US20040104118A1 - Method for manufacturing very low roughness electrodeposited copper foil and electrodeposited copper foil manufactured thereby - Google Patents
Method for manufacturing very low roughness electrodeposited copper foil and electrodeposited copper foil manufactured thereby Download PDFInfo
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- US20040104118A1 US20040104118A1 US10/720,579 US72057903A US2004104118A1 US 20040104118 A1 US20040104118 A1 US 20040104118A1 US 72057903 A US72057903 A US 72057903A US 2004104118 A1 US2004104118 A1 US 2004104118A1
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- copper foil
- electrodeposited copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
Definitions
- the present invention relates to a method for manufacturing an electrodeposited copper foil adhered to a prepreg for a PCB(Printed Circuit Board) and an electrodeposited copper foil manufactured thereby, and in particular to a method for manufacturing an electrodeposited copper foil which does not have a residual copper by decreasing a roughness of a matte side of an electrodeposited copper foil even when a fine pattern is formed.
- a PCB is widely used in a home appliance such as a radio, television, washing machine, VCR, etc., and an industrial electric/electronic instrument such as a computer, wireless communication instrument, various controllers, etc.
- the PCB is formed of an insulated substrate such as a prepreg of a frame retardant formed in such a manner that a glass fiber is impregnated in foil is adhered to an insulation substrate at a high temperature and pressure, and then the electrodeposited copper foil is etched based on a circuit design.
- the electrodeposited copper foil adhered to the insulation substrate is manufactured by the following processes.
- a raw foil is manufactured in a copper sulphate solution by a continuous electrodepositing method.
- a nodule process is performed with respect to a raw copper foil for forming a copper nodule for thereby enhancing an adhesion to an insulation substrate and a barrier layer is formed on the copper foil surface.
- a corrosion resist chromating process is performed.
- a first method is to divide an electrolytic section into two sections and then to enhance a current density of a second section rather than a first section for thereby obtaining a low roughness copper foil.
- a super anode is attached to a foil manufacturing apparatus of the above manufacturing facility.
- the super anode is adapted, it is possible to change the size of a nucleus when a nucleus is initially generated by adjusting the current applied to the super anode and the main anode. Therefore, it is possible to manufacture the low roughness copper foil by accurately adjusting the size of the initial nucleus. However, it is impossible to manufacture a low roughness copper foil corresponding to the recent fine circuit pattern with the above described method.
- a second method is directed to decreasing the concentration of a chloride ion in an electrolyte below 1 ppm for thereby obtaining a low roughness copper foil.
- concentration of a chloride ion below 1ppm based on only an experimental condition.
- a copper scrap is generally used as a source material.
- the copper scrap is used for the mass production system, there is no suitable economic method for preventing a chloride ion generated by a waste electric wire. Therefore, it is impossible to implement an actual practicality.
- a third method is directed to obtaining a low roughness copper foil by mechanically polishing a conventional electrodeposited copper foil through a buffing method.
- the above method is needed to have an additional manufacturing facility. If there is a surplus during the buffing process, a residual copper may be formed during the manufacture of the PCB.
- a fourth method is directed to adjusting morphology of a copper foil by changing an additive added to an electrolyte.
- the above fourth method is directed to implementing a low roughness copper foil by adding a low molecular weight water-soluble cellulose ether, a low molecular weight water-soluble polyalkylene glycol ether, a low molecular weight water-soluble polyethyleneimine, and a water soluble sulfonated organic sulfur compound.
- a mechanical polishing process like a buffing process is not needed. It is not needed to manage a chloride ion at a very low degree.
- the above method is more economical compared to the other methods.
- the copper foil manufactured by the above method has a roughness Rz of a matte side of 3.81 ⁇ m, the above method does not satisfy the demand of the recent low roughness copper foil.
- a fifth method is directed to manufacturing a low roughness copper foil using an electrolyte including a small amount of polyethylene glycol, tin ion, iron ion and a chloride ion of below 0.1 ppm.
- an electrolyte including a small amount of polyethylene glycol, tin ion, iron ion and a chloride ion of below 0.1 ppm.
