A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（1 ) 【發明所屬之技術領域】 本發明有關處理基板表面所用之裝置，更詳細爲關於 完全分離處理基板表面後之處理廢液與淸洗液，並且，將 所回收之處理廢液再調整至處理液就可循環使用處理液之 基板表面之處理裝置。 【習知技術】 於半導體元件，液晶顯示元件等種種電子元件之製造 ，首先，在基板表面形成絕緣體層，半導體層，導電體層 等薄膜。其次，在所形成之薄膜上塗布抗蝕劑層之後，施 加曝光處理，由顯像液及蝕刻液形成圖案。並且，藉塗布 抗蝕剝離液除去殘留於基板表面之抗蝕劑。又，並且，在 基板表面給與淸洗液（rinse liq )(例如異丙醇（isopropy 1 alcohol )等醇類，純水等），以去除尙殘留之微細抗蝕 劑粒子，處理液等。像這樣於電子元件之製造，進行使用 複數處理液及淸洗液之濕式處理。 於上述濕式處理，晶圓等基板係使用下列方法； (1 )直接浸滲於含有處理液之處理槽內與含有淸洗 液之淸洗槽內之方法，（2)固定於迴轉自如之晶圓夾具 (wafer chuck)，對於基板表面使用噴吹噴嘴（spray η ο z z 1 e )或直接噴嘴（s t r a i g li t η ο z z 1 e )依序噴吹處理液與 淸洗液，利用晶圓夾具之迴轉處理全部基板之旋轉器（ spinner )的方法，（3 )在滾輪運送機（roller conveyer )上配置基板，向基板處理方向依序塗布處理液與淸洗液 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公釐） -4 - 447026 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（2 ) 之方法，或，（4)在卡匣配置多數之基板，在基板表面 使用噴霧噴嘴噴吹處理液與淸洗液的方法= 但是，於上述利用浸滲之方法，係隨著處理多數晶 圓處理液中之成分濃度就發生變化，具有不能進行安定之 表面處理之問題。另一方面，使用旋轉器或滾輪運送機時 ，則具有會產生混合處理液之廢液（處理廢液）與淸洗液 之廢液（淸洗廢液）之龐大廢液之問題。 爲了欲將由這種基板處理所產生之廢液分離爲處理廢 液與淸洗液提案有各種旋轉器。 例如，曰本特開平5 — 190442號公報，掲示有 在晶圓夾具周圍裝設外側杯（outer cup )與內側杯（inner cup )之二層構造杯之旋轉器。旋轉器’係內側杯爲升降 自如，由於內側杯之上下移動就可分離回收處理液°所分 離回收之處理廢液更容易地加以廢液處理’或再利用。 於曰本特開平8 — 8 8 1 6 8號公報，揭示有構成爲 在晶圓夾具周圍裝設升降自如之內環（inner rins ) ’當內 環位於上部時其下端爲變成隔間壁之內側’內環位於下部 時其下端爲變成隔間壁外側之旋轉器。 另者，於日本特開平5 — 2 8 3 3 9 5號公報’揭示 有在固定於迴轉自如之支持器上之基板’透過儲存容器給 與處理液，回收其處理廢液送還儲存容器之薄材之清淨化 裝置。此淸淨化裝置爲可循環使用處理液° 又，於日本特許2 6 0 2 1 7 9號公報，揭不有作爲 處理液使用鏈院醇胺（alkano1 amine )與有機溶媒’將處 本纸張尺度適用中國國家標準（CNS)A4規格（210x 297公釐）_ 5 - ! ------^!l·— — — 訂·ίι· — — —·線 (請先間讀背面之注意事項再填寫本頁) 4 470 2 6 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（3 ) 理廢液（抗蝕劑剝離廢液）內之鏈烷醇胺濃度以吸光光度 計檢測，並且，補給不足成分來再生處理液之抗蝕劑剝離 液管理裝置。並且，於日本特開平1 0 — 2 2 2 6 1號公 報，揭示有作爲處理液使用鏈焼醇胺（alkanol amine )與 有機溶媒與純水，將處理廢液（抗蝕劑剝離廢液）內之純 水濃度使用吸光光度計檢測，並且，補給不足成分來再生 處理液之抗蝕劑剝離液管理裝置。這些管理裝置係檢測處 理液內之特定成分，加以補給，所以不至於使處理液劣化 ，可調整成不斷具有一定處理性能之處理液。 【發明所欲解決之問題】 上述日本特開平5 — 1 9 0 4 4 2號公報所記載之旋 轉器，係只有分離回收處理廢液而已，反復循環處理或處 理廢液之中處理液中之成分濃度就發生變化，具有對於基 板之處理能力降低之問題》 又，日本特開平5 — 283395號公報所記載之裝 置，因只將處理廢液送還儲存容器，所以反復循環處理處 理液或處理廢液之中處理液中之成分濃度就發生變化，具 有對於基板之處理能力降低之問題 同樣，日本特開平5 — 2 8 3 3 9 5號公報所記載之 旋轉器，係只分離回收處理廢液而已，所以反復循環處理 處理液或處理廢液之中處理液中之成分濃度就發生變化， 具有對於基板之處理能力降低之問題。 又，日本特許2 6 0 2 1 7 9號公報及日本特開平 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ~ — -------- 裝 --訂·！----線 (請先閲讀背面之注意事項再填寫本頁) 4470 2 6 經濟部智慧財產局員工消費合作社印驳 A7 B7 五、發明說明（4 ) 1 0 — 2226 1號公報所記載之管理裝置，係適用於利 用旋轉器之基板表面處理裝置時，淸洗液係以處理液相等 或更多之量使用之情形居多，因不能分離回收處理廢液， 所以由於稀釋致使有效成分大幅度地降低從再生效率上之 觀點具有浪費多之問題。 於半導體或液晶基板之抗蝕劑剝離製程，係倂用實施 由氧電漿之乾灰化（dry ashing )製程與由抗蝕劑剝離液 之濕式剝離製程。在經過氧電漿之乾灰化製程之基板因殘 留有堅固之抗蝕劑變質物或矽氧化物等之金屬氧化物，所 以，在其後之濕式剝離製程，係欲將這些完全剝離去除事 實上變成困難。因此，雖然採取提高處理液之溫度，延長 處理時間，但是具有安全上之問題，又，從生產效率之觀 點也有問題。又，爲了提高物理性之處理能力，雖然利用 旋轉器，在其表面上施加0 . 5〜5kg/cm2 G程度 之壓力進行處理液之塗布，但是，其係認爲由於迴轉自如 之旋轉器與壓力塗布之相乘效果而處理能力會提高° 又，雖然提案有藉使用複數台之旋轉器，將處理液與 淸洗液由各個旋轉器做另外之處理，但是’因具有基板表 面處理裝置之尺寸變大的問題並非現實。 另者，若將處理液與淸洗液由同一旋轉器處理時’恐 有不能使用如上述之管理裝置之虞，而變成作爲實際問題 不能生產製品之事態。 從這些情形強烈地要求下列情形；欲將基板表面處理 裝置或管理裝置儘量變小，處理液係欲一般地使用’並且 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -- --------- ^ ' I I--r I--^--- - -- 翁 — $ (請先Μ婧背面之沒意事項再填寫本頁) A7 B7 五、發明說明（5 ) ’有效地再利用其處理液，淸洗液係由處理液之處理後欲 立即塗布，減少處理廢液。 (靖先閱讀背面之注$項再填寫本頁> 本發明係爲了解決上述問題所開發者，其目的係提供 一種，將處理基板表面後之處理廢液與淸洗廢液完全分離 回收’對於所回收之處理廢液補給因應液中之成分濃度之 變化之處理調整液，藉再調整處理液，而可循環使用處理 液，並且，即使反復循環也可持續保持處理液本身性能之 基板表面處理裝置。 【解決問題之手段】 爲了達成上述目的，本發明之基板表面處理裝置，係 由備有；對於配置於處理台上之基板依序給與處理液與淸 洗液以處理基板表面之處理手段；將處理廢液與淸洗液另 外回收之液體回收手段；將該處理廢液之廢液貯留手段； 將處理廢液中之至少1種成分之濃度使用導電率計及/或 吸光光度計加以檢測，依據檢測値補給處理調整液，調整 處理液之濃度檢測，液補給手段；及將所調整處理液供給 於上述處理手段之處理液供給手段所構成。 經濟部智慧財產局員工消費合作社印製 又，本發明之基板表面處理裝置，其特徵爲備有；對 於配置於處理台上之基板依序給與處理液與淸洗液以處理 基板表面之處理手段；將處理廢液與淸洗液另外回收之液 體回收手段；貯留該處理廢液，將處理廢液中之至少1種 成分之濃度使用導電率計及/或吸光光度計加以檢測，依 據檢測値補給處理調整液，調整處理液之廢液貯留，濃度 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） · 8 - 4 4 7 0 2 6 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（6 ) 檢測，液補給手段：及將所調整處理液供給於上述處理手 段之處理液供給手段（參照第1圖〜第5圖）。 於上述之發明，於其一實施形態，廢液貯留手段，係 具有攪拌處理廢液，並且加以過濾之攪拌過濾部。 於上述之本發明裝置，於其一實施形態，係具有廢液 貯留，濃度檢測，液補給手段係攪拌所調整之處理液，並 且過濾之攪拌，過濾部。 於上述本發明裝置，其一實施形態，係更且因應回收 上述淸洗廢液，從該淸洗廢液之回收開始之時間經過一定 時間，分離爲回收開始即後之含有異物淸洗廢液與從回收 開始經過一定時間後之（未含有異物）之第2淸洗廢液之 淸洗廢液分離手段爲連接於液回收手段（參照第3圖，第 4圖，第5圖）。 於上述本發明之裝置，其一實施形態，上述基板係印 刷電路板，液晶基板，半導體基板或電漿液晶器基板。 於上述之本發明裝置，於另外實施形態，上述處理台 係迴轉自如之晶圓夾具（參照第3圖，第4圖），滾輪運 送機（參照第1圖，第2圖）及卡匣（參照第5圖）之任 -* α 於另外實施形態，上述處理台係晶圓夾具，並且上述 液回收手段，具有外壁與內壁之可升降之杯，與包圍該杯 之外殼。亦即》於這些本發明之裝置，上述處理台係載置 基板而迴轉自如之圓晶夾具，上述液回收手段係具有可在 遮蔽基板之位置與露出基板周圍之位置升降之內壁，與在 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ~''―* — II--^ illr-111 ---I----^ (請先閱讀背面之注意事項再填寫本頁) A7 A7 經濟部智慧財產局員Η消費合作社印製 五、發明說明（7 ) 該內壁外周一體地連設而形成可升降之杯之外壁 由內壁與外壁所形成之可升降之該杯之外殻之構 第3圖）° 另外實施形態，上述處理台爲晶圓夾具，並 液回收手段，係具有固定於該晶圓夾具周圍之隔 內裙部及具有外裙部之內杯，與包圍該隔間壁及 外殼，該內杯若位於較該晶圓夾具更上側時，該 配置於該隔間壁內側，並且，若較該晶圓夾具更 該外裙部係配置於該隔間壁外側。亦即，於這些 裝置，上述處理台，係載倉基板而迴轉自如之晶 上述回收手段係具有；將基板繞轉狀包圍所裝設 及外裙部之可升降之內杯’與包圍該內杯之外殼 固定在該外殼底面之內裙部下方與外裙部下方間 ，該內杯若位於基板上側時，從基板之廢物由內 入於該隔間壁內側’該內壁爲位於下側時’從基 由外裙部被導入於該隔間壁外側之構成（參照第 於上述本發明之裝置，其1個實施態樣’上 爲顯像液。 於上述本發明之裝置’另外實施形態’上述 鹼性物質，與對於鹼鹼性物質1 0 0重量部含有 重量部〜2 5重量部純水之液體。 此時，由導電計及/或吸光光度計所檢測之 顯像液中之鹼性物質及溶解抗触劑之至少之一。 又，含在顯像液之鹼性物質’係由氫氧化鉀 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐）-10 ，與包圍 成（參照 且，上述 間壁，與 該內杯之 內裙部係 下側時， 本發明之 圓夾具， 之內裙部 ，與位於 之隔間壁 裙部被導 板之廢液 4圖）。 述處理液 顯像液係 0.04 成分，係 ，氫氧化 f —I! ^----^----i Ϊ I -----^ <請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 --------B7 五、發明說明（8 ) 鈉’碳酸鈉，碳酸氫鈉，磷酸鈉，矽酸鈉，四甲基銨羥基 物（t e t r a m e t h y 1 e a m m m i u m h y d r ο X i d e )，三甲單錢羥基物 (trimethyle monoethanol ammonium )所形成之群所選擇 之至少~種。 於上述之本發明裝置，其一實施形態*上述處理液係 透明導電膜用蝕刻液。 於上述之本發明裝置，另一實施形態，上述蝕刻液， 係鹽酸與硝酸之混合水溶液，鹽酸與氯化二鐡之混合水溶 液，溴化氫酸水溶液，溴化氫酸與鹽酸二鐵之混合水溶液 ’碘化氫酸與氯化二鐵之混合水溶液及草酸水溶液之至少 —種。 此時，由導電計及/或吸光光度計所檢測之成分，係 透明導電膜用蝕刻液中之酸及溶解銦之至少一種。 於上述本發明之裝置，另外實施形態，上述處理液係 抗蝕劑剝離液。 於上述之本發明裝置，另一實施形態，上述抗蝕劑剝 離液係鏈烷醇胺（alkanolannne )，與對該鏈烷醇胺100 重量部含有2 0重量部〜8 0 0重量部之有機溶媒之液體 〇 此時，由導電計及/或吸光光度計所檢測之成分，係 抗蝕劑剝離液中之溶解抗蝕劑及鏈烷醇胺之至少之一。於 上述之本發明裝置，另一實施形態，上述抗蝕劑剝離液係 鏈烷醇胺（alkanolamine )，與對該鏈烷醇胺10 0重量部 含有2 0重量部〜8 0 0重量部之有機溶媒，與5重量部 I t---— *裝-----：---—訂---------線 <請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用令國國家標準（CNS)A4規格（210 X 297公釐） -11 - J/ 經濟部智慧財產局員工消費合作社印製 170 2 6 Ki ___B7_____五、發明說明（9 ) 〜900重量部純水之液體。 此時，由導電計及/或吸光光度計所檢測之成分，係 抗蝕劑剝離液中之溶解抗蝕劑，鏈烷醇胺及純水之一。 又，於上述之本發明裝置，另一實施形態，上述抗蝕 劑剝離液係鏈烷醇胺，與對該鏈烷醇胺1 0 0重量部含有 2 0重量部〜8 0 0重量部之有機溶媒，與5重量部 〜9 0 0重量部之純水，與含有1重量部〜3 0 0重量部 之經胺（hydroxylamine )之液體。 此時，由導電計及/或吸光光度計所檢測之成分，係 抗蝕劑剝離液中之溶解抗蝕劑，鏈烷醇胺，純水及羥胺之 至少之一。 含在抗蝕劑剝離液之鏈烷醇胺，爲由乙醇胺（monoeth anolamine )，次醇胺（diethanolamine )，三醇胺（trietha nolamine ) ，N，N —二甲胺（N，N — dimethylamine ) ，N，N — 二乙醇胺（N，N — diethanoleamine )，氣基 乙醇胺（aminoethanoleamine) ’ N —甲基一N ’ N —二乙 醇胺（N — diethanoleamine ) ，N，N —二丁醇胺（N ’ N — dibutylamine ) ，N—甲醇胺（N * N — methlethanolamine )及 3 —氨一 1—两醇（3 — amino -1- propanol )所形成之群所選擇之至少一種胺。 【發明之實施形態】 茲就有關本發明之實施形態詳細說明如下’但是本發 明係不由下述實施形態受到任何限制，而是可適當變更實 本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公釐） -12- -------I I! ^ ίιιΓί — ^ --- (請先閱讀背面之注意事項再填寫本頁) A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明〇〇 ) 施者。 第1圖係表示本發明之實施第1形態之基板表面處理 裝置。本實施形態，係在滾輪運送機上配置基板，向基板 之處理方向依序給與處理液與淸洗液。 如第1圖所示，配置於滾輪運送機1 0之基板1 2， 係向圖中之箭頭方向移動，首先被導入於處理液供給裝置 1 4。導入於處理液供給裝置1 4之外殼1 6內之基板 1 2 ’係從噴霧噴嘴1 8供給處理液。 由處理液經過表面處理之基板1 2，係繼續導入於淸 洗液供給裝置2 0 =在導入於淸洗液供給裝置2 0之機殼 22內之基板12，就從噴霧噴嘴24供給淸洗液。作爲 淸洗液，係使用醇類（例如，異丙醇）或純水。 按，替代噴霧噴嘴1 8，2 4 3也可以使用直線噴嘴 或其他噴嘴等·•並且，基板1 2從處理液供給裝置1 4導 入於淸洗液供給裝置之前，在基板1 2表面及背面，從送 風機（未圖示）等從空氣刀或氮氣刀噴吹空氣或氮氣，以 去除附著於基板之處理液較佳。藉此，就可防止由基板帶 出之處理液及處理液供給裝置14所產生之處理液之煙霧 進入於淸洗液供給裝置2 0內。於本實施形態，係處理液 供給裝置1 4及淸洗液供給裝置2 0將成爲處理手段。 於處理液供給裝置1 4，給與基板表面後之處理液（ 處理廢液），係從廢液池部2 6底部排出輸送到廢液回收 ，液體補給裝置2 8。貯留於廢液回收，液體補給裝置 2 8之處理廢液，係由導電率計3 0及/或吸光光度計 --- ------波 i I — ----訂---I !-線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -13- 經濟部智慧財產局員工消費合作社印製 70 2 6 A7 -*___ B7___五、發明說明（11 ) 3 2測定導電率及/或吸光度，其測定値係輸入於控制器 6 2 ’檢測處理廢液中之1或更多之成分濃度。因應其檢 測濃度藉來自控制器6 2之訊號調節控制閥6 4及/或控 制閥6 5之開度，對於處理廢液則從處理調整液槽3 4及 /或處理調整液槽3 5補給含有調整所需成分之既定量處 理調整液以調整處理液。3 6係溫度調節用之加熱器3 6 而爲了將處理液之溫度保持爲一定所設置者。3 8係液面 感測器3 8，爲了控制處理液之液面液位所裝設者。 所調整之處理液，係由幫浦4 0輸送到過濾器4 2， 由過濾器4 2所過濾後，供給於噴霧噴嘴1 8循環使用於 在處理液供給裝置1 4給與基板表面。此時，如第1圖所 示，將由過濾器4 2過濾之處理液之一部送回廢液回收， 液體補給裝置2 8較佳，爲了提高處理液調整時之攪拌效 果，例如可使用噴霧噴嘴4 4送回廢液回收，液體補給裝 置2 8之構成。按，對應於所補給之處理調整液之量，或 由溢流處理廢液之一部將排出於處理廢液槽46。48， 5 0係壓力錶。 於本實施形態，有時將貯留處理廢液之廢液貯留槽裝 設於廢液池部2 6與廢液回收，液體補給裝置2 8之間。 另一方面，於淸洗液供給裝置2 0，淸洗液之廢液（淸洗 廢液），爲從廢液貯留部52底部所排放’與處理廢液另 外回收，或加以廢棄（未圖示）。5 4係幫浦’ 5 6係過 濾淸洗液所用之過濾器，5 8，6 0係壓力錶。 茲依據第2圖於廢液回收，液體補給裝置2 8之濃度 本紙張疋度適用尹國國家標準（CNS)A4規格（210 X 297公釐） -14 - I-- ----袭---I l· — I 1 訂.！--線 (請先閱讀背面之注意事項再填寫本頁) 4 經濟部智慧財產局員工消費合作社印製 70 2 6 A7 __B7五、發明說明（〗2 ) 檢測，液體補給之具體例說明如下。貯留於廢液回收，液 體補給裝置2 8之處理廢液係由導電率計3 0及/或吸光 光度計3 2測定導電率及/或吸光度，其測定値爲輸入於 控制器6 2，檢測出處理廢液中之1或更多成分之濃度。 因應其檢測濃度由來自控制器6 2之訊號調節控制閥6 4 及/或控制閥6 5之開度，對於處理廢液從處理調整液槽 3 4及/或處理調整液槽3 5補給含有需要調整成分之既 定量之處理調整液來調整處理液。此時，從處理調整液槽 3 4之處理調整液，係例如由從氮氣槽6 6之加壓氮氣所 壓送補給於處理廢液。6 8係控制閥。按，關於處理調整 液槽3 5，雖然省略詳細圖示，但是與處理調整液槽3 4 之情形相同。 於此，關於處理廢液中之成分濃度之檢測方法及調整 方法具體地說明如下。 於鹼系顯像液，將鹼濃度與導電率之關係依實驗加以 檢討，而確認了對於導電率鹼濃度爲支配性而可由高度直 線相關關係測定，所以，將減少鹼濃度由導電率計檢測’ 補給較處理液其鹼濃度更大之鹼系顯像原液加以調整。 又，抗蝕劑濃度與吸光度之關係由實驗檢討，確認了 對於可視部之波長（例如，4 8 0 nm)之吸光度其抗蝕 劑濃度爲支配性可由直線關係測定，所以將抗蝕劑濃度增 大之事由吸光光度計檢測，而補給未含有抗蝕劑之鹼系顯 像新液加以調整。 