500985 . .........，也 Α7 Β7 口 弋 -五丄發職 明（1 ) 相關申請案 (請先閱讀背面之注意事項再填寫本頁) 本案係1 9 9 9年9月3曰申請之其懸而未決的美國 申請案09/389，788之連續申請案，而其係 1 9 9 8年5月2 7日申請之共懸而未決的美國申請案 09/085，391之連續申請案，請求1997年5 月27日申請的美國臨時申請案60/047 ，739之 優先權，在此全部倂入本文中以爲參考。 本案亦請求1999年1 1月2日申請的美國臨時申 請案60/163，116、 1999年11月2日申請 的美國臨時申請案60/163，120及2000年4 月25日申請的美國臨時申請案60/199 ，661之 優先權，在此全部倂入本文以爲參考。 發明之範圍 本發明關係到自基板上除去光阻劑和殘餘物之範圍。 尤其，本發明關係利用超臨界二氧化碳自基板上除去光阻 劑和殘餘物之範圍。 經濟部智慧財產局員工消費合作社印製 發明之背景 半導體製造在離子注入、鈾刻及其他加工步驟中使用 光阻劑。在進子注入步驟中，半導體基板之光阻劑遮罩面 積並未注入摻雜物。在蝕刻步驟中，半導體基板之光阻劑 遮罩面積並未受到腐蝕。其他加工步驟之實施例包括使用 光阻劑當作加工晶片之覆蓋保護塗層或Μ E M S (微電機 -4- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 500985 A7 ___B7___ 五、發明說明（2 ) 系統）裝置之覆蓋保護塗層。 . 接著離子注入步驟，光阻劑具有硬質外殼覆蓋著果凍 般的核心。硬質外殼導致除去光阻劑之困難度。 接著飩刻步驟，維持原先光阻劑具有導致除去光阻劑 困難度之硬化特徵。接下來的飩刻步驟，光阻劑殘餘物與 蝕刻殘餘物覆蓋著蝕刻特徵圖案側壁。視餽刻類型及鈾刻 材料而定，光阻劑殘餘物與飩刻殘餘物混合變成一種棘手 的移除問題因爲光阻劑殘餘物與鈾刻殘餘物混合經常強而 有力的黏附至蝕刻特徵圖案之側壁。 通常，在先前技藝中，光阻劑和光阻劑殘餘物係藉著 在氧氣電漿中電漿灰化接著在剝離浴中剝離。 圖1圖示一個η — p — n F Ε Τ (場效電晶體）結 構1 0在光阻劑除去之前先注入離子。該η — p — η場效 電晶體結構1 0包括一個來源區1 2、一個光栅區1 4及 一個具有單立溝渠的排放區1 6分隔該η - ρ — η場效電 晶體結構1 0與相鄰的電子裝置。第一種光阻劑2 0罩住 所有區域除了來源及排放區，1 2及1 6以外。在離子注 入時’高能離子源將η -型摻雜物注入來源及排放區， 1 2及1 6中。高能離子源還將第一種光阻劑2 0暴露於 η -型摻雜物底下其於第一種光阻劑2 〇上表面2 2形成 一層硬殼。在先前技藝中，第一種光阻劑2 0藉由電漿灰 化及先前技藝之剝離浴去除。 圖2圖示接著R I Ε (反應性離子飩刻）蝕刻之後並 且在光阻劑和殘餘物去除之前的先前技藝之第一種導通孔 (請先閱讀背面之注意事項再填寫本頁) n ·__1 n n n n n 一SWJI n n emmm 1 ϋ —β I & 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） -5- 經濟部智慧財產局員工消費合作社印製 500985 A7 B7_____ 五、發明說明（3 ) 結構3 0。該第一種導通孔結構3 0包括一個導通孔3 2 其係蝕刻到第一層二氧化矽層3 4及第一層氮化鈦層3 6 中。在第一種導通孔結構3 0中，導通孔3 2停在第一層 氮化鈦層3 6因爲第一層氮化鈦層3 6製成一層用於第一 層二氧化矽層3 4之反應性離子蝕刻之飩刻阻擋物。穿透 第一層氮化鈦層3 6之鈾刻使反應性離子蝕刻變得複雜必 需外加用於第一層氮化鈦層3 6之蝕刻化學物；所以對於 這個指定的飩刻，氮化鈦層3 6並未_刻到。第一層氮化 鈦層3 6舖在第一層鋁層3 8上，其舖在第一層鈦層4 0 上。第一種殘餘物，其包含光阻劑殘餘物4 2混著二氧化 矽蝕刻殘餘物4 4，覆蓋著導通孔3 2之側壁4 6。第二 種光阻劑4 8保持在第一層二氧化矽層3 4之曝光表面 5 0上。在先前技藝中，第二種光阻劑4 8、光阻劑殘餘 物4 2及二氧化矽触刻殘餘物4 4係利用電漿灰化及先前 技藝之剝離浴去除。 注意說明之指定層材料及指定結構關係到第一種導通 孔結構3 0，以及其他在此討論之薄膜結構，係列示。許 多其他層材料及其他結構通常係用於半導體製造。 圖3圖示接著反應性離子蝕刻之後並且在光阻劑和殘 餘物去除之前的先前技藝之第二種導通孔結構6 0。第二 種導通孔結構6 0包括第二種導通孔6 2其係蝕刻穿透第 一層二氧化矽層3 4及第一層氮化鈦層3 6至第一層鋁層 3 8。經由蝕刻穿透第一層氮化鈦層3 6，裝置之特性便 得到改善因爲與第一層鋁層3 8之接觸阻抗低於與第一層 {請先閱讀背面之注意事項再填寫本頁)500985 ............., also Α7 Β7 口 弋-五 丄 发 职 明 (1) related applications (please read the notes on the back before filling this page) This case is 1 9 9 9 9 On March 3rd, the pending US application 09 / 389,788 consecutive applications, which were filed on May 27, 1998, the co-pending U.S. application 09 / 085,391 consecutive applications Filed in the U.S. Provisional Application No. 60 / 047,739 filed on May 27, 1997, which is incorporated herein by reference in its entirety. This case also requested US Provisional Application 60 / 163,116 filed on November 2, 1999, US Provisional Application 60 / 163,120 filed on November 2, 1999, and US Provisional Application filed on April 25, 2000 The priority of application 60 / 199,661 is incorporated herein by reference in its entirety. Scope of the invention The invention relates to the scope of removing photoresist and residues from a substrate. In particular, the present invention relates to the use of supercritical carbon dioxide to remove photoresist and residues from a substrate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics Background of the Invention Semiconductor manufacturing uses photoresist in ion implantation, uranium etching and other processing steps. In the sub-implantation step, the photoresist mask area of the semiconductor substrate is not implanted with dopants. During the etching step, the photoresist mask area of the semiconductor substrate was not corroded. Examples of other processing steps include the use of photoresist as a protective coating for processing wafers or MEMS (Micromotors 4- This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) 500985 A7 ___B7___ V. Description of the Invention (2) System) The protective coating of the device. Following the ion implantation step, the photoresist has a hard shell covering a jelly-like core. The hard case causes difficulty in removing the photoresist. A subsequent engraving step maintains the hardening characteristics of the original photoresist, making it difficult to remove the photoresist. In the next engraving step, the photoresist residue and the etching residue cover the sidewall of the etched feature pattern. Depending on the type of feed and the uranium engraving material, mixing photoresist residues with engraving residues can become a tricky removal problem because photoresist residues and uranium engraving residues often mix strongly and strongly to the etching features Patterned sidewall. Generally, in the prior art, the photoresist and the photoresist residue are ashed by plasma in an oxygen plasma and then stripped in a peel bath. FIG. 1 illustrates a η — p — n F ET (field-effect transistor) structure 10 in which ions are implanted before the photoresist is removed. The η — p — η field-effect transistor structure 10 includes a source region 1 2, a grating region 14, and an emission region 16 with a single trench. 6 separates the η-ρ — η field-effect transistor structure 1 0 And adjacent electronic devices. The first photoresist 20 covers all areas except the source and discharge areas, 12 and 16. At the time of ion implantation, a high energy ion source injects n-type dopants into the source and discharge regions, 12 and 16. The high-energy ion source also exposes the first photoresist 20 to the n-type dopant and forms a hard shell on the upper surface 22 of the first photoresist 20. In the prior art, the first photoresist 20 was removed by plasma ashing and the stripping bath of the prior art. Figure 2 illustrates the first vias of the prior art after RI E (reactive ion engraving) etching and before photoresist and residue removal (please read the precautions on the back before filling this page) n · __1 nnnnn a SWJI nn emmm 1 ϋ —β I & Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 Regulation (210 X 297 mm) -5- Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 500985 A7 B7_____ V. Description of Invention (3) Structure 30. The first via structure 30 includes a via 32 which is etched into the first silicon dioxide layer 34 and the first titanium nitride layer 36. In the first via structure 30, the via 32 stops at the first titanium nitride layer 3 6 because the first titanium nitride layer 36 is made into a layer for the first silicon dioxide layer 3 4 Engraved barrier for reactive ion etching. The uranium etch that penetrates the first titanium nitride layer 36 complicates reactive ion etching. An additional etch chemistry for the first titanium nitride layer 36 is required; so for this specified etch, nitriding The titanium layer 36 is not etched. The first titanium nitride layer 36 is laid on the first aluminum layer 38, which is laid on the first titanium layer 40. The first residue comprises a photoresist residue 4 2 mixed with a silicon dioxide etching residue 4 4, and covers a sidewall 46 of the via 32 2. The second photoresist 48 is held on the exposed surface 50 of the first silicon dioxide layer 34. In the prior art, the second photoresist 48, photoresist residue 42, and silicon dioxide contact residue 4 4 were removed by plasma ashing and the stripping bath of the previous technology. Note that the specified layer material and specified structure are related to the first via structure 30, and other thin film structures discussed here, shown in series. Many other layer materials and other structures are commonly used in semiconductor manufacturing. Fig. 3 illustrates a second via structure 60 of the prior art following the reactive ion etching and before the photoresist and residue removal. The second via structure 60 includes a second via 62 which is etched through the first silicon dioxide layer 34 and the first titanium nitride layer 36 to the first aluminum layer 38. By etching through the first titanium nitride layer 36, the characteristics of the device are improved because the contact resistance with the first aluminum layer 38 is lower than with the first layer {Please read the precautions on the back before filling this page )
