201224210 六、發明說明： 相關專利申請案之對照參考資料 本申請案請求於2010年1〇月28日於韓國專利局申請之 韓國專利申請案第10-2010-0106026號案之利益，此案之揭 露内容在此完整併入本案以為參考資料。 C ^^明戶斤屬^^冬奸々貝】 1. 發明領域 本發明係有關於-種用於半導體裝置之含銅金屬薄膜 之蝕刻劑組成物，及使用其之一種蝕刻方法。 、 ^ 2. 相關技藝說明 於半導體裝置，於-基材上製造一金屬佈線之方法— 般係藉由於一基材上藉由喷濺形成一金屬層，於其上塗覆 一光阻劑’將光阻劑曝光，將經曝光之光阻劑顯影於 欲區域上形成-光阻劑圖案，及將金屬層_而實施，其 中，一清洗處理係於蝕刻操作之前或之後實施。蝕刻處理 係指金屬層係藉由使用光阻劑作為一遮罩而於一所欲區域 上形成’且-般係藉由制錢之乾式㈣或使賴刻劑 之濕式蝕刻而實施。 用於半導體裝置之金屬電路之電阻係造成RC信號延 遲之一關鍵因素，且特別地，降低金屬佈線之電阻係增加 面板尺寸及薄膜電晶體液晶顯示器（TFT LCD)之高解析度 之關鍵。 因此，為降低RC信號延遲，其對於製造具有大尺寸之 3 201224210 TFT-LCD係必然需要’具有低電阻之膜已被作為— 金屬薄膜。但是，係難以將—光阻劑塗覆於銅薄膜且及將 其上之光阻劑圖案化’且銅薄膜與—錢緣膜具有 著強度。 為解決銅薄膜之缺點，係提議使用—多金屬薄膜，例 如，-銅(CU)/鈦(Ti)薄膜。Cu/Ti薄膜具有特別之化學性質， 且因此’於缺乏氟料巾不被⑽。當使I含諸子餘 刻劑，-玻璃基材及任何賴之⑦層（―”體層及 石夕薄膜形成之-純化層）皆被㈣，且因此，缺陷會於 方法中發生。另-方面’當Cu/Mo薄膜之厚度經適當調整 時，一Cu/鉬（Mo)薄膜可具有與Cu/Ti薄膜者相似或更佳之 性質，且所欲地係Cu/Mo薄膜係使用一無氟離子之蝕刻劑 名虫刻。 韓國專利公告第1999-17836號案揭示碟酸 '确酸，及 乙酸之混合物，作為用於一含Cu多金屬薄膜之一蝕刻劑， 且韓國專利公告第2000-32999號案揭示含有氯化鐵六水合 物及氫氟酸(HF)之混合物之一蝕刻劑。但是，當此一酸混 合物作為一蚀刻劑，一蚀刻方法實施太快，使得處理界限 問題會發生。此外，錐角係90°或更大，使得難以實施其後 之處理。當使用HF酸，一玻璃基材或一矽層被钮刻，其係 於使用Cu/Ti薄膜時發生之問題。 為解決Cu/Ti薄膜及Cu/Mo薄膜之問題，一Cu/Ti-Mo薄 膜最近被用於金屬佈線。作為用於Cu/Ti-Mo薄膜之一蝕刻 劑組成物，韓國專利公告第2010-40352號案揭示一種蝕刻 201224210 劑組成物，其含有5至20重量％之過氧化氫溶液，1至5重量 %之碟酸’ 0.1至5重量％之磷酸鹽，〇1至1〇重量％之螯合 劑’0.1至5重量％之一環狀胺化合物，及使組成物總量為1〇〇 重夏％之水。但是，此蝕刻劑組成物係用於自含有Cu(Cu合 金)/Ti、Mo，或一Mo合金之一多金屬薄膜選擇性蝕刻一Cu 或Cu合金層，因此’此一蝕刻方法係不同於一多金屬薄膜 之餘刻方法。 Γ ^^明内溶1 3 發明概要 本發明提供一種用於一含銅(Cu)金屬薄膜之蝕刻劑組 成物，其能共同地触刻含Cu金屬多薄膜，而不會損及一玻 璃基材。 本發明亦提供一種使用此蝕刻劑組成物之蝕刻方法。 依據本發明之一方面，提供一種用於一含銅金屬薄膜 之姓刻劑組成物，此蚀刻劑組成物包括：0.1至30重量％之 過氧化氫，0.1至7.〇重量％之磷酸，0.〇1至5.〇重量％之一環 狀胺化合物’ 0.1至5.0重量％之硫酸鹽，0.1至ΐ·〇重量％之氟 棚酸’及使姓刻劑組成物之總重量為1〇〇重量％之水。 依據本發明之另一方面，提供一種蝕刻一含銅金屬薄 膜之方法，此方法包括：將一含銅金屬薄膜沉積於〆基材 上；於含鋼金屬薄膜上形成一光阻劑圖案；以及藉由使用 上述#刻劑組成物蝕刻含銅金屬薄膜。 圖式簡單說明 本發明之如上及其它之特徵與優點藉由參考所附圖式 5 201224210 詳細說明其例示實施例會變得更曰明顯，其中·· 第1圖係例示依據本發明之一實施例之一蝕刻方法之 不意圖； 第2圖係使用依據範例i之一蝕刻方法蝕刻之—薄膜電 晶體(TFT)之掃瞄電子顯微(SEM)影像； 第3圖係使用依據範例2之一蝕刻方法蝕刻之—τ f τ之 SEM影像； 第4圖係使用依據範例3之一餘刻方法触刻之一 TFT之 SEM影像； 第5圖係使用依據範例4之一姓刻方法餘刻之一 TFT之 SEM影像； 第6圖係使用依據比較例1之一蝕刻方法蝕刻之一TFT 之SEM影像；且 第7圖係使用依據比較例2之一蝕刻方法蝕刻之一 TFT 之SEM影像。 C ΆΓ方包】 本發明之詳細說明 其後，一蝕刻劑組成物及使用其之一蝕刻方法之例示 實施例將被更詳細說明。 諸如至少一”之表示當前面係列示之元素時係修飾 整個列示之元素，且非修飾此列示之個別元素。 依據本發明之一實施例，用於含銅(Cu)金屬薄膜之一 蝕刻劑組成物包括(U至3〇重量％之過氧化氫，〇1至7 〇重量 %之磷酸’ 0.01至5.0重量％之一環狀胺化合物，〇.1至5.0重201224210 VI. INSTRUCTIONS: RELATED STATEMENT OF RELATED PATENT APPLICATIONS This application claims the benefit of the Korean Patent Application No. 10-2010-0106026 filed on the Korean Patent Office on January 28, 2010. The disclosure is hereby incorporated by reference in its entirety. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etchant composition for a copper-containing metal thin film used in a semiconductor device, and an etching method using the same. 2. 2. Description of the Related Art In semiconductor devices, a method of fabricating a metal wiring on a substrate is generally performed by forming a metal layer on a substrate by sputtering to apply a photoresist The photoresist is exposed, the exposed photoresist is developed on the desired region to form a photoresist pattern, and the metal layer is applied, wherein a cleaning process is performed before or after the etching operation. The etching treatment means that the metal layer is formed on a desired region by using a photoresist as a mask, and is generally performed by dry etching (4) or by wet etching of a photoresist. The resistance of the metal circuit used in the semiconductor device is one of the key factors for RC signal delay, and in particular, reducing the resistance of the metal wiring increases the size of the panel and the high resolution of the thin film transistor liquid crystal display (TFT LCD). Therefore, in order to reduce the RC signal delay, it is necessary to manufacture a film having a large size. The 201224210 TFT-LCD system necessarily requires a film having a low electrical resistance to be used as a metal thin film. However, it is difficult to apply a photoresist to the copper film and to pattern the photoresist thereon, and the copper film and the film have strength. In order to solve the shortcomings of copper films, it is proposed to use a multi-metal film, for example, a copper (CU) / titanium (Ti) film. The Cu/Ti film has particular chemical properties and is therefore not (10) in the absence of a fluoride wipe. When I have the remainder of the formulation, the glass substrate and any of the 7 layers ("" body layer and the formation layer - the purification layer) are all (4), and therefore, defects may occur in the method. 