556055 A7 ____B7__ 五、發明說明（ί ) 【發明之詳細說明】 (請先閱讀背面之注意事項再填寫本頁) 【發明所屬之技術領域】 本發明係有關於半導體元件與光微影（lith〇graPhy) 等之製程所使用的感光性樹脂洗淨用稀釋劑（thinner)組 成物，特別是有關混合至少1種之共溶劑於丙二醇單甲醚 丙酸酯中所形成之稀釋劑組成物者，如此般的稀釋劑組成 物不僅相對感光性樹脂之溶解性優異，而且其蒸氣壓低， 並具有低揮發性與低毒性，在無用之感光膜的去除上可發 揮優異的效果。 【習知技術】 一般，半導體積體電路或全平面面板顯示器（Flat Panel Display，FPD)電路具有極微細的構造，故須經過多 階段的製程來製造。如此微細構造電路，係藉由將感光性 樹脂均一地塗佈於基板上所形成之氧化膜類的絕緣膜或鋁 合金膜類的導電性金屬膜，再對前述感光性樹脂進行曝光/ 顯像來形成既定的圖案，然後將圖案化成爲既定形狀的感 光性樹脂作爲光罩來蝕刻前述絕緣膜或導電性金屬膜，使 前述感光性樹脂的圖案複製於基板上。最後，以剝離液除 去前述感光性樹脂圖案。在如此的製程中，所謂「旋塗製 程」係指藉由在基板上塗佈感光性樹脂後，藉由旋轉所產 生的離心力，使塗佈膜均一地形成於基板上之製程。在進 行如此般的塗佈製程時，在基板的邊緣部分與後面部分存 在有因離心力所形成、呈粒子（particle)狀之無用的殘留 ____j___ 木紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 556055 _____B7_____ 五、發明說明（少） 感光性樹脂。於是，在前述塗佈製程之後續製程中，前述 殘留的粒子狀感光性樹脂，將成爲在微細構造電路受曝光 之過程中導致散焦（defocus)、散射等現象之原因，進而 使全體製程之產率降低。 欲除去如此般的殘留感光性樹脂，係在基板的邊緣部 分與後面部分設置感光膜去除裝置（Edge Bead Remover， EBR)，由此裝置的噴嘴噴射出洗淨用稀釋劑組成物來除 去前述殘留感光性樹脂。在決定作爲如此般稀釋劑組成物 性能之因素方面，可舉出如溶解速度、揮發性、黏度、感 光膜除去交界面之線性度（linearity)。 以下對前述稀釋劑之性能的決定因素作具體說明。 溶解速度 溶解速度係溶解/除去感光性樹脂之重要因素之一，其 對感光膜除去交界面之線性度具有極大的影響。亦即，在 溶解速度遠低於揮發速度的情況下，塗佈於基板上之感光 性樹脂方面，有可能呈現出所謂殘留（tailing)，即部分 被溶解之感光性樹脂殘留物（photoresist tail)的流動現象 之憂慮；相反地溶解速度遠高於揮發速度的情況下，在塗 佈於基板上之感光性樹脂的洗淨（rinse)製程中，有可能 呈現出所謂感光性樹脂受鈾（photoresist attack)的感光性 樹脂過度侵蝕現象之憂慮。這種相對於感光性樹脂之殘留 或侵蝕現象，在後續製程上將成爲不良的原因。因而，在 感光性樹脂洗淨用稀釋劑上，適當的溶解速度被要求。 _4_________ 衣紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱1 ^~' ---------------I----* 訂-------線 i (請先閱讀背面之注意事項再填寫本頁) 556055 A7 ___ B7___ 五、發明說明（；）） 揮發性 (請先閱讀背面之注意事項再填寫本頁) 揮發性係有關除去感光性樹脂後，稀釋劑如何地快速 揮發而不致殘留在基板表面者。在揮發性非常低的情況下 ，稀釋劑將不揮發而殘留，此不僅在感光膜除去交界面上 導致殘留現象，且在後續製程中將成爲妨礙粒子而存在， 而發生所謂使製程之生產性降低的問題。另一方面，在揮 發性非常高的情況下，因基板急速地被冷卻，故將發生： 於所塗佈的感光性樹脂上形成浮渣（scum)之現象，以及 在藉由感光膜去除裝置的噴嘴來噴射稀釋劑時，此稀釋劑 無法完全地溶解/除去感光性樹脂便揮發掉之問題。更者， 在操作過程中，因其揮發至大氣中，故有可能引發潔淨室 的污染、爆炸危險等之問題。 黏度 稀釋劑黏度，係藉由感光膜去除裝置的噴嘴來噴射稀 釋劑時應考慮之因素。在黏度太高的情況下’藉由噴嘴所 產生的噴射壓有過高之虞，無用之稀釋劑的使用量增加’ 而降低其經濟性。另一方面，在稀釋劑的黏度太低之情況 下，因感光性樹脂無法集中於感光膜除去交界面上’故有 導致不良之虞。 線性度 感光膜除去交界面之線性度，係與前述溶解速度、揮 發性及黏度有關連之因素，若不適當地整合溶解速度' 揮 ______5 ____ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 556055 A7 _ __B7_ ——___ 五、發明說明（命） 發性及黏度，則無法得到漂亮的交界面之線性度。因而’ 線性度可說是判斷感光性樹脂洗淨用稀釋劑組成物之性能 的最大因素。 另一方面，若考察以往的感光性樹脂洗淨用稀釋劑組 成物，則如下所述。其眾所皆知者有使用如丙二醇醚、丙 二醇醚醋酸酯的酯類；醚醋酸酯類；如丙酮、丁酮、曱基 異丁酮、2-庚酮、環己酮之酮類；以及如甲基乳酸酯、乙 基乳酸酯、甲基醋酸酯、乙基醋酸酯、丁基醋酸酯之酯類 的稀釋劑組成物（日本特開昭63 - 69563號公報）’使用 丙二醇單甲醚醋酸酯（propylene glycol monomethyl ether acetate，PGMEA)之稀釋劑組成物，以及使用烷基烷氧基 丙酸酯之稀釋劑組成物（日本特開平4 一 42523號公報）。 雖然如此般之以往的稀釋劑組成物係廣泛地使用主要 爲正丁基醋酸酯（n—butyl acetate，η—BA)、乙二醇單乙 基醚醋酸酯（ethylene glycol monomethyl ether acetate， ECA )、丙二醇單甲基醚醋酸酯（propylene glycol monomethyl ether acetate，PGMEA)以及乙基乳酸酯（ethyl lactate, EL)等之單一溶劑，然而此種單一溶劑在低溶解速 度、高揮發性、高黏度等方面皆具有問題。 爲了彌補如此單一組成物之缺點，係開發混合溶劑， 例如有由丙二醇烷基醚與3-烷氧基丙酸烷酯類之混合物 所構成之稀釋劑組成物（日本特開平7 - 146562號公報） ，或丙二醇烷基醚、丁基醋酸酯及乙基乳酸酯之混合物（ 日本特開平7- 128867號公報）等。 幸、紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 丨丨丨丨丨丨丨丨丨-------訂·--：------I J— (請先閱讀背面之注意事項再填寫本頁) 556055 A7 ___Β7______ 五、發明說明（< ) 又，在美國專利第4,983,490號中揭示由丙二醇烷基 醚醋酸酯與丙二醇烷基醚之混合溶劑的稀釋劑組成物，然 而此組成物除了因惡臭而給予作業者不舒適感與厭惡感， 同時因具有毒性而有傷害健康之憂慮。 更者，以往的混合溶劑因在其溶解性、揮發性、有毒 性、交界面的線性度、洗淨效果上成爲問題，故難適用於 高積體化半導體元件類的製造上。 【發明所欲解決之課題】 本發明係爲了解決如上所述之以往感光性樹脂洗淨用 稀釋劑與混合溶劑之問題點而被提案者，其目的係提供下 述之感光性樹脂洗淨用稀釋劑組成物：（1)在感光性樹脂 洗淨時具有優異之溶解性，（2)蒸氣壓低且低毒性、無潔 淨室的污染與爆炸危險性、並無損害作業者健康之疑慮， (3)黏度低且能降低藉由噴嘴所產生的噴射壓，因此可減 少其使用量來提升經濟性，（4)在藉由感光膜去除裝置的 噴嘴來噴射時，能顯示出感光性樹脂交界面之漂亮的線性 度。 【用以解決課題之手段】 爲了達成上記目的，本發明所提供之感光性樹脂洗淨 用稀釋劑組成物，係將10〜90重量％之丙二醇單甲醚丙酸 酯，與擇自丙二醇單烷基醚類、丙二醇單烷基醚醋酸酯類 _-__7 ____ 木紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------i I -----訂--^-------1 (請先閱讀背面之注意事項再填寫本頁) 556055 A7 _ — _B7__ 五、發明說明（k ) 、單羥基羧酸酯類、烷基酯類以及酮類所構成群中之至少 一種的共溶劑相混合而形成者。 其中，前述共溶劑若擇自丙二醇單甲基醚、丙二醇單 甲基醚醋酸酯、正丁基醋酸酯、乙基乳酸酯、乙基乙氧基 丙酸酯、甲基甲氧基丙酸酯、2-庚酮、r -丁內酯等所構 成群中之者，則較佳。 又，前述稀釋劑組成物若係將10〜50重量％之丙二 醇單甲醚丙酸酯與1種或2種的前述共溶劑混合所形成之 2成分系或3成分系稀釋劑組成物者，則更佳。 有關本發明之稀釋劑組成物，因其相對感光性樹脂之 溶解度優異，且具有適宜的揮發性與低毒性，故可發揮將 在半導體元件與光微影等之製程中，感光膜的旋佈製程中 於基板邊緣部分與後面部分所產生之無用感光膜加以除去 的優異效果，而能在藉由邊緣部分的無用感光膜去除之裝 置的噴嘴來噴射本發明的稀釋劑組成物時，得到相對於感 光膜交界面爲漂亮的線性度。 因而，在使用有關本發明之感光性樹脂洗淨用稀釋劑 組成物的情況下，藉由如感光膜洗淨（Edge Bead Rinse) 處理特性的增強、感光性樹脂的處理截面改善之效果，能 使半導體元件與光微影製程之生產性提升。 【發明之實施形態】 在本發明的稀釋劑組成物中，前述丙二醇單甲醚丙酸 - -8_ — - __ f、紙張尺度適用中國國家標準（CNs)A4規格（210 X 297公釐） --------------------* 訂---------線 1 (請先閲讀背面之注意事項再填寫本頁) 556055 B7 五、發明說明（V| ) 酯，其相對於各種樹脂之溶解度優異、且黏度低。又，即 使暴露於空氣中其安定性高、揮發性低。更者，LD50 (經 口）爲12g/kg，幾乎無毒性與因臭味所造成的不舒適感， 且具環境親和性。其物理性質爲沸點160°C、閃燃點（以 封閉蓋方式測定）56°C、黏度（在25°C下）l」8cps、蒸氣 壓（在20°C下）0_9mmHg、溶解度參數4.8。 然而，在僅以前述丙二醇單甲醚丙酸酯作爲感光性樹 脂洗淨用稀釋劑來使用的情況下’若與高溶解速度相比則 有所謂揮發性低的問題，且因低黏度導致在除去感光膜時 無法集中於交界面而可能會有招致不良之問題。 