WO2021090893A1 - 導電性パターン付構造体及びその製造方法 - Google Patents
導電性パターン付構造体及びその製造方法 Download PDFInfo
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- WO2021090893A1 WO2021090893A1 PCT/JP2020/041415 JP2020041415W WO2021090893A1 WO 2021090893 A1 WO2021090893 A1 WO 2021090893A1 JP 2020041415 W JP2020041415 W JP 2020041415W WO 2021090893 A1 WO2021090893 A1 WO 2021090893A1
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- WIPO (PCT)
- Prior art keywords
- copper
- main surface
- conductive pattern
- surface side
- region
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- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
- H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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- C09D11/00—Inks
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- C23C18/1601—Process or apparatus
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
Definitions
- the present invention relates to a structure with a conductive pattern and a method for manufacturing the same.
- the circuit board has a structure in which conductive wiring is applied on the base material.
- the method for manufacturing a circuit board is generally as follows. First, a photoresist is applied on a base material to which a metal foil is bonded. Next, the photoresist is exposed and developed to obtain a negative shape of a desired circuit pattern. Next, the metal foil of the portion not covered with the photoresist is removed by chemical etching to form a pattern. This makes it possible to manufacture a high-performance circuit board.
- the conventional method has drawbacks such as a large number of steps, complexity, and the need for a photoresist material.
- a metallic film for example, copper fine particles and / or copper oxide particles
- a metallic film was used on the base material by applying the above paste material on the base material (as a support) and then firing the base material.
- a copper-containing film can be formed.
- silicon oxide colloidal silica as a base layer on a base material for the purpose of improving the adhesion between a support and a metallic film (see, for example, Patent Document 1).
- colloidal silica used for the base layer as described in Patent Document 1 has excellent adhesion to metal, but poor adhesion to resin. Therefore, when the material of the base material is resin, peeling may occur between the base layer and the base material due to the invasion of chemicals and thermal expansion, and the reliability of the product may be lowered. In addition, there is a drawback that the number of steps is increased due to the need for a step of applying colloidal silica on the base material.
- an object of the present invention is to provide a structure with a conductive pattern which can be obtained by a simple manufacturing process and has good interlayer adhesion, and a method for manufacturing the same.
- a structure with a conductive pattern comprising a base material and a conductive layer containing copper arranged on the surface of the base material.
- the conductive layer is said to be the same. It has a porosity of 0.01% by volume or more and 50% by volume or less in the region on the first main surface side from the first main surface to a depth of 100 nm in the thickness direction of the conductive layer, and is conductive from the second main surface.
- the conductivity according to the above aspect 1 or 2 wherein the elemental ratio of the oxygen atom to the copper atom in the first main surface side region is larger than the elemental ratio of the oxygen atom to the copper atom in the second main surface side region. Structure with sex pattern.
- a method for manufacturing a structure with a conductive pattern including. [11] The method for producing a structure with a conductive pattern according to the above aspect 10, further comprising a developing step of removing a laser beam unirradiated portion of the coating film between the irradiation step and the plating step. [12] The structure with a conductive pattern according to the above aspect 10 or 11, wherein the plating is performed by applying a plating solution having a copper concentration of 1.5 g / L or more and 5.0 g / L or less to the copper-containing film. Production method.
- the present embodiment will be described in detail for the purpose of exemplifying, but the present invention is not limited to the present embodiment.
- the present inventors have diligently studied a structure with a conductive pattern obtained by a simple manufacturing process and having good interlayer adhesion, and a manufacturing method thereof. As a result, it has been found that this characteristic can be achieved by the presence of a predetermined amount of voids in a predetermined region in the conductive layer.
- the structure with a conductive pattern of the present embodiment has excellent drug resistance and can also exhibit the effect that peeling due to thermal expansion is unlikely to occur.
- the conductive patterned structure 100 provides a conductive patterned structure comprising a substrate and a conductive layer containing copper arranged on the surface of the substrate.
- the conductive patterned structure 100 includes a base material 11 and a copper-containing conductive layer 12 arranged on the surface of the base material 11.
- the main surface of the conductive layer 12 facing the base material 11 is the first main surface S1 and the main surface opposite to the first main surface S1 is the second main surface S2.
- the conductive layer 12 has a porosity of 0.01% by volume or more and 50% by volume or less in the first main surface side region R1 from the first main surface S1 to a depth of 100 nm in the thickness direction of the conductive layer. It has a porosity of 10% by volume or less in the second main surface side region R2 from the second main surface S2 to a depth of 100 nm in the thickness direction of the conductive layer.
- the first main surface side region has a porosity of 0.01% by volume or more, the stress due to the expansion of copper can be relaxed, so that it can withstand thermal shock. Further, the fact that the first main surface side region has a porosity of 50% by volume or less means that the interlayer adhesion (more specifically, the adhesion between the base material and the conductive layer) is good. It is preferable in that peeling by a chemical does not easily occur and that the surface area is small and the oxidation resistance is good.
- the void ratio of the first main surface side region is preferably 0.05% by volume or more, more preferably 0.1% by volume or more, more preferably 0.15% by volume or more, and more preferably 0.2% by volume or more. More preferably 0.25% by volume or more, even more preferably 0.3% by volume or more, still more preferably 0.35% by volume or more, still more preferably 0.4% by volume or more, most preferably 0.5% by volume or more. Is. Further, preferably 45% by volume or less, more preferably 40% by volume or less, still more preferably 35% by volume or less, still more preferably 30% by volume or less, still more preferably 25% by volume or less, still more preferably 20% by volume or less. It is more preferably 15% by volume or less, further preferably 10% by volume or less, still more preferably 7% by volume or less, still more preferably 5% by volume or less, and most preferably 3% by volume or less.
- the second main surface side region has a porosity of 10% by volume or less, the interlayer adhesion (more specifically, the adhesion between the base material and the conductive layer) is good, and the drug is used. Is unlikely to peel off.
- the conductive layer has excellent oxidation resistance stability.
- the porosity of the second main surface side region is 0.0001% by volume or more, the stress due to the expansion of copper can be relaxed and the thermal shock can be withstood, which is preferable.
- the porosity is more preferably 0.0002% by volume or more, more preferably 0.0003% by volume or more, still more preferably 0.001% by volume or more, still more preferably 0.01% by volume or more, still more preferably 0. 05% by volume or more.
- the porosity is preferably 9% by volume or less, more preferably 8% by volume or less, further preferably 5% by volume or less, still more preferably 3% by volume or less, still more preferably 1 volume. % Or less, more preferably 0.5% by volume or less, and most preferably 0.1% by volume or less.
- the porosity in the first main surface side region can be controlled, for example, by adjusting the output and / or speed and / or wavelength of the irradiation laser used when forming the conductive layer. For example, the stronger the laser output and the slower the irradiation speed, the smaller the porosity of the first main surface side region, and the weaker the laser output and the faster the irradiation speed, the lower the porosity of the first main surface side region. growing.
- the porosity in the second main surface side region is determined by, for example, adjusting the degreasing step before plating and / or the plating temperature and / or the plating time and / or the composition of the plating solution and / or the copper concentration of the plating solution.
- the porosity of the second main surface side region is reduced.
- the porosity of the two regions, the first main surface side region and the second main surface side region can be set to a specific range.
- the porosity of the first main surface side region is larger than the porosity of the second main surface side region.
- the difference in porosity (unit: volume%) between the first main surface side region and the second main surface side region is preferably 0.05% by volume or more, or 0, from the viewpoint of excellent drug resistance. .1% by volume or more, or 0.2% by volume or more is preferable.
- the above difference may be, for example, 10% by volume or less, 5% by volume or less, or 1% by volume or less from the viewpoint of obtaining good interlayer adhesion.
- the porosity of the present disclosure is an index of the amount of voids present in the conductive layer.
- the void is a portion where the constituent material (more specifically, the conductive metal) of the conductive layer does not exist, and is typically an independent void (void V in FIG. 1) surrounded by a continuous phase of the constituent material.
- the porosity of the present disclosure was obtained by fusing the conductive layer to an epoxy resin, then performing FIB (focused ion beam) processing so that cross-sectional analysis by SEM (scanning electron microscope) is possible, and observing by SEM.
- FIB focused ion beam
- the major axis of the present disclosure is the maximum distance when any two points on the peripheral edge of one independent black portion are taken in the processed image.
- the porosity of the copper-containing film and the like, which will be described later, is also a value obtained from a cross-sectional image obtained by a scanning electron microscope (SEM) in the above procedure.
- the first main surface side region R1 is parallel to the first main surface S1 from the first main surface S1 of the conductive layer 12 (that is, the surface on the side facing the base material 11). It is a region up to the surface S1a, which is a surface moved inward by 100 nm in the thickness direction of the conductive layer. Further, the second main surface side region R2 is formed from the second main surface S2 of the conductive layer 12 (that is, the surface opposite to the base material 11) so as to be parallel to the second main surface S2. It is a region up to the surface S2a, which is a surface moved 100 nm inward of the conductive layer in the thickness direction.
- each surface (which may be an exposed surface or an interface with another member) of the members constituting the conductive patterned structure of the present disclosure is not limited, and may be a flat surface or a curved surface, for example, having a step or the like. You may.
- a region extending inward to 100 nm in the thickness direction of the conductive layer in parallel with each of these surfaces is first.
- the main surface side area and the second main surface side area are first.
- the first main surface side region preferably has a void with a major axis of 80 nm or less.
- the major axis is 78 nm or less, more preferably the major axis is 75 nm or less, and further preferably the major axis is 65 nm or less.
- the volume ratio of the voids having a major axis in the above range (major axis 80 nm or less in one embodiment) to the entire voids is preferably 0.1% or more, more preferably 0.2% or more, still more preferably 0. .3% or more.
- the volume ratio is preferably 99% or less, more preferably 98% or less, still more preferably 97% or less from the viewpoint of adhesion.
- the characteristic values (specifically, void ratio and element composition) of the present disclosure obtained by analyzing the cross section in the thickness direction of the conductive layer are as follows using SEM (scanning electron microscope) or STEM (scanning transmission electron microscope). It is obtained based on the first main surface S1 and the second main surface S2 on the cross section of the conductive layer defined as described above. That is, the first main surface S1 and the second main surface S2 on the cross section of the conductive layer are defined as follows according to the arithmetic mean roughness measurement of each of the actual first main surface and the second main surface. ..
- the arithmetic mean roughness is the measurement length of 2 ⁇ m arbitrarily selected for each of the first main surface and the second main surface in the cross section of the conductive layer in the thickness direction (the cross section can be observed in advance by FIB processing or the like). It is the arithmetic mean roughness obtained from the roughness curve obtained in the range of. In addition, the maximum height, the minimum height, and the average line are also obtained from the roughness curve.
- the first main surface S1 and the second main surface S2 on the cross section of the conductive layer are lines extending parallel to the average line and passing through the points giving the maximum height (when the arithmetic average roughness Ra is less than 1.0 ⁇ m). ) Or a line extending parallel to the average line passing through the point giving the minimum height (when the arithmetic mean roughness Ra is 1.0 ⁇ m or more).
- the arithmetic mean roughness of the second main surface is not particularly limited, but is preferably 10.0 ⁇ m or less, more preferably 9.0 ⁇ m or less, still more preferably 8.0 ⁇ m from the viewpoint of suppressing variation in the resistance value of the conductor. It is as follows.
- the elemental ratio of the oxygen atom to the copper atom in the first main surface region is larger than the elemental ratio of the oxygen atom to the copper atom in the second main surface region.
