JP2014224304A - Copper plating solution composition for printed wiring board, and via hole filling method using the same - Google Patents

Abstract

In the process of filling a via hole by an electrolytic copper plating method, an organic additive and a reducing agent used for the mechanism of the chemical copper plating method are added to prevent voids, dimples and overfill phenomenon in the via hole. An effective copper plating solution composition for a printed circuit board and a via hole filling method using the same are provided. The copper plating solution composition for printed circuit boards of the present invention comprises a copper salt, an acid, a gloss auxiliary, a brightener, polyvinylpyrrolidone, and a reducing agent. [Selection figure] None

Description

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

  Recently, as the density of printed circuit boards has increased or the number of printed circuit boards has increased with the progress of electronic equipment, a build-up method has been introduced as a method for manufacturing a new multilayer printed circuit board to cope with this. In the build-up method, the inner wall of the via hole is made conductive by plating as an interlayer connection method of different conductors. Normally, planarization is performed after filling the inner wall of the via hole with an insulating resin or conductive paste to form an insulating layer, but in this case, there is a limit to planarization.

  Therefore, in order to solve such problems, a resin multilayer substrate having an all-layer inner via structure in which arbitrary layers are electrically connected and a printed circuit board using interlayer connection by fine bumps have been devised. On the other hand, as the conductor pattern is further miniaturized, the via hole filling method in which the inside of the via hole is filled with copper plating has attracted attention as a method excellent in process and connection reliability.

  As a conventionally applied via hole filling method, there is a method of making the via hole spherical and then filling the inside of the via hole with an insulating resin or a conductive paste.

  However, when such a method is used, a void is generated inside the via hole, and the surface is dented. In addition, the difference in the thermal expansion coefficient between the metal and the insulating resin adversely affects the connection reliability. There is a problem that conductivity becomes low.

  Therefore, the via hole filling method of filling the inside of the via hole with metal copper in the process of further miniaturization of the wiring enables via on via or stack via, and the circuit wiring is further densified. In addition, since the connection reliability is stable, its application is further expanded.

  As the present via hole filling method, a method of filling a via hole by electrolytic copper plating is most widely applied.

  However, when the via hole is filled using an additive for electrolytic copper plating and a bath composition by the conventional copper electroplating technique, the via hole is not filled or the via hole is not filled even if the filling is performed. There is a problem that voids are generated inside. Therefore, there is an urgent need for a copper plating solution composition and a filling method capable of completely filling a via hole without generating voids and improving the uniformity and flatness of the plating film.

  On the other hand, Patent Document 1 discloses an electrolytic copper plating solution composition containing polyvinylpyrrolidone, but a reducing agent used in a chemical copper plating method is used as a reaction solvent instead of the composition. There was a problem that fine and uniform via hole filling could not be performed.

Korean Published Patent No. 2011-0063810

  Therefore, the present inventor has proposed that a copper plating solution composition containing polyvinylpyrrolidone and a reducing agent in a copper plating solution composition for a printed circuit board and a via hole filling method using the same prevent voids, dimples and overfill phenomenon in the via hole. Based on this, the present invention has been completed.

  Accordingly, an object of the present invention is to provide a copper plating solution composition for printed circuit boards which prevents voids, dimples and overfill development in via holes.

  Another object of the present invention is to provide a via hole filling method in which defects in via holes are improved with the copper plating solution composition.

  According to one aspect of the present invention, a copper plating solution composition for printed circuit boards (hereinafter referred to as “first invention”) comprising a copper salt, an acid, a gloss auxiliary, a brightener, polyvinylpyrrolidone, and a reducing agent. ").

  In the first invention, the composition comprises 0.1 to 0.3% by weight of copper salt, 1 to 2% by weight of acid, 0.0002 to 0.0008% by weight of gloss auxiliary, 0.05 to 0.00%. It contains 2% by weight brightener, 0.001 to 0.01% by weight polyvinylpyrrolidone, 10 to 30% by weight reducing agent, and the balance water.

