TWI558478B - 基材用金屬箔 - Google Patents
基材用金屬箔 Download PDFInfo
- Publication number
- TWI558478B TWI558478B TW100142081A TW100142081A TWI558478B TW I558478 B TWI558478 B TW I558478B TW 100142081 A TW100142081 A TW 100142081A TW 100142081 A TW100142081 A TW 100142081A TW I558478 B TWI558478 B TW I558478B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- metal foil
- thickness
- substrate
- containing metal
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 165
- 239000002184 metal Substances 0.000 title claims description 165
- 239000011888 foil Substances 0.000 title claims description 108
- 239000000463 material Substances 0.000 title description 9
- 239000000758 substrate Substances 0.000 claims description 58
- 229910000831 Steel Inorganic materials 0.000 claims description 45
- 239000010959 steel Substances 0.000 claims description 45
- 229910045601 alloy Inorganic materials 0.000 claims description 41
- 239000000956 alloy Substances 0.000 claims description 41
- 229910000765 intermetallic Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 18
- 238000005401 electroluminescence Methods 0.000 claims description 18
- 229910015372 FeAl Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000007747 plating Methods 0.000 description 44
- 239000010949 copper Substances 0.000 description 42
- 239000010408 film Substances 0.000 description 41
- 238000005096 rolling process Methods 0.000 description 39
- 230000007797 corrosion Effects 0.000 description 24
- 238000005260 corrosion Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 12
- 238000005452 bending Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910004613 CdTe Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 238000007743 anodising Methods 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- PZKBIVOXIFYDRI-UHFFFAOYSA-N CC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound CC(C(OCC)(OCC)OCC)CCCCCCCC PZKBIVOXIFYDRI-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ZGTWUOAFEWVAQQ-UHFFFAOYSA-N [Al+3].[Al+3].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O.[O-][Cr]([O-])=O Chemical compound [Al+3].[Al+3].[O-][Cr]([O-])=O.[O-][Cr]([O-])=O.[O-][Cr]([O-])=O ZGTWUOAFEWVAQQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/012—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of aluminium or an aluminium alloy
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- 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
-
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Description
本發明係有關於一種能夠使用作為化合物系太陽電池、薄膜系太陽電池、使該等複數層積層而成之混合型太陽電池、及有機電致發光(Organic Electro-Luminescence)照明的基材之金屬箔。
