1275907 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關設於基板上，含具孤立電子對原子之層 ’例如，氮化矽、四氮化三矽、磷•矽酸玻璃、硼•磷· 矽酸玻璃或氮化鈦層上形成抗蝕圖型時，可形成高解析度 ’而無基腳等缺陷，剖面形狀優之抗蝕圖型之感光性層合 物中之化學放大型正型抗蝕組成物。 【先前技術】 近年來，半導體裝置之積體密度日高，同時設計法則 (Design Rule )在0 · 20微米附近之LS I已開始量 產，不久設計法則0 · 1 5微米附近之L S I ，其量產亦 將出現。 最近有化學放大型正型抗蝕組成物之提議，因其相較 於用清漆樹脂作基材樹脂，用萘醌二迭氮磺酸酯作感光劑 之習知非化學放大型抗蝕物解析度、感度優，故已漸受採 用。 如此之化學放大型正型抗蝕組成物，已知有例如，用 對（1 一乙氧基乙氧基）苯乙烯及對羥基苯乙烯共聚物作 基材樹脂，用雙（環己基磺醯基）重氮基甲烷之類的磺醯 基重氮基甲烷系酸產生劑作爲酸產生劑者。（日本專利特 開平5 — 249682號公報）。 其因係溶解物制基，相對弱酸亦可解離之縮醛基，及 產生相對弱酸之磺醯基重氮基甲烷系化合物之組合，而可 1275907 (2) 形成高解析度之抗鈾圖型。當使用僅具縮醛基之基材樹脂 時，除一旦形成之抗蝕圖型有隨時間經過變細之傾向外， 亦未必有滿意之耐熱性、基板隨從性等，難以實用化。 爲克服這類缺點，有使用含縮醛基再加上三級丁氧基 類基、三級丁基、四氫吡喃基等弱酸難解離，強酸解離之 酸解離基之共聚物、混合樹脂，及磺醯基重氮基甲烷系酸 產生劑之化學放大型抗蝕組成物之提議，目前這些亦已成 爲主流。 另一方面，半導體裝置之製造中，隨其使用目的，係 於基材上設絕緣層、半導體層、金屬層等，再用設有抗蝕 層所成之感光性層合物，形成抗蝕圖型。 通常，該絕緣層係用氧化矽（S i〇2 )、氮化矽（ s i N )、四氮化三矽（S i 3 N 4 )、五氧化二鉅（ T a 2 0 5 )、磷•矽酸玻璃（PSG)、硼•磷•矽酸 玻璃（BPSG)、有機SOG、聚醯亞胺層等，半導體 層係用多晶矽層，金屬層用鋁、鋁·矽合金、鋁•矽•銅 合金、矽化鎢（WSi)、氮化鈦（TiN)等之層。 至於設有這些層之感光性層合物，目前爲止可形成 〇 · 3 0微米左右之微細圖型即充分達到目的，但隨最微 細設計法則所要求之0 · 1 5微米附近之L S I之量產， 對這些感光性層合物亦已有0 · 2 5微米左右之圖型尺寸 之要求。 然而，使用如此之感光性層合物形成上述之微細圖型 時，於含具有孤立電子對原子之SiN、SisN4、 1275907 (3) P SG、BP SG或T i N等之層與抗蝕圖型層之邊界難 免產生基腳，剖面形狀受損。 【發明內容】 發明槪要 本發明鑒於上情，其目的在提供，於如S i N、 S i 3N4、P SG、BP SG或T i N層之含具有孤立 電子對原子之層上形成抗蝕圖型時，可防這些層與抗蝕層 邊界產生基腳之感光性層合物之化學放大型正型抗蝕組成 物。 本發明人等對於在基板上，介以含具有孤立電子對原 子之層，設化學放大型正型抗蝕層之感光性層合物，用以 形成抗蝕圖型之際，抑制基腳產生之手段一再加以種種硏 究’結果發現，使用含特定樹脂成分、特定膜減量之酸產 生劑及胺之組合之化學放大型正型抗蝕物，即可達該目的 ，基於該見解終於完成本發明。 亦即，本發明係在提供，於基板上介以含具有孤立電 子對原子之層，設化學放大型正型抗蝕層之感光性層合物 ，其特徵爲：含（A )含（a 1 )羥基苯乙烯或α -甲基 羥基苯乙烯單元，及（a 2 )羥基苯乙烯或α —甲基羥基 苯乙烯之羥基，其氫原子經低級烷氧基烷基取代之單元， 藉酸之作用使對碱之溶解度增大之樹脂成分，（β )藉活 性光線之照射可產生酸之酸產生劑，其中羥基中3 5 %之 氫原子經1 一乙氧基乙基取代，重均分子量1 2，0 〇 〇 1275907 (4) ，分散度1 · 2之聚羥基苯乙烯對其18質量份，該酸產 生劑以5質量份之比例配合形成之膜，以2 . 3 8質量％ 之氫氧化四甲銨水溶液於2 3 °C處理1分鐘時，膜減量爲 0 · 6奈米/秒以上之酸產生劑，及（C)胺，以及其特 徵爲：使用該感光性層合物，以活性線作選擇性照射，後 加熱之後，以碱顯像之抗蝕圖型之形成方法。 發明之實施形態 本發明之感光性層合物，係於基板上設含具有孤立電 子對原子之第一層，及其上所設化學放大型正型抗蝕組成 物所成之第二層而構成。而基板係用通常慣用於半導體裝 置之基板，例如砂晶圓。 又，設於該基板上，含具有孤立電子對原子之第一層 ，有例如氮化砂（T i N )層，磷•政酸玻璃（P S G ) 層、硼•磷•矽酸玻璃（BPSG)層、氮化矽（S iN )層、四氮化三矽（S i 3 N 4 )層等。如此之層係以例 如化學蒸鑛（CVD)法、有機或無機SOG法、有機聚 合之旋塗法，於基板上設厚0·02至0·5微米之層。 設於該第一層上之第二層，係將化學放大型正型抗蝕 組成物，以旋塗法、塗旋（coat-and-spin)法等塗布成厚 0.3至3.0微米之層。 該化學放大型正型抗蝕組成物含（A )樹脂成分、（ B )酸產生劑及（C )胺。 該（A)成分之樹脂有’ （a 1 )經基本乙嫌或α — -8- 1275907 (5) 甲基羥基苯乙烯單元，及（a 2 )羥基苯乙烯或α -甲基 羥基苯乙烯中羥基之氫原子以低級烷氧基烷基取代之單元 所成之聚羥基苯乙烯，或由（al) 、（a2)及（a3 )羥基苯乙烯或α-甲基羥基苯乙烯中羥基之氫原子以比 低級烷氧基烷基難以酸解離之基，即選自三級丁氧基羰基 、三級丁基、四氫吡喃基及四氫呋喃基中之至少1種酸解 離性溶解抑制基取代之單元所成者。 其中之（a 1 )單元係賦予碱可溶性、基板密合性之 φ 單元，係羥基苯乙烯或α —甲基羥基苯乙烯之乙烯式雙鍵 開裂衍生之單元。羥基之取代位置可係鄰位、間位、對位 之任一，因易於取得價格低，以對位爲最佳。 又，（ a 2)單元係上述羥基苯乙烯或α -甲基羥基 苯乙烯單元中羥基之氫原子以低級烷氧基烷基取代之單元 ，具有該單元時，曝光部經活性光線之照射所產生酸之作 用下，低級烷氧基烷基脫離，變成酚式羥基，使曝光前不 溶於碱之（A )成分在曝光後變成可溶於碱。 φ 上述低級烷氧基烷基之例有1-乙氧基乙基、1一甲 氧基乙基、1一甲氧基丙基、正丙氧基乙基、異丙氧基乙 基、正丁氧基乙基等。 如此之具酸解離性溶解抑制基之聚羥基苯乙烯，有例 如特開平5 — 2 4 9 6 8 2號公報所揭示者。 本發明所用之（A )成分，必要時可有（a 3 )含比 低級烷氧基烷基難解離之溶解抑制基之單元。如此之溶解 抑制基有，三級烷氧基羰基、三級烷基或環狀醚基，例如 -9- 1275907 (6) 三級丁氧基羰基、三級丁基、四氫毗喃基、四氣13夫喃基。 這些具酸解離性溶解抑制基之聚趨基苯乙燃’有例如 專利第2 6 9 0 6 5 6號說明書，特開平9 一 211866號公報，特開平10-48826號公報及 特開平1 1 一 9 5 4 3 4號公報所揭示者。 如此之具酸解離性抑制基之聚羥基苯乙烯’可係具2 種以上之酸解離性溶解抑制基之共聚物’或這些之混合物 如此之聚羥基苯乙烯，較佳例有以下（甲）至（己） 之聚合物或混合物。 (甲）聚羥基苯乙烯中羥基之3 0至6 0%氫原子經 低級烷氧基烷基取代之聚合物。 (乙）（甲）之聚合物，及聚羥基苯乙烯中羥基之 3 0至6 0%氫原子經三級丁氧基羰基取代之聚合物，其 質量比1:9至9:1之混合物。 (丙）（甲）之聚合物，及聚羥基苯乙烯中羥基之 肇 3 0至6 0%氫子經四氫吡喃基取代之聚合物，其質量比 1 : 9至9 : 1之混合物。 (丁）羥基之氫原子以三級丁氧基羰基取代之羥基苯 乙烯單元1 0至4 9莫耳％，羥基之氫原子以1 一乙氧基 乙基取代之羥基苯乙烯單元1 〇至4 9莫耳，及羥基苯乙 烯單元2至8 0莫耳％所成之聚合物。 (戊）經基之氫原子以三級丁基取代之羥基苯乙烯單 元1 0至4 9莫耳％，羥基之氫原子以1 一乙氧基乙基取 -10- 1275907 (7) 代之經基苯乙烯單元1 〇至4 9莫耳％，及羥基苯乙烯單 元2至80莫耳％所成之聚合物。 (3)之氫原子以四氫吡喃基取代之羥基苯乙烯 單元1 0至4 9莫耳％，羥基之氫原子以χ 一乙氧基乙基 取代之經基苯乙烯單元1 〇至4 9莫耳％，及羥基苯乙烯 單兀2至8 0莫耳％所成之聚合物。 這些樹脂成分，以重均分子量3，〇〇〇至 30 ’ 〇〇〇 ’分散度1 · 〇至6 · 〇範圍內者，因可賦 予高解析度、高耐熱性抗蝕圖型而爲較佳。分散度愈小則 可賦予高解析度、高耐熱性抗蝕圖型，以i · 〇至1 · 5 之範圍內者爲佳。 本發明中，亦可取代上述聚羥基苯乙烯，改用對應之 聚（α —甲基羥基苯乙烯）。 其次’本發明所用抗鈾組成物中必須配合有（Β )成 分’酸產生劑，其係可通過下述溶解試驗者。亦即，該酸 產生劑5質量份，及樹脂成分羥基中3 5%之氫原子以1 一乙氧基乙基取代，重均分子量12，000，分散度 1·2之聚羥基苯乙烯18質量份，於其有機溶劑，如丙 二醇單甲醚醋酸酯8 2質量份，調製成抗蝕組成物溶液， 於基板上形成之乾燥被膜，以2 · 3 8質量％之氫氧化四 甲銨水溶液在2 3 °C接觸1分鐘，其被膜減量，即膜厚之 減少在0 . 6奈米/秒以上之酸產生劑。 目前爲止之化學放大型正型抗鈾組成物中，樹脂成分 若用含低級烷氧基烷基等之相對弱酸可解離之溶解抑制基 -11- 1275907 (8) ，及三級丁氧基羰基、三級丁基或四氫吡喃基等之非強酸 難以解離之溶解抑制基之組合之樹脂成分時，因對K 1： F 準分子雷射光高度透明，且曝光產生之酸具有膨鬆之基， 曝光後加熱下擴散距離合適之理由，酸產生劑主要係用雙 (環己基磺醯基）重氮基$甲烷，必要時更以鎗鹽組合使用 〇 然而，現今因抗飩圖型有進一步微細化之要求，與含 具有孤立電子對原子之層相接設抗蝕層形成圖型時，這些 接觸部份難免有所謂基腳之捲曲之發生。此乃抗蝕物在曝 光部及未曝光部之邊界部位其酸產生量低，且經曝光由酸 產生劑所產生之酸與孤立電子對結合、失活而雙（環己基 磺醯基）重氮基甲烷係具膨鬆基之酸產生劑，在邊界部位 附近其對碱呈顯溶解抑制基之特性，並在曝光後加熱之際 ，所產生之酸難以擴散所致。 至於鑰鹽，因有陰離子部份及陽離子部份，邊界附近 之陰離子與經曝光產生之酸之質子結合而失活，而_鹽具 有如苯基之膨鬆基，故可於邊界附近對碱呈顯溶解抑制基 之作用。因此，本發明之（B )成分必須使用不具如此缺 點之酸產生劑。如此之酸產生劑不具環己基、苯基等膨鬆 基，係碱溶解性相對較高之酸產生劑。亦即，宜係上述溶 解試驗中，膜減量在0 . 6奈米/秒以上之酸產生劑。而 這些雙（環己基磺醯基）重氮基甲烷、鑰鹽等之酸產生劑 ，因上述溶解試驗中，膜減量均低於0 . 6奈米/秒，故 不適作本發明之酸產生劑。 -12- 1275907 (9) 本發明中，可用作（B )成分之酸產生劑，有例如一 般式 R1 — S〇2—C(N2)— S〇2 — R2 (I) (式中R1及R2各係碳原子數3至1 0之直鏈或分 枝烷基）之重氮基甲烷系化合物。該R1及R2有正丙基 、異丙基、正丁基、異丁基、三級丁基等。 鲁 特佳之重氮基甲烷系化合物，係上述一般式中R1及 R 2各係碳原子數3或4之分枝烷基之化合物，例如雙（ 異丙基磺醯基）重氮基甲烷、雙（異丁基磺醯基）重氮基 甲烷、雙（三級丁基磺醯基）重氮基甲烷。 這些（B )成分化合物可單獨使用，亦可2種以上組 合使用。其配合量係對（A)成分1 0 0質量份，在 0·5至30質量份，以1至10質量份爲佳。若該配合 量不及0·5質量份，則圖型無法充分形成，若超出30 Φ 質量份則難得均勻溶液，使溶液之保存安定性下降。 本發明所用之化學放大型正型抗蝕組成物，除上述（ A)成分及（B)成分以外，尙須配合（C)成分胺。如 此之胺成分，有例如脂族胺、芳族胺、雜環胺等。