TW201219601A - Composition for etching metal layer - Google Patents

Composition for etching metal layer Download PDF

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TW201219601A
TW201219601A TW100115598A TW100115598A TW201219601A TW 201219601 A TW201219601 A TW 201219601A TW 100115598 A TW100115598 A TW 100115598A TW 100115598 A TW100115598 A TW 100115598A TW 201219601 A TW201219601 A TW 201219601A
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Taiwan
Prior art keywords
acid
etching
composition
metal film
agent
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TW100115598A
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Chinese (zh)
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TWI503451B (en
Inventor
Wook Chang
Jong-Hee Park
Ji-Chan Kim
Jee-Hyun Hahn
Se-In Yang
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Oci Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66409—Unipolar field-effect transistors
    • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
    • H01L29/66742—Thin film unipolar transistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/45—Ohmic electrodes
    • H01L29/456—Ohmic electrodes on silicon
    • H01L29/458—Ohmic electrodes on silicon for thin film silicon, e.g. source or drain electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)

Abstract

Disclosed is a composition for etching a metal film, more particularly a composition for etching a metal film used as a gate electrode and a data electrode of a thin-film transistor for a flat panel display, particularly, a single-layer or multi-layer film including one or more selected from copper, molybdenum, titanium and molybdenum-titanium alloy by wet etching, which includes an oxidizing agent, an etching control agent, a chelating agent, an undercut-inhibiting agent, a copper etching inhibition agent, a residue removing agent, and water. The disclosed composition provides superior stability of the etchant, low taper angle of the etched metal film, adequately controlled critical dimension (CD) loss, and good etching profile with reduced residual molybdenum, titanium or molybdenum-titanium alloy. In addition, when an evaporation inhibiting agent is further added, improved productivity and reduced defect can be achieved due to decrease in mosses and deposition formed in the etching apparatus.

Description

201219601 * 六、發明說明： 【考务明戶斤屬椅々貝j 相關申請案之相互參照 本申請案在35 U.S.C. §119下，對2010年11月12日於韓 國智慧財產權部中所提出之韓國專利申請案案號 10-2010-0112948主張優先權，此揭示其全文以參考之方式 併入本文。 發明領域 本發明係關於一種用以蝕刻金屬膜之組成物，其中該 金屬膜使用作為用於平板顯示器的薄膜電晶體之開極電極 及資料電極，特別是，藉由以批次方式溼式蝕刻一包含一 或多種選自於銅、鉬、鈦及鉬-鈦合金的單層或多層膜。 ^tr ]| 發明背景 薄膜電晶體係藉由在基材上形成金屬線獲得。典型來 說，透過物理吸附形成金屬膜，接著使用光阻經由曝光及 蝕刻圖形化來製備一圖形化的薄膜。在此當中，該蝕刻製 程係-根齡曝光製辛呈中所形成的圖案來選擇性钱刻該金 屬膜之製程。 當需要具有較好的性能之薄膜電晶體液晶顯示器時， 對快速驅動來說，有需要具有低電阻的金屬膜。為了滿足 此需求，對該薄膜電晶體之金屬配線使用諸如銅及銀的金 屬材料。目前，工業應用上廣泛使用鋼。因為純銅難以被 沉積在基材上，通常首先沉積鉬、鈦或鉬_鈦合金，然後沉 201219601 =銅’ u形成—多層膜°當使用包含過氧化氫作為主要M 分的鋼_ 総式侧此多層膜時，時常由於在銅、翻 太臈中的不同蝕刻速率而獲得差的蝕刻曲線圖。例如， 在銅層下的鉬或鈦滯留會發生諸如在接下來的模組加工中 紐路之問題’從而降低生產力。 1 士 在尊丰國專利公告案號1〇-2006-0134380及韓國專 案號10-0839428中，將氫氟酸加入至钱刻劑以移除 歹堯冷曰 。但是，因為氫敗酸會姓刻玻璃基材，薄膜電晶 體的厚度均勻性會大大地受損。為了解決此問題，韓國專 案號10-2007-0097922以較不會触刻玻璃基材的氟化 物鹽置換氫氟酸。 田’堅式姓刻包含一或多種選自於銅、鉬、鈦及鉬_鈦合 金的單層或多層膜時，在㈣劑中製備多種添加劑以克服 下歹丨問題.在不同金屬層間之蝕刻速率降低、對整體基材 及圖案的钱刻均勻性、及在銅離子與過氧化氫間過度反應 性問題等等。 韓國專利公告案號10-2004-0051502使用有機酸（諸如 I乙酸)作為餘刻控制劑。但是，被蝕刻的薄膜顯示出陡峭 的錐角’且無法有效地降低在銅離子與過氧化氫間之反應 陡。韓國專利公告案號10-2006-0099089揭示出一種蝕刻 ^其包含硫酸鹽作為蝕刻控制劑、磷酸鹽作為凹蝕抑制 齊J及以ga酸為基底的螯合劑作為螯合劑 。雖然其在銅離子 與過氧化氫間提供優良的抑制反應效應 ，但其趨向於在排 出口及蝕刻設備的沖洗單位處發生沉積，因此降低生產力。 201219601 大部分用於銅、鉬、鈦或鉬-鈦合金膜的蝕刻劑已經發 展，用以改善鉬、鈦或鉬-鈦合金臈殘餘的問題、藉由控制 銅的钮刻速顿得好的綱曲線圖、料低在鋼離子與過 氧化氫間之反應。雖關於殘餘物㈣纽_已經達成 許多改良，但在蝕刻設備中沉積仍是問題。再者，需要保 證較好的穩定性以改善生產力。 ” 【韻'明内容_】 發明概要 本發明的發明家已經努力發展出用以姓刻金屬膜（其 使用作為用於平板顯示器的薄膜電⑽之金屬㈣ 刻劑組成物’特別是，包含-或多種選自於銅、銷、= ㈣太合金的單層或多層膜，其具有優異的㈣曲線圖 徵、保證均勻性 '降低在_子過氧化氫狀反應性 少鉬、鈦及鉬-鈦合金殘餘物、及減 / 穑m⑽γ ^在蝕刻攻備中形成沉 積及台。他們已經發展出-種包含氧化劑、钮刻控制 劑、螯合劑、凹㈣制劑、触刻抑制劑、殘餘物移㈣ ，水的組成物’且已證實該组成物可使用絲刻包含—或 夕種選自於H鈦及銷_鈦合金的單層或多層膜而沒有 特別處理。 在一個共通的觀點中，本發明提供一種用來蚀刻金屬 膜的組成物，其包含：7_30重量％的氧化劑；〇 ι 5食量％的 餘刻控制劑；（U.5重量％的螯合劑；MU重量⑽凹餘抑 制劑；0.G1-5重量％的鋼钱刻抑制劑；⑽15重^的殘餘 物移除劑；及適當的水量，至總重量⑽重量％。 201219601 以下將描述本發明之域及其它觀點及特徵。 圖式簡單說明 現在，將詳細描述本發明的上述及其它目標、特徵及 優點，伴隨著參照在伴隨的圖形中所_之其某些典型的 具體實例’其在下文中僅提供_用，因此非為本揭示之 限制，及其中： 第1圖顯示出當使用具有現存的組成物之_劑時，在 蝕刻設備的排出口處形成之沉積物； 第2圖顯示出當使用包含根據本發明的蒸發抑制劑之 ㈣劑時’該沉積問題明顯改善’如與當使用現存用於姓 刻之組成物時比較；及 第3圖係一電子顯微圖，其顯示出使用稂據本發明之蝕 刻劑組成物（實施例12)蝕刻的銅/鉬-鈦合金多層膜（銅層： 2000埃’合金層：3〇〇埃）之蝕刻曲線圖。 應瞭解所附加的圖形不需成比例，其呈現出闡明本揭 示的基本原理之多種較佳特徵的稍微簡化表示。本揭示如 於本文中所揭示的特定設計特徵（包括例如特定尺寸、定 向、位置及形狀）將部分由特別想要的應用及使用環境決 定。201219601 * VI. Description of the invention: [Certificate of the examination of the household, the chair of the house, and the reference of the application. This application is filed under 35 USC §119 and submitted to the Ministry of Intellectual Property of Korea on November 12, 2010. The Korean Patent Application No. 10-2010-0112948, the entire disclosure of which is incorporated herein by reference. FIELD OF THE INVENTION The present invention relates to a composition for etching a metal film using an open electrode and a data electrode as a thin film transistor for a flat panel display, in particular, by batch etching A single or multilayer film comprising one or more selected from the group consisting of copper, molybdenum, titanium, and molybdenum-titanium alloys. ^tr ]| BACKGROUND OF THE INVENTION Thin film electro-crystalline systems are obtained by forming metal lines on a substrate. Typically, a patterned metal film is formed by physical adsorption, followed by patterning by exposure and etching using photoresist. In this case, the etching process is a pattern formed by the aging process to selectively moly the metal film. When a thin film transistor liquid crystal display having better performance is required, there is a need for a metal film having low resistance for fast