WO2015122258A1 - キャリア付き極薄銅箔、並びにこれを用いて作製された銅張積層板、プリント配線基板及びコアレス基板 - Google Patents
キャリア付き極薄銅箔、並びにこれを用いて作製された銅張積層板、プリント配線基板及びコアレス基板 Download PDFInfo
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- carrier
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- copper foil
- ultrathin copper
- plating
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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
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
- C25D1/22—Separating compounds
-
- 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
-
- 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
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- 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
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
- H05K3/4658—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern characterized by laminating a prefabricated metal foil pattern, e.g. by transfer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0147—Carriers and holders
- H05K2203/0156—Temporary polymeric carrier or foil, e.g. for processing or transferring
Definitions
- the present invention relates to an ultra-thin copper foil with a carrier, and a copper-clad laminate, a printed wiring board and a coreless board manufactured using the same.
- coreless substrates In recent years, build-up substrates used for semiconductor packages and the like are being replaced by coreless substrates. With the progress of miniaturization and thinning of electronic devices, circuit board manufacturers are considering the production of multilayer laminates using a thin board called a coreless board. However, since the coreless substrate does not have a core layer that supports the wiring layer, the coreless substrate has poor rigidity, and there are concerns that defects such as bending, warping, and cracking may occur during the formation of the wiring layer.
- the build-up board has fine wiring layers (build-up layers) stacked on both sides of the core layer as a support to form high-density wiring.
- a printed circuit board technology using glass epoxy resin or the like is employed for the core layer, but this core layer is a cause of deteriorating electrical characteristics.
- the large inductance component of the plated through hole that penetrates the core layer is a factor that increases the power supply noise of the semiconductor chip. Therefore, the movement to adopt a coreless substrate without the core layer is rapidly progressing.
- the coreless substrate is manufactured by sequentially performing the steps shown in FIGS.
- the prepreg 4 is bonded to the ultrathin copper foil 2 side of the ultrathin copper foil 3 with a carrier for a support (FIG. 1A).
- the ultrathin copper foil 6 side of the ultrathin copper foil 7 with the wiring forming carrier is attached to the other surface of the prepreg 4 (FIG. 1B).
- the wiring forming carrier foil 5 is peeled off from the bonded ultrathin copper foil 7 with carrier, and the ultrathin copper foil 6 is etched into a predetermined wiring pattern to form fine wiring 8 (FIG. 1C).
- the prepreg 4 is bonded again on the fine wiring 8, thereby completing the first layer of the coreless substrate (FIG. 1 (d)).
- the steps of FIG. 1B to FIG. 1D are repeated until the required number of fine wirings 8 are formed, so that the ultrathin copper foil with carrier 3 serving as the support is formed.
- a coreless substrate 9 is formed on the substrate (FIG. 1E).
- the carrier foil 1 of the ultrathin copper foil 3 with the carrier for support is peeled off (FIG. 1 (f)), and finally, the exposed ultrathin copper foil 2 is removed by etching or the like, whereby the coreless substrate 9 is removed. It can be manufactured (FIG. 1 (g)).
- the peel strength when peeling the carrier foil 1 for support from the ultrathin copper foil 3 with a carrier is the production such as pressing or etching during the formation (lamination) of the layers constituting the coreless substrate.
- Patent Document 1 considers the temperature applied when manufacturing a multi-layer laminate, and makes it easy to form a carrier foil and an ultrathin copper foil even when placed in an environment at a high temperature of 300 ° C. to 400 ° C.
- the main purpose is to make it easy to peel off by defining the metal ratio of the peeling layer consisting of two layers and having two peeling interfaces.
- Patent Document 2 defines the contents of two types of metals A and B constituting the release layer in order to reduce the peel strength and suppress the occurrence of swelling.
- Patent Documents 1 and 2 both peel off the carrier foil from the ultrathin copper foil with a carrier even after pressing under high temperature (300 ° C to 400 ° C) heating that is applied during the production of the laminate.
- a copper plate with a carrier having such a low carrier peel strength is used as a support to produce a laminate, particularly a coreless substrate. Defects that occur between the carrier foil and the ultra-thin copper foil that serve as a support at an unintended stage during the lamination process due to the force applied during the manufacturing process such as pressing or etching during formation (lamination) There was a risk of occurrence.
- the ultrathin copper foil 7 with a carrier similar to the ultrathin copper foil 3 with a carrier to be a support is used also in the formation (lamination) of the layers constituting the coreless substrate.
- the peel strength when the wiring forming carrier foil 5 is peeled off from the carrier forming ultrathin copper foil 7 is as follows. If the carrier strength 1 is not lower than the peel strength at which the support carrier foil 1 is peeled off, there is a concern that the carrier foil 1 used as the support may be unintentionally peeled during the coreless substrate manufacturing process.
- the foil can be used only for the support during the production of the coreless substrate, and there is a problem in that its use is limited.
- the carrier in the manufacture of a coreless substrate, in the layer formation (lamination) process of fine wiring, the carrier after heating load at an applied temperature (mostly in the range of 150 ° C. to 220 ° C., depending on the type of prepreg).
- ultra-thin copper foils There is a need for ultra-thin copper foils.
- An object of the present invention is to provide an ultra-thin copper foil with a carrier that satisfies such requirements, and a copper-clad laminate, a copper printed wiring board, and a coreless board manufactured using the same.
- the ultrathin copper foil with a carrier of the present invention is an ultrathin copper foil with a carrier in which a diffusion preventing layer, a release layer, and an ultrathin copper foil are laminated in this order on the carrier foil, and the unheated carrier
- the carrier foil is peeled off from the attached ultra-thin copper foil, and composition analysis in the depth direction by Auger electron spectroscopy (AES) is performed on the peeled surface of the peeled carrier foil, and Cu, Co, Mo, Ni, Fe , W, Cr, C and O as the denominator, the maximum value of the element ratio of Cu existing up to a depth position within 15 nm from the peeled surface is 9 at. % To 91 at. %. More preferably, it is desirable that Cu is contained at a position within 5 nm from the peeling interface so as to have such an element ratio.
- the ultrathin copper foil with a carrier of the present invention has a peel strength T1 of less than 0.02 kN / m when the carrier foil is peeled off from the ultrathin copper foil with a carrier after heat treatment at 220 ° C. for 1 hour, and
- the peel strength T2 when the carrier foil is peeled off from the ultrathin copper foil with carrier after heat treatment at 350 ° C. for 10 minutes is preferably 0.02 kN / m to 0.1 kN / m, particularly 350 ° C.
