KR20220134193A - Method for forming metal pattern selectively using metal oxide - Google Patents

Abstract

One embodiment of the present invention provides a method of forming a selective metal pattern using a metal oxide. The method comprises: a step (S100) of forming a first metal oxide layer (20) by applying a first metal oxide coating solution on a substrate (10); a step (S200) of forming an etching pattern (40) by emitting a laser (30) on the surface of the substrate on which the first metal oxide layer (20) is formed; a step (S300) of forming a catalyst layer (50) by applying a catalyst coating solution on the substrate (11) on which the etching pattern (40) is formed; a step (S400) of removing the first metal oxide layer (21) so that only the catalyst layer (51) remains on the etching pattern (40); and a step (S500) of performing electroless plating to form an electroless plating layer (60) on the catalyst layer (51). According to an embodiment of the present invention, a selective metal pattern can be formed by electroless plating by removing the metal oxide layer again after forming the metal oxide layer so that the catalyst layer remains only in the etching pattern.

Description

Method for forming metal pattern selectively using metal oxide

The present invention relates to a method for forming a selective metal pattern, and more particularly, to a method for forming a selective metal pattern using a metal oxide.

With the miniaturization and integration of electronic components, the demand for a technology for selectively coating and depositing metals only on desired parts on the surface of the base material is increasing.

Conventionally, a vacuum deposition method using PVD and CVD has been used as a technology for selectively and precisely depositing metals in this way.

For example, Korean Patent Registration No. 10-1607519 (Name: Method of Forming a Circuit Pattern Using Plasma and a Metal Material) discloses a method of forming a pattern by disposing a mask on a substrate and performing plasma treatment.

However, the techniques for forming a pattern by the deposition process require a separate mask for selective deposition and are difficult to apply to a curved shape, so there are limitations in production efficiency and process flexibility when applied to mass production.

Therefore, there is a need to study a technology capable of metal patterning in various shapes on various substrates while simplifying the process.

Republic of Korea Patent Publication No. 10-1607519

An object of the present invention is to provide a method for forming a selective metal pattern using a metal oxide capable of selectively forming a metal pattern without using a mask.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. There will be.

In order to achieve the above technical object, an embodiment of the present invention provides a method for forming a selective metal pattern using a metal oxide.

In an embodiment of the present invention, a method for forming a selective fine metal pattern using a metal oxide includes: forming a first metal oxide layer by applying a first metal oxide coating solution on a substrate; forming an etching pattern by irradiating a laser on the surface of the substrate on which the first metal oxide layer is formed; forming a catalyst layer by applying a catalyst coating solution on the substrate on which the etching pattern is formed; removing the first metal oxide layer so that the catalyst layer remains only in the etch pattern; and performing electroless plating to form an electroless plating layer on the catalyst layer; includes

In an embodiment of the present invention, the first metal oxide coating solution includes a Si _x O _y material having a non-stoichiometric composition with artificial defects to enable dissolution depending on pH, and x and y may be real numbers greater than zero. .

In an embodiment of the present invention, the first metal oxide layer may be formed by a spray method, a spin coating method, or a deep coating method.

In an embodiment of the present invention, the etching pattern may be formed by laser etching from a laser irradiation area to the first metal oxide layer and a partial area of the substrate.

In an embodiment of the present invention, the laser may be a solid laser, a gas laser, or a fiber laser.

In an embodiment of the present invention, the catalyst coating solution includes metal-second metal oxide catalyst particles, and the second metal oxide may be different from the first metal oxide.

In an embodiment of the present invention, in the metal-second metal oxide catalyst particle, the metal is gold (Au), silver (Ag), platinum (Pt), cobalt (Co), nickel (Ni), tin (Sn) ), palladium (Pd) or iridium (Ir), and the second metal oxide is Al _m O _n , Zn _m O _n , Ru _m O _n , Zr _m O _n , Cu _m O _n , Co _m O _n , Ce _m O _n , Nb _m O _n , Ta _m O _n or Ti _m O _n , where m and n may be real numbers greater than zero.