- an electrodeposited copper foil in which a rotating drum and an anode plate formed of a curve distanced from an outer surface of the drum by a certain distance are drowned in an electrolyte, said electrolyte consists of a sulfuric acid, copper ion and chloride ion, and an electrodeposited copper foil is deposited on a surface of the drum as a negative current is applied to the drum and a positive current is applied to the anode plate, there is provided a method for manufacturing an electrodeposited copper foil which is characterized in that an additive which consists of a gelatin of 0.1 ⁇ 100 ppm, a HEC(Hydroxyethyl Cellulose) of 0.05 ppm ⁇ 50 ppm, and a SPS(bis(sodiumsulfopropyl)disulfide) of 0.05 ⁇ 20 ppm is added to the electrolyte.
- an additive which consists of a gelatin of 0.1 ⁇ 100 ppm, a HEC(Hy
- the amount of the addition of the gelatin is preferably 2 ⁇ 5 ppm.
- the amount of the addition of the HEC is preferably 1 ⁇ 3 ppm.
- the amount of the addition of the SPS is preferably 0.5 ⁇ 3 ppm.
- the molecular weight of the gelatin is preferably above 10000.
- a roughness of a matte side of the electrodeposited copper foil is larger than that of a shiny side.
- FIG. 1 is a view illustrating the construction of a copper manufacture apparatus for describing a method for manufacturing an electrodeposited copper foil according to the present invention
- FIG. 2 is a picture obtained by photographing an electrodeposited copper foil manufactured according to an embodiment 1 of the present invention using a SEM;
- FIG. 3 is a picture obtained by photographing an electrodeposited copper foil manufactured according to a comparison example 2 using a SEM.
- FIG. 1 is a view illustrating a copper foil manufacture apparatus for describing a method for manufacturing an electrodeposited copper foil according to the present invention.
- the copper foil manufacture apparatus is constructed in such a manner that a rotating drum 100 and a circular shaped anode plate 200 are spaced apart by a certain distance.
- the drum 100 and the anode plate 200 are provided within a tank 500 having an electrolyte 600 .
- a lower portion of the rotation center of the drum 100 is drowned in the electrolyte 600 .
- the anode plate 200 is drowned in the electrolyte 600 in such a manner that the drowned shape of the drum 100 corresponds to the drowned shape of the anode plate 200 .
- the negative and positive currents are applied to the drum 100 and the anode plate 200 , respectively.
- the electrolyte 600 filled in the tank 500 consists of H 2 SO 4 of about 50 ⁇ 200 g/l, Cu 2+ of about 30 ⁇ 150 g/l, and Cl ⁇ of below about 200 mg/l.
- the temperature of the electrolyte 600 is about 20 ⁇ 80° C., and the current density is about 20 ⁇ 150 A/dm 2 .
- An electrolytic process is performed between the drum 100 and the anode plate 200 , such that an electrodeposited copper foil 400 is deposited on a surface of the drum 100 .
- the electrodeposited copper foil 400 is rolled up by the roller 300 installed in the upper right side.
- a certain additive is usually provided into the electrolyte 600 for adjusting a material property of the electrodeposited copper foil 400 in the above method.
- the electrodeposited copper foil 400 having a fine circuit pattern is manufactured by using a gelatin, and HEC(Hydroxyethyl cellulose), SPS(bis(sodiumsulfopropyl)disulfide) as an additive.
- HEC Hydrochloric acid
- SPS bis(sodiumsulfopropyl)disulfide
- a low roughness electrodeposited copper foil 400 which may be used as an electrode material of a lithium ion battery is manufactured.
- the gelatin used as an additive is a kind of a drived protein and has a molecular weight of above 10000. If the gelatin having molecular weight below 10000 is used, an interaction between SPS and HEC is weakened, so that an electrodeposited copper foil having ununiform roughness and gloss is manufactured. In the case that the molecular weight of the gelatin is above 10000, it is possible to manufacture a low roughness copper foil having a uniform roughness and gloss.
- the amount of the addition of the gelatin is minimum about 0.1 ppm through maximum about 100 ppm.
- the amount range of the addition of the gelatin is about 1 ⁇ 10 ppm. More preferably, the amount range of the same is about 2 ⁇ 5 ppm.
- the amount of the addition of the HEC is minimum about 0.05 ppm through maximum about 50 ppm.
- the amount range of the addition of the HEC is about 0.5 ⁇ 5 ppm. More preferably, the amount range of the same is about 1-3 ppm.
- an electrodeposited copper foil with a lower roughness can be manufactured by an interaction of the additives.
