TW200916606A - Etching composition - Google Patents

Etching composition Download PDF

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Publication number
TW200916606A
TW200916606A TW097135588A TW97135588A TW200916606A TW 200916606 A TW200916606 A TW 200916606A TW 097135588 A TW097135588 A TW 097135588A TW 97135588 A TW97135588 A TW 97135588A TW 200916606 A TW200916606 A TW 200916606A
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Taiwan
Prior art keywords
alloy
etching
layer
composition
acid
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TW097135588A
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Chinese (zh)
Inventor
Yoshitaka Nishijima
Hidekuni Yasue
Takafumi Yamabe
Yoshihiro Mukai
Hideo Murata
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Nagase Chemtex Corp
Hitachi Metals Ltd
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Publication of TW200916606A publication Critical patent/TW200916606A/en

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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
    • C23F1/32—Alkaline compositions
    • C23F1/38—Alkaline compositions for etching refractory metals
    • 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
    • C23F1/32—Alkaline compositions
    • C23F1/34—Alkaline compositions for etching copper or alloys thereof
    • 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching

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

Abstract

This invention provides an etching composition that obtains non-lateral etching and an etching cross-section having better inclination angle that is difficultly achieved by conventional techniques while etching a laminated metal layer containing copper (Cu) or Cu alloy and molybdenum (Mo) or Mo alloy. The etching composition of this invention is used for simultaneously etching Cu or Cu alloy and Mo or Mo alloy of the multi-layered metal layer composed of one or more layers of copper or copper alloy and one or more layers of molybdenum or molybdenum alloy. The essential components of this composition contain at least one salt selected from the group consisting of phosphate whose aqueous solution is base and carboxylate whose aqueous solution is base, hydroperoxide, and water.

Description

200916606 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種構成電子機器用陣列基板（尤其是 TFT-LCD用陣列基板）之銅配線形成用之蝕刻組成物。 【先前技術】 於TFT-LCD用陣列基板等之電子機器用陣列基板，係 具有閘極f極、間極配線（gate wiring)、源極電極、源極配 線（source wiring)、汲極電極、汲極配線（drain评卜丨叫）等之[Technical Field] The present invention relates to an etching composition for forming a copper wiring for forming an array substrate for an electronic device (particularly, an array substrate for a TFT-LCD). [Prior Art] The array substrate for an electronic device such as an array substrate for a TFT-LCD has a gate f-pole, a gate wiring, a source electrode, a source wiring, a drain electrode, and Bungee wiring (drain commentary)

電極及配線，以用於將訊號傳遞至元件。目前該配線材料， 主要係使用AU A1合金。…或A1合金之配線，由於會形 成氧化被膜、發生電移、或會往Si發生擴散等，因此並不 使用A1或A1合金單膜。亦即’為了防止該等問題，必須 以表面保護金屬（eap metal)、底層（福以k㈣來加以積層 化’製成2層金屬層或3層金屬層來使用。其所積層之金 屬種類可為翻（以下，亦稱為M〇)、Ti等，一般，由於可 ㈣形成配線’因此係使用可進行濕絲刻之M。。而用以 同時對由M。所積層而成之M〇/A1多層金屬層之Μ。盘乂 之兩者進行敍刻的蚀刻組成物，-般則是使用由磷酸：硝 酸、醋酸所形成之混酸溶液。 然而’伴隨液晶電視等之液 了〜狀日日顯不裝置的大型化， 其是18吋以上之大面積且高解 —^ ^ % m度之液晶顯不裝置，A1 A1合金之配線會有因電阻所；生士、^ 电I所k成之訊號傳遞延遲的 用於解決此問題之配線材料，俜 π 7寸係奴出電阻低於Α1或A1入 金，且為廉價金屬之銅（以 ° 邛％為C u )配線。 200916606 而Cu配線，亦為了防止擴散於Si及密合性問題、氧 化被膜專與A1配線同樣地並不使用Cu單膜，而必須以 M〇等作為表面保護金屬、底層來加以積層化。至少，為了 防止擴散及密纟性問題、氧化被冑，必帛製成包含底層之2 層金屬層’較佳為，由於在^表層容易形成氧化被膜，因 此較理想係再形成表面保護金屬而製成3層金屬層。雖然 會有因合金化而導致電阻上升的缺點，但亦正在研究藉由 Cu之合金化來省略底層及表面保護金屬之方法。 ,又，由於Mo本身亦容易生成氧化鉬（鉬酸），而不會 幵/成不動‘癌膜，缺乏耐腐則生，因此亦對會形成不動態膜， 具有耐腐蝕性之Mo合金進行研究。 因此’對於Cu或Cii合金與Mo之積層膜，及cu或 «金與Mo合金所形成之積層膜，必須要有同時可蝕刻 或Cu合金與Mo或M〇合金之兩者的蝕刻組成物。然而， 著Mo之合金化，若使用以往之蝕刻組成物，與相較 之下蝕刻輪廓（etching profile)大為不同，蝕刻非常困難。 又3層積層膜之蝕刻，亦容易引起電池腐蝕等，並且蝕刻 亦變得困難。即使是A1配線所使用之由麟酸、硝酸、醋酸 所形成之混酸溶液’雖然可對Cu、M〇A M〇合金之各單膜 ^凋整蝕刻速度，但是由於積層膜之各金屬的蝕刻速度會 生變化’故Cu層之蝕刻量會變大，積層膜中之Cu層會 Mo合金嗳到更深的蝕刻，而引起產生稱之為側蝕 之底切形狀的現象等’蝕刻控制非常困難。為了形成積層 金屬層之配線’必須要不會產生側蝕，而以往之混酸溶液， 200916606 並沒有於基板之製造步驟中可使用之控制性。 於專利文獻1’揭示有一種由硫酸、過氧化氫、醋酸鈉、 剩餘部分為水所形成之蝕刻組成物，於專利文獻2，則揭示 有一種由鹽酸、無機酸或無機酸鹽與過氧化氫、剩餘部分 為水所形成之Cu單膜用蚀刻液，並揭示無機酸可為硫酸^ 磷酸、硝酸、硼酸，無機酸鹽則可為除硼酸外之前述無機 I的鹼性鹽（alkali sait)及銅鹽，但是無論何者，皆有a 會發生側蝕的問題。又，於使用M〇合金時，由於Cu更加 會發生側蝕，因此完全不適合於製造步驟。又，於使用醋 -文過氧化氫溶液系、過硫酸錢作為姓刻組成物時，亦同様 不適合。 、 用以同時對所積層之Cu、M〇之2層金屬層進行蝕刻的 蝕刻組成物，已知有氟化氫系溶液與氧系溶液。然而，氟 化氫系蝕刻組成物，具有亦會同時對使用作為陣列基板之 玻璃基板、與蒸鍍在玻璃基板上作為絕緣膜之氮化矽膜 (siNx)或氧化矽膜（Si〇2)侵蝕的問題。 氧系溶液，於專利文獻3中，係揭示使用包含選自中 f生鹽、無機酸與有機酸中之至少一者及過氧化氫之蝕刻組 成物，來進行Cu ( Cu合金）與M〇的總括蝕刻，並分別揭 允中！生鹽可為KHS〇4、KI〇4、NaCi及KC1，無機酸可為鹽 次&酸、確酸及磷酸，有機酸可為醋酸。然而，此種組Electrodes and wiring for transmitting signals to components. At present, the wiring material mainly uses AU A1 alloy. ... or the wiring of the A1 alloy, since an oxide film is formed, electromigration occurs, or diffusion occurs in Si, the A1 or A1 alloy single film is not used. That is to say, in order to prevent such problems, it is necessary to use a surface metal (eap metal) and a bottom layer (fused by k (four) to form a layer of two metal layers or three metal layers. The metal type of the layer can be used. In order to turn over (hereinafter, also referred to as M〇), Ti, etc., generally, since the wiring can be formed (4), it is possible to use M which can be wet-nicked. /A1 The layer of the multi-layer metal layer. The etching composition of the two sides of the disk is generally used as a mixed acid solution formed of phosphoric acid: nitric acid or acetic acid. However, the liquid accompanying the liquid crystal television has been used. The large-scale device of the Japanese display device is a liquid crystal display device with a large area of 18 吋 or more and a high solution - ^ ^ % m degree. The wiring of the A1 A1 alloy has a resistance due to the resistance; The wiring material used to solve this problem is a wiring material with a delay of less than Α1 or A1, and is a copper of cheap metal (with °% being C u ). 200916606 and Cu Wiring, also to prevent diffusion of Si and adhesion problems, oxide film specifically with A1 In the same manner, the wiring does not use a Cu single film, but it is necessary to laminate the surface protective metal or the underlayer with M 〇 or the like. At least, in order to prevent the problem of diffusion and blocking, and the oxidized bedding, it is necessary to form the underlayer 2 The layered metal layer 'preferably, since the oxide film is easily formed on the surface layer, it is preferable to form a surface protective metal to form three metal layers. Although there is a disadvantage that the resistance is increased due to alloying, it is also The method of omitting the underlying layer and the surface protective metal by alloying of Cu is studied. Moreover, since Mo itself is also prone to generate molybdenum oxide (molybdic acid), it does not become a non-moving 'cancer film, and lacks corrosion resistance. Therefore, it is also studied for Mo alloys which have a non-dynamic film and have corrosion resistance. Therefore, it is necessary to have a laminated film of Cu or Cii alloy and Mo, and a laminated film formed of cu or «gold and Mo alloy. An etch composition that can be etched or both a Cu alloy and a Mo or M bismuth alloy. However, alloying of Mo, if a conventional etch composition is used, is significantly different from the etching profile. Etching is very difficult. The etching of three layers of laminated film is also likely to cause corrosion of the battery, etc., and etching becomes difficult. Even the mixed acid solution formed of linonic acid, nitric acid, and acetic acid used in the A1 wiring can be used. The etching speed of each single film of Cu, M〇AM〇 alloy, but the etching rate of each metal of the laminated film changes, so the etching amount of the Cu layer becomes large, and the Cu layer in the laminated film will be Mo alloy. It is very difficult to etch into a deeper etching, which causes an undercut shape called side etching. Etching control is very difficult. In order to form a wiring of a laminated metal layer, side etching must not occur, and the conventional mixed acid solution, 200916606 There is no controllability that can be used in the manufacturing steps of the substrate. Patent Document 1' discloses an etching composition formed of sulfuric acid, hydrogen peroxide, sodium acetate, and the remainder being water. In Patent Document 2, a hydrochloric acid, an inorganic acid or a mineral acid salt and peroxidation are disclosed. Hydrogen, the remaining part is an etching solution for Cu single film formed by water, and reveals that the inorganic acid may be sulfuric acid, nitric acid, boric acid, and the inorganic acid salt may be an alkaline salt of the above inorganic I other than boric acid (alkali sait) And copper salt, but no matter what, there will be a problem of side erosion. Further, when the M bismuth alloy is used, since Cu is more likely to cause side etching, it is not suitable for the manufacturing step at all. Moreover, when using a vinegar-form hydrogen peroxide solution system or a persulfate money as a surname composition, it is also unsuitable. A hydrogen fluoride-based solution and an oxygen-based solution are known as an etching composition for simultaneously etching two layers of Cu and M layers of the deposited layer. However, the hydrogen fluoride-based etching composition has corrosion of a tantalum nitride film (SiNx) or a tantalum oxide film (Si〇2) which is used as an insulating film on the glass substrate which is used as an insulating film. problem. In the oxygen-based solution, in Patent Document 3, it is disclosed that Cu (Cu alloy) and M〇 are used by using an etching composition containing at least one selected from the group consisting of a raw salt, an inorganic acid, and an organic acid, and hydrogen peroxide. The general etch is etched separately and revealed separately! The raw salt may be KHS〇4, KI〇4, NaCi and KC1, the inorganic acid may be salt & acid, acid and phosphoric acid, and the organic acid may be acetic acid. However, this group