因而，最好混合能將單獨使用丙二醇單甲醚丙酸酯來 作爲感光性樹脂洗淨用稀釋劑時之缺點加以彌補的共溶劑 來製造稀釋劑組成物。 若舉例出欲去除丙二醇單甲醚丙酸酯之缺點而可作爲 共溶劑來使用者，則如下列所示。 首先，在本發明的稀釋劑組成物中作爲混合用共溶劑 而被使用之丙二醇單甲基醚，相對於感光性樹脂中之酚酸 樹脂與光活性物質具優異溶解性，其毒性數値LD50 (經口 )爲4.4g/kg，若吸入人體中，因其將快速地分解成丙二醇 與乙醇而使毒性減少，故不會傷害到作業者。然而’因其 高蒸氣造成其揮發性高，故若經長時間使用則會因惡臭而 給予作業者不舒適感，或因黏度高而難以單獨使用。物理 性質爲沸點132.8°C、閃燃點（以封閉蓋方式測定）32°C、 ______9 _ 木紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---I-----------I--丨 I *訂-----I I I I 1 (請先閱讀背面之注意事項再填寫本頁) 556055 A7 _B7_ __________ — -1 1 ................................................... ....... 1 丨丨丨_ 1 ' … 五、發明說明（各） 黏度（在25 °C下）1.86cps、蒸氣壓（在25 °C下） 12.6mmHg、表面張力26.5dyne/cm2、溶解度參數1〇·4。 其他，在本發明中作爲共溶劑而被使用之丙二醇單甲 基醚醋酸酯、正丁基醋酸酯、乙基乳酸酯、乙基乙氧基丙 酸酯、甲基甲氧基丙酸酯、2 —庚酮、7 —丁內酯等，亦因 具有如前述丙二醇單甲基醚之問題點，故難以單獨使用。 因此，在本發明中係以丙二醇單甲醚丙酸酯作爲主成 分，然後於當中混合一定比例之至少1種的前述共溶劑來 製造稀釋劑組成物。如此的稀釋劑組成物，可維持相對感 光性樹脂之高溶解性能、適宜的揮發性及黏度’亦可發揮 相對感光性樹脂除去交界面之線性度的優異特性。又，前 述所混合之組成物，在環境層面上能減低因惡臭所導致的 不舒適感，在安定面上則因低毒性/低閃燃點而無傷害作業 者健康之危險與爆炸危險之虞。 有關本發明之感光性樹脂洗淨用稀釋劑組成物，可藉 由以下的實施例來更明確地瞭解。 〔實施例〕 1.稀釋劑組成物的製浩 對於以一定比例混合丙二醇單甲醚丙酸酯與共溶劑所 成之稀釋劑組成物改變其組成比而如實施例1至28般地來 製造，另製造比較例組成物1與2，其結果顯示於下面的 〔表1〕中。 ____Η)_______ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） —-----------------訂---------Awi 1 (請先閱讀背面之注意事項再填寫本頁) 556055 A7 _B7______ 五、發明說明（1 ) 〔表1〕各實施例與比較例之稀釋劑組成物的製造（單位 :重量％) 區分 各稀釋劑的組成比 區分 各稀釋劑的組成比 實施例1 PMP ： PGME=90 ： 10 實施例16 PMP ： MMP ： EL=35 ： 50 ： 15 實施例2 PMP ： PGME = 80 ： 20 實施例17 PMP ： MMP ： EL=55 ： 30 ： 15 實施例3 PMP ： PGME = 70 ： 30 實施例18 PMP ： PGME ： MAKN= 10 ： 70 ： 20 實施例4 PMP ： PGME = 50 ： 50 實施例19 PMP ： PGME ： MAKN= 10 ： 80 ： 10 實施例5 PMP ： PGME = 30 ： 70 實施例20 PMP : PGME : nBA= 10 : 80 : 10 實施例6 PMP ： PGME = 20 ： 80 實施例21 PMP ： PGME ： nBA=30 ： 60 ： 10 實施例7 PMP ： PGME=10 ： 90 實施例22 PMP ： PGME ： nBA=50 ： 40 ： 10 實施例8 PMP ： EL=25 ： 75 實施例23 PMP ： EA ： GBL=30 ： 65 ： 5 實施例9 PMP ： EL=75 ： 25 實施例24 PMP ： EA ： GBL = 60 ： 35 ： 5 實施例10 PMP ： MMP = 75 ： 25 實施例25 PMP ： EA ： GBL=80 ： 15 ： 5 實施例11 PMP ： MMP = 25 ： 75 實施例26 PMP : PGMEA : EA= 10 : 10 : 80 實施例12 PMP ： EEP ： EL=20 ： 60 ： 20 實施例27 PMP ： PGMEA ： EA=40 ： 10 ： 50 實施例13 PMP ： EEP ： EL=40 ： 40 ： 20 實施例28 PMP ： PGMEA ： EA=60 ： 10 ： 30 實施例14 PMP ： EEP ： EL=60 ： 20 ： 20 比較例1 EL ： EEP = 20 ： 80 實施例15 PMP ： MMP ： EL=25 ： 60 ： 15 比較例2 EL ： PGME = 50 ： 50 其中 PMP :丙二醇單甲醚丙酸酯 PGME :丙二醇單甲基醚 EL :乙基乳酸酯 GBL : r — 丁內酯 MMP :甲基甲氧基丙酸酯 EEP :乙基乙氧基丙酸酯 nBA :正丁基醋酸酯 EA :乙基醋酸酯 PGMEA :丙二醇單甲基醚醋酸酯 MAKN : 2 —庚酮 _11 衣紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------1 (請先閱讀背面之注意事項再填寫本頁) 556055 A7 ___— —____B7_______ 五、發明說明（) 2.相對正型[感1忤樹脂之稀釋劑組成物的溶解速度評價 將一般所使用的感光性樹脂組成物中之g一1ine正型 感光性樹脂組成物塗佈於4 inch的氧化矽晶圓上，在110 °C下做軟烘烤90秒後，再切成lcmX lcm的試驗片並於室 溫下使其沈澱於前述〔表丨〕的各稀釋劑溶液中’測定完 全除去感光性樹脂之時間。將作爲其結果的彳谷解速度顯不 於以下的〔表2〕中。 〔表2〕相對感光性樹脂之各稀釋劑組成物的溶解速度評 價（單位：A/sec) 溶解速度 區分 溶解速度 實施例1 7200 實施例16 10358 實施例2 7568 實施例17 9238 實施例3 8625 一 實施例18 13758 實施例4 10781 實施例19 14820 實施例5 12778 實施例20 14532 實施例6 13687 — 實施例21 12456 實施例7 15682 實施例22 10220 實施例8 10835 實施例23 15202 實施例9 8423 實施例24 10462 實施例10 9232 實施例25 9230 實施例11 12330 — 實施例26 14438 實施例12 12330 實施例27 11897 實施例13 9456 實施例28 8432 實施例14 8720 9945 實施例15 12563 ____ 8222 12 本·紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 556055 A7 ____B7_ 五、發明說明（\() 3.各稀釋劑組成物之揮發件評價 爲了測定各稀釋劑組成物的揮發性，使用旋塗機（ Spin Coater，瑪他斯社）在4 inch的晶圓上滴下各稀釋劑 組成物ImL，然後一邊將旋轉速度變化成1〇〇〇、2000、 3000rpm，一邊測定至晶圓的邊緣部分之稀釋劑完全揮發 所需的時間。其結果顯示於以下的〔表3〕中。 〔表3〕各稀釋劑組成物之揮發性評價（單位：sec) 區分 揮發時間 區分 ^ 揮發時間 lOOOrpm 2000rpm 3000rpm lOOOrpm 2000rpm 3000rpm 實施例1 26.3 13.1 9.2 實施例16 23.6 11.7 8.2 實施例2 25.1 12.5 8.8 實施例17 25.8 12.7 8.3 實施例3 24.2 12.0 8.5 實施例18 11.6 6.1 4.6 實施例4 22.1 11.1 8.1 實施例19 11.1 6.0 4.5 實施例5 20.1 10.1 7.1 實施例20 17.1 8.6 6.4 實施例6 19.1 9.6 6.8 實施例21 19.2 9.6 6.8 實施例7 18.0 9.0 6.4 實施例22 21.2 10.6 7.5 實施例8 34.9 16.4 11.2 實施例23 16.2 7.9 5.6 實施例9 30.2 14.8 10.4 實施例24 23.4 11.5 8.0 實施例10 24.6 12.2 8.6 實施例25 28.2 13.8 9.7 實施例11 19.2 9.7 6.7 實施例26 7.4 3.6 2.7 實施例12 34.8 16.9 11.8 實施例27 14.5 7.2 5.1 實施例13 33.1 16.1 11.3 實施例28 19.3 9.5 6.8 實施例14 31.3 15.3 10.7 比較例1 36.0 17.4 12.1 實施例15 22.6 11.2 7.8 比較例2 48.2 23.8 11.7 _______13 幸、紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---I----- I 丨皿 i — I 丨 — 丨訂丨 — (請先閱讀背面之注意事項再填寫本頁) 556055 A7 B7 五、發明說明（l>) 4.各稀釋劑組成物之線性度評價 使用各稀釋劑組成物，在除去邊緣部分之無用感光性 樹脂後，測定其交界面之線性度。使用旋塗機（Spin Coater，瑪他斯社），以1500rpm塗佈各感光性樹脂於4 inch的晶圓上，然後在EBR的噴嘴壓力l.〇kg.f/cm、稀釋 劑流量12mL/min、旋塗機2000rpm的條件下除去感光性 樹脂後，使用光學顯微鏡測定處理截面。其結果顯示於以 下的〔表4〕與圖1〜圖9中。 