑而成。 冷媒而被冷 氣液化之程 理室之內壓 述臭氧氣體 水蒸氣經由 由於係在較 蒸氣混合， 生之臭氧水 水蒸氣間之 前述臭氧氣 。在本發明 臭氧氣體與 性。 裝置，係在 中，具備以 蒸氣壓之差 後再使其氣 來進行。藉 體供給至前 〇 裝置，係在 高濃度臭氧 構，係爲在 由於處理室 卻，因此， 200908133 若是包含有臭氧之水蒸氣與前述底部相接觸，則混合有前 述臭氧之水蒸氣係結露。 申請專利範圍第6項所記載之基板表面處理方法，其 特徵爲：係在藉由於較大氣壓爲更低壓的狀態下，使臭氧 氣體與水蒸氣混合，而後將包含有此臭氧之水蒸氣冷卻並 使其結露所製造出的高濃度臭氧水中，將基板浸漬，而將 基板表面之有機物除去。藉由在較大氣壓爲更低壓的狀態 下，將臭氧氣體與水蒸氣混合而得到高濃度臭氧水，並將 基板浸漬於其之中，能夠在較1 〇 爲更低溫的狀態下， 將基板表面上之前述有機物除去。故而，不會產生在高劑 量離子注入光阻中所會見到的爆裂（popping )現象。前 述臭氧氣體，係只要使用臭氧濃度爲數十％以上者即可。 在本發明中，由於係在較大氣壓爲更低壓的狀態下而將臭 氧氣體與水蒸氣作混合，因此，係能夠避免爆炸的危險性 〇 申請專利範圍第7項之基板表面處理方法，係在申請 專利範圍第6項之基板表面處理方法中，具備以下特徵： 前述臭氧氣體，係爲基於蒸氣壓之差異而對臭氧含有氣體 僅將臭氧作液化分離，而後再使其氣化所得到的超高濃度 臭氧氣體。由於係藉由利用此超高濃度臭氧氣體而有效率 的製造高濃度臭氧水，因此能夠有效率的將前述有機物除 去。 申請專利範圍第8項之基板表面處理方法，係在如申 請專利範圍第6項又或是第7項所記載之基板表面處理方 -8- 200908133 法中，具備有以下特徵：將藉由前述高濃度臭氧水而處理 後之基板，以超純水來作洗淨。藉由前述臭氧氣體與水蒸 氣所被處理之基板的有機物成分，係藉由與前述臭氧氣體 以及水蒸氣之反應，而被氧化分解爲水溶性之成分（例如 醛或是氫氧化物）。故而，藉由以超純水來洗淨基板，能 夠將由基板表面之前述水溶性成分所成的殘渣容易的除去 申請專利範圍第9項之基板表面裝置，其特徵爲，具 備有：在將於表面具備有有機物之基板作儲存的同時，被 供給有臭氧氣體與水蒸氣之處理室；和將此處理室之內壓 控制在較大氣壓爲更低壓之幫浦；和將前述處理室之內側 面與天花板面作加熱之加熱手段；和將前述處理室之底面 部作冷卻之冷卻機構，經由前述加熱手段，而將前述處理 室加熱至不會使水蒸氣液化之程度的溫度，同時，經由前 述幫浦，而將前述處理室之內壓控制在較大氣壓爲更低壓 ，在此狀態下，將前述臭氧氣體與前述水蒸氣混合，而後 ，將此包含有臭氧之水蒸氣經由前述冷卻機構來冷卻，而 在底面部使其結露並產生高濃度臭氧水，並將前述基板浸 漬在該高濃度臭氧水中’來除去前述有機物。藉由在較大 氣壓爲更低壓的狀態下’將臭氧氣體與水蒸氣混合而得到 高濃度臭氧水’並將基板浸漬於其之中，能夠在較1 〇 〇 °c 爲更低溫的狀態下，將基板表面上之有機物除去。故而， 不會產生在高劑量離子注入光阻中所會見到的爆裂（ popping )現象。前述臭氧氣體，係只要使用臭氧濃度爲 -9- 200908133 數十％以上者即可。在本發明中，由於係在較大氣壓爲更 低壓的狀態下而將臭氧氣體與水蒸氣作混合，因此，係能 夠避免爆炸的危險性。 申請專利範圍第1 〇項之基板表面處理裝置，係在申 請專利範圍第9項之基板表面處理裝置中，具備以下特徵 :前述臭氧氣體之供給，係爲藉由基於蒸氣壓之差異而對 臭氧含有氣體僅將臭氧作液化分離，而後再使其氣化，以 產生超高濃度臭氧氣體之臭氧產生裝置來進行。藉由從此 臭氧產生裝置而將前述超高濃度臭氧氣體供給至前述處理 室處，能夠有效率的製造高濃度臭氧水，因此能夠有效地 將有機物除去。 申請專利範圍第1 1項之基板表面處理裝置，係在如 申請專利範圍第9項又或是第1 0項所記載之基板表面處 理裝置中，具備有以下特徵：在前述處理室中，係爲了將 藉由前述高濃度臭氧水而處理後之基板作洗淨，而被供給 有超純水。基板表面上之有機物的殘渣，係經由超純水而 被洗淨除去。 申請專利範圍第1 2項之基板表面處理裝置，係在如 申請專利範圍第9項乃至第1 1項中之任一項所記載之基 板表面處理裝置中，具備有以下特徵：前述冷卻機構，係 爲在前述處理室之底部埋設冷媒之流通路徑而成。由於處 理室之底部係經由在流通路中所流通之冷媒而被冷卻，因 此’若是包含有臭氧之水蒸氣與前述底部相接觸，則混合 有前述臭氧之水蒸氣係結露。 -10 - 200908133 以上之基板表面處理方法與其裝置，特別在對於G 線、I線之光而具有感光性的酚醛系之光阻劑的除去中， 係爲有效。 故而，若是藉由以上的發明之高濃度臭氧水製造方法 及其裝置，則能夠有效率的製造高濃度臭氧水。而，藉由 將基板浸漬在此高濃度臭氧水中，能夠將前述基板上之有 機物除去。特別是，在高劑量離子注入光阻中，能夠不產 生爆裂現象地而進行除去。 【實施方式】 圖1，係爲展示本發明之實施形態的高濃度臭氧水製 造裝置（以下，稱爲臭氧水製造裝置）之槪略構成的剖面 圖。 臭氧水製造裝置1，係具備有處理室2與真空幫浦3 和加熱器4以及冷卻機構5。 ί 於處理室2’係導入臭氧氣體（〇3)與水蒸氣（Η2〇 - )。處理室2’係由處理容器20與將其密封之蓋21所成 。臭氧氣體（〇3)以及水蒸氣（η2ο )，係經由被加熱爲 不會使水蒸氣32結露的溫度之配管6而被導入。配管6 係被設置於蓋2 1處。蓋21，係經由身爲輔助密封構件之 0型環22而將處理室2密封。作爲〇型環22，例如係採 用由矽橡膠一般之耐臭氧性的材料所成之密封環。又，在 處理室2之底部23處，係被形成有用以將高濃度臭氧水 排出之配管7。配管7係具備有排液閥8。處理室2、蓋 -11 - 200908133 2 1、配管類以及閥類，係只要藉由如同不鏽鋼一般之對於 臭氧而具備有耐性之材料來形成即可。特別是，在以要求 低金屬不純物濃度的半導體製造爲代表之細微加工領域中 ，係以在內面處藉由鐵弗龍（登錄商標）等而被作了被覆 者爲理想。 作爲臭氧氣體，係使用超高濃度臭氧氣體。超高濃度 臭氧氣體，例如係藉由基於蒸氣壓之差異而對臭氧含有氣 體僅將臭氧作液化分離，而後再使其氣化，而可得之。更 具體而言，係可列舉出：由日本特開2001-304756或是日 本特開2 003 -2 0209之專利文獻中所揭示之臭氧產生裝置 而得到的臭氧氣體。前述臭氧氣體產生裝置，係爲基於臭 氧與其他之氣體成分（例如氧）的蒸氣壓之差異，而僅將 臭氧作液化分離，藉由此來製造超高濃度（臭氧濃度# 100%)之臭氧氣體。特別是，日本特開2003-20209之臭 氧供給裝置，係具備有複數之僅將臭氧液化以及氣化的處 理室，並藉由對此些之處理室個別地進行溫度控制，而成 爲能夠將超高濃度臭氧氣體作連續性的供給。而，作爲依 循此超高濃度臭氧氣體連續供給方式之市販的臭氧產生裝 置，例如係可列舉有明電舍製之純臭氧產生器（MPOG-HM1A1)。 臭氧氣體，係並不限定於前述超高濃度臭氧氣體。例 如，係可列舉有臭氧濃度爲數十％以上之臭氧氣體。在大 氣壓下，於14.3〜38vol%之臭氧濃度下，係爲持續性分 解區域，在〜44vol %之臭氧濃度下，係爲突燃區域，而 -12- 200908133 在〜44 vol%之臭氧濃度下，則係成爲爆發區域（杉光英 俊’臭氧之基礎與應用’光琳社，1996，ppl87)。在臭 氧水製造裝置1中’由於係在較大氣壓爲更低壓的狀態下 而將臭氧氣體與水蒸氣作混合，因此，係能夠避免爆炸的 危險性。 真空幫浦3,係爲用以將處理室2內作減壓之幫浦。 將處理室2與真空幫浦3作連接之配管1〇，係具備有閥 1 1 °閥1 1 ’係以使處理室2內之壓力成爲特定之値的方 式，而將處理室2內之氣相作密封。處理室2'配管1〇 以及閥11 ’係亦只要藉由如同不鏽鋼一般之對於臭氧而 具備有耐性之材料來構成即可。 加熱器4 ’係將蓋2 1、配管6以及處理室2之側面， 加熱至至少不會使被導入至處理室2內之水蒸氣液化的程 度。加熱器4，係只要適用在半導體技術中所被採用之既 知者即可。 冷卻機構5,係以在處理室2之底部而使包含有臭氧 之水蒸氣結露的方式，來將前述底部冷卻。冷卻機構5， 係藉由於處理室2之底部23處埋設例如身爲冷卻水之冷 媒的流通路24所成。流通路24，係以將處理室2之底面 部盡可能地均等冷卻的方式而被設置。 接下來，一面參考圖1以及圖3，一面針對臭氧水製 造裝置1之動作例作說明。 在減壓下之處理室2內，係被密封有超高濃度臭氧氣 體’接下來，水蒸氣係被導入。此時，係將處理室2之內 -13- 200908133 側面以及天花板面（蓋21之下面）加熱至使水蒸氣不會 被液化的程度。例如，當處理室2之內壓係爲1 00 hP a的 情況時’前述內側面以及天花板面之溫度，係根據圖3之 飽和蒸氣壓曲線，而被保持在較45 °C更高之溫度，例如 被保溫於100°C。另一方面，處理室2之底部，係經由在 所埋設之流通路24中所流通的冷卻水，而被作冷卻。例 如’當處理室2之內壓係爲1 〇〇hPa的情況時，前述底部 之溫度’係根據圖3之飽和蒸氣壓曲線，而被冷卻至45 °C以下’例如被冷卻至2 0〜4 0 °C。藉由此，混入有臭氧 之水蒸氣’係在處理室2之底面部作爲結露25而被液化 。以上之工程，係被反覆進行，而在處理室2內，係被儲 存有並不包含NOx或是〇2等之03以外的不純物之高濃 度臭氧水26。若是被儲存有一定量，則超高濃度臭氧氣 體與水蒸氣之供給係被停止。所儲存之高濃度臭氧水26 ，係經由閥8而被排出。 圖2，係爲展示本發明之實施形態的基板表面處理裝 置之槪略構成的剖面圖。 基板表面處理裝置30，係將基板31表面之包含有光 阻劑的有機物，藉由高濃度臭氧水來除去。基板表面處理 裝置30’除了在處理室2內之底面部被形成有放置用以 進行前述有機物之除去的基板3 1之保持部3 2以外，係爲 與臭氧水製造裝置1相同之構成。