KR20140135007A - Copper plating solution composition for printed circuit board and via hole filling method using the same - Google Patents

Abstract

The present invention provides: a copper plating solution composition, including cooper salt, acid, a gloss supplement, a brightener, polyvinylpyrrolidone, and a reducing agent, for a printed circuit board; and a method for filling a via hole using the same. According to the present invention, the copper plating solution composition can prevent the via hole from being void, having dimples, and being over filled when the via hole is filled during an electrical copper plating process.

Description

Technical Field [0001] The present invention relates to a copper plating solution composition for a printed circuit board, and a via hole filling method using the copper plating solution composition.

The present invention relates to a copper plating solution composition for a printed circuit board and a via hole filling method using the copper plating solution composition.

In recent years, a build-up method has been introduced as a new multi-layer printed circuit board manufacturing method in order to cope with the advancement of electronic devices and the progress of densification or multilayering of printed circuit boards. In the build-up method, as the interlayer connection method of another conductor, the inner wall of the via hole is plated to conduct the connection. In general, planarization is performed after an insulating resin or a conductive paste is filled in an inner wall of a via hole to form an insulating layer. However, in this case, planarization is limited.

Therefore, in order to solve the above problems, there has been devised a resin multi-layer substrate of a full-layer inner-via structure and a printed circuit board using an interlayer connection through a fine bump. On the other hand, as the conductor pattern gradually becomes finer, the via hole filling method of filling the inside of the via hole with copper plating is focused as an excellent method in terms of process and connection reliability.

Conventionally, a via hole filling method is a method of filling the via hole with an insulating resin or an electrically conductive paste after the via hole is made conductive in a hollow form. However, when such a method is used, voids are generated inside the via-hole and the surface is dented, and the difference in thermal expansion coefficient between the metal and the insulating resin adversely affects the connection reliability and the electric conductivity is lowered . Therefore, the via hole filling method of filling the via holes with metal copper in the course of increasingly miniaturization of the wiring allows via on vias or stack vias to further increase the densification of the circuit wiring, And its application is further expanded because it is stable in connection reliability.

Currently, as a method of filling via holes, a method of filling via holes through copper electroplating is widely applied. However, when the via holes are filled using the composition of the copper electroplating additive and the bath through the conventional copper electroplating technique, even if charging is not performed in the via holes or charging is performed, voids are formed in the via holes There is a problem that occurs. Therefore, a copper plating solution composition and a charging method which can completely fill the via hole without generating voids and improve the uniformity and flatness of the plating film are urgently required.

On the other hand, Patent Document 1 discloses a copper electroplating solution composition containing polyvinylpyrrolidone. However, a reducing agent used in the chemical copper plating method is used as a reaction solvent rather than the above composition to form fine and uniform via hole filling There is a problem that it can not do.

Patent Document 1: Korea Patent Publication No. 2011-0063810

Accordingly, the present invention provides a copper plating solution composition for a printed circuit board, which comprises polyvinylpyrrolidone and a copper plating solution composition containing a reducing agent, and a via hole filling method using the copper plating solution composition to prevent voids, dimples and overfills in via holes And the present invention has been completed on the basis thereof.

Accordingly, one aspect of the present invention is to provide a copper plating solution composition for a printed circuit board that prevents voids, dimples and overfilling in via holes.

Another aspect of the present invention is to provide a via hole filling method in which the copper plating solution composition has improved via hole defects.

A copper plating solution composition for a printed circuit board (hereinafter referred to as "first invention") according to the present invention for achieving the above one aspect comprises: a copper salt; mountain; Gloss aids; Brightener; Polyvinylpyrrolidone; And a reducing agent.

In a first invention, the composition comprises 0.1 to 0.3% by weight of a copper salt, 1 to 2% by weight of an acid, 0.0002 to 0.0008% of a gloss aid, 0.05 to 0.2% of a polishing agent, 0.001 to 0.01% Vinyl pyrrolidone, 10 to 30% by weight of a reducing agent and the balance of water.