driving. In order to meet this demand, a metal material such as copper and silver is used for the metal wiring of the thin film transistor. Currently, steel is widely used in industrial applications. Since pure copper is difficult to deposit on the substrate, it is usually first deposited with molybdenum, titanium or molybdenum-titanium alloy, then sinked 201219601 = copper 'u formed - multilayer film ° when using steel containing hydrogen peroxide as the main M point _ 総 side In this multilayer film, a poor etching profile is often obtained due to different etching rates in copper and overturned. For example, molybdenum or titanium retention under the copper layer can cause problems such as in the next module processing, thereby reducing productivity. In the Zun Fengguo Patent Publication No. 1〇-2006-0134380 and Korean Patent No. 10-0839428, hydrofluoric acid is added to the money engraving agent to remove the ruthenium. However, since the hydrogen septic acid will be a glass substrate, the thickness uniformity of the thin film transistor will be greatly impaired. In order to solve this problem, Korean Patent No. 10-2007-0097922 replaces hydrofluoric acid with a fluoride salt which does not touch the glass substrate. When Tian's name contains one or more single or multi-layer films selected from copper, molybdenum, titanium and molybdenum-titanium alloys, various additives are prepared in the (iv) agent to overcome the problem of squatting. Between different metal layers Reduced etch rate, uniformity of the overall substrate and pattern, and excessive reactivity between copper ions and hydrogen peroxide. Korean Patent Publication No. 10-2004-0051502 uses an organic acid such as I acetic acid as a residual control agent. However, the etched film exhibits a steep taper angle and does not effectively reduce the steep reaction between copper ions and hydrogen peroxide. Korean Patent Publication No. 10-2006-0099089 discloses an etching which comprises a sulfate as an etching control agent, a phosphate as a etch inhibiting agent, and a chelating agent based on gaic acid as a chelating agent. Although it provides an excellent suppression reaction effect between copper ions and hydrogen peroxide, it tends to deposit at the discharge unit of the discharge port and the etching apparatus, thereby reducing productivity. 201219601 Most of the etchants for copper, molybdenum, titanium or molybdenum-titanium alloy films have been developed to improve the residual problems of molybdenum, titanium or molybdenum-titanium alloys, and to control the copper by the button speed. The graph is low in the reaction between steel ions and hydrogen peroxide. Although many improvements have been made with respect to the residue (four) New Zealand, deposition in etching equipment is still a problem. Furthermore, better stability is needed to improve productivity. SUMMARY OF THE INVENTION The inventors of the present invention have endeavored to develop a metal film for the surname of a metal film (which is used as a thin film electric (10) for flat panel displays', in particular, including - Or a plurality of single-layer or multi-layer films selected from the group consisting of copper, pin, and (4) titanium alloys, which have excellent (four) curve signs, ensure uniformity, and reduce the reactivity of molybdenum, titanium and molybdenum in the form of hydrogen peroxide. Titanium alloy residues, and /m(10)γ^ form deposits and stages in etch attack. They have developed oxidants, button control agents, chelating agents, concave (four) preparations, etch inhibitors, residue shifts (4) , a composition of water 'and it has been confirmed that the composition may be used in a single layer or a multilayer film selected from the group consisting of H titanium and pin-titanium alloy without special treatment. In a common point of view, The invention provides a composition for etching a metal film, comprising: 7-30% by weight of an oxidizing agent; a residual controlling agent of 〇ι 5% by weight; (U. 5 wt% of a chelating agent; MU weight (10) a residual inhibitor; 0.G1-5% by weight of steel money engraved Formulation; (10) 15% residue remover; and appropriate amount of water, to total weight (10)% by weight. 201219601 The domain of the present invention and other points and features will be described below. Brief Description of the Drawings Now, the present invention will be described in detail. The above and other objects, features and advantages are accompanied by reference to certain typical embodiments of the accompanying drawings which are merely provided hereinafter, and thus are not limiting of the disclosure, and wherein: FIG. Shows the deposit formed at the discharge port of the etching apparatus when the agent having the existing composition is used; FIG. 2 shows that when the (four) agent containing the evaporation inhibitor according to the present invention is used, the deposition problem is conspicuous Improvements as compared to when using existing compositions for surnames; and Figure 3 is an electron micrograph showing copper etched using an etchant composition (Example 12) according to the present invention. An etching curve of a molybdenum-titanium alloy multilayer film (copper layer: 2000 angstroms alloy layer: 3 angstroms). It should be understood that the attached figures are not necessarily to scale and represent the basic principles of the present disclosure. Species preferred feature somewhat simplified showing. The specific design features of the present disclosure as disclosed herein (including, for example, specific dimensions, fixed to, location and shape) of the desired part by the particular application and use environment decision.

