TW202348407A - Laminated structure with ptru alloy thin film - Google Patents
Laminated structure with ptru alloy thin film Download PDFInfo
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- TW202348407A TW202348407A TW112108650A TW112108650A TW202348407A TW 202348407 A TW202348407 A TW 202348407A TW 112108650 A TW112108650 A TW 112108650A TW 112108650 A TW112108650 A TW 112108650A TW 202348407 A TW202348407 A TW 202348407A
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- thin film
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- metal layer
- laminated structure
- ptru alloy
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 132
- 239000000956 alloy Substances 0.000 title claims abstract description 132
- 239000010409 thin film Substances 0.000 title claims abstract description 127
- 229910002849 PtRu Inorganic materials 0.000 claims abstract description 116
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000010970 precious metal Substances 0.000 claims abstract description 22
- 229910000510 noble metal Inorganic materials 0.000 claims description 77
- 239000010408 film Substances 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 42
- 238000005260 corrosion Methods 0.000 abstract description 42
- 239000010410 layer Substances 0.000 description 206
- 238000007747 plating Methods 0.000 description 58
- 239000010949 copper Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 17
- 238000009713 electroplating Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000003475 lamination Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910002669 PdNi Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- YNDUPGQMECPWKD-UHFFFAOYSA-N [O-][N+](=O)S[N+]([O-])=O Chemical compound [O-][N+](=O)S[N+]([O-])=O YNDUPGQMECPWKD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000007542 hardness measurement Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- DMFGNRRURHSENX-UHFFFAOYSA-N beryllium copper Chemical compound [Be].[Cu] DMFGNRRURHSENX-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 inorganic acid salt Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000000504 luminescence detection Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明係關於構成各種連接器、端子表面的金屬膜的層積構造。詳細而言，關於包含中間層和貴金屬層，作為前述貴金屬層適用由PtRu合金(鉑釕合金)所成的薄膜的層積構造。The present invention relates to a laminated structure of metal films constituting the surfaces of various connectors and terminals. Specifically, as for the noble metal layer including an intermediate layer and a noble metal layer, a laminated structure of thin films made of PtRu alloy (platinum-ruthenium alloy) is suitable.
在電子·電子機器或半導體機器中，使用各種連接器、端子。此等連接器類中，在確保導電性的同時，要求安定的接觸可靠性，大多具有特定的層積構造。作為具有層積構造的連接器，有在由Cu或Cu合金等所成的基材上形成Ni等基底層，進而在其上形成貴金屬層者。貴金屬層係為了保護位於其下方的基底層及基材、確保安定的通電而形成的。尤其，連接器類係以反復插拔使用為前提之故，在與對方側的連接器之間會產生摩擦。為了防止該摩擦造成的基底層或基材的露出而形成貴金屬層。Various connectors and terminals are used in electronic and electronic equipment or semiconductor equipment. These connectors require stable contact reliability while ensuring conductivity, and most of them have a specific lamination structure. As a connector having a laminated structure, there are those in which a base layer such as Ni is formed on a base material made of Cu or a Cu alloy, and a noble metal layer is further formed thereon. The noble metal layer is formed to protect the base layer and base material located below it and ensure stable electrical conduction. In particular, since connectors are designed to be used repeatedly by plugging and unplugging, friction will occur between the connector and the connector on the other side. The precious metal layer is formed in order to prevent the base layer or the base material from being exposed due to this friction.
又，貴金屬層係作為環境遮隔層，為了抑制基材等的腐蝕亦是必要的。智能手機等之電子機器的連接器類係接觸人體的機會多，有鹽分或水分造成的腐蝕之疑慮。貴金屬層係由於是化學安定的金屬，亦可有用於作為腐蝕抑制的保護層。In addition, the noble metal layer serves as an environmental barrier and is necessary to suppress corrosion of the base material and the like. Connectors of electronic devices such as smartphones have many opportunities to come into contact with the human body, and there is a risk of corrosion caused by salt or moisture. Since the precious metal layer is a chemically stable metal, it can also be used as a protective layer to inhibit corrosion.
作為在連接器類的基材上形成，並作為保護層等之作用的上述貴金屬層，迄今為止，Au鍍膜的適用例較多。之後，代替較軟質的Au，使用Pt或RhRu合金等之貴金屬鍍膜。 [先前技術文獻] [專利文獻] As the noble metal layer formed on the base material of connectors and functioning as a protective layer, Au plating has been used in many applications. After that, instead of softer Au, noble metal coating such as Pt or RhRu alloy is used. [Prior technical literature] [Patent Document]
[專利文獻1]日本實用新案第3211820號公報 [專利文獻2]日本特開2005-256163號公報 [Patent Document 1] Japanese Utility Model Publication No. 3211820 [Patent Document 2] Japanese Patent Application Publication No. 2005-256163
[發明欲解決之課題][Problem to be solved by the invention]
近年以來，隨著智能手機或平板終端等電子機器的大幅度普及或其小型化，對於包含適用於此等連接器類的貴金屬層的層積構造，與以往相較，有增加硬度高、耐蝕性優異的要求。在此，本發明係提供對於保護電子機器等之連接器類的貴金屬層及其層積構造，在明確耐摩耗性優異的貴金屬層的同時，能夠最佳化此貴金屬層的耐蝕性的層積構造。 [為解決課題之手段] In recent years, as electronic devices such as smartphones and tablet terminals have become widely popularized or miniaturized, laminate structures including precious metal layers suitable for these connectors have become more durable and corrosion-resistant than ever before. Excellent requirements. Here, the present invention provides a noble metal layer for protecting connectors of electronic equipment and the like and a lamination structure thereof, which can identify a noble metal layer with excellent wear resistance and optimize the corrosion resistance of the noble metal layer. Construct. [To solve the problem]
本發明人等在進行上述課題解决之檢討時，首先進行貴金屬層的最佳化，其結果，思及作為貴金屬層，由PtRu合金所成的薄膜之適用。Ru係貴金屬的一種，相對於Pt為高硬度的金屬之故，被期待經由Pt的合金化而實現高硬度化。又，由於Ru係與Pt或Rh相較為低廉的貴金屬之故，經由Ru的合金化，也可被期待貴金屬層的低成本化。更且，由於Ru亦與Pt同樣在化學上安定之故，PtRu合金鍍膜係預想在耐蝕性上亦為優異。然後，本發明人等係由Pt或Ru所成的貴金屬膜，由於為成膜的鍍敷液的構成係分別為公知之故，根據此等為基礎時，預測亦可進行PtRu合金鍍敷之形成。When the present inventors examined how to solve the above problem, they first optimized the noble metal layer, and as a result, considered the application of a thin film made of PtRu alloy as the noble metal layer. Ru is a type of noble metal and is a metal with higher hardness than Pt. Therefore, it is expected that alloying of Pt will achieve higher hardness. In addition, since Ru is a noble metal that is relatively inexpensive compared to Pt or Rh, alloying of Ru can also be expected to reduce the cost of the noble metal layer. Furthermore, since Ru is chemically stable like Pt, the PtRu alloy plating system is also expected to be excellent in corrosion resistance. Furthermore, the present inventors predicted that PtRu alloy plating can also be performed on the basis of a noble metal film made of Pt or Ru, and the composition of the plating solution used to form the film is known. form.
但是，關於由PtRu合金薄膜所成的貴金屬層，關於作為保護膜之實用例的報告則很少。在此，本發明人等對由PtRu合金薄膜所成的貴金屬層之形成之可否及其各特性，進行了詳細的檢討。其結果，本發明人等確認了PtRu合金薄膜中，對於迄今為止已知的Pt等貴金屬、貴金屬合金薄膜具有適切的硬度、耐摩耗性。然後，發現PtRu合金薄膜雖本身的耐蝕性亦良好，但經由成為在基材或基底層與貴金屬層之間設定最佳的中間層的層積構造，可發揮更高的耐蝕性，而思及了本發明。However, there are few reports on practical examples of the noble metal layer made of PtRu alloy thin film as a protective film. Here, the present inventors examined in detail the feasibility of forming a noble metal layer made of a PtRu alloy thin film and its various characteristics. As a result, the present inventors confirmed that the PtRu alloy thin film has hardness and wear resistance suitable for conventionally known noble metals such as Pt and noble metal alloy thin films. Then, they found that although the PtRu alloy thin film itself has good corrosion resistance, it can exhibit even higher corrosion resistance through a laminate structure in which an optimal intermediate layer is provided between the base material or base layer and the noble metal layer. It was thought that of the present invention.