In the first invention, wherein the copper salt is copper sulfate _{(CuSO 4 · 5H 2 O)} , copper nitrate _{(Cu (NO 3) 2)} , formic acid, copper (Cu (HCOO) ₂₎ and cupric chloride (CuCl ₂ · 2H ₂ O).

In the first invention, the acid is at least one selected from the group consisting of sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), acetic acid (CH ₃ COOH) and boron fluoride acid (HBF ₄ ).

In the first aspect of the present invention, the gloss assistant may be selected from the group consisting of chloride ions (Cl), hydrochloric acid (HCl), and sodium chloride (NaCl).

In the first invention, the brightening agent is bis-sodium sulfopropyl-disulfide, bipyridine, or a mixture thereof.

In the first invention, the amount of the polyvinylpyrrolidone used is 0.004 to 0.006% by weight.

In the first invention, the molecular weight of the polyvinyl pyrrolidone is 100,000 to 5,000,000.

In the first invention, the amount of the reducing agent used is 17 to 25% by weight.

In the first aspect of the present invention, the reducing agent is at least one selected from the group consisting of acetaldehyde, dimethyl formamide, and formic acid.

(Hereinafter referred to as "second invention") for achieving another aspect of the present invention is a method for filling a via hole for a printed circuit board, Immersing the object to be plated in a copper plating electrolytic solution containing a copper plating solution composition containing a reducing agent; And

Electrolyzing and plating at a high current density working environment of 3.0 to 5.0 A / dm < ² > and a temperature condition of 20 to 60 DEG C; .

In the second invention, the copper plating solution composition may contain 0.1 to 0.3 wt% of a copper salt, 1 to 2 wt% of an acid, 0.0002 to 0.0008 wt% of a polishing aid, 0.05 to 0.2 wt% of a polishing agent, 0.001 to 0.01 wt% By weight of polyvinylpyrrolidone, 10 to 30% by weight of a reducing agent and the balance of water.

In the second invention, the brightening agent is bis-sodium sulfopropyl-disulfide, bipyridine, or a mixture thereof.

In the second invention, the amount of the polyvinylpyrrolidone used is 0.004 to 0.006% by weight.

In the second invention, the molecular weight of the polyvinyl pyrrolidone is 100,000 to 5,000,000.

In the second invention, the amount of the reducing agent used is 17 to 25% by weight.

In the second aspect of the present invention, the reducing agent is at least one selected from the group consisting of acetaldehyde, dimethyl formamide, and formic acid.

The copper plating liquid composition for a printed circuit board according to the present invention and the method for filling a via hole using the copper plating solution according to the present invention are characterized by adding a reducing agent used in an organic additive and a mechanism of chemical copper plating in the process of filling the via hole according to the copper electroplating method, It has an effect of preventing voids, dimples and overfills in the holes.

The features and advantages of the present invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings.

FIGS. 1A, 1B, and 1C are cross-sectional views of a via hole of a printed circuit board copper-plated with a copper plating solution composition containing an inhibitor, a brightener, and a leveling agent, which are organic additives added to a copper plating solution composition for a printed circuit board.
2 is a cross-sectional view of a via hole of a printed circuit board filled with a copper plating solution composition according to Example 1 of the present invention.
3 is a cross-sectional view of a via hole of a printed circuit board filled with a copper plating solution composition according to a second embodiment of the present invention.
4 is a cross-sectional view of a via hole of a printed circuit board filled with a copper plating solution composition according to Example 3 of the present invention.
5 is a cross-sectional view of a via hole of a printed circuit board filled with a copper plating solution composition according to Comparative Example 1 of the present invention.
6 is a cross-sectional view of a via hole of a printed circuit board filled with a copper plating solution composition according to Comparative Example 2 of the present invention.

