WO1993010652A1 - Procede d'adhesion ameliore entre un oxyde metallique et une surface polymere - Google Patents

Procede d'adhesion ameliore entre un oxyde metallique et une surface polymere Download PDF

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Publication number
WO1993010652A1
WO1993010652A1 PCT/US1991/008777 US9108777W WO9310652A1 WO 1993010652 A1 WO1993010652 A1 WO 1993010652A1 US 9108777 W US9108777 W US 9108777W WO 9310652 A1 WO9310652 A1 WO 9310652A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper
acidic solution
oxide
layer
oxide coating
Prior art date
Application number
PCT/US1991/008777
Other languages
English (en)
Inventor
Therese M. Harryhill
Gary M. Marasovich
Lee Burger
James Czaja
Original Assignee
Electrochemicals, Inc.
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 Electrochemicals, Inc. filed Critical Electrochemicals, Inc.
Priority to PCT/US1991/008777 priority Critical patent/WO1993010652A1/fr
Priority to TW081100211A priority patent/TW197985B/zh
Publication of WO1993010652A1 publication Critical patent/WO1993010652A1/fr

Links

Classifications

    • 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
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0315—Oxidising metal
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1157—Using means for chemical reduction
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards

Definitions

  • the present invention is directed to an improved method for bonding a layer of copper or a copper alloy, via its oxide coating, to a polymeric material.
  • the present invention is useful because it provides an improved method that has applicability in the manufacture of multi-layer electronic circuit boards.
  • U.S. Patent No. 4,642,161 teaches a method of bonding a layer of copper to a layer of polymer wherein the surface of the layer of copper is first oxidized to cupric oxide, then reduced to metallic copper prior to bonding. It recognizes that the disclosure of the alkaline reduction post-oxide treatment in Japanese Patent Laid-Open No. 153797/1981 (the "797" patent) , teaches the reduction of cupric oxide to cuprous oxide.
  • U.S. Patent No. 5,006,200 which is incorporated by reference herein, also suggests that bond strength is greater between cuprous oxide and the polymeric material than between cupric oxide and the polymeric material.
  • the '200 patent teaches the reduction of cupric oxide to cuprous oxide without metallization by using an alkaline reducing solution of between pH 7 and 12 in a temperature range of between 20° and 35° C, in a carefully controlled, continuously circulating reaction, to reduce pink- ring problems.
  • the purpose of this alkaline reduction is to form a network of adhesion, between the copper atoms of the copper layer and the carbon atoms of the polymer layer via the oxygen atoms of the cuprous oxide, to act as a bridge between the copper and the carbon.
  • cupric oxide to either cuprous oxide or metallic copper
  • the chemically reduced cuprous oxide or copper metal tends to reoxidize to cupric oxide after only a few days of contact with atmospheric oxygen, or as a result of baking to dry the reduced layer prior to bonding to a polymer.
  • reduced copper oxide is best laminated immediately after formation.
  • oxidizing acid such as chromic
  • a highly acidic pH i.e., 2.5.
  • step (c) bonding the layer of copper or copper alloy from step (p) to a polymeric material.
  • This invention is directed to a process for bonding a layer of copper or a copper alloy to a layer of polymeric material, the process comprising the steps of:
  • step (c) bonding the layer of copper or copper alloy from step (b) to a polymeric material.
  • Citric/Phosphate 6.5 g/L citric acid; 18.7 g/L trisodium phosphate; pH adjust with Sulfuric acid.
  • Example 7 is the preferred acid treatment for the thick black oxide of Example 6.
  • EXAMPLE 1 The surface of a copper layer was oxidized to a black oxide by dipping it for six minutes in a solution at 165° F and comprising 72 g/L sodium chlorite, 25 g/L NaOH, and 12.5 g/L trisodium phosphate dodecahydrate. After the dip, the copper layer was removed and subjected to a running water rinse for two minutes. A black oxide coating of about 0.4 mg/cm 2 resulted.
  • Copper clad laminate was coated with an oxide according to Example 1.
  • the copper clad laminate with the oxide coating was immersed in a solution of
  • EXAMPLE 3 Copper clad laminate was coated with oxide according to Example 1. The copper clad laminate with the oxide treatment were immersed in a solution of 6.5 g/L citric acid and 18.7 g/L trisodium phosphate, pH adjusted to 5.0 using sulfuric acid, for 3 minutes, at 120°F.
  • Copper clad laminate was coated with oxide according to Example 1.
  • the copper clad laminate with the oxide treatment were immersed in a solution of 0.5M acetic acid and 0.5M sodium acetate, pH 4.3, for 4 minutes, at 120°F.
  • EXAMPLE 7 Copper clad laminate was coated with an oxide according to Example 6. The copper clad laminate with the oxide treatment was immersed in a solution of 20 g/L citric acid and 7.5 g/L trisodium phosphate dodecahydrate at pH 3.0, for 8 minutes at 120°F.

