CN103210112A - 基材用金属箔 - Google Patents
基材用金属箔 Download PDFInfo
- Publication number
- CN103210112A CN103210112A CN2011800547272A CN201180054727A CN103210112A CN 103210112 A CN103210112 A CN 103210112A CN 2011800547272 A CN2011800547272 A CN 2011800547272A CN 201180054727 A CN201180054727 A CN 201180054727A CN 103210112 A CN103210112 A CN 103210112A
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- CN
- China
- Prior art keywords
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- thickness
- tinsel
- mentioned
- base material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 79
- 239000002184 metal Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims description 54
- 239000011888 foil Substances 0.000 title abstract description 14
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 46
- 239000010959 steel Substances 0.000 claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 44
- 239000000956 alloy Substances 0.000 claims abstract description 44
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims description 30
- 229910015372 FeAl Inorganic materials 0.000 claims description 14
- 229910015392 FeAl3 Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 42
- 238000012545 processing Methods 0.000 description 36
- 238000007747 plating Methods 0.000 description 31
- 238000005260 corrosion Methods 0.000 description 26
- 238000000576 coating method Methods 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 230000009466 transformation Effects 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 12
- 238000009499 grossing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 230000002950 deficient Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000006378 damage Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000011669 selenium Substances 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 241000220317 Rosa Species 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
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- 239000002362 mulch Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 230000000007 visual effect Effects 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 229910052710 silicon 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
