WO2023282482A1

WO2023282482A1 - Method for manufacturing copper foil for semiconductor and copper foil for semiconductor using same

Info

Publication number: WO2023282482A1
Application number: PCT/KR2022/008214
Authority: WO
Inventors: 이대인; 이종인; 이이근
Original assignee: 주식회사 다이브; 이대인; 이종인
Priority date: 2021-07-09
Filing date: 2022-06-10
Publication date: 2023-01-12
Also published as: KR102517417B1; TW202302912A; KR20230009650A

Abstract

The present specification relates to a method for manufacturing a copper foil for a semiconductor, which is manufactured by a copper foil manufacturing apparatus including a negative electrode rotating plate rotating in one direction and first to fifth electrolytic cells spaced apart from each other at a predetermined interval along the negative electrode rotating plate, the method comprising the steps of: depositing a carrier metal layer on the negative electrode rotating plate by the first electrolytic cell; depositing a separation layer on the carrier metal layer by the second electrolytic cell; depositing an ultra-thin copper foil layer on the separation layer by the third electrolytic cell; and forming a roughening treatment layer on the surface of the ultra-thin copper foil layer by the fourth electrolytic cell and the fifth electrolytic cell, wherein as the negative electrode rotating plate rotates, the first to fifth electrolytic cells are sequentially electroformed with the negative electrode rotating plate to form a single semiconductor copper foil.

Description

Manufacturing method of copper foil for semiconductor and copper foil for semiconductor using the same

The present invention relates to a method for manufacturing copper foil for semiconductors, which is sequentially deposited on one cathode rotating plate and provided, and to a copper foil for semiconductors using the same.

As the demand for small and thin electronic products capable of transmitting high frequency signals increases, the demand for copper foil and copper clad laminates for semiconductors is also increasing.

The copper clad laminate for semiconductors refers to a substrate in which a copper plate having a thickness of 10 μm or less is attached to an insulating substrate. The copper-clad laminate can form a more complex and precise circuit on the printed circuit board as the thickness of the copper foil attached thereto becomes thinner. However, when the thickness of the copper foil is 5 μm or less, the mechanical strength of the copper foil is rapidly reduced, and damage or cracking may occur during the manufacturing or attachment process of the copper foil.

In order to solve the above problem, a method of forming a copper foil on a carrier metal layer that supplements the strength of the copper foil, attaching the copper foil to a substrate, and then peeling off the carrier metal layer is disclosed in Japanese Patent Registration No. 6860706, Japanese Patent Registration No. 3250994 and Korean Patent Registration No. 10-1889087 is being studied in various fields.

However, in the method presented in the above-mentioned documents, an apparatus for manufacturing a carrier metal layer and an apparatus for manufacturing copper foil must be provided separately, and in the process of forming an ultra-copper foil layer, there is a large variation in the quality of the copper foil layer depending on the surface state of the carrier metal layer. There is a problem that occurs.

For this reason, there is a demand for a manufacturing method of a copper foil for semiconductors capable of improving productivity and quality by simultaneously manufacturing the ultra-copper foil layer and the carrier metal layer using the same device.

In order to solve the above problems, the present invention is a semiconductor copper foil manufacturing method for manufacturing one semiconductor copper foil by sequentially depositing a carrier metal layer, a separation layer, an electrode copper foil layer and a roughening treatment layer on one cathode rotating plate, and using the same A copper foil for semiconductors can be provided.

One embodiment of the present invention for achieving the above object is manufactured by a copper foil manufacturing apparatus including a cathode rotating plate rotating in one direction and first to fifth electrolysis cells spaced apart from each other at predetermined intervals along the cathode rotating plate, , depositing a carrier metal layer on the cathode rotating plate by the first electrolytic cell, depositing a separation layer on the carrier metal layer by the second electrolytic cell, and an ultra-copper foil layer on the separation layer by the third electrolytic cell. and forming a roughened layer on the surface of the copper foil layer by the fourth and fifth electrolytic cells, wherein as the cathode rotating plate rotates, the first to fifth electrolytic cells It relates to a method for manufacturing a copper foil for semiconductors, characterized in that forming one copper foil for semiconductors by sequentially electroforming with the cathode rotating plate.

In the above embodiment, the first to fifth electrolytic cells include an electrolyte solution and a cathode material therein, and currents and electrolyte solutions having different sizes may be independently supplied to each electrolysis cell.

In the above embodiment, the carrier metal layer is formed by spraying a first electrolyte into the first electrolytic cell and then passing a first current, and the first cathode material included in the first electrolytic cell has solubility. It can be provided as a metal plate or a metal ball.

In the above embodiment, the separation layer is formed by spraying a second electrolyte into the second electrolytic cell and then passing a second current, and the second anode material included in the second electrolytic cell is iridium oxide ( Ir ₂ O ₃ ) may be provided as a titanium (Ti) plate.

In the above embodiment, the copper foil layer is formed by spraying a third electrolyte into the third electrolytic cell and then passing a third current, and the third anode material included in the third electrolytic cell is iridium oxide ( Ir ₂ O ₃ ) may be provided as a titanium (Ti) plate.

