TWI223661B - Etchant formulation for ITO film - Google Patents

Abstract

Disclosed is the etchant composition for the etching of the transparent conductive ITO film's pattern in manufacturing process of the thin-film-transistor liquid-crystal-display. The disclosed composition comprises 0.1 to 20 wt% MHSO4 aqueous solution, in which M=K, Na, or NH4. This invention relates to the adjustment of characteristics regarding etching speed and etched patterns by adjusting the concentration of MHSO4 and the addition of at least one of the additives chosen among KMnO4, H2O2, H2SO4, MHSO5 (M=K, Na, or NH4), HNO3, HClO4, NaClO4, M2S2O8 (M=K, Na, or NH4), KClO4, HIO4, and/or KIO4, in which the concentration for the additive(s) is 0.1 to 30 wt%. This invention relates to the removal of representative etching problems of residue resulting phenomenon, i.e. etching phenomenon of cell pattern in addition to the ITO film derived from the aluminum or aluminum/niobium alloy or the molybdenum or molybdenum/wolfram alloy, in order to increase the yield of the process.

Description

1223661 五、發明說明（l) 【發明之詳細說明】 發明.屬的技術# $ 本發明係有關在平板顯干 ^ p 丁低顯不|§用液晶顯不裝置犛 成透明電極之微細圖荦睥所田沾於儿加μ , 直寺方面开/ 务、^ 间系崎所用的乳化錮錫（以下稱作ττη 膜）之透明導變膜之蝕刻液組成物。 卜稱作ΙΤ0 習知拮m 透明導電膜係被廣泛使用於薄膜電晶液晶顯示裝置、 電漿顯示板顯示裝置、電致發光顯示裝置等的平板顯示器 用顯不裝置之薄膜，為於前述平板顯示器顯示裝置上形成 透明導電膜而使形成令人期待的微細圖案之蝕刻步驟係必 需的。 至於此時所用的透明導電膜，係主要採用IT〇膜。1223661 V. Description of the invention (l) [Detailed description of the invention] 发明 的 属 技术 # $ This invention is about showing dryness on a flat panel. Hiroshi Soda dipped in the composition of the etching solution of the transparent conductive film of emulsion tin (hereinafter referred to as ττη film) used by Nagasaki, Naji Temple, etc. Known as ITO, the conventionally known transparent conductive film is widely used in thin-film electro-crystal liquid crystal display devices, plasma display panel display devices, and electroluminescence display devices. An etching step of forming a transparent conductive film on a display device to form a desired fine pattern is necessary. As for the transparent conductive film used at this time, the IT0 film is mainly used.

前述I TO膜之使用係於玻璃等的基板上形成ΙΤ〇膜後， 以光阻為掩膜光罩並予塗布，蝕刻ΙΤ〇膜，至於既有的ΙΤ0 膜用钱刻液，係採用鹽酸、硝酸混合水溶液（王水系）、鹽 酸、醋酸混合水溶液，氣化鐵水溶液，眼酸水溶液、磷酸 水溶液、草酸水溶液等，惟此種習用的丨Τ〇膜用蝕刻液係 内含有下述般的問題點。 第一點係鹽酸、硝酸混合水溶液與鹽酸、醋酸混合水The use of the aforementioned I TO film is to form an ITO film on a substrate such as glass, and then apply a photoresist as a mask to the ITO film, and then etch the ITO film. As for the existing ITO film, the etching solution is hydrochloric acid. , Nitric acid mixed aqueous solution (aqua regia system), hydrochloric acid, acetic acid mixed aqueous solution, gasified iron aqueous solution, ocular acid aqueous solution, phosphoric acid aqueous solution, oxalic acid aqueous solution, etc. However, the conventional etching solution for the film for Too contains the following: question. The first point is a mixed aqueous solution of hydrochloric acid and nitric acid and a mixed solution of hydrochloric acid and acetic acid.

