CN111295055A - Preparation method of composite metal foil - Google Patents
Preparation method of composite metal foil Download PDFInfo
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- CN111295055A CN111295055A CN201811514600.4A CN201811514600A CN111295055A CN 111295055 A CN111295055 A CN 111295055A CN 201811514600 A CN201811514600 A CN 201811514600A CN 111295055 A CN111295055 A CN 111295055A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 382
- 239000002184 metal Substances 0.000 title claims abstract description 382
- 239000011888 foil Substances 0.000 title claims abstract description 168
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000004888 barrier function Effects 0.000 claims abstract description 84
- 239000010410 layer Substances 0.000 claims description 722
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 39
- 239000000956 alloy Substances 0.000 claims description 35
- 239000002356 single layer Substances 0.000 claims description 35
- 229910045601 alloy Inorganic materials 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 239000012790 adhesive layer Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000007788 roughening Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000002265 prevention Effects 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000007747 plating Methods 0.000 description 32
- 230000008569 process Effects 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 13
- 239000011889 copper foil Substances 0.000 description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910000990 Ni alloy Inorganic materials 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 238000009713 electroplating Methods 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
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- 239000003795 chemical substances by application Substances 0.000 description 6
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- 229910052708 sodium Inorganic materials 0.000 description 6
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 239000000080 wetting agent Substances 0.000 description 6
- 229910001182 Mo alloy Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 229910000531 Co alloy Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 3
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 239000011651 chromium Substances 0.000 description 2
- 239000000788 chromium alloy Substances 0.000 description 2
- QNHZQZQTTIYAQM-UHFFFAOYSA-N chromium tungsten Chemical compound [Cr][W] QNHZQZQTTIYAQM-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of materials, and discloses a preparation method of a composite metal foil, which comprises the following steps of firstly, forming a carrier layer, then forming a metal bonding layer on one side of the carrier layer, then forming a high-temperature resistant layer on the metal bonding layer to enable the metal bonding layer and the high-temperature resistant layer to form a barrier layer, then forming a stripping layer on the barrier layer, and finally forming a metal foil layer on the stripping layer to obtain the composite metal foil; in addition, the metal bonding layer is arranged between the carrier layer and the high-temperature resistant layer, so that the barrier layer is not easy to separate from the carrier layer, and the separation between the barrier layer and the carrier layer is prevented.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a preparation method of a composite metal foil.
Background
At present, the substrate is a processing material of a Flexible Printed Circuit board (FPC), which is generally composed of a Flexible insulating base film and a composite metal foil. In the prior art, when a substrate is prepared, a side of a composite metal foil (including a carrier layer and a metal foil layer) provided with a metal foil layer is generally pressed with a flexible insulating base film to obtain a substrate, and when the substrate is used, the carrier layer needs to be peeled off. However, since the composite metal foil and the flexible insulating base film need to be laminated at a high temperature, the carrier layer and the metal foil layer are easily diffused into each other at a high temperature, and the carrier layer and the metal foil layer are bonded to each other, so that the carrier layer and the metal foil layer are difficult to peel.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method of a composite metal foil, which can avoid bonding caused by mutual diffusion of a carrier layer of the composite metal foil and a metal foil layer of the composite metal foil at high temperature, so that the carrier layer and the metal foil layer are easy to peel.
In order to solve the above technical problem, an embodiment of the present invention provides a method for preparing a composite metal foil, including the following steps:
forming a carrier layer;
forming a metal adhesive layer on one side of the carrier layer;
forming a high-temperature resistant layer on the metal bonding layer, wherein the metal bonding layer and the high-temperature resistant layer form a barrier layer;
forming a release layer on the barrier layer;
a metal foil layer is formed on the release layer.
Preferably, the peel strength between the carrier layer and the barrier layer is greater than the peel strength between the release layer and the metal foil layer at a temperature of 20-400 ℃.
Preferably, the carrier layer and the barrier layer have a Peger test rating of 0 or 1 or 2 and the peel strength between the peel layer and the metal foil layer is 0.001 to 2N/cm.
Preferably, the peel strength between the peel layer and the metal foil layer is greater than or equal to the peel strength between the peel layer and the barrier layer.
Preferably, the metal bonding layer formed on one side of the carrier layer is specifically:
forming a single metal layer on one side of the carrier layer;
wherein the single metal layer formed on one side of the carrier layer is made of a first type of metal that is easily bonded to the carrier layer or a second type of metal that is easily bonded to the high temperature-resistant layer.
Preferably, the forming of the metal bonding layer on one side of the carrier layer is specifically:
forming a single layer alloy structure on one side of the carrier layer;
wherein the single-layered alloy structure formed on one side of the carrier layer is made of a first type of metal that is a metal that is easily bonded to the carrier layer and a second type of metal that is a metal that is easily bonded to the high temperature-resistant layer.
Preferably, the metal bonding layer formed on one side of the carrier layer is specifically:
forming a multilayer structure on one side of the carrier layer;
wherein the multi-layered structure formed on one side of the carrier layer includes a single metal layer made of a first type of metal and connected to the carrier layer, and the multi-layered structure formed on one side of the carrier layer further includes a single metal layer made of a second type of metal and connected to the high temperature resistant layer, the first type of metal being a metal easily bonded to the carrier layer, the second type of metal being a metal easily bonded to the high temperature resistant layer.
