WO2016056788A2 - Glass substrate manufacturing method for increasing bonding force with electroless plating layer - Google Patents

Abstract

The present invention relates to a glass substrate manufacturing method and, more specifically, to a glass substrate manufacturing method capable of increasing a bonding force with an electroless plating layer to be plated on the surface. To this end, the present invention provides a glass substrate manufacturing method for increasing a bonding force with an electroless plating layer, comprising: a first etching step of immersing a glass substrate into a hydrofluoric acid (HF) solution; and a second etching step of forming a three-dimensional network structure in the inner direction on the surface of the glass substrate on which the electroless plating layer is to be plated, by immersing, into a saturated silica solution, the glass substrate etched through the first etching step.

Description

Glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer

The present invention relates to a glass substrate manufacturing method, and more particularly, to a glass substrate manufacturing method that can increase the bonding strength with the electroless plating layer plated on the surface.

Glass exhibits high transmittance of materials, excellent thermal stability and mechanical properties, and has been applied to many fields such as various functional containers, automobiles, building materials, and electronic devices such as smart phones and displays. As the modern industry is a technology-intensive field, the demand for the material bonded to the application increases, so that there are continuous industrial fields that require such excellent properties of glass. In particular, in electrical devices such as touch screens, displays, and semiconductor substrate materials, electrical connections between devices forming fine electrical circuit patterns are important. In this case, when the glass material is used for the electrical devices as described above, the deposition of a metal material such as copper (Cu) to implement the electrical circuit on the glass material is essential.

In general, when glass is applied to a display process, sputter equipment is used to form a seed layer on the glass for strengthening bonding strength, and then copper is deposited thereon. However, the use of vacuum equipment, such as sputters, are expensive, equipment and operating cost of the equipment, the equipment occupies a large volume, and the overall process time also takes a lot of problems occur. In particular, conventionally, since copper is mainly deposited in two dimensions, i.e., in one direction, structural modification of equipment is required for homogeneous deposition in all three dimensions, which leads to additional cost and increase in equipment volume. do.

On the other hand, electroless case of Cu plating, the step of plating to precipitate the Cu on the medium to be coated by chemical reduction of the Cu ^{2 +} ions, being the whole procedure performed in solution-based, may be coated all of the entire sample As it is possible to mass-produce processes, it is applied to various industrial fields. However, glass-based materials are basically poor in bonding strength with Cu, and thus, there is a demand for a method or technology capable of strengthening bonding strength between them.

EP-0507719 introduces metallizing pastes to increase the adhesion of the glass. This patent describes a method of increasing the adhesion of glass by incorporating organic carriers, copper powder, alloy metals, and the like into the paste. In addition, Korean Patent Publication No. 10-2009-0119500 describes a method for forming a seed layer for electroless copper plating with silver. In this patent, silane is used to form a self-assembled monolayer on the surface, and a silver seed layer is formed, followed by electroless copper plating to increase the bonding strength of the glass substrate and copper. In addition, US Patent US6441213, which introduces a bonding enhancer as a method for increasing the bonding strength of a substrate such as glass, describes the contents of various bonding enhancers having low volatility. In addition, International Publication WO2004 / 020525 introduces a bonding agent that can be cured at room temperature, and describes a material for adding bonding force.

However, the above-mentioned prior patent documents are all related to a technique for increasing adhesion by forming additional coatings and seed layers on the glass surface, and there is a problem in that the construction and processing are complicated, and thus the process time and cost are increased. .

The present invention has been made to solve the problems of the prior art as described above, an object of the present invention is to provide a method for manufacturing a glass substrate that can increase the bonding strength with the electroless plating layer to be plated on the surface.

To this end, the present invention, the first etching step of immersing the glass substrate in hydrofluoric acid (HF) solution; And a second etching step of immersing the glass substrate etched through the first etching step in a saturated silica solution to form a three-dimensional network structure inwardly on the surface of the glass substrate on which the electroless plating layer is plated. It provides a glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer, characterized in that.

In the first etching step, the glass substrate may be immersed in the hydrofluoric acid (HF) solution of 1 to 3 wt.% For at least 2 minutes.

As the glass substrate, any one of soda-lime glass and alkali-free glass may be used.

In the second etching step, the silica solution may be maintained at 30 to 50 ° C., and then the glass substrate may be immersed for 10 to 45 minutes.

In addition, the saturated silica solution is stirred in an excess of silica (SiO ₂ ) or silicic acid (SiO ₂ · H ₂ O) powder in a solution of 10 to 25wt.% Silica fluoride (H ₂ SiF ₆ ), at least 10㎛ or less It can be prepared by filtering.

In this case, a boric acid solution (B (OH) ₂ ) or potassium fluoride (KF) solution may be added to the saturated silica solution.

In addition, after the first etching step and the second etching step, cleaning and drying of the glass substrate may be performed.