- the HEC is added below 0.05 ppm in the electrolyte, a uniform electrodeposited copper foil may not be manufactured due to the decrease of the interaction.
- the HEC is added above 50 ppm, protrusion may be extracted from the electrodeposited copper foil.
- the inferiority of the PCB is caused.
- the amount of the addition of the SPS is minimum about 0.05 ppm through maximum about 20 ppm.
- the amount range of the addition of the SPS is about 0.1 ⁇ 10 ppm. More peferably, the amount range of the same is about 0.5 ⁇ 3 ppm.
- the SPS is a material used as a brightener for an electrodepositing process. In the case that the SPS is added into the electrolyte 600 , it is possible to decrease the roughness of the electrodeposited copper foil in accordance with an interaction with the HEC and the gelatin.
- the electrolysis condition is as follows.
- the electrolyte 600 basically consists of H 2 SO 4 of about 100 g/l, Cu 2+ of about 100 g/l, and Cl ⁇ of below about 30 mg/l.
- the temperature of the electrolyte 600 is about 60° C., and the current density is about 100 A/dm 2 .
- comparison example 1 that HEC is not added as an additive
- comparison example 2 that Thiourea is newly added without adding HEC and SPS
- the comparison examples are performed for comparing the material properties of the electrodeposited copper foil 400 which is manufactured when the additives according to the present invention are all added with those of the electrodeposited copper foil which is manufactured when a certain additive among the additives according to the present invention is not added.
- FIG. 2 is a picture obtained by photographing an electrodeposited copper foil manufactured according to an embodiment 1 of the present invention using a SEM
- FIG. 3 is a picture obtained by photographing an electrodeposited copper foil manufactured according to a comparison example 2 using a SEM.
- FIGS. 2 and 3 illustrate the pictures of the SEM of the electrodeposited copper foil manufactured based on the embodiment 1 of the present invention and the electrodeposited copper foil manufactured based on the comparison example 2, respectively, before the post-treatments are performed.
- the electrodeposited copper foil 400 manufactured based on the embodiment 1 of the present invention has a more smooth surface compared to the surface of the electrodeposited copper foil manufactured based on the comparison example 2.
- the above consequence represents that the roughness of the surface of the electrodeposited copper foil 400 manufactured based on the embodiment 1 of the present invention is relatively lower than that of the electrodeposited copper foil 400 manufactured based on the comparison example 2.
- the roughness of the electrodeposited copper foils manufactured according to the embodiments 1 through 3 are 1.61 ⁇ m through 2.1 pm, and the roughness of the electrodeposited copper foils manufactured according to the comparison examples 1 through 2 are about 2.5 pm through 3.5 ⁇ m.
- the electrodeposited copper foils manufactured according to the preferred embodiments of the present invention have a lower roughness, respectively, compared to the roughness of the electrodeposited copper foils manufactured according to the comparison examples.
- the electrodeposited copper foil manufactured according to the present invention can be implemented with a conventional post-treatment for manufacturing the copper clad laminates which is used for printed circuit substrate.
- a nodule process adapted to further form a nodule on one side or both sides of the electrodeposited copper foil for increasing an adhesion with a resin
- a barrier process adapted to prevent a copper from being diffused into a resin layer
- a corrosion resisting process adapted to prevent an oxidation of a copper foil
- a silane coupling agent process adapted to enhance a adhesion reliability when being adhered with a resin.
- the electrodeposited copper foil 400 manufactured according to the present invention is formed of a copper clad laminate with an insulation film layer and an adhesive layer.
- the copper clad laminate is etched based on a circuit design and is adapted to manufacture a printed circuit substrate.
- the amounts of additives cited in each embodiment are not limited thereto.
- various embodiments may be implemented in the addition ranges of the additives cited in the present invention.
- the electrodeposited copper foils 400 having various material properties may be adapted to the production of the copper clad laminate and the circuit substrate.
Abstract
Description
- Not applicable.
- Not applicable.
- Not applicable.
- The present invention relates to a method for manufacturing an electrodeposited copper foil adhered to a prepreg for a PCB(Printed Circuit Board) and an electrodeposited copper foil manufactured thereby, and in particular to a method for manufacturing an electrodeposited copper foil which does not have a residual copper by decreasing a roughness of a matte side of an electrodeposited copper foil even when a fine pattern is formed.
