CN1179611C - 铝和铜的复合箔 - Google Patents
铝和铜的复合箔 Download PDFInfo
- Publication number
- CN1179611C CN1179611C CNB99117545XA CN99117545A CN1179611C CN 1179611 C CN1179611 C CN 1179611C CN B99117545X A CNB99117545X A CN B99117545XA CN 99117545 A CN99117545 A CN 99117545A CN 1179611 C CN1179611 C CN 1179611C
- Authority
- CN
- China
- Prior art keywords
- layer
- copper
- alumina supporter
- foil
- deposition
- 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.)
- Expired - Fee Related
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 243
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 134
- 239000010949 copper Substances 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000011888 foil Substances 0.000 title claims abstract description 57
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000004411 aluminium Substances 0.000 title description 25
- 239000010410 layer Substances 0.000 claims abstract description 167
- 239000011889 copper foil Substances 0.000 claims abstract description 113
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 81
- 239000011701 zinc Substances 0.000 claims abstract description 81
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000011241 protective layer Substances 0.000 claims abstract description 33
- 238000003475 lamination Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 103
- 238000004070 electrodeposition Methods 0.000 claims description 57
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 238000002161 passivation Methods 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000009413 insulation Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000009713 electroplating Methods 0.000 description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 8
- 239000005030 aluminium foil Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- LJCNRYVRMXRIQR-UHFFFAOYSA-L potassium sodium tartrate Chemical class [Na+].[K+].[O-]C(=O)C(O)C(O)C([O-])=O LJCNRYVRMXRIQR-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011158 industrial composite Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- -1 zinc metals Chemical class 0.000 description 1
Images
Classifications
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
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- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
提供一种复合箔,包含一层铝载体层、一层超薄铜箔和位于两者之间的一层保护层,该保护层是具有穿透于其中的电淀积锌的电淀积铜多孔层,铜的量为500-4000mg/m2铝载体层,锌的量为15-150mg/m2铝载体层,它足以提供合适的铝载体层和超薄铜箔之间的粘合强度,并在分离铝载体层后保护超薄铜箔。一种制备这些复合箔的方法,包括如下步骤:清洗铝载体层表面除去氧化铝,在铝载体层上电淀积多孔铜层,然后电淀积锌层,从不会除去锌层的浴液中电淀积第一层铜层,再电淀积第二层铜层形成超薄铜箔。本发明还包括由这些复合箔制得的层压板和由层压板制得的印刷线路板。
Description
技术领域
本发明总体上涉及制备和使用超薄铜箔,更具体的是涉及便于在制备印刷线路板的过程中处理超薄铜箔的复合箔。本发明还涉及一种复合箔,其中有一层独特的金属层放置在铝载体和超薄铜箔之间,以及制备和使用这一复合箔的方法。
背景技术
随着电子设备和相关电路的小型化,印刷线路板上电路的布线图案宽度和间距变得非常窄。结果,用来制备电路的铜箔变得越来越薄,例如使用12微米厚的箔,而不是常规的35微米和18微米的箔。近年来,对这些薄铜箔的需求增加了,人们已经在尝试超薄铜箔。然而,处理12微米或更薄的铜箔是困难的。例如,当制备和/或加工时它会起皱或撕裂。将超薄铜箔用作多层印刷线路板的外层时也会发生类似的问题。需要一种对超薄铜箔进行加工而避免这些问题的方法。
早先有人提出将超薄铜箔支承在金属载体层上,该金属载体层在铜箔层压到底材上之后剥去。通常在铜箔和金属载体之间使用一层剥离层。由这些载体上的超薄铜箔制备印刷线路板可以如下进行:在厚18-70微米的金属载体层上淀积一层厚度为1-12微米的铜层,然后将铜层的外露表面施加到一种预浸渍体(如玻璃增强的环氧树脂或类似物质)上,用热压进行层压。最后,分离金属载体层,留下敷铜箔层压板,由它可以制备印刷线路板。
已经提出了多种载体金属和剥离层类型。当铝用作载体层时,已经提出了多种类型的剥离层,例如:
1.Cr、Pb、Ni和Ag的硫化物或氧化物构成的剥离层(例如于美国专利No.3,998,601和EPO No.208 177 A中所披露的);
2.在先镀锌或用锌酸盐处理之后用镍或镍合金镀敷形成的剥离层(例如于美国专利No.3,936,548和3,990,926中所披露的);
3.氧化铝剥离层(例如于日本专利申请公开(经审查)No.昭60-31915、美国专利No.4,293,617和英国专利No.GB 1,458,260中所披露的);或
4.二氧化硅剥离层(例如于美国专利No.4,357,395中所披露的)。
然而,人们发现这些常规的载体上的铜箔存在着问题。
当剥离层在载体层表面上不均匀时,载体层和超薄铜箔之间的粘合强度会不均匀。结果,在层压成复合箔之后剥去载体层时,如果粘合强度高,则一些超薄铜箔会留在载体层上,不能制得所需的电路图案。如果粘合强度弱,则在制备和使用复合箔的过程中超薄铜箔会从载体层上过早地脱离。
