201040316 六、發明說明： 【發明所屬之技術領域】 本發明為有關於一種半導體等所使用的積層膜之蝕刻 液。 【先前技術】 由於液晶顯示裝置顯示面積之大型化，與薄膜電晶體 接續之閘線與信號線亦須加長，這些配線之電阻也變高， 因而產生訊號延遲等的問題。先前液晶顯示裝置之金屬配 線中使用A丨’但大型基板中係使用電阻較低2Cu配線。 在銅配線的閘極金屬中’為防止Cu擴散至半導體膜， 且為提高與半導體膜之密合性，故使用Ti、M〇、Cr等金屬 膜。亦即，構成Cu/Mo、Cu/Ti、Cu/Cr等之積層膜。將如此 之積層膜構造進行蝕刻加工時，有經蝕刻加工(：11膜後再蝕 刻加工屬基底膜之Mo或Ti之2段操作方式，及Cu/M〇4Cu/Ti 積層膜以單一液一次蝕刻加工之同步蝕刻方式的2種方 法。後者之同步蝕刻方式在作業步驟方面較佳，惟對耐蝕 性不同之金屬積層膜以單一液蝕刻並不易’且在因考量電 池效果等之影響而將積層膜製成無段差之錐形時，同步蝕 刻亦不易操作。甚且，基於配線加工之精密度方面，必須 盡可能避免橫向產生過度蝕刻（邊蝕刻），因此同步蝕刻液之 開發極為不易。 / 在如此之背景下，目前係探討選擇對構成各層之各金 屬有效的氧化劑’對Cu/Mo或Cu_Cu/Cr等進行同步侧 之方法。 "例如在專利文獻W，係揭示使用溶解Cu之氧化劑的過 氧硫酸-氫鉀之侧技術，其中係探討配合基底積層金屬 4/19 201040316 传以刻液。亦即’其中揭示之_組成物， 二酸-氫鉀為必須成分，在㈣崎再配合氣酸或 匕氧H鹽與氟化物之組合，在Cu/M。時再配合磷酸與確酸 之組〇 ’ Cu/Cr時再配合鹽酸之組合。 又 "在專利文獻2至4中，則揭示使用溶解cu之氧化劑 的過氧化氫之㈣技術，探討併用各種有機酸或中性鹽丄 再加上各獅加物，騎Cu/M(^Cu/Ti積層社同步^。201040316 VI. Description of the Invention: [Technical Field] The present invention relates to an etching solution for a laminated film used for a semiconductor or the like. [Prior Art] Due to the increase in the display area of the liquid crystal display device, the gate line and the signal line which are connected to the thin film transistor must be lengthened, and the resistance of these wirings is also increased, thereby causing problems such as signal delay. In the metal wiring of the prior liquid crystal display device, A丨' was used, but in the large substrate, a lower resistance 2Cu wiring was used. In the gate metal of the copper wiring, in order to prevent Cu from diffusing to the semiconductor film and to improve adhesion to the semiconductor film, a metal film such as Ti, M〇 or Cr is used. That is, a laminated film of Cu/Mo, Cu/Ti, Cu/Cr or the like is formed. When such a laminated film structure is etched, there is a two-stage operation mode in which Mo or Ti is a base film, and a Cu/M〇4Cu/Ti laminated film is once a single liquid. Two methods of synchronous etching of etching process. The latter synchronous etching method is preferable in terms of work steps, but it is not easy to etch a metal laminated film having different corrosion resistance by a single liquid, and it is affected by the influence of the battery effect or the like. Synchronous etching is also difficult to operate when the laminated film is formed into a stepless taper. Moreover, it is necessary to avoid over-etching (edge etching) in the lateral direction as much as possible in terms of precision of wiring processing, and thus development of a synchronous etching solution is extremely difficult. / In this context, the current method of selecting the oxidant 'effective for the metals constituting each layer' to synchronize the side of Cu/Mo or Cu_Cu/Cr, etc. is discussed. For example, in Patent Document W, it is disclosed that the use of dissolved Cu is disclosed. The side technology of oxidant peroxysulfate-potassium hydrogen, which is discussed in conjunction with the underlying layered metal 4/19 201040316. The engraving is also known as the composition. Acid-hydrogen potassium is an essential component, and in combination with gas or acid and H salt and fluoride, in Cu/M, it is combined with phosphoric acid and acid group 〇' Cu/Cr with hydrochloric acid. In addition, in Patent Documents 2 to 4, the technique of using hydrogen peroxide which dissolves cu oxidizing agent is disclosed, and various organic acids or neutral salts are added together with each lion additive, and Cu/M is riding. (^Cu/Ti laminate company synchronization ^.
膜 最近’為取代Cu/M〇、〇^積層膜之積層膜，又再開 發包含銅合金氧化層之積賴。此等不祕細特性佳， 亦具有在顧步射可以同—裝置將積層之各層成膜之優 點。然而，目前對此新開發之含銅合金氧化層之積層 仍完全未冒探討其有效之飯刻方法。 先前技術文獻 專利文獻 專利文獻1曰本專利第3974305號公報 專利文獻2曰本特開2002-302780號公報 專利文獻3美國專利申請公開第2〇〇6/1 〇5579號說明書 專利文獻4日本特開2004-193620號公報 【發明内容】 發明欲解決之課題 本發明人等在前述先前技術下，再試驗開發由The film has recently been replaced by a laminated film of Cu/M〇 and 〇^ laminated films, and has been developed to contain a copper alloy oxide layer. These characteristics are not good, and they also have the advantage of being able to form a film in each layer of the laminate. However, at present, the newly developed copper-containing alloy oxide layer is still not explored for its effective cooking method. PRIOR ART DOCUMENT Patent Document Patent Document No. 3,974, 305, Patent Document 2, JP-A-2002-302780, Patent Document 3, US Patent Application Publication No. 2/6/1, No. 5579, Patent Document 4, Japanese Patent SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The inventors of the present invention have re-experienced development by the aforementioned prior art.
