201231625 六、發明說明： 【發明所屬之技術領域】 本發明係關於金屬氧化物被膜的蝕刻液組成物，特別係適 用於含有銦-錫氧化物（以下簡稱ΓΙΤ0」）、銦_鋅氧化物（以 下簡稱「ΙΖΟ」）等氧化銦之氧化錮系被膜的加工用之蝕刻液。 【先前技術】 透明導電膜等所使用之氧化銦系被膜的濕式蝕刻之相關 技術，已知有各種技術，從廉價且蝕刻速度佳的觀點而言， 大多係將含有鹽酸的水溶液當作蝕刻液組成物使用。但是， 鹽酸因為氯化氫的揮發與強腐蝕性，會有臭氣產生、及裝置 或被餘刻基材等的腐餘劣化問題。又，除此之外，當使用鹽 酸的情況’會_讀得氧化銦系健、與基材或其他層間 之I虫刻選擇性的問題。 為改善此種問題，就未含有鹽酸的氧化銦系被膜之蝕刻液 、卫成物已進行檢討，並有各種報告。例如專利文獻1揭示： 為了對由銀或銀合金構成的金屬膜與透明導電膜利用單液 施行蝕刻，而含有銅離子、硝酸及氟化合物作為必要成分的 組成物。另，作為該必要成分的氟化化合物係例示氟化銨， 作為任意成分則揭示了甲酸、醋酸、草酸、檸檬酸等羧酸。 再者，專利文獻2揭示含有多元羧酸與氫氟酸鹽的ΙΤ〇 蝕刻液組成物。多元羧酸係例示草酸、檸檬酸，而氟化物鹽 係揭示氟化鈉、氟化鉀、氟化銨。 100144791 Λ 201231625 [先行技術文獻 [專利文獻] [專利文獻1]日本專利特開2009_206462號公報 [專利文獻2]日本專利特開2010-67823號公報 【發明内容] (發明所欲料之問題） ^而上述所揭示之蝕刻液組成物的蝕刻速度慢，且 選擇性亦尚嫌不足。 Xl 緣疋，本發明係為了解決上述問題而完成，其目的在於指 供經抑制臭氣產生及裝置或被_基材等的舰劣化，特另I 係對氧化㈣被駭現充分㈣速度與似彳選擇性的餘pi (解決問題之手段） 本發明者等為解決上述問題經深入鑽研，結果發現藉由^ 2-經基乙俩與氟化化合物依特定比 例併用，便可解氺 問題，遂完成本發明。 ~ ^ I7本I日月的金屬氧化物被膜之射彳液組成物係由含有下 、〔成刀的水4液所構成：（A)2•經基乙績酸或其鹽依2·經基 乙械換算為5〜2G質量％ ;以及⑻從氫氟酸、氟化錄、氣 化鉀、氟㈣及氣⑽所構成群財之至少丨種氣化化 合物0.05〜5質量％。 (發明效果) 100144791 4 201231625 根據本發明，可提供對氧化銦系被膜具有充分蝕刻速度與 名虫刻選擇性的钱刻液組成物。 【實施方式】 本發明的金屬氧化物被膜之蝕刻液組成物（以下亦簡稱 钱刻液組成物」）係以：（A)2-羥基乙磺酸或其鹽依2-羥基 乙％酸換算為5〜20質量％ ;以及(B)從氫氟酸、氟化銨、氟 化鉀、氟化鈉及氟化鋰所構成群組中選擇之至少丨種氟化化 合物0.05〜5質量％作為必要成分並含有。且，視需要在不 致阻礙本發明效果的範圍内，亦可含有添加劑。本發明的蝕 刻液組成物較佳係含有上述(A)、（B)成分及視需要使用的添 加劑，其餘則為水。 作為本發明蝕刻液組成物的(A)成分係2 -羥基乙磺酸之鹽 的情況之例，可舉例如鈉鹽、鉀鹽、鋰鹽、銨鹽等的水溶性 鹽。通常(A)成分係可使用2_羥基乙磺酸。其含有量係依2_ 羥基乙磺酸換算為5〜20質量％、較佳為5〜15質量％。若(a) 成分的含有量低於上述範圍的下限，便無法獲得充分的蝕刻 速度。另一方面，即便成分的含有量多於上述範圍的上 限，仍無法提升蝕刻速度，反而導致發生對裝置構件造成腐 名虫專不良情況。 本發明之蝕刻液組成物中，（B)成分的氟化化合物係選擇 自氫氟酸、氟化銨、氟化卸、氟仙及氟化賴構成群組中， 該等係可為1種、亦可混合使用2種以上。其中，氟化卸係 100144791 , 201231625 從安全性、衛生性上 ”、而s屬較佳。（B)之含有量係0.05〜5 質料、較佳係（U〜2 f量％。又，雜)之含有量少於上述 ㈣的:限’則無法獲得充分⑽刻速度。另—方面，若⑻ 之3有里夕於上述㈣的上限，會有對裝置或基材的腐钱性 變大之不良情況發生。 再者’本發明的餘刻液組成物中，除上述(A)成分與(B 成分之外，在不致阻礙本發明效果的範_，可配合周知汗 加劑。該添加劑係可舉例如則()液組成物的安定化劑、各成 分的可溶化、pH調整劑、比重調整劑 '黏度調 整4、制性改善劑、s合劑、界面活性鮮，使用該等時 的濃度’一般係在0.001質量％〜1〇質量％的範圍内。 本發明的㈣m組成物係在對金屬氧化物被膜施行姓刻 時使用。被侧對象的金屬氧化物係可舉例如氧切、氧化 紹、氧化鋅、氧化紀、氧化銦、IT0、IZ0、紹-辞氧化物⑽⑺ 等。本發日㈣㈣液組成物係於料之中，特別對氧化姻、 ΙΤΟ、ΙΖΟ等含有氧化銦的氧化銦系被膜顯示良好餘刻速 度。又，對該等氧化銦系被膜特別顯示良好钱刻選擇性。 因為本發明的姓刻液組成物具有上述特性，因而適用於太 陽電池、顯示元件、觸控面板或照明器具等所使用之屬於透 明導電膜的ΙΤΟ被膜、ΙΖ0被膜之蝕刻。 在使用本發明之蝕刻液組成物將被膜予以除去時，只要使 被加工基材浸潰於上述本發明蝕刻液組成物中、或對被加工 100144791 6 201231625 =材噴壤本發日祕刻液組成物等即可。浸漬條件係依昭構件 了形狀與膜厚“有所差異，故只要配合該_選擇即 右溫度屬低溫則_效率會變差所以較恤 10〜80C、更佳係依20〜6(rc實施。 彻上述浸潰、噴灑等施行的_時間並無㈣㈣定， 】^行直到除去賴為止的時，可。騎_通常所使 膜請〜職刻只要施行數秒〜 =刀^便可。又，因為本發日_液組成物的_選擇性 理义，亦不rjr在被膜祕刻結束後仍施行過剩時間的處 .膜等遭顧化的_。特難魏化銦系被 膜肩不更良好的飯刻選擇性。 [實施例] :下’利用實施例與比較例針對本發明進行詳細說明，惟 本發明並不因該等而受限制。201231625 VI. Description of the Invention: [Technical Field] The present invention relates to an etching liquid composition of a metal oxide film, and particularly to an indium-tin oxide (hereinafter referred to as ΓΙΤ0), indium-zinc oxide (hereinafter) Hereinafter, an etching solution for processing a cerium oxide-based film of indium oxide, such as "ΙΖΟ"). [Prior Art] Various techniques are known for wet etching of an indium oxide-based