WO2011145647A1 - 表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物 - Google Patents
表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物 Download PDFInfo
- Publication number
- WO2011145647A1 WO2011145647A1 PCT/JP2011/061414 JP2011061414W WO2011145647A1 WO 2011145647 A1 WO2011145647 A1 WO 2011145647A1 JP 2011061414 W JP2011061414 W JP 2011061414W WO 2011145647 A1 WO2011145647 A1 WO 2011145647A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- plating
- silver
- electrosilver
- oxide layer
- layer
- Prior art date
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 65
- 239000004332 silver Substances 0.000 title claims abstract description 65
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 47
- 238000007747 plating Methods 0.000 claims abstract description 160
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 24
- 239000000956 alloy Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000002310 reflectometry Methods 0.000 description 8
- 238000005486 sulfidation Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009279 wet oxidation reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- IOBIJTFWSZQXPN-UHFFFAOYSA-N [Rh].[Ag] Chemical compound [Rh].[Ag] IOBIJTFWSZQXPN-UHFFFAOYSA-N 0.000 description 1
- JMGVPAUIBBRNCO-UHFFFAOYSA-N [Ru].[Ag] Chemical compound [Ru].[Ag] JMGVPAUIBBRNCO-UHFFFAOYSA-N 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ISDDBQLTUUCGCZ-UHFFFAOYSA-N dipotassium dicyanide Chemical compound [K+].[K+].N#[C-].N#[C-] ISDDBQLTUUCGCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- JZHLPJQGSBLRGM-UHFFFAOYSA-N potassium;ruthenium(3+);tetracyanide Chemical compound [K+].[Ru+3].N#[C-].N#[C-].N#[C-].N#[C-] JZHLPJQGSBLRGM-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- FKPZGVRTVJWAST-UHFFFAOYSA-N tripotassium;rhodium(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Rh+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] FKPZGVRTVJWAST-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C23C28/023—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 only coatings of metal elements only
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
-
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- 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
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
- G02B5/0808—Mirrors having a single reflecting layer
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
Definitions
- the present invention relates to an electrosilver plating and / or an electrosilver alloy plating product having an oxide layer on the surface.
- Silver films have high light reflectivity (hereinafter abbreviated as reflectivity), and therefore are widely used for reflectors for downlight illumination and for reflective surfaces of LED (Lighting Emitting Diode) packages.
- reflectivity high light reflectivity
- LED Lighting Emitting Diode
- the LED package since the input current to the LED is increased until a predetermined light output is obtained, if the reflectance of the reflecting surface that affects the light output that can be taken out is low, the life of the LED is greatly affected. For this reason, in high-power LED packages applied to main lighting such as residential lighting and automotive headlights, the reflectivity and spectral characteristics of the reflecting surface are extremely important factors that affect product performance, especially as high as possible. Reflectance is required.
- the silver film is required to have a high reflectivity in the entire wavelength region (370 to 700 nm) of visible light including near ultraviolet light.
- a silver film is manufactured by an electroless plating process, it takes about 10 to 30 minutes even when a commonly used film thickness of 200 nm is formed. Very low.
- the lifetime of the bath used for a plating process is short, there existed problems, such as a running cost becoming high.
- silver is active, and the surface of the silver film is easily discolored by chlorination and the like, and is corroded particularly in an atmosphere containing sulfur and changes its color to brown or blue black.
- metals other than silver, metal oxides, and sulfides exist in the base of the silver film, these substances easily diffuse into the silver film and migrate to the surface of the silver film. Affects and degrades its performance.
- the configuration of the LED package when a silver film is formed as a light reflecting portion on the copper forming the lead frame, the copper diffuses into the silver film and reaches the surface of the silver film, and the reflectance decreases. Will be invited.
- a diffusion prevention layer comprising any of the platinum group metals palladium, rhodium, platinum, ruthenium, iridium or an alloy thereof.