CuMg/CuMgO、CuCa/CuCaO、Cu/CuCaO、Cu/CuA1Mg〇 等 銅與銅合金氧化物形成的新積層膜之同步蝕刻技術，其中 遭遇例如在Cu單層膜之蝕刻及Cu/M〇、Cu/Ti、Cu/Cr等既存 銅積層膜用之同步蝕刻中，所使用之FeCl3、CuCl2系混合酸 系之蝕刻液，因對CuMg〇&CuCa〇等下層膜之溶解性高， 5/19 201040316 因而基底膜之邊触刻變大，以致無法形成錐形的問題。 亦即本發明之目的’在提供一種可解決前述問題，可 使用於Cu金屬層及cu合金氧化物層之同步蝕刻，可控制高 溶解性銅合金氧化物層之溶解，且對同步触刻對象之在積 層中包含Cu合金氧化物層之全部層，，可實現在適當平衡 的條件下進行溶解之蝕刻液及蝕刻方法。 課題解決之手段 本發明人等為解決上述問題，經一再專精之研究，意 外地發現使用含過氧化物財機酸之侧液，可良好地用 以同步侧上述積層膜，再進_步探討之結果完成本發明。 亦即，本發明為有關於用以將包含與基板相接之銅氧 化物層或銅合金氧化物層的基板上之含銅積層膜進行餘刻 之餘刻液’前祕贿巾含過氧化物與有機酸。 再者，本發明亦為有關於前述蝕刻液，其中含銅声 膜為Cu/CuX0或CuX/CuX〇(式中之乂為呢、〜或曰。 又’本發明亦為有關於前述姓刻液，其阳為3至6。 為過K氫本發明亦為有關㈣舰刻液，其中過氧化物 又，本發明亦為有關於前述餘刻液，其更含螯合劑。 樣酸或甘胺酸 乙二有關於前祕刻液，其中螯合劑為 -八鹼皿、或二伸乙三胺五乙酸及其鹼鹽。 又：i'r月亦為有關於前述蝕刻液’其中有機“檸 再者’本發明亦騎關於前賴麻，其中過 各過硫酸或過硫酸鹽。 勿 又’本發明亦為有關於前述韻刻液，其中過硫酸鹽係 6/19 201040316 選自 khs〇5、NaHS〇5、K2s2〇8、Na2S2〇8、及(ΝΗ4)2 之群。 再者，本發明亦為有關前述餘刻液，其中有機酸為乙 酸。 又，本發明亦為有關於一種餘刻方法，係將其中包含 與基板相接之銅氧化物層或銅合金氧化物層的基板 銅積層膜進行_之方法，且前述方法包含以含過氧化物 與有機酸之蝕刻液進行蝕刻之步驟。 Ο ❹ 發明之效果 本餐明之上述構成，對含銅積層膜與基板相接之層 銅氧化物層或銅合金氧化物層之作用，可抑制銅合金氧化 物層之溶解速度，達㈣何使Cu/CUXQ(X^意之金 積層膜形成錐形而邊飯刻少之同步钱刻。 此可❹下加以制’既存之銅積層膜用同步餘刻 屬之氧化溶解，惟在銅合金氧化物積層膜之溶 2中，銅知並無變化，即應非進行氧化溶解而係進行 ，解’因此對仏合金氧化物膜以如Cu0、Cu02等氧化物推 =安電位侦狀態曲線中，PH4以下並非氧化 物之女疋輕圍而形成Cu離子’因此藉由控制在Cu0 2定範®與(:_子之安定範圍之邊界條件附近(_ “ )’可以控制Cu合金氧化物膜之溶解速度。 【實施方式】 树明之一實施形態中，提供用以將包含與基板相接 1乳化物層或銅合金氧化物層的基板上之含銅積層膜進 仃虫=之綱液，前述·包含過氧化物與有機酸、。 其中之基板，任何可用於半導體之基板等均可，典型 7/19 201040316 之例可舉如玻璃、石英、陶瓷等。 本發明t，含銅制膜係包含鋼或銅合金(峨任 ，之合金)之層、及銅氧化物或銅合金氧 、制之 典型為2層’惟3層以上亦可幌刻。又，銅:金 銅^卜的金屬元素，與銅合金氧化物層中之銅以^ =二可相同亦可不同。本發日种之含銅積層膜以Cu/CuX〇 或CuX/CuX0(式中之乂為岣、^、細㈣為佳。 本發明巾，_液之pH並無_之限定，惟在積層膜 類及膜厚、錐形形狀、邊姓刻量等之觀點上，以如為 酿二寺別=3.5至5·5更佳。阳之調整可利用有機酸或有機酸 、或加PH調節劑操作，低時，下層之銅氧化 ’不易製成良好之錐形;PH高時，會有⑽之 之^應無法進行或在實用性之钮刻速度下無法進行㈣ 限定本用之氧化劑（過氧化物）並無特別之 Λ㈣°+ σ過氧化氫、過硫酸、過硫酸鹽、過乙酸、過 性二ΐ碳Ϊ、過碳酸鹽等。特別是在過氧化物之安定 、易取4、轉作、及價袼等之觀點上， =:、過硫酸鹽為佳。過硫_之例可舉如khs二 物Γ 錢、喊〇8、及(贿4)2桃等。又，過氧化 物亦可使用適當之2種以上之組合。 、晶-^ t中過氧化物之濃度並無特別之限定，在使用 夺，以_至3.〇，佳，〇 〇5至2 〇 ^ 又更佳。過氧化氫之濃度低日_之速 ft可Ϊ 之速度過快，所獲得之圖樣有不易控 8/19 201040316 使用過硫酸或過硫酸鹽時，過硫酸之濃度以〇.01至3 〇 m〇1/L為佳，0,05至2.0m〇l/L更佳，0.1 至i.〇m〇i/L又更佳。 過石欠之辰度低時，蝕刻之速度慢，濃度高時，蝕刻之速 度過快，所得之圖樣有不易控制之可能。 本發明之蝕刻液中可使用的有機酸並無特別之限定， :例舉如擰檬酸、甘麟、乙酸、酒石酸、_酸、乳酸、 苯=曱酸等。特別在PH緩衝能力及溶解性、易取得、及價 格等之觀點上’以擰檬酸、甘胺酸、乙酸為佳。又， 酸亦可使用適當之2種以上之組合。 本發明中，有機酸之濃度並無特別之限定，以0.05至5.0 ㈣况為佳，〇.05至3.0励1几更佳，0.1至2.0mol/L尤佳，〇] 至1.0 mol/L又最佳。有機酸之濃度低時，pH緩衝劑之作用 不足L蝕刻液難以維持於蝕刻液預定之pH範圍内。而有機 ，之濃度高時，會發生溶解性之_，可能無法充分獲得 南;辰度化所帶來的效果。 本發明蝕刻液中使用之螯合劑並無特別之限定，可舉 如乙-胺四乙酸及其驗鹽、二伸乙三胺五乙酸及其驗鹽、 二乙酸胺及其鹼鹽等。特別在螯合化能力、螯合劑之溶解 性等觀點上，以乙二胺四乙酸及其鹼鹽、二伸乙三胺五乙 酸及其鹼鹽為佳。螯合劑可使用適當之2種以，上之組合。摻 ，此等螯合劑時，可使藉餘刻溶解出之Cu、Ca、Mg等金屬 離子螯合化，因此有抑制蝕刻反應物在溶液中析出之效 果’例如可抑制Cu離子所導致過氧化氫發生之分解反應。 本發明中螯合劑之濃度並無特別之限定，以〇 〇1至〇2 mol/L為佳，〇.03至0.15 m〇I/L更佳，〇 〇5至〇 丨 m〇i/L又更 佳。螯合劑之濃度低時，螯合劑之作用不足，濃度高時， 9/19 201040316 溶解度可能會不足，因此無法形成均勾之溶液。 ❹种之過氧化物使用過氧化氫時，有機酸以使用 檸㈣或甘胺酸為佳。此時再含螯合劑之乙二胺四乙酸二 =-伸乙―&五乙酸二納更佳。如此含過氧化氫、有機 ，、及§合_，各濃度並無_之限定，例如對過氧化 虱0.01至3.0m〇i/L，有機酸可加〇.〇5至3 〇m视，更好加 至2.0 moi/L ’又更好加〇.!至！ 〇 ，·整合劑可加㈣至μ m〇l/L ’更好加0.03至〇.〗5 m视，又更好加⑽$至〇.】则此。 本發月中過氧化物使用過硫酸或過硫酸鹽時，有機酸 以使用乙酸為佳。此時各敍並無制之限定，可以如對 過硫酸或過硫酸鹽_至3·〇励1/L ,加乙敵〇5至 為佳’（^、视更佳’力心至心舰又更^乙酸 濃度低時，pH緩衝劑之作用不足，因此侧液難以維持在 預定之PH翻内，敍高時，會有乙酸臭氣之問題，且可 月b無法充分獲得高濃度化所帶來的效果。 本考X月之韻刻方法之一形態為用以將其中包含與基板 相，之銅氧化物層或銅合金氧化物層的基板上含銅積層膜 進行關之綠’且㈣方法包含使肖含過氧化物與有機 酸之触刻液進行餘刻之步驟。 卜因此，除蝕刻對象是含銅積層膜與基板相接之層為銅 氧化物層或鋼合金氧化物層，且細液使用含過氧化物與 有機酸之㈣m卜，並無制之限定，可以適當、已往 以來使用之目的為飯刻之步驟操作。 實施例 1 · CuMg/CuIV[gO/glass基板之處理(實施例丨至6) 在玻璃基板上先濺鍍500人之CuMgO膜，其上再濺鍍 10/19 201040316 3000Α之CuMg膜，形成CuMg/CuMg〇二層積層膜。之後再 於該CuMg/CuMgO二層積層膜上進行光阻塗布後，再選擇 性地曝光及轉形成綱光罩。另補如表丨所示之钮刻液 (No.l至6)，將上述基板在溶液溫度3〇艺、攪拌之條件下浸 >貝處理。以目視確定達適量蝕刻時間(JET)，以正丁之15倍 時間處理。 σ 表1 Ο 〇 溶液 No. H202 (mol/L) 0.5 2 3 4 5 0.100 0.5 0.5 0.5 0.5 0.5 0.090 0073 ^052~ 0.030 0.020 表2所示 表2 實施例 —— 溶液 No. JET (sec) JT 施例1 1 79 j施例2 2 76 貫施例3 3 73 實施例4 4 76 實施例5 5 83 實施例6 6 94 〇： 良好，X :不良 擰檬酸 Jmol/L) 擰檬酸鈉 (mol/L) EDTA.2Na (mol/L) pH 0.025 0.1 3.3— 0.035 0.1 3.5— 0.052 0.1 4.0 0.073 0.1 0.095 0.1 5.0— 0.105 —~~---- 0.1 5.3 ~ 形狀 邊I虫刻 (μηι) —〇 1.0 1.1 -〇 1.2 —〇 1.3 —〇 1.3 —〇 ~~L6~ 在實施例丨至6中，斷面均形成錐形，祕刻量均抑低 =^則’6,。又，在玻璃基板上均可確定無烟殘 又，典型之斷面觀察圖_式電子顯微鏡(聰)之照 11/19 201040316 片。倍率：40,000倍)如圖1(以No.3溶液處理CuMg/CuMgO 基板之結果’經110 sec (JETx 1.5)進行蝕刻處理後(實施例3》 所示。 2. Cu/Mo/glass基板之處理（比較例2至6) 在玻璃基板上先濺鍍250A之Mo膜，其上再濺鍵4〇〇〇人 之Cu膜’形成Cu/Mo二層積層膜。再於該cu/Mo二層積層膜 上進行光阻塗布後，選擇性地曝光及顯像形成触刻光罩。 與實施例同樣地調製表1所示之蝕刻液(Ν〇·2至6)，將上述基 板在溶液溫度30°C、攪拌之條件下浸潰處理。以目視確定 達適量蝕刻時間(JET) ’以JET之1.5倍時間處理。 以溶液No.2至6處理Cu/Mo/glass基板之結果如表3所 示。 另外，使用溶液No.l之比較例1之實驗，該溶液]^〇1之 pH為3.3，由溶液Νο·2至6中之結果已知形狀不良，因此並 未進行。Synchronous etching technique of a new laminated film formed of copper and copper alloy oxides such as CuMg/CuMgO, CuCa/CuCaO, Cu/CuCaO, Cu/CuA1Mg〇, etc., in which etching such as Cu single layer film and Cu/M〇, Cu are encountered. In the simultaneous etching for existing copper-clad laminates such as /Ti and Cu/Cr, the FeCl3 and CuCl2 mixed acid-based etching solutions used have high solubility in the underlayer film such as CuMg〇&CuCa〇, 5/19 201040316 Therefore, the edge of the base film becomes large in contact, so that the problem of the taper cannot be formed. That is, the object of the present invention is to provide a solution to the foregoing problems, which can be used for simultaneous etching of a Cu metal layer and a cu alloy oxide layer, can control dissolution of a highly soluble copper alloy oxide layer, and can simultaneously etch a target object. The entire layer of the Cu alloy oxide layer is included in the laminate, and an etching solution and an etching method which are dissolved under appropriate balance conditions can be realized. Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have unexpectedly discovered that the use of a side liquid containing a peroxide-containing acid can be used to synchronize the above-mentioned laminated film with a refinement. The results of the investigation complete the present invention. That is, the present invention relates to the use of a copper-containing laminated film on a substrate comprising a copper oxide layer or a copper alloy oxide layer which is in contact with a substrate, and the residual etching liquid contains a peroxidation. And organic acids. Furthermore, the present invention is also related to the foregoing etching solution, wherein the copper-containing acoustic film is Cu/CuX0 or CuX/CuX〇 (wherein the yttrium, yt or yttrium. Also the invention is also related to the aforementioned surname The liquid has a yang of 3 to 6. The present invention is also related to (4) ship engraving liquid, wherein the peroxide, in addition, the invention also relates to the aforementioned residual liquid, which further contains a chelating agent. Amino acid B is related to the former secret engraving solution, wherein the chelating agent is - octagonal dish, or diethylene triamine pentaacetic acid and its alkali salt. Also: i'r month is also related to the aforementioned etching liquid 'which is organic" The invention of the vine is also used in the present invention. It also has a persulfate or persulfate. The invention is also related to the above rhyme, wherein the persulfate system 6/19 201040316 is selected from khs〇. 5. The group of NaHS〇5, K2s2〇8, Na2S2〇8, and (ΝΗ4)2. Further, the present invention is also related to the aforementioned remnant, wherein the organic acid is acetic acid. Further, the present invention is also related to The remaining method is to perform a copper-clad laminate film comprising a copper oxide layer or a copper alloy oxide layer which is in contact with the substrate. And the above method comprises the step of etching with an etching solution containing a peroxide and an organic acid. Ο ❹ Effect of the invention The above-mentioned constitution of the present invention is a layer of copper oxide layer or copper which is in contact with the substrate containing the copper laminated film. The role of the alloy oxide layer can suppress the dissolution rate of the copper alloy oxide layer, up to (4) What makes Cu/CUXQ (X^Yi's gold laminated film form a cone while the rice is less engraved.) The existing copper-clad film is oxidized and dissolved by the synchronous residual genus, but in the solution 2 of the copper alloy oxide laminated film, the copper is not changed, that is, it should be carried out without oxidative dissolution, so The bismuth alloy oxide film is in the oxide state of Cu0, Cu02, etc., and the voltage is below the PH4, which is not the oxide of the female 疋 形成 形成 形成 形成 形成 因此 因此 因此 因此 因此 因此 ' 因此 ' ' ' ' ' ' ' ' ' ' ' 因此 ' ' ' ' 因此The vicinity of the boundary condition of the sub-stable range (_")' can control the dissolution rate of the Cu alloy oxide film. [Embodiment] In one embodiment of the invention, an emulsion layer or copper is provided to be attached to the substrate. Substrate of alloy oxide layer The copper-containing laminated film is introduced into the aphid = the liquid, and the above includes the peroxide and the organic acid, and the substrate, any substrate that can be used for the semiconductor, etc., and the typical example of 7/19 201040316 is glass, Quartz, ceramics, etc. In the present invention, the film containing copper includes a layer of steel or a copper alloy, and a copper oxide or a copper alloy, which is typically two layers of 'only three layers or more. It can be engraved. In addition, the metal element of copper: gold and copper, and the copper in the copper alloy oxide layer may be the same or different. The copper-containing laminated film of the present day is Cu/CuX〇 or CuX. /CuX0 (wherein the formula is 岣, ^, fine (four) is preferred. The pH of the invention, the pH of the liquid is not limited, but in the laminated film and the film thickness, the cone shape, the side name, etc. In terms of opinion, it is better to use the likes of the two temples = 3.5 to 5. 