Preferably, the metal bonding layer formed on one side of the carrier layer is specifically:
forming a multilayer structure on one side of the carrier layer;
wherein the multi-layer structure formed on one side of the carrier layer includes an alloy layer made of a first type metal that is a metal easily bonded to the carrier layer and a single metal layer made of a first type metal or a second type metal that is a metal easily bonded to the high temperature resistant layer, and the alloy layer of the multi-layer structure formed on one side of the carrier layer is made of a first type metal that is a metal easily bonded to the carrier layer and a second type metal that is a metal easily bonded to the high temperature resistant layer.
Preferably, the first metal is copper or zinc, and the second metal is nickel or iron or manganese.
Preferably, the forming of the metal bonding layer on one side of the carrier layer is specifically: forming a metal adhesion layer on one side of the carrier layer by sputtering; and/or the presence of a gas in the gas,
the forming of the high-temperature resistant layer on the metal bonding layer specifically comprises: forming a high temperature resistant layer on the metal bonding layer by sputtering; and/or the presence of a gas in the gas,
the step of forming the stripping layer on the barrier layer is specifically as follows: a release layer is formed on the barrier layer by sputtering.
Preferably, the method further comprises the following steps after the carrier layer is formed:
and roughening the carrier layer to obtain the roughened carrier layer.
Preferably, the preparation method of the composite metal foil further comprises the following steps:
and forming a first oxidation preventing layer on the roughened carrier layer.
Preferably, the carrier layer is formed and then comprises:
annealing the carrier layer under heat treatment conditions;
wherein the heat treatment conditions are as follows: the heat treatment temperature is 200-300 ℃, and the heating time is 30-300 minutes.
Preferably, after the metal foil layer is formed on the release layer, the method further comprises the steps of: and roughening the surface of the metal foil layer far away from the carrier layer.
Preferably, after the roughening treatment is performed on the side of the metal foil layer away from the carrier layer, the method further comprises the following steps: and forming a second oxidation prevention layer on one surface of the roughened metal foil layer, which is far away from the carrier layer.
The preparation method of the composite metal foil provided by the embodiment of the invention comprises the steps of firstly, forming a carrier layer, then forming a metal bonding layer on one side of the carrier layer, then forming a high-temperature-resistant layer on the metal bonding layer to enable the metal bonding layer and the high-temperature-resistant layer to form a barrier layer, then forming a stripping layer on the barrier layer, and finally forming a metal foil layer on the stripping layer to obtain the composite metal foil, so that the carrier layer, the barrier layer, the stripping layer and the metal foil layer are sequentially stacked, the stripping layer is arranged between the carrier layer and the metal foil layer to facilitate stripping of the carrier layer, and the barrier layer is arranged between the carrier layer and the metal foil layer to prevent the carrier layer and the metal foil layer from being mutually diffused at high temperature to cause bonding, so that the carrier layer and the; in addition, the metal bonding layer is arranged between the carrier layer and the high-temperature resistant layer, so that the barrier layer is not easy to separate from the carrier layer, and the separation between the barrier layer and the carrier layer is prevented.
Drawings
FIG. 1 is a schematic structural view of one embodiment of a composite metal foil provided by the present invention;
FIG. 2 is a schematic structural view of another embodiment of a composite metal foil provided by the present invention;
FIG. 3 is a schematic view of a peel-off of an embodiment of a composite metal foil provided by the present invention;
FIG. 4 is another schematic view of a peel-away of an embodiment of a composite metal foil provided by the present invention;
FIG. 5 is a schematic flow chart diagram of one embodiment of a method of making a composite metal foil provided by the present invention;
wherein, 1, a carrier layer; 2. a barrier layer; 21. a high temperature resistant layer; 22. a metal bonding layer; 221. a first-type metal single-layer structure; 222. a second metal monolayer structure; 3. a peeling layer; 4. a metal foil layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, to solve the above technical problem, an embodiment of the present invention provides a composite metal foil, including a carrier layer 1, a barrier layer 2, a peeling layer 3, and a metal foil layer 4;
In the embodiment of the invention, the carrier layer 1 and the metal foil layer 4 are easily peeled off by arranging the peeling layer 3 between the carrier layer 1 and the metal foil layer 4 so as to facilitate peeling of the carrier layer 1 and by arranging the barrier layer 2 between the carrier layer 1 and the metal foil layer 4 so as to avoid bonding caused by mutual diffusion of the carrier layer 1 and the metal foil layer 4 at high temperature; in addition, by providing the metal adhesive layer 22 between the carrier layer 1 and the high temperature resistant layer 21, the barrier layer 2 is not easily separated from the carrier layer 1, thereby preventing the occurrence of peeling between the barrier layer 2 and the carrier layer 1.
In the embodiment of the present invention, in order to ensure that the carrier layer 1, the barrier layer 2 and the peeling layer 3 are peeled off simultaneously when the composite metal foil is used, the peel strength between the carrier layer 1 and the barrier layer 2 is greater than the peel strength between the peeling layer 3 and the metal foil layer 4 at a temperature of 20 to 400 ℃. Preferably, the carrier layer 1 and the barrier layer 2 have a Peterge test rating of 0 or 1 or 2 and the peel strength between the peel layer 3 and the metal foil layer 4 is 0.001-2N/cm. The hundred grid test grade in this embodiment is an ISO grade, and reference may be made to the standard "GBT 9286-1998 cut and break test of paint and varnish films", and in addition, the hundred grid test grade in this embodiment may correspond to an ASTM grade, for example, a hundred grid test grade of 0 corresponds to an ASTM grade of 5B, a hundred grid test grade of 1 corresponds to an ASTM grade of 4B, and so on, and further description is not given herein. The louver test grade can show the peel strength between the carrier layer 1 and the barrier layer 2, and the more advanced the grade, the greater the peel strength between the carrier layer 1 and the barrier layer 2. The carrier layer 1 with the hunger test grade between barrier layer 2 is at first tertiary, promptly the carrier layer 1 with the adhesion between the barrier layer 2 is bigger, and peel ply 3 with peel strength between the metal foil layer 4 is very little, consequently makes carrier layer 1 with peel strength between the barrier layer 2 is all far greater than peel ply 3 with peel strength between the metal foil layer 4, consequently, when using composite metal foil, can conveniently with carrier layer 1, barrier layer 2 and peel ply 3 follow simultaneously peel off on the metal foil layer 4.