将氧化物、硫化物、铬或无机物质(如铬等)用作剥离层时,在剥去载体层后会有一些无机物质留在超薄铜箔的表面上。
最后,当于高温下将复合箔层压在底材(如环氧预浸渍体)上时,通常难以剥除载体层,可能需要使用化学蚀刻来除去载体。层压中所用的高温还容易导致铜箔由于表面氧化而褪色。
由于这些问题,尽管已经有了上面提出的方法,目前工业上并未普遍使用超薄铜箔在载体层上的复合材料。
发明内容
因此,本发明的发明人旨在寻找一种能够克服上述问题的复合箔,以及这些复合箔的制备方法。他们研究了已有技术中按常规提出的作为复合箔剥离层的金属和/或金属化合物。
本发明的发明人发现,将铜直接淀积在铝表面或涂覆有氧化铝的表面上,由于其粘合强度太弱而不够理想。结果,在加工或层压至绝缘底材的过程中超薄铜箔会很容易地从铝载体层上脱离。
本发明的发明人还发现,将锌用作剥离层时,如已有技术所指出的,粘合强度太高以致于不能容易地除去铝载体。因此,需要蚀刻除去铝,这些过程会带来不希望有的结果。较好的是机械剥离铝载体,这样可以避免蚀刻。
将锌淀积在铝上通常用一个化学置换反应来进行,这一反应被称为“锌酸盐反应”。溶液中锌化合物提供的锌离子与铝载体接触。铝表面发生溶解,被锌金属置换。可以在非常短的时间内淀积足够的锌金属。因此,尽管锌酸盐方法不易控制,但它很简便。锌的电淀积较易控制。但是即使是使用电淀积,锌对于铝的粘合力还是太强以致于不易除去铝载体。
在另一个共同转让的专利申请中,使用某些有机化合物作为剥离层来克服超薄铜箔和金属载体之间与粘合强度有关的问题。以下,本发明会说明如何成功地在超薄铜箔和铝载体之间使用锌。
本发明中所用术语“粘合强度”是指从超薄铜箔上分离载体层所需的力。术语“剥离强度”是指从已经层压了超薄铜箔的底材上分离该超薄铜箔所需的力。
本发明的复合箔包含一层铝载体层和一层超薄铜箔层,在这两层之间有一层含锌的保护层。该保护层是具有穿透于其中的电淀积锌的电淀积铜多孔层,电淀积铜的量为每平方米所述铝载体层上的约500-4000毫克,电淀积锌的量为每平方米所述铝载体层上的约15-150毫克,它足以提供合适的铝载体层和超薄铜箔之间的粘合强度,并且在分离铝载体层之后对所述超薄铜箔进行保护。
在本发明的复合箔中,粘合强度足够高以允许对复合箔的加工,而且该粘合强度又足够低以允许在超薄铜箔层压到绝缘底材上之后容易地从超薄铜箔上分离铝载体。据信,锌能够提供所需的粘合强度,而且它还在除去铝载体露出铜之后对超薄铜箔具有保护作用。
在一个实施方案中,保护层包含一层在所述铝载体上的约500-3000mg/m2的电淀积铜的多孔层。穿透其中的锌是电淀积在多孔铜层上。所淀积的锌的量较好约为50-100mg/m2铝载体。
在另一个实施方案中,本发明是一种制备复合箔的方法,所述复合箔包含位于一层铝载体层上的一层超薄铜箔,其中所述方法包括以下步骤:
(a)清洗铝载体层的表面并除去氧化铝;
(b)在步骤(a)之后的铝载体上电淀积一层保护层,所述保护层是在所述铝载体层上的一层多孔铜层和在该多孔铜层上并穿透它的锌层,所述铜的量为每平方米所述铝载体层上的约500-4000毫克,所述锌的量为每平方米所述铝载体层上的约15-150毫克;
(c)从浴液中电淀积第一层铜层,该浴液不会除去步骤(b)中淀积的锌;和
(d)电淀积第二层铜层,该铜层足以提供超薄铜箔的所需厚度。
在随后的步骤中,复合箔的外露铜箔表面可以进行附加的结节化处理和钝化处理,以提高粘合力并防止层压之前超薄铜箔的氧化。
本发明的一个方面是一种复合箔,它含有上述有锌穿透于其中的多孔铜层,该层位于一层铝载体层(它也可以是一层箔)和一层超薄铜箔之间。
本发明的敷铜箔层压板包含本发明的复合箔层压在一块绝缘底材上。或者,敷铜箔层压板包含其外露表面用锌保护的超薄铜箔,它层压在绝缘底材上,在除去铝载体层之后该超薄铜箔仍保留。
本发明的印刷线路板包含上述敷铜箔层压板,在外露的超薄铜箔上形成有布线图案。该印刷线路板可以如下制得:从上述敷铜箔层压板上剥离铝载体层,使超薄铜箔露在外面,由该外露的超薄铜箔形成布线图案。
本发明的多层印刷线路板可如下形成:在一块其上已预先形成布线图案的内层板的至少一面上层压本发明的复合箔,得到敷铜箔层压板,从敷铜箔层压板上分离铝载体层以使超薄铜箔外露,并由所述超薄铜箔形成布线图案,由此得到多层印刷线路板。
