TW201900928A - Etching liquid composition and etching method - Google Patents

Etching liquid composition and etching method Download PDF

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TW201900928A
TW201900928A TW107114896A TW107114896A TW201900928A TW 201900928 A TW201900928 A TW 201900928A TW 107114896 A TW107114896 A TW 107114896A TW 107114896 A TW107114896 A TW 107114896A TW 201900928 A TW201900928 A TW 201900928A
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etching
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mass
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TWI779028B (en
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齊藤康太
檜垣忠弘
森貴裕
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日商Ａｄｅｋａ股份有限公司
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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
    • 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
    • C23F1/28—Acidic compositions for etching iron group 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
    • H01L21/302—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
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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

Abstract

Provided is an etching liquid composition capable, even when etching a laminate comprising a copper-based layer and a metal layer containing nickel and/or chromium at one time, of forming fine lines with few tapering widths, good linearity and limited occurrence of large chips. The etching liquid composition is for etching a layer containing at least one kind of metal selected from the group consisting of copper, nickel and chromium. Said etching liquid composition contains: (A) 0.1-10 mass% of ferric ions; (B) 0.1-10 mass% of chloride ions; (C) 0.01-5 mass% of formate ions; (D) 0.01-10 mass% of at least one kind of compound selected from the group consisting of compounds represented by general formula (1) and C1-4 straight and branched alcohols; (E) 0.01-10 mass% of at least one kind of compound selected from a group consisting of compounds represented by general formula (2), phosphonic acid compounds and salts thereof, aminocarboxylic acid compounds and salts thereof, polycarboxylic acid compounds and salts thereof, and mono-anhydrides and dianhydrides obtained by dehydration of polycarboxylic acid compounds; and water.

Description

蝕刻液組成物及蝕刻方法  Etching liquid composition and etching method  

本發明係關於蝕刻液組成物、及使用其之蝕刻方法。更詳言之，係關於用於對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬之層施行蝕刻的蝕刻液組成物，及使用其之蝕刻方法。 The present invention relates to an etching liquid composition and an etching method using the same. More specifically, it relates to an etching liquid composition for etching a layer containing at least one metal selected from the group consisting of copper, nickel, and chromium, and an etching method using the same.

用於對含有銅、鎳、及鉻中至少任一者之層施行蝕刻的濕式蝕刻相關技術，已知有各種技術。 Various techniques are known for wet etching related techniques for etching a layer containing at least one of copper, nickel, and chromium.

例如專利文獻1所提案的蝕刻液組成物，係用於統括對由氧化銦系被膜與金屬系被膜所構成積層膜施行蝕刻，含有：鐵(III)離子成分、氯化氫成分、及特定化合物成分的水溶液。專利文獻1揭示有：當利用該蝕刻液組成物，對含有氧化銦錫(ITO)膜與銅(Cu)膜的積層膜施行統括蝕刻時，在ITO膜與Cu膜間不致發生較大梯度，且窄化幅度少，能獲得直線性佳的細線。 For example, the etching liquid composition proposed in Patent Document 1 is used to collectively etch a laminated film composed of an indium oxide-based coating film and a metal-based coating film, and contains an iron (III) ion component, a hydrogen chloride component, and a specific compound component. Aqueous solution. Patent Document 1 discloses that when the etching liquid composition is used to collectively etch a laminated film containing an indium tin oxide (ITO) film and a copper (Cu) film, a large gradient does not occur between the ITO film and the Cu film. Moreover, the narrowing range is small, and a thin line with good linearity can be obtained.

專利文獻2所揭示的蝕刻液，係能提升與樹脂等被黏材間之密接性的不銹鋼用蝕刻液，含有：酸、鐵(III)離子、鹵化物離子、兩性界面活性劑、及特定金屬離子。 The etching liquid disclosed in Patent Document 2 is an etching liquid for stainless steel which can improve the adhesion to a material such as a resin, and includes an acid, iron (III) ion, a halide ion, an amphoteric surfactant, and a specific metal. ion.

再者，專利文獻3所揭示的蝕刻液，係恆範鋼合金用蝕刻液，含有：氯化銅(II)或三氯化鐵、鹽酸、聚乙二醇衍生物、以及蠟或防銹油等親油性碳氫化合物類。 Further, the etching liquid disclosed in Patent Document 3 is an etching liquid for a constant-van steel alloy, and contains: copper (II) chloride or ferric chloride, hydrochloric acid, a polyethylene glycol derivative, and wax or rust preventive oil. Equivalent lipophilic hydrocarbons.

再者，專利文獻4所揭示的蝕刻劑，係含鉻基材用蝕刻劑組成物，含有鐵氰化鉀(potassium ferricyanide)與螯合劑。 Further, the etchant disclosed in Patent Document 4 is an etchant composition containing a chromium substrate, and contains potassium ferricyanide and a chelating agent.

[先前技術文獻]  [Previous Technical Literature]   [專利文獻]  [Patent Literature]  

[專利文獻1]國際公開第2013/136624號 [Patent Document 1] International Publication No. 2013/136624

[專利文獻2]日本專利特開2017-014607號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2017-014607

[專利文獻3]日本專利特開2004-238666號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-238666

[專利文獻4]日本專利特開2004-277854號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-277854

但是，例如使用習知蝕刻液組成物，對分別由銅層、鎳層、及鉻層所形成之基體施行蝕刻時，有藉蝕刻所形成之細線的窄化幅度變大、直線性降低、出現蛇行之情形。又，例如使用習知蝕刻液組成物，欲對由銅層、鎳層、及鉻層所構成積層體統括施行蝕刻時，大多無法統括蝕刻。此情況，假設即使可統括蝕刻，但所形成細線的直線性低、細線出現蛇行、或細線出現所謂「鼠囓」(mouse bite)的較大缺損(長度3μm以上的缺損)。 However, for example, when a substrate formed of a copper layer, a nickel layer, and a chromium layer is etched by using a conventional etching liquid composition, the narrowing width of the thin line formed by the etching is increased, and the linearity is lowered and appears. The situation of snakes. Further, for example, when a conventional etching liquid composition is used, it is often impossible to collectively etch a laminate including a copper layer, a nickel layer, and a chromium layer. In this case, it is assumed that even if the etching is integrated, the linearity of the formed thin lines is low, the fine lines appear serpentine, or the thin lines have a large defect called "mouse bite" (a defect having a length of 3 μm or more).

緣是，本發明在於提供：即使統括對含有銅系層、與含鎳及鉻中至少其中一者之金屬系層的積層體施行蝕刻的情況，仍可形成窄化幅度少、直線性佳、且抑制發生較大缺損之細線，用於對含有銅、鎳、及鉻中至少1種之層施行蝕刻用的蝕刻液組成物。又，本發明在於提供：使用上述蝕刻液組成物的蝕刻方法。 In the meantime, the present invention provides that even if a laminate including a copper-based layer and a metal-based layer containing at least one of nickel and chromium is etched, the narrowing width and the linearity are small. Further, a thin line for suppressing occurrence of a large defect is used for an etching liquid composition for etching a layer containing at least one of copper, nickel, and chromium. Moreover, the present invention provides an etching method using the above etching liquid composition.

本發明者等經深入鑽研，結果發現藉由依特定範圍量含有特定成分的蝕刻液組成物，即使統括對上述積層體施行蝕刻的情況，因蝕刻造成的窄化幅度少、能獲得直線性佳的細線，遂完成本發明。 As a result of intensive studies, the inventors of the present invention have found that the etching liquid composition containing a specific component in a specific range amount can reduce the narrowing by etching and obtain good linearity even when the laminated body is etched. Thin lines, 遂 completed the present invention.

即，本發明所提供的蝕刻液組成物，係用於對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬之層，施行蝕刻的蝕刻液組成物；含有：(A)鐵(III)離子0.1~10質量%；(B)氯化物離子0.1~10質量%；(C)甲酸離子0.01~5質量%；(D)從下述一般式(1)所示化合物與碳原子數1~4之直鏈或分支狀醇所構成群組中選擇至少1種化合物0.01~10質量%；(E)從下述一般式(2)所示化合物、膦酸化合物及其鹽、胺基羧酸化合物及其鹽、二元以上羧酸化合物及其鹽、及由二元以上羧酸化合物施行脫水的單酐與二酐所構成群組中選擇至少1種化合物0.01~10質量%；以及水。 That is, the etching liquid composition provided by the present invention is an etching liquid composition for etching a layer containing at least one metal selected from the group consisting of copper, nickel, and chromium; and contains: (A) Iron (III) ion 0.1 to 10% by mass; (B) chloride ion 0.1 to 10% by mass; (C) formic acid ion 0.01 to 5% by mass; (D) compound and carbon represented by the following general formula (1) At least one compound selected from the group consisting of linear or branched alcohols having 1 to 4 atoms is 0.01 to 10% by mass; (E) a compound represented by the following general formula (2), a phosphonic acid compound and a salt thereof, At least one compound selected from the group consisting of an aminocarboxylic acid compound and a salt thereof, a divalent or higher carboxylic acid compound and a salt thereof, and a monoanhydride and a dianhydride which are dehydrated by a divalent or higher carboxylic acid compound are 0.01 to 10% by mass. ; and water.

