200535970 九、發明說明： 【發明所屬之技彳軒領域】 領域領域 本發明係關於可用來作為透明導電膜之形成材料的含 5氟銦-錫氧化物燒結體（，，Flu〇rine c〇ntaining mdium-Tin-Oxide”：以組成式Ini_xSnxFy〇z表示；以下有時簡 稱為「F—ITO」）。 L先前技術】 背景技術 10 IT0薄膜由於具有高度導電性與優良透光性，故被廣泛 利用作為液晶顯示器等多種表示裝置之透明導電膜。 ΙΤΟ薄膜之製造方法，雖有喷霧法，浸潰法真空蒸鍛 法，濺鏟法等，從其製造成本，生產性，膜質，麟性（導 電性，透光性）等觀點言，相對優良之麟法成為現在生產 15 技術之主流。 濺鍍法有使用銦及錫的合金靶(ΙΤ靶)之方法，與使用氧 化銦及氧化錫的燒結體所形成之氧化物燒結體丁〇靶）的 方法。在於使用IT靶之方法中，薄膜製作時氧導入量之變 動對於膜導電率之依存性極大，且成膜之再現性差，故在 20於大面積的基板上，很難獲得導電性均勻之膜。故使用ITO 靶之方法在大面積化、製作均質膜等方面是有利的。 近年來，在液晶顯示器、有機EL顯示器等方面，為了 使顯不器具有高顯示品質，對於透明導電膜除了要求具有 问‘甩性及南透光性以外，更要求高度之表面平滑性。為 200535970 了因應此種要求’目前正嘗試絲材的金屬氧化物中之— 部分氧以氟取代。 例如，專利文獻m明了以說化銦、氟化锡等作 原料，ϋ使其與氧等進行電漿反應，以製造透明導電膜: 5方法。另，亦有研究以，以使用四氟化碳等氣體作為氣 分之原料之報告(非專利文獻υ。但是，誠如該等習知文獻 所說明，在以氣體作為薄膜形成原料之反應成膜法中盘 前述使用之氧導入成獏之情形相同，由於膜中渗入^ 氣量會不均’且其量亦不足，結果無法獲得展現所=望特 10性之薄膜。因此，可預測的是與使用ιτο乾之情形相同，利 用使用含氟的靶的濺鍍法來製成膜較為適合。實際上，在 專利文獻2中’純告朗了使用含有氟化銦及氧灿的乾 之濺鍍成膜方法，可獲得導電性高於習知者之高導電性薄 膜。 / 15 衫，有關含氣ΙΤ〇革巴之製造方》，幾乎未見於相關報 告。前述專利文獻2揭示使用將氟化銦及氧化銦粉末加壓成 形後之薄片作為靶之實施例，但因成形所得之薄片密度低 且導電性低，所以會產生成膜時放電電壓昇高，成膜速度 低等重大困難。因此，雖有人推測以使用經燒結之高密度 20靶為佳，但目前尚無有關根據燒結法製造F — ITO靶的報告 ，這是因為ΙΤΟ為難燒結性陶瓷的緣故。ΙΤ〇靶通常是由成 形銦及錫與氧所形成之粉末，且藉由在電爐等145〇〜165〇 C高溫下，熱處理約10小時而製成（例如專利文獻3)。但是 ，將該方法使用在依原樣利用含氟銦—錫氧化物粉末來製 6 200535970 造F — ITO靶時，由於高溫、長時間的熱處理，氟將與原料 粉脫離，只能獲得不含氟之ΙΤ〇靶。為抑制氟脫離，例如， 考慮將原料粉末密閉於密閉系内，進行較低溫且短時間之 熱處理，但尚未見由該方法製成F—ITO靶之報告例。 5 因此結論是，為了製作高品質顯示器及使其普及，開 發以簡便且短時間之製程來製造F — ΙΤΟ靶之技術是不可或 缺的。 專利文獻1特開昭60— 121272號公報 非專利文獻 lJ.N.Avaritsiotis and R.P.Howson，Thin 10 Solid Films, vol.80, pp. 63-66(1981) 專利文獻2特開2 〇 〇 〇 — 27 3 618號公報 專利文獻1特開平10 — 7 225 3號公報 【考务明内3 發明概要 15 發明所要解決之問題 因此，本發明之主要目的係提供一種可在低溫且短時 間製造F—ITO靶用高密度燒結體之新技術，以形成具有優 良的表面平滑性之透明導電膜。 本發明人鑑於前述所示之傳統技術上問題，專心一再 20研究結果發現一邊加壓含有銦、錫、氧與氣之混合粉末， 一邊轭加直流脈衝電流(通電燒結）時，在短時間内可製作高 密度之IT0燒結體，並且發現所得之燒結體適於作為透明導 電膜製作用靶，並因而完成本發明。 即’本發明提供以下之含氟銦-錫氧化物燒結體與使 7 200535970 用5亥含鼠銦一錫氧化物燒結體之濺鍍用革巴材。 第1項：一種含氟銦一錫氧化物燒結體之製造方法，其 特徵在於在加壓之情形下對含有銦、錫、氧及氟的粉狀原 料施加直流脈衝電流。 5 第2項：如第1項記載之含氟銦一錫氧化物燒結體之製 造方法，其中前述粉末原料選自於由銦一錫氧化物與氫 氟酸反應所得之粉末；（2)將氧化銦與氫氟酸反應所得之粉 末與氧化錫混合所得之粉末；（3)將氧化錫與氫氟酸反應所 得之粉末與氧化銦混合所得之粉末；⑷氧化姻，氣化鋼與 10氧化錫之混合粉末；（5)氧化銦，氧化錫魏化錫之混合粉 末；⑹氧化姻與氫該反應所得之粉末；⑺氧化姻與氣化 姻之混合粉末；及⑻將前述⑴〜⑺所示之粉末再熱處理後 之粉末所構成之群之至少一種。 第3項：-種含氟銦-錫氧化物燒結體，係由申請專利 15範圍第1或2項之方法製得者。 第4項：-種濺鑛用乾材，係由申請專利範圍第3項之 含氟銦一錫氧化物燒結體形成者。 第5項：-種薄膜’係使用申請專利範圍第4項記載之 濺鍍用靶材製成者。 2〇 帛6項：如第5項記載之薄膜’其膜厚之平均值⑷相對 於薄膜凹凸之高低差（ΔΖ;膜厚的最大值與最小值之差）的 比例（表面平滑度；ΛΖ/d)不超過10%。 發明之效果 根據本發明，可在短時間内穩定地製造高密度之f— 8 200535970 ιτ〇燒結體。 使用本㈣之卜1观結體作為舰脉材時，可制 造表面平滑性優e、 μ 衣 π揮4電性及高透紐之透明導 钱月万法，亦可適用於製作具有多種組成 明導電膜製作用的妒供釦亂透 的濺鍍靶材枓，例如，製造含氟氧化鋅 粗材料。#’ _本發明方法， 辛糸 作以m & 了在独㈣α %、定地製200535970 IX. Description of the invention: [Technical field to which the invention belongs] Field of the invention The present invention relates to a sintered body containing 5 fluorine indium-tin oxide which can be used as a material for forming a transparent conductive film. "mdium-Tin-Oxide": It is expressed by the composition formula Ini_xSnxFy〇z; sometimes referred to as "F-ITO" hereinafter). [Previous Technology] Background Art 10 IT0 films are widely used as transparent conductive films for various display devices such as liquid crystal displays because of their high conductivity and excellent light transmission. The manufacturing method of ΙΤ thin film includes spray method, dipping method, vacuum steam forging method, and shovel method. From the viewpoints of manufacturing cost, productivity, film quality, and permeability (conductivity, light transmission), etc., relatively The excellent Linlin method has become the mainstream of production technology. The sputtering method includes a method using an alloy target (ITO target) of indium and tin, and a method using an oxide sintered body (but not a target) formed from a sintered body of indium oxide and tin oxide. In the method using the IT target, the variation in the amount of oxygen introduced during film production has a great dependence on the conductivity of the film, and the reproducibility of the film is poor. Therefore, it is difficult to obtain a film with uniform conductivity on a large-area substrate. . Therefore, the method using an ITO target is advantageous in terms of large area and production of a homogeneous film. In recent