WO2007040046A1 - Agent de gravure pour alliage nickel-chrome - Google Patents

Agent de gravure pour alliage nickel-chrome Download PDF

Info

Publication number
WO2007040046A1
WO2007040046A1 PCT/JP2006/318576 JP2006318576W WO2007040046A1 WO 2007040046 A1 WO2007040046 A1 WO 2007040046A1 JP 2006318576 W JP2006318576 W JP 2006318576W WO 2007040046 A1 WO2007040046 A1 WO 2007040046A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
chromium alloy
etching
copper
etching solution
Prior art date
Application number
PCT/JP2006/318576
Other languages
English (en)
Japanese (ja)
Inventor
Kiichi Tanimoto
Nobuo Kobayashi
Original Assignee
Ebara-Udylite Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ebara-Udylite Co., Ltd. filed Critical Ebara-Udylite Co., Ltd.
Priority to JP2007538690A priority Critical patent/JPWO2007040046A1/ja
Publication of WO2007040046A1 publication Critical patent/WO2007040046A1/fr

Links

Classifications

    • 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
    • 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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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
    • H05K3/067—Etchants
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer

Definitions

  • the present invention relates to an etching solution for a nickel-chromium alloy. More specifically, the nickel-chromium alloy layer is removed, and the etching capability does not decrease even if the copper concentration in the solution increases during the etching.
  • the present invention relates to an etching solution for a chromium alloy and a method for etching a nickel-chromium alloy using the same. Background art
  • a 10 to 50 nm dissimilar metal layer is formed on a polyimide film by sputtering, then copper sputtering of 50 to 100 nm is performed, and a copper film of about 10 m is formed on the copper sputtered film.
  • the underlying dissimilar metal layer, which forms the adhesion layer, is called the seed layer or the noble layer, and a nickel-chromium alloy is often used for this purpose. It is for improvement.
  • the adhesion between the polyimide resin and the copper layer is improved by the effect of the seed layer, a new problem has arisen.
  • the nickel-chromium alloy layer is not sufficiently etched with the conventional etching solution for removing the copper layer, and the nickel-chromium alloy layer may remain after the wiring is formed, causing a short circuit between the wirings. There was a thing.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2004-190054
  • the present invention provides an etching solution for a nickel chromium alloy that can sufficiently remove the nickel chromium alloy layer and that does not decrease the etching ability even if the copper concentration in the solution becomes high during the etching. Let it be an issue. Means for solving the problem
  • the present invention provides the following components (a) to (c)
  • the present invention is a method for etching a nickel-chromium alloy, characterized in that the above-mentioned nickel-chromium alloy etching solution is allowed to act on the nickel-chromium alloy.
  • the etching solution for nickel-chromium alloy of the present invention does not decrease the etching property with respect to the nickel-chromium alloy even when the concentration of copper in the solution becomes high during etching, and the strength and etching property with respect to copper also increase. It is a thing. Accordingly, the nickel-chromium alloy etching solution of the present invention can be used, for example, for efficiently removing the nickel-chromium alloy remaining in the removed portion of the copper layer in the production of a printed wiring board.
  • the sulfuric acid or sulfonic acid compound as the component (a) used in the etching solution for nickel chromium alloy of the present invention includes sulfuric acid, methane sulfonic acid, ethane sulfone.
  • examples include acids, alkane sulfonic acids such as hydroxymethane sulfonic acid and hydroxyethane sulfonic acid or derivatives thereof, and sulfonic acid compounds such as phenol sulfonic acid or derivatives thereof.