保持部32，係因應於 基板之形狀，而將前述底面部控刨而形成。 一面參考圖2，一面針對基板表面處理裝置30之動 -14 - 200908133 作例作說明。 在減壓下之處理室2內，係被密封有超高濃度臭氧氣 體，接下來，水蒸氣係被導入。此時，係將處理室2之內 側面以及天花板面（蓋2 1之下面）如圖3所示一般而加 熱至使水蒸氣不會被液化的程度。例如，當處理室2之內 壓係爲120hPa (臭氧分壓90hPa、水蒸氣分壓30hPa)的 情況時，前述內側面以及天花板面之溫度，係根據圖3之 飽和蒸氣壓曲線，而被保持在較45 °C更高之溫度，例如 被保溫於1 〇 〇 °C。另一方面，處理室2之底部2 3，係經由 在所埋設之流通路24中所流通的冷卻水（冷媒），而被 作冷卻。例如，當處理室2之內壓係爲120hPa (臭氧分 壓90hPa、水蒸氣分壓30hPa )的情況時，保持部32之溫 度，係根據前述飽和蒸氣壓曲線，而被冷卻至45 °C以下 ，例如被冷卻至20〜4〇°C。藉由此，混入有臭氧之水蒸 氣，係在處理室2之底面部結露。以上之工程，係被反覆 進行，而被儲存有並不包含NOx或是02等之03以外的 不純物之高濃度臭氧水26。而後，此工程係繼續被實行 5直到處理室2內之基板31成爲被浸漬爲止。右是被儲 存有一定量，則超高濃度臭氧氣體與水蒸氣之供給係被停 止。而，前述所儲存之高濃度臭氧水26，係經由閥8而 被排出。經由高濃度臭氧水而被處理後之基板3 1，係經 由超純水而更進一步的被洗淨。前述超純水，係只要從配 管6來導入即可。藉由臭氧氣體與水蒸氣所被處理之基板 3 1的有機物成分，係藉由與臭氧氣體以及水蒸氣之反應 -15- 200908133 ，而被氧化分解爲水溶性之成分（例如醛或是氫氧化物） 。（社團法人日本化學會編，季刊化學總說，No · 7，活性 氧之化學，1990年4月20日發行，pp.36〜37)。故而， 藉由以超純水來洗淨基板3 1，能夠將由基板3 1表面之前 述水溶性成分所成的殘渣容易的除去。又，亦可想見，藉 由以超純水來作洗淨而變質的光阻劑係被除去，而可將其 變薄。 表1，係展示經由基板表面處理裝置3 0而將作爲有 機物之其中一例的光阻劑的有機物除去後之試驗例。將作 爲酚醒/重氮萘醌（diazoNaphthoquinone)系光阻劑而具 備有東京應用化學工業製之 OFPR- 800 (對於G線（ 4 3 6nm )之光而具備有感光性的光阻劑）的Si基板，儲存 於處理室2中。以使處理室2之側壁的溫度成爲1 〇〇 °C左 右、使保持部3 2之溫度成爲4 0 °C ( 3 6〜4 0 °C )以下的方 式而作了調整。接下來，在此處理室2內供給超高濃度臭 氧氣體與水蒸氣，並令其結露至使前述基板被浸漬爲止的 程度。在供給前述超高濃度臭氧氣體之臭氧產生裝置9處 ，係使用有明電舍製之純臭氧產生器（MPO-HM1A1)。 在臭氧分壓9000Pa以及水蒸氣分壓3 000Pa的狀態下，將 前述基板作5分鐘之密封，而後，經由超純水來作洗淨。 於表1中，展示處理前與處理後之光阻劑的膜厚〔nm〕 、處理前與處理後之膜厚〔nm〕的差，以及剝離速度〔 nm/分〕。在表1中，係揭示有對3個的試料S 1〜S 3 (具 備有前述光阻劑之基板）作了灰化處理後之結果。 -16- 200908133 [表i] 經由高濃度臭氧水而對光阻劑作了處理 !後之情況 試料 光阻劑膜厚 差 剝離速度 處理前[nm] 處理後[nm] [nml [nm/分] S1 1144.4 501.2 643.2 128.6 S2 1144.4 504.1 640.3 128_1 — S3 1144.4 468.2 676.2 135.2 在經由高濃度臭氧水而對光阻劑作了處理後，以純水來作 洗淨之情況 試料 光阻劑膜厚 差 [nml 剝離速度 [nm/分] 處理前[nm] 處理後[nm] S1 1 144.4 368.1 776.3 155.3 S2 1144.4 342.8 801.6 160.3 S3 1 144.4 399.2 745.2 149.0 從表1中所示之結果，可以明顯得知，係確認了：若 藉由本發明之基板表面處理方法’則能夠在較1 〇〇°c爲更 I. 低溫之下，將以光阻劑爲例示之有機物除去。又，亦確認 • 了：在兩者之基板中，均未發生有爆裂現象。 【圖式簡單說明】 [圖1 ]展示本發明之實施形態的高濃度臭氧水製造裝 置之槪略構成的剖面圖。 [圖2]展示本發明之實施形態的基板表面處理裝置之 槪略構成的剖面圖。 [圖3 ]飽和水蒸氣壓曲線。 -17- 200908133 【主要元件符號說明】 1 :臭氧水製造裝置 2 :處理室 3 :真空幫浦 4 :加熱器 5 :冷卻機構 6 :配管 7 :配管 8 :排液閥 9 :臭氧產生裝置 1 〇 :配管 1 1 :閥 2 0 :處理容器 21 :蓋 22 : Ο型環 2 3 :底部 24 :流通路徑 2 5 :結露 2 6 :高濃度臭氧水 3 〇 :基板表面處理裝置 3 1 :基板 3 2 :保持部 -18 -BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for removing an organic substance having a photoresist as an example on a surface of a substrate. [Prior Art] The method of removing the organic substance exemplified by the photoresist on the substrate is, for example, the dry method and the wet method disclosed in Patent Document 1. As the dry method, an aerobic plasma ashing method is exemplified. This method does not cause pollution, but has a problem of causing damage to the substrate and a device for generating oxygen gas plasma. In the wet method, an organic or inorganic solvent is used as a stripping solvent. The solvent of the organic system may, for example, be a phenol or a halogen solvent as a main component. Examples of the inorganic solvent include those containing sulfuric acid and hydrogen peroxide, those containing ammonia and hydrogen peroxide, those containing hydrofluoric acid, and those containing hydrochloric acid and hydrogen peroxide. Such dissolving liquids, because they are harmful, are devices which are required to detoxify the waste liquid from which the photoresist is removed. In order to solve the problems of the dry method and the wet method described above, the photoresist removal method disclosed in Patent Document 1 is a method of removing ozone by using water or ethanol or a solvent molecule formed therefrom. The removal of the photoresist of the substrate and the cleaning of the substrate are performed. However, when vapor is condensed on the substrate, it is desirable to carry out the decomposing of the photoresist due to ozone, so that it does not dew on the substrate. -4- 200908133 Further, although the semiconductor etching method of Document 2 is not a photoresist, the ozone gas containing ozone gas in the ultrapure water is supplied to the substrate at the same time. At this time, the temperature of the groove is set to be higher than that of the substrate, and the surface of the substrate is dew condensation, oxygen and an alkaline component, and etching is performed at a high speed. Ozone