第6頁 1223661 五、發明說明（2) ' " 一—· 各液為餘刻速度快且女疋，但餘刻液之經時變化出現的 =，由鹽酸引起的裝置腐蝕現象，與使在薄膜電晶體製造 步驟用作閘電極之鋁或鋁、鈮合金蝕刻的缺點。 第二點係，氯化鐵水溶液為蝕刻速度快且安定，但 蝕量相對的多，且有導致鐵污染的缺點。 第三點係，m酸水溶液為側蝕量相對的少，具有良好 的蝕刻特性，惟有蝕刻液之經時變化較大的缺點。 第四點係，磷酸水溶液為有使用作閘電極之鋁或鋁、 鈮合金蝕刻的缺點。 士第五點係，草酸水溶液為蝕刻特性安定，蝕刻液之經 ^變化亦不致引起’故雖然良好，但有蝕刻時容易發 渣的缺點。 免..明_欲解決的誤籲 本發明係提供可解決既有的IT0膜用蝕刻液之鹽酸、 硝酸混合水溶液[王水系]、鹽酸、醋酸混合水溶液、氣化 鐵水溶液、咏酸水溶液、磷酸水溶液、草酸水溶液時所發 生的誠現象，經時變化現象、_時生成殘潰的現象， 銘或鋁、鈮合金等ΙΤ0膜以外的其他薄膜之姓刻現象等的Page 61223661 V. Description of the invention (2) 'I — · Each liquid is fast and son-in-law, but the time-dependent change of the remaining liquid appears =, the corrosion of the device caused by hydrochloric acid, and the use of Disadvantages of aluminum or aluminum, niobium alloy etching used as the gate electrode in the thin film transistor manufacturing step. The second point is that the ferric chloride aqueous solution has a fast and stable etching speed, but a relatively large amount of corrosion, and has the disadvantage of causing iron pollution. The third point is that the m-acid aqueous solution has a relatively small amount of side etching and has good etching characteristics, but has the disadvantage that the etching solution changes greatly with time. The fourth point is that the phosphoric acid aqueous solution has the disadvantage of using aluminum, aluminum, or niobium alloy as a gate electrode for etching. The fifth point is that the oxalic acid aqueous solution has stable etching characteristics, and the change of the etching solution does not cause ′. Therefore, although it is good, it has the disadvantage of easily slagging during etching. Free .. Ming _ The misunderstanding to be solved The present invention provides hydrochloric acid, nitric acid mixed aqueous solution [aqueous water system], hydrochloric acid, acetic acid mixed aqueous solution, vaporized iron aqueous solution, aqueous acid solution, etc. Phosphorus, phosphoric acid and oxalic acid aqueous solutions occur with time, change over time, and the phenomenon of generation of crumbling, engraving phenomenon of other films other than ITO film such as aluminum, niobium alloy, etc.

第7頁 1223661 五、發明說明（3) 缺點之透明導電膜的ITO膜用蝕刻液之組成物，至於Iτο膜 用蝕刻液之主反應劑，係以MHS04(M = K或Na、NH4)及添加劑 與水所構成的’可予完全的去除習用的IT0膜用蝕刻液之 缺點。 尤其，藉由去除使形成習用的I TO蝕刻液之主要問題Page 7 1223661 V. Description of the invention (3) Disadvantages The composition of the etching solution for ITO film of the transparent conductive film, as for the main reactant of the film etching solution for Iτο, is MHS04 (M = K or Na, NH4) and The shortcomings of additives and water can completely remove the conventional etching solution for IT0 film. In particular, the main problem of forming conventional I TO etchant by removing