As shown in fig. 3, in the embodiment of the present invention, the peel strength between the peel layer 3 and the metal foil layer 4 is greater than or equal to the peel strength between the peel layer 3 and the barrier layer 2. Since the peel strength between the peel layer 3 and the metal foil layer 4 is greater than or equal to the peel strength between the peel layer 3 and the barrier layer 2, the peel layer 3 can be partially or entirely left on the metal foil layer 4 when peeling the composite metal foil, so that the metal foil layer 4 can be prevented from being oxidized, thereby effectively protecting the metal foil layer 4. Of course, the peel strength between the peel layer 3 and the metal foil layer 4 may also be smaller than the peel strength between the peel layer 3 and the barrier layer 2, so that when the composite metal foil is peeled, the peel layer 3 can be partially or completely left on the barrier layer 2, and is peeled from the metal foil layer 4 along with the carrier layer 1 and the barrier layer 2, as shown in fig. 4, which is not described herein again.
Referring to FIG. 1, the thickness of the barrier layer 2 is greater than or equal to
Preferably, the thickness of the barrier layer 2 is preferably such that
Wherein the high temperature resistant layer 21 is organicA high-temperature layer 21; alternatively, the high temperature resistant layer 21 is made of any one or more of tungsten, chromium, zirconium, titanium, nickel, molybdenum, cobalt, and graphite. Preferably, the high temperature resistant layer 21 is a single layer alloy structure; or, the high temperature resistant layer 21 is a multilayer structure composed of a single material layer or a multilayer structure composed of an alloy layer and a single material layer, wherein the single material layer is made of the same chemical element. Specifically, the single-layer alloy structure is a single-layer structure made of an alloy material, for example, a single-layer structure made of a tungsten-chromium alloy; the high temperature resistant layer 21 is a multilayer structure composed of a single material layer or a multilayer structure composed of an alloy layer and a single material layer, for example, a multilayer structure composed of a tungsten metal layer and a chromium metal layer, or a multilayer structure composed of a tungsten-chromium alloy layer and a zirconium metal layer.
As shown in fig. 1 and 2, in order to prevent delamination between the barrier layer 2 and the carrier layer 1, the metal adhesive layer 22 is made of any one or more materials of a first metal; alternatively, the metal bonding layer 22 is made of any one or more materials of a second type of metal; alternatively, the metal bonding layer 22 is made of any one or more materials of a first type of metal and any one or more materials of a second type of metal; wherein the first type of metal is a metal that is easily bonded to the carrier layer, and the second type of metal is a metal that is easily bonded to the high temperature-resistant layer 21, thereby preventing peeling from between the carrier layer 1 and the barrier layer 2. Preferably, the first type of metal is copper or zinc and the second type of metal is nickel or iron or manganese. By providing the metal adhesive layer 22, the barrier layer 2 can be firmly connected with the carrier layer 1, thereby preventing the peeling between the barrier layer 2 and the carrier layer 1. In addition, since the adhesion force between the first type metal and the carrier layer 1 is stronger and the adhesion force between the second type metal and the high temperature resistant layer 21 is stronger, the barrier layer 2 is not easily separated from the carrier layer 1 by connecting the mono-metal layer made of the first type metal to the carrier layer 1 and simultaneously connecting the mono-metal layer made of the second type metal to the high temperature resistant layer 21.
In the embodiment of the present invention, the structure of the metal bonding layer 22 may include, but is not limited to, the following cases: (1) the metal bonding layer 22 is a single metal layer made of the first metal; (2) the metal bonding layer 22 is a single metal layer made of the second metal; (3) the metal bonding layer 22 is a single-layer alloy structure made of the first metal and the second metal, for example, a single-layer alloy structure made of a copper-nickel alloy; (4) the metal bonding layer 22 comprises a single metal layer made of a first metal and connected to the carrier layer 1, and the metal bonding layer 22 further comprises a single metal layer made of a second metal and connected to the high temperature resistant layer 21, for example, a multilayer structure of a copper metal layer and a nickel metal layer, and the copper metal layer and the nickel metal layer
The carrier layer 1 is connected, and the nickel metal layer is connected with the high temperature resistant layer 21; (5) the metal bonding layer 22 includes a multilayer structure composed of an alloy layer and a single metal layer; wherein the alloy layer of the metal bonding layer 22 is made of the first type of metal and the second type of metal, and the single metal layer of the metal bonding layer 22 is made of the first type of metal or the second type of metal; such as an alloy layer made of a copper-nickel alloy and a single metal layer made of manganese.
As shown in fig. 2, in the present embodiment, the metal bonding layer 22 is made of a first metal single-layer structure 221 and a second metal single-layer structure 222, wherein the first metal single-layer structure 221 is a single metal layer made of a first metal and connected to the carrier layer 1, and the second metal single-layer structure 222 is a single metal layer made of a second metal and connected to the high temperature resistant layer 21.
