KR20150109100A

KR20150109100A - Method for Manufacturing Metal Pattern Structure having High Bonding between Polymer Substrate and Metal Film using Nano Structure Surface based on Nano Imprint Method and Metal Pattern Structure manufactured by the same

Info

Publication number: KR20150109100A
Application number: KR1020140032130A
Authority: KR
Inventors: 박인규; 엄현진; 김재한; 김택수; 정준호; 이응숙
Original assignee: 한국과학기술원; 한국기계연구원
Priority date: 2014-03-19
Filing date: 2014-03-19
Publication date: 2015-10-01

Abstract

A method for manufacturing a metal pattern structure according to the present invention comprises the following steps: preparing a polymer film; deriving a nanoimprint substrate in which a pattern is formed through nanoimprint processing on one side of the polymer film; and depositing a metal film on one side of the nanoimprint substrate in which the pattern is formed. Accordingly, the adhesion between the polymer substrate and the metal film is enhanced.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing a metal pattern structure for achieving high adhesive bonding between a polymer substrate and a metal film by using a nano structure surface based on a nanoimprint method, and Metal Film using Nano Structure Surface based on Nano Imprint Method and Metal Pattern Structure manufactured by the same}

The present invention relates to a technique of using a nanoimprint method to increase the adhesion between a polymer substrate and a metal film. More specifically, the present invention not only increases the roughness of a polymer substrate by using a nanoimprint method, To increase the adhesion between the polymer substrate and the metal film by increasing the adhesion at the corners of the embossed and intaglio angles.

Indium tin oxide (ITO) films are used as the electrode materials used in existing devices, and metal nanowire networks, carbon nanotubes (CNTs) , And grephene have been actively studied as alternative materials.

Recently, studies on flexible devices have been actively carried out, and metal films which are excellent in mechanical rigidity and easy to handle and easy to process are most widely used as flexible electrode electrodes.

However, most of them are limited to local parts, and there is almost no research on large - area flexible materials and devices using metal film as electrodes. The metal film formed on the most flexible film has flexibility, but the adhesion property between the metal and the flexible polymer substrate is poor. It is particularly vulnerable to moisture and is susceptible to bending and fatigue tests, making it practically difficult to apply to flexible devices without high packaging.

Conventionally, in order to solve such a problem, research has been carried out to increase the roughness of the polymer and the bonding period of the polymer by increasing the adhesion force between the flexible substrate and the metal, .

That is, most of the conventional techniques for increasing the adhesive force between the metal film and the polymer film are mostly employing an oxygen plasma treatment method, or using an ion plasma such as argon, helium, or nitrogen, or using chromium or titanium as an intermediate layer .

The plasma treatment is mainly based on a vacuum, in which the etching gas is injected or the plasma treatment is performed with a strong energy. Most of the researches have been carried out in such a manner that an atmospheric plasma treatment is carried out in order not to apply physical force to the polymer substrate Was also used.

However, in the case of using the plasma treatment as described above, there is a disadvantage in that it is difficult to apply to a large-area device because it has insufficient adhesion force for application to a bendable large-area device. In addition, it has a disadvantage in that it is vulnerable to moisture, weakens the adhesive force, weakens the metal electrode particularly in a wet process or a solution process, and is mechanically weak such as peel off phenomenon is accelerated in a high temperature moisture.

On the other hand, Japanese Patent Application Laid-Open No. 10-2013-0096613 discloses a polyimide film surface treatment method and a polyimide film having a metal layer formed thereon. The polyimide film is subjected to a wet process followed by a UV or plasma dry process, A method for producing a polyimide film having improved adhesion is provided.

However, the above prior art discloses only the technical content of improving the adhesion to metal by UV or plasma dry treatment after wet processing on the polyimide film. However, the polymer film itself is nano-imprinted without a wet process or chemical treatment, There is a problem that a technique for increasing the adhesion between a polymer and various metals is not disclosed.

(Patent Document 1) KR10-2013-0096613 A

In order to solve the above-described problems, the present invention aims to increase the roughness of the polymer substrate by using the nanoimprinting technique, to uniformly form roughness in each section, to increase the roughness, It is an object of the present invention to provide a method of manufacturing a metal pattern structure that enhances the adhesion between the polymer substrate and the metal film by enhancing the adhesion effect of the nano imprinted polymer substrate at the corners of the embossed and intaglio angles.