脂族胺 有例如，甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺 、正丙胺、二正丙胺、三正丙胺、異丙胺等。芳族胺有例 如，苯甲胺、苯胺、N —甲基苯胺、N，N -二甲基苯胺 、鄰一、間一及對甲苯胺、N，N —二乙基苯胺、二苯胺 -13- 1275907 (10) 、二對甲苯胺等。而雜環胺有例如，吡啶、鄰甲基吡啶、 鄰乙基吡啶、2 ，3 —二甲基吡啶、4 一乙基一2 —甲基 吡啶、3 —乙基一 4 —甲基吡啶等。尤以，本發明中含具 有孤立電子對原子之第一層，及設於其上之抗蝕物中樹脂 成分及酸產生劑之相互關係，預烘烤（pre-baking)時不 易揮散，曝光後熱處理之際不易擴散，若配合以沸點 1 5 0 °C以上之烷醇胺，即可改善抗蝕圖型頂部形狀，提 升矩形性故較佳。如此之烷醇胺係以三乙醇胺、三異丙醇 胺、三丁醇胺之類的三級胺，尤以三乙醇胺爲佳。這些胺 化合物可單獨使用，或2種以上組合使用。其配合量係對 (A)成分1〇〇質量份，在〇 · 〇1至1 · 〇質量份。 本發明所用化學放大型正型抗蝕組成物，除上述（A )、(B ) 、 （C)成分外，必要時可配合（D)羧酸及 以往慣用於化學放大型正型抗蝕組成物之暈光防止劑、用 以防輝紋（striation )之界面活性劑等。 如此之羧酸可用例如醋酸、檸檬酸、琥珀酸、丙二酸 、馬來酸等脂族羧酸，苯甲酸、水楊酸等芳族羧酸。這些 可單獨使用’或2種以上組合使用。這些羧酸通常係於對 (A)成分1〇〇質量份，在〇 · 至1 · 〇質量份之 範圍使用。 上述化學放大型正型抗蝕組成物係將（A )成分、（ B )成分、（C )成分及必要時之添加成分溶於有機溶劑 ’用作塗布液。此時所用之有機溶劑，可溶解上述諸成分 成均勻溶液者即可’可適當選用已知化學放大型抗蝕劑溶 -14- 1275907 (11) 劑中之任意1種或2種以上。 如此之有機溶劑有例如丙酮、丁酮、環己酮、甲基異 戊基酮、2 —庚酮等酮類，乙二醇、乙二醇單醋酸酯、二 乙二醇、二乙二醇單醋酸酯、丙二醇、丙二醇單醋酸酯、 二丙二醇，或二丙二醇單醋酸酯之單甲醚、單乙醚、單丙 醚、單丁醚或單苯醚等多元醇類及其衍生物，二噁烷之類 的環式醚類、乳酸甲酯、醋酸甲酯、醋酸乙酯、醋酸丁酯 、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙 酸乙酯等之酯類。 本發明之感光性層合物，可於基材上設上述之第一層 ，以如上調製之化學放大型正型抗蝕組成物之塗布液，塗 布而形成乾燥後其厚度0·3至3.0微米之塗布層作爲 第二層而製造。 本發明之感光性層合物，如同通常之感光性層合物， 係以例如K r F準分子雷射光之活性線，透過光罩圖型照 射，加熱。其次，用碱顯像液，例如〇 · 1至1 〇質量％ 之氫氧化四甲銨水溶液作其顯像處理。如此即可形成光罩 圖型之忠實圖型。 此時之活性線除K r F準分子雷射光以外，可用波長 較短之A r F準分子雷射光、F2雷射光、EUV (遠紫 外線）、V U V (真空紫外線）、電子束、X線、軟X線 等。 其次以實施例更詳細說明本發明。而各例中諸物性係 如下量測。 -15- 1275907 (12) 【實施方式】 (1 )感度 用旋塗機將試樣（抗蝕組成物溶液）塗布於設有特定 之第一層之基板上，使其在熱板上於1 0 0 °C乾燥9 0秒 ，形成膜厚0 · 7 0微米之抗飩膜’該膜透過光罩’用縮 小投影曝光裝置FPA — 3000EX3 ( Canon公司製 )，以每階段增加1毫焦耳/平方公分之KrF準分子雷 射光光量照射後，於1 1 〇 °C作9 0秒之曝光後烘烤（ PEB)，以2 · 3 8質量％之氫氧化四甲銨水溶液於 2 3 °C顯像6 0秒，水洗3 0秒後乾燥，以顯像後曝光部 膜厚爲0之最小曝光量爲感度’以毫焦耳/平方公分（能 量密度）單位記錄。 (2 )基腳之有無： 經上述（1 )之操作所得之〇 · 2 5微米線與間隙（ line-and-space)之抗蝕圖型之斷面以S EM (掃瞄式電 子顯微鏡）相片觀察，上述第一層及抗鈾圖型之界面無基 腳發生者以〇表示，有小基腳發生者以△表示’有大基腳 發生者以X表示。 (3 )解析度： 經上述（1 )之操作所得之線條圖型’檢視其臨界解 析度。 -16- 1275907 (13) 參考例1 羥基之3 5%氫原子經1 -乙氧基乙基取代之重均分 子量12，〇〇〇，分散度1 · 2之聚羥基苯乙烯18質 量份’及雙（三級丁基磺醯基）重氮基甲烷5質量份溶於 丙二醇單甲基醋酸酯8 2質量份，調製化學放大型抗蝕組 成物。其次，將該組成物塗布於基板上成厚7 〇 〇奈米之 抗蝕層，再滴下2·38質量％之氫氧化四甲銨水溶液， 於2 3 t保持1分鐘。經該水溶液處理，膜厚減至6 6 〇 奈米。 因此，膜減量爲0 . 6 7奈米/秒。 參考例2 參考例1之化學放大型抗蝕組成物中，取代雙（三級 丁基磺醯基）重氮基甲烷，改用同量之雙（異丙基磺醯基 )重氮基甲烷以外，同樣調製化學放大型抗蝕組成物。其 次，同樣以氫氧化四甲銨水溶液處理後，膜厚減至6 5 〇 奈米。 因此，膜減量爲0·83奈米/秒。 參考例3 #考例1之化學放大型抗蝕組成物中，取代雙（三級 τ _ 5黃醯基）重氮基甲烷，改用質量比1 : 1之雙（三級 擴醯棊）重氮基甲烷及雙（異丙基磺醯基）重氮基甲 -17- 1275907 (14) 烷之混合物5質量份以外，同樣調製化學放大型抗蝕組成 物。其次，同樣以氫氧化四甲銨水溶液處理後，膜厚減至 6 6 0奈米。 因此，膜減量爲0 · 6 7奈米/秒。 參考例4 參考例1之化學放大型抗鈾組成物中，取代雙（三級 丁基磺醯基）重氮基甲烷，改用同量之雙（環己基磺醯基 )重氮基甲烷以外，同樣調製化學放大型抗蝕組成物。其 次同樣以氫氧化四甲銨水溶液處理後，膜厚減至6 7 0奈 米。 因此，膜減量爲0 . 50奈米/秒。 參考例5 參考例1之化學放大型抗蝕組成物中，取代雙（三級 丁基礦醯基）重氮基甲院’改用同量之三氟甲纟完;gg酸雙（ 4 -二級丁基苯基）确鐵以外，同樣調製化學放大型抗貪虫 組成物。其次同樣以氫氧化四甲銨水溶液處理後，膜厚減 至6 9 5奈米。 因此，膜減量爲0·08奈米/秒。 參考例6 參考例1之化學放大型抗蝕組成物中，取代雙（三級 丁基磺醯基）重氮基甲烷，改用雙（環己基磺酶基）重氮 •18- 1275907 (15) 基甲烷3·6質量份及三氟甲烷磺酸三苯銃1·4質量份 之混合物以外，同樣調製化學放大型抗蝕組成物。其次， 同樣以氫氧化四甲銨水溶液處理，膜厚減爲6 7 5奈米。 因此，膜減量爲〇 . 4 2奈米/秒。 實施例11275907 (1) Field of the Invention The present invention relates to a layer comprising an isolated electron pair atom on a substrate, for example, tantalum nitride, tantalum nitride, and phosphoric acid glass. When a resist pattern is formed on a boron/phosphorus-tantalum glass or a titanium nitride layer, a high-resolution 'without defects such as a footing can be formed, and the cross-sectional shape is excellent in a resist pattern photosensitive layer. A chemically amplified positive resist composition. [Prior Art] In recent years, the integrated density of semiconductor devices has been increasing, and the design rule of LS I near 0 · 20 μm has been mass-produced. Soon, the design law is LSI near 0 · 15 μm. Mass production will also appear. Recently, there has been a proposal for a chemically amplified positive resist composition because it is a conventional non-chemically amplified resist using naphthoquinonediazide sulfonate as a sensitizer compared to a varnish resin as a substrate resin. Degree and sensitivity are excellent, so it has been gradually adopted. Such a chemically amplified positive-type resist composition is known, for example, by using p-(cyclohexylsulfonyl) as a base resin using p-(1-ethoxyethoxy)styrene and a p-hydroxystyrene copolymer. A sulfonyldiazomethane-based acid generator such as diazomethane is used as an acid generator. (Japanese Patent Laid-Open No. Hei-5-249682). It is a combination of lysate base, acetal group which can be dissociated with weak acid, and sulfonyldiazomethane compound which produces relatively weak acid, and can form high-resolution anti-uranium pattern by 1275907 (2) . When a base resin having only an acetal group is used, the resist pattern formed once has a tendency to become thinner over time, and there is no need to have satisfactory heat resistance, substrate followability, etc., and it is difficult to put it into practical use. In order to overcome such disadvantages, there are copolymers and mixed resins which use an acetal group plus a tertiary butoxy group, a tertiary butyl group, a tetrahydropyranyl group, etc., which are difficult to dissociate, a strong acid dissociated acid dissociable group. And the proposal of a chemically amplified resist composition of a sulfonyldiazomethane