(上述一般式(1)中，R1與R3係表示各自獨立的氫原子、或碳原子數1~4之直鏈或分支狀烷基；R2係表示碳原子數1~4之直鏈或分支狀伸烷基；n係表示1~3之數值。) (In the above general formula (1), R 1 and R 3 each represent a hydrogen atom independently or a linear or branched alkyl group having 1 to 4 carbon atoms; and R 2 represents a straight carbon number of 1 to 4; Chain or branched alkyl; n is a value from 1 to 3.)

(上述一般式(2)中，R4係表示碳原子數2~6之伸烷基；X1、X2及X3係表示下述一般式(3)所示基；X4係表示氫原子、或下述一般式(3)所示基；z係表示1~5之數值。) (In the above general formula (2), R 4 represents an alkylene group having 2 to 6 carbon atoms; X 1 , X 2 and X 3 represent a group represented by the following general formula (3); and X 4 represents hydrogen; An atom, or a group represented by the following general formula (3); a z system representing a value of 1 to 5.)

(上述一般式(3)中、R5與R6係表示伸乙基或伸丙基；當R5為伸乙基時，R6為伸丙基；當R5為伸丙基的情況，R6為伸乙基；p與q係表示上述一般式(2)所示化合物之數量平均分子量為200~30,000、且環氧乙烷基含有量成為10~80質量%的數值；*係表示鍵結手。環氧乙烷與環氧丙烷的加成形態可為無規狀與嵌段狀之任一種。) (In the above general formula (3), R 5 and R 6 represent an ethyl group or a propyl group; when R 5 is an ethyl group, R 6 is a propyl group; and when R 5 is a propyl group, R 6 is an ethylidene group; and p and q are numbers indicating that the compound of the above general formula (2) has a number average molecular weight of 200 to 30,000 and an oxirane group content of 10 to 80% by mass; * indicates Bonding. The addition form of ethylene oxide and propylene oxide can be either random or block.)

再者，本發明所提供的蝕刻方法，係包括使用上述蝕刻液組成物，對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬之層施行蝕刻的步驟。 Furthermore, the etching method according to the present invention includes the step of etching a layer containing at least one metal selected from the group consisting of copper, nickel, and chromium by using the etching liquid composition.

根據本發明可提供即使統括對含有銅系層、以及鎳與鉻中至少其中一者之金屬系層的積層體施行蝕刻時，仍可形成窄化幅度少、直線性佳、且抑制了較大缺損發生的細線，用於對含有銅、鎳、及鉻中至少1種之層施行蝕刻用的蝕刻液組成物。又，根據本發明可提供使用上述蝕刻液組成物的蝕刻方法。 According to the present invention, it is possible to provide a laminate having a copper-based layer and a metal-based layer of at least one of nickel and chromium, and it is possible to form a narrowing width, a good linearity, and a large suppression. The thin line in which the defect occurs is used for an etching liquid composition for etching a layer containing at least one of copper, nickel, and chromium. Further, according to the present invention, an etching method using the above etching liquid composition can be provided.

以下，針對本發明實施形態進行具體說明。本發明一實施形態的蝕刻液組成物(以下亦簡稱「蝕刻液組成物」)，係用於對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬的層(以下亦稱「被蝕刻材」)施行蝕刻者。該蝕刻液組成物係分別依後述特定濃度含有後述(A)~(E)成分，且含有水。所以，利用該蝕刻液組成物，即使對含有銅系層、及含有鎳與鉻中至少其中一者之金屬系層的積層體施行統括蝕刻時，仍可形成窄化幅度少、具有所需寬度的細線。又，此時可形成直線性佳、且抑制了較大缺損發生的細線。 Hereinafter, embodiments of the present invention will be specifically described. An etching liquid composition (hereinafter also referred to as "etching liquid composition") according to an embodiment of the present invention is used for a layer containing at least one metal selected from the group consisting of copper, nickel, and chromium (hereinafter also referred to as The "etched material" is applied to the etcher. Each of the etching liquid compositions contains components (A) to (E) described below at a specific concentration described later, and contains water. Therefore, even if the etching liquid composition is subjected to a general etching process for a laminate including a copper-based layer and a metal-based layer containing at least one of nickel and chromium, a narrowing width and a desired width can be formed. Thin line. Further, at this time, it is possible to form a thin line which is excellent in linearity and which suppresses generation of a large defect.

本說明書中所謂「蝕刻」係指利用化學藥物等腐蝕作用的塑形或表面加工技法。蝕刻液組成物的具體用途係可舉例如：除去劑、表面平滑化劑、表面粗化劑、圖案形成用藥劑、基體上微量附著成分的洗淨液等。蝕刻液組成物因為對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬之層的除去速度快速，因而適合用作為除去劑。又，若使用於具三次元構造之微細形狀圖案的形成，可獲得矩 形等所需形狀的圖案，因而亦適合用作為圖案形成用藥劑。 The term "etching" as used herein refers to a shaping or surface processing technique using a corrosive action such as a chemical drug. Specific examples of the use of the etching liquid composition include a removing agent, a surface smoothing agent, a surface roughening agent, a pattern forming agent, and a cleaning solution for a trace amount of a component on a substrate. The etchant composition is suitable as a remover because it has a high removal rate for a layer containing at least one metal selected from the group consisting of copper, nickel, and chromium. Further, when it is used for the formation of a fine-shaped pattern having a three-dimensional structure, a pattern having a desired shape such as a rectangular shape can be obtained, and thus it is also suitable as a medicine for pattern formation.

本說明書的「銅系層」係包含銅(純銅)層、及以銅為主成分的合金(銅合金)層之總稱。銅合金層係含有銅50質量%以上(較佳60質量%以上)的合金層。銅合金層係可含有例如：鋅、鉛、錫、鐵、鋁、鎳、鉻、及錳等中之1或2以上的銅以外金屬。 The "copper layer" in the present specification is a general term for a copper (pure copper) layer and an alloy (copper alloy) layer mainly composed of copper. The copper alloy layer contains an alloy layer of 50% by mass or more (preferably 60% by mass or more) of copper. The copper alloy layer may contain, for example, a metal other than copper of one or more of zinc, lead, tin, iron, aluminum, nickel, chromium, and manganese.

本說明書所謂「含有鎳與鉻中至少其中一者的金屬系層」，若為上述銅系層以外的金屬層，且含有鎳與鉻中之至少其中一者，其餘並無特別的限定。該金屬系層係可舉例如：鎳層、鉻層、以及含有鎳與鉻中之至少其中一者的合金層等。該合金層中可含的鎳與鉻以外之金屬，係可舉例如：銅、鐵、銀、白金、金、鋁、鈦、鉬、鈷、鎢、及鈀等。 In the present specification, the "metal layer containing at least one of nickel and chromium" is not particularly limited as long as it is a metal layer other than the copper layer and contains at least one of nickel and chromium. The metal layer may be, for example, a nickel layer, a chromium layer, or an alloy layer containing at least one of nickel and chromium. Examples of the metal other than nickel and chromium which may be contained in the alloy layer include copper, iron, silver, platinum, gold, aluminum, titanium, molybdenum, cobalt, tungsten, and palladium.

蝕刻液組成物係含有(A)鐵(III)離子(以下亦稱「(A)成分」)。藉由蝕刻液組成物中使用能供應(生成)鐵(III)離子的化合物，可使蝕刻液組成物含有鐵(III)離子。可對蝕刻液組成物中供應鐵(III)離子的化合物係可舉例如：氯化鐵(III)、溴化鐵(III)、碘化鐵(III)、硫酸鐵(III)、硝酸鐵(III)、及醋酸鐵(III)等。該等化合物係可為無水物、亦可為水合物。又，可對蝕刻液組成物中供應鐵(III)離子的化合物係可單獨使用1種、亦可併用2種以上。可供應(A)成分的化合物中，較佳係使用氯化鐵(III)。 The etching liquid composition contains (A) iron (III) ions (hereinafter also referred to as "(A) component"). The etching liquid composition contains iron (III) ions by using a compound capable of supplying (generating) iron (III) ions in the etching liquid composition. The compound which can supply iron (III) ions to the etching liquid composition may, for example, be iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate or iron nitrate ( III), and iron (III) acetate and the like. These compounds may be anhydrous or hydrated. Further, the compound which can supply the iron (III) ion to the etching liquid composition may be used singly or in combination of two or more kinds. Among the compounds which can supply the component (A), iron (III) chloride is preferably used.