In the embodiment of the present invention, a structure made of a single-layer structure of the first metal and/or a single-layer structure of the second metal may be further disposed between the first metal single-layer structure 221 and the second metal single-layer structure 222. By providing a structure made of a single-layer structure of the first type metal and/or a single-layer structure of the second type metal between the first type metal single-layer structure 221 and the second type metal single-layer structure 222, the connection between the barrier layer 2 and the carrier layer 1 is further secured, thereby further preventing the peeling between the barrier layer 2 and the carrier layer 1.
In the present embodiment, the peeling layer 3 is made of any one or more materials of nickel, silicon, molybdenum, graphite, titanium, and niobium; alternatively, the peeling layer 3 is made of an organic polymer material. Wherein the thickness of the peeling layer 3 is preferably
Since it is difficult to form a uniform metal foil layer 4 when the peeling layer 3 is too thick, a large number of pinholes are easily generated in the metal foil layer 4 (when pinholes are formed in the metal foil layer 4, a disconnection phenomenon is easily generated after it is etched into a wiring); when the peeling layer 3 is too thin, it is liable to cause difficulty in peeling from the metal foil layer 4; therefore, the thickness of the peeling layer 3 is preferably set to be thick
Thereby ensuring that a uniform metal foil layer 4 can be formed, avoiding the generation of a large number of pinholes in the metal foil layer 4, while allowing easy peeling between the peeling layer 3 and the metal foil layer 4.
In the present embodiment, the thickness of the metal foil layer 4 is less than or equal to 9 μm. In order to meet the requirement of circuit board fine circuit production, the thickness of the metal foil layer 4 may be preferably 6 μm, 5 μm, 4 μm or 2 μm, so as to obtain an extremely thin metal foil layer 4 which is advantageous for forming a fine circuit board. In addition, in order to peel off from the carrier layer 1 to obtain the complete ultrathin metal foil layer 4 with few pinholes (especially, a metal foil layer with a thickness of 2 μm, 4 μm, etc.), in the present embodiment, the metal adhesive layer 22 is provided, so that the metal adhesive layer 22 not only enables the barrier layer 2 and the carrier layer 1 to have a strong peel strength, but also effectively ensures that the carrier layer 1 can be stably peeled off from the metal foil layer 4 to obtain the complete ultrathin metal foil layer 4, and the surface of the carrier layer 1 is processed by the metal adhesive layer 22, so that the whole surface of the carrier layer 1 is more uniform and compact, thereby being beneficial to peeling off from the carrier layer 1 to obtain the ultrathin metal foil layer 4 with few pinholes, and further being beneficial to the manufacture of subsequent circuits. Further, the metal foil layer 4 is preferably a copper foil or an aluminum foil; the carrier layer 1 can be carrier copper, carrier aluminum, or organic film, etc., and a certain thickness is needed because the carrier layer 1 mainly plays a role of carrying, and when the carrier layer 1 is carrier copper or carrier aluminum, the thickness of the carrier layer 1 is preferably 9-50 μm; when the support layer 1 is an organic thin film, the thickness of the support layer 1 is preferably 20 to 100 μm.
In the embodiment of the present invention, the roughness Rz of the side of the carrier layer 1 near the metal foil layer 4 is less than or equal to 5 μm; and/or the roughness Rz of the side of the metal foil layer 4 facing away from the carrier layer 1 is less than or equal to 3.0 μm. When the metal foil layer 4 is a copper foil, the larger the roughness of the copper foil is, the larger the adhesion force between the copper foil and other materials is, but when the roughness of the copper foil is too large, the copper foil cannot be applied to a circuit board for high-frequency signal transmission, so that the roughness Rz of a general copper foil is 0.5 to 3.0 μm; when the copper foil is applied at high frequency, the roughness of the copper foil is set to be less than 0.5 μm, so that the copper foil can be applied to a circuit board for high frequency signal transmission on the premise of ensuring the adhesive force between the copper foil and other materials.
In the embodiment of the present invention, in order to prevent the carrier layer 1 from being oxidized, a first oxidation preventing layer is disposed on a side of the carrier layer 1 close to the barrier layer 2 in the embodiment; the carrier layer 1 is protected by providing a first oxidation preventing layer on the side of the carrier layer 1 adjacent to the barrier layer 2 to prevent oxidation of the carrier layer 1. In order to prevent the metal foil layer 4 from being oxidized, a second oxidation preventing layer is arranged on one side, away from the barrier layer 2, of the metal foil layer 4, and the second oxidation preventing layer is arranged on one side, away from the barrier layer 2, of the metal foil layer 4, so that the metal foil layer 4 is prevented from being oxidized, and the metal foil layer 4 is protected.
Referring to fig. 5, in order to solve the same technical problem, an embodiment of the present invention further provides a method for preparing the composite metal foil, including the following steps:
s11, forming a carrier layer 1;
s12, forming a metal adhesive layer 22 on one side of the carrier layer 1;
s13, forming a high temperature resistant layer 21 on the metal bonding layer 22, wherein the metal bonding layer 22 and the high temperature resistant layer 21 form a barrier layer 2;
s14, forming a release layer 3 on the barrier layer 2;
s15, forming a metal foil layer 4 on the peeling layer 3.
