201224208 六、發明說明： 【發明所屬之技術領域】 關於一種用於_同時存在有金屬氧化物層和 =被處理物’而選擇性地_ 用前述蝕刻劑的蝕刻方法。 变^ ^及便 【先前技術】 先前，由氧化銦錫(ΙΤΟ)或氧化銦鋅(1 電性金屬氧化物層，由於電阻低並顯示出高此， 作=導電體而被廣泛應用。另外，也正在研究將由201224208 VI. Description of the Invention: [Technical Field] The present invention relates to an etching method for selectively using a metal oxide layer and a material to be processed, and optionally using the foregoing etchant. ^^和便 [Prior Art] Previously, indium tin oxide (yttrium) or indium zinc oxide (1 electrical metal oxide layer, due to low resistance and showed high, is widely used as = conductor. Is also being studied by
In2^Zn(^I(3ZQ #㈣朗金屬氧化物 子紙等各種裝置中。在將這種金屬氧化 物應用於各種衷置中時，通常是以與經圖案化而成 形狀等的金屬層共存的形態來使用。 Μ —电 工成_存在有金魏化物層和經圖案化的金 屬層的形恶的方法’已知有如下方法： 有金屬氧化物層的被加工物、或金屬氧化物層L；積= 屬層的被加工物、或金屬氧化物層鄰設有金屬層的被加工 物等的同時存在有金屬氧化物層和金屬層的被加工物，使 用蝕刻劑選擇性地蝕刻前述金屬層。 U 在下述專利文獻丨巾，記载有—種製造同時存 在有ΙΤΟ層和經圖案化的鋁層的液晶元件的方法，其使用 包括填酸、乙酸及硝酸的混合酸作為紹層的 [先前技術文獻] χ 1=1 (專利文獻） 專利文獻1 :曰本特開平10-96937號公報 4/16 201224208 【發明内容】 [發明所欲解決的課題] 近年來，尤其對方\顯+ gg、^ , 化、高精細化的要求，傾向、;使肝=:線’因大晝面 -種電阻比罐更低的電極使田配線的，希望獲得 極來代替紹電極。然而，對於 正在研究使用銅電 二究可以從同時存在有金屬氧:物= = ，成:尤其: 不斷發展，如果前述透明金屬 勿::二口 餘，將會成為致命的缺陷。因此，希望浸 金屬=物層而可以選擇性地健刻銅層 曰4 ，發明找於上述情心完成，其提供I# 叫存在有金屬氧化物層和銅 駄姓刻 法。^ _劑及使用前祕刻劑的钱刻方 [用以解決課題的手段] 刻同== = =發明是-種㈣劑’其_ 二=層 氧化物層是包含選自二？ ^ a中的1種以上金屬的氧化物， 剞述蝕刻劑的特徵在於： ο 1 =括以銅離子計為0,1〜3.0重量0/〇的銅(11)離子源. 重旦〜。1_°的碳數為6以下的有機酸；….1〜^) 以上虱原子的雜環化合物以及碳數為8以下的 5 / 16 4 4201224208 含氛基化合物所構相群巾的丨種以上， 其pH為5.0〜1〇 5。 並且’本發明的網方法是使祕 金屬氧化物層和銅層的被處理物 4同時存在有 對前述靖妨剝彳，_金龜制ΓΛ’=選擇性地In2^Zn(^I(3ZQ#(4)) is used in various devices such as metal oxide paper. When this metal oxide is used in various places, it is usually a metal layer patterned with a shape or the like. The coexistence of the form is used. Μ - Electrician _ There is a method of forming a gold-based layer and a patterned metal layer. The following methods are known: a processed material having a metal oxide layer, or a metal oxide The layer L; the product of the genus layer, or the workpiece having the metal oxide layer and the metal layer, and the metal oxide layer and the metal layer, are selectively etched using an etchant. The metal layer is described in the following patent document, which describes a method for producing a liquid crystal element having both a tantalum layer and a patterned aluminum layer, using a mixed acid comprising acid, acetic acid and nitric acid. [Prior Art Document] χ 1 = 1 (Patent Document) Patent Document 1: Japanese Patent Application Laid-Open No. Hei 10-96937 No. 4/16 201224208 [Disclosed] [Problems to be Solved by the Invention] In recent years, especially the other party\ Display + gg, ^, chemistry, high definition The requirements, tendencies,; make the liver =: line 'because of the large surface - the resistance of the lower electrode than the tank to make the field wiring, I hope to obtain the pole to replace the electrode. However, for the study of the use of copper electricity can be from At the same time, there is metal oxygen: material = =, into: especially: continuous development, if the aforementioned transparent metal does not:: two, it will become a fatal flaw. Therefore, it is hoped that the metal layer = layer can be selectively engraved The copper layer 曰4, the invention