Cu亦會發生側蝕，蝕刻控制非常困難。又，於Μ〇合 金之情报 n s.Side etching also occurs in Cu, and etching control is very difficult. Also, Yu Qihe Jinzhi Information n s.

Lu更加會發生側蝕。因此，無法完全使用於製 迈步驟中之積層膜之配線形成。 200916606 因此，Cu單膜之蝕刻組成物、及Cu ( Cu合金）與M〇 之2層積層膜之蝕刻組成物雖被研究，但是不會發生側敍 得到較佳之傾角（taper angle)是困難的。 [專利文獻1 ]日本特開昭61 -591號公報 [專利文獻2]曰本特開昭5 1-2975號公報 [專利文獻3]日本特開2002-302780號公報 【發明内容】 因此，本發明之目的，在於提供一種於蝕刻由Cu或 Cu合金與Mo或Mo合金所構成之多層積層金屬層時，可 得到以先前技術難以達成之無侧蝕、具有較佳傾角之蝕刻 截面形狀的姓刻組成物。 本發明，為一種蝕刻組成物，用以同時對由銅或銅合 金之1層或複數層與鉬或鉬合金之丨層或複數層所構成之 多層積層金屬層的銅或銅合金及鉬或鉬合金進行蝕刻，必 要成分係含有選自由水溶液為鹼性之磷酸鹽及水溶液為鹼 性之羧酸鹽所構成之群之至少一種鹽與過氧化氫與水而 成。 (1) 本發明之蝕刻組成物，藉由上述之構成，可於蝕 刻由Cu或Cu合金與Mo或M〇合金所構成之多層積層金屬 層時，得到以先前技術難以達成之無側触、具有較佳傾角 之蝕刻截面形狀。 (2) 本發明之蝕刻組成物，藉由上述之構成，由於可 同時對由Cu或Cu合金與河〇或⑽合金所構成之多層積層 金屬層的Cu· Cu合金# M“ M〇合金進行蝕刻，二可： 200916606 少步驟數。 【實施方式】 上述磷酸鹽，只要是水溶液為驗性之磷酸鹽，則並I 特別限制，例如可為磷酸三銨等鹼性之磷酸銨鹽、磷酸三 胺鹽（碟酸三單乙醇胺鹽、碟酸三正丙醇胺鹽、♦酸三異 丙醇胺鹽等）等鹼性之磷酸胺鹽等，可使用此等之其中^ 種或2種以上。此等之中，較佳為磷酸三銨、磷酸三單乙 醇胺鹽等之磷酸三胺鹽或此等之合併使用。磷酸鹽於蝕刻 液中之濃度，較佳在lwt%以上，若未達lwt%，則由於敍 ?速度將會變f曼，故不佳。上限雖無特別限定，但因溶解 里之上限，一般在20wt%以下，更佳在15wt%以下。 上述羧酸鹽，只要是水溶液為鹼性之羧酸鹽，則並無 特別限制，例如可為醋酸胺冑（例如，醋酸單乙醇胺鹽’:、 醋酸正丙醇胺鹽、醋酸異丙醇胺鹽等），草酸二單乙=胺 鹽等之羧酸（醋酸、草酸以外，例如可為曱酸、丙酸、丁 酸、乳酸、蘋果酸、檸檬酸、丙二酸、琥珀酸、反丁烯二 酸、順丁烯二酸等）之鹼性胺鹽。此等之中， 單乙醇胺鹽等之醋酸胺鹽…驗性鹽並無特別限= 為鹼金屬鹽（alkali metal salt)(例如醋酸鈉、醋酸鉀、檸 檬酸三鈉、檸檬酸三鉀等）、其他之胺鹽（例如二乙醇胺、 三乙醇胺之鹽）等。此等可使用其丨種或2種以上。羧酸 鹽於#刻液中之濃度’較佳在1 以上，若未達1 , 則由於蝕刻速度將會變慢，故不佳。上限 但因溶解量之上限，一般在一以下，更佳、= 9 200916606 下。 於本發明中，亦可使用上述磷酸鹽之1種或2種以上， 或使用上述羧酸鹽之丨種或2種以上，或者是合併使用上 述鱗酸鹽之1種或2種以上與上述羧酸鹽之1種或2種以 上。合併使用時之鹽於蝕刻液中之濃度，較佳在i wt%以上， 若未達1 wt%，則由於蝕刻速度將會變慢，故不佳。上限雖 無特別限定，但因溶解量之上限，一般在2〇wt%以下，更 佳在15wt°/〇以下。Lu is more likely to have side eclipses. Therefore, it is impossible to completely use the wiring formation of the laminated film in the step of making the step. 200916606 Therefore, although the etching composition of the Cu single film and the etching composition of the Cu (Cu alloy) and the two-layer laminated film of M〇 have been studied, it is difficult to obtain a better taper angle. . [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION It is an object of the invention to provide a method for etching a multi-layer laminated metal layer composed of a Cu or Cu alloy and a Mo or Mo alloy, which results in a etched cross-sectional shape which is difficult to achieve in the prior art and which has a preferred inclination angle. Engraved composition. The present invention is an etching composition for simultaneously copper or copper alloy and molybdenum or a multilayered metal layer composed of one or more layers of copper or a copper alloy and a tantalum or a plurality of layers of molybdenum or molybdenum alloy The molybdenum alloy is etched, and the essential component is obtained by containing at least one salt selected from the group consisting of a phosphate which is alkaline in an aqueous solution and a carboxylate which is alkaline in an aqueous solution, and hydrogen peroxide and water. (1) The etching composition of the present invention can be obtained by etching the multilayer laminated metal layer composed of Cu or a Cu alloy and Mo or M bismuth alloy, thereby obtaining a sideless touch which is difficult to achieve by the prior art. An etched cross-sectional shape having a preferred tilt angle. (2) The etching composition of the present invention, by the above constitution, can be simultaneously performed on a Cu·Cu alloy # M “M〇 alloy of a multi-layer laminated metal layer composed of Cu or a Cu alloy and a river raft or a (10) alloy. Etching, the second can be: 200916606, the number of steps is small. [Embodiment] The phosphate is not particularly limited as long as it is an aqueous solution, and may be, for example, an alkaline ammonium phosphate such as triammonium phosphate or a phosphoric acid. An amine phosphate salt such as an amine salt (disc triethanolamine salt, a tri-n-propanolamine salt, or a triisopropanolamine salt) may be used, or two or more of these may be used. Among these, a triamine phosphate such as triammonium phosphate or trimonoethanolamine phosphate is preferably used in combination. The concentration of the phosphate in the etching solution is preferably at least 1% by weight. Lwt%, because the speed will be changed to f, so it is not preferable. The upper limit is not particularly limited, but the upper limit of the dissolution is generally 20% by weight or less, more preferably 15% by weight or less. The aqueous solution is a basic carboxylate, and is not particularly limited, and for example, An acid amine hydrazine (for example, monoethanolamine acetate::, n-propanolamine acetate, isopropanol acetate, etc.), carboxylic acid such as oxalic acid monoethylamine = amine salt (other than acetic acid or oxalic acid, for example, hydrazine) a basic amine salt of acid, propionic acid, butyric acid, lactic acid, malic acid, citric acid, malonic acid, succinic acid, fumaric acid, maleic acid, etc. Among these, monoethanolamine salt The amine acetate salt...the organic salt is not particularly limited to = alkali metal salt (such as sodium acetate, potassium acetate, trisodium citrate, tripotassium citrate, etc.), other amine salts (for example, two Ethanolamine, a salt of triethanolamine, etc.. These may be used in combination or in combination of two or more. The concentration of the carboxylate in the #刻液 is preferably 1 or more, and if it is less than 1, the etching rate will change. In the present invention, one or more of the above phosphates may be used, or the above-mentioned carboxylic acid may be used. One or more of the above-mentioned acid salts, or one or more of the above-mentioned sulphates One or two or more kinds of carboxylates. The concentration of the salt in the etching solution when used in combination is preferably i wt% or more. If it is less than 1 wt%, the etching rate will be slow, so it is not good. The upper limit is not particularly limited, but is usually 2% by weight or less, and more preferably 15% by weight or less, depending on the upper limit of the amount of dissolution.