In order to ensure that the carrier layer 1, the barrier layer 2 and the peeling layer 3 can be easily peeled from the metal foil layer 4 at the same time when the composite metal foil is used, in the embodiment of the present invention, the peel strength between the carrier layer 1 and the barrier layer 2 is greater than the peel strength between the peeling layer 3 and the metal foil layer 4 at a temperature of 20 to 400 ℃. Preferably, the carrier layer and the barrier layer have a Peger test rating of 0 or 1 or 2 and the peel strength between the peel layer 3 and the metal foil layer 4 is 0.001-2N/cm at a temperature of 20-400 ℃.
In the embodiment of the present invention, the first metal is a metal that is easily bonded to the carrier layer 1, and the second metal is a metal that is easily bonded to the high temperature resistant layer 21, preferably, the first metal is copper or zinc, and the second metal is nickel or iron or manganese.
Because adopt the electroplating mode to lead to easily the barrier layer 2 with the roughness of peel ply 3 receives the influence of electric current when electroplating, thereby makes the formation the barrier layer 2 with the surface roughness of peel ply 3 is very inhomogeneous, thereby leads to follow-up formation the surface roughness of metal foil layer 4 is also inhomogeneous, is unfavorable for forming good peeling stability and pinhole quantity then, also does not benefit to the preparation of follow-up circuit simultaneously. Based on this, in the embodiment of the present invention, the step S12, the step S13, and the step S14 preferably adopt a sputtering method, the current of the sputtering method preferably adopts 6-12A, and the voltage preferably adopts 300-500V. The metal bonding layer 22 and the high temperature resistant layer 21 formed by sputtering constitute the barrier layer 2 to ensure that a uniform and dense barrier layer 2 is obtained, and the uniform and dense peeling layer 3 is formed by sputtering, thereby facilitating improvement of peeling stability of the composite metal foil and enabling effective reduction of the number of pinholes; in addition, the metal foil layer 4 is preferably formed by electroplating, and before the metal foil layer 4 is formed, the uniform and dense barrier layer 2 and the peeling layer 3 are formed by sputtering, so that the metal foil layer 4 is uniformly electroplated, the surface roughness of the formed metal foil layer 4 is uniform, the subsequent circuit is further facilitated to be manufactured, and the thinner metal foil layer 4 is facilitated to be manufactured.
In the embodiment of the present invention, the metal bonding layer 22 formed on one side of the carrier layer 1 is specifically: forming a single metal layer on one side of the carrier layer 1; wherein the single metal layer formed on one side of the carrier layer 1 is made of a first type of metal or a second type of metal.
In the embodiment of the present invention, the metal bonding layer 22 formed on one side of the carrier layer 1 may specifically be: forming a single layer alloy structure on one side of the carrier layer 1; wherein the single-layer alloy structure formed on one side of the carrier layer 1 is made of a first type of metal and a second type of metal.
In the embodiment of the present invention, the metal bonding layer 22 formed on one side of the carrier layer 1 may specifically be: forming a multilayer structure on one side of the carrier layer 1; wherein the multilayer structure formed on one side of the carrier layer 1 includes a single metal layer made of a first metal type and connected to the carrier layer 1, and the multilayer structure formed on one side of the carrier layer 1 further includes a single metal layer made of a second metal type and connected to the high temperature-resistant layer 21.
In the embodiment of the present invention, the metal bonding layer 22 formed on one side of the carrier layer 1 may specifically be: forming a multilayer structure on one side of the carrier layer; wherein the multilayer structure formed on one side of the carrier layer 1 includes an alloy layer made of a first type of metal and a second type of metal and a single metal layer made of a first type of metal or a second type of metal.
The high temperature resistant layer 21 may be an organic high temperature resistant layer 21; or, the high temperature resistant layer 21 is a single-layer alloy structure; or, the high temperature resistant layer 21 is a multilayer structure composed of a single material layer or a multilayer structure composed of an alloy layer and a single material layer, and the single material layer is made of the same chemical element; the high temperature resistant layer 21 is an organic high temperature resistant layer, or the high temperature resistant layer 21 is made of any one or more of tungsten, chromium, zirconium, titanium, nickel, molybdenum, cobalt and graphite.
In an embodiment of the present invention, the forming of the carrier layer 1 further includes the following steps:
s111, roughening the carrier layer 1 to obtain a roughened carrier layer 1;
s112, forming a first anti-oxidation layer on the roughened carrier layer 1;
wherein the carrier layer 1 may be a carrier copper or a carrier aluminum. The support layer 1 may be formed by electroplating, and a plating solution forming the support layer 1 may include a copper sulfate solution, wherein the copper content of the plating solution forming the support layer 1 is: 15-25g/L, and the PH value is 6-9; the plating solution for forming the carrier layer 1 further comprises additives, wherein the additives comprise brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene glycol, the mass fraction of the brightener sodium sulfonate is preferably 0.1-2g/L, the mass fraction of the leveling agent thiourea is preferably 0.01-1g/L, and the mass fraction of the wetting agent polyethylene glycol is preferably 0.1-5 g/L. The carrier layer 1 is roughened by means of acid electroplating, wherein the plating solution for acid copper plating can comprise a copper sulfate solution, the copper content of the plating solution for acid copper plating is 10-15g/L, the acid content is 90-100g/L, and the molybdenum content is 600-800 PPM. Wherein, the first oxidation prevention layer can be formed in a zinc-nickel alloy plating mode; after the first oxidation preventing layer is formed on the roughened carrier layer 1, the first oxidation preventing layer may be plasma cleaned (plasma), wherein the voltage for plasma cleaning is preferably 1500-.
