CN106164327B - 表面处理铜箔及其制造方法、印刷电路板用覆铜层叠板、以及印刷电路板 - Google Patents
表面处理铜箔及其制造方法、印刷电路板用覆铜层叠板、以及印刷电路板 Download PDFInfo
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- CN106164327B CN106164327B CN201580016727.1A CN201580016727A CN106164327B CN 106164327 B CN106164327 B CN 106164327B CN 201580016727 A CN201580016727 A CN 201580016727A CN 106164327 B CN106164327 B CN 106164327B
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- copper foil
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 239000011889 copper foil Substances 0.000 title claims abstract description 171
- 238000004381 surface treatment Methods 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 41
- 229920005989 resin Polymers 0.000 claims abstract description 79
- 239000011347 resin Substances 0.000 claims abstract description 79
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 47
- 239000010703 silicon Substances 0.000 claims abstract description 46
- 238000004544 sputter deposition Methods 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000007792 gaseous phase Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010410 layer Substances 0.000 description 148
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
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- 239000000523 sample Substances 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 230000006978 adaptation Effects 0.000 description 9
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- 238000000576 coating method Methods 0.000 description 9
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
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- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
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- 239000012776 electronic material Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
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- 238000007639 printing Methods 0.000 description 2
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- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101001134276 Homo sapiens S-methyl-5'-thioadenosine phosphorylase Proteins 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 102100022050 Protein canopy homolog 2 Human genes 0.000 description 1
- 244000044283 Toxicodendron succedaneum Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- C23C14/0005—Separation of the coating from the substrate
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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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
- 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
- C23C14/0605—Carbon
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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
- 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
- C23C14/0635—Carbides
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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
- 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
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
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Abstract
本发明提供一种表面处理铜箔,其具备:铜箔、和在铜箔的至少单面设置的、氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的表面处理层。该表面处理铜箔可以如下制造:准备铜箔;在该铜箔的至少单面通过物理气相成膜或化学气相成膜形成氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的表面处理层。通过本发明能够提供具备表面处理层的铜箔,其即便在通过溅射等蒸镀法形成的极平坦的铜箔表面也能够实现与树脂层的高的密合强度并且具有适合于印刷电路板的细距化的、优选的绝缘电阻。
Description
技术领域
本发明涉及表面处理铜箔及其制造方法、印刷电路板用覆铜层叠板、以及印刷电路板。
背景技术
伴随着近年的便携式电子设备等电子设备的小型化和高功能化,对于印刷电路板要求布线图案的更加微细化(细距化)。为了应对所述要求,对于印刷电路板制造用铜箔要求比以往更薄且低的表面粗糙度。
另一方面,印刷电路板制造用铜箔与绝缘树脂基板贴合而使用,重要的是如何确保铜箔与树脂绝缘基板的密合强度。之所以这样是因为如果密合强度低,则印刷电路板制造时容易产生布线的剥离,从而产品成品率降低。从该点出发,通常的印刷电路板制造用铜箔,对铜箔的贴合面实施粗糙化处理而形成凹凸,通过压制加工将该凹凸咬入绝缘树脂基材的内部来发挥锚固效果,从而提高密合性。然而,使用了该粗糙化处理的方法是为了应对如上述的细距化的、与比以往薄且低表面粗糙度的铜箔不相容的方法。
也已知有不实施粗糙化处理而提高铜箔与绝缘树脂基材的密合性的印刷电路板用铜箔。例如,专利文献1(日本特开2010-18855号公报)中公开了在与绝缘树脂基材贴合而制造覆铜层叠板时所使用的铜箔的贴合面设置了表面处理层的表面处理铜箔,所述表面处理层是用干式成膜法在实施了清洗化处理的所述铜箔的贴合面附着熔点1400℃以上的高熔点金属成分和碳成分而形成的。
现有技术文献
专利文献
专利文献1:日本特开2010-18855号公报
发明内容
本发明人等此次得到如下见解:通过在铜箔的至少单面形成以规定的浓度添加了氢和/或碳的硅系表面处理层,从而能够提供带有表面处理层的铜箔,其即便在通过溅射等蒸镀法形成的极平坦的铜箔表面也能够实现铜箔表面与树脂层的高的密合强度并且具有适合于印刷电路板的细距化的、优异的绝缘电阻。
