Layered structure

Abstract

[Problem] The purpose of the present invention is to provide a layered structure that comprises a plating film and an intermediate film and exhibits good adhesion as well as good insulation characteristics, throwing power, etching resistance, wiring formability, and migration resistance or seed layer removability. [Solution] Provided is a layered structure having a plating film formed on a substrate and containing an intermediate film between the substrate and plating film. The intermediate film is made from a metal oxide having a surface resistivity according to JIS K 6911 of at least 1.0 × 1010 Ω / sq. The film thickness of the intermediate film is at least 40 nm.

Description

Laminated structure

[0001] This invention relates to a laminated structure useful for electrical and electronic products and the like.

[0002] In recent years, the smoothness, dimensional stability, and insulating properties of substrates have become crucial for improving communication speeds in electronic devices and the information processing capabilities of computer processors. Therefore, there is a need to deposit plating on smooth substrates such as glass or ceramic substrates to improve adhesion, insulating properties, through-hole penetration, etching resistance, wiring formation properties, migration resistance, or seed layer removal properties.

[0003] Coating technology for non-conductive materials plays a crucial role, particularly in the evolution of electronic devices. In wet chemical metallization processes, the general procedure involves treating the surface of a non-conductive substrate with a catalyst such as Pd, followed by electroless metallization. Conventional organic substrates suffer from poor dimensional stability and flatness, making them unsuitable for applications requiring particularly high I / O pitches. Silicon and glass interposers offer advantages such as easy matching of thermal expansion coefficients and high compatibility with silicon chips. Furthermore, glass has superior electrical properties compared to silicon, enabling larger panel sizes and contributing to cost reduction. A key requirement when using glass substrates in electronic packaging is reliable plating technology for ensuring copper adhesion to the glass. Metallization of glass substrates with a surface roughness of less than 10 nm is particularly challenging. Recently, interlayers have been investigated to improve adhesion (see Patent Document 1). However, the method described in Patent Document 1 makes it difficult to obtain an interlayer with excellent adhesion strength, and is still not satisfactory for improving adhesion on glass substrates. Therefore, there has been a great need for a method that can form a plating film with excellent adhesion, as well as excellent insulation properties, through-hole penetration, etching resistance, wiring formation properties, migration resistance, or seed layer removal properties.

[0004] Japanese Patent Publication No. 2009-24203

[0005] The present invention aims to provide a laminated structure comprising a plating film and an interlayer having good adhesion, and further good insulation properties, slipperiness, etching resistance, wiring formation ability, migration resistance, or seed layer removal ability.

[0006] The inventors, through diligent research to achieve the above objective, discovered that the adhesion of the plating film is improved by forming one or more interlayer films containing metal oxides with a thickness of 40 nm or more on a smooth substrate surface. They found that such interlayer films can solve the above-mentioned conventional problems all at once. Furthermore, after obtaining the above findings, the inventors conducted further research and completed the present invention.

[0007] In other words, the present invention relates to the following invention: [1] A laminated structure in which a plating film is formed on a substrate, wherein a 1.0 × 10 １０[1] A laminated structure comprising an interlayer made of tin oxide, titanium oxide, or zinc oxide having a surface resistivity of Ω / □ or greater as defined in JIS K 6911, wherein the thickness of the interlayer is 40 nm or more. [2] The laminated structure according to [1], wherein a reducing agent and a catalyst are contained between the substrate and the interlayer. [3] The laminated structure according to [2], wherein the catalyst comprises one or more noble metals. [4] The laminated structure according to [2], wherein the catalyst comprises silver and palladium. [5] The laminated structure according to [1], wherein a second catalyst is contained between the interlayer and the plating film. [6] The laminated structure according to [5], wherein a third catalyst and a reducing agent are further contained between the interlayer and the plating film. [7] A product comprising a laminated structure, wherein the laminated structure is the laminated structure according to [1]. [8] A laminated structure in which an electroless plating film and / or an electroplating film are laminated on a substrate via one or more interlayer films, wherein the interlayer film contains a metal oxide, the metal oxide contains two or more metal elements having a metallic bonding radius of 110 to 145 pm (picometers), and the thickness of the interlayer film is 40 nm or more. [9] The laminated structure according to [8], wherein the metal oxide contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

[10] The laminated structure according to [8], wherein the metal oxide contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

[11] The laminated structure according to [8], wherein the metal oxide contains two or more metal elements that are D-block elements.

[12] The laminated structure according to [8], wherein the content of one of the metal elements is 60 at% or more relative to the total metal elements contained in the interlayer film.

[13] The laminated structure according to [8], wherein the composition ratio between at least two of the two or more metal elements is inclined in the direction of the film thickness of the interlayer.

[14] The laminated structure according to [8], comprising an electroless plating film, wherein the electroless plating film comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[15] The laminated structure according to [8], comprising an electroplating film, wherein the electroplating film comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[16] The laminated structure according to [8], wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

[17] A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure according to [8].

[18] A laminated structure comprising a substrate on which a first interlayer, a second interlayer, an electroless plating layer, and an electroplating layer are laminated in this order, wherein the first interlayer consists of a first metal oxide layer containing one type of metal element, the second interlayer consists of a second metal oxide layer containing two or more types of metal elements, and the thickness of the first interlayer is 40 nm or more.

[19] The laminated structure according to

[18] , wherein the first interlayer contains a metal element having a metallic bonding radius of 110 to 145 pm (picometers).

[20] The laminated structure according to

[18] , wherein the second interlayer contains two or more types of metal elements having a metallic bonding radius of 110 to 145 pm.

[21] The laminated structure according to

[18] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

[22] The laminated structure according to

[18] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

[23] The laminated structure according to

[18] , characterized in that the second interlayer contains two or more metal elements that are D-block elements.

[24] The laminated structure according to

[18] , characterized in that the electroless plating layer contains Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[25] The laminated structure according to

[18] , characterized in that the electroplating layer contains Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[26] The laminated structure according to

[18] , characterized in that the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

[27] A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure described in

[18] .

[28] A laminated structure comprising a first interlayer, a second interlayer, an electroless plating layer and an electroplating layer laminated in this order on a substrate, wherein the first interlayer consists of a first metal oxide layer containing one type of metal element, the second interlayer consists of a second metal oxide layer containing two or more types of metal elements, and the thickness of the second interlayer is 40 nm or more.

[29] The laminated structure according to

[28] , characterized in that the first interlayer contains a metal element having a metallic bonding radius of 110 to 145 pm (picometers).

[30] The laminated structure according to

[28] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 110 to 145 pm.

[31] The laminated structure according to

[28] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

[32] The laminated structure according to

[28] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

[33] The laminated structure according to

[28] , characterized in that the second interlayer contains two or more metal elements that are D-block elements.

[34] The laminated structure according to

[28] , characterized in that the electroless plating layer contains Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[35] The laminated structure according to

[28] , wherein the electroplating layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[36] The laminated structure according to

[28] , wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

[37] A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure according to

[28] .

[38] A laminated structure comprising a substrate on which a first interlayer, a second interlayer, an electroless plating layer, and an electroplating layer are laminated in this order, wherein the first interlayer consists of a first metal oxide layer containing one type of metal element, the second interlayer consists of a second metal oxide layer containing two or more types of metal elements, the ratio of the thickness of the first interlayer to the total thickness of the first and second interlayers is 30% or more, and the thickness of the first or second interlayer is 40 nm or more.

[39] The laminated structure according to

[38] , characterized in that the first interlayer contains a metal element having a metallic bonding radius of 110 to 145 pm (picometers).

[40] The laminated structure according to

[38] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 110 to 145 pm.

[41] The laminated structure according to

[38] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

[42] The laminated structure according to

[38] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

[43] The laminated structure according to

[38] , characterized in that the second interlayer contains two or more metal elements that are D-block elements.

[44] The laminated structure according to

[38] , characterized in that the electroless plating layer contains Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[45] The laminated structure according to

[38] , characterized in that the electroplating layer contains Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[46] The laminated structure according to

[38] , wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

[47] A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure according to

[38] .

[48] ​​A laminated structure comprising a substrate on which a first interlayer, a second interlayer, an electroless plating layer, and an electroplating layer are laminated in this order, wherein the first interlayer consists of a first metal oxide layer containing one type of metal element, the second interlayer consists of a second metal oxide layer containing two or more types of metal elements, the ratio of the thickness of the second interlayer to the total thickness of the first and second interlayers is 30% or more, and the thickness of the first or second interlayer is 40 nm or more.

[49] The laminated structure according to

[48] , wherein the first interlayer contains a metal element having a metallic bonding radius of 110 to 145 pm (picometers).

[50] The laminated structure according to

[48] , wherein the second interlayer contains two or more types of metal elements having a metallic bonding radius of 110 to 145 pm.

[51] The laminated structure according to

[48] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

[52] The laminated structure according to

[48] , characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

[53] The laminated structure according to

[48] , characterized in that the second interlayer contains two or more metal elements that are D-block elements.

[54] The laminated structure according to

[48] , characterized in that the electroless plating layer contains Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[55] The laminated structure according to

[48] , characterized in that the electroplating layer contains Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

[56] The laminated structure according to

[48] , wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

[57] A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure according to

[48] .

[0008] The laminated structure of the present invention includes a plating film with good adhesion, and further exhibits excellent insulation properties, penetration resistance, etching resistance, wiring formation properties, migration resistance, or seed layer removal properties.

[0009] This diagram shows the flowcharts for each step in Examples 1 to 5. The laminated structure obtained in Example 1 (alkali-free glass, SnO2, 10, 116, 11, 2.36 × 10) 11 This is an SEM cross-sectional view of the interlayer film of the laminated structure obtained in Example 6 (alkali-free glass, ZnO, 1 minute, 70°C, 202, 14, 8.80 × 10⁻¹). This is an SEM photograph showing the surface of the interlayer film in Figure 2. This is a flowchart of each step in Examples 6 to 8. 14 This is an SEM cross-sectional view of the interlayer film (300°C, 1 hour, 200°C, 1 hour, 370°C, 1 hour, 9.5, ○). This is an SEM photograph showing the surface of the interlayer film in Figure 5. This is a flowchart of each process in Examples 9, 20, 31, 42, and 53. This is an SEM cross-sectional photograph of the interlayer film obtained in Example 9-1. This is a 45° SEM photograph of the fracture surface of the interlayer film in Figure 8. This is a cross-sectional photograph of the through-hole obtained in Example 9-1. This is an SEM image of the wiring obtained in Example 31-1. This is a metallurgical microscope cross-sectional photograph of the wiring obtained in Example 31-1. This is a metallurgical microscope cross-sectional photograph of the wiring obtained in Comparative Example 13. This is an SEM image of Figure 12. This is the HAST test result using the pattern substrate in Example 42-1. This is the XPS analysis result of the substrate surface between wiring formed in Example 53-1.

[0010] The following describes specific embodiments of the inventions described in [1] to [7] above, but the present invention is not limited to these descriptions. The laminated structure of the present invention is a laminated structure in which a plating film is formed on a substrate, wherein a 1.0 × 10 １０The invention is characterized by including an interlayer made of tin oxide, titanium oxide, or zinc oxide having a surface resistivity of Ω / □ or greater (in accordance with the measurement method specified in JIS K 6911).

[0011] The aforementioned interlayer is 1.0 × 10 １０ The interlayer is made of tin oxide, titanium oxide, or zinc oxide and has a surface resistivity of Ω / □ or greater (according to the measurement method specified in JIS K 6911), but is not particularly limited.

[0012] In the present invention, it is preferable that the thickness of the interlayer film is 40 nm or more. Such a preferred range allows for better adhesion. Furthermore, in the present invention, it is preferable that a reducing agent and a catalyst are contained between the substrate and the interlayer film. The catalyst preferably contains one or more metals. Examples of the metals include noble metals, nickel, and cobalt. In the present invention, it is preferable that the catalyst is a noble metal catalyst, more preferably contains palladium, platinum, gold, silver, rhodium, ruthenium, etc., and most preferably contains silver and palladium. Furthermore, in the present invention, it is preferable that one or more second catalysts and / or one or more reducing agents are contained between the interlayer film and the plating film. In the present invention, it is preferable that one or more second catalysts and one or more reducing agents are contained between the interlayer film and the plating film. Examples of the second catalysts include metal catalysts containing the aforementioned metals, but noble metal catalysts are preferred. Examples of the reducing agents include metals or metal compounds that have reducing properties. Suitable examples of the reducing metal or metal compound include, for example, a tin-containing metal or metal compound. The third catalyst may be the same as the second catalyst.

[0013] The interlayer can be manufactured by a known film formation method. The plating film can also be manufactured by a known film formation method. The catalyst can be supported or formed between the substrate and the interlayer, or between the interlayer and the plating film, using known means.

[0014] The present invention will be described in detail below.

[0015] 1. Laminated Structure The laminated structure of the present invention is preferably a laminated structure comprising a metal catalyst layer, a metal oxide layer, an electroless copper plating film, and an electrolytic copper plating film. A preferred configuration of the laminated structure of the present invention involves supporting a metal catalyst on a substrate and forming a metal oxide thereon, thereby creating a 1.0 × 10⁻¹⁰ １０ An interlayer having excellent surface resistivity of Ω / □ or greater (according to the measurement method specified in JIS K 6911) is formed. Furthermore, a preferred laminated structure of the present invention preferably has an electroless plating film and an electrolytic copper plating film on a metal oxide layer, and is subjected to appropriate annealing treatment. According to such a preferred embodiment, the adhesion between these layers is further improved.

[0016] (Metal catalyst layer) The metal catalyst layer can be manufactured by known film formation methods. Specifically, it is preferable to support a metal catalyst nucleus such as a Sn catalyst, Ag catalyst, or Pd catalyst, and then apply a metal oxide layer. (Metal oxide layer) The oxide used to form the metal oxide layer is 1.0 × 10 １０ The oxide is not particularly limited as long as it is capable of forming an interlayer film made of tin oxide, titanium oxide, or zinc oxide having a surface resistivity of Ω / □ or higher as defined in JIS K 6911. The means for forming the interlayer film is not particularly limited as long as it can form an interlayer film made of tin oxide, titanium oxide, or zinc oxide having the aforementioned surface resistivity, and may be any known forming means.

[0017] The thickness of the metal oxide layer is not particularly limited, but is preferably 40 nm or more, and more preferably 80 nm or more. Within this preferred range, the adhesion of the plating film can be further improved.

[0018] Furthermore, in the present invention, it is preferable to perform annealing (1) after the formation of the metal oxide film. The temperature of the annealing (1) is not particularly limited, but in the present invention, it is preferably less than 400°C, and more preferably 250 to 350°C.

[0019] As the annealing (1) means, for example, a method of putting it in a constant temperature bath, a method of putting it in a heating furnace, an electric furnace, etc. can be mentioned. The atmosphere for the annealing (1) treatment is not particularly limited, and examples include an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc.

[0020] The annealing (1) time is not particularly limited as long as it is the degree of heating in the formation of the plating film usually, and it may be about 5 minutes to 3 hours.

[0021] (Electroless plating film) Since the plating film of the present invention has the metal oxide layer, the adhesion between the metal oxide layer and the electroless plating film is excellent, so a known electroless plating film may be formed. Examples of such an electroless plating film include an electroless nickel-phosphorus (Ni-P) plating film, an electroless nickel-boron (Ni-B) plating film, an electroless copper plating film, etc. Among these, an electroless copper plating film is preferable in terms of further improving the adhesion with the metal oxide layer.

[0022] By performing annealing (2) after forming the electroless copper plating film, the adhesion can be further improved.

[0023] The annealing (2) temperature is preferably 40 to 400 °C, more preferably 200 to 300 °C.

[0024] As the annealing (2) means, for example, a method of putting it in a constant temperature bath, a method of putting it in a heating furnace, an electric furnace, etc. can be mentioned. The atmosphere for the annealing (2) treatment is not particularly limited, and examples include an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of the inert gas include argon, helium, nitrogen, ammonia, etc. In the present invention, it is preferable that the annealing (2) atmosphere is a non-oxygen atmosphere, and an inert gas atmosphere is more preferable.

[0025] The annealing (2) time is not particularly limited as long as it is the degree of heating in the formation of the plating film usually, and it may be about 5 minutes to 3 hours.

[0026] The film thickness of the electroless plating film is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, and most preferably 0.5 μm or more. Further, the film thickness of the electroless plating film is preferably 3.0 μm or less, more preferably 2.0 μm or less. When the film thickness of the electroless plating film is within the above range, the stress is reduced and the plating adhesion is further improved.

[0027] (Electrolytic copper plating film) The plating film in the laminated structure of the present invention preferably has an electrolytic copper plating film on the electroless plating film.

[0028] The electrolytic copper plating film is not particularly limited, and examples thereof include known electrolytic copper plating films used for circuit boards.

[0029] The copper plating film is not particularly limited, and examples thereof include a copper sulfate plating film, a pyrophosphate copper plating film, and a neutral copper plating film. Among these, a copper sulfate plating film is preferable in terms of better plating adhesion.

[0030] The film thickness of the electrolytic copper plating film is preferably 0.5 μm or more, more preferably 0.7 μm or more, still more preferably 1.0 μm or more. The upper limit value of the film thickness of the electrolytic copper plating film is not particularly limited. When the electrolytic copper plating film of the plating film of the present invention is within the above range, the plating adhesion is further improved.

[0031] By performing annealing (3) after forming the electrolytic copper plating film, the adhesion can be further improved.

[0032] The annealing (3) temperature is preferably 40 to 600 ° C, more preferably 300 to 500 ° C.

[0033] Examples of the annealing (3) means include a method of putting it in a constant temperature bath, a method of putting it in a heating furnace or an electric furnace. The atmosphere of the annealing (3) treatment is not particularly limited, and examples thereof include an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, and an inert gas atmosphere. Examples of the inert gas include argon, helium, nitrogen, ammonia, and the like. In the present invention, the annealing (3) atmosphere is preferably a non-oxygen atmosphere, and more preferably an inert gas atmosphere.

[0034] The annealing time (3) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0035] 2. Laminated Structure

[0036] (Glass Substrate) The laminated structure of the present invention can use various substrates as the substrate, but in the present invention, it is preferable that the substrate is a glass substrate. The glass substrate is not particularly limited, and known glass substrates used as circuit boards for various electronic devices can be used. Preferably, the glass substrate is, for example, a base material for forming wiring, and is a glass substrate used in the manufacture of electronic devices where communication speeds are increasing.

[0037] The glass substrate is an amorphous substrate consisting of a silica network, and may contain network formers (network-forming oxides) such as aluminum, boron, and phosphorus, and network modifiers (network-modifying oxides) such as alkali metals, alkaline earth metals, and magnesium.