〔表4〕各稀釋劑組成物之線性度評價 區分 線性度 對應圖式 區分 線性度 對應圖式 實施例4 Δ 實施例15 ◎ 圖6 實施例5 ◎ 圖1 實施例19 ◎ — 實施例ό ◎ 圖2 實施例21 ◎ 圖7 實施例7 ◎ 圖3 實施例23 ◎ — 實施例8 Δ — 實施例27 ◎ — 實施例11 ◎ 圖4 比較例1 Δ 圖8 實施例12 Δ 圖5 比較例2 X 圖9 其中 ◎:處理截面漂亮（線性度普通） △:處理截面稍被侵蝕（線性度普通、受蝕現象） X:在處理截面上殘留有過量的殘留物（線性度低、殘留現象） 由以上可知，與比較例1與2之結果相比，本發明之 感光性樹脂洗淨用稀釋劑組成物，係如顯示於〔袠2〕〜 〔表4〕之相對溶解速度、揮發性、線性度的各實驗與其 ____14_______ 幸、紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " '' --------------------訂—^-------ί (請先閱讀背面之注意事項再填寫本頁) A7 556055 ___B7___ 五、發明說明) (請先閱讀背面之注意事項再填寫本頁) 結果所示般，具有優異的前述各特性。例如在個別的性能 上，即使類似於比較例，在整體的特性上仍可說優於比較 例。特別是，如前所述，因稀釋劑組成物的感光膜除去交 界面之線性度係與溶解速度、揮發性、黏度有關連之因素 ，故由相對於〔表4〕與圖1〜圖9之線性度程度的光學顯 微鏡照片中可明白地知道，其顯著地優於比較例1與2。 除圖1〜圖9所示有關本發明之各實施例的光學顯微鏡照 片外，其他實施例的照片亦顯示出類似的線性度。 本發明之保護範圍並不受前述稀釋劑組成物的各實施 例所限制。 【發明之效果】 如上所述，有關本發明之感光性樹脂洗淨用稀釋劑組 成物，係有（1)在感光性樹脂洗淨時具有優異之溶解性 ，（2)蒸氣壓低且低毒性、無潔淨室的污染與爆炸危險 性、並無損害作業者健康之疑慮，（3)黏度低且能降低 藉由噴嘴所產生的噴射壓，因此可減少其使用量來提升經 濟性，（4)在藉由感光膜去除裝置的噴嘴來噴射時，能 顯示出感光性樹脂交界面之漂亮線性度；等效果。 【圖式之簡單說明】 圖1〜圖9係檢查與本發明之感光性樹脂洗淨用稀釋 劑組成物的各實施例及比較例有關之線性度程度的光學顯 微鏡照片。 __15___-__ 木紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）556055 A7 ____B7__ V. Description of the invention (Detailed description of the invention) (Please read the notes on the back before filling out this page) [Technical field to which the invention belongs] The present invention relates to semiconductor elements and photolithography (lithography). graPhy) and other thinner compositions for cleaning of photosensitive resins used in manufacturing processes, especially those containing at least one type of co-solvent in propylene glycol monomethyl ether propionate, Such a diluent composition not only has excellent solubility with respect to a photosensitive resin, but also has low vapor pressure, low volatility and low toxicity, and can exhibit excellent effects in removing useless photosensitive films. [Known Technology] Generally, semiconductor integrated circuits or flat panel display (FPD) circuits have extremely fine structures, so they must be manufactured through a multi-stage process. Such a finely structured circuit is an oxide film-based insulating film or an aluminum alloy film-based conductive metal film formed by uniformly coating a photosensitive resin on a substrate, and then exposing / developing the photosensitive resin. A predetermined pattern is formed, and then the photosensitive resin patterned into a predetermined shape is used as a mask to etch the insulating film or the conductive metal film, and the pattern of the photosensitive resin is copied on a substrate. Finally, the photosensitive resin pattern is removed with a peeling solution. In such a process, the "spin coating process" refers to a process in which a coating film is uniformly formed on a substrate by applying a centrifugal force generated by rotation after a photosensitive resin is coated on the substrate. During such a coating process, there are useless residues in the shape of particles that are formed by the centrifugal force on the edge and the back of the substrate. 210 X 297 mm) A7 556055 _____B7_____ 5. Description of the invention (less) Photosensitive resin. Therefore, in the subsequent processes of the coating process, the residual particulate photosensitive resin will cause defocus, scattering and other phenomena during the exposure of the micro-structured circuit, which will further increase the overall system process. Yield decreases. To remove such residual photosensitive resin, a photosensitive film removal device (Edge Bead Remover, EBR) is installed on the edge portion and the rear portion of the substrate, and the nozzle of the device sprays a thinner composition for cleaning to remove the residual Photosensitive resin. Factors that determine the performance of such a diluent composition include, for example, the dissolution rate, volatility, viscosity, and linearity of the photosensitive film without the interface. The factors that determine the performance of the aforementioned diluent will be specifically described below. Dissolution rate The dissolution rate is one of the important factors for dissolving / removing the photosensitive resin, and it has a great influence on the linearity of the interface where the photosensitive film is removed. That is, when the dissolution rate is much lower than the volatilization rate, the photosensitive resin coated on the substrate may exhibit so-called tailing, that is, the partially-dissolved photosensitive