因此,本发明的目的在于,能够提供具备表面处理层的铜箔,所述表面处理层即便在通过溅射等蒸镀法形成的极平坦的铜箔表面也能够实现铜箔表面与树脂层的高的密合强度并且具有适合于印刷电路板的细距化的、优异的绝缘电阻。
通过本发明的一个实施方式,提供表面处理铜箔,其具备:铜箔、和
在前述铜箔的至少单面设置的、氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的表面处理层。
通过本发明的其他的实施方式,提供印刷电路板用覆铜层叠板,其具备:上述实施方式的表面处理铜箔、和与该表面处理层密合而设置的树脂层。
通过本发明的另一实施方式,提供印刷电路板,其包含依次层叠有树脂层、氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的层、以及铜层的层结构。
通过本发明的另一实施方式,提供上述实施方式的表面处理铜箔的制造方法,其包括:
准备铜箔的工序;和
在前述铜箔的至少单面通过物理气相成膜或化学气相成膜形成氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的表面处理层的工序。
附图说明
图1是表示例1~15的带有载体的铜箔的制造工序的流程图。
图2是表示例1~15的覆铜层叠板的制造工序的流程图。
图3是表示例1~15的剥离强度测定用样品的制造工序的流程图。
图4是表示例1~15的微细布线图案的形成工序的流程图。
图5是例5中观察的微细布线图案的SEM照片。
图6A是利用STEM-EDS对例5中得到的覆铜层叠板中的极薄铜箔层18、表面处理层20和底漆树脂层20的界面进行观察得到的图像。
图6B是图6A的放大图像所示的界面部分的Si元素映射图像。
图6C是图6A的放大图像所示的界面部分的Cu元素映射图像。
具体实施方式
表面处理铜箔
本发明的表面处理铜箔具备:铜箔、和在该铜箔的至少单面设置的表面处理层。也可以根据需要将表面处理层设置于铜箔的双面。并且,表面处理层是氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的层。这样,通过形成以规定的浓度添加了氢和/或碳的硅系表面处理层,由此能够提供具备表面处理层的铜箔,其即便在通过溅射等蒸镀法形成的极平坦的铜箔表面也能够实现铜箔表面与树脂层的高的密合强度并且具有适合于印刷电路板的细距化优异的绝缘电阻。
特别是,在高度微细化至线宽/间距(L/S)为13μm以下/13μm以下(例如,12μm/12μm、10μm/10μm、5μm/5μm、2μm/2μm)这样程度的布线图案的形成中,优选使用薄至目前为止没有的程度的极薄铜箔(例如,厚度1μm以下)。但是,想要通过电解制箔的手法来制造这样的极薄铜箔时,由于过薄的厚度容易产生针孔形成等问题。另外,也提出了不是通过现有的电解制箔的手法而是通过溅射来制造厚度3μm以下的极薄铜箔的技术,但由于这样形成的极薄铜箔具有极其平坦的铜箔表面(例如,算术平均粗糙度Ra:200nm以下),因此,不能够期待活用了铜箔表面凹凸的锚固效果而极难确保所述极薄铜箔与树脂层的高的密合强度。对于该点,本发明的表面处理铜箔并非像现有的极薄铜箔这样利用上述锚固效果的物理的手法来确保密合性,而是采用通过控制表面处理层的组成的化学的手法来实现提高与树脂层的密合性。即,通过在铜箔的至少单面形成氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的表面处理层,即便是通过溅射等蒸镀法形成的极平坦的铜箔表面也能实现与树脂层的高的密合强度。并且,上述组成的表面处理层能够实现适合于印刷电路板的细距化优异的绝缘电阻,由此,能够防止和降低细距化的布线图案中的布线间的泄露电流的产生。
因此,本发明的表面处理铜箔优选用于印刷电路板用覆铜层叠板的制造,该制造中,表面处理层层叠树脂层(典型地,绝缘树脂层)。
构成本发明的表面处理铜箔的铜箔可以用任意的方法制造。因此,铜箔可以为电解铜箔、压延铜箔;以带有载体的铜箔的形式准备铜箔的情况下,也可以为通过化学镀铜法和电解镀铜法等湿式成膜法、溅射和真空蒸镀等物理气相成膜法、化学气相成膜或它们的组合形成的铜箔。从容易应对由极薄化(例如,厚度3μm以下)导致的细距化的观点出发,特别优选的铜箔为通过溅射法和真空蒸镀等物理气相成膜制造的铜箔,最优选为通过溅射法制造的铜箔。另外,铜箔优选为无粗糙化的铜箔,但只要是在印刷电路板制造时不对布线图案形成带来障碍,则也可以为通过预粗糙化、软蚀刻处理、清洗处理、氧化还原处理产生了二次粗糙化的铜箔。对于铜箔的厚度没有特别的限定,为了应对如上述的细距化,优选为50~3000nm,更优选为75~2000nm,进而优选为90~1500nm,特别优选为100~1000nm,最优选为100~700nm。从成膜厚度的面内均匀性、片状或辊状的生产率的观点出发,这样范围内厚度的铜箔优选通过溅射法来制造。