點在蝕刻時的殘渣發生現象與鋁或鋁、鈮合金與鉬或鉬、 鶴合金等的IT0膜以外之水墨圖案（ceH pauern)的其他 薄膜蝕刻的現象，使於I TO膜蝕刻步驟之蝕刻不良率減 少，可使製程產率提高。 MAA題而换用的丰段 BB道ί發明係含有171^1^0之平板顯示器用顯示裝置之透 經時轡Γ1Τ0膜在圖案蝕刻時適用的1το蝕刻液，蝕刻液之 :時飯刻之各種特性良好且餘刻時不生成殘 鉬威π 被用作電極材料之鋁或鋁、鈮合金盥 液y、鎮合金㈣的㈣選擇性的⑽膜用水溶液餘刻、 之水溶液’為調整餘刻速度=m4)為主要成分 刻液之主成分的，之漠度或追加添加劑予整 1223661 五、發明說明（4) 以添加使用 至於此時所用的添加劑，為KMn〇4、H2〇2、H2S〇4、M2S2 〇8(M = K 或Na、NH4)、MHS〇5(M = l^Na、NH4)、HN〇3、HC104、Residues during dot etching and other thin film etching phenomena other than IT0 films such as aluminum or aluminum, niobium alloys, molybdenum or molybdenum, crane alloys, etc., cause the etching of the I TO film etching step The reduction of the defective rate can improve the process yield. Feng Duan BB Road, which was replaced by MAA, is an invention that contains 171 ^ 1 ^ 0 of a display device for a flat panel display. Γ1Τ0 film is suitable for pattern etching in the pattern etching. The etching solution: Shifanshizhi Various characteristics are good and no residual molybdenum is generated in the remaining time. Aluminium or aluminum, niobium alloy bath solution, and town alloy are used as the electrode material. Engraving speed = m4) is the main component of the main component of the etching liquid, the degree of indifference or additional additives to improve the 1223661 V. Description of the invention (4) To add and use the additives used at this time, KMn〇4, H202, H2S〇4, M2S2 08 (M = K or Na, NH4), MHS〇5 (M = 1 ^ Na, NH4), HN〇3, HC104,

NaCl〇4、HI〇4、KI〇4之中一種或二種以上可同時使用，適 當的添加量為〇·1〜30重量％。 本發明之I TO蝕刻液之蝕刻機構如下述所示。 IT0因係由iri2〇3及sn〇2之混合物而成，係由各氧化物 及ιτο蝕刻液之主成分的MHS〇4(M=K或以、之反應而 成’若試著以與KHSO4間之反應式表示時，如下述般 代表性的表示。 丁One or two or more of NaClO4, HI04, and KI04 can be used simultaneously, and the appropriate addition amount is 0.1 to 30% by weight. The etching mechanism of the I TO etchant of the present invention is as follows. IT0 is made of a mixture of iri203 and sn02, and it is formed by the reaction of MHS〇4 (M = K or Y2) as the main component of each oxide and ιτο etching solution. If you try to react with KHSO4 When the reaction equation is expressed, it is represented as follows.

In2 03 + 6KHS04^ In2(S04)3 + 3K2S04 + 3H20 Sn02 + 4KHS04^ Sn(S04)2 + 2K2S04 + 2H20 為獲得餘 追加添加 又’為圖案餘刻而採的各種要求特性之中 刻速度及钱刻prof i 1 e及CD損失與姓刻均勻性， 劑予以添加使用。In2 03 + 6KHS04 ^ In2 (S04) 3 + 3K2S04 + 3H20 Sn02 + 4KHS04 ^ Sn (S04) 2 + 2K2S04 + 2H20 In order to obtain additional additions, the various required characteristics adopted for the pattern's remaining time are inscribed speed and money The loss of prof i 1 e and CD and the uniformity of the last name are added.

本發明之I TO蝕刻液，係採用主反應劑之〇 . 之MHS04(M = K或Na、NH4)，於其中採用〇·；[〜30重量％ 量 劑，餘量以水所構成的。 添加The I TO etching solution of the present invention uses MHS04 (M = K or Na, NH4) of 0.1% of the main reactant, in which 0 ·; [~ 30% by weight of the agent, and the remainder is composed of water. Add to