Before describing the invention in more detail, it is to be understood that the words or words used in the specification and claims are not to be construed in a conventional or dictionary sense, It should be interpreted based on the principle that it can be defined and the meaning and the concept corresponding to the technical idea of the present invention. Therefore, it is to be understood that the constitution of the embodiments described herein is merely a preferred example of the present invention, and does not represent all of the technical ideas of the present invention, so that various equivalents and modifications It should be understood.

Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

1A, 1B, and 1C are cross-sectional views of a mechanism in which a via hole is filled when an inhibitor, a brightener, and a flatting agent, which are organic additives, are added to a composition containing a copper salt, an acid, to be.

FIG. 1A is a cross-sectional view of a via hole copper plating by adding an inhibitor, which is an organic additive, to a copper plating solution composition containing a copper salt, an acid, and a luster assistant. Referring to FIG. 1A, the first insulating layer 10, (20) and a second insulating layer (12) are continuously laminated. A via hole is formed in the second insulating layer 12 of the printed circuit board by using a laser or the like and the inhibitor is added to the copper plating solution when the copper is filled with the copper plating solution. Since the inhibitor has a high molecular weight as a high molecular component, it has small mobility and is present on the surface of the substrate, thereby preventing the coating thickness of the substrate surface to be thick and the thickness of the plating in the hole to be thin. Thus, the second copper layer 22 filled with the via-hole with improved uniformity of the plated film is formed.

FIG. 1B is a cross-sectional view of a via hole copper plating by adding an inhibitor, which is an organic additive, to a copper plating solution composition containing a copper salt, an acid and a luster assistant. Referring to FIG. 1B, the first insulating layer 10, (20) and a second insulating layer (12) are continuously laminated. A via hole is formed in the second insulating layer 12 of the printed circuit board using a laser or the like, and when the via is filled with the copper plating solution, the brightener is added to the copper plating solution to form a second copper layer (22). The brightening agent is adsorbed to the crystal nucleus growth point to inhibit further growth of crystals. As a result, a large number of new nuclei are generated and the crystal becomes finer, and a glossy film excellent in film properties is obtained.

FIG. 1C is a cross-sectional view of a via hole copper plating by adding an inhibitor, which is an organic additive, to a copper plating solution composition containing a copper salt, an acid, and a luster assistant. Referring to FIG. 1C, the first insulating layer 10, (20) and a second insulating layer (12) are continuously laminated. A via hole is formed in the second insulating layer (12) of the printed circuit board using a laser or the like. When filling the via with the copper plating solution, the flatting agent is added to the copper plating solution to form a second copper Layer 22 is formed. Since the flattening agent is dominated by the diffusion of the adsorbing action on the Cu surface, a large amount is adsorbed on the surface of the substrate on which the plating liquid agitates sufficiently, and a small amount is adsorbed on the bottom portion of the via hole with small agitation. Cu precipitation reaction is suppressed on the surface of the substrate, Cu metal is precipitated first in the bottom portion of the via hole to obtain plating flatness.

In the present invention, in order to prevent voids, dimples and overfilling in the via-holes in the process of filling copper plating solution composition for printed circuit board according to the copper electroplating method and via-hole filling method using the copper plating solution composition, Wherein the copper salt is selected from the group consisting of 0.3% by weight of copper salt, 1 to 2% by weight of acid, 0.0002 to 0.0008% by weight of a polishing aid, 0.05 to 0.2% by weight of a polishing agent, 0.001 to 0.01% by weight of polyvinylpyrrolidone, The reductant and remainder include water.