构成本发明的表面处理铜箔的铜箔的表面处理层侧的表面优选具有根据JIS B0601-2001测定的200nm以下的算术平均粗糙度Ra,更优选为1~180nm,进一步优选为2~175nm,特别优选为3~130nm,最优选为5~100nm。这样,算术平均粗糙度越小,则越能够在在使用表面处理铜箔制造的印刷电路板上形成被高度微细化至线宽/间距(L/S)为13μm以下/13μm以下(例如,12μm/12μm~2μm/2μm)这样程度的布线图案。需要说明的是,这样,对于极平坦的铜箔表面不能期待活用了铜箔表面凹凸的锚固效果,但是本发明的表面处理铜箔不是通过利用上述锚固效果那样的物理手法来确保密合性而是采用通过控制表面处理层的组成的化学的手法来实现与树脂层的密合性的提高。
如上所述,本发明的表面处理铜箔也可以以带有载体的铜箔的形式提供。为极薄铜箔的情况下,可以通过制成为带有载体的铜箔来提高处理性。特别是,通过溅射法等真空蒸镀制造铜箔的情况下,优选通过采用带有载体的铜箔的形式来制造。如图1的(a)所示,带有载体的铜箔10可以为在载体12上依次具备剥离层16、极薄铜箔层18和表面处理层20的铜箔,也可以在载体12与剥离层16之间进一步设置耐热金属层14。另外,也可以为在载体12的双面依次上下对称地具备上述的各种层的结构。带有载体的铜箔除了具备上述的极薄铜箔层18和表面处理层20以外,也可以采用公知的层结构,没有特别的限定。作为载体的例子,可列举出:除了铜箔、镍箔、不锈钢箔、铝箔等金属箔之外,还可以列举出PET薄膜、PEN薄膜、芳香族聚酰胺薄膜、聚酰亚胺薄膜、尼龙薄膜、液晶聚合物等树脂薄膜;在树脂薄膜上具备金属层涂层的金属涂层树脂薄膜等,优选为铜箔。作为载体的铜箔也可以为压延铜箔和电解铜箔的任一者。载体的厚度典型地为210μm以下,从带有载体的铜箔的输送性与防止载体剥离时的破裂的观点出发,优选为10~210μm。作为构成耐热金属层14的金属优选的例子,可列举出铁、镍、钛、钽和钨,其中特别优选为钛。在进行高温压制加工等时,这些金属作为相互扩散势垒的稳定性高,特别是钛的钝化膜由非常强硬的氧化物构成,因此表现出优异的高温耐热性。该情况下,钛层优选通过溅射等物理气相成膜来形成。钛层等耐热金属层14的换算厚度优选为1~50nm,更优选为4~50nm。优选在耐热金属层14(特别是钛层)上作为剥离层16设置碳层和金属氧化物层的至少一者,更优选为碳层。碳与载体的相互扩散性和反应性小、即便在超过300℃的温度下受到压制加工等,也能够防止铜箔层与接合界面之间的由高温加热导致的金属结合,从而维持载体的剥离去除容易的状态。该碳层也优选使用溅射等物理气相成膜而形成。碳层的换算厚度优选为1~20nm。需要说明的是,“换算厚度”是指对于每单位面积的成分附着量进行化学地定量分析,由该分析量计算出的厚度。
构成本发明的表面处理铜箔的表面处理层是氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的硅系表面处理层。构成硅系表面处理层的硅典型地为非晶硅。可以认为,通过使硅系表面处理层以上述量含有氢和碳的至少任一者,能够实现与树脂层的密合性以及绝缘电阻两者,硅系表面处理层优选具有氢浓度1~35原子%和碳浓度1~15原子%。另外,构成表面处理层的硅系材料也可以包含起因于原料成分、成膜工序等而不可避免地混入的不可避免的杂质。例如,溅射靶材中微量添加有为了能够进行DC溅射的硼等导电性掺杂剂的情况下,这样的掺杂剂不可避免地微量地混入表面处理层,这样的不可避免的杂质的混入是被允许的。另外,在不脱离本发明的主旨的范围内,硅系表面处理层也可以包含其他的掺杂剂。另外,硅成膜后被曝露于大气中,因此而混入的氧气的存在是被允许的。
另外,硅系表面处理层中的硅原子含有率优选为50~98原子%,更优选为55~95原子%,进一步优选为65~90原子%。在这样的范围内时,能够使非晶硅的绝缘性和耐热性显著地起作用。需要说明的是,该硅元素的含有率是用高频辉光放电光谱表面分析装置(GDS)测定的。
硅系表面处理层的氢浓度优选为1~35原子%,更优选为10~31原子%,进而优选为15~30原子%,特别优选为20~30原子%,最优选为22~26原子%。硅系表面处理层的碳浓度优选为1~15原子%,更优选为3~13原子%,进而优选为4~12原子%,特别优选为5~12原子%,最优选为6~11原子%。碳浓度和/或氢浓度、优选碳浓度和氢浓度在上述范围内时,能够显著地提高与树脂层的密合性和绝缘电阻。