A method of fabricating a metal pattern structure according to one aspect of the present invention includes: preparing a polymer film; The method comprising: nanoimprinting one surface of the polymer film to obtain a patterned nanoimprint substrate; And depositing a metal film on one side of the patterned nanoimprint substrate, thereby increasing the adhesion between the polymer substrate and the metal film.

The metal film includes a case where the metal film is obliquely deposited on the nanoimprint substrate.

The step of depositing the metal film proceeds to any one of physical vapor deposition (PVD), thermal evaporation, e-beam evaporation, and sputtering.

The nanoimprint process uses a thermal nano imprint lithography or a UV nano imprint lithography technique.

The pattern formed on the nanoimprint substrate is a pattern in which embossed and intaglio angles are alternately arranged, and protrusions are formed on the embossed or intaglio areas to increase the sticking effect.

The protrusions are anchor-shaped.

The arrangement pattern of the patterns formed on the nanoimprint substrate is one of a group including a mesh, a line array, a hexagonal, and a network.

The metal film includes a plurality of metal layers.

The present invention provides a metal pattern structure manufactured according to the above-described method.

The metal pattern structure is a transparent substrate, and the transparent substrate maintains a transparent property because the metal film is formed only on one side of the transparent substrate.

The present invention provides an electrode, a polarizing plate, and an electronic device including the above-described metal pattern structure.

The adhesion structure between the nanoimprint and the metal film having the high adhesion property of the present invention can be readily applied to the industry since it uses the existing nanoimprint technology and can be widely applied to flexible materials and devices by improving the mechanical properties of the electrode have.

The high adhesive strength of the present invention utilizes the nano-imprinted sticking effect characteristics of the embossed or depressed structure, so that it has a high adhesive strength without any adhesive, chemical surface treatment or plasma treatment, so that the substrate including various polymers and polymer layers Can be applied. In addition, adhesion can be improved by forming a nanoimprint shape and a metal deposition on a material such as a conventional PDMS which has poor metal adhesion even if chemical treatment is performed with high adhesion.

In addition, since the nanoarray array and the nano-imprint structure having all embossed and intaglio angles such as a nano-dot array are used to maximize the number of embossed or engraved portions without any special design, the interface between the highly adhesive metal film and the polymer So that the nanoimprint structure can be widely and widely used by large area or patterning.

FIGS. 1A to 1C are views showing an embodiment of a nanoimprint substrate on which a pattern is formed by nanoimprinting a polymer film;
FIGS. 2A to 2C are views showing an embodiment in which a metal film is deposited on a patterned nanoimprint substrate,
3 is a view for explaining an attaching effect of the metal pattern structure,
4 is a view showing various embodiments of the shape of a metal pattern structure,
5 is a view for explaining a metal film deposited on a metal pattern structure,
FIG. 6 is a graph comparing the states of the accelerated wet-environment peeling test and the bending test after depositing titanium and gold on the PMMA film in the untreated state, the PMMA film in the plasma treatment, and the PMMA film in which the nanoimprint imprint structure is formed ,
FIG. 7A is a graph showing a comparison of adhesive force between a PMMA substrate and a metal film after depositing gold on a PMMA film without a treatment and a PMMA film with a nanoimprint structure,
FIG. 7B is a graph showing a comparison of adhesive strength between a PMMA substrate and a metal film after depositing titanium and gold on a PMMA film without a treatment, a PMMA film with a plasma treatment, and a PMMA film with a nanoimprint structure,
7C is a view showing a specimen for measuring an adhesion force between a PMMA film and a metal film,
7D is a photograph showing the specimen state after the experiment of measuring the adhesion force between the PMMA film and the metal film, and Fig.
8 is a view showing an embodiment in which a metal film can be partially or largely formed on a patterned nanoimprint substrate.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be understood, however, that the invention is not limited to the disclosed embodiments, but is capable of other various forms of implementation, and that these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of invention to those skilled in the art. It is provided to let you know completely. Wherein like reference numerals refer to like elements throughout.

