200400238 (1) 玫、發明說明 【發明所屬之技術領域】 本發明係關於多孔性奈米複合薄膜及其形成方法。 【先前技術】 隨著電子元件及多層配線板等逐漸精細化及高集積化 ’爲適用於此’所以要求較低的電容率之絕緣膜。在此， 將既有的材料多孔性化，將電容率爲1之空氣相導入膜中 之手法廣受檢討。使用氧化矽作爲骨架材料者，已知有特 開2001— 2992號公報及特開2001— 98224號公報等。使 用耐熱性有機聚合物爲骨架材料者，已知有美國特許第 6 1 72 1 28號說明書等。依據這些技術，可將孔徑爲20nm 以下大小的空孔導入膜中，可得到電容率爲2 · 1至2.5之 膜。 然而’上述之既存技術上有2個大問題。其一，因爲 導入空孔導致膜的機械強度極端地降低，例如使表面平滑 步驟之化學機械硏磨 （CMP ·· ChemicalMechanical Polishing)時，發生剝離之問題。因此，實際上不增大空 孔率於某程度以上而得到電容率爲2以下的膜係不可能的 。另一個問題係關於空孔的形狀。S爲空孔彼此間相聯結 ，也就是存在非常多的連續孔，所以於蝕刻後，除去光阻 之步驟時，電漿中之活性粒子及洗淨藥液等容易侵入膜內 ，造成膜變質或污染等問題。這2個問題爲製造電子元件 及多層配線板時之致命缺陷，非常期待將其改善。 -4- (2) (2)200400238 爲改善多孔性膜之機械強度，於形成多孔質膜後，於 其上再形成緻密膜以補強多孔性構造之手法，記載於美國 特許6 1 7 1 687號說明書。然而，該手法有改善機械強度之 效果，但是相對的亦造成塗膜之空孔率降低，電容率升高 ，無法解決問題的本質。 【發明內容】 發明之揭示 本發明的目的係解決上述之問題點，更詳細而言，係 提供電容率低而且機械特性、耐電漿性及耐藥品性優異的 塗膜。 本發明係提供含有氧化矽（A )及耐熱性有機聚合物 (B )，而且平均孔徑爲1 〇nm以下之多孔性爲特徵之多 孔性奈米複合薄膜。 另外，本發明係提供由含有氧化矽（A )之前驅物、 耐熱性有機聚合物（B )、薄膜形成後可除去之成份（C )及溶劑之組成物形成薄膜後，將上述成份（C )除去爲 特徵之多孔性奈米複合薄膜之形成方法。 用以實施發明之最佳型態 、 本發明中之所謂含有氧化矽（A )及耐熱性有機聚合 物（B )之多孔性奈米複合薄膜，爲平均孔徑爲1 〇nm以 下之多孔性薄膜。平均孔徑係以5 nm以下爲宜，以3 nm 以下尤佳。另外，本發明中之所謂平均孔徑係依據小角度 -5 - (3) (3)200400238 X 光散射（Small Angle X-ray Scattering)所求出之平均 孔徑。氧化矽（A )及耐熱性有機聚合物（B )之各自的 領域尺寸（domain size )係以數l〇nm以下爲佳。 因爲電子元件之配線間隔年年變窄，未來將成爲數 1 Onm ’所以各構成成份之領域尺寸如上所述之大小爲宜 。另外’平均孔徑若超過lOnm時，製造元件時之電漿中 之活性粒子或洗淨藥液容易侵入空孔中而造成膜的損壞。 本發明中之所謂多孔性係以空孔率爲5至7 0 %之 多孔性爲宜，進而以1 0至6 0 %尤佳。 本發明中之氧化矽（A)實際上爲下述式（1)所表 示者，係由後述之氧化矽（A )前驅物（以下，稱爲氧化 矽前驅物）所形成者尤佳。 (X]X2SiO) a ( X3Si03/2) b ( Si02) c 式（1 ) 在此，X1、X2及X3係表示氫原子、氟原子、碳原子 數爲1至8個之烷基、芳基或乙烯基，彼此可爲相同或相 異。a、b及c分SU單獨爲0以上，1以下之數。但是，a + b + c 二 1 〇 X1、X2及X3爲氫原子、甲基或苯基時之耐熱性、機 械特性良好，所以適宜，以氫原子、甲基或苯基最佳。a 若大時，所得之氧化矽之電容率雖然^變小，但爲保持充份 的耐熱性及機械特性’以〇 · 5以下爲宜，進而以〇 · 3以下 尤佳。c係爲使耐熱性及機械特性良好，以〇 · 2以上爲宜 ，爲保持低的電容率，以〇 · 9以下爲宜。進而，c係以〇. 3 以上，0.9以下爲宜。 -6 - (4) (4)200400238 本發明中之所謂耐熱性有機聚合物（B )係指熱分解 溫度爲400°C以上之聚合物。該熱分解溫度係以425艺以 上爲宜，進而以45 0 °C以上尤佳，並且，通常以55(rc以 下爲宜。在此，所謂熱分解溫度係指依據於不活性氣體環 境下’ 1 0 °C /分之升溫條件下之熱重量分析（T G A )測定 ，減少3 %重量之溫度。本發明中之耐熱性有機聚合物（ B )之電容率係以4以下爲宜，以3以下尤佳。尤其以熱 分解溫度爲450 °C以上，且電容率爲3以下最好。相關的 耐熱性有機聚合物（B )，可舉例如特開平9 — 2 02 82 3號 公報及特開平1 0 — 247646號公報所記載之polyarylene ether (聚芳烯基醚）、w〇 02/083 08號公報所記載之支鏈 型熱硬化聚合物、特開 2000 — 191752號公報所記載之 polyphenylene等之含有芳環之聚合物及含有氟原子之聚 合物爲適合例。另外，因爲可使電容率板降低，所以重覆 單位中以不含極性基爲宜。 作爲上述之含有芳環之聚合物係以具有含芳環之重覆 單位之聚合物爲宜。 上述含有氟原子之聚合物之含氟量，爲增大電容率之 減低效果，以1 0質量％以上爲宜，進而以3 0質量％尤佳 。另外’爲保持對溶劑充份的溶解性^，含氟量係以70質 量％以下爲宜。尤其係以30至60質量％爲宜。 作爲本發明中之耐熱性有機聚合物（B )係以具有氟 原子而且具有含芳環之重覆單位之聚合物最好。 另外，本發明中之耐熱性有機聚合物（B )，由耐熱 (5) 200400238 性及耐溶劑性之觀點而言，以具有交聯性官能基 作爲交聯性官能基，係以熱、光及電子束等自交 基爲宜。以加熱自交聯之官能基，因爲對於電子 層配線板等之電子零件製造步驟之適用性優異， 。另外，不含極性基之交聯性官能基因爲可使聚 容率降低所以適宜。相關之交聯性官能基作爲 前驅物形成共價鍵之官能基，亦可使用。 交聯性官能基之具體例，可舉例如乙文 oxocyclopenta-2，5-dien-3-yl 基（以下，稱爲環 基，cyclopentadienone )、氰基、烷氧基甲石: alkoxysilyl groups)、二芳基羥基甲基及羥基芴 耐熱性等之觀點而言，以乙炔基爲宜。 上述之交聯性官能基之含量係相對於1莫耳 有機聚合物（B)之重覆單位，以〇.〇5至6莫 〇·〇5莫耳以上時，可保持充份的耐熱性及耐藥品 耳以下時，可保持低的電容率，並且可以保持強 述含量係以0 · 1至4莫耳之比率尤佳。 本發明中之耐熱性有機聚合物（Β )之適合 ’可舉例如含有二烯基（diene )之化合物及含 和物基（d i e η 〇 p h i 1 e )之化合物間、之迪耳阿德 Alder)型之聚合反應所合成之p〇iyphenylene， 含氟芳環化合物與含有2個以上苯酚性羥基之化 親核取代型之脫HF縮聚反應所合成之含氟聚芳 fluorinated polyarylene ether) 〇 者爲宜。 聯之官能 元件及多 更加適宜 合物之電 與氧化矽 夹基、卜 戊二烯酮 夕烷基（ 基等。由 之耐熱性 耳爲宜。 性，6莫 韌性。上 的具體例 有二烯新 (Diels· 以及含有 合物間之 烯基醚（ (6) (6)200400238 上述之polyphenylene係以具有2個以上之二烯基之 化合物與具有3個以上之二烯新和物基之化合物間之迪耳 阿德（Diels-Alder)型之聚合反應生成物爲宜。作爲二烯 基係以環戊二烯酮基爲宜’作爲具有2個以上二烯基之雙 環戊二烯酮衍生物，可舉例如1，4 一雙（1 —氧—2，4， 5 —三苯基一環戊一 2，5 —二烯—3 —基）苯、4，4，—雙 (1 一氧—2，4，5 —三苯基—環戊—2，5 —二嫌—3 -基 )聯苯、4，4，—雙（1—氧一 2，4，5 —三苯基—環戊— 2，5-二烯—3—基）1，1’ 一羥基聯苯、4，4’ 一雙（1 一氧一 2，4，5 —二苯基一環戊—2，5 — 一綠—3 -基）1 ，1’ —硫代聯苯、1，4一雙（1—氧—2 ’5 —雙一 〔4 — 氟苯〕一 4 —苯基—環戊—2，5 —二烯一 3 —基）苯、4，4 ’ 一雙（1 —氧—2，4’ 5 —二苯基—環戊—2，5 —二嫌— 3 —基）1，1’一 （1，2—乙烷二基）聯苯及4，4’ 一 雙（1—氧—2，4，5 —三苯基—環戊—2，5 —二烯一 3 — 基）1，1’ — （1，3 -丙烷二基）聯苯等。這些雙環戊 二烯酮衍生物中，就耐熱性之觀點而言，以全芳香族骨架 之雙環戊二烯酮衍生物爲宜。這些可單獨使用，亦可倂用 2種以上。 作爲上述之二烯新和物基係以乙、炔基爲宜，具有3個 以上之二烯新和物基之化合物，可舉例如1，3，5 —三乙 炔基苯、1，2，4一三乙炔基苯、1，3，5 —三（苯基乙炔 基）苯、1，2, 4 —三（苯基乙炔基）苯及1，2，3，5-四（苯基乙炔基）苯等。這些可單獨使用，亦可倂用2種 -9- (7) 200400238 以上。 具有2個以上之二烯基之化合物與具有3個以上 烯新和物基之化合物間之迪耳阿德（Diels-Alder)型 合反應係以於溶媒中加熱進行爲宜。作爲溶媒係只要 反應爲不活性即可，並無特別的限制，例如均二甲苯 —丁內酯等。反應條件係以1 5 0至2 5 0 °C，1至6 0小 宜。二烯基：二烯新和物基之莫耳比爲1 ·· 1至1 : 3 適合的是以1: 1至1: 2之範圍進行該聚合反應時， 到耐熱性優異之polyphenylene爲宜。就防止該聚合 中之凝膠化之觀點而言，全部的二烯基及二烯新和物 ，以10至30%左右未反應爲宜。反應率係以反應溫 時間控制爲宜。聚合物中殘存之二烯基及二烯新和物 作爲製膜後之加熱而反應之交聯性官能基運作的同時 可作爲與氧化矽前驅物及/或成份（C)之反應部位使 上述之含氟聚芳烯基醚係於芳環上直接鍵結氟之 含氟芳環化合物與含有2個以上苯酚性羥基之化合物 脫HF縮聚反應所合成。 作爲上述之含有含氟芳環化合物係以具有全氟芳 爲宜，可舉例如全氟聯苯、全氟萘、全氟聯三苯、全 1，3，5-三苯基苯）及全氟（1，2、，5-三苯基苯） 這些可單獨使用，亦可倂用2種以上。這些含有含氟 化合物中，具有支鏈構造之全氟（1，3，5-三苯基 及全氟（1，2，5-三苯基苯），因爲所得之含氟聚 基醚之耐熱性良好，所以適宜。 之二 之聚 對本 及r 時爲 ，更 可得 反應 基中 度及 基係 ，亦 用。 含有 間之 環者 氟（ 等。 芳環 苯） 芳烯 -10- (8) (8)200400238 作爲上述之含有2個以上苯酚性羥基之化合物係以多 官能苯酚類爲宜。其具體例，可舉例如二羥基苯、二键基 聯苯、二羥基聯三苯、二羥基萘、二羥基蒽、二羥基菲、 二羥基一 9，9一二苯基芴、二羥基二苯并呋喃、二羥基二 本基醚、一經基一苯基硫醚、二經基苯酿苯、二經基〜2 ，2—二苯基丙烷、二羥基一 2，2 —二苯基六氟丙烷、二 經基聯一萘、四苯基氨輕、六苯基二經基聯苯、三經基苯 、三羥基聯苯、三羥基萘、四羥基苯、四羥基聯苯、四羥 基聯一萘及四經基spiroindan類等。 其中’爲使所得到之聚合物之電容率値低，耐熱性良 好，係以二羥基苯、二羥基—9，9 —二苯基芴、二羥基〜 2’ 2—二苯基六氟丙院、四苯基氫輥及三羥基苯爲宜。 上述之含氟聚芳烯基醚係以含有作爲交聯性官能基之 乙炔基爲宜。乙炔基因熱而自交聯，而且可完成與氧化矽 前驅物生成共價鍵。作爲導入乙炔基之方法係於上述之縮 聚反應合時，使具有乙炔基之單體共聚之方法爲宜。作爲 具有乙炔基之單體，可舉例如五氟苯基乙炔及九氟聯苯基 乙炔等之含氟芳基乙炔類、苯基乙炔基五氟苯、苯基乙炔 基九氟聯苯及十氟二苯基乙炔等之含氟二芳基乙炔類、苯 基乙烯基苯酚及二羥基二苯基乙炔雙之含羥基乙炔類。這 些可單獨使用，亦可倂用2種以上。 作爲上述之縮聚反應之脫HF劑係以鹼性化合物爲宜 ，尤其以鹼金屬之碳酸鹽、碳酸氫鹽或氫氧化物爲宜。可 舉具體例，如碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、氫 -11 - (9) 200400238 氧化鈉及氫氧化鉀等。 脫HF劑之使用量係以相對於苯酚性羥基之莫耳 1倍以上爲宜，以1 · 1至3倍尤佳。上述之縮聚反應 極性溶媒中進行爲宜。作爲極性溶媒’係以含有N ’ 二甲基乙醯胺、Ν’ N—二甲基甲醯胺、N —甲基吡咯 、二甲基亞硕及環丁碩等之非質子性之極性溶媒之溶 宜。極性溶媒中，只要不降低所生成之聚合物之溶解 於不造成縮聚反應不良影響之範圍內’含有甲苯、二 、苯、三氟甲基苯及六氟二甲苯等亦可。 作爲聚合反應條件係於10至20(TC下，1至80 爲宜。以40至180 °C下，2至60小時尤佳。以60至 °C下，3至2 4小時最好。 本發明中之耐熱性有機聚合物（B)之數目平均 量係以5 00至5 00，000爲宜。於此範圍時，氧化矽 物與成份（C )之相溶性良好，所得之多孔性奈米複 膜中之各成份之領域尺寸及平均孔徑小者，而且可得 有良好耐熱性、機械特性及耐藥品性等之膜。上述分 係以1，000至100,000尤佳，以1，500至50,000最好 本發明中之所謂氧化矽前驅物係以酸或鹼等之催 、氧等之氧化劑或熱而形成上述式（1)所表示之氧 (A )者，係以將1種或2種以上選自下述式（2 ) )及（4 )所表示烷氧基矽烷之成群，部份水解聚合 宜。 Χϋί ( OR1 ) 2 式（2 ) -12- 比之 係於 N - 烷酮 媒爲 性， 甲苯 小時 160 分子 前驅 合薄 到具 子量 〇 化劑 化矽 '(3 者爲 200400238 do) X3Si ( OR2 ) 3 式（3 ) si ( 〇R3) 4 式（4 ) 在此，X1、X2及X3係與上述式（1 )相同。Rl、R2 及R3係表示氫原子或碳原子數爲丨至8之烷基。 式（2 )所表示之烷氧基矽烷之具體例，可舉例如二 甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二乙基二甲氧 基矽烷、二乙基二乙氧基矽烷、二甲氧基矽烷、二乙氧基 矽烷、二氟二甲氧基矽烷及二氟二乙氧基矽烷等。這些可 單獨使用，亦可混合2種以上使用。以二甲基二甲氧基矽 烷及二甲基二乙氧基矽烷爲宜。 式（3 )所表示之烷氧基矽烷之具體例，可舉例如甲 基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三異丙氧基矽 烷、辛基三甲氧基矽烷、辛基三乙氧基矽烷、乙烯基三甲 氧基矽烷、乙烯基三乙氧基矽烷、苯基三甲氧基矽烷、苯 基三乙氧基矽烷、三甲氧基矽烷、三乙氧基矽烷、三異丙 氧基矽烷、氟代三甲氧基矽烷及氟代三乙氧基矽烷等。這 些可單獨使用，亦可混合2種以上使用。以甲基三甲氧基 矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙 氧基矽烷、三甲氧基矽烷及三乙氧基矽烷爲宜。 式（4 )所表示之烷氧基矽烷之^具體例，可舉例如四 甲氧基矽烷、四乙氧基矽烷、四異丙氧基矽烷及四丁氧基 矽烷等。這些可單獨使用，亦可混合2種以上使用。以四 甲氧基矽烷及四乙氧基矽烷爲宜。 式（2 )所表示之烷氧基矽烷、式（3 )所表示之烷氧 -13- (11)200400238 基矽烷 (1 ) 4 式 水解聚 耳之烷 以添加 至5.0 ，可良 作 合物及 酸、丁 、馬來 丁酸、 脂酸、 、對甲 、三氟 檬酸及 酸、氟 作 吡咯烷 胺、二 醇胺、 一烯及 氨、氫 及式（4)所表示之烷氧基矽烷之比率決定上述式 3之a、b及c。 (2 } 、 （3)及（4)所表示之烷氧基矽烷之部份 合反應係以添加催化劑及水所進行者爲宜。每1莫 氧基甲矽烷基，以添加0.3至5.0莫耳的水爲宜， 〇·5至2.0莫耳的水尤佳。只要所添加水量於〇.3 莫耳之範圍內’即可保持所得薄膜之均勻性，另外 好地保持該薄膜形成用之組成物之保存安定性。 爲催化劑’可舉例如有機酸、無機酸、有機鹼性化 無機驗性化合物等。作爲有機酸可舉例如乙酸、丙 酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、草酸 酸、甲基丙二酸、己二酸、癸二酸、沒食子酸、正 苯六甲酸、花生浸烯酸、2 —乙基己酸、油酸、硬 亞油酸、亞油精、水楊酸、苯甲酸、對胺基苯甲酸 苯磺酸、苯磺酸、單氯乙酸、二氯乙酸、三氯乙酸 乙酸、甲酸、丙二酸、磺酸、苯二酸、富馬酸、檸 酒石酸等。作爲無機酸，可舉例如鹽酸、硝酸、硫 酸及磷酸等。 爲有機鹼性化合物，可舉例如吡啶、吡咯、哌嗪、 、哌啶、甲基吡啶、三甲基胺、、三乙基胺、單乙醇 乙醇胺、二甲基單乙醇胺、單甲基二乙醇胺、三乙 二氮雜雙環辛烷、二氮雜雙環壬烷、二氮雜雙環十 氫氧化四甲銨等。作爲無機鹼性化合物，可舉例如 氧化鈉、氫氧化鉀、氫氧化鋇及氫氧化鈣等。催化 -14- (12) (12)200400238 劑之使用量係相對於式（2 ) 、 （ 3 )及（4 )所表示之化 合物總量之莫耳比爲0.000 1至1，以0.001至〇·1爲宜。 本發明中之氧化砍前驅物之數目平均分子量係以3〇〇 至1 0 0，0 0 0爲宜。於該範圍時，該氧化砂前驅物與耐熱性 有機聚合物（Β )之相溶性以及該氧化砂前驅物與成份（ C )之相溶性良好，所得之多孔性奈米複合薄膜中之氧化 砂（A )與耐熱性有機聚合物（Β )之範圍尺寸小者，而 且可得到平均孔徑爲1 0 // m以下，具有良好耐熱性、機 械特性及耐藥品性等之薄膜。上述分子量係以 5 00至 50,000爲宜，以600至20,000尤佳。 本發明中之成份（C)係只要薄膜形成後可除去者即 可，並無特別的限制，可舉下述例。（1 )因熱而揮發之 物質或因熱所分解之該分解物爲揮發物質、（2 )因紫外 線或電子束等之電磁波等之照射所分解之該分解物爲揮發 物質及（3 )因藥液而溶出之物質或因藥液所分解之該分 解物爲溶出物質等。其中，因爲與電子元件及多層配線板 等之電子零件之製造步驟之適合性高，以（1 )或（2 )之 物質爲宜。以（1 )之物質尤佳。具體上可舉例如常壓下 之沸點爲200至400 °C之化合物及熱分解性聚合物等。 常壓下之沸點爲200至40(TC之化合物之具體例，可 舉例如戊基苯、環己基苯、二甲基萘、十四烷、萘烷、萘 滿、癸醇、十一醇、十二烷醇、戊二醇、甘油、草酸二丁 酯、酒石酸二丁酯及鄰苯二酸二甲酯等。 上述之熱分解性聚合物係熱分解溫度約爲4 0 0 °C以下 -15- (13) 200400238 之聚合物，以熱分解溫度約爲3 5 (TC以下之聚合物 在此之熱分解溫度係與上述之耐熱性有機聚合物< 述者爲相同定義。具體上可舉例如脂肪族聚鏈烴烯 族聚醚、脂肪族聚酯、丙烯系聚合物及苯乙烯系聚 。其中，脂肪族聚醚、脂肪族聚酯及丙烯系聚合物 性有機聚合物（B )及氧化矽前驅物之相溶性良好 約10nm以下之範圍尺寸，因爲其結果係該熱分解 物分解揮發後，形成平均孔徑爲1 〇nm以下之多孔 適宜。 另外，樹枝狀高分子（Dendorimer)及星型聚 之作爲一次構造之具有支鏈構造者爲宜。使用具有 時，聚合物之佔有體積變小，所以可以容易地得到 徑爲1 Onm以下之多孔性。熱分解性聚合物之數目 子量係以300至100,000爲宜，以500至20,000 數目平均分子量於此範圍時，與耐熱性有機聚合衫 及氧化矽前驅物之相溶性良好，可得約1 Onrn以下 尺寸，因爲其結果係該熱分解性聚合物分解揮發後 平均孔徑爲1 Onm以下之多孔性所以適宜。 本發明中之耐熱性有機聚合物（B)之質量： 解聚合物換算之氧化矽（A )之質量、（以下，稱爲 化矽質量）之比率係5 : 9 5至9 5 : 5。於此範圍時 性奈米複合薄膜之耐藥品性及耐電漿性良好，不會 性有機聚合物（B )之熱交聯時之軟化而發生空孔 可得到充份的空孔率。上述之比率係以1 〇 : 9 0至 爲宜。 B)所 、脂肪 合物等 與耐熱 ，可得 性聚合 性所以 合物等 支鏈者 平均孔 平均分 尤佳。 1(B) 之範圍 ，形成 完全水 換算氧 ，多孔 因耐熱 消滅， 9 0 ·· 10 -16- (14) (14)200400238 尤佳。 本發明中之成份（c )的量，爲得到充份的空孔率， 所以相對於耐熱性有機聚合物（B )之質量與換算氧化砂 質量之合計，係以5質量％以上爲宜。另外，爲保持充份 的機械特性，相對於耐熱性有機聚合物（B )之質量與換 算氧化砂質量之合計’係以3 00質量％以下爲宜。（C ) 的量係以10至200質量％尤佳。 爲使本發明中之耐熱性有機聚合物（B )及氧化矽（ A)之範圍尺寸爲數1 Onm以下，而且使本發明中之平均 孔徑爲1 Onm以下’係以至少2個以上選自耐熱性有機聚 合物（B )及氧化矽前驅物之間（a )、耐熱性有機聚合物 (B )及成份（C )之間（b )以及氧化矽前驅物及成份（ C )之間（c )之成群’具有分子間相互作用爲宜。作爲分 子間相互作用，可舉例如共價鍵、離子鍵、氫鍵、；r 一 7Γ 相互作用、配位化合物形成及靜電相互作用等。以至少2 個選自上述之（a) 、 （b)及（c)之成群，具有因共價 鍵或氫鍵之分子間相互作用尤佳。具有相關之分子間相互 作用時，可抑制各成份之互相分離，範圍尺寸變小。其結 果係可得到機械特性、耐電漿及耐藥性優異之多孔性奈米 複合薄膜。 、 作爲耐熱性有機聚合物（B )及氧化矽前驅物之間（a )之分子間相互作用’係以共價鍵最好。因爲依據二者間 爲共價鍵而可提升多孔性奈米複合薄膜之機械特性。使二 者共價鍵結的方法係只要耐熱性有機聚合物（B )及氧化 -17· (15) (15)200400238 矽前驅物分別具有i種以上之可互相反應之官能基即可， 已知的手法均可適用。作爲具體例，可舉例如於耐熱性有 機聚合物（B)中，導入烷氧基甲矽烷基，與氧化矽前驅 物混合，或合成氧化矽前驅物時，與該耐熱性有機聚合物 (B ) —起進行水解反應而形成矽氧烷之方法，以及於耐 熱性有機聚合物（B)中，導入鏈烯基或炔基，使與含有 Si-H基之氧化砂前驅物反應（羥化，hydroxylation)之方 法等。其中係以於耐熱性有機聚合物（B )中，導入乙炔 基，與含有Si-H基之氧化矽前驅物反應之方法尤佳。 作爲耐熱性有機聚合物（B )及成份（C )之間（b ) 之分子間相互作用，係以共價鍵或氫鍵爲宜。方法係可採 用各種周知的方法’以下係以使用熱分解性聚合物作爲成 份（C )爲例說明。耐熱性有機聚合物（b )及熱分解性 聚合物，依據共價鍵賦予分子間相互作用之方法，可舉例 如耐熱性有機聚合物（B )及熱分解性聚合物之嵌段化或 交聯化。對於嵌段化或交聯化方法，已知方法可適用。例 如使用具有分子內可與耐熱性有機聚合物（B )反應或共 聚之部位之熱分解性聚合物之方法，使用具有分子內可使 熱分解性聚合物開始聚合之部位，或可與熱分解性聚合物 反應或共聚之部位之耐熱性有機聚含物（B )之方法。作 爲具體例’可舉例如依據合成支鏈上含有羥基之耐熱性有 機聚合物（B )，以該羥基爲開始部位，將環氧乙院、環 氧丙院及ε —己內酯等開環聚合，而得到交聯脂肪族聚醚 或脂肪族聚酯等之耐熱性有機聚合物（Β )之方法。 •18- (16) (16)200400238 作爲氧化矽前驅物及成份（c )之間（c )之分子間相 互作用係以共價鍵或氫鍵爲宜。氧化矽前驅物具有矽烷醇 (Si-OH )基時，以氫鍵最好，作爲成份（c )，以使用 含有羥基及羰基等之可氫鍵鍵結之部位之化合物爲宜。 作爲上述之分子間相互作用係以（a )或（b )上存在 共價鍵爲宜，尤其係以（a)或（b)上存在共價鍵，而且 (c )上存在氫鍵最好。 本發明之多孔性奈米複合薄膜係可由含有耐熱性有機 聚合物（B )、氧化矽前驅物、成份（C )及溶劑之組成 物形成薄膜後，除去上述成份（C )而得到。 