201127950 六、發明說明： 【發明所屬之技術領域】 本文所闡述之實施例大體而言係關於一種清洗液、一種 清洗方法、一種清洗系統及一種用於製造微細構造之方 法。 相關申請案之交又參考 此申請案係基於2009年9月25日申請之第20〇9·21989〇號 先前日本專利申請案並主張該申請案之優先權之利益，該 申請案之全部内容以引用方式併入本文中。 【先前技術】 在諸如半導體裝置及MEMS(微機電系統）之領域中具 有細微壁體之微細構造係使用微影技術製造於表面上。在 製造製红期間形成且然後變得非必要之抗蝕劑係使用 SPM(硫酸過氧化氫混合物）溶液（亦即，濃硫酸與過氧化氫 水溶液之混合液）來移除（例如，參見Jp_A 2〇〇7_12333〇 (Kokai)) 〇 在此SPM溶液+包含藉由混合濃硫酸與過氧化氣水溶液 產生之氧化物質（例如，過氧單硫酸）。 此外，已提出使用藉由電解硫酸水溶液產生之氧化物質 (例如’過氧單硫酸)來移除黏附至晶圓及類似物之抗蝕劑 之技術（參見 JP-A 2006-lll943(Kokai))。 JP-A 2007-123330(Kokai)AJP-A 2006-111943(Kokai) t 所論述之技術使用所產生氧化物質之高氧化分解能力分解 並移除抗蝕劑，亦即有機物質。 150733.doc 201127950 此處’在#自卩高劑量植入雜質製造高速運作半導體裝 置時，藉由以該高劑量植入該雜質在該抗蝕劑之表面中形 成經改動層。纟中形成有此經改動層之該抗㈣不能容易 地移除；且遺憾的是’不能僅藉由上文所述氧化物質之氧 化分解能力獲得所期望移除邊際。 【發明内容】 大體而言’根據-個實施例’一種清洗液包含氧化物質 及氫氟酸且表現酸性。 在另-實施射，本發明揭示—種清洗方法。該方法包 含藉由選自電解硫酸溶液、電解添加至硫酸溶液之氫氟酸 及混合硫酸溶液與過氧化氫水溶液中之—者產生包含氧化 物質之氧化溶液。該方法& j 4 /力凌包3將氣化溶液及氫氟酸供應至 欲清洗之物件之表面。 在另f施例中’清洗系統包含硫酸電解單元、硫酸供 應單元、清洗處理單元、第-氫氟酸供應單元及氧化溶液 供應單元。硫酸電解單元包含陽極、陰極、提供於該陽極 與該陰極之間的隔膜、提供於㈣極與該㈣之間的陽極 室及提供於該陰極與該隔膜之間的陰極室，該硫酸電解單 元電解硫酸溶液以在該陪榀—+ 士， 。隹極至中產生氧化物質。該硫酸供 應早元將硫酸溶液供靡$兮睞 愿至5亥陽極室及該陰極室。該清洗處 理單元執行對欲清洗之物件之清洗處理。該第—氫說酸供 應單元將氫氣酸供應至該清洗處理單b另外，該氧化溶 液供應單元將包含該氧化物質之氧化溶液供應至該清洗處 理單元。 150733.doc 201127950 :另=施例中：清洗系統包含硫酸電解單元、硫酸供 洗處理單凡、第二氫氟酸供應單元及氧化溶液 供應皁兀。硫酸電解單元包合 -平兀匕3 %極、陰極、提供於該陽極 ^亥陰極之間的隔膜、提供於該陽極與該隔膜之間的陽極 至及提供於該陰極與該隔膜之間的陰極室’該硫酸電解單 兀電解硫酸溶液以在該陽極室中產生氧化物質。該硫酸供 應Γ兀將硫酸溶液供應至該陽極室及該陰極室。該清洗處 ::元：㈣欲清洗之物件之清洗處理。該第二氣氣酸供 應早謂錢酸供應至該陽極室。料，該氧化溶液供應 早疋將包含該氧化物質之氧化溶液供應至該清洗處理單 元0 在另f %例中，本發明揭示一種用於製造微細構造之 方法。該方法包含藉由上述清洗方法清洗欲清洗之物件且 形成微細構造；。 【實施方式】 現在將參照圖式闡述實施例。該等圖式中之類似組件用 相同參考編號標記，且酌情省略詳細闡述。 圖1係圖解說明根據此實施例之清洗系統之示意圖。 "如圖1中所圖解說明，清洗系統5包含硫酸電解單元1 〇、 風氣酸供應單元5G、清洗處理單元12、溶液循環草元14及 硫酸供應單元1 5。 硫^電解單元10具有電解硫酸溶液並在陽極室3〇中產生 氧化物質之功能°雖然當包含氧化物質之溶液用於移除黏 附至欲清洗之物件之污染物(例如，沈積物，諸如抗蝕 150733.doc 201127950 劑、金屬雜質、顆粒、幹触刻殘渣、二氧化石夕、函化物 等）時’該包含氧化物質之溶液之氧化能力降低，但硫酸 電解單元ίο亦具有恢復降低之氧化能力之功能。 硫酸電解單元10包含陽極32、陰極42、提供於陽極32與 陰極42之間的隔膜20 '提供於陽極32與隔膜2〇之間的陽極 室30及提供於陰極42與隔膜2〇之間的陰極室40。 上端密封單元22提供於隔膜2〇、陽極室3〇及陰極室4〇之 上端處；且下端密封單元23提供於隔膜2〇、陽極室3〇及陰 極室40之下端處。陽極32與陰極42相對，其之間插入有隔 膜20。陽極32係由陽極支撐體33支撐；且陰極42係由陰極 支撐體43支撐。在陽極32與陰極42之間連接直流電源％。 陽極32係由導電陽極基底構件34及形成於陽極基底構件 34之表面上之陽極導電膜35製成。陽極基底構件34係由陽 極支樓體33之内面支撐；且陽極導電膜35面對陽極室3〇。 陰極42係由導電陰極基底構件44及形成於陰極基底構件 44之表面上之陰極導電膜45製成。陰極基底構件料係由陰 極支樓體43之内面支撐；且陰極導電膜45面對陰極室4〇。 陽極入口 19形成於陽極室3〇之下端側上；且陽極出口 17 形成於上端側上。陽極入口 19及陽極出口 17與陽極室3〇連 通。陰極入口 18形成於陰極室40之下端側上；且陰極出口 16形成於上端側上。陰極入口 18及陰極出口 16與陰極室4〇 連通。 氫氣酸供應單元50包含保持氟化氫（HF)水溶液（亦即， 氫氟酸）之罐51、幫浦52及開/關閥71。罐SI、幫浦52及開/ 150733.doc 201127950 關閥71經由管道線路53及管道線路74連接至分配單元6i。 罐51中所保持之氫氟酸可藉由幫浦52之運作經由管道線路 53及管道線路74供應至分配單元61。換言之，氫氟酸供應 單元50具有將罐51中所保持之氫氟酸供應至清洗處理單元 12之分配單元61之功能；且可將供應至分配單元61之氫氟 酸供應至欲清洗之物件w之表面4可藉由提供與管道線 路74及分配單元61不同之未圖解說明之管道線路及分配單 元自與包含氧化物質之溶液(氧化溶液)之彼管道系統不同 之管道系統將氫氟酸供應至欲清洗之物件w。 清洗處理單元12具有使用硫酸電解單元1〇中所獲得之包 含”物質之溶液(氧化溶液)及由氫氟酸供應單元5〇供應 之氫氟酸清洗欲清洗之物件W之功能。 =電解單中所獲得之氧化溶液經由溶液 Μ供應至提供於清洗處理單元12中之分配單元μ。 酸由氫氟酸供應單元5〇供瘅 應至鍉供於清洗處理單元12中之 刀配早疋6卜可依序供應該氧化溶液及該氣氣酸； 質上同時地供應該氧化溶液及該氫氟酸。 ^ 可混合該氧化溶液與該氫敦酸 洗液)。在其中將由氨氟酸供應單元：應合液(清 硫酸電解單元1G供應之氧 〜之職酸與由 線路74之情況中，管道㈣7貫質上同時地供應至管道 元。 S道線路74形錢合兩種㈣之混合單 ’可提供未圖解說明之 氫氟酸。在此情況中，琴夫J用以遂合該氧化溶液與該 4未圖解說明之罐形成混合單元。 150733.doc 201127950 藉由提供該未圖解說明之罐，可緩衝該混合液（清洗液）之 流動速率波動，可調整混合速率等。此外，可使該混合液 (清洗液）之混合速率之性質更均勻。 分配單元61具有用於將該氧化溶液、該氫氟酸及該氧化 溶液與該氫氟酸之混合液（清洗液）分配至欲清洗之物件w 上之为配噴嘴。提供旋轉台62，將欲清洗之物件w放置於 旋轉臺上以與該分配噴嘴相對。旋轉台62提供於蓋29之内 4中。藉由自分配單元61朝向欲清洗之物件w分配該氧化 溶液、該氫氟酸及該氧化溶液與該氫氟酸之混合液（清洗 液）’可自欲清洗之物件W之頂部移除污染物（例如，沈積 物，諸如抗㈣j、金屬雜質、顆纟、幹餘刻㈣、二氧化 矽、_化物等）。 :然在圖i中所圖解說明之清洗處理單元。中使用所謂 的單晶圓處理，但亦可使用批量處理。 硫酸電解單元财所產生之I化溶液經由溶液循環單元 !4自陽極出ϋ17供應至清洗處理單元12。作為溶液維持單 兀’陽極出口 17經由其中提供開/關閥…之管道線路乃連 接至罐28。罐職由管道線路74連接至分配單⑽。罐^ 中所保持之氧化溶液藉由幫浦81之運作經由管道線路叫共 應至分配單元61。在管道線路74中幫浦81之分配側上提供 開/關閥74a。在此實施例中’罐28、幫浦81等形成將包含 氧化物質之氧化溶液供應至清洗處理單幻2之氧化溶液供 應早P在此情況中，硫酸電解單元1()中所產生之氧化容 液之流動速率波動可藉由將氧化溶液保持及維持於罐辦 150733.doc 201127950 來得到緩衝。可藉由給罐28提供加熱器來 液之溫度控制。 λ 合 自清洗處理單元12排放之氧化溶液可藉由溶液循環單元 ::回收且可再供應至清洗處理單元&例如，自清洗處理 :心排放之氧化溶液係可藉由依次通過回流罐〇、過遽 益64、幫浦82及開/關閥76供應至硫酸電解單元w之陽極 入口 19。換言之，該氧化溶液可在硫酸電解單元⑺與清洗 處理單元12之間循環。在此情況中，視需要，可將該清洗 處/月間所使用 < 氧化溶液供應至硫酸電解單元1 〇 ;隨 後’可使藉由在硫酸電解單元附執行電解獲得之包含= 化物質之氧化溶液通過罐28等；且可將該氧化溶液供應至 清洗處理單元12。 匆視的要，可藉由將經稀釋硫酸自硫酸供應單元！ 5 供應至硫酸電解單元10以及將使用過之氧化溶液供應至硫 酸電解單元H)且然後執行電解來產生該氧化溶液。可使此 處所獲得之氧化溶液通過罐28等’且供應至清洗處理單元 12°藉由盡可能多地重複該氧化溶液之再利用，可減少產 生該氧化溶液所必需之材料（化學溶液等）之量及在欲清洗 之物件W之清洗處理期間之廢液之量。 另一選料’自清洗處理單元12排放之氧化溶液係可藉 由錢通過回流罐63、過遽器64、幫浦82及開/關間…供 應：罐28，亦即，不通過硫酸電解單元10。此處，接著， 可藉由將氧化洛液自罐28供應至清洗處理單元η來執行欲 清洗之物件W之清洗處理。在此情況中，可再利用在該清 150733.doc 201127950 洗處理中使用之後之氧化溶液。藉由 稽由盡可能多地重複該氧 化溶液之此再利用，可減少產生該氧 孔化冷液所必需之材料 (化學溶液等）之量及廢液之量。 亦可類似地循環及再利用自清洗處理單元12排放之該氫 I酸及該氧化溶液與該氫氟酸之混合液（清洗液卜可針對 該氫氣酸將未圖解說明之回流罐、開/_等連接至清洗 處理單元12以分離並回收該氫氧酸及該氧化溶液。在二情 況中’藉由依序供應該減酸及該氧化溶液，可在其各自月 供應期間執行分離及回收。單獨再則可藉由單獨再處理 等來實現。 回流罐63提供有具有將在清洗處理單心中所清洗及所 移除之污染物排放至該系統外部之功能之排放管道線路75 及排放閥75a。過遽器64具有過壚自清洗處理單元12排放 之氧化溶液、氫氟酸及混合液（清洗液）巾所包含之污毕物 之功能。 硫酸供應單元15具有將稀硫酸溶液供應至硫酸電解單元 10(陽極㈣及陰極室40)之功能。硫酸供應單元15包含將 該稀硫酸溶液供應至陽極室3〇及陰極室4〇之幫浦8〇、保持 該稀硫酸之罐60及開/關閥70及72。 具有（例如）不低於30重量百分比且不高於7〇重量百分比 之硫酸濃度之稀硫酸溶液保持於罐⑼中。驅動幫㈣以使 得罐60中之稀硫酸溶液通過開/關閥7〇且經由開/關闕^之 下游側上之管道線路及陽極入口 19供應至陽極室3(^此 外’驅動幫浦80以使得罐6〇中之稀硫酸溶液通過開/關閥 150733.doc -12· 201127950 72且經由開/關閥72之下游側上之管道線路％及陰極入口 18供應至陰極室40。 在此實施例中，可抑制由於該硫酸之電解所致隔膜此 損壞’此乃因供應至該陰極側之溶液之硫酸濃度係低。換 言之，在該硫酸之電解反應期間該陰極侧上之水移動至該 陽極側；該陰極側上之溶液之硫酸濃度增加；且隔膜_ 於j化。此外，在其中離子交換膜用作隔㈣之情況中， 隨著水含量在該濃硫酸溶液中減少，該 增加;且帽不合意地增加。因此，同樣為減輕此等I， 題，可藉由將稀硫酸供應至陰極側以將水供應至該離子交 換膜來抑制該電阻增加。 藉由減少供應至硫酸電解單元1〇之硫酸之濃度，可增加 該氧化溶液中所包含之氧化物質（例如，過氧單硫酸i過 氧二硫酸)之產生效率。下文閣述增加該氧化物 效率。 上文所闈述之開/關閥70、71、72、〜、74a、％ 及91亦具有控制各種溶液之流動速率之功能。幫浦 及亦具有控制各種溶液之流動速度之功能。 自耐化學性之態樣而言，陽極支撐體Μ、陰極支撐體 43、陰極出口16 '陽極出口 17 '陰極入口 18、陽極入口 Η 及清洗處理單元12之蓋29之材料可有利地包含（例如）諸如 聚四氟乙烯之氟碳樹脂。 將該氧化溶液、該氫氟酸及該氧化溶液與該氫氣酸之混 合液(清洗液)供應至清洗處理單元12之管道可包含纏繞有 150733.doc -13- 201127950 隔熱物等之氟碳樹脂管。此管道亦可提供有由氟碳樹脂製 成之内嵌式加熱β。抽送該氧化溶液、該氫氟酸及該氧化 溶液與該氫說酸之混合液(清洗液)之幫浦可包含由具有耐 熱性及耐化學性之氟碳樹脂製成之伸縮幫浦。 保持該硫酸溶液之罐之材料可包含（例如）石#。保㈣ 氫氟酸及該氧化溶液與該氫氟酸之混合液（清洗液）之罐中 之每-者之材料可包含(例如)氟碳樹脂。該等罐中之每一 者亦可酌情包含溢流控制裝置、溫度控制裝置等。 此處處理時間可藉由增加溶液溫度（處理溫度）(藉由給 罐提供溫度控制裝置、給管道提供内嵌式加熱器等）以增 加與抗蝕劑等之反應性來縮短 '然而，過高增加該溫度可 導致關於該清㈣統之組件（例如，每—單元之管道線 路、開/關閥、幫浦及罐’清洗處理單元之蓋等）之可容許 溫度及強度之問題，組件通常係由(例如)氟碳樹月旨等 形成以增加與該氫氟酸、該硫酸及該氧化溶液接觸之部分 之耐化學性。在此情況中，該所需強度在其中溫度係過高 之情況中係不可獲得的。 因此，端視縮短該處理時間及該清洗系統之可容許溫 度、強度等’該氫氟酸、該硫酸及該氧化溶液之溫度係不 低於loot且不高於110它係有利的。 隔膜20可包含（例如）中性膜（儘管已經歷親水處理），其 包^如彼具有產品名PGreflGn等之pTFE#孔隔膜及諸如 彼等具有產品名Nafion、Aciplex、Flemi〇n等之正離子交 換膜。隔联20之尺寸係（例如）約5〇平方爱米。上端密封單 150733.doc 14 201127950 元22及下端密封單元23包含（例如）塗佈有氟碳樹脂之〇環 係適合的。 陽極導電基底構件34之材料可包含（例如型石夕及諸如 銳之閥用金屬。本文中，「閥用金屬」係指藉由陽極氧化 使其金屬表面均勻地覆蓋有氧化物膜且具有優良耐腐蝕性 之金屬。陰極導電基底構件44可包含（例如卜型石夕。 山陽極導電膜35及陰極導電膜45之材料可包含（例如）玻璃 碳自财久性之態樣而言，在其中供應具有相對高硫酸濃 又之冷液及添加有氫氟酸之溶液之情況中適合使用導電金 剛石膜。 ^ 對於•亥陽極及$陰極二者，該導電膜及該基底構件可由 相同材料开/成。例如，在其中將玻璃碳用作該陰極基底構 牛之障況中及在其中將導電金剛石自支樓膜用作該陽極基 底構件之If況中，該基底構件本身形成具有可有助於該電 解反應之電催化特性之導電膜。 雖然金剛石具有穩Μ化學、機械及熱特性，但由於不 良導電f生’-直難以在電化學系統中使用金剛石。狹而， =由使_絲化學氣相沈積（hf_cvd)在供應侧氣體及 氮氣體的同時形成夾獾彡日 成來獲仵導電金剛石膜。該導電金剛石膜 具有（例如）3至5伏之官r啻从咖 %電位匈」及（例如）5至100毫_歐姆_ 釐米之電阻。 此處，該電位窗係用於 1 萆解水所4之最小電位（不低於 】·2伏)。该電位窗因材料品質而不 電位窗之材料 U使用具有寬 電位窗内之電位下執行電解之情況 I50733.doc 201127950 中，可優先於水之電解進行具有在該電位窗内之氧化-還 原電位之電解反應；且存在其中可優决 、 傻无進仃不易電解之物 質之氧化反應或還原反應之情況。因&，對於不能經歷習 用電化學反應之物質，可藉由使用此導電金剛石實現分解 及合成。 在HF-CVD中，藉由將源材料氣體供應至處於高溫狀態 中之鎢絲來執行分解。形成用於形成該膜所需之自由基。 隨後’擴散至該基板表面中之自由基與其他反應性氣體反 應以在所需基板上形成該膜。 現在將闡述氧化物質在硫酸電解單元i 〇中之產生機制。 圖2A及2B係圖解說明該氧化物質之產生機制之示意 圖。圖2A係該硫酸電解單元之示意性側剖視圖。圖2b = 圖解說明沿圖2A之線A-A之剖面之示意圖。 如圖2A及2B中所圖解說明，提供陽極32及陰極42以彼 此相對，其之間插入有隔膜20。陽極32係由陽極支撐體Μ 支撐，其中陽極32之陽極導電膜35面對陽極室3〇。陰極42 係由陰極支撐體43支撐，其中陰極42之陰極導電膜45面對 陰極室40。在隔膜2〇、陽極支撐體33及陰極支撐體43中之 每一者之兩端部分上提供電解單元外殼24。 經由陽極入口 19將（例如）7〇重量百分比之硫酸溶液（稀硫 酸溶液）自罐60供應至陽極室3〇。經由陰極入口 18將（例如） 该70重量百分比硫酸溶液（該稀硫酸溶液）亦自罐6〇供應至 陰極室40〇 藉由施加正電壓至陽極32及施加負電壓至陰極42，電解 150733.doc •16· 201127950 反應發生於陽極室30及陰極室40中之每一者中。化學式 1、化學式2及化學式3之反應發生於陽極室30中。 化學式1 2HS04' S2〇82' + 2H+ + 2e" 化學式2 HS04' + H2〇 -> HS〇5* + 2H+ + 2e' 化學式3 2H2〇 -» 4H+ + 4e' + 02 t 此處，化學式2及化學式3中之水（Ηβ)係作為該70重量 百分比硫酸溶液之3 0百分比所包含之水。在陽極室3 〇中， 化學式2之反應產生過氧單硫酸離子（HSCV)。藉由化學式 1及化學式3之基本反應發生化學式4之總反應以產生過氧 單硫酸離子（HSO5·)及硫酸。過氧單硫酸具有比硫酸之彼 清洗能力較強之清洗能力。 化學式4 S2〇82- + H+ + H20 — hso5- + H2S04 另一選擇為’在某些情況中，化學式4之過氧單硫酸離 子（HS(v)係在產生過氧化氫（H2〇2)之後產生，如來自化學 式1及化學式3之基本反應之化學式5所圖解說明。在某些 情況中’藉由化學式1之反應產生過氧二硫酸（H2S208)。化 學式4及化學式5係來自化學式1之二級反應。 化學式5 S2〇82 + H+ + h2〇 h2〇2 + HzS〇4 在陰極室40中產生氫氣，如由化學式6所圖解說明。此 150733.doc 17 201127950 係由於在陽極處產生之氫離子（H+)經由隔膜20移動至陰極 且發生電解反應而發生。該氫氣經由陰極出口 16自陰極室 40排放。 化學式6201127950 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The embodiments described herein relate generally to a cleaning fluid, a cleaning method, a cleaning system, and a method for fabricating a microstructure. RELATED APPLICATIONS This application is based on and claims the benefit of priority of the priority of the Japanese Patent Application No. PCT Application No. This is incorporated herein by reference. [Prior Art] A fine structure having a fine wall in a field such as a semiconductor device and a MEMS (Micro Electro Mechanical System) is fabricated on a surface using lithography. The resist that is formed during the manufacture of the red and then becomes unnecessary is removed using a SPM (sulfuric acid hydrogen peroxide mixture) solution (ie, a mixture of concentrated sulfuric acid and aqueous hydrogen peroxide) (for example, see Jp_A) 2〇〇7_12333〇(Kokai)) The SPM solution + contains an oxidizing substance (for example, peroxymonosulfuric acid) produced by mixing concentrated sulfuric acid with an aqueous solution of peroxidation gas. Further, a technique of removing a resist adhered to a wafer and the like by using an oxidizing substance (for example, 'peroxymonosulfuric acid) produced by electrolyzing an aqueous sulfuric acid solution has been proposed (see JP-A 2006-lll943 (Kokai)) . JP-A 2007-123330 (Kokai) AJP-A 2006-111943 (Kokai) t The technique described uses the high oxidative decomposition ability of the oxidizing substance produced to decompose and remove the resist, that is, the organic substance. 