Copper salt

Copper plating obtained from the copper salt plating liquid can be suppressed from cracking due to expansion and contraction of the material due to temperature change with high ductility. The copper salt in the present invention is copper sulfate _{(CuSO 4 · 5H 2 O)} , copper nitrate _{(Cu (NO 3) 2)} , formic acid, copper (Cu (HCOO) ₂₎ and cupric chloride (CuCl ₂ · 2H ₂ O) And is not particularly limited, but it is preferable that the copper plating solution composition contains 0.1 to 0.3% by weight in the copper plating solution composition. If the amount of the copper salt is less than 0.1% by weight, tumbling tends to occur at a high current density portion, and when it exceeds 0.3% by weight, pits tend to occur.

mountain

In the present invention, the acid is at least one selected from the group consisting of sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), acetic acid (CH ₃ COOH) and borofluoric acid (HBF ₄ ) It is preferable that the plating liquid composition contains 1 to 2% by weight. The acid which is the main component of the copper plating solution composition should be supplemented regularly by analysis.

Brightening agent

In the present invention, the brightening aid is at least one selected from the group consisting of chloride (Cl), hydrochloric acid (HCl), and sodium chloride (NaCl), and is not particularly limited. . A small amount of polishing adjuvant is needed to aid in gloss.

Polish ( brightner )

The brightener accelerates plating and atomizes Cu crystals to provide gloss of the plating film. The reaction mechanism of the brightener is shown in the following reaction formula (1).

[Reaction Scheme 1]

1/2 SPS + H ⁺ + e ^- → MPS

2MPS + Cu ^{2 +} → Cu (I) thiolate + 1 / 2SPS + 2H ⁺

Cu (I) thiolate + H ⁺ + e ^- → Cu + MPS

Cu ^{2 +} + 2e ^- ? Cu

As the SS bond of bis-sodium sulfopropyl disulfide is broken, the 3-mercapto-1-propanesulfonic acid and electrons are generated, and the dehydrogenated thiolate of the 3-mercapto-1-propanesulfonic acid Is coupled with Cu ⁺ ions. Cu (I) thiolate reacts with electrons and hydrogen ions to deposit Cu metal on the Cu surface of the substrate and convert back to the 3-mercapto-1-propanesulfonic acid seed. The brightener is adsorbed to the substrate surface and the via hole as a whole, and the amount of adsorption is increased at the bottom of the via hole where the surface area becomes smaller with the growth of the plating, thereby promoting the via-hole bottom-up plating.

The effect of the polishing agent on leveling is as follows.

Since the above-mentioned brightening agent as an electrolytic deposition promoting component remains on the surface of the plating film without being vacant, the amount of adsorption increases in the concave-convex portion where the surface area becomes smaller with the growth of the plating. As a result, electrolytic precipitation of the concave-convex portion is promoted and leveling is obtained. Such a mechanism of the polishing agent is called a memorization.

In the present invention, the brightener is selected from any one of bis-sodium sulfopropyl disulfide and bipyridine, and is preferably bis-sodium sulfopropyl disulfide in the sulfur compound series.

The bis-sodium sulfopropyl disulfide is not particularly limited, but preferably contains 0.05 to 0.2% by weight in the copper plating solution composition. When the amount of bis-sodium sulfopropyl disulfide is less than 0.05% by weight, the crystal nuclei generated in the initial stage of plating are first grown at the time of plating on the substrate, and the crystal grows in the longitudinal direction to a large extent, . In addition, when bis-sodium sulfopropyl disulfide is added, it is adsorbed to the crystal nucleus growth point when plated on a substrate to inhibit further growth of crystals. As a result, a large number of new nuclei are generated and the crystals are made finer to obtain a glossy film excellent in film properties. However, if the bis-sodium sulfopropyl disulfide exceeds 0.2% by weight, an over-fill phenomenon may occur.

Polyvinylpyrrolidone  ( polyvinylpyrrolidone )

In the present invention, polyvinylpyrrolidone has a role of both an inhibitor and a flatting agent since it easily forms a complex with a metal.

The inhibitor is known as a polymer component of polyethylene glycol, polypropylene glycol, homo polymer and copolymer. The inhibitor has the role of inhibiting plating growth and improving the uniformity of the plating film.