'When the thickness of the Cu/Mo film is properly adjusted, a Cu/molybdenum (Mo) film may have similar or better properties than those of the Cu/Ti film, and the desired Cu/Mo film system uses a fluorine-free ion. The etchant name is insect. Korean Patent Publication No. 1999-17836 discloses a mixture of a dish acid and an acetic acid as an etchant for a Cu-containing multimetal film, and Korean Patent Publication No. 2000-32999 The exemplifying agent discloses an etchant containing a mixture of ferric chloride hexahydrate and hydrofluoric acid (HF). However, when the acid mixture is used as an etchant, an etching method is performed too fast, so that a treatment boundary problem occurs. Further, the taper angle is 90 or more, making it difficult to carry out the subsequent treatment. When HF acid is used, a glass substrate or a layer of a layer is engraved, which is a problem that occurs when a Cu/Ti film is used. Solve the problem of Cu/Ti film and Cu/Mo film, a Cu/Ti-Mo film Recently used as a metal wiring. As an etchant composition for a Cu/Ti-Mo film, Korean Patent Publication No. 2010-40352 discloses an etching 201224210 agent composition containing 5 to 20% by weight of peroxidation. Hydrogen solution, 1 to 5% by weight of dish acid '0.1 to 5% by weight of phosphate, 〇1 to 1% by weight of chelating agent '0.1 to 5% by weight of one of cyclic amine compounds, and the total amount of the composition It is a water of 1% by weight. However, the etchant composition is used for selectively etching a Cu or Cu alloy layer from a polymetallic film containing Cu (Cu alloy) / Ti, Mo, or a Mo alloy. Therefore, this etching method is different from the residual method of a multi-metal film. Γ ^^明内1 1 SUMMARY OF THE INVENTION The present invention provides an etchant composition for a copper-containing (Cu) metal film, The Cu metal-containing multiple film can be collectively engraved without damaging a glass substrate. The present invention also provides an etching method using the etchant composition. According to an aspect of the present invention, a copper-containing material is provided. a surname composition of a metal film, the etchant composition comprising: 0.1 to 30% by weight of hydrogen peroxide, 0.1 to 7% by weight of phosphoric acid, 0. 〇1 to 5. 〇% by weight of one cyclic amine compound '0.1 to 5.0% by weight of sulphate, 0.1 to ΐ· 5% by weight of fluoro succinic acid' and water having a total weight of the surname composition of 1% by weight of water. According to another aspect of the present invention, there is provided a method of etching a copper-containing metal film, the method comprising: Depositing a copper-containing metal film on the tantalum substrate; forming a photoresist pattern on the steel-containing metal film; and etching the copper-containing metal film by using the above-described #marking composition. And other features and advantages will become more apparent by the detailed description of the exemplary embodiments thereof with reference to FIG. 5 201224210, wherein: FIG. 1 illustrates a schematic illustration of an etching method according to one embodiment of the present invention; Figure 2 is a scanning electron microscopy (SEM) image of a thin film transistor (TFT) etched according to one of the etching methods of Example i; Figure 3 is a τ f τ etched using an etching method according to Example 2. SEM image; Figure 4 is based on the use of the standard 3 one of the remaining methods to engrave one of the SEM images of the TFT; the fifth picture is based on the SEM image of one of the TFTs according to the method of the first example of the example 4; the sixth figure uses an etching method according to the comparative example 1 An SEM image of one of the TFTs is etched; and FIG. 7 is an SEM image of one of the TFTs etched using one of the etching methods of Comparative Example 2. C ΆΓ 包 包 】 Detailed Description of the Invention Hereinafter, an etchant composition and an exemplary embodiment using one of the etching methods will be described in more detail. The elements of the present invention, such as at least one of the above, are intended to modify the entire listed elements, and the individual elements listed are not modified. According to one embodiment of the invention, one of the metal films containing copper (Cu) is used. The etchant composition comprises (U to 3% by weight of hydrogen peroxide, 〇1 to 7% by weight of phosphoric acid '0.01 to 5.0% by weight of one cyclic amine compound, 〇.1 to 5.0 重量