--—訂---1--!線 I 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) -6 - 500985 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（4 ) 氮化鈦層3 6之接觸阻抗。第二種導通孔結構6 0還包括 第一層鈦層4 0。第一種殘餘物，其包含光阻劑殘餘物 4 2混以二氧化矽鈾刻殘餘物4 4，覆蓋著第二種導通孔 6 2之第二種側壁6 4。第二種殘餘物，其包含光阻劑殘 餘物4 2混以氮化鈦蝕刻殘餘物6 6，覆蓋著第一種殘餘 物。第二種光阻劑4 8則留在第一層二氧化矽層3 4之曝 光表面50上。在先前技藝中，第二種光阻劑48、光阻 劑殘餘物4 2、二氧化矽飩刻殘餘物4 4以及氮化鈦蝕刻 殘餘物6 6係利用電漿灰化及先前技藝之剝離浴去除之。 注意一種殘餘物（圖2及3 )及第二種殘餘物（圖3 )係最糟的情況。視指定之飩刻方法而定，第一種殘餘或 第二種殘餘物可能不會出現。 圖4列示接著金屬反應性離子蝕刻之後並且在殘餘物 除去之前之一種金屬線結構7 0。該金屬線結構7 0包括 第二層鋁層7 4其位於第二層鈦層7 6上之第二層氮化鈦 層7 2。該第二層氮化鈦層7 2、第二層鋁層7 4及第二 層鈦層7 6形成一種金層線。第二層鈦層7 6接觸到一個 W導通孔7 8，其反過來接觸到第一層鋁層3 8。該W導 通孔7 8藉由側壁阻擋物8 0分離第一層二氧化矽層3 4 。第三種殘餘物，其包含一種鹵素殘餘物8 2混以金屬蝕 刻殘餘物8 4，舖在第一層二氧化矽層3 4之曝光表面 5 0上。該第三種殘餘物，其包含鹵素殘餘物8 2及金屬 蝕刻殘餘物8 4，並且還舖在第二層氮化鈦層7 2之第二 種曝光表面8 6上。第四種殘餘物，其包含光阻劑殘餘物 τ (請先閱讀背面之注意事項再填寫本頁) — —訂· — --線- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -7- 500985 A7 B7 五、發明說明（5 ) {請先閱讀背面之注意事項再填寫本頁) 4 2混以金屬蝕刻殘餘物8 4之組合，覆蓋著金屬線之側 邊。第四種殘餘物之邊緣9 0延伸到第二層氮化鈦層7 2 之第二種曝光表面8 6之上。在先前技藝中，光阻劑殘餘 物4 2、鹵素殘餘物8 2及金屬殘餘物8 4係利用電漿灰 化及先前技藝之剝離浴去除之。 圖5列示接著雙重蝕刻反應性離子飩刻之後並且在光 阻劑及光阻劑殘餘物去除之前的一種先前技藝之雙重蝕刻 結構1 0 0。雙重触刻結構1 0 〇包括一種形成於雙重触 刻導通孔1 0 4上靣之雙重蝕刻線1 〇 2。該雙重蝕刻線 1 0 2係飩刻穿透第二層二氧化矽層1 〇 6及第一層氮化 矽層1 0 8。該雙重蝕刻導通孔1 〇 4係飩刻穿透第三層 二氧化矽層1 1 0及第二氮化矽層1 1 2。該雙重触刻導 通孔係飩刻至銅層1 1 4的下方。 加工過程中接著光阻劑及殘餘物去除之後，雙重蝕刻 線及導通孔，1 0 2及1 0 4，之曝光表面，係覆蓋著阻 擋物層接著雙重飩刻線及導通孔，1 0 2及1 0 4，塡滿 銅。 經濟部智慧財產局員工消費合作社印製 回到圖5，第五種殘餘物，其包含光阻劑殘餘物4 2 混以二氧化矽蝕刻殘餘物4 4，覆蓋著線的側壁1 1 6及 導通孔側壁1 1 8。第六種殘餘物，其包含光阻劑殘餘物 4 2混以氮化矽蝕刻殘餘物1 2 0，覆蓋著第五種殘餘物 。第七種殘餘物，其包含光阻劑殘餘物4 2混以銅飩刻殘 餘物1 2 2，覆蓋著第六種殘餘物。光阻劑4 8殘留於第 二層二氧化矽層1 0 6之第二種曝光表面上。在先前技藝 -8- 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） 500985 A7 ^"ΐββΒΙββΙΙβββΙβ™^^*βΙ>βΙΒ"Β"ΒΙβΙβΙβΙΙ>ΒΙΒΙ>Β>βΙΒΒβΙΜΙβΙ>>βΙ"ΒΙΙβ>ββ^^^^^™*Ι^^*™Ιβ™"^^^βΜΜΙΙ<·*^™^^™™^™>·™^^^^β·Ι™^^***™*βιι·^^^*«*^*β*^^^^βϋ··Ι·β^βΒβιιΙΜ^^Μββ|Μ|(^^βΒΜ||Β|^^^βΜΜ|1Ββ|^^βΜΜ||>Μβ 五、發明說明（6 ) 中，光阻劑4 8、光阻劑殘餘物4 2、二氧化矽蝕刻殘餘 物4 4、氮化矽蝕刻殘餘物1 2 0及銅蝕刻殘餘物1 2 2 係利用電漿灰化及先前技藝之剝離浴去除之。 注意第五、第六及第七種殘餘物係最糟的情況。視指 定的蝕刻方法而定，第五、第六或第七種殘餘物可能不會 出現。 最近在半導體技術之發展已經趨向建議利用低介電常 數材料來取代雙重蝕刻結構之第二及第三層介電層， 1 0 6及1 1 〇。利用低介電常數材料來取代雙重蝕刻結 構之第二及第三層介電層，106及丨1〇，將增強電子 裝置速度。現今致力發展低介電常數材料已經產生低介電 常數材料之第一及第二類。第一類的低介電常數材料係碳 -二氧化矽材料其中碳降低二氧化矽之介電常數。第二類 介電材料係旋壓之聚合物，其係高交聯聚合物特別設計用 於低介電常數。該旋壓聚合物之實施例係DOW Chemical公 司的SILK。SILK係DOW Chenncal公司之註冊商標。 導通孔及線之幾何形狀係設計成類似的尺寸及較大的 深度寬度比。當導通孔及線之幾何形狀係發展成相似的尺. 寸及較大的深度寬度比時，電漿灰化及先前技藝之剝離浴 在除去光阻劑及光阻劑殘餘物時將變得較沒有效率。再者 ，二氧化矽利用低介電常數材料之取代配合電漿灰化之持 續使用將增加差異性。對於碳一二氧化矽材料，氧氣電漿 攻擊碳。對於碳-二氧化矽材料，氧氣電漿可以利用氫氣 電漿取代但是這會降低整個電漿灰化之效率。對於旋壓聚 (請先閱讀背面之注意事項再填寫本頁) 訂ii!線j 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） -9- 500985 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（7 ) 合物’尤其是DOW Chemical公司的SILK ,電漿灰化並非 一個除去光阻劑或光阻劑殘餘物之可行方法因爲電漿灰化 將會攻擊旋壓聚合物。 需要的是除去光阻劑更有效的方法。 需要的是除去殘餘物更有效的方法。 需要的是除去光阻劑更高效的方法。 需要的是除去殘餘物更高效的方法。 需要的是自基板其中導通孔及線幾何形狀具有小尺寸 者除去光阻劑之方法。 需要的是自基板其中導通孔及線幾何形狀具有小尺寸 者除去殘餘物之方法。 需要的是自基板其中導通孔及線幾何形狀具有較大深 度寬度比者除去光阻劑之方法。 需要的是自基板其中導通孔及線幾何形狀具有較大深 度寬度比者除去殘餘物之方法。 需要的是自基板其中特徵國案係蝕刻到碳一二氧化矽 低介電常數材料者除去光阻劑之方法。 需要的是自基板其中特徵圖案係蝕刻到碳一二氧化矽 低介電常數材料者除去殘餘物之方法。 需要的是自基板其中特徵圖案係飩刻到旋壓聚合物低 介電常數材料者除去光阻劑之方法。 需要的是自基板其中特徵圖案係蝕刻到旋壓聚合物低 介電常數材料者除去殘餘物之方法。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- 1114 (請先閱讀背面之注意事項再填寫本頁) -i — 丨·! 訂— ------線- 500985 A7 B7 五、發明說明（8 ) 發明總結 本發明係一種自基板上除去光阻劑及殘餘物之方法。 通常’光阻劑或光阻劑及殘餘物，或殘餘物殘留在基板上 之後接著前段的半導體加工步驟例如離子注入或蝕刻。該 方法藉著保持超臨界二氧化碳、胺類及溶劑與基板接觸以 致胺類及溶劑溶解大部份的光阻劑及殘餘物。 較佳者，胺類係二級胺或三級胺。更佳者，胺類係三 級胺。又更佳者，該胺類係選自2 -（甲基胺基）乙醇、 五甲基二乙撐三胺、三乙醇胺、三乙胺、及彼之混合物。 較佳者’溶劑係選自二甲基亞硕、碳酸次乙酯、N —甲基 一 2 —吡咯烷醒、乙醯丙酮、丁內酯、醋酸、二甲基乙醯 胺、碳酸次丙酯及彼之混合物。 接著，光阻劑和殘餘物係自基板周圍除去。較佳者， 該方法持續保持沖洗步驟其中該基板係於超臨界二氧化碳 及沖洗劑中沖洗。較佳者，沖洗劑係選自水、醇、酮及彼 之混合物。更佳者，沖洗劑係醇及水之混合物。較佳地， 醇係選異丙醇、乙醇及其他低分子量醇類。更佳者，該醇 係乙醇。 在第一個替代系統中，胺類及溶劑係利用水溶性氟化 物取代之。在第二個替代系統中，該溶劑係添加至第一個 替代體系之水溶性氟化物中。在第三個替代體系中，胺類 係添加至水溶性氟化物及第二個替代體系之溶劑中。 _ 圖形之簡單說明 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） -11- <請先閱讀背面之注意事項再填寫本頁} H 1 n ϋ· Β— I · emmm mmmmm 1 n mmmmm emmmm I ‘ 經濟部智慧財產局員工消費合作社印製 -T · 500985 A7 B7__ 五、發明說明（9) 圖1列示接著離子注入之後並且在光阻劑除去之前的 一個先前技藝之η - P - η場效電晶體結構。 圖2列示接著反應性離子蝕刻之後並且在光阻劑和殘 餘物除去之前的第一種導通孔結構。 圖3列示接著反應性離子飩刻之後並且在光阻劑和殘 餘物除去之前的第二種導通孔結構。 圖4列示接著反應性離子鈾刻之後並且在殘餘物除去 之前的先前技藝之金屬線結構。 圖5列示接著反應性離子飩刻之後並且在光阻劑和殘 餘物除去之前的先前技藝之雙重飩刻結構。 圖6係列示本發明較佳方法之流程圖。 圖7列示本發明之較佳加工系統。 圖8係本發明之時程。 符號說明 10 η - ρ - η型場效電晶體結構 12 來源區 14 光柵區 16 排放區 18 分隔溝渠 20 第一種光阻劑 2 2 上表面 30 第一種導通孔結構 3 2 導通孔 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -12 - (請先閱讀背面之注意事項再填寫本頁) --訂---------線一 經濟部智慧財產局員工消費合作社印製 500985 A7 _B7 五、發明說明（1〇) 經濟部智慧財產局員Η消費合作社印製 3 4 第 — 層 二 氧 化矽 層 3 6 第 一 層 氮 化 it 層 3 8 — 層 鋁 層 4 0 第 -—* 層 鈦 層 4 2 光 阻 劑 殘 餘 物 4 4 — 氧 化矽 蝕 刻 殘 餘物 4 6 側 壁 4 8 第 二 種 光 阻 劑 5 0 曝 光 表 面 6 0 第 二 種 導 通 孔 結 構 6 2 第 一 種 導 通 孔 6 4 第 一 種 側 壁 6 6 氮 化 鈦 餽 刻 殘 餘 物 7 0 金 屬 線 結 構 7 2 第 二 層 氮 化 鈦 層 7 4 第 層 鋁 層 7 6 第 — 層 鈦 層 7 8 W 導 通 孔 8 0 側 壁 阻 擋 物 8 2 鹵 素 殘 餘 物 8 4 金 屬 飩 刻 殘 餘 物 8 6 第 —. 種 曝 光 表 面 8 8 側 邊 9 0 邊 緣 (請先_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規袼（210 X 297公釐） -13- 500985 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明說明（11) 100 雙重蝕刻結構 102 雙重蝕刻線 104 雙重蝕刻導通孔 106 第二層二氧化矽層 108 第一層氮化矽層 110 第三層二氧化矽層 112 第二層氮化矽層 114 銅層 116 線側壁 118 導通孔側壁 120 氮化矽餽刻殘餘物 122 銅飩刻殘餘物 2 0 0 適當方法 202 第一個加工步驟 204 第二個加工步驟 206 第三個加工步驟 2 0 8 第四個加工步驟 2 10 第五個加工步驟 212 第六個加工步驟 214 第七個加工步驟 2 2 0 超臨界加工系統 222 二氧化碳供給容器 224 二氧化碳幫浦‘ 2 2 6 壓力室 (請先閱讀背面之注意事項再填寫本頁) Τ -m mmme Mmtm ft— n n I J 、i Mil mtmm n -4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14- 500985 A7 ————’ —_ B7五、發明說明（12) 2 2 8 化 學 物 供 給 容 SB 播 2 3 0 循 IBS m 幫 浦 2 3 4 廢 氣 收 集 容 器 2 3 6 — 氧 化 碳 配 管 2 3 8 二 氧 化 碳 加 熱 器 2 4 0 加 壓 室 加 熱 器 2 4 2 循 環 管 線 2 4 4 循 環 入 □ 2 4 6 循 環 出 □ 2 4 8 化 學 物 供 給 管 線 2 4 9 第 一 個 注射 幫 浦 2 5 0 沖 洗 劑 供 給 容 器 2 5 2 沖 洗 供 給 管 線 2 5 3 第 一 個 注 射 幫 浦 2 5 4 排 氣 配 管 2 5 6 晶 片 腔 2 6 0 時 程 2 6 2 壓 力 (請先閱讀背面之注意事項再填寫本頁) .線·· 經濟部智慧財產局員工消費合作社印製 較佳體系之詳細說明 。本發明利用超臨界二氧化礙自基板上除去光阻劑和 殘餘物之方法。該殘餘物包括光阻劑殘餘物及蝕刻殘餘物 。通常，該基板係半導體晶片。或者，該基板係非晶片基 板例如橡膠圓盤。通常，光阻劑係置於晶片上在進行半導 本紙張尺度適用中國國家標準(CNS)A4規袼（210 X 297公釐) .15 - "" 500985 A7 B7 五、發明說明（13) 體製造加工步驟中罩住晶片之一部份。此前置加工步驟包 括離子注入及鈾刻步驟。 在離子注入步驟中，光阻劑罩住晶片之區域其未被植 任摻雜物而讓摻雜物植入晶片未遮罩區域。離子注入步驟 在光阻劑上形成硬殼在硬殼下留下果凍般的核心。 在飩刻步驟中，光阻劑遮罩晶片區域其並未被蝕刻而 未被遮罩區域則被触刻了。在触刻步驟中，光阻劑及晶片 係餽刻產生蝕刻特徵圖案而且還產生光阻劑殘餘物及蝕刻 殘餘物。光阻劑之蝕刻產生了光阻劑殘餘物。触刻特徵圖 案之飩刻產生了蝕刻殘餘物。光阻劑和触刻殘餘物經常覆 蓋著蝕刻特徵圏案之側壁。 在某些飩刻步驟中，光阻劑並未飩刻完全以致在飩刻 之後一部份光阻劑殘留在晶片上。在這些蝕刻步驟中，鈾 刻法硬化了殘留的光阻劑。在其他蝕刻步驟中，光阻劑係 蝕刻完全所以在這些蝕刻步驟中沒有光阻劑殘留在晶片上 。在後面例子中只有殘餘物，其係光阻劑殘餘物及蝕刻殘 餘物，殘留在晶片上。 對於0 · 2 5微米及更小幾何形狀者本發明宜直接除 去光阻劑。換句話說，本發明宜直接除去I -線曝光光阻 劑及較短波長曝光光阻劑。這些係紫外光、深紫外光及較 小的幾何形狀之光阻劑。或者，本發明係針對除去較大的 幾何形狀之光阻劑。 其對熟於此藝之士極爲顯而易見的同時本發明係從除 去光阻劑和殘餘物之觀點來敘述其同樣適合於除去光阻齊jj 本紙張尺度適用中國國家標準（CNS〉A4規格（210 X 297公釐） {請先閱讀背面之注意事項再填寫本頁) ίφ^α —---訂-----|線| 經濟部智慧財產局員Η消費合作社印製 16--- Order --- 1--! Line I This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -6-500 985 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of the Invention (4) The contact resistance of the titanium nitride layer 36. The second via structure 60 also includes a first titanium layer 40. The first residue comprises a photoresist residue 4 2 mixed with a uranium dioxide etched residue 4 4 to cover a second sidewall 64 of a second via hole 62. The second residue, which contains the photoresist residue 4 2 mixed with the titanium nitride etching residue 6 6, is covered with the first residue. The second photoresist 48 is left on the exposed surface 50 of the first silicon dioxide layer 34. In the prior art, the second photoresist 48, photoresist residue 4 2, silicon dioxide engraving residue 4 4 and titanium nitride etching residue 6 6 are plasma ashing and stripping of the previous technology. Remove it from the bath. Note that one residue (Figures 2 and 3) and the second residue (Figure 3) are the worst case. Depending on the specified engraving method, the first or second residue may not appear. Fig. 4 shows a metal wire structure 70 following metal reactive ion etching and before residue removal. The metal wire structure 70 includes a second aluminum layer 74 and a second titanium nitride layer 72 located on the second titanium layer 76. The second titanium nitride layer 72, the second aluminum layer 74, and the second titanium layer 76 form a gold layer wire. The second titanium layer 76 is in contact with a W via 78, which in turn contacts the first aluminum layer 38. The W via hole 78 separates the first silicon dioxide layer 34 by a side wall barrier 80. The third kind of residue, which contains a halogen residue 8 2 mixed with a metal etching residue 8 4, is laid on the exposed surface 50 of the first silicon dioxide layer 34. The third residue, which includes a halogen residue 82 and a metal etching residue 84, is also deposited on the second exposed surface 86 of the second titanium nitride layer 72. The fourth kind of residue, which contains the photoresist residue τ (please read the precautions on the back before filling this page) — — Order · —-Line-This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -7- 500985 A7 B7 V. Description of the invention (5) {Please read the precautions on the back before filling this page) 4 2 The combination of metal etching residue 8 4 covers the side of the metal wire side. The edge 90 of the fourth residue extends above the second exposed surface 86 of the second titanium nitride layer 72. In the prior art, the photoresist residue 42, the halogen residue 82, and the metal residue 84 were removed by plasma ashing and the stripping bath of the previous technology. FIG. 5 shows a double-etched structure of a prior art after the double-etched reactive ion etching and before the photoresist and photoresist residues are removed. The double-etched structure 100 includes a double-etched line 102 formed on the double-etched via 104. The double etching line 102 is etched through the second silicon dioxide layer 106 and the first silicon nitride layer 108. The double-etched via 104 is etched through the third silicon dioxide layer 110 and the second silicon nitride layer 112. The double-contact vias are etched under the copper layer 1 1 4. After the photoresist and residues are removed during processing, the exposed surfaces of the double etched lines and vias, 102 and 104, are covered with a barrier layer followed by double etched lines and vias, 102 And 1 0 4, full of copper. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, back to Figure 5, the fifth residue, which contains photoresist residue 4 2 mixed with silicon dioxide etching residue 4 4, covering the side walls of the line 1 1 6 and Via hole sidewall 1 1 8. The sixth residue, which contains the photoresist residue 4 2 mixed with silicon nitride etching residue 1 2 0, is covered with the fifth residue. The seventh residue, which contains the photoresist residue 4 2 mixed with copper engraving residue 1 2 2, is covered with the sixth residue. The photoresist 48 remains on the second exposure surface of the second silicon dioxide layer 106. In the previous technique-8- This paper size applies the Chinese National Standard (CNS) A4 regulation (210 X 297 mm) 500985 A7 ^ " ΐββΒΙββΙΙβββΙβ ™ ^^ βΙ > βΙΒ " Β " ΒΙβΙβΙβΙΙΙ > ΒΙΙΙ > Β > ΙΙΙΙ > βΙ " ΒΙΙβ > ββ ^^^^^ ™ * Ι ^^ * ™ Ιβ ™ " ^^^ βΜΜΙΙ < · * ^ ™ ^^ ™™ ^ ™ > · ™ ^^^^ β · Ι ™ ^^ *** ™ * βιι · ^^^ * «* ^ * β * ^^^^ βϋ ·· Ι · β ^ βΒβιιΙΜ ^^ Μββ | Μ | (^^ βΒΜ || Β | ^^^ βΜΜ | 1Ββ | ^^ βΜΜ || > Μβ 5. In the description of the invention (6), photoresist 4 8, photoresist residue 4 4, silicon dioxide etching residue 4 4, silicon nitride etching residue 1 2 0 and copper etching residues 1 2 2 are removed by plasma ashing and stripping baths of previous techniques. Note that the fifth, sixth, and seventh residues are the worst case. Depending on the specified etching method, The fifth, sixth, or seventh residue may not appear. Recently, in the development of semiconductor technology, it has been proposed to use a low dielectric constant material to replace the second and third dielectric layers of the double-etched structure, 1 0 6 and 1 1 0. The use of low dielectric constant materials to replace the second and third dielectric layers of the double-etched structure, 106 and 10, will increase the speed of electronic devices. Now efforts to develop low dielectric constant materials have been produced The first and second types of low dielectric constant materials. The first type of low dielectric constant materials are carbon-silicon dioxide materials in which carbon reduces the dielectric constant of silicon dioxide. The second type of dielectric materials is spin-on Polymer, which is a highly cross-linked polymer specifically designed for low dielectric constants. Examples of this spin-on polymer are SILK from DOW Chemical. SILK is a registered trademark of DOW Chenncal. Geometry of vias and wires It is designed with similar dimensions and larger depth-to-width ratios. When the geometry of the vias and lines develops into similar dimensions. Inches and larger depth-to-width ratios, the plasma ashing and the stripping bath of the previous technology are Removal of photoresist and photoresist residues will become less efficient. Furthermore, the replacement of silicon dioxide with low dielectric constant materials and the continued use of plasma ashing will increase the difference. For carbon monoxide Silicon material Oxygen plasma attacks carbon. For carbon-silicon dioxide materials, oxygen plasma can be replaced with hydrogen plasma but this will reduce the efficiency of the entire plasma ashing. For spinning poly (Please read the precautions on the back before filling this page ) Order ii! Line j Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with the Chinese National Standard (CNS) A4 Regulation (210 X 297 mm) -9- 500985 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) Compound 'especially SILK from DOW Chemical, plasma ashing is not a feasible method to remove photoresist or photoresist residue because plasma ashing will attack spinning polymerization Thing. What is needed is a more effective method of removing photoresist. What is needed is a more efficient method of removing residue. What is needed is a more efficient method of removing the photoresist. What is needed is a more efficient method of removing residues. What is needed is a method of removing the photoresist from a substrate in which the vias and line geometries have small dimensions. What is needed is a method for removing residues from substrates where vias and line geometries have small dimensions. What is needed is a method to remove the photoresist from the substrate where the vias and line geometry have a greater depth-to-width ratio. What is needed is a method of removing residues from the substrate in which the vias and line geometry have a greater depth-to-width ratio. What is needed is a method to remove the photoresist from the substrate in which the characteristic case is etched to a carbon-silicon dioxide low dielectric constant material. What is needed is a method for removing residues from a substrate in which a feature pattern is etched to a carbon-silicon dioxide low dielectric constant material. What is needed is a method of removing the photoresist from the engraving of the feature pattern in the substrate to the spin-on polymer low dielectric constant material. What is needed is a method of removing residues from the substrate in which the feature pattern is etched to a spin polymer low dielectric constant material. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) -10- 1114 (Please read the precautions on the back before filling this page) -i — 丨 ·! Order — ------ Line-500985 A7 B7 V. Description of the invention (8) Summary of the invention The present invention is a method for removing photoresist and residues from a substrate. Usually, the photoresist or photoresist and residues, or residues remain on the substrate, followed by the previous semiconductor processing steps such as ion implantation or etching. This method keeps the supercritical carbon dioxide, amines, and solvents in contact with the substrate so that the amines and solvents dissolve most of the photoresist and residues. Preferably, the amine is a secondary or tertiary amine. More preferably, the amines are tertiary amines. Even more preferably, the amines are selected from the group consisting of 2- (methylamino) ethanol, pentamethyldiethylenetriamine, triethanolamine, triethylamine, and mixtures thereof. The preferred solvent is selected from the group consisting of dimethylasco, ethylidene carbonate, N-methyl-2-pyrrolidine, acetoacetone, butyrolactone, acetic acid, dimethylacetamide, and propylene carbonate. Esters and their mixtures. Next, the photoresist and residue are removed from around the substrate. Preferably, the method continuously maintains a washing step in which the substrate is washed in supercritical carbon dioxide and a washing agent. Preferably, the rinsing agent is selected from the group consisting of water, alcohol, ketone, and mixtures thereof. More preferably, the rinse agent is a mixture of alcohol and water. Preferably, the alcohol is selected from isopropyl alcohol, ethanol and other low molecular weight alcohols. More preferably, the alcohol is ethanol. In the first alternative system, amines and solvents were replaced with water-soluble fluorides. In the second alternative system, the solvent is added to the water-soluble fluoride in the first alternative system. In the third alternative system, amines are added to the water-soluble fluoride and the solvent of the second alternative system. _ Brief description of graphics This paper size is subject to Chinese National Standard (CNS) A4 (210 X 297 mm) -11- < Please read the notes on the back before filling this page} H 1 n ϋ · Β— I · Emmm mmmmm 1 n mmmmm emmmm I 'Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-T · 500985 A7 B7__ V. Description of the invention (9) Figure 1 shows a previous one after the ion implantation and before the photoresist removal Η-P-η field-effect transistor structure of technology. Figure 2 shows the first via structure after the reactive ion etching and before the photoresist and residue are removed. Figure 3 shows a second via structure following reactive ion etching and before photoresist and residue removal. Fig. 4 shows the metal wire structure of the prior art following the reactive ion uranium engraving and before the residue is removed. Figure 5 shows the double engraved structure of the prior art following reactive ion engraving and before removal of photoresist and residues. Figure 6 shows a flowchart of a preferred method of the present invention. FIG. 7 illustrates a preferred processing system of the present invention. FIG. 8 is a time chart of the present invention. DESCRIPTION OF SYMBOLS 10 η-ρ-η field effect transistor structure 12 Source area 14 Grating area 16 Emission area 18 Separation trench 20 First photoresist 2 2 Upper surface 30 First via structure 3 2 Via Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) -12-(Please