硅系表面处理层的氢浓度和碳浓度的测定通过卢瑟福背散射分析法(RBS,Rutherford Backscattering Spectrometry)、氢前向散射分析法(HFS)或核反应解析法(NRA)进行深度分布的测定来实施。作为这样的测定中所使用的装置,可列举出:Pelletron3SDH(National Electrostatics Corporation制)等。该浓度测定可以从刚成膜于铜箔上之后的硅系表面处理层进行。另外,即便对于后述的使用本发明的表面处理铜箔制造的印刷电路板、电子部件的形态中,通过从表面进行研磨直至来自表面处理铜箔的布线图案露出为止,之后对布线图案进行蚀刻,制成使表面处理层露出的状态,由此能够进行上述的浓度测定。
表面处理层优选具有0.1~100nm的厚度,更优选为2~100nm,进而优选为2~20nm,特别优选为4~10nm。设在这样的范围内时,能够显著地提高与树脂层的密合性和绝缘电阻。
制造方法
本发明的表面处理铜箔可以如下制造:准备上述的铜箔,在该铜箔的至少单面,通过物理气相成膜或化学气相成膜形成氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅表面处理层,从而来进行制造。如前所述,也可以根据需要在铜箔的双面形成表面处理层。
本发明的制造方法所使用的铜箔可以按照任意的方法来制造,对于其详细内容,如上所述。因此,从容易应对由极薄化(例如,厚度1μm以下)导致的细距化的观点出发,特别优选的铜箔是通过溅射法等物理气相成膜来制造的铜箔,最优选的是通过溅射法制造的铜箔,这样的铜箔优选以带有载体的铜箔的形式准备。
本发明的制造方法中,表面处理层的形成通过物理气相成膜或化学气相成膜来形成。通过使用物理气相成膜或化学气相成膜,能够容易地控制氢和/或碳的含量并且使表面处理层形成为期望的极其薄的厚度(0.1~100nm)的膜。因此,能够优选制造氢浓度1~35原子%和/或碳浓度1~15原子%的硅系表面处理层。
表面处理层优选通过物理气相成膜来形成。作为物理气相成膜的例子,可列举出溅射法、真空蒸镀法和离子镀法,最优选为溅射法。通过溅射法,能够不有损铜箔表面的平坦性(优选算术平均粗糙度Ra:200nm以下)而极其良好地形成极薄的表面处理层。另外,采用如图1的(a)所示的带有载体的铜箔10的构成的情况下,从能够通过溅射法形成设置于载体12上的耐热金属层14、剥离层16、极薄铜箔层18和表面处理层20的所有层的观点出发,还存在制造效率格外高的优点。
物理气相成膜优选使用硅靶材和/或碳化硅靶材,在非氧化性气氛下、与包含碳源和氢源的至少一种添加成分一起进行。此时,添加成分优选以选自由甲烷、乙烷、丙烷、丁烷、乙炔和四乙氧基硅烷组成的组中的至少一种气体作为原料。这些原料均能够以1个成分起到碳源和氢源两者的作用,因而优选。
物理气相成膜只要使用公知的物理气相成膜装置、按照公知的条件进行即可,没有特别的限定。例如,采用溅射法的情况下,溅射方式可以为磁控溅射、两极溅射法等公知的各种方法,从成膜速度快且生产率高的观点出发,优选磁控溅射。另外,溅射可以以DC(直流)和RF(高频)的任一电源进行,在进行DC溅射的情况下,为了对硅靶材赋予导电性,从提高制膜效率的观点出发,优选微量(例如,0.01~500ppm)添加导电性掺杂剂。作为该导电性掺杂剂的例子,可列举出硼、铝、锑、磷等,从成膜速度的效率、避免毒性、溅射成膜的耐湿性能等观点出发,最优选为硼。另外,在开始溅射前的腔室内的到达真空度优选小于1×10- 4Pa。作为溅射所使用的气体,优选组合使用氩气等非活性气体以及应该作为添加成分原料的气体(优选为甲烷、乙烷、丙烷、丁烷、乙炔、四乙氧基硅烷或它们的任意的组合)。最优选的气体是氩气与甲烷气体的组合。氩气的流量只要根据溅射腔室尺寸和成膜条件适宜决定即可,没有特别的限定。另外,从没有异常放电、等离子体照射不良等运行不良而保持连续稳定制膜性的观点出发,优选在制膜时的压力为0.1~2.0Pa的范围进行。该压力范围根据装置结构、容量、真空泵的排气容量、制膜电源的额定容量等,调节制膜功率、氩气的流量而设定即可。另外,溅射功率可以考虑制膜的膜厚均匀性、生产率等在靶材的每单位面积0.05~10.0W/cm2的范围内适宜设定即可。
印刷电路板用覆铜层叠板
根据本发明优选的方式,提供具备本发明的表面处理铜箔、和与该表面处理层密合而设置的树脂层的印刷电路板用覆铜层叠板。表面处理铜箔可以设置在树脂层的单面,也可以设置在双面。
树脂层包含树脂、优选为绝缘性树脂。树脂层优选为预浸料和/或树脂片。预浸料是指使合成树脂板、玻璃板、玻璃织布、玻璃无纺布、纸等基材浸渍合成树脂而成的复合材料的总称。作为绝缘性树脂优选的例子,可列举出环氧树脂、氰酸酯树脂、双马来酰亚胺三嗪树脂(BT树脂)、聚苯醚树脂、酚醛树脂等。另外,作为构成树脂片的绝缘性树脂的例子,可列举出环氧树脂、聚酰亚胺树脂、聚酯树脂、聚苯醚树脂等绝缘树脂。另外,从提高绝缘性等观点出发,也可以使树脂层含有氧化硅、滑石、氧化铝等各种无机填料等。对于树脂层的厚度,没有特别的限定,优选为1~1000μm,更优选为2~400μm,进一步优选为3~200μm。树脂层可以用多层构成,例如,可以在内层预浸料的双面以每个单面各设置1张(以双面计2张)外层预浸料来构成树脂层,该情况下,内层预浸料也可以以2层或2层以上的层构成。从铜箔的粘接强度的稳定性、铜箔表面的防擦伤等观点出发,优选通过预先涂布于铜箔表面的底漆树脂层在表面处理铜箔设置预浸料和/或树脂片等树脂层。