6 201224210 量％之硫酸鹽，0·1至1.0重量％之氟硼酸，及使組成物總重 量為100重量％之水。特別地，此蝕刻劑組成物包括18重量 %之過氧化氫，3重量％之磷酸，0.8重量％之一環狀胺化合 物，1.5重量％之硫酸鹽，0.5重量％之氟棚酸，及76.2重量％ 之水。 含Cu金屬薄膜可為由Cu或一Cu合金形成之單一薄 膜，或含有Cu與Mo及Ti之至少一者之一多層薄膜。 含有Cu與Mo及Ti之至少一者之多層薄膜包括一雙層 物，其包括一Cu薄膜及形成於Cu薄膜上之Mo及Ti之至少一 者之一薄膜’或相反，及一多層物，其中，一 Cu薄膜與Mo 及Ti之至少一者之一薄膜係被交替置放 '有關於此，一多 層薄膜結構可藉由用以形成一下或上薄膜之材料的型式或 其間之黏著性而決定。此外，Cu薄膜與Mo及Ti之至少一者 之薄膜的厚度可不同地調整。例如，Cu薄膜之厚度可為大 於Mo及Ti之至少一者之薄膜者。 當一薄膜係由Mo及Ti形成時，此二金屬可以一合金型 式存在。 包含於蝕刻劑組成物内之過氧化氫、磷酸、硫酸鹽， 及環狀胺化合物可使用此項技藝已知之方法製備，且可具 有用於半導體製造操作之純度。此外，水可為用於半導體 製造操作之去離子水。 此外，具有用於半導體製造操作之純度之呈水溶液之 可購得產品可作為氟硼酸(hbf4)，或氟硼酸可被製備。 蝕刻劑組成物可進一步包括一普遍使用之添加劑。6 201224210 % by weight of sulfate, 0.1 to 1.0% by weight of fluoroboric acid, and water having a total weight of the composition of 100% by weight. In particular, the etchant composition comprises 18% by weight of hydrogen peroxide, 3% by weight of phosphoric acid, 0.8% by weight of one of cyclic amine compounds, 1.5% by weight of sulfate, 0.5% by weight of fluorochemical, and 76.2. % by weight of water. The Cu-containing metal thin film may be a single thin film formed of Cu or a Cu alloy, or a multilayer thin film containing at least one of Cu and Mo and Ti. The multilayer film comprising at least one of Cu and Mo and Ti comprises a bilayer comprising a Cu film and a film of at least one of Mo and Ti formed on the Cu film or vice versa, and a multilayer Wherein, a film of at least one of the Cu film and at least one of Mo and Ti is alternately disposed. In this regard, a multilayer film structure may be formed by a pattern for forming a material of the lower or upper film or a bond therebetween. Sexually decided. Further, the thickness of the Cu film and at least one of Mo and Ti may be adjusted differently. For example, the thickness of the Cu film may be greater than that of at least one of Mo and Ti. When a film is formed of Mo and Ti, the two metals may exist in an alloy form. Hydrogen peroxide, phosphoric acid, sulfate, and cyclic amine compounds contained within the etchant composition can be prepared using methods known in the art and can be used in semiconductor manufacturing operations. Additionally, water can be deionized water for semiconductor manufacturing operations. Further, a commercially available product having an aqueous solution having a purity for a semiconductor manufacturing operation can be prepared as fluoroboric acid (hbf4), or fluoroboric acid can be prepared. The etchant composition may further comprise a commonly used additive.
S 7 201224210 用於姓刻劑組成物之過氧化氫及磷酸係用以蝕刻一 C u 溥膜及一Mo薄膜之主要組份，且可具有用於半導體製造操 作之純度，使得金屬雜質之含量係低於ppb量。 触刻劑組成物之過氧化氫之量可為0·1至30重量％之範 圍内，例如，於1〇至25重量％之範。當過氧化氫之量太大， 於金屬離子存在於溶液時具有藉由催化劑反應之爆炸的危 險。另一方面’當過氧化氫之量太小，係難以平滑地蝕刻 一金屬薄膜，且因此，欲被蝕刻之一金屬薄膜可能留下作 為殘質。 蚀刻劑組成物之磷酸之量可為〇1至7〇重量％之範 圍，例如，於2至5重量％之範圍。磷酸調整蝕刻劑組成物 之pH使一含Cu-金屬薄膜被触刻。触刻劑組成物之可藉 由磷酸調整至0.5至4.5之範圍。此外，磷酸與氧化之〇11離子 結合形成填酸鹽，藉此，增加於水中之可溶性，且因此， 於蝕刻處理後，欲被蝕刻之一含(^金屬薄膜不會留下作為 殘質。但疋，當使用過量磷酸時，含Cu金屬薄膜會被過度 蚀刻。另-方面，當磷酸之量太小，含以金屬薄膜之钮刻 速率會降低。 蝕刻劑組成物之硫酸鹽量可為〇1至5〇重量％之範 圍，例如，0-5至3重量％之範圍。硫醆鹽係用於增加一m〇 薄膜之關速率之-成份，且不被特別限制。例如，硫酸 鹽牙為其巾硫酸之氫係以錄 ' ―驗金屬，或―驗土金屬取 代之鹽’諸如，硫酸録、過硫_、俩納、過硫酸納、 硫酸鉀，或過硫酸鉀。顧鹽增加_仏_之敍速率，藉 201224210 此，避免一含Cu金屬薄膜具有一階級形狀之錐狀輪廓其係 於Μ 〇薄膜被蝕刻時C u薄膜被過度蝕刻而形成。若c u薄膜皮 過度蝕刻，因於Cu薄膜之一上部份之大的臨界尺寸損失 Cu薄膜之線寬度變小，且因此，cu薄膜之電阻增加。因匕 對於使用具低電阻之金屬並無優點。 蝕刻劑組成物之氟硼酸之量可於〇1至1〇重量7之矿 圍’例如’ 0.2至1.0重量％之範圍。不同於一般之含氣離子 化合物，用於蝕刻劑組成物之氟硼酸不會損害—破璃美材 或-含♦基材，且使-含Cu金屬薄膜被共同地餘刻。此外， 氟硼酸能增加一下Mo薄膜、一Μο-Ti薄膜，或—Ti薄膜之 蝕刻速率，且可避免形成一階級形狀之錐狀輪廓。 此外，當LCD裝置被大量製造，數個基材需使用相同 侧劑組錢處理。但是，#含以金屬多層物使用一傳統 姓刻劑組成物㈣時’產生之Cl^M。離子再次錢刻劑植 成物反應快速改變_劑組成物之組成，且因此，㈣劑 組成物之㈣性質於處理某些數量之基材後改變。另一 ^ 面’ g«作為-含氟離子化合物，#制組成物之钱 刻性質.改變之時·延遲，關此，以相_刻劑組成物 處理之基㈣數量增加。特別地，#❹氟硼酸時，以一 下薄膜形成之一M〇薄膜或—Mo-Ti薄膜被平滑祕刻。更 _地’ _酸與__成物之過氧化氫及雜一起於 降低由於訂欲被㈣之薄膜作為殘f之佈線缺陷及維持 蝕刻劑組成物之蝕刻力扮演重要角色。 用於姓刻劑、，且成物之環狀胺化合物調整一含&金屬薄 201224210 膜之蝕刻速率及降低—含Cu金屬薄膜圖案之臨界尺寸(CD) 才貝失，藉此，增加處理界限。環狀胺化合物之例子不受限 地包括胺基四唑、咪唑、吲、嘌呤、吡唑 '吡啶、嘧啶、 吡咯、吡咯烷、二氫吡咯，及其它水溶性環狀胺化合物。 環狀胺化合物調整蝕刻速率且能獲得具有欲寬度之一金屬 佈線。 依據本發明之另一實施例，蝕刻一含Cu金屬薄膜之一 方法包括將一含Cu金屬薄膜沉積於一基材上；於含Cu金屬 薄膜上形成一光阻劑圖案；以及藉由使用上述之蝕刻劑組 成物蝕刻含Cu金屬薄膜。 第1圖係例示依據本發明之一實施例之一姓刻方法之 示意圖。依據本發明之一實施例之一蝕刻方法現將參考第1 圖而更詳細地說明。 一 Mo-Ti合金薄膜12及一 Cu薄膜14係藉由化學蒸氣沉 積依序沉積於一玻璃基材1〇上（參考第1A圖）。