150733.doc 201127950 Here, when a high-speed operation semiconductor device is fabricated from high-dose implanted impurities, a modified layer is formed in the surface of the resist by implanting the impurity at the high dose. The resistance (4) in which the modified layer is formed in the crucible cannot be easily removed; and unfortunately, the desired removal margin cannot be obtained only by the oxidative decomposition ability of the oxidizing substance described above. SUMMARY OF THE INVENTION Generally, a cleaning liquid according to an embodiment contains an oxidizing substance and hydrofluoric acid and exhibits acidity. In another embodiment, the present invention discloses a cleaning method. The method comprises producing an oxidizing solution comprising an oxidizing substance by a hydrofluoric acid selected from the group consisting of an electrolytic sulfuric acid solution, electrolytically added to a sulfuric acid solution, and a mixed sulfuric acid solution and an aqueous hydrogen peroxide solution. The method & j 4 / Li Ling package 3 supplies a gasification solution and hydrofluoric acid to the surface of the article to be cleaned. In another embodiment, the cleaning system comprises a sulfuric acid electrolysis unit, a sulfuric acid supply unit, a cleaning treatment unit, a first hydrofluoric acid supply unit, and an oxidation solution supply unit. The sulfuric acid electrolysis unit comprises an anode, a cathode, a separator provided between the anode and the cathode, an anode chamber provided between the (four) pole and the (four), and a cathode chamber provided between the cathode and the separator, the sulfuric acid electrolysis unit Electrolyze the sulfuric acid solution in the accompanying 榀-+士,. Oxide is produced in the bungee to the middle. The sulfuric acid supply is supplied to the 5 amp anode chamber and the cathode chamber as early as possible. The cleaning processing unit performs a cleaning process on the object to be cleaned. The first hydrogen-based acid supply unit supplies hydrogen acid to the cleaning treatment unit b. The oxidizing solution supply unit supplies an oxidation solution containing the oxidized material to the cleaning treatment unit. 150733.doc 201127950 : In addition: In the example: the cleaning system comprises a sulfuric acid electrolysis unit, a sulfuric acid washing treatment unit, a second hydrofluoric acid supply unit and an oxidizing solution supply saponin. The sulfuric acid electrolysis unit comprises a 兀匕3 极 pole, a cathode, a separator provided between the anode and the cathode, an anode provided between the anode and the separator, and a cathode provided between the cathode and the separator The cathode chamber 'the sulfuric acid electrolysis single-electrolytic sulfuric acid solution to generate an oxidizing substance in the anode chamber. The sulfuric acid supply 供应 supplies a sulfuric acid solution to the anode chamber and the cathode chamber. The cleaning department :: Yuan: (4) Cleaning of the items to be cleaned. The second gas acid supply is said to be supplied to the anode chamber as early as possible. The oxidizing solution is supplied to the rinsing treatment unit 0. The oxidizing solution containing the oxidizing material is supplied to the cleaning processing unit 0. In another example, the present invention discloses a method for manufacturing a fine structure. The method comprises cleaning the object to be cleaned by the above cleaning method and forming a fine structure; [Embodiment] Embodiments will now be described with reference to the drawings. Similar components in the drawings are labeled with the same reference numerals, and the detailed description is omitted as appropriate. Figure 1 is a schematic diagram illustrating a cleaning system in accordance with this embodiment. " As illustrated in Fig. 1, the cleaning system 5 includes a sulfuric acid electrolysis unit 1 〇, an oleic acid supply unit 5G, a cleaning treatment unit 12, a solution circulating grass unit 14, and a sulfuric acid supply unit 15. The sulfur electrolysis unit 10 has a function of electrolyzing a sulfuric acid solution and generating an oxidizing substance in the anode chamber 3, although a solution containing an oxidizing substance is used to remove contaminants (for example, deposits such as anti-deposition) adhering to the object to be cleaned. Eclipse 150733.doc 201127950 agent, metal impurities, particles, dry-touch residue, dioxide, cerium, etc.) when the oxidizing agent solution has reduced oxidation capacity, but the sulfuric acid electrolysis unit ίο also has reduced oxidation The ability to function. The sulfuric acid electrolysis unit 10 includes an anode 32, a cathode 42, a separator 20' provided between the anode 32 and the cathode 42, and an anode chamber 30 provided between the anode 32 and the separator 2, and between the cathode 42 and the separator 2'. Cathode chamber 40. The upper end sealing unit 22 is provided at the upper ends of the diaphragm 2, the anode chamber 3, and the cathode chamber 4''; and the lower end sealing unit 23 is provided at the lower end of the diaphragm 2, the anode chamber 3, and the cathode chamber 40. The anode 32 is opposed to the cathode 42 with a separator 20 interposed therebetween. The anode 32 is supported by the anode support 33; and the cathode 42 is supported by the cathode support 43. A DC power source % is connected between the anode 32 and the cathode 42. The anode 32 is made of a conductive anode base member 34 and an anode conductive film 35 formed on the surface of the anode base member 34. The anode base member 34 is supported by the inner surface of the anode branch body 33; and the anode conductive film 35 faces the anode chamber 3''. The cathode 42 is made of a conductive cathode base member 44 and a cathode conductive film 45 formed on the surface of the cathode base member 44. The cathode base member material is supported by the inner surface of the cathode support body 43; and the cathode conductive film 45 faces the cathode chamber 4''. The anode inlet 19 is formed on the lower end side of the anode chamber 3''; and the anode outlet 17 is formed on the upper end side. The anode inlet 19 and the anode outlet 17 are connected to the anode chamber 3A. A cathode inlet 18 is formed on the lower end side of the cathode chamber 40; and a cathode outlet 16 is formed on the upper end side. The cathode inlet 18 and the cathode outlet 16 are in communication with the cathode chamber 4A. The hydrogen acid supply unit 50 includes a tank 51 holding a hydrogen fluoride (HF) aqueous solution (i.e., hydrofluoric acid), a pump 52, and an on/off valve 71. The tank SI, the pump 52 and the opening / 150733.doc 201127950 closing valve 71 are connected to the distribution unit 6i via a pipe line 53 and a pipe line 74. The hydrofluoric acid held in the tank 51 can be supplied to the distribution unit 61 via the piping line 53 and the piping line 74 by the operation of the pump 52. In other words, the hydrofluoric acid supply unit 50 has a function of supplying the hydrofluoric acid held in the tank 51 to the distribution unit 61 of the cleaning processing unit 12; and the hydrofluoric acid supplied to the distribution unit 61 can be supplied to the object to be cleaned The surface 4 of w can be hydrofluoric acid by providing a different piping circuit and distribution unit than the piping line 74 and the distribution unit 61 from a piping system different from the piping system containing the oxidizing substance solution (oxidizing solution). Supply to the item w to be cleaned. The cleaning processing unit 12 has a function of cleaning the object to be cleaned by using the solution containing the substance (oxidation solution) obtained in the sulfuric acid electrolysis unit 1 and the hydrofluoric acid supplied from the hydrofluoric acid supply unit 5〇. The oxidizing solution obtained in the solution is supplied to the dispensing unit μ provided in the cleaning processing unit 12 via the solution 。. The acid is supplied from the hydrofluoric acid supply unit 5 to the knives supplied to the cleaning processing unit 12 The oxidizing solution and the sulphuric acid are sequentially supplied; the oxidizing solution and the hydrofluoric acid are simultaneously supplied in a mass. ^ The oxidizing solution and the hydrogen absorbing acid solution may be mixed. Among them, the fluorinated acid is supplied. Unit: The liquid should be mixed (the oxygen supplied by the 1G of the sulphuric acid electrolysis unit is supplied to the pipeline element simultaneously with the pipeline (4) 7 in the case of the line 74. The S-line line 74 is a mixture of the two types (four) The hydrofluoric acid may be provided as a single illustration. In this case, the hammer J is used to knead the oxidizing solution to form a mixing unit with the canister not illustrated. 