於透明導電膜用蝕刻液，係將溴化氫氧濃度與導電率 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- 447026A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) [Technical field to which the invention belongs] The device for treating the substrate surface of the present invention is more detailed about the processing waste liquid after the substrate surface is completely separated and processed And a cleaning solution, and a processing device for reusing the recovered processing waste liquid to the processing liquid to recycle the processing liquid on the substrate surface. [Known Technology] For the manufacture of various electronic components such as semiconductor elements, liquid crystal display elements, etc., first, a thin film such as an insulator layer, a semiconductor layer, and a conductor layer is formed on a substrate surface. Next, after a resist layer is coated on the formed thin film, an exposure process is applied to form a pattern with a developing solution and an etching solution. Then, the resist remaining on the substrate surface is removed by applying a resist stripping solution. Furthermore, a rinse liquid (e.g., alcohol such as isopropy 1 alcohol, pure water, etc.) is applied to the surface of the substrate to remove fine resist particles, treatment liquid, and the like remaining on the substrate. In this way, in the manufacture of electronic components, a wet process using a plurality of processing liquids and a washing liquid is performed. In the above wet processing, the following methods are used for substrates such as wafers: (1) a method of directly impregnating in a processing tank containing a processing solution and a cleaning tank containing a cleaning solution, and (2) fixed to a freely rotating For wafer chuck, use a spray nozzle (spray η ο zz 1 e) or a direct nozzle (straig li t η ο zz 1 e) to sequentially spray the processing liquid and cleaning liquid on the substrate surface. The method of rotating the fixture to spinner all substrates. (3) Dispose the substrate on a roller conveyer, and apply the treatment liquid and cleaning liquid in order to the substrate processing direction (please read the note on the back first) Please fill in this page again for this matter) This paper size applies to Chinese National Standards < CNS) A4 size (210 X 297 mm) -4-447026 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Method, or (4) a method of arranging a large number of substrates on a cassette, and spraying a processing liquid and a cleaning solution on the surface of the substrate using a spray nozzle = However, in the above-mentioned method using infiltration, the processing is performed with the majority of wafers Of the liquid Component concentration change occurs, is a problem of stability of the surface treatment can not be performed. On the other hand, when a spinner or a roller conveyor is used, there is a problem that a large amount of waste liquid that generates mixed waste liquid (treatment waste liquid) and washing liquid waste liquid (washing waste liquid) is generated. Various spinners have been proposed in order to separate the waste liquid generated by such substrate processing into a processing waste liquid and a cleaning solution. For example, Japanese Patent Application Laid-Open No. 5-190442 discloses a spinner in which a two-layer structure cup of an outer cup and an inner cup is provided around a wafer holder. The spinner's inner cup can be raised and lowered freely, because the inner cup can be moved up and down to separate and recover the treatment liquid. The separated and recovered treatment waste liquid can be more easily treated with waste liquid or reused. In the Japanese Patent Publication No. 8-8 8 1 6 8, it is disclosed that an inner ring (inner rins) is provided around the wafer jig. 'When the inner ring is located at the upper part, its lower end becomes a partition wall. The inner 'inner ring' is located at the lower part and its lower end is a spinner which becomes the outer side of the partition wall. In addition, in Japanese Patent Application Laid-Open No. 5-2 8 3 3 9 5 'disclosed a substrate fixed on a freely rotating supporter' to give a processing liquid through a storage container, recover the processing waste liquid and return it to the storage container. Material purification equipment. This purifying device is a recyclable treatment solution. In Japanese Patent No. 2 60 2 179, it was revealed that there is no use of alkano1 amine and organic solvents as the treatment solution. The scale is applicable to the Chinese National Standard (CNS) A4 specification (210x 297 mm) _ 5-! ------ ^! L · — — — Order · ίι · — — — · (Please read the note on the back first Please fill in this page for further details) 4 470 2 6 A7 B7 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) Alkanolamine concentration in the physical waste solution (resist stripping waste solution) in terms of absorbance The meter detects and supplies a resist stripping liquid management device that supplies insufficient components to regenerate the processing liquid. In addition, in Japanese Patent Application Laid-Open No. 10-22.2 26.1, it is disclosed that alkanol amine, an organic solvent, and pure water are used as a treatment liquid, and a treatment waste liquid (resist stripping waste liquid) is used. The concentration of pure water in the apparatus is detected by an absorbance photometer, and a resist stripping liquid management device for regenerating the processing liquid by supplying insufficient components is regenerated. These management devices detect specific components in the processing liquid and replenish them, so that the processing liquid is not deteriorated, and can be adjusted to a processing liquid that constantly has a certain processing performance. [Problems to be Solved by the Invention] The spinner described in the aforementioned Japanese Patent Application Laid-Open No. 5-1 9 0 4 4 2 is only for separating and recovering the processing waste liquid, and repeatedly recycling or treating the processing liquid in the processing waste liquid. The concentration of the component changes, and there is a problem that the processing capacity of the substrate is reduced. Also, the device described in Japanese Patent Application Laid-Open No. 5-283395 discloses that only the processing waste liquid is returned to the storage container, so the processing liquid or processing waste is repeatedly recycled The concentration of the components in the processing solution in the liquid changes, and there is a problem that the processing capacity of the substrate is reduced. Similarly, the spinner described in Japanese Patent Application Laid-Open No. 5-2 8 3 3 9 5 only separates and recycles the processing waste liquid. That is why the component concentration in the processing liquid in the processing liquid or the processing waste liquid is repeatedly circulated, which has the problem of reducing the processing capacity of the substrate. In addition, Japanese Patent No. 2 6 0 2 1 7 9 and Japanese Unexamined Patent Publication No. apply to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ~ — -------- binding-ordering ·! ---- Line (Please read the precautions on the back before filling this page) 4470 2 6 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (4) 1 0 — 2226 The management device is applicable to the substrate surface treatment device using a spinner. The cleaning liquid is mostly used in the processing liquid phase or more. Since the waste liquid cannot be separated and recovered, the effective component is large due to dilution. From the viewpoint of regeneration efficiency, there is a lot of waste. The resist stripping process for semiconductor or liquid crystal substrates is carried out using a dry ashing process using an oxygen plasma and a wet stripping process using a resist stripping solution. On the substrate that has undergone the dry ashing process of the oxygen plasma, there are metal oxides such as strong resist deterioration or silicon oxide. Therefore, in the subsequent wet peeling process, it is intended to completely remove these. In fact it becomes difficult. Therefore, although the temperature of the treatment liquid is increased and the treatment time is prolonged, there are problems in terms of safety and problems in terms of production efficiency. In addition, in order to improve the physical processing ability, although a spinner is used to apply a pressure of about 0.5 to 5 kg / cm2 G on the surface, the treatment liquid is applied. The multiplying effect of pressure coating will increase the processing ability. Also, although the proposal has adopted the use of multiple spinners, the processing liquid and the cleaning solution are separately processed by each spinner, but 'because of the substrate surface treatment device The problem of larger sizes is not a reality. On the other hand, if the processing liquid and the washing liquid are processed by the same spinner, there is a risk that the management device as described above cannot be used, and a situation in which a product cannot be produced as a practical problem may arise. From these situations, the following situations are strongly required; if the substrate surface treatment device or management device is to be as small as possible, the treatment liquid is intended to be used in general 'and this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------- ^ 'I I--r I-^ -----Weng — $ (please fill in this page with the unintentional matter on the back of M Jing) A7 B7 V. Description of the invention (5) 'The treatment liquid is effectively reused, and the cleaning liquid is to be applied immediately after the treatment liquid is treated to reduce the treatment waste liquid. (Jing first read the note on the back before filling in this page> The present invention was developed by the developer to solve the above problems, and its purpose is to provide a method that completely separates