KR102036334B1 - Electroless plating solution and electroless plating method - Google Patents

Abstract

The present specification relates to an electroless plating solution and an electroless plating method.

Description

ELECTROLESS PLATING SOLUTION AND ELECTROLESS PLATING METHOD}

The present invention relates to an electroless plating solution and an electroless plating method.

Electroless plating reduces metal ions without applying electricity and has advantages such as wear resistance, corrosion resistance, uniform plating thickness, and ease of processing. Therefore, electroless plating has been utilized as heat-resistant coatings for automobiles and aircrafts, and corrosion-resistant coatings for semiconductor manufacturing equipment piping due to the above advantages.

In particular, semiconductor manufacturing equipment piping has problems such as shortening the life of the equipment due to contamination by foreign substances in the piping, corrosion by strong air, and decrease in process yield.

In order to solve the problem, conventionally, a method of directly removing a contaminant film formed on a semiconductor manufacturing equipment pipe was used. However, when the contaminant film is directly removed, the base material is damaged during the contaminant film removal process, and the life of the semiconductor manufacturing equipment is still reduced.

Thus, in order to solve the above problem, a method of using electroless plating for coating the mass transfer pipe of the semiconductor manufacturing equipment has been attempted.

In particular, a method has been attempted to reduce all of the plurality of metal materials included in the electroless plating solution and to ensure the stability and the life of the plating solution.

Protection of Metals, Vol. 41, No. 1, 2005, pp. 55-62.

The present invention seeks to provide an electroless plating solution and an electroless plating method.

However, the problem to be solved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention, the nickel precursor; Tungsten precursors; Complexing agents; reducing agent; And a fluorine-based lubricating polymer, wherein the content of the complexing agent is 0.9 g or more and 20 g or less per g of the tungsten precursor.

In addition, another embodiment of the present invention provides an electroless plating method.

One embodiment of the present invention, preparing a material to be plated; Injecting the material to be plated into the electroless plating solution; And a plating layer forming step of forming a plating layer on the surface of the material to be plated.

The electroless plating solution according to the exemplary embodiment of the present invention has an advantage of providing a plating layer having excellent non-adhesive properties.

The electroless plating solution according to the exemplary embodiment of the present invention has an advantage of manufacturing a plating layer having excellent physical properties while using an inexpensive precursor.

The electroless plating solution according to an exemplary embodiment of the present invention has an advantage of providing a plating layer having a high hardness.

In addition, the electroless plating solution according to an exemplary embodiment of the present invention has an advantage of providing a plating layer having stability. Specifically, the plating layer derived from the electroless plating solution according to the exemplary embodiment of the present invention has an advantage that the composition thereof is hardly changed even when exposed to the outside for a long time.

Since the electroless plating solution according to the exemplary embodiment of the present invention has high stability, the nickel and tungsten contained therein are simultaneously plated, and there is a wide range of pH and temperature at which the fluorine-based lubricity polymer can be stably dispersed. .

The electroless plating method according to an exemplary embodiment of the present invention may be performed at a lower temperature than the existing plating method, and thus, there is an advantage of securing economical efficiency in terms of cost consumed when heating the plating liquid.

1 shows an image of the surface of a plating layer formed according to the electroless plating method according to Example 6 taken with a scanning electron microscope.
FIG. 2 shows an image obtained by scanning electron microscopy of the surface of the plating layer according to Examples 1 to 3. FIG.
Figure 3 shows an image taken with a scanning electron microscope of the surface of the plating layer according to Reference Example 1, Examples 4 to 7.
FIG. 4 shows the images taken by the scanning electron microscope of the surface of the plating layer which concerns on Example 8 and Example 9. FIG.
FIG. 5 shows an image obtained by scanning electron microscopy of the surface of the plating layer before and after stability evaluation of Example 10. FIG.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise.

As used throughout this specification, the term "step to" or "step of" does not mean "step for."

The present inventors solve the problem that all metal materials are not reduced and the stability and lifetime of the plating solution are reduced when the plating layer is manufactured using the same electroless plating solution, for example, an electroless plating solution containing no complexing agent. As a result of conducting various studies to achieve the following inventions.

Specifically, the present inventors further include a complexing agent in the conventional electroless plating solution, and by adjusting the relative content with respect to the content of the tungsten precursor thereof, while ensuring the stability of the plating solution, all metals included in the electroless plating solution It has come to invent an electroless plating solution in which the material can be reduced.