- the difference between the elemental ratio of oxygen atoms to copper atoms in the first main surface region and the elemental ratio of oxygen atoms to copper atoms in the second main surface region is preferably 0.001 or more, more preferably 0.003 or more, and more. It is preferably 0.005 or more, more preferably 0.01 or more.
- the above difference may be, for example, 0.60 or less, 0.55 or less, 0.50 or less, or 0.45 or less from the viewpoint of ease of forming the conductive layer.
- the elemental ratio of oxygen atoms to copper atoms in the first main surface side region is larger than 0.025.
- the elemental ratio of the oxygen atom to the copper atom in the first main surface side region is more preferably 0.026 or more, more preferably 0.027 or more, more preferably 0.028 or more, more preferably 0.03 or more, and more. It is preferably 0.05 or more, more preferably 0.06 or more, more preferably 0.07 or more, more preferably 0.08 or more, more preferably 0.09 or more, and even more preferably 0.10 or more.
- the element ratio may be, for example, 1.0 or less, 0.9 or less, or 0.8 or less from the viewpoint of ensuring good conductivity.
- the base material is a main member constituting the structure with a conductive pattern.
- the material of the base material is preferably a material having an insulating property in order to secure the electrical insulating property between the conductive patterns.
- the entire base material does not necessarily have to be a material having an insulating property, and it is sufficient if the portion constituting the surface on which the conductive layer is arranged has an insulating property.
- the surface of the base material on which the conductive layer is arranged may be a flat surface or a curved surface, or may be a surface including a step or the like.
- the conductive layer of the present embodiment can be satisfactorily formed on the base material, for example, as wiring, even when the surface of the base material is not flat.
- the substrate may be a substrate (eg, a plate, film or sheet), or a housing.
- the plate-shaped body is a support used for a circuit board such as a printed circuit board, for example.
- the film or sheet is, for example, a base film which is a thin film-like insulator used for a flexible printed circuit board.
- the housing has a three-dimensionally processed shape, and may have various shapes depending on the usage pattern.
- Examples of cases where the base material is a three-dimensional processed product include a housing of an electric device such as a mobile phone terminal, a smartphone, smart glasses, a television, and a personal computer.
- Other examples of three-dimensional objects include dashboards, instrument panels, handles, chassis, etc. in the field of automobiles.
- the material of the base material is not particularly limited and may be composed of an inorganic material or an organic material.
- the inorganic material examples include soda lime glass, non-alkali glass, borosilicate glass, glass such as quartz glass, and ceramic materials such as alumina.
- organic materials include polymer materials (resin film, paper, non-woven fabric, etc.).
- resin film examples include polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), etc.), polyether sulfone (PES), polycarbonate (PC), polyvinyl alcohol (PVA).
- PI polyimide
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PES polyether sulfone
- PC polycarbonate
- PVA polyvinyl alcohol
- the thickness of the substrate can be, for example, 1 ⁇ m to 10 mm, preferably 25 ⁇ m to 250 ⁇ m.
- the manufactured electronic device can be made lighter, space-saving, and flexible, which is preferable.
- Examples of paper include general paper made from pulp (high-quality paper, medium-quality paper, coated paper, cardboard, Western paper such as corrugated cardboard, etc.), paper made from cellulose nanofibers, and the like.
- a composite base material obtained by impregnating and curing or laminating a solution of a polymer material, a sol-gel material, or the like on paper can also be used.
- Examples thereof include a composite base material of paper and alumina, a composite base material of paper and low-temperature and low-humidity simultaneous firing ceramics (LTCC), and a composite base material of paper and a silicon wafer.
- the conductive layer is a layer containing copper (as a conductive metal).
- the conductive layer is, for example, a wiring, a metal layer of a heat dissipation sheet (for example, a sheet (that is, a solid metal film) or a mesh), or a metal layer of an electromagnetic wave shield (for example, a sheet or a mesh), an antenna.
- Etc. but are not particularly limited.
- the wiring is, for example, wiring for connecting a plurality of components arranged on a support, wiring for a printed board, wiring in an integrated circuit, wiring for connecting between electric devices or electronic devices (for example, wiring). , Wiring between a switch and a device such as a lighting, wiring between a sensor and an ECU (Electronic Control Unit), etc. in a vehicle such as an automobile), but is not particularly limited.
- the conductive layer 12 may have a third region R3 between the first main surface side region and the second main surface side region.
- at least a part of the third region may have the same characteristics as the first main surface side region or the second main surface side region.
- the same characteristic means that the value of the element ratio and / or the porosity is within ⁇ 3.0% of the value of the first main surface side region or the second main surface side region.
- the third region R3 is a region R31 (hereinafter, also simply referred to as a region R31) that is continuous with the first main surface side region R1 and has the same characteristics as the first main surface side region R1.
- a part R32 (hereinafter, also simply referred to as a part R2) which is continuous with the two main surface side area R2 and has the same characteristics as the second main surface side area R2, and another part R33 (hereinafter, also simply referred to as a part R33). Or may be occupied by site R31 and site R32. Further, the characteristics may be continuously changed from the site R31 to the site R33 and further toward the site 32.
- the first main surface side region and the second main surface side region can be formed by the method for manufacturing a structure with a conductive pattern, which will be described later, respectively.
- the site R31 can be formed at the same time as the formation of the first main surface side region R1.
- the site R32 can be formed at the same time as the formation of the second main surface side region R2.
- the concentration of each element in the conductive layer is determined by FIB (focused ion beam) processing in the sample so that cross-sectional analysis by STEM (scanning transmission electron microscope) is possible after solidifying the conductive layer on epoxy resin.
- FIB focused ion beam
- STEM scanning transmission electron microscope
- the element ratio in each of the first main surface side region and the second main surface side region can be controlled by, for example, the composition of the dispersion described later, the composition of the plating solution, and the like.
- the first main surface side region preferably contains copper (ie, unoxidized metallic copper) or is substantially composed of copper.
- the copper is a sintered body.
- the copper is reduced copper.
- the reduced copper means a sintered body obtained by reducing and sintering copper oxide. Reduced copper is advantageous in the adhesion between the base material and the conductive layer.
- Reduced copper can be formed by irradiating a coating film formed by coating a conductive layer material with laser light.
- the laser light irradiation may be performed by, for example, a light firing method.
- a desired conductive pattern can be formed by selectively irradiating only a part of the coating film with laser light.
- a flash light method and a laser light method using a discharge tube such as xenon as a light source can be applied.
- These methods are methods in which high-intensity light is exposed for a short time, and the copper oxide ink applied on the substrate is raised to a high temperature in a short time and fired.
- This is a method of forming a copper-containing film as a conductive film by converting and decomposing organic components. Since the firing time is very short, it can be applied to a resin film substrate or the like having low heat resistance by a method that causes less damage to the base material.
- the flash light method is a method that uses a xenon discharge tube to instantly discharge the electric charge stored in the capacitor. By generating a large amount of pulsed light and irradiating the copper oxide ink formed on the substrate. This is a method of instantly heating copper oxide to a high temperature to change it into a copper-containing film as a conductive film.
- the exposure amount can be adjusted by the light intensity, the light emission time, the light irradiation interval, and the number of times, and if the light transmission of the base material is large, the resin substrate having low heat resistance, for example, PET, PEN, paper, etc., can also be exposed. It is possible to form a conductive pattern with copper oxide ink.
- the thickness of the conductive layer is preferably 0.5 ⁇ m or more and 50 ⁇ m or less, and more preferably 1 ⁇ m or more and 35 ⁇ m or less.
- the conductive patterned structure may contain nickel and / or gold on the second main surface of the conductive layer.
- the inclusion of nickel and / or gold in the second main surface is preferable because oxidation of the conductive pattern can be prevented and soldering is improved.
- the content of nickel and / or gold is not particularly specified, but from the viewpoint of antioxidant, the total of nickel and gold is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably. From the viewpoint of 3% by mass or more, low internal stress and excellent adhesion, it is preferably 100% by mass or less, 99% by mass or less, or 98% by mass or less.
- the amount of nickel or gold on the second main surface is a value measured by the cross-section SEM-EDX method of the second main surface.
- the conductive patterned structure may further comprise a resin (such as resin 13 in FIG. 1).
- a resin such as resin 13 in FIG. 1.
- a resin layer is a sealing material layer.
- the resin layer can be formed by, for example, transfer molding, compression molding, photopolymerization, thermosetting, casting method or the like.
- the resin used include polypropylene (PP), polyimide (PI), polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutyl terephthalate (PBT), etc.), polyether sulfone (PES), and polycarbonate.
- PC polyvinyl alcohol
- PVA polyvinyl butyral
- POM polyacetal
- PA polyarylate
- PAI polyamide
- PEI polyetherimide
- PPE Polyphenylene ether
- m-PPE modified polyphenylene ether
- PPS polyphenylene sulfide
- PES polyether ketone
- PEEK polyether ether ketone
- PPA polyether nitrile
- BIO polybenzimidazole
- silicone polymer polysiloxane
- silicone polymer polysiloxane
- polymethacrylamide nitrile rubber
- acrylic rubber polyethylene tetrafluoride
- PMMA polymethyl methacrylate resin
- PMMA polymethyl methacrylate resin
- PMMA polymethyl methacrylate resin
- PMMA polymethyl methacrylate resin
- PMMA polymethyl methacrylate resin
- PMMA polymethyl methacrylate resin
- PMMA polymethyl methacrylate resin
- PMMA polymethyl methacryl
- the resin layer preferably contains a hydroxyl group.
- the hydroxyl group improves the adhesion to the copper foil.
- the preferable thickness of the resin layer is 0.1 ⁇ m or more and 1 mm or less, or 0.5 ⁇ m or more and 800 ⁇ m or less.
- the encapsulant layer protects the conductive pattern from external stress in the finished product (the structure with the conductive pattern itself and the product containing it) after production, and provides long-term stability of the structure with the conductive pattern. Can be improved.
- the moisture permeability of the encapsulant layer which is an example of the resin layer, is preferably 1.0 g / m 2 / day or less, more preferably 0.8 g / m 2 / day, from the viewpoint of ensuring good long-term stability. Hereinafter, it is more preferably 0.6 g / m 2 / day or less.
- the moisture permeability is a value measured by the cup method.
- the encapsulant layer can be a functional layer that imparts an oxygen barrier function to the structure with a conductive pattern even after the oxygen barrier layer used in manufacturing is peeled off, but as another function, the conductive pattern Scratch resistance when handling the attached structure, antifouling property to protect the conductive patterned structure from contamination from the outside, improved rigidity of the conductive patterned structure when a tough resin is used, etc. It may have a function.
- solder layer is formed on a part of the surface of the conductive layer, particularly a part of the second main surface.
- the solder layer can connect the conductive layer to other members.
- the solder layer can be formed, for example, by the reflow method.
- the solder layer is Sn-Pb system, Pb-Sn-Sb system, Sn-Sb system, Sn-Pb-Bi system, Bi-Sn system, Sn-Cu system, Sn-Pb-Cu system, Sn-In system, It may be a solder layer of Sn-Ag system, Sn-Pb-Ag system, Pb-Ag system or the like.
- the solder layer preferably contains a flux component.
- the flux component preferably contains an activator containing a carboxylic acid group.
- the solder layer may enter the voids of the conductive layer. By entering the solder layer into the voids of the conductive layer, the adhesion to the conductive layer is improved.
- the thickness of the solder layer is preferably 0.1 ⁇ m or more and 2 mm or less, and more preferably 0.5 ⁇ m or more and 1 mm or less.
