KR100994730B1 - Method for plating circuit surface of printed circuit board - Google Patents

Method for plating circuit surface of printed circuit board Download PDF

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Publication number
KR100994730B1
KR100994730B1 KR1020100049786A KR20100049786A KR100994730B1 KR 100994730 B1 KR100994730 B1 KR 100994730B1 KR 1020100049786 A KR1020100049786 A KR 1020100049786A KR 20100049786 A KR20100049786 A KR 20100049786A KR 100994730 B1 KR100994730 B1 KR 100994730B1
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KR
South Korea
Prior art keywords
silver
plating
tin
layer
alloy
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KR1020100049786A
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Korean (ko)
Inventor
이남철
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주식회사 써피스텍
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Priority to KR1020100049786A priority Critical patent/KR100994730B1/en
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Publication of KR100994730B1 publication Critical patent/KR100994730B1/en
Priority to PCT/KR2011/003874 priority patent/WO2011149289A2/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1637—Composition of the substrate metallic substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

According to the present invention, a dense silver or silver alloy is first plated on a surface of a copper circuit formed on a surface of a printed circuit board by a substitution plating method, and then a second layer is plated on a tin or tin alloy by a substitution plating method to form a double layer. The silver or silver alloy plating layer serves as an anti-diffusion layer that prevents diffusion of the copper circuit layer and the tin or tin alloy layer of the surface layer, and the tin or tin alloy layer of the surface layer protects the silver or silver alloy layer of the underlying layer. It relates to a circuit surface plating method of a printed circuit board to act as a protective layer,
As a method of plating on the surface of the copper (110) circuit formed on the surface of the printed circuit board 100,
A first step of primary substitution plating silver (120) or silver alloy as a diffusion barrier layer on a surface of the copper (110) circuit formed on the surface of the printed circuit board (100); And
A second step of forming a double layer by secondary substitution plating tin 130 or tin alloy as the protective layer of silver 120 or silver alloy on the substituted plated silver 120 or silver alloy;
Characterized in that it comprises a.
The present invention as described above, the first surface of the dense silver 120 or silver alloy plated by the substitution plating method on the surface of the copper (110) circuit formed on the surface of the printed circuit board 100 to form a diffusion barrier layer, the substitution plating thereon In this manner, the tin 130 or tin alloy is secondary plated to form a double layer to form a protective layer protecting the silver or silver alloy plating layer. Therefore, the present invention, unlike the conventional tin plating, it is possible to prevent the intermetallic compound and whisker generation between the tin and copper by the silver or silver alloy diffusion barrier layer, thereby preventing the short circuit of the circuit. In addition, in the present invention, unlike the conventional silver plating, the tin or tin alloy plating of the surface layer prevents the discoloration of silver and the silver ion migration phenomenon by blocking the silver from the external environment. In addition, the present invention has the effect of significantly solving problems such as black pads or component dropping due to a decrease in the adhesion of nickel as in nickel / gold plating by using silver or a silver alloy without using nickel as the diffusion barrier layer.

Description

Method for plating circuit surface of printed circuit board

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of plating a circuit surface of a printed circuit board (PCB), and more particularly, by first plating a dense silver or silver alloy on the surface of a copper circuit formed on the surface of a printed circuit board by a substitution plating method. Thereafter, by plating a tin or tin alloy on the secondary by a substitution plating method to form a double layer, the silver or silver alloy plating layer serves as a diffusion barrier layer that prevents diffusion between the copper circuit layer and the tin or tin alloy layer of the surface layer. The tin or tin alloy layer of the surface layer relates to a circuit surface plating method of a printed circuit board to serve as a protective layer to protect the silver or silver alloy layer of the lower layer.

In accordance with the trend of miniaturization and high functionality of electronic devices, the circuits of printed circuit boards are becoming smaller, denser, and highly integrated, and parts are becoming smaller and smaller, making mounting on printed circuit boards increasingly difficult. Technology is required.

In mounting components on high density printed circuit boards, the method of treating the surface of copper circuits is very important. Among them, the type of plating and the characteristics of the metal plating have a great influence on the reliability of the mounting. It is becoming an important item to determine performance.

In this regard, in the plating method for mounting, that is, soldering (soldering) of the high density printed circuit board according to the related art, mainly substituted tin plating, substituted silver plating, and electroless nickel plating / substituted gold plating methods are widely applied. There are very specific problems and deficiencies, and in applying them, they do not meet the requirements of reliability, economics and eco-friendliness.

First, in the case of substituted tin plating, the plated tin forms a copper-to-metal compound that forms a circuit, thereby deteriorating physical properties and solderability, and whiskers generate short circuits.

