A7 B7 438996 五、發明説明（1 ) 技街範圍 本發明係两於透明導電膜形成時所用作為濺射靶料的 有用的ΪΤΟ燒結體，Μ及由該燒結體製得之I TO透明導電膜 和該透明導電膜的形成方法〇 本發明之IT0燒结體具有高燒结髏密度，由該燒結體 可製得電粗係數小的透明導電膜，此種透明導電膜特別適 用於液晶潁示器，電致發光（ELECTROLUMINESCENCE)、電 鉻顯示器（ELECTHOCHROMICDISPLAY)。 背景技術 爲人所熟知之透明導電膜係將白金等金靥或氧化錕、 氧化銦李氧化物被覆於基板上而成薄膜者。其中主要作為 液晶顯示器等使用者係於氧化銦中添加氧化錫而成IT0 (Indium-nn-Oxideb其主要原因除ITQ具高透明性、低 電阻特性之外，尚具有耐蝕刻性、化學安定性、及良好的 基板附著性等。 透明導電膜之製成方法包含有：真空蒸鍍、離子植入 、濺射等物理蒸鍍法；Μ熱分解等化學反臁製成薄膜之化 學蒸鍍法；和噴鍍、浸漬等之塗敷法。其中以物理蒸鍍法 裂成之薄膜具高密度性和低電阻係數，而其中更Μ濺射法 爲主流。 Μ濺射法製成ΙΤ0膜時，大多以氧化組添加氧化錫而 成之ΪΤ0燒結體用作為朦射橒靶。 I TO燒結體通常俤Μ氧化纗添加氧化錫之粉末，或將 之預燒成粉末後再經冷整、澆鑄成型，之後再將該成型體 本纸浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ;---_------- 裝------訂------j 線 - - , (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 4 438996 經濟部中央標準局員工消費合作社印製 A7 ____B7_____五、發明説明（2 ) 置於大氣中Μ 1200Ϊ!以上溫度燒製而成。然而，ITO粉末 因燒結性不佳，故僅能製得密度約為4.9g/c*3 (M理論密 度為7 · Os/cii3時之相對密度70% )之燒结體。 另外，藉由原子價控制方法之半導體化機構來製成低 電阻值之ΙΤ0透明導電膜之技術有下述例子。 例子，待開昭59-163707係於IT0添加氧化釕、氧化鉛 、氧化銅，特開昭59-71205係於ΙΤ0添加氧化磷、特開昭 61-294703、特開昭63-78404則於氧化絪、ΙΤ0分別添加氟 化鋁，待開昭63-178414則於I T0添加氧化碲，特開昭64-10507係於I T0添加氧化矽，特開平1-283369係於ΙΤ0添加 氧化硒或氟化錫，特開平3-199373則於I TO添加1、Br據此 分別製成低電阻值之透明導電膜。 另一方面，利用邇原之半導醱化方法Μ製成低電阻係 數之透明導電膜之例子有例如美國專利第4399194號。於 該例子中係於氧化铟中添加40〜60wt%之氧化結。據此可 製得電阻係數為4.4X 10_4Ωηη，光透過率為80%之特性。 以低密度之燒結體作為濺射檫靶時，1片相同尺寸之 檫靶所能使用之ΙΤ0之量變為較少，檫靶壽命變短，橒靶 之交換頻度變多，則濺射裝置之蓮轉率變低。另外，當燒 結密度越低時，截射所產生於檷靶表面之黑化現象越顯著 ，膜之形成速度變得越慢，因而導致透明導電膜之罨阻係 數變高。因此，若欲消除表面之黑化物，則實質上之標靶 之使用置變得更少*導致濺射裝置之蓮轉率變得更低。 因此，為了使每一片檫靶之I TO可使用置能增加，同 ：---_------I 裝------訂-----.丨線 - (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 5 438996 A7 B7 五、發明説明（3 ) 時提高濺射裝置之運轉率，並達到操作之穩定性，則蒲要 提高i TO燒結體榡靶之密度*具體而言至少需大於相對密 度70妬。 焦了達成此棰要求，故於習知成型燒成裂程中，係藉 由熱壓、HIP *並控制燒成環境之方法來實現高密度化， 最高可得相對密度為98%者（特開平3-207858}，然而，其 設備和生產成本均相對地提高，此為問題點。 此外，亦有人提案過Μ控制原料ΙΤ0粉之粉粒來實現 燒結醱之高密度化（特開昭62-12009、特開平3-218924等） ，然而，因原料之調製棰困難，成本亦高*致未達實用階 段。 解決上述成本過高且能實現燒結髅之高密度化之方法 亦可利用添加燒結助剤之方法來實現。 特開昭61-136954(特公平卜21109)傈Μ添加矽Κ及/ 或Ge之氧化物作爲燒結助劑而製成最大相對密度為90%之 燒結體。然而，經由本案發明人試驗得知，膜質特性最佳 者之組成為於ΙΤ0添加0.5wt%之Ge02，成膜之電阻係數為 2.0X ΙΟ^Ω cb，不遇燒結體密度僅停留於79%。若添加 15wt%之GeOa，則燒結鱧密度可達90%，然而成膜之雷阻 係數則為2.9X10-*Qcn *明顯惡化。 另外，於待開昭59-198602掲示有於ΙΤ0添加AU W、A7 B7 438996 V. Description of the invention (1) Technical scope The present invention relates to a useful ITO sintered body used as a sputtering target when a transparent conductive film is formed. Method for forming the transparent conductive film. The IT0 sintered body of the present invention has a high sintered cross-section density, and a transparent conductive film with a small coefficient of electrical coarseness can be produced from the sintered body. This transparent conductive film is particularly suitable for a liquid crystal display. ELECTROLUMINESCENCE, ELECTROCHROMIC DISPLAY. BACKGROUND ART A well-known transparent conductive film is a thin film formed by coating gold substrates such as platinum, hafnium oxide, and indium oxide plum oxide on a substrate. Among them, IT0 (Indium-nn-Oxideb) is mainly used as a liquid crystal display by adding tin oxide to indium oxide. In addition to ITQ's high transparency and low resistance, it also has etching resistance and chemical stability. , And good substrate adhesion, etc. The methods for making transparent conductive films include: physical vapor deposition methods such as vacuum evaporation, ion implantation, sputtering, etc .; chemical vapor deposition methods such as M thermal decomposition to form thin films And coating methods such as thermal spraying, dipping, etc. Among which the thin film cracked by physical evaporation method has high density and low resistivity, of which the M sputtering method is the mainstream. When the M sputtering method is used to make ITO films Most of the sintered ITO sintered bodies obtained by adding tin oxide to the oxidation group are used as haze targets. I TO sintered bodies are usually oxidized with tin oxide powder, or pre-fired into powder, and then cold-formed and cast. After molding, the paper size of the molded body is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm); ----------------------------------- --j line--, (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Quasi Bureau 4 438996 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 ____B7_____ V. Description of the invention (2) It is fired in the air at a temperature above 1200Ϊ! However, ITO powder is sinterable Poor, so only sintered bodies with a density of about 4.9 g / c * 3 (the relative density at a theoretical density of 7 · Os / cii3 of 70%) can be obtained. In addition, semiconductorization by atomic value control methods The technology of making ITO transparent conductive film with low resistance by the mechanism is as follows. For example, to be developed in 59-163707 is to add ruthenium oxide, lead oxide and copper oxide to IT0, and JP 59-71205 is added to ITO 0 Phosphorous oxide, JP-A 61-294703, and JP-A 63-78404 are added with aluminum fluoride to ytterbium oxide and ITO, respectively. To Kai-Sho 63-178414, tellurium oxide is added to I T0. JP-A 64-10507 is based on I T0 is added with silicon oxide, JP-A Hei 1-283369 is based on ITO and selenium oxide or tin fluoride is added, and JP-A 3-199373 is added with I TO and 1, Br, which are respectively made into transparent conductive films with low resistance. On the one hand, the semiconductive method of EBARA is used to make a transparent conductive film with low resistivity. An example of the film is, for example, U.S. Patent No. 4,399,194. In this example, an oxidation junction of 40 to 60% by weight is added to indium oxide. Based on this, characteristics such as a resistivity of 4.4X 10_4Ωηη and a light transmittance of 80% can be obtained. When a low-density sintered body is used as a sputtering target, the amount of ITO that can be used for one target of the same size becomes smaller, the life of the target becomes shorter, and the exchange frequency of the target becomes larger. Lotus conversion rate becomes low. In addition, as the sintering density is lower, the blackening phenomenon produced by the interception on the surface of the target becomes more pronounced, and the film formation rate becomes slower, resulting in a higher resistance coefficient of the transparent conductive film. Therefore, if the black matter on the surface is to be eliminated, the actual use of the target becomes less *, resulting in a lower lotus conversion rate of the sputtering device. Therefore, in order to increase the useable energy of I TO for each target, the same as: ---_------ I equipment ------ order -----. 丨 line- (please first Read the notes on the back and fill in this page again.) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 5 438996 A7 B7 V. Description of the invention (3) Increase the operating rate of the sputtering device and achieve The stability of the operation is to increase the density of the i TO sintered compact target. Specifically, at least the relative density should be greater than 70. In order to achieve this requirement, in the conventional molding and firing cracking process, high density is achieved by hot pressing, HIP * and controlling the firing environment. The highest available relative density is 98% (special Kaiping 3-207858}, however, its equipment and production costs are relatively high, which is a problem. In addition, some people have also proposed that M control the powder of the raw material ITO powder to achieve a high density of sintering tin (Japanese Patent Application No. 62 -12009, Japanese Unexamined Patent Publication No. 3-218924, etc.) However, due to the difficulty in the preparation of raw materials, the cost is also high * and has not reached the practical stage. The method to solve the above-mentioned high cost and achieve high density of the sintered skeleton can also be added by using The method of sintering assists sintering. Japanese Patent Application Laid-Open No. Sho 61-136954 (Japanese Patent No. 21109) 傈 M adds silicon K and / or Ge oxides as sintering aids to produce a sintered body having a maximum relative density of 90%. However, According to the experiments conducted by the inventors of this case, the composition with the best film quality characteristics is the addition of 0.5 wt% Ge02 to ITO, and the film formation resistivity is 2.0X ΙΟ ^ Ω cb. The density of the sintered body only stays at 79%. Adding 15wt% GeOa, the density of sintered rhenium can reach 90% However, the film formation lightning resistance coefficient is 2.9X10- * Qcn *. It is significantly deteriorated. In addition, it is shown in the to-be-opened 59-198602 that AU W,
Th、Mo等元素而成之透明導電膜*其成膜之電阻係數亦高 速1.2xi0_a〜2_42父1〇-3£2^»，而經本案發明人試驗結 果，該燒結鼸之密度（相對於理論密度之相對密度}未達70 本紙張尺度通用中國國家標準（CNS ) Μ規格（210Χ297公蝥） ；----^------裝------訂-------J 線 -^ - - (請先閱讀背面之注意事項再填寫本頁) 經濟部中央檁率局員Η消費合作社%製 6 ^ i nt 3 0 1^ *商被糸"激锄—卻薄他薇Mi/ 1¾ 4、s_潘sweRZ^C腔ί k掛咳鄉讲辄澉3^薇飯樹^13 ss^u^®-s-^i-8ss^stai^rs@i-®-^^»u o 0S、洧 i s w- I s ® e V ,£ s I ® s w> i @ $ , s ^ β sn ^ ® I s。—® sfi 爾 i^lll^c 球 2000AS8iss — Λ、悉0酒iM鸾雜、ss谢8茺雜&雖辛链热蜮@8^^ I 8^、路i菽葫？嚇。^ s wn S ^ I kn s s > lift > WSSR®3$S 麻丨 8S* si 规 ITasi 雕 wesk® ——朋 3^E*^ss —— sm 谢热 W8SSI 細 1 N s s $ 獎 2 X 10-*£20_ 一磡面參薄 ^ !p i 5 Λ5 次飯播*雜®、ii — s®、趙硌诹谢额3ITO I S β爾廊ο 钟赌SM1參48¾ 1 S Η Η o s ^ ® * 批吵地Ms叶oH swibo3M^am^3_i^ * 苕骑 一 1¾ 却 MsioN — wiao3BI^ ^r Ji 1¾ ^ Λυ / Mu / E y ^ w s ί 0.0 ^ o e , o >o ^ i- o Sin 0-00 ^ · o 1 2 -0 8 3^¾ (_雕舳傷ii>W4g㈣) 4389 9 6 Α7 Β7 五、發明説明（5 ) D 12.0 0.001 Ε 0.001 0.001 經濟部中央擦準扃負工消費合作社印敢 本發明之另一目的係提供具有上述51〇2和&12〇=>組成 之ITO透明導電膜。 本發明之再另一目的係提供一捶ιτο透明導電膜之形 成方法，其係Μ具上述組成之I το燒結髏爲檫靶，並於真 空槽内將惰性氣釀單獨或是將惰性氣體與選自氧氣或氣氣 中之一種所合成之混合氣體，於全歷lxl〇'3torr〜5X 10_3torr下導入Μ進行濺射者。 實施本發明之最佳形態 如第1圖所示，其中 線 Α-Β 表示 Bi2〇3 * 9.0 wt·% 線 B-C 表示（Bi2〇3 + Si〇2) = 18·0 wt.* 線 C-D 表示 Si〇2 = 12.0 線 D-E 表示 Bi2〇3 = 0-001 wt·% 線 ENA表示 Si〇2 = 0.001 wt.% 線 F-G 表示 Bi2〇3 = 6.0 wt.% 線 G-H 表示 SiC^ » 4.0 wt.% 線H-I表示 Bi_2〇3 ^ 0*02 wt·% 線；L-F 表示 Si〇2 = 0,001 wtj 線 J-K 表示 Βΐ·2〇3 =： 6.0 wt.% 線 K-L 表示（5Bi2〇3 + 26Si〇2) = S6.0 wt.ii .線 L-M 表示 Bi2〇3 = 〇..8〇 wt-% 線 M-J 表示 0Bi2〇；3 — 52〇Si〇2> = 2,00 wt.% 於ITO燒結醱及ITO透明導電膜中，相對於氧化銦，錫 俤Μ氧化物之混合物或固溶髏之形態存在。而本發明之燒 結體以及導電膜中》BiK及Si應該亦分別Η氧化物混合、 度適用中國國家梂孪（CNS )六4規格（2丨0X 297公辏) -8 _ ：------^---厂,裝------訂------银 (請先閲讀背面之注意事項再填'寫本頁) 4 3 8 9 9 6 A7 B7 五、發明説明（6 ) 或複合氧化物、或固溶醻、或是上逑之混合狀態存在。因 該狀態難以正確認定，故本發明中爲了方便起見，分別以 其氧化物之組成來表示。 本發明之燒結體以及透明導電膜，其特戡係含有相當 於如第1圖所示5丨〇3-8“〇3二成分条圈中表示上述組成份 之點A、B、C、DM及E所包圍直域內之Si〇2以及BU〇3 之組成份者（即 0.001 wt.% 芸 Bi3〇3 g 9.0 wtj、ΪΚ001 wtj 盔 Si〇2 蝱 12.0 wt,3£、（Bi2〇3 + Si〇3)迄 18.0 wt·%)。滿足M要件之透明導電膜，其具有之電阻係數約 為2.0Χ 10~4Ω cB Μ下。燒結體以及透明導鼋膜係分別含 有相當於第1圖所示Si〇s-BU〇3二成份糸中表示下述組成 份之黏F、G、Η，Μ及I所包睡之區域（邸0.02 wt·% 芸 BisiCh 彡 6.0 wt·%、O.OOlwt.X g SiOst 忘 4.0 wt.X )，更好則為表示下逑组成份之點J、 K、 LM及M所包 圍之區域（即 0.80 wt.% 运 Bi2Q3 忘 6.0 wt.3：、<5Bia〇3 + 26Si〇3)爸 56.0wt.；ii、2.00 wt.X 容（9Bi2〇3 -520Si〇a>内之Si〇2以及BU〇3之组成份。 -----_------、〆裝------訂------银 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 黏_ sin* (vt.9^ ) BiaOsftft%) F 0.001 6.0 G 4.0 6.0 Η 4.0 0.02 I 0.001 0.02 J 0.1 6.0 Κ 1.0 6.0 L 2.0 0.8 Μ 0.01 0.8 本紙張尺度適用令國國家標準（CN_S ) A4現格（210X 297公釐） 438"6 $ 經濟部中央標準局員工消費合作社印製 五、發明説明（7) Si〇2及Bis〇3之組成份相當於點F、G、及I所包圍 之匾域>和點J、 K、 LM及Μ所包圍之匾域時，其透明 導電膜之霄阻係數分別為1.5Χ caM下和l.OX 1(Τ* Ω cbM 下。 本發明之ITO燒結釅K及透明導電膜最好是含有0.05 〜25wt%之氧化篇。若氧化錫的Μ小於0.05wt%，或是大 於25wt^，則其所製成之透明導電膜之電阻係數將變大。 亦卽，本發明之燒結體以及透明導電膜最好是含有上述範 圍之氧化錫之量，且含有之Bia〇3M及Si〇s之組成份最好 在上逑組成份範圍内。 關於燒結體之製迪，一般均Μ絪之氧化物作為氧化鑛 之原始原料，或者是亦可使用銦金屬、氫氧化物、氟化物 、硫酸鹽、硝酸鹽等。不過，若使用氧化物以外之原料時 餺在氧化環境下藉由預嫌或燒結使形成氧化物条燒結體。 氧化錫之原始原料一般均為氧化物，或是亦可使用錫金屬 、氬氧化物、氟化物、碇化物、礙睃鹽、硝酸鹽等。錫和 銦最終均成為氧化物。 氧化鉍之原始原料一般均為氧化物，或是亦可使用鉍 金靥、氫氧化物、碘化物、硫化物、硫酸鹽、硝酸邇等。 不過，若使用鉍之氧化物Μ外之原料，於燒製時在到逹燒 結開始之950Ό之前變成氧化物即可。氧化緒之原始原料 一般均為氧化物，或亦可使用矽單體、氣化物、氦化物、 磺化物、硫化物等。矽和Bi亦同樣地在燒結時之950Τ：之 前變成氧化物卽可。 (請先閱讀背面之注意事項再填寫本頁) 裝. 訂 ''猓 本紙乐尺度適用中國國家標準（CMS ) Α4規格（2〖0Χ 297公釐） 10 鯉濟部中央榡準局員工消費合作衽印製 4 3 8 9 9 6 A7 B7 ' ' — I ---- --- ------------------------------- .. I、發明説明（8 ) 将該4捶元素之原料化合物同時混合亦可。或是事先 将2種元素Μ上之化合物混合預燒，之後再將預燒粉末和 其他元素之化合物混合亦可。 原料之混合可使用乳缽混合、球磨機混合。原料粉末 較好爲2μβΜ下。將混合之粉末在400〜1500t!下進行預燒 0 将聚乙烯醇<PVA>、聚乙烯醇縮丁庭（PVB)等助黏劑添 加於裂得之粉末*並K噴蓀乾燥機製成1〜5〇μΒ之粉粒， 再於500〜8000kg/cn2左右之壓力下成型。亦可於添加PVA 等助鈷爾後拌成漿料，再澆鏵成型，再將成型體乾燥，脫 脂。 將所製成之成型體於1200〜160〇υ、於大氣中進行燒 結使成高密度化。當然亦可經由熱歷、HIP、激氣調整進 行燒製。 一般而言，形成透明導電膜之方法除濺射法、電子束 沈稹法之外，亦可採用離子植入法、化學沈稹法、塗覆法 等。可逋各成膜之形成原料而選擇適當之方法。濺射法以 及電子束沈積法之沈積原料（target)可使用銦和添加元素 之氧化物之燒結體或其合金。 當使用本發明之ΙΤ0燒結體Μ濺射法形成薄瞑時*將 檷靶用之燒結體和成膜用基板安置後，抽成IX 10—s t〇rr 以下之真空後，若是燒結體之情況，則將惰性氣體，或由 惰性氣體和〇3氣醱以及Ha氣體混合而成之氣醴導入Μ形成 薄膜。 本紙張尺度適用中國國家標準（CNS ) A4現格（210X297公釐） 11 ^---!----^---裝------訂------線 t - (請先閲讀背面之注意事項再填寫本頁) A7 B7 9 4389 9 6 五、發明説明（ (請先閣讀背面之注意事項再填寫本頁) 惰性氣鱧可菡擇使用Ar、He、Ne、Kr、Xe、Rn或1中 之任一種*不過若從功能和經濟面因素來考置則以Ar和N* 較佳。特別是Ar為最佳。其中於濺射或沈積過程中會產 生氮化合物故較不好〇 使用本發明之燒結體作爲棰靶進行濺射時，於真空槽 内所導入之惰性氣體或是惰性氣體和氧氣Μ及/或氳氣所 混合而成之氣體係於全壓爲IX 10—3torr〜5Χ 10—Uorr下 被導入。 於此時，若濺射氣體中氧氣分壓變高則透過率變高。 電阻係數降低。但是若太高則電阻係數反而會增加。若不 添加氧氣而只Μ氬等惰性氣體作為濺射氣體，則氧化物中 之氧原子亦會扮演混合雔射氣體中之氧氣之功能，因此電 阻俤數等膜質特性亦不致於惡化。然而，某一比例Μ上之 氧氣存在會較有利。因此，於本發明之導電膜形成方法中 *較好是在濺射混合氣體中含有2ρρβ〜20%比率之氧氣。 經濟部中央標準局員工消費合作社印裝 雖然不導入氳氣亦能實現低電阻係數。但導入氳氣則 可在不損及成膜之光透過率之情況下實現低電阻係數°然 而，若氬氣之分壓大於lx 10—3torr則光透過率將降低。 因此*本發明之導電膜形成方法中較好是於濺射混合氣體 中含有2ppb〜20%比率之氫氣。 若濺射氣體之全壓不及ixi〇_3t〇rr則無法產生穩定 的電漿，另外，若大於5X l〇-storr之高壓則膜質之電阻 係數将惡化。 