read the precautions on the back before filling this page)-Order ---------- Wisdom of the Ministry of Economy Printed by the Consumer Cooperative of the Property Bureau 500985 A7 _B7 V. Description of the invention (10) Printed by the Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 4 The first layer—a layer of silicon dioxide 3 6 The first layer—nitride it layer 3 8—layer Aluminium layer 4 0 —- * Ti layer 4 2 Photoresist residue 4 4 — Silicon oxide etching residue 4 6 Side wall 4 8 Second photoresist 5 0 Exposed surface 6 0 Second via structure 6 2 The first type of via 6 6 The first type of sidewall 6 6 The titanium nitride feed residue 7 0 The metal wire structure 7 2 The second layer of titanium nitride 7 4 The first layer of aluminum 7 6 The first — layer of titanium 7 8 W vias 8 0 Side wall barriers 8 2 Halogen residues 8 4 Metal engraving residues 8 6 — — An exposed surface 8 8 Sides 9 0 Edges (Please read the precautions on the back side before filling out this page ) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -13- 500985 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (11) 100 Double etched structure 102 Double Etching lines 104 Double-etched vias 106 Second silicon dioxide layer 108 First silicon nitride layer 110 Third silicon dioxide layer 112 Second silicon nitride layer 114 Copper layer 116 Line sidewall 118 Via sidewall 120 Silicon Nitride Feed Residue 122 Copper Engraving Residue 2 0 0 Appropriate Method 202 First Processing Step 204 Second Processing Step 206 Third Processing Step 2 0 8 Fourth Processing Step 2 10 Fifth Processing Step 212 Sixth processing step 214 Seventh processing step 2 2 0 Supercritical processing system 222 CO2 supply container 224 CO2 pump '2 2 6 Pressure chamber (please read the Please fill in this page again if necessary) Τ -m mmme Mmtm ft— nn IJ, i Mil mtmm n -4 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -14- 500985 A7 ——— — '—_ B7 V. Description of the invention (12) 2 2 8 Chemical supply capacity SB broadcast 2 3 0 IBS m pump 2 3 4 Exhaust gas collection container 2 3 6 — Carbon oxide piping 2 3 8 Carbon dioxide heater 2 4 0 Pressurized chamber heater 2 4 2 Circulation line 2 4 4 Circulation in □ 2 4 6 Circulation out □ 2 4 8 Chemical supply line 2 4 9 First injection pump 2 5 0 Flushing agent supply container 2 5 2 Flushing Supply line 2 5 3 First injection pump 2 5 4 Exhaust pipe 2 5 6 Wafer cavity 2 60 Time schedule 2 6 2 Pressure (please read the precautions on the back before filling this page). Line ·· Ministry of Economy A detailed description of a better system printed by the Intellectual Property Bureau employee consumer cooperatives. The present invention uses a method of supercritical dioxide to remove photoresist and residues from a substrate. The residue includes a photoresist residue and an etching residue. Generally, the substrate is a semiconductor wafer. Alternatively, the substrate is a non-wafer substrate such as a rubber disc. Generally, the photoresist is placed on the wafer for semiconducting. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). 15-" " 500985 A7 B7 V. Description of the invention (13 ) A part of the wafer is covered in the body manufacturing process step. This pre-processing step includes ion implantation and uranium engraving steps. In the ion implantation step, the area where the photoresist covers the wafer is not implanted with dopants and the dopants are implanted into the unmasked areas of the wafer. The ion implantation step forms a hard shell on the photoresist, leaving a jelly-like core under the hard shell. During the engraving step, the photoresist masked wafer area was not etched and the unmasked area was etched. In the etching step, the photoresist and the wafer are etched to produce an etched feature pattern, and photoresist residues and etching residues are also generated. Photoresist etching creates photoresist residues. Etching of the feature pattern creates etch residue. Photoresist and etch residue often cover the sidewalls of etched features. In some engraving steps, the photoresist is not etched completely so that a part of the photoresist remains on the wafer after the engraving. During these etching steps, the uranium etch hardens the remaining photoresist. In other etching steps, the photoresist is completely etched so no photoresist remains on the wafer during these etching steps. In the following examples, there are only residues, which are photoresist residues and etching residues, which remain on the wafer. For geometries of 0. 25 microns and smaller, the present invention preferably removes the photoresist directly. In other words, the present invention preferably removes I-line exposure photoresist and shorter-wavelength exposure photoresist directly. These are UV, deep UV, and smaller geometry photoresists. Alternatively, the present invention is directed to removing photoresist having a larger geometry. It is very obvious to those skilled in the art, and the present invention is described from the perspective of removing photoresist and residues. It is also suitable for removing photoresist. This paper size applies Chinese national standard (CNS> A4 specification (210 X 297 mm) {Please read the notes on the back before filling out this page) ίφ ^ α —--- Order ----- | Line | Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 16
湖985 五、發明說明（14) 和殘餘物’或者只除去光阻劑，或只除去殘餘物。 本發明之較佳體系利用超臨界二氧化碳、胺類及溶劑 自基板上除去光阻劑和殘餘物。較佳者，胺類係選自二級 胺及三級胺。更佳者胺類係第三級基胺。又更佳者，胺類 係選自2 -（甲基胺基）乙醇、五甲基二乙撐三胺、三乙 醇胺、三乙胺及彼之混合物。更佳者，胺類係選自2 一（ 甲基胺基）乙醇、五甲基二乙撐三胺及彼之混合物。較佳 者，溶劑係選自二甲基亞碾、碳酸次乙酯、N —甲基一 2 一吡咯烷酮、乙醯丙酮、丁內酯、醋酸、二甲基乙醯胺、 碳酸次丙酯及彼之混合物。更佳者，該溶劑係選自二甲基 亞碼、碳酸次乙酯、N —甲基一 2 —吡咯烷酮、乙醯丙酮 、丁內酯、冰醋酸及彼之混合物。 本發明之較佳方法係列示如圖6中之區塊圖。 適當方法2 0 0開始於放置晶片，光阻劑和殘餘物在 晶片上，於壓力室內並且在第一個加工步驟2 0 2中密封 壓力室。在第二個加工步驟2 0 4中，壓力室利用二氧化 碳加壓直到二氧化矽變成超臨界二氧化碳（S C C. 0 2 )。 在第三個加工步驟2 0 6中，超臨界二氧化碳帶著胺類及 溶劑至加工室中。在第四個加工步驟2 0 8中’保持超臨 界二氧化碳、胺類、溶劑與基板接觸直到光阻劑和殘餘物 自晶片除去爲止。在第五個加工步驟2 1 0中’壓力室係 部份排氣。在第六個加工步驟2 1 2中’沖洗晶片。在第 七個加工步驟2 1 4中’適當方法2 0 0結束於壓力室卸 壓並且移開晶片。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱）_ ] 7 _ (請先閱讀背面之注意事項再填寫本頁) 一ISJ n 1— ϋ Mi 1 n n I i 經濟部智慧財產局員工消費合作社印製 500985 A7 --- B7___ 五、發明說明（15) 適當的超臨界加工系統2 2 0包括二氧化碳供給容器 222、二氧化碳幫浦224、壓力室226、化學物供 給容器2 2 8、循環幫浦2 3 0及廢氣收集容器2 3 4。 二氧化碳供給容器2 2 2經由二氧化碳幫浦2 2 4及二氧 化碳配管2 3 6接到壓力室2 2 6。該二氧化碳配管 2 3 6包括位於二氧化碳幫浦2 2 4及壓力室2 2 6之間 的二氧化碳加熱器2 3 8在內。壓力室2 2 6包括壓力室 加熱器2 4 0在內。循環幫浦2 3 0位於循環管線2 4 2 上’其循環入口 2 4 4及循環出口 2 4 6接到壓力室 2 2 6。化學物供給容器2 2 8經由化學物供給管線 2 4 8接到循環管線2 4 2，其包括第一個注射幫浦 2 4 9在內。沖洗劑供給容器2 5 0經由沖洗供給管線 2 5 2接到循環管線2 4 2，其包括第二個注射幫浦 2 5 3。廢氣收集容器2 3 4經由排氣配管2 5 4接到壓 力室2 2 6。對熟於此藝之士極爲顯而易見的是適當的超 臨界加工系統2 2 0包括閥門、控制電子、過濾器及有用 的接線其係典型的超臨界流體加工系統。 對於熟於此藝之士極爲顯而易見的是額外的化學物供 給容器可以接到第一個注射幫浦2 4 9或額外化學物供給 容器及額外的注射幫浦可以接到循環管線2 4 2。 參照圖6及7兩個圖，適當方法2 0 0之實施開始於 第一個加工步驟2 0 2 ’其中晶片，其具有光阻劑或殘餘 物或光阻劑和殘餘物兩者，係置於壓力室2 2 6內之晶片 腔2 5 6中並且，接著，壓力室2 2 6係密封。在第二個 (請先閲讀背面之注意事項再填寫本頁) -«I ϋ ϋ I 一§*· · 1 n n n n n I I _ 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） -18- 500985 A7 B7 五、發明說明（16) (請先閱讀背面之注意事項再填寫本頁) 加工步驟2 0 4 ’壓力室2 2 6利用得自二氧化碳供給容 器2 2 2之二氧化碳藉著二氧化碳幫浦2 2 4來加壓。在 第二個加工步驟2 0 4中，二氧化碳係利用二氧化碳加熱 器2 3 8加熱同時壓力室2 2 6係利用壓力室加熱器 2 3 8加熱以確保壓力室2 2 6中二氧化碳之溫度超過臨 界溫度以上。二氧化碳之超臨溫度係3 1 °C。較佳地，在 壓力室2 2 6中二氧化碳之溫度係介於4 5 °C至7 5 °C之 間。或者，壓力室2 2 6中二氧化碳之溫度保持於3 1 °C 至大約1 0 0 °C之範圍內。 經濟部智慧財產局員工消費合作社印製 視達到初始超臨界條件而定，第一個注射幫浦2 4 9 將胺及溶劑由化學物供給容器2 2 8經由循環管線2 4 2 抽到壓力室2 2 6同時在第三個加工步驟2 0 6中二氧化 碳幫浦還加壓超臨界二氧化碳。一旦胺及溶劑想要的量已 經抽到壓力室2 2 6中並且達到了想要的超臨界條件，二 氧化碳幫浦2 2 4便停止加壓壓力室2 2 6，第一個注射 幫浦2 4 9停止將胺及溶劑抽到壓力室2 2 6中，而且在 第四個加工步驟2 0 8中循環幫浦2 3 0開始循超臨界二 氧化碳、胺及溶劑。藉著循環超臨界二氧化碳、胺及溶劑 ，超臨界二氧化碳將保持胺及溶劑與晶片接觸。另外，藉 著循環超臨界二氧化碳、胺及溶劑，流體流動增強了自晶 片除去光阻劑和殘餘物。 較佳地，晶片在第四個加工步驟2 0 8期間係於加壓_ 室2 2 6中保持靜態。或者，在第四個加工步驟2 〇 8中 晶片係於壓力室2 2 6中加工出線形。 -19- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 500985 A7 B7 五、發明說明（17) 在光阻劑和殘餘物已經從晶片上除去之後，壓力室 2 2 6係藉著排放某些超臨界二氧化碳、胺及溶劑而卸壓 ’移除光阻劑，並且移除殘餘物至廢氣收集容器2 3 4以 恢復壓力室2 2 6至幾近第四個加工步驟2 1 0之初始超 臨界條件。 在第六個加工步驟2 1 2中，第二個注射幫浦2 5 3 由沖洗劑供給容器2 5 0經由循環管線將沖洗劑抽入壓力 室2 2 6中同時二氧化碳幫浦2 2 4加壓壓力室2 2 6至 幾近想要的超臨界條件並且，接著，循環幫浦2 3 0循環 超臨界一氧化碳及沖洗劑以便沖洗晶片。較佳地，沖洗劑 係選自水、醇、酮及彼之混合物。更佳者，沖洗劑係醇及 水之混合物。較佳地，該醇係選異丙醇、乙醇及其他低分 子量醇類。更佳者，該醇係選自異丙醇及乙醇。最佳者， 該醇係乙醇。 較佳地’晶片在第六個加工步驟2 1 2期間保持靜態 於壓力室2 2 6中。或者，在第六個加工步驟期間晶片係 加工出線形。 在第七個加工步驟2 1 4中，壓力室2 2 6係卸壓， 藉著使壓力室2 2 6排氣至廢氣收集容器2 3 4並且，最 後，晶片自壓力室226中移出。 本發明之適當時程係圖示於圖8中。適當的時程 2 6 0指示適當方法2 〇 〇爲時間之函數並且還指示壓力 2 6 2爲時間之函數。對熟於此藝之士而言極爲顯而易見 的是圖8中的時間軸只是示範性的並且因此沒有依比例指 本紙張尺度適用中國國家標準（CNS)A4規袼（21〇 X 297公釐） <請先閱讀背面之注意事項再填寫本頁> -n mmmmm l n 4 經濟部智慧財產局員Η消費合作社印製 經濟部智慧財產局員Η消費合作社印製 500985 A7 __ B7_____ 五、發明說明（18) 出相對的時段。理想上，當然，所有時間在合於商業及有 效加工方法下都將縮至最短。 在初始時間t D之前，在第一個加工步驟中晶片係置於 壓力室2 2 6中並且壓力室係封密。從初始時間經過第一 時間t :至第二時間t 2，壓力室2 2 6係於第二個加工步 驟2 0 4中加壓。在第一時間t i時壓力室達到超臨界壓力 P。。二氧化碳之超臨界壓力係1，070ps i。較佳地 ，在第三個加工步驟2 0 6第一時間t 1及第二時間t 2之 間胺及溶劑係注入壓力室2 2 6。較佳地，胺及溶劑注射 開始於達到大約1 1 0 0 — 1 2 0 0 p s i時。或者，在 第二時間t 2左右或第二時間t 2以後胺及溶劑係注入壓力 室。在第二時間t 2時壓力室達到操作壓力P。P。較佳地 ，操作壓力P。p係大約2，8 0 0 P s i。或者，操作壓 力Pop係介於1，070ps i至大約6，OOOps i ο 適當的時程2 6 0第四個加工步驟2 0 8接著保持超 臨界二氧化碳、胺類、溶劑與基板接觸直到光阻劑和殘餘 物自晶片除去爲止，其發生於第二時間t 2至第三時間t 3 。