印刷电路板
本发明的表面处理铜箔优选用于印刷电路板的制作。即,通过本发明还提供具备来自于表面处理铜箔的层结构的印刷电路板。该情况下,印刷电路板含有依次层叠有树脂层、氢浓度1~35原子%和/或碳浓度1~15原子%的主要包含硅的层、以及铜层的层结构。主要包含硅的层是来自本发明的表面处理铜箔的硅系表面处理层的层;铜层是来自本发明的表面处理铜箔的铜箔的层。另外,对于树脂层,其如上述的覆铜层叠板中。所有情况下,印刷电路板除了使用本发明的表面处理铜箔以外,也可以采用公知的层结构。作为关于印刷电路板的具体例,可列举出:在将预浸料的单面或双面与本发明的表面处理铜箔粘接并使之固化制成层叠体(CCL)的基础上形成有电路的单面或双面印刷电路板;将它们多层化的多层印刷电路板等。另外,作为其他的具体例,还可列举出:在树脂薄膜上形成本发明的表面处理铜箔且形成电路的挠性·印刷电路板、COF、TAB带等。进而,作为其他的具体例,可列举出:在本发明的表面处理铜箔上涂布上述的树脂层而形成带有树脂的铜箔(RCC),将树脂层作为绝缘粘接材料层与上述的印刷基板层叠之后,以表面处理铜箔作为布线层的全部或一部分通过模拟半加成(MSAP)法、减成法等手法形成了电路的积层布线板;在半导体集成电路上交互地重复进行带有树脂的铜箔的层叠和电路形成的直接积层晶圆(directbuildup on wafer)等。作为进一步发展的具体例,还可列举出:将上述带有树脂的铜箔与基材层叠并形成了电路的天线元件;通过粘合剂层与玻璃、树脂薄膜层叠并形成了图案的面板·显示器用电子材料、车窗玻璃用电子材料;在本发明的表面处理铜箔涂布有导电性粘合剂的电磁波屏蔽·薄膜等。
实施例
通过以下的例子对本发明进一步具体地进行说明。
例1~15
(1)带有载体的铜箔的制作
如图1所示,在作为载体12的电解铜箔上依次形成耐热金属层14、剥离层16、极薄铜箔层18和表面处理层20而制作带有载体的铜箔10,进而在带有载体的铜箔10上形成底漆树脂层22,从而得到带有载体的铜箔24。此时,表面处理层20的成膜按照表1和2所示的各种条件进行。具体的步骤如下。
(1a)载体的准备
准备厚度18μm、具有算术平均粗糙度Ra 60~70nm的光泽面的电解铜箔(MITSUIMINING&SMELTING CO.,LTD.制)作为载体12。对该载体进行酸洗处理。该酸洗处理如下进行:将载体浸渍于硫酸浓度150g/l、液温30℃的稀硫酸溶液中30秒,去除表面氧化覆膜,水洗之后进行干燥。
(1b)耐热金属层的形成
在酸洗处理后的载体12(电解铜箔)的光泽面侧利用以下的装置和条件、通过溅射形成换算厚度为10nm的钛层作为耐热金属层14。
‐装置:卷取型DC溅射装置(日本真空技术株式会社制、SPW-155)
‐靶材:300mm×1700mm尺寸的钛靶材
‐到达真空度Pu:小于1×10-4Pa
‐溅射压PAr:0.1Pa
‐溅射功率:30kW
(1c)剥离层的形成
在耐热金属层14(钛层)的上面利用以下的装置和条件、通过溅射形成换算厚度为2nm的碳层作为剥离层16。
‐装置:卷取型DC溅射装置(日本真空技术株式会社制、SPW-155)
‐靶材:300mm×1700mm尺寸的碳靶材
‐到达真空度Pu:小于1×10-4Pa
‐溅射压PAr:0.4Pa
‐溅射功率:20kW
(1d)极薄铜箔层的形成
在剥离层16(碳层)的上面利用以下的装置和条件、通过溅射形成膜厚250nm的极薄铜箔层18。得到的极薄铜箔层具有算术平均粗糙度(Ra)46nm的表面。
‐装置:卷取型DC溅射装置(日本真空技术株式会社制、SPW-155)
‐靶材:直径8英寸(203.2mm)的铜靶材
‐到达真空度Pu:小于1×10-4Pa
‐气体:氩气(流量:100sccm)
‐溅射压:0.45Pa
‐溅射功率:1.0kW(3.1W/cm2)
(1e)表面处理层的形成
在极薄铜箔层18的上面利用以下的装置和条件、通过溅射形成硅层作为表面处理层20,从而制作带有载体的铜箔。
‐装置:卷取型DC溅射装置(日本真空技术株式会社制、SPW-155)
‐靶材:直径8英寸(203.2mm)的掺杂了硼200ppm的硅靶材
‐到达真空度Pu:小于1×10-4Pa
‐气体:氩气(流量:100sccm)
甲烷气体(流量:0~3.0sccm)
‐溅射压:0.45Pa
‐溅射功率:250W(0.8W/cm2)
此时,例1~8中,如表1所示,将表面处理层的膜厚设为恒定(6nm),除此以外,控制气体中的甲烷气体流量,从而使硅层中的氢浓度和碳浓度变化。另一方面,例9~15中,如表2所示,将甲烷气体流量设为恒定(1.5sccm),除此以外,使硅层的膜厚在0~100nm的范围内变化。所有的例子中,表面处理层的形成按照以下的条件进行。