and recycles the processing waste liquid and the cleaning waste liquid after processing the surface of the substrate ' The recovered processing waste liquid is replenished with the processing adjustment liquid corresponding to the change in the concentration of the components in the liquid. By adjusting the processing liquid again, the processing liquid can be recycled, and the surface of the substrate can maintain the performance of the processing liquid itself even after repeated circulation. Processing device [Means for solving problems] In order to achieve the above-mentioned object, the substrate surface processing device of the present invention is provided; for the substrate disposed on the processing table, a processing liquid and a cleaning solution are sequentially given to process the substrate surface. Treatment means; liquid recovery means for separately recovering the treatment waste liquid and the washing liquid; storage means for the treatment waste liquid; using a conductivity meter and / or absorbance for the concentration of at least one component in the treatment waste liquid To measure, replenish the processing liquid according to the test, replenish the processing liquid concentration detection, liquid replenishment means; and supply the adjusted processing liquid It is constituted by the supply means of processing liquid based on the above-mentioned processing means. Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs and printed on the substrate surface treatment device of the present invention, which is characterized in that the substrates arranged on the processing table are sequentially given. Treatment means for treating the surface of the substrate with the treatment liquid and the cleaning solution; liquid recovery means for separately recovering the processing waste liquid and the cleaning solution; storing the processing waste liquid, and using the conductivity of the concentration of at least one component in the processing waste liquid Take into account and / or absorbance photometer to detect, replenish the adjustment liquid according to the test, adjust the waste liquid storage of the treatment liquid, and adjust the concentration of this liquid to the Chinese National Standard (CNS) A4 (210 X 297 mm). 8-4 4 7 0 2 6 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) Detection, liquid replenishment means: and treatment liquid supply means for supplying the adjusted treatment liquid to the above treatment means (refer to Section 1) (Figures to 5). In the above-mentioned invention, in one embodiment, the waste liquid storage means includes agitating and treating the waste liquid, and filtering and stirring. In the above-mentioned device of the present invention, in one embodiment, the device includes waste liquid storage, concentration detection, and liquid replenishing means that agitates the adjusted treatment liquid, and filters the stirred, filtering portion. In the above-mentioned device of the present invention, According to an embodiment, the washing liquid is recovered in response to the above. After a certain period of time has elapsed since the time when the washing liquid was recovered, it is separated into a washing liquid containing foreign matter immediately after the start of recycling and a certain period of time has elapsed from the start of recycling. The second (waste-free) second washing liquid separation means is connected to the liquid recovery means (refer to FIG. 3, FIG. 4, and FIG. 5). In the device of the present invention described above, In one embodiment, the substrate is a printed circuit board, a liquid crystal substrate, a semiconductor substrate, or a plasma liquid crystal substrate. In the above-mentioned device of the present invention, in another embodiment, the processing table is a wafer holder that can rotate freely (see FIG. 3). (Figure 4), any of the roller conveyor (refer to Figure 1 and Figure 2) and the cassette (refer to Figure 5)-* α In another embodiment, the processing table is a wafer holder, and In addition, the liquid recovery means includes a cup capable of being raised and lowered on the outer wall and the inner wall, and a shell surrounding the cup. That is, in these apparatuses of the present invention, the processing table is a wafer holder for freely revolving the substrate, and the liquid recovery means has an inner wall that can be raised and lowered at a position where the substrate is shielded and where it is exposed around the substrate, and This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ~ '' ― * — II-^ illr-111 --- I ---- ^ (Please read the precautions on the back before (Fill in this page) A7 A7 Printed by a member of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives V. Invention Description (7) The inner wall is connected to the outside to form a cup that can be raised and lowered. The structure of the shell of the cup (Figure 3) ° In another embodiment, the processing table is a wafer holder, and the liquid recovery means is provided with an inner skirt fixed around the wafer holder and an inner skirt with an outer skirt. A cup, and an enclosure that surrounds the partition wall and the outer shell, if the inner cup is located on an upper side than the wafer jig, the inner cup is disposed inside the partition wall, and if the outer skirt is disposed more than the wafer jig, The compartment wall is outside. That is, in these devices, the above-mentioned processing table is a substrate that can be revolved freely, and the above-mentioned recovery means is provided; the substrate is wrapped around the mounted and outer skirt's liftable inner cup 'and the inner The shell of the cup is fixed between the bottom of the inner skirt and the bottom of the outer skirt. If the inner cup is located on the upper side of the substrate, the waste from the substrate enters the inside of the partition wall. The inner wall is on the lower side. At the time, 'the base is formed by the outer skirt being introduced outside the partition wall (refer to the device of the present invention described above, and one embodiment of the present invention is a developing solution. The device of the present invention described above is implemented separately. Form 'The basic substance mentioned above is a liquid containing 100 to 25 weight parts of pure water for the basic alkaline substance. At this time, in the imaging liquid detected by the conductivity meter and / or the absorbance photometer At least one of alkaline substances and dissolving anti-contact agents. In addition, the alkaline substance contained in the developing solution is made of potassium hydroxide. The paper size applies the Chinese National Standard (CNS) A4 specification (210x297 mm) -10 , And the surrounding (refer to the above, the partition When the inner skirt of the inner cup is connected to the lower side, the circular clamp of the present invention, the inner skirt of the present invention, and the waste liquid of the partition wall skirt guided by the guide plate (Fig. 4). 0.04 Ingredient, Department, Hydroxide f —I! ^ ---- ^ ---- i Ϊ I ----- ^ < Please read the notes on the back before filling out this page) Staff of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the consumer cooperative A7 -------- B7 V. Description of the invention (8) Sodium 'sodium carbonate, sodium bicarbonate, sodium phosphate, sodium silicate, tetramethylammonium hydroxyl (tetramethy 1 eammmiumhydr ο X ide ), At least one species selected from the group formed by trimethyle monoethanol ammonium. In the above-mentioned apparatus of the present invention, one embodiment of the above-mentioned treatment liquid is an etching solution for a transparent conductive film. In the above-mentioned apparatus of the present invention, in another embodiment, the etching solution is a mixed aqueous solution of hydrochloric acid and nitric acid, a mixed aqueous solution of hydrochloric acid and diphosphonium chloride, an aqueous solution of hydrobromic acid, and a mixture of hydrobromic acid and ferrous chloride. Aqueous solution 'At least one of a mixed aqueous solution of hydrogen iodide and ferric chloride and an aqueous oxalic acid solution. At this time, the component detected by the conductive meter and / or the absorbance photometer is at least one of an acid in a transparent conductive film etching solution and dissolved indium. In another aspect of the apparatus of the present invention, the treatment liquid is a resist stripping solution. In another aspect of the apparatus of the present invention described above, the resist stripping liquid-based alkanolannne and the 100-weight part of the alkanolamine contain 20 to 80 weight parts of organic Liquid of the solvent ○ At this time, the component detected by the conductivity meter and / or the absorbance photometer is at least one of the dissolved resist and the alkanolamine in the resist stripping solution. In another aspect of the apparatus of the present invention described above, the resist stripping liquid-based alkanolamine and the alkanolamine at 100 parts by weight contain 20 to 80 parts by weight. Organic solvent, with 5 weight parts I t ----- * installation -----: ----- order --------- line < please read the precautions on the back before filling this page) The paper size is applicable to the national standard (CNS) A4 