- the method comprises a coating film forming step of applying a dispersion containing copper oxide particles to a substrate to obtain a coating film, a drying step of drying the coating film, and a coating film after the drying step. It includes an irradiation step of irradiating the copper-containing film with a laser beam to obtain a copper-containing film, and a plating step of plating the copper-containing film to form a conductive layer including the copper-containing film and the plating layer. In one aspect, a developing step of removing the unirradiated portion of the coating film from the laser beam may be further included between the irradiation step and the plating step.
- the reduced copper layer can be formed in a desired pattern by firing the coating film by laser irradiation, so that the productivity can be improved as compared with the conventional method using a photoresist. it can. Further, the reduced copper thus produced has a large surface area, and the growth rate of plating on the copper-containing film can be increased. Further, in one aspect, since the second main surface side region having a relatively low porosity can be formed by plating, the resistance of the conductive patterned structure can be reduced.
- reduced copper can be produced only by irradiating with laser light, so that a conventional mask or printing plate is not required, and it is easy for each product. You can change the pattern. Further, the method of the present embodiment has an advantage that wiring can be satisfactorily produced without restrictions on the shape of the base material (for example, even for a base material which is a three-dimensional object).
- preferred examples of each step will be described.
- a dispersion containing copper oxide particles (also referred to as copper oxide ink in the present disclosure) is applied to a base material to obtain a coating film.
- the dispersion contains copper oxide particles and a dispersion medium, and in one embodiment further contains a dispersant and / or a reducing agent.
- Copper oxide examples include cuprous oxide (Cu 2 O) and cupric oxide (Cu O), with cuprous oxide being preferred. Copper oxide is easy to reduce among metal oxides, it is easy to sintered in the form of fine particles, and because it is copper in terms of price, it is cheaper than precious metals such as silver, and migration. As the copper oxide, which is advantageous in that it is unlikely to occur, a commercially available product or a synthetic product may be used.
- a method for synthesizing cuprous oxide the following method can be mentioned.
- Water and a copper acetylacetonato complex are added to a polyol solvent to dissolve the organic copper compound by heating, then water necessary for the reaction is added afterwards, and the temperature is further raised to reduce the organic copper.
- a method of heating and reducing by heating with. (2) A method of heating an organic copper compound (for example, a copper-N-nitrosophenylhydroxyamine complex) at a high temperature of about 300 ° C. in an inert atmosphere in the presence of a protective agent such as hexadecylamine.
- a method of reducing a copper salt dissolved in an aqueous solution with hydrazine the method (3) is preferable because the operation is simple and cuprous oxide having a small average particle size can be obtained.
- Examples of the method for synthesizing cupric oxide include the following methods. (1) A method in which sodium hydroxide is added to an aqueous solution of cupric chloride or copper sulfate to generate copper hydroxide, and then heating is performed. (2) A method of thermally decomposing copper nitrate, copper sulfate, copper carbonate, copper hydroxide, etc. by heating them to a temperature of 600 ° C. in the air. Among these, the method (1) is preferable because cupric oxide having a small particle size can be obtained.
- the product solution and copper oxide are separated by a known method such as centrifugation.
- the dispersion medium described below and optionally the dispersant described below are added to the obtained copper oxide, and the mixture is stirred and dispersed by a known method such as a homogenizer.
- copper oxide may be difficult to disperse and the dispersion may be insufficient.
- alcohols for example, butanol
- Copper oxide can be satisfactorily dispersed in a desired dispersion medium by substituting with a desired dispersion medium and concentrating to a desired concentration. Examples of the method include concentration with a UF membrane, a method of repeating dilution and concentration with an appropriate dispersion medium, and the like.
- the copper oxide dispersion thus obtained is used for coating such as printing.
- the copper oxide is in the form of fine particles, and the average particle size thereof is preferably 3 nm or more and 50 nm or less, and more preferably 5 nm or more and 40 nm or less.
- the average particle size is the particle size at the time of dispersion in the dispersion, and is a value measured by the cumulant method using FPAR-1000 manufactured by Otsuka Electronics. That is, the average particle size is not limited to the primary particle size, but may be the secondary particle size.
- the average particle size is 50 nm or less, low-temperature firing is possible, the versatility of the base material is expanded, and a fine pattern tends to be easily formed on the base material, which is preferable.
- the size is 3 nm or more, the dispersion stability of the copper oxide particles in the dispersion is good, the long-term storage stability of the dispersion is good, and a uniform thin film can be produced, which is preferable.
- the mass ratio of copper oxide in 100% by mass of the dispersion is preferably 5% by mass or more, 10% by mass or more, or 15% by mass or more, and preferably 60% by mass or less, or 55% by mass or less. Or 50% by mass or less.
- the dispersion medium is one capable of dispersing copper oxide particles.
- the dispersion medium can dissolve the dispersant.
- the volatility of the dispersion medium affects workability. Therefore, it is preferable that the dispersion medium is suitable for a method for forming a conductive pattern, for example, a coating method (for example, printing). That is, it is preferable to select the dispersion medium according to the dispersibility and the workability of coating (printing, etc.).
- the dispersion medium examples include propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol.
- a monoalcohol having 10 or less carbon atoms is more preferable.
- the carbon number of the monoalcohol is further 8 or less from the viewpoint of suppressing the decrease in the dispersibility of copper oxide and from the viewpoint of more stably dispersing copper oxide in the interaction between the dispersion medium and the dispersant.
- the fact that the monoalcohol has 8 or less carbon atoms is also advantageous in terms of reducing the resistance value of the copper-containing film.
- monoalcohols having 8 or less carbon atoms ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, and t-butanol are dispersible, volatile, and viscous coatings. It is particularly suitable for and even more preferable. These monoalcohols may also be used alone or in admixture of a plurality of types.
- the content of the dispersion medium is preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass or more and 95% by mass or less, and most preferably 50% by mass or more and 90% by mass or less in the entire dispersion. ..
- the dispersant a compound capable of dispersing copper oxide in a dispersion medium can be used.
- the number average molecular weight of the dispersant is preferably 300 to 300,000, or 350 to 200,000, or 400 to 150,000.
- the number average molecular weight of the present disclosure is a value obtained in terms of standard polystyrene using gel permeation chromatography. When the number average molecular weight is 300 or more, the insulating property tends to be excellent and the contribution to the dispersion stability of the dispersion tends to be large, and when it is 300,000 or less, it is easily calcined in the irradiation step and is preferable.
- the dispersant preferably has a group having an affinity for copper oxide, and from this viewpoint, a phosphorus-containing organic compound is preferable, and a phosphoric acid group-containing organic compound is particularly preferable.
- a preferred example of a phosphorus-containing organic compound is a polymer phosphate ester.
- the phosphoric acid ester of the polymer for example, the following chemical formula (1):
- l is an integer from 1 to 10000
- m is an integer from 1 to 10000
- n is an integer from 1 to 10000.
- the structure represented by is preferable because it has excellent adsorptivity to copper oxide, particularly cuprous oxide, and adhesion to a substrate.
- l is more preferably 1 to 5000, still more preferably 1 to 3000.
- m is more preferably 1 to 5000, still more preferably 1 to 3000.
- n is more preferably 1 to 5000, still more preferably 1 to 3000.
- the phosphorus-containing organic substance is preferably easily decomposed or vaporized by light or heat in that a residue of the organic substance does not easily remain after firing and a conductive pattern having a low resistivity can be formed.
- the decomposition temperature of the phosphorus-containing organic substance is preferably 600 ° C. or lower, more preferably 400 ° C. or lower, and even more preferably 200 ° C. or lower.
- the decomposition temperature may be 50 ° C. or higher, 80 ° C. or higher, or 100 ° C. or higher from the viewpoint of facilitating the selection of a dispersant having an excellent effect of improving the dispersion stability of the dispersion.
- the boiling point of the phosphorus-containing organic substance is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, and even more preferably 150 ° C. or lower.
- the boiling point may be 30 ° C. or higher, 50 ° C. or higher, or 80 ° C. or higher.
- the decomposition temperature is a value measured by a thermogravimetric differential thermal analysis method.
- the phosphorus-containing organic substance can absorb the light used for firing copper oxide.
- a phosphorus-containing organic substance that absorbs light having a laser light emission wavelength (for example, 355 nm, 405 nm, 445 nm, 450 nm, 532 nm, and / or 1056 nm) is preferable.
- a phosphorus-containing organic substance that absorbs light having wavelengths of 355 nm, 405 nm, 445 nm, and / or 450 nm is preferable.
- a known dispersant may be used.
- examples thereof include polymers having a basic group such as a salt of a long-chain polyaminoamide and a polar acid ester, an unsaturated polycarboxylic acid polyaminoamide, a polycarboxylic acid salt of the polyaminoamide, and a salt of a long-chain polyaminoamide and an acid polymer.
- examples thereof include alkylammonium salts, amine salts and amidamine salts of polymers such as acrylic (co) polymers, modified polyester acids, polyether ester acids, polyether carboxylic acids and polycarboxylic acids.
- a commercially available one can also be used.
- Examples of the commercially available products include DISPERBYK (registered trademark) -101, DISPERBYK-102, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-118, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPER.
- DISPERBYK registered trademark
- the acid value (mgKOH / g) of the dispersant is preferably 20 or more and 130 or less, more preferably 30 or more and 100 or less.
- the acid value in the above range is effective.
- "DISPERBYK-102" (acid value 101), "DISPERBYK-140” (acid value 73), “DISPERBYK-142” (acid value 46), “DISPERBYK-145" (acid value 76) manufactured by Big Chemie. ), "DISPERBYK-118" (acid value 36), “DISPERBYK-180” (acid value 94) and the like are preferably mentioned.
- the difference between the amine value (mgKOH / g) of the dispersant and the acid value ([amine value]-[acid value]) is preferably -50 or more and 0 or less.
- the amine value indicates the total amount of the free base and the free base-derived site
- the acid value indicates the total amount of the free fatty acid and the free fatty acid-derived site.
- the amine value and acid value are measured by a method conforming to JIS K 7700 or ASTM D2074, respectively.
- the value of [amine value]-[acid value] is -50 or more and 0 or less, the dispersion stability of the dispersion is good, which is preferable.
- the value of [amine value]-[acid value] is more preferably -40 or more and 0 or less, and further preferably -20 or more and 0 or less.
- the content of the dispersant should be adjusted in proportion to the amount of copper oxide and in consideration of the required dispersion stability.
- the mass ratio of the dispersant to copper oxide in the dispersion is preferably 0.0050 or more and 0.30 or less, and more preferably 0.050 or more and 0.25 or less. , More preferably 0.10 or more and 0.23 or less.
- the amount of the dispersant affects the dispersion stability of the dispersion. When the amount is small, copper oxide tends to aggregate, and when the amount is large, the dispersion stability of the dispersion tends to be improved.
- the amount of the dispersant in 100% by mass of the dispersion is preferably 0.5% by mass or more, 0.8% by mass or more, or 1.0% by mass or more, preferably 35% by mass. % Or less, or 30% by mass or less, or 25% by mass or less.
- the dispersion may further contain a reducing agent.
- Reducing agents include hydrazine, hydrazine hydrate, sodium, sodium hydride, potassium iodide, sulfite, sodium thiosulfate, formic acid, oxalic acid, ascorbic acid, iron (II) sulfide, tin (II) chloride. , Diisobutylaluminum hydride, carbon and the like.
- Hydrazine and hydrazine hydrate are the most suitable reducing agents from the viewpoint of contributing to the reduction of copper oxide, especially cuprous oxide, and forming a reduced copper layer (as a copper-containing film) having lower resistance in the firing treatment. preferable. Hydrazine and hydrazine hydrate are also advantageous in maintaining the dispersion stability of the dispersion.
- the content of the reducing agent should be adjusted in proportion to the amount of copper oxide and in consideration of the required reducing property.