acid generator, which has now become mainstream. On the other hand, in the manufacture of a semiconductor device, an insulating layer, a semiconductor layer, a metal layer, or the like is provided on a substrate for the purpose of use, and a photosensitive layer formed of a resist layer is used to form a resist. Graphic type. Usually, the insulating layer is made of yttrium oxide (S i 〇 2 ), yttrium nitride ( si N ), arsenic trioxide (S i 3 N 4 ), bismuth pentoxide (T a 2 0 5 ), phosphorus. • Capric acid glass (PSG), boron, phosphorus, bismuth acid glass (BPSG), organic SOG, polyimide, etc., polycrystalline germanium layer for semiconductor layer, aluminum, aluminum, tantalum alloy, aluminum layer for metal layer A layer of copper alloy, tungsten germanium (WSi), titanium nitride (TiN), or the like. As for the photosensitive layer having these layers, a fine pattern of about 30,000 micrometers has been formed so far, which is sufficient for the purpose, but the amount of LSI near 0. 15 micrometers required by the finest design rule is sufficient. For these photosensitive laminates, there is also a requirement for a pattern size of about 0.25 μm. However, when such a photosensitive layer is used to form the above-described fine pattern, a layer and a resist pattern containing SiN, SisN4, 1275907 (3) P SG, BP SG or T i N having an isolated electron pair atom are used. The footing of the layer is inevitably caused by the footing and the shape of the section is damaged. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an anti-formation on a layer having an isolated electron pair atom such as a S i N, S i 3N4, P SG, BP SG or T i N layer. In the case of an etch pattern, a chemically amplified positive resist composition which forms a photosensitive laminate of the base at the boundary between the layers and the resist layer can be prevented. The present inventors have suppressed the formation of a base on a substrate by providing a photosensitive laminate having a chemically amplified positive resist layer on a layer containing an isolated electron pair atom for forming a resist pattern. The method has repeatedly been studied. It has been found that a chemically amplified positive resist containing a specific resin component, a specific membrane-reducing acid generator and an amine combination can achieve this purpose, and based on this knowledge, the present invention is finally completed. invention. That is, the present invention provides a photosensitive laminate comprising a layer having an isolated electron pair atom and a chemically amplified positive resist layer on a substrate, characterized in that: (A) contains (a) 1) a hydroxystyrene or α-methylhydroxystyrene unit, and a hydroxyl group of (a 2 )hydroxystyrene or α-methylhydroxystyrene, a unit in which a hydrogen atom is substituted by a lower alkoxyalkyl group, and an acid is used. The action of the resin component which increases the solubility of the alkali, (β) by the irradiation of the active light can generate an acid generator, wherein 35 % of the hydrogen atoms in the hydroxyl group are substituted by 1-ethoxyethyl group, and the average weight a molecular weight of 1 2,0 〇〇1275907 (4), a polyhydroxystyrene having a degree of dispersion of 1 · 2 of 18 parts by mass, the acid generator is blended in a ratio of 5 parts by mass to form a film, to 2.38 mass% When the aqueous solution of tetramethylammonium hydroxide is treated at 23 ° C for 1 minute, the film is reduced to an acid generator of 0.6 nm/sec or more, and (C) an amine, and characterized in that the photosensitive laminate is used. The object is formed by selective irradiation of the active line, and after heating, the formation of the resist pattern by alkali imaging . [Embodiment of the Invention] The photosensitive laminate of the present invention is provided with a first layer comprising an isolated electron pair atom and a second layer of a chemically amplified positive resist composition provided thereon. Composition. The substrate is a substrate which is conventionally used for a semiconductor device, such as a sand wafer. Further, the substrate is provided on the substrate, and comprises a first layer having isolated electron pair atoms, such as a layer of nitriding sand (T i N ), a layer of phosphoric acid (PSG), and a glass of boron/phosphoric acid (BPSG). a layer, a tantalum nitride (S iN ) layer, a tetrazolium nitride (S i 3 N 4 ) layer, or the like. Such a layer is provided with a layer having a thickness of from 0.02 to 0.5 μm on the substrate by, for example, a chemical vapor deposition (CVD) method, an organic or inorganic SOG method, or an organic polymerization spin coating method. The second layer provided on the first layer is a chemically amplified positive resist composition which is applied by a spin coating method, a coat-and-spin method or the like to a layer having a thickness of 0.3 to 3.0 μm. The chemically amplified positive resist composition contains (A) a resin component, (B) an acid generator, and (C) an amine. The resin of the component (A) has '(a 1 ) via a basic or a - 8 - 1275907 (5) methyl hydroxystyrene unit, and (a 2 ) hydroxystyrene or α-methyl hydroxy styrene a polyhydroxystyrene formed by a unit in which a hydrogen atom of a hydroxyl group is substituted with a lower alkoxyalkyl group, or a hydroxyl group derived from (al), (a2) and (a3) hydroxystyrene or α-methylhydroxystyrene The hydrogen atom is difficult to be acid-dissociated with a lower alkoxyalkyl group, that is, at least one acid dissociable dissolution inhibiting group selected from the group consisting of a tertiary butoxycarbonyl group, a tertiary butyl group, a tetrahydropyranyl group and a tetrahydrofuranyl group. Replaced by the unit. Among them, the (a 1 ) unit is a unit of φ unit which imparts alkali solubility and substrate adhesion, and is a unit derived from a vinyl double bond cracking of hydroxystyrene or α-methylhydroxystyrene. The substitution position of the hydroxyl group may be any of the ortho, meta and para positions, and the alignment is optimal because it is easy to obtain a low price. Further, the unit (a 2) is a unit in which a hydrogen atom of a hydroxyl group in the above hydroxystyrene or α-methylhydroxystyrene unit is substituted with a lower alkoxyalkyl group, and when the unit is provided, the exposed portion is irradiated with active light. Under the action of acid generation, the lower alkoxyalkyl group is detached to become a phenolic hydroxyl group, and the component (A) which is insoluble in alkali before exposure becomes soluble in alkali after exposure. Examples of the above lower alkoxyalkyl group are 1-ethoxyethyl, 1-methoxyethyl, 1-methoxypropyl, n-propoxyethyl, isopropoxyethyl, and Butoxyethyl and the like. Such a polyhydroxystyrene having an acid dissociable dissolution inhibiting group is disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei. The component (A) used in the present invention may have (a3) a unit containing a dissolution inhibiting group which is more difficult to dissociate than a lower alkoxyalkyl group, if necessary. Such a dissolution inhibiting group is a tertiary alkoxycarbonyl group, a tertiary alkyl group or a cyclic ether group, for example, 9-1275907 (6) tert-butoxycarbonyl group, tert-butyl group, tetrahydropyranyl group, Four gas 13 fumonyl. For example, the invention discloses a polythiophene acetophenone having an acid-dissociating dissolution-inhibiting group. For example, JP-A-H09-211866, JP-A-10-48826, and JP-A No. 1 1 The one disclosed in the Gazette of 9 5 4 3 4 . Such a polyhydroxystyrene having an acid dissociative inhibition group can be a copolymer of two or more acid dissociable dissolution inhibiting groups or a mixture of such polyhydroxystyrenes, preferably having the following (a) a polymer or mixture of (by). (A) A polymer in which a 30 to 60% hydrogen atom of a hydroxyl group in a polyhydroxystyrene is substituted with a lower alkoxyalkyl group. (b) a polymer of (a), and a polymer in which a hydroxyl group of 30 to 60% of a hydrogen atom in the polyhydroxystyrene is substituted with a tertiary butoxycarbonyl group, and a mass ratio of 1:9 to 9:1 . (C) a polymer of (a), and a polyhydric hydroxystyrene having a hydroxy group of 30 to 60% of a hydrogen-substituted tetrahydropyranyl group, a mass ratio of 1:9 to 9:1 . a hydroxystyrene unit in which a hydrogen atom of a hydroxyl group is substituted with a tertiary butyloxycarbonyl group of 10 to 49 mol%, and a hydrogen atom of a hydroxyl group is substituted with a monoethoxyethyl group of a hydroxystyrene unit. 4 9 moles, and hydroxystyrene units 2 to 80 mole % of the polymer. (e) a hydroxystyrene unit substituted with a tertiary butyl group via a hydrogen atom of 10 to 49 mol%, and a hydrogen atom of a hydroxyl group as a 1-ethoxyethyl group - 10 1275907 (7) A polymer formed from a styrene unit of 1 to 49 mol%, and a hydroxystyrene unit of 2 to 80 mol%. (3) The hydroxystyrene unit in which the hydrogen atom is substituted with a tetrahydropyranyl group is 10 to 49 mol%, and the hydrogen atom of the hydroxyl group is substituted with a styrene-ethoxyl group via a styrene unit 1 to 4 9 mole %, and hydroxystyrene monoterpene 2 to 80 mole % of the polymer. These resin components are in the range of weight average molecular weight 3, 〇〇〇 to 30 ' 〇〇〇 'dispersion 1 · 〇 to 6 · ,, because they can impart a high-resolution, high-heat-resistance resist pattern. good. The smaller the degree of dispersion, the higher the resolution and the high heat resistance resist pattern can be imparted, and it is preferably in the range of i · 〇 to 1 · 5. In the present invention, the above polyhydroxystyrene may be used instead, and the corresponding poly(?