resin residue (photoresist tail). Contrary to the phenomenon of flow phenomenon; on the contrary, when the dissolution rate is much higher than the volatilization rate, during the rinse process of the photosensitive resin coated on the substrate, the so-called photosensitive resin may be exposed to uranium (photoresist). Anxiety is concerned about excessive erosion of photosensitive resin. This kind of residue or erosion with respect to the photosensitive resin will be a cause of failure in subsequent processes. Therefore, an appropriate dissolution rate is required for the thinner for washing photosensitive resins. _4_________ Applicable to China National Standard (CNS) A4 specifications (210 X 297 Public Love 1 ^ ~ '--------------- I ---- * Order ----- --Line i (Please read the precautions on the back before filling this page) 556055 A7 ___ B7___ V. Description of the invention (;)) Volatility (Please read the precautions on the back before filling this page) Volatility is about removing photosensitivity How does the thinner evaporate quickly after the resin is not retained on the surface of the substrate. In the case of very low volatility, the diluent will not volatilize and remain. This will not only cause a residual phenomenon at the interface where the photosensitive film is removed, but will also be an obstacle to particles in subsequent processes. Reduced problems. On the other hand, in the case of very high volatility, the substrate is rapidly cooled, so that scum will be formed on the coated photosensitive resin, and the device will be removed by a photosensitive film. When the thinner is sprayed with a thin nozzle, the thinner cannot completely dissolve / remove the photosensitive resin and volatilize. Moreover, during operation, it may cause problems such as pollution and explosion hazards in the clean room because it volatilizes into the atmosphere. Viscosity The viscosity of the thinner is a factor to be considered when spraying the thinner through the nozzle of the photosensitive film removal device. In the case where the viscosity is too high, 'the injection pressure generated by the nozzle may be too high, and the use amount of an unnecessary diluent increases', thereby reducing its economical efficiency. On the other hand, when the viscosity of the diluent is too low, the photosensitive resin cannot be concentrated on the removal interface of the photosensitive film ', which may cause a defect. Linearity The linearity of the photosensitive film except for the interface is a factor related to the aforementioned dissolution speed, volatility and viscosity. If the dissolution speed is inappropriately integrated, it is _______5 ____ This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 556055 A7 _ __B7_ ——___ V. Description of the invention (Life) The properties and viscosity of the interface can not obtain the linearity of the beautiful interface. Therefore, the linearity can be said to be the biggest factor in judging the performance of the thinner composition for cleaning of photosensitive resin. On the other hand, if a conventional thinner composition for cleaning a photosensitive resin is examined, it will be as follows. It is known to use esters such as propylene glycol ethers, propylene glycol ether acetates; ether acetates; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and Diluent compositions such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, and butyl acetate (Japanese Patent Laid-Open No. 63-69563) using propylene glycol alone A diluent composition of propylene glycol monomethyl ether acetate (PGMEA), and a diluent composition using an alkyl alkoxypropionate (Japanese Patent Laid-Open No. 4-42523). In spite of this, conventional diluent compositions are widely used mainly n-butyl acetate (η-BA) and ethylene glycol monomethyl ether acetate (ECA). , Propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) and other single solvents, but this single solvent at low dissolution rate, high volatility, high viscosity There are problems in other aspects. In order to make up for the shortcomings of such a single composition, a mixed solvent has been developed. For example, a diluent composition composed of a mixture of propylene glycol alkyl ether and alkyl 3-alkoxypropionate (Japanese Patent Application Laid-Open No. 7-146562 ), Or a mixture of propylene