TW200413264A - Method for forming transparent thin film, transparent thin film formed by the method and transparent substrate with transparent thin film - Google Patents

Abstract

This invention is to provide a method for forming a transparent thin film by the chemical vapor deposition method using a gaseous raw material ,which comprises forming a transparent thin film comprising at least one element selected from carbon (C) and oxygen (O), nitrogen (N), hydrogen (H), and silicon (Si) at a film forming speed of 8 nm/s or more. The method allows the formation of a transparent thin film which is less prone to exfoliation from a substrate due to the relaxation of the tensile stress therein and exhibits high transmissivity in the region of visible lights on a glass ribbon in a float bath.

Description

200413264 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（Si N)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「CVD」）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（Si N)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 透光率高’故適用於作為建物、車輛或者顯示器用之基板 使用。 氮化矽薄膜之形成方法已知有將甲矽烷（SiH4)與氨 (NH3)以常壓CVD法進行成膜之方法。但是，在習知之成膜 方法中’原料氣體中甲石夕烧之濃度例如為01raol%，屬較 低者。氮切薄膜中若財張力變大，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 氧製成氧氮化石夕⑻⑽）膜，以使張力下降之技術。例如， 在特開平1G-3G9777號公報，記載有卩gvd法於玻璃基板 200413264 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200卜100川號公報中，則著眼於氮化石夕薄 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cv"去中，將原 料氣體F錢與氨之流量比（SiVNH3)設定為肖之 低值。 不過’習知之制GVD法之氮切與氧氮切之成膜 ，度’雖依成膜裝置有所不同，但大約都在數四/s左右， 是很小的1別在浮法玻璃之製程巾，在浮式浴内浮於溶 融錫上之玻璃帶表面上欲以CVD法形成上述薄膜時（以下， 、—、·在上CVD法」稱啤该形成方法），以習知之成膜速度要 使薄臈厚度成長到能夠充分發揮特性之程度有固難。在線 上⑽法中，形成以氮切及氧氮切為主成分的薄膜時 :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] 一本發明係著眼於以上之問題點所產生。其目的為提 速膜之方法’其能以適用於線上CVD法之高成 錢形成薄膜中張力緩和、不易由基板上剝離且在可見 =光率高之透明薄膜。再者’係提供具備以該方法所 等薄膜之透明基體’其係適用於建物、車輛或顯示 寺用地之具備透明薄膜透明基板。 為達到上述目的’本發明提供„_種透明薄膜之成形 2UU413264 了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8nm/s卩上，且係形成含有擇自碳原子⑹及 氧（〇)中至少一者、氮（N)、氫原子（H)及石夕㈤之透明薄膜。 [實施方式] 本心月之形成方法以原料氣體中含梦化合物含量為 〇. 2mol%以上較佳。 原料氣體以含有切化合物及氨為佳。原料氣體中氨 對3矽化合物之莫耳比為4〇〜4〇〇即可。 原料氣體中所含之切化合物以甲梦烧（s^)為佳。 原料氣體可以對已事先裁斷之玻璃板喷附，但以向浮 =之玻璃帶表面喷附較佳。玻璃帶之表面溫度，例如 3rc為適當的。玻璃帶為具有_以下厚度者， 者者亦可為具有能成形為4随以下厚度左右之較高線速度 之方另、一方：提供一種透明薄膜，其係以本發明 之透明薄臈，其氫原子之含 %，以5〜20原子％為佳。 U原子 ， 勹佳攻透明薄膜即使厚度在4〇nffl以上 ”可見光透光率仍能在83%以上。 本表明在另一方面提供一綠且供、凑卩口 ％ ，苴含右、类μ I触 ，、種，、備透明4膜之透明基體 而^ 與在該透明基體上所形成之透明薄膜， 板較佳。二=述透明薄联。透明基❹玻璃 v /、備透明濤膜之透明基體亦可進一步含有 透月薄膜表面上所形成之機能性薄膜。 200413264 明 以下 對於本發明之較佳實施 形態參照圖式進一步說 早及圖Λ顯示—透明基體（例如玻璃基板〗），其被含有碳原 氮、氫原子及石夕原子等各元素為主成分所形成 :透明缚…被覆。薄膜2可利用濺錢法、離子植入或 ”空蒸鍍法等所謂物理蒸鍍法形成，但本發明使用cvd法 :物理蒸鑛法雖然膜厚均一性良好，但是，若考慮薄膜形 成叙耐久性等，以CVD法成膜者為較佳。cyD法中特別又 以常塵熱CVD為適合。依情況亦可利用觸㉟GV])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。卩CVD法進行成膜，可藉由將氣體狀原料向裁成 I定大小並加熱之透明基體喷附來進行。例如，將玻璃板 衣载在網孔輸送帶上，於通過加熱爐時供給原料氣體，在 ”、、至既疋溫度之玻璃基板表面上使原料進行反應。 "亥透明溥膜之原料氣體較佳為，至少含有含矽化合物 及氨此處之含矽化合物不僅包含以SinH2n+2所示之氫化 夕亦包含有機矽化合物。例如，除了甲矽烧（sih4)、乙 矽烷（Sl2He)等氫化矽以外，亦可使用四氯化矽（SiCl4)、二 虱矽烷（SiH2Cl2)、三氯矽烷（SiHCi3)、四氟化矽（SiF4)等 以i素取代一部分氫原子之氫化矽，四曱基矽烷 *^CH3)4Sl)等含烷基矽烷。其中特別以使用曱矽烷者較佳 因為曱石夕燒容易與氨反應，故成膜時副產物少，且，對 透明4膜中之碳原子、氧及氫原子之含有率可以在廣範圍 中進行調整。 200413264 /為CVD法中以往就開始使用之氮原料，容易取得且 氨乂外之氮原料’先前冒使用氮氣、胺類及聯胺類 ，有機物等，氮氣缺乏反應性，而有機物在工業生產規 板，原料調度上有困難，且工#化之使用上其毒性會產生 問^又’若將氨作為原料氣體使㈣，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 ?虎公報中之實施例， 己載以碎:¾及乙胺作為原料形成氮化碎薄膜之成膜速度為 6〇nm/mi㈣nm/s。對此，本發明中若以使用含氫化石夕與氨 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 ^ 疋以’成膜速度之目標以8〜15nm/s為佳。 原料氣體中含矽化合物之濃度以〇· 2m〇1%以上較佳。 、、又不滿〇 · 2mo 1 %日xj·，即使透明基體表面溫度在8 〇 〇以 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 過同’則因與氨之莫耳比要位於上述範圍内會有困難，故 200413264 在CVD法中合矽化合物之濃度上限以2· 為適當者。 又έ矽化合物之濃度若太咼，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，在原料氣體當中之含石夕化合物會有***之 危險1±因此，含矽化合物之濃度以在1. 4mol%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 夕化口物之莫耳幻以4〇〜4〇〇較佳。若該比值比“小，則 因S卜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。另一方面，該比 成比值右大於400，則不僅要使 原料氣體中含石夕化合物、、毚_ ^ 口物濃度“變得困難，且氨會開始抑 制含矽化合物之分解，佶成 刀解使成膑逮度下降。順帶一提，此氨 對含石夕化合物之莫耳比其 彡耳比*與㈣2G0H圆i號公報中所 §己載之各知方法加以比較，氨之比率高出了數倍。 一拉？月薄膜中之氧係由原料氣體中所添加之-氧 盾氧化奴及-氧化碳等氧化原料所提供。且，即 -接觸！氣體中不添加該等氧化原料下，藉由成膜後盘大 氧接觸產生自然氧化，有 ’、大 备 丁力曰在透明薄膜表面附近杈入 溥膜中之碳原子，可能是上述有機 石夕化合物殘潰的情況， 疋有機 汔7 Μ拉， 月田原枓風1體中所添加的乙执 或乙烯等低級烴類（為抑 们乙炔 化合物反應性）所提供。 疋各矽 俨笙入女斤人 破拉入透明薄膜中之氫原子為石々 烷專含有氫之含矽化合物 卞為矽 哕笼；吝h 卜 或風之殘潰。據推測，藉由脾 θ4兀素拉入氮化矽之莫 棺田將 土本a架中，使氮-矽之鍵結在 200413264 ^料氣體巾除域切化合物、A、氧化補及低級 二<外，亦可添加氮、氦或氫等。 形成有透明薄膜之透明㈣，只要具有 練及耐熱性、且能利用於上述建物㈣等用= p可’其種類不特別限定。例如，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㈣後述線i 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 ⑽法的優點較多。線±⑽法，係在浮式浴中於具有軟 化點以上熱度之玻料表面進行錢，補氣體之熱分解 反應會被玻璃帶之熱度所促進。其結果，+需要熱分解反 應用之加# ’可減少總能量成本。再者，可提高成膜速度 及成膜反應效率，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了故 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’藉由在透明薄臈即將形成前對玻璃 基板或玻璃帶表面吹送氨氣，可使成膜速度更進一步提高 。據信，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，而使含矽化合物在供給之時點急速進行熱分解 反應所造成。再者，為促進氨之分解，亦可在玻璃基板或 玻璃帶之表面附近配置觸媒。 線上CVD法係使用如圖 ^ , Λ …不之震置。該裝置中，玻 璃π 10係從熔融爐（浮式窯） 嫌山* ;U /现出到浮式浴12内，並從 页狀移動於錫浴15上之玻璃 m、 坡螭帶10表面間隔既定之距離， 於斤式冷内配置既定個數之 哭 土覆益16(圖示中有3個塗覆 口口 16a、16b、16c)。從該孳涂·庐突似 主覆态仏給原料氣體，並在玻 可：“ 成薄膜。又，若利用複數之塗覆器，則 :在玻璃冑10上積層薄膜。玻璃帶之溫度，可藉由浮式 f内配置：加熱器及冷卻器(圖示省略)而在塗覆器16之前 周整至既疋之溫度。形成有各薄膜之玻璃帶B被滾筒Η 往上“送人緩冷M 13。又，在緩冷爐13中被緩冷之玻 璃板係藉由圖示省略之浮式法通用之裁斷裝置裁為既定尺 寸0 猎由於浮式浴内之上游部進行成膜，可使朝向未與炼 融狀態錫接觸之面(玻璃帶上面;頂面)之錫熱擴散(錫蒸氣 之擴散)抑制在最小限度。當玻璃帶上面之錫擴散量多時 右透明薄膜薄，易使其保護層機能變不足。例如，在透 明薄膜上塗布以銀為主成分的糊狀物進行燒成製成電極時 ’若銀或錫穿過透明薄膜，銀與錫會反應並著色，在作為 頌不器用途使用時經常會產生問題。即，藉由在浮式浴内 之上游部形成透明薄膜，不須使透明薄膜變厚即可解決娘 或錫之穿透的問題。 線上CVD法一般在玻璃帶表面溫度為5〇〇〜850°C之範 圍内成臈。