finds the above-mentioned feelings to complete, which provides I# called the presence of a metal oxide layer and a copper sputum method. ^ _ agent and the use of the former secret agent for money engraving [to solve the problem means The same as the == = = invention is a kind of (four) agent 'the _ two = layer oxide layer is an oxide containing one or more metals selected from the group, the etchant is characterized by: ο 1 = include a copper (11) ion source with a copper ion count of 0,1 to 3.0 wt0/〇. An organic acid having a carbon number of 6 or less in a heavy denier ~.1_°;....1~^) a heterocyclic compound and a group having a carbon number of 8 or less 5 / 16 4 4201224208 containing an occlusive compound, and having a pH of 5.0 to 1 〇 5. And the net method of the present invention is that the metal oxide layer and the copper layer of the object to be treated 4 are simultaneously present, and the 龟金龟ΓΛΓΛ=selectively
Sn、ΑΙ、:η以及Ga中的1種以上金屬的\:物3選自Ζη、 其特徵在於：前龍刻劑是上述本發明的钱 另外，在上述本發明的姓刻劑以及_方、= 層”既可以由銅構成’也可以由 ：：’ “銅 明書中“銅”是指銅或銅合金。 〜Μ且，本說 [發明的效果]The \: thing 3 of one or more metals of Sn, ΑΙ, η, and Ga is selected from Ζη, and is characterized by the fact that the former stencil is the above-mentioned money of the present invention, and the above-mentioned surname and the squaring of the present invention. , = layer "can be made of copper" or ":" "Bronze" in copper means copper or copper alloy. ~Μ,, this said [effect of invention]
t果S本發明_刻劑以及_方法，在 ，子有金屬氧化物層和銅層的被處理 二I 僅㈣前雜層。由此，例如在製朝時存在=== 物層和經圖案化的金屬層的裝置時，可以提高成品ΐ% 低製造成本。 【實施方式】 本發明的I虫刻劑是以用於姓刻同時存在有金屬氧化物 層和銅層理物，而選擇性地蝕刻前述銅層的蝕刻劑 為對象’前述金屬氧化物層是包含選自Zn、Sn、Μ，以 及Ga中的1種以上金屬的氧化物。構成前述金屬氧化物層 的金屬氧化物既可以是單一的金屬氧化物，也可以是複合 金屬氧化物，例如可以列舉：Zn〇、Sn〇2、Ab〇3、氧化銦 錫(ITO)、氧化銦鋅(IZO)、in_Ga_Zn〇4 或 In2_Ga2_Zn〇7 等 IGZO等。從钱刻銅層時防止金屬氧化物層的浸蝕觀點來 看’較佳為包含選自由Zn、Sn及A1中的1種以上金屬的 6/16 201224208 =物的金屬氧化物層，更佳為包含選自由Zn〇、Sn〇2、 aj2o3、ITO、IZO 以;5 l 層氧化物層。及1GZ0中的】種以上金屬氧化物的金 (銅(Π)離子源） 而私禮㈣1 續射’銅(_子源是做為綱氧化劑 二斤 的成分。前述銅(Π)離子源，例如可以列舉：下 錯合物、氣氧化銅；下述有機酸的銅錯 m’或者氯化銅或漠化銅等 月中，可以使用它們中的-種或多種組 乙酸銅、氯物料看，錄為甲酸銅、 更佳為0.5〜2.0重量％。 為0.25〜2.5重量％， (石厌數為6以下的有機酸） 作為f容6«下的有機酸來 螂'，、二乳化的銅的成分。從提高鋼的交护 f，前述有機酸的碳數較佳為卜5 /彳硯點來 :述有機酸既可以單獨調配至姓刻劑中=〜4。另外， 物的形式調配至_射。 切以以鋼錯合 前述有機酸例如可以例示：脂肪 寺。前物肪酸的具體例可列舉^ 7香族缓酸 丙酸、丁酸、戊酸及已酸等脂肪族飽和—° ·:，、乙酸、 巴頌及異巴豆酸等脂肪族不飽和 ，’叫酸、 _丁一s义、戍一s义、己二酸及庚二 次、丙 顿峻；馬練等麟财飽和二元、g肪族飽和二 久’己醇酸、乳酸、 7/16 201224208 蘋果酸及檸檬酸等羥基羧酸；氨基磺酸、沒―氣丙酸、煙酸、 抗壞血酸、羥基新戊酸及乙醯丙酸等具有取代基的羧酸； 以及其衍生物等。在本發明中，可以使用它們中的一種或 多種組合使用。其中，從不阻礙銅的氧化作用，且不會有 導致姓刻劑黏度上升的顧慮等觀點來看，較佳為脂肪族飽 和一元羧酸、脂肪族飽和二元羧酸、羥基羧酸，更佳為曱 酸、乙酸、丙酸、丁酸、已酸、乙二酸、乳酸、蘋果酸及 檸檬酸。 ' 前述有機酸的含量為化丨〜邓刃重量％，較佳為0.5〜 20.0重1%，更佳為ί ο〜;1〇 〇重量。/。。如果前述有機酸的 含量在0.1重量％以上，氧化銅的溶解性將提高。並且，如 果前述有機酸的含量在30.〇重量％以下，可以抑制銅的溶 解穩定性降低，並且可以防止有機酸結晶析出。 (含氮化合物） 在本發明的蝕刻劑中，調配選自由環内具有2個以上 氮原子的雜環化合物以及碳數為8以下的含胺基化合物所 構成的群中的1種以上的含氮化合物，係用以使溶解的銅 以錯5物的形式做為保持在钱刻刻中之成分而調配。在本 發明中，可以使用一種或多種含氮化合物。另外，前述含 氮化合物既可以單獨調配至蝕刻劑中，也可以以銅錯合物 的形式調配至蝕刻劑中。並且，前述含氮化合物不包括前 述有機酸。 前述雜環化合物只要是環内具有2個以上氮原子即 可’並無特別限定，例如可以例示：咪唑類、吡唑類、三 唑類、四唑類及它們的衍生物等唑類等。從其與溶解的鋼 之間的錯合性觀點來看，較佳為咪唑或笨并咪唑等咪唑 8/16 201224208 類、或者吡唑等吡唑類。具體可以例示：咪唑、2 u-二乙基t坐、苯并咪。坐、㈣、三唾及笨并三^等= 中較佳為糾、2•曱基料、1;2_二乙基料、笨并味_ 〇比π坐。 久 前述含胺基化合物只要是碳數為8以下即可，並 別限定，但從其與溶_銅之間的錯合性觀點來看，較^ 碳數為0〜7，更佳碳數為〇〜5。 t 如述含胺基化合物例如可以例示：氨；甲基胺、一 胺、三曱胺等烧基胺；烧醇胺；苯胺等芳香族胺等1並:甲 也可以使用乙二胺等含有2個以上胺基的胺化合物或 銨等四級胺化合物。