即，解决上述課題的本發明包含基材、形成在前述基材表面的至少一部分上的中間層、和形成在前述中間層上的貴金屬層的層積構造，前述貴金屬層由PtRu合金薄膜所成，前述中間層係由Pt薄膜所成的層積構造。That is, the present invention that solves the above-mentioned problems includes a laminated structure of a base material, an intermediate layer formed on at least a part of the surface of the base material, and a noble metal layer formed on the intermediate layer, and the noble metal layer is made of a PtRu alloy thin film. , the aforementioned intermediate layer is a laminated structure composed of Pt thin films.
在上述層積構造中，PtRu合金薄膜係由2質量%以上20質量%以下的Ru、和由殘留部Pt及不可避免不純物所成的PtRu合金所成為佳。又，PtRu合金薄膜係維氏硬度為450Hv以上為佳。In the above-mentioned laminated structure, the PtRu alloy thin film is preferably a PtRu alloy composed of 2 mass % or more and 20 mass % or less Ru, and residual Pt and inevitable impurities. In addition, the PtRu alloy thin film preferably has a Vickers hardness of 450 Hv or more.
然後，在本發明的層積構造中，亦可在基材和中間層之間，含有至少一層基底層。此時，前述基底層係由Ni、Cr、Mn、Fe、Co、Cu、Au、Ag、Pd、W的純金屬或此等金屬的合金的任一者所成為佳。Furthermore, the laminated structure of the present invention may include at least one base layer between the base material and the intermediate layer. In this case, the base layer is preferably made of any one of pure metals such as Ni, Cr, Mn, Fe, Co, Cu, Au, Ag, Pd, and W or alloys of these metals.
然而，基材係可以適用由Cu或Cu合金、Fe或Fe合金的任一者所成者。然後，本發明係提供具有上述層積構造的連接器或端子。 [發明效果] However, the base material may be made of any one of Cu or Cu alloy, Fe or Fe alloy. Then, the present invention provides a connector or a terminal having the above-described laminate structure. [Effects of the invention]
如上所說明，本發明係在將PtRu合金薄膜適用作為貴金屬層的同時，具備適切的中間層的層積構造。PtRu合金薄膜係可以電鍍法等形成，具有高硬度且適切的耐摩耗性。又，PtRu合金薄膜係具有均勻的金屬光澤，外觀上亦良好。然後，本發明係作為中間層具備用於更提升關於適切的貴金屬層的耐蝕性的Pt薄膜。本發明的層積構造係對手機等之連接器、端子的保護層為有用，對返復的插拔亦具有耐久性。As described above, the present invention is a laminate structure in which a PtRu alloy thin film is used as a noble metal layer and an appropriate intermediate layer is provided. The PtRu alloy thin film can be formed by electroplating, etc., and has high hardness and appropriate wear resistance. In addition, the PtRu alloy thin film has uniform metallic luster and good appearance. Then, the present invention includes a Pt thin film as an intermediate layer for further improving the corrosion resistance of an appropriate noble metal layer. The laminated structure of the present invention is useful as a protective layer for connectors and terminals of mobile phones, etc., and has durability against repeated plugging and unplugging.
以下，對於本發明之實施形態加以說明。圖1係例示關於本發明之層積構造之實施形態之圖。在圖1中，本發明的基本形態係由基材10、和由在基材10上形成的Pt薄膜所成的中間層11、和由在中間層11的表面上形成的PtRu合金薄膜所成的貴金屬層12所成的層積構造(圖1(a))。另外，如上所述，在本發明的層積構造中，亦可在基材10和中間層11之間形成基底層13(圖1(b)、(c))。基底層13係可為單層，亦可為複數層(13a、13b)所構成。以下，對構成關於本發明的層積構造的貴金屬層(A)、中間層(B)、基底層(C)的各構成，進行詳細說明。Hereinafter, embodiments of the present invention will be described. FIG. 1 is a diagram illustrating an embodiment of the laminate structure of the present invention. In FIG. 1, the basic form of the present invention is composed of a base material 10, an intermediate layer 11 formed of a Pt thin film formed on the base material 10, and a PtRu alloy thin film formed on the surface of the intermediate layer 11. A laminated structure composed of precious metal layers 12 (Fig. 1(a)). Moreover, as mentioned above, in the laminated structure of this invention, the base layer 13 may be formed between the base material 10 and the intermediate layer 11 (FIG. 1(b), (c)). The base layer 13 may be a single layer or may be composed of multiple layers (13a, 13b). Hereinafter, each structure of the noble metal layer (A), the intermediate layer (B), and the base layer (C) constituting the laminated structure of the present invention will be described in detail.
(A)貴金屬層(PtRu合金薄膜) 在本發明中，作為基材及基底膜的保護層起作用的貴金屬層，則適用PtRu合金薄膜。構成此PtRu合金薄膜的PtRu合金的組成係Ru濃度為2質量%以上20質量%以下者為佳。Ru濃度不足2質量%時，缺乏硬度上升的效果。又，對Pt之Ru合金化所成硬度上升作用雖伴隨Ru濃度的增大而增大，但即使超過20質量%，亦不會有期待太大的上升幅度。 (A) Noble metal layer (PtRu alloy film) In the present invention, a PtRu alloy thin film is suitable for the noble metal layer that functions as a protective layer for the base material and base film. The PtRu alloy constituting the PtRu alloy thin film preferably has a Ru concentration of 2 mass % or more and 20 mass % or less. When the Ru concentration is less than 2% by mass, the hardness increasing effect is insufficient. In addition, the hardness-increasing effect of Ru alloying on Pt increases as the Ru concentration increases, but even if it exceeds 20 mass %, a large increase is not expected.
本發明的PtRu合金薄膜係實質上僅由Pt和Ru所成。Pt和Ru的純度係90質量%以上為佳，更佳為99.0質量%以上。惟，在關於本發明的PtRu合金薄膜中，可允許含有不可避免不純物。作為此不可避免不純物，可列舉Fe、Ni、Cr、Co、Mn、Cu、Au、Ag、Pd、W、Mg、Na、Rh、Ge、Zn、Sn、Re等。此等之不可避免不純物係起因於薄膜的形成過程。在鍍敷法所成PtRu合金薄膜的情況下，PtRu合金鍍敷液中的成分，例如有金屬鹽(Pt鹽及Ru鹽)中的不純物、鍍敷液的添加劑等成分中之不可避免不純物之混入。作為不可避免不純物之含有量，合計為1000ppm以下為佳。The PtRu alloy thin film of the present invention is essentially composed only of Pt and Ru. The purity of Pt and Ru is preferably 90 mass% or more, more preferably 99.0 mass% or more. However, in the PtRu alloy thin film of the present invention, it is allowed to contain unavoidable impurities. Examples of such unavoidable impurities include Fe, Ni, Cr, Co, Mn, Cu, Au, Ag, Pd, W, Mg, Na, Rh, Ge, Zn, Sn, Re, and the like. These unavoidable impurities originate from the film formation process. In the case of PtRu alloy thin films formed by plating methods, the components in the PtRu alloy plating solution include, for example, impurities in metal salts (Pt salts and Ru salts), additives in the plating solution, and other inevitable impurities. Mix in. The total content of unavoidable impurities is preferably 1000 ppm or less.
然而，對PtRu合金薄膜之合金組成(Ru濃度)或不純物之含有量係對膜之表面或剖面，可經由進行電子束微探針分析(EPMA)、能量色散型X線光譜分析(EDX)、螢光X線分析(XRF)等測定。又，對於溶解PtRu合金薄膜的溶液，亦可經由電感耦合電漿發光光譜分析(ICP)進行分析。However, the alloy composition (Ru concentration) or impurity content of the PtRu alloy film can be determined by electron beam microprobe analysis (EPMA), energy dispersive X-ray spectroscopy (EDX), Fluorescence X-ray analysis (XRF) and other measurements. In addition, the solution in which the PtRu alloy thin film is dissolved can also be analyzed by inductively coupled plasma luminescence spectroscopy (ICP).