In the above embodiment, the step of forming the roughened layer includes a first roughening step of forming and fixing copper nuclei and a second roughening step of growing the copper nuclei, wherein the first roughening step may be performed by a fourth anode material provided as a titanium (Ti) plate coated with iridium oxide (Ir ₂ O ₃ ).

In the above embodiment, the second roughening step is a fifth material provided with any one of a soluble metal piece (Metal plate) or a titanium (Ti) plate coated with iridium oxide (Ir ₂ O ₃ ). Characterized in that it is carried out by a cathode material, a method of manufacturing a copper foil for semiconductors.

According to another embodiment of the present invention, the separation layer precipitated on the upper surface of the carrier metal layer, the ultra-copper foil layer precipitated on the upper surface of the separation layer, the roughened layer formed on the surface of the ultra-copper thin layer, and the surface of the roughened layer A copper foil for semiconductors including a formed anti-corrosion plating layer, wherein the copper foil for semiconductors includes a cathode rotating plate rotating in one direction and first to fifth electrolytic cells spaced apart from each other along the cathode rotating plate at predetermined intervals. It is manufactured by the apparatus, and as the cathode rotating plate rotates, the first to fifth electrolytic cells are sequentially electroformed with the cathode rotating plate to form a single semiconductor copper foil. It is about.

In the above embodiment, the first to fifth electrolytic cells contain an electrolyte solution and a cathode material therein, and independently supply currents of different magnitudes to each electrolysis cell to independently electroform the cathode rotating plate. It can be manufactured by a copper foil manufacturing apparatus.

In the above embodiment, the carrier metal layer is made of copper (Cu), nickel (Ni), chromium (Cr), aluminum (Al) or an alloy containing the same, and may have a thickness of 5 to 50 μm. .

In the above embodiment, the separation layer is provided as an alloy layer of indium (In), zinc (Zr), and chromium (Cr), and may have a thickness of 0.01 μm or less.

According to the above-described features, the present invention deposits the carrier metal layer, the separation layer, the ultra-copper foil layer, and the roughening layer on one cathode rotating plate in one-pass, and the time and cost required when manufacturing copper foil for semiconductors. can save

In addition, the present invention can prevent the copper foil from being folded or torn by directly depositing the copper foil layer on the carrier metal layer and the separation layer.

In addition, the present invention divides the step of forming the roughened layer into two steps, and at this time, the temperature of the cathode material and the electrolyte solution is provided differently to form the roughened layer in the most optimized way.

1 is a flowchart illustrating a method of manufacturing a copper foil for semiconductors according to an embodiment of the present invention.

2 is a view for explaining a copper foil for semiconductors according to an embodiment of the present invention.

3 is a view for explaining an apparatus for manufacturing copper foil for semiconductors according to an embodiment of the present invention.

Hereinafter, a method for manufacturing a copper foil for semiconductors according to the present invention and a copper foil for semiconductors using the same will be described in detail. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Therefore, the present invention may be embodied in other forms without being limited to the drawings presented below, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, unless there is another definition in the technical terms and scientific terms used, they have meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may unnecessarily obscure are omitted.

One feature of the present invention relates to a method for manufacturing a copper foil for semiconductors. More preferably, it can be manufactured by a copper foil manufacturing apparatus including a cathode rotating plate rotating in one direction and a plurality of electrolytic cells spaced apart from each other at predetermined intervals along the cathode rotating plate. In addition, as the cathode rotating plate rotates, the plurality of electrolytic cells may be electroformed sequentially with the cathode rotating plate to be produced in one-pass.

That is, the copper foil for semiconductor according to an embodiment of the present invention can be manufactured as one finished product by performing the deposition process of each layer in real time through one operation cycle (One cycle) using one device.

Typically, a copper foil for a semiconductor may include a carrier metal layer provided as an electrodeposited copper foil or the like. This means that in order to manufacture the copper foil for semiconductors, the carrier metal layer must be purchased separately or a device for manufacturing the carrier metal layer must be separately provided.

In addition, when the thickness of the ultra-copper foil layer is reduced to 5 μm or less, there is a problem in that the quality of the ultra-copper foil layer laminated on the carrier metal layer is greatly affected by the surface state of the carrier metal layer. For example, when the surface of the carrier metal layer is uneven or fine foreign substances are inserted, the ultra-copper foil layer is damaged or cracked, resulting in a rapid deterioration in quality. In order to prevent this, the surface state of the carrier metal layer should be continuously managed, and if the surface state of the carrier metal layer is below a certain level, the entire amount should be discarded.

That is, cost and time are continuously required to produce, purchase, and manage the carrier metal layer, which means that product productivity may be reduced.

In order to improve this, the present invention can manufacture a carrier metal layer through one copper foil manufacturing apparatus, and deposit a separation layer, an ultra-copper foil layer, and a roughened layer on the carrier metal layer in real time. Through this, it is possible to reduce the cost of separately purchasing equipment for manufacturing the carrier metal layer and to reduce the management cost of the carrier metal layer.