其巾，從紅溶解的銅的錯合性 來看，較佳為氨、烷醇胺。 … 前述烷醇胺的具體示例，例如可以列舉：單乙醇胺、 N·甲基乙醇胺、N_乙基乙醇胺、Ν_τ基乙醇胺、㈣_ ^乙醇胺、Ν，Ν-二乙基乙醇胺、2_(2_雜)乙氧基乙醇_ 早乙醇胺及其衍生物；二乙醇胺、Ν·ψ基二乙醇胺、財 基二醇胺等二乙醇胺及其衍生物；三乙醇胺；丙醇胺； 異丙醇胺；經乙基纟；以及它們的衍生物等。其中，從 其與溶解的銅之間的錯合性觀點來看，較佳為單’乙醇胺Γ —乙醇胺及三乙醇胺。 人從其與溶解的銅之間的錯合性觀點來看，前述含氮化 合物較佳為咪销、t坐類、氨及烧醇胺，更佳為^、 曱基米唾、1，2·二乙基_。坐、苯并〇米。坐、〇比唾、、。 醇胺、二乙醇胺及三乙醇胺。 早 岫述含氮化合物的含量為〇,】〜3〇.〇重量％，較佳為1 〇 〜25.0重量％ ’更佳為】〇 〇〜2〇 〇重量％。如果前述含氮化 9/16 201224208 合物的含量在G.1重量％以上’可以提高㈣速度。並且， 如果前述含氣化合物的含量在3〇〇重量％以下，可以抑制 I虫刻劑的黏度上升。 (其他添加劑） 為了提高銅的溶解性和溶解穩定性並减高餘刻速 度’也可以在本發明的餘刻劑中調配齒離子源。前述齒離 子源的具體示例例如可以列舉：氫氯酸、氫演酸及氫班酸 等無機酸；氯化銅、漠化銅、氣化鐵、氣化納、峨化納及 氣化敍等無機鹽。另外，為了進行均勾的飯刻，本發明的 _劑中也可以調配有聚亞焼基二醇或聚亞烧基二醇衍生 物=面=劑等。這些添加劑在_劑中的含量為_ 〜10重罝％左右。 從钱刻銅層時防止金屬氧化物 I明的嶋的PH為 為5.0〜7.0。尤其是從防止包含Zn、Sn、Ai 的，物層的軸點來看，較佳二 == 另外’可以通過調整前述有機酸心 μ 3虱化&物的含量來控制蝕刻劑的pH。 本發明_刻劑藉由使前述各成分溶解於水中 ^地_ ° f述水較佳為去離子水。並且，本發明的钱 分調配成使用時的特定濃度，也可 使=絲備—液，並在即將使用前將前述濃縮液稀釋後 被處理物上的方法、將前述被處理物浸潰在心 10/16 201224208 士等。由於當使用浸潰法時，是將因 中所產生的鋼⑴離子氧化成銅(π)離子，因此刻劑 氣泡等吹人空氣。進行__時 10〜机，處理時間較佳為1〇〜12()秒。U的酿度優選為 和經=;r:rj適用於製造同時存在有金屬氧化物層 晶广前述元件可列舉例如:液 等。 I 觸控硫、電子缺光電轉換元件 [實施例] 明 另、> 比較例對本發明的姓刻劑的實施例進行說 ’並非將本發明理解為限定於以下實施例。 (銅層的蝕刻速度）The result of the invention is as follows: in the case where the metal oxide layer and the copper layer are treated, the second I (only) pre-hybrid layer. Thus, for example, when a device having a === layer and a patterned metal layer is present at the time of manufacture, it is possible to improve the manufacturing cost and the manufacturing cost. [Embodiment] The etchant of the present invention is an etchant for selectively etching a copper layer while a metal oxide layer and a copper layer are simultaneously present, and the metal oxide layer is included. An oxide of one or more metals selected from the group consisting of Zn, Sn, bismuth, and Ga. The metal oxide constituting the metal oxide layer may be a single metal oxide or a composite metal oxide, and examples thereof include Zn〇, Sn〇2, Ab〇3, indium tin oxide (ITO), and oxidation. IGZO such as indium zinc (IZO), in_Ga_Zn〇4 or In2_Ga2_Zn〇7. From the viewpoint of preventing corrosion of the metal oxide layer when engraving the copper layer, it is preferably a metal oxide layer containing 6/16 201224208 = one selected from one or more metals selected from the group consisting of Zn, Sn, and A1, more preferably The layer comprises an oxide layer selected from the group consisting of Zn〇, Sn〇2, aj2o3, ITO, and IZO; And 1GZ0] gold (copper (Π) ion source) of the above metal oxides and private gifts (4) 1 continued to emit 'copper (_ sub-source is a component of the oxidant, which is the oxidant, the copper source) For example, there may be mentioned a lower complex, a copper oxide; a copper wrong m' of the following organic acid, or a copper chloride or a desert copper, etc., and the copper or chlorine materials of the above-mentioned species or groups may be used. It is recorded as copper formate, more preferably 0.5 to 2.0% by weight. It is 0.25 to 2.5% by weight, (the organic acid having a stone anisotropy of 6 or less) is used as an organic acid under the f-capacity 6«, and is emulsified. The composition of copper. From the improvement of the steel f, the carbon number of the organic acid is preferably 5 / 彳砚: the organic acid can be separately formulated into the surname = 〜4. In addition, the form of the substance For example, it can be exemplified by the above-mentioned organic acid, which is exemplified by the fat temple. Specific examples of the fatty acid of the precursor can be exemplified by aliphatic aliphatic acid, butyric acid, valeric acid and acid. Saturated-° ·:,, acetic acid, saponin and isocrotonic acid are unsaturated, such as acid, _ 丁丁s, 戍一s, adipic acid And Geng secondary, Bing Dunjun; Ma Lian and other Lin Cai saturated binary, g aliphatic saturated two long 'hexanol, lactic acid, 7/16 201224208 malic acid and citric acid and other hydroxycarboxylic acid; sulfamic acid, no a carboxylic acid having a substituent such as a gas propionic acid, nicotinic acid, ascorbic acid, hydroxypivalic acid or acetyl propionic acid; and a derivative thereof, etc. In the present invention, one or a combination of them may be used in combination. It is preferably an aliphatic saturated monocarboxylic acid, an aliphatic saturated dicarboxylic acid, or a hydroxycarboxylic acid, from the viewpoint of not hindering the oxidation of copper and causing no concern that the viscosity of the surname is increased. It is citric acid, acetic acid, propionic acid, butyric acid, acid, oxalic acid, lactic acid, malic acid and citric acid. 'The content of the above organic acid is phlegm to Dengjian weight%, preferably 0.5 to 20.0 weight 1 %, more preferably ί ο~; 1 〇〇 weight. If the content of the aforementioned organic acid is 0.1% by weight or more, the solubility of copper oxide will increase. And, if the content of the aforementioned organic acid is 30. Below %, it is possible to suppress a decrease in the dissolution stability of copper, and In the etchant of the present invention, a group selected from a heterocyclic compound having two or more nitrogen atoms in the ring and an amine group-containing compound having a carbon number of 8 or less is prepared. One or more kinds of nitrogen-containing compounds are used to prepare dissolved copper in the form of a faulty substance as a component to be retained in the engraving. In the present invention, one or more nitrogen-containing compounds may be used. Further, the nitrogen-containing compound may be formulated separately into the etchant or may be formulated into the etchant in the form of a copper complex. The nitrogen-containing compound does not include the organic acid. The number of the nitrogen atoms is not particularly limited, and examples thereof include azoles such as imidazoles, pyrazoles, triazoles, tetrazoles, and derivatives thereof. From the viewpoint of the mismatch between the steel and the dissolved steel, it is preferably an imidazole such as imidazole or stupid imidazole 8/16 201224208 or a pyrazole such as pyrazole. Specifically, it can be exemplified by imidazole, 2 u-diethyl t sitting, and benzopyrene. Sitting, (four), three saliva and stupid and three ^ etc. = better in the correction, 2 • 曱 base material, 1; 2_ diethyl material, stupid and _ 〇 〇 than π sitting. The long-term amino group-containing compound may be a carbon number of 8 or less, and is not limited