蝕刻液組成物中的(A)成分(鐵(III)離子)濃度(含有量)係0.1~10 質量%。若(A)成分的濃度未滿0.1質量%，無法獲得充分的蝕刻速度。另一方面，若(A)成分的濃度超過10質量%，則導致蝕刻速度變快，難以控制蝕刻速度。(A)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(A)成分的濃度較佳係0.2~5質量%、更佳係0.5~3質量%。 The concentration (content) of the component (A) (iron (III) ion) in the etching liquid composition is 0.1 to 10% by mass. If the concentration of the component (A) is less than 0.1% by mass, a sufficient etching rate cannot be obtained. On the other hand, when the concentration of the component (A) exceeds 10% by mass, the etching rate is increased, and it is difficult to control the etching rate. The concentration of the component (A) is appropriately adjusted within the above concentration range in accordance with the thickness and width of the material to be etched. The concentration of the component (A) is preferably 0.2 to 5% by mass, more preferably 0.5 to 3% by mass.

蝕刻液組成物係含有(B)氯化物離子(以下亦稱「(B)成分」)。藉由蝕刻液組成物中使用可供應(生成)氯化物離子的化合物，可使蝕刻液組成物含有氯化物離子。可對蝕刻液組成物中供應氯化物離子的化合物，係可舉例如：氯化鐵(III)、氯化氫、氯化銨、氯化鈉、氯化鉀、及氯化鋰等。可對蝕刻液組成物中供應氯化物離子的化合物係可單獨使用1種、亦可併用2種以上。可供應(B)成分的化合物中，較佳係使用氯化鐵(III)、氯化氫，更佳係組合使用氯化鐵(III)與氯化氫。 The etching liquid composition contains (B) chloride ions (hereinafter also referred to as "(B) component"). The etching liquid composition contains chloride ions by using a compound capable of supplying (generating) chloride ions in the etching liquid composition. Examples of the compound which can supply a chloride ion to the etching liquid composition include iron (III) chloride, hydrogen chloride, ammonium chloride, sodium chloride, potassium chloride, and lithium chloride. The compound which can supply a chloride ion to the etchant composition can be used singly or in combination of two or more. Among the compounds which can supply the component (B), iron (III) chloride and hydrogen chloride are preferably used, and more preferably, iron (III) chloride and hydrogen chloride are used in combination.

蝕刻液組成物中的(B)成分(氯化物離子)濃度(含有量)係0.1~10質量%。若(B)成分濃度未滿0.1質量%，則蝕刻速度變為過慢，生產性降低。另一方面，若(B)成分的濃度超過10質量%，則蝕刻速度變為過快，會有較難控制蝕刻速度、或使被蝕刻材周邊構件、光阻等劣化的情況。(B)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(B)成分的濃度較佳係0.2~8質量%、更佳係0.5~5質量%。 The concentration (content) of the component (B) (chloride ion) in the etching liquid composition is 0.1 to 10% by mass. When the concentration of the component (B) is less than 0.1% by mass, the etching rate becomes too slow and the productivity is lowered. On the other hand, when the concentration of the component (B) exceeds 10% by mass, the etching rate becomes too fast, and it may be difficult to control the etching rate or deteriorate the peripheral member, the photoresist, or the like of the material to be etched. The concentration of the component (B) is appropriately adjusted within the above concentration range in accordance with the thickness and width of the material to be etched. The concentration of the component (B) is preferably 0.2 to 8% by mass, more preferably 0.5 to 5% by mass.

蝕刻液組成物係含有(C)甲酸離子(以下亦稱「(C)成分」)。藉 由蝕刻液組成物中使用可供應(生成)甲酸離子的化合物，可使蝕刻液組成物含有甲酸離子。可對蝕刻液組成物供應甲酸離子的化合物係可舉例如：甲酸、甲酸鈉、甲酸鎂、甲酸鉀、甲酸鈣、甲酸錳、甲酸鈷、甲酸鎳、甲酸銅、甲酸鋅、甲酸鍶、甲酸鎘、及甲酸鋇等。可對蝕刻液組成物中供應甲酸離子的化合物係可單獨使用1種、亦可併用2種以上。可供應(C)成分的化合物中，較佳係使用甲酸。 The etching liquid composition contains (C) formic acid ions (hereinafter also referred to as "(C) component"). By using a compound capable of supplying (forming) formic acid ions in the composition of the etching liquid, the etching liquid composition can contain formic acid ions. Examples of the compound which can supply formic acid ions to the etching liquid composition include formic acid, sodium formate, magnesium formate, potassium formate, calcium formate, manganese formate, cobalt formate, nickel formate, copper formate, zinc formate, cesium formate, and cadmium formate. And cesium formate and the like. The compound which can supply the formic acid ion to the etchant composition can be used singly or in combination of two or more. Among the compounds which can supply the component (C), formic acid is preferably used.

蝕刻液組成物中的(C)成分(甲酸離子)濃度(含有量)係0.01~5質量%。若(C)成分的濃度未滿0.01質量%，則蝕刻速度變為過慢，生產性降低。另一方面，若(C)成分的濃度超過5質量%，則蝕刻速度過快，有難以控制蝕刻速度的情況。(C)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(C)成分的濃度較佳係0.05~3質量%、更佳係0.1~2質量%。 The concentration (content) of the component (C) (formate ion) in the etching liquid composition is 0.01 to 5% by mass. When the concentration of the component (C) is less than 0.01% by mass, the etching rate becomes too slow and the productivity is lowered. On the other hand, when the concentration of the component (C) exceeds 5% by mass, the etching rate is too fast, and it may be difficult to control the etching rate. The concentration of the component (C) can be appropriately adjusted within the above concentration range in accordance with the thickness and width of the material to be etched. The concentration of the component (C) is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass.

蝕刻液組成物係含有從(D)下述一般式(1)所示化合物、及碳原子數1~4之直鏈或分支狀醇所構成群組中選擇至少1種化合物(以下亦稱「(D)成分」)。 The etching liquid composition contains at least one compound selected from the group consisting of (D) a compound represented by the following general formula (1) and a linear or branched alcohol having 1 to 4 carbon atoms (hereinafter also referred to as " (D) Ingredients").

一般式(1)中，R1與R3係表示各自獨立的氫原子、或碳原子數1~4之直鏈或分支狀烷基。R2係表示碳原子數1~4之直鏈或分支狀伸烷基。n係表示1~3之數值。 In the general formula (1), R 1 and R 3 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. R 2 represents a linear or branched alkyl group having 1 to 4 carbon atoms. The n system represents the value of 1 to 3.

一般式(1)中，R1與R3所示碳原子數1~4之直鏈或分支狀烷基，係可舉例如：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、及異丁基等。R1與R3較佳係氫原子、甲基、乙基、丙基、正丁基。 In the general formula (1), a linear or branched alkyl group having 1 to 4 carbon atoms represented by R 1 and R 3 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a n-butyl group. Base, second butyl, tert-butyl, and isobutyl. R 1 and R 3 are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a n-butyl group.

一般式(1)中，R2所示碳原子數1~4之直鏈或分支狀伸烷基係可舉例如：亞甲基、伸乙基、伸正丙基、異伸丙基、伸正丁基、伸第二丁基、伸第三丁基、及伸異丁基等。R2較佳係伸丙基或異伸丙基、更佳係異伸丙基。 In the general formula (1), the straight-chain or branched alkyl group having 1 to 4 carbon atoms represented by R 2 may, for example, be a methylene group, an exoethyl group, an exo-propyl group, an exo-propyl group or a di-n-butyl group. The base, the second butyl group, the third butyl group, and the isobutyl group. R 2 is preferably a propyl or exo-propyl group, more preferably an exo-propyl group.

能使用為(D)成分的一般式(1)所示化合物係可舉例如：乙二醇單甲醚、二乙二醇單甲醚、三乙二醇單甲醚、乙二醇單異丙醚、二乙二醇單異丙醚、乙二醇單丁醚、二乙二醇單丁醚、三乙二醇單丁醚、乙二醇單異丁醚、二乙二醇單異丁醚、丙二醇單甲醚、二丙二醇單甲醚、三丙二醇單甲醚、丙二醇單丙醚、二丙二醇單丙醚、丙二醇單丁醚、二丙二醇單丁醚、三丙二醇單丁醚、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、二乙二醇甲基***、二乙二醇二***、二乙二醇二丁醚、及二丙二醇二甲醚等二醇醚類。 The compound represented by the general formula (1) which can be used as the component (D) may, for example, be ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether or ethylene glycol monoisopropyl ester. Ether, diethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether , propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, ethylene glycol Methyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether Alcohol ethers.

再者，能使用為(D)成分的碳原子數1~4之直鏈或分支狀醇，係可舉例如：甲醇、乙醇、丙醇、異丙醇、丁醇、2-丁醇、異丁醇、及第三丁醇等醇類。 Further, a linear or branched alcohol having 1 to 4 carbon atoms which is a component (D) can be used, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, and the like. An alcohol such as butanol or tert-butanol.