Hereinafter, this specification is demonstrated in detail.

One embodiment of the present invention, the nickel precursor; Tungsten precursors; Complexing agents; reducing agent; And a fluorine-based lubricating polymer, wherein the content of the complexing agent is 0.9 g or more and 20 g or less per g of the tungsten precursor.

According to an exemplary embodiment of the present invention, the nickel (Ni) precursor is Ni (CH ₃ COO) ₂ , Ni (CH ₃ COO) ₂ · 4H ₂ O, Ni (NO ₃ ) ₂ · 6H ₂ O, NiSO ₄ · At least one selected from the group consisting of 6H ₂ O, C ₃₂ H ₁₆ N ₈ Ni, NiCl ₂ and NiCl ₂ .6H ₂ O, preferably Ni (CH ₃ COO) ₂ , Ni (CH ₃ COO) _2. At least one selected from the group consisting of 4H ₂ O, NiSO ₄ · 6H ₂ O, NiCl _2, and NiCl ₂ · 6H ₂ O, more preferably NiSO ₄ · 6H ₂ O, Ni (CH ₃ COO) _2, and Ni (CH ₃ COO) ₂ · 4H ₂ O It may be one or more selected from the group consisting of.

Conventionally, nickel precursors generally used in the art were used, but the present invention specifically specifies the type of the nickel precursor, thereby increasing compatibility with the fluorine-based lubricity polymer contained in the electroless plating solution. In addition, the fluorine-based lubricating polymer may be evenly dispersed in the plating layer using the electroless plating solution, thereby achieving excellent non-adhesive properties of the plating layer.

According to an exemplary embodiment of the present invention, when the nickel precursor is used to form a plating layer on the surface of the material to be plated using the electroless plating solution, the nickel precursor may provide nickel included in the plating layer. That is, nickel included in the plating layer may be derived from the nickel precursor.

According to an exemplary embodiment of the present invention, the tungsten (W) precursor is Na ₂ WO ₄ , WCl ₄ , WCl ₆ , WOCl ₄ and H ₂ WO ₄ It may be one or more selected from the group consisting of, preferably Na ₂ WO ₄ , the tungsten (W) precursor may be an ammonium para tungstate (Ammonium Para Tungstate; APT) is excluded.

Conventionally, tungsten precursors commonly used in the art, such as ammonium paratungstate, were used. However, in the case of the conventional method, compatibility with the fluorine-based lubricity polymer cannot be ensured. Fluorinated lubricating polymers are agglomerated and there is a problem in that they are not evenly dispersed.

Accordingly, the present invention specifically specifies the type of the tungsten precursor, thereby improving compatibility with the fluorine-based lubricity polymer, and when the plating layer is formed using the electroless plating solution, the fluorine-based polymer is uniformly dispersed without agglomeration in the plating layer, thereby excellent non-adhesion of the plating layer. It is possible to secure the characteristics and to secure a high hardness of the plating layer by tungsten derived from the tungsten precursor.

According to an exemplary embodiment of the present invention, when the tungsten precursor is used to form a plating layer on the surface of the material to be plated using the electroless plating solution, the tungsten precursor may provide tungsten included in the plating layer. That is, tungsten included in the plating layer may be derived from the tungsten precursor.

According to an exemplary embodiment of the present invention, the complexing agent is malic acid (malic acid), malonic acid (malonic acid), gluconic acid (gluconic acid), succinic acid (succinic acid), citric acid and their It may include one or more selected from the group consisting of metal salts.

Preferably, the complexing agent may comprise malic acid or gluconic acid, more preferably gluconic acid and metal salts thereof.

According to an exemplary embodiment of the present invention, the complexing agent may refer to a molecule or ion generating coordination around a metal ion derived from the nickel precursor and the tungsten precursor. Specifically, the complexing agent may prevent the metal ions derived from the nickel precursor and the tungsten precursor from being precipitated in the form of a hydroxide or the like, and by shifting the precipitation potential of the metal ions in the basic direction, an appropriate plating rate may be achieved. It can be secured.

According to an exemplary embodiment of the present invention, the reducing agent may include dimethylamino borane (DMAB).

According to the exemplary embodiment of the present invention, when the reducing agent includes DMAB, when the plating layer is formed on the material to be plated using the electroless plating solution, boron may be included in the plating layer. When boron is included in the plating layer, oxidation of the plating layer becomes difficult, thereby securing high hardness characteristics of the plating layer.