thereto. However, from the viewpoint of the compatibility with the copper-soluble copper, the carbon number is 0 to 7, and the carbon number is more preferable. For 〇~5. t As the amine-containing compound, for example, ammonia; an alkylamine such as methylamine, monoamine or tridecylamine; an alkoxyamine; an aromatic amine such as aniline; and the like: An amine compound having two or more amine groups or a quaternary amine compound such as ammonium. The towel is preferably ammonia or an alkanolamine from the viewpoint of the misalignment of red-dissolved copper. Specific examples of the aforementioned alkanolamines include, for example, monoethanolamine, N.methylethanolamine, N-ethylethanolamine, Ν_tauethanolamine, (iv) _^ethanolamine, hydrazine, hydrazine-diethylethanolamine, 2_(2-hetero Ethoxyethanol_preethanolamine and its derivatives; diethanolamine, hydrazinodiethanolamine, diethanolamine and its derivatives; triethanolamine; propanolamine; isopropanolamine; Bases; and their derivatives, etc. Among them, from the viewpoint of the mismatch between the copper and the dissolved copper, mono-ethanolamine oxime-ethanolamine and triethanolamine are preferred. From the viewpoint of the mismatch between the copper and the dissolved copper, the nitrogen-containing compound is preferably a rice pin, a t-sodium, an ammonia or an alkalamine, more preferably a thiophene saliva, 1, 2 · Diethyl _. Sit, benzo glutinous rice. Sitting, squatting, and. Alcoholamine, diethanolamine and triethanolamine. The content of the nitrogen-containing compound is 〇, 〜3〇.〇% by weight, preferably 1 〇 to 25.0% by weight ‘more preferably 〇 〇~2〇 〇% by weight. If the content of the above-mentioned nitride-containing 9/16 201224208 is more than G.1% by weight or more, the speed can be increased. Further, if the content of the gas-containing compound is 3% by weight or less, the increase in the viscosity of the insect etchant can be suppressed. (Other Additives) To increase the solubility and dissolution stability of copper and to reduce the residual speed, it is also possible to prepare a tooth ion source in the remnant of the present invention. Specific examples of the above-mentioned tooth ion source include inorganic acids such as hydrochloric acid, hydrogen acid, and hydrogen peroxide; copper chloride, desert copper, gasified iron, gasification sodium, sodium hydride, gasification, and the like. Inorganic salt. Further, in order to carry out the uniform cooking, the polyalkylene glycol or the polyalkylene glycol derivative = surface = agent may be formulated in the agent of the present invention. The content of these additives in the agent is about _10% by weight. The pH of the metal oxide is prevented from being 5.0 to 7.0 when the copper layer is carved. In particular, from the viewpoint of preventing the axial point of the layer containing Zn, Sn, and Ai, it is preferable that the pH of the etchant can be controlled by adjusting the content of the organic acid core μ 3 && The present invention is preferably deionized water by dissolving the above components in water. Further, the money of the present invention is blended into a specific concentration