150733.doc 201127950 By providing this unillustrated Can, can be buffered The flow rate of the mixed liquid (washing liquid) fluctuates, the mixing rate can be adjusted, etc. Further, the mixing rate of the mixed liquid (washing liquid) can be made more uniform. The dispensing unit 61 has a function for the oxidizing solution, the hydrogen fluoride The acid and the mixed solution of the oxidizing solution and the hydrofluoric acid (cleaning liquid) are distributed to the nozzle to be cleaned. The rotary table 62 is provided, and the object to be cleaned w is placed on the rotary table to be distributed with the distribution. The nozzles are opposed to each other. The rotary table 62 is provided in the inside of the cover 29. The oxidizing solution, the hydrofluoric acid, and the mixture of the oxidizing solution and the hydrofluoric acid are dispensed from the dispensing unit 61 toward the object w to be cleaned (cleaning Liquid) 'can remove contaminants from the top of the object W to be cleaned (for example, deposits such as anti-(four) j, metal impurities, ruthenium, dry residue (four), cerium oxide, _ ing, etc.): The cleaning processing unit illustrated in i uses so-called single-wafer processing, but batch processing can also be used. The I-form solution produced by the sulfuric acid electrolysis unit is supplied from the anode outlet 17 to the cleaning treatment via the solution circulation unit !4 Element 12. As a solution maintenance unit, the anode outlet 17 is connected to the tank 28 via a pipe line in which an on/off valve is provided. The tank is connected to the distribution sheet (10) by a pipe line 74. The oxidation solution held in the tank ^ The operation of the pump 81 is called via the pipeline to the distribution unit 61. An on/off valve 74a is provided on the distribution side of the pump 81 in the pipeline line 74. In this embodiment, the tank 28, the pump 81, etc. are formed. Supplying an oxidizing solution containing an oxidizing substance to the oxidizing solution of the cleaning process No. 2 Supply early P. In this case, the flow rate fluctuation of the oxidizing agent generated in the sulphuric acid electrolysis unit 1 () can be maintained by oxidizing the solution The buffer is maintained at the canister 150733.doc 201127950. The temperature control of the liquid can be provided by providing the heater 28 with a heater. The oxidizing solution discharged from the cleaning processing unit 12 can be recovered by the solution recycling unit:: and can be re-supplied to the cleaning processing unit & for example, self-cleaning treatment: the oxidizing solution of the heart discharge can be passed through the reflux tank in turn The excess benefit 64, the pump 82, and the on/off valve 76 are supplied to the anode inlet 19 of the sulfuric acid electrolysis unit w. In other words, the oxidizing solution can be circulated between the sulfuric acid electrolysis unit (7) and the cleaning treatment unit 12. In this case, the <oxidizing solution used in the cleaning/month may be supplied to the sulfuric acid electrolysis unit 1 视 as needed; subsequently, the oxidation of the chemical substance obtained by performing electrolysis in the sulfuric acid electrolysis unit may be performed. The solution passes through the tank 28 or the like; and the oxidizing solution can be supplied to the washing treatment unit 12. If you want to hurry, you can supply the unit from the sulfuric acid by diluting sulfuric acid! 5 is supplied to the sulfuric acid electrolysis unit 10 and supplies the used oxidation solution to the sulfuric acid electrolysis unit H) and then electrolysis is performed to produce the oxidation solution. The oxidizing solution obtained here can be passed through the tank 28 or the like and supplied to the cleaning treatment unit 12°. By repeating the reuse of the oxidizing solution as much as possible, the material (chemical solution, etc.) necessary for generating the oxidizing solution can be reduced. The amount and amount of waste liquid during the cleaning process of the article W to be cleaned. Another optional material, the oxidizing solution discharged from the cleaning processing unit 12, can be supplied by money through the reflux tank 63, the damper 64, the pump 82, and the opening/closing chamber: the tank 28, that is, without sulfuric acid electrolysis Unit 10. Here, next, the cleaning process of the object W to be cleaned can be performed by supplying the oxidizing liquid from the tank 28 to the cleaning processing unit η. In this case, the oxidizing solution after use in the washing process of the clearing 150733.doc 201127950 can be reused. By repeating the reuse of the oxidizing solution as much as possible, the amount of the material (chemical solution, etc.) necessary for generating the oxidized cold liquid and the amount of the effluent can be reduced. The hydrogen acid and the mixture of the oxidizing solution and the hydrofluoric acid discharged from the cleaning processing unit 12 may be similarly recycled and reused (the cleaning liquid may be used for the hydrogen acid acid, and the reflux tank, unillustrated, may be And the like is connected to the cleaning treatment unit 12 to separate and recover the oxyacid and the oxidizing solution. In the second case, by sequentially supplying the acid-reducing and the oxidizing solution, separation and recovery can be performed during their respective monthly supply. Separately, it can be realized by separate reprocessing, etc. The reflux tank 63 is provided with a discharge pipe line 75 and a discharge valve 75a having a function of discharging the cleaned and removed contaminants in the cleaning process single core to the outside of the system. The filter 64 has a function of the oxidizing solution discharged from the cleaning processing unit 12, the hydrofluoric acid, and the mixed material contained in the mixed liquid (cleaning liquid). The sulfuric acid supply unit 15 has a dilute sulfuric acid solution supplied to the sulfuric acid. The function of the electrolysis unit 10 (anode (four) and cathode chamber 40). The sulfuric acid supply unit 15 comprises a pump 8 that supplies the dilute sulfuric acid solution to the anode chamber 3 and the cathode chamber 4, and holds the dilute sulfuric acid tank. 60 and on/off valves 70 and 72. A dilute sulfuric acid solution having a sulfuric acid concentration of, for example, not less than 30% by weight and not more than 7% by weight is held in the tank (9). The driving aid (4) is driven so that it is in the tank 60 The dilute sulfuric acid solution is supplied to the anode chamber 3 through the on/off valve 7〇 and via the pipe line on the downstream side of the opening/closing port and the anode inlet 19 (further than the 'drive pump 80' to make the dilute sulfuric acid in the tank 6〇 The solution is supplied to the cathode chamber 40 through the opening/closing valve 150733.doc -12·201127950 72 and via the pipe line % on the downstream side of the opening/closing valve 72 and the cathode inlet 18. In this embodiment, the sulfuric acid can be suppressed The damage caused by the electrolysis of the separator is because the concentration of sulfuric acid in the solution supplied to the cathode side is low. In other words, the water on the cathode side moves to the anode side during the electrolysis reaction of the sulfuric acid; The concentration of sulfuric acid in the solution is increased; and the separator is in the case of j. In addition, in the case where the ion exchange membrane is used as the partition (four), the increase is accompanied as the water content is reduced in the concentrated sulfuric acid solution; and the cap is undesirably increased. Therefore, also to alleviate these I The increase in resistance can be suppressed by supplying dilute sulfuric acid to the cathode side to supply water to the ion exchange membrane. By reducing the concentration of sulfuric acid supplied to the sulfuric acid electrolysis unit 1 , the inclusion in the oxidation solution can be increased. The efficiency of the production of oxidizing species (eg, peroxymonosulfate monoperoxy disulfate). The efficiency of the oxide is increased as described below. The on/off valves 70, 71, 72, ~, 74a, % are recited above. And 91 also has the function of controlling the flow rate of various solutions. The pump also has the function of controlling the flow speed of various solutions. From the