5 . The adjustment of the yang can be carried out by using an organic acid or an organic acid, or by adding a pH adjusting agent. When low, the oxidation of the underlying copper is not easy to make a good cone; when the pH is high, there is a possibility that (10) can not be carried out or is practical. It is impossible to carry out the sulphuric acid (peroxide). (4) °+ σ hydrogen peroxide, persulfate, persulfate, peracetic acid, perylene, carbonic acid, percarbonic acid Salt and so on. Especially in the viewpoints of stability, easy-to-use, conversion, and price of peroxide, =:, persulfate is preferred. Examples of sulfur may be khs two things, money, shouting 8, and (bribery 4) 2 peaches. Further, a peroxide may be used in a combination of two or more kinds as appropriate. The concentration of the peroxide in the crystal is not particularly limited, and is preferably _ to 3. 〇, preferably, 〇 〇 5 to 2 〇 ^. The concentration of hydrogen peroxide is low, the speed of ft can be too fast, and the obtained pattern is not easy to control. 8/19 201040316 When using persulfate or persulfate, the concentration of persulfate is 〇.01 to 3 〇m. 〇1/L is better, 0,05 to 2.0 m〇l/L is better, and 0.1 to i.〇m〇i/L is better. When the low temperature of the stone is low, the etching speed is slow, and when the concentration is high, the etching speed is too fast, and the obtained pattern is difficult to control. The organic acid which can be used in the etching solution of the present invention is not particularly limited, and examples thereof include citric acid, ganolin, acetic acid, tartaric acid, _acid, lactic acid, benzene = decanoic acid and the like. In particular, it is preferable to use citric acid, glycine, or acetic acid from the viewpoints of pH buffering ability, solubility, availability, and price. Further, the acid may be used in a combination of two or more kinds as appropriate. In the present invention, the concentration of the organic acid is not particularly limited, and is preferably from 0.05 to 5.0 (d), preferably from 〇.05 to 3.0, more preferably from 0.1 to 2.0 mol/L, and from 〇] to 1.0 mol/L. The best. When the concentration of the organic acid is low, the effect of the pH buffer is insufficient. The etching solution is difficult to maintain in the predetermined pH range of the etching solution. However, when the concentration is high, the solubility will occur, and the effect of the south will not be fully obtained. The chelating agent to be used in the etching solution of the present invention is not particularly limited, and examples thereof include ethyl-amine tetraacetic acid and a salt thereof, diethylenetriamine pentaacetic acid and a salt thereof, diacetic acid amine and an alkali salt thereof. Particularly, from the viewpoints of the chelating ability and the solubility of the chelating agent, ethylenediaminetetraacetic acid and an alkali salt thereof, diethylenetriamine pentaacetic acid and an alkali salt thereof are preferred. The chelating agent may be used in a combination of two or more kinds. When such a chelating agent is blended, the metal ions such as Cu, Ca, and Mg which are dissolved by the residue can be sequestered, thereby suppressing the precipitation of the etching reactant in the solution, for example, suppressing peroxidation caused by Cu ions. Decomposition reaction of hydrogen generation. The concentration of the chelating agent in the present invention is not particularly limited, and is preferably 〇〇1 to 〇2 mol/L, more preferably 〇.03 to 0.15 m〇I/L, 〇〇5 to 〇丨m〇i/L. Better yet. When the concentration of the chelating agent is low, the effect of the chelating agent is insufficient. When the concentration is high, the solubility of 9/19 201040316 may be insufficient, so that the solution of the homogenate cannot be formed. When hydrogen peroxide is used as the peroxide of the seed, the organic acid is preferably a lemon (tetra) or a glycine. At this time, the chelating agent further contains ethylenediaminetetraacetic acid 2 =-extension B-& Such a concentration of hydrogen peroxide, organic, and §, _, each concentration is not limited, for example, ruthenium peroxide 0.01 to 3.0 m 〇 i / L, organic acid can be added 〇 至 5 to 3 〇 m view, Better added to 2.0 moi / L 'and better crowned.! To! 〇,·Integrator can add (4) to μ m〇l/L ‘more preferably 0.03 to 〇. 