WO2022224684A1

WO2022224684A1 - Copper member

Info

Publication number: WO2022224684A1
Application number: PCT/JP2022/013649
Authority: WO
Inventors: 直貴小畠; 牧子佐藤
Original assignee: ナミックス株式会社
Priority date: 2021-04-20
Filing date: 2022-03-23
Publication date: 2022-10-27
Also published as: JPWO2022224684A1; TW202311563A; KR20230170899A; CN116670326A

Abstract

The purpose of the present invention is to provide a novel copper member. Provided is a copper member in which a layer containing a copper oxide is formed on at least part of the surface thereof, wherein: the peak S/N ratio corresponding to a substance derived from a resin base material at the surface of the copper member, as obtained by attenuated total reflection absorption Fourier transform infrared spectrometry (FT-IR/ATR method) when the copper member is thermal-pressure-bonded to a resin base material and then separated from the resin base material, is not more than 10 in the wavelength range of 700-4,000 cm^-1; the compositional ratio of the total of metal/(C+O) at the surface of the copper member, as obtained by EDS elemental analysis, is not less than 0.4; and the thickness of a seed layer formed in the resin base material is 0.1-2.0 μm.

Description

copper material

The present invention relates to copper members.

In recent years, the demand for miniaturization of wiring has increased, and a subtractive method (JP 2005-223226; JP 2010-267891) of etching away unnecessary copper parts using a conventional insulating resin with copper foil. The wiring according to Japanese Patent Application Laid-Open No. 2002-176242 cannot satisfy the demand for miniaturization. Therefore, wiring techniques such as the semi-additive (SAP) method and the modified semi-additive (MSAP) method are used. Compared to the subtractive method, the MSAP method enables miniaturization of wiring because the film thickness of the copper to be etched is thin due to the method.

In the MSAP method, an ultra-thin copper foil with a carrier having a copper layer with a thickness of several μm formed on a support via a peeling layer is used, and after forming a seed layer on an insulating resin, a resist is laminated. This is a technique of wiring by removing the resist and seed layer after forming a thick electrolytic copper plating on the patterned portion (see FIG. 1A). Compared to the subtractive method, the copper film thickness to be etched is thinner than the subtractive method, so the wiring can be made finer.

In the SAP method, it is common to form a seed layer made of copper on a resin substrate. Roughened by processing. At this time, the surface roughness (Ra) of the roughened surface of the insulating resin layer is 300 nm or more. Subsequently, a seed layer made of copper is formed on the insulating resin layer by electroless plating or the like. Next, a resist is formed on the portion of the seed layer where the wiring layer is not arranged. Further, a thick copper plating layer is formed by electroplating on the portions where the resist is not formed. Finally, after removing the resist, the exposed seed layer is etched. Thereby, a wiring pattern composed of the seed layer and the metal plating layer is formed on the resin substrate.

An object of the present invention is to provide a novel copper member.

[1] A copper member having a layer containing copper oxide formed on at least part of its surface,
When the copper member is peeled off from the resin base material after being thermocompression bonded to the resin base material,
The S/N ratio of the peak corresponding to the substance derived from the resin base material on the surface of the copper member obtained by attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR/ATR method) is in the wavelength range of 700- 10 or less at 4000 cm ⁻¹ ,
The composition ratio of the sum of the metals on the surface of the resin base material/(C+O) obtained by EDS elemental analysis is 0.4 or more,
A copper member, wherein a seed layer formed on the resin base material has a thickness of 0.1 μm or more and 2.0 μm or less.
[2] The copper member according to [1], wherein the peak S/N ratio is 7 or less.
[3] A copper member having a layer containing copper oxide formed on at least a part of the surface of the copper member, wherein the copper member is thermally compressed to a resin base material and then peeled off from the resin base material. ,
By Survey spectrum analysis of X-ray photoelectron spectroscopy (XPS), metal atoms contained in the layer containing copper oxide are detected from the surface of the resin base material from which the copper member is peeled off,
The composition ratio of the sum of the metals on the surface of the resin base material/(C+O) obtained by EDS elemental analysis is 0.4 or more,
A copper member, wherein a seed layer formed on the resin base material has a thickness of 0.1 μm or more and 2.0 μm or less.
copper material.
[4] The copper member according to item [3], wherein the total intensity of the main peaks of the metal elements detected from the surface of the resin base material from which the copper member has been peeled off is greater than the C1s peak intensity.
[5] [Total surface atomic composition percentage (atom%) of metal elements]/[C1s surface atomic composition percentage calculated from XPS measurement results on the surface of the resin base material from which the copper member was peeled off (atom%)]
is 0.010 or more, the copper member according to item [4].
[6] The copper member according to [4], wherein the total surface atomic composition percentage of Cu2p3 and Ni2p3 detected by the Survey spectrum analysis is 1.5 atom % or more.
[7] The copper member according to [4], wherein the surface atomic composition percentage of Cu2p3 detected by the Survey spectrum analysis is 1.0 atom % or more.
[8] The surface on which the layer containing the copper oxide is formed has an Ra of 0.04 μm or more, and the ratio of the Ra of the surface of the copper member peeled off from the resin base material to the Ra is 100. %, the copper member according to any one of [1] to [7].
[9] of [1] to [8], wherein the ratio of the surface area of the copper member peeled off from the resin substrate to the surface area of the surface on which the layer containing the copper oxide is formed is less than 100%. The copper member according to any one of the items.
[10] The color difference (ΔE ^* ab) between the surface on which the layer containing copper oxide is formed and the surface of the copper member peeled off from the resin substrate is 15 or more, [1] to [9] The copper member according to any one of .
[11] The resin base material is polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), or thermoplastic polyimide (TPI). ), containing at least one insulating resin selected from the group consisting of fluororesin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide and cyanate resin, [1]- The copper member according to any one of [10].
[12] The copper member is thermocompression bonded to the resin substrate under the conditions of a temperature of 50° C. to 400° C., a pressure of 0 to 20 MPa, and a time of 1 minute to 5 hours, [1] to [11] ] The copper member as described in any one of ].
[13] The copper member according to any one of [1] to [12], wherein the layer containing copper oxide contains a metal other than copper.
[14] The copper member according to item [13], wherein the metal other than copper is Ni.
[15] A method for selecting a copper member having a layer containing copper oxide formed on at least part of the surface thereof, comprising:
a step of peeling off the copper member from the resin base material after thermocompression bonding to the resin base material;
a step of analyzing the surface of the copper member peeled off from the resin base material by attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR/ATR method);
performing EDS elemental analysis on the surface of the resin base material from which the copper member has been removed; measuring the thickness of a seed layer formed on the resin base material from which the copper member has been removed;
The S/N ratio of the peak corresponding to the substance derived from the resin base material on the surface of the copper member obtained by the FT-IR/ATR method is 10 or less in the wavelength range of 700-4000 cm ^-1 ,
The composition ratio of the sum of the metals on the surface of the copper member/(C+O) obtained by the EDS elemental analysis is 0.4 or more,
a step of selecting a copper member having a thickness of the seed layer of 0.1 μm or more and 2.0 μm or less;
Selection method including.
[16] A method for selecting a copper member having a layer containing copper oxide formed on at least a part of the surface, comprising:
a step of peeling off the copper member from the resin base material after thermocompression bonding to the resin base material;
a step of performing Survey spectrum analysis of X-ray photoelectron spectroscopy (XPS) on the surface of the copper member peeled off from the resin base;
performing EDS elemental analysis on the surface of the resin base material from which the copper member has been removed; measuring the thickness of a seed layer formed on the resin base material from which the copper member has been removed;
metal atoms contained in the layer containing the copper oxide are detected from the surface of the resin base material from which the copper member has been peeled off;
The composition ratio of the sum of the metals on the surface of the copper member/(C+O) obtained by the EDS elemental analysis is 0.4 or more,
The seed layer has a thickness of 0.1 μm or more and 2.0 μm or less.
selecting a copper member;
Selection method including.
[17] partially coating the surface of the copper member with a silane coupling agent or a rust inhibitor;
forming a layer containing the copper oxide by oxidizing the partially coated surface;
The selection method of item [16], further comprising:
[18] The selection method according to item [17], wherein the surface of the copper member is oxidized with an oxidizing agent.
[19] The silane coupling agent is silane, tetraorgano-silane, aminoethyl-aminopropyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea). ) ((l-[3-(Trimethoxysilyl)propyl]urea)), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy) ( vinyl)silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, ethylene-trimethoxysilane, [17] or [18] Selection method described in section.
[20] The rust inhibitor is 1H-tetrazole, 5-methyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-phenyl-1H-tetrazole, 1,2,3-triazole, 1,2,4 -triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 5-amino-1H-benzotriazole, 2-mercaptobenzothiazole, 1,3-dimethyl-5-pyrazolone, pyrrole, 3- methylpyrrole, 2,4-dimethylpyrrole, 2-ethylpyrrole, pyrazole, 3-aminopyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole, thiazole, 2-aminothiazole, 2-methylthiazole, 2- amino-5-methylthiazole, 2-ethylthiazole, benzothiazole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 5-aminoimidazole, 6-aminoimidazole, benzimidazole, 2-(methylthio) The selection method according to item [17] or [18], which is selected from the group consisting of benzimidazoles.
[21] The selection method according to any one of [17] to [20], further comprising forming a layer containing a metal other than copper on the oxidized surface.
[22] The selection method according to item [21], wherein the metal other than copper is Ni.
[23] oxidizing the surface of the copper member;
forming a layer containing the copper oxide by treating the oxidized surface with a dissolving agent;
The selection method of item [16], further comprising:
[24] The selection method according to item [23], wherein the surface of the copper member is oxidized with an oxidizing agent.
[25] The dissolving agent contains Ni chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, potassium chloride, ammonium sulfate, ammonium chloride, nickel ammonium sulfate, ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetic acid tetra sodium, ethylenediamine-N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl)iminodiacetic acid The selection method according to item [23], which is selected from the group consisting of disodium, sodium gluconate, tin(II) chloride, and citric acid.
[26] The selection method according to any one of [23] to [25], further comprising forming a layer containing a metal other than copper on the surface treated with the dissolving agent.
[27] The selection method according to item [26], wherein the metal other than copper is Ni.
[28] A method for manufacturing a copper member according to any one of [1] to [14],
1) a step of partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor; and 2) a step of oxidizing the partially coated surface to form a layer containing the copper oxide;
A method of manufacturing a copper member, comprising:
[29] A method for manufacturing a copper member according to item [13] or [14],
1) a step of partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor; 2) a step of oxidizing the partially coated surface to form a layer containing the copper oxide;
3) forming a layer containing a metal other than copper on the oxidized surface;
A method of manufacturing a copper member, comprising:
[30] A method for manufacturing a copper member according to any one of [1] to [14],
1) forming a layer containing the copper oxide by oxidizing the partially coated surface; and 2) treating the oxidized surface with a dissolving agent. Production method.
[31] A method for manufacturing a copper member according to [13] or [14],
1) forming a layer containing the copper oxide by oxidizing the surface of the copper member;
2) treating the oxidation-treated surface with a dissolving agent; and 3) forming a layer containing a metal other than copper on the surface treated with the dissolving agent;
including
A method for producing a copper member, wherein the dissolving agent contains a component that dissolves the copper oxide.
[32] The dissolving agent is Ni chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, potassium chloride, ammonium sulfate, ammonium chloride, nickel ammonium sulfate, ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetic acid tetra sodium, ethylenediamine-N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, N-(2-hydroxyethyl)iminodiacetic acid The method for producing a copper member according to item [30] or [31], which contains a compound selected from the group consisting of disodium, sodium gluconate, tin(II) chloride, and citric acid.
[33] The method for producing a copper member according to item [29] or [31], wherein the metal other than copper is Ni.