In the first invention, the copper salt includes copper sulfate (CuSO ₄ .5H ₂ O), copper nitrate (Cu (NO ₃ ) ₂ ), copper formate (Cu (HCOO) ₂ ), and cupric chloride (CuCl _2). · 2H 2 _O), wherein the selected at least one from the group consisting of.

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 fluoroboric acid (HBF ₄ ). And

  In the first invention, the gloss auxiliary agent is selected from the group consisting of chloride ion (Cl), hydrochloric acid (HCl) and sodium chloride (NaCl).

  In the first invention, the brightener is bis-sodium sulfopropyl-disulphide, bipyridine, or a mixture thereof.

  1st invention WHEREIN: The usage-amount of the said polyvinyl pyrrolidone is 0.004-0.006 weight%, It is characterized by the above-mentioned.

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

  1st invention WHEREIN: The usage-amount of the said reducing agent is 17-25 weight%, It is characterized by the above-mentioned.

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

According to another aspect of the present invention, the object to be plated is immersed in a copper plating electrolyte containing a copper plating solution composition containing a copper salt, an acid, a gloss auxiliary, a brightener, polyvinylpyrrolidone, and a reducing agent. , 3.0 to 5.0 A / dm ² high current density working environment and 20 to 60 ° C. electrolyzing and plating step for filling a printed circuit board via hole (hereinafter “second invention”) ").

  2nd invention WHEREIN: The said copper plating liquid composition is 0.1 to 0.3 weight% copper salt, 1 to 2 weight% acid, 0.0002 to 0.0008 weight% gloss adjuvant, 0.05 -0.2% by weight brightener, 0.001-0.01% by weight polyvinylpyrrolidone, 10-30% by weight reducing agent, and the balance water.

  In the second invention, the brightener is bis-sodium sulfopropyl-disulphide, bipyridine, or a mixture thereof.

  2nd invention WHEREIN: The usage-amount of the said polyvinyl pyrrolidone is 0.004-0.006 weight%, It is characterized by the above-mentioned.

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

  2nd invention WHEREIN: The usage-amount of the said reducing agent is 17-25 weight%, It is characterized by the above-mentioned.

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

  The copper plating solution composition for a printed circuit board according to the present invention and a via hole filling method using the same are reduced in the process of filling the via hole by an electrolytic copper plating method and used for the mechanism of the organic additive and the chemical copper plating method. The addition of an agent has the effect of preventing voids, dimples and overfill phenomena in the via hole.

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

Sectional drawing which shows that the via hole of the printed circuit board was copper-plated with the copper plating liquid composition which contained the inhibitor as an organic additive added to the copper plating liquid composition for printed circuit boards, a brightener, and a flattening agent, respectively. It is. Sectional drawing which shows that the via hole of the printed circuit board was copper-plated with the copper plating liquid composition which contained the inhibitor as an organic additive added to the copper plating liquid composition for printed circuit boards, a brightener, and a flattening agent, respectively. It is. Sectional drawing which shows that the via hole of the printed circuit board was copper-plated with the copper plating liquid composition which contained the inhibitor as an organic additive added to the copper plating liquid composition for printed circuit boards, a brightener, and a flattening agent, respectively. It is. It is sectional drawing (photograph) which shows having filled the via hole of the printed circuit board with the copper plating liquid composition which concerns on Example 1 of this invention. It is sectional drawing (photograph) which shows having filled the via hole of the printed circuit board with the copper plating composition which concerns on Example 2 of this invention. It is sectional drawing (photograph) which shows having filled the via hole of the printed circuit board with the copper plating liquid composition which concerns on Example 3 of this invention. It is sectional drawing (photograph) which shows having filled the via hole of the printed circuit board with the copper plating liquid composition which concerns on the comparative example 1 of this invention. It is sectional drawing (photograph) which shows having filled the via hole of the printed circuit board with the copper plating liquid composition which concerns on the comparative example 2 of this invention.

  Before describing the present invention more specifically, the terms or words used in the specification and claims should not be limited to the ordinary and lexical meaning, and the invention is best practiced. Based on the principle that the terminology can be appropriately defined for the purpose of explanation, it should be interpreted with the meaning and concept consistent with the technical idea of the present invention. Therefore, the structure of the Example described in this specification is only a suitable example of this invention, and does not represent all the technical thoughts of this invention. Thus, it should be understood that there are various equivalents and variations that can be substituted at the time of this application.

  Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily carry out the present invention. In describing the present invention, detailed descriptions of known techniques that may obscure the subject matter of the present invention are omitted.

  1A, FIG. 1B, and FIG. 1C are the results of adding an inhibitor, a brightener, and a flattening agent as organic additives to a composition containing a copper salt, an acid, and a brightening auxiliary agent made of a copper plating solution for printed circuit boards, respectively. It is sectional drawing of the mechanism with which a via hole is filled.

  FIG. 1A is a cross-sectional view showing that an inhibitor as an organic additive is added to a copper plating solution composition containing a copper salt, an acid, and a gloss auxiliary agent, and via holes are copper-plated with the composition.

  Referring to FIG. 1A, a printed circuit board in which a first insulating layer 10, a first copper foil layer 20, and a second insulating layer 12 are successively laminated. A via hole is formed in the second insulating layer 12 of the printed board using a laser or the like, and the inhibitor is added to the copper plating solution when the via is filled with the copper plating solution. Since the inhibitor is a polymer component and has a large molecular weight, it has low mobility and is present on the surface of the substrate in a large amount. Accordingly, the inhibitor prevents the phenomenon that the plating thickness on the substrate surface is thick and the plating thickness in the hole is thin. Therefore, the second copper foil layer 22 filled with the via hole with improved uniformity of the plating film is formed.

  FIG. 1B is a cross-sectional view showing that an inhibitor as an organic additive is added to a copper plating solution composition containing a copper salt, an acid, and a luster auxiliary agent, and via holes are copper-plated with the composition.

  Referring to FIG. 1B, a printed circuit board in which a first insulating layer 10, a first copper foil layer 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 a copper plating solution, the brightener is added to the copper plating solution, whereby the second filled via hole is formed. A copper foil layer 22 is formed. The brightener is adsorbed on the growth point of the crystal nucleus and suppresses further growth of the crystal. For this reason, a lot of new nuclei are generated, the crystal is refined, and a glossy film having excellent film properties can be obtained.

  FIG. 1C is a cross-sectional view showing that an inhibitor as an organic additive is added to a copper plating solution composition containing a copper salt, an acid and a luster auxiliary agent, and via holes are copper-plated with the composition.

  Referring to FIG. 1C, a printed circuit board in which a first insulating layer 10, a first copper foil layer 20, and a second insulating layer 12 are sequentially stacked. A via hole is formed in the second insulating layer 12 of the printed circuit board using a laser or the like, and when filling the via with a copper plating solution, the flattening agent is added to the copper plating solution to fill the via hole with the second copper foil filled with the via hole. Layer 22 is formed. Since the flattening agent governs the adsorption action on the Cu surface due to diffusion, a large amount is adsorbed on the surface of the substrate where the plating solution is sufficiently stirred, and a small amount is adsorbed on the bottom of the via hole where stirring is small. To do. Cu precipitation reaction is suppressed on the substrate surface, and Cu metal is first deposited on the bottom of the via hole to obtain plating flatness.

  In the present invention, in order to prevent voids, dimples and overfill phenomenon in the via hole in the process of filling with a copper plating solution composition for a printed circuit board by an electrolytic copper plating method and a via hole filling method using the same, As a plating solution composition, 0.1 to 0.3 wt% copper salt, 1 to 2 wt% acid, 0.0002 to 0.0008 wt% gloss auxiliary, 0.05 to 0.2 wt% Brightener, 0.001 to 0.01% by weight of polyvinylpyrrolidone, 10 to 30% by weight of reducing agent, and the balance water.

(Copper salt)
The copper plating obtained from the copper salt plating solution is highly soft and can suppress the occurrence of cracks due to the expansion and contraction of the material accompanying a change in temperature. In the present invention, the copper salts include copper sulfate (CuSO ₄ .5H ₂ O), copper nitrate (Cu (NO ₃ ) ₂ ), copper formate (Cu (HCOO) ₂ ) and cupric chloride (CuCl ₂ · 2H). ₂ O), which is selected from the group consisting of ₂ O) and is not particularly limited, but is preferably contained in the copper plating solution composition in an amount of 0.1 to 0.3% by weight. When the copper salt is less than 0.1% by weight, the high current density portion tends to be burnt, and when it exceeds 0.3% by weight, pits tend to be generated.