film used for a transparent conductive film or the like. From the viewpoint of inexpensiveness and high etching speed, an aqueous solution containing hydrochloric acid is often used as an etching method. The liquid composition is used. However, due to the volatilization and strong corrosive nature of hydrogen chloride, hydrochloric acid may cause odor generation and deterioration of the apparatus or the residual substrate or the like. Further, in addition to the case where hydrochloric acid is used, the problem of indium oxide resistance and the selectivity to the substrate or other layers can be read. In order to improve the problem, the etching solution and the sterilizing agent of the indium oxide-based film which does not contain hydrochloric acid have been reviewed, and various reports have been made. For example, Patent Document 1 discloses a composition in which a metal film made of silver or a silver alloy and a transparent conductive film are etched by a single liquid, and copper ions, nitric acid, and a fluorine compound are contained as essential components. Further, the fluorinated compound as the essential component is exemplified by ammonium fluoride, and as an optional component, a carboxylic acid such as formic acid, acetic acid, oxalic acid or citric acid is disclosed. Further, Patent Document 2 discloses a ruthenium etching composition containing a polyvalent carboxylic acid and a hydrofluoric acid salt. The polycarboxylic acid is exemplified by oxalic acid and citric acid, and the fluoride salt is disclosed by sodium fluoride, potassium fluoride or ammonium fluoride. [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. 2010-20623 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2010-67823 (Summary of the Invention) The etchant composition disclosed above has a slow etching rate and is insufficient in selectivity. The present invention has been made to solve the above problems, and its object is to provide for the suppression of odor generation and the deterioration of the device or the substrate of the substrate, etc., in particular, the oxidation of the (four) is fully (four) speed and The inventors of the present invention have intensively studied to solve the above problems, and as a result, it has been found that the problem can be solved by using a combination of a 2- and a fluorinated compound in a specific ratio. , 遂 completed the present invention. ~ ^ I7 This is the composition of the metal oxide film of the metal oxide film. It consists of a liquid containing 4 liquids: (A) 2 • Meridian acid or its salt The base group is converted into 5 to 2 G mass%; and (8) at least 0.05 to 5 mass% of the vaporized compound of the group consisting of hydrofluoric acid, fluoride, potassium carbonate, fluorine (tetra), and gas (10). (Effect of the Invention) 100144791 4 201231625 