In an embodiment of the present invention, the step of forming the catalyst layer may be performed by a spray method, a spin coating method, or a deep coating method.

In an embodiment of the present invention, the removing of the first metal oxide layer may include removing the first metal oxide layer by impregnating it in a basic aqueous solution, or removing the first metal oxide layer by ultrasonication after impregnation.

In an embodiment of the present invention, the electroless plating layer may be copper (Cu), nickel (Ni), silver (Ag), or an alloy layer thereof.

In order to achieve the above technical object, another embodiment of the present invention provides a metal pattern film prepared by a selective metal pattern forming method using a metal oxide.

According to an embodiment of the present invention, a selective metal pattern can be formed by electroless plating by removing the metal oxide layer again after forming the metal oxide layer so that the catalyst layer remains only in the etch pattern.

In addition, by forming the etching pattern using a laser, it is possible to pattern a metal having a precise, fine, and various shapes.

In addition, since a separate mask is not used, it is easy to apply to a flexible substrate or a curved substrate, and the production efficiency is excellent because the process time is shortened.

The effects of the present invention are not limited to the above effects, and it should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a flowchart of a method for forming a selective metal pattern using a metal oxide according to an embodiment of the present invention.
2 is a schematic diagram of a method for forming a selective metal pattern using a metal oxide according to an embodiment of the present invention.
3 is a selectively formed metal pattern according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is "connected (connected, contacted, coupled)" with another part, it is not only "directly connected" but also "indirectly connected" with another member interposed therebetween. "Including cases where In addition, when a part "includes" a certain component, this means that other components may be further provided without excluding other components unless otherwise stated.

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

A method of forming a selective metal pattern using a metal oxide according to an embodiment of the present invention will be described.

1 is a flowchart of a method for forming a selective metal pattern using a metal oxide according to an embodiment of the present invention.

2 is a schematic diagram of a method for forming a selective metal pattern using a metal oxide according to an embodiment of the present invention.

1 and 2, the selective metal pattern forming method using a metal oxide includes the steps of forming a first metal oxide layer 20 by applying a first metal oxide coating solution on a substrate 10 (S100); forming an etching pattern 40 by irradiating a laser 30 on the surface of the substrate on which the first metal oxide layer 20 is formed (S200); forming a catalyst layer 50 by applying a catalyst coating solution on the substrate 11 on which the etching pattern 40 is formed (S300); removing the first metal oxide layer 21 so that the catalyst layer 51 remains only in the etching pattern 40 (S400); and performing electroless plating to form an electroless plating layer 60 on the catalyst layer 51 (S500); includes

In a first step, a first metal oxide coating solution is applied on the substrate 10 to form a first metal oxide layer 20 (S100) (FIG. 2(a)).

The substrate 10 may include an electrically non-conductive material.

For example, the substrate 10 may include glass or a flexible or stretchable polymer material.

Again, for example, the substrate 10 is glass, epoxy, phenolic resin, liquid crystal polymer (LCP), polyimide (PI), polyester (PE), glass epoxy, It may include silicone rubber, polydimethylsiloxane (PDMS), or polyvinylidene difluoride (PVDF), but is not limited thereto if the substrate is an electrically non-conductive material.

The first metal oxide may include a non-stoichiometric Si _x O _y material having artificial defects such that the coating solution can be dissolved according to pH, and x and y may be real numbers greater than zero.

For example, the first metal oxide coating solution may include tetraethyl orthosilicate (TEOS) or methyl triethoxysilane (MTES).

The first metal oxide coating solution may have a dissolution property depending on pH.

The first metal oxide coating solution includes a Si _x O _y material by a sol-gel method, and the solution was prepared by artificially forming a defect so that it could be easily removed in a basic solution.