【實施方式;J 較佳實施例之詳細說明 現在，將於此之後詳細地參照本發明的多個具體實 例，此等實施例在伴隨的圖形中闡明且描述在下列。雖然 本揭示將以相關的典型具體實例描述，將要了解本描述不 201219601 相==限於那些典型具體實例。相反 二ΓΓΓ型的具體實例，而且亦涵蓋多種代用品、 =由相4物及其它具體實例，其可包括在本揭示如由 的申請專· _定義之精神及範圍内。 本發歧供-種以_金屬膜的㈣物，其包含 =:刻控制劑、f合劑、凹_卜 殘餘物移除劑及水。 h X氧化Μ氧化-鋼薄膜表面。特別是，可使用過氧化 氧其^亥組成物中可包含的量係7-30重量％。當該含量低 於7重里％時’製程效率會降低，因為銅㈣速率降低。及 當其超過30重量％日年，Α f因為與銅離子差的穩定性，所加工 的破璃數會受限制。 »亥姓刻控制劑會離子化銅膜之經氧化的表面，以便將 鋼離子從薄膜表面分離出。特別是，可使用有機酸。該有 機酸的特定實施例可包括一或多種具有一或多_基的 酸，諸如醋酸、檸檬酸、草酸、馬來酸、紅酸、破賴、 酒石g文、反丁烯二酸、水揚酸、蘋果酸、三甲基乙酸等等。 特別是，該蝕刻控制劑在該組成物中可包含的量係〇15重 量％。當該蝕刻控制劑之含量低於〇1重量％時，蝕刻速率 可減低。及當其超過5重量％時，蝕刻曲線圖_臨界尺寸(CD) 損失及錐角可令人不滿意。 該螯合劑會螯合已溶解在蝕刻劑中的銅離子，因此防 止鋼離子與氧化劑反應及改善氧化劑與钮刻劑之穩定性。 其增加由蝕刻劑加工的玻璃數及藉由防止過氧化氫快速分 201219601 解而改善安全性。典型來說，可使用以醋酸為基底的螯合 劑、以膦酸為基底的螯合劑、胺基酸或其混合物。更特別 的是，該以醋酸為基底的螯合劑之實施例可包括氮基三醋 酸(NTA)、亞胺二醋酸(IDA)、曱基亞胺二醋酸(MIDA)、羥 乙基亞胺二醋酸(HIDA)、二伸乙基三胺五醋酸(DPTA)、乙 二胺四醋酸(EDTA)、N-羥乙基乙二胺四醋酸(HEDTA)、甲 基乙二胺四醋酸(MEDTA)、三伸乙基四胺六醋酸(TTHA)等 等；該以膦酸為基底的螯合劑之實施例可包括乙二胺四亞 曱基膦酸（EDTPA)、二伸乙基三胺五亞曱基膦酸 (DTPMPA)、羥基亞乙基二膦酸(HEDP)、胺基三亞甲基膦 酸(ATMP)等等；及該胺基酸的實施例可包括甘胺酸、精胺 酸、麵胺酸、丙胺酸、半胱胺酸、麵醯胺酸、草甘膦、甘 胺醯酸(glycylic acid)等等。特別是，該螯合劑在該用以触 刻金屬膜之組成物中可包含的量係0.1-5重量％。當該整合 劑之含量低於〇·1重量％時，穩定性可減低，因為在氧化劑 與銅離子間過度反應。及當其超過5重量％，蝕刻曲線圖_CD 損失及錐角可令人不滿意。 該凹触抑制劑調整金屬的氧化還原位能，因此防止局 部電池反應及保證在包含銅、銦、鈦等等的多層膜之金屬 層中一致的触刻速率。在本發明中’可使用無機磷酸鹽及 有機酸的銨鹽作為該凹蝕抑制劑。在現存的蝕刻劑中，普 遍地使用無機磷酸鹽，但是它們藉由與其它以有機為基礎 的添加劑結合趨向於在蝕刻設備中造成苔蘚物形成。在本 發明中，可藉由一起使用有機酸的銨鹽與無機磷酸鹽明顯 201219601 減少苔蘚物形成。該無機磷酸鹽可為一或多種選自於磷酸 錢、碟酸氫銨、伽二氫銨、_納、雜氫鈉及磷酸二 風鈉者；及該有機酸的錢鹽可為—或多種選自於醋酸銨、 、呈齒化的醋酸及檸檬酸録者。特別是，無機填酸鹽對有 機k的叙鹽之重1㈣可為t : Q 25々。若該有機酸的敍鹽 =重里比例太小時’會在_設備中形成苔蘚物^比較上， 太大時’钱刻曲線圖可由於❿損失減少而不令人滿 。4凹财卩制劑在該組成物中的含量可為⑽卜3重量％。 若該凹触抑制劑的含量太少時，會在！目、鈦或減層中發 凹姓比較上’若其超過3重量％時，難以獲得想要的姓 刻曲線圖。 °划抑制劑來控制銅的蝕刻速率（其比鉬及鈦 、、便獲％•優異的似彳曲線圖。典型來說，可使用雜環 胺特別疋’可使用胺基四唾、畔唑、。引哚、。票呤、吼嗤、 p H叫、料咬、鱗。定、笨并三嗤或其混合 %。。該銅ϋ抑制劑在該組成物中可包含的量係讀-5重量 备3里太夕時，該在多層膜中的勉刻曲線圖可令人 時，U因為銅_速率增加4較上，若其超過5重量％ 力會因為ϋ刻速率降低而降低。 用無物移除劑移_、鈦及__鈦合金殘餘物。可使 多種選= 物餘物移除劑。特別是，可使用-或 銨、二氟化鈉Τ氟::r氟化〜^ 刻金屬膜之組成物Φ者、亥殘餘物移除劑在該用以蝕 、之、，且成物中可包含的量係__5重量％。若其含量 201219601 低於〇·〇!重量%時 超過5重量％時，舍—’殘餘物可餘留。比較上，若其 若需要的話，根方的層及玻璃基材。 可進-步包含—笑 明之用以蝕刻金屬Μ的組物 瘵發抑制劑。β外， 發，因此维持居4 5亥凑發抑制劑抑制蝕刻劑蒸 積。藉由加入蒸的沉積物之溶解度，因此減少沉 可明顯減少。”：:劑，接近蝕刻設備的排出口之沉積 元醇。例如；制劑可為具有二或更多個經基的多 物。該蒸發抑制劑可加入的量係重^二料其混合 於0.1重量％時，I 重里％。右加入量低 “入旦 …、法足夠地抑制蝕刻劑蒸發 17里超過7重量％，其效應 範圍最好。 員因此，維持上述 旦刚除重了^前描述的構成物外，可加人適當量的水(至她重 里100重里％)以獲得用以儀刻本發明之金屬膜的U物 當使用來_包含-或多種選自 ，，成物。 入令的m 7多種選自於銅、鉬、欽及翻-欽 &金的早層或多層時，本發明之触刻劑組成物可提供優異 的蝕刻曲線圖及藉由減少苔蘚物形成及沉積來改善生產 力。再者，其可保證較低的錐角，如與習知的_ 實施例 現在將描述實施例及實驗。下列實施例及實驗係僅用 於闡明的目的且不想要限制本揭示之範圍。 實施例1-18及比較例1-2DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S) DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments embodiments Although the present disclosure will be described in relation to typical exemplary embodiments, it will be understood that this description is not intended to be limited to the specific embodiments. The specific examples of the opposite type, and also encompasses a variety of substitutes, = phase 4, and other specific examples, which may be included in the spirit and scope of the application. The invention relates to a (four) material of a metal film comprising: a control agent, an f mixture, a concave residue removal agent, and water. h X yttria oxidation - steel film surface. In particular, it is possible to use oxygen peroxide in an amount of 7 to 30% by weight which may be contained in the composition. When the content is less than 7% by weight, the process efficiency is lowered because the copper (tetra) rate is lowered. And when it exceeds 30% by weight of the day, Α f is limited by the stability of the copper ion. »Hai's name control agent ionizes the oxidized surface of the copper film to separate the steel ions from the surface of the film. In particular, organic acids can be used. Particular embodiments of the organic acid may include one or more acids having one or more groups, such as acetic acid, citric acid, oxalic acid, maleic acid, erythric acid, ruthenium, tartar, fumaric acid, Salicylic acid, malic acid, trimethyl acetic acid, and the like. In particular, the etch control agent may be included in the composition in an amount of 15% by weight. When the content of the etching control agent is less than 〇1% by weight, the etching rate can be lowered. And when it exceeds 5% by weight, the etching profile_critical dimension (CD) loss and taper angle can be unsatisfactory. The chelating agent sequesters copper ions that have been dissolved in the etchant, thereby preventing the reaction of the steel ions with the oxidizing agent and improving the stability of the oxidizing agent and the marking agent. It increases the number of glass processed by the etchant and improves safety by preventing the rapid resolution of hydrogen peroxide by 201219601. Typically, an acetic acid based