1251840 九、發明說明： 【發明所屬之技術領域】 本發明涉及使用旋轉噴塗法、噴霧沉積法或CVD法在 各種基板的表面形成含鋰絕緣膜或者含矽酸鋰絕緣膜的絕 緣膜成膜用原料及使用該原料的成膜方法。 【先前技術】 作爲用於液晶顯示器（LCD)等的純平顯示器（FPD)的絕 緣薄膜’有Si02、Si3N4、PSG(磷矽玻璃）、BPSG(硼磷矽玻 璃）。另外，近年，從這些絕緣膜開發了耐熱性優良的 Li2Si〇3(:&夕酸錐）（例如’特開平8 — 45723號公報、特開2002 一 2 6 5 8 1 7號公報）。另外，作爲在基板的表面形成矽酸鋰膜 的方法，特開平8 — 45723號公報及特開2002 — 265 8 1 7號公 報公開了將由Li20及Si02組成的矽酸鋰水溶液被覆在基板 上進行乾燥的方法。進而，特表2000— 509100號公報公開 了用濺射法形成含有鋰膜的成膜方法。 另外，也考慮用旋轉噴塗法、噴霧沉積法或CVD法形 成矽酸鋰膜的成膜方法，但如果絕緣膜成膜用原料爲如上 所述的水溶液則爲凝膠狀，存在不能以均勻狀態霧化或氣 化的缺點。另外，即使只將原料中的水替換成有機溶劑， 其溶解度也較小，不能均勻地混合。爲此，用這些方法成 膜絕緣膜時，反而製成比溶膠-凝膠法或者濺射法品質低 的絕緣膜。所以不能用這些方法進行矽酸鋰膜的成膜。 特別是在用CVD法將把固體原料溶解在四氫呋喃等的 溶劑的液體原料供給到氣化器進行氣化時，除了上述的原 料難以均勻化的問題之外，由於固體原料的氣化溫度和溶 1251840 劑的氣化溫度有很大不同，所以存在加熱後僅溶劑氣化容 易析出固體原料的問題。 專利文獻1 :特開平8 — 4 5 7 2 3號公報 專利文獻2 :特開2 0 0 〇 — 5 0 9 1 0 0號公報 專利文獻3 :特開2 0 0 2 — 2 6 5 8 1 7號公報 【發明內容】 綜上所述，矽酸鋰絕緣膜從以前開始被認爲使用旋轉噴 塗法、噴霧沉積法或CVD法形成膜是困難的，但可期待用 這些方法進行絕緣膜的成膜，特別是用CVD法形成的絕緣 膜是高品質、高純度。 因此，本發明要解決的課題在於提供用旋轉噴塗法、噴. 霧沉積法或CVD法在各種基板的表面形成高品質、高純度 的含鋰絕緣膜或者含矽酸鋰絕緣膜用的絕緣膜成膜用原料 及使用該原料的成膜方法。 本發明者們爲了解決這些課題進行銳意硏究的結果發 現’由於鋰的烷氧基化合物容易均勻地溶解在醚、酮、酯、 醇或烴中；鋰的烷氧基化合物或鋰的羧酸鹽、四甲氧基矽 烷或四乙氧基矽烷及有機溶劑可容易均勻地混合·，以及作 爲原料使用這些混合物，可防止在氣化時僅是溶劑氣化、 固體原料和溶劑分離等，而完成本發明。 即，本發明爲一種絕緣膜成膜用原料，其特徵爲由（A) 鋰的烷氧基化合物選自醚、酮、酯、醇及烴且一種以上之 (B)有機溶劑所組成。 另外，本發明爲上述的絕緣膜成膜用原料進一步含有（C) 四甲氧基矽烷或四乙氧基矽烷。 1251840 又，本發明爲一種絕緣膜成膜用原料，其特徵是由（A，） 鋰的羧酸鹽、（C)四甲氧基矽烷或者四乙氧基矽烷、及（B ) 有機溶劑所組成。 另外，本發明爲一種成膜方法，其特徵是使用上述的絕 緣膜成膜用原料，用旋轉噴塗法、噴霧沉積法或C V D法在 基板的表面形成含鋰的絕緣膜或含矽酸鋰的絕緣膜。 按照本發明，可以將以往不能均勻成膜的含鋰絕緣膜成 膜用的原料、含矽酸鋰的絕緣膜成膜用的原料均勻地配 製。其結果，使用這些原料經旋轉噴塗法、噴霧沉積法或 CVD法，可在基板的表面均勻地形成上述的膜，得到高品 質、高純度的絕緣膜。 【實施方式】 本發明適用於在各種基板的表面形成含有矽酸鋰等鋰 的絕緣膜之絕緣膜成膜用原料及使用其原料在各種基板的 表面形成絕緣膜的方法。 在本發明的絕緣膜成膜用原料中，作爲鋰源可使用（A) 鋰的烷氧基化合物或（A，）鋰的羧酸鹽。另外，使用矽源時， 作爲矽源，可使用（C)四甲氧基矽烷或四乙氧基矽烷。進 而，爲了將原料作成均勻的液體，在上述原料中添加醚、 酮、酯、醇、烴等的（B)有機溶劑。 本發明中使用的（A)鋰的烷氧基化合物，可舉出甲醇 鋰、乙醇鋰、正丙醇鋰、異丙醇鋰、正丁醇鋰、異丁醇鋰、 第二丁醇鋰、第三丁醇鋰等。另外，作爲（A，）鋰的羧酸鹽， 可舉出甲酸鋰、乙酸鋰、丙酸鋰等。另外，醚、酮、酯、 醇、烴等的（B)有機溶劑通常是具有4〇°c〜18(rc的沸點， 1251840 也可使用這些中的一種或二種以上。 上述的醚，可舉出丙醚、甲基丁基醚、乙基丙基醚、乙 基丁基醚、1，3 -環氧丙烷、四氫呋喃、四氫吡喃等，酮可 舉出丙酮、乙基甲基酮、異丙基甲基酮、異丁基甲基酮等， 酯可舉出甲酸乙酯、甲酸丙酯、甲酸異丁酯、乙酸甲酯、 乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸異丁酯、丙酸甲醋、 丙酸丙酯、丁酸甲酯、丁酸乙酯等，醇可舉出甲醇、乙醇、 丙醇、丁醇等，烴可舉出己烷、庚烷、辛烷等。 本發明的由（A)鋰的烷氧基化合物及（B)有機溶劑組成 的絕緣膜成膜用原料中，鋰的烷氧基化合物相對於原料總 量的含量，通常是5〜80wt%、較佳爲20〜80wt%。又，在 由（A)鋰的烷氧基化合物（鋰源）、（〇四甲氧基矽烷或四乙氧 基矽烷（矽源）及（B)有機溶劑組成的絕緣膜成膜用原料中， 相對於總量，鋰源含量通常是5〜8 0 w t %，較佳爲2 0〜 80 wt%，相對於原料總量矽源含量通常是5〜75 wt%、較佳 爲20〜75wt%。又，在由（A，）鋰的羧酸鹽（鋰源）、（C)四甲氧 基矽烷或四乙氧基矽烷（矽源）及（B)有機溶劑組成的絕緣膜 成膜用原料中，相對於總量，鋰源含量通常是1〜50wt%、 較佳爲2〜30wt%，相對於原料總量，矽源含量通常是5〜 75wt%、較佳爲 20 〜75wt%。 對於配製的方法沒有特別限制，例如在配製由（A’）鋰的 羧酸鹽、（C)四甲氧基矽烷或四乙氧基矽烷及（B)有機溶劑組 成的原料中，可在這些鋰源、矽烷源、有機溶劑中，混合 任何二成分後，加入剩餘的另一成分、混合後配製原料或 者將所有成分同時混合後進行配製。可是，四甲氧基矽烷 1251840 或四乙氧基容易因水分解，所以最好是預先將這 成分進行混合後，最後混合四甲氧基矽烷或四乙 烷。 這樣配製的原料是均勻的，在室溫或室溫附近 〜40°C)、常壓或常壓附近的壓力（sc^uOkPa)、 的氛圍下是穩定的。 另外’在本發明中，可進一步添加界面活性劑 界面活性劑時，相對於總液量，通常添加5wt%以 爲1 w t %以下。 另外’本發明的絕緣膜成膜用原料實質上是由 組成的原料，即使含有少量鋰源鋰的烷氧基化合 羧酸鹽以外之原料時，或者含有少量矽源的四甲 烷、四乙氧基矽烷以外的原料時，只要不對混合 性有大的負面影響，亦在本發明的絕緣膜成膜用 圍內。進而，即使含有少量不對原料的均勻性、 品質有負面影響之其他成分，也在本發明的絕緣 原料的範圍內。例如，在絕緣膜成膜用原料中也 的添加量添加作爲摻雜劑的ρ 2 〇 5、P 0⑴C Η 3) 3。 本發明的成膜方法是使用如上所述配製的絕泰 用原料’用旋轉噴塗法、噴霧沉積法或CVD法，在 陶瓷基板、玻璃基板、金屬基板、合金基板等的 面形成含有鋰的絕緣膜或形成含有矽酸鋰的絕緣 方法。 在使用旋轉噴塗法、噴霧沉積法形成絕緣膜時 明的絕緣膜成膜用原料中，通常使用由鋰源、矽 些以外的 氧基矽 :的溫度（0 惰性氣體 。在添加 下、較佳 上述成分 物、鋰的 氧基矽 後的均勻 原料的範 絕緣膜的 膜成膜用 可以適宜 I膜成膜 矽基板、 基板的表 膜的成膜 =，在本發 源及有機 Ϊ251840 溶劑組成的原料，用C V D法形成絕緣膜時，也可使用本發 明的任何絕緣膜成膜用原料。 第1圖是表示用旋轉噴塗法形成絕緣膜的裝置、第2 圖是表示用噴霧沉積法形成絕緣膜的裝置、第3〜5圖是表 示用CVD法形成絕緣膜的裝置之構成圖，但實施本發明的 裝置不受這些限制。 在第1圖及第2圖中，從惰性氣體供給管線1供給的惰 性氣體的壓力將原料容器3中的絕緣膜成膜用原料2輸入 到旋轉噴塗器7或噴霧沉積法裝置8中。 在用旋轉噴塗法的成膜中，如第1圖所示，通常在旋轉 噴塗器7上設置以局速旋轉的旋轉圓盤1 4及加熱器。在絕 緣膜成膜時，將旋轉噴塗器內設定成指定的溫度、壓力後， 以高速旋轉旋轉圓盤及設置在旋轉圓盤上的基板1 3的同 時’從原料容器3通過惰性氣體的壓力將絕緣膜成膜用原 料滴入到基板的中心部。此時，通過離心力將本發明的均 勻性優良的原料向著基板上的外周方向均勻擴大，而後， 將其在150〜800 °C左右進行熱處理，在基板上得到高品 質、高純度的絕緣膜。 在用噴霧沉積法的成膜中，如第2圖所示，通常在噴霧 ί几積法裝置8上設置將原料作成霧狀供給到基板的噴淋頭 1 5、接受器1 6及加熱器。在絕緣膜成膜時，將噴霧沉積法 裝置8內設定成所規定的溫度、壓力後，從原料容器3通 過惰性氣體的壓力將絕緣膜成膜用原料供給到噴淋頭1 5。 此時，由於可將本發明的均勻性優良的原料進行均勻的霧 化’而後通過將基板在150〜800C左右進行熱處理，在基 -10- 1251840 板上得到高品質、高純度的絕緣膜。 在用CVD法的成膜中，如第3〜5圖所示，通常除了設 置液體品質流控制益寺的液體流量控制器5、氣化器9、C V D 裝置10之外’根據需要’ g受置脫氣器4。進而，在氣化器 9上連接氣體流量控制器1 1、載氣供給管線1 2，且設置絕 熱材料6。另外，進而將氣體預熱器1 7、氧供給管線1 §與 CVD裝置10連接。在絕緣膜成膜時，將氣化器內、CVD裝 置設定成指定的溫度、壓力後，從原料容器3通過惰性氣 體的壓力將絕緣膜成fl吴用原料2供給到氣化器9氣化，進 而供給到C V D裝置1 0。此時，由於可將本發明的均勻性優 良的原料均勻氣化，所以在基板上可得到高品質、高純度 的絕緣膜。 另外，在第4、5圖的裝置中’作爲一方的原料容器， 設置塡充了將鋰的烷氧基化合物溶解在從醚、酮、酯、醇 或烴選出的一種以上的有機溶劑的原料的原料容器，作爲 另外一方的原料容器，設置塡充了任意原料，例如四甲氧 基矽烷、四乙氧基矽烷的原料容器。 另外，在用CVD法的成膜中，通常在將含有氣化的原 料之氣體供給到CVD裝置前或供給到CVD裝置後立即添加 從氧、臭氧及水蒸氣選出的一種以上的氣體或含有此等之 氣體。 作爲在本發明使用的氣化器9，沒有特別限制，例如可 舉出如第6圖所示，原料供給部2 1的內部由氟系樹脂、聚 酸亞胺系樹脂等的耐腐蝕性合成樹脂24所構成的氣化 器、向氣化室20噴出液體原料使其氣化的噴出管25，是由 -11- 1251840 噴出液體原料的內管和噴出載氣的外管組成的雙層構造之 噴出管的热化器、或者具有在e v D原料供給部的側面具有 流過冷卻水的手段26之氣化器等。另外，在本發明中，除 了熟化一種液體原料的氣化器之外，可使用同時氣化二種 以上液體原料的氣化器。 以下’用貫施例具體地說明本發明，但本發明不受這些 限制。 實施例1 (絕緣膜成膜用原料的配製） 在內徑8cm、高…㈣的不銹鋼（SUS316)製的容器中， 從惰性氣體供給管線供給氮氣，使容器內部成爲氮氣氛 圍。接著，在容器中投入作爲鋰的烷氧基化合物之第三丁 醇鋰30g，加入作爲有機溶劑的辛烷70g，溶解第三丁醇鋰， 在25 °C、常壓的狀態下攪拌混合液，配製絕緣膜成膜用原 料。 (絕緣膜成膜用原料的均勻性檢查） 一邊保持上述的條件，一邊混合，在0.5小時後、2小 時後、1 0小時後、2 4小時後、1 〇 〇小時後，取樣絕緣膜成 膜用原料，檢查是否均勻混合。其結果如表1所示。 實施例2〜5 在實施例1的絕緣膜成膜用原料的配製中，除了改變第 三丁醇鋰的含有率之外，與實施例1相同地配製絕緣膜成 膜用原料。對於這些絕緣膜成膜用原料的均勻性，進行與 實施例1相同地檢查，其結果如表1所示。 實施例6〜1 2 -12- 1251840 在實施例1的絕緣膜成膜用原料的配製中，除了代替第 三丁醇鋰分別使用甲醇鋰、乙醇鋰、正丙醇鋰、異丙醇鋰、 正丁醇鋰、異丁醇鋰、第二丁醇鋰之外，與實施例1相同 地配製絕緣膜成膜用原料。對於這些絕緣膜成膜用原料的 均勻性，進行與實施例1相同地檢查，其結果如表1所示。 實施例1 3〜1 5 在實施例1的絕緣膜成膜用原料的配製中，除了使用丙 酮、乙酸乙酯、乙醇分別替代辛烷之外，與實施例1相同 地配製絕緣膜成膜用原料。對於這些絕緣膜成膜用原料的 均勻性，進行與實施例1柑同地檢查，其結果如表1所示。 實施例1 6 在實施例1的絕緣膜成膜用原料的配製中，除了將辛烷 的添加量作成40g的同時，添加四乙氧基矽烷30g之外， 與實施例1相同地配製絕緣膜成膜用原料（第三丁醇鋰： 30wt%、四乙氧基矽烷：30wt%、辛烷：40wt%)。對於這些 絕緣膜成膜用原料的均勻性，進行與實施例1相同地檢 查’其結果如表1所示。 實施例1 7、1 8 在實施例1 6的絕緣膜成膜用原料的配製中，除了改變 第三丁醇鋰的含有率之外，與實施例1 6相同地配製絕緣膜 成膜用原料。對於這些絕緣膜成膜用原料的均勻性，進行 與實施例1相同地檢查，其結果如表1所示。 實施例19、20 在實施例1 6的絕緣膜成膜用原料的配製中，除了改變 四乙氧基矽烷的含有率之外，與實施例1 6相同地配製絕緣 -13- 1251840 膜成膜用原料。對於這些絕緣膜成膜用原料的均勻性，進 行與實施例1相同地檢查，其結果如表1所示。 實施例2 1〜2 7 在實施例1 6的絕緣膜成膜用原料的配製中，除了分別 使用甲醇鋰、乙醇鋰、正丙醇鋰、異丙醇鋰、正丁醇鋰、 異丁醇鋰、第二丁醇鋰替代第三丁醇鋰之外，與實施例1 6 相同地配製絕緣膜成膜用原料。對於這些絕緣膜成膜用原 料的均勻性，進行與實施例i相同地檢查，其結果如表1 所示。 實施例2 8 在實施例1 6的絕緣膜成膜用原料的配製中，除了使用 四甲氧基砍院代替四乙氧基砂院之外，與實施例1 6相同地 配製絕緣膜成膜用原料。對於該絕緣膜成膜用原料的均勻 性，進行與實施例1相同地檢查，其結果如表1所示。 實施例2 9〜3 1 在實施例1 6的絕緣膜成膜用原料的配製中，除了分別 使用丙酮、乙酸乙酯、乙醇代替辛烷之外，與實施例1 6相 同地配製絕緣膜成膜用原料。對於這些絕緣膜成膜用原料 的均勻性，進行與實施例1相同地檢查，其結果如表1所 示。 實施例1〜3 1的結果 如按表1所示的經過時間的均勻性表明，在由本發明的 (A)鋰的烷氧基化合物及（B)有機溶劑組成的絕緣膜成膜用 原料（實施例1〜1 5)中，絕緣膜成膜用原料配製1 0小時以 上時，有一部分稍微不均勻但是實用的。另外，在由本發 -14· 1251840 明的（A)鋰的院氧基化合物、（C )四甲氧基砂j；完或四乙氧基 矽烷及（B )有機溶劑組成的絕緣膜成膜用原料（實施例丨6〜 3 1)中，絕緣膜成膜用原料配製24小時以上時，有一部分 稍微不均勻但是是實用的。 實施例3 2 (氣化器的製作） 製作原料供給部2 1，其內部由氟系合成樹脂（PFA)所構 成’其內部與氣化器外部的接觸部由不錄鋼（S u S 3 1 6)所構 成。氟系合成樹脂的構成部24是外徑16mm、高34.2mm的 圓柱狀，其外側的不銹鋼厚度是2 · 0mm。另外，頂端是雙 層構造，設置有內管是原料的流路、外管是載氣的流路之 噴出管2 5 一個。另外’在原料供給部的側面設置可流過冷 卻水冷卻CVD原料供給部的冷卻管26。 除了上述的原料供給部2 1之外，製作具有氣化氣體排 出口 22、加熱器23的如第6圖所示的不銹鋼製（SUS316) 的氣化器9(但是，具有二個向氣化室的噴出管25)。