- 239000000758 substrate Substances 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005275 alloying 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
- 238000004166 bioassay Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005097 cold rolling 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
- 150000001896 cresols Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
-
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Abstract
本发明涉及一种基材用金属箔，其具有厚度为10～200μm的钢层、在所述钢层上生成的含有Fe和Al的合金层、以及在所述合金层上配置的含Al金属层，其中，当将所述含Al金属层表面的切断线作为轮廓曲线，并将对所述轮廓曲线进行近似处理所得到的直线作为轮廓平均直线时，所述轮廓曲线并不存在距所述轮廓平均直线的距离超过10μm的极大点；关于所述合金层，其厚度为0.1～8μm，而且包含Al7Cu2Fe金属间化合物或者FeAl3基金属间化合物。
Description
技术领域
本发明涉及一种能够作为化合物系太阳能电池、薄膜系太阳能电池、将它们多层层叠而成的混合型太阳能电池以及有机电致发光照明的基材使用的金属箔。
本申请基于2010年11月17日提出的日本专利申请特愿2010-257322号并主张其优先权，这里引用其内容。
背景技术
在CIGS（Copper-Indium-Gallium-Selenium）、CIS（Copper-Indium-Selenium）、CdTe（Cadmium-Tellur）等化合物系太阳能电池、非晶Si等薄膜系太阳能电池、将它们多层层叠而成的混合型太阳能电池以及有机EL（Electroluminescence）照明中，为了有强度地支撑CIGS层、CIS层、CdTe层、非晶Si层和有机EL层等，可以使用被称之为基材的基台。
以前，作为上述基材，正如专利文献1所记载的那样，大多使用玻璃基材。但是，玻璃由于容易开裂，为了确保一定的强度，需要厚膜化。如果使玻璃厚膜化，则太阳能电池和有机EL照明本身加重。
另一方面，近年来，作为上述基材，正尝试使用难以开裂、且适于薄膜化的金属箔以代替玻璃基材。基材用金属箔要求耐蚀性、表面平滑性以及弹塑性变形性均良好。
关于上述耐蚀性，用作基材的金属箔需要能够在室外环境下长期曝露20年之久。
上述表面平滑性对于避免在存在于基材表面的突起状缺陷的作用下，层叠于基材上的太阳能电池层或有机EL层受到物理的损伤是很必要的。基材表面优选的是没有突起状缺陷的平滑的表面。
上述弹塑性变形性对于硬质的玻璃基材是不可能的，需要能够将基材用金属箔卷绕成辊的形状。其结果是，如果能够将Batch处理（批处理）制造变更为Roll to Roll处理（卷绕式处理）的连续制造，则可以大幅度降低太阳能电池和有机EL的制造成本。
一般地说，作为基材用金属箔，耐蚀性优良的不锈钢（SUS）箔的使用正在推进。正如专利文献2所记载的那样，有时也使用在SUS箔上进一步形成有有机覆盖膜的基材。
SUS箔由于具有优良的耐蚀性，因而作为基材用金属箔使用。但是，SUS箔具有材料昂贵的问题。除此以外，SUS箔由于硬度高、不容易轧制，因而也存在制造成本升高的问题。因此，与玻璃基材相比，现实情况是它的使用并不那么广泛。
另一方面，普通钢（碳素钢）箔与SUS相比，材料自身更为廉价，而且具有较高的塑性变形能，因而制造成本也能够大幅度地降低。但是，普通钢箔就那样不能满足作为基材用金属箔所要求的耐蚀性。如果满足基材用金属箔所要求的上述特性的普通钢箔的利用成为可能，则可以大幅度地降低太阳能电池以及有机EL的制造成本。因此，目前一直强烈期待上述普通钢箔的开发。
现有技术文献
专利文献
专利文献1：日本特开2006-80370号公报
专利文献2：日本特开2006-295035号公报
发明内容
发明所要解决的课题
本发明的一实施方式是鉴于上述事情而完成的，其目的在于提供一种同时满足作为太阳能电池和有机EL的基材用金属箔所要求的耐蚀性、表面平滑性以及弹塑性变形性的廉价的基材用金属箔。
用于解决课题的手段
本发明的要旨如下所述。
（1）本发明的一实施方式涉及一种基材用金属箔，其具有厚度为10～200μm的钢层、在所述钢层上生成的含有Fe和Al的合金层、以及在所述合金层上配置的含Al金属层，其中，当将所述金属箔以与轧制方向正交的板宽度方向成为观察面的方式用平面沿板厚方向切断而得到切断面，将表示在该切断面的所述含Al金属层表面的切断线作为轮廓曲线，并将对所述轮廓曲线进行近似处理所得到的直线作为轮廓平均直线时，所述轮廓曲线并不存在距所述轮廓平均直线的距离超过10μm的在所述含Al金属层的表面侧凸出来的极大点；关于所述合金层，其厚度为0.1～8μm，而且包含Al7Cu2Fe金属间化合物或者FeAl3基金属间化合物。