chelating agent, a phosphonic acid based chelating agent, an amino acid or a mixture thereof can be used. More particularly, examples of the acetic acid-based chelating agent may include nitrogen triacetate (NTA), imine diacetic acid (IDA), mercaptoimide diacetic acid (MIDA), hydroxyethyl imine II. Acetic acid (HIDA), di-ethyltriamine pentaacetic acid (DPTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetetraacetic acid (HEDTA), methylethylenediaminetetraacetic acid (MEDTA) , tri-ethyltetramine hexaacetic acid (TTHA), etc.; examples of the phosphonic acid-based chelating agent may include ethylenediamine tetradecylphosphonic acid (EDTPA), di-extended ethyltriamine pentia Mercaptophosphonic acid (DTPMPA), hydroxyethylidene diphosphonic acid (HEDP), aminotrimethylenephosphonic acid (ATMP), and the like; and examples of the amino acid may include glycine, arginine, Amylin, alanine, cysteine, acetophene, glyphosate, glycyllic acid, and the like. In particular, the chelating agent may be included in an amount of from 0.1 to 5% by weight in the composition for etching the metal film. When the content of the integrator is less than 〇·1% by weight, the stability can be lowered because of excessive reaction between the oxidizing agent and the copper ion. And when it exceeds 5% by weight, the etching profile _CD loss and taper angle can be unsatisfactory. The concave touch inhibitor modulates the redox potential of the metal, thereby preventing local cell reactions and ensuring a consistent etch rate in the metal layer of the multilayer film comprising copper, indium, titanium, and the like. In the present invention, an inorganic phosphate and an ammonium salt of an organic acid can be used as the etch inhibitor. In existing etchants, inorganic phosphates are commonly used, but they tend to cause moss formation in etching equipment by combining with other organic based additives. In the present invention, the formation of moss can be reduced by using an ammonium salt of an organic acid together with an inorganic phosphate. The inorganic phosphate may be one or more selected from the group consisting of phosphoric acid, ammonium hydrogen hydride, ammonium dihydrogen ammonium, sodium hydride, sodium hydrogen hydride, and sodium dinitrogen phosphate; and the acid salt of the organic acid may be - or a plurality of It is selected from ammonium acetate, chiral acetic acid and citric acid. In particular, the weight of the inorganic acid salt to the salt of the organic k may be t: Q 25 々. If the salt of the organic acid = the proportion of the weight is too small, 'will form a moss in the equipment. ^ When it is too large, the 'money curve' may not be full due to the reduction of the enthalpy loss. The content of the 4 concave sputum preparation in the composition may be (10) 3% by weight. If the content of the concave touch inhibitor is too small, it will be! In the case of titanium, or in the reduced layer, it is difficult to obtain the desired surname curve if it exceeds 3% by weight. °Inhibitors are used to control the etching rate of copper (which is better than molybdenum and titanium, and the % is excellent). Typically, heterocyclic amines can be used, and amines can be used. , 哚 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , When the weight is 5 GHz, the etched graph in the multilayer film can be tempered, because the copper _ rate is increased by 4, and if it exceeds 5% by weight, the force is lowered because the etch rate is lowered. Use the removal agent to remove _, titanium and __ titanium alloy residue. A variety of options can be used to remove the residue. In particular, you can use - or ammonium, sodium difluoride Τ fluoride:: r fluorination ~^ The composition of the metal film Φ, the sea residue remover can be included in the amount of etched, and, and the amount of __5 wt%. If its content 201219601 is lower than 〇·〇! When the weight % exceeds 5% by weight, the residue may remain. In comparison, if necessary, the root layer and the glass substrate can be further included. The metal ruthenium group oxidizes the inhibitor of the ruthenium. Therefore, it maintains the immersion inhibitor to inhibit the evaporation of the etchant. By adding the solubility of the vaporized deposit, the reduction in sinking can be significantly reduced." The agent is a depositional alcohol close to the discharge port of the etching apparatus. For example, the preparation may be a plurality of substances having two or more warp groups. The evaporation inhibitor may be added in an amount of two weights mixed with 0.1 weight. %, I re-%. The right addition amount is low "Into the