該組成物只要爲各成份混合所成者即可，但以使用預 先介由共價鍵，使耐熱性有機聚合物（B )與氧化矽前驅 物完成反應之反應生成物，或預先介由共價鍵，使成份（ C )與氧化矽前驅物完成反應之反應生成物爲宜。具體上 ，該組成物之調製方法，可舉例如①將預先合成之耐熱性 有機聚合物（B )與氧化矽前驅物之反應物，與成份（c )及溶劑混合之方法，②將預先合成之耐熱性有機聚合物 (B )與成份（C )之反應物，與氧化矽前驅物及溶劑混 合之方法，以及③於成份（C )及/或溶劑之存在下，完成 生成耐熱性有機聚合物（Β)與氧化、砂前驅物之反應物之 方法等。 由該組成物形成薄膜之後，除去成份（C )之前，使 氧化矽前驅物凝膠化而固定化氧化矽爲宜。 作爲上述溶劑，係溶解或分散耐熱性有機聚合物（Β -19· (17) (17)200400238 )、氧化矽前驅物及成份（C )之3種成份，只要以防p Z尸灯需 之方法，得到具有所需之膜厚度、均勻性或埋入平坦性之 薄膜即可，並無特別的限制，可舉例如芳香族烴類、偶極 非質子系溶劑類 '酮類、酯類、醚類及鹵化烴類。 作爲芳香族烴類，可舉例如苯、甲苯、二甲苯、乙基 苯、異丙苯、均三甲苯、萘滿及甲基萘等。 作爲偶極非質子系溶劑類，可舉例如N -甲基吡咯丈完 酮、N，N—二甲基甲醯胺、N，N—二甲基乙醯胺、T — 丁內酯及二甲基亞硕等。 作爲酮類，可舉例如甲基異丁基甲酮、環戊酮、環S 酮、環庚酮、環辛酮及甲基戊基甲酮等。 作爲醚類，可舉例如四氫呋喃、吡喃、二噚烷、二甲 氧基乙烷、二乙氧基乙烷、二苯基醚、茴香醚、苯乙醚' 二乙二醇二甲醚（diglyme) 、triglyme、丙二醇單甲醚、 丙二醇單乙醚、丙二醇單丙醚及丙二醇單丁醚等。 作爲酯類，可舉例如乳酸乙酯、苯甲酸甲酯、苯甲酸 乙酯、苯甲酸丁酯、苯甲酸苯甲酯、醋酸甲基溶纖素（ Methyl Cellosolve Acetate)、醋酸乙基溶纖素及两一酉孚 單乙醚醋酸等。 作爲鹵化烴類，可舉例如四氯化碳、氯仿、二氣Φ ^ 、四氯乙烷、氯苯及二氯苯等。 耐熱性有機聚合物（Β )、氧化砂（A )(換算氧化 矽質量）及成份（C )之濃度合計係以1至8 0質量％爲且 ，以5至60質量％尤佳。 -20 - (18) (18)200400238 作爲薄膜之形成方法係以採用被覆於適當的基材上之 方法爲宜。可舉例如旋轉被覆法、浸漬被覆法、噴霧被覆 法 '壓模被覆法、條形被覆法、刮刀被覆法、押出被覆法 '掃描被覆法、刷塗法及罐泡法（potting )等之已知之被 覆方法。作爲電子元件用絕緣膜使用時，由膜厚度之均勻 性之觀點而言，係以旋轉被覆法及掃描被覆法爲宜。 膜的厚度係以0.01至50//m爲宜，以0.1至30#m 尤佳。 氧化矽前驅物之凝膠化係依據前驅物中之Si-OH基、 Si-〇R基、及/或Si-H基之聚合反應而進行。進行聚合反 應、的方法係可舉例如加熱方法以及暴露於含有鹼性催化劑 及水之環境之方法等。以加熱凝膠化時，爲使凝膠化充份 地進行，該溫度係以50 °C以上爲宜，以10(TC以上尤佳， 以1 5 0 °C以上最好。 暴露於含有鹼性催化劑及水之環境之方法，尤其適合 使用於進行Si-H基之聚合反應。作爲鹼性催化劑係以氨 、氫氧化銨及胺類爲宜。作爲胺類，可使用一級胺、二級 胺及三級胺。作爲具體例，可舉例如甲基胺、乙基胺、丁 基胺、烯丙胺、二甲基胺、二乙基胺、三甲基胺及三乙基 胺等。以上述之暴露於含有鹼性催化^劑蒸氣及水蒸氣之環 境’進行聚合反應爲宜。 除去成份（C )之方法係如上所述之加熱或電磁波等 之照射爲宜。以倂用加熱及電磁波照射爲宜。加熱及/或 電磁波照射之環境，可舉例如氮及氬等之不活性氣體環境 -21 · (19) (19)200400238 、空氣、氧氣及減壓等，以不活性氣體環境及減壓爲宜。 加熱條件係以2 0 0至4 5 0 °C下，1至1 2 0分鐘爲宜， 以3 0 0至42 5 °C下，2至60分鐘尤佳。爲控制氧化矽前驅 物之凝膠化反應速度及除去成份（C)之速度，或爲確保 塗膜表面平滑性或提升塗膜之微細空間埋入性，以追加 50至3 5 0 °C左右之預備加熱步驟，或將加熱步驟分成數階 段實施爲宜。 作爲電磁波照射條件’例如使用電子束時，以照射能 量爲〇·1至50keV爲宜，照射量以1至looG^c/cm2爲宜 〇 以加熱除去成份（C )時，凝膠化氧化矽前驅物之聚 合反應更進一步進行時，形成上述式（1)所表示之氧化 矽骨架。依據此步驟，實際上形成無Si-OH基及Si-OR基 或非常少之氧化矽相，因爲低電容率化、高機械強度化及 疏水化，所以適宜。另外，耐熱性有機聚合物（B )因熱 而具有自交聯性官能基時，因爲該官能基進行交聯反應， 提升耐熱性有機聚合物（B )相之耐熱性及耐藥品性，所 以適宜。 本發明中之含有耐熱性有機聚合物（B )、氧化矽前 驅物、成份（C )及溶劑之組成物係、以中和、再沈澱、萃 取及過濾等方法精製爲宜。關於電子零件相關用途時，聚 合反應催化劑之鉀或鈉等之金屬及游離鹵素原子成爲引起 電晶體之運作不良或配線腐蝕等之原因物質，所以充份地 精製爲宜。 -22- (20) (20)200400238 作爲本發明之多孔性奈米複合薄膜之用途，可舉例如 各種絕緣膜 '保護膜及燃料電池等之各種電池用膜材料、 光阻、反射防止膜、光導波材料、被覆材料、電子用零件 、密封劑、保護劑、透明薄膜材料、粘著劑、纖維材料、 耐候性塗料、撥水劑、撥油劑、防濕被覆劑等。尤其，電 子元件用絕緣膜或多層配線板用絕緣膜之用途爲宜。 作爲電子元件，可舉例如二級體、電晶體、化合物半 導體、熱敏電阻、變阻器及閘流體等之個別半導體、 DRAM (動態隨機存取記憶體）、SRAM (靜態隨機存取 記憶體）、EPROM (可抹式唯讀記憶體）、Masked ROM (固定程式）、EEPROM (代表可電子抹除可輸入程式的 僅讀記憶体）及快閃記憶體產品等之記憶元件、微處理器 、DSP (數位訊號處理器）及ASIC (特殊應用積體電路 )等之理論電路元件、MMIC (單石微波積體電路）所 代表之化合物半導體等之積體電路元件、混合積體電路（ hybrid 1C )、發光二極體及電荷結合元件等之光電變換元 件等。 所謂多層配線板係指實際裝有電子元件等之各種基板 ，可舉例如印刷配線板、疊層（Buildup )配線板及MCM (多晶片模組）等之高密度配線板等、。作爲絕緣板可舉例 如應力緩衝膜（Buffer coat)、鈍化膜（Passivation) 、層間絕緣膜及α粒子遮蔽膜 （α - particle barrier coat )等。 本發明之多孔性奈米複合薄膜係與其他膜複合化爲宜 -23- (21) (21)200400238 ° W ’適用半導體元件鈍化膜或半導體元件用層間絕緣 膜時’於多孔性奈米複合薄膜之下層及/或上層上，形成 無機膜爲宜。 {乍胃無機膜，以常壓、減壓或電漿化學氣相成長（ cvd )法或塗佈法所形成之膜，可舉例如於矽酸化膜上， 因應需要，塗佈磷或硼，即所謂的PSG膜或BPSG膜，矽 酸化膜、矽氮化膜、矽酸化氮化膜、Si OC膜及旋塗式玻 璃（SOG)膜等。 本：發明之多孔性奈米複合薄膜與金屬配線間，形成無 機膜’而可容易地防止金屬配線之剝落及容易進行鑲嵌（ damascene )形狀等之蝕刻加工。無機膜係於依據蝕刻法 或CMP法部份地削除多孔性奈米複合薄膜後，形成於多 孔性奈米複合薄膜上層爲宜。 於本發明之多孔性奈米複合薄膜上層，形成無機膜時 ’多孔性奈米複合薄膜與無機膜之密著性若不足時，或蝕 刻加工後除去光阻時之氧拋光有造成膜損壞之可能性時， 多孔性奈米複合薄膜表面以能量線處理爲宜。作爲能量線 處理，例如包括光之廣義的電磁波，亦即UV光照射、雷 射光照射、微波照射等或利用電子束處理，亦即電子束照 射、輝光放電處理、電暈放電處理及、電漿處理等之處理。 其中，適合半導體元件之量產步驟之處理方法，可舉 例如U V光照射、雷射光照射、電暈放電處理及電漿處理 〇 電漿處理造成半導體元件之損害小，尤其適宜。作爲 -24- (22) 200400238 進行電漿處理之裝置，於裝置內導入所需之氣體， 外加電場者即可，並無特別的限制，市售的桶型及 板型之電漿發生裝置即適合使用。作爲導入電漿裝 體，只要可有效地處理表面者即可，並無特別的限 舉例如氬、氨、氮、氧及這些之混合氣體等。以氮 處理係於多孔性奈米複合薄膜之最表面上，形成緻 化層，具有防止除去光阻時之氧拋光所造成膜的損 果，所以適宜。 【實施方式】 實施例 本發明係以下述之實施例及比較例具體地說明 發明不以這些爲限。例1至1 4爲合成例，例1 5 : 29及30爲實施例，例25至28爲比較例。 另外，例1至1 3中之分子量係依據使用輸送 四氫呋喃之凝膠液相層析儀（GPC )所測定之聚苯 之數目平均分子量。 [例1 ]耐熱性有機聚合物之合成 於容量爲1L之燒瓶中，放入18、· 9 0g之全氟（ 5 —三苯基苯）、8.32g之 4 一苯基乙炔基九氟 3.78g之1，3，5 -三羥基苯及279g之Ν，Ν·二甲 胺（以下，稱爲DMAc )。邊攪拌邊於油浴上加溫 溫達6 (TC時，快速添加2 7.3 g之碳酸鉀’繼續攪 只要可 平行平 置之氣 制，可 氣電漿 密的氮 害的效 ，但本 g 24、 溶媒之 烯換算 聯苯、 基乙醯 ，當液 拌，於 -25- (23) 200400238 6 0°C下，加熱4小時。之後，將反應液冷卻至室溫，緩 加入激烈攪拌之2 L之約含3 0 g之醋酸之純水/甲醇（容 比約1 /1 )時，白色粉末狀物沈澱。過濾該白色粉末狀 ，再以純水洗淨5次後，於8 CTC下，進行真空乾燥1 5 時，而得白色粉末狀之聚合物（以下，稱爲P 1 ) 。P 1 分子量約爲5,000。 [例2]耐熱性有機聚合物之合成 於容量爲l〇〇ml之燒瓶中，放入2.35g之3，3’ — 羥基二—1，4 —亞苯基）雙（2，4，5 —三苯基環戊二 酮）、1.14g之1，3，5 —三（苯基乙炔基）苯及之8. 之7 - 丁內酯，於氮氣環境，2 00 °C下，加熱48小時。 卻至1 〇 〇 °C左右，添加環己酮，使固形物成份濃度成爲 質量％，而得分子量約爲6,000之聚合物溶液（以下， 爲 P 2 )。 [例3 ]耐熱性有機聚合物之合成 於容量爲1L之燒瓶中，放入18.90g之全氟（1，3 5-三苯基苯）、l〇.72g之五氟二苯乙炔、5.04g之1，3 5-三羥基苯及312g之DM Ac。邊攪拌邊於油浴上加溫 當液溫達60°C時，快速添加36.4g之碳酸鉀，繼續攪拌 於6(TC下，加熱4小時。之後，將反應液冷卻至室溫 緩緩加入激烈攪拌之約1 L之1 N之鹽酸水溶液時，白 粉末狀物沈澱。過濾該白色粉末狀物，再以純水洗淨5 緩 積 物 小 之 ( 烯 5g 冷 20 稱 色 次 -26- (24) (24)200400238 後，於8 0 °C下，進行真空乾燥1 5小時，而得白色粉末狀 之聚合物（以下，稱爲P3 ) 。P3之分子量約爲3,5 00。 [例4]氧化矽前驅物之合成 於容量爲l〇〇ml之燒瓶中，放入5.00g之三乙氧基矽 烷、16.40g之甲基三甲氧基矽烷及39.07g之環己酮。於 室溫下邊激烈攪拌，邊以約40分鐘滴入6.68g之1%之馬 來酸水溶液，滴下終了後，於6 0 °C下，加熱2小時。之 後，使用蒸發器，濃縮至總重量成爲48.8g，而得固形成 份濃度（完全水解物換算）爲20質量％之氧化矽前驅物 (以下，稱爲S1)。分子量約爲1，200。 [例5]氧化矽前驅物之合成 於容量爲200ml之燒瓶中，放入8.02g之四甲氧基砂 烷、2 5.66g之甲基三甲氧基矽烷及63.6 4g之丙二醇單丙 醚。於室溫下邊激烈攪拌，邊以約5 0分鐘滴入1 2 · 7 0 g之 1 %之馬來酸水溶液，滴下終了後，於6 0 °C下，加熱2小 時。之後，使用蒸發器，濃縮至總重量成爲7 7 · 8 g，而得 固形成份濃度（完全水解物換算）爲20質量％之氧化石夕 前驅物（以下，稱爲S2 )。分子量玲爲1，000。 [例6]熱分解性聚合物之合成 於容量爲50ml之燒瓶中，放入1.24g之乙二醇、 22.82g之ε —己內酯及〇.〇lg之2 —乙基己酸錫。於氮氣 -27- (25) (25)200400238 環境，1 2 0 °C下，加熱2 0小時，而得到具有2個烴基作爲 分子內末端基之聚己內酯（以下，稱爲D1)。分子量約 爲 1 5 2 0 0。 [例7 ]熱分解性聚合物之合成 取代乙二醇，改使用2.2 7g之2，2—雙（經甲基）— 1 ’ 3 —丙二醇以外，與例6同樣地，得到具有*個烴基作 爲分子內末端基之聚己內酯（以下，稱爲D2)。分子量 約爲1，1 0 0。 [例8 ]熱分解性聚合物之合成 取代乙二醇，改使用1 · 8 9 g之乙二醇單叔丁醚以外， 與例6同樣地，得到具有丨個烴基作爲分子內末端基之聚 己內酯（以下，稱爲D3)。分子量約爲1，700。 [例9]耐熱性有機聚合物與氧化矽前驅物之反應物之合成 將溶解0.5 0 g之例1所得到之聚合物P 1於2 · 8 5 g之 環己酮之溶液，以及5 · 1 0 g之例4所得到之氧化矽前驅物 溶液S 1，放入容量爲2 5 m 1之燒瓶中，系統內以氮氣取代 。於其中，添加3 " 1之二乙烯基四、矽氧烷鉑配位化合物 (3 %之甲苯溶液），於70°C下，加熱2小時。再添加4 二乙烯基四矽氧烷鉑配位化合物（3 %之甲苯溶液），於 7 5 °C下，加熱1小時，而得到耐熱性有機聚合物與氧化矽 前驅物之反應物溶液（以下，稱爲P S 1 )。 -28- (26) (26)200400238 [例i 〇]耐熱性有機聚合物與氧化矽前驅物之反應物之合成 將5.00g之例2所得到之聚合物P2，以及5.〇〇g之例 4所得到之氧化矽前驅物溶液s 1，放入容量爲2 5 m 1之燒 瓶中’系統內以氮氣取代。於其中，添加5 " 1之二乙烯 基四砂氧烷鉑配位化合物（3 %之甲苯溶液），於7 5。(：下 ’加熱2小時’而得到耐熱性有機聚合物與氧化矽前驅物 之反應物溶液（以下，稱爲p S 2 )。 [例1 1 ]耐熱性有機聚合物與氧化矽前驅物之反應物之合成 將溶解3.0 g之例3所得到之聚合物P 3於1 7 g之甲苯 ’以及〇.59g之三乙氧基矽烷，放入容量爲50ml之燒瓶 中，系統內以氮氣取代。於其中，添加2 0 1之二乙烯基 四矽氧烷鉑配位化合物（3 %之甲苯溶液），於8 0 °C下， 加熱2小時。冷卻後，將反應溶液緩緩投入過剩的己烷中 ，將所得到的白色粉末，於8 0 °C下，真空乾燥1 5小時， 而得含有三乙氧基甲矽烷基之聚合物（以下，稱爲P4) 〇 將〇.95g之聚合物P4、1.2g之四乙氧基矽烷、3.68g 之甲基三乙氧基矽烷以及 20g之寧己酮，放入容量爲 10 0ml之燒瓶中，於室溫下攪拌成均勻溶液。於室溫下邊 激烈攪拌，邊以約40分鐘滴入1.57g之1%之馬來酸水溶 液，滴下終了後，於60 °C下，加熱2小時。之後，使用 蒸發器，濃縮至總重量成爲14.8g，而得到耐熱性有機聚 -29- (27) (27)200400238 合物與氧化矽前驅物之反應物溶液（以下，稱爲PS3 )。 [例12]耐熱性有機聚合物與熱分解性聚合物之反應物之合 成 將溶解2 5 . 1 1 g之例8所得到之聚合物D 3於1 0 0.4 g 之四氫呋喃，放入容量爲3 00ml之燒瓶中。於其中加入 l〇.3g之吡啶、20.99g之六甲基二矽氨烷以及14.1g之氯 化三甲基砂院，於氮氣環境，5 0。(：下，反應2 0小時。蒸 餾除去揮發成份後，加入78.9g之二氯甲烷溶解。進行使 用濾紙之吸引過濾，除去不溶成份後，蒸餾除去揮發成份 後，而得到末端具有三甲基砂氧院基（methylsilyloxy) 之聚己內酯。 溶解2.5g之本聚己內酯及2.5g之例1所得之聚合物 P1於20g之二甲基甲醯胺，放入容量爲50ml之燒瓶中。 再加入0.7 5 g之氟化鉋，於氮氣下，以7 0 °C下，加熱4小 時。冷卻後，加入8.0g之三氟乙酸，於室溫下攪拌10小 時。投入大量之約〇 · 1 N之鹽酸水溶液中，而回收白色粉 狀聚合物，於8 0 °C下，進行真空乾燥1 2小時，而得到耐 熱性有機聚合物與熱分解性聚合物之反應物（以下’稱爲 PD1 ) 〇 、 [例1 3]耐熱性有機聚合物與熱分解性聚合物之反應物之合 成 將3.0g之例1所得之聚合物PI、〇.78g之2—（ 4一 -30- (28) (28)200400238 羥基苯基）乙醇及27g之DMAc，放入容量爲50ml之燒 瓶中，於6 0 °C下，攪拌成均勻溶液。於此溫度下，一次 加入1.2g之碳酸鉀，，於60°C下，攪拌持續加熱6小時 。冷卻後，投入大量的約1N之鹽酸水溶液，而回收白色 粉狀聚合物，於8 (TC下，進行真空乾燥12小時，而得到 具有分子內一級烴基之聚合物。 將〇.6g之本聚合物、1.8g之ε —己內酯及0.004g之 2 —乙基己酸錫，放入容量爲2 0ml之燒瓶中。於氮氣環境 ，1 2 0 °C下，加熱2 0小時，而得到於耐熱性有機聚合物 P1上交聯聚己內酯之聚合物（以下，稱爲PD2)。分子 量爲 1 0,000。 [例1 4]於熱分解性聚合物之存在下之耐熱性有機聚合物與 氧化矽前驅物之反應物之合成 將l.OOg之例1 1所得到之聚合物P4、3.47g之四乙 氧基矽烷、l.〇〇g之聚甲基丙烯酸甲酯（Aldrich社製，分 子量約爲15,000)及12g之甲基異丁基甲酮’放入容量爲 5 0ml之燒瓶中，於室溫下’攪拌成均勻溶液。再加入20g 之0.0 1 %之馬來酸水溶液’於室溫下，激烈攪拌約1小時 。之後，分取甲基異丁基甲酮層’使、用蒸發器’濃縮至總 重量成爲1 5 g ’而得到含有熱分解性聚合物 '耐熱性有機 聚合物與氧化矽前驅物之反應物溶液（以下，稱爲P S D 1 -31 - (29) 200400238 [例 15] 於1 00質量份之例9所得到之耐熱性有機 化矽前驅物之反應物溶液PS 1 (耐熱性有機聚 氧化砂質量爲3 : 7，固形份濃度之總計爲1 8 溶解1 2.6質量份之例6所得之熱分解性聚合 如表1所示組成比之組成物。在此，氧化矽前 換算氧化矽質量。該組成物係以孔徑〇 · 2 m , 過濾器過濾，於4英寸矽圓上旋轉噴霧，形成 薄膜。於加熱鐵板上進行1 5 0 °C X 1 8 0秒鐘， 秒鐘之預備加熱後，接著於縱型爐425 °C X 1 環境下之進行加熱（燒成）。對於所得到之多 合薄膜，進行下述評估之結果，如表1所示。 電容率：使用SSM社製之SSM— 495，進 探針之循環伏安法（cyclic voltammetry; CV 出1MHz之電容率。膜厚度係使用依據分光橢 求得之値。 機械強度：使用 MTS社製之DCM - SA2 硬度測試法（n a η 〇 i n d e n t a t i ο η )，測定彈性模_ 平均孔徑：使用理學電機社製ATX- G， X光散射，求出多孔性薄膜中之平均、孔徑。 另外，依據該薄膜斷面之掃描式電子顯微 觀察到30nm以上之相構造。依據分光橢圓對 之於63 0nm時之該薄膜之折射率値爲1.28。 未含熱分解性聚合物D1，僅由PS 1，以同樣 聚合物與氧 合物：換算 質量％ )， 3 D1，作成 驅物係使用 之 PTFE製 :5 5 Onm 之 2 5 0 °C X 1 8 0 小時，氮氣 孔性奈米複 行依據水銀 )測定，求 圓測厚儀所 ，依據納米 t。 依據小角度 鏡觀察，未 稱計所求得 另一方面， 的塗佈條件 -32- (30) (30)200400238 所得膜之折射率爲1 · 4 3。該折射率降低係表示空氣相（折 射率値1 )存在於膜中，亦即表示形成多孔性，空孔率如 下述計算之3 5 %。 ( 1.43— 1.28) +( 1.43— 1) χ 1 0 0 = 3 5 [例16至例28] 使用表1中所示之原料，以表1中所示之組成比，調 整含有氧化矽前驅物、耐熱性有機聚合物、熱分解性聚合 物及溶劑之組成物。例2 7中，使用環己酮作爲溶劑。由 這些組成物，以與例1 5同樣的方法，形成薄膜，進行膜 特性之評估。另外，調整組成物之固形成份濃度及旋轉次 數以使膜厚度進入400至7 OOnm之範圍內。調整組成物 之固形成份濃度，需要稀釋時，使用環己酮作爲稀釋溶劑 。其結果如表1所示。 將例1 6至例2 7所得到之薄膜斷面，以掃描式電子顯 微鏡觀察時，未觀察到3 Onm以上之相構造。另外，例2 8 之組成物雖爲均勻透明，但是旋轉包覆時，觀測到認爲因 // m階級以上之相分離所引起之膜之粗糙及白濁，無法評 估膜的特性（表中記載爲不可評估）。 -33- (31) (31)200400238 表1 原料 組成比（質量） 塗膜特性 二氧化矽 先驅物 耐熱性有 機聚合物 熱分解性 聚合物 電容率 彈性模數 (GPa) 平均孔徑 (nm) 例15 PS1、D1 7 3 7 2.0 4.2 2 例16 PS 1、D1 7 3 10 1 .7 4.0 3 例17 PS2 、 D2 5 5 7 1.8 4.1 2 例18 PS3 、 D2 7 3 5 1 .9 4.5 2 例1 9 S2 、 PD1 7 3 3 2.2 5.8 1 例20 S2 、 PD1 5 5 5 2.1 5.1 2 例21 S2 、 PD1 3 7 7 1.8 4.5 2 例2 2 S2、PD2 7 3 9 1.7 3.8 3 例23 SI 、 PD2 7 3 9 1.8 4.0 2 例24 p S D 1 5 5 5 2.0 6.2 2 例25 SI、D2 10 0 5 2.2 2.0 5 例26 SI、D2 10 0 10 1 .7 1 .0 10 例27 PD 1 0 10 10 2.5 2.5 2 例28 P1、S 1 、D2 7 3 7 不可評估 [例2 9 ]作爲層閭絕緣腠之δ平估（積層構造之安定性） 依據例1 9中所調整之溶液組成物，以下述之方法作 成矽圓/P-SiO ( 3 00nm) /多孔性奈米複合薄膜（5〇〇nm) y p-SiN ( 50nm) / p-Si〇 ( 500nm)之積層膜。 -34- (32) (32)200400238 於形成ρ-SiO膜（膜厚爲3 0 0nm)之矽圓上’旋轉包 覆溶液，與例1 4同樣地形成膜厚爲5 OOnm之多孔性奈米 複合薄膜。其次，於單矽烷、氨及氮之混合氣體下’形成 5 0 n m之氧化矽氮化膜，之後，於單矽烷及二氮化氧之混 合氣體下，形成500nm厚之氧化砂氧化膜。 將所得之積層膜，於氫氣環境下，以425 °C，進行60 分鐘燒烤，於金屬顯微鏡下，調查因熱壓力之斷裂耐性時 ，未發生斷裂及其他缺陷。 [例3 0]作爲層間絕緣膜之評估（微細加工及耐藥品性） 依據例1 9中所調整之溶液組成物，以與例1 4同樣的 條件旋轉包覆，於矽圓上，形成膜厚爲40 Onm之多孔性 奈米複合薄膜。於其上形成光阻，以曝光顯影技術（ Photolithography )形成堆焊後，以使用氮/氫/氬之混合氣 體之反應式離子飽刻法（RIE， Reactive Ion Etching ) ，進行多孔性奈米複合薄膜之蝕刻。經過以光阻剝離液 EKC265 (商品名，EKC社製）之洗淨步驟後之塗膜，以 金屬顯微鏡調查時，未觀察到缺陷等。另外，顯示電容率 値爲2· 1 ’與剛製膜後之値並無差異。亦即確認以精細加 工及光阻除去步驟，對於多孔性奈米、複合薄膜並未造成損 害。 產業上利用性 本發明之多孔性奈米複合薄膜爲電容率低，而且以彈 -35- (33) (33)200400238 性模數所表示之機械特性優異。對於電子元件用絕緣膜及 多層線板用絕緣膜之製造步驟中之電漿處理及洗淨處理之 耐性高，該多孔性奈米複合薄膜作爲電子元件用絕緣膜及 多層線板用絕緣膜之適用性優異。