又，本發明之貴金屬層之PtRu合金薄膜係維氏硬度為450Hv以上為佳。PtRu合金薄膜的硬度值係伴隨Ru濃度的上昇而增大。然後，本發明的PtRu合金薄膜的前述硬度係在相同的基底時，相對於以往技術的Pt薄膜而言成為高硬度，作為連接器類等的保護層，可發揮適切的耐摩耗性。PtRu合金薄膜之硬度係更佳為500Hv以上。然而，關於硬度值的上限，會由於基底等而不同，但在上述Ru濃度的上限，可以發揮到900Hv的硬度。In addition, the PtRu alloy thin film of the noble metal layer of the present invention preferably has a Vickers hardness of 450 Hv or more. The hardness value of PtRu alloy film increases with the increase of Ru concentration. Furthermore, when the aforementioned hardness of the PtRu alloy thin film of the present invention is the same as that of the conventional Pt thin film, it can exhibit appropriate wear resistance as a protective layer for connectors and the like. The hardness of the PtRu alloy film is preferably above 500Hv. However, the upper limit of the hardness value varies depending on the substrate, etc., but at the upper limit of the Ru concentration mentioned above, a hardness of 900 Hv can be exerted.
然而，貴金屬層之硬度測定係除了維氏硬度計、微小硬度計之外，可經由奈米壓痕法加以測定。在本發明的層積構造中，有將各層的膜厚設定得極薄之情形。奈米壓痕法適合於針對相關薄膜的層積構造，可靠地進行貴金屬層的硬度測定。在奈米壓痕法中，可以根據測定值(接觸剛性(剛度)、接觸深度)計算硬度(GPa)，此硬度係可以換算為維氏硬度。However, the hardness of the precious metal layer can be measured by the nanoindentation method in addition to Vickers hardness tester and micro hardness tester. In the laminated structure of the present invention, the film thickness of each layer may be set extremely thin. The nanoindentation method is suitable for reliably measuring the hardness of precious metal layers in the lamination structure of relevant films. In the nanoindentation method, the hardness (GPa) can be calculated based on the measured values (contact rigidity (stiffness), contact depth), and this hardness can be converted into Vickers hardness.
本發明層積構造中的貴金屬層的厚度係0.1μm以上5.0μm以下為佳。0.1μm以下時，難以長期維持對基底的保護效果。又，對超過5.0μm的PtRu合金薄膜，以鍍敷法製造時，膜中有包含龜裂等缺陷之疑慮。The thickness of the noble metal layer in the laminated structure of the present invention is preferably 0.1 μm or more and 5.0 μm or less. Below 0.1 μm, it is difficult to maintain the protective effect on the substrate for a long time. In addition, when a PtRu alloy thin film exceeding 5.0 μm is produced by plating, there is a concern that defects such as cracks may be included in the film.
本發明之貴金屬層(PtRu合金薄膜)係如後述，為鍍敷法(電解電鍍)所成鍍膜為佳。經由鍍敷法形成的PtRu合金薄膜係由微細緻密的PtRu合金的結晶子所構成，由此可發揮上述適切的硬度特性和耐蝕性。然而，此PtRu合金的結晶子的粒徑係平均為1Å以上100Å以下為佳，更佳為1Å以上10Å以下。PtRu合金鍍膜的結晶子徑的測定、計算係可以根據經由X線繞射分析(XRD)所得之繞射尖峰的半峰全寬，由Scherrer式加以計算。The noble metal layer (PtRu alloy thin film) of the present invention is preferably a plating film formed by a plating method (electrolytic plating) as will be described later. The PtRu alloy thin film formed by the plating method is composed of fine and dense crystallites of the PtRu alloy, thereby exhibiting the above-mentioned appropriate hardness characteristics and corrosion resistance. However, the average particle size of the crystallites of the PtRu alloy is preferably from 1 Å to 100 Å, more preferably from 1 Å to 10 Å. The crystallon diameter of the PtRu alloy coating can be measured and calculated by the Scherrer formula based on the full width at half maximum of the diffraction peak obtained through X-ray diffraction analysis (XRD).
(B)中間層(Pt薄膜) 上述PtRu合金薄膜雖伴隨硬度，耐蝕性亦優異，經由在其下具備由Pt薄膜所成的中間層，發揮更高的耐蝕性。經由形成由Pt薄膜所成的中間層，其表面上的PtRu合金薄膜的耐蝕性提升的理由則未必清楚。作為其理由，本發明人等考察了經由在基材或基底層先形成Pt薄膜來提升PtRu合金薄膜的緻密性和密合性，或者基底層與貴金屬層的電位差的緩和作用在中間層等之情形。本發明人等雖認為前述複數之因素被複合地發揮作用，但並不確定。當然，由於中間層的存在所成貴金屬層的耐蝕性的上昇效果，則經由後述的實驗驗證而變得明確。 (B) Intermediate layer (Pt film) The above-mentioned PtRu alloy thin film has excellent corrosion resistance despite its hardness. By providing an intermediate layer made of a Pt thin film under the PtRu alloy thin film, it exhibits higher corrosion resistance. It is not necessarily clear why the corrosion resistance of the PtRu alloy thin film on the surface is improved by forming an intermediate layer made of a Pt thin film. As reasons for this, the present inventors considered improving the density and adhesion of the PtRu alloy thin film by first forming a Pt thin film on the base material or base layer, or the moderating effect of the potential difference between the base layer and the noble metal layer on the intermediate layer, etc. situation. The present inventors believe that the above-mentioned plural factors act in a complex manner, but they are not certain. Of course, the effect of increasing the corrosion resistance of the noble metal layer due to the presence of the intermediate layer will become clear through the experimental verification described below.
中間層的Pt薄膜係純度為90質量%以上為佳，更佳為99.0質量%以上。又，與貴金屬層同樣地允許含有不可避免不純物，此時，可以含有上述種類的不純物元素。作為不可避免不純物之含有量，合計為1000ppm以下為佳。然而，中間層的Pt薄膜的純度或不純物含有量係可以用與貴金屬層相同的方法確認。The purity of the Pt thin film in the middle layer is preferably 90 mass% or more, more preferably 99.0 mass% or more. In addition, the inclusion of unavoidable impurities is allowed in the same manner as the noble metal layer. In this case, the above-mentioned types of impurity elements may be included. The total content of unavoidable impurities is preferably 1000 ppm or less. However, the purity or impurity content of the Pt thin film in the intermediate layer can be confirmed by the same method as that of the noble metal layer.
本發明層積構造的中間層的Pt薄膜的厚度係0.1μm以上5.0μm以下為佳。5.0μm以下的中間層係實質上不存在，缺乏貴金屬層的耐蝕性提昇作用。又，5.0μm以上的中間層係在電鍍等形成之時，有會產生龜裂之情形。然而，中間層的Pt薄膜亦經由鍍敷法形成者為佳。The thickness of the Pt thin film in the intermediate layer of the laminated structure of the present invention is preferably 0.1 μm or more and 5.0 μm or less. The intermediate layer system below 5.0 μm essentially does not exist, and lacks the corrosion resistance improvement effect of the noble metal layer. In addition, when an intermediate layer of 5.0 μm or more is formed by electroplating, cracks may occur. However, it is preferable that the Pt thin film of the intermediate layer is also formed by plating.
(C)基底層 上述之中間層及貴金屬層係直接成膜於基材上亦可。惟，在適用於連接器類等各種用途時，大多在基材和中間層之間形成基底層。 (C) Basal layer The above-mentioned intermediate layer and noble metal layer can also be directly formed on the substrate. However, when applied to various applications such as connectors, a base layer is often formed between the base material and the intermediate layer.