glycol alkyl ether, butyl acetate, and ethyl lactate (Japanese Patent Laid-Open No. 7-128867) and the like. Fortunately, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 丨 丨 丨 丨 丨 丨 丨 丨 丨 ------ Order ·-: ------ IJ— ( Please read the precautions on the back before filling out this page) 556055 A7 ___ Β7 ______ 5. Description of the invention (<) Also disclosed in US Patent No. 4,983,490 is the dilution of a mixed solvent of propylene glycol alkyl ether acetate and propylene glycol alkyl ether Agent composition, however, in addition to giving the operator discomfort and aversion due to malodor, it also has the concern of harming health due to its toxicity. Furthermore, conventional mixed solvents have problems in terms of solubility, volatility, toxicity, interface linearity, and cleaning effect, and are therefore difficult to apply to the manufacture of high-integration semiconductor devices. [Problems to be Solved by the Invention] The present invention was proposed by the present invention in order to solve the problems of conventional thinners and mixed solvents for cleaning of photosensitive resins as described above, and its purpose is to provide the following cleaning of photosensitive resins Diluent composition: (1) excellent solubility when the photosensitive resin is cleaned, (2) low vapor pressure and low toxicity, no pollution and explosion hazard in clean rooms, and no concerns about harming the health of workers, ( 3) Low viscosity and can reduce the injection pressure generated by the nozzle, so it can reduce the amount of use to improve economic efficiency. (4) When sprayed through the nozzle of the photosensitive film removal device, it can show the photosensitive resin Beautiful linearity of the interface. [Means to solve the problem] In order to achieve the above purpose, the thinner composition for cleaning of photosensitive resin provided by the present invention is composed of 10 to 90% by weight of propylene glycol monomethyl ether propionate and a propylene glycol monomethyl ether Alkyl ethers, propylene glycol monoalkyl ether acetates _-__ 7 ____ Wood paper standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) ------------ i I ----- Order-^ ------- 1 (Please read the notes on the back before filling out this page) 556055 A7 _ — _B7__ V. Description of the invention (k), monohydroxycarboxylic acid esters, A cosolvent in which at least one of the group consisting of alkyl esters and ketones is mixed is formed. The co-solvent is selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, n-butyl acetate, ethyl lactate, ethyl ethoxy propionate, and methyl methoxy propionic acid. Ester, 2-heptanone, r-butyrolactone and the like are more preferred. In addition, if the diluent composition is a two-component or three-component diluent composition formed by mixing 10 to 50% by weight of propylene glycol monomethyl ether propionate and one or two of the co-solvents, Even better. The diluent composition of the present invention has excellent solubility with respect to a photosensitive resin, and has suitable volatility and low toxicity. Therefore, the thinner composition of the photoresist can be used in the fabrication of semiconductor films and photolithography. The excellent effect of removing the unnecessary photosensitive film generated at the edge and the rear part of the substrate during the manufacturing process can be obtained when the thinner composition of the present invention is sprayed through the nozzle of the device for removing the unnecessary photosensitive film at the edge. Beautiful linearity at the interface of the photosensitive film. Therefore, when the thinner composition for cleaning a photosensitive resin according to the present invention is used, the effects such as enhancement of the processing characteristics of the edge film cleaning (Edge Bead Rinse) and improvement of the processed cross-section of the photosensitive resin can be achieved. Improve the productivity of semiconductor devices and photolithography processes. [Embodiment of the invention] In the diluent composition of the present invention, the aforementioned propylene glycol monomethyl ether propionic acid--8_ —-__ f. The paper size applies the Chinese National Standard (CNs) A4 specification (210 X 297 mm)- ------------------- * Order --------- Line 1 (Please read the notes on