1298315 玖、發明說明： [發明所屬之技術領域] 本發明係關於一種薄膜形成方法，其係以拉入碳原子 等之氮化矽（SiN)作為基本骨架以形成可見光透光率高的薄 膜。再者，係關於一種具備依據本方法所製造之透明薄膜 的透明基體，例如，適用於建築物、車輛或顯示器等用途 之具備透明薄膜的透明基體。 [先前技術] 利用化學氣相沉積法（以下，稱rCVD」）於玻璃基板上 形成薄膜的技術是眾所周知的。所形成之薄膜種類很多， 例如有氮化矽（SiN)膜等。氮化矽薄膜在半導體領域中被廣 泛用為絕緣膜使用。且，氮化矽薄膜因構造之緻密度，亦 可利用為鈉或銀等各種離子之擴散障壁、例如作為耐酸遮 罩等使用。具備氮化矽薄膜之玻璃基板因為在可見光區之 透光率尚，故適用於作為建物、車輛或者顯示器用之基板 使用。 氣化石夕薄膜之形成方法已知有將甲矽烷（SiH4)與氨 (随3)以常壓CVD法進行成膜之方法。但是，在習知之成膜 方法中，原料氣體中甲矽烷之濃度例如為〇 ·丨m〇丨％，屬較 低者。氮化矽薄膜中若膜中張力變大，則有時會有由玻璃 基板上剝離的問題。為解決此問題，已知有在薄膜中拉入 氧製成氧氮化矽（SiON)膜，以使張力下降之技術。例如， 在特開平10-309777號公報，記載有以CVD法於玻璃基板 1298315 上形成以氮化矽及氧氮化矽為主成分之薄膜的技術。 又’特開2001-1 0081 1號公報中，則著眼於氮化矽薄 膜之保護層功能’為形成完全的氮化石夕薄膜、即不含雜質 之氮化矽薄膜，其記載的方法，係在電漿CVD法中，將原 料氣體甲石夕烧與氨之流量比（Sil/NH3)設定為約0·086之 低值。 不過，習知之利用CVD法之氮化石夕與氧氮化石夕之成膜 速度，雖依成膜裝置有所不同，但大約都在數nm/s左右， 是很小的。特別在浮法玻璃之製程中，在浮式浴内浮於熔 融錫上之玻璃帶表面上欲以CVD法形成上述薄膜時（以下， 以「線上CVD法」稱呼該形成方法），u習知之成膜速度要 使薄膜厚度成長到能夠充分發揮特性之程度有困難。在線 上CVD法中，形成以氮化石夕及氧氮化石夕為主成分的薄膜時 ’要想成長到能充分發揮特性之膜厚，雖依玻璃帶之移動 速度而異’但大概需要在8nm/s以上。 [發明内容] 本發明係著眼於以上之問者員 工心问磚點所產生。其目的為提$ 一種形成薄膜之方法，JL能以褕田认从，^ ，、此以適用於線上CVD法之高成月 速度形成薄膜中張力緩和、不具± +易由基板上剝離且在可見》 區透光率高之透明簿蹬。蔽土 y , 溥胰再者’係提供具備以該方法所; 到透明薄膜之透明基體，苴孫尨m & ^其係適用於建物、車輛或顯示ϋ 等用途之具備透明薄膜透明基板。 為達到上述目的，本發明括 +赞月挺供一種透明薄膜之成形方 1298315 法，其係以利用原料氣體之化學氣相沉積法形成透明薄膜 ，成膜速度在8nin/s以上’且係形成含有擇自碳原子（〇及 氧（〇)中至少一者、氮（N)、氫原子（H)及矽（Si)之透明薄膜。 [實施方式] 本發明之形成方法以原料氣體中含矽化合物含量為 〇· 2mol%以上較佳。 原料氣體以含有含石夕化合物及氨為@ u氣體中氨 對含矽化合物之莫耳比為40〜400即可。 原料就體中所含之含石夕化合物以甲石夕烧（SiH4)為佳。 、原料氣體可以對已事先裁斷之玻璃板喷附，但以向浮 式洛内之玻璃帶表面喷附較佳。玻璃帶之表面溫度，例如 以700〜83(TC為適當的。玻璃帶為具彳4隨以下厚度者， 或者亦可為具有能成形& —以下厚度左右之較高線速度 本毛月在另一方面提供一種透明薄膜，其係以本發明 方、法所形成之透明薄冑，其氫原子之含有率為4〜20原子 以5’原子％為佳。該透明薄膜即使厚度在術m以上 ，其可見光透光率仍能在83%以上。 本發明在另—t & 方面棱供一種具備透明薄膜之透明基 ’其含有透明基體盥為 而該透明薄膜為本：形成之透明薄膜 、 毛明之上述透明薄臈。透明基體以玻 =佳。又，該具備透㈣膜之透明基 在透明薄膜表面上所形成之機能性薄膜。 1298315 以下，對於本發明之較佳實施形態參照圖式進一步說 明 圖1顯示一透明基體（例如玻璃基板υ，其被含有碳原 子及/或氧、氮、氫原子及矽原子等各元素為主成分所形成 之透明薄膜2所被覆。薄膜2可利用滅錢法、離子植入或 真空蒸鍍法等所謂物理蒸鍍法形成，但本 。物理蒸錢法雖然膜厚均-性良好，但是，二慮薄膜形 成後之耐久性等，以CVD法成膜者為較佳。_法中特別又 以常壓熱CVD為適合。依情況亦可利用觸女某cv])法，其係 利用透明基體旁邊所設置之觸媒體與原料氣體進行接觸分 解反應。以CVD法進行成膜，可藉由將氣體狀原料向裁成 既定大小並加熱之透明基體嘴附來進行。例如，將玻璃板 裝載在網孔輸送帶上，於通過加熱爐時供給原料氣體，在 加熱至既疋溫度之玻璃基板表面上使原料進行反應。 該透明薄膜之原料氣體較佳為，至少含有切化合物 及乳。此處之含石夕化合物不僅…Siu示之氫化 石夕，亦包含有機石夕化合物。例如，除了甲石夕燒（Μ)、乙 魏（Sl2H6)等氫切以外，亦可使用四氯切、二 氣石夕貌（siH2n2)、三氯#(SiHei3)、四款切（叫）等 以鹵素取代一部分遗溽 ((CH ) ^ ^ 、 虱化矽，四甲基矽烷 。因ίΓ:燒基石夕炫…特別以使用”夕炫者較佳 石夕烷谷易與氨反應’故成膜時副產物少，且，對 透明薄膜中之碳原子、氧及氫原 ' 令進行調整。 乳及風原子之含有率可以在廣範圍 1298315 氨為CVD法中以往就開始使用之氮原料，容易取得且 便宜。氨料之氮料’先前曾使用氮氣、胺類及聯胺類 之有機物等，但氮氣缺乏反應性，而有機物在工業生產規 模之原料調度上有困難，且工業化之使用上其毒性會產生 問題。又，若將氨作為原料氣體使用時，可防止透明薄膜 中混入碳原子，故可提高成膜速度。 透明薄膜之成膜速度若以工業化生產作為前提，以越 快越好。例如，在特開平1〇_3〇9777號公報中之實施例， η己載以矽烷及乙胺作為原料形成氮化矽薄膜之成膜速度為 6〇mn/min=lnm/s。對此，本發明中若以使用含氫化矽與氨 之原料氣體’成膜速度可在8nm/s以上。另一方面，在實 際生產時’成膜速度越快越容易使透明薄膜之均一性受損 ，例如，膜厚在某些情形下會有數倍差距或者會有產生針 孔等之缺點。因此，成膜速度本身就有極限，即使在要求 高成膜速度之線上CVD法中，也大概在15nm/s左右時，即 可在必須加快線速度之lmm玻璃帶上形成足夠厚度之透明 薄膜。是以，成膜速度之目標以8〜I5nm/S為佳。 原料氣體中含矽化合物之濃度以〇· 2m〇i%以上較佳。 其濃度不滿0· 2mol%時，即使透明基體表面溫度在8〇(rc以 上成膜速度亦達不到8nm/s，成膜會太費時間。特別在線 上CVD法中，若成膜速度不到8nm/s，雖依成膜裝置或操 作條件而異，還是會有可利用之玻璃帶厚度被限定於大於 4mm之範圍等問題發生。另一方面，若含矽化合物之濃度 過高’則因與氨之莫耳比要位於上述範圍内會有困難，故 1298315 在CVD法中含矽化合物之濃度上限以2.4mol%為適當者。 又，含碎化合物之濃度若太高，則氣相中會進行熱分解反 應變成粉末狀’使透明薄膜上產生針孔等缺陷，或是不僅 成膜速度下降在原料氣體當巾之含♦化合物會有爆炸之 危險性。因此’含矽化合物之濃度以在1.4m〇l%以下為實 用的。 原料氣體中氨對含矽化合物之莫耳比(氨之莫耳數/含 夕化&物之莫耳數）以4〇〜4〇〇較佳。若該比值比小，則 因Si-Si鍵結變多，會形成在可見光區具有吸收帶之透明 度低的薄膜。另-方面，該比值若大於權，則不僅要使 原料氣體中含石夕化合物濃度提高變得困難，且氨會開始抑 制3石夕化口物之分解，使成媒速度下降。順帶一提，此 對含梦化合物之莫耳4总 、 ’、特開2〇〇1-1〇〇811號公報中所 記載之習知方法加以比較，氨之比率高出了數倍。 ^拉入透明薄膜中之氧係由原料氣體令所添加 化-乳氧化碳及二氧化碳等氧化原料所提供。且 使在原料氣體中不添加該等 氣接觸產生自然氧化，有時亦合乂 /切精由成膜後與大 氧。此外，被拉入透明!==明 面附近拉入 ^ ^ 溥膜中之妷原子，可能是上述有機 :化5物私逢的情況，亦可能由原料氣體中所添加的乙供 =等低級烴類(為抑制如”炫這種反應性高之含= 化合物反應性）所提供。被拉入透明薄^夕 烧等含有氮之含石夕化合物、或氛之殘渣。據推測原2石夕 該等元素拉入氮化石夕之基曰由將 月木中使氮—矽之鍵結在多 1298315 處被切斷，其結果會使透明薄膜之張力被緩和，並使透明 薄膜從透明基體上剝離變困難。 原料氣體中除上述含矽化合物、氨、 ^ ^ 奶氰虱化原料及低級 二之外，亦可添加氮、氦或氫等。 形成有透明薄膜之透明基體，只要具有能耐cvd法成 =:夺之耐餘性及耐熱性、且能利用於上述建物用窗等用途 =2種類不特別限定，如’可舉例者有玻璃板、 耐熱塑膠等。 以玻璃板作為透明基體時，可於裁成適當尺寸之玻璃 板上形成透明薄膜，亦可利用後述線上CVD法，在玻璃板 成形的同時形成透明薄膜。在工業生產上，後者之線上 D法的優點較多。線上GVD法，係在浮式浴中於具有軟 化點以上熱度之玻璃帶表面進行成膜，原料氣體之轨分解 ^應會被玻璃帶之熱度所促進。其結果，不需要熱分解反 & 心此里成本。再者，可提高成膜速度 成膜反應效率’並且抑制針孔等缺陷產生。同時，具有 軟化點以上熱度之玻璃帶因為具有大表面尺寸自由度:故 以線上CVD法可使氮化石夕系薄膜特有之膜中張力減低，形 成附著力及機械強度高的透明薄膜。 又’在CVD法中，藉由在透明薄膜即將开》成前對玻璃 基板或玻璃帶表面吹送氨氣，可使成臈速度更進一步提高 據L，係因與玻璃基板或玻璃帶接觸之氨進行分解並吸 附於該處，而使含石夕4卜人仏 口物在供給之時點急速進行熱分解 反應所造成。再者，為彳4 χ ' 為促進氰之分解，亦可在玻璃基板或 12 1298315 玻璃帶之表面附近配置觸媒。 線上CVD法係使用如圖2所示之裝置。該裝置中，玻 璃帶10係從溶融爐（浮式窯）u流出到浮式浴12内，並從 帶狀移動於錫浴15上之玻璃帶10表面間隔既定之距離， 於浮式浴内配置既定個數之塗覆器16(圖示中冑3個塗覆 器16a、16b、16c)。從該等塗覆器供給原料氣體，並在玻 璃帶1〇上連續形成薄膜…若利用複數之塗覆巧，則 可在玻料1G上積層薄膜。玻璃帶之溫度，可藉由浮式 浴内配置之加熱器及冷卻器（圖示省略）而在塗覆器Μ之前 調整至既定之溫度。形成有各薄膜之麵帶1G被滾筒17 往上推:送人緩料13。又，在緩冷爐13中被緩冷之玻 璃板係藉由圖示省略之淳或、土、s 料之子式法通用之裁斷裝置裁為既定尺 寸。 f由於浮式浴内之上游部進行成膜，可使朝向未與溶 融狀態錫接觸之面（玻璃帶上 夕雜w )之錫熱擴散（錫蒸氣 抑制在最小限度。當玻璃帶上面之錫擴散量多時 =透明薄膜薄，易使其保護層機能變不^。例如， 明j臈上塗布以銀為主成分的糊狀物進行燒成製成電極時 貝:=锡穿過透明薄膜’銀與錫會反應並著色，在作為 途使料經常會產生問題藉由在浮式浴内 之上游部形成透明薄膜， 或锡之穿透的問題 相^變厚即可解決銀 :上CVD法一般在玻璃帶表面溢度為5。〇〜 圍内成膜。該透明薄膜較佳為，在即將成膜前之玻璃帶; 13 1298315 面》皿度為700〜830°C之蘇in 你士、.. 〇川H轭圍内形成。若在此溫度範圍，不 僅成膜速度可加快，且依玻璃帶表面之尺寸自由度，使氮 化石夕膜特有之薄膜中張力可以降低，可形成附著力提高、 機械強度高的透明薄膜。 一該透明薄膜因係以氮化石夕為基本骨架，堅硬且透明度 高且在可見光區之吸收低。透明薄膜中石夕與氮之原子含有 率以石夕：35~45原子％、氮：3〇〜6〇原子％為佳。若石夕原子之含 有率不滿35原子％，則透明薄膜之緻密性會劣化，且對各 種離子之擴散障壁能力會下降。