該透明薄膜較佳為，在即將成膜前之玻璃帶表200413264 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for forming a thin film, which uses silicon nitride (Si N) with carbon atoms or the like as the basic skeleton to form a thin film with high visible light transmittance. . Furthermore, the present invention relates to a transparent substrate provided with a transparent film manufactured according to this method, for example, a transparent substrate provided with a transparent film which is suitable for applications such as buildings, vehicles, and displays. [Prior Art] A technique for forming a thin film on a glass substrate by a chemical vapor deposition method (hereinafter, referred to as "CVD") is well known. There are many types of thin films formed, such as silicon nitride (Si N) films. Silicon nitride films are widely used as insulating films in the semiconductor field. In addition, the silicon nitride film can be used as a diffusion barrier for various ions such as sodium or silver due to its dense structure, for example, it can be used as an acid-resistant mask. A glass substrate with a silicon nitride film is suitable for use as a substrate for a building, a vehicle, or a display because of its high light transmittance in the visible light region. As a method for forming a silicon nitride film, a method of forming a film of silane (SiH4) and ammonia (NH3) by a normal pressure CVD method is known. However, in the conventional film-forming method, the concentration of kaishi yaki in the 'source gas' is, for example, 01raol%, which is relatively low. If the carbon tension in the nitrogen-cut film is increased, there is a problem that it may peel off from the glass substrate. In order to solve this problem, a technique is known in which oxygen is drawn into a thin film to form an oxynitride (silicon oxynitride) film to reduce the tension. For example, Japanese Patent Application Laid-Open No. 1G-3G9777 describes a technique of forming a thin film containing silicon nitride and silicon oxynitride as a main component on a glass substrate 200413264 by a gvd method. Furthermore, in JP 200, 100, and 100, the focus is on the protective layer function of the nitride nitride film. In order to form a complete nitride nitride film, that is, a silicon nitride film containing no impurities, the method described in it is described in Plasma cv " sets the flow rate (SiVNH3) of the raw material gas F to ammonia to a low value. However, the film formation degree of nitrogen cutting and oxygen nitrogen cutting of the conventional GVD method is different according to the film forming device, but it is about four / s, which is very small. 1 It is not in the float glass. When manufacturing the process towel, the above-mentioned film is formed by CVD on the surface of the glass ribbon floating on the molten tin in a floating bath (hereinafter, the above-mentioned CVD method is called the beer formation method), and the film is formed by the conventional method. It is difficult to speed up the thickness of the thin cymbal to the extent that the characteristics can be fully exerted. When forming a film mainly composed of nitrogen-cutting and oxygen-nitrogen-cutting in the online winding method: if it is to grow to a film thickness that can fully exhibit its characteristics, it depends on the moving speed of the glass ribbon, but it needs to be about 8nm / s the above. [Summary of the Invention] The present invention is made by focusing on the above problems. The purpose is to speed up the film method ', which can form a transparent film with low tension in the high-cost thin film suitable for the in-line CVD method, which is not easily peeled off from the substrate, and has a high visible light ratio. Furthermore, 'the transparent substrate provided with a film such as this method' is a transparent substrate provided with a transparent film suitable for a building, a vehicle, or a display temple. In order to achieve the above purpose, the present invention provides __ a variety of transparent thin film forming 2UU413264 is a transparent thin film formed by chemical vapor deposition method using a raw material gas, the film forming speed is 8nm / s 且, and the system contains selected carbon atoms透明 and at least one of oxygen (0), nitrogen (N), hydrogen atom (H) and Shi Xiyin's transparent film. [Embodiment] The method of forming the heart of the month, the content of the dream compound in the raw material gas is 0. 2 mol% or more is preferred. The raw material gas preferably contains a cutting compound and ammonia. The molar ratio of ammonia to 3 silicon compounds in the raw material gas may be 40 to 400. The cutting compound contained in the raw material gas is methyl dream. It is better to burn (s ^). The raw material gas can be sprayed on the glass sheet that has been cut in advance, but it is better to spray on the surface of the glass ribbon. The surface temperature of the glass ribbon, such as 3rc is appropriate. The glass ribbon is Those who have a thickness of _ or less may also have a high linear velocity that can be formed to a thickness of about 4 or less. The other side is to provide a transparent film, which is based on the transparent thin film of the present invention, and its hydrogen atom. Contains%, preferably 5 to 20 atomic% U atom, Bao good tapping transparent thin film thickness 4〇nffl even more "visible light transmittance is still more than 83% can be. This indication provides a green, transparent, and transparent interface on the other hand, including a transparent, transparent, and transparent substrate with a μ-like, transparent, and transparent film, and a transparent film formed on the transparent substrate. The board is better. Two = the transparent sheet. The transparent base glass v /, the transparent substrate