- the difference (T2 ⁇ T1) between the peel strength T2 after heat treatment at 10 minutes and the peel strength T1 after heat treatment at 220 ° C. is in the range of 0.015 to 0.080 kN / m. is there.
- the carrier foil is peeled off from an unheated ultrathin copper foil with a carrier, and the composition analysis in the depth direction performed on the peeled surface of the peeled carrier foil is measured by Auger electron spectroscopy (AES).
- AES Auger electron spectroscopy
- the value is 9 at. % To 96 at. %.
- the depth from the peeling surface refers to a value converted by the speed at the time of sputtering SiO 2 with an Ar ion beam.
- the release layer preferably contains Cu and at least one element selected from the group consisting of Mo, W, Fe, Co, Ni and Cr. Further, even when Cu is contained in an organic release layer such as benzotriazole mainly composed of C, N, and O elements, high carrier peel strength after heat treatment can be realized. However, when the carrier foil and the ultra-thin copper foil are peeled off, the structure of such an organic release layer may remain on the surface of the ultra-thin copper foil, resulting in a problem that hinders etching of the ultra-thin copper foil. ,Caution must be taken.
- the diffusion preventing layer is preferably formed of at least one metal or alloy selected from the group of Fe, Ni, Co or alloys containing these elements.
- the carrier foil is preferably copper or a copper alloy.
- the ultra-thin copper foil with a carrier of the present invention is preferably used for producing a copper-clad laminate, a printed wiring board, and a coreless board.
- the ultra-thin copper foil with carrier of the present invention is based on the premise that only one type of ultra-thin copper foil with carrier is used, and the ultra-thin copper foil with carrier used as a support is heat-treated at a high temperature (for example, 350 ° C.).
- the carrier peel strength is increased within the range where mechanical peeling is possible, while the ultrathin copper foil with a carrier used for wiring formation is applied in the fine wiring layer formation (lamination) step.
- the temperature is set so that the carrier peel strength does not increase at a temperature (for example, 150 ° C. to 220 ° C.).
- the ultra-thin copper foil with a carrier of the present invention has an epoch-making feature that can be used in various scenes with one product.
- FIGS. 1A to 1G are schematic views for explaining a general process flow for manufacturing a coreless substrate using an ultrathin copper foil with a carrier.
- FIG. 2 is a cross-sectional view showing one layer structure of an ultrathin copper foil with a carrier according to the present invention.
- FIG. 2 is a typical embodiment of an ultrathin copper foil with a carrier according to the present invention.
- an ultrathin copper foil 10 with a carrier includes a carrier foil 11, a diffusion prevention layer 12 formed on the surface of the carrier foil 11, a release layer 13 formed on the surface of the diffusion prevention layer 12, It consists of an ultrathin copper foil 16 formed on the surface of the release layer 13.
- the release layer 13 may be composed of a single layer, but as shown in FIG. 2, the first release layer 14 formed on the carrier foil 11 side and the second layer formed on the ultrathin copper foil 16 side. It is preferable to comprise the release layer 15. As shown in FIG.
- the release layer 13 when the release layer 13 is composed of two layers of the first release layer 14 and the second release layer 15, when the carrier foil 11 is peeled off from the ultrathin copper foil 10 with a carrier, The release layer 14 remains on the carrier foil 11 side, and the second release layer 15 remains on the ultrathin copper foil 16 side. Even if the release layer 13 has a single-layer configuration consisting of only the first release layer 14, it is possible to achieve the same high carrier peel strength. After the formation of 14 and before the formation of the ultrathin copper foil 16, it is easy to dissolve in a plating solution used in a copper strike plating process that is often performed in general. Therefore, in order to prevent dissolution of the first release layer 14, it is more preferable to form the second release layer 15 on the first release layer 14 so that the first release layer 14 does not directly contact the copper strike plating solution. preferable.
- the carrier foil 11 constituting the ultrathin copper foil 10 with a carrier.
- the carrier foil 11 used for ultrathin copper foil or ultrathin copper alloy foil (hereinafter collectively referred to simply as “ultrathin copper foil” when it is not necessary to distinguish between the two) is easy to handle. From this point, electrolytic copper foil, electrolytic copper alloy foil, rolled copper foil or rolled copper alloy foil is preferable. Further, it is preferable to use a foil having a thickness of 7 ⁇ m to 200 ⁇ m.
- the thickness of the carrier foil 11 is less than 7 ⁇ m, the carrier foil 11 has a low mechanical strength, so that the carrier foil 11 functions as a support during the production of the coreless substrate. As a result, the coreless substrate manufactured may be damaged.
- the thickness of the carrier foil 11 exceeds 200 ⁇ m, the weight per unit coil (coil single weight) increases, which greatly affects the productivity and requires a larger tension on the equipment, which makes the equipment larger. Therefore, it is not preferable. Therefore, the thickness of the carrier foil 11 is preferably 7 ⁇ m to 200 ⁇ m.
- the release layer 13 contains Cu and preferably contains at least one element selected from the group consisting of Mo, W, Fe, Co, Ni and Cr.
- the carrier foil 11 is peeled off from the unheated ultrathin copper foil 10 with a carrier, and the element which exists in the peeling surface at the side of the peeled carrier foil 11 (FIG. 2, an element contained in the first release layer 14 is subjected to composition analysis in the depth direction (depth profile) by Auger electron spectroscopy (AES), and Cu, Co, Mo, Ni, Fe, W, Cr , C and O as the denominator, the maximum value of the element ratio of Cu existing at a depth position within 15 nm from the peeled surface is 9 at. % To 91 at. % Is preferred. More preferably, it is desirable that Cu is contained at a position within 5 nm from the peeling interface so as to have such an element ratio.
- AES Auger electron spectroscopy
- the maximum value of the Cu element ratio is 9 at. When it is less than%, even if the ultrathin copper foil with a carrier is subjected to a heat treatment at a high temperature (for example, 350 ° C.), the carrier peel strength cannot be increased to the expected level. That is, the maximum value of the Cu element ratio is 9 at. When using an ultra-thin copper foil with a carrier of less than 10% as a support for a coreless substrate, unintentional peeling of the carrier foil from the ultra-thin copper foil with a carrier as a support during the layer formation (lamination) process of the coreless substrate There is a concern that this will occur. The maximum value of the Cu element ratio is 96 at.