In the case of the following substitution silver plating, there is a problem that silver discoloration and ion migration phenomenon occurs.

In addition, in the case of electroless nickel plating / substituted gold plating, nickel has a high melting point and is a relatively stable metal such as used as a diffusion barrier layer, so it is less prone to diffusion with other metals, so it is easy to cause component drop-off due to a decrease in the bondability with solder, and nickel plating I have a problem with a black pad that turns black.

In addition, the order in which the printed circuit board is generally made is as follows.

First, make a hole in the insulating resin plate bonded with copper foil, copper plating with chemical plating and electrolytic plating, and then construct a circuit with a corrosion resist.The copper foil other than the circuit is etched with a corrosion solution to form a desired circuit, and then remove the corrosion resist. do.

The copper circuit formed on the insulating resin plate then prints the solder resist except where the component is to be mounted, and the exposed copper circuit is a metal that is compatible with solder, such as tin, to ensure that the copper surface does not oxidize and is well soldered. , Tin alloy, silver, silver alloy, nickel / gold, and palladium.

After processing to the required shape and specification of the printed circuit board, the manufacturing process is completed by checking the electrical performance of the circuit.

In this manufacturing process, the surface treatment process of the copper circuit which is related to the mounting of the product is very important. The surface treatment methods include molten solder coating, plating, and osp coating. Among them, plating is performed by electroplating and electroless plating. The electroless plating is divided into reduction plating and substitution plating.

In order to improve the efficiency of soldering and improve efficiency, the surface plating of printed circuit boards is made of tin, silver, nickel / gold, palladium and other solders (tin-lead or tin-silver-copper alloy, etc.) according to the type of metal used. The use of a metal with conversion, the mounting effect such as soldering varies depending on the type of metal applied, the characteristics of the metal, the plating method and the like.

Surface plating for soldering such as this requires a reliable, economical and environmentally friendly plating method.

In the related art, a method of plating a surface of a copper circuit of a printed circuit board according to the related art includes a substituted tin plating method, a substituted silver plating method, and an electroless nickel / substituted gold plating method.

However, in this conventional technique, the replacement tin plating is relatively inexpensive to manufacture, but when soldering, the intermetallic compound between the copper circuit and the tin layer is generated, thereby deteriorating the physical properties of the joint and reducing the solderability. Whiskers generate | occur | produce by an intermetallic compound, and there exist a fault, such as a short circuit between circuits.

Substituted silver plating has a problem in that the surface of the silver is easily discolored by fingerprints, sulfides in the atmosphere, and the like, resulting in poor preservability, thereby lowering solderability, and causing ion transfer to occur due to the use environment, causing short circuits.

In the case of electroless nickel / substituted gold plating, nickel is high in melting point and used as a diffusion barrier layer, so it is stable and diffusion of other metals is small. There is a problem in that the soldering is not possible because the black pad phenomenon that the nickel surface turns black.

In addition, nickel and nickel plating chemicals cause hypersensitivity reactions to the human body or cause skin diseases, and phosphorus compounds used in nickel plating have a drawback of causing adverse environmental effects such as stream eutrophication, and therefore, their use is actively regulated.

The present invention has been made in order to solve the above-described problems, the first surface of the dense silver or silver alloy by the substitution plating method on the surface of the copper circuit formed on the surface of the printed circuit board, then tin or by a substitution plating method thereon Secondary plating of the tin alloy to form a double layer, whereby the silver or silver alloy plating layer acts as a diffusion barrier to prevent diffusion of the copper circuit layer and the tin or tin alloy layer of the surface layer, and the tin or tin alloy layer of the surface layer An object of the present invention is to provide a method of plating a circuit surface of a printed circuit board to serve as a protective layer for protecting a silver or silver alloy layer under a silver layer. That is, according to the present invention, the intermetallic compound of the substitutional tin plating, which is a problem with the conventional surface treatment method, the limitation of the number of solders and the short circuit of the circuit due to the whisker generation, the discoloration of silver in the silver plating and the ion migration phenomenon The purpose of the present invention is to provide a circuit surface plating method of a printed circuit board to fundamentally solve short circuits and component dropouts and black pads in electroless nickel / substituent plating.

In order to achieve this object,

According to one embodiment of the present invention,

As a method of plating on the surface of the copper (110) circuit formed on the surface of the printed circuit board 100,

A first step of primary substitution plating silver (120) or silver alloy as a diffusion barrier layer on a surface of the copper (110) circuit formed on the surface of the printed circuit board (100); And

A second step of forming a double layer by secondary substitution plating tin 130 or tin alloy as the protective layer of silver 120 or silver alloy on the substituted plated silver 120 or silver alloy;

Characterized in that it comprises a.

delete

The plating thickness of the silver 120 or silver alloy is characterized in that 0.1 ㎛ to 1 ㎛.