That is, the present invention can perform the precipitation process of each layer in real time through one cycle using one device, and can manufacture a finished product with one device. Through this, the present invention can improve productivity and reduce cost of the copper foil for semiconductors.

In addition, the present invention can perform a roughening treatment to generate fine particles on the surface of the ultra-copper foil layer through the above-described single copper foil manufacturing apparatus. Through this, it is possible to form a roughened layer on the surface of the copper foil layer. At this time, the fine particles may be provided as copper (Cu) particles, but are not limited thereto.

That is, the copper foil for semiconductors according to an embodiment of the present invention can be manufactured by a copper foil manufacturing apparatus including a cathode rotating plate rotating in one direction and a plurality of electrolytic cells spaced apart from each other at predetermined intervals along the cathode rotating plate. A carrier metal layer, a separation layer, an ultra-copper foil layer, and a roughening treatment layer are sequentially deposited through the device of, so that one copper foil for a semiconductor can be manufactured.

In addition, the copper foil manufacturing apparatus according to an embodiment of the present invention may include a plurality of electrolysis cells in one apparatus. At this time, the user can diversify the properties of the metal layer by independently supplying current and electrolyte of different sizes to each electrolysis cell.

For example, when the electrolytic cells are provided as first to fifth electrolytic cells, the carrier metal layer may be formed by passing a first current after spraying a first electrolyte into the first electrolytic cell, and the separation The layer may be formed by passing a second current after spraying a second electrolyte into the second electrolytic cell. In addition, the copper foil layer is formed by spraying a third electrolyte into the third electrolysis cell and then passing a third current, and the roughening layer is formed by spraying a fourth electrolyte into the fourth electrolysis cell and then passing a third current through the fourth electrolytic cell. It may be formed through a process of passing current and a process of passing a fifth current after spraying a fifth electrolyte into the fifth electrolytic cell.

That is, the copper foil for semiconductors according to an embodiment of the present invention is manufactured through a single device including a plurality of electrolysis cells, and by independently supplying current and electrolyte to the plurality of electrolysis cells, the material, thickness, characteristics can be independently controlled.

According to another embodiment of the present invention, anti-rust treatment may be performed on the copper foil for semiconductors.

The configuration of the copper foil for semiconductors according to an embodiment of the present invention has been described above. Hereinafter, a method of manufacturing a copper foil for semiconductors according to an embodiment of the present invention will be described with reference to FIGS. 1 to 3.

1 is a flowchart for explaining a manufacturing method of a copper foil for semiconductors according to an embodiment of the present invention, FIG. 2 is a diagram for explaining a copper foil for semiconductors according to an embodiment of the present invention, and FIG. 3 is an embodiment of the present invention. It is a figure for explaining the copper foil manufacturing apparatus for semiconductors according to an example.

1, in the copper foil 100 for semiconductor according to an embodiment of the present invention, a carrier metal layer is deposited on the cathode rotating plate by a first electrolytic cell (S10), and a carrier metal layer is deposited on the carrier metal layer by a second electrolytic cell. Depositing a separation layer (S20), depositing an ultra-copper foil layer on the separation layer by a third electrolytic cell (S30), and a roughening treatment layer on the surface of the ultra-copper foil layer by the fourth and fifth electrolysis cells. It may include a forming step (S40), a step of peeling the manufactured copper foil for semiconductors (S50), and a step of anticorrosive treatment of the copper foil for semiconductors (S60).

As described above, the copper foil 100 for semiconductors according to an embodiment of the present invention can be manufactured as a single device, and more preferably, a copper foil including one cathode rotating plate 200 and a plurality of electrolysis cells 300. It can be manufactured by the manufacturing apparatus 1000.

Specifically, referring to FIG. 2 , the copper foil manufacturing apparatus 1000 includes a cathode rotating plate 200 rotating in one direction and a plurality of electrolytic cells 300 spaced apart from each other along the cathode rotating plate 200 at predetermined intervals. can include

The cathode rotating plate 200 may be provided by welding a plurality of titanium plates (Ti plates) in a ring shape, more preferably in an endless plate ring shape.

According to an embodiment, the titanium plate constituting the cathode rotating plate 200 may be provided in a width of 0.1 to 2 m, a length of 5 to 50 m, and a thickness of 1 to 30 mm, but is not limited thereto, and the manufacturing environment can be changed at any time according to

In addition, a plurality of conduction rolls may be formed on the inner surface of the cathode rotating plate 200, and may be rotated in one direction using the plurality of conduction rolls. In addition, the cathode rotating plate 200 may be energized as a cathode through the conduction roll.

That is, the conduction roll may serve to charge the cathode rotary plate 200 and may also serve as a driving roll to rotate the cathode rotary plate 200 in one direction.

According to an embodiment, the cathode rotating plate 200 may perform additional heat treatment after welding and assembling. Through this, the cathode rotating plates 200 can be strongly coupled to each other, and stress formed during the coupling process can be removed to prevent deformation or peeling of the thin film during the manufacturing process.