According to the exemplary embodiment of the present invention, when the reducing agent is used to form a plating layer on the surface of the material to be plated using the electroless plating solution, boron included in the plating layer may be provided. That is, boron included in the plating layer may be derived from the reducing agent.

In addition, the reducing agent may be to reduce each of the nickel cation and tungsten cation derived from each of the nickel precursor and the tungsten precursor contained in the electroless plating solution.

According to an exemplary embodiment of the present invention, the fluorine-based lubricity polymer may include polytetrafluoroethylene (PTFE).

According to one embodiment of the present invention, the fluorine-based lubricity polymer may provide fluorine included in the plating layer when the plating layer is formed on the surface of the material to be plated using the electroless plating solution. That is, the fluorine contained in the plating layer may be derived from the fluorine-based lubricity polymer.

Specifically, the particles of the fluorine-based lubricity polymer may be dispersed in the plating layer, and the fluorine-based lubricity polymer is chemically stable, has a relatively high melting point, and low surface energy, thereby realizing non-adhesive properties of the plating layer. have.

In addition, according to an exemplary embodiment of the present invention, the fluorine-based lubricity polymer may be included in the electroless plating solution as a solution type polymer in which an emulsion is formed. Specifically, the fluorine-based lubricating polymer may be included in about 60% by weight in an emulsion form in a solution using water as a solvent. More specifically, the fluorine-based lubricating polymer may be a solution resin (665800 ALDRICH, SIGMA-ALDRICH) in which an emulsion of polytetrafluoroethylene (PTFE) is dispersed at about 60% by weight in water. In addition, the particle size of the PTFE emulsion contained in the solution may be about 500 nm.

The size of the emulsion particles may refer to the maximum distance from one end of one of the emulsion particles contained in the solution to the other end.

According to an exemplary embodiment of the present invention, the content of the complexing agent is 0.9 g or more and 20 g or less, 0.9 g or more and 10 g or less, 2 g or more and 20 g or less, 2 g or more and 10 g or less, 2 g per 1 g of the tungsten precursor. 6 g or less, 3 g or more and 10 g or less, or 3 g or more and 6 g or less.

Specifically, the content may mean a relative content of the complexing agent relative to the tungsten precursor.

In the content range, the nickel precursor and the tungsten precursor included in the electroless plating solution may be ionized, and nickel and tungsten may be included in the plating layer formed using the electroless plating solution.

In addition, in the content range, it is possible to maximize the surface activity by the nickel precursor and the high hardness characteristics by the tungsten precursor of the plating layer.

According to an exemplary embodiment of the present invention, the electroless plating solution may further include a solvent. That is, each of the nickel precursor, the tungsten precursor, the complexing agent, the reducing agent, and the fluorine-based lubricity polymer may be added to the solvent.

According to one embodiment of the present invention, the solvent may be an aqueous solvent, specifically, distilled water, deionized water, or ultrapure water.

According to the exemplary embodiment of the present invention, the content of the nickel precursor is 5 g or more and 20 g or less, 5 g or more and 15 g or less, 10 g or more and 20 g or less, 10 g or more and 15 g or less per liter of the electroless plating solution, 10 g or more and 14 g or less, 12 g or more and 15 g or less, or 12 g or more and 14 g or less.

In the content range, it is possible to maximize the surface activity by the nickel precursor of the plating layer formed using the electroless plating solution.

According to an exemplary embodiment of the present invention, the content of the tungsten precursor is 0.4 g or more and 20 g or less, 0.4 g or more and 15 g or less, 10 g or more and 20 g or less, 10 g or more and 15 g or less per liter of the electroless plating solution, 10 g or more and 14 g or less, 12 g or more and 15 g or less, or 12 g or more and 14 g or less.

In the content range, it is possible to maximize the high hardness characteristics of the tungsten precursor of the plating layer formed using the electroless plating solution.

According to an exemplary embodiment of the present invention, the content of the complexing agent may be 10 g or more and 60 g or less, 20 g or more and 60 g or less, or 30 g or more and 60 g or less per liter of the electroless plating solution.

In the content range, the nickel precursor and the tungsten precursor included in the electroless plating solution may be ionized, and nickel and tungsten may be included in the plating layer formed using the electroless plating solution.