specification (210 X 297 mm) -11-J / Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 170 2 6 Ki ___B7_____ V. Description of the invention (9) ~ 900 Liquid by weight of pure water. At this time, the component detected by the conductivity meter and / or the absorbance photometer is one of dissolved resist, alkanolamine, and pure water in the resist stripping solution. In another aspect of the apparatus of the present invention described above, the resist stripping liquid-based alkanolamine and the alkanolamine 100 parts by weight contain 20 to 80 parts by weight. Organic solvent, pure water with 5 parts by weight to 900 parts by weight, and liquid containing hydroxylamine by 1 part by weight with 300 parts by weight. At this time, the component detected by the conductivity meter and / or the absorbance photometer is at least one of a dissolved resist, alkanolamine, pure water, and hydroxylamine in the resist stripping solution. The alkanolamine contained in the resist stripping solution is composed of monoeth anolamine, diethanolamine, trietha nolamine, N, N-dimethylamine (N, N-dimethylamine) , N, N — diethanoleamine, N, N —diethanoleamine ”N —Methyl-N’ N —N —diethanoleamine ”, N, N —Dibutanolamine (N” At least one amine selected from the group consisting of N-dibutylamine, N * N-methlethanolamine, and 3-amino-1-propanol. [Embodiments of the Invention] The following describes the embodiments of the present invention in detail. However, the present invention is not limited by the following embodiments, but the actual paper size can be appropriately changed to apply the Chinese National Standard (CNS) A4 specification ( 210x 297 mm) -12- ------- II! ^ ΊιιΓί — ^ --- (Please read the notes on the back before filling out this page) A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2. Description of the invention Fig. 1 shows a substrate surface treatment apparatus according to a first embodiment of the present invention. In this embodiment, the substrate is arranged on a roller conveyor, and the processing liquid and the cleaning liquid are sequentially supplied to the processing direction of the substrate. As shown in FIG. 1, the substrates 12 arranged on the roller conveyor 10 are moved in the direction of the arrows in the figure, and are first introduced into the processing liquid supply device 14. The substrate 1 2 ′ introduced into the casing 16 of the processing liquid supply device 14 is supplied with the processing liquid from the spray nozzle 18. The substrate 12 subjected to the surface treatment by the treatment liquid is continuously introduced into the cleaning liquid supply device 2 0 = the substrate 12 in the casing 22 introduced into the cleaning liquid supply device 20 is supplied from the spray nozzle 24 liquid. As the cleaning solution, alcohol (for example, isopropyl alcohol) or pure water is used. Press, instead of spray nozzles 18, 2 4 3, you can use linear nozzles or other nozzles, etc. • Also, before the substrate 12 is introduced from the processing liquid supply device 14 to the cleaning liquid supply device, it is on the surface and back of the substrate 12 It is preferable to blow air or nitrogen from an air knife or a nitrogen knife from a blower (not shown) to remove the processing liquid attached to the substrate. Thereby, it is possible to prevent the processing liquid carried out from the substrate and the processing liquid generated by the processing liquid supply device 14 from entering the cleaning liquid supply device 20. In this embodiment, the processing liquid supply device 14 and the washing liquid supply device 20 will be processing means. In the processing liquid supply device 14, the processing liquid (processing waste liquid) after the substrate surface is supplied is discharged from the bottom of the waste liquid pool part 26 and transported to the waste liquid recovery, and the liquid replenishment device 28. The waste liquid stored in the waste liquid recovery, liquid replenishing device 28 is treated by the conductivity meter 30 and / or the absorbance photometer --- ------ wave i I----- order --- I! -Line (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -13- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 70 2 6 A7-* ___ B7___ V. Description of the invention (11) 3 2 Determine the conductivity and / or absorbance. The measurement is input to the controller 6 2 'to detect the concentration of one or more components in the waste liquid. The opening of the control valve 6 4 and / or the control valve 65 is adjusted by a signal from the controller 6 2 according to its detection concentration, and the waste liquid is replenished from the treatment adjustment liquid tank 3 4 and / or the treatment adjustment liquid tank 3 5 An adjustment solution containing a predetermined amount of a composition required for adjustment to adjust the treatment solution. 3 6 Series heater for temperature adjustment 3 6 It is set to keep the temperature of the processing liquid constant. 3 8 series liquid level sensor 3 8 is installed to control the liquid level of the processing liquid. The adjusted processing liquid is transferred from the pump 40 to the filter 42, and is filtered by the filter 42 and then supplied to the spray nozzle 18 for recycling to the substrate surface of the processing liquid supply device 14. At this time, as shown in FIG. 1, one part of the processing liquid filtered by the filter 42 is returned to the waste liquid recovery. The liquid replenishing device 28 is preferable. In order to improve the stirring effect when the processing liquid is adjusted, for example, a spray can be used. The nozzle 44 returns the waste liquid to be recovered, and the liquid replenishing device 28 is configured. Press, corresponding to the amount of processing adjustment fluid to be replenished, or a part of the overflow processing waste liquid will be discharged to the processing waste liquid tank 46. 48, 50 series pressure gauge. In this embodiment, a waste liquid storage tank for storing the waste liquid for treatment is sometimes installed between the waste liquid tank portion 26 and the waste liquid recovery and liquid replenishing device 28. On the other hand, in the washing liquid supply device 20, the waste liquid (washing waste liquid) of the washing liquid is discharged from the bottom of the waste liquid storage unit 52 and is separately collected or discarded (not shown) Show). 5 4 series pump ’5 6 series filter used for filtering and washing liquid, 5 8, 60 series pressure gauge. The waste liquid is recovered in accordance with the second figure. The density of the liquid replenishment device 28 is based on the national standard (CNS) A4 specification (210 X 297 mm). -14-I-- ---- Strike- --I l · — I 1 Order.! -Line (Please read the notes on the back before filling this page) 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 70 2 6 A7 __B7 V. Description of the invention (〗 2) The specific examples of liquid replenishment are described below. Residual liquid stored in the waste liquid recovery. The waste liquid treated by the liquid replenishing device 28 is measured by the conductivity meter 30 and / or the absorbance photometer 32, and the measurement is input to the controller 62 and detected. Show the concentration of 1 or more components in the treatment waste. The opening of the control valve 6 4 and / or the control valve 65 is adjusted by a signal from the controller 6 2 in accordance with its detection concentration. The processing waste liquid is replenished from the processing adjustment liquid tank 3 4 and / or the processing adjustment liquid tank 3 5 It is necessary to adjust a predetermined amount of the processing adjusting liquid to adjust the processing liquid. At this time, the processing adjustment liquid from the processing adjustment liquid tank 34 is fed to the processing waste liquid under pressure by, for example, pressurized nitrogen gas from the nitrogen tank 66. 6 8 series control valve. Although the detailed illustration of the process adjustment liquid tank 3 5 is omitted, it is the same as the case of the process adjustment liquid tank 3 4. Here, the detection method and adjustment method of the component concentration in the treatment waste liquid are specifically described below. In the alkali-based imaging solution, the relationship between the alkali concentration and the conductivity was reviewed experimentally, and it was confirmed that the alkali concentration is dominant for the conductivity and can be measured by a highly linear correlation. Therefore, the reduced alkali concentration is detected by the conductivity meter 'Adjust the supply of alkali-based imaging stock solution with greater alkali concentration than the treatment solution. In addition, the relationship between the resist concentration and the absorbance was examined experimentally, and it was confirmed that the resist concentration is dominant in terms of the absorbance of the wavelength (for example, 480 nm) of the visible portion. The resist concentration can be measured by a linear relationship. The increase is detected by an absorbance photometer, and a new alkali-based imaging solution containing no resist is adjusted for adjustment. The etching solution for transparent conductive film is based on the concentration of hydrogen bromide and conductivity (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -15- 447026