〗 5 m, and even better (10)$ to 〇.] Then this. When persulfuric acid or persulfate is used as the peroxide in the month, the organic acid is preferably acetic acid. At this time, there is no limit to the system. For example, for persulfate or persulfate _ to 3· encourage 1/L, plus B to 5 is better. (^, 视更佳'力心心心Further, when the concentration of acetic acid is low, the effect of the pH buffering agent is insufficient, so that it is difficult to maintain the side liquid within the predetermined pH turnover. When the height is high, there is a problem of acetic acid odor, and the high concentration of the liquid can not be obtained. The effect of the X-ray rhyme method in this test is to form a copper-clad film on the substrate containing the copper oxide layer or the copper alloy oxide layer with the substrate phase, and (4) The method comprises the step of engraving the etchant containing the peroxide and the organic acid. Therefore, the layer to be etched is a layer containing a copper-clad laminate and the substrate is a copper oxide layer or a steel alloy oxide layer. And the fine liquid uses the (four) m-containing peroxide and the organic acid, and there is no limitation on the preparation, and the operation can be suitably carried out for the purpose of the cooking process. Example 1 · CuMg/CuIV [gO/glass substrate Treatment (Examples 丨 to 6) Sputtering a 500-person CuMgO film on a glass substrate, and then splashing thereon 10/19 201040316 3000M CuMg film, CuMg/CuMg〇 two-layer laminated film is formed. After the photoresist coating on the CuMg/CuMgO two-layer laminated film, it is selectively exposed and transferred to form a mask. The button engraving liquid (No. 1 to 6) shown in Table , is added, and the above substrate is immersed in a solution temperature of 3 °, stirring, and the shell is treated. The optimum etching time (JET) is visually determined to 15 times time treatment of n-butyl. σ Table 1 Ο 〇 solution No. H202 (mol / L) 0.5 2 3 4 5 0.100 0.5 0.5 0.5 0.5 0.5 0.090 0073 ^ 052 ~ 0.030 0.020 Table 2 Table 2 Example - Solution No. JET (sec) JT Example 1 1 79 j Example 2 2 76 Example 3 3 73 Example 4 4 76 Example 5 5 83 Example 6 6 94 〇: Good, X: Bad citric acid Jmol/L) Sodium citrate (mol/L) EDTA.2Na (mol/L) pH 0.025 0.1 3.3- 0.035 0.1 3.5- 0.052 0.1 4.0 0.073 0.1 0.095 0.1 5.0— 0.105 —~~---- 0.1 5.3 ~ Shape edge I insect (μηι) - 〇 1.0 1.1 - 〇 1.2 - 〇 1.3 - 〇 1.3 - 〇 ~ ~ L6 ~ In the examples 丨 to 6, the section is tapered, secret The amount of the mark is low = ^ then '6,. Moreover, the smokeless residue can be determined on the glass substrate, and the typical cross-sectional view is taken by the electron microscope (Cong) 11/19 201040316. Magnification: 40,000 times) as shown in Fig. 1 (result of treating CuMg/CuMgO substrate with No. 3 solution) after etching treatment at 110 sec (JETx 1.5) (Example 3) 2. Cu/Mo/glass substrate Treatment (Comparative Examples 2 to 6) A 250A Mo film was first sputtered on a glass substrate, and a Cu-Mo layer film was formed by sputtering a double-layered Cu film to form a Cu/Mo two-layer laminated film. After photoresist coating on the laminated film, selective exposure and development were carried out to form a etch mask. The etching liquids shown in Table 1 (Ν〇·2 to 6) were prepared in the same manner as in the examples, and the substrate was placed in a solution. The temperature was 30 ° C and the impregnation treatment was carried out under the conditions of stirring. The optimum etching time (JET) was visually determined to be processed at 1.5 times the JET time. The results of treating the Cu/Mo/glass substrate with the solutions No. 2 to 6 are shown in the table. Further, in the experiment of Comparative Example 1 using the solution No. 1, the pH of the solution was 3.3, and the results from the solutions Νο·2 to 6 were known to be inferior in shape, and thus were not carried out.
表3 比較例 溶液 No. JET (sec) 處理時間~ JETxl.5 (sec、 比較例2 2 125 188 比較例3 3 114 171 ~ 比較例4 4 110 165 ~ 比較例5 5 107 161 比較例ό 6 119 179 ~ 〇：良好，X :不良 Cu/Mo二層積層膜中 ，不論何種處理溶液，其美底^!〇 膜溶解均快速，致使斷面形狀呈『〈之字形』，難以土形成正 常之配線。本形態中之蝕刻液組成物係調整以使用於 CuX/CuXO二層積層膜中，重點為銅合金氧化物膜可以適當 12/19 201040316 之速度溶解。因此，無法單純地適用在既存之Cu/Mo二層積 層膜上。 又，典型之斷面觀察圖（掃瞄式電子顯微鏡(SEM)之照 片。倍率：40,000倍)如圖2(以No.3溶液處理Cu/Mo基板之結 果’經Π1 sec (JETxl.5)進行蝕刻處理後(比較例3))所示。 3 · CuMg/CuMgO/glass基板之處理(實施例7至9) 製備與實施例1至6中使用為基板相同之CuMg/CuMgO 二層積層膜’以如下述表4中所示之溶液(N〇.7至9)實施蝕刻 處理。以溶液溫度30°C、攪拌之條件下浸潰處理，以目視 確定達適量餘刻時間(JET)，以JET之1.5倍時間處理。 表4 溶液No, 過硫酸敍 (moI/L) 乙酸 (mol/L) 乙酸銨 (mol/L) pH 7 0.5 0.06 0.065 4.5 8 0.5 0.24 0.26 4.5 9 0.5 0.48 0.52 4.5 以溶液No. 7至9處理CuMg/CuMgO/glass基板之結果如 表5所示。 實施例 溶液 No. JET (sec) 一處理時間 JETx 1.5 (sec) 形狀 邊蚀刻 (uni) 實施例7 7 24 36 〇 0.9 實施例8 8 64 96 Ο 1.3 實施例9 9 88 132 〇 0.9 〇：良好，X :不良 實施例7至9中，斷面均呈錐形，邊蝕刻量抑制至較低 為0.9至1.3 μιη。又，玻璃基板上均可確定無蝕刻殘留物等。 其典.型之斷面觀察圖（掃瞄式電子顯微鏡(SEM)之照 片。倍率：40,000倍)如圖3(以No.8溶液處理CuMg/CuMg〇 13/19 201040316 基板之結果’經96 sec (JETM.5)進行蝕刻處理後(實施例8)) 及圖4(以No.9溶液處理CuMg/CuMgO基板之結果，經132 sec (JETxl.5)進行蝕刻處理後(實施例9))所示。 4. Cu/Mo/glas s基板之處理（比較例7至9) 使用與前述比較例2至6中同樣之Cu/Mo二層積層膜為 比較例，與實施例相同地利用表4中所示之蝕刻液(No.7至 9)，在溶液溫度30°C、攪拌之條件下浸潰處理。以目視確定 達適量蝕刻時間(JET)，以JET之1.2倍時間處理。 以溶液No.7至9處理Cu/Mo/glass基板之結果如表6所 示。 