At this time, the heat treatment is preferably performed at 500 to 700 ° C for 10 to 100 minutes. If the heat treatment is performed at less than 500 ° C or less than 10 minutes, stress remains between the cathode rotating plate 200 and the metal In the process of manufacturing the thin film, deformation and peeling may occur.

Conversely, if the heat treatment is performed at 700° C. or longer than 100 minutes, productivity may decrease and thermal deformation may occur.

For this reason, the heat treatment may be performed at 500 to 700°C for 10 to 100 minutes, more preferably at 600 to 650°C for 30 to 50 minutes.

The plurality of electrolytic cells 300 may include first to fifth

electrolytic cells

300a, 300b, 300c, 300d1, and 300d2, and may further include more electrolytic cells. In addition, the first to fifth

electrolytic cells

300a, 300b, 300c, 300d1, and 300d2 may be spaced apart from each other at predetermined intervals along one cathode rotation plate 200, and as the cathode rotation plate 200 rotates, Accordingly, the first to fifth

electrolytic cells

300a, 300b, 300c, 300d1, and 300d2 may be electroformed simultaneously with the cathode rotating plate 200 to form one copper foil 100 for semiconductors.

According to the embodiment, a predetermined space may be formed inside the electrolysis cell 300, and the cathode material 310 and the electrolyte supply nozzle 330 may be included in the space. In addition, the electrolyte may be injected into the inner space of the electrolysis cell 300 through the electrolyte supply nozzle 330 .

For example, the first electrolysis cell 300a may include a first positive electrode material 310a and a first electrolyte supply nozzle 330a therein, and the first electrolyte supply nozzle 330a may include the first electrolytic solution supply nozzle 330a. The first electrolyte may be filled between the cathode rotating plate 200 and the first positive electrode material 410a by spraying the first electrolyte into the cell 310a.

In this specification, only the configuration of the first electrolysis cell 300a has been described, but it is not limited thereto, and the second electrolysis cell 300b, the third electrolysis cell 300c, the fourth electrolysis cell 300d-1 and the fifth electrolysis cell 300d-1 are described. The same can be applied to the cell 300d-2, and can be equally applied to more electrolysis cells.

Referring to FIGS. 1 to 3 , in step S10, a first current is passed between the cathode rotating plate 200 and the first anode material 310a after spraying the first electrolyte into the first electrolysis cell 300a. This is a step of depositing the carrier metal layer 110 by conducting a current.

The carrier metal layer 110 means a metal layer for preventing scratches, wrinkles, and bending of the ultra-copper foil layer 150 to be described later and protecting the glossy surface of the ultra-copper foil layer 150 from being exposed to foreign substances.

According to an embodiment, the carrier metal layer 110 is made of copper (Cu), nickel (Ni), chromium (Cr), aluminum (Al) or an alloy containing the same, and is formed through electroplating or sputtering. It can be. Hereinafter, in this specification, the carrier metal layer is described as an example of an electrodeposited copper foil containing copper (Cu), but is not limited thereto.

According to an embodiment, the carrier metal layer 110 may be formed to have a thickness of 5 to 50 μm. When the thickness of the carrier metal layer 110 is less than 5 μm, the copper foil layer 150 may be scratched, wrinkled, or bent due to lack of rigidity. On the other hand, when the thickness of the carrier metal layer 110 exceeds 50 μm, residues remain during the peeling process of the carrier metal layer 110, which can reduce electrical characteristics of the insulation layer on which the copper foil layer 150 is stacked. . For this reason, the carrier metal layer 110 may have a thickness of 5 to 50 μm, more preferably 9 to 30 μm.

According to an embodiment, the first electrolyte solution may be provided as an electrolyte solution in which one or more metal ions of copper (Cu), nickel (Ni), and aluminum (Al) are dissolved in a sulfuric acid (H ₂ SO ₄ ) solution, and more preferably More specifically, it may be provided as an electrolyte solution in which copper (Cu) ions are dissolved in a sulfuric acid (H ₂ SO ₄ ) solution.

According to an embodiment, the first positive electrode material 310a may be provided as a metal plate or metal ball having solubility. That is, the first cathode material 310a may be provided as a soluble copper plate or a copper ball.

If a conventional insoluble cathode material is used as the first cathode material 310a, an excess of oxygen (O ₂ ) is generated on the surface of the first cathode material 310a during the electrolysis process.

Excessive oxygen (O ₂ ) generated on the surface of the first positive electrode material 310a may be attached to the surface of the negative electrode rotating plate 200 to be electrodeposited and cause surface defects of the carrier metal layer 110, and the carrier metal layer 110 ) may be oxidized to weaken the electrical properties.

To prevent this, the present invention provides the first positive electrode material 310a in the form of a soluble copper piece (Cu plate) or a copper ball (Cu ball) so that the excess oxygen (O ₂ ) is removed from the cathode rotating plate (200). ) It can be discharged into the space formed between copper plates or copper balls without being attached to the surface. Through this, the quality of the carrier metal layer 110 can be improved.

In addition, the insoluble cathode material has a problem in that the required power increases during electroforming because the voltage required is higher than that of the soluble cathode material. The downside is that it requires equipment.