另外， 氣化室20是內徑65mm、高92.5mm的圓柱狀，底部的突起 是高27.5mm，另外，在距離底部15mm的高度設置氣化氣 體排出口 2 2。 (氣化供給裝置的製作） 將上述的氣化器9與脫氣器4、液體品質流控制器5、 載氣供給管線1 2、氧供給管線1 8、氣體預熱器1 7、氣體流 量控制器11、CVD裝置10等連接，設置絕熱材料6，製作 如第4圖所不的氣化供給裝置。另外，氧供給管線1 8設定 成可在反應器之前添加氧者。接著，連接塡充了實施例1的 -15- 1251840 絕緣膜成膜用原料的原料容器及塡充四乙氧基砂院的原料 容器。 (矽酸鋰膜的製作） 用貫施例1的絕緣β吴成膜用原料’使用上述的氣化供給 裝置，用C V D法在直徑5 0 m m的鐵-鎳合金基板上如下形 成以矽酸鋰作爲主成分的絕緣膜。 在氣化供給裝置內、CVD裝置內供給氮氣後，使氣化 器內形成160°C、常壓的同時，將CVD裝置內保持680°C、 常壓。接著，使用液體品質流控制器，分別以0.75 g/min、 1 · 1 5g/min將實施例1的絕緣膜成膜用原料及四乙氧基矽烷 供給到氣化器的同時，以5000ml/min的流量將來自載氣供 給管線而被加熱1 5 0 °C的氮氣供給到氣化器，將原料氣化後 供給到CVD裝置。另外，在CVD裝置之前以2000ml/min 的流量添加加熱到160 °C的氧氣。 (矽酸鋰膜的評價） 用原子間力顯微鏡分析這樣得到的絕緣膜的結果確 認、得到膜厚是〇 · 3 0 // m，高純度且均勻的矽酸鋰作爲主成 分的絕緣膜。 實施例3 3 (氣化供給裝置的製作） 在實施例3 2的氣化供給裝置的製作中，除了連接塡充 有實施例1 6的絕緣膜成膜用原料的原料容器以外，與實施 例3 2相同地製作如第3圖所示的氣化供給裝置。 (矽酸鋰膜的製作） 用實施例1 6的絕緣膜成膜用原料，使用上述氣化供給 -16 - 1251840 裝置，用C V D法在直徑5 0 m m的鐵-鎳合金基板上如下形成 以矽酸鋰作爲主成分的絕緣膜。 在氣化供給裝置內，C V D裝置內供給氮氣後，將氣化 器內作成160°C、常壓的同時，將CVD裝置內保持680°C、 常壓。接著，使用液體品質流控制器，以1.9g/min將實施 例1 6的絕緣膜成膜用原料供給到氣化器的同時，以 5 0 0 0 m 1 / m i η的流量將來自載氣供給管線被加熱1 5 0 °C的氮 氣供給到氣化器，將原料氣化後供給到C V D裝置。另外， 在CVD裝置之前以2000ml/min的流量添加加熱到16(TC的 氧氣。 (矽酸鋰膜的評價） 用原子間力顯微鏡分析這樣得到的絕緣膜的結果確 認，得到膜厚是0.2 8 μιη，高純度且均勻的矽酸鋰作爲主成 分的絕緣膜。 實施例3 4 (絕緣膜成膜用原料的配製） 在內徑8cm、高10cm的不銹鋼（SUS316)製的容器中從 惰性氣體供給管線供給氮氣，將容器的內部作成氮氣氛 圍。接著，在容器中投入作爲鋰的羧酸鹽之乙酸鋰10g，向 其中添加作爲有機溶劑的甲醇86g、丙酮4g，溶解乙酸鋰， 進而，添加四乙氧基矽100g，在25°C、常壓的狀態下攪拌 混合液（乙酸鋰：5wt%、四乙氧基矽：50wt%、有機溶劑： 4 5 w t % ) 〇 (絕緣膜成膜用原料的均勻性檢查） 一邊保持上述的熟化條件，一邊混合各成分，在0.5小 -17- 1251840 時後、2小時後、1 〇小時後、24小時後、丨00小時後，取 樣絕緣膜成膜用原料，檢查是否均勻混合。其結果如表2 所示。 實施例3 5〜3 8 在實施例3 4的絕緣膜成膜用原料的配製中，除了改變 各成分的含有率之外，與實施例3 4相同地配製絕緣膜成膜 用原料。對於這些絕緣膜成膜用原料由於熟化時間的均勻 性，進行與實施例3 4相同地檢查，其結果如表2所示。 實施例3 9〜4 1 在實施例34的絕緣膜成膜用原料的配製中，除了分別 使用四氫呋喃、乙酸丁酯、辛烷代替丙酮之外，與實施例 3 4相同地配製絕緣膜成膜用原料。對於這些絕緣膜成膜用 原料由於熟化時間的均勻性，進行與實施例34相同地檢 查，其結果如表2所示。 實施例4 2 在實施例34的絕緣膜成膜用原料的配製中，除了使用 乙醇代替甲醇之外，與實施例3 4相同地配製絕緣膜成膜用 原料。對於這些絕緣膜成膜用原料因熟化時間的均勻性’ 進行與實施例34相同地檢查’其結果如表2所示。 實施例3 4〜4 2的結果 如按表2所示經過時間的均勻性表明，在由（A ’）鋰的羧 酸鹽、（C)四甲氧基矽烷或四乙氧基矽烷及（B)有機溶劑組成 的絕緣膜成膜用原料中’絕緣膜成膜用原料配製1 〇小時以 上時，有一部分稍微不均勻但是實用。 實施例4 3 -18- 1251840 使用貫施例3 4的絕緣膜成膜用原料（熟化時間：2小 時）’使用第1圖的裝置，用旋轉噴塗法在直徑5 〇mm的鐵 一鎳合金基板上形成以矽酸鋰作爲主成分的絕緣膜。在絕 緣膜成膜時，將旋轉噴塗器內保持室溫（25它）、常壓，以 5 000rpm旋轉基板的同時，以2g/min的流量將絕緣膜成膜 用原料滴入到基板的中心部、塗覆，然後，取出基板在6 8 0 °C下進行3 0分鐘的熱處理。 用原子間力顯微鏡分析這樣得到的絕緣膜的結果，可確 認得到膜厚是0 · 3 // m，高純度且均勻的以矽酸鋰作爲主成 分的絕緣膜。 實施例4 4 使用實施例3 4的絕緣膜成膜用原料（熟化時間：2小 時）’使用第2圖的裝置，用噴霧沉積法在直徑5〇mm的鐵 鎳口金基板上形成以砂酸鋰作爲主成分的絕緣膜。在絕 緣膜成膜時，將噴霧沉積裝置內保持室溫（25。(：）、常壓的 同時，以2g/min的流量將絕緣膜成膜用原料供給到噴淋頭 上塗覆基板’然後，取出基板在680 °C下進行30分鐘的熱 處理。 用原子間力顯微鏡分析這樣得到的絕緣膜的結果，可確 認得到膜厚是0 · 5 // m，高純度且均勻的矽酸鋰作爲主成分 的絕緣膜。 實施例45 使用實施例34的絕緣膜成膜用原料（熟化時間：2小 時）’使用第3圖的裝置，用CVD法在直徑50mm的鐵一鎳 合金基板上如下形成以矽酸鋰作爲主成分的絕緣膜。另 -19- 1251840 外，氣化器使用以氟系樹脂（PFA)構成原料供給部的內部， 以不銹鋼（SUS 3 16)構成與氣化器外部的接觸部，向氣化室 的噴出管是由內管噴出原料、外管噴出載氣的管組成的雙 層結構。 向氣化供給裝置內、CVD裝置供給氮氣後，將CVD裝 置保持在6 8 0 °C、常壓的同時，將氣化器內保持在190°C、 常壓。接著，使用液體品質流控制器，以2g/min將絕緣膜 成膜用原料供給到氣化器的同時，將來自載氣供給管線被 加熱到21(TC的氮氣以5 000ml/min的流量供給到氣化器， 將氣化絕緣膜成膜用原料供給到CVD裝置。 用原子間力顯微鏡分析這樣得到的絕緣膜的結果，可確 認得到膜厚是0 · 5 // m，高純度且均勻的矽酸鋰作爲主成分 的絕緣膜。 比較例1 在實施例1的絕緣膜成膜用原料的配製中，除了使用氧 化鋰（Li20)代替第三丁醇鋰之外，與實施例1相同地配製絕 緣膜成膜用原料。對於該絕緣膜成膜用原料的均勻性，進 行與實施例1相同地檢查，其結果如表3所示。 比較例2 在實施例1 6的絕緣膜成膜用原料的配製中，除了使用 氧化鋰（Li20)代替第三丁醇鋰之外，與實施例16相同地配 製絕緣膜成膜用原料。對於該絕緣膜成膜用原料的均勻 性，進行與實施例1相同地檢查，其結果如表3所示。 比較例1、2的結果 如表3所示經過時間的均勻性表明，在比較例丨、2中， 絕緣膜成膜用原料配製1 〇 〇小時以上時，不均勻而且不實 用。 -20- 1251840 表1 絕緣膜成膜用原料(wt%) 隨時間經過的均勻性(hr) 鋰源 矽源 溶劑 0.5 2 10 24 100 實施例1 第三丁醇鋰(30) 一 辛烷 Δ 〇 〇 〇 〇 實施例2 第三丁醇鋰(1〇) 一 辛烷 〇 〇 〇 〇 〇 實施例3 第三丁醇鋰(20) — 辛烷 Δ 〇 〇 〇 〇 實施例4 第三丁醇鋰(40) — 辛烷 X Δ 〇 〇 〇 實施例5 第三丁醇鋰(50) — 辛烷 X X Δ 〇 〇 實施例6 甲醇鑛30) 一 辛烷 X X Δ 〇 〇 實施例7 乙醇鋰(30) — 辛烷 X Δ △ 〇 〇 實施例8 正丙醇鋰(30) — 辛烷 Δ △ 〇 〇 〇 實施例9 異丙醇鋰(30) — 辛烷 X Δ 〇 〇 〇 實施例10 正丁醇鋰(30) — 辛烷 X X Δ 〇. 〇 實施例11 異丁醇鋰(30) — 辛烷 X Δ 〇 〇 〇 實施例12 第二丁醇鋰(30) 一 辛烷 Δ 〇 〇 〇 〇 實施例13 第三丁醇鋰(30) — 丙酮 Δ Δ 〇 〇 〇 實施例14 第三丁醇鋰(30) — 乙酸乙酯 Δ 〇 〇 〇 〇 實施例15 第三丁醇鋰(30) 一 乙醇 X X Δ 〇 〇 實施例16 第三丁醇鋰(30) TE〇S(30) 辛烷 Δ 〇 〇 〇 〇 實施例17 第三丁醇鋰(10) TE〇S(30) 辛烷 〇 〇 〇 〇 〇 實施例18 第三丁醇鋰(50) TE〇S(30) 辛烷 X △ 〇 〇 〇 實施例19 第三丁醇鋰(30) TEOS(IO) 辛烷 〇 〇 〇 〇 〇 實施例20 第三丁醇鋰(30) TEOS(50) 辛烷 X X Δ 〇 〇 實施例21 甲醇鋰(30) TE〇S(30) 辛烷 X X X Δ 〇 實施例22 乙醇鋰(30) TE〇S(30) 辛烷 X X X Δ 〇 -21 - 1251840 實施例23 正丙醇鋰(30) TEOS(30) 辛烷 X X X Δ 〇 實施例24 異丙醇鋰(30) TE〇S(3〇） 辛烷 X X Δ 〇 〇 實施例25 正丁醇鋰(30) TE〇S(30) 辛烷 X X X △ 〇 實施例26 異丁醇鋰(30) TE〇S(3〇） 辛烷 X X X Δ 〇 實施例27 第二丁醇鋰(30) TE〇S(30) 辛烷 X △ 〇 〇 〇 實施例28 第三丁醇鋰 TM〇S(30) 辛烷 Δ 〇 〇 〇 〇 實施例29 第三丁醇鋰 TE〇S(30) 丙酮 Δ 〇 〇 〇 〇 實施例30 第三丁醇鋰 TE〇S(30) 乙酸乙酯 Δ 〇 〇 〇 〇 實施例31 第三丁醇鋰 TE〇S(30) 乙醇 X X 〇 〇 〇 ◦表示均勻，△表示稍不均勻，X表示鋰化合物不能溶解 等的不均勻 表2 絕緣膜成膜用原料的成分(wt%) 經熟化時間的均勻性(hr) 鋰源 矽源 溶劑 0.5 2 10 24 100 實施例34 乙酸鋰⑸ TE〇S(50) 甲醇(43)、丙酮(2) △ 〇 〇 〇 〇 實施例35 乙酸鋰⑷ TE〇S(51) 甲醇(43)、丙酮(2) △ 〇 〇 〇 〇 實施例36 乙酸鋰(6) TE〇S(49) 甲醇(43)、丙酮(2) △ △ 〇 〇 〇 實施例37 乙酸鋰⑷ TE〇S(40) 甲醇(54)、丙酮(2) Δ 〇 〇 〇 〇 實施例38 乙酸鋰(6) TE〇S(60) 甲醇(32)、丙酮(2) △ △ 〇 〇 〇 實施例39 乙酸鋰(5) TE〇S(50) 甲醇(43)、THF⑵ X Δ Δ 〇 〇 實施例40 乙酸鎖5) TEOS(50) 甲醇(43)、乙酸丁酯(2) X Δ 〇 〇 〇 實施例41 乙酸鋰(5) TEOS(50) 甲醇(43)、辛烷(2) X X Δ 〇 〇 實施例42 乙酸鋰(5) TEOS(50) 乙醇(43)、丙酮(2) X Δ 〇 〇 〇 〇表示均勻，△表示稍不均勻，X表示鋰化合物不能溶解 等的不均勻 -22· 1251840 表3[Technical Field] The present invention relates to the formation of a lithium-containing insulating film or an insulating film containing a lithium niobate insulating film on the surface of various substrates by a spin coating method, a spray deposition method, or a CVD method. A raw material and a film forming method using the same. [Prior Art] As an insulating film for a flat panel display (FPD) such as a liquid crystal display (LCD), there are SiO 2 , Si 3 N 4 , PSG (phosphorus phosphide), and BPSG (boron phosphide glass). In addition, in recent years, Li2Si〇3 (: & sorbic acid cone) which is excellent in heat resistance has been developed from these insulating films (for example, Japanese Patent Publication No. Hei 8-45723, and JP-A-2002-269-181). In addition, as a method of forming a lithium niobate film on the surface of a substrate, an aqueous lithium niobate solution composed of Li20 and SiO 2 is coated on a substrate, and is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Dry method. Further, Japanese Laid-Open Patent Publication No. 2000-509100 discloses a method of forming a film containing a lithium film by a sputtering method. In addition, a film forming method for forming a lithium niobate film by a spin coating method, a spray deposition method, or a CVD method is also considered. However, if the raw material for forming an insulating film is an aqueous solution as described above, it is gel-like, and it may not be in a uniform state. Disadvantages of atomization or gasification. Further, even if only water in the raw material is replaced with an organic solvent, the solubility is small and it is not possible to uniformly mix. For this reason, when the insulating film is formed by these methods, an insulating film having a lower quality than the sol-gel method or the sputtering method is formed instead. Therefore, the film formation of the lithium niobate film cannot be performed by these methods. In particular, when a liquid raw material in which a solid raw material is dissolved in a solvent such as tetrahydrofuran is supplied to a gasifier for gasification by a CVD method, in addition to the problem that it is difficult to homogenize the above-mentioned raw materials, the vaporization temperature and dissolution of the solid raw material are high. The vaporization temperature of the 1251840 agent is very different, so there is a problem that only the solvent is vaporized after heating, and the solid raw material is easily precipitated. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. 2 - No. 2, No. 2, No. 2, No. 2, No. 0, No. 5, No. 0, No. 0, No. 0, No. 2, No. 2 0 0 2 - 2 6 5 8 1 In the above, the lithium niobate insulating film is considered to be difficult to form a film by a spin coating method, a spray deposition method, or a CVD method, but it is expected that the insulating film can be formed by these methods. The film formation, in particular, the insulating film formed by the CVD method is high in quality and high in purity. Therefore, the object of the present invention is to provide a high-quality, high-purity lithium-containing insulating film or an insulating film for a lithium niobate-containing insulating film on the surface of various substrates by a spin coating method, a spray coating method, or a CVD method. A raw material for film formation and a film forming method using the same. As a result of intensive studies to solve these problems, the present inventors have found that 'the alkoxy compound of lithium is easily dissolved uniformly in an ether, a ketone, an ester, an alcohol or a hydrocarbon; an alkoxy compound of lithium or a carboxylic acid of lithium Salt, tetramethoxy decane or tetraethoxy decane and an organic solvent can be easily and uniformly mixed, and these mixtures can be used as a raw material, thereby preventing only vaporization of a solvent, separation of a solid raw material and a solvent, etc. at the time of gasification. The present invention has been completed. That is, the present invention is a material for forming an insulating film, characterized in that the (A) lithium alkoxide compound is selected from the group consisting of an ether, a ketone, an ester, an alcohol, and a hydrocarbon, and one or more (B) organic solvents. Moreover, in the present invention, the raw material for forming an insulating film further contains (C) tetramethoxy decane or tetraethoxy decane. Further, the present invention is a raw material for forming an insulating film, which is characterized by (A,) a carboxylate of lithium, (C) tetramethoxynonane or tetraethoxydecane, and (B) an organic solvent. composition. Further, the present invention is a film forming method which comprises forming a lithium-containing insulating film or lithium niobate-containing material on a surface of a substrate by a spin coating method, a spray deposition method or a CVD method using the above-mentioned raw material for forming an insulating film. Insulating film. According to the present invention, it is possible to uniformly prepare a raw material for forming a lithium-containing insulating film which cannot be uniformly formed in the past, and a raw material for forming an insulating film containing lithium niobate. As a result, by using a spin coating method, a spray deposition method or a CVD method, the above-mentioned film can be uniformly formed on the surface of the substrate to obtain a high-quality, high-purity insulating film. [Embodiment] The present invention is applied to a material for forming an insulating film for forming an insulating film containing lithium such as lithium niobate on the surface of various substrates, and a method for forming an insulating film on the surface of each substrate using the raw material. In the raw material for forming an insulating film of the present invention, (A) an alkoxy compound of lithium or a carboxylate of lithium (A) may be used as a lithium source. Further, when a ruthenium source is used, (C) tetramethoxy decane or tetraethoxy decane can be used as a ruthenium source. Further, in order to form a raw material into a uniform liquid, (B) an organic solvent such as an ether, a ketone, an ester, an alcohol or a hydrocarbon is added to the above raw material. The (A) lithium alkoxide compound used in the present invention may, for example, be lithium methoxide, lithium ethoxide, lithium n-propoxide, lithium isopropoxide, lithium n-butoxide, lithium isobutoxide or lithium second butoxide. Lithium tert-butoxide and the like. Further, examples of the carboxylate of lithium (A) include lithium formate, lithium acetate, lithium propionate and the like. Further, the (B) organic solvent such as an ether, a ketone, an ester, an alcohol or a hydrocarbon usually has a boiling point of 4 ° C to 18 (rc, and 1251840 may be used alone or in combination of two or more kinds thereof. Examples thereof include propyl ether, methyl butyl ether, ethyl propyl ether, ethyl butyl ether, 1,3-propylene oxide, tetrahydrofuran, tetrahydropyran, etc., and ketones include acetone and ethyl methyl ketone. , isopropyl methyl ketone, isobutyl methyl ketone, etc., esters can be mentioned ethyl formate, propyl formate, isobutyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate Examples of the ester include methyl acetate, propyl propionate, propyl propionate, methyl butyrate, and ethyl butyrate. The alcohol may, for example, be methanol, ethanol, propanol or butanol. Examples of the hydrocarbon include hexane, heptane and octane. In the raw material for forming an insulating film composed of the (A) lithium alkoxide compound and the (B) organic solvent of the present invention, the content of the lithium alkoxide compound relative to the total amount of the raw material is usually 5 to 80 wt. %, preferably 20 to 80% by weight. Also, in the (A) lithium alkoxide (lithium source), (p-tetramethoxynonane or tetraethoxysilane) In the raw material for forming an insulating film composed of an organic solvent and a solvent, the lithium source content is usually 5 to 80% by weight, preferably 20 to 80% by weight, based on the total amount, relative to the total amount of