（2）根据上述（1）所述的基材用金属箔，其中，在所述钢层和所述合金层之间，也可以进一步具有厚度为2～10μm的Cu层或者厚度为2～10μm的Ni层。
（3）根据上述（1）或者（2）所述的基材用金属箔，其中，所述含Al金属层的厚度也可以为0.1～30μm。
（4）根据上述（1）～（3）中任一项所述的基材用金属箔，其中，在所述含Al金属层上，也可以进一步具有厚度为0.01～0.08μm的AlN层或者厚度为0.01～50μm的Al2O3层。
（5）根据上述（1）～（3）中任一项所述的基材用金属箔，其中，在所述含Al金属层上，也可以进一步具有厚度为0.1～8μm的Cr层或者厚度为0.1～8μm的Ni层。
（6）根据上述（1）～（3）中任一项所述的基材用金属箔，其中，在所述含Al金属层上，也可以进一步具有选自溶胶凝胶层以及层叠层之中的至少1种薄膜。
发明的效果
根据本发明的上述实施方式，能够提供一种廉价的基材用金属箔，其与玻璃基材相比较，难以开裂且适于薄膜化，除此以外，同时满足作为基材用金属箔所要求的耐蚀性、表面平滑性以及弹塑性变形性。因此，能够以低成本制造薄型轻量的CIGS、CIS、CdTe等化合物系太阳能电池、非晶Si等薄膜系太阳能电池、将它们多层层叠而成的混合型太阳能电池以及有机EL照明。
具体实施方式
下面就本发明优选的实施方式进行详细的说明。首先，就基材用金属箔的技术构成和数值限定理由进行详细的说明。
为了提高普通钢（碳素钢）的耐蚀性，对普通钢镀覆含Al镀层。通过该含Al镀层，便将含Al金属层配置在钢层上。通过该含Al金属层，作为基材用金属箔所要求的耐蚀性便得以提高。
上述含Al金属层优选的是含有60～100质量%的Al、0～15质量%的Si、0～40质量%的Cu的组成。其原因在于：在该组成中，镀槽（或镀液：plating bath）的熔点下降，所以镀覆工序变得简便。更优选将上述含Al金属层设定为如下的组成：以68.2质量%Al-4.7质量%Si-27.1质量%Cu或者68质量%Al-32质量%Cu这一组成为基础，各成分在±5质量%以内的范围变化。该组成使镀槽的熔点进一步下降。另外，上述含Al金属层的厚度优选为0.1～30μm。其原因在于：低于0.1μm时，不能得到优选的耐蚀效果，而超过30μm时，需要大量镀覆Al，从而生产成本升高。优选将上述含Al金属层的厚度设定为1～30μm。更优选将上述含Al金属层的厚度设定为3～30μm。最优选将上述含Al金属层的厚度设定为8～30μm。
一般地说，在为含Al镀层时，在钢层和含Al金属层的界面，以层状的方式形成有Fe-Al系合金相（例如FeAl3、Fe2Al8Si、FeAl5Si等金属间化合物）。该合金层非常硬而脆。如果镀覆有含Al镀层的金属箔在操作等时发生弹塑性变形，则该合金层不能追随金属箔的变形，最终诱发钢层和含Al金属层的剥离以及含Al金属层的开裂。也就是说，如果对普通钢箔镀覆含Al镀层，则虽然能够满足作为基材用金属箔所要求的耐蚀性，但并不满足弹塑性变形性。
为了满足作为基材用金属箔所要求的弹塑性变形性，对于在钢层和含Al金属层的界面生成的上述合金层，需要其厚度为0.1～8μm，且含有Al7Cu2Fe金属间化合物或者FeAl3基金属间化合物。该Al7Cu2Fe金属间化合物或者FeAl3基金属间化合物在上述合金层中，以面积%计优选含有50%以上，更优选含有90%以上。
在此，所谓FeAl3基金属间化合物，是指在FeAl3金属间化合物中，固溶有构成系统的元素（例如Si和Cu等构成含Al金属层的元素、Ni和Cu等构成预镀膜的元素、或者C、P、Cr、Ni、Mo等构成钢层的元素）的金属间化合物，以及由构成上述系统的元素、Fe和Al以新的组成比形成的金属间化合物。该FeAl3基金属间化合物特别优选的是固溶有Cu的FeAl3基金属间化合物或者固溶有Ni的FeAl3基金属间化合物。但是，如后所述，该合金层的维氏硬度只要达到500～600Hv左右，则固溶的元素并不局限于Ni或者Cu。
上述的含有Al7Cu2Fe金属间化合物或者FeAl3基金属间化合物的合金层通过在对普通钢镀覆含Al镀层时，由后述的Cu或者Ni预镀膜、钢层、含Al金属层构成系统的元素扩散并与Fe以及Al合金化而形成。这样一来，为了适当地形成含有上述的Al7Cu2Fe金属间化合物或者FeAl3基金属间化合物的合金层，在镀覆含Al镀层前，优选的是事先对普通钢镀覆Cu或者Ni预镀层，从而在钢层上形成Cu或者Ni的预镀膜。不过，上述合金层例如也可以通过构成钢层以及含Al金属层的元素的扩散而形成，所以Cu或Ni预镀膜不是必须的技术构成。
包含该Al7Cu2Fe金属间化合物或者FeAl3基金属间化合物的合金层的维氏硬度为500～600Hv。上述以前的硬而脆的合金层的维氏硬度为900Hv左右。这样一来，通过将合金层控制为比较软质的层，便可以提高金属箔的弹塑性变形性。另外，在上述合金层的厚度低于0.1μm时，则不能得到作为软质合金层的上述效果。在其厚度超过8μm时，构成系统的元素的扩散过于进行，容易生成柯肯达尔（Kirkendall）孔隙，因而是不优选的。
为了进一步提高金属箔的弹塑性变形性，优选将上述金属层的厚度设定为0.1～5μm。另外，如果将其厚度设定为3～8μm，则金属箔的耐蚀性进一步提高，因而是优选的。如果将上述金属层的厚度设定为3～5μm，则可以同时得到两种效果，因而是最优选的。
