1258056 玫、發明說明： 【發明所屬之技術領域】 本發明關於一種感光性聚醯亞胺/氧化矽有機無機混成薄膜材料及其 製備方法。 依據本發明方法製得之薄膜材料具有優異耐熱性、低熱膨脹係數、低 介電常數與極佳之光學性質。進行微影製程時並具有良好之微影解析度及 尺寸穩定性。可適於微電子、半導體器件製造與光學波導器件製造之用。 【先前技術】 金屬、陶瓷、高分子以及電子材料為現今材料科學的四個主要領域。 每種材料各有其特殊性質與優缺點。例如高分子具有易加工、強韌、具彈 性、抗腐及便宜等優點，但其耐紐機械強度較差；而陶 竟材料則具有堅硬、擬性、絕麵耐紐與機砸度優點，但重量較重 I胃碎。μ能夠結合各種材料的優點而彌補其缺點就能鱗到擁有優秀 性質的薪珊料。此—概纽引了有機—無觀成材料（hybrid materiai) 的廣泛研究。 傳統的複合材料（composite)其大小（d〇腿in)通常為數百微米級至 爱米級’此類㈣㈣錢或域成份主要扮紐變結構或魏的角色， 主要利用_錢合（blend)的方式贿，硫成鼎的製備方式主要為 膠凝膠法（Sol-Gel)或是自組裝法（self_assefflbly)等化學方式，藉 由有機與無機成份自她獨齡纽善其賴。勤ι，將有機材料導入 無機主體中，可以改善無機材料易碎的性質並提供多樣顏色等。反之將 無機材料導人錢域中時，财叫加其機械強度 、耐熱性、改善吸濕 TP030120 1258056 性質等，而藉由分子設計更可開發出嶄新的性質。 一般的有機-無機材料通常需要加熱到較高的溫度以除去系統中的溶 劑，並使無機成份完成交聯反應以除去水氣。其中聚醯亞胺因為較一般常 用的高分子擁有更優異的機械與耐熱性質已廣泛的使用在半導體、印刷電 路板等產業中。因此聚醯亞胺/氧化梦（polyijuide/ silica)混成材料引 起廣泛注意並有眾多研究，以期得到更優異的性質與改善其缺點。 目前之聚醯亞胺/氧化矽混成材料的製備方式，茲敘述如下： (1) 將二酸酐與二胺加入常用的溶劑如二甲基乙醯胺(DMAc)或N一甲基 11比洛烧_(NMP)中反應成為聚醯胺酸(p〇ly(amic acid)) (paa);使四乙氧 基矽烧(TE0S)或四甲氧基矽烷(TM0S)在乙醇或四氫呋喃（THF)中，加入水 及催化劑（可為酸催化或鹼催化），使TE0S或TM0S進行水解與聚縮合反應 形成养聚氧化梦微粒或分子團，再將該PAA溶液與氧化石夕溶液均勻攪拌後 得到聚醯亞胺/氧化矽混成材料之前驅溶液，最後以前驅溶液進行薄膜塗佈 與加熱固化等製程。 (2) 將二酸酐與二胺加入常用的溶劑如DMAC或nmp中反應成為聚醯胺 酸’然後直接將TE0S或TM0S單體加入PM溶液中，利用醯胺酸作為催化 劑直接進行氧化矽的水解與聚縮合反應，最後得到聚醯亞胺/氧化矽混成材 料之前驅溶液。 (3) 將二酸酐與二胺反應成為聚醯胺酸，加入3-胺基丙基三乙氧基石夕烷 (APrTEOS)等偶合劑於PM端之酸酐，再加入TE0S或TM0S行水解縮合反 應’使得有機相的聚醯亞胺藉由偶合劑與無機相的氧化矽之間產生共價鍵 TP030120 7 1258056 結，提高有機她無__她性，_小氧化·㈣大小並提高其 分布均勻性而獲得較佳的性質。 (4) 將_触與二紐應成絲養酸，然後直接將丽或麵$單體 加入PAA溶液中，利用醯胺酸作為催化劑直接進行氧辨的水解與聚縮合 反應除此之外並加X —縮水甘&氧基㊅基三甲氧基魏(G職）等偶合 劑’猎由氫鍵等分子間作用力提高有機相與無機烟的相容性，以縮小氧 化石夕顆粒的大小並提高其分布均句性，獲得較佳性質。 (5) 將二酸酐與二胺反應成為聚醯胺酸，加入3—胺基丙基三乙氧基石夕烷 (APrTEOS)等偶合劑於pm端之酸酐，再加入TE〇s或TM〇s行水解縮合反 應，此外並加入_縮水甘油氧基丙基三甲氧基石夕烷(GTM〇s)等偶合劑，同 時藉由分子内共價鍵（由APrTEOS輕合劑提供）與氫鍵等分子間作用力（由 GTM0S耦合劑提供）以提高有機相與無機相間的相容性，來縮小氧化石夕顆粒 的大小並提高其分布均勻性。 綜合前述聚醯亞胺/氧化矽混成材料的方式雖可得到性質較原本之聚 酿亞胺為佳之高性能有機無機混成材料，但以此材料欲於晶圓或玻璃基板 上製作微結構或具功能之特疋圖案時’由於材料不具感光性，在薄膜固化 之後，必須利用傳統的微影製程來製作圖型，其步驟包括：丨、光阻塗佈； 2、光阻曝光顯影；3、以活性離子蝕刻等方式進行混成材料薄膜之钱刻；4、 以臭氧及特定化學品進行殘餘光阻之剝離洗淨等步驟，製程步驟複雜較為 耗時，且聚醯亞胺/氧化矽混成材料之抗姓刻性佳，進行姓刻時之參數設計 不易。同時餘刻後之圖型易有侧璧粗糙度大與蝕刻不完全，以及光阻易殘 TP030120 8 1258056 留於圖型上等缺點。 因此本發明為了改善一般非感光性聚醯亞胺/氧化矽有機無機混成材 料之上述缺點，針對其製備方法進行廣泛研究，而完成本發明。本發明之 方法可直接應用至以上述⑴—⑸所製備之聚酿亞胺/氧化石夕混成材料前驅 /谷液’使其成為具感光性之聚醯亞胺/氧化石夕有機無機混成材料 ，由於感光 性之聚酿亞胺/氧化辦機無機混册料本脚可視為_種光阻，可直接進 打曝光顯影之步驟以製作所需之圖型，可大幅減少製程步驟，提高產量以 及產品良率。 【發明内容】 本發明有關-種製賴光性聚醯亞胺/氧切有機無觀成薄膜材料 之方法，包括下列步驟： )、芳族一酸酐及芳族二胺在35。。或低於坑之溫度反應，以製備 聚酿胺酸，其中該芳族二酸酐莫耳數大於或等於該芳族二胺； —(b)添2加式H2N{Si(R2)3所示之胺基偶合劑（其中ri代表⑽烧基、 伸^基，R2彼此可相同或不同且代表G e烧氧基）使其中之胺基與步驟⑷ 〜x級之酸酐基反應，得到胺基偶合劑封端之聚酿胺酸，其中胺 基偶合劑之莫耳數小於芳族二胺之莫耳數； / )於/驟（b)製得的溶液中加入式所示之烧氧化石夕單體（其 中R3彼此可相同或恤細素、C,观基補氧基及芳氧基），^ 用聚釀胺酸本身作為催化劑在少量水存在下，於肌至副。C之溫度範圍 内於/合劑中進仃水解及縮合反應’因而&奶4中之矽烷醇基與進行水解 -應後之聚醯胺酸末端之胺基偶合劑產生共價鍵結 ，可提高相容性； TP030120 1258056 ⑷於步驟（c)所製得之溶液中，加入式攸的所示之分子間作用 力偶合劑單體（其巾以末端帶有魏基之基，R5彼断烟或不同且代 表齒素、G道氧基、㈣氧基及芳氧基）進行水解縮合反雜並與氧化石夕 部份產生共價鍵結，環氧細環形趣基㈣聚醯驗上贿基形成氳 鍵，形成有機無機混成材料前驅溶液； (e) 於步驟⑷所製得之溶液中，加入式R8N(R9)2所示之單體（其中R8 為末端帶有不飽和基之基，R9彼此可_或獨且代表G禮基），此單體 中之三級胺與有機無機混成材料前驅溶液中气聚醯胺酸之羰酸基形成酸/ 驗離子鹽類，使聚醯胺酸帶有可感光聚合之不飽和侧鏈基； (f) 於步驟(e)所製得之溶液中，加入可感光產生自由基以進行光起始 反應之分子（光起始劑），形成感光性之聚醯亞胺/氧化矽有機無機混成材料 前驅溶液；及 (g) 將所得感光性有機無機混成材料前驅溶液塗佈於基材上成膜獲得 有機無機混成材料薄膜。 本發明方法中，該成膜製程之進行包括使感光性有機無機混成材料前 驅溶液塗佈於基材上，於加熱板或烘箱中以40-200°C之溫度進行軟烤去除 部份溶劑後’利用一其上具有預先設計圖型之光罩以接觸或非接觸之方 式’將光源透過該光罩照射或投影至軟烤後之低體積收縮性之感光性有機 無機混成材料薄膜，或者利用電子束或雷射等聚焦光源照射至軟烤後之感 光性有機無機混成材料薄膜，使其進行感光交聯聚合之反應，獲得感光性 有機無機混成材料薄膜。 TP030120 10 1258056 進仃感光交連聚合後之轉請得之縣性有機錢减材料薄膜， t& 4G-2GG°(：之溫度it行紐烤絲雜㈣直方向之 干涉情形與大部份溶舰，_以有機溶齡主體之顯，使曝光後所 得之感光性有機無機混成材料薄膜浸泡其中，或將顯影劑以適當方式喷灑 塗佈於低體積收縮性之感光性有機無機混成材料薄膜上，使薄膜上未經曝 光之區域溶解去除’再以合適之有機鋪進行清洗(Hnse)、將溶劑以氮氣 人送或使基板快速旋轉乾燥等方式去除，可得到所需之圖型。 將圖型化後之低體積收縮性之感光性有機無機混成材料薄膜加熱至鲁 200-600 C進行熱固化烘烤，使聚醯胺酸部份閉環形成聚醯亞胺，氧化矽部 伤縮合元成，可在基板上得到以低體積收縮性之感光性有機無機混成材料 所製成之特定圖型。 此低體積收縮性之感光性有機無機混成材料所製成之特定圖型可為微 電子或半導體製造中所需之特定圖型，或為平面光波導器件中所需之各可 使光傳導之各種圖型。 本發明又有關一種製備感光性聚醯亞胺/氧化矽有機無機混成薄膜材鲁 料之方法，包括下列步驟： (al)以芳族二酸酐及芳族二胺在35t或低於35〇c之溫度反應，以製 ’ 備聚醯胺酸’其中該芳族二酸酐莫耳數大於或等於該芳族二胺； (bl)添加式HW-R1-Si(R2)3所示之胺基偶合劑（其中R1代表Cm伸烷基、 伸芳基’ R2彼此可相同或不同且代表Ci-6烧氧基）使其中之胺基與步驟（ai) 製得之聚醯胺酸之酸酐基反應，得到胺基偶合劑封端之聚醯胺酸，其中胺 TP030120 11 1258056 基偶合劑之莫耳數小於芳族二胺之莫耳數； (cl)以式Si(R3)4所示之烷氧化石夕單體（其中R3彼此可相同或不同且 代表i素、Cm烧氧基、(^6稀氧基及芳氧基），利用酸或驗作為催化劑在少 量水存在下，於15°C至l〇(TC之溫度範圍内，於溶劑中進行水解及縮合反 應，形成氧化石夕之分子團（cluster)或顆粒(particle); (dl)使步(al)所製得之溶液與步驟(c3)所製得之溶液或使步驟(b3) 所製得之溶液與步驟(c3)所製得之溶液均勻混合，使其形成聚醯亞胺/氧化 矽有機無機混成薄膜材料前驅溶液； (el)於步驟(dl)所製得之溶液中，加入式R8N(R9)2所示之單體（其中 R8為末端帶有不飽和基之基，R9彼此可相同或不同且代表Ci e烷基），此單體 中之二級胺與有機無機混成材料前驅溶液中之聚醯胺酸之羰酸基形成酸/ 驗離子鹽類，使聚醯胺酸帶有可感光聚合之不飽和側鏈基； (Π)於步驟(el)所製得之溶液中，加入可感光產生自由基以進行光起 始反應之分子（光起始劑），形成感光性之聚醯亞胺/氧化石夕有機無機混成材 料前驅溶液；及 (gl)將所得感光性有機無機混成材料前驅溶液塗佈於基材上成膜獲得 有機無機混成材料薄膜。 本發明方法中，該成膜製程之進行包括使感光性有機無機混成材料前 驅溶液塗佈於基材上，於加熱板或烘箱中以4〇-2〇〇°C之溫度進行軟烤去除 部份溶劑後，利用一其上具有預先設計圖型之光罩以接觸或非接觸之方 式，將光源透過該光罩照射或投影至軟烤後之低體積收縮性之感光性有機 TP030120 12 1258056 無機混成材料薄膜，或者利用電子束或雷射等聚焦光源照射至軟烤後之感 光性有機無機混成材料薄膜，使其進行感光交聯聚合之反應，獲得感光性 有機無機混成材料薄膜。 進行感光交連聚合後之經曝光所得之感光性有機無機混成材料薄膜， 可於加熱板或烘箱中以40-20(TC之溫度進行曝後烤去除薄膜内垂直方向之 干涉情形與大部份溶劑後，利用以有機溶劑為主體之顯影劑，使曝光後所 得之感光性有機無機混成材料薄膜浸泡其中，或將顯影劑以適當方式喷灑 塗佈於低體積收縮性之感光性有機無機混成材料薄膜上，使薄膜上未經曝 光之區域溶解去除，再以合適之有機溶劑進行清洗、將溶劑以氮氣吹送或 使基板快速旋轉乾燥等方式去除，可得到所需之圖型。 將圖型化後之低體積收縮性之感光性有機無機混成材料薄膜加熱至 200-600°C進行熱固化烘烤，使聚醯胺酸部份閉環形成聚醯亞胺，氧化石夕部 份縮合完成，可在基板上得到以低體積收縮性之感光性有機無機混成材料 所製成之特定圖型。 此低體積收縮性之感光性有機無機混成材料所製成之特定圖型可為微 電子或半導體製造中所需之特定圖型，或為平面光波導器件中所需之各可 使光傳導之各種圖型。 【實施方式】 本發明方法中所用之”聚醯胺酸，，一詞意指由雙胺及雙酐反應所得之 含有-NH-CO-官能基之產物，而”聚醯亞胺，，一詞則為該聚醯胺酸在升溫固 化使聚醯胺酸上之-NH-CO-官能基與羧酸官能基環化產生之產物。 本發明方法中R3及R5所示之”鹵素，，意指氟、氯、溴或碘，較好為氣。 TP030120 13 1258056 本發明方法中RHR5所示之” k烷氧基，，意指_〇-烧基之基，該烷 基為含1-6個碳原子之直鏈或分纽基且經由氧原子鍵結 ，其實例包含例 如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三 丁氧基、正戊氧基、新戊氧基、己氧基等。 本發明方法中R3及R5所示之” q·6婦氧基，，意指_〇-稀基之基，該稀基 為含2 6個碳軒之直鏈或分纽基麟崎軒麟，其實例包含例如 乙烯氧基、丙烯氧基、丁烯氧基、戊稀氧基、己烯氧基等。 本發明方法巾R3及R5所示之，，魏基，，意指—㈣基之基，該芳基為例 如苯基或萘基；芳氧基之實例包含例如苯氧基及萘氧基。 本發明方法中R1所不之’’（^6伸燒基，，意指自含丨至6個碳原子之烧類 移除兩個氫原子所形成二價(^_6伸絲，其實例包含例如伸甲基、伸乙基、 伸丙基、1 -曱基伸丙基、2-甲基伸丙基、伸丁基、丨一甲基伸丁基、2—甲基 伸丁基、伸戊基、伸己基等。 本發明方法中R1所示之”伸芳基，，意指自仏七芳族烴移除兩個氫原子 所形成之二價芳基，實例包含例如伸苯基及伸萘基等。 本發明方法中R9所示之，’ Cw烷基，，意指自含1至6個碳原子之烷基， 其實例包含例如甲基、乙基、正丙基、異丙基、i一甲基丙基、2一甲基丙基、 正丁基、異丁基、新丁基、；[一甲基丁基、2一甲基丁基、戊基、己基等。 本發明方法中R4所示之末端帶有環氧基之基可為例如縮水甘油氧基曱 基、縮水甘油氧基乙基、縮水甘油氧基丙基等。 本發明方法中R8所示之，，末端帶有不飽和基之基”意指末端帶有乙烯 TP030120 14 1258056 屬不飽和基之基’其實例包含乙烯基、烯丙基、乙烯基苯基、烯丙基苯基、 丙烯氧基甲基、丙烯氧基乙基、丙烯氧基丙基、丙烯氧基丁基、丙烯氧基 戊基、丙烯氧基己基、甲代丙烯氧基甲基、甲代丙烯氧基乙基、甲代丙烯 氧基丙基、甲代丙職基τ基、甲代丙稀氧基絲及f代丙職基己基等。 本發明製備錢織絲賴機之枝巾，响之絲二酸肝實例 包含（但不限於）例如笨均㈣二針⑽A)、4,4_二敗酸二軒(麵）、4,4一 六氟亞異丙基二酞酸二酐⑽A)、K三氟？