Mo-Ti合金薄 膜12之厚度係於約50至約5〇〇之範圍，且Cu薄膜14之範圍 係於約1，500至約2,000之範圍。用於一顯示裝置之一結構 (未示出）可被夾置於玻璃基材10與Mo-Ti合金薄膜12之 間。用於一顯示裝置之結構係指一圖案係形成於一導電 層，諸如，任何種類之氧化物層或氮化物層（例如，氧化石夕 層或氮化矽層）、一半導體層（例如，非結晶性之矽層或聚矽 層）、一經摻雜之非結晶性聚矽層’或任何種類之金屬層上 且上述層之至少一者係彼此堆疊之一結構。此外，一般之 清洗處理係於基材10、Cu薄膜14,及Mo-Ti合金薄膜12上實 10 201224210 施0 其次，為於一所欲區域上形成Cu/M〇 Ti之一雙薄犋， -光阻劑16塗覆於Cu薄膜14上(參考第_)，且藉由使用 -遮罩選擇性曝光’且光阻劑16係使用―齡彡溶液部份移 除（參考第ic圖）。*此方面，*阻劑16可為其中未經曝光 之部份被顯影之-負型光阻劑，或其中經曝光之部份被顯 影之-正型光阻劑。此外，於光阻劑處理，諸如灰化、熱 處理等之一般處理可被進一步實施。 其次’ Cu/Μο-Ή雙薄膜係使用此關劑組成物姓刻。 第1D圖例示Cu薄膜14已經飯刻後之一狀態。然後，M〇_Ti 合金薄膜12係'使用相同㈣劑組成物㈣（參考第正圖卜 第1E圖係薄膜之厚度等之—放大圖。Cu/MQ_Ti雙薄膜之姓 刻處理可使用此項㈣已知方法實拖，諸如，浸潰或喷灑。 於姓刻處理，侧·成物之溫度可為赃饥之範圍， 且I虫刻時間-般可於約5〇至⑽秒之範圍。最後，光阻齊⑽ 被王部移除以獲得如第1F圖所例示之結構。 藉由使用上述钱刻方法，可製造一 LCD裝置及一半導 體裝置。 於此情況’-半導體結構可於一基材與—含以金屬薄 膜之間I纟此半導體結構包括用於諸如lcd、pDp等之顯 不裝置之半導體結構，且係指包括選自藉由化學蒸氣沉積 形成之-絕緣薄膜、藉由喷濺形成之一導電薄膜，及諸如 非結晶性或多結晶性㈣膜之—半導體薄膜之至少一者且 係藉由光微影術或蝕刻製造之—結構。 201224210 製造LCD裝置之TFT之一方法包括於一基材上形成— 閘極電極；於基材上形成一閘極絕緣層以覆蓋閉極電極. 於閘極絕緣層上形成一半導體層；於半導體層上形成原極 及〉及極電極，及形成與汲極電極連接之一像素電極。古 有關 於此，閘極電極、源極及汲極電極，及像素電極可藉由上 述蝕刻方法形成。換言之，含Cu金屬薄膜可經蝕刻形成構 成TFT-LCD之資料線之閘極佈線及源極/沒極佈線。特別 地，TFT-LCD之源極/汲極佈線會具有與電阻有關之問題， 且因此，一含Cu金屬薄膜，特別是Cu/Mo_Ti、Ti，或M〇之 —多薄膜可作為源極/汲極佈線，且使用上述蝕刻劑組成物 輕易蝕刻，藉此，獲得一大尺寸之TFT-LCD。 本發明之一或多個實施例現將參考下列範例更詳細地 說明。但是，此等範例僅係用於例示目的，且非意欲限制 本發明之範圍。 製備範例1至6 包含於下第1表中所示含量之組份及剩餘量之水的組 成物被製備。 12 201224210 <第1表> 過氧化氮 (重量％) 磷酸 (重量％) 硫酸銨 (重量％) 胺基四唑 (重量％) 氟硼酸 (重量％) 氫氟酸 (重量％) 製備例1 18 3.0 1.5 0.8 0.9 0 製備例2 18 3.0 0.5 0.8 0.7 0 製備例3 15 3.0 1.0 0.4 0.5 0 製備例4 10 3.0 0.5 0.2 0.3 0 製備例5 18 3.0 1.5 0.8 0 0.5 製備例6 25 5.0 3.0 1.0 1.5 0 範例1 一 Mo-Ti合金薄膜（50:50)及一 Cu薄膜係藉由化學蒸氣 沉積依序沉積於一玻璃基材上。Mo-Ti合金薄膜之厚度係約 300至400 且Cu薄膜之厚度係約2,000至2,500 。 其次，為於一所欲區域上形成Cu/Mo-Ti雙層物，一光 阻劑係塗覆於Cu薄膜上，且藉由使用一遮罩選擇性曝光， 且光阻劑係藉由使用一顯影溶液部份移除。其後，Cu/Mo-Ti 層之蝕刻處理係使用依據製備例1製備之蝕刻劑組成物藉 由喷灑實施。於蝕刻處理，蝕刻劑組成物之溫度係33°C， 且蝕刻時間係約70秒。終點檢測(EPD，金屬被蝕刻之時間） 係使用肉眼測量以獲得隨時間之蝕刻速率。蝕刻處理終結 後，實施沖洗處理及乾燥處理。最後，光阻劑被全部移除。 13 201224210 使用上賴刻處理糊之Cu/M()_Ti層之輪廓係使用一 橫截面掃猫電子顯微鏡(魏)(由Hltachi製造，型號：s_42〇〇) 觀察。 範例2至4 蝕刻處理係以與範例1相同方式實施，但依據製備例2 至4製備之#刻劑組成物被個別使用，且獲得银刻速率及藉 由橫截面SEM之雙層物輪廓。 比較例1 -1虫刻處理係以與範例丨相同方式實施，但使用依據製 備例5製備之银刻劑組成物，且獲得银刻速率及藉由橫截面 SEM之雙層物輪廓。 比較例2 -關處理係以與範例！相同方式實施，但使用依據製 備例6製備之餘刻劑組成物，且獲郷刻速率及藉由橫截面 SEM之雙層物輪廓。 依據範例1至4與比較例丨及2之蝕刻處理之每一者之蝕 刻速率、CD損失、錐角’及尾長之評估係顯示於下之第2 表。 同時’ 1，000 ppm之Cu粉添加至製備m之餘刻劑組成 物’且於其内溶解4小時。具有5 \5尺寸之一基材係以與範 例1相同之方式藉由使用含有溶於㈣之以之㈣劑組成 物蝕刻，且蝕刻輪廓係藉由場發射(FE)_SEM分析。其後， 1，000 ppm之Cu粉進一步添加至含有溶於其内之Cu之蝕刻 劑組成物，且且此方法係重複實施至添加之Cu粉之總量係 14 201224210 6,000至8,000 ppm為止。與—起始蝕刻輪廓（參考)(其中 粉未被包括之情況）比較，作為污染增加度之於輪廓變化時 添加之Cu粉之量被測量，且用以依據基材尺寸及沉積Cu薄 膜之厚度考量面積而回算蝕刻劑組成物之累積處理數量。 於累積處理數量之計算處理，基材尺寸未固定，因此，範 例1之蝕刻劑組成物之累積處理數量係經由依據Cu粉累積 度之分析結果回算。結果係顯示於下之第2表。此處理係個 別使用製備例2至6之蝕刻劑組成物重複實施，以計算於範 例2至4與比較例1及2之蝕刻處理使用之蝕刻劑組成物之每 一者之累積處理數量。 <第2表> 蝕刻速率（/秒） CD損失 (/zm) 錐角 Γ ) 尾長 (脾） 累積處理 數量 (ppm) Cu薄膜 Mo-Ti 薄膜 範例 90-100 30-35 0.515 45 0 6500 範例2 85-90 20-25 0.458 55 0.348 6500 範例3 70-75 18-22 0.304 40 0.241 6500 範例4 60-65 10〜14 0.121 50 0.660 6500 比較例1 45-50 55-60 0.212 55 0 2000 比較例2 130-140 50-55 1.086 65 0 3000 第2至7圖係例示使用範例1至4與比較例丨及2之餘刻方 法蝕刻之TFT之FE-SEM影像。參考第2至5圖，確認當使用 15 201224210 依據本發明之一實施例之蝕刻劑組成物，對玻璃基材不具 損害，且一多層物被共同地蝕刻。此外，如上之第2表所示， 當使用依據本發明之一實施例之蝕刻劑組成物，累積處理 數量增加。 另一方面，於比較例1及2之情況，觀察到對玻璃基材 之損害，玻璃基材被蝕刻造成如第6圖所例示之階級式差 異，且一下薄膜之下切缺陷係如第7圖所例示般確認。此 外，如上之第2表所示，累積處理數量確認係減少。 換言之，於比較例1之情況，其中，使用氫氟酸替代氟 硼酸，玻璃基材上之攻擊係如第6圖所例示般嚴重，且累積 處理數量如上之第2表中所示般係顯著減少。此外，於比較 例2之情況，其中，氟硼酸之量係大於1.0重量％，當蝕刻速 率快速時，累積處理數量顯著減少。再者，當钱刻速率大 於100 /秒，係難以控制蝕刻處理，且缺陷速率由於如第7 圖所例示般之下薄膜之資料開口缺陷及下切缺陷而增加， 因此，降低生產率。 因此，如第2表及圖式所示’依據本發明之一實施例之 姓刻劑組成物包含一特定量範圍之氟硼酸，因此，當姓刻 處理使用此蝕刻劑組成物實施時，不同於傳統蝕刻劑組成 物，對玻璃基材係不具損害，且累積處理數量大，其大量 促成生產率增加。 如上所述，依據本發明之一或多個實施例，一蝕刻劑 組成物能共同地钱刻一含Cu金屬薄膜而不會損害一玻璃基 材，因此，玻璃基材係可再利用，且蝕刻劑組成物之累積 16 201224210 處理數量增加，藉此，增加半導體裝置之生產率。 雖然本發明已參考其例示實施例而特別顯示及說明， 但熟習此項技藝者會瞭解於型式及細節之各種改變可於其 内在未偏離如下列申請專利範圍中界定之本發明的精神及 範圍下進行。 I：圖式簡單說明3 第1圖係例示依據本發明之一實施例之一蝕刻方法之 示意圖； 第2圖係使用依據範例1之一蝕刻方法蝕刻之一薄膜電 晶體(TFT)之掃瞄電子顯微(SEM)影像； 第3圖係使用依據範例2之一蝕刻方法蝕刻之一TFT之 SEM影像； 第4圖係使用依據範例3之一蝕刻方法蝕刻之一TFT之 SEM影像； 第5圖係使用依據範例4之一蝕刻方法蝕刻之一TFT之 SEM影像； 第6圖係使用依據比較例1之一蝕刻方法蝕刻之一TFT 之SEM影像；且 第7圖係使用依據比較例2之一蝕刻方法蝕刻之一TFT 之SEM影像。 【主要元件符號說明】 10.. .玻璃基材 16...