另外，在上述钢层和上述合金层之间，以2～10μm的厚度残存有Cu或Ni预镀膜，当设计为Cu层或者Ni层时，则钢层和合金层之间的附着力进一步增加，从而弹塑性变形性得以提高，因而是优选的。其结果是，在冲压成形和深拉深等时即使进行苛刻的加工，上述合金层的剥离也难以发生。
即使在钢层和合金层之间存在上述的Cu层或者Ni层，也不会妨碍上述合金层所具有的效果。但是，如果Cu层或者Ni层的厚度低于2μm，则不能得到提高钢层和合金层之间的附着力的效果。另外，当其厚度超过10μm时，上述效果达到饱和，而且形成预镀膜的成本也上升，因而是不优选的。
另外，金属箔的钢层的厚度设定为10～200μm。为了制造厚度低于10μm的箔，需要慎重地控制高精度的装置，从而成本升高。另外，当厚度超过200μm时，金属箔的重量加重，不能充分获得使用箔的优点。为了减轻基材的重量，厚度优选为10～150μm。另外，为了提高材料的强度，从而在基材上载置重物，厚度优选为100～200μm。如果将上述钢层的厚度设定为100～150μm，则可以同时得到两种效果，因而是最优选的。
太阳能电池或有机EL的基材用金属箔重要的是除了满足上述的耐蚀性以及弹塑性变形性以外，还同时满足表面平滑性。
为了满足作为基材用金属箔所要求的表面平滑性，含Al金属层的表面必须是一定程度的平滑面。具体地说，当将金属箔以与轧制方向正交的板宽度方向成为观察面的方式用平面沿板厚方向切断而得到切断面，将表示在该切断面的含Al金属层表面的切断线作为轮廓曲线，并将对轮廓曲线进行近似处理所得到的直线作为轮廓平均直线时，需要使上述轮廓曲线并不存在距该轮廓平均直线的距离超过10μm的极大点。
在此，所谓上述极大点，是指上述轮廓曲线在含Al金属层的表面侧凸出来的极值点。此外，轮廓曲线的极小点（上述轮廓曲线在含Al金属层的表面上呈凹状的极值点）由于不会对基材用金属箔上层叠的太阳能电池层或有机EL层产生物理的损伤，因而即使存在也不成问题。
另外，上述轮廓曲线既可以从上述切断面的金属组织照片中通过图像处理求出其轨迹，也可以通过人工求出其轨迹。在通过图像处理求出轮廓曲线的情况下，同样，可以通过图像处理，使用相位补偿型滤波器而求出轮廓平均直线。在通过人工求出轮廓曲线的情况下，可以采用最小二乘法由各极值点的坐标求出轮廓平均直线。
如果在含Al金属层表面存在超过10μm的突起状缺陷，则有可能对基材用金属箔上层叠的太阳能电池层或有机EL层产生物理的损伤。例如，在太阳能电池中，如果基材上的太阳能电池层受到上述的损伤，则其区域的光电转换效率有可能下降。
另外，为了获得充分的光电转换效率，优选的是并不存在距轮廓平均直线的距离超过5μm的极大点。进一步优选的是并不存在超过1μm的极大点。
上述含Al金属层表面优选的是光泽度以银镜比计为75%以上。例如，在太阳能电池中，存在入射时无助于光电转换而到达作为基材的金属箔的太阳光。该透过光借助于金属箔而反射，由此再度供给光电转换使用。如果光泽度以银镜比计为75%以上，则透过光以高效率再度供给光电转换使用，因而是优选的。更为优选的是光泽度以银镜比计为80%以上。
上述的金属箔的表面平滑性以及光泽度通过在上述第2轧制处理时使用镜面状态的轧辊、或者对第2轧制处理后的金属箔实施表皮光轧来实现。关于本发明的实施方式的制造方法，容后详述。
在上述含Al金属层的表面优选进一步具有厚度为0.01～0.08μm的AlN层或者厚度为0.01～50μm的Al2O3层。如果Fe原子从钢层向太阳能电池层或有机EL层等扩散，则有可能损害这些层的功能。例如，如果Fe原子从钢层向太阳能电池的CIGS层或CIS层等扩散，则使带隙狭窄，从而产生太阳能电池的转换效率下降这一不良情况。上述AlN层或者上述Al2O3层作为阻挡膜而发挥作用，从而能够防止构成钢层的Fe原子发生扩散而达到CIGS层或CIS层等。但是，在这些层的厚度低于0.01μm时，不能得到上述的效果。生成厚度超过0.08μm的AlN层或者厚度超过50μm的Al2O3层由于导致生产成本的上升，因而是不优选的。如果Al2O3层的膜厚过厚，则阳极氧化膜从铝上剥离，因而50μm以下是适当的。更优选为15μm以下。从铝的热伸缩抑制以及绝缘性的角度考虑，最优选的是0.08μm以下。另外，当AlN层或者Al2O3层是自然形成的层时，则不能得到上述的扩散防止效果，因而需要有意地形成致密层。
也可以在上述含Al金属层的表面具有厚度为0.1～8μm的Cr层或者厚度为0.1～8μm的Ni层以代替上述AlN层以及Al2O3层。通过具有Cr层或者Ni层，可以得到与AlN层以及Al2O3层同样的效果。当Cr层或者Ni层的厚度低于0.1μm时，则不能得到上述的效果。当厚度超过8μm时，则生产成本上升。
也可以在上述含Al金属层的表面具有溶胶凝胶层以代替上述AlN层以及Al2O3层，该溶胶凝胶层具有厚度为0.001～8μm的发达成三维网络结构状的以硅氧烷键为主骨架的无机骨架，并且该骨架的交联氧的至少1个被有机基和/或氢原子取代。通过具有溶胶凝胶层，可以得到与AlN层以及Al2O3层同样的效果。如果将厚度更优选设定为0.1μm以上，则上述的效果更为增加。当溶胶凝胶层的厚度低于0.001μm时，则不能得到上述的效果。当厚度超过8μm时，则生产成本上升。