years, in order to achieve high display quality for displays such as liquid crystal displays and organic EL displays, transparent conductive films are required to have a high degree of surface smoothness in addition to the characteristics of slopping and transmissivity. In response to this requirement, 200535970, one of the metal oxides of the wire material that is currently being tried-part of the oxygen is replaced by fluorine. For example, Patent Document m describes a method for manufacturing a transparent conductive film by using indium, tin fluoride, and the like as raw materials and performing a plasma reaction with oxygen and the like. In addition, there have been reports on the use of gases such as carbon tetrafluoride as raw materials for gas (non-patent document υ. However, as described in these conventional documents, the reaction In the membrane method, the same situation is used for the introduction of oxygen as described above. Since the amount of gas infiltrated in the membrane will be uneven and its amount is insufficient, the result will not be able to obtain a thin film exhibiting the desired properties. Therefore, it is predictable that As in the case of using ιτο dry, it is more suitable to form a film by a sputtering method using a fluorine-containing target. In fact, in Patent Document 2, the use of dry sputtering containing indium fluoride and oxygen can be described. The film-forming method can obtain a highly conductive thin film with higher conductivity than a conventional one. / 15 shirts, related to the manufacturer of gas containing ITO Geba ", hardly seen in related reports. The aforementioned Patent Document 2 discloses the use of fluorine An example of the target in which the indium oxide and indium oxide powder are press-molded is used as a target. However, since the flakes obtained by the molding have a low density and a low conductivity, there will be major difficulties such as an increase in discharge voltage during film formation and a low film formation speed. therefore Although some people speculate that it is better to use a sintered high-density 20 target, there is no report on the manufacture of F-ITO targets by sintering method because ITO is a difficult-to-sinter ceramic. ITO targets are usually formed from shaped indium. And a powder formed by tin and oxygen, and is prepared by heat-treating for about 10 hours at an electric furnace or the like at a high temperature of 145 to 1650C (for example, Patent Document 3). However, this method is used to use fluorine as it is Indium-tin oxide powder is used to make 6 200535970 When making F — ITO target, due to high temperature and long-term heat treatment, fluorine will be detached from the raw material powder, and only ITO target without fluorine can be obtained. In order to suppress the detachment of fluorine, for example, It is considered that the raw material powder is sealed in a closed system and subjected to a relatively low temperature and short time heat treatment, but there have been no reported examples of F-ITO targets made by this method. 5 Therefore, in order to make high-quality displays and popularize them, It is indispensable to develop a technology for manufacturing F-ITO targets in a simple and short-time process. Patent Document 1 JP-A-60-121272 Non-Patent Document 1J.N. Avaritsiotis and RPHowson, Thin 10 Solid Films, vol. 80, pp. 63-66 (1981) Patent Document 2 Japanese Patent Application Publication No. 2000- 27 3 618 Patent Document 1 Japanese Patent Application Publication No. Hei 10-7 225 3 SUMMARY OF THE INVENTION 15 Problem to be Solved by the Invention Therefore, the main object of the present invention is to provide a new technology capable of manufacturing a high-density sintered body for an F-ITO target at a low temperature and in a short time to form a transparent conductive film having excellent surface smoothness. In view of the conventional technical problems shown above, the present inventors have intensively studied the results repeatedly and found that while