The polyethylene glycol and the Cu ⁺ cationic complex bind to the chloride ion (Cl) adsorbed on the surface of the substrate Cu by an electrical force, and form a monomolecular film on the surface of the Cu to inhibit Cu ions from precipitating into the metal. Since the inhibitor has a high molecular weight as a high molecular component, it has small mobility and is very present on the surface of the substrate. Therefore, the plating thickness of the substrate surface is thick and the thickness of the plating in the hole is prevented from being thinned. Improvement.

The flatting agent interacts with the inhibitor to improve plating growth and to improve the uniformity of the plating film. It is known that amine compounds such as Janus Green B, polyethyleneimine and imidazole series are used. It is bonded with chloride ion (Cl) by electric attraction and adsorbed on the surface of the substrate Cu, Thereby suppressing precipitation of ions into the metal.

Since the flattening agent is dominated by the diffusion of the adsorbing action on the Cu surface, a large amount is adsorbed on the surface of the substrate on which the plating liquid agitates sufficiently, and a small amount is adsorbed on the bottom portion of the via hole with small agitation. Cu precipitation reaction is suppressed on the surface of the substrate, Cu metal is precipitated first in the bottom portion of the via hole to obtain plating flatness.

Therefore, the Cu deposition reaction is suppressed on the surface of the substrate via the polyvinylpyrrolidone, and the Cu metal is precipitated first in the bottom of the via hole, and the plating flatness is obtained.

The polyvinyl pyrrolidone may have a molecular weight of 100,000 to 5,000,000, preferably 100,000. When the polyvinylpyrrolidone having a molecular weight of less than 100,000 is used, the capping effect due to the coordination with the metal using the polymer is lowered, and an effective performance as a flatting agent may not be realized. Further, when the above-mentioned polyvinylpyrrolidone having a molecular weight of 5,000,000 or more is used, the solubility in the solution is lowered and the compatibility is lowered.

The polyvinyl pyrrolidone is represented by the following Chemical Formula 1 and is characterized by containing 0.001 to 0.01 wt%, preferably 0.004 to 0.006 wt%, in the copper plating solution composition. If the amount of the polyvinylpyrrolidone is less than 0.001% by weight, the flatness of the plating tends to decrease. If the amount of the polyvinylpyrrolidone is more than 0.01% by weight, overfilling in the via hole may occur.

[Chemical Formula 1]

The polyvinylpyrrolidone enables via-hole filling through adsorption in the substrate and control of copper plating rate. The mechanism of the polyvinylpyrrolidone is represented by the following Chemical Formula 2 and functions to cap Cu particles.

(2)

reducing agent

In the process of filling a via hole for a printed circuit board according to the copper electroplating method of the present invention, voids, dimples and overfill phenomenon in the via hole are added by adding a reducing agent used in the oxidation / reduction mechanism of the copper copper plating method prevent. The reducing agent acts as the largest composition among the copper electroplating solution compositions of the present invention, and is effective when filling minute holes. The reducing agent is at least one selected from the group consisting of acetaldehyde, dimethyl formamide and formic acid, and is preferably dimethylformamide.

In the present invention, the reduction mechanism of Cu through dimethylformamide is as shown in Scheme 2.

[Reaction Scheme 2]

HCONMe ₂ + Cu ^{2 +} + H ₂ O - > Cu ⁰ + Me ₂ NCOOH + 2H ⁺

Me ₂ NCOOH - > CO ₂ + Me ₂ NH

The formed cabamic acid is easily degradable.

Since dimethylformamide has a higher flash point (60 to 100 ° C) than room temperature, it can be activated, and does not rapidly react to fill the fine portion of the via hole.

The dimethylformamide is represented by the following Chemical Formula 3 and is contained in the copper plating solution composition for a printed circuit board in an amount of 10 to 30% by weight, preferably 17 to 25% by weight. If the amount of dimethylformamide is less than 10% by weight, the reducing agent tends to be difficult to be reduced. When the amount of dimethylformamide is more than 30% by weight, control of the reaction and control of the reduction rate may be difficult.