又，基板溫度在150〜50〇υ，棰靶之投入電力為0.5 12 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇X：297公釐） ㈣缽㈣麵isA transparent conductive film made of elements such as Th, Mo, etc. * The film formation resistivity is also high-speed 1.2xi0_a ~ 2_42 Father 1〇-3 £ 2 ^ », and according to the test results of the inventor of this case, the density of the sintered rhenium (relative to Relative Density of Theoretical Density} Less than 70 paper sizes Common Chinese National Standard (CNS) M specifications (210 × 297 cm); ---- ^ ------ installation ------ order ---- --- J line-^--(Please read the notes on the back before filling out this page) Member of the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives% 6 ^ i nt 3 0 1 ^ * 商 被 糸 " 激 锄 — But Bo Tawei Mi / 1¾ 4, s_ 潘 sweRZ ^ C cavity ίkhangke township talk 辄 澉 3 ^ 薇 饭 树 ^ 13 ss ^ u ^ ®-s- ^ i-8ss ^ stai ^ rs @ i- ®-^^ »uo 0S, 洧 is w- I s ® e V, £ s I ® s w > i @ $, s ^ β sn ^ ® I s. —® sfi er i ^ lll ^ c ball 2000AS8iss — Λ, 00 wine iM 鸾 鸾, sss8 茺 茺 & Although the chain is hot 蜮 @ 8 ^^ I 8 ^, the road i 菽 hu? Scary. ^ S wn S ^ I kn ss > lift > WSSR ®3 $ S Hemp 丨 8S * si ITasi Carved wesk® ——3 3E * ^ ss —— sm Xiere W8SSI Fine 1 N ss $ Prize 2 X 10- * £ 20_ One face is thin ^! Pi 5 Λ5 meals * Miscellaneous®, ii s®, Zhao Xie, Xie 3ITO IS β Erlang ο Zhong gambling SM1 ginseng 48¾ 1 S Η Η os ^ ® * Noisy ground Ms Ye o swibo3M ^ am ^ 3_i ^ * 苕 骑 一 1¾ but MsioN — wiao3BI ^ ^ r Ji 1 ¾ Λυ / Mu / E y ^ ws ί 0.0 ^ oe, o > o ^ i- o Sin 0-00 ^ · o 1 2 -0 8 3 ^ ¾ (_ 雕 舳 伤 ii > W4g㈣) 4389 9 6 Α7 Β7 V. Description of the invention (5) D 12.0 0.001 Ε 0.001 0.001 The central government of the Ministry of Economic Affairs of the People's Republic of China should cooperate with the Consumers' Cooperatives. Another object of the present invention is to provide a combination of ITO transparent conductive film. Another object of the present invention is to provide a method for forming a transparent conductive film, which is a target of I το sintered skeleton having the above composition, and inert gas alone or in a vacuum tank. It is a mixed gas synthesized by an inert gas and one selected from the group consisting of oxygen or gas, and is sputtered under the full calendar 1xl0'3torr ~ 5X 10_3torr. The best mode for carrying out the present invention is shown in Fig. 1, where line A-B represents Bi2 03 * 9.0 wt ·% line BC represents (Bi2〇3 + Si〇2) = 18.0 wt. * Line CD represents Si〇2 = 12.0 line DE represents Bi203 = 0-001 wt.% Line ENA represents Si〇2 = 0.001 wt.% Line FG represents Bi203 = 6.0 wt.% Line GH represents SiC ^ »4.0 wt.% Line HI represents Bi_2〇3 ^ 0 * 02 wt ·% line; LF represents Si〇2 = 0,001 wtj Line JK represents Bΐ · 2〇3 =: 6.0 wt.% Line KL represents (5Bi2〇3 + 26Si〇2) = S6.0 wt.ii. Line LM means Bi2〇3 = 〇.8〇wt-% Line MJ means 0Bi2〇; 3-52〇Si〇2> = 2,00 wt.% In ITO sintering and ITO transparent In the conductive film, in the form of a mixture of tin 俤 oxides or a solid solution with respect to indium oxide. In the sintered body and the conductive film of the present invention, "BiK and Si should also be mixed with oxide, respectively, and the degree is applicable to China National Twin (CNS) Sixty Four Specification (2 丨 0X 297 cm) -8 _ ---- ---- ---- ---- -^ --- factory, install ------ order ------ silver (please read the precautions on the back before filling 'write this page) 4 3 8 9 9 6 A7 B7 V. Description of the invention (6) Either a composite oxide, a solid solution osmium, or a mixed state of osmium. Since this state is difficult to determine correctly, in the present invention, for the sake of convenience, the oxide composition is expressed separately. The sintered body and the transparent conductive film of the present invention specifically contain the points A, B, C, and DM corresponding to the above-mentioned components in the two-component circle shown in FIG. 5 as shown in FIG. And components of Si〇2 and BU〇3 in the direct range surrounded by E (that is, 0.001 wt.% Yun Bi3 03 g 9.0 wtj, ΪΚ001 wtj helmet Si〇2 蝱 12.0 wt, 3 £, (Bi2 03 + Si〇3) up to 18.0 wt ·%). The transparent conductive film that meets the M requirements has a resistivity of about 2.0 × 10 ~ 4Ω cB Μ. The sintered body and the transparent conductive film respectively contain the equivalent of the first The two components SiOs-BU03 shown in the figure indicate the areas covered by the following components: F, G, Η, M, and I (Di 0.02 wt ·%, BisiCh 彡 6.0 wt ·%, O .OOlwt.X g SiOst forget 4.0 wt.X), more preferably the area surrounded by points J, K, LM, and M representing the lower component (ie 0.80 wt.% Yun Bi2Q3 forget 6.0 wt.3 :, < 5Bia〇3 + 26Si〇3) Da 56.0wt .; ii, 2.00 wt.X capacity (9Bi2〇3-520Si〇a > the composition of Si〇2 and BU〇3. -----_ ------, Outfit ------ Order ------ Silver (Please read the notes on the back before filling Page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs_ sin * (vt.9 ^) BiaOsftft%) F 0.001 6.0 G 4.0 6.0 Η 4.0 0.02 I 0.001 0.02 J 0.1 6.0 Κ 1.0 6.0 L 2.0 0.8 Μ 0.01 0.8 copies Paper size applicable national standard (CN_S) A4 now (210X 297 mm) 438 " 6 $ Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) Components of Si〇2 and Bis〇3 Corresponding to the plaque fields surrounded by points F, G, and I> and the plaque fields surrounded by points J, K, LM, and M, the resistance coefficients of the transparent conductive film are 1.5 × caM and 1.OX, respectively. 1 (Τ * Ω cbM. It is preferable that the ITO sintered 酽 K and the transparent conductive film of the present invention contain 0.05 to 25% by weight of oxide. If the M of tin oxide is less than 0.05% by weight, or more than 25% by weight, The resistivity of the produced transparent conductive film will become larger. Also, it is preferable that the sintered body and the transparent conductive film of the present invention contain the amount of tin oxide in the above range, and the components of Bia〇3M and SiOs. Preferably, it is within the range of the upper part. Regarding the production of sintered bodies, oxides of M 絪 are generally used as raw materials for oxidized ore, or indium metal, hydroxide, fluoride, sulfate, nitrate, etc. can also be used. However, when raw materials other than oxides are used, sintered bodies of oxide bars are formed by anticipation or sintering in an oxidizing environment. The raw materials of tin oxide are generally oxides, or tin metals, argon oxides, fluorides, sulfides, thallium salts, nitrates, etc. can also be used. Both tin and indium eventually become oxides. The raw materials of bismuth oxide are generally oxides, or bismuth gold rhenium, hydroxide, iodide, sulfide, sulfate, rhenium nitrate, etc. can also be used. However, if a raw material other than the oxide M of bismuth is used, it can be converted to an oxide before firing at 950 ° C during the firing. The original raw materials of the oxide are generally oxides, or silicon monomers, gaseous compounds, helium compounds, sulfide compounds, and sulfide compounds can also be used. Silicon and Bi similarly became oxides