表6 比較例 溶液 No. JET (sec) 處理時間 JETxl.2 (sec) 形狀 邊1虫刻 (陣） 比較例7 7 66 79 X 3.8 比較例8 8 132 158 X 3.0 比較例9 9 300< 無法触刻 X - 〇：良好，X :不良Table 3 Comparative Example Solution No. JET (sec) Treatment Time ~ JETxl.5 (sec, Comparative Example 2 2 125 188 Comparative Example 3 3 114 171 ~ Comparative Example 4 4 110 165 ~ Comparative Example 5 5 107 161 Comparative Example ό 6 119 179 ~ 〇: Good, X: In the poor Cu/Mo two-layer laminated film, no matter what kind of treatment solution, the beauty of the film is fast, so that the shape of the cross section is "Zigzag", which is difficult to form. Normal wiring. The composition of the etching solution in this embodiment is adjusted for use in a CuX/CuXO two-layer laminated film, with the emphasis that the copper alloy oxide film can be dissolved at a rate of 12/19 201040316. Therefore, it cannot be simply applied. On the existing Cu/Mo two-layer laminated film. Also, a typical cross-sectional view (photograph of scanning electron microscope (SEM). Magnification: 40,000 times). Figure 2 (Processing Cu/Mo substrate with No. 3 solution) The result was shown after etching treatment (Comparative Example 3) by Π 1 sec (JETxl. 5). 3 · Treatment of CuMg/CuMgO/glass substrate (Examples 7 to 9) Preparation and use in Examples 1 to 6 The CuMg/CuMgO two-layer laminated film of the same substrate has a solution (N〇.7 to 9) as shown in Table 4 below. The etching treatment was carried out by dipping at a solution temperature of 30 ° C under stirring, and visually determined to obtain an appropriate amount of time (JET), which was treated at 1.5 times the JET time. Table 4 Solution No, Persulfate (moI/L) Acetic acid (mol/L) Ammonium acetate (mol/L) pH 7 0.5 0.06 0.065 4.5 8 0.5 0.24 0.26 4.5 9 0.5 0.48 0.52 4.5 The results of treating CuMg/CuMgO/glass substrates with solution Nos. 7 to 9 are shown in Table 5. EXAMPLES Solution No. JET (sec) One treatment time JETx 1.5 (sec) Shape edge etching (uni) Example 7 7 24 36 〇 0.9 Example 8 8 64 96 Ο 1.3 Example 9 9 88 132 〇 0.9 〇 : Good, X: In the poor examples 7 to 9, the cross section is tapered, and the etching amount is suppressed to a low level of 0.9 to 1.3 μm. Further, no etching residue can be determined on the glass substrate. Cross-sectional view of the type (photograph of the scanning electron microscope (SEM). Magnification: 40,000 times) as shown in Figure 3 (result of CuMg/CuMg〇13/19 201040316 substrate treated with No. 8 solution) after 96 sec (JETM .5) After the etching treatment (Example 8)) and Figure 4 (the result of treating the CuMg/CuMgO substrate with the No. 9 solution, after 132 sec (JETxl.5) After the etching process (Example 9)) in FIG. 4. Treatment of Cu/Mo/glas s substrate (Comparative Examples 7 to 9) The Cu/Mo two-layer laminated film similar to the above Comparative Examples 2 to 6 was used as a comparative example, and the same as in the examples, the same as in the examples. The etching liquid (No. 7 to 9) shown was immersed under the conditions of a solution temperature of 30 ° C and stirring. The optimum etching time (JET) was determined visually and processed at 1.2 times the JET time. The results of treating the Cu/Mo/glass substrate with the solutions No. 7 to 9 are shown in Table 6. Table 6 Comparative Example Solution No. JET (sec) Processing Time JETxl.2 (sec) Shape Side 1 Insect (Array) Comparative Example 7 7 66 79 X 3.8 Comparative Example 8 8 132 158 X 3.0 Comparative Example 9 9 300< Touch X - 〇: good, X: bad
Cu/Mo二層積層膜中’不論何種處理溶液，基底M〇膜 均快速溶解’致使斷面形狀呈『垂直至稍呈反〈之字形』， 其邊蝕刻量亦為3.0 μιη以上，因此難以形成正常之配線。本 形態中之姓刻液組成物係調整以使用於CuX/CuXO二層積 層膜中’其重點為銅合金氧化物膜可以適當之速度溶解。 因此，無法適用於既存之Cu/Mo二層積層膜。 又’典型之斷面觀察圖（掃瞄式電子顯微鏡(；SEM)之照 片。倍率：40,〇〇〇倍)如圖5(以No.8溶液處理Cu/Mo基板之結 果，經158 sec (JETxl.2)進行蝕刻處理後(比較例8))所示。 5，各種Cu積層膜之處理(實施例1〇至12及比較例1〇) 14/19 201040316 在玻璃基板上先濺鍍500 A之(^(^(^膜，其上再濺鍍 3000A之Cu膜或CuCa膜，製成Cu/CuCa〇二層積層膜及 CuCa/CuCaO二層積層膜。另外再於玻璃基板上先濺鍍5〇〇 A之CuMgAio膜為基底層，其上再濺鍍3〇〇〇AiCu膜，製成 Cu/CuMgAlO二層積層膜。此等二層積層膜上進行光阻塗布 後，選擇性地曝光及顯像形成蝕刻光罩。之後另調製如表7 所示之蝕刻液(No.10) ’針對上述各二層積層膜基板在溶液 溫度30 C、授拌之條件下浸潰處理。以目視確定達適量蚀 刻時間(JET)，以JET之1.5倍時間處理。 另外，比較例10係使用如上述比較例2至6之cu/m〇二層 積層膜，與實施例同樣地利用表7中所示之蝕刻液(N〇.1〇)， 在溶液溫度30°C、攪拌之條件下浸潰處理。再以目視確定 達適量蝕刻時間(JET)，以JET之1.5倍時間處理。 表7 溶液 No. h2o2 (mol/L) 檸檬酸鈉 (mol/L) 擰檬酸 (mol/L) EDTA.2Na (mol/L) 鱗酸二氫 納(mol/L) pH 10 0.5 0.053 0.072 0.1 0.01 4.0 以溶液No. 10處理各種Cu積層膜之結果如表8所示。 表8 實施例 溶液 No. 積層膜/ 基板 JET (sec) 處理時間 JETxl.5(sec) 形 狀 邊I虫刻 (μιη) 實施例 10 10 Cu/CuCaO/ glass 35 53 〇 0.6 實施例 11 10 CuCa/CuCaO/ glass 30 45 〇 1.3 實施例 12 10 Cu/CuMgAlO/ glass 46 69 〇 0.8 比較例 10 10 Cu/Mo/ glass 236 354 X 3.0 〇：良好，X :不良 15/19 201040316 所有Cu/CuCaO、CuCa/CuCaO、Cu/CuMgA10之二層積 層膜，斷面均呈純粹之錐形，邊蝕刻量亦抑制至較少量為 0.6至1.3 μιη。又，在玻璃基板上均可確定無蝕刻殘留物等。 斷面觀察圖（掃瞄式電子顯微鏡(SEM)之照片。倍率： 40,000倍)如圖6(以价.1〇溶液處理(：11/(：1^〇基板之結果，經 53sec (JETxl·5)進行蝕刻處理後(實施例1〇))所示。 另一方面’ Cii/Mo二層積層膜中，基底M〇膜溶解快速， 致使斷面形狀呈『倒錐形』，且邊蝕刻量大為3.0 μηι，玻璃 基板上可確定有微細粒狀殘渣，因此難以形成正常之配 ❹ 線。