本發明係基於2010年11月17日向日本申請之特願2010-257322號而主張優先權，並且將其內容引用於此。
在CIGS(銅-銦-鎵-硒；Copper-Indium-Gallium-Sele nium)、CIS(銅-銦-硒；Copper-Indium-Selenium,)、CdTe(鉻-碲；Cadmium-Tellur)等的化合物系太陽電池、非晶Si等的薄膜系太陽電池、使該等複數層積層而成之混合型太陽電池及有機EL(電致發光；Electro-Luminescence)照明，為了堅強地支撐CIGS層、CIS層、CdTe層、非晶Si層和有機EL層等之目的，係使用稱為基材之基座。
先前，作為上述基材，如專利文獻1所記載，多半是使用玻璃基材。但是，因為玻璃係容易產生裂紋，為了確保一定的強度，厚膜化係有必要的。將玻璃厚膜化時，太陽電池、有機EL照明本身會變重。
另一方面，近年來，作為上述基材，係嘗試使用不容易產生裂紋而且適合於薄膜化的金屬箔來代替玻璃基材。
基材用的金屬箔係被要求耐蝕性、表面平滑性及彈塑性變形性的任一者均良好。
因為使用作為基材之金屬箔，係有可能在屋外環境被長期間曝露使用長達20年，上述耐蝕性係被認為有必要的。
因為避免在基材表面存在之突起狀缺陷造成在基材上所積層的太陽電池層和有機EL層蒙受物理性的損傷，上述表面平滑性係被認為有必要的。基材表面係被期望是不具有突起狀缺陷之平滑的表面。
為了使硬質的玻璃基材為不可能之將基材用金屬箔捲取成為捲物形狀成為可能，上述彈塑性變形性係被認為有必要的。其結果，若能夠將使用批次處理之製造變更為使用捲裝進出(roll to roll)處理之連續製造時，能夠大幅度地減低太陽電池和有機EL的製造成本。
作為基材用金屬箔，通常耐蝕性優良的不鏽鋼(SUS)箔的使用係進展中。如專利文獻2所記載，亦有使用在SUS箔上進一步形成有機被膜而成之基材。
因為SUS箔係具有優良的耐蝕性，能夠使用作為基材用金屬箔。但是，SUS箔係有材料昂貴之問題。並且，因為SUS箔係硬度高而不容易輥軋，亦有製造成本高之問題。因此，相較於玻璃基材，現狀其使用係不怎麼普遍。
另一方面，相較於SUS，普通鋼(碳鋼)箔的材料本身係比較便宜，而且，因為具有高塑性變形性能，製造成本亦能夠大幅度地減低。但是，普通鋼箔的直接狀態係無法滿足作為基材用金屬箔所被要求的耐蝕性。若能夠利用可滿
足基材用金屬箔所被要求的上述特性之普通鋼箔時，能夠大幅度地減低太陽電池及有機EL的製造成本。因此，目前其開發係被強烈地期待。
[專利文獻1]日本專利特開2006-80370號公報
[專利文獻2]日本專利特開2006-295035號公報
本發明的一實施態樣，係鑒於上述情形而進行，其目的係提供一種能夠同時滿足作為太陽電池和有機EL的基材用金屬箔被要求之耐蝕性、表面平滑性及彈塑性變形性之價廉的基材用金屬箔。
本發明的要旨係如以下。
(1)本發明的一態樣之基材用金屬箔，其係具備厚度為10~200μm之鋼層、生成於前述鋼層上之含Fe及Al的合金層、及配置於前述合金層上之含Al金屬層之金屬箔；以與輥軋前述金屬箔的方向正交之板寬度方向作為觀察面沿著板厚度方向平面截斷，將截斷面所出現之前述含Al金屬層的表面之截斷線設作輪廓曲線，且將近似前述輪廓曲線的直線設作輪廓平均直線時，不存在與前述輪廓平均直線的距離超過10μm之在前述輪廓曲線的前述含Al金屬層表面
側凸出之極大點；前述合金層係厚度為0.1~8μm且含有Al7Cu2Fe金屬間化合物、或FeAl3基的金屬間化合物。
(2)如上述(1)之基材用金屬箔，其係在前述鋼層與前述合金層之間，可以進一步具有厚度為2~10μm的Cu層、或厚度為2~10μm的Ni層。
(3)如上述(1)或(2)之基材用金屬箔，其中前述含Al金屬層的厚度係可以是0.1~30μm。
(4)如上述(1)至(3)項中任一項之基材用金屬箔，其係在前述含Al金屬層上，可以進一步具有厚度為0.01~0.08μm的AlN層、或厚度為0.01~50μm的Al2O3層。
(5)如上述(1)至(3)項中任一項之基材用金屬箔，其係在前述含Al金屬層上，可以進一步具有厚度為0.1~8μm的Cr層、或厚度為0.1~8μm的Ni層。
(6)如上述(1)至(3)項中任一項之基材用金屬箔，其係在前述含Al金屬層上，可以進一步具有選自溶膠凝膠層及疊合層之至少1種皮膜。
依照本發明的上述態樣，能夠提供一種相較於玻璃基材，不容易產生裂紋而且適合於薄膜化，並且能夠滿足作為基材用金屬箔所被要求之耐蝕性、表面平滑性及彈塑性變形性之價廉的基材用金屬箔及其製造方法。因此，能夠製造低成本且薄型輕量的CIGS、CIS、CdTe等的化學系太陽電池、非晶Si等的薄膜系太陽電池、使該等複數層積層而成之混合型太陽電池及有機EL照明。
以下，詳細地說明本發明的較佳實施形態。首先，針對基材用金屬箔的技術結構及數值限定理由進行詳細地說明。
為了提升普通鋼(碳鋼)的耐蝕性，係對普通鋼施行含Al鍍覆。藉由該含Al鍍覆而在鋼層上配置含Al金屬層。藉由該含Al金屬層來提升作為基材用金屬箔被要求之耐蝕性。
上述含Al金屬層係以含有60~100質量%的Al、0~15質量%的Si、0~40質量%的Cu之組成為佳。這是因為該組成之鍍覆浴的熔點降低，使得鍍覆步驟變為簡便之緣故。更佳是使上述含Al金屬層的以下各成分為從為68.2質量%Al-4.7質量%Si-27.1質量%Cu、或68質量%Al-32質量%Cu的組成±5質量%以內的範圍之組成。該組成係鍍覆浴的熔點進一步降低。又，上述含Al金屬層的厚度係以0.1~30μm為佳。小於0.1μm時，無法得到適當的耐蝕效果，超過30μm時，係因為必須大量地鍍覆Al致使生產成本提高。較佳是使上述含Al金屬層的厚度為1~30μm。更佳是使上述含Al金屬層的厚度為3~30μm。最佳是使上述含Al金屬層的厚度為8~30μm。
通常，含Al的鍍覆時，在鋼層及含Al金屬層之界面係形成Fe-Al系合金相(例如FeAl3,Fe2Al8Si、FeAl5Si等的金屬間化合物)。該合金層係非常地硬而脆。經施行含Al鍍覆之