In the following description, the term 'nanoimprinted substrate' is defined as a polymer structure having a pattern formed with embossed and intaglio patterns through a mold or lithography process with respect to a polymer film to be provided, and the 'metal pattern structure' Is defined as a substrate structure in which a metal pattern is adhered on a substrate with a high adhesive force through a nanoimprint type processing method.

Referring to FIGS. 1A to 1C, there are shown embodiments of a patterned nanoimprint substrate through nanoimprinting of a polymer film.

First, a first embodiment 10 of a nanoimprint substrate will be described with reference to FIG. 1A. A pattern 12 is formed on a polymer film 11 through a mold disposed on the top or bottom of the polymer film 11 . Here, the mold functions as a template for forming a pattern on the polymer film 11, and the metal nanopattern may be formed on a preparation substrate made of a material such as silicon, and then a polymer having high rigidity or And then removing the preparation substrate after pouring a hybrimer thereon. Or directly onto the polymer or hybrid to form the mold 10 having the metal nanostructure embedded therein.

Meanwhile, the nanoimprint substrate 10 can be obtained by using a thermal nano imprint lithography. The polymer can be obtained by applying a polymer cured to ultraviolet (UV) on a flexible polymer substrate and then irradiating ultraviolet nanoimprint lithography (uv nano imprint lithography).

Through this, the nanoimprinted substrate 10 is finally formed as a template for forming a metal film structure on the surface of the nanoimprinted substrate 10 and having flexibility and high adhesion.

Next, the second and third embodiments 20 and 30 of the nanoimprint substrate will be described with reference to FIGS. 1B and 1C. A separate base substrate (not shown) 23, 33) are reinforced.

Referring to FIGS. 2A to 2C, there are shown embodiments of a metal pattern structure in which a metal film is deposited on a patterned nanoimprint substrate.

2A, a polymer film 11 is subjected to nanoimprinting by applying heat and pressure to the polymer film 11, and then the metal film 110 is subjected to PVD, thermal evaporation, e-beam evaporation ), Or a sputtering method to form the metal pattern structure 100. The metal film 110 is continuously attached along the pattern 12. [

Next, the second embodiment 200 of the metal pattern structure will be described with reference to FIG. 2B. The metal film 210 can be deposited only on the upper surface of the pattern. That is, the metal film 210 may be attached only on the upper surface, not the inclined surfaces of the embossed and engraved patterns, which constitute the pattern.

Referring to FIG. 2C, the third embodiment 300 of the metal pattern structure will be described. The metal film 310 can be deposited on the upper surface and a part of the sloped surface of the pattern. That is, the metal film 310 may be attached only to a part of the upper surface and the inclined surface of the embossing constituting the pattern.

In addition, oblique deposition may be performed to increase the sticking effect according to the present invention.

Since such a metal pattern structure has a structure in which a metal film is formed on the upper portion of the structure, the metal pattern is not attached to the side portion, so that it is easy to increase the transmittance and easily form a uniform pattern structure. Therefore, Transparent electrodes, transparent displays, polarizers, polarizing elements, and the like.

Next, the effect of attaching the metal pattern structure 100 will be described with reference to FIG.

The principle of high adhesion of the metal film 110 using the structure of the nanoimprint substrate 10 of the present invention is as follows. The most important principle of high adhesion of the present invention is that a large amount of an attachment structure capable of inducing a sticking effect such as an anchor shape is formed on a relief or depressed portion of a pattern constituting the nanoimprint substrate 10 , It is possible to form a good adhesive force with the metal film formed on the attachment structure. That is, it is possible to increase the roughness and increase the adhesive force.

Particularly, by using the nanoimprint technique and process, it is possible to improve the adhesion to the metal through nano-structuring of the polymer in a pure manner, and to form a large number of such structures in sticking form, Can be formed.

4A to 4F show various embodiments of the metal pattern structure shape. FIGS. 4A, 4D and 4E illustrate a pattern in which a metal film is continuously deposited on a pattern, while the shapes of the patterns are in the order of a simple square, a bolt, and an inverted triangle, respectively.

FIGS. 4B, 4C, and 4F show a state in which the metal film is discontinuously deposited on the pattern, while the shapes of the patterns are simple rectangles or inverted triangles, respectively. 4B and 4F show a state in which the metal film covers only the upper face and the side face of the relief formed by the pattern, and FIG. 4C shows the form in which the metal film covers only the relief face between the reliefs forming the pattern.