基底層係在連接器類的層積構造中，根據各種目的而形成。例如，基底層係除了確保中間層與基材的密合性(接合強度)或賦予基材的耐蝕性之外，還以阻障層、接觸電阻的減低、擴散防止等目的而形成。作為基底層的材質，由Ni、Cr、Mn、Fe、Co、Cu、Au、Ag、Pd、W的純金屬或此等金屬的合金的任一者所構成。The base layer is formed in the laminate structure of connectors for various purposes. For example, in addition to ensuring the adhesion (joining strength) between the intermediate layer and the base material or imparting corrosion resistance to the base material, the base layer is formed to serve as a barrier layer, reduction of contact resistance, prevention of diffusion, etc. The base layer is made of pure metals such as Ni, Cr, Mn, Fe, Co, Cu, Au, Ag, Pd, and W, or any alloy of these metals.
作為基底層的具體構成，例如，為確保中間層及貴金屬層與基材的密合性，在中間層下形成由Au、Ag、Pd、Pt等貴金屬的純金屬或此等的合金所成的基底層。又，為了防止基材等金屬屬的溶出或成為阻障層，形成Ni、Ni合金(NiP、NiW、NiMo、CoW、CoMo)作為基底層。此基底層係形成在由中間層或上述貴金屬所成的基底層之下。更且，在基材表面，有形成由NiP、NiPW、CoP所成的基底層之情形。NiP鍍層是緻密且硬質的金屬層，賦予基材耐蝕性或耐摩耗性。然而，由NiP、NiPW、CoP所成的基底層係可為結晶質構造或非晶質構造的任一者。As a specific structure of the base layer, for example, in order to ensure the adhesion between the intermediate layer and the noble metal layer and the base material, a layer made of pure metals of noble metals such as Au, Ag, Pd, Pt or their alloys is formed under the intermediate layer. basal layer. In addition, in order to prevent the metal metal such as the base material from eluting or becoming a barrier layer, Ni or Ni alloy (NiP, NiW, NiMo, CoW, CoMo) is formed as a base layer. This base layer is formed under the base layer made of the intermediate layer or the above-mentioned noble metal. Furthermore, a base layer made of NiP, NiPW, or CoP may be formed on the surface of the base material. NiP plating is a dense and hard metal layer that gives the base material corrosion resistance or wear resistance. However, the base layer system composed of NiP, NiPW, and CoP may have either a crystalline structure or an amorphous structure.
在本發明的層積構造中，基底層係對應於目的至少形成1層作為上述金屬、合金的薄膜。即，可以在中間層和基材之間，形成複數之基底層。對構成基底層的薄膜的層數及各個薄膜的厚度則沒有特別限制。In the laminated structure of the present invention, at least one layer of a thin film of the above-mentioned metal or alloy is formed in the base layer according to the purpose. That is, a plurality of base layers may be formed between the intermediate layer and the base material. The number of thin films constituting the base layer and the thickness of each thin film are not particularly limited.
(D)基材 關於本發明的層積構造係在基材上成膜以上說明的貴金屬層、中間層、基底層而形成。對基材的材質或形狀、尺寸則沒有限制。作為基材材質，可列舉Cu或Cu合金(磷青銅、黃銅、鈹銅、洋白、科爾森銅)或Fe或Fe合金(Fe-Ni合金、Fe-Ni-Co合金、不鏽鋼)等。又，可為前述材質以外的基材，亦也可為形成Cu或Ag等導電圖案者。基材形狀，亦可為晶片狀、帶狀等，沒有特別規定。 (D)Substrate The laminated structure of the present invention is formed by forming the above-described noble metal layer, intermediate layer, and base layer on a base material. There are no restrictions on the material, shape, or size of the substrate. Examples of the base material include Cu or Cu alloys (phosphor bronze, brass, beryllium copper, galvanized steel, Corson copper) or Fe or Fe alloys (Fe-Ni alloy, Fe-Ni-Co alloy, stainless steel), etc. . Moreover, it may be a base material other than the above-mentioned material, or it may be one in which a conductive pattern such as Cu or Ag is formed. The shape of the substrate may also be wafer-shaped, strip-shaped, etc., and is not particularly specified.
又，沒有基材中的基底層、中間層、貴金屬層的形成部位之限制。基底層等係形成在基材的至少一部分即可。例如，可以在基材的一部分設定電性接點部，在此電性接點部形成基底層和中間層以及貴金屬層。In addition, there is no restriction on the formation locations of the base layer, the intermediate layer, and the precious metal layer in the base material. The base layer and the like may be formed on at least a part of the base material. For example, an electrical contact portion may be provided on a part of the base material, and a base layer, an intermediate layer, and a noble metal layer may be formed on the electrical contact portion.
然後，具備關於本發明的PtRu合金薄膜和Pt薄膜的層積構造，係能夠適用於電子、電氣機器、半導體裝置等的連接器、端子。連接器係可適用於公、母(插塞插座)兩者。Furthermore, having a laminated structure of the PtRu alloy thin film and the Pt thin film of the present invention can be applied to connectors and terminals of electronics, electrical equipment, semiconductor devices, and the like. The connector system can be applied to both male and female (plug and socket).
(E)關於本發明之層積構造之製造方法 以上說明關於本發明的層積構造係在基材上依次形成構成基底層、中間層、貴金屬層的薄膜而製造的。對於在基材形成基底層時的方法，鍍敷法(電解電鍍及無電解電鍍)、濺鍍法、化學蒸鍍法(CVD、ALD)、真空蒸鍍法等皆可以適用。 (E) Method for manufacturing the laminated structure of the present invention The laminate structure of the present invention described above is produced by sequentially forming thin films constituting a base layer, an intermediate layer, and a noble metal layer on a base material. As a method for forming a base layer on a base material, plating methods (electrolytic plating and electroless plating), sputtering methods, chemical vapor deposition methods (CVD, ALD), vacuum evaporation methods, etc. can be applied.
對於中間層的Pt薄膜的形成，亦可適用上述的薄膜形成法。惟、較佳為電解電鍍法。此係為了覆蓋性良好地成膜緻密且缺陷少的Pt薄膜。在Pt薄膜的電解電鍍法中，可以使用公知的Pt鍍敷液。作為較佳的Pt鍍敷液，可列舉含有硫酸基(SO 4)或磺基(SO 3)、硝基(NO 2)、硝酸基(NO 3)、胺基(NH 3)、乙醯基(H 2O)、羥基(OH)之至少任一者的2價Pt的無機酸鹽。作為具體例，可列鹽硫酸Pt(PtSO 4)、二硝基硫化Pt(Pt(SO 4)(NO 3) 2)、硝酸Pt(Pt(NO 3) 2)、二硝基二胺Pt(Pt(NH 3) 2(NO 3) 2)、二胺二氯Pt(Pt(NH 3) 2Cl 2)、三氯胺Pt酸(HPtCl 3(NH 3))或其鹽、四硝基Pt酸(H 2PtCl 4)或其鹽、四磺基Pt(H 6Pt(SO 3) 4)或其鹽四胺Pt磷酸(H 2Pt(NH 3) 4)或其鹽等。其中，特別作為Pt鹽較佳為硫酸Pt、二硝基硫化Pt、二硝基二胺Pt。又，Pt鍍敷液係可添加公知的添加劑，例如pH緩衝劑、錯合劑、安定劑等。 The above-mentioned thin film formation method can also be applied to the formation of the Pt thin film of the intermediate layer. However, the electrolytic plating method is preferred. This is to form a dense Pt thin film with good coverage and few defects. In the electrolytic plating method of a Pt thin film, a known Pt plating solution can be used. Preferable Pt plating solutions include those containing sulfate group (SO 4 ) or sulfo group (SO 3 ), nitro group (NO 2 ), nitric acid group (NO 3 ), amine group (NH 3 ), and acetyl group. An inorganic acid salt of divalent Pt of at least one of (H 2 O) and hydroxyl group (OH). Specific examples include Pt sulfate (PtSO 4 ), Pt dinitro sulfide (Pt (SO 4 ) (NO 3 ) 2 ), Pt nitric acid (Pt (NO 3 ) 2 ), and dinitrodiamine Pt ( Pt(NH 3 ) 2 (NO 3 ) 2 ), diamine dichloride Pt (Pt(NH 3 ) 2 Cl 2 ), trichloramine Pt acid (HPtCl 3 (NH 3 )) or its salt, tetranitroPt Acid (H 2 PtCl 4 ) or its salt, tetrasulfoPt (H 6 Pt (SO 3 ) 4 ) or its salt, tetraamine Pt phosphate (H 2 Pt (NH 3 ) 4 ) or its salt, etc. Among them, particularly preferred Pt salts are Pt sulfate, Pt dinitrosulfide, and Pt dinitrodiamine. In addition, known additives such as pH buffers, complexing agents, stabilizers, etc. may be added to the Pt plating liquid system.