本發明之過氧化氫於蝕刻液中之濃度，並無特別限 制較仏在0.5wt/〇以上’若未達〇 5wt%，則银刻速度將會 變慢，故不佳。上限並盔牯 π： I ,…将別限疋，例如較佳在35〜％以 下’更佳在20wt%以下。 〜口《«小浴攸為鹼性之磷酸鹽 及水溶液為㈣讀酸鹽所構成之群之至少—種鹽與過氧 I、匕氣之合計量的剩餘部分為上限，並視需要添加有下述所 =之其他成分時，該種其他成分與上述鹽與過氧化氮之 &叶的剩餘部分。 可為添加有可使Cu提 Cr、V、Nb、Ni、Ag、 上述Cu合金，並無特別限制， 升耐腐蝕性之元素（例如Ti、Ζι·、 A1、Zn、Sn )之合金。 升細* ^ 列’可為添加有可使Μ 汁耐腐蝕性之元素（例如Ti、Ζι·、⑴ 乙r、Hf、v、n π 或 Ni 夕 1 碰彳 9 锸 ”；ι·、 Nb、Ta、Cr、 乂⑴之1種或2種以上）之合金。 合金、λ/ττ.人么、隹此从 令 < 中’尤其以Μ 盍'Moh合金、進一步於此等添加 ’ Nl之Mo合金為， 10 200916606 於本發明中，視雪 γ你人 穩定劑，例如可為草s^ 過氧化氣穩定劑。上述 合物及其鹽、聚袈一類萘磧酸仏縮 酸、乙二醇—甲^%酸及其料W合物或膦 等之乙-L 乙二醇一乙基越、乙二醇-丁基驗 族@ ·乙％、正丙醇等之低級飽和脂肪 族酉子類。於蝕刻液中 η nn，+〇/ <，晨厪並無特別限制，較佳為 鹽時，可^π7。之乾圍。惟’於上述必要成分中使用缓酸 文/ U摻合過氧化氫穩定劑，但在不會對本發明 之效果造成不良影響 .„ y, 固77 T進—步混合其他1種以 上之過軋化虱穩定劑。 鬥、^亦可在不會對本發明之效果造成不良影響的範 活性劑來提高潤濕性等，以謀求消除敍刻不 i ，1面/# 11劑’並無特別限制，例如可為屬非離子 雜：且面活性劑或於親油基含有氟而成之界面活性劑、於 親水基具有續酸而点 成之界面活性劑等。於蝕刻液中之濃 度，並無特別限制，較佳為0.001wt%〜lwt%之範圍。 又▲’為了調整蚀刻時間及錐形，視需要’可添加公知 抗餘劑_L述Cu抗钱劑，例如可使用三岐系化合物 :1,2,3·三唑、以，4-三唑、5_苯基-1，2,4-三唑、5-胺基-H4· “苯并—唑、1 _甲基_苯并三唑或曱苯基三唑。於蝕刻 液中之濃度’並無特別限制，較佳為。⑽罐〜…。/。之範 圍0The concentration of the hydrogen peroxide in the etching solution of the present invention is not particularly limited to 0.5 wt/〇 or more. If it is less than 5 wt%, the silver engraving speed will be slow, which is not preferable. The upper limit and the helmet 牯 π: I , ... will be limited to, for example, preferably less than 35 to %, and more preferably less than 20% by weight. ~ The mouth of the "small bath 攸 is alkaline phosphate and the aqueous solution is the group of (4) reading acid salt, the remaining part of the salt and the peroxygen I, helium gas is the upper limit, and if necessary, In the case of the other components described below, the other components and the remaining salts of the above salts and the nitrogen peroxide & An alloy containing Cr, V, Nb, Ni, Ag, and the above Cu alloy, which is not particularly limited, and which is resistant to corrosion resistance (e.g., Ti, Ζ, · A1, Zn, Sn) may be added. The ascending order * ^ column ' can be added with an element that can make the juice resistant to corrosion (for example, Ti, Ζι·, (1) B, R, Hf, v, n π or Ni 1 1 彳 9 锸 ;; ι·, Nb An alloy of one or more of Ta, Cr, and yttrium (1). Alloy, λ/ττ. Person, 隹 从 令 中 中 中 尤其 尤其 尤其 Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo Mo The Mo alloy is, 10 200916606 In the present invention, the snow γ is a stabilizer for the person, for example, it can be a grass s ^ peroxide gas stabilizer. The above compound and its salt, a kind of naphthoic acid phthalic acid, B Diol-methic acid and its compound W or phosphine, such as B-L ethylene glycol monoethyl, ethylene glycol-butyl test group @ · B%, n-propanol and other low-grade saturated aliphatic Tweezers. In the etching solution, η nn, + 〇 / <, morning 厪 is not particularly limited, preferably salt, can be π7. The dry circumference. Only 'use the slow-acid text in the above essential ingredients / U is blended with a hydrogen peroxide stabilizer, but does not adversely affect the effect of the present invention. „y, solid 77 T is further mixed with one or more other over-rolled bismuth stabilizers. The hopper or the pharmaceutically active agent which does not adversely affect the effects of the present invention can be used to improve the wettability and the like, so as to eliminate the simplification, and the 1 surface/#11 agent is not particularly limited, and for example, it can be a genus. Nonionic impurities: a surfactant, a surfactant containing fluorine in a lipophilic group, a surfactant having a hydrophilic group and a point of addition to a hydrophilic group. The concentration in the etching solution is not particularly limited, and is preferably in the range of 0.001% by weight to 1% by weight. ▲ 'In order to adjust the etching time and taper, if necessary, add a known anti-surplus agent _L to describe the Cu anti-money agent, for example, a triterpenoid compound can be used: 1,2,3 · triazole, to, 4-three Oxazole, 5-phenyl-1,2,4-triazole, 5-amino-H4· "benzoxazole, 1-methyl-benzotriazole or fluorenylphenyl triazole. In etching solution The concentration 'is not particularly limited, preferably. (10) Cans ~.. /. Range 0