For example, the first metal oxide coating solution is 0.1 to 1.0 mole of tetraethyl orthosilicate (TEOS), 0.1 to 1.0 mole of methyl triethoxysilane (MTES), 5 to 15 moles mol of ethanol, 1 mol to 10 mol of distilled water, and 0.01 mol to 0.1 mol of hydrochloric acid may be included in the sol-gel method.

The first metal oxide layer 20 may be formed by a spray method, a spin coating method, or a deep coating method.

As a specific example, the first metal oxide layer 20 may be formed by applying the first metal oxide coating solution on a liquid crystal polymer (LCP) substrate by a dip coating method.

In the second step, an etching pattern 40 is formed by irradiating the laser 30 on the surface of the substrate on which the first metal oxide layer 20 is formed (S200) (FIG. 2(b)(c)).

When the laser 30 is irradiated on the substrate 10 on which the first metal oxide layer 20 is formed, the first metal oxide layer 21 disappears only in the laser irradiation area, and a part of the surface of the substrate 11 is is etched to form an etch pattern 40 .

That is, the etching pattern 40 may be formed by laser etching from the laser irradiation area to the first metal oxide layer 21 and a partial area of the substrate 11 .

Accordingly, the laser irradiation area is etched up to a partial area of the upper portion of the substrate 11 including the first metal oxide layer 21 , and the laser non-irradiation area does not damage the first metal oxide layer 21 . It remains coated on the substrate 11 (FIG. 2(c)).

Accordingly, the etched pattern 40 is formed by laser etching only the desired portion to form the pattern, and the metal pattern can be formed by selectively electroless plating only the etched pattern in a subsequent step.

The laser 30 may be a solid laser, a gas laser, or a fiber laser.

For example, the solid-state laser may be a ruby laser, an Nd:YAG laser, an Nd:glass laser, or a Ti:Sapphire laser.

For example, the gas laser may be a CO ₂ laser, an Ar laser, or a He-Ne laser.

For example, the fiber laser may be a fiber laser doped with a rare earth element such as Yb, Er, or Nd.

By delicately controlling the type, wavelength, or intensity of the laser 30, an etching pattern or a fine etching pattern of a required shape can be formed.

For example, the laser irradiation conditions may include a laser irradiation intensity of 10 to 20 W, a frequency of 20 to 70 kHz, a pulse duration of 20 to 100 ns, a speed of 1.5 to 2.5 m/s, and the number of repetitions of 2 to 5 times. can

As a specific example, the etching pattern 40 may be formed by irradiating a YTTERBIUM PULSED FIBER laser on a liquid crystal polymer (LCP) substrate coated with a Si _x O _y layer. .

In the third step, the catalyst layer 50 is formed by applying a catalyst coating solution on the substrate 11 on which the etching pattern 40 is formed (S300) (FIG. 2(d)).

The catalyst coating solution may include metal-second metal oxide catalyst particles, and the second metal oxide may be a material different from that of the first metal oxide.

This is because, when the first metal oxide and the second metal oxide must be different materials, the second metal oxide layer may not be removed in the subsequent step of removing the first metal oxide layer. Since the second metal oxide is a catalyst layer for electroless plating, it should remain.

In the metal-second metal oxide catalyst particles, the metal is gold (Au), silver (Ag), platinum (Pt), cobalt (Co), nickel (Ni), tin (Sn), palladium (Pd) or iridium (Ir), wherein the second metal oxide is Al _m O _n , Zn _m O _n , Ru _m O _n , Zr _m O _n , Cu _m O _n , Co _m O _n , Ce _m O _n , Nb _m O _n , Ta _m O _n or Ti _m O _n , where m and n may be greater than zero real numbers.

The second metal oxide may be a sol-gel-based metal oxide.

In order to perform electroless plating in a subsequent step, the catalyst coating layer 50 is formed, and the electroless plating method is a method in which a metal is coated on a substrate through an autocatalytic chemical reduction reaction without an applied current. In order to cause the reaction, the activation process of the surface is essential, and a metal catalyst is used for activation.