the raw materials. The cerium source content is usually 5 to 75 wt%, preferably 20 to 75 wt%. Further, in the (A,) lithium carboxylate (lithium source), (C) tetramethoxynonane or tetraethoxy group In the raw material for forming an insulating film composed of decane (a source of lanthanum) and (B) an organic solvent, the lithium source content is usually 1 to 50% by weight, preferably 2 to 30% by weight based on the total amount, based on the total amount of the raw materials. The content of the cerium source is usually 5 to 75 wt%, preferably 20 to 75 wt%. The method of formulation is not particularly limited, for example, in the preparation of a carboxylate of (A') lithium, (C) tetramethoxynonane or tetra In the raw material composed of ethoxy decane and (B) organic solvent, any two components may be mixed in these lithium sources, decane sources, and organic solvents, and the remaining other components may be added, and the raw materials may be mixed or mixed at the same time. After mixing, it is prepared. However, tetramethoxy decane 1251840 or tetraethoxy is easily decomposed by water, so it is preferable to pre- After mixing the ingredients, the final mixture of tetramethoxynonane or tetraethane is prepared. The raw materials thus prepared are homogeneous, at room temperature or near room temperature ~ 40 ° C), at or near atmospheric pressure (sc Further, in the present invention, when the surfactant surfactant is further added, it is usually added in an amount of 5 wt% or less to 1 wt% or less with respect to the total amount of the liquid. The raw material for forming an insulating film is a raw material consisting essentially of a raw material other than the alkoxylated carboxylate containing a small amount of lithium source lithium, or a raw material other than tetramethane or tetraethoxy decane containing a small amount of cerium source. In the case of the film formation for the insulating film of the present invention, as long as it does not have a large negative effect on the miscibility. Further, even if it contains a small amount of other components which do not adversely affect the uniformity and quality of the raw materials, it is within the range of the insulating raw material of the present invention. For example, ρ 2 〇 5 and P 0(1)C Η 3) 3 as dopants are added to the raw material for forming an insulating film. In the film forming method of the present invention, the lithium-containing insulating material is formed on the surface of a ceramic substrate, a glass substrate, a metal substrate, an alloy substrate, or the like by a spin coating method, a spray deposition method, or a CVD method using the raw material for the use of the above-mentioned materials. The film or an insulating method comprising lithium niobate. In the raw material for forming an insulating film which is formed by a spin coating method or a spray deposition method, a temperature of a ruthenium oxide other than a lithium source or the like is usually used (0 inert gas. The film formation film of the above-mentioned component and the uniform insulating material of the lithium oxyhydrazine may be suitable for film formation of the film of the I film, the film of the substrate, and the raw material of the solvent of the source and the organic 251,840. When the insulating film is formed by the CVD method, any material for forming an insulating film of the present invention may be used. Fig. 1 is a view showing an apparatus for forming an insulating film by a spin coating method, and Fig. 2 is a view showing an insulating film formed by a spray deposition method. The apparatus and the third to fifth figures are diagrams showing the configuration of an apparatus for forming an insulating film by the CVD method. However, the apparatus for carrying out the invention is not limited thereto. In the first and second figures, the supply is supplied from the inert gas supply line 1. The pressure of the inert gas is input to the rotary sprayer 7 or the spray deposition apparatus 8 by the insulating film forming material 2 in the raw material container 3. In the film formation by the spin coating method, as shown in Fig. 1, usually in The rotary sprayer 7 is provided with a rotating disk 14 and a heater that rotate at a local speed. When the insulating film is formed, the rotating sprayer is set to a predetermined temperature and pressure, and then the rotating disk is rotated at a high speed and set at While rotating the substrate 13 on the disk, the material for film formation of the insulating film is dropped from the material container 3 by the pressure of the inert gas to the center portion of the substrate. At this time, the material having excellent uniformity of the present invention is directed by centrifugal force. The outer circumferential direction of the substrate is uniformly enlarged, and then heat-treated at 150 to 800 ° C to obtain a high-quality, high-purity insulating film on the substrate. In the film formation by the spray deposition method, as shown in Fig. 2 It is to be noted that a shower head 15 for supplying a raw material to a substrate, a receiver 16 and a heater are usually provided in the spray device 8. When the insulating film is formed, the spray deposition device 8 is placed. After the predetermined temperature and pressure are set, the raw material container 3 is supplied to the shower head 15 by the pressure of the inert gas by the pressure of the inert gas. In this case, the raw material having excellent uniformity of the present invention can be uniformly obtained. The atomization is followed by heat treatment of the substrate at about 150 to 800 C to obtain a high-quality, high-purity insulating film on the base -10- 1251840. In the film formation by the CVD method, as shown in Figures 3 to 5. It is to be noted that, in addition to the liquid flow controller 5, the gasifier 9, and the CVD device 10, which are provided with the liquid quality flow control, the degasser 4 is disposed as needed. Further, the gas is connected to the gasifier 9. The flow controller 1 1 and the carrier gas supply line 12 are provided with a heat insulating material 6. Further, the gas preheater 17 and the oxygen supply line 1 are connected to the CVD apparatus 10. When the insulating film is formed, the gas is supplied. After the CVD apparatus is set to a predetermined temperature and pressure, the raw material container 3 is supplied to the vaporizer 9 by vaporization of the insulating film into the vaporizer 