aspect of chemical resistance, the anode support body, the cathode support 43, and the cathode outlet 16 The material of the 'anode outlet 17' cathode inlet 18, the anode inlet Η and the lid 29 of the cleaning treatment unit 12 may advantageously comprise, for example, a fluorocarbon resin such as polytetrafluoroethylene. The oxidizing solution, the hydrofluoric acid, and the mixture of the oxidizing solution and the hydrogen acid (cleaning liquid) supplied to the cleaning processing unit 12 may include fluorocarbon wrapped with 150733.doc -13-201127950 insulation or the like. Resin tube. The pipe can also be provided with an in-line heating β made of fluorocarbon resin. The pump for pumping the oxidizing solution, the hydrofluoric acid, and the mixture of the oxidizing solution and the hydrogen acid (cleaning liquid) may comprise a telescopic pump made of a fluorocarbon resin having heat resistance and chemical resistance. The material of the tank holding the sulfuric acid solution may comprise, for example, stone #. The material of each of the tanks of the hydrofluoric acid and the mixture of the oxidizing solution and the hydrofluoric acid (cleaning liquid) may contain, for example, a fluorocarbon resin. Each of the tanks may also include an overflow control device, a temperature control device, etc., as appropriate. Here, the processing time can be shortened by increasing the solution temperature (treatment temperature) (providing a temperature control device to the tank, providing an in-line heater to the pipe, etc.) to increase the reactivity with the resist or the like. Increasing this temperature can lead to problems with the allowable temperature and strength of the components of the cleaning system (eg, the piping of each unit, the opening/closing valve, the cover of the pump and the tank 'cleaning unit, etc.) It is usually formed, for example, by a fluorocarbon tree or the like to increase the chemical resistance of a portion in contact with the hydrofluoric acid, the sulfuric acid, and the oxidizing solution. In this case, the required strength is not available in the case where the temperature is too high. Therefore, it is advantageous to shorten the processing time and the allowable temperature, strength, etc. of the cleaning system. The temperature of the hydrofluoric acid, the sulfuric acid and the oxidizing solution is not lower than the loot and not higher than 110. The membrane 20 may comprise, for example, a neutral membrane (although it has undergone a hydrophilic treatment), such as a pTFE# pore membrane having the product name PGreflGn, and the like having the product names Nafion, Aciplex, Flemi〇n, etc. Ion exchange membrane. The size of the spacer 20 is, for example, about 5 square meters. The upper end seal unit 150733.doc 14 201127950 element 22 and the lower end seal unit 23 are, for example, suitably coated with a fluorocarbon resin. The material of the anode conductive base member 34 may include (for example, a type of stone and a metal such as a sharp valve. Here, the "metal for valve" means that the metal surface is uniformly covered with an oxide film by anodization and is excellent. Corrosion-resistant metal. The cathode conductive base member 44 may comprise (for example, a type of material. The material of the mountain anode conductive film 35 and the cathode conductive film 45 may include, for example, glassy carbon in terms of the long-term nature, A conductive diamond film is suitably used in the case of supplying a solution having a relatively high sulfuric acid concentration and a solution containing hydrofluoric acid. ^ For both the anode and the cathode, the conductive film and the base member may be opened by the same material. For example, in the case where glassy carbon is used as a barrier to the cathode substrate and in which a conductive diamond self-supporting floor film is used as the anode base member, the base member itself is formed to have A conductive film that contributes to the electrocatalytic properties of the electrolytic reaction. Although diamond has stable chemical, mechanical, and thermal properties, it is difficult to be in an electrochemical system due to poor electrical conductivity. Using a diamond. Narrowly, a conductive diamond film is obtained by causing a chemical vapor deposition (hf_cvd) to form a crucible on the supply side gas and a nitrogen gas. The conductive diamond film has, for example, 3 to 5 volts of the official r啻 from the coffee% potential Hungarian and (for example) 5 to 100 milli-ohm _ cm resistance. Here, the potential window is used for the minimum potential of the 1 萆 solution 4 (not less than) · 2 volts. The potential window is not materialized by the material U and the material U is used to perform electrolysis at a potential within a wide potential window. I50733.doc 201127950 can be prioritized over the electrolysis of water with the potential window Electrolytic reaction of oxidation-reduction potential; and there are cases in which an oxidation reaction or a reduction reaction of a substance which is excellent in silencing, which is difficult to electrolyze, and which is difficult to electrolyze, may be used for substances which cannot undergo conventional electrochemical reactions. Decomposition and synthesis are achieved by using this conductive diamond. In HF-CVD, decomposition is performed by supplying a source material gas to a tungsten wire in a high temperature state, forming a radical required for forming the film. The radicals in the surface of the substrate react with other reactive gases to form the film on the desired substrate. The mechanism of generation of the oxidizing species in the sulfuric acid electrolysis unit i 现在 will now be explained. Figures 2A and 2B illustrate the oxidizing species. Figure 2A is a schematic side cross-sectional view of the sulfuric acid electrolysis unit. Figure 2b = Schematic diagram illustrating a cross section along line AA of Figure 2A. As illustrated in Figures 2A and 2B, an anode 32 and a cathode 42 are provided. Opposite to each other, a diaphragm 20 is interposed therebetween. The anode 32 is supported by an anode support body ,, wherein the anode conductive film 35 of the anode 32 faces the anode chamber 3. The cathode 42 is supported by the cathode support 43, wherein the cathode 42 The cathode conductive film 45 faces the cathode chamber 40. The electrolytic unit outer casing 24 is provided on both end portions of each of the diaphragm 2, the anode support 33, and the cathode support 43. For example, a 7 wt% sulfuric acid solution (dilute sulfuric acid solution) is supplied from the tank 60 to the anode chamber 3 through the anode inlet 19. The 70% by weight sulfuric acid solution (the dilute sulfuric acid solution) is also supplied from the tank 6〇 to the cathode chamber 40 via the cathode inlet 18, by applying a positive voltage to the anode 32 and applying a negative voltage to the cathode 42 to electrolyze 150733. Doc •16·201127950 The reaction takes place in each of the anode chamber 30 and the cathode chamber 40. The reaction of Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3 occurs in the anode chamber 30. Chemical Formula 1 2HS04' S2〇82' + 2H+ + 2e" Chemical Formula 2 HS04' + H2〇-> HS〇5* + 2H+ + 2e' Chemical Formula 3 2H2〇-» 4H+ + 4e' + 02 t Here, Chemical Formula 2 And water (Ηβ) in Chemical Formula 3 is water contained in 30% of the 70% by weight sulfuric acid solution. In the anode chamber 3, the reaction of Chemical Formula 2 produces peroxomonosulfate ions (HSCV). The total reaction of Chemical Formula 4 is carried out by the basic reaction of Chemical Formula 1 and Chemical Formula 3 to produce peroxymonosulfate ion (HSO5·) and sulfuric acid. Peroxymonosulfuric acid has a cleaning ability superior to that of sulfuric acid. Chemical Formula 4 S2〇82- + H+ + H20 — hso5- + H2S04 Another option is 'In some cases, the peroxymonosulfate ion of Chemical Formula 4 (HS(v) is in the production of hydrogen peroxide (H2〇2) Thereafter, it is produced as shown in Chemical Formula 5 from the basic reaction of Chemical Formula 1 and Chemical Formula 3. In some cases, 'peroxy disulfuric acid (H2S208) is produced by the reaction of Chemical Formula 1. Chemical Formula 4 and Chemical Formula 5 are from Chemical Formula 1 The secondary reaction. Chemical formula 5 S2〇82 + H+ + h2〇h2〇2 + HzS〇4 Hydrogen is generated in the cathode chamber 40 as illustrated by the chemical formula 6. This 150733.doc 17 201127950 is due to being produced at the anode Hydrogen ions (H+) are generated by moving to the cathode via the separator 20 and an electrolytic reaction occurs. The hydrogen gas is discharged from the cathode chamber 40 via the cathode outlet 16. Chemical Formula 6