the back before filling this page) 556055 B7 V. Invention Explain that (V |) ester has excellent solubility in various resins and low viscosity. In addition, it has high stability and low volatility even when exposed to air. Furthermore, LD50 (oral) is 12g / kg, which is almost non-toxic and uncomfortable due to odor, and has environmental compatibility. Its physical properties are a boiling point of 160 ° C, a flash point (measured by a closed lid) of 56 ° C, a viscosity (at 25 ° C) of 1 ”8cps, a vapor pressure (at 20 ° C) of 0-9mmHg, and a solubility parameter of 4.8. However, when the propylene glycol monomethyl ether propionate is used only as a thinner for washing photosensitive resins, there is a problem of so-called low volatility when compared with a high dissolution rate, and the low viscosity causes When the photosensitive film is removed, it cannot concentrate on the interface and may cause problems. Therefore, it is desirable to produce a diluent composition by mixing a co-solvent which can make up for the shortcomings of using propylene glycol monomethyl ether propionate alone as a thinner for cleaning photosensitive resins. The following is an example of using propylene glycol monomethyl ether propionate as a co-solvent to remove the disadvantages of propylene glycol monomethyl ether propionate. First, the propylene glycol monomethyl ether used as a co-solvent for mixing in the diluent composition of the present invention has excellent solubility with respect to the phenolic resin and the photoactive substance in the photosensitive resin, and has a toxicity number LD50. It is 4.4 g / kg (orally). If it is inhaled into the human body, it will quickly decompose into propylene glycol and ethanol and reduce the toxicity, so it will not hurt the operator. However, because of its high volatility, it has high volatility. If it is used for a long time, it will give an uncomfortable feeling to the operator due to malodor, or it will be difficult to use it alone because of its high viscosity. The physical properties are boiling point 132.8 ° C, flash point (measured by closed lid) 32 ° C, ______9 _ Wood paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) --- I ---- ------- I-- 丨 I * Order ----- IIII 1 (Please read the notes on the back before filling this page) 556055 A7 _B7_ __________ — -1 1 ........ .......................................................... 1 丨 丨 丨 _ 1 '… 5. Description of the invention (each) Viscosity (at 25 ° C) 1.86cps, vapor pressure (at 25 ° C) 12.6mmHg, surface tension 26.5dyne / cm2, solubility parameter 1〇 · 4. In addition, propylene glycol monomethyl ether acetate, n-butyl acetate, ethyl lactate, ethyl ethoxy propionate, and methyl methoxy propionate used as co-solvents in the present invention , 2-heptanone, 7-butyrolactone, etc., are also difficult to use alone because they have the same problems as the aforementioned propylene glycol monomethyl ether. Therefore, in the present invention, a diluent composition is produced by using propylene glycol monomethyl ether propionate as a main component, and then mixing at least one of the aforementioned co-solvents in a certain proportion. Such a diluent composition can maintain high solubility of a relatively photosensitive resin, suitable volatility, and viscosity ', and can also exhibit excellent characteristics of linearity with respect to a photosensitive resin except for an interface. In addition, the above-mentioned mixed composition can reduce the discomfort caused by malodor on the environmental level, and on the stable surface, it has no danger of harming the health and explosion of the operator due to low toxicity / low flash point. The thinner composition for cleaning a photosensitive resin of the present invention will be more clearly understood from the following examples. [Examples] 1. Preparation of a diluent composition The diluent composition prepared by mixing propylene glycol monomethyl ether propionate and a co-solvent at a certain ratio was changed to a composition ratio and manufactured as in Examples 1 to 28. Comparative Examples 1 and 2 were produced separately, and the results are shown in [Table 1] below. ____ Η) _______ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----------- Order --------- Awi 1 (Please read the precautions on the back before filling out this page) 556055 