pressing a mixed powder containing indium, tin, oxygen, and gas, and applying a DC pulse current (current sintering) in a short time, A high-density IT0 sintered body can be produced inside, and the obtained sintered body is found to be suitable as a target for producing a transparent conductive film, and thus the present invention has been completed. That is, the present invention provides the following fluorine-containing indium-tin oxide sintered body and a leather material for sputtering using a sintered body containing 5 μm of indium-tin oxide. Item 1: A method for producing a sintered body containing fluorine-containing indium-tin oxide, characterized in that a DC pulse current is applied to a powdery raw material containing indium, tin, oxygen, and fluorine under pressure. 5 Item 2: The method for producing a sintered body of fluorine-containing indium-tin oxide as described in item 1, wherein the aforementioned powder raw material is selected from the powder obtained by the reaction of indium-tin oxide with hydrofluoric acid; Powder obtained by mixing the powder obtained by reacting indium oxide with hydrofluoric acid and tin oxide; (3) Powder obtained by mixing the powder obtained by reacting tin oxide with hydrofluoric acid and indium oxide; (5) a mixed powder of tin; (5) a mixed powder of indium oxide, tin oxide, and tin oxide; a powder obtained by the reaction of oxygen oxide and hydrogen; a mixed powder of oxide oxide and gasified marriage; and At least one type of group consisting of powder after powder heat treatment. Item 3: A fluorine-containing indium-tin oxide sintered body, which is obtained by the method of item 1 or 2 of the scope of application for patent 15. Item 4: A dry material for splattering is formed by a sintered body containing fluorine indium-tin oxide in item 3 of the scope of patent application. Item 5: A kind of thin film 'is made by using the sputtering target described in item 4 of the patent application scope. Item 20 帛 6: The ratio of the film's average value of film thickness as described in item 5 to the height difference (ΔZ; difference between the maximum and minimum film thickness) of the film asperities (surface smoothness; ΛZ / d) not more than 10%. Effects of the Invention According to the present invention, it is possible to stably produce a high density f-8 200535970 ιτ〇 sintered body in a short time. When using the structure of this article as the vessel material, it can produce transparent surface guides with excellent surface smoothness e, μ, π, 4 electrical properties, and high transparency. It can also be used to produce a variety of compositions The jealousy for making conductive film can be used as a sputter target, for example, to produce a fluorozinc oxide rough material. # ’_In the method of the present invention, Xin Zhi made m &
以4之外熱錢結衫㈣作之含氟高密度 把0 10 【實方包冷式】 較佳貫施例之詳細說明 以下詳細說明本發明方法所使用的起始原料，燒結方 法，所得的燒結體等。 起始原| 15 娜起始原料用之各成分原料粉末，未料限制。例 如，銦源可舉例如氧化銦，氯化銦，靖酸鋼，硫酸鋼，氣 化:’漠化銦等。錫源可舉例如氧化錫，氯化錫，石肖酸錫 ，硫酸錫’氟化錫，漠化錫等。氟源可舉例如氫款酸，氟 化銦，氟化錫，乙醯氟等。 20 起始原料可使用摻合該等成分原料的>'昆合物，或該等 成分原料之間的反應生成物，或該等反應生成物經熱處理 或水熱處理生成的粉末。 起始原料中的氟成分，銦成分及錫成分之比例，可因 應依薄成而定的姆料之必要組成，適當地選擇。 200535970 起始原料雖無特別限制，但較佳之混合粉末可舉例如 ⑴銦-錫氧化物錢氣較錢狀粉末；⑵氧化鋼斑气 敗酸反應所得之粉末，再混合氧化錫所得之粉末；⑶氧化 錫與氫氣酸反應所得之粉末，再混合氧化銦所得之粉末； 5 (4)氧化銦，氟化銦與氧化錫之混合粉末；⑶氧化銦，氧化 錫與氣化錫之混合粉末；⑹氧化銦與氫敦酸反應所得之粉 末’（7)氧化銦與氟化銦之混合粉末；及（8)選自於該（1)〜(？) 所表示之粉末，再經熱處理（通常約於1〇〇〜6〇〇它熱處理） 的粉末。由於經前述之熱處理，可除去殘存於混合粉末中 10之未反應殘留物等，改善燒結體的性狀。例如（1)的粉末係 以水溶液反應之生成粉末，羥基等之殘留物存在之可能性 尚，且其於後續之通電燒結時氣化，故有無法得到緻密的 燒結體之情形。此種情形時，在燒結前約於1〇〇〜6〇(rc· 處理粉末，預先除去殘留物，故於通電燒結時之氣體發生 15 量減少，易於獲得緻密之燒結體。 I因與錫之混合比例，以兩者的合計重量作為基準，錫 含有量約為0〜30%，而以約1〜30%較佳。氧與氟之混合 比例，以兩者的合計重量作為基準，氟含有量約為1〜30% ，而以約2〜20%為佳。 20 混合粉末之粒徑雖未特予限制，為要達成燒結體的高 密度化，通常約為0.01〜10//m，而以約〇·〇5〜5// m較佳。 結 本發明中，以脈衝通電燒結前述的起始原料粉，ϋ通 常從昇溫開始起至燒結結束約為100分鐘或較短之短時間（ 200535970 、、勺10 100刀4里）之燒結操作，藉此可製造高密度1丁〇_ 結體。 70 通包k釔法係對原料粉末於加壓加熱下施加脈衝電流 來進仃之燒結方法。更具體而言，在本發明中，採用通電 5燒結（亦稱為脈衝通電燒結、脈衝大電流燒結、放電電聚燒 結、放電燒結）等之ON_OFF脈衝通電之燒結法，且預先將 放入於預疋杈具内之原料粉末加壓成為壓粉體，並且在該 壓粉體於脈衝狀電流通電之同時，控制該尖輋電流與脈衝 寬度並且控制材料溫度，可進行壓縮燒結。 