at the time of use, and the method of dipping the liquid to the object to be treated immediately before use, and immersing the object to be treated in the heart 10/16 201224208 士等. Since the steel (1) ion generated by the oxidation is converted into copper (π) ions when the dipping method is used, the air bubbles are blown by the engraving bubbles or the like. When performing __ 10~ machine, the processing time is preferably 1〇~12() seconds. The degree of brewing of U is preferably and ==; r: rj is suitable for the production of a metal oxide layer at the same time. The above-mentioned elements may be, for example, liquid or the like. I. Touch sulfur and electron-deficient photoelectric conversion element [Embodiment] The following is a description of an embodiment of the surname of the present invention. The present invention is not construed as being limited to the following examples. (etching speed of copper layer)
Works cH 16 _ 的松下電工公司（PanaS〇niC E〗ectric 氧多層板^^、:^麵板（產品名稱：玻璃環 50 g/L、剩餘邻八貝於姓刻液（硫酸200机、過氧化氫 箱，使用自、。卩”為去離子水）巾，完全除去該層驗的銅 Ltd )制、生六野製樂工業公司（〇kun〇 Chemical Industries Co.， 右· Γ·^Τ的非電解鑛敷液（產品名稱：0PC C0PPER H )， 的^電解=環氧基材的一側全面施行厚度約為h5㈣ 板。使用=，並將其切割成50 mmx50 mm，作為試驗基 秒的一涂^ 1中所記載的各蝕刻劑（溫度：3〇。〇)通過30 麸徭，t处理塗塵：〇.05 MPa)對前述基板進行姓刻。 速声η處理前後的試驗基板的重量，根據下式計算餘刻 字結果示於表2中。另外，表2中的“無法測定” 生變化。進仃3〇秒的蝕刻處理，試驗基板的重量也未發 11/16 201224208 蝕刻速度（分）=[處理前的重量(g)—處理後的重 量(g)]+基板面積(m2)+8.92(g/cm3)+處理時間（分） (ITO層以及IGZO層的蝕刻速度） 使用通過喷塗法在100 mmxlOO mm、厚度為2 mm的 浮法玻璃基材（旭硝子公司(Asahi Glass Co” Ltd.)製造）上 形成厚度為0.2 /zm的ITO覆膜或IGZO覆膜的基材作為 試驗基板。使用表1中所記載的各蝕刻劑（溫度：3〇〇c )， 通過噴塗處理（喷塗壓：〇.1MPa)對這些試驗基板進行蝕 刻，並通過XPS測定每經過3〇秒處理的表面。然後，從組 成，分之一的In的峰值消失的時間開始，根據以下公式計 :十开姓，刻速度。將結果示於表2中。另外’表2中的“無 法測定”技g卩使進行1G分鐘㈣處理七的峰值私 生變化。 & 餘刻速度Um/分）=〇 2 的處理時間（分)] [至In的峰值消失為止 12/16 201224208 蝕刻劑（剩餘部分為去離子水） _ 1 'ό 00 ίτΐ 〇 5 卜 in 00 'd 寸 Tf Γ— ιτΐ 5 〇〇 Ρ P 含氮化合物 含氮化合 物的總含 量（重量 %) ο ο 20.00 〇 30.00 〇 〇 〇 CN 20.00 〇 in 20.00 ο ο on 40.00 〇 〇 〇 〇 tri 30.00 15.40 含胺基化合物 含量（重 量％) _1 10.00 ο ο 10.00 1 30.00 S 〇 10.00 〇 1 15.00 1 15.00 20.00 1 10.00 〇 20.00 10.00 種類 _ _1 三乙醇胺 二乙醇胺 單乙醇胺 I 三乙醇胺 二乙醇胺 24重量％氨水 二乙醇胺 1 單乙醇胺 1 三乙醇胺 單乙醇胺 1 三乙醇胺 二乙醇胺 1 單乙醇胺 24重量％氨水 雜環化合物 Ifftlt ο ο ιΧ ο 10.00 15.00 I 〇 10.00 15.00 15.00 〇 15.00 1 20.00 〇 〇 〇 iri 10.00 10.00 13.00 種類 σ米嗤 2-甲基17米哇 。米°坐 味α坐 1 2-甲基。米°坐 1,2-二乙基咪唑 11 米嗤 2-甲基咪唑 α米嗤 1 i 味嗤 2-甲基咪唑 咪峻 ;1,2-二乙基咪吐 2-曱基咪唑 有機酸 含量 (重量％) ο ο ο 10.00 10.00 〇 10.00 10.00 30.00 〇 d 10.00 Ο Ο ιτΐ ο 30.00 〇 〇 ;50.00 〇 〇 〇 〇 種類 蘋果酸 «π S- 乙酸 乙二酸 丁酸 丙酸 蘋果酸 乙酸 乙酸 乙酸 蘋果酸 乙酸 乙酸 乙酸 曱酸 蘋果酸 蘋果酸 銅(II)離子源 以銅離子 計算的含 量 (重量％) 1 ο ο ο ο Γ〇 〇 〇 〇 〇 〇 〇 〇 CN 〇 〇 (N d 〇 p 10.00 5 Ο 〇 〇 〇 〇 〇 〇 _ _ $ 伞1 ο ο ri 10.00 d 〇 〇 rn in 〇 〇 〇 r-i 〇 〇 〇 oi 30.00 s ο 〇 rn 〇 〇 ΓΊ 〇 (N 〇 〇 〇 〇 (N 種類 1 乙酸銅(II) 一水合物 漠化銅 甲酸銅 漠化銅 漠化銅 漠化銅 乙酸銅(丨丨)一水合物 乙酸銅(丨丨)一水合物 乙酸銅(丨丨)一水合物 甲酸銅 漠化銅 乙酸銅(Π) —水合物 乙酸銅(丨丨)一水合物 臭化鲖 甲酸銅 乙酸銅(丨丨)一水合物 漠化銅 甲酸銅 1實施例1 1實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例丨〇 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 比較例8 201224208 [表2] 姓刻速度（,t/m/分） 銅層 ΙΤΟ層 IGZO 層 實施例1 1.50 無法測定(与0) 無法測定(^0) 實施例2 1.50 無法測定(与0) 無法測定（与0)) 實施例3 0.80 無法測定(与0) 無法測定(与0) 實施例4 0.90 無法測定(与0) 無法測定(与0) 實施例5 1.20 無法測定(与0) 無法測定(与0) 實施例6 1.00 無法測定(与0) 無法測定(与0) 實施例7 1.60 無法測定〇0) 無法測定(与0) 實施例8 0.70 無法測定(与0) 無法剥定(与0) 實施例9 0.40 無法測定(与0) 無法測定(与0) 實施例10 1.30 無法測定(与0) 無法測定(与0) 比較例1 0.40 0.07 0.03 比較例2 0.01 無法測定(与0) 無法測定(与0) 比較例3 0.01 無法測定(与0) 0.20 比較例4 無法測定(与0) 無法測定(与0) 無法測定(与0) 比較例5 因結晶析出而無法1虫刻 0.01 0.08 比較例6 無法測定(与0) 0.08 0.06 比較例7 0.90 0.10 0.10 比較例8 0.09 0.10 0.50 如表2所示，根據本發明的實施例，與比較例相比， 均可擴大銅層的姓刻速度與ITO層或IGZO層的I虫刻速度 之間的差。