In addition, the bonding strength between the substrate 11 and the electroless plating layer may be improved by the second metal oxide.

Therefore, the metal-second metal oxide catalyst particles reduce the electroless plating metal only in the etch pattern to form the electroless plating layer, while improving the bonding strength between the substrate 11 and the electroless plating layer.

For example, when the electroless plating layer is a copper (Cu) or nickel (Ni) layer, Sn-Pd-Ti _m O _n may be used as the metal-second metal oxide catalyst particles.

In the copper electroless plating process, a palladium catalyst may be preferably used among various metal catalysts because palladium has a higher reduction potential than copper and has relatively excellent catalytic properties compared to other metal catalysts.

The metal-second metal oxide catalyst particles may be prepared by precipitating the metal particles on the surface of the second metal oxide, for example, may be prepared by a sol-gel (Sol-Gel) method.

For example, including the Sn-Pd-Ti _m O _n The catalyst coating solution is 0.1 to 1.0 mol of titanium tetraisopoxide as a precursor, 0.01 to 0.03 mol of palladium salt (PdCl ₂ ), 0.1 to 0.5 mol of tin salt (SnCl ₂ 2H ₂ O) as the catalyst metal particles. By adding alcohol (Isopropyl alcohol, IPA), distilled water, hydrochloric acid, etc., a synthetic solution can be prepared by a sol-gel method.

In addition, a coupling agent may be further included in the catalyst coating solution including the metal-second metal oxide catalyst particles.

The coupling agent may be used to increase the bonding strength of dissimilar materials.

For example, the coupling agent may include any one or more selected from the group consisting of a zirconia coupling agent and a titanate coupling agent.

The catalyst layer 50 may be formed by wet coating.

For example, the wet coating may include a spray method, a spin coating method, or a deep coating method.

As a specific example, a Sn-Pd-Ti _m O _n catalyst coating solution may be applied by a dip coating method on a liquid crystal polymer (LCP) substrate on which an etching pattern is formed to form a Sn-Pd-Ti _m O _n catalyst layer. .

By the catalyst layer 50 , the electroless plating layer 60 to be performed in a later step is easily formed on the substrate 11 , and the electroless plating layer 60 has a strong bonding force with the substrate 11 . can

In a fourth step, the first metal oxide layer 21 is removed so that the catalyst layer 51 remains only in the etching pattern 40 (S400) (FIG. 2(e)).

In the step of removing the first metal oxide layer 21, the first metal oxide layer may be removed by impregnating it in a basic aqueous solution, or removing it by ultrasonication after impregnation.

For example, the step of removing the first metal oxide layer 21 may be conveniently performed by immersion in a basic aqueous solution or ultrasonic treatment in a basic aqueous solution for 30 seconds to 3 minutes at room temperature.

By removing the first metal oxide layer 21 , the catalyst layer 51 remains only in the etch pattern 40 , and all coating layers previously formed on the surface of the substrate other than the etch pattern 40 may be removed.

In the fifth step, electroless plating is performed to form the electroless plating layer 60 on the catalyst layer 51 (S500) (FIG. 2(f)).

The electroless plating layer 60 may be formed by performing metal electroless plating on the catalyst layer 51 as a seed layer.

The source material used in the electroless plating process may include copper (Cu), nickel (Ni), silver (Ag), or an alloy thereof, that is, the electroless plating layer 60 according to the type of the source material. ) may be different.

Accordingly, the electroless plating layer 60 may be formed of copper (Cu), nickel (Ni), silver (Ag), or an alloy layer thereof depending on the electroless plating source material.

As a specific example, an electroless plating layer may be formed by performing electroless nickel plating using nickel on a liquid crystal polymer (LCP) substrate on which a Sn-Pd-Ti _m O _n catalyst layer is formed only in the etching pattern.