- the carrier peel strength becomes too high beyond the range that can be mechanically peeled by heat treatment at a high temperature (for example, 350 ° C.). That is, the maximum value of the Cu element ratio is 96 at. %. If the carrier-less ultra-thin copper foil is used as the support for the coreless substrate, the carrier foil is removed from the ultra-thin copper foil with the carrier used as the support after the layer formation (lamination) process of the coreless substrate is completed. At the time of peeling, there is a concern that a large force acts on the coreless substrate, and as a result, the coreless substrate may be broken or warped. Therefore, in the present invention, the maximum value of the element ratio of Cu is 9 at. % To 91 at. %.
- the diffusion prevention layer 12 is formed on the surface of the carrier foil 11 in order to stabilize the peelability of the carrier foil 11 from the ultrathin copper foil 10 with a carrier.
- the diffusion prevention layer 12 By providing the diffusion prevention layer 12 in this manner, Cu contained in the carrier foil 11 is prevented from thermally diffusing into the release layer 13, and the carrier foil 11 and the ultrathin copper foil 16 are mechanically peeled off. Excessive bonding beyond the possible range can be prevented, and the peelability of the release layer 13 can be stabilized.
- the material of the diffusion preventing layer 12 include Fe, Ni, Co, or an alloy formed of these elements.
- the thickness of the diffusion preventing layer 12 is preferably 10 to 200 nm from the viewpoint of preventing Cu diffusion of the carrier foil.
- the method of forming the diffusion preventing layer 12 include a method of forming by electrolytic plating such as Ni plating, Fe plating, and Co plating.
- the first release layer 14 is formed on the diffusion prevention layer 12 formed on the carrier foil 11, and then the second release layer 15 is formed.
- Each of the release layers 14 and 15 can be formed, for example, by electrolytic plating as described later.
- a technique of changing the Cu concentration in the plating bath for forming the first release layer 14 can be mentioned.
- the above-described method is merely an example, and a method of controlling the amount of deposited Cu by controlling the potential at the time of plating of the first release layer 14 may be employed.
- the method for controlling the Cu ratio in the release layer 13 is not particularly limited, and various methods can be employed.
- the thickness of the release layer 13 is preferably in the range of about 5 to 15 nm in order to realize the peeling between the carrier foil and the ultrathin copper foil and the carrier peel strength defined in the present invention. The reason for this is that if the thickness of the release layer 13 is too thin than the above range, the ultrathin copper foil may not be peeled from the carrier foil, whereas if it is too thick, the carrier peel strength will be low. This is because it may be too much.
- the composition of the release layer 13 preferably includes, for example, Cu, and further includes at least one element selected from the group of Mo, W, Fe, Co, Ni, and Cr.
- Mo, W, Fe, Co, Ni, and Cr For example, Co—Mo—Cu alloy plating Fe—Mo—Cu alloy plating, Ni—Mo—Cu alloy plating, Ni—Cu alloy plating, Cr—Cu alloy plating and the like.
- the ultrathin copper foil 16 is formed by electrolytic plating using a copper sulfate bath, a copper pyrophosphate bath, a copper cyanide bath, or the like on the release layer 13 or the second release layer 15 in FIG.
- the second release layer 15 in the plating solution in the electroplating step of forming an ultrathin copper foil 16 by an element contained in the second release layer 15 is used. It is assumed that damage such as dissolution occurs at the dipping time, current value, plating solution draining of plating finish, washing with water, and plating solution pH immediately after metal plating. Because of the occurrence of such damage, be careful about the plating bath composition, plating conditions, etc. in the electrolytic plating process for forming an ultrathin copper foil in relation to the elements constituting the second release layer 15. Must be selected.
- the ultrathin copper foil 16 it is more preferable to perform strike copper plating in a copper pyrophosphate bath or the like before forming the ultrathin copper foil 16 on the release layer 13 (second release layer 15 in FIG. 2). .
- a dense underlying Cu plating layer (not shown) having good adhesion can be formed on the release layer 13. That is, by applying copper plating on the underlying Cu plating layer, a uniform ultrathin copper foil 16 can be formed on the release layer 13, and the number of pinholes generated in the ultrathin copper foil 16 is drastically reduced. The occurrence of blisters resulting from poor adhesion can be prevented.
- the thickness of the underlying Cu plating layer deposited by the strike plating is preferably 0.01 ⁇ m to 0.5 ⁇ m from the viewpoint of making the thickness so as not to impair the peelability of the release layer 13.
- the conditions vary depending on the type of plating bath, but the current density is preferably 0.1 A / dm 2 to 20 A / dm 2 , and the plating time is preferably 0.1 seconds or more.
- the thermal history during pressure heating applied in the coreless substrate layer forming (lamination) step varies depending on the type of prepreg, but is usually within a range of 150 ° C. to 220 ° C. It's about time.
- the peel strength when the carrier foil 11 is peeled off from the ultrathin copper foil 10 with the carrier is when the coreless substrate layer is formed (laminated) when the ultrathin copper foil 10 with the carrier is used as a support. Does not peel off with the force of peeling the carrier foil from the ultrathin copper foil with carrier for wiring formation, and mechanically peels off after the coreless substrate layer forming (lamination) step It is necessary to be within a possible range. Specifically, the preferred range is 0.02 kN / m to 0.1 kN / m.
- the ultrathin copper foil with a carrier of the present invention has a peel strength T1 of less than 0.02 kN / m when the carrier foil is peeled off from the ultrathin copper foil with a carrier after heat treatment at 220 ° C. for 1 hour.
- the peel strength T2 when the carrier foil is peeled off from the ultrathin copper foil with carrier after heat treatment at 350 ° C. for 10 minutes is preferably 0.02 kN / m to 0.1 kN / m.
- the peel strength T1 after heat treatment at 220 ° C. for 1 hour is less than 0.02 kN / m
- the work of peeling the carrier foil from the ultrathin copper foil with a carrier for wiring formation is facilitated.
- the peel strength T2 after heat treatment at 350 ° C. for 10 minutes is less than 0.02 kN / m
- the carrier foil is changed from an ultrathin copper foil with a carrier for wiring formation in a coreless substrate layer formation (lamination) step. Since the carrier foil may be unintentionally peeled off from the ultrathin copper foil with a carrier used as a support when peeling the film, it is not preferable.
- the difference (T2 ⁇ T1) between the peel strength T2 after heat treatment at 350 ° C. for 10 minutes and the peel strength T1 after heat treatment at 220 ° C. for 1 hour is 0.015 to 0.080 kN. More preferably, the range is / m.