-methylhydroxystyrene) may be used instead. Next, the anti-uranium composition used in the present invention must be compounded with a (Β) component' acid generator which can be tested by the following dissolution tester. That is, 5 parts by mass of the acid generator, and 35% of the hydrogen atoms in the hydroxyl group of the resin component are substituted with 1-ethoxyethyl group, and the polyhydroxystyrene 18 having a weight average molecular weight of 12,000 and a degree of dispersion of 1.2 is used. a part by mass of an organic solvent, such as propylene glycol monomethyl ether acetate (2 2 parts by mass), prepared into a resist composition solution, and a dried film formed on the substrate, and a 2·38 % by mass aqueous solution of tetramethylammonium hydroxide After contact at 2 3 ° C for 1 minute, the film was reduced, that is, the acid generator having a film thickness reduction of 0.6 nm/sec or more. In the chemically amplified positive anti-uranium composition of the prior art, the resin component is dissolved by a relatively weak acid such as a lower alkoxyalkyl group, and the dissolution inhibiting group is 11-1175907 (8), and the tertiary butoxycarbonyl group is used. When a resin component such as a tertiary butyl group or a tetrahydropyranyl group which is difficult to dissociate and dissolves the inhibiting group, which is difficult to dissociate, is highly transparent to the K 1: F excimer laser light, and the acid produced by the exposure has a bulky Base, the reason for the proper diffusion distance under heating after exposure, the acid generator mainly uses bis(cyclohexylsulfonyl)diazoyl group methane, and if necessary, it is used in combination with gun salt. However, due to the anti-mite pattern, Further miniaturization requires that when the resist layer is formed with a layer having isolated electron pair atoms, the contact portion is inevitably caused by the so-called base curl. This is because the resist has a low acid generation amount at the boundary between the exposed portion and the unexposed portion, and the acid generated by the acid generator is combined with the isolated electron pair and deactivated by the exposure, and the bis(cyclohexylsulfonyl) group is heavy. The nitrogen-based methane-based acid generator has a property of exhibiting a dissolution inhibiting group to the alkali in the vicinity of the boundary portion, and is difficult to diffuse when the acid is heated after exposure. As for the key salt, due to the anionic portion and the cationic portion, the anion near the boundary is inactivated by the proton of the acid generated by the exposure, and the salt has a bulky group such as a phenyl group, so the base can be adjacent to the boundary. It shows the effect of dissolving the inhibitory group. Therefore, the component (B) of the present invention must use an acid generator which does not have such a deficiency. Such an acid generator does not have a swelling group such as a cyclohexyl group or a phenyl group, and is an acid generator having a relatively high alkali solubility. That is, it is preferable to use an acid generator having a membrane reduction of 0.6 nm/sec or more in the above dissolution test. The acid generators such as bis(cyclohexylsulfonyl)diazomethane and key salts are not suitable for the acid production of the present invention because the membrane reduction is less than 0.6 nm/sec in the above dissolution test. Agent. -12- 1275907 (9) In the present invention, an acid generator which can be used as the component (B) has, for example, the general formula R1 - S〇2 - C(N2) - S〇2 - R2 (I) (wherein R1 And a diazomethane-based compound in which R2 is a linear or branched alkyl group having 3 to 10 carbon atoms. The R1 and R2 may be n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl. The compound of the diazonium methane compound of the above formula is a compound of the above formula wherein each of R1 and R 2 is a branched alkyl group having 3 or 4 carbon atoms, such as bis(isopropylsulfonyl)diazomethane, Bis(isobutylsulfonyl)diazomethane, bis(tertiary butylsulfonyl)diazomethane. These (B) component compounds may be used singly or in combination of two or more. The blending amount is preferably 10 parts by mass of the component (A), and is preferably 0.5 to 30 parts by mass, preferably 1 to 10 parts by mass. If the amount is less than 0.5 parts by mass, the pattern cannot be sufficiently formed. If it exceeds 30 Φ parts by mass, it is difficult to obtain a uniform solution, and the storage stability of the solution is lowered. The chemically amplified positive resist composition used in the present invention is not required to contain the amine of the component (C) in addition to the components (A) and (B). As the amine component, for example, an aliphatic amine, an aromatic amine, a heterocyclic amine or the like can be mentioned. The aliphatic amine is, for example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, isopropylamine or the like. Aromatic amines are, for example, benzylamine, aniline, N-methylaniline, N,N-dimethylaniline, o-, m- and p-toluidine, N,N-diethylaniline, diphenylamine-13 - 1275907 (10), di-p-toluidine, etc. The heterocyclic amines are, for example, pyridine, o-methylpyridine, o-ethylpyridine, 2,3-lutidine, 4-ethyl-2-methylpyridine, 3-ethyl-4-methylpyridine, and the like. . In particular, the present invention contains a first layer having an isolated electron pair atom, and