before 950T: during sintering. (Please read the notes on the back before filling in this page.) Binding. Ordering 猓 The paper scale is applicable to the Chinese National Standard (CMS) Α4 specification (2 〖0 × 297 mm)衽 Print 4 3 8 9 9 6 A7 B7 '' — I ---- --- ---------------------------- --- .. I. Description of the invention (8) It is also possible to mix the raw material compounds of the element 4 at the same time. Alternatively, the compounds on the two elements M may be mixed and pre-fired beforehand, and then the pre-fired powder and other elements may be mixed. The raw materials can be mixed using a mortar mixing or a ball mill. The raw material powder is preferably at 2 µM. Premix the mixed powder at 400 ~ 1500t! 0 Add polyvinyl alcohol < PVA >, polyvinyl butyrate (PVB) and other adhesion promoters to the cracked powder * and spray drying mechanism It is formed into 1 ~ 50μB powder, and then formed under the pressure of about 500 ~ 8000kg / cn2. It is also possible to add PVA and other cobalt-assisted cobalt and then mix to form a slurry, which is then poured into a mold, and then the molded body is dried and degreased. The formed article is sintered in the air at 1200 to 160 ° to increase the density. Of course, it can also be adjusted by thermal calendar, HIP, and agitation. Generally speaking, in addition to the sputtering method and the electron beam deposition method, a method for forming a transparent conductive film can also be an ion implantation method, a chemical deposition method, a coating method, or the like. An appropriate method can be selected for each film-forming raw material. As a sputtering target and an electron beam deposition method, a sintered body of an indium and an oxide of an additive element or an alloy thereof can be used. When the thin sintered body is formed using the ITO sintered body M sputtering method of the present invention * After the sintered body for the target and the substrate for film formation are set, a vacuum of IX 10-st0rr or less is drawn, and in the case of a sintered body Then, an inert gas, or a gaseous gas formed by mixing an inert gas with a gas of 03 and a gas of Ha, is introduced into M to form a thin film. This paper size applies Chinese National Standard (CNS) A4 now (210X297 mm) 11 ^ ---! ---- ^ --- Packing ------ Order ------ Line t-( Please read the precautions on the back before filling this page) A7 B7 9 4389 9 6 V. Description of the invention ((Please read the precautions on the back before filling out this page) Inert gas can choose to use Ar, He, Ne, Any one of Kr, Xe, Rn, or 1 *, but Ar and N * are preferred when considering functional and economic factors. Ar is particularly preferred. Nitrogen is generated during sputtering or deposition Compounds are not good. When using the sintered body of the present invention as a radon target for sputtering, an inert gas introduced into a vacuum tank or a gas system made of a mixture of an inert gas and oxygen M and / or radon gas is used in the entire system. The pressure is introduced under IX 10-3torr ~ 5 × 10-Uorr. At this time, if the partial pressure of oxygen in the sputtering gas becomes higher, the transmittance becomes higher. The resistivity decreases. However, if it is too high, the resistivity will increase instead. If no inert gas such as argon is used as the sputtering gas without adding oxygen, the oxygen atoms in the oxide will also act as the oxygen in the mixed projection gas. Energy, so the film quality characteristics such as resistance number will not be deteriorated. However, the presence of oxygen at a certain ratio M will be more advantageous. Therefore, in the conductive film forming method of the present invention *, it is preferable to include in the sputtering mixed gas 2ρρβ ~ 20% oxygen. Although printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, low resistivity can be achieved without the introduction of radon. However, the introduction of radon can be achieved without compromising the light transmittance of the film. Low resistivity ° However, if the partial pressure of argon gas is greater than lx 10-3torr, the light transmittance will decrease. Therefore, in the method for forming a conductive film of the present invention, it is preferable to contain a ratio of 2ppb to 20% in the sputtering mixed gas. Hydrogen. If the total pressure of the sputtering gas is less than ixi0_3t〇rr, a stable plasma cannot be generated. In addition, if the pressure is higher than 5X l0-storr, the resistivity of the film will be deteriorated. Also, the substrate temperature is 150 ~ 50〇υ, the target's input power is 0.5 12 This paper size applies the Chinese National Standard (CNS) A4 specification (21〇X: 297 mm)
> 3 m ΰ Θ ① Α7 ΒΤ (衅婶㈣4雖趣) A7 B7 經濟部中央標準局員工消費合作社印製 438996 五、發明説明（u ) 法可使用三甲氧絪、四異丙氧鐲、四乙氧烷、三異丙氧秘 等作為原料。 亦可利用塗S法（雖較濺射法為差）來形成透明導電膜 :亦卽，將碕酸铟、氯化錫、TEOS(四乙氧烷）、硝酸鉍之 乙酰丙詷<2,4-< >夕 才 >)溶液之丙酮稀釋掖等，藉 由心軸塗覆，浸潰塗覆、印刷法等予以塗覆並進行熱分解 Μ袈得ITO膜。此時亦可於塗覆液中添加觸變劑、肋粘劑 此外，若適當地遴擇原料再經凝膠法、水溶液熱分解 法等塗覆亦可製成膜〇 成膜基板可採用玻璃、塑膠薄片或薄膜，或是上面施 加有保護膜或功能性膜者。 因氧化箱中僅添加有氧化錫之ΙΤΟ於燒結時之蒸氣整 較高，故採用蒸發和凝縮之燒結機構，然因收縮較困難* 故難Μ實現燒結體之高密度化。然而令人驚奇的是，若添 加Bi2〇3等燒结助剤則於大約830Τ：時彤成液相，該掖相會 阻止ITO之蒸發，故蒸發和凝縮之燒結將被抑制，藉由下 述液相之燒結機稱可改善燒結情況。亦即，液相燎結係因 篏相之存在使物質移動，伴隨著收縮將可實現燒結體之高 密度化。 但是，若不添加Si〇2而只添Bi2〇，則高密度之改善效 果有限。邸使添加16wt%之BU〇3相對密度亦僅逹79¾。 而依本發明上述Si〇2-Bi2〇3組成分則可加速液相燒结，實 現高密度化，形成良好之透明導電膜。 本紙張尺度適用中國國家標準i CNS ) A4規格（2丨OXM7公釐） I---------------IT------ ----------------- ΐ I 、一 - ; (請先閱讀背面之注意事項再填寫本頁) ， 14 4 389 9 6 A7 B7 五、發明説明（12 ) 經濟部中央標準局員工消費合作社印製 經由後述實施例可印證，添加上述指定之Si〇2-Bi2〇3 組成分於1T0則可製得柑對密度大於90%之高密度燒結體 。再者》Μ此燒结體以棟靶並藉濺射法等則可製得電阻係 數棰低、可視光透遇率大、產業上極有利用價值的IΤ0導 霣膜。 上述指定之Si02-Bi2〇3之組成分係臨界狀態，例如， 和不添加BU〇3之倩況（fcb較例10〜13:燒結髖柑對密度72 〜88、導電膜電阻係數2.0〜2.3xi0_*£tca>比較，含有 一定置Bi2〇3之情況（實施例21〜24 :燒结醱柑對密度95〜 93、導電膜電阻係數1.2〜1.3)，其燒結鶄密度較髙，導 電膜電阻係數極低。 接著以實施例和比較例具髅說明本發明之燒結體以及 透明導電膜和該膜的形成方法。 實施例1〜47、比較例1〜23 將900g之氧化銦（同和化學製氧化絪N、純度99.99% ，平均粒度<15(1=0.93μιι〇和100g之氧化錫 <新日本金靥製 、純度99.9%、粒度《3!|1]=0.72|^)，以容量4.8升之球磨 機經24小時混合時，再於大氣中，1450=條件下進行15小 時預燒，據Μ製得ΙΤ0粉末。再將氧化鉍（之津和化學藥品 製、纯度99.9%、粒度dSD=0,78Kii〇和氧化矽（和光純裂 藥*純度99.9999%，粒度dsa = 1. 1μΒ)Μ表1所示之比率 混合於該ΙΤ0粉末，表1〜表1中氧化鉍和氧化矽之混合 董係Μ重量％表示，其餘部分則為ΙΤ0。混合係Μ球磨機 進行。於各該混合物末中加入0.05wt%之PVA溶液據Μ製 1----^------「裝-- • · 一 - (請先聞讀背面之注意事項再填寫本頁) 訂 本紙張尺度適用中國國家橾準（CNS〉Α4規格（210X 297公釐） 15 A7 B7 438996 五、發明説明（13 ) 成固態濃度為20wt%之漿料，再以噴蓀烘乾機對該漿料進 行噴琢烘乾據Μ製成平均粒徑2〇μ·之顆粒。 將該顆粒於Iton/C»3下以一軸加歴使之成型，據此可 得直徑9〇B!E<fr、厚3-5B*之鬮盤狀成型體。 將該圓盤狀成塱體置於大氣中並在1450*0溫度下進行 10小時燒製。該燒結體之組成分（化學分析）以及相對密度 如表1〜3所示。 使用各該燒結髏作爲榡靶，並置於直滾磁控式濺射裝 置内，油成IX 10-8torr之真空後，Μ分壓真空針一遴監 控，一邊將氫氣於3X 10”t〇rr下，將氧氣於3X 10_etorr 下導入，之後，將氬氣於全壓達5xi(T3torr之前予Μ導 入。將玻璃基板（尺寸76X 26X 於300¾下加熱，在投 入電力100W、基板間距離65mB之條件下製成透明導電膜。 以任一實施例之棲靶反複進行濺射*結果棟靶之黑化 現象極淡，濺射速率為10A/sec幾乎沒有效率。