201026819 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種在液晶顯示器（LCD)或電致發光 顯示器（ELD)顯示元件等之中所使用的透明導電膜用的餘 刻液組成物。 【先前技術】 φ 作為在液晶顯示器或電致發光顯示器顯示元件等之 中所使用的透明導電膜，有氧化銦錫（IT〇)、氧化銦鋅 (ΙΖΟ)、氧化銦、氧化錫、氧化辞等，其中ΙΤ〇膜及ιζ〇 膜被廣泛地使用。作為透明導電膜的圖案化方法，通常的 方法係在玻璃等的基板上，先藉由濺鍍法等形成透明導電 膜後，藉由光微影法形成光阻圖案，然後利用將透明導電 膜蝕刻來形成電極圖案。 作為透明導電膜的蝕刻液，先前有提案一種蝕刻液， ®其含有：（1)氣化鐵水溶液、⑺蛾酸水溶液、（3)鱗酸水溶 液、（4)鹽酸_硝酸混合液（王水）及（5)草酸水溶液等的溶解 氧化銦的成分。 作為ΙΊΌ膜，先前係制比電阻或透射率等的作為 透明導電膜的基本特性良好之多结自ΙΤ〇膜，但是近年 來，伴隨著顯示元件的大型化、高精細化、高性能化，被 要求加工精確度的提升、製程溫度的低溫化、表面平拉性 的提升等，因而作為滿足該等要求之透明導電膜係使用 3 201026819 非晶質ITO膜或IZO膜。 作為非晶質ΙΤΟ媒或ίζο媒等的透明導電膜之钱刻 液’草酸水溶液由於價廉且安定性優良，而且具有實用性 的姓刻速度且對Α1配線的損傷小’所以被廣泛地使用。 但是’使用草酸水溶液來蝕刻透明導電膜時，會有容易析 出草酸銦的結晶這樣的問題。 通常’因為蝕刻液係在蝕刻裝置内使其重複循環而使 Φ 用，所以若使用含有草酸的蝕刻液來蝕刻透明導電膜時， 因為蝕刻液中的銦濃度上升，致使草酸銦的結晶容易析 出。一旦析出時’會以其作為核而進行結晶成長並形成粗 大的結晶物，並黏附在裝置内》其結果，會發生裝置的動 作不良、過濾器的網眼堵塞或是對基板造成損傷等之問 題。 因為草酸銦係具有相當難溶性的鹽，難以在蝕刻液中 再溶解，又’亦難以在水中溶解。因此，為了將裝置内所 ® 析出的結晶物除去’只有在將裝置内的蝕刻液抽除後，藉 由手工作業除去或是藉由藥液溶解除去等的某些方法來 除去，但是這會造成生產量降低及成本提高。又，網眼堵 塞的過濾器，可藉由某些方法來除去結晶物或是不得不將 過濾器更新’但是這亦會造成生產量降低及成本提高。如 此’使用含有草酸的蝕刻液之透明導電膜的蝕刻時，草酸 銦的結晶容易析出’將成為一個重大的問題。 作為該問題的對策’可舉出使用前述草酸以外之溶液 氧化銦之成分，但是氣化鐵水溶液，其侧面蝕刻量大且具 201026819 有含有對半導體造成不良影響的Fe之缺點。又，碘酸水 /谷液，不但容易游離而缺乏安定性，而且有昂貴之缺點。 而且，磷酸水溶液，會損傷A1配線，且具有容易產生蝕 刻殘渣之缺點。又，鹽酸-硝酸混合液（王水），其經時變 化顯著’且具有製程控制困難而無法輪送之缺點。 而且，使用以草酸作為主成分的餘刻液來餘刻非晶質 ITO膜或IZO膜等的透明導電膜時，會有容易產生蝕刻殘 渣之問題。 ❿ 作為解決該問題之方法’本發明人，已提案揭示一種 ITO膜用蝕刻液組成物（專利文獻1}，其係含有草酸、選 自由聚磺酸化合物及聚氧乙烯-聚氧丙烯嵌段共聚物所組 成群組之1種或2種以上的化合物。又，已提案揭示一種 含有草酸及胺基羧酸或三乙醇胺之ITO膜用蝕刻液組成 物（專利文獻2)，一種含有草酸及缓酸之非晶質ιτο膜用 蝕刻劑（專利文獻3); —種含有含全氟烷基的磷酸酯鹽、 ❹草酸及水之ΙΤΟ膜及ΙΖΟ膜用蝕刻液組成物（專利文獻4) 及一種含有草酸及氟系界面活性劑之ΙΤ〇膜及ΙΖ〇膜用 蝕刻液組成物（專利文獻5)等，雖然該等含有草酸之餘刻 液經確認具有實用性的蝕刻速度且具有能夠抑制蝕刻殘 渣之效果，但是前述草酸銦的結晶析出的問題，係未被完 全認識而仍然是未解決的狀態。 而且’作為未含有草酸的餘刻液，有提案揭示一種由 含有胺基磺酸、聚氧乙烯烷基醚硫酸鹽、聚氧乙稀烧基苯 基醚硫酸鹽或聚氧化烯烷基醚磷酸酯的水溶液所組成之 5 201026819 非晶質ITO膜用㈣劑（專利文獻6)等雖㈣含未含 草酸的㈣液，其草酸銦的結晶未析出，且定 防止蝕刻殘渣之效果，但是與含有草酸的水溶液比較：會 有蝕刻速度慢且生產量降低等之問題。201026819 VI. Description of the Invention: [Technical Field] The present invention relates to a composition for a transparent conductive film used in a liquid crystal display (LCD) or an electroluminescence display (ELD) display element or the like Things. [Prior Art] φ is a transparent conductive film used in a display element or the like of a liquid crystal display or an electroluminescence display, and includes indium tin oxide (IT〇), indium zinc oxide (yttrium), indium oxide, tin oxide, and oxidized words. Etc., in which the ruthenium film and the ζ〇 film are widely used. As a method of patterning a transparent conductive film, a usual method is to form a transparent conductive film by sputtering or the like on a substrate such as glass, and then form a photoresist pattern by photolithography, and then use a transparent conductive film. Etching to form an electrode pattern. As an etching solution for a transparent conductive film, an etching liquid has been proposed, which contains: (1) an aqueous solution of an iron oxide, (7) an aqueous solution of molybdic acid, (3) an aqueous solution of scaly acid, and (4) a mixture of hydrochloric acid and nitric acid (aqua regia) And (5) a component of dissolved indium oxide such as an aqueous oxalic acid solution. As a ruthenium film, a ruthenium film which is excellent in basic characteristics as a transparent conductive film, such as a resistance and a transmittance, has been conventionally formed, but in recent years, with the increase in size, high definition, and high performance of display elements, It is required to improve the processing accuracy, to lower the temperature of the process, and to improve the flatness of the surface. Therefore, as a transparent conductive film that satisfies such requirements, 3 201026819 amorphous ITO film or IZO film is used. The etched liquid oxalic acid solution of the transparent conductive film, such as an amorphous or a medium, is widely used because it is inexpensive and has excellent stability, and has a practical surname speed and little damage to the Α1 wiring. . However, when the transparent conductive film is etched using an aqueous oxalic acid solution, there is a problem that crystals of indium oxalate are easily precipitated. In general, since the etching liquid is repeatedly circulated in the etching apparatus and used for Φ, when the transparent conductive film is etched using an etching solution containing oxalic acid, the crystal of indium oxalate is easily precipitated because the concentration of indium in the etching liquid rises. . Once precipitated, 'the crystal will grow as a core and form a coarse crystal, and it will adhere to the inside of the device." As a result, malfunction of the device, clogging of the filter, or damage to the substrate may occur. problem. Since indium oxalate has a salt which is relatively insoluble, it is difficult to redissolve in the etching liquid, and it is also difficult to dissolve in water. Therefore, in order to remove the crystals precipitated in the apparatus, 'only after removing the etching liquid in the apparatus, it is removed by manual work or by some means such as dissolution of the