基)_2,3,5,6_苯讀酸二野 (P3FDA)、1，4-雙(三氟甲基)-2,3,5,6-笨四竣酸二軒⑽觸㈣，，4, _ 二羧基苯基)-1，3, 3-三甲基茚滿-5, 6-二鲮酸二酐、卜(3， 4，羧某苯 基)-1，3, 3-三甲基茚滿-6, 7-二羧酸二酐、卜(3,，4,—二緩基苯基)一3一甲 基節滿-5,6-二紐二酐、H3,，4’ 基笨基基節滿二7_二叛 酸二酐、2’ 3’ M0-二萘絲四缓酸二奸、L 4,5,8_蔡四_二肝、& 6_二 氯萘-1，4,5,8-四賴二酐、2,7-二氣萘4, 5,8-四緩酸二野、& & 6, 7_ 四氣萘-2,4, 5, 8-四羧酸二酐、菲-1，8, 9,10-四羧酸二酐、3, 3， 4 4，一二 苯甲嗣四叛酸二肝、以，，3’3,-二苯甲酮四驗二奸、3 3, Μ聯 苯四叛酸二肝、3,3,，4,4,-二苯甲酮四_二奸、2 2,，3 3，-聯苯四 _亞異丙基二峨二肝、 4,4’ -氧基二酞酸二酐、4,4’ -續醯基二駄酸二酐、3 τ — 一 ’ <3 -氧暴二敌酸二 肝、4’ 4’ -亞甲基二酞酸二酐、4,4,-硫基二酞酸二酐、4, *，亞乙基二 酞酸二酐、2,3,6, 7-萘四誠讀、i，2,4, 5一萘賤酸二肝、12,5, 蔡 四羧酸二Sf、苯-1，2,3,4-四贼二酐、哪-2,3, 5, 6-四練二肝等，其 TP030120 15 1258056 中較好為笨均四酸二酐⑽a)、44h 二酞酸二奸(咖）、卜(三氟f基)_2 1、氟亞異丙基 雙㈣甲基…Λ6-苯四魏二二四練二- 本發明製備有機錢混朗蹄料之方法中 妳_例w-a__fb)、略=^自 2, 2, -5’ 5,-四氣聯苯胺⑽、3, 3,—二氣聯笨胺⑽）、3, 3,二甲基七， '2>" 4, ' 2,, 4, _ 1基聯#)、2,2’ -雙(3,絲基)六氣峨、2,2,胺基苯^ 六氣丙烧、4’4 -氧基-雙[3-(三氟曱基)苯胺、3,5一二胺基三氟甲苯 (diaminobenzotrifluoride)、1，4-四氟伸苯二胺（tetraflu〇r〇phenylene diamine)、四氟-間-伸苯二胺、4, 4’ -氧基二苯胺(〇da)、1，4-雙(4-胺基 苯氧基)-2-第三丁基苯(BATB)、2, 2，-二甲基-4,4，-雙(4-胺基苯氧基)聯 苯(DBAPB)、2, 2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷(BAppH)、2, 2，-雙 [4-(4-胺基苯氧基)苯基]原冰片烧(BAPN)、5-胺基-1-(4’ -胺基苯 基)-1，3, 3-三甲基茚滿、6-胺基-1 -(4’ -胺基苯基)-1，3, 3-三甲基茚滿、 4, 4’ -亞甲基雙(鄰-氯苯胺）、3, 3’ -二氣二苯胺、3, 3’ -確醯基二苯胺、 4, 4’ -二胺基二苯甲酮、1，5-二胺基萘、雙(4-胺基苯基)二乙基石夕烷、雙 (4-胺基苯基)二苯基梦烷、雙(4-胺基苯基）乙基膦氧化物、N-(雙(4-胺基 苯基))-N-甲基胺、N-(雙(4-胺基苯基))-N-苯基胺、4,4’ -亞甲基雙(2-甲 基苯胺）、4,4’ -亞甲基雙(2-甲氧基苯胺）、5, 5’ _亞甲基雙(2-胺基苯 酚）、4,4’ -亞甲基雙(2-甲基苯胺）、4,4’ -氧基雙(2-甲氧基苯胺）、4,4’ - TP030120 16 1258056 氧基雙(2-氯笨胺）、2,2，-雙(4-胺基苯酚）、5, 5，-氧基雙(2_胺基苯酚）、 4,4’ -硫基雙(2—甲基苯胺）、4,4’ _硫基雙(2一甲氧基苯胺）、4,4’ -硫基 雙氯苯胺）、4, 4’ -橫醯基雙(2-甲基苯胺）、4,4’ -續酿基雙(2-乙氧基 苯胺）、4,4,〜續醯基雙(2-氯苯胺）、5,5,-續醯基雙(2-胺基苯酚）、3,3,-二甲基-4,4,-二胺基二苯甲酮、3, 3,-二甲氧基-4,4,-二胺基二苯曱 嗣、3, 3’ —二氣-4,4，_二胺基二苯甲酮、4,4’ _二胺基聯苯、間-苯二胺、 對一苯二胺、4,4，-亞甲基二苯胺、4,4，-硫基二苯胺、4,4，-績醯基二苯 胺、4, 4’ -亞異丙基二苯胺、3,3，-二甲基聯苯胺、3, 3，-二曱氧基聯苯 胺、3, 3’ -二羧基聯苯胺、2,4-甲苯基二胺、2, 5-甲苯基二胺、2,6-甲苯 基二胺、間-二甲苯基二胺、2,4-二胺基-5-氯甲苯、2,4-二胺基-6-氣甲苯 等。較好為4,4，-氧基二苯胺(0DA)或4,4, -八氟聯苯胺(0FB)。 本發明方法中式Si (R3)4所示之烷氧化矽實例包含(但不限於)例如四甲 氧基矽烷、四乙氧基石夕烷、四丙氧基石夕烷、四丁氧基石夕烷等。 本發明方法中步驟(a)、（b)、（al)、（bl)、（cl)之反應宜在溶劑中進 行。所用溶劑只要可用以溶解本發明所使用之單體即可，並無特別限制。 該溶劑之具體實例包含(但不限於)例如二甲基亞碾(DMS0)、N，N-二甲基乙 酿胺(DMAc)、1-甲基吡咯烷酮(NMP)、N，N-二甲基甲醯胺(DMF)、四氫咲嗔 (THF)、二噚烷、甲基乙基酮(MEK)、氯仿(CHCh)、二氣甲烷、r—丁内醋、 乙酸丁酯、環戊酮、丙二醇單甲基醚乙酸酯（PGMEA)、糠醇(THFA)、甲基 戊基酮(2-庚酮）、二乙二醇單己基醚(DGME)、丙二醇單曱基越(pGjjg)、乙 酸正丁酯(nBA)、丙二醇單乙醚、丙二醇單-正-丙基醚、二乙二醇單丁基鍵 TP030120 17 1258056 乙酸酯等。其中較好使用1 -甲基吡咯烷酮(NMP)。 本發明方法中步驟(b)及(bl)之式腿-R^SKR2)3之胺基偶合劑實例包 含(但不限於)例如3-胺基丙基三甲氧基石夕烧(APrTMOS)、3-胺基丙基三乙氧 基矽烷(APrTEOS)、3-胺基苯基三曱氧基矽烷(aptmos)、3—胺基苯基三乙氧 基矽烷(APTE0S)等。 本發明方法中步驟⑷中式R3-Si(R4)3所示之分子間作用力之偶合劑實 例包含(但不限於）r-縮水甘油氧基丙基三甲氧基石夕燒(GTM〇s)、I縮水甘 油氧基丙基三乙氧基矽燒(GTE0S)等。 本發明方法中步驟(e)、（el)中式R8N(R9)2所示之含末端帶有不飽和基 侧鏈基之三級胺單體實例包含(但不限於）甲代丙烯酸2一二甲胺基乙酯、甲 代丙浠酸2-二乙胺基乙酯、甲代丙烯酸2-二丙胺基乙酯、3一甲代丙烯氧基 丙基二甲基胺、3-甲代丙烯氧基丙基二乙胺、3一甲代丙烯氧基丙基二丙基 胺、3-丙婦氧基丙基二甲基胺、3-丙烯氧基丙基二乙基胺、3—丙烯氧基丙 基二丙基胺、3-甲基甲代丙烯氧基丙基二甲基胺、3一甲基甲代丙烯氧基丙 基二乙基胺、3-甲基甲代稱氧基丙基二丙基胺、4-(甲代丙職基丙基） 苯基二甲基胺、4-(甲代丙烯氧基丙基)苯基二乙基胺、4—(甲代丙稀氧基丙 基)苯基二丙基胺、4-(甲代丙職基乙基)苯基二f基胺、4—(甲代丙稀氧 基乙基)苯基二乙基胺、4-（甲代丙烯氧基乙基)苯基二丙基胺、4一（甲代丙 烯氧基甲基)苯基二甲基胺、4-(甲代丙烯氧基甲基)苯基二乙基胺、4一（甲 代丙烯氧基甲基)苯基二丙基胺、稀丙基三甲基胺、稀丙基二乙基胺、稀丙 基二丙基胺、4-稀丙基二甲基胺、4—烯丙基二乙基胺、4—稀丙基二丙基胺、 TP030120 18 1258056 稀基—甲基胺、4_乙婦基二乙基n乙稀基二丙基胺。 本發明方法巾步驟㈦及⑹巾，氧切絲醯胺酸或練亞胺之混合 •可為任何比例，在任何比例下所得之所有溶液均不會有沉殿或使溶液 渾濁之情況發生。 本發明方法巾賴之可絲產生自由基以進行光起始反應之分子(光 起始劑)實例包含(但不限於)例如i，卜二甲基+苯基二苯甲嗣(如⑽BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide/iridium oxide organic-inorganic hybrid film material and a process for producing the same. The film material produced by the method of the present invention has excellent heat resistance, low coefficient of thermal expansion, low dielectric constant and excellent optical properties. It has good lithography resolution and dimensional stability when performing lithography. It can be used for microelectronics, semiconductor device manufacturing and optical waveguide device manufacturing. [Prior Art] Metals, ceramics, polymers, and electronic materials are the four main areas of today's materials science. Each material has its own special properties and advantages and disadvantages. For example, polymers have the advantages of easy processing, toughness, elasticity, corrosion resistance and low cost, but their mechanical strength is poor. However, Taojing materials have the advantages of hard, pseudo, and excellent resistance to the new machine and machine. Heavier weight I stomach broken. μ can combine the advantages of various materials to make up for its shortcomings and scale up to have excellent quality. This - the introduction of the organic - non-observation of materials (hybrid materiai) extensive research. The traditional composite (composite) its size (d〇 leg in) is usually hundreds of micrometers to the Amy class. (4) (4) Money or domain components mainly play the role of the structure or the role of Wei, mainly use _ Qianhe (blend The way to make bribes, the preparation of sulfur into the tripod is mainly by the gel method (Sol-Gel) or self-assembly method (self_assefflbly) and other chemical methods, through organic and inorganic ingredients from her own age. Diligently, the introduction of organic materials into inorganic bodies can improve the fragile nature of inorganic materials and provide a variety of colors. On the contrary, when the inorganic material is introduced into the money field, it is called mechanical strength, heat resistance, and improved moisture absorption TP030120 1258056, and the molecular design can develop new properties. Typical organic-inorganic materials typically require heating to a higher temperature to remove the solvent from the system and to complete the crosslinking reaction to remove the moisture. Among them, polyimine has been widely used in industries such as semiconductors and printed circuit boards because of its superior mechanical and heat resistance properties to commonly used polymers. Therefore, polyijuide/silica hybrid materials have attracted extensive attention and many studies have been conducted in order to obtain more excellent properties and to improve their disadvantages. The preparation method of the current polyimine/cerium oxide mixed material is as follows: (1) The dianhydride and the diamine are added to a common solvent such as dimethylacetamide (DMAc) or N-methyl 11 pir. The reaction in the combustion (_NMP) becomes p〇ly (amic acid) (paa); the tetraethoxy oxime (TE0S) or tetramethoxy decane (TMOS) in ethanol or tetrahydrofuran (THF) In addition, adding water and a catalyst (which may be acid catalyzed or base catalyzed), the TE0S or TM0S is subjected to hydrolysis and polycondensation to form agglomerated oxidized dream particles or molecular groups, and then the PAA solution and the oxidized stone solution are uniformly stirred. The solution of the polyimine/cerium oxide mixed material is obtained, and finally the solution is applied to the film coating and heat curing. (2) The dianhydride and diamine are added to a common solvent such as DMAC or nmp to form polylysine. Then TEOS or TMOS monomer is directly added to the PM solution, and the hydrolysis of cerium oxide is directly carried out by using proline as a catalyst. The polycondensation reaction is carried out, and finally the solution of the polyimine/iridium oxide mixed material is obtained. (3) The dianhydride is reacted with a diamine to form a poly-proline, and a coupling agent such as 3-aminopropyltriethoxy oxalate (APrTEOS) is added to the anhydride at the PM end, and then TEOS or TMOS is added to carry out a hydrolysis condensation reaction. 