9 by the pressure of the inert gas, and is supplied to the CVD apparatus 10. In this case, since the material having excellent uniformity of the present invention can be uniformly vaporized, a high-quality, high-purity insulating film can be obtained on the substrate. Further, in the apparatus of Figs. 4 and 5, 'a raw material container is provided as a raw material for dissolving a lithium alkoxide compound in one or more organic solvents selected from ethers, ketones, esters, alcohols or hydrocarbons. The raw material container is provided as a raw material container of the other one, and a raw material container filled with an arbitrary raw material such as tetramethoxy decane or tetraethoxy decane is provided. Further, in the film formation by the CVD method, usually, one or more gases selected from oxygen, ozone, and water vapor are added or supplied before the gas containing the vaporized raw material is supplied to the CVD apparatus or immediately after being supplied to the CVD apparatus. Wait for the gas. The gasifier 9 used in the present invention is not particularly limited, and for example, as shown in Fig. 6, the inside of the raw material supply unit 21 is synthesized by corrosion resistance of a fluorine resin or a polyamic acid resin. The vaporizer composed of the resin 24 and the discharge pipe 25 that ejects the liquid material to the vaporization chamber 20 to vaporize it are a two-layer structure composed of an inner tube that discharges the liquid material from -11 to 1251840 and an outer tube that discharges the carrier gas. The heating device of the discharge pipe or the gasifier having the means 26 for flowing the cooling water on the side surface of the EV D raw material supply unit. Further, in the present invention, in addition to a gasifier which cures a liquid raw material, a gasifier which simultaneously vaporizes two or more kinds of liquid raw materials can be used. The invention will be specifically described below by the following examples, but the invention is not limited thereto. Example 1 (Preparation of raw material for forming an insulating film) In a container made of stainless steel (SUS316) having an inner diameter of 8 cm and a height (4), nitrogen gas was supplied from an inert gas supply line to make a nitrogen atmosphere inside the container. Next, 30 g of lithium alkoxide as an alkoxy compound of lithium was placed in a container, 70 g of octane as an organic solvent was added, lithium tributoxide was dissolved, and the mixture was stirred at 25 ° C under normal pressure. A raw material for forming an insulating film is prepared. (Checking the uniformity of the raw material for forming an insulating film) While maintaining the above conditions, the mixture was mixed, and after 0.5 hours, 2 hours, 10 hours, 24 hours, and 1 hour, the insulating film was sampled. Raw materials for the membrane, check for uniform mixing. The results are shown in Table 1. (Examples 2 to 5) In the preparation of the raw material for forming an insulating film of Example 1, a material for forming an insulating film was prepared in the same manner as in Example 1 except that the content of lithium tributyl hydride was changed. The uniformity of the raw materials for forming the insulating film was examined in the same manner as in Example 1. The results are shown in Table 1. Example 6 to 1 2 -12 to 1251840 In the preparation of the raw material for forming an insulating film of Example 1, in place of lithium third lithium butoxide, lithium ethoxide, lithium ethoxide, lithium n-propoxide, and lithium isopropoxide were used. A raw material for forming an insulating film was prepared in the same manner as in Example 1 except that lithium n-butoxide, lithium isobutoxide, and lithium second butoxide were used. The uniformity of the raw material for film formation of these insulating films was examined in the same manner as in Example 1. The results are shown in Table 1. Example 1 3 to 1 5 In the preparation of the raw material for film formation of the insulating film of Example 1, the film formation for the insulating film was carried out in the same manner as in Example 1 except that acetone, ethyl acetate and ethanol were used instead of octane. raw material. The uniformity of the raw materials for film formation of these insulating films was examined in the same manner as in Example 1, and the results are shown in Table 1. [Example 1] In the preparation of the raw material for film formation of the insulating film of Example 1, an insulating film was prepared in the same manner as in Example 1 except that 30 g of octane was added and 30 g of tetraethoxysilane was added. Raw material for film formation (lithium third butanol: 30% by weight, tetraethoxy decane: 30% by weight, octane: 40% by weight). The uniformity of the raw materials for forming the insulating film was examined in the same manner as in Example 1. The results are shown in Table 1. [Example 1] 7 and 1 8 In the preparation of the raw material for film formation of the insulating film of Example 16 , the raw material for forming an insulating film was prepared in the same manner as in Example 16 except that the content of lithium tert-butoxide was changed. . The uniformity of the raw materials for film formation of these insulating films was examined in the same manner as in Example 1. The results are shown in Table 1. [Examples 19 and 20] In the preparation of the raw material for film formation of the insulating film of Example 16, the film formation of the insulating-13-1251840 film was carried out in the same manner as in Example 16 except that the content of tetraethoxydecane was changed. Use raw materials. The uniformity of the raw materials for forming the insulating film was examined in the same manner as in Example 1. The results are shown in Table 1. Example 2 1 to 2 7 In the preparation of the raw material for film formation of the insulating film of Example 16, except that lithium methoxide, lithium ethoxide, lithium n-propoxide, lithium isopropoxide, lithium n-butoxide, and isobutanol were used, respectively. A raw material for forming an insulating film was prepared in the same manner as in Example 16 except that lithium or lithium butoxide was used instead of lithium t-butoxide. The uniformity of the raw material for film formation of these insulating films was examined in the same manner as in Example i, and the results are shown in Table 1. [Example 2] In the preparation of the raw material for film