chemical solution, but this causes Reduced production and increased costs. Also, mesh plugging filters can be used to remove crystals or have to be renewed by filters' but this also results in reduced throughput and increased costs. When etching using a transparent conductive film containing an etchant containing oxalic acid, crystallization of indium oxalate is likely to precipitate, which becomes a major problem. The countermeasure for this problem is a component in which indium oxide is used as the solution other than oxalic acid. However, the vaporized iron aqueous solution has a large amount of side etching and has a disadvantage of containing Fe which adversely affects the semiconductor in 201026819. Moreover, iodic acid water/gluten solution is not only easy to dissociate but lacks stability, and has the disadvantage of being expensive. Further, the phosphoric acid aqueous solution may damage the A1 wiring and have a drawback that etch residue is liable to occur. Further, the hydrochloric acid-nitric acid mixed solution (Aqua regia) has a remarkable change over time and has a drawback that it is difficult to carry out the process control and cannot be rotated. Further, when a transparent conductive film such as an amorphous ITO film or an IZO film is left by using a residual liquid containing oxalic acid as a main component, there is a problem that etching residue is likely to occur. As a method for solving this problem, the present inventors have proposed an etchant composition for an ITO film (Patent Document 1) which contains oxalic acid and is selected from a polysulfonic acid compound and a polyoxyethylene-polyoxypropylene block. One or two or more compounds of the group of copolymers. Further, it has been proposed to disclose an etchant composition for an ITO film containing oxalic acid, an aminocarboxylic acid or triethanolamine (Patent Document 2), which contains oxalic acid and An etchant for an acid-like amorphous ιτο film (Patent Document 3); an etchant composition containing a perfluoroalkyl group-containing phosphate salt, shikimic acid, and water, and an etchant for a ruthenium film (Patent Document 4) And an etchant composition for ruthenium film and ruthenium film containing oxalic acid and a fluorine-based surfactant (Patent Document 5), etc., and the etchant containing oxalic acid has a practical etching rate and is capable of Although the effect of suppressing the etching residue is suppressed, the problem of crystal precipitation of the indium oxalate is not fully understood and remains unresolved. Moreover, as a residual liquid containing no oxalic acid, there is a proposal to disclose a An aqueous solution containing an aminosulfonic acid, a polyoxyethylene alkyl ether sulfate, a polyoxyethylene alkyl phenyl ether sulfate or a polyoxyalkylene alkyl ether phosphate. 5 201026819 Amorphous ITO film (4) (Patent Document 6), etc. (4) In the case of (iv) liquid containing no oxalic acid, the crystal of indium oxalate is not precipitated, and the effect of preventing etching residue is determined. However, compared with the aqueous solution containing oxalic acid, the etching rate is slow and the production amount is lowered. The problem.
如上述，以草酸以外之溶解氧化銦的無機酸作為主成 分而成之原有的蝕刻液時，就蝕刻特性及蝕刻液的安定性 等而言，在使用上具有重大的問題，未存在有比得上以草 酸作為主成分的蝕刻液匹敵的優良特性之蝕刻液。又以 草酸作為主成分的蝕刻叫能夠維持其優良特性且能夠 抑制草酸銦的結晶析出之蝕刻液，係尚未存在。 因此’目前作為將以草酸作為主成分的银刻液，使用 於含銦之透明導電膜的蝕刻製程時之結晶#出對策，現狀 係只有進行將使用後的餘刻液藉由奈米過濾膜過渡而再 生之方法、裝置的定期性維修、及製成結晶不容易析出的 裝置結構等的在裝置方面的對策（專利文獻7及非專利文 獻1)。 [專利文獻1]曰本特開2002_164332號公報 [專利文獻2]曰本特開2〇〇2_〇333〇4號公報 [專利文獻3]日本特開2〇〇3-3〇6676號公報 [專利文獻4]日本特開2〇〇5 1 16542號公報 [專利文獻5]曰本特開2〇〇5_244〇83號公報 [專利文獻6]日本特開2002-367974號公報 [專利文獻7]曰本特開2006_013158號公報 [非專利文獻1] 2GG7年12月17日第i版、情報_^ 201026819 公司發行「最近透明導電膜大全集」第556〜557頁 【發明内容】 [發明所欲解決之問題] 因此，本發明之課題係提供一種透明導電膜用敍刻液 組成物，針對在液晶顯示器等之中所使用的非晶質ιτ〇 及ιζο等的透明導電膜之蝕刻處理，能夠防止草酸銦的 _結晶析出而有助於提高生產量及降低成本。 [解決問題之技術手段] 為了解決上述的課題，本發明人在重複專心研究之 •中’發現含有草酸及鹼性化合物之透明導電膜用蝕刻液組 成物’具有以草酸作為主成分的蝕刻液之優良的特性且能 夠抑制草酸銦的結晶析出，進一步進行研究後之結果，而 完成了本發明。 亦即，本發明係有關於一種含有草酸及鹼性化合物 ® (但是三乙醇胺除外）之透明導電膜用蝕刻液組成物。 又，本發明係有關於前述透明導電膜用蝕刻液組成 物，其中鹼性化合物係選自由氫氧化第四級銨類、鹼金屬 類的氫氧化物、烷醇胺類（但是三乙醇胺除外）及羥基胺類 所组成群組之1種或2種以上。 而且，本發明且係有關於前述透明導電膜用蝕刻液組 成物，其中pH為1.1〜5.0。 又，本發明係有關於前述透明導電膜用蝕刻液組成 物，其係進而含有選自由聚磺酸化合物、聚氧乙烯聚氧 7 201026819 丙烯嵌段共聚物及磺酸鹽型陰離子界面活性劑所組成群 組之1種或2種以上的化合物。 而且，本發明係有關於前述透明導電膜用蝕刻液組成 物，其係進而含有1種或2種上的水溶性聚合物。 又’本發明且係有關於前述透明導電膜用蝕刻液組成 物，其係使用於含有氧化鋼的透明導電膜之餘刻。 而且，本發明係有關於一種透明導電膜的蝕刻方法， 參其係使用前述透明導電膜用蝕刻液組成物。 草酸銦的結晶容易析出之原因，被認為係銦在草酸水 溶液中的溶解度低。依照本發明人之調查，清楚明白銦在 草酸水溶液令的溶解量係300ppm左右’其以上的濃度時 草酸銦的結晶容易析出。亦即認為使銦在草酸水溶液令的 溶解量增加-事，係與抑制草酸鋼的結晶析出有關聯。 本發明的透明導電膜用蝕刻液組成物，藉由含有鹼性 化合物，能夠抑制草酸銦的結晶析出之理由，雖然尚未清 ©楚’可認為係因為隨著液中的阳變高，成為相對於姻， 草酸更容易與OH基或胺、第4級錄生成錯合物之條件， 所以能夠抑制草酸銦的生成，結果能夠增加銦的溶 [發明之功效] 藉由本發明的透明導電膜用敍刻液組成物，因為能夠 在透明導電膜的蚀刻製程時’抑制草酸銦的結晶析出所 以能夠延長蝕刻液的液體使用期限且能夠減輕除去結晶 的作業，因而能夠提升生產量及降低成本。 8 201026819 【實施方式】 以下，詳細地說明本發明。本發明的透明導電膜，係 由氧化銦錫（ITO)、氧化銦鋅（IZO)及氧化銦等所構成之透 明導電膜’特別是由非晶質ITO及IZO膜所構成之透明 導電膜。又，本發明的透明導電膜用蝕刻液組成物，係在 液晶顯示器及電致發光顯示器等的製程之上述透明導電 膜的蝕刻製程中所使用的蝕刻液組成物。 在本發明的蝕刻液組成物中所使用的草酸的濃度，係 考慮蝕刻速度在實用方面是充分、草酸的結晶不會析出等 而適當地決定，以0.1〜10重量％為佳’以〇 3〜8重量％ 為更佳，以0.5〜6重量％為特佳。