with a transparent film can further contain a functional film formed on the surface of the meniscus film. 200413264 In the following, the preferred embodiment of the present invention will be further explained with reference to the drawings. As shown in the figure, a transparent substrate (such as a glass substrate), which is composed of carbon elements such as nitrogen, hydrogen atoms, and stone atoms. Formed: transparent bondage ... covered. The thin film 2 can be formed by a so-called physical vapor deposition method such as a sputtering method, ion implantation, or “air evaporation method”, but the present invention uses a cvd method. Although the physical vapor deposition method has good film thickness uniformity, For durability, etc., it is better to use CVD method. CyD method is especially suitable for dust and thermal CVD. Depending on the situation, it is also possible to use the GV]) method, which uses a contact medium and a transparent substrate. The raw material gas undergoes a contact decomposition reaction. 卩 CVD method for film formation can be carried out by spraying a gaseous raw material onto a transparent substrate that is cut to a size of I and heated. For example, a glass plate clothing is loaded on a mesh conveyor belt When the raw material gas is supplied while passing through the heating furnace, the raw material is reacted on the surface of the glass substrate at a temperature of up to a predetermined temperature. " The raw material gas of the transparent film is preferably at least a silicon-containing compound and ammonia. The silicon-containing compound here includes not only a hydrogenated compound represented by SinH2n + 2, but also an organic silicon compound. For example, in addition to silicon hydride (sih4), silane (Sl2He) and other hydrogenated silicon, silicon tetrachloride (SiCl4), disilane (SiH2Cl2), trichlorosilane (SiHCi3), silicon tetrafluoride ( SiF4) and other silicon-containing silanes, such as silicon hydride, in which a part of hydrogen atoms are replaced with i element, tetrafluorinyl silane * ^ CH3) 4S1) and the like. Among them, it is particularly preferred to use osmium silane because vermiculite is easy to react with ammonia, so there are fewer by-products during film formation, and the content of carbon atoms, oxygen, and hydrogen atoms in the transparent 4 film can be in a wide range. Make adjustments. 200413264 / It is a nitrogen raw material that has been used in the CVD method in the past. It is easy to obtain and it is a nitrogen raw material other than ammonia. 'Nitrogen, amines and hydrazines, organic matter, etc. were previously used. It is difficult to schedule raw materials, and its toxicity will cause problems in the use of industrial chemicals. If ammonia is used as the raw material gas, carbon atoms can be prevented from being mixed in the transparent film, so the film formation speed can be increased. If the film formation speed of the transparent film is premised on industrial production, the faster the better. For example, in the example disclosed in Japanese Patent Application Laid-Open No. 10-30907777, the film formation speed of a nitrided thin film that has been prepared using crushing: ¾ and ethylamine as a raw material is 60 nm / mi㈣nm / s. On the other hand, in the present invention, if a raw material gas containing hydrogenated stone and ammonia is used, the film formation speed can be 8 nm / s or more. On the other hand, in actual production, the faster the film formation speed, the easier the uniformity of the transparent film will be impaired. For example, the film thickness may be several times different in some cases, or there may be disadvantages such as pinholes. Therefore, the film-forming speed itself has a limit, and even in a line CVD method that requires a high film-forming speed, at about 15 nm / s, a transparent film of sufficient thickness can be formed on a lmm glass ribbon that must accelerate the line speed ^ 'The target of' film formation speed 'is preferably 8 ~ 15nm / s. The concentration of the silicon-containing compound in the raw material gas is preferably 0.2% or more. It is less than 0 · 2mo 1% day xj ·, even if the surface temperature of the transparent substrate is above 800, the film formation speed cannot reach 8nm / S, and the film formation will take too much time. In particular, in the online CVD method, if the film formation speed is less than 8 nm / s, although the film formation apparatus or operating conditions are different, there may be problems such that the thickness of the available glass ribbon is limited to a range greater than 4 mm. On the other hand, if the concentration of the silicon-containing compound is too the same, it will be difficult to locate the molar ratio with ammonia in the above range. Therefore, the upper limit of the concentration of the silicon compound in the CVD method is 2 ·, which is appropriate. If the concentration of silicon compound is too high, thermal decomposition reaction in the gas phase will turn into powder, causing defects such as pinholes on the transparent film, or not only the film-forming speed will decrease, but also the stone-containing compounds in the raw material gas. There is a danger of explosion 1 ±. Therefore, the concentration of the silicon-containing compound is less than 1.4 mol% is practical. The molar ratio of ammonia to silicon-containing compounds in the raw material gas (the molar number of ammonia / the molar content of the chemical substance containing the chemical substance is preferably 40 to 400. If the ratio is smaller than ", it