- an ultrathin copper foil with a carrier for wiring formation in a coreless substrate layer formation (lamination) step After peeling the carrier foil from the coreless substrate layer, the carrier foil is further prevented from unintentionally peeling from the ultra-thin copper foil with carrier used as a support.
- the carrier foil can be mechanically peeled from the ultrathin copper foil with a carrier used as a support.
- the release layer 13 of the present invention includes the first release layer 14 and the second release layer 15, and further the outermost layer of the first release layer 14 (ie, the boundary between the first release layer 14 and the second release layer 15). It is preferable that a metal oxide layer is formed on the portion. This oxide layer is easily broken mechanically and is considered to be a peeling interface. A metal oxide can be formed on the outermost layer by adjusting the plating conditions when forming the first release layer 14. When heat treatment is performed at a high temperature (for example, 350 ° C.), Cu present in the first release layer 14 diffuses into the above-described oxide layer, so that a clear oxide layer disappears. It is considered that high carrier peel strength is realized by the second release layer 15 being closely bonded via the diffused Cu.
- a high temperature for example, 350 ° C.
- the depth is within 15 nm (more preferably within 5 nm) from the outermost layer (or release surface) of the first release layer 14.
- Cu, Co, Mo, Ni, Fe, W, Cr, C, and O are used as denominators up to a position, Cu is present up to a depth position within 15 nm (more preferably within 5 nm) from the peeled surface.
- the maximum value of the element ratio is 9 at. % To 91 at. % Is preferable.
- the release layer 13 is a single layer consisting of only the first release layer 14, a high carrier peel strength is caused by the same phenomenon.
- the configuration in which the release layer 13 is only the first release layer 14 may cause the first release layer 14 to be dissolved and the ultrathin copper foil 16 to be completely peeled off depending on the type of plating solution used in the strike plating process of the next step. Since it arises, it is preferable to form the structure of the peeling layer 13 from the 1st peeling layer 14 and the 2nd peeling layer 15 which protects it.
- Examples 1 to 6 A copper foil (thickness: 18 ⁇ m) having a surface roughness Rz of 1.1 ⁇ m on one side is used as a carrier foil 11, Ni plating is performed on the carrier foil 11 under the Ni plating conditions shown below, and a 100 nm thick diffusion is performed.
- the prevention layer 12 was formed.
- Ni plating condition Ni 50.0g-200g / L H 3 BO 3 5.00-100 g / L pH 3.0-5.0 Bath temperature 30-60 ° C Current density 10-40A / dm 2 Plating time 5.00-30.0s
- Co—Mo—Cu alloy plating conditions Mo 1.0 to 20 g / L Co 0.50-15g / L Cu 0.50-10g / L Citric acid 10.0-200g / L pH 4.0-7.0 Bath temperature 20-40 ° C
- the same Co—Mo—Cu alloy plating bath composition as described above was used, soaked for 5.0 s in this Co—Mo—Cu alloy plating bath, and then the same plating solution was used.
- a second release layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 1.5 to 3 nm was formed.
- the ultrathin copper foil 16 was formed to produce an ultrathin copper foil 10 with a carrier.
- Substrate Cu plating condition Copper pyrophosphate 10-50g / L Potassium pyrophosphate 50.0-500g / L pH 8.0-10.0 Bath temperature 30-50 °C Current density 0.5 to 3.0 A / dm 2 Plating time 20.0-100s
- Example 7 A diffusion prevention layer 12 similar to that in Example 1 was formed on the carrier foil 11 similar to that in Example 1. On the carrier foil 11 on which the diffusion prevention layer 12 was formed, a first release layer 14 having a thickness of about 5 nm was formed under the following Fe—Mo—Cu alloy plating conditions.
- Fe-Mo-Cu alloy plating conditions Mo 1.0-20g / L Fe 0.50-15g / L Cu 0.60-10g / L Citric acid 10.0-200g / L pH 4.0-7.0 Bath temperature 20-40 ° C Current density 1.0-10A / dm 2 Plating time 1.0-10s
- the same Fe—Mo—Cu alloy plating bath composition as described above was used and immersed in an Fe—Mo—Cu alloy plating bath for 5.0 s.
- the second release layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed.
- copper strike plating and copper plating are performed on the release layer 15 in the same manner as in Example 1 to form an ultrathin copper foil 16 having a thickness of 3 ⁇ m including the underlying Cu plating, and the ultrathin copper foil 10 with a carrier is formed.
- Example 8 A diffusion prevention layer 12 similar to that in Example 1 was formed on the carrier foil 11 similar to that in Example 1.
- a first release layer 14 having a thickness of about 5 nm was formed on the carrier foil 11 on which the diffusion prevention layer 12 was formed, using the Ni—Mo—Cu alloy plating bath shown below.
- Ni-Mo-Cu alloy plating conditions Mo 1.0-20g / L Ni 0.50-15g / L Cu 0.60-10g / L Citric acid 10.0-200g / L pH 4.0-7.0 Bath temperature 20-40 ° C Current density 1.0-10A / dm 2 Plating time 1.0-10s
- the first release layer 14 After forming the first release layer 14, it was immersed in a Ni—Mo—Cu alloy plating bath for 5.0 s. After dipping in the plating bath, the second release layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Next, copper strike plating and copper plating are performed on the release layer 15 in the same manner as in Example 1 to form an ultrathin copper foil 16 having a thickness of 3 ⁇ m including the underlying Cu plating, and the ultrathin copper foil 10 with a carrier is formed. Produced.
- Example 9 A diffusion prevention layer 12 similar to that in Example 1 was formed on the carrier foil 11 similar to that in Example 1. On the carrier foil 11 on which the diffusion prevention layer 12 was formed, a first release layer 14 having a thickness of about 5 nm was formed under the following Ni—W—Cu alloy plating conditions.
- Ni-W-Cu alloy plating conditions W 1.0 to 20 g / L Ni 0.50-15g / L Cu 0.60-10g / L Citric acid 10.0-200g / L pH 4.0-7.0 Bath temperature 20-40 ° C Current density 1.0-10A / dm 2 Plating time 1.0-10s
- the first release layer 14 After forming the first release layer 14, it was immersed in a Ni—W—Cu alloy plating bath for 5.0 s. After dipping in the plating bath, the second release layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Next, copper strike plating and copper plating are performed on the release layer 15 in the same manner as in Example 1 to form an ultrathin copper foil 16 having a thickness of 3 ⁇ m including the underlying Cu plating, and the ultrathin copper foil 10 with a carrier is formed. Produced.