經由ΕΡΜΑ 確認得知所製成之透明導電膜之組成分大致和棟靶之組成 分相同。該製得之透明導電膜之厚度、可見光之平均透過 率Μ及電阻係數如表1〜3所示。 ---^------i:·裝------訂-----線 . - > .. (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標隼（CNS ) A4規格（210 X 297公釐） -1 ^ - 16 438996 A7 B7 五、發明説明（14 ) 經濟部中央標準局員工消費合作社印製 〔表1〕 實施例No 混合比(wt%) 燒結體組成分<wt%> 燒結醱 相對密度 (96) 成膜特性 Si〇z Bi 2〇3 SiOz BiaOa 可見光平均 透遇率㈣ 電阻係數 (X 10'4Ωοι) 實施例1 0.001 0.02 0.001 0.011 90 90 1.40 實施例2 0.05 0.02 0.051 0.013 91 90 1.24 實施例3 0.1 0.02 0.09 0.010 91 90 1.15 實施例4 0.5 0.02 0.50 0.009 92 90 1.19 實施例5 1 0.02 1.02 0.011 93 90 1.30 實施例6 2 0.02 2.01 0.014 95 90 1.45 實施例7 4 0.02 4.00 0.012 94 90 1.69 實施例8 6 0.02 6.02 0.012 93 90 1.84 實施例9 8 0.02 8.02 0.011 91 90 2.15 實施例10 0.001 1.5 0.001 0.84 91 90 1.41 實施例11 0.01 1.5 0.009 0.81 92 90 0.91 實施例12 0.025 1.5 0.023 0.78 92 90 0.82 實施例13 0.05 1.5 0.052 0.78 92 90 0.70 實_14 0.075 1.5 0.075 0.82 93 90 0.58 實施例15 0.1 1.5 0,11 0.81 93 90 0.68 實施例16 0.5 1.5 0.49 0.81 94 90 0.72 實施例17 1 1.5 0.99 0.84 95 90 0.S2 實施例18 2 1.5 2.02 0.79 97 90 0.% 實施例19 4 1.5 3.97 0.83 % 90 1.22 實施例20 6 1.5 6.00 0.82 94 90 1.45 實施例21 8 1.5 8.01 0.83 92 90 L88 (請先閔讀背面之注意事碩再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格U10X297公釐） 17 438996 五、發明説明（15 〔表2〕 A7 B7 經濟部中央標準局員工消費合作杜印製 實施例No 混合比祕） 燒結體組成分(wt%) 燒結體 相對密度 (96) 成膜特性 Si〇2 Βί ζ〇3 SiOa Bi2〇3 可見光平均 透過率(¾) 電阻係數 (Xl〇-4Qca) 實删22 0.001 6 0.001 3.36 95 90 1.53 實施例23 0.1 6 o.n 3.30 % 90 0.79 實施例24 1 6 0.98 3.37 97 90 0.93 實施例25 2 6 2.03 3.34 99 90 1.10 實施例26 4 6 3.99 3.35 98 90 1.34 實施例27 6 6 5.98 3.29 97 90 1.59 實施例28 8 6 7.98 3.41 95 90 1.93 實施例29 0.001 11 0.001 6.14 94 90 1.58 實施例30 0.1 11 0.12 6.09 95 90 0.90 實_31 1 11 1.00 6.16 96 90 1.00 實施例32 2 11 1.% 6.11 98 90 1.20 實施例33 4 η 3.% 6.12 98 90 1.40 實施例34 6 11 6.07 6.09 % 90 1.62 實施例35 8 11 8.11 6.21 95 90 1.% 實施例％ 0.001 13 0.001 7.30 93 90 1.61 實施例37 0.1 13 0.11 7.28 94 90 0.99 實施例38 1 13 1.01 7.14 95 90 1.14 實施例39 2 13 1.92 7.31 9S 90 1.32 實施例40 4 13 4.04 7.34 97 90 1.48 實施例41 6 13 6.02 7.22 95 90 1.68 實施例42 0.001 16 0.001 8.96 92 90 1.65 資施例43 0.1 16 0.10 9.00 93 90 1.11 實施例44 1 16 0.98 8.99 95 90 1.29 實施例45 2 16 1.98 9.04 97 90 1.57 實施例46 4 16 4.01 9.01 % 90 1.76 實施例47 6 16 5.99 9.01 94 90 2.02 (請先閱讀背面之注意事項再填寫本頁) .1"裝- -3 .線 本紙張尺度適用t國國家標準（CNS ) A4規格（2 ί Ο X 297公釐） 18 經濟部中央標準局員工消費合作社印製 4389 9 6 A7 五、發明説明（16 ) 〔表3〕 比較例No 混合比(wt%) 燒結體W分(wt%) 燒結髏 相對密度 (96) 成膜恃性 SiOa ΒΪ2〇3 Si02 Bi a〇a 可見光平均 透過率(％) 電阻係數 (xi〇-4Qcm) 比較例1 0 0 0 0 69 90 2.01 bh較例2 0 0.02 0 0.011 70 比較例3 0 1,5 0 0.82 72 90 5.13 比較例4 0 3 0 1.66 76 t：b較例5 0 6 0 3.31 79 90 6.42 比較例S 0 11 0 6.10 79 90 16.5 比較例7 0 Β 0 7.26 79 90 24.1 比較例8 0 16 0 8.98 79 90 40.8 比較例9 0.1 0 0.09 0 71 90 1.97 比較例10 1 0 1.01 0 72 90 2.01 比較例11 2 0 2.00 0 76 90 2.23 比較例12 4 0 3.95 0 83 90 2.40 比較例13 6 0 5.98 0 87 90 2.71 比較例14 8 0 8.02 0 90 90 2.88 比較例15 10 0 10.11 0 91 90 3.04 比較例16 10 1.5 9.99 0.83 91 90 2.05 比較例17 10 6 9.97 3.34 93 90 2.33 比較例18 10 11 10.08 8.95 93 90 2.61 比較例19 16 IS 16.01 10.08 94 90 2.09 比較例20 8 13 8.10 7.29 92 90 2.07 比較例21 0.1 18 0.10 10.11 91 90 2.01 bh較例22 2 18 1.98 10.06 % 90 1.% 比較例23 4 18 3.97 10.14 95 90 2.03 1 ^ ( i-- I ~ {請先閱讀背面之注意事項再填寫本頁) 訂 '線 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 19 - 經濟部中夬標芈局員工消費合作社印製 43 89 9 6 A7 B7 五、發明説明（17 ) 實施例48〜50，比較例24、25 使用和實施例1相同原料之粉末並變化氧化錫童據以 製成試料。 氧化銦和氧化錫之混合量係如表4之比率所示。在和 實施例1相同條件下進行預燒以製成ΙΤ0粉末。再於各該 ΙΤ0粉末中混合O.lwt%之氧化矽，以及1.5wt%之氧化鉍 。其他條件則同實施例1 一樣，據Μ製得燒結體，並Μ此 製成透明導電膜。 燒結匾組成分，密度Μ及膜質特性如表4所示。 〔表4〕 混合量 焼結體 成膜 特性 tWiNo Ir)2〇3 (g) SnOz («) SnOa Sidz Bl2〇3 m 可躺平均 wmm 電阻係數 (xi〇-4Qca) tt^J24 1000 0 0.0 0.10 0.80 96 90 3.1 950.0 50.0 4.9 0.09 0.82 95 90 1.1 ^915 900.0 100.0 9.6 0.11 0.81 93 90 0.68 850.0 150.0 14.8 0.10 0.79 93 90 0.79 wsm mo 250.0 24.1 0.13 0.80 92 90 1.6 mm 700.0 mo 28.8 0.09 0.81 91 90 2.5 實施例51〜94,比較例26〜39 使用實施例14所製成之檷靶，並以長5、6所示之置之 氧氣和氫氣而其餘部分方氬氣之混合氣髖作為濺射氣豔， 除此之外其餘條件均同實施例1，據此製得透明導電膜。 該瞑質特性如表5、 6所示。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） -.20 ^ ^ 1裝 訂 線 < · (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局男工消費合作社印製 438996 A7 B7 五、發明説明（U ) 〔表5〕 實施例No 比較例No $級㈣ 全壓 (Torr) 導入氣SS分E 成膜 恃性 IPP·， \Torr) 可見光平均 透遇率(％) 電阻係數 (X 10·，Sea) 0« Η> Q> Ha 贾施例5ί 0 0 5Χ10'3 .0 0 90 1.5 實施例52 0 2ρρι 5Χ10-* 0 L0X10'3 90 ΙΛ S施例53 0 2〇ρρ· 5X1(TJ 0 I.〇X1〇-T 90 1.4 實施例54 0 60ρρ· 5X10,3 0 1·〇Χΐ〇-τ 90 1.3 Κ施例55 0 0.2¾ 5ΧΙ0-* 0 L0X10-* 90 1·3 實施例56 0 296 5xi〇-a 0 1.0X1D'11 90 L4 Κ施娜7 0 20% 5X10—* 0 1.0X10—* 90 1.8 比較例26 0 50% 5X10'* 0 1.0X10-4 90 2.4 寅施例58 2ρρ· 0 5X10'a L〇xi〇-s 0 90 1.5 真施例59 2ppm 2ρρ· 5X10-* 1.0X10-* 1.0X10-， 90 1.1 難例60 2ρρ· 20ρρ· 5XKT1 1.0X10-* L0X10-7 90 0.93 ΪΪ施例61 2ρρ· 6〇ρρ 環 5X10-* 1.0X10-， l.〇xi〇-T 90 0.88 實施钶62 2ρρ· 0.2¾ 5X1Q-* 1.0X10·* 1.0X10-* 90 0.95 賞施例63 2ρρ· 7% 5>α〇-· 1·〇Χΐ〇-· l.〇Xl〇-a 90 LI 實施例64 2ρρ* 2096 5X10-1 Ι-ΟΧΙΟ-» 1.0X10-4 90 1.6 比較财 2ρρ爾 50¾ 5X10-， 1.0X10-3 i.〇xi〇-4 90 2.3 S施例65 20ρρ« 0 5X10·， 1.0X10-7 0 90 1.4 實施例66 20ρρ· 2ρρ* 5X10'* 1.〇X1〇-T l.oxio'1 90 0.81 ®施例67 2〇ρρμ 20ppa 5X10-* l.〇Xl〇-T l.〇Xl〇-T 90 0,67 «施例68 20ρρι 6〇ρρ· 5X10-， l.〇Xl〇-T l.〇xl〇-T 90 0.62 實施卿 20ρρν 0.2¾ 5X10-， 1·〇Χΐ〇-τ 1,0X10'· 90 0,91 寅施例70 20ρρ· 2% 5X10'* l.〇xi〇-T 1.0X10·* 90 1.3 貢施例71 20ρρ· 2D96 5X10"1 l-〇xi〇-T 1.0X10-* 90 1.5 tfc較钶28 20ρρ* 5096 5X10-* l.〇Xl〇-T L0X10-* 90 2.3 S施例72 0.2¾ 0 5X10—· l.oxio-5 0 90 1.3 ΙΪ施例73 0.2¾ 2ρρ· 5X10*11 1，〇X1〇-· 1.0X10'3 90 0.76 »施例·74 0.2¾ 20ρρι 5X10·， 1.0X10·， l，〇xl〇-T 90 0.64 實施例75 0.2¾ 6〇ρρ« 5xl〇-a 1.0X10-* l.〇Xl〇-T 90 0.60 實施例76 0.2¾ 0.2% 5X10·* 1.0X10-· 1.0X10-*. 90 0.89 霣施例77 0.2¾ 296 5x10—a 1.0X10-* l.〇xl〇-a 90 L2 實施例78 0.2% 2096 5X10·* L0X1O*1 1.0X10，* 90 1.5 實施例29 0.2¾ 50¾ 5xi〇-a 1.0X10-3 l.oxio·* 90 2,2 Ι^ϋ· ^^^1 ^^^1 ^^^1 ^^^1 ^^^1 ^^^1 I In -- 1^^^ ^^^1 \ , I 1— n , 0¾-9髮 - ~ - (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X 297公釐） -21 - 經濟部中央標準局員工消費合作社印裝 43899 6 A7 B7 五、發明説明（19 ) 〔表6 ] 實施例No 比較例No 氣簏濃度 (ppm > %) 全壓 (Torr) 導入氣體分壓 (Torr) 成膜特性 可見光平均 透過率(％) 電阻係數 (Xl〇-*£2cm) 〇3 Ha 0. Ha 筲施例79 2% 0 5X10"3 1.0X10-® 0 90 1.3 貿施例SO 2% 2ppm 5X10^ 1.0X10'8 l.oxio-3 90 0.73 實施例81 7% 20 ppm 5X10-3 l.〇Xl〇-B l.oxio·7 90 0.62 貫施例82 2% 6Qppm 5X10-3 i.〇xicra 3.0X10'T 90 0.59 實施例83 m 0.2¾ 5X10-3 l.〇Xl〇-B 1.0X10'6 90 0.86 實施例84 1Ρ/〇 2% 5X10'3 1.0X10-5 l.oxio-8 90 1.1 實施例85 TP/o 20¾ 5X10-3 1.0X10-8 1.0X10·* 90 1.5 比較例30 m 50¾ 5X10-3 1.0X10-5 2.5X10-* 90 2.1 賁施例86 im 0 5X10-=* l.oxio-* 0 90 1.6 實施例87 20% 2ppi 5X10-3 1.0X10— l.oxio·3 90 1.1 實施例88 20% 20ppm 5X10-3 1.0X10-* l.oxio*7 90 0.91 實施例89 20¾ 60ppm 5X10-3 1.0X10-* 3.0X10—7 90 0.87 實施例90 20% 0.2% 5X10*3 l.oxicr4 l.〇xi〇-E 90 1.2 賁施例91 20% m 5xl0~3 1.0X10〃 l.