2H+ + 2e· — H2 T 在此實施例中’如由化學式7所圖解說明，藉由電解該 硫酸溶液可獲得諸如（例如）過氧單硫酸（HjOj、過氧二硫 酸（HjW8)等之氧化物質；且可獲得包含此等氧化物質之 氧化洛液。雖然氫氣作為副產物產生，但該氫氣並不影響 該抗钮劑等之移除。 化學式7 H2S〇4+H20 —氧化物質 +η2 在其中使用過氧單硫酸之情況中，過氧單硫酸與諸如抗 ㈣之有機物質之反應速率係高。因&，甚至其中欲移除 之量係相對大之抗蝕劑移除亦可在短時間段中完成。此 外’在其中使用過氧單硫酸之情況中，亦可在低溫下實現 和示因此#對恤度斜升及諸如此類之微調時間係非必 要的。此外’可収地大量產生過氧單硫酸。因此，甚至 在低溫下亦可增加該過氧單硫酸與移除之物件之反應速 此處，為藉由縮短處理時間 儿从所 > 旦Υ 3加生屋效率’增加該氧 化物質之量係足夠的。在 孔 小、增加所施加之功率 大 產生之氧化物質之量 '然而 物加所 寺丁為導致較南生產成本 J50733.doc 2011279502H+ + 2e·—H2 T In this embodiment, as illustrated by Chemical Formula 7, oxidation of, for example, peroxymonosulfuric acid (HjOj, peroxodisulfuric acid (HjW8), etc., can be obtained by electrolyzing the sulfuric acid solution. a substance; and an oxidizing solution containing such an oxidizing substance. Although hydrogen is produced as a by-product, the hydrogen does not affect the removal of the anti-knocking agent, etc. Chemical formula 7 H2S〇4+H20-oxidizing substance + η2 In the case where peroxymonosulfuric acid is used, the reaction rate of peroxymonosulfuric acid with an organic substance such as anti-(iv) is high. Because of the &, even the amount to be removed is relatively large, and the resist removal can also be It is completed in a short period of time. In addition, in the case where peroxymonosulfuric acid is used, it can also be realized at a low temperature, and thus it is not necessary to adjust the skewness of the neckline and the like. Peroxymonosulfuric acid is produced. Therefore, the reaction rate of the peroxymonosulfuric acid and the removed article can be increased even at a low temperature, here, by reducing the processing time from the > Increase the oxidizing substance An amount in sufficient small hole, large oxidation amount of generated power is increased by the applied substances' but was added to cause the temple butoxy production cost than the southern J50733.doc 201127950
及環境影響。因此，# i M 該氧化物質。需要藉由增加電解效率來有效地產生 2據由發明者所獲得之知識，在恒定電解參數（例如， 門；流動逮率、溫度等)之情況令，可藉由減少電解期 二硫酸遭度來產生更多氧化物質。以，可藉由減少 :、應至硫酸電解單元10之硫酸濃度來增加該氧化溶液中所 ，含之氧化物質(例如’過氧單硫酸及過氧二硫旬之產生 效率。 圖3係圖解說明該等氧化物質之濃度及該硫酸之濃度對 該剝除時_除㈣）之料之圖表。絲化物質濃度係 繪製於水平轴上。該剝除時間（移除時間）料製於垂直軸 上。在圖3中，B1係其中硫酸濃度係7〇重量百分比之情 況；B2係其中硫酸濃度係8〇重量百分比之情況⑼係其 中硫酸濃度係85重量百分比之情況；B4係其中硫酸濃度係 9〇重量百分比之情況；謂係其中硫酸濃度係％重量百分 比之情況。 圖3顯示隨著硫酸濃度減少，i生更多氧化物質；且該 等氧化物質之濃度因此增加。此外，對於相同硫酸濃度， 隨著該等氧化物質之濃度增加（隨著該等氧化物質之量增 加）’該剝除時間（移除時間）縮短。 換言之，隨著在氧化物質之產生階段中硫酸濃度減少可 產生更多氧化物質。結果，可縮短剝除時間（移除時間）。 因此，在此實施例中，將具有不低於3〇重量百分比且不 高於70重量百分比之硫酸濃度之稀硫酸溶液供應至硫酸電 150733.doc •19· 201127950 解單元ίο。 因此，可藉由增加硫酸電解單元1〇之電解效率來產生更 多氧化物質。結果，可將包含大量氧化物質之氧化溶液供 應至欲清洗之物件w之表面。因此，可縮短該處理時間。 此處，在藉由以高劑量植入雜質製造高速運作半導體穿 置時，藉由以該高劑量植入該雜質在該抗蝕劑之表面中形 成經改動層。其中形成有此經改動層之抗蝕劑不易移除； 且遺憾的是，不可僅藉由上文所述氧化物質之氧化分解能 力獲得所期望移除邊際。 在此情況中，可感知藉由使用高於氧化物質之彼等分解 此力及分移除能力之分解能力及移除能力之物質移除在其 表面中形成有經改動層之抗蝕劑。舉例而言，用於移除氧 化物膜及天然氧化物膜之氫氟酸具有高分解能力及高移除 能力。因此，可想想使用氫氟酸移除在其表面中形成由經 改動層之抗钮劑。 然而’用於移除氧化物膜及天然氧化物膜之氫氟酸具有 分解及移除氧化物（例如’二氧化矽膜等）及氮化物（例如， 氮化石夕膜等）之能力。因此，可不合意地移除形成於晶圓 上之氧化物膜及氮化物膜；且可發生所謂之膜減少。特定 而言’在其中氧化物膜、氮化物膜及類似膜曝露於未用抗 蚀劑覆蓋之部分處之情況中，可不合意地移除此等部分。 因此’認為氫氟酸在具有移除諸如抗蝕劑之有機物質之 目標之應用中係不用的。 作為發明者之調查結果，獲得以下知識：可抑制氫氟酸 150733.doc •20· 201127950 在包含氧化物質之酸性溶液中對氧化物（例如，二氧化石夕 膜等）及氮化物（例如，氮切膜等）之移除能h亦獲得以 下知識：在此情況中，即使抑制了移除氧化物及氮化物之 能力’亦可藉由包含氫_而增加移除抗㈣之能力。 表！比較移除氧化物膜、氮化物膜及其中形成有經改動 層之抗姓劑之能力。 二氧切膜_2)係藉由形成氧化物膜之熱氧化物膜方 法形成於石夕基板上。氮切膜（SiN)係藉由形錢化物膜 之LP CVD形成於矽基板上。為形成其中形成有經改動層 之抗蝕劑，將抗蝕劑塗佈於矽基板上、曝光、顯影及圖案 化；且抗钱劑表面係藉由，原子/cm2劑量之石申來改動。 SPM溶液係藉由以3:1之容積比（硫酸溶液：過氧化氮水 溶液=3:1)混合具有98重量百分比之硫酸漠度之硫酸溶液 與具有35重量百分比之過氧化氫濃度之過氧化氫水溶液來 產生m兄中’混合硫酸溶液與過氧化氫水溶液產生 氧化物質（例如，過氧單硫酸（HJ05)、過氧二硫酸 _2〇8)等）。因此，SPM溶液亦係包含氧化物質之氧化溶 液。 包3氧化物質之氧化溶液係藉由電解具有7〇重量百分比 之硫酸濃度之稀硫酸溶液而產生。 氫氟&L水洛液係藉由將氫氟酸添加至水以形成具有1 〇〇〇 PPm之氫氟酸濃度之水溶液而製成。 氫氟酸添加至其之硫酸溶液係藉由將氫氟酸添加至具有 98重里百分比之硫酸濃度之硫酸溶液以提供1⑽〇叩爪之氫 150733.doc 201127950 氟酸濃度而製成。 氫氟酸添加至其之氧化溶液係藉由將氫氟酸添加至藉由 電解70重量百分比之硫酸濃度之稀硫酸溶液產生之溶液以 獲得1 〇〇〇 ppm之氫氟酸濃度而製成。 藉由蝕刻速率評估氧化物膜（二氧化矽膜，亦即Si〇2)及 氮化物膜（氮化矽膜，亦即SiN)之移除；且在60。(：之處理 溫度下針對3分鐘之處理時間量測钱刻量。 藉由用肉眼觀察來s平估其中形成有經改動層之抗姓劑之 移除。移除其中形成有經改動層之抗蝕劑時之處理溫度在 其中使用氫氟酸水溶液之情況中係8〇°C且在其中使用其他 溶液之情況中係130°C。 表1 蝕刻速率(A/3分鐘） 具有經改動層之抗 蝕劑之剝除條件 Si〇2 SiN SPM溶液 0 0 存在剝除殘餘 藉由電解硫酸產生之氧化溶液 0 0 存在剝除殘餘 具有1000 PPM之氫氟酸濃度之 水溶液 22 31 未剝除 具有1000 ppm之氫氟酸濃度之 硫酸溶液 21 13 未剝除 具有1000 ppm之氫氟酸濃度之 氧化溶液 0 5 剝除且不具有剝$ 殘餘 如表1中所圖解說明，在其中僅使用SPM溶液（藉由混合 石爪酸浴液及過氧化氫水溶液產生之包含氧化物質之氧化溶 液）之情況中及其中僅使用藉由電解稀硫酸溶液產生之包 含氧化物質之氧化溶液之情況中未移除二氧化矽膜（Si〇2) 150733.doc -22· 201127950 及^切膜（SiN)。換言之，在其中僅使用包含氧化物質 =—化洛液來移除諸如抗蝕劑之有機物質之情況中，未損 裒一氧化矽膜（Si〇2)及氮化矽膜（SiN)。然而，當移除其表 - 中形成有經改動層之抗蝕劑時，未完全移除該抗蝕劑且 留下所謂的剝除殘餘（殘渣）。 在其中透過下-製程之處理仍然存在此剝除殘餘（殘淺） 凊況中，存在良率可顯著降低之風險。雖然可想像藉由 在先則製程中使用更嚴格之幹钮刻條件及執行其他化學溶 液處理來解決此等問題，但成本會增加且可發生新的問 題，例如晶圓之氧化。 在其中使用具有1000 ppm之氫氟酸濃度之水溶液之情況 中’蝕刻且不合意地移除二氧化矽膜(si02)及氮化矽膜 (SlN)。換言之，在其中僅使用氫氟酸水溶液移除諸如抗 钮劑之有機物質之情況中，存在對二氧化石夕膜_2)及氮 化石夕膜（SiN)之損壞之風險。 根據由發明者執行之實驗，斷^在其中使用氫氟酸水溶 液之情況中不能移除其表面中形成有經改動層之抗蝕劑。 換言之，斷定氫氟酸水溶液不適合移除該抗蝕劑。 在其中將氫氟酸添加至硫酸溶液且使用具有1〇〇〇卯⑺之 氫氟酸濃度之硫酸溶液之情況中，不合意地蝕刻及移除二 氧化矽膜（Si〇2)及氮化矽膜（SiN)。換言之，在其中僅使用 氫氟酸添加至其之硫酸溶液釋出諸如抗蝕劑之有機物質之 情況中，存在對二氧化矽膜（si02)及氮化矽膜（siN)之損壞 之風險。 150733.doc ^ 201127950 此外，根據由發明者執行之實驗，斷定在其中使用氫氟 酸添加至其之硫酸溶液之情況中，不能移除其表面中形成 有經改動層之抗蝕劑。換言之，斷定氫氟酸添加至其之硫 酸溶液不適合移除該抗蝕劑^ 相反，在其中使用氫氟酸添加至其之氧化溶液（在此實 驗中，該氧化溶液具有1000 ppm之氫氟酸濃度）之情況 中，輕微地蝕刻及移除氮化矽膜（siN)，但抑制二氧化矽 膜（S^2)之蝕刻及移除。此外，可移除其表面中形成有麫 改動層之抗蝕劑而不具有剝除殘餘（殘渣）。 因此，藉由使用氫氟酸添加至其之氧化溶液作為清洗 液，可移除其表面中形成有經改動層之抗蝕劑（其傳統上 係難以移除）而不留下剝除殘餘（殘旬且不損壞二氧化石 (Si02)及氮化矽膜（SiN)。 、 1寻现上 稽田稭助祚蝕刻進行灰化移除抗蝕劑表面 之經改動層且隨後藉由執行使用spM溶液之處理移除剩餘 抗钱劑。因此，此導致更多處理製程、更多處理設、 型、更長處理時間等。相反’藉由使用氣氣酸添加至其之 氧化溶液作為清洗液’可藉由—種類型處理來料盆表And environmental impact. Therefore, # i M the oxidizing substance. It is necessary to effectively generate 2 knowledge obtained by the inventors by increasing the electrolysis efficiency, and by reducing the electrolysis period of disulfuric acid in the case of constant electrolysis parameters (for example, gate; flow rate, temperature, etc.) To produce more oxidizing substances. Therefore, by reducing the sulfuric acid concentration of the sulfuric acid electrolysis unit 10, the oxidizing substance contained in the oxidizing solution (for example, the production efficiency of peroxymonosulfuric acid and peroxodisulfide can be increased. Fig. 3 is a diagram A graph indicating the concentration of the oxidized species and the concentration of the sulfuric acid for the stripping at the time of stripping (four). The concentration of the silk fibroin is plotted on the horizontal axis. The stripping time (removal time) is made on the vertical axis. In Fig. 3, B1 is a case where the concentration of sulfuric acid is 7〇 by weight; B2 is a case where the concentration of sulfuric acid is 8〇 by weight (9) is a case where the concentration of sulfuric acid is 85 weight%; and B4 is a concentration of sulfuric acid of 9〇. The case of weight percentage; that is, the case where the concentration of sulfuric acid is % by weight. Figure 3 shows that as the concentration of sulfuric acid decreases, i produces more oxidizing species; and the concentration of such oxidizing species thus increases. Further, for the same sulfuric acid concentration, as the concentration of the oxidizing substances increases (as the amount of the oxidizing substances increases), the stripping time (removal time) is shortened. In other words, more oxidizing species can be produced as the concentration of sulfuric acid decreases during the stage of production of the oxidizing species. As a result, the stripping time (removal time) can be shortened. Therefore, in this embodiment, a dilute sulfuric acid solution having a sulfuric acid concentration of not less than 3 〇 by weight and not more than 70% by weight is supplied to the sulphuric acid 150733.doc • 19·201127950 solution unit ίο. Therefore, more oxidizing substances can be produced by increasing the electrolysis efficiency of the sulfuric acid electrolysis unit. As a result, an oxidizing solution containing a large amount of oxidizing substance can be supplied to the surface of the object w to be cleaned. Therefore, the processing time can be shortened. Here, when a high speed operation semiconductor is fabricated by implanting impurities at a high dose, a modified layer is formed in the surface of the resist by implanting the impurity at the high dose. The resist in which the modified layer is formed is not easily removed; and unfortunately, the desired removal margin cannot be obtained only by the oxidative decomposition ability of the oxidizing substance described above. In this case, it is perceived that the resist having the modified layer formed in the surface thereof is removed by using a substance which decomposes the oxidizing substance and the ability to decompose and remove the removing ability. For example, hydrofluoric acid for removing an oxide film and a natural oxide film has high decomposition ability and high removal ability. Therefore, it is conceivable to use hydrofluoric acid to remove an anti-knocking agent which forms a modified layer in its surface. However, the hydrofluoric acid used to remove the oxide film and the natural oxide film has the ability to decompose and remove oxides (e.g., 'cerium oxide film, etc.) and nitrides (e.g., nitride film, etc.). Therefore, the oxide film and the nitride film formed on the wafer can be undesirably removed; and so-called film reduction can occur. Specifically, in the case where an oxide film, a nitride film, and