另外一方面，若超過45 原子％，則在可見光區之吸收會變大，透明薄膜之透明性 曰下降X，在透明薄膜中氮之原子含有率對於石夕之原子 含有率比以越接近氮化矽之化學計量組成比之3較佳。 又’在透明薄膜中氮之原子含有率對於石夕之原子含有率比 若低於0.9’其可見光區之吸收會變大，薄膜之透明性會 下降。故，該透明薄膜氮之原子含有率對於石夕之原子含有 率比以調整為0.9〜1.3為適當的。 透明薄膜以含有碳或氧中至少一者卜1〇原子％為佳。 碳，依其含有率可變化透明薄膜之可見光區吸收率。另一 方面’氧可使透明薄膜之張力緩和使應力減輕，並使對於 透月基板之附著力提南並隨之使機械強度亦提高。為使該 等機能有效發揮，較佳為碳或氧之原子含 Β之範圍内。又，碳與氧可任選一種，或者亦可兼含 兩種。再者’該透明薄膜以氫為必要構成元素。若氛之含 ❹^高’透明薄臈之緻密度會劣化’對各種離子之擴散 14 1298315 障壁力下降，故其含有率以4〜20原子％為佳。 ，j明薄膜厚度為確保其保護層機能，必需為2。抓以上 ，另「方面，為確保可見光透光率，以300nm以下為佳。 又，透明薄膜之折射率，由於與後述透明導電膜或透明基 -之折射率差越大時反射率越高，故較佳為與一般由氧化 錫所構成之透明導電膜及玻璃基板折射率較接近之 1· 8〜2. 1 〇 又，透明薄膜之穿透率越高越好，本透明薄膜即使在 厚度為40nm下仍可確保可見光穿透率為83%。 ”圖3顯示玻璃基板之一例，其係將以氧化錫（_)、 二氧化矽（Si〇2)、矽氧化錫（SnSiO)、氧碳化矽（Si〇c)、碳 化矽UiC)或二氧化鈦（Ti〇2)為主成分製成之薄膜3積層= 透明薄膜2上。薄m 3為機能性薄膜，以氧化錫為主成分 ^薄膜係、作為透明導電膜，以二氧切切氧化錫為主成 分之薄膜係作為保護膜或絕緣性膜，以碳化矽為主成分之 薄膜係作為保護膜或絕緣性膜或進一步為茶色性之著色膜 ，二氧化鈦可作為具有熱線反射或光觸媒機能之膜。藉由 將該等機能性薄膜3與薄膜2組合，不會損害透明薄膜之 各種機能，並且可以適當調整反射率、導電性或保護層機 能等’並可使其耐久性提高。 圖3係在玻璃基板表面上之薄膜2上形成機能性薄膜 3 ’但其積層之順序及積層數不特別限定.，可依用途及所 需之機能適當改變。例如，如依圖3之構成，由於用機能 性薄膜3覆蓋化學安定性及物理強度高之透明薄膜2， 15 1298315 付到耐久性更高之機能性玻璃基板。 透明薄膜可在其膜厚深度方向上為實質均一之組成， 亦可具有組成梯度。特毅，機能性薄膜可在與透明薄膜 接觸之界面附近變化組成。藉此’可將透明薄膜與機能性 薄膜之密合性提高。 具備該透明薄媒之透明基板，可充分滿足建物或車輛 用所要求之特性，特別是由於不會發生銀之著色，亦可作 為顯示器肖，特別是可作為要求嚴格之電漿顯示器面板使 依習慣係指構成成分之 又，本發明中之「主成分」 重量含有率為50重量％以上者。 實施例 以下’利用實施例說明本發明，作太 知a彳一本發明不限定於以 下之實施例。 (實施例1) 將事先裁斷為每邊1Gcm正方形、厚度u咖之以浮法 製造之低鹼玻璃洗淨並乾燥。在該玻璃版上以常壓㈣法 形成以氮化矽為主成分之透明薄膜。成臈係於約㈣。c之 爐内將玻璃板以1.5m/min之速度搬送之條件下進疒。由[Technical Field] The present invention relates to a film forming method in which tantalum nitride (SiN) in which carbon atoms or the like is drawn is used as a basic skeleton to form a film having high visible light transmittance. Further, it relates to a transparent substrate having a transparent film produced by the method, for example, a transparent substrate having a transparent film suitable for use in buildings, vehicles, displays, and the like. [Prior Art] A technique of forming a thin film on a glass substrate by chemical vapor deposition (hereinafter referred to as rCVD) is well known. There are many types of films formed, such as a tantalum nitride (SiN) film. A tantalum nitride film is widely used as an insulating film in the field of semiconductors. Further, the tantalum nitride film can be used as a diffusion barrier of various ions such as sodium or silver, for example, as an acid-resistant mask, etc. due to the density of the structure. A glass substrate having a tantalum nitride film is suitable for use as a substrate for buildings, vehicles, or displays because of its light transmittance in the visible light region. A method of forming a gasified stone film is known as a method of forming a film by using a normal pressure CVD method of methane (SiH4) and ammonia (with 3). However, in the conventional film forming method, the concentration of formane in the material gas is, for example, 〇·丨m〇丨%, which is a lower one. In the tantalum nitride film, if the tension in the film is increased, there is a problem that the film is peeled off from the glass substrate. In order to solve this problem, there is known a technique in which oxygen is drawn into a film to form a yttrium oxynitride (SiON) film to lower the tension. For example, Japanese Laid-Open Patent Publication No. Hei 10-309777 discloses a technique of forming a thin film containing tantalum nitride and hafnium oxynitride as a main component on a glass substrate 1298315 by a CVD method. In the Japanese Patent Publication No. 2001-1 0081, the method of focusing on the protective layer function of the tantalum nitride film is to form a complete nitride film, that is, a tantalum nitride film containing no impurities. In the plasma CVD method, the flow ratio (Sil/NH3) of the raw material gas and the ammonia flow rate (Sil/NH3) is set to a low value of about 0·086. However, the film forming speed of the conventional CVD method of nitriding cerium and oxynitride is different depending on the film forming apparatus, but it is about several nm/s, which is small. In particular, in the process of the float glass, when the film is formed by the CVD method on the surface of the glass ribbon floating on the molten tin in the floating bath (hereinafter, the "on-line CVD method" is called the formation method), The film formation speed is difficult to grow the thickness of the film to such an extent that the characteristics can be sufficiently exhibited. In the on-line CVD method, when a film containing nitriding cerium and oxynitride diarrhea as a main component is formed, 'the thickness of the film which can fully exhibit the characteristics is different depending on the moving speed of the glass ribbon', but it is necessary to be 8 nm. /s above. SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problem. The purpose is to propose a method for forming a film, JL can be recognized by Putian, ^, which is suitable for the high-month speed of the on-line CVD method to form a tension relaxation in the film, without ± + easy to peel off from the substrate and Visible in the area of high transparency of the transparent book. Covering