10 树明中’對於含有銦、錫、氧與II之混合原料粉末 壓粉體，以例如通常約16〜6〇MPa，較佳約2〇〜5〇Mpa之壓 力，施加例如約2000〜10000A，較佳約5〇〇〇〜8〇〇〇a之直 流脈衝電流，在從昇溫開始起至燒結結束為止約1〇〇分鐘或 100分鐘以内之短時間内，可製作高密度F_IT〇燒結體。燒 15結時之溫度可考慮原料之組成，原料粉之粒徑及粒徑分布 ，燒結體之大小，加壓力，施加電流量等來選擇即可，但 通常約為900〜1400°c，且以約1000〜13〇(rc較佳。 本發明之較佳實施形態中，使用通電燒結（，，放電電漿 燒結”或’’Spark- Plasma- Sintering”，亦可稱sps)用枣置，進 2〇行含有銦、錫、氧與氟之原料粉末壓粉體之燒結。用以實 施該SPS法之放電電聚燒結機及其作動原理等係揭示在例 如專利第3007929號說明書（特開平1〇〜251〇7〇號公報）等中 〇 本發明中，例如工模使用石墨時，所得的燒結體之表 11 200535970 面附近，有可能含有工模成分之石墨。此種在燒結體表面 附近所含之石墨等不純物，可藉由研磨燒結體表面，或在 大氣中熱處理而輕易去除。 根據本發明方法所得之含氟銦一錫氧化物燒結體，具 5 有以組成式Ini_xSnxFyOz表示之組成。該組成式中，通常X 及y各在約為〇$x$l及0Sy$0.3之範圍内，z為以z=(x_y + 3)/2所規定之值。 【實施例】 以下顯示實施例及比較例，使本發明之特徵更加明確 10 ° 再者，下述之實施例及比較例中，銦源係使用粒徑約i 〜5//m之氧化銦(ln2〇3)粉末，而錫源係使用粒徑約1〜 m之氧化錫（Sn02)粉末。 【貫施例1】 15 起始原料粉末之調_ 首先，將氧化銦約305g及氧化錫約46g均勻混合後，在 黾爐以1400 C，培燒2小時。該燒成物放入市售的氫氣酸( 濃度約為47%)之1〇倍稀釋溶液約7〇〇mL中，於具排氣設備 的排煙櫃中一邊攪拌，一邊以約8〇它加熱，蒸發乾固。所 20得固形物於電爐以5〇〇°C，處理2小時後，粉碎混合作為起 始原料粉末。 燒結體之製作 通電燒結時，使用放電電漿燒結裝置(住友石碳礦業股 份有限公司製，” SPS — 3 20MK—IV，，）。另工模使用石墨製 12 200535970 ，内徑10cm之圓筒形物。該工模内均勻放入前述所得之起 始原料粉末約350g。在上下鋪滿氧化鋁粉約10g，且約施加 30MPa之壓力，於燒結室内脫氣至約lOMPa。其次，在工模 内約使用1000〜6000A之直流脈衝電流，約以20°C/分鐘之 5 昇溫速度加熱原料周邊至預定溫度1000〜1200°C。維持於 此種狀態約30分鐘後，停止施加電流及加壓，並將生成的 燒結體冷却至室溫，再使燒結室内回復至大氣壓，取出燒 結生成物。 所得之燒結生成物均呈直徑約10cm，厚度約7mm之圓 10 盤狀。其次，藉由研磨去除各燒結生成物之上下兩面所存 在之氧化鋁層，以獲得深藍綠色之圓盤狀燒結體。 所得各燒結體之密度係如第1圖所示，例如，1200°C之燒 結體為6.4g/cm3，而以ITO之理論密度（約7.1g/cm3)為基 準，則約相當為90%。該1200°C之燒結體，從第2圖之X射 15 線繞射圖形可知，係ITO與InOF之混合物(F—ITO)。該燒結 體之元素分析結果如第1表所示，錫含有量（Sn/Sn + In)約 為10%，而氟含有量(F/F+O)約為4%。 第1表Fluorine-containing high density made of hot money knots other than 4 0 10 [Solid package cold type] Detailed description of preferred embodiments The following describes in detail the starting materials used in the method of the present invention, the sintering method, and the obtained Sintered body and so on. Starter | 15 Na Raw material powder for each ingredient. For example, the source of indium may be, for example, indium oxide, indium chloride, acid steel, sulfuric acid steel, gasification: ' Examples of the tin source include tin oxide, tin chloride, tin lignostearate, tin sulfate'tin fluoride, and desert tin. Examples of the fluorine source include hydrogen acid, indium fluoride, tin fluoride, ethidium fluoride, and the like. 20 As the starting material, a > kun compound blended with these component raw materials, or reaction products between the component raw materials, or powders generated by heat or hydrothermal treatment of the reaction products can be used. The proportions of the fluorine component, the indium component, and the tin component in the starting material can be appropriately selected according to the necessary composition of the ingredients depending on the thickness. 200535970 Although there are no particular restrictions on the starting materials, the preferred mixed powders can be, for example, osmium indium-tin oxide money gas-like powder; rhenium oxide powder obtained from the gas spot acid reaction, and powder obtained by mixing tin oxide; (3) Powder obtained by reaction of tin oxide with hydrogen acid, and powder obtained by mixing indium oxide; 5 (4) Powder of mixed powder of indium oxide, indium fluoride, and tin oxide; (3) Powder of mixed powder of indium oxide, tin oxide, and vaporized tin;粉末 The powder obtained by the reaction of indium oxide and hydrotonic acid '(7) a mixed powder of indium oxide and indium fluoride; and (8) selected from the powders represented by (1) ~ (?), And then heat-treated (usually It is heat-treated (about 100 ~ 600) powder. By the aforementioned heat treatment, unreacted residues and the like remaining in the mixed powder 10 can be removed, and the properties of the sintered body can be improved. For example, the powder of (1) is a powder produced by reaction with an aqueous solution, and residues of hydroxyl groups and the like may exist, and it may be vaporized during subsequent electric sintering, so that a dense sintered body may not be obtained. In this case, before sintering, the powder is treated at about 100 ~ 60 (rc ·, the residue is removed in advance, so the amount of gas generated during electric sintering is reduced, and it is easy to obtain a dense sintered body. The mixing ratio is based on the total weight of the two. The tin content is about 0 to 30%, and preferably about 1 to 30%. The mixing ratio of oxygen and fluorine is based on the total weight of the two. The content is about 1 to 30%, and preferably about 2 to 20%. 