200903173 九、發明說明 【發明所屬之技術領域】 本發明係關於經由在基板上塗佈硬化’形成具有矽和 氧鍵結之膜的塗佈液，令其在室溫或以上之溫度下的保存 安定性提高。又，係關於半導體裝置之製造步驟中，可用 於形成光阻膜形成前所設置之光阻下層膜的塗佈液。 【先前技術】 包含令特定之至少二種烷氧基矽烷化合物，於水和觸 媒存在下於特定之有機溶劑中進行水解所得之具有矽烷醇 基（Si-OH鍵）之化合物的形成被膜用塗佈液爲已知（參 照專利文獻1)。二個矽烷醇基爲縮合形成Si-0-Si鍵， 成爲具有Si-O-Si鍵的聚合物。 又，作爲半導體基板上所形成的光阻下層膜，已知使 用有機基聚矽氧烷的硬化膜（參照專利文獻2)。該硬化 膜爲以光阻之圖型作爲光罩，並使用CF4氣體予以乾式蝕 刻。其後’除去該光阻之圖型時，可令該硬化膜殘存。 此類塗佈液所要求的特性之一，可列舉保存安定性。 即，要求即使於室溫經過一定時間，亦不會引起塗佈液之 化學性變化及物理性變化。於專利文獻1中，記載使用二 價醇之單醚或二價醇之二醚作爲溶劑的塗佈液，於膠化上 需要的日數爲1 00日以上，比使用二價醇作爲溶劑之例的 保存安定性更爲優良。 於專利文獻3中，記載根據使用溶液狀之光阻下層膜 -5- 200903173 用組成物所形成之被膜膜厚增加率，評價溶液之保存安定 性的結果。評價實施例1至4及比較例1爲保存安定性良 好，比較例2爲保存安定性不良。其次，比較例2中，所 用之溶劑爲蒸餾醋酸丁醋此點，與使用蒸餾丙二醇單丙醚 作爲溶劑之實施例1至4及比較例1不同，指出溶劑的差 異乃對於溶液的保存安定性造成影響。 於專利文獻4中，記載經由使用具有羥基且沸點爲 1 1 0〜1 3 0 °C之丙二醇單甲醚或丙二醇單乙醚作爲溶劑，取 得具有優良塗佈性，且具有良好之保存安定性的光阻下層 膜用組成物。 專利文獻1 :特開平3-045 5 1 0號公報 專利文獻2 :特開平2- 1 03052號公報 專利文獻3 :特開200 1 -022083號公報 專利文獻4 :特開2002-040668號公報 【發明內容】 (發明所欲解決之課題） 經由水解及縮合反應所製造之包含具有矽烷醇基之聚 合物的形成被膜用塗佈液中，易硬化者乃具有保存安定性 差的課題。此類形成被膜用塗佈液’根據膠滲透層析（以 下，於本說明書中簡稱爲GPC)測定的分子量分佈爲依據 該塗佈液之保存期間而顯示出變化。其主要原因認爲係因 即使未以熱板等之加熱手段予以加熱’於室溫下亦慢慢進 行矽烷醇基的縮合反應。爲了抑制矽烷醇基的縮合反應， -6- 200903173 乃考慮予以冷藏保存，但費用比室溫下保存高。所謂GPC ，係利用高分子化合物的稀薄溶液若通過已充塡多孔質膠 之柱，則由分子尺寸大者依序溶出，係爲測定高分子化合 物之分子量分佈及相對分子量的方法。 使用此類保存安定性差之形成被膜用塗佈液時，即使 於基板上形成被膜時的條件相同，亦察見所用塗佈液之保 存期間愈長則所形成的被膜厚度變得愈厚之傾向。所謂同 一條件，係意指旋塗器的迴轉速度及迴轉時間、及熱板的 加熱溫度及加熱時間爲相同。 根據形成被膜用塗佈液之溶劑種類，矽烷醇基的份量 爲不同，保存安定性亦不同。若列舉具體例，則使用丙二 醇單甲醚醋酸酯（CH3OCH2CHCH3OCOCH3 )作爲溶劑之 形成被膜用塗佈液，經由加熱易硬化而具有室溫中之保存 安定性差的問題。丙二醇單甲醚醋酸酯中，矽烷醇基即使 於室溫之環境亦比Si-0-Si鍵之狀態難以安定存在，推測 係因保存安定性差之理由。 (解決課題之手段） 本發明係根據經由添加順型之二價羧酸（亦稱爲二羧 酸），例如順丁烯二酸、順-5-原冰片烯-內-2,3-二羧酸、 順-5-原冰片烯-外-2,3-二羧酸、順-1,2-環己烷二羧酸、順_ 4 -環己烯· 1，2 -二羧酸、順-環丁烷-1，2 -二羧酸、甲基順丁 烯二酸（檸康酸）、二甲基順丁烯二酸，提高形成被膜用 塗佈液的保存安定性。於本說明書中，順型之二價羧酸（ 200903173 二羧酸）爲經由脫水反應而變成酸酐的化合物。 (發明之效果） 本發明之形成被膜用塗佈液爲經由添加順型 酸（二羧酸），例如順丁烯二酸，比先前製品於 上之溫度（不超過35 °C )中的保存安定性優良。 用式 R1 (OCH2CHCH3) nOCOCH3(式中，R1 爲 子數1至4之烷基，η爲表示1或2)所示之有 爲溶劑，具有易硬化特性的形成被膜用塗佈液， GPC所測定之分子量分佈爲隨著保存期間的經過 化，於保存安定性方面無法令人滿足。但是’根 ，可取得易硬化特性和保存安定性兩者令人滿足 膜用塗佈液。 經由順型二價羧酸（二羧酸）之添加而提高 用塗佈液之保存安定性的理由’認爲係因順型之 (二羧酸）於有機溶劑中令矽烷醇基安定化’其 抑制矽烷醇基進行縮合反應。 本發明之形成被膜用塗佈液因不必冷卻保存 低保存及輸送費用。因爲於室溫或其以上之溫度 3 5。(：）下的保存期間中分子量分佈幾乎無變化’ 選擇比飛機之輸送費更爲便宜但耗費長時間之船 送手段。 【實施方式】 之二價羧 室溫或其 特別，使 表示碳原 機溶劑作 以往’依 而大爲變 據本發明 的形成被 形成被膜 二價羧酸 結果，可 ，故可減 (不超過 故例如可 舶等之輸 -8- 200903173 本發明之第一態樣爲包含具有Si-O-Si鍵，同時具有 矽烷醇基之聚合物、式1^( 〇CH2CHCH3) n0C0CH3 (式 中，R1爲表示碳原子數1至4之烷基’ η爲表示1或2) 所示之有機溶劑，可溶解順型之二價羧酸（二羧酸）之有 機溶劑及順型之二價羧酸（二羧酸）的形成被膜用塗佈液 〇 本發明之第二態樣爲包含具有Si-0-Si鍵，同時具有 有機基及矽烷醇基之聚合物、式 R1 ( OCH2CHCH3 ) n0C0CH3(式中，R1爲表示碳原子數1 至4之烷基，n爲表示1或2)所示之有機溶劑，可溶解 順型之二價羧酸（二羧酸）之有機溶劑及順型之二價羧酸 (二羧酸）的形成被膜用塗佈液。 上述聚合物，係爲式R2mSi ( OR3 ) 4_m (式中，R2爲 表示有機基，R3爲表示碳原子數1至4之烷基，m爲表示 〇、1或2 )所示之至少一種化合物之水解及縮合反應所得 之產物。 上述有機基可採用由芳基、烯基、烷基、羥烷基、環 氧基、胺基、醯基、丙烯醢基、甲基丙烯醯基、氫硫基所 組成群中選出至少一種之基或組合二種以上之基。芳基可 歹!J舉例如苯基、烯基爲具有碳彼此間之雙鍵之基，可列舉 例如乙烯基。烷基可列舉例如甲基、乙基、丙基、丁基。 所謂由組合上述群中選出二種以上之基，係包含該二種以 ±2基者’可列舉例如芳烷基。烷基可爲直鏈狀、分支狀 之任一者。 -9- 200903173 順型之二價羧酸（二羧酸），例如順丁烯二酸、順-5 -原冰片烯-內-2,3-二羧酸、順-5-原冰片烯-外-2,3-二羧酸等 爲幾乎完全不溶解於式R1 ( 〇CH2CHCH3) n0C0CH3 (式 中，R1爲表示碳原子數1至4之烷基，η爲表示1或2) 所示之有機溶劑，例如丙二醇單甲醚醋酸酯。因此，另外 需要令順型二價羧酸（二羧酸）溶解的溶劑。順型之二價 羧酸（二羧酸）爲溶解於水等之極性溶劑，但式 R1 ( OCH2CHCH3 ) n〇COCH3(式中，R1爲表示碳原子數1 至4之烷基，η爲表示1或2)所示之有機溶劑爲難溶解 於水。因此，令順型之二價羧酸（二羧酸）溶解之溶劑可 使用例如具有羥基的有機溶劑。 此類有機溶劑之具體例可列舉甲醇、乙醇、丙醇、丁 醇般之一價醇；乙二醇、二乙二醇、丙二醇、甘油般之多 價醇；及乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、 乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙 二醇單丙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單 乙醚、丙二醇單丙醚、丙二醇單丁醚般之多價醇之單醚類 。又，其他例可列舉乳酸乙酯等之光阻溶劑。若考慮對於 基板之塗佈性以外，則於具有羥基之有機溶劑中’以丙二 醇單丙醚（C3H7OCH2CHCH3OH )或丙二醇單甲醚（ CH3OCH2CHCH3OH)爲佳。 相對於形成被膜用塗佈液1〇〇質量份含有〇·〇ι質量 份以上之順型二價羧酸（二羧酸）爲佳’且相對於形成被 膜用塗佈液中之固形成分100質量份含有1質量份以上之 -10- 200903173 順型二價羧酸（二羧酸）爲佳。所謂固形成分，係爲塗佈 液中除去溶劑之成分。順型之二價羧酸（二羧酸）的濃度 上限’例如相對於形成被膜用塗佈液1 0 0質量份若爲1質 量份即可，且相對於形成被膜用塗佈液中之固形成分100 質量份若爲1 0質量份即可。 又，相對於形成被膜用塗佈液1 0 0質量份，上述固形 成分例如含有1質量份以上5 0質量份以下，且較佳爲1 質量份以上20質量份以下，式 R1 ( OCH2CHCH3) n〇COCH3(式中，R1爲表示碳原子數1 至4之烷基，n爲表示1或2)所示之有機溶劑爲例如含 有5質量份以上90質量份以下，可溶解順型之二價羧酸 (二羧酸）之溶劑爲例如含有5質量份以上90質量份以 下。相對於上述固形成分100質量份，具有前述矽烷醇基 之聚合物爲例如含有50質量份以上99質量份以下。 於本發明之形成被膜用塗佈液中，亦可再含有四級銨 鹽。四級銨鹽可列舉例如氯化苄基三乙基銨、氯化苄基三 甲基銨、氯化苄基三丁基銨、氯化四甲基銨、溴化四乙基 銨、氯化四乙基銨、溴化四丙基銨、溴化四丁基銨、氯化 三丁基甲基銨、氯化三辛基甲基銨、氯化苯基三甲基銨等 ，且可選擇例如氯化苄基三乙基銨。相對於上述固形成分 100質量份，四級銨鹽爲例如含有0·005質量份以上5質 量份以下。 本發明之第三態樣爲具有於基板上塗佈本發明之第一 態樣或第二態樣之形成被膜用塗佈液，硬化形成光阻下層 -11 - 200903173 膜之步驟、於該光阻下層膜上形成光阻膜之步驟，令該光 阻膜曝光、顯像形成光阻圖型之步驟及以該光阻圖型作爲 光罩’將該光阻下層膜予以乾式蝕刻之步驟之半導體裝置 的製造方法。 於上述基板’亦可形成具有絕緣性之膜（有機膜或無 機膜）’具有導電性之膜（金屬膜等）之至少一者，於此 情形中於此些膜上形成上述光阻下層膜。有機膜或無機膜 爲根據旋塗法於矽晶圓等之基板上塗佈後，硬化形成者爲 佳。上述半導體裝置爲包含使用矽晶圓等之半導體基板、 或玻璃基板或塑膠基板等之絕緣基板所製造的半導體元件 (二極管、電晶體等）、及使用該半導體元件所製造之電 子機器（行動電話機、電視受像機、個人電腦等）。 本發明之第四態樣爲包含使式R2mSi ( OR3 ) 4.m (式 中’ R2爲表示有機基，R3爲表示碳原子數爲1至4之烷 基，m爲表示0、1或2)所示之至少一種化合物於第一有 機溶劑中水解，再進行縮合反應，製作具有S i - Ο - S i鍵並 且又具有矽烷醇基之聚合物的步驟，至少令式R3 OH所示 之化合物經由蒸發除去（餾去）之步驟及添加式 R1 ( OCH2CHCH3 ) n〇COCH3(式中，R1爲表示碳原子數1 至4之烷基，η爲表示1或2)所示之第二有機溶劑，可 溶解順型二價羧酸（二羧酸）之第三有機溶劑、及順型之 二價羧酸（二羧酸）之步驟之形成被膜用塗佈液之製造方 法。 本發明之第五態樣爲包含使式R2mSi ( OR3 ) 4_m (式 -12- 200903173 中，R2爲表示有機基，R3爲表示碳原子數爲1至4之烷 基，m爲表示〇、丨或2)所示之至少一種化合物於第一有 機溶劑中水解，再進行縮合反應，製作具有si-〇-si鍵並 且又具有矽烷醇基之聚合物的步驟’至少使式R3〇H所示 之化合物經由蒸發除去（餾去）之步驟、添加式 R1 (OCH2CHCH3) n〇COCH3 (式中，Rl爲表示碳原子數1 至4之院基，η爲表示1或2)所不之弟一有機溶劑之步 驟及可溶解順型二價羧酸（二羧酸）之第三有機溶劑及順 型之二價羧酸（二羧酸）之步驟之形成被膜用塗佈液之製 造方法。 於蒸發除去之步驟前，進行添加前述第二有機溶劑， 例如丙二醇單甲醚醋酸酯（於1 0 1 _ 3 kP a之沸點爲約1 4 6 °C )之步驟爲有效，第一有機溶劑於101.3 kPa (大氣壓）之 沸點爲1 〇〇 °C以下，例如乙醇般之情況，爲特別有效。因 爲，經由蒸發，溶液爲過度濃縮，矽烷醇基之縮合反應過 度進行，其結果可防止消滅矽烷醇基。矽烷醇基之份量愈 少，則愈難令塗佈液硬化形成被膜。又，使用溶解於水之 酸作爲促進水解（及縮合反應）之觸媒時，於低極性溶劑 丙二醇單甲醚醋酸酯存在下並以減壓進行蒸發，則可輕易 除去該酸。 於上述式R2mSi ( OR3 ) 4.m中，R2可採用芳基、烯基 、烷基、羥烷基、環氧基、胺基、醯基、丙烯醯基、甲基 丙烯醯基、氫硫基所組成群中選出至少一種之基或組合二 種以上之基。芳基可列舉例如苯基，烯基爲具有碳彼此間 -13- 200903173 之雙鍵之基，可列舉例如乙烯基。烷基可列舉例如甲基' 乙基、丙基、丁基。所謂由組合上述群中選出二種以上之 基，係包含該二種以上之基者，可列舉例如芳焼基。病基 爲直鏈狀、分支狀之任一者。 上述式R2mSi ( OR3 ) 4 — m所示之化合物的具體例可列 舉四甲氧基矽烷、四乙氧基矽烷、四正丙氧基砂院、四異 丙氧基矽烷、四正丁氧基矽烷、四異丁氧基砍焼、四第一 丁氧基矽烷、四第三丁氧基矽烷、甲基三甲氧基砂院、甲 基三乙氧基矽烷、甲基三正丙氧基矽烷、甲基三異丙氧基 矽烷、甲基三正丁氧基矽烷、甲基三異丁氧基砍院、甲基 三第二丁氧基矽烷、甲基三第三丁氧基矽烷、乙基三甲氧 基矽烷、乙基三乙氧基矽烷、乙基三正丙氧基砂院、乙基 三異丙氧基矽烷、乙基三正丁氧基矽烷、乙基三異丁氧基 矽烷、乙基三第二丁氧基矽烷、乙基三第三丁氧基砂院、 正丙基三甲氧基矽烷、正丙基三乙氧基矽烷、正丙基二正 丙氧基矽烷、正丙基三異丙氧基矽烷、正丙基三正丁氧基 矽烷、正丙基三異丁氧基矽烷、正丙基三第二丁氧基较院 、正丙基三第三丁氧基矽烷、異丙基三甲氧基砂院、異丙 基三乙氧基矽烷、異丙基三正丙氧基砂院、異丙基三異丙 氧基砂烷、異丙基三正丁氧基矽烷、異丙基三異丁氧基矽 院、異丙基三第二丁氧基矽烷、異丙基二第二丁氧基矽烷 、正丁基三甲氧基矽烷、正丁基三乙氧基矽烷、正丁基三 正丙氧基矽烷、正丁基三異丙氧基砂院、正丁基三正丁氧 基矽烷、正丁基三異丁氧基矽烷、正丁基三第二丁氧基矽 -14- 200903173 烷、正丁基三第三丁氧基矽烷、第二丁基三甲氧基矽烷、 第二丁基三乙氧基矽烷、第二丁基三正丙氧基矽烷、第二 丁基三異丙氧基矽烷、第二丁基三正丁氧基矽烷、第二丁 基三異丁氧基矽烷、第二丁基三第二丁氧基矽烷、第二丁 基三第三丁氧基矽烷、第三丁基三甲氧基矽烷、第三丁基 三乙氧基矽烷、第三丁基三正丙氧基矽烷、第三丁基三異 丙氧基矽烷、第三丁基三正丁氧基矽烷、第三丁基三異丁 氧基矽烷、第三丁基三第二丁氧基矽烷、第三丁基三第三 丁氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷 、乙烯基三正丙氧基矽烷、乙烯基三異丙氧基矽烷、乙烯 基三正丁氧基矽烷、乙烯基三異丁氧基矽烷、乙烯基三第 二丁氧基矽烷、乙烯基三第三丁氧基矽烷、苯基三甲氧基 矽烷、苯基三乙氧基矽烷、苯基三正丙氧基矽烷、苯基三 異丙氧基矽烷、苯基三正丁氧基矽烷、苯基三異丁氧基矽 烷、苯基三第二丁氧基矽烷、苯基三第三丁氧基矽烷、二 甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二正丙 氧基矽烷、二甲基二異丙氧基矽烷、二甲基二正丁氧基矽 烷、二甲基二異丁氧基矽烷、二甲基二第二丁氧基矽烷、 二甲基二第三丁氧基矽烷、二乙基二甲氧基矽烷、二乙基 二乙氧基矽烷、二乙基二正丙氧基矽烷、二乙基二異丙氧 基矽烷、二乙基二正丁氧基矽烷、二乙基二異丁氧基矽烷 、二乙基二第二丁氧基矽烷、二乙基二第三丁氧基矽烷、 二正丙基二甲氧基矽烷、二正丙基二乙氧基矽烷、二正丙 基二正丙氧基矽烷、二正丙基二異丙氧基矽烷、二正丙基 -15- 200903173 二正丁氧基矽烷、二正丙基二異丁氧基矽烷、二正丙基二 第二丁氧基矽烷、二正丙基二第三丁氧基矽烷、二異丙基 二甲氧基矽烷、二異丙基二乙氧基矽烷、二異丙基二正丙 氧基矽烷、二異丙基二異丙氧基矽烷、二異丙基二正丁氧 基矽烷、二異丙基二異丁氧基矽烷、二異丙基二第二丁氧 基矽烷、二異丙基二第三丁氧基矽烷、二正丁基二甲氧基 矽烷、二正丁基二乙氧基矽烷、二正丁基二正丙氧基矽烷 、二正丁基二異丙氧基矽烷、二正丁基二正丁氧基矽烷、 二正丁基二異丙氧基矽烷、二正丁基二第二丁氧基矽烷、 二正丁基二第三丁氧基矽烷、二異丁基二甲氧基矽烷、二 異丁基二乙氧基矽烷、二異丁基二正丙氧基矽烷、二異丁 基二異丙氧基矽烷、二異丁基二正丁氧基矽烷、二異丁基 二異丁氧基矽烷、二異丁基二第二丁氧基矽烷、二異丁基 二第三丁氧基矽烷、二第二丁基二甲氧基矽烷、二第二丁 基二乙氧基矽烷、二第二丁基二正丙氧基矽烷、二第二丁 基二異丙氧基矽烷、二第二丁基二正丁氧基矽烷、二第二 丁基二異丁氧基矽烷、二第二丁基二第二丁氧基矽烷、二 第二丁基二第三丁氧基矽烷、二第三丁基二甲氧基矽烷、 二第三丁基二乙氧基矽烷、二第三丁基二正丙氧基矽烷、 二第三丁基二異丙氧基矽烷、二第三丁基二正丁氧基矽烷 、二第三丁基二異丁氧基矽烷、二第三丁基二第二丁氧基 矽烷、二第三丁基二第三丁氧基矽烷、二乙烯基二甲氧基 矽烷、二乙烯基二乙氧基矽烷、二乙烯基二正丙氧基矽烷 、二乙烯基二異丙氧基矽烷、二乙烯基二正丁氧基矽烷、 -16- 200903173 二乙烯基二異丁氧基矽烷、二乙烯基二第二丁氧基矽烷、 二乙烯基二第三丁氧基矽烷、二苯基二甲氧基矽烷、二苯 基二乙氧基矽烷、二苯基二正丙氧基矽烷、二苯基二異丙 氧基矽烷、二苯基二正丁氧基矽烷、二苯基二異丁氧基矽 烷、二苯基二第二丁氧基矽烷、二苯基二第三丁氧基矽烷 等。 上述第一有機溶劑若選擇將水解之上述式 R2mSi ( OR3 ) 4_m所示之化合物予以稀釋者即可，可列舉 例如丙二醇單甲醚、丙二醇單丙醚、丙二醇單甲醚醋酸酯 、丙酮、乙基甲基酮、甲醇、乙醇、丙醇、丁醇。 上述式 R1 (OCH2CHCH3) nOCOCH3 (式中，R1 爲表 示碳原子數1至4之烷基，η爲表示1或2)所示之第二 有機溶劑，可列舉例如丙二醇單甲醚醋酸酯。 溶解順型之二價羧酸（二羧酸），例如順丁烯二酸之 上述第三有機溶劑，可使用具有羥基之有機溶劑，其具體 例可列舉甲醇、乙醇、丙醇、丁醇般之一價醇；乙二醇、 二乙二醇、丙二醇、甘油般之多價醇；及乙二醇單甲醚、 乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇 單甲醚、二乙二醇單乙醚、二乙二醇單丙醚、二乙二醇單 丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙 二醇單丁醚般之多價醇的單醚類。又，其他例可列舉乳酸 乙酯等之光阻溶劑。以丙二醇單丙醚或丙二醇單甲醚作爲 第三有機溶劑爲佳。第一有機溶劑與第三有機溶劑可爲相 同或相異亦可。 -17- 200903173 促進水解（及縮合反應）的觸媒，可將酸溶解於水或 第一有機溶劑中供使用。此酸可使用鹽酸、硝酸、磷酸、 硫酸等之無機酸、磺酸、對-甲苯磺酸、苯磺酸、甲酸、 醋酸、丙酸等之有機酸。可使用氨、氫氧化鈉、氫氧化鉀 、氫氧化鈣、三甲胺、三乙胺、單乙醇胺、二乙醇胺、二 甲基單乙醇胺、單甲基二乙醇胺、三乙醇胺、氫氧化四甲 基銨、吡啶、吡咯、哌畊、吡咯烷等之鹼代替酸。 上述式R3OH所示之化合物爲將上述式 R2^ Si ( OR3 ) 41所示之至少一種化合物水解而成的副產 物。式R3OH所示之化合物以蒸發除去時，進一步除去水 、第一有機溶劑、上述酸等之觸媒中之至少一種爲佳。經 由除去酸等之觸媒與水之一者或兩者，則可期待抑制水解 及/或縮合反應之效果。第一有機溶劑及上述酸等之觸媒 ，若使用沸點或共沸點爲1 0 1 . 3 kP a例如1 2 0 °c以下者，則 可經由減壓下之蒸發而輕易除去且爲佳。 以蒸發除去之步驟可在大氣壓下進行，若以減壓，即 比101_3kPa (大氣壓）更低之壓力進行，則比大氣壓下進 行可更加降低加熱溫度’故爲佳。於本發明中，所謂除去 或餾去’並非意指必定將一般式R3〇H所示之化合物等之 對象物完全除去’其對象物最終殘留亦可。即，包含令除 去或餾去之對象物減少之意義。 實施例 以下，根據合成例及實施例具體說明本發明。但，本 -18- 200903173 發明並非被限定於下述合成例及實施例之記載。 本說明書所示之聚合物的平均分子量爲以GPC之測 定結果。所使用之裝置、條件等爲如下。 GPC 裝置：HLC-8220GPC (東梭（股）製） GPC 柱：Shodex〔註冊商標〕KF803L、KF802、 KF801 ( B召和電工（股）製）200903173 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a coating liquid which is formed by hardening on a substrate to form a film having a bond of hydrazine and oxygen, and is preserved at a temperature of room temperature or higher. Stability is improved. Further, in the manufacturing step of the semiconductor device, it is possible to use a coating liquid for forming a photoresist underlayer film which is provided before the formation of the photoresist film. [Prior Art] A film comprising a compound having a stanol group (Si-OH bond) obtained by hydrolyzing at least two kinds of alkoxydecane compounds in a specific organic solvent in the presence of water and a catalyst The coating liquid is known (refer to Patent Document 1). The two stanol groups are condensed to form a Si-0-Si bond, and become a polymer having a Si-O-Si bond. Further, as a photoresist underlayer film formed on a semiconductor substrate, a cured film using an organopolysiloxane is known (see Patent Document 2). The cured film was patterned using a pattern of photoresist and dry etched using CF4 gas. Thereafter, when the pattern of the photoresist is removed, the cured film can remain. One of the properties required for such a coating liquid is storage stability. That is, it is required that the chemical change and the physical change of the coating liquid are not caused even after a certain period of time elapses at room temperature. Patent Document 1 describes a coating liquid using a monoether of a divalent alcohol or a diether of a divalent alcohol as a solvent, and the number of days required for gelation is 100 or more, which is higher than the use of a divalent alcohol as a solvent. The preservation stability of the example is more excellent. Patent Document 3 describes the results of evaluating the storage stability of a solution according to the increase rate of the film thickness formed by the composition using a solution-like photoresist underlayer film -5-200903173. Evaluation Examples 1 to 4 and Comparative Example 1 showed good storage stability, and Comparative Example 2 showed poor storage stability. Next, in Comparative Example 2, the solvent used was distilled acetic acid butyl vinegar, and Examples 1 to 4 and Comparative Example 1 using distilled propylene glycol monopropyl ether as a solvent, indicating that the difference in solvent is the preservation stability of the solution. Make an impact. Patent Document 4 describes that by using propylene glycol monomethyl ether or propylene glycol monoethyl ether having a hydroxyl group and having a boiling point of 110 to 130 ° C as a solvent, excellent coating properties are obtained, and good storage stability is obtained. A composition for a photoresist underlayer film. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. 2002-040668. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The coating liquid for forming a film containing a polymer having a stanol group produced by a hydrolysis and a condensation reaction has a problem that the storage stability is poor. The molecular weight distribution measured by the coating liquid for forming a film according to gel permeation chromatography (hereinafter, abbreviated as GPC in the present specification) is changed in accordance with the storage period of the coating liquid. The reason for this is considered to be that the condensation reaction of the stanol group is gradually carried out at room temperature even if it is not heated by a heating means such as a hot plate. In order to inhibit the condensation reaction of stanol groups, -6-200903173 is considered to be stored refrigerated, but the cost is higher than that at room temperature. The GPC is a method in which a thin solution of a polymer compound is dissolved in a column of a porous gel and sequentially eluted from a large molecular size, and is a method for measuring a molecular weight distribution and a relative molecular weight of a polymer compound. When such a coating liquid for forming a film having poor stability is used, even when the conditions for forming a film on the substrate are the same, it is observed that the longer the storage period of the coating liquid used is, the more the film thickness becomes thicker. . The same condition means that the spin speed and the turn-off time of the spinner, and the heating temperature and heating time of the hot plate are the same. The amount of the stanol group is different depending on the type of the solvent in which the coating liquid for coating film is formed, and the storage stability is also different. When a specific example is used, the coating liquid for forming a film using propylene glycol monomethyl ether acetate (CH3OCH2CHCH3OCOCH3) as a solvent is easily cured by heating, and has a problem of poor storage stability at room temperature. Among the propylene glycol monomethyl ether acetates, the stanol group is more difficult to settle than the Si-0-Si bond even in the environment at room temperature, and it is presumed that the storage stability is poor. (Means for Solving the Problem) The present invention is based on the addition of a cis-type divalent carboxylic acid (also referred to as a dicarboxylic acid) such as maleic acid, cis-5-formylene-internal-2,3-di Carboxylic acid, cis-5-formylene-exo-2,3-dicarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, cis-4-cyclohexene·1,dicarboxylic acid, The cis-cyclobutane-1,2-dicarboxylic acid, methyl maleic acid (citraconic acid), and dimethyl maleic acid improve the storage stability of the coating liquid for forming a coating film. In the present specification, a cis-type divalent carboxylic acid (200903173 dicarboxylic acid) is a compound which becomes an acid anhydride via a dehydration reaction. (Effects of the Invention) The coating liquid for forming a film of the present invention is a storage temperature (not more than 35 ° C) higher than that of the prior art product by adding a cis acid (dicarboxylic acid) such as maleic acid. Excellent stability. A coating liquid for forming a film having a hardening property, which is represented by the formula R1 (OCH2CHCH3) nOCOCH3 (wherein R1 is an alkyl group having 1 to 4, and η is 1 or 2), and a coating liquid for forming a film, GPC The molecular weight distribution measured was unsatisfactory in terms of preservation stability as it was passed through the storage period. However, in the "root", both the hardenability property and the storage stability can be obtained to satisfy the film coating liquid. The reason for improving the storage stability of the coating liquid by the addition of a cis-divalent carboxylic acid (dicarboxylic acid) is considered to be due to the cis-type (dicarboxylic acid) sterol group-stabilizing in an organic solvent. It inhibits the condensation reaction of the stanol group. The coating liquid for forming a film of the present invention does not require cooling to save low storage and transportation costs. Because of the temperature at room temperature or above 3 5 . There is almost no change in the molecular weight distribution during the storage period under (:). A ship that is cheaper than the aircraft's transportation cost but takes a long time is selected. [Embodiment] The divalent carboxy group at room temperature or in particular, the carbon source solvent is conventionally changed, and the result of forming the film-forming divalent carboxylic acid of the present invention is as large as possible, so that it can be reduced (not more than Therefore, for example, it can be exported. 8-200903173 The first aspect of the present invention is a polymer comprising a Si-O-Si bond and having a stanol group, and a formula 1^(〇CH2CHCH3)n0C0CH3 (wherein R1) An alkyl group having a carbon number of 1 to 4, which is an organic solvent represented by 1 or 2), an organic solvent capable of dissolving a cis-type divalent carboxylic acid (dicarboxylic acid) and a cis-type divalent carboxylic acid (Dicarboxylic acid) forming coating film for coating film The second aspect of the invention is a polymer comprising an organic group and a stanol group having a Si-0-Si bond, and a formula of R1 ( OCH 2 CHCH 3 ) n0 C0 CH 3 (formula) Wherein R1 is an alkyl group having 1 to 4 carbon atoms, n is an organic solvent represented by 1 or 2), an organic solvent capable of dissolving a cis-type divalent carboxylic acid (dicarboxylic acid), and a cis-form 2 A coating liquid for forming a film of a valent carboxylic acid (dicarboxylic acid). The above polymer is a formula of R2mSi(OR3) 4_m (wherein R2 is The organic group, R3 is an alkyl group having 1 to 4 carbon atoms, and m is a product obtained by hydrolysis and condensation reaction of at least one compound represented by ruthenium, 1 or 2). The above organic group may be an aryl group, At least one selected from the group consisting of an alkenyl group, an alkyl group, a hydroxyalkyl group, an epoxy group, an amine group, a decyl group, an acryl fluorenyl group, a methacryl fluorenyl group, and a thiol group, or a combination of two or more groups. The aryl group may, for example, be a phenyl group or an alkenyl group which is a group having a double bond between carbons, and examples thereof include a vinyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. In the above-mentioned group, two or more kinds of groups are selected, and those having two or more kinds of bases are exemplified by, for example, an aralkyl group. The alkyl group may be either linear or branched. -9- 200903173 Divalent carboxylic acid (dicarboxylic acid), such as maleic acid, cis-5-formylene-endo-2,3-dicarboxylic acid, cis-5-formylene-exo-2,3-di The carboxylic acid or the like is an organic solvent which is almost completely insoluble in the formula R1 (〇CH2CHCH3) n0C0CH3 (wherein R1 is an alkyl group having 1 to 4 carbon atoms, and η is 1 or 2) For example, propylene glycol monomethyl ether acetate is required. Therefore, a solvent for dissolving a cis-type divalent carboxylic acid (dicarboxylic acid) is required. A cis-divalent carboxylic acid (dicarboxylic acid) is a polar solvent dissolved in water or the like, but The organic solvent represented by the formula R1 ( OCH 2 CHCH 3 ) n 〇 COCH 3 (wherein R 1 is an alkyl group having 1 to 4 carbon atoms, and η is 1 or 2) is difficult to dissolve in water. The solvent in which the carboxylic acid (dicarboxylic acid) is dissolved may be, for example, an organic solvent having a hydroxyl group. Specific examples of such an organic solvent include methanol, ethanol, propanol, butanol-like monovalent alcohol; ethylene glycol, diethylene glycol Alcohol, propylene glycol, glycerin-like polyvalent alcohol; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethers of polyvalent alcohols such as alcohol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether. Further, as another example, a photoresist solvent such as ethyl lactate may be mentioned. In addition to the coating property to the substrate, it is preferred to use propylene glycol monopropyl ether (C3H7OCH2CHCH3OH) or propylene glycol monomethyl ether (CH3OCH2CHCH3OH) in an organic solvent having a hydroxyl group. It is preferable to contain a cis-type divalent carboxylic acid (dicarboxylic acid) in an amount of not less than 1 part by mass based on 1 part by mass of the coating liquid for forming a coating film, and to form a solid component in the coating liquid for forming a coating film. The mass part contains 1 part by mass or more of the -10 200903173 cis-type divalent carboxylic acid (dicarboxylic acid). The solid component is a component which removes a solvent in a coating liquid. The upper limit of the concentration of the cis-divalent carboxylic acid (dicarboxylic acid) is, for example, 1 part by mass based on 100 parts by mass of the coating liquid for forming a coating film, and is solid relative to the coating liquid for forming a coating film. The component 100 parts by mass may be 10 parts by mass. In addition, the solid content is, for example, 1 part by mass or more and 50 parts by mass or less, and preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the coating liquid for forming a coating film, and the formula R1 (OCH2CHCH3) n The organic solvent represented by 〇COCH3 (wherein R1 is an alkyl group having 1 to 4 carbon atoms and n is 1 or 2) is, for example, 5 parts by mass or more and 90 parts by mass or less, and the divalent valence can be dissolved. The solvent of the carboxylic acid (dicarboxylic acid) is, for example, 5 parts by mass or more and 90 parts by mass or less. The polymer having the aforementioned stanol group is, for example, contained in an amount of 50 parts by mass or more and 99 parts by mass or less based on 100 parts by mass of the solid content. Further, the coating liquid for forming a film of the present invention may further contain a quaternary ammonium salt. Examples of the quaternary ammonium salt include benzyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltributylammonium chloride, tetramethylammonium chloride, tetraethylammonium bromide, and chlorination. Tetraethylammonium, tetrapropylammonium bromide, tetrabutylammonium bromide, tributylmethylammonium chloride, trioctylmethylammonium chloride, phenyltrimethylammonium chloride, etc., and optionally chlorine Benzyltriethylammonium. The quaternary ammonium salt is, for example, contained in an amount of 0. 