本发明的多层印刷线路板还可以是通过层压多个上述印刷线路板而形成的。
附图说明
图1是说明在铝载体上淀积各种数量的铜的一系列照片。
图2是说明表中所记录的铜箔褪色情况的一系列照片。
具体实施方式
总的来说,本发明复合箔的特征是在铝载体层和超薄铜箔之间具有一层多孔铜和穿透于其中的锌的保护层。该保护层的一个作用是用作剥离层,在铝载体和超薄铜箔之间提供这样一种粘合强度,该粘合强度既足够高以允许加工和层压至绝缘底材,又足够弱以允许在层压后分离铝载体。该保护层的另一个作用是保护铜箔表面免受氧化,以使其在层压时处于高温下不会褪色。
铝载体层的厚度不是很严格,它可以是厚约18-70微米的箔。由于一般的载体层较薄,因此这种载体层也可以称为箔,但是应该理解,载体层可能比普通箔要厚。例如,可以使用厚达约5毫米的较重的载体板。
形成于保护层上的超薄铜箔层的厚度通常不超过12微米,可以更薄,例如5-7微米或更小。厚度超过12微米的铜箔可以用常规方法制备,无需载体层就能加工。尽管需要时本文所述的方法也可用来淀积厚度大于12微米的铜箔。超薄铜箔层较好的是通过电淀积来形成,尽管气相淀积或无电镀敷也可以使用,只要超薄铜箔层适于制备电路图案且具有可接受的粘合强度和剥离强度。
如上所述,本发明的发明人发现,直接在铝载体上电淀积锌(或者使用锌酸盐方法),然后电淀积超薄铜箔,得到的复合材料的粘合强度太高以致于在超薄铜箔层压至绝缘底材上之后不能容易地剥离铝载体。因此,铝载体通常用化学蚀刻方法除去,而化学蚀刻是不希望使用的方法,它较昂贵且涉及苛性碱溶液的处理。然而,如果将铜直接电淀积在铝载体上,粘合强度又太弱了。本发明提供了一种方法能得到合适的粘合强度,同时在剥离铝载体后对超薄铜箔起到保护作用。
在按日本标准JIS-C-6481测量粘合力的情况下,超薄铜箔和铝载体之间的粘合强度的范围约为1-50gf/cm(克力/厘米宽度),较好为1-2gf/cm,以确保在复合箔层压在绝缘底材上之后载体层可以从超薄铜箔上脱离下来。该粘合强度较弱,但足以允许加工。该粘合强度是均匀的,在超薄铜箔层压至底材上之后能够容易地除去该载体。当粘合强度低于1gf/cm时,该粘合强度太弱,以致于在层压超薄铜箔和底材的过程中或者在对层压板或电路板进行冲孔或钻孔的过程中,会发生超薄铜箔的凸出或脱离。当粘合强度大于50gf/cm时,则该粘合强度太大,以致于不能分离载体,或者需要进行特殊的处理,例如使用美国专利No.3,886,022中的水性介质。
本发明的复合箔的铝载体层和超薄铜箔之间的粘合强度几乎没有或没有变化。在单个复合箔的各处和多个实施例的复合箔之间比较,粘合强度都是一致的。
在本发明复合箔的制备过程中,在铝载体层上形成保护层,此后在保护层上淀积超薄铜箔层。较好的是进行铝载体层的预处理,以清洗铝载体层并除去氧化铝,从而得到清洁的表面用于淀积保护层。如果要容易地从超薄铜箔上剥离载体,粘合强度应该是均匀的,因此对铝载体层的预处理有助于确保稳定的结果。一般来说,将苛性碱浴用于铝载体的预处理。在以下的实施例中,使用含有氢氧化钠、四水合酒石酸钠钾和碳酸钠的水浴。将铝浸入该水浴中,然后用去离子水漂洗,接着电淀积多孔铜和穿透于其中的锌的保护层。
在准备好铝载体的表面之后,电淀积多孔铜层。多孔铜层可以在焦磷酸铜浴中电淀积(如实施例中),尽管据信也可以使用硫酸铜浴或其它适于电淀积铜的浴。从实施例中可见,铜层可能太厚或太薄。铜层应该具有足够的多孔性以使锌可以穿透。所得的含锌层具有所需的粘合强度。据发现,在每m2铝上约500-4000mg的铜层是合适的,较好的是约500-3000mg/m2铝的铜层,如下表中可见。如果所淀积的铜的量太小,则粘合强度会太高。如果铜的量太大,则粘合强度会太弱。锌较好的是电淀积的,约15-150mg/m2铝的锌具有合适的粘合强度,较好的约50-100mg/m2。