According to an exemplary embodiment of the present invention, the content of the reducing agent is 0.1 g or more and 10 g or less, 0.1 g or more and 5 g or less, 0.5 g or more and 10 g or less, 0.5 g or more and 5 g or less, 0.5 per liter of the electroless plating solution. g or more and 3 g or less, 1 g or more and 5 g or less, or 1 g or more and 3 g or less.

In the content range, it is possible to secure the high hardness characteristics of the plating layer formed using the electroless plating solution.

According to an exemplary embodiment of the present invention, the content of the fluorine-based lubricity polymer is 1 ml or more and 30 ml or less, 1 ml or more and 20 ml or less, 5 ml or more and 30 ml or less, 5 ml or more and 20 ml or less per liter of the electroless plating solution. , 5 ml or more and 15 ml or less, 10 ml or more and 20 ml or less, or 10 ml or more and 15 ml or less.

In the content range, it is possible to maximize the non-adhesive properties of the fluorine-based lubricity polymer of the plating layer formed using the electroless plating solution. Specifically, the aggregation of the fluorine-based lubricity polymer in the content range can be prevented, and the fluorine-based lubricity polymer may be dispersed in the plating layer without being mixed in the plating layer.

According to an exemplary embodiment of the present invention, the electroless plating solution may further include a buffer. Specifically, the buffer may include boric acid. That is, according to an exemplary embodiment of the present invention, the electroless plating solution may further include a buffer containing boric acid.

The buffer may adjust the acidity of the electroless plating solution to provide an appropriate pH range of the electroless plating solution which enables electroless plating using the same in the future. Specifically, when the electroless plating solution does not contain the buffer, the electroless plating solution becomes chemically unstable within a short time, specifically 30 minutes to 1 hour, so that the electroless plating of the electroless plating solution does not proceed. Problems may arise.

According to an exemplary embodiment of the present invention, the buffer may be included in the electroless plating solution to maintain a constant pH of the electroless plating solution.

According to an exemplary embodiment of the present invention, the content of the buffer is 0.1 g or more and 5 g or less, 0.1 g or more and 4 g or less, 0.5 g or more and 5 g or less, 0.5 g or more and 4 g or less, 0.5 per liter of the electroless plating solution. may be greater than or equal to 1 g and greater than or equal to 0.7 g and less than or equal to 4 g, or greater than or equal to 0.7 g and less than or equal to 1 g.

In the content range, it is possible to maximize the optimum pH conditions that the electroless plating solution can be reduced to the plating layer and the reaction rate to reduce the electroless plating solution to the plating layer.

According to one embodiment of the present invention, the pH of the electroless plating solution may be 2 or more and 5 or less, 2 or more and 4 or less, 3 or more and 5 or less, or 3 or more and 4 or less.

Another embodiment of the present invention provides an electroless plating method.

One embodiment of the present invention, preparing a material to be plated; Injecting the material to be plated into the electroless plating solution; And a plating layer forming step of forming a plating layer on the surface of the material to be plated.

According to an exemplary embodiment of the present invention, the electroless plating method may include preparing a material to be plated.

According to one embodiment of the present invention, the material to be plated may be copper (Cu), iron (Fe), silver (Ag), or an alloy containing at least two of them, but the type thereof is not limited.

According to one embodiment of the invention, the electroless plating method comprises the steps of preparing the material to be plated; Then injecting a material to be plated into the electroless plating solution; Washing the plated material before, and etching the surface of the material to be plated; may further include, whereby the electroless plating can be made efficiently.

By etching the surface of the material to be plated, the surface of the material to be plated may be modified and / or activated, and reactivity between the material to be plated and the electroless plating solution may be increased.

According to one embodiment of the present invention, when washing the plated material, an appropriate method may be used according to general technical knowledge in the art, and the method is not limited to any one method.

In addition, when etching the surface of the material to be plated, an appropriate method may be used in accordance with general technical knowledge in the art, the method is not limited to any one method.

According to an exemplary embodiment of the present invention, the step of inputting the material to be plated into the electroless plating solution; may include.

According to an exemplary embodiment of the present invention, the description of the electroless plating solution is as described above. In addition, the method of injecting the plated material is not particularly limited.

According to one embodiment of the present invention, the electroless plating method may include a plating layer forming step of forming a plating layer on the surface of the material to be plated.

According to one embodiment of the present invention, the plating layer forming step; may be that the plating layer is formed by the reduction reaction of the metal cations included in the electroless plating solution and the oxidation reaction of the non-metal anions. Specifically, the plating layer may be formed by a reduction reaction of tungsten cations and nickel cations and an oxidation reaction of boron anions in the electroless plating solution. In addition, the fluorine-based lubricity polymer contained in the electroless plating solution may be dispersed in the plating layer.