对表面处理层20(硅层)中的氢浓度和碳浓度进行测定。该测定使用Pelletron3SDH(National Electrostatics Corporation制),通过卢瑟福背散射分析法(RBS)、氢前向散射分析法(HFS)或核反应解析法(NRA)来进行。另外,使用高频辉光放电光谱表面分析装置(GDS)测定表面处理层20(硅层)中的硅元素含有率。它们的结果如表1和2所示。
(1f)底漆树脂层的形成
作为评价样品,使用表面处理层上形成了底漆树脂层的样品、和表面处理层上没有形成底漆树脂层的样品。形成了底漆树脂层的样品的制作如下进行。首先,准备邻甲酚酚醛清漆型环氧树脂(东都化成株式会社制、YDCN-704)、可溶于溶剂的芳香族聚酰胺树脂聚合物与溶剂的混合清漆(日本化药株式会社制、BPAM-155)作为原料。向该混合清漆中添加作为固化剂的酚醛树脂(DIC Corporation制、VH-4170)和固化促进剂(四国化成工业株式会社制、2E4MZ),得到具有以下所示的配混比例的树脂组合物。
<树脂组合物的配混比例>
‐邻甲酚酚醛清漆型环氧树脂:38重量份
‐芳香族聚酰胺树脂聚合物:50重量份
‐酚醛树脂:18重量份
‐固化促进剂:0.1重量份
向该树脂组合物中添加甲乙酮进行调节以使树脂固体成分成为30重量%,从而得到树脂溶液。如图1所示,将得到的树脂溶液21使用凹版涂布机涂布于带有载体的铜箔10的表面处理层20(硅层)上。接着,进行5分钟的风干,之后在140℃的空气加热气氛中进行3分钟的干燥处理,形成半固化状态的厚度1.5μm的底漆树脂层22。
(2)覆铜层叠板的制作
如图2所示,使用上述带有载体的铜箔24和树脂基材26,如下制作覆铜层叠板28。
(2a)树脂基材的制作
将加入了玻璃纤维布、包含双马来酰亚胺·三嗪树脂的预浸料(MITSUBISHI GASCHEMICAL COMPANY,INC.制、GHPL-830NS、厚度45μm)层叠4张,制作树脂基材26。
(2b)层叠
将上述树脂基材26的双面(图2中,为了简化仅显示单面的层叠)用带有载体的铜箔24夹住,在压制温度:220℃、压制时间:90分钟、压力:40MPa的条件下将树脂基材26和带有载体的铜箔24层叠。这样,得到带有载体的覆铜层叠体25。
(2c)载体的剥离
由带有载体的覆铜层叠体25的剥离层16,手动剥离载体12,使极薄铜箔层18的表面露出。需要说明的是,耐热金属层14和剥离层16以附着于载体12(电解铜箔)侧的状态被剥离。这样,得到覆铜层叠板28。
(3)评价
对于这样得到的覆铜层叠板,进行:(3a)剥离强度的评价、(3c)微细布线图案形成的评价以及(3d)利用STEM-EDS的界面观察和元素映射测定。另外,另行制作与上述覆铜层叠板所具有的表面处理层相同的表面处理层,也进行(3b)表面处理层的绝缘电阻的评价。具体如下。
(3a)剥离强度的评价
如图3所示,由覆铜层叠板28制作剥离强度测定用样品32,对于极薄铜箔18的表面处理层20与底漆树脂层22的剥离强度进行评价。剥离强度测定用样品32通过对覆铜层叠板28使用硫酸铜镀液形成厚度18μm的电镀铜层30、之后进行图案形成而制作。另外,图案形成通过将形成的电镀铜层以10mm宽度进行遮掩,用氯化铜水溶液蚀刻来进行。
剥离强度的测定如下进行:以角度90°、速度50mm/分钟的条件测定3点样品的剥离强度,采用其平均值。另外,对于这样得到的剥离强度(平均值)按照以下的基准以A、B和C三个等级进行评价。结果如表1和2所示。
<评价基准>
A:400gf/cm以上
B:300gf/cm以上且小于400gf/cm
C:小于300gf/cm
(3b)表面处理层的绝缘电阻的评价
制作分别对应于例1~15的表面处理层的绝缘电阻测定用样品,进行绝缘电阻的评价。绝缘电阻测定用样品的制作如下进行:在玻璃基板(Corning Incorporated制、#1737)上,按照与上述的“(1e)表面处理层的形成”中记载的条件同样的条件形成厚度100nm的表面处理层(硅层)。将这样得到的测定用样品供于使用半导体设备·分析仪(AgilentTechnologies Japan,Ltd.制、B1500A)利用四探针法进行的测定中,采用将得到的比电阻值ρ(Ω·cm)换算成6nm的膜厚而成为(ρ×100/6)的薄层电阻值(Ω·□)作为绝缘电阻的评价指标。另外,对于得到的薄层电阻值按照以下的基准,以A、B和C三个等级进行评价。结果如表1和2所示。
<评价基准>
A:1.0×1012Ω/□以上
B:1.0×1010Ω/□以上且小于1×1012Ω/□
C:小于1.0×1010Ω/□
[表1]
[表2]
(3c)微细布线图案形成的评价