the like are exposed to a portion not covered with a resist, these portions may be undesirably removed. Therefore, it is considered that hydrofluoric acid is not used in applications having the objective of removing organic substances such as resists. As a result of the investigation by the inventors, the following knowledge is obtained: hydrofluoric acid can be suppressed 150733.doc • 20·201127950 In an acidic solution containing an oxidizing substance, an oxide (for example, a dioxide film, etc.) and a nitride (for example, The removal energy of the nitrogen cut film or the like also obtains the knowledge that in this case, even if the ability to remove oxides and nitrides is suppressed, the ability to remove the anti-(four) can be increased by including hydrogen. table! The ability to remove the oxide film, the nitride film, and the anti-surname agent in which the altered layer is formed is compared. The dioxic film 2) is formed on the Shih-hs substrate by a thermal oxide film forming an oxide film. The nitrogen cut film (SiN) is formed on the tantalum substrate by LP CVD of a bulk crystal film. To form a resist in which the modified layer is formed, a resist is applied to the tantalum substrate, exposed, developed, and patterned; and the surface of the anti-money agent is modified by the atomic/cm2 dose. The SPM solution was prepared by mixing a sulfuric acid solution having 98% by weight of sulfuric acid inversion with a volume ratio of 3:1 (sulfuric acid solution: aqueous solution of nitrogen peroxide = 3:1) and peroxidation having a concentration of hydrogen peroxide of 35 weight percent. The aqueous hydrogen solution is used to produce a mixed sulfuric acid solution and an aqueous hydrogen peroxide solution to produce an oxidizing substance (for example, peroxymonosulfuric acid (HJ05), peroxydisulfate 2〇8), and the like. Therefore, the SPM solution is also an oxidizing solution containing an oxidizing substance. The oxidizing solution of the oxidized material of the package 3 was produced by electrolyzing a dilute sulfuric acid solution having a sulfuric acid concentration of 7 〇 by weight. Hydrofluoro&L aqueous solution is prepared by adding hydrofluoric acid to water to form an aqueous solution having a hydrofluoric acid concentration of 1 〇〇〇 PPm. The sulfuric acid solution to which hydrofluoric acid was added was prepared by adding hydrofluoric acid to a sulfuric acid solution having a sulfuric acid concentration of 98% by weight to provide a hydrogen fluoride concentration of 1 (10) of the claws 150733.doc 201127950. The oxidizing solution to which hydrofluoric acid is added is prepared by adding hydrofluoric acid to a solution produced by electrolyzing 70 wt% of a sulfuric acid concentration of a dilute sulfuric acid solution to obtain a hydrofluoric acid concentration of 1 〇〇〇 ppm. The removal of the oxide film (cerium oxide film, i.e., Si〇2) and the nitride film (yttrium nitride film, i.e., SiN) were evaluated by etching rate; and at 60. (: The processing time is measured for the processing time of 3 minutes. By visual observation, the removal of the anti-surname agent in which the modified layer is formed is evaluated. The removed layer is formed. The treatment temperature at the time of the resist was 8 ° C in the case where an aqueous solution of hydrofluoric acid was used and 130 ° C in the case where other solutions were used. Table 1 Etching rate (A / 3 minutes) with modified layer Resin stripping conditions Si〇2 SiN SPM solution 0 0 Exfoliation residuals Oxidation solution produced by electrolytic sulfuric acid 0 0 Exfoliated residual aqueous solution having a hydrofluoric acid concentration of 1000 PPM 22 31 Unstripped 1000 ppm hydrofluoric acid concentration of sulfuric acid solution 21 13 Undoped oxidizing solution with 1000 ppm hydrofluoric acid concentration 0 5 Stripping and no stripping residue Residue as illustrated in Table 1, in which only SPM solution is used (in the case of an oxidizing solution containing an oxidizing substance produced by mixing a salt acid bath and an aqueous hydrogen peroxide solution) and in the case where only an oxidizing solution containing an oxidizing substance produced by electrolytic dilute sulfuric acid solution is used Remove the ruthenium dioxide film (Si〇2) 150733.doc -22·201127950 and cut film (SiN). In other words, use only the oxidized substance=-chemical solution to remove organic substances such as resist In the case, the niobium monoxide film (Si〇2) and the tantalum nitride film (SiN) are not damaged. However, when the resist having the modified layer formed therein is removed, the The resist leaves a so-called stripping residue (residue). In the case where the stripping residue (residual light) still exists through the process of the lower-process, there is a risk that the yield can be significantly reduced. Although it is conceivable Solving these problems by using more stringent dry button conditions and performing other chemical solution treatments in prior processes, but the cost increases and new problems can occur, such as oxidation of the wafer. 1000 ppm is used in it. In the case of an aqueous solution of hydrofluoric acid concentration, 'etching and undesirably removing the cerium oxide film (si02) and the cerium nitride film (S1N). In other words, in which only a hydrofluoric acid aqueous solution is used, such as a resisting agent is removed. In the case of organic matter, there is a pair of dioxide dioxide film _ 2) The risk of damage to the Nitrogen Fossil Film (SiN). According to the experiment performed by the inventors, the resist having the modified layer formed on the surface thereof could not be removed in the case where the hydrofluoric acid aqueous solution was used. In other words, it is concluded that the hydrofluoric acid aqueous solution is not suitable for removing the resist. In the case where hydrofluoric acid is added to a sulfuric acid solution and a sulfuric acid solution having a hydrofluoric acid concentration of 1 〇〇〇卯(7) is used, the ruthenium dioxide film (Si〇2) and nitridation are undesirably etched and removed. Diaphragm (SiN). In other words, in the case where only a sulfuric acid solution to which hydrofluoric acid is added is used to release an organic substance such as a resist, there is a risk of damage to the ceria film (si02) and the tantalum nitride film (siN). Further, according to an experiment performed by the inventors, it was judged that in the case where a sulfuric acid solution to which hydrofluoric acid was added was used, the resist having a modified layer formed on the surface thereof could not be removed. In other words, it is concluded that the sulfuric acid solution to which the hydrofluoric acid is added is not suitable for removing the resist. In contrast, an oxidizing solution to which hydrofluoric acid is added is used (in this experiment, the oxidizing solution has 1000 ppm of hydrofluoric acid). In the case of concentration, the tantalum nitride film (siN) is slightly etched and removed, but the etching and removal of the hafnium oxide film (S^2) is suppressed. Further, the resist having the ruthenium modified layer formed on the surface thereof can be removed without the peeling residue (residue). Therefore, by using an oxidizing solution to which hydrofluoric acid is added as a cleaning liquid, a resist having a modified layer formed on the surface thereof (which is conventionally difficult to remove) can be removed without leaving a peeling residue ( Residual and does not damage the SiO 2 (SiO 2 ) and tantalum nitride film (SiN). 1 寻 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上 上The treatment of the spM solution removes the remaining anti-money agent. Therefore, this results in more processing processes, more processing settings, types, longer processing times, etc. Conversely 'by using an oxidizing solution added to the oxidizing solution as a cleaning solution 'Can be used to treat the type of pots