金屬箔在操作等的情況進行彈塑性變形時，該合金層係無法追隨金屬箔的變形，最後，鋼層與含Al金屬層產生剝離、以及誘發含Al金屬層產生裂紋。亦即，在普通鋼箔施行含Al鍍覆時，雖然能夠滿足作為基材用金屬箔被要求的耐蝕性，但是無法滿足彈塑性變形性。
為了滿足作為基材用金屬箔被要求的彈塑性變形性，生成於鋼層與含Al金屬層的界面之上述合金層，係厚度為0.1~8μm且含有Al7Cu2Fe金屬間化合物、或FeAl3基的金屬間化合物為必要的。該Al7Cu2Fe金屬間化合物、或FeAl3基的金屬間化合物係在上述合金層中，面積%計係以含有50%以上為佳，以含有90%以上為更佳。
在此，所謂FeAl3基的金屬間化合物，係指在FeAl3金屬間化合物中，固溶有構成系的元素(例如Si和Cu等構成含Al金屬層之元素、Ni和Cu等構成預鍍覆膜之元素、或C、P、Cr、Ni、Mo等構成鋼層之元素)之金屬間化合物、及由構成上述系之元素、Fe、Al以新的組成比形成之金屬間化合物。該FeAl3基的金屬間化合物，係以固溶有Cu之FeAl3基的金屬間化合物、或固溶有Ni之FeAl3基的金屬間化合物為特佳。但是如後述，只要該合金層的維氏硬度(Vickers hardness)為500~600Hv左右，固溶之元素係不限定於Ni或Cu。
含有上述的Al7Cu2Fe金屬間化合物或FeAl3基的金屬間化合物之合金層，係藉由在對普通鋼施行含Al鍍覆時，構成系的元素係從述之Cu或Ni預鍍覆膜、鋼層、含Al金屬層
擴散，而且與Fe及Al合金化而形成。如此，為了適當地形成含有上述Al7Cu2Fe金屬間化合物、或FeAl3基的金屬間化合物之合金層，以在施行含Al鍍覆之前，藉由預先對普通鋼施行Cu或Ni預鍍覆而在鋼層上預先形成Cu或Ni的預鍍覆膜為佳。但是因為上述合金層係例如藉由構成鋼層及含Al金屬層之元素的擴散亦能夠形成，Cu或Ni預鍍覆膜不是必須的技術結構。
該含有Al7Cu2Fe金屬間化合物或FeAl3基的金屬間化合物之合金層，其維氏硬度為500~600Hv。上述先前硬而脆的合金層，其維氏硬度為900Hv左右。如此，藉由將合金層控制為比較軟質之層，能夠提升金屬箔的彈塑性變形性。又，上述合金層的厚度小於0.1μm時，作為軟質合金層，係無法得到上述的效果。其厚度超過8μm時，構成系之元素的擴散係過度進行，因為容易產生克肯達耳孔洞(Kirkendall voids)，乃是不佳。
為了進一步提高金屬箔的彈塑性變形性，較佳是使上述金屬層的厚度為0.1~5μm。又，藉由使其度為3~8μm，因為金屬箔的耐蝕性進一步提高，乃是適合的。藉由使上述金屬層的厚度為3~5μm時，因為能夠同時得到兩種效果，乃是最佳。
又，在上述鋼層與上述合金層之間，使Cu或Ni預鍍覆膜以2~10μm的厚度殘留而成為Cu層或Ni層時，因為鋼層與合金層之間的密著性進一步增加且彈塑性變形性提升，乃是較佳。其結果，即便在加壓成形或深壓縮時進行嚴酷的
加工，上述合金層亦不容易產生剝離。
在鋼層與合金層之間，即便上述的Cu層或Ni層存在，亦不會妨礙上述合金層所具有的效果。但是Cu層或Ni層的厚度小於2μm時，無法得到提升鋼層與合金層之間的密著性之效果。又，其厚度超過10μm時，上述效果飽和而且形成預鍍覆膜的成本亦上升，乃是不佳。
又，金屬箔的鋼層之厚度係設為10~200μm。製造厚度小於10μm的箔係會產生謹慎地控制高精密度的裝置之必要性，而成為高成本。又，厚度超過200μm時，金屬箔的重量變重，致使無法充分地得到使用箔之優點。為了減輕基材的重量，厚度係以10~150μm為佳。又，為了提高材料的強度而在基材上載置重物，厚度係以100~200μm為佳。又。將上述鋼層的厚度設為100~150μm時，因為能夠同時得到兩種效果，乃是最佳。
太陽電池和有機EL的基材用金屬箔係除了上述耐蝕性及彈塑性變形性以外，亦同時滿足表面平滑性係重要的。
為了滿足作為基材用金屬箔被要求之表面平滑性，含Al金屬層的表面為一定程度的平滑面係必要的。具體上，以與金屬箔的輥軋方向正交之板寬度方向作為觀察面的方式沿著板厚度方向平面截斷，將截斷面所出現之含Al金屬層的表面之截斷線設作輪廓曲線，而且將近似輪廓曲線的直線設作輪廓平均直線時，不存在與輪廓平均直線的距離超過10μm之上輪廓曲線的極大點係必要的。
在此，上述所謂極大點，係在上述輪廓曲線的含Al金
屬層表面側凸出之極點。又，因為輪廓曲線的極小點(在上述輪廓曲線的含Al金屬層表面上呈凹狀的極點)係不會對在基材用金屬箔上所積層的太陽電池層和有機EL層造成物理上的損傷，即便存在亦不會有問題。
又，上述輪廓曲線係可以從上述截斷面的金屬組織照片且藉由影像處理來求得其軌跡，亦可藉由人工來求得其軌跡。藉由影像處理來求得輪廓曲線時，同樣地，藉由影像處理且應用相位補償型濾波器而求取輪廓平均直線即可。藉由人工求得輪廓曲線時，能夠從各極點的座標藉由最小二乘方法來求得輪廓平均直線。
在含Al金屬層表面存在有超過10μm之突起狀缺陷時，有造成在基材用金屬箔上所積層的太陽電池層和有機EL層造成物理上的損傷之可能性。例如太陽電池時，基材上的太陽電池層受到上述的損傷時，其區域的光電轉換效率係有低落之可能性。
又，為了得到充分的光電轉換效率，從前述輪廓平均直線的距離係以不存在超過5μm之極大點為佳。而且，以不存在超過1μm之極大點為更佳。
上述含Al金屬層表面，其光澤度係以銀鏡比為75%以上為佳。例如太陽電池係存在有入射時未能夠對光電轉換有貢獻而到達基材亦即金屬箔之太陽光。該透射光係能夠藉由金屬箔反射而再次提供給光電轉換使用。光澤度係銀鏡比為75%以上時，因為高效率且透射光能夠再次提供給光電轉換使用，乃是較佳。更佳是光澤度係銀鏡比為80%
以上。
上述之金屬箔的表面平滑性及光澤度，係能夠藉由在上述第2輥軋處理時使用鏡面狀態的軋輥，或是對第2輥軋處理後的金屬箔施行平整(skin pass)輥軋而達成。針對本發明的實施形態之製造方法，係詳細地後述。