soil y, 溥 再 再 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到In order to achieve the above object, the present invention includes a method of forming a transparent film 1298315, which is formed by a chemical vapor deposition method using a material gas to form a transparent film at a film formation speed of 8 nin/s or more. A transparent film containing at least one selected from the group consisting of carbon atoms (anthracene and oxygen (N), a hydrogen atom (H), and cerium (Si). [Embodiment] The formation method of the present invention is contained in a raw material gas. The content of the ruthenium compound is preferably 〇·2 mol% or more. The raw material gas may contain 40% to 400% of the cerium-containing compound in the gas containing the cerium compound and the ammonia in the gas of @u. The raw material is contained in the body. The stone-containing compound is preferably Siheite (SiH4). The raw material gas can be sprayed on the glass plate which has been cut beforehand, but it is preferably sprayed onto the surface of the glass ribbon of the floating type. For example, 700 to 83 (TC is suitable. The glass ribbon has a thickness of 4 or less, or may have a higher linear velocity capable of forming and/or having the following thicknesses. Transparent film, which is based on the method and method of the present invention The transparent thin crucible formed has a hydrogen atom content of 4 to 20 atoms and preferably 5' atom%. The transparent film can have a visible light transmittance of 83% or more even if the thickness is more than m. Another -t & aspect is provided by a transparent substrate having a transparent film which contains a transparent substrate which is: a transparent film formed, a transparent thin film of the hair, and a transparent substrate of glass. The functional film having the transparent substrate of the (four) film formed on the surface of the transparent film. 1298315 Hereinafter, the preferred embodiment of the present invention will be further described with reference to the drawings. FIG. 1 shows a transparent substrate (for example, a glass substrate, which is The transparent film 2 containing carbon atoms and/or oxygen, nitrogen, hydrogen atoms and germanium atoms as main components is coated. The film 2 can be so-called physical steaming such as a money-killing method, ion implantation or vacuum evaporation. Although the plating method is formed, the physical vapor deposition method has a good film thickness uniformity, but it is preferable to form a film by a CVD method, such as durability after formation of a film. CVD is Suitable. It is also possible to use a cv]) method, which uses a contact medium disposed beside a transparent substrate to carry out a contact decomposition reaction with a material gas. The film formation by the CVD method can be performed by cutting the gaseous material. A transparent base nozzle of a predetermined size and heated is attached. For example, a glass plate is loaded on a mesh conveyor belt, a raw material gas is supplied while passing through a heating furnace, and a raw material is reacted on a surface of a glass substrate heated to a temperature of the same temperature. Preferably, the raw material gas of the transparent film contains at least a dicing compound and milk. The cerium compound contained herein is not only a hydrogenated stone of Siu, but also an organic stone compound. For example, in addition to a slate (Μ In addition to hydrogen cutting such as SEI (Sl2H6), it is also possible to replace some of the remains with halogen by using tetrachlorocene, dihedral (siH2n2), trichloro# (SiHei3), and four cuts (called). CH ) ^ ^ , 虱 矽, tetramethyl decane. Because Γ Γ: burning base stone 炫 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... The content of milk and wind atoms can be in a wide range of 1298315. Ammonia is a nitrogen raw material that has been used in the CVD method in the past. It is easy to obtain and cheap. The nitrogen material of ammonia material has previously used nitrogen, amines and hydrazines. Organic matter, etc., but nitrogen lacks reactivity, and organic matter has difficulty in scheduling raw materials on an industrial scale, and its toxicity causes problems in industrial use. Moreover, when ammonia is used as a raw material gas, it can be prevented from being in a transparent film. When the carbon atom is mixed, the film formation rate can be increased. The film formation rate of the transparent film is premised on industrial production, and the faster, the better. For example, in the embodiment of Japanese Laid-Open Patent Publication No. Hei No. Hei. The film formation rate of the tantalum nitride film formed by using decane and ethylamine as raw materials is 6 〇 mn / min = 1 nm / s. For this reason, in the present invention, the film formation rate of the raw material gas containing hydrazine hydride and ammonia can be used. Above 8nm/s On the other hand, in actual production, the