is because SbSi As more bonds are formed, a film with low transparency with an absorption band in the visible light region will be formed. On the other hand, the ratio of the ratio to the right is greater than 400, which not only makes the raw material gas contain stone compounds, 毚 _ ^ "It becomes difficult, and ammonia will start to inhibit the decomposition of silicon-containing compounds, and the cleavage will reduce the degree of entrapment. By the way, this ammonia has a molar ratio of stone-containing compounds to its molar ratio * and ㈣2G0H round Compared with the known methods in § I, the ratio of ammonia is several times higher. The oxygen in the one-layer film is the oxygen shield oxide and carbon oxide added in the raw material gas. Provided by oxidation raw materials. And, that is, contacting! Without adding these oxidation raw materials to the gas, natural oxidation occurs through the contact of large oxygen on the disc after film formation. The carbon atoms in it may be the case of the above organic stone compound , 疋 Organic 汔 7 Μ pull, provided by lower hydrocarbons such as ethylene or ethylene (for the reactivity of acetylene compounds) added to Yuetianyuan 枓 1 body. The hydrogen atom in the transparent film is berberane, which is a silicon-containing compound containing hydrogen, and the silicon cage; 吝 h or the wind is broken. It is speculated that the spleen θ4 element is pulled into the silicon nitride coffin field. In the soil frame A, the nitrogen-silicon bond is bonded to 200413264. In addition to the domain cutting compound, A, oxidation supplement, and lower two, nitrogen, helium, or hydrogen can be added. A transparent film is formed. As long as it is transparent and has heat resistance and can be used for the above-mentioned building materials, etc., the type is not particularly limited. Examples include glass plates and heat-resistant plastics. When a glass plate is used as a transparent substrate A transparent film can be formed on a glass plate cut to an appropriate size. The line i CVD method described below can also be used to form a transparent film while the glass plate is being formed. In industrial production, the latter method has many advantages. ± ⑽ method, with a softening point in a floating bath When the surface of the frit with the above heat is used for money, the thermal decomposition reaction of the make-up gas will be promoted by the heat of the glass ribbon. As a result, the addition of the thermal decomposition reaction required # 'can reduce the total energy cost. Furthermore, it can improve the film formation Speed and film-forming reaction efficiency, and suppress pinholes and other defects. At the same time, glass ribbons with heat above the softening point have a large surface size freedom, so the in-line CVD method can make the tension in the nitride-based film unique to the film Reduced, forming a transparent film with high adhesion and mechanical strength. Also in the CVD method, by blowing ammonia gas on the surface of the glass substrate or glass ribbon just before the formation of the transparent thin film, the film formation speed can be further improved. According to It is believed that ammonia was in contact with the glass substrate or glass ribbon and decomposed and adsorbed there, which caused the silicon-containing compound to undergo a rapid thermal decomposition reaction at the time of supply. Furthermore, in order to promote the decomposition of ammonia, a catalyst may be disposed near the surface of the glass substrate or the glass ribbon. The online CVD method is used as shown in Figure ^, Λ ... In this device, the glass π 10 is taken from the melting furnace (floating kiln) to the mountain *; U / is appeared in the floating bath 12 and moved from the sheet to the glass m on the tin bath 15 and the surface of the slope belt 10 At a predetermined distance, a predetermined number of crying soil covers 16 are arranged in the cold type (three coating ports 16a, 16b, 16c are shown in the figure). The raw material gas is supplied from this coating-like structure, and the glass is: "formed into a thin film. If multiple coaters are used, the film is laminated on the glass. The temperature of the glass ribbon, It can be arranged in the floating type f: heater and cooler (not shown) and it can be rounded to the existing temperature before the applicator 16. The glass ribbon B formed with each film is lifted up by the roller Η Slowly cool M 13. In addition, the slow-cooled glass plate in the slow-cooling furnace 13 is cut to a predetermined size by a cutting device commonly used in the float method, which is omitted in the figure. Thermal diffusion of tin (diffusion of tin vapor) on the surface in contact with tin in the molten state (upper glass ribbon; top surface) is minimized. When the amount of tin diffusion on the glass ribbon is large, the right transparent film is thin, which makes its protective layer function insufficient. For example, when a paste containing silver as the main component is coated on a transparent film and fired to form an electrode, 'if silver or tin passes through the transparent film, silver and tin react and color. Will cause problems. That is, by forming a transparent film upstream in the floating bath, it is possible to solve the problem of penetrating mother or tin without thickening the transparent film. The in-line CVD method is generally performed within a range of a surface temperature of the glass ribbon of 500 to 850 ° C. The transparent film is preferably a glass tape surface just before film formation.