a relationship between a resin component and an acid generator in a resist disposed thereon, which is not easily volatilized during pre-baking, and is exposed. It is not easy to diffuse during the post-heat treatment. If an alkanolamine having a boiling point of 150 ° C or higher is blended, the top shape of the resist pattern can be improved, and the rectangular shape is improved. Such an alkanolamine is preferably a tertiary amine such as triethanolamine, triisopropanolamine or tributylolamine, particularly preferably triethanolamine. These amine compounds may be used singly or in combination of two or more. The blending amount is 1 part by mass of the component (A), and is 〇1 to 1 · 〇 by mass. The chemically amplified positive resist composition used in the present invention may be combined with (D) a carboxylic acid and a conventionally used chemically amplified positive resist composition in addition to the above components (A), (B), and (C). A smudge prevention agent, a surfactant for preventing striation, and the like. As such a carboxylic acid, an aliphatic carboxylic acid such as acetic acid, citric acid, succinic acid, malonic acid or maleic acid, or an aromatic carboxylic acid such as benzoic acid or salicylic acid can be used. These may be used singly or in combination of two or more. These carboxylic acids are usually used in an amount of from 1 part by mass to the part (A) and from 〇 to 1 part by mass. The chemically amplified positive resist composition is used as a coating liquid by dissolving (A) component, (B) component, (C) component and, if necessary, an additive component in an organic solvent. In the organic solvent to be used at this time, any of the above-mentioned components may be dissolved in a homogeneous solution. Any one or two or more of the known chemically amplified resist-dissolved -14-127075907 (11) agents may be appropriately selected. Such organic solvents are, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, and diethylene glycol. Monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and other polyols and derivatives thereof, dioxins Cyclic ethers such as alkane, methyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate Etc. In the photosensitive laminate of the present invention, the first layer described above may be provided on the substrate, and the coating liquid of the chemically amplified positive resist composition prepared as described above may be applied to form a thickness of 0·3 to 3.0 after drying. A coating layer of micron is produced as the second layer. The photosensitive laminate of the present invention, like a usual photosensitive laminate, is heated by, for example, an active line of K r F excimer laser light through a reticle pattern. Next, an alkali developing solution such as 〇·1 to 1% by mass of an aqueous solution of tetramethylammonium hydroxide is used as the development treatment. This creates a faithful pattern of the reticle pattern. In addition to the K r F excimer laser light, the active line at this time can be used with shorter wavelengths of A r F excimer laser light, F2 laser light, EUV (extreme ultraviolet light), VUV (vacuum ultraviolet light), electron beam, X-ray, Soft X line and so on. Next, the present invention will be described in more detail by way of examples. The physical systems in each case were measured as follows. -15- 1275907 (12) [Embodiment] (1) Sensitivity A sample (resist composition solution) is applied onto a substrate provided with a specific first layer by a spin coater to be placed on a hot plate at 1 After drying at 0 0 °C for 90 seconds, an anti-crack film having a film thickness of 0·70 μm was formed. The film was passed through a reticle with a reduced projection exposure apparatus FPA-3000EX3 (manufactured by Canon Inc.), and each stage was increased by 1 mJ/ After the KrF excimer laser light amount of square centimeter is irradiated, it is subjected to exposure post-baking (PEB) at 19 ° C for 90 seconds, and 2 3 38 % by mass aqueous solution of tetramethylammonium hydroxide at 23 ° C. The image was developed for 60 seconds, washed with water for 30 seconds, and dried. The minimum exposure amount with a film thickness of 0 after exposure was recorded as the sensitivity 'in millijoules per square centimeter (energy density) unit. (2) The presence or absence of the base: The cross section of the 抗蚀·25 5 micron line and the line-and-space resist pattern obtained by the above operation (1) is S EM (scanning electron microscope) In the photograph observation, the interface of the first layer and the anti-uranium pattern is represented by 〇 without the occurrence of the foot, and the person with the small foot is represented by △ 'The occurrence of the large foot is represented by X. (3) Resolution: The degree of resolution of the line pattern obtained by the operation of the above (1) is examined. -16- 1275907 (13) Reference Example 1 35% of a hydroxyl group substituted by 1-ethoxyethyl group having a weight average molecular weight of 12, 〇〇〇, a degree of dispersion of 1 · 2 of