作為上述之鍍敷液所成鍍敷條件，係Pt濃度1g/L以上15g/L以下、鍍敷液溫度45℃以上65℃以下、成膜時之電流密度2.0A/dm 2以上10A/dm 2以下為佳。 The plating conditions for the above-mentioned plating solution include a Pt concentration of 1g/L or more and 15g/L or less, a plating solution temperature of 45°C or more and 65°C or less, and a current density during film formation of 2.0A/dm or more and 10A/dm or more. 2 or less is better.
然後，貴金屬層的PtRu合金薄膜的形成係亦可適用上述各種成膜法，但與中間層(Pt薄膜)相同，電鍍法為佳。此係因在獲得良好膜質的PtRu合金薄膜的同時，電鍍法係亦容易調整PtRu合金薄膜的組成(Ru濃度)。Then, the formation system of the PtRu alloy thin film of the noble metal layer can be applied to the above-mentioned various film forming methods, but like the intermediate layer (Pt thin film), the electroplating method is preferred. This is because while obtaining a PtRu alloy thin film with good film quality, the electroplating method can also easily adjust the composition (Ru concentration) of the PtRu alloy thin film.
以電解電鍍法形成PtRu合金薄膜時的鍍敷液係可使用必須含有Pt鹽和Ru鹽的PtRu合金鍍敷液。於本發明適切的PtRu合金鍍敷液係含有作為必要成分的2價Pt鹽及3價Ru鹽的金屬鹽、和硫酸及磺胺酸的PtRu合金鍍敷液。When forming a PtRu alloy thin film by electrolytic plating, a PtRu alloy plating liquid that must contain Pt salt and Ru salt can be used. A suitable PtRu alloy plating solution for the present invention is a PtRu alloy plating solution containing metal salts of divalent Pt salts and trivalent Ru salts as essential components, and sulfuric acid and sulfonamide acid.
作為2價Pt鹽，可以適用與上述Pt鍍敷液中所適用的2價Pt鹽相同者。另一方面，對於3價Ru鹽，可以適用硫酸Ru(RuSO 4)或硝酸Ru(Ru(NO 3) 2)、氯化Ru(RuCl 3)。然後，PtRu合金鍍敷液之各構成之含有量係Pt濃度1g/L以上15g/L以下，Ru濃度0.1g/L以上10g/L以下，總硫酸濃度為10g/L以上200g/L以下、磺胺酸濃度為0.1g/L以上20g/L以下為佳。然而，對於PtRu合金鍍敷液，可適宜添加添加劑。 As the divalent Pt salt, the same divalent Pt salt as used in the above-mentioned Pt plating solution can be used. On the other hand, as a trivalent Ru salt, Ru sulfate (RuSO 4 ), Ru nitric acid (Ru (NO 3 ) 2 ), and Ru chloride (RuCl 3 ) can be used. Then, the content of each component of the PtRu alloy plating solution is that the Pt concentration is 1g/L or more and 15g/L or less, the Ru concentration is 0.1g/L or more and 10g/L or less, the total sulfuric acid concentration is 10g/L or more and 200g/L or less, The sulfamic acid concentration is preferably 0.1g/L or more and 20g/L or less. However, for the PtRu alloy plating solution, additives may be appropriately added.
又，PtRu合金薄膜的組成係可經由PtRu合金鍍敷液的Pt濃度與Ru濃度之比加以調整。例如，上述中，作為貴金屬層適切之PtRu合金薄膜的Ru濃度係Ru濃度2質量%以上20質量%以下。為了形成該適切組成的PtRu合金薄膜，PtRu合金鍍敷液的Pt濃度與Ru濃度之比(Ru濃度(g/L)/Pt濃度(g/L))為0.1以上0.8以下為佳。In addition, the composition of the PtRu alloy thin film can be adjusted by the ratio of the Pt concentration and the Ru concentration of the PtRu alloy plating solution. For example, among the above, the Ru concentration of the PtRu alloy thin film suitable as the noble metal layer is 2 mass % or more and 20 mass % or less. In order to form a PtRu alloy thin film with this appropriate composition, the ratio of Pt concentration to Ru concentration (Ru concentration (g/L)/Pt concentration (g/L)) in the PtRu alloy plating solution is preferably 0.1 or more and 0.8 or less.
作為PtRu合金鍍敷液所進行電解電鍍的條件，PtRu合金鍍敷液的pH為1以下為佳，溫度為45℃以上65℃以下，電流密度為2.0A/dm2以上10A/dm2以下為佳。 [實施例] As conditions for electrolytic plating of PtRu alloy plating liquid, the pH of the PtRu alloy plating liquid is preferably 1 or less, the temperature is 45°C or more and 65°C or less, and the current density is 2.0A/dm2 or more and 10A/dm2 or less. [Example]
第1實施形態：首先，作為預備性檢討，為了確認PtRu合金薄膜作為貴金屬層的適用性，在Cu板基材上，形成組成(Ru濃度)不同的PtRu合金薄膜，以測定硬度。First Embodiment: First, as a preliminary check, in order to confirm the suitability of the PtRu alloy thin film as a noble metal layer, PtRu alloy thin films with different compositions (Ru concentration) were formed on the Cu plate base material to measure the hardness.
準備作為基材Cu板(20mm×40mm×0.1mm)，在該基材上成膜貴金屬層的PtRu合金薄膜。PtRu合金薄膜係使用PtRu合金鍍敷液成膜。PtRu合金鍍敷液係將二硝基硫化Pt(Pt(SO 4)(NO 3) 2)和硫酸Ru(RuSO 4)，添加硫酸和磺胺酸，製作總硫酸濃度為80g/L的基本浴，調整到pH1，形成鍍敷液。在此，作為PtRu合金鍍敷液的Pt、Ru的濃度，將Pt濃度設為10g/L，另一方面，關於Ru濃度，為了控制PtRu合金薄膜的Ru濃度，在1g/L~5g/L(Ru濃度(g/L)/Pt濃度(g/L)=0.1~0.5)的範圍內進行調整，製造5種類PtRu合金鍍敷液(Ru濃度(g/L)/Pt濃度(g/L)=0.1~0.5)。 A Cu plate (20 mm × 40 mm × 0.1 mm) was prepared as a base material, and a PtRu alloy thin film of a noble metal layer was formed on the base material. The PtRu alloy thin film is formed using PtRu alloy plating solution. The PtRu alloy plating solution is made of dinitro sulfide Pt (Pt(SO 4 )(NO 3 ) 2 ) and Ru sulfate (RuSO 4 ), with sulfuric acid and sulfonamide added to make a basic bath with a total sulfuric acid concentration of 80g/L. Adjust to pH 1 to form a plating solution. Here, as the Pt and Ru concentrations of the PtRu alloy plating solution, the Pt concentration is 10 g/L. On the other hand, the Ru concentration is 1 g/L to 5 g/L in order to control the Ru concentration of the PtRu alloy thin film. Adjust within the range of (Ru concentration (g/L)/Pt concentration (g/L) = 0.1~0.5) to produce 5 types of PtRu alloy plating solutions (Ru concentration (g/L)/Pt concentration (g/L) )=0.1~0.5).