上述一般式(1)所示化合物較佳係下述一般式(1-A)所示化合物。下述一般式(1-A)中的R1、R3、及n分別係與一般式(1)中的R1、R3、及n同義。 The compound represented by the above formula (1) is preferably a compound represented by the following general formula (1-A). R 1 , R 3 and n in the following general formula (1-A) are synonymous with R 1 , R 3 and n in the general formula (1), respectively.

若(D)成分係使用上述一般式(1-A)所示化合物、及碳原子數3或4之分支狀醇中至少其中一者，則藉由使用蝕刻液組成物施行的蝕刻，可輕易形成窄化幅度小、且直線性佳的細線，故屬較佳。又，當使用二丙二醇單甲醚與異丙醇中至少其中一者的情況，可更加提高上述效果故屬更佳，特佳係二丙二醇單甲醚。 When the component (D) is at least one of the compound represented by the above general formula (1-A) and the branched alcohol having 3 or 4 carbon atoms, the etching by the etching liquid composition can be easily performed. It is preferable to form a thin line having a small narrowing width and good linearity. Further, when at least one of dipropylene glycol monomethyl ether and isopropyl alcohol is used, the above effect can be further improved, and it is more preferable to use dipropylene glycol monomethyl ether.

蝕刻液組成物中的(D)成分濃度(含有量)係0.01~10質量%。若(D)成分的濃度未滿0.01質量%，無法顯現出(D)成分的摻合效果。另一方面，即使(D)成分的濃度超過10質量%，但(D)成分的摻合效果並無法獲得進一步的提升。(D)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(D)成分的濃度較佳係0.05~8質量%、更佳係0.1~5質量%。 The concentration (content) of the component (D) in the etching liquid composition is 0.01 to 10% by mass. When the concentration of the component (D) is less than 0.01% by mass, the blending effect of the component (D) cannot be exhibited. On the other hand, even if the concentration of the component (D) exceeds 10% by mass, the blending effect of the component (D) cannot be further improved. The concentration of the component (D) is appropriately adjusted within the above concentration range in accordance with the thickness and width of the material to be etched. The concentration of the component (D) is preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

蝕刻液組成物係含有從(E)下述一般式(2)所示化合物、膦酸化合物及其鹽、胺基羧酸化合物及其鹽、二元以上羧酸化合物及其鹽、以及由二元以上羧酸化合物進行脫水而形成的單酐及二酐所構成群組中選擇至少1種化合物(以下亦稱「(E)成分」)。 The etching liquid composition contains (E) a compound represented by the following general formula (2), a phosphonic acid compound and a salt thereof, an aminocarboxylic acid compound and a salt thereof, a divalent or higher carboxylic acid compound and a salt thereof, and At least one compound (hereinafter also referred to as "(E) component") is selected from the group consisting of monoanhydride and dianhydride formed by dehydration of a carboxylic acid compound.

一般式(2)中，R4係表示碳原子數2~6之伸烷基；z係表示1~5之數值。X1、X2及X3係表示下述一般式(3)所示基；X4係表示氫原子、或下述一般式(3)所示基。 In the general formula (2), R 4 represents an alkylene group having 2 to 6 carbon atoms; and z is a numerical value of 1 to 5. X 1 , X 2 and X 3 represent a group represented by the following general formula (3); and X 4 represents a hydrogen atom or a group represented by the following general formula (3).

一般式(3)中，R5與R6係表示伸乙基或伸丙基；若R5為伸乙基的情況，R6為伸丙基；R5為伸丙基的情況，R6為伸乙基。p與q係表示使一般式(2)所示化合物成為數量平均分子量為200~30,000、且環氧乙烷基含有量成為10~80質量%的數值；*係表示鍵結手。環氧乙烷與環氧丙烷的加成形態為無規狀或嵌段狀之任一種。 In the general formula (3), R 5 and R 6 represent an ethyl group or a propyl group; if R 5 is an ethyl group, R 6 is a propyl group; and R 5 is a propyl group, R 6 For the extension of ethyl. The p and q systems represent a numerical value of the compound represented by the general formula (2) in a number average molecular weight of 200 to 30,000 and an oxirane group content of 10 to 80% by mass; * means a bonding hand. The addition form of ethylene oxide and propylene oxide is either a random form or a block form.

一般式(2)中，R4所示碳原子數2~6之伸烷基係可舉例如：伸乙基、伸丙基、伸丁基、伸戊基、及伸己基等。該等基可鍵結於任何位置，亦可為分支。R5或R6所示伸丙基可為-CY1H-CY2H-(Y1及Y2係表示其中一者為氫原子、另一者為甲基)，亦可為-CH2-CH2-CH2-。一般式(2)所示化合物中，R4為伸乙基、z為1、X1~X4為一般式(3)所示基的多元醇，取得較為容易。上述一般式(2) 所示化合物的數量平均分子量係200~30,000，從蝕刻速度的觀點而言，較佳係200~7,500。又，上述一般式(2)所示化合物的環氧乙烷基含有量係10~80質量%，從蝕刻速度的觀點而言，較佳係10~50質量%。 In the general formula (2), the alkylene group having 2 to 6 carbon atoms represented by R 4 may, for example, be an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. The groups can be bonded to any position or branch. The propyl group represented by R 5 or R 6 may be -CY 1 H-CY 2 H- (Y 1 and Y 2 means that one of them is a hydrogen atom and the other is a methyl group), and may also be -CH 2 -CH 2 -CH 2 -. Among the compounds represented by the general formula (2), R 4 is a polyhydric alcohol having an ethyl group extending, z being 1, and X 1 to X 4 being a group represented by the general formula (3), which is relatively easy to obtain. The number average molecular weight of the compound represented by the above formula (2) is from 200 to 30,000, and is preferably from 200 to 7,500 from the viewpoint of etching rate. Further, the compound represented by the above formula (2) has an oxirane group content of 10 to 80% by mass, and preferably 10 to 50% by mass from the viewpoint of etching rate.

能使用為(E)成分的膦酸化合物及其鹽，最好使用例如：羥亞乙基二膦酸、次氮基三亞甲基參(膦酸)、2-膦醯基丁烷-1,2,4-三羧酸、伸乙二胺四(亞甲膦酸)、二伸乙三胺五亞甲膦酸、及該等的鹼金屬(較佳係鈉)鹽等。 A phosphonic acid compound (E) component and a salt thereof can be used, and for example, hydroxyethylidene diphosphonic acid, nitrilotrimethylene phosphite (phosphonic acid), and 2-phosphonium butane-1 are preferably used. 2,4-tricarboxylic acid, ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriamine penta methylene phosphonic acid, and alkali metal (preferably sodium) salts.

能使用為(E)成分的胺基羧酸化合物及其鹽之較佳具體例，係可舉例如：天冬醯胺、絲胺酸、天冬胺酸、谷胺酸、麩胺酸、蘇胺酸、精胺酸、組胺酸、溶胞素、酪胺酸、及半胱氨酸等胺基酸；以及該等的鹼金屬(較佳係鈉)鹽等。胺基羧酸化合物及其鹽的更佳具體例，係可舉例如：伸乙二胺四醋酸、氮基三醋酸、二伸乙三胺五醋酸、N-(2-羥乙基)伸乙二胺三醋酸、三伸乙四胺六醋酸、1,3-伸丙二胺四醋酸、1,3-二胺基-2-羥丙烷四醋酸、2-羥乙基亞胺二醋酸、N,N-二(2-羥乙基)甘胺酸、二醇醚二胺四醋酸、N,N-二(羧甲基)麩胺酸、伸乙二胺二琥珀酸、四伸乙五胺七醋酸、及該等的鹼金屬(較佳係鈉)鹽等。該等之中，更佳係伸乙二胺四醋酸四鈉。 Preferred examples of the aminocarboxylic acid compound and the salt thereof which can be used as the component (E) include aspartame, serine, aspartic acid, glutamic acid, glutamic acid, and sulphate. Amino acids such as aminic acid, arginine, histidine, lysin, tyrosine, and cysteine; and such alkali metal (preferably sodium) salts and the like. More preferable examples of the aminocarboxylic acid compound and salts thereof include, for example, ethylenediaminetetraacetic acid, nitrogen triacetic acid, diethylenetriamine pentaacetic acid, and N-(2-hydroxyethyl) Diamine triacetic acid, triamethylenetetraamine hexaacetic acid, 1,3-propanediamine tetraacetic acid, 1,3-diamino-2-hydroxypropane tetraacetic acid, 2-hydroxyethylimine diacetic acid, N , N-bis(2-hydroxyethyl)glycine, glycol ether diamine tetraacetic acid, N,N-bis(carboxymethyl)glutamate, ethylenediamine disuccinic acid, tetraamethylene pentamine Heptaacetic acid, and such alkali metal (preferably sodium) salts and the like. Among these, it is more preferred to extend tetrasodium ethylenediaminetetraacetate.