- the mass ratio of the reducing agent to copper oxide in the dispersion is preferably 0.0001 or more and 0.1 or less, more preferably 0.0001 or more and 0.05 or less. More preferably, it is 0.0001 or more and 0.03 or less.
- the mass ratio of the reducing agent is 0.0001 or more, the dispersion stability of the dispersion is good and the resistance of the reducing copper layer is low, which is preferable.
- the mass ratio is 0.1 or less, the dispersion is stable for a long period of time. Good sex.
- FIG. 2 is a schematic cross-sectional view showing the relationship between copper oxide and a phosphate ester salt in a dispersion (copper oxide ink) that can be used in one aspect of the present invention.
- the phosphate ester salt 23 is surrounded by the copper oxide 22. Surrounds the phosphorus 23a on the inside and the ester salt 23b on the outside.
- the phosphoric acid ester salt 23 exhibits electrical insulation, the electrical conduction between the copper oxides 22 adjacent to each other is hindered by the phosphoric acid ester salt 23. Further, the phosphoric acid ester salt 23 suppresses the aggregation of the copper oxide ink 200 due to the steric hindrance effect. Therefore, although the copper oxide 22 is a semiconductor (that is, has a certain degree of conductivity), it is covered with the phosphoric acid ester salt 23 which exhibits electrical insulation, so that the copper oxide ink 200 exhibits electrical insulation.
- the conductive pattern regions separated from each other by the copper oxide ink 200 can be insulated by the copper oxide ink 200.
- the copper oxide 22 is reduced to copper, and the copper oxides 22 that are adjacent to each other are fired and integrated. As a result, a conductive pattern region having excellent electrical conductivity is formed.
- the phosphorus element remains in the conductive pattern region.
- the phosphorus element exists as at least one of elemental phosphorus, phosphorus oxide and phosphorus-containing organic matter. However, since such residual phosphorus element is usually segregated and present in the conductive pattern region, there is no possibility that the resistance in the conductive pattern region will increase.
- a printing method such as screen printing, concave plate direct printing, concave plate offset printing, flexo printing, offset printing, inkjet printing, reverse transfer printing, or a dispenser drawing method can be used.
- the coating can be carried out by using a method such as die coating, spin coating, slit coating, bar coating, knife coating, spray coating, dip coating and the like.
- the layer thickness of the coating film after drying is preferably 1 nm or more and 10000 nm or less, more preferably 10 nm or more and 8000 nm or less, and further preferably 100 nm or more and 7000 nm or less in that a uniform reduced copper layer can be formed.
- the drying step is a step for vaporizing the dispersion medium.
- the dispersion medium may be vaporized at room temperature, or may be vaporized by a method such as oven or vacuum drying. Considering the heat resistance of the base material, it is preferable to dry at a temperature of 150 ° C. or lower, and more preferably at a temperature of 100 ° C. or lower.
- the coating film after the drying step is irradiated with laser light to obtain a copper-containing film.
- Copper oxide particles in the coating film can be reduced to generate copper, and a copper-containing film (reduced copper layer) can be formed by fusing and integrating the copper itself.
- the dispersion contains copper particles, fusion and integration of the copper particles and reduced copper also occur. As described above, the copper-containing film is formed.
- the wavelength of the laser light can be freely selected, and can be selected in consideration of the absorption wavelength of the dispersion and the base material. Further, according to the laser, exposure by beam scanning is possible, and it is easy to adjust the exposure range such as exposure to the entire surface of the base material or selection of partial exposure.
- YAG yttrium aluminum garnet
- YVO yttrium vanadate
- Yb ytterbium
- semiconductor laser GaAs, GaAlAs, GaInAs
- carbon dioxide gas etc.
- Harmonics may be taken out and used as needed.
- the central wavelength of the laser light is preferably 300 nm or more and 1500 nm or less.
- the center wavelength is 355 nm or more and 532 nm or less, these wavelengths are included in the absorption wavelength of the coating film containing copper oxide, which is preferable.
- the central wavelengths of the laser light are particularly preferably 355 nm, 405 nm, 445 nm, 450 nm, and 532 nm.
- the center wavelengths are preferably 355 nm and 532 nm.
- a desired void can be formed and a copper-containing film having a desired porosity can be easily produced.
- the porosity of the copper-containing film can be controlled by adjusting the output and speed of the laser that irradiates the coating film. For example, slowing down the scanning speed of the laser contributes to reducing the porosity.
- a part of the coating film is irradiated with laser light.
- the selective irradiation of the laser light is performed, for example, by irradiating the coating film with a light beam through a mask in the laser light method, and by directly drawing a desired pattern on the coating film by beam scanning in the laser light method. be able to.
- irradiation is preferably performed in a non-oxidizing atmosphere.
- the irradiation surface to which the laser beam is irradiated may be flat or not flat, and may be, for example, a housing in which the base material is a three-dimensional object.
- the unfired region may be removed with a suitable cleaning solution. In this case, only the fired region is left on the substrate. On the other hand, the unfired region may remain together with the fired region without performing the cleaning step. In either case, a base material to which conductivity is imparted by the firing region as the conductive pattern (hereinafter, also referred to as a conductive base material) can be obtained.
- a liquid that disperses or dissolves copper oxide can be used as the cleaning liquid for cleaning.
- Specific examples include water, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-butyl acetate, ethoxyethyl propionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol tascia.
- the above solvent is suitable because copper oxide can be washed off well, especially when the coating film contains a dispersant.
- a dispersant water, ethanol, butanol, i-propanol, and acetone are particularly preferable.
- a dispersant may be added to the above cleaning liquid.
- the dispersant those described above can be used, and more preferably a phosphorus-containing organic substance.
- the copper-containing film after the laser light irradiation step preferably has a porosity of 0.5% by volume or more.
- the porosity is more preferably 0.7% by volume or more, more preferably 1.0% by volume or more, more preferably 1.5% by volume or more, more preferably 2.0% by volume or more, and more preferably 2. 5% by volume or more.
- the porosity is preferably 60% by volume or less, more preferably 58% by volume or less, more preferably 55% by volume or less, and more preferably 53% by volume or less. , More preferably 51% by volume or less.
- the method of the present disclosure may further include a degreasing step of degreasing the copper-containing film.
- the degreasing method include a UV method and a wet degreasing method.
- the degreasing step increases the subsequent growth rate of plating and improves productivity.
- this step contributes to the reduction of the porosity of the conductive layer after plating, that is, the final porosity of the conductive layer.
- the degreasing step is preferably performed by immersing the conductive base material in a degreasing solution containing a compound containing an amino group.
- Compounds containing an amino group include amino acids such as alanine, arginine, asparagine, cysteine, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine, and methylamine.
- Examples thereof include aminosulfonic acids such as taurine, aminothiols such as 2-aminoethanethiol, and nitrogen-containing heterocyclic compounds such as 3-picorylamine and 3-pyridinemethanol.
- 2-Aminoethanol is particularly preferable from the viewpoint of contributing to the growth rate of plating.
- the degreasing solution may be a commercially available product. Specifically, ALC-009 of Uemura Kogyo Co., Ltd. (including 2-aminoethanol as a compound having an amino group) and Cleaner Securigant 902 of Atotech Japan Co., Ltd. (Amino). Examples of the compound having a group include 2-aminoethanol) and the like.
- the concentration of the compound containing an amino group in the degreasing solution is preferably 5 mmol / L or more, more preferably 10 mmol / L or more, and more preferably 20 mmol / L or more from the viewpoint of removing the inhibitor of the plating reaction. Further, from the viewpoint of accelerating the plating reaction, 100 mmol / L or less is preferable, 90 mmol / L or less is more preferable, and 80 mmol / L is more preferable.
- the immersion time of the conductive base material in the degreasing liquid is preferably 1 minute or more, more preferably 2 minutes or more from the viewpoint of contributing to the growth rate of plating. Further, from the viewpoint of reducing damage to the base material, 15 minutes or less is preferable, and 10 minutes or less is more preferable. Immersion under stirring is preferable from the viewpoint of uniform degreasing.
- the immersion temperature is preferably 15 ° C. or higher, more preferably 30 ° C. or higher, and even more preferably 40 ° C. or higher in order to enhance the effect of promoting the growth rate of plating. Further, from the viewpoint of reducing damage to the base material, 70 ° C. or lower is preferable, and 60 ° C. or lower is more preferable.
- the cleaning liquid is preferably 15 ° C. or higher, more preferably 20 ° C. or higher. Further, from the viewpoint of reducing damage to the base material, 70 ° C. or lower is preferable, and 60 ° C. or lower is more preferable.
- the copper-containing film that has undergone or has not undergone the degreasing step is plated.
- electrolytic plating or non-electrolytic plating on the copper-containing film (reduced copper layer) of the conductive base material obtained as described above, a plating layer having a desired layer thickness (for example, a plated copper layer) is formed.
- a conductive pattern composed of a reduced copper layer and a plating layer is obtained. As a result, a structure with a conductive pattern can be manufactured.
- Electrolytic plating is more preferable from the viewpoint of wide applicability to patterns.
- electroless plating is preferable for wiring in which a pattern is produced by a laser.
- a general electroplating method can be applied to electrolytic plating. For example, in a solution containing copper ions (plating bath), an electrode is placed on one side and a conductive base material to be plated is placed on the other side. Then, a direct current is applied between the electrode and the conductive base material from the external direct current power source. A current can be applied to the reduced copper layer by connecting a jig (for example, a clip) connected to one electrode of an external DC power supply to the reduced copper layer on the conductive base material. As a result, copper is deposited on the surface of the reduced copper layer on the conductive substrate by the reduction of copper ions, and a plated copper layer is formed.
- a jig for example, a clip
- a copper sulfate bath for example, a copper sulfate bath, a borofluorinated copper bath, a copper cyanide bath, and a pyrophosphate bath can be used. From the viewpoint of safety and productivity, a copper sulfate bath and a pyrophosphate bath are preferable.
- the copper sulfate plating bath for example, a copper sulfate acidic copper sulfate plating bath containing copper sulfate pentahydrate, sulfuric acid and chlorine is preferably used.
- the concentration of copper sulfate pentahydrate in the copper sulfate plating bath is preferably 50 g / L to 300 g / L, more preferably 100 g / L to 200 g / L.
- the concentration of sulfuric acid is preferably 40 g / L to 160 g / L, more preferably 80 g / L to 120 g / L.
- the solvent for the plating bath is usually water.
- the temperature of the plating bath is preferably 20 to 60 ° C, more preferably 30 to 50 ° C.
- the current density during the electrolytic treatment is preferably 1 to 15 A / dm 2 , and more preferably 2 to 10 A / dm 2 .
- the copper pyrophosphate plating bath for example, a plating bath containing copper pyrophosphate and potassium pyrophosphate is suitable.
- the concentration of copper pyrophosphate in the copper pyrophosphate plating bath is preferably 60 g / L to 110 g / L, and more preferably 70 g / L to 90 g / L.
- the concentration of potassium pyrophosphate is preferably 240 g / L to 470 g / L, and more preferably 300 g / L to 400 g / L.
- the solvent for the plating bath is usually water.
- the pH of the plating bath is preferably 8.0 to 9.0, more preferably 8.2 to 8.8. Ammonia water or the like may be added to adjust the pH value.
- the temperature of the plating bath is preferably 20 to 60 ° C, more preferably 30 to 50 ° C.
- the current density during the electrolytic treatment is preferably 0.5 to 10 A / dm 2 , and more preferably 1 to 7 A / dm 2 .
- the plating bath for electrolytic plating may further contain a surfactant.