PtRu合金薄膜之成膜係浴温60℃、電流密度為4.0A/dm 2、鍍敷時間25分鐘，製造具有膜厚5μm之PtRu合金薄膜之層積構造(No.1~5)。然而，本實施形態中，為了對比，亦製造Pt薄膜(膜厚5μm)及RhRu合金薄膜(膜厚5μm)之貴金屬層(No.6、7)。Pt薄膜係使用Pt鍍敷液(日本Electroplating Engineers股份有限公司製 PRECIOUSFAB Pt2000)。又，RhRu合金薄膜之成膜係使用RhRu合金鍍敷液(日本Electroplating Engineers股份有限公司製 PRECIOUSFAB Rh2000)。 The PtRu alloy thin film was formed using a bath temperature of 60°C, a current density of 4.0A/dm 2 , and a plating time of 25 minutes to produce a laminated structure of PtRu alloy thin films with a film thickness of 5 μm (No. 1~5). However, in this embodiment, for comparison, noble metal layers (No. 6 and 7) of a Pt thin film (film thickness: 5 μm) and a RhRu alloy thin film (film thickness: 5 μm) were also produced. For the Pt thin film, a Pt plating solution (PRECIOUSFAB Pt2000 manufactured by Nippon Electroplating Engineers Co., Ltd.) was used. In addition, a RhRu alloy plating solution (PRECIOUSFAB Rh2000 manufactured by Nippon Electroplating Engineers Co., Ltd.) was used to form the RhRu alloy thin film.
然後，對於製造的具有5種類PtRu合金膜及Pt薄膜、RhRu合金薄膜的層積構造，測定其表面(貴金屬層表面)的硬度。在硬度測定中，經由微硬度計在荷重10g下，測定維氏硬度(Hv)。將該測定結果和經由EDX測定的貴金屬層的組成(Ru濃度)，示於表1。Then, the hardness of the surface (noble metal layer surface) of the produced laminated structure including five types of PtRu alloy films, Pt thin films, and RhRu alloy thin films was measured. In the hardness measurement, Vickers hardness (Hv) was measured under a load of 10 g via a microhardness tester. Table 1 shows the measurement results and the composition (Ru concentration) of the noble metal layer measured by EDX.
本實施形態中成膜的PtRu合金鍍膜(No.1~No.5)的Ru比率係伴隨鍍敷液的Ru濃度的增加而上昇，確認由3質量%~12.3質量%的PtRu合金所構成。然後，從表1可以確認，PtRu合金鍍膜的硬度係在任何基板上皆為450Hv以上。此等PtRu合金鍍膜係與Pt鍍膜(No.6)相較為高硬度，可以確認為與RhRu合金薄膜相同程度的高硬度。The Ru ratio of the PtRu alloy plating films (No. 1 to No. 5) formed in this embodiment increased as the Ru concentration of the plating solution increased, and it was confirmed that the films were composed of 3 mass % to 12.3 mass % PtRu alloy. Then, from Table 1, it can be confirmed that the hardness of the PtRu alloy coating is 450Hv or more on any substrate. These PtRu alloy coatings have a higher hardness than the Pt coating (No. 6) and can be confirmed to have the same level of high hardness as the RhRu alloy thin film.
PtRu合金鍍膜的硬度係基本上對應Ru濃度的上昇而變高，顯示最大760Hv的維氏硬度。又，在任何PtRu合金鍍膜中，都沒有發現龜裂的產生，因此亦可期待耐蝕性之狀態。然而，PtRu合金鍍膜係皆呈現均勻的金屬光澤，外觀亦良好。The hardness of the PtRu alloy coating basically increases as the Ru concentration increases, showing a maximum Vickers hardness of 760Hv. In addition, no cracks were found in any of the PtRu alloy coatings, so corrosion resistance can be expected. However, PtRu alloy coating systems all exhibit uniform metallic luster and good appearance.
第2實施形態：在本實施形態中，在基材上依次形成基底層(Ni薄膜)、中間層(Pt薄膜)及貴金屬層(PtRu合金薄膜)，製作層積構造，評估貴金屬層的硬度和耐蝕性。將本實施形態中製造的層積構造的構成，示於圖2。Second Embodiment: In this embodiment, a base layer (Ni film), an intermediate layer (Pt film), and a noble metal layer (PtRu alloy film) are sequentially formed on a base material to create a laminated structure, and the hardness and thickness of the noble metal layer are evaluated. Corrosion resistance. The structure of the laminated structure produced in this embodiment is shown in FIG. 2 .
實施例1:準備與第1實施形態相同的基材(Cu板)，在該基材上成膜基底層的Ni薄膜(厚度3.0μm)。Ni薄膜係使用電解電鍍Ni(日本Electroplating Engineers股份有限公司製 MICROFAB Ni200)。之後，成膜中間層的Pt薄膜。Pt鍍敷液與第1實施形態相同，鍍敷條件為浴溫55℃，電流密度為5A/dm 2，鍍敷時間為1分鐘，形成膜厚1.0μm的Pt薄膜所成的中間層。 Example 1: The same base material (Cu plate) as in the first embodiment was prepared, and a Ni thin film (thickness: 3.0 μm) of the base layer was formed on the base material. The Ni thin film system uses electrolytic plating Ni (MICROFAB Ni200 manufactured by Nippon Electroplating Engineers Co., Ltd.). After that, the Pt thin film of the intermediate layer is formed. The Pt plating solution is the same as the first embodiment. The plating conditions are a bath temperature of 55° C., a current density of 5 A/dm 2 , and a plating time of 1 minute. An intermediate layer of a Pt thin film with a film thickness of 1.0 μm is formed.
然後，使用與第1實施形態相同的PtRu合金鍍敷液，成膜貴金屬層之PtRu合金薄膜。本實施形態中，使用Pt濃度為4g/L、Ru濃度為4g/L之PtRu合金鍍敷液，在相同條件下，在鍍敷時間5分鐘內成膜1.0μm的貴金屬層PtRu合金薄膜，製造實施例1的層積構造(Cu/Ni/Pt/PtRu)。對於該實施例1的層積構造，進行EDX所成貴金屬層的組成(Ru濃度)的測定之結果，為Ru濃度13質量%。Then, the same PtRu alloy plating solution as in the first embodiment is used to form a PtRu alloy thin film of the noble metal layer. In this embodiment, a PtRu alloy plating solution with a Pt concentration of 4g/L and a Ru concentration of 4g/L is used, and under the same conditions, a 1.0 μm noble metal layer PtRu alloy thin film is formed within 5 minutes of plating time, and is manufactured. Laminated structure (Cu/Ni/Pt/PtRu) of Example 1. Regarding the laminated structure of Example 1, the composition (Ru concentration) of the noble metal layer formed by EDX was measured, and the result was that the Ru concentration was 13% by mass.
接著，作為用於與上述實施例1的層積構造進行對比的參考例及比較例，製造下述的層積構造。Next, the following laminated structure was produced as a reference example and a comparative example for comparison with the laminated structure of Example 1 described above.
參考例1:在基材/Ni(基底層)，不成膜中間層之Pt薄膜，形成作為貴金屬層之PtRu合金薄膜(2.0μm)的層積構造(Cu/Ni/PtRu)。 比較例1:在基材/Ni(基底層)，不成膜中間層，形成作為貴金屬層之Pt薄膜(2.0μm)的層積構造(Cu/Ni/Pt)。 比較例2:在基材/Ni(基底層)，不成膜中間層，形成作為貴金屬層之RhRu合金薄膜(2.0μm)的層積構造(Cu/Ni/RhRu)。 Reference Example 1: A laminated structure (Cu/Ni/PtRu) in which a PtRu alloy thin film (2.0 μm) is formed as a noble metal layer without forming a Pt thin film as an intermediate layer on the base material/Ni (base layer). Comparative Example 1: A laminated structure (Cu/Ni/Pt) in which a Pt thin film (2.0 μm) was formed as a noble metal layer without forming an intermediate layer on the base material/Ni (base layer). Comparative Example 2: A laminated structure (Cu/Ni/RhRu) of a RhRu alloy thin film (2.0 μm) as a noble metal layer was formed on the base material/Ni (base layer) without forming an intermediate layer.