In addition, as the first cathode material 310a is dissolved in the first electrolyte solution, the user can visually check the remaining amount and replacement period of the first cathode material 310a. Through this, there is an advantage in that it is easy to check the replacement cycle of the first cathode material 310a and optimize process conditions.

In the step S20, the separation layer 130 is formed by spraying the second electrolyte into the second electrolysis cell 310b and then passing a second current between the cathode rotating plate 200 and the second anode material 310b. This is the step of precipitation.

The peeling layer 130 is a metal layer provided between the carrier metal layer 110 and the copper foil layer 150 to be described later. When the semiconductor copper foil 100 is bonded to the insulating layer, the carrier metal layer 110 ) can be separated to adhere the copper foil layer 150 to the insulating layer.

According to an embodiment, the separation layer 130 may be provided as a nano-scale metal layer, and more preferably may have a thickness of less than 20 nm. When the thickness of the separation layer exceeds 20 nm, the peel strength required to peel the separation layer 130 increases, so that the carrier metal layer 110 and the copper foil layer 150 are separated. There are difficulties. For example, when the thickness of the separation layer 130 exceeds 20 nm, the peel force of the separation layer 130 may increase to 50 N/m or more. This is because the carrier metal layer 110 is not easily separated, and an additional process is required.

On the other hand, if the thickness of the separation layer 130 is less than 1 nm, the separation layer 130 is too thin and may be separated from the carrier metal layer 110 before the semiconductor copper foil 100 is adhered to the insulating layer. That is, it is difficult to properly attach the copper foil 100 for a semiconductor to a position desired by a user.

For this reason, the thickness of the separation layer 130 is preferably less than 20 nm, more preferably 1 to 10 nm.

According to an embodiment, the separation layer 130 is provided with metal to finely adjust the thickness. More preferably, the separation layer 130 is indium (In), chromium (Cr), zinc (Zr), nickel (Ni), molybdenum (W), cobalt (Co), silver (Ag), copper (Cu) , It may be provided in the form of one or more metals or alloys selected from the group consisting of aluminum (Al), manganese (Mn), iron (Fe), tin (Sn), and vanadium (V). Hereinafter, in the present specification, the separation layer 130 includes a metal layer made of indium (In), chromium (Cr), and zinc (Zn), or at least one of indium (In), chromium (Cr), and zinc (Zn). Provided as an alloy layer is described as an example, but is not limited thereto.

According to an embodiment, the second electrolyte solution may be provided as an electrolyte solution containing indium (In), chromium (Cr), and zinc (Zr) ions, but is not limited thereto, and according to the judgment of a person skilled in the art, indium (In ), chromium (Cr), zinc (Zr), nickel (Ni), molybdenum (W), cobalt (Co), silver (Ag), copper (Cu), aluminum (Al), manganese (Mn), iron (Fe ), can be used as an electrolyte solution containing at least one metal selected from the group consisting of tin (Sn) and vanadium (V).

According to the embodiment, the second cathode material 310b may be provided as an insoluble cathode material unlike the first cathode material 310a, and more preferably coated with insoluble iridium oxide (Insoluble Ir ₂ O ₃ ). It may be provided as a titanium (Ti) plate.

In the step S30, after spraying the third electrolyte into the third electrolysis cell 300c, a third current is passed between the cathode rotating plate 200 and the third anode material 310c to form the copper foil layer 150. This is the step of precipitation.

The ultra thin copper foil 150 means an ultra thin copper (Cu) thin film precipitated on the carrier metal layer 110 and the separation layer 130 so that the ultra thin copper foil is adhered to the insulating layer.

According to an embodiment, the copper foil layer 150 may be deposited to a thickness of 10 μm or less, more preferably 1 to 5 μm. When the thickness of the ultra-copper foil layer 150 is less than 1 μm, the ultra-thin copper foil layer 150 is too thin and it is difficult to sufficiently realize electrical characteristics when adhered to the insulating layer. In addition, when the thickness of the ultra-copper foil layer 150 is less than 1 μm, it is very difficult to evenly deposit the same thickness on the separation layer 130. Conversely, if the thickness of the copper foil layer 150 exceeds 10 μm, the thickness of the printed circuit board may increase and thus the semiconductor adhesion may be reduced, and a carrier layer is not required. For this reason, the thickness of the polar copper foil layer 150 is preferably 10 μm or less, and more preferably, it may be deposited to a thickness of 1 to 5 μm.

According to an embodiment, the third electrolyte may be provided as a sulfuric acid (H ₂ SO ₄ ) solution containing copper (Cu) ions. More preferably, it may be provided as a solution in which 30 to 80 g/L of copper (Cu) ions are mixed with 100 to 200 g/L of sulfuric acid.

According to the embodiment, the third positive electrode material 310c may be provided as an insoluble positive electrode material similar to the second positive electrode material 310b, and more preferably coated with insoluble iridium oxide (Insoluble Ir ₂ O ₃ ). It may be provided as a titanium (Ti) plate.