A7 _B7______ V. Description of the invention (1) [Table 1] Manufacturing of thinner compositions for each example and comparative example (unit: weight%) Composition ratio of thinners Composition ratio of each diluent Example 1 PMP: PGME = 90: 10 Example 16 PMP: MMP: EL = 35: 50: 15 Example 2 PMP: PGME = 80: 20 Example 17 PMP : MMP: EL = 55: 30: 15 Example 3 PMP: PGME = 70: 30 Example 18 PMP: PGME: MAKN = 10: 70: 20 Example 4 PMP: PGME = 50: 50 Example 19 PMP: PGME : MAKN = 10: 80: 10 Example 5 PMP: PGME = 30: 70 Example 20 PMP: PGME: nBA = 10: 80: 10 Example 6 PMP: PGME = 20: 80 Example 21 PMP: PGME: nBA = 30: 60: 10 Example 7 PMP: PGME = 10: 90 Example 22 PMP: PGME: nBA = 50: 40: 10 Example 8 PMP: EL = 25 75 Example 23 PMP: EA: GBL = 30: 65: 5 Example 9 PMP: EL = 75: 25 Example 24 PMP: EA: GBL = 60: 35: 5 Example 10 PMP: MMP = 75: 25 Implementation Example 25 PMP: EA: GBL = 80: 15: 5 Example 11 PMP: MMP = 25: 75 Example 26 PMP: PGMEA: EA = 10: 10: 80 Example 12 PMP: EEP: EL = 20: 60: 20 Example 27 PMP: PGMEA: EA = 40: 10: 50 Example 13 PMP: EEP: EL = 40: 40: 20 Example 28 PMP: PGMEA: EA = 60: 10: 30 Example 14 PMP: EEP: EL = 60: 20: 20 Comparative Example 1 EL: EEP = 20: 80 Example 15 PMP: MMP: EL = 25: 60: 15 Comparative Example 2 EL: PGME = 50: 50 where PMP: propylene glycol monomethyl ether propionic acid Ester PGME: propylene glycol monomethyl ether EL: ethyl lactate GBL: r — butyrolactone MMP: methyl methoxypropionate EEP: ethyl ethoxy propionate nBA: n-butyl acetate EA : Ethyl acetate PGMEA: Propylene glycol monomethyl ether acetate MAKN: 2 —Heptanone_11 The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------------------- Order --------- 1 (Please read the notes on the back before filling this page) 556055 A7 ___ — —____ B7_______ 5. Explanation of the invention () 2. Relative positive type [Evaluation of the dissolution rate of the diluent composition of the resin 1 忤 resin The g-1ine positive photosensitive resin in the photosensitive resin composition generally used is evaluated The composition was coated on a 4 inch silicon oxide wafer, and after soft baking at 110 ° C for 90 seconds, the test piece was cut into lcm x lcm and precipitated at room temperature in the above [Table 丨]. In each diluent solution, the time until the photosensitive resin was completely removed was measured. The results of the Kariya solution rate are not shown in the following [Table 2]. [Table 2] Evaluation of the dissolution rate of each thinner composition of the photosensitive resin (unit: A / sec) Dissolution rate Differentiation of dissolution rate Example 1 7200 Example 16 10358 Example 2 7568 Example 17 9238 Example 3 8625 An example 18 13758 Example 4 10781 Example 19 14820 Example 5 12778 Example 20 14532 Example 6 13687 — Example 21 12456 Example 7 15682 Example 22 10220 Example 8 10835 Example 23 15202 Example 9 8423 Example 24 10462 Example 10 9232 Example 25 9230 Example 11 12330-Example 26 14438 Example 12 12330 Example 27 11897 Example 13 9456 Example 28 8432 Example 14 8720 9945 Example 15 12563 ____ 8222 12 This · Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------------------- Order --------- Line (Please read the precautions on the back before filling this page) 556055 A7 ____B7_ V. Description of the invention (\ () 3. Evaluation of volatile components of each diluent composition In order to determine the volatility of each diluent composition, use a spin coater (Spin Coater, Matas Co., Ltd.) ImL of each diluent composition was dripped onto a 4-inch wafer, and the time required for the diluent to completely volatilize to the edge of the wafer was measured while changing the rotation speed to 1,000, 2000, and 3000 rpm. The results are shown in the following [Table 3]. [Table 3] Volatility evaluation (unit: sec) of each diluent composition Distinguishing volatility time ^ Volatile time 1000 rpm 2000 rpm 3000 rpm 1000 rpm 2000 rpm 3000 rpm Example 1 26.3 13.1 9.2 Example 16 23.6 11.7 8.2 Example 2 25.1 12.5 8.8 Example 17 25.8 12.7 8.3 Example 3 24.2 12.0 8.5 Example 18 11.6 6.1 4.6 Example 4 22.1 11.1 8.1 Example 19 11.1 6.0 4.5 Example 5 20.1 10.1 7.1 Example 20 17.1 8.6 6.4 Example 6 19.1 9.6 6.8 Example 21 19.2 9.6 6.8 Example 7 18.0 9.0 6.4 Example 22 21.2 10.6 7.5 Example 8 34.9 16.4 11.2 Example 23 16.2 7.9 5.6 Example 9 30.2 14.8 10.4 Example 24 23.4 11.5 8.0 Example 10 24.6 12.2 8.6 Example 25 28.2 13.8 9.7 Example 11 19.2 9.7 6.7 Example 26 7.4 3.6 2.7 Example 12 34.8 16.9 11. 