KR20170029838A

KR20170029838A - Conducting film, method for preparing the same and electrode comprising the same

Info

Publication number: KR20170029838A
Application number: KR1020150126916A
Authority: KR
Inventors: 이형진; 이윤구
Original assignee: 재단법인대구경북과학기술원
Priority date: 2015-09-08
Filing date: 2015-09-08
Publication date: 2017-03-16

Abstract

The present invention relates to a conductive film comprising a conductive pattern layer in the form of a Penrose tiling, a method for producing the same, and an electrode including the conductive film. More particularly, the present invention relates to a conductive film having excellent optical, electrical and physical properties, .

Description

TECHNICAL FIELD The present invention relates to a conductive film, a method of manufacturing the same, and an electrode including the conductive film.

The present invention relates to a conductive film comprising a conductive pattern layer in the form of a penrose tiling, a method for producing the same, and electrodes comprising the same, and more particularly to a conductive film having excellent optical, electrical and physical properties, And an electrode comprising the same.

Recently, as display panels have become larger and flexible devices are beginning to attract attention, flexible electrodes are becoming a serious problem for the next generation. The widely used indium tin oxide (ITO) has been widely applied because it has excellent resistance to small and medium sized devices and exhibits excellent optical characteristics. However, due to concerns about the supply and demand of indium, a rare earth element, the difficulty of implementing flexible devices, and the limitations of large-scale applications due to resistance increase, it is becoming difficult to apply the next step. Therefore, development of substitute electrode capable of providing the lowest cost with existing ITO performance is getting attention.

Alternative electrodes that are considered include carbon nanotubes (CNTs), graphenes, nanowires using metal materials, and metal grids. However, these approaches are still blocked by several technical limitations. In terms of optics, most of them have excellent properties, but carbon materials have high price of materials, problems of process development, and relatively high resistance values.

In this connection, a transparent electrode using an ITO film has a sheet resistance of 30 to 80 / / sq with a transmittance of 90% and a transmittance of 97% with a graphene film, It has been experimentally proven that the sheet resistance can be lowered to 30? / Sq or less.

However, the high conductivity (low sheet resistance) of such graphene is experimentally observed only in graphene obtained by using micro-mechanical peeling method for highly ordered pyrolytic graphite (HOPG). Actually, graphene- There is a problem that a graphene having a low quality (having a sheet resistance of 100 times or more than the theoretical value) can be obtained in a method of producing graphene by growing graphene on a metal substrate, which is widely used in the production of graphene [Korean Patent No. 10-1513136 Reference]. In the case of metal nanowires, it is also a problem due to the difference in the partial resistance value from the connection of the random nanowires and the increase in the resistance value occurring at the junction between many nanowires.

For this reason, a metal grid, which is advantageous for realizing a large area because of high electric conductivity and high electromigration resistance, is attracting attention. Recently, a patterning technique using an ultra-short pulse laser with an appropriate line width has been developed for such a patterning technique (see Korean Patent No. 10-1262173).

However, in order to maintain high transmittance of the metal grid, a technique of patterning the metal width to 5 μm or less is required, and a moire phenomenon occurs due to interference between the black matrix (BM) of the display panel and the metal grid. In addition to the moire phenomenon, when a metal mesh is used, a starburst phenomenon occurs that causes glare to the user due to reflection, diffraction, and interference of light generated from the metal surface.

The moiré phenomenon is a phenomenon in which the French refer to the wave patterns appearing on the silk imported from ancient China, and interference fringes appear when two or more periodic patterns overlap. Moire patterns are widely applied to non-contact profile measurement, stress analysis and vibration analysis, linear displacement and rotational displacement measurement, object motion measurement, refractive index measurement, image processing, and three-dimensional object shape measurement. However, this moire phenomenon must be eliminated in the display field.

In a display, the moire phenomenon is caused by the interference between the optical element and the grid structure of the pixel. To address this serious problem, several researchers are working on new forms of grid formation.

Patterns made of only equilateral triangles, squares, and regular hexagons in the plane show a repetitive pattern as a whole. However, it is not possible to make a pattern of repeating patterns with only a pentagon.

Penrose, a professor of mathematics at Oxford University in 1974, can not fill a plane with a pentagon but can fill a flat surface with different shapes of kite and dart, which are separated from a pentagon. I found that I could. This is called Penrose tiling. It is a tiling form that is partially repeated but not repeated as a whole, and is called a quasiperiodic structure.