Abstract

L'invention concerne un procédé de liaison d'une couche de cuivre ou d'un alliage de cuivre sur une couche de matière polymère. Ce procédé consiste à: (a) oxyder la surface d'une couche de cuivre ou d'alliages de cuivre avec une solution d'oxydation afin de former un revêtement d'oxyde sur la surface; (b) à soumettre le revêtement d'oxyde sur la couche de cuivre ou d'alliage de cuivre à une solution acide afin d'enlever une quantité de revêtement d'oxyde efficace pour renforcer la liaison avec la matière polymère, la solution acide étant caractérisée par un niveau de pH compris entre 3,0 et 5,5, de préférence entre 3,0 et 4,0; et (c) à procéder à la liaison de la couche de cuivre ou d'alliage de cuivre avec une matière polymère à partir de l'étape (b).
PCT/US1991/008777 1991-11-22 1991-11-22 Procede d'adhesion ameliore entre un oxyde metallique et une surface polymere WO1993010652A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1991/008777 WO1993010652A1 (fr) 1991-11-22 1991-11-22 Procede d'adhesion ameliore entre un oxyde metallique et une surface polymere
TW081100211A TW197985B (fr) 1991-11-22 1992-01-14

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1991/008777 WO1993010652A1 (fr) 1991-11-22 1991-11-22 Procede d'adhesion ameliore entre un oxyde metallique et une surface polymere

Publications (1)

Publication Number Publication Date
WO1993010652A1 true WO1993010652A1 (fr) 1993-05-27

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Application Number Title Priority Date Filing Date
PCT/US1991/008777 WO1993010652A1 (fr) 1991-11-22 1991-11-22 Procede d'adhesion ameliore entre un oxyde metallique et une surface polymere

Country Status (2)

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TW (1) TW197985B (fr)
WO (1) WO1993010652A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995027808A1 (fr) * 1994-04-11 1995-10-19 Electrochemicals, Inc. Procede de traitement d'une feuille de cuivre oxydee
US6482740B2 (en) 2000-05-15 2002-11-19 Asm Microchemistry Oy Method of growing electrical conductors by reducing metal oxide film with organic compound containing -OH, -CHO, or -COOH
US6679951B2 (en) 2000-05-15 2004-01-20 Asm Intenational N.V. Metal anneal with oxidation prevention
US6878628B2 (en) 2000-05-15 2005-04-12 Asm International Nv In situ reduction of copper oxide prior to silicon carbide deposition
US7067407B2 (en) 2003-08-04 2006-06-27 Asm International, N.V. Method of growing electrical conductors
US7491634B2 (en) 2006-04-28 2009-02-17 Asm International N.V. Methods for forming roughened surfaces and applications thereof
US7494927B2 (en) 2000-05-15 2009-02-24 Asm International N.V. Method of growing electrical conductors
US7498242B2 (en) 2005-02-22 2009-03-03 Asm America, Inc. Plasma pre-treating surfaces for atomic layer deposition
US7541284B2 (en) 2006-02-15 2009-06-02 Asm Genitech Korea Ltd. Method of depositing Ru films having high density
US7799680B2 (en) 2003-08-04 2010-09-21 Asm America, Inc. Surface preparation prior to deposition on germanium
US7927942B2 (en) 2008-12-19 2011-04-19 Asm International N.V. Selective silicide process
US8545936B2 (en) 2008-03-28 2013-10-01 Asm International N.V. Methods for forming carbon nanotubes
US8927403B2 (en) 2005-03-15 2015-01-06 Asm International N.V. Selective deposition of noble metal thin films
US9129897B2 (en) 2008-12-19 2015-09-08 Asm International N.V. Metal silicide, metal germanide, methods for making the same
US9139906B2 (en) 2001-03-06 2015-09-22 Asm America, Inc. Doping with ALD technology
US9379011B2 (en) 2008-12-19 2016-06-28 Asm International N.V. Methods for depositing nickel films and for making nickel silicide and nickel germanide
US9587307B2 (en) 2005-03-15 2017-03-07 Asm International N.V. Enhanced deposition of noble metals
US9607842B1 (en) 2015-10-02 2017-03-28 Asm Ip Holding B.V. Methods of forming metal silicides
CN117690869A (zh) * 2024-01-30 2024-03-12 安徽大学 一种在空气环境中的铜-铜低温直接键合方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5106454A (en) * 1990-11-01 1992-04-21 Shipley Company Inc. Process for multilayer printed circuit board manufacture