本發明之組成物之 並無特別需要調整pH pH較佳為8〜11。本發明之組成物 但視需要’亦可使用公知之pH調 11 200916606 整劑。 本發明之組成物，係使用作為用以同時對由Cu或Cu 合金之1層或複數層與M〇4Mo合金之丨層或複數層所構 成之多層積層金屬層的Cu或Cu合金及厘〇或1^1〇合金進行 蝕刻之組成物。上述多層積層金屬層，可為Cu或cu合金 與Mo或Mo合金之2層或3層或3層以上之積層金屬;， 積層構成並無特別限制，例如，可為Cu或Cu合金層/m〇 或Mo合金層之積層構成的2層積層金屬層，或者是或 Mo合金層心或。合金層/M(^M。合金層之積層構成的 3層積層金屬層等，更具體而言，例如，可為a層或 M〇合金層之積層構錢2層積層金屬層（例如Cu/Mo、 Cu/Mo合金），或者是M〇或M〇合金層心層/編或 合金層之積層構成的3層積層金屬層（例如m〇/Cu/m〇'M〇 合金/CU/M。合金、Mg/Cu/m。合金等）。本發明之組成物， 即使是控制Cu之姓刻速度，且藉由M。之合金化來提升耐 腐蚀性’亦可以下述方式來進行㈣控制^亦即，若為Μ。 合金層心或CU合金層之積層構成的2層積層金屬層，則 蚀刻截面形狀之錐形（傾角），無論M〇合金種類為何，幾 t不具有差異，皆具有較佳之錐形，可防止Mo合金之侧蝕 ’、即底切形狀。又，M〇合金層心或Cu合金層/Mo合金層 3層積層金屬層，由於可視合金種類來調： :相同2 可得到最佳之錐形。肖2層積層金屬 曰° '、β防止下層之Mo合金之側蝕。 [實施例] 12 200916606 以下，藉由實施例進一步具體說明本發明，惟以下之 記載僅專用以説明，本發明並不限定於此等之實施例。 實施例1 使用以2.5wt%之磷酸三銨三水合物、i.5wt%之醋酸單 乙醇胺鹽、1.5wt%之過氧化氫、剩餘部分為水所調合之蝕 刻組成物（pH9_05 ) ’並使用由光阻圖案化之以Cu與M〇There is no particular need to adjust the pH of the composition of the present invention to a pH of preferably from 8 to 11. The composition of the present invention may be used as needed. A known pH adjusting agent 11 200916606 may also be used. The composition of the present invention is a Cu or Cu alloy and a decant which is used as a multi-layered metal layer for simultaneously forming a bismuth layer or a plurality of layers of a Cu or Cu alloy and a bismuth layer or a plurality of layers of an M〇4Mo alloy. Or a composition of 1^1 〇 alloy for etching. The multilayer laminated metal layer may be a layered metal of two or three or more layers of Cu or a cu alloy and Mo or a Mo alloy; the laminated structure is not particularly limited, and for example, may be a Cu or Cu alloy layer/m A two-layer laminated metal layer composed of a layer of tantalum or a Mo alloy layer, or a layer of a Mo alloy layer. Alloy layer/M (^M. A three-layer laminated metal layer composed of a laminate of alloy layers, etc., more specifically, for example, a layer of a layer or a layer of M〇 alloy layer can be constructed with two layers of a metal layer (for example, Cu/ Mo, Cu/Mo alloy), or a three-layer laminated metal layer composed of a laminate of M〇 or M〇 alloy layer/layer or alloy layer (for example, m〇/Cu/m〇'M〇 alloy/CU/M Alloy, Mg/Cu/m, alloy, etc.) The composition of the present invention can be improved in the following manner even if the etching speed of Cu is controlled and the alloying of M is used to improve the corrosion resistance. The control ^ is, for example, a two-layered metal layer composed of a laminate of an alloy layer core or a CU alloy layer, and the taper (inclination angle) of the cross-sectional shape is etched, and there is no difference in the number of the M 〇 alloy, regardless of the type of the M 〇 alloy. Both have a better taper to prevent the side etching of the Mo alloy, that is, the undercut shape. Also, the M〇 alloy layer core or the Cu alloy layer/Mo alloy layer 3 layer metal layer is adjusted by the type of visible alloy: The same two can obtain the best taper. The two-layer laminated metal 曰°, β prevents the undercut of the underlying Mo alloy. [Embodiment] 12 2009 The invention is further illustrated by the following examples, but the following description is only intended to be illustrative, and the invention is not limited to the examples. Examples 1 using 2.5 wt% of triammonium phosphate trihydrate, I. 5 wt% of acetic acid monoethanolamine salt, 1.5 wt% of hydrogen peroxide, and the remainder is an etch composition (pH 9_05 ) blended with water' and patterned by photoresist to Cu and M〇

合金（A)(添加有5wt°/〇之Nb的Mo)或Mo合金（B)(添 加有10wt%之Nb的Mo合金）所構成之M〇合金/Cu/M〇合 金之3層積層金屬層（Cu . 2000A，各Mo合金：50〇A，計 3000A)的基板。處理溫度為23t，以至金屬層完全溶解為 止之時間（Just.Etch.Time.)進行蝕刻處理。藉由以上述條 件之#刻處理所得之配線之截面錐形的掃瞄型電子顯微鏡 照片，分別示於圖1 (左圖（使用Mo合金（a)),中圖 (使用Mo合金（B ))。 從圖1 (左圖，中圖）可知，可同時蝕刻Cu與M〇合 金之3層積層金屬層，且沒有側蝕，可得到良好之截面錐 形。 實施例2 使用以2.5wt%之麟酸三錢三水合物、3 75〜％之醋酸單 乙醇胺鹽、Uwt%之過氧化氫、剩餘部分為水所調合之触 刻組成物（PH8.95)，並使用由光阻圖案化之以^與m〇 合金（添加有10wt%之Nb的M〇合金）所構成iM〇合金 /Cu/Mo合金之3層積層金屬層（Cu:2〇〇〇A，各m〇合金： 5〇〇人，計3000A)的基板。處理溫度為23χ：，以至金屬層 13 200916606Three-layer laminated metal of M〇 alloy/Cu/M〇 alloy composed of alloy (A) (Mo with 5wt/〇Nb) or Mo alloy (B) (Mo alloy with 10wt% Nb added) A substrate (Cu. 2000A, each Mo alloy: 50 A, 3000 A). The treatment temperature was 23 t, and the etching treatment was performed for the time until the metal layer was completely dissolved (Just. Etch. Time.). The scanning electron micrographs of the cross-section taper of the wiring obtained by the above-mentioned conditions are shown in Fig. 1 (left drawing (using Mo alloy (a)), middle drawing (using Mo alloy (B) It can be seen from Fig. 1 (left image, middle panel) that a three-layer laminated metal layer of Cu and M〇 alloy can be simultaneously etched without side etching, and a good cross-sectional taper can be obtained. Example 2 Using 2.5 wt% The linonic acid triethanol trihydrate, 3 75~% acetic acid monoethanolamine salt, Uwt% hydrogen peroxide, the balance of the water is blended with the etchant composition (pH 8.95), and patterned by photoresist A three-layer laminated metal layer of iM〇 alloy/Cu/Mo alloy composed of a m与 alloy (M〇 alloy with 10% by weight of Nb added) (Cu: 2〇〇〇A, each m〇 alloy: 5 〇〇人, 3000A) substrate. Processing temperature is 23χ:, to metal layer 13 200916606