005 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the solid content. A third aspect of the present invention is a step of coating a coating film for coating a first aspect or a second aspect of the present invention on a substrate, and hardening to form a photoresist lower layer-11 - 200903173 film, a step of forming a photoresist film on the underlayer film, a step of exposing and developing the photoresist film to form a photoresist pattern, and a step of dry etching the photoresist underlayer film using the photoresist pattern as a mask A method of manufacturing a semiconductor device. At least one of an insulating film (organic film or inorganic film) having conductivity (a metal film or the like) may be formed on the substrate ', and in this case, the photoresist underlayer film is formed on the film. . The organic film or the inorganic film is preferably formed by coating on a substrate such as a tantalum wafer according to a spin coating method. The semiconductor device includes a semiconductor device (a diode, a transistor, or the like) manufactured using a semiconductor substrate such as a germanium wafer or an insulating substrate such as a glass substrate or a plastic substrate, and an electronic device (mobile phone) manufactured using the semiconductor device. , TV receivers, personal computers, etc.). A fourth aspect of the present invention comprises the formula R2mSi(OR3) 4.m (wherein R2 represents an organic group, R3 represents an alkyl group having 1 to 4 carbon atoms, and m represents 0, 1 or 2 a step of hydrolyzing at least one compound shown in a first organic solvent, followed by a condensation reaction to produce a polymer having a S i - Ο - S i bond and having a stanol group, at least as shown by the formula R3 OH a step of removing (distilling) the compound by evaporation and adding a second organic compound of the formula R1 ( OCH 2 CHCH 3 ) n 〇 COCH 3 (wherein R 1 is an alkyl group having 1 to 4 carbon atoms, and η is 1 or 2) The solvent is a method for producing a coating liquid for forming a film by dissolving a third organic solvent of a cis-divalent carboxylic acid (dicarboxylic acid) and a cis-divalent carboxylic acid (dicarboxylic acid). The fifth aspect of the present invention comprises the formula R2mSi(OR3)4_m (in the formula -12-200903173, R2 represents an organic group, R3 represents an alkyl group having 1 to 4 carbon atoms, and m represents 〇, 丨Or the step of hydrolyzing at least one compound shown in 2) in a first organic solvent, followed by a condensation reaction to produce a polymer having a si-〇-si bond and having a stanol group, at least as shown by the formula R3〇H The step of removing (distilling off) the compound by evaporation, adding the formula R1 (OCH2CHCH3) n〇COCH3 (wherein, R1 is a hospital group representing a carbon number of 1 to 4, and η is a ratio of 1 or 2) The step of forming an organic solvent and the step of forming a coating liquid for a coating film by a step of dissolving a third organic solvent of a cis-divalent carboxylic acid (dicarboxylic acid) and a cis-type divalent carboxylic acid (dicarboxylic acid). Before the step of evaporating and removing, the step of adding the aforementioned second organic solvent, such as propylene glycol monomethyl ether acetate (boiling point of about 1 4 6 ° C at a temperature of about 1 4 6 ° C) is effective, the first organic solvent It is particularly effective at a boiling point of 10 kPa (atmospheric pressure) of 1 〇〇 ° C or less, for example, in the case of ethanol. Since the solution is excessively concentrated by evaporation, the condensation reaction of the stanol group is excessively performed, and as a result, the stanol group can be prevented from being eliminated. The smaller the amount of the stanol group, the harder it is to harden the coating liquid to form a film. Further, when an acid dissolved in water is used as a catalyst for promoting hydrolysis (and condensation reaction), the acid can be easily removed by evaporating under reduced pressure in the presence of a low-polar solvent propylene glycol monomethyl ether acetate. In the above formula R2mSi ( OR3 ) 4.m, R 2 may be an aryl group, an alkenyl group, an alkyl group, a hydroxyalkyl group, an epoxy group, an amine group, a decyl group, an acryl fluorenyl group, a methacryl fluorenyl group or a hydrogen sulphur group. At least one of the groups or a combination of two or more groups is selected from the group consisting of the groups. The aryl group may, for example, be a phenyl group, and the alkenyl group is a group having a double bond of -13 to 200903173 between carbons, and examples thereof include a vinyl group. The alkyl group may, for example, be a methyl 'ethyl group, a propyl group or a butyl group. In the above-mentioned group, two or more kinds of groups are selected, and those having two or more types are included, and examples thereof include an aryl group. The disease base is either linear or branched. Specific examples of the compound represented by the above formula R2mSi(OR3) 4 - m include tetramethoxydecane, tetraethoxydecane, tetra-n-propoxylate, tetraisopropoxydecane, tetra-n-butoxy Decane, tetraisobutoxy chopping, tetra-butoxy decane, tetra-butoxy decane, methyl trimethoxy sand, methyl triethoxy decane, methyl tri-n-propoxy decane , methyl triisopropoxy decane, methyl tri-n-butoxy decane, methyl triisobutoxy sulfoxide, methyl tri-n-butoxy decane, methyl tri-tert-butoxy decane, B Trimethoxy decane, ethyl triethoxy decane, ethyl tri-n-propoxy oxalate, ethyl triisopropoxy decane, ethyl tri-n-butoxy decane, ethyl triisobutoxy decane , Ethyl tri-tert-butoxy decane, Ethyl tri-tert-butoxylate, n-propyl trimethoxy decane, n-propyl triethoxy decane, n-propyl di-n-propoxy decane, positive Propyl triisopropoxy decane, n-propyl tri-n-butoxy decane, n-propyl triisobutoxy decane, n-propyl tri-n-butoxy, propyl, n-propyl Butoxy decane, isopropyl trimethoxy sand, isopropyl triethoxy decane, isopropyl tri-n-propoxy sand, isopropyl triisopropoxy sane, isopropyl tri-n-butyl Butoxy decane, isopropyl triisobutoxy fluorene, isopropyl tri-n-butoxy decane, isopropyl di-butoxy decane, n-butyl trimethoxy decane, n-butyl three Ethoxy decane, n-butyl tri-n-propoxy decane, n-butyl triisopropoxy sand, n-butyl tri-n-butoxy decane, n-butyl triisobutoxy decane, n-butyl three Second butoxy 矽-14- 200903173 alkane, n-butyl tri-tert-butoxy decane, second butyl trimethoxy decane, second butyl triethoxy decane, second butyl tri-n-propoxy Base decane, second butyl triisopropoxy decane, second butyl tri-n-butoxy decane, second butyl triisobutoxy decane, second butyl tri-butoxy decane, second Butyl tributoxybutane, tert-butyltrimethoxydecane, tert-butyltriethoxydecane, tert-butyltri-n-propoxydecane, tert-butyltriisopropoxydecane , Third butyl tri-n-butoxy decane, tert-butyl triisobutoxy decane, tert-butyl tri-second butoxy decane, tert-butyl tri-tert-butoxy decane, vinyl trimethoxy Base decane, vinyl triethoxy decane, vinyl tri-n-propoxy decane, vinyl triisopropoxy decane, vinyl tri-n-butoxy decane, vinyl triisobutoxy decane, vinyl three Second butoxy decane, vinyl tri-tert-butoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl triisopropoxy decane, Phenyl tri-n-butoxy decane, phenyl triisobutoxy decane, phenyl tri-tert-butoxy decane, phenyl tri-tert-butoxy decane, dimethyl dimethoxy decane, dimethyl Diethoxy decane, dimethyl di-n-propoxy decane, dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, dimethyl diisobutoxy decane, dimethyl di Second butoxydecane, dimethylditributoxydecane, diethyldimethoxydecane, diethyldiethoxydecane, diethyl Di-n-propoxy decane, diethyl diisopropoxy decane, diethyl di-n-butoxy decane, diethyl diisobutoxy decane, diethyl di-butoxy decane, diethyl Di-tert-butoxy decane, di-n-propyl dimethoxy decane, di-n-propyl diethoxy decane, di-n-propyl di-n-propoxy decane, di-n-propyl diisopropoxy decane Di-n-propyl-15- 200903173 di-n-butoxy decane, di-n-propyl diisobutoxy decane, di-n-propyl di-butoxy decane, di-n-propyl bis-butoxy decane , diisopropyldimethoxydecane, diisopropyldiethoxydecane, diisopropyldi-n-propoxyoxydecane, diisopropyldiisopropoxydecane, diisopropyldi-n-butyl Oxy decane, diisopropyl diisobutoxy decane, diisopropyl bis second butoxy decane, diisopropyl bis 3 butyl decane, di-n-butyl dimethoxy decane, n-Butyldiethoxydecane, di-n-butyldi-n-propoxyoxydecane, di-n-butyldiisopropoxydecane, di-n-butyldi-n-butoxyoxane, di-n-butyldiisopropyloxide base Decane, di-n-butyldi-second butoxy decane, di-n-butyldi-butoxybutane, diisobutyldimethoxydecane, diisobutyldiethoxydecane, diisobutyl Di-n-propoxy decane, diisobutyl diisopropoxy decane, diisobutyl di-n-butoxy decane, diisobutyl diisobutoxy decane, diisobutyl bis second butoxy Decane, diisobutyldi-tert-butoxydecane, di-tert-butyldimethoxydecane, di-tert-butyldiethoxydecane, di-tert-butyldi-n-propoxy decane, dip Dibutyl diisopropoxy decane, di-tert-butyl di-n-butoxy decane, di-tert-butyl diisobutoxy decane, di-second butyl di-butoxy decane, second Butyl di-butoxy decane, di-tert-butyl dimethoxy decane, di-t-butyl diethoxy decane, di-tert-butyl di-n-propoxy decane, di-tert-butyl Isopropoxydecane, di-tert-butyldi-n-butoxydecane, di-tert-butyldiisobutoxydecane, di-tert-butyldi-second-butoxydecane, di-t-butyldi-di Tributoxy Base decane, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl di-n-propoxy decane, divinyl diisopropoxy decane, divinyl di-n-butoxy decane , -16- 200903173 Divinyl diisobutoxy decane, divinyl bis second butoxy decane, divinyl bis-butoxy decane, diphenyl dimethoxy decane, diphenyl bis Ethoxy decane, diphenyl di-n-propoxy decane, diphenyl diisopropoxy decane, diphenyl di-n-butoxy decane, diphenyl diisobutoxy decane, diphenyl di Dibutoxydecane, diphenyldi-t-butoxydecane, and the like. The first organic solvent may be prepared by diluting a compound represented by the above formula R2mSi(OR3) 4_m which is hydrolyzed, and examples thereof include propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, acetone, and B. Methyl ketone, methanol, ethanol, propanol, butanol. The second organic solvent represented by the above formula R1 (OCH2CHCH3) nOCOCH3 (wherein R1 is an alkyl group having 1 to 4 carbon atoms and η is 1 or 2) may, for example, be propylene glycol monomethyl ether acetate. For dissolving a cis-type divalent carboxylic acid (dicarboxylic acid), for example, the above-mentioned third organic solvent of maleic acid, an organic solvent having a hydroxyl group can be used, and specific examples thereof include methanol, ethanol, propanol, and butanol. One-valent alcohol; ethylene glycol, diethylene glycol, propylene glycol, glycerin-like polyvalent alcohol; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether Monoethyl ethers of polyvalent alcohols. Further, as another example, a photoresist solvent such as ethyl lactate may be mentioned. It is preferred to use propylene glycol monopropyl ether or propylene glycol monomethyl ether as the third organic solvent. The first organic solvent and the third organic solvent may be the same or different. -17- 200903173 Catalyst for promoting hydrolysis (and condensation reaction), which can be dissolved in water or a first organic solvent for use. As the acid, an organic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, an organic acid such as sulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, formic acid, acetic acid or propionic acid can be used. Ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyldiethanolamine, triethanolamine, tetramethylammonium hydroxide can be used. A base such as pyridine, pyrrole, piperazine or pyrrolidine is used instead of the acid. The compound represented by the above formula R3OH is a by-product obtained by hydrolyzing at least one compound represented by the above formula R2^Si(OR3)41. When the compound represented by the formula: R3OH is removed by evaporation, it is preferred to further remove at least one of water, a first organic solvent, and a catalyst such as the above acid. The effect of suppressing the hydrolysis and/or condensation reaction can be expected by removing one or both of a catalyst and water such as an acid. When the first organic solvent and the above-mentioned acid or the like are used, if the boiling point or the azeotropic point is 10 1 3 kP a, for example, 1 2 0 °c or less, it can be easily removed by evaporation under reduced pressure. The step of removing by evaporation can be carried out under atmospheric pressure, and if it is carried out under reduced pressure, i.e., at a pressure lower than 101_3 kPa (atmospheric pressure), the heating temperature can be further lowered than at atmospheric pressure. In the present invention, the term "removal or distillation" does not mean that the object of the compound represented by the general formula R3〇H or the like is completely removed, and the object may eventually remain. That is, it includes the meaning of reducing the object to be removed or distilled. EXAMPLES Hereinafter, the present invention will be specifically described based on Synthesis Examples and Examples. However, the invention of the present invention is not limited to the description of the following synthesis examples and examples. The average molecular weight of the polymer shown in this specification is the result of measurement by GPC. The apparatus, conditions, and the like used are as follows. GPC device: HLC-8220GPC (made by Tosoh Corporation) GPC column: Shodex [registered trademark] KF803L, KF802, KF801 (B call and electrician (share) system)
柱溫：4 0 °C 溶劑：四氫呋喃（T H F ) 流量：1.0毫升/分鐘 標準試料：聚苯乙烯（昭和電工（股）製） (合成例1 ) 本合成例中，使用四乙氧基矽烷作爲式 R2mSi ( OR3 ) 4_m (式中’ R2爲表示有機基，R3爲表示碳 原子數爲1至4之烷基’ m爲表示0、1或2)所示之化合 物。 將四乙氧基矽烷84.63克及乙醇84.63克於300毫升 之燒瓶中混合’將所得之混合溶液一邊以磁性攪拌子攪拌 一邊加溫’並且令其迴流。其次，於混合溶液中添加離子 交換水29.26克中溶解鹽酸1.48克的水溶液，反應1小時 後，將所得之反應溶液冷卻至室溫。取代鹽酸，作用爲促 進反應之觸媒的其他酸，例如亦可使用硝酸、磷酸。反應 後，生成副產物乙醇。 其後’於反應溶液中加入丙二醇單甲醚醋酸酯200克 -19- 200903173 ，並將乙醇、水、及鹽酸減壓餾去，取得含有水解縮合物 (聚合物）的溶液。於所得溶液之溶劑中’丙二醇單甲醚 醋酸酯爲以接近100 %之重量比含有。根據本合成例之聚 合物以GPC的分子量，換算爲聚苯乙烯之重量平均分子 量 Mw 爲 6200。 (合成例2 ) 本合成例中，使用四乙氧基矽烷和苯基三甲氧基矽烷 作爲式R2mSi ( OR3 ) 4-m (式中’ R2爲表示有機基，R3爲 表示碳原子數爲1至4之院基，m爲表示〇、1或2)所示 之化合物。 將四乙氧基矽烷76.76克、苯基三甲氧基矽烷8_12克 、及乙醇8 4.8 8克於3 0 0毫升之燒瓶中混合，將所得之混 合溶液一邊以磁性攪拌子攪拌一邊加溫，並且令其迴流。 其次，於混合溶液中添加離子交換水28.75克中溶解鹽酸 1.49克的水溶液，反應2小時後，將所得之反應溶液冷卻 至室溫。取代鹽酸，作用爲促進反應之觸媒的其他酸，例 如亦可使用硝酸、隣酸。反應後，生成副產物乙醇及甲醇 〇 其後’於反應溶液中加入丙二醇單甲醚醋酸酯200克 ’並將乙醇、甲醇、水、及鹽酸減壓餾去，取得含有水解 縮合物（聚合物）的溶液。於所得溶液之溶劑中，丙二醇 單甲醚醋酸酯爲以接近100 %之重量比含有。根據本合成 例之聚合物以GPC的分子量，換算爲聚苯乙烯之重量平 -20- 200903173 均分子量Mw爲4500。 (合成例3) 本合成例中，使用四乙氧基矽烷和苯基三甲氧基矽燒 作爲式R2mSi ( OR3 ) 4.m (式中，R2爲表示有機基，R3爲 表不碳原子數爲1至4之垸基，m爲表示〇、1或2)所示 之化合物。 將此四乙氧基砂院 60.65克、苯基二甲氧基砂院 24·74克、及乙醇85.39克於300毫升之燒瓶中混合，將 所得之混合溶液一邊以磁性攪拌子攪拌一邊加溫，並且令 其迴流。其次，於混合溶液中添加離子交換水27.72克中 溶解鹽酸1 .5 1克的水溶液，反應2小時後，將所得之反 應溶液冷卻至室溫。取代鹽酸，作用爲促進反應之觸媒的 其他酸，例如亦可使用硝酸、磷酸。反應後，生成副產物 乙醇及甲醇。 其後，於反應溶液中加入丙二醇單甲醚醋酸酯200克 ，並將乙醇、甲醇、水、及鹽酸減壓餾去，取得含有水解 縮合物（聚合物）的溶液。於所得溶液之溶劑中，丙二醇 單甲醚醋酸酯爲以接近100 %之重量比含有。根據本合成 例之聚合物以GPC的分子量，換算爲聚苯乙烯之重量平 均分子量Mw爲2000。 (合成例4 ) 本合成例中，使用四乙氧基矽烷、苯基三甲氧基砂院 -21 - 200903173 、乙烯基三甲氧基矽烷、及甲基三乙氧基砂院作爲式 R2mSi(〇R3) 4-m(式中，R2爲表示有機基’ r3爲表示碳 原子數爲1至4之烷基，m爲表示〇、1或2)所示之化合 物。 將四乙氧基矽烷62.47克、苯基三甲氧基砂院8.49克 乙烯基三甲氧基矽烷6.35克 '甲基三乙氧基砍院7.64克 、及乙醇8 4.9 5克於3 0 0毫升之燒瓶中混合’將所得之混 合溶液一邊以磁性攪拌子攪拌一邊加溫，並且令其迴流。 其次，於混合溶液中添加離子交換水中溶解鹽酸的水溶液 ，反應2小時後，將所得之反應溶液冷卻至室溫。取代鹽 酸，作用爲促進反應之觸媒的其他酸，例如亦可使用硝酸 、磷酸。反應後，生成副產物乙醇及甲醇。 其後，於反應溶液中加入丙二醇單甲醚醋酸酯200克 ，並將乙醇、甲醇、水、及鹽酸減壓餾去，取得含有水解 縮合物（聚合物）的溶液。於所得溶液之溶劑中，丙二醇 單甲醚醋酸酯爲以接近100%之重量比含有。根據本合成 例之聚合物以GPC的分子量，換算爲聚苯乙烯之重量平 均分子量Mw爲6000。 (合成例5 ) 本合成例中’使用四乙氧基矽烷、苯基三甲氧基矽烷 及乙烯基三甲氧基矽烷作爲式R2mSi ( 〇R3 ) 4-m (式中， R2爲表示有機基’ R3爲表示碳原子數爲1至4之烷基，m 爲表不0、1或2)所示之化合物。 -22- 200903173 將四乙氧基矽烷63.28克、苯基三甲氧基矽;t 、乙烯基三甲氧基矽烷12.86克、及乙醇84.75 毫升之燒瓶中混合，將所得之混合溶液一邊以磁 攪拌一邊加溫，並且令其迴流。其次，於混合溶 離子交換水中溶解鹽酸的水溶液，反應2小時後 之反應溶液冷卻至室溫。取代鹽酸，作用爲促進 媒的其他酸，例如亦可使用硝酸、磷酸。反應後 產物乙醇及甲醇。 其後，於反應溶液中加入丙二醇單甲醚醋酸j ，並將乙醇、甲醇、水、及鹽酸減壓餾去，取得 縮合物（聚合物）的溶液。於所得溶液之溶劑中 單甲醚醋酸酯爲以接近100 %之重量比含有。根 例之聚合物以GPC的分子量，換算爲聚苯乙烯 均分子量Mw爲4400。 (合成例6) 本合成例中’使用四乙氧基矽烷、苯基三甲 及甲基三乙氧基矽烷作爲式R2mSi ( OR3 ) 4_m ( 爲表示有機基’ R3爲表示碳原子數爲1至4之院 表示0、1或2 )所示之化合物。 將四乙氧基矽烷67.54克、苯基三甲氧基矽$ 、甲基三乙氧基砂院8.26克、及乙醇84.98克於 之燒瓶中混合，將所得之混合溶液一邊以磁性攪 一邊加溫’並且令其迴流。其次，於混合溶液中 完8.60克 克於300 性攪拌子 液中添加 ，將所得 反應之觸 ，生成副 贈200克 含有水解 ，丙二醇 據本合成 之重量平 氧基矽烷 式中，R2 基，m爲 完9_18克 3 00毫升 拌子攪拌 添加離子 -23- 200903173 交換水中溶解鹽酸的水溶液，反應2小時後，將 應溶液冷卻至室溫。取代鹽酸，作用爲促進反應 其他酸，例如亦可使用硝酸、磷酸。反應後，生 乙醇及甲醇。 其後，於反應溶液中加入丙二醇單甲醚醋酸 ’並將乙醇、甲醇、水、及鹽酸減壓餾去，取得 縮合物（聚合物）的溶液。於所得溶液之溶劑中 單甲醚醋酸酯爲以接近100 %之重量比含有。根 例之聚合物以GPC的分子量，換算爲聚苯乙烯 均分子量Mw爲5000。 (合成例7) 本合成例中，使用四乙氧基矽烷、苯基三甲 及甲基三乙氧基矽烷作爲式R^Si ( OR3 ) 4.m ( 爲表示有機基’ R3爲表示碳原子數爲1至4之院 表示0、1或2)所示之化合物。 將四乙氧基矽烷57.99克、苯基三甲氧基砂; 、甲基三乙氧基矽烷22.90克、及乙醇85.14克 升之燒瓶中混合，將所得之混合溶液一邊以磁性 梓一邊加溫’並且令其迴流。其次，於混合溶液 子交換水2 8 . 1 4克中溶解鹽酸1 · 5 7克的水溶液， 時後’將所得之反應溶液冷卻至室溫。取代鹽酸 促進反應之觸媒的其他酸，例如亦可使用硝酸、 應後，生成副產物乙醇及甲醇。 所得之反 之觸媒的 成副產物 酯200克 含有水解 ，丙二醇 據本合成 之重量平 氧基矽烷 式中，R2 基，m爲 院4.25克 於3 00毫 攪拌子攪 中添加離 反應2小 ，作用爲 磷酸。反 -24- 200903173 其後，於反應溶液中加入丙二醇單甲醚醋酸酯200克 ，並將乙醇、甲醇、水、及鹽酸減壓餾去，取得含有水解 縮合物（聚合物）的溶液。於所得溶液之溶劑中，丙二醇 單甲醚醋酸酯爲以接近100%之重量比含有。根據本合成 例之聚合物以GPC的分子量，換算爲聚苯乙烯之重量平 均分子量Mw爲7700。將所得之溶液以丙二醇單甲醚醋酸 酯稀釋，固形成分爲1 3 .9質量％。 <矽烷醇基之確認> 使用FT-IR及FT-NIR測定合成例4所得之溶液中之 矽烷醇基（Si-OH鍵）的存在。所使用之裝置及條件爲如 下述。Column temperature: 40 ° C Solvent: Tetrahydrofuran (THF) Flow rate: 1.0 ml/min Standard sample: Polystyrene (manufactured by Showa Denko Co., Ltd.) (Synthesis Example 1) In the present synthesis example, tetraethoxy decane was used. R2mSi(OR3)4_m (wherein R2 represents an organic group, and R3 represents an alkyl group having 1 to 4 carbon atoms, m is a compound represented by 0, 1, or 2). 84.63 g of tetraethoxydecane and 84.63 g of ethanol were mixed in a 300 ml flask. The resulting mixed solution was heated while stirring with a magnetic stirrer and allowed to reflux. Next, an aqueous solution of 1.28 g of hydrochloric acid dissolved in 29.26 g of ion-exchanged water was added to the mixed solution, and after reacting for 1 hour, the resulting reaction solution was cooled to room temperature. Instead of hydrochloric acid, it acts as an acid for promoting the catalyst of the reaction, and for example, nitric acid or phosphoric acid can also be used. After the reaction, by-product ethanol is formed. Then, propylene glycol monomethyl ether acetate 200 g -19-200903173 was added to the reaction solution, and ethanol, water, and hydrochloric acid were distilled off under reduced pressure to obtain a solution containing a hydrolysis condensate (polymer). In the solvent of the resulting solution, 'propylene glycol monomethyl ether acetate was contained in a weight ratio close to 100%. According to the molecular weight of the polymer of the present synthesis, the weight average molecular weight Mw of polystyrene was 6,200. (Synthesis Example 2) In the present synthesis example, tetraethoxydecane and phenyltrimethoxydecane were used as the formula R2mSi(OR3)4-m (wherein R2 represents an organic group, and R3 represents a carbon number of 1). To a hospital base of 4, m is a compound represented by hydrazine, 1 or 2). 60.76 g of tetraethoxy decane, 8-12 g of phenyltrimethoxydecane, and 84.8 g of ethanol were mixed in a 300 ml flask, and the resulting mixed solution was heated while stirring with a magnetic stirrer, and Let it flow back. Next, an aqueous solution of 1.49 g of hydrochloric acid dissolved in 28.75 g of ion-exchanged water was added to the mixed solution, and after reacting for 2 hours, the resulting reaction solution was cooled to room temperature. Instead of hydrochloric acid, it acts as a catalyst for promoting the reaction catalyst, and for example, nitric acid or an acid can also be used. After the reaction, a by-product of ethanol and methanol is formed, and then propylene glycol monomethyl ether acetate 200 g is added to the reaction solution, and ethanol, methanol, water, and hydrochloric acid are distilled off under reduced pressure to obtain a hydrolysis-containing condensate (polymer). )The solution. In the solvent of the obtained solution, propylene glycol monomethyl ether acetate was contained in a weight ratio close to 100%. The polymer according to this synthesis example was converted to the weight of polystyrene by the molecular weight of GPC -20-200903173, and the average molecular weight Mw was 4500. (Synthesis Example 3) In the present synthesis example, tetraethoxydecane and phenyltrimethoxysulfonium were used as the formula R2mSi(OR3)4m (wherein R2 represents an organic group, and R3 represents a non-carbon number. Is a fluorenyl group of 1 to 4, and m is a compound represented by hydrazine, 1 or 2). 60.65 g of the tetraethoxy sand pot, 24.74 g of the phenyl dimethoxy sand pot, and 85.39 g of the ethanol were mixed in a 300 ml flask, and the obtained mixed solution was heated while stirring with a magnetic stir bar. And let it flow back. Next, an aqueous solution of 17.72 g of ion-exchanged water and 1.51 g of hydrochloric acid was added to the mixed solution, and after reacting for 2 hours, the resulting reaction solution was cooled to room temperature. Instead of hydrochloric acid, it acts as a catalyst for promoting the reaction catalyst, and for example, nitric acid or phosphoric acid can also be used. After the reaction, by-products of ethanol and methanol were formed. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and ethanol, methanol, water, and hydrochloric acid were distilled off under reduced pressure to obtain a solution containing a hydrolyzed condensate (polymer). In the solvent of the obtained solution, propylene glycol monomethyl ether acetate was contained in a weight ratio close to 100%. The polymer according to the present synthesis example has a weight average molecular weight Mw of 2000 in terms of the molecular weight of GPC in terms of polystyrene. (Synthesis Example 4) In the present synthesis example, tetraethoxy decane, phenyltrimethoxy sand court-21 - 200903173, vinyl trimethoxy decane, and methyl triethoxy sand sand were used as the formula R2mSi (〇 R3) 4-m (wherein R2 represents a compound represented by an organic group 'r3 is an alkyl group having 1 to 4 carbon atoms, and m is 〇, 1 or 2). 62.47 g of tetraethoxy decane, 8.49 g of vinyl trimethoxy decane, 6.35 g of 'methyl triethoxy chopping 7.64 g, and 84.9 5 g of ethanol in 300 ml of phenyl trimethoxy decane. Mixing in the flask 'The resulting mixed solution was warmed while stirring with a magnetic stirrer, and allowed to reflux. Next, an aqueous solution of hydrochloric acid dissolved in ion-exchanged water was added to the mixed solution, and after reacting for 2 hours, the resulting reaction solution was cooled to room temperature. Instead of a hydrochloric acid, it acts as a catalyst for promoting the reaction catalyst, and for example, nitric acid or phosphoric acid can also be used. After the reaction, by-products of ethanol and methanol were formed. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and ethanol, methanol, water, and hydrochloric acid were distilled off under reduced pressure to obtain a solution containing a hydrolyzed condensate (polymer). In the solvent of the obtained solution, propylene glycol monomethyl ether acetate was contained in a weight ratio close to 100%. The polymer according to the present synthesis example has a weight average molecular weight Mw of 6,000 in terms of the molecular weight of GPC in terms of polystyrene. (Synthesis Example 5) In the present synthesis example, 'tetraethoxydecane, phenyltrimethoxydecane, and vinyltrimethoxydecane were used as the formula R2mSi(〇R3)4-m (wherein R2 represents an organic group' R3 is an alkyl group having 1 to 4 carbon atoms, and m is a compound represented by 0, 1 or 2). -22- 200903173 A mixture of 63.28 g of tetraethoxynonane, phenyltrimethoxyanthracene; t, vinyltrimethoxydecane 12.86 g, and ethanol 84.75 ml was mixed, and the obtained mixed solution was magnetically stirred. Warm up and let it flow back. Next, an aqueous solution of hydrochloric acid was dissolved in mixed dissolved ion exchange water, and the reaction solution after 2 hours of reaction was cooled to room temperature. Instead of hydrochloric acid, it acts to promote other acids of the medium. For example, nitric acid or phosphoric acid can also be used. After the reaction, the products were ethanol and methanol. Thereafter, propylene glycol monomethyl ether acetate j was added to the reaction solution, and ethanol, methanol, water, and hydrochloric acid were distilled off under reduced pressure to obtain a solution of the condensate (polymer). In the solvent of the resulting solution, monomethyl ether acetate was contained in a weight ratio close to 100%. The polymer of the root was converted to a polystyrene average molecular weight Mw of 4,400 in terms of the molecular weight of GPC. (Synthesis Example 6) In the present synthesis example, 'tetraethoxydecane, phenyltrimethyl, and methyltriethoxydecane are used as the formula R2mSi(OR3) 4_m (indicating that the organic group 'R3 represents a carbon number of 1 to The hospital of 4 represents the compound shown in 0, 1 or 2). Mixing 67.54 g of tetraethoxydecane, phenyltrimethoxyanthracene, 8.26 g of methyltriethoxylate, and 84.98 g of ethanol, and mixing the resulting mixed solution while stirring with magnetic stirring 'And let it flow back. Next, in the mixed solution, 8.60 g of the solution was added to the 300-grit stirrer solution, and the resulting reaction was contacted to form a 200 g portion containing hydrolyzed propylene glycol. The weight of the isobutyl decane was synthesized according to the present formula, R2 group, m. For the completion of 9_18 g of 300 ml of the mixing stirrer, add ion -23-200903173. Discharge the aqueous solution of hydrochloric acid in the exchange water. After reacting for 2 hours, the solution should be cooled to room temperature. Instead of hydrochloric acid, it acts to promote the reaction of other acids. For example, nitric acid or phosphoric acid can also be used. After the reaction, ethanol and methanol were produced. Thereafter, propylene glycol monomethyl ether acetate was added to the reaction solution, and ethanol, methanol, water, and hydrochloric acid were distilled off under reduced pressure to obtain a solution of a condensate (polymer). In the solvent of the resulting solution, monomethyl ether acetate was contained in a weight ratio close to 100%. The polymer of the root was converted to a polystyrene average molecular weight Mw of 5,000 in terms of the molecular weight of GPC. (Synthesis Example 7) In the present synthesis example, tetraethoxydecane, phenyltrimethyl, and methyltriethoxydecane were used as the formula R^Si(OR3)4m (to indicate that the organic group 'R3 represents a carbon atom A hospital having a number of 1 to 4 represents a compound represented by 0, 1, or 2). Mixing 57.99 g of tetraethoxy decane, phenyltrimethoxy sand, 22.90 g of methyltriethoxy decane, and 85.14 g of ethanol, and mixing the resulting mixed solution with magnetic enthalpy And let it flow back. Next, an aqueous solution of 1.7 g of hydrochloric acid was dissolved in 28.1 g of the mixed solution of sub-exchanged water, and then the resulting reaction solution was cooled to room temperature. Instead of hydrochloric acid, other acids which promote the catalyst of the reaction, for example, nitric acid may be used, and after-products, ethanol and methanol may be formed. 200 g of the by-product ester obtained by the reverse reaction of the catalyst contains hydrolysis, and the propylene glycol is synthesized according to the weight of the isobutyl decane, R 2 group, m is 4.25 g in the yard, and the addition reaction is 2 small. The role is phosphoric acid. Anti-24-200903173 Thereafter, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and ethanol, methanol, water, and hydrochloric acid were distilled off under reduced pressure to obtain a solution containing a hydrolyzed condensate (polymer). In the solvent of the obtained solution, propylene glycol monomethyl ether acetate was contained in a weight ratio close to 100%. The polymer according to the present synthesis example has a weight average molecular weight Mw of 7700 in terms of the molecular weight of GPC in terms of polystyrene. The obtained solution was diluted with propylene glycol monomethyl ether acetate to form a solid content of 13.9% by mass. <Confirmation of stanol group> The presence of a stanol group (Si-OH bond) in the solution obtained in Synthesis Example 4 was measured by FT-IR and FT-NIR. The apparatus and conditions used are as follows.
• FT-IR 裝置：Nicο 1 et5 700 ( ThermoFisher SCIENTIFIC 公司 製） 測定波數：4000〜WOcnT1 掃描次數：3 2次 分解能：Scnr1 測定法：ATR法（金剛石）• FT-IR unit: Nicο 1 et 5 700 (manufactured by ThermoFisher SCIENTIFIC) Wavenumber: 4000~WOcnT1 Number of scans: 3 2 times Decomposition: Scnr1 Assay: ATR method (diamond)
• FT-NIR 裝置：Antaris ( ThermoFisher SCIENTIFIC 公司製） 測定波長：1 〇〇〇〜2500nm 掃描次數：1 6次 分解能：ScnT1 -25- 200903173 測定法：穿透法 由圖1所示之合成例4所得之丙二醇單甲醚醋酸酯溶 液（以下，稱爲「試料」）的FT-IR光譜，於3700〜3 200 cnT1中觀測到OH基的吸收（波峯），且OH基的波頂爲 3380 cnT1。添加乙醇之丙二醇單甲醚醋酸酯、添加甲醇之 丙二醇單甲醚醋酸酯、及添加水之丙二醇單甲醚醋酸酯的 FT-IR光譜，關於OH基的波頂，與“試料”之FT-IR光譜 所觀測之波數3 3 80(^1^1不同。由此結果，認爲於“試料”中 ，存在與乙醇、甲醇、水不同的OH基，且所觀測之波峰 爲來自矽烷醇基的波峯。 於圖2所示之FT-NIR光譜中，於1400〜1600nm特徵 性觀測到OH基的波峯。如水的OH基與乙醇的OH基般 ，FT-IR光譜中重疊的波峯，於FT-NIR光譜中可輕易觀 測到分離。 由“試料”之FT-NIR光譜，於1 400〜1 600nm觀測到2 個寬帶波峯。關於以己烷洗淨“試料”的沈澱物，亦觀測到 示出上述同樣波峯形狀之OH基的波峯。另一方面，由添 加乙醇之丙二醇單甲醚醋酸酯、添加甲醇之丙二醇單甲醚 醋酸酯、及添加水之丙二醇單甲醚醋酸酯之FT-NIR光譜 ，於1 400〜1 5 00nm觀測到大的波峯。此波長形狀爲與“試 料”之FT-NIR光譜所觀測的波峯形狀大爲不同。即使改變 丙二醇單甲醚醋酸酯中之乙醇、甲醇、水各別的濃度並且 測定，亦不會令所觀測的波峯形狀變化。因此，由“試料” 之FT-NIR光譜中於1 400〜1 600nm所觀測的波峯，推定係 -26- 200903173 爲來自矽烷醇基的波峯。 <耐溶劑評價> 於合成例1所得之溶液2 3克中，添加丙二醇單甲醚 醋酸酯77克’再適量添加順丁烯二酸及丙二醇單甲醚， 調製形成被膜用塗佈液。於合成例2所得之溶液2 3克中 添加丙二醇單甲醚醋酸酯77克，同上述調製形成被膜用 塗佈液。於合成例3所得之溶液2 5克中添加丙二醇單甲 醚醋酸酯75克，同上述調製形成被膜用塗佈液。於合成 例4所得之溶液23克中添加丙二醇單甲醚醋酸酯77克， 同上述調製形成被膜用塗佈液。於合成例5所得之溶液2 3 克中添加丙二醇單甲醚醋酸酯77克，同上述調製形成被 膜用塗佈液。於合成例6所得之溶液23克中添加丙二醇 單甲醚醋酸酯77克，同上述調製形成被膜用塗佈液。 於矽晶圓上，令使用合成例1至合成例7之溶液如前 述所調製的塗佈液，使用自旋器以旋塗法予以塗佈。其後 ，於保持在240°C溫度之熱板上將此矽晶圓加熱1分鐘令 塗佈液硬化，形成被膜。將形成被膜的矽晶圓，於使用作 爲光阻溶劑的丙二醇單甲醚醋酸酯中浸漬1分鐘。浸漬前 與浸漬後之被膜的膜厚變化，於使用任何合成例所得之溶 液所調製的塗佈液時均爲2nm以下。此結果，顯示所形成 之被膜可適用於光阻下層膜。 <耐顯像液評價> -27- 200903173 於矽晶圓上，令使用合成例1至合成例7之溶液如前 述所調製的塗佈液，使用自旋器以旋塗法予以塗佈。其後 ，於保持在240 °C溫度之熱板上將此矽晶圓加熱1分鐘令 塗佈液硬化，形成被膜。將形成被膜的矽晶圓，於一般使 用作爲光阻顯像液的2.3 8質量％氫氧化四甲基銨水溶液中 浸漬1分鐘。浸漬前與浸漬後的膜厚變化，於使用任何合 成例所得之溶液所調製的塗佈液時均爲2nm以下。此結果 ，顯示所形成之被膜可適於光阻下層膜。 <光學常數> 於矽晶圓上，令使用合成例1至合成例7之溶液如前 述所調製的塗佈液，使用自旋器以旋塗法予以塗佈。其後 ，於保持在240°C溫度之熱板上將此矽晶圓加熱1分鐘令 塗佈液硬化，形成膜厚〇.〇9 // m之被膜。使用分光橢圓計 (J.A. Woollam 公司製，VUV-VASE VU-302)，於矽晶圓 上所形成被膜之波長193 nm的折射率η及光學吸光係數（ 亦稱爲衰減係數）k之測定結果示於表1。 〔表1〕 折射率η 光學吸光係數k 1.48 0.00 1.67 0.23 1.85 0.55 1.66 0.23 1.69 0.25 1.65 0.25 1.60 0.10 使用由合成例1之溶液所調製的塗佈液 使用由合成例2之溶液所調製的塗佈液 使用由合成例3之溶液所調製的塗佈液 使用由合成例4之溶液所調製的塗佈液 使用由合成例5之溶液所調製的塗佈液 使用由合成例6之溶液所調製的塗佈液 使用由合成例7之溶液所調製的塗佈液 -28- 200903173 <乾式蝕刻速度> 於矽晶圓上，令使用合成例1至合成例3及合成例7 之溶液如前述所調製的塗佈液，使用自旋器以旋塗法予以 塗佈。其後，於保持在240 °C溫度之熱板上將此矽晶圓加 熱1分鐘令塗佈液硬化，形成膜厚0.09#m之被膜。又， 根據同樣之方法，於矽晶圓上塗佈光阻溶液（Shipley公 司製，商品名UV113)，形成光阻膜。 其次，對於所形成的被膜及光阻膜，使用CF4及〇2 作爲蝕刻氣體進行乾式蝕刻，測定乾式蝕刻速度。乾式蝕 刻所用之蝕刻劑，爲CF4氣體乾式蝕刻用之ES401 (曰本 Scienticific公司製），〇2氣體乾式蝕刻用之RIE-1 0NR ( samco公司製）。其次，求出被膜之乾式蝕刻速度相對於 光阻膜之乾式蝕刻速度之比（被膜之乾式蝕刻速度/光阻 膜之乾式蝕刻速度）的結果示於表2。此結果，顯示所形 成之被膜適用作爲光阻下層膜。 〔表2〕 cf4 〇2 使用由合成例1之溶液所調製的塗佈液 1.32 0.01 使用由合成例2之溶液所調製的塗佈液 1.44 0.02 使用由合成例3之溶液所調製的塗佈液 1.55 0.04 使用由合成例7之溶液所調製的塗佈液 1.66 0.02 上述之耐溶劑評價、耐顯像液評價、光學常數、及乾 式蝕刻速度，即使使用添加丙二醇單丙醚代替丙二醇單甲 -29- 200903173 醚之塗佈液所形成的被膜，於實質上亦無變化。又，使用 未添加順丁烯二酸之塗佈液（保存期間0日）所形成被膜 之情形’關於上述之耐溶劑評價、耐顯像液評價、光學常 數、及乾式蝕刻速度，與使用添加順丁烯二酸之塗佈液所 形成被膜之情形相比較，無實質上之變化。 (實施例1 ) 於合成例4之溶液1 2 5 · 4 6克中，添加順丁嫌二酸 0.73克（12.6毫莫耳/公斤）、丙二醇單甲醚237.50克、 丙二醇單甲醚醋酸酯136.31克，調製本發明之形成被膜 用塗佈液。 (實施例2 ) 於合成例4之溶液1 2 5 · 4 6克中，添加順丁烯二酸 0.73克（12.6毫莫耳/公斤）、丙二醇單甲醚237.50克、 丙二醇單甲醚醋酸酯136.31克，調製本發明之形成被膜 用塗佈液。本實施例爲在使用丙二醇單丙醚代替丙二醇單 甲醚此點，與實施例1不同。 (實施例3 ) 於合成例4之溶液142.04克中，添加氯化苄基三乙 基銨0.06克、順丁烯二酸0.197克、丙二醇單丙醚240.00 克、丙二醇單甲醚醋酸酯21.70克、丙二醇單甲醚96.00 克，調製本發明之形成被膜用塗佈液。 -30- 200903173 (實施例4 ) 於合成例7之溶液142.04克中，添加氯化苄基三乙 基銨0.06克、順-5 -原冰片烯·內_2,3 -二竣酸〇_95克、丙 二醇單丙醚240.00克、丙二醇單甲醚醋酸酯26·35克、丙 二醇單甲醚96.00克，調製本發明之形成被膜用塗佈液。• FT-NIR device: Antaris (manufactured by ThermoFisher SCIENTIFIC) Measurement wavelength: 1 〇〇〇~2500nm Scanning times: 1 6 decomposition energy: ScnT1 -25- 200903173 Measurement method: Penetration method Synthesis example 4 shown in Fig. 1 The FT-IR spectrum of the obtained propylene glycol monomethyl ether acetate solution (hereinafter referred to as "sample") observed the absorption (peak) of the OH group in 3700 to 3 200 cnT1, and the wave top of the OH group was 3380 cnT1. . FT-IR spectrum of propylene glycol monomethyl ether acetate added with ethanol, propylene glycol monomethyl ether acetate added with methanol, and propylene glycol monomethyl ether acetate added with water, the top of the OH group, and the FT- of the "sample" The wave number observed by IR spectrum is 3 3 80 (^1^1 is different. From this result, it is considered that there is an OH group different from ethanol, methanol, and water in the "sample", and the observed peak is derived from stanol The peak of the base. In the FT-NIR spectrum shown in Fig. 2, the peak of the OH group is characteristically observed at 1400~1600 nm. Like the OH group of water and the OH group of ethanol, the overlapping peaks in the FT-IR spectrum are Separation can be easily observed in the FT-NIR spectrum. From the FT-NIR spectrum of the "sample", two broadband peaks were observed at 1 400 to 1 600 nm. It was also observed that the precipitate of the "sample" was washed with hexane. The peak of the OH group of the same peak shape is shown. On the other hand, the FT- of propylene glycol monomethyl ether acetate added with ethanol, propylene glycol monomethyl ether acetate added with methanol, and propylene glycol monomethyl ether acetate added with water NIR spectrum, a large peak was observed at 1 400 to 1 500 nm. The long shape is much different from the shape of the peak observed by the FT-NIR spectrum of the "sample". Even if the concentration of ethanol, methanol, and water in the propylene glycol monomethyl ether acetate is changed and measured, it will not be observed. The shape of the peak changes. Therefore, from the peak observed at 1 400 to 1 600 nm in the FT-NIR spectrum of the "sample", it is estimated that the line -26-200903173 is a peak derived from a decyl alcohol group. <Solvent resistance evaluation> In a solution of 2 g of the solution obtained in Example 1, 77 g of propylene glycol monomethyl ether acetate was added, and maleic acid and propylene glycol monomethyl ether were added in an appropriate amount to prepare a coating liquid for a coating film. The solution 2 obtained in Synthesis Example 2 77 g of propylene glycol monomethyl ether acetate was added to 3 g, and the coating liquid for film formation was prepared as described above. 