According to one embodiment of the present invention, the plating layer forming step; may be pH 3.5 or more pH 6 or less, pH 3.5 or more pH 4.5 or less, pH 4 or more pH 6 or less, or pH 4 or more pH 4.5 or less. Specifically, an acidic solution or a basic solution may be appropriately added to form the pH atmosphere. In addition, a buffer as described above may be added to the electroless plating solution to maintain the pH atmosphere.

Plating of the electroless plating solution may be possible in the pH atmosphere, and components included in the plating layer may be appropriately dispersed. Specifically, when the pH is exceeded, a problem may occur in that the plating layer is not formed or the components included in the plating layer are not evenly dispersed.

Specifically, the type of the acidic solution or the basic solution may mean a general acidic solution or basic solution used in the art, the type is not limited to any one.

According to an exemplary embodiment of the present invention, the plating layer forming step; may be performed at a temperature of 65 ℃ or less than 90 ℃, 65 ℃ or more 80 ℃ or less, 65 ℃ or more 75 ℃ or less, or 65 ℃ or more and 70 ℃ or less. have.

To be carried out in the temperature range, it is possible to ensure an appropriate formation rate of the plating layer, it is possible to prevent the problem that the plating layer is decomposed by high temperature treatment.

Another embodiment of the present invention provides a plating layer formed according to the electroless plating method.

An exemplary embodiment of the present invention provides a plating layer provided on a material to be plated, formed by the electroless plating method, and containing nickel, tungsten, boron, and fluorine.

According to an exemplary embodiment of the present invention, the plating layer may be formed of the electroless plating solution. Specifically, the plating layer may be formed on the surface of the material to be plated using the electroless plating solution. In addition, the formation method of the said plating layer is not limited by either method.

One embodiment of the present invention, specifically, the image of the surface of the plating layer according to Example 6 photographed with a scanning electron microscope is shown in FIG.

According to Figure 1, it was confirmed that the fluorine-based lubricity polymer corresponding to the black point is not agglomerated with each other, evenly dispersed in the plating layer, through which the non-adhesive properties of the plating layer is sufficiently realized, while ensuring a high hardness of the plating layer Could confirm.

According to the exemplary embodiment of the present invention, the plating layer may be nickel metal and tungsten metal plated, the boron atoms may be included in a nonmetal form, and the fluorine-based lubricity polymer including the fluorine may be dispersed in the metal layer. have.

According to an exemplary embodiment of the present invention, the nickel may be derived from the nickel precursor contained in the electroless plating solution. Specifically, in the electroless plating solution, the nickel precursor may be converted into the form of nickel cations, and the nickel cations may be included in the plating layer while being reduced to nickel metal. That is, the nickel may be included in the metal layer in the form of a metal.

According to an exemplary embodiment of the present invention, the tungsten may be derived from the tungsten precursor contained in the electroless plating solution. Specifically, the tungsten precursor is converted into the form of tungsten cation in the electroless plating solution, and the tungsten cation is reduced to tungsten metal, and may be included in the plating layer. That is, the tungsten may be included in the metal layer in the form of a metal.

According to one embodiment of the present invention, the boron may be derived from the reducing agent contained in the electroless plating solution. Specifically, while the boron contained in the reducing agent in the electroless plating solution to reduce the metal cation contained in the electroless plating solution, boron in the form of various compounds such as Ni ₂ B, H ₃ BO ₃ , B (OH) ₃ While being converted, some boron may be included in the plating layer.

According to one embodiment of the present invention, the fluorine may be derived from the fluorine-based lubricity polymer contained in the electroless plating solution.

Specifically, the fluorine-based lubricating polymer may be present in a dispersed form in the electroless plating solution, and the fluorine-based lubricating polymer may be present in a form dispersed in the plating layer in the plating process using the electroless plating solution.

In addition, since the fluorine-based lubricity polymer includes a fluorine atom, the plating layer may include the fluorine atom. That is, the fluorine may be included in the plating layer in an atomic form.

According to one embodiment of the present invention, the nickel content may be 70 wt% or more and 85 wt% or less.

According to an exemplary embodiment of the present invention, the content of tungsten may be 1 wt% or more and 25 wt% or less.