denier..., the method is sufficient to suppress the evaporation of the etchant by more than 7 wt% in 17, and the effect range is the best. Therefore, the above-mentioned description has been maintained. In addition to the constituents, an appropriate amount of water (to 100% by weight of her weight) may be added to obtain a U-material for etching the metal film of the present invention when used - including - or a plurality of selected from, and a product. When more than 7 kinds of early layers or layers selected from the group consisting of copper, molybdenum, chin and turn-champion & gold, the etchant composition of the present invention can provide an excellent etching profile and reduce moss formation and deposition. Improve productivity. Furthermore, it guarantees a low cone angle, such as Conventional Examples and Experiments The following examples and experiments are intended to be illustrative only and are not intended to limit the scope of the disclosure. Examples 1-18 and Comparative Examples 1-2

製備一用於I虫刻的組成物，其包含氧化劑、_控制 劑、螯合劑、凹#抑制劑、銅钮刻抑制劑、殘餘物移心齊I 201219601 及水。關於構成物及組成物的細節提供在表1中。 表1 構成物 組成物 ~~~ I 實施例1 過氧化氫/IDA/馬來酸/ 磷酸銨及檸檬酸銨/胺 基四唑/二氟化銨/水 15.0/1.6/1.5/1.0/0,40/0.05/剩 〜 實施例2 19.0/2.0/1.0/1.0/0.70/0.05/剩^^^ 實施例3 23 ·0/1.6/1.5/1.0/0.40/0.05/剩^^^' 實施例4 23.0/1.6/0.5/1.0/0.40/0.05/剩 ^' 實施例5 Π .5/2.0/2.0/1 ·0/0· 15/0.05/剩 ^ 實施例6 17.0/2.0/0.8/0.1/0.35/0.05/剩^5' 比較例1 — 過氧化氫/IDA/硫酸鉀/ 磷酸銨/胺基四唑/二氟 化鉀/水 · 21.5/3.0/1 _0/1·0/0_80/0·05/剩餘者 比較例2 過氧化氫/IDA/羥乙酸/ 碟酸納/胺基四《坐/二氟 化銨/水 23.0/1.3/1.0/1.0/0.80/0.05/剩餘者 _^施例7 過氧化氫/IDA/馬來酸/ 磷酸銨及檸檬酸銨/胺 基四唑/二氟化銨/乙二 醇/水 19.0/2.1/2.8/0.23/0.3/0.05/5.0/^^- 實施例8 11.5/2.0/2.0/0.23/0.3/0.05/5.0/¾¾^ 例 9 14.5/2.0/2.1/0.23/0.3/0.05/5.0¾^^ 實施例10 17.5/2.1/2.0/0.23/0.3/0.05/5.0/¾¾^ 例 11 ^例 12 實施例13 實施例14 "" — 實施例15 19.0/2.9/1.5/0.23/0.3/0.05/5.0/¾¾^ 19.0/1.5/2.9/0.23/0.3/0.05/5. 19.0/2.3/1.9/0.23/0.3/0.05/5. 19.0/2.3/2.1/0.23/0.3/0.05/5. 19.0/2.0/2.5/0.23/0.3/0.05/5. 實施例16 例 17 19.0/2.0/2.3/0.23/0.3/0.05/5. 19.0/2.1/2.4/0.23/0.3/0.05/5.0/¾^^- 實施例18 19_0/2_1/2_8/0.23/0_3/0_〇5/5.〇/ϋ^^~ 例7-18 :進一步加入蒸發抑制劑。 (檸以重量比率丨：丨.3混合無機鱗酸鹽（鱗酸敍）與有機酸的銨鹽 链刻性能的評估 為了測試根據本發明之蝕刻劑組成物的性能，製備— 鋼/銷-鈦合金雙層基材。該鉬-鈦合金具有1 : 1重量比率。 鋼及銷-鈦合金係藉由濺鍍沉積在基材上，如在LCI)破璃基 材製造方法中般。以二種不同厚度來沉積銅層及鉬-鈦合金 11 201219601 層。該厚度各別為銅2000埃/鉬-鈦300埃，及銅2500埃/鉬_ 鈦100埃。 在喷灑型溼式蝕刻設備(蝕刻器（Etcher)(TFT)，KC科技 (KC Tech))中加熱實施例1-18及比較例1-2的每種蝕刻劑， 及蚀刻該雙層基材伴隨著將溫度維持在33±〇5»c。過度蝕 刻（Ο/E)該基材，每層皆超過終點偵測(EpD)6〇%。在蝕刻完 成後’以超純水沖洗基材及使用乾燥器乾燥。在使用光阻 剝除劑移除光阻後，使用掃描式電子顯微鏡（SEM ; NOVA-200,飛利浦（Phimps))評估錐角、臨界尺寸（CD)損 失、触刻殘餘物等等。再者，為了研究蝕刻劑的穩定性， 當銅離子濃度增加時，測量蝕刻劑仍然穩定的最大銅離子 濃度。 表2 錐角 (。） CD損失 (微米） MoTi 突 出（微米） Ο/E比 率(％) 殘 沉積 敢大鋼 離子濃 度(ppm) 評估 實施例1 65.7 1.1 0.14 60 無 發生 11,980 好 實施例2 64.5 1.0 0.13 60 無 發生 11,500 好 實施例3 66.7 1.7 0.11 60 無 發生 10,600 好 實施例4 69.2 1.5 0.13 60 無 發生 9,825 好 實施例5 60.2 1.4 0.13 60 無 發生 15,360 好 實施例6 62.3 1.4 0.13 60 無 發生 11,950 好 比較例1 65.2 1.4 0.15 60 無 發生 4,000^1 尚可 比較例2 64.0 1.4 0.11 60 無 發生 4,0〇〇 尚可 表2比較根據本發明之用以蝕刻的組成物（其包含氧化 劑、蝕刻控制劑、螯合劑、凹蝕抑制劑、銅蝕刻抑制劑、A composition for insect imaging comprising an oxidizing agent, a controlling agent, a chelating agent, a concave #inhibitor, a copper buttoning inhibitor, a residue shifting heart I 201219601 and water was prepared. Details regarding the constituents and compositions are provided in Table 1. Table 1 Composition of composition ~~~ I Example 1 Hydrogen peroxide/IDA/maleic acid/ammonium phosphate and ammonium citrate/aminotetrazole/ammonium difluoride/water 15.0/1.6/1.5/1.0/0 40/0.05/remaining~ Example 2 19.0/2.0/1.0/1.0/0.70/0.05/remaining ^^^ Example 3 23 ·0/1.6/1.5/1.0/0.40/0.05/remaining ^^^' Example 4 23.0/1.6/0.5/1.0/0.40/0.05/remaining^' Example 5 Π .5/2.0/2.0/1 ·0/0· 15/0.05/remaining^ Example 6 17.0/2.0/0.8/0.1/ 0.35/0.05/remaining^5' Comparative Example 1 - Hydrogen peroxide / IDA / Potassium sulphate / Ammonium phosphate / Aminotetrazole / Potassium difluoride / water · 21.5/3.0/1 _0/1·0/0_80/0 ·05/Remaining Comparative Example 2 Hydrogen Peroxide/IDA/Glycolic Acid/Sodium Oleate/Amine IV “Sit/Ammonium Difluoride/Water 23.0/1.3/1.0/1.0/0.80/0.05/Remaining _^ Example 7 Hydrogen peroxide / IDA / maleic acid / ammonium phosphate and ammonium citrate / aminotetrazole / ammonium difluoride / ethylene glycol / water 19.0 / 2.1 / 2.8 / 0.23 / 0.3 / 0.05 / 5.0 / ^ ^ - Example 8 11.5/2.0/2.0/0.23/0.3/0.05/5.0/3⁄43⁄4^ Example 9 14.5/2.0/2.1/0.23/0.3/0.05/5.03⁄4^^ Example 10 17.5/2.1/2.0/0.23/0.3 /0.05/5.0/3⁄43⁄4^ Example 11 ^Example 12 Example 13 Example 14 "" - Example 15 1 9.0/2.9/1.5/0.23/0.3/0.05/5.0/3⁄43⁄4^ 19.0/1.5/2.9/0.23/0.3/0.05/5. 19.0/2.3/1.9/0.23/0.3/0.05/5. 19.0/2.3/2.1/ 0.23/0.3/0.05/5. 19.0/2.0/2.5/0.23/0.3/0.05/5. Example 16 Example 17 19.0/2.0/2.3/0.23/0.3/0.05/5. 