(acid)
In the present invention, the acid is selected from the group consisting of sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), acetic acid (CH ₃ COOH), and fluoroboric acid (HBF ₄ ). Although not particularly limited, it is preferable that the copper plating solution composition contains 1 to 2% by weight. The acid that is the main component of the copper plating solution composition must be periodically replenished by analysis.

(Glossy auxiliary)
In the present invention, the gloss adjuvant is at least one selected from the group consisting of chloride ions (Cl), hydrochloric acid (HCl) and sodium chloride (NaCl), and is not particularly limited. It is preferable to contain 0.0002 to 0.0008% by weight in the product. A small amount of gloss auxiliary is needed to aid the gloss effect.

(Brightener [brightner])
The brightening agent has a role of promoting plating and a role of giving the gloss of the plating film by atomizing Cu crystals. The reaction mechanism of the brightener is as shown in the following reaction formula 1.

[Reaction Formula 1]
1/2 SPS + H ⁺ + e ⁻ → MPS
^{2MPS + Cu 2+ → Cu (I} ) thiolate (thiolate) + 1 / 2SPS + 2H +
Cu (I) thiolate + H ⁺ + e ⁻ → Cu + MPS
Cu ²⁺ + 2e ⁻ → Cu

While the S—S bond of bis-sodium sulfopropyl disulfide is broken, 3-mercapto-1-propanesulfonic acid and electrons are generated, and the dehydrogenated thiolate of the 3-mercapto-1-propanesulfonic acid becomes Cu ⁺ ion. Join. Cu (I) thiolate reacts with electrons and hydrogen ions, precipitates as Cu metal on the Cu surface of the substrate, and is further converted into 3-mercapto-1-propanesulfonic acid. The brightener generally adsorbs to the surface of the substrate and the via hole, and promotes the upward plating of the via hole by increasing the amount of adsorption at the bottom of the via hole whose surface area decreases as the plating grows.

  The effect of the brightener on leveling is as follows.

  The brightening agent, which is an electrolytic deposition promoting component, remains on the surface without being co-deposited on the plating film, so that the amount of adsorption on the concave and convex portions whose surface area decreases as the plating grows increases. Eventually, the electrolytic deposition of the convex and concave portions is promoted to obtain leveling. Such a mechanism of the brightener is called a memory theory.

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

  Further, the bis-sodium sulfopropyl disulfide is not particularly limited, but it is preferable to contain 0.05 to 0.2% by weight in the copper plating solution composition.

  When the bis-sodium sulfopropyl disulfide is less than 0.05% by weight, when plating on a substrate, crystal nuclei generated in the initial stage of plating first grow and crystals grow greatly in the vertical direction. A dull film can be obtained. Further, when the bis-sodium sulfopropyl disulfide is added, when it is plated on the substrate, it adsorbs to the growth point of the crystal nucleus and suppresses further growth of the crystal. For this reason, a lot of new nuclei are generated, the crystal is refined, and a glossy film having excellent film properties can be obtained. However, when the bis-sodium sulfopropyl disulfide exceeds 0.2% by weight, an overfill phenomenon may occur.

(Polyvinylpyrrolidone)
In the present invention, polyvinylpyrrolidone can easily form a complex with a metal, and thus has a role of an inhibitor and a leveling agent at the same time.

  The inhibitor is known as a polymer component of polyethylene glycol (polyethylene glycol), polypropylene glycol (polypropylene glycol), a homopolymer, and a copolymer. The inhibitor serves to suppress plating growth and improve the uniformity of the plating film.

After the complex of polyethylene glycol and Cu ⁺ cation is combined with chloride ions (Cl) adsorbed on the Cu surface of the substrate by electrical attraction, a monomolecular film is formed on the Cu surface, whereby the Cu ions are converted into metal. To suppress precipitation. Since the inhibitor is a high molecular component and has a large molecular weight, it has a low mobility and is very much present on the surface of the substrate. Accordingly, the inhibitor improves the uniformity of the plating film by preventing the phenomenon that the plating thickness on the substrate surface is large and the plating thickness in the hole is thin.