- Generally, a PCB is widely used in a home appliance such as a radio, television, washing machine, VCR, etc., and an industrial electric/electronic instrument such as a computer, wireless communication instrument, various controllers, etc. The PCB is formed of an insulated substrate such as a prepreg of a frame retardant formed in such a manner that a glass fiber is impregnated in foil is adhered to an insulation substrate at a high temperature and pressure, and then the electrodeposited copper foil is etched based on a circuit design.
- The electrodeposited copper foil adhered to the insulation substrate is manufactured by the following processes. A raw foil is manufactured in a copper sulphate solution by a continuous electrodepositing method. Next, a nodule process is performed with respect to a raw copper foil for forming a copper nodule for thereby enhancing an adhesion to an insulation substrate and a barrier layer is formed on the copper foil surface. Finally, a corrosion resist chromating process is performed.
- Recently, as an electric/electro instrument is made thin, a printed circuit for a substrate need have a fine and high intensive and compact construction. For this, a method for developing a very low roughness copper foil has been provided.
- In a conventional electrodeposited copper foil manufacturing method, a first method is to divide an electrolytic section into two sections and then to enhance a current density of a second section rather than a first section for thereby obtaining a low roughness copper foil.
- A super anode is attached to a foil manufacturing apparatus of the above manufacturing facility. In the case that the super anode is adapted, it is possible to change the size of a nucleus when a nucleus is initially generated by adjusting the current applied to the super anode and the main anode. Therefore, it is possible to manufacture the low roughness copper foil by accurately adjusting the size of the initial nucleus. However, it is impossible to manufacture a low roughness copper foil corresponding to the recent fine circuit pattern with the above described method.
- A second method is directed to decreasing the concentration of a chloride ion in an electrolyte below 1 ppm for thereby obtaining a low roughness copper foil. However, it is possible to decrease the concentration of a chloride ion below 1ppm based on only an experimental condition. In the case that the electrodeposited copper foil is manufactured, a copper scrap is generally used as a source material. When the copper scrap is used for the mass production system, there is no suitable economic method for preventing a chloride ion generated by a waste electric wire. Therefore, it is impossible to implement an actual practicality.
- A third method is directed to obtaining a low roughness copper foil by mechanically polishing a conventional electrodeposited copper foil through a buffing method. However, the above method is needed to have an additional manufacturing facility. If there is a surplus during the buffing process, a residual copper may be formed during the manufacture of the PCB.
- A fourth method is directed to adjusting morphology of a copper foil by changing an additive added to an electrolyte. In more detail, the above fourth method is directed to implementing a low roughness copper foil by adding a low molecular weight water-soluble cellulose ether, a low molecular weight water-soluble polyalkylene glycol ether, a low molecular weight water-soluble polyethyleneimine, and a water soluble sulfonated organic sulfur compound. In the above method, it is possible to manufacture a low roughness copper foil by changing only an additive of an electrolyte without changing or modifying a conventional copper manufacture apparatus. In addition, a mechanical polishing process like a buffing process is not needed. It is not needed to manage a chloride ion at a very low degree. The above method is more economical compared to the other methods.
- However, since the copper foil manufactured by the above method has a roughness Rz of a matte side of 3.81 μm, the above method does not satisfy the demand of the recent low roughness copper foil.
- A fifth method is directed to manufacturing a low roughness copper foil using an electrolyte including a small amount of polyethylene glycol, tin ion, iron ion and a chloride ion of below 0.1 ppm. In the above method, there is a limit for substantially maintaining the concentration of the chloride ion below 0.1 ppm for a mass production.
- Accordingly, it is a first object of the present invention to provide a method for manufacturing a low roughness electrodeposited copper foil and an electrodeposited copper foil manufactured by the method which does not need a design change or modification of a conventional copper manufacture apparatus and directly uses a source material of a low cost waste electric wire without using a conventional facility like a mechanical polishing apparatus and an additional process and is capable of manufacturing an electrodeposited copper foil having a low roughness by adjusting the amount of an additive.
- It is a second object of the present invention to provide a method for manufacturing a low roughness electrodeposited copper foil and an electrodeposited copper foil manufactured by the same which are well adapted to an electrode of a lithium ion battery or copper clad laminates which is used in an electronic instrument such as a PCB and a flexible circuit substrate, etc.