faster the film formation speed, the more easily the uniformity of the transparent film is impaired. For example, the film thickness may be several times different in some cases or may cause pinholes or the like. The film formation speed itself has a limit, and even in a line CVD method requiring a high film formation speed, at about 15 nm/s, a transparent film having a sufficient thickness can be formed on a lmm glass ribbon which must accelerate the linear velocity. Therefore, the target of the film formation rate is preferably 8 to 1.5 nm/s. The concentration of the ruthenium-containing compound in the material gas is preferably 〇·2 m〇i% or more. When the concentration is less than 0.2 mol%, even the surface temperature of the transparent substrate At 8 〇 (the film formation rate above rc is also less than 8 nm/s, film formation will take too much time. Especially in the on-line CVD method, if the film formation rate is less than 8 nm/s, depending on the film forming apparatus or operating conditions However, there is still a problem that the thickness of the glass ribbon that can be used is limited to a range of more than 4 mm. On the other hand, if the concentration of the ruthenium-containing compound is too high, the molar ratio with ammonia is within the above range. Difficult, so 1298315 contains bismuth in CVD The upper limit of the concentration of the substance is suitably 2.4 mol%. Further, if the concentration of the compound containing the compound is too high, the thermal decomposition reaction in the gas phase becomes powdery, so that defects such as pinholes are formed on the transparent film, or not only The film speed decreases when the raw material gas is a compound containing ♦, which may cause an explosion. Therefore, the concentration of the ruthenium-containing compound is practically less than 1.4 m〇l%. The molar ratio of ammonia to the ruthenium-containing compound in the raw material gas (Mole of ammonia / morbidity & mole number of the object) is preferably 4 〇 to 4 。. If the ratio is small, the Si-Si bond is increased, and it is formed in the visible light region. The film having a low transparency of the absorption band. On the other hand, if the ratio is greater than the weight, it is difficult to increase the concentration of the compound containing the compound in the raw material gas, and ammonia will start to inhibit the decomposition of the 3 stone-like substance. The rate of media formation has dropped. Incidentally, this compares the conventional methods described in the publication of the Mohs 4 of the Dream Compound, and the publication of the Japanese Patent Publication No. 21-11-1811, and the ratio of ammonia is several times higher. The oxygen which is pulled into the transparent film is supplied from the raw material gas to the oxidation-oxidation raw materials such as emulsified carbon oxide and carbon dioxide. Further, natural gas oxidation is caused by not adding such gas contact to the material gas, and sometimes the enthalpy/cutting is performed by film formation and oxygen. In addition, it is pulled into the transparent! == The 妷 atom in the 溥 film near the bright surface may be the above-mentioned organic: the case of the 5th material, or the lower hydrocarbon added by the raw material gas It is provided by the class (in order to suppress the reactivity of the compound such as "Hypothesis", which is high in reactivity, etc.), and is contained in a transparent, thin, smouldering or the like containing a nitrogen-containing compound or a residue of the atmosphere. These elements are pulled into the base of the nitrite, and the nitrogen-ruthenium bond in the moon wood is cut at a number of 1298315, which results in the tension of the transparent film being moderated and the transparent film being on the transparent substrate. It is difficult to peel off. In addition to the above-mentioned cerium-containing compound, ammonia, ^ ^ milk cyanide raw material and lower two, nitrogen, hydrazine or hydrogen may be added to the raw material gas. A transparent substrate having a transparent film is formed as long as it has cvd resistance. In the case of the above-mentioned construction window, the type of the product is not particularly limited. For example, there are glass plates, heat-resistant plastics, etc. When the glass plate is used as a transparent substrate Can be cut into a glass plate of appropriate size As a transparent film, a transparent film can be formed at the same time as the glass plate is formed by the on-line CVD method described later. In industrial production, the latter method has many advantages in the line D method. The line GVD method has softening in a floating bath. The surface of the glass ribbon above the heat is formed into a film, and the decomposition of the raw material gas should be promoted by the heat of the glass ribbon. As a result, there is no need for thermal decomposition and the cost of the core. Further, the film