Time.)進行钱刻處理。藉 配線之截面錐形的掃瞄型 完全溶解為止之時間（JusiEtch. 由以上述條件之蝕刻處理所得之 電子顯微鏡照片示於圖1 (右圖) (右圖）可知’可同時钱刻Cu與Mo合金 »_ » . 層積層金屬層 …興驗合名 L又有側蝕’可得到良好之截面錐形。 之下、：’ Μ金之银刻速度-般係小於&，與Cu相較 即二在:=易控制_速度’因此本發明之㈣容液， 有t 金膜之制料行總括㈣時，亦沒 有側蝕，可得到良好之截面錐形。 實施例3 ▲使用以2.5wt%之罐酸三錄三水合&、心⑼之醋酸單 乙醇胺鹽、0.75wt%之過氧化氫、剩餘部分為水所調合之蝕 刻組成物（ΡΗ9·〇7 )，並使用由光阻圖案化之以Cu與 所構成之M〇/Cui 2層積層金屬層（Cu:3〇〇〇a，m〇:3〇〇a， 計3300A)的基板。處理溫度為2rc，以至金屬層完全溶 解為止之B守間（Just Etch Time.)進行钱刻處理。藉由以上 述條件之蝕刻處理所得之配線之截面錐形的掃瞄型電子顯 微鏡照片示於圖2。 從圖2可知，可同時蝕刻cu與Mo之2層積層金屬層， 且沒有側I虫，可得到良好之截面錐形。 比較例1 使用以23.2 wt%之麟酸、57.5 wt%之醋酸、3.3 wt%之硝 酸、剩餘部分為水所調合之蝕刻組成物，並使用由光阻圖 案化之以Cu與Mo、Cu與Mo合金（添加有l〇wt%之Nb 200916606 的Mo )所構成之Mo ( Mo合金）/Cu/Mo ( Mo合金）之3 層積層金屬層（Cu: 2000人，Mo及Mo合金：500A，計3000A) 的基板。處理溫度為231：，以至金屬層完全溶解為止之時 間（Just.Etch.Time.)進行蝕刻處理。所得之配線之截面錐 形的掃瞄型電子顯微鏡照片分別示於圖3。 從圖3’由於上層與下層之Mo (Mo合金）尚未溶解， 而中間層之Cu已溶解’因此可觀察到上層之m〇( Mo合金） 垂下的模樣。因此，磷酸、醋酸、硝酸之混酸溶液雖然可 蝕刻Cu、Mo或Mo合金，但是Cu會發生側蝕，係無法使 用作為配線之形狀。 比較例2 使用以5wt%之硫酸、5_2wt°/〇之過氧化氫、剩餘部分為 水所調合之蝕刻組成物，並使用光阻圖案化之以Cu與Mo 及Cu與Mo合金（添加有1 〇wt%之Nb的Mo)所構成之Time.) Carry out the money processing. The time until the scanning type of the cross section of the wiring is completely dissolved (JusiEtch. The electron micrograph obtained by the etching treatment under the above conditions is shown in Fig. 1 (right) (right). Mo alloy»_ » . Layered metal layer... Prosperously named L and side etched' can get a good cross-section taper. Below,: 'The gold-engraved speed of the sheet metal is less than & That is, in the following: = easy control _ speed ' Therefore, the (4) liquid of the present invention, when there is a t-gold film preparation line (4), there is no side eclipse, and a good cross-sectional taper can be obtained. Example 3 ▲ use 2.5 The wt% of the candidum trihydrate trihydrate &, the heart (9) of the acetic acid monoethanolamine salt, 0.75 wt% of hydrogen peroxide, the remainder of the water is blended with the etching composition (ΡΗ9·〇7), and used by the photoresist The substrate is patterned with Cu and a M〇/Cui 2 layered metal layer (Cu: 3〇〇〇a, m〇: 3〇〇a, 3300A). The processing temperature is 2rc, so that the metal layer is completely The B stagnation (Just Etch Time.) is dissolved and processed by etching treatment under the above conditions. A scanning electron micrograph of the cross-section of the line is shown in Fig. 2. As can be seen from Fig. 2, the two-layer metal layer of cu and Mo can be simultaneously etched, and no side I worm is obtained, and a good cross-sectional taper can be obtained. Example 1 An etching composition blended with 23.2 wt% of cinnamic acid, 57.5 wt% of acetic acid, 3.3 wt% of nitric acid, and the balance of water was used, and Cu and Mo, Cu and Mo were patterned by photoresist. A three-layer metal layer of Mo (Mo alloy)/Cu/Mo (Mo alloy) composed of an alloy (Mo added with Nb 200916606) (Cu: 2000 persons, Mo and Mo alloy: 500A, 3000A) substrate. The processing temperature is 231:, and the etching time is performed until the metal layer is completely dissolved (Just.Etch.Time.). The scanning electron micrographs of the cross-section of the obtained wiring are shown in Fig. 3, respectively. From Fig. 3', since the upper and lower layers of Mo (Mo alloy) have not been dissolved, and the Cu of the intermediate layer has been dissolved', it is observed that the upper layer of m〇 (Mo alloy) hangs down. Therefore, phosphoric acid, acetic acid, nitric acid Although the mixed acid solution can etch Cu, Mo or Mo alloy, Cu will cause side etching. It is not possible to use the shape as a wiring. Comparative Example 2 An etching composition in which 5 wt% of sulfuric acid, 5-2 wt%/〇 of hydrogen peroxide, and the balance of water was used was used, and Cu and Mo were patterned using photoresist. And Cu and Mo alloy (Mo added with 1% by weight of Nb)

Mo ( Mo合金）/Cu/Mo (Mo合金）之3層積層金屬層（Cu: 2000A ’ Mo及]Mo合金：50〇A，計3000A)的基板。處理 溫度為40 °C ，以至金屬層完全溶解為止之時間 (Just.Etch.Time.)進行蝕刻處理《於處理溫度為23。(：下亦 進行相同之處理。藉由以上述條件之蝕刻處理所得之配線 之截面錐形的掃瞄型電子顯微鏡照片，分別示於圖4 (上半 圖）。比較例2之蝕刻組成物，係專利文獻3所示成分之 蝕刻組成物。 從圖4(上段圖），由於上層與下層之]vio(Mo合金） 尚未溶解，而中間層之Cu已溶解，因此可觀察到上層之 15 200916606A substrate of a three-layer laminated metal layer of Mo (Mo alloy) / Cu / Mo (Mo alloy) (Cu: 2000A 'Mo and Mo alloy: 50 Å A, 3000 A). The etching temperature was 23 at a treatment temperature of 40 ° C until the time when the metal layer was completely dissolved (Just. Etch. Time.). (The same processing is performed next. The scanning electron micrograph of the cross-sectional taper of the wiring obtained by the etching treatment under the above conditions is shown in Fig. 4 (top half), respectively. The etching composition of Comparative Example 2 It is an etching composition of the composition shown in Patent Document 3. From Fig. 4 (upper drawing), since the upper and lower layers of vio (Mo alloy) have not been dissolved, and the Cu of the intermediate layer has been dissolved, the upper layer can be observed. 200916606

