200916605 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於銅/鉬兩層複合金屬層（Cu/m〇 bilayer)之蝕刻液組成物，其可用於定義銅/鉬兩層複合金 屬層之蝕刻圖形。本發明之蝕刻液組成物可應用於平面顯 示器、積體電路、覆晶封裝（Flip Chip)、印刷電路板、彩 色濾光片、微機電、或銅/鉬兩層複合金屬層之其他應用 之姓刻製程中。 【先前技術】 隨著半導體、平面顯示器及微機電製程往大尺寸及高速 反應趨勢發展，傳統上使用的紹金屬導線已無法滿足電子 遷移速率的需求，所以採用更低電阻值的金屬材料（例如 銅金屬）做為導線，具有改善電流傳導速度的優勢。然 而雖然鋼金屬有低阻抗的優點，卻也有容易氧化及無法 進行乾式㈣的缺f卜再者’由於銅金屬與玻璃基板或石夕 基板的結合性不佳，所以銅金屬導線的應用面臨使用上的 因難。倘若在銅金屬與基板之間填上—層纟目金屬則可以解 :銅金屬導線附著在基板上的問題。因此，銅/鉬兩層複 口金屬層漸漸成為金屬導線發展的主要結構。 然而，以銅/鉬兩層複合金屬層為主的蝕刻製程中，仍 有下列問題尚待克服： 1、 鋼/鉬的蝕刻率選擇比差異，不易克服。 2、 鋼/鉬導線的側蝕（CD Loss)太大。 3、 銅以目導線的側邊斜角角度會大於或等於90。。 I23643.doc 200916605 之組成 本案發明人經廣泛研究發現’具有本文中所定義 之蝕刻液組成物’可有效解決上述問題。 【發明内容】 釔此纟發明之—目的為提供一種用於銅，鉬金屬之蝕 刻液組成物，其句合.说备化# ^ /….過氧化虱，其含量範圍以蝕刻液組 重計為1至25重量胺基酸，其含量範圍以蝕刻 液組成物總重計為Μ至15重量％; PH值穩定劑，其含量範 圍^刻液組成物總重計狀丨至15重量％;含氟酸，其含 量範圍以㈣液組成物總重計為請至2重量％ ;酸性pH值 調整劑，其含量範圍以蝕刻液組成物總重計為〇〇1至3重 量％ ;及水性介質。 本發明之蝕刻液組成物使用於銅/鉬電子線路圖案之成 形上，、有餘刻速率穩疋、均勻、側钱（under cut)小及線 路邊緣斜角（tape angle)合適之優點。 本發明之主要目的為提供一種使用本發明蝕刻液組成物 姓刻銅/鉬金屬之方法。 【實施方式】 本發明之用於銅/鉬金屬之姓刻液組成物，其包含：過 氧化氫、胺基酸、pH值穩定劑、含氟酸、酸性pH值調整 劑及水性介質。 不欲受理論所限制，咸信本發明所使用之過氧化氫可用 於氧化銅金屬及鉬金屬。根據本發明之一具體實施態樣， 過氧化氫之含量以钱刻液組成物總重量計’為1至2 5重量 % ;較佳為3至20重量％。 123643.doc 200916605 不欲受理論所限制’咸信本發明所使用之胺基酸可用於 蝕刻銅金屬及鉬金屬。根據本發明之一具體實施態樣，適 合用於本發明之胺基酸包含但不限於甘胺酸（Glycine)、丙 月女酸（Alanine)或其混合物，此處混合物意指一或多種上述 任何胺基酸之混合物^適合用於本發明之胺基酸較佳係甘 胺酸或丙胺酸。胺基酸之含量以蝕刻液組成物總重量計， 為〇.1至1 5重量％ ;較佳為0.5至5重量％。 本發明所使用之p Η值穩定劑係用於穩定蝕刻液組成物之 酸驗值。根據本發明之一具體實施態樣，適合用於本發明 之pH值穩定劑包含但不限於氟化銨（NH4F)、氟化氫銨 ((NH4)HF2)、乙烯二胺四乙酸鹽（EDTA-salt)或其混合物， 此處混合物意指—或多種上述任何pH值穩定劑之混合物。 適合用於本發明之PH值穩定劑較佳係氟化銨。pH值穩定 劑之含量以蝕刻液組成物總重量計，為〇 ·丨至丨5重量％ ;較 佳為0.8至3重量％。 不名人觉理論所限制’咸信本發明所使用之含氟酸可用於 移除基板表面殘存的鉬金屬。根據本發明之一具體實施態 樣’適合用於本發明之含氟酸包含但不限於氫氟酸（HF)、 氟矽酸（HjiF4)或其混合物，此處混合物意指一或多種上 述任何含氟酸之混合物。適合用於本發明之含氟酸較佳係 氫氣酸。含氟酸之含量以蝕刻液組成物總重量計，為〇〇工 至2重量❶/〇 ;較佳為〇 〇丨至〇 3重量0/〇。 根據本發明之一具體實施態樣，適合用於本發明之酸性 pH值調整劑包含但不限於磷酸（H3P〇4)、磷酸銨 123643.doc 200916605 ((NH4)H2P04)、醋酸（CH3COOH)、草酸（c2H2〇4)、檸檬酸 (C6H8〇7)或其混合物，此處混合物意指—或多種上述任何 pH值調整劑之混合物。適合用於本發明之酸性pH值調整 劑較佳係磷酸或磷酸銨。酸性pH值調整劑之含量以蝕刻液 組成物總重量計，為0.01至3重量％;較佳為〇〇2至〇5重量 % 〇 本發明所使用之酸性pH值調整劑可用於調整蝕刻液組成 物之酸鹼值，可藉此得到銅/鉬適合的蝕刻選擇比❶根據 本發明之一具體實施態樣，本發明蝕刻液組成物之pH值範 圍為4至6.5 ’較佳為5。 本發明所使用的水性介質對於此技術領域中具有通常知 識者而言，係顯而易知的’例如在製備過程中，可使用 水’較佳係使用去離子水。 本發明之蝕刻液組成物中可視需要進一步包含此技術領 域中具有通常知識者所熟知但不致對本發㈣刻液組成物 產生不利影響之其他成份。 本發明之蝕刻液組成物使用於銅/鉬電子線路圖案之成 形上’具有蝕刻速率穩定、均勻、側蝕小及線路邊緣斜角 合適之優點〆根據本發明之一具體實施態樣，本發明之蝕 刻液組成物可應用於平面顯示器、積體電路、覆晶封裝、 P刷電路板、彩色濾光片、微機電、或銅，鉬兩層金屬層 之其他應用之餘刻製程中。 據此，本發明另提供一種銅/鉬金屬之蝕刻方法，其包 括： 123643.doc 200916605 提供一基板； 於該基板上形成鉬金屬層； 於该鉬金屬層上形成銅金屬層； 於該銅金屬層上形成一圖案化罩幕層及 ”圖案化罩幕層為罩幕’使用具有如前所 疋義及組份比例之餘刻液組合物對 ：組份 層進行一蝕刻製程。 屬層及鉬金屬 根據本發明之一具體實施態 蝕刻方法中，該翻金屬層為’ 1明銅/銷金屬之 或鋼合金，且形成兮_▲ s，D金及該銅金屬層為鋼 生且形成该鉬金屬層及鋼金屬居夕士、“ 獅 相沈積法、化學氣相沈積法 =法為物理氣 本發明㈣方法t之基板可==電鑛法。 類，例如玻璃基板、矽晶圓 基板種 月旨銅箱基板。 圓基板、聚酿亞胺基板或環氧樹 根據本發明之一且微眘 钱刻方法中，所使用之圏亲 在本發明銅Μ目金屬之 圖案化罩幕層為光阻。 敍刻明：一具體實施態樣’在本發明鋼/銷金屬之 至抑。，㈣製程之溫度範圍為15至赋，較佳為乃 行二=例將對本發明钱刻液組成物的組成及以其所進 ==明，唯非用以限制本發明之範圍，任何熟 改變，的… 有^吊知識之人士可輕易達成之修飾及 句涵蓋於本發明之範圍内。 實施例 123643.doc 200916605 (1) 蝕刻液組成物之製作 製作具有如下組成之銅/钥金屬钱刻液組成物·· 8重量％之過氧化氫； 3重量％之甘胺酸； 2重量％之氟化銨； 0.02重量。/。之氫氟酸； 0.08重量％之填酸；及 86.9重量％之去離子水。 (2) 蝕刻操作 於玻璃基板上，使用本領域慣用物理氣相沈積法依 序形成鉬金屬層及銅金屬層，接著’於銅金屬層上 形成银刻圖案用之保護光阻，形成一試驗基板。將 該試驗基板浸潰於具有上述組成之蝕刻液組成物 中，以進行飾刻程序。詳細之钱刻操作條件如下所 不 · 銅/鉬金屬膜厚：銅3000 A /鉬300 A ; 姓刻溫度：2 5 °C ;及 姓刻時間：90秒。 (3) 結果 圖1為蝕刻後試驗基板之掃瞄式電子顯微鏡（SEM)侧視 圖，其中符號1為光阻層、符號2為銅金屬層、符號3為鉬 金屬層、符號4為玻璃基板。圖2則為蝕刻後試驗基板之光 學顯微鏡（OM)放大1000倍俯視圖，顯示蝕刻後之清晰圖 案。