formation speed can be increased. The film formation reaction efficiency 'and suppresses the occurrence of defects such as pinholes. At the same time, since the glass ribbon having the heat above the softening point has a large degree of surface size freedom, the in-line CVD method can reduce the tension in the film unique to the nitride film. A transparent film having high adhesion and high mechanical strength is formed. Further, in the CVD method, by blowing ammonia gas to the surface of the glass substrate or the glass ribbon before the transparent film is about to open, the growth rate can be further improved according to L, The ammonia which is in contact with the glass substrate or the glass ribbon is decomposed and adsorbed thereto, and the heat-decomposing reaction is carried out at the point of supply. Furthermore, it is 彳4 χ ' In order to promote the decomposition of cyanide, a catalyst may be disposed near the surface of the glass substrate or the 12 1298315 glass ribbon. The in-line CVD method uses a device as shown in Fig. 2. The belt 10 is discharged from the melting furnace (floating kiln) u into the floating bath 12, and the surface of the glass ribbon 10 which is moved from the strip to the tin bath 15 is spaced apart by a predetermined distance, and a predetermined number is placed in the floating bath. An applicator 16 (three applicators 16a, 16b, 16c in the figure). The raw material gas is supplied from the applicators, and a thin film is continuously formed on the glass ribbon 1 ... if a plurality of coatings are used, The film can be laminated on the glass 1G. The temperature of the glass ribbon can be adjusted to a predetermined temperature before the coater by the heater and cooler (not shown) disposed in the floating bath. The face band 1G on which the respective films are formed is pushed up by the drum 17: the person 13 is sent. Further, the glass plate which has been slowly cooled in the slow cooling furnace 13 is cut into a predetermined size by a cutting device which is not shown in the drawings or the sub-type method of the soil or the s material. fSince the film is formed in the upstream part of the floating bath, the tin can be thermally diffused toward the surface that is not in contact with the molten tin (the glass ribbon is mixed with w). The tin vapor is suppressed to a minimum. When the tin is on the glass ribbon When the amount of diffusion is large, the transparent film is thin, and it is easy to change the function of the protective layer. For example, when a paste containing silver as a main component is coated and fired to form an electrode, the shell: = tin passes through the transparent film. 'Silver and tin react and color, which often causes problems in the process of forming a transparent film in the upstream part of the floating bath, or the problem of penetration of tin can be solved by thickening: silver CVD Generally, the surface of the glass ribbon has a surface roughness of 5. 〇 ~ film formation. The transparent film is preferably a glass ribbon immediately before film formation; 13 1298315 face" is 700~830 ° C. In the temperature range, not only the film formation speed can be accelerated, but also the degree of freedom of the surface of the glass ribbon can reduce the tension in the film unique to the nitride film, which can be formed. a transparent film with improved adhesion and high mechanical strength. It is based on the nitrite as the basic skeleton, which is hard and has high transparency and low absorption in the visible light region. The atomic content of Shixia and nitrogen in the transparent film is as follows: 35~45 atom%, nitrogen: 3〇~6〇 atom% It is preferable that if the content of the Shi Xi atom is less than 35 atom%, the denseness of the transparent film may be deteriorated, and the barrier property against diffusion of various ions may be lowered. On the other hand, if it exceeds 45 atom%, it is in the visible region. The absorption becomes large, and the transparency of the transparent film decreases by X. In the transparent film, the atomic content of nitrogen is preferably 3 to the ratio of the atomic ratio of the cerium to the stoichiometric composition ratio of the tantalum nitride. The atomic content of nitrogen in the transparent film is larger than the atomic content ratio of the stone in the case of less than 0.9', and the transparency of the film is decreased. Therefore, the atomic content of the transparent film is lower than that of the stone. The atomic content ratio is suitably adjusted to be 0.9 to 1.3. The transparent film preferably contains at least one of carbon or oxygen, and carbon is contained in the visible light region of the transparent film. On the other hand, 'oxygen can relax the tension of the transparent film to reduce the stress, and increase the adhesion to the moon-permeable substrate and then increase the mechanical strength. In order to make these functions work effectively, carbon is preferred. Or the atom of oxygen contains yttrium. In addition, carbon and oxygen may be selected one or both. In addition, 'the transparent film uses hydrogen as an essential constituent element. If the atmosphere contains ❹^high' transparent The density of the thin enamel will deteriorate. 