In the embodiment of the present invention, in order to further prevent the adhesion between the carrier layer 1 and the metal foil layer 4, the carrier layer 1 is formed by:
s113, annealing the carrier layer 1 under the heat treatment condition; wherein the heat treatment conditions are as follows: the heat treatment temperature is 200-300 ℃, and the heating time is 30-300 minutes. Preferably, the heating time is 1 hour. The carrier layer 1 is annealed under heat treatment conditions to suppress crystal growth of the carrier layer 1 in the heating process, thereby delaying diffusion of the carrier layer 1 in the heating process and further preventing adhesion between the carrier layer 1 and the metal foil layer 4.
In the present embodiment, the peeling layer 3 may be made of any one or more materials of nickel, silicon, molybdenum, graphite, titanium, and niobium.
In the embodiment of the present invention, the metal foil layer 4 may be a copper foil or an aluminum foil. The metal foil layer 4 may be formed by electroplating, and a plating solution for forming the metal foil layer 4 may include a copper sulfate solution, wherein the copper content of the plating solution for forming the metal foil layer 4 is: 15-25g/L, and the PH value is 6-9; the plating solution for forming the metal foil layer 4 comprises additives, wherein the additives comprise brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene glycol, the mass fraction of the brightener sodium sulfonate is preferably 0.1-2g/L, the mass fraction of the leveling agent thiourea is preferably 0.01-1g/L, and the mass fraction of the wetting agent polyethylene glycol is preferably 0.1-5 g/L. In the embodiment of the present invention, in order to avoid the warpage of the composite metal foil, in the embodiment, the plating solutions for preparing the carrier layer 1 and the metal foil layer 4 are set to be the same, so that the stress action and the tensile action of the carrier layer 1 and the metal foil layer 4 are the same, the bending degrees of the carrier layer 1 and the metal foil layer 4 are the same, and the warpage of the composite metal foil is avoided.
In an embodiment of the present invention, the method for preparing the composite metal foil further includes the steps of:
and S31, roughening the side of the metal foil layer 4 away from the carrier layer 1.
And S32, forming a second oxidation prevention layer on one surface of the roughened metal foil layer 4, which is far away from the carrier layer 1.
Wherein, the surface of the metal foil layer 4 far away from the carrier layer 1 is roughened by an acid electroplating mode, wherein, the plating solution for acid copper plating can comprise a copper sulfate solution, the copper content of the plating solution for acid copper plating is 10-15g/L, the acid content is 90-100g/L, and the molybdenum content is 600-800 PPM; wherein, the second oxidation prevention layer can be formed in a zinc-nickel alloy plating mode; after the second oxidation preventing layer is formed, plasma cleaning (plasma) may be performed on the second oxidation preventing layer, wherein the voltage during plasma cleaning is preferably 1500-.
The following examples are provided to illustrate the preparation of composite metal foils, in particular as follows:
example 1
S41, forming a carrier layer 1 by adopting an electroplating mode, roughening the carrier layer 1, forming a first anti-oxidation layer on the carrier layer 1, and annealing the carrier layer 1 under a heat treatment condition; wherein the heat treatment conditions are as follows: the heat treatment temperature is 250 ℃, and the heating time is 1 hour; the carrier layer 1 is carrier copper, and the plating solution for forming the carrier layer 1 includes a copper sulfate solution, wherein the copper content of the plating solution for forming the carrier layer 1 is: 20g/L and the PH value is 7; the plating solution for forming the carrier layer 1 further comprises additives, wherein the additives comprise brightener sodium sulfonate, leveling agent thiourea and wetting agent polyethylene glycol, the mass fraction of the brightener sodium sulfonate is 0.8g/L, the mass fraction of the leveling agent thiourea is 0.5g/L, and the mass fraction of the wetting agent polyethylene glycol is 3 g/L. In addition, the carrier layer 1 is roughened by means of acid plating, wherein the plating solution for acid copper plating comprises a copper sulfate solution, the copper content of the plating solution for acid copper plating is 13g/L, the acid content is 95g/L, and the molybdenum content is 700 PPM. Wherein, the first oxidation prevention layer is formed in a zinc-nickel alloy plating mode.
S42, forming a metal adhesive layer 22 on one side of the carrier layer 1 by sputtering; the metal bonding layer 22 is a structure formed by a copper metal layer and a nickel metal layer, the copper metal layer is connected with the carrier layer 1, and the nickel metal layer is connected with the high temperature resistant layer 21;
s43, forming a high temperature resistant layer 21 on the metal bonding layer 22 by sputtering, wherein the metal bonding layer 22 and the high temperature resistant layer 21 form a barrier layer 2; wherein the high temperature resistant layer 21 is a single-layer alloy structure made of tungsten-titanium alloy;
s44, forming a peeling layer 3 on the barrier layer 2 by sputtering; wherein the stripping layer 3 is a graphite layer;
s45, forming a metal foil layer 4 on the stripping layer 3 by adopting an electroplating mode; wherein the metal foil layer 4 is a copper foil; the plating solution used for forming the metal foil layer 4 is the same as that used for the carrier layer 1;
s46, roughening the surface of the metal foil layer 4 away from the carrier layer 1, and forming a second anti-oxidation layer on the roughened surface of the metal foil layer 4 away from the carrier layer 1 by adopting an acid electroplating mode; the plating solution for acid copper plating comprises a copper sulfate solution, wherein the copper content of the plating solution for acid copper plating is 13g/L, the acid content is 95g/L, and the molybdenum content is 700 PPM; wherein, the second oxidation prevention layer can be formed in a zinc-nickel alloy plating mode.