草酸的濃度低時蝕 刻速度降低，草酸的濃度高時，草酸的結晶會有析出之傾 向，草酸的濃度在上述範圍時，能夠得到實用性的蝕刻速 度且不會有草酸的結晶析出而造成保存性或輸送時的障 礙之可能性，乃是較佳。 # 在本發明的蝕刻液組成物中所使用的鹼性化合物，係 考慮銦溶解量及蝕刻速度等而選擇，本發明的蝕刻液組成 物’其特徵係添加鹼性化合物時之蝕刻&度的降低為較 小，且銦溶解量與蝕刻速度的平衡係特別重要。作為在本 發明的蝕刻液組成物中所使用的鹼性化合物典型的可舉 出氫氧化第四級銨類、鹼金屬類的氫氧化物、烷醇胺類（但 是三乙醇胺除外）及羥基胺類等。 具體上’作為氫氧化第四級錢類，可舉出例如氣氧化 四甲銨、氫氧化四乙錄、膽鹼等。 9 201026819 又，作為鹼金屬類的氫氧化物 鈉、氫氧化卸等。 了舉出例如氫氧化 而且，作為貌醇胺類，可舉出··—㈣㈣、二㈣ 可舉出㈣相三糾㈣等。料—㈣胺類， W —乙醇胺、2-甲胺基乙醇、2-乙胺基乙醇、 ❹ ::胺基乙氧基)乙醇、,…丙醇、一丙醇胺二尹 胺基乙醇及該等的鹽等。又’作為二垸醇胺類，可舉出例 如.-乙醇胺、N-甲基二乙醇胺、二丁醇胺及該等的鹽等。 上述燒醇胺類之中’從銦溶解量及钱刻速度等之觀點，可 舉出較佳是一烷醇胺類、二烷醇胺類等可舉出更佳是一 烷醇胺類等，可舉出特佳是一乙醇胺等。 而且，作為經基胺類，可舉出例如：經基胺、n基 經基胺、Ν，Ν·二曱基經基胺、N，义二乙基經基胺、硫酸羥 基胺、鹽酸羥基胺等，可舉出較佳是羥基胺等。 又，該等鹼性化合物，可按照用途而含有〗種或2 種以上》 在本發明的蝕刻液組成物中所使用的鹼性化合物的 濃度，係考慮錮溶解量、草酸銦的結晶析出、蝕刻液組成 物的pH及钱刻速度等而適當地決定，以〇1〜1〇重量〇/〇 為佳，以0.3〜7重量％為更佳，以〇.5〜5重量％為特佳。 鹼性化合物的濃度低時，草酸銦的結晶容易析出，濃度高 時，蝕刻速度會有降低的傾向，鹼性化合物的濃度在上述 範圍時’因為能夠得到充分的防止草酸銦的結晶析出之效 果及實用性的蝕刻速度，乃是較佳β 10 201026819 本發月的蝕刻液組成物的pH，係考慮銦溶解量草 酸銦的結晶析出及韻刻速度等而適當地決定以lko 為佳，以1.2〜4.0為更佳’以13〜3〇為特佳。pH低時 草酸銦的結晶容易析出，pH高時，餘刻速度會有降低的 傾向，PH在上述範圍時，因為能夠得到充分的防止草酸 銦的結晶析出之效果及實用性的蝕刻速度，乃是較佳。 本發明的飯刻液組成物，比較含有草酸及驗性化合物 〇之本發明的組成物的pH與除了未含有驗性化合物以外係 同一組成的組成物的pH時，因添加鹼性化合物而產生的 pH的變化量△ pH ’係考慮銦溶解量、草酸銦的結晶析出 及姓刻速度等而適當地決定，且藉由所添加的驗性化合物 之種類及濃度等來適當地調整。 △PH的範圍以（M〜4.〇為佳，以〇3〜3〇為更佳， 以〇·5〜2.G為特佳。△ pH小時草酸銦的結晶容易析出， △ pH大時蝕刻速度會有降低的傾向，ΔρΗ在上述範圍 _時，因為能夠得到充分的防止草酸銦的結晶析出之效果及 實用性的蝕刻速度，乃是較佳。 本發明的蝕刻液組成物的蝕刻速度，係考慮處理時間 及均勻的蝕刻等而藉由草酸的濃度，加上鹼性化合物的種 類及濃度等來適當地調整。 又，本發明的钱刻液組成物，在不妨礙前述效果的範 圍，能夠進而使其含有用以除去蝕刻殘渣之成分。作為此 種目的所使用的成分，以聚磺酸化合物、聚氧乙烯聚氧 丙烯嵌段共聚物、磺酸鹽型陰離子界面活性劑等為佳。 201026819 作為聚磺酸化合物，可舉出例如：萘磺酸甲醛縮合物 及其鹽、聚苯乙烯磺酸及其鹽、木質磺酸及其鹽等。作為 萘磺酸曱醛縮合物及其鹽，具體上係以RunoxlOOOC、 1500A、IONET D-2、三洋 Levelon PHL(以上、東邦化學 工業股份公司）、LOMAR PWA-40(SAN NOPCO股份公司 製）、Demol N(花王股份公司）、POLITY N-100K(LION 股 份公司）、Labelin FH-P(第一工業製藥股份公司）等的商品 赢 名銷售。作為木質磺酸及其鹽，具體上係以Sorpol 9〇47k(東邦化學工業股份公司）、SunEkis(曰本製紙 CHEMICAL股份公司）等的商品名銷售。該等聚磺酸化合 物之中，含有鈉等的金屬者係不適合使用作為電子工業 用，但是藉由使用離子交換樹脂等進行處理來除去鈉，變 為能夠使用。 聚氧乙烯-聚氧丙烯嵌段共聚物，係因聚氧乙烯與氧 丙稀的比例及分子量而有各種型式，具體上係例如以 • NEWPOL PE系列（三洋化成工業股份公司）、Epan系列（第 一工業製藥股份公司）等的商品名銷售。 作為磺酸鹽型陰離子界面活性劑，可舉出例如：十二 烷基苯磺酸之烷基笨磺酸酯及其鹽、烷基硫酸酯等其鹽、 磺酸基琥拍酸的二烷酯及其鹽、聚氧乙烯烷基醚磺酸及其 鹽、聚氧乙烯烯丙基醚磺酸及其鹽等。其中因為發泡較 少，以聚氧乙烯烷基醚磺酸及其鹽、聚氧乙烯烯丙基醚磺 酸及其鹽為特佳，係以Newcol系列（日本乳化劑股份公司） 等的商品名銷售。又，該等化合物可按照用途而含有1 12 201026819 種或2種以上。 從得到充分的除去蝕刻殘渣的效果之觀點，在本發明 的蝕刻液組成物中所使用的聚磺酸化合物、聚氧乙稀_聚 氧丙烯嵌段共聚物、及/或磺酸鹽型陰離子界面活性劑之 漠度，以0.0001〜1〇重量％為佳，以0 〇〇1〜10重量％為 特佳。 而且，本發明的蝕刻液組成物，在不妨礙前述效果的 φ範圍，能夠進而使其含有用以抑制草酸銦的結晶析出之成 分。作為此種目的所使用的成分，以具有防止水垢的效果 之水溶性聚合物為佳。 作為水溶性聚合物，可舉出例如：聚丙烯酸聚順丁 烯二酸、丙烯酸-順丁烯二酸共聚物、丙烯酸_磺酸系共聚 物、丙烯酸-苯乙烯共聚物及該等的鹽等。具體上係例如 以Acalic系列（日本觸媒股份公司）、ar〇n系列（東亞合As described above, when the original etching liquid in which the inorganic acid which dissolves indium oxide other than oxalic acid is used as a main component, the etching property and the stability of the etching liquid have significant problems in use, and there is no problem. It is comparable to an excellent etching solution which is superior to an etching solution containing oxalic acid as a main component. Further, etching using oxalic acid as a main component is an etching liquid capable of maintaining its excellent characteristics and capable of suppressing crystallization of indium oxalate, which is not present. Therefore, as a silver engraving liquid containing oxalic acid as a main component, it is used for the crystallization process in the etching process of a transparent conductive film containing indium, and the current state is only to carry out the transition of the remaining solution after use by the nanofiltration membrane. In addition, the method of the regeneration, the periodic maintenance of the apparatus, and the device configuration for forming a device structure in which crystals are not easily precipitated (Patent Document 7 and Non-Patent Document 1). [Patent Document 1] JP-A-2002-164332 (Patent Document 2) JP-A-2002-A No. 2 〇〇 〇 〇 〇 〇 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 [Patent Document 5] Japanese Patent Laid-Open Publication No. JP-A-2002-367974 (Patent Document No. JP-A-2002-367974) [Patent Document 7]曰 特 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2 2 2 2 2 2 2 2 2 2 2 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 268 In order to solve the problem, the object of the present invention is to provide a composition for a transparent conductive film, and to etch a transparent conductive film such as amorphous yttrium or yttrium used in a liquid crystal display or the like. It can prevent the precipitation of crystallization of indium oxalate to help increase production and reduce costs. [Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have found that an etching liquid composition for a transparent conductive film containing oxalic acid and a basic compound has an etching liquid containing oxalic acid as a main component. The present invention has been completed by further improving the crystallization of indium oxalate by suppressing the crystallization of the indium oxalate. That is, the present invention relates to an etching liquid composition for a transparent conductive