The three-dimensional network structure may be formed to a depth of 30 ~ 200nm in the inward direction from the surface of the glass substrate.

According to the present invention, by forming the three-dimensional network structure by etching inward from the surface of the glass substrate on which the electroless plating layer is plated, the anchoring effect on the electroless plating layer during plating for forming the electroless plating layer (anchoring effect) It is possible to implement, through which, it is possible to increase the bonding strength with the electroless plating layer without using additional materials or media for strengthening the bonding.

1 is a schematic diagram showing a glass substrate manufactured according to an embodiment of the present invention.

Figure 2 is a schematic diagram showing a three-dimensional network structure formed on the surface of the glass substrate prepared according to the embodiment of the present invention.

3 is a photograph taken with a scanning electron microscope of the etched glass substrate surface (left) and the unetched glass substrate surface (right).

Figure 4 is a schematic diagram showing a state in which an electroless plating layer is plated on the surface of the glass substrate prepared according to the embodiment of the present invention.

5 is a photograph taken with a scanning electron microscope of an electroless copper plating layer (left) plated on an etched glass substrate surface (left) and an electroless copper plating layer (right) plated on an unetched glass substrate surface.

Hereinafter, a glass substrate manufacturing method according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

In addition, in describing the present invention, when it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

Glass substrate manufacturing method according to an embodiment of the present invention, unlike the conventional, glass substrate that can increase the bonding strength with the electroless plating layer (20 of FIG. 4) without using additional materials or media for strengthening the bonding (Fig. 1 of 100). The glass substrate manufacturing method includes a first etching step and a second etching step.

First, the first etching step is a step of pre-etching the glass substrate (100 in FIG. 1) prior to the second etching step, which is the main etching. In this first etching step, the glass substrate (100 in FIG. 1) is immersed in a hydrofluoric acid (HF) solution. Specifically, in the first etching step, it is preferable to immerse the glass substrate (100 in FIG. 1) for at least 2 minutes in the hydrofluoric acid (HF) solution of 1 to 3 wt.%. At this time, after immersing the glass substrate (100 in FIG. 1) in the hydrofluoric acid (HF) solution as described above, after removing the glass substrate (100 in FIG. 1) from the hydrofluoric acid (HF) solution, the glass substrate (100 in FIG. 1) After washing, it is dried.

This first etching step is carried out to remove the oxide film and contaminants on the surface of the glass substrate (100 in FIG. 1), that is, the surface on which the electroless plating layer (20 in FIG. 4) is to be plated.

On the other hand, in the embodiment of the present invention, as the glass substrate (100 of FIG. 1) on which the electroless plating layer (20 of FIG. 4) is plated, one of soda-lime glass and alkali-free glass may be used.

Next, as shown in FIGS. 1 and 2, the second etching step is performed by pre-etching, ie, removing the surface oxide film and contaminants from the glass substrate 100 to the saturated silica solution. Immersion step. In addition, the second etching step is a step of forming the three-dimensional network structure 110 inward on the surface of the glass substrate 100 on which the electroless plating layer 20 is plated. That is, in the second etching step, the glass substrate 100 is immersed in a saturated silica solution for a predetermined time, thereby removing alumina and boron, which are alkali and alkaline earth elements or meshes, on the surface of the glass substrate 100. The three-dimensional network structure 110 is formed inward from the surface of the.

Here, in the saturated silica solution used for etching the glass substrate 100, an excessive amount of silica (SiO ₂ ) or silicic acid (SiO ₂ · H ₂ O) powder is added to a 10-25 wt.% Silica fluoride (H ₂ SiF ₆ ) solution. After stirring, it can manufacture by filtering to at least 10 micrometers or less. In this case, depending on the type of glass substrate 100 used or for controlling the reaction rate, a boric acid solution (B (OH) ₂ ) or potassium fluoride (KF) solution may be added to the prepared silica solution.

Specifically, in the second etching step, the saturated silica solution prepared as described above is maintained at 30 to 50 ° C., and then the glass substrate 100 pre-etched through the first etching step is applied to the saturated silica solution for 10 to 45 minutes. Immerse. Thereafter, the glass substrate 100 is taken out of the saturated silica solution, and then washed and dried.

As such, when the first etching step and the second etching step are performed in sequence, the glass substrate 100 having the three-dimensional network structure 110 formed at a depth of 30 to 200 nm in the inward direction from the surface is manufactured.

For example, when a glass substrate 100 made of soda-lime glass is used and immersed in a saturated silica solution at 45 ° C. for 45 minutes, the three-dimensional network 100 may be formed to a depth of about 100 to 120 nm. Can be.