- Example 10 A diffusion prevention layer 12 similar to that in Example 1 was formed on the carrier foil 11 similar to that in Example 1.
- a first release layer 14 having a thickness of about 5 nm was formed on the carrier foil 11 on which the diffusion prevention layer 12 was formed under the following Cr—Cu alloy plating conditions.
- the first release layer 14 After forming the first release layer 14, it was immersed in a Cr—Cu alloy plating bath for 5.0 s. After dipping in the plating bath, the second release layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Next, copper strike plating and copper plating are performed on the release layer 15 in the same manner as in Example 1 to form an ultrathin copper foil 16 having a thickness of 3 ⁇ m including the underlying Cu plating, and the ultrathin copper foil 10 with a carrier is formed. Produced.
- Example 11 A diffusion prevention layer 12 similar to that in Example 1 was formed on the carrier foil 11 similar to that in Example 1. On the carrier foil 11 on which the diffusion preventing layer 12 was formed, a first release layer 14 having a thickness of about 5 nm was formed under the following Ni—Cu alloy plating conditions.
- Ni-Cu alloy plating condition Ni 0.50-15g / L Cu 0.60-10g / L pH 4.0-6.0 Bath temperature 20-40 ° C Current density 1.0-10A / dm 2 Plating time 1.0-10s
- the first release layer 14 After forming the first release layer 14, it was immersed in a Ni—Cu alloy plating bath for 5.0 s. After dipping in the plating bath, the second release layer 15 having a current density of 0.1 to 0.9 A / dm 2 and a plating time of 5.0 to 30 s and a thickness of about 2 nm was formed. Next, copper strike plating and copper plating are performed on the release layer 15 in the same manner as in Example 1 to form an ultrathin copper foil 16 having a thickness of 3 ⁇ m including the underlying Cu plating, and the ultrathin copper foil 10 with a carrier is formed. Produced.
- Example 1 A diffusion prevention layer 12 similar to that in Example 1 was formed on the carrier foil 11 similar to that in Example 1.
- a Co—Mo alloy plating bath not containing Cu (components other than Cu are the same as those in Examples 1 to 6), the same bath temperature as in Examples 1 to 6,
- a first release layer 14 having a thickness of about 4 nm was formed in terms of current density and plating time.
- the first release layer 14 After the formation of the first release layer 14, it was immersed in a Co—Mo alloy plating bath containing no Cu for 5.0 seconds, and then Using a Co—Mo alloy plating bath not containing Cu, the second release layer 15 having a thickness of about 2 nm was formed under the same plating conditions as in Example 1. Next, copper strike plating and copper plating are performed on the release layer 15 in the same manner as in Example 1 to form an ultrathin copper foil 16 having a thickness of 3 ⁇ m including the underlying Cu plating, thereby producing an ultrathin copper foil 10 with a carrier. did.
- Example 2 A diffusion prevention layer 12 similar to that in Example 1 was formed on the carrier foil 11 similar to that in Example 1.
- a first release layer 14 having a thickness of about 4 nm is formed at the same bath temperature, current density, and plating time as those of 1 to 6, and after the formation of the first release layer 14, a Co—Mo—Cu containing 0.15 g / L of Cu is formed.
- Example 2 Immerse in an alloy plating bath for 5.0 seconds, and then use a Co—Mo—Cu alloy plating bath containing 0.15 g / L of Cu to form a second release layer having a thickness of about 2 nm under the same plating conditions as in Example 1. 15 was formed. Next, copper strike plating and copper plating are performed on the release layer 15 in the same manner as in Example 1 to form an ultrathin copper foil 16 having a thickness of 3 ⁇ m including the underlying Cu plating, and the ultrathin copper foil 10 with a carrier is formed. Produced.
- Example 3 A diffusion prevention layer 12 similar to that in Example 1 was formed on the carrier foil 11 similar to that in Example 1.
- Examples 1 to 6 were carried out using Co—Mo—Cu alloy plating baths having the same composition as in Examples 1 to 6 except that the Cu concentration was set to 20 g / L on the carrier foil 11 on which the diffusion prevention layer 12 was formed.
- a first release layer 14 having a thickness of about 8 nm is formed at the same bath temperature, current density, and plating time as in Example 1, and after the formation of the first release layer 14, a Co—Mo—Cu alloy plating bath containing 20 g / L of Cu is formed.
- a second release layer 15 having a thickness of about 3 nm was formed under the same plating conditions as in Example 1 using a Co—Mo—Cu alloy plating bath containing 20 g / L of Cu.
- copper strike plating and copper plating are performed on the release layer 15 in the same manner as in Example 1 to form an ultrathin copper foil 16 having a thickness of 3 ⁇ m including the underlying Cu plating, thereby producing an ultrathin copper foil 10 with a carrier. did.
- Example 4 A Co-Mo alloy plating bath containing no Cu and containing no diffusion preventing layer on the same carrier foil 11 as in Example 1 (components other than Cu are the same as those in Examples 1 to 6).
- a first release layer 14 having a thickness of about 4 nm is formed at the same bath temperature, current density, and plating time, and after the formation of the first release layer 14, it is placed in a Co-Mo alloy plating bath containing no Cu for 5.0 seconds. Then, a second release layer 15 having a thickness of about 2 nm was formed under the same plating conditions as in Example 1 using a Co—Mo alloy plating bath not containing Cu.
- Example 5 A Co—Mo—Cu alloy plating bath under the same conditions as in Example 1 without forming a diffusion prevention layer on the carrier foil 11 similar to that in Example 1, with the same bath temperature, current density and plating as in Examples 1-6.
- the first release layer 14 having a thickness of about 4 nm was formed over time, and after the formation of the first release layer 14, the same Co—Mo—Cu alloy plating bath composition as described above was used.
- a release layer 15 was formed.
- the carrier foil 11 is peeled off from the ultrathin copper foil 10 with a carrier of each of the produced unheated samples, and the composition analysis in the depth direction (depth profile) of the elements remaining on the peeling surface on the carrier foil 11 side is performed by Auger Electronics. It measured with the spectroscopic analyzer (PHI5400 by ULVAC-PHI). The sputter rate was 15.9 nm / min (Sio 2 conversion), and the size of the measurement area was 1 mm square. Of the measured element ratio profile in the depth direction, it exists up to a depth position within 15 nm from the peeled surface when Cu, Co, Mo, Ni, Fe, W, Cr, C and O are used as the denominator. The maximum value of the element ratio of Cu to be measured was measured. The values are shown in Table 1.