== Cross-reference with related literature ==
This application claims priority based on Japanese Patent Application No. 2021-071460 filed on April 20, 2021, and is incorporated herein by reference to the basic application. .

FIG. 1 is a diagram showing scanning electron microscope observation photographs of a cross section produced by (A) the laminate manufacturing method (B) in one embodiment of the present invention, in comparison with the MSAP method of the prior art. (A-1) and (B-1) represent the MSAP method, and (A-2) and (B-2) represent the method of the present embodiment. FIG. 1B is a schematic diagram of a seed layer, in accordance with one embodiment of the present invention. The gray portion represents the insulating substrate layer, and the black portion represents the portion of the copper member transferred to the insulating substrate layer. When the copper member is peeled off from the insulating base layer, (A) an example of the case where the copper member is peeled off just at the surface of the insulating base layer (B) is separated from the surface of the insulating base layer and the copper member is peeled off. An example of the case where the copper member is peeled off on the inner side of the trunk portion from the convex portion is shown. The two straight lines respectively correspond to the surface of the peeled copper member and the positions of the planes configured to include the bottoms of the recesses formed in the insulating base layer by the protrusions of the copper member. The portion sandwiched between these two straight lines is the seed layer, and the distance between the two straight lines indicated by arrows is the thickness of the seed layer. FIG. 2 is a diagram showing the results of visual observation after the composite copper foils of Examples 1 to 6 and Comparative Examples 2 to 6 were pressure-bonded to a resin substrate and peeled off, and representative photographs of both surfaces. is. The result of visual observation is indicated by 〇 when the surface of the copper foil is transferred to the resin side, and by × when it is not transferred. FIG. 3 shows the results of XPS analysis of the resin substrates of Examples 1-3 and Comparative Examples 1-4. FIG. 4 shows that the composite copper foils of Examples 1 to 3 and Comparative Examples 2 to 4 were thermally crimped to a resin substrate (R5670KJ) and peeled off, and then the surface of the composite copper foil was measured by the FT-IR/ATR method. These are the results of measurements. FIG. 5 shows the results of measuring the surfaces of the composite copper foils of Example 3 and Comparative Example 3 by the FT-IR/ATR method after the composite copper foils of Example 3 and Comparative Example 3 were thermocompression bonded to a resin substrate (R1551GG) and peeled off. be. FIG. 6 shows that the composite copper foils of Examples 4 to 6 and Comparative Examples 5 to 6 were thermocompression bonded to a resin base material (R5680J) and peeled off, and then the surface of the composite copper foil was subjected to the FT-IR/ATR method. This is the result of the measurement. FIG. 7 shows the results of measuring the surfaces of the composite copper foils of Example 3 and Comparative Example 3 by the FT-IR/ATR method after the composite copper foils of Example 3 and Comparative Example 3 were thermally bonded to a resin substrate (NX9255) and then peeled off. be. FIG. 8 shows the composite copper foils of Example 3 and Comparative Example 3 after thermal compression bonding to the resin base material (CT-Z) and peeling, and then the surfaces of the composite copper foils were measured by the FT-IR/ATR method. This is the result. FIG. 9 is a secondary electron image and an EDS image of Cu obtained by analyzing the surface of the resin base material with a field emission scanning electron microscope after the composite copper foil was thermally compressed to and peeled off from the resin base material. FIG. 10 shows the cross section of the seed layer formed on the resin substrate after the composite copper foils of Examples 1, 2 and 3 and Comparative Examples 3 and 7 were thermally compressed and peeled off from the resin substrate. SEM image. FIG. 11 shows SEM images (magnification: 30,000) of cross sections of resins having seed layers of Examples 1, 2, and 3 and Comparative Example 7 that were plated.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not necessarily limited to these. It should be noted that the objects, features, advantages, and ideas of the present invention are apparent to those skilled in the art from the description of the present specification, and those skilled in the art can easily reproduce the present invention from the description of the present specification. can. DETAILED DESCRIPTION OF THE INVENTION The embodiments, specific examples, and the like set forth below are indicative of preferred embodiments of the invention, and are presented by way of illustration or description, without regard to the invention. It is not limited. Based on the description herein, it will be apparent to those skilled in the art that various alterations and modifications can be made within the spirit and scope of the invention disclosed herein.

==Method for manufacturing laminate of insulating substrate layer and copper member==
One embodiment of the disclosure of the present specification is a method for manufacturing a laminate of an insulating base layer and a copper member, comprising a step of bonding an insulating base layer and a copper member having protrusions on the surface; forming a seed layer by peeling off the member to transfer the projections to the surface of the insulating base layer; forming a resist on a predetermined location on the surface of the seed layer; a method of manufacturing comprising the steps of depositing copper by copper plating the areas where the resist is not deposited, removing the resist, and removing the seed layer exposed by the removal of the resist. be. In this specification, the seed layer refers to the surface of the peeled copper member and the surface configured to include the bottom of the recesses formed in the insulating base layer by the protrusions of the copper member. Refers to the layer formed in between (FIG. 1B), so that the recess and the metal from the copper member transferred to the recess are contained within that layer. The bottom of the recess refers to the farthest bottom from the surface of the stripped copper member among the bottoms of the plurality of recesses, and the surface configured to include the bottom of the recess is the surface of the stripped copper member. parallel to the surface.

[1] Step of bonding an insulating base layer and a copper member <copper member>
The surface of the copper member has fine protrusions.
The arithmetic mean roughness (Ra) of the surface of the copper member is preferably 0.03 μm or more, more preferably 0.05 μm or more, and is preferably 0.3 μm or less, more preferably 0.2 μm or less. .

The maximum height roughness (Rz) of the surface of the copper member is preferably 0.2 μm or more, more preferably 1.0 μm or more, and is preferably 2.0 μm or less, more preferably 1.7 μm or less. preferable.

If Ra and Rz are too small, the adhesion to the resin substrate will be insufficient, and if they are too large, fine wiring formability and high frequency characteristics will be inferior.

Here, the arithmetic average roughness (Ra) is Z (x) (that is, the height of the convex portion and the depth of the concave portion) in the contour curve (y = Z (x)) represented by the following formula at the reference length l It represents the average of the absolute values of

The maximum height roughness (Rz) represents the sum of the maximum value of the height Zp of the convex portion and the maximum value of the depth Zv of the concave portion of the contour curve (y=Z(x)) at the reference length l.

　Ra and Rz can be calculated by the method specified in JIS B 0601:2001 (in accordance with the international standard ISO4287-1997).

The average length (RSm) of the surface roughness curve element of the copper member is not particularly limited, but is 1500 nm or less, 1400 nm or less, 1300 nm or less, 1200 nm or less, 1100 nm or less, 1000 nm or less, 900 nm or less, 800 nm or less, 750 nm or less, It is preferably 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 450 nm or less, or 350 nm or less, and preferably 100 nm or more, 200 nm or more, or 300 nm or more. Here, RSm represents the average length of unevenness for one cycle included in the roughness curve at a certain reference length (lr) (that is, the length of the contour curve element: Xs1 to Xsm), It is calculated by the following formula.

Here, 10% of the arithmetic mean roughness (Ra) is defined as the minimum height of the unevenness, and 1% of the reference length (lr) is defined as the minimum length, and the unevenness for one cycle is defined. As an example, RSm can be measured and calculated according to "Method for measuring surface roughness of fine ceramic thin film by atomic force microscope (JIS R 1683:2007)".