'The organic phase of the polyimine makes a covalent bond between the coupling agent and the inorganic phase of yttrium oxide TP030120 7 1258056 knot, improve the organic she has no __ her sex, _ small oxidation · (four) size and improve its uniform distribution Better properties are obtained. (4) The _ touch and the second nucleus should be made into a silk acid, and then the granules can be directly added to the PAA solution, and the hydrolytic acid and the polycondensation reaction can be directly carried out by using proline as a catalyst. Adding a coupling agent such as X-shrinking gan & oxyhexyltrimethoxy-Wei (G), and hunting, enhance the compatibility of the organic phase with inorganic smoke by intermolecular forces such as hydrogen bonding, to reduce the oxidized granules Size and improve the distribution of the sentence, get better properties. (5) The dianhydride is reacted with a diamine to form a poly-proline, and a coupling agent such as 3-aminopropyltriethoxy oxalate (APrTEOS) is added to the anhydride at the pm end, and then TE〇s or TM〇s are added. Hydrolysis condensation reaction, and addition of a coupling agent such as _glycidoxypropyltrimethoxy oxalate (GTM〇s), while being intramolecular covalent bond (provided by APrTEOS light combination agent) and hydrogen bonding The force (provided by the GTM0S coupling agent) to increase the compatibility between the organic phase and the inorganic phase to reduce the size of the oxidized stone particles and improve the uniformity of their distribution. The method of synthesizing the polyimine/cerium oxide mixed material can obtain a high-performance organic-inorganic hybrid material having better properties than the original poly-imine, but the material is intended to be fabricated on a wafer or a glass substrate. When the function is special, the pattern is not sensitive. After the film is cured, the conventional lithography process must be used to make the pattern. The steps include: 丨, photoresist coating; 2. photoresist exposure development; The method of performing reactive ion etching and the like is carried out on the film of the mixed material; 4. the step of removing the residual photoresist by ozone and a specific chemical, the process steps are complicated and time consuming, and the polyamidene/cerium oxide mixed material is used. The anti-surname is good, and the parameter design when the surname is engraved is not easy. At the same time, the pattern after the engraving is easy to have the side roughness and the etching is incomplete, and the photoresist is easy to be disabled TP030120 8 1258056 is left in the pattern and other disadvantages. Therefore, in order to improve the above-mentioned disadvantages of the general non-photosensitive polyimide/iridium oxide organic-inorganic hybrid material, the present invention has been extensively studied for its preparation method, and completed the present invention. The method of the invention can be directly applied to the poly-imine/oxidized stone precursor material precursor/column liquid prepared by the above (1)-(5) to make it a photosensitive polyimine/oxidized stone organic-inorganic hybrid material. Because the photosensitive polyimide/oxidation machine inorganic mixed material can be regarded as a kind of photoresist, it can directly enter the exposure and development steps to produce the required pattern, which can greatly reduce the process steps and increase the output. And product yield. SUMMARY OF THE INVENTION The present invention relates to a method for producing a photopolymerizable polyimine/oxygen-cut organic film material comprising the following steps:), an aromatic mono-anhydride, and an aromatic diamine at 35. . Or lower than the temperature reaction of the pit to prepare polylactoic acid, wherein the aromatic diamine molar number is greater than or equal to the aromatic diamine; - (b) adding 2 plus H2N{Si(R2)3 An amine-based coupling agent (wherein ri represents (10) an alkyl group, a stretching group, and R2 may be the same or different from each other and represents a G e-alkoxy group), and an amine group thereof is reacted with an acid anhydride group of the step (4) to the x-th group to obtain an amine group. a coupler-terminated poly-araminic acid, wherein the number of moles of the amine-based coupling agent is less than the number of moles of the aromatic diamine; /) the oxidized stone of the formula is added to the solution prepared in the step (b) Evening monomers (wherein R3 may be the same as each other or the melamine, C, alkoxy and aryloxy groups), and the polystyryl itself is used as a catalyst in the presence of a small amount of water, in the muscle to the secondary. In the temperature range of C, the hydrolysis and condensation reaction in the mixture is carried out. Thus, the sterol group in the milk 4 is covalently bonded to the amine coupling agent at the end of the polyamine. Improve compatibility; TP030120 1258056 (4) In the solution prepared in the step (c), add the intermolecular force coupling monomer shown in the formula (the towel has a Wei group at the end, R5 is broken Or different and representing dentate, G-channel oxy group, (tetra)oxy group and aryloxy group), hydrolyzed and condensed, and covalently bonded to the oxidized stone, and the epoxy ring-shaped group (4) Forming a ruthenium bond to form a precursor solution of the organic-inorganic hybrid material; (e) adding a monomer represented by the formula R8N(R9)2 to the solution prepared in the step (4) (wherein R8 is a group having an unsaturated group at the terminal) , R9 can _ or stand alone and represent G ritual), the tertiary amine in the monomer and the carbonyl acid group of the gas-polymeric lysine in the precursor solution of the organic-inorganic hybrid material form an acid/ion salt, The amine acid has a photopolymerizable unsaturated side chain group; (f) in the solution prepared in the step (e), a molecule (photoinitiator) which generates a radical for photoinitiation reaction, forms a photosensitive polyimine/cerium oxide organic-inorganic hybrid material precursor solution; and (g) a precursor of the obtained photosensitive organic-inorganic hybrid material The solution is coated on a substrate to form a film to obtain a film of an organic-inorganic hybrid material. In the method of the present invention, the film forming process comprises: applying a photosensitive organic-inorganic hybrid material precursor solution to a substrate, and performing soft baking at a temperature of 40-200 ° C in a heating plate or an oven to remove a part of the solvent. 