光阻劑 12.. .Mo-Ti合金薄膜 14.. .CU 薄膜 17S 7 201224210 Hydrogen peroxide and phosphoric acid for the surname composition are used to etch a main component of a Cu film and a Mo film, and may have a purity for semiconductor manufacturing operations such that the content of metal impurities It is lower than the amount of ppb. The amount of hydrogen peroxide of the etchant composition may range from 0.1 to 30% by weight, for example, from 1 Torr to 25% by weight. When the amount of hydrogen peroxide is too large, there is a risk of explosion by the catalyst reaction when metal ions are present in the solution. On the other hand, when the amount of hydrogen peroxide is too small, it is difficult to smoothly etch a metal thin film, and therefore, a metal thin film to be etched may remain as a residue. The amount of phosphoric acid of the etchant composition may range from 〇1 to 7〇% by weight, for example, in the range of from 2 to 5% by weight. The phosphoric acid adjusts the pH of the etchant composition to cause a Cu-containing metal film to be etched. The composition of the etchant can be adjusted to a range of from 0.5 to 4.5 by phosphoric acid. Further, phosphoric acid is combined with oxidized cerium 11 ions to form a sulphate salt, thereby increasing the solubility in water, and therefore, after etching treatment, one of the metal films to be etched does not remain as a residue. However, when excessive phosphoric acid is used, the Cu-containing metal film is over-etched. On the other hand, when the amount of phosphoric acid is too small, the rate of the button containing the metal film is lowered. The amount of sulfate in the etchant composition can be The range of 〇1 to 5〇% by weight, for example, in the range of 0-5 to 3% by weight. The sulfonium salt is used for increasing the rate of the shutdown rate of the film, and is not particularly limited. For example, sulfate The tooth is the hydrogen of the sulphuric acid of the sulphuric acid, or the salt of the soil-replaced metal, such as sulfuric acid, persulfate, sodium, sodium persulfate, potassium sulfate, or potassium persulfate. Increasing the rate of _仏_, by 201224210, avoiding a tapered shape of a Cu-containing metal film having a class shape which is formed by over-etching the Cu film when the film is etched. If the cu film is over-etched Due to the large part of the upper part of the Cu film The line width of the Cu film is reduced, and therefore, the resistance of the cu film is increased because there is no advantage in using a metal having a low electrical resistance. The amount of the fluoroboric acid of the etchant composition can be from 1 to 1 Torr. The mineral range of 7 is, for example, in the range of 0.2 to 1.0% by weight. Unlike the general gas-containing ionic compound, the fluoroboric acid used in the etchant composition does not damage the glazed or ♦ substrate, and - The Cu-containing metal film is collectively remnant. In addition, fluoroboric acid can increase the etching rate of the Mo film, the Μ-Ti film, or the -Ti film, and avoid the formation of a tapered shape of a class shape. LCD devices are manufactured in large quantities, and several substrates need to be treated with the same side agent group. However, #containing a metal multilayer using a conventional surname composition (4) when the 'produced Cl ^ M. Ion again money engraving The composition reaction rapidly changes the composition of the composition of the agent, and therefore, the (four) nature of the (iv) agent composition changes after processing a certain amount of the substrate. The other surface 'g« acts as a fluorine-containing ionic compound, The nature of the money of the object. When the time changes Delay, close, increase the number of bases (4) treated with the phase composition. In particular, when #❹ fluoroboric acid is formed, one of the films formed by the lower film or the film of Mo-Ti is smoothed and secreted. The hydrogen peroxide and the impurities of the _ acid and __ together play a important role in reducing the etching resistance of the film (4) as a residual f and maintaining the etching force of the etchant composition. And the cyclic amine compound of the product adjusts the etching rate of the film containing & metal thin 201224210 and reduces the critical dimension (CD) of the pattern of the metal film containing Cu, thereby increasing the processing limit. Examples include, without limitation, aminotetrazole, imidazole, indole, indole, pyrazole 'pyridine, pyrimidine, pyrrole, pyrrolidine, dihydropyrrole, and other water-soluble cyclic amine compounds. The cyclic amine compound adjusts the etching rate and can obtain a metal wiring having a desired width. According to another embodiment of the present invention, a method of