- Patent Document 2 a diffusion prevention layer comprising any of the platinum group metals palladium, rhodium, platinum, ruthenium, iridium or an alloy thereof.
- the present invention has been made in order to solve the above-mentioned problems, and the object thereof is silver plating and / or silver alloy having high productivity, high reflectivity in the visible light region, and excellent sulfidation resistance. It is to provide a plated product. Another object of the present invention is to provide a light-reflecting material and a light-emitting diode device having, as a reflecting surface, a film having high productivity, high reflectivity in the visible light region, and excellent sulfidation resistance. is there.
- the inventors of the present invention formed a silver plating layer and / or a silver alloy plating layer by electroplating, formed an oxide layer on the outermost surface of the plating layer, and preferably reduced the thickness of the oxide layer to 0. It was found that by setting the thickness to 0.05 ⁇ m or more, a plated product having a high reflectance of about 80 to 99% in the visible light region can be obtained. Moreover, it discovered that it was excellent also in sulfidation resistance by forming an oxide layer, and resulted in this invention.
- the oxide layer refers to a layer in which oxygen is diffused in silver or a silver alloy.
- the present invention is as follows. (1) After forming a silver plating layer and / or a silver alloy plating layer by electro silver plating and / or electro silver alloy plating on the substrate, an oxidation treatment was performed, and an oxide layer was formed on the surface of the plating layer Electrosilver plating and / or electrosilver alloy plating product having an oxide layer on the surface. (2) Electrosilver plating and / or electrosilver alloy plating having an oxide layer on the surface according to (1), wherein the oxide layer formed on the surface of the plating layer has a thickness of 0.05 ⁇ m or more. object.
- the electrosilver plating and / or electrosilver alloy plating product having an oxide layer on the surface thereof according to any one of the above (1) to (3).
- the electrosilvering having an oxide layer on the surface according to any one of (1) to (4), wherein the oxidation treatment is performed in an oxidizing gas atmosphere at 50 to 600 ° C. and / or Or electroplated silver alloy plating.
- the oxidation layer is formed on the surface according to any one of the above (1) to (4), wherein the oxidation treatment is performed by a wet treatment boiling in water or a wet treatment using an oxidizing agent. Electric silver plating and / or electric silver alloy plating product.
- An electrosilver plating and / or an electrosilver alloy plating product comprising: (8) A light-emitting diode device comprising the light reflecting material according to (7).
- an electrosilver plating and / or electrosilver alloy plating product having high productivity, high reflectivity in the visible light region, and excellent sulfidation resistance.
- the light reflecting material and the light emitting diode device according to the present invention there are provided a light reflecting material and a light emitting diode device that have high productivity, have high reflectance in the visible light region, and are excellent in sulfidation resistance. be able to.
- a silver plating layer and / or a silver alloy plating layer is formed on the substrate by electrosilver plating and / or electrosilver alloy plating. Thereafter, an oxidation treatment is performed to oxidize silver, and an oxide layer is formed on the surface of the plating layer.
- Productivity can be improved by forming a silver plating layer and / or a silver alloy plating layer by electroplating.
- the substrate is not particularly limited as long as it can be plated with silver or silver alloy, and examples thereof include copper, silver, nickel, tin, zinc, and alloys thereof.
- the base material is copper
- an oxide layer of 0.5 ⁇ m or more it is possible to prevent copper diffusion even in a silver plating layer having a film thickness of 4 ⁇ m or less, and it is possible to prevent copper diffusion even if the thickness is reduced to 3 ⁇ m.
- the clear mechanism is not known, it is considered that the diffusion of the underlying copper is suppressed by the disappearance or disappearance of the crystal grain boundary due to the oxide film having an amorphous structure.
- the surface roughness Ra of the substrate is desirably 0.5 ⁇ m or less. According to such a configuration, since the high reflectance can be realized while minimizing the film thickness of the silver plating layer and the silver alloy plating layer, the productivity can be increased. Moreover, when forming the base-material surface with nickel, it is desirable for nickel not to contain sulfur. According to such a configuration, even when the silver plating layer and the silver alloy plating layer are thin, it is possible to obtain a reflectance equivalent to that when the film thickness is large and improve the corrosion resistance. .