本形態中之蝕刻液組成物係調整以使用KCuX/CuX〇二 層積層膜中，重點為銅合金氧化物膜可以適當之速度溶 解。因此’無法適用於既存之Cu/Mo二層積層膜。 斷面觀察圖（掃瞒式電子顯微鏡(SEM)之照片。倍率： 40,000倍)如圖7(以No.10溶液處理Cu/Mo基板之結果，經354 sec (JETxl.5)進行蝕刻處理後（比較例1〇))所示。 6.各種Cu積層膜之處理(實施例丨3至15及比較例11) 對實施例10至12中使用之Cu/CuCaO、CuCa/CuCaO、 Cu/CuMgAlO之各二層積層膜，調製如表4所示之蝕刻液 ◎ (No.7)，在溶液溫度3〇°C、攪拌之條件下浸潰處理。以目視 確定達適量蝕刻時間(JET)，以JET之1.5倍時間處理。 比較例11中使用與上述比較例2至6同樣之Cu/Mo二層 積層膜，與實施例相同地利用表4所示之蝕刻液(No.7)，在 溶液溫度30°C、攪拌之條件下浸潰處理。以目視確定達適 量蝕刻時間(JET) ’以JET之1.5倍時間處理。以溶液No.7處 理各種Cu積層膜之結果如表9所示。 16/19 201040316 表9 實施例 溶液 No. 積層膜/ 基板 JET (sec) 處理時間 JETxl.5 (sec) 形狀 邊1虫刻 (m) 實施例 13 7 Cu/CuCaO/ glass 25 38 〇 0.5 實施例 14 7 CuCa/CuCaO/ glass 21 32 〇 1.0 實施例 15 7 Cu/CuMgA10/ glass 30 45 〇 0.8 比較例 11 7 Cu/Mo/ glass 151 圓·— — 227 X 8.3 〇 •良好，X :不良 — ~~^—In the Cu/Mo two-layer laminated film, 'no matter what kind of treatment solution, the base M 〇 film dissolves quickly', so that the cross-sectional shape is “vertical to slightly reverse zigzag”, and the etching amount is also 3.0 μmη or more. It is difficult to form a normal wiring. The surname composition in this form is adjusted for use in a CuX/CuXO two-layer film. The focus is on the copper alloy oxide film which can be dissolved at an appropriate rate. Therefore, it cannot be applied to the existing Cu/Mo two-layer laminated film. Also, a typical cross-sectional view (photograph of a scanning electron microscope (SEM). Magnification: 40, 〇〇〇) is shown in Figure 5 (result of Cu/Mo substrate treated with No. 8 solution, after 158 sec (JETxl.2) is shown after the etching treatment (Comparative Example 8)). 5, treatment of various Cu laminated films (Examples 1 to 12 and Comparative Example 1) 14/19 201040316 Sputtering 500 A on the glass substrate (^(^(^(), which is further sputtered with 3000A Cu film or CuCa film is used to form Cu/CuCa〇 two-layer laminated film and CuCa/CuCaO two-layer laminated film. Further, a CuMgAio film of 5〇〇A is sputtered on the glass substrate as a base layer, and then sputtered thereon. 3〇〇〇AiCu film was formed into Cu/CuMgAlO two-layer laminated film. After the photoresist coating on these two-layer laminated film, selective exposure and development were performed to form an etching mask, and then another modulation was shown in Table 7. Etching solution (No. 10) 'The above two-layer laminated film substrate was subjected to a dipping treatment at a solution temperature of 30 C under the conditions of mixing. The optimum etching time (JET) was visually determined and processed at 1.5 times the JET time. Further, in Comparative Example 10, the cu/m 〇 two-layer laminated film of Comparative Examples 2 to 6 was used, and the etching liquid (N 〇.1 〇) shown in Table 7 was used in the same manner as in the Example, at the solution temperature. Immersion treatment was carried out under stirring at 30 ° C. The optimum etching time (JET) was visually determined and treated at 1.5 times the JET time. Table 7 Solution No. h2o2 ( Mol/L) sodium citrate (mol/L) citric acid (mol/L) EDTA.2Na (mol/L) sodium dihydrogen phosphate (mol/L) pH 10 0.5 0.053 0.072 0.1 0.01 4.0 in solution No. The results of treating various Cu laminated films are shown in Table 8. Table 8 Example solution No. Laminated film / substrate JET (sec) Treatment time JETxl.5 (sec) Shape edge I insect (μιη) Example 10 10 Cu /CuCaO/ glass 35 53 〇0.6 Example 11 10 CuCa/CuCaO/glass 30 45 〇1.3 Example 12 10 Cu/CuMgAlO/glass 46 69 〇0.8 Comparative Example 10 10 Cu/Mo/ glass 236 354 X 3.0 〇: Good , X: Poor 15/19 201040316 All Cu/CuCaO, CuCa/CuCaO, Cu/CuMgA10 two-layer laminated film, the section is purely tapered, and the amount of etching is also suppressed to a small amount of 0.6 to 1.3 μηη. Further, no etching residue or the like can be determined on the glass substrate. Cross-sectional observation (photograph of a scanning electron microscope (SEM). Magnification: 40,000 times) as shown in Fig. 6 (at a price of 1 〇 solution (: 11 The result of /(:1^〇substrate was etched after 53 sec (JETxl·5) (Example 1〇)). On the other hand, in the Cii/Mo two-layer laminated film, the base M film dissolves rapidly, resulting in a "reverse taper" in the cross-sectional shape, and the etching amount is 3.0 μm, and fine granular residue can be determined on the glass substrate. Therefore, it is difficult to form a normal distribution line. The etching liquid composition in this embodiment is adjusted to use a KCuX/CuX〇 two-layer laminated film, and it is important that the copper alloy oxide film can be dissolved at an appropriate speed. Therefore, it cannot be applied to the existing Cu/Mo two-layer laminated film. Cross-sectional observation (photograph of a broom-type electron microscope (SEM). Magnification: 40,000 times) as shown in Fig. 7 (the result of processing the Cu/Mo substrate with No. 10 solution, after etching treatment at 354 sec (JETxl. 