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5106454A (en) * 1990-11-01 1992-04-21 Shipley Company Inc. Process for multilayer printed circuit board manufacture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 14, no. 563 (M-1058)14 December 1990 *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995027808A1 (fr) * 1994-04-11 1995-10-19 Electrochemicals, Inc. Procede de traitement d'une feuille de cuivre oxydee
US6482740B2 (en) 2000-05-15 2002-11-19 Asm Microchemistry Oy Method of growing electrical conductors by reducing metal oxide film with organic compound containing -OH, -CHO, or -COOH
US6679951B2 (en) 2000-05-15 2004-01-20 Asm Intenational N.V. Metal anneal with oxidation prevention
US6878628B2 (en) 2000-05-15 2005-04-12 Asm International Nv In situ reduction of copper oxide prior to silicon carbide deposition
US6887795B2 (en) 2000-05-15 2005-05-03 Asm International N.V. Method of growing electrical conductors
US6921712B2 (en) 2000-05-15 2005-07-26 Asm International Nv Process for producing integrated circuits including reduction using gaseous organic compounds
US7241677B2 (en) 2000-05-15 2007-07-10 Asm International N.V. Process for producing integrated circuits including reduction using gaseous organic compounds
US7494927B2 (en) 2000-05-15 2009-02-24 Asm International N.V. Method of growing electrical conductors
US9139906B2 (en) 2001-03-06 2015-09-22 Asm America, Inc. Doping with ALD technology
US7799680B2 (en) 2003-08-04 2010-09-21 Asm America, Inc. Surface preparation prior to deposition on germanium
US7067407B2 (en) 2003-08-04 2006-06-27 Asm International, N.V. Method of growing electrical conductors
US7498242B2 (en) 2005-02-22 2009-03-03 Asm America, Inc. Plasma pre-treating surfaces for atomic layer deposition
US9587307B2 (en) 2005-03-15 2017-03-07 Asm International N.V. Enhanced deposition of noble metals
US8927403B2 (en) 2005-03-15 2015-01-06 Asm International N.V. Selective deposition of noble metal thin films
US9469899B2 (en) 2005-03-15 2016-10-18 Asm International N.V. Selective deposition of noble metal thin films
US7541284B2 (en) 2006-02-15 2009-06-02 Asm Genitech Korea Ltd. Method of depositing Ru films having high density
US7923382B2 (en) 2006-04-28 2011-04-12 Asm International N.V. Method for forming roughened surface
US7491634B2 (en) 2006-04-28 2009-02-17 Asm International N.V. Methods for forming roughened surfaces and applications thereof
US8252703B2 (en) 2006-04-28 2012-08-28 Asm International N.V. Methods for forming roughened surfaces and applications thereof
US8545936B2 (en) 2008-03-28 2013-10-01 Asm International N.V. Methods for forming carbon nanotubes
US7927942B2 (en) 2008-12-19 2011-04-19 Asm International N.V. Selective silicide process
US9379011B2 (en) 2008-12-19 2016-06-28 Asm International N.V. Methods for depositing nickel films and for making nickel silicide and nickel germanide
US9129897B2 (en) 2008-12-19 2015-09-08 Asm International N.V. Metal silicide, metal germanide, methods for making the same
US8293597B2 (en) 2008-12-19 2012-10-23 Asm International N.V. Selective silicide process
US9634106B2 (en) 2008-12-19 2017-04-25 Asm International N.V. Doped metal germanide and methods for making the same
US10553440B2 (en) 2008-12-19 2020-02-04 Asm International N.V. Methods for depositing nickel films and for making nickel silicide and nickel germanide
US10043880B2 (en) 2011-04-22 2018-08-07 Asm International N.V. Metal silicide, metal germanide, methods for making the same
US9607842B1 (en) 2015-10-02 2017-03-28 Asm Ip Holding B.V. Methods of forming metal silicides
US10199234B2 (en) 2015-10-02 2019-02-05 Asm Ip Holding B.V. Methods of forming metal silicides
CN117690869A (zh) * 2024-01-30 2024-03-12 安徽大学 一种在空气环境中的铜-铜低温直接键合方法
CN117690869B (zh) * 2024-01-30 2024-05-07 安徽大学 一种在空气环境中的铜-铜低温直接键合方法

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Publication number Publication date
TW197985B (fr) 1993-01-11

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