- a general electroless plating method can be applied to electroless plating.
- electroless plating is performed together with a degreasing step or a cleaning step.
- a plating solution containing copper ions and a reducing agent can be used as the electroless plating bath.
- the copper ions in the plating solution are reduced, copper is deposited on the surface of the reduced copper layer, and the plated copper layer is formed.
- Examples of the electroless plating bath include CuSO 4 as a copper ion source, EDTA (ethylenediaminetetraacetic acid) or Rochelle salt as a complexing agent, formaldehyde (CH 2 O) as a reducing agent, potassium tetrahydroate, dimethylamine borane, and glioxylic acid.
- a plating solution containing phosphinic acid can be used.
- Commercially available products include Sulcup PEA-6 and Sulcup ELC-SP from Uemura Kogyo Co., Ltd., Melplate CU-390 and Melplate CU-5100P from Meltex Inc., OPC Copper HFS and OPC Copper NCA from Okuno Pharmaceutical Co., Ltd.
- a plating solution is used for electroless plating.
- the plating solution preferably contains EDTA (ethylenediaminetetraacetic acid). Since EDTA functions as a complexing agent and forms a highly stable complex with copper ions, it suppresses side reactions in the plating bath, stabilizes the bath, and promotes plating precipitation uniformly, thereby forming a coating film. It is considered that it contributes to the prevention of peeling.
- the amount of EDTA in the plating solution is preferably 7 g / L or more, 10 g / L or more, or 15 g / L or more from the viewpoint of obtaining the advantages of EDTA well, and reduces impurities in the plating precipitate. From the viewpoint of lowering the electrical resistance, it is preferably 50 g / L or less, 45 g / L or less, or 40 g / L or less.
- the temperature of the electrolysis-free plating bath is preferably 25 to 80 ° C, and more preferably 30 ° C to 70 ° C or 35 ° C to 65 ° C because faster plating growth can be expected.
- the plating time is preferably 5 to 60 minutes, more preferably 5 to 50 minutes, and even more preferably 10 to 40 minutes.
- the plating bath for electroless plating may further contain a surfactant.
- Electrolytic plating is preferably performed using a plating solution having a copper concentration in the range of 1.5 g / L or more and 5.0 g / L or less.
- a concentration of 1.5 g / L or more is preferable in order to improve the plating speed, and a concentration of 5.0 g / L or less is preferable from the viewpoint of uniformity of the plating film.
- the copper concentration is more preferably 1.5 g / L or more and 4.0 g / L or less, still more preferably 1.8 g / L or more and 3.5 g / L or less, still more preferably 2.0 g / L or more and 3.0 g //. It is L or less.
- the cleaning liquid is preferably 15 ° C. or higher, more preferably 20 ° C. or higher. Further, from the viewpoint of reducing damage to the base material, 70 ° C. or lower is preferable, and 60 ° C. or lower is more preferable.
- the thickness of the plated layer is preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 1 ⁇ m or more and 50 ⁇ m or less, in that the current required for the conductive patterned structure can be passed. More preferably, it is 2 ⁇ m or more and 30 ⁇ m or less.
- the porosity of the region on the first main surface side of the copper-containing film after laser light irradiation can be reduced.
- the rate of decrease in the porosity of the first main surface side region can be controlled by adjusting the composition of the plating solution, the plating time, and the plating temperature. For example, increasing the plating time contributes to reducing the porosity of the copper-containing film.
- the reduction rate at this time is also affected by the above-mentioned degreasing step. For example, lengthening the degreasing time in the degreasing step contributes to reducing the porosity of the copper-containing film.
- the reduction rate of the porosity is preferably 1.0% by volume or more, more preferably 1.5% by volume or more, further preferably 2.0% by volume or more, and more preferably 2.0% by volume or more, from the viewpoint of improving the conductivity of the copper-containing film. 50% by volume or less is preferable from the viewpoint of preventing peeling of the conductive layer due to the stress accompanying the decrease.
- the second main surface side region of the conductive layer is a plated copper layer formed by the above-mentioned plating step.
- the porosity of the second main surface side region can be controlled by the plating conditions. For example, increasing the plating time contributes to reducing the porosity of the plating layer.
- the third region when the third region is formed so that at least a part of the above-mentioned third region has the same characteristics as the first main surface side region, for example, laser light irradiation conditions and / or By controlling the plating conditions, the porosity of the copper-containing film can be changed to a desired range, and the porosity of the first main surface side region and the third region can be controlled to a desired range. Further, in one embodiment, when the third region is formed so that at least a part of the above-mentioned third region has the same characteristics as the second main surface side region, the plating conditions are controlled.
- the porosity of the copper-containing film can be changed to a desired range and the porosity of the plating layer can be adjusted to control the porosity of the second main surface side region and the third region to a desired range.
- the porosity of the first main surface side region, the second main surface side region, and the third main surface side region can be controlled within a desired range by optimizing the conditions of the series of steps of laser light irradiation, degreasing, and plating described above.
- a portion having a porosity of the first main surface side region (for example, when at least a part of the third region has a porosity similar to that of the first main surface side region, the portion is also included. ) Is preferably 0.001 to 10 ⁇ m, more preferably 0.01 to 8 ⁇ m, and even more preferably 0.1 to 7 ⁇ m. Further, a portion having a porosity of the second main surface side region (for example, when at least a part of the third region has a porosity similar to that of the second main surface side region, the portion is also included) (typically.
- the preferred thickness of the plated copper layer is as described above as the layer thickness of the plated copper layer, that is, preferably 1 ⁇ m or more and 100 ⁇ m or less, more preferably 1 ⁇ m or more and 50 ⁇ m or less, and further preferably 2 ⁇ m or more and 30 ⁇ m or less. ..
- the coating film is selectively irradiated with laser light, a part of the coating film is selectively fired, and copper oxide is reduced to copper.
- FIG. 3H a single layer was formed on the base material in which an insulating region containing copper oxide and a dispersant and a reduced copper layer containing copper were arranged adjacent to each other. A conductive substrate is obtained.
- the insulating region containing copper oxide and the dispersant may be removed using an appropriate developer. This process is called a developing process. In this case, only the fired region (that is, the reduced copper layer) can be left on the base material. After cleaning, as shown in FIG. 3 (j), a conductive base material in which only the reduced copper layer is left on the base material is obtained.
- the developer contains a solvent that is an organic solvent or water or a mixture thereof, and a dispersant.
- the organic solvent is one or more selected from the group consisting of alcohols, ketones, esters and ethers.
- the coating components of the dry coating film can be satisfactorily dispersed in the developer due to the contribution of the dispersant, so that alcohols, ketones and esters can be used.
- Good development can be achieved even with a solvent system such as an organic solvent selected from the group consisting of and ether and / or water that does not easily damage the metal wiring and the base material.
- a solvent system such as an organic solvent selected from the group consisting of and ether and / or water that does not easily damage the metal wiring and the base material.
- the solvent may be one kind or a combination of two or more kinds, preferably containing a polar solvent, and more preferably composed of a polar solvent.
- the polar solvent is particularly advantageous in terms of developability because it has excellent dispersibility of copper oxide particles.
- the solvent contained in the developer (which may be one or a combination of two or more) is preferably at least one of the dispersion media (which may be one or a combination of two or more) contained in the dispersion. It contains the same kind of compound as, or is composed of the same kind of compound as the dispersion medium.
- Examples of the alcohol include methanol, ethanol, propanol, butanol, isopropyl alcohol, normal propyl alcohol, tertiary butanol, butandiol, ethylene glycol, glycerin and the like.
- ketone examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and the like.
- ester examples include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like.
- ether examples include diethyl ether, diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 1,4 diethylene oxide, vinyl ethylene carbonate, tetrahydrofuran and the like.
- the solvent in the developer preferably contains one or more selected from the group consisting of water, ethanol, propanol, butanol, and isopropyl alcohol, and is composed of one or more of them, because the polarity can be increased. Is particularly preferable.
- the developer contains a dispersant.
- the dispersant can efficiently disperse (that is, efficiently remove) the copper oxide particles adhering to the substrate in the developing solution.
- the dispersant those described above are preferable as the dispersant that can be contained in the dispersion of the present disclosure.
- the examples of suitable compounds for the dispersant in the developer are the same as the examples of suitable compounds for the dispersant described above in the section on dispersants.
- the content of the dispersant in the developing solution is preferably 0.1% by mass or more in that the copper oxide particles adhering to the substrate can be efficiently dispersed (that is, efficiently removed) in the developing solution.
- the conductive base material is immersed in a degreasing liquid containing a compound containing an amino group, and a degreasing step is performed.
- a plated copper layer is formed on the reduced copper layer.
- ⁇ Evaluation method> Hydrazine was quantified by the standard addition method. To 50 ⁇ L of the sample (dispersion), 33 ⁇ g of hydrazine, 33 ⁇ g of a surrogate substance (hydrazine 15 N 2 H 4 ), and 1 ml of a 1 mass% acetonitrile solution of benzaldehyde were added. Finally, 20 ⁇ L of phosphoric acid was added, and after 4 hours, GC / MS measurement was performed.
- the mass of the added hydrazine / the mass of the added surrogate substance was taken on the x-axis, and the peak area value of hydrazine / the peak area value of the surrogate substance was taken on the y-axis to obtain a calibration curve by the standard addition method.
- the value of the Y-intercept obtained from the calibration curve was divided by the mass of the added hydrazine / the mass of the added surrogate substance to obtain the mass of hydrazine.
- the average particle size of the dispersion was measured by the cumulant method using FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
- the threshold value at the time of binarization was determined by the determination method "Isodata" incorporated in the software. Then, the profile was quantified using the Analyze line graph, the roughness curve was extracted, and the maximum height, the minimum height, the average line, and the arithmetic average roughness Ra were obtained. Since the arithmetic mean roughness in each example and comparative example was less than 1.0 ⁇ m, the first main surface on the cross section of the conductive layer was defined as a line extending through the point giving the maximum height and parallel to the average line. The second main surface on the cross section of the conductive layer was defined as a line extending through the point giving the maximum height and parallel to the average line. Porosity measurement and elemental analysis were performed based on the first and second main surfaces on the cross section of the conductive layer defined above.
- the area of the void was calculated by Analyze Practicle.
- the major axis of the void was measured as the maximum distance when any two points were taken at the periphery of each independent black portion in the processed image.
- the element ratio was measured by EDX analysis in the same observation range.
- Adhesion evaluation tape peeling test
- the adhesiveness of the structure with a conductive pattern was evaluated by peeling at 90 ° using OPP tape 618 for light packaging manufactured by 3M Co., Ltd. The evaluation was performed with 1 point for complete peeling, 2 points for peeling an area larger than 50% and less than 100% of the conductive pattern area, and 3 points for peeling 0% or more and 50% or less.
- Stress relaxation The structure with a conductive pattern was bent at 90 ° to evaluate its stress relaxation property. The evaluation was performed with 1 point for complete peeling, 2 points for peeling an area larger than 50% and less than 100% of the conductive pattern area, and 3 points for peeling 0% or more and 50% or less.
- the structure with a conductive pattern was immersed in 0.1 M hydrochloric acid and then washed with water.
- the resistance value before and after the treatment is measured, and the ratio of the resistance value after the treatment to that before the treatment is 3 points when it is less than 110%, 2 points when it is 110% or more and less than 150%, and 1 point when it is 150% or more. Evaluation was performed.
- the resistance was measured using the 4-terminal method.