- Any plating solution may be used for the electrosilver plating and electrosilver alloy plating as long as it can form a silver plating layer and a silver alloy plating layer, and a known plating solution can be used.
- the silver plating solution and the silver alloy plating solution may be either a high cyan bath or a low cyan bath, but a low cyan bath is preferred when an oxide layer is formed by heat treatment.
- the total thickness of the silver plating layer and the silver alloy plating layer is preferably 0.5 to 8 ⁇ m.
- a plated product in which an electroplated silver layer is formed on a substrate and an oxide layer is formed on the surface realizes high reflectivity and increases productivity even when the film thickness of the silver plated layer is thin. be able to.
- the silver plating layer may have a film thickness of 4 ⁇ m or more.
- a plated product in which an electrosilver alloy plating layer is formed on a substrate and an oxide layer is formed on the surface thereof has an effect that the silver alloy plating film itself prevents diffusion of the material to be plated from copper. Even when the plating film thickness is thin, it is possible to prevent a decrease in reflectance.
- This effect is obtained by including 0.01 to 5 wt% of at least one metal selected from zinc, gallium, indium, germanium, tin, antimony, gold, bismuth, palladium, platinum, rhodium, iridium, and ruthenium. I found.
- a more preferable content is 0.1 to 1 wt%.
- the film thickness of the silver alloy plating layer is preferably from 0.1 to 8 ⁇ m, more preferably from 0.5 to 6 ⁇ m.
- oxidation treatment wet oxidation treatment or dry oxidation treatment in the atmosphere or an oxidizing gas atmosphere such as O 2 gas or ozone gas can be used. It is preferable to use a wet oxidation treatment from the viewpoint of mass productivity, and a large amount and a uniform treatment can be performed by the wet oxidation treatment. Also, the dry treatment is preferable from the viewpoint of environmental maintenance because no waste liquid is produced. Further, since the dry process does not require liquid management, process management becomes easy.
- a method of wet oxidation treatment a method of boiling in water or a method of treating with an aqueous solution to which an appropriate amount of an oxidizing agent is added can be used, but in consideration of productivity, an aqueous solution to which an appropriate amount of an oxidizing agent is added is used. It is preferred to use a method of processing.
- the oxidizing agent there can be used oxidizing agents such as nitrates such as nitric acid and sodium nitrate, hydrogen peroxide, manganese peroxide, potassium permanganate, potassium persulfate and sodium hypochlorite.
- the silver plating layer and the silver alloy plating layer may be heated in an oxidizing gas atmosphere at a temperature of 50 to 600 ° C., preferably at a temperature of 100 to 400 ° C. for 30 seconds or more. preferable.
- an oxidizing gas atmosphere at a temperature of 50 to 600 ° C., preferably at a temperature of 100 to 400 ° C. for 30 seconds or more. preferable.
- by reducing the crystal grain boundary it is possible to increase the reflectance in the entire wavelength region (370 to 700 nm) of visible light including near ultraviolet light, which is close to the excitation wavelength of the blue LED. .
- the potassium cyanide concentration in the low silver bath electrosilver alloy plating solution is preferably 0.1 to 10 g / L.
- the surface of the silver plating layer or the silver alloy plating layer becomes an oxide layer and becomes inactive, and it becomes possible to prevent discoloration due to sulfurization or chloride. Further, the reflectance of visible light on the surface of the oxide layer is the same as that in the case where the oxidation treatment is not performed, and there is no concern about the decrease in reflectance, and the decrease in reflectance due to sulfurization or chlorination can be prevented.