也可以在上述含Al金属层的表面，具有厚度为0.1～8μm的由选自聚烯烃、聚酯、聚酰胺、聚酰亚胺之中的塑料薄膜等构成的层叠层以代替上述AlN层以及Al2O3层。另外，也可以使用由聚酰亚胺构成的耐热树脂以代替层叠层。通过具有层叠层或者耐热树脂，可以得到与AlN层以及Al2O3层同样的效果。当层叠层的厚度低于0.1μm时，则不能得到上述的效果。当厚度超过8μm时，则生产成本上升。
通过设计为上述的构造，在例如由CIGS的太阳能电池单元串联连接而成的模块电路中，可以确保500V以上的耐电压，能够避免绝缘破坏。另外，即使不至于绝缘破坏，如果存在漏电流，则可能导致太阳能电池模块的光电转换效率的下降，但通过设定为上述的构造，可以防止这样的泄漏。
作为测定上述各层的厚度以及组成的方法，一边通过溅射法从金属箔的表面沿膜厚方向往深掘一边进行分析的手法、或者在金属箔的膜厚方向的切断面进行线分析或者点分析的手法是有效的。在前者的手法中，如果测定深度增大，则过于耗费测定时间，而在后者的手法中，则比较容易进行整个断面的浓度分布的测定和重现性的确认等。在采用线分析或者点分析而欲提高分析精度的情况下，在线分析中缩短分析间隔而进行分析、或者在点分析中扩大分析区域而进行分析也是有效的。各层的鉴定通过预先测定标准试料（即浓度为100%）的值、再用上述组成分析判别其浓度为50%以上的区域来进行。作为在这些分析中使用的分析装置，可以利用EPMA（电子探针微观分析：Electron Probe MicroAnalysis）、EDX（能量分散型X射线分析：Energy Dispersive X-RayAnalysis）、AES（俄歇电子能谱法：Auger Electron Spectroscopy）、TEM（透射型电子显微镜：Transmission Electron Microscope）等。此外，各层厚度是否满足上述数值限定的判定通过各层的平均厚度来进行评价。即使有各层厚度局部并不满足数值限定的情况，在上述判定中也不予考虑。
通过将金属箔设定为上述的技术构成，便能够同时满足作为基材用金属箔所要求的耐蚀性、表面平滑性以及弹塑性变形性，可以作为太阳能电池或有机EL的基材使用。
作为在基材上形成的光电转换层，可以用作CIGS、CIS、CdTe等化合物系太阳能电池、非晶Si等薄膜系太阳能电池、将它们多层层叠而成的混合型太阳能电池，或者在基材上可以形成有机EL照明电路。特别地，上述的CIGS、CIS的主成分并没有特别的限制，优选的是至少1种黄铜矿型结构的化合物半导体，另外，光电转换层的主成分优选的是含有Ib族元素、IIIb族元素和VIb族元素的至少1种化合物半导体。再者，由于光吸收率高，且可以得到较高的光电转换效率，因而上述光电转换层的主成分优选的是包含选自Cu以及Ag等之中的至少1种Ib族元素、选自Al、Ga以及In等之中的至少1种IIIb族元素、和选自S、Se以及Te等之中的至少1种VIb族元素的至少1种化合物半导体。具体地说，作为上述化合物半导体，可以使用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以及Ag（In1-xGax）（S,Se）2等。
接着，就本发明的实施方式的基材用金属箔的制造方法进行详细的说明。
对任选成分的普通钢（碳素钢）板进行轧制，直至达到200～500μm的厚度，将其作为第1轧制处理。该轧制方法无论是热轧还是冷轧均可。当钢板的厚度低于200μm时，因过薄而难以进行后面工序时的操作。另外，当钢板的厚度超过500μm时，因过厚而给后面工序过于施加负荷。
考虑到后面工序的生产率，作为第1轧制处理，优选进行轧制，直至达到250～350μm的厚度。
对于上述第1轧制处理后的钢板，进行镀覆Cu或者Ni预镀层的预镀处理、镀覆含Al镀层的镀覆处理以及第2轧制处理。关于这些处理的顺序，（1）预镀处理、镀覆处理、然后第2轧制处理，（2）预镀处理、第2轧制处理、然后镀覆处理，（3）第2轧制处理、预镀处理、然后镀覆处理中的任一种均可。
作为上述预镀处理，使用Cu或者Ni的镀槽，进行电镀法或化学镀法。如果Cu预镀膜和Ni预镀膜加在一起而将预镀膜的初期厚度设定为0.05～4μm，则在为含Al镀层时，钢层和含Al金属层之间形成的合金层的厚度为0.1～8μm。例如，当为含Al镀层时，在欲将形成的合金层的厚度控制为上述最合适的3～5μm的情况下，预镀膜的初期厚度可以控制为1.5～2.5μm。
另外，为了在钢层和合金层之间残存Cu或者Ni预镀膜而配置Cu层或者Ni层，预镀膜的初期厚度以4μm为基准，可以事先与欲残存的厚度相应地稍厚一些地成膜。厚度为4μm以下的Cu或者Ni预镀膜在为含Al镀层时向形成的合金层扩散而消失。超过4μm而成膜的预镀膜残存有从其膜厚减去4μm所得到的厚度，从而成为Cu层或者Ni层。例如，为了在钢层和合金层之间存在厚度为5μm的Cu层或者Ni层，可以事先将预镀膜的初期厚度设定为4＋5＝9μm的厚度。
在不进行预镀处理而欲形成上述合金层的情况下，可以适当调整钢层以及含Al金属层的成分组成。
作为上述镀覆处理，使用含有60～100质量%的Al、0～15质量%的Si以及0～40质量%的Cu的镀槽进行镀覆。作为该镀覆方法，可以使用电镀法以及化学镀法。通过含有0～15质量%的Si以及0～40质量%的Cu，可以降低镀槽的熔点。因此，设定为上述组成的镀槽。