  The leveling agent suppresses plating growth and improves the uniformity of the plating film by interaction with the inhibitor. It is known that amine compounds such as Janus Green B, polyethyleneimine, and imidazole are used, and it binds with chloride ions (Cl) by an electric attractive force. It is adsorbed on the Cu surface and suppresses the precipitation of Cu ions as metal.

  In the flattening agent, the adsorption action on the Cu surface is governed by diffusion, so that a large amount is adsorbed on the surface of the substrate where the stirring of the plating solution sufficiently works, and the stirring is small, so that the bottom of the via hole. A small amount is adsorbed. Cu precipitation reaction is suppressed on the substrate surface, and Cu metal is first deposited on the bottom of the via hole to obtain plating flatness.

  Therefore, Cu precipitation reaction is suppressed on the surface of the substrate through the polyvinyl pyrrolidone, and Cu metal is first deposited on the bottom of the via hole, thereby providing an effect of obtaining plating flatness.

  The polyvinyl pyrrolidone can be used in a molecular weight of 100,000 to 5,000,000, and preferably has a molecular weight of 100,000.

  When the polyvinyl pyrrolidone having a molecular weight of less than 100,000 is applied, a capping effect due to coordination with a metal using a polymer is lowered, and an effective performance as a flattening agent may not be realized. . Moreover, when the said polyvinyl pyrrolidone with a molecular weight of 5,000,000 or more is applied, the solubility in a solution will fall and there exists a tendency for compatibility to fall.

  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.

  When the amount of the polyvinyl pyrrolidone used is less than 0.001% by weight, the flatness of the plating tends to decrease, and when it exceeds 0.01% by weight, the problem of overfill phenomenon in the via hole occurs. There is also.

  The polyvinyl pyrrolidone makes it possible to fill a via hole by adsorption in a substrate and adjusting a copper plating rate. Further, the mechanism of the polyvinyl pyrrolidone is represented by the following chemical formula 2 and plays a role of capping Cu particles.

(Reducing agent)
In the process of filling via holes for printed circuit boards by the electrolytic copper plating method of the present invention, voids, dimples and overfill phenomenon in the via holes are added by adding a reducing agent used for the oxidation / reduction mechanism of the chemical copper plating method. To prevent.

  The reducing agent acts as the largest composition in the electrolytic copper plating solution composition of the present invention and is effective when filling fine holes. The reducing agent is at least one selected from the group consisting of acetaldehyde, dimethylformamide and formic acid, and is preferably dimethylformamide.

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

[Reaction Formula 2]
^{_{HCONMe 2 + Cu 2+ + H 2}} O → Cu 0 + Me 2 NCOOH + 2H +
Me ₂ NCOOH → CO ₂ + Me ₂ NH

  The formed carbamic acid is easily degradable.

  The dimethylformamide can be activated because its flash point (60-100 ° C.) is higher than room temperature, and since it does not react abruptly, it fills the fine portions of the via hole.

  The dimethylformamide is represented by the following chemical formula 3 and is characterized in that it is contained in an amount of 10 to 30% by weight, preferably 17 to 25% by weight, in a copper plating solution composition for a printed circuit board.

  When the amount of dimethylformamide is less than 10% by weight, it tends to be difficult to exhibit reducing power as a reducing agent, and when it exceeds 30% by weight, it may be difficult to control the reaction and control the process by adjusting the reduction rate. .

In the present invention, an object to be plated is immersed in a copper plating electrolyte containing a copper plating solution composition containing a copper salt, an acid, a gloss auxiliary, a brightener, polyvinyl pyrrolidone, and a reducing agent. Provided is a via hole filling method for a printed circuit board that is electrolyzed and plated under a working environment with a high current density of dm ² and a temperature condition of 20 to 60 ° C.

  If the environment in the workplace is less than 20 ° C., there is a problem in the solubility between the compositions, and if the environment in the workplace is 60 ° C. or higher, it is included in the flash point range of the reducing agent, which is dangerous. There is.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The scope of the present invention is not limited to these examples.