由圖1可知，蝕刻後銅/鉬導線的側蝕（CD乙〇^)輕微， 123643.doc 200916605 導線邊緣呈梯形斜角，且㈣屬層沒有内縮⑽如C叫 钱刻結果非常優異。 接著，將触刻後試驗基板上層之光阻層移除，其掃瞎式 電子顯微鏡（SEM)俯視圖係如圖3所心圖3顯示銅/翻導^ 之邊緣平順，玻璃基板表面乾淨且無金屬殘留。 "200916605 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to an etchant composition for a copper/molybdenum two-layer composite metal layer (Cu/m〇bilayer), which can be used to define two layers of copper/molybdenum An etched pattern of a composite metal layer. The etchant composition of the present invention can be applied to other applications such as flat panel display, integrated circuit, flip chip package, printed circuit board, color filter, MEMS, or copper/molybdenum two-layer composite metal layer. The surname is in the process of engraving. [Prior Art] With the development of semiconductors, flat panel displays, and microelectromechanical processes toward large-size and high-speed reaction trends, the conventionally used metal wires have been unable to meet the requirements of electron transport rate, so metal materials with lower resistance values are used (for example). Copper metal) as a wire has the advantage of improving the current conduction speed. However, although steel metal has the advantage of low impedance, it is also easy to oxidize and cannot be dry (4). In addition, due to the poor bonding of copper metal to glass substrate or Shishi substrate, the application of copper metal wire is faced. The difficulty of the above. If a layer of metal is filled between the copper metal and the substrate, the problem can be solved: the copper metal wire is attached to the substrate. Therefore, the copper/molybdenum double-layered metal layer has gradually become the main structure for the development of metal wires. However, in the etching process based on the copper/molybdenum two-layer composite metal layer, the following problems still remain to be overcome: 1. The steel/molybdenum etching rate selection ratio is not easy to overcome. 2. The side loss (CD Loss) of the steel/molybdenum wire is too large. 3. The angle of the side bevel of the copper wire will be greater than or equal to 90. . I23643.doc Composition of 200916605 The inventors of the present invention have extensively discovered that 'having an etchant composition as defined herein' can effectively solve the above problems. SUMMARY OF THE INVENTION The object of the present invention is to provide an etchant composition for copper and molybdenum metal, which is succinctly said to be succinct #^ /.... ruthenium peroxide, the content of which is in the range of etchant Calculated as 1 to 25 weights of amino acid in an amount ranging from Μ to 15% by weight based on the total weight of the etchant composition; pH stabilizer, the content range of the total composition of the engraved composition to 15% by weight a fluorine-containing acid in an amount ranging from 2% by weight based on the total weight of the (IV) liquid composition; and an acidic pH adjusting agent in an amount ranging from 1 to 3% by weight based on the total weight of the etching liquid composition; Aqueous medium. The etching liquid composition of the present invention is used for the formation of a copper/molybdenum electronic circuit pattern, and has the advantages of a stable rate, a uniform rate, a small undercut, and a suitable tap angle of the line. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a method of using a etchant composition of the present invention to name a copper/molybdenum metal. [Embodiment] The composition for a copper/molybdenum metal of the present invention comprises: hydrogen peroxide, an amino acid, a pH stabilizer, a fluorine-containing acid, an acidic pH adjuster, and an aqueous medium. Without wishing to be bound by theory, it is believed that the hydrogen peroxide used in the present invention can be used for copper oxide metal and molybdenum metal. According to an embodiment of the present invention, the hydrogen peroxide content is from 1 to 25 wt%, preferably from 3 to 20 wt%, based on the total weight of the engraved liquid composition. 123643.doc 200916605 Not intended to be limited by theory. The amino acid used in the present invention can be used to etch copper metal and molybdenum metal. According to one embodiment of the present invention, an amino acid suitable for use in the present invention includes, but is not limited to, Glycine, Alanine, or a mixture thereof, and the mixture herein means one or more of the above. Any mixture of amino acids suitable for use in the present invention is preferably glycine or alanine. The content of the amino acid is from 0.1 to 15% by weight, based on the total weight of the etching liquid composition; preferably from 0.5 to 5% by weight. The p Η value stabilizer used in the present invention is used to stabilize the acid value of the etchant composition. According to one embodiment of the invention, pH stabilizers suitable for use in the present invention include, but are not limited to, ammonium fluoride (NH4F), ammonium hydrogen fluoride ((NH4)HF2), ethylene diamine tetraacetate (EDTA-salt) Or a mixture thereof, where the mixture means - or a mixture of any of the above various pH stabilizers. The pH stabilizer suitable for use in the present invention is preferably ammonium fluoride. The pH stabilizer is present in an amount of from 〇 丨 to 丨 5% by weight, based on the total weight of the etchant composition; more preferably from 0.8 to 3% by weight. Unrestricted by the Theory of Unknown Persons The fluorinated acid used in the present invention can be used to remove molybdenum metal remaining on the surface of the substrate. According to one embodiment of the present invention, a fluorine-containing acid suitable for use in the present invention includes, but is not limited to, hydrofluoric acid (HF), fluoroantimonic acid (HjiF4) or a mixture thereof, and the mixture herein means one or more of any of the above. a mixture of fluorine-containing acids. The fluorine-containing acid suitable for use in the present invention is preferably a hydrogen acid. The fluorine-containing acid is present in an amount of up to 2 parts by weight based on the total weight of the etching liquid composition; preferably from 〇 〇丨 to 〇 3 parts by weight. According to an embodiment of the present invention, an acidic pH adjusting agent suitable for use in the present invention includes, but is not limited to, phosphoric acid (H3P〇4), ammonium phosphate 123643.doc 200916605 ((NH4)H2P04), acetic acid (CH3COOH), Oxalic acid (c2H2?4), citric acid (C6H8?7) or mixtures thereof, where the mixture means - or a mixture of any of the above various pH adjusting agents. The acidic pH adjuster suitable for use in the present invention is preferably phosphoric acid or ammonium phosphate. The content of the acidic pH adjusting agent is 0.01 to 3% by weight based on the total weight of the etching liquid composition; preferably 〇〇2 to 5% by weight 〇 The acidic pH adjusting agent used in the present invention can be used for adjusting the etching liquid The pH value of the composition can thereby be used to obtain a suitable etching selectivity for copper/molybdenum. According to one embodiment of the present invention, the pH of the etching solution composition of the present invention ranges from 4 to 6.5', preferably 5. The aqueous medium used in the present invention is well known to those of ordinary skill in the art. For example, water can be used in the preparation process, preferably using deionized water. The etchant composition of the present invention may further comprise other ingredients which are well known to those of ordinary skill in the art and which do not adversely affect the composition of the present invention. The etching liquid composition of the present invention is used for forming a copper/molybdenum electronic circuit pattern to have the advantages of stable etching rate, uniformity, small side etching, and suitable line edge bevel angle. According to an embodiment of the present invention, the present invention The etchant composition can be applied to a planar display, an integrated circuit, a flip chip package, a P-brush circuit board, a color filter, a micro-electromechanical, or a copper/molybdenum two-layer metal layer for other applications. Accordingly, the present invention further provides a copper/molybdenum metal etching method, comprising: 123643.doc 200916605 providing a substrate; forming a molybdenum metal layer on the substrate; forming a copper metal layer on the molybdenum metal layer; Forming a patterned mask layer on the metal layer and "patterning the mask layer as a mask" uses an engraved composition having a ratio of components as previously defined and component ratio to perform an etching process on the component layer. And molybdenum metal according to an embodiment of the present invention, the metallized layer is '1 copper/pin metal or steel alloy, and forms 兮_▲ s, D gold and the copper metal layer is steel and The formation of the molybdenum metal layer and the steel metal, "the lion phase deposition method, the chemical vapor deposition method = the method is the physical gas. The substrate of the invention (4) method t == electric ore method. Classes, such as glass substrates, germanium wafers, and substrate types. Round substrate, polyimine substrate or epoxy tree According to one of the inventions and the method of the method of the invention, the patterned mask layer of the copper metal of the present invention is used as a photoresist. It is stated that: a specific embodiment is in the steel/pin metal of the present invention. (4) The temperature range of the process is 15 to Fu, preferably the second = the example will be the composition of the money engraving composition of the present invention and the input thereof == Ming, but not to limit the scope of the present invention, any cooked Modifications and sentences that are readily achievable by those skilled in the art are within the scope of the invention. Example 123643.doc 200916605 (1) Preparation of etching liquid composition A copper/key metal engraving composition having the following composition was prepared. 