200400238 (1) Description of the invention [Technical field to which the invention belongs] The present invention relates to a porous nano composite film and a method for forming the same. [Prior art] As electronic components and multilayer wiring boards become more refined and highly integrated, ‘is an insulating film that is suitable for this’ and requires a lower permittivity. Here, the technique of making existing materials porous and introducing an air phase with a permittivity of 1 into the membrane has been widely reviewed. As those who use silicon oxide as a framework material, Japanese Patent Application Laid-Open No. 2001-2992 and Japanese Patent Application Laid-Open No. 2001-98224 are known. Those using a heat-resistant organic polymer as a skeleton material are known from US Patent No. 6 1 72 1 28 and the like. According to these techniques, voids having a pore size of 20 nm or less can be introduced into the film, and a film having a permittivity of 2.1 to 2.5 can be obtained. However, there are two major problems with the existing technologies mentioned above. First, the mechanical strength of the film is extremely reduced due to the introduction of voids. For example, in the case of chemical mechanical polishing (CMP · · Chemical Polishing) in the step of smoothing the surface, the problem of peeling occurs. Therefore, it is practically impossible to obtain a film system having a permittivity of 2 or less without increasing the porosity to a certain degree or more. Another question concerns the shape of the holes. S is that the pores are connected to each other, that is, there are a lot of continuous pores. Therefore, after the photoresist removal step after etching, the active particles in the plasma and the cleaning chemical solution easily penetrate into the film, causing the film to deteriorate Or pollution. These two problems are fatal flaws in the manufacture of electronic components and multilayer wiring boards, and they are very much expected to be improved. -4- (2) (2) 200400238 In order to improve the mechanical strength of a porous membrane, a method of forming a dense membrane on top of a porous membrane to reinforce the porous structure is described in US Patent 6 1 7 1 687 Number manual. However, this method has the effect of improving the mechanical strength, but it also causes the porosity of the coating film to decrease and the permittivity to increase, which cannot solve the essence of the problem. SUMMARY OF THE INVENTION The object of the present invention is to solve the above problems, and more specifically, to provide a coating film having a low permittivity and excellent mechanical properties, plasma resistance, and chemical resistance. The present invention provides a porous nano-composite film containing silicon oxide (A) and a heat-resistant organic polymer (B) and having an average pore size of 10 nm or less, which is characterized by porosity. In addition, the present invention provides a thin film formed from a composition containing a precursor of silicon oxide (A), a heat-resistant organic polymer (B), a component (C) that can be removed after film formation, and a solvent, and then the component (C A method for forming a porous nano-composite film characterized by removal. The porous nano-composite film containing silicon oxide (A) and heat-resistant organic polymer (B) in the present invention is the best form for carrying out the invention, and is a porous film having an average pore diameter of 10 nm or less. . The average pore size is preferably 5 nm or less, and more preferably 3 nm or less. In addition, the so-called average pore diameter in the present invention is an average pore diameter obtained by small angle -5-(3) (3) 200400238 X-ray scattering (Small Angle X-ray Scattering). The domain size of each of the silicon oxide (A) and the heat-resistant organic polymer (B) is preferably several 10 nm or less. Since the wiring interval of electronic components becomes narrower every year, it will be several ohms in the future, so the size of the field of each component is as described above. In addition, if the average pore diameter exceeds 100 nm, the active particles or the cleaning solution in the plasma when the device is manufactured may easily penetrate into the pores and cause damage to the membrane. The so-called porosity in the present invention is preferably a porosity having a porosity of 5 to 70%, and more preferably 10 to 60%. The silicon oxide (A) in the present invention is actually represented by the following formula (1), and is particularly preferably formed by a silicon oxide (A) precursor (hereinafter, referred to as a silicon oxide precursor) described later. (X) X2SiO) a (X3Si03 / 2) b (Si02) c Formula (1) Here, X1, X2 and X3 represent a hydrogen atom, a fluorine atom, an alkyl group and an aryl group having 1 to 8 carbon atoms Or vinyl, they may be the same or different. The points a, b, and c are each a number of 0 or more and 1 or less. However, when a + b + c di 1 X 1, X 2, and X 3 are hydrogen atoms, methyl groups, or phenyl groups, they have good heat resistance and mechanical properties. Therefore, hydrogen atoms, methyl groups, or phenyl groups are preferred. When a is large, the specific permittivity of the obtained silicon oxide is small, but in order to maintain sufficient heat resistance and mechanical characteristics, it is preferably 0.5 or less, and more preferably 0.3 or less. The c-system is preferably 0.02 or more in order to improve heat resistance and mechanical characteristics, and is preferably 9.9 or less in order to keep the permittivity low. Further, c is preferably 0.3 or more and 0.9 or less. -6-(4) (4) 200400238 The heat-resistant organic polymer (B) in the present invention refers to a polymer having a thermal decomposition temperature of 400 ° C or higher. The thermal decomposition temperature is preferably 425 ° C or higher, and more preferably 45 ° C or higher, and is generally 55 ° C or lower. Here, the so-called thermal decomposition temperature is based on an inert gas environment. Thermogravimetric analysis (TGA) measurement at a temperature rise of 10 ° C / min, which reduces the temperature by 3% by weight. The permittivity of the heat-resistant organic polymer (B) in the present invention is preferably 4 or less, and 3 The following is particularly preferred. Especially, the thermal decomposition temperature is 450 ° C or higher, and the permittivity is preferably 3 or lower. Related heat-resistant organic polymers (B) include, for example, Japanese Patent Application Laid-Open No. 9-2 02 82 3 and special features Polyarylene ether described in Kaiping No. 10 — 247646, polyarylene ether described in WO 00/083 08, and polyphenylene described in JP 2000 — 191752 Polymers containing an aromatic ring and polymers containing a fluorine atom are suitable examples. In addition, since the permittivity plate can be reduced, it is preferable that the repeating unit does not contain a polar group. As the above-mentioned polymer containing an aromatic ring Repeating order A polymer having a suitable position is preferred. The fluorine content of the above-mentioned fluorine atom-containing polymer is preferably 10% by mass or more, and more preferably 30% by mass in order to increase the permittivity reduction effect. In addition, it is to maintain For sufficient solvent solubility, the fluorine content is preferably 70% by mass or less. Especially, it is preferably 30 to 60% by mass. The heat-resistant organic polymer (B) in the present invention is one having a fluorine atom. In addition, the polymer having an aromatic ring-containing repeating unit is the best. In addition, the heat-resistant organic polymer (B) in the present invention is crosslinked from the viewpoint of heat resistance (5) 200400238 and solvent resistance. As a crosslinkable functional group, it is preferable to use a self-crosslinking group such as heat, light, and an electron beam. The self-crosslinking functional group is used for heating, because it has excellent applicability to the manufacturing steps of electronic parts such as electronic layer wiring boards. In addition, a crosslinkable functional gene that does not contain a polar group is suitable for reducing the capacity. The related crosslinkable functional group can also be used as a precursor to form a covalent bond functional group. Crosslinkable function For specific examples, for example, oxocyclopenta-2,5-dien-3-yl group (hereinafter, referred to as cyclopentadienone), cyano group, alkoxymethylate: alkoxysilyl groups), diarylhydroxymethyl group, and hydroxyhydrazone In terms of preference, ethynyl is preferred. The content of the above-mentioned crosslinkable functional group is a repeating unit of 1 mole organic polymer (B), and when it is 0.05 to 6 moles or more, sufficient heat resistance can be maintained. When it is below the chemical resistant ear, the permittivity can be kept low, and the content can be kept at a ratio of 0.1 to 4 moles. A suitable example of the heat-resistant organic polymer (B) in the present invention is, for example, a compound containing a diene group (diene) and a compound containing a compound group (die η 〇phi 1 e), a Di Ade Alder Poiyphenylene synthesized by) type polymerization, fluorinated polyarylene fluorinated polyarylene ether synthesized by a deHF polycondensation reaction between a fluorinated aromatic ring compound and a nucleophilic substitution type containing two or more phenolic hydroxyl groups. should. Combined functional elements and many more suitable compounds, such as silicon and silicon oxide, blendadione alkyl group, etc. The heat resistant ear is preferred. The property is 6 mol toughness. There are two specific examples above. Diene (Diels · and alkenyl ethers containing compounds ((6) (6) 200400238) The above polyphenylene is based on a compound having two or more diene groups and a compound having three or more diene groups. Diels-Alder type polymerization reaction products between the compounds are preferable. As the diene group, a cyclopentadienone group is preferable, and as the dicyclopentadienone having two or more diene