在保护层中,对于铜的量而言锌是少量的。即使如此,铝载体表面也只是部分地覆盖有铜淀积物,如图1所示。这必将使得锌接触到铝载体表面,这可能会产生不均匀的粘合强度。实施例中所示的结果使人认为,锌不是直接淀积在铝上,而是优先地淀积在铜上,穿透过铜到达铝上。不论这是否是正确的结论,这对于铝载体和超薄铜箔之间粘合强度的作用(如实施例中所示)是明显的。可以看出,粘合强度不随所淀积的铜的量而明显地变化。当铜的量为1000mg/m2时,铝表面仍有很大一都分是外露的(图1)。在该量以下,试验结果表明粘合强度太强了。随着铜淀积量的增大(图1),可进入的铝的量减少了,直至约4000mg/m2,据信这时锌不再能够穿透过铜层达到铝表面上。当只有铜与铝表面接触时,粘合强度太弱。然而,当淀积了对于铜淀积物来说较大量的锌时,可能产生过大的粘合强度。这一结果的原因不完全清楚,但是可能是因为有太多的锌达到了铝载体表面上,而锌与铝形成了太高的粘合强度。
较好的是将超薄铜箔电淀积在预先置于铝载体上的保护层的顶部。以使用两种电淀积铜的方法为宜。焦磷酸铜浴能够对铜进行更均匀的电淀积。更重要的是,它没有溶解锌的倾向,而如果使用酸式硫酸铜浴时可能会发生锌的溶解。焦磷酸铜电镀是较佳的,因为其有利于环境、操作安全,但也可以使用氰化铜浴。如果考虑到生产率和成本的话,硫酸铜电镀浴是有利的。因此,较好的是先是在焦磷酸铜浴中进行首次镀铜步骤,得到足以覆盖锌的厚度,通常至少为3000mg/m2,然后使用硫酸铜电镀浴进行二次电镀步骤,得到所需的超薄铜箔的厚度。该方法被用于以下实施例中。
焦磷酸铜电镀的条件不是很严格。然而,较好的是焦磷酸铜电镀浴中铜的浓度约为10-50克/升,焦磷酸钾的浓度约为100-700克/升。电解溶液的pH值应以约7-12为宜。浴温应约为30-60℃,电流密度约1-10安培/分米2。
酸式硫酸铜电镀的条件也不很严格。然而,较好的是硫酸铜电镀浴中铜的浓度约为30-100克/升,硫酸的浓度约为50-200克/升。电解溶液的浴温以约30-80℃为宜,电流密度约10-100安培/分米2。
锌电镀的条件不很严格。然而,较好的是按焦磷酸锌计的锌浓度约为1-10克/升,焦磷酸钾以约50-500克/升的浓度存在。浴温较好的约为20-60℃,电流密度约为0.1-5安培/分米2。
为了增强超薄铜箔的外露表面对绝缘底材的粘合力,可以用常规方法对超薄铜箔层进行剥离强度增强处理,例如通过调节电镀条件在箔表面上形成结节状的铜淀积物。结节化处理(nodularization process)的一个例子可见于美国专利No.3,674,656中。在剥离强度增强处理完成以后,可以对超薄铜箔表面进行常规钝化处理,例如在结节化的超薄铜层上淀积锌、铬酸锌、镍、锡、钴和铬。这些方法的一个例子可见于美国专利No.3,625,844。
使用热压将用上述方法制得的经处理的超薄铜箔的表面与绝缘底材进行层压,得到覆盖铜箔的层压板。可用来制备电子设备电路板的任何树脂底材都可用作绝缘底材。这些树脂底材可以包括FR-4(玻璃-纤维-环氧树脂)、纸-酚醛树脂、纸-环氧树脂、聚酰亚胺等。然后分离铝载体层,留下由超薄铜箔及其外露的保护层和绝缘底材组成的敷铜箔层压板。由外露的超薄铜箔形成布线图案,如此制得印刷线路板。
以下参考实施例进一步说明本发明。
实施例1
选择厚度为40微米的铝箔作为铝载体层。对该箔进行预处理,然后电淀积多孔铜层,接着电淀积锌。然后,用如下方法对覆盖有铜和锌的保护层的铝进行首次镀铜步骤和二次镀铜步骤。
A.
铝载体的预处理
将厚40微米的铝箔浸入40℃的含有30克/升NaOH、46克/升四水合酒石酸钠钾和46克/升碳酸钠的水溶液中27秒,取出,在去离子水中漂洗10秒,准备好用于电淀积保护层的铝表面。
B.
淀积多孔铜层
将经过预处理的铝载体箔放入一焦磷酸铜水浴中,其pH值为8.5,含有55.89克/升的焦磷酸铜和290克/升的焦磷酸钾,浴温为50℃。使用2.7安培/分米2的电流密度。在铝上电镀铜一段足以淀积所需量铜的时间,如下表所示。
C.
在多孔铜层上淀积锌
将含有所需量铜的铝箔放入40℃、pH值为10.5的焦磷酸锌浴中,以淀积所需量的锌。该浴含有14克/升焦磷酸锌和100克/升焦磷酸钾。
D.
首次镀铜步骤
用浴温为50℃、pH值为8.5的焦磷酸铜电镀浴以2.7安培/分米2的电流密度进行阴极电镀处理。该浴含有55.89克/升的焦磷酸铜和290克/升的焦磷酸钾。在保护剥离层上淀积约3000mg/m2、厚度为0.3微米的铜淀积层。
E.