- To achieve the above objects, in a method for manufacturing an electrodeposited copper foil in which a rotating drum and an anode plate formed of a curve distanced from an outer surface of the drum by a certain distance are drowned in an electrolyte, said electrolyte consists of a sulfuric acid, copper ion and chloride ion, and an electrodeposited copper foil is deposited on a surface of the drum as a negative current is applied to the drum and a positive current is applied to the anode plate, there is provided a method for manufacturing an electrodeposited copper foil which is characterized in that an additive which consists of a gelatin of 0.1˜100 ppm, a HEC(Hydroxyethyl Cellulose) of 0.05 ppm˜50 ppm, and a SPS(bis(sodiumsulfopropyl)disulfide) of 0.05˜20 ppm is added to the electrolyte.
- The amount of the addition of the gelatin is preferably 2˜5 ppm. The amount of the addition of the HEC is preferably 1˜3 ppm. The amount of the addition of the SPS is preferably 0.5˜3 ppm.
- The molecular weight of the gelatin is preferably above 10000.
- There is preferably further provided a post-treatment for forming a nodule on one surface or both surfaces of the electrodeposited copper foil.
- A roughness of a matte side of the electrodeposited copper foil is larger than that of a shiny side.
- The present invention will become better understood with reference to the accompanying drawings which are given only by way of illustration and thus are not limitative of the present invention, wherein;
- FIG. 1 is a view illustrating the construction of a copper manufacture apparatus for describing a method for manufacturing an electrodeposited copper foil according to the present invention;
- FIG. 2 is a picture obtained by photographing an electrodeposited copper foil manufactured according to an embodiment1 of the present invention using a SEM; and
- FIG. 3 is a picture obtained by photographing an electrodeposited copper foil manufactured according to a comparison example 2 using a SEM.
- FIG. 1 is a view illustrating a copper foil manufacture apparatus for describing a method for manufacturing an electrodeposited copper foil according to the present invention.
- As shown in FIG. 1, the copper foil manufacture apparatus is constructed in such a manner that a rotating
drum 100 and a circular shapedanode plate 200 are spaced apart by a certain distance. Here, thedrum 100 and theanode plate 200 are provided within atank 500 having anelectrolyte 600. - Here, a lower portion of the rotation center of the
drum 100 is drowned in theelectrolyte 600. Theanode plate 200 is drowned in theelectrolyte 600 in such a manner that the drowned shape of thedrum 100 corresponds to the drowned shape of theanode plate 200. The negative and positive currents are applied to thedrum 100 and theanode plate 200, respectively. - Preferably, the
electrolyte 600 filled in thetank 500 consists of H2SO4 of about 50˜200 g/l, Cu2+ of about 30˜150 g/l, and Cl− of below about 200 mg/l. The temperature of theelectrolyte 600 is about 20˜80° C., and the current density is about 20˜150 A/dm2. - An electrolytic process is performed between the
drum 100 and theanode plate 200, such that anelectrodeposited copper foil 400 is deposited on a surface of thedrum 100. The electrodepositedcopper foil 400 is rolled up by theroller 300 installed in the upper right side. - A certain additive is usually provided into the
electrolyte 600 for adjusting a material property of theelectrodeposited copper foil 400 in the above method. In the present invention, theelectrodeposited copper foil 400 having a fine circuit pattern is manufactured by using a gelatin, and HEC(Hydroxyethyl cellulose), SPS(bis(sodiumsulfopropyl)disulfide) as an additive. In addition, a low roughnesselectrodeposited copper foil 400 which may be used as an electrode material of a lithium ion battery is manufactured. - The gelatin used as an additive is a kind of a drived protein and has a molecular weight of above 10000. If the gelatin having molecular weight below 10000 is used, an interaction between SPS and HEC is weakened, so that an electrodeposited copper foil having ununiform roughness and gloss is manufactured. In the case that the molecular weight of the gelatin is above 10000, it is possible to manufacture a low roughness copper foil having a uniform roughness and gloss.
- The amount of the addition of the gelatin is minimum about 0.1 ppm through maximum about 100 ppm. Preferably, the amount range of the addition of the gelatin is about 1˜10 ppm. More preferably, the amount range of the same is about 2˜5 ppm.