五、發明說明（13 ) <請先聞讀背面之注意事項再填寫本頁) 之關係以實驗檢討，確認了對於導電率，溴化氫氧濃度爲 支配性可具直線關係測定，所以，將減少溴化氫氧濃度之 事由導電率計加以檢測，補給較處理液其溴化氫氧濃度爲 大之蝕刻劑原液加以調整。 又，將溶解銦濃度與吸光度之關係以實驗檢討’確認 了對於紫外部或可視部之波長（例如，3 4 2 τι m )之吸 光度溶解銦濃度爲支配性具直線關係可測定，所以’溶解 銦濃度增大之事由吸光光度計檢測，補給未含有蝕刻劑新 液加以調整。 於含有鏈烷胺與有機溶媒之抗蝕劑剝離液，由實驗檢 討單乙醇濃度與吸光度之關係，確認了對於近紅外部之波 長（例如，1 0 4 8 ηπι)吸光度而單乙醇濃度爲支配性 可由高度之直線關係加以測定，所以，單乙醇濃度濃度減 少之事由吸光光度計加以檢測，補給較處理液而單乙醇濃 度爲大之蝕刻劑剝離原液加以調整。 經濟部智慧財產局員工消費合作社印製 又，將抗餽劑濃度與吸光度之關係以抗蝕濃度與吸光 度之關係由實驗加以檢討，確認了對於可視部之波長（例 如，5 5 0 nm)之吸光度抗蝕劑濃度爲支配性可具直線 關加以測定，所以，抗蝕劑濃度增大之事由吸光光度計檢 測，補給未含有蝕刻劑剝離新液加以調整。 於含有鏈烷胺與有機溶媒與純水之抗蝕劑剝離液，關 於水分濃度與吸光度之關係由實驗加以檢討，確認了對於 近紅外部之波長（例如’ 9 7 6 nm)之吸光度水分濃度 爲支配性具有高度可由直線關係加以測定’所以，水分濃 本紙張尺度適用中國國家標準（CNS>A4规格（210 X 297公釐） -16- 經濟部智慧財產局員工消費合作社印製 70 2 6 A7 ____B7__五、發明說明Ο4 ) 度減少之事由吸光光度計檢測，補給純水加以調整。 又，將抗蝕劑濃度與吸光度之關係由吸光度實驗加以 檢討，確認了對於可視部之波長（例如，5 5 0 nm)之 吸光度抗蝕劑濃度爲支配性可具直線關係加以測定’所以 ，抗蝕劑濃度增大之事由吸光光度計檢測，補給未含有蝕 刻劑剝離新液加以調整。 於含有鏈烷胺與有機溶媒與純水與羥基胺之抗蝕劑剝 離液，由實驗檢討水分濃度與吸光度之關係，確認了對於 近紅外部之波長（例如，9 7 6 n m )吸光度以水分濃度 爲支配性可由高度之直線關係加以測定，所以，將水分濃 度減少之事由吸光光度計加以檢測，補.給純水加以調整。 又，將羥胺濃度與吸光度之關係以實驗加以檢討，確 認了對於近紅外部之波長（例如’ 1 0 7 n m )之吸光度 以羥胺濃度爲支配性可具直線關係加以測定，所以，將羥 胺濃度減少之事由吸光光度計檢測，補給羥胺溶液加以調 整。 又，將抗蝕劑濃度與吸光度之關係由實驗加以檢討， 確認了對於可視部之波長（例如，5 5 0 n m )之吸光度 以抗蝕劑濃度爲支配性可具直線關係加以測定，所以，將 抗蝕劑濃度增大之事由吸光光度計檢測，補給未含有蝕刻 劑剝離新液加以調整。 按，欲同時以良好精度控制成處理廢液中之主成分濃 度與溶解抗蝕劑濃度（或溶解銦濃度）變成一定，將處理 液欲維持一定處理性能爲極爲重要之事。 (請先閱讀背面之注意事項再填寫本頁> 本紙張尺度適用中國國家標準（CNS〉A4規格（210 X 297公釐） -17- 14702 6 A7 B7 經濟部智慧財產局員工消费合作社印製 五、發明說明Ο5 ) 第3圖係表示本發明之第2實施形態之基板表面處理 裝置。本實施形態係將基板固定於迴轉自如之晶圓夾具， 而對於基板表面依序給與處理液與淸洗液者，由備有外壁 與內壁之可升降之杯，將處理廢液與淸洗液另外回收》 如第3圖所示，於處理裝置（旋轉器）70，由驅動 馬達7 2在迴轉自如之晶圓夾具7 4上，基板1 2爲例如 由公知之靜電性手段或吸引性手段加以固定（載置），基 板1 2迴轉之狀態，從噴霧噴嘴7 6供給處理液對於基板 表面給與處理液，其次，從噴霧噴嘴7 8對於基板表面給 與淸洗液。8 0係淸洗液槽。按，替代噴霧噴嘴7 6， 7 8也可以使用直線噴嘴或其他噴嘴等。本實施形態，處 理裝置（旋轉器）7 0將變成處理手段。 在晶圓夾具7 4周圍，如繞轉被固定（載置）之基板 1 2設有滑槽（chute )型之杯（槽（trough ) 8 2，此杯 (槽）8 2係由升降裝置（未圖示）構成對於機殼8 8底 部可向垂直方向升降。具體上爲杯8 2之內壁8 4爲在如 遮蔽基板1 2之位置與基板1 2周圍露出位置之間進行上 下移動，即使杯8 2之外壁8 6 ’裝設成在較內壁8 4更 高位置下降時較基板1 2高度爲低。亦即，杯8 2之外壁 8 6上部，即使杯（槽）8 2最下降時’裝設成經常較基 板1 2之處理表面更位於上方位置。8 8係包圍杯（槽） 8 2之外殼。 於第3圖，從噴霧噴嘴7 6供給處理液時，杯（槽） 8 2係於外殼8 8位於最下降狀態之位置。所供給之處理 本&張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱1 :18- ~ I — — — — —III! - I ---Γ I I II ^--—III! !^. (請先閲讀背面之注意事項再填寫本頁) Μ 70 2 η 經濟部智慧財產局員工消費合作社印製 Β7 五、發明說明（16 ) 液係給與連同晶圓夾具7 4迴轉之基板1 2表面。給與表 面之處理液，係由於基板12之迴轉（離心力），向外周 均勻地擴展。並且，從基板1 2甩掉之處理廢液，係在內 壁8 4與外壁8 6之間，亦即，排出於杯（槽）8 2之中 。另一方面，從噴霧噴嘴7 8供給淸洗液時，杯（槽） 8 2係位於在外殼8 8內最上升狀態之位置。所供給之淸 洗液係給與連同晶圓夾具7 4迴轉之基板1 2表面。給與 表面之淸洗液，係由基板12之迴轉（離心力），向外周 均勻地擴展。並且，從基板1 2甩掉之淸洗廢液，就排出 於內壁8 4內側，亦即排出於外殼8 8。 杯（槽）82內之處理廢液，係輸送到廢液回收•液 補給裝置2 8。貯留於廢液回收，液體補給裝置2 8之處 理廢液，係由導電率計3 0及/或吸光光度計3 2測定導 電率及/或吸光度，其測定値將輸入於控制器6 2，檢測 出處理廢液中之一種或更多之成分濃度。因應其檢測濃度 由來自控制器6 2之訊號調節控制閥6 4及/或控制閥 6 5之開度，對於處理廢液從處理調整液槽3 4及/或處 理調整液槽3 5補給含有調整所需成分之既定量之處理調 整液來調整處理液。圖中包括以一點鏈線所圍住之導電率 計3 0及/或吸光光度計3 2之構成爲濃度檢測部。 所調整之處理液，係由幫浦4 0輸送到過濾器4 2， 由過濾器4 2過濾之後，供給於噴霧噴嘴7 6作爲在處理 裝置（旋轉器）7 0給與基板表面之循環使用。此時，如 第3圖所示，將在過濾器4 2過濾之處理液之一部爲經由 I-- ----表---— r----訂------！線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -19 -V. Description of the invention (13) < Please read the notes on the back before filling in this page) The experimental review has confirmed that for conductivity, the concentration of hydrogen bromide and oxygen can be determined as a linear relationship, so, The reduction of the hydrogen bromide oxygen concentration is detected by a conductivity meter, and the supply of the etchant stock solution having a larger hydrogen bromide oxygen concentration than the treatment liquid is adjusted. In addition, the relationship between the dissolved indium concentration and the absorbance was experimentally reviewed. It was confirmed that the dissolved indium concentration for the absorbance of the ultraviolet or visible wavelength (for example, 3 4 2 τι m) has a linear relationship with the dominance. Therefore, 'dissolution Increasing the indium concentration is detected by an absorbance photometer, and a new liquid containing no etchant is adjusted for adjustment. In a resist stripping solution containing an alkaneamine and an organic solvent, the relationship between monoethanol concentration and absorbance was examined experimentally, and it was confirmed that the monoethanol concentration was dominant for the near-red outer wavelength (for example, 10 8 ηπι) absorbance. The property can be measured by the linear relationship of the height. Therefore, the decrease of the concentration of the monoethanol concentration is detected by an absorbance photometer, and the supply of the etchant with a higher monoethanol concentration than the processing liquid is stripped and adjusted to adjust the concentration. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The relationship between the concentration of the antifeedant and the absorbance and the relationship between the concentration of the resist and the absorbance were reviewed by experiments to confirm that the wavelength of the visible part (for example, 5 50 nm). The absorbance resist concentration can be measured with a linear relationship as it is dominant. Therefore, the increase in the resist concentration is detected by an absorbance photometer, and a new liquid containing no etchant is removed for adjustment. In a resist stripping solution containing an alkaneamine, an organic solvent, and pure water, the relationship between the water concentration and the absorbance was reviewed experimentally, and the absorbance water concentration for a near-red outer wavelength (for example, '9 7 6 nm) was confirmed. For the dominance, it can be measured by a linear relationship. Therefore, the paper size of the paper is applicable to the Chinese national standard (CNS > A4 specification (210 X 297 mm)). A7 ____B7__ 5. Description of the invention 〇4) The reduction of the degree is detected by the absorbance photometer, and the pure water is adjusted. In addition, the relationship between the resist concentration and the absorbance was examined by an absorbance experiment, and it was confirmed that the absorbance resist concentration at the wavelength of the visible portion (for example, 50 nm) can be measured as a dominant linear relationship. Therefore, The increase in the resist concentration is detected by an absorbance photometer, and a new liquid containing no etchant is removed for adjustment. In a resist stripping solution containing an alkaneamine, an organic solvent, pure water, and a hydroxylamine, the relationship between the water concentration and the absorbance was examined experimentally. The concentration is dominant and can be measured by the linear relationship of the height. Therefore, the decrease of the water concentration is detected by an absorbance photometer, and the pure water is adjusted. In addition, the relationship between hydroxylamine concentration and absorbance was examined experimentally, and it was confirmed that the absorbance for a wavelength near the outer red (for example, '107 nm) can be measured with a linear relationship dominated by the hydroxylamine concentration. Therefore, the hydroxylamine concentration The reduction is detected by an absorbance photometer and adjusted by replenishing the hydroxylamine solution. In addition, the relationship between the resist concentration and the absorbance was examined experimentally, and it was confirmed that the absorbance of the wavelength (for example, 50 nm) in the visible region can be measured with a linear relationship based on the resist concentration. Therefore, The increase in the resist concentration is detected by an absorbance photometer, and a new liquid containing no etchant is removed for adjustment. It is important to control the concentration of the main component and the dissolved resist concentration (or dissolved indium concentration) in the treatment waste liquid with good accuracy at the same time, and it is extremely important to maintain a certain treatment performance in the treatment liquid. (Please read the precautions on the back before filling in this page> This paper size applies to Chinese national standards (CNS> A4 size (210 X 297 mm) -17- 14702 6 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention 〇5) Figure 3 shows a substrate surface processing apparatus according to the second embodiment of the present invention. This embodiment fixes the substrate to a freely rotating wafer holder, and sequentially supplies the processing liquid and the substrate surface to the substrate. As for the washing liquid, the waste liquid and washing liquid are recovered separately from the cups provided with an outer wall and an inner wall. As shown in FIG. 3, the processing device (rotator) 70 is driven by a driving motor 7 2 On the revolving wafer holder 74, the substrate 12 is fixed (mounted) by, for example, a known electrostatic means or attractive means. The substrate 12 is rotated, and the processing liquid is supplied to the substrate from the spray nozzle 76. The surface is provided with a treatment liquid, and then, a cleaning solution is applied to the substrate surface from the spray nozzle 78. The 80 type cleaning solution tank is used. Instead of using the spray nozzles 7, 6, 7, 8, a straight nozzle or other nozzle may be used. This embodiment , The processing device (rotator) 70 will become a processing means. Around the wafer holder 74, if the substrate 12 is fixed (mounted) around, a chute cup (trough) is provided. 