〇Xl〇-B 90 1.6 實施例92 20% 20¾ 5xl〇-J 1.0X10-* 1.0X10-* 90 2.0 1±較例31 20% 50¾ 5X10-1 1.0X10-* 2.5X10-‘ 90 2.7 比較例32 50% 0 5X10-1 1.0X10'‘ 0 90 3.4 比較例33 50% 2ppn 5X10·3 1.0X10-* l.oxio,3 90 3.1 比較例34 50% 20ppm 5X10-3 1.0X10'4 l.oxio-7 90 2.7 比較例35 50% 60ppm 5xi〇-3 1.0X10-* 3.0X10-7 90 2.9 ϋ較例36 50¾ 0.2% 5xi〇-a 1.0X10-* l.oxio-s 90 3.5 比較例37 50¾ 20% 5X10-3 l.oxitr* 1.0X10-* 90 6.3 比較例38 0.1% 0.1% 5X10'3 1.0X10-3 l.oxio-3 不成膜 實施例93 lOppia 60ppm 5X10—3 1.0X10-3 6.0X10'3 90 1.1 贸施例94 2ppm 60ppa 5X10-3 1.0X10-7 3.OX10'3 90 1.8 比較例39 2ppm 60ppia 5X1ET3 1.0X1Q-7 6.0X1Q-3 90 3.1 --------裝 II -. (請先閱讀背面之注意事項再填寫本頁) 訂 線 本紙張尺度適用中國國家標準（CMS ) A4規格（210X297公釐） 22 4 3 8 9 S 6 A7 B7> 3 m ΰ Θ ① Α7 ΒΤ (Although 4 is interesting) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 438996 V. Description of the invention (u) method can use trimethoxine, tetraisopropoxy bracelet, four As raw materials, ethoxylate and triisopropoxy are used. You can also use the S coating method (although worse than the sputtering method) to form a transparent conductive film: Also, indium osmate, tin chloride, TEOS (tetraethoxylate), and bismuth nitrate acetopropene <2 4- < > Xicai >) The solution was diluted with acetone, etc., and coated by mandrel coating, dip coating, printing method, etc. and thermally decomposed to obtain an ITO film. At this time, a thixotropic agent and a rib adhesive can also be added to the coating liquid. In addition, if the raw materials are appropriately selected and then coated by a gel method, an aqueous solution thermal decomposition method, etc., a film can also be formed. The film-forming substrate can be glass. , Plastic sheet or film, or with a protective or functional film applied to it. Since only ITO with tin oxide added to the oxidation box has a higher vapor level during sintering, a sintering mechanism using evaporation and condensation is used. However, it is difficult to shrink *, making it difficult to achieve high density of the sintered body. However, it is surprising that if sintering aids such as Bi2O3 are added, it will become a liquid phase at about 830T: this phase will prevent the evaporation of ITO, so the sintering of evaporation and condensation will be suppressed. The liquid phase sintering machine is said to improve sintering. In other words, the liquid-phase rhenium knots cause matter to move due to the presence of the rhenium phase, and the sintered body can be made denser with shrinkage. However, if Si02 is not added and only Bi20 is added, the improvement effect of high density is limited. The relative density of BU03 added with 16wt% is only 逹 79¾. According to the present invention, the above-mentioned Si02-Bi203 composition can accelerate liquid phase sintering, achieve high density, and form a good transparent conductive film. This paper size applies to Chinese National Standard i CNS) A4 specification (2 丨 OXM7 mm) I --------------- IT ------ -------- --------- ΐ I 、 一-; (Please read the notes on the back before filling out this page), 14 4 389 9 6 A7 B7 V. Description of the invention (12) Employees ’consumption by the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printing can be verified through the examples described later, and by adding the above-specified Si02-Bi203 component to 1T0, a high-density sintered body with an orange pair density greater than 90% can be obtained. Furthermore, the sintered body can be used to build a target and use the sputtering method to produce an ITO film having a low coefficient of resistance, a large visible light transmittance, and an extremely valuable industrial value. The composition of the Si02-Bi2 03 specified above is critical, for example, and the condition without the addition of BU 03 (fcb comparative example 10 to 13: sintered hip orange pair density 72 to 88, conductive film resistivity 2.0 to 2.3 xi0_ * £ tca > In comparison, a case containing a certain amount of Bi203 (Examples 21 to 24: sintered mandarin orange has a density of 95 to 93, and the conductive film has a resistivity of 1.2 to 1.3). The resistivity is extremely low. Next, examples and comparative examples are used to explain the sintered body of the present invention, the transparent conductive film, and a method for forming the film. Examples 1 to 47 and Comparative Examples 1 to 23 900 g of indium oxide (Dongwa Chemical Made of osmium oxide N, purity 99.99%, average particle size < 15 (1 = 0.93μιιο and 100g of tin oxide < made by New Japan Gold Co., Ltd., purity 99.9%, particle size "3! | 1] = 0.72 | ^), When the ball mill with a capacity of 4.8 liters was mixed for 24 hours, it was then calcined in the air at 1450 = for 15 hours, and ITO powder was obtained according to M. Then, bismuth oxide (made by Izuzu and chemicals, purity 99.9%, Particle size dSD = 0,78Kii〇 and silica (Wako Pure Chemicals * purity 99.9999%, particle size dsa = 1.1 μB) M Table 1 The ratio shown is mixed with the ITO powder, and the weight ratio of the mixed system of bismuth oxide and silicon oxide in Table 1 to Table 1 is expressed as% by weight, and the rest is ITO. The mixing system is performed by a ball mill. Add 0.05wt to the end of each mixture % Of PVA solution is made according to M 1 ---- ^ ------ "Packing-• ·--(Please read the precautions on the back before filling out this page) The size of the paper is applicable to Chinese standards (CNS> A4 specification (210X 297 mm) 15 A7 B7 438996 V. Description of the invention (13) A slurry with a solid concentration of 20% by weight is spray-dried by a spray dryer to obtain the slurry. Granules with an average particle diameter of 20 μ · were made. The granules were shaped by adding an axis under Iton / C »3, and a diameter of 90B! E < fr and a thickness of 3-5B * were obtained. Disc shaped body. The disc shaped body was placed in the air and fired at a temperature of 1450 * 0 for 10 hours. The composition (chemical analysis) and relative density of the sintered body are shown in Tables 1 to 3. . Use each sintered cross as a target and place it in a direct-rolling magnetron sputtering device. After the oil reaches a vacuum of IX 10-8torr, the M partial pressure vacuum needle monitors it. While introducing hydrogen at 3X 10 ”torr, oxygen was introduced at 3X 10_etorr, and then argon gas was introduced at a full pressure of 5xi (T3torr before M. Introduce a glass substrate (size 76X 26X at 300¾), A transparent conductive film was made under the conditions of 100W of input power and 65mB between substrates. Repeated sputtering using the dwelling target of any of the examples * As a result, the blackening phenomenon of the target was extremely weak, and the sputtering rate of 10 A / sec was almost inefficient. It was confirmed through EPMA that the composition of the transparent conductive film produced was approximately the same as that of the target. The thickness of the prepared transparent conductive film, the average transmittance M of visible light, and the resistivity are shown in Tables 1 to 3. --- ^ ------ i: · install ------ order ----- line.