- the formed oxide layer preferably has a film thickness of 0.05 ⁇ m or more. Preferably, it is 0.05 to 5 ⁇ m. If it is less than 0.05 ⁇ m, the sulfidation resistance is lowered. A natural oxide film is formed on the surface of the silver plating film in the atmosphere, but it is less than 0.05 ⁇ m. On the other hand, a layer in which oxygen is diffused to a depth of 0.05 ⁇ m or more is formed by performing the oxidation treatment.
- the surface of the silver plating and silver alloy plating film having an oxide layer is preferably such that L is 70 or more, a is ⁇ 1.0 to 1.0, and b is ⁇ 1 to 4 in the Lab color system solid coordinates. If it is in the said range, it is a color tone comparable to a silver film.
- a silver plating and / or silver alloy plating product having the above oxide layer may be used as a light reflecting material, and an LED device is manufactured using the silver plating layer or silver alloy plating layer having the oxide layer as a reflecting surface. May be. According to such an LED device, light emitted from the LED can be efficiently reflected. Further, in this case, the LED device forms a circuit pattern by forming a conductive film on the substrate surface, patterning the conductive film, forming a copper plating layer on the circuit pattern, and a nickel plating layer on the copper plating layer. It is desirable to manufacture by forming a silver plating layer on the nickel plating layer.
- Example 1 and Comparative Example 1 Electro-silver plating was performed on a copper base material under the following silver plating bath and plating conditions.
- Silver plating bath Ag 2.5 g / L (As silver, potassium cyanide is used)
- KCN 5g / L Plating temperature: 25 ° C Plating area: 0.1 dm 2 (25 mm x 20 mm)
- Material to be plated Copper plate Current density: 2 A / dm 2
- the oxidation treatment was performed as follows under the conditions shown in Table 1, and after the oxidation treatment, the thickness and the reflectance of the oxide layer were measured before and after the sulfurization treatment.
- Comparative Example 1 the oxidation treatment was not performed, and the thickness and the reflectance of the oxide layer were measured before and after the sulfidation treatment.
- the film thickness of the silver plating film and / or silver alloy plating film was determined by fluorescent X-ray analysis. The results are shown in Table 1.
- Oxidation treatment Dry processing was performed. Using a hot plate, heat in air for 10 minutes at a given temperature. The thickness of the oxide layer formed on the surface was analyzed by SIMS from the surface, and the thickness of the oxide layer was defined as the depth at which the change in etching rate and the measured oxygen value suddenly decreased from the surface and became flat once.
- Example 2 instead of electro silver plating, the following silver alloy plating bath and plating conditions were used, and plating was performed in the same manner as in Example 1 except that the oxidation treatment temperature was set to the temperature described in Table 1.
- Example 2 3 and 3 were obtained and evaluated in the same manner as in Example 1.
- a plated product of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that silver alloy plating was performed in the following silver alloy plating bath and plating conditions instead of electrosilver plating. And evaluated in the same manner.
- Silver-palladium plating bath Ag 2.5 g / L (As silver, silver potassium cyanide is used)
- Pd 5.0 g / L (using potassium potassium cyanide)
- KCN 5g / L
- Plating temperature 25 ° C
- Plating area 0.1 dm 2 (25 mm x 20 mm)
- Material to be plated Copper plate Current density: 2 A / dm 2
- the alloy composition of the silver alloy plating film was determined from the strength of the formed silver alloy plating.
- Example 4 Comparative Example 3
- Example 1 the following silver alloy plating bath and plating conditions were used instead of electrosilver plating, and plating was performed in the same manner as in Example 1 except that the oxidation treatment temperature was set to the temperature described in Table 1.
- Example 4 A plated product was obtained and evaluated in the same manner as in Example 1.
- Comparative Example 1 a plated product of Comparative Example 3 was obtained in the same manner as Comparative Example 1 except that silver alloy plating was performed using the following silver alloy plating bath and plating conditions instead of electrosilver plating. And evaluated in the same manner.