再者，为了使镀槽的熔点下降，从而使镀覆工序变得简便，优选使用如下组成的含Al镀槽：以68.2质量%Al-4.7质量%Si-27.1质量%Cu或者68质量%Al-32质量%Cu这一组成为基础，各成分在±5质量%以内的范围变化。
作为上述第2轧制处理，进行轧制从而达到10～250μm的厚度。该轧制条件采用通常的轧制条件即可。当金属箔的厚度低于10μm时，作为基材用金属箔，因过薄而强度不足。另外，当金属箔的厚度超过250μm时，作为基材用金属箔，因过厚而过重。
除此以外，为了控制金属箔的含Al金属层表面的突起状缺陷以及含Al金属层表面的光泽度，在该第2轧制处理中，上述轧机优选使用表面粗糙度Ra为200μm以下的镜面状态的轧辊。将上述轧辊的表面粗糙度Ra设定为200μm以下的理由，是为了优选控制含Al金属层表面。
再者，为了控制含Al金属层表面的突起状缺陷以及含Al金属层表面的光泽度，根据需要，优选对上述第2轧制处理后的金属箔进行光亮精轧而作为表皮光轧处理。在该表皮光轧处理中，优选使用表面粗糙度Ra为1μm以下的镜面状态的轧辊。将上述轧辊的表面粗糙度Ra设定为1μm以下的理由，是为了优选控制含Al金属层表面。
第2轧制处理或者表皮光轧处理后的上述金属箔的含Al金属层的厚度优选为0.1～30μm。当低于0.1μm时，不能得到充分的耐蚀效果，而超过30μm时，需要大量镀覆Al，从而生产成本升高。上述含Al金属层的厚度优选为1～30μm。上述含Al金属层的厚度更优选为3～30μm。上述含Al金属层的厚度最优选为8～30μm。
另外，根据需要，为了使AlN层以致密的状态形成于第2轧制处理或者表皮光轧处理后的上述金属箔的含Al金属层表面，优选进行加热处理。这是将上述金属箔配置于含有10体积%±2体积%的氨或者肼的不活泼气体（氩、氮、氮＋氢等）中，在500～600℃的温度范围进行1～10小时的加热的处理。
同样，为了使Al2O3层以致密的状态形成于第2轧制处理或者表皮光轧处理后的上述金属箔的含Al金属层表面，作为阳极氧化处理，优选采用阳极氧化法使含Al金属层表面氧化。处理条件可以利用一直以来为人所知的硫酸氧化铝膜处理法、草酸氧化铝膜处理法或者铬酸氧化铝膜处理法等，其中，硫酸氧化铝膜处理法是最经济的，适于工业生产。但是，上述金属箔较薄，从而在阳极氧化处理中有上述金属箔发生变形的危险性，因而阳极氧化处理结束后，迅速进行水冷在维持上述金属箔的平坦度方面是重要的。
另外，为了在含Al金属层的表面形成Cr层或者Ni层，可以采用溅射法或者蒸镀法比较简单地成膜。但是，为了形成致密且均匀的Cr层或者Ni层，优选使用电镀法。因此，为了使Cr层或者Ni层以致密的状态形成于第2轧制处理或者表皮光轧处理后的上述金属箔的含Al金属层表面，作为电镀处理，优选实施镀覆。
同样，为了使溶胶凝胶层形成于第2轧制处理或者表皮光轧处理后的上述金属箔的含Al金属层表面，优选进行溶胶凝胶层的成膜处理。首先，调配在最终烘烤工序得到的覆盖膜中的氢浓度［H］（mol/l）与硅浓度［Si］（mol/l）之比为0.1≤［H］/［Si］≤10的溶胶。接着，将调配好的溶胶涂布于上述金属箔的含Al金属层表面，并使其干燥。最后，在干燥后进行烘烤，从而可以制造出具有无机有机混合覆盖膜的金属箔。
同样，为了使层叠层形成于第2轧制处理或者表皮光轧处理后的上述金属箔的含Al金属层表面，优选进行层叠层的成膜处理。使用由选自聚烯烃、聚酯、聚酰胺、聚酰亚胺之中的塑料薄膜等构成的层叠膜，用尼龙系粘结剂使其与上述金属箔的含Al金属层表面接触，然后进行加热，便可以用以1MPa左右的压力实施热压接的热层叠法进行成膜。
（实施例）
下面基于实施例就本发明的一实施方式的效果进行更具体的说明，但实施例的条件是为了确认本发明的实施可能性以及效果而采用的一个条件例，本发明并不局限于该一个条件例。本发明只要不脱离本发明的宗旨，可以实现本发明的目的，就可以采用各种条件。
[实验例1]
在实验例1中，作为第一轧制处理，对极低碳素钢进行热轧和冷轧，从而制成板厚为300μm的轧制钢板。作为预镀处理，采用电镀法在该轧制钢板上形成纯Cu或者纯Ni预镀膜。作为电镀Ni的镀槽，使用瓦特镀槽，作为电镀Cu的镀槽，使用硫酸铜镀槽。作为镀覆处理，将预镀处理后的轧制钢板在含Al的金属中浸渍20秒而进行热浸镀Al。作为第2轧制处理，将镀覆处理后的轧制钢板以各个道次10～20%的压下率进行轧制，从而制造出金属箔。一部分金属箔根据需要，在第二轧制处理后实施表皮光轧处理。关于上述的预镀膜以及含Al金属层的厚度，事先计算而进行决定，从而使箔化后的各层达到表1所述的厚度。
关于上述制造的金属箔的表面状态、各构成层的状态，通过观察以金属箔的与轧制方向正交的板宽度方向成为观察面的方式用平面沿板厚方向切断所得到切断面的金属组织而进行确认。金属组织观察以观察视场在板宽度方向为20μm以内的倍率进行、且板宽度方向的合计视场为300μm以上的方式，至少观察15个视场以上。轮廓曲线以及轮廓平均直线通过图像解析而求出。各构成层通过对上述切断面实施能量分散型X射线分析（EDX）而进行了鉴定。合金层的硬度采用维氏硬度计对上述切断面进行了测定。这些结果如表1所示。表中，用下划线表示的数值意味着在本发明的范围外。在切断面的观察时，如果观察到被称之为孔隙的空隙，则在表1中表示“有”孔隙。
另外，使用上述制造的金属箔，进行了耐蚀试验、180度附着弯曲试验以及光泽度测定试验。同样，这些结果如表1所示。表中，用下划线表示的数值意味着在本发明的范围外。