- > .. (Please read the precautions on the back before filling this page) Central Standard of the Ministry of Economy The paper size printed by the Bureau ’s Consumer Cooperatives applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) -1 ^-16 438996 A7 B7 V. Description of the invention (14) [Table 1] Example No Mixing ratio (wt%) Sintered body composition < wt% > Sintered 酦 Relative density (96) Film forming characteristics Si〇z Bi 2〇3 SiOz BiaOa Average visible light transmittance㈣ Resistance Coefficient (X 10'4Ω) Example 1 0.001 0.02 0.001 0.011 90 90 1.40 Example 2 0.05 0.02 0.051 0.013 91 90 1.24 Example 3 0.1 0.02 0.09 0.010 91 90 1.15 Example 4 0.5 0.02 0.50 0.009 92 90 1.19 Example 5 1 0.02 1.02 0.011 93 90 1.30 Example 6 2 0.02 2.01 0.014 95 90 1.45 Example 7 4 0.02 4.00 0.012 94 90 1.69 Example 8 6 0.02 6.02 0.012 93 90 1.84 Example 9 8 0.02 8.02 0.011 91 90 2.15 Example 10 0.001 1.5 0.001 0.84 91 90 1.41 Example 11 0.01 1.5 0.009 0.81 92 90 0.91 Example 12 0.025 1.5 0.023 0.78 92 90 0.82 Example 13 0.05 1.5 0.052 0.78 92 90 0.70 Real_14 0.075 1.5 0.075 0.82 93 90 0.58 Example 15 0.1 1.5 0, 11 0.81 93 90 0.68 Example 16 0.5 1.5 0.49 0.81 94 90 0.72 Example 17 1 1.5 0.99 0.84 95 90 0.S2 Example 18 2 1.5 2.02 0.79 97 90 0.% Example 19 4 1.5 3.97 0.83% 90 1.22 Example 20 6 1.5 6.00 0.82 94 90 1.45 Example 21 8 1.5 8.01 0.83 92 90 L88 (Please read the cautions on the back before filling in this page) This paper size is applicable to Chinese National Standard (CNS) A4 specification U10X297 mm 17 438996 V. Description of invention (15 [Table 2] A7 B7 Consumption Cooperation by Employees of Central Standards Bureau, Ministry of Economic Affairs, Du Printed Example No. Mixture ratio) Sintered body composition (wt%) Relative density of sintered body (96) Film formation characteristics Si〇2 Βί ζ〇3 SiOa Bi2〇3 Average visible light Transmittance (¾) Resistivity (Xl0-4Qca) Real delete 22 0.001 6 0.001 3.36 95 90 1.53 Example 23 0.1 6 on 3.30% 90 0.79 Example 24 1 6 0.98 3.37 97 90 0.93 Example 25 2 6 2.03 3.34 99 90 1.10 Example 26 4 6 3.99 3.35 98 90 1.34 Example 27 6 6 5.98 3.29 97 90 1.59 Example 28 8 6 7.98 3.41 95 90 1.93 Example 29 0.001 11 0.001 6.14 94 90 1.58 Example 30 0.1 11 0.12 6.09 95 90 0.90 Real_31 1 11 1.00 6.16 96 90 1.00 Example 32 2 11 1.% 6.11 98 90 1.20 Example 33 4 η 3.% 6.12 98 90 1.40 Example 34 6 11 6.07 6.09% 90 1.62 Example 35 8 11 8.11 6.21 95 90 1.% Example % 0.001 13 0.001 7.30 93 90 1.61 Example 37 0.1 13 0.11 7.28 94 90 0.99 Example 38 1 13 1.01 7.14 95 90 1.14 Example 39 2 13 1.92 7.31 9S 90 1.32 Example 40 4 13 4.04 7.34 97 90 1.48 Example 41 6 13 6.02 7.22 95 90 1.68 Example 42 0.001 16 0.001 8.96 92 90 1.65 Example 43 0.1 16 0.10 9.00 93 90 1.11 Example 44 1 16 0.98 8.99 95 90 1.29 Example 45 2 16 1.98 9.04 97 90 1.57 Implementation Example 46 4 16 4.01 9.01% 90 1.76 Example 47 6 16 5.99 9.01 94 90 2.02 (Please read the precautions on the back before filling out this page) .1 " Packing--3. The paper size of the paper is applicable to the national standard of the country ( CNS) A4 size (2 ί Ο X 297 mm) 18 Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 4389 9 6 A7 V. Description of the invention (16) [Table 3] Comparative example No Mixing ratio (wt%) W content of sintered body (wt%) Relative density of sintered cross (96) Film formation 恃SiOa ΒΪ2〇3 Si02 Bi a〇a Average visible light transmittance (%) Resistivity (xi〇-4Qcm) Comparative example 1 0 0 0 0 69 90 2.01 bh Comparative example 2 0 0.02 0 0.011 70 Comparative example 3 0 1, 5 0 0.82 72 90 5.13 Comparative example 4 0 3 0 1.66 76 t: b Comparative example 5 0 6 0 3.31 79 90 6.42 Comparative example S 0 11 0 6.10 79 90 16.5 Comparative example 7 0 Β 0 7.26 79 90 24.1 Comparative example 8 0 16 0 8.98 79 90 40.8 Comparative Example 9 0.1 0 0.09 0 71 90 1.97 Comparative Example 10 1 0 1.01 0 72 90 2.01 Comparative Example 11 2 0 2.00 0 76 90 2.23 Comparative Example 12 4 0 3.95 0 83 90 2.40 Comparative Example 13 6 0 5.98 0 87 90 2.71 Comparative Example 14 8 0 8.02 0 90 90 2.88 Comparative Example 15 10 0 10.11 0 91 90 3.04 Comparative Example 16 10 1.5 9.99 0.83 91 90 2.05 Comparative Example 17 10 6 9.97 3.34 93 90 2.33 Comparative Example 18 10 11 10.08 8.95 93 90 2.61 Comparative Example 19 16 IS 16.01 10.08 94 90 2.09 Comparative Example 20 8 13 8.10 7.29 92 90 2.07 Comparative Example 21 0 .1 18 0.10 10.11 91 90 2.01 bh Comparative Example 22 2 18 1.98 10.06% 90 1.% Comparative Example 23 4 18 3.97 10.14 95 90 2.03 1 ^ (i-- I ~ {Please read the notes on the back before filling in this Page) Ordering the paper size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 19-Printed by the Employees' Cooperatives of the China National Standards Bureau of the Ministry of Economic Affairs 43 89 9 6 A7 B7 V. Description of the invention (17) Examples 48 to 50 and Comparative Examples 24 and 25 The same raw material powder as in Example 1 was used and tin oxide was changed to prepare samples. The mixing amounts of indium oxide and tin oxide are shown in the ratios in Table 4. Pre-firing was performed under the same conditions as in Example 1 to prepare an ITO powder. Then, 0.1 wt% of silicon oxide and 1.5 wt% of bismuth oxide were mixed in each of the ITO powders. The other conditions were the same as in Example 1. A sintered body was prepared according to M, and a transparent conductive film was prepared. The sintered plaque composition, density M and film quality characteristics are shown in Table 4. [Table 4] Film formation characteristics of mixed mass 焼 junctions tWiNo Ir) 2〇3 (g) SnOz («) SnOa Sidz Bl2 0 3 m average lying wmm resistivity (xi〇-4Qca) tt ^ J24 1000 0 0.0 0.10 0.80 96 90 3.1 950.0 50.0 4.9 0.09 0.82 95 90 1.1 ^ 915 900.0 100.0 9.6 0.11 0.81 93 90 0.68 850.0 150.0 14.8 0.10 0.79 93 90 0.79 wsm mo 250.0 24.1 0.13 0.80 92 90 1.6 mm 700.0 mo 28.8 0.09 0.81 91 90 2.5 Example 51 ~ 94, Comparative Examples 26 ~ 39 Using the target made in Example 14 and using a mixture of oxygen and hydrogen as shown in lengths 5 and 6 and the rest of the square argon as the sputtering gas, Except for the other conditions, the same conditions as in Example 1 were used to prepare a transparent conductive film. The quality characteristics are shown in Tables 5 and 6. This paper size applies to China National Standard (CNS) Α4 size (210 X 297 mm) -.20 ^ ^ 1 gutter < · (Please read the precautions on the back before filling out this page) Male Worker, Central Bureau of Standards, Ministry of Economic Affairs Printed by a consumer cooperative 438996 A7 B7 V. Description of the invention (U) [Table 5] Example No Comparative Example No $ Class ㈣ Total pressure (Torr) Introduced gas SS E E Film-forming IPIPP ·, \ Torr) Visible light average transmission Case ratio (%) Resistivity (X 10 ·, Sea) 0 «Η > Q > Ha Jia Shi Example 5ί 0 0 5 × 10'3 .0 0 90 1.5 Example 52 0 2ρρι 5 × 10- * 0 L0X10'3 90 ΙΛS Example 53 0 2〇ρρ · 5X1 (TJ 0 I.