'The diffusion of various ions is 14 1298315. The barrier force is reduced, so the content is preferably 4 to 20 atom%. The thickness of the film is required to ensure the protective layer function. In addition, in order to ensure the visible light transmittance, it is preferably 300 nm or less. Further, the refractive index of the transparent film is higher as the refractive index difference with a transparent conductive film or a transparent group described later is higher. The refractive index of the transparent conductive film and the glass substrate which are generally composed of tin oxide is relatively close to 1·8~2. 1 〇 In addition, the higher the transmittance of the transparent film, the better, even if the thickness of the transparent film is 40 nm. Can still ensure visible light penetration The rate is 83%. Figure 3 shows an example of a glass substrate which is made of tin oxide (-), cerium oxide (Si〇2), antimony-oxide (SnSiO), antimony oxynitride (Si〇c), niobium carbide (UiC) or titanium dioxide. (Ti〇2) Film 3 layer made of the main component = transparent film 2. Thin m 3 is a functional film, with tin oxide as the main component, film, as a transparent conductive film, and oxidized by tin dioxide. The film of the main component is used as a protective film or an insulating film, and the film containing ruthenium carbide as a main component is used as a protective film or an insulating film or a color film of a further color, and titanium dioxide can be used as a film having heat ray reflection or photocatalytic function. By combining the functional film 3 and the film 2, various functions of the transparent film are not impaired, and reflectance, conductivity, protective layer function, etc. can be appropriately adjusted, and durability can be improved. The functional film 3' is formed on the film 2 on the surface of the glass substrate. However, the order of lamination and the number of layers are not particularly limited. They may be appropriately changed depending on the application and the required function. For example, according to the configuration of Fig. 3, due to the function Film 3 The transparent film 2, 15 1298315 covering high chemical stability and physical strength is applied to a functional glass substrate with higher durability. The transparent film can be substantially uniform in the film thickness depth direction, and can also have a composition gradient. Yi, the functional film can be changed in the vicinity of the interface with the transparent film. This can improve the adhesion between the transparent film and the functional film. The transparent substrate with the transparent thin film can fully satisfy the construction or vehicle. The required characteristics, especially since the color of silver does not occur, can also be used as a display, especially as a rigorous plasma display panel, which is a component of the customary component, and the "principal component" of the present invention. The weight content is 50% by weight or more. EXAMPLES Hereinafter, the present invention will be described by way of examples, and the invention is not limited to the following examples. (Example 1) The low alkali glass produced by float method, which was previously cut into 1 Gcm square and thickness u coffee, was washed and dried. A transparent film containing cerium nitride as a main component was formed on the glass plate by a normal pressure (four) method. Cheng Yu is attached to the covenant (4). In the furnace, the glass plate is conveyed at a speed of 1.5 m/min. by
内设置之塗覆器，在氨對甲矽烷之莫 V 六π π Z u u下，供給甲 矽烷濃度〇· 5mol%且以氮翕作兔恭名私2 、 ’、、 見乱作為載乳所組成之原料氣體， 在玻璃基板表面上形成厚度4_之以氮化♦為 明薄膜。此時成臈速度為10nm/s。 16 1298315 …由、x射線激發光電分光分析及拉塞福後方散射分析， t ^ A透H膜之組成為石夕4〇原子％、氮α原子％、氧2 原子^氫15原子％。利用分光光度計測定該透明薄膜之可 見光穿透率的結果，為88. 7%，以橢圓測厚儀 (Ellipsometer)測定550nm之折射率結果為139〇。該特 f生不僅於建物或汽車等之用*，在要求高透明性之顯示器 用’是作為要求嚴袼之電漿顯示器面板用基板使用上 都疋在實際使用無問題的等級。又，透明薄膜之表面電 阻值為1〇ηΩ/□以上，絕緣性可判定為是高的。 再者’為確認該透明薄膜之保護層機能，於透明薄膜 上塗布銀糊，並於500°C下施以1小時之燒成處理。結果 ，並未見到銀產生著色（黃色變化）。該低鹼玻璃因係以浮 法製造’可藉由是否有銀著色判別錫是否穿透透明薄膜。 亦即，可說該透明薄膜充分具備顯示器用途所要求之保護 層機能。 關於上述成膜條件及透明薄膜之特性，整理表示於下 述（表1)及（表2)中。 (實施例2) 使用如圖2所示之裝置，以線上CVD法，於玻璃帶之 表面上形成以氮化矽為基本骨架之薄膜。於浮式浴内流入 1500〜1600C、以通常之鈉#5玻璃組成所構成之炼融玻璃原 材料。於玻璃帶之溫度為830 °C時，自位於最上游側之第i 塗覆器（圖3中16a)，在氨對甲矽烷之莫耳比為100下， 17 !298315 ^所含甲#濃度為om且以氮氣作為載氣之原料 乳體:並於厚度2.8龍之玻璃帶表面上形成厚度為4511111之 =明薄膜。此時之成膜速度^ Wse將該玻璃帶於緩冷 -内使其緩冷’再以配置於運送下游側之切斷機裁成既定 之尺寸以製作成玻璃基板。 對該透明薄膜，與實施例 性。其結果，透明薄膜之組成構成為矽：44原子％、一氮、.Ο 原子％、氧：2原子％及氫13原子％，其可見光穿透率為 85.1%、折射率L97、表面電阻為1〇1Gd/□以上。又，未 見到銀之著色。 關於上述成膜條件及透明薄膜之特性，整理表示於下 述（表1)及（表2)。 ’ 、 (比較例1) 、除了將實施Μ 2原料氣體改為使用氨對f㈣之莫耳 $為450、且甲矽烷濃度為〇15111〇1%之原料氣體以外，與 也例2以相同之方法形成薄膜。此時之成膜速度為 Snm/s且薄膜之厚度為15nm。對該薄膜以與實施例ι相同 之方法檢查其特性。其結果，透明薄膜之組成構成為矽:36 」子氮· 原子％、氧·· 2原子％及氫：22原子％，其可見 光穿透率A 89.5%、折射率u5、表面電阻為1〇1Gq/〇以 上。