19.0/2.1/2.4/0.23/0.3 /0.05/5.0/3⁄4^^- Example 18 19_0/2_1/2_8/0.23/0_3/0_〇5/5.〇/ϋ^^~ Example 7-18: Further addition of an evaporation inhibitor. (Lime is a weight ratio 丨: 丨.3 mixed inorganic sulphate (squamous acid) and ammonium salt chaining performance evaluation of organic acid In order to test the performance of the etchant composition according to the present invention, preparation - steel / pin - Titanium alloy double-layer substrate. The molybdenum-titanium alloy has a weight ratio of 1:1. Steel and pin-titanium alloy are deposited on the substrate by sputtering, as in the LCI) glass substrate manufacturing method. The copper layer and the molybdenum-titanium alloy 11 201219601 layer are deposited in two different thicknesses. The thickness is each 2000 angstroms/molybdenum-titanium 300 angstroms, and copper 2500 angstroms/molybdenum _ titanium 100 angstroms. Each of the etchants of Examples 1-18 and Comparative Examples 1-2 was heated in a spray type wet etching apparatus (Etcher (TFT), KC Tech), and the double layer was etched The material is accompanied by maintaining the temperature at 33 ± 〇 5»c. Excessive etching (Ο/E) of the substrate, each layer exceeding the endpoint detection (EpD) 6〇%. After the etching is completed, the substrate is rinsed with ultrapure water and dried using a dryer. After the photoresist was removed using a photoresist stripper, a scanning electron microscope (SEM; NOVA-200, Phimps) was used to evaluate cone angle, critical dimension (CD) loss, etch residue, and the like. Further, in order to study the stability of the etchant, when the concentration of copper ions was increased, the maximum copper ion concentration at which the etchant was still stable was measured. Table 2 Cone angle (.) CD loss (micron) MoTi protrusion (micron) Ο/E ratio (%) Residual deposition dad steel ion concentration (ppm) Evaluation Example 1 65.7 1.1 0.14 60 No occurrence 11,980 Good example 2 64.5 1.0 0.13 60 No occurrence 11,500 Good example 3 66.7 1.7 0.11 60 No occurrence 10,600 Good example 4 69.2 1.5 0.13 60 No occurrence 9,825 Good example 5 60.2 1.4 0.13 60 No occurrence 15,360 Good example 6 62.3 1.4 0.13 60 No occurrence 11,950 Good Comparative Example 1 65.2 1.4 0.15 60 No occurrence 4,000^1 Comparative Example 2 64.0 1.4 0.11 60 No occurrence 4,0 〇〇 Table 2 Comparison of the composition for etching according to the present invention (which contains an oxidizing agent, etching Control agent, chelating agent, corrosion inhibitor, copper etching inhibitor,

S 12 201219601 殘餘物移除劑及水)與現存用於⑽之組㈣其對銅，翻_ 、太。金(厚度2000埃/300埃）雙層基材之蝕刻性能。鑑於現存 用以飯刻的組成物具有最大銅離子濃度約4，_卯爪，本發 明之組成物具有最大銅離子濃度超過6,000 ppm且在蝕刻 °又備中無觀察到苔蘚物或沉積。也就是說，本發明之組成 物顯不出改善的穩定性，如與現存的餘刻劑比較。及當與 現存的钮刻雜較時，其顯示出可比較的cd損失、雜角及 殘餘物。 表3 錐角 (。） CD損失 (微米） MoTi 突 出（微米） Ο/E比 率(％) 殘 餘 物 沉 積 最大銅 離子濃 (ppm) 評估 實施例7 實施例8 實施例9 50.6 1.59 0.09 60 無 無 8,530 優異 52.0 ^5.0 1.06 0.06 60 無 無 9,890 優異 1.24 0.07 60 無 無 10,260 優異 實施例10 57.2 1.20 — 0.07 60 無 無 9,240 優異 實施例11 52.9 1.15 0.23 60 無 無 13,000 優異 實施例12 47.6 1.40 0.15 60 無 無 9,825 優異 表3顯示出根據本發明之蚀刻劑組成物的姓刻性能，其 ' ' 用於鋼/銷-鈦合金(2000埃/300埃在厚度)雙層 基材之蒸發抑_。其具有最大銅離子濃度超過6，_ ppm 且在似j叹備中無觀察到苔蘚物或沉積。當與顯示在表2中 的比較例1-2之結果比較時，因為錐角低至少5。，可更容易 地進行接下來的薄膜沉積及圖形化方法。 13 201219601 表4S 12 201219601 Residue remover and water) and existing (10) group (4) for copper, turn _, too. Etching performance of gold (thickness 2000 angstroms / 300 angstroms) double layer substrate. In view of the fact that the composition for cooking has a maximum copper ion concentration of about 4, _ paw, the composition of the present invention has a maximum copper ion concentration of more than 6,000 ppm and no moss or deposit is observed in the etching. That is, the compositions of the present invention show no improved stability, as compared to existing remnants. And when compared to existing button ingots, it shows comparable cd loss, horns and residue. Table 3 Cone angle (.) CD loss (micron) MoTi protrusion (micron) Ο/E ratio (%) Residue deposition maximum copper ion concentration (ppm) Evaluation Example 7 Example 8 Example 9 50.6 1.59 0.09 60 No 8,530 Excellent 52.0 ^5.0 1.06 0.06 60 No 9,890 Excellent 1.24 0.07 60 No 10,260 Excellent Example 10 57.2 1.20 — 0.07 60 No 9,240 Excellent Example 11 52.9 1.15 0.23 60 No 13,000 Excellent Example 12 47.6 1.40 0.15 60 None No 9,825 Excellent Table 3 shows the surrogate performance of the etchant composition according to the present invention, which is used for the evaporation of a double layer substrate of steel/pin-titanium alloy (2000 angstroms/300 angstroms in thickness). It has a maximum copper ion concentration of more than 6, _ ppm and no moss or deposit is observed in the sigh. When compared with the results of Comparative Example 1-2 shown in Table 2, the cone angle was at least 5 because it was low. The next film deposition and patterning method can be performed more easily. 13 201219601 Table 4

