TWI252383B - Photosensitive polysilazane composition, pattern-forming method using it, and calcination method of its coating film - Google Patents

Photosensitive polysilazane composition, pattern-forming method using it, and calcination method of its coating film Download PDF

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TWI252383B
TWI252383B TW90121123A TW90121123A TWI252383B TW I252383 B TWI252383 B TW I252383B TW 90121123 A TW90121123 A TW 90121123A TW 90121123 A TW90121123 A TW 90121123A TW I252383 B TWI252383 B TW I252383B
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Taiwan
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photosensitive
film
composition
coating film
pattern
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TW90121123A
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Chinese (zh)
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Tatsuro Nagahara
Hideki Matsuo
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Az Electronic Materials Japan
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  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Description

1252383 五、發明說明（1 ) 技術領域 本發明係有關一種使用感光性聚矽胺烷組成物經由圖案 化以形成聚矽胺烷膜之方法、以及使圖案化的感光性聚矽 胺烷塗膜經煅燒以形成二氧化矽系陶瓷膜的方法、以及此 等方法中所使用的較佳感光性聚矽胺烷組成物。 先前技術 於以製作半導體裝置或液晶顯示裝置等爲始的各種領域 中，爲予以微細加工或圖案化時使用正型或負型光阻劑。 以往，該光阻劑有由酚醛淸漆樹脂與醌二疊氮感光劑所成 的正型感光性組成物、化學放大型正型或負型感光性組成 物、聚乙烯基肉桂酸酯系感光性組成物、雙疊氮-橡膠系 感光性組成物、光聚合系感光性組成物等負型光阻劑等之 各種習知物。該光阻劑係視其使用目的而被要求具有各種 特性。例如於半導體裝置之加工中，被要求具有高感度、 高解像度、耐蝕刻性等特性。 另外，於半導體裝置、液晶顯示裝置、印刷電路基板等 中’使用以層間絕緣膜爲始的各種圖案膜。一般而言，該 圖案膜係塗覆膜形成性有機或無機材料、或使此等材料自 氣相堆積形成被膜後，經由光阻劑使該被膜鈾刻形成。於 該蝕刻必須形成微細圖案時，一般利用氣相鈾刻。然而， 氣相蝕刻一般有裝置成本高、且處理速度慢的問題。 另外’於半導體裝置等之製造工程（例如藉由CVD之配 線蒸鍍工程）等中，使裝置暴露於大於400°C之高溫中。因 1252383 五、發明說明（2) 此’該暴露於高溫下之裝置中所使用的層間絕緣膜等材料 ’就耐熱性而言有機材料無法充分予以對應、以使用無機 材料爲宜。該無機材料大多使用耐熱性、耐摩擦性、耐蝕 性、絕緣性、透明性等優異的二氧化矽系陶瓷膜。 該圖案化二氧化矽系陶瓷膜一般使用習知之圖案化光阻 劑作爲触刻光罩、藉由使陶瓷膜蝕刻所形成者，會有成本 等的問題。因此’企求不使用氣相鈾刻、以形成微細化的 層間絕緣膜方法。 對該要求而言提案有塗覆感光性聚矽胺烷組成物、使所 形成的感光性聚矽胺烷塗膜曝光後顯像以形成圖案化的聚 石夕胺烷膜’再使該圖案化的聚矽胺烷膜轉化成二氧化矽系 陶瓷膜’形成陶瓷膜圖案的方法。例如日本特開平5 _ 88 3 7 3號公報中記載在基板上塗覆含有聚矽胺烷之塗覆液 以形成塗膜，且在該塗膜上、氧化氣氛中以圖案狀照射紫 外線、且使紫外線曝光部分硬化後、除去紫外線未曝光部 分’然後使圖案化的聚矽胺烷膜轉化成二氧化矽系陶瓷膜 ’以形成陶瓷膜圖案的方法。該方法由於使光照射部分硬 化、殘留，故爲負型光阻劑。 另外’半導體裝置等之加工係採用微細化一途，因此， 企求光阻劑之型式爲高解度的正型、耐氧電漿性等耐蝕刻 性局的材料。而且，以圖案化的被膜作爲層間絕緣膜殘留 使用時’該被膜材料除伴隨上述微細化之要件外，尙企求 層間絕緣膜所要求的高耐熱性、低介電常數、透明性等各 1252383 五、發明說明（3) b丨生優異的材料。爲對應於該要求，本發明人等於特願平 11-283106號（特開2000-181069號）公報中提案含有聚石夕 胺院與光酸發生劑之具正型機能的感光性聚矽胺烷組成物 及使用該感光性聚矽胺烷組成物、塗覆該物以形成塗膜， 且在上述塗膜上圖案狀照射光後、溶解除去上述塗膜經照 射的部份，以、形成圖案化的聚砂胺院膜方法及使該圖案化 的聚矽胺烷膜放置於周圍氣氛中或予以煅燒、以轉化成二 氧化矽系陶瓷膜、形成圖案化的絕緣膜方法。 而且，本發明人等於特願平1 2 - 1 08023號中提案藉由使 用改質聚矽倍半胺烷，改善保存安定性、且具有正型機能 之感光性聚矽胺烷組成物。 此等使用正型感光性聚矽胺烷組成物的方法中，感光性 聚矽胺烷塗膜之曝光部分會生成酸，該生成的酸會使聚矽 胺烷之Si - N鍵解裂，與H20分子反應形成矽烷醇（Si -〇H) 鍵，引起聚矽胺烷分解。然而，於此等習知技術中企圖使 聚矽胺烷分解的方法中，具體處理方法係於曝光後使感光 性聚矽胺烷與水接觸的方法。 此等提案的正型感光性聚矽胺烷組成物與負型感光性聚 矽胺烷組成物相比時具有高解像度’惟對圖案微細化而言 必須另外改善解像度。而且，經曝光的感光性聚矽胺烷組 成物企圖與水接觸、使聚砂胺院分解’惟此時聚砂胺院之 分解僅在感光性聚矽胺烷組成物之膜表面附近進行’無法 視其分解處理條件而定藉由繼後的驗水溶液充分除去顯像 1252383 五、發明說明（4) 時曝光部分之塗膜，於顯像後於圖案上仍存在有顯像殘渣 、且會有感光性聚矽胺烷塗膜與基板之密接性不充分的問 題產生。因此，亦要求不具該問題之感光性聚矽胺烷塗膜 的分解法。另外，藉由使感光性聚矽胺烷塗膜經煅燒以轉 化成二氧化矽系陶瓷膜時，僅單純使聚矽胺烷塗膜加熱、 無法充分進行聚矽胺烷之氧化，形成被膜中殘留有很多聚 砂胺烷之S i - N鍵的二氧化矽陶瓷膜，很難形成作爲層間 絕緣膜時要求具有十分低介電常數之膜。此外，在該二氧 化矽系陶瓷膜內殘留有很多S 1 - N鍵時，會有很容易產生 吸濕情形、形成具有不安定物性之膜的問題。因此，使感 光性聚矽胺烷塗膜經煅燒、使該膜中之聚矽胺烷轉化成二 氧化矽系陶瓷時，企求可容易且充分進行轉化、藉此製得 具有優異的介電常數等特性、膜內不會殘留有S i - N鍵之 二氧化矽系陶瓷膜之感光性聚矽胺烷塗膜的煅燒方法。 有鑑於上述問題，本發明以提供使用感光性聚矽胺烷組 成物之形成圖案聚矽胺烷塗膜的方法中，於曝光後使感光 性聚矽胺烷組成物之聚矽胺烷分解所需時間縮短、且與基 板之密接性佳、顯像後在圖案上不會有顯像殘渣、形成圖 案化的聚矽胺烷膜方法爲目的。 另外，本發明以提供即使僅單純藉由加熱，仍可充分進 行聚矽胺烷之氧化、形成在膜內沒有或幾乎沒有Si-N鍵 存在之二氧化矽系陶瓷膜之感光性聚矽胺烷塗膜之煅燒方 法爲目的。 1252383 五、發明說明（5 ) 此外’本發明以提供可形成具有低介電常數、優異的耐 熱性、耐摩擦性、耐蝕性、絕緣性、透明性之作爲層間絕 緣膜極爲有用的二氧化矽系陶瓷膜的感光性聚矽胺烷組成 物、圖案感光性聚矽胺烷膜之形成方法及感光性聚矽胺烷 塗膜之煅燒方法爲目的。 而且’本發明以提供具有高解像度之感光性聚矽胺烷組 成物爲目的。 本發明人等爲達成上述目的、再三深入硏究的結果發現 下述之見解。換言之，發現使用如含聚矽胺烷與光酸發生 劑之感光性聚矽胺烷組成物、具正型機能之感光性組成物 形成圖案化的聚矽胺烷膜時，藉由使曝光的感光性聚矽胺 烷塗膜與含水蒸氣之氣體接觸、即加濕處理、在短時間內 進行聚矽胺烷分解、且於顯像後在圖案上沒有產生顯像殘 渣、此時增加氣體之水蒸氣含量，或另於加濕處理後使感 光性聚矽胺烷塗膜加熱時縮短分解時間、且於該膜加熱後 緩和結露於膜表面之條件，更爲提高加濕處理氣氛之水蒸 氣氛壓，就藉此可更爲縮短聚矽胺烷分解所需時間而言藉 由顯像時之加熱亦可提高聚矽胺烷塗膜與基板之密接性。 而且，發現於使感光性聚矽胺烷塗膜經煅燒時，於煅燒 前使該塗膜曝光、且進行上述加濕處理，可容易且充分地 進行轉化成二氧化矽系陶瓷，藉此可得各特性優異、且膜 內不會有S 1 - N鍵殘留的二氧化矽系陶瓷膜。 另外，發現藉由在含有特定改質聚砂倍半胺院與光酸發 1252383 五、 發明說明（6) 生 劑之 感 光性組成物中添加作爲形狀 t-f-t 女疋 化 劑 之 水 溶 性 化 合 物， 可 提高解像度，且該感光性組 成物 於 煅 燒 後 可 形 成 介 電常 數 、絕緣性、機械特性優異的 層間 絕 緣 膜 等 之 微 細 化 圖案 〇 本發 明 係爲基於此等之見解者。 發 明之 揭 示 本發 明 係有關由下述構成所成的聚 矽胺 烷 膜 之 形 成 方 法 感光 性 聚矽胺烷塗膜之煅燒方法及 感光 性 聚 矽 胺 院 組 成 物 〇 [1] 一 種圖案形成方法，其係爲藉 由使 感 光性 聚 矽 胺 烷 組 成物 之 塗膜於曝光後顯像、形成圖 案化 的 聚 矽 胺 院 膜 之 方 法， 其 特徵爲使經曝光的感光性聚 矽胺 烷 塗 膜 於加 濕 處 理 後顯 像 〇 [2] 如 上述[1 ]項之圖案形成方法 ，其 中 於 加 濕 處 理 時 使 感光性 聚矽胺烷塗膜加熱。 [3] 一 種感光性聚矽胺烷塗膜之煅 燒方 法 其係 爲 使 感 光性聚 矽 胺烷塗膜經煅燒的方法，其 特徵 爲 設 有使 咸 VQiN 光性 聚 矽胺 院 塗膜曝光的工程及加濕處理 的工 程 作 爲 該 煅 燒 的 刖 處理 工 程。 [4] 如 上述[3 ]項之感光性聚矽胺 烷塗 膜 的 煅 燒 方 法 其 中使 感 光性聚矽胺烷塗膜圖案化。 [5] 如 上述[3 ]項之感光性聚矽胺 烷塗 膜 之 煅 燒 方 法 1 其 中於加 濕處理時使感光性聚矽胺烷: ~ 8 - 塗膜: 加i 孰 / V \\ 〇 1252383 五、發明說明（9) 煅燒。 藉由上述本發明方法所形成的圖案聚矽胺烷膜可直接利 用於例如蝕刻光阻劑或顯示元件等元件中之圖案被膜。由 於於本發明中所使用的感光性聚矽胺烷組成物爲正型，故 解像度高、且較習知有機材料系光阻劑具較高的耐氧電漿 性。而且，由於藉由本發明之煅燒方法所形成的二氧化矽 系陶瓷膜係爲耐熱性、低介電性、透明性等優異的被膜， 故特別適合作爲層間絕緣膜。 另外，藉由本發明時，上述[6 ]項記載的含有特定改質 聚矽倍半胺烷與光酸發生劑之感光性聚矽胺烷組成物中添 加作爲形狀安定化劑之水溶性化合物，可藉由光更爲提高 圖案加工之解像度。 此外，藉由使由上述[6 ]〜[1 7 ]項記載之感光性聚矽胺 烷組成物所形成的塗膜長時間放置或經煅燒，可製得適合 作爲層間絕緣膜之高耐熱性、低介電常數、透明性、等優 異的圖案二氧化矽系陶瓷被膜。 而且，於本發明中藉由在感光性聚矽胺烷組成物中含有 增感色素’可使用高壓水銀燈等低價光源予以圖案化。 另外’於本發明中藉由在含增感色素之感光性聚矽胺烷 組成物中含有氧化觸媒，可於圖案化後被膜煅燒時使該增 感色素分解’且製得作爲液晶顯示裝置等之層間絕緣膜極 爲有用的無色透明二氧化矽系陶瓷被膜。 另外’於本發明中藉由在感光性聚矽胺烷組成物中添加 -11- 1252383 五、發明說明（1〇) 顏料，可製作耐熱性、絕緣性、硬度優異的圖案精度佳之 濾色器或黑色基體。 圖式之簡單說明 第1圖係爲不含形狀安定化劑之水溶性化合物的感光性 聚矽胺烷組成物之圖案截面側壁形狀的簡略截面圖。 第2圖係爲含形狀安定化劑之水溶性化合物的感光性聚 矽胺烷組成物之圖案截面側壁形狀的簡略截面圖。 第3圖係爲本發明之感光性組成物所使用的改質聚矽倍 半胺烷之紅外線吸收光譜圖。 第4圖係爲本發明實施例所形成的煅燒膜之紅外線吸收 光譜圖。 第5圖係爲比較例所形成的煅燒膜之紅外線吸收光譜圖 〇 於下述中更詳細地說明本發明。 本發明之聚矽胺烷膜的圖案形成方法，於此沒有特別的 限制，惟含有（a )將感光性聚矽胺烷組成物塗覆或印刷於 基板上以形成塗膜的塗膜形成工程、（b )於上述塗膜上圖 案狀照射光之曝光工程、（c )使經圖案曝光的基板視其所 需在基板加熱的狀態下與含有水蒸氣之氣體接觸、使聚矽 胺烷分解的加濕處理工程、（d )使上述塗膜經光照射的部 分溶解除去的顯像工程。於下述中以該例示的方法具體地 說明本發明之圖案聚矽胺烷膜之形成方法。 首先，於本發明聚矽胺烷膜之形成圖案方法中，感光性 -12- 1252383 五、發明說明（彳1) 組成物可使用含有聚矽胺院與光酸發生劑之感光性聚5夕胺 烷組成物之具有正型機能的感光性組成物。 該正型感光性聚矽胺烷組成物中所使用的聚矽胺烷例如 以下述者爲典型物。 (A )含有通式： (其中，R1、R2及R3係各自獨立地表示氫原子、烷基、 烯基、環烷基、芳基、此等之基外鍵結於矽或氮部分爲碳 的基、烷基矽烷基、烷基胺基或烷氧基）所示架構之數量 平均分子量100〜50，000的聚矽胺烷或其改質物。 (B)含有通式： -〔S i R4 (NR5) ,· 5〕，厂 (Π) (其中，R4及R5係各自獨立地表不氫原子、院基、烯基 、環烷基、芳基、此等之基外鍵結於矽或氮部分爲碳的基 、烷基矽烷基、烷基胺基或烷氧基，η係表示任意的整數） 所示架構之數量平均分子量100〜100, 〇〇〇的聚矽倍半胺 烷或其改質物。 (C)含有以-(1^丨1)-、-(1^11〇)-、-(1^州02)-及-(Rs 1 03)-(其中，R係表示烷基、烯基、環烷基、芳基、烷 基胺基或烷基矽烷基）之數量平均分子量300〜100,〇〇〇的 聚有機矽胺烷。 -13- 1252383 五、發明說明（12 ) (D )含有以通式： -〔S i R6 (NR7) ! 5〕一 (Π) 爲基本構成單位、及以通式： -〔S i R62nr、〕— (IV) 及/或 〔S i R63 (NR7)。5〕一 （v) (其中，R6係各表示碳數1〜3之烷基或經取代或未經取 代的苯基，R7係表示氫原子、碳數1〜3之烷基或經取代 或未經取代的苯基）所示其它構成單位，對上述基本構成 單位而言含有0.1〜100莫耳％、較佳者爲0.5〜40莫耳％ 、更佳者爲1〜20莫耳％之數量平均分子量1〇〇〜1〇〇,000 的聚矽倍半胺烷。 該改質聚矽倍半胺烷中，其它構成單位對基本構成而言 以無規鍵結。而且，改質聚砂倍半胺院中R6、R7中任一個 可單獨地選自於具體的基，基本構成單位間可爲相同或不 同，而基本構成單位與其它構成單位間可爲相同或不同。 例如，基本構成單位中部分R6爲甲基、其餘部分爲苯基， R7部分爲氫原子、其餘部分爲甲基，基本構成單位之R6爲 甲基、其它構成單位之R6爲甲基或苯基，基本構成單位之 R7爲氫、其它的構成單位R7爲甲基、等，皆有可能。較佳 者基本構成單位及其它構成單位兩方中，R6爲甲基或苯基 、特別是甲基最佳。此外，基本構成單位及其它的構成單 位兩方中R7以氫較佳。 -14- 1252383 五、發明說明（13) 上述（D )的改質聚矽倍半胺烷中，僅含有通式（丨v )構成 單位作爲其它構成單位時，通式（丨V )之構成單位對上述基 本構成單位而言含有〇 · 1莫耳％〜i 〇〇莫耳％、較佳者爲1 莫耳％〜20莫耳％。而且’僅含有通式（v)構成單位作爲其 它構成單位時，通式（V )之構成單位對上述基本構成單位 而言含有0.1莫耳％〜50莫耳％、較佳者爲0.5莫耳％〜2〇 莫耳％。若其它構成單位小於〇 . 1莫耳％時，聚合物本身之 安定性低、於保存時聚合物間會引起聚合。反之，若其它 構成單位大於1 〇〇莫耳％時，聚合物之分子量不充分而使 塗膜產生流動性，故不爲企求。 上述（D)中所使用的改質聚矽倍半胺烷之數量平均分子 量爲100〜1 00,000、較佳者爲500〜5000。若改質聚矽倍 半胺烷之數量平均分子量小於1〇〇時塗膜會產生流動性， 而若大於1 00 , 000時不易溶解於溶劑中，故不爲企求。 本發明中聚矽胺烷係使用含有上述聚矽倍半胺烷及聚有 機矽胺烷等者。而且，於本發明中聚矽胺烷當然爲單獨的 聚矽胺烷、亦可以爲2種以上聚矽胺烷、或聚矽胺烷與其 它聚合物之共聚物或聚矽胺烷與其它聚合物或化合物之混 合物。所使用的聚矽胺烷可以爲具有鏈狀、環狀或交聯構 造者、或在分子內同時具有此等數個構造者，此等可以單 獨或混合物利用。此等聚矽胺烷就所得的膜之硬度或緻密 性而言以過氫聚矽胺烷較佳，就可撓性而言以有機聚矽胺 烷較佳。此等聚矽胺烷之選擇係當業者視其用途適當地進 -15- 1252383 五、發明說明（μ ) 行。 上述之聚矽胺烷爲習知者或可以習知的方法製造者◦具 體而言聚矽胺烷之製造例如日本特公昭6 3 _ 1 6 3 2 5號公報 、特開昭61- 892 3 0號公報、同62 - 1 56 1 3 5號公報、 D.Seyferth 等人，。〇〇1〇1111^。2“〇11(^八[11.〇61*.3〇(：·，。-Π ’ January(1983) 、 Polym. Prepr. ， Am· Chem. Soc.， Div· P〇lym_ chem.，11，1 0 ( 1 984 )等記載。 而且’分子內具有交聯構造的聚矽胺烷如特開昭49 _ 69717 號公報、D. Seyferth 等人、Communication of Am. Cei:. Soc.，C-132，July( 1 984 )中報告者，或此等中含有 金屬原子之聚金屬矽胺烷。 其它如特開昭62 - 1 95024號公報中重複單位爲 [(31[12)11(關）„1]及[(31[121〇](其中，n、m、r 係爲 1、2 或 3 )所示聚矽氧烷、特開平2 - 8 4 4 3 7號公報中揭示聚矽胺烷 中使硼化合物反應製造之具有優異的耐熱性聚硼矽院、特 開昭63 - 8 1 1 22號、同63 - 1 9 1 832號、特開平2 - 77427號 公報揭示使聚矽胺烷與金屬烷氧化物反應製得的聚金屬矽 胺烷、特開平卜1 38 1 08號、同1 - 1 38 1 07號、同1 - 203429 號、同1 - 203430號、同4 - 63 8 3 3號、同3 - 320 1 67號公報 中揭示的增加分子量（上述公報之前4者）、耐加熱分解性 經提高（後2者）的無機矽烷高聚合物或改質聚矽胺烷、特 開平 2 - 1 7 5 726 號、同 5 - 86200 號、同 5-33 1 29 3 號、同 3-3 1 3 26號公報中揭示的聚矽胺烷中導入有機成分的有利於 6 1252383 五、發明說明（15) 膜厚化之共聚合聚矽胺院、特開平5-238827號、同6- 122852 號、同 6-299188 號、同 6-306329 號、同 6- 240208號、同7 - 1 96986號公報中揭示在聚矽胺烷中加成 或添加爲促進陶瓷化之觸媒化合物對塑膠或鋁等金屬施工 ，在較低溫下同樣地使用陶瓷化的低溫陶瓷聚矽胺院等。 本發明中適合使用的聚矽胺烷係爲主要爲含有上述通式 (II)所示架構、數量平均分子量100〜100,000、較佳者爲 300〜1 0,000之聚矽倍半胺烷及其衍生物，更佳的聚矽倍 半胺烷係式（II)中R4爲甲基且R5爲氫之聚苯基矽胺院。 該聚矽胺烷係於合成一般聚矽胺烷時之胺解作用藉由使用 R4S i C 13作爲出發原料容易製得。合成聚矽胺烷時之胺解 作用參照例如特開昭6 3 - 1 6 3 2 5號公報。 此外，上述（C )之聚有機矽胺烷亦可以爲適合本發明所 使用的聚矽胺烷。該聚有機矽胺烷一般可以藉由通式 RnSiX4_n(其中R係爲烷基、烯基、環烷基、芳基、烷基胺 基或烷基矽烷基，X係爲鹵素原子，η係爲1或2)所示有 基矽烷與銨及水反應製得。該聚有機矽胺烷可藉由通式 RnSiX4_n(其中，R係表示烷基、烯基、環烷基、芳基、烷 基胺基或烷基矽烷基，X係表示鹵素原子，η係表示1或2) 所示有機鹵化矽烷、與銨及水反應製得。該聚有機矽胺烷 由於即使在高溫下處理時仍可得具有低介電常數之煅燒膜 ，故作爲層間絕緣膜之前驅體特別有用。而且，爲聚有機 矽胺烷時可藉由變化主鏈所含有的含氧量來控制煅燒膜之 -17- 1252383 五、發明說明（16 ) 比介電常數’故具有可以容易地得到所企求的比介電常數 之優點。該具有機砂胺丨兀及其製法之詳細說明可參照特願 平 1 0 - 5 286 3 3 號說明書（W098 / 029475 )。 而且，於本發明中上述（D )所記載的改質聚矽倍半胺院 作爲聚矽胺烷特別有用。該改質聚矽倍半胺院於一般聚石夕 胺烷合成時之胺解作用中可藉由使作爲出發原料之 R6SiCl3、R^SiCl2及/或R^SiCl以後者爲對應於上述其它 構成單位之含有比率的莫耳比率、可容易製得。例如含有 20莫耳％作爲其它構成單位之通式：[SlR62NR7]i，，可使 用對R6SiCl3而言混合有20莫耳％之的R62SiCi2矽烷原料 進行胺解作用，同樣地含有1 〇莫耳％作爲其它構成單位之 通式：[SiR63(NR7)〇.5]-時，可使用對R6SlCl3而言混合有 10莫耳％之的R^SiCl。於合成聚矽胺烷時之胺解作用的詳 細說明，參照例如特公昭63 - 1 63 25號公報。 上述（D)所示之改質聚矽倍半胺烷的安定性高、於實質 上保存時不會另外聚合成分子量高者。不爲特定理論所限 制者’惟僅由三官能形之基本構成單位所成的聚合物時， 分子內大多存在有歪斜的環構造、且此等於保存時會產生 開裂 '藉由該開裂部分與其它同樣開裂的分子再鍵結而成 分子量高者。在三官能形之基本構成單位中導入二官能形 及/或一官能形之構成單位時，爲減少歪斜的環構造時不 易產生開裂•再結晶情形，可控制聚合物之高分子量化者 -18- 1252383 五、發明說明（17) 本發明或本發明中所使用的感光性組成物包含光酸發生 劑。光酸發生劑可藉由原有的感光波長範圍之光直接照射 、或使用增感色素時藉由其增感色素激勵的波長範圍之光 間接照射而成激勵狀態。藉由激勵狀態的光酸發生劑使聚 矽胺烷之S i - N鍵開裂、經解裂的S 1 - N鍵與水分反應、生 成矽烷醇（S i - 0H )鍵。矽烷醇由於可溶於下述顯像液中， 僅溶解除去感光性組成物塗膜之光照射部分，達成正型圖 案化。 該正型感光性聚矽胺烷組成物中所使用的光酸發生劑例 ，具體例如過氧化物、萘醌二疊氮磺酸酯、硝基苯甲酯等 。而且，苯醯基甲苯磺醯亦極爲有用。其它光酸發生劑有 硝基苯甲基磺酸類、鏺鹽類[例如雙（4 -第3 - 丁基苯基）碘 鏺鹽或三苯基毓鹽]等亦極爲有用。此等之光酸發生劑視 其所需可組合2種以上使用。 於下述中表示過氧化物系、萘醌二疊氮磺酸酯系、及硝 基苯甲酸酯系之光酸發生劑之具體例。然而，下述例示僅 爲說明者，本發明所使用的光酸發生劑不受下述記載者所 說明。 過氧化物系光酸發生劑： 3，3’，4,4’-四（第3 -丁基過氧化羰基）二苯甲酮、第3_丁 基過氧化苯甲酸酯、甲基乙酮過氧化物、環己烷過氧化物 、甲基環己烷過氧化物、甲基乙醯基乙酸酯過氧化物、乙 酿基丙酮過氧化物、1，1-雙（第3 -己基過氧化）3, 3, 5 -三甲 -19- 1252383 五、發明說明（18) 基環己烷、1，1-雙（第3 -己基過氧化）環己烷、丨，丨-雙（第 3-丁基過氧化）3,3,5 -三甲基環己烷、二-第3 -丁基過氧化 -2 -甲基環己院、1,1-雙（弟3-丁基過氧化）環己院、ι,ι_ 雙（第3 -丁基過氧化）環十二烷、2,2 -雙（第3 -丁基過氧化） 丁烷、正丁基4 ,4-雙（第3-丁基過氧化）戊酸酯、2 ,2-雙 (4，4 -二-第3 - 丁基過氧化環己基）丙烷、對-盏烷氫過氧化 物、二異丙基苯氫過氧化物、1,1,3,3 -四甲基丁基氫過氧 化物、枯烯氫過氧化物、第3 -己基氫過氧化物、第3 - 丁 基氫過氧化物、α，α’-雙（第3 -丁基過氧化）二異丙基苯 、枯烯基過氧化物、2，5 -二甲基-2，5 -雙（第3 - 丁基過氧化） 己烷、第3 - 丁基枯烯基過氧化物、二-第3 - 丁基過氧化物 、2，5-二甲基-2,5-雙（第3 -丁基過氧化）己炔-3、異次丁 基過氧化物、3,5,5 -三甲基己醯基過氧化物、辛醯基過氧 化物、月桂醯基過氧化物、硬脂醯基過氧化物、琥珀酸過 氧化物、間-甲苯醯基苯甲醯基過氧化物、苯甲醯基過氧 化物、二-正丙基過氧化二碳酸酯、二異丙基過氧化二碳 酸酯、雙（4 -第3 -丁基環己基）過氧化二碳酸酯、二-2-乙 氧基乙基過氧化二碳酸酯、二-2-乙基己基過氧化二碳酸 酯、二-3 -甲氧基丁基過氧化二碳酸酯、二（3 -甲基-3-甲 氧基丁基）過氧化二碳酸酯、α，α’-雙（新癸醯基過氧化） 二異丙基苯、枯烯基過氧化新癸酸酯、1，1，3, 3 -四甲基丁 基過氧化新癸酸酯、1 -環己基-1 _甲基乙基過氧化新癸酸 酯、第3 -己基過氧化新癸酸酯、第3 _ 丁基過氧化新癸酸 -20- 1252383 五、發明說明（19) 酯、第3 -己基過氧化三甲基乙酸酯、第3 - 丁基過氧化三 甲基乙酸酯、1,1,3 ,3 -四甲基丁基過氧化-2-乙基己酸酯 、2，5-二甲基- 2,5-雙（2-乙基己醯基過氧化）己烷、1-環 己基-1-甲基乙基過氧化-2-乙基己酸酯、第3 -己基過氧化 -2 -乙基己酸酯 '第3 - 丁基過氧化-2 -乙基己酸酯、第3 -丁基過氧化異丁酸酯、第3 _己基過氧化異丙基單碳酸酯、 第3 -丁基過氧化馬來酸、第3 -丁基過氧化-3, 5,5 -三甲基 己酸酯、第3 - 丁基過氧化月桂酸酯、2，5 -二甲基-2，5 -(間 -甲苯醯基過氧化）己烷、第3 -丁基過氧化異丙基單碳酸酯 、第3 -丁基過氧化-2-乙基己基單碳酸酯、第3 -己基過氧 化苯甲酸酯、2,5-二甲基-2,5 -雙（苯甲醯基過氧化）己烷 、第3-丁基過氧化乙酸酯、第3 -丁基過氧化-間-甲苯醯 基苯甲酸酯、雙（第3 -丁基過氧化）異酞酸酯、第3 -丁基 過氧化烯丙基單碳酸酯、第3 -丁基三甲基甲矽烷基過氧化 物、1，3-二-(第3-丁基過氧化羰基）苯、等。 萘醌二疊氮磺酸酯系光酸發牛劑： 1，2 -萘醌-(2 )-二疊氮基-5 -磺酸氯化物、1 , 2 -萘醌-(2) -二疊氮-4-磺酸氯化物、2, 3,4 -三羥基二苯甲酮與6-疊氮基-5, 6 -二氫-5-羰基-萘-1-磺酸之（單〜三）酯、 2,3,4, 4’-三羥基二苯甲酮與6-疊氮基-5, 6-二氫-5-羰基-萘-1 -磺酸之（單〜三）酯、等。 硝基苯甲酯系光酸發生劑： 硝基苯甲基甲苯磺醯酸酯、二硝基苯甲基甲苯磺醯酸 -21 - 1252383 五、發明說明（2〇) 酯、硝基苯甲基氯化物、二硝基苯甲基氯化物、硝基苯 甲基溴化物、二硝基苯甲基溴化物、硝基苯甲基乙酸酯 '二硝基苯甲基乙酸酯、硝基苯甲基三氯乙酸酯、硝基 苯甲基三氟乙酸酯、等。 此等光酸發生劑在感光性聚矽胺烷組成物中之含量係視 光酸發生劑的種類及感光性組成物之用途予以適量化，惟 一般而言對聚矽胺烷重量而言爲0.0 5〜5 0重量％、較佳者 爲0 . 1〜20重量％、更佳者爲1〜20重量％。若光酸發生劑 之含量小於0.0 5重量％時分解反應速度極慢，而若大於50 重量％時例如使用改質聚矽倍半胺烷時很難得到改質聚矽 倍半胺烷原有特徵之緻密膜。 此外，聚矽胺烷例如含改質聚矽倍半胺烷與光酸發生劑 之感光性組成物必須保存一定期間以上時，部分以硝基苯 甲基磺酸酯爲始的光酸發生劑恐會因於感光性組成物保存 時自聚矽胺烷游離的微量NH3而分解。此時，藉由選擇耐 鹼性光酸發生劑，可提高感光性組成物之保存安定性。該 耐鹼性光酸發生劑例如有亞胺基磺酸酯衍生物、二礪衍生 物、二疊氮甲烷衍生物、以及4 -甲氧基-α - (((( 4 -甲氧基 苯基）磺醯基）氧）亞胺基）苯乙醯苯胺之亞楓鏺鹽系化合物 及如下式化合物之三畊系化合物。 -22- 1252383 五、發明說明（21)1252383 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Field of the Invention The present invention relates to a method of forming a polyimide film via patterning using a photosensitive polyamidane composition, and a patterned photosensitive polyimide film A method of calcining to form a ceria-based ceramic film, and a preferred photosensitive polyamidene composition used in the methods. Prior Art In various fields from the production of semiconductor devices or liquid crystal display devices, positive or negative photoresists have been used for microfabrication or patterning. In the past, the photoresist has a positive photosensitive composition made of a phenolic enamel resin and a quinonediazide sensitizer, a chemically amplified positive or negative photosensitive composition, and a polyvinyl cinnamate-based photosensitive material. Various conventional materials such as a negative composition such as a bismuth-rubber-based photosensitive composition or a photopolymerizable photosensitive composition. The photoresist is required to have various characteristics depending on the purpose of use. For example, in the processing of a semiconductor device, characteristics such as high sensitivity, high resolution, and etching resistance are required. Further, in the semiconductor device, the liquid crystal display device, the printed circuit board, or the like, various pattern films starting from the interlayer insulating film are used. In general, the pattern film is formed by coating a film-forming organic or inorganic material, or by depositing such materials from a vapor phase to form a film, and then etching the film uranium via a photoresist. When the etching must form a fine pattern, gas phase uranium engraving is generally utilized. However, vapor phase etching generally has the problems of high device cost and slow processing speed. Further, in a manufacturing process of a semiconductor device or the like (for example, a wiring vapor deposition process by CVD) or the like, the device is exposed to a high temperature of more than 400 °C. 1252383 V. Inventive Note (2) The material such as the interlayer insulating film used in the device exposed to high temperature is not sufficiently compatible with the organic material in terms of heat resistance, and an inorganic material is preferably used. As the inorganic material, a ceria-based ceramic film excellent in heat resistance, abrasion resistance, corrosion resistance, insulation, transparency, and the like is used. The patterned cerium oxide-based ceramic film generally has a problem such as cost by using a conventional patterned photoresist as a etch mask and etching the ceramic film. Therefore, there is a method of not using a gas phase uranium engraving to form a fine interlayer insulating film. For this requirement, it is proposed to apply a photosensitive polyamidane composition, and to expose the formed photosensitive polyamidamine coating film to develop a pattern to form a patterned polyoxin film, and to make the pattern A method of forming a ceramic film pattern by converting a polyalkane film into a cerium oxide ceramic film. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. After the ultraviolet exposure is partially hardened, the ultraviolet unexposed portion is removed, and then the patterned polyamidane film is converted into a ceria-based ceramic film to form a ceramic film pattern. This method is a negative photoresist because the light irradiation portion is hardened and left. Further, since the processing of semiconductor devices and the like is carried out by miniaturization, the type of the photoresist is a material having high etching resistance such as positive type and oxygen-resistant plasma resistance. In addition, when the patterned film is used as an interlayer insulating film, the film material is required to have the high heat resistance, low dielectric constant, transparency, etc. required for the interlayer insulating film, in addition to the requirements for the above-mentioned miniaturization. , invention description (3) b excellent materials. In order to cope with this requirement, the inventors of the present invention have the positive function of a polyacrylamide having a positive function in the publication of the Japanese Patent Publication No. Hei 11-283106 (JP-A-2000-181069). An alkane composition, a photosensitive polyamine composition, a coating film, a coating film, and a pattern-like irradiation light on the coating film, and then removing and removing the irradiated portion of the coating film to form A patterned polythene film method and a method in which the patterned polyamidene film is placed in a surrounding atmosphere or calcined to be converted into a ceria-based ceramic film to form a patterned insulating film. Further, the present inventors have exemplified a proposal for a photosensitive polyamidene composition which has a positive function and a positive function by using a modified polydecaine sulphamine in the use of a modified polypime sesquiamine. In such a method of using a positive photosensitive polyamidone composition, an exposed portion of the photosensitive polyamidamine coating film generates an acid which causes the Si-N bond of the polyamine to be cleaved. Reacts with the H20 molecule to form a stanol (Si-〇H) bond, causing the polyamine to decompose. However, in the above-mentioned conventional techniques for attempting to decompose polyamines, the specific treatment method is a method in which a photosensitive polyamidone is brought into contact with water after exposure. The positive-type photosensitive polyalkane composition of the above-mentioned proposals has a high resolution when compared with the negative photosensitive polyimide composition. However, it is necessary to additionally improve the resolution for pattern miniaturization. Moreover, the exposed photosensitive polyamido composition is attempted to contact with water to decompose the polyamine chamber. However, the decomposition of the polyamine is only performed near the surface of the photosensitive polyamine composition. It is not possible to sufficiently remove the image of the exposed portion by the subsequent aqueous solution according to the decomposition treatment conditions. 5. The coating film of the exposed portion at the time of the invention (4), after the development, there is still a development residue on the pattern, and There is a problem that the adhesion between the photosensitive polyamide substrate and the substrate is insufficient. Therefore, a decomposition method of a photosensitive polyimide substrate having no such problem is also required. In addition, when the photosensitive polyamipene coating film is calcined to be converted into a ceria-based ceramic film, only the polyamidene coating film is heated, and the polyamine oxide is not sufficiently oxidized to form a film. A cerium oxide ceramic film in which a plurality of polyamidones have a S i -N bond remains, and it is difficult to form a film having a very low dielectric constant as an interlayer insulating film. Further, when a large number of S 1 -N bonds remain in the cerium oxide ceramic film, there is a problem in that moisture absorption is likely to occur and a film having unstable physical properties is formed. Therefore, when the photosensitive polyimide substrate is calcined and the polyamidene in the film is converted into a cerium oxide ceramic, it is desired to be easily and sufficiently converted, thereby obtaining an excellent dielectric constant. A method of calcining a photosensitive polyamidamine coating film having a characteristic and a cerium oxide-based ceramic film in which no S i -N bond remains in the film. In view of the above problems, the present invention provides a method for forming a patterned polyamidene coating film using a photosensitive polyamidane composition, and decomposing a polyamidene of a photosensitive polyamidene composition after exposure. The method requires a short time, good adhesion to the substrate, no development residue on the pattern after development, and a method for forming a patterned polyalkane film. Further, the present invention provides a photosensitive polyamine which can sufficiently oxidize a polyamidamine even if it is merely heated, and forms a cerium oxide-based ceramic film having no or almost no Si-N bond in the film. The calcination method of the alkane coating film is for the purpose. 1252383 V. Inventive Note (5) Further, the present invention is extremely useful as an interlayer insulating film which can form an interlayer insulating film having a low dielectric constant, excellent heat resistance, abrasion resistance, corrosion resistance, insulation, and transparency. It is an object of a photosensitive polyamidone composition of a ceramic film, a method of forming a pattern photosensitive polyalkane film, and a calcination method of a photosensitive polyimide film. Further, the present invention has an object of providing a photosensitive polyamidiamine composition having high resolution. The inventors of the present invention found the following findings in order to achieve the above object and further intensively study. In other words, it has been found that when a patterned polyimide substrate is formed using a photosensitive polyamilane composition containing a polyamidamine and a photoacid generator, and a photosensitive composition having a positive function, by exposure The photosensitive polyimide substrate is contacted with a gas containing water vapor, that is, humidified, and the polyamine is decomposed in a short time, and no development residue is formed on the pattern after development, and the gas is increased at this time. The steam content, or the temperature of the photosensitive polyamipene coating film after heating, shortens the decomposition time, and relaxes the conditions of condensation on the surface of the film after heating the film, thereby improving the steaming of the humidifying atmosphere. The atmosphere pressure can further improve the adhesion between the polyamide film and the substrate by heating during development by shortening the time required for the decomposition of the polyamine. Further, it has been found that when the photosensitive polyamide substrate is subjected to calcination, the coating film is exposed to light before the calcination, and the humidification treatment is carried out, whereby the conversion into the ceria-based ceramic can be easily and sufficiently performed. A cerium oxide-based ceramic film having excellent properties and having no S 1 -N bond remaining in the film is obtained. In addition, it has been found that by adding a water-soluble compound as a shape tft female hydrating agent to a photosensitive composition containing a specific modified polysapphire compound and photoacid hair 1252383 5, invention (6) In order to improve the resolution, the photosensitive composition can form a fine pattern of an interlayer insulating film having excellent dielectric constant, insulating property, and mechanical properties after firing, and the present invention is based on the above findings. Disclosure of the Invention The present invention relates to a method for forming a polyimide channel formed by the following method, a method for calcining a photosensitive polyamidamine coating film, and a photosensitive polyamido compound composition [1] a pattern forming method It is a method for forming a patterned polyimide film by exposing a coating film of a photosensitive polyamidane composition to an exposed polyimide film. The film is imaged after the humidification treatment [2] The pattern forming method according to the above [1], wherein the photosensitive polyimide substrate is heated during the humidification treatment. [3] A method for calcining a photosensitive polyamidamine coating film, which is a method for calcining a photosensitive polyamidamine coating film, which is characterized in that a coating film for salty VQiN photopolyamide is provided. The engineering and humidification treatment works as the calcined crucible treatment project. [4] A method for calcining a photosensitive polyimide film according to the above [3], wherein the photosensitive polyimide film is patterned. [5] The calcination method 1 of the photosensitive polyamipene coating film according to the above [3], wherein the photosensitive polyamidone is used in the humidification treatment: ~ 8 - coating film: i 孰 / V \\ 〇 1252383 V. Description of the invention (9) Calcination. The patterned polyamidamine film formed by the above method of the present invention can be directly used for, for example, etching a pattern film in an element such as a photoresist or a display element. Since the photosensitive polyamidene composition used in the present invention is a positive type, the resolution is high, and the conventional organic material-based photoresist has a high oxygen-resistant plasma property. In addition, the ceria-based ceramic film formed by the calcination method of the present invention is particularly excellent as an interlayer insulating film because it is a film excellent in heat resistance, low dielectric property, transparency, and the like. Further, according to the present invention, the water-soluble compound which is a shape-stabilizing agent is added to the photosensitive polyamidene composition containing the specific modified polydecyl sesquiamine and the photo-acid generator described in the above [6]. The resolution of pattern processing can be further improved by light. Further, by applying the coating film formed of the photosensitive polyamidone composition described in the above [6] to [1 7] for a long time or by calcination, high heat resistance suitable as an interlayer insulating film can be obtained. An excellent pattern of cerium oxide ceramic film, such as low dielectric constant, transparency, and the like. Further, in the present invention, the sensitizing dye □ is contained in the photosensitive polyimide composition, and can be patterned using a low-cost light source such as a high-pressure mercury lamp. Further, in the present invention, the sensitizing dye is decomposed when the film is fired after patterning by containing an oxidizing catalyst in the photosensitive polyamidone composition containing the sensitizing dye, and is obtained as a liquid crystal display device. A colorless transparent cerium oxide ceramic film which is extremely useful as an interlayer insulating film. In addition, in the present invention, a color filter having excellent pattern precision, which is excellent in heat resistance, insulation, and hardness, can be produced by adding -11-1252383 to the photosensitive polyamidane composition, and the pigment (1〇). Or black matrix. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a pattern cross-sectional side wall shape of a photosensitive polyamidene composition containing no water-soluble compound of a shape stabilizer. Fig. 2 is a schematic cross-sectional view showing a pattern cross-sectional side wall shape of a photosensitive polyamidene composition containing a water-soluble compound of a shape stabilizer. Fig. 3 is a chart showing the infrared absorption spectrum of the modified polyfluorinated sesquiamine used in the photosensitive composition of the present invention. Fig. 4 is a chart showing the infrared absorption spectrum of the calcined film formed in the examples of the present invention. Fig. 5 is an infrared absorption spectrum of the calcined film formed in the comparative example. The present invention will be described in more detail below. The pattern forming method of the polyamidamine film of the present invention is not particularly limited, but contains (a) a coating film forming process in which a photosensitive polyamidene composition is coated or printed on a substrate to form a coating film. And (b) exposing the pattern to the light on the coating film, and (c) contacting the substrate subjected to the pattern with a gas containing water vapor in a state where the substrate is heated, and decomposing the polyamine (d) a developing process in which a portion of the coating film which is irradiated with light is dissolved and removed. The method for forming the patterned polyamidamine film of the present invention will be specifically described below by way of the exemplified method. First, in the method for forming a polyalkane film of the present invention, the photosensitive -12-1252383 V. The invention (彳1) composition can use a photosensitive poly-5 containing a polyamine amine and a photoacid generator. A photosensitive composition having a positive function of an alkane composition. The polyamidene used in the positive photosensitive polyamidene composition is typically exemplified by the following. (A) contains a general formula: (wherein R1, R2 and R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or the like, the bond is externally bonded to the ruthenium or the nitrogen moiety is carbon Polyalkylene oxide having a number average molecular weight of from 100 to 50,000, or a modification thereof, of the structure shown by the group, alkylalkylalkyl group, alkylamino group or alkoxy group. (B) Containing the formula: -[S i R4 (NR5) , · 5], plant (Π) (wherein R4 and R5 each independently represent a hydrogen atom, a deutero group, an alkenyl group, a cycloalkyl group, an aryl group The basis of these structures is bonded to a ruthenium or a nitrogen moiety, a alkyl sulfonyl group, an alkylamino group or an alkoxy group, and η represents an arbitrary integer. The number average molecular weight of the structure shown is 100 to 100, A polypeptidylamine or a modified substance thereof. (C) contains -(1^丨1)-, -(1^11〇)-, -(1^州02)-, and -(Rs 1 03)- (wherein R represents an alkyl group, an alkenyl group , a cycloalkyl group, an aryl group, an alkylamino group or an alkylalkylene group) having a number average molecular weight of 300 to 100, a polyorganoguanamine of hydrazine. -13- 1252383 V. INSTRUCTION DESCRIPTION (12) (D) contains the general formula: -[S i R6 (NR7) ! 5]-(Π) as the basic structural unit, and the general formula: -[S i R62nr, 〕—(IV) and/or [S i R63 (NR7). 