在上述含Al金屬層的表面，以進一步具有厚度為0.01~0.08μm的AlN層或厚度為0.01~50μm的Al2O3層為佳。Fe原子從鋼層擴散至太陽電池層和有機EL層等時，有損害該等層的功能之可能性。例如，Fe原子從鋼層擴散至太陽電池的CIGS層和CIS層等時，因為會使能帶隙(band gap)變為狹窄，而產生太陽電池的轉換效率低落之不良。藉由上述AlN層或上述Al2O3層作為阻障膜之作用，能夠防止構成鋼層之Fe原子擴散而到達CIGS層和CIS層之情形。但是，該等層的厚度小於0.01μm時，無法得到上述的效果。生成厚度超過0.08μm的AlN層或厚度超過50μm的Al2O3層時，因為生產成本上升，乃是不佳。因為Al2O3層的膜厚度太厚時，陽極氧化膜會從鋁剝離，以50μm以下為適當。以15μm以下為更佳。從抑制鋁的熱伸縮及絕緣性的觀點，以0.08μm以下為最佳。又，因為AlN層或Al2O3層為自然地形成之層時，係無法得到防止上述擴散的效果，所以蓄意地使其緻密地形成係有必要的。
代替上述AlN層或Al2O3層，亦可以在上述含Al金屬層的表面具有厚度為0.1~8μm的Cr層、或厚度為0.1~8μm的Ni層。藉由具有Cr層或Ni層，能夠得到與AlN層及Al2O3層同
樣的效果。Cr層或Ni層的厚度小於0.1μm時，無法得到上述的效果。厚度超過8μm時，生產成本上升。
代替上述AlN層或Al2O3層，亦可以在上述含Al金屬層的表面具有溶膠凝膠層，該溶膠凝膠層係具有以成長為厚度為0.001~8μm之三維網狀結構狀的矽氧烷鍵作為主骨架之無機骨架，且該骨架的交聯氧的至少1個係被有機基及/或水原子取代。藉由具有溶膠凝膠層，能夠得到與AlN層及Al2O3層同樣的效果。0.1μm以上的厚度時，上述的效果進一步增加，乃是較佳。溶膠凝膠層的厚度小於0.001μm時，無法得到上述的效果。厚度超過8μm時，生產成本上升。
代替上述AlN層及Al2O3層，在上述含Al金屬層的表面上亦可以具有由選自厚度為0.1~8μm的聚烯烴、聚酯、聚醯胺、聚醯亞胺的塑膠薄膜等所構成之疊合層。又，亦可使用由聚醯胺構成之耐熱樹脂代替疊合層。藉由具有疊合層或耐熱樹脂，能夠得到與AlN層及Al2O3層同樣的效果。疊合層的厚度小於0.1μm時，無法得到上述的效果。厚度超過8μm時，生產成本上升。
藉由設為上述的結構，例如在CIGS的太陽電池串聯地連接而成之模組電路，能夠確保500V以上的耐電壓且能夠避免絕緣破壞。又，即便未達到絕緣破壞，若漏電存在時會成為太陽電池的轉換效率低落之原因，藉由設為上述結構，能夠防止此種漏電。
測定上述各層的厚度及組成之方法，下列手法係有效的：使用濺鍍法從金屬箔的表面在膜厚度方向邊往下挖邊
分析之手法；及對金屬箔之膜厚度方向的截斷面進行線分析或點分析之手法。前者的手法係測定深度變大時需要過多的測定時間，後者的手法係進行測定剖面整體的濃度分布和確認再現性等為比較容易。藉由線分析或點分析，欲提升分析的精確度時，在線分析時將分析間隔狹窄化而進行分析、或在點分析時擴大分析區域而進行分析均是有效的。各層的鑑定係能夠預先將標準試料(亦即濃度100%)的值測定好，且在上述組成分析進行辨別其濃度為50%以上的區域。作為該等分析所使用之分析裝置，能夠利用EPMA(電子射線微分析；Electron Probe Micro Analysis)、EDX(能量分散型X射線分析：Energy Dispersive X-Ray Analysis)、AES(歐傑電子能譜儀；Auger Electron Spectroscopy)、TEM(透射型電子顯微鏡；Transmission Electron Microscope)等。又，判定各層的厚度是否滿足上述的數值限定，係使用各層的平均厚度來評價。即便各層厚度係局部性地有不滿足數值限定之情形，亦不考慮上述判定。
藉由將金屬箔設為上述的技術結構，能夠同時滿足作為基材用金屬箔被要求之耐蝕性、表面平滑性及彈塑性變形性，且能夠作為太陽電池和有機EL的基材而使用。
作為在基材上所形成之光電轉換層，能夠使用CIGS、CIS、CdTe等的化合物系太陽電池、非晶Si等的薄膜系太陽電池、使該等複數層積層而成之混合型太陽電池，以及在基材上形成有機EL照明電路。特別是上述的CIGS、CIS之
主成分係沒有特別限制，以至少1種黃銅礦(chalcopyrite)結構的化合物半導體為佳，又，光電轉換層的主成分係以至少1種含有Ib族元素及IIIb族元素及VIb族元素之化合物半導體為佳。而且，因為光吸收率高而能夠得到高光電轉換效率，上述光電轉換層的主成分係以含有至少1種選自Cu及Ag之至少1種的Ib族元素、選自Al、Ga及In等之至少1種的IIIb族元素、及選自S、Se及Te等之至少1種的VIb族元素之化合物半導體為佳。具體上，作為上述化學半導體，能夠使用CuAlS2、CuGaS2、CuInS2、CuAlSe2、CuGaSe2、CuInSe2(CIS)、AgAlS2、AgGaS2、AgInS2、AgAlSe2、AgGaSe2、AgInSe2、AgAlTe2、AgGaTe2、AgInTe2、Cu(In1-xGax)Se2(CIGS)、Cu(In1-xAlx)Se2、Cu(In1-xGax)(S,Se)2、Ag(In1-xGax)Se2及Ag(In1-xGax)(S,Se)2等。
其次，詳細地說明本發明的實施形態之基材用金屬箔之製造方法。
作為第1輥軋處理，係將任意成分的普通鋼(碳鋼)板，進行輥軋至成為200~500μm的厚度。該輥軋方法係可以是熱軋或冷軋之任一者。鐵板的厚度小於200μm時，因為太薄致使後步驟時操作上有困難。又，鐵板的厚度超過500μm時，因為太厚致使後步驟時所需要的負荷過量。
考慮後步驟的生產性時，作為第1輥軋處理，係以進行輥軋至250~350μm厚度為佳。
對上述第1輥軋處理後的鋼板，施行Cu或Ni預鍍覆處理、施行含Al鍍覆處理及進行第2輥軋處理。該等處理的順
序係(1)預鍍覆處理、鍍覆處理、然後第2輥軋處理，(2)預鍍覆處理、第2輥軋處理、然後鍍覆處理，(3)第2輥軋處理、預鍍覆處理、然後鍍覆處理之任一者均可。