etching a Cu-containing metal film comprises depositing a Cu-containing metal film on a substrate; forming a photoresist pattern on the Cu-containing metal film; and using the above The etchant composition etches a Cu-containing metal film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a method of surname according to an embodiment of the present invention. An etching method according to an embodiment of the present invention will now be described in more detail with reference to FIG. A Mo-Ti alloy film 12 and a Cu film 14 are sequentially deposited on a glass substrate 1 by chemical vapor deposition (refer to Fig. 1A). The thickness of the Mo-Ti alloy film 12 is in the range of about 50 to about 5 Å, and the Cu film 14 is in the range of about 1,500 to about 2,000. A structure (not shown) for a display device can be sandwiched between the glass substrate 10 and the Mo-Ti alloy film 12. The structure for a display device means that a pattern is formed on a conductive layer, such as any kind of oxide layer or nitride layer (for example, a oxidized layer or a tantalum nitride layer), a semiconductor layer (for example, An amorphous non-crystalline layer or a polyfluorene layer, a doped non-crystalline polylayer layer or any type of metal layer and at least one of the above layers is stacked on one another. In addition, the general cleaning process is performed on the substrate 10, the Cu film 14, and the Mo-Ti alloy film 12. 10 201224210 0 Next, a double thin crucible of Cu/M〇Ti is formed on a desired region. - Photoresist 16 is applied to Cu film 14 (refer to _), and is selectively exposed by using a mask - and photoresist 16 is partially removed using a aging solution (refer to the ic diagram) . * In this respect, the *resistant 16 may be a negative-type photoresist in which an unexposed portion is developed, or a positive-type photoresist in which an exposed portion is developed. Further, general treatment such as ashing, heat treatment or the like can be further carried out in the photoresist treatment. Next, the 'Cu/Μο-Ή double film system uses the composition of the agent to be surnamed. Fig. 1D illustrates a state in which the Cu film 14 has been cooked. Then, the M〇_Ti alloy film 12 is made using the same (four) agent composition (4) (refer to the thickness of the film of the first image of FIG. 1E, etc.). The Cu/MQ_Ti double film can be used for the last name processing. (4) Known methods such as dipping or spraying. In the case of surname processing, the temperature of the side and the object may be the range of hunger, and the time of the I insect can generally range from about 5 〇 to (10) seconds. Finally, the photoresist (10) is removed by the king to obtain the structure as illustrated in Fig. 1F. By using the above-described money engraving method, an LCD device and a semiconductor device can be fabricated. In this case, the semiconductor structure can be used. A substrate and a metal film are included. The semiconductor structure includes a semiconductor structure for a display device such as lcd, pDp, etc., and is comprised of an insulating film selected from the group consisting of chemical vapor deposition. A conductive film is formed by sputtering, and at least one of a semiconductor film such as an amorphous or polycrystalline (tetra) film is fabricated by photolithography or etching. 201224210 Manufacturing of TFTs for LCD devices A method includes forming a gate on a substrate An electrode; a gate insulating layer is formed on the substrate to cover the closed electrode; a semiconductor layer is formed on the gate insulating layer; a primary electrode and a gate electrode are formed on the semiconductor layer, and a gate electrode is formed A pixel electrode. In this regard, the gate electrode, the source and the drain electrode, and the pixel electrode can be formed by the above etching method. In other words, the Cu-containing metal film can be etched to form a gate of the data line constituting the TFT-LCD. Polar wiring and source/polar wiring. In particular, the source/drain wiring of a TFT-LCD may have resistance-related problems, and therefore, a Cu-containing metal film, particularly Cu/Mo_Ti, Ti, or M A multi-film can be used as a source/drain wiring and can be easily etched using the above etchant composition, thereby obtaining a large-sized TFT-LCD. One or more embodiments of the present invention will now refer to the following examples. The examples are for illustrative purposes only, and are not intended to limit the scope of the invention. Preparation Examples 1 to 6 include the components of the content shown in Table 1 below and the remaining amount of water. The composition was prepared. 