The step S40 is a step of forming the roughened layer 170 on the surface of the ultra-copper foil layer 150 by the fourth electrolytic cell 300d1 and the fifth electrolytic cell 300d2.

The roughened layer 170 means a metal layer created to increase the adhesive strength between the copper foil layer 150 and the insulating layer. More preferably, the roughened layer 170 may be provided by generating a metal core provided as copper (Cu) on the surface of the copper foil layer 150 and growing the generated metal core.

That is, the roughened layer 170 means a layer in which copper is grown on the surface of the ultra-copper foil layer 150 so as to improve the adhesion of the ultra-copper foil layer. However, if the surface roughness of the copper foil layer 150 after the step S40 is 1.0 μm or more, electrical characteristics may be reduced due to excessive surface roughness. It is desirable to increase the surface roughness within the range of maintaining less than 1.0 μm.

According to an embodiment, the step S40 may be performed by separately electroforming two different types of electrolysis cells and the cathode rotating plate 200, unlike steps S10 to S30 described above. Hereinafter, a step in which the fourth electrolytic cell 300d1 and the cathode rotary plate 200 are electroformed is defined as a first roughening step, and the fifth electrolytic cell 300d2 and the cathode rotary plate 200 are electroformed. This step is defined as the second harmonization step.

The first roughening step is a step of generating and fixing copper nuclei on the surface of the ultra-copper foil layer 150.

Specifically, the first roughening process is performed by injecting a fourth electrolyte into the fourth electrolytic cell 300d1 and then passing a fourth current between the cathode rotating plate 200 and the fourth anode material 310d1. Copper nuclei may be generated on the surface of the ultra-copper thin layer 150, and the generated nuclei may be fixed to the surface of the ultra-poisonous thin layer 150.

According to an embodiment, the fourth electrolyte may be provided as a solution obtained by mixing 50 to 150 g/L of sulfuric acid with 10 to 30 g/L of copper (Cu) ions, and may be maintained at 15 to 25°C.

In addition, the first roughening process may be performed by injecting a current density of 5 to 15 A/dm 2 into the fourth electrolysis cell 300d1 for 5 to 20 seconds.

According to an embodiment, through the first roughening step, the surface roughness (Rz) of the present invention can be increased to 0.05 to 0.3 μm compared to the surface of the ultra-copper foil layer 150 that has not been roughened.

After performing the first roughening process, a second roughening process may be performed. Through this, copper nuclei formed on the surface of the ultra-copper foil layer 150 can grow to form a roughened layer.

Specifically, the second roughening treatment step is performed by injecting a fifth electrolyte into the fifth electrolytic cell 300d2 and then passing a fifth current between the cathode rotating plate 200 and the fifth anode material 310d2. It can be. That is, the first roughening treatment may be performed using a different electrolytic cell and in a different type of electrolyte and current state.

The fifth electrolyte solution may be provided as a solution in which 50 to 100 g/L of copper (Cu) ions are mixed with 100 to 200 g/L of sulfuric acid. That is, the fifth electrolyte has a higher concentration of copper (Cu) ions than the fourth electrolyte. Due to this difference, the second roughening process can grow the copper core to a sufficient size.

In addition, the fifth electrolyte is preferably provided at 30 to 60 °C, unlike the fourth electrolyte provided at 15 to 25 °C. That is, in the first electrolytic treatment step, the temperature of the electrolyte solution is limited to 25° C. or less, so that a small number of nuclei may be prevented from excessively growing, and more nuclei may be generated. On the other hand, in the second electrolytic treatment step, the growth rate of the copper nuclei may be improved by providing the temperature of the electrolyte at 30° C. or higher.

According to an embodiment, through the second roughening step, the present invention may finally form the surface of the ultra-copper foil layer 150 to 1.5 to 4.0 Rz.

In addition, the fourth positive electrode may be provided as an insoluble positive electrode material, more preferably, a titanium (Ti) plate coated with iridium oxide (Insoluble Ir ₂ O ₃ ) like the second and third positive electrode materials.

Specifically, since the first roughening process is a process of generating and fixing nuclei, the voltage condition must be kept constant during the nucleation process, so that the fourth cathode material 310d1 is provided as insoluble. it is desirable

On the other hand, the fifth cathode material is provided as a soluble cathode material provided as a copper piece (Cu plate) or a copper ball (Cu ball) having solubility, or a titanium (Ti) plate coated with lithium oxide (Insoluble Ir ₂ O ₃ ) Any one of insoluble cathode materials may be provided.

According to an embodiment, the fourth positive electrode material is provided as an insoluble positive electrode material of a titanium (Ti) plate coated with iridium oxide (Insoluble Ir ₂ O ₃ ), and the fifth positive electrode material is a copper piece (Cu plate) or a copper ball. It can be provided as a soluble cathode material provided in (Cu ball).

In this case, since the second roughening step is performed using a soluble anode agent, oxygen (O ₂ ) is easily discharged, and additional facilities for supplying copper (Cu) ions are not required, so that copper nuclei can be stably grown.

Thereafter, the copper foil 1000 for semiconductors may be peeled off from the cathode rotating plate 200 through the step S50.