75 g of propylene glycol monomethyl ether acetate was added to 25 g of the solution obtained in Synthesis Example 3, and the film was formed as described above. A coating liquid was added to a solution obtained in Synthesis Example 4, and 77 g of propylene glycol monomethyl ether acetate was added thereto to prepare a coating liquid for coating film. The propylene glycol monomethyl ether was added to 2 3 g of the solution obtained in Synthesis Example 5. Acetate 77 In the same manner as described above, a coating liquid for a coating film was prepared, and 77 g of propylene glycol monomethyl ether acetate was added to 23 g of the solution obtained in Synthesis Example 6 to prepare a coating liquid for a coating film as described above. The solutions of Examples 1 to 7 were coated as described above using a spinner by spin coating. Thereafter, the wafer was heated on a hot plate maintained at a temperature of 240 ° C. The coating liquid was hardened to form a film, and the ruthenium wafer on which the film was formed was immersed in propylene glycol monomethyl ether acetate as a photoresist solvent for 1 minute. The film thickness of the film before immersion and after immersion was changed. The coating liquid prepared by the solution obtained by any of the synthesis examples was 2 nm or less. As a result, it was revealed that the formed film can be applied to the photoresist underlayer film. <Evaluation of the image-resistant liquid> -27- 200903173 On the wafer, the solution of the synthesis examples 1 to 7 was applied as described above, and the coating solution was applied by spin coating using a spinner. . Thereafter, the crucible wafer was heated on a hot plate maintained at a temperature of 240 ° C for 1 minute to harden the coating liquid to form a film. The tantalum wafer on which the film was formed was immersed for 1 minute in an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide which is generally used as a photoresist developing solution. The film thickness before and after the immersion was changed to 2 nm or less when using the coating liquid prepared by using the solution obtained in any of the synthetic examples. As a result, it was revealed that the formed film can be adapted to the photoresist underlayer film. <Optical constant> On the enamel wafer, the solutions prepared in Synthesis Example 1 to Synthesis Example 7 were applied by spin coating using a spinner prepared as described above. Thereafter, the crucible wafer was heated on a hot plate maintained at a temperature of 240 ° C for 1 minute to harden the coating liquid to form a film having a film thickness of //. Using a spectroscopic ellipsometer (VUV-VASE VU-302, manufactured by JA Woollam Co., Ltd.), the measurement results of the refractive index η at a wavelength of 193 nm and the optical absorption coefficient (also referred to as an attenuation coefficient) k of the film formed on the germanium wafer are shown. In Table 1. [Table 1] Refractive index η Optical absorption coefficient k 1.48 0.00 1.67 0.23 1.85 0.55 1.66 0.23 1.69 0.25 1.65 0.25 1.60 0.10 Using the coating liquid prepared by the solution of Synthesis Example 1 using the coating prepared by the solution of Synthesis Example 2 The coating liquid prepared by the solution of Synthesis Example 3 was used as the coating liquid prepared by the solution of Synthesis Example 4, and the coating liquid prepared by the solution of Synthesis Example 5 was used to prepare the coating liquid prepared by the solution of Synthesis Example 6. The coating liquid was prepared by using the coating liquid prepared by the solution of Synthesis Example 7-28-200903173 <dry etching rate> on the wafer, and the solutions using Synthesis Example 1 to Synthesis Example 3 and Synthesis Example 7 were as described above. The prepared coating liquid was applied by spin coating using a spinner. Thereafter, the crucible wafer was heated for 1 minute on a hot plate maintained at a temperature of 240 ° C to cure the coating liquid to form a film having a film thickness of 0.09 #m. Further, according to the same method, a photoresist solution (trade name: UV113) manufactured by Shipley Co., Ltd. was applied onto the wafer to form a photoresist film. Next, the formed film and the photoresist film were dry-etched using CF4 and 〇2 as an etching gas, and the dry etching rate was measured. The etchant used for dry etching is ES401 (manufactured by Shoic Scienticific Co., Ltd.) for dry etching of CF4 gas, and RIE-1 0NR (manufactured by Samco Co., Ltd.) for dry etching of 〇2 gas. Next, the results of the ratio of the dry etching rate of the film to the dry etching rate of the photoresist film (the dry etching rate of the film/the dry etching rate of the photoresist film) are shown in Table 2. As a result, it was revealed that the formed film was applied as a photoresist underlayer film. [Table 2] cf4 〇2 Using the coating liquid prepared by the solution of Synthesis Example 1.32 0.01 Using the coating liquid prepared by the solution of Synthesis Example 1.44 0.02 The coating liquid prepared by the solution of Synthesis Example 3 was used. 1.55 0.04 Using the coating liquid prepared by the solution of Synthesis Example 1.66 0.02 Solvent resistance evaluation, development liquid resistance evaluation, optical constant, and dry etching speed, even if propylene glycol monopropyl ether was used instead of propylene glycol monomethyl -29 - 200903173 The film formed by the ether coating solution did not change substantially. Moreover, the case where the film formed by the coating liquid which does not add a maleic acid (0 day of storage period) is used, and the solvent resistance evaluation, the image-resistance evaluation, the optical constant, and the dry etching speed are added, and the use is added. There is no substantial change in the case of the film formed by the coating liquid of maleic acid. (Example 1) In the solution 1 2 5 · 4 6 g of the synthesis example 4, 0.73 g (12.6 mmol/kg) of cis-succinic acid, 237.50 g of propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate were added. 136.31 g, the coating liquid for forming a film of the present invention was prepared. (Example 2) In the solution 1 2 5 · 4 6 g of the synthesis example 4, 0.73 g of maleic acid (12.6 mmol/kg), 237.50 g of propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate were added. 136.31 g, the coating liquid for forming a film of the present invention was prepared. This example is different from Example 1 in that propylene glycol monopropyl ether is used instead of propylene glycol monomethyl ether. (Example 3) In 142.04 g of the solution of Synthesis Example 4, 0.06 g of benzyltriethylammonium chloride, 0.197 g of maleic acid, 240.00 g of propylene glycol monopropyl ether, and 21.70 g of propylene glycol monomethyl ether acetate were added. Further, 96.00 g of propylene glycol monomethyl ether was used to prepare a coating liquid for forming a film of the present invention. -30-200903173 (Example 4) In 142.04 g of the solution of Synthesis Example 7, 0.06 g of benzyltriethylammonium chloride, cis-5-formylene·intra-2,3-didecanoate 〇 was added. 95 g of propylene glycol monopropyl ether (240.00 g), propylene glycol monomethyl ether acetate (26.35 g, and propylene glycol monomethyl ether 96.00 g) were used to prepare a coating liquid for forming a film of the present invention.
㈧ 順-5 -原冰片烯-內-2，3 -二竣酸爲例如令上述式（Α ) 所示’由東京化成工業（股）等可取得之5_原冰片烯_2,3. 二羧酸酐（Hymic Acid Anhydride)水解並將其反應產物 精製則可取得。直接’取得式（A )所示之化合物（ Sigma-Aldrich公司製），並且使用亦可。 (比較例1 ) 未添加順丁烯二酸此點、及未添加丙二醇單甲醚或丙 二醇單丙醚此點’與實施例1及實施例2爲不同之例。即 ，於合成例4之溶液23克中添加丙二醇單甲醚醋酸酯77 克’調製形成被膜用塗佈液。 -31 - 200903173 (參考例1 ) 使用反型之二價羧酸（二羧酸）之反丁烯二酸丨丨丨貞 丁烯二酸此點，與實施例1及實施例2爲不同之例。％， 於合成例4之溶液125·46克中添加反丁烯二酸0.73克（ 12.6毫莫耳/公斤）、丙二醇單甲醚237.50克、芮二醇單 甲醚醋酸酯136.31克，調製形成被膜用塗佈液。 (比較例2) 使用DL-蘋果酸代替順丁烯二酸此點，與實施例1及 實施例2爲不同之例。即，於合成例4之溶液1 2 4.8 9克 中添加DL-蘋果酸0.84克（12.5毫莫耳/公斤）、丙二醇 單甲醚23 7.5 0克、丙二醇單甲醚醋酸酯1 3 6.77克，調製 形成被膜用塗佈液。 (參考例2 ) 使用號拍酸代替順丁烯二酸此點，與實施例1及實施 例2爲不同之例。即，於合成例4之溶液1 2 5.4 〇克中添 加琥珀酸〇·74克（ι2·5毫莫耳/公斤）、丙二醇單甲醚 2 3 7.5 0克、丙二醇單甲醚醋酸酯1 36 77克，調製形成被 膜用塗佈液。 (比較例3 ) 於未添加順丁烯二酸此點爲與實施例2不同之例。即 於合成例4之溶液ι29.22克中添加丙二醇單丙醚 -32- 200903173 237.50克、丙二醇單甲醚醋酸酯13327克，調製形成被 膜用塗佈液。 (比較例4 ) 於未添加順丁烯二酸此點爲與實施例3不同之例。即 ，於合成例7之溶液143.45克中添加氯化苄基三乙基銨 0.06克、丙二醇單丙醚240.00克、丙二醇單甲醚醋酸酯 20.49克、丙二醇單甲醚96.00克，調製形成被膜用塗佈 液。 (比較例5 ) 使用例如下述式（B )所示之5-原冰片烯-2-內，3- 外-二羧酸代替順-5-原冰片烯-內-2,3-二羧酸此點爲與實施 例4不同之例。即，於合成例7之溶液1 3 6.6 4克中，添 加氯化节基三乙基錢〇.06克、5-原冰片稀-2-內，3-外-二 羧酸（Sigma-Aldrich公司製）〇_95克、丙二醇單丙醚 240.00克、丙二醇單甲醚醋酸酯26.35克、丙二醇單甲醚 96.00克，調製形成被膜用塗佈液。 [化2](8) cis-5-formylbornene-endo-2,3-dicarboxylic acid is, for example, the above-mentioned formula (Α), which is obtained by Tokyo Chemical Industry Co., Ltd., etc. It can be obtained by hydrolyzing a Hymic Acid Anhydride and refining the reaction product. The compound represented by the formula (A) (manufactured by Sigma-Aldrich Co., Ltd.) was directly obtained and used. (Comparative Example 1) The point at which no maleic acid was added and the case where propylene glycol monomethyl ether or propylene glycol monopropyl ether was not added was different from Examples 1 and 2. Specifically, 77 g of propylene glycol monomethyl ether acetate was added to 23 g of the solution of Synthesis Example 4 to prepare a coating liquid for film formation. -31 - 200903173 (Reference Example 1) The use of the trans-divalent carboxylic acid (dicarboxylic acid) of maleic acid methacrylic acid is different from that of Example 1 and Example 2. example. %, 0.73 g of fumaric acid (12. 6 mmol/kg), 237.50 g of propylene glycol monomethyl ether and 136.31 g of decanediol monomethyl ether acetate were added to 125.46 g of the solution of Synthesis Example 4. Coating liquid for film. (Comparative Example 2) The case of using DL-malic acid instead of maleic acid was different from Example 1 and Example 2. That is, 0.84 g (12.5 mmol/kg) of DL-malic acid, 237.50 g of propylene glycol monomethyl ether, and 6.37 g of propylene glycol monomethyl ether acetate were added to the solution 1 2 4.8 9 g of the synthesis example 4, The coating liquid for film formation is prepared. (Reference Example 2) This is an example different from Example 1 and Example 2, except that the acid was used instead of maleic acid. Namely, ytterbium succinate·74 g (1⁄2·5 mmol/kg), propylene glycol monomethyl ether 2 3 7.5 0 g, and propylene glycol monomethyl ether acetate 1 36 were added to the solution 1 2 5.4 g of the synthesis example 4. 77 g was prepared to form a coating liquid for a film. (Comparative Example 3) This point is different from Example 2 in that no maleic acid was added. In the solution of the solution of Synthesis Example 4, 139.22 g of propylene glycol monopropyl ether-32-200903173 and 13327 g of propylene glycol monomethyl ether acetate were added to prepare a coating liquid for coating. (Comparative Example 4) This is an example different from Example 3 in that no maleic acid was added. That is, 0.036 g of benzyltriethylammonium chloride, 240.00 g of propylene glycol monopropyl ether, 20.49 g of propylene glycol monomethyl ether acetate, and 96.00 g of propylene glycol monomethyl ether were added to 143.45 g of the solution of Synthesis Example 7, and the film was prepared to form a film. Coating solution. (Comparative Example 5) Using, for example, 5-norbornene-2-one, 3-exo-dicarboxylic acid, as shown in the following formula (B), instead of cis-5-formylene-endo-2,3-dicarboxylate The acid point is an example different from that of the fourth embodiment. That is, in the solution 1 3 6.6 4 g of the synthesis example 7, chlorinated benzyl triethyl ketone .06 g, 5-oriole borneol dilute 2-, 3-exo-dicarboxylic acid (Sigma-Aldrich) was added. The company made 〇_95 g, propylene glycol monopropyl ether 240.00 g, propylene glycol monomethyl ether acetate 26.35 g, and propylene glycol monomethyl ether 96.00 g, and prepared to form a coating liquid for a film. [Chemical 2]