8 2, This cup (groove) 8 2 is composed of a lifting device (not shown). The bottom of the casing 8 8 can be vertically raised and lowered. Specifically, the inner wall 8 4 of the cup 8 2 is a shielding substrate 1 2 It moves up and down between the position of the substrate 12 and the exposed position around the substrate 12, even if the cup 8 2 has an outer wall 8 6 ′ installed at a higher position than the inner wall 8 4 and is lower than the height of the substrate 12. That is, the cup 8 2 The upper part of the outer wall 8 6, even when the cup (slot) 8 2 is lowered the most, is installed more often than the processing surface of the substrate 1 2. 8 8 is a shell surrounding the cup (slot) 8 2. Figure 3, when the treatment liquid is supplied from the spray nozzle 76, the cup (tank) 8 is attached to the housing 8 at the most lowered position. The supplied treatment book & Zhang dimensions are applicable to China National Standard (CNS) A4 specifications ( 210 X 297 Public Love 1: 18- ~ I — — — — — III!-I --- Γ II II ^ --— III!! ^. (Please read the note on the back first (Please fill in this page again) Μ 70 2 η Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economics B7 V. Description of the invention (16) The liquid system is given the surface of the substrate 1 2 with the wafer holder 7 4 rotating. The surface is treated Due to the rotation (centrifugal force) of the substrate 12, the liquid spreads evenly to the outer periphery. Moreover, the processing waste liquid thrown away from the substrate 12 is tied between the inner wall 84 and the outer wall 86, that is, discharged into the cup (Slot) 8 2 out. On the other hand, when the scouring liquid is supplied from the spray nozzle 78, the cup (tank) 8 2 is positioned at the most raised state in the casing 88. The supplied cleaning solution is applied to the surface of the substrate 12 which is rotated together with the wafer holder 74. The cleaning solution applied to the surface is uniformly expanded to the outer periphery by the rotation (centrifugal force) of the substrate 12. In addition, the washing waste liquid thrown away from the substrate 12 is discharged to the inside of the inner wall 84, that is, to the housing 88. The waste liquid in the cup (tank) 82 is sent to the waste liquid recovery / liquid replenishing device 28. The waste liquid stored in the waste liquid recovery and liquid replenishing device 28 is measured by the conductivity meter 30 and / or the absorbance meter 32 and the conductivity and / or absorbance is measured. The measurement value will be input to the controller 62. The concentration of one or more components in the treatment waste liquid was detected. The opening of the control valve 6 4 and / or the control valve 65 is adjusted by a signal from the controller 62 according to its detection concentration, and the processing waste liquid is supplied from the processing adjustment liquid tank 3 4 and / or the processing adjustment liquid tank 3 5 The treatment liquid is adjusted by adjusting a predetermined amount of the treatment adjustment liquid of a desired component. The figure includes a structure in which the conductivity meter 30 and / or the absorbance meter 32 surrounded by a one-point chain line constitute a concentration detection section. The adjusted processing liquid is sent from the pump 40 to the filter 42, and after being filtered by the filter 42, it is supplied to the spray nozzle 76 to be used as a circulation to the substrate surface in the processing device (rotator) 70. . At this time, as shown in Fig. 3, one part of the processing liquid to be filtered in the filter 42 is passed through I ------ Table ----- r ---- Order ------! Line (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -19-
ft 4 7 0 2 C Α7 Β7 經濟部智慧財產局員工消费合作杜印製 五、發明說明（17 ) 處理液還流管4 3流還廢液回收，液體補給裝置2 8較佳 ，爲了提高處理液調整時之攪拌效果’例如’使用噴霧噴 嘴4 4就可送還廢液回收，液體補給裝置2 8。圖中包括 由一點鏈線所圍住之幫浦4 0，過濾器4 2及處理液還流 管4 3之構成爲攪拌，過濾部。 另一方面，外殻8 8內之淸洗廢液，係從外殻8 8底 部抽出，與處理廢液另外回收。此時，若從淸洗廢液之開 始回收不太經過長時間時（例如，最初之1 5秒程度）， 係在淸洗廢液可能摻混有處理廢液或其他異物，所以，打 開控制閥9 0閉合控制閥9 2，對於回收含有異物淸洗廢 液所用之第一淸洗廢液槽9 4排出清洗廢液。又，從淸洗 廢液之開始回收經過一定時間之後（例如，約經過1 5秒 後），在淸洗廢液未摻混處理廢液或其他異物，或即使有 摻混但是其係極爲微量，所以相反地打開控制閥9 2閉合 控制閥9 0，在第二淸洗廢液槽9 6排出淸洗廢液。在第 二淸洗廢液槽9 6所回收之淸洗廢液係未另外再調整可再 加利用。 按，於本實施形態，也可在外殼8 8底部回收處理廢 液，將淸洗廢液由杯（槽）82回收。此時，廢液回收， 液體補給裝置28，係與外殼88底部連接。 其他構成及作用，係與實施第1形態時同樣。 第4圖係表示由本發明之實施第3形態之基板表面處 理裝置。本實施形態，係將基板固定於迴轉自如之晶圓夾 具，在基板表面依序給與處理液與淸洗液者，由備有內裙 本紙適用中國國家標準（CNS>A4規4各(210 X 297公釐） - 20- f — — — — - Ή^·ι!ΓΙΙΙ^^*ι!ί--^ (請先閱讀背面之注意事項再填寫本頁) Α7 經濟部智慧財產局員工消費合作社印製 Β7 __五、發明說明（18 ) 部及外裙部之可升降之內杯與設置在機殼底部之隔間壁’ 將處理廢液與淸洗廢液另外回收° 如第4圖所示’於處理裝置（旋轉器）7 〇 a ’由驅 動馬達7 2在迴轉自如之晶圓夾具7 4上有基板1 2，爲 例如由公知之靜電性手段或吸引性手段所固定（載置）’ 在基板1 2迴轉狀態下’從噴霧噴嘴7 6供給處理液給與 處理液於基板表面，接著’從噴霧噴嘴7 8給與淸洗液給 與基板表面。即使於本實施形態之處理裝置7 0 a ’替代 噴霧噴嘴7 6，78也可以使用其他之噴嘴等。 在晶圓夾具7 4周圍，設有如繞轉所載置之基板1 2 之裙形狀之內杯（導引部）98，此內杯（導引部）98 係由升降裝置（未圖示）對於外殻8 8底部構成爲可向垂 直方向升降。並且，此內杯（導引部）98係由內裙部 1 0 0與外裙部1 0 2所構成，繞轉狀地設置成設於位在 外殼8 8底部之隔間壁1 0 4爲與內裙部1 0 0與外裙部 102下方之間。具體上，爲內杯（導引部）98位於基 板1 2上側位置時（圖中之二點鏈線）導引成內裙部 1 0 0至來自基板1 2之廢液（淸洗廢液）進入於隔間壁 1 0 4內側，內杯（導引部）9 8爲位於基板1 2下側位 置時（圖中之實線），外裙部10 2爲將來自基板12之 廢液（處理廢液）導引至隔間壁1 0 4外側。 於第4圖，從噴霧噴嘴7 6供給處理液時，內杯（導 引部）98係於外殼88內位於最下降狀態之位置。所供 給之處理液，將給與連同晶圓夾具7 4迴轉之基板1 2表 - I 政----l·! —訂---------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -21 - 4702 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明Ο9 ) 面。給與表面之處理液，係由於基板1 2之迴轉（離心力 )，向外周均勻地擴展。並且，從基板12甩掉之處理廢 液就從外裙部1 0 2上面（外面）排出於隔間壁1 0 4外 側。另一方面，從噴霧噴嘴7 8供給淸洗液時，內杯（導 引部）9 8係於外殼8 8內位於最爲上升狀態之位置。所 供給之淸洗液將給與連同晶圓夾具7 4迴轉之基板1 2表 面。給與表面之淸洗液係由於基板1 2之迴轉（離心力） ，向外周均勻地擴展。並且，從基板1 2所甩掉之淸洗液 ，就從內裙部1 0 0下面（內面）排出於隔間壁1 0 4內 側。隔間壁1 0 4外側之處理廢液，係從外殼8 8底部抽 出，而運送到廢液回收，液體補給裝置2 8。貯留於廢液 回收，液體補給裝置2 8之處理廢液係由導電率計3 0及 /或吸光光度計3 2測定導電率及/或吸光度，其測定値 爲輸入於控制器6 2，而檢測處理廢液之一種或較其更多 之成分濃度。因應其檢測濃度由來自控制器6 2之訊號調 節控制閥6 4及/或控制閥6 5之開度對於處理廢液補給 從處理調整液槽3 4及/或處理調整液槽3 5含有調整所 需既定量之處理調整液來調整處理液。由包括圖中之一點 鏈線所圍住之導電率3 0及/或吸光光度計3 2之構成爲 濃度檢測部。 所調整之處理液，係由幫浦4 0輸送到過濾器4 2， 由過濾器4 2所過濾之後，供給於噴霧噴嘴7 6爲了在處 理裝置（旋轉器）7 0 a給與基板表面循環使用。此時， 如第4圖所示，在過濾器4 2過濾之處理液之一部經由處 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -22 -~ I --------- I 1 1 l· I--^ *---— II (請先閲讀背面之注意事項再填寫本頁) 4 Υ ϋ 2 6 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明（20 ) 理液還流管4 3送還廢液回收’液體補給裝置2 8較佳’ 爲了提高處理液調整時之攪拌效果’例如’使用噴霧噴嘴 4 4可構成爲送還廢液回收，液體補給裝置2 8之構成。 包括圖中之一點鏈線所圍住之幫浦4 0 ’過濾器4 2及處 理液還流管4 3之構成爲攪拌.過濾部。 另一方面，隔間壁1 0 4內側之淸洗廢液，係從外殼 8 8底部被抽出，而與處理廢液另外回收。此時，若從淸 洗廢液之開始回收不太經過長時間時（例如，最初之1 5 秒鐘程度），係在淸洗廢液可能摻混有處理廢液或其他異 物，所以，打開控制閥9 0閉合控制閥9 2，對於回收含 有異物淸洗廢液所用之第一淸洗廢液槽9 4排出淸洗廢液 〇 又，從淸洗廢液之開始回收經過一定時間之後（例如 ，約經過1 5秒鐘後），在淸洗廢液未摻混處理廢液或其 他異物，或即使有摻混但是其係極爲微量，所以相反地打 開控制閥9 2閉合控制閥9 0 ’在第二淸洗廢液槽9 6排 出淸洗廢液。在第二淸洗廢液槽9 6所回收之淸洗廢液係 未另外再調整可再加利用。 按，於本實施形態，也可將處理廢液於在外殼8 8底 部之隔間壁1 0 4內側回收’將淸洗廢液在外殼8 8底部 之隔間壁1 0 4外側回收加以回收°此時，廢液回收，液 體補給裝置2 8係與隔間壁1 0 4內側之外殼8 8底部連 接。其他構成及作用係與實施第1形態之情形相同。 第5圖係表示本發明之第4形態之基板表面處理裝置 本紙張尺度適用中國國家標準（CNS)A4規格(21〇χ 297公釐） ' - !ί — ιίι -展- —III·! — 訂·！ ---線 {請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作杜印製 ΰ 2 ο Α7 __Β7__ 五、發明說明<2〗） 。本實施形態，係卡匣處理方式，由裝載機進行卡匣 106之運入，運出，在卡匣106排列有基板12 (例 如，半導體製造用之矽晶圓有20片）。 如第5圖所示，對運入於外殼88內之基板12，從 噴霧噴嘴7 6供給處理液對於基板表面給與處理液，其後 ，從噴霧噴嘴7 8給與淸洗液。 處理廢液，係從外殼8 8底部被抽出，打開控制閥 8 9閉合控制閥9 0，9 2輸送到廢液回收，液體補給裝 置2 8。貯留於廢液回收，液體補給裝置2 8之處理廢液 ，係由導電率計3 0及/或吸光光度計3 2測定導電率及 /或吸光度，其測定値爲輸入於控制器6 2，而檢測處理 廢液之一種或較其更多之成分濃度。因應其檢測濃度由來 自控制器6 2之訊號調節控制閥6 4及/或控制閥6 5之 開度對於處理廢液補給從處理調整液槽34及/或處理調 整液槽3 5含有調整所需既定量之處理調整液來調整處理 液。由包括圖中之一點鏈線所圍住之導電率3 0及/或吸 光光度計3 2之構成爲濃度檢測部。 所調整之處理液，係由幫浦4 0輸送到過濾器4 2 ’ 由過濾器4 2所過濾之後，供給於噴霧噴嘴7 6爲了在處 理外殻8 8內給與基板表面作爲循環使用。此時，如第5 圖所示，在過濾器4 2過濾之處理液之一部經由處理液還 流管4 3送還廢液回收，液體補給裝置2 8較佳，爲了提 高處理液調整時之攪拌效果，例如，使用噴霧噴嘴4 4可 構成爲送還廢液回收，液體補給裝置2 8之構成。包括圖 t — 11111 - I I — κ---—訂—— — — — — !線 <請先閱讀背面之注項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規輅（2〗0 X 29?公釐） -24 - 經濟部智慧財產局員工消費合作社印製 A7 ____B7五、發明說明（22 ) 中之一點鏈線所圍住之幫浦4 0，過濾器4 2及處理液還 流管4 3之構成爲攪拌.過濾部。 另一方面，淸洗廢液係從外殼8 8底部被抽出，而閉 合控制閥8 9與處理廢液另外回收。此時，若從淸洗廢液 之開始回收經過不太長時間時（例如，最初之1 5秒鐘程 度），在淸洗廢液可能摻混有處理廢液或其他異物，所以 ，打開控制閥9 0閉合控制閥9 2，對於回收含有異物淸 洗廢液所用之第一淸洗廢液槽9 4排出淸洗廢液。又，從 淸洗廢液之開始回收經過一定時間之後（例如，約經過 1 5秒鐘後），在淸洗廢液未摻混處理廢液或其他異物， 或即使有摻混但是其係極爲微量，所以相反地打開控制閥 9 2閉合控制閥9 0，在第二淸洗廢液槽9 6排出淸洗廢 液。在第二淸洗廢液槽9 6所回收之淸洗廢液係未另外再 調整可再加利用》 其他構成及作用係與實施之第1形態之情形相同。 【發明效果】 本發明係構成爲如上述，所以可發揮如下效果。 (1)可提供一種處理液之循環使用變成效率良好， 並且，即使反復循環也可持續處理液本身性能之基板表面 處理裝置。 (2 )不僅可將處理液之廢液（處理廢液）與淸洗液 之廢液（淸洗廢液）另外回收，同時，因對於所回收之處 理廢液補給處理調整液維持處理液之處理性能’所以，可 — — — — —1!· .llIl·! — 訂-------- (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -25 - 經濟部智慧財產局員工消費合作社印製 70 ? 6 A7 ___ Β7__.. _____ 五、發明說明（23 ) 減低於基板表面處理之一系列製程所需之處理液之量，並 且，可達成有效再利甩其處理液之目的。又，欲廢棄之處 理廢液量會變少。 (3 )不必於處理液與淸洗液個別地裝設旋轉器，所 以可將基板表面處理裝置之小型化。又’將淸洗液由處理 液之處理後可立即塗布。圖式之簡單說明 第1圖係表示本發明之實施第一形態之基板表面處理 裝置之系統性槪略構成圖。 第2圖係表示第1圖所示基板表面處理裝置之濃度檢 測•液體補給之詳細系統說明圖。 第3圖係表示本發明之實施第二形態之基板表面處理 裝置之系統性槪略構成圖。 第4圖係表示本發明之實施第三形態之基板表面處理 裝置之系統性槪略構成圖。 第5圖係表示本發明之實施第四形態之基板表面處理 裝置之系統性槪略構成圖。 【符號之說明】 10 浪輪運送機 1 2 基板 14 處理液供給裝置 1 6，2 2，8 8 外殼 18，24，44，76，78 噴霧噴嘴 20 淸洗液供給裝置 ί I------------ I ---^---—訂-- -----I I I (請先閲讀背面之注t事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -26 - 44702 6 Λ7 Ά.ί Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明<24 ) 2 6-52 2 8 3 0 3 2 3 4，3 5 3 6 3 8 4 0-54 4 2 - 5 6 4 3 4 6 4 8，5 0， 6 2 6 4-65-6 6 6-70 廢液池部 廢液回收·液體補給裝置 導電率計 吸光光度計 處理調整液槽 加熱器 液面感測器 幫浦 過濾器 處理液還流管 處理廢液槽 8，6 0 壓力錶 控制器 8，8 9，9 0， 氮氣槽 a 處理裝置（旋轉器） 7 0 7 2 驅 動 馬 達 7 4 晶 圓 夾 具 8 0 淸 洗 液 槽 8 2 杯 ( 槽 ) 8 4 內 壁 8 6 外 壁 9 4 第 _* 淸 洗 淸洗廢液槽 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） -27 - 2 控制閥 ------1 I ------ - ----— 訂--- ·線 (請先閱讀背面之注意事項再填寫本頁) 14^0 2 6 A7 _B7五、發明說明（25 ) 9 8 內杯（導引部） 100 內裙部 102 外裙部 104 隔間壁 10 6 卡匣 1---- ------— I-滅！ pill 訂· - -----線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工湞費合作社印製 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐） -28-ft 4 7 0 2 C Α7 Β7 Consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed 5. Description of the invention (17) Process liquid return pipe 4 3 stream return liquid waste recovery, liquid supply device 2 8 is better, in order to improve the treatment liquid The stirring effect during the adjustment is, for example, 'the waste liquid can be returned by using the spray nozzle 4 4 and the liquid replenishing device 28 can be used. The figure includes a pump 40 surrounded by a one-point chain line, a filter 42 and a treatment liquid return pipe 43 which are constituted as a stirring and filtering section. On the other hand, the washing waste liquid in the casing 88 is extracted from the bottom of the casing 88 and recovered separately from the processing waste liquid. At this time, if it does not take a long time to recover the decontaminated waste liquid (for example, about 15 seconds at the beginning), the decontaminated waste liquid may be mixed with the treatment waste liquid or other foreign matter, so open the control The valve 90 closes the control valve 92 and discharges the cleaning waste liquid to the first cleaning waste liquid tank 94 used for recovering the cleaning waste liquid containing foreign matter. In addition, after a certain period of time has elapsed since the washing liquid was recovered (for example, after about 15 seconds), the waste liquid or other foreign matter was not mixed with the washing liquid, or even if it was mixed, the amount was extremely small. Therefore, on the contrary, the control valve 92 is opened, the control valve 90 is closed, and the cleaning waste liquid is discharged in the second cleaning waste liquid tank 96. The washing waste liquid recovered in the second washing waste liquid tank 96 can be reused without further adjustment. According to this embodiment, the waste liquid can be recovered at the bottom of the casing 8 8, and the washing waste liquid can be recovered from the cup (tank) 82. At this time, the waste liquid is recovered, and the liquid supply device 28 is connected to the bottom of the casing 88. Other structures and functions are the same as those in the first embodiment. Fig. 4 shows a substrate surface processing apparatus according to a third embodiment of the present invention. In this embodiment, the substrate is fixed to a freely rotatable wafer holder, and the processing liquid and the cleaning liquid are sequentially given on the surface of the substrate. The inner skirt paper is equipped with Chinese national standards (CNS > A4 Regulation 4 each (210 X 297 mm)-20- f — — — —-Ή ^ · ι! ΓΙΙΙ ^^ * ι! Ί-^ (Please read the notes on the back before filling this page) Α7 Employees ’Consumption of Intellectual Property, Ministry of Economic Affairs Printed by the cooperative B7 __ V. Description of the invention (18) The inner cup that can be lifted and the outer skirt and the partition wall set at the bottom of the cabinet 'recycle the treatment waste liquid and the washing waste liquid ° As shown in the figure, 'the processing device (rotator) 7 〇a' has a substrate 12 on a revolving wafer holder 7 4 by a drive motor 72, and is fixed by, for example, a known electrostatic means or attractive means ( (Mounting) 'With the substrate 1 2 rotating,' the processing liquid is supplied from the spray nozzle 76 to the substrate surface, and then the cleaning liquid is supplied from the spray nozzle 78 to the substrate surface. Even in this embodiment Treatment device 7 0 a 'instead of spray nozzle 7 6, 78 can also use other nozzles Around the wafer holder 74, there is provided an inner cup (guide portion) 98 in the shape of a skirt such as the substrate 1 2 placed around the substrate. The inner cup (guide portion) 98 is provided by a lifting device (not shown). ) The bottom of the casing 8 is configured to be vertically movable. In addition, the inner cup (guide portion) 98 is composed of an inner skirt portion 100 and an outer skirt portion 102, and is arranged in a rotating manner. The partition wall 104 located at the bottom of the casing 8 is located between the inner skirt portion 100 and the outer skirt portion 102. Specifically, the inner cup (guide portion) 98 is located on the upper side of the substrate 12 (The two-point chain line in the figure) is guided into the inner skirt 100 to the waste liquid (washing waste liquid) from the substrate 12 into the inside of the partition wall 104, and the inner cup (the guide) When 9 8 is located on the lower side of the substrate 12 (the solid line in the figure), the outer skirt portion 102 is for guiding the waste liquid (treatment waste liquid) from the substrate 12 to the outside of the partition wall 104. In Fig. 4, when the processing liquid is supplied from the spray nozzle 76, the inner cup (guide portion) 98 is located in the lowermost position inside the casing 88. The supplied processing liquid will be supplied together with the wafer holder 74 and rotated. base Form 1 2-I Government ---- l ·! —Order --------- Line (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -21-4702 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The treatment liquid applied to the surface spreads evenly to the outer periphery due to the rotation (centrifugal force) of the substrate 12. In addition, the processing waste liquid thrown off from the substrate 12 is discharged from the upper side (outside) of the outer skirt portion 102 to the outside of the partition wall 104. On the other hand, when the scouring liquid is supplied from the spray nozzle 78, the inner cup (lead portion) 9 8 is positioned at the most raised position inside the outer casing 8 8. The supplied cleaning solution will be applied to the surface of the substrate 12 which is rotated together with the wafer holder 74. The cleaning solution applied to the surface spreads evenly to the outer periphery due to the rotation (centrifugal force) of the substrate 12. In addition, the scouring liquid removed from the substrate 12 is discharged from the lower surface (inner surface) of the inner skirt portion 100 to the inner side of the partition wall 104. The processing waste liquid on the outside of the partition wall 104 is extracted from the bottom of the casing 8 8 and transported to the waste liquid recovery and liquid supply device 28. Residual liquid stored in the waste liquid is recovered. The waste liquid treated by the liquid replenishing device 28 is measured by the conductivity meter 30 and / or the absorbance photometer 32, and the measurement is input to the controller 62, and Detect the concentration of one or more components of the treatment waste liquid. The opening of the control valve 6 4 and / or the control valve 6 5 is adjusted by a signal from the controller 6 2 in accordance with the detection concentration thereof. The process adjustment liquid tank 3 4 and / or the process adjustment liquid tank 3 5 contain adjustments for the treatment waste liquid replenishment. A predetermined amount of the process adjustment liquid is required to adjust the process liquid. The concentration detection unit is constituted by a conductive line 30 surrounded by a chain line including one point in the figure and / or an absorbance photometer 32. The adjusted processing liquid is sent from the pump 40 to the filter 4 2 and filtered by the filter 42 and then supplied to the spray nozzle 76 to circulate the substrate surface in the processing device (rotator) 7 0 a. use. At this time, as shown in Figure 4, one part of the processing liquid filtered by the filter 4 2 applies the Chinese national standard (CNS) A4 specification (210 X 297 mm) to the paper size. -22-~ I- ------- I 1 1 l · I-^ * ---— II (Please read the notes on the back before filling this page) 4 Υ Υ 2 6 Α7 Β7 Intellectual Property Bureau Employees ’Cooperatives, Ministry of Economic Affairs Printing 5. Description of the invention (20) Physical liquid return pipe 4 3 Waste liquid recovery and return 'Liquid replenishment device 2 8 is better' In order to improve the stirring effect when adjusting the processing liquid 'For example,' Using the spray nozzle 4 4 can be configured to return waste The structure of the liquid recovery and liquid supply device 28. The pump 4 0 ′ filter 4 2 and the treatment liquid return pipe 43 surrounded by a chain line at one point in the figure are constituted as a stirring and filtering unit. On the other hand, the washing waste liquid on the inner side of the partition wall 104 is extracted from the bottom of the casing 88, and is recovered separately from the processing waste liquid. At this time, if it does not take a long time to recover the decontaminated waste liquid (for example, the first 15 seconds), the decontaminated waste liquid may be mixed with the treatment waste liquid or other foreign matter, so open it. The control valve 90 closes the control valve 92, and discharges the cleaning waste liquid 9 to the first cleaning waste liquid tank 9 for recovering the cleaning waste liquid containing foreign matter. Furthermore, after a certain period of time has elapsed since the recovery of the cleaning waste liquid ( For example, after about 15 seconds has elapsed, the waste liquid is not mixed with the waste liquid or other foreign matter, or even if it is mixed, it is extremely small, so the control valve 9 is opened instead. 