[0038] Specifically, the glass used to constitute the glass substrate may include, for example, soda-lime glass, alkali-free glass, borosilicate glass, or quartz glass. Alkali-free glass and borosilicate glass are particularly preferred.

[0039] The thickness of the glass substrate is not particularly limited and can be set appropriately depending on the purpose, but it is generally around 150 to 1000 μm.

[0040] Furthermore, even when other substrates are used instead of the glass substrate, good adhesion can be observed between the other substrate and the metal oxide layer. Examples of such other substrates include metal substrates, carbon substrates, resin substrates, resin films, ceramic substrates, and silicon substrates. Among the substrates, glass substrates are preferred because they are smooth, have low dielectric constant and dielectric loss tangent, excellent signal characteristics, have low thermal expansion coefficients resulting in good dimensional stability, and can be mass-produced at low cost. The laminated structure of the present invention is useful because it can exhibit excellent adhesion between the glass substrate and the metal oxide layer.

[0041] Examples of metals that form the above-mentioned metal substrate include aluminum, magnesium, iron, titanium, nickel, zinc, niobium, zirconium, molybdenum, brass, neodymium, stainless steel, Kovar, ferrite, and the like.

[0042] Examples of the above-mentioned resin substrates include fiber-reinforced plastic substrates (FRP, CFRP, GFRP), paper phenolic substrates (FR-1, FR-2), paper epoxy substrates (FR-3), glass epoxy substrates (FR-4, FR-5), glass composite substrates (CEM-3), glass polyimide substrates (GPY), fluororesin substrates (PTFE, PFA, PVDF), and polyphenylene oxide substrates (PPO).

[0043] Examples of resins used to form the above-mentioned resin film include polyethylene terephthalate (PET), polyimide (PI), polyetheretherketone (PEEK), and liquid crystal polymer (LCP).

[0044] Examples of the ceramic substrates mentioned above include alumina substrates, alumina-zirconia substrates, aluminum nitride substrates (AlN), and silicon nitride substrates (Si3N4).

[0045] The laminated structure can be adapted to various products or components using known means. Examples of such products or components include automobiles, transportation equipment, medical equipment, communication equipment, information equipment, computers, home appliances, electronic equipment, industrial machinery, industrial products, etc., or their components (including materials, etc.). (Examples)

[0046] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

[0047] Example 1 Three commercially available samples were processed using the following manufacturing method (all on 5.0 × 5.0 cm slides) to produce the laminated structures shown in Table 1. All of the resulting laminated structures exhibited good adhesion. Alkali-free glass (Ra < 10 nm) Borosilicate glass (Ra < 10 nm) Ceramic substrate Al₂O₃ (Ra = 450 nm)

[0048] A laminated structure was formed using the process shown in Figure 1, in which a plated film was formed on two types of glass substrates and a ceramic substrate. Specifically, alkali-free glass, borosilicate glass, and a ceramic substrate were prepared as glass substrates. As a pre-cleaning step, the glass substrates were immersed in 4M sodium hydroxide under ultrasonic irradiation for 5 minutes, then immersed in a glass cleaning solution (manufactured by Okuno Pharmaceutical Co., Ltd.) under ultrasonic irradiation at 25°C for 5 minutes, and then washed with pure water.

[0049] Next, the catalyst for reduction precipitation was applied by immersing the sample in a 100 ml / L aqueous solution of Sn catalyst (product name: Technoclear SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes, then in a 10 ml / L aqueous solution of Ag catalyst (product name: Technoclear AG, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute, and finally in a 50 ml / L aqueous solution of Pd catalyst (product name: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute. Rinsing with water was performed between each of the above treatments.

[0050] Next, the workpiece to be treated, to which the catalyst had been applied using the method described above, was immersed in an aqueous solution containing a metal oxide film forming treatment solution (tin complexing solution for tin plating, trade name: Substar SN-YA, manufactured by Okuno Pharmaceutical Co., Ltd.) at a liquid temperature of 40°C for 10 minutes to form a tin oxide film.

[0051] Furthermore, after washing with water, the material was immersed in a 50 ml / L aqueous solution of Pd catalyst (trademark name: Activator, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 3 minutes to deposit the catalyst onto the metal oxide layer.

[0052] The glass substrate on which the metal oxide layer was formed, prepared as described above, was subjected to annealing (1) treatment at the temperature and time shown in Table 1.

[0053] After annealing (1), the glass substrate on which the metal oxide layer was formed was immersed in a 60 ml / L aqueous solution of a reducing agent (trademark name: OPC-Crystar 150R, manufactured by Okuno Pharmaceutical Co., Ltd.) with 6 g / L of boric acid added, at 25°C for 2 minutes, washed with pure water, and then immersed in an electroless copper plating bath at 32°C for 30 minutes to form a 500 nm electroless copper layer.

[0054] A glass substrate coated with electroless copper plating was placed in a constant temperature bath and annealed (2) at the temperature and time shown in Table 1.

[0055] The following electrolytic copper plating process was applied to the electroless copper plating film.

[0056] (Electrolytic copper plating process) Composition and concentration: Copper sulfate pentahydrate: 70 g / L, 98% sulfuric acid: 200 g / L, 35% hydrochloric acid: 0.15 g / L, Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature and time: 25°C, 30 minutes, Current density: 2.3 A / dm ２ (Film thickness 15 μm)

[0057] A glass substrate with an electrolytic copper plating film was washed with pure water, then treated with rust prevention, washed again with pure water, and dried.

[0058] After drying, the glass substrate was placed in a constant temperature bath and annealed (3) at the temperature and time shown in Table 1.

[0059] A laminated structure was formed on the substrate using the method described above.

[0060] (Evaluation) The plating films of the examples and comparative examples manufactured as described above were evaluated by the following method. Comparative Example 1 used a laminated structure without a metal oxide film (interlayer). Comparative Example 2 used a laminated structure with a metal oxide film (interlayer) thickness of 36 nm, which is less than 40 nm (see Table 1).

[0061] (1) Thickness of the interlayer: The thickness was measured by observing the fracture surface of the substrate with an FE-SEM. (2) Surface resistivity of the interlayer: The surface resistivity (unit, Ω / □) was measured using a Hi-Resta UX: MCP-HT800 and a J-Box X-type: MCP-JB04 (manufactured by Nitto Seikou Analytech) in accordance with the resistivity measurement method of JIS K 6911 (General test methods for thermosetting plastics). (3) Surface roughness of the interlayer: The surface roughness (Ra, unit, nm) of the interlayer was measured using an atomic force microscope (AFM, SPM-9600 series, manufactured by Shimadzu Corporation). (4) Adhesion of Laminated Structure (Peel Strength) The peel strength was measured using a benchtop precision universal testing machine (AGS-X, manufactured by Shimadzu Corporation) under the conditions of a crosshead speed of 50 mm / min, a measurement direction of 90°, and a test stroke of 50 mm, and was evaluated according to the following evaluation criteria. ○: 3 N / cm or more, ×: less than 3 N / cm or peeling

[0062] The results are shown in Table 1 below.

[0063]

[0064] Example 2 The same procedure as in Figure 1 was performed up to the annealing (1) treatment after metal oxide film formation, and then the material was immersed in a 50 ml / L aqueous solution of Pd catalyst (trademark name: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 3 minutes to apply the catalyst.

[0065] As described above, after applying the second catalyst, the processes from electroless copper plating onwards shown in Table 1 were carried out, and the same evaluation as in Example 1 was performed. All of the resulting laminated structures exhibited good adhesion.

[0066] Example 3 The same procedure as in Figure 1 was performed up to the annealing (1) treatment after metal oxide film formation. After that, the sample was immersed in a 100 ml / L aqueous solution of Sn catalyst (trademark: Technoclear SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes, and then immersed in a 50 ml / L aqueous solution of Pd catalyst (trademark: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 3 minutes.

[0067] After applying the third catalyst and the reducing agent as described above, the processes after electroless copper plating in Table 1 were carried out, and the same evaluation as in Example 1 was performed. In addition, all of the obtained laminated structures had good adhesion.

[0068] The results of Example 2 and Example 3 are shown in Table 2 below.

[0069]

[0070] Example 4 A laminated structure was obtained in the same manner as in Example 1, except that a titanium solution was used as the metal oxide film-forming treatment liquid. The obtained laminated structure had good adhesion, similar to the laminated structure of Example 1. In addition, the surface resistivity of all the metal oxide films was 1.0 × 10 １０ Ω / □ or more (conforming to the measurement method specified in JIS K 6911).

[0071] Example 5 Laminated structures were obtained in the same manner as in Examples 2 and 3, except that a titanium solution was used as the metal oxide film-forming treatment liquid. All of the obtained laminated structures had good adhesion, similar to the laminated structures of Examples 2 and 3. In addition, the surface resistivity of all the metal oxide films was 1.0 × 10 １０ Ω / □ or more (conforming to the measurement method specified in JIS K 6911).

[0072] Example 6 A metal oxide film was obtained in the same manner as in Example 1, except that a zinc solution (trade name, Technoclear ZN-V2, manufactured by Okuno Pharmaceutical Co., Ltd.) was used as the metal oxide film-forming treatment liquid.

[0073] The glass and ceramic substrates with the metal oxide layer formed as adjusted above were subjected to annealing (1) treatment at the temperature and for the time shown in Table 3.

[0074] After the annealing (1) treatment, the glass substrate with the metal oxide layer formed was immersed in an electroless copper plating bath at 32°C for 30 minutes to form a 500-nm-thick electroless copper layer.

[0075] The glass substrate with electroless copper plating was placed in a thermostat and subjected to annealing (2) at the temperature and for the time shown in Table 3.

[0076] Electrolytic copper plating was applied to the electroless copper plating film under the same conditions as the electrolytic copper plating process described above.

[0077] A glass substrate with an electrolytic copper plating film was washed with pure water, then treated with rust prevention, washed again with pure water, and dried.

[0078] After drying, the glass substrate was placed in a constant temperature bath and annealed (3) at the temperature and time shown in Table 3.

[0079] The obtained laminated structures were evaluated in the same manner as in Example 1. The results of Example 6 are shown in Table 3 below. All of the obtained laminated structures exhibited good adhesion.

[0080] Example 7 The same procedure as in Figure 4 was performed up to annealing (1) after metal oxide film formation, and then the material was immersed in a 50 ml / L aqueous solution of Pd catalyst (trademark name: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 3 minutes to apply the catalyst.

[0081] As described above, after applying the second catalyst, the electroless copper plating process shown in Figure 4 was carried out, and the same evaluation as in Example 1 was performed.

[0082] Example 8 The same procedure as in Figure 4 was performed up to annealing (1) after metal oxide film formation, and then the sample was immersed in a 100 ml / L aqueous solution of Sn catalyst (trademark: Technoclear SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes, and then immersed in a 50 ml / L aqueous solution of Pd catalyst (trademark: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 3 minutes.

[0083] As described above, after applying the third catalyst and reducing agent, the electroless copper plating process shown in Figure 4 was carried out, and the same evaluation as in Example 1 was performed.

[0084] The results of Examples 7 and 8 are shown in Table 4 below.

[0085] The following describes specific embodiments of the invention described in [8] to

[17] above, but the present invention is not limited to these descriptions. The laminated structure of the present invention is a laminated structure in which an electroless plating film and / or an electroplating film are laminated on a substrate via one or more interlayer films, wherein the interlayer film contains a metal oxide, and the metal oxide contains two or more metal elements having a metal bonding radius of 110 to 145 pm. The interlayer film can be manufactured by a known film formation method by including the metal elements in a raw material solution. The blending ratio of other metal elements to the raw material solution is not particularly limited, but is preferably 0.1 wt% to 10 wt%. In addition, in the present invention, after the formation of the interlayer film, a diffusion film containing other metal elements may be formed, and then the laminated structure may be manufactured by diffusing the other metal elements into the interlayer film by heat treatment or the like. The diffusion film may be a plating film or a metal compound film. The metal compound film is not particularly limited and may be a metal oxide film or a metal hydroxide film.

[0086] In the present invention, it is preferable that the thickness of the interlayer film is 40 nm or more. Such a preferred range allows for better adhesion and through-hole penetration. Furthermore, in the present invention, it is preferable that a reducing agent and a catalyst are contained between the substrate and the interlayer film. The catalyst preferably contains one or more metals. Examples of the metals include noble metals, Ni, Co, etc. In the present invention, it is preferable that the catalyst is a noble metal catalyst, more preferably containing Pd, Pt, Au, Ag, Rh, Ru, etc., and most preferably containing Ag and Pd. Furthermore, in the present invention, it is preferable that one or more second catalysts and / or one or more reducing agents are contained between the interlayer film and the plating film. In the present invention, it is preferable that one or more second catalysts and one or more reducing agents are contained between the interlayer film and the plating film. Examples of the second catalysts include metal catalysts containing the aforementioned metals, but noble metal catalysts are preferred. Examples of the reducing agents include metals or metal compounds that have reducing properties. Suitable examples of the reducing metal or metal compound include, for example, a metal or metal compound containing Sn. The third catalyst may be the same as the second catalyst.

[0087] The substrate is not particularly limited as long as it can support the interlayer. The material of the substrate is also not particularly limited as long as it does not hinder the objective of the present invention, and may be a known substrate, an organic compound, or an inorganic compound. It may also be a porous structure. The shape of the substrate can be any shape and is effective for any shape, for example, plate-like such as a flat plate or disc, fibrous, rod-like, cylindrical, prismatic, tubular, helical, spherical, or ring-like, but in the present invention, a substrate is preferred.

[0088] The substrate is not particularly limited as long as it is in the form of a plate and serves as a support for the film to be formed. It may be an insulating substrate, a semiconductor substrate, a metal substrate, or a conductive substrate. Furthermore, substrates on which at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—is formed on part or all of their surfaces can also be suitably used as the substrate. In the present invention, it is preferable that the substrate is a glass substrate. The glass substrate may include a glass substrate having at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—on its surface.

[0089] The present invention will be described in detail below.

[0090] The laminated structure of the present invention is preferably a laminated structure comprising a metal catalyst layer, an intermediate layer as an interlayer, an electroless plating film, and an electroplating film. In a preferred embodiment of the laminated structure of the present invention, the metal catalyst is supported on the substrate and a metal oxide is formed thereon, thereby forming the metal oxide interlayer (hereinafter also referred to as the metal oxide layer). Furthermore, a preferred laminated structure of the present invention preferably has an electroless plating film and an electroplating film on the metal oxide layer and is subjected to appropriate annealing treatment. According to such a preferred embodiment, the adhesion between these layers and the through-hole penetration are further improved.

[0091] (Metal catalyst layer) The metal catalyst layer can be manufactured by known film formation methods. Specifically, it can be an ionic catalyst such as a Sn catalyst, Ag catalyst, or Pd catalyst, or a colloidal catalyst. As for colloidal catalysts, it is preferable to support a metal catalyst nucleus such as a Pd-Sn colloid and then apply a metal oxide layer. (Interlayer) As a method for forming the metal oxide layer, the interlayer formation method described above is a preferred method.

[0092] The metal oxide layer of the present invention contains two or more metal elements having a metallic bonding radius of 110 to 145 pm. For convenience, the metallic bonding radius in this invention may be the value specified in the "Basic Chemical Handbook, Revised 5th Edition, Published 2004" edited by the Chemical Society of Japan. Examples of the metal elements having a metallic bonding radius of 110 to 145 pm include Be, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. Preferably, the metal oxide layer of the present invention contains two or more metal elements having a metallic bonding radius of 120 to 145 pm. Examples of the metal elements having a metallic bonding radius of 120 to 145 pm include Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. The metal oxide layer of the present invention more preferably contains two or more metal elements having a metallic bonding radius of 125 to 145 pm. Examples of the metal elements having a metallic bonding radius of 125 to 145 pm include Al, Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. The metal oxide layer of the present invention is more preferably composed of two or more metal elements that are D-block elements. Examples of the metal elements that are D-block elements include Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and through-hole coverage of the plating film can be further improved.

[0093] Preferably, the content of one of the aforementioned metal elements is 60 at% or more, more preferably 70 at% or more, and even more preferably 90 at% or more, relative to the total metal elements contained in the interlayer film. Preferably, it is less than 99.9 at%, more preferably less than 99 at%, and even more preferably less than 98 at%. According to such a preferred range, the adhesion and through-hole coverage of the plating film can be further improved.

[0094] Furthermore, the composition ratio between at least two of the two or more metal elements may be tilted in the direction of the film thickness of the interlayer film. This tilt can further improve the adhesion and through-hole penetration of the plating film.

[0095] The thickness of the metal oxide layer is not particularly limited, but is preferably 40 nm or more, more preferably 60 nm or more, and even more preferably 80 nm or more. Within this preferred range, the adhesion and through-hole coverage of the plating film can be further improved.

[0096] Furthermore, in this invention, it is preferable to perform annealing (1) after the formation of the metal oxide film. The temperature of the annealing (1) is not particularly limited, but in this invention, it is preferably 200°C or higher, more preferably 250°C or higher, less than 400°C, and more preferably less than 350°C. Within this preferred range, the adhesion of the plating film and the through-hole coverage can be further improved.

[0097] Examples of the annealing (1) methods include placing the product in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (1) process is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. According to this preferred range, the adhesion and through-hole penetration of the plating film can be further improved.

[0098] The annealing time (1) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0099] (Electroless Plating Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion between the metal oxide layer and the plating film and excellent through-hole coverage, so a known electroless plating film can be formed. Examples of such electroless plating films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. Among these, an electroless copper plating film is more preferred.

[0100] By performing annealing (2) after forming the electroless plating film, adhesion and through-hole penetration can be further improved.

[0101] The annealing (2) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 100°C or higher, and even more preferably 200°C or higher. It is preferably less than 400°C, more preferably less than 350°C, and even more preferably less than 300°C. Within this preferred range, the adhesion of the plating film and the through-hole coverage can be further improved.

[0102] Examples of the annealing (2) method include placing the material in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (2) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, in order to further improve the adhesion and through-hole penetration of the plating film, the annealing (2) atmosphere is preferably an oxygen-free atmosphere, and an inert gas atmosphere is more preferably preferred.

[0103] The annealing time (2) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0104] The thickness of the electroless plating film is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more, and most preferably 0.5 μm or more. Furthermore, the thickness of the electroless plating film is preferably 3.0 μm or less, and more preferably 2.0 μm or less. When the thickness of the electroless plating film is within the above range, the adhesion between the metal oxide layer and the electroless plating film and the through-hole coverage are further improved.