(B) -33- 200903173 • <保存安定性評價> 將調製之塗佈液以高於室溫之35°C溫度下最多保存1 個月，根據保存前與保存期間經過後的分子量分佈變化’ 進行保存安定性之評價。 關於實施例1所調製之塗佈液（保存期間0日）’根 據GPC所測定之分子量分佈示於圖3(A)。關於此塗佈 液以35 °C之溫度保存1週者’以同溫度保存2週者’以同 溫度保存1個月者，根據G Pc所測定之分子量分佈分別 示於圖3(B)、圖3(C)、圖3(D)。其次’將圖3( A)至圖3 (D)所示之分子量分佈全部重疊的結果不於圖 4。若參照圖4，可知經由以3 51之溫度至少保存1個月 ，則塗佈液的分子量分佈無實質上變化。即，顯示出保存 安定性優良。 關於實施例2所調製之塗佈液（保存期間0日）、和 3 51：之溫度保存1個月之塗佈液，根據GPC之分子量分 佈爲與圖3(A)、圖3(D)大約相同。因此’經由以35 。(：之溫度至少保存1個月，則塗佈液的分子量分佈爲與實 施例1同樣地無實質上變化。 關於比較例1所調製，不含有順丁嫌二酸的塗佈液（ 保存期間〇日）、和此塗佈液以3 5 °C之溫度保存1週者’ 以同溫度保存2週者’以同溫度保存1個月者’將GPC 所測定之分子量分佈全部重疊的結果示於圖5 °經由以3 5 。(：之溫度保存2週及1個月，則塗佈液的分子量分佈變化 ，具體而言’相對地高分子量聚合物的比例增加’另一方 -34- 200903173 面，相對地低分子量聚合物的比例減少。即，與添加 烯二酸之情況相比較，顯示保存安定性差。 關於參考例1所調製，含有反丁烯二酸代替順丁 酸之塗佈液（保存期間〇日）、和此塗佈液以3 51之 保存1個月者，將GPC所測定之分子量分佈全部重 結果示於圖6。經由以3 5 °C之溫度保存1個月，則塗 的分子量分佈變化，具體而言，相對地商分子量聚合 比例增加，另一方面，相對地低分子量聚合物的比例 。即，與添加順丁烯二酸之情況相比較，顯示保存安 爲不佳。但是，若比較圖5與圖6，則參考例1所調 塗佈液爲較比較例1所調製之塗佈液更加察見保存安 的提高。 關於比較例2所調製’含有DL-蘋果酸代替順丁 酸之塗佈液（保存期間〇日）、和此塗佈液以3 5 °c之 保存1個月者，將GP C所測定之分子量分佈全部重 結果示於圖7。經由以3 5 °C之溫度保存1個月’則塗 的分子量分佈變化，具體而言’相對地高分子量聚合 比例增加，另一方面，相對地低分子量聚合物的比例 。即，與添加順丁烯二酸之情況相比較’顯示保存安 差。 關於參考例2所調製’含有琥珀酸代替順丁烯二 塗佈液（保存期間〇日）、和此塗佈液以3 5 °C之溫度 1個月者，將GPC所測定之分子量分佈全部重疊的結 於圖8。經由以3 51之溫度保存1個月’則塗佈液的 順丁 烯二 溫度 疊的 佈液 物的 減少 定性 製之 定性 烯二 溫度 疊的 佈液 物的 減少 定性 酸之 保存 果示 分子 -35- 200903173 量分佈變化，具體而言，相對地高分子量聚合物的比例增 加’另一方面，相對地低分子量聚合物的比例減少。即， 與添加順丁烯二酸之情況相比較，顯示保存安定性爲不佳 。但是，若比較圖5與圖8，則參考例2所調製之塗佈液 爲較比較例1所調製之塗佈液更加察見保存安定性的提高 〇 關於比較例3所調製，不含有順丁烯二酸之塗佈液（ 保存期間〇日）、和此塗佈液以3 5 °c之溫度保存1週者， 以同溫度保存2週者，以同溫度保存1個月者，將GPC 所測定之分子量分佈全部重疊的結果示於圖9。經由以35 。(：之溫度保存2週及1個月，則塗佈液的分子量分佈變化 ，具體而言，相對地高分子量聚合物的比例增加’另一方 面，相對地低分子量聚合物的比例減少。即，與添加順丁 烯二酸之情況相比較，顯示保存安定性差。 關於實施例3所調製，含有順丁烯二酸及氯化苄基三 乙基銨之塗佈液（保存期間〇日）、和此塗佈液以3 5 °C之 溫度保存2週者’將GPC所測定之分子量分佈全部重疊 的結果示於圖1 〇。經由以3 5 °C之溫度保存至少2週，則 塗佈液的分子量分佈無實質上的變化。即’顯示保存安定 性優良。 關於實施例4所調製’含有順_ 5 _原冰片嫌-內·2，3 _ — 羧酸及氯化苄基三乙基銨之塗佈液（保存期間0日）、和 此塗佈液以3 5。(：之溫度保存2週者’將G P C所測定之分 子量分佈全部重疊的結果示於圖n。經由以3 5 °C之溫度 -36- 200903173 保存2週，則塗佈液的分子量分佈變化，具體而_ ’相對 地高分子量聚合物的比例增加’另一方面’相對地低分子 量聚合物的比例減少。但是，若比較圖1 1與後述之圖1 2 ，則實施例4所調製之塗佈液爲較比較例4所調製之塗佈 液更加察見保存安定性的提高。 關於比較例4所調製’含有氯化节基三乙基銨但不含 順丁烯二酸及順-5 -原冰片烯-內-2，3 -二羧酸之塗佈液（保 存期間0日）、和此塗佈液以3 5 °C之溫度保存2週者’將 G P C所測定之分子量分佈全部重疊的結果示於圖1 2。經 由以3 5 °C之溫度保存2週’則塗佈液的分子量分佈變化， 具體而言’相對地高分子量聚合物的比例增加’另一方面 ，相對地低分子量聚合物的比例減少。即，與添加順丁烯 二酸或順-5-原冰片烯-內-2,3-二羧酸之情況相比較，顯示 保存安定性差。 關於比較例5所調製，含有5-原冰片烯-2-內，3-外-二羧酸及氯化苄基三乙基銨之塗佈液（保存期間〇日）、 和此塗佈液以3 5 °C之溫度保存2週者，將GPC所測定之 分子量分佈全部重疊的結果示於圖1 3。經由以3 5 °C之溫 度保存2週，則塗佈液的分子量分佈變化，具體而言，相 對地高分子量聚合物的比例增加，另一方面，相對地低分 子量聚合物的比例減少。即，與添加順丁烯二酸或順-5-原 冰片烯-內-2，3 -二羧酸之情況相比較’則顯示保存安定性 差。 -37- 200903173 <形成光阻圖型之評價> 本發明之形成被膜用塗佈液，可使用於基板與光阻之 間形成光阻下層膜。 令2-乙烯基萘30克、甲基丙烯酸縮水甘油酯3.5克 、甲基丙烯酸1-丁氧乙酯4.5克溶解於環己酮112克後， 將燒瓶內以氮氣更換並升溫至60 °C。升溫後，將溶解於環 己酮48克之偶氮雙異丁腈1.9克於氮加壓下添加，並以 6 0 °C反應24小時。將反應溶液冷卻後，投入甲醇，令聚 合物再沈澱、加熱乾燥取得下述式（C )所示之聚合物。 所得聚合物以GPC之分子量，換算爲聚苯乙烯之重量平 均分子量Mw爲12000。(B) -33- 200903173 • <Preservation stability evaluation> The prepared coating liquid is stored for up to 1 month at a temperature higher than room temperature of 35 ° C, and the molecular weight distribution after passing through the storage period before storage Change ' to evaluate the preservation stability. The coating liquid prepared in Example 1 (0 day of storage period) is shown in Fig. 3(A) based on the molecular weight distribution measured by GPC. The coating solution was stored at a temperature of 35 ° C for one week. The person who stored at the same temperature for 2 weeks was stored at the same temperature for one month. The molecular weight distribution measured according to G Pc is shown in Fig. 3 (B). 3(C) and 3(D). Next, the results of overlapping the molecular weight distributions shown in Figs. 3(A) to 3(D) are not shown in Fig. 4. Referring to Fig. 4, it is understood that the molecular weight distribution of the coating liquid does not substantially change by being stored at a temperature of 3 51 for at least one month. That is, it shows that the preservation stability is excellent. The coating liquid prepared in Example 2 (0 days in the storage period) and the coating liquid stored at a temperature of 3 51 were stored for 1 month, and the molecular weight distribution according to GPC was as shown in Fig. 3 (A) and Fig. 3 (D). About the same. So 'via 35'. (The temperature of the coating liquid was not substantially changed in the same manner as in Example 1 when the temperature was kept at least for one month. The coating liquid prepared in Comparative Example 1 did not contain the succinic acid (during storage period) 〇 ) 、 、 、 、 、 、 、 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以 以In Fig. 5 °, the temperature distribution of the coating liquid changes by storing at a temperature of 3 5 ° (for 2 weeks and 1 month), specifically, the ratio of 'relatively high molecular weight polymer increases'. The other side -34-200903173 The ratio of the relatively low molecular weight polymer is reduced, that is, the storage stability is poor as compared with the case of adding the enedic acid. The coating liquid containing the fumaric acid instead of the cis-butyric acid prepared in Reference Example 1 (The day after the storage period), and the coating liquid was stored at 301 for one month, and the results of all the molecular weight distributions measured by GPC are shown in Fig. 6. The sample was stored at a temperature of 35 ° C for one month. Then the molecular weight distribution of the coating changes, specifically, relative The ratio of the molecular weight polymerization is increased, and on the other hand, the ratio of the relatively low molecular weight polymer, that is, the storage safety is poor compared with the case of adding maleic acid. However, if FIG. 5 and FIG. 6 are compared, Then, the coating liquid adjusted in Reference Example 1 was more improved than the coating liquid prepared in Comparative Example 1. The coating liquid containing DL-malic acid instead of cis-butyric acid was prepared in Comparative Example 2 (preservation) In the next day, and the coating liquid was stored at 35 ° C for one month, the results of the molecular weight distribution measured by GP C were all shown in Fig. 7. The temperature was maintained at 35 ° C for one month. 'The molecular weight distribution of the coating is changed, specifically the 'relatively high molecular weight polymerization ratio is increased, on the other hand, the ratio of the relatively low molecular weight polymer. That is, compared with the case of adding maleic acid' The molecular weight measured by GPC is the same as that prepared in Reference Example 2, where succinic acid is substituted for the maleic coating solution (the day after the storage), and the coating liquid is at a temperature of 35 ° C for one month. The distribution of all overlapping is shown in Figure 8. Via 3 The temperature of 51 is stored for 1 month', then the decrease of the liquid content of the butadiene temperature of the coating liquid is qualitatively determined by the qualitative determination of the temperature of the liquid mixture of the olefinic temperature. The preservation of the qualitative acid molecule -35- 200903173 The change in the amount distribution, specifically, the proportion of the relatively high molecular weight polymer increases. On the other hand, the proportion of the relatively low molecular weight polymer decreases. That is, the preservation stability is shown as compared with the case of adding maleic acid. However, when comparing FIG. 5 with FIG. 8, the coating liquid prepared in Reference Example 2 is more improved in storage stability than the coating liquid prepared in Comparative Example 1, and is prepared in Comparative Example 3. The coating liquid containing no maleic acid (the day after the storage period), and the coating liquid stored at a temperature of 35 ° C for one week, and stored at the same temperature for 2 weeks, and stored at the same temperature for 1 week. The results of overlapping the molecular weight distributions measured by GPC are shown in Fig. 9. Via 35. (When the temperature is stored for 2 weeks and 1 month, the molecular weight distribution of the coating liquid changes, specifically, the ratio of the relatively high molecular weight polymer increases. On the other hand, the ratio of the relatively low molecular weight polymer decreases. Compared with the case of adding maleic acid, the storage stability was poor. The coating liquid containing maleic acid and benzyltriethylammonium chloride prepared in Example 3 (the day after the storage period) And the result that the coating liquid was stored at a temperature of 35 ° C for 2 weeks. The results of overlapping the molecular weight distribution measured by GPC are shown in Fig. 1. The coating liquid is stored at a temperature of 35 ° C for at least 2 weeks, and then coated. The molecular weight distribution of the cloth liquid did not change substantially. That is, it showed excellent preservation stability. The preparation of Example 4 contained cis_5_original borneol-inner·2,3 _carboxylic acid and benzyl chloride three. The coating solution of ethylammonium (on the 0th day of storage) and the coating liquid were 35. (The temperature at which the temperature was stored for 2 weeks, and the results of overlapping the molecular weight distribution measured by GPC are shown in Fig. n. 3 5 °C temperature -36- 200903173 2 weeks, the liquid of the coating liquid The amount distribution changes, specifically, the ratio of the relatively high molecular weight polymer increases, and the ratio of the relatively low molecular weight polymer decreases. However, if FIG. 11 is compared with FIG. 12 described later, Example 4 The prepared coating liquid was more improved in storage stability than the coating liquid prepared in Comparative Example 4. The preparation of Comparative Example 4 contained 'chlorinated triethylammonium chloride but no maleic acid. And the coating solution of the cis-5-formary norbornene-endo-2,3-dicarboxylic acid (0 days during storage), and the coating solution was stored at a temperature of 35 ° C for 2 weeks. The results of the overlapping of the molecular weight distributions are shown in Fig. 12. The molecular weight distribution of the coating liquid is changed by storing at a temperature of 35 ° C for 2 weeks, specifically, the ratio of the relatively high molecular weight polymer is increased. On the other hand, the ratio of the relatively low molecular weight polymer is decreased, that is, the storage stability is poor as compared with the case of adding maleic acid or cis-5-formylene-endo-2,3-dicarboxylic acid. Prepared in Comparative Example 5, containing 5-norbornene-2-inner, 3-exo-dicarboxylic acid and benzyl chloride The coating liquid of triethylammonium (the day after the storage period) and the coating liquid were stored at a temperature of 35 ° C for 2 weeks, and the results of overlapping the molecular weight distributions measured by GPC are shown in Fig. 13. When stored at a temperature of 35 ° C for 2 weeks, the molecular weight distribution of the coating liquid changes, specifically, the ratio of the relatively high molecular weight polymer increases, and on the other hand, the ratio of the relatively low molecular weight polymer decreases. Compared with the case of adding maleic acid or cis-5-formylbornene-endo-2,3-dicarboxylic acid, it shows poor preservation stability. -37- 200903173 <Evaluation of formation of photoresist pattern> The coating liquid for forming a film of the present invention can be used to form a photoresist underlayer film between the substrate and the photoresist. 30 g of 2-vinylnaphthalene, 3.5 g of glycidyl methacrylate and 4.5 g of 1-butoxyethyl methacrylate were dissolved in 112 g of cyclohexanone, and the flask was replaced with nitrogen and heated to 60 ° C. . After the temperature was raised, 1.9 g of azobisisobutyronitrile dissolved in cyclohexanone (48 g) was added under a nitrogen pressure, and reacted at 60 ° C for 24 hours. After cooling the reaction solution, methanol was introduced, the polymer was reprecipitated, and dried by heating to obtain a polymer represented by the following formula (C). The obtained polymer had a weight average molecular weight Mw of 12,000 in terms of molecular weight of GPC in terms of polystyrene.