- the produced ultrathin copper foil with each carrier was pressed under a condition of a press pressure of 30 kgf / cm 2 with a heat history of 220 ° C. for 1 hour or 350 ° C. for 10 minutes, and the ultrathin copper foil and the prepreg were bonded together. Thereafter, a circuit having a width of 10 mm was prepared, and the carrier peel strength was peeled off in a 90-degree direction using a tensile tester (manufactured by Toyo Baldwin, UTM-4-100) based on JIS C 6481-1996. .
- the peel strength T1 after heat treatment at 220 ° C. for 1 hour and the peel strength T2 after heat treatment at 350 ° C. for 10 minutes when the carrier foil was peeled from the ultrathin copper foil with carrier were measured. The measurement results are shown in Table 1.
- the Ni plating layer is a diffusion prevention layer.
- the present inventors also said the case where Fe plating layer and Co plating layer are made into a diffusion prevention layer, the above-mentioned The same evaluation was performed, and it was confirmed that the same effect as the Ni plating layer was obtained.
- Comparative Example 1 is a carrier foil obtained by treating the first release layer and the second release layer with a Co—Mo alloy plating bath not containing Cu, and peeling the carrier foil from the ultrathin copper foil with carrier.
- the maximum value of the element ratio of Cu existing at a depth position within 15 nm from the peeled surface is 0 at. Therefore, even after the heat treatment at 350 ° C. for 10 minutes, the high carrier peel strength did not occur. That is, since carrier peel strength does not occur, the carrier foil may be peeled off from the ultrathin copper foil with a carrier used as a support at an unintended stage in the laminating process when manufacturing the coreless substrate.
- the first release layer and the second release layer were treated with a Co—Mo—Cu alloy plating bath, but 15 nm from the release surface of the carrier foil when the carrier foil was peeled from the ultrathin copper foil with carrier.
- the first release layer and the second release layer were treated with a Co—Mo—Cu alloy plating bath, but 15 nm from the release surface of the carrier foil when the carrier foil was peeled from the ultrathin copper foil with a carrier.
- the maximum value of the element ratio of Cu existing up to a depth position within 96.1 at. %, which is larger than the appropriate range of the present invention, has been achieved for high carrier peel strength after heat treatment at 350 ° C. for 10 minutes.
- the carrier peel strength becomes too high and the coreless substrate is damaged such as bent or bent when the carrier foil is peeled off.
- Comparative Example 4 was obtained by treating the first release layer and the second release layer with a Co—Mo alloy plating bath containing no Cu as in Comparative Example 1, but did not form a diffusion prevention layer.
- the maximum value of the element ratio of Cu existing from the peeling surface of the carrier foil to a depth position within 15 nm when the carrier foil is peeled off from the ultrathin copper foil with carrier is that the peeling layer does not contain Cu. Nevertheless, 99.6 at. %, But this is probably due to picking up the copper signal on the carrier foil.
- the carrier peel strength exceeds 0.020 kN / m after pressing at 220 ° C., the carrier peel strength becomes too high, and when the carrier foil is peeled off, damage such as bending or bending occurs in the coreless substrate. Was recognized.
- Comparative Example 5 has a form obtained by removing the diffusion prevention layer from Example 1. Since there was no diffusion prevention layer, the diffusion of Cu from the carrier foil progressed, and the carrier peel strength exceeded 0.020 kN / m after 220 ° C. pressing. Thus, when the carrier peel strength was excessively high, damage such as bending or bending occurred in the coreless substrate when the carrier foil was peeled off.