According to the present invention, it is possible to provide a money engraving composition having a sufficient etching rate and a pseudo-etching selectivity for an indium oxide-based film. [Embodiment] The etching liquid composition of the metal oxide film of the present invention (hereinafter also referred to as "money engraving composition") is based on: (A) 2-hydroxyethanesulfonic acid or a salt thereof in terms of 2-hydroxyethyl acid 5 to 20% by mass; and (B) at least 0.05 to 5% by mass of the fluorinated compound selected from the group consisting of hydrofluoric acid, ammonium fluoride, potassium fluoride, sodium fluoride, and lithium fluoride Essential ingredients and contain. Further, an additive may be contained as long as it does not impair the effects of the present invention. The etching composition of the present invention preferably contains the above components (A) and (B) and an additive to be used as needed, and the remainder is water. Examples of the case where the component (A) of the composition of the etching solution of the present invention is a salt of 2-hydroxyethanesulfonic acid may, for example, be a water-soluble salt such as a sodium salt, a potassium salt, a lithium salt or an ammonium salt. Usually, the component (A) can be used as 2-hydroxyethanesulfonic acid. The content thereof is 5 to 20% by mass, preferably 5 to 15% by mass, based on 2% of hydroxyethanesulfonic acid. If the content of the component (a) is less than the lower limit of the above range, a sufficient etching rate cannot be obtained. On the other hand, even if the content of the component is more than the upper limit of the above range, the etching rate cannot be increased, and on the contrary, it causes a problem of caustic rot of the device member. In the etching liquid composition of the present invention, the fluorinated compound of the component (B) is selected from the group consisting of hydrofluoric acid, ammonium fluoride, fluorination, fluorinated, and fluorinated lysate, and the system may be one type. Two or more types may be used in combination. Among them, the fluorination unloading system 100144791, 201231625 is safe and hygienic, and s is preferred. The content of (B) is 0.05~5, preferably (U~2 f%%. Also, miscellaneous If the content of the material is less than the above (4): limit, then sufficient (10) speed cannot be obtained. On the other hand, if (3) 3 has the upper limit of (4) above, the rot of the device or substrate will become larger. In addition, in the remnant composition of the present invention, in addition to the above-mentioned component (A) and (component B, it is possible to blend with the known sweat additive without inhibiting the effects of the present invention. For example, the stabilizer of the liquid composition, the solubilization of each component, the