concentration in ozone water, solubility, and contact with water), therefore, even at atmospheric pressure, the concentration is only a few hundred is to increase the ozone concentration, but for the gas (most of the components) The ozone concentration of ozone water is still further. If it is used in the industry, there is a silent discharge type, but it is necessary to add nitrogen, and the resulting Ν , X, and dissolved in water, is not expected. [Patent Document 1] Japanese Patent Laid-Open (Patent Document 2) Japanese Patent Application Laid-Open Publication No. Hei. Or the alkaline gas system is formed by the temperature of the stage for holding the substrate for performing the foaming described above, and the water vapor and the odor after the dew condensation are made to achieve the G a A s-based material. It is determined that the ozone is dependent on the partial pressure of ozone in the water gas. Under Henry's law, 100% of the ozone gas is connected to the water by about ppm. In general, even if the ozone concentration is about 10%, the ozone is oxygen. Pressurization to increase the partial pressure of ozone to stay at around tens of ppm. Although the ozone generator is widely used, in order to increase the concentration of ozone, it is necessary to contain ozone and contain nitric acid. In the high-concentration ozone water production method described in the first aspect of the invention, the ozone is made in a state where the atmospheric pressure is lower and the pressure is lower. The gas is mixed with water vapor, and then the water vapor containing the ozone is cooled and dew condensation to produce a high concentration of ozone water. Since the ozone gas is mixed with water vapor at a relatively low pressure, the ozone gas is mixed with water vapor. Therefore, the mixing ratio is optimized, whereby a high concentration of ozone water having an ozone concentration higher than that of ozone water generated at atmospheric pressure can be generated. Further, by mixing the ozone gas and the water vapor The concentration of the ozone gas can be freely changed as long as the ozone concentration is tens% or more. In the present invention, The ozone gas is mixed with water vapor at a relatively high pressure and a lower pressure, so that the risk of explosion can be avoided. The method for manufacturing high-concentration ozone water according to the second application of the patent scope is in the scope of patent application. In the high-concentration ozone water production method of the first aspect, the ozone gas is characterized in that the ozone gas is obtained by liquefying and separating the ozone-containing gas based on the difference in vapor pressure, and then vaporizing the ozone. The high-concentration ozone water production device according to the third aspect of the invention is characterized in that the ozone gas is supplied with ozone. a treatment chamber for gas and water vapor; and a pump for controlling the internal pressure of the processing chamber to a lower pressure; and heating means for heating the inner side surface and the ceiling surface of the processing chamber; and The cooling mechanism for cooling the bottom portion is controlled by the above-mentioned -6-200908133 heating means, and the temperature is controlled to be larger and the aforementioned water is steamed as described above. The atmospheric pressure of the machine is even higher, so that it can be modified with a higher concentration of high-concentration, as long as it is due to the application of water vapor as a hybrid application for the ozonization of the characteristics of the patent application. The application is made to apply the patented water-making device to the bottom of the processing chamber, and the above-mentioned portion is simultaneously cooled by the air pressure to be lower, and the ozone is dehydrated in a low-pressure state. It is possible to use ozone to concentrate on a large gas pressure. Therefore, the ozone gas containing gas in the fourth paragraph of the fourth range of the profit range is only an ultra-high concentration odor generating device, and it is effective in the fifth range and the