  • the content of these components ( a ) in the etching solution is particularly preferably 0.5 to 3N, preferably 0.2 to 4N as the acid concentration. In addition, the effect may not be obtained if the acid concentration is S0.2N or less, and if it is 4N or more, the effect depending on the added concentration may not be obtained.
  • hydrochloric acid or chlorine compound which is component (b) of the etching solution of the present invention hydrochloric acid or sodium chloride, sodium chloride, potassium salt, ammonium salt, calcium salt
  • examples include chlorine compounds such as lithium chloride, copper chloride, nickel chloride, iron chloride, zinc chloride, tin chloride, and lead chloride.
  • the content of these components (b) in the etching solution is particularly preferably 5 to 30 gZL, preferably 1 to 50 gZL as the chlorine concentration. If the chlorine concentration is less than lgZL, the effect may not be obtained. If the chlorine concentration is more than 50 gZL, the effect corresponding to the added concentration may not be obtained, and the etching amount for copper may further increase.
  • examples of the nitrite as the component (c) of the etching solution of the present invention include nitrites such as sodium nitrite, potassium nitrite, ammonium nitrite and calcium nitrite.
  • the content of these components (c) in the etching solution is preferably 1 mgZL to 5 gZL, particularly preferably 5 mgZL to lgZL as nitrite ions. Note that if the nitrite ion concentration is 1 mgZL or less, the effect may not be obtained, and if it is 5 gZL or more, the removal effect may decrease, and the force and the etching amount for copper may increase.
  • the etching agent of the present invention is produced by mixing the components (a) to (c) described above according to a conventional method.
  • the nitrite of component (c) contained in the etching solution of the present invention The nitrite ion produced is low in stability and is naturally consumed, so it cannot be used for a long time. Therefore, it is preferable to add nitric acid or a nitric acid compound as the component (d) and an iron (III) compound as the component (e) to the etching solution.
  • nitrite ions are generated as a side reaction during the etching process, so that the etching agent can be used for a long time.
  • the nitric acid or nitric acid compound of component (d) added to the etching solution of the present invention includes nitric acid or nitric acid such as sodium nitrate, potassium nitrate, ammonium nitrate, copper nitrate, nickel nitrate, lead nitrate, etc. ⁇ composites.
  • the content of these components (d) in the etching solution is particularly preferably 5 to 50 gZL, preferably 2 to: LOOgZL as nitric acid.
  • the nitric acid concentration is 2 gZL or less, the effect may not be obtained, and if it is 10 gZL or more, the removal effect is not changed, and the amount of etching with respect to copper may increase.
  • component (e) iron (III) compound added to the etching solution of the present invention salt iron (III), iron nitrate (III), iron sulfate (III), ammonium iron nitrate (III) etc. are mentioned.
  • the content of these components ( e ) in the etching solution is preferably 5 mgZL to 2 gZL, preferably 1 mgZL to 10 gZL as iron. If the iron concentration is less than lmgZL, the effect may not be obtained. If the iron concentration is more than lOgZL, the removal effect may be reduced, and the etching amount for copper may be increased.
  • components such as an organic acid and a surfactant can be added to the etching solution of the present invention to the extent that the effects of the present invention are not impaired.
  • the etching solution of the present invention thus obtained can be etched by acting on a nickel-chromium alloy.
  • the nickel-chrome alloy to be etched with the etching solution of the present invention may have any composition, but an alloy having a chromium content of 15 to 25% by mass is particularly preferable.