Through the above-described process, the semiconductor copper foil 100 is obtained by sequentially depositing the carrier metal layer 110, the separation layer 130, the copper foil layer 150, and the roughening treatment layer 170 by one copper foil manufacturing device. The copper foil 100 for semiconductors can be manufactured by one-pass.

According to the embodiment, the copper foil 100 for semiconductors manufactured through steps S10 to S50 may be subjected to anti-rust treatment through step S60.

The anti-corrosive treatment can form a zinc alloy layer on the surface of the roughened copper foil 100 for semiconductors to improve softening resistance and prevent the copper foil 100 for semiconductors from being discolored during storage and processing.

Specifically, in the step S60, a current of 10 to 20 / dm 2 is applied in a state in which the copper foil 100 for a semi-structure is supported in a sulfuric acid (H ₂ SO ₄ ) solution in which 20 to 80 g / ℓ of zinc (Zn) is dissolved. The anti-rust treatment may be performed by pouring for 20 seconds.

According to an embodiment, after performing the anti-corrosive treatment, the chromate treatment layer may be formed by supporting the anti-corrosive copper foil for semiconductors in a chromic acid (CrO ₃ ) solution at 20 to 30 °C.

The manufacturing method of the copper foil for semiconductors according to the embodiment of the present invention has been described above. Hereinafter, the copper foil for semiconductors will be described in more detail through specific examples.

As described above, the copper foil 100 for semiconductors according to an embodiment of the present invention is manufactured with a plurality of electrolytic cells including at least first to fifth

electrolytic cells

300a, 300b, 300c, 300d1, and 300d2. It can be manufactured by the device 1000, and through one device, the carrier metal layer 110, the separation layer 130, the copper foil layer 150, and the roughened layer 170 are sequentially deposited to form one copper foil for semiconductors. (100) can be formed.

According to the embodiment, the first to fifth

electrolytic cells

300a, 300b, 300c, 300d1, and 300d2 are supplied with a cathode material, electrolyte, and current under the conditions shown in Table 1 below, and the carrier metal layer ( 110), the separation layer 130, the copper foil layer 150, and the roughened layer 170 may be sequentially deposited.

	음극재cathode material	전해액electrolyte	전해액 온도electrolyte temperature	양극재cathode material	전류electric current	두께thickness
캐리어 금속층carrier metal layer	Ti PlateTi Plate	H₂SO₄: 150g/ℓ Cu ion: 90g/ℓH ₂ SO ₄ : 150g/ℓ Cu ion: 90g/ℓ	45℃45℃	- Soluble - Cu metal ball-Soluble - Cu metal ball	30A/dm² 30A/ ^dm2	9㎛9㎛
분리층separating layer		In ion: 10g/ℓ Cr ion: 20g/ℓ Zn ion: 15g/ℓ C₆H₅Na₃O₇: 100g/ℓIn ion: 10g/ℓ Cr ion: 20g/ℓ Zn ion: 15g/ℓ C ₆ H ₅ Na ₃ O ₇ : 100 g/ℓ	45℃45℃	- Insoluble - Ti plate coated by Ir₂O₃ - Insoluble -Ti plate coated by Ir ₂ O ₃	5A/dm² 5A/ ^dm2	0.01㎛0.01 μm
극동박층Far East Laminate		H₂SO₄: 150g/ℓ Cu ion: 65g/ℓH ₂ SO ₄ : 150g/ℓ Cu ion: 65g/ℓ	40℃40℃	- Insoluble - Ti plate coated by Ir₂O₃ - Insoluble -Ti plate coated by Ir ₂ O ₃	15A/dm² 15A/ ^dm2	2㎛2㎛
조화처리층Coordination treatment layer		H₂SO₄: 100g/ℓ Cu ion: 15g/ℓH ₂ SO ₄ : 100g/ℓ Cu ion: 15g/ℓ	20℃20℃	-Insoluble - Ti plate coated by Ir₂O₃ -Insoluble -Ti plate coated by Ir ₂ O ₃	10A/dm² 10A/ ^dm2	0.1㎛0.1㎛
조화처리층Coordination treatment layer		H₂SO₄: 150g/ℓ Cu ion: 65g/ℓH ₂ SO ₄ : 150g/ℓ Cu ion: 65g/ℓ	40℃40℃	- Soluble - Cu metal ball-Soluble - Cu metal ball	15A/dm² 15A/ ^dm2	0.1㎛0.1㎛

That is, in the copper foil 100 for semiconductors according to an embodiment of the present invention, the carrier metal layer 110, the separation layer 130, and the copper foil layer 150 are formed on one cathode rotating plate 200 according to the conditions disclosed in Table 1 above. And it is possible to manufacture one copper foil 100 for semiconductors by sequentially depositing the roughened layer 170 . Through this, the production process can be simplified by using one copper foil manufacturing apparatus 1000, and the precipitation process of each layer can be performed in real time through one cycle to be manufactured as one finished product.