third item. The bottom burying is heated by the flow path chamber to the above-mentioned pump, and after pressing, the package is placed under the bottom portion, and the odor is larger, by the degree of freedom of the concentration. Ten% of the lower pressure system can avoid the supply of high concentration and high concentration of ozone, and the ozone is used as the odor of liquid oxygen gas, and the high concentration of the super high rate is also the fourth characteristic: In the circulation of the refrigerant, the water is not steamed, and in the above state, the ozone is contained before it is dew condensation. Oxygen gas and ozone gas produced under water pressure change with the ground. The above-mentioned dangers of explosion can be made in the state of ozone water. The water-making apparatus is formed by the above-described cooling machine path by the separation of oxygen generation apparatus and the ozone gas concentration ozone water ozone water production item. In the process chamber where the refrigerant is liquefied by cold air, the ozone gas is vaporized. The ozone gas is mixed between the ozone water and the steam generated by the vapor. In the present invention, ozone gas and sex. The device is equipped with a vapor pressure difference and then gas. Since the donor is supplied to the front-end device in a high-concentration ozone system because it is in the processing chamber, 200908133, if the water vapor containing ozone is in contact with the bottom portion, the water vapor condensation of the ozone described above is mixed. The substrate surface treatment method according to claim 6, wherein the ozone gas is mixed with water vapor by a relatively low pressure, and then the water vapor containing the ozone is cooled and The high-concentration ozone water produced by the dew condensation is immersed in the substrate to remove the organic matter on the surface of the substrate. By mixing ozone gas with water vapor at a relatively high pressure and obtaining a high concentration of ozone water, and immersing the substrate therein, the substrate surface can be cooled at a lower temperature than 1 Torr. The aforementioned organic matter is removed. Therefore, there is no popping phenomenon that can be seen in high dose ion implantation photoresists. The ozone gas described above may be used as long as the ozone concentration is tens% or more. In the present invention, since the ozone gas and the water vapor are mixed in a state where the atmospheric pressure is lower and lower, the risk of explosion can be avoided, and the substrate surface treatment method of the seventh application patent is attached. In the substrate surface treatment method of the sixth aspect of the invention, the ozone gas is characterized in that the ozone gas is obtained by liquefying and separating ozone from the ozone-containing gas based on the difference in vapor pressure, and then vaporizing the ozone. High concentration of ozone gas. Since the high-concentration ozone water is efficiently produced by utilizing the ultra-high concentration ozone gas, the organic matter can be efficiently removed. The method for processing a substrate surface according to Item 8 of the Patent Application No. 6-200908133, as described in the sixth or the seventh aspect of the patent application, has the following features: The substrate treated with high concentration of ozone water is washed with ultrapure water. The organic component of the substrate treated by the ozone gas and the water vapor is oxidatively decomposed into a water-soluble component (e.g., an aldehyde or a hydroxide) by reaction with the ozone gas and water vapor. Therefore, by washing the substrate with ultrapure water, the substrate surface device of the ninth application of the patent application can be easily removed from the residue of the water-soluble component on the surface of the substrate, and is characterized in that it is a substrate having an organic substrate for storage while being supplied with ozone gas and water vapor; and a chamber for controlling the internal pressure of the processing chamber to a lower pressure; and the inner side of the processing chamber