能使用為(E)成分的二元以上羧酸化合物及其鹽，係可舉例如：草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、順丁烯二酸、反丁烯二酸、蘋果酸、酒石酸、檸檬酸、以及該等的無水物及鹼金 屬(較佳係鈉)鹽等。 The divalent or higher carboxylic acid compound and the salt thereof which may be used as the component (E) may, for example, be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid or maleic acid. Fumaric acid, malic acid, tartaric acid, citric acid, and such anhydrates and alkali metal (preferably sodium) salts and the like.

能使用為(E)成分之由二元以上羧酸化合物施行脫水而形成的單酐與二酐，係可例如：藉由使上述二元以上羧酸化合物施行脫水縮合而獲得的化合物。 A monoanhydride and a dianhydride which are formed by dehydration of a divalent or higher carboxylic acid compound as the component (E) can be used, for example, a compound obtained by subjecting the above-mentioned dicarboxylic acid compound to dehydration condensation.

上述(E)成分係可從該等之中單獨使用1種、亦可併用2種以上。較佳係併用2種以上(E)成分，其中更佳係組合使用一般式(2)所示化合物、與胺基羧酸化合物或其鹽。藉由使用此種組合的(E)成分，當對含有銅系層、與含鎳與鉻中至少其中一者之金屬系層的積層體施行統括蝕刻時，能更加提高可形成直線性佳、不易發生較大缺損之細線的效果。 The above-mentioned (E) component may be used alone or in combination of two or more kinds. It is preferred to use two or more (E) components in combination, and it is more preferred to use a compound represented by the general formula (2) in combination with an aminocarboxylic acid compound or a salt thereof. By using the (E) component of such a combination, when the laminate including the copper-based layer and the metal-based layer containing at least one of nickel and chromium is collectively etched, the linearity can be further improved. The effect of thin lines that are less prone to large defects.

蝕刻液組成物中的(E)成分濃度(含有量)係0.01~10質量%。若(E)成分的濃度未滿0.01質量%，無法顯現出(E)成分的摻合效果。另一方面，即使(E)成分的濃度超過10質量%，但(E)成分的摻合效果並無法獲得進一步提升。(E)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(E)成分的濃度較佳係0.05~8質量%、更佳係0.1~5質量%。 The concentration (content) of the component (E) in the etching liquid composition is 0.01 to 10% by mass. When the concentration of the component (E) is less than 0.01% by mass, the blending effect of the component (E) cannot be exhibited. On the other hand, even if the concentration of the component (E) exceeds 10% by mass, the blending effect of the component (E) cannot be further improved. The concentration of the component (E) is appropriately adjusted within the above concentration range in accordance with the thickness and width of the material to be etched. The concentration of the component (E) is preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass.

蝕刻液組成物係更進一步含有水。蝕刻液組成物中可將水使用為溶劑，將蝕刻液組成物作成水溶液的形態。蝕刻液組成物中的水含有量最好配合前述(A)~(E)成分的濃度，將其餘部分設為水。使用後述添加劑的情況，較佳係配合(A)~(E)成分、及添加劑的濃度，其 餘部分使用水。蝕刻液組成物中的水濃度(含有量)較佳係55~99質量%左右。 The etchant composition further contains water. In the etching liquid composition, water can be used as a solvent, and the etching liquid composition can be used as an aqueous solution. The water content in the etching solution composition is preferably adjusted to the concentration of the above components (A) to (E), and the remaining portion is made into water. In the case of using an additive described later, it is preferred to blend the components (A) to (E) and the concentration of the additive, and the remainder is water. The water concentration (content) in the etching liquid composition is preferably about 55 to 99% by mass.

再者，在蝕刻液組成物中，除前述(A)~(E)成分之外，於不致妨礙本發明效果之範圍內，亦可含有周知添加劑。添加劑係可舉例如：還原劑、蝕刻液組成物的安定化劑、各成分的可溶化劑、消泡劑、比重調節劑、黏度調節劑、潤濕性改善劑、及氧化劑等。使用該等添加劑時，蝕刻液組成物中的添加劑濃度(含有量)一般分別可設為0.001~40質量%範圍。 Further, in the etching liquid composition, in addition to the above components (A) to (E), well-known additives may be contained within a range that does not impair the effects of the present invention. Examples of the additive include a reducing agent, a stabilizer for the etching liquid composition, a solubilizing agent for each component, an antifoaming agent, a specific gravity adjusting agent, a viscosity adjusting agent, a wettability improving agent, and an oxidizing agent. When these additives are used, the concentration (content) of the additive in the etching liquid composition can be generally set to be in the range of 0.001 to 40% by mass.

再者，蝕刻液組成物中，除前述(A)~(E)成分之外，在不致妨礙本發明效果之範圍內，亦可含有配合蝕刻液組成物用途的周知任意成分。任意成分係可舉例如：界面活性劑、有機酸、唑類化合物、嘧啶類化合物、硫脲類化合物、胺類化合物、烷基吡咯啶酮類化合物、聚丙烯醯胺類化合物、過氧化氫、及過硫酸鹽等。使用該等任意成分時，蝕刻液組成物中的任意成分濃度(含有量)一般分別可設為0.001質量%~10質量%範圍。當蝕刻液組成物含有上述添加劑與任意成分的情況，蝕刻液組成物中的添加劑與任意成分之合計濃度(含有量)，最好設為0.001~40質量%範圍。 Further, the etching liquid composition may contain, in addition to the above components (A) to (E), any known components which are used in combination with the use of the etching liquid composition, insofar as the effects of the present invention are not impaired. Examples of the optional component include a surfactant, an organic acid, an azole compound, a pyrimidine compound, a thiourea compound, an amine compound, an alkylpyrrolidone compound, a polypropylene guanamine compound, hydrogen peroxide, and the like. And persulfate and the like. When these optional components are used, the concentration (content) of any component in the etching liquid composition can be generally in the range of 0.001% by mass to 10% by mass. When the etching liquid composition contains the above-mentioned additive and an optional component, the total concentration (content) of the additive and the optional component in the etching liquid composition is preferably in the range of 0.001 to 40% by mass.

界面活性劑係可舉例如：氟化烷基甜菜、及氟化烷基聚氧乙烯醚等氟系兩性界面活性劑。 The surfactant may be, for example, a fluorinated alkyl beet. And a fluorine-based amphoteric surfactant such as a fluorinated alkyl polyoxyethylene ether.

有機酸係可舉例如：醋酸、丙酸、丁酸、吉草酸、己酸、丙烯 酸、巴豆酸、異巴豆酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、順丁烯二酸、反丁烯二酸、蘋果酸、酒石酸、檸檬酸、甘醇酸、乳酸、磺胺酸、菸鹼酸、抗壞血酸、羥三甲基乙酸、乙醯丙酸(levulinic acid)、及β-氯丙酸等。 Examples of the organic acid include acetic acid, propionic acid, butyric acid, oxalic acid, caproic acid, acrylic acid, crotonic acid, isocrotonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid. , maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, glycolic acid, lactic acid, sulfamic acid, nicotinic acid, ascorbic acid, hydroxytrimethylacetic acid, levulinic acid And β-chloropropionic acid.

唑類化合物係可舉例如：咪唑、2-甲基咪唑、2-十一烷基-4-甲基咪唑、2-苯基咪唑、及2-甲基苯并咪唑等烷基咪唑類；苯并咪唑、2-甲基苯并咪唑、2-十一烷基苯并咪唑、2-苯基苯并咪唑、及2-巰基苯并咪唑等苯并咪唑類；1,2,3-***、1,2,4-***、5-苯基-1,2,4-***、5-胺基-1,2,4-***、1,2,3-苯并***、1-胺基苯并***、4-胺基苯并***、1-雙胺基甲基苯并***、1-甲基-苯并***、甲苯***、1-羥基苯并***、5-甲基-1H-苯并***、及5-氯苯并***等***類；1H-四唑、5-胺基-1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-巰基-1H-四唑、1-苯基-5-巰基-1H-四唑、1-環己基-5-巰基-1H-四唑及5,5'-雙-1H-四唑等四唑類；以及苯并噻唑、2-巰基苯并噻唑、2-苯基噻唑、2-胺基苯并噻唑、2-胺基-6-硝基苯并噻唑、2-胺基-6-甲氧基苯并噻唑、及2-胺基-6-氯苯并噻唑等噻唑類等。 Examples of the azole compound include imidazole, 2-methylimidazole, 2-undecyl-4-methylimidazole, 2-phenylimidazole, and alkylimidazoles such as 2-methylbenzimidazole; benzene; Benzimidazoles such as imidazole, 2-methylbenzimidazole, 2-undecylbenzimidazole, 2-phenylbenzimidazole, 2-mercaptobenzimidazole, etc.; 1,2,3-triazole 1,2,4-triazole, 5-phenyl-1,2,4-triazole, 5-amino-1,2,4-triazole, 1,2,3-benzotriazole, 1 -Aminobenzotriazole, 4-aminobenzotriazole, 1-diaminomethylbenzotriazole, 1-methyl-benzotriazole, tolyltriazole, 1-hydroxybenzotriazole , 5-methyl-1H-benzotriazole, and triazoles such as 5-chlorobenzotriazole; 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole , 5-phenyl-1H-tetrazole, 5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-cyclohexyl-5-mercapto-1H-tetrazole and 5, Tetrazolium such as 5'-bis-1H-tetrazole; and benzothiazole, 2-mercaptobenzothiazole, 2-phenylthiazole, 2-aminobenzothiazole, 2-amino-6-nitrobenzene And thiazoles such as thiazole, 2-amino-6-methoxybenzothiazole, and 2-amino-6-chlorobenzothiazole.