- Example 1 806 g of cupric acetate (II) monohydrate (manufactured by Kanto Chemical Co., Inc.) was dissolved in a mixed solvent of 7560 g of distilled water (manufactured by Kyoei Pharmaceutical Co., Ltd.) and 3494 g of 1,2-propylene glycol (manufactured by Kanto Chemical Co., Inc.). The liquid temperature was adjusted to -5 ° C by an external temperature controller. Add 235 g of hydrazine monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) over 20 minutes and stir for 30 minutes in a nitrogen atmosphere, then bring the liquid temperature to 25 ° C with an external temperature controller and stir for 90 minutes in a nitrogen atmosphere. did.
- II cupric acetate
- the dispersion was well dispersed and the average particle size was 21 nm.
- the amount of hydrazine was 3000 mass ppm.
- the obtained dispersion was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and held in an oven at 90 ° C. for 2 hours to volatilize the solvent in the coating film to prepare a sample. I got 1.
- the coating film thickness of the obtained sample 1 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.5 ⁇ m and the porosity was 11.7% by volume in the first main surface side region.
- the resistance value of the conductive pattern region was 30 ⁇ cm.
- the sample 1 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry it at room temperature.
- the resistance value of the conductive layer which is the laminated portion of the conductive pattern region and the plated copper layer, was measured by the 4-terminal measurement method and found to be 7.3 ⁇ cm. It has been shown that the resistance value is low enough to form an electrical circuit.
- the porosity was 1.0% by volume in the first main surface side region and 0.06% by volume in the second main surface side region, and the elemental composition was the first main surface side region.
- Example 2 The dispersion obtained in the same manner as in Example 1 was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and kept in an oven at 90 ° C. for 2 hours in the coating film. Sample 2 was obtained by volatilizing the solvent of. The coating film thickness of the obtained sample 2 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.5 ⁇ m and the porosity was 40% by volume in the first main surface side region.
- the resistance value of the conductive pattern region was 50 ⁇ cm.
- the sample 2 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry it at room temperature.
- the porosity was 1.6% by volume in the first main surface side region and 0.6% by volume in the second main surface side region, and the elemental composition was the first main surface side.
- Example 3 The dispersion obtained in the same manner as in Example 1 was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and kept in an oven at 90 ° C. for 2 hours in the coating film. The solvent of No. 3 was volatilized to obtain Sample 3. The coating film thickness of the obtained sample 3 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.5 ⁇ m and the porosity was 11.7% by volume in the first main surface side region.
- the resistance value of the conductive pattern region was 30 ⁇ cm.
- the sample 3 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry it at room temperature.
- the porosity was 5.4% by volume in the first main surface side region and 0.9% by volume in the second main surface side region, and the elemental composition was on the first main surface side.
- Example 4 The dispersion obtained in the same manner as in Example 1 was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and kept in an oven at 90 ° C. for 2 hours in the coating film. The solvent of No. 4 was volatilized to obtain Sample 4. The coating film thickness of the obtained sample 4 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.5 ⁇ m and the porosity was 35% by volume in the first main surface side region.
- the resistance value of the conductive pattern region was 45 ⁇ cm.
- the sample 4 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry it at room temperature.
- the porosity was 23.4% by volume in the first main surface side region and 0.9% by volume in the second main surface side region, and the elemental composition was on the first main surface side.
- Example 5 The dispersion obtained in the same manner as in Example 1 was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and kept in an oven at 90 ° C. for 2 hours in the coating film. The solvent of No. 5 was volatilized to obtain Sample 5. The coating film thickness of the obtained sample 5 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.5 ⁇ m and the porosity was 40% by volume in the first main surface side region.
- the resistance value of the conductive pattern region was 50 ⁇ cm.
- the sample 5 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry it at room temperature.
- the porosity was 27.2% by volume in the first main surface side region and 0.9% by volume in the second main surface side region, and the elemental composition was on the first main surface side.
- Example 6 The dispersion obtained in the same manner as in Example 1 was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and kept in an oven at 90 ° C. for 2 hours in the coating film. Sample 6 was obtained by volatilizing the solvent of. The coating film thickness of the obtained sample 6 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.6 ⁇ m and the porosity was 45% by volume in the first main surface side region.
- the resistance value in the conductive pattern region was 53 ⁇ cm.
- the sample 6 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry it at room temperature.
- the porosity was 34.3% by volume in the first main surface side region, 3.1% by volume in the second main surface side region, and the elemental composition was the first main surface side.
- Example 7 The dispersion obtained in the same manner as in Example 1 was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and kept in an oven at 90 ° C. for 2 hours in the coating film. Sample 7 was obtained by volatilizing the solvent of. The coating film thickness of the obtained sample 7 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.5 ⁇ m and the porosity was 22% by volume in the first main surface side region.
- the resistance value of the conductive pattern region was 35 ⁇ cm.
- the sample 7 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry at room temperature.
- a treatment liquid prepared by dissolving ACL-009 of Uyemura & Co., Ltd. in water so as to be 50 mL / L was heated to 50 ° C., and sample 7 was immersed for 5 minutes. After the treatment, the sample 7 was taken out and washed with water.
- a pulseless plating treatment liquid C. Uyemura & Co., Ltd.'s Sulcup PEA-6 ver. 3 was used and treated at 33 ° C. for 30 minutes. The thickness of the formed plated copper layer was about 1.0 ⁇ m.
- the electrolytic plating copper layer was laminated on the plated copper layer by further performing electrolytic plating on the above sample.
- An electrolytic plating solution M-1 manufactured by Kiyokawa Plating Industry Co., Ltd. was used as the electrolytic plating solution, and a current value of 0.01 A was passed for 5 minutes for treatment.
- the thickness of the laminated copper was about 1.0 ⁇ m.
- the porosity was 6.4% by volume in the first main surface side region and 9.8% by volume in the second main surface side region, and the elemental composition was the first main surface side.
- Example 8> Using a copper paste with an average particle size of 5 ⁇ m, apply it to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by bar coating, and hold it in an oven at 90 ° C. for 2 hours to volatilize the solvent in the coating film. Sample 8 was obtained. The coating film thickness of the obtained sample 8 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.8 ⁇ m and the porosity was 53.2% by volume in the first main surface side region.
- the resistance value in the conductive pattern region was 122 ⁇ cm.
- the porosity was 2.2% by volume in the first main surface side region and 1.8% by volume in the second main surface side region, and the elemental composition was the first main surface side.
- ⁇ Comparative example 1> A PET substrate was placed in the vacuum chamber and evacuated to a back pressure of 8 ⁇ 10-Pa.
- the copper vapor deposition source temperature was set to 1350 ° C., and vacuum deposition was performed at a vapor deposition rate of 1 ⁇ / sec.
- the copper film thickness after vapor deposition was 500 nm.
- the copper film was a vapor-deposited film, so that the first main surface had no voids.
- Example 2 The dispersion obtained in the same manner as in Example 1 was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and kept in an oven at 90 ° C. for 2 hours in the coating film. Sample 10 was obtained by volatilizing the solvent of. The coating film thickness of the obtained sample 10 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.5 ⁇ m and the porosity was 11.7% by volume in the first main surface side region.
- the resistance value of the conductive pattern region was 30 ⁇ cm.
- the sample 10 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry it at room temperature.
- the electrolytic plated copper layer was laminated by subjecting the above sample to electrolytic plating.
- An electrolytic plating solution M-1 manufactured by Kiyokawa Plating Industry Co., Ltd. was used as the electrolytic plating solution, and a current value of 0.1 A was passed for 10 minutes for treatment.
- the thickness of the laminated copper was about 10 ⁇ m.
- the porosity was 11.7% by volume in the first main surface side region and 50.9% by volume in the second main surface side region, and the elemental composition was the first main surface side.
- Example 3 The dispersion obtained in the same manner as in Example 1 was applied to a polyimide film (manufactured by Toray DuPont, Kapton 500H, thickness 125 ⁇ m) by a spin coating method, and kept in an oven at 90 ° C. for 2 hours in the coating film. The solvent of No. 11 was volatilized to obtain Sample 11. The coating film thickness of the obtained sample 11 was 1000 nm.
- the desired size of 0.5 mm ⁇ 5 mm can be obtained.
- a conductive pattern region (copper-containing film) containing copper was obtained.
- a coating film remained in the area not irradiated with the laser beam.
- the thickness was 0.5 ⁇ m and the porosity was 11.7% by volume in the first main surface side region.
- the resistance value of the conductive pattern region was 30 ⁇ cm.
- the sample 11 in which the conductive pattern region was formed was immersed in ultrapure water and shaken for 1 minute, then immersed in ethanol and shaken for 1 minute to wash away the uncalcined region and dry it at room temperature.
- Example 2 the dispersion obtained in the same manner as in Example 1 was applied to the above sample by the spin coating method, and held in an oven at 90 ° C. for 2 hours to volatilize the solvent in the coating film. It was fired in a plasma firing device at 1.5 kW for 240 seconds with a pressure of 140 Pa and a small amount of a mixed gas of 3% hydrogen / 97% nitrogen (v / v) flowing. Through the above procedure, a structure with a conductive pattern according to Comparative Example 3 was obtained.
- the porosity was 6,4% by volume in the first main surface side region, 12.9% by volume in the second main surface side region, and the elemental composition was the first main surface side.
- Table 1 shows the results of porosity evaluation, oxygen atomic weight evaluation, adhesion evaluation (tape peeling test), stress relaxation property evaluation, drug resistance evaluation, and oxidation stability evaluation of each sample of Examples and Comparative Examples. .. Adhesion evaluation, stress relaxation evaluation, drug resistance evaluation, and oxidative stability evaluation were each given a score of 1 to 3, and the total score is also shown in the table.
- the present invention is not limited to the above-described embodiments and examples. Design changes and the like may be added to the above-described embodiments and examples based on the knowledge of those skilled in the art, and the above-mentioned embodiments and examples may be arbitrarily combined, and such changes and the like are added. Aspects are also included in the scope of the present invention.
- the present invention can be suitably applied to the manufacture of printed wiring boards, antennas, electronic devices, electromagnetic wave shields, antistatic films and the like.