a heating means for heating the ceiling surface; and a cooling means for cooling the bottom surface portion of the processing chamber, wherein the processing chamber is heated to a temperature that does not liquefy the water vapor via the heating means, and a pump, wherein the internal pressure of the processing chamber is controlled to a lower pressure at a higher pressure, in which state the ozone gas is mixed with the water vapor, and then the ozone-containing water vapor is cooled by the cooling mechanism. And dew condensation on the bottom portion to generate high-concentration ozone water, and immersing the substrate in the high-concentration ozone water to remove Organic matter. By mixing the ozone gas with water vapor to obtain a high concentration of ozone water at a relatively low pressure, and immersing the substrate therein, it can be at a lower temperature than 1 〇〇 °c. The organic matter on the surface of the substrate is removed. Therefore, there is no popping phenomenon that can be seen in high-dose ion implantation photoresists. The ozone gas may be used in an amount of tens of or more of -9-200908133. In the present invention, since the ozone gas and the water vapor are mixed in a state where the atmospheric pressure is lower, the risk of explosion can be avoided. The substrate surface treatment apparatus according to the first aspect of the invention is the substrate surface treatment apparatus according to the ninth aspect of the invention, characterized in that the ozone gas is supplied by ozone based on a difference in vapor pressure. The gas containing gas is only liquefied and separated, and then gasified to produce an ozone generating device of ultra-high concentration ozone gas. By supplying the ultra-high concentration ozone gas to the processing chamber from the ozone generating device, it is possible to efficiently produce high-concentration ozone water, so that the organic matter can be effectively removed. The substrate surface treatment apparatus according to the ninth aspect of the invention, wherein the substrate surface treatment apparatus according to claim 9 or the item 10 is characterized in that, in the processing chamber, In order to wash the substrate treated by the high-concentration ozone water, ultrapure water is supplied. The residue of the organic matter on the surface of the substrate is washed and removed by ultrapure water. The substrate surface treatment apparatus according to any one of the items of the first aspect of the present invention, characterized in that the cooling mechanism, the cooling mechanism, The flow path of the refrigerant is buried in the bottom of the processing chamber. Since the bottom of the treatment chamber is cooled by the refrigerant flowing through the flow passage, if the steam containing ozone is in contact with the bottom portion, the water vapor of the ozone is mixed. -10 - 200908133 The above substrate surface treatment method and apparatus are particularly effective for removing a phenolic photoresist which is photosensitive to G-line or I-line light. Therefore, according to the above-described high-concentration ozone water production method and apparatus of the invention, it is possible to efficiently produce high-concentration ozone water. Further, by immersing the substrate in the high-concentration ozone water, the organic matter on the substrate can be removed. In particular, in the high-dose ion-implanted photoresist, the removal can be performed without causing a burst phenomenon. [Embodiment] FIG. 1 is a cross-sectional view showing a schematic configuration of a high-concentration ozone water producing apparatus (hereinafter referred to as an ozone water producing apparatus) according to an embodiment of the present invention. The ozone water producing apparatus 1 is provided with a processing chamber 2, a vacuum pump 3, a heater 4, and a cooling mechanism 5. ίIn the treatment chamber 2', ozone gas (〇3) and water vapor (Η2〇 - ) are introduced. The processing chamber 2' is formed by the processing container 20 and a lid 21 that seals it. The ozone gas (〇3) and the water vapor (η2ο) are introduced through a pipe 6 heated to a temperature