- If the gelatin is added below 0.1 ppm in the
electrolyte 600, more delicate initial structure may be obtained, but an electrodeposited copper foil with high roughness is obtained by promoting the growth of thecopper foil 400. Accordingly, an electrodeposited copper foil with low roughness cannot be manufactured. On the other hand, if the gelatin is added above 100 ppm, an electrodeposited copper foil with low roughness may be obtained, but the characteristic of HTE(High Temperature Elongation, measured at 180° C.) which is one of the important characteristics of the copper foil can be deteriorated. - The amount of the addition of the HEC is minimum about 0.05 ppm through maximum about 50 ppm. Preferably, the amount range of the addition of the HEC is about 0.5˜5 ppm. More preferably, the amount range of the same is about 1-3 ppm. In the case that the HEC is added with the SPS and the gelatin in the
electrolyte 600, an electrodeposited copper foil with a lower roughness can be manufactured by an interaction of the additives. - If the HEC is added below 0.05 ppm in the electrolyte, a uniform electrodeposited copper foil may not be manufactured due to the decrease of the interaction. On the other hand, if the HEC is added above 50 ppm, protrusion may be extracted from the electrodeposited copper foil. In the case that copper clad laminates are produced by the electrodeposited copper foil with protrusion and then a PCB(Printed Circuit Board) is produced by the above copper clad laminates, the inferiority of the PCB is caused.
- The amount of the addition of the SPS is minimum about 0.05 ppm through maximum about 20 ppm. Preferably, the amount range of the addition of the SPS is about 0.1˜10 ppm. More peferably, the amount range of the same is about 0.5˜3 ppm. The SPS is a material used as a brightener for an electrodepositing process. In the case that the SPS is added into the
electrolyte 600, it is possible to decrease the roughness of the electrodeposited copper foil in accordance with an interaction with the HEC and the gelatin. - If the SPS is added by below 0.05 ppm, the ability of the interaction is decreased, so that an
electrodeposited copper foil 400 having ununiform roughness is manufactured. On the other hand, if the SPS is added by the amount of above 20 ppm, there is not a certain effect, but the cost is increased. - Three embodiments for manufacturing an
electrodeposited copper foil 400 in such a manner that the amounts of the gelatin, HEC, and SPS added to theelectrolyte 600 as an additive are different by the unit of ppm will be described in the following. - According to the embodiments of the present invention, the electrolysis condition is as follows. The
electrolyte 600 basically consists of H2SO4 of about 100 g/l, Cu2+ of about 100 g/l, and Cl− of below about 30 mg/l. The temperature of theelectrolyte 600 is about 60° C., and the current density is about 100 A/dm2. - The amounts of the additives added to the
electrolyte 600 are shown in Table 1.TABLE 1 Gelatin HEC SPS Embodiment 1 2.5 ppm 3 ppm 1.5 ppm Embodiment 2 3.5 ppm 1 ppm 2.5 ppm Embodiment 3 4.5 ppm 2 ppm 0.5 ppm - In the following, the comparison example 1 that HEC is not added as an additive and the comparison example 2 that Thiourea is newly added without adding HEC and SPS will be described. The comparison examples are performed for comparing the material properties of the
electrodeposited copper foil 400 which is manufactured when the additives according to the present invention are all added with those of the electrodeposited copper foil which is manufactured when a certain additive among the additives according to the present invention is not added. - The electrolysis condition of the electrolyte of the comparisons except for the components of the additives is the same as the electrolysis condition of the electrolyte of the above embodiments of the present invention. The amounts of the additives added are shown in Table 2.
TABLE 2 Gelatin HEC SPS Thiourea Comparison example 1 2.5 ppm — 1.5 ppm — Comparison example 2 3.5 ppm — — 0.4 ppm - FIG. 2 is a picture obtained by photographing an electrodeposited copper foil manufactured according to an embodiment1 of the present invention using a SEM, and FIG. 3 is a picture obtained by photographing an electrodeposited copper foil manufactured according to a comparison example 2 using a SEM. As shown therein, FIGS. 2 and 3 illustrate the pictures of the SEM of the electrodeposited copper foil manufactured based on the embodiment 1 of the present invention and the electrodeposited copper foil manufactured based on the comparison example 2, respectively, before the post-treatments are performed.