嘧啶類化合物係可舉例如：二胺基嘧啶、三胺基嘧啶、四胺基嘧啶、及巰基嘧啶等。 Examples of the pyrimidine compound include diaminopyrimidine, triaminopyrimidine, tetraaminopyrimidine, and mercaptopyrimidine.

硫脲類化合物係可舉例如：硫脲、乙烯硫脲、硫二甘醇(thiodiglycol)、及硫醇等。 Examples of the thiourea compound include thiourea, ethylene thiourea, thiodiglycol, and mercaptan.

胺類化合物係可舉例如：二戊胺、二丁基胺、三乙胺、三戊胺、單乙醇胺、二乙醇胺、三乙醇胺、單異丙醇胺、二異丙醇胺、三異丙醇胺、乙醇異丙醇胺、二乙醇異丙醇胺、乙醇二異丙醇胺、聚烯丙胺、聚乙烯吡啶、及該等之鹽酸鹽等等。 Examples of the amine compound include dipentylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanol. Amine, ethanol isopropanolamine, diethanol isopropanolamine, ethanol diisopropanolamine, polyallylamine, polyvinylpyridine, and the like.

烷基吡咯啶酮類化合物係可舉例如：N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-丙基-2-吡咯啶酮、N-丁基-2-吡咯啶酮、N-戊基-2-吡咯啶酮、N-己基-2-吡咯啶酮、N-庚基-2-吡咯啶酮、及N-辛基-2-吡咯啶酮等。 The alkylpyrrolidone compound may, for example, be N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone or N-butyl- 2-pyrrolidone, N-pentyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, and N-octyl-2-pyrrolidone .

聚丙烯醯胺類化合物係可舉例如：聚丙烯醯胺、及第三丁基丙烯醯胺磺酸等。 Examples of the polypropylene amide compound include polypropylene decylamine and t-butyl acrylamide sulfonate.

過硫酸鹽係可舉例如：過硫酸銨、過硫酸鈉、及過硫酸鉀等。 Examples of the persulfate salt include ammonium persulfate, sodium persulfate, and potassium persulfate.

本發明一實施形態的蝕刻方法係包括有：使用上述蝕刻液組成物，對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬的層施行蝕刻之步驟。該蝕刻方法所使用的蝕刻液組成物係如上述，可對含有銅系層、及含有鎳與鉻中至少其中一者之金屬系層的積層體，統括施行蝕刻。所以，該蝕刻方法更佳係適用於對含有銅系層、及含有鎳與鉻中至少其中一者之金屬系層的積層體，統括施行蝕刻的情況。特佳係該蝕刻方法係適用於對含有銅(Cu)層、與含有鎳(Ni)層與鉻(Cr)層中至少其中一者之金屬系層的積層體，統括施行蝕刻的情況。 An etching method according to an embodiment of the present invention includes the step of etching a layer containing at least one metal selected from the group consisting of copper, nickel, and chromium by using the etching liquid composition. As described above, the etching liquid composition used in the etching method can be integrally etched on a laminate including a copper-based layer and a metal-based layer containing at least one of nickel and chromium. Therefore, the etching method is more preferably applied to a laminate including a copper-based layer and a metal-based layer containing at least one of nickel and chromium, and etching is generally performed. Particularly preferably, the etching method is applied to a laminate in which a copper (Cu) layer and a metal layer containing at least one of a nickel (Ni) layer and a chromium (Cr) layer are collectively etched.

積層體的銅系層與金屬系層分別可為1層、亦可為2層以上。又，積層體的銅系層與金屬系層之配置關係並無特別的限定，金屬系層係可配置於銅系層的上層、亦可配置於下層、亦可上層與下層均有配置。又，銅系層與金屬系層亦可交替積層。 The copper-based layer and the metal-based layer of the laminate may be one layer or two or more layers. Further, the arrangement relationship between the copper-based layer and the metal-based layer of the laminated body is not particularly limited, and the metal-based layer may be disposed on the upper layer of the copper-based layer, or may be disposed in the lower layer, or may be disposed in both the upper layer and the lower layer. Further, the copper layer and the metal layer may be alternately laminated.

具體的蝕刻方法並無特別的限定，可採用一般的蝕刻方法。例如可利用浸漬式、噴霧式、及旋轉式等進行的蝕刻方法。又，亦可依照批次式、流動式、以及利用蝕刻劑的氧化還原電位、比重、或酸濃度進行之自動控制式等一般方式使用蝕刻液組成物。 The specific etching method is not particularly limited, and a general etching method can be employed. For example, an etching method such as a dipping type, a spray type, or a rotary type can be used. Further, the etching liquid composition may be used in a general manner such as a batch type, a flow type, and an automatic control method using an oxidation-reduction potential, a specific gravity, or an acid concentration of an etchant.

例如利用浸漬式蝕刻方法，對在矽基板、玻璃基板等基體上，形成有由Cu層、Ni層、及Cr層所構成積層體的基材施行蝕刻時，將該基材依適當蝕刻條件浸漬於蝕刻液組成物中之後，經上拉，則可統括地對基體上的Cu層、Ni層、及Cr層施行蝕刻。 For example, when a substrate having a layered body composed of a Cu layer, a Ni layer, and a Cr layer is formed on a substrate such as a tantalum substrate or a glass substrate by an immersion etching method, the substrate is immersed under appropriate etching conditions. After the etching liquid composition, the Cu layer, the Ni layer, and the Cr layer on the substrate are collectively etched by pulling up.

浸漬式蝕刻方法的蝕刻條件並無特別的限定，可配合被蝕刻材的形狀、膜厚等任意設定。例如蝕刻溫度較佳係10~60℃、更佳係20~40℃。因為蝕刻液組成物的溫度將因反應熱而上升，因而視需要為了使蝕刻液組成物的溫度能維持於上述範圍內，亦可利用公知手段進行溫度控制。又，蝕刻時間係只要設定為被蝕刻材能被完全蝕刻的充分必要時間即可，並無特別的限定。例如若為膜厚10~1000nm左右的被蝕刻材，只要依上述溫度範圍施行1分鐘~24小時左右的蝕刻即可。 The etching conditions of the immersion etching method are not particularly limited, and can be arbitrarily set in accordance with the shape and film thickness of the material to be etched. For example, the etching temperature is preferably 10 to 60 ° C, more preferably 20 to 40 ° C. Since the temperature of the etching liquid composition rises due to the heat of reaction, temperature control can be performed by a known means in order to maintain the temperature of the etching liquid composition within the above range as needed. Further, the etching time is not particularly limited as long as it is set to a sufficient time for the etching material to be completely etched. For example, in the case of an object to be etched having a thickness of about 10 to 1000 nm, etching may be performed for about 1 minute to 24 hours in the above temperature range.

例如利用噴霧式蝕刻方法，對在矽基板、玻璃基板等基體上，形成有由Cu層、Ni層、及Cr層所構成積層體的基材施行蝕刻時，藉由將蝕刻液組成物依適當條件朝該基材施行噴霧，可統括地對基體上的Cu層、Ni層、及Cr層施行蝕刻。 For example, when a substrate having a layered body composed of a Cu layer, a Ni layer, and a Cr layer is formed on a substrate such as a tantalum substrate or a glass substrate by a spray etching method, the etching liquid composition is appropriately adjusted. Conditions The spray is applied to the substrate, and the Cu layer, the Ni layer, and the Cr layer on the substrate are collectively etched.