- Silver-ruthenium plating bath Ag 2.5 g / L (As silver, silver potassium cyanide is used) Ru: 5.0 g / L (uses ruthenium potassium cyanide) KCN: 5g / L Plating temperature: 25 ° C Plating area: 0.1 dm 2 (25 mm x 20 mm) Material to be plated: Copper plate Current density: 2 A / dm 2
- Example 5 Comparative Example 4
- Example 1 instead of electrosilver plating, the following silver alloy plating bath and plating conditions were used, and plating was performed in the same manner as in Example 1 except that the oxidation treatment temperature was set to the temperature described in Table 1.
- Example 5 A plated product was obtained and evaluated in the same manner as in Example 1.
- Comparative Example 1 a plated product of Comparative Example 4 was obtained in the same manner as Comparative Example 1 except that silver alloy plating was performed using the following silver alloy plating bath and plating conditions instead of electrosilver plating. And evaluated in the same manner.
- Silver-rhodium plating bath Ag 2.5 g / L (As the Ag, use silver potassium cyanide) Rh: 5.0 g / L (using potassium rhodium cyanide) KCN: 5g / L Plating temperature: 25 ° C Plating area: 0.1 dm 2 (25 mm x 20 mm) Material to be plated: Copper plate Current density: 2 A / dm 2
- Example 6 The oxidation treatment of the silver plating product obtained in Example 1 was changed to a wet treatment, and the oxidation treatment was performed by immersing in an aqueous solution containing 50 g / L manganese peroxide and 40 g / L sodium hydroxide at 80 ° C. for 5 minutes.
- a plated product of Example 6 was obtained in the same manner as in Example 1 except that the evaluation was performed in the same manner as in Example 1.
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Abstract
Description
しかし、特許文献1記載の方法では、無電解めっき処理により銀膜が製造されているために、通常用いられる膜厚200nmを形成する場合でも10~30分程度の時間を要し、生産性が極めて低い。また、めっき処理に用いられる浴の寿命が短いためにランニングコストが高くなるなどの問題があった。
前記銀皮膜中への拡散を防止するための技術については例えば、銀めっき皮膜の形成前に、白金族金属のパラジウム、ロジウム、白金、ルテニウム、イリジウムのいずれかまたはそれらの合金からなる拡散防止層を設けることが提案されている(特許文献2)。
しかし、銀皮膜の光反射性能の改善、特に硫黄を含む雰囲気中での変色による光反射性能の低下に対する対策については、まだ有効な技術開発がなされておらず、特に白色光源としての利用促進に資する上でこうした改善が要望されている。
また、本発明の他の目的は、生産性が高く、可視光領域において高い反射率を有し、かつ耐硫化性に優れる膜を反射面として有する光反射材及び発光ダイオードデバイスを提供することにある。
尚、本発明において前記酸化層とは、銀中、又は銀合金中に酸素が拡散している層のことを言う。