- As shown in FIGS. 2 and 3, it is known that the
electrodeposited copper foil 400 manufactured based on the embodiment 1 of the present invention has a more smooth surface compared to the surface of the electrodeposited copper foil manufactured based on the comparison example 2. The above consequence represents that the roughness of the surface of theelectrodeposited copper foil 400 manufactured based on the embodiment 1 of the present invention is relatively lower than that of theelectrodeposited copper foil 400 manufactured based on the comparison example 2. - In Table 3, there are a roughness, tensile strength, elongation, high temperature tensile strength, and high temperature elongation of the electrodeposited copper foil manufactured based on each embodiment of the present invention and the electrodeposited copper foil manufactured based on each comparison example.
TABLE 3 High High temper- Rough- Tensile Elon- temperature ature ness strength gation tensile strength elonga- Rz(μm) (kgf/mm2) (%) (kgf/mm2) tion(%) Embodiment 1 1.8 33.3 15.9 18.3 16.3 Embodiment 2 1.6 34.6 18.1 18.2 15.1 Embodiment 3 2.1 32.8 16.3 19.1 15.3 Comparison 2.5 34.1 5.8 20.1 8.5 example 1 Comparison 3.5 33.8 8.3 20.3 2.1 example 2 - As shown in Table 3, it is known that the roughness of the electrodeposited copper foils manufactured according to the embodiments 1 through 3 are 1.61 μm through 2.1 pm, and the roughness of the electrodeposited copper foils manufactured according to the comparison examples 1 through 2 are about 2.5 pm through 3.5 μm. As a result, it is known that the electrodeposited copper foils manufactured according to the preferred embodiments of the present invention have a lower roughness, respectively, compared to the roughness of the electrodeposited copper foils manufactured according to the comparison examples.
- The electrodeposited copper foil manufactured according to the present invention can be implemented with a conventional post-treatment for manufacturing the copper clad laminates which is used for printed circuit substrate.
- As a conventional post-treatment of the
electrodeposited copper foil 400, there are a nodule process adapted to further form a nodule on one side or both sides of the electrodeposited copper foil for increasing an adhesion with a resin, a barrier process adapted to prevent a copper from being diffused into a resin layer, a corrosion resisting process adapted to prevent an oxidation of a copper foil, and a silane coupling agent process adapted to enhance a adhesion reliability when being adhered with a resin. - In addition, the
electrodeposited copper foil 400 manufactured according to the present invention is formed of a copper clad laminate with an insulation film layer and an adhesive layer. The copper clad laminate is etched based on a circuit design and is adapted to manufacture a printed circuit substrate. - In the method for manufacturing a low roughness electrodeposited copper foil and an electrodeposited copper foil manufactured thereby, the amounts of additives cited in each embodiment are not limited thereto. In the present invention, various embodiments may be implemented in the addition ranges of the additives cited in the present invention. The electrodeposited copper foils400 having various material properties may be adapted to the production of the copper clad laminate and the circuit substrate.
- As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described examples are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.
Claims (15)
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Application Number | Priority Date | Filing Date | Title |
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KR10-2002-0075411A KR100454270B1 (en) | 2002-11-29 | 2002-11-29 | Low Roughness Electrodeposited Copper Foil Manufacturing Method And Electrodeposited Copper Foil Thereby |
KR10-2002-0075411 | 2002-11-29 |
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US20040104118A1 true US20040104118A1 (en) | 2004-06-03 |
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US10/720,579 Abandoned US20040104118A1 (en) | 2002-11-29 | 2003-11-24 | Method for manufacturing very low roughness electrodeposited copper foil and electrodeposited copper foil manufactured thereby |
Country Status (2)
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US (1) | US20040104118A1 (en) |
KR (1) | KR100454270B1 (en) |
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US20080142249A1 (en) * | 2006-12-13 | 2008-06-19 | International Business Machines Corporation | Selective surface roughness for high speed signaling |