I Η 0 - ？-〇(CH2)3CH3 ch3 (C) 於式（C)中’若將全部重複單位視爲100旲耳％， 則含有2 -乙烯基萘之重複單位爲80莫耳％，含有甲基丙 烯酸1-丁氧乙酯之重複單位爲10莫耳％，含有甲基丙烯 酸縮水甘油酯之重複單位爲1 〇莫耳％之比例。 於所得之聚合物5克中，混合界面活性劑（大日本油 墨化學工業（股）製’商品名：Megafac R-30) 〇.〇3克， 並作成溶解於環己酮23克及丙二醇單甲醚23克之溶液。 -38- 200903173 其後，使用孔徑0.10/^m之聚乙烯製微濾器過濾，再使用 孔徑0.0 5 /zm之聚乙烯製微濾器過濾，調製光刻蝕步驟中 所用的形成光阻下層膜組成物。由此組成物所形成不含矽 之光阻下層膜（A層）、與本發明之形成被膜用塗佈液所 形成之含矽的光阻下層膜（B層）組合，構成多層膜。 將調製之形成光阻下層膜組成物（包含式（C )所示 之聚合物）於矽晶圓上塗佈，並於熱板上以2 4 0 °C加熱1 分鐘，形成膜厚25 Onm之光阻下層膜（A層）。於其上， 將本說明書之實施例3及4以及比較例4及5之形成被膜 用塗佈液，分別使用旋塗器塗佈，並於熱板上以240 °C加 熱1分鐘，形成膜厚80nm之含矽光阻下層膜（B層）。 所使用之形成被膜用塗佈液爲保存期間〇日者，和35°C保 存2週者。於其上將市售之光阻溶液（住友化學（股）製 ，商品名：PAR855)以旋塗器塗佈，並於熱板上以100°C 加熱1分鐘，形成膜厚l5〇nm之光阻膜（C層）。 使用掃描器（ASML公司製’ PAS5 500/1 1 00、波長 pSnm、ΝΑ，σ : 0.75，0.89/0.59 (雙極））’進行形成 光阻膜（C層）之圖型。標的物爲透過顯像後之光阻圖型 的線寬及其線間之寬度爲〇.08 # m之所謂線/空間（濃線 )設定成形成9根線數的光罩進行曝光。其後’於熱板上 以105 °c加熱60秒鐘，冷卻後’以工業規格之60秒鐘單 獎式步驟以顯像液（2·3 8質量％氫氧化四甲基錢水溶液） 予以顯像。 於各種光阻下層膜（B層）上所形成之光阻圖型的形 -39- 200903173 狀示於表3。光阻圖型無所謂之下切、拉末端等大約直末 端形狀之情況以“良好”表示。其次，光阻圖型倒壞之情況 以“圖型倒塌”表示。表3之結果，顯示經由含有順型之二 價羧酸（二羧酸）之順丁烯二酸或順-5-原冰片烯-內-2,3-二羧酸之塗佈液所形成之光阻下層膜（B層）的存在，則 不會令上層所形成的光阻圖型倒壞並且顯示出形成所欲形 狀的效果。 〔表3〕 塗佈液之保存條件 〇曰 35〇C 2 週 實施例3 良好 良好 實施例4 良好 良好 比較例4 良好 圖型倒塌 比較例5 良好 圖型倒塌 <半導體裝置之製造> 於形成有機膜之矽晶圓的有機膜上，將前述實施例1 或實施例2所調製之塗佈液，以使用自旋器之旋塗法予以 塗佈。其後，於保持在24CTC溫度之熱板上將此矽晶圓加 熱1分鐘令塗佈液硬化，形成光阻下層膜。 其後，於光阻下層膜上塗佈光阻溶液（Shipley公司 製，商品名UV113)，令其硬化，形成光阻膜。光阻膜的 形成法若使用與形成光阻下層膜同樣之方法即可。 將所形成之光阻膜透過標線（光罩）曝光。曝光後， 以1 5 0 °C以下之溫度例如1 〇 〇 °C，加熱指定之時間例如1 分鐘即可。由此，經由顯像，形成指定形狀之光阻圖型。 -40- 200903173 顯像液可使用例如2.3 8質量％氫氧化四甲基銨水溶液。其 後，以此光阻圖型作爲光罩，使用含CF4氣體對於光阻下 層膜進行乾式蝕刻，形成光阻下層膜之圖型。 以所形成之光阻下層膜的圖型及光阻圖型作爲光罩， 使用含〇2氣體對於矽晶圓上所形成之有機膜進行乾式蝕 刻。此時，雖殘存光阻下層膜，但光阻圖型被除去。如此 ，於矽晶圓上形成有機膜之圖型。 接著，根據公知技術經過加工矽晶圓等之步驟，可製 作各種半導體裝置。另外，於最終所製作的半導體裝置中 ，有機膜的圖型及光阻下層膜的圖型被除去。如上述，本 發明之形成被膜用塗佈液可使用於製造半導體裝置時的光 刻蝕步驟。 (產業上之可利用性） 本發明之形成被膜用塗佈液爲使用於根據旋塗法等， 在基板上塗佈後、硬化，形成具有Si-o-Si鍵之矽氧烷聚 合物膜。作爲此類使用之用途可列舉於光阻膜下方所形成 的光阻下層膜，於基板之凹凸面上所形成的平坦化膜。 【圖式簡單說明】 圖1爲示出合成例4所得溶液之FT-IR光譜圖。 圖2爲示出合成例4所得溶液之FT-NIR光譜圖。 圖3爲示出實施例1對應之保存期間0日之塗佈液（ A )，以3 5 °C之溫度保存1週之塗佈液（B )、以同溫度 -41 - 200903173 保存2週之塗佈液（C )、以同溫度保存1個月之塗佈液 (D )以GPC (膠滲透層析）所測定之分子量分佈圖。 圖4爲示出圖3(A)至圖3(D)之分子量分佈全部 重疊之狀態圖。 圖5爲示出比較例1對應之以GPC (膠滲透層析）所 測定之分子量分佈圖。 圖6爲示出參考例1對應之以GPC (膠滲透層析）所 測定之分子量分佈圖。 圖7爲示出比較例2對應之以GPC (膠滲透層析）所 測定之分子量分佈圖。 圖8爲示出參考例2對應之以GPC (膠滲透層析）所 測定之分子量分佈圖。 圖9爲示出比較例3對應之以GPC (膠滲透層析）所 測定之分子量分佈圖。 圖1 〇爲示出實施例3對應之以GPC (膠滲透層析） 所測定之分子量分佈圖。 圖1 1爲示出實施例4對應之以GPC (膠滲透層析） 所測定之分子量分佈圖。 圖12爲示出比較例4對應之以GPC (膠滲透層析） 所測定之分子量分佈圖。 圖13爲示出比較例5對應之以GPC (膠滲透層析） 所測定之分子量分佈圖。 -42-I Η 0 - ? -〇(CH2)3CH3 ch3 (C) In the formula (C) 'If all the repeating units are regarded as 100% by mole, the repeating unit containing 2-vinylnaphthalene is 80% by mole, containing methacrylic acid 1 The repeating unit of -butoxyethyl ester is 10 mol%, and the repeating unit containing glycidyl methacrylate is a ratio of 1 mol%. In 5 g of the obtained polymer, a surfactant (manufactured by Dainippon Ink Chemical Industry Co., Ltd., trade name: Megafac R-30) 〇.〇3 g, and dissolved in cyclohexanone 23 g and propylene glycol alone were mixed. A solution of 23 grams of methyl ether. -38- 200903173 Thereafter, it was filtered using a polyethylene microfilter having a pore diameter of 0.10/mm, and then filtered using a polyethylene microfilter having a pore diameter of 0.05 /zm to modulate the composition of the photoresist underlayer film used in the photolithography step. Things. The underlayer film (layer A) containing no ruthenium formed by the composition and the ruthenium-containing photoresist underlayer film (layer B) formed by the coating liquid for forming a film of the present invention are combined to form a multilayer film. The prepared photoresist film forming underlayer film (including the polymer represented by formula (C)) was coated on a germanium wafer and heated on a hot plate at 250 ° C for 1 minute to form a film thickness of 25 Onm. The underlying film of the photoresist (layer A). The film coating liquids of Examples 3 and 4 and Comparative Examples 4 and 5 of the present specification were applied by a spin coater and heated on a hot plate at 240 ° C for 1 minute to form a film. An underlying photoresist film (layer B) having a thickness of 80 nm. The coating liquid for forming a film to be used is one in the storage period and stored at 35 ° C for two weeks. A commercially available photoresist solution (manufactured by Sumitomo Chemical Co., Ltd., trade name: PAR855) was coated with a spin coater and heated on a hot plate at 100 ° C for 1 minute to form a film thickness of 15 nm. Photoresist film (layer C). A pattern of a resist film (C layer) was formed using a scanner (manufactured by ASML Corporation, PAS5 500/1 100, wavelength pSnm, ΝΑ, σ: 0.75, 0.89/0.59 (bipolar)). The target object is the line width of the photoresist pattern after the development and the width between the lines is 〇.08 # m, the so-called line/space (dense line) is set to form a mask of 9 lines for exposure. Thereafter, it was heated at 105 ° C for 60 seconds on a hot plate, and after cooling, it was subjected to a 60-second single-step process in an industrial standard with a developing solution (2.38% by mass aqueous solution of tetramethylammonium hydroxide). Visualization. The shape of the photoresist pattern formed on the underlayer film (layer B) of various photoresists is shown in Table 3. The pattern of the photoresist pattern does not matter whether the shape of the straight end or the like at the end of the cutting or pulling end is expressed as "good". Secondly, the situation in which the photoresist pattern is broken is indicated by "pattern collapse". The results of Table 3 are shown to be formed via a coating liquid containing maleic acid of a cis-type divalent carboxylic acid (dicarboxylic acid) or cis-5-原bornene-endo-2,3-dicarboxylic acid. The presence of the photoresist underlayer film (layer B) does not cause the photoresist pattern formed by the upper layer to be deteriorated and exhibits the effect of forming a desired shape. [Table 3] Storage conditions of coating liquid 〇曰 35 〇 C 2 weeks Example 3 Good good Example 4 Good good Comparative Example 4 Good pattern collapse Comparative Example 5 Good pattern collapse <Production of semiconductor device> On the organic film on which the organic film was formed, the coating liquid prepared in the above Example 1 or Example 2 was applied by a spin coating method using a spinner. Thereafter, the ruthenium wafer was heated for 1 minute on a hot plate maintained at a temperature of 24 CTC to cure the coating liquid to form a photoresist underlayer film. Thereafter, a photoresist solution (trade name: UV113) manufactured by Shipley Co., Ltd. was applied onto the underlayer film of the photoresist to form a photoresist film. The method of forming the photoresist film may be the same as the method of forming the photoresist underlayer film. The formed photoresist film is exposed through a reticle (mask). After exposure, heat at a temperature of 150 ° C or lower, for example, 1 〇 〇 °C, for a specified period of time, for example, 1 minute. Thereby, a photoresist pattern of a predetermined shape is formed through development. -40- 200903173 For the developing liquid, for example, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide can be used. Thereafter, the photoresist pattern is used as a mask, and the photoresist underlayer film is dry-etched using CF4 gas to form a pattern of the photoresist underlayer film. The pattern of the underlying film of the photoresist and the pattern of the photoresist are used as a mask, and the organic film formed on the wafer is dry-etched using a gas containing ruthenium 2 gas. At this time, although the photoresist underlayer film remains, the photoresist pattern is removed. Thus, the pattern of the organic film is formed on the wafer. Next, various semiconductor devices can be fabricated by a process of processing a wafer or the like according to a known technique. Further, in the semiconductor device finally produced, the pattern of the organic film and the pattern of the photoresist underlayer film were removed. As described above, the coating liquid for forming a film of the present invention can be used for the photolithography step in the production of a semiconductor device. (Industrial Applicability) The coating liquid for forming a coating film of the present invention is used after being applied onto a substrate by a spin coating method or the like, and is cured to form a siloxane polymer film having a Si-o-Si bond. . The use of such a use is exemplified by a photoresist underlayer film formed under the photoresist film and a planarization film formed on the uneven surface of the substrate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a FT-IR spectrum chart showing a solution obtained in Synthesis Example 4. 2 is a FT-NIR spectrum chart showing the solution obtained in Synthesis Example 4. 3 is a coating liquid (A) showing 0 days of the storage period corresponding to Example 1, and the coating liquid (B) stored at a temperature of 35 ° C for one week, and stored at the same temperature -41 - 200903173 for 2 weeks. The coating liquid (C) and the coating liquid (D) stored at the same temperature for one month were measured by GPC (gel permeation chromatography). Fig. 4 is a view showing a state in which the molecular weight distributions of Figs. 3(A) to 3(D) are all overlapped. Fig. 5 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Comparative Example 1. Fig. 6 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Reference Example 1. Fig. 7 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Comparative Example 2. Fig. 8 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Reference Example 2. Fig. 9 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Comparative Example 3. Fig. 1 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Example 3. Fig. 11 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Example 4. Fig. 12 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Comparative Example 4. Fig. 13 is a graph showing the molecular weight distribution measured by GPC (gel permeation chromatography) corresponding to Comparative Example 5. -42-