在第五個加工步驟2 1 0中，壓力室2 2 6從第三時間 t 3至第四時間t 4部份排氣。較佳地，這藉著第一次排氣 從操作壓力P。p降至大約1，1 0 0 — 1，2 0 0 p s i 而完成，在第一次壓力回塡時從1 ，100 — 1 ，200 P s 1至升至操作壓力P。。，在第二次排氣時再降至 1，100 — 1，200ps i 。或者，壓力回塡及第二 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -21 - (請先閱讀背面之注意事項再填寫本頁) -· I I I I I I I 訂---->線< 500985 A7 ---—_____ B7 五、發明說明（19) 次排氣並非第五個加工步驟2 1 〇之一部份。又或者，額 外的充氣及排氣係第五個加工步驟2 1 〇之一部份其中一 次全排氣可能分成一次或更多次排氣。 適當的時程2 6 0在第六個加工步驟中從第四時間t 4 經過第五時間t 5至第六時間t 6持續沖洗晶片。第六加工 步驟2 1 2開始於第二次壓力回塡在彼期間沖洗劑宜注入 壓力室2 2 6從第四時間t 4至第五時間t 5。在第七個加 工步驟2 1 4 ’壓力室2 2 6排氣從第六時間t 6至第七時 間t 7。較佳地，這係藉著在第三次排氣時降低操作壓力 Pep至大約1，100 — 1，200ps i ，藉著在第三 次壓力回塡從1 ，100— 1 ，200ps i升至操作壓 力Ρ ，最後在最後一次排氣中降至大氣壓力而完成。或 者，第三次排氣及第三次壓力回塡並非屬於第七個加工步 驟2 1 4的一部份。又或者，其餘的排氣及回塡都屬於第 五個加工步驟2 1 0。 本發明第一個替代體系將一種水溶性氟化物添加至適 當體系中。在第一個替代體系中，超臨界二氧化碳、胺、 溶液及水溶性氟化物除去了光阻劑和殘餘物。較佳地，水 溶性氟化物係選自鹼性氟化物及酸性氟化物。更佳地，水 溶性氟化物係選自水溶性氟化銨（水溶性Ν Η 4 F )，及水 溶性氫氟酸（H F )。 第一個替代體系係有用的當大部份光阻劑或大部份殘 餘物係自二氧化矽（S i 0 2 )表面除去。水溶性氟化物藉 著稍微蝕刻二氧化矽表面，自光阻劑和殘餘物向下切掉二 (請先閲讀背面之注意事項再填寫本頁) ^Mwilti! * 訂-----I----線* 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -22 - 500985 經濟部智慧財產局員工消費合作社印製 A7 B7_____ 五、發明說明（20) 氧化矽表面。然而水溶液係有用於自晶片之二氧化矽表面 除去光阻劑或殘餘物，當晶片包括曝光鋁層在內時則水溶 性氟化物無法使用。 ， 本發明第二個替代體系添加額外的水至第一個替代體 系中。額外的水增強了第一個替代體系因爲光阻劑係親水 性的同時二氧化矽表面係疏水性的。由此，額外的水隔離 了光阻劑及二氧化矽表面。 本發明第三個替代體系使用了超臨界二氧化碳及水溶 性氟化物以除去光阻劑和殘餘物。在第三個替代體系中’ 不使用胺並且不使用溶劑。 本發明第四個替代體系添加額外的水至超臨界二氧化 碳及水溶性氟化物。 本發明第五個替代體系添加溶劑至第三個替代體系中 〇 在第一個替代時程中，第四個加工步驟2 0 8在初始 淸洗壓力及最終淸洗壓力時進行。較佳地，初始淸洗壓力 係大約1 ，100 — 1 ，200ps i而最後淸洗壓力大 約2，8 0 0 p s i 。在最初淸洗壓力時，某些化學物之 第一溶解度低於最終淸洗壓力之第二溶解度。在發生於初 始淸洗壓力之初始淸洗階段期間，較低溶解度化學物凝結 在晶片上。這形成較高濃度之低溶解度化學物於光阻劑和 殘餘物上並且，由此，增強了光阻劑和殘餘物與晶片之隔 離。在發明於最終淸洗壓力之最終淸洗階段期間，較低溶 解度化學物不再凝結或凝結少於於晶片上並且，由此，預 I ——-i — ----訂！！線· m - (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） -23- 經濟部智慧財產局員工消費合作社印製 500985 A7 _——— B7 五、發明說明（21) 期兀成弟四個加工步驟2 0 8時在晶片上之較低溶解度化 學物之濃度將會降低。 在本發明第二個替代體系中，第二次沖洗在執行第一 次沖洗之後進行。 指定體系 本發明第一個至第七個特定體系都在以下討論。第一 個至第七個體系之中任何一者都是指定化學物及指定方法 都是實驗室系統之總結，相似於適當超臨界加工系統 2 2 0。實驗室系統用於除去光阻劑，或除去光阻劑和殘 餘物，或自試驗晶片上除去殘餘物。實驗室系統特徵爲合 倂壓力室2 2 6、循環幫浦2 3 0及循環管線2 4 2之內 部體積爲大約1.8公升。第一至第七個指定體系屬於槪 代驗證可能性硏究之一部份企_展示本發明用於半導體製 造之可能性。在將本發明引用於半導體製造之前，已預見 可以完成更進一步之加工精製。 第一個指定體系 在第一個指定體系中，光阻劑自前述導通孔蝕刻步驟 生成之二氧化矽導通孔結構除去，其中飩刻步驟結束於達 到鋁餽刻阻擋物時。使用之該指定化學物如下：2毫升2 —甲基胺基乙醇（胺）、20毫升二甲基亞碼（溶劑之第 一種成份），及2 0毫升碳酸次乙酯（溶劑之第二種成份 )。壓力室保持於50°C。胺及溶劑在2，8〇〇Ps 1 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） _ 24 - I---.1-丨-.1|丨4||^!!訂_^---- 線· 嫌 - {請先閱讀背面之注意事項再填寫本頁) 500985 A7 B7 五、發明說明（22) 下循環5分鐘。在除去及沖洗洗步驟之間進行兩次部份排 氣及一次全排氣其中部份排氣時壓力從2，700p s i 降至1，1 0 0 p s i而全排氣時壓力從 2，7 0 0 p s i降至大氣壓力。用於沖洗步驟之沖洗劑 係5 6毫升之丙酮。沖洗劑及超臨界二氧化碳循環5分鐘 。一次部份排氣在進行完全排氣之前接著沖洗步驟之後執 行。 在第一個指定體系中接著光阻劑和殘餘物除去之後拍 得第一張掃描式電子顯微照片。第一張掃描式電子顯微照 片顯示在第一個指定體系中光阻劑和殘餘物係除去。 第二個指定體系 在第二個指定體系中，殘餘物，其包括光阻劑殘餘物 及蝕刻殘餘物，係自前述金屬線鈾步驟生成之金屬線結構 除去，其中飩刻步驟結束於達到氧化物触刻阻擋物時。（ 用於第二個指定體系之試驗晶片承蒙Lucent Technologies提 供。）使用之指定化學物如下：1 · 5毫升五甲基二乙撐 三胺（胺）、7 · 5毫升N —甲基一 2 -吡咯烷酮（溶劑 之第一種成份）及6毫升乙醯丙酮（溶劑之第二種成份） 。胺及溶劑在2，8 0 0 p s i下循環2分鐘。在除去及 沖洗洗步驟之間進行兩次部份排氣及一次全排氣。用於沖 洗步驟之沖洗劑係2 0毫升之8 0 %乙醇及2 0 %水混合 物，體積比例。沖洗劑及超臨界二氧化碳循環1分鐘。一 次部份排氣接著沖洗步驟之後執行。 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） -25 - (請先閱讀背面之注意事項再填寫本頁) -«ΪI I----訂·1 線- 經濟部智慧財產局員工消費合作社印製 500985 A7 B7 五、發明說明（23) (請先閱讀背面之注意事項再填寫本頁) 在第二個指定體系中在光阻劑和殘餘物除去之前拍得 第二張掃描式電子顯微照片。第張次掃描式電子顯微照片 顯示金屬線側壁上之殘餘物，並且顯示殘餘物殘留在金屬 線頂端。在第二個指定體系中接著光阻劑和殘餘物除去之 後拍得第三及第四張掃描式電子顯微照片。第三及第四張 掃描式電子顯微照片顯示在第二個指定體系中殘餘物係除 去。 第三個指定體系 經濟部智慧財產局員工消費合作社印製 在第三個指定體系中，光阻劑自中等強度離子注入之 後的晶片除去。使用之指定化學物如下：0 · 1 5毫升體 積比例2 4 %之水溶性氟化銨（水溶性氟化物）、2 0毫 升丁內酯（溶劑之第一種成份）、2 0毫升二甲基亞碼（ 溶劑之第二種成份）、0 · 1 5毫升冰醋酸（溶劑之第三 種成份）及1毫升外加的水。壓力室保持於7 0 °C，水溶 性氟化物及溶劑在1，2 5 0 p s i下循環2分鐘其後壓 力室加壓至2，8 0 0 p s i 。在除去及沖洗洗步驟之間 進行兩次部份排氣及一次全排氣其中部份排氣時壓力從 2，700ps i降至1 ，lOOps i而全排氣時壓力 從2，7 0 0 p s i降至大氣壓力。用於沖洗步驟之沖洗 劑係2 0毫升之8 0 %乙醇及2 0 %水之混合物。沖洗劑 及超臨界二氧化碳循環1分鐘。一次部份排氣在進行全排 氣之前接著沖洗步驟之後執行。 在X P S ( X射線光電子光譜）試驗前後證實第三個 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -26 - 500985 A7 ——___Β7_______ 五、發明說明（24) 指定體系中光阻劑係除去。 第四個指定體系 在第四個指定體系中，光阻劑自高強度離子注入之後 的晶片除去。使用之該指定化學物如下：〇 · 2 2毫升體 積比例2 4 %之水溶性氟化銨（水溶性氟化物）、2 0毫 升二甲基亞碾（溶劑之第一種成份）、2 0毫升碳酸次乙 酯（溶劑之第二種成份）及2毫升外加的水。壓力室保持 於70t。水溶性氟化物及溶劑在2，80 0p s i下循 環2分鐘。在除去及沖洗洗步驟之間進行兩次部份排氣及 一次全排氣其中部份排氣時壓力從2，7 0 0 p s i降至 1，lOOps i而全排氣時壓力從2，700ps i降 至大氣壓力。用於沖洗步驟之沖洗劑係2 0毫升之8 0 % 乙醇及2 0 %水之混合物。沖洗劑及超臨界二氧化碳循環 1分鐘。一次部份排氣在進行全排氣之前接著沖洗步驟之 後執行。 在X射線光電子光譜試驗前後證實第四個指定體系中 光阻劑係除去。 第五個指定體系 在第五個指定體系中，光阻劑自前述導通孔餽刻步驟 生成之二氧化矽導通孔結構除去，其中蝕刻步驟結束於達 到氮化鈦餽刻阻擋物時。使用之該指定化學物如下： 0 · 1 5毫升體積比例2 4 %之水溶性氟化銨（水溶性氟 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -27 - (請先閱讀背面之注意事項再填寫本頁} -身！ —訂ί 纛 線- 經濟部智慧財產局員Η消費合作社印製 經濟部智慧財產局員工消費合作社印製 500985 A7 ______ B7 五、發明說明（25) 化物）及8毫升外加的水。壓力室保持於5 0 °C。水溶性 氟化物及外加的水在1，5 0 0 p s i下循環2分鐘。在 除去步驟及第一次沖洗洗步驟之間進行兩次部份排氣及一 次全排氣其中部份排氣時壓力從1，5 0 0 p s i降至 1’ 〇50ps i而全排氣時壓力從1 ，500ps i降 至大氣壓力。用於第一次沖洗步驟之沖洗劑係1 2毫升之 水。在第一次沖洗步驟中，沖洗劑及超臨界二氧化碳在 1 ’ 500ps i下循環1分鐘接著壓力係升至 2 ’ 8 0 0 p s i 。在第一次沖洗步驟及第二次沖洗洗步 驟之間進行兩次部份排氣及一次全排氣其中部份排氣時壓 力從2，800ps i降至1 ，lOOps i而全排氣時 壓力從2，800ps i降至大氣壓力。用於第二次沖洗 步驟之沖洗劑係2 0毫升之甲醇。在第二次沖洗步驟中， 沖洗劑及超臨界二氧化碳在2，8 0 0 p s i下循環1分 鐘。一次部份排氣在進行全排氣之前接著第二次沖洗步驟 之後執行。 在第五個指定體系中接著光阻劑除去之前拍得第五張 掃描式電子顯微照片。第五張掃描式電子顯微照片顯示在 二氧化矽導通孔結構上之光阻劑及導通孔底部之氮化鈦飩 刻阻擋物。在第五個指定體系中接著光阻劑除去之後拍得 第六張掃描式電子顯微照片。第六張掃描式電子顯微照片 顯示在第五個指定體系中光阻劑係除去。 第六個指定體系 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _ 28 _ (請先閱讀背面之注意事項再填寫本頁) —i κϋ^dJi mtmm mmmf Ml n IB ϋ n I | 500985 A7 __— ............. B7 五、發明說明（26) 在第六個指定體系中，光阻劑自前述導通孔飩刻步驟 生成之二氧化矽導通孔結構除去。使用之該指定化學物如 下：1 · 5毫升體積比例2 4 %之水溶性氟化銨（水溶性 氟化物）及8毫升二甲基亞碼（溶液）及4毫升外加的水 。壓力室保持於5 0 °C。水溶性氟化物、溶液及外加的水 在2 ’ 8 0 0 ps i下循環2分鐘。在除去步驟及沖洗洗 步驟之間進行兩次部份排氣及一次全排氣。沖洗劑係2 0 毫升之8 0%乙醇及2 0%水。沖洗劑及超臨界二氧化碳 在2，7 0 0 p s i下循環1分鐘。一次部份排氣在進行 全排氣之前接著沖洗步驟之後執行。 在第六個指定體系中接著光阻劑除去之後拍得第七張 掃描式電子顯微照片。第七張掃描式電子顯微照片顯示在 第六個指定體系中光阻劑係除去。 第七個指定體系 在第七個指定體系中，光阻劑和殘餘物自前述導通孔 蝕刻步驟生成之碳-二氧化矽蝕刻結構除去。使用之該指 定化學物如下：0 · 1 5毫升體積比例2 4 %之水溶性氟 化銨（水溶性氟化物）、2 0毫升丁內酯（溶液之第一種 成份）、2 0毫升二甲基亞碼（溶劑之第二種成份）、 〇 · 1 5毫升冰醋酸（溶劑之第三種成份）及1毫升外加 的水。壓力室保持於7 0 °C。水溶性氟化物、溶液及外加 的水在2，8 0 0 ps i下循環2分鐘。在除去步驟及沖 洗洗步驟之間進行兩次部份排氣及一次全排氣。沖洗劑係 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _ 29 - (請先閱讀背面之注意事項再填寫本頁) ---—訂i 蠢 線* 經濟部智慧財產局員Η消費合作社印製 500985 A7 ____B7____ 五、發明說明（27) 2 0毫升之5 0%乙醇及5 0%水。沖洗劑及超臨界二氧 化碳在2，700ps i下循環1分鐘。一次部份排氣在 進行全排氣之前接著沖洗步驟之後執行。 在第七個指定體系中接著光阻劑和殘餘物除去之後拍 得第八張掃描式電子顯微照片。第八張掃描式電子顯微照 片顯示在第七個指定體系中光阻劑和殘餘物係除去。 對熟於此藝之士而言極爲顯易見的是其他不同的改良 可以實施於適當體系而不會背離本發明附屬申請專利範画 定義之精神及範圍。 (請先閱讀背面之注意事項再填寫本頁) 訂！！線秦 經濟部智慧財產局員Η消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -30 -Lake 985 V. Invention Description (14) and Residue 'either remove only photoresist or only residue. The preferred system of the present invention uses supercritical carbon dioxide, amines, and solvents to remove photoresist and residues from the substrate. Preferably, the amines are selected from secondary amines and tertiary amines. The more preferred amines are tertiary amines. Even more preferably, the amines are selected from the group consisting of 2- (methylamino) ethanol, pentamethyldiethylenetriamine, triethanolamine, triethylamine, and mixtures thereof. More preferably, the amines are selected from the group consisting of 2-mono (methylamino) ethanol, pentamethyldiethylenetriamine, and mixtures thereof. Preferably, the solvent is selected from the group consisting of dimethylmethylene, ethylidene carbonate, N-methyl-2-pyrrolidone, acetoacetone, butyrolactone, acetic acid, dimethylacetamide, propylene carbonate, and Another mixture. More preferably, the solvent is selected from the group consisting of dimethylene code, ethylidene carbonate, N-methyl-2-pyrrolidone, acetoacetone, butyrolactone, glacial acetic acid, and mixtures thereof. A series of preferred methods of the present invention is shown in the block diagram in FIG. 6. Appropriate method 2000 starts with placing the wafer, photoresist and residues on the wafer, in a pressure chamber and sealing the pressure chamber in the first processing step 202. In the second processing step 204, the pressure chamber is pressurized with carbon dioxide until the silicon dioxide becomes supercritical carbon dioxide (S C C. 0 2). In the third processing step 206, supercritical carbon dioxide carries amines and solvents into the processing chamber. In the fourth processing step 208 ', the supercritical carbon dioxide, amines, solvents are kept in contact with the substrate until the photoresist and residue are removed from the wafer. In the fifth processing step 210, the 'pressure chamber is partially vented. In the sixth processing step 2 1 2 'the wafer is rinsed. In the seventh processing step 2 1 4 'the appropriate method 2 0 0 ends with depressurization of the pressure chamber and the wafer is removed. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) _] 7 _ (Please read the precautions on the back before filling out this page) One ISJ n 1— ϋ Mi 1 nn I i Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau 500985 A7 --- B7___ V. Description of the invention (15) Appropriate supercritical processing system 2 2 0 includes carbon dioxide supply container 222, carbon dioxide pump 224, pressure chamber 226, and chemical supply container 2 2 8. Circulating pump 2 3 0 and exhaust gas collecting container 2 3 4. The carbon dioxide supply container 2 2 2 is connected to the pressure chamber 2 2 6 through a carbon dioxide pump 2 2 4 and a carbon dioxide pipe 2 3 6. The carbon dioxide pipe 2 3 6 includes a carbon dioxide heater 2 3 8 located between the carbon dioxide pump 2 2 4 and the pressure chamber 2 2 6. The pressure chamber 2 2 6 includes a pressure chamber heater 2 4 0. The circulation pump 2 30 is located on the circulation line 2 4 2 and its circulation inlet 2 4 4 and the circulation outlet 2 4 6 are connected to the pressure chamber 2 2 6. The chemical supply container 2 2 8 is connected to the circulation line 2 4 2 through the chemical supply line 2 4 8 and includes the first injection pump 2 4 9. The rinsing agent supply container 2 50 is connected to the circulation line 2 4 2 via the flushing supply line 2 5 2 and includes a second injection pump 2 5 3. The exhaust gas collection container 2 3 4 is connected to the pressure chamber 2 2 6 through an exhaust pipe 2 5 4. It is very obvious to those skilled in the art that a suitable supercritical processing system 220 includes valves, control electronics, filters and useful wiring. It is a typical supercritical fluid processing system. It is very obvious to those skilled in the art that the additional chemical supply container can be connected to the first injection pump 2 4 9 or the additional chemical supply container and the additional injection pump can be connected to the circulation line 2 4 2. With reference to Figures 6 and 7, the implementation of the appropriate method 200 begins with the first processing step 2 0 2 'wherein the wafer, which has a photoresist or residue or both photoresist and residue, is mounted. In the wafer cavity 2 5 6 in the pressure chamber 2 2 6 and, then, the pressure chamber 2 2 6 is sealed. In the second one (please read the precautions on the back before filling this page)-«I ϋ ϋ I 一 § * · · 1 nnnnn II _ Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) -18- 500 985 A7 B7 V. Description of the invention (16) (Please read the precautions on the back before filling this page) Processing step 2 0 4 'Pressure chamber 2 2 6 Use The carbon dioxide obtained from the carbon dioxide supply container 2 2 2 is pressurized by a carbon dioxide pump 2 2 4. In the second processing step 204, the carbon dioxide is heated by the carbon dioxide heater 2 3 8 while the pressure chamber 2 2 6 is heated by the pressure chamber heater 2 3 8 to ensure that the temperature of the carbon dioxide in the pressure chamber 2 2 6 exceeds the threshold. Above temperature. The supercritical temperature of carbon dioxide is 3 1 ° C. Preferably, the temperature of the carbon dioxide in the pressure chamber 2 2 6 is between 45 ° C and 75 ° C. Alternatively, the temperature of the carbon dioxide in the pressure chamber 2 2 6 is maintained in a range of 3 1 ° C to about 100 ° C. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, depending on the initial supercritical conditions reached. The first injection pump 2 4 9 feeds the amine and solvent from the chemical container 2 2 8 to the pressure chamber through the circulation line 2 4 2 2 2 6 At the same time, the carbon dioxide pump also pressurizes the supercritical carbon dioxide in the third processing step 20. Once the desired amount of amine and solvent has been pumped into the pressure chamber 2 2 6 and the desired supercritical conditions have been reached, the carbon dioxide pump 2 2 4 stops pressurizing the pressure chamber 2 2 6 and the first injection pump 2 4 9 Stop pumping the amine and solvent into the pressure chamber 2 2 6, and in the fourth processing step 2 0 8 circulate the pump 2 3 0 to start the supercritical carbon dioxide, the amine and the solvent. By cycling supercritical carbon dioxide, amines and solvents, supercritical carbon dioxide will keep the amines and solvents in contact with the wafer. In addition, by cycling supercritical carbon dioxide, amines, and solvents, fluid flow enhances the removal of photoresist and residues from the wafer. Preferably, the wafer is held static in the pressurized chamber 2 2 6 during the fourth processing step 2008. Alternatively, in the fourth processing step 2008, the wafer is processed into a linear shape in the pressure chamber 226. -19- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 500985 A7 B7 V. Description of the invention (17) After the photoresist and residue have been removed from the wafer, the pressure chamber 2 2 Series 6 releases pressure by removing certain supercritical carbon dioxide, amines, and solvents to remove the photoresist and remove the residue to the exhaust gas collection container 2 3 4 to restore the pressure chamber 2 2 6 to almost the fourth process Step 2 10 Initial supercritical conditions. In the sixth processing step 2 1 2, the second injection pump 2 5 3 is supplied from the flushing agent container 2 5 0 and the flushing agent is drawn into the pressure chamber 2 2 6 through the circulation line while the carbon dioxide pump 2 2 4 is added. The pressure chamber 2 2 6 is almost to the desired supercritical condition and, then, the circulation pump 2 30 circulates the supercritical carbon monoxide and a flushing agent to flush the wafer. Preferably, the rinsing agent is selected from the group consisting of water, alcohol, ketone and mixtures thereof. More preferably, the rinse agent is a mixture of alcohol and water. Preferably, the alcohol is selected from isopropanol, ethanol and other low molecular weight alcohols. More preferably, the alcohol is selected from isopropyl alcohol and ethanol. Most preferably, the alcohol is ethanol. Preferably, the wafer is held static in the pressure chamber 2 2 6 during the sixth processing step 2 1 2. Alternatively, the wafer is processed into a linear shape during the sixth processing step. In the seventh processing step 2 1 4, the pressure chamber 2 2 6 is depressurized, and the pressure chamber 2 2 6 is exhausted to the exhaust gas collection container 2 3 4 and, finally, the wafer is removed from the pressure chamber 226. A suitable time course of the present invention is illustrated in FIG. 8. A suitable time schedule 2 6 0 indicates a suitable method 2 0 0 as a function of time and also indicates a pressure 2 6 2 as a function of time. It is extremely obvious to those who are familiar with this art that the time axis in Figure 8 is only exemplary and therefore does not refer to the scale of this paper to apply the Chinese National Standard (CNS) A4 Regulation (21 × X 297 mm) < Please read the notes on the back before filling in this page > -n mmmmm ln 4 Member of the Intellectual Property Office of the Ministry of Economic Affairs 印 Printed by the Consumer Cooperative Cooperatives Member of the Intellectual Property Bureau of the Ministry of Economics ΗPrinted by the Consumer Cooperatives 500985 A7 __ B7_____ V. Description of Invention ) Show relative periods. Ideally, of course, all time will be minimized with commercial and efficient processing methods. Before the initial time t D, the wafer system is placed in the pressure chamber 2 2 6 and the pressure chamber system is sealed in the first processing step. From the initial time to the first time t: to the second time t2, the pressure chamber 2 2 6 is pressurized in the second processing step 2 0 4. At the first time t i, the pressure chamber reaches a supercritical pressure P. . The supercritical pressure of carbon dioxide is 1,070 ps i. Preferably, the amine and the solvent are injected into the pressure chamber 2 2 6 during the third processing step 20 6 between the first time t 1 and the second time t 2. Preferably, the amine and solvent injections begin at about 1 1 0-1 2 0 0 p s i. Alternatively, the amine and the solvent are injected into the pressure chamber around the second time t 2 or after the second time t 2. At a second time t 2, the pressure chamber reaches the operating pressure P. P. Preferably, the operating pressure P. p is about 2,800 P s i. Alternatively, the operating pressure Pop is between 1,070 ps i and about 6,000 ps i. Appropriate time course 2 6 0 Fourth processing step 2 0 8 Then keep the supercritical carbon dioxide, amines, solvents in contact with the substrate until the photoresist Until the agent and residue are removed from the wafer, it occurs from a second time t 2 to a third time t 3. In the fifth processing step 2 10, the pressure chamber 2 2 6 is partially vented from the third time t 3 to the fourth time t 4. Preferably, this is from the operating pressure P by the first exhaust. p is reduced to approximately 1, 100-1, 2, 0 p s i and is completed, from 1, 100-1, 200 P s 1 to the operating pressure P at the first pressure recovery. . During the second exhaust, it drops to 1,100-1,200 ps. Alternatively, the pressure return and the second paper size apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -21-(Please