pH adjuster, the specific gravity adjuster 'viscosity adjustment 4, the system improver, the s mixture, and the interface activity are fresh, and when used, The concentration 'is generally in the range of 0.001% by mass to 1% by mass. The (iv)m composition of the present invention is used when the metal oxide film is subjected to a surname. The metal oxide of the side object may be, for example, oxygen cut. Oxidation, zinc oxide, oxidized period, indium oxide, IT0, IZ0, sulphur-oxidation (10) (7), etc. The liquid composition of the present day (4) and (4) is in the form of a material, and particularly exhibits a good residual speed for an indium oxide-based film containing indium oxide such as oxidized samarium, lanthanum or cerium. Further, the indium oxide-based film is particularly shown. Since the surname composition of the present invention has the above characteristics, it is suitable for etching of a ruthenium film or a ruthenium film which is a transparent conductive film used for a solar cell, a display element, a touch panel or a lighting fixture. When the film is removed by using the etching liquid composition of the present invention, the substrate to be processed is immersed in the above-described etching liquid composition of the present invention, or is processed for 100144791 6 201231625 The liquid composition or the like may be used. The impregnation condition is different depending on the shape and the film thickness of the member. Therefore, if the temperature is low, the temperature is low, so the efficiency is deteriorated, so the shirt is 10 to 80 C, which is better. According to 20~6 (rc implementation. The _ time of the above-mentioned impregnation, spraying, etc. is not (4) (four) fixed, 】 ^ line until the removal of the reliance, can be. _ _ usually make the film please ~ job as long as the application A few seconds ~ = knife ^ can. Also, because of the _ selectivity of the composition of the _ liquid composition, and not rjr after the end of the film secrets still carry out the excess time. The film is subject to consideration. The indium-based indium-based coating film shoulder does not have a better cooking selectivity. [Examples]: The present invention will be described in detail by way of examples and comparative examples, but the invention is not limited thereto.
[實施例1J /夺表1所記载濃度的2_經基乙續酸、以及表1所記載的 乱化化合物调製為含有括號内所記載濃度的敍刻液組成物 10 S外’其餘全部為水。在經調溫為贼的各 』液尹/又項著經在PET薄膜上利用減鑛形成膜厚⑵ ㈣之ITO膜的基材，測定朗仰膜被除去為止 的時間。 s 100144791 7 201231625 表1 :實施例的各餘刻液之主組成與飯刻速度 蝕刻液 2-羥基乙磺酸 (濃度：質量％) 氟化化合物 質量 °/。）_ NHaFro.n 時間：分 No.l 10 4 No.2 10 NH4Fn.0'> 1 No.3 10 NH4FC5.(n 1 No.4 10 KFfo.n 4 No.5 10 1 No.6 10 KFfO.S'i 2 No.7 7 KFi〇.5、 4 No.8 12 KF(〇.5、 2 No.9 10 KFfl.O) 1 No.10 10 NaF(O.n 4 [比較例1] 調製由經溶解表2所記載溶質之水溶液所構成的比較用 蝕刻液組成物A〜L。施行與上述實施例同樣的操作，測定 直到ITO膜被除去為止的時間。 