'Using a photomask with a pre-designed pattern to contact or non-contact the light source through the reticle to be irradiated or projected to a soft-baked low-volume shrinkable photosensitive organic-inorganic hybrid material film, or to utilize A photosensitive organic-inorganic hybrid material film such as an electron beam or a laser is irradiated onto the soft-baked photosensitive organic-inorganic hybrid material film to carry out a photocrosslinking polymerization reaction to obtain a photosensitive organic-inorganic hybrid material film. TP030120 10 1258056 After the sensitization of the photographic cross-linking polymerization, the county organic money reduction material film, t& 4G-2GG° (: the temperature it is the line of the wire-to-wire (four) straight direction interference and most of the dissolved ships _ immersing the photosensitive organic-inorganic hybrid material film obtained after exposure with an organic aging body, or spraying the developer on a film of a low volume shrinkable photosensitive organic-inorganic hybrid material in an appropriate manner The unexposed areas of the film are dissolved and removed, and then washed with a suitable organic shop (Hnse), the solvent is sent by nitrogen or the substrate is rapidly spin-dried, and the desired pattern can be obtained. The film of the low-volume shrinkable photosensitive organic-inorganic hybrid material after heating is heated to Lu 200-600 C for heat curing baking, and the poly-proline is partially closed to form a polyimine, and the yttrium oxide is condensed. A specific pattern made of a photosensitive organic-inorganic hybrid material having a low volume shrinkage can be obtained on a substrate. The specific pattern made of the low volume shrinkable photosensitive organic-inorganic hybrid material can be A specific pattern required for microelectronics or semiconductor fabrication, or various patterns required for light transmission in a planar optical waveguide device. The invention further relates to a method for preparing photosensitive polyimine/cerium oxide organic inorganic The method for mixing a film material includes the following steps: (al) reacting an aromatic dianhydride and an aromatic diamine at a temperature of 35t or lower to prepare a 'poly-proline' The dianhydride has a molar number greater than or equal to the aromatic diamine; (bl) an amine-based coupling agent of the formula HW-R1-Si(R2)3 (wherein R1 represents a Cm alkyl group, an aryl group R2) The same or different and representing Ci-6 alkoxy) can be reacted with an acid anhydride group of the polyamic acid prepared in the step (ai) to obtain an amine-based coupling-capped poly-proline, wherein the amine TP030120 11 1258056 The molar number of the base coupling agent is less than the molar number of the aromatic diamine; (cl) the alkoxyus oxide monomer represented by the formula Si(R3)4 (wherein R3 may be the same or different from each other and represent i , Cm alkoxy, (^6 diloxy and aryloxy), using acid or test as a catalyst in the presence of a small amount of water, at 15 ° C to l (in the temperature range of TC, hydrolysis and condensation reaction are carried out in a solvent to form a cluster or a particle of oxidized stone; (dl) a solution obtained by step (al) and step (c3) Preparing the solution or uniformly mixing the solution prepared in the step (b3) with the solution prepared in the step (c3) to form a precursor solution of the polyimine/yttria organic-inorganic hybrid film material; (el) In the solution prepared in the step (d1), a monomer represented by the formula: R8N(R9)2 (wherein R8 is a group having an unsaturated group at the terminal, and R9 may be the same or different from each other and represents a Ci ealkyl group). The carboxylic acid group of the polyamine in the precursor solution of the monomer and the organic-inorganic hybrid material forms an acid/ion salt, and the poly-proline has a photopolymerizable unsaturated side chain group. (Π) In the solution prepared in the step (el), a molecule capable of photo-generated to generate a radical for photoinitiation reaction (photoinitiator) is added to form a photosensitive polyimine/oxidized oxide organic a precursor solution of an inorganic mixed material; and (gl) applying a precursor solution of the obtained photosensitive organic-inorganic hybrid material to a substrate Forming an organic-inorganic hybrid material film is obtained. In the method of the present invention, the film forming process comprises performing a method for applying a photosensitive organic-inorganic hybrid material precursor solution on a substrate, and performing a soft baking removal portion at a temperature of 4〇-2〇〇°C in a heating plate or an oven. After the solvent is used, the light source is irradiated or projected to the low-volume shrinkable photosensitive organic TP030120 12 1258056 by means of a reticle having a pre-designed pattern in a contact or non-contact manner. The film of the mixed material or the photosensitive organic-inorganic hybrid material film which is soft-baked by a focusing light source such as an electron beam or a laser is subjected to a photocrosslinking polymerization reaction to obtain a photosensitive organic-inorganic hybrid material film. The photosensitive organic-inorganic hybrid material film obtained by the photosensitive cross-linking polymerization can be subjected to exposure in a hot plate or an oven at 40-20 (temperature of TC) to remove the interference in the vertical direction of the film and most of the solvent. Thereafter, the photosensitive organic-inorganic hybrid material film obtained after exposure is immersed therein by using a developer mainly composed of an organic solvent, or the developer is spray-coated in a suitable manner on a low-volume shrinkable photosensitive organic-inorganic hybrid material. On the film, the unexposed areas of the film are dissolved and removed, and then washed with a suitable organic solvent, the solvent is blown by nitrogen or the substrate is rapidly spin-dried, and the desired pattern can be obtained. The film of the low-volume shrinkable photosensitive organic-inorganic hybrid material is heated to 200-600 ° C for heat curing baking, and the poly-proline is partially closed to form a polyimine, and the oxidation of the oxidized stone is completed. A specific pattern made of a photosensitive organic-inorganic hybrid material having a low volume shrinkage is obtained on a substrate. The specific pattern made by the hybrid material may be a specific pattern required for microelectronics or semiconductor fabrication, or various patterns required for light transmission in a planar optical waveguide device. The term "polyamic acid" as used in the method means a product containing a -NH-CO-functional group obtained by the reaction of a bisamine and a dianhydride, and the term "polyimine", the term "poly" A product in which the amine acid is condensed at a temperature to cure the -NH-CO-functional group on the polyphthalic acid and the carboxylic acid functional group. In the method of the present invention, R3 and R5 are represented by "halogen," meaning fluorine, chlorine, Bromine or iodine, preferably gas. TP030120 13 1258056 The "k alkoxy group represented by RHR5 in the process of the present invention, which means a group of _ 〇-alkyl group, which is a straight line containing 1-6 carbon atoms. a chain or a fluorenyl group and bonded via an oxygen atom, examples of which include, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, a third butoxy group , n-pentyloxy, neopentyloxy, hexyloxy, etc. In the process of the present invention, R 3 and R 5 are represented by "q · 6 methoxyl, meaning _ 〇 - The dilute group is a linear or branched Nylon-like sulphate containing 26 carbon porphyrins, and examples thereof include, for example, a vinyloxy