The plating thickness of the silver 120 or silver alloy is characterized in that 0.2 ㎛ to 0.4 ㎛.

delete

delete

The plating thickness of the tin 130 or tin alloy is characterized in that 0.1 ㎛ to 1 ㎛.

The plating thickness of the tin 130 or tin alloy is characterized in that the 0.2㎛ to 0.5㎛.

The present invention, by plating the dense silver 120 or silver alloy on the surface of the copper (110) circuit formed on the surface of the printed circuit board 100 by primary plating to form a diffusion barrier layer, and the substitution plating method thereon Secondary plating of tin 130 or tin alloy forms a double layer to form a protective layer protecting the silver or silver alloy plating layer. Therefore, the present invention, unlike the conventional tin plating, it is possible to prevent the intermetallic compound and whisker generation between the tin and copper by the silver or silver alloy diffusion barrier layer, thereby preventing the short circuit of the circuit. In addition, in the present invention, unlike the conventional silver plating, the tin or tin alloy plating of the surface layer prevents the discoloration of silver and the silver ion migration phenomenon by blocking the silver from the external environment. In addition, the present invention has the effect of significantly solving problems such as black pads or component dropping due to a decrease in the adhesion of nickel as in nickel / gold plating by using silver or a silver alloy without using nickel as the diffusion barrier layer.

1 is a cross-sectional view showing a circuit formed of copper on the surface of a printed circuit board during the process of the circuit surface plating method of the printed circuit board according to the present invention.
2 is a cross-sectional view illustrating a step of plating the surface of a copper circuit formed on the surface of the printed circuit board of FIG. 1 with silver.
3 is a cross-sectional view illustrating a step of plating tin on the surface of silver plated in FIG. 2.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a cross-sectional view showing a circuit formed of copper 110 on the surface of the printed circuit board 100 during the process of the circuit surface plating method of the printed circuit board according to the present invention, Figure 2 is a printed circuit board shown in FIG. 3 is a cross-sectional view illustrating a step of plating a surface of a copper 110 circuit formed on a surface of 100 with silver 120, and FIG. 3 illustrates plating of tin 130 on a surface of silver 120 plated in FIG. 2. A cross-sectional view illustrating a step includes a printed circuit board 100, copper 110, silver 120, and tin 130.

1 to 3, since the copper 110 circuit formed on the surface of the printed circuit board 100 as shown in FIG. 1 has already been contaminated and oxidized during the manufacturing process, the copper 110 in the degreasing process before the plating process is performed. 110) Contamination of the circuit surface is removed and oxides are removed by soft etching.

Next, on the surface of the copper 110 circuit formed on the surface of the printed circuit board 100 as shown in FIG. 1, silver 120 or a silver alloy is plated and washed with substitution plating as shown in FIG. 2. The plating thickness of the silver 120 or the silver alloy may serve as a diffusion barrier layer of 0.1 μm to 1 μm, but it is preferably 0.2 μm to 0.4 μm in consideration of the diffusion preventing effect and the solderability and economical efficiency when soldering. Do.

Thus, the plating of the silver 120 on the surface of the copper 110 by the substitution plating method is represented by the formula, Cu 0 + 2Ag + -> Cu 2+ + 2Ag 0 . The composition of the substituted silver plating solution was 35 g / l of nitric acid, 2.5 g / l of silver nitrate, 10 g / l of EDTA, 10 g / l of imidazole, 10 g / l of polyoxyethylene glycol nonylphenyl, and plated at 50 ° C. for 3 minutes to obtain 0.15 μm. The plating thickness was obtained.

On the plated silver 120 or silver alloy, tin 130 or tin alloy is plated and washed with substitution plating as shown in FIG. 3. The plating thickness of the tin 130 or the tin alloy may be 0.1 μm to 1 μm to protect the underlying silver 120 or the silver alloy layer, but the thickness of 0.2 μm to 0.5 μm may be used to improve the protection effect and the solderability of the lower layer. It is preferable.