耐蚀试验通过盐雾试验（SST）进行了评价。将保持于35℃的5%NaCl水进行喷雾，将400小时以上用肉眼不能确认腐蚀的情况设定为VG（Very Good：优良），将300小时以上设定为G（Good：良），将100小时以上设定为NG（Not Good：不良），将低于100小时设定为B（Bad：差）。而且将NG和B设定为不合格。
作为更加苛刻的耐蚀性试验，将保持于50℃的10%NaCl水对切成150mm×70mm的金属箔进行喷雾。如果即使经过600小时金属箔表面也没有腐蚀，则耐蚀性最为良好，将其设定为EG（Extremely Good：极好）。如果即使经过500小时金属箔表面也没有腐蚀，则设定为GG（Greatly Good：大好）。如果即使经过400小时金属箔表面也没有腐蚀，则设定为VG（Very Good：优良）。如果即使经过300小时金属箔表面也没有腐蚀，则设定为G（Good：良）。如果即使经过100小时金属箔表面也没有腐蚀，则设定为NG（Not Good：不良）。如果低于100小时金属箔表面就发生腐蚀，则设定为B（Bad：差）。而且将NG和B设定为不合格。
180度附着弯曲试验通过在金属箔上反复进行内侧半径为零、弯曲角度为180°的180度附着弯曲加工，以调查产生薄膜的剥离或者龟裂的加工次数而实施。薄膜的剥离或者龟裂的观察通过采用光学显微镜在每一次循环的180度附着弯曲加工中，对金属箔的弯曲外周部进行观察来进行。将用光学显微镜观察到薄膜的剥离或者龟裂的时间点的加工次数设定为薄膜破坏次数。薄膜破坏次数在3次以上，判断为弹塑性变形性良好。
光泽度测定试验通过使用光泽度计，以入射角60°向金属箔入射光，测定相对于银镜面的反射率的比率而实施。光泽度低于75%者，评价为（Not Good：不良），在75%以上且低于80%者，评价为G（Good：良），在80以上且低于90%者，评价为VG（Very Good：优良），在90%以上者，评价为GG（Greatly Good：大好）。而且将NG设定为不合格。
如表1所示，在实施例1～31中，钢层、Cu层或者Ni层、合金层以及含Al金属层的状态都达到了目标，其结果是，显示出优良的耐蚀性、弹塑性变形性、表面平滑性和光泽度。
与此相对照，在比较例1～4中，钢层、Cu层或者Ni层、合金层以及含Al金属层的状态中的任一项未达到目标，其结果是，耐蚀性、弹塑性变形性、表面平滑性以及光泽度中的任一项并不充分。
比较例1由于没有合金层，因而是耐蚀性、180度附着弯曲性并不充分的例子。
比较例2由于合金层的厚度超过8μm，因而是在切断面观察到孔隙、180度附着弯曲性并不充分的例子。
比较例3由于合金层为以前的硬而脆的合金层，因而是合金层的维氏硬度为900Hv、180度附着弯曲性并不充分的例子。
比较例4是存在距轮廓平均直线的距离超过0.5μm的极大点的例子。光泽度也不充分。
[实验例2]
实验例2在与实验例1同样制作的金属箔上，形成AlN层、Al2O3层、Cr层、Ni层、溶胶凝胶层以及层叠层，通过改变其膜厚而调查了CIGS光电转换效率。关于CIGS光电转换效率，低于8%者评价为NG（Not Good：不良），在8%以上且低于10%者评价为G（Good：良），在10以上且低于12%者评价为VG（Very Good：优良），在12%以上者评价为GG（Greatly Good：大好）。而且将NG设定为不合格。
AlN层通过使用含有氨的不活泼气体的加热处理而进行制作。Al2O3层采用硫酸氧化铝膜处理进行制作。Cr层以及Ni层采用溅射法进行制作。
在溶胶凝胶层的形成中，作为调配溶胶的起始原料，使用10摩尔的甲基三乙氧基硅烷和10摩尔的四乙氧基硅烷的混合物，并在该混合物中添加20摩尔的乙醇而进行充分的搅拌。其后，一边搅拌一边滴加混合有2摩尔的醋酸和100摩尔的水的醋酸水溶液而进行水解。在这样得到的溶胶中添加100摩尔的乙醇，从而得到最终的溶胶。采用浸渍涂布法而在普通镀覆钢箔的两面涂布该溶胶，然后在空气中于100℃下，进行1分钟的干燥。然后，在氮气氛中以10℃/分钟的升温速度从室温升温至400℃，在400℃下烘烤30分钟而得到溶胶凝胶层。
在层叠层的形成中，在甲酚和二甲苯的质量比为70∶30的混合溶剂中使尼龙系粘结剂以15质量%的浓度溶解，将其溶解物涂布在树脂上，然后将该树脂以1MPa的压力热压接在加热至300℃的普通镀覆钢箔上，由此进行热层叠。其结果如表2所示。
如表2所示，实施例32～63都表现出优良的光电转换效率。特别地，AlN层、Al2O3层、Cr层、Ni层、溶胶凝胶层以及层叠层的厚度被控制为最合适的实施例表现出更为优良的光电转换效率。
实施例33～35以及实施例53～55由于将AlN层的厚度控制为最合适，因而表现出更为优良的光电转换效率。
实施例37～39由于将Cr层的厚度控制为最合适，因而表现出更为优良的光电转换效率。
实施例41～43由于将Ni层的厚度控制为最合适，因而表现出更为优良的光电转换效率。
实施例45～47以及实施例49～51由于将Al2O3层的厚度控制为最合适，因而表现出更为优良的光电转换效率。
实施例57～59由于将溶胶凝胶层的厚度控制为最合适，因而表现出更为优良的光电转换效率。
实施例61～63由于将层叠层的厚度控制为最合适，因而表现出更为优良的光电转换效率。