group, a propyleneoxy group, a butenyloxy group, a pentyloxy group, a hexeneoxy group, and the like. In the method of the invention, R3 and R5, a thiol group, which means a group of a group, the aryl group is, for example, a phenyl group or a naphthyl group; and examples of the aryloxy group include, for example, a phenoxy group and a naphthyloxy group. In the method of the invention, R1 does not have a ''(6) extension, which means that two hydrogen atoms are formed by the removal of two hydrogen atoms from a pyrene containing 6 to carbon atoms, and examples thereof include, for example, Methyl, ethyl, propyl, 1-mercaptopropyl, 2-methylpropyl, butyl, fluorenylmethyl, 2-methyl-butyl, pentyl And a aryl group represented by R1 in the method of the present invention, meaning a divalent aryl group formed by removing two hydrogen atoms from a hepta-arylene hydrocarbon, and examples include, for example, a phenylene group and a naphthene group. Base. In the process of the present invention, R9 represents a 'Cw alkyl group, meaning an alkyl group having from 1 to 6 carbon atoms, and examples thereof include, for example, methyl, ethyl, n-propyl, isopropyl, i-A. Propyl, 2-methylpropyl, n-butyl, isobutyl, neobutyl, [monomethylbutyl, 2-methylbutyl, pentyl, hexyl, and the like. The group having an epoxy group at the terminal represented by R4 in the method of the present invention may be, for example, a glycidoxycarbonyl group, a glycidoxyethyl group, a glycidoxypropyl group or the like. In the method of the present invention, the group having an unsaturated group at the end" means a group having an unsaturated group such as ethylene TP030120 14 1258056 at the end, and examples thereof include a vinyl group, an allyl group, a vinyl phenyl group, Allyl phenyl, propyleneoxymethyl, propyleneoxyethyl, propyleneoxypropyl, propyleneoxybutyl, propyleneoxypentyl, propyleneoxyhexyl, methacryloxymethyl, A a propylene oxyethyl group, a methacryloxypropyl group, a methyl propyl group τ group, a methacryloxy group and a f propyl group hexyl group, etc. The invention provides a branch of a money woven silk machine Examples of the liver of the spirulina acid include (but are not limited to), for example, stupid (four) two needles (10) A), 4, 4 bis succinic acid bismuth (face), 4,4 hexafluoro isopropylidene dicarboxylic acid Anhydride (10) A), K trifluoro) 2,3,5,6-benzene-reading acid di-field (P3FDA), 1,4-bis(trifluoromethyl)-2,3,5,6-stupid Acid Erxuan (10) Touch (tetra), 4, _ dicarboxyphenyl)-1,3, 3-trimethylindan-5,6-dicarboxylic acid dianhydride, Bu (3, 4, carboxy-phenyl) -1,3,3-trimethylindan-6,7-dicarboxylic dianhydride, Bu (3,4,2-di-hydroxyphenyl)-3-methyl moiety -5,6-Di-Nu-dianhydride, H3,, 4'-based stupid base, 2, 7-dot-reagent dianhydride, 2' 3' M0-d-naphthene, acid-dissolving, L 4,5, 8_蔡四_二肝, & 6_dichloronaphthalene-1,4,5,8-tetralais dianhydride, 2,7-di-naphthalene 4, 5,8-tetra-acidic acid two fields, && 6, 7_ Tetralina-2,4,5, 8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 3, 3, 4 4, benzophenone嗣四叛叛酸二肝,以,3'3,-benzophenone four test two rape, 3 3, Μbiphenyl four tacrotic acid liver, 3,3,,4,4,-benzophenone 4_2, 2 2,, 3 3,-biphenyltetra-isopropylidene di-hepatic, 4,4'-oxydiphthalic acid dianhydride, 4,4'-continued decyl didecanoic acid Diacetate, 3 τ — a ' < 3 - oxygen turbid dimer acid di-hepatic, 4' 4'-methylene dicarboxylic acid dianhydride, 4,4,-thiodiphthalic acid dianhydride, 4, * , Ethylene dicarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracheng, i,2,4,5-naphthoic acid di-hepatic, 12,5, tetracycline di Sf, benzene- 1,2,3,4-four thief dianhydride, which-2,3, 5,6-four training two liver, etc., its TP030120 15 1258056 is preferably stupid tetracarboxylic dianhydride (10) a), 44h diterpenic acid Second rape (coffee), Bu (trifluorof-based)_2 1, Isopropyl bis(tetra)methyl...Λ6-benzenetetrazole dimethylene bis-2 - The method for preparing organic money mixed hoof material in the invention 妳 _ example w-a__fb), slightly = ^ from 2, 2, -5 '5,-four-gas benzidine (10), 3, 3,-di-gas stearamine (10)), 3, 3, dimethyl-7, '2>" 4, ' 2,, 4, _ 1 基联# ), 2,2'-bis(3,silyl)hexahydroquinone, 2,2,aminobenzene^hexafluoropropane, 4'4-oxy-bis[3-(trifluoromethyl)aniline, 3,5-diaminobenzotrifluoride, 1,4-tetrafluoroanthrene phenylene diamine, tetrafluoro-m-phenylenediamine, 4,4'-oxyl Diphenylamine (〇da), 1,4-bis(4-aminophenoxy)-2-t-butylbenzene (BATB), 2, 2,-dimethyl-4,4,-bis (4 -aminophenoxy)biphenyl (DBAPB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BAppH), 2, 2,-bis [4-( 4-Aminophenoxy)phenyl]born borneol (BAPN), 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amine Base-1 -(4'-aminophenyl)-1,3,3-trimethylindan, 4,4'-methylenebis(o-chloroaniline), 3,3'-dioxin Aniline, 3, 3' - 醯 醯Amine, 4, 4'-diaminobenzophenone, 1,5-diaminonaphthalene, bis(4-aminophenyl)diethylcarbazide, bis(4-aminophenyl)diphenyl Benmantan, bis(4-aminophenyl)ethylphosphine oxide, N-(bis(4-aminophenyl))-N-methylamine, N-(bis(4-aminophenyl) ))-N-phenylamine, 4,4'-methylenebis(2-methylaniline), 4,4'-methylenebis(2-methoxyaniline), 5, 5'- Methyl bis(2-aminophenol), 4,4'-methylenebis(2-methylaniline), 4,4'-oxybis(2-methoxyaniline), 4,4' - TP030120 16 1258056 oxybis(2-chloromoutamine), 2,2,-bis(4-aminophenol), 5,5,-oxybis(2-aminophenol), 4,4'-sulfur Bis(2-methylaniline), 4,4'-thiobis(2-methoxyaniline), 4,4'-thiobischloroaniline), 4,4'-diazonyl double (2 -Methylaniline), 4,4'-continuous-branched bis(2-ethoxyaniline), 4,4,~-decyl bis(2-chloroaniline), 5,5,-continuation thiol 2-aminophenol), 3,3,-dimethyl-4,4,-diaminobenzophenone, 3,3,-dimethoxy-4,4,-diaminodiphenylhydrazine嗣, 3, 3' - digas-4,4, _diamine Benzophenone, 4,4'-diaminobiphenyl, m-phenylenediamine, p-phenylenediamine, 4,4,-methylenediphenylamine, 4,4,-thiodiphenylamine, 4 , 4,-M-decyldiphenylamine, 4,4'-isopropylidenediphenylamine, 3,3,-dimethylbenzidine, 3,3,-dimethoxyoxybenzidine, 3, 3' - Dicarboxybenzidine, 2,4-tolyldiamine, 2,5-tolyldiamine, 2,6-tolyldiamine, m-xylylenediamine, 2,4-diamino-5- Chlorotoluene, 2,4-diamino-6-gas toluene, and the like. It is preferably 4,4,-oxydiphenylamine (0DA) or 4,4,-octafluorobenzidine (0FB). Examples of the alkoxylated oxime represented by the formula Si(R3)4 in the process of the present invention include, but are not limited to, for example, tetramethoxynonane, tetraethoxy oxacyclohexane, tetrapropoxy oxacyclohexane, tetrabutoxy oxane, and the like. . The reaction of steps (a), (b), (al), (bl), (cl) in the process of the invention is preferably carried out in a solvent. The solvent to be used is not particularly limited as long as it can be used to dissolve the monomer used in the present invention. Specific examples of the solvent include, but are not limited to, for example, dimethyl submilling (DMS0), N,N-dimethyletheneamine (DMAc), 1-methylpyrrolidone (NMP), N,N-dimethyl Mercaptoamine (DMF), tetrahydroanthracene (THF), dioxane, methyl ethyl ketone (MEK), chloroform (CHCh), di-methane, r-butyrolactone, butyl acetate, cyclopentane