中形成有㈣動層之抗㈣。因&，可增加生產率了 少生產成本等。 A 雖然在此實施例中預先圖解說明其中將氫1酸添加 質兄上但亦可藉由(例如)將該氧化溶液及該氫氟 酉夂依序或，質上同時地供應至欲清洗之物件w之表面 4钱劑等之移除。該移除可不僅在其表面中形成㈣改 150733.doc -24- 201127950 動層之抗蝕劑上而且在其表面中未形成有經改動層之抗蝕 劑上執行。然而，其可尤其用於移除其表面十形成有經改 動層之抗蝕劑’該抗蝕劑傳統上係難以移除。 現在將闡述根據此實施例之一種清洗方法。 圖4係圖解說明該清洗方法之流程圖。 首先，藉由電解硫酸溶液產生包含氧化物質（例如，過 氧單硫酸及過氧二硫酸）之氧化溶液（步驟sl_〇。在此情況 中，可藉由使該硫酸溶液之硫酸濃度不低於3〇重量百分比 且不高於70重量百分比來有效地產生該等氧化物質。 然後，調整所產生氧化溶液之溫度（步驟S1_2)。雖然此 溫度調整並非總是必需的，但端視處理時間之縮短、清洗 系統之可允許溫度及強度等，將該氧化溶液之溫度調整為 不低於100。。且不高於110。。係有利的。可對所產生氧化溶 液、產生期間（電解期間）之氧化溶液、及為該電解供應之 硫酸溶液中之任何溶液執行該溫度調整。 調整氫氟酸之溫度（步驟S2)。雖然此溫度調整並非總是 必需的，但端視處理時間之縮短、清洗系統之可允許溫度 及強度等，將氫氟酸之溫度調整為不低於1〇〇艽且不高於 110 °c係有利的。 ° 然後’將氫氟酸與氧化溶液依序地或實質上同時地供應 至=清洗之物件W之表面（步驟S3)。可針對欲清洗且將依 序π入於a亥氫氟酸及該氧化溶液中之物件W中之每一者而 自分配單元等執行該供應。此外，例如，可自針對該氫氟 酸及該氧化溶液之單獨管道系統依序地或實質上同時地來 150733.doc -25· 201127950 執行該供應。可使用所謂的單晶圓處理、批量處理及諸如 此類。 圖5係圖解說明根據另一實施例之清洗方法之流程圖。 在此實施例中’混合該氧化溶液及該氫氟酸，且將該混 合物供應至欲清洗之物件W之表面。 首先’藉由電解硫酸溶液來產生包含氧化物質（例如， 過氧單硫酸及過氧二硫酸）之氧化溶液（步驟S丨〇)。在此情 況中，可藉由使該硫酸溶液之硫酸濃度不低於30重量百分 比且不高於7 0重量百分比來有效地產生該等氧化物質。 然後，將該氧化溶液及該氫氟酸混合以產生清洗液（步 驟S11)。此時’適當地調整該清洗液中之該無機酸濃度及 該等氧化物質之量。 接著，調整所產生清洗液之溫度（步驟S12)。雖然此溫 度調整並非總是必需的，但端視處理時間之縮短及清洗系There is (4) the resistance of the moving layer (4). Because &, it can increase productivity and reduce production costs. A, although in this embodiment, it is previously illustrated that hydrogen acid is added to the brethren, but the oxidizing solution and the hydrofluoro fluorene may be supplied to the liquid to be cleaned, for example, simultaneously or qualitatively. The surface of the object w is removed by 4 money and the like. This removal can be performed not only on the resist formed on the surface of the layer, but also on the resist in which no altered layer is formed in the surface. However, it can be used in particular to remove a resist whose surface is formed with a modified layer. The resist is conventionally difficult to remove. A cleaning method according to this embodiment will now be explained. Figure 4 is a flow chart illustrating the cleaning method. First, an oxidizing solution containing an oxidizing substance (for example, peroxymonosulfuric acid and peroxodisulfuric acid) is produced by electrolyzing a sulfuric acid solution (step s1_〇. In this case, the sulfuric acid concentration of the sulfuric acid solution can be made low) The oxidizing species are effectively produced at a weight percentage of 3 Å and not more than 70% by weight. Then, the temperature of the oxidizing solution produced is adjusted (step S1_2). Although this temperature adjustment is not always necessary, the processing time is not necessary. The shortening, the allowable temperature and strength of the cleaning system, etc., the temperature of the oxidizing solution is adjusted to not less than 100. and not higher than 110. It is advantageous. The oxidizing solution generated, during the production period (electrolysis period) The temperature adjustment is performed on the oxidizing solution and any solution in the sulfuric acid solution supplied to the electrolysis. The temperature of the hydrofluoric acid is adjusted (step S2). Although this temperature adjustment is not always necessary, the end processing time is shortened. It is advantageous to adjust the temperature of the hydrofluoric acid to not less than 1 〇〇艽 and not more than 110 ° C. The temperature and strength of the cleaning system are favorable. The fluoric acid and the oxidizing solution are sequentially or substantially simultaneously supplied to the surface of the object to be cleaned (step S3), and may be applied to the object to be cleaned and sequentially placed in a hydrofluoric acid and the oxidizing solution. Each of the Ws performs the supply from the dispensing unit or the like. Further, for example, the separate piping system for the hydrofluoric acid and the oxidizing solution may be sequentially or substantially simultaneously 150733.doc -25· 201127950 This supply is performed. So-called single wafer processing, batch processing, and the like can be used. Fig. 5 is a flow chart illustrating a cleaning method according to another embodiment. In this embodiment, 'the oxidizing solution and the hydrofluoric acid are mixed And supplying the mixture to the surface of the article W to be cleaned. First, an oxidizing solution containing an oxidizing substance (for example, peroxymonosulfuric acid and peroxodisulfuric acid) is produced by electrolytic sulfuric acid solution (step S丨〇). In this case, the oxidizing substance can be efficiently produced by making the sulfuric acid concentration of the sulfuric acid solution not less than 30% by weight and not more than 70% by weight. Then, the oxidizing solution and the hydrogen are produced. The fluoric acid is mixed to produce a cleaning liquid (step S11). At this time, the concentration of the inorganic acid in the cleaning liquid and the amount of the oxidizing substances are appropriately adjusted. Next, the temperature of the generated cleaning liquid is adjusted (step S12). This temperature adjustment is not always necessary, but the processing time is shortened and the cleaning system is
液及該氫氟酸執行該溫度調整。The liquid and the hydrofluoric acid perform this temperature adjustment.
溶孜之後將氫氟酸添加至該氧化溶液 巴含氧化物質之氧化 之情況，但可將該氫 150733.doc -26- 201127950 氟酸添加至硫酸溶液，該硫酸溶液係氧化溶液之源材料； 且然後可電解此溶液來產生包含氧化物質且氫氟酸添加至 其之清洗液（參照圖6)。 此外，可藉由透過混合硫酸溶液與過氧化氫水溶液產生 包含氧化物質之氧化溶液（SPM溶液）且將氫氟酸添加至其 來產生清洗液。此外，可藉由混合硫酸溶液、過氧化氫水 溶液及氫氟酸來產生包含氧化物質及具有添加至其之氫氟 酸之清洗液。 換言之，清洗液係表現酸性且包含氧化物質及氫氟酸之 溶液係足夠的。其製造方法可包含在產生包含氧化物質之 酸性溶液（氧化溶液）之後添加氫氟酸或自具有添加至其之 氫氣酸之硫酸溶液產生氧化物質。 圖6係圖解說明其中電解具有添加至其之氫氟酸之硫酸 溶液之清洗系統之示意圖。 如圖6中所圖解說明，氫氟酸供應單元50包含保持氫氟 酉文之罐5 1、幫浦5 2及開/關閥71。罐5 1、幫浦5 2及開/關閥 71經由管道線路53a連接至硫酸供應單元15側上之管道線 路。換言之，管道線路53a連接至開/關閥7〇之下游側上之 &道線路。保持在罐5 1中之氫氟酸可藉由幫浦52之運作經 由管道線路53a供應至硫酸電解單元1〇之陽極室3〇 ^換言 之，氫氟酸供應單元5〇具有將保持在罐51中之氫氟酸供應 至硫酸電解單元10之陽極室30之功能；且可藉由電解具有 添加至其之氫氟酸之硫酸溶液來產生包含氧化物質及具有 添加至其之氫氟酸之清洗液。 150733.doc •27· 201127950 端視氫氟酸之添加，至少陽極導電膜35係由導電金剛石 膜製成係有利的。 現在將闡述根據此實施例之一種用於製造微細構造之方 法。 一種用於製造微細構造之方法之實例包含（例如）一種用 於製造半導體裝置之方法。此處，該半導體裝置之製造製 程包含所謂的前端製程，諸如藉由膜形成、抗蝕劑塗佈、 曝光、顯影、#刻、抗触劑移除等在基板（晶圓）上形成圖 案之製程、檢查製程、清洗製程、熱處理製程、雜質弓I入 製程、擴散製程、平坦化製程等。所謂的後端製程包含切 割、安裝、接合、囊封等之組裝製程’功能性及可靠性檢 查製程等。 在此情況中，可藉由在抗蝕劑移除過程期間使用上文所 述（例如）該等清洗液、該等清洗方法及該等清洗系統來增 加該抗姓劑之可移除性。特定而言，可移除其表面中形成 有經改動層之抗蝕劑（其傳統上係難以移除）而不留下剝除 殘餘（殘渣）且不損壞二氧化矽膜（si02)及氮化矽膜（siN)。 傳統上，需要藉由藉助幹蝕刻進行灰化移除抗蝕劑表面 之經改動層且隨後藉由執行使用S p M溶液之處理移除剩餘 抗蝕劑。因此，此導致更多處理製程、更多處理設備類 型、更長處理時間等。相反’藉由使用上文所述該等清洗 . 液”亥等清洗方法及言亥等清洗系统，可藉由—種類型處理 來移除其表面中形成有經改動層之抗钱劑。因此，可增加 生產率，可減少生產成本等。 150733.doc -28· 201127950 習知技術可應用於除根據上文所闡述此實施例之清洗方 法及清洗系統之彼等製程以外之製程，且因此省略其詳細 闡述。 雖然將用於製造半導體裝置之方法圖解說明為用於製造 該微細構造之该方法之一個實例，但用於製造該微細構造 之方法並不限於此。例如，在諸如液晶顯示裝置、相位移 遮罩、MEMS領域中之微機械、精密光學組件等之領域 中，可實現應用。 在上文所闡述之清洗系統中，並非總是需要提供循環該 溶液之組態。如圖7中所圖解說明，清洗處理單元12中所 使用之溶液可與污染物及諸如此類一起回收至回流罐Μ中 且然後經由排放管道線路75排放至該系統外部。 此處理可不制於移除由有機物質製成之抗姓劑，亦可 用於類似地移除金屬雜質、顆粒及幹蝕刻殘渣等。 例如，在圖案化具有大的縱橫比之金屬互連件期間，沈 積幕多互連金屬、該等互連金屬之氧化物及i化物、障壁 金屬及該等障壁金屬之氧化物及鹵化物等。此外，在圖案 化具有大的縱橫比之矽系統期間’沈積眾多二氧化矽及南 化物。在眾多情況中，Λ等物質不能僅藉由SPM溶液之氧 化物質之氧化能力來移除。 然而，可藉由氫氟酸分解及移除此等沈積物中之眾多沈 積物。藉由使用上文所述該等清洗液、該等清洗方法及該 等清洗系統，可在不損壞二氧化石夕膜(Si〇2)及氮化石夕膜 (SlN)之情形下實現此移除。 150733.doc -29- 201127950 換言之，當移除黏附至微細構造之污染物時可實現眾多 應用。在此情況中，當氧化物及氮化物位於該表面上時其 係尤其有用，此乃因可在抑制該等氧化物及該等氮化物之 移除之同時移除該等污染物。 可提供機器人以傳送欲清洗之物件^持該硫酸溶液之 罐60及保持該氫氟酸之罐51中之每一者可連接至工廠之線 路以自動地補充該溶液。可提供沖洗槽以用於在移除該等 污染物之後沖洗欲清洗之物件。此沖洗槽可包含溢流控制 裝置及使用内嵌式加熱器之溫度控制裝置。適合將石英用 作該沖洗槽之材料。 在上文，對實施例進行圖解說明。然而，本發明並不限 於其闡述。 關於上文所闡述之實施例熟習此項技術者所適當做出之 设計修改就包含本發明之特徵而言亦系包含於本發明之範 疇内。 例如’上文所闡述之該等清洗系統之該等組件之組態、 尺寸、材料品質、佈置等並不限於本文所圖解說明之彼等 且可適當地修改。 此外’上文所闡述之實施例之組件可在可行性範圍内進 行組合；且此等組合就包含本發明之特徵而言亦系包含於 本發明之範疇内。 雖然已闡述某些實施例，但此等實施例已僅以實例之方 式來呈現’且並不意欲限制本發明之範疇。實際上，本文 所闡述之新穎液體、清洗方法、清洗系統及製造方法玎以 150733.doc 30- 201127950 多種其他形式來體現；此外，可在不背離本發明之精神的 條件下做出本文所闡述之液體、清洗方法、清洗系統及製 造方法之形式之各種省略、替代及改變。隨附申請專利範 圍及其等效物意欲涵蓋將屬於本發明之範疇及精神之此等 形式或修改。 【圖式簡單說明】 圖1係圖解說明根據此實施例之清洗系統之示意圖； 圖2A及2B係圖解說明氧化物質之產生機制之示意圖； 圖3係圖解說明該等氧化物質之濃度及硫酸之濃度對該 移除時間之影響之圖表； 圖4係圖解說明該清洗方法之流程圖； 圖5係圖解說明根據另一實施例之清洗方法之流程圖； 圖6係圖解說明其中電解具有添加至其之氫氟酸之硫酸 之清洗系統之示意圖；及 圖7係圖解說明不提供有循環溶液之組態之清洗系統之 示意圖。 【主要元件符號說明】 5 清洗系統 10 硫酸電解單元 12 清洗處理單元 14 溶液循環單元 15 硫酸供應單元 16 陰極出口 17 陽極出口 150733.doc •31· 201127950 18 陰極入口 19 陽極入口 20 隔膜 22 上端密封單元 23 下端密封單元 24 電解單元外殼 26 直流電源 28 罐 29 蓋 30 陽極室 32 陽極 33 陽極支撐體 34 陽極基底構件 35 陽極導電膜 40 陰極室 42 陰極 43 陰極支撐體 44 陰極基底構件 45 陰極導電膜 50 氫氟酸單元 51 罐 52 幫浦 53 管道線路 53a 管道線路 150733.doc -32- 201127950 60 罐 61 分配單元 62 旋轉台 63 回流罐 64 過濾器 70 開/關閥 71 開/關閥 72 開/關閥 73 管道線路 73a 開/關閥 74, 85 管道線路 74a 開/關閥 75 管道線路 75a 開/關閥 76 開/關閥 80 幫浦 81 幫浦 82 幫浦 86 管道線路 91 開/關閥 150733.doc -33-After the solvent is dissolved, hydrofluoric acid is added to the oxidation of the oxidizing solution containing the oxidizing substance, but the hydrogen 150733.doc -26-201127950 fluoric acid may be added to the sulfuric acid solution, which is the source material of the oxidizing solution; And this solution can then be electrolyzed to produce a cleaning solution containing an oxidizing substance and hydrofluoric acid added thereto (refer to Fig. 6). Further, a cleaning liquid can be produced by permeating a sulfuric acid solution and an aqueous hydrogen peroxide solution to produce an oxidizing solution (SPM solution) containing an oxidizing substance and adding hydrofluoric acid thereto. Further, a cleaning liquid containing an oxidizing substance and having hydrofluoric acid added thereto can be produced by mixing a sulfuric acid solution, a hydrogen peroxide aqueous solution, and hydrofluoric acid. In other words, the cleaning liquid is acidic and the solution containing the oxidizing substance and hydrofluoric acid is sufficient. The manufacturing method may include the addition of hydrofluoric acid or the formation of an oxidizing substance from a sulfuric acid solution having a hydrogen acid added thereto after generating an acidic solution (oxidizing solution) containing an oxidizing substance. Fig. 6 is a schematic view showing a cleaning system in which a sulfuric acid solution having hydrofluoric acid added thereto is electrolyzed. As illustrated in Fig. 6, the hydrofluoric acid supply unit 50 includes a tank 5 1 for holding a hydrofluorocarbon, a pump 5 2, and an on/off valve 71. The tank 5 1, the pump 5 2 and the on/off valve 71 are connected to the pipeline line on the side of the sulfuric acid supply unit 15 via the piping line 53a. In other words, the pipe line 53a is connected to the & track line on the downstream side of the opening/closing valve 7〇. The hydrofluoric acid held in the tank 51 can be supplied to the anode chamber of the sulfuric acid electrolysis unit 1 via the piping line 53a by the operation of the pump 52. In other words, the hydrofluoric acid supply unit 5 has the tank 51 to be held in the tank 51. The hydrofluoric acid is supplied to the anode chamber 30 of the sulfuric acid electrolysis unit 10; and the sulfuric acid containing the hydrofluoric acid added thereto can be used to produce the cleaning containing the oxidizing substance and having the hydrofluoric acid added thereto liquid. 