Example 2
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a tungsten-nickel alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 3
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a tungsten-molybdenum alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 4
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a chromium-nickel alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 5
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a zirconium-titanium alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 6
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a titanium-nickel alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 7
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a titanium-molybdenum alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 8
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a titanium-cobalt alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 9
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a nickel-molybdenum alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 10
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a single layer alloy structure made of a molybdenum-cobalt alloy. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 11
The present embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a structure made of a tungsten metal layer and a graphite layer, the tungsten metal layer is connected to the metal bonding layer 22, and the graphite layer is connected to the peeling layer 3. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 12
The present embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a structure made of a chromium metal layer and a graphite layer, the chromium metal layer is connected to the metal bonding layer 22, and the graphite layer is connected to the peeling layer 3. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 13
The present embodiment is different from embodiment 1 in that the high temperature resistant layer 21 has a structure made of a nickel metal layer and a graphite layer, the nickel metal layer is connected to the metal bonding layer 22, and the graphite layer is connected to the peeling layer 3. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 14
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 is a structure made of a tungsten-nickel alloy and a chromium metal layer, the tungsten-nickel alloy is connected to the metal bonding layer 22, and the chromium metal layer is connected to the peeling layer 3. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 15
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 is a structure made of a nickel-molybdenum alloy and a chromium metal layer, the nickel-molybdenum alloy is connected to the metal bonding layer 22, and the chromium metal layer is connected to the peeling layer 3. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 16
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 is a structure made of a molybdenum-cobalt alloy and a chromium metal layer, the molybdenum-cobalt alloy is connected to the metal bonding layer 22, and the chromium metal layer is connected to the peeling layer 3. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 17
This embodiment is different from embodiment 1 in that the high temperature resistant layer 21 is a structure made of a titanium-nickel alloy and a chromium metal layer, the titanium-nickel alloy is connected to the metal bonding layer 22, and the chromium metal layer is connected to the peeling layer 3. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Comparative example 1
This embodiment differs from embodiment 1 in that the barrier layer 2 is not produced after the carrier layer 1 is formed, but a release layer 3 is formed directly on the carrier layer 1. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Comparative example 2
This embodiment is different from embodiment 1 in that the release layer 3 is formed directly on the metal adhesive layer 22 without forming the high temperature resistant layer 21 after forming the metal adhesive layer 22. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Comparative example 3
This embodiment is different from embodiment 1 in that the metal adhesive layer 22 is not formed after the carrier layer 1 is formed, but the high temperature resistant layer 21 is directly formed on the carrier layer 1. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Table 1 shows the peel strength between the carrier layer 1 and the barrier layer 2 and the peel strength between the peel layer 3 and the metal foil layer 4, which were measured as a result of a plurality of tests performed on the composite metal foils prepared in examples 1 to 17 under normal temperature conditions (for example, 16 to 27 ℃, 25 ℃), or a plurality of tests performed under normal temperature conditions after being laminated with the flexible insulating base film at different temperatures (200 ℃ and 340 ℃), respectively.
TABLE 1
Since the carrier layer 1 and the metal foil layer 4 are mutually diffused to a certain degree under the high temperature condition, and the carrier layer 1 and the metal foil layer 4 are bonded to each other to a certain degree, the peel strength between the carrier layer 1 and the barrier layer 2 and the peel strength between the peel layer 3 and the metal foil layer 4 are increased with the increase of the temperature, but as can be seen from table 1, the composite metal foils prepared in examples 1 to 17 have the hundred grid test grades between the carrier layer 1 and the barrier layer 2 at the first three levels regardless of the normal temperature or the high temperature condition, that is, the adhesion between the carrier layer 1 and the barrier layer 2 is relatively large, and the peel strength between the peel layer 3 and the metal foil layer 4 is very small, so that the peel strength between the carrier layer 1 and the barrier layer 2 is always far greater than the peel strength between the peel layer 3 and the metal foil layer 4 Accordingly, when the composite metal foil is used, the carrier layer 1, the barrier layer 2 and the peeling layer 3 can be easily peeled from the metal foil layer 4 at the same time. The interdiffusion of the composite metal foils prepared in comparative examples 1 to 3 occurs more seriously under high temperature conditions, and thus the carrier layer 1 is bonded to the metal foil layer 4 to a greater extent, resulting in inconvenience in simultaneously peeling the carrier layer 1, the barrier layer 2 and the peeling layer 3 from the metal foil layer 4 when the composite metal foils are used.
To sum up, the embodiment of the invention provides a composite metal foil and a preparation method thereof, wherein the composite metal foil comprises a carrier layer 1, a barrier layer 2, a peeling layer 3 and a metal foil layer 4 which are sequentially stacked, the barrier layer 2 comprises a metal bonding layer 22 and a high temperature resistant layer 21 which are stacked, the metal bonding layer 22 is arranged between the carrier layer 1 and the high temperature resistant layer 21, the peeling layer 3 is arranged between the carrier layer 1 and the metal foil layer 4 so as to facilitate peeling of the carrier layer 1, and the barrier layer 2 is arranged between the carrier layer 1 and the metal foil layer 4 so as to prevent the carrier layer 1 and the metal foil layer 4 from being mutually diffused at high temperature to cause bonding, so that the carrier layer 1 and the metal foil layer 4 are easy to peel; in addition, by providing the metal adhesive layer 22 between the carrier layer 1 and the high temperature resistant layer 21, the barrier layer 2 is not easily separated from the carrier layer 1, thereby preventing the occurrence of peeling between the barrier layer 2 and the carrier layer 1.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (15)
1. The preparation method of the composite metal foil is characterized by comprising the following steps of:
forming a carrier layer;
forming a metal adhesive layer on one side of the carrier layer;
forming a high-temperature resistant layer on the metal bonding layer, wherein the metal bonding layer and the high-temperature resistant layer form a barrier layer;
forming a release layer on the barrier layer;
a metal foil layer is formed on the release layer.