2 Close the control valve 9 0 'Drain the washing liquid in the second washing waste liquid tank 9 6. The cleaning waste liquid recovered in the second cleaning waste liquid tank 96 can be reused without further adjustment. According to this embodiment, the processing waste liquid can also be recovered on the inside of the partition wall 1 0 4 at the bottom of the casing 8 8. The washing waste liquid can be recovered and recovered on the outside of the partition wall 1 0 4 at the bottom of the casing 8 8. ° At this time, the waste liquid is recovered, and the liquid supply device 2 8 is connected to the bottom of the casing 8 8 inside the partition wall 104. The other structures and functions are the same as those in the first embodiment. FIG. 5 shows the substrate surface treatment device of the fourth form of the present invention. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm). '-! Ί — ιίι-展-—III ·! — Order! --- Line {Please read the notes on the back before filling out this page) Printed by the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs 印 2 ο Α7 __Β7__ 5. Description of the invention < 2〗). In this embodiment, the cassette processing method is used. The loading and unloading of the cassette 106 is performed by a loader, and the substrate 106 is arranged in the cassette 106 (for example, there are 20 silicon wafers for semiconductor manufacturing). As shown in Fig. 5, the substrate 12 carried in the housing 88 is supplied with a processing liquid from the spray nozzle 76 to give a processing liquid to the surface of the substrate, and thereafter, a cleaning liquid is supplied from the spray nozzle 78. The waste liquid is drawn out from the bottom of the casing 8 and the control valve 8 9 is closed. The control valve 9 0, 9 2 is sent to the waste liquid recovery, and the liquid replenishing device 28 is used. The waste liquid stored in the waste liquid recovery and liquid replenishing device 28 is measured by the conductivity meter 30 and / or the absorbance photometer 32, and the measurement is input to the controller 62, The concentration of one or more components of the treatment waste liquid is detected. The opening of the control valve 6 4 and / or the control valve 6 5 is adjusted by a signal from the controller 6 2 in accordance with the detection concentration thereof. The process adjustment liquid tank 34 and / or the process adjustment liquid tank 3 5 contain an adjustment unit for the treatment waste liquid replenishment. Need to adjust the treatment liquid with a given amount of treatment adjustment liquid. The concentration detection section is constituted by a conductive line 30 and / or an absorbance photometer 32 surrounded by a chain line including one point in the figure. The adjusted treatment liquid is transferred from the pump 40 to the filter 4 2 ′ and filtered by the filter 42, and then supplied to the spray nozzle 76 to recycle the substrate surface in the processing case 88. At this time, as shown in FIG. 5, one part of the processing liquid filtered by the filter 42 is returned to the waste liquid recovery through the processing liquid return pipe 4 3, and the liquid replenishing device 28 is preferable. In order to improve the stirring of the processing liquid adjustment The effect is, for example, that the spray nozzle 44 can be used to recover waste liquid, and the liquid supply device 28 can be configured. Including figure t — 11111-II — κ --- — order — — — —! Line <Please read the note on the back before filling out this page) This paper size applies Chinese National Standard (CNS) A4 regulations ( 2 〖0 X 29? Mm） -24-printed by A7 ____B7 in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. One of the points in the description of the invention (22) is surrounded by a chain 40, a filter 4 2 and The treatment liquid return pipe 43 is configured as a stirring and filtering unit. On the other hand, the washing waste liquid is withdrawn from the bottom of the casing 88, and the closed control valve 89 and the processing waste liquid are recovered separately. At this time, if it does not take too long to recover the washing waste liquid (for example, the first 15 seconds), the washing waste liquid may be mixed with the treatment waste liquid or other foreign matter, so turn on the control The valve 90 closes the control valve 92, and discharges the washing waste liquid to the first washing waste liquid tank 94 for recovering the washing waste liquid containing foreign matter. In addition, after a certain period of time has elapsed since the recovery of the cleaning waste liquid (for example, after about 15 seconds), the processing waste liquid or other foreign matter is not mixed with the cleaning waste liquid, or even if it is mixed, the system is extremely Since it is a small amount, the control valve 92 is opened and the control valve 90 is closed, and the cleaning waste liquid is discharged in the second cleaning waste liquid tank 96. The cleaning waste liquid recovered in the second cleaning waste liquid tank 96 is not readjusted and can be reused. The other structures and functions are the same as those in the first embodiment. [Effects of the Invention] Since the present invention is configured as described above, the following effects can be exhibited. (1) It is possible to provide a substrate surface processing apparatus that has a high efficiency in the recycling of the processing liquid, and that can continuously perform the performance of the processing liquid itself even after repeated cycling. (2) Not only can the waste liquid of the treatment liquid (treatment waste liquid) and the waste liquid of the washing liquid (washing waste liquid) be recovered separately, at the same time, because the recovered processing waste liquid is replenished with the processing adjustment liquid to maintain the treatment liquid Processing performance 'So, you can — — — — — 1! · .LlIl ·! — Order -------- (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS ) A4 specification (210 X 297 mm) -25-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 70? 6 A7 ___ Β7__ .. _____ V. Description of the invention (23) Reduced to less than one series of substrate surface treatment The amount of the treatment liquid, and the purpose of effectively re-shaping the treatment liquid can be achieved. In addition, the amount of waste liquid to be discarded will be reduced. (3) It is not necessary to separately install a spinner in the processing liquid and the cleaning liquid, so that the substrate surface processing apparatus can be miniaturized. Furthermore, the cleaning solution can be applied immediately after being treated by the treatment solution. Brief Description of the Drawings Fig. 1 is a schematic diagram showing a systematic structure of a substrate surface treatment apparatus according to a first embodiment of the present invention. Fig. 2 is a detailed system explanatory diagram showing the concentration detection and liquid replenishment of the substrate surface processing apparatus shown in Fig. 1. Fig. 3 is a systematic schematic configuration diagram showing a substrate surface processing apparatus according to a second embodiment of the present invention. Fig. 4 is a systematic schematic configuration diagram showing a substrate surface processing apparatus according to a third aspect of the present invention. Fig. 5 is a systematic schematic configuration diagram showing a substrate surface treatment apparatus according to a fourth embodiment of the present invention. [Explanation of symbols] 10 Wave carrier 1 2 Substrate 14 Processing liquid supply device 1 6, 2 2, 8 8 Casing 18, 24, 44, 76, 78 Spray nozzle 20 淸 Washing liquid supply device I I ---- -------- I --- ^ ----- Order------ III (Please read the note t on the back before filling out this page) This paper size applies to Chinese National Standards (CNS) A4 specification (210 X 297 mm) -26-44702 6 Λ7 Ά.ί Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention < 24) 2 6-52 2 8 3 0 3 2 3 4, 3 5 3 6 3 8 4 0-54 4 2-5 6 4 3 4 6 4 8, 5 0, 6 2 6 4-65-6 6 6-70 Conductivity meter for waste liquid recovery and liquid replenishment device in waste liquid tank Absorbance photometer processing adjustment tank heater liquid level sensor pump filter treatment liquid flow pipe treatment waste tank 8,6 0 pressure gauge controller 8, 8 9, 9 0, nitrogen tank a processing device (rotator ) 7 0 7 2 Drive motor 7 4 Wafer holder 8 0 Washing liquid tank 8 2 cups (slots) 8 4 Inner wall 8 6 Outer wall 9 4 No. ** Washing liquid waste tank The paper dimensions are applicable to Chinese national standards (CNS) A4 specifications ( 210 x 297 mm) -27-2 control valve ------ 1 I ------------ order --- · line (Please read the precautions on the back before filling this page ) 14 ^ 0 2 6 A7 _B7 V. Description of the invention (25) 9 8 Inner cup (guide) 100 Inner skirt 102 Outer skirt 104 Partition wall 10 6 Cassette 1 ---- ----- -— I-off! pill order------- line (please read the notes on the back before filling this page) Printed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs, this paper is printed in accordance with Chinese national standards (CNS > A4 specifications (210 X 297 Mm) -28-