13 200413264 面溫度為700〜83(rc之範圍内形成。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：之薄膜中張力可以降低，可形成附著力提高、 機械強度尚的透明薄膜。 古該透明薄膜因係以氮化石夕為基本骨架，堅硬且透明度 门、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 種料之擴散障壁能力會下降。另外―方面，若㈣α 2子％ ’則在可見光區之吸收會變大，透明薄膜之透明性 曰下降。又’在透明薄膜中氮之原子含有率對於石夕之原子 含有率比以越接近氮化石夕之化學計量組成比之13較佳。 又’在透明薄膜令氮之原子含有率對於石夕之原子含有率比 若低於0.9，且开目止广 3¾手比 八見光區之吸收會變大，薄膜之透明性會 争文°亥透明薄膜氮之原子含有率對於矽之原子含有 率比以調整為〇.9〜丨.3為適當的。 山、薄膜以含有碳或氧中至少一者卜J 〇原子％為佳。 石反’依f含有率可變化透明薄膜之可見光區吸收率。另一 、 氧可使透明薄膜之張力緩和使應力減輕，並使對於 透明基板之附著力接古 、 、 等機能有效發揮，# J二之使機械強度亦提间。為使該 車乂“為碳或氧之原子含有率位於1〜1 Q 子^ 2範圍内。又 ” 兩 反與^可任選一種，或者亦可兼含有 Α ^ η亥透明薄膜以氫為必要構成元素。若氫之含 有率變向，读 透月薄膜之緻密度會劣化，對各種離子之擴散 200413264 障壁力下降，故其含有率以4〜20原子％為佳。 透明溥膜厚度為確保其保護層機能，必需為2以上 ，另一方面，為確保可見光透光率，以3〇〇nm以下為佳。 =，透明薄膜之折射率，由於與後述透明導電膜或透明基 體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 112.1。 又，透明薄膜之穿透率越高越好，本透明薄膜即使名 厚度為4〇nm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（如〇2)、 二氧化矽（Si〇2)、矽氧化錫（SnSi0)、氧碳化矽（si〇c)2、碳 化石夕⑻⑺或二氧化鈦（Ti〇2)為主成分製成之薄膜3積層於 透明薄膜2上。薄膜3為機能性薄膜，以氧化錫為主^分 ^薄膜係作為透明導電膜，以二氧切切氧化錫為主成 分之溥膜係作為保護膜或絕緣性膜，以碳化矽為主成分 薄膜係作為保護膜或絕緣性膜或進—步為茶色性之著= ’-氧化鈦可作為具有熱線反射或光觸媒機能 將該等機能性薄膜3與薄膜2組合，不會損害透明心之 以適當調整反射率、導電性或保護層機 月b 4 ’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 -八積層之順序及積層數不特別限定，可依 、 需之機能適當改變。例如，如依圖3之 "途及所 性薄膜3覆蓋化學安定性及物理強度高之透明機， 200413264 得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。特別A，機能性薄膜可在與透明薄媒 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。 具備該透明薄膜之透明 用所要求之特性，特別是由 為顯示器用，特別是可作為 用0 基板，可充分滿足建物或車輛 於不會發生銀之著色，亦可作 要求嚴格之電漿顯示器面板使13 200413264 The surface temperature is within the range of 700 ~ 83 (rc. If this temperature range is used, not only the film formation speed can be accelerated, but also the degree of freedom of the size of the surface of the glass ribbon, so that the nitride film can be characterized: the tension in the film can be Reduced, it can form a transparent film with improved adhesion and high mechanical strength. This transparent film is based on nitride stone as the basic framework, and it has a hard and transparent door with low absorption in the visible light region. The transparent film contains the atoms of nitrogen and nitrogen. The ratio is preferably Shixi: 35 to 45 atomic%, nitrogen: 30 to 60 atomic%. If the content of Shixi atom is less than 35 atomic%, the denseness of the transparent film will be deteriorated, and diffusion of various materials will be caused. Barrier capacity will be reduced. In addition-in one aspect, if ％ α 2 sub %% ', the absorption in the visible light region will increase, and the transparency of the transparent film will decrease. Also, the atomic content of nitrogen in the transparent film will The ratio is preferably closer to the stoichiometric composition ratio of the nitrided stone. The ratio of the atomic content of nitrogen to that of the stone is more than 0.9 in the transparent film, and it is wide open. The absorption of 3¾ hand than that in the Yamiami area will become larger, and the transparency of the film will be discussed. The atomic content ratio of nitrogen in the transparent film is appropriate to adjust the atomic content ratio of silicon to 0.9 ~ 丨 3. It is preferable that the film and the film contain at least one of carbon or oxygen. The atomic percentage of the transparent film can be changed in accordance with the content ratio of f. The oxygen can relax the tension of the transparent film and make it stress. Lighten and make the adhesion to the transparent substrate function effectively, #J 二 之 makes the mechanical strength also improved. In order to make the car's "carbon or oxygen atom content rate is located in the 1 ~ 1 Q ^ Within the range of 2 "and" two opposites "and" ^ "can be selected either, or they can also contain A ^ η transparent film with hydrogen as an essential constituent element. If the hydrogen content rate is changed, reading the density of the moon film will be Deterioration, diffusion of various ions 200413264 The barrier force is reduced, so its content rate is preferably 4 to 20 atomic%. The thickness of the transparent film must be 2 or more in order to ensure its protective layer function. On the other hand, in order to ensure visible light transmission The ratio is preferably 300 nm or less. = The refractive index of the transparent thin film is higher as the refractive index difference with the transparent conductive film or transparent substrate described later becomes higher, so it is preferably closer to the refractive index of the transparent conductive film and glass substrate generally composed of tin oxide. 112.1. The higher the transmittance of the transparent film, the better. The transparent film can ensure a visible light transmittance of 83% even at a nominal thickness of 40 nm. Figure 3 shows an example of a glass substrate, which will be oxidized. It is made of tin (such as 〇2), silicon dioxide (Si〇2), silicon oxide (SnSi0), silicon oxycarbide (si〇c) 2, carbonized carbide or titanium dioxide (Ti〇2). The thin film 3 is laminated on the transparent thin film 2. The thin film 3 is a functional thin film, which is mainly composed of tin oxide, and the thin film system is used as a transparent conductive film. Film, with silicon carbide as the main component. The thin film system is used as a protective film or an insulating film or further-brown works. '-Titanium oxide can be used as a heat-reflective or photocatalyst. Combine these functional films 3 and 2 Without compromising transparency It can improve the reflectivity, conductivity, or protective layer b 4 ′ and improve its durability. Figure 3 shows the formation of a functional thin film on the thin film 2 on the surface of a glass substrate. The order and number of eight laminations is not particularly limited, and can be appropriately changed depending on the required function. For example, if a transparent machine with high chemical stability and high physical strength is covered by the " transistor film 3 according to Fig. 3, 200413264, a functional glass substrate with higher durability can be obtained. The transparent thin film may have a substantially uniform composition in a thickness direction of the film, or may have a composition gradient. In particular, the functional film can change its composition near the interface in contact with the transparent thin medium. Thereby, the adhesion between the transparent film and the functional film can be improved. It has the characteristics required for the transparency of the transparent film, especially for display, especially as a substrate, which can fully meet the building or vehicle's color without silver, and can also be used as a strict plasma display. Panel make