5) (Comparative Example 1))). 6. Treatment of various Cu laminated films (Examples 至 3 to 15 and Comparative Example 11) The two-layer laminated films of Cu/CuCaO, CuCa/CuCaO, Cu/CuMgAlO used in Examples 10 to 12 were prepared as shown in the table. The etching liquid ◎ (No. 7) shown in 4 was impregnated under the conditions of a solution temperature of 3 ° C and stirring. The optimum etching time (JET) was determined by visual inspection and processed at 1.5 times the JET time. In Comparative Example 11, the Cu/Mo two-layer laminated film similar to the above Comparative Examples 2 to 6 was used, and the etching liquid (No. 7) shown in Table 4 was used in the same manner as in the Example, and the solution was stirred at a solution temperature of 30 ° C. Immersion treatment under conditions. It was visually determined that the optimum etching time (JET) was treated at 1.5 times the JET time. The results of treating various Cu laminated films in the solution No. 7 are shown in Table 9. 16/19 201040316 Table 9 Example solution No. Laminated film/substrate JET (sec) Treatment time JETxl.5 (sec) Shape side 1 insect (m) Example 13 7 Cu/CuCaO/glass 25 38 〇0.5 Example 14 7 CuCa/CuCaO/ glass 21 32 〇 1.0 Example 15 7 Cu/CuMgA10/glass 30 45 〇0.8 Comparative Example 11 7 Cu/Mo/ glass 151 Round·— 227 X 8.3 〇•Good, X: Bad—~ ~^—
所有Cu/CuCaO、CuCa/CuCaO、Cu/CuMgAlO之二層積 層膜，斷面均呈純粹之錐形，邊蝕刻量亦抑制至較少量為 0.5至1.0 μιη。又，在玻璃基板上均可確定無蝕刻殘留物等。 另方面，Cu/Mo二層積層臈中基底jyj〇膜溶解快速， 致使斷面雜呈m邊侧料83 μιη，因此難以形成 正常之配線。All the two-layer laminated films of Cu/CuCaO, CuCa/CuCaO, and Cu/CuMgAlO have a purely tapered cross section, and the amount of etching is also suppressed to a small amount of 0.5 to 1.0 μm. Further, no etching residue or the like can be determined on the glass substrate. On the other hand, in the Cu/Mo two-layered tantalum, the base jyj tantalum film dissolves rapidly, resulting in a section of m-side material of 83 μm, which makes it difficult to form a normal wiring.
本形態中之蝕刻液組成物係調整以使用於CuX/CuX〇 一層積層膜中，重點為銅合金氧化物膜可 解。因此，無法適用於既存之Cu/Mo二層積^ 産業上之可利用性 本發明之飯刻液及钱刻方法，在含鋼積層膜之與基板 相接之層為銅氧化物層或銅合金氧化物層的新半導體等之 積層體基板巾’可達成形成錐形且邊_少的同步银刻。 【圖式簡單說明】 圖1係以No.3溶液處理CuMg/CuMg〇基板之結果，為經 17/19 201040316 110 sec (JETxl.5)進行蝕刻處理後之斷面觀察圖（實施例3)。 圖2係以No.3溶液處理Cu/Mo基板之結果，為經171 Sec (JETX1.5)進彳亍触刻處理後之斷面觀察圖（比較例3)。 圖3係以1^〇‘8溶液處理(：11]^/(：111^0基板之結果，為經 96 36〇仰丁><1.5)進行蝕刻處理後之斷面觀察圖（實施例8)。 圖4係以No.9溶液處理CuMg/CuMg〇基板之結果，為經 132 sec (JETM.5)進行蝕刻處理後之斷面觀察圖（實施例％。 圖5係以No.8溶液處理Cu/Mo基板之結果，為經158 sec (JETx 1.2)進行蝕刻處理後之斷面觀察圖（比較例8)。 圖6係以No.10溶液處理Cu/CuCaO基板之結果，為經53 sec (JETxl.5)進行蝕刻處理後之斷面觀察圖（實施例1〇)。 圖7係以No.10溶液處理Cu/Mo基板之結果，為 經354 sec (J E T X1.5 )進行蝕刻處理後之斷面觀察圖（比較例丨〇)。 【主要元件符號說明】 無 18/19The etching liquid composition in this embodiment is adjusted for use in a CuX/CuX(R) layered film, with the emphasis being that the copper alloy oxide film is solvable. Therefore, it is not applicable to the existing Cu/Mo two-layer product industry. The rice engraving and the engraving method of the present invention, the layer in contact with the substrate of the steel-clad laminate film is a copper oxide layer or copper. In the laminated body substrate towel of a new semiconductor or the like of the alloy oxide layer, a simultaneous silver engraving in which a taper is formed and the side is small can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional observation view of a CuMg/CuMg(R) substrate treated with No. 3 solution, and subjected to etching treatment at 17/19 201040316 110 sec (JETxl.5) (Example 3) . Fig. 2 shows the results of a Cu/Mo substrate treated with a No. 3 solution, and is a cross-sectional observation view (Comparative Example 3) after 171 Sec (JETX 1.5). Fig. 3 is a cross-sectional view showing the result of etching treatment with a solution of 1 : 〇 '8 solution (: 11 ] / / : 111 ^ 0 substrate, which is subjected to etching treatment with 96 36 〇 & &>< 1.5 Example 8) Fig. 4 is a cross-sectional observation view of a CuMg/CuMg(R) substrate treated with a No. 9 solution, and subjected to etching treatment for 132 sec (JETM. 5) (Example %. Fig. 5 is No. The result of the solution treatment of the Cu/Mo substrate was a cross-sectional observation view after etching at 158 sec (JETx 1.2) (Comparative Example 8). Fig. 6 shows the result of treating the Cu/CuCaO substrate with No. 10 solution. A cross-sectional observation view after etching treatment at 53 sec (JETxl.5) (Example 1A). Figure 7 shows the result of processing a Cu/Mo substrate with a No. 10 solution for 354 sec (JET X1.5). Cross-sectional observation chart after etching treatment (Comparative Example) [Main component symbol description] No 18/19