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 PDFInfo
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229920000642 polymer Polymers 0.000 title description 11
- 229910044991 metal oxide Inorganic materials 0.000 title description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052802 copper Inorganic materials 0.000 claims abstract description 60
- 239000010949 copper Substances 0.000 claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 239000003929 acidic solution Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 72
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 25
- 239000001488 sodium phosphate Substances 0.000 claims description 23
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 21
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 19
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 19
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 17
- 239000001632 sodium acetate Substances 0.000 claims description 17
- 235000017281 sodium acetate Nutrition 0.000 claims description 17
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- GOMCKELMLXHYHH-UHFFFAOYSA-L dipotassium;phthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1C([O-])=O GOMCKELMLXHYHH-UHFFFAOYSA-L 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 238000012546 transfer Methods 0.000 description 18
- 238000011282 treatment Methods 0.000 description 17
- 229960004643 cupric oxide Drugs 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 7
- 229940112669 cuprous oxide Drugs 0.000 description 7
- 238000005553 drilling Methods 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000013459 approach Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- -1 nitrogen- containing compound Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 1
- 229940046817 hypophosphorus acid Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Treatment Of Metals (AREA)
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).
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 |
Family
ID=22225987
Family Applications (1)
| 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)
| Country | Link |
|---|---|
| TW (1) | TW197985B (fr) |
| WO (1) | WO1993010652A1 (fr) |
Cited By (22)
| 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 |
| US7563715B2 (en) | 2005-12-05 | 2009-07-21 | Asm International N.V. | Method of producing thin films |
| 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 |
| US12354877B2 (en) | 2020-06-24 | 2025-07-08 | Asm Ip Holding B.V. | Vapor deposition of films comprising molybdenum |
| US12359315B2 (en) | 2019-02-14 | 2025-07-15 | Asm Ip Holding B.V. | Deposition of oxides and nitrides |
Citations (1)
| 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 |
-
1991
- 1991-11-22 WO PCT/US1991/008777 patent/WO1993010652A1/fr active Application Filing
-
1992
- 1992-01-14 TW TW081100211A patent/TW197985B/zh not_active IP Right Cessation
Patent Citations (1)
| 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)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 14, no. 563 (M-1058)14 December 1990 * |
Cited By (34)
| 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 |
| US6887795B2 (en) | 2000-05-15 | 2005-05-03 | Asm International N.V. | Method of growing electrical conductors |
| US6878628B2 (en) | 2000-05-15 | 2005-04-12 | Asm International Nv | In situ reduction of copper oxide prior to silicon carbide deposition |
| US6921712B2 (en) | 2000-05-15 | 2005-07-26 | Asm International Nv | Process for producing integrated circuits including reduction using gaseous organic compounds |
| US6679951B2 (en) | 2000-05-15 | 2004-01-20 | Asm Intenational N.V. | Metal anneal with oxidation prevention |
| 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 |
| 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 |
| 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 |
| US9469899B2 (en) | 2005-03-15 | 2016-10-18 | Asm International N.V. | Selective deposition of noble metal thin films |
| US8927403B2 (en) | 2005-03-15 | 2015-01-06 | Asm International N.V. | Selective deposition of noble metal thin films |
| US7563715B2 (en) | 2005-12-05 | 2009-07-21 | Asm International N.V. | Method of producing thin films |
| US7541284B2 (en) | 2006-02-15 | 2009-06-02 | Asm Genitech Korea Ltd. | Method of depositing Ru films having high density |
| 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 |
| US7923382B2 (en) | 2006-04-28 | 2011-04-12 | Asm International N.V. | Method for forming roughened surface |
| US8545936B2 (en) | 2008-03-28 | 2013-10-01 | Asm International N.V. | Methods for forming carbon nanotubes |
| US9634106B2 (en) | 2008-12-19 | 2017-04-25 | Asm International N.V. | Doped metal germanide and methods for making the same |
| 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 |
| US7927942B2 (en) | 2008-12-19 | 2011-04-19 | Asm International N.V. | Selective silicide process |
| 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 |
| 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 |
| US12359315B2 (en) | 2019-02-14 | 2025-07-15 | Asm Ip Holding B.V. | Deposition of oxides and nitrides |
| US12354877B2 (en) | 2020-06-24 | 2025-07-08 | Asm Ip Holding B.V. | Vapor deposition of films comprising molybdenum |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW197985B (fr) | 1993-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1993010652A1 (fr) | Procede d'adhesion ameliore entre un oxyde metallique et une surface polymere | |
| US4775444A (en) | Process for fabricating multilayer circuit boards | |
| EP0170414B1 (fr) | Procédé de traitement de surfaces métalliques | |
| EP1006763A2 (fr) | Feuille de cuivre pour des panneaux à circuit imprimé ayant une excellente résistance chimique et résistance à la chaleur | |
| US4717439A (en) | Process for the treatment of copper oxide in the preparation of printed circuit boards | |
| TWI439364B (zh) | A conductive layer and a base layer using the same, and a method of manufacturing the same | |
| JPH1121517A (ja) | 高分子材料の金属表面への接着改良法 | |
| GB2134140A (en) | Treating resin substrates with permanganate solution | |
| US5538616A (en) | Process for copper plating a wiring board | |
| EP0408205B1 (fr) | Substrat en polyimide à surface texturée et métallisation d'un tel substrat | |
| EP0926263B1 (fr) | Procédé pour la fabrication des panneaux à circuit imprimé multicouches | |
| GB1598182A (en) | Multi-layer circuit boards and their manufacture | |
| JP2008109111A (ja) | 対樹脂接着層及びこれを用いた積層体の製造方法 | |
| US5616230A (en) | Method for direct-electroplating an electrically nonconductive substrate | |
| JP3069476B2 (ja) | 多層プリント配線板およびその製造方法 | |
| CN111902570A (zh) | 表面处理铜箔、覆铜层叠板及印刷电路板的制造方法 | |
| EP0310010B1 (fr) | Fabrication d'un circuit imprimé multicouche | |
| TW200428920A (en) | Bonding layer forming solution, method of producing copper-to-resin bonding layer using the solution, and layered product obtained thereby | |
| US6579568B2 (en) | Copper foil for printed wiring board having excellent chemical resistance and heat resistance | |
| JPH10245444A (ja) | ポリイミド樹脂表面への導電性皮膜形成方法 | |
| JP2003096593A (ja) | 粗化処理方法及び電解銅メッキ装置 | |
| JP2004349693A (ja) | 銅表面の対樹脂接着層 | |
| JPH06316768A (ja) | フッ素を含有するポリイミド樹脂の無電解めっき方法 | |
| JPH0637452A (ja) | 多層プリント配線板の製造方法 | |
| JPH0637447A (ja) | 多層プリント配線板の製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP KR US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE |
|
| NENP | Non-entry into the national phase |
Ref country code: CA |
|
| 122 | Ep: pct application non-entry in european phase |