作為上述預鍍覆處理，係使用Cu或Ni的鍍覆浴而行電解鍍覆法和無電解鍍覆法。將Cu預鍍覆膜及Ni預鍍覆膜同時，使預鍍覆膜的初期厚度為0.05~4μm時，在含Al鍍覆時之鋼層與含Al金屬層之間所形成之合金層的厚度成為0.1~8μm。例如，欲將在含Al鍍覆時所形成之合金層的厚度控制為上述之最適當的3~5μm時，將預鍍覆膜的初期厚度控制為1.5~2.5μm即可。
又，為了在鋼層與合金層之間使Cu或Ni預鍍覆膜殘留而配置Cu層或Ni層，係將預鍍覆膜的初期厚度以4μm作為基準而以欲使其殘留的厚度程度較厚地成膜即可。4μm以下的厚度之Cu或Ni預鍍覆膜會擴散至在含Al鍍覆時所形成之合金層而消失。超過4μm而成膜之預鍍覆膜，從該膜厚度減去4μm後的厚度程度會殘留而成為Cu層或Ni層。例如為了在鋼層與合金層之間使厚度5μm的Cu層或Ni層存在，使預鍍覆膜的初期厚度為4+5=9μm的厚度即可。
不進行預鍍覆膜而欲形成上述合金層時，適當地調整鋼層及含Al金屬層的成分組成即可。
作為上述鍍覆處理，係使用含有60~100質量%的Al、0~15質量%的Si、及0~40質量%的Cu之鍍覆浴進行鍍覆。作為該鍍覆方法，係能夠使用電解鍍覆法及無電解鍍覆法。藉由使其含有0~15質量%的Si、及0~40質量%的Cu，能夠減
低鍍覆浴的熔點。因此，設為上述組成的鍍覆浴。
而且，為了使鍍覆浴的熔點降低而使鍍覆步驟簡便，以使用含Al鍍覆浴為具有以下各成分為從68.2質量%Al-4.7質量%Si-27.1質量%Cu、或68質量%Al-32質量%Cu的組成±5質量%以內的範圍之組成為佳。
作為第2輥軋處理，係以成為10~250μm的厚度之方式，進行輥軋。該輥軋條件係通常的輥軋條即可。金屬箔的厚度小於10μm時，作為基材用金屬箔係太薄而強度不足。又，金屬箔的厚度超過250μm時，作為基材用金屬箔係太厚且太重。
並且，為了控制金屬箔的含Al金屬層表面之突起狀缺陷、及含Al金屬層表面的光澤度，係在該第2輥軋處理，以使用在上述輥軋機之表面粗糙度為Ra200μm以下的鏡面狀態之軋輥為佳。使上述軋輥的表面粗糙度為Ra200μm以下的理由，係為了適當地控制含Al金屬層表面。
而且，為了控制含Al金屬層表面的突起狀缺陷及含Al金屬層表面的光澤度，以按照必要將上述第2輥軋處理後的金屬箔，進行亮面精加工輥軋作為平整輥軋處理為佳。該平整輥軋處理係以使用表面粗糙度為Ra1μm以下的鏡面狀態之軋輥為佳。使上述軋輥的表面粗糙度為Ra1μm以下之理由，係為了適當地控制含Al金屬層表面。
第2輥軋處理或平整輥軋處理後之上述金屬箔的含Al金屬層的厚度係以0.1~30μm為佳。因為小於0.1μm時，無法得到充分的耐蝕效果，超過30μm時，必須大量地鍍覆Al致
使生產成本上升。較佳是上述含Al金屬層的厚度為1~30μm。更佳是上述含Al金屬層的厚度3~30μm。最佳是上述含Al金屬層的厚度為8~30μm。
又，為了使第2輥軋處理或平整輥軋處理後的上述金屬箔的含Al金屬層表面以緻密狀態形成AlN層，以按照必要進行加熱處理為佳。這是將上述金屬箔，配置在含有10體積%±2體積%之氨或肼之惰性氣體(氬、氮、氮+氫等)中，於500~600℃的溫度範圍內進行加熱1~10小時之加熱處理。
同樣地，為了使第2輥軋處理或平整輥軋處理後的上述金屬箔的含Al金屬層表面以緻密狀態形成Al2O3層，作為陽極氧化處理，係以使用陽極氧化法使含Al金屬層表面氧化為佳。處理條件係能夠利用先前已知之硫酸氧皮鋁、草酸氧皮鋁或鉻酸氧皮鋁等，其中以硫酸氧皮鋁為最經濟，在工業上係適合的。但是因為上述金屬箔係較薄，在陽極氧化處理中，上述金屬箔有變形之危險性，就維持上述金屬箔的平坦度而言，陽極氧化處理結束之後，迅速地進行水冷卻係重要的。
又，為了使含Al金屬層的表面形成Cr層或Ni層，能夠使用濺鍍法、蒸鍍法而比較簡單地進行成膜。但是為了形成緻密且均質的Cr層或Ni層，以使用電解鍍覆為佳。因此，為了使第2輥軋處理或平整輥軋處理後之上述金屬箔的含Al金屬層表面，以緻密狀態形成Cr層或Ni層，係以電解鍍覆處理的方式來施行鍍覆為佳。
同樣地，為了使第2輥軋處理或平整輥軋處理後的上述
金屬箔的含Al金屬層表面形成溶膠凝膠層，以進行溶膠凝膠層的成膜處理為佳。首先，調製在最後的烘烤步驟所得到之被膜中的氫濃度[H](mol/l)與矽濃度[Si](mol/l)的比為0.1≦[H]/[Si]≦10的方式之溶膠。隨後，藉由將所調製的溶膠塗布在上述金屬箔之含Al金屬層表面且乾燥。最後藉由在乾燥之後進行烘烤，能夠製造具備無機有機混合型膜被覆之金屬箔。
同樣地，為了使第2輥軋處理或平整輥軋處理後的上述金屬箔的含Al金屬層表面形成疊合層，以進行疊合層的成膜處理為佳。能夠使用由選自聚烯烴、聚酯、聚醯胺、聚醯亞胺的塑膠薄膜等所構成之疊合材料且使用耐綸系接著劑使其與上述金屬箔的含Al金屬層表面接觸之後進行加熱，而且使用以1MPa左右的壓力熱壓黏之熱貼合法進行成膜。
藉由實施例來更具體地說明本發明的一態樣之效果，但是實施例的條件係為了確認本發明的實施可能性及效果而採用之一條件例，本發明係不被該一條件例限定。本發明係只要不脫離本發明的要旨，為了達成本發明的目的，能夠採用各種的條件。
在實驗例1，作為第一輥軋處理，係將軟鋼進行熱軋及冷軋而成為板厚度為300μm的輥軋鋼板。作為預鍍覆處理，係在該輥軋鋼板上使用電解電極法，形成純Cu或純Ni
預鍍覆膜。作為電解Ni鍍覆的鍍覆浴，係使用瓦特浴，作為電解Cu鍍覆的鍍覆浴，係使用硫酸銅浴。作為鍍覆處理，係藉由將預鍍覆處理後的輥軋鋼板浸漬於含Al金屬中20秒來進行熔融Al鍍覆。作為第2輥軋處理，係將鍍覆處理後的輥軋鋼板以平均各次為10~20%的壓下率進行輥軋而製造金屬箔。一部分的金屬箔係按照必要在第二輥軋處理後實施平整輥軋處理。上述的預鍍覆膜及含Al金屬層的厚度，係以箔化後的各層係成為表1所記載的厚度之方式，預先計算而決定。