5]-(v) (wherein R6 each represents an alkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted phenyl group, and R7 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or substituted or The other constituent unit represented by the unsubstituted phenyl group contains 0.1 to 100 mol%, preferably 0.5 to 40 mol%, more preferably 1 to 20 mol%, of the above basic constituent unit. A polyanthraquinone having a number average molecular weight of 1 〇〇 1 〇〇 10,000. In the modified polydecyl sesquiamine, other constituent units are randomly bonded to the basic structure. Moreover, any one of R6 and R7 in the modified polysapphire compound may be individually selected from a specific group, and the basic constituent units may be the same or different, and the basic constituent units may be the same as the other constituent units or different. For example, in the basic constituent unit, a part of R6 is a methyl group, the remaining part is a phenyl group, a part of R7 is a hydrogen atom, and the remainder is a methyl group, and R6 of a basic constituent unit is a methyl group, and R6 of a other constituent unit is a methyl group or a phenyl group. It is possible that R7 in the basic constituent unit is hydrogen, and other constituent units R7 are methyl groups and the like. Among the basic constituent units and other constituent units, R6 is preferably a methyl group or a phenyl group, particularly a methyl group. Further, in the basic constituent unit and the other constituent units, R7 is preferably hydrogen. -14- 1252383 V. INSTRUCTION OF THE INVENTION (13) In the modified polydecyl sesquiamine of the above (D), when the constituent unit of the general formula (丨v) is contained as another constituent unit, the constitution of the general formula (丨V) The unit contains 〇·1 mol% to i mol%, preferably 1 mol% to 20 mol%, of the above basic constituent unit. Further, when the constituent unit of the general formula (v) is contained as another constituent unit, the constituent unit of the general formula (V) contains 0.1 mol% to 50 mol%, preferably 0.5 mol%, to the above basic constituent unit. %~2〇% by mole. If the other constituent unit is less than 〇1 mol%, the stability of the polymer itself is low, and polymerization occurs between the polymers during storage. On the other hand, if the other constituent unit is more than 1% by mole, the molecular weight of the polymer is insufficient and the coating film is fluid, so it is not desirable. The modified polyfluorinated sesquiamine used in the above (D) has a number average molecular weight of from 100 to 1,000,000, preferably from 500 to 5,000. If the number average molecular weight of the modified polyhydrazine sesquiamine is less than 1 〇〇, the coating film will have fluidity, and if it is more than 100,000, it is not easily dissolved in the solvent, so it is not desirable. In the present invention, the polyamined alkane is used in the form of the above-mentioned polyindolide and polyorganosalkane. Further, in the present invention, the polyamidamine is of course a single polyamine, or may be a polymer of two or more kinds, or a copolymer of polyamine and another polymer, or a polyalkylene oxide and other polymerization. a mixture of substances or compounds. The polyamine to be used may be a chain, a ring or a crosslinked structure, or may have such a plurality of structures in the molecule, and these may be used singly or in a mixture. These polyamines are preferably a perhydropolyamine for the hardness or compactness of the obtained film, and an organic polyamine for flexibility. The choice of such polyamines is based on the use of the phthalocyanine as appropriate. -15-1252383 V. Illustrative (μ). The above-mentioned polyamidamine is a conventional or known method manufacturer. Specifically, the production of polyamidamine is disclosed, for example, in Japanese Patent Publication No. Sho 63 3 _ 1 6 3 2 5 and JP-A-61-892 3 Bulletin No. 0, the same as 62- 1 56 1 3 5, D. Seyferth, etc. 〇〇1〇1111^. 2"〇11(^八[11.〇61*.3〇(:·,.-Π ' January(1983) , Polym. Prepr. , Am· Chem. Soc., Div· P〇lym_ chem.,11 , 1 0 (1 984), etc. Further, 'polyamines having a crosslinked structure in the molecule, for example, JP-A-49-69717, D. Seyferth et al., Communication of Am. Cei:. Soc., C -132, Reporter in July (1 984), or a polymetallic guanamine containing such a metal atom. Others, such as the ones in the Japanese Patent Laid-Open Publication No. 62-1 95024, are [(31[12)11 (off) ) „1] and [(31[121〇] (where n, m, r are 1, 2 or 3) are disclosed in the polypyroxane, and the polypyrene is disclosed in JP-A-2-48 4 3 7 In the alkane, the boron compound is produced by the reaction of the boron compound, and the heat-resistant polyboron broth is disclosed in Japanese Laid-Open Patent Publication No. SHO-63-81-112, No. 63-119, 832, and JP-A-2-77427. Polymetallic guanamine, which is prepared by reacting an alkane with a metal alkoxide, and the same as 1 - 1 38 1 07, 1 - 203429, 1 - 203430, and 4 - Increased molecular weight as disclosed in the Gazette of 63 8 3 No. 3, the same as 3 - 320 1 67 (on (Before the publication) (4), the inorganic decane high polymer or the modified polyamidamine which is improved in heat decomposition resistance (the latter two), the special Kaiping 2 - 1 7 5 726, the same 5 - 86200, the same 5- The introduction of an organic component into the polyamidamine disclosed in the publication No. 33 1 29 3 and 3-3 1 3 26 is advantageous for 6 1252383. 5. Description of the invention (15) Film thickening of a copolymerized polyamine plant, special It is disclosed in JP-A No. 5-238827, No. 6-122852, No. 6-299188, No. 6-306329, No. 6-240208, and No. 7-1 96986, added or added to polyamine. The catalyst compound for promoting ceramization is applied to a metal such as plastic or aluminum, and a ceramic low-temperature ceramic polyamine furnace or the like is used in the same manner at a lower temperature. The polyamine gas which is suitably used in the present invention mainly contains the above-mentioned pass. The structure represented by the formula (II), the number average molecular weight of 100 to 100,000, preferably 300 to 1 0,000 of polydecyl sesquiamine and derivatives thereof, and more preferably polypyridylsamine (II) Polyphenylamine which is a methyl group and R5 is hydrogen. The polyamine is used in the synthesis of a general polyamine. R4S i C 13 used as a starting material easily produced. The amine hydrolysis in the case of synthesizing polyamidamine is described, for example, in JP-A-63-1665. Further, the polyorganosalkonane of the above (C) may also be a polyamidene suitable for use in the present invention. The polyorganoguanamine can generally be represented by the formula RnSiX4_n (wherein R is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group or an alkylalkyl group, the X system is a halogen atom, and the η system is 1 or 2) is prepared by reacting a decane with ammonium and water. The polyorganosalkonane may be represented by the formula RnSiX4_n (wherein R represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group or an alkylalkyl group, the X system represents a halogen atom, and the η system represents The organic halogenated decane shown in 1 or 2) is obtained by reacting with ammonium and water. The polyorganoguanamine is particularly useful as an interlayer insulating film precursor because a calcined film having a low dielectric constant can be obtained even when treated at a high temperature. Further, in the case of polyorganoguanamine, the calcined film can be controlled by changing the oxygen content contained in the main chain. -17- 1252383 5. The invention (16) specific dielectric constant is easy to obtain. The advantage of the specific dielectric constant. A detailed description of the organic amine and its preparation can be found in the specification of the Japanese Patent Application No. 1 0 - 5 286 3 3 (W098 / 029475). Further, in the present invention, the modified polypeptazone which is described in the above (D) is particularly useful as a polyamidamine. The modified polyfluorinated sesquiamine compound can be used as the starting material for R6SiCl3, R^SiCl2 and/or R^SiCl in the amination of the general polyazaamine. The molar ratio of the unit content ratio can be easily obtained. For example, a formula containing 20 mol% as another constituent unit: [SlR62NR7]i, an amine solution can be used by using R62SiCi2 decane raw material mixed with 20 mol% of R6SiCl3, and similarly contains 1 〇 mol%. As a general formula: [SiR63(NR7)〇.5]-, it is possible to use R^SiCl in which 10 mol% is mixed with R6SlCl3. For a detailed description of the amination reaction in the synthesis of polyamidamine, reference is made, for example, to Japanese Patent Publication No. Sho 63-1363. The modified polydecyl sesquiamine represented by the above (D) has high stability and does not polymerize to a high molecular weight when stored substantially. A polymer that is not limited by a particular theory, but consists only of the basic constituent units of the trifunctional form, has a skewed ring structure in the molecule, and this is equivalent to the occurrence of cracking during storage by the cracking portion Other molecules that are also cracked are then bonded to form a higher molecular weight. When a difunctional and/or monofunctional constituent unit is introduced into the basic constituent unit of the trifunctional form, it is difficult to cause cracking/recrystallization in order to reduce the skewed ring structure, and the polymer can be controlled to be highly polymerized-18 - 1252383 V. INSTRUCTION DESCRIPTION (17) The photosensitive composition used in the present invention or the present invention contains a photoacid generator. The photoacid generator can be indirectly excited by direct irradiation of light in the original photosensitive wavelength range or by indirect irradiation of light in a wavelength range excited by the sensitizing dye when the sensitizing dye is used. The S i - N bond of the polyamidamine is cleaved by the photoacid generator in an excited state, and the cleaved S 1 - N bond reacts with moisture to form a stanol (S i - 0H ) bond. Since the stanol is soluble in the following developing solution, only the light-irradiated portion of the photosensitive composition coating film is dissolved and removed, and a positive pattern is achieved. Specific examples of the photoacid generator used in the positive-type photosensitive polyamidene composition include, for example, a peroxide, a naphthoquinonediazide sulfonate, a nitrobenzyl ester or the like. Moreover, benzoyltoluenesulfonate is also extremely useful. Other photoacid generators such as nitrobenzylsulfonic acid and phosphonium salts [e.g., bis(4-tributylphenyl)iodonium salt or triphenylsulfonium salt] are also extremely useful. These photoacid generators may be used in combination of two or more kinds as needed. Specific examples of the peroxide-based, naphthoquinonediazide sulfonate-based, and nitrobenzoate-based photoacid generators are shown below. However, the following exemplifications are merely illustrative, and the photoacid generator used in the present invention is not described by the following. Peroxic photoacid generator: 3,3',4,4'-tetra (3rd-butylperoxycarbonyl)benzophenone, 3rd-butylperoxybenzoate, methyl b Ketone peroxide, cyclohexane peroxide, methylcyclohexane peroxide, methyl ethyl ketone acetate peroxide, ethyl ketone acetone peroxide, 1, 1-double (3 - Hexyl peroxy) 3, 3, 5 - trimethyl-19- 1252383 V. Description of the invention (18) Cyclohexane, 1,1-bis(3-hexylperoxy)cyclohexane, hydrazine, hydrazine-bis ( 3-butyl peroxy) 3,3,5-trimethylcyclohexane, di-tert-butylperoxy-2-methylcyclohexan, 1,1-bis(di-3-butyl Peroxidation) Cyclohexa, ι,ι_bis (3rd-butylperoxy)cyclododecane, 2,2-bis (3 -butylperoxy) butane, n-butyl 4,4-double (3-butylperoxy) valerate, 2,2-bis(4,4-di-butyl-3-cyclohexyl)propane, p-decane hydroperoxide, diisopropyl Benzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, 3rd-hexyl hydroperoxide, 3rd-butyl hydrogen peroxide Oxide, α,α'-bis(3 -butylperoxy)diisopropylbenzene, cumenyl peroxide, 2,5-dimethyl-2,5-bis(3 - butyl Peroxidation) Hexane, 3 - butyl cumyl peroxide, di- 3 - butyl peroxide, 2,5-dimethyl-2,5-bis (3 -butyl peroxide) Hexyne-3, isobutyl peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, lauryl peroxide, stearyl peroxide, Succinic acid peroxide, m-tolylbenzyl benzhydryl peroxide, benzhydryl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis ( 4 - 3 -butylcyclohexyl)peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3-methoxy Butyl peroxydicarbonate, bis(3-methyl-3-methoxybutyl)peroxydicarbonate, α,α'-bis(indenyl peroxy)diisopropylbenzene, Cycloalkenyl peroxy neodecanoate, 1,1,3,3-tetramethylbutylperoxide Acid ester, 1-cyclohexyl-1 -methylethyl peroxy neodecanoate, 3 - hexyl peroxy neodecanoate, 3 - butyl peroxy neodecanoic acid-20 - 1252383 V. Description of the invention (19) Ester, 3'-hexylperoxyacetoxyacetate, 3rd-butylperoxytrimethylacetate, 1,1,3,3-tetramethylbutylperoxy-2- Ethyl hexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, 3rd-hexylperoxy-2-ethylhexanoate-3-3-butylperoxy-2-ethylhexanoate, 3rd-butyl peroxyisobutyrate, 3rd _Hexyl isopropyl isopropyl monocarbonate, 3 -butylperoxy maleic acid, 3 -butylperoxy-3,5,5 -trimethylhexanoate, 3 -butylperoxy peroxide Laurate, 2,5-dimethyl-2,5-(m-tolylperyl peroxide) hexane, 3 -butylperoxyisopropyl monocarbonate, 3 -butylperoxy- 2-ethylhexyl monocarbonate, 3rd-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzimidyl peroxy)hexane, 3-butyl Acetate, ternary 3-peroxy-m-tolyl benzoate, bis(tert-butylperoxy)isodecanoate, -3-butylperoxyallyl monocarbonate Ester, tert-butyltrimethylformamidine peroxide, 1,3-di-(3-butylperoxycarbonyl)benzene, and the like. Naphthoquinonediazide sulfonate photoacid generator: 1,2-naphthoquinone-(2)-diazido-5-sulfonic acid chloride, 1,2-naphthoquinone-(2)-two Azide-4-sulfonic acid chloride, 2,3,4-trihydroxybenzophenone and 6-azido-5,6-dihydro-5-carbonyl-naphthalene-1-sulfonic acid (single ~ 3) (mono-tri) ester of ester, 2,3,4,4'-trihydroxybenzophenone and 6-azido-5,6-dihydro-5-carbonyl-naphthalene-1-sulfonic acid ,Wait. Nitrobenzyl ester photoacid generator: nitrobenzyltoluene sulfonate, dinitrobenzyltoluenesulfonate-21 - 1252383 V. Description of invention (2〇) Ester, nitrobenzene Chloride, dinitrobenzyl chloride, nitrobenzyl bromide, dinitrobenzyl bromide, nitrobenzyl acetate 'dinitrobenzyl acetate, nitrate Benzobenzyl trichloroacetate, nitrobenzyltrifluoroacetate, and the like. The content of such a photoacid generator in the photosensitive polyamidene composition is appropriately quantified by the type of the photoacid generator and the use of the photosensitive composition, but generally speaking, for the weight of the polyamine 0.0 5 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 1 to 20% by weight. If the content of the photoacid generator is less than 0.05% by weight, the decomposition reaction rate is extremely slow, and if it is more than 50% by weight, for example, it is difficult to obtain the modified polypeptase. Features a dense membrane. In addition, when the polyimide composition containing the modified polypime sesquiamine and the photoacid generator must be stored for a certain period of time or more, the photoacid generator is partially based on nitrobenzylsulfonate. It may be decomposed due to a trace amount of NH3 free from polyamidamine when the photosensitive composition is stored. At this time, by selecting the alkali-resistant photoacid generator, the storage stability of the photosensitive composition can be improved. The alkali-resistant photoacid generator is, for example, an imidosulfonate derivative, a dioxane derivative, a diazidomethane derivative, and 4-methoxy-α-((((4-(4-methoxybenzene))) a sulfonium oxy)imino)imino)phenidinium quinone salt-based compound and a compound of the following formula; -22- 1252383 V. Description of invention (21)