[0105] (Electroplated Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion between the metal oxide layer and the plating film and excellent through-hole coverage, so it is sufficient to form a known electroplated film. Examples of such electroplated films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. In the laminated structure of the present invention, it is preferable to have an electroplated film on top of an electroless plating film. In the laminated structure of the present invention, electroplated copper is more preferable for the electroplated film. The electroplated copper film is not particularly limited, and examples include known electroplated copper films used on circuit boards. For example, copper sulfate plating films, copper pyrophosphate plating films, and neutral copper plating films are examples. Among these, copper sulfate plating films are even more preferable in terms of excellent plating adhesion and through-hole coverage.

[0106] The thickness of the electrolytic copper plating film is preferably 0.5 μm or more, more preferably 0.7 μm or more, and even more preferably 1.0 μm or more. There is no particular upper limit to the thickness of the electrolytic copper plating film. When the electrolytic copper plating film of the present invention is within the above range, the plating adhesion between the metal oxide layer and the electroless plating film and the through-hole coverage are further improved.

[0107] By performing annealing (3) after the formation of the electrolytic copper plating film, the plating adhesion and through-hole coverage can be further improved.

[0108] The annealing (3) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 200°C or higher, and even more preferably 300°C or higher. It is preferably less than 600°C, more preferably less than 550°C, and even more preferably less than 500°C. Within this preferred range, the adhesion of the plating film and the through-hole coverage can be further improved.

[0109] Examples of the annealing (3) methods include placing the material in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (3) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, it is preferable that the annealing (3) atmosphere is a non-oxygen atmosphere, and more preferably an inert gas atmosphere. Within such a preferred range, the adhesion of the plating film and the through-hole penetration can be further improved.

[0110] The annealing time (3) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0111] (Glass Substrate) The laminated structure of the present invention can use various substrates as the substrate, but in the present invention, it is preferable that the substrate is a glass substrate. The glass substrate is not particularly limited, and known glass substrates used as circuit boards for various electronic devices can be used. Preferably, the glass substrate is, for example, a base material for forming wiring, and is a glass substrate used in the manufacture of electronic devices where communication speeds are increasing.

[0112] The glass substrate is an amorphous substrate consisting of a silica network, and may contain network formers (network-forming oxides) such as Al, B, and P, and network modifiers (network-modifying oxides) such as alkali metals, alkaline earth metals, and magnesium.

[0113] Specifically, the glass used to constitute the glass substrate may include, for example, soda-lime glass, soda-lime glass, alkali-free glass, borosilicate glass, or quartz glass. Alkali-free glass and borosilicate glass are particularly preferred.

[0114] The thickness of the glass substrate is not particularly limited and can be set appropriately depending on the purpose, but it is generally around 150 to 1000 μm.

[0115] Furthermore, even when other substrates are used instead of the glass substrate, good adhesion and through-hole penetration can be observed between the other substrate and the metal oxide layer. Examples of such other substrates include metal substrates, carbon substrates, resin substrates, resin films, ceramic substrates, and silicon substrates. Among the substrates, glass substrates are preferred because they are smooth, have low dielectric constant and dielectric loss tangent, excellent signal characteristics, have low thermal expansion coefficients resulting in good dimensional stability, and can be mass-produced at low cost. The laminated structure of the present invention is useful because it can exhibit excellent adhesion and through-hole penetration between the glass substrate and the metal oxide layer.

[0116] Examples of metals used to form the above-mentioned metal substrate include Al, Mg, Fe, Ti, Ni, Zn, Nb, Zr, Mo, Nd, brass, stainless steel, Kovar, ferrite, and the like.

[0117] Examples of the above-mentioned resin substrates include fiber-reinforced plastic substrates (FRP, CFRP, GFRP), paper phenolic substrates (FR-1, FR-2), paper epoxy substrates (FR-3), glass epoxy substrates (FR-4, FR-5), glass composite substrates (CEM-3), glass polyimide substrates (GPY), fluororesin substrates (PTFE, PFA, PVDF), and polyphenylene oxide substrates (PPO).

[0118] Examples of resins used to form the above-mentioned resin film include polyethylene terephthalate (PET), polyimide (PI), polyetheretherketone (PEEK), and liquid crystal polymer (LCP).

[0119] Examples of the ceramic substrates mentioned above include alumina substrates, alumina-zirconia substrates, aluminum nitride (AlN) substrates, and silicon nitride (Si3N4) substrates.

[0120] The laminated structure can be adapted to various products or components using known means. Examples of such products or components include automobiles, transportation equipment, medical equipment, communication equipment, information equipment, computers, home appliances, electronic equipment, industrial machinery, industrial products, etc., or their components (including materials, etc.). (Examples)

[0121] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

[0122] Example 9 Three commercially available substrates were processed using the following manufacturing method (all on 5.0 × 5.0 cm slides) to produce the laminated structures shown in Table 5. All of the obtained laminated structures exhibited good adhesion and through-hole penetration. The surface roughness of the substrates was as follows: Alkali-free glass (Ra < 10 nm) Borosilicate glass (Ra < 10 nm) Ceramic substrate Al₂O₃ (Ra = 450 nm)

[0123] A laminated structure with a plated film formed on a substrate was created using the process shown in Figure 7. Specifically, alkali-free glass, borosilicate glass, and ceramics were prepared as glass substrates. As a pre-cleaning step, the glass substrate was immersed in 4M sodium hydroxide under ultrasonic irradiation for 5 minutes, then immersed in a glass cleaning solution (manufactured by Okuno Pharmaceutical Co., Ltd.) under ultrasonic irradiation at 25°C for 5 minutes, and then washed with pure water.

[0124] Next, the catalyst for reduction precipitation was applied by immersing the sample in a 100 ml / L aqueous solution of Sn catalyst (product name: Technoclear SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes, then in a 10 ml / L aqueous solution of Ag catalyst (product name: Technoclear AG, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute, and finally in a 100 ml / L aqueous solution of Pd catalyst (product name: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute. Rinsing with water was performed between each of the above treatments.

[0125] Next, a metal oxide film was formed using a Zn (metallic bonding radius 133 pm) solution containing Ni (metallic bonding radius 125 pm) and a reducing agent as a metal oxide film forming treatment solution.

[0126] The glass and ceramic substrates on which the metal oxide layer was formed, as prepared as described above, were subjected to annealing (1) treatment at the temperatures and times shown in Table 5.

[0127] After annealing (1), the glass substrate on which the metal oxide layer was formed was immersed in an electroless copper plating bath at 32°C for 30 minutes to create a 500 nm thick electroless copper layer.

[0128] A glass substrate coated with electroless copper plating was placed in a constant temperature bath and annealed (2) at the temperature and time shown in Table 5.

[0129] The following electrolytic copper plating was applied to the electroless copper plating film.

[0130] (Electrolytic copper plating conditions) Composition and processing conditions: Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２ , film thickness 5 μm

[0131] A glass substrate with an electrolytic copper plating film was washed with pure water, then treated with rust prevention, washed again with pure water, and dried.

[0132] After drying, the glass substrate was placed in a constant temperature bath and annealed (3) at the temperature and time shown in Table 5.

[0133] Using the method described above, a laminated structure containing the desired interlayer film was formed on the substrate.

[0134] Example 10 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Zn solution containing Be, a metal element with a metallic bonding radius of 111 pm, and a reducing agent were used.

[0135] Example 11 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Zn solution containing Fe, a metal element with a metallic bonding radius of 124 pm, and a reducing agent were used.

[0136] Example 12 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9, a Zn solution containing Al (metallic bonding radius 143 pm), which is a metal element other than D-block atoms, and a reducing agent were used as the metal oxide film forming treatment solution.

[0137] Example 13 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Zn solution containing Ti, a metal element with a metallic bonding radius of 145 pm, and a reducing agent were used.

[0138] Example 14 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Zn solution containing Ni and a reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Ti solution containing Co, a metal element with a metallic bonding radius of 135 pm, and a reducing agent were used.

[0139] Example 15 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Co solution containing Cu, a metal element with a metallic bonding radius of 135 pm, and a reducing agent were used.

[0140] In Example 16, a laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Cu solution containing Au, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used, and instead of using the electroless Cu plating described in Example 9, electroless Au plating was used.

[0141] In Example 17, a laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9, a Zn solution containing Ag, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used as the metal oxide film forming treatment solution, and instead of using the electroless Cu plating described in Example 9, electroless Pd plating was used.

[0142] In Example 18, a laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9, a Zn solution containing V, a metal element with a metallic bonding radius of 133 pm, and a reducing agent were used as the metal oxide film forming treatment solution; instead of using the electroless Cu plating described in Example 9, electroless Ag plating was used; and instead of using the electrolytic Cu plating described in Example 9, electrolytic Ag plating was used.

[0143] Example 19 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9, a Ti solution containing W with a metallic bonding radius of 137 pm and a reducing agent were used as the metal oxide film forming treatment solution; instead of using the electroless Cu plating described in Example 9, electroless Ni plating was used; and instead of using the electrolytic Cu plating described in Example 9, electrolytic Au plating was used. (Comparative Example)

[0144] Comparative Example 3 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Zn solution containing Ce, a metal element with a metallic bonding radius of 183 pm, and a reducing agent were used. The surface resistivity of the interfilm of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0145] Comparative Example 4 A laminated structure was formed in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Zn solution containing Bi, a metal element with a metallic bonding radius of 156 pm, and a reducing agent were used. The surface resistivity of the interfilm of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0146] Comparative Example 5 A laminated structure was obtained in the same manner as in Example 9, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 9 as the metal oxide film forming treatment solution, a Zn solution (without other metal elements) and a reducing agent were used. However, due to an over-addition of catalyst, the surface resistivity of the interlayer film was 1.0 × 10⁻⁶. １０ The result was less than Ω / □.

[0147] (Evaluation) The plating films of the examples and comparative examples manufactured as described above were evaluated by the following method.

[0148] (1) Measurement of interlayer thickness The fracture surface of the substrate was observed with an FE-SEM (JEOL, JSM-7900F) and the thickness was measured. (2) Calculation of metal elements contained in the interlayer An X-ray photoelectron spectrometer (XPS, ULVAC-PHI PHI5000 VersaProbeIII) was used for elemental analysis and thickness measurement of each interlayer. The analysis area was a circular area with a diameter of 200 μm at any position on the plated surface of the sample, and sputtering was performed in the depth direction with Ar ions, and the elemental composition (at%) was measured at regular sputtering depths. The sputtering conditions were as follows: X-ray source: monochromatic AlKα (1486.7 eV), voltage: 15 kV, beam diameter: 100 μmφ, extraction angle: 45°, acceleration voltage: 2 kV, Pass Energy: 112 eV, Time per step: 10 ms, Sputter Mode: Alternating. For convenience, the sputtering rate was calculated using a value converted to SiO2. From the elemental composition of the interlayer, the content of one metal element among the total metal elements contained in the interlayer was calculated as at%. If necessary, to obtain a film thickness suitable for XPS measurement, the plated film was drilled using GD-OES (GD-Profiler 2, Horiba, Ltd.) to a film thickness of approximately 500 nm or less, and then XPS measurement was performed. (3) Adhesion of Laminated Structure (Peel Strength) The peel strength was measured using a benchtop precision universal testing machine (AGS-X, manufactured by Shimadzu Corporation) under the conditions of a crosshead speed of 50 mm / min, a measurement direction of 90°, and a test stroke of 50 mm, and was evaluated according to the following evaluation criteria. ○: 3 N / cm or more ×: Less than 3 N / cm or peeling In order to eliminate the influence of differences in plating film thickness on the measured values, electrolytic copper plating was additionally applied to the plated film of the obtained laminated structure so that the total thickness of the plating film was constant, and then the peel strength was measured. (Electrolytic Copper Plating Process) Composition and Processing Conditions Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２, Film thickness: Total film thickness of the plating film was 15 μm (4) Through-hole penetration The plating penetration inside the through-holes was evaluated using a substrate with through-hole processing (substrate thickness: 0.7 mm, opening diameter: 80 μm, waist diameter: 50 μm) according to the following evaluation criteria. ○: No defects inside the through-hole ×: Defects inside the through-hole

[0149] The results are shown in Table 5 below. Figure 8 shows a cross-sectional SEM image of the interlayer obtained in Example 9-1, Figure 9 shows a 45° SEM image of the fracture surface of the interlayer, and Figure 10 shows a cross-sectional image of the through-hole plating penetration performance evaluated in Example 9-1. These results indicate that the example product exhibits excellent adhesion and through-hole penetration.

[0150]

[0151] The following describes specific embodiments of the invention described in

[18] to

[27] above, but the present invention is not limited to these descriptions. The laminated structure of the present invention is a laminated structure in which (1) an interlayer 1: a first metal oxide layer containing one type of metal, (2) an interlayer 2: a second metal oxide layer containing two or more types of metals, (3) an electroless plating layer, and (4) an electroplating layer are laminated on a substrate in that order, characterized in that the thickness of the interlayer 1 is 40 nm or more.

[0152] The interlayer films 1 and 2 can be manufactured by incorporating the metal element into a raw material solution and using a known film-forming method. The blending ratio of other metal elements to the raw material solution is not particularly limited, but is preferably 0.1 wt% to 10 wt%. In addition, in the present invention, after forming the interlayer film, a diffusion film containing other metal elements may be formed, and then the laminated structure may be manufactured by diffusing the other metal elements into the interlayer film by heat treatment or the like. The diffusion film may be a plated film or a metal compound film. The metal compound film is not particularly limited and may be a metal oxide film or a metal hydroxide film. In this embodiment, the interlayer film has a two-layer structure, but is not limited to this, and depending on the purpose, an interlayer film having one or more layers of a metal layer, a metal oxide layer, an inorganic compound layer, and / or an organic compound layer may be appropriately laminated between the interlayer film 1 and the interlayer film 2.

[0153] In the present invention, the thickness of the interlayer 1 is 40 nm or more. Such a range allows for better adhesion and etching resistance. Furthermore, in the present invention, it is preferable that a reducing agent and a catalyst are included between the substrate and the interlayer 1. The catalyst preferably contains one or more metals. Examples of the metals include noble metals, Ni, Co, etc. In the present invention, the catalyst is preferably a noble metal catalyst, more preferably Pd, Pt, Au, Ag, Rh, Ru, etc., and most preferably Ag and Pd. Furthermore, in the present invention, it is preferable that one or more second catalysts and / or one or more reducing agents are included between the interlayer 2 and the plating film. Examples of the second catalysts include metal catalysts containing the aforementioned metals, but noble metal catalysts are preferred. Examples of the reducing agents include metals or metal compounds having reducing properties. For example, metals or metal compounds containing Sn are preferred examples of metals or metal compounds having reducing properties. The third catalyst may be the same as the second catalyst.

[0154] The substrate is not particularly limited as long as it can support the interlayer. The material of the substrate is also not particularly limited as long as it does not hinder the objective of the present invention, and may be a known substrate, an organic compound, or an inorganic compound. It may also be a porous structure. The shape of the substrate can be any shape and is effective for any shape, for example, plate-like such as a flat plate or disc, fibrous, rod-like, cylindrical, prismatic, tubular, helical, spherical, or ring-like, but in the present invention, a substrate is preferred.

[0155] The substrate is not particularly limited as long as it is in the form of a plate and serves as a support for the film to be formed. It may be an insulating substrate, a semiconductor substrate, a metal substrate, or a conductive substrate. Furthermore, substrates on which at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—is formed on part or all of their surfaces can also be suitably used as the substrate. In the present invention, it is preferable that the substrate is a glass substrate. The glass substrate may include a glass substrate having at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—on its surface.

[0156] The present invention will be described in detail below.

[0157] The laminated structure of the present invention is preferably a laminated structure comprising a metal catalyst layer, an intermediate layer as an interlayer, an electroless plating film, and an electroplating film. In a preferred embodiment of the laminated structure of the present invention, the metal catalyst is supported on the substrate and a metal oxide is formed thereon, thereby forming the metal oxide interlayer (hereinafter also referred to as the metal oxide layer). Furthermore, a preferred laminated structure of the present invention preferably has an electroless plating film and an electroplated copper plating film on the metal oxide layer and is subjected to appropriate annealing treatment. According to such a preferred embodiment, the adhesion between these layers and the etching resistance are further improved.

[0158] (Metal catalyst layer) The metal catalyst layer can be manufactured by known film formation methods. Specifically, it can be an ionic catalyst such as a Sn catalyst, Ag catalyst, or Pd catalyst, or a colloidal catalyst. As for colloidal catalysts, it is preferable to support a metal catalyst nucleus such as a Pd-Sn colloid and then apply a metal oxide layer. (Interlayer) As a method for forming the metal oxide layer, the interlayer formation method described above is a preferred method.

[0159] The first metal oxide layer of the present invention preferably contains one metal element having a metallic bonding radius of 110 to 145 pm. The second metal oxide layer of the present invention preferably contains two or more metal elements having a metallic bonding radius of 110 to 145 pm. For convenience, the metallic bonding radius in the present invention may be the value listed in "Chemical Handbook Basic Edition Revised 5th Edition, published in 2004" edited by the Chemical Society of Japan. Examples of the metal elements having a metallic bonding radius of 110 to 145 pm include Be, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, and Au.

[0160] The first metal oxide layer of the present invention more preferably contains one metal element having a metallic bonding radius of 120 to 145 pm. Furthermore, the second metal oxide layer of the present invention more preferably contains two or more metal elements having a metallic bonding radius of 120 to 145 pm. Examples of the metal elements having a metallic bonding radius of 120 to 145 pm include Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and etching resistance of the plating film can be further improved.

[0161] The first metal oxide layer of the present invention is more preferably composed of one metal element having a metallic bonding radius of 125 to 145 pm. Furthermore, the second metal oxide layer of the present invention is more preferably composed of two or more metal elements having a metallic bonding radius of 125 to 145 pm. Examples of the metal elements having a metallic bonding radius of 125 to 145 pm include Al, Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and etching resistance of the plating film can be further improved.

[0162] The first metal oxide layer of the present invention most preferably contains one metal element that is a D-block element. The second metal oxide layer of the present invention most preferably contains two or more metal elements that are D-block elements. Examples of the metal elements that are D-block elements include Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and etching resistance of the plating film can be further improved.

[0163] The thickness of the interlayer 1 is 40 nm or more, more preferably 60 nm or more, and even more preferably 80 nm or more. According to this preferred range, the adhesion and etching resistance of the plating film can be further improved.

[0164] The content of one metal element in the second metal oxide layer is preferably 60 at% or more, more preferably 70 at% or more, and even more preferably 90 at% or more, relative to the total metal elements contained in the second metal oxide layer. It is preferably less than 99.9 at%, more preferably less than 99 at%, and even more preferably less than 98 at%. According to such a preferred range, the adhesion and etching resistance of the plating film can be further improved.