at which the water vapor 32 is not dew condensation. The piping 6 is provided at the cover 21. The lid 21 seals the processing chamber 2 via an O-ring 22 which is an auxiliary sealing member. As the 〇-shaped ring 22, for example, a seal ring made of a material which is generally resistant to ozone by ruthenium rubber is used. Further, at the bottom portion 23 of the processing chamber 2, a pipe 7 for discharging high-concentration ozone water is formed. The piping 7 is provided with a drain valve 8. Processing chamber 2, cover -11 - 200908133 2 1. The piping and the valve are formed by a material having resistance to ozone as in stainless steel. In particular, in the field of fine processing, which is representative of semiconductor manufacturing requiring low metal impurity concentration, it is preferable to be coated with Teflon (registered trademark) or the like at the inner surface. As the ozone gas, an ultra-high concentration ozone gas is used. The ultra-high concentration ozone gas can be obtained, for example, by liquefying the ozone-containing gas based on the difference in vapor pressure, and then vaporizing it. More specifically, the ozone gas obtained by the ozone generating apparatus disclosed in Japanese Patent Laid-Open Publication No. 2001-304756 or Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. The ozone gas generating device is based on the difference in vapor pressure between ozone and other gas components (for example, oxygen), and only ozone is liquefied and separated, thereby producing ozone having an extremely high concentration (ozone concentration #100%). gas. In particular, the ozone supply device of JP-A-2003-20209 includes a plurality of processing chambers for liquefying and vaporizing only ozone, and by individually controlling the temperature of the processing chambers, it is possible to super High concentration ozone gas is supplied as a continuous supply. Further, as a commercially available ozone generating device that follows this ultra-high concentration ozone gas continuous supply method, for example, a pure ozone generator (MPOG-HM1A1) made of a bright electric power can be cited. The ozone gas is not limited to the above-mentioned ultra-high concentration ozone gas. For example, an ozone gas having an ozone concentration of several tens of % or more can be cited. At atmospheric pressure, at a concentration of 14.3 to 38 vol% of ozone, it is a continuous decomposition zone, at a concentration of ~44 vol% ozone, which is a deflagration zone, and -12-200908133 at an ozone concentration of ~44 vol%. , is the area of the outbreak (Shuguang handsome 'basis and application of ozone' Guanglin, 1996, ppl87). In the ozone water producing apparatus 1, since the ozone gas and the steam are mixed in a state where the atmospheric pressure is lower, the risk of explosion can be avoided. The vacuum pump 3 is a pump for decompressing the inside of the processing chamber 2. A pipe 1 that connects the processing chamber 2 and the vacuum pump 3 is provided with a valve 1 1 ° valve 1 1 ' to make the pressure in the processing chamber 2 a specific one, and the inside of the processing chamber 2 The gas phase is used for sealing. The treatment chamber 2' piping 1〇 and the valve 11' may be configured by a material having resistance to ozone as in stainless steel. The heater 4' heats the side faces of the lid 21, the piping 6, and the processing chamber 2 to at least the extent that the water vapor introduced into the processing chamber 2 is not liquefied. The heater 4 is suitable for use by a person skilled in the art of semiconductor technology. The cooling mechanism 5 cools the bottom portion so that the water vapor containing ozone is dew condensation at the bottom of the processing chamber 2. The cooling mechanism 5 is formed by a flow passage 24 in which a refrigerant such as cooling water is buried in the bottom portion 23 of the processing chamber 2. The flow path 24 is provided to uniformly cool the bottom surface of the processing chamber 2 as much as possible. Next, an operation example of the ozone water producing apparatus 1 will be described with reference to Figs. 1 and 3 . In the