formation of the insulating film of Example 16, the film formation of the insulating film was carried out in the same manner as in Example 16 except that tetramethoxy chopping was used instead of the tetraethoxy sand yard. Use raw materials. The uniformity of the raw material for film formation of the insulating film was examined in the same manner as in Example 1. The results are shown in Table 1. Example 2 9 to 3 1 In the preparation of the raw material for forming an insulating film of Example 16 except that acetone, ethyl acetate or ethanol was used instead of octane, an insulating film was prepared in the same manner as in Example 16. Raw material for film. The uniformity of the raw materials for forming the insulating film was examined in the same manner as in Example 1. The results are shown in Table 1. The results of Examples 1 to 3 1 show the raw materials for film formation of an insulating film composed of the (A) lithium alkoxide compound and (B) organic solvent of the present invention as shown in Table 1 for the uniformity of the elapsed time. In the examples 1 to 1 5), when the raw material for forming an insulating film is prepared for 10 hours or longer, a part thereof is slightly uneven but practical. In addition, an insulating film composed of (A) an epoxy compound of lithium, (C) tetramethoxy sand j; or tetraethoxy decane and (B) an organic solvent, which is described by the present invention, is formed. In the raw material (Examples 〜6 to 31), when the raw material for forming an insulating film was prepared for 24 hours or more, some of them were slightly uneven but practical. Example 3 2 (Production of gasifier) The raw material supply unit 2 was fabricated, and the inside thereof was composed of a fluorine-based synthetic resin (PFA). The contact portion between the inside and the outside of the vaporizer was not recorded (S u S 3 1 6) constitutes. The constituent portion 24 of the fluorine-based synthetic resin has a cylindrical shape of an outer diameter of 16 mm and a height of 34.2 mm, and the outer stainless steel has a thickness of 2 mm. Further, the top end is a two-layer structure, and one of the discharge pipes 25 is provided with a flow path in which the inner pipe is a raw material and the outer pipe is a flow path of the carrier gas. Further, a cooling pipe 26 for cooling the CVD material supply portion through the cooling water is provided on the side surface of the raw material supply portion. In addition to the raw material supply unit 21 described above, a vaporizer 9 made of stainless steel (SUS316) having a vaporized gas discharge port 22 and a heater 23 as shown in Fig. 6 is produced (however, there are two gasifications) The chamber's discharge tube 25). Further, the vaporization chamber 20 has a cylindrical shape with an inner diameter of 65 mm and a height of 92.5 mm, and the protrusion at the bottom is 27.5 mm high, and the gasification gas discharge port 2 2 is provided at a height of 15 mm from the bottom. (Production of gasification supply device) The gasifier 9 and the deaerator 4, the liquid quality flow controller 5, the carrier gas supply line 12, the oxygen supply line 18, the gas preheater 17, and the gas flow rate described above are used. The controller 11, the CVD apparatus 10, and the like are connected, and the heat insulating material 6 is provided to produce a vaporization supply device as shown in Fig. 4. Further, the oxygen supply line 18 is set to be oxygen added before the reactor. Next, a raw material container filled with the raw material for film formation of -15 to 1251840 of Example 1 and a raw material container filled with tetraethoxy sand were attached. (Preparation of Lithium Niobate Film) The raw material for insulating β-forming film of Example 1 was formed by using the above-described gasification supply device by a CVD method on an iron-nickel alloy substrate having a diameter of 50 mm as follows. An insulating film containing lithium as a main component. After supplying nitrogen gas into the vaporization supply device and the CVD device, the inside of the vaporizer was maintained at 680 ° C and normal pressure while 160 ° C and normal pressure were formed. Next, using the liquid-quality flow controller, the insulating film-forming raw material of Example 1 and tetraethoxy decane were supplied to the gasifier at 0.75 g/min and 1 · 15 g/min, respectively, at 5000 ml/ The flow rate of min is supplied from the carrier gas supply line to the gasifier by nitrogen gas heated at 150 ° C, and the raw material is vaporized and supplied to the CVD apparatus. Further, oxygen heated to 160 ° C was added at a flow rate of 2000 ml/min before the CVD apparatus. (Evaluation of the lithium niobate film) The results of the analysis of the insulating film thus obtained were confirmed by an atomic force microscope to obtain an insulating film having a film thickness of 〇 · 3 0 // m and a high purity and uniform lithium niobate as a main component. Example 3 3 (Production of gasification supply device) In the production of the gasification supply device of Example 32, except that the raw material container filled with the raw material for forming an insulating film of Example 16 was connected, and Examples 3 2 The gasification supply device shown in Fig. 3 was produced in the same manner. (Production of Lithium Niobate Film) The material for forming an insulating film of Example 16 was formed on the iron-nickel alloy substrate having a diameter of 50 mm by a CVD method using the above-described vaporization supply -16 - 1251840 apparatus. An insulating film containing lithium niobate as a main component. In the gasification supply device, after supplying nitrogen gas into the C V D device, the inside of the vaporizer was maintained at 160 ° C and normal pressure, and the inside of the CVD device was maintained at 680 ° C and normal pressure. Next, using the liquid-quality flow controller, the insulating film-forming raw material of Example 16 was supplied to the gasifier at 1.9 g/min, and the carrier gas was supplied at a flow rate of 5,000 m 1 /mi η. The supply line was supplied with nitrogen gas heated at 150 ° C to the gasifier, and the raw material was vaporized and supplied to the CVD apparatus. In addition, the oxygen was heated to 16 (TC of TC) at a flow rate of 2000 ml/min before the CVD apparatus. (Evaluation of Lithium Niobate Film) The results of the analysis of the insulating film thus obtained by an atomic force microscope