12 201224210 <Table 1> Nitrogen peroxide (% by weight) Phosphoric acid (% by weight) Ammonium sulfate (% by weight) Aminotetrazole (% by weight) Fluoroboric acid (% by weight) Hydrofluoric acid (% by weight) Preparation Example 1 18 3.0 1.5 0.8 0.9 0 Preparation Example 2 18 3.0 0.5 0.8 0.7 0 Preparation Example 3 15 3.0 1.0 0.4 0.5 0 Preparation Example 4 10 3.0 0.5 0.2 0.3 0 Preparation Example 5 18 3.0 1.5 0.8 0 0.5 Preparation Example 6 25 5.0 3.0 1.0 1.5 0 Example 1 A Mo-Ti alloy film (50:50) and a Cu film were sequentially deposited on a glass substrate by chemical vapor deposition. The thickness of the Mo-Ti alloy film is about 300 to 400 and the thickness of the Cu film is about 2,000 to 2,500. Secondly, in order to form a Cu/Mo-Ti double layer on a desired region, a photoresist is applied on the Cu film and selectively exposed by using a mask, and the photoresist is used by using A developing solution is partially removed. Thereafter, the etching treatment of the Cu/Mo-Ti layer was carried out by spraying using the etchant composition prepared in accordance with Preparation Example 1. During the etching treatment, the temperature of the etchant composition was 33 ° C, and the etching time was about 70 seconds. End point detection (EPD, time when the metal was etched) was measured using the naked eye to obtain an etch rate over time. After the etching treatment is terminated, the rinsing treatment and the drying treatment are carried out. Finally, the photoresist is completely removed. 13 201224210 The contour of the Cu/M()_Ti layer of the paste was processed using a cross-section scanning cat electron microscope (Wei) (manufactured by Hltachi, model: s_42〇〇). Examples 2 to 4 Etching treatments were carried out in the same manner as in Example 1, except that the #刻刻 compositions prepared according to Preparation Examples 2 to 4 were used individually, and a silver engraving rate and a bilayer profile by cross-sectional SEM were obtained. Comparative Example 1-1 Insect treatment was carried out in the same manner as in the Example ,, except that the silver engraving composition prepared in accordance with Preparation Example 5 was used, and a silver engraving rate and a bilayer profile by cross-sectional SEM were obtained. Comparative Example 2 - Off the process with the example! This was carried out in the same manner, except that the residual agent composition prepared according to Preparation Example 6 was used, and the engraving rate and the bilayer profile by cross-sectional SEM were obtained. The evaluation of the etch rate, CD loss, taper angle, and tail length for each of the etching treatments of Examples 1 to 4 and Comparative Examples 丨 and 2 is shown in Table 2 below. At the same time, '1,000 ppm of Cu powder was added to prepare the remnant composition of m' and dissolved therein for 4 hours. One of the substrates having a size of 5 \5 was etched in the same manner as in Example 1 by using a composition containing a solvent (4), and the etching profile was analyzed by field emission (FE)_SEM. Thereafter, 1,000 ppm of Cu powder is further added to the etchant composition containing Cu dissolved therein, and this method is repeated until the total amount of added Cu powder is 14 201224210 6,000 to 8,000 ppm. Compared with the initial etching profile (reference) (where the powder is not included), the amount of Cu powder added as the contamination increase degree to the profile change is measured and used to separate the Cu film according to the substrate size. The thickness is considered to be the area and the cumulative processing amount of the etchant composition is counted back. In the calculation process of the cumulative treatment amount, the substrate size was not fixed, and therefore, the cumulative treatment amount of the etchant composition of the example 1 was counted back based on the analysis result based on the Cu powder accumulation degree. The results are shown in Table 