(1)基材上に電気銀めっき及び/又は電気銀合金めっきにより銀めっき層及び/又は銀合金めっき層を形成した後、酸化処理を行い、前記めっき層表面に酸化層を形成したことを特徴とする表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
(2)前記めっき層表面に形成された酸化層の膜厚が0.05μm以上であることを特徴とする前記(1)記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
(3)前記銀合金めっき層において、亜鉛、ガリウム、インジウム、ゲルマニウム、錫、アンチモン、金、ビスマス、パラジウム、白金、ロジウム、イリジウム、ルテニウムから選ばれる少なくとも1種以上の金属を0.01~5wt%含むことを特徴とする前記(1)又は(2)記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
(4)前記酸化層を有する銀めっき及び/又は電気銀合金めっき層が、Lab表色系立体座標において、Lが70以上、aが-1.0~1.0、bが-1~4であることを特徴とする前記(1)~(3)のいずれかに記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
(5)前記酸化処理が、酸化性ガス雰囲気中50~600℃で行われることを特徴とする前記(1)~(4)のいずれかに記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
(6)前記酸化処理が、水中で煮沸する湿式処理、又は酸化剤を用いた湿式処理で行われることを特徴とする前記(1)~(4)のいずれかに記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
(7)前記表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物が光反射材であることを特徴とする前記(1)~(6)のいずれかに記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
(8)前記(7)記載の光反射材を有することを特徴とする発光ダイオードデバイス。
銀めっき層及び/又は銀合金めっき層を電気めっきにより形成することにより生産性を高めることができる。
銀めっき液および銀合金めっき液は、高シアン浴でも低シアン浴でも良いが、加熱処理により酸化層を形成する際は、低シアン浴が好ましい。また光沢剤を添加しなくてもよい。電気めっきに用いられる光沢剤濃度を測定することは現状の分析技術では不可能であるため、めっき浴中の光沢剤濃度を厳密に定量、維持、管理することは実質上できない。このため、光沢剤を含まないめっき浴の方が製造上一定品質を維持しやすい。
基材上に電気銀めっき層を形成し、その表面に酸化層を形成しためっき物は、該銀めっき層の膜厚が薄い場合であっても、高い反射率を実現し、生産性を高めることができる。一方で、銀めっき層は4μm以上の膜厚を有していてもよい。
基材上に電気銀合金めっき層を形成し、その表面に酸化層を形成しためっき物は、該銀合金めっき膜が、それ自体で被めっき材の銅からの拡散を防止する効果を有し、めっき膜厚が薄い場合でも反射率の低下を防ぐことが可能である。この効果は亜鉛、ガリウム、インジウム、ゲルマニウム、錫、アンチモン、金、ビスマス、パラジウム、白金、ロジウム、イリジウム、ルテニウムから選ばれる少なくとも1種以上の金属を0.01~5wt%含むことにより得られることを見出した。より好ましい含有量は0.1~1wt%である。
銀合金めっき層の膜厚は0.1~8μmが好ましく、0.5~6μmがより好ましい。
湿式酸化処理の方法としては、水中で煮沸する方法や、適量の酸化剤を添加した水溶液で処理する方法などを使用することができるが、生産性を考慮すると適量の酸化剤を添加した水溶液で処理する方法を使用するのが好ましい。酸化剤としては、硝酸、硝酸ナトリウムなどの硝酸塩、過酸化水素、過酸化マンガン、過マンガン酸カリウム、過硫酸カリウム、次亜塩素酸ナトリウムなどの酸化剤を使用することができる。
また、銀めっき膜表面には大気中では自然酸化膜が形成されるが0.05μm未満に過ぎない。一方、酸化処理を行うことにより0.05μm以上の深さまで酸素が拡散した層が形成される。
実施例1及び比較例1
銅基材に以下の銀めっき浴及びめっき条件で電気銀めっきを行った。
銀めっき浴
Ag:2.5g/L(Agとしてはシアン化銀カリウムを使用)
KCN:5g/L
めっき温度:25℃
めっき面積:0.1dm2(25mm×20mm)
被めっき材:銅板
電流密度:2A/dm2
次に、実施例1では表1記載の条件で以下のように酸化処理を行い、酸化処理後、硫化処理を行う前後で酸化層の膜厚及び反射率を測定した。また、比較例1では酸化処理を行わず、硫化処理を行う前後で酸化層の膜厚及び反射率を測定した。
尚、銀めっき膜及び/又は銀合金めっき膜の膜厚は、蛍光X線分析により求めた。
結果を表1に示す。
乾式処理を行った。ホットプレートを用い、大気中で10分間所定の温度で加熱。
表面に形成された酸化層の厚みは、表面からSIMS分析を行い、エッチングレートの変化と酸素の測定値が表面から急減して一旦平坦になる深さを持って酸化層の厚みとした。