根據該結果可以確認，如果利用本發明，可以 從同時存在有金屬氧化物層和銅層的被處理物選擇性地僅 I虫刻銅層。 【圖式簡單說明】 無。 【主要元件符號說明】 14/16 201224208Works cH 16 _ of Matsushita Electric Works Co., Ltd. (PanaS〇niC E) ectric oxygen multi-layer board ^^, :^ panel (product name: glass ring 50 g / L, the remaining neighboring eight shells in the surname engraving (sulphuric acid 200 machine, over The hydrogen peroxide tank, using the 卩 为 为 去 去 , 完全 完全 完全 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 The electroless plating solution (product name: 0PC C0PPER H), ^ electrolysis = one side of the epoxy substrate is fully applied to a thickness of about h5 (four) plate. Use =, and cut it into 50 mm x 50 mm, as the test base Each of the etchants (temperature: 3 〇. 〇) described in the coating 1 was subjected to a surname of 30 gluten, t-treated dust: 〇.05 MPa). The test substrate before and after the speed η treatment The weight is calculated according to the following formula. The results of the engraving are shown in Table 2. In addition, the "unable to measure" change in Table 2. The etching process of 3 sec., the weight of the test substrate was not issued 11/16 201224208 Etching Speed (minutes) = [weight before treatment (g) - weight after treatment (g)] + substrate area (m2) + 8.92 (g/cm3) + Processing time (minutes) (etching speed of ITO layer and IGZO layer) was formed by a spray method on a float glass substrate (manufactured by Asahi Glass Co. Ltd.) of 100 mm x 100 mm and a thickness of 2 mm. A substrate having an ITO film or an IGZO film having a thickness of 0.2 /zm was used as a test substrate. Each of the etchants (temperature: 3 〇〇c) described in Table 1 was used, and spray treatment was performed (spray pressure: 〇.1 MPa). These test substrates were etched, and the surface treated every 3 sec. was measured by XPS. Then, from the time when the composition of one of the peaks of In disappeared, the following formula was calculated according to the following formula: The results are shown in Table 2. In addition, the "unable to measure" technique in Table 2 allows the peak stagnation change of 1 G minutes (4) to be processed. & Residual velocity Um/min) = processing time of 〇2 (分)] [To the peak of In disappears 12/16 201224208 Etchant (the remainder is deionized water) _ 1 'ό 00 ίτΐ 〇5 卜 in 00 'd inch Tf Γ — ιτΐ 5 〇〇Ρ P Nitrogen-containing compound Total content of nitrogen-containing compounds (% by weight) ο ο 20.00 〇 30.00 〇〇〇CN 20.00 〇in 20.00 ο ο on 40.00 〇〇〇〇tri 30.00 15.40 Amino group content (% by weight) _1 10.00 ο ο 10.00 1 30.00 S 〇10.00 〇1 15.00 1 15.00 20.00 1 10.00 〇20.00 10.00 Species _ _1 Triethanolamine Diethanolamine Monoethanolamine I Triethanolamine Diethanolamine 24% by weight Ammonia Diethanolamine 1 Monoethanolamine 1 Triethanolamine Monoethanolamine 1 Triethanolamine Diethanolamine 1 Monoethanolamine 24% by weight Ammonia Heterocyclic Compound Ifftlt ο ο