A layer containing copper oxide is formed on at least a part of the surface of the copper member. The copper member specifically includes, but is not limited to, copper foils such as electrolytic copper foil, rolled copper foil, and copper foil with a carrier, copper wires, copper plates, and copper lead frames. The copper member contains Cu as a main component, which is part of the structure, but a material made of pure copper with a Cu purity of 99.9% by mass or more is preferable, and is made of tough pitch copper, deoxidized copper, or oxygen-free copper. More preferably, it is made of oxygen-free copper with an oxygen content of 0.001% by mass to 0.0005% by mass.

When the copper member is a copper foil, its thickness is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 50 μm or less.

<Manufacturing method of copper member>
The layer containing copper oxide is formed on the surface of the copper member and contains copper oxide (CuO) and/or cuprous oxide (Cu ₂ O). This layer containing copper oxide can be formed by oxidizing the surface of the copper member. This oxidation treatment roughens the surface of the copper member.

Before this oxidation step, a surface roughening treatment step such as soft etching or etching is not necessary, but may be performed. In addition, before oxidation treatment, degreasing treatment, acid cleaning for uniformizing the surface by removing a natural oxide film, or alkali treatment for preventing acid from being brought into the oxidation process may be performed after acid cleaning. The method of alkali treatment is not particularly limited, but preferably 0.1 to 10 g/L, more preferably 1 to 2 g/L alkaline aqueous solution, such as sodium hydroxide aqueous solution, at 30 to 50 ° C. for 0.5 to 2 minutes. It should be treated to some extent.

The oxidizing agent is not particularly limited, and for example, an aqueous solution of sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, etc. can be used. Various additives (eg, phosphates such as trisodium phosphate dodecahydrate) and surface active molecules may be added to the oxidizing agent. Surface active molecules include porphyrins, porphyrin macrocycles, extended porphyrins, ring contracted porphyrins, linear porphyrin polymers, porphyrin sandwich coordination complexes, porphyrin sequences, silanes, tetraorgano-silanes, aminoethyl-aminopropyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea) ((l-[3-(Trimethoxysilyl)propyl]urea)), (3-aminopropyl)triethoxysilane , ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyl triacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy)(vinyl)silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chloro Examples include triethoxysilane, ethylene-trimethoxysilane, amines and sugars. The oxidation reaction conditions are not particularly limited, but the liquid temperature of the oxidizing chemical is preferably 40 to 95°C, more preferably 45 to 80°C. The reaction time is preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.

For the layer containing copper oxide, the protrusions on the surface of the oxidized copper member may be adjusted using a dissolving agent. The dissolving agent used in this dissolving step is not particularly limited, but is preferably a chelating agent, particularly a biodegradable chelating agent, such as ethylenediaminetetraacetic acid, diethanolglycine, tetrasodium L-glutamic acid diacetate, ethylenediamine-N,N'. -disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, sodium gluconate, etc. I can give an example. The pH of the solution for dissolution is not particularly limited, but it is preferably alkaline, more preferably pH 8 to 10.5, still more preferably pH 9.0 to 10.5, and pH 9.8 to 10.5. 2 is more preferred.

Further, the surface of the layer containing copper oxide may be subjected to reduction treatment with a reducing agent, in which case cuprous oxide may be formed on the surface of the layer containing copper oxide. Examples of the reducing agent used in this reduction step include dimethylamine borane (DMAB), diborane, sodium borohydride, hydrazine and the like.

Pure copper has a specific resistance of 1.7×10 ^-8 (Ωm), while copper oxide has a specific resistance of 1 to 10 (Ωm).
, Cuprous oxide is 1×10 ⁶ to 1×10 ⁷ (Ωm), so the layer containing copper oxide has low conductivity. At most, transmission loss due to the skin effect is less likely to occur when forming a circuit of a printed wiring board or a semiconductor package substrate using the copper member according to the present invention.

The layer containing copper oxide may contain a metal other than copper. The contained metal is not particularly limited, but contains at least one metal selected from the group consisting of Sn, Ag, Zn, Al, Ti, Bi, Cr, Fe, Co, Ni, Pd, Au and Pt. good too. In particular, in order to have acid resistance and heat resistance, it is preferable to contain metals having higher acid resistance and heat resistance than copper, such as Ni, Pd, Au and Pt.

A layer containing a metal other than copper may be formed on the layer containing copper oxide. This layer can be formed on the outermost surface of the copper member by plating. The plating method is not particularly limited. Plating can be performed by electrolytic plating, electroless plating, vacuum deposition, chemical conversion treatment, or the like, but electrolytic plating is preferred because it is preferable to form a uniform and thin plating layer.

In the case of electrolytic plating, nickel plating and nickel alloy plating are preferable. Metals formed by nickel plating and nickel alloy plating include, for example, pure nickel, Ni—Cu alloy, Ni—Cr alloy, Ni—Co alloy, Ni—Zn alloy, Ni—Mn alloy, Ni—Pb alloy, Ni— P alloy etc. are mentioned.

Examples of metal salts used for plating include nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, zinc oxide, zinc chloride, diamminedichloropalladium, iron sulfate, iron chloride, chromic anhydride, chromium chloride, sodium chromium sulfate, copper sulfate, copper pyrophosphate, cobalt sulfate, manganese sulfate, and the like;

In nickel plating, the bath composition is, for example, nickel sulfate (100 g/L or more and 350 g/L or less), nickel sulfamate (100 g/L or more and 600 g/L or less), nickel chloride (0 g/L or more and 300 g/L or less). and mixtures thereof are preferred, but sodium citrate (0 g/L or more and 100 g/L or less) or boric acid (0 g/L or more and 60 g/L or less) may be contained as additives.

When electrolytic plating is applied to the surface of a copper foil that has been oxidized, the copper oxide on the surface is first reduced, and an electric charge is used to turn it into cuprous oxide or pure copper. After that, the metal that forms the metal layer begins to deposit. The amount of charge varies depending on the type of plating solution and the amount of copper oxide. For example, when Ni plating is applied to a copper member, 10 C per area dm ² of the copper member to be electrolytically plated is required to keep the thickness within a preferable range. It is preferable to apply an electric charge of 90C or more, and it is more preferable to apply an electric charge of 20C or more and 65C or less.

Although the amount of metal deposited on the outermost surface of the copper member by plating is not particularly limited, it is preferably 0.8 to 6.0 mg/dm ² . The amount of adhered metal can be calculated by, for example, dissolving in an acidic solution, measuring the amount of metal by ICP analysis, and dividing the amount by the plane visual field area of the structure.

In order to facilitate the breakage of the layer containing copper oxide from the copper member, 1) the surface of the copper member is partially coated with a coating agent such as a silane coupling agent or an antiseptic before the oxidation treatment; Steps such as treating the oxide-containing layer with a dissolving agent may be performed. By partially coating the surface of the copper member with a coating agent such as a silane coupling agent or a preservative, the portion is prevented from being subjected to oxidation treatment, and voids are generated in the layer containing copper oxide, and the copper is removed from the copper member. Layers containing oxides tend to break. Here, the dissolving agent is an agent that dissolves copper oxide, and by treating with the dissolving agent, the copper oxide near the interface between the copper member and the layer containing copper oxide is partially dissolved, The layer containing copper oxide is likely to break from the copper member.

Silane coupling agents are not particularly limited, but silane, tetraorgano-silane, aminoethyl-aminopropyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea ) ((l-[3-(Trimethoxysilyl)propyl]urea)), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy) ( vinyl)silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, and ethylene-trimethoxysilane.

Rust inhibitors are not particularly limited, but 1H-tetrazole, 5-methyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-phenyl-1H-tetrazole, 1,2,3-triazole, 1,2,4 -triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 5-amino-1H-benzotriazole, 2-mercaptobenzothiazole, 1,3-dimethyl-5-pyrazolone, pyrrole, 3- methylpyrrole, 2,4-dimethylpyrrole, 2-ethylpyrrole, pyrazole, 3-aminopyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole, thiazole, 2-aminothiazole, 2-methylthiazole, 2- amino-5-methylthiazole, 2-ethylthiazole, benzothiazole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 5-aminoimidazole, 6-aminoimidazole, benzimidazole, 2-(methylthio) It may be selected from benzimidazoles.

The treatment with a silane coupling agent or antiseptic may be performed at any time before the oxidation treatment, such as degreasing, acid cleaning for uniform treatment by removing the native oxide film, or acid to the oxidation process after acid cleaning. may be carried out with an alkaline treatment to prevent the introduction of
Treatment with a silane coupling agent or preservative partially (e.g., 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% or more and less than 100%), preferably at a concentration of 0.1%, 0.5%, 1% or 2% or more at room temperature for 30 seconds, 1 minute or 2 minutes It is preferable to carry out the above reactions.

The dissolving agent for making it easier to break the layer containing copper oxide from the copper member is not limited to Ni chloride, as long as it contains a component that dissolves copper oxide, and chlorides (potassium chloride, zinc chloride , iron chloride, chromium chloride, etc.), ammonium salts (ammonium citrate, ammonium chloride, ammonium sulfate, nickel ammonium sulfate, etc.), chelating agents (ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetic acid/tetrasodium, ethylenediamine-N, N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, sodium gluconate etc.), tin(II) chloride, and citric acid.

In the case of treatment with Ni chloride, there is no particular limitation, but the copper member on which the layer containing copper oxide is formed is immersed in a Ni chloride solution (concentration of 45 g/L or more) at room temperature or at a temperature higher than room temperature for 5 seconds or more. is preferred. In addition to treatment with Ni chloride alone, treatment may be performed simultaneously with oxidation treatment, or treatment may be performed simultaneously with plating treatment after oxidation treatment. For example, Ni chloride is contained in the plating solution, and a layer containing copper oxide is formed in the plating solution for 5 seconds, 10 seconds, 15 seconds, 20 seconds, 30 seconds, 1 minute, or 2 minutes before plating. The formed copper member may be immersed. The immersion time can be appropriately changed depending on the oxide film thickness.