Cu/MoTi 層 厚度（埃） 錐角 η CD損失 (微米） MoTi 突 出（微米） 蝕刻時 間（秒） 殘 餘 評估 實施例13 2000/300 46.2 1.45 0.22 75 無 尚可 實施例14 48.2 1.40 0.30 75 無 尚可 實施例15 51.6 1.61 0.18 75 無 優良 實施例16 50.3 1.72 0.20 75 無 優良 實施例17 51.7 1.44 0.25 75 無 尚可 實施例18 54.1 1.60 0.16 75 無 優良 實施例13 2500/100 51.1 1.32 0.08 60 無 優良 實施例14 48.2 1.41 0.08 60 無 優良 實施例15 47.5 1.27 0.08 60 無 優良 實施例16 51.2 1.36 0.08 60 無 優良 實施例17 48.4 1.35 0.08 60 無 優良 實施例18 50.6 1.59 0.09 60 無 優良 表4顯示出蝕刻性能與銅/鉬-鈦合金雙層膜的合金層厚 度相依。通常來說，銅層及於此之下的合金層之厚度變化 造成蝕刻控制劑的性能降低，由於在多層膜中的不同電子 傳遞速率，因此在合金層中發生殘餘物問題。但是，根據 本發明用於蝕刻的組成物具有好的蝕刻曲線圖且在合金層 中無殘餘物或突出。此外，其對製程堅固性將為大的優點， 因為其具有好的蝕刻曲線圖，甚至當層厚度改變時。 當使用來触刻包含一或多種選自於銅、銦、欽及錮-欽 合金的不同單層或多層膜基材（其使用作為用於平板顯示 器的薄膜電晶體之閘極及資料電極）時，用以蝕刻本發明之 金屬膜的組成物可提供優異的蝕刻曲線圖及特徵，及保證 均勻性。再者，若進一步包含蒸發抑制劑時，可改善生產 力，因為在蝕刻設備中的苔蘚物及沉積形成減少。隨著比Cu/MoTi layer thickness (Angstrom) Cone angle η CD loss (μm) MoTi protrusion (μm) Etching time (seconds) Residual evaluation Example 13 2000/300 46.2 1.45 0.22 75 No feasibility Example 14 48.2 1.40 0.30 75 No Example 15 51.6 1.61 0.18 75 No good example 16 50.3 1.72 0.20 75 No good example 17 51.7 1.44 0.25 75 No feasibility Example 18 54.1 1.60 0.16 75 No good example 13 2500/100 51.1 1.32 0.08 60 No good Example 14 48.2 1.41 0.08 60 No good example 15 47.5 1.27 0.08 60 No excellent example 16 51.2 1.36 0.08 60 No good example 17 48.4 1.35 0.08 60 No good example 18 50.6 1.59 0.09 60 No good Table 4 shows etching The performance is dependent on the thickness of the alloy layer of the copper/molybdenum-titanium alloy double layer film. In general, variations in the thickness of the copper layer and the underlying alloy layer result in a decrease in the performance of the etch control agent, which causes residue problems in the alloy layer due to the different electron transfer rates in the multilayer film. However, the composition for etching according to the present invention has a good etching profile and no residue or protrusion in the alloy layer. In addition, it will be a great advantage for process robustness because it has a good etch profile even when the layer thickness is changed. When used to etch one or more different single or multilayer film substrates selected from copper, indium, bismuth and bismuth alloys, which are used as gate and data electrodes for thin film transistors for flat panel displays The composition for etching the metal film of the present invention can provide excellent etching patterns and features, and ensure uniformity. Further, if the evaporation inhibitor is further contained, the productivity can be improved because the formation of moss and deposition in the etching apparatus is reduced. With ratio

S 14 201219601 銅離子濃度，本發明之組成㈣ 多金屬膜糾錢成本，因為可與之處理更 計缺陷比率在接下來的==的：低之錐角’預 銅Hu 少。此外，因為在包含 ,A 鉬'鈦合金的多層膜中之較低層的突出受控 積方好的飾刻曲線圖。除此之外，甚至當在薄膜沉 /的層厚度改變時，亦可獲得好義刻曲線圖。 β本發明已經伴隨著參《特定具體鈔m細地描述。 仁疋將由热f該項技術者察知可在這些具體實例t製;p 多種改變及改質而沒有離開本揭示的原理及精神，其範= 在所附加的申請專利範圍及其相等物中定義。 【圖式簡單說明】 第1圖顯示出當使用具有現存的組成物之關劑時，在 蝕刻設備的排出口處形成之沉積物； 第2圖顯示出當使用包含根據本發明的蒸發抑制劑之 蝕刻劑時’該沉積問題明顯改善，如與當使用現存用於蝕 刻之組成物時比較；及 第3圖係-電子顯微圖，其顯示出使用根據本發明之蚀 刻劑組成物（實施例12)蝕刻的銅/鉬-鈦合金多層膜(銅層： 2000埃，合金層.300埃)之钮刻曲線圖。 【主要凡件符號說明】 (無） 15S 14 201219601 Copper ion concentration, composition of the present invention (IV) The cost of multi-metal film rectification, because the defect ratio can be treated with the following == low: taper angle 'pre-copper Hu is less. In addition, because of the well-precision plot of the lower layer of the lower layer in the multilayer film comprising the A-molybdenum titanium alloy. In addition to this, even when the thickness of the layer of the film is changed, a good-character plot can be obtained. The present invention has been described in detail with reference to "specific specific banknotes m".仁 疋 疋 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项 该项. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows deposits formed at the discharge port of an etching apparatus when a shutdown agent having an existing composition is used; Fig. 2 shows the use of an evaporation inhibitor according to the present invention when used In the case of an etchant, the deposition problem is significantly improved, as compared to when using existing compositions for etching; and Figure 3 is an electron micrograph showing the use of an etchant composition according to the invention (implementation Example 12) A button plot of an etched copper/molybdenum-titanium alloy multilayer film (copper layer: 2000 angstroms, alloy layer. 300 angstroms). [Major symbol description] (None) 15