film containing oxalic acid and a basic compound ® (excluding triethanolamine). Further, the present invention relates to the etching liquid composition for a transparent conductive film, wherein the basic compound is selected from the group consisting of a fourth-order ammonium hydroxide, an alkali metal hydroxide, and an alkanolamine (except for triethanolamine). And one or more of the group consisting of hydroxylamines. Further, the present invention relates to the above etchant composition for a transparent conductive film, wherein the pH is from 1.1 to 5.0. Further, the present invention relates to the etching liquid composition for a transparent conductive film, which further comprises a polysulfonic acid compound, a polyoxyethylene polyoxygen 7 201026819 propylene block copolymer, and a sulfonate type anionic surfactant. One or two or more compounds of the group are formed. Furthermore, the present invention relates to an etchant composition for a transparent conductive film, which further contains one or two kinds of water-soluble polymers. Further, the present invention relates to an etching liquid composition for a transparent conductive film, which is used in the case of a transparent conductive film containing oxidized steel. Further, the present invention relates to a method of etching a transparent conductive film, which is the use of the etching liquid composition for a transparent conductive film. The reason why the crystal of indium oxalate is easily precipitated is considered to be a low solubility of indium in an aqueous solution of oxalic acid. According to the investigation by the present inventors, it is clear that the amount of indium in the aqueous solution of oxalic acid is about 300 ppm, and the concentration of indium oxalate is likely to precipitate. That is, it is considered that the amount of indium dissolved in the aqueous oxalic acid solution is increased, which is related to the inhibition of crystallization of oxalic acid steel. The etching liquid composition for a transparent conductive film of the present invention can suppress the reason for crystal precipitation of indium oxalate by containing a basic compound, and although it is not clear, it is considered to be because the cation in the liquid becomes high and becomes relatively In the case of oxalic acid, oxalic acid is more likely to form a complex with the OH group or the amine and the fourth stage, so that the formation of indium oxalate can be suppressed, and as a result, the dissolution of indium can be increased. [Effect of the invention] By the transparent conductive film of the present invention In the etching composition, since the crystallization of indium oxalate can be suppressed during the etching process of the transparent conductive film, the liquid life of the etching liquid can be prolonged, and the operation for removing the crystal can be reduced, so that the throughput can be increased and the cost can be reduced. 8 201026819 [Embodiment] Hereinafter, the present invention will be described in detail. The transparent conductive film of the present invention is a transparent conductive film made of indium tin oxide (ITO), indium zinc oxide (IZO), or indium oxide, and particularly a transparent conductive film made of amorphous ITO and an IZO film. Further, the etching liquid composition for a transparent conductive film of the present invention is an etching liquid composition used in an etching process of the transparent conductive film in a process such as a liquid crystal display or an electroluminescence display. The concentration of the oxalic acid to be used in the etching liquid composition of the present invention is appropriately determined in consideration of the etching rate, the oxalic acid crystal is not precipitated, and the like, and is preferably 0.1 to 10% by weight. It is more preferably 8% by weight, more preferably 0.5 to 6% by weight. When the concentration of oxalic acid is low, the etching rate is lowered, and when the concentration of oxalic acid is high, the crystal of oxalic acid tends to precipitate. When the concentration of oxalic acid is in the above range, a practical etching rate can be obtained, and crystallization of oxalic acid does not occur and is preserved. The possibility of sexual or transport disorders is preferred. # The basic compound used in the etching liquid composition of the present invention is selected in consideration of the amount of indium dissolved, the etching rate, etc., and the etching liquid composition of the present invention is characterized by etching and ampere degree when a basic compound is added. The reduction is small, and the balance between the amount of indium dissolved and the etching rate is particularly important. Typical examples of the basic compound used in the etching liquid composition of the present invention include hydroxides of the fourth-order ammonium hydroxide, alkali metal hydroxides, alkanolamines (except triethanolamine) and hydroxylamines. Classes, etc. Specifically, as the fourth-grade hydrogen hydroxide, for example, tetramethylammonium oxide, tetraethylammonium hydroxide, choline or the like can be mentioned. 