<Insulating base layer>
The base material of the insulating base material layer should be such that when the surface of the copper member on which the unevenness is formed is bonded to the insulating base material layer, the surface profile including the uneven shape of the copper member is transferred to the resin base material. Although not particularly limited, a resin substrate is preferable. The resin base material is a material containing resin as a main component, but the type of resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin, polyphenylene ether (PPE), Epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), thermoplastic polyimide (TPI), fluororesin, polyetherimide, polyetheretherketone, polycyclo Olefins, bismaleimide resins, low dielectric constant polyimides, cyanate resins, or mixed resins thereof can be exemplified. The resin base material may further contain an inorganic filler or glass fiber. The dielectric constant of the insulating substrate layer used is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.8 or less.

<Lamination>
When the surface of the copper member having the unevenness is attached to the insulating substrate layer, the surface profile including the uneven shape of the copper member is transferred to the resin substrate. Accordingly, recesses that complement the protrusions on the surface of the copper member and protrusions that complement the recesses are formed on the surface of the insulating base layer.

The bonding method is not particularly limited, but thermal press fitting is preferred. In order to bond the resin base material to the surface of the copper member by thermocompression, for example, the resin base material and the copper member may be adhered and laminated, and then heat treated under predetermined conditions. As predetermined conditions (eg, temperature, pressure, time, etc.), conditions recommended by each substrate manufacturer may be used. Predetermined conditions include, for example, the following conditions.

1) When the resin base material contains or consists of an epoxy resin, a copper member is heated to the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 300 ° C. for 1 minute to 5 hours. Crimping is preferred.

for example,
1-1) When the resin substrate is R-1551 (manufactured by Panasonic), heat under a pressure of 1 MPa, reach 100 ° C., and hold at that temperature for 5 to 10 minutes;
After that, it is further heated under a pressure of 3.3 MPa, and after reaching 170 to 180° C., it is held at that temperature for 50 minutes for thermocompression bonding.

1-2) When the resin substrate is R-1410A (manufactured by Panasonic), heat under a pressure of 1 MPa, and after reaching 130 ° C., hold at that temperature for 10 minutes; Then further heat under a pressure of 2.9 MPa. After reaching 200° C., the temperature is maintained for 70 minutes for thermocompression bonding.

1-3) When the resin substrate is EM-285 (manufactured by EMC), heat under a pressure of 0.4 MPa, and after reaching 100° C., increase the pressure to 2.4 to 2.9 MPa and further heat, After reaching 195° C., the temperature is maintained for 50 minutes for thermocompression bonding.

1-4) When the resin substrate is GX13 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), it is heated while being pressurized at 1.0 MPa and held at 180° C. for 60 minutes for thermocompression bonding.

2) When the resin base material contains or consists of a PPE resin, a copper member is attached to the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50° C. to 350° C. for 1 minute to 5 hours. Thermocompression bonding is preferred.　

for example,
2-1) When the resin substrate is R5620 (manufactured by Panasonic), the temperature and pressure are increased to 2.0 to 3.0 MPa after thermocompression bonding while heating to 100 ° C. under a pressure of 0.5 MPa. , 200 to 210° C. for 120 minutes for further thermocompression bonding.

2-2) When the resin base material is R5670 (manufactured by Panasonic), the temperature and pressure are increased to 2.94 MPa and 210° C. after thermocompression bonding while heating to 110° C. under a pressure of 0.49 MPa. It is thermocompression bonded by holding for 120 minutes.

2-3) When the resin base material is R5680 (manufactured by Panasonic), the temperature and pressure are increased to 3.0 to 4.0 MPa after thermocompression bonding while heating to 110 ° C. under a pressure of 0.5 MPa. , and 195° C. for 75 minutes for thermocompression bonding.

2-4) When the resin substrate is N-22 (manufactured by Nelco), heat while pressurizing at 1.6 to 2.3 MPa, hold at 177° C. for 30 minutes, further heat, and heat at 216° C. for 60 minutes. It is thermocompression bonded by holding.

3) When the resin base material contains or is made of PTFE resin, the heat of the copper member is applied to the resin base material by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 400 ° C. for 1 minute to 5 hours. Crimping is preferred.

for example,
3-1) When the resin base material is NX9255 (manufactured by Park Electrochemical), heat to 260°C while applying pressure at 0.69 MPa, and increase the pressure to 1.03 to 1.72 MPa to reach 385°C. and held at 385° C. for 10 minutes for thermocompression bonding.

3-2) When the resin base material is RO3003 (manufactured by Rogers), after 50 minutes (approximately 220° C.) from the start of pressing, a pressure of 2.4 MPa is applied and held at 371° C. for 30 to 60 minutes for thermocompression bonding.

4) When the resin substrate contains or consists of a liquid crystal polymer (LCP), a copper member is formed on the resin substrate by applying a pressure of 0 to 20 MPa at a temperature of 50 ° C. to 400 ° C. for 1 minute to 5 hours. Heat crimping is preferred. For example, when the resin substrate is CT-Z (manufactured by Kuraray), it is heated under a pressure of 0 MPa, held at 260 ° C. for 15 minutes, further heated while being pressurized at 4 MPa, and held at 300 ° C. for 10 minutes. heat press.

[2] Step of peeling off the copper member After the copper member is attached to the insulating base layer, when the copper member is peeled off from the insulating base layer under predetermined conditions, the protrusions on the surface of the copper member are removed from the insulating base layer. to form a seed layer on the surface of the insulating base layer. Therefore, the surface of the insulating base layer becomes flat.

The thickness of the seed layer may be 2.50 μm or less, more preferably 2.00 μm or less, and even more preferably 1.70 μm or less. Moreover, it is preferably 0.01 μm or more, more preferably 0.10 μm or more, and even more preferably 0.36 μm or more. If the thickness is less than 0.01 μm, the plating formability is poor and the adhesion to the insulating substrate is lowered. If it exceeds 2.50 μm, the wiring formability is deteriorated. The method for measuring the thickness of the seed layer is not particularly limited, and for example, the thickness of the seed layer may be measured in the SEM image.

In the method of the present disclosure, the seed layer thus produced is used as it is as part of the circuit. By omitting the step of removing the protrusions on the surface of the copper member transferred to the insulating base layer, the adhesion between the copper and the insulating base layer is improved.

The conditions for peeling off the copper member from the insulating base layer are not particularly limited, but a 90° peeling test (Japanese Industrial Standards (JIS) C5016 "Flexible printed wiring board test method"; corresponding international standards IEC249-1: 1982, IEC326- 2:1990). The method of peeling off the copper member from the insulating base material layer is not particularly limited, but a machine may be used, or a manual operation may be performed.

The metal transferred to the surface of the insulating substrate layer after peeling off the copper member can be analyzed by various methods (e.g., X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), ICP emission spectroscopy). (Inductively Coupled Plasma Emission Spectroscopy, ICP-OES/ICP-AES)). For example, the metal contained in the layer containing copper oxide is transferred to the insulating substrate layer after peeling off the copper member having the layer containing copper oxide on the surface.

XPS is a technique for performing energy analysis by irradiating an object with X-rays and capturing photoelectrons e ⁻ emitted as the object is ionized. By XPS, it is possible to examine the types, abundances, chemical bonding states, etc. of elements present on the surface of the sample or from the surface to a predetermined depth (for example, up to a depth of 6 nm). The diameter of the analysis spot (that is, the diameter of the cross section of the cylindrical portion that can be analyzed so that the cross section is circular) is suitably 1 μm or more and 1 mm or less. Here, the metal atoms contained in the layer containing copper oxide may be detected from the surface of the insulating base material from which the copper member has been peeled off by XPS Survey spectrum analysis.

The metal contained in the convex part of the copper member is insulated so as to fill 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, or 99.9% or more of the concave part of the transferred surface profile. Transfer to the substrate layer is preferred. When the metal fills most of the recesses in the insulating base layer, when the surface of the insulating base layer is measured by XPS, the total peak intensity of the main peaks of the spectrum of metal atoms is higher than the peak intensity of the main peak of the spectrum of C1s. will also grow. The main peak is the peak with the highest intensity among multiple peaks of the metal element. For example, Cu is 2p3 orbital, Sn is 3d5 orbital, Ag is 3d5 orbital, Zn is 2p3 orbital, Al is 2p orbital, Ti is 2p3 orbital, Bi is 4f7 orbital, Cr is 2p3 orbital, Fe is 2p3 orbital, Co is 2p3 The main peak is the 2p3 orbital of Ni, the 3d5 orbital of Pd, the 4f7 orbital of Au, and the 4f7 orbital of Pt. The peak intensity of the spectrum referred to here means the height in the vertical axis direction of the XPS spectrum data.

The ratio of Cu2p3 to the total atoms on the surface of the insulating base layer from which the copper member is peeled off, as measured by XPS, is 1.0 atom% or more, 1.8 atom% or more, 2.8 atom% or more, 3.0 atom% or more, It is preferably 4.0 atom % or more, 5.0 atom % or more, or 6.0 atom %. Alternatively, when the copper member surface after transfer is measured by XPS, the ratio of the surface atomic composition percentage of Cu2p3 / the surface atomic composition percentage of C1s is 0.010 or more, 0.015 or more, 0.020 or more, 0 It is preferably 0.025 or more, 0.030 or more, 0.035 or more, 0.040 or more, 0.045 or more, 0.050 or more, or 0.10 or more.