JIS H 8502に基づく硫化水素ガス試験は、硫化水素を使用し危険であるため、簡便な代替試験として一般に行われる以下の試験を行い、外観の変化を反射率の変化として評価した。表では「硫化処理」として表示する。
硫化アンモン試薬0.3%水溶液
液温度 25℃
浸漬時間 5分
反射率:
分光光度計(島津製作所製UV-2200)を用い、硫酸Ba粉末標準で、波長550nmにて測定した。一般に白色を得るために波長550nmの黄色のLEDを光源として用い、更にその光を蛍光体を用いて調整している。反射率の評価にはその光源の波長を用いて評価した。
実施例1において、電気銀めっきの代わりに以下の銀合金めっき浴及びめっき条件を使用し、酸化処理温度を表1記載の温度とした以外は実施例1と同様にめっきを行い、実施例2及び3のめっき物を得、実施例1と同様に評価した。
また、比較例1において、電気銀めっきの代わりに以下の銀合金めっき浴及びめっき条件で銀合金めっきを行った以外は比較例1と同様にして比較例2のめっき物を得、比較例1と同様に評価した。
銀-パラジウムめっき浴
Ag:2.5g/L(Agとしてはシアン化銀カリウムを使用)
Pd:5.0g/L(シアン化パラジウムカリウムを使用)
KCN:5g/L
めっき温度:25℃
めっき面積:0.1dm2(25mm×20mm)
被めっき材:銅板
電流密度:2A/dm2
尚、銀合金めっき膜の合金組成は形成された銀合金めっきの強度により求めた。
実施例1において、電気銀めっきの代わりに以下の銀合金めっき浴及びめっき条件を使用し、酸化処理温度を表1記載の温度とした以外は実施例1と同様にめっきを行い、実施例4のめっき物を得、実施例1と同様に評価した。
また、比較例1において、電気銀めっきの代わりに以下の銀合金めっき浴及びめっき条件で銀合金めっきを行った以外は比較例1と同様にして比較例3のめっき物を得、比較例1と同様に評価した。
銀-ルテニウムめっき浴
Ag:2.5g/L(Agとしてはシアン化銀カリウムを使用)
Ru:5.0g/L(シアン化ルテニウムカリウムを使用)
KCN:5g/L
めっき温度:25℃
めっき面積:0.1dm2(25mm×20mm)
被めっき材:銅板
電流密度:2A/dm2
実施例1において、電気銀めっきの代わりに以下の銀合金めっき浴及びめっき条件を使用し、酸化処理温度を表1記載の温度とした以外は実施例1と同様にめっきを行い、実施例5のめっき物を得、実施例1と同様に評価した。
また、比較例1において、電気銀めっきの代わりに以下の銀合金めっき浴及びめっき条件で銀合金めっきを行った以外は比較例1と同様にして比較例4のめっき物を得、比較例1と同様に評価した。
銀-ロジウムめっき浴
Ag:2.5g/L(Agとしてはシアン化銀カリウムを使用)
Rh:5.0g/L(シアン化ロジウムカリウムを使用)
KCN:5g/L
めっき温度:25℃
めっき面積:0.1dm2(25mm×20mm)
被めっき材:銅板
電流密度:2A/dm2
実施例1において得られた銀めっき物の酸化処理を湿式処理に変更し、過酸化マンガン50g/L、水酸化ナトリウム40g/Lを含有する水溶液に80℃で5分間浸漬して酸化処理を行った以外は実施例1と同様にして実施例6のめっき物を得、実施例1と同様に評価した。
また銀合金の場合は被めっき材の銅からの拡散を防止することができるため、めっき膜厚が薄い場合でも反射率の低下を防ぐことができる。
Claims (8)
- 基材上に電気銀めっき及び/又は電気銀合金めっきにより銀めっき層及び/又は銀合金めっき層を形成した後、酸化処理を行い、前記めっき層表面に酸化層を形成したことを特徴とする表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
- 前記めっき層表面に形成された酸化層の膜厚が0.05μm以上であることを特徴とする請求項1記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
- 前記銀合金めっき層において、亜鉛、ガリウム、インジウム、ゲルマニウム、錫、アンチモン、金、ビスマス、パラジウム、白金、ロジウム、イリジウム、ルテニウムから選ばれる少なくとも1種以上の金属を0.01~5wt%含むことを特徴とする請求項1又は2記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
- 前記酸化層を有する銀めっき及び/又は電気銀合金めっき層が、Lab表色系立体座標において、Lが70以上、aが-1.0~1.0、bが-1~4であることを特徴とする請求項1~3のいずれかに記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
- 前記酸化処理が、酸化性ガス雰囲気中50~600℃で行われることを特徴とする請求項1~4のいずれかに記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
- 前記酸化処理が、水中で煮沸する湿式処理、又は酸化剤を用いた湿式処理で行われることを特徴とする請求項1~4のいずれかに記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