[0165] Furthermore, in the present invention, it is preferable to perform annealing (1) after the formation of the metal oxide film. The temperature of the annealing (1) is not particularly limited, but in the present invention, it is preferably 200°C or higher, more preferably 250°C or higher, less than 400°C, and more preferably less than 350°C. Within this preferred range, the adhesion and etching resistance of the plated film can be further improved.

[0166] Examples of the annealing (1) methods include placing the plate in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (1) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. According to this preferred range, the adhesion and etching resistance of the plated film can be further improved.

[0167] The annealing time (1) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0168] (Electroless Plating Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion and etching resistance between the metal oxide layer and the plating film, so a known electroless plating film can be formed. Examples of such electroless plating films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. Among these, an electroless copper plating film is more preferred.

[0169] By performing annealing (2) after forming the electroless plating film, adhesion and etching resistance can be further improved.

[0170] The annealing (2) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 100°C or higher, and even more preferably 200°C or higher. It is preferably less than 400°C, more preferably less than 350°C, and even more preferably less than 300°C. Within this preferred range, the adhesion and etching resistance of the plating film can be further improved.

[0171] Examples of the annealing (2) method include placing the plate in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (2) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, in order to further improve the adhesion and etching resistance of the plated film, the annealing (2) atmosphere is preferably an oxygen-free atmosphere, and an inert gas atmosphere is more preferably preferred.

[0172] The annealing time (2) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0173] The thickness of the electroless plating film is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more, and most preferably 0.5 μm or more. Furthermore, the thickness of the electroless plating film is preferably 3.0 μm or less, and more preferably 2.0 μm or less. When the thickness of the electroless plating film is within the above range, adhesion and etching resistance are further improved.

[0174] (Electroplated Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion and etching resistance between the metal oxide layer and the plating film, so it is sufficient to form a known electroplated film. Examples of such electroplated films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. In the laminated structure of the present invention, it is preferable to have an electroplated film on top of an electroless plating film. In the laminated structure of the present invention, electroplated copper is more preferable for the electroplated film. The electroplated copper film is not particularly limited, and examples include known electroplated copper films used on circuit boards. For example, copper sulfate plating films, copper pyrophosphate plating films, and neutral copper plating films are examples. Among these, copper sulfate plating films are even more preferable in terms of excellent plating adhesion and etching resistance.

[0175] The thickness of the electroplated film is preferably 0.5 μm or more, more preferably 0.7 μm or more, and even more preferably 1.0 μm or more. There is no particular upper limit to the thickness of the electroplated film. When the electroplated film of the present invention is within the above range, the adhesion between the metal oxide layer and the electroless plating film and the etching resistance are further improved.

[0176] By performing annealing (3) after the formation of the electroplated film, adhesion and etching resistance can be further improved.

[0177] The annealing (3) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 200°C or higher, and even more preferably 300°C or higher. It is preferably less than 600°C, more preferably less than 550°C, and even more preferably less than 500°C. Within this preferred range, the adhesion and etching resistance of the plating film can be further improved.

[0178] Examples of the annealing (3) methods include placing the material in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (3) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, it is preferable that the annealing (3) atmosphere be an oxygen-free atmosphere, and more preferably an inert gas atmosphere. Within this preferred range, the adhesion and etching resistance of the plated film can be further improved.

[0179] The annealing time (3) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0180] (Glass Substrate) The laminated structure of the present invention can use various substrates as the substrate, but in the present invention, it is preferable that the substrate is a glass substrate. The glass substrate is not particularly limited, and known glass substrates used as circuit boards for various electronic devices can be used. Preferably, the glass substrate is, for example, a base material for forming wiring, and is a glass substrate used in the manufacture of electronic devices where communication speeds are increasing.

[0181] The glass substrate is an amorphous substrate consisting of a silica network, and may contain network formers (network-forming oxides) such as aluminum, boron, and phosphorus, and network modifiers (network-modifying oxides) such as alkali metals, alkaline earth metals, and magnesium.

[0182] Specifically, the glass used to constitute the glass substrate may include, for example, soda-lime glass, soda-lime glass, alkali-free glass, borosilicate glass, or quartz glass. Alkali-free glass and borosilicate glass are particularly preferred.

[0183] The thickness of the glass substrate is not particularly limited and can be set appropriately depending on the purpose, but it is generally around 150 to 1000 μm.

[0184] Furthermore, even when other substrates are used instead of the glass substrate, good adhesion and etching resistance can be observed between the other substrate and the metal oxide layer. Examples of such other substrates include metal substrates, carbon substrates, resin substrates, resin films, ceramic substrates, and silicon substrates. Among the substrates, glass substrates are preferred because they are smooth, have low dielectric constant and dielectric loss tangent, excellent signal characteristics, have low thermal expansion coefficients resulting in good dimensional stability, and can be mass-produced at low cost. The laminated structure of the present invention is useful because it can exhibit excellent adhesion and etching resistance between the glass substrate and the metal oxide layer.

[0185] Examples of metals used to form the above-mentioned metal substrate include Al, Mg, Fe, Ti, Ni, Zn, Nb, Zr, Mo, Nd, brass, stainless steel, Kovar, ferrite, and the like.

[0186] Examples of the above-mentioned resin substrates include fiber-reinforced plastic substrates (FRP, CFRP, GFRP), paper phenolic substrates (FR-1, FR-2), paper epoxy substrates (FR-3), glass epoxy substrates (FR-4, FR-5), glass composite substrates (CEM-3), glass polyimide substrates (GPY), fluororesin substrates (PTFE, PFA, PVDF), and polyphenylene oxide substrates (PPO).

[0187] Examples of resins used to form the above-mentioned resin film include polyethylene terephthalate (PET), polyimide (PI), polyetheretherketone (PEEK), and liquid crystal polymer (LCP).

[0188] Examples of the ceramic substrates mentioned above include alumina substrates, alumina-zirconia substrates, aluminum nitride substrates (AlN), and silicon nitride substrates (Si3N4).

[0189] The laminated structure can be adapted to various products or components using known means. Examples of such products or components include automobiles, transportation equipment, medical equipment, communication equipment, information equipment, computers, home appliances, electronic equipment, industrial machinery, industrial products, etc., or their components (including materials, etc.). (Examples)

[0190] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

[0191] Example 20 Three commercially available samples were processed using the following manufacturing method (all on 5.0 × 5.0 cm slides) to produce the laminated structures shown in Table 6. All of the obtained laminated structures exhibited good adhesion and etching resistance. Alkali-free glass (Ra < 10 nm) Borosilicate glass (Ra < 10 nm) Ceramic substrate Al₂O₃ (Ra = 450 nm)

[0192] A laminated structure was formed using the process shown in Figure 7, in which a plated film was formed on two types of glass substrates and a ceramic substrate. Specifically, alkali-free glass, borosilicate glass, and a ceramic substrate were prepared as glass substrates. As a pre-cleaning step, the glass substrates were immersed in 4M sodium hydroxide under ultrasonic irradiation for 5 minutes, then immersed in a glass cleaning solution (manufactured by Okuno Pharmaceutical Co., Ltd.) under ultrasonic irradiation at 25°C for 5 minutes, and then washed with pure water.

[0193] Next, the catalyst for reduction precipitation was applied by immersing the sample in a 100 ml / L aqueous solution of Sn catalyst (product name: Technoclear SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes, then in a 10 ml / L aqueous solution of Ag catalyst (product name: Technoclear AG, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute, and finally in a 100 ml / L aqueous solution of Pd catalyst (product name: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute. Rinsing with water was performed between each of the above treatments.

[0194] Next, a first metal oxide layer was formed using a Zn (metallic bonding radius 133 pm) solution and a reducing agent as a metal oxide film forming treatment solution.

[0195] Next, a second metal oxide layer was formed using a Zn solution containing Ni (metallic bonding radius 125 pm) and a reducing agent as a metal oxide film formation treatment solution.

[0196] The glass and ceramic substrates on which the metal oxide layer was formed, prepared as described above, were subjected to annealing (1) treatment at the temperatures and times shown in Table 6.

[0197] After annealing (1), the glass substrate on which the metal oxide layer was formed was immersed in an electroless copper plating bath at 32°C for 30 minutes to create a 500 nm thick electroless copper layer.

[0198] A glass substrate coated with electroless copper plating was placed in a constant temperature bath and annealed (2) at the temperature and time shown in Table 6.

[0199] The following electrolytic copper plating process was applied to the electroless copper plating film.

[0200] (Electrolytic copper plating conditions) Composition and processing conditions: Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２ , film thickness 5 μm

[0201] A glass substrate with an electrolytic copper plating film was washed with pure water, then treated with rust prevention, washed again with pure water, and dried.

[0202] After drying, the glass substrate was placed in a constant temperature bath and annealed (3) at the temperature and time shown in Table 6.

[0203] Using the method described above, a laminated structure containing the desired interlayer film was formed on the substrate.

[0204] In Example 21, a laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Zn solution containing Be, a metal element with a metallic bonding radius of 111 pm, and a reducing agent were used to form the second metal oxide layer.

[0205] In Example 22, a laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Zn solution containing Fe, a metal element with a metallic bonding radius of 124 pm, and a reducing agent were used to form a second metal oxide layer.

[0206] In Example 23, a laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Zn solution containing Al (metallic bonding radius 143 pm), a metal element other than D-block atoms, and a reducing agent were used to form a second metal oxide layer.

[0207] Example 24 In Example 24, instead of using the Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Ti (metallic bonding radius 145 pm) solution and reducing agent were used to form the first metal oxide layer. Then, a laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Ti-containing Zn solution and reducing agent were used to form the second metal oxide layer.

[0208] In Example 25, instead of using the Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Cu (metallic bonding radius 135 pm) solution and reducing agent were used to form a first metal oxide layer. Then, instead of using the Zn solution containing Ni and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Ti solution containing Co, a metal element with a metallic bonding radius of 135 pm, and a reducing agent were used to form a second metal oxide layer, except that the laminated structure was formed in the same manner as in Example 20.

[0209] Example 26 In Example 26, instead of using the Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Co solution and reducing agent were used to form the first metal oxide layer. Then, a laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Cu-containing Co solution and reducing agent were used to form the second metal oxide layer.

[0210] In Example 27, a laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Cu solution containing Au, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used to form a second metal oxide layer, and instead of using the electroless Cu plating described in Example 20, electroless Au plating was used as the electroless plating.

[0211] In Example 28, a laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Zn solution containing Ag, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used to form a second metal oxide layer, and instead of using the electroless Cu plating described in Example 20, electroless Pd plating was used.

[0212] In Example 29, a laminated structure was formed in the same manner as in Example 20, except that, instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Zn solution containing V, a metal element with a metallic bonding radius of 133 pm, and a reducing agent were used to form a second metal oxide layer; instead of using the electroless Cu plating described in Example 20, electroless Ag plating was used; and instead of using the electrolytic Cu plating described in Example 20, electrolytic Ag plating was used.

[0213] Example 30 A laminated structure was formed in the same manner as in Example 20, except that, instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Ti solution containing W with a metallic bonding radius of 137 pm and a reducing agent were used to form a second metal oxide layer; instead of using the electroless Cu plating described in Example 20, electroless Ni plating was used; and instead of using the electrolytic Cu plating described in Example 20, electrolytic Au plating was used. (Comparative Example)

[0214] Comparative Example 6 A laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Zn solution containing Ce, a metal element with a metallic bonding radius of 183 pm, and a reducing agent were used to form the second metal oxide layer. The surface resistivity of the interlayer 2 of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0215] Comparative Example 7 A laminated structure was formed in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Zn solution containing Bi, a metal element with a metallic bonding radius of 156 pm, and a reducing agent were used to form the second metal oxide layer. The surface resistivity of the interlayer 2 of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0216] Comparative Example 8 A laminated structure was obtained in the same manner as in Example 20, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Zn solution (without other metal elements) and a reducing agent were used to form the second metal oxide layer. However, due to an over-addition of catalyst, the surface resistivity of the interlayer 2 was 1.0 × 10⁻⁶. １０ The result was less than Ω / □.

[0217] Comparative Examples 9 and 10: A laminated structure was obtained in the same manner as in Example 20, except that the thickness of the interlayer 1 was less than 40 nm.

[0218] Comparative Example 11 A laminated structure was obtained in the same manner as in Example 20, except that instead of using the Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Ce solution and reducing agent were used to form the first metal oxide layer.

[0219] Comparative Example 12 A laminated structure was obtained in the same manner as in Example 20, except that instead of using the Zn solution and reducing agent described in Example 20 as the metal oxide film forming treatment solution, a Bi solution and reducing agent were used to form the first metal oxide layer.

[0220] (Evaluation) The plating films of the examples and comparative examples manufactured as described above were evaluated by the following method.

[0221] (1) Measurement of interlayer thickness An X-ray photoelectron spectrometer (XPS, ULVAC-PHI PHI5000 VersaProbeIII) was used for elemental analysis and thickness measurement of each interlayer. The analysis area was a circular region with a diameter of 200 μm at any position on the plated surface of the sample. Sputtering was performed in the depth direction with Ar ions, and the elemental composition (at%) was measured at regular sputtering depths. The sputtering conditions were as follows: X-ray source: monochromatic AlKα (1486.7 eV), voltage: 15 kV, beam diameter: 100 μmφ, extraction angle: 45°, acceleration voltage: 2 kV, Pass Energy: 112 eV, Time per step: 10 ms, Sputter Mode: Alternating. For convenience, the sputtering rate was calculated using an SiO2 equivalent value. A depth profile was created from the sputtering rate and number of sputtering passes, and the film thickness was measured. If necessary, to ensure a film thickness suitable for XPS measurement, the plated film was drilled using GD-OES (GD-Profiler 2, Horiba, Ltd.) to a thickness of approximately 500 nm or less before XPS measurement was performed. (2) Adhesion of Laminated Structure (Peel Strength) The peel strength was measured using a benchtop precision universal testing machine (AGS-X, manufactured by Shimadzu Corporation) under the conditions of a crosshead speed of 50 mm / min, a measurement direction of 90°, and a test stroke of 50 mm, and was evaluated according to the following evaluation criteria. ○: 3 N / cm or more ×: Less than 3 N / cm or peeling In order to eliminate the influence of differences in plating film thickness on the measured values, electrolytic copper plating was additionally applied to the plated film of the obtained laminated structure so that the total thickness of the plating film was constant, and then the peel strength was measured. (Electrolytic Copper Plating Process) Composition and Processing Conditions Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２, Film thickness: Total film thickness of the plating film was 15 μm (3) Etching resistance of the laminated structure The same procedure as in Figure 7 was performed up to annealing (2), and the structure was immersed in a 100 ml / L aqueous solution of a degreasing agent (product name: DP-320 Clean, manufactured by Okuno Pharmaceutical Co., Ltd.) at 45°C for 15 minutes and evaluated according to the evaluation criteria below. ○: No change, ×: Dissolution or film peeling

[0222] The results are shown in Table 6 below. These results indicate that the sample material exhibits excellent adhesion and etching resistance.

[0223]

[0224] The following describes specific embodiments of the invention described in

[28] to

[37] above, but the present invention is not limited to these descriptions. The laminated structure of the present invention is a laminated structure in which (1) an interlayer 1: a first metal oxide layer containing one type of metal, (2) an interlayer 2: a second metal oxide layer containing two or more types of metals, (3) an electroless plating layer, and (4) an electroplating layer are laminated on a substrate in that order, characterized in that the thickness of the interlayer 2 is 40 nm or more. The interlayers 1 and 2 can be manufactured by a known film formation method by including the metal elements in a raw material solution. The blending ratio of other metal elements to the raw material solution is not particularly limited, but is preferably 0.1 wt% to 10 wt%. In addition, in the present invention, after the formation of the interlayer, a diffusion film containing other metal elements may be formed, and then the laminated structure may be manufactured by diffusing the other metal elements into the interlayer by heat treatment or the like. The diffusion film may be a plating film or a metal compound film. The aforementioned metal compound film is not particularly limited and may be a metal oxide film or a metal hydroxide film. In this embodiment, the interlayer has a two-layer structure, but it is not limited to this, and depending on the purpose, an interlayer having one or more layers of a metal layer, a metal oxide layer, an inorganic compound layer, and / or an organic compound layer may be appropriately laminated between interlayer 1 and interlayer 2.

[0225] In the present invention, the thickness of the interlayer film 2 is 40 nm or more. Such a range allows for better adhesion and wiring formation. Furthermore, in the present invention, it is preferable that a reducing agent and a catalyst are included between the substrate and the interlayer film 1. The catalyst preferably contains one or more metals. Examples of the metals include noble metals, Ni, Co, etc. In the present invention, the catalyst is preferably a noble metal catalyst, more preferably Pd, Pt, Au, Ag, Rh, Ru, etc., and most preferably Ag and Pd. Furthermore, in the present invention, it is preferable that one or more second catalysts and / or one or more reducing agents are included between the interlayer film 2 and the plating film. Examples of the second catalysts include metal catalysts containing the aforementioned metals, but noble metal catalysts are preferred. Examples of the reducing agents include metals or metal compounds having reducing properties. For example, metals or metal compounds containing Sn are preferred examples of metals or metal compounds having reducing properties. The third catalyst may be the same as the second catalyst.

[0226] The substrate is not particularly limited as long as it can support the interlayer. The material of the substrate is also not particularly limited as long as it does not hinder the objective of the present invention, and may be a known substrate, an organic compound, or an inorganic compound. It may also be a porous structure. The shape of the substrate can be any shape and is effective for any shape, for example, plate-like such as a flat plate or disc, fibrous, rod-like, cylindrical, prismatic, tubular, helical, spherical, or ring-like, but in the present invention, a substrate is preferred.

[0227] The substrate is not particularly limited as long as it is in the form of a plate and serves as a support for the film to be formed. It may be an insulating substrate, a semiconductor substrate, a metal substrate, or a conductive substrate. Furthermore, substrates on which at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—is formed on part or all of their surfaces can also be suitably used as the substrate. In the present invention, it is preferable that the substrate is a glass substrate. The glass substrate may include a glass substrate having at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—on its surface.

[0228] The present invention will be described in detail below.

[0229] The laminated structure of the present invention is preferably a laminated structure comprising a metal catalyst layer, an intermediate layer as an interlayer, an electroless copper plating film, and an electrolytic copper plating film. In a preferred embodiment of the laminated structure of the present invention, a metal catalyst is supported on the substrate, and a metal oxide is formed thereon to form a metal oxide interlayer. Furthermore, a preferred laminated structure of the present invention has an electroless plating film and an electrolytic copper plating film on the metal oxide layer, and is preferably subjected to appropriate annealing treatment. According to such a preferred embodiment, the adhesion between these layers and the ability to form wiring are improved.