According to one embodiment of the present invention, the boron content may be 0.1 wt% or more and 10 wt% or less.

According to one embodiment of the present invention, the fluorine content may be 2 wt% or more and 16 wt% or less.

According to one embodiment of the present invention, the nickel, the tungsten, the boron, and the content of the fluorine may refer to the content of the metal layer, respectively.

In addition, according to one embodiment of the present invention, the nickel, the tungsten, the boron, and the content of the fluorine may be represented by weight percent of the metal layer, respectively.

According to one embodiment of the present invention, the nickel, the tungsten, the boron, and the content of the fluorine are respectively measured by Scanning Electron Microscope-Energy Dispersive X-ray Spectroscopy (EDX); It may be measured using).

By including nickel, tungsten, boron, and fluorine in the above ranges, the plating layer can exhibit excellent non-adhesive properties and can have high hardness.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those skilled in the art.

Plated  Preparation of the material

A copper substrate cut to 10 mm X 10 mm X 0.35 mm (width X length X height) was used.

The copper substrate was washed with a degreasing solution, an oxide film on the surface of copper was etched using a 10% sulfuric acid solution, washed with ultrapure water, and the copper substrate was pretreated.

[ Experimental Example  1] When tungsten precursor content is fixed, Complexing agent  According to the content change Plating  Furtherance

In order to show a tendency of the composition of the plating layer according to the content of the complexing agent in the electroless plating solution, an electroless plating solution was prepared by adding 1 L of water and a substance of the content shown in Table 1 below.

division nickel
Precursor
(g) tungsten
Precursor
(g) Complexing agent
(g) reducing agent
(g) Fluorinated Lubricating Polymer
(Ml) Buffer
(g) pH Temperature
(℃) Example 1 15 11 34.5 2.5 15 One 5 70 Example 2 15 11 45 2.5 15 One 4.95 70 Example 3 15 11 60 2.5 15 One 5 70

The pre-plated material was placed in a reactor containing the electroless plating solution, and electroless plating was performed according to the temperature and pH conditions shown in Table 1 to form a plating layer on the surface of the material to be plated.

The content of constituent elements of the plating layers according to Examples 1 to 3 was measured by an energy dispersive X-ray spectrometer (Multilab-2000, Thermo Scientific), and the results are shown in Table 2 below.

Furthermore, an image of the surface of the plating layer according to Examples 1 to 3 taken by a scanning electron microscope is shown in FIG. 2.

division Ni (% by weight) F (% by weight) W (% by weight) B (% by weight) Example 1 74.95 13.4 11.55 0.1 Example 2 80.75 9.45 9.22 0.58 Example 3 75.95 6.45 7.92 9.68

According to Table 1 and Table 2, when the content of the tungsten precursor is fixed at 11 g, and the content of the complexing agent in the plating solution is increased, the content of boron in the plating layer increases, and the content of fluorine and tungsten decreases. there was.

In addition, according to FIG. 2, when the content of the complexing agent in the electroless plating solution satisfies the range according to the exemplary embodiment of the present invention, it was confirmed that particles of the fluorine-based lubricity polymer included in the electroless plating solution were evenly dispersed.

However, the results according to Table 2 and FIG. 2 show the tendency of the content change of the constituents in the plating layer according to the content of the complexing agent, and the examples shown in Table 2 and FIG. 2 show the complexing agent in the electroless plating solution. By including in the range according to the exemplary embodiment of the present invention, it was confirmed that it is possible to reduce to nickel and tungsten from the nickel precursor and tungsten precursor contained in the electroless plating solution, respectively.

[ Experimental Example  2] Electroless  According to the pH range of the plating liquid Plated layer  Furtherance

An electroless plating solution was prepared in the same manner as in Experimental Example 1, except that the composition shown in Table 3 was used.

division nickel
Precursor
(g) tungsten
Precursor
(g) Complexing agent
(g) reducing agent
(g) Fluorinated Lubricating Polymer
(Ml) Buffer
(g) pH Temperature
(℃) Reference Example 1 13.2 13.2 50 2.0 12 One 3.47 70 Example 4 13.2 13.2 50 2.0 12 One 4.0 70 Example 5 13.2 13.2 50 2.0 12 One 4.5 70 Example 6 13.2 13.2 50 2.0 12 One 5 70 Example 7 13.2 13.2 50 2.0 12 One 6 70 Comparative Example 1 13.2 13.2 50 2.0 12 One 7 70

The pre-plated material was placed in a reactor containing the electroless plating solution, and electroless plating was performed at the temperature and pH conditions as shown in Table 3 to form a plating layer on the surface of the material to be plated. For reference, Reference Example 1 means the plating solution itself which is not subjected to a separate acid / base treatment.