1223661 五、發明說明（5) 發明之膏施形態 以下說明本發明之實施例。 f施例1 於0· 1重量％ iKHS04内添加1 〇重量％之〇03及0· 5重量％ 之H2 02與水以製造蝕刻液。 將採用此蝕刻液並以光阻已形成圖案的I TO膜基板 (IT 0膜之厚度5 0 0A )在4 0 °C以塗布並蝕刻1 〇分鐘後，利用 超純水清洗約1分鐘’並採用氮氣予以乾燥。 如此結束蝕刻後，利用電子顯微鏡觀察基板表面的結 果，於基板表面上亦未發現有任何殘渣，於鋁、銳膜與鉬 膜上亦刻姓現象’可確認出IT 0膜係經予良好的姓刻。 實施例2 於2· 5重量％ 2KHS04内添加25重量❶/。之HN03及1. 5重量％ 之H2 02與水以製造蝕刻液。 將採用此蝕刻液並以光阻已形成圖案的丨TO膜基板 (IT0膜之厚度200A)在40 °C予以塗布並蝕刻5分鐘後，利 用超純水清洗約1分鐘，並採用氮氣予以乾燥。1223661 V. Description of the invention (5) Application form of the invention The following describes embodiments of the present invention. fExample 1 In 0.1% by weight of iKHS04, 10% by weight of 03 and 0.5% by weight of H2 02 and water were added to produce an etching solution. The I TO film substrate (IT 0 film thickness 50 0A) that has been patterned with photoresist using this etchant is coated and etched at 40 ° C for 10 minutes, and then washed with ultrapure water for about 1 minute ' And dried with nitrogen. After the etching was finished in this way, the substrate surface was observed with an electron microscope. No residue was found on the substrate surface, and the surname phenomenon was also engraved on the aluminum, sharp film, and molybdenum film. 'It can be confirmed that the IT 0 film system has been well-prepared. Last name carved. Example 2 25% by weight was added to 2.5% by weight of 2KHS04. HN03 and 1.5% by weight of H2 02 and water to make an etching solution. The TO film substrate (IT0 film thickness 200A) that has been patterned with photoresist using this etching solution is coated and etched at 40 ° C for 5 minutes, then washed with ultrapure water for about 1 minute, and dried with nitrogen. .

第10頁 1223661 五、發明說明（6) 如此結束姓刻後，利用電子顯微鏡觀察基板表面的結 果’於基板表面上亦未發現有任何殘潰，於紹、銳膜與顧 膜上亦無蝕刻現象，可確認出I το膜經予良好的钱刻。 膏施例3 於5重量％ iKHS04内添加25重量％之龍03及1 · 5重量％之 H2 〇2與水以製造蚀刻液。Page 10 1223661 V. Description of the invention (6) After the end of the last name engraving, the result of observing the surface of the substrate with an electron microscope was not found on the substrate surface, and there were no residues, and there was no etching on Shao, sharp film and Gu film. It can be confirmed that the I το film is well carved. Paste Example 3 25% by weight of Dragon 03 and 1.5% by weight of H2O2 and water were added to 5% by weight of iKHS04 to produce an etching solution.

將採用此蝕刻液並以光阻已形成圖案的IT〇膜基板 (ΙΤ0膜之厚度2000Α )在40 °C予以塗布並蝕刻5分鐘後，利 用超純水清洗約1分鐘，並採用氮氣予以乾燥。 如此結束银刻後’利用電子顯微鏡觀察基板表面的結 果於基板表面上亦未發現有任何殘潰。於銘、銳膜與顧 膜上亦無蝕刻現象，可確認出丨T〇膜係經予良好的蝕刻。 實施例4 於20重量％ iKHS〇4内添加15重量％之ην〇3及1· 〇重量％之 Η2 02與水以製造蝕刻液。The IT0 film substrate (ITO film thickness 2000A) which has been patterned with photoresist using this etching solution is coated and etched at 40 ° C for 5 minutes, then washed with ultrapure water for about 1 minute, and dried with nitrogen. . After the silver engraving was finished in this way, the results of observing the surface of the substrate with an electron microscope showed no residue on the surface of the substrate. There was no etching on Yu Ming, sharp film, and Gu film. It can be confirmed that T0 film was well etched. Example 4 In 20% by weight of iKHS04, 15% by weight of ην03 and 1.0% by weight of Η2 02 and water were added to produce an etching solution.