9 201026819 Further, it is used as an alkali metal hydroxide or hydrogen hydroxide. For example, hydrogen peroxide is used, and examples of the alkanoamines include (4) (4) and (4), and (4) phase 3 (4). - (4) amines, W - ethanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, hydrazine :: aminoethoxy) ethanol, ... propanol, monopropanolamine diindoline ethanol and Such salts and the like. Further, examples of the sterolamines include -ethanolamine, N-methyldiethanolamine, dibutanolamine, and the like. In the above-mentioned alkoxylated amines, from the viewpoints of the amount of indium dissolved, the rate of enrichment, etc., it is preferable that the monoalkanolamines, the dialkanolamines, and the like are more preferably monoalkanolamines. It is particularly preferable to be monoethanolamine or the like. Further, examples of the transamines include, for example, a transamine, an n-based transamine, an anthracene, a fluorenyldiamine, an N, a diethylamine, a hydroxylamine sulfate, a hydroxyl group. The amine or the like is preferably a hydroxylamine or the like. In addition, the basic compound may be contained in accordance with the use, or two or more kinds of the basic compound used in the etching liquid composition of the present invention, in consideration of the amount of cerium dissolved, crystal precipitation of indium oxalate, The pH of the etching liquid composition, the speed of the etching, and the like are appropriately determined, preferably 〇1 to 1 〇, 〇/〇, more preferably 0.3 to 7% by weight, and most preferably 5% to 5% by weight. . When the concentration of the basic compound is low, the crystal of indium oxalate is likely to be precipitated, and when the concentration is high, the etching rate tends to decrease, and when the concentration of the basic compound is in the above range, the effect of sufficiently preventing the crystal precipitation of indium oxalate can be obtained. And the practical etching rate is preferably pH of the etching liquid composition of the present invention, and it is preferable to appropriately determine lko by considering the crystal precipitation of the indium dissolved amount, the crystallization rate of the indium oxalate, and the like. 1.2 to 4.0 for better '13 to 3 〇 is especially good. When the pH is low, the crystal of indium oxalate is likely to be precipitated. When the pH is high, the residual speed tends to decrease. When the pH is in the above range, the effect of sufficiently preventing the crystal precipitation of indium oxalate and the practical etching rate can be obtained. It is better. In the rice engraving composition of the present invention, when the pH of the composition of the present invention containing oxalic acid and the test compound 比较 is compared with the pH of the composition having the same composition except for the test compound, the basic compound is added. The amount of change in pH Δ pH ' is appropriately determined in consideration of the amount of indium dissolved, the crystal precipitation of indium oxalate, the surname rate, and the like, and is appropriately adjusted by the type and concentration of the test compound to be added. The range of ΔPH is preferably (M~4.〇, preferably 〇3~3〇, especially 〇·5~2.G. △ pH hour crystallization of indium oxalate is easy to precipitate, △ pH is large The etching rate tends to decrease. When ΔρΗ is in the above range, it is preferable to obtain an effect of sufficiently preventing the precipitation of crystals of indium oxalate and a practical etching rate. The etching rate of the etching liquid composition of the present invention is preferable. In consideration of the treatment time, uniform etching, etc., it is appropriately adjusted by the concentration of oxalic acid, the type and concentration of the basic compound, etc. Further, the money engraving composition of the present invention does not hinder the above effects. Further, it is possible to further contain a component for removing the etching residue. The component used for such a purpose is a polysulfonic acid compound, a polyoxyethylene polyoxypropylene block copolymer, a sulfonate type anionic surfactant, or the like. 201026819 The polysulfonic acid compound may, for example, be a naphthalenesulfonic acid formaldehyde condensate or a salt thereof, polystyrenesulfonic acid or a salt thereof, lignosulfonic acid or a salt thereof, etc., as a naphthalenesulfonic acid furfural condensate and Its salt, with The system is based on RunoxlOOOC, 1500A, IONET D-2, Sanyo Levelon PHL (above, Toho Chemical Industry Co., Ltd.), LOMAR PWA-40 (made by SAN NOPCO Co., Ltd.), Demol N (Kao Co., Ltd.), POLITY N-100K ( LION Co., Ltd., Labelin FH-P (First Industrial Pharmaceutical Co., Ltd.) and other commodities win sales. As