CCI3CCI3

OCH3 另外，於感光性聚矽胺烷組成物中另藉由添加作爲形狀 安定化劑之水溶性化合物，可提高解像度。該效果於聚砂 胺烷爲上述（D )之改質聚矽倍半胺烷時特別顯著。此處， 形狀安定化劑係指可使藉由除去光照射部所形成的圖案截 面側壁更爲急峻化之劑。 如上述般聚矽胺烷藉由光照射使S 1 - N鍵開裂，然後藉 由與氣氛中之水分反應生成矽烷醇鍵。此時，鄰接於含水 氣氛之塗膜表面附近會快速引起矽烷醇鍵之生成。然而， 例如上述（D)改質聚矽倍半胺烷由於疏水性高，沒有鄰接 於含水氣氛之塗膜內部浸透自接近塗覆基板界面之塗膜表 面浸透的水份量很少，不易引起砂垸醇鍵。因此，改質聚 石夕倍半肢院自其表面對基板界面會有降低感光性之感度差 。本發明人等發現藉由該感度差會產生下述之問題。 -23- 1252383 五、發明說明（22) 如第1圖所示，改質聚矽倍半胺烷塗膜5除經由光罩1 之開口部直接照射的部分外、以光罩1遮蔽的改質聚矽倍 半胺烷部分藉由照射光之「滲出」間接照射的部分4。此 處，塗膜上存在有上述感度差時’接近於塗膜表面容易生 成矽烷醇鍵、藉由顯像容易解溶解除去。結果，如第1圖 所示，圖案截面側壁3成平穩狀’可知該現象係爲限制圖 案微細化、或解像度提高的原因之一。 本發明人發現添加作爲形狀安定化劑之水溶性化合物時 ，可使圖案截面側壁急峻化、提局解像度。換言之，藉由 添加水溶性化合物可降低感光性塗膜之疏水性、且可促進 自鄰接於含水氣氛之塗膜表面至塗膜內部之吸收。因此， 在塗膜表面附近與基板界面附近間之矽烷醇鍵的生成速度 稍差，即感度差小。如此可降低使在光罩開口部之塗膜部 分在基板界面附近充分溶解除去的必要照射光能量，進而 降低對光罩遮蔽部分之「滲出光」的能量。「滲出光」之 能量係直至使改質聚矽倍半胺烷之S i - NH季開裂過小的低 下部分，由於即使藉由該「滲出光」間接照射的部分4不 會生成矽烷醇鍵，故於顯像時不易溶解除去。結果，藉由 減少光罩遮蔽部分之溶解除去部分，可使圖案截面側壁急 峻化、且最佳者如第2圖所示之直立。 可知該圖案截面側壁之急峻化係有關達成感光性組成物 之感光度高低。換言之，基板附近之感光性組成物的感光 度變高時’如上述藉由降低照射光能量以使圖案截面側壁 -24- 1252383 五、發明說明（23) 急峻化。而且，例如於本發明中藉由添加水溶性化合物以 降低全體感光性組成物之感光度時，必須提高使光罩開口 部之塗膜邰分在基板界面附近充分溶解除去的必要照射光 能量而製得，惟由於提高光罩遮蔽的改質聚矽倍半胺烷部 分的S i - N Η鍵開裂之必要「滲出光」的能量，故塗膜感度 差變小時同樣會使圖案截面側壁急峻化。因此，無關感光 性組成物之感光度的高低，藉由使塗膜表面附近與基板界 面附近間之感光度差變小，可使圖案截面側壁急峻化。 該水溶性化合物係爲不溶於中性水、可溶於酸性水或鹼 性水、極爲有用。此係因溶於酸性水時輻射線照射部因自 光酸發生劑生成的酸而成酸性，或溶於鹼性水時藉由鹼水 溶液、於顯像時促進顯像液之浸透性。爲任一種時皆可促 進自塗膜表面至塗膜內部之水分吸收，故塗膜表面附近與 基板界面附近間之感度差變小。 本發明之水溶性化合物可以爲單一化合物或聚合物。該 水溶性化合物之水溶性程度對中性水、酸性水或鹼性水中 任一種而言爲O.Olg/lOOmL，惟不需易溶。而且，該水溶 性化合物由於以下述感光性組成物均句混合較佳，故必須 對聚矽胺烷或其溶劑具有充分的混合性。 該化合物之具體例如2 -硝基苯胺、3 -硝基苯胺、4 -硝基 苯胺、2 -硝基-4 -胺基甲苯、3 -硝基-2 -胺基甲苯、3 -硝基 -4 -胺基甲苯、4 -硝基-2 -胺基甲苯、5 -硝基-2 -胺基甲苯 、6 -硝基-2-胺基甲本、4 -硝基苯-偶氮-翔基吩瞳哄嗣、 -25- 1252383 五、發明說明（24) 1-(4 -硝基苯磺醯基）-1Η-1，2,4 -三哄、5 -硝基苯并咪唑啉 、4 -硝基苯甲基乙酸酯、2 -硝基苯甲醇、3 -硝基苯甲醇、 4 -硝基苯甲醇、硝基環己烷、1 -硝基丙烷、2 -硝基丙烷、 硝基苯吡啶、2 , 7 -二硝基聚四氯乙烯、2 , 7 -二硝基-9 -芴 酮、3,3，-二硝基二苯甲酮、3 ,4’ -二硝基二苯甲酮、碳酸 伸丙酯、碳酸伸乙酯、三氟乙烯醯胺之醯胺化合物、三氟 醋酸銨鹽、水溶性丙烯酸聚合物、水溶性環氧聚合物、水 溶性黑色素聚合物、等。特別適合的水溶性化合物係爲2 -硝基苯胺、3 -硝基苯胺、4 -硝基苯胺、2 -硝基-4 -胺基甲 苯、碳酸伸丙酯、碳酸伸乙酯及水溶性丙烯酸聚合物。 此等形狀安定化劑之水溶性化合物例如通常對改質聚矽 倍半胺烷而言添加0 . 01〜50重量％聚矽胺烷。視各種水溶 性化合物之特性、最適的混合比不同，惟含有量小於〇 . 〇 1 重量％時圖案側壁之傾斜改善效果小，反之，若大於50重 量％時顯像後之膜物性會產生瑕疵或強度不足的問題。水 溶性化合物對聚矽胺烷而言之添加量以0 . 05〜40重量％較 佳、更佳者爲0.1〜30重量％。 於調製感光性組成物時，可藉由在聚矽胺烷中添加上述 光酸發生劑及作爲形狀安定化劑之水溶性化合物予以進行 。以使光酸發生劑及該水溶性化合物均勻混合較佳，因此 以使聚矽胺烷與光酸發生劑及該水溶性化合物充分攪拌、 混合、或使其溶解於下述溶劑予以稀釋後混合爲宜◦特別 是於混合時使其溶解於溶劑後混合更佳。 -26- 1252383 五、發明說明（25 ) 添加時之溫度或壓力沒有特別的限制，可在室溫、大氣 壓下進行添加。惟以不會使光酸發生劑激勵下、自添加時 至下述顯像工程爲止在所使用的光酸發生劑不含感光波長 之環境下、較佳者爲暗處作業爲所企求。 另外，本發明所使用的含有聚矽胺烷與光酸發生劑之感 光性聚矽胺烷組成物中視其所需亦可含有增感色素。例如 於光酸發生劑必須爲如3, 3,4, 4’-四（第3-丁基過氧化羰 基）二苯甲酮、其本身被激勵的波長範圍約較3 30nm爲短 者。在該短波長範圍中具有感光範圍之光酸發生劑使用 KrF系（ 248nm)、ArF系（193nm)等準分子雷射光予以光照 射時，由於藉由此等照射光直接激勵故不須使用增感色素 。而且，使用高壓水銀燈（360〜43Onm)等低價光源時，藉 由組合該波長範圍所激勵的增感色素可間接激勵光酸發生 劑、於曝光時高壓水銀燈（360〜43Onm)等較低價的光源進 行曝光。增感色素例如有香豆素、異香豆素極其衍生物、 吡錠鹽及硫化吡錠鹽、或喹啉藍染料、碳化喹啉藍染料、 苯乙烯基染料等之染料。此等增感色素通常對聚矽胺烷而 言使用〇.〇5〜50重量％、較佳者爲1〜20重量％。 感光性聚矽胺烷組成物中所使用的增感色素，具體例如 對-雙（鄰-甲基苯乙烯基）苯、7 -二甲基胺基-4-甲基喹啉 酮-2, 7 -胺基-4-甲基香豆素、4，6 -二甲基-7-乙基胺基香 豆素、2 -(對-二甲基胺基苯乙烯基）-吡啶基甲基碘化物、 7 -二乙基胺基香豆素、7 -二乙基胺基-4-甲基香豆素、 -27- 1252383 五、發明說明（26) 2,3,5,6-1Η,4Η -四氫-8-甲基喹啉基-<9,9a,l-gh>香豆素 、7 -二乙基胺基-4-三氟甲基香豆素、7 -二甲基胺基-4-三 氟甲基香豆素、7 -胺基-4-三氟甲基香豆素、2,3,5,6-1H，4H-四氫卩奎啉基-<9,9a，l-gh>香豆素、7-乙基胺基-6-甲基-4-三氟甲基香豆素、7 -乙基胺基-4-三氟甲基香豆素 、2,3,5,6-111，4[1-四氫-9-碳化乙氧基卩奎啉基-<9,92，1-211>香豆素、3-(2’-N-甲基苯并咪唑啉）-7-N，N-二乙基胺 基香豆素、N -甲基-4-三氟甲基吡啶基-<3,2-g>香豆素、 2-(對-二甲基胺基苯乙烯基）-苯并噻唑基乙基碘化物、3-(2、苯并咪唑啉）-7-N，N -二乙基胺基香豆素、3-(2’-苯并 噻唑基）-7-N,N -二乙基胺基香豆素、以及以下式所示之吡 錠鹽及硫化吡錠鹽。OCH3 Further, by adding a water-soluble compound as a shape stabilizer to the photosensitive polyamidene composition, the resolution can be improved. This effect is particularly remarkable when the polyalkane is the modified polydecyl sesquiamine of the above (D). Here, the shape stabilizer is an agent which can make the side wall of the pattern cut surface formed by removing the light-irradiating portion more sharp. As described above, the polyamine is caused to cleave the S 1 -N bond by light irradiation, and then reacts with moisture in the atmosphere to form a stanol linkage. At this time, the vicinity of the surface of the coating film adjacent to the aqueous atmosphere rapidly causes the formation of stanol linkages. However, for example, the above-mentioned (D) modified polyphosphazene is highly hydrophobic, and the amount of water which is not soaked in the surface of the coating film which is adjacent to the interface of the coating substrate which is not adjacent to the aqueous atmosphere is small, and is not likely to cause sand. Sterol key. Therefore, the modified poly-stone compound has a sensitivity difference that reduces the sensitivity of the substrate from the surface to the substrate. The present inventors have found that the following problems occur due to the difference in sensitivity. -23- 1252383 V. INSTRUCTION OF THE INVENTION (22) As shown in Fig. 1, the modified polydecyl sesquiamine coating film 5 is shielded by the mask 1 except for the portion directly irradiated through the opening of the mask 1. The portion 4 of the polyphosphoric acid moiety which is indirectly irradiated by "exudation" of the irradiated light. Here, when the above-mentioned sensitivity difference is present on the coating film, it is easy to generate a stanol linkage near the surface of the coating film, and it is easily dissolved and removed by development. As a result, as shown in Fig. 1, the pattern section side wall 3 is formed in a smooth state, and this phenomenon is considered to be one of the reasons for limiting the pattern miniaturization or improving the resolution. The present inventors have found that when a water-soluble compound as a shape stabilizer is added, the side wall of the pattern cross section can be sharpened and the resolution can be improved. In other words, by adding a water-soluble compound, the hydrophobicity of the photosensitive coating film can be lowered, and absorption from the surface of the coating film adjacent to the aqueous atmosphere to the inside of the coating film can be promoted. Therefore, the rate of formation of sterol bonds between the vicinity of the surface of the coating film and the vicinity of the substrate interface is slightly inferior, that is, the difference in sensitivity is small. In this way, the necessary irradiation light energy for sufficiently dissolving and removing the coating film portion in the opening portion of the mask at the interface of the substrate can be reduced, and the energy of "bleeding light" to the mask portion of the mask can be reduced. The energy of "exuding light" is such that the lower portion of the S i - NH cleavage of the modified poly sesquiamine is too small, since even the portion 4 which is indirectly irradiated by the "bleeding light" does not form a stanol linkage. Therefore, it is not easy to dissolve and remove during development. As a result, by reducing the portion of the reticle shielding portion which is dissolved and removed, the side wall of the pattern cross section can be sharpened, and the best one is as shown in Fig. 2 upright. It is understood that the sharpness of the side wall of the pattern cross section is related to the sensitivity of the photosensitive composition. In other words, when the sensitivity of the photosensitive composition in the vicinity of the substrate becomes high, the above-described invention (23) is sharpened by reducing the irradiation light energy as described above to make the pattern cross-section side wall -24 - 1252383. Further, for example, in the present invention, when a water-soluble compound is added to reduce the sensitivity of the entire photosensitive composition, it is necessary to increase the necessary irradiation light energy for allowing the coating film of the opening of the mask to be sufficiently dissolved and removed in the vicinity of the substrate interface. However, since the energy of "exuding light" which is necessary for the S i - N Η bond cracking of the modified polydecyl sesquiamine moiety which is masked by the reticle is improved, the difference in the sensitivity of the coating film also causes the sidewall of the pattern section to be steep. Chemical. Therefore, irrespective of the sensitivity of the photosensitive composition, the difference in sensitivity between the vicinity of the surface of the coating film and the vicinity of the substrate interface can be made small, so that the side wall of the pattern cross section can be sharpened. The water-soluble compound is extremely insoluble in neutral water and soluble in acidic water or alkaline water. This is because the radiation ray irradiation portion is acidic when it is dissolved in acidic water due to the acid generated from the photoacid generator, or the alkaline water solution is used to promote the permeability of the developing solution at the time of development. In either case, the moisture absorption from the surface of the coating film to the inside of the coating film can be promoted, so that the difference in sensitivity between the vicinity of the surface of the coating film and the vicinity of the substrate interface becomes small. The water-soluble compound of the present invention may be a single compound or a polymer. The water-soluble compound has a water solubility of 0.1 mol/lOOmL for any of neutral water, acidic water or alkaline water, but does not require easy dissolution. Further, since the water-soluble compound is preferably mixed uniformly in the following photosensitive composition, it is necessary to have sufficient mixing property with the polyamine or its solvent. Specific examples of the compound are, for example, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-nitro-4-aminotoluene, 3-nitro-2-aminotoluene, 3-nitro- 4-aminotoluene, 4-nitro-2-aminotoluene, 5-nitro-2-aminotoluene, 6-nitro-2-aminomethyl, 4-nitrobenzene-azo-xiang Basement, -25- 1252383 V. Description of the invention (24) 1-(4-Nitrophenylsulfonyl)-1Η-1,2,4-tris-, 5-nitrobenzimidazoline, 4-nitrobenzyl acetate, 2-nitrobenzyl alcohol, 3-nitrobenzyl alcohol, 4-nitrobenzyl alcohol, nitrocyclohexane, 1-nitropropane, 2-nitropropane, Nitrophenylpyridine, 2,7-dinitropolytetrachloroethylene, 2,7-dinitro-9-fluorenone, 3,3,-dinitrobenzophenone, 3,4'-dinitrate Benzophenone, propyl carbonate, ethyl carbonate, guanamine compound of trifluoroethylene decylamine, ammonium trifluoroacetate, water-soluble acrylic polymer, water-soluble epoxy polymer, water-soluble melanin polymer ,Wait. Particularly suitable water-soluble compounds are 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-nitro-4-aminotoluene, propyl carbonate, ethyl carbonate and water-soluble acrylic acid. polymer. The water-soluble compound of such a shape stabilizer is, for example, usually added to the modified polydecyl sesquiamine by 0.01 to 50% by weight of polyamine. Depending on the characteristics of the various water-soluble compounds and the optimum mixing ratio, the content of the side wall of the pattern is less improved when the content is less than 〇. 〇1% by weight. Conversely, if it is more than 50% by weight, the film properties after development may occur. Or the problem of insufficient strength. The amount of the water-soluble compound added to the polyamidene is preferably from 0.05 to 40% by weight, more preferably from 0.1 to 30% by weight. When the photosensitive composition is prepared, it can be carried out by adding the above photoacid generator and a water-soluble compound as a shape stabilizer to polyamine. In order to uniformly mix the photoacid generator and the water-soluble compound, the polyamine, the photoacid generator, and the water-soluble compound are sufficiently stirred, mixed, or dissolved in the following solvent to be diluted and mixed. It is preferred to mix it after it is dissolved in a solvent, especially when mixing. -26- 1252383 V. INSTRUCTIONS (25) There is no particular limitation on the temperature or pressure at the time of addition, and it can be added at room temperature or atmospheric pressure. In the case where the photoacid generator to be used is not excited by the photoacid generator, and the photoacid generator to be used does not contain a photosensitive wavelength, it is preferable to operate in a dark place. Further, the photosensitive polyamidene composition containing a polyamidamine and a photoacid generator used in the present invention may contain a sensitizing dye as needed. For example, the photoacid generator must be, for example, 3,3,4,4'-tetra(3-butylperoxycarbonyl)benzophenone, which is itself excited to a wavelength range of about 3 30 nm. When the photoacid generator having a photosensitive range in the short-wavelength range is irradiated with excimer laser light such as KrF (248 nm) or ArF (193 nm), since it is directly excited by such irradiation light, it is not necessary to use Sensitive pigment. Further, when a low-cost light source such as a high-pressure mercury lamp (360 to 43 Onm) is used, the photoacid generator can be indirectly excited by combining the sensitizing dye excited by the wavelength range, and the low-pressure mercury lamp (360 to 43 Onm) at the time of exposure is lower. The light source is exposed. The sensitizing dyes include, for example, coumarin, isocoumarin extreme derivatives, pyridinium salts and sulfurized pyridinium salts, or quinoline blue dyes, carbonated quinoline blue dyes, styryl dyes, and the like. These sensitizing dyes are usually used in the form of polyamines in an amount of from 5 to 50% by weight, preferably from 1 to 20% by weight. The sensitizing dye used in the photosensitive polyamidene composition is specifically, for example, p-bis(o-methylstyryl)benzene or 7-dimethylamino-4-methylquinolinone-2. 7-Amino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2-(p-dimethylaminostyryl)-pyridylmethyl Iodide, 7-diethylamino coumarin, 7-diethylamino-4-methylcoumarin, -27- 1252383 V. Description of invention (26) 2,3,5,6-1Η , 4Η-tetrahydro-8-methylquinolinyl-<9,9a,l-gh>coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethyl Amino-4-trifluoromethylcoumarin, 7-amino-4-trifluoromethylcoumarin, 2,3,5,6-1H,4H-tetrahydrofurfuryl quinolyl-<9,9a,l-gh>coumarin,7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin , 2,3,5,6-111,4[1-tetrahydro-9-carboethoxy quinolinyl-<9,92,1-211> Coumarin, 3-(2'-N -Methylbenzimidazoline)-7-N,N-diethylaminocoumarin, N-methyl-4-trifluoromethylpyridyl-<3,2-g> Coumarin, 2-(p-dimethylamine Styryl)-benzothiazolylethyl iodide, 3-(2,benzimidazoline)-7-N,N-diethylamine coumarin, 3-(2'-benzothiazolyl -7-N,N-diethylamino coumarin, and a pyridinium salt and a thiopyridinium salt represented by the following formula.