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Abstract
Description
[1] 基材と、前記基材の表面に配置された、銅を含む導電性層とを備える導電性パターン付構造体であって、
前記導電性層の、前記基材に対向する側の主面を第1主面、前記第1主面と反対側の主面を第2主面としたときに、前記導電性層が、前記第1主面から導電性層厚み方向深さ100nmまでの第1主面側領域において0.01体積%以上50体積%以下の空隙率を有しており、かつ前記第2主面から導電性層厚み方向深さ100nmまでの第2主面側領域において10体積%以下の空隙率を有している、導電性パターン付構造体。
[2] 前記第1主面側領域における空隙率が前記第2主面側領域における空隙率よりも大きい、上記態様1に記載の導電性パターン付構造体。
[3] 前記第1主面側領域における銅原子に対する酸素原子の元素比が、前記第2主面側領域における銅原子に対する酸素原子の元素比よりも大きい、上記態様1又は2に記載の導電性パターン付構造体。
[4] 前記第1主面側領域における銅原子に対する酸素原子の元素比が、0.025よりも大きい、上記態様1~3のいずれかに記載の導電性パターン付構造体。
[5] 前記第2主面にニッケル及び/又は金を含む、上記態様1~4のいずれかに記載の導電性パターン付構造体。
[6] 前記導電性層の一部が樹脂で覆われている、上記態様1~5のいずれかに記載の導電性パターン付構造体。
[7] 前記導電性層の表面の一部に配置されたハンダ層を更に備える、上記態様1~6のいずれかに記載の導電性パターン付構造体。
[8] 前記導電性層がアンテナである、上記態様1~7のいずれかに記載の導電性パターン付構造体。
[9] 前記導電性層がプリント基板の配線である、上記態様1~8のいずれかに記載の導電性パターン付構造体。
[10] 酸化銅粒子を含む分散体を基材に塗布して、塗布膜を得る塗布膜形成工程と、
前記塗布膜を乾燥する乾燥工程と、
前記乾燥工程後の塗布膜にレーザー光を照射して、銅含有膜を得る照射工程と、
前記銅含有膜にめっきを行って、前記銅含有膜とめっき層とを含む導電性層を得るめっき工程と、
を含む、導電性パターン付構造体の製造方法。
[11] 前記照射工程と前記めっき工程との間に、前記塗布膜のレーザー光未照射部を除去する現像工程を更に含む、上記態様10に記載の導電性パターン付構造体の製造方法。
[12] 銅濃度1.5g/L以上5.0g/L以下のめっき液を前記銅含有膜に適用することによって前記めっきを行う、上記態様10又は11に記載の導電性パターン付構造体の製造方法。
本発明の一態様は、基材と、該基材の表面に配置された、銅を含む導電性層とを備える導電性パターン付構造体を提供する。図1を参照し、本発明の一態様に係る導電性パターン付構造体100は、基材11と、基材11の表面に配置された、銅を含む導電性層12とを備える。一態様においては、導電性層12の基材11に対向する側の主面を第1主面S1、該第1主面S1と反対側の主面を第2主面S2としたときに、導電性層12が、第1主面S1から導電性層厚み方向深さ100nmまでの第1主面側領域R1において0.01体積%以上50体積%以下の空隙率を有しており、かつ第2主面S2から導電性層厚み方向深さ100nmまでの第2主面側領域R2において10体積%以下の空隙率を有している。
基材は導電性パターン付構造体を構成する主な部材である。基材の材質は、導電性パターン間の電気絶縁性を確保するため、絶縁性を有する材料であることが好ましい。ただし、必ずしも基材の全体が絶縁性を有する材料である必要はなく、導電性層が配置される面を構成する部分が絶縁性を有する材料であれば足りる。
導電性層は、銅(導電性金属として)を含む層である。導電性層は、例えば配線、放熱シートの金属層(例えば、シート状(すなわち金属のベタ膜)、又はメッシュ状)、又は、電磁波シールドの金属層(例えば、シート状、又はメッシュ状)、アンテナ等であってよいが、特に限定されない。ここで、配線は、例えば、支持体上に配置された複数の部品間を繋ぐための配線、プリント基板の配線、集積回路内の配線、電気機器又は電子機器の間を繋ぐための配線(例えば、自動車等の乗り物において、スイッチと照明等の機器との間の配線、センサとECU(Electronic Control Unit)との間の配線)等であってよいが、特に限定されない。
一態様において、導電性パターン付構造体は樹脂(図1中の樹脂13のような)を更に含んでよい。一態様においては、導電性層の一部が樹脂で覆われていることが好ましい。導電性層の一部が樹脂で覆われていることにより、導電性パターンの酸化が防止され、信頼性が向上する。また、導電性層に樹脂で覆われていない部分が存在することで、部品を電気的に接合することができる。
一態様において、導電性層の表面の一部、特に第2主面の一部にハンダ層が形成されていることが好ましい。ハンダ層によって導電性層と他の部材とを接続できる。ハンダ層は例えばリフロー法によって形成できる。ハンダ層は、Sn-Pb系、Pb-Sn-Sb系、Sn-Sb系、Sn-Pb-Bi系、Bi-Sn系、Sn-Cu系、Sn-Pb-Cu系、Sn-In系、Sn-Ag系、Sn-Pb-Ag系、Pb-Ag系等のハンダ層であってよい。ハンダ層はフラックス成分を含むことが好ましい。フラックス成分はカルボン酸基を含む活性剤を含んでいることが好ましい。この構成により、導電性層とハンダ層との密着性が高くなる。一態様において、導電性層の空隙部にハンダ層が入り込んでいてもよい。導電性層の空隙部にハンダ層が入り込むことにより、導電性層との密着性が向上する。ハンダ層の厚みは、好ましくは0.1μm以上2mm以下、より好ましくは0.5μm以上1mm以下である。
本発明の一態様は、導電性パターン付構造体の製造方法を提供する。一態様において、当該方法は、酸化銅粒子を含む分散体を基材に塗布して、塗布膜を得る塗布膜形成工程と、該塗布膜を乾燥する乾燥工程と、該乾燥工程後の塗布膜にレーザー光を照射して、銅含有膜を得る照射工程と、銅含有膜にめっきを行って、銅含有膜とめっき層とを含む導電性層を形成するめっき工程とを含む。一態様においては、照射工程とめっき工程との間に、塗布膜のレーザー光未照射部を除去する現像工程を更に含んでよい。
以下、各工程の好適例について説明する。
本工程では、酸化銅粒子を含む分散体(本開示で、酸化銅インクともいう。)を基材に塗布して、塗布膜を得る。
分散体(酸化銅インク)は、酸化銅粒子と分散媒とを含み、一態様においては、分散剤及び/又は還元剤を更に含む。
酸化銅としては、酸化第一銅(Cu2O)及び酸化第二銅(CuO)が挙げられるが、酸化第一銅が好ましい。酸化第一銅は、金属酸化物の中でも還元が容易であり、微粒子形状での焼結が容易であり、価格的にも銅であるがゆえに銀等の貴金属類と比較し安価であり、マイグレーションが生じ難い点で有利である、酸化銅としては、市販品又は合成品を用いてよい。
(1)ポリオール溶剤中に、水と銅アセチルアセトナト錯体を加え、いったん有機銅化合物を加熱溶解させ、次に、反応に必要な水を後添加し、さらに昇温して有機銅の還元温度で加熱して加熱還元する方法。
(2)有機銅化合物(例えば銅-N-ニトロソフェニルヒドロキシアミン錯体)を、ヘキサデシルアミン等の保護剤存在下、不活性雰囲気中で、300℃程度の高温で加熱する方法。
(3)水溶液に溶解した銅塩をヒドラジンで還元する方法。
この中では(3)の方法は操作が簡便で、かつ、平均粒子径の小さい酸化第一銅が得られるので好ましい。
(1)塩化第二銅又は硫酸銅の水溶液に水酸化ナトリウムを加えて水酸化銅を生成させた後、加熱する方法。
(2)硝酸銅、硫酸銅、炭酸銅、水酸化銅等を空気中で600℃の温度に加熱して熱分解する方法。
この中で(1)の方法は粒子径が小さい酸化第二銅が得られるので好ましい。
分散媒は、酸化銅粒子を分散させることができるものである。一態様において、分散媒は、分散剤を溶解させることができる。酸化銅インクを用いて導電性パターンを形成するという観点から、分散媒の揮発性が作業性に影響を与える。したがって、分散媒は、導電性パターンの形成方法、例えば塗布の方式(例えば印刷等)に適するものであることが好ましい。すなわち、分散媒は分散性と塗布(印刷等)の作業性とに合わせて選択することが好ましい。
分散剤としては、酸化銅を分散媒中に分散させることができる化合物を使用できる。分散剤の数平均分子量は、300~300,000、又は350~200,000、又は400~150,000であることが好ましい。なお本開示の数平均分子量は、ゲルパーミエーションクロマトグラフィを用い標準ポリスチレン換算で求められる値である。数平均分子量が300以上であると、絶縁性に優れ、分散体の分散安定性への寄与も大きい傾向があり、300,000以下であると、照射工程において容易に焼成され好ましい。分散剤は、酸化銅に対する親和性を有する基を有していることが好ましく、この観点から、リン含有有機化合物が好ましく、リン酸基含有有機化合物が特に好ましい。リン含有有機化合物の好適例はポリマーのリン酸エステルである。ポリマーのリン酸エステルとして、例えば、下記化学式(1):
で示される構造は、酸化銅、特に酸化第一銅への吸着性、及び基材への密着性に優れるため、好ましい。
化学式(1)中、lは、より好ましくは1~5000、更に好ましくは1~3000である。
化学式(1)中、mは、より好ましくは1~5000、更に好ましくは1~3000である。
化学式(1)中、nは、より好ましくは1~5000、更に好ましくは1~3000である。
分散体は、還元剤を更に含んでよい。還元剤としては、ヒドラジン、ヒドラジン水和物、ナトリウム、水素化ホウ酸ナトリウム、ヨウ化カリウム、亜硫酸塩、チオ硫酸ナトリウム、蟻酸、シュウ酸、アスコルビン酸、硫化鉄(II)、塩化スズ(II)、水素化ジイソブチルアルミニウム、カーボン等が挙げられる。焼成処理において、酸化銅、特に酸化第一銅の還元に寄与し、より抵抗の低い還元銅層(銅含有膜として)を形成する観点から、還元剤としては、ヒドラジン及びヒドラジン水和物が最も好ましい。ヒドラジン及びヒドラジン水和物は、分散体の分散安定性の維持においても有利である。
図2は、本発明の一態様で使用できる分散体(酸化銅インク)における酸化銅とリン酸エステル塩との関係を示す断面模式図である。図2を参照し、本発明の一態様において、酸化銅インク200が、酸化銅22とリン酸エステル塩23(分散剤として)とを含む場合、酸化銅22の周囲を、リン酸エステル塩23が、リン23aを内側に、エステル塩23bを外側にそれぞれ向けて取り囲んでいる。リン酸エステル塩23は電気絶縁性を示すため、互いに隣接する酸化銅22間の電気的導通は、リン酸エステル塩23によって妨げられている。また、リン酸エステル塩23は、立体障害効果により酸化銅インク200の凝集を抑制している。したがって、酸化銅22は半導体である(すなわちある程度の導電性を有する)が、電気絶縁性を示すリン酸エステル塩23で覆われているので、酸化銅インク200は電気絶縁性を示す。このような酸化銅インク200で互いに隔てられた導電性パターン領域は、酸化銅インク200によって絶縁されていることができる。
分散体の塗布方法としては、スクリーン印刷、凹版ダイレクト印刷、凹版オフセット印刷、フレキソ印刷、オフセット印刷、インクジェット印刷、反転転写印刷等の印刷法、又はディスペンサー描画法等を用いることができる。塗布は、ダイコート、スピンコート、スリットコート、バーコート、ナイフコート、スプレーコート、ディツプコート等の方法を用いて実施できる。
本工程では、塗布膜形成工程で得た塗布膜を乾燥させる。乾燥工程は分散媒を気化させるための工程である。分散媒は、室温で気化させてもよいし、オーブン、真空乾燥等の方法で気化させてもよい。基材の耐熱性を考慮すると、150℃以下の温度で乾燥させることが好ましく、100℃以下の温度で乾燥させることがさらに好ましい。
本工程では、乾燥工程後の塗布膜にレーザー光を照射して、銅含有膜を得る。塗布膜中の酸化銅粒子を還元して銅を生成させ、銅自体の融着及び一体化により銅含有膜(還元銅層)を形成することができる。分散体が銅粒子を含む場合は当該銅粒子と還元された銅との融着及び一体化も生じる。以上のようにして、銅含有膜が形成される。
レーザー照射後、未焼成領域は、適切な洗浄液を用いて除去してもよい。この場合、基材の上に焼成領域だけが残される。一方、洗浄工程を行わず、焼成領域とともに未焼成領域を残存させてもよい。いずれの場合も、導電性パターンとしての焼成領域によって導電性が付与された基材(以下、導電性基材ともいう。)が得られる。
本開示の方法は、一態様において、銅含有膜を脱脂する脱脂工程を更に含んでもよい。脱脂方法としては、UV法、湿式脱脂法等が挙げられる。脱脂工程により、その後のめっきの成長速度が速くなり、生産性が向上する。また、本工程は、めっき後の導電性層の空隙率低減、すなわち、最終的な導電性層の空隙率に寄与する。