在上述參考例和比較例1、2的層積構造的製造中，Ni薄膜、Pt薄膜、PtRu合金薄膜的形成係使用與實施例1相同的鍍敷液。膜厚係由鍍敷時間控制。又，RhRu合金薄膜係使用與第1實施形態相同的鍍敷液，浴溫為50℃，電流密度為4.0A/dm 2，鍍敷時間為2分鐘。然而，比較例2的RhRu合金薄膜的組成(Ru濃度)為Ru濃度4質量%。 In the production of the laminated structures of the above-mentioned Reference Examples and Comparative Examples 1 and 2, the same plating solution as in Example 1 was used to form the Ni thin film, Pt thin film, and PtRu alloy thin film. Film thickness is controlled by plating time. In addition, the same plating solution as that of the first embodiment was used for the RhRu alloy thin film, the bath temperature was 50° C., the current density was 4.0 A/dm 2 , and the plating time was 2 minutes. However, the composition (Ru concentration) of the RhRu alloy thin film of Comparative Example 2 was a Ru concentration of 4% by mass.
然後，測定實施例1及各比較例的層積構造的硬度。在本實施形態中，考量貴金屬層的膜厚，以奈米壓痕法進行硬度測定。在該硬度測定中，經由奈米壓痕儀劑(Bruker公司製，Hysitron TS77)測定貴金屬薄膜的接觸剛性(剛度)和接觸深度，算出硬度(GPa)，換算成維氏硬度。Then, the hardness of the laminated structure of Example 1 and each comparative example was measured. In this embodiment, the nanoindentation method is used to measure the hardness in consideration of the film thickness of the precious metal layer. In this hardness measurement, the contact rigidity (stiffness) and contact depth of the noble metal thin film were measured using a nanoindenter agent (Hysitron TS77 manufactured by Bruker), and the hardness (GPa) was calculated and converted into Vickers hardness.
更且，進行了用於評估實施例1及參考例和比較例的層積構造(貴金屬層)的耐蝕性的電解周期試驗。電解周期試驗之條件係將各樣本在1.1質量%氯化鈉溶液中(溫度:室溫)，以30秒施加5V電壓，將其作為1周期返復進行。然後，計數對基底層(Ni)被露出之前的周期數，評估耐蝕性。Furthermore, an electrolysis cycle test was performed to evaluate the corrosion resistance of the laminated structures (noble metal layers) of Example 1, Reference Examples, and Comparative Examples. The conditions for the electrolysis cycle test were to place each sample in a 1.1 mass% sodium chloride solution (temperature: room temperature), apply a voltage of 5V for 30 seconds, and repeat it as one cycle. Then, the number of cycles until the base layer (Ni) was exposed was counted, and the corrosion resistance was evaluated.
將對以上實施例1及參考例1、比較例1、2的層積構造的硬度測定結果和耐蝕性評估結果，示於表2。Table 2 shows the hardness measurement results and corrosion resistance evaluation results of the laminated structures of the above Example 1, Reference Example 1, and Comparative Examples 1 and 2.
從表2可知，關於表面的貴金屬層的硬度，與第1實施形態相同，由實施例1的層積構造的PtRu合金薄膜所成的貴金屬層係超過比較例1的層積構造的貴金屬層的Pt薄膜。然後，如實施例1所示，經由形成Pt薄膜的中間層，PtRu合金薄膜的硬度則增大。又，實施例1的PtRu合金薄膜係相對於比較例2的RhRu合金薄膜，亦具有不遜色的硬度，耐摩耗性亦良好。As can be seen from Table 2, the hardness of the surface precious metal layer is the same as in the first embodiment. The precious metal layer made of the PtRu alloy thin film with the laminated structure of Example 1 exceeds the hardness of the precious metal layer with the laminated structure of Comparative Example 1. Pt film. Then, as shown in Example 1, through the intermediate layer forming the Pt thin film, the hardness of the PtRu alloy thin film increases. In addition, the PtRu alloy thin film of Example 1 also has a hardness comparable to that of the RhRu alloy thin film of Comparative Example 2, and has good wear resistance.
對各層積構造的貴金屬層的耐蝕性進行檢討時，PtRu合金薄膜係可稱本身的耐蝕性良好。即，如參考例1所示，PtRu合金薄膜係即使沒有中間層(Pt薄膜)，直至基底露出為止的周期數也較比較例1(貴金屬層:Pt薄膜)及比較例2(貴金屬層：RhRu合金薄膜)為多。然後，由PtRu合金薄膜所成貴金屬層的耐蝕性，係由於中間層的Pt薄膜的存在而明確提昇。從直至基底露出為止的周期數視之，對於沒有中間層的參考例而言，在實施例1中為5倍。因此，為了使硬度和耐蝕性之兩者皆最佳化，可稱需要由Pt薄膜所成的中間層。When examining the corrosion resistance of the precious metal layers in each laminated structure, it can be said that the PtRu alloy thin film itself has good corrosion resistance. That is, as shown in Reference Example 1, even if there is no intermediate layer (Pt thin film) in the PtRu alloy thin film system, the number of cycles until the base is exposed is longer than that in Comparative Example 1 (noble metal layer: Pt thin film) and Comparative Example 2 (noble metal layer: RhRu). alloy film) for many. Then, the corrosion resistance of the noble metal layer formed by the PtRu alloy film is clearly improved due to the presence of the Pt film in the intermediate layer. The number of cycles until the base is exposed is 5 times that of the reference example without the intermediate layer in Example 1. Therefore, in order to optimize both hardness and corrosion resistance, it can be said that an intermediate layer made of a Pt thin film is required.
第3實施形態：在本實施形態中，相對於實施例1的層積構造，製造變更基底層的構成和中間層及貴金屬層的膜厚的層積構造。在與實施例1相同的基材(Cu)，形成基底層(Ni：3μm)之後，將Au薄膜作為另一層基底層成膜0.25μm。之後，成為令中間層Pt的薄膜的膜厚成為0.5μm，令貴金屬層PtRu合金薄膜的膜厚為0.5μm的層積構造(實施例2：Cu/Ni/Au/Pt/PtRu)。Third Embodiment: In this embodiment, a laminate structure is produced in which the composition of the base layer and the film thickness of the intermediate layer and the precious metal layer are changed with respect to the laminate structure of Example 1. After forming a base layer (Ni: 3 μm) on the same base material (Cu) as in Example 1, an Au thin film was formed as another base layer to a thickness of 0.25 μm. Thereafter, a laminated structure was established in which the film thickness of the intermediate layer Pt film was 0.5 μm and the film thickness of the noble metal layer PtRu alloy film was 0.5 μm (Example 2: Cu/Ni/Au/Pt/PtRu).
在本實施形態適用的追加基底層的Au薄膜係以衝擊鍍敷進行成膜(鍍敷液：PRECIOUSFAB HG-GVC，鍍敷條件：2A/dm2-5秒)。用於形成除此以外的各層的鍍敷液及鍍敷條件係基本上與實施例1相同，以鍍敷時間調整膜厚。又，同樣地，在本實施形態中，作為參考例及比較例所成層積構造，製造下述者。將本實施形態中製造的層積構造的構成，示於圖2。The Au thin film for the additional base layer applied to this embodiment is formed by impact plating (plating liquid: PRECIOUSFAB HG-GVC, plating conditions: 2A/dm2-5 seconds). The plating solution and plating conditions used to form each other layer were basically the same as those in Example 1, and the film thickness was adjusted with the plating time. Moreover, similarly in this embodiment, the following ones were produced as the laminated structures of the reference example and the comparative example. The structure of the laminated structure produced in this embodiment is shown in FIG. 2 .