By filling in the etched pattern selectively formed on the substrate 11 by the formation of the electroless plating layer 60 , a metal pattern may be formed in the same pattern as the etched pattern.

A metal pattern film manufactured by a method for forming a selective metal pattern using a metal oxide according to another embodiment of the present invention will be described.

Referring to FIG. 2(f), the metal pattern film manufactured by the selective metal pattern forming method using the metal oxide includes: a substrate 11; a catalyst layer 51 selectively positioned on the substrate 11; and an electroless plating layer 60 positioned on the catalyst layer 51 .

First, the substrate 11 may include an electrically non-conductive material.

For example, the substrate 11 may include glass or a flexible or stretchable polymer material.

Again, for example, the substrate 11 is glass, epoxy, phenolic resin, liquid crystal polymer (LCP), polyimide (PI), polyester (PE), glass epoxy, It may include silicone rubber, polydimethylsiloxane (PDMS), or polyvinylidene difluoride (PVDF), but is not limited thereto if the substrate is an electrically non-conductive material.

Next, the catalyst layer 51 may be selectively positioned on the substrate 11 .

The selective position is an area in which the metal pattern, which is the electroless plating layer 60 , is to be located on the substrate 11 .

Accordingly, the catalyst layer 51 may have the same pattern as the finally formed metal pattern.

The catalyst layer 51 may include metal-second metal oxide catalyst particles.

In the metal-second metal oxide catalyst particle, the metal is gold (Au), silver (Ag), platinum (Pt), cobalt (Co), nickel (Ni), tin (Sn), palladium (Pd) or iridium (Ir), wherein the second metal oxide is Al _m O _n , Zn _m O _n , Ru _m O _n , Zr _m O _n , Cu _m O _n , Co _m O _n , Ce _m O _n , Nb _m O _n , Ta _m O _n or Ti _m O _n , where m and n may be greater than zero real numbers.

The second metal oxide may be a sol-gel-based metal oxide.

In the metal-second metal oxide catalyst particles, the metal is such that the electroless plating layer 60 is reduced during electroless plating, and the second metal oxide is formed of the substrate 11 and the electroless plating layer 60 . The bonding strength can be improved.

Accordingly, the electroless plating layer 60 can be easily formed by the catalyst layer 51 , and the bonding force of the electroless plating layer 60 with the substrate 11 can be strengthened.

For example, when the electroless plating layer is a nickel (Ni) layer, Sn-Pd-Ti _m O _n may be used as the metal-second metal oxide catalyst particles.

Next, the electroless plating layer 60 may be positioned on the catalyst layer 51 .

The material of the electroless plating layer 60 may be different depending on the source material used in the electroless plating process.

The source material may include copper (Cu), nickel (Ni), silver (Ag), or an alloy thereof.

Accordingly, the electroless plating layer 60 may be formed of copper (Cu), nickel (Ni), silver (Ag), or an alloy layer thereof depending on the electroless plating source material.

For example, the metal pattern film according to an embodiment of the present invention, Sn-Pd-Ti _m O _n catalyst layer selectively positioned on the polymer substrate; An electroless nickel plating layer positioned on the Sn-Pd-Ti _m O _n catalyst layer may be included.

Example

SixOy was coated on a liquid crystal polymer (LCP) substrate by dip coating to form a first metal oxide layer. Next, by using YTTERBI YTTERBIUM PULSED FIBER laser on the surface of the substrate on which the first metal oxide layer is formed, the etch pattern was formed by irradiating the laser under the conditions of 14 W, 50 kHz, 50 ns pulse duration, 2 m/s speed, and 2 cycles. formed. Next, a Sn-Pd-Ti _m O _n catalyst layer was formed by dip coating a catalyst coating solution containing Sn-Pd-Ti _m O _n catalyst particles on the substrate on which the etching pattern was formed. Next, the first metal oxide layer was removed by immersion in a basic aqueous solution, so that the Sn-Pd-Ti _m O _n catalyst layer remained only in the etch pattern. Next, a selective metal pattern was formed by performing electroless plating using a nickel source to form an electroless nickel plating layer on the catalyst layer.