Ketone, propylene glycol monomethyl ether acetate (PGMEA), decyl alcohol (THFA), methyl amyl ketone (2-heptanone), diethylene glycol monohexyl ether (DGME), propylene glycol monodecyl group (pGjjg) , n-butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, diethylene glycol monobutyl bond TP030120 17 1258056 acetate and the like. Among them, 1-methylpyrrolidone (NMP) is preferably used. Examples of the amine coupling agent of the legs of the formula (b) and (bl) in the method of the present invention include, but are not limited to, for example, 3-aminopropyltrimethoxycarbazite (APrTMOS), 3 - Aminopropyltriethoxydecane (APrTEOS), 3-aminophenyltrimethoxyoxydecane (aptmos), 3-aminophenyltriethoxydecane (APTEOS), and the like. Examples of the coupling agent of the intermolecular force represented by the formula R3-Si(R4)3 in the step (4) of the method of the present invention include, but are not limited to, r-glycidoxypropyltrimethoxy sulphur (GTM〇s), I glycidoxypropyl triethoxy oxime (GTE0S) and the like. Examples of the tertiary amine monomer having a terminal group having an unsaturated group at the terminal represented by the formula (e), (el) in the step (e), (el) of the present invention include, but are not limited to, methacrylic acid 21-2. Methylaminoethyl ester, 2-diethylaminoethyl formate, 2-dipropylaminoethyl methacrylate, 3-monopropoxypropyl dimethylamine, 3-methyl propylene Oxypropyldiethylamine, 3-monopropoxypropyldipropylamine, 3-propylmethoxypropyldimethylamine, 3-propoxypropyldiethylamine, 3-propene Oxypropylpropylpropylamine, 3-methylmethacryloxypropyldimethylamine, 3-methylmethacryloxypropyldiethylamine, 3-methylmethyloxypropyl Dipropylamine, 4-(methylpropionylpropyl)phenyldimethylamine, 4-(methacryloxypropyl)phenyldiethylamine, 4-(methacrylic acid) Propyl)phenyldipropylamine, 4-(methylpropionylethyl)phenyldifylamine, 4-(methylpropoxyethyl)phenyldiethylamine, 4- (methacryloxyethyl)phenyldipropylamine, 4-(methacryloxymethyl)phenyldimethylamine, 4-(methacrylic) Oxymethyl)phenyldiethylamine, 4-(methacryloxymethyl)phenyldipropylamine, propyltrimethylamine, propyldiethylamine, propylpropyl Propylamine, 4-propylpropyldimethylamine, 4-allyldiethylamine, 4-propylpropylpropylamine, TP030120 18 1258056 dilute-methylamine, 4_ethylglycosyl Ethyl n-diethyldipropylamine. Mixing steps (7) and (6) of the method of the present invention, mixing of oxygen-cut lysine or imipenem • Any solution obtained at any ratio in any ratio will not have a sink or turbidity of the solution. Examples of molecules (photoinitiators) which can generate free radicals for photoinitiation reaction by the method of the present invention include, but are not limited to, for example, i, dimethyldimethyl phenyl benzophenone (e.g., (10)
Geigy公司銷售之1聊脱韻）、卜絲-環己基-苯基酮、以及雙(2, 4, 6一 -甲基苯甲醯基)苯基膦氧化物(如CIBAGeigy公司銷售之Ir职819)。 本發明方法中於基材上塗佈之方法可利用本技藝悉知之塗佈方法，包 含例如輥塗(rolling coating)、流塗(fl〇w coating)、含浸塗佈法(dip coating)、喷霧塗佈法(spray c〇ating)、旋轉塗佈法(spin c〇ating)、簾 塗法(curtain coating)等，其中以獲得均勻薄膜之觀點而言，較好使用旋 轉塗佈法。 本發明方法中使塗佈膜軟烤、曝後烤及固化之方法可使用加熱板或烘 箱進行烘烤步驟，固化宜採用多段式升溫烘烤法，藉多段式升溫烘烤可使 其中所含之溶劑緩慢蒸發，可避免薄膜龜裂。所採用之軟烤包含(但不限於) 例如在40-200°C烘烤1-60分鐘，所採用之曝後烤包含(但不限於)例如在 40-200°C之溫度烘烤1-120分鐘，所採用之多段硬烤固化包含(但不限於） 例如在40-200°C之溫度烘烤10-120分鐘，在200-400°C之溫度烘烤10-120 分鐘，在200-600°C之溫度烘烤10-300分鐘。 本發明方法中使用之曝光光源包含(但不限於)例如波長100-500 nm之 TP030120 19 1258056 紫外光或可見光源’光源可為連續波長之寬頻汞燈或經濾片之單一波長光 源，或包含(但不限於)例如聚焦之雷射及電子束。 本發明方法中使用之基板包含(但不限於)例如不具可撓性之石夕晶圓、 鍺晶圓、玻璃、石英、與具可撓性之聚乙稀(PE)、聚醋(pet)、聚醯亞胺(pi) 基板等。 本發明方法中所使用之顯影劑為包含(但不限於)例如二甲基亞碾 (DMS0)、N，N-二甲基乙醯胺(DMAc)、1-甲基吡咯烷酮(NMP)、N，N-二甲基甲 醯胺(DMF)、四氫呋喃(THF)、二噚烷、甲基乙基酮(MEK)、氯仿(CHC13)、二 氯甲烧、甲醇、乙醇、異丙醇、正丁醇、PEGDA、r-丁内酯、乙酸丁酯、 環戊酮、丙二醇單甲基醚乙酸酯（PGMEA)、四氫糠基醇(THFA)、甲基戊基 酮(2-庚酮）、二乙二醇單己基醚(DGME)、丙二醇單甲基醚(PGME)、乙酸正 丁基酯（nBA)、丙二醇單乙基醚、丙二醇單-正-丙基醚、二乙二醇單丁基醚 乙酸酯、以及水(IfcO)之二成份、三成份或四成份混合物。其中之一成份必 定為包含(但不限於)例如二甲基亞碉、N，N-二甲基乙醯胺(DMAc)、1-甲基 吡咯烷酮(NMP)、N，N-二甲基甲醯胺(DMF)等非質子性溶劑。 本發明方法中所使用之清洗溶劑為包含(但不限於)例如四氫咲喃 (THF)、二曙烷、甲基乙基酮(MEK)、氯仿(CHCls)、二氣甲烷、甲醇、乙醇、 異丙醇、正丁醇、PEGDA、丁内醋、乙酸丁醋、環戊_、丙二醇單甲基 醚乙酸酯(PGMEA)、四氫糠醇(THFA)、甲基戊基酮(2-庚嗣）、二乙二醇單己 基醚(DGME)、丙二醇單甲基醚(PGME)、乙酸正丁基酯(nBA)、丙二醇單乙基 醚、丙二醇單-正-丙基醚、二乙二醇單丁基醚乙酸酯等之單一溶劑或溶劑 TP030120 20 1258056 混合物。 本發明將以下列實施例進一步加以說明，惟該等實施例僅用以說明而 不限制本發明之範圍。 實施例1 取1· 602克(8晕莫耳)之4,4 -氧基一苯胺(0M)溶於二甲基乙酿胺 (DMAc)中，溶解後緩慢加入4·443克（10毫莫耳)之4,4〜六i亞異丙基二 駄酸二酐(6FDA)，通入氮氣並予以激烈攪拌，於室溫下反應24小時，得到 澄清黏滯之聚醯胺酸(ΡΜ)溶液。加入886毫克(4毫莫耳）的3-胺基丙基三 乙氧基石夕烷(APrTEOS)，於室溫下擾拌反應4小時，使其接上聚醯亞胺末端， 隨後加入1· 250克的四甲氧基石夕烷(TM0S)，攪拌30分鐘後加入3〇毫克的 去離子水使其於室溫下反應24小時後，再加入3· 144g之甲代丙稀酸2-二 甲胺基乙基醋(MDAE)，室溫下授拌反應4小時，最後加入1〇〇呢的雙(2,4, 6-三甲基苯曱醯基)苯基膦氧化物作為光起始劑，攪拌30分鐘使其溶解並分 散均勻後，可得到感光性聚醯亞胺/氧化矽有機無機混成薄膜材料之前驅溶 液，稱為溶液（A)。 將所得溶液（A)藉旋轉塗佈法以i500rpm轉速在4吋矽晶圓上塗佈30 秒，接著在加熱板上以120°C軟烤4分鐘，然後以空白光罩與波長365nm之 紫外光源進行曝光，曝光能量為18〇〇mj/cm2，曝光後在加熱板以120°C曝後 烤10分鐘，然後以加熱板進行多段式硬烤固化。固化溫度與時間分別為： 150°C烘烤30分鐘；200°C烘烤30分鐘；250°C烘烤30分鐘；300°C烘烤30 分鐘。可得到6FDA/0DA之感光聚醯亞胺/氧化石夕混成材料薄膜。 TP030120 21 1258056 比較例1 取1.602克(8毫莫耳)之4,4’ -氧基二苯胺(0DA)溶於二甲基乙醯胺 (DMAc)中，溶解後緩慢加入4· 443克（10毫莫耳)之4,4-六氟亞異丙基二 酞酸二酐(6FDA)，通入氮氣並予以激烈攪拌，於室溫下反應24小時，得到 澄清黏滯之聚醯胺酸(PM)溶液。加入886毫克(4毫莫耳）的3-胺基丙基三 乙氧基石夕烧(APrTEOS)，於室溫下授拌反應4小時，使其接上聚醯亞胺末端， 再加入3· 144g之2-甲基丙烯酸2-二甲胺基乙基酯(MDAE)，室溫下擾拌反 應4小時，最後加入100 mg的雙(2,4, 6-三甲基苯甲醯基苯基膦氧化物作 為光起始劑，授拌30分鐘使其溶解並分散均勻後，可得到感光性聚醢亞胺 之前驅溶液，稱為溶液（A1)。將所得溶液（A1)藉旋轉塗佈法以i500rpm 轉速在4对石夕晶圓上塗佈30秒，接著在加熱板上以12(TC軟烤4分鐘，然 後以空白光罩與波長365nm之紫外光源進行曝光，曝光能量為i8〇〇mj/cm2， 曝光後在加熱板以120 C曝後烤10分鐘，然後以加熱板進行多段式硬烤固 化。固化溫度與時間分別為：150°C烘烤30分鐘；200°C烘烤30分鐘；250 °C烘烤30分鐘；300°C烘烤30分鐘。可得到感光聚醯亞胺薄膜。 比較例2 重覆比較例1之程序，但比較例2中之雙酐改變為苯均四酸二酐 (PMDA)，可得到PMDA/0DA之感光性聚醯亞胺前驅溶液(稱為溶液(B1))及其 薄膜。 實施例2 以實施例1、比較例1及比較例2所得之溶液（A)、（Al)、（B1)經由 TP030120 22 1258056 旋轉塗佈並烘烤固化所製成之薄膜，測量其於波長633nm與波長1319簡之 折射率與波長1310nm及1550nm時之光傳損失，結果波長633nm之折射率 分別為1.5817、1.5659與1· 6990，波長1319nm之折射率分別為1 5578、 1.5454與1.6635。此乃由於氧化砍擁有較低之本性（intrinsic)折射率， 而PMDA/ODA擁有較6FDA/ODA高之本性（intrinsic)折射率所致。上述结果 表示本發明所製備之混成薄膜可藉由聚醯亞胺之選擇與氧化石夕含量之控 制，在一寬廣之範圍内調整其折射率。溶液（A)與（A1)所製備之平面光 波導，其測得之光傳損失在波長1310nm時分別為0· 97dB/cm與1. 04dB/cm， 在波長1550nm時分別為〇· 92dB/cm與L 〇3dB/cin，表示無機之氧化矽顆粒 分布均勻並未對㈣絲造細权舰損失，本發騎製備材料可調折 射率低光傳損失特性，表示其可作為光學波導材料之用。 實施例3 以實施例1及比較例i所得之溶液⑴及⑻於鐵氣龍盤上輯、 曝光、固化後製成厚度200微米的厚膜，進行TGA、脱、雇之熱性質測 试。TGA所得到之熱裂解溫度（Td)分別為斌⑴、肌⑻；玻璃 (Tg) 272〇c (A> 264〇c (A1}; 5?6 ppm/ c (a)、737_rc⑻。顯示本發明所製備感光性聚醯亞胺/氧化石夕有機 …、機混成材Ht單純感紐雜亞胺材料有更佳之熱穩紐與更低之 …、膨脹係數可作為光學波導、半導體或微電子製造巾所需之紐能材料。 實施例4 將實施例1所得溶液⑴藉旋轉塗佈法以·咖轉速在4偏圓 ΤΡ030120 23 1258056 上塗佈30秒，接著在加熱板上以120°C軟烤4分鐘，然後以具有圖型之光 罩與波長365nm之紫外光源進行曝光，曝光能量為18〇〇 mJ/cm2，曝光後在 加熱板以120°C曝後烤10分鐘。然後以DMSO/r-丁内酯/%0：=70/2〇/1〇為 重量比例所調製之混合溶液為顯影劑。將晶圓浸泡於該顯影液中3分鐘後 取出，以甲醇為沖洗液將顯影液沖洗去除，再以氮氣將甲醇吹乾後，最後 以加熱板進行多段式硬烤固化。固化溫度與時間分別為：15〇°c烘烤3〇分 鐘；200°C烘烤30分鐘；250°C烘烤30分鐘；30(TC烘烤30分鐘。可得到 6FDA/0DA感光聚醯亞胺/氧化石夕混成材料薄膜所形成之圖型。 以實施例1及比較例1所得之薄膜進行之性質分析，包括紅外光譜、 近紅外光譜、104、05(：、1似、}^結果可見於第2至6圖。以實施例4所 得之微影圖型SEM圖可見於第7圖。 由第2圖之紅外光譜顯示聚醯亞胺/氧化矽（A)已反應完成，且（A) 之圖譜可明顯未觀察到於1000-1200CDT1之Si-O-Si振動吸收。由第3圖之 近紅外線光譜顯示1310nm波長處主要之吸收損失自於附近的c-η鍵第二倍 頻吸收與震動轉動結合吸收，因此混成薄膜的光傳損失可藉由C-H鍵密度 較低而降低。第4圖至第6圖分別為實施例3所製得薄膜之TGA、DSC與ΤΜΑ 圖，顯示聚醯亞胺/氧化矽混成薄膜較單純聚醯亞胺的性質為佳。第7圖為 實施例4所製作直線圖型之SEM照片，線寬為1〇微米，顯示本材料具備良 好之微影圖型解析度。 綜上所述，本發明所使用的感光性聚醯亞胺/氧化矽有機無機混成材 料，具有優秀之微影圖型解析度與尺寸穩定性。其所製備之薄膜經固化後 TP030120 24 1258056 具有良好之耐熱性質、光學性質、低熱膨脹係數、低光傳損失等，可作為 耐高溫之高性能光學波導或微電子與半導體製造中之介電材料。 