本工程では、脱脂工程を経た又は経ていない銅含有膜にめっきを行う。上述のようにして得られた導電性基材の銅含有膜(還元銅層)上に電解めっき又は無電解めっきを施すことで、所望の層厚のめっき層(例えばめっき銅層)を形成し、還元銅層及びめっき層で構成された導電性パターンを得る。この結果、導電性パターン付構造体を製造することができる。
第1主面側領域の空隙率の減少率=[(銅含有膜形成直後の第1主面側領域の空隙率)-(めっき工程後の第1主面側領域の空隙率)]/[銅含有膜形成直後の第1主面側領域の空隙率]
で求められる値である。
例えば、空隙率の減少率は、銅含有膜の導電性向上の観点から、1.0体積%以上が好ましく、1.5体積%以上がより好ましく、2.0体積%以上がさらに好ましく、空隙減少に伴う応力によって導電性層のはがれが発生することを防ぐ観点から50体積%以下が好ましい。
以下、図3を参照して、導電性パターン付構造体の製造方法のより具体的な好適例を説明する。
図3(a)に示す塗布膜形成工程において、水とプロピレングリコール(PG)との混合溶媒中に酢酸銅を溶かし、ヒドラジンを加えて攪拌する。
次いで、図3(b)及び(c)に示すように、生成物溶液(上澄み)と酸化第一銅(沈殿物)とを遠心分離する。
次いで、図3(d)に示すように、沈殿物に、分散剤及びアルコールを加え、沈殿物を分散させる。
次いで、図3(e)及び(f)に示すように、酸化銅を含む分散体を、スプレーコート法等によって基材上に塗布し、酸化銅及び分散剤を含む塗布膜を形成する。
次いで、図3(l)に示すように、還元銅層上にめっき銅層を形成する。
以上の手順で、導電性パターン付構造体を製造できる。
[ヒドラジン定量方法]
標準添加法によりヒドラジンの定量を行った。
サンプル(分散体)50μLに、ヒドラジン33μg、サロゲート物質(ヒドラジン15N2H4)33μg、ベンズアルデヒド1質量%アセトニトリル溶液1mlを加えた。最後にリン酸20μLを加え、4時間後、GC/MS測定を行った。
分散体の平均粒子径は、大塚電子製FPAR-1000を用いてキュムラント法によって測定した。
(第1主面及び第2主面の画定)
導電性層をエポキシ樹脂に固結した後、SEM(走査型電子顕微鏡)による断面分析が可能となるようにFIB(集束イオンビーム)加工し、SEM断面観察に供した。観察は5万倍の倍率で行った。試料中の導電性層部分について、第1主面及び第2主面の各々の、任意に選択した測定長2μmの範囲で画像処理ソフトImageJを用い、平滑化後にコントラスト調整を行い、8bit化後、Smoothでスムージング、MedianFilter(Radius;3pixels)を実施した。その後、Thresholdによる2値化を実行した。2値化の際の閾値は、ソフト上に組み込まれている判定方法、「Isodata」により決定した。その後、Analyze line graphを用いてプロファイルを数値化し、粗さ曲線を抽出し、最大高さ、最小高さ、平均線及び算術平均粗さRaを求めた。各実施例及び比較例における算術平均粗さは1.0μm未満であったため、導電性層断面上の第1主面は、最大高さを与える点を通りかつ平均線と平行に延びる線として画定し、導電性層断面上の第2主面は、最大高さを与える点を通りかつ平均線と平行に延びる線として画定した。上記で画定した導電性層断面上の第1主面及び第2主面に基づいて、空隙率測定及び元素分析を行った。
第1主面から導電性層厚み方向深さ100nmまでの範囲、及び第2主面から導電性層厚み方向深さ100nmまでの範囲のそれぞれにおける、2μm×100nmの長方形の観察範囲(観察倍率5万倍)において、NIH(米国国立衛生研究所)のImageJソフトによってSEMによって得られた画像を8bit化後、Smoothでスムージング、MedianFilter(Radius;4pixels)を実施した。その後、Thresholdによる2値化を実行した。2値化の際の閾値は、ソフト上に組み込まれている判定方法、「Triangle法」により決定した。空隙部の面積はAnalyze Practicleにより算出した。なお空隙の長径は、上記処理後の画像において、各々の独立した黒色部分の周縁における任意の2点を取ったときの最大距離として測定した。
また、同じ観察範囲で、EDX分析により元素比を測定した。
装置:S4700(日立ハイテク)
二次電子像(SE)観察時;加速電圧 1kV
EDX分析時;加速電圧 5kV
上記のSEM断面像より厚みを算出した。
抵抗計(ADVANTEST社製のAD7461A)を用い、4端子測定法によって測定した。
導電性パターン付構造体について、スリーエム株式会社の軽包装用OPPテープ618を用いて、90°剥離にて密着性を評価した。完全剥離の場合を1点、導電性パターン面積のうち50%より大きく100%未満の面積が剥離した場合を2点、0%以上50%以下が剥離した場合を3点として評価を行った。
導電性パターン付構造体について、90°の折り曲げを行い、応力緩和性を評価した。完全剥離の場合を1点、導電性パターン面積のうち50%より大きく100%未満の面積が剥離した場合を2点、0%以上50%以下が剥離した場合を3点として評価を行った。
導電性パターン付構造体について、0.1Mの塩酸に浸漬した後、水洗を行った。処理前後の抵抗値を測定し、抵抗値の処理前に対する処理後の比率が110%未満の場合を3点、110%以上150%未満の場合を2点、150%以上の場合を1点として評価を行った。抵抗の測定は4端子法を用いた。
導電性パターン付構造体について、大気下で80℃加熱を5時間行った。処理前後の抵抗値を測定し、抵抗値の処理前に対する処理後の比率が110%未満の場合を3点、110%以上150%未満の場合を2点、150%以上の場合を1点として評価を行った。抵抗の測定は4端子法を用いた。
蒸留水(共栄製薬株式会社製)7560g、1,2-プロピレングリコール(関東化学株式会社製)3494gの混合溶媒中に酢酸銅(II)一水和物(関東化学株式会社製)806gを溶かし、外部温調器によって液温を-5℃にした。ヒドラジン一水和物(東京化成工業株式会社製)235gを20分間かけて加え、窒素雰囲気中で30分間攪拌した後、外部温調器によって液温を25℃にし、窒素雰囲気中で90分間攪拌した。攪拌後、遠心分離で上澄みと沈殿物に分離した。得られた沈殿物390gに、DISPERBYK-145(ビッグケミー製、リン酸基含有有機化合物)13.7g(分散剤含有量4g)及びエタノール(関東化学株式会社製)907gを加え、窒素雰囲気中でホモジナイザーを用いて分散し、酸化第一銅を含む分散体1365gを得た。
実施例1と同様にして得られた分散体を、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にスピンコート法によって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料2を得た。得られた試料2の塗布膜厚は1000nmであった。
実施例1と同様にして得られた分散体を、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にスピンコート法によって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料3を得た。得られた試料3の塗布膜厚は1000nmであった。
実施例1と同様にして得られた分散体を、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にスピンコート法によって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料4を得た。得られた試料4の塗布膜厚は1000nmであった。
実施例1と同様にして得られた分散体を、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にスピンコート法によって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料5を得た。得られた試料5の塗布膜厚は1000nmであった。
実施例1と同様にして得られた分散体を、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にスピンコート法によって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料6を得た。得られた試料6の塗布膜厚は1000nmであった。
実施例1と同様にして得られた分散体を、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にスピンコート法によって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料7を得た。得られた試料7の塗布膜厚は1000nmであった。
平均粒子径5μmの銅ペーストを用い、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にバーコートによって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料8を得た。得られた試料8の塗布膜厚は1000nmであった。
真空チャンバー内にPET基板を設置し、背圧8×10-Paまで真空引きした。銅の蒸着源温度を1350℃に設定し、1Å/秒の蒸着速度で真空蒸着した。蒸着後の銅膜厚は、500nmであった。以上の手順で、比較例1に係る導電性パターン付構造体を得た。
実施例1と同様にして得られた分散体を、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にスピンコート法によって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料10を得た。得られた試料10の塗布膜厚は1000nmであった。
実施例1と同様にして得られた分散体を、ポリイミドフィルム(東レ・デュポン社製、カプトン500H、厚み125μm)にスピンコート法によって塗布し、90℃のオーブンで2時間保持して塗布膜内の溶媒を揮発させて試料11を得た。得られた試料11の塗布膜厚は1000nmであった。
11 基材
12 導電性層
13 樹脂
200 酸化銅インク
22 酸化銅
23 リン酸エステル塩
23a リン
23b エステル塩
R1 第1主面側領域
R2 第2主面側領域
R3 第3の領域
R31 第1主面側領域R1と同様の特性を有する部位
R32 第2主面側領域R2と同様の特性を有する部位
R33 その他の部位
S1 第1主面
S2 第2主面
S1a,S2a 面
V ボイド
Claims (12)
- 基材と、前記基材の表面に配置された、銅を含む導電性層とを備える導電性パターン付構造体であって、
前記導電性層の、前記基材に対向する側の主面を第1主面、前記第1主面と反対側の主面を第2主面としたときに、前記導電性層が、前記第1主面から導電性層厚み方向深さ100nmまでの第1主面側領域において0.01体積%以上50体積%以下の空隙率を有しており、かつ前記第2主面から導電性層厚み方向深さ100nmまでの第2主面側領域において10体積%以下の空隙率を有している、導電性パターン付構造体。 - 前記第1主面側領域における空隙率が前記第2主面側領域における空隙率よりも大きい、請求項1に記載の導電性パターン付構造体。
- 前記第1主面側領域における銅原子に対する酸素原子の元素比が、前記第2主面側領域における銅原子に対する酸素原子の元素比よりも大きい、請求項1又は2に記載の導電性パターン付構造体。
- 前記第1主面側領域における銅原子に対する酸素原子の元素比が、0.025よりも大きい、請求項1~3のいずれか一項に記載の導電性パターン付構造体。
- 前記第2主面にニッケル及び/又は金を含む、請求項1~4のいずれか一項に記載の導電性パターン付構造体。
- 前記導電性層の一部が樹脂で覆われている、請求項1~5のいずれか一項に記載の導電性パターン付構造体。
- 前記導電性層の表面の一部に配置されたハンダ層を更に備える、請求項1~6のいずれか一項に記載の導電性パターン付構造体。
- 前記導電性層がアンテナである、請求項1~7のいずれか一項に記載の導電性パターン付構造体。
- 前記導電性層がプリント基板の配線である、請求項1~8のいずれか一項に記載の導電性パターン付構造体。
- 酸化銅粒子を含む分散体を基材に塗布して、塗布膜を得る塗布膜形成工程と、
前記塗布膜を乾燥する乾燥工程と、
前記乾燥工程後の塗布膜にレーザー光を照射して、銅含有膜を得る照射工程と、
前記銅含有膜にめっきを行って、前記銅含有膜とめっき層とを含む導電性層を得るめっき工程と、
を含む、導電性パターン付構造体の製造方法。 - 前記照射工程と前記めっき工程との間に、前記塗布膜のレーザー光未照射部を除去する現像工程を更に含む、請求項10に記載の導電性パターン付構造体の製造方法。
- 銅濃度1.5g/L以上5.0g/L以下のめっき液を前記銅含有膜に適用することによって前記めっきを行う、請求項10又は11に記載の導電性パターン付構造体の製造方法。
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