groups. Derivatives include, for example, 1,4-bis (1-oxy-2,4,5-triphenyl-cyclopenta-2,5-diene-3-yl) benzene, 4,4, -bis (1-1 Oxy-2,4,5-triphenyl-cyclopentane-2,5-diphenyl-3, yl) biphenyl, 4,4, -bis (1-oxy-2,4,5-triphenyl- Cyclopentyl-2,5-diene-3-yl) 1,1'-hydroxybiphenyl, 4,4'-bis (1-oxy-2,4,5-diphenyl-cyclopentane-2,5— Mono green-3 -yl) 1,1'-thiobiphenyl 1,1,4-bis (1-oxy-2'5-bis (4-fluorobenzene] -1,4-phenyl-cyclopent-2,5-diene-3, yl) benzene, 4,4'-1 Bis (1-oxo-2,4 '5-diphenyl-cyclopentane-2,5-diphenyl-3-yl) 1,1'-(1,2-ethanediyl) biphenyl and 4, 4 'One bis (1-oxy-2,4,5-triphenyl-cyclopentane-2,5-diene-3-yl) 1,1'-(1,3-propanediyl) biphenyl, etc. Among these dicyclopentadienone derivatives, from the viewpoint of heat resistance, a dicyclopentadione derivative having a wholly aromatic skeleton is preferable. These may be used alone or in combination of two or more kinds. As the above The diene neo-base is preferably an ethynyl or alkynyl group. Compounds having more than three diene neo-bases can be exemplified by 1,3,5-triethynylbenzene, 1,2,4-a Triethynylbenzene, 1,3,5-tris (phenylethynyl) benzene, 1,2,4-tris (phenylethynyl) benzene and 1,2,3,5-tetrakis (phenylethynyl) Benzene, etc. These can be used alone or in combination of 9-9 (7) 200400238 or more. There are 2 or more The Diels-Alder type reaction between a diene-based compound and a compound having more than 3 alkene groups is preferably carried out by heating in a solvent. As a solvent system, as long as the reaction is inactive Yes, there are no special restrictions, such as mesitylene-butyrolactone, etc. The reaction conditions are from 150 to 250 ° C, 1 to 60 ° C. Dienyl: a new compound of diene When the molar ratio is from 1 ·· 1 to 1: 3, when the polymerization reaction is performed in a range of 1: 1 to 1: 2, polyphenylene having excellent heat resistance is preferred. From the viewpoint of preventing gelation in the polymerization, it is preferable that all of the diene group and the diene novel compound are left unreacted at about 10 to 30%. The reaction rate is preferably controlled by the reaction temperature and time. The diene groups and diene compounds remaining in the polymer function as crosslinkable functional groups that react by heating after film formation, and can be used as reaction sites with silica precursors and / or component (C) to make the above The fluorine-containing polyarylalkenyl ether is synthesized by de-HF polycondensation of a fluorine-containing aromatic ring compound directly bonded to fluorine on an aromatic ring and a compound containing more than two phenolic hydroxyl groups. The fluorine-containing aromatic ring-containing compound is preferably a perfluoroaromatic compound, and examples thereof include perfluorobiphenyl, perfluoronaphthalene, perfluorobitriphenyl, per1,3,5-triphenylbenzene) and perfluorobiphenyl. Fluorine (1,2, 5-triphenylbenzene) These can be used alone or in combination of two or more. Of these fluorinated compounds, perfluoro (1,3,5-triphenyl and perfluoro (1,2,5-triphenylbenzene)) having a branched structure because of the heat resistance of the obtained fluoropolyether It has good properties, so it's suitable. The second is the poly-paraben and r, which can be used to obtain a moderate reaction group and a basic system. It is also used. Those containing an intermediate ring (such as aromatic benzene) arene-10- (8 (8) 200400238 As the above-mentioned compound containing two or more phenolic hydroxyl groups, polyfunctional phenols are preferred. Specific examples include dihydroxybenzene, dibonded biphenyl, dihydroxybitriphenyl, and diphenyl. Hydroxynaphthalene, dihydroxyanthracene, dihydroxyphenanthrene, dihydroxy-9,9-diphenylfluorene, dihydroxydibenzofuran, dihydroxydibenzyl ether, triphenyl disulfide, diphenyl benzene Benzene, dibasic group ~ 2,2-diphenylpropane, dihydroxy-2,2-diphenylhexafluoropropane, dibasic binaphthalene, tetraphenylamino light, hexaphenyl dibasic biphenyl , Tribasic benzene, trihydroxybiphenyl, trihydroxynaphthalene, tetrahydroxybenzene, tetrahydroxybiphenyl, tetrahydroxybinaphthalene and tetracycline spiroindan. Among them, in order to lower the permittivity of the obtained polymer and to have good heat resistance, dihydroxybenzene, dihydroxy-9,9-diphenylfluorene, and dihydroxy ~ 2 '2-diphenylhexafluoropropane are used. It is preferable to use a hydrogen atom, tetraphenyl hydrogen roller and trihydroxybenzene. The above-mentioned fluorine-containing polyarylene ether is preferably to contain an ethynyl group as a crosslinkable functional group. The acetylene gene is self-crosslinking due to heat, and can be completed with The silicon oxide precursor generates a covalent bond. As a method for introducing an ethynyl group, it is preferable to copolymerize a monomer having an acetylene group during the above-mentioned polycondensation reaction. As the monomer having an acetylene group, for example, pentafluoro Fluorine-containing arylacetylenes such as phenylacetylene and nonafluorobiphenylacetylene, fluorinated diarylacetylenes such as phenylacetylene pentafluorobenzene, phenylacetylene nonafluorobiphenyl, and decafluorodiphenylacetylene Type, phenylvinylphenol and dihydroxydiphenylacetylene bis-containing hydroxyacetylenes. These can be used alone or in combination of two or more. As the above-mentioned HF-removing agent for the polycondensation reaction, a basic compound is suitable. , Especially for carbonates, bicarbonates or hydroxides of alkali metals as Specific examples include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, hydrogen-11-(9) 200400238 sodium oxide and potassium hydroxide, etc. The amount of de-HF agent used is relative to that of phenol. The molar ratio of the hydroxyl group is preferably 1 time or more, and preferably 1.1 to 3 times. The above polycondensation reaction is preferably performed in a polar solvent. As the polar solvent, N 'dimethylacetamide and N'N are contained. —Aprotic polar solvents, such as —dimethylformamide, N-methylpyrrole, dimethylasyl, and cyclidine, are suitable. In polar solvents, as long as the solubility of the polymer produced is not reduced, As long as it does not cause adverse effects on the polycondensation reaction, it may contain toluene, diphenyl, benzene, trifluoromethylbenzene, hexafluoroxylene, etc. The polymerization reaction conditions are 10 to 20 (TC, 1 to 80 is preferred). At 40 to 180 ° C, 2 to 60 hours are particularly preferred. At 60 to ° C, 3 to 24 hours is best. The number-average amount of the heat-resistant organic polymer (B) in the present invention is preferably from 5,000 to 500,000. When it is in this range, the compatibility between the silicon oxide and the component (C) is good, and the area size and average pore diameter of each component in the obtained porous nano-film are small, and good heat resistance, mechanical properties, and Film with chemical resistance, etc. The above-mentioned series are preferably 1,000 to 100,000, and most preferably 1,500 to 50,000. The so-called silicon oxide precursor in the present invention is formed by an acid or an alkali, an oxidizing agent such as oxygen, or heat to form the above formula (1 As for the oxygen (A) represented by), one or two or more kinds are selected from the group consisting of alkoxysilanes represented by the following formulae (2)) and (4), and partial hydrolysis polymerization is preferred. Χϋί (OR1) 2 Formula (2) -12- Compared with N-alkanone medium, it is 160 molecules per hour when toluene is thinned to a small amount with silicon molecule (200400238 do). X3Si ( OR2) 3 Formula (3) si (〇R3) 4 Formula (4) Here, X1, X2 and X3 are the same as the formula (1). R1, R2 and R3 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Specific examples of the alkoxysilane represented by the formula (2) include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethyl. Oxysilane, dimethoxysilane, diethoxysilane, difluorodimethoxysilane and difluorodiethoxysilane. These can be used alone or in combination of two or more. Dimethyldimethoxysilane and dimethyldiethoxysilane are preferred. Specific examples of the alkoxysilane represented by the formula (3) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, octyltrimethoxysilane, and octyl. Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trimethoxysilane, triethoxysilane, triiso Propoxysilane, fluorotrimethoxysilane, and fluorotriethoxysilane. These can be used alone or in combination of two or more. Methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trimethoxysilane, and triethoxysilane are suitable. Specific examples of the alkoxysilane represented by the formula (4) include, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. These can be used alone or in combination of two or more. Tetramethoxysilane and tetraethoxysilane are preferred. The alkoxysilane represented by the formula (2) and the alkoxy-13- (11) 200400238 based silane (1) 4 represented by the formula (3) are hydrolyzed to form polyalkanes to be added to 5.0. Acid, butyric acid, maleic acid, fatty acid, p-methyl, trifluorocitric acid and acid, fluorine as pyrrolidinamine, glycolamine, monoene and ammonia, hydrogen and alkoxy group represented by formula (4) The ratio of silanes determines a, b, and c of Formula 3 above. (2), (3) and (4) The partial reaction of the alkoxysilane is preferably performed by adding a catalyst and water. For each 1 oxysilyl group, 0.3 to 5.0 mol is added. Ear water is suitable, and 0.5 to 2.0 moles is particularly preferable. As long as the amount of water added is within the range of 0.3 moles, the uniformity of the obtained film can be maintained, and the film formation is well maintained for formation. Storage stability of the composition. Examples of the catalyst include organic acids, inorganic acids, and organic alkaline inorganic test compounds. Examples of the organic acids include acetic acid, propionic acid, valeric acid, hexanoic acid, heptanoic acid, and octanoic acid. , Nonanoic acid, capric acid, oxalic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, n-mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, hard Linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid benzenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, formic acid, malonic acid, sulfonic acid, Phthalic acid, fumaric acid, citric tartaric acid, etc. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. Examples of organic basic compounds include pyridine, pyrrole, piperazine, piperidine, methylpyridine, trimethylamine, triethylamine, monoethanolethanolamine, dimethylmonoethanolamine, and monomethyldiethanolamine. , Triethyldiazabicyclooctane, diazabicyclononane, diazabicyclotetramethylammonium decahydroxide, etc. Examples of the inorganic basic compound include sodium oxide, potassium hydroxide, barium hydroxide, and hydrogen Calcium oxide, etc. The amount of catalyst-14- (12) (12) 200400238 agent used is 0.0001 to 1 with respect to the total molar ratio of the compound represented by formulas (2), (3) and (4), It is preferably from 0.001 to 0.1. The number average molecular weight of the oxidized precursor in the present invention is preferably from 3,000 to 100,000. In this range, the oxidized sand precursor and heat resistance The compatibility of the organic polymer (B) and the compatibility of the precursor of the oxidized sand with the component (C) are good. The obtained oxidized sand (A) and the heat-resistant organic polymer (B) in the obtained porous nano composite film If the range size is small, and the average pore diameter is less than 1 0 // m, it has good heat resistance Thin film, mechanical properties, chemical resistance, etc. The above molecular weight is preferably from 500 to 50,000, and more preferably from 600 to 20,000. The component (C) in the present invention is only required to be removed after the film is formed. Specific restrictions include the following examples: (1) a substance that is volatilized by heat or a decomposition product that is decomposed by heat is a volatile substance; (2) a substance that is decomposed by irradiation of ultraviolet rays, electron beams, or other electromagnetic waves Decomposed substances are volatile substances and (3) substances dissolved by chemical solutions or decomposed substances decomposed by chemical solutions are dissolved substances, etc. Among them, they are suitable for the manufacturing steps of electronic components such as electronic components and multilayer wiring boards. High sex, the substance of (1) or (2) is suitable. The substance of (1) is particularly preferred. Specific examples include compounds having a boiling point of 200 to 400 ° C under normal pressure, and thermally decomposable polymers. Specific examples of compounds having a boiling point of 200 to 40 ° C. under normal pressure include pentylbenzene, cyclohexylbenzene, dimethylnaphthalene, tetradecane, decalin, naphthyl, decanol, undecanol, Dodecyl alcohol, pentanediol, glycerin, dibutyl oxalate, dibutyl tartrate, dimethyl phthalate, etc. The thermal decomposition temperature of the above thermally decomposable polymer is about 40 ° C or lower- 15- (13) 200400238 polymer, with a thermal decomposition temperature of about 3 5 (The thermal decomposition temperature of polymers below TC is the same as the heat-resistant organic polymer described above. < The author is the same definition. Specific examples thereof include aliphatic polyalkene-based polyethers, aliphatic polyesters, propylene-based polymers, and styrene-based polyethers. Among them, aliphatic polyethers, aliphatic polyesters, propylene-based polymer organic polymers (B), and silica precursors have a good range of about 10 nm or less in size because the thermal decomposition products are decomposed and volatilized. It is suitable to form a porous having an average pore diameter of 10 nm or less. In addition, dendrimers and star clusters are preferred as those having a branched structure as a primary structure. When used, the occupied volume of the polymer becomes small, so that porosity with a diameter of 1 nm or less can be easily obtained. The number of thermally decomposable polymers is preferably 300 to 100,000. When the number average molecular weight is 500 to 20,000, the compatibility with the heat-resistant organic polymer shirt and silica precursor is good, and about 1 Onrn can be obtained. The following dimensions are suitable because the thermally decomposable polymer is porous with an average pore diameter of 1 Onm or less after decomposition and volatilization. The mass of the heat-resistant organic polymer (B) in the present invention: the mass of the silicon oxide (A) converted from the depolymerized polymer (hereinafter, referred to as the mass of the silicon oxide) is 5: 9 5 to 9 5: 5. When it is in this range, the chemical resistance and plasma resistance of the flexible nanocomposite film are good, and the organic polymer (B) will not be softened during thermal crosslinking to cause voids, and a sufficient porosity can be obtained. The above ratio is preferably 10:90 to. B) Sodium, fatty compounds, etc. are heat-resistant and polymerizable, so branched compounds such as compounds have an average average pore average score. In the range of 1 (B), complete water conversion oxygen is formed. Porosity is eliminated due to heat resistance. 9 0 ·· 10 -16- (14) (14) 200400238 is particularly preferred. In order to obtain a sufficient porosity, the amount of the component (c) in the present invention is preferably 5% by mass or more relative to the total mass of the heat-resistant organic polymer (B) and the converted sand oxide mass. In addition, in order to maintain sufficient mechanical properties, it is desirable that the total weight of the heat-resistant organic polymer (B) and the total mass of the converted oxidized sand is 3,000 mass% or less. The amount of (C) is particularly preferably from 10 to 200% by mass. In order to make the range size of the heat-resistant organic polymer (B) and silicon oxide (A) in the present invention be 1 Onm or less, and to make the average pore size in the present invention 1 Onm or less, at least two or more are selected. Between the heat-resistant organic polymer (B) and the silicon oxide precursor (a), between the heat-resistant organic polymer (B) and the component (C) (b), and between the silicon oxide precursor and the component (C) ( c) The clusters' preferably have intermolecular interactions. Inter-molecular interactions include, for example, covalent bonds, ionic bonds, hydrogen bonds, r-7Γ interactions, coordination compound formation, and electrostatic interactions. With at least two groups selected from (a), (b) and (c) above, intermolecular interactions due to covalent bonds or hydrogen bonds are particularly preferred. When there are related intermolecular interactions, the separation of each component can be suppressed, and the size of the range becomes smaller. As a result, a porous nano-composite film having excellent mechanical properties, plasma resistance, and chemical resistance can be obtained. As the intermolecular interaction 'between the heat-resistant organic polymer (B) and the silica precursor (a)', covalent bonds are preferred. Because the two are covalent bonds, the mechanical properties of the porous nanocomposite film can be improved. The method for making the two covalently bonded is as long as the heat-resistant organic polymer (B) and the oxidized -17 · (15) (15) 200400238 silicon precursors have i or more functional groups that can react with each other. Known techniques are applicable. Specific examples include, for example, introduction of an alkoxysilyl group into a heat-resistant organic polymer (B), mixing with a silica precursor, or synthesis of a silica precursor with the heat-resistant organic polymer (B ) — A method for forming a siloxane by performing a hydrolysis reaction, and introducing an alkenyl group or an alkynyl group into the heat-resistant organic polymer (B) to react with a precursor of a sand oxide containing a Si-H group (hydroxylation) , Hydroxylation) and so on. Among them, the method of introducing an acetylene group into a heat-resistant organic polymer (B) and reacting with a silicon oxide precursor containing a Si-H group is particularly preferable. As the intermolecular interaction between the heat-resistant organic polymer (B) and the component (C) (b), a covalent bond or a hydrogen bond is preferred. The method may be any of various well-known methods. Hereinbelow, the use of a thermally decomposable polymer as a component (C) is described as an example. The heat-resistant organic polymer (b) and the thermally decomposable polymer are based on a method for imparting intermolecular interaction by a covalent bond. United. For the block or cross-linking method, a known method is applicable. For example, a method using a thermally decomposable polymer having a site capable of reacting or copolymerizing with a heat-resistant organic polymer (B) in a molecule, using a site having a site capable of initiating polymerization of a thermally decomposable polymer, or using thermal decomposition A method of heat-resistant organic polymer (B) at a site where a polymer is reacted or copolymerized. As a specific example, for example, based on the synthesis of a heat-resistant organic polymer (B) containing a hydroxyl group on a branched chain, and using the hydroxyl group as a starting point, ethylene oxide, propylene oxide, and ε-caprolactone are ring-opened. Polymerization to obtain a heat-resistant organic polymer (B) such as a cross-linked aliphatic polyether or aliphatic polyester. • 18- (16) (16) 200400238 The intermolecular interaction between the silicon oxide precursor and the component (c) (c) is preferably a covalent bond or a hydrogen bond. When the silicon oxide precursor has a silanol (Si-OH) group, hydrogen bonding is preferred, and as the component (c), it is preferable to use a compound containing a hydrogen bondable site containing a hydroxyl group, a carbonyl group, and the like. As the above-mentioned intermolecular interaction, it is preferable to have a covalent