This kite and dart shape also has a remarkable mathematical attribute. First, a pattern consisting of a finite number of kites and darts is infinitely divided into any part, smaller kites, and darts. But the same pattern is a quasi-periodic pattern that is not repeated. In other words, Penrose tiling does not have any small pattern that can create an entire pattern by iteration.

Second, as you fill the plane with kite and dart, the ratio of kite and dart approaches the golden ratio. The rain of the short side and the long side is also golden. In other words, since the whole pattern is not formed by repetition, the pattern appears to have no regularity, but the pattern is extended by a certain rule, and the ratio becomes a golden ratio.

In a conductive film including a general metal grid, a moire phenomenon occurs due to interference between the black matrix (BM) of the display panel and the metal grid, and the reflection, diffraction, and interference of light generated from the metal surface cause a glare to the user A star burst phenomenon occurs.

Accordingly, the present invention overcomes the problems of conventional metal grids and provides a conductive film having excellent optical, electrical and physical properties, a method of manufacturing the same, and an electrode including the same.

In order to solve the above problems, the present invention proposes a conductive film including a conductive pattern layer of the Penrose tiling type, a method for manufacturing the conductive film, and an electrode including the conductive film, thereby overcoming the problems of the conventional general metal grid. And an electrode comprising the same.

In one embodiment of the present invention, a substrate comprises a substrate; And a conductive pattern layer formed on the substrate and having a pattern in the form of a Penrose tiling.

In one embodiment of the present invention, the line width of the pattern may be 0.5 to 20 占 퐉.

In one embodiment of the present invention, the transmittance of the conductive film may be 70% or more.

In one embodiment of the present invention, the sheet resistance of the conductive film may be 0.1? / Sq to 3000? / Sq.

In one embodiment of the present invention, the substrate may be transparent.

In one embodiment of the invention, the substrate may be flexible.

In one embodiment of the present invention, the substrate is a polyether sulfone (PES), a polyacrylate (PAR), a polyetherimide (PEI), a polyethylene naphthalate (PEN), a polyethylene terephthalate (PET) (PPS), polyarylate (PA), polyimide (PI), polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), glass and arylite And < / RTI >

In one embodiment of the present invention, the conductive pattern layer may include at least one selected from the group consisting of a metal, a metal oxide, a metal nitride, a metal oxynitride, and a metal alloy.

In one embodiment of the present invention, the conductive pattern layer is formed of a material selected from the group consisting of Ag, silver oxide, silver nitride, silver oxide nitride, gold (Au), gold oxide, gold nitride, gold oxide nitride, platinum , Platinum nitride, platinum oxynitride, nickel (Ni), nickel oxide, nickel nitride, nickel oxide nitride, palladium (Pd), palladium oxide, palladium nitride, palladium oxynitride, copper, copper oxide, copper nitride, (Al), aluminum oxide, aluminum nitride, aluminum oxynitride, molybdenum (Mo), molybdenum oxide, molybdenum nitride, molybdenum oxynitride, and combinations thereof. Alloys, and alloys thereof.

In one embodiment of the present invention, the conductive film may be flexible.

In another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a conductive metal layer on a substrate;

Forming a photoresist on the conductive metal layer;

Patterning the photoresist in the form of a Penrose tiling; And

And etching the conductive metal layer. The present invention also provides a method of manufacturing a conductive film.

In an embodiment of the present invention, the linewidth of the photoresist patterned in the Penrose tiling form may be 0.5 [mu] m to 20 [mu] m.

In another embodiment of the present invention, there is provided an electrode comprising the conductive film.

In one embodiment of the present invention, the electrode may be transparent.

The conductive film of the present invention and the electrode including the conductive film include a conductive pattern layer having excellent reproducibility at the time of manufacture and have excellent optical, electrical and physical properties by minimizing a star burst phenomenon and a moire phenomenon occurring in a general metal grid.

Figure 1 shows a silver (Ag) grid in the form of a Penrose tiling formed on a glass substrate.
FIG. 2 is a photograph of a conductive film prepared by forming a conductive pattern layer in the form of a 3 μm thick Penrose tiling on a polyethylene naphthalate (PEN) substrate.
Figure 3 shows a conductive pattern layer in the form of square, hexagonal and penrozed tilings formed on a glass substrate.
FIG. 4 shows the results of measurement of the transmittance of a conductive film including a conductive pattern layer having a pattern of square, regular hexagon, and pentose tiling patterns on a glass substrate.
Fig. 5 shows the starburst phenomenon of a conductive film including a conductive pattern layer having a pattern of square, regular hexagon, and pentose tiling patterns on a glass substrate.
6 shows a metal grid in the form of a Penrose tiling with line widths of 3 탆, 4 탆, 6 탆, 8 탆, 10 탆 and 20 탆 formed on a polyethylene naphthalate (PEN) substrate.
FIG. 7 is a graph showing the transmittance of a conductive film formed on a polyethylene naphthalate (PEN) substrate at 550 nm of a conductive film comprising a conductive pattern layer having a pattern of a Penrose tiling pattern with line widths of 3, 4, 6, 8, The transmittance is shown in FIG.
8 shows the measurement results of the transmittance (5 times) of the conductive film including the conductive pattern layer in the form of Penrose tiling with a line width of 3 mu m formed on the glass substrate.