20 Although the particle size of the mixed powder is not particularly limited, in order to achieve high density of the sintered body, it is usually about 0.01 to 10 // m In the present invention, the aforementioned starting material powder is sintered by pulse current. Generally, rhenium is about 100 minutes or shorter from the start of the temperature rise to the end of the sintering. The sintering operation of time (200535970, spoon, 10, 100 knives, 4 miles) can be used to produce a high-density 1-but __ body. 70 Tong Bao k yttrium method applies a pulse current to the raw material powder under pressure heating Sintering method. More specifically, in the present invention, energization 5 sintering (also known as pulse energization sintering) is used. , Pulse high-current sintering, discharge electropolymerization sintering, discharge sintering) and other ON_OFF pulse energization sintering methods, and the raw material powder placed in the pre-clamp is pressed into a compacted body in advance, and the compacted body While the pulsed current is energized, the sintering current and pulse width can be controlled, and the material temperature can be controlled. Compression sintering can be performed. 10 Shumingzhong 'For powdered powders containing mixed raw materials containing indium, tin, oxygen and II, for example, Usually a pressure of about 16 to 60 MPa, preferably about 20 to 50 MPa. A DC pulse current of, for example, about 2000 to 10,000 A, preferably about 5000 to 800,000a is applied. High-density F_IT0 sintered body can be produced in a short time of about 100 minutes or less than 100 minutes until the end of sintering. The temperature at the time of firing 15 junctions can consider the composition of the raw material, the particle size and particle size distribution of the raw material powder, and sintering. The size of the body, the pressure, and the amount of current to be applied may be selected, but usually about 900 to 1400 ° C, and preferably about 1000 to 13 ° (rc is preferred. In a preferred embodiment of the present invention, electric sintering is used (,, discharge plasma sintering Or "Spark-Plasma-Sintering", also known as sps), using jujube set, and sintering powder powders containing raw material powder containing indium, tin, oxygen and fluorine in 20 rows. Used to implement the discharge power of the SPS method The poly sintering machine and its operating principle are disclosed in, for example, Patent No. 3007929 (Japanese Patent Application Laid-Open Nos. 10 to 25107) and the like. In the present invention, for example, when graphite is used as a mold, a table of a sintered body is obtained. 11 200535970 There may be graphite in the mold near the surface. Impurities such as graphite contained near the surface of the sintered body can be easily removed by grinding the surface of the sintered body or heat treatment in the atmosphere. The fluorine-containing indium-tin oxide sintered body obtained according to the method of the present invention has a composition represented by a composition formula Ini_xSnxFyOz. In this composition formula, usually X and y are each within a range of about 0 $ x $ l and 0Sy $ 0.3, and z is a value prescribed by z = (x_y + 3) / 2. [Examples] Examples and comparative examples are shown below to make the features of the present invention more clear. 