bond on (a) or (b), especially a covalent bond on (a) or (b), and it is best to have a hydrogen bond on (c). . The porous nanocomposite film of the present invention is obtained by removing the above-mentioned component (C) after forming a film from a composition containing a heat-resistant organic polymer (B), a silica precursor, a component (C), and a solvent. The composition may be formed by mixing the components, but it is a reaction product that allows the heat-resistant organic polymer (B) to react with the silicon oxide precursor through a covalent bond in advance, or via a The valence bond is suitable to make the reaction product of the component (C) and the silicon oxide precursor complete the reaction. Specifically, the method for preparing the composition may include, for example, ① a method in which a heat-resistant organic polymer (B) synthesized in advance and a precursor of silica are mixed with the component (c) and a solvent, ② will be synthesized in advance The method of mixing the heat-resistant organic polymer (B) with the component (C), the method of mixing with the silica precursor and the solvent, and ③ completing the formation of the heat-resistant organic polymerization in the presence of the component (C) and / or the solvent (B) and the oxidation, sand precursor reaction method. After forming a thin film from this composition, it is preferable to gel the silica precursor and fix the silica before removing the component (C). As the above-mentioned solvents, the three components of the heat-resistant organic polymer (B-19 · (17) (17) 200400238), the precursor of silicon oxide, and the component (C) are dissolved or dispersed, as long as it is necessary to prevent The method is only required to obtain a thin film having a desired film thickness, uniformity, or buried flatness, and is not particularly limited. Examples include aromatic hydrocarbons, dipolar aprotic solvents such as' ketones, esters, Ethers and halogenated hydrocarbons. Examples of the aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, tetralin, and methylnaphthalene. Examples of dipolar aprotic solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, T-butyrolactone, and Methyl Yashuo et al. Examples of the ketones include methyl isobutyl ketone, cyclopentanone, cyclos-one, cycloheptanone, cyclooctanone, and methylpentyl ketone. Examples of the ethers include tetrahydrofuran, pyran, dioxane, dimethoxyethane, diethoxyethane, diphenyl ether, anisole, phenyl ether, diethylene glycol dimethyl ether (diglyme ), Triglyme, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. Examples of the esters include ethyl lactate, methyl benzoate, ethyl benzoate, butyl benzoate, benzyl benzoate, Methyl Cellosolve Acetate, and ethyl cellosolve And two hydrazine monoethyl ether acetate. Examples of the halogenated hydrocarbons include carbon tetrachloride, chloroform, digas Φ ^, tetrachloroethane, chlorobenzene, and dichlorobenzene. The total concentration of the heat-resistant organic polymer (B), oxidized sand (A) (calculated silicon oxide mass), and the concentration of the component (C) is 1 to 80% by mass, and more preferably 5 to 60% by mass. -20-(18) (18) 200400238 The method for forming a thin film is preferably a method of coating on a suitable substrate. For example, the spin coating method, the dipping coating method, the spray coating method, such as the 'compression coating method, the strip coating method, the doctor blade coating method, the extrusion coating method', the scanning coating method, the brush coating method, and the potting method, etc. Know the coating method. When used as an insulating film for electronic components, a rotation coating method and a scanning coating method are preferred from the viewpoint of uniformity of the film thickness. The thickness of the film is preferably 0.01 to 50 // m, and more preferably 0.1 to 30 # m. The gelation of the silicon oxide precursor is performed according to the polymerization reaction of the Si-OH group, Si-OR group, and / or Si-H group in the precursor. Examples of the method for carrying out the polymerization reaction include a heating method and a method of exposure to an environment containing an alkaline catalyst and water. In the case of gelation by heating, in order to fully gelate, the temperature is preferably 50 ° C or higher, preferably 10 ° C or higher, and more preferably 150 ° C or higher. Exposure to alkali The method of environmental catalyst and water environment is especially suitable for the polymerization reaction of Si-H group. As the basic catalyst, ammonia, ammonium hydroxide and amines are suitable. As the amines, primary amines and secondary amines can be used. Amine and tertiary amine. Specific examples include methylamine, ethylamine, butylamine, allylamine, dimethylamine, diethylamine, trimethylamine, and triethylamine. It is advisable to perform the polymerization reaction by exposing to the environment containing alkaline catalyst vapor and water vapor as described above. The method of removing the component (C) is preferably heating or electromagnetic wave irradiation as described above. It is preferred to use heating and electromagnetic waves. The irradiation is suitable. The environment of heating and / or electromagnetic wave irradiation may include inert gas environments such as nitrogen and argon, etc. -21 · (19) (19) 200400238, air, oxygen, and reduced pressure, etc. Decompression is preferred. Heating conditions are from 2 to 120 minutes at 2 0 to 4 5 0 ° C. It is suitable, at 300 to 42 5 ° C, especially for 2 to 60 minutes. In order to control the gelation reaction speed of the silicon oxide precursor and the speed of removing the component (C), or to ensure the smoothness of the surface of the coating film Or it is better to improve the embedding of the fine space of the coating film, and it is better to add a preliminary heating step of about 50 to 350 ° C, or to divide the heating step into several steps. As the electromagnetic wave irradiation conditions, for example, when using an electron beam, the irradiation The energy is preferably from 0.1 to 50 keV, and the irradiation dose is preferably from 1 to looG ^ c / cm2. When the component (C) is removed by heating, the polymerization reaction of the gelled silica precursor proceeds further, forming the above formula (1) The silicon oxide skeleton represented by this step. According to this step, a silicon oxide phase without Si-OH groups and Si-OR groups or very few silicon oxide phases is formed. Because of low permittivity, high mechanical strength, and hydrophobicity, In addition, when the heat-resistant organic polymer (B) has a self-crosslinking functional group due to heat, the functional group undergoes a cross-linking reaction to improve the heat resistance and chemical resistance of the heat-resistant organic polymer (B) phase. Therefore, it is suitable. Organic polymer (B), silica precursor, component (C), and solvent composition system should be refined by methods such as neutralization, reprecipitation, extraction, and filtration. For electronic parts related applications, polymerization catalysts Metals such as potassium or sodium, and free halogen atoms are the substances that cause the malfunction of the transistor or the corrosion of the wiring, so it is advisable to fully refine it. -22- (20) (20) 200400238 As the porosity of the present invention The applications of nano composite films include various battery film materials such as various insulation films, protective films, and fuel cells, photoresist, antireflection film, light guide materials, coating materials, electronic parts, sealants, and protective agents. , Transparent film materials, adhesives, fiber materials, weather-resistant coatings, water repellents, oil repellents, moisture-proof coatings, etc. In particular, the use of an insulating film for electronic components or an insulating film for multilayer wiring boards is preferred. Examples of the electronic component include individual semiconductors such as a secondary body, a transistor, a compound semiconductor, a thermistor, a varistor, and a thyristor, DRAM (dynamic random access memory), SRAM (static random access memory), Memory components, microprocessors, DSPs, such as EPROM (Erasable Read Only Memory), Masked ROM (Fixed Program), EEPROM (e.g., Read Only Memory that can erase programs and input programs electronically) and Flash memory products (Digital signal processor), ASIC (special application integrated circuit), theoretical circuit components, compound semiconductor components such as MMIC (monolithic microwave integrated circuit), integrated integrated circuit (hybrid integrated circuit) (hybrid integrated circuit) , Photoelectric conversion elements such as light-emitting diodes and charge-binding elements. The so-called multilayer wiring board refers to various substrates on which electronic components and the like are actually mounted, and examples thereof include high-density wiring boards such as printed wiring boards, buildup wiring boards and MCM (multi-chip module). Examples of the insulating plate include a buffer buffer film, a passivation film, an interlayer insulating film, and an α-particle barrier coating. The porous nano-composite thin film of the present invention is preferably compounded with other films -23- (21) (21) 200 400 238 ° W 'Applicable to semiconductor element passivation film or interlayer insulating film for semiconductor elements' for porous nano-composite It is preferable to form an inorganic film on the lower layer and / or the upper layer of the film. {Zhuwei inorganic film, a film formed by atmospheric pressure, reduced pressure, or plasma chemical vapor growth (cvd) method or coating method, for example, can be coated on a silicified film, and phosphorus or boron can be applied as required, The so-called PSG film or BPSG film, silicidated film, silicon nitride film, silicidated nitride film, Si OC film, and spin-on-glass (SOG) film. This invention: The porous nano-composite thin film of