ιΧ ο 10.00 15.00 I 〇10.00 15.00 15.00 〇15.00 1 20.00 〇〇〇iri 10.00 10.00 13.00 Type σ m嗤 2-methyl 17 mw. The rice sits on the taste α sitting 1 2-methyl. Rice, 1,2-diethylimidazole, 11 m嗤2-methylimidazole α m嗤1 i miso 2-methylimidazolium; 1,2-diethylimiprop-2-mercaptoimidazole organic acid Content (% by weight) ο ο ο 10.00 10.00 〇10.00 10.00 30.00 〇d 10.00 Ο Ο ιτΐ ο 30.00 〇〇; 50.00 〇〇〇〇 type malic acid «π S- acetic acid oxalic acid butyrate propionic acid malic acid acetic acid acetic acid Malic acid acetic acid acetic acid acetic acid phthalic acid malic acid malic acid copper (II) ion source calculated by copper ion content (% by weight) 1 ο ο ο ο Γ〇〇〇〇〇〇〇〇CN 〇〇 (N d 〇p 10.00 5 Ο 〇〇〇〇〇〇 _ _ $ Umbrella 1 ο ο ri 10.00 d 〇〇rn in 〇〇〇ri 〇〇〇oi 30.00 s ο 〇rn 〇〇ΓΊ 〇(N 〇〇〇〇(N species 1 acetic acid Copper(II) monohydrate desertification copper formate copper desertification copper desertification copper desertification copper copper acetate (丨丨) monohydrate copper acetate (丨丨) monohydrate copper acetate (丨丨) monohydrate copper formate Desertification copper copper acetate (Π) - hydrate copper acetate (丨丨) monohydrate odorized bismuth formate copper copper acetate (丨) monohydrate desertification copper formate 1 Example 1 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 丨〇 Comparative Example 1 Comparative Example 2 Comparison Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 201224208 [Table 2] Name engraving speed (, t/m/min) Copper layer IG IGZO layer Example 1 1.50 Unable to measure (and 0) Measurement (^0) Example 2 1.50 Unable to measure (and 0) Unable to measure (and 0)) Example 3 0.80 Cannot be measured (and 0) Unmeasurable (and 0) Example 4 0.90 Unmeasurable (and 0) Unable to measure (And 0) Example 5 1.20 Unable to measure (and 0) Unable to measure (and 0) Example 6 1.00 Unable to measure (and 0) Unable to measure (and 0) Example 7 1.60 Unable to measure 〇0) Unable to measure (with 0 Example 8 0.70 Cannot be measured (and 0) Unable to be stripped (and 0) Example 9 0.40 Unmeasured (and 0) Unmeasurable (and 0) Example 10 1.30 Unmeasurable (and 0) Unmeasurable (with 0) Comparative Example 1 0.40 0.07 0.03 Comparative Example 2 0.01 Unable to measure (and 0) Unable to measure (with 0) Comparative Example 3 0.01 Unable to measure (with 0) 0.20 ratio Example 4 Unable to measure (and 0) Unable to measure (and 0) Unable to measure (and 0) Comparative example 5 Cannot be insulted by crystal precipitation 0.01 0.08 Comparative Example 6 Unable to measure (with 0) 0.08 0.06 Comparative Example 7 0.90 0.10 0.10 Comparative Example 8 0.09 0.10 0.50 As shown in Table 2, according to the embodiment of the present invention, the difference between the surname speed of the copper layer and the I-injection speed of the ITO layer or the IGZO layer can be expanded as compared with the comparative example. From this result, it was confirmed that, according to the present invention, it is possible to selectively etch only the copper layer from the object to be treated in which the metal oxide layer and the copper layer are simultaneously present. [Simple description of the diagram] None. [Main component symbol description] 14/16 201224208