(3)

The present invention relates to a copper plating solution comprising a copper plating solution containing a copper salt, an acid, a brightening aid, a brightener, a polyvinylpyrrolidone and a reducing agent, ^{2 at} a high current density and at a temperature of 20 to 60 DEG C to provide a via hole charging method for a printed circuit board. When the environment in the workplace is less than 20 ° C, there is a problem in the solubility between the compositions. When the environment is more than 60 ° C, it is included in the range of the flash point of the reducing agent.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to the following examples.

Example 1

Under a via hole (via hole) for processing by a current density of 3.0 A / dm ² in a bath (bath) that includes the electric copper plating solution having the following composition therein having a depth of 50 ㎛ diameter and 45 ㎛ of the printed circuit board After plating at room temperature (25 캜), the plated shape and filling degree of the filled via hole section were confirmed.

Composition:

CuSO ₄ .5H ₂ O 1.47 g / l

H ₂ SO ₄ 13.44 g / l

Cl 5.0 mg / l

Bis-sodium sulfopropyl disulfide 0.755 g / l

45 mg / l polyvinylpyrrolidone

Dimethylformamide 219.27 g / l

The cross section of the via hole filled through the above copper plating liquid composition is shown in Fig. As can be seen from FIG. 2, the via hole was completely filled without generating voids, and the deposition state of the plating layer was also very dense.

Example 2

The procedure of Example 1 was repeated, except that the amount of polyvinylpyrrolidone and dimethylformamide was changed in the copper plating solution composition, and the plated shape and filling degree of the filled via hole section were confirmed.

Composition:

CuSO ₄ .5H ₂ O 1.47 g / l

H ₂ SO ₄ 13.44 g / l

Cl 5.0 mg / l

Bis-sodium sulfopropyl disulfide 0.755 g / l

40 mg / l polyvinylpyrrolidone

Dimethylformamide 250 g / l

The cross section of the via hole filled with the above copper plating liquid composition is shown in Fig. As shown in FIG. 3, the via hole was filled without generating voids, and the deposition state of the plating layer was also dense.

Example 3

The procedure of Example 1 was repeated, except that the amount of polyvinylpyrrolidone and dimethylformamide was changed in the copper plating solution composition, and the plated shape and filling degree of the filled via hole section were confirmed.

Composition:

CuSO ₄ .5H ₂ O 1.47 g / l

H ₂ SO ₄ 13.44 g / l

Cl 5.0 mg / l

Bis-sodium sulfopropyl disulfide 0.755 g / l

Polyvinylpyrrolidone 60 mg / l

Dimethylformamide 170 g / l

The cross section of the via hole filled with the above copper plating solution composition is shown in Fig. As can be seen from FIG. 4, the via hole was filled without generating voids, and the deposition state of the plating layer was also dense.

Comparative Example 1

The copper plating solution composition was subjected to the same procedure as in Example 1 except for polyvinylpyrrolidone, and then the coated shape and filling degree of the filled via hole section were confirmed.

Composition:

CuSO ₄ .5H ₂ O 1.47 g / l

H ₂ SO ₄ 13.44 g / l

Cl 5.0 mg / l

Bis-sodium sulfopropyl disulfide 0.755 g / l

Dimethylformamide 219.27 g / l

5 shows a cross section of the via hole plated with the copper plating solution composition not containing polyvinylpyrrolidone. As can be seen from FIG. 5, the via hole was not completely filled, and voids were formed in the via hole.

Comparative Example 2

The copper plating solution composition was performed in the same manner as in Example 1 except for dimethylformamide, and then the plated shape and filling degree of the filled via hole section were confirmed.

Composition:

CuSO ₄ .5H ₂ O 1.47 g / l

H ₂ SO ₄ 13.44 g / l

Cl 5.0 mg / l

Bis-sodium sulfopropyl disulfide 0.755 g / l

45 mg / l polyvinylpyrrolidone

The cross section of the via hole plated with the copper plating solution composition not containing dimethylformamide is shown in Fig. As can be seen from FIG. 6, the via holes were not completely filled, and dimples were formed in the via holes.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, the same is by way of illustration and example only and is not to be construed as limiting the present invention. It is obvious that it can be modified or improved.