As described above, the technique of providing a high adhesive force according to the present invention is a deformation of the pattern of the nanoimprint substrate 10, and the nanoimprint substrate 10 may be a substrate of a different kind of material, And a structure for imparting a high adhesive force, which is obtained by forming a structure for nanoimprinting a polymer layer formed on the substrate or increasing the adhesion effect.

FIG. 5 is a view for explaining a metal film deposited on the metal pattern structure of the present invention. FIG. 5 shows a state in which a metal nanofilm is deposited using gold having a width of 100 nm on a nano imprint structure in the form of a nanowire array. On the other hand, a photograph showing a section of the deposited state is shown in the upper right corner. Adhesive strength between the metal film and the nanoimprint substrate can be enhanced by using an anchor-shaped attached pillar formed on the circular dotted line.

FIG. 6 compares the states of the accelerated wet environment peeling test and the bending test after depositing titanium and gold on the PMMA film in the untreated state, the PMMA film in the plasma treatment, and the PMMA film in which the nanoimprint structure is formed.

6A, 6D, and 6G, which are arranged vertically on the left side, are a process of depositing 20 nm of Ti and 200 nm of Au on a PMMA film that has undergone no treatment and then performing an accelerated wet environment peeling test and a bending test sequentially . Herein, the accelerated wet environment peeling test is to perform the experiment for 2 hours after immersing the metal pattern structure in water at 80 ° C, and the bending test is to perform bending repetition 10,000 times with a bending radius of 1 cm.

6B, 6E, and 6H arranged vertically at the center are formed by depositing 20 nm of Ti and 200 nm of Au on a plasma-treated PMMA film, which is a conventional adhesion increasing method, and then performing an accelerated wet environment peeling test and a bending test sequentially . Here, the plasma treatment is to treat the O ₂ plasma for 30 minutes under atmospheric pressure and a power supply condition of 100 W.

6C, 6F, and 6I arranged vertically on the right side sequentially show accelerated and bending experiments after depositing 20 nm of Ti and 200 nm of Au on a PMMA film having a nanoimprint structure according to the present invention.

Comprehensive analysis of the above contents shows that the PMMA film having the nanoimprint structure according to the present invention has little change or less deformation compared to the PMMA film without the treatment and the PMMA film treated with the plasma.

FIG. 7A is a graph comparing the adhesion between the PMMA substrate and the metal film after gold is deposited on the PMMA film without the treatment and the PMMA film with the nanoimprint structure, FIG. 7B is a graph showing the adhesion between the PMMA film, A graph showing adhesion between a PMMA substrate and a metal film after depositing titanium and gold on a PMMA film having a plasma treatment and a PMMA film having a nanoimprint structure, respectively.

As described above, in the case of depositing gold on a PMMA film that has undergone no treatment, the interfacial fracture energy is only about 1 to 2 (J / m 2), which is higher than 50 (J / m 2) It can be seen that the adhesion is significantly lower than that of a PMMA film having a nanoimprint structure having energy.

In addition, the interfacial fracture energy is about 15 (J / m 2) when the gold and titanium are deposited on the untreated PMMA film and the plasma treated PMMA film, It can be seen that the adhesive force is significantly lower than that of the PMMA film having the nanoimprint structure having the interface fracture energy.

On the other hand, FIG. 7C shows the specimen for measuring the adhesive force between the PMMA film and the metal film, and FIG. 7D shows the specimen after the experiment for measuring the adhesive force between the PMMA film and the metal film.

As shown in FIG. 7C, the PMMA film was laminated in thicknesses of 20 nm and 200 nm respectively for planes, oxygen plasma treatments, and nanoimprinted three cases, Is fixed with an adhesive.

In the photographs at the left and the center of FIG. 7D, the degree of detachment of the metal film adhered on the PMMA film after the adhesive force measurement experiment can be confirmed. First, the planar state and the oxygen plasma treatment state of the PMMA film show that a considerable part of the metal film adhered on the PMMA film is separated.

On the other hand, as can be seen from the photograph on the right side of FIG. 7D, the nanoimprinted state of the PMMA film shows that most of the metal film adhered on the PMMA film remains attached to the PMMA film .