150733.doc •27· 201127950 The addition of hydrofluoric acid is advantageous, at least the anode conductive film 35 is made of a conductive diamond film. A method for manufacturing a fine structure according to this embodiment will now be explained. An example of a method for fabricating a fine structure includes, for example, a method for fabricating a semiconductor device. Here, the manufacturing process of the semiconductor device includes a so-called front-end process, such as forming a pattern on a substrate (wafer) by film formation, resist coating, exposure, development, etching, anti-contact removal, and the like. Process, inspection process, cleaning process, heat treatment process, impurity-injection process, diffusion process, flattening process, etc. The so-called back-end process includes assembly processes such as cutting, mounting, joining, and encapsulation, and functional and reliability inspection processes. In this case, the removability of the anti-surname agent can be increased by using the above-described cleaning liquids, such cleaning methods, and the cleaning systems during the resist removal process. In particular, a resist having a modified layer formed on its surface (which is conventionally difficult to remove) may be removed without leaving a residue (residue) and not damaging the cerium oxide film (si02) and nitrogen.矽 film (siN). Conventionally, it is necessary to remove the altered layer of the resist surface by ashing by dry etching and then remove the remaining resist by performing a process using the Sp M solution. Therefore, this leads to more processing processes, more processing device types, longer processing times, and the like. On the contrary, by using the above-mentioned cleaning methods such as the cleaning solution, and the cleaning system such as Yanhai, the type of treatment can be used to remove the anti-money agent having the modified layer formed on the surface thereof. The productivity can be increased, the production cost can be reduced, etc. 150733.doc -28· 201127950 The prior art can be applied to processes other than the processes of the cleaning method and the cleaning system according to the embodiment described above, and thus omitted Although the method for manufacturing a semiconductor device is illustrated as an example of the method for manufacturing the fine structure, the method for manufacturing the fine structure is not limited thereto. For example, in a liquid crystal display device, for example. In the field of phase shift masks, micromachines in the field of MEMS, precision optics, etc., applications can be realized. In the cleaning system described above, it is not always necessary to provide a configuration for circulating the solution. As illustrated in the solution, the solution used in the cleaning treatment unit 12 can be recycled to the reflux tank together with contaminants and the like and then via the discharge line. 75 is discharged to the outside of the system. This treatment may not be used to remove anti-surnames made of organic substances, and may be used to similarly remove metal impurities, particles, dry etching residues, etc. For example, having large cross-sections in patterning During the period of the metal interconnect, the deposition curtain has a plurality of interconnecting metals, oxides and imides of the interconnect metals, barrier metals, oxides and halides of the barrier metals, etc. Further, the patterning has a large During the aspect ratio system, a large number of cerium oxide and a sulphate are deposited. In many cases, substances such as ruthenium cannot be removed only by the oxidizing ability of the oxidizing substance of the SPM solution. However, it can be decomposed by hydrofluoric acid and Removing a plurality of deposits in such deposits. By using the above-described cleaning liquids, the cleaning methods, and the cleaning systems, the dioxide film (Si〇2) and nitrogen can be prevented from being damaged. This removal is achieved in the case of a fossil film (SlN). 150733.doc -29- 201127950 In other words, many applications can be realized when removing contaminants adhering to a fine structure. In this case, when oxides and nitrides Located in the It is especially useful when it is on the surface, because the contaminants can be removed while suppressing the removal of the oxides and the nitrides. A robot can be provided to transfer the object to be cleaned and hold the sulfuric acid solution. Each of the canister 60 and the canister holding the hydrofluoric acid can be connected to the factory line to automatically replenish the solution. A rinse tank can be provided for rinsing the article to be cleaned after removal of the contaminants. The rinsing tank may include an overflow control device and a temperature control device using an in-line heater. It is suitable to use quartz as the material of the rinsing tank. The embodiment is illustrated above. However, the invention is not limited to It is to be understood that the above-described embodiments of the present invention are intended to be included within the scope of the present invention. For example, the configuration, dimensions, material qualities, arrangements, etc. of such components of the cleaning systems set forth above are not limited to those illustrated herein and may be modified as appropriate. Further, the components of the embodiments set forth above may be combined within the scope of the invention; and such combinations are also included in the scope of the invention, including the features of the invention. Although certain embodiments have been described, these embodiments have been shown by way of example only and are not intended to limit the scope of the invention. In fact, the novel liquids, cleaning methods, cleaning systems, and manufacturing methods described herein are embodied in a variety of other forms, in the form of 150733.doc 30-201127950; in addition, the description herein can be made without departing from the spirit of the invention. Various omissions, substitutions, and changes in the form of liquids, cleaning methods, cleaning systems, and methods of manufacture. The accompanying claims and their equivalents are intended to cover such forms and modifications BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view illustrating a cleaning system according to this embodiment; FIGS. 2A and 2B are schematic views illustrating a mechanism for generating an oxidizing substance; FIG. 3 is a diagram illustrating concentrations of the oxidizing substances and sulfuric acid. Figure 4 is a flow chart illustrating the cleaning method; Figure 5 is a flow chart illustrating a cleaning method according to another embodiment; Figure 6 is a diagram illustrating that the electrolysis has an addition to A schematic diagram of a hydrofluoric acid sulfuric acid cleaning system; and FIG. 7 is a schematic diagram illustrating a cleaning system that does not provide a configuration of a circulating solution. [Main component symbol description] 5 Cleaning system 10 Sulfuric acid electrolysis unit 12 Cleaning processing unit 14 Solution circulation unit 15 Sulfuric acid supply unit 16 Cathode outlet 17 Anode outlet 150733.doc • 31· 201127950 18 Cathode inlet 19 Anode inlet 20 Separator 22 Upper end sealing unit 23 Lower end sealing unit 24 Electrolytic unit housing 26 DC power supply 28 Tank 29 Cover 30 Anode chamber 32 Anode 33 Anode support 34 Anode base member 35 Anode conductive film 40 Cathode chamber 42 Cathode 43 Cathode support 44 Cathode base member 45 Cathode conductive film 50 Hydrofluoric acid unit 51 Tank 52 Pump 53 Pipe line 53a Pipe line 150733.doc -32- 201127950 60 Tank 61 Distribution unit 62 Rotary table 63 Return tank 64 Filter 70 Open/close valve 71 Open/close valve 72 On/Off Valve 73 Pipe line 73a Open/close valve 74, 85 Line line 74a Open/close valve 75 Line line 75a Open/close valve 76 Open/close valve 80 Pump 81 Pump 82 Pump 86 Pipe line 91 Open/close valve 150733 .doc -33-