Experimental example

3 is a selectively formed metal pattern according to an embodiment of the present invention.

Referring to FIG. 3 , a metal pattern selectively formed on the substrate can be confirmed.

According to an embodiment of the present invention, a selective metal pattern can be formed by electroless plating by removing the metal oxide layer again after forming the metal oxide layer so that the catalyst layer remains only in the etch pattern.

In addition, by forming the etching pattern using a laser, it is possible to pattern a metal having a precise, fine, and various shapes.

In addition, since a separate mask is not used, it is easy to apply to a flexible substrate or a curved substrate, and the production efficiency is excellent because the process time is shortened.

The foregoing description of the present invention is for illustration, and those of ordinary skill in the art to which the present invention pertains can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and likewise components described as distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention.

10, 11: Substrate
20, 21: first metal oxide layer
30: laser
40: etching pattern
50, 51: catalyst layer
60: electroless plating layer

Claims (11)

forming a first metal oxide layer by applying a first metal oxide coating solution on a substrate;
forming an etching pattern by irradiating a laser on the surface of the substrate on which the first metal oxide layer is formed;
forming a catalyst layer by applying a catalyst coating solution on the substrate on which the etching pattern is formed;
removing the first metal oxide layer so that the catalyst layer remains only in the etch pattern; and
forming an electroless plating layer on the catalyst layer by performing electroless plating; A method for forming a selective metal pattern using a metal oxide, comprising: According to claim 1,
In the step of forming the first metal oxide layer,
The first metal oxide coating solution includes a non-stoichiometric Si _x O _y material with artificial defects to enable dissolution depending on pH, and x and y are a selective metal using a metal oxide, characterized in that it is a real number greater than zero. How to form a pattern. According to claim 1,
The method of forming a selective metal pattern using a metal oxide, characterized in that the first metal oxide layer is formed by a spray method, a spin coating method, or a deep coating method. According to claim 1,
The etching pattern is a selective metal pattern forming method using a metal oxide, characterized in that formed by laser etching from the laser irradiation area to the first metal oxide layer and a partial area of the substrate. The method of claim 1,
In the step of forming the etching pattern,
The laser is a selective metal pattern forming method using a metal oxide, characterized in that the solid laser, gas laser or fiber laser. According to claim 1,
In the step of forming the catalyst layer,
The catalyst coating solution includes metal-second metal oxide catalyst particles, wherein the second metal oxide is different from the first metal oxide. 7. The method of claim 6,
In the metal-second metal oxide catalyst particle, the metal is gold (Au), silver (Ag), platinum (Pt), cobalt (Co), nickel (Ni), tin (Sn), palladium (Pd) or iridium (Ir), wherein the second metal oxide is Al _m O _n , Zn _m O _n , Ru _m O _n , Zr _m O _n , Cu _m O _n , Co _m O _n , Ce _m O _n , Nb _m O _n , Ta _m O _n or Ti _m O _n , and m and n are real numbers greater than 0. A method for forming a selective metal pattern using a metal oxide. According to claim 1,
The forming of the catalyst layer is a selective metal pattern forming method using a metal oxide, characterized in that performed by a spray method, a spin coating method, or a deep coating method. According to claim 1,
The step of removing the first metal oxide layer comprises removing the first metal oxide layer by impregnating it in a basic aqueous solution, or removing the first metal oxide layer by ultrasonication after impregnation. According to claim 1,
In the step of forming the electroless plating layer,
The electroless plating layer is a selective metal pattern forming method using a metal oxide, characterized in that copper (Cu), nickel (Ni), silver (Ag) or an alloy layer thereof. A metal pattern film prepared by the selective metal pattern formation method using the metal oxide of claim 1.

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