lignosulfonic acid and its salts, it is specifically Sorpol 9〇47k (Toho Chemical Industry Co., Ltd.), SunEkis ( In the case of the above-mentioned polysulfonic acid compound, a metal containing sodium or the like is not suitable for use in the electronics industry, but it is treated by using an ion exchange resin or the like to remove sodium. The polyoxyethylene-polyoxypropylene block copolymer has various types depending on the ratio of the polyoxyethylene to the oxypropylene and the molecular weight, and specifically, for example, the NEWPOL PE series (Sanyo Chemical Industry Co., Ltd.) ), the Epan series (First Industrial Pharmaceutical Co., Ltd.) and other trade names are sold. As the sulfonate type anionic surfactant, for example, dodecylbenzene Acid alkyl sulfonate and its salts, alkyl sulfates and the like thereof, sulfonate sulphonic acid dialkyl esters and salts thereof, polyoxyethylene alkyl ether sulfonic acids and salts thereof, polyoxyethylene olefins Propyl ether sulfonic acid and its salts, etc. Among them, because of less foaming, polyoxyethylene alkyl ether sulfonic acid and its salts, polyoxyethylene allyl ether sulfonic acid and its salts are particularly preferred, and Newcol series is used. In addition, these compounds may be sold in accordance with the use of 1 12 201026819 or more than 2 types. The etching liquid of the present invention is obtained from the viewpoint of obtaining an effect of sufficiently removing the etching residue. The polysulfonic acid compound, the polyoxyethylene-polyoxypropylene block copolymer, and/or the sulfonate-type anionic surfactant used in the composition are preferably in the range of 0.0001 to 1% by weight, 0 〇〇 1 to 10% by weight is particularly good. Further, the etching liquid composition of the present invention can further contain a component for suppressing crystal precipitation of indium oxalate without departing from the above-described range of φ. As the component to be used for such a purpose, a water-soluble polymer having an effect of preventing scale is preferred. Examples of the water-soluble polymer include polyacrylic acid polymaleic acid, acrylic acid-maleic acid copolymer, acrylic acid-sulfonic acid copolymer, acrylic acid-styrene copolymer, and the like. . Specifically, for example, the Acalic series (Japan Catalyst Co., Ltd.) and the ar〇n series (East Asia
成股份公司）、P〇LITY系列（L應股份公㈣的商品: 銷售。該等水溶性聚合物之中，含有_的金屬者係不適 合使用作為電子卫業用，以藉由使用離子㈣樹脂等處 理來除去納’可變為能夠使用。料水溶性聚合物可按照 用途而含有1種或2種以上。 從能夠得到充分的拍j也丨^^ s ^ 抑制結日日析出的效果之觀點，在 發明的蝕刻液組成物中所祛 所使用的水溶性聚合物之濃度， 0.001〜10重量。/。為佳， 以0.01〜10重量❶/D為特佳。又， 該等水溶性聚合物之分早县 刀子量’以200〜1〇0，_為佳 500〜10,000為特佳。 13 201026819 本發明的蝕刻液組成物’能夠在室溫或加熱而使用， 且係以能夠得到需要的蝕刻速度及蝕刻時間的方式，適當 地设定條件而使用。 作為使用本發明的银刻液組成物之透明導電膜的银 刻方法’可舉出：藉由喷霧喷嘴將蝕刻液供給至基板上之 喷灑處理、及將基板直接浸潰在蝕刻液中並搖動基板本身 或攪拌蝕刻液之浸潰處理等。 Φ 以下，顯示出本發明的實施例及比較例，來更詳細地 說明本發明’但是本發明未限定於這些實施例，在未悖離 本發明的技術思想之範圖，能夠進行各種的變更。 [實施例] (蝕刻液之組成） 本發明的實施例及比較例蝕刻液之組成，係如表1 所示。 201026819 [表l] 例子編號 草酸 鹼性化合物 聚磺酸化合物 水 實施例1 3.4重量％ TMAH 1.5重量％ - 殘餘部分 實施例2 3.4重量％ TMAH 2.0重量％ - 殘餘部分 實施例3 3.4重量％ TMAH 2.7重量％ - 殘餘部分 實施例4 3.4重量％ TMAH 3.8重量％ - 殘餘部分 實施例5 0.5重量％ TMAH 0.4重量％ - 殘餘部分 實施例6 1.0重量％ TMAH 0.7重量％ 殘餘部分 實施例7 5.0重量％ TMAH 3.2重量％ 殘餘部分 實施例8 3.4重量％ 膽鹼 2.6重量％ - 殘餘部分 實施例9 3.4重量％ MEA 1.4重量％ - 殘餘部分 實施例10 3.4重量％ 羥基胺 0.8重量％ - 殘餘部分 實施例11 3.4重量％ 氫氧化鈉 0.7重量％ - 殘餘部分 實施例12 3.4重量°/〇 TMAH 2.4重量％ Demol N 1.0重量°/〇 殘餘部分 實施例13 3.4重量％ TMAH 3.0重量％ Demol N 1.0重量％ 殘餘部分 比較例1 3.4重量％ - - 殘餘部分 比較例2 0.5重量％ - - 殘餘部分 比較例3 1.0重量％ - - 殘餘部分 比較例4 5.0重量°/〇 - - 殘餘部分 比較例5 3.4重量°/〇 - Demol N 1.0重量％ 殘餘部分 ΤΜΑΗ :氫氧化四曱銨 ΜΕΑ : —乙醇胺Into the company), P〇LITY series (L should be the shares of the company (four) of the goods: sales. Among these water-soluble polymers, the metal containing _ is not suitable for use as an electronic health industry, by using ion (four) resin The water-soluble polymer can be used in one or two or more types depending on the application. It is also possible to obtain a sufficient amount of j^^ s ^ to suppress the effect of precipitation on the day of the knot. It is preferable that the concentration of the water-soluble polymer used in the etching liquid composition of the invention is 0.001 to 10% by weight, preferably 0.01 to 10% by weight/D. Further, the water solubility It is particularly preferable that the amount of the knife of the early stage of the polymer is 200 to 1 〇 0, _ is preferably 500 to 10,000. 13 201026819 The etching liquid composition of the present invention can be used at room temperature or under heating, and is capable of being obtained. The etching rate and the etching time required are appropriately set and used. As a silver etching method using the transparent electroconductive film of the silver engraving composition of the present invention, the etching liquid is supplied by a spray nozzle. Spray treatment on the substrate And impregnating the substrate directly in the etching solution, shaking the substrate itself or stirring the etching solution, etc. Φ Hereinafter, the present invention will be described in more detail by showing examples and comparative examples of the present invention. The present invention can be variously modified without departing from the scope of the technical idea of the present invention. [Examples] (Composition of Etching Liquid) The composition of the etching liquid of the examples and comparative examples of the present invention is as follows. Table 1 shows. 