二次镀铜步骤
在去离子水中漂洗初次铜淀积层的表面,然后使用浴温为40℃、含有216克/升五水合硫酸铜和150克/升硫酸的硫酸铜电镀浴以10安培/分米2的电流密度进行电镀,淀积厚度约为5微米的铜。
将复合箔层叠在四张FR-4上,然后在25千克/厘米2的压力下,于175℃进行热压60分钟,得到敷铜箔层压板。在层压前后,按JIS-C-6481测量超薄铜箔和45微米的铝载体层之间的粘合强度。还测定分离载体层后外露铜箔表面的褪色情况,在下表中给出等级。这些等级由图2的照片说明。
由实施例1的结果可以得出以下一般的结论。首先,因为组成超薄铜箔的两层铜在每种情况下都是相同的,所以多孔铜和锌淀积物(保护层)的相对尺寸是粘合强度和测得的表面褪色情况的主要原因。看来增加锌的存在量会使褪色较少。这表明锌穿透过铜淀积物而达到铝-铜界面。较好的是对于每平方米的铝使用至少50毫克的锌。铜与锌的比值看来对于层压后的粘合强度没有显著的影响,这是出人意料的发现。然而,看来可以淀积的锌有一个最大量,即使当铜淀积物较重时也是这样。当多孔铜为3700mg/m2、锌为145mg/m2时,发现粘合强度较高。该结果与比较例4中所表明的一致。因此得出结论,每平方米铝表面上的铜在约500-4000毫克(mg)之间时,得到合适的粘合强度。锌的量可以在每平方米铝表面约有15-150毫克之间,但较好的是约50-100mg/m2。
比较例1
用实施例1相同的方法制备复合箔,不同的是只淀积多孔铜,而省略锌的淀积和第一层薄铜层的淀积。结果见下表。层压前的粘合强度太弱,层压后的粘合强度可忽略不计。表面褪色等级为差。
因此可得出结论,锌淀积物对于提供所需的粘合强度和保护铜表面是必要的。
比较例2
用实施例1相同的方法制备复合箔,不同的是省去了多孔铜层,用锌酸盐置换反应淀积锌。结果见下表。在层压前后,铝箔载体都不能剥离。
当用锌的电淀积来代替锌酸盐处理时,层压前的粘合强度高得不合要求,层压后铝箔不能剥离。
因此可得出结论,在缺少多孔铜的情况下,粘合强度太高,以致于铝载体箔不能与超薄铜分离。
比较例3
用实施例1相同的方法制备复合箔,不同的是多孔铜淀积物太重。如下表所示,层压前后的粘合强度都太弱。
因此可得出结论,如果淀积的铜的量阻碍了锌的穿透的话,锌的接触就不足以提供所需的粘合强度。
比较例4
用实施例1相同的方法制备复合箔,不同的是通过锌酸盐处理来提供锌。在这种情况下,在层压后铝箔不能与超薄铜箔分离。
比较例5
用实施例1相同的方法制备两片复合箔,不同的是省去了第一层的超薄铜。仅仅使用硫酸铜浴来淀积超薄铜箔。结果见下表,粘合强度低得不合要求。
可以得出结论,锌在酸性浴中被除去了,主要留下对铝箔结合力很弱的多孔铜层。
表
用多种加工步骤进行热压粘合之后的评定
铝箔预处理后的电淀积金属的量 | ||||
多孔铜(mg/m2) | 锌(mg/m2) | 第一层铜(mg/m2) | 第二层铜 | |
实施例1 | 500 | 15 | 3000 | 5微米 |
1000 | 15 | 3000 | 5微米 | |
1700 | 50 | 3000 | 5微米 | |
2400 | 126 | 3000 | 5微米 | |
3000 | 126 | 3000 | 5微米 | |
3700 | 80 | 3000 | 5微米 | |
3700 | 145 | 3000 | 5微米 | |
比较例1 | 3000 | 无 | 无 | 5微米 |
比较例2 | --- | 锌酸盐 | 3000 | 5微米 |
--- | 120 | 3000 | 5微米 | |
比较例3 | 4400 | 145 | 3000 | 5微米 |
比较例4 | 3000 | 锌酸盐 | 3000 | 5微米 |
比较例5 | 3000 | 120 | 无 | 5微米 |
3000 | 180 | 无 | 5微米 |
超薄铜箔的性能 | |||
室温下 | 热压粘合后 | ||
粘合强度(gf/cm) | 粘合强度(gf/cm) | 表面褪色(1) | |
实施例1 | N/A | 4.8 | 2 |
N/A | 5.5 | 2 | |
3.8 | 4.3 | 3 | |
N/A | 5.0 | 3 | |
3.0 | 5.0 | 3 | |
N/A | 5.5 | 3 | |
N/A | 16.1 | 3 | |
比较例1 | 0.5 | 0.0 | 1 |
比较例2 | 不能剥离 | 不能剥离 | * |
9.4 | 不能剥离 | * | |