The content of the constituent elements of the plating layer according to Reference Example 1, Example 4 to Example 7 and Comparative Example 1 was measured by an energy dispersive X-ray spectrometer (Multilab-2000, Thermo Scientific), and the results are shown in Table 4 below. Indicated.

3 shows an image obtained by scanning electron microscopy of the surface of the plating layer according to Reference Example 1 and Examples 4 to 7.

division Ni (% by weight) F (% by weight) W (% by weight) B (% by weight) Reference Example 1 44.47 0.01 13.8 41.72 Example 4 39.66 3.78 9.96 46.60 Example 5 41.01 0.36 8.79 49.84 Example 6 53.54 13.16 6.92 26.38 Example 7 77.88 11.73 9.67 0.72 Comparative Example 1 No plating

According to Table 4, as the pH of the electroless plating solution increased, the content of nickel in the plating layer increased, but when the pH was 7 or more, it was confirmed that the plating layer was not formed. That is, it was confirmed that plating of the electroless plating solution was possible only if the pH of the electroless plating solution was maintained in the range according to the exemplary embodiment of the present invention.

In addition, according to FIG. 3, as the pH of the electroless plating solution increases in the range of 3.5 or more and 6 or less, particles of the fluorine-based lubricity polymer included in the electroless plating solution are uniformly dispersed, and in the case of Comparative Example 1 having a pH of 7, the plating layer is It was confirmed that it was not formed.

In summary, the electroless plating solution according to the exemplary embodiment of the present invention was able to confirm that smooth plating using the electroless plating solution should be maintained in the above-described pH range.

[ Experimental Example  3] Electroless  According to the temperature range of the plating liquid Plated layer  Furtherance

An electroless plating solution was prepared in the same manner as in Experimental Example 1, except that the composition shown in Table 5 was used.

division nickel
Precursor
(g) tungsten
Precursor
(g) Complexing agent
(g) reducing agent
(g) Fluorinated Lubricating Polymer
(Ml) Buffer
(g) pH Temperature
(℃) Example 8 13.2 13.2 50 2.0 6 One 5 65 Example 9 13.2 13.2 50 2.0 6 One 5 85 Comparative Example 2 13.2 13.2 50 2.0 6 One 5 90

The pre-plated material was placed in a reactor containing the electroless plating solution, and electroless plating was performed under the conditions of the temperature and pH shown in Table 5 to form a plating layer on the surface of the material to be plated.

 In addition, the content of the constituent elements of the plating layer according to Example 8, Example 9 and Comparative Example 2 was measured by an energy dispersive X-ray spectrometer (Multilab-2000, Thermo Scientific), which is shown in Table 6 below.

Moreover, the image which image | photographed the surface of the plating layer which concerns on Example 8 and Example 9 with the scanning electron microscope is shown in FIG.

division Ni (% by weight) F (% by weight) W (% by weight) B (% by weight) Example 8 51.05 6.55 8.06 34.34 Example 9 75.54 4.21 17.72 2.53 Comparative Example 2 Plating but plating solution decomposes by heat

According to Table 6, although the nickel content in the plating layer increases as the temperature of the electroless plating solution increases, in the case of Comparative Example 2 in which the temperature of the electroless plating solution is 90 ° C. or higher, the plating layer can be formed, but the electroless plating solution is heated. It could be confirmed that the decomposition itself.

For reference, in Example 8 in which the temperature of the electroless plating solution was 65 ° C., it was possible to form the plating layer, but it was confirmed that the plating layer was formed at a slow speed.

In addition, according to Figure 4 it can be seen that in the case of Example 8 and Example 9 can be formed of the plating layer, even if the plating layer is formed in the temperature range according to an embodiment of the present invention that the particles of the fluorine-based lubricant polymer is evenly dispersed. I could confirm it.

In summary, the electroless plating solution according to the exemplary embodiment of the present invention was able to confirm that smooth plating using the electroless plating solution should be maintained in the above-described temperature range.