Mo ( Mo合金）垂下的模樣。因此，cu顯著發生侧蝕，係 無法使用作為配線之形狀。與M〇合金之積層金屬層之情 形’ Cu之側蝕量顯著增加。又，即使是在處理溫度為231 (圖4上半之右圖），亦與處理溫度4〇。〇 (圖*上半之左 圖、中圖）相同，Cu發生侧蝕，且蝕刻時間在5分鐘以上， 故並不適用於工業生產。 比較例3 除了使比較例2之钮刻組成物為5wt°/〇之硫酸、 0.867wt%之過氧化氫、剩餘部分為水，並將蝕刻對象改變 為由光阻圖案化之以Cu與Mo所構成之Mo/Cu/Mo之3層 積層金屬層（Cu ·· 2000人’ Mo : 500人，計3000人）的基板 以外’其餘皆進行與比較例2相同之處理。所得之配線之 截面錐形的掃瞄型電子顯微鏡照片示於圖4 (下左圖）。比 較例3之蝕刻組成物，係專利文獻3所示成分之蝕刻組成 物。 比較例4 除了使比較例2之蝕刻組成物為5wt°/〇之硫酸、8.67wt0/〇 過氧化氫、剩餘部分為水，並將蝕刻對象改變為由光阻圖 案化之以Cu與Mo所構成之m〇/Cu/Mo之3層積層金屬層 (Cu : 2000A，Mo : 500A，計 3000A)的基板以外，其餘 白進行與比較例2相同之處理。所得之配線之截面錐形的 掃目苗型電子顯微鏡照片示於圖4 (下右圖）。比較例4之蝕 亥J組成物’係專利文獻3所示成分之姓刻組成物。 從圖4(下左圖、下右圖），由於上層與下層之M〇尚 16 200916606 未/合解，而中間層之Cu已溶解，因此可觀察到上層之 垂下的模樣。因此，比較例3、4，Cu皆發生側蝕，係無法 使用作為配線之形狀。從比較例2〜4 ’與M〇合金之積層 金屬層之情形，Cu側蝕量之増加更為顯著。比較例2、3、 4,為成分相同，組成比不同之蝕刻組成物。此等之蝕刻組 成物，係專利文獻3所示之實施例圖之圖形兩端及中心值 所示成分的蝕刻組成物。 比較例5 除了使用以5wt。/。之醋酸、5.2wt°/〇之過氧化氫、剩餘部 分為水所調合之蝕刻組成物，並將蝕刻對象改變為由光阻 圖案化之以Cu與Mo及Cu與Mo合金（添加有1〇wt%之 Nb的Mo )所構成之Mo ( Mo合金）/Cu/Mo ( Mo合金）之 3層積層金屬層（Cu : 2000A，Mo合金：500A，計3000A) 的基板、與以Cu與Mo所構成之Mo/cu之2層積層金屬層 (Cu : 2000A，Mo : 500A，計 2500A)的基板以外，其餘 皆進行與比較例2相同之處理。所得之配線之截面錐形的 掃猫型電子顯微鏡照片分別示於圖5(左圖、中圖、右圖）。 比較例5之蝕刻組成物’係專利文獻3所示成分之蝕刻組 成物。 從圖5’由於上層與下層之Mo (Mo合金）尚未溶解， 而中間層之Cu已溶解’因此可觀察到上層之M〇合金垂下 的模樣（圖5中圖）。又，可觀察到上層之cu層已溶解， 而下層之Mo層尚未溶解的模樣（圖5右圖）。因此，與比 較例2相較之下，雖然cu側蝕量減少’但Cu發生側姓， 17 200916606 係無法使用作為配線之截 狀可知4由從M〇改變為 M〇 口金，該傾向更加明顯。於2 # 發生側餘。 …積層之情形CU亦同樣 比較例6 除了將餘刻組成物改變為卩5奶％之KHs〇4、5 2wt%之 過氧化氫、剩餘部分為水所調合之_组成物以外，其餘 皆進行與比㈣5相同之處理。所得之配線之截面雜形的 掃晦型電子顯微鏡照片示於圖6 (左圖、中圖、右圖）。比 車乂例6之㈣組成物’係專利文獻3所示成分之#刻組成 物。 於比較例6，由於上層與下層之M〇 ( M〇合金）尚未溶 解，而中間層之Cu已溶解，因此可觀察到上層2M〇(M〇 合金）垂下或捲進的模樣（圖6左圖、中圖）。又，可觀 察到上層之Cu層溶解，而下層之M〇層尚未溶解的模樣（圖 6右圖）。因此’與比較例5相同，Cu側蝕量亦多。於2 層積層之情形Cu亦同樣發生側蝕。 比較例7 除了將蝕刻組成物改變為以2wt%之醋酸、0.7wt%之過 氧化氫、剩餘部分為水所調合之蝕刻組成物以外，其餘皆 進行與比較例2相同之處理。所得之配線之截面錐形的掃 瞄型電子顯微鏡照片示於圖7 (左圖、右圖）。比較例7之 蝕刻組成物’係專利文獻1所示成分之蝕刻組成物。 比較例7，由於上層與下層之Mo( Mo合金）尚未溶解， 而中間層之Cu已溶解，因此可觀察到上層之Mo( Mo合金） 200916606 垂下的模樣（圖7左圖、右圖）。係成分與比較例5相同， 但組成比不同之#刻組成物。結果，與比較例5相同，Cu 亦發生側蚀。 比較例8 除了將蝕刻組成物改變為以14界1%之HC1、丨丨7评(％之 硫酸、H.kt%之過氧化氫、剩餘部分為水所調合之蚀刻組 成物以外，其餘皆進行與比較例2相同之處理。比較例8 之蝕刻組成物，係專利文獻2所示成分之蝕刻組成物。 於比較例8，Cu發生侧蝕。 [産業上之可利用性] 本發明之蝕刻組成物，如上述，可用以形成價格低廉， 且電阻亦低之高品質的Cu配線。又，由於亦適用於合 金之積層膜，故可將Cu之低電阻特性作最大限度的有效利 用，可生產電阻小，且動作特性經改善之電子機器用大面 積陣列基板。 【圖式簡單說明】 圖1，係顯示實施例丨（左圖及中圖）、實施例2 (右 圖）之以Cu與Mo合金所構成之3層積層金屬層於蝕刻處 理後之配線之截面錐形的掃瞄型電子顯微鏡照片（5萬倍）。 圖2 ’係顯示實施例3之以cu與Mo所構成之2層積 層金屬層於触刻處理後之配線之截面錐形的掃瞄型電子顯 微鏡照片（5萬倍）。 圖3 ’係顯示比較例1之以cu與Mo所構成之3層積 層金屬層（左圖）及以Cu與Mo合金所構成之3層積層金 19 200916606 屬層（右圖）於蚀刻處 子顯微鏡照片（5萬倍） 示側姓寬度。 理後之配線之截面形狀的掃瞄型電 。圖中，水平具有兩箭頭之線係表 圖4 ’係顯示比較例2 (上半各圖）、比較例3 (下 左圖）、、比較例4(下半右圖）之以Cu# Μ〇& %。合金 所構成之3層積層金屬層於㈣處理後之配線之截面形狀 的掃瞄型電子顯微鏡照片（丨萬倍）。圖中，水平具有兩箭 頭之線係表示側蚀寬度。 * 圖5，係顯示比較例5之以Cu與M〇及合金所構 成之2層積層金屬層（右圖）及3層積層金屬層（左圖及 中圖）於蝕刻處理後之配線之截面形狀的掃瞄型電子顯微 鏡照片（5帛倍）。圖巾，水平具有兩箭頭4線係表示側姓 寬度。 圖6，係顯示比較例6之以Cu與M〇及M〇合金所構 成之2層積層金屬層（右圖）及3層積層金屬層（左圖及 中圖）於ϋ刻處理後之配線之截面形狀的掃猫型電子顯微 鏡照片（左圖：5萬倍’中圖：1萬倍，右圖：5萬倍）。 圖中’水平具有兩箭頭之線係表示側蝕寬度。 圖7，係顯示比較例7之以Cu與Mo所構成之3層積 層金屬層（左圓）及以Cu與Mo合金所構成之3層積層金 屬層（右圖）於蝕刻處理後之配線之戴面形狀的掃瞄型電 子顯微鏡照片（1萬倍）。圖中，水平具有兩箭頭之線係表 示側蚀寬度。 【圖式簡單說明】 20 200916606 圖1 ’係顯示實施例i (左圖及中圖）、實施例2 (右 圖）之以Cu與Mg合金所構成之3層積層金屬層於餘刻處 理後之配線之截面錐形的掃晦型電子顯微鏡照片（5萬倍）。 圖2’係顯示實施例3之以〜與M。所構成之積 層金屬層錢刻處理後之配線之截面錐形的掃目㈣電子顯 微鏡照月（5萬倍）。 ’ 圖3,係顯示比較例i之以“與編所構成之3層積 層金屬層（左圖）及以合金所構成之3層積層金 屬層（右圖）力蝕刻處理後之配線之截面形狀的掃瞄型電 子顯微鏡照片（5萬倍）。圖中，水平具有兩箭頭之線係表 示側姓寬度。 丨尔顯不比較例 —_ - V , ^ ^ y ，疋早父例3 (下半 左圖）、比較例4(下半右圖）之以Ci^Mqm〇合金 所，成之3 |積層金屬層於姓刻處理後之配線之截面形狀 的掃晦型電子顯微鏡照片（1萬倍）。圖中，水平具有兩箭 頭之線係表示侧姓寬度。 圖5，係顯示比較例5之以Cu與Mo及Mo合金所構 成之2層積層金屬層（右圖）及3層積層金屬| (左圖及 ;钱刻處理後之配線之截面形狀的掃瞄型電子顯微 ，照片（5萬倍）。圖中，水平具有兩箭頭之線係表示側钱 圖6 ’係顯示比較例6之以Cu肖Mo及Mo合金所構 成之2層積層金屬層（右圖）及3層積層金屬f (左圖及 中圖）於蝕刻處理後之配線之截面形狀的掃瞄型電子顯微 21 200916606 鏡照片（左圖：5萬倍，中圖：1萬倍，右圖：5萬倍）。 圖中，水平具有兩箭頭之線係表示側蝕寬度。 圖7，係顯示比較例7之以Cu與Mo所構成之3層積 層金屬層（左圖）及以Cu與Mo合金所構成之3層積層金 屬層（右圖）於蝕刻處理後之配線之截面形狀的掃瞄型電 子顯微鏡照片（1萬倍）。圖中，水平具有兩箭頭之線係表 示側蝕寬度。 【主要元件符號說明】 無 22The appearance of Mo (Mo alloy) hanging down. Therefore, cu significantly causes side etching, and it cannot be used as a wiring shape. The amount of side etching of the 'Cu' is significantly increased with the laminated metal layer of the M 〇 alloy. Moreover, even at a processing temperature of 231 (the right half of Fig. 4), the processing temperature is 4 Torr. 〇 (Fig. * left, middle, and middle) is the same. Cu has side etching and the etching time is more than 5 minutes, so it is not suitable for industrial production. Comparative Example 3 except that the button composition of Comparative Example 2 was 5 wt/〇 sulfuric acid, 0.867 wt% hydrogen peroxide, and the remainder was water, and the etching target was changed to resist patterning with Cu and Mo. The same treatment as in Comparative Example 2 was carried out except for the substrate of the three-layer laminated metal layer of Mo/Cu/Mo (Cu··2000 person 'Mo: 500 persons, 3,000 persons). A scanning electron micrograph of the cross section of the obtained wiring is shown in Fig. 4 (bottom left). The etching composition of Comparative Example 3 is an etching composition of the component shown in Patent Document 3. Comparative Example 4 except that the etching composition of Comparative Example 2 was 5 wt/〇 sulfuric acid, 8.67 wt0/〇 hydrogen peroxide, and the remainder was water, and the etching target was changed to be patterned by photoresist to Cu and Mo. The same treatment as in Comparative Example 2 was carried out except for the substrate of the three-layered metal layer (Cu: 2000A, Mo: 500A, 3000A) of m〇/Cu/Mo. A cross-sectional taper of the obtained wiring is shown in Fig. 4 (bottom right). The etched J composition of Comparative Example 4 is the surname composition of the component shown in Patent Document 3. From Fig. 4 (bottom left and bottom right), since the upper layer and the lower layer are not integrated, and the Cu in the middle layer is dissolved, the appearance of the upper layer can be observed. Therefore, in Comparative Examples 3 and 4, since Cu was partially etched, it was not possible to use it as a wiring. From the case of the laminated metal layers of Comparative Examples 2 to 4' and M〇 alloy, the amount of Cu side etching was more remarkable. Comparative Examples 2, 3, and 4 are etching compositions having the same composition and different composition ratios. These etching compositions are the etching compositions of the components shown at both ends of the graph of the embodiment shown in Patent Document 3 and the center values. Comparative Example 5 was used in addition to 5 wt. /. Acetic acid, 5.2wt ° / 〇 hydrogen peroxide, the remainder is the etching composition of water, and the etching object is changed to resist the patterning of Cu and Mo and Cu and Mo alloy (added 1 添加a substrate of a three-layered metal layer of Mo (Mo alloy) / Cu / Mo (Mo alloy) composed of Mo of wt% Nb (Cu: 2000A, Mo alloy: 500A, 3000A), and Cu and Mo The same treatment as in Comparative Example 2 was carried out except for the substrate of the two-layer laminated metal layer of Mo/cu (Cu: 2000A, Mo: 500A, 2500A). The cross-sectional conical scanning electron micrographs of the obtained wiring are shown in Fig. 5 (left, middle, and right), respectively. The etching composition of Comparative Example 5 is an etching composition of the component shown in Patent Document 3. From Fig. 5', since the upper layer and the lower layer of Mo (Mo alloy) have not been dissolved, and the Cu of the intermediate layer has been dissolved, the appearance of the upper layer of the M 〇 alloy is observed (Fig. 5). Further, it was observed that the upper layer cu layer was dissolved, and the lower layer Mo layer was not dissolved (Fig. 5 right side). Therefore, compared with Comparative Example 2, although the amount of cu side etching is reduced, but the Cu generation side is surnamed, 17 200916606 cannot be used as a truncated shape of the wiring. 