比较例3 | 0.5 | 0.0 | 1 |
比较例4 | N/A | 不能剥离 | * |
比较例5 | 0.5 | 0.0 | 1 |
0.5 | 0.0 | 1 |
注:"N/A"表示不能获得
(1)1=50-100%褪色
2=2-49%褪色
3=<1%褪色
参见图2
Claims (24)
1.一种复合箔,它包含一层铝载体层、一层超薄铜箔和一层位于两者之间的保护层,其中所述保护层是具有穿透于其中的电淀积锌的电淀积铜多孔层,所述电淀积铜的量为每平方米所述铝载体层上的500-4000毫克,所述电淀积锌的量为每平方米所述铝载体层上的15-150毫克,它足以提供合适的铝载体层和超薄铜箔之间的粘合强度,并且在分离铝载体层之后对所述超薄铜箔进行保护。
2.如权利要求1所述的复合箔,其中所述电淀积铜的多孔层包含每平方米所述铝载体层上的500-3000毫克的铜,所述电淀积锌包含每平方米所述铝载体层上的50-100毫克的锌。
3.如权利要求1所述的复合箔,其中所述超薄铜箔和所述铝载体层之间的粘合强度为1-50克力/厘米宽度。
4.如权利要求1所述的复合箔,其中所述超薄铜箔的厚度小于12微米。
5.如权利要求1所述的复合箔,其中所述铝载体层的厚度最厚达5毫米。
6.如权利要求5所述的复合箔,其中所述铝载体层的厚度为18-70微米。
7.如权利要求1所述的复合箔,其中还对所述超薄铜箔的外露铜表面进行结节化处理,以增强超薄铜箔外露表面和底材之间的剥离强度。
8.如权利要求7所述的复合箔,其中还对所述超薄铜箔的外露表面进行钝化处理,以防超薄铜箔外露表面的氧化。
9.如权利要求8所述的复合箔,其中所述钝化处理包含在所述结节化的超薄铜层上淀积选自锌、铬酸锌、镍、锡、钴和铬中的至少一种物质。
10.一种敷铜箔层压板,它包含层压在一片底材上的复合箔,所述复合箔包含一层铝载体层、一层超薄铜箔和一层位于两者之间的保护层,其中所述保护层是具有穿透于其中的电淀积锌的电淀积铜多孔层,所述电淀积铜的量为每平方米所述铝载体层上的500-4000毫克,所述电淀积锌的量为每平方米所述铝载体层上的15-150毫克,它足以提供合适的铝载体层和超薄铜箔之间的粘合强度,并且在分离铝载体层之后对所述超薄铜箔进行保护。
11.如权利要求10所述的敷铜箔层压板,其中除去了铝载体层以使所述超薄铜箔外露。
12.一种印刷线路板,它含敷铜箔层压板,该敷铜箔层压板包含层压在一片底材上的复合箔,所述复合箔包含一层铝载体层、一层超薄铜箔和一层位于两者之间的保护层,其中所述保护层是具有穿透于其中的电淀积锌的电淀积铜多孔层,所述电淀积铜的量为每平方米所述铝载体层上的500-4000毫克,所述电淀积锌的量为每平方米所述铝载体层上的15-150毫克,它足以提供合适的铝载体层和超薄铜箔之间的粘合强度,并且在分离铝载体层之后对所述超薄铜箔进行保护,其中除去了铝载体层以使所述超薄铜箔外露,外露的超薄铜箔上形成有布线图案。
13.一种多层印刷线路板,它是用下述方法形成的:在一块其上已预先形成布线图案的内层板的至少一面上层压复合箔,得到敷铜箔层压板,所述复合箔包含一层铝载体层、一层超薄铜箔和一层位于两者之间的保护层,其中所述保护层是具有穿透于其中的电淀积锌的电淀积铜多孔层,所述电淀积铜的量为每平方米所述铝载体层上的500-4000毫克,所述电淀积锌的量为每平方米所述铝载体层上的15-150毫克,它足以提供合适的铝载体层和超薄铜箔之间的粘合强度,并且在分离铝载体层之后对所述超薄铜箔进行保护;
从敷铜箔层压板上分离铝载体层以使超薄铜箔外露,并由所述超薄铜箔形成布线图案,由此得到多层印刷线路板。
14.一种多层印刷线路板,它是通过层压多个印刷线路板而形成的,后者用下述方法形成:
在一块其上已预先形成布线图案的内层板的至少一面上层压复合箔,得到敷铜箔层压板,所述复合箔包含一层铝载体层、一层超薄铜箔和一层位于两者之间的保护层,其中所述保护层是具有穿透于其中的电淀积锌的电淀积铜多孔层,所述电淀积铜的量为每平方米所述铝载体层上的500-4000毫克,所述电淀积锌的量为每平方米所述铝载体层上的15-150毫克,它足以提供合适的铝载体层和超薄铜箔之间的粘合强度,并且在分离铝载体层之后对所述超薄铜箔进行保护;
从敷铜箔层压板上分离铝载体层以使超薄铜箔外露,并由所述超薄铜箔形成布线图案。
15.一种制备复合箔的方法,所述复合箔包含位于一层铝载体层上的一层超薄铜箔,所述方法包括以下步骤:
(a)清洗所述铝载体层的表面并除去氧化铝;