[0230] (Metal catalyst layer) The metal catalyst layer can be manufactured by known film formation methods. Specifically, it can be an ionic catalyst such as a Sn catalyst, Ag catalyst, or Pd catalyst, or a colloidal catalyst. As for colloidal catalysts, it is preferable to support a metal catalyst nucleus such as a Pd-Sn colloid and then apply a metal oxide layer. (Interlayer) As a method for forming the metal oxide layer, the interlayer formation method described above is a preferred method.

[0231] The first metal oxide layer of the present invention preferably contains one metal element having a metallic bonding radius of 110 to 145 pm. The second metal oxide layer of the present invention preferably contains two or more metal elements having a metallic bonding radius of 110 to 145 pm. For convenience, the metallic bonding radius in the present invention may be the value listed in "Chemical Handbook Basic Edition Revised 5th Edition, published in 2004" edited by the Chemical Society of Japan. Examples of the metal elements having a metallic bonding radius of 110 to 145 pm include Be, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au.

[0232] The first metal oxide layer of the present invention more preferably contains one metal element having a metallic bonding radius of 120 to 145 pm. Furthermore, the second metal oxide layer of the present invention more preferably contains two or more metal elements having a metallic bonding radius of 120 to 145 pm. Examples of the metal elements having a metallic bonding radius of 120 to 145 pm include Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and wiring formation properties of the plating film can be further improved.

[0233] The first metal oxide layer of the present invention more preferably contains one metal element having a metallic bonding radius of 125 to 145 pm. Furthermore, the second metal oxide layer of the present invention more preferably contains two or more metal elements having a metallic bonding radius of 125 to 145 pm. Examples of the metal elements having a metallic bonding radius of 125 to 145 pm include Al, Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and wiring formation properties of the plating film can be further improved.

[0234] The first metal oxide layer of the present invention most preferably contains one metal element that is a D-block element. The second metal oxide layer of the present invention most preferably contains two or more metal elements that are D-block elements. Examples of the metal elements that are D-block elements include Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and wiring formation properties of the plating film can be further improved.

[0235] The thickness of the interlayer 2 is preferably 40 nm or more, more preferably 60 nm or more, and even more preferably 80 nm or more. Within this preferred range, the adhesion and wiring formation properties of the plating film can be further improved.

[0236] The content of one metal element in the second metal oxide layer is preferably 60 at% or more, more preferably 70 at% or more, and even more preferably 90 at% or more, relative to the total metal elements contained in the second metal oxide layer. It is preferably less than 99.9 at%, more preferably less than 99 at%, and even more preferably less than 98 at%. According to such a preferred range, the adhesion and wiring formation properties of the plating film can be further improved.

[0237] Furthermore, in this invention, it is preferable to perform annealing (1) after the metal oxide film is formed. The temperature of the annealing (1) is not particularly limited, but in this invention, it is preferably 200°C or higher, more preferably 250°C or higher, less than 400°C, and more preferably less than 350°C. Within this preferred range, the adhesion and wiring formation properties of the plated film can be further improved.

[0238] Examples of the annealing (1) methods include placing the material in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (1) process is not particularly limited and can include an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, or an inert gas atmosphere. Within this preferred range, the adhesion and wiring formation properties of the plated film can be further improved.

[0239] The annealing time (1) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0240] (Electroless Plating Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion between the metal oxide layer and the plating film and excellent wiring formation properties, so a known electroless plating film can be formed. Examples of such electroless plating films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. Among these, an electroless copper plating film is more preferred.

[0241] By performing annealing (2) after forming an electroless copper plating film, adhesion and wiring formation properties can be further improved.

[0242] The annealing (2) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 100°C or higher, and even more preferably 200°C or higher. It is preferably less than 400°C, more preferably less than 350°C, and even more preferably less than 300°C. Within this preferred range, the adhesion and wiring formation properties of the plating film can be further improved.

[0243] Examples of the annealing (2) method include placing the product in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (2) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, in order to further improve the adhesion and wiring formation properties of the plated film, the annealing (2) atmosphere is preferably an oxygen-free atmosphere, and an inert gas atmosphere is more preferably preferred.

[0244] The annealing time (2) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0245] The thickness of the electroless plating film is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more, and most preferably 0.5 μm or more. Furthermore, the thickness of the electroless plating film is preferably 3.0 μm or less, and more preferably 2.0 μm or less. When the thickness of the electroless plating film is within the above range, adhesion and wiring formation performance are further improved.

[0246] (Electroplated Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion between the metal oxide layer and the plating film and excellent wiring formation properties, so it is fine to form a known electroplated film. Examples of such electroplated films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. In the laminated structure of the present invention, it is preferable to have an electroplated film on top of an electroless plating film. In the laminated structure of the present invention, electroplated copper is more preferable for the electroplated film. The electroplated copper film is not particularly limited, and examples include known electroplated copper films used on circuit boards. For example, copper sulfate plating films, copper pyrophosphate plating films, and neutral copper plating films are examples. Among these, copper sulfate plating films are even more preferable in terms of excellent plating adhesion and wiring formation properties.

[0247] The thickness of the electroplated film is preferably 0.5 μm or more, more preferably 0.7 μm or more, and even more preferably 1.0 μm or more. There is no particular upper limit to the thickness of the electroplated film. When the electroplated film of the present invention is within the above range, the adhesion between the metal oxide layer and the electroless plating film and the wiring formation properties are further improved.

[0248] By performing annealing (3) after the formation of the electroplated film, adhesion and wiring formation properties can be further improved.

[0249] The annealing (3) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 200°C or higher, and even more preferably 300°C or higher. It is preferably less than 600°C, more preferably less than 550°C, and even more preferably less than 500°C. Within this preferred range, the adhesion and wiring formation properties of the plating film can be further improved.

[0250] Examples of the annealing (3) methods include placing the material in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (3) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, it is preferable that the annealing (3) atmosphere is a non-oxygen atmosphere, and more preferably an inert gas atmosphere. Within this preferred range, the adhesion and wiring formation properties of the plating film can be further improved.

[0251] The annealing time (3) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0252] (Glass Substrate) The laminated structure of the present invention can use various substrates as the substrate, but in the present invention, it is preferable that the substrate is a glass substrate. The glass substrate is not particularly limited, and known glass substrates used as circuit boards for various electronic devices can be used. Preferably, the glass substrate is, for example, a base material for forming wiring, and is a glass substrate used in the manufacture of electronic devices where communication speeds are increasing.

[0253] The glass substrate is an amorphous substrate consisting of a silica network, and may contain network formers (network-forming oxides) such as aluminum, boron, and phosphorus, and network modifiers (network-modifying oxides) such as alkali metals, alkaline earth metals, and magnesium.

[0254] Specifically, the glass used to constitute the glass substrate may include, for example, soda-lime glass, soda-lime glass, alkali-free glass, borosilicate glass, or quartz glass. Alkali-free glass and borosilicate glass are particularly preferred.

[0255] The thickness of the glass substrate is not particularly limited and can be set appropriately depending on the purpose, but it is generally around 150 to 1000 μm.

[0256] Furthermore, even when other substrates are used instead of the glass substrate, good adhesion and wiring formation properties can be observed between the other substrate and the metal oxide layer. Examples of such other substrates include metal substrates, carbon substrates, resin substrates, resin films, ceramic substrates, and silicon substrates. Among the substrates, glass substrates are preferred because they are smooth, have low dielectric constant and dielectric loss tangent, excellent signal characteristics, have low thermal expansion coefficients resulting in good dimensional stability, and can be mass-produced at low cost. The laminated structure of the present invention is useful because it can exhibit excellent adhesion and wiring formation properties between the glass substrate and the metal oxide layer.

[0257] Examples of metals used to form the above-mentioned metal substrate include Al, Mg, Fe, Ti, Ni, Zn, Nb, Zr, Mo, Nd, brass, stainless steel, Kovar, ferrite, and the like.

[0258] Examples of the above-mentioned resin substrates include fiber-reinforced plastic substrates (FRP, CFRP, GFRP), paper phenolic substrates (FR-1, FR-2), paper epoxy substrates (FR-3), glass epoxy substrates (FR-4, FR-5), glass composite substrates (CEM-3), glass polyimide substrates (GPY), fluororesin substrates (PTFE, PFA, PVDF), and polyphenylene oxide substrates (PPO).

[0259] Examples of resins used to form the above-mentioned resin film include polyethylene terephthalate (PET), polyimide (PI), polyetheretherketone (PEEK), and liquid crystal polymer (LCP).

[0260] Examples of the ceramic substrates mentioned above include alumina substrates, alumina-zirconia substrates, aluminum nitride substrates (AlN), and silicon nitride substrates (Si3N4).

[0261] The laminated structure can be adapted to various products or components using known means. Examples of such products or components include automobiles, transportation equipment, medical equipment, communication equipment, information equipment, computers, home appliances, electronic equipment, industrial machinery, industrial products, etc., or their components (including materials, etc.). (Examples)

[0262] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

[0263] Example 31 Three commercially available samples were processed using the following manufacturing method (all on 5.0 × 5.0 cm slides) to produce the laminated structures shown in Table 7. All of the obtained laminated structures exhibited good adhesion and wiring formation properties. Alkali-free glass (Ra < 10 nm) Borosilicate glass (Ra < 10 nm) Ceramic substrate Al₂O₃ (Ra = 450 nm)

[0264] A laminated structure was formed using the process shown in Figure 7, in which a plated film was formed on two types of glass substrates and a ceramic substrate. Specifically, alkali-free glass, borosilicate glass, and a ceramic substrate were prepared as glass substrates. As a pre-cleaning step, the glass substrates were immersed in 4M sodium hydroxide under ultrasonic irradiation for 5 minutes, then immersed in a glass cleaning solution (manufactured by Okuno Pharmaceutical Co., Ltd.) under ultrasonic irradiation at 25°C for 5 minutes, and then washed with pure water.

[0265] Next, the catalyst for reduction precipitation was applied by immersing the sample in a 100 ml / L aqueous solution of Sn catalyst (product name: Technoclear SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes, then in a 10 ml / L aqueous solution of Ag catalyst (product name: Technoclear AG, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute, and finally in a 100 ml / L aqueous solution of Pd catalyst (product name: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute. Rinsing with water was performed between each of the above treatments.

[0266] Next, a first metal oxide layer was formed using a Zn (metallic bonding radius 133 pm) solution and a reducing agent as a metal oxide film forming treatment solution.

[0267] Next, a second metal oxide layer was formed using a Zn solution containing Ni (metallic bonding radius 125 pm) and a reducing agent as a metal oxide film formation treatment solution.

[0268] The glass and ceramic substrates on which the metal oxide layer was formed, as prepared as described above, were subjected to annealing (1) treatment at the temperatures and times shown in Table 3.

[0269] After annealing (1), the glass substrate on which the metal oxide layer was formed was immersed in an electroless copper plating bath at 32°C for 30 minutes to create a 500 nm thick electroless copper layer.

[0270] A glass substrate coated with electroless copper plating was placed in a constant temperature bath and annealed (2) at the temperature and time shown in Table 7.

[0271] The following electrolytic copper plating process was applied to the electroless copper plating film.

[0272] (Electrolytic copper plating conditions) Composition and processing conditions: Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２ , film thickness 5 μm

[0273] A glass substrate with an electrolytic copper plating film was washed with pure water, then treated with rust prevention, washed again with pure water, and dried.

[0274] After drying, the glass substrate was placed in a constant temperature bath and annealed (3) at the temperature and time shown in Table 7.

[0275] Using the method described above, a laminated structure containing the desired interlayer film was formed on the substrate.

[0276] In Example 32, a laminated structure was formed in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Zn solution containing Be, a metal element with a metallic bonding radius of 111 pm, and a reducing agent were used to form the second metal oxide layer.

[0277] In Example 33, a laminated structure was formed in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Zn solution containing Fe, a metal element with a metallic bonding radius of 124 pm, and a reducing agent were used to form the second metal oxide layer.

[0278] In Example 34, a laminated structure was formed in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Zn solution containing Al (metallic bonding radius 143 pm), a metal element other than D-block atoms, and a reducing agent were used to form a second metal oxide layer.

[0279] In Example 35, instead of using the Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Ti (metallic bonding radius 145 pm) solution and reducing agent were used to form a first metal oxide layer. Then, a second metal oxide layer was formed in the same manner as in Example 31, except that instead of using the Zn solution and reducing agent containing Ni described in Example 31 as the metal oxide film forming treatment solution, a Zn solution containing Ti and a reducing agent were used to form a second metal oxide layer.

[0280] Example 36 In Example 36, instead of using the Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Cu (metallic bonding radius 135 pm) solution and reducing agent were used to form a first metal oxide layer. Then, a second metal oxide layer was formed in the same manner as in Example 31, except that instead of using the Zn solution containing Ni and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Ti solution containing Co, a metal element with a metallic bonding radius of 135 pm, and a reducing agent were used to form a second metal oxide layer.

[0281] Example 37 In Example 37, instead of using the Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Co solution and reducing agent were used to form a first metal oxide layer. Then, a laminated structure was formed in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Cu-containing Co solution and reducing agent were used to form a second metal oxide layer.

[0282] In Example 38, a laminated structure was formed in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Cu solution containing Au, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used to form a second metal oxide layer, and instead of using the electroless Cu plating described in Example 31, electroless Au plating was used as the electroless plating.

[0283] In Example 39, a laminated structure was formed in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Zn solution containing Ag, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used to form a second metal oxide layer, and instead of using the electroless Cu plating described in Example 31, electroless Pd plating was used.

[0284] In Example 40, a laminated structure was formed in the same manner as in Example 31, except that, instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Zn solution containing V, a metal element with a metallic bonding radius of 133 pm, and a reducing agent were used to form a second metal oxide layer; instead of using the electroless Cu plating described in Example 31, electroless Ag plating was used; and instead of using the electrolytic Cu plating described in Example 31, electrolytic Ag plating was used.

[0285] Example 41 A laminated structure was formed in the same manner as in Example 31, except that, instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Ti solution containing W with a metallic bonding radius of 137 pm and a reducing agent were used to form the second metal oxide layer; instead of using the electroless Cu plating described in Example 31, electroless Ni plating was used; and instead of using the electrolytic Cu plating described in Example 31, electrolytic Au plating was used. (Comparative Example)

[0286] Comparative Example 13 A laminated structure was formed in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Zn solution containing Ce, a metal element with a metallic bonding radius of 183 pm, and a reducing agent were used to form the second metal oxide layer. The surface resistivity of the interlayer 2 of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0287] Comparative Example 14 A laminated structure was formed in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Zn solution containing Bi, a metal element with a metallic bonding radius of 156 pm, and a reducing agent were used to form the second metal oxide layer. The surface resistivity of the interlayer 2 of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0288] Comparative Example 15 A laminated structure was obtained in the same manner as in Example 31, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Zn solution (without other metal elements) and a reducing agent were used to form the second metal oxide layer. However, due to an over-addition of catalyst, the surface resistivity of the interlayer 2 was 1.0 × 10⁻⁶. １０ The result was less than Ω / □.

[0289] Comparative Examples 16 and 17: A laminated structure was obtained in the same manner as in Example 31, except that the thickness of the interlayer 2 was less than 40 nm.

[0290] Comparative Example 18 A laminated structure was obtained in the same manner as in Example 31, except that instead of using the Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Ce solution and reducing agent were used to form the first metal oxide layer.

[0291] Comparative Example 19 A laminated structure was obtained in the same manner as in Example 31, except that instead of using the Zn solution and reducing agent described in Example 31 as the metal oxide film forming treatment solution, a Bi solution and reducing agent were used to form the first metal oxide layer.

[0292] (Evaluation) The plating films of the examples and comparative examples manufactured as described above were evaluated by the following method.

[0293] (1) Measurement of interlayer thickness An X-ray photoelectron spectrometer (XPS, ULVAC-PHI PHI5000 VersaProbeIII) was used for elemental analysis and thickness measurement of each interlayer. The analysis area was a circular region with a diameter of 200 μm at any position on the plated surface of the sample. Sputtering was performed in the depth direction with Ar ions, and the elemental composition (at%) was measured at regular sputtering depths. The sputtering conditions were as follows: X-ray source: monochromatic AlKα (1486.7 eV), voltage: 15 kV, beam diameter: 100 μmφ, extraction angle: 45°, acceleration voltage: 2 kV, Pass Energy: 112 eV, Time per step: 10 ms, Sputter Mode: Alternating. For convenience, the sputtering rate was calculated using an SiO2 equivalent value. A depth profile was created from the sputtering rate and number of sputtering passes, and the film thickness was measured. If necessary, to ensure a film thickness suitable for XPS measurement, the plated film was drilled using GD-OES (GD-Profiler 2, Horiba, Ltd.) to a thickness of approximately 500 nm or less before XPS measurement was performed. (2) Adhesion of Laminated Structure (Peel Strength) The peel strength was measured using a benchtop precision universal testing machine (AGS-X, manufactured by Shimadzu Corporation) under the conditions of a crosshead speed of 50 mm / min, a measurement direction of 90°, and a test stroke of 50 mm, and was evaluated according to the following evaluation criteria. ○: 3 N / cm or more ×: Less than 3 N / cm or peeling In order to eliminate the influence of differences in plating film thickness on the measured values, electrolytic copper plating was additionally applied to the plated film of the obtained laminated structure so that the total thickness of the plating film was constant, and then the peel strength was measured. (Electrolytic Copper Plating Process) Composition and Processing Conditions Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２, Film thickness: Total film thickness of the plating film was 15 μm (3) Wiring formation properties of the laminated structure The same process as in Figure 7 was performed up to (2) annealing to produce a patterned substrate. (DFR: RD-3015, manufactured by Resonaq, exposure machine: manufactured by Adtec Engineering, INPREX-4V2). The process shown below was then carried out. (Electrolytic copper plating process) Composition and concentration Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina FRV (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature and time 25°C, 45 minutes Current density 1.0 A / dm ２ (Film thickness 10 μm) (Resist stripping process) The dry film resist was stripped by immersion in a 200 ml / L aqueous solution of resist stripping solution (trademark: OPC Parsory 312, manufactured by Okuno Pharmaceutical Co., Ltd.) at 65°C for 3 minutes. (Seed etching process) Spray etching was performed at 30°C for 3 minutes at 0.1 MPa using a mixed aqueous solution of 300 ml / L seed etching solution (trademark: OPC Seed Etchant NE, manufactured by Okuno Pharmaceutical Co., Ltd.) and 100 ml / L 35% hydrogen peroxide solution to form wiring, and the annealing (3) process shown in Figure 7 was performed. (Evaluation of wiring formation ability) The substrate with wiring formed (comb-tooth wiring with line width 5 μm and space width 5 μm) was confirmed with FE-SEM (JEOL Ltd., JSM-7900F). Then, cross-sectional observation was performed using a metallurgical microscope to check for the presence or absence of undercuts. Cross-sectional observation was further performed with FE-SEM on those that were confirmed to have no undercuts by metallurgical microscope. In cross-sectional observation using FE-SEM, samples without undercuts were marked with ○, while those with undercuts were marked with ×.