When the convex portion of the copper member contains a metal other than copper, the total atomic composition percentage of the metal atoms on the surface of the peeled insulating base layer measured by X-ray photoelectron spectroscopy (XPS) is 1.0 atom. % or more, 1.5 atom % or more, 1.8 atom % or more, 2.8 atom % or more, 3.0 atom % or more, 4.0 atom % or more, 5.0 atom % or more, or 6.0 atom %. Alternatively, the value of the ratio of (total atomic composition percentage of metal atoms on the surface of the peeled insulating base layer):(atomic composition percentage of C1s on the surface of the peeled insulating base layer) is 0.010. 0.015 or more, 0.020 or more, 0.025 or more, 0.030 or more, 0.035 or more, 0.040 or more, 0.045 or more, 0.050 or more, or 0.10 or more preferable.

In addition, regarding the elemental composition of the surface of the insulating base material layer from which the copper member was peeled off, measured by EDS, the ratio of Cu should be 1 atom% or more, preferably 4 atom% or more, and 7 atom% or more. It is more preferably 10 atom % or more, further preferably 11.4 atom % or more. As the proportion of Cu increases, the transfer efficiency of the projections of the copper member improves, and the plating formability improves.
Here, the transfer efficiency indicates the rate at which the metal contained in the protrusions formed on the copper member is transferred to the insulating base layer.

In addition, the composition ratio of the sum of the metals on the surface of the insulating base layer from which the copper member has been peeled off/(C+O) measured by EDS may be 0.38 or more, preferably 0.40 or more. , is more preferably 0.42 or more, and more preferably 0.43 or more. The smaller the metal/(C+O) composition ratio, the worse the plating formability. This is because a high proportion of C indicates poor transfer efficiency, and a high proportion of O indicates inhibition of plating adhesion.

The amount of substances derived from the insulating base layer detected from the surface of the copper member peeled off from the insulating base layer is preferably below the detection limit or, if detected, is a small amount. This is because, in that case, when the copper member is peeled off, breakage in the insulating base material layer can be sufficiently suppressed. The method for detecting substances derived from the insulating base layer is not particularly limited, and a method suitable for the target substance may be used. For example, in the case of organic substances, attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR method) ("Infrared and Raman Spectroscopy: Principles and Spectral Interpretation" by Peter Larkin). The FT ^- IR method is an infrared spectroscopic method in which the substance to be measured is irradiated with infrared rays, and the compound is identified and / or quantified using the infrared absorption spectrum. The N ratio is preferably 10 or less and 9 or less, more preferably 8 or less and 7 or less, and preferably no peak derived from the resin substrate is detected.

The ratio of Ra after peeling to Ra before bonding on the surface of the copper member on which the layer having the protrusions is formed is less than 100%, less than 96%, less than 95%, less than 94%, less than 93%, and 92%. preferably less than, less than 91%, less than 90%, less than 80%, less than 70%, less than 65% or less than 60%. A smaller ratio means that the metal forming the layer having protrusions transferred to the insulating base layer.

The ratio of the surface area after peeling to the surface area before bonding of the copper member on which the layer having the convex portion is formed is less than 100%, less than 98%, less than 97%, less than 96%, less than 95%, less than 94%. , less than 93%, less than 92%, less than 91%, less than 90%, less than 80% or less than 75%. A smaller ratio means that the metal forming the layer having protrusions transferred to the insulating base layer. The surface area can be measured using a confocal microscope or an atomic force microscope.

It is preferable that ΔE ^* ab between the surface of the copper member before thermocompression bonding and the surface of the copper member after peeling is 13 or more, 15 or more, 20 or more, 25 or more, 30 or more, or 35 or more. It means that the larger the difference, the more the metal forming the protrusions transferred to the insulating base layer.

In the conventional SAP method, as described above, the adhesiveness between the resin substrate and the seed layer is enhanced by forming irregularities that serve as anchors in the resin. At that time, relatively large unevenness was formed on the surface to ensure adhesion, but this caused copper to precipitate deep from the resin surface layer, so when the seed layer was etched and removed, a small amount of copper remained. tended to A deep etching process was necessary because this trace amount of remaining copper could cause a short circuit between wirings. Furthermore, the effect of increasing adhesion by unevenness forming treatment and electroless copper plating film is that selectivity to resin substrates is high, and sufficient adhesion effect can be obtained only in some cases such as ABF (Ajinomoto Build-Up Film). It is only a resin base material.

In the conventional MSAP method, an ultra-thin copper foil with a carrier is used, but the thickness of the ultra-thin copper foil layer must be 1.5 μm or more from the viewpoint of handling, etc. In addition, roughening treatment of 1 μm or more is performed. ing. By forming the roughened seed layer on the resin, the adhesion between the resin substrate and the seed layer is enhanced. At that time, since it is necessary to remove the copper layer with a thickness of several μm including the ultra-thin copper foil layer and the roughened portion, a deep etching process was required.

However, in recent fine patterns, when a large amount of copper is etched, pattern skipping occurs due to side etching, and the pattern may disappear. Further, since the wiring layer is formed on the roughened surface of the resin substrate, if the unevenness is large, transmission loss of high-frequency signals is likely to occur.

The seed layer obtained by the method of the present disclosure has a smaller surface roughness than the case where the surface is roughened by desmear treatment in the conventional SAP method or the case where the ultra-thin copper foil with a carrier is roughened in the conventional MSAP method. Also, it is possible to avoid problems such as residual copper after etching, pattern skipping due to side etching in fine patterns, and transmission loss of high-frequency signals due to unevenness. In addition, although the surface roughness is small, fine unevenness is densely present, so that the insulating base material and copper are sufficiently adhered to each other.

[3] Step of Forming Resist at Predetermined Locations on the Surface of the Seed Layer After peeling off the copper member, resist is formed at predetermined locations on the surface of the seed layer. The position where the resist is formed is the part where the copper which later becomes the circuit is not laminated.

The resist may contain, for example, a material that is cured or dissolved by exposure to light, and is not particularly limited, but is preferably formed of a dry film resist (DFR), a positive liquid resist, or a negative liquid resist.

DFR preferably contains a binder polymer that contributes to film formability, a monomer that undergoes a photopolymerization reaction upon UV irradiation (for example, an acrylic ester-based or methacrylic ester-based monomer), and a photopolymerization initiator. A dry film having a three-layer structure of cover form/photoresist/carrier film is preferably used for forming the DFR. A DFR, which is a resist, can be formed on the structure by laminating the photoresist on the structure while peeling off the cover film, and then peeling off the carrier film after the lamination.

Liquid resists include novolak resins that are soluble in organic solvents. As for the liquid resist, the resist can be formed by coating the surface of the structure, drying it, and then dissolving or curing the resist by light irradiation.

Although the thickness of the resist is not particularly limited, it is preferably 1 μm to 200 μm.

After forming the seed layer and before forming the resist, the surface of the seed layer may be plated to form a second seed layer. The method of plating treatment is not particularly limited, and may be electrolytic plating or electroless plating. A film may be formed by a plating method. Here, the second seed layer refers to a metal thin film formed by plating. The thickness of the second seed layer is not particularly limited, and may be about 0.02 to 2 μm. .

[4] Copper Lamination Step Next, copper is laminated by copper-plating a region on the surface of the seed layer where the resist is not laminated. This laminated copper later functions as a circuit.
The method of copper plating treatment is not particularly limited, and plating treatment can be performed using a known method.

[5] Resist Removal Step The method of removing the resist is not particularly limited, and known methods such as a method using fuming nitric acid or sulfuric acid-hydrogen peroxide mixture, and a dry ashing method using O ₂ plasma or the like can be used.

[6] Step of Removing Seed Layer The method for removing the seed layer is not particularly limited, and known methods such as quick etching and flash etching using a sulfuric acid-hydrogen peroxide-based etchant can be used.

== How to select copper materials ==
One embodiment of the present invention is a method for selecting a copper member having a layer containing copper oxide formed on at least part of the surface thereof, wherein the copper member is thermally compressed to a resin base material and then pulled from the resin base material. A step of peeling, a step of analyzing the surface of the copper member peeled off from the resin base material by attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR / ATR method), and a resin base material with the copper member peeled off. A step of performing EDS elemental analysis on the surface of the copper member, a step of measuring the thickness of the seed layer formed on the resin base material from which the copper member is peeled off, and a copper member obtained by the FT-IR / ATR method. The S/N ratio of the peak corresponding to the substance derived from the resin substrate on the surface is 10 or less in the wavelength range 700-4000 cm ^-1 , and the total metal on the surface of the copper member obtained by EDS elemental analysis / ( C+O) composition ratio is 0.4 or more, and the thickness of the seed layer is 0.1 μm or more and 2.0 μm or less, selecting a copper member.

Another embodiment of the present invention is a method for selecting a copper member having a layer containing copper oxide formed on at least part of the surface thereof, wherein the copper member is thermally compressed to a resin base material, and then A step of peeling off, a step of performing Survey spectrum analysis of X-ray photoelectron spectroscopy (XPS) on the surface of the copper member peeled off from the resin substrate, and a surface of the resin substrate from which the copper member was peeled off , a step of performing EDS elemental analysis, a step of measuring the thickness of the seed layer formed on the resin base material from which the copper member has been peeled off, and The composition ratio of total metal on the surface of the copper member/(C+O) detected from the surface of the peeled resin base material and obtained by EDS elemental analysis is 0.4 or more, and the thickness of the seed layer is 0.4. selecting a copper member having a thickness of 1 μm or more and 2.0 μm or less.

Each step can be performed according to the details described in the manufacturing method of the laminate. By this selection method, it is possible to select a copper member having good plating and wiring forming properties when a circuit is formed.