(b)在所述铝载体层上电淀积一层保护层,所述保护层是在所述铝载体层上的一层多孔铜层和在该多孔铜层上并穿透它的锌层,所述铜的量为每平方米所述铝载体层上的500-4000毫克,所述锌的量为每平方米所述铝载体层上的15-150毫克;
(c)从不会除去步骤(b)中所述锌层的浴液中电淀积第一层铜层;
(d)在步骤(c)中的第一层铜层上电淀积足够的铜以提供所需的超薄铜箔。
16.如权利要求15所述的方法,其中步骤(b)中的所述多孔铜层是在每平方米所述铝载体层上有500-3000毫克的铜,所述锌层是在每平方米所述铝载体层上有50-100毫克的锌。
17.如权利要求15所述的方法,其中步骤(c)中的所述电淀积使用不含酸的电解浴。
18.如权利要求17所述的方法,其中所述电解浴是氰化铜或焦磷酸铜浴。
19.如权利要求17所述的方法,其中用步骤(c)中的所述电淀积在步骤(b)中的所述锌上淀积至少3000mg/m2的铜。
20.如权利要求15所述的方法,其中步骤(c)中的所述电淀积使用了含有焦磷酸铜的首次电解浴来淀积第一层铜,接着步骤(d)中的所述电淀积使用了含有硫酸铜和硫酸的二次电解浴在所述第一层铜上淀积第二层铜。
21.如权利要求20所述的方法,其中所述第一层的厚度至少为0.3微米,所述第一层和第二层的厚度最多达12微米。
22.如权利要求15所述的方法,该方法还包括以下步骤:对所述超薄铜层进行结节化处理,以提高所述超薄铜层外露表面与底材的粘合力。
23.如权利要求22所述的方法,该方法还包括以下步骤:对所述结节化的超薄铜层进行钝化处理,以防止所述超薄铜层的氧化。
24.如权利要求23所述的方法,其中所述钝化处理包括在所述结节化的超薄铜层上淀积选自锌、铬酸锌、镍、锡、钴和铬中的至少一种物质。
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SE9203327L (sv) | 1992-11-06 | 1993-12-20 | Metfoils Ab | Förfarande vid mönsterkortstillverkning samt användning därvid |
-
1998
- 1998-08-07 US US09/131,160 patent/US6183880B1/en not_active Expired - Fee Related
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1999
- 1999-08-02 JP JP21855599A patent/JP3180101B2/ja not_active Expired - Fee Related
- 1999-08-05 EP EP99306233A patent/EP0987931A3/en not_active Withdrawn
- 1999-08-06 MY MYPI99003357A patent/MY115624A/en unknown
- 1999-08-06 CN CNB99117545XA patent/CN1179611C/zh not_active Expired - Fee Related
- 1999-08-06 KR KR1019990032251A patent/KR100614859B1/ko not_active IP Right Cessation
- 1999-08-06 SG SG1999003848A patent/SG77265A1/en unknown
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SG77265A1 (en) | 2000-12-19 |
EP0987931A2 (en) | 2000-03-22 |
JP2000059035A (ja) | 2000-02-25 |
JP3180101B2 (ja) | 2001-06-25 |
KR100614859B1 (ko) | 2006-08-22 |
US6183880B1 (en) | 2001-02-06 |
EP0987931A3 (en) | 2002-04-24 |
CN1244460A (zh) | 2000-02-16 |
MY115624A (en) | 2003-07-31 |
KR20000017134A (ko) | 2000-03-25 |
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