201026819 [Table 1] Example No. oxalic acid basic compound polysulfonic acid compound Water Example 1 3.4 wt% TMAH 1.5 wt% - Residue Example 2 3.4 wt% TMAH 2.0 wt% - Residual Example 3 3.4 wt% TMAH 2.7 wt% - Residue Example 4 3.4 wt% TMAH 3.8 wt% - Residue Example 5 0.5 wt% TMAH 0.4 wt% - Residue Example 6 1.0 wt% TMAH 0.7 wt% Residue implementation Example 7 5.0 wt% TMAH 3.2 wt% Residue Example 8 3.4 wt% Choline 2.6% by weight - Residue Example 9 3.4 wt% MEA 1.4 % by weight - Residue Example 10 3.4% by weight Hydroxylamine 0.8% by weight - Residual part Example 11 3.4% by weight Sodium hydroxide 0.7% by weight - Residual part Example 12 3.4 Weight ° / 〇 TMAH 2.4% by weight Demol N 1.0 Weight °/〇 Residual Example 13 3.4 wt% TMAH 3.0 wt% Demol N 1.0 wt% Residue Comparative Example 1 3.4 wt% - - Residue Comparative Example 2 0.5 wt% - - Residue Comparative Example 3 1.0 wt% - - Residue Comparative Example 4 5.0 wt ° / 〇 - - Residual Comparative Example 5 3.4 Weight ° / 〇 - Demol N 1.0 wt% Residual portion ΤΜΑΗ : tetraammonium hydroxide ΜΕΑ : - ethanolamine
Demol Ν:萘績酸曱搭縮合物的鈉鹽（花王股份公司製） (銦的溶解性評價） 將如表1所示之各餘刻液，一邊加溫至50°C，一邊 以成為規定的銦濃度之方式，添加氧化銦粉末（平均粒徑 15 201026819 1微米、純度99.99%)，並攪拌2〜3小時。目視確認氧化 銦粉末係充分地溶解後，將各蝕刻液使用0.2微米過濾器 過濾，並將濾液密閉在容器中且靜置於設定為3 7°C的恆 溫槽内，目視確認在各規定時間有無結晶析出。又，測定 各银刻液的pH。又，银刻液中的銦溶解量係由所添加的 銦之重量、蝕刻液的容量及過濾前後的過濾器重量變化而 算出。其結果係如表2所示。Demol Ν: The sodium salt of the naphthoic acid condensate (manufactured by Kao Co., Ltd.) (Evaluation of the solubility of indium) The remaining etchants shown in Table 1 were heated to 50 ° C. Indium oxide powder (average particle diameter 15 201026819 1 μm, purity 99.99%) was added in the form of indium concentration, and stirred for 2 to 3 hours. After visually confirming that the indium oxide powder was sufficiently dissolved, each etching solution was filtered using a 0.2 μm filter, and the filtrate was sealed in a container and left to stand in a thermostat set at 37 ° C, and visually confirmed at each predetermined time. Whether or not crystals are precipitated. Further, the pH of each silver kerogen was measured. Further, the amount of indium dissolved in the silver engraving solution was calculated from the weight of the added indium, the capacity of the etching solution, and the change in the weight of the filter before and after the filtration. The results are shown in Table 2.
[表2][Table 2]
例子編號 pH In溶解量 液體安定性 實施例1 1.3 2,000ppm 〇 實施例2 1.5 3,000ppm 〇 實施例3 1.8 5,000ppm 〇 實施例4 3.0 5,000ppm 〇 實施例5 2.0 l,000ppm 〇 實施例6 1.8 l，000ppm 〇 實施例7 1.5 2,000ppm 〇 實施例8 1.5 2,000ppm 〇 實施例9 1.5 2,000ppm 〇 實施例10 1.5 l，000ppm 〇 實施例11 1.3 l，000ppm 〇 實施例12 1.5 3,000ppm 〇 實施例13 1.8 5,000ppm 〇 比較例1 1.0 l，000ppm X 比較例2 1.5 l,000ppm X 比較例3 1.3 l，000ppm X 比較例4 0.8 l’OOOppm X 比較例5 0.9 l,000ppm X ※銦溶解性的評價基準 〇：168小時（7天）以上結晶未析出。 X : 24小時（1天）以内結晶析出。 如表2所示，如比較例1〜5之未含有驗性化合物的 16 201026819 蝕刻液時，能夠確認銦溶解量小且在24小時以内結晶析 出。相對地’本發明的實施例丨〜13之含有鹼性化合物的 银刻液’係姻溶解篁大且經過1 6 8小時（7天）以上未產生 結晶析出’液體安定性非常優良。由此結果，得知增加銦 溶解量具有抑制草酸銦的結晶析出之效果。本發明的蝕刻 液組成物時’上述銦溶解量及液體安定性、與後述的蝕刻 速度的平衡係特別重要。Example No. pH In Dissolving Amount Liquid Stability Example 1 1.3 2,000 ppm 〇 Example 2 1.5 3,000 ppm 〇 Example 3 1.8 5,000 ppm 〇 Example 4 3.0 5,000 ppm 〇 Example 5 2.0 l, 000 ppm 〇 Example 6 1.8 l , 000 ppm 〇 Example 7 1.5 2,000 ppm 〇 Example 8 1.5 2,000 ppm 〇 Example 9 1.5 2,000 ppm 〇 Example 10 1.5 l, 000 ppm 〇 Example 11 1.3 l, 000 ppm 〇 Example 12 1.5 3,000 ppm 〇 Example 13 1.8 5,000 ppm 〇Comparative Example 1 1.0 l,000 ppm X Comparative Example 2 1.5 l,000 ppm X Comparative Example 3 1.3 l,000 ppm X Comparative Example 4 0.8 l'OOOppm X Comparative Example 5 0.9 l,000 ppm X * Evaluation of Indium Solubility Benchmark 〇: 168 hours (7 days) or more crystals were not precipitated. X : Crystallization occurred within 24 hours (1 day). As shown in Table 2, in the case of the 16 201026819 etching solution which did not contain the test compound of Comparative Examples 1 to 5, it was confirmed that the amount of indium dissolved was small and crystallized within 24 hours. In contrast, the silver sputum containing the basic compound in the examples 丨 to 13 of the present invention was dissolved in a large amount and did not cause crystal precipitation after 168 hours (7 days) or more. The liquid stability was extremely excellent. As a result, it was found that increasing the amount of indium dissolved has an effect of suppressing crystallization of indium oxalate. In the etching liquid composition of the present invention, the balance between the amount of indium dissolved and the liquid stability and the etching rate to be described later is particularly important.