依習慣係指構成成分之 ’但本發明不限定於以 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 下之實施例。 (實施例1)Conventionally, it refers to the constituent components, but the present invention is not limited to those in which the "main component" in the present invention has a weight content ratio of 50% by weight or more. Examples Hereinafter, examples of the present invention will be described using examples. (Example 1)

將事先裁斷為每邊10cm正方形、厚度i imm之以浮 製造之低鹼玻璃洗淨並乾燥。在該玻璃版上以常壓㈣ 形成以氮化矽為主成分之透明薄膜。成膜係於約謂。 c 爐内將玻璃板以i.Wdn之速度搬送之條件 内設置之塗覆器’在氨對甲錢之莫耳比_下，供給 砍炫？辰度0.5mol%且以氮教作么番 在玻璃基板表面上形成厚度4Gnm之以氮切為 的 明薄膜。此時成膜速度為1〇nm/s。 16 200413264 由χ射線激發光電分光分析及拉塞福後方散射分析， 確認:亥透明薄膜之組成為矽4〇原子％、氮43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 (⑴⑽咖⑷敎55Qnm之折射率結果為139卜該特 性不僅於建物或汽車等之用豸，在要求高透明性之顯示器 用，特別是作為要求嚴格之電漿顯示器面板用基板使用上 ’都是在實際❹無問題的等級。又’透明薄膜之表面電 阻值為101ΰΩ/□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5G(rc下施以丨小時之燒成處理。結果 並未見到銀產生著色（黃色變化）。該低驗玻璃因係以浮 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 &，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 150(M600 C、以通常之鈉鈣玻璃組成所構成之熔融玻璃原 材料。於玻璃帶之溫度為830。(：時，自位於最上游側之第ι 塗覆器（圖3中16a)，在氨對甲矽烷之莫耳比為1〇〇下， 200413264 供給所含甲石夕烧濃度為O.lm〇1%且以氮氣作為載氣之原料 軋體，並於厚度2.8mm之玻璃帶表面上形成厚度為45枷之 透明薄膜。此時之成膜速度A 9nm/se將該玻璃帶於緩冷 爐内使其緩冷，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 々曰丨K方法，檢查其书 性。其結果，透明薄膜之組成構成為矽：44原子％、氮.4The low-alkali glass cut into a square of 10 cm on each side and having a thickness of imm in advance was washed and dried. A transparent film mainly composed of silicon nitride is formed on the glass plate by atmospheric pressure. Film formation is based on appointments. c The condition that the glass plate is transported in the furnace at the speed of i.Wdn. The coater installed in the furnace is supplied under the molar ratio of ammonia to nail money. A film with a thickness of 4 Gnm and a thickness of 4 Gnm was formed on the surface of the glass substrate with a mole of 0.5 mol% and nitrogen as the substrate. The film-forming speed at this time was 10 nm / s. 16 200413264 Analysis by X-ray excitation photoelectron spectroscopy and Lassefer rear scattering analysis confirmed that the composition of the transparent film was 40 atomic% silicon, 43 atomic% nitrogen, and 2 atomic% oxygen 15 atomic% hydrogen. The result of measuring the visible light transmittance of the transparent film by a spectrophotometer was 88.7%, and the refractive index result of the elliptical thickness gauge (55 ° nm of ⑴⑽ Coffee ⑷ 敎 55Qnm was 139). This characteristic is not only used for buildings or automobiles.豸, for displays that require high transparency, especially for substrates for plasma display panels with strict requirements, are all practically non-problematic. Also, the surface resistance of transparent films is 101ΰΩ / □ or more. Insulation can be judged to be high. In order to confirm the protective layer function of the transparent film, a silver paste was coated on the transparent film and subjected to a firing treatment at 5G (rc). Silver is colored (yellow change). Because the low inspection glass is manufactured by float method, it can be judged whether tin penetrates the transparent film by the presence or absence of silver coloration. That is, it can be said that the transparent film has the protection required for display applications. Layer function. Regarding the above-mentioned film formation conditions and the characteristics of the transparent film, finishing is shown in the following (Table 1) and (Table 2). (Example 2) Using the apparatus shown in FIG. 2, online CVD & A thin film with silicon nitride as the basic framework is formed on the surface of the glass ribbon. A 150 (M600 C, molten glass raw material composed of a normal soda-lime glass composition) flows into the floating bath. The temperature of the glass ribbon is 830. ( : At the time, from the first coater (16a in Fig. 3) located at the most upstream side, at a molar ratio of ammonia to silane of 100, 200413264 was supplied at a concentration of 0.1 mg. A rolling body of 1% with nitrogen as a carrier gas, and a transparent film having a thickness of 45 形成 is formed on the surface of a glass ribbon having a thickness of 2.8 mm. At this time, the film forming speed A 9 nm / se puts the glass ribbon in a slow cooling furnace. It was allowed to cool slowly inside, and then cut to a predetermined size by a cutting machine arranged on the downstream side of the conveyance to produce a glass substrate. The transparent film was examined for its bookability with the method of Example 丨 K. As a result, The composition of the transparent film is silicon: 44 atomic%, nitrogen. 4

原子％、氧：2原子％及氫13原子％，其可見光穿透率声 85.1%、折射率1.97、表面電阻為1〇1Qi}/□以上。又，^ 見到銀之著色。 整理表示於下 關於上述成膜條件及透明薄膜之特性， 述（表1)及（表2)。 (比較例1)Atomic%, Oxygen: 2 Atomic% and 13 Atomic% hydrogen. The visible light transmittance is 85.1%, the refractive index is 1.97, and the surface resistance is more than 10Qi} / □. Also, ^ see the color of silver. The finishing is described below. The above-mentioned film formation conditions and characteristics of the transparent film are described in (Table 1) and (Table 2). (Comparative example 1)