Comprehensively, the high-adhesive nanoimprint structure film according to the present invention has a higher adhesive force than the conventional PMMA film and plasma-treated PMMA film, Is almost not peeled off.

Conventional nanoimprint technology uses nanoimprint lithography to obtain optical characteristics for patterning. However, in the present invention, a nanoimprint technique is applied to a polymer substrate to enhance adhesion between a metal film and a polymer film First, the adhesion between the metal film and the nanoimprint polymer substrate was experimentally demonstrated.

8A and 8B are views showing a metal film adhered to a patterned nanoimprint substrate partially or largely.

The high-adhesion nanoimprint metal film of the present invention can be formed not only as a large area as shown in FIG. 8B but also partially formed as shown in FIG. 8A, so that it can be applied to a metal electrode having excellent adhesion when formed partially patterned Do.

In addition, the technique of providing a high adhesive force of the present invention can be applied to both a flexible material and a device having a high mechanical property, and it is possible to selectively pattern a portion having a high adhesive strength partially, .

As described above, the technique of providing the high adhesive force of the present invention uses a nano-imprinted sticking effect characteristic of the embossed or negative angle structure, so that it has a high adhesive force without an adhesive agent, a chemical surface treatment or a plasma treatment, Layer substrate. In addition, adhesion can be improved by forming a nanoimprint shape and a metal deposition on a material such as a conventional PDMS which has poor metal adhesion even if chemical treatment is performed with high adhesion.

Although the preferred embodiments of the present invention have been described, the present invention is not limited to the specific embodiments described above. It will be apparent to those skilled in the art that numerous modifications and variations can be made in the present invention without departing from the spirit or scope of the appended claims. And equivalents should also be considered to be within the scope of the present invention.

10, 20, 30: Nanoimprint substrate
11, 21, 31: Polymer film
12, 22, 32: pattern
100, 200, 300: metal pattern structure
110, 210, 310: metal film

Claims

Preparing a polymer film;
The method comprising: nanoimprinting a surface of the polymer film to form a patterned nanoimprinted substrate; And
And depositing a metal film on the patterned nanoimprint substrate,
Wherein the nanoimprinting process increases the roughness of the pattern and at the same time uses the sticking effect characteristic of the pattern formed on the nanoimprinted substrate through the relief or depression structure so that the polymer film and the metal Characterized in that the bonding force between the films is increased,
A method for manufacturing a metal pattern structure by a nanoimprint method.

The method according to claim 1,
Wherein the metal film is obliquely deposited on the nanoimprint substrate.
A method for manufacturing a metal pattern structure by a nanoimprint method.

The method according to claim 1,
Wherein the step of depositing the metal film proceeds to any one of PVD, thermal evaporation, e-beam evaporation, and sputtering.
A method for manufacturing a metal pattern structure by a nanoimprint method.

The method according to claim 1,
Wherein the nanoimprinting is performed using a thermal nano imprint lithography or an ultraviolet nano imprint lithography method.
A method for manufacturing a metal pattern structure by a nanoimprint method.

5. The method of claim 4,
Wherein the pattern formed on the nanoimprint substrate is a pattern in which embossing and engraving are alternately arranged and protrusions are formed on the embossed or intaglio areas to increase the sticking effect.
A method for manufacturing a metal pattern structure by a nanoimprint method.

6. The method of claim 5,
Characterized in that said protrusions are in the form of nano-anchor structures.
A method for manufacturing a metal pattern structure by a nanoimprint method.

6. The method of claim 5,
Wherein the arrangement pattern of the patterns formed on the nanoimprint substrate is one of a group including a mesh, a line array, a hexagonal, and a network.
A method for manufacturing a metal pattern structure by a nanoimprint method.

The method according to claim 1,
Characterized in that the metal film comprises a plurality of metal layers.
A method for manufacturing a metal pattern structure by a nanoimprint method.

9. A process for the preparation of a compound according to any one of claims 1 to 8,
Metal pattern structure.

10. The method of claim 9,
Wherein the metal pattern structure is a transparent substrate, and the transparent substrate maintains a transparent property as the metal film is formed only on one side of the transparent substrate.
Metal pattern structure.

An electrode comprising the metal pattern structure according to claim 9.

A polarizer comprising the metal pattern structure according to claim 9.

An element comprising the metal pattern structure according to claim 9.