Example 1
A via hole having a diameter of 50 μm and a depth of 45 μm is processed on a printed circuit board, and the inside of the via hole is subjected to a current density of 3.0 A / dm ^{2 in} a bath containing an electrolytic copper plating solution having the following composition. After plating at room temperature (25 ° C.), the plated shape of the filled via hole cross section and the degree of filling were confirmed.

Composition:
_{CuSO 4 · 5H 2 O 1.47g /} L
H ₂ SO ₄ 13.44 g / L
Cl 5.0mg / L
Bis-sodium sulfopropyl disulfide 0.755 g / L
Polyvinylpyrrolidone 45mg / L
Dimethylformamide 219.27 g / L

  FIG. 2 shows a cross section of the via hole filled with the copper plating solution composition described above. As can be seen from FIG. 2, the via hole was completely filled without the generation of voids, and the deposition state of the plating layer was very dense.

(Example 2)
After the same procedure as in Example 1 except that the amounts of polyvinylpyrrolidone and dimethylformamide used were changed in the copper plating solution composition, the plated shape and the degree of filling of the filled via-hole cross section were confirmed.

Composition:
_{CuSO 4 · 5H 2 O 1.47g /} L
H ₂ SO ₄ 13.44 g / L
Cl 5.0mg / L
Bis-sodium sulfopropyl disulfide 0.755 g / L
Polyvinylpyrrolidone 40mg / L
Dimethylformamide 250g / L

  A cross section of the via hole filled with the copper plating solution composition described above is shown in FIG. As can be seen from FIG. 3, the via hole was filled without the generation of voids, and the plating layer was densely deposited.

Example 3
After the same procedure as in Example 1 except that the amounts of polyvinylpyrrolidone and dimethylformamide used were changed in the copper plating solution composition, the plated shape and the degree of filling of the filled via-hole cross section were confirmed.

Composition:
_{CuSO 4 · 5H 2 O 1.47g /} L
H ₂ SO ₄ 13.44 g / L
Cl 5.0mg / L
Bis-sodium sulfopropyl disulfide 0.755 g / L
Polyvinylpyrrolidone 60mg / L
Dimethylformamide 170g / L

  FIG. 4 shows a cross section of the via hole filled with the copper plating solution composition described above. As can be seen from FIG. 4, the via hole was filled without generation of voids, and the deposition state of the plating layer was dense.

(Comparative Example 1)
After the same procedure as in Example 1 except that polyvinylpyrrolidone was excluded from the copper plating solution composition, the plated shape and the degree of filling of the filled via hole cross section were confirmed.

Composition:
_{CuSO 4 · 5H 2 O 1.47g /} L
H ₂ SO ₄ 13.44 g / L
Cl 5.0mg / L
Bis-sodium sulfopropyl disulfide 0.755 g / L
Dimethylformamide 219.27 g / L

  Thus, the cross section of the via hole plated with the copper plating solution composition not added with polyvinylpyrrolidone is shown in FIG. As can be seen from FIG. 5, the via hole was not completely filled, and voids were generated inside.

(Comparative Example 2)
After performing in the same manner as in Example 1 except that dimethylformamide was excluded from the copper plating solution composition, the plated shape of the filled via hole cross section and the degree of filling were confirmed.

Composition:
_{CuSO 4 · 5H 2 O 1.47g /} L
H ₂ SO ₄ 13.44 g / L
Cl 5.0mg / L
Bis-sodium sulfopropyl disulfide 0.755 g / L
Polyvinylpyrrolidone 45mg / L

  FIG. 6 shows a cross section of the via hole plated with the copper plating solution composition to which dimethylformamide is not added. As can be seen from FIG. 6, the via hole was not completely filled, and dimples were generated inside the via hole.

  The present invention has been described in detail on the basis of specific embodiments. However, the present invention is intended to specifically describe the present invention, and the present invention is not limited thereto. It will be apparent to those skilled in the art that modifications and improvements within the technical idea of the present invention are possible.