It is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

10: first insulating layer
12: second insulating layer
20: first copper layer
22: a second copper layer filled with via holes
110: Suppressor
120: Brightener
130: leveler

Claims (16)

Copper salt;
mountain;
Gloss aids;
Brightener;
Polyvinylpyrrolidone; And
reducing agent; Wherein the copper plating liquid composition for a printed circuit board comprises copper.
The method according to claim 1,
Wherein the copper plating solution composition contains 0.1 to 0.3 wt% of copper salt, 1 to 2 wt% of an acid, 0.0002 to 0.0008 wt% of a polishing aid, 0.05 to 0.2 wt% of a polishing agent, 0.001 to 0.01 wt% of polyvinylpyrrolidone , 10 to 30 wt% of a reducing agent, and the balance of water.
The method according to claim 1 or 2,
The copper salt is the group consisting of copper sulfate _{(CuSO 4 · 5H 2 O)} , copper nitrate _{(Cu (NO 3) 2)} , formic acid, copper (Cu (HCOO) ₂₎ and cupric chloride (CuCl ₂ · 2H ₂ O) Wherein the copper plating liquid composition is at least one selected from the group consisting of copper and copper.
The method according to claim 1 or 2,
Wherein the acid is at least one selected from the group consisting of sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), acetic acid (CH ₃ COOH) and boron fluoric acid (HBF ₄ ).
The method according to claim 1 or 2,
Wherein the luster auxiliary is at least one selected from the group consisting of chloride ions (Cl), hydrochloric acid (HCl), and sodium chloride (NaCl).
The method according to claim 1 or 2,
Wherein the brightener is bis-sodium sulfopropyl-disulfide, bipyridine, or a mixture thereof. The copper plating solution composition of claim 1, wherein the brightener is bis-sodium sulfopropyl-disulfide, bipyridine or a mixture thereof.
The method according to claim 1 or 2,
Wherein the amount of the polyvinyl pyrrolidone used is 0.004 to 0.006% by weight.
The method according to claim 1 or 2,
Wherein the polyvinyl pyrrolidone has a molecular weight of 100,000 to 5,000,000.
The method according to claim 1 or 2,
Wherein the reducing agent is used in an amount of 17 to 25% by weight.
The method according to claim 1 or 2,
Wherein the reducing agent is at least one selected from the group consisting of acetaldehyde, dimethyl formamide, and formic acid.
Immersing the object to be plated in a copper plating electrolyte solution containing a copper plating solution composition comprising a copper salt, an acid, a brightening aid, a brightener, a polyvinylpyrrolidone and a reducing agent; And
Electrolyzing and plating at a high current density working environment of 3.0 to 5.0 A / dm < ² > and a temperature condition of 20 to 60 DEG C; And a via-hole filling method for a printed circuit board.
The method of claim 11,
The copper plating solution composition may contain 0.1 to 0.3 wt% of a copper salt, 1 to 2 wt% of an acid, 0.0002 to 0.0008 wt% of a polishing aid, 0.05 to 0.2 wt% of a polishing agent, 0.001 to 0.01 wt% of polyvinylpyrrolidone , 10 to 30 wt% of a reducing agent, and the balance of water.
The method of claim 11,
Wherein the polyvinyl pyrrolidone is used in an amount of 0.004 to 0.006% by weight.
The method of claim 11,
Wherein the molecular weight of the polyvinyl pyrrolidone is 100,000 to 5,000,000.
The method of claim 11,
Wherein the reducing agent is used in an amount of 17 to 25 wt%.
The method of claim 11,
Wherein the reducing agent is at least one selected from the group consisting of acetaldehyde, dimethyl formamide, and formic acid.

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