polyhydroxystyrene 18 parts by mass And 5 parts by mass of bis(tris-butylsulfonyl)diazomethane dissolved in propylene glycol monomethyl acetate (82 parts by mass) to prepare a chemically amplified resist composition. Next, the composition was applied onto a substrate to form a resist layer having a thickness of 7 Å, and a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was added thereto, and the mixture was kept at 2 3 t for 1 minute. After treatment with the aqueous solution, the film thickness was reduced to 6 6 奈 nm. Therefore, the membrane reduction was 0.77 nm/sec. Reference Example 2 In the chemically amplified resist composition of Reference Example 1, the bis(tris-butylsulfonyl)diazomethane was substituted, and the same amount of bis(isopropylsulfonyl)diazomethane was used instead. In addition, a chemically amplified resist composition was also prepared. Secondly, after treatment with an aqueous solution of tetramethylammonium hydroxide, the film thickness was reduced to 65 〇 nm. Therefore, the membrane reduction was 0.083 nm/sec. Reference Example 3 In the chemically amplified resist composition of the test example 1, the bis (three-stage τ _ 5 xanthene) diazomethane was replaced by a double (three-stage expanded diazonium) mass ratio of 1:1. A chemically amplified resist composition was prepared in the same manner as in the case of 5 parts by mass of a mixture of methane and bis(isopropylsulfonyl)diazomethyl-17- 1275907 (14) alkane. Secondly, after treatment with an aqueous solution of tetramethylammonium hydroxide, the film thickness was reduced to 660 nm. Therefore, the membrane reduction was 0 · 67 nm/sec. Reference Example 4 In the chemically amplified anti-uranium composition of Reference Example 1, the bis(tertiary butylsulfonyl)diazomethane was substituted, and the same amount of bis(cyclohexylsulfonyl)diazomethane was used instead. The chemically amplified resist composition was also prepared. The film thickness was also reduced to 670 nm after treatment with an aqueous solution of tetramethylammonium hydroxide. Therefore, the membrane reduction was 0.55 nm/sec. Reference Example 5 In the chemically amplified resist composition of Reference Example 1, the substituted bis(tertiary butyl orthoquinone)diazocarbazide was replaced with the same amount of trifluoromethyl hydrazine; gg acid bis(4- In addition to iron, secondary chemically amplified anti-invasive components are also prepared. Secondly, after treatment with an aqueous solution of tetramethylammonium hydroxide, the film thickness was reduced to 695 nm. Therefore, the film reduction was 0.08 nm/sec. Reference Example 6 In the chemically amplified resist composition of Reference Example 1, a bis(tertiary butylsulfonyl)diazomethane was substituted, and a bis(cyclohexylsulfonyl)diazoite•18-1275907 (15) was used instead. A chemically amplified resist composition was prepared in the same manner as in the mixture of 3 to 6 parts by mass of the base methane and 1 part by mass of the triphenylsulfonium trifluoromethanesulfonate. Secondly, it was treated with an aqueous solution of tetramethylammonium hydroxide, and the film thickness was reduced to 675 nm. Therefore, the membrane reduction is 〇. 4 2 nm/sec. Example 1
(A)成分用羥基之3 5%氫原子經1 一乙氧基乙基 取代，重均分子量12，000，分散度1 · 2之聚羥基 H 苯乙烯10 0質量份，（B)成分用雙（三級丁基磺醯基 )重氮基甲烷1 0質量份，連同三乙醇胺0 · 3質量份， 溶於丙二醇單甲醚醋酸酯5 0 0質量份，以孔徑0 · 2微 米之濾膜過濾，調製化學放大型正型抗蝕組成物之塗布液 〇 其次，於設有表1之第一層之矽晶圓上，用旋塗機塗 布該塗布液，於1 0 0 °C之熱板上乾燥9 0秒鐘，形成厚 0 . 7 0微米之抗蝕膜，製造感光性層合物。其物性列於 Φ 表1。 實施例2 (A)成分用羥基之3 5%氫原子經1 一乙氧基乙基 取代，重均分子量12，000，分散度1 · 2之聚羥基 苯乙烯1 00質量份，（B)成分用雙（異丙基磺醯基） 重氮基甲烷1 0質量份，連同三乙醇胺〇 · 3質量份及馬 來酸0 · 0 7質量份，溶於丙二醇單甲醚醋酸酯5 0 0質 -19- l2759〇7 (16) 毚份，過濾調製成塗布液，用以如同實施例1製造感光性 層合物。其物性列於表1。 寶施例3 (A)成分用羥基之3 5%氫原子經1 一乙氧基乙基 取代，重均分子量12，000，分散度1 · 2之聚羥基 本乙烯6 0質量份’及羥基之3 5%氫原子以三級丁氧基 幾基取代，重均分子量12，00〇，分散度1 · 2之聚 麵綦苯乙烯40質量份之混合物，（B)成分用雙（三級 丁綦磺醯基）重氮基甲烷1 0質量份，連同三乙醇胺 0·3質量份及丙二酸0·07質量份，溶於丙二醇單甲 _醋酸酯5 0 0質量份，過濾調製塗布液。其次用之如同 實施例1製造感光性層合物。其物性列於表1。 實施例4 (A)成分用羥基之3 5%氫原子經1 一乙氧基乙基 取代，重均分子量12，000，分散度1 · 2之聚羥基 苯乙烯7 0質量份，及羥基之3 0%氫原子經三級丁基取 代’重均分子量12，000，分散度1 · 2之聚羥基苯 乙烯3 0質量份之混合物，（B)成分用雙（三級丁基磺 醯基）重氮基甲烷5質量份，連同三乙醇胺〇·2質量份 及水楊酸0 · 2質量份，溶於丙二醇單甲醚醋酸酯5 0 0 質量份，過濾調製塗布液。其次以之如同實施例1製造感 光性層合物。其物性列於表1。 -20- 1275907 (17) 實施例5 (A)成分用羥基之3 5%氫原子經1 一乙氧基乙基 取代，重均分子量12 ’ 000 ’分散度1 · 2之聚經基 苯乙烯5 0質量份，及羥基之3 5%氫原子經四氫吡喃基 取代，重均分子量12，000，分散度1 · 2之聚羥基 苯乙烯5 0質量份之混合物，（B)成分用雙（三級丁基 磺醯基）重氮基甲烷及雙（異丙基磺醯基）重氮基甲烷之 等量混合物1 0質量份，連同三乙醇胺〇 · 2質量份及馬 來酸0·05質量份，溶於丙二醇單甲醚醋酸酯500質 量份，過濾調製塗布液。其次以之如同實施例1製造感光 層合物。其物性列於表1。 比較例1 (B)成分用雙（環己基磺醯基）重氮基甲烷1 〇質 量份以外，如同實施例1製造感光性層合物。其物性列於 φ 表1 。 比較例2 (B )成分用三氟甲烷磺酸雙（4 -三級丁基苯基磺 醯基）碘_ 3質量份以外，如同實施例1製造感光性層合 物。其物性列於表1。 比較例3 -21- 1275907 (18) (B )成分用雙（環己基磺醯基）重氮基甲烷5質量 份及三氟甲烷磺酸三苯銃2質量份之混合物以外，如同實 施例3製造感光性層合物。其物性列於表1。 