-28- 1252383 五、發明說明（27) X r2 r3 Y S 〇c4h9 H H BF4 S 〇c4h9 H H B F 4 S o c 4h9 O C H 3 〇 ch3 B F 4 S Η O CH 3 〇ch3 B F 4 S n(ch3)2 H H C 1 02 〇 〇c4h9 H H S bF6 另外，其它的增感色素之具體例如 -29- 1252383-28- 1252383 V. INSTRUCTIONS (27) X r2 r3 YS 〇c4h9 HH BF4 S 〇c4h9 HHBF 4 S oc 4h9 OCH 3 〇ch3 BF 4 S Η O CH 3 〇ch3 BF 4 S n(ch3)2 HHC 1 02 〇〇c4h9 HHS bF6 In addition, other sensitizing pigments such as -29-1252383

1252383 五、發明說明（29) 更佳的增感色素爲7 -二乙基胺基-4-甲基香豆素及7 -二 乙基胺基-4-三氟甲基香豆素。 使用增感色素時，所得的被膜著色。使用該被膜作爲蝕 刻光阻劑等之光阻劑時，由於所企求的圖案加工完成後除 去該光阻劑、故不會有光阻劑著色的問題。而且，使圖案 被膜煅燒、且於圖案化後不除去該被膜時，例如煆燒後之 被膜使用作爲顯示元件之層間絕緣膜等時，煅燒後之被膜 對可視光而言必須爲透明。此時，通常於被膜煆燒時因感 光性聚矽胺烷組成物中所含的光酸發生劑使增感色素分解 被膜被透明化後，故不會有相當的問題發生，惟視其所使 用的目的而定亦有必須爲透明無著色的被膜。此時，可另 外添加於感光性聚矽胺烷組成物中於被膜煅燒時使增感色 素分解之與光反應無關的氧化觸媒。該氧化觸媒例如有丙 酸鈀、醋酸鈀、異醯基乙酸鉛、乙基乙酸鈾、鈀微粒子、 鉑微粒子等金屬有機化合物或微粒子等。添加氧化觸媒時 ’氧化觸媒之量^彳聚砂胺院而言一般爲0 . 0 5〜1 0重量％、 較佳者爲0.1〜5重量％。藉由添加該氧化觸媒，可使不需 的色素分解、脫色外，且可促進聚矽胺烷陶瓷化。 另外，藉由於感光性聚砂胺烷組成物中添加顏料，可得 耐熱性、絕緣性、硬度優異、圖案精度佳的濾色器或黑色 基體。聚矽胺烷組成物中所添加的顏料例如石墨、碳黑、 鈦黑、氧化鐵、銅鉻系黑、銅鐵錳系黑、鈷鐵鉻系黑等。 顏料添加量一般對聚矽胺烷而言爲0.05〜1〇〇〇重量％、較 -3 1 - 1252383 五、發明說明（3〇 ) 佳者爲10〜500重量％。 此外，爲提高顯像效率時，在該技術範圍內在感光性聚 矽胺烷組成物中可添加作爲溶解防止劑之習知化合物。一 般的溶解防止劑藉由其疏水性可防止塗膜之未曝光部分之 聚合物溶出鹼顯像液中，曝光部分藉由曝光或藉由光酸發 生劑使溶解防止劑本身被分解成親水性，具有促進聚合物 分解之作用。如上述由於聚矽胺烷不會溶解於顯像液中， 幾乎沒有享受到溶解防止劑之未曝光部分的溶出防止作用 優點，惟對曝光部之溶解促進作用極爲有力。換言之，藉 由在感光性聚矽胺烷組成物中添加溶解防止劑，就提高曝 光部之溶解速度而言可提高顯像效率。該溶解防止劑之具 體例如第3 - 丁氧基羰基（以下稱爲t - BOC )化兒茶酚、t -BOC化氫錕、二苯甲酮- 4,4’-二羧酸第3-丁酯、4,4、氧化 二苯甲酸第3 - 丁酯、等。溶解防止劑對感光性組成物而言 添加0.1〜40重量％、較佳者爲1〜30重量％。 於感光性聚矽胺烷組成物中使用溶劑時，以使用苯、甲 苯、二甲苯、乙苯、二乙苯、三甲苯、三乙苯等芳香族化 合物；環己烷烷、環己烯；十氫萘；二戊烯；正戊烷、異 戊烷、正己烷、異己烷、正庚烷、異庚烷、正辛烷、異辛 烷、正壬烷、異壬烷、正癸烷、異癸烷等飽和烴化合物； 乙基環己烷；甲基環己烷；對-荖烷；二丙醚、二丁醚等 醚類；甲基異丁酮（MISK)等之酮類；醋酸丁酯、醋酸環己 酯、硬脂酸丁酯、乳酸乙酯等酯類；乙二醇單甲醚、乙二 -32- 1252383 五、發明說明（31) 醇單乙醚等乙二醇單烷醚類；乙二醇單甲醚乙酸酯、乙二 醇單乙醚乙酸酯等乙二醇單烷醚乙酸酯類；丙二醇單甲醚 、丙二醇單乙醚等丙二醇單烷醚類；丙二醇單甲醚乙酸酯 (PGMEA)、丙二醇單乙醚乙酸酯等丙二醇單烷醚乙酸酯類 等較佳。使用此等溶劑時，爲調節聚矽胺烷之溶解度或溶 劑之蒸發速度時可以2種以上混合使用。 溶劑之使用量（比例）係考慮所採用塗覆方法之作業性、 或感光性組成物之各成分的溶解性、感光性組成物之塗覆 性、塗覆膜厚等予以決定。視所使用的聚矽胺烷的平均分 子量、分子量分布、其構造而定對溶劑之溶解性不同。而 且，考慮聚矽胺烷之安定性或製造效率、塗覆性等時，通 常聚矽胺烷濃度爲0 . 1〜50重量％、較佳者爲0 . 1〜40重 量％。 而且，本發明之感光性組成物中視其所需可加入適當的 塡充劑及/或增量劑。塡充劑例如以二氧化矽、氧化鋁、 氧化鉻、雲母爲始的氧化物系無機物或碳化矽、氮化矽等 非氧化物系無機物的微粉等◦此外，視用途而定亦可添加 鋁、鋅、銅等金屬粉末。此等塡充劑可單獨使用針狀（包 含晶鬚）、粒狀、鱗片狀等各種形狀者或2種以上混合使 用。而且’此等塡充劑之粒子大小以比可適用1次之膜厚 較小爲宜。另外，塡充劑之添加量對1重量份聚矽胺烷而 言爲0.05〜10重量份、更佳的添加量爲〇·2〜3重量份。 本發明之感光性組成物中視其所需另加入水平劑、消泡 -33- 1252383 五、發明說明（32) 劑、抗靜電劑、紫外線吸收劑、pH直調整劑、分散劑、表 面改質劑、可塑劑、乾燥促進劑、防止流動劑。 感光性聚矽胺烷組成物可藉由輥塗覆 '浸漬塗覆、棒塗 覆、旋轉塗覆、噴霧塗覆、流動塗覆、刷毛塗覆等習知塗 覆法’塗覆於矽基板、玻璃基板等任意基板上以形成塗膜 。此時可使用印刷法取代塗覆法。於本發明中，塗膜包含 藉由印刷法形成的膜。塗膜視其所需爲使該塗膜乾燥且減 少繼後之脫氣量時，必須進行預煅燒（加熱處理）。預煅燒 係在40〜200°C、較佳者60〜120°C之溫度下、藉由熱板 時實施10〜180秒、較佳者30〜90秒，藉由乾淨烤箱時 實施1〜30分、較佳者爲5〜1 5分。視其所需可藉由重複 塗覆感光性組成物，使塗膜爲企求的膜厚。所企求的膜厚 例如光阻劑時爲0 · 05〜2 // m、層間絕緣膜時爲〇 . 5〜4 // m ’濾色器或黑色基體時爲0.3〜3// m。 然後使由感光性聚矽胺烷組成物所形成的塗膜曝光。於 該曝光工程中組合感光性聚矽胺烷組成物之感光範圍，可 使用高壓水銀燈、低壓水銀燈、金屬鹵化物燈、氙燈、準 分子雷射光、X光線、電子線等。圖案狀之光照射通常使 用光罩進行。照射光係除如半導體之超微細加工外，可使 用一般360〜430nm之光（高壓水銀燈）。其中，爲液晶顯 示裝置時大多使用430nm之光。此時，如上述於本發明之 感光性組成物中組合增感色素極爲有利。 曝光時之照射光能量係藉由所使用的光源或塗膜之膜厚 -34- 1252383 五、發明說明（35) 處理裝置內，惟加濕處理當然可在沒有使用處理裝置之大 氣中進行。另外，基板之加熱除藉由上述加熱板予以加熱 外，且可預先使加熱處理所使用的氣體加溫’使其導入加 濕裝置等任意方法進行。 聚矽胺烷之分解促進工程後，感光性聚矽胺烷組成物膜 係使用攪拌顯像、浸漬顯像、淋浴顯像等習知的顯像方法 ，藉由鹼顯像液予以顯像。藉此可除去感光性聚矽胺烷組 成物膜之曝光部分、且未曝光部分殘留於基板上形成正型 圖案。未曝光部分之聚矽胺烷膜由於在鹼顯像液幾乎不會 膨脹，照射光之圖案與經分解除去的聚矽胺烷之圖案幾乎 完全一致、且可得良好的圖案精度。 鹼顯像液例如四甲銨氫氧化物（TMAH)、膽鹼、矽酸鈉、 氫氧化鈉、氫氧化鉀等之水溶液。鹼之濃度係考慮顯像對 象之材料、所要求的顯像速度、解像性等各種條件予以決 定，以使用業界標準之鹼顯像液爲約2%之TMAH水溶液爲 便利。聚矽胺烷膜使用作爲半導體裝置之蝕刻圖案時，或 轉化成二氧化矽系陶瓷後作爲層間絕緣膜使用時，以使用 在顯像液中不含金屬離子的鹼水溶液爲宜。顯像時所需時 間係視膜厚與所使用的顯像液決定，惟一般爲2 0〜5 0 °C、 較佳者爲2 0〜3 0 °C。 顯像後圖案化的聚矽胺烷膜視其所需以純水洗淨、乾燥 、直接作爲蝕刻光罩使用，或於純水洗淨後、藉由長時間 例如放置或煆燒1日以上轉化成二氧化矽系陶瓷被膜，作 -37- 1252383 五、發明說明（36 ) 爲層間絕緣膜等使用。煅燒溫度及煅燒時間係視感光性聚 矽胺烷組成物之組成、塗膜之膜厚、基板、電子零件等耐 熱性而定，惟一般煅燒溫度爲50〜1 000°C、較佳者爲1〇0 〜1 0 0 0 °C、更佳者爲1 5 0〜4 5 0 °C。而且，一般煅燒時間爲 5分以上、較佳者爲1 〇分以上◦煅燒氣氛一般爲周圍氣氛 (大氣中）即可，爲促進聚矽胺烷之氧化時可採用使氧含量 及/或水蒸氣分壓豐富的氣氛。 進行該聚矽胺烷膜之煅燒時，藉由作爲煅燒前處理工程 之使圖案化的聚矽胺烷膜曝光即加濕處理，可容易形成適 於層間絕緣膜等之具有低介電常數、優異的耐熱性、耐摩 擦性、耐蝕性、絕緣性、透明性二氧化矽系陶瓷膜。換言 之，由於含有聚矽胺烷與光酸發生劑之感光性聚矽胺烷組 成物爲正型，故作爲圖案殘留的感光性聚矽胺烷塗膜上會 殘留有當初的光酸發生劑。因此，作爲煅燒之前處理工程 進行的感光性聚矽胺烷塗膜之曝光及加濕處理時，與上述 說明的感光性聚矽胺烷塗膜圖案形成時相同，藉由曝光在 塗膜內生成酸、且藉由該酸之觸媒作用使聚矽胺烷的S i - N 鍵解裂、藉由加濕處理促進Si-OH化。如此經SiOH化的 聚矽胺烷膜可藉由煅燒容易SiOSi化、且煅燒後轉化成在 膜上不會或幾乎不會存在有Si NH鍵的二氧化矽系陶瓷膜 於感光性聚矽胺烷塗膜進行煅燒的前處理工程之曝光可 以感光性聚砂胺院塗膜之圖案曝光爲基準進行。換言之， -38- 1252383 五、發明說明（37) 曝光光源可藉由感光性聚矽胺烷組成物之感光範圍而定、 使用高壓水銀燈、低壓水銀燈、金屬鹵化物燈、氙氣燈、 準分子雷射光、X光線、電子線等任意者。該煅燒之前處 理工程的曝光係以全部一起曝光者較佳，惟視其所需僅形 成圖案的部份或僅部分基板曝光、再予以數次曝光。另外 ’曝光強度係視所使用的光源或膜厚、感光性組成物之感 度決疋’通常爲O.SmJ/cm2以上、較佳者爲0.1 m】/cm2以 上，惟上限沒有特別的限制，以1 0000 mJ/cm2以下較爲實 用。曝光氣氛可以與圖案化時之曝光相同、在周圍氣氛（ 大氣中）或氮氣氣氛，爲促進聚矽胺烷分解、可採用含氧 量豐富的氣氛。 而且，作爲煅燒的前處理工程之加濕處理亦可與感光性 聚矽胺烷膜於圖案曝光後之加濕處理相同、使經曝光的感 光性聚矽胺烷膜與含水蒸氣之氣體接觸。本發明感光性聚 矽胺烷膜煅燒之前處理工程的加濕處理與感光性聚矽胺烷 膜之煅燒前處理工程中於曝光時藉由氣氛中之水分同時進 行加濕處理時，於該曝光時加濕處理兼具煅燒之前處理工 程的加濕處理工程。然而，就處理時間短縮化而言採用藉 由於曝光後另增大水分含量之高濕度氣體以使塗膜加濕處 理的方法較佳。而且，於加濕處理時塗覆膜在加熱的狀態 下進行加濕處理時，促進聚矽胺烷之S i 0H化係與使圖案 曝光的感光性聚矽胺烷膜加濕處理時相同。因此，例如使 具有曝光塗膜之基板載負於加熱板上、使基板在加熱的狀 -39- 1252383 五、發明說明（40)1252383 V. INSTRUCTION DESCRIPTION (29) A more preferred sensitizing dye is 7-diethylamino-4-methylcoumarin and 7-diethylamino-4-trifluoromethylcoumarin. When a sensitizing dye is used, the obtained film is colored. When the film is used as a photoresist for etching a photoresist or the like, since the photoresist is removed after the desired pattern processing is completed, there is no problem that the photoresist is colored. Further, when the pattern film is fired and the film is not removed after patterning, for example, when the film after firing is used as an interlayer insulating film of a display element, the film after firing must be transparent to visible light. In this case, the photo-acid generator contained in the photosensitive polyamidene composition is usually made to be transparent after the film is calcined, so that there is no considerable problem, but it is not considered to be a problem. For the purpose of use, there is also a film which must be transparent and non-colored. In this case, an oxidation catalyst which is decomposed by the sensitizing dye and which is not related to the photoreaction when the film is calcined may be additionally added to the photosensitive polyamidene composition. The oxidation catalyst may, for example, be a metal organic compound such as palladium propionate, palladium acetate, lead isodecyl acetate, uranium ethyl acetate, palladium fine particles or platinum fine particles, or fine particles. When the oxidation catalyst is added, the amount of the oxidizing catalyst is generally from 0.5 to 10% by weight, preferably from 0.1 to 5% by weight. By adding the oxidation catalyst, it is possible to decompose and decolorize the unnecessary pigment, and to promote the ceramization of the polyamidene. Further, by adding a pigment to the photosensitive polyamidane composition, a color filter or a black matrix excellent in heat resistance, insulation, hardness, and pattern accuracy can be obtained. The pigment added to the polyamine composition is, for example, graphite, carbon black, titanium black, iron oxide, copper chromium black, copper iron manganese black, cobalt iron chromium black or the like. The amount of the pigment to be added is generally 0.05 to 1% by weight based on the polyamidamine, and is more than -3 1 to 1252383. 5. The invention (3 〇) is preferably 10 to 500% by weight. Further, in order to improve the development efficiency, a conventional compound as a dissolution preventing agent can be added to the photosensitive polyamine composition in the technical range. A general dissolution preventing agent prevents the polymer of the unexposed portion of the coating film from being eluted into the alkali developing solution by the hydrophobicity thereof, and the exposed portion is decomposed into hydrophilicity by exposure or by a photoacid generator. It has the function of promoting the decomposition of the polymer. As described above, since the polyamine is not dissolved in the developing liquid, the elution preventing action of the unexposed portion of the dissolution preventing agent is hardly obtained, but the dissolution promoting action of the exposed portion is extremely strong. In other words, by adding a dissolution preventing agent to the photosensitive polyamidene composition, the development efficiency can be improved by increasing the dissolution rate of the exposed portion. Specific examples of the dissolution preventing agent are, for example, a 3-butoxycarbonyl group (hereinafter referred to as t-BOC) catechin, t-BOC hydrazine, benzophenone-4,4'-dicarboxylic acid, 3- Butyl ester, 4, 4, butyl 3-benzoate, etc. The dissolution preventing agent is added to the photosensitive composition in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight. When a solvent is used for the photosensitive polyamidene composition, an aromatic compound such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene or triethylbenzene; cyclohexanetane or cyclohexene; Decalin; dipentene; n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isodecane, n-decane, a saturated hydrocarbon compound such as isodecane; ethylcyclohexane; methylcyclohexane; p-decane; ethers such as dipropyl ether and dibutyl ether; ketones such as methyl isobutyl ketone (MISK); Esters such as butyl ester, cyclohexyl acetate, butyl stearate, ethyl lactate, etc.; ethylene glycol monomethyl ether, ethylene-32- 1252383 V. Description of invention (31) Ethylene glycol monoalkane such as monoethyl ether Ethers; ethylene glycol monoether ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; propylene glycol monomethyl ether; Preferred are propylene glycol monoalkyl ether acetates such as ether acetate (PGMEA) and propylene glycol monoethyl ether acetate. When such a solvent is used, two or more kinds may be used in combination to adjust the solubility of the polyamidane or the evaporation rate of the solvent. The amount (proportion) of the solvent to be used is determined in consideration of the workability of the coating method to be used, the solubility of each component of the photosensitive composition, the coatability of the photosensitive composition, the thickness of the coating film, and the like. The solubility of the solvent differs depending on the average molecular weight, molecular weight distribution, and structure of the polyamine. Further, the concentration of the polyamidane is usually from 0.1 to 50% by weight, preferably from 0.1 to 40% by weight, in view of the stability of the polyamine, the production efficiency, the coating property and the like. Further, as