【圖式簡單說明】 第1圖係依據本發明方法製備感光性聚醯亞胺/氧化矽有機無機混成材 料之製程流程圖。 第2圖為本發明實例1及比較例1所製得之溶液（A)及（A1)於塗佈、 軟烤、曝光、固化後之薄膜之紅外線光譜圖。 第3圖為本發明實例1及比較例1所製得之溶液（A)及（A1)於塗佈、 軟烤、曝光、固化後之薄膜之近紅外線光譜圖。 第4圖為本發明實例4中由實例1及比較例1之溶液（A)及（A1)於 塗佈、軟烤、曝光、固化後所得薄膜之TGA圖。 第5圖為本發明實例4中由實例1及比較例1之溶液（A)及（A1)於 塗佈、軟烤、曝光、固化後所得薄膜之DSC圖。 第6圖為本發明實例4中由實例1及比較例1之溶液（a)及（μ)於 塗佈、軟烤、曝光、固化後之薄膜之TMA圖。 第7圖為本發明實例4中由實例1之溶液（a)於塗佈、軟烤、曝光、 顯影、固化後所得圖型之SEM圖。 TP030120 25Geigy sells 1 chat, rhyme, cyclohexyl-phenyl ketone, and bis(2,4,6-methylbenzylidene) phenylphosphine oxide (such as Ir, which is sold by CIBA Geigy) 819). The method of coating on a substrate in the method of the present invention may utilize coating methods known in the art, including, for example, rolling coating, flow coating, dip coating, and spraying. A spin coating method is preferred from the viewpoints of spray coating, spin coating, curtain coating, and the like, in which a uniform film is obtained. In the method of the invention, the method of soft baking, exposing, baking and solidifying the coating film can be carried out by using a heating plate or an oven for baking, and the curing should adopt a multi-stage heating baking method, and the multi-stage heating baking can be included therein. The solvent evaporates slowly to avoid film cracking. The soft roasting used includes, but is not limited to, for example, baking at 40-200 ° C for 1-60 minutes, and the post-exposure roasting comprises (but is not limited to) baking, for example, at a temperature of 40-200 ° C. For 120 minutes, the multi-stage hard bake curing used includes, but is not limited to, for example, baking at a temperature of 40-200 ° C for 10-120 minutes, baking at a temperature of 200-400 ° C for 10-120 minutes, at 200- Bake at a temperature of 600 ° C for 10-300 minutes. The exposure light source used in the method of the present invention includes, but is not limited to, TP030120 19 1258056, for example, having a wavelength of 100-500 nm. The ultraviolet or visible light source can be a continuous wavelength broadband mercury lamp or a single wavelength source through the filter, or (but not limited to), for example, focused lasers and electron beams. The substrate used in the method of the present invention includes, but is not limited to, for example, a non-flexible stone wafer, a germanium wafer, a glass, a quartz, a flexible polyethylene (PE), and a polyester (pet). , polyimine (pi) substrate, and the like. The developer used in the method of the present invention comprises, but is not limited to, for example, dimethyl submilling (DMS0), N,N-dimethylacetamide (DMAc), 1-methylpyrrolidone (NMP), N. , N-dimethylformamide (DMF), tetrahydrofuran (THF), dioxane, methyl ethyl ketone (MEK), chloroform (CHC13), methylene chloride, methanol, ethanol, isopropanol, positive Butanol, PEGDA, r-butyrolactone, butyl acetate, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofurfuryl alcohol (THFA), methyl amyl ketone (2-heptanone) ), diethylene glycol monohexyl ether (DGME), propylene glycol monomethyl ether (PGME), n-butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, diethylene glycol A mono-, tri- or tetra-component mixture of monobutyl ether acetate and water (IfcO). One of the ingredients must include, but is not limited to, for example, dimethyl hydrazine, N,N-dimethylacetamide (DMAc), 1-methylpyrrolidone (NMP), N,N-dimethyl An aprotic solvent such as guanamine (DMF). The cleaning solvent used in the method of the present invention includes, but is not limited to, for example, tetrahydrofuran (THF), dioxane, methyl ethyl ketone (MEK), chloroform (CHCls), di-methane, methanol, ethanol. , isopropanol, n-butanol, PEGDA, butane vinegar, butyl acetate, cyclopentane _, propylene glycol monomethyl ether acetate (PGMEA), tetrahydrofurfuryl alcohol (THFA), methyl amyl ketone (2- Glycerol), diethylene glycol monohexyl ether (DGME), propylene glycol monomethyl ether (PGME), n-butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, diethyl A single solvent such as diol monobutyl ether acetate or a mixture of solvents TP030120 20 1258056. The invention is further illustrated by the following examples, which are intended to illustrate and not to limit the scope of the invention. Example 1 1 602 g (8 halo) of 4,4-methoxy-aniline (0 M) was dissolved in dimethyl ethanoamine (DMAc), and 4,443 g (10 m) was slowly added after dissolution. 4,4~6i isopropylidenediphthalic acid dianhydride (6FDA), reacted with nitrogen gas and vigorously stirred at room temperature for 24 hours to obtain a clear viscous poly-proline (ΡΜ ) solution. Add 886 mg (4 mmol) of 3-aminopropyltriethoxy oxalate (APrTEOS), and then scramble the reaction for 4 hours at room temperature, then attach it to the polyimine end, then add 1· 250 g of tetramethoxy oxalate (TM0S), stirred for 30 minutes, then added 3 mM of deionized water to react at room temperature for 24 hours, then add 3. 144 g of methacrylic acid 2-two Methylaminoethyl vinegar (MDAE), mixed reaction at room temperature for 4 hours, and finally added 1 bis (2,4,6-trimethylphenyl fluorenyl) phenylphosphine oxide as light After the initiator is stirred for 30 minutes to be dissolved and dispersed uniformly, a photosensitive polyimine/cerium oxide organic-inorganic hybrid film material precursor solution is obtained, which is called a solution (A). The resulting solution (A) was coated on a 4 吋矽 wafer by spin coating at a speed of i500 rpm for 30 seconds, followed by soft baking at 120 ° C for 4 minutes on a hot plate, followed by a blank mask and a wavelength of 365 nm. The light source was exposed to light, and the exposure energy was 18 〇〇mj/cm 2 . After exposure, it was baked at 120 ° C for 10 minutes on the heating plate, and then subjected to multi-stage hard baking curing with a heating plate. The curing temperature and time were respectively: baking at 150 ° C for 30 minutes; baking at 200 ° C for 30 minutes; baking at 250 ° C for 30 minutes; baking at 300 ° C for 30 minutes. A 6FDA/0DA photosensitive polyimide/oxide oxide blending material film is available. TP030120 21 1258056 Comparative Example 1 1.602 g (8 mmol) of 4,4'-oxydiphenylamine (0DA) was dissolved in dimethylacetamide (DMAc), and 4,443 g was slowly added after dissolution ( 4 mM hexafluoroisopropylidene dicarboxylic acid dianhydride (6FDA), passed through nitrogen and vigorously stirred, and reacted at room temperature for 24 hours to obtain a clear viscous poly-proline (PM) solution. Add 886 mg (4 mmol) of 3-aminopropyltriethoxy sulphur (APrTEOS), stir the reaction for 4 hours at room temperature, attach it to the end of the polyimine, and add 3· 144 g of 2-dimethylaminoethyl methacrylate (MDAE), scrambled for 4 hours at room temperature, and finally added 100 mg of bis(2,4,6-trimethylbenzhydrylbenzene) After the base phosphine oxide is used as a photoinitiator, it is mixed for 30 minutes to be dissolved and dispersed uniformly, and a photosensitive polyimine precursor solution is obtained, which is called a solution (A1). The obtained solution (A1) is spin-coated. The cloth was coated on 4 pairs of Shixi wafers at i500rpm for 30 seconds, then soft-baked on a hot plate for 12 minutes (TC) for 4 minutes, then exposed with a blank mask and an ultraviolet light source with a wavelength of 365 nm. The exposure energy was i8. 