3 is a photograph of the etched glass substrate surface (left) and the unetched glass substrate surface (right) by scanning electron microscopy. When the glass substrate is manufactured by the glass substrate manufacturing method according to an embodiment of the present invention, FIG. Unlike the surface of the glass substrate which is not etched, it can be visually confirmed that a three-dimensional network structure is formed inward from the surface of the glass substrate to a depth of about 115 nm.

On the other hand, as shown in Figure 4, when the metal, for example, the electroless copper plating process on the surface of the glass substrate 100 manufactured according to an embodiment of the present invention, first, from the surface of the glass substrate 100 After the copper plating solution penetrates or fills the irregular holes and grooves of the three-dimensional network structure 110 formed inward, the electroless plating layer 20 is plated and formed on the surface of the glass substrate 100. In this case, the electroless plating layer 20 formed on the surface of the glass substrate 100 and the copper filled in the irregular hole and groove of the three-dimensional network structure 110 is present in the form of being connected to each other, in this case, electroless The plating layer 20 is fixed or supported by the copper filled in the irregular holes and grooves of the three-dimensional network structure 110, that is, the copper filled in the irregular holes and grooves of the three-dimensional network structure 110 are connected thereto. Since the electroless plating layer 20 is held, the bonding force between the glass substrate 100 and the electroless plating layer 20 is increased.

That is, after forming the three-dimensional network structure 110 in the inward direction from the surface of the glass substrate 100 through the glass substrate manufacturing method according to an embodiment of the present invention, if the copper plating process thereon, as described above Anchoring effect on the electroless plating layer 20 can be realized, and through this, bonding strength with the electroless plating layer 20 can be increased without using additional materials or media for strengthening the bonding. .

FIG. 5 is a photograph of an electroless copper plating layer (left) plated on an etched glass substrate surface and an electroless copper plating layer (right) plated on an unetched glass substrate surface by scanning electron microscope. First, looking at the electroless copper plated layer (left) photograph plated on the surface of the etched glass substrate, it can be visually confirmed that the falling effect of the electroless copper plated layer is generated on the glass substrate on which the three-dimensional network structure is formed. On the other hand, when looking at the electroless copper plating layer (right) plated on the surface of the glass substrate not etched, it can be seen that there is no change in the interface between the glass substrate and the electroless copper plating layer.

On the other hand, after plating the electroless copper plating layer on the surface of the glass substrate prepared by the glass substrate manufacturing method according to an embodiment of the present invention, as a result of evaluating the adhesion strength (adhesion strength) of the glass substrate and the electroless copper plating layer, the bonding strength This was measured at about 3.0 N / mm 2. On the other hand, after the electroless copper plating layer was plated on the surface of the non-etched glass substrate, the bonding force between the glass substrate and the electroless copper plating layer was evaluated. As a result, the bonding force was measured to be about 1.5 N / mm 2. That is, when a glass substrate having a three-dimensional network structure is manufactured through the glass substrate manufacturing method according to the embodiment of the present invention, the bonding force with the electroless plating layer is increased by about two times or more than otherwise.

As described above, although the present invention has been described with reference to the limited embodiments and the drawings, the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains various modifications and variations from such descriptions. This is possible.

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below but also by the equivalents of the claims.

Claims (8)

1. A first etching step of dipping the glass substrate in a hydrofluoric acid (HF) solution; And

   A second etching step of immersing the glass substrate etched through the first etching step in a saturated silica solution to form a three-dimensional network structure inwardly on the surface of the glass substrate on which the electroless plating layer is plated;

   Glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer comprising a.
2. The method of claim 1,

   And in the first etching step, the glass substrate is immersed in the hydrofluoric acid (HF) solution at 1 to 3 wt.% For at least 2 minutes or more.
3. The method of claim 1,

   The glass substrate is a glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer, characterized in that using any one of soda-lime glass, alkali-free glass as the glass substrate.
4. The method of claim 1,

   In the second etching step, after maintaining the silica solution at 30 ~ 50 ℃, the glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer, characterized in that the glass substrate is immersed for 10 to 45 minutes.
5. The method of claim 1,

   The saturated silica solution was stirred with an excess of silica (SiO ₂ ) or silicic acid (SiO ₂ · H ₂ O) powder in a 10-25 wt.% Silica fluoride (H ₂ SiF ₆ ) solution, followed by filtering at least 10 μm. A glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer, characterized in that the manufacturing.
6. The method of claim 5,

   Boric acid solution (B (OH) ₂ ) or potassium fluoride (KF) solution is added to the saturated silica solution, glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer.
7. The method of claim 1,

   After the first etching step and the second etching step, the glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer, characterized in that the cleaning and drying process for the glass substrate is involved.
8. The method of claim 1,

   The three-dimensional network structure is a glass substrate manufacturing method for increasing the bonding strength with the electroless plating layer, characterized in that formed in a depth of 30 ~ 200nm inward direction from the surface of the glass substrate.

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