confirmed that the film thickness was 0.28. Μιη, an ultra-purity and uniform lithium niobate as an insulating film as a main component. Example 3 4 (Preparation of a raw material for forming an insulating film) In a container made of stainless steel (SUS316) having an inner diameter of 8 cm and a height of 10 cm, an inert gas was used. Nitrogen gas was supplied to the supply line, and the inside of the container was made into a nitrogen atmosphere. Then, 10 g of lithium acetate as a carboxylate of lithium was placed in the container, and 86 g of methanol and 4 g of acetone as an organic solvent were added thereto to dissolve lithium acetate, and further, 100 g of tetraethoxy ruthenium, and the mixture was stirred at 25 ° C under normal pressure (lithium acetate: 5 wt%, tetraethoxy ruthenium: 50 wt%, organic solvent: 4 5 wt %) 〇 (insulation film formation) Inspecting the uniformity of the raw materials) While maintaining the above-mentioned ripening conditions, the components were mixed, and the insulating film was sampled at 0.5 -17 - 1251840, 2 hours later, 1 hour later, 24 hours later, and 00 hours later. Film formation The raw materials were examined for uniform mixing. The results are shown in Table 2. Example 3 5 to 3 8 In the preparation of the raw material for forming an insulating film of Example 34, in addition to changing the content of each component, In the same manner as in Example 34, the material for film formation of these insulating films was examined in the same manner as in Example 34, and the results are shown in Table 2. The results are shown in Table 2. ～4 1 In the preparation of the raw material for film formation of the insulating film of Example 34, a raw material for forming an insulating film was prepared in the same manner as in Example 34 except that tetrahydrofuran, butyl acetate and octane were used instead of acetone. The material for film formation of the insulating film was examined in the same manner as in Example 34, and the results are shown in Table 2. Example 4 2 In the preparation of the raw material for film formation of the insulating film of Example 34, A raw material for forming an insulating film was prepared in the same manner as in Example 34 except that ethanol was used instead of methanol. The raw material for film formation of these insulating films was examined in the same manner as in Example 34 for the uniformity of the aging time. As shown in Table 2. Example 3 The results of 4 to 4 2 as shown in Table 2 show the uniformity of time, in the carboxylate from (A ') lithium, (C) tetramethoxynonane or four When the raw material for forming an insulating film of the insulating film forming material composed of the ethoxy decane and the (B) organic solvent is prepared for 1 hour or longer, some of them are slightly uneven but practical. Example 4 3 -18- 1251840 The raw material for film formation of the insulating film of Example 34 (curing time: 2 hours) was formed by using a device of Fig. 1 by spin coating on a nickel-nickel alloy substrate having a diameter of 5 mm to form lithium niobate as a main component. Insulating film of ingredients. When the insulating film is formed, the inside of the rotary sprayer is kept at room temperature (25 Å), normal pressure, and the substrate is rotated at 5 000 rpm, and the material for film formation of the insulating film is dropped into the center of the substrate at a flow rate of 2 g/min. After the coating, the substrate was taken out and heat-treated at 380 ° C for 30 minutes. As a result of analyzing the thus obtained insulating film by an atomic force microscope, it was confirmed that an insulating film having a film thickness of 0 · 3 // m and having high purity and uniformity with lithium niobate as a main component was confirmed. Example 4 4 Using the insulating film forming material of Example 3 4 (curing time: 2 hours) ' Using a device of FIG. 2, a sand acid was formed by a spray deposition method on an iron-nickel gold plate having a diameter of 5 mm. An insulating film containing lithium as a main component. When the insulating film is formed, the inside of the spray deposition apparatus is kept at room temperature (25. (:), normal pressure, and the raw material for film formation of the insulating film is supplied to the shower head on the coated substrate at a flow rate of 2 g/min') The substrate was taken out and heat-treated at 680 ° C for 30 minutes. The results of the insulating film thus obtained were analyzed by an atomic force microscope, and it was confirmed that a lithium niobate having a high purity and uniformity was obtained as a film thickness of 0.5 /5 m. In the insulating film of the main component. Example 45 The raw material for forming an insulating film of Example 34 (curing time: 2 hours) was formed by the CVD method on an iron-nickel alloy substrate having a diameter of 50 mm by using the apparatus of Fig. 3 as follows. An insulating film containing lithium niobate as a main component. In addition, the gasifier uses a fluorine-based resin (PFA) to form a raw material supply unit, and is made of stainless steel (SUS 3 16) and external to the gasifier. The contact portion and the discharge pipe to the vaporization chamber are a two-layer structure in which a raw material is discharged from the inner tube and a tube in which the outer tube discharges the carrier gas. After supplying nitrogen gas to the vaporization supply device and the CVD device, the CVD device is maintained at 6 8 At 0 °C and atmospheric pressure, the gas will be The inside of the reactor was maintained at a constant pressure of 190 ° C. Then, using a liquid quality flow controller, the raw material for film formation of the insulating film was supplied to the gasifier at 2 g/min, and the carrier gas supply line was heated to 21 (The nitrogen gas of TC is supplied to the vaporizer at a flow rate of 5,000 ml/min, and the raw material for vapor deposition insulating film formation is supplied to the CVD apparatus. The result of analyzing the insulating film thus obtained by an atomic force microscope confirmed that the film thickness was obtained. It is an insulating film containing 0.5 5 / m of high-purity and uniform lithium niobate as a main component. Comparative Example 1 In the preparation of the raw material for forming an insulating film of Example 1, lithium oxide (Li20) was used instead of A raw material for forming an insulating film was prepared in the same manner as in Example 1 except for the lithium