[1] Production of composite copper foil Examples 1 to 6 and Comparative Examples 2 to 3 are copper foils (DR-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd. Shiny surface (glossy surface. A surface that is flat when compared.) was used. In Comparative Example 4, a matte surface of a copper foil (FV-WS, thickness: 18 μm) manufactured by Furukawa Electric Co., Ltd. was used as an untreated test piece. In Comparative Examples 5 and 6, the shiny side (glossy side, flat side compared to the opposite side) of Furukawa Electric Co., Ltd. copper foil (DR-WS, thickness: 18 μm) was used. In Comparative Example 7, an ultra-thin copper foil with a carrier (MT18FL, ultra-thin copper foil thickness: 1.5 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. was used as it was. In addition, Comparative Example 1 does not use a composite copper foil as described later.

(1) Pretreatment First, a copper foil was immersed in the solution described below at 25°C for 1 minute. i.e.
In Examples 1 and 2, potassium carbonate 2.5 g / L; KBE-903 (3-aminopropyltriethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.) 1 vol%,
Example 3 contains 2.5 g/L of potassium carbonate; 0.06 g/L of potassium bicarbonate;
Examples 4 to 6 contain 5 g/L of potassium hydroxide,
Comparative Example 2 is a solution of 2.5 g/L of potassium carbonate,
Comparative Example 3 is a solution of potassium carbonate 2.5 g / L; potassium hydrogen carbonate 0.06 g / L; Comparative Example 5 is potassium hydroxide 5 g / L; KBM-603 (N-2-(aminoethyl)-3 -Aminopropyltrimethoxysilane; manufactured by Shin-Etsu Silicone Co., Ltd.) 5 vol%,
Comparative Example 6 contains potassium hydroxide 5 g/L; BTA (benzotriazole) 1 wt%;
was used.

(2) Oxidation Treatment The pretreated copper foil was immersed in an oxidizing agent for oxidation treatment.
In Examples 1 and 2 and Comparative Examples 2, 5 and 6, a solution of 58.3 g/L of sodium chlorite, 20 g/L of potassium hydroxide and 39.1 g/L of potassium carbonate was used as the oxidizing agent.
In Examples 3 to 6, sodium chlorite 45 g/L; potassium hydroxide 12 g/L; Using.
Comparative Example 3 contains sodium chlorite 58.8 g/L as an oxidizing agent; potassium hydroxide 8.8 g/L; potassium carbonate 3 g/L; KBM-403 (3-glycidoxypropyltrimethoxysilane; Shin-Etsu Silicone Co., Ltd.) 2 g/L solution was used.
Examples 1 and 2 and Comparative Examples 5 and 6 were immersed in the oxidizing agent at 73° C. for 6 minutes, and Examples 3 to 6 and Comparative Examples 2 and 3 were immersed in the oxidizing agent at 73° C. for 2 minutes.

(3) Plating Pretreatment After oxidation treatment, Examples 4 to 6 were subjected to plating pretreatment using a dissolving agent as follows.
Example 4 was treated at 45° C. for 10 seconds using a solution of 45 g/L of tin(II) chloride dihydrate and 1 mL/L of hydrochloric acid.
Example 5 was treated at 45° C. for 60 seconds using a solution of 45 g/L of ammonium chloride.
Example 6 was treated at 45° C. for 60 seconds using a 50% citric acid solution of 45 mL/L.

(4) Electroplating treatment After oxidation treatment, in Examples 2 and 3 and Comparative Example 3, the first Ni electroplating solution (240 g/L nickel sulfate; 45 g/L nickel chloride; 20 g/L sodium citrate) was used. electroplating was performed. In Examples 4 to 6, electroplating was performed using a second Ni electroplating solution (240 g/L of nickel sulfate; 20 g/L of sodium citrate) after pretreatment for plating. Example 3 was immersed in the Ni electrolytic plating solution for 1 minute before electrolytic plating. In Example 2, electrolytic plating was performed at 50° C. with a current density of 0.5 A/dm ² ×116 seconds (=58 C/dm ² copper foil area). In Examples 3 to 6 and Comparative Example 3, electrolytic plating was performed at 50° C. with a current density of 0.5 A/dm ² ×45 seconds (=22.5 C/dm ² copper foil area).

For Examples and Comparative Examples, a plurality of test pieces were produced under the same conditions described above. Table 1 summarizes the above conditions.

<2. Crimping and peeling of resin substrate>
(1) Method For the test pieces of Examples 1 to 6 and Comparative Examples 2 to 7, R5670KJ (manufactured by Panasonic), R5680J (manufactured by Panasonic), CT-Z (manufactured by Kuraray), NX9255 (manufactured by Park Electrochemical) as prepregs ), and R1551GG (manufactured by Panasonic), a resin substrate peeling test was performed.

First, a laminate sample was obtained by laminating prepreg on a test piece and thermocompression bonding in a vacuum using a vacuum high pressure press. When the resin base material is R5670KJ (manufactured by Panasonic), the temperature and pressure are increased to 2.94 MPa and 210° C. for 120 minutes after thermocompression bonding while heating to 110° C. under a pressure of 0.49 MPa. It was thermocompression bonded by holding. When the resin base material is R5680J (manufactured by Panasonic), after heat-pressing while heating to 110 ° C. under a pressure of 0.5 MPa, the temperature and pressure are increased, and held for 75 minutes at 3.5 MPa and 195 ° C. It was thermocompression bonded by doing. When the resin substrate is NX9255 (manufactured by Park Electrochemical), it is heated to 260°C while pressurizing at 0.69 MPa, and the pressure is increased to 1.5 MPa and heated to 385°C. It was thermocompression bonded by holding for 1 minute. When the resin substrate is R1551GG (manufactured by Panasonic), it is heated under a pressure of 1 MPa, and after reaching 100 ° C., it is held at that temperature for 10 minutes, and then further heated under a pressure of 3.3 MPa to 180 ° C. After the temperature was reached, the temperature was maintained for 50 minutes for thermocompression bonding. When the resin substrate is CT-Z (manufactured by Kuraray Co., Ltd.), it is heated under a pressure of 0 MPa, held at 260° C. for 15 minutes, further heated while being pressurized at 4 MPa, and held at 300° C. for 10 minutes. crimped. The copper member was peeled off from the resin substrate according to the 90° peeling test (Japanese Industrial Standards (JIS) C5016) for these laminate samples (Fig. 1). Visual observation results are shown in Figure 2-1. Photographs of the surfaces of the resin side and the copper foil side after peeling off are shown in Fig. 2-2 for representative combinations.

From FIG. 2, it can be easily observed that the surface of the copper foil is transferred to the resin side in Examples and Comparative Examples 5 and 6, whereas in Comparative Examples 2 and 4, the surface of the copper foil is on the resin side. had not metastasized to
In order to prove this as a substance, surface analysis was performed as follows.

<3. Surface analysis of resin substrate after peeling off>
Elemental analysis was performed on the surface of the resin base material after peeling off. Specifically, the obtained resin base material was analyzed using Quantera SXM (manufactured by ULVAC-PHI) under the following conditions. As a negative control, an untreated resin base material (R5670KJ; MEGTRON6) was analyzed (Comparative Example 1).
(1) Survey spectrum
First, elements were detected under the following conditions.
X-ray source: monochromatic Al Kα (1486.6 eV)
X-ray beam diameter: 100 μm (25w15kV)
Pass energy: 280 eV, 1 eV step Point analysis: φ100 μm
Accumulated times 8 times

The results are shown in Table 2 and FIG.
In Examples and Comparative Examples 5 and 6, the peak intensity of the Cu2p3 spectrum derived from the transferred copper atoms is greater than the peak intensity of the C1s spectrum derived from the resin base material, whereas in Comparative Examples 1 to 4 The Cu2p3 spectrum peak was not detected or its intensity was lower than that of the C1s spectrum. This indicates that, in the comparative example, almost no copper atoms were transferred to the resin base material, or almost no copper atoms were present in the surface layer of the resin base material detectable by XPS.

In Example 1, since the composite copper foil was not plated, only Cu atoms were transferred and detected on the resin substrate side. In Examples 2 and 3, since Ni plating was performed, Cu atoms and Ni atoms were transferred and detected on the resin side.

In addition, the ratio of C1s was smaller in both Examples and Comparative Examples 5 and 6 than in Comparative Examples 1 to 4. In the examples, it is believed that the proportion of C1s on the surface was relatively decreased due to the transfer of cupric oxide or cuprous oxide.

<4. Measurement of Ra and Surface Area of Composite Copper Foil Before Thermocompression and After Peeling>
(1) Method For the composite copper foil test pieces of Examples 1 to 6 and Comparative Examples 2 to 6, the surface area before thermocompression bonding and after peeling was calculated using a confocal microscope OPTELICS H1200 (manufactured by Lasertec Co., Ltd.). . As measurement conditions, the mode is confocal mode, the scan area is 100 μm × 100 μm, the light source is Blue, and the cutoff value is 1/5.
and The object lens was set to x100, the contact lens was set to x14, the digital zoom was set to x1, and the Z pitch was set to 10 nm.

(2) Results
As shown in Table 3, before thermal compression bonding and after peeling, Ra and surface area decreased in Examples and Comparative Examples 5 and 6, whereas they increased in Comparative Examples 2 and 4. This indicates that all or part of the protrusions of the composite copper foil were transferred to the resin side in the examples, whereas in Comparative Examples 2 to 4, part of the resin was transferred to the composite copper foil. there is

<5. Calculation of ΔE ^* ab of Composite Copper Foil Before Thermocompression and After Peeling>
(1) Method The color difference (L ^* , a ^* , b ^* ) of the copper foil surface of each composite copper foil test piece before thermocompression bonding and after peeling was measured, and from the obtained values, ΔE ^* ab was calculated.
ΔE ^* ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2

(2) Results
As shown in Table 4, before thermocompression bonding and after peeling, ΔE ^* ab was 15 or more in Examples and Comparative Examples 5 and 6, while it was less than 15 in Comparative Examples 2 and 4. This is because in Examples and Comparative Examples 5 and 6, the metal contained in the layer containing copper oxide is transferred to the resin base material, so that the color change of the copper member increases, whereas in Comparative Examples 2 and 4, the color change is large. Since the layer containing copper oxide remains as it is on the copper member, the color change of the copper member becomes small, so the more the metal contained in the layer containing copper oxide transfers, the greater the difference therebetween. In fact, even in the photograph of FIG. 2, after peeling off, the resin side of Example and Comparative Examples 5 and 6 is highly colored, while the resin side of Comparative Examples 2 and 4 remains almost white.