the invention and the metal wiring are formed into an inorganic film, and the metal wiring can be easily prevented from being peeled off and the damascene shape can be easily etched. The inorganic film is preferably formed on the porous nano-composite film by partially removing the porous nano-composite film according to the etching method or the CMP method. On the upper layer of the porous nano-composite film of the present invention, if the adhesion between the porous nano-composite film and the inorganic film is insufficient when the inorganic film is formed, or when the photoresist is removed after the etching process, the film may be damaged due to oxygen polishing. When possible, the surface of the porous nanocomposite film is preferably treated with energy rays. As the energy line treatment, for example, a broad electromagnetic wave including light, that is, UV light irradiation, laser light irradiation, microwave irradiation, or the use of electron beam processing, that is, electron beam irradiation, glow discharge treatment, corona discharge treatment, and plasma Processing, etc. Among them, the processing method suitable for the mass production step of the semiconductor element may include, for example, UV light irradiation, laser light irradiation, corona discharge treatment, and plasma treatment. Plasma treatment is particularly suitable because it causes less damage to the semiconductor element. As -24- (22) 200400238, a plasma processing device, the required gas can be introduced into the device, as long as an electric field is applied. There are no special restrictions. Commercially available barrel and plate type plasma generators are Suitable for use. The introduction of the plasma body is not limited as long as it can effectively treat the surface, and examples thereof include argon, ammonia, nitrogen, oxygen, and a mixed gas thereof. Nitrogen treatment is suitable on the outermost surface of the porous nanocomposite thin film to form an activated layer, which prevents damage to the film caused by oxygen polishing when removing the photoresist, so it is suitable. [Embodiments] Examples The present invention is specifically explained by the following examples and comparative examples. The present invention is not limited to these. Examples 1 to 14 are synthesis examples, Examples 15: 29 and 30 are examples, and Examples 25 to 28 are comparative examples. In addition, the molecular weights in Examples 1 to 13 are based on the number-average molecular weight of polybenzene measured by a gel liquid chromatography (GPC) using tetrahydrofuran. [Example 1] Synthesis of heat-resistant organic polymer In a flask with a capacity of 1 L, put 18, · 90 g of perfluoro (5-triphenylbenzene), 8.32 g of 4-monophenylethynyl nonafluoro 3.78 g of 1,3,5-trihydroxybenzene and 279 g of N, N · dimethylamine (hereinafter, referred to as DMAc). Heat the oil bath to 6 ° C while stirring (at TC, add 2 7.3 g of potassium carbonate quickly 'and continue to stir as long as it can be made in a flat and horizontal position, and the effect of gas-plasma dense nitrogen damage can be achieved, but this g 24. Diene and acetofluorene are converted into olefin in the solvent. When the solution is mixed, heat at -25- (23) 200400238 60 ° C for 4 hours. After that, cool the reaction solution to room temperature, and slowly add vigorously stirring When 2 L of pure water / methanol containing about 30 g of acetic acid (capacity ratio is about 1/1), a white powder precipitates. The white powder is filtered, washed with pure water 5 times, and then at 8 CTC When vacuum drying was performed for 15 minutes, a white powdery polymer (hereinafter referred to as P 1) was obtained. The molecular weight of P 1 was approximately 5,000. [Example 2] The heat-resistant organic polymer was synthesized at a capacity of 100. In a ml flask, 2.35 g of 3,3'-hydroxydi-1,4-phenylene) bis (2,4,5-triphenylcyclopentanedione) and 1.14 g of 1,3, 5-Tris (phenylethynyl) benzene and 8. of 7-butyrolactone, heated in a nitrogen atmosphere at 200 ° C for 48 hours. However, to about 100 ° C, cyclohexanone was added so that the solid content concentration became mass%, and a polymer solution with a molecular weight of about 6,000 (hereinafter, P 2) was obtained. [Example 3] Synthesis of heat-resistant organic polymer In a flask with a capacity of 1 L, 18.90 g of perfluoro (1,3 5-triphenylbenzene), 10.72 g of pentafluorodiphenylacetylene, 5.04 g of 1,3 5-trihydroxybenzene and 312 g of DM Ac. Warm on the oil bath while stirring. When the liquid temperature reaches 60 ° C, quickly add 36.4 g of potassium carbonate, continue to stir at 6 ° C, and heat for 4 hours. After that, cool the reaction solution to room temperature and slowly add When vigorously stirring about 1 L of 1 N hydrochloric acid aqueous solution, a white powder precipitated. The white powder was filtered, and then washed with pure water. 5 Slow build-up product (ene 5g cold 20 called color number -26- (24) (24) 200400238, and then vacuum-dried at 80 ° C for 15 hours to obtain a white powdery polymer (hereinafter referred to as P3). The molecular weight of P3 is about 3,500. [ Example 4] Synthesis of silica precursors In a 100 ml flask, 5.00 g of triethoxysilane, 16.40 g of methyltrimethoxysilane, and 39.07 g of cyclohexanone were placed in a flask. While vigorously stirring at a warm temperature, 6.68 g of a 1% aqueous maleic acid solution was added dropwise over about 40 minutes. After the dripping was completed, the mixture was heated at 60 ° C for 2 hours. After that, it was concentrated to 48.8 using an evaporator. g, and a silicon oxide precursor (hereinafter, referred to as S1) having a solid content concentration (in terms of complete hydrolysate) of 20% by mass was obtained. It is 1,200. [Example 5] Synthesis of silica precursors In a 200-ml flask, 8.02 g of tetramethoxysarane, 2 5.66 g of methyltrimethoxysilane, and 63.6 4 g of propylene glycol were placed. Monopropyl ether. While vigorously stirring at room temperature, a 1% maleic acid aqueous solution (12.70 g) was added dropwise over about 50 minutes. After the dropwise addition was completed, the mixture was heated at 60 ° C for 2 hours. Using an evaporator, it is concentrated to a total weight of 7 7 · 8 g, and a oxidized stone precursor (hereinafter, referred to as S2) having a solid content concentration (completely hydrolyzed product conversion) of 20% by mass is obtained. The molecular weight is 1, 000. [Example 6] Synthesis of thermally decomposable polymer In a 50-ml flask, 1.24 g of ethylene glycol, 22.82 g of ε-caprolactone, and 0.02-lg of 2-ethylhexanoic acid were placed. Tin. Heated under nitrogen-27- (25) (25) 200400238 environment at 120 ° C for 20 hours to obtain polycaprolactone (hereinafter referred to as D1) having two hydrocarbon groups as intramolecular terminal groups. ). The molecular weight is about 1520. [Example 7] Synthesis of thermally decomposable polymer instead of ethylene glycol, use 2.2 7g of 2,2-bis (via methyl) -1 Except for propylene glycol, in the same manner as in Example 6, polycaprolactone (hereinafter, referred to as D2) having * hydrocarbon groups as intramolecular terminal groups was obtained. The molecular weight was about 1,100. [Example 8] Thermal decomposition Polymer synthesis was replaced by ethylene glycol, and 1.89 g of ethylene glycol mono-tert-butyl ether was used instead. In the same manner as in Example 6, polycaprolactone (hereinafter, Called D3). The molecular weight is about 1,700. [Example 9] Synthesis of a reactant of a heat-resistant organic polymer and a silica precursor The solution of 0.5 0 g of the polymer P 1 obtained in Example 1 in a cyclohexanone solution of 2 · 8 5 g, and 5 · 10 g of the silicon oxide precursor solution S 1 obtained in Example 4 was placed in a flask with a capacity of 25 m 1, and the system was replaced with nitrogen. To this was added 3 " 1 bis vinyl tetra and siloxane platinum complex (3% toluene solution), and heated at 70 ° C for 2 hours. Then add 4 divinyltetrasiloxane platinum complex (3% toluene solution), and heat at 75 ° C for 1 hour to obtain a reactant solution of a heat-resistant organic polymer and a precursor of silicon oxide ( Hereinafter, it is called PS 1). -28- (26) (26) 200400238 [Example i 〇] Synthesis of reactant of heat-resistant organic polymer and silica precursors 5.00 g of polymer P2 obtained in Example 2 and 5.00 g of The silicon oxide precursor solution s 1 obtained in Example 4 was placed in a flask having a capacity of 25 m 1 'and replaced with nitrogen in the system. To this, add 5 " 1 bis vinyl tetrasarane platinum complex compound (3% toluene solution) at 7 5. (: 'Heating for 2 hours' to obtain a reactant solution of a heat-resistant organic polymer and a silica precursor (hereinafter, referred to as p S 2). [Example 1 1] A heat-resistant organic polymer and a silica precursor Synthesis of Reactants Dissolve 3.0 g of the polymer P 3 obtained in Example 3 in 17 g of toluene ′ and 0.59 g of triethoxysilane, and place them in a 50 ml flask. The system is replaced with nitrogen. . To this, add 210 bisvinyltetrasiloxane platinum complex (3% toluene solution), and heat at 80 ° C for 2 hours. After cooling, slowly put the reaction solution into the excess The obtained white powder was dried under vacuum at 80 ° C for 15 hours to obtain a triethoxysilyl-containing polymer (hereinafter, referred to as P4). 