Hereinafter, the present invention will be described in detail. However, it should be understood that the present invention may be embodied in many other specific forms without departing from the spirit or essential characteristics thereof.

Conductive film

The present invention

Board; And a conductive pattern layer formed on the substrate and having a pattern in the form of a Penrose tiling.

The Penrose tiling form is a tiling form of a quasiperiodic structure that is partially repeated, but not entirely repeated. Penrose shapes can be illustrated by the following examples, but are not limited thereto.

In one embodiment of the present invention, the Penrose tiling may be of an original shape and may be a combination of a pentagon, a pentagon, a boat (about 3/5 of a pentagon), and a diamond (a thin rhombus).

In one embodiment of the present invention, the penrose tiling is a kite & dart type, symmetrical pentagonal structure made by using different shapes of rhombic kites and darts separated from a pentagon Lt; / RTI >

In one embodiment of the present invention, the Penrose tiling may be of rhombus type and may be composed of a combination of two different types of rhombus.

Penrose tiling of the rhombus type>

In one embodiment of the present invention, the line width of the pattern may be 0.5 탆 to 20 탆, and preferably 1 탆 to 5 탆. If the line width of the pattern is excessively narrow, patterning may not be performed uniformly, so that a constant current flow on the conductive film may not be maintained. If the line width is excessively wide, the transmittance of the conductive film may be low and the optical characteristics may be deteriorated.

In one embodiment of the present invention, the transmittance of the conductive film may be 80% or more. When the conductive film shows a transmittance of 80% or more, the conductive film has excellent optical characteristics, and when the transmittance is too low, it may be difficult to produce a transparent conductive film.

In one embodiment of the present invention, the sheet resistance of the conductive film may be 0.1? / Sq to 3000? / Sq. The sheet resistance of the conductive film may be varied depending on the application, for example, it may be 5? / Sq to 35? / Sq and may be 14? Sq to 32? / Sq. When the conductive film has a sheet resistance value within the above range, it is particularly suitable for a touch panel, an electronic paper, a plastic liquid crystal, a sensitized solar cell, or an EL.

In one embodiment of the present invention, the substrate may be transparent.

In one embodiment of the invention, the substrate may be flexible.

In one embodiment of the present invention, the substrate is a polyether sulfone (PES), a polyacrylate (PAR), a polyetherimide (PEI), a polyethylene naphthalate (PEN), a polyethylene terephthalate (PET) (PPS), polyarylate (PA), polyimide (PI), polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), glass and arylite , And preferably the substrate may be polyethylene naphthalate (PEN) or glass.

In one embodiment of the present invention, the conductive pattern layer is formed of a material selected from the group consisting of Ag, silver oxide, silver nitride, silver oxide nitride, gold (Au), gold oxide, gold nitride, gold oxide nitride, platinum , Platinum nitride, platinum oxynitride, nickel (Ni), nickel oxide, nickel nitride, nickel oxide nitride, palladium (Pd), palladium oxide, palladium nitride, palladium oxynitride, copper, copper oxide, copper nitride, (Al), aluminum oxide, aluminum nitride, aluminum oxynitride, molybdenum (Mo), molybdenum oxide, molybdenum nitride, molybdenum oxynitride, and combinations thereof. Alloys, and preferably the conductive pattern layer may be silver (Ag). This allows the conductive film to have high electrical conductivity and exhibit excellent electrical properties.

Method for manufacturing conductive film

The present invention provides a method of manufacturing a semiconductor device, comprising: forming a conductive metal layer on a substrate;

Forming a photoresist over the conductive metal layer;

Patterning the photoresist in the form of a Penrose tiling; And

In one embodiment of the present invention, the line width of the photoresist patterned in the Penrose tiling form may be between 0.5 μm and 20 μm and may be between 3 μm and 5 μm. If the line width of the pattern is excessively narrow, patterning may not be performed uniformly, so that a constant current flow on the conductive film may not be maintained. If the line width is excessively wide, the transmittance of the conductive film may be low and the optical characteristics may be deteriorated.

electrode

The present invention provides an electrode comprising the conductive film.