<6. Analysis of Composite Copper Foil Surface after Transfer by Attenuated Total Reflection Absorption Fourier Transform Infrared Spectroscopy (FT-IR/ATR Method)>
(1) Method After thermal compression using R1551GG (epoxy), R5670KJ, R5680J (all PPE), NX9255 (PTFE), or CT-Z (LCP) as the resin substrate, and peeling off Each composite copper foil test piece was analyzed by the FT-IR/ATR method under the following measurement conditions.
Measurement conditions Specrtum 100 made by Parkin Elmer
ATR method Crystal: Germanium Resolution: 4
Number of scans: 4 Pressure (force gauge): 40±5 [N]
Spectral display: Absorbance

(2) Calculation of S/N (signal/noise) ratio After heating and pressurizing only the resin substrate under the same conditions as when thermocompression bonding with the composite copper foil, the resin substrate was measured by FT-IR, and the resin An arbitrary wavelength with no originating peak was chosen in the range of 50 cm ⁻¹ . In this example, 3800-3850 cm ⁻¹ was set as a wavelength without a resin-derived peak.
Furthermore, the wavelength at which the maximum peak was detected was identified in the wavelength range of 700-4000 cm ⁻¹ . When using R1551GG as a resin base material, it is around 1200 cm ^-1 , when using R5670KJ and R5680J, it is around 1190 cm ^-1 , when using NX9255, it is around 1232 cm -1, and when CT ^- Z is used, it is 1741 cm ^-1 . The maximum peak detectable wavelength was taken to be around ¹ (the arrows in FIGS. 4 to 8 indicate the maximum peak detectable wavelength).

Measure the surface of the copper member after the transfer by FT-IR, draw a baseline connecting the poles of both ends of the peak at the maximum peak detection wavelength with a straight line, and measure the difference between the maximum height of the baseline and the peak as the signal value (S ). The S/N ratio was calculated using the noise value (N) as the difference between the maximum and minimum values of the peaks detected at a wavelength of 3800-3850 cm ⁻¹ .

(3) Results Results are shown in FIGS.

As shown in Table 5, in Examples and Comparative Examples 5 and 6, no peak with an S/N ratio of 10 or more corresponding to resin-derived organic substances was detected on the composite copper foil side, but in Comparative Examples 2 and 4, , a peak with an S/N ratio of 10 or more corresponding to the resin-derived organic matter was detected on the composite copper foil side.

This is because in Comparative Examples 2 to 4, the metal on the surface of the composite copper foil hardly transferred, and cohesive failure of the resin occurred when the composite copper foil was peeled off from the resin substrate, and the broken resin was transferred to the surface of the composite copper foil. This is because the peak corresponding to the resin-derived organic matter was detected due to adhesion. On the other hand, in Examples and Comparative Examples 5 and 6, since the metal on the surface of the composite copper foil was transferred to the resin base material, the resin hardly adhered to the composite copper foil after the composite copper foil was peeled off from the resin base material. , peaks with an S/N ratio of 10 or more corresponding to resin-derived organic substances were not detected.

That is, in Comparative Examples 2 to 4, the adhesion strength between the layer containing copper oxide and the copper member is greater than the adhesion strength between the layer containing copper oxide and the resin base material, so the metal on the surface of the composite copper foil does not transfer. Cohesive failure of the resin occurs. On the other hand, in Examples and Comparative Examples 5 and 6, the adhesive strength between the copper oxide-containing layer and the copper member is smaller than the adhesive strength between the copper oxide layer and the resin base material, so the metal on the surface of the composite copper foil transfers. Therefore, there is almost no adhesion of resin.

[2] Analysis of Resin Surface and Seed Layer The composite copper foil prepared in [1] was thermally bonded to the resin substrate and then peeled off from the resin substrate, and the surface and seed layer on the resin substrate side were analyzed. R5670KJ (manufactured by Panasonic) is used as the resin base material, and after thermal compression bonding while heating to 110 ° C. under a pressure of 0.49 MPa, the temperature and pressure are increased, and held at 2.94 MPa and 210 ° C. for 120 minutes. It was thermo-compressed.

<1. Elemental Analysis by EDS (Energy Dispersive X-ray Spectrometer)>
First, elemental analysis was performed using an EDS (energy dispersive X-ray spectroscope) (manufactured by Oxford, trade name: X-Max Extreme) (conditions: acceleration voltage of 10 kV, magnification of 30,000 times). FIG. 9 shows a typical secondary electron image and an EDS elemental mapping image of Cu, and Table 6 (Example) and Table 7 (Comparative Example) show the ratio of each element of C, O, Ni, Cu, and Sn ( atom %), and the value of the ratio (sum of ratios of metal elements/(sum of ratios of C and O)) calculated from these values.

In the examples, the ratio of Cu is 10 atom % or more, and Cu transfers at a high ratio, and (the sum of the ratios of metal elements/(the sum of the ratios of C and O)) is 0.4 or more. , good plating formability. On the other hand, in Comparative Examples 2 and 3, the proportion of Cu was 0.1 atom % or less, and almost no Cu was transferred, resulting in poor plating formability. In Comparative Examples 5 and 6, (the sum of the proportions of the metal elements/(the sum of the proportions of C and O)) is as low as less than 0.4, and these are also poor in plating formability.

Thus, the resin having a seed layer produced using the composite copper foil of the example has good plating formability in terms of surface element composition.

<2. Seed layer thickness>
The thickness of the seed layer was then measured. Specifically, in the cross section of SEM (magnification: 10,000 times), for the layer in which the copper protrusions are embedded in the resin base material, the upper side corresponding to the upper surface of the layer and the lower side corresponding to the lower surface of the layer are in contact with each other. The maximum distance between two parallel straight lines was examined, and the distance was taken as the thickness of the seed layer. FIG. 10 shows a representative SEM image, and Tables 6 and 7 show the thickness measurement results.

In the example, since the seed layer has a thin thickness of 0.36 to 1.70 μm, the wiring formability is good. On the other hand, in Comparative Examples 2 and 3, since the thickness of the seed layer was 0 μm and metal transfer did not occur, almost no plating was formed. In Comparative Example 7, since the seed layer is too thick, it is difficult to miniaturize the circuit, and the wiring formability is also poor as shown in <3> below.

As described above, the resin having a seed layer produced using the composite copper foil of the example has good wiring formability in terms of the thickness of the seed layer.

<3. Plating formability>
(1) The resins having seed layers of Examples 1 to 6 and Comparative Examples 2 to 7 were electroless plated and then plated to form second seed layers.

First, it was pretreated with a 100 mL/L HCl solution at 25°C for 1 minute. After that, it was treated with a 250 mL/L HCl solution containing catalyst OPC-80 Catalyst M (manufactured by Okuno Seiyaku Co., Ltd.) at 30° C. for 5 minutes, washed with water, and then subjected to activation treatment. After washing with water, it was treated with an electroless copper plating solution OPC-700 (manufactured by Okuno Seiyaku Co., Ltd.) at 80° C. for 10 minutes, and then washed with water.

Next, a commercially available photosensitive dry film was attached, exposed through a mask, and developed with 0.8% sodium hydrogen carbonate to form a plating resist. Then, using a commercially available electrolytic copper plating solution, electrolytic copper plating was performed at a current density of 1 A/dm ² at 30° C. for 30 minutes to form an electrolytic copper plating film with a thickness of 15 μm.

Further, after the plating resist was peeled off with 5% potassium hydroxide, the seed layer under the plating resist was dissolved and removed by etching using a mixed solution of sulfuric acid and hydrogen peroxide to obtain a laminated wiring circuit board.
(2) The resin having the seed layer of Example 3 was subjected to electroplating alone to form a second seed layer. Specifically, using a commercially available electrolytic copper plating solution, an electrolytic copper plating film was formed at a current density of 1 A/dm ² at 30°C.

(3) After the copper plating film is formed, Cellotape (registered trademark) (manufactured by Nichiban) is attached, and after removing the Cellotape (registered trademark), an SEM cross-sectional image (30000 times) is analyzed, and plating of 0.1 μm or more is formed. If it was formed, it was evaluated as 〇, and if it was not formed, it was evaluated as ×. FIG. 11 shows SEM cross-sectional images (30000 times) of Examples 1, 2 and 3 and Comparative Example 7. FIG.

<4. Wiring Formability>
For the resin having a seed layer, a commercially available photosensitive dry film is pasted on the formed seed layer, exposed through a mask, and developed with 0.8% sodium bicarbonate to form a plating resist. did.

Then, using a commercially available electrolytic copper plating solution, electrolytic copper plating was performed at a current density of 1 A/dm ² at 30° C. for 30 minutes to form an electrolytic copper plating film with a thickness of 15 μm.

Furthermore, after the plating resist was removed with 5% potassium hydroxide, the seed layer under the plating resist was dissolved and removed by etching using a mixed solution of sulfuric acid and hydrogen peroxide to obtain a laminated wiring circuit board.

From the SEM cross-sectional image of the test piece, the etching factor was calculated using the following formula. The results are shown in Tables 6 and 7.

The smaller the etching factor, the greater the width difference between the upper and lower sides of the trapezoidal wiring, and the trapezoidal shape becomes extreme. If the width of the base is shortened for miniaturization, the width of the upper base cannot be secured, which is not suitable for miniaturization.