將上述所製造的金屬箔之表面狀態、各結構層的狀態，藉由以與金屬箔的輥軋方向正交之板寬度方向為觀察面的方式，觀察在沿著板厚度方向平面截斷之截斷面的金屬組織來確認。觀察金屬組織係以觀察視野在板寬度方向為20μm以內的倍率來進行，且以板寬度方向的合計視野為300μm以上的方式觀察至少15視野以上。輪廓曲線及輪廓平均直線係藉由影像解析來求得。各構成層係藉由對上述截斷面進行能量分散型X射線分析(EDX)來鑑定。合金層的硬度係藉由使用維氏硬度計測定上述截斷面。將該等結果顯示在表1。表中以下線表示之數值，係表示本發明的範圍外之情形。觀察截斷面時，能夠觀察到被稱為孔洞之空隙時，在表1以「有」孔洞表示。
又，使用上述所製造的金屬箔而進行耐蝕試驗、180度密著彎曲試驗及光澤度測定試驗。同樣地，將該等結果顯示在表1。表中以下線表示之數值，係表示本發明的範圍外
之情形。
耐蝕試驗係依據鹽水噴霧試驗(SST)而評價。將保持在35℃之5%的NaCl水進行噴霧，將400小時以上而目視無法確認有腐蝕之情況評價為VG(Very Good)，將300小時以上評價為G(Good)，將100小時以上評價為NG(Not Good)，將小於100小時評價為B(Bad)。而且，將NG及B評價為不合格。
作為更嚴酷的耐蝕性試驗，係對在以150mm×70mm切取的金屬箔，將保持在50℃之10%NaCl水進行噴霧。經過600小時，金屬箔表面亦無腐蝕時係耐蝕性特別良好而評價為EG(Extremely Good)。經過500小時，金屬箔表面亦無腐蝕時評價為GG(Greatly Good)。經過400小時，金屬箔表面亦無腐蝕時評價為VG(Very Good)。經過300小時，金屬箔表面亦無腐蝕時評價為G(Good)。經過100小時，金屬箔表面亦無腐蝕時評價為NG(Not Good)。小於100小時而金屬箔表面產生腐蝕時評價為B(Bad)。而且將NG及B當作不合格。
180度密著彎曲試驗，係藉由對金屬箔重複實施內側半徑為零且彎曲角度成為180°之180度密著彎曲加工，並且調查皮膜的剝離或產生龜裂之加工次數。觀察皮膜的剝離或龜裂，係藉由在180度密著彎曲加工的每一循環，使用光學顯微鏡觀察金屬箔的彎曲外周部來進行。皮膜的剝離或龜裂係將使用光學顯微鏡觀察的時點之加工次數設作皮膜破壞次數。皮膜破壞次數係3次以上時，判斷彈塑性變形性為良好。
光澤度測定試驗係使用光澤度計且藉由對金屬箔以入
射角60°使光線入射，而測定相對於銀鏡面的反射率之比率來實施。光澤度係將小於75%判斷為(Not Good)，75%以上且小於80%為G(Good)，80以上且小於90%為VG(Very God)，90%以上為GG(Greatly Good)。而且將NG當作不合格。
如表1所表示，實施例1~31係鋼層、Cu層或Ni層、合金層、及含Al金屬層的狀態之任一者均達成目標，其結果，顯示優良的耐蝕性、彈塑性變形性、表面平滑性及光澤度。
對此，比較例1~4係鋼層、Cu層或Ni層、合金層、及含Al金屬層的狀態之任一者均未達成目標，其結果，顯示耐蝕性、彈塑性變形性、表面平滑性及光澤度的任一者係不充分。
比較例1係因為不具有合金層，為耐蝕性、180度密著彎曲性不充分之例子。
比較例2係因為合金層的厚度超過8μm，在截斷面能夠觀察到孔洞，且為180度密著彎曲性不充分之例子。
比較例3係因為合金層為先前硬而脆的合金層，合金層的維氏硬度為900Hv，且為180度密著彎曲性不充分之例子。
比較例4係存在有與輪廓平均直線的距離超過0.5微米的極大點之例子。光澤度亦不充分。
實驗例2係使在實驗例1的實施例1所製造的金屬箔，形成AlN層、Al2O3層、Cr層、Ni層、溶膠凝膠層、及疊合層，並且藉由變化其膜厚度而調查CIGS光電轉換效率。CIGS光電轉換效率係將小於8%評價為NG(Not good)、8%以上且小於10%評價為G(Good)、10以上且小於12%評價為VG(Very Good)、12%以上評價為GG(Greatly Good)。而且將NG當作不合格。
AlN層係藉由使用含氨的惰性氣體之加熱處理來製
造。Al2O3層係藉由硫酸氧皮鋁處理來製造。Cr層及Ni層係使用濺鍍法來製造。
溶膠凝膠層的形成，係使用10mol的甲基三乙氧基矽烷及10mol的四乙氧基矽烷之混合物作為調製溶膠的起始原料，且在該混合物添加20mol的乙醇而充分地攪拌。隨後，邊攪拌邊滴下將2mol的乙酸與100mol的水混合而成之乙酸水溶液滴下來進行加水分解。在如此進行而得到之溶膠，添加100mol的乙醇而得到的最後的溶膠。使用浸漬法而在鍍覆普通鋼箔的兩面塗布該溶膠之後，在空氣中於100℃進行乾燥1分鐘。隨後，在氮氣環境中以升溫速度10℃/分鐘，從室溫升溫至400℃且於400℃烘烤30分鐘而得到溶膠凝膠層。
疊合層的形成係藉由將耐綸系接著劑以15質量%的濃度溶解在甲酚與二甲苯的質量比為70：30的混合溶劑，且將該溶解物塗布在樹脂之後，將該樹脂以1MPa的壓力熱壓黏在經加熱至300℃之鍍覆普通鋼板來進行熱貼合。將其結果顯示在表2。
如表2所表示，實施例32~63係任一者均顯示優良的光電轉換效率。特佳是將AlN層、Al2O3層、Cr層、Ni層、溶膠凝膠層及疊合層的厚度控制為最佳之實施例，係顯示更優良的光電轉換效率。
因為實施例33~35及實施例53~55係將AlN層的厚度控制為最佳，而顯示更優良的光電轉換效率。
因為實施例37~39係將Cr層的厚度控制為最佳，而顯示更優良的光電轉換效率。
因為實施例41~43係將Ni層的厚度控制為最佳，而顯示更優良的光電轉換效率。
因為實施例45~47及實施例49~51係將Al2O3層的厚度控制為最佳，而顯示更優良的光電轉換效率。
因為實施例57~59係將溶膠凝膠層的厚度控制為最佳，而顯示更優良的光電轉換效率。
因為實施例61~63係將疊合層的厚度控制為最佳，而顯示更優良的光電轉換效率。
依照本發明的上述態樣，相較於玻璃基板，係不容易產生裂紋而且適合於薄膜化，並且能夠提供作為基材用金屬箔被要求的耐蝕性、表面平滑性及彈塑性變形性之價廉的基材用金屬箔。
Claims (8)