processing chamber 2 under reduced pressure, an ultra-high concentration ozone gas is sealed. Next, water vapor is introduced. At this time, the side of the -2 - 200908133 inside the processing chamber 2 and the ceiling surface (below the lid 21) are heated to such an extent that the water vapor is not liquefied. For example, when the internal pressure of the processing chamber 2 is 100 kPa, the temperature of the inner side surface and the ceiling surface is maintained at a temperature higher than 45 ° C according to the saturated vapor pressure curve of FIG. 3 . For example, it is kept at 100 °C. On the other hand, the bottom of the processing chamber 2 is cooled by the cooling water flowing through the buried flow path 24. For example, when the internal pressure system of the processing chamber 2 is 1 〇〇hPa, the temperature of the bottom portion is cooled to below 45 ° C according to the saturated vapor pressure curve of FIG. 3 'for example, cooled to 20 0 4 0 °C. Thereby, the water vapor mixed with ozone is liquefied as the condensation 25 on the bottom surface portion of the processing chamber 2. The above-described work is carried out in a reverse manner, and in the processing chamber 2, high-concentration ozone water 26 which does not contain impurities other than NOx or cesium 2 or the like 03 is stored. If a certain amount is stored, the supply of ultra-high concentration ozone gas and water vapor is stopped. The stored high concentration ozone water 26 is discharged through the valve 8. Fig. 2 is a cross-sectional view showing a schematic configuration of a substrate surface treatment apparatus according to an embodiment of the present invention. The substrate surface treatment apparatus 30 removes an organic substance containing a photoresist from the surface of the substrate 31 by high-concentration ozone water. The substrate surface treatment apparatus 30' has the same configuration as that of the ozone water producing apparatus 1 except that the bottom portion of the processing chamber 2 is formed with the holding portion 3 2 on which the substrate 31 for removing the organic matter is placed. The holding portion 32 is formed by controlling the bottom surface portion in accordance with the shape of the substrate. Referring to Fig. 2, an explanation will be given of an example of the substrate surface treatment device 30-14 - 200908133. In the treatment chamber 2 under reduced pressure, an ultra-high concentration ozone gas is sealed, and then water vapor is introduced. At this time, the inner side surface of the processing chamber 2 and the ceiling surface (the lower surface of the lid 21) are heated as shown in Fig. 3 to such an extent that the water vapor is not liquefied. For example, when the internal pressure system of the processing chamber 2 is 120 hPa (ozone partial pressure 90 hPa, water vapor partial pressure 30 hPa), the temperatures of the inner side surface and the ceiling surface are maintained according to the saturated vapor pressure curve of FIG. At a temperature higher than 45 °C, for example, it is kept at 1 °C. On the other hand, the bottom portion 23 of the processing chamber 2 is cooled by the cooling water (refrigerant) flowing through the buried flow path 24. For example, when the internal pressure system of the processing chamber 2 is 120 hPa (ozone partial pressure 90 hPa, water vapor partial pressure 30 hPa), the temperature of the holding portion 32 is cooled to 45 ° C or less according to the saturated vapor pressure curve. For example, it is cooled to 20~4〇 °C. Thereby, the steam of ozone is mixed, and condensation is formed on the bottom surface of the processing chamber 2. The above-mentioned work is carried out repeatedly, and high-concentration ozone water 26 which does not contain impurities other than NOx or 02 or the like 03 is stored. Then, the engineering is continued until the substrate 31 in the processing chamber 2 is immersed. On the right, if there is a certain amount stored, the supply of ultra-high concentration ozone gas and water vapor is stopped. The high-concentration ozone water 26 stored as described above is discharged through the valve 8. The substrate 3 1 treated