〇X1〇-T 90 1.4 Example 54 0 60ρρ · 5X10, 3 0 1 · 〇Χΐ〇-τ 90 1.3 Κ Example 55 0 0.2¾ 5 × Ι0- * 0 L0X10- * 90 1 · 3 Example 56 0 296 5xi0-a 0 1.0X1D'11 90 L4 KE Shina 7 0 20% 5X10— * 0 1.0X10— * 90 1.8 Comparative Example 26 0 50% 5X10 '* 0 1.0X10-4 90 2.4 Example 58 2ρρ · 0 5X10'a L〇xi〇-s 0 90 1.5 True example 59 2ppm 2ρρ 5X10- * 1.0X10- * 1.0X10-, 90 1.1 Hard case 60 2ρρ 20ρρ 5XKT1 1.0X10- * L0X10-7 90 0.93 ΪΪExample 61 2 ρ · 6〇ρρ ring 5X10- * 1.0X10-, l.〇xi〇-T 90 0.88 implementation 钶 62 2ρρ · 0.2¾ 5X1Q- * 1.0X10 · * 1.0X10- * 90 0.95 reward example 63 2ρρ · 7% 5 > α〇- · 1 · 〇Χΐ〇- · l.〇Xl〇-a 90 LI Example 64 2ρρ * 2096 5X10-1 Ι-ΟΧΙΟ- »1.0X10-4 90 1.6 Comparative wealth 2ρρ 尔 50¾ 5X10-, 1.0X10-3 i.〇xi〇-4 90 2.3 S Example 65 20ρρ «0 5X10 ·, 1.0X10-7 0 90 1.4 Example 66 20ρρ · 2ρρ * 5X10 '* 1.〇X1〇-T l.oxio '1 90 0.81 ® Example 67 2〇ρρμ 20ppa 5X10- * l.〇Xl0-T l.〇Xl0-T 90 0,67 «Example 68 20ρρι 6〇ρρ 5X10-, l.〇Xl〇 -T l.〇xl0-T 90 0.62 Implementation 20 ρρν 0.2¾ 5X10-, 1 · 〇Χΐ〇-τ 1,0X10 '· 90 0,91 Yin Example 70 20ρρ · 2% 5X10' * l.〇xi 〇-T 1.0X10 · * 90 1.3 Gongshi 71 71 20ρρ · 2D96 5X10 " 1 l-〇xi〇-T 1.0X10- * 90 1.5 tfc 钶 28 20ρρ * 5096 5X10- * l.〇Xl〇-T L0X10 -* 90 2.3 S Example 72 0.2¾ 0 5X10— · l.oxio-5 0 90 1.3 ΙΪ Example 73 0.2¾ 2ρρ 5X10 * 11 1, 〇X1〇- · 1.0X10'3 90 0.76 »Example · 74 0.2¾ 20ρρι 5X10 ·, 1.0X 10 ·, l, 0 × 10-T 90 0.64 Example 75 0.2¾ 6〇ρρ «5xl0-a 1.0X10- * l.〇Xl0-T 90 0.60 Example 76 0.2¾ 0.2% 5X10 · * 1.0X10 -· 1.0X10- *. 90 0.89 霣 Example 77 0.2¾ 296 5x10-a 1.0X10- * l.〇xl〇-a 90 L2 Example 78 0.2% 2096 5X10 · * L0X1O * 1 1.0X10, * 90 1.5 Example 29 0.2¾ 50¾ 5xi〇-a 1.0X10-3 l.oxio ** 90 2,2 Ι ^ ϋ · ^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 ^^^ 1 I In-1 ^^^ ^^^ 1 \, I 1— n, 0¾-9 rounds-~-(Please read the precautions on the back before filling out this page) This paper size applies Chinese National Standard (CNS) Μ specifications (210X 297 mm) -21-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 43899 6 A7 B7 V. Description of the invention (19) [Table 6] Example No Comparative Example No Gas concentration (ppm >% ) Total pressure (Torr) Introduced gas partial pressure (Torr) Film formation characteristics Average visible light transmittance (%) Resistivity (Xl0- * £ 2cm) 〇3 Ha 0. Ha 筲 例 79 2% 0 5X10 " 3 1.0 X10-® 0 90 1.3 Commercial Example SO 2% 2ppm 5X10 ^ 1.0X10'8 l.oxio-3 90 0.73 Example 81 7% 20 ppm 5X10-3 l.〇Xl〇-B l.oxio · 7 90 0.6 2 Example 82 2% 6Qppm 5X10-3 i.〇xicra 3.0X10'T 90 0.59 Example 83 m 0.2¾ 5X10-3 1.0.0X10-B 1.0X10'6 90 0.86 Example 84 1P / 〇2 % 5X10'3 1.0X10-5 l.oxio-8 90 1.1 Example 85 TP / o 20¾ 5X10-3 1.0X10-8 1.0X10 · * 90 1.5 Comparative example 30 m 50¾ 5X10-3 1.0X10-5 2.5X10- * 90 2.1 Example 86 im 0 5X10-= * l.oxio- * 0 90 1.6 Example 87 20% 2ppi 5X10-3 1.0X10— l.oxio · 3 90 1.1 Example 88 20% 20ppm 5X10-3 1.0 X10- * l.oxio * 7 90 0.91 Example 89 20¾ 60ppm 5X10-3 1.0X10- * 3.0X10-7 90 0.87 Example 90 20% 0.2% 5X10 * 3 l.oxicr4 l.〇xi〇-E 90 1.2贲 Example 91 20% m 5xl0 ~ 3 1.0X10〃 l.〇Xl〇-B 90 1.6 Example 92 20% 20¾ 5xl0-J 1.0X10- * 1.0X10- * 90 2.0 1 ± Comparative Example 31 20% 50¾ 5X10-1 1.0X10- * 2.5X10- '90 2.7 Comparative Example 32 50% 0 5X10-1 1.0X10' '0 90 3.4 Comparative Example 33 50% 2ppn 5X10 · 3 1.0X10- * l.oxio, 3 90 3.1 Comparison Example 34 50% 20ppm 5X10-3 1.0X10'4 l.oxio-7 90 2.7 Comparative Example 35 50% 60ppm 5xi〇-3 1.0X10- * 3.0X10-7 90 2.9 ϋ Comparative Example 36 50¾ 0.2% 5xi〇-a 1.0X10- * l.oxio-s 90 3.5 Compare 37 50¾ 20% 5X10-3 l.oxitr * 1.0X10- * 90 6.3 Comparative Example 38 0.1% 0.1% 5X10'3 1.0X10-3 l.oxio-3 Non-film-forming Example 93 lOppia 60ppm 5X10-3 1.0X10- 3 6.0X10'3 90 1.1 Trade example 94 2ppm 60ppa 5X10-3 1.0X10-7 3.OX10'3 90 1.8 Comparative example 39 2ppm 60ppia 5X1ET3 1.0X1Q-7 6.0X1Q-3 90 3.1 ------- -Pack II-. (Please read the precautions on the back before filling this page) The paper size of the booklet applies the Chinese National Standard (CMS) A4 (210X297 mm) 22 4 3 8 9 S 6 A7 B7
五、發明説明（2G 經濟部中央標準局員工消費合作社印製 產業上之利用可能性 依據本發明之特定SiG2-Bia〇3組成分，卽可容易製得 相對密度高逹90%以上之高密度ITO燒結髏，利用該燒結 髏並可製得低電粗係數，高透光率之I T0透明導電膜。該 電阻係數約為2.0X 10·*Ω cbM下，較佳則為1.5X 10_4Ω cm Μ下*更好則爲1.0 x 10—4 QcbM下。 利用燒結體並藉濺射法製成透明導電膜之際，在檁靶 表面不會發生黑化現象，膜之形成速率亦能維持穩定，膜 之電阻係數亦不致於惡化。另外，在工業上*為去除表面 之黑化物而不得不取下標靶，或是因檫靶壽命短導致檷靶 之交換頻率多，進而導致降低濺射裝置之蓮轉效率等之問 題亦可因本發明而得以解決。 另外，將透明導電膜形成更薄，可縮短蝕刻時間。同 時亦能提高良品率。 因此，本發明之透明導電膜特別適合使用於液晶顯示 器、電致發光、m鉻顯示器等之透明電捶上。 圈面之簡單說明 第1豳為Si02-Bi8〇3二成分集圃，表示ΙΤ0燒結體及 ΙΤ0透明導霉膜之Si02M及BU03之组成分〇 11* ^ 裝 1 ϋ 訂 II ^ - / -(請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Λ4規格（2L0X297公廋） 23V. Description of the invention (2G Utilization possibilities in the printing industry by the Central Consumers Bureau, Ministry of Economic Affairs, Consumer Cooperatives) According to the specific SiG2-Bia03 composition of the present invention, it is easy to produce high density with a relative density of more than 90% ITO sintered crossbones can be used to produce I T0 transparent conductive films with low electrical coefficient and high light transmittance. The resistivity is about 2.0X 10 · * Ω cbM, preferably 1.5X 10_4Ω cm Μ The lower * better is 1.0 x 10-4 QcbM. When using a sintered body and making a transparent conductive film by sputtering, the blackening phenomenon does not occur on the surface of the target, and the film formation rate can be maintained stable. The resistivity of the film will not be deteriorated. In addition, in the industry * the target has to be removed in order to remove the black matter on the surface, or the exchange rate of the target is high due to the short target life, which leads to a reduction in the sputtering device. The problems of lotus transfer efficiency and the like can also be solved by the present invention. In addition, forming the transparent conductive film to be thinner can shorten the etching time. At the same time, the yield can be improved. Therefore, the transparent conductive film of the present invention is particularly suitable for use in LCD display Display, electroluminescence, m-chromium display, etc. The simple description of the circle is the first two components Si02-Bi80 03, which represents the Si02M and BU03 of the ITO sintered body and ITO transparent transparent mold mold. Composition 〇11 * ^ Pack 1 ϋ Order II ^-/-(Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2L0X297) 廋 23