In addition, by directly depositing the ultra-copper foil layer 150 on the separation layer 130, it is possible to minimize damage and cracks occurring during the deposition process of the ultra-copper foil layer 150. For this reason, even a very thin ultra-thin copper foil layer 150 having a thickness of 5 μm or less can be stably produced.

It can be seen that this is an advanced technology with improved productivity and quality compared to the existing manufacturing method in which the device for producing the carrier metal layer 110 and the device for depositing the copper foil layer 150 are separately required.

In addition, the present invention is an additional process required to maintain the bonding strength of the metal layers by depositing the carrier metal layer 110, the separation layer 130, the copper foil layer 150, and the roughened layer 170 in real time with one device, or Heat treatment may be omitted, thereby minimizing damage or thermal deformation of the copper foil layer 150 during the manufacturing process.

Lastly, according to the present invention, process conditions such as the type, concentration, and current density of the electrolyte solution supplied to the first to fifth

electrolytic cells

300a, 300b, 300c, 300d1, and 300d2 can be independently controlled. Through this, the electrical, physical and mechanical properties of the copper foil 100 for semiconductors can be diversified, and the electrical properties, thickness, material, etc. of each metal layer can be easily converted as needed.

In the above, the present invention has been described in detail using preferred embodiments, but the scope of the present invention is not limited to specific embodiments, and should be interpreted according to the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

Claims

Manufactured by a copper foil manufacturing apparatus including a cathode rotating plate rotating in one direction and first to fifth electrolytic cells spaced apart from each other at predetermined intervals along the cathode rotating plate and containing an electrolyte solution and a cathode material therein,

depositing a carrier metal layer on the cathode rotating plate by the first electrolysis cell;

depositing a separation layer on the carrier metal layer by the second electrolysis cell;

depositing an ultra-copper foil layer on the separation layer by the third electrolysis cell; and

Forming a roughened layer on the surface of the copper foil layer by the fourth electrolytic cell and the fifth electrolytic cell;

As the cathode rotation plate rotates, the first to fifth electrolysis cells are sequentially electroformed with the cathode rotation plate to form a single semiconductor copper foil.
According to claim 1,

The first to fifth electrolytic cells,

A method for manufacturing a copper foil for semiconductors, characterized in that each electrolytic cell is independently supplied with a current and an electrolyte of different sizes.
According to claim 1,

The carrier metal layer is

Formed by injecting a first electrolyte solution into the first electrolysis cell and then passing a first current;

The method of manufacturing copper foil for semiconductors, characterized in that the first cathode material included in the first electrolysis cell is provided as a metal plate or metal ball having solubility.
According to claim 1,

The separation layer is

Formed by injecting a second electrolyte into the second electrolysis cell and then passing a second current;

The second anode material included in the second electrolysis cell is provided as a titanium (Ti) plate coated with iridium oxide (Ir 2 O 3 ).
According to claim 1,

The far copper thin layer is

Formed by injecting a third electrolyte into the third electrolysis cell and then passing a third current;

The third anode material included in the third electrolysis cell is provided as a titanium (Ti) plate coated with iridium oxide (Ir2O3).
According to claim 1,

The step of forming the roughened layer is

A first roughening step of forming and fixing copper cores; and

A second roughening step of growing the copper core,

The first roughening step is characterized in that performed by the fourth anode material provided as a titanium (Ti) plate coated with iridium oxide (Ir2O3), a method for manufacturing copper foil for semiconductors.
According to claim 6,

Characterized in that the second roughening step is performed by the fifth anode material provided with any one of a soluble metal plate or a titanium (Ti) plate coated with iridium oxide (Ir2O3) , Manufacturing method of copper foil for semiconductors.
a carrier metal layer;

a separation layer precipitated on the upper surface of the carrier metal layer;

an ultra-copper foil layer precipitated on the upper surface of the separation layer;

a roughening layer formed on the surface of the copper foil layer; and

In the copper foil for semiconductors comprising a; anti-rust plating layer formed on the surface of the roughened layer,

The copper foil for semiconductors,

a cathode rotating plate rotating in one direction; and

It is manufactured by a copper foil manufacturing apparatus including; first to fifth electrolytic cells spaced apart from each other at predetermined intervals along the cathode rotating plate and containing an electrolyte solution and a cathode material therein;

As the cathode rotating plate rotates, the first to fifth electrolytic cells are sequentially electroformed with the cathode rotating plate to form a single semiconductor copper foil.
According to claim 8,

The first to fifth electrolysis cells,

A copper foil for semiconductors, characterized in that it is produced by a copper foil manufacturing apparatus that independently supplies currents of different magnitudes to each electrolysis cell and electrolytically molds it independently of the cathode rotating plate.
According to claim 8,

The carrier metal layer is made of copper (Cu), nickel (Ni), chromium (Cr), aluminum (Al) or an alloy containing the same, characterized in that formed to a thickness of 5 to 50㎛, copper foil for semiconductors.
According to claim 8,

The separation layer is provided with indium (In), zinc (Zr), chromium (Cr) or an alloy layer containing the same, characterized in that the thickness is formed to 0.01㎛ or less, copper foil for semiconductors.