tributoxide. The uniformity of the raw material for film formation of the insulating film was examined in the same manner as in Example 1. The results are shown in Table 3. (Comparative Example 2) In the preparation of the raw material for forming an insulating film of Example 16 except that lithium oxide (Li20) was used instead of lithium tributoxide, a raw material for forming an insulating film was prepared in the same manner as in Example 16. The uniformity of the raw material for film formation of the insulating film The results were examined in the same manner as in Example 1. The results are shown in Table 3. The results of Comparative Examples 1 and 2 are shown in Table 3. The uniformity of the elapsed time indicates that, in Comparative Examples 2 and 2, the insulating film-forming material was prepared. When it is more than 1 hour, it is uneven and not practical. -20- 1251840 Table 1 Raw material for film formation of insulating film (wt%) Uniformity with time (hr) Lithium source source solvent 0.5 2 10 24 100 Example 1 Lithium third butanol (30) monooctane Δ 〇〇〇〇 Example 2 Lithium third butanol (1 〇) monooctane 〇〇〇〇〇 Example 3 Lithium third butanol (20) — 辛Alkane Δ 〇〇〇〇 Example 4 Lithium third butanol (40) — octane X Δ 〇〇〇 Example 5 Lithium third butanol (50) — octane XX Δ 〇〇 Example 6 Methanol ore 30) 1-octane XX Δ 〇〇 Example 7 Lithium ethoxide (30) - octane X Δ △ 〇〇 Example 8 Lithium n-propanolate (30) - octane Δ △ 〇〇〇 Example 9 Lithium isopropoxide (30 — — Octane X Δ 〇〇〇 Example 10 Lithium n-butoxide (30) — Octane XX Δ 〇. 〇 Example 11 Lithium isobutoxide (30) — Octane X Δ 〇〇 Example 12 Lithium second butanol (30) monooctane Δ 〇〇〇〇 Example 13 Lithium third butanol (30) - Acetone Δ Δ 〇〇〇 Example 14 Lithium third butanol (30) — Ethyl acetate Δ 〇〇〇〇 Example 15 Lithium third butanol (30) Monoethanol XX Δ 〇〇 Example 16 Lithium third butanol (30) TE〇S (30) Octane Δ 〇〇〇〇 Example 17 Lithium tert-butoxide (10) TE〇S (30) octane oxime Example 18 Lithium third butanol (50) TE〇S (30) Octane X △ 〇〇〇 Example 19 Lithium tert-butoxide (30) TEOS (IO) octane oxime Example 20 Lithium third butanol (30) TEOS (50) Octane XX Δ 〇〇 Example 21 Lithium methoxide (30) TE〇 S(30) octane XXX Δ 〇 Example 22 Lithium ethoxide (30) TE〇S (30) Octane XXX Δ 〇-21 - 1251840 Example 23 Lithium n-propanolate (30) TEOS (30) Octane XXX Δ Example 24 Lithium isopropoxide (30) TE〇S (3〇) Octane XX Δ 〇〇 Example 25 Lithium n-butoxide (30) TE〇S (30) Octane XXX △ 〇 Example 26 Isobutyl Lithium Alcohol (30) TE〇S (3〇) Octane XXX Δ 〇 Example 27 Lithium butoxide (30) TE〇S (30) octane X △ 〇〇〇 Example 28 Lithium third butanol TM 30 S (30) Octane Δ 〇〇〇〇 Example 29 Lithium third butanol TE 〇 S(30) Acetone Δ 〇〇〇〇 Example 30 Lithium third butanol TE〇S (30) Ethyl acetate Δ 〇〇〇〇 Example 31 Lithium third butanol TE〇S (30) Ethanol XX 〇〇 〇◦ indicates uniformity, △ indicates slight unevenness, X indicates unevenness in which lithium compound cannot be dissolved, etc. Table 2 Composition of raw material for film formation of insulating film (wt%) Uniformity of aging time (hr) Lithium source lanthanum solvent 0.5 2 10 24 100 Example 34 Lithium acetate (5) TE〇S (50) Methanol (43), acetone (2) △ 〇〇〇〇 Example 35 Lithium acetate (4) TE〇S (51) Methanol (43), acetone (2 △ 〇〇〇〇 Example 36 Lithium acetate (6) TE〇S (49) Methanol (43), acetone (2) △ △ 〇〇〇 Example 37 Lithium acetate (4) TE〇S (40) Methanol (54) Acetone (2) Δ 〇〇〇〇 Example 38 Lithium acetate (6) TE〇S (60) Methanol (32), Acetone (2) △ △ 〇〇〇 Example 39 Lithium acetate (5) TE〇S ( 50) Methanol (43), THF (2) X Δ Δ Example 40 Acetic acid lock 5) TEOS (50) Methanol (43), butyl acetate (2) X Δ 〇〇〇 Example 41 Lithium acetate (5) TEOS (50) Methanol (43), octane (2) XX Δ Example 42 Lithium acetate (5) TEOS (50) Ethanol (43), acetone (2) X Δ 〇〇〇〇 indicates uniformity, Δ indicates slight unevenness, and X indicates unevenness of lithium compound insolubility, etc.-22 · 1251840 Table 3
絕緣膜成膜用原料的成分(wt%) 隨時間經過的均勻性(hr) 鋰源 矽源 溶劑 0.5 2 10 24 100 比較例1 Li2O(30) — 辛烷 X X X X X 比較例2 Li2〇(30) TE〇S(30) 辛烷 X X X X X 〇表示均勻，△表示稍不均勻’ X表示鋰化合物不能溶解 等的不均勻 【圖式簡單說明】 第1圖是表示用旋轉噴塗法實施本發明成膜方法的裝 置之一例的構成圖。 第2圖是表示用噴霧沉積法實施本發明成膜方法的裝 置之一例的構成圖。 第3圖是表示用CVD法實施本發明成膜方法的裝置之 一*例的構成圖。 第4圖是表示用CVD法實施本發明成膜方法的裝置之 第3圖以外的一例的構成圖。 第5圖是表示用CVD法實施本發明成膜方法的裝置之 第3圖、第4圖以外的一例的構成圖。 第6圖是表示用於本發明經CVD的成膜方法之氣化器 的一例的構成圖。 【主要元件符號說明】 1…惰性氣體供給管線 2…絕緣膜成膜用原料 3···原料容器 4…脫氣器 -23· 1251840 5、1 1…液體流量控制器 6···絕熱材料 7…旋轉噴塗器 8···噴霧沉積法裝置 9、20···氣化器 10…CVD裝置 12…載氣供給管線 13…基板 1 4…旋轉圓盤 1 5…噴淋頭 16…接受器 1 7…氣體預熱器 1 8…氧、臭氧、水蒸氣供給管線 19…氣體混合器 21…原料供給部 22···氣化氣體排出口 23·.·力口熱器 24…合成樹脂構成部 25…二重構造的噴出管 26…流過冷谷P 7jc之手段 -24-Composition of the raw material for insulating film formation (wt%) Uniformity with time (hr) Lithium source source solvent 0.5 2 10 24 100 Comparative Example 1 Li2O(30) - octane XXXXX Comparative Example 2 Li2〇(30) TE〇S(30) octane XXXXX 〇 means uniform, △ means slightly uneven 'X' indicates unevenness of lithium compound insolubility, etc. [Simplified illustration] Fig. 1 is a view showing a film forming method of the present invention by a spin coating method A diagram of an example of a device. Fig. 2 is a view showing the configuration of an apparatus for carrying out the film forming method of the present invention by a spray deposition method. Fig. 3 is a view showing a configuration of an apparatus for carrying out the film forming method of the present invention by a CVD method. Fig. 4 is a view showing a configuration of an example other than the third embodiment of the apparatus for performing the film formation method of the present invention by the CVD method. Fig. 5 is a view showing a configuration of an example other than the third and fourth figures of the apparatus for performing the film formation method of the present invention by the CVD method. Fig. 6 is a view showing the configuration of an example of a vaporizer used in the film formation method by CVD of the present invention. [Explanation of main component symbols] 1...Inert gas supply line 2...Insulation film forming material 3···Material container 4...Deaerator-23· 1251840 5,1 1...Liquid flow controller 6···Insulation material 7...Rotary sprayer 8··· Spray deposition apparatus 9 and 20······································· 1 7...gas preheater 1 8...oxygen, ozone, water vapor supply line 19...gas mixer 21...material supply unit 22···gasification gas discharge port 23·.·forcer 24...synthetic resin The constituent portion 25 is a double-structured discharge pipe 26... a means of flowing through the cold valley P 7jc-24-