As can be seen from Tables 6 and 7, no wiring can be formed in Comparative Examples 2, 3, 5 and 6, and Comparative Example 7 has a low etching factor and poor wiring formability.

Claims

A copper member having a layer containing copper oxide formed on at least part of the surface,
When the copper member is peeled off from the resin base material after being thermocompression bonded to the resin base material,
The S/N ratio of the peak corresponding to the substance derived from the resin base material on the surface of the copper member obtained by attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR/ATR method) is in the wavelength range of 700- 10 or less at 4000 cm −1 ,
The composition ratio of the sum of the metals on the surface of the resin base material/(C+O) obtained by EDS elemental analysis is 0.4 or more,
A copper member, wherein a seed layer formed on the resin base material has a thickness of 0.1 μm or more and 2.0 μm or less.
The copper member according to claim 1, wherein the peak S/N ratio is 7 or less.
A copper member having a layer containing copper oxide formed on at least part of the surface of the copper member,
When the copper member is peeled off from the resin base material after being thermocompression bonded to the resin base material,
By Survey spectrum analysis of X-ray photoelectron spectroscopy (XPS), metal atoms contained in the layer containing copper oxide are detected from the surface of the resin base material from which the copper member is peeled off,
The composition ratio of the sum of the metals on the surface of the resin base material/(C+O) obtained by EDS elemental analysis is 0.4 or more,
A copper member, wherein a seed layer formed on the resin base material has a thickness of 0.1 μm or more and 2.0 μm or less.
copper material.
The copper member according to claim 3, wherein the total intensity of the main peaks of the metal elements detected from the surface of the resin base material from which the copper member has been peeled off is greater than the peak intensity of C1s.
On the surface of the resin base material from which the copper member was peeled off, [sum of surface atomic composition percentages (atom%) of metal elements] / [surface atomic composition percentage (atom%) of C1s calculated from XPS measurement results )]
is 0.010 or more, the copper member according to claim 4.
The copper member according to claim 4, wherein the total surface atomic composition percentage of Cu2p3 and Ni2p3 detected by the Survey spectrum analysis is 1.5 atom% or more.
5. The copper member according to claim 4, wherein the surface atomic composition percentage of Cu2p3 detected by the Survey spectrum analysis is 1.0 atom % or more.
The Ra of the surface on which the layer containing the copper oxide is formed is 0.04 μm or more, and the Ra ratio of the surface of the copper member peeled off from the resin base material to the Ra is less than 100%. A copper member according to any one of claims 1 to 7.
The ratio of the surface area of the copper member peeled off from the resin substrate to the surface area on which the layer containing copper oxide is formed is less than 100%, according to any one of claims 1 to 8 A copper member as described.
10. The color difference (ΔE * ab) between the surface on which the layer containing copper oxide is formed and the surface of the copper member peeled off from the resin substrate is 15 or more. The copper member as described in .
The resin base material includes polyphenylene ether (PPE), epoxy, polyphenylene oxide (PPO), polybenzoxazole (PBO), polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), thermoplastic polyimide (TPI), fluorine Any one of claims 1 to 10, containing at least one insulating resin selected from the group consisting of resin, polyetherimide, polyetheretherketone, polycycloolefin, bismaleimide resin, low dielectric constant polyimide and cyanate resin. The copper member according to claim 1.
12. The copper member is thermocompression bonded to the resin substrate under conditions of a temperature of 50° C. to 400° C., a pressure of 0 to 20 MPa, and a time of 1 minute to 5 hours. The copper member according to the item.
The copper member according to any one of claims 1 to 12, wherein the layer containing copper oxide contains a metal other than copper.
The copper member according to claim 13, wherein the metal other than copper is Ni.
A method for selecting a copper member having a layer containing copper oxide formed on at least a part of the surface thereof, the method comprising the step of thermally compressing the copper member to a resin base material and then peeling the copper member off the resin base material;
a step of analyzing the surface of the copper member peeled off from the resin base material by attenuated total reflection absorption Fourier transform infrared spectroscopy (FT-IR/ATR method);
performing EDS elemental analysis on the surface of the resin base material from which the copper member has been removed; measuring the thickness of a seed layer formed on the resin base material from which the copper member has been removed;
The S/N ratio of the peak corresponding to the substance derived from the resin base material on the surface of the copper member obtained by the FT-IR/ATR method is 10 or less in the wavelength range of 700-4000 cm -1 ,
The composition ratio of the sum of the metals on the surface of the copper member/(C+O) obtained by the EDS elemental analysis is 0.4 or more,
a step of selecting a copper member having a thickness of the seed layer of 0.1 μm or more and 2.0 μm or less;
Selection method including.
A method for selecting a copper member having a layer containing copper oxide formed on at least a part of the surface thereof, the method comprising the step of thermally compressing the copper member to a resin base material and then peeling the copper member off the resin base material;
a step of performing Survey spectrum analysis of X-ray photoelectron spectroscopy (XPS) on the surface of the copper member peeled off from the resin base;
performing EDS elemental analysis on the surface of the resin base material from which the copper member has been removed; measuring the thickness of a seed layer formed on the resin base material from which the copper member has been removed;
metal atoms contained in the layer containing the copper oxide are detected from the surface of the resin base material from which the copper member has been peeled off;
The composition ratio of the sum of the metals on the surface of the copper member/(C+O) obtained by the EDS elemental analysis is 0.4 or more,
The seed layer has a thickness of 0.1 μm or more and 2.0 μm or less.
selecting a copper member;
Selection method including.
a step of partially coating the surface of the copper member with a silane coupling agent or a rust inhibitor;
forming a layer containing the copper oxide by oxidizing the partially coated surface;
17. The method of claim 16, further comprising:
The selection method according to claim 17, wherein the surface of the copper member is oxidized with an oxidizing agent.
The silane coupling agent is silane, tetraorgano-silane, aminoethyl-aminopropyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea) (( l-[3-(Trimethoxysilyl)propyl]urea)), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxysilane), (3-chloropropyl)trimethoxysilane, (3- glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy)(vinyl)silane , chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, ethylene-trimethoxysilane. .
The rust inhibitor is 1H-tetrazole, 5-methyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-phenyl-1H-tetrazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H-benzotriazole, 5-amino-1H-benzotriazole, 2-mercaptobenzothiazole, 1,3-dimethyl-5-pyrazolone, pyrrole, 3-methylpyrrole, 2,4-dimethylpyrrole, 2-ethylpyrrole, pyrazole, 3-aminopyrazole, 4-methylpyrazole, 3-amino-5-hydroxypyrazole, thiazole, 2-aminothiazole, 2-methylthiazole, 2-amino-5 - from methylthiazole, 2-ethylthiazole, benzothiazole, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 5-aminoimidazole, 6-aminoimidazole, benzimidazole, 2-(methylthio)benzimidazole 19. The selection method according to claim 17 or 18, selected from the group consisting of:
The selection method according to any one of claims 17 to 20, further comprising the step of forming a layer containing a metal other than copper on the oxidized surface.
The selection method according to claim 21, wherein the metal other than copper is Ni.
oxidizing the surface of the copper member;
forming a layer containing the copper oxide by treating the oxidized surface with a dissolving agent;
17. The method of claim 16, further comprising:
The selection method according to claim 23, wherein said surface of said copper member is oxidized with an oxidizing agent.
The dissolving agent is Ni chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, potassium chloride, ammonium sulfate, ammonium chloride, nickel ammonium sulfate, ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetate/tetrasodium, ethylenediamine. -N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, 24. The method of selection according to claim 23, selected from the group consisting of sodium gluconate, tin(II) chloride, and citric acid.
The selection method according to any one of claims 23 to 25, further comprising forming a layer containing a metal other than copper on the surface treated with the dissolving agent.
The selection method according to claim 26, wherein the metal other than copper is Ni.
A method for manufacturing a copper member according to any one of claims 1 to 14,
1) a step of partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor; and 2) a step of oxidizing the partially coated surface to form a layer containing the copper oxide;
A method of manufacturing a copper member, comprising:
A method for manufacturing a copper member according to claim 13 or 14,
1) a step of partially coating the surface of a copper member with a silane coupling agent or a rust inhibitor; 2) a step of oxidizing the partially coated surface to form a layer containing the copper oxide;
3) forming a layer containing a metal other than copper on the oxidized surface;
A method of manufacturing a copper member, comprising:
A method for manufacturing a copper member according to any one of claims 1 to 14,
1) forming a layer containing the copper oxide by oxidizing the partially coated surface; and 2) treating the oxidized surface with a dissolving agent. Production method.
A method for manufacturing a copper member according to claim 13 or 14,
1) forming a layer containing the copper oxide by oxidizing the surface of the copper member;
2) treating the oxidation-treated surface with a dissolving agent; and 3) forming a layer containing a metal other than copper on the surface treated with the dissolving agent;
including
A method for producing a copper member, wherein the dissolving agent contains a component that dissolves the copper oxide.
The dissolving agent is Ni chloride, zinc chloride, iron chloride, chromium chloride, ammonium citrate, potassium chloride, ammonium sulfate, ammonium chloride, nickel ammonium sulfate, ethylenediaminetetraacetic acid, diethanolglycine, L-glutamic acid diacetate/tetrasodium, ethylenediamine. -N,N'-disuccinic acid, sodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, tetrasodium aspartate diacetate, disodium N-(2-hydroxyethyl)iminodiacetate, a compound selected from the group consisting of sodium gluconate, tin(II) chloride, and citric acid;
A method for manufacturing a copper member according to claim 30 or 31.
The method for producing a copper member according to claim 29 or 31, wherein the metal other than copper is Ni.