read the precautions on the back before filling this page)-· IIIIIII Order --- -> Line < 500985 A7 -----_____ B7 V. Description of the invention (19) The exhaust gas is not part of the fifth processing step 2 1 0. Alternatively, the additional inflation and exhaust are part of the fifth processing step 21, and one full exhaust may be divided into one or more exhausts. The appropriate time course 2 6 0 in the sixth processing step continues from the fourth time t 4 through the fifth time t 5 to the sixth time t 6 to continuously rinse the wafer. The sixth processing step 2 1 2 starts with the second pressure recovery. During that time, the flushing agent should be injected into the pressure chamber 2 2 6 from the fourth time t 4 to the fifth time t 5. In the seventh processing step 2 1 4 ', the pressure chamber 2 2 6 is exhausted from the sixth time t 6 to the seventh time t 7. Preferably, this is increased from 1,100-1,200ps i to 1,100-1,200ps i by reducing the operating pressure Pep to about 1,100-1,200ps i during the third exhaust. The operating pressure P is finally reduced to atmospheric pressure during the last exhaust. Or, the third exhaust and the third pressure return are not part of the seventh processing step 2 1 4. Or, the rest of the exhaust and recirculation belong to the fifth processing step 2 1 0. The first alternative system of the present invention adds a water-soluble fluoride to a suitable system. In the first alternative system, supercritical carbon dioxide, amines, solutions, and water-soluble fluorides removed photoresist and residues. Preferably, the water-soluble fluoride is selected from basic fluoride and acid fluoride. More preferably, the water-soluble fluoride system is selected from water-soluble ammonium fluoride (water-soluble NΗ4F) and water-soluble hydrofluoric acid (HF). The first alternative system is useful when most photoresist or most residues are removed from the surface of silicon dioxide (S i 0 2). By slightly etching the surface of the silicon dioxide, the water-soluble fluoride is cut off from the photoresist and the residue (please read the precautions on the back before filling this page) ^ Mwilti! * Order ----- I-- --Line * Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed to the Chinese National Standard (CNS) A4 (210 X 297 mm) -22-500985 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_____ 5 2. Description of the invention (20) Silicon oxide surface. However, the aqueous solution is used to remove photoresist or residue from the silicon dioxide surface of the wafer. When the wafer includes an exposed aluminum layer, water-soluble fluoride cannot be used. The second alternative system of the present invention adds additional water to the first alternative system. The additional water enhanced the first alternative system because the photoresist was hydrophilic and the silica surface was hydrophobic. As a result, additional water isolates the photoresist and the silica surface. The third alternative system of the present invention uses supercritical carbon dioxide and water-soluble fluoride to remove photoresist and residues. In the third alternative system ', no amine is used and no solvent is used. The fourth alternative system of the present invention adds additional water to supercritical carbon dioxide and water-soluble fluoride. In the fifth alternative system of the present invention, a solvent is added to the third alternative system. In the first alternative time course, the fourth processing step 208 is performed at the initial washing pressure and the final washing pressure. Preferably, the initial scrubbing pressure is about 1,100-1, 200 ps i and the final scrubbing pressure is about 2,800 ps i. At the initial rinse pressure, the first solubility of some chemicals is lower than the second solubility of the final rinse pressure. During the initial scrubbing phase, which occurs during the initial scrubbing pressure, lower solubility chemicals condense on the wafer. This forms a higher concentration of a low solubility chemical on the photoresist and the residue and, thereby, enhances the isolation of the photoresist and the residue from the wafer. During the final scrubbing phase invented at the final scrubbing pressure, the lower-solubility chemicals no longer coagulate or coagulate less than on the wafer and, therefore, pre-I --- i----- order! !! Line · m-(Please read the precautions on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -23- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 500985 A7 _———— B7 V. Description of the invention (21) The concentration of the lower-solubility chemical on the wafer at the time of the four processing steps of 208 will be reduced. In a second alternative system of the present invention, the second rinse is performed after performing the first rinse. Designated systems The first to seventh specific systems of the invention are discussed below. Each of the first to seventh systems is a designated chemical and a designated method are a summary of a laboratory system, similar to an appropriate supercritical processing system 2 2 0. Laboratory systems are used to remove photoresist, or to remove photoresist and residues, or to remove residues from test wafers. The laboratory system is characterized by a combined internal volume of pressure chamber 2 2 6, circulating pump 2 3 0 and circulating line 2 4 2 of approximately 1.8 liters. The first to seventh designated systems are part of the research on the possibility of generation verification. _ Show the possibility of the present invention for semiconductor manufacturing. Before the invention is incorporated into semiconductor manufacturing, it has been foreseen that further processing refinement can be accomplished. First designated system In the first designated system, the photoresist is removed from the silicon dioxide via structure generated in the aforementioned via etching step, where the engraving step ends when the aluminum feed block is reached. The specified chemicals used are as follows: 2 ml of 2-methylaminoethanol (amine), 20 ml of dimethyl sub code (the first component of a solvent), and 20 ml of ethyl carbonate (the second component of a solvent) Ingredients). The pressure chamber is maintained at 50 ° C. Amines and solvents at 2,800 Ps 1 This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) _ 24-I ---. 1- 丨 -.1 | 丨 4 || ^ !! Order _ ^ ---- Line · Suspect-{Please read the notes on the back before filling this page) 500985 A7 B7 V. Description of the invention (22) Cycle for 5 minutes. Two partial exhausts and one full exhaust were performed between the removal and flushing steps. Partial exhaust was reduced from 2,700 p si to 1,100 psi and the exhaust pressure was 2,7 0 0 psi to atmospheric pressure. The rinse agent used in the rinse step was 56 ml of acetone. The rinse agent and supercritical carbon dioxide are circulated for 5 minutes. A partial exhaust is performed before the full exhaust followed by the flushing step. The first scanning electron micrograph was taken in the first designated system, followed by the removal of photoresist and residues. The first scanning electron micrograph showed the removal of photoresist and residues in the first designated system. Second designated system In the second designated system, residues, including photoresist residues and etching residues, are removed from the metal wire structure generated in the aforementioned metal wire uranium step, where the engraving step ends when oxidation When objects touch the barrier. (Test wafers for the second designated system are courtesy of Lucent Technologies.) The designated chemicals used are as follows: 1.5 ml of pentamethyldiethylenetriamine (amine), and 7 · 5 ml of N-methyl-2 -Pyrrolidone (the first component of the solvent) and 6 ml of acetamidine (the second component of the solvent). The amine and solvent were cycled at 2,800 p s i for 2 minutes. Two partial exhausts and one full exhaust were performed between the removal and flushing steps. The rinsing agent used in the rinsing step was a mixture of 80% ethanol and 20% water in 20 ml, volume ratio. The rinse agent and supercritical carbon dioxide were circulated for 1 minute. A partial exhaust is performed after the flushing step. This paper size applies Chinese National Standard (CNS) A4 Regulations (210 X 297 mm) -25-(Please read the notes on the back before filling this page)-«ΪI I ---- Order · 1 Line-Economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau 500985 A7 B7 V. Description of Invention (23) (Please read the notes on the back before filling this page) Photographed in the second designated system before the photoresist and residue are removed Second scanning electron micrograph. The first scanning electron micrograph shows residues on the side walls of the wire and shows that the residue remains on the top of the wire. The