2. The method of claim 1, wherein a peel strength between the carrier layer and the barrier layer is greater than a peel strength between the peel layer and the metal foil layer at a temperature of 20-400 ℃.
3. The method of claim 2, wherein the barrier layer has a Pegge test rating of 0 or 1 or 2 and the peel layer has a peel strength of 0.001 to 2N/cm from the metal foil layer.
4. The method of manufacturing a composite metal foil of claim 1, wherein a peel strength between the peel ply and the metal foil layer is greater than or equal to a peel strength between the peel ply and the barrier layer.
5. The method of manufacturing a composite metal foil according to claim 1,
forming a metallic bonding layer on one side of the carrier layer is in particular:
forming a single metal layer on one side of the carrier layer;
wherein the single metal layer formed on one side of the carrier layer is made of a first type of metal that is easily bonded to the carrier layer or a second type of metal that is easily bonded to the high temperature-resistant layer.
6. The method of manufacturing a composite metal foil according to claim 1,
the forming of the metal bonding layer on one side of the carrier layer is specifically:
forming a single layer alloy structure on one side of the carrier layer;
wherein the single-layered alloy structure formed on one side of the carrier layer is made of a first type of metal that is a metal that is easily bonded to the carrier layer and a second type of metal that is a metal that is easily bonded to the high temperature-resistant layer.
7. The method of manufacturing a composite metal foil according to claim 1,
forming a metallic bonding layer on one side of the carrier layer is in particular:
forming a multilayer structure on one side of the carrier layer;
wherein the multi-layered structure formed on one side of the carrier layer includes a single metal layer made of a first type of metal and connected to the carrier layer, and the multi-layered structure formed on one side of the carrier layer further includes a single metal layer made of a second type of metal and connected to the high temperature resistant layer, the first type of metal being a metal easily bonded to the carrier layer, the second type of metal being a metal easily bonded to the high temperature resistant layer.
8. The method of manufacturing a composite metal foil according to claim 1,
forming a metallic bonding layer on one side of the carrier layer is in particular:
forming a multilayer structure on one side of the carrier layer;
wherein the multi-layer structure formed on one side of the carrier layer includes an alloy layer made of a first type metal that is a metal easily bonded to the carrier layer and a single metal layer made of a first type metal or a second type metal that is a metal easily bonded to the high temperature resistant layer, and the alloy layer of the multi-layer structure formed on one side of the carrier layer is made of a first type metal that is a metal easily bonded to the carrier layer and a second type metal that is a metal easily bonded to the high temperature resistant layer.
9. A method of producing a composite metal foil according to any one of claims 5 to 8,
the first metal is copper or zinc, and the second metal is nickel or iron or manganese.
10. A method of producing a composite metal foil according to any one of claims 1 to 8,
the forming of the metal bonding layer on one side of the carrier layer is specifically: forming a metal adhesion layer on one side of the carrier layer by sputtering; and/or the presence of a gas in the gas,
the forming of the high-temperature resistant layer on the metal bonding layer specifically comprises: forming a high temperature resistant layer on the metal bonding layer by sputtering; and/or the presence of a gas in the gas,
the step of forming the stripping layer on the barrier layer is specifically as follows: a release layer is formed on the barrier layer by sputtering.
11. The method of manufacturing a composite metal foil according to any one of claims 1 to 8, further comprising the step of, after forming the carrier layer:
and roughening the carrier layer to obtain the roughened carrier layer.
12. The method of manufacturing a composite metal foil according to claim 11, further comprising the step of, prior to forming the metal adhesive layer on one side of the carrier layer:
and forming a first oxidation preventing layer on the roughened carrier layer.
13. The method of manufacturing a composite metal foil according to any one of claims 1 to 8, further comprising, after forming the carrier layer:
annealing the carrier layer under heat treatment conditions;
wherein the heat treatment conditions are as follows: the heat treatment temperature is 200-300 ℃, and the heating time is 30-300 minutes.
14. The method of manufacturing a composite metal foil according to any one of claims 1 to 8, further comprising, after the forming of the metal foil layer on the peeling layer, the steps of: and roughening the surface of the metal foil layer far away from the carrier layer.
15. The method of manufacturing a composite metal foil according to claim 14, further comprising, after the roughening of the side of the metal foil layer facing away from the carrier layer: and forming a second oxidation prevention layer on one surface of the roughened metal foil layer, which is far away from the carrier layer.
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| CN108699673A (en) * | 2016-02-29 | 2018-10-23 | 三井金属矿业株式会社 | The manufacturing method of copper foil with carrier and centreless supporter and printed circuit board with wiring layer |
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| JP2012096527A (en) * | 2011-07-08 | 2012-05-24 | Fukuda Metal Foil & Powder Co Ltd | Composite metal foil, method for manufacturing the same, and printed wiring board |
| CN105378150A (en) * | 2014-02-14 | 2016-03-02 | 古河电气工业株式会社 | Carrier-equipped ultrathin copper foil, and copper-clad laminate, printed circuit substrate and coreless substrate manufactured using same |
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