  All simple variations and modifications of the present invention belong to the scope of the present invention, and the specific scope of protection of the present invention will be apparent from the appended claims.

  The present invention is applicable to a copper plating solution composition for printed circuit boards and a via hole filling method using the same.

DESCRIPTION OF SYMBOLS 10 1st insulating layer 12 2nd insulating layer 20 1st copper foil layer 22 2nd copper foil layer with which the via hole was filled 110 Inhibitor (suppressor)
120 brightener
130 Leveler

Claims (16)

Copper salt,
acid,
Gloss auxiliary,
Brightener,
A copper plating solution composition for printed circuit boards, comprising polyvinylpyrrolidone and a reducing agent.   The copper plating solution composition is 0.1 to 0.3 wt% copper salt, 1 to 2 wt% acid, 0.0002 to 0.0008 wt% gloss auxiliary, 0.05 to 0.2 wt% 2. The copper for printed circuit boards according to claim 1, comprising: 1% brightener, 0.001 to 0.01 wt% polyvinylpyrrolidone, 10 to 30 wt% reducing agent, and the balance water. Plating solution composition. The copper salt is made of copper sulfate (CuSO ₄ .5H ₂ O), copper nitrate (Cu (NO ₃ ) ₂ ), copper formate (Cu (HCOO) ₂ ) and cupric chloride (CuCl ₂ · 2H ₂ O). The copper plating solution composition for printed circuit boards according to claim 1 or 2, wherein at least one selected from the group consisting of: The at least one acid is selected from the group consisting of sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), acetic acid (CH ₃ COOH), and fluoroboric acid (HBF ₄ ). 3. A copper plating solution composition for printed circuit boards according to 1 or 2.   The copper for printed circuit boards according to claim 1, wherein the gloss auxiliary is at least one selected from the group consisting of chloride ions (Cl), hydrochloric acid (HCl), and sodium chloride (NaCl). Plating solution composition.   3. The copper plating solution for a printed circuit board according to claim 1, wherein the brightener is bis-sodium sulfopropyl-disulfide, bipyridine, or a mixture thereof. 4. Composition.   The copper plating solution composition for printed circuit boards according to claim 1 or 2, wherein the amount of the polyvinylpyrrolidone used is 0.004 to 0.006% by weight.   The copper plating solution composition for printed circuit boards according to claim 1 or 2, wherein the polyvinyl pyrrolidone has a molecular weight of 100,000 to 5,000,000.   The copper plating solution composition for a printed circuit board according to claim 1 or 2, wherein the amount of the reducing agent used is 17 to 25% by weight.   The copper for printed circuit boards according to claim 1 or 2, wherein the reducing agent is at least one selected from the group consisting of acetaldehyde, dimethylformamide, and formic acid. Plating solution composition. Immersing an object to be plated in a copper plating electrolyte containing a copper plating solution composition containing a copper salt, an acid, a gloss auxiliary, a brightener, polyvinylpyrrolidone and a reducing agent;
A via hole filling method for a printed circuit board comprising the steps of electrolysis and plating under a working environment having a high current density of 3.0 to 5.0 A / dm ² and a temperature condition of 20 to 60 ° C.   The copper plating solution composition is 0.1 to 0.3 wt% copper salt, 1 to 2 wt% acid, 0.0002 to 0.0008 wt% gloss auxiliary, 0.05 to 0.2 wt% The printed circuit board via hole according to claim 11, comprising: 1% brightener, 0.001 to 0.01 wt% polyvinylpyrrolidone, 10 to 30 wt% reducing agent, and the balance water. Filling method.   The method for filling a via hole for a printed circuit board according to claim 11, wherein the amount of the polyvinylpyrrolidone used is 0.004 to 0.006% by weight.   The method for filling a via hole for a printed circuit board according to claim 11, wherein the polyvinyl pyrrolidone has a molecular weight of 100,000 to 5,000,000.   The method of filling a via hole for a printed circuit board according to claim 11, wherein the amount of the reducing agent used is 17 to 25% by weight.   The method for filling a via hole for a printed circuit board according to claim 11, wherein the reducing agent is at least one selected from the group consisting of acetaldehyde, dimethylformamide, and formic acid. .