將採用此姓刻液並以光阻已形成圖案的ΙΤ〇膜基板 (ΙΤ0膜之厚度2〇〇〇Α)在4〇 予以塗布並蝕刻5分鐘後，利 用超純水清洗約1分鐘，並採用氮氣予以乾燥。 1223661An ITO film substrate (thickness of ITO film with a thickness of 2000A) which has been patterned with a photoresist using this last solution is coated and etched for 5 minutes at 40, and then washed with ultrapure water for about 1 minute, and Dry with nitrogen. 1223661

如此結束蝕刻後，利用電子顯微鏡觀察基板表 果，於基板表面上亦未發現有任何殘清， 的〜 膜上亦無蝕刻現象，可確認出ITO膜經予良好的餘刻、。/、錦 發明之功效After the etching was finished in this way, the results of the substrate were observed with an electron microscope, and no residue was found on the surface of the substrate. There was no etching phenomenon on the film. It was confirmed that the ITO film had a good after-treatment. / 、 The effect of the invention

本發明之ITO膜用钱刻液’在適用於含有薄膜電晶體 液晶顯示裝置之平板顯示器用顯示裝置之透明導電膜的 I TO膜之圖案蝕刻時，由於與習用的丨丁^)膜蝕刻液不同，不 致生成蝕刻時之殘渣發生現象或鋁或鋁、鈮合金與鉬或 銦、鎢合金類I TO膜以外的其他薄膜之蝕刻現象之問題 點，成為可獲致使製造原價節省及製程產率提高的效果。The etching solution for the ITO film of the present invention is suitable for pattern etching of the I TO film of a transparent conductive film suitable for a display device for a flat-panel display including a thin-film transistor liquid crystal display device. The difference is that it does not cause the phenomenon of residues during etching or the phenomenon of etching of aluminum or aluminum, niobium alloys and other thin films other than ITO films of molybdenum or indium and tungsten alloys, which can lead to savings in manufacturing cost and process yield. Improved effect.

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Claims (1)

1223661 修正/愛. ' 六、申請專利範圍 1、 一種透明導電膜之蝕刻液組成物，其特徵在於含有薄 膜電晶體一液晶顯示裝置之平板顯示器用顯示裝置之透明 導電膜I TO膜在圖案蝕刻時所使用的蝕刻液，由主反應劑 之MHS04(M = K或Na、NΗ 4)及添加劑與水所構成；其中，姓刻 液之主反應劑MHS04(M = K或Na、ΝΗ4)為0.卜20重量％。 2、 如申請專利範圍第1項之透明導電膜之蝕刻液組成物， 其中添加劑係 KMn04、H 20 2、H2S04、M2S 20 8(M = K或 Na、ΝΗ4)、 MHS〇5(M = K或 Na、 NH4)、 HN〇3、 HC104、KC14、 HI04、ΚΙΟ^ 中一種或二種以上可同時使用，添加劑之重量為（K 1〜3 0重 量％ 〇1223661 Amendment / Love. 六. Application for Patent Scope 1. An etching solution composition of transparent conductive film, which is characterized in that the transparent conductive film I TO film of a display device for a flat panel display containing a thin film transistor-a liquid crystal display device is etched in a pattern The etching solution used at this time is composed of MHS04 (M = K or Na, NΗ 4) as the main reactant and additives and water. Among them, the main reactant MHS04 (M = K or Na, ΝΗ4) as the last name is 0. Bu 20% by weight. 2. For example, the etching solution composition of the transparent conductive film of the scope of application for the patent, where the additives are KMn04, H 20 2, H2S04, M2S 20 8 (M = K or Na, ΝΗ4), MHS〇5 (M = K Or Na, NH4), HN〇3, HC104, KC14, HI04, ΚΙΟ ^ can be used at the same time, the weight of the additive is (K 1 ~ 30% by weight 〇 第14頁Page 14