10 In addition, in the following examples and comparative examples, the indium source uses indium oxide with a particle diameter of about i to 5 // m. (ln2 03) powder, and the tin source is a tin oxide (Sn02) powder having a particle diameter of about 1 to m. [Example 1] 15 Preparation of starting material powder_ First, about 305 g of indium oxide and about 46 g of tin oxide were mixed uniformly, and then baked in an oven at 1400 C for 2 hours. The fired product was put into about 700 mL of a 10-fold diluted solution of a commercially available hydrogen acid (concentration of about 47%), and stirred in a fume hood with an exhaust device while about 80% of it was stirred. Heat and evaporate to dryness. The obtained solid was treated in an electric furnace at 500 ° C for 2 hours, and then pulverized and mixed as a starting material powder. For the sintered body, the electric plasma sintering device is used for electric sintering (manufactured by Sumitomo Stone Carbon Mining Co., Ltd., “SPS — 3 20MK — IV,”). The mold is made of graphite 12 200535970, a cylinder with an inner diameter of 10 cm. About 350g of the starting material powder obtained previously was uniformly placed in the mold. About 10g of alumina powder was spread on the top and bottom, and a pressure of about 30MPa was applied, and the gas was degassed to about 10MPa in the sintering chamber. In the mold, a DC pulse current of about 1000 to 6000 A is used, and the periphery of the raw material is heated to a predetermined temperature of 1000 to 1200 ° C at a heating rate of 5 ° C / minute. After maintaining in this state for about 30 minutes, stop applying current and applying heat. Pressure, and the resulting sintered body is cooled to room temperature, and then the sintering chamber is returned to atmospheric pressure, and the sintered products are taken out. All the obtained sintered products are in the shape of a circle of 10 disks with a diameter of about 10 cm and a thickness of about 7 mm. Grinding removes the alumina layers present on the upper and lower sides of each sintered product to obtain a dark blue-green disc-shaped sintered body. The density of each sintered body is shown in Figure 1, for example, sintered at 1200 ° C. The body is 6.4g / cm3, and it is about 90% based on the theoretical density of ITO (about 7.1g / cm3). The 1200 ° C sintered body has a 15-ray diffraction pattern from X-ray in Fig. 2 It is known that it is a mixture of ITO and InOF (F-ITO). The elemental analysis results of this sintered body are shown in Table 1. The tin content (Sn / Sn + In) is about 10%, and the fluorine content (F / F + O) is about 4%. Table 1
Sn/(In + Sn) F/(〇 + F) 實施例1 10.4% 3.9% 實施例2 9.0% 〇.〇% 從該結果顯示，根據本發明可製作高密度F—ITO燒結 體。 13 20 200535970 薄膜之形成 使用前述在燒結溫度12〇〇°C製成之F—ΙΤΟ燒結體作為 革巴’並於玻璃基板上以濺鍍法進行成膜。在成膜中之基板 溫度為20CTC或300°C，濺鍍電力=DC : 200W，成膜壓力= 5 3mTorr，成膜時間=15分鐘等情形ητ進行。 所得的膜之膜厚、比電阻、表面高低差、表面平滑度 及透光度係如第2表所示。比電阻約為2〜6x10 —4Qcm， 550nm之透光為89〜90%，該等數值與使用傳統ITO靶之薄 膜的報告值【1x10—4Qcm及91%;R丄atz，K. Michael，andM. 10 Scherer，Jpn· J. Appl· Phys·, 30, L149( 1991)】大致為同等值 第2表 成膜 溫度 薄膜厚 度 d(nm) 比電阻p (l〇~4Qcm) 表面高低 差△Z(nm) 表面平滑度 △ Z/d(%) 透光度 T(%)(550nm) 300°C 147.9 2.829 13.235 8.9 89.84 200°C 148.7 5.884 6.179 4.2 88.92 【比較例2】 成膜 溫度 薄膜厚 度 d(nm) 比電阻p (l(T4Qcm) 表面高低 差 AZOm) 表面平滑度 △ Z/d(%) 透光度 T(%)(550nm) 300°C 153.9 1.731 54.981 35.7 89.92 200°C 151.6 3.214 45.898 30.3 86.47Sn / (In + Sn) F / (〇 + F) Example 1 10.4% 3.9% Example 2 9.0% 0.00% From the results, it is shown that a high-density F-ITO sintered body can be produced according to the present invention. 13 20 200535970 Thin film formation The aforementioned F-ITO sintered body made at a sintering temperature of 12,000 ° C was used as a Geba 'and formed on a glass substrate by sputtering. The substrate temperature during film formation is 20CTC or 300 ° C, sputtering power = DC: 200W, film formation pressure = 53mTorr, film formation time = 15 minutes, and so on. The film thickness, specific resistance, surface level difference, surface smoothness, and light transmittance of the obtained film are shown in Table 2. The specific resistance is about 2 ~ 6x10-4Qcm, and the light transmission at 550nm is 89 ~ 90%. These values are compared with the reported values of thin films using traditional ITO targets [1x10-4Qcm and 91%; R 丄 atz, K. Michael, andM 10 Scherer, Jpn · J. Appl · Phys ·, 30, L149 (1991)] Approximately the same value. Table 2 Film formation temperature Film thickness d (nm) Specific resistance p (l0 ~ 4Qcm) Surface height difference △ Z (nm) Surface smoothness △ Z / d (%) Transmittance T (%) (550nm) 300 ° C 147.9 2.829 13.235 8.9 89.84 200 ° C 148.7 5.884 6.179 4.2 88.92 [Comparative Example 2] Film formation temperature Film thickness d (nm) Specific resistance p (l (T4Qcm) Surface height difference AZOm) Surface smoothness △ Z / d (%) Transmittance T (%) (550nm) 300 ° C 153.9 1.731 54.981 35.7 89.92 200 ° C 151.6 3.214 45.898 30.3 86.47