CN103060859A (en) * | 2012-12-27 | 2013-04-24 | 东强(连州)铜箔有限公司 | An additive for improving the peak shape of the rough surface of rough foil, and a production process for electrolytic copper foil |
CN104805478A (en) * | 2014-01-29 | 2015-07-29 | 金居开发铜箔股份有限公司 | Electrolytic copper foil for negative current collector and manufacturing method thereof |
CN106191939A (en) * | 2015-04-13 | 2016-12-07 | 财团法人工业技术研究院 | Thick copper layer and method for forming the same |
CN106521564A (en) * | 2016-10-27 | 2017-03-22 | 建滔(连州)铜箔有限公司 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
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CN111020643A (en) * | 2019-12-30 | 2020-04-17 | 中国科学院青海盐湖研究所 | Double-sided smooth copper foil and preparation method and device thereof |
CN114032586A (en) * | 2021-11-11 | 2022-02-11 | 浙江花园新能源股份有限公司 | Electrolyte for improving uniformity of M-surface particles of electrolytic copper foil, production process and product |
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TWI518210B (en) * | 2013-01-31 | 2016-01-21 | 三井金屬鑛業股份有限公司 | Electrolytic copper foil and method for manufacturing the same and surface-treated copper foil using the electrolytic copper foil |
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JPH10330983A (en) * | 1997-05-30 | 1998-12-15 | Fukuda Metal Foil & Powder Co Ltd | Electrolytic copper foil and its production |
JP4419161B2 (en) * | 1999-10-27 | 2010-02-24 | Dowaホールディングス株式会社 | Method for producing electrolytic copper foil |
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US5215646A (en) * | 1992-05-06 | 1993-06-01 | Circuit Foil Usa, Inc. | Low profile copper foil and process and apparatus for making bondable metal foils |
US5834140A (en) * | 1995-09-22 | 1998-11-10 | Circuit Foil Japan Co., Ltd. | Electrodeposited copper foil for fine pattern and method for producing the same |
US5863410A (en) * | 1997-06-23 | 1999-01-26 | Circuit Foil Usa, Inc. | Process for the manufacture of high quality very low profile copper foil and copper foil produced thereby |
US5863666A (en) * | 1997-08-07 | 1999-01-26 | Gould Electronics Inc. | High performance flexible laminate |
US6562222B1 (en) * | 2000-01-20 | 2003-05-13 | Nikko Materials Company, Limited | Copper electroplating liquid, pretreatment liquid for copper electroplating and method of copper electroplating |
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US20080142249A1 (en) * | 2006-12-13 | 2008-06-19 | International Business Machines Corporation | Selective surface roughness for high speed signaling |
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CN106191939A (en) * | 2015-04-13 | 2016-12-07 | 财团法人工业技术研究院 | Thick copper layer and method for forming the same |
EP3327838A4 (en) * | 2015-07-24 | 2019-02-20 | KCF Technologies Co., Ltd. | Electrolytic copper foil for lithium secondary battery and lithium secondary battery comprising same |
US10243216B2 (en) | 2015-07-24 | 2019-03-26 | Kcf Technologies Co., Ltd. | Electrolytic copper foil for lithium secondary battery and lithium secondary battery comprising the same |
CN106560009A (en) * | 2015-07-24 | 2017-04-05 | Ls美创有限公司 | Electrolytic copper foil and the lithium secondary battery comprising the electrolytic copper foil for lithium secondary battery |
JP2017069471A (en) * | 2015-09-30 | 2017-04-06 | 大日本印刷株式会社 | Substrate for light-emitting device, module and method for manufacturing substrate for light-emitting device |
CN106521564A (en) * | 2016-10-27 | 2017-03-22 | 建滔(连州)铜箔有限公司 | Composite additive for producing low-profile electrolytic copper foil and sedimentation process of composite additive |
CN109750334A (en) * | 2019-02-28 | 2019-05-14 | 灵宝华鑫铜箔有限责任公司 | A kind of production technology of 6 μm of double light high tensile additive for electrolytic copper foil and the electrolytic copper foil |
CN111020643A (en) * | 2019-12-30 | 2020-04-17 | 中国科学院青海盐湖研究所 | Double-sided smooth copper foil and preparation method and device thereof |
EP4163420A1 (en) * | 2021-10-07 | 2023-04-12 | Circuit Foil Luxembourg | Copper foil with high energy at break and secondary battery comprising the same |
WO2023057067A1 (en) * | 2021-10-07 | 2023-04-13 | Circuit Foil Luxembourg | Copper foil with high engery at break and secondary battery comprising the same |
CN114032586A (en) * | 2021-11-11 | 2022-02-11 | 浙江花园新能源股份有限公司 | Electrolyte for improving uniformity of M-surface particles of electrolytic copper foil, production process and product |
CN114561673A (en) * | 2022-03-10 | 2022-05-31 | 九江德福科技股份有限公司 | Method for reducing high-temperature high-ductility copper foil surface copper nodules |
Also Published As
Publication number | Publication date |
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KR100454270B1 (en) | 2004-10-26 |
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