third and fourth scanning electron micrographs were taken in the second designated system, followed by the removal of photoresist and residues. The third and fourth scanning electron micrographs show the removal of residues in the second designated system. The third designated system is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the third designated system, the photoresist is removed from the wafer after medium-intensity ion implantation. The specified chemicals used are as follows: 0 · 15 ml of water-soluble ammonium fluoride (water-soluble fluoride) with a volume ratio of 24%, 20 ml of butyrolactone (the first component of the solvent), and 20 ml of dimethylformamide GIA (the second component of the solvent), 0 · 15 ml of glacial acetic acid (the third component of the solvent) and 1 ml of additional water. The pressure chamber was maintained at 70 ° C, and the water-soluble fluoride and the solvent were circulated at 1,250 p s for 2 minutes, and then the pressure chamber was pressurized to 2,800 p s i. Between the removal and flushing steps, two partial exhausts and one full exhaust were performed. Partial exhaust pressure decreased from 2,700 ps i to 1,100 ps and full exhaust pressure from 2,7 0 0 psi drops to atmospheric pressure. The rinse agent used in the rinse step was a mixture of 20 ml of 80% ethanol and 20% water. The rinse agent and supercritical carbon dioxide were circulated for 1 minute. A partial exhaust is performed before the full exhaust followed by the flushing step. Before and after the XPS (X-ray photoelectron spectroscopy) test, it was confirmed that the third paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -26-500985 A7 ——___ Β7 _______ V. Description of the invention (24) Designated system Medium photoresist is removed. Fourth Designated System In the fourth specified system, the photoresist is removed from the wafer after high intensity ion implantation. The specified chemicals used are as follows: 0.2 ml of a water-soluble ammonium fluoride (water-soluble fluoride) with a volume ratio of 24%, 20 ml of dimethylimine (the first component of a solvent), and 20 Ml of ethylene carbonate (the second component of the solvent) and 2 ml of additional water. The pressure chamber is maintained at 70t. The water-soluble fluoride and solvent were circulated at 2,800 p s i for 2 minutes. Two partial exhausts and one full exhaust were performed between the removal and flushing steps. Partial exhaust was reduced from 2,700 psi to 1,100 ps i and exhaust pressure was 2,700 ps. i drops to atmospheric pressure. The rinse agent used in the rinse step is a mixture of 20 ml of 80% ethanol and 20% water. The rinse agent and supercritical carbon dioxide were circulated for 1 minute. A partial exhaust is performed before the full exhaust followed by the flushing step. The removal of the photoresist system in the fourth designated system was confirmed before and after the X-ray photoelectron spectroscopy test. Fifth Specified System In the fifth designated system, the photoresist is removed from the silicon dioxide via structure generated in the aforementioned via feeding step, wherein the etching step ends when the titanium nitride feed barrier is reached. The specified chemicals used are as follows: 0 · 15 ml of water-soluble ammonium fluoride with a volume ratio of 24% (water-soluble fluorine. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -27- (Please read the precautions on the back before filling this page} -Body! — Order 纛--Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Η Printed by the Consumer Cooperative Cooperative, printed by the Consumers ’Cooperative of the Ministry of Economic Affairs 500985 A7 ______ B7 V. Description of the Invention (25) compounds) and 8 ml of additional water. The pressure chamber is maintained at 50 ° C. Water-soluble fluoride and additional water are circulated at 1,500 psi for 2 minutes. During the removal step and the first rinse Two partial exhausts and one full exhaust were performed between the steps. The pressure of part of the exhaust was reduced from 1,500 psi to 1 '050ps i and the pressure of full exhaust was reduced from 1,500ps i to atmospheric pressure. The flushing agent used in the first flushing step was 12 ml of water. In the first flushing step, the flushing agent and supercritical carbon dioxide were circulated at 1 '500ps i for 1 minute and then the pressure was raised to 2' 8 0 0 psi. During the first flush step and the second flush During the washing step, two partial exhausts and one full exhaust were performed. Part of the exhaust pressure dropped from 2,800ps i to 1,100ps i and the pressure during full exhaust decreased from 2,800ps i to atmospheric pressure. The flushing agent used in the second flushing step was 20 ml of methanol. In the second flushing step, the flushing agent and supercritical carbon dioxide were circulated for 1 minute at 2,800 psi. Part of the exhaust was at Performed before full exhaust followed by the second rinse step. A fifth scanning electron micrograph was taken in the fifth designated system followed by photoresist removal. The fifth scanning electron micrograph is shown in The photoresist on the silicon dioxide via structure and the titanium nitride etch stop at the bottom of the via. In the fifth designated system, the sixth scanning electron micrograph was taken after the photoresist was removed. Six scanning electron micrographs show that the photoresist system was removed in the fifth designated system. The sixth designated system is based on the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ 28 _ ( Please read the notes on the back first (Fill in this page) —i κϋ ^ dJi mtmm mmmf Ml n IB ϋ n I | 500985 A7 __— ............. B7 V. Description of the invention (26) In the sixth designated system The photoresist is removed from the silicon dioxide via structure generated in the aforementioned via engraving step. The specified chemical used is as follows: 1.5 ml of water-soluble ammonium fluoride (water-soluble fluoride) with a volume ratio of 24% And 8 ml of dimethylformite (solution) and 4 ml of additional water. The pressure chamber is maintained at 50 ° C. The water-soluble fluoride, solution and additional water were circulated at 2 '800 ps i for 2 minutes. Two partial exhausts and one full exhaust were performed between the removal step and the rinse step. Rinse agent is 20 ml of 80% ethanol and 20% water. The rinsing agent and supercritical carbon dioxide were circulated for 1 minute at 2,700 p s i. A partial exhaust is performed before the full exhaust followed by the flushing step. A seventh scanning electron micrograph was taken in the sixth designated system, followed by removal of the photoresist. The seventh scanning electron micrograph showed removal of the photoresist system in the sixth designated system. Seventh Designated System In the seventh specified system, photoresist and residues are removed from the carbon-silicon dioxide etched structure generated in the aforementioned via etching step. The specified chemicals used are as follows: 0 · 15 ml of water-soluble ammonium fluoride (water-soluble fluoride) with a volume ratio of 24%, 20 ml of butyrolactone (the first component of the solution), and 20 ml of Methyl methylene (the second component of the solvent), 0.15 ml glacial acetic acid (the third component of the solvent), and 1 ml of additional water. The pressure chamber is maintained at 70 ° C. The water-soluble fluoride, solution and additional water were circulated at 2,800 ps i for 2 minutes. Two partial degassing and one full degassing were performed between the removing step and the rinsing step. Rinse agent is the size of the paper applicable to China National Standard (CNS) A4 (210 X 297 mm) _ 29-(Please read the precautions on the back before filling this page) ----- Order i stupid line * Ministry of Economic Affairs wisdom Printed by a member of the property bureau and a consumer cooperative 500985 A7 ____B7____ V. Description of the invention (27) 50 ml of 50% ethanol and 50% water. The rinse agent and supercritical carbon dioxide were circulated for 1 minute at 2,700 ps. A partial exhaust is performed before the full exhaust followed by the flushing step. An eighth scanning electron micrograph was taken in the seventh designated system, followed by removal of the photoresist and residue. The eighth scanning electron micrograph showed the removal of photoresist and residues in the seventh designated system. It is very obvious to those skilled in the art that other different improvements can be implemented in the appropriate system without departing from the spirit and scope of the definition of the patent application for the subsidiary patent of the present invention. (Please read the notes on the back before filling this page) Order! !! Printed by Xian Qin, Member of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -30-