- 一種基材用金屬箔，係太陽電池及有機電致發光的基材用金屬箔，且係具備厚度為10~200μm之鋼層、生成於前述鋼層上之含Fe及Al的合金層、及配置於前述合金層上之含Al金屬層者，其特徵在於：以與輥軋前述金屬箔的方向正交的方式截斷出一截斷面，該截斷面所呈現之前述含Al金屬層的表面之截斷線的極大點與前述截斷線之近似直線的距離在10μm以下，於此，前述截斷線係輪廓曲線，前述極大點係前述含Al金屬層表面側凸出之極點，且前述近似直線係藉由對前述截斷線應用相位補償型濾波器求得之直線、或係從前述截斷線之各極點的座標藉由最小二乘方法求得之直線；前述合金層係厚度為0.1~8μm且含有Al7Cu2Fe金屬間化合物、或FeAl3基的金屬間化合物。
- 如申請專利範圍第1項之基材用金屬箔，其係在前述鋼層與前述合金層之間，進一步具有厚度為2~10μm的Cu層、或厚度為2~10μm的Ni層。
- 如申請專利範圍第1項之基材用金屬箔，其中前述含Al金屬層的厚度為0.1~30μm。
- 如申請專利範圍第1項之基材用金屬箔，其係在前述含Al金屬層上，進一步具有厚度為0.01~0.08μm的AlN層、或厚度為0.01~50μm的Al2O3層。
- 如申請專利範圍第1項之基材用金屬箔，其係在前述含 Al金屬層上，進一步具有厚度為0.1~8μm的Cr層、或厚度為0.1~8μm的Ni層。
- 如申請專利範圍第1項之基材用金屬箔，其係在前述含Al金屬層上，進一步具有溶膠凝膠層。
- 如申請專利範圍第1項之基材用金屬箔，其係在前述含Al金屬層上，進一步具有疊合層。
- 如申請專利範圍第1項之基材用金屬箔，其係在前述含Al金屬層上，進一步具有溶膠凝膠層及疊合層。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010257322 | 2010-11-17 |
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| Publication Number | Publication Date |
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| TW201240746A TW201240746A (en) | 2012-10-16 |
| TWI558478B true TWI558478B (zh) | 2016-11-21 |
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| TW100142081A TWI558478B (zh) | 2010-11-17 | 2011-11-17 | 基材用金屬箔 |
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| Country | Link |
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| US (1) | US9296180B2 (zh) |
| JP (1) | JP5816615B2 (zh) |
| CN (1) | CN103210112B (zh) |
| TW (1) | TWI558478B (zh) |
| WO (1) | WO2012067146A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013122075A (ja) * | 2011-12-12 | 2013-06-20 | Nippon Steel & Sumitomo Metal Corp | 溶融Ａｌ系めっき鋼板とその製造方法 |
| JP6286821B2 (ja) * | 2012-11-26 | 2018-03-07 | 東洋製罐グループホールディングス株式会社 | フレキシブルデバイス用基板およびその製造方法 |
| US20160017501A1 (en) * | 2013-03-14 | 2016-01-21 | United Technologies Corporation | Corrosion Protection Material and Method for Protecting Aluminum Coatings |
| CN104073856A (zh) * | 2014-06-26 | 2014-10-01 | 深圳惠科精密工业有限公司 | 一种金属件的氧化方法 |
| WO2018123818A1 (ja) * | 2016-12-27 | 2018-07-05 | 日立化成株式会社 | 金属箔付伸縮性部材 |
| CN108501471B (zh) * | 2017-03-29 | 2019-08-06 | 东洋钢钣株式会社 | 电子设备用轧制接合体及电子设备用壳体 |
| CN108355658B (zh) * | 2018-02-09 | 2019-06-14 | 深圳市中金岭南科技有限公司 | 一种Fe合金/Al2O3催化剂载体材料的制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6428349A (en) * | 1987-07-24 | 1989-01-30 | Nippon Steel Corp | Manufacture of aluminum-plated steel sheet and steel foil using stainless steel as base material |
| CN1527071A (zh) * | 2003-09-23 | 2004-09-08 | 甘国工 | 有增强附着力的金属保护层的高反射镜及其制造方法 |