15 再者，所得薄膜之AZ/d(表面平滑度）約為4〜9%， 與一般ITO靶所產生之薄膜值（約20%以上）相比，其表面平 滑度顯著提高。 從以上的結果可知，以本發明方法所得之F—ITO燒結 14 200535970 體，作為製作表面平滑性極高的透明導電膜之濺鍍靶時， 顯然可發揮優良之效果。 【實施例2】 將氧化銦粉末（約305g)及氫氟酸(市售的濃度約為47% 5溶液之10倍稀釋溶液約3500mL)反應後，約在8〇艺蒸發乾固 後调製成粉末，再混合氧化錫（約46g)，且將混合物於電爐 中以500。(3熱處理2小時。 以前述所得熱處理生成物作為起始原料，根據與實施 例1相同之通電燒結法，以120(rc，燒結3〇分鐘。 ° 所得燒結體元素分析結果，Sn/(In+Sn)= 10.9%，F /(0 + F)= 18.5% 〇 前述燒結體作為革巴材料，根據與實施例_同之通電燒結 法，在玻璃基板上進行成膜。所得的膜特性如第3表所示。 第3表15 Furthermore, the AZ / d (surface smoothness) of the obtained film is about 4-9%, and the surface smoothness is significantly improved compared with the film value (about 20% or more) produced by a general ITO target. From the above results, it is clear that the F-ITO sintered body 14 200535970 obtained by the method of the present invention can obviously exert excellent effects as a sputtering target for producing a transparent conductive film with extremely high surface smoothness. [Example 2] After reacting indium oxide powder (about 305 g) and hydrofluoric acid (commercially available concentration of about 47% 5 solution of 10 times diluted solution of about 3500 mL) after reaction, it was prepared after about 80% evaporation and solidification. Into powder, and then mix tin oxide (about 46g), and put the mixture in an electric furnace to 500. (3 heat treatment for 2 hours. Using the obtained heat treatment product as a starting material, sintering was performed at 120 ° C for 30 minutes according to the same electric sintering method as in Example 1. ° Elemental analysis result of the obtained sintered body, Sn / (In + Sn) = 10.9%, F / (0 + F) = 18.5% 〇 The aforementioned sintered body was used as a leather material, and the film was formed on a glass substrate according to the same electric sintering method as in Example_. The obtained film characteristics are as follows Shown in Table 3. Table 3
【實施例3】 將氧化銦粉末（約290g)，及氟化銦粉末（約25g)與氧化 錫粉末（約46g)均勻混合後，於電爐中以5〇(rc熱處理2祕 20後調製成起始原料财末根據與實施朗目同之 通電燒結法，以120(rc，燒結30分鐘而獲得燒結體。 燒結體元素分析結果，確認為Siv/(In+Sn)=i〇4%， 15 200535970 F/(0 + F))=8 。 ^述燒結體作為乾材料’根據與實施例1相同之方法， 在玻璃基板上進行成膜。所得的膜特性如第4表所示。 第4表 成膜 溫度 薄膜厚 度 d(nm) 比電阻 (10'4Ωοιη) 表面高低 差簡腿） 表面平滑度 △Z/d(%) 透光度 T (%)550nm) 100°c 150.9 9.830 7.017 4.6 87.85 【實施例4】 將氧化銦粉末（約250g)及氫氟酸(市售的濃度約為47% 溶液之10倍稀釋溶液約400mL)反應後，約在80°C蒸發乾固 後調製成粉末，並於電爐中&5〇〇°c熱處理2小時。 1〇 以前述所得熱處理生成物作為起始原料，根據與實施例 1相同之通電燒結法，以1200°C，燒結30分鐘獲得燒結體。 所得燒結體元素分析結果，Sn/(In+Sn) = 〇.〇%，F/ (〇 + F) = 8.0% 〇 别述燒結體作為革巴材料，根據與實施例丨相同之通電燒結 15法，在玻璃基板上進行成膜。所得的膜特性如第5表所示。 第5表 成膜 溫度 薄膜厚 度 d(nm) 比電阻p (l〇'4Qcm) 表面南低 差△Z(nm) 表面平滑度 △Z/d(%) 透光度 T(%)(550nm) 100°c 145.0 3.674 12.75 8.8 88.75 【比較例1】 將氧化麵約305g與氧化錫約46g之混合粉末，經1400 16 200535970 °〇熱處理後，添加氫氟酸溶液（濃度約4.7%)，經蒸發乾固 後，將以500。(：熱處理後之原料混合物約350g，均勻放入直 徑10cm之圓筒型工模，經約5〇Mpa加壓成型後，從治具取 出成型體，再於一般電爐中以HOCTC，燒結2小時。 5 所彳于燒結體呈直徑約10cm，厚度約1.4cm之圓盤狀，其 密度約相當於ΓΓΟ理論密度（約7.1g/cm3)的45%之低值。該 燒結體可如第2圖所示之X射線繞射圖形所示般地僅由IT〇 構成。 再者，進行燒結體元素分析時，如同前述之第丨表所示 10 ’可知幾乎不含有氟。據推測其原因是在1400°C燒結時氟 脫離的緣故。 從前述結果可知，一般電爐等之燒結方法無法製作F — ITO燒結體。 【比較例2】 15 使用不含氟之一般ITO靶（密度6.7g/cm3，相對密度約 94%) ’與實施例丨相同之條件下，在玻璃基板上進行成膜 。所得之膜的特性係顯示於前述第2表中。 膜之比電阻及透光度係顯示與實施例丨之膜大致相同 之值，但當表面平滑度（ΑΖ/οΙ)為30%以上，與實施例1 20之情形相比，降低了 3倍以上，無法獲得導電性，透光度及 表面平滑性均高之薄膜。X射線繞射圖形 【圖式簡單說明】 第1圖是顯示在以實施例1中以通電燒結法製成之燒結 體中，密度與燒結溫度之相關性的圖。 17 200535970[Example 3] After indium oxide powder (about 290 g), indium fluoride powder (about 25 g) and tin oxide powder (about 46 g) were uniformly mixed, they were heat-treated in an electric furnace at 50 (rc for 20 minutes) and then prepared into At the end of the starting material, the sintered body was obtained at 120 (rc, sintered for 30 minutes according to the same electric sintering method as that used for Langmu. The elemental analysis of the sintered body confirmed that Siv / (In + Sn) = 104%. 