[ Experimental Example  4] Electroless  Evaluation of stability of plating solution

An electroless plating solution was prepared by the same method as Experimental Example 1, except that the composition shown in Table 7 was used.

division nickel
Precursor
(g) tungsten
Precursor
(g) Complexing agent
(g) reducing agent
(g) Fluorinated Lubricating Polymer
(Ml) Buffer
(g) pH Temperature
(℃) Example 10 12 13.2 50 2.0 12 One 4.9 70

The pre-plated material was placed in a reactor containing the electroless plating solution, and electroless plating was performed at the temperature and pH conditions as shown in Table 7 to form a plating layer on the surface of the material to be plated.

In addition, the content of the constituent elements of the plating layer according to Example 10 was measured by an energy dispersive X-ray spectrometer (Multilab-2000, Thermo Scientific), and the plating layer according to Example 10 was left for about 1 week. By measuring the content of the constituent elements of the plating layer in the same manner it is shown in Table 8 below.

Furthermore, the image which image | photographed the surface of the plating layer which concerns on Example 10 before one week and after one week left with a scanning electron microscope is shown in FIG.

division Ni (% by weight) F (% by weight) W (% by weight) B (% by weight) 1 week ago 72.18 7.82 16.58 3.42 1 week after curing 70.84 9.38 16.26 3.53

In FIG. 5, the scanning electron microscope image of the surface before the one week progress of the plating layer which concerns on Example 10 is shown on the left side, and the scanning electron microscope image of the surface after the one week course is shown on the right side.

According to FIG. 5, even when one week passed in the form of evenly dispersed particles of the fluorine-based lubricity polymer represented by black dots on the surface of the plating layer according to Example 10, no significant change was observed.

In addition, according to Table 8, it can be confirmed that even if one week passes, there is no significant change in the surface composition of the plating layer according to Example 10.

In summary, the plating layer formed using the electroless plating solution according to the exemplary embodiment of the present invention can be confirmed that there is no significant change in composition over time, and thus, the electroless according to the exemplary embodiment of the present invention. It can be seen that the solution solution can provide a plating layer having excellent stability over time.

Claims (14)

Nickel precursors; Tungsten precursors; Complexing agents; Reducing agents including dimethylaminoborate; And a fluorine-based lubricity polymer comprising polytetrafluoroethylene;
The content of the complexing agent is 0.9 g or more and 20 g or less per 1 g of the tungsten precursor,
An electroless plating solution having a pH of 4-6. The method according to claim 1,
The nickel precursor may be Ni (CH ₃ COO) ₂ , Ni (CH ₃ COO) ₂ .4H ₂ O, Ni (NO ₃ ) ₂ .6H ₂ O, NiSO ₄ .6H ₂ O, C ₃₂ H ₁₆ N ₈ Ni, An electroless plating solution, which is at least one selected from the group consisting of NiCl ₂ and NiCl ₂ .6H ₂ O. The method according to claim 1,
The tungsten precursor is Na ₂ WO ₄ , WCl ₄ , WCl ₆ , WOCl ₄ and H ₂ WO ₄ Electroless plating solution that is one or more selected from the group consisting of. The method according to claim 1,
The complexing agent is an electroless plating solution that is at least one selected from the group consisting of malic acid, malonic acid, gluconic acid, succinic acid and citric acid. The method according to claim 1,
The content of the nickel precursor is an electroless plating solution that is 5 g or more and 20 g or less per liter of the electroless plating solution. The method according to claim 1,
The content of the tungsten precursor is an electroless plating solution of 0.4 g or more and 20 g or less per liter of the electroless plating solution. The method according to claim 1,
The content of the complexing agent is an electroless plating solution that is 10 g or more and 60 g or less per liter of the electroless plating solution. The method according to claim 1,
The amount of the reducing agent is an electroless plating solution that is 0.1 g or more and 10 g or less per liter of the electroless plating solution. The method according to claim 1,
The content of the fluorine-based lubricity polymer is an electroless plating solution of 1 ml or more and 30 ml or less per liter of the electroless plating solution. The method according to claim 1,
The electroless plating solution further comprises a buffer containing boric acid. The method according to claim 10,
The content of the buffer is an electroless plating solution that is 0.1 g or more and 5 g or less per liter of the electroless plating solution. Preparing a material to be plated;
Injecting the material to be plated into the electroless plating solution according to claim 1; And
Electroless plating method comprising; forming a plating layer on the surface of the material to be plated. delete The method according to claim 12,
The plating layer forming step; is performed at a temperature of less than 90 ℃ 65 ℃ electroless plating method.

Images