表1 第一層之 種類 酸產生劑之 膜減量 (nm/秒） 感度 (m J/cm2) 基腳之 有姐 Π3 j\\\ 解析度 (μ m) 1 TiN 0.67 35 〇 0.18 實 2 TiN 0.83 28 〇 0.20 施 3 Si3N4 0.67 33 〇 0.18 例 4 TiN 0.67 3 8 〇 0.19 5 BPSG 0.67 30 〇 0.20 比 1 TiN 0.50 5 1 Δ 0.20 較 2 Si3N4 0.08 3 1 X 0.22 例 3 Si3N4 0.42 34 X 0.22The component (A) is substituted with 1 ethoxyethyl group of 3 5% hydrogen atom of the hydroxyl group, and has a weight average molecular weight of 12,000 and a polyhydroxy H styrene having a degree of dispersion of 1 · 2 parts by mass. 10 parts by mass of bis(tertiary butylsulfonyl)diazomethane, together with 0.3 parts by mass of triethanolamine, dissolved in 500 parts by mass of propylene glycol monomethyl ether acetate, and filtered at a pore diameter of 0 · 2 μm Membrane filtration, preparing a coating solution of a chemically amplified positive resist composition, and then coating the coating liquid on a crucible having the first layer of Table 1 by a spin coater at 100 ° C The hot plate was dried for 90 seconds to form a resist film having a thickness of 0.70 μm to prepare a photosensitive laminate. Its physical properties are listed in Φ Table 1. Example 2 (A) component is substituted with 1 ethoxyethyl group of 3 5% hydrogen atom of a hydroxyl group, and the weight average molecular weight is 12,000, and the polyhydroxy styrene having a degree of dispersion of 1.2 is 100 parts by mass, (B) 10 parts by mass of bis(isopropylsulfonyl)diazomethane, together with triethanolamine hydrazine · 3 parts by mass and maleic acid 0 · 0 parts by mass, dissolved in propylene glycol monomethyl ether acetate 5 0 0 -19-19- l2759〇7 (16) A portion was filtered and prepared into a coating liquid for producing a photosensitive laminate as in Example 1. Its physical properties are listed in Table 1. Example 3 (A) is substituted with a 3 5% hydrogen atom of a hydroxyl group by a 1-ethoxyethyl group, a weight average molecular weight of 12,000, a polyhydroxyl group having a degree of dispersion of 1.2, and 60 parts by mass of a hydroxyl group. 3 5% of a hydrogen atom is substituted with a tertiary butoxy group, a weight average molecular weight of 12,00 Å, a dispersion of 1 / 2 of a mixture of 40 parts by mass of styrene, and a component (B) of double (third) 10 parts by mass of diazomethane, together with 0.3 parts by mass of triethanolamine and 0.07 parts by mass of malonic acid, dissolved in 500 parts by mass of propylene glycol monomethyl acetate, filtered and coated liquid. Next, a photosensitive laminate was produced as in Example 1. Its physical properties are listed in Table 1. Example 4 (A) component was substituted with 3 5% of a hydroxyl group by a 1-ethoxyethyl group, a weight average molecular weight of 12,000, a polyhydroxystyrene having a degree of dispersion of 1.2, 70 parts by mass, and a hydroxyl group. 30% hydrogen atom is substituted with a tertiary butyl group, a mixture having a weight average molecular weight of 12,000, a polyhydroxystyrene having a degree of dispersion of 1.2, and a mixture of 30 parts by mass, and a component (B) having a bis (tertiary butyl sulfonyl group) 5 parts by mass of diazomethane, together with 2 parts by mass of triethanolamine oxime and 0.2 parts by mass of salicylic acid, dissolved in 500 parts by mass of propylene glycol monomethyl ether acetate, and filtered to prepare a coating liquid. Next, a photosensitive laminate was produced as in Example 1. Its physical properties are listed in Table 1. -20- 1275907 (17) Example 5 (A) component is substituted with 3 5% hydrogen atom of a hydroxyl group via 1 -ethoxyethyl group, and the weight average molecular weight is 12 ' 000 '. 50 parts by mass, and 35% by weight of a hydroxyl group is substituted with a tetrahydropyranyl group, a weight average molecular weight of 12,000, a dispersion of 1 / 2 of a polyhydroxystyrene of 50 parts by mass, and a component (B) An equivalent mixture of bis(tertiary butylsulfonyl)diazomethane and bis(isopropylsulfonyl)diazomethane, 10 parts by mass, together with triethanolamine hydrazine · 2 parts by mass and maleic acid ·05 parts by mass, dissolved in 500 parts by mass of propylene glycol monomethyl ether acetate, and filtered to prepare a coating liquid. Next, a photosensitive laminate was produced as in Example 1. Its physical properties are listed in Table 1. Comparative Example 1 (B) A photosensitive laminate was produced as in Example 1 except that bis(cyclohexylsulfonyl)diazomethane was used as the component. Its physical properties are listed in φ Table 1. Comparative Example 2 (B) A photosensitive laminate was produced as in Example 1 except that trifluoromethanesulfonic acid bis(4-tributylphenylsulfonyl)iodine was used in an amount of 3 parts by mass. Its physical properties are listed in Table 1. Comparative Example 3 -21 - 1275907 (18) The component (B) was obtained by using a mixture of 5 parts by mass of bis(cyclohexylsulfonyl)diazomethane and 2 parts by mass of triphenylsulfonium trifluoromethanesulfonate, as in Example 3. A photosensitive laminate is produced. Its physical properties are listed in Table 1. Table 1 Film loss of the first layer of acid generator (nm / sec) Sensitivity (m J / cm2) The base of the foot has a sister 3 j \ \ resolution (μ m) 1 TiN 0.67 35 〇 0.18 real 2 TiN 0.83 28 〇0.20 Application 3 Si3N4 0.67 33 〇0.18 Example 4 TiN 0.67 3 8 〇0.19 5 BPSG 0.67 30 〇0.20 Ratio 1 TiN 0.50 5 1 Δ 0.20 Compared with 2 Si3N4 0.08 3 1 X 0.22 Example 3 Si3N4 0.42 34 X 0.22
-22--twenty two-