表2:比較例的各银刻液之主組成與餘刻速度 比較用姓刻 液組成物 A 溶質 _(質量％) 溶質 (質量 時間：分 氣化氫（10) 4 B — KF(0.5) 即便15分鐘仍無法除本 C _ 硫酸no) KF(0.1) 5 D 硝酸（10) KF(0.1) 4 E 曱酸Π0) KF(0,5) 3 F 草酸（10) KF(0.5) 2 G 檸檬酸(10) KF(0.5) ----- 8 Η 2_羥基乙磺酸no) — 14 I 2-羥基乙磺酸（10) NH4C1(5.0) ---- 13 J 2_羥基乙磺酸（10) NH4C1(10.0) 12 κ 2-羥基乙磺酸（10) NaCl(10) 11 L 2-羥基乙磺酸（10) KC1(10) 14 100144791 8 201231625 從餘刻液No.l〜1〇、與比較用敍刻液組成物A的比較，確 認本發明_液可獲得與贼同等級以上的ito钱刻速 度。又，從各自含有氟化化合物Oj質量％的蝕刻液^^〇3、 4、10與餘刻液c、D的比較’得知本發⑽刻液相較於將 2-羥基乙磺酸改變為硫酸、硝酸的情況，可賦予同等級戋同 等級以上的ITO㈣速度。由該等結果可確認到本發· 刻液能改善習知蝕刻液中構成問題之臭氣產生、對襞置與被 蝕刻基材等的腐蝕劣化、蝕刻選擇性等問題，且為蝕刻速度 優異的钮刻液。 再者，由含有2-羥基乙磺酸1〇質量％與氟化化合物〇.5 質量％的蝕刻液Νο·6、與分別含有氟化化合物〇 5質量％的 比較用㈣液Ε、F、G進行錄，可確認本發㈣刻液相 較於將2-羥基乙磺酸改變為其他有機酸的情況，可賦予同 專級以上的ITO钮刻速度。 再者，由蝕刻液No.1〜10與比較用蝕刻液 的比較(例如No.3與I的比較），可確認到本發明蝕刻液相較 於將氟化化合物改變為氯化化合物的情況，可賦予優異蝕刻 速度。 [實施例2、比較例2] 針對上述實施例1所記載之蝕刻液No.6、與比較例丨所 記載之蝕刻液F，施行對鋁及鈦的腐蝕試驗。腐蝕試驗係將 各基材的測試片（5cmx2.5cmx厚度1mm)在40。(：蝕刻液中浸 100144791 〇 201231625 潰7小時，依浸潰後的質量減少程度施行評價。結果如表3 所示。 表3 :對鋁及鈦的腐姓試驗[Example 1J / 2 - mercapto acid as described in Table 1 and the chaotic compound described in Table 1 were prepared to contain the engraved composition 10 S of the concentration described in parentheses" All are water. In the case of the ITO film which was subjected to temperature reduction to a thief, the substrate of the ITO film having a film thickness (2) (4) was formed on the PET film by demineralization, and the time until the swell film was removed was measured. s 100144791 7 201231625 Table 1: Main composition and cooking speed of each of the residual solutions of the examples Etching liquid 2-Hydroxyethanesulfonic acid (concentration: mass%) Fluorinated compound mass °/. )_ NHaFro.n Time: Min. No.l 10 4 No.2 10 NH4Fn.0'> 1 No.3 10 NH4FC5.(n 1 No.4 10 KFfo.n 4 No.5 10 1 No.6 10 KFfO.S'i 2 No.7 7 KFi〇.5, 4 No.8 12 KF(〇.5, 2 No.9 10 KFfl.O) 1 No.10 10 NaF (On 4 [Comparative Example 1] Modulation The comparative etching liquid compositions A to L composed of the aqueous solution of the solute described in Table 2 were subjected to the same operation as in the above Example, and the time until the ITO film was removed was measured. Table 2: Silver of Comparative Example Comparison of the main composition of the engraving and the speed of the engraving with the surname engraving composition A Solute_(% by mass) Solute (mass time: hydrogen sulfide (10) 4 B - KF (0.5) Even if it is still 15 minutes, this C cannot be removed. _ sulfuric acid no) KF(0.1) 5 D nitric acid (10) KF(0.1) 4 E bismuth citrate 0) KF(0,5) 3 F oxalic acid (10) KF(0.5) 2 G citric acid (10) KF (0.5 ----- 8 Η 2_hydroxyethanesulfonic acid no) — 14 I 2-hydroxyethanesulfonic acid (10) NH4C1(5.0) ---- 13 J 2_hydroxyethanesulfonic acid (10) NH4C1 (10.0 12 κ 2-hydroxyethanesulfonic acid (10) NaCl(10) 11 L 2-hydroxyethanesulfonic acid (10) KC1(10) 14 100144791 8 201231625 From the residual liquid No.1~1〇, Comparison was engraved with the