  • the nickel-chromium alloy is preferably formed on a resin such as polyimide resin by sputtering or the like. Further, a copper layer is once formed on the nickel-chromium alloy layer, and then the copper layer is formed. Particularly preferred is a nickel-chromium alloy remaining in the portion from which copper has been removed, and a nickel-chromium alloy remaining in the vicinity of the end of the copper wiring of the printed wiring board is preferred.
  • a processing method and temperature for allowing the etching solution of the present invention to act on a nickel-chromium alloy The conditions such as time are not particularly limited, but examples of the processing method include a method of immersing in an etching solution or a method of spraying an etching solution with a spray.
  • the treatment temperature is preferably 20 to 60 ° C, particularly preferably 30 to 50 ° C. Note that the effect may not be obtained at a processing temperature of 20 ° C or lower, and the temperature of 60 ° C or higher is not preferable because the removal effect does not change and the etching force and the etching amount for copper may increase.
  • the treatment time is preferably 20 seconds to 3 minutes, particularly preferably 30 seconds to 2 minutes.
  • the removability of the nickel-chromium alloy may be insufficient in less than 20 seconds, and if it is longer than 3 minutes, the removal effect will not change, and the rinsing force and the etching amount for copper may be increased. It ’s not.
  • ⁇ 2 were prepared by a conventional method, and their etching amount, nickel chromium alloy layer removability, and etching solution stability were investigated.
  • the copper-clad laminate and copper coupons, nichrome alloy plate (chromium 20 mass 0/0) nickel - were chromium specimen. These test pieces are immersed in the test solutions prepared above (45 to 1 ° C and 1 minute of the test product) and the mass difference before and after treatment of each test piece. Was used to calculate the etching amount. The results are shown in Table 3.
  • a nickel - chromium (chromium content of 20 mass 0/0) alloy layer is 15nm is formed, then, the copper layer was lOOnm formed. Copper sulfate plating was further performed on the copper layer formed by sputtering to form a copper layer of 10 / zm. Thereafter, a wiring pattern of L / S 30/30 m was formed on the polyimide film by the subtractive method, and this was used as a test piece. A nickel-chromium alloy layer remained around 3-5 ⁇ m around the copper wiring formed by this subtractive method. After the specimen was treated, the residual state of the nickel chrome alloy layer was observed with a transmission electron microscope (SEM) and evaluated according to the following evaluation criteria. The results are also shown in Table 3.
  • SEM transmission electron microscope
  • a copper-clad laminate was immersed in each test solution and dissolved until the amount of copper in each test solution was 0.5 gZL, and each test solution was in the same state as was etched several times. Next, the etching amount and the nickel chromium alloy layer removal property were evaluated by the same method as in the above (1) and (2). The results are also shown in Table 3.
  • the etching solution of the present invention containing at least components (a) to (c) has a nickel-chromium etching amount larger than the copper etching amount, and has a nickel-chromium alloy.
  • the removability of the layer was high.
  • the etching liquid of the present invention containing the components (a) to (e) has a nickel chrome etching amount larger than the copper etching amount even in a continuous state where the copper concentration is high, and the nickel-chromium alloy layer Removability was high.
  • the nickel-chromium alloy etching solution of the present invention can efficiently remove the nickel-chromium alloy without damaging the copper wiring in the production of the flexible printed wiring board. It can be suitably used for the production of a wiring board.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