产业上的可利用性
根据本发明的上述实施方式，能够提供一种廉价的基材用金属箔，其与玻璃基材相比较，难以开裂且适于薄膜化，除此以外，同时满足作为基材用金属箔所要求的耐蚀性、表面平滑性以及弹塑性变形性。
Claims (6)
1.一种太阳能电池以及有机电致发光的基材用金属箔，其特征在于：
具有厚度为10～200μm的钢层、在所述钢层上生成的含有Fe和Al的合金层、以及在所述合金层上配置的含Al金属层，其中，
当将所述金属箔以与轧制方向正交的板宽度方向成为观察面的方式用平面沿板厚方向切断而得到切断面，将表示在该切断面的所述含Al金属层表面的切断线作为轮廓曲线，并将对所述轮廓曲线进行近似处理所得到的直线作为轮廓平均直线时，所述轮廓曲线并不存在距所述轮廓平均直线的距离超过10μm的在所述含Al金属层的表面侧凸出来的极大点；
关于所述合金层，其厚度为0.1～8μm，而且包含Al7Cu2Fe金属间化合物或者FeAl3基金属间化合物。
2.根据权利要求1所述的金属箔，其特征在于：在所述钢层和所述合金层之间，进一步具有厚度为2～10μm的Cu层或者厚度为2～10μm的Ni层。
3.根据权利要求1所述的金属箔，其特征在于：所述含Al金属层的厚度为0.1～30μm。
4.根据权利要求1所述的金属箔，其特征在于：在所述含Al金属层上，进一步具有厚度为0.01～0.08μm的AlN层或者厚度为0.01～50μm的Al2O3层。
5.根据权利要求1所述的金属箔，其特征在于：在所述含Al金属层上，进一步具有厚度为0.1～8μm的Cr层或者厚度为0.1～8μm的Ni层。
6.根据权利要求1所述的金属箔，其特征在于：在所述含Al金属层上，进一步具有选自溶胶凝胶层以及层叠层之中的至少1种薄膜。
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| 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 |
| BRPI1007387B1 (pt) | 2009-01-16 | 2019-11-19 | Nippon Steel & Sumitomo Metal Corp | material de aço revestido com liga de zn-al-mg-si-cr por imersão a quente e seu método para produção |
| 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 |
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- 2011-11-16 JP JP2012508683A patent/JP5816615B2/ja not_active Expired - Fee Related
- 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 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
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| 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 |
| 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 |
| JPH04250995A (ja) * | 1991-01-08 | 1992-09-07 | Daido Steel Co Ltd | 刃物材とその製造方法 |
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| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108501471A (zh) * | 2017-03-29 | 2018-09-07 | 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 |
| CN108355658A (zh) * | 2018-02-09 | 2018-08-03 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012067146A1 (ja) | 2012-05-24 |
| CN103210112B (zh) | 2015-10-21 |
| TW201240746A (en) | 2012-10-16 |
| US9296180B2 (en) | 2016-03-29 |
| TWI558478B (zh) | 2016-11-21 |
| JP5816615B2 (ja) | 2015-11-18 |
| US20130236737A1 (en) | 2013-09-12 |
| JPWO2012067146A1 (ja) | 2014-05-12 |
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