In one embodiment of the present invention, the electrode may be transparent.

Hereinafter, preferred embodiments and the like are provided to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.

Example 1. Formation of a conductive pattern layer in the form of a Penrose tiling on glass

1-1. A silver (Ag) deposition

The substrate was cleaned to deposit the metal on the substrate. 0.7T (thickness) glass was cleaned using micro wiper and acetone, and cleaned in an ultrasonic washing machine for 10 minutes each in the order of acetone, purified water and isopropyl alcohol (IPA). The cleaned substrate was dried using nitrogen and stored in an oven at 60 ° C. Then, silver (Ag) was completely deposited on the substrate to a thickness of 100 nm in the evaporator.

1-2. Metal grid pattern formation on the substrate (photolithography)

A positive photoresist was spin-coated at 1500 rpm for 40 seconds on the substrate on which silver (Ag) was deposited. After the application of the photoresist on the substrate was completed, a soft bake was performed at 100 DEG C for 1 minute and 30 seconds on a hot plate to completely dry the applied photoresist. After the drying, the exposure process was performed for 2 seconds with a shadow mask in which Penrose tiling was formed. After exposure, development was carried out at room temperature for 90 seconds using a developing solution. Thereafter, the substrate was washed with purified water for 1 minute and dried using nitrogen.

The dried substrate was subjected to hard bake at 120 ° C for 2 minutes. The substrate on which the photoresist was developed in accordance with the Penrose tiling pattern was etched using a etchant. DME-300 (Dongjin Semichem Co., Ltd.) was used as the etching solution, and the substrate was immersed in the etching solution for 10 seconds at room temperature to remove the silver (Ag) thin film not coated with the photoresist. After the etching process, the substrate was cleaned with purified water for 1 minute to remove the etching solution remaining on the substrate.

To remove the photoresist on the cleaned substrate, PGMEA (propylene glycol monomethyl ether acetate) was used as a photoresist stripper. The substrate was immersed in the photoresist stripper for 4 minutes at room temperature for removal, Then rinsed with acetone for 1 minute and dried with nitrogen. A silver (Ag) grid Penrose tiling pattern patterned on a glass substrate is shown in FIG.

Example 2 A conductive pattern layer of a Penrose tiling type was formed on a polyethylene naphthalate (PEN) substrate to prepare a conductive film

According to the procedure of Example 1, a conductive pattern layer of 3 占 퐉 in the form of Penrose tiling was formed on a polyethylene naphthalate (PEN) substrate to prepare a conductive film. A photograph of the produced conductive film is shown in Fig.

As shown in FIG. 2, the Penrose tiling pattern formed on the flexible PEN substrate has a problem in that the visibility of the pattern is improved compared with that of the conventional square or regular hexagon, and the patterning is performed through the photomask, The reproducibility was very good compared to the grid - based method.

In addition, it was confirmed that the number of kite and dart shapes, which are characteristic of the Penrose tiling pattern, is advantageous to have a desired transmittance and resistance value as compared with a random pattern that can not be controlled by a different ratio.

Experimental Example 1. Confirmation of transmittance and star burst phenomenon by pattern shape

According to the process of Example 1, a metal grid of square, regular hexagonal or pentose tiling type was formed on a 0.7 T man glass with a line width of 3 μm, respectively, to confirm the transmittance and star burst phenomenon of each pattern. Since the starburst phenomenon is caused by the light reflected from the surface of the metal grid, the LED lamp is turned on so as to be perpendicular to the substrate as much as possible within a photographable angle. 3, the transmittance of each pattern is shown in Fig. 4, and the star burst phenomenon by pattern is shown in Fig.

As shown in Fig. 4, the transmittance of each pattern was similar within about 95% to 98%. It can be seen that the metal grid in the shape of Penrose tiling has an excellent transmittance similar to that of the square and square metal grid.

As shown in FIG. 5, in the case of the square pattern, a cross-shaped starburst phenomenon was observed. When the light was shot in the hexagonal pattern, the star burst phenomenon in which the light was scattered in six directions Respectively. In the Penrose tiling pattern, a star burst phenomenon was observed in which the light spreads in various directions and the shape did not show any uniform shape. Therefore, it can be seen that the starburst phenomenon is a unique phenomenon of metal and closely related to the pattern shape.