L’invention concerne un agent de gravure pour alliages nickel-chrome, capable d’éliminer de manière suffisante une couche d’alliage nickel-chrome, et dont la capacité de gravure n’est pas affectée, même lorsque la concentration de cuivre dans l’agent de gravure augmente pendant la gravure. L’agent de gravure pour alliages nickel-chrome est caractérisé en ce qu’il contient les composants (a) à (c) suivants. (a) acide sulfurique ou composé d’acide sulfonique, (b) acide chlorhydrique ou composé de chlore, (c) nitrite
PCT/JP2006/318576 2005-10-03 2006-09-20 Agent de gravure pour alliage nickel-chrome WO2007040046A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007538690A JPWO2007040046A1 (ja) 2005-10-03 2006-09-20 ニッケル−クロム合金用エッチング液

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005289537 2005-10-03
JP2005-289537 2005-10-03

Publications (1)

Publication Number Publication Date
WO2007040046A1 true WO2007040046A1 (fr) 2007-04-12

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PCT/JP2006/318576 WO2007040046A1 (fr) 2005-10-03 2006-09-20 Agent de gravure pour alliage nickel-chrome

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JP (1) JPWO2007040046A1 (fr)
WO (1) WO2007040046A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009161788A (ja) * 2007-12-28 2009-07-23 Nihon Kagaku Sangyo Co Ltd めっき方法及びその方法に用いられるめっき前処理液。
WO2012073816A1 (fr) * 2010-12-03 2012-06-07 荏原ユージライト株式会社 Procédé d'entretien de liquide de gravure et système associé
JP2012144791A (ja) * 2011-01-13 2012-08-02 National Institute Of Advanced Industrial Science & Technology 無電解ニッケル合金膜のパターニング方法
US8486281B2 (en) 2009-10-05 2013-07-16 Kesheng Feng Nickel-chromium alloy stripper for flexible wiring boards
KR101298766B1 (ko) 2011-05-20 2013-08-21 주식회사 익스톨 니켈, 크롬, 니켈-크롬 합금의 에칭 용액 조성물 및 이를 이용한 에칭 방법
KR20160005237A (ko) * 2014-07-04 2016-01-14 오씨아이 주식회사 니켈을 포함하는 금속층의 식각용 조성물
JP2017017360A (ja) * 2011-03-11 2017-01-19 フジフィルム・エレクトロニック・マテリアルズ・ユーエスエイ・インコーポレイテッドＦｕｊｉＦｉｌｍ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＵＳＡ， Ｉｎｃ． 新規なエッチング組成物
CN112064027A (zh) * 2020-09-14 2020-12-11 深圳市志凌伟业光电有限公司 复合铜膜结构用蚀刻液
CN112064028A (zh) * 2020-09-14 2020-12-11 深圳市志凌伟业光电有限公司 复合铜膜结构用蚀刻药水
CN112649270A (zh) * 2018-09-17 2021-04-13 沈阳市启光科技有限公司 一种用于枝晶腐蚀低倍检验的腐蚀剂

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005154899A (ja) * 2003-11-07 2005-06-16 Mec Kk エッチング液、その補給液、それらを用いるエッチング方法及び配線基板の製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005154899A (ja) * 2003-11-07 2005-06-16 Mec Kk エッチング液、その補給液、それらを用いるエッチング方法及び配線基板の製造方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009161788A (ja) * 2007-12-28 2009-07-23 Nihon Kagaku Sangyo Co Ltd めっき方法及びその方法に用いられるめっき前処理液。
US8486281B2 (en) 2009-10-05 2013-07-16 Kesheng Feng Nickel-chromium alloy stripper for flexible wiring boards
JP5911145B2 (ja) * 2010-12-03 2016-04-27 株式会社Ｊｃｕ エッチング液の維持管理方法
WO2012073816A1 (fr) * 2010-12-03 2012-06-07 荏原ユージライト株式会社 Procédé d'entretien de liquide de gravure et système associé
JPWO2012073816A1 (ja) * 2010-12-03 2014-05-19 株式会社Ｊｃｕ エッチング液の維持管理方法およびそのためのシステム
JP2012144791A (ja) * 2011-01-13 2012-08-02 National Institute Of Advanced Industrial Science & Technology 無電解ニッケル合金膜のパターニング方法
JP2017017360A (ja) * 2011-03-11 2017-01-19 フジフィルム・エレクトロニック・マテリアルズ・ユーエスエイ・インコーポレイテッドＦｕｊｉＦｉｌｍ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＵＳＡ， Ｉｎｃ． 新規なエッチング組成物
KR101298766B1 (ko) 2011-05-20 2013-08-21 주식회사 익스톨 니켈, 크롬, 니켈-크롬 합금의 에칭 용액 조성물 및 이를 이용한 에칭 방법
KR101590258B1 (ko) 2014-07-04 2016-02-01 오씨아이 주식회사 니켈을 포함하는 금속층의 식각용 조성물
KR20160005237A (ko) * 2014-07-04 2016-01-14 오씨아이 주식회사 니켈을 포함하는 금속층의 식각용 조성물
CN112649270A (zh) * 2018-09-17 2021-04-13 沈阳市启光科技有限公司 一种用于枝晶腐蚀低倍检验的腐蚀剂
CN112064027A (zh) * 2020-09-14 2020-12-11 深圳市志凌伟业光电有限公司 复合铜膜结构用蚀刻液
CN112064028A (zh) * 2020-09-14 2020-12-11 深圳市志凌伟业光电有限公司 复合铜膜结构用蚀刻药水

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