the photosensitive composition of the present invention, a suitable chelating agent and/or extender may be added as needed. The chelating agent is, for example, an oxide-based inorganic material such as cerium oxide, aluminum oxide, chromium oxide or mica, or a fine powder of a non-oxide-based inorganic material such as cerium carbide or cerium nitride, and may be added depending on the application. , metal powder such as zinc and copper. These chelating agents may be used alone or in combination of two or more kinds of needles (including whiskers), granules, and scaly shapes. Further, it is preferable that the particle size of such a chelating agent is smaller than the film thickness which is applicable once. Further, the amount of the chelating agent to be added is 0.05 to 10 parts by weight based on 1 part by weight of the polyamidamine, and more preferably 2 to 3 parts by weight. The photosensitive composition of the present invention may be further added with a horizontal agent, defoaming-33- 1252383, the invention description (32) agent, antistatic agent, ultraviolet absorber, pH straight adjuster, dispersant, surface modification Agent, plasticizer, drying accelerator, flow preventive agent. The photosensitive polyamidene composition can be applied to the ruthenium substrate by a conventional coating method such as roll coating, dipping coating, bar coating, spin coating, spray coating, flow coating, brush coating, and the like. A coating film is formed on any substrate such as a glass substrate. At this time, a printing method can be used instead of the coating method. In the present invention, the coating film contains a film formed by a printing method. The coating film is required to be pre-calcined (heat treatment) in order to dry the coating film and reduce the amount of subsequent degassing. The pre-calcination is carried out at a temperature of 40 to 200 ° C, preferably 60 to 120 ° C, by a hot plate for 10 to 180 seconds, preferably 30 to 90 seconds, and 1 to 30 by a clean oven. The score is preferably 5 to 15 points. The coating film can be made to have a desired film thickness by repeating application of the photosensitive composition as needed. The film thickness to be obtained is, for example, 0. 05 to 2 // m for the photoresist, and 〇 for the interlayer insulating film. 5 to 4 // m ' of the color filter or the black matrix is 0.3 to 3 // m. Then, the coating film formed of the photosensitive polyamidene composition was exposed. In the exposure process, a photosensitive high-temperature mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a quasi-molecular laser beam, an X-ray, an electron beam, or the like can be used in combination with the photosensitive range of the photosensitive polyamidene composition. Patterned light illumination is typically performed using a reticle. In addition to the ultra-fine processing of semiconductors, the illumination light system can generally use light of 360 to 430 nm (high-pressure mercury lamp). Among them, in the case of a liquid crystal display device, light of 430 nm is often used. In this case, it is extremely advantageous to combine the sensitizing dyes in the photosensitive composition of the present invention as described above. The irradiation light energy at the time of exposure is carried out by the light source or the film thickness of the coating film used in the treatment apparatus, but the humidification treatment can of course be carried out in the atmosphere without using the treatment device. Further, the heating of the substrate can be carried out by any method such as heating the gas used in the heat treatment and introducing it into the humidifying device in advance, in addition to heating by the heating plate. After the decomposition-promoting process of the polyamidamine, the photosensitive polyamidene composition film is developed by a conventional developing method such as stirring development, immersion development, or shower development using an alkali developing solution. Thereby, the exposed portion of the photosensitive polyimide substrate film can be removed, and the unexposed portion remains on the substrate to form a positive pattern. The polyamidane film in the unexposed portion hardly expands in the alkali developing solution, and the pattern of the irradiated light almost completely coincides with the pattern of the polyamine which is decomposed and removed, and good pattern precision can be obtained. An alkali developing solution such as an aqueous solution of tetramethylammonium hydroxide (TMAH), choline, sodium citrate, sodium hydroxide, potassium hydroxide or the like. The concentration of the alkali is determined in consideration of various conditions such as the material of the developing object, the required developing speed, and the resolution, and it is convenient to use an industry standard alkali developing solution of about 2% aqueous TMAH solution. When the polyimide film is used as an etching pattern for a semiconductor device or converted into a ceria-based ceramic and used as an interlayer insulating film, an aqueous alkali solution containing no metal ions in the developing solution is preferably used. The time required for development is determined by the film thickness and the developing solution used, but it is generally 20 to 50 ° C, preferably 20 to 30 ° C. After the development, the patterned polyamidamine film is washed with pure water, dried, and used directly as an etching mask, or after being washed with pure water, for example, by standing or simmering for more than one day. It is converted into a cerium oxide ceramic film, and it is used as an interlayer insulating film, etc., as -37- 1252383. The calcination temperature and the calcination time depend on the composition of the photosensitive polyamidene composition, the film thickness of the coating film, the heat resistance of the substrate, the electronic component, etc., but the general calcination temperature is 50 to 1 000 ° C, preferably 1〇0 ～1 0 0 0 °C, and more preferably 1 5 0~4 5 0 °C. Further, the calcination time is generally 5 minutes or more, preferably 1 part or more, and the calcination atmosphere is generally in the surrounding atmosphere (in the atmosphere), and the oxygen content and/or water may be used to promote the oxidation of the polyamido. A vapor-rich atmosphere. When the polyalkane film is calcined, it is easy to form a low dielectric constant suitable for the interlayer insulating film or the like by exposing and drying the patterned polyamidamine film as a pre-baking process. Excellent heat resistance, abrasion resistance, corrosion resistance, insulation, and transparency of cerium oxide ceramic film. In other words, since the photosensitive polyaminicene composition containing the polyamidamine and the photoacid generator is a positive type, the original photoacid generator remains on the photosensitive polyimide substrate which remains as a pattern. Therefore, in the exposure and humidification treatment of the photosensitive polyaminice coating film which is carried out before the baking, the photosensitive polyamipene coating film pattern described above is formed in the coating film by exposure as in the case of forming the photosensitive polyimide film pattern described above. The acid, and the S i -N bond of the polyamine is decomposed by the action of the acid catalyst, and the Si-OH is promoted by the humidification treatment. The SiOH-treated polyamidene film can be easily SiO-activated by calcination, and after calcination, it can be converted into a cerium oxide-based ceramic film having no or almost no Si NH bond on the film. The exposure of the pretreatment process in which the alkane coating film is calcined can be carried out based on the pattern exposure of the photosensitive polysalamine film. In other words, -38-1252383 V. Description of the invention (37) The exposure light source can be determined by the photosensitive range of the photosensitive polyamidene composition, using a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer thunder Any of the light, X-ray, and electron beam. The exposure of the processing prior to calcination is preferred for all of the exposures, but only a portion of the pattern or only a portion of the substrate is exposed as needed, and then exposed several times. In addition, the exposure intensity depends on the light source or film thickness used, and the sensitivity of the photosensitive composition is usually 'O.SmJ/cm2 or more, preferably 0.1 m】/cm2 or more, but the upper limit is not particularly limited. It is more practical to use 1 0000 mJ/cm2 or less. The exposure atmosphere may be the same as the exposure at the time of patterning, in the surrounding atmosphere (atmosphere) or in a nitrogen atmosphere, in order to promote decomposition of the polyamidane, an oxygen-rich atmosphere may be employed. Further, the humidification treatment as the pretreatment of the calcination may be carried out in the same manner as the humidification treatment after the photosensitive exposure of the photosensitive polyamidamine film, and the exposed photosensitive polyalkane membrane is brought into contact with the gas containing water vapor. When the humidifying treatment of the photosensitive polyami amide film before the calcination process of the present invention and the pre-calcination treatment of the photosensitive polyami amide film are simultaneously humidified by the moisture in the atmosphere during the exposure, the exposure is performed. The humidification treatment is a humidification treatment process that combines the processing before calcination. However, in the case of shortening the processing time, a method of humidifying the coating film by using a high-humidity gas having an increased moisture content after exposure is preferred. Further, when the coating film is subjected to humidification treatment in a heated state during the humidification treatment, the SiOH formation of the polyamidene is the same as that in the case of humidifying the photosensitive polyimide substrate for exposing the pattern. Therefore, for example, the substrate having the exposed coating film is carried on the heating plate, and the substrate is heated. -39-1252383 5. Description of the Invention (40)