[0294] The results are shown in Table 7 below. Figure 11 shows an SEM image of the wiring obtained in Example 31-1. Figures 12 and 13 show cross-sectional images of the wiring obtained in Example 31-1 and Comparative Example 13, observed using a metallurgical microscope. Figure 14 shows a cross-sectional SEM image of the cross-section of Figure 12, further observed using SEM. These results demonstrate that the example products exhibit excellent adhesion and wiring formation properties.

[0295]

[0296] The following describes specific embodiments of the invention described in

[38] to

[47] above, but the present invention is not limited to these descriptions. The laminated structure of the present invention is a laminated structure in which (1) an interlayer 1: a first metal oxide layer containing one type of metal, (2) an interlayer 2: a second metal oxide layer containing two or more types of metal, (3) an electroless plating layer, and (4) an electroplating layer are laminated on a substrate in that order, characterized in that the ratio of the thickness of the interlayer 1 to the total thickness of the interlayer 1 and the interlayer 2 is 30% or more.

[0297] The interlayer can be manufactured by incorporating the metal element into a raw material solution and using a known film-forming method. The proportion of other metal elements in the raw material solution is not particularly limited, but is preferably 0.1% to 10%. In addition, in the present invention, after forming the interlayer, a diffusion film containing other metal elements may be formed, and then the laminated structure may be manufactured by diffusing the other metal elements into the interlayer by heat treatment or the like. The diffusion film may be a plated film or a metal compound film. The metal compound film is not particularly limited and may be a metal oxide film or a metal hydroxide film. In this embodiment, the interlayer has a two-layer structure, but is not limited to this, and depending on the purpose, an interlayer having one or more layers of a metal layer, a metal oxide layer, an inorganic compound layer, and / or an organic compound layer may be appropriately laminated between interlayer 1 and interlayer 2.

[0298] In the present invention, it is preferable that the thickness of each of the interlayer films is 40 nm or more. Such a preferred range allows for better adhesion and migration resistance. In addition, in the present invention, it is preferable that a reducing agent and a catalyst are contained between the substrate and the interlayer film 1. The catalyst preferably contains one or more metals. Examples of the metals include noble metals, Ni, Co, etc. In the present invention, it is preferable that the catalyst is a noble metal catalyst, more preferably contains Pd, Pt, Au, Ag, Rh, Ru, etc., and most preferably contains Ag and Pd. In addition, in the present invention, it is preferable that one or more second catalysts and / or one or more reducing agents are contained between the interlayer film 2 and the plating film. Examples of the second catalysts include metal catalysts containing the aforementioned metals, but noble metal catalysts are preferred. Examples of the reducing agents include metals or metal compounds having reducing properties. For example, metals or metal compounds containing Sn are preferred examples of metals or metal compounds having reducing properties. The third catalyst may be the same as the second catalyst.

[0299] The substrate is not particularly limited as long as it can support the interlayer. The material of the substrate is also not particularly limited as long as it does not hinder the objective of the present invention, and may be a known substrate, an organic compound, or an inorganic compound. It may also be a porous structure. The shape of the substrate can be any shape and is effective for any shape, for example, plate-like such as a flat plate or disc, fibrous, rod-like, cylindrical, prismatic, tubular, helical, spherical, or ring-like, but in the present invention, a substrate is preferred.

[0300] The substrate is not particularly limited as long as it is in the form of a plate and serves as a support for the film to be formed. It may be an insulating substrate, a semiconductor substrate, a metal substrate, or a conductive substrate. Furthermore, substrates on which at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—is formed on part or all of their surfaces can also be suitably used as the substrate. In the present invention, it is preferable that the substrate is a glass substrate. The glass substrate may include a glass substrate having at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—on its surface.

[0301] The present invention will be described in detail below.

[0302] The laminated structure of the present invention is preferably a laminated structure comprising a metal catalyst layer, a metal oxide layer, an electroless copper plating film, and an electrolytic copper plating film. In a preferred embodiment of the laminated structure of the present invention, a metal catalyst is supported on the substrate, and a metal oxide is formed thereon to form a zinc oxide interlayer. Furthermore, a preferred laminated structure of the present invention has an electroless plating film and an electrolytic copper plating film on the metal oxide layer, and is preferably subjected to appropriate annealing treatment. According to such a preferred embodiment, the adhesion between these layers and the migration resistance are improved.

[0303] (Metal catalyst layer) The metal catalyst layer can be manufactured by known film formation methods. Specifically, it can be an ionic catalyst such as a Sn catalyst, Ag catalyst, or Pd catalyst, or a colloidal catalyst. As for colloidal catalysts, it is preferable to support a metal catalyst nucleus such as a Pd-Sn colloid and then apply a metal oxide layer. (Interlayer) As a method for forming the metal oxide layer, the interlayer formation method described above is a preferred method.

[0304] The first metal oxide layer of the present invention preferably contains one metal element having a metallic bonding radius of 110 to 145 pm. The second metal oxide layer of the present invention preferably contains two or more metal elements having a metallic bonding radius of 110 to 145 pm. For convenience, the metallic bonding radius in the present invention may be the value listed in "Chemical Handbook Basic Edition Revised 5th Edition, published in 2004" edited by the Chemical Society of Japan. Examples of the metal elements having a metallic bonding radius of 110 to 145 pm include Be, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au.

[0305] The first metal oxide layer of the present invention more preferably contains one metal element having a metallic bonding radius of 120 to 145 pm. Furthermore, the second metal oxide layer of the present invention more preferably contains two or more metal elements having a metallic bonding radius of 120 to 145 pm. Examples of the metal elements having a metallic bonding radius of 120 to 145 pm include Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and migration resistance of the plating film can be further improved.

[0306] The first metal oxide layer of the present invention more preferably contains one metal element having a metallic bonding radius of 125 to 145 pm. Furthermore, the second metal oxide layer of the present invention more preferably contains two or more metal elements having a metallic bonding radius of 125 to 145 pm. Examples of the metal elements having a metallic bonding radius of 125 to 145 pm include Al, Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and migration resistance of the plating film can be further improved.

[0307] The first metal oxide layer of the present invention most preferably contains one metal element that is a D-block element. The second metal oxide layer of the present invention most preferably contains two or more metal elements that are D-block elements. Examples of the metal elements that are D-block elements include Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion and migration resistance of the plating film can be further improved.

[0308] The thickness of the interlayer 1 is preferably such that it accounts for 30% or more, more preferably 40% or more, and even more preferably 50% or more of the total thickness of the interlayer 1 and the interlayer 2. Within this preferred range, the adhesion and migration resistance of the plating film can be further improved.

[0309] The content of one metal element in the second metal oxide layer is preferably 60 at% or more, more preferably 70 at% or more, and even more preferably 90 at% or more, relative to the total metal elements contained in the second metal oxide layer. It is preferably less than 99.9 at%, more preferably less than 99 at%, and even more preferably less than 98 at%. According to such a preferred range, the adhesion and migration resistance of the plating film can be further improved.

[0310] Furthermore, in the present invention, it is preferable to perform annealing (1) after the formation of the metal oxide film. The temperature of the annealing (1) is not particularly limited, but in the present invention, it is preferably 200°C or higher, more preferably 250°C or higher, less than 400°C, and more preferably less than 350°C. Within this preferred range, the adhesion and migration resistance of the plated film can be further improved.

[0311] Examples of the annealing (1) method include placing the plate in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (1) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Within this preferred range, the adhesion and migration resistance of the plated film can be further improved.

[0312] The annealing time (1) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0313] (Electroless Plating Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion and migration resistance between the metal oxide layer and the plating film, so a known electroless plating film can be formed. Examples of such electroless plating films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. Among these, an electroless copper plating film is more preferred.

[0314] By performing annealing (2) after forming the electroless plating film, adhesion and migration resistance can be further improved.

[0315] The annealing (2) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 100°C or higher, and even more preferably 200°C or higher. It is preferably less than 400°C, more preferably less than 350°C, and even more preferably less than 300°C. Within this preferred range, the adhesion and migration resistance of the plated film can be further improved.

[0316] Examples of the annealing (2) method include placing the plate in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (2) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, in order to further improve the adhesion and migration resistance of the plated film, the annealing (2) atmosphere is preferably an oxygen-free atmosphere, and an inert gas atmosphere is more preferably preferred.

[0317] The annealing time (2) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0318] The thickness of the electroless plating film is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more, and most preferably 0.5 μm or more. Furthermore, the thickness of the electroless plating film is preferably 3.0 μm or less, and more preferably 2.0 μm or less. When the thickness of the electroless plating film is within the above range, stress is reduced, and the plating adhesion and migration resistance are further improved.

[0319] (Electroplated Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion and migration resistance between the metal oxide layer and the plating film, so it is sufficient to form a known electroplated film. Examples of such electroplated films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. In the laminated structure of the present invention, it is preferable to have an electroplated film on top of an electroless plating film. In the laminated structure of the present invention, electroplated copper is more preferable for the electroplated film. The electroplated copper film is not particularly limited, and examples include known electroplated copper films used on circuit boards. For example, copper sulfate plating films, copper pyrophosphate plating films, and neutral copper plating films are examples. Among these, copper sulfate plating films are even more preferable in terms of excellent plating adhesion and migration resistance.

[0320] The thickness of the electroplated film is preferably 0.5 μm or more, more preferably 0.7 μm or more, and even more preferably 1.0 μm or more. There is no particular upper limit to the thickness of the electroplated film. When the electroplated film of the present invention is within the above range, the adhesion between the metal oxide layer and the electroless plating film and the migration resistance are further improved.

[0321] By performing annealing (3) after the formation of the electroplated film, adhesion and migration resistance can be further improved.

[0322] The annealing (3) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 200°C or higher, and even more preferably 300°C or higher. It is preferably less than 600°C, more preferably less than 550°C, and even more preferably less than 500°C. Within this preferred range, the adhesion and migration resistance of the plating film can be further improved.

[0323] Examples of the annealing (3) methods include placing the plate in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (3) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, it is preferable that the annealing (3) atmosphere is a non-oxygen atmosphere, and more preferably an inert gas atmosphere. Within this preferred range, the adhesion and migration resistance of the plated film can be further improved.

[0324] The annealing time (3) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0325] (Glass Substrate) The laminated structure of the present invention can use various substrates as the substrate, but in the present invention, it is preferable that the substrate is a glass substrate. The glass substrate is not particularly limited, and known glass substrates used as circuit boards for various electronic devices can be used. Preferably, the glass substrate is, for example, a base material for forming wiring, and is a glass substrate used in the manufacture of electronic devices where communication speeds are increasing.

[0326] The glass substrate is an amorphous substrate consisting of a silica network, and may contain network formers (network-forming oxides) such as aluminum, boron, and phosphorus, and network modifiers (network-modifying oxides) such as alkali metals, alkaline earth metals, and magnesium.

[0327] Specifically, the glass used to constitute the glass substrate may include, for example, soda-lime glass, soda-lime glass, alkali-free glass, borosilicate glass, or quartz glass. Alkali-free glass and borosilicate glass are particularly preferred.

[0328] The thickness of the glass substrate is not particularly limited and can be set appropriately depending on the purpose, but it is generally around 150 to 1000 μm.

[0329] Furthermore, even when other substrates are used instead of the glass substrate, good adhesion and migration resistance can be observed between the other substrate and the metal oxide layer. Examples of such other substrates include metal substrates, carbon substrates, resin substrates, resin films, ceramic substrates, and silicon substrates. Among the substrates, glass substrates are preferred because they are smooth, have low dielectric constant and dielectric loss tangent, excellent signal characteristics, have low thermal expansion coefficients resulting in good dimensional stability, and can be mass-produced at low cost. The laminated structure of the present invention is useful because it can exhibit excellent adhesion and migration resistance between the glass substrate and the metal oxide layer.

[0330] Examples of metals used to form the above-mentioned metal substrate include Al, Mg, Fe, Ti, Ni, Zn, Nb, Zr, Mo, Nd, brass, stainless steel, Kovar, ferrite, and the like.

[0331] Examples of the above-mentioned resin substrates include fiber-reinforced plastic substrates (FRP, CFRP, GFRP), paper phenolic substrates (FR-1, FR-2), paper epoxy substrates (FR-3), glass epoxy substrates (FR-4, FR-5), glass composite substrates (CEM-3), glass polyimide substrates (GPY), fluororesin substrates (PTFE, PFA, PVDF), and polyphenylene oxide substrates (PPO).

[0332] Examples of resins used to form the above-mentioned resin film include polyethylene terephthalate (PET), polyimide (PI), polyetheretherketone (PEEK), and liquid crystal polymer (LCP).

[0333] Examples of the ceramic substrates mentioned above include alumina substrates, alumina-zirconia substrates, aluminum nitride substrates (AlN), and silicon nitride substrates (Si3N4).

[0334] The laminated structure can be adapted to various products or components using known means. Examples of such products or components include automobiles, transportation equipment, medical equipment, communication equipment, information equipment, computers, home appliances, electronic equipment, industrial machinery, industrial products, etc., or their components (including materials, etc.). (Examples)

[0335] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

[0336] Example 42 Three commercially available samples were processed using the following manufacturing method (all on 5.0 × 5.0 cm slides) to produce the laminated structures shown in Table 8. All of the obtained laminated structures exhibited good adhesion and migration resistance. Alkali-free glass (Ra < 10 nm) Borosilicate glass (Ra < 10 nm) Ceramic substrate Al₂O₃ (Ra = 450 nm)

[0337] A laminated structure was formed using the process shown in Figure 7, in which a plated film was formed on two types of glass substrates and a ceramic substrate. Specifically, alkali-free glass, borosilicate glass, and a ceramic substrate were prepared as glass substrates. As a pre-cleaning step, the glass substrates were immersed in 4M sodium hydroxide under ultrasonic irradiation for 5 minutes, then immersed in a glass cleaning solution (manufactured by Okuno Pharmaceutical Co., Ltd.) under ultrasonic irradiation at 25°C for 5 minutes, and then washed with pure water.

[0338] Next, the catalyst for reduction precipitation was applied by immersing the sample in a 100 ml / L aqueous solution of Sn catalyst (product name: Technoclear SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes, then in a 10 ml / L aqueous solution of Ag catalyst (product name: Technoclear AG, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute, and finally in a 100 ml / L aqueous solution of Pd catalyst (product name: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute. Rinsing with water was performed between each of the above treatments.

[0339] Next, a first metal oxide layer was formed using a Zn (metallic bonding radius 133 pm) solution and a reducing agent as a metal oxide film forming treatment solution.

[0340] Next, a second metal oxide layer was formed using a Zn solution containing Ni (metallic bonding radius 125 pm) and a reducing agent as a metal oxide film formation treatment solution.

[0341] The glass and ceramic substrates on which the metal oxide layer was formed, as prepared as described above, were subjected to annealing (1) treatment at the temperatures and times shown in Table 8.

[0342] After annealing (1), the glass substrate on which the metal oxide layer was formed was immersed in an electroless copper plating bath at 32°C for 30 minutes to create a 500 nm thick electroless copper layer.

[0343] A glass substrate coated with electroless copper plating was placed in a constant temperature bath and annealed (2) at the temperature and time shown in Table 8.

[0344] The following electrolytic copper plating process was applied to the electroless copper plating film.

[0345] (Electrolytic copper plating conditions) Composition and processing conditions: Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２ , film thickness 5 μm

[0346] A glass substrate with an electrolytic copper plating film was washed with pure water, then treated with rust prevention, washed again with pure water, and dried.

[0347] After drying, the glass substrate was placed in a constant temperature bath and annealed (3) at the temperature and time shown in Table 8.

[0348] Using the method described above, a laminated structure containing the desired interlayer film was formed on the substrate.

[0349] In Example 43, a laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Zn solution containing Be, a metal element with a metallic bonding radius of 111 pm, and a reducing agent were used to form the second metal oxide layer.

[0350] In Example 44, a laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Zn solution containing Fe, a metal element with a metallic bonding radius of 124 pm, and a reducing agent were used to form the second metal oxide layer.

[0351] Example 45 A laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Zn solution containing Al (metallic bonding radius 143 pm), a metal element other than D-block atoms, and a reducing agent were used to form the second metal oxide layer.

[0352] Example 46 In Example 46, instead of using the Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Ti (metallic bonding radius 145 pm) solution and reducing agent were used to form a first metal oxide layer. Then, a laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Ti-containing Zn solution and reducing agent were used to form a second metal oxide layer.

[0353] Example 47 In Example 47, instead of using the Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Cu (metallic bonding radius 135 pm) solution and reducing agent were used to form a first metal oxide layer. Then, a second metal oxide layer was formed in the same manner as in Example 42, except that instead of using the Zn solution containing Ni and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Ti solution containing Co, a metal element with a metallic bonding radius of 135 pm, and a reducing agent were used to form a second metal oxide layer.

[0354] Example 48 In Example 48, instead of using the Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Co solution and reducing agent were used to form a first metal oxide layer. Then, a laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Cu-containing Co solution and reducing agent were used to form a second metal oxide layer.

[0355] In Example 49, a laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Cu solution containing Au, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used to form a second metal oxide layer, and instead of using the electroless Cu plating described in Example 42, electroless Au plating was used.

[0356] In Example 50, a laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Zn solution containing Ag, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used to form a second metal oxide layer, and instead of using the electroless Cu plating described in Example 42, electroless Pd plating was used.

[0357] In Example 51, a laminated structure was formed in the same manner as in Example 42, except that, instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Zn solution containing V, a metal element with a metallic bonding radius of 133 pm, and a reducing agent were used to form a second metal oxide layer; instead of using the electroless Cu plating described in Example 42, electroless Ag plating was used; and instead of using the electrolytic Cu plating described in Example 42, electrolytic Ag plating was used.