〇〇mj/cm2, after exposure, it is baked at 120 C for 10 minutes on the heating plate, and then subjected to multi-stage hard baking curing with a heating plate. The curing temperature and time are respectively: baking at 150 ° C for 30 minutes; drying at 200 ° C Bake for 30 minutes; bake at 250 ° C for 30 minutes; bake at 300 ° C for 30 minutes to obtain a photosensitive polyimide film. Comparative Example 2 Repeat the procedure of Comparative Example 1, but The dianhydride in Comparative Example 2 was changed to pyromellitic dianhydride (PMDA) to obtain a photosensitive polyamidiamine precursor solution (referred to as solution (B1)) of PMDA/0DA and a film thereof. The films (A), (Al), and (B1) obtained in Example 1, Comparative Example 1 and Comparative Example 2 were spin-coated and cured by TP030120 22 1258056, and were measured at a wavelength of 633 nm and a wavelength of 1319. The refractive index and the optical transmission loss at the wavelengths of 1310 nm and 1550 nm result in refractive indices of 1.51817, 1.5659 and 1.9990, respectively, and refractive indices of 1319 nm at wavelengths of 1 5578, 1.5454 and 1.6635, respectively. The lower intrinsic refractive index, while PMDA/ODA has higher intrinsic refractive index than 6FDA/ODA. The above results indicate that the mixed film prepared by the present invention can be selected by polyimine. The control of the content of the oxidized oxide is adjusted within a wide range. The planar optical waveguide prepared by the solutions (A) and (A1) has a measured optical transmission loss of 0.97 dB at a wavelength of 1310 nm. Cm and 1. 04dB/cm, respectively at the wavelength of 1550nm 〇· 92d B/cm and L 〇3dB/cin, indicating that the inorganic cerium oxide particles are evenly distributed and are not lost to the (four) silk-making fine-weight ship. The hair-reducing material has a variable refractive index and low light transmission loss characteristic, indicating that it can be used as an optical waveguide. Example 3 The solutions (1) and (8) obtained in Example 1 and Comparative Example i were prepared, exposed and cured on an iron gas plate to form a thick film having a thickness of 200 μm, and subjected to TGA, heat and heat. Nature test. The thermal cracking temperatures (Td) obtained by TGA are bin (1), muscle (8), and glass (Tg) 272 〇c (A > 264 〇 c (A1}; 5-6 ppm / c (a), 737_rc (8). The prepared photosensitive polyimine / oxidized stone organic ..., machine mixed material Ht simple neo-imine material has better thermal stability and lower ..., expansion coefficient can be used as optical waveguide, semiconductor or microelectronics manufacturing The required energetic material of the towel. Example 4 The solution (1) obtained in Example 1 was applied by spin coating at a speed of 4 ounces on 030120 23 1258056 for 30 seconds, followed by softness at 120 ° C on a hot plate. Bake for 4 minutes, then expose with a patterned mask and an ultraviolet light source with a wavelength of 365 nm, the exposure energy is 18 〇〇mJ/cm2, and after exposure, expose it to 120 ° C for 10 minutes, then DMSO/ R-butyrolactone /%0:=70/2〇/1〇 The mixed solution prepared by the weight ratio is a developer. The wafer is immersed in the developer for 3 minutes, and then taken out, and developed with methanol as a rinse solution. The liquid is removed by rinsing, and then the methanol is blown dry with nitrogen, and finally the multi-stage hard baking curing is performed by a hot plate. The two are: 15 ° ° c baking for 3 minutes; 200 ° C for 30 minutes; 250 ° C for 30 minutes; 30 (TC baking for 30 minutes. Can get 6FDA / 0DA photosensitive polyimide / oxidation The pattern formed by the film of the Shixia mixed material. The properties of the film obtained in Example 1 and Comparative Example 1, including infrared spectrum, near-infrared spectrum, 104, 05 (:, 1, like, }^ results can be seen in the first 2 to 6. The SEM image of the lithogram obtained in Example 4 can be seen in Fig. 7. The infrared spectrum of Fig. 2 shows that the polyimine/iridium oxide (A) has been reacted, and (A) The Si-O-Si vibration absorption of 1000-1200 CDT1 is obviously not observed in the spectrum. The near-infrared spectrum of Figure 3 shows that the main absorption loss at the wavelength of 1310 nm is from the second c-band absorption and vibration of the nearby c-η bond. Rotational combined absorption, so the light transmission loss of the mixed film can be reduced by the lower density of the CH bond. Figures 4 to 6 are the TGA, DSC and ΤΜΑ diagrams of the film prepared in Example 3, respectively, showing the poly The amine/yttria mixed film is better than the pure polyimine. Fig. 7 is the SE of the straight line pattern produced in Example 4. M photo, the line width is 1 〇 micron, indicating that the material has a good lithographic pattern resolution. In summary, the photosensitive polyimide/cerium oxide organic-inorganic hybrid material used in the present invention has excellent properties. The lithography pattern resolution and dimensional stability. After the prepared film is cured, TP030120 24 1258056 has good heat resistance, optical properties, low thermal expansion coefficient, low light transmission loss, etc., and can be used as a high temperature resistant high performance optical waveguide. Or dielectric materials in microelectronics and semiconductor manufacturing. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a process flow diagram for preparing a photosensitive polyimine/cerium oxide organic-inorganic hybrid material according to the method of the present invention. Fig. 2 is an infrared spectrum diagram of a film obtained by coating, soft-baked, exposed, and cured solutions (A) and (A1) obtained in Example 1 and Comparative Example 1 of the present invention. Fig. 3 is a near-infrared spectrum chart of the films (A) and (A1) prepared in Example 1 and Comparative Example 1 of the present invention after coating, soft baking, exposure, and curing. Fig. 4 is a TGA chart of the film obtained by coating, soft baking, exposing and curing the solutions (A) and (A1) of Example 1 and Comparative Example 1 in Example 4 of the present invention. Fig. 5 is a DSC chart of the film obtained by coating, soft baking, exposing and curing the solutions (A) and (A1) of Example 1 and Comparative Example 1 in Example 4 of the present invention. Fig. 6 is a TMA diagram of the film of Example 4 and Comparative Example 1 in Example 4 of the present invention, after coating, soft baking, exposure, and curing. Fig. 7 is a SEM image of the pattern obtained by the solution (a) of Example 1 after coating, soft baking, exposure, development, and curing in Example 4 of the present invention. TP030120 25