by the high concentration of ozone water is further washed by ultrapure water. The ultrapure water may be introduced from the pipe 6. The organic component of the substrate 31 treated by the ozone gas and the water vapor is oxidatively decomposed into a water-soluble component (for example, an aldehyde or a hydroxide by reaction with ozone gas and water vapor -15-200908133). ()). (Edited by the Japan Chemical Society, the general manager of the quarterly journal, No. 7, Chemistry of Reactive Oxygen, issued on April 20, 1990, pp. 36~37). Therefore, by washing the substrate 31 with ultrapure water, the residue formed by the water-soluble component described above on the surface of the substrate 31 can be easily removed. Further, it is also conceivable that the photoresist which is deteriorated by washing with ultrapure water is removed, and it can be thinned. Table 1 shows a test example in which the organic substance which is one example of the organic material of the organic material is removed by the substrate surface treatment apparatus 30. It is a photoresist of the phthalate/diazonaphthoquinone-based photoresist, and has OFPR-800 (a photo-resistance photoresist for G-line (436 °) light) manufactured by Tokyo Applied Chemical Industry Co., Ltd. The Si substrate is stored in the processing chamber 2. The temperature of the side wall of the processing chamber 2 was adjusted to about 1 〇〇 ° C and the temperature of the holding portion 3 2 was changed to 40 ° C (3 6 to 40 ° C) or less. Next, an ultra-high concentration ozone gas and water vapor are supplied into the processing chamber 2, and the condensation is caused to the extent that the substrate is immersed. At the ozone generating device 9 for supplying the above-mentioned ultra-high concentration ozone gas, a pure ozone generator (MPO-HM1A1) made of a bright electricity is used. The substrate was sealed for 5 minutes in a state where the partial pressure of ozone was 9000 Pa and the partial pressure of water vapor was 3 000 Pa, and then washed with ultrapure water. In Table 1, the film thickness [nm] of the photoresist before and after the treatment, the difference between the film thickness [nm] before and after the treatment, and the peeling speed [nm/min] are shown. In Table 1, the result of ashing the three samples S 1 to S 3 (substrate having the photoresist) was revealed. -16- 200908133 [Table i] The photoresist was treated with high concentration of ozone water! After that, the sample photoresist thickness difference peeling speed before treatment [nm] after treatment [nm] [nml [nm/min ] S1 1144.4 501.2 643.2 128.6 S2 1144.4 504.1 640.3 128_1 — S3 1144.4 468.2 676.2 135.2 After the photoresist is treated with high concentration of ozone water, the thickness of the photoresist film is poor when it is washed with pure water [ Nml stripping speed [nm/min] before treatment [nm] after treatment [nm] S1 1 144.4 368.1 776.3 155.3 S2 1144.4 342.8 801.6 160.3 S3 1 144.4 399.2 745.2 149.0 From the results shown in Table 1, it is obvious that It was confirmed that, by the substrate surface treatment method of the present invention, it is possible to remove the organic substance exemplified by the photoresist at a temperature lower than 1 〇〇 ° C. Also, it was confirmed that: No cracking occurred in the substrates of both. [Brief Description of the Drawings] Fig. 1 is a cross-sectional view showing a schematic configuration of a high-concentration ozone water producing apparatus according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing a schematic configuration of a substrate surface treatment apparatus according to an embodiment of the present invention. [Fig. 3] Saturated water vapor pressure curve. -17- 200908133 [Description of main components] 1 : Ozone water production equipment 2 : Processing chamber 3 : Vacuum pump 4 : Heater 5 : Cooling mechanism 6 : Piping 7 : Piping 8 : Discharge valve 9 : Ozone generating device 1 〇: piping 1 1 : valve 2 0 : processing container 21 : cover 22 : Ο type ring 2 3 : bottom 24 : flow path 2 5 : condensation 6 6 : high concentration ozone water 3 〇 : substrate surface treatment device 3 1 : substrate 3 2 : Keeping section -18 -