[0358] Example 52 A laminated structure was formed in the same manner as in Example 42, except that, instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Ti solution containing W with a metallic bonding radius of 137 pm and a reducing agent were used to form the second metal oxide layer; instead of using the electroless Cu plating described in Example 42, electroless Ni plating was used; and instead of using the electrolytic Cu plating described in Example 42, electrolytic Au plating was used. (Comparative Example)

[0359] Comparative Example 20 A laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Zn solution containing Ce, a metal element with a metallic bonding radius of 183 pm, and a reducing agent were used to form the second metal oxide layer. The surface resistivity of the interlayer 2 of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0360] Comparative Example 21 A laminated structure was formed in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Zn solution containing Bi, a metal element with a metallic bonding radius of 156 pm, and a reducing agent were used to form the second metal oxide layer. The surface resistivity of the interlayer 2 of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0361] Comparative Example 22 A laminated structure was obtained in the same manner as in Example 42, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Zn solution (without other metal elements) and a reducing agent were used to form the second metal oxide layer. However, due to an over-addition of catalyst, the surface resistivity of the interlayer 2 was 1.0 × 10⁻⁶. １０ The result was less than Ω / □.

[0362] Comparative Examples 23 and 24: A laminated structure was obtained in the same manner as in Example 42, except that the proportion of the thickness of interlayer 1 to the total thickness of interlayer 1 and interlayer 2 was less than 30%.

[0363] Comparative Example 25 A laminated structure was obtained in the same manner as in Example 42, except that instead of using the Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Ce solution and reducing agent were used to form the first metal oxide layer.

[0364] Comparative Example 26: A laminated structure was obtained in the same manner as in Example 42, except that instead of using the Zn solution and reducing agent described in Example 42 as the metal oxide film forming treatment solution, a Bi solution and reducing agent were used to form the first metal oxide layer.

[0365] (Evaluation) The plating films of the examples and comparative examples manufactured as described above were evaluated by the following method.

[0366] (1) Film Thickness Ratio of Interlayer 1 An X-ray photoelectron spectrometer (XPS, ULVAC-PHI PHI5000 VersaProbeIII) was used for elemental analysis and film thickness measurement of each interlayer. The analysis area was a circular region with a diameter of 200 μm at any position on the plated surface of the sample. Sputtering was performed in the depth direction with Ar ions, and the elemental composition (at%) was measured at regular sputtering depths. The sputtering conditions were as follows: X-ray source: monochromatic AlKα (1486.7 eV), voltage: 15 kV, beam diameter: 100 μmφ, extraction angle: 45°, acceleration voltage: 2 kV, Pass Energy: 112 eV, Time per step: 10 ms, Sputter Mode: Alternating. For convenience, the sputtering rate was calculated using an SiO2 equivalent value. A depth profile was created from the sputtering rate and number of sputtering passes, and the film thickness was measured. If necessary, to ensure a film thickness suitable for XPS measurement, the plated film was drilled using GD-OES (GD-Profiler 2, Horiba, Ltd.) to a thickness of approximately 500 nm or less before XPS measurement was performed.

[0367] (2) Adhesion of Laminated Structure (Peel Strength) The peel strength was measured using a benchtop precision universal testing machine (AGS-X, manufactured by Shimadzu Corporation) under the conditions of a crosshead speed of 50 mm / min, a measurement direction of 90°, and a test stroke of 50 mm, and was evaluated according to the following evaluation criteria. ○: 3 N / cm or more ×: Less than 3 N / cm or peeling In order to eliminate the influence of differences in plating film thickness on the measured values, electrolytic copper plating was additionally applied to the plated film of the obtained laminated structure so that the total thickness of the plating film was constant, and then the peel strength was measured. (Electrolytic Copper Plating Process) Composition and Processing Conditions Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２ Film thickness: 15 μm as the total thickness of the plating film.

[0368] (3) Migration resistance of the laminated structure The same process as in Figure 7 was performed up to electroless copper plating to fabricate a patterned substrate. (DFR: RD-3015, manufactured by Resonaq, exposure machine: manufactured by Adtec Engineering, INPREX-4V2). The following steps were then carried out. (Electrolytic copper plating process) Composition and concentration Copper sulfate pentahydrate: 100 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina FRV (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature and time 25°C, 45 minutes Current density 1.0 A / dm ２(Film thickness 10 μm) (Resist stripping process) The dry film resist was stripped by immersion in a 200 ml / L aqueous solution of resist stripping solution (trademark: OPC Parsory 312, manufactured by Okuno Pharmaceutical Co., Ltd.) at 65°C for 3 minutes. (Seed etching process) Spray etching was performed at 30°C for 3 minutes at 0.1 MPa using a mixed aqueous solution of seed etching solution (trademark: OPC Seed Etchant NE, manufactured by Okuno Pharmaceutical Co., Ltd.) at 300 ml / L and 100 ml / L of 35% hydrogen peroxide solution to form wiring, and the annealing (3) process shown in Figure 7 was performed. (HAST Test) Preconditioning was performed on a substrate with wiring formed on it (comb-tooth wiring with line width 10 μm and space width 10 μm) before the HAST test (according to J. STANDARD, "JESD22-A113D", 2003, 125°C, 24 hours → 60°C, 60% RH, 40 hours → reflow 260°C, 3 times). Subsequently, migration resistance was evaluated by the HAST test (Advanced Accelerated Life Testing System, ESPEC, Model: EHS-411M, AMI-050-U-5, according to J. STANDARD, "JESD22-A110B", 1999, Temperature: 110°C, Humidity: 85% RH, Applied voltage: 3.5 V, Measurement time: 200 hours, Threshold: 1.0 × 10⁻⁶). ６ Ω). Migration resistance was evaluated according to the following evaluation criteria. ○: Resistance value 1.0 × 10 ６ Ω or more / , ×: Resistance value 1.0 × 10 ６ Less than Ω or unmeasurable

[0369] The results are shown in Table 8 below. The HAST test results are shown in Figure 15. These results indicate that the example product exhibits excellent adhesion and migration resistance.

[0370]

[0371] The following describes specific embodiments of the invention described in

[48] to

[57] above, but the present invention is not limited to these descriptions. The laminated structure of the present invention is a laminated structure in which (1) an interlayer 1: a first metal oxide layer containing one type of metal, (2) an interlayer 2: a second metal oxide layer containing two or more types of metal, (3) an electroless plating layer, and (4) an electroplating layer are laminated on a substrate in that order, characterized in that the ratio of the thickness of the interlayer 2 to the total thickness of the interlayer 1 and the interlayer 2 is 30% or more.

[0372] The interlayer can be manufactured by incorporating the metal element into a raw material solution and using a known film-forming method. The proportion of other metal elements in the raw material solution is not particularly limited, but is preferably 0.1% to 10%. In addition, in the present invention, after forming the interlayer, a diffusion film containing other metal elements may be formed, and then the laminated structure may be manufactured by diffusing the other metal elements into the interlayer by heat treatment or the like. The diffusion film may be a plated film or a metal compound film. The metal compound film is not particularly limited and may be a metal oxide film or a metal hydroxide film. In this embodiment, the interlayer has a two-layer structure, but is not limited to this, and depending on the purpose, an interlayer having one or more layers of a metal layer, a metal oxide layer, an inorganic compound layer, and / or an organic compound layer may be appropriately laminated between interlayer 1 and interlayer 2.

[0373] In the present invention, it is preferable that the thickness of each of the interlayer films is 40 nm or more. Such a preferred range allows for better adhesion and seed layer removal. In addition, in the present invention, it is preferable that a reducing agent and a catalyst are contained between the substrate and the interlayer film 1. The catalyst preferably contains one or more metals. Examples of the metals include noble metals, Ni, Co, etc. In the present invention, it is preferable that the catalyst is a noble metal catalyst, more preferably contains Pd, Pt, Au, Ag, Rh, Ru, etc., and most preferably contains Ag and Pd. In addition, in the present invention, it is preferable that one or more second catalysts and / or one or more reducing agents are contained between the interlayer film 2 and the plating film. Examples of the second catalysts include metal catalysts containing the aforementioned metals, but noble metal catalysts are preferred. Examples of the reducing agents include metals or metal compounds having reducing properties. For example, metals or metal compounds containing Sn are preferred examples of metals or metal compounds having reducing properties. The third catalyst may be the same as the second catalyst.

[0374] The substrate is not particularly limited as long as it can support the interlayer. The material of the substrate is also not particularly limited as long as it does not hinder the objective of the present invention, and may be a known substrate, an organic compound, or an inorganic compound. It may also be a porous structure. The shape of the substrate can be any shape and is effective for any shape, for example, plate-like such as a flat plate or disc, fibrous, rod-like, cylindrical, prismatic, tubular, helical, spherical, or ring-like, but in the present invention, a substrate is preferred.

[0375] The substrate is not particularly limited as long as it is in the form of a plate and serves as a support for the film to be formed. It may be an insulating substrate, a semiconductor substrate, a metal substrate, or a conductive substrate. Furthermore, substrates on which at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—is formed on part or all of their surfaces can also be suitably used as the substrate. In the present invention, it is preferable that the substrate is a glass substrate. The glass substrate may include a glass substrate having at least one of the following films—a metal film, a semiconductor film, a conductive film, or an insulating film—on its surface.

[0376] The present invention will be described in detail below.

[0377] The laminated structure of the present invention is preferably a laminated structure comprising a metal catalyst layer, a metal oxide layer, an electroless copper plating film, and an electrolytic copper plating film. In a preferred embodiment of the laminated structure of the present invention, a metal catalyst is supported on the substrate, and a metal oxide is formed thereon to form a zinc oxide interlayer. Furthermore, a preferred laminated structure of the present invention has an electroless plating film and an electrolytic copper plating film on the metal oxide layer, and is preferably subjected to appropriate annealing treatment. According to such a preferred embodiment, the adhesion between these layers and the ease of seed layer removal are improved.

[0378] (Metal catalyst layer) The metal catalyst layer can be manufactured by known film formation methods. Specifically, it can be an ionic catalyst such as a Sn catalyst, Ag catalyst, or Pd catalyst, or a colloidal catalyst. As for colloidal catalysts, it is preferable to support a metal catalyst nucleus such as a Pd-Sn colloid and then apply a metal oxide layer. (Interlayer) As a method for forming the metal oxide layer, the interlayer formation method described above is a preferred method.

[0379] The first metal oxide layer of the present invention preferably contains one metal element having a metallic bonding radius of 110 to 145 pm. The second metal oxide layer of the present invention preferably contains two or more metal elements having a metallic bonding radius of 110 to 145 pm. For convenience, the metallic bonding radius in the present invention may be the value listed in "Chemical Handbook Basic Edition Revised 5th Edition, published in 2004" edited by the Chemical Society of Japan. Examples of the metal elements having a metallic bonding radius of 110 to 145 pm include Be, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au.

[0380] The first metal oxide layer of the present invention more preferably contains one metal element having a metallic bonding radius of 120 to 145 pm. Furthermore, the second metal oxide layer of the present invention more preferably contains two or more metal elements having a metallic bonding radius of 120 to 145 pm. Examples of the metal elements having a metallic bonding radius of 120 to 145 pm include Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion of the plating film and the ease of removing the seed layer can be further improved.

[0381] The first metal oxide layer of the present invention is more preferably composed of one metal element having a metallic bonding radius of 125 to 145 pm. Furthermore, the second metal oxide layer of the present invention is more preferably composed of two or more metal elements having a metallic bonding radius of 125 to 145 pm. Examples of the metal elements having a metallic bonding radius of 125 to 145 pm include Al, Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Sn, Sb, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion of the plating film and the ease of removing the seed layer can be further improved.

[0382] The first metal oxide layer of the present invention most preferably contains one metal element that is a D-block element. The second metal oxide layer of the present invention most preferably contains two or more metal elements that are D-block elements. Examples of the metal elements that are D-block elements include Ti, V, Cr, Co, Ni, Cu, Zn, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Ta, W, Re, Os, Ir, Np, Pt, or Au. By including such preferred metal elements, the adhesion of the plating film and the ease of removing the seed layer can be further improved.

[0383] The thickness of the interlayer 2 is preferably such that the ratio of the thickness of the interlayer 2 to the total thickness of the interlayer 1 and the interlayer 2 is 30% or more, more preferably 40% or more, and even more preferably 50% or more. According to this preferred range, the adhesion of the plating film and the ease of removing the seed layer can be further improved.

[0384] The content of one metal element in the second metal oxide layer is preferably 60 at% or more, more preferably 70 at% or more, and even more preferably 90 at% or more, relative to the total metal elements contained in the second metal oxide layer. It is preferably less than 99.9 at%, more preferably less than 99 at%, and even more preferably less than 98 at%. Including such preferred metal elements can further improve the adhesion of the plating film and the ease of removing the seed layer.

[0385] Furthermore, in the present invention, it is preferable to perform annealing (1) after the formation of the metal oxide film. The temperature of the annealing (1) is not particularly limited, but in the present invention, it is preferably 200°C or higher, more preferably 250°C or higher, less than 400°C, and more preferably less than 350°C. Within this preferred range, the adhesion of the plating film and the ease of removing the seed layer can be further improved.

[0386] Examples of the annealing (1) method include placing the plate in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (1) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. According to such a preferred range, the adhesion of the plating film and the ability to remove the seed layer can be further improved.

[0387] The annealing time (1) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0388] (Electroless Plating Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion between the metal oxide layer and the plating film and excellent seed layer removal properties, so a known electroless plating film can be formed. Examples of such electroless plating films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. Among these, an electroless copper plating film is more preferred.

[0389] By performing annealing (2) after forming the electroless plating film, adhesion and seed layer removal can be further improved.

[0390] The annealing (2) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 100°C or higher, and even more preferably 200°C or higher. It is preferably less than 400°C, more preferably less than 350°C, and even more preferably less than 300°C. Within this preferred range, the adhesion of the plating film and the ease of removing the seed layer can be further improved.

[0391] Examples of the annealing (2) method include placing the material in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (2) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, in order to improve the adhesion of the plating film and the ability to remove the seed layer, the annealing (2) atmosphere is preferably an oxygen-free atmosphere, and an inert gas atmosphere is more preferable.

[0392] The annealing time (2) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0393] The thickness of the electroless plating film is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more, and most preferably 0.5 μm or more. Furthermore, the thickness of the electroless plating film is preferably 3.0 μm or less, and more preferably 2.0 μm or less. When the thickness of the electroless plating film is within the above range, stress is reduced, and the plating adhesion and seed layer removal properties are further improved.

[0394] (Electroplated Film) Since the laminated structure of the present invention has the metal oxide layer, it has excellent adhesion between the metal oxide layer and the plating film and excellent seed layer removal properties, so it is sufficient to form a known electroplated film. Examples of such electroplated films include Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au. In the laminated structure of the present invention, it is preferable to have an electroplated film on top of an electroless plating film. In the laminated structure of the present invention, electroplated copper is more preferable for the electroplated film. The electroplated copper film is not particularly limited and examples include known electroplated copper films used on circuit boards. For example, copper sulfate plating films, copper pyrophosphate plating films, and neutral copper plating films are examples. Among these, copper sulfate plating films are even more preferable in terms of excellent plating adhesion and seed layer removal properties.

[0395] The thickness of the electroplated film is preferably 0.5 μm or more, more preferably 0.7 μm or more, and even more preferably 1.0 μm or more. There is no particular upper limit to the thickness of the electroplated film. When the electroplated film of the present invention is within the above range, the adhesion between the metal oxide layer and the electroless plating film and the seed layer removal performance are further improved.

[0396] By performing annealing (3) after the formation of the electroplated film, adhesion and seed layer removal can be further improved.

[0397] The annealing (3) temperature is not particularly limited, but in the present invention, it is preferably 40°C or higher, more preferably 200°C or higher, and even more preferably 300°C or higher. It is preferably less than 600°C, more preferably less than 550°C, and even more preferably less than 500°C. Within this preferred range, the adhesion of the plating film and the ease of removing the seed layer can be further improved.

[0398] Examples of the annealing (3) methods include placing the material in a constant temperature bath, a heating furnace, or an electric furnace. The atmosphere for the annealing (3) treatment is not particularly limited and includes an air atmosphere, a reduced pressure atmosphere, a vacuum atmosphere, an inert gas atmosphere, etc. Examples of inert gases include argon, helium, nitrogen, and ammonia. In the present invention, it is preferable that the annealing (3) atmosphere is a non-oxygen atmosphere, and more preferably an inert gas atmosphere. Within this preferred range, the adhesion of the plating film and the ability to remove the seed layer can be further improved.

[0399] The annealing time (3) described above is not particularly limited as long as it is heated to the extent that the plating film is normally formed, and can be as long as it is between 5 minutes and 3 hours.

[0400] (Glass Substrate) The laminated structure of the present invention can use various substrates as the substrate, but in the present invention, it is preferable that the substrate is a glass substrate. The glass substrate is not particularly limited, and known glass substrates used as circuit boards for various electronic devices can be used. Preferably, the glass substrate is, for example, a base material for forming wiring, and is a glass substrate used in the manufacture of electronic devices where communication speeds are increasing.

[0401] The glass substrate is an amorphous substrate consisting of a silica network, and may contain network formers (network-forming oxides) such as aluminum, boron, and phosphorus, and network modifiers (network-modifying oxides) such as alkali metals, alkaline earth metals, and magnesium.

[0402] Specifically, the glass used to constitute the glass substrate may include, for example, soda-lime glass, soda-lime glass, alkali-free glass, borosilicate glass, or quartz glass. Alkali-free glass and borosilicate glass are particularly preferred.

[0403] The thickness of the glass substrate is not particularly limited and can be set appropriately depending on the purpose, but it is generally around 150 to 1000 μm.

[0404] Furthermore, even when other substrates are used instead of the glass substrate, good adhesion and seed layer removal properties can be observed between the other substrate and the metal oxide layer. Examples of such other substrates include metal substrates, carbon substrates, resin substrates, resin films, ceramic substrates, and silicon substrates. Among the substrates, glass substrates are preferred because they are smooth, have low dielectric constant and dielectric loss tangent, excellent signal characteristics, have low thermal expansion coefficients resulting in good dimensional stability, and can be mass-produced at low cost. The laminated structure of the present invention is useful because it can exhibit excellent adhesion and seed layer removal properties between the glass substrate and the metal oxide layer.

[0405] Examples of metals used to form the above-mentioned metal substrate include Al, Mg, Fe, Ti, Ni, Zn, Nb, Zr, Mo, Nd, brass, stainless steel, Kovar, ferrite, and the like.

[0406] Examples of the above-mentioned resin substrates include fiber-reinforced plastic substrates (FRP, CFRP, GFRP), paper phenolic substrates (FR-1, FR-2), paper epoxy substrates (FR-3), glass epoxy substrates (FR-4, FR-5), glass composite substrates (CEM-3), glass polyimide substrates (GPY), fluororesin substrates (PTFE, PFA, PVDF), and polyphenylene oxide substrates (PPO).

[0407] Examples of resins used to form the above-mentioned resin film include polyethylene terephthalate (PET), polyimide (PI), polyetheretherketone (PEEK), and liquid crystal polymer (LCP).