Thus, the plating of tin on the surface of the silver 120 by the substitution plating method is represented by the formula, it is equal to 2Ag 0 + Sn 2+ -> 2Ag + + Sn 0 . Substitutive plating is a plating technique using an electrochemical standard electrode potential of a metal, and a metal of a high potential is usually replaced on a metal of a low potential by a potential difference of each metal to be plated. However, with suitable complexing agents it is possible, but not as common, as with the lower potential tin (-0.14 V) plated on copper (0.16 V) with thiourea. Substituting a lower potential metal on a higher potential metal has different characteristics of the metal species, so the chemical and metallographic responses are different. Does not apply equally. In particular, the technique of substitution-plating tin (-0.14V) 130 having a significantly lower potential than silver on silver (0.8V) 120 in the present invention has not been theoretically established and is not technically actualized. There is no example applied. In the present invention to overcome this technical limitation, plating of tin 130 or tin alloy is performed by substituting and depositing tin (-0.14V) 130 of lower potential on higher potential silver (0.8V) 120. Realized. The composition of this substituted tin plating solution was 72 g / l of methanesulfonic acid, 30 g / l of methanesulfonic acid, 350 g / l of citric acid, 130 g / l of thiourea, and 30 g / l of tartaric acid. The thickness was obtained.

delete

Since the present invention plated the surface of the circuit formed of copper 110 on the surface of the printed circuit board 100 twice with silver 120 and tin 130 by the substitution plating method, silver, tin alone In this case, it is possible to prevent the conventional drawbacks, that is, the formation of intermetallic compounds, the occurrence of whiskers and the resulting short circuit, surface oxidation, and silver ion migration.

Although the technical spirit of the present invention has been described above with reference to the accompanying drawings, this is intended to describe exemplary embodiments of the present invention by way of example and not to limit the present invention. In addition, it is obvious that any person skilled in the art can make various modifications and imitations without departing from the scope of the technical idea of the present invention.

100: printed circuit board
110: copper
120: silver
130: annotation

Claims (8)

As a method of plating on the surface of the copper (110) circuit formed on the surface of the printed circuit board 100,
A first step of primary substitution plating silver (120) or silver alloy as a diffusion barrier layer on a surface of the copper (110) circuit formed on the surface of the printed circuit board (100); And
A second step of forming a double layer by secondary substitution plating tin 130 or tin alloy as the protective layer of silver 120 or silver alloy on the substituted plated silver 120 or silver alloy;
Circuit surface plating method of a printed circuit board comprising a.
The method according to claim 1,
The plating surface of the silver (120) or silver alloy is 0.1㎛ to 1㎛ characterized in that the circuit surface plating method of the printed circuit board.
The method according to claim 2,
Plating thickness of the silver (120) or silver alloy is 0.2 to 0.4 ㎛ circuit surface plating method of a printed circuit board, characterized in that.
The method according to claim 1,
Plating thickness of the tin (130) or tin alloy is 0.1㎛ to 1㎛ the circuit surface plating method of the printed circuit board.
The method according to claim 4,
Plating thickness of the tin (130) or tin alloy is a circuit surface plating method of a printed circuit board, characterized in that 0.2㎛ to 0.5㎛. delete delete delete
KR1020100049786A 2010-05-27 2010-05-27 Method for plating circuit surface of printed circuit board KR100994730B1 (en)

Priority Applications (2)

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KR1020100049786A KR100994730B1 (en) 2010-05-27 2010-05-27 Method for plating circuit surface of printed circuit board
PCT/KR2011/003874 WO2011149289A2 (en) 2010-05-27 2011-05-26 Method for plating a circuit surface of a printed circuit board

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Application Number Priority Date Filing Date Title
KR1020100049786A KR100994730B1 (en) 2010-05-27 2010-05-27 Method for plating circuit surface of printed circuit board

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100442519B1 (en) 2002-04-09 2004-07-30 삼성전기주식회사 Alloy Plating Solution for Surface Treatment of Modular PCB
KR100489869B1 (en) * 2004-09-07 2005-05-17 (주)유일재료기술 Method for forming single ag-au plating on printed circuit board for high density interconnection, and printed circuit board for high density interconnection having single ag-au plating
KR100512811B1 (en) * 2004-05-19 2005-09-06 (주)유일재료기술 Method for plating on printed circuit board for semi-conductor package and printed circuit board produced therefrom

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394419A (en) * 1981-06-12 1983-07-19 Oak Industries Inc. Printed circuit material
JPH08102578A (en) * 1994-09-30 1996-04-16 Matsushita Electric Works Ltd Ceramic printed wiring board and its manufacture

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100442519B1 (en) 2002-04-09 2004-07-30 삼성전기주식회사 Alloy Plating Solution for Surface Treatment of Modular PCB
KR100512811B1 (en) * 2004-05-19 2005-09-06 (주)유일재료기술 Method for plating on printed circuit board for semi-conductor package and printed circuit board produced therefrom
KR100489869B1 (en) * 2004-09-07 2005-05-17 (주)유일재료기술 Method for forming single ag-au plating on printed circuit board for high density interconnection, and printed circuit board for high density interconnection having single ag-au plating

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WO2011149289A3 (en) 2012-03-22
WO2011149289A2 (en) 2011-12-01

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