噴霧式蝕刻方法的蝕刻條件並無特別的限定，可配合被蝕刻材的形狀、膜厚等任意設定。例如噴霧條件係可從0.01~1.0MPa範圍內選擇，較佳係0.03~0.2MPa範圍、更佳係0.05~0.15MPa範圍。又，當使用蝕刻液組成物利用噴霧式形成細線的情況，在噴霧壓0.05~0.15MPa時，可獲得細線上寬與下寬差非常小的細線，故特佳。又，蝕刻溫度較佳係10~60℃、更佳係20~40℃。因為蝕刻液組成物的溫度將因反應熱而上升，因而視需要為了使蝕刻液組成物的溫度能維持於上述範圍內，亦可利用公知手段進行溫度控制。又，蝕刻時間係只要設定為被蝕刻材能被完全蝕刻的充分必要時間即可，並無特別的限定。例如若為膜厚800nm左右的被蝕刻材，只要依上述溫度範圍施行60~600秒左右的蝕刻即可。 The etching conditions of the spray etching method are not particularly limited, and can be arbitrarily set in accordance with the shape and film thickness of the material to be etched. For example, the spray conditions may be selected from the range of 0.01 to 1.0 MPa, preferably in the range of 0.03 to 0.2 MPa, more preferably in the range of 0.05 to 0.15 MPa. Further, when the fine liquid is formed by the spray type using the etching liquid composition, it is particularly preferable to obtain a fine line having a very small width and a small difference in width at a spray pressure of 0.05 to 0.15 MPa. Further, the etching temperature is preferably 10 to 60 ° C, more preferably 20 to 40 ° C. Since the temperature of the etching liquid composition rises due to the heat of reaction, temperature control can be performed by a known means in order to maintain the temperature of the etching liquid composition within the above range as needed. Further, the etching time is not particularly limited as long as it is set to a sufficient time for the etching material to be completely etched. For example, in the case of an object to be etched having a thickness of about 800 nm, etching may be performed for about 60 to 600 seconds in the above temperature range.

本發明一實施形態的蝕刻方法，為了使因重複進行蝕刻而劣化的蝕刻液組成物復原，亦可更進一步設有對蝕刻液組成物添加補充液的步驟。例如上述自動控制式蝕刻方法的情況，若預先在蝕刻裝置中安裝補充液，可對蝕刻液組成物添加補充液。補充液係可使用例如：(A)成分、(B)成分、及(C)成分中之至少任一成分的水溶液；以及(D)成分的水溶液等。該等水溶液(補充液)中的各成分濃度係例 如設為蝕刻液組成物中各成分濃度的3~20倍左右即可。又，在補充液中視需要亦可添加含有蝕刻液組成物必要成分、或任意成分的前述各成分。 In the etching method according to the embodiment of the present invention, in order to restore the etching liquid composition which is deteriorated by repeated etching, a step of adding a replenishing liquid to the etching liquid composition may be further provided. For example, in the case of the above-described automatic control type etching method, if a replenishing liquid is previously attached to the etching apparatus, a replenishing liquid can be added to the etching liquid composition. For the replenishing liquid, for example, an aqueous solution of at least one of the components (A), (B), and (C); and an aqueous solution of the component (D) may be used. The concentration of each component in the aqueous solution (supplemental solution) may be, for example, about 3 to 20 times the concentration of each component in the etching liquid composition. Further, the above-described respective components containing an essential component of the etching liquid composition or an optional component may be added to the replenishing liquid as needed.

上述蝕刻液組成物、及使用其的蝕刻方法，係當形成微細圖案電路佈線時可提供精密蝕刻。所以，上述蝕刻液組成物及蝕刻方法係除印刷電路板之外，尚可使用於要求超細間距的封裝用基板、COF(chip on film,chip on flexible，薄膜覆晶)、及TAB(tape automated bonding，捲帶式自動接著)用途之移除法、半加成法。 The etching liquid composition and the etching method using the same can provide precision etching when forming a fine pattern circuit wiring. Therefore, the etching liquid composition and the etching method can be used for a package substrate requiring ultra-fine pitch, COF (chip on film, chip on flexible), and TAB (tape) in addition to a printed circuit board. Sub-bonding, tape-and-reel automatic removal) use removal method, semi-additive method.

[實施例]  [Examples]  

以下，利用實施例與比較例，針對本發明進行更詳細說明，惟本發明並不因該等而受限定。 Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto.

<蝕刻液組成物>  <etching liquid composition>   (實施例1~5)  (Examples 1 to 5)  

將表1所示化合物及水，依蝕刻液組成物中的(A)~(E)成分成為表2所示濃度方式進行混合，獲得實施例1~5的蝕刻液組成物。另外，依所摻合化合物與水的合計成為100質量%方式摻合水。(A)成分(鐵(III)離子)的濃度係利用氯化鐵(III)進行調整，(B)成分(氯化物離子)的濃度係利用氯化鐵(III)與氯化氫進行調整。(E)成分係使用下示「E-1」、「E-2」、及「E-3」。 The compound shown in Table 1 and water were mixed in the concentration shown in Table 2 in the composition of the etching liquid composition, and the etching liquid compositions of Examples 1 to 5 were obtained. Further, water was blended in such a manner that the total of the blended compound and water became 100% by mass. The concentration of the component (A) (iron (III) ion) is adjusted by iron (III) chloride, and the concentration of the component (B) (B) is adjusted by using iron (III) chloride and hydrogen chloride. For the component (E), use "E-1", "E-2", and "E-3" as shown below.

E-1：伸乙二胺四醋酸四鈉 E-1: Ethylenediamine tetraacetate tetrasodium

E-2：ADEKA公司製商品名「Adeka PullulonicTR-702」[由環 氧丙烷及環氧乙烷嵌段加成於伸乙二胺之活性氫上的化合物(數量平均分子量3500、環氧乙烷含有量20質量%，一般式(2)中，R4=伸乙基、z=1、R5=伸丙基、R6=伸乙基、X4≠氫原子)] E-2: Adeka Pullulonic TR-702, manufactured by ADEKA Co., Ltd. [A compound of propylene oxide and ethylene oxide which is added to the active hydrogen of ethylenediamine (quantitative molecular weight: 3,500, ethylene oxide) The content is 20% by mass, in the general formula (2), R 4 = ethyl, z = 1, R 5 = propyl, R 6 = ethyl, X 4 ≠ hydrogen atom)

E-3：ADEKA公司製商品名「Adeka PullulonicTR-704」[由環氧丙烷及環氧乙烷嵌段加成於伸乙二胺之活性氫上的化合物(數量平均分子量5000、環氧乙烷含有量40質量%、一般式(2)中，R4=伸乙基、z=1、R5=伸丙基、R6=伸乙基、X4≠氫原子)] E-3: Adeka Pullulonic TR-704, manufactured by ADEKA Co., Ltd. [A compound of propylene oxide and ethylene oxide which is added to the active hydrogen of ethylenediamine (quantitative molecular weight: 5000, ethylene oxide) The content is 40% by mass, in the general formula (2), R 4 = ethyl, z = 1, R 5 = propyl, R 6 = ethyl, X 4 ≠ hydrogen atom)

(比較例1~3)  (Comparative examples 1 to 3)  

將表3所示化合物及水，依蝕刻液組成物中的(A)~(E)成分成為表4所示濃度方式進行混合，獲得比較例1~3的蝕刻液組成物。另外，依所摻合化合物與水的合計成為100質量%方式摻合水。(A)成分(鐵(III)離子)的濃度係利用氯化鐵(III)進行調整，(B)成分(氯化物離子)的濃度係利用氯化鐵(III)與氯化氫進行調整。 The compound shown in Table 3 and water were mixed in the concentration shown in Table 4 in accordance with the components (A) to (E) in the etching liquid composition, and the etching liquid compositions of Comparative Examples 1 to 3 were obtained. Further, water was blended in such a manner that the total of the blended compound and water became 100% by mass. The concentration of the component (A) (iron (III) ion) is adjusted by iron (III) chloride, and the concentration of the component (B) (B) is adjusted by using iron (III) chloride and hydrogen chloride.

<蝕刻方法>  <etching method>   (實施例6~10)  (Examples 6 to 10)  

對在玻璃基體上依序積層著：Cu層(厚度300nm)、Ni層(厚度 150nm)、及Cr層(厚度150nm)的基材。使用正型液狀光阻形成寬30μm、開口部30μm的光阻圖案。將已形成光阻圖案的基材裁剪為長20mm×寬20mm而獲得測試片。對所獲測試片，使用實施例1~5之蝕刻液組成物，依30℃、噴霧壓0.07MPa、180秒的條件，利用噴霧式施行圖案蝕刻，而製得屬於細線狀圖案的實施例圖案No.1~5。 A substrate of a Cu layer (thickness: 300 nm), a Ni layer (thickness: 150 nm), and a Cr layer (thickness: 150 nm) was sequentially laminated on a glass substrate. A photoresist pattern having a width of 30 μm and an opening of 30 μm was formed using a positive liquid photoresist. The substrate on which the photoresist pattern had been formed was cut into a length of 20 mm × a width of 20 mm to obtain a test piece. Using the etching liquid compositions of Examples 1 to 5, the obtained test pieces were subjected to pattern etching by a spray method at 30 ° C and a spray pressure of 0.07 MPa for 180 seconds to obtain an example pattern belonging to a fine line pattern. No.1~5.