4 The change from M〇 to M〇口金 is more obvious. . On the 2 # occurrence side surplus. The case of the layered layer CU is also the same as in Comparative Example 6 except that the composition of the residue is changed to KHs 〇 4, 5% by weight of hydrogen peroxide of 卩5 milk%, and the remaining part is a composition of water. The same processing as (4) 5. A broom-type electron micrograph of the cross-section of the obtained wiring is shown in Fig. 6 (left, middle, and right). The composition of the (four) composition of the vehicle example 6 is a composition of the composition shown in Patent Document 3. In Comparative Example 6, since the upper layer and the lower layer of M〇 (M〇 alloy) were not dissolved, and the Cu of the intermediate layer was dissolved, the upper layer 2M〇 (M〇 alloy) was observed to be drooped or wound up (Fig. 6 left) Figure, middle picture). Further, it was observed that the upper layer of the Cu layer was dissolved, and the lower layer of the M layer was not dissolved (Fig. 6 right). Therefore, as in Comparative Example 5, the amount of Cu side etching was also large. In the case of 2 layers, Cu also has side etching. Comparative Example 7 The same treatment as in Comparative Example 2 was carried out, except that the etching composition was changed to an etching composition in which 2 wt% of acetic acid, 0.7 wt% of hydrogen peroxide, and the remainder were water. A scanning electron micrograph of the cross section of the obtained wiring is shown in Fig. 7 (left side, right side). The etching composition of Comparative Example 7 is an etching composition of the component shown in Patent Document 1. In Comparative Example 7, since the Mo (Mo alloy) of the upper layer and the lower layer was not dissolved, and the Cu of the intermediate layer was dissolved, the appearance of the Mo (Mo alloy) 200916606 of the upper layer was observed (the left diagram and the right diagram of Fig. 7). The composition was the same as that of Comparative Example 5, but the composition ratio was different. As a result, in the same manner as in Comparative Example 5, side etching also occurred in Cu. Comparative Example 8 except that the etching composition was changed to an etch composition composed of 14% of 1% of HC1, 丨丨7 (% of sulfuric acid, H.kt% of hydrogen peroxide, and the remainder being water) The same treatment as in Comparative Example 2 was carried out. The etching composition of Comparative Example 8 was an etching composition of the component shown in Patent Document 2. In Comparative Example 8, side etching occurred in Cu. [Industrial Applicability] The present invention As described above, the etching composition can be used to form a high-quality Cu wiring which is inexpensive and has a low electric resistance. Further, since it is also suitable for an alloy laminated film, the low resistance characteristic of Cu can be utilized to the maximum extent. It is possible to produce a large-area array substrate for an electronic device having a small electric resistance and improved operational characteristics. [Simplified Schematic] FIG. 1 shows an embodiment (left and middle) and an embodiment 2 (right). A scanning electron micrograph (50,000 times) of a cross-sectional taper of a wiring of a three-layer laminated metal layer composed of Cu and Mo alloy after etching treatment. Fig. 2 ' shows a composition of cu and Mo in the third embodiment. 2 layers of metal layer in the process of engraving Scanning electron micrograph (50,000 times) of the cross-section of the wiring of the wiring. Fig. 3 ' shows a three-layer laminated metal layer of cu and Mo of Comparative Example 1 (left) and Cu and Mo alloy The three-layer laminated gold 19 200916606 genus layer (right) is shown in the etched submicrograph (50,000 times) showing the side width. The cross-sectional shape of the wiring is the scanning type. In the figure, the horizontal has two arrows. Fig. 4' shows the comparison example 2 (top half of each figure), comparative example 3 (lower left figure), and comparative example 4 (lower half right figure) of Cu# Μ〇 & %. A scanning electron micrograph (a million times) of the cross-sectional shape of the wiring of the three-layer laminated metal layer after the (four) treatment. In the figure, the line with two arrows at the horizontal line indicates the side etching width. * Figure 5 shows In Comparative Example 5, a scanning electron of a cross-sectional shape of a wiring layer formed by etching a two-layer laminated metal layer (right image) composed of Cu and M〇 and an alloy and a three-layer laminated metal layer (left and middle) Microscopic photo (5帛 times). Towel, horizontal with two arrows, 4 lines, indicating side width Fig. 6 shows a two-layer laminated metal layer (right image) composed of Cu, M〇 and M〇 alloys of Comparative Example 6, and a three-layer laminated metal layer (left and middle) after engraving treatment. Scanning electron micrograph of the cross-sectional shape of the wiring (left: 50,000 times 'middle: 10,000 times, right: 50,000 times). In the figure, the line with two arrows at the horizontal indicates the width of the undercut. 7, showing the three-layer laminated metal layer (left circle) composed of Cu and Mo in Comparative Example 7 and the three-layer laminated metal layer (right image) composed of Cu and Mo alloy on the wiring after the etching treatment. Scanning electron micrograph (10,000 times) of the surface shape. In the figure, the horizontal line with two arrows indicates the side etching width. [Simplified illustration] 20 200916606 Fig. 1 ' shows the example i (left and Fig. 2 and Fig. 2 (right) A broom-type electron micrograph (50,000 times) of a cross-sectional taper of a wiring of a three-layer laminated metal layer composed of Cu and Mg alloy after the remaining treatment. Fig. 2' shows the use of ~ and M in Example 3. The laminated metal layer formed by the layered metal layer is subjected to a cross-sectional taper of the wiring (4) electron microscopy (50,000 times). Figure 3 shows the cross-sectional shape of the wiring after the force etching treatment of the three-layer laminated metal layer (left) and the three-layer laminated metal layer (right) formed by the alloy of Comparative Example i. Scanning electron micrograph (50,000 times). In the figure, the line with two arrows at the horizontal line indicates the width of the side surname. The comparison example is - _ - V , ^ ^ y , 疋 early parent example 3 (below In the semi-left image), in Comparative Example 4 (the lower half of the right figure), the Cu^Mqm〇 alloy, and the 3; laminated metal layer is a broom-type electron micrograph of the cross-sectional shape of the wiring after the surname treatment (10,000) In the figure, the line with two arrows at the horizontal line indicates the width of the side surname. Fig. 5 shows the two-layer laminated metal layer (pictured right) and three layers of the composite of Cu and Mo and Mo alloy of Comparative Example 5. Metal | (Left figure and scanning electron microscopy of the cross-sectional shape of the wiring after the money engraving, photo (50,000 times). In the figure, the line with two arrows at the horizontal indicates the side money Figure 6' shows the comparison Example 6 is a two-layer laminated metal layer composed of Cu Xiao Mo and Mo alloy (right) and three layers of laminated metal f (left and Middle) Scanning electron microscopy of the cross-sectional shape of the wiring after etching treatment 200916606 Mirror photograph (left: 50,000 times, middle: 10,000 times, right: 50,000 times). The line with two arrows indicates the side etching width. Fig. 7 shows a three-layer laminated metal layer composed of Cu and Mo in Comparative Example 7 (left) and a three-layer laminated metal layer composed of Cu and Mo alloy. (Right) Scanning electron micrograph (10,000 times) of the cross-sectional shape of the wiring after the etching process. In the figure, the line with two arrows at the horizontal line indicates the side etching width. [Main component symbol description] None 22