參考例2：與實施例2相較，在沒有中間層的情況下，形成貴金屬層的PtRu合金薄膜(1.0μm)的層積構造(Cu/Ni/Au/PtRu)。 比較例3：在基材/Ni(基底層)/Au(基底層)，無中間層之情況下，作為貴金屬層形成Pt薄膜(1.0 μm)的層積構造(Cu/Ni/Pt)。 比較例4：在基材/Ni(基底層)/Au(基底層)，於中間層Pt薄膜(0.4μm)形成PdNi薄膜(0.4μm)之後，作為貴金屬層形成PtRu合金薄膜(0.4μm)的層積構造(Cu/Ni/Au/Pt/PdNi/PtRu)。 Reference Example 2: Compared with Example 2, a laminated structure (Cu/Ni/Au/PtRu) of a PtRu alloy thin film (1.0 μm) of a noble metal layer was formed without an intermediate layer. Comparative Example 3: In the case of base material/Ni (base layer)/Au (base layer) without an intermediate layer, a laminated structure (Cu/Ni/Pt) of a Pt thin film (1.0 μm) was formed as a noble metal layer. Comparative Example 4: In base material/Ni (base layer)/Au (base layer), a PdNi thin film (0.4 μm) was formed on an intermediate Pt thin film (0.4 μm), and then a PtRu alloy thin film (0.4 μm) was formed as a noble metal layer. Laminated structure (Cu/Ni/Au/Pt/PdNi/PtRu).
然後，對實施例2、參考例2、比較例3、4的層積構造，進行耐蝕性的評估。在本實施形態的耐蝕性的評估試驗中，在1.1質量%氯化鈉溶液中(溫度：室溫)，以30秒施加12V的電壓，將其作為1周期返復進行。然後，計數對基底層(Ni)被露出之前的周期數，評估耐蝕性。將此評估試驗之結果示於表3。Then, the corrosion resistance of the laminated structures of Example 2, Reference Example 2, and Comparative Examples 3 and 4 was evaluated. In the corrosion resistance evaluation test of this embodiment, a voltage of 12 V was applied for 30 seconds in a 1.1 mass % sodium chloride solution (temperature: room temperature), and this was repeated as one cycle. Then, the number of cycles until the base layer (Ni) was exposed was counted, and the corrosion resistance was evaluated. The results of this evaluation test are shown in Table 3.
根據表3，在本實施形態中檢討的層積構造中，基本上與第2實施形態有相同的傾向。將實施例2的中間層和PtRu合金薄膜成為貴金屬層的層積構造係相對於將Pt薄膜成為貴金屬層的層積構造(比較例3)，明顯耐蝕性優異。又，實施例2係使PtRu合金薄膜成為貴金屬層，但對於沒有中間層的層積構造(參考例2)而言，耐蝕性則為良好。由此可以理解，由Pt薄膜所成的中間層的設置是重要的。According to Table 3, the laminate structure examined in this embodiment basically has the same tendency as in the second embodiment. The laminated structure in which the intermediate layer and the PtRu alloy thin film of Example 2 are used as noble metal layers has significantly better corrosion resistance than the laminated structure in which the Pt thin film is used as the noble metal layer (Comparative Example 3). Furthermore, in Example 2, the PtRu alloy thin film was used as a noble metal layer, but the corrosion resistance was good in the laminated structure without an intermediate layer (Reference Example 2). From this, it can be understood that the arrangement of the intermediate layer made of Pt thin film is important.
然後，在本實施形態中，進行在貴金屬層的PtRu合金薄膜和中間層的Pt薄膜之間，具有其他金屬層(PdNi合金薄膜)的層積構造的檢討(比較例4)。該比較例4係具有與參考例2(Cu/Ni/Au/PtRu)相同程度的耐蝕性，但較實施例2明顯不佳。為了獲得中間層的Pt薄膜的PtRu合金薄膜的耐蝕性提昇的效果，可稱選在Pt薄膜表面上形成PtRu合金薄膜為佳。Next, in this embodiment, a laminated structure having another metal layer (PdNi alloy thin film) between the PtRu alloy thin film of the noble metal layer and the Pt thin film of the intermediate layer was examined (Comparative Example 4). Comparative Example 4 has the same level of corrosion resistance as Reference Example 2 (Cu/Ni/Au/PtRu), but is significantly inferior to Example 2. In order to obtain the effect of improving the corrosion resistance of the PtRu alloy film of the Pt film in the middle layer, it is better to form a PtRu alloy film on the surface of the Pt film.
第4實施形態：在本實施形態中，變更中間層的Pt薄膜的膜厚和貴金屬層的PtRu合金薄膜的膜厚，以檢討層積構造的耐蝕性。層積構造的構成係與實施例1相同，為Cu(基材)/Ni(基底層)/Pt(中間層)/PtRu合金(貴金屬層)。基材及各層的形成方法係與第1實施形態相同，在鍍敷處理時的鍍敷時間，調整膜厚。Fourth Embodiment: In this embodiment, the film thickness of the Pt thin film in the intermediate layer and the film thickness of the PtRu alloy thin film in the noble metal layer are changed to examine the corrosion resistance of the laminated structure. The composition of the laminated structure is the same as in Example 1, which is Cu (base material)/Ni (base layer)/Pt (intermediate layer)/PtRu alloy (noble metal layer). The base material and the formation method of each layer are the same as those in the first embodiment, and the film thickness is adjusted during the plating time during the plating process.
然後，對製造的各層積構造，進行與第2實施形態相同的耐蝕性的評估試驗。將此結果示於表4。Then, the same corrosion resistance evaluation test as in the second embodiment was performed on each of the produced laminated structures. The results are shown in Table 4.
從表4，在中間層(Pt薄膜)的膜厚為共通的情況下，可稱伴隨貴金屬層(PtRu合金薄膜)的膜厚的增加，層積構造的耐蝕性(周期數)則提昇。又，相同膜厚的PtRu合金薄膜之時，則膜厚較厚的中間層的層積構造的耐蝕性較為良好。考慮到成本方面，想要降低高價Pt的使用量時，即使中間層的Pt薄膜為薄至1μm，亦可經由PtRu合金薄膜的膜厚控制，以確保充分的耐蝕性。由此可知，貴金屬層的PtRu合金薄膜和中間層的Pt薄膜的組合，係在確保耐蝕性和耐摩耗性上為適切的。 [產業上的可利用性] From Table 4, when the film thickness of the intermediate layer (Pt thin film) is the same, it can be said that as the film thickness of the noble metal layer (PtRu alloy thin film) increases, the corrosion resistance (number of cycles) of the laminated structure increases. In addition, when the PtRu alloy thin film has the same film thickness, the corrosion resistance of the laminated structure of the intermediate layer with a thicker film thickness is relatively good. Considering the cost, if you want to reduce the usage of expensive Pt, even if the Pt film in the middle layer is as thin as 1 μm, the film thickness of the PtRu alloy film can be controlled to ensure sufficient corrosion resistance. From this, it can be seen that the combination of the PtRu alloy thin film of the noble metal layer and the Pt thin film of the intermediate layer is suitable for ensuring corrosion resistance and wear resistance. [Industrial availability]
如以上所說明，具備由關於本發明的PtRu合金薄膜所成的貴金屬層和由Pt薄膜所成的中間層的層積構造，在硬度(耐磨損)和耐蝕性之兩方面，都顯示良好的特性。本發明係適用於智能手機或平板終端等連接器、端子中的層積構造。As described above, a laminate structure including a noble metal layer made of the PtRu alloy thin film of the present invention and an intermediate layer made of a Pt thin film shows good performance in both hardness (wear resistance) and corrosion resistance. characteristics. The present invention is suitable for laminate structures in connectors and terminals such as smartphones and tablet terminals.
10:基材 11:中間層層 12:貴金屬層 13,13a,13b:基底層 10:Substrate 11: middle layer 12:Precious metal layer 13,13a,13b: basal layer
[圖1]例示關於本發明之層積構造之形態之圖。 [圖2]係顯示第1實施形態的實施例1等的層積構成的構造圖。 [圖3]係顯示第1實施形態的實施例2等的層積構成的構造圖。 [Fig. 1] A diagram illustrating the form of a layered structure according to the present invention. [Fig. 2] Fig. 2 is a structural diagram showing the lamination structure of Example 1 of the first embodiment. [Fig. 3] is a structural diagram showing the lamination structure of Example 2 and the like of the first embodiment.
10:基材 10:Substrate
11:中間層層 11: middle layer
12:貴金屬層 12:Precious metal layer
13,13a,13b:基底層 13,13a,13b: basal layer
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