- 前記表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物が光反射材であることを特徴とする請求項1~6のいずれかに記載の表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物。
- 請求項7記載の光反射材を有することを特徴とする発光ダイオードデバイス。
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US13/380,946 US20120097545A1 (en) | 2010-05-20 | 2011-05-18 | Silver electroplated and/or silver alloy electroplated article having an oxidation layer on its surface |
KR1020137032232A KR20130139381A (ko) | 2010-05-20 | 2011-05-18 | 광반사재 및 발광다이오드 디바이스 |
KR1020127001485A KR101374466B1 (ko) | 2010-05-20 | 2011-05-18 | 표면에 산화층을 갖는 전기 은도금 및/또는 전기 은합금 도금물 |
CN2011800031019A CN102471895B (zh) | 2010-05-20 | 2011-05-18 | 表面具有氧化层的电镀银和/或电镀银合金的镀件 |
EP11783581.9A EP2573208A4 (en) | 2010-05-20 | 2011-05-18 | ELECTROLYTIC SILVER PLATED AND / OR ELECTROLYTIC SILVER ALLOY PLATED ARTICLES WITH AN OXID SURFACE LAYER |
JP2011552265A JP5382888B2 (ja) | 2010-05-20 | 2011-05-18 | 表面に酸化層を有する電気銀めっき及び/又は電気銀合金めっき物 |
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JP2020053599A (ja) * | 2018-09-27 | 2020-04-02 | 日亜化学工業株式会社 | 光半導体装置用金属材料、及びその製造方法、及びそれを用いた光半導体装置 |
US10875127B2 (en) | 2017-09-22 | 2020-12-29 | Nichia Corporation | Method for bonding electronic component and method for manufacturing bonded body |
WO2023120239A1 (ja) * | 2021-12-21 | 2023-06-29 | Dowaメタルテック株式会社 | 複合材、複合材の製造方法および端子 |
JP7490134B1 (ja) | 2023-11-30 | 2024-05-24 | 松田産業株式会社 | 銀めっき皮膜及び該銀めっき皮膜を備えた電気接点 |
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US9847468B1 (en) * | 2016-06-20 | 2017-12-19 | Asm Technology Singapore Pte Ltd | Plated lead frame including doped silver layer |
CN111247645B (zh) * | 2017-10-25 | 2024-04-26 | 松下控股株式会社 | 光半导体装置用封装、光半导体装置及光半导体装置用封装的制造方法 |
CN113061948A (zh) * | 2021-03-17 | 2021-07-02 | 厦门乐钢材料科技有限公司 | 一种金属铜基底电化学镀银的方法及其复合结构 |
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JPWO2011145647A1 (ja) | 2013-07-22 |
EP2573208A4 (en) | 2014-05-21 |
CN102471895A (zh) | 2012-05-23 |
CN102471895B (zh) | 2013-12-18 |
KR101374466B1 (ko) | 2014-03-17 |
US20120097545A1 (en) | 2012-04-26 |
TW201202488A (en) | 2012-01-16 |
KR20130139381A (ko) | 2013-12-20 |
JP5382888B2 (ja) | 2014-01-08 |
TWI428479B (zh) | 2014-03-01 |
KR20120024985A (ko) | 2012-03-14 |
EP2573208A1 (en) | 2013-03-27 |
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