In addition, when the scattered light is magnified and observed, it can be seen that the moire phenomenon occurs in the dispersed direction in the case of the square pattern. In the case of the regular hexagon pattern, the moire phenomenon does not appear clearly, Respectively.

On the other hand, in the case of the Penrose tiling pattern, the light was spread in various directions and it was observed that there was no constant shape. As shown in the enlarged figure, it was confirmed that the starburst phenomenon is minimized by the Penrose tiling pattern and the visibility problem of the pattern and the moire phenomenon can be reduced.

EXPERIMENTAL EXAMPLE 2. Determination of Transmittance and Sheet Resistance according to Line Width of Metal Grid of Penrose Tiling Type

According to the process of Example 1, a metal grid of the form of Penrose tiling was formed on a polyethylene naphthalate (PEN) substrate with a line width of 3 탆, 4 탆, 6 탆, 8 탆, 10 탆 or 20 탆, The transmittance and sheet resistance of each line width were confirmed. 6, the transmittance of each line width is shown in Fig. 7 and Table 1, and the sheet resistance of each line width is shown in Table 1. Fig.

Line width Transmittance (%) Sheet resistance (Ω / sq) 3 탆 81.01 31.75 4 탆 80.22 14.08 6 탆 79.34 8.35 8 탆 77.01 5.00 10 탆 76.10 2.02 20 탆 66.79 1.77

As shown in FIG. 7 and Table 1, it can be seen that the smaller the line width, the higher the transmittance. Therefore, it can be seen that the metal grid having a line width of about 6 탆 or less has a transmittance of 80% or more, thereby imparting excellent optical properties to the conductive film.

Also, as shown in Table 1, it can be seen that the metal grid having a line width of 3 m has a relatively low sheet resistance of 31.75? / Sq .

Experimental Example 3. Confirmation of Reproducibility of Pattern Formation

According to the procedure of Example 1, the metal grid of the same Penrose tiling type was formed 5 times on the 0.7T man glass with a line width of 3 mu m, and then the transmittance was confirmed. The results are shown in Fig.

As shown in FIG. 8, when the process was carried out in the same pattern, the respective conductive films showed almost the same transmittance. That is, since the Penrose tiling pattern has a quasi-periodic pattern, it can be confirmed that the optical characteristics of the conductive film have high reproducibility.

Claims

Board; And
And a conductive pattern layer formed on the substrate and having a pattern in the form of a penrose tiling.

The conductive film according to claim 1, wherein the line width of the pattern is 0.5 to 20 占 퐉.

The conductive film according to claim 1, wherein the conductive film has a transmittance of 70% or more.

The conductive film according to claim 1, wherein the sheet resistance of the conductive film is 0.1? / Sq to 3000? / Sq.

The conductive film according to claim 1, wherein the substrate is transparent.

The conductive film according to claim 1, wherein the substrate is flexible.

The method of claim 1, wherein the substrate is selected from the group consisting of polyethersulfone (PES), polyacrylate (PAR), polyetherimide (PEI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyphenylene sulfide ), Polyarylate (PA), polyimide (PI), polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), glass and arylite &Lt; / RTI >

The conductive film according to claim 1, wherein the conductive pattern layer comprises at least one selected from the group consisting of a metal, a metal oxide, a metal nitride, a metal oxynitride, and a metal alloy.

The method according to claim 1, wherein the conductive pattern layer is formed of a material selected from the group consisting of Ag, silver oxide, silver nitride, silver oxide nitride, gold (Au), gold oxide, gold nitride, gold oxide nitride, platinum (Pt) (Pd), palladium oxide, palladium nitride, palladium oxynitride, copper (Cu), copper oxide, copper nitride, copper oxynitride Chromium (Cr), chromium oxide, chromium nitride, chromium oxynitride, aluminum (Al), aluminum oxide, aluminum nitride, aluminum oxynitride, molybdenum (Mo), molybdenum oxide, molybdenum nitride, molybdenum oxide nitride and alloys thereof &Lt; / RTI > wherein the conductive film comprises at least one selected from the group consisting of polyethylene,

The conductive film according to claim 1, wherein the conductive film is flexible.

Forming a conductive metal layer on the substrate;
Forming a photoresist on the conductive metal layer;
Patterning the photoresist in the form of a Penrose tiling; And
Etching the conductive metal layer;
&Lt; / RTI >

12. The method of claim 11, wherein the line width of the photoresist patterned in the Penrose tiling form is 0.5 to 20 占 퐉.

An electrode comprising the conductive film according to any one of claims 1 to 10.

14. The electrode of claim 13, wherein the electrode is transparent.