- the ultra-thin copper foil with carrier of the present invention is based on the premise that only one type of ultra-thin copper foil with carrier is used, and the ultra-thin copper foil with carrier used as a support is heat-treated at a high temperature (for example, 350 ° C.).
- the carrier peel strength is increased within the range where mechanical peeling is possible, while the ultrathin copper foil with a carrier used for wiring formation is applied in the fine wiring layer formation (lamination) step.
- the temperature is set so that the carrier peel strength does not increase at a temperature (for example, 150 ° C. to 220 ° C.).
- the ultra-thin copper foil with a carrier of the present invention has an epoch-making feature that can be used in various scenes with one product.
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Abstract
Description
本発明では、キャリア付き極薄銅箔10からキャリア箔11の剥離性を安定させるために、キャリア箔11の表面に拡散防止層12を形成する。このように拡散防止層12を設けることで、キャリア箔11中に含まれるCuが剥離層13に熱拡散することを防止して、キャリア箔11と極薄銅箔16とが、機械的に剥離できる範囲を超えて過度に接合されるのを防止でき、剥離層13の剥離性を安定化させることができる。拡散防止層12の材質としては、例えばFe、Ni、Coまたはこれらの元素により形成された合金が挙げられる。拡散防止層12の厚さは、10~200nmであることがキャリア箔のCuの拡散を防止する点で好ましい。また、拡散防止層12の形成方法は、例えば、Niめっき、Feめっき、Coめっきなどの電解めっきで形成する方法が挙げられる。
キャリア付き極薄銅箔10の作製工程において、図2で示す実施形態では、キャリア箔11上に形成した拡散防止層12上に、第一剥離層14を形成し、次いで第二剥離層15を形成する。上記各剥離層14、15は、例えば後述するように電解めっきで形成することができる。第一剥離層14中に含まれるCu割合を変化させる手段としては、例えば第一剥離層14を形成するためのめっき浴中のCu濃度を変化させる手法が挙げられる。前述の手法はあくまで一例を示したものであって、第一剥離層14のめっき時における電位を制御することによりCuの析出量を制御する手法を採用してもよい。つまり、本発明では、剥離層13中のCu割合の制御法に関しては、特に限定はせず、種々の手法を採用することができる。剥離層13の厚さは約5~15nmの範囲であることが、キャリア箔と極薄銅箔の剥離を実現し、かつ本発明で規定するキャリアピール強度を実現する点で好ましい。この理由は、剥離層13の厚さが上記範囲よりも薄すぎると、極薄銅箔をキャリア箔から剥離不能になることがある一方、上記範囲よりも厚すぎると、キャリアピール強度が低くなりすぎることがあるからである。また、剥離層13を第一剥離層14と第二剥離層15との2層で構成する場合には、第一剥離層14の厚さと第二剥離層と15の厚さの比は、約2:1~4:1の範囲にすることが好ましい。剥離層13の組成は、例えばCuを含み、さらにMo、W、Fe、Co、Ni及びCrの群から選択される少なくとも一種類の元素を含むことが好ましく、例えば、Co-Mo-Cu合金めっき、Fe-Mo-Cu合金めっき、Ni-Mo-Cu合金めっき、Ni-Cu合金めっき、Cr-Cu合金めっき等が挙げられる。
極薄銅箔16は、硫酸銅浴、ピロリン酸銅浴、シアン化銅浴などを使用し、剥離層13上、図2では第二剥離層15上に電解めっきを行なうことによって形成する。なお、極薄銅箔を製膜するにあたっては、第二剥離層15が、第二剥離層15中に含まれる元素によって、極薄銅箔16を製膜する電解めっき工程の、めっき液中のディップ時間、電流値、めっき仕上げのめっき液切り時、水洗時、及び金属めっき直後のめっき液pHで、溶解等のダメージを受ける場合が想定される。このようなダメージの発生が想定されるため、極薄銅箔を製膜する電解めっき工程におけるめっき浴組成、めっき条件等については、第二剥離層15を構成する元素との関係で注意して選択する必要がある。
片面の表面粗さRzが1.1μmである銅箔(厚さ:18μm)をキャリア箔11とし、キャリア箔11上に、下記に示すNiめっき条件でNiめっき処理を行い、厚さ100nmの拡散防止層12を形成した。
Ni 50.0g~200g/L
H3BO3 5.00~100g/L
pH 3.0~5.0
浴温 30~60℃
電流密度 10~40A/dm2
めっき時間 5.00~30.0s
Mo 1.0~20g/L
Co 0.50~15g/L
Cu 0.50~10g/L
クエン酸 10.0~200g/L
pH 4.0~7.0
浴温 20~40℃
ピロリン酸銅 10~50g/L
ピロリン酸カリウム 50.0~500g/L
pH 8.0~10.0
浴温 30~50℃
電流密度 0.5~3.0A/dm2
めっき時間 20.0~100s
Cu 10~100g/L
H2SO4 30~200g/L
Cl 10~50ppm
浴温 30~70℃
電流密度 10~50A/dm2
めっき時間 20.0~100.0s
実施例1と同様のキャリア箔11に、実施例1と同様の拡散防止層12を形成した。拡散防止層12を形成したキャリア箔11上に、下記に示すFe-Mo-Cu合金めっき条件で厚さ約5nmの第一剥離層14を形成した。
Mo 1.0~20g/L
Fe 0.50~15g/L
Cu 0.60~10g/L
クエン酸 10.0~200g/L
pH 4.0~7.0
浴温 20~40℃
電流密度 1.0~10A/dm2
めっき時間 1.0~10s
実施例1と同様のキャリア箔11に、実施例1と同様の拡散防止層12を形成した。拡散防止層12を形成したキャリア箔11上に、下記に示すNi-Mo-Cu合金めっき浴を用い、厚さ約5nmの第一剥離層14を形成した。
Mo 1.0~20g/L
Ni 0.50~15g/L
Cu 0.60~10g/L
クエン酸 10.0~200g/L
pH 4.0~7.0
浴温 20~40℃
電流密度 1.0~10A/dm2
めっき時間 1.0~10s
実施例1と同様のキャリア箔11に、実施例1と同様の拡散防止層12を形成した。拡散防止層12を形成したキャリア箔11上に、下記に示すNi-W-Cu合金めっき条件で、厚さ約5nmの第一剥離層14を形成した。
W 1.0~20g/L
Ni 0.50~15g/L
Cu 0.60~10g/L
クエン酸 10.0~200g/L
pH 4.0~7.0
浴温 20~40℃
電流密度 1.0~10A/dm2
めっき時間 1.0~10s
実施例1と同様のキャリア箔11に、実施例1と同様の拡散防止層12を形成した。拡散防止層12を形成したキャリア箔11上に、下記に示すCr-Cu合金めっき条件で、厚さ約5nmの第一剥離層14を形成した。
Cr 1.0~20g/L
Cu 0.60~10g/L
pH 3.5~5.0
浴温 20~30℃
電流密度 1.0~10A/dm2
めっき時間 1.0~10s