[0408] Examples of the ceramic substrates mentioned above include alumina substrates, alumina-zirconia substrates, aluminum nitride substrates (AlN), and silicon nitride substrates (Si3N4).

[0409] The laminated structure can be adapted to various products or components using known means. Examples of such products or components include automobiles, transportation equipment, medical equipment, communication equipment, information equipment, computers, home appliances, electronic equipment, industrial machinery, industrial products, etc., or their components (including materials, etc.). (Examples)

[0410] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

[0411] Example 53 Three commercially available samples were processed using the following manufacturing method (all on 5.0 × 5.0 cm slides) to produce the laminated structures shown in Table 9. All of the obtained laminated structures exhibited good adhesion and seed layer removal properties. Alkali-free glass (Ra < 10 nm) Borosilicate glass (Ra < 10 nm) Ceramic substrate Al₂O₃ (Ra = 450 nm)

[0412] A laminated structure was formed using the process shown in Figure 7, in which a plated film was formed on two types of glass substrates and a ceramic substrate. Specifically, alkali-free glass, borosilicate glass, and a ceramic substrate were prepared as glass substrates. As a pre-cleaning step, the glass substrates were immersed in 4M sodium hydroxide under ultrasonic irradiation for 5 minutes, then immersed in a glass cleaning solution (manufactured by Okuno Pharmaceutical Co., Ltd.) under ultrasonic irradiation at 25°C for 5 minutes, and then washed with pure water.

[0413] Next, the catalyst for reduction precipitation was applied by immersing the sample in a 100 ml / L aqueous solution of Sn catalyst (product name: Technoclear SN, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 2 minutes, then in a 10 ml / L aqueous solution of Ag catalyst (product name: Technoclear AG, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute, and finally in a 100 ml / L aqueous solution of Pd catalyst (product name: Technoclear PD, manufactured by Okuno Pharmaceutical Co., Ltd.) at 25°C for 1 minute. Rinsing with water was performed between each of the above treatments.

[0414] Next, a first metal oxide layer was formed using a Zn (metallic bonding radius 133 pm) solution and a reducing agent as a metal oxide film forming treatment solution.

[0415] Next, a second metal oxide layer was formed using a Zn solution containing Ni (metallic bonding radius 125 pm) and a reducing agent as a metal oxide film formation treatment solution.

[0416] The glass and ceramic substrates on which the metal oxide layer was formed, prepared as described above, were subjected to annealing (1) treatment at the temperatures and times shown in Table 3.

[0417] After annealing (1), the glass substrate on which the metal oxide layer was formed was immersed in an electroless copper plating bath at 32°C for 30 minutes to create a 500 nm thick electroless copper layer.

[0418] A glass substrate coated with electroless copper plating was placed in a constant temperature bath and annealed (2) at the temperature and time shown in Table 9.

[0419] The following electrolytic copper plating process was applied to the electroless copper plating film.

[0420] (Electrolytic copper plating conditions) Composition and processing conditions: Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２ , film thickness 5 μm

[0421] A glass substrate with an electrolytic copper plating film was washed with pure water, then treated with rust prevention, washed again with pure water, and dried.

[0422] After drying, the glass substrate was placed in a constant temperature bath and annealed (3) at the temperature and time shown in Table 9.

[0423] Using the method described above, a laminated structure containing the desired interlayer film was formed on the substrate.

[0424] Example 54 A laminated structure was formed in the same manner as in Example 53, except that a second metal oxide layer was formed using a Zn solution containing Be, which is a metal element with a metallic bonding radius of 111 pm, and a reducing agent, instead of using the Ni-containing Zn solution and the reducing agent described in Example 53.

[0425] Example 55 A laminated structure was formed in the same manner as in Example 53, except that a second metal oxide layer was formed using a Zn solution containing Fe, which is a metal element with a metallic bonding radius of 124 pm, and a reducing agent, instead of using the Ni-containing Zn solution and the reducing agent described in Example 53.

[0426] Example 56 A laminated structure was formed in the same manner as in Example 53, except that a second metal oxide layer was formed using a Zn solution containing Al (metallic bonding radius 143 pm), which is a metal element other than D-block atoms, and a reducing agent, instead of using the Ni-containing Zn solution and the reducing agent described in Example 53.

[0427] Example 57 As the metal oxide film-forming treatment liquid, a first metal oxide layer was formed using a Ti (metallic bonding radius 145 pm) solution and a reducing agent, instead of using the Zn solution and the reducing agent described in Example 53. Then, a laminated structure was formed in the same manner as in Example 53, except that a second metal oxide layer was formed using a Zn solution containing Ti and a reducing agent, instead of using the Ni-containing Zn solution and the reducing agent described in Example 53.

[0428] Example 58 As the metal oxide film-forming treatment liquid, a first metal oxide layer was formed using a Cu (metallic bonding radius 135 pm) solution and a reducing agent, instead of using the Zn solution and the reducing agent described in Example 53. Then, a laminated structure was formed in the same manner as in Example 53, except that a second metal oxide layer was formed using a Ti solution containing Co, which is a metal element with a metallic bonding radius of 135 pm, and a reducing agent, instead of using the Ni-containing Zn solution and the reducing agent described in Example 53.

[0429] Example 59 In Example 59, instead of using the Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Co solution and reducing agent were used to form a first metal oxide layer. Then, a laminated structure was formed in the same manner as in Example 53, except that instead of using the Zn solution and reducing agent containing Ni described in Example 53 as the metal oxide film forming treatment solution, a Co solution containing Cu and a reducing agent were used to form a second metal oxide layer.

[0430] In Example 60, a laminated structure was formed in the same manner as in Example 53, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Cu solution containing Au, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used to form a second metal oxide layer, and instead of using the electroless Cu plating described in Example 53, electroless Au plating was used.

[0431] In Example 61, a laminated structure was formed in the same manner as in Example 53, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Zn solution containing Ag, a metal element with a metallic bonding radius of 144 pm, and a reducing agent were used to form a second metal oxide layer, and instead of using the electroless Cu plating described in Example 53, electroless Pd plating was used.

[0432] In Example 62, a laminated structure was formed in the same manner as in Example 53, except that, instead of using the Ni-containing Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Zn solution containing V, a metal element with a metallic bonding radius of 133 pm, and a reducing agent were used to form a second metal oxide layer; instead of using the electroless Cu plating described in Example 53, electroless Ag plating was used; and instead of using the electrolytic Cu plating described in Example 53, electrolytic Ag plating was used.

[0433] Example 63 A laminated structure was formed in the same manner as in Example 53, except that, instead of using the Ni-containing Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Ti solution containing W with a metallic bonding radius of 137 pm and a reducing agent were used to form the second metal oxide layer; instead of using the electroless Cu plating described in Example 53, electroless Ni plating was used; and instead of using the electrolytic Cu plating described in Example 53, electrolytic Au plating was used. (Comparative Example)

[0434] Comparative Example 27 A laminated structure was formed in the same manner as in Example 53, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Zn solution containing Ce, a metal element with a metallic bonding radius of 183 pm, and a reducing agent were used to form the second metal oxide layer. The surface resistivity of the interlayer 2 of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0435] Comparative Example 28 A laminated structure was formed in the same manner as in Example 53, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Zn solution containing Bi, a metal element with a metallic bonding radius of 156 pm, and a reducing agent were used to form the second metal oxide layer. The surface resistivity of the interlayer 2 of the obtained laminated structure was 1.0 × 10⁻⁶. １０ It was less than Ω / □.

[0436] Comparative Example 29 A laminated structure was obtained in the same manner as in Example 53, except that instead of using the Ni-containing Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Zn solution (without other metal elements) and a reducing agent were used to form the second metal oxide layer. However, due to an over-addition of catalyst, the surface resistivity of the interlayer 2 was 1.0 × 10⁻⁶. １０ The result was less than Ω / □.

[0437] Comparative Examples 30 and 31: A laminated structure was obtained in the same manner as in Example 53, except that the proportion of the thickness of interlayer 2 to the total thickness of interlayer 1 and interlayer 2 was less than 30%.

[0438] Comparative Example 32 A laminated structure was obtained in the same manner as in Example 53, except that instead of using the Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Ce solution and reducing agent were used to form the first metal oxide layer.

[0439] Comparative Example 33: A laminated structure was obtained in the same manner as in Example 53, except that instead of using the Zn solution and reducing agent described in Example 53 as the metal oxide film forming treatment solution, a Bi solution and reducing agent were used to form the first metal oxide layer.

[0440] (Evaluation) The plating films of the examples and comparative examples manufactured as described above were evaluated by the following method.

[0441] (1) Film Thickness Ratio of Interlayer 2 An X-ray photoelectron spectrometer (XPS, ULVAC-PHI PHI5000 VersaProbeIII) was used for elemental analysis and film thickness measurement of each interlayer. The analysis area was a circular region with a diameter of 200 μm at any position on the plated surface of the sample. Sputtering was performed in the depth direction with Ar ions, and the elemental composition (at%) was measured at regular sputtering depths. The sputtering conditions were as follows: X-ray source: monochromatic AlKα (1486.7 eV), voltage: 15 kV, beam diameter: 100 μmφ, extraction angle: 45°, acceleration voltage: 2 kV, Pass Energy: 112 eV, Time per step: 10 ms, Sputter Mode: Alternating. For convenience, the sputtering rate was calculated using an SiO2 equivalent value. A depth profile was created from the sputtering rate and number of sputtering passes, and the film thickness was measured. If necessary, to ensure a film thickness suitable for XPS measurement, the plated film was drilled using GD-OES (GD-Profiler 2, Horiba, Ltd.) to a thickness of approximately 500 nm or less before XPS measurement was performed.

[0442] (2) Adhesion of Laminated Structure (Peel Strength) The peel strength was measured using a benchtop precision universal testing machine (AGS-X, manufactured by Shimadzu Corporation) under the conditions of a crosshead speed of 50 mm / min, a measurement direction of 90°, and a test stroke of 50 mm, and was evaluated according to the following evaluation criteria. ○: 3 N / cm or more ×: Less than 3 N / cm or peeling In order to eliminate the influence of differences in plating film thickness on the measured values, electrolytic copper plating was additionally applied to the plated film of the obtained laminated structure so that the total thickness of the plating film was constant, and then the peel strength was measured. (Electrolytic Copper Plating Process) Composition and Processing Conditions Copper sulfate pentahydrate: 70 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina SF (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature 25°C, current density 2.3 A / dm ２ Film thickness: 15 μm as the total thickness of the plating film.

[0443] (3) The same process as in Figure 7 was performed up to electroless copper plating to remove the seed layer of the laminated structure, and a pattern substrate was fabricated. (DFR: RD-3015, manufactured by Resonaq, exposure machine: INPREX-4V2, manufactured by Adtec Engineering). The following steps were then carried out. (Electrolytic copper plating process) Composition and concentration Copper sulfate pentahydrate: 100 g / L 98% sulfuric acid: 200 g / L 35% hydrochloric acid: 0.15 g / L Toplutina FRV (copper sulfate plating additive manufactured by Okuno Pharmaceutical Co., Ltd.) Temperature and time 25°C, 45 minutes Current density 1.0 A / dm ２(Film thickness 10 μm) (Resist stripping process) The dry film resist was stripped by immersion in a 200 ml / L aqueous solution of resist stripping solution (trademark: OPC Parsory 312, manufactured by Okuno Pharmaceutical Co., Ltd.) at 65°C for 3 minutes. (Seed etching process) Spray etching was performed at 30°C for 3 minutes at 0.1 MPa using a mixed aqueous solution of seed etching solution (trademark: OPC Seed Etchant NE, manufactured by Okuno Pharmaceutical Co., Ltd.) at 300 ml / L and 100 ml / L of 35% hydrogen peroxide solution to form wiring, and the annealing (3) process shown in Figure 7 was performed. (Seed layer removalability evaluation) Elemental analysis was performed between the wirings using XPS (ULVAC-PHI, PHI 5000 Versa Probe III) on a patterned substrate (comb-tooth wiring with line width 10 μm and space width 10 μm). A score of ○ was used if the amount of metal elements in the interlayer was less than 0.1 at%, and a score of × was used if the amount of metal elements in the interlayer was 0.1 at% or more.

[0444] The results are shown in Table 9 below. The XPS analysis results are shown in Figure 16. These results indicate that the sample used in the example exhibits excellent adhesion and seed layer removal properties.

[0445]

[0446] The laminated structure of the present invention is useful for, for example, electrical and electronic products.

Claims

1. A laminated structure in which a plated film is formed on a substrate, wherein a 1.0 × 10 １０ A laminated structure characterized by comprising an interlayer made of tin oxide, titanium oxide, or zinc oxide having a surface resistivity of Ω / □ or higher as specified in JIS K 6911, wherein the thickness of the interlayer is 40 nm or more.

2. The laminated structure according to claim 1, wherein a reducing agent and a catalyst are included between the substrate and the interlayer film.

3. The laminated structure according to claim 2, wherein the catalyst comprises one or more precious metals.

4. The laminated structure according to claim 2, wherein the catalyst comprises silver and palladium.

5. The laminated structure according to claim 1, wherein a second catalyst is included between the interlayer and the plating film.

6. The laminated structure according to claim 5, further comprising a third catalyst and a reducing agent between the interlayer and the plating film.

7. A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure described in claim 1.

8. A laminated structure in which an electroless plating film and / or an electroplating film are laminated on a substrate via one or more interlayer films, wherein the interlayer film contains a metal oxide, the metal oxide contains two or more metal elements having a metallic bonding radius of 110 to 145 pm (picometers), and the thickness of the interlayer film is 40 nm or more.

9. The laminated structure according to claim 8, characterized in that the metal oxide contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

10. The laminated structure according to claim 8, characterized in that the metal oxide contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

11. The laminated structure according to claim 8, characterized in that the metal oxide contains two or more metal elements which are D-block elements.

12. The laminated structure according to claim 8, wherein the content of one of the metal elements is 60 at% or more relative to the total metal elements contained in the interlayer film.

13. The laminated structure according to claim 8, wherein the composition ratio of at least two of the two or more metal elements is inclined in the direction of the film thickness of the interlayer.

14. The laminated structure according to claim 8, comprising an electroless plating film, wherein the electroless plating film comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

15. The laminated structure according to claim 8, comprising an electroplated film, wherein the electroplated film comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

16. The laminated structure according to claim 8, wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

17. A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure described in claim 8.

18. A laminated structure comprising a first interlayer, a second interlayer, an electroless plating layer, and an electroplating layer laminated in this order on a substrate, wherein the first interlayer consists of a first metal oxide layer containing one type of metal element, the second interlayer consists of a second metal oxide layer containing two or more types of metal elements, and the thickness of the first interlayer is 40 nm or more.

19. The laminated structure according to claim 18, characterized in that the first interlayer contains a metal element having a metallic bonding radius of 110 to 145 pm (picometers).

20. The laminated structure according to claim 18, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 110 to 145 pm.

21. The laminated structure according to claim 18, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

22. The laminated structure according to claim 18, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

23. The laminated structure according to claim 18, characterized in that the second interlayer contains two or more metal elements that are D-block elements.

24. The laminated structure according to claim 18, wherein the electroless plating layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

25. The laminated structure according to claim 18, wherein the electroplated layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

26. The laminated structure according to claim 18, wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

27. A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure described in claim 18.

28. A laminated structure comprising a first interlayer, a second interlayer, an electroless plating layer, and an electroplating layer laminated in this order on a substrate, wherein the first interlayer consists of a first metal oxide layer containing one type of metal element, the second interlayer consists of a second metal oxide layer containing two or more types of metal elements, and the thickness of the second interlayer is 40 nm or more.

29. The laminated structure according to claim 28, characterized in that the first interlayer contains a metallic element having a metallic bonding radius of 110 to 145 pm (picometers).

30. The laminated structure according to claim 28, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 110 to 145 pm.

31. The laminated structure according to claim 28, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

32. The laminated structure according to claim 28, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

33. The laminated structure according to claim 28, characterized in that the second interlayer contains two or more metal elements that are D-block elements.

34. The laminated structure according to claim 28, wherein the electroless plating layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

35. The laminated structure according to claim 28, wherein the electroplated layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

36. The laminated structure according to claim 28, wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

37. A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure described in claim 28.

38. A laminated structure comprising a first interlayer, a second interlayer, an electroless plating layer, and an electroplating layer laminated in this order on a substrate, wherein the first interlayer consists of a first metal oxide layer containing one type of metal element, the second interlayer consists of a second metal oxide layer containing two or more types of metal elements, the ratio of the thickness of the first interlayer to the total thickness of the first and second interlayers is 30% or more, and the thickness of either the first or second interlayer is 40 nm or more.

39. The laminated structure according to claim 38, characterized in that the first interlayer contains a metal element having a metallic bonding radius of 110 to 145 pm (picometers).

40. The laminated structure according to claim 38, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 110 to 145 pm.

41. The laminated structure according to claim 38, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

42. The laminated structure according to claim 38, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

43. The laminated structure according to claim 38, characterized in that the second interlayer contains two or more metal elements that are D-block elements.

44. The laminated structure according to claim 38, wherein the electroless plating layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

45. The laminated structure according to claim 38, wherein the electroplated layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

46. ​​The laminated structure according to claim 38, wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

47. A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure described in claim 38.

48. A laminated structure comprising a first interlayer, a second interlayer, an electroless plating layer, and an electroplating layer laminated in this order on a substrate, wherein the first interlayer consists of a first metal oxide layer containing one type of metal element, the second interlayer consists of a second metal oxide layer containing two or more types of metal elements, the ratio of the thickness of the second interlayer to the total thickness of the first and second interlayers is 30% or more, and the thickness of either the first or second interlayer is 40 nm or more.

49. The laminated structure according to 48, characterized in that the first interlayer contains a metal element having a metallic bonding radius of 110 to 145 pm (picometers).

50. The laminated structure according to claim 48, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 110 to 145 pm.

51. The laminated structure according to claim 48, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 120 to 145 pm.

52. The laminated structure according to 48, characterized in that the second interlayer contains two or more metal elements having a metallic bonding radius of 125 to 145 pm.

53. The laminated structure according to claim 48, characterized in that the second interlayer contains two or more metal elements that are D-block elements.

54. The laminated structure according to claim 48, wherein the electroless plating layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

55. The laminated structure according to claim 48, wherein the electroplated layer comprises Cu, Ni, Ag, Pt, Rh, Ru, Pd, or Au.

56. The laminated structure according to claim 48, wherein the substrate is a glass substrate, a ceramic substrate, a silicon substrate, a resin substrate, or a metal substrate.

57. A product or component comprising a laminated structure, wherein the laminated structure is the laminated structure described in claim 48.

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