8 Example 27 14.5 7.2 5.1 Example 13 33.1 16.1 11.3 Example 28 19.3 9.5 6.8 Example 14 31.3 15.3 10.7 Comparative Example 1 36.0 17.4 12.1 Example 15 22.6 11.2 7.8 Comparative Example 2 48.2 23.8 11.7 _______13 Fortunately, the paper size is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) --- I ----- I 丨 Ware i — I 丨 — 丨 Order 丨 — (Please read the precautions on the back before filling this page) 556055 A7 B7 V. Description of the invention (l >) 4. Evaluation of linearity of each diluent composition Using each diluent composition, after removing the useless photosensitive resin at the edge portion, measure the linearity of the interface. Using a spin coater (Spin Coater, Matas), each photosensitive resin was coated on a 4-inch wafer at 1500 rpm, and then the EBR nozzle pressure was 1.0 kg.f / cm, and the diluent flow rate was 12 mL / After removing the photosensitive resin under a spin coater at 2000 rpm, the treated cross section was measured using an optical microscope. The results are shown in the following [Table 4] and Figs. 1 to 9. [Table 4] Linearity evaluation of each diluent composition Distinguish linearity corresponding pattern Distinguish linearity corresponding pattern Example 4 Δ Example 15 ◎ Figure 6 Example 5 ◎ Figure 1 Example 19 ◎ — Example ◎ Figure 2 Example 21 ◎ Figure 7 Example 7 ◎ Figure 3 Example 23 ◎ — Example 8 Δ — Example 27 ◎ — Example 11 ◎ Figure 4 Comparative Example 1 Δ Figure 8 Example 12 Δ Figure 5 Comparative Example 2 X Figure 9 Among them: ◎: beautiful cross-section (normal linearity) △: slightly eroded cross-section (normal linearity, corroded phenomenon) X: excessive residue left on the processed cross-section (low linearity, residual phenomenon) From the above, it can be seen that, compared with the results of Comparative Examples 1 and 2, the thinner composition for cleaning the photosensitive resin of the present invention has the relative dissolution rate, volatility, as shown in [袠 2] to [Table 4]. The experiments of linearity and its ____14_______ Fortunately, the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " '' ------------------ --Order — ^ ------- ί (Please read the notes on the back before filling out this page) A7 556 055 ___B7___ V. Description of the invention) (Please read the precautions on the reverse side before filling out this page) The results are as shown, and have the excellent characteristics mentioned above. For example, in terms of individual performance, even if it is similar to the comparative example, it can be said that the overall characteristics are better than the comparative example. In particular, as described above, the linearity of the thin film composition's photosensitive interface except the interface is related to the dissolution rate, volatility, and viscosity. It can be clearly seen from the optical microscope photograph of the degree of linearity that it is significantly superior to Comparative Examples 1 and 2. Except for the optical microscope photographs related to the embodiments of the present invention shown in Figs. 1 to 9, the photographs of other embodiments also show similar linearity. The scope of protection of the present invention is not limited by the embodiments of the aforementioned diluent composition. [Effects of the Invention] As mentioned above, the thinner composition for cleaning the photosensitive resin of the present invention has (1) excellent solubility when the photosensitive resin is washed, and (2) low vapor pressure and low toxicity. No pollution and explosion hazards in clean rooms, no concerns about operator's health, (3) Low viscosity and can reduce the injection pressure generated by the nozzle, so it can reduce its usage to improve economy, (4 ) When sprayed through the nozzle of the photosensitive film removal device, it can show the beautiful linearity of the interface of the photosensitive resin; and other effects. [Brief description of the drawings] Figs. 1 to 9 are optical microscope photographs examining the degree of linearity related to the respective examples and comparative examples of the thinner composition for cleaning photosensitive resins of the present invention. __15 ___-__ Wood paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)