2 below. This treatment was repeatedly carried out using the etchant compositions of Preparation Examples 2 to 6 to calculate the cumulative treatment amount for each of the etchant compositions used in the etching treatments of Examples 2 to 4 and Comparative Examples 1 and 2. <Table 2> Etching rate (/sec) CD loss (/zm) Cone angle Γ) Tail length (spleen) Cumulative treatment amount (ppm) Cu film Mo-Ti film example 90-100 30-35 0.515 45 0 6500 Example 2 85-90 20-25 0.458 55 0.348 6500 Example 3 70-75 18-22 0.304 40 0.241 6500 Example 4 60-65 10~14 0.121 50 0.660 6500 Comparative Example 1 45-50 55-60 0.212 55 0 2000 Comparison Example 2 130-140 50-55 1.086 65 0 3000 Figures 2 through 7 illustrate FE-SEM images of TFTs etched using the remnants of Examples 1 through 4 and Comparative Examples 2 and 2. Referring to Figures 2 through 5, it is confirmed that when 15 201224210 is used, an etchant composition according to an embodiment of the present invention is not damaged to the glass substrate, and a multilayer is collectively etched. Further, as shown in the second table above, when the etchant composition according to an embodiment of the present invention is used, the cumulative processing amount is increased. On the other hand, in the case of Comparative Examples 1 and 2, damage to the glass substrate was observed, the glass substrate was etched to cause a class difference as illustrated in Fig. 6, and the undercut defect of the film was as shown in Fig. 7. Confirmed as exemplified. Further, as shown in the second table above, the cumulative processing number confirmation is reduced. In other words, in the case of Comparative Example 1, in which hydrofluoric acid was used instead of fluoroboric acid, the attack on the glass substrate was as severe as illustrated in Fig. 6, and the cumulative treatment amount was as remarkable as shown in the second table above. cut back. Further, in the case of Comparative Example 2, in which the amount of fluoroboric acid was more than 1.0% by weight, when the etching rate was fast, the cumulative treatment amount was remarkably reduced. Further, when the rate of the engraving is more than 100 / sec, it is difficult to control the etching treatment, and the defect rate is increased by the data opening defect and the undercut defect of the film as illustrated in Fig. 7, thereby lowering the productivity. Therefore, as shown in the second table and the drawings, the composition of the surname according to an embodiment of the present invention contains a specific amount of fluoroboric acid, and therefore, when the surname treatment is carried out using the etchant composition, In the conventional etchant composition, the glass substrate system is not damaged, and the cumulative processing amount is large, which greatly contributes to an increase in productivity. As described above, according to one or more embodiments of the present invention, an etchant composition can collectively engrave a Cu-containing metal film without damaging a glass substrate, and therefore, the glass substrate can be reused, and Accumulation of etchant composition 16 201224210 The number of processes is increased, thereby increasing the productivity of the semiconductor device. Although the present invention has been particularly shown and described with reference to the embodiments of the present invention, it will be understood by those skilled in the art Go on. I: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing an etching method according to an embodiment of the present invention; FIG. 2 is a view of etching a thin film transistor (TFT) using an etching method according to Example 1. Electron microscopy (SEM) image; Fig. 3 is an SEM image of one TFT etched according to one of the etching methods of Example 2; FIG. 4 is an SEM image of one TFT etched according to one of the etching methods of Example 3; The SEM image of one of the TFTs is etched according to one of the etching methods of Example 4; the SEM image of one of the TFTs is etched according to one of the etching methods of Comparative Example 1; and the seventh image is used according to Comparative Example 2. An etching method etches an SEM image of one of the TFTs. [Description of main component symbols] 10.. Glass substrate 16... Photoresist 12.. Mo-Ti alloy film 14.. .CU film 17