❹ 又，如比較例2及3般地使草酸濃度降低，即便pH 為1.3〜1.5之組成’亦能夠確認有結晶析出，由此得知 只是單純地提高含草酸的蝕刻液之pH時並無效果，而使 其含有鹼性化合物時，對於抑制草酸銦的結晶析出係非常 有效的。 (姓刻速度的評價） 將如表1所示之#刻液加溫至40°C，並將在8〇〇入膜 厚度的非晶ITO膜上形成有光阻圖案之基板，浸潰於# ® 刻液各1分鐘後，水洗、乾燥後將光阻剝離，使用觸針式 臈厚度計，測定蝕刻量且計算蝕刻速度◊結果係如表3 所示。 17 201026819 [表3] 例子編號 PH 蝕刻速度(Α/分鐘） ---- 實施例1 1.3 620 ----- 實施例2 1.5 600 --— 實施例3 1.8 580 ----- 實施例4 1 3.0 440 -——. 實施例5 2.0 500 — 實施例6 1.8 560 ~~---* 實施例7 1.5 590 ----- 實施例8 1.5 600 實施例9 1.5 570 ----- 實施例10 — 1.5 570 實施例11 1.3 570 --- 實施例12 1.5 600 實施例13 1·8 580 --- 比較例1 1.0 640 比較例2 1.5 530 比較例3 1.3 590 比較例4 0.8 640 比較例5 0.9 640 ---- 如表3所示’得知本發明的實施例1〜13之含有驗性 _化合物的蝕刻液，相較於比較例1〜5之未含有鹼性化合 物的蝕刻液，雖然蝕刻速度稍微較小，但是對非晶質 膜具有實用上充分的蝕刻速度。 (殘渣除去性評價） 對於將在玻璃基板上形成有ΙΤ〇膜之基板，以從蝕刻 速度所算出的適量蝕刻時間之1.4倍時間蝕刻處理過者， 進行電子顯微鏡觀察來評價蝕刻後的殘渣。又，對將在玻 璃基板上形成氮化矽（SiN)膜並進而形成ΙΤΟ膜而成之基 板，同樣地對以從餘刻速度所算出的適量银刻時間之1.4 18 201026819 倍時間姓刻處理過者， 的殘渣。結果係如表4Further, when the oxalic acid concentration was lowered as in Comparative Examples 2 and 3, even if the pH was 1.3 to 1.5, it was confirmed that crystal precipitation was observed, and it was found that the pH of the etchant containing oxalic acid was not increased simply. The effect is that when it contains a basic compound, it is very effective for suppressing the crystal precipitation system of indium oxalate. (Evaluation of the surname speed) The #etching liquid shown in Table 1 was heated to 40 ° C, and a substrate having a photoresist pattern formed on the amorphous ITO film having a thickness of 8 Å was immersed in After each time of 1 ® engraving, the photoresist was peeled off after washing with water and dried. The amount of etching was measured using a stylus type thickness gauge and the etching rate was calculated. The results are shown in Table 3. 17 201026819 [Table 3] Example No. PH Etching speed (Α/min) ---- Example 1 1.3 620 ----- Example 2 1.5 600 --- Example 3 1.8 580 ----- Example 4 1 3.0 440 - -. Example 5 2.0 500 - Example 6 1.8 560 ~~---* Example 7 1.5 590 ----- Example 8 1.5 600 Example 9 1.5 570 ----- Example 10 - 1.5 570 Example 11 1.3 570 --- Example 12 1.5 600 Example 13 1·8 580 --- Comparative Example 1 1.0 640 Comparative Example 2 1.5 530 Comparative Example 3 1.3 590 Comparative Example 4 0.8 640 Comparison Example 5 0.9 640 - As shown in Table 3, 'the etching liquid containing the test compound of Examples 1 to 13 of the present invention was found to be etched without the basic compound as compared with Comparative Examples 1 to 5. Although the etching rate is slightly small, the liquid has a practically sufficient etching rate for the amorphous film. (Residue Removal Evaluation) The substrate on which the ruthenium film was formed on the glass substrate was subjected to etching treatment at a time of 1.4 times the appropriate etching time calculated from the etching rate, and the residue after the etching was evaluated by electron microscope observation. Further, a substrate obtained by forming a tantalum nitride (SiN) film on a glass substrate and further forming a tantalum film is similarly processed in the same manner as the amount of silver engraved time calculated from the residual speed of 1.4 18 201026819 times. Passer, the residue. The results are shown in Table 4.
進行電子顯微鏡觀察來評價蝕刻後 所示。Electron microscopic observation was performed to evaluate the results after etching.
※殘渣除去性之評價基準 〇：完全未觀察到殘渣 X :全面可觀察到殘渣 如表4所示’得知比較例丨之只含有草酸的㈣液時， 在玻璃基板上及SiN膜上，均全面地可觀察到殘渣，相對 地實施例12及13之含有草酸、鹼性化合物及聚磺酸化 口物的餘刻液時，具有與比較例5之含有草酸及聚續酸的 蝕刻液同等的殘渣除去性。 從上述表1〜4的結果，得知：因為本發明的蝕刻液 組成物，其銦溶解量大，且將銦溶解後之液體安定性非常 ifj，所以抑制草酸銦的結晶析出之效果非常優良。 又’得知：具有與未含有鹼性化合物之先前的以草酸 作為主成分的蝕刻液同等之實用上充分的蝕刻速度。 而且’得知：與未含有鹼性化合物之先前的以草酸作 為主成分的蝕刻液同樣地’藉由添加聚磺酸化合物等，能 夠賦予優良的殘渣除去性。 19 201026819 [產業上之利用可能性] 依照本發明’因為藉由使用含有草酸及鹼性化合物之 钱刻液組成物’來蝕刻在玻璃等的基板上所形成的IT〇 及ΙΖΟ等的透明導電膜’能夠有效地抑制在蝕刻裝置内 之草酸姻的結晶析出’能夠延長蝕刻液的液體使用期限且 能夠減輕用以除去結晶的作業及過濾器的交換頻率，所以 倉b夠提升生產量及降低成本。因此，在使用ΙΤ〇膜或ΐζ〇 ❹膜等的透明導電膜之液晶顯示器或電致發光顯示器等的 製造技術領域，係特別有用的。 【圖式簡單說明】 無 【主要元件符號說明】 無 20* Evaluation criteria for residue removal: No residue was observed at all X: Residues were observed as shown in Table 4. When the (4) liquid containing only oxalic acid was found in the comparative example, on the glass substrate and on the SiN film, The residue was observed in a comprehensive manner, and the etching solution containing the oxalic acid, the basic compound, and the polysulfonated mouth of Examples 12 and 13 was equivalent to the etching liquid containing the oxalic acid and the polyacid in Comparative Example 5. Residue removal. From the results of the above Tables 1 to 4, it is found that the etching solution composition of the present invention has a large amount of indium dissolved, and the liquid stability after dissolving indium is very strong, so that the effect of suppressing crystal precipitation of indium oxalate is excellent. . Further, it has been found that it has a practically sufficient etching rate equivalent to the previous etching liquid containing oxalic acid as a main component which does not contain a basic compound. Further, it has been found that, similarly to the etching liquid containing oxalic acid as a main component which does not contain a basic compound, it is possible to impart excellent residue removal property by adding a polysulfonic acid compound or the like. 19 201026819 [Industrial Applicability] According to the present invention, the transparent conductive material such as IT 〇 and ΙΖΟ formed on a substrate such as glass is etched by using a money engraving composition containing oxalic acid and a basic compound. The film 'effectively suppresses crystal precipitation of oxalic acid in the etching apparatus' can extend the liquid life of the etching liquid and can reduce the frequency of the operation for removing crystals and the frequency of exchange of the filter, so that the chamber b can increase the throughput and reduce the throughput. cost. Therefore, it is particularly useful in the field of manufacturing technology such as a liquid crystal display or an electroluminescence display using a transparent conductive film such as a ruthenium film or a ruthenium film. [Simple diagram description] None [Main component symbol description] None 20