如图4所示,在各例中得到的覆铜层叠板28形成微细布线图案38,进行图案加工性的评价。首先,如下制作微细布线图案评价用样品。
(i)光致抗蚀剂涂布
在覆铜层叠板28的极薄铜箔层18上面涂布正型光致抗蚀剂(TOKYO OHKA KOGYOCo.,Ltd.制、TMMRP-W1000T)。
(ii)曝光处理
对涂布了光致抗蚀剂的覆铜层叠板28按照以下的条件进行曝光处理。
‐图案:线宽/间距(Line/Space)=2/2μm、图案长度2mm
‐玻璃掩模:铬蒸镀掩模
‐曝光量:180mJ/cm2(波长:365nm换算值、汞光谱射线)
(iii)显影
对于经曝光处理的覆铜层叠板28按照以下的条件进行显影处理,将光致抗蚀膜34如图4的(a)所示进行图案化。
‐显影液:TMAH水溶液(TOKYO OHKA KOGYO Co.,Ltd.制、NMD-3)
‐温度:23℃
‐处理方法:浸渍1分钟×2次
(iv)电镀铜层
在利用显影处理实施了图案化的覆铜层叠板28的极薄铜箔层18之上,如图4的(b)所示,利用硫酸铜镀液形成厚度2μm的电镀铜层36。
(v)光致抗蚀剂的剥离
从实施了电镀铜层36的覆铜层叠板28按照以下的条件剥离光致抗蚀膜34,成为图4的(c)所示的状态。
‐剥离液:ST106水溶液(TOKYO OHKA KOGYO Co.,Ltd.制)
‐温度:60℃
‐时间:5分钟
(vi)铜蚀刻(闪蚀)
对剥离了光致抗蚀膜34的覆铜层叠板28,按照以下的条件进行铜蚀刻,如图4的(d)所示,形成微细布线图案38。
‐蚀刻液:硫酸过氧化氢系蚀刻液(MEC Co.,Ltd.制、QE7300)
‐处理方法:浸渍
‐温度:30℃
‐时间:30秒
(vii)显微镜观察
对于得到的微细布线图案的外观用光学显微镜(1750倍)进行观察,确认了布线剥离的不良发生率。按照以下的评价基准评价不良发生率。
<评价基准>
A:不良发生率小于5%(最好)
B:不良发生率6~10%(良)
C:不良发生率11~20%(可允许)
D:不良发生率21%以上(不良)
将得到的评价结果示于表1和2。另外,将例5(实施例)中观察到的微细布线图案的SEM照片示于图5。
(3d)利用STEM-EDS的界面观察以及元素映射测定
对于例5(实施例)中制作的、涂布了底漆树脂层22的带有载体的覆铜层叠板25的载体12、极薄铜箔层18、表面处理层20和底漆树脂层22的界面利用STEM-EDS进行了观察的结果,得到图6A所示的图像。图6A的上侧的图像是下侧的照片的用圆所包围的界面部分的放大图像。将该放大图像所示的界面部分的Si元素映射图像示于图6B;将该界面部分的Cu元素映射图像示于图6C。由这些图像的比较可知,极薄铜箔层18的表面形成有硅系表面处理层20。
Claims (13)
1.一种表面处理铜箔,其具备:
铜箔、和
在所述铜箔的至少单面设置的、氢浓度10~35原子%和碳浓度3~15原子%的主要包含硅的表面处理层。
2.根据权利要求1所述的表面处理铜箔,其中,所述表面处理铜箔是在印刷电路板用覆铜层叠板的制造中使用的,在该制造中,在所述表面处理层上层叠树脂层。
3.根据权利要求1所述的表面处理铜箔,其中,所述表面处理层具有0.1~100nm的厚度。
4.根据权利要求1所述的表面处理铜箔,其中,所述铜箔的所述表面处理层侧的表面具有根据JIS B 0601-2001测定的、100nm以下的算术平均粗糙度Ra。
5.根据权利要求1所述的表面处理铜箔,其中,所述表面处理层的氢浓度为10~30原子%。
6.根据权利要求1所述的表面处理铜箔,其中,所述表面处理层的碳浓度为3~13原子%。
7.根据权利要求1所述的表面处理铜箔,其中,所述铜箔具有50~1000nm的厚度。
8.一种印刷电路板用覆铜层叠板,其具备:权利要求1~7中的任一项所述的表面处理铜箔、和与该表面处理层密合而设置的树脂层。
9.一种印刷电路板,其包括依次层叠有树脂层、氢浓度10~35原子%和碳浓度3~15原子%的主要包含硅的层、和铜层的层结构。
10.一种权利要求1~7中的任一项所述的表面处理铜箔的制造方法,该方法包括:
准备铜箔的工序;和
在所述铜箔的至少单面通过物理气相成膜或化学气相成膜来形成氢浓度10~35原子%和碳浓度3~15原子%的主要包含硅的表面处理层的工序。
11.根据权利要求10所述的方法,其中,所述表面处理层通过物理气相成膜来形成、且该物理气相成膜通过溅射来进行。
12.根据权利要求10所述的方法,其中,所述物理气相成膜使用硅靶材和/或碳化硅靶材,在非氧化性气氛下、在伴随包含碳源和氢源的至少一种添加成分下进行。
13.根据权利要求12所述的方法,其中,所述添加成分以选自由甲烷、乙烷、丙烷、丁烷、乙炔和四乙氧基硅烷组成的组中的至少一种气体作为原料。
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