| TWI237334B (en) * | 2002-04-05 | 2005-08-01 | Nippon Steel Corp | A gold bonding wire for a semiconductor device and a method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4686155A (en) | 1985-06-04 | 1987-08-11 | Armco Inc. | Oxidation resistant ferrous base foil and method therefor |
| JPH01150404A (ja) * | 1987-12-07 | 1989-06-13 | Nippon Steel Corp | アルミニウムめっき不銹鋼箔の圧延方法 |
| JP2932700B2 (ja) * | 1991-01-08 | 1999-08-09 | 大同特殊鋼株式会社 | 刃物材とその製造方法 |
| KR100212596B1 (ko) | 1995-02-24 | 1999-08-02 | 하마다 야스유키(코가 노리스케) | 용융 알루미늄 도금 강판과 그 제조방법 및 합금층 제어 장치 |
| DE69602226T2 (de) * | 1995-05-19 | 1999-08-19 | Matsushita Electric Works Ltd | Eisenlegierung mit Fe-Al Diffusionsschicht und Verfahren zu ihrer Herstellung |
| CN1209481A (zh) | 1998-08-19 | 1999-03-03 | 重庆菲尔达技术公司 | 无废液排放的制纸浆方法 |
| JP2002093573A (ja) * | 2000-09-14 | 2002-03-29 | Nisshin Steel Co Ltd | 有機ｅｌ素子用絶縁性封止部材 |
| US7601672B2 (en) | 2002-11-20 | 2009-10-13 | Nippon Steel Corporation | High Al stainless steel sheet and honeycomb bodies employing them |
| JP2006080370A (ja) | 2004-09-10 | 2006-03-23 | Matsushita Electric Ind Co Ltd | 太陽電池 |
| JP2006295035A (ja) | 2005-04-14 | 2006-10-26 | Matsushita Electric Ind Co Ltd | 絶縁層が形成された太陽電池用基板およびその製造方法、ならびにそれを用いた太陽電池およびその製造方法 |
| NZ594317A (en) | 2009-01-16 | 2013-01-25 | Hot-dip Zinc-Aluminium-Magnesium-Silicon-Chromium alloy-coated steel material | |
| CN101817128B (zh) | 2009-04-21 | 2012-01-11 | 兰州理工大学 | 一种低熔点铝基钎料的制备方法 |
-
2011
- 2011-11-16 CN CN201180054727.2A patent/CN103210112B/zh not_active Expired - Fee Related
- 2011-11-16 WO PCT/JP2011/076400 patent/WO2012067146A1/ja active Application Filing
- 2011-11-16 JP JP2012508683A patent/JP5816615B2/ja not_active Expired - Fee Related
- 2011-11-16 US US13/885,278 patent/US9296180B2/en not_active Expired - Fee Related
- 2011-11-17 TW TW100142081A patent/TWI558478B/zh not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6428349A (en) * | 1987-07-24 | 1989-01-30 | Nippon Steel Corp | Manufacture of aluminum-plated steel sheet and steel foil using stainless steel as base material |
| TWI237334B (en) * | 2002-04-05 | 2005-08-01 | Nippon Steel Corp | A gold bonding wire for a semiconductor device and a method for producing the same |
| CN1527071A (zh) * | 2003-09-23 | 2004-09-08 | 甘国工 | 有增强附着力的金属保护层的高反射镜及其制造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103210112A (zh) | 2013-07-17 |
| JP5816615B2 (ja) | 2015-11-18 |
| US20130236737A1 (en) | 2013-09-12 |
| JPWO2012067146A1 (ja) | 2014-05-12 |
| TW201240746A (en) | 2012-10-16 |
| US9296180B2 (en) | 2016-03-29 |
| CN103210112B (zh) | 2015-10-21 |
| WO2012067146A1 (ja) | 2012-05-24 |
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