8 wt% of hydrogen peroxide; 3 wt% of glycine; 2 wt% Ammonium fluoride; 0.02 weight. /. Hydrofluoric acid; 0.08 wt% acid; and 86.9 wt% deionized water. (2) etching operation on the glass substrate, sequentially forming a molybdenum metal layer and a copper metal layer by physical vapor deposition in the art, and then forming a protective photoresist for the silver engraved pattern on the copper metal layer to form a test Substrate. The test substrate was immersed in an etching liquid composition having the above composition to carry out a grading process. The detailed operating conditions are as follows: Copper/molybdenum metal film thickness: copper 3000 A / molybdenum 300 A; surname temperature: 2 5 ° C; and surname time: 90 seconds. (3) Results FIG. 1 is a scanning electron microscope (SEM) side view of the test substrate after etching, wherein the symbol 1 is a photoresist layer, the symbol 2 is a copper metal layer, the symbol 3 is a molybdenum metal layer, and the symbol 4 is a glass substrate. . Fig. 2 is a top view of the optical microscope (OM) magnified 1000 times after the etching of the test substrate, showing a clear pattern after etching. It can be seen from Fig. 1 that the copper/molybdenum wire has a slight side etching (CD 〇^) after etching, and the edge of the wire has a trapezoidal oblique angle, and (4) the genus layer has no retraction (10), and the result is very excellent. Next, the photoresist layer on the upper layer of the test substrate is removed after being inscribed, and the top view of the scanning electron microscope (SEM) is as shown in FIG. 3, FIG. 3 shows that the edge of the copper/flip guide is smooth, and the surface of the glass substrate is clean and free. Metal residue. "
雖然本發明已以較佳實施例揭露如上’然其並非用以限 f本發明，任何熟習此技藝者，在不脫離本發明之精神與 範圍内，當可作些許之更動與潤飾，因此本發明之保護範 圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 藉由以下附圖及說明’可充分了解本發明之目的、特徵 及其優點。其中： 圖1為以本發明蝕刻液組成物蝕刻後之層板側視圖。 圖2為以本發明钱刻液組成物钱刻後層板表面之光學顯 微鏡1000X放大照片。 圖3為以本發明蝕刻液組成物蝕刻及去光阻後之層板俯 視圖。 【元件符號說明】 1 光阻 2 銅金屬層 3 钥金屬層 4 玻璃基板 123643.doc -12-Although the present invention has been described in the above preferred embodiments, it is intended that the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The objects, features and advantages of the present invention will be fully understood from the following description and appended claims. 1 is a side view of a laminate after etching with the etchant composition of the present invention. Fig. 2 is an enlarged photograph of an optical microscope 1000X of the surface of the laminate after the engraving composition of the present invention. Figure 3 is a top plan view of the laminate after etching and photoresist removal of the etchant composition of the present invention. [Description of component symbols] 1 Photoresist 2 Copper metal layer 3 Key metal layer 4 Glass substrate 123643.doc -12-