又，雖然透明性高，但可見到銀之著色。故，可以說 此薄膜之保濩層機能低，且不能利用於要求高透明性之顯 示器用途上。 18 1298315 對上述成膜條件及薄膜特性，整理表示於下述（表i) 及（表2)。 (比較例2) 除了將實施例2之氨以乙胺代替，並使用乙胺對甲矽 烷莫耳比為25、且甲矽烷濃度為〇 5m〇1%之原料氣體，且 將成膜速度改為lnm/s、厚度改為4nm以外，與實施例2 以相同之方法形成薄膜。對該薄膜以與實施例丨相同之方 法，查其特性。其結果，透明薄膜之組成構成為矽:33原 子％氮· 31原子％、氧：16原子％及碳：21原子％。雖未測定 。亥薄膜之可見光穿透率與折射率，但以目視之觀察，其外 觀具備與實施例1 $ $ 1之透明薄膜同程度之透明性。又，雖然 表面電阻為1〇10门/门、7 L u /U以上，但可見到銀之著色。故，可以 判斷此薄膜之保護層機能低。 性，整理表示於下述（表 關於上述成膜條件及薄膜特 1)及（表2)。 19 1298315 (1¾ i 薄膜組成(原子％) 〇 〇 ο O 〇3 LO CO o 〇 OJ CN1 οα CO ίζ 导 CO cB §8 η 成膜速度 (nm/s) α CO s 玻璃溫度 CC) 8 s § 域〇 拎3 LO CZD c=> LO <=> LO CZ5 NH3/SiH4 (莫耳比） § s § oa 實施例1 實施例2 比較例1 比較例2 涟 鈹 因熱處理產生之著色 黃色 黃色 ώ /^ν 55 ® α ^1010 ^1010 ^1010 ^1010 折射率 05 τ-Η 1.85 未測定 穿透率 (°/〇) 88.7 85.1 89.5 未測定 膜厚 (nm) LO LO 實施例1 實施例2 比較例1 比較例2 1298315 藉由將上述實施例與比較例進行對比可知，藉由在 CVD法中變化原料氣體中甲矽烷與氨濃度之濃度，可調整 透明薄膜之組成構成。且可知，以本發明之成膜條件所形 成之透明薄膜具有高可見光穿透性、高絕緣性及高保護層 /、體上，藉由比較實施例1、2及比較例丨可知，原料 氣體中氨對甲錢之莫耳比越高，則所形成之薄膜切含 有率越低。再者可知，隨矽含有率上升，薄膜之可見光穿 透率會下降且折射率上升。 本發明因具有如以上之構成，可以發揮如下效果。若 依本發明透明薄膜之形成方法，可以達到線上CVD法所能 =私度之快速成膜速度。χ，藉由適當維持原料氣體中 石3有化合物濃度，並適當調整含矽化合物與氨之含有率 ^不但可以保持高成膜速度，且可確實形成透明度高且不 由透明基體上剝離之透明薄膜。 内带成^ 用線i為成膜方法，可在短時間 =大面積、無針孔等缺陷之透明薄膜。且，因為在綠 C1^中原料氣體熱分解反應所需之能量係由玻璃 到，^以削減具備透明薄膜之玻璃基板之總能量成本。 輛用之ϋ之具備透明薄膜玻璃基板可充分滿足建物或車 作為顯示器^性，特別是因為不會發生銀之著色，適用於 板使用。5 ’特別適用於要求嚴格之電漿顯示器面板基 21 1298315 [圖式之簡單說明] (一） 圖式部分 圖1為本發明之具備透明薄膜透明基體之一實施形態 的截面圖。 圖2為線上CVD法所使用裝置的示意圖。 圖3為積層有透明薄膜及機能性薄膜而成之透明基體 之一實施形態的截面圖。 (二） 元件代表符號 1玻璃基板 2透明薄膜 3薄膜（機能性薄膜） 10玻璃帶 11熔融爐 12浮式浴 13緩冷爐 1 5錫浴 16， 16a， 16b， 16c 塗覆器 17滚筒 22The applicator provided is supplied with a concentration of 矽································· The raw material gas is formed to have a thickness of 4 mm on the surface of the glass substrate to form a thin film of nitride. At this time, the enthalpy speed was 10 nm/s. 16 1298315 ... by x-ray excitation photoelectric spectroscopic analysis and rasafy back scattering analysis, the composition of t ^ A transparent H film is 4 〇 atomic %, nitrogen α atom%, oxygen 2 atom ^ hydrogen 15 atom%. The result of measuring the visible light transmittance of the transparent film by a spectrophotometer was 88.7%, and the refractive index at 550 nm was 139 Å as measured by an Ellipsometer. This special product is used not only for construction or automobiles, but also for displays that require high transparency. It is used as a substrate for plasma display panels that are required to be used. Further, the surface resistivity of the transparent film was 1 〇 η / □ or more, and the insulating property was judged to be high. Further, in order to confirm the protective layer function of the transparent film, a silver paste was applied onto the transparent film, and a firing treatment was performed at 500 ° C for 1 hour. As a result, silver coloration (yellow change) was not observed. The low alkali glass is produced by a float method. It is possible to discriminate whether or not tin penetrates the transparent film by whether or not there is silver coloration. That is, it can be said that the transparent film sufficiently possesses the protective layer function required for display use. The film formation conditions and the properties of the transparent film are shown in the following (Table 1) and (Table 2). (Example 2) Using a device as shown in Fig. 2, a film having tantalum nitride as a basic skeleton was formed on the surface of a glass ribbon by a line CVD method. The fused glass raw material composed of 1500 to 1600 C in a floating bath and composed of a usual sodium #5 glass composition. When the temperature of the glass ribbon is 830 °C, from the i-th applicator on the most upstream side (16a in Fig. 3), the molar ratio of ammonia to formazan is 100, 17 !298315 ^ A raw material emulsion having a concentration of om and nitrogen as a carrier gas: and a thin film having a thickness of 4511111 was formed on the surface of the glass ribbon having a thickness of 2.8. At this time, the film forming speed is Wse, and the glass is slowly cooled and cooled in the inside. Then, the cutter placed on the downstream side of the conveyance is cut into a predetermined size to prepare a glass substrate. The transparent film is of an example. As a result, the composition of the transparent film was 矽: 44 atom%, nitrogen, Ο atom%, oxygen: 2 atom%, and hydrogen atom%, and the visible light transmittance was 85.1%, the refractive index L97, and the surface resistance was 1〇1Gd/□ or more. Also, I did not see the color of silver. The film formation conditions and the properties of the transparent film are shown in the following (Table 1) and (Table 2). 