実施例1と同様のキャリア箔11に、実施例1と同様の拡散防止層12を形成した。拡散防止層12を形成したキャリア箔11上に、下記に示すNi-Cu合金めっき条件で、厚さ約5nmの第一剥離層14を形成した。
Ni 0.50~15g/L
Cu 0.60~10g/L
pH 4.0~6.0
浴温 20~40℃
電流密度 1.0~10A/dm2
めっき時間 1.0~10s
実施例1と同様のキャリア箔11に、実施例1と同様の拡散防止層12を形成した。拡散防止層12を形成したキャリア箔11上に、Cuを含まないCo-Mo(Cu以外の成分は実施例1~6と同じ)合金めっき浴で、実施例1~6と同様の浴温、電流密度、めっき時間で厚さ約4nmの第一剥離層14を形成し、第一剥離層14の形成後、Cuを含まないCo-Mo合金めっき浴中に5.0秒間浸漬し、その後、Cuを含まないCo-Mo合金めっき浴を用い、実施例1と同様のめっき条件で厚さ約2nmの第二剥離層15を形成した。
次いでこの剥離層15上に実施例1と同様に銅ストライクめっきと銅めっきを行い、下地Cuめっきを含めて厚さ3μmの極薄銅箔16を形成してキャリア付き極薄銅箔10を作製した。
実施例1と同様のキャリア箔11に、実施例1と同様の拡散防止層12を形成した。拡散防止層12を形成したキャリア箔11上に、Cu濃度を0.15g/Lとし、それ以外は実施例1~6と同様の組成のCo-Mo-Cu合金めっき浴を用いて実施例1~6と同様の浴温、電流密度、めっき時間で厚さ約4nmの第一剥離層14を形成し、第一剥離層14の形成後、Cuを0.15g/L含むCo-Mo-Cu合金めっき浴に5.0秒間浸漬し、その後、Cuを0.15g/L含むCo-Mo-Cu合金 めっき浴を用い、実施例1と同様のめっき条件で厚さ約2nmの第二剥離層15を形成した。
次いでこの剥離層15上に、実施例1と同様に銅ストライクめっきと銅めっきを行い、下地Cuめっきを含めて厚さ3μmの極薄銅箔16を形成してキャリア付き極薄銅箔10を作製した。
実施例1と同様のキャリア箔11に、実施例1と同様の拡散防止層12を形成した。拡散防止層12を形成したキャリア箔11上に、Cu濃度を20g/Lとし、それ以外は実施例1~6と同様の組成のCo-Mo-Cu合金めっき浴を用いて実施例1~6と同様の浴温、電流密度、めっき時間で厚さ約8nmの第一剥離層14を形成し、第一剥離層14の形成後、Cuを20g/L含むCo-Mo-Cu合金めっき浴に5.0秒間浸漬し、その後、Cuを20g/L含むCo-Mo-Cu合金めっき浴を用い、実施例1と同様のめっき条件で厚さ約3nmの第二剥離層15を形成した。次いでこの剥離層15上に実施例1と同様に銅ストライクめっきと銅めっきを行い、下地Cuめっきを含めて厚さ3μmの極薄銅箔16を形成してキャリア付き極薄銅箔10を作製した。
実施例1と同様のキャリア箔11に拡散防止層を形成しないで、Cuを含まないCo-Mo(Cu以外の成分は実施例1~6と同じ)合金めっき浴で、実施例1~6と同様の浴温、電流密度、めっき時間で厚さ約4nmの第一剥離層14を形成し、第一剥離層14の形成後、Cuを含まないCo-Mo合金めっき浴中に5.0秒間浸漬し、その後、Cuを含まないCo-Mo合金めっき浴を用い、実施例1と同様のめっき条件で厚さ約2nmの第二剥離層15を形成した。
次いでこの剥離層15上に実施例1と同様に銅ストライクめっきと銅めっきを行い、下地Cuめっきを含めて厚さ3μmの極薄銅箔16を形成してキャリア付き極薄銅箔10を作製した。
実施例1と同様のキャリア箔11に拡散防止層を形成しないで、実施例1と同条件のCo-Mo-Cu合金めっき浴で、実施例1~6と同様の浴温、電流密度、めっき時間で厚さ約4nmの第一剥離層14を形成し、第一剥離層14の形成後、上記と同様のCo-Mo-Cu合金めっき浴組成を用い、このCo-Mo-Cu合金めっき浴中に5.0s浸漬し、その後同一のめっき液を用い、電流密度0.1~0.9A/dm2で、めっき時間を5.0~30sで厚さ約1.5~3nmの第二剥離層15を形成した。
次いでこの剥離層15上に実施例1と同様に銅ストライクめっきと銅めっきを行い、下地Cuめっきを含めて厚さ3μmの極薄銅箔16を形成してキャリア付き極薄銅箔10を作製した。
実施例1~11は、キャリア付き極薄銅箔からキャリア箔を引き剥がした際に、キャリア箔側の剥離面から15nm以内の深さに存在するCuの元素割合の最大値が、9.6~91.0at.%となった。また、220℃で1時間の熱処理後では、いずれも0.002~0.015kN/mの範囲にあって、0.02kN/m未満の低キャリアピール強度を示した。一方、350℃で10分間の熱処理後では、いずれも0.020~0.091kN/mの範囲にあって、0.02~0.1kN/mの範囲内の高キャリアピール強度を示した。前述した測定結果から明らかなとおり、熱処理条件の違いによって微細配線形成用途及びコアレス基板製造時の支持体用途のどちらにも適するキャリアピール強度が実現されている。なお、上記実施例は、いずれもNiめっき層を拡散防止層とした場合である。なお、Feめっき層やCoめっき層を拡散防止層とした場合についての実施例は示していないが、本発明者らは、Feめっき層やCoめっき層を拡散防止層とした場合についても、上記と同様の評価を行い、Niめっき層と同様の効果が得られることを確認した。
2 極薄銅箔
3 支持体用キャリア付き極薄銅箔
4 プリプレグ
5 キャリア箔
6 極薄銅箔
7 配線形成用キャリア付き極薄銅箔
8 微細配線
9 コアレス基板
10 キャリア付き極薄銅箔
11 キャリア箔
12 拡散防止層
13 剥離層
14 第一剥離層
15 第二剥離層
16 極薄銅箔
Claims (8)
- キャリア箔上に、拡散防止層、剥離層および極薄銅箔がこの順で積層されてなるキャリア付き極薄銅箔であって、未加熱の前記キャリア付き極薄銅箔からキャリア箔を引き剥がし、引き剥がされたキャリア箔の剥離面にて、オージェ電子分光分析法(AES)による深さ方向組成分析を行ない、Cu、Co、Mo、Ni、Fe、W、Cr、C及びOを分母としたときの、前記剥離面から15nm以内の深さ位置までに存在するCuの元素割合の最大値が、9at.%~91at.%であることを特徴とするキャリア付き極薄銅箔。
- 前記剥離層はCuが含まれ、かつMo、W、Fe、Co、Ni及びCrの群から選択される少なくとも一種類の元素を含むことを特徴とする請求項1に記載のキャリア付き極薄銅箔。
- 220℃で1時間熱処理した後のキャリア付き極薄銅箔からキャリア箔を引き剥がしたときの20℃におけるピール強度T1が、0.02kN/m未満であり、かつ350℃で10分間熱処理した後のキャリア付き極薄銅箔からキャリア箔を引き剥がしたときの20℃におけるピール強度T2が、0.02kN/m~0.1kN/mであるキャリア付き極薄銅箔。
- 350℃で10分間熱処理した後の20℃における前記ピール強度T2と、220℃で1時間熱処理した後の20℃における前記ピール強度T1の差(T2-T1)が、0.015~0.080kN/mの範囲である、請求項3に記載のキャリア付き極薄銅箔。
- 前記拡散防止層がFe、Ni、Co、またはこれらの元素により形成された合金で形成されている請求項1~4のいずれか1項に記載のキャリア付き極薄銅箔。
- 請求項1~5のいずれか1項に記載のキャリア付き極薄銅箔を用いて作製された銅張積層板。
- 請求項1~5のいずれか1項に記載のキャリア付き極薄銅箔を用いて作製されたプリント配線基板。
- 請求項1~5のいずれか1項に記載のキャリア付き極薄銅箔を用いて作製されたコアレス基板。
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JP2017095791A (ja) * | 2015-11-28 | 2017-06-01 | キヤノン株式会社 | 貫通配線基板の製造方法及びこれを用いたデバイスの製造方法 |
US20210392749A1 (en) * | 2018-12-10 | 2021-12-16 | Guangzhou Fangbang Electronics Co., Ltd. | Metal foil with carrier and preparation method thereof |
JP2022060296A (ja) * | 2017-03-28 | 2022-04-14 | 昭和電工マテリアルズ株式会社 | コアレス基板用プリプレグ、コアレス基板用プリプレグの製造方法及び製造装置、並びにコアレス基板及びその製造方法 |
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