除了將實施例2原料氣體改為使用氨對甲錢之莫 士為45。、且甲石夕烧濃度為。·15m〇1%之原料氣體以外： 貫施例2以相同之方法形成薄膜。此時之成膜速产 且薄膜之厚度為15⑽。對該薄膜以與實施例^ ^方法檢查其特性。其結果’透明薄膜之組成構成為石夕. :、子％、氮·，原《、氧：2原子％及氫：22原子％，並可 牙透率為89.5%、折射率h85、表面電阻為ι〇ΐ0』 上。又，雖然透明性高’但可見到銀之著色。 此薄膜之保護層機能低’且^ 示器用途上。 巾於要“透明性之！ 18 200413264 對上述成膜條件及薄臈特性，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、且曱矽烷濃度為〇 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Except that the raw material gas of Example 2 was changed to 45 using ammonia to methyl chloride. , And the concentration of kaishi yaki is. • Except 15% 001% raw material gas: In the same manner as in Example 2, a thin film was formed. The film formation at this time was rapid and the thickness of the film was 15 ⑽. The film was examined for its characteristics in the same manner as in Example ^^. As a result, the composition of the transparent film was Shi Xi.:, Zi%, nitrogen, 《, oxygen: 2 atomic% and hydrogen: 22 atomic%, and the tooth permeability was 89.5%, the refractive index h85, and the surface resistance Ι〇ΐ0 』on. In addition, although the transparency was high, silver color was seen. This film has a low protective layer function and is used for display applications. It is necessary to "transparency!" 18 200413264 The above film forming conditions and thin film properties are summarized and shown in the following (Table i) and (Table 2). (Comparative Example 2) Except that the ammonia of Example 2 is ethylamine Instead, a raw material gas having a molar ratio of ethylamine to silane of 25 and a concentration of 0.5% of silazane was used, and the film-forming speed was changed to 1 nm / s and the thickness was changed to 4 nm. A thin film was formed in the same manner. The thin film was formed in the same manner as in Example 丨.

法檢查其特性。其結果，透明薄膜之組成構成為石夕·Μ原Method to check its characteristics. As a result, the composition of the transparent film was Ishigaki · Mhara

=、氮：31原子％、氧：16原子％及碳：21原子％。雖未測定 ”亥溥膜之可見光穿透率血折I 站 斤射率，但以目視之觀察，其外 觀具備與實施例1之透明薄 攻a溥Μ同程度之透明性。 表面電阻為101()Ω /□以卜, 雖然 u以上’但可見到銀菩 判斷此薄膜之保護層機能低。 色。支可以 關於上述成膜條件及薄膜特性 1)及（表2)。 金里表不於下迷（表=, Nitrogen: 31 atomic%, oxygen: 16 atomic%, and carbon: 21 atomic%. Although the visible light transmittance of the "Hierium film" was not determined, the appearance of the film had the same degree of transparency as the transparent thin film a 溥 M of Example 1 by visual observation. The surface resistance was 101. () Ω / □ Eb, although it is above u, it can be seen that Yinpu judges that the protective function of this film is low. Color. The above conditions and film characteristics 1) and (Table 2) can be mentioned. Yuxia Mi (Table

19 200413264 (I<) 薄膜組成（原子％) ◦ 〇 〇 ο μ LO CO τ—Η o 〇 οα οα CO CO CO 奉 η S CJD CO CD 玻璃溫度 CC) 〇〇 § 泛 曱矽烷濃度 (mol%) LO <Z=> C3 LO d> LO i s oa 實施例1 實施例2 比較例1 比較例2 因熱處理產生之著色 黃色 黃色 表面電阻值 (〇/□) ^1010 ^1010 ^1010 ^1010 折射率 r-H r-H 1.85 未測定 穿透率 (%) 88.7 1—Η LO oo 89.5 未測定 膜厚 (nm) LO LO τ—Η 寸 實施例1 實施例2 比較例1 比較例2 200413264 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石夕貌與氨濃度之濃度，^周整 ，明薄膜之組成構成。且可知’以本發明之成膜條件所形 透明薄膜具有高可見光穿透性、高絕緣性及高保護層 機能。 具體上，藉由比較實施例 氣 有 透 4汉比杈例1可知，原； 體中氨對f㈣之莫耳比越高，則所形叙薄膜中石h19 200413264 (I <) Thin film composition (atomic%) ◦ 〇〇ο μ LO CO τ—Η o 〇οα οα CO CO CO Feng η S CJD CO CD Glass temperature CC) 〇〇§ Panthanilane concentration (mol%) LO < Z = > C3 LO d > LO is oa EXAMPLE 1 EXAMPLE 2 COMPARATIVE EXAMPLE 1 COMPARATIVE EXAMPLE 2 Colored yellow yellow surface resistance value (0 / □) due to heat treatment ^ 1010 ^ 1010 ^ 1010 ^ 1010 Refraction Rate rH rH 1.85 Not measured transmittance (%) 88.7 1—Η LO oo 89.5 Not measured film thickness (nm) LO LO τ—Η Inch Example 1 Example 2 Comparative Example 1 Comparative Example 2 200413264 By implementing the above The comparison between the examples and the comparative examples shows that by changing the concentration of formazan appearance and ammonia concentration in the source gas in the CVD method, the composition of the thin film is clear. It is also known that the transparent thin film formed under the film forming conditions of the present invention has high visible light permeability, high insulation, and high protective layer function. Specifically, according to the comparative example, it is known from Example 1 that the ratio of ammonia to f㈣ in the body is higher.

率越低。再者可知，隨石夕含有率上升，薄膜之可見光1 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㈣法所能 利用程度之快速成膜速度4，藉由適當維持原料氣體中 石夕含有化合物濃度，並適t調整切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 易由透明基體上剝離之透明薄膜。The lower the rate. Furthermore, it can be seen that as the content rate of Shi Xi is increased, the visible light 1 ratio of the film is decreased and the refractive index is increased. Since the present invention has the structure as described above, the following effects can be exhibited. According to the method for forming a transparent thin film according to the present invention, a fast film-forming speed 4 that can be utilized by the on-line method can be achieved. By appropriately maintaining the concentration of the compound contained in the raw material gas, and adjusting the content of the compound and ammonia appropriately, Not only can maintain a high film formation speed ', but also can form a transparent film with high transparency and difficult to peel off from a transparent substrate.