'Comparative Example 1', except that the raw material gas of the Μ 2 raw material gas was changed to the raw material gas in which the molar amount of the ammonia (f) was 450 and the concentration of the decane was 〇15111〇1%, the same as in the case of the second embodiment. The method forms a film. The film formation speed at this time was Snm/s and the thickness of the film was 15 nm. The film was examined for its characteristics in the same manner as in Example ι. As a result, the composition of the transparent film is 矽: 36 子 sub-nitrogen atom%, oxygen · 2 atom%, and hydrogen: 22 atom%, and its visible light transmittance A 89.5%, refractive index u5, and surface resistance are 1〇. 1Gq/〇 or more. Moreover, although the transparency is high, the color of silver can be seen. Therefore, it can be said that the film has a low barrier layer and cannot be used for display applications requiring high transparency. 18 1298315 The film formation conditions and film properties described above are shown in the following (Table i) and (Table 2). (Comparative Example 2) The ammonia of Example 2 was replaced with ethylamine, and a raw material gas having a molar ratio of ethylamine to methane to 25 and a concentration of decane of 〇5 m〇1% was used, and the film formation rate was changed. A film was formed in the same manner as in Example 2 except that the thickness was changed to 1 nm/s and the thickness was changed to 4 nm. The film was examined for its characteristics in the same manner as in Example 。. As a result, the composition of the transparent film was 矽: 33 atom% nitrogen 31 atom%, oxygen: 16 atom%, and carbon: 21 atom%. Although not measured. The visible light transmittance and refractive index of the film were observed, but visually observed to have the same degree of transparency as the transparent film of Example 1 $1. Further, although the surface resistance was 1 〇 10 gates/gate and 7 L u /U or more, the color of silver was observed. Therefore, it can be judged that the protective layer of the film has low function. The properties are shown below (the table on the film formation conditions and film characteristics 1) and (Table 2). 19 1298315 (13⁄4 i film composition (atomic %) 〇〇ο O 〇3 LO CO o 〇OJ CN1 οα CO ίζ CO cB §8 η film formation rate (nm/s) α CO s glass temperature CC) 8 s § Domain 〇拎3 LO CZD c=> LO <=> LO CZ5 NH3/SiH4 (Morby) § s § oa Example 1 Example 2 Comparative Example 1 Comparative Example 2 Coloring yellow due to heat treatment Yellow ώ /^ν 55 ® α ^1010 ^1010 ^1010 ^1010 Refractive index 05 τ-Η 1.85 Unmeasured transmittance (°/〇) 88.7 85.1 89.5 Unmeasured film thickness (nm) LO LO Example 1 Example 2 Comparative Example 1 Comparative Example 2 1298315 By comparing the above examples with the comparative examples, it is understood that the composition of the transparent film can be adjusted by changing the concentration of the concentration of methotin and ammonia in the material gas in the CVD method. It is also known that the transparent film formed by the film forming conditions of the present invention has high visible light transmittance, high insulating property, and high protective layer/body. By comparing Examples 1, 2 and Comparative Examples, the material gas is known. The higher the molar ratio of the ammonia to the money, the lower the cut ratio of the formed film. Further, it is understood that as the content of ruthenium increases, the visible light transmittance of the film decreases and the refractive index increases. According to the present invention, the present invention has the following effects. According to the method for forming a transparent film of the present invention, the rapid film formation speed of the on-line CVD method can be achieved. Further, by appropriately maintaining the concentration of the compound in the raw material gas 3 and appropriately adjusting the content of the cerium-containing compound and ammonia, it is possible to maintain a high film forming speed and to form a transparent film which is highly transparent and which is not peeled off from the transparent substrate. The inner tape forming wire i is a film forming method, and can be a transparent film having a large area and no pinhole defects in a short time. Further, since the energy required for the thermal decomposition reaction of the raw material gas in the green C1 is from glass to the total energy cost of the glass substrate having the transparent film. The transparent film glass substrate that can be used in a vehicle can fully satisfy the construction or the car as a display, especially because it does not cause silver coloring, and is suitable for use in a board. 5 ' is particularly suitable for demanding plasma display panel bases 21 1298315 [Simplified description of the drawings] (1) Drawings Fig. 1 is a cross-sectional view showing an embodiment of a transparent substrate having a transparent film of the present invention. Figure 2 is a schematic illustration of the apparatus used in the in-line CVD process. Fig. 3 is a cross-sectional view showing an embodiment of a transparent substrate in which a transparent film and a functional film are laminated. (2) Symbols of components 1 Glass substrate 2 Transparent film 3 Film (functional film) 10 Glass tape 11 Melting furnace 12 Floating bath 13 Slow cooling furnace 1 5 Tin bath 16, 16a, 16b, 16c Applicator 17 Roller 22