(C2H5)2N(C2H5) 2N

(2) 將溶液分成二份，在一份中對改質聚矽倍半胺烷而言添 加2重量硝基苯胺。沒有添加2-硝基苯胺之溶液作爲 比較例1。 使各溶液以200 Or pm旋轉塗覆於矽基板上（膜厚：0 · 4// m)。在該塗膜上使用作爲曝光裝置之KrF準分子雷射曝光 裝置、以40mJ/cm2之曝光量、經由〇.5//m孤立圖案光罩 、煅燒相同的圖案。然後，以2 . 38重量％TMAH(四甲銨氫 氧化物）水溶液顯像。 將所得附有圖案膜之矽基板切斷，自截面方向以電子顯 微鏡（SEM)觀察劈開面之傾斜角。 實施例2 除對改質聚矽倍半胺烷而言添加1重量％2 -硝基丙烷取 代2 -硝基苯胺外，與實施例1相同地予以實施。 實施例3 除對改質聚矽倍半胺烷而言添加5重量％碳酸伸丙酯取 代2 -硝基苯胺外，與實施例1相同地予以實施。 實施例4 除對改質聚矽倍半胺烷而言添加1 〇重量％水溶性丙烯酸 聚合物（東亞合成股份有限公司製丙烯酸系聚合物「阿龍（ -42- 1252383 五、發明說明（41 ) 譯苜）A-20P」（商品名））取代2_硝基苯胺外，與實施例1 相同地予以實施。 [傾斜角之比較] 實施例1〜 例 實施例1 實施例2 實施例3 實施例4 比較例1 及比較例1所得圖案膜之傾斜角如下所述 / 90 90 90 90 70 [煅燒膜之特性比較] 然後，使實施例1〜4及比較例1所得的圖案膜以下述 條件煅燒’且以下述方法測定煅燒膜之介電常數及膜硬度 ，觀察煅燒膜作爲層間絕緣膜之有用性。 (煅燒條件） 使各圖案膜以熱板在150°C下預加熱1分鐘後，在400 °C之煅燒爐中放置30分鐘。 (介電常數測定法） 在煅燒膜上方形成面積爲1 mm2之鋁作爲上方電極。另外 ，在矽基板上形成合金層作爲下方電極’且集合全體構成 MOS電容器。使用休雷特巴卡頓（譯音）公司製HP4192A阻 抗分析器、對該MOS電容器施加偏壓電壓，測定電容器 -43- 1252383 五、發明說明（42) (C - V特性），自該特性算出介電常數。 (硬度之測定） 以MTS系統公司製Nano IndenterXP測定 (特性之比較） 測定結果如下所述。 例 介電常數 硬度（G p a ) 實施例 1 〜2 . 6 1 . 0 實施例 2 〜2 · 6 1 . 0 實施例 3 〜2 . 6 1.0 實施例 4 〜1 Λ 0 . 7 比較例 1 〜2 . 6 1.0 上述介電常數及硬度之結果係表市藉由本發明所得自勺瑕 燒膜具有作爲層間絕緣膜之有用特性者。 實施例5 以參考例所記載的順序調製以-[S i CH3 ( NH ) ! . 5 ]-爲基本 構成、且含5莫耳之改質聚矽倍半胺 烷。對該改質聚矽倍半胺烷而言添加1重量％作爲光酸發 生劑之式： -44 - 1252383 五、發明說明（43 )(2) The solution was divided into two portions, and 2 parts of nitroaniline was added to the modified polyhydrazine sesquiamine in one portion. A solution of 2-nitroaniline was not added as Comparative Example 1. Each solution was spin-coated on a ruthenium substrate (film thickness: 0 · 4 // m) at 200 Or pm. The same pattern was fired on the coating film by using a KrF excimer laser exposure apparatus as an exposure apparatus at an exposure amount of 40 mJ/cm 2 via a 图案.5//m isolated pattern mask. Then, it was developed with a 2.38 wt% TMAH (tetramethylammonium hydroxide) aqueous solution. The obtained ruthenium substrate with the pattern film was cut, and the inclination angle of the cleavage surface was observed by an electron microscope (SEM) from the cross-sectional direction. Example 2 The same procedure as in Example 1 was carried out except that 1% by weight of 2-nitropropane was added to the modified polydecyl sesquiamine to replace 2-nitroaniline. Example 3 The same procedure as in Example 1 was carried out except that 5% by weight of propylene carbonate was added to the modified polydecyl sesquiamine to replace 2-nitroaniline. Example 4 In addition to the modified polyfluorinated sesquiamine, 1% by weight of a water-soluble acrylic polymer (acrylic polymer manufactured by Toagosei Co., Ltd.) "Aaron (-42- 1252383 V. Inventive Note (41) ) A-20P" (trade name)) was carried out in the same manner as in Example 1 except that 2-nitroaniline was replaced. [Comparison of Tilt Angles] Example 1 to Example Example 1 Example 2 Example 3 Example 4 The inclination angle of the pattern film obtained in Comparative Example 1 and Comparative Example 1 was as follows / 90 90 90 90 70 [Characteristics of the calcined film Comparative] Then, the pattern films obtained in Examples 1 to 4 and Comparative Example 1 were fired under the following conditions, and the dielectric constant and film hardness of the fired film were measured by the following methods, and the usefulness of the fired film as an interlayer insulating film was observed. (Calcination Conditions) Each of the pattern films was preheated at 150 ° C for 1 minute on a hot plate, and then placed in a calcination oven at 400 ° C for 30 minutes. (Dielectric constant measurement method) Aluminum having an area of 1 mm 2 was formed as an upper electrode above the calcined film. Further, an alloy layer is formed on the tantalum substrate as the lower electrode', and the entire assembly constitutes a MOS capacitor. Using a HP4192A impedance analyzer manufactured by Hugh Barkerton, a bias voltage was applied to the MOS capacitor, and the capacitor was measured - 43 - 1252383 5. The invention (42) (C - V characteristic) was calculated from the characteristic. Dielectric constant. (Measurement of hardness) Measurement by Nano Indenter XP manufactured by MTS Systems, Inc. (comparison of characteristics) The measurement results are as follows. Example dielectric constant hardness (G pa ) Example 1 to 2. 6 1 . 0 Example 2 to 2 · 6 1 . 0 Example 3 to 2 . 6 1.0 Example 4 to 1 Λ 0 . 7 Comparative Example 1 ~ 2. 6 1.0 The result of the above dielectric constant and hardness is obtained by the present invention. The self-drilled film obtained by the present invention has useful characteristics as an interlayer insulating film. Example 5 In the order described in the reference example, a modified polyfluorinated sesquiamine containing 5 mol was used as a basic structure of -[S i CH3 (NH ) ! . 5 ]-. To the modified polydecyl sesquiamine, 1% by weight is added as a photoacid generator: -44 - 1252383 V. Description of the invention (43)

CCI3 所示之三畊衍生物，且以丙二醇單甲醚乙酸酯（PGMEA )稀 釋成全固體成分濃度爲1 0重量％之濃度以調製感光性聚矽 胺烷組成物。使該感光性聚矽胺烷組成物以1 000 r pm旋轉 塗覆於矽基板上，在90°C下預煅燒90秒、形成0.4// m厚 塗膜。然後，使具有該感光性聚矽胺烷組成物塗膜之基板 使用作爲曝光裝置之KrF準分子雷射曝光裝置、通過具有 各種線寬之1 : 1線與空間的光罩、以10mJ/cm2〜 1 000mJ/cm2之照射量15m〗/cm2階段照射量曝光。然後，在 2 5°C、6 0%RH下進行加濕處理5分鐘、使基板以2 · 38重量 %TMAH水溶液顯像1分鐘、再使基板藉由醇水洗淨、以 SEM觀察所得圖案，以可完全除去曝光部膜之曝光量作爲 感度予以定義觀察，結果如表1所示。 比較例2 除加濕處理條件如表1記載的條件外，與實施例5相同 地進行，可得表1之結果。 -45- 1252383 五、發明說明（44) 表1 一-___ 加濕處理1 谋件 感度（m〗/ cm2) 溫度（°c) 濕度（％RH) 處理時間（分） 實施例5 25 60 5 70 比較例2 25 35 〇 > 1000The three-till derivative represented by CCI3 was diluted with propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 10% by weight of the total solid content to prepare a photosensitive polyamidene composition. The photosensitive polyamidene composition was spin-coated on a ruthenium substrate at 1 000 rpm, and pre-calcined at 90 ° C for 90 seconds to form a 0.4 / / m thick coating film. Then, the substrate having the photosensitive polyimide substrate coating film was used as a KrF excimer laser exposure apparatus as an exposure apparatus, and a reticle having a line width of 1: 1 line and space was used at 10 mJ/cm 2 . Exposure amount of ~1 000 mJ/cm2 is 15 m〗/cm2 Exposure exposure. Then, the substrate was subjected to humidification treatment at 25° C. and 60% RH for 5 minutes, and the substrate was developed with a 2·38 wt% TMAH aqueous solution for 1 minute, and the substrate was washed with alcohol water to observe the pattern by SEM. The exposure amount which can completely remove the exposed film was defined as the sensitivity, and the results are shown in Table 1. Comparative Example 2 The results of Table 1 were obtained in the same manner as in Example 5 except that the conditions for the humidification treatment were as shown in Table 1. -45- 1252383 V. INSTRUCTIONS (44) Table 1 I-___ Humidification treatment 1 Mould sensitivity (m〗 / cm2) Temperature (°c) Humidity (%RH) Treatment time (minutes) Example 5 25 60 5 70 Comparative Example 2 25 35 〇> 1000

由表1之結果可知，藉由使處理時之氣氛濕度提高，可 提局感光性聚矽胺烷組成物之感度、且藉此可縮短處理時 間。 實施例6〜8 以參考例所記載的順序調製以-[S 1 CH3 ( NH ),. 5 ]-爲基本 構成、且含10莫耳％-[Si(CH3)2(NH)]-之改質聚矽倍半胺 烷。對該改質聚矽倍半胺烷而言添加5重量％作爲光酸發 生劑之式： ch3〇As is apparent from the results of Table 1, by increasing the humidity of the atmosphere during the treatment, the sensitivity of the photosensitive polyamidene composition can be improved, and the treatment time can be shortened. Examples 6 to 8 were prepared in the order described in the reference examples, and had a basic structure of -[S 1 CH 3 (NH ), . 5 ]- and contained 10 mol%-[Si(CH3)2(NH)]- Modified polyfluorenated sesquiamine. To the modified polydecyl sesquiamine, 5 wt% was added as a photoacid generator: ch3〇

所示之亞楓鐵鹽衍生物、1 〇重量％作爲增感色素之式： (C2H5)2N\^^〇、^The arsenic salt derivative shown in the figure, 1% by weight as a sensitizing dye: (C2H5)2N\^^〇, ^

ch3 -46- 1252383 五、發明說明（45) 所示之香豆素衍生物，且以醋酸丁酯稀釋成全固體成分濃 度爲1 0重量％之濃度以調製感光性聚矽胺烷組成物。使該 感光性聚矽胺烷組成物以lOOOr pm旋轉塗覆於矽基板上， 藉由旋轉乾式方法乾燥、形成0 · 4 // m厚塗膜。然後，使 用1線曝光裝置、通過具有各種線寬之1 : 1線與空間圖 案的光罩、以0.1mJ/cm2〜lmJ/cm2之照射量0.1mJ/cm2階 段照射量、InU/cm2〜l〇m J/cm2之照射量lmJ/cm2階段照射 量、10W / cm2〜10 0m J / cm2之照射量l〇m J / cm2階段照射量 予以、曝光。然後’使該經曝光的基板放置於加濕處理裝 置內之加熱板上，以表2記載的加濕處理條件處理、與實 施例5相同地進行顯像處理、洗淨處理、可得表2記載的 感度。 比較例3 除加濕處理條件如表2記載的條件外，與實施例6相同 地進行，可得表2之結果。 表2 ____^濕處理條1 牛 感度（mJ /cm2) 溫度（°C ) 濕度（％RH) 處理時間（分） 實施例6 25 60 5 70 實施例7 50 50 3 10 實施例8 90 50 1 0.2 > 1000 比較例3 25 35 0 -47- 1252383 五、發明說明（46) 由表1及表2可知，於進行處理時藉由加熱可使處理時 間縮短、且即使在相同溫度下進行處理、在加熱條件下進 行加濕處理時可提高感度、並藉此更爲縮短處理時間。 實施例9〜1 1 以參考例所記載的順序調製以-[S 1 CH3 ( NH ) ! . 5 ]-爲基本 構成、且含10莫耳％-[31(?1〇2(_)]-之改質聚矽倍半胺 烷（Ph :苯基）。對該改質聚矽倍半胺烷而言添加1重量％ 作爲光酸發生劑之式：Ch3-46- 1252383 V. The coumarin derivative shown in (45), which was diluted with butyl acetate to a concentration of 10% by weight of the total solid content to prepare a photosensitive polyamidene composition. The photosensitive polyamidene composition was spin-coated on a ruthenium substrate at 100 pm, and dried by a rotary dry method to form a 0. 4 // m thick coating film. Then, using a 1-line exposure apparatus, a reticle having a 1:1 line and a space pattern having various line widths, an irradiation amount of 0.1 mJ/cm 2 at an irradiation amount of 0.1 mJ/cm 2 lmJ/cm 2 , and InU/cm 2 〜1 〇m J/cm2 irradiation amount lmJ/cm2 stage irradiation amount, 10W / cm2~10 0m J / cm2 irradiation amount l〇m J / cm2 stage irradiation amount, exposure. Then, the exposed substrate was placed on a hot plate in the humidification treatment apparatus, and subjected to the humidification treatment conditions described in Table 2, and subjected to development processing and washing treatment in the same manner as in Example 5, and Table 2 was obtained. The sensitivity of the record. Comparative Example 3 The results of Table 2 were obtained in the same manner as in Example 6 except that the conditions for the humidification treatment were as shown in Table 2. Table 2 ____^Wet treatment strip 1 Cow sensitivity (mJ / cm2) Temperature (°C) Humidity (%RH) Treatment time (minutes) Example 6 25 60 5 70 Example 7 50 50 3 10 Example 8 90 50 1 0.2 > 1000 Comparative Example 3 25 35 0 -47- 1252383 V. Description of Invention (46) It can be seen from Tables 1 and 2 that the treatment time can be shortened by heating and processed even at the same temperature. When the humidification treatment is performed under heating conditions, the sensitivity can be improved, and the treatment time can be further shortened. Examples 9 to 1 1 In the order described in the reference example, -[S 1 CH3 ( NH ) ! . 5 ]- was used as a basic structure, and 10 mol%-[31 (?1〇2(_)] was included. - modified polydecyl sesquiamine (Ph: phenyl). Add 1% by weight of the modified polydecyl sesquiamine as a photoacid generator:

(CH3)3COOC 〇(CH3)3COOC 〇

所示之過氧化物，且使該混合物以PGMEA稀釋成全固體 成分濃度爲30重量％之濃度以調製感光性聚矽胺烷組成物 。使該感光性聚矽胺烷組成物以3000 rpm旋轉塗覆於矽基 板上，在6(TC下預煅燒60秒、形成0.8// m厚之塗膜。然 後，使具有該感光性聚矽胺烷組成物塗膜之基板使用作爲 曝光裝置之電子線曝光裝置、通過具有各種線寬之1:1 線與空間圖案之光罩，以80// C/cm2之曝光量進行圖案锻 燒。然後，在表3記載的加濕處理條件下進行基板之處理 後，以2 . 38重量％TMAH水溶液顯像1分鐘、再使基板以醇 水洗淨、以SEM觀察所得的圖案，確認圖案破壞的情形。 沒有遭受破壞的最小圖案線寬如表3所示。 -48- 1252383 五、發明說明（47) ^__3 加濕處理條件 不會被破壞的最小圖案 溫度（°c) 濕度（％RH) 處理時間（分） (β m) 實施例9 25 50 10 0.5 實施例10 30 50 3 0.3 實施例11 70 50 3 0.075 由表3之結果可知，藉由在加濕條件下之顯像處理，不 易引起圖案之破壞情形、即可改善圖案對基板之密接性。 實施例12 以參考例所記載的順序調製以-[S i CH3 ( NH ) , . 5 ]-爲基本 構成、且含 5莫耳莫耳 [Si(CH3)2(NH)]_之改質聚矽倍半胺烷。對該改質聚矽倍半 胺烷而言添加1重量％作爲光酸發生劑^ ί <The peroxide was shown, and the mixture was diluted with PGMEA to a concentration of 30% by weight of the total solid content to prepare a photosensitive polyamidene composition. The photosensitive polyamidene composition was spin-coated on a ruthenium substrate at 3000 rpm, and pre-calcined at 6 (TC for 60 seconds to form a coating film having a thickness of 0.8/m). Then, the photosensitive polyimide was obtained. The substrate of the alkane composition coating film was subjected to pattern calcination at an exposure amount of 80//C/cm 2 by using an electron beam exposure apparatus as an exposure apparatus through a mask having a line width and a 1:1 line and a space pattern. Then, the substrate was treated under the humidification treatment conditions described in Table 3, and then developed with a 3.8 wt% TMAH aqueous solution for 1 minute, and the substrate was washed with alcohol water, and the obtained pattern was observed by SEM to confirm pattern breakage. The minimum pattern line width without damage is shown in Table 3. -48- 1252383 V. Description of invention (47) ^__3 Minimum pattern temperature (°c) for humidification treatment conditions not to be destroyed Humidity (%RH Processing time (minutes) (β m) Example 9 25 50 10 0.5 Example 10 30 50 3 0.3 Example 11 70 50 3 0.075 From the results of Table 3, it is known that the development treatment under humidification conditions It is not easy to cause damage to the pattern, and the pattern can be improved to the substrate. Continuing Example 12. The sequence described in the reference example was prepared with -[S i CH3 ( NH ) , . 5 ]- as a basic structure and contained 5 molimo [Si(CH3)2(NH)]_ Modified polydecyl sesquiamine. Add 1% by weight to the modified poly sesquiamine to be a photoacid generator ^ ί <

所示之三哄衍生物，且使混合物以丙二醇單甲醚乙酸酯 (PGMEA)稀釋成全固體成分濃度爲1〇重量％之濃度以調製 感光性聚矽胺烷組成物。使該感光性聚矽胺烷組成物以 -49 - 1252383 五、發明說明（48) lOOOrpm旋轉塗覆於矽基板上’在90°C下預煅燒90秒、 形成0 . 4 // m厚塗膜。然後’使塗膜藉由低壓水銀燈、以 100m〗/cm2之曝光量全面一起進行曝光後，在25°C、50%rH 下加熱處理5分鐘、且在400°C下煅燒30分鐘。觀察所得 锻燒膜之介電常數及有無S i NH殘存。結果如表4所示。 比較例4 除不進行全面曝光及加濕處理外，與實施例12相同地 進行，可得表4之結果。比較例4所形成煅燒膜之紅外線 吸收光譜如第5圖所示。 表4 實施例12 比較例4 煅燒前處理條件 低壓水銀燈 不處理 (全部一起曝光） 100mJ/cm2 煅燒前處理條件 25〇C 50%RH 不處理 (加濕條件） 5分 燒條件 40(TC 30 分 400°C 30 分 介電常數 2.7 3.8 SiNH之殘份 迦 j \ w 有 (紅外分光） (參照第4圖） (參照第5圖） 由上述表4之結果可知，藉由在煅燒前使感光性聚矽胺 院塗膜曝光、加濕處理，煅燒後之膜上沒有SiNH鍵、且 可形成低介電常數膜。 -50- 1252383 五、發明說明（49) 實施例1 3〜1 5 以參考例所記載的順序調製以-[S 1 CH3 ( NH ) , . 5 ]-爲基本 構成、且含20莫耳^[SUCIMNH)]-之改質聚矽倍半胺 烷。對該改質聚矽倍半胺烷而言添加1重量％作爲光酸發 生劑之式：The triterpene derivative is shown, and the mixture is diluted with propylene glycol monomethyl ether acetate (PGMEA) to a concentration of 1% by weight of the total solid content to prepare a photosensitive polyamidene composition. The photosensitive polyamidene composition was spin-coated on a ruthenium substrate at -48 - 1252383, invention (48) 1000 rpm 'pre-calcined at 90 ° C for 90 seconds to form a 0.4 4 m thick coating membrane. Then, the coating film was exposed to light at a total pressure of 100 m/cm2 by a low pressure mercury lamp, and then heat-treated at 25 ° C, 50% rH for 5 minutes, and calcined at 400 ° C for 30 minutes. The dielectric constant of the obtained calcined film and the presence or absence of S i NH were observed. The results are shown in Table 4. Comparative Example 4 The results of Table 4 were obtained in the same manner as in Example 12 except that the full exposure and the humidification treatment were not carried out. The infrared absorption spectrum of the calcined film formed in Comparative Example 4 is shown in Fig. 5. Table 4 Example 12 Comparative Example 4 Pre-calcination treatment conditions Low-pressure mercury lamp was not treated (all exposed together) 100 mJ/cm2 Pre-calcination treatment conditions 25 〇C 50% RH No treatment (humidification conditions) 5 minutes of burning condition 40 (TC 30 points 400 ° C 30 minutes dielectric constant 2.7 3.8 SiNH residue can j \ w Yes (infrared spectroscopy) (refer to Figure 4) (refer to Figure 5) From the results of Table 4 above, by sensitizing before calcination The polyacrylamide film is exposed and humidified, and the film after calcination has no SiNH bond and can form a low dielectric constant film. -50-1252383 V. Description of the invention (49) Example 1 3~1 5 The modified polydecyl sesquiamine having a basic structure of -[S 1 CH 3 (NH ) , . 5 ]- and containing 20 mol [^CIMNH]]- was prepared in the order described in the reference example. To the modified polydecyl sesquiamine, 1% by weight was added as a photoacid generator:

所示之亞楓鏺鹽衍生物，且以PGMEA稀釋成全固體成分 濃度爲1 0重量％之濃度以調製感光性聚矽胺烷組成物。使 該感光性聚矽胺烷組成物以1 000 r pm旋轉塗覆於矽基板上 ，藉由旋轉乾式方法乾燥、形成0 . 4 // ni厚之塗膜。然後 ，使用高壓水銀燈、以100m〗/cm2之曝光量全面一起進行 曝光。使該經曝光的基板放置於加濕處理裝置內之加熱板 上，以表5記載的加濕處理條件處理、在400°C下锻燒30 分鐘。與實施例1 2相同地觀察所得煅燒膜之介電常數及 有無S i NH殘存。結果如表5所示。 比較例5 除加濕處理條件如表5記載的條件外，與實施例13相 同地進行，可得表5之結果。 -51 - 1252383 五、發明說明（50 ) 表5 實施例13 實施例14 實施例15 比較例5 煅燒前處理條件 低壓水銀燈 低壓水銀燈 低壓水銀燈 不處理 (全部一起曝光） 100mJ/cm2) 100mJ/cm2) 1OOmJ/ cm2) 煅燒前處理條件 25〇C 50%RH 30°C 80%RH 70°C 50%RH 不處理 (加濕條件） 1分 1分 1分 煅燒條件 400°C 30 分 4〇0°C 30分 400°C 30 分 40〇r 30 分 介電常數 3.3 2.7 2.7 3.8 SiNH之殘份 Μ ^ \\\ Μ y\\\ te j\ w 有 (紅外分光） 由上述表5可知，在高濕度下加濕及伴隨加熱之加濕者 與在低溫下之加濕處理相比，在煅燒後之膜中沒有殘留 S i NH、且可製得介電常數低的煅燒膜。由該結果可知，藉 由加濕條件爲高濕、加熱下進行時，可縮短工程時間。 發明之效果 如上所述，本發明可得下述結果。 (1 )藉由使感光性聚砂胺院組成物於曝光後使用含水蒸 氣之氣體進行聚矽胺烷分解促進處理時，可在短時間內進 行加濕處理◦而且，藉由使此時之氣體濕度提高可改善感 度，並可縮短處理時間。另外，此時使基板在加熱的狀態 下進行加濕處理時，可在高濕度條件下處理，而且可得改 善感度、提高處理速度、可改善基板與感光性聚矽胺烷組 成物之密接性的效果。 -52- 1252383 五、發明說明（51) (2 )此外，於使經圖案化或未經圖案化的感光性聚矽胺 院塗膜煅燒時，藉由使聚矽胺烷塗膜曝光、加濕處理、藉 由低溫、短時間加熱作爲煅燒前處理工程，可形成煅燒膜 中沒有殘存聚矽胺烷由來的S 1 - N鍵、以低介電常數具有 優異的絕緣性、耐熱性、耐摩擦性、耐蝕性、透明性二氧 化5夕系陶瓷膜。另外，藉由使用高濕度氣體作爲煆燒前處 理工程之加濕處理條件，且藉由加濕處理時使感光性聚矽 胺院塗膜加熱、在較短時間的處理時間內可進行較佳的膜 內聚矽胺烷之S i 0H化、可縮短全體之處理時間的縮短化 〇 (3 )藉由在含有特定改質聚矽倍半胺烷之感光性聚矽胺 院組成物中添加作爲形狀安定化劑之水溶性化合物，可以 解除感光性組成物之膜厚方向的感度差，藉此可使以光照 射之圖案截面側必較爲急峻化、且可提高圖案解像度。而 且’所得的絕緣膜具有低介電常數特性、且可形成具備有 優異的耐摩擦性等機械特性、具有作爲層間絕緣膜之優異 特性之微細圖案。 (4 )本發明之圖案形成方法、或藉由新穎感光性聚矽胺 烷組成物所得的圖案聚矽胺烷膜可直接利用於蝕刻光阻劑 等之光阻劑或構成顯示元件等之被膜，藉由轉化爲二氧化 矽系陶瓷被膜、可使用作爲半導體裝置或液晶顯示裝置等 之層間絕緣膜等。 -53-The flavonoid salt derivative shown was diluted with PGMEA to a concentration of 10% by weight of the total solid content to prepare a photosensitive polyamidene composition. The photosensitive polyamidene composition was spin-coated on a ruthenium substrate at 1 000 rpm, and dried by a rotary dry method to form a coating film of 0.4% thick. Then, using a high-pressure mercury lamp, exposure was performed in a total amount of 100 m/cm2. The exposed substrate was placed on a hot plate in a humidification treatment apparatus, and treated under the humidification treatment conditions shown in Table 5, and calcined at 400 ° C for 30 minutes. The dielectric constant of the obtained calcined film and the presence or absence of S i NH were observed in the same manner as in Example 12. The results are shown in Table 5. Comparative Example 5 The results of Table 5 were obtained in the same manner as in Example 13 except that the conditions for the humidification treatment were as shown in Table 5. -51 - 1252383 V. INSTRUCTIONS (50) Table 5 Example 13 Example 14 Example 15 Comparative Example 5 Pre-calcination treatment conditions Low-pressure mercury lamp Low-pressure mercury lamp Low-pressure mercury lamp is not treated (all exposed together) 100mJ/cm2) 100mJ/cm2) 1OOmJ/cm2) Pre-calcination conditions 25〇C 50%RH 30°C 80%RH 70°C 50%RH No treatment (humidification conditions) 1 minute 1 minute 1 minute Calcination condition 400°C 30 minutes 4〇0° C 30 minutes 400 ° C 30 minutes 40 〇 r 30 minutes dielectric constant 3.3 2.7 2.7 3.8 SiNH residue Μ ^ \\\ Μ y\\\ te j\ w Yes (infrared spectroscopy) As can be seen from Table 5 above, The humidifier under humidification at high humidity and the humidification accompanying heating have no residual S i NH in the film after calcination, and a calcined film having a low dielectric constant can be obtained as compared with the humidification treatment at a low temperature. From this result, it is understood that the engineering time can be shortened when the humidifying conditions are high humidity and heating. EFFECTS OF THE INVENTION As described above, the present invention can provide the following results. (1) When the photosensitive poly-salamine composition is subjected to polyamine decomposition treatment by a gas containing water vapor after exposure, the humidification treatment can be performed in a short time, and by this time, Increased humidity in the gas improves sensitivity and reduces processing time. Further, at this time, when the substrate is subjected to humidification treatment in a heated state, it can be treated under high humidity conditions, and the sensitivity can be improved, the treatment speed can be improved, and the adhesion between the substrate and the photosensitive polyamidene composition can be improved. Effect. -52- 1252383 V. INSTRUCTIONS (51) (2) Further, when the patterned polyimide film which is patterned or unpatterned is calcined, the polyimide film is exposed and exposed. Wet treatment, low-temperature, short-time heating as a pre-calcination treatment, can form an S 1 -N bond from the calcined film without residual polyamine, and has excellent insulation, heat resistance and resistance with a low dielectric constant. Friction, corrosion resistance, and transparency of the cerium oxide ceramic film. In addition, by using a high-humidity gas as the humidification treatment condition of the pre-burning treatment process, and heating the photosensitive polyamine film by the humidification treatment, it is preferable to perform the treatment in a short period of time. The S i 0H of the intramolecular polyamidamine can shorten the processing time of the entire process (3) by adding to the photosensitive polyamine compound composition containing the specific modified polypime sesquiamine As the water-soluble compound of the shape stabilizer, the difference in sensitivity in the film thickness direction of the photosensitive composition can be released, whereby the cross-sectional side of the pattern irradiated with light must be sharpened, and the pattern resolution can be improved. Further, the obtained insulating film has low dielectric constant characteristics, and can form a fine pattern having excellent mechanical properties such as excellent abrasion resistance and excellent characteristics as an interlayer insulating film. (4) The pattern forming method of the present invention or the patterned polyamidamine film obtained by the novel photosensitive polyamidene composition can be directly used for a photoresist such as an etching photoresist or a film constituting a display element or the like. By conversion to a cerium oxide-based ceramic film, an interlayer insulating film or the like which is used as a semiconductor device or a liquid crystal display device can be used. -53-

Claims (1)

1252383 六、申請專利範圍 第901 21 1 23號「感光性聚矽胺烷組成物，使用它之圖案形成 方法，及其塗膜之煅燒方法」專利案 (2005年12月I2日修正） A申請專利範圍： 1 . 一種圖案形成方法，其係爲藉由使感光性聚矽胺烷組成 物之塗膜於曝光後顯像、形成圖案化聚矽胺烷膜之方法 ，其特徵爲使經曝光的感光性聚矽胺烷塗膜接觸相對於 基板溫度之相對濕度爲35%〜90%的含水蒸氣之氣體後予 以顯像。 2 ·如申請專利範圍第1項之圖案形成方法，其中於與含水 蒸氣之氣體接觸時將感光性聚矽胺烷塗膜加熱。 3. —種感光性聚矽胺烷塗膜之煅燒方法，其係爲使感光性 聚矽胺烷塗膜經煅燒的方法，其特徵爲設置使感光性聚 矽胺烷塗膜曝光的工程及接觸相對於基板溫度之相對濕 度爲35%〜90%的含水蒸氣之氣體的工程作爲該煅燒的前 處理工程，且具有將在該煅燒的前處理工程中曝光及與 含水蒸氣之氣體接觸的塗膜煅燒之工程。 4 .如申請專利範圍第3項之感光性聚矽胺烷塗膜之煅燒方 法，其中使感光性聚矽胺烷塗膜圖案化。 5 ·如申請專利範圍第3項之感光性聚矽胺烷塗膜之煅燒方 法，其中於加濕處理時將感光性聚矽胺烷塗膜加熱。 6 . —種感光性聚矽胺烷組成物，其特徵爲由含有以通式： -[Sil^NRU-爲基本構成單位、以通式： 1252383 六、申請專利範圍 -[SiR62NR7]-及/或[SiRMNR7)。」]-所示其它構成單位、 且對基本構成單位而言含有0.1莫耳％〜100莫耳％、數 量平均分子量100〜1 00,000之改質聚矽倍半胺烷（其中 ’ R6係各表示獨立的碳數1〜3之烷基或經取代或未經 取代的苯基，R7係各表示獨立的氫、碳數1〜3之院基 或未經取代的苯基）、與光酸發生劑、與作爲形狀安定 化劑之水溶性化合物所成。 7 .如申請專利範圍第6項之感光性聚矽胺烷組成物，其中 光酸發生劑係爲選自於亞楓鐵鹽系化合物及三哄系化合 物。 8 ·如申請專利範圍第6或7項之感光性聚矽胺烷組成物， 其更含有溶解防止劑。 9 .如申請專利範圍第8項之感光性聚矽胺烷組成物，其中 溶解防止劑係選自於第3 - 丁氧基羰基化兒茶酚、第3 _ 丁氧基羰基化氫醌、二苯甲酮-4,4’-二羧酸第3-丁酯及 4,4’-氧化二苯甲酸第3-丁酯，且對感光性聚矽胺烷組 成物而言含有0.1〜40重量％。 1 0 .如申請專利範圍第6項之感光性聚矽胺烷組成物，其 中水溶性化合物係爲含有硝基之化合物。 1 1 .如申請專利範圍第6項之感光性聚矽胺烷組成物，其 中水溶性化合物爲含有碳酸酯之化合物。 1 2 .如申請專利範圍第6項之感光性聚矽胺烷組成物，其 中另含有增感色素。 ---- 1252383 六、申請專利範圍 1 3 .如申請專利範圍第6項之感光性聚矽胺烷組成物，其 中感光性聚矽胺烷組成物爲層間絕緣膜用。 1 4 . 一種層間絕緣膜的圖案形成方法，其特徵爲形成由含 有通式：-[SiI^NR7)!」]-爲基本構成單位、以通式： -[SiR62NR7]-及/或[SiR63(NR7)Q.5]-所示其它構成單位、 且對基本構成單位而言含有〇·1莫耳％〜1〇〇莫耳％、數 量平均分子量1〇〇〜1〇〇,〇〇〇之改質聚矽倍半矽烷（其中 ，R6係各表示獨立的碳數1〜3之烷基或經取代或未經 取代的苯基，R7係各表示獨立的氫、碳數1〜3之烷基 或未經取代的苯基）、與光酸發生劑、與作爲形狀安定 化劑之水溶性化合物的塗膜’且在該塗膜上圖案狀照射 光、使該塗膜經照射的部分溶解除去、再使圖案塗膜於 周圍氣氛中放置或經锻燒。1252383 VI. Patent Application No. 901 21 1 23 "Photosensitive Polyamidane Composition, Patterning Method Using It, and Calcination Method of Its Coating Film" Patent Case (Revised December 12, 2005) A Application Patent Range: 1. A method for forming a pattern by exposing a coating film of a photosensitive polyamidene composition to a patterned polyimamide film by exposure to light, which is characterized by exposure The photosensitive polyaminice coating film is exposed to a gas containing water vapor having a relative humidity of 35% to 90% with respect to the substrate temperature. 2. The pattern forming method of claim 1, wherein the photosensitive polyimide substrate is heated while being in contact with a gas containing water vapor. 3. A method for calcining a photosensitive polyaminice coating film, which is a method for calcining a photosensitive polyimide substrate, characterized in that a process for exposing a photosensitive polyimide film is provided Engineering for contacting a vapor containing water having a relative humidity of 35% to 90% with respect to the substrate temperature as a pretreatment project of the calcination, and having a coating which is exposed to the gas of the vapor containing in the pretreatment of the calcination. Film calcination project. 4. A method of calcining a photosensitive polyaminice coating film according to claim 3, wherein the photosensitive polyamidamine coating film is patterned. 5. A method of calcining a photosensitive polyimide substrate according to claim 3, wherein the photosensitive polyimide film is heated during the humidification treatment. 6. A photosensitive polyamidene composition characterized by containing the formula: -[Sil^NRU- as a basic constituent unit, and having the formula: 1252383, the patent application scope-[SiR62NR7]-and/ Or [SiRMNR7). "]--the other constituent unit, and the basic constituent unit contains 0.1 mol% to 100 mol%, and the number average molecular weight is 100 to 1 00,000 modified polydecyl sesquiamine (wherein 'R6 system An independent alkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted phenyl group, each of which represents an independent hydrogen, a phenyl group having 1 to 3 carbon atoms or an unsubstituted phenyl group, and a photoacid The agent is formed with a water-soluble compound as a shape stabilizer. 7. The photosensitive polyamidane composition according to claim 6, wherein the photoacid generator is selected from the group consisting of a sulphate salt compound and a triterpenoid compound. 8. The photosensitive polyamidane composition according to claim 6 or 7, which further contains a dissolution preventing agent. 9. The photosensitive polyamidene composition according to claim 8, wherein the dissolution preventing agent is selected from the group consisting of a 3-butoxycarbonylated catechol, a tert-butoxycarbonylhydroquinone, 3-butanone of benzophenone-4,4'-dicarboxylic acid and 3-butyl ester of 4,4'-dibenzoic acid, and 0.1 to 40 for photosensitive polyamidone composition weight%. 10. The photosensitive polyamidene composition of claim 6, wherein the water-soluble compound is a compound containing a nitro group. 1 1. The photosensitive polyamidane composition of claim 6, wherein the water-soluble compound is a carbonate-containing compound. 1 2 . The photosensitive polyamidane composition of claim 6 of the patent application, further comprising a sensitizing dye. ---- 1252383 VI. Application Patent Range 1 3. The photosensitive polyamidene composition of claim 6 of the patent application, wherein the photosensitive polyamidane composition is an interlayer insulating film. A method for forming a pattern of an interlayer insulating film, which is characterized in that the composition is composed of a formula: -[SiI^NR7)!"- is a basic constituent unit, and the formula: -[SiR62NR7]- and/or [SiR63 (NR7) Q.5]- other constituent units, and the basic constituent unit contains 〇·1 mol%%1〇〇mol%, number average molecular weight 1〇〇~1〇〇,〇〇〇 The modified polyfluorene sesquioxane (wherein R6 each represents an independent alkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted phenyl group, and R7 each represents an independent hydrogen and a carbon number of 1 to 3; a portion of an alkyl group or an unsubstituted phenyl group, a photo-acid generator, and a water-soluble compound as a shape-stabilizing agent, and which is irradiated with light on the coating film to irradiate the coating film The solution is removed by dissolution, and the pattern coating film is placed in the surrounding atmosphere or calcined.
TW90121123A 2001-08-28 2001-08-28 Photosensitive polysilazane composition, pattern-forming method using it, and calcination method of its coating film TWI252383B (en)

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