0.95 g of Polymer P4, 1.2 g of tetraethoxysilane, 3.68 g of methyltriethoxysilane, and 20 g of hexanone were put into a 100 ml flask and stirred at room temperature to form a homogeneous solution. While vigorously stirring at room temperature, 1.57 g of a 1% aqueous maleic acid solution was added dropwise over about 40 minutes. After dripping, Heat at 60 ° C for 2 hours, and then use an evaporator to concentrate to a total weight of 14.8 g to obtain a reactant solution of a heat-resistant organic poly-29- (27) (27) 200400238 compound and a silica precursor (Hereinafter, referred to as PS3.) [Example 12] Synthesis of a reactant of a heat-resistant organic polymer and a thermally decomposable polymer The polymer D 3 obtained in Example 8 of 2 5.1 1 g was dissolved at 10 0.4 g of tetrahydrofuran was put into a flask with a capacity of 300 ml. 10.3 g of pyridine, 20.99 g of hexamethyldisilazane, and 14.1 g of trimethyl chloride were added to the flask. In a nitrogen atmosphere, 50: (:, reaction for 20 hours. After distilling off the volatile components, 78.9g of dichloromethane is added to dissolve. The filter paper is used for suction filtration to remove insoluble components. After distilling off the volatile components, the end has three Polymethylcaprolactone of methylsilyloxy. Dissolve 2.5g of this polycaprolactone and 2.5g of polymer P1 obtained in Example 1 in 20g of dimethylformamide, and put it in a volume of 50ml. Into a flask, add 0.7 5 g of fluorinated shaver, and heat under nitrogen at 70 ° C for 4 hours. After cooling, add 8.0 g of trifluoroacetic acid and stir at room temperature for 10 hours. Put a large amount of about 0.1 N hydrochloric acid aqueous solution to recover the white powdery polymer, and proceed at 80 ° C. Vacuum drying for 12 hours to obtain a reaction product of the heat-resistant organic polymer and the thermally decomposable polymer (hereinafter referred to as PD1). [Example 1 3] A reaction product of the heat-resistant organic polymer and the thermally decomposable polymer Synthesis: 3.0 g of the polymer PI obtained in Example 1, 0.78 g of 2- (4- 30- (28) (28) 200400238 hydroxyphenyl) ethanol, and 27 g of DMAc were placed in a 50 ml flask. , At 60 ° C, stir to a homogeneous solution. At this temperature, 1.2 g of potassium carbonate was added in one portion, and the mixture was continuously heated at 60 ° C with stirring for 6 hours. After cooling, a large amount of about 1N hydrochloric acid aqueous solution was put in to recover a white powdery polymer, and vacuum-dried at 8 ° C for 12 hours to obtain a polymer having a primary hydrocarbon group in the molecule. 0.6 g of the present polymer was polymerized Substance, 1.8 g of ε-caprolactone and 0.004 g of 2-ethylhexanoate, were placed in a 20 ml flask. Under a nitrogen atmosphere at 120 ° C, heated for 20 hours to obtain A polymer of polycaprolactone (hereinafter, referred to as PD2) is crosslinked on the heat-resistant organic polymer P1. The molecular weight is 10,000. [Example 1 4] Heat-resistant organic polymer in the presence of a thermally decomposable polymer Synthesis of reactant with silica precursor: 1,000 g of polymer P4 obtained in Example 11; 3.47 g of tetraethoxysilane; 1.0 g of polymethyl methacrylate (manufactured by Aldrich) (Molecular weight is about 15,000) and 12 g of methyl isobutyl ketone are put into a 50 ml flask and 'stirred into a homogeneous solution at room temperature. Then add 20 g of a 0.01% aqueous maleic acid solution' to the chamber. Stir vigorously at room temperature for about 1 hour. After that, separate the methyl isobutyl ketone layer and use an evaporator. Concentrated to a total weight of 15 g 'to obtain a reactant solution containing a thermally decomposable polymer' a heat-resistant organic polymer and a silica precursor (hereinafter referred to as PSD 1-31-(29) 200400238 [Example 15] The reactant solution PS 1 of the heat-resistant organic silicon precursor obtained in Example 9 at 100 parts by mass (the mass of the heat-resistant organic poly-oxide sand is 3: 7, and the total solid concentration is 1 8 dissolved 1 2.6 parts by mass The thermally decomposable polymer obtained in Example 6 is a composition having a composition ratio shown in Table 1. Here, the silicon oxide mass is converted before the silicon oxide. The composition is filtered with a pore size of 0.2 m, and filtered in 4 inches of silicon. Rotate and spray on the circle to form a thin film. Perform heating at 150 ° CX for 180 seconds on a hot iron plate, and then heat (firing) in a vertical furnace at 425 ° CX 1 The results of the following evaluations were performed on the obtained poly films, as shown in Table 1. Permittivity: SSM-495 manufactured by SSM Corporation, cyclic voltammetry into the probe (cyclic voltammetry; CV out of 1MHz) Permittivity. The thickness of the film is calculated using the spectroscopic ellipse. Mechanical strength: DCM-SA2 hardness test method (na η 〇indentati ο η) made by MTS company is used to measure the elastic modulus._Average pore diameter: ATX-G manufactured by Rigaku Electric Co., Ltd., and X-ray scattering are used to determine the Average, pore diameter. In addition, the phase structure of the film above 30 nm was observed by scanning electron microscopy based on the cross section of the film. The refractive index 値 of the film when the spectroscopic ellipse pair was at 63 nm was 1.28. It does not contain thermally decomposable polymer D1, only from PS 1, based on the same polymer and oxygenate: converted mass%), 3 D1, made of PTFE used as flooding system: 5 5 Onm 2 5 0 ° CX 1 At 80 hours, the nitrogen porosity nanometers were re-measured based on mercury), and the circular thickness gauge was determined, based on the nanometer t. According to the observation with a small-angle mirror, it was not calculated. On the other hand, the coating conditions of -32- (30) (30) 200400238 have a refractive index of 1. 4 3. The decrease in the refractive index indicates that the air phase (refractive index 値 1) exists in the film, that is, the formation of porosity, and the porosity is 35% calculated as described below. (1.43— 1.28) + (1.43— 1) χ 1 0 0 = 3 5 [Examples 16 to 28] Using the raw materials shown in Table 1 with the composition ratio shown in Table 1, the precursor containing silicon oxide was adjusted A composition of heat-resistant organic polymer, thermally decomposable polymer and solvent. In Examples 2 and 7, cyclohexanone was used as a solvent. From these compositions, a thin film was formed in the same manner as in Example 15 to evaluate the film characteristics. In addition, the solid content concentration and the number of rotations of the composition are adjusted so that the film thickness falls within a range of 400 to 700 nm. Adjust the solids concentration of the composition. When dilution is required, use cyclohexanone as the dilution solvent. The results are shown in Table 1. When the cross-sections of the thin films obtained in Examples 16 to 27 were observed with a scanning electron microscope, a phase structure of 3 nm or more was not observed. In addition, although the composition of Example 2 8 was uniform and transparent, when the coating was rotated, it was observed that the film was rough and turbid due to phase separation above the // m class, and the characteristics of the film could not be evaluated. Is not evaluable). -33- (31) (31) 200400238 Table 1 Raw material composition ratio (mass) Coating characteristics Silicon dioxide precursor Heat-resistant organic polymer Thermal decomposition polymer Permittivity modulus of elasticity (GPa) Average pore size (nm) Example 15 PS1, D1 7 3 7 2.0 4.2 2 Case 16 PS 1, D1 7 3 10 1 .7 4.0 3 Case 17 PS2, D2 5 5 7 1.8 4.1 2 Case 18 PS3, D2 7 3 5 1 .9 4.5 2 Case 1 9 S2, PD1 7 3 3 2.2 5.8 1 case 20 S2, PD1 5 5 5 2.1 5.1 2 case 21 S2, PD1 3 7 7 1.8 4.5 2 case 2 2 S2, PD2 7 3 9 1.7 3.8 3 case 23 SI, PD2 7 3 9 1.8 4.0 2 cases 24 p SD 1 5 5 5 2.0 6.2 2 cases 25 SI, D2 10 0 5 2.2 2.0 5 cases 26 SI, D2 10 0 10 1 .7 1 .0 10 cases 27 PD 1 0 10 10 2.5 2.5 2 Example 28 P1, S 1, D2 7 3 7 Non-evaluable [Example 2 9] As the δ level estimation of the layer 闾 insulation （(stability of the laminated structure) According to the solution composition adjusted in Example 19, use the following In this way, a laminated film of silicon circle / P-SiO (300 nm) / porous nano composite film (500 nm) and p-SiN (50 nm) / p-Si0 (500 nm) was prepared. -34- (32) (32) 200400238 A spin coating solution was formed on a silicon circle forming a ρ-SiO film (thickness of 300 nm) to form a porous nano-film having a thickness of 500 nm as in Example 14. Rice composite film. Next, a 50 nm silicon oxide nitride film was formed under a mixed gas of monosilane, ammonia, and nitrogen, and then a 500 nm-thick oxide sand oxide film was formed under a mixed gas of monosilane and oxygen dinitride. The obtained laminated film was grilled under hydrogen atmosphere at 425 ° C for 60 minutes. When the resistance to fracture due to thermal pressure was investigated under a metal microscope, no fracture or other defects occurred. [Example 3 0] Evaluation as an interlayer insulating film (fine processing and chemical resistance) According to the solution composition adjusted in Example 19, it was spin-coated under the same conditions as in Example 14 and formed on a silicon circle to form a film. Porous nano composite film with a thickness of 40 Onm. A photoresist is formed thereon, and a photolithography method is used to form a overlay, and then a reactive ion saturation method (RIE, Reactive Ion Etching) using a nitrogen / hydrogen / argon mixed gas is used to perform porous nanocompositing. Etching of thin films. When the coating film after the washing step with the photoresist stripping solution EKC265 (trade name, manufactured by EKC) was examined with a metal microscope, no defects were observed. In addition, the display permittivity 値 is 2 · 1 ′ and there is no difference between 电容 immediately after film formation. That is, it was confirmed that the fine processing and photoresist removal steps did not cause damage to the porous nano and composite films. Industrial Applicability The porous nanocomposite film of the present invention has a low permittivity and is excellent in mechanical properties expressed by elastic modulus of -35- (33) (33) 200400238. The porous nano-composite thin film is used as an insulation film for electronic components and an insulation film for multilayer wiring boards in the manufacturing steps of the insulation film for electronic components and the insulation film for multilayer wiring boards. Excellent applicability.
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