Claims (1)

201219601 七、申請專利範圍： · 1. 一種用以蝕刻金屬膜的組成物，其包含： 7-30重量％的氧化劑； 0.1-5重量％的蝕刻控制劑； 0.1-5重量％的螯合劑； 0.01 -3重量％的凹蝕抑制劑； 0.01-5重量％的銅蝕刻抑制劑； 0.01-5重量％的殘餘物移除劑；及 適當的水量，至總重量100重量％。 2. 如申請專利範圍第1項之用以蝕刻金屬膜的組成物，其 中該氧化劑係過氧化氫。 3. 如申請專利範圍第1項之用以蝕刻金屬膜的組成物，其 中該蝕刻控制劑係一或多種選自於醋酸、檸檬酸、草 酸、馬來酸、經乙酸、琥ίή酸、酒石酸、反丁浠二酸、 水楊酸、蘋果酸及三甲基乙酸者。 4. 如申請專利範圍第1項之用以蝕刻金屬膜的組成物，其 中該螯合劑係一或多種選自於氮基三醋酸、亞胺二醋 酸、曱基亞胺二醋酸、羥乙基亞胺二醋酸、二伸乙基三 胺五醋酸、乙二胺四醋酸、Ν-羥乙基乙二胺四醋酸、曱 基乙二胺四醋酸、三伸乙基四胺六醋酸、乙二胺四亞甲 基膦酸、二伸乙基三胺五亞曱基膦酸、羥基亞乙基二膦 酸、胺基三亞曱基膦酸、甘胺酸、精胺酸、麩胺酸、丙 胺酸、半胱胺酸、麩醯胺酸、草甘膦及甘胺醯酸者。 5. 如申請專利範圍第1項之用以蝕刻金屬膜的組成物，其 S 16 201219601 中該凹I虫抑制劑係一或多種選自於礙酸鍵、填酸氫銨、 磷酸二氫銨、磷酸鈉、磷酸氫鈉及磷酸二氫鈉的無機磷 酸鹽；及一或多種選自於醋酸銨、經函化的醋酸銨及檸 檬酸敍之有機酸的敍鹽。 6. 如申請專利範圍第5項之用以蝕刻金屬膜的組成物，其 中該無機構酸鹽對有機酸的銨鹽之重量比率係1 : 0.25-2 。 7. 如申請專利範圍第1項之用以蝕刻金屬膜的組成物，其 中該銅#刻抑制劑係胺基四。坐、味。坐、吲°朵、嘌吟、0比 吐、α比咬、°定、。比D各、°比D各。定、°比α各。定、苯并三。坐或 其混合物。 8. 如申請專利範圍第1項之用以蝕刻金屬膜的組成物，其 中該殘餘物移除劑係一或多種選自於氟化銨、It化氫 敍、氟化鈉、氟化鉀、二II化銨、二氟化納及二氟化鉀 者。 9. 如申請專利範圍第1項之用以蝕刻金屬膜的組成物，其 更包含0.1-7重量％的蒸發抑制劑。 10. 如申請專利範圍第9項之用以蝕刻金屬膜的組成物，其 中該蒸發抑制劑係乙二醇、丙二醇、聚乙二醇或其混合 物。 11. 如申請專利範圍第1至10項的任何一項之用以蝕刻金屬 膜之組成物，其中該金屬膜係包含一或多種選自於銅、 銦、鈦及鉬-鈦合金的單層或多層。 17201219601 VII. Patent application scope: 1. A composition for etching a metal film, comprising: 7-30% by weight of an oxidizing agent; 0.1-5 wt% of an etching control agent; 0.1-5 wt% of a chelating agent; 0.01-3 wt% of the etch inhibitor; 0.01-5 wt% of the copper etch inhibitor; 0.01-5 wt% of the residue remover; and a suitable amount of water to 100 wt% of the total weight. 2. The composition for etching a metal film according to the first aspect of the patent application, wherein the oxidant is hydrogen peroxide. 3. The composition for etching a metal film according to claim 1, wherein the etching control agent is one or more selected from the group consisting of acetic acid, citric acid, oxalic acid, maleic acid, acetic acid, succinic acid, and tartaric acid. , butyric acid, salicylic acid, malic acid and trimethylacetic acid. 4. The composition for etching a metal film according to claim 1, wherein the chelating agent is one or more selected from the group consisting of nitrogen triacetic acid, imine diacetic acid, mercaptoimine diacetic acid, and hydroxyethyl group. Imine diacetic acid, di-extension ethyltriamine pentaacetic acid, ethylenediaminetetraacetic acid, hydrazine-hydroxyethylethylenediaminetetraacetic acid, mercaptoethylenediaminetetraacetic acid, triamethylenetetraamine hexaacetate, ethylene Amine tetramethylene phosphonic acid, di-ethyltriamine pentadecylphosphonic acid, hydroxyethylidene diphosphonic acid, aminotrimethylenephosphonic acid, glycine, arginine, glutamic acid, propylamine Acid, cysteine, glutamic acid, glyphosate and glycine acid. 5. The composition for etching a metal film according to item 1 of the patent application, wherein the one or more concave insect inhibitors in S 16 201219601 are selected from the group consisting of an acid-blocking bond, ammonium hydrogen phosphate, ammonium dihydrogen phosphate An inorganic phosphate of sodium phosphate, sodium hydrogen phosphate and sodium dihydrogen phosphate; and one or more salts of an organic acid selected from the group consisting of ammonium acetate, functionalized ammonium acetate and citric acid. 6. The composition for etching a metal film according to item 5 of the patent application, wherein the weight ratio of the non-mechanical acid salt to the ammonium salt of the organic acid is 1: 0.25-2. 7. The composition for etching a metal film according to item 1 of the patent application, wherein the copper-based inhibitor is an amine group IV. Sit and taste. Sitting, 吲 °, 嘌吟, 0 than spit, α than bite, ° set. It is more than D and each has a ratio D. Set, ° ratio α. Ding, benzo tri. Sit or mix it. 8. The composition for etching a metal film according to claim 1, wherein the residue removing agent is one or more selected from the group consisting of ammonium fluoride, It hydrogen, sodium fluoride, potassium fluoride, Di-ammonium dichloride, sodium difluoride and potassium difluoride. 9. The composition for etching a metal film according to item 1 of the patent application, further comprising 0.1 to 7% by weight of an evaporation inhibitor. 10. The composition for etching a metal film according to claim 9, wherein the evaporation inhibitor is ethylene glycol, propylene glycol, polyethylene glycol or a mixture thereof. 11. The composition for etching a metal film according to any one of claims 1 to 10, wherein the metal film comprises one or more single layers selected from the group consisting of copper, indium, titanium, and molybdenum-titanium alloys. Or multiple layers. 17
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