Claims (1)

200916606 十、申請專利範園：200916606 X. Applying for a patent garden: 含有選自由水溶液為鹼性之磷酸鹽及水溶液為 或銅合金之1層 構成之多層積層 刻’必要成分係 液為驗性之缓酸 鹽所構成之群之至少一種鹽與過氧化氫與水而成。 2·如申請專利範圍第丨項之蝕刻組成物，其中，該璃 鹽係選自由磷酸三銨及磷酸三胺鹽所構成之群之至少 3. 如申請專利範圍第1項之蝕刻組成物，其中，該羧酸 鹽為醋酸胺鹽。 4. 如申請專利範圍第2項之蝕刻組成物，其中，該羧酸 鹽為醋酸胺鹽。 5·如申請專利範圍第1至4項中任一項之蝕刻組成物， 其pH為8〜11。 6·如申請專利範圍第1項之蝕刻組成物，其係用以同時 對由銅之1層或複數層與鉬合金之1層或複數層所構成之 多層積層金屬層之銅及鉬合金進行蝕刻。 十一、圈式·· 如次頁 23a multi-layered layered layer containing a layer of a phosphate selected from an aqueous solution of an alkaline solution and an aqueous solution of a copper alloy or a copper alloy, wherein the essential component liquid is at least one salt of the group consisting of a test acid retardant and hydrogen peroxide and water. Made. The etch composition of the invention of claim 1, wherein the glass salt is selected from the group consisting of triammonium phosphate and triammonium phosphate. Wherein the carboxylate is an amine acetate salt. 4. The etching composition of claim 2, wherein the carboxylate is an ammonium acetate salt. 5. The etching composition according to any one of claims 1 to 4, which has a pH of from 8 to 11. 6. The etching composition of claim 1 is for simultaneously performing copper and molybdenum alloy of a multi-layer laminated metal layer composed of one or more layers of copper and one or more layers of a molybdenum alloy. Etching.十一,圈式·· 如次页 23
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CN102687251B (en) * 2009-12-15 2016-02-17 三菱瓦斯化学株式会社 Etching solution and use its manufacture method of semiconductor device
KR101825493B1 (en) 2010-04-20 2018-02-06 삼성디스플레이 주식회사 Etchant for electrode and method of fabricating thin film transistor array panel using the same
KR20120015485A (en) * 2010-08-12 2012-02-22 동우 화인켐 주식회사 Texture etching solution compositon and texture etching method of crystalline silicon wafers
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WO2013005631A1 (en) * 2011-07-04 2013-01-10 三菱瓦斯化学株式会社 Etching liquid for copper or compound having copper as primary component
KR102048022B1 (en) * 2012-12-18 2019-12-02 주식회사 동진쎄미켐 Composition for etching metal layer and method for etching using the same
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TWI789741B (en) * 2020-04-14 2023-01-11 美商恩特葛瑞斯股份有限公司 Method and composition for etching molybdenum
CN112981405B (en) * 2021-02-23 2022-11-15 江苏艾森半导体材料股份有限公司 Titanium-tungsten etching solution and preparation method and application thereof
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