,本發明藉由使用線上CVD法為成臈方法，可在短時間 内形成大面積、無針孔等缺陷之透明薄膜。a，因為在線 上CVD法中原料氣體熱分解反應所需之能量係由玻璃帶得 到’故可以削減具備透明薄膜之玻璃基板之總能量成本。 本發明之具備透明薄膜玻璃基板可充分滿足建物或車 輛用之要求特性’特別是因為不會發生銀之著色，適用於 作為顯示n用’特別適用於要求嚴格之電漿顯示器面板基 21 200413264 [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。By using the in-line CVD method as a hafnium method, the present invention can form a transparent film with a large area and no defects such as pinholes in a short time. a, because the energy required for the thermal decomposition reaction of the raw material gas in the online CVD method is obtained from a glass ribbon, the total energy cost of a glass substrate having a transparent film can be reduced. The transparent glass substrate provided by the present invention can fully meet the required characteristics of buildings or vehicles. 'Especially because silver coloration does not occur, it is suitable for display n'. It is particularly suitable for plasma display panel substrates with strict requirements 21 200413264 [ Brief Description of the Drawings] (I) Drawing Part FIG. 1 is a cross-sectional view of one embodiment of a transparent substrate with a transparent film according to the present invention. FIG. 2 is a schematic diagram of an apparatus used for the in-line CVD method. Fig. 3 is a cross-sectional view of one embodiment of a transparent substrate in which a transparent film and a functional film are laminated.

(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）(II) Symbols for components 1 glass substrate 2 transparent film 3 film (functional film)

10玻璃帶 11熔融爐 12浮式洛 13缓冷爐 1 5錫浴 16， 16a， 16b， 16c 塗覆器 17滾筒 2210 Glass ribbon 11 Melting furnace 12 Floating furnace 13 Slow cooling furnace 1 5 Tin bath 16, 16a, 16b, 16c Applicator 17 Drum 22

Claims (1)

200413264 拾、申請專利範圍： :目-種透明薄膜之形成方法，係以 ::相沉積法進行透明薄臈之形成，其成膜迷= 乂上，且該透明薄膜含有擇自碳（c)及氧（〇 氮（N)、氫（H)及矽（Si)。 至 >、一者、 2·如申請專利_帛丨項之相薄 '該原料氣體中含有切化合物成方法 兮斥^專利乾圍第1項之透明薄膜之形成方法 5亥原料氡體中含有含矽化合物及氨。 ί.如申請專利範圍第3項之透明薄膜之形成方法 違原料氣體中氨對切化合物之莫耳比為 ^如申請專利範圍第】項之透明薄膜之形成方法 该原料氣體含有甲矽烷（SiJJ4)。 =如申請專利範圍第i項之透明薄膜之形成方法 係將該原料氣體喷附於浮式浴内之玻璃帶表面。 如申請專利範圍第6項之透明薄膜之形成方法： 该玻璃帶表面温度為700〜830°C。 ^如申請專利範圍第i項之透明薄膜之形成方法，其 中’该玻璃帶係具“襲以下厚度或成形為4隨以下厚度 中 中 中 中 中 中 其 其 其 其 其 其 9·二種透明薄臈，係以中請專利範圍第}項之方法形 成，其氫原子含有率為4〜2〇原子％。 少 10.如申請專利範圍帛9項之透明薄膜，其厚度為 40nm以上且可見光穿透率為83%以上。 ， 23 200413264 明基體及 媒為申請 之透明基 …一％…土… 诉含有3 形成於該透明臬麯# A , & ^ ^ 專利… 表面上之透明薄膜，該透明薄 專利乾圍弟9項之透明薄臈。 專 以如申請專利範圍帛u項之具備透明 體，其中，該透明基體為玻璃板。 ’、 13 ·如申請專利範圍第π項之具備 ^ 體，係進一步含有於透明薄膜表面形 月薄膜之透明基 之機能性薄膜。 拾壹、囷式·· 如次頁。 24200413264 Scope of application and patent application: The method of forming a transparent thin film is to form a transparent thin film with a phase deposition method. The film forming fan is on the thin film, and the transparent film contains carbon (c). And oxygen (0 nitrogen (N), hydrogen (H), and silicon (Si). To >, one, 2 · as thin as the application for the patent _ 帛 丨 the phase is thin, the raw material gas contains cutting compounds into the method ^ Method for forming the transparent film of item 1 in the patent. The raw material carcass contains silicon-containing compounds and ammonia. Ί. The method of forming the transparent film of item 3 in the scope of the patent application violates the ammonia-cut compound in the raw material gas. The molar ratio is ^ as in the method of forming a transparent thin film according to the scope of the patent application] The raw material gas contains silane (SiJJ4). = If the method of forming a transparent thin film in the scope of patent application i is sprayed on the raw material gas The surface of the glass ribbon in the floating bath. For example, the method for forming a transparent film in the scope of patent application No. 6: The surface temperature of the glass ribbon is 700 ~ 830 ° C. ^ If the method for forming the transparent film in scope i of the patent application, Where 'The glass ribbon is attached' The thickness or shape is 4 according to the following thickness. Zhongzhongzhongzhongzhongzhong and other 9 · 2 kinds of transparent thin 臈, which are formed by the method of the scope of the patent application}. Its hydrogen atom content rate is 4 ~ 2. 〇atomic%. Less 10. If the transparent film of the 9th scope of the patent application, the thickness is more than 40nm and the visible light transmittance is more than 83%., 23 200413264 The clear substrate and the medium are the transparent substrate of the application ... one% ... soil … V. Contains 3 transparent patents formed on the transparent 臬 曲 # A, & ^ ^ patents ... The transparent film on the surface, the transparent thin patent is the transparent thin film of the 9th item of the patent. A transparent body, wherein the transparent substrate is a glass plate. ', 13 · If the π body of the scope of application for a patent has a ^ body, it is a functional film further comprising a transparent substrate with a moon-shaped film on the surface of the transparent film. Type ·· Like the next page.