(比較例4~6)  (Comparative examples 4 to 6)  

對在玻璃基體上依序積層著：Cu層(厚度300nm)、Ni層(厚度150nm)、及Cr層(厚度150nm)的基材。使用正型液狀光阻形成寬30μm、開口部30μm的光阻圖案。將已形成光阻圖案的基材裁剪為長20mm×寬20mm而獲得測試片。對所獲測試片，使用比較例1~3之蝕刻液組成物，依30℃、噴霧壓0.07MPa、180秒的條件，利用噴霧式施行圖案蝕刻，而製得屬於細線狀圖案的比較例圖案No.1~3。 A substrate having a Cu layer (thickness: 300 nm), a Ni layer (thickness: 150 nm), and a Cr layer (thickness: 150 nm) was sequentially laminated on a glass substrate. A photoresist pattern having a width of 30 μm and an opening of 30 μm was formed using a positive liquid photoresist. The substrate on which the photoresist pattern had been formed was cut into a length of 20 mm × a width of 20 mm to obtain a test piece. With respect to the obtained test piece, the etching liquid composition of Comparative Examples 1 to 3 was used, and the pattern of the comparative example belonging to the thin line pattern was obtained by spray pattern etching at 30 ° C, spray pressure of 0.07 MPa, and 180 seconds. No.1~3.

<評價>  <evaluation>  

從圖案上方使用雷射顯微鏡進行觀察，確認屬於光阻開口部之部分的積層體(Cu層、Ni層、及Cr層之積層體)是否被完全除去。將已完全除去者評為「+」，將無法完全除去者評為「-」。又，亦針對所形成圖案的形狀進行評價。將發現圖案呈蛇行、或觀察到長度達3μm以上缺損者評為「-」，將圖案未出現蛇行、或未發現長度達3μm以上缺損者評為「+」。結果如表5所示。 Observation was carried out from the upper side of the pattern using a laser microscope, and it was confirmed whether or not the laminated body (the laminated layer of the Cu layer, the Ni layer, and the Cr layer) belonging to the portion of the photoresist opening portion was completely removed. Those who have been completely removed are rated as "+", and those who cannot be completely removed are rated as "-". Moreover, the shape of the formed pattern was also evaluated. The pattern was found to be meandering, or a defect of 3 μm or more in length was evaluated as "-", and the pattern was not found to be meandering, or a defect having a length of 3 μm or more was not evaluated as "+". The results are shown in Table 5.

由表5所示結果，確認到使用實施例1~5之蝕刻液組成物的實施例6~10，可乾淨除去光阻開口部之由Cu層、Ni層、及Cr層構成的積層體，能形成細線狀圖案。又，得知所獲得圖案的直線性佳、亦未發現缺損產生。另一方面，使用比較例1之蝕刻液組成物的比較例4，並無法除去光阻開口部之由Cu層、Ni層、及Cr層構成的積層體。又，使用比較例2與3之蝕刻液組成物的比較例5與6，確認到所獲得圖案的直線性低、且發生較大缺損。 From the results shown in Table 5, it was confirmed that Examples 6 to 10 using the etching liquid compositions of Examples 1 to 5 can cleanly remove the laminated body composed of the Cu layer, the Ni layer, and the Cr layer in the photoresist opening portion. Can form a thin line pattern. Further, it was found that the obtained pattern had good linearity and no defect was found. On the other hand, in Comparative Example 4 using the etching liquid composition of Comparative Example 1, the laminated body composed of the Cu layer, the Ni layer, and the Cr layer could not be removed. Further, in Comparative Examples 5 and 6 using the etching liquid compositions of Comparative Examples 2 and 3, it was confirmed that the obtained pattern had low linearity and a large defect occurred.

Claims (5)

一種蝕刻液組成物，係用於對含有從銅、鎳及鉻所構成群組中選擇之至少1種金屬之層施行蝕刻的蝕刻液組成物；其含有：(A)鐵(III)離子0.1~10質量%；(B)氯化物離子0.1~10質量%；(C)甲酸離子0.01~5質量%；(D)從下述一般式(1)所示化合物與碳原子數1~4之直鏈或分支狀醇所構成群組中選擇之至少1種化合物0.01~10質量%；(E)從下述一般式(2)所示化合物、膦酸化合物及其鹽、胺基羧酸化合物及其鹽、二元以上羧酸化合物及其鹽、及由二元以上羧酸化合物施行脫水而成的單酐與二酐所構成群組中選擇之至少1種化合物0.01~10質量%；以及水； (上述一般式(1)中，R 1與R 3係各自獨立表示氫原子、或碳原子數1~4之直鏈或分支狀烷基；R 2係表示碳原子數1~4之直鏈或分支狀伸烷基；n係表示1~3之數值)； (上述一般式(2)中，R 4係表示碳原子數2~6之伸烷基；X 1、X 2及X 3係表示下述一般式(3)所示基；X 4係表示氫原子、或下述一般式(3)所示基；z係表示1~5之數值)； (上述一般式(3)中，R 5與R 6係表示伸乙基或伸丙基；當R 5為伸乙基時，R 6為伸丙基；當R 5為伸丙基時，R 6為伸乙基；P與q係表示上述一般式(2)所示化合物之數量平均分子量為200~30,000、且環氧乙烷基含有量成為10~80質量%的數值；*係表示鍵結手；環氧乙烷與環氧丙烷的加成形態係可為無規狀與嵌段狀之任一種)。 An etching liquid composition for etching an etching liquid layer containing at least one metal selected from the group consisting of copper, nickel, and chromium; comprising: (A) iron (III) ion 0.1 ~10% by mass; (B) 0.1 to 10% by mass of chloride ion; (C) 0.01 to 5% by mass of formic acid ion; (D) a compound represented by the following general formula (1) and a carbon number of 1 to 4 At least one compound selected from the group consisting of a linear or branched alcohol is 0.01 to 10% by mass; (E) a compound represented by the following general formula (2), a phosphonic acid compound and a salt thereof, and an aminocarboxylic acid compound And a salt thereof, a divalent or higher carboxylic acid compound and a salt thereof, and at least one compound selected from the group consisting of a monoanhydride and a dianhydride obtained by dehydrating a divalent or higher carboxylic acid compound, 0.01 to 10% by mass; water; (In the above general formula (1), R 1 and R 3 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; and R 2 represents a linear chain having 1 to 4 carbon atoms. Or branched alkyl; n is a value of 1 to 3); (In the above general formula (2), R 4 represents an alkylene group having 2 to 6 carbon atoms; X 1 , X 2 and X 3 represent a group represented by the following general formula (3); and X 4 represents hydrogen; An atom, or a group represented by the following general formula (3); a z system representing a value of 1 to 5); (In the above general formula (3), R 5 and R 6 represent an exoethyl or a propyl group; when R 5 is an exoethyl group, R 6 is a propyl group; when R 5 is a propyl group, R 6 is an ethyl group; P and q are numbers indicating that the compound of the above general formula (2) has a number average molecular weight of 200 to 30,000 and an oxirane group content of 10 to 80% by mass; * indicates a bond The end of the reaction; the addition form of ethylene oxide and propylene oxide can be any of random and block shapes). 如請求項1之蝕刻液組成物，其中，上述一般式(1)所示化合物係下述一般式(1-A)所示化合物： (上述一般式(1-A)中，R 1與R 3係各自獨立表示氫原子、或碳原子數1~4之直鏈或分支狀烷基；n係表示1~3之數值)。 The etching liquid composition according to claim 1, wherein the compound represented by the above general formula (1) is a compound represented by the following general formula (1-A): (In the above general formula (1-A), R 1 and R 3 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; and n represents a value of 1 to 3). 如請求項1之蝕刻液組成物，其中，上述(D)成分係含有二丙二醇單甲醚與異丙醇中之至少其中一者。  The etching liquid composition according to claim 1, wherein the component (D) contains at least one of dipropylene glycol monomethyl ether and isopropyl alcohol.   如請求項1之蝕刻液組成物，其係用於統括對含有銅系層、及含有鎳與鉻中至少其中一者之金屬系層的積層體施行蝕刻。  The etching liquid composition of claim 1, which is used for collectively etching a laminate including a copper layer and a metal layer containing at least one of nickel and chromium.   一種蝕刻方法，係包括有：使用請求項1至4中任一項之蝕刻液組成物，對含有從銅、鎳及鉻所構成群組中選擇之至少1種金屬之層，施行蝕刻的步驟。  An etching method comprising the step of performing etching on a layer containing at least one metal selected from the group consisting of copper, nickel, and chromium, using the etching liquid composition according to any one of claims 1 to 4. .  
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