classification of composition A, according to the present invention was confirmed _ money obtained ito engraved speed above the same level of thieves. Further, from the comparison of the etching liquids ^, 3, 4, 10 containing the fluorinated compound Oj, and the residual liquids c, D, it is known that the liquid phase of the present invention is changed from that of 2-hydroxyethanesulfonic acid. In the case of sulfuric acid or nitric acid, the ITO (four) speed of the same grade or higher can be given. From these results, it has been confirmed that the present invention can improve the problem of odor generation in the conventional etching solution, corrosion deterioration of the substrate and the substrate to be etched, etching selectivity, and the like, and is excellent in etching speed. Button engraving. Further, the etching liquid Νο·6 containing 1% by mass of 2-hydroxyethanesulfonic acid and 5% by mass of the fluorinated compound, and (4) liquid Ε, F containing 5% by mass of the fluorinated compound 分别, respectively. When G is recorded, it can be confirmed that the liquid phase of the present invention is changed to other organic acids by the liquid phase of the (4) engraving, and the ITO buttoning speed of the same grade or higher can be given. Further, by comparison of the etching liquid Nos. 1 to 10 with the comparative etching liquid (for example, comparison of No. 3 and I), it was confirmed that the etching liquid phase of the present invention was changed from the fluorinated compound to the chlorinated compound. Can give excellent etching speed. [Example 2, Comparative Example 2] Corrosion tests on aluminum and titanium were carried out on the etching liquid No. 6 described in the first embodiment and the etching liquid F described in the comparative example. In the corrosion test, test pieces (5 cm x 2.5 cm x thickness 1 mm) of each substrate were placed at 40. (: immersion in etchant 100144791 〇 201231625 for 7 hours, according to the degree of quality reduction after immersion. The results are shown in Table 3. Table 3: Test on the corrosion of aluminum and titanium
由上述可確認到本發明姓刻液N〇 6相較於將2-羧基乙石黃 酸改變為草酸的情況，對鋁及鈦的腐蝕性較小。 [實施例3] 使用上述實施例丨所記載之蝕刻液N〇.6及No.7，針對 50nm氧化釔膜、3〇nm氧化矽臈的各被膜施行蝕刻試驗。具 體而έ係將各個膜基材浸潰於45Ϊ蝕刻液中，浸潰15分 鐘。結果確認到各個膜均被除去。 100144791From the above, it was confirmed that the N 〇 6 phase of the present invention is less corrosive to aluminum and titanium than the case where carboxy oxalic acid is changed to oxalic acid. [Example 3] Using the etching liquids N〇.6 and No. 7 described in the above Examples, an etching test was performed on each of the films of the 50 nm yttrium oxide film and the 3 Å nm yttrium oxide. Specifically, the film substrate was immersed in a 45 Ϊ etching solution and immersed for 15 minutes. As a result, it was confirmed that each film was removed. 100144791