15 200535970 F / (0 + F)) = 8. ^ The sintered body was used as a dry material. 'Film formation was performed on a glass substrate according to the same method as in Example 1. The obtained film characteristics are shown in Table 4. Table 4 Film formation temperature Film thickness d (nm) Specific resistance (10'4Ωοιη) Surface height difference leg) Surface smoothness △ Z / d (%) Transmittance T (%) 550nm) 100 ° c 150.9 9.830 7.017 4.6 87.85 [Example 4] After reacting indium oxide powder (about 250 g) and hydrofluoric acid (commercially available solution with a concentration of about 47% of a solution of about 10 times a diluted solution of about 400 mL), it was evaporated to dryness at about 80 ° C to prepare a solution. The powder was heat-treated in an electric furnace at 500 ° C for 2 hours. 10 Using the obtained heat-treated product as a starting material, a sintered body was obtained by sintering at 1200 ° C for 30 minutes according to the same electric sintering method as in Example 1. Elemental analysis results of the obtained sintered body, Sn / (In + Sn) = 0.00%, F / (〇 + F) = 8.0% 〇 Other sintered bodies were used as the leather materials, and were sintered according to the same electric current as in Example 丨 15 Method, forming a film on a glass substrate. The obtained film characteristics are shown in Table 5. Table 5 Film formation temperature Film thickness d (nm) Specific resistance p (10'4Qcm) Surface south difference △ Z (nm) Surface smoothness △ Z / d (%) Transmittance T (%) (550nm) 100 ° c 145.0 3.674 12.75 8.8 88.75 [Comparative Example 1] A mixed powder of about 305 g of oxidized surface and about 46 g of tin oxide was heat-treated at 1400 16 200535970 °°, and a hydrofluoric acid solution (concentration of about 4.7%) was added and evaporated. After drying, it will start at 500. (: About 350g of raw material mixture after heat treatment, uniformly put into a cylindrical mold with a diameter of 10cm, and after pressure molding at about 50Mpa, take out the molded body from the jig, and sinter it in a general electric furnace with HOCTC for 2 hours 5 The sintered body has a disk shape with a diameter of about 10 cm and a thickness of about 1.4 cm, and its density is about 45% of the theoretical density of ΓΓΟ (about 7.1 g / cm3). The sintered body can be as described in Section 2 The X-ray diffraction pattern shown in the figure is composed only of IT0. Further, when elemental analysis of the sintered body was performed, it was found that 10 'as shown in the above table 丨 contains almost no fluorine. It is speculated that the reason is The reason why fluorine is released during sintering at 1400 ° C. From the foregoing results, it can be seen that F-ITO sintered bodies cannot be produced by sintering methods such as general electric furnaces. [Comparative Example 2] 15 A general ITO target containing no fluorine (density 6.7g / cm3) (Relative density: about 94%) 'Under the same conditions as in Example 丨, a film was formed on a glass substrate. The characteristics of the obtained film are shown in the aforementioned Table 2. The specific resistance and transmittance of the film are shown in the same manner as in Example 丨. The film of Example 丨 has approximately the same value, but when the surface smoothness ΑZ / οΙ) is 30% or more, which is reduced by more than 3 times compared to the case of Example 1 20, and a thin film having high conductivity, light transmittance and surface smoothness cannot be obtained. X-ray diffraction pattern [Schematic Brief description] Fig. 1 is a graph showing the correlation between the density and the sintering temperature in the sintered body produced by the electric sintering method in Example 1. 17 200535970
第2圖是顯示由實施例1與比較例1所得之燒結體的X射 線繞射圖形之圖。 【主要元件符號說明】 (無） 18Fig. 2 is a diagram showing X-ray diffraction patterns of the sintered bodies obtained in Example 1 and Comparative Example 1. [Description of Symbols of Main Components] (None) 18