KR20180045606A - Mesh with modified stacked-structure for transparent electrode and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a transparent electrode mesh having an oxide-metal-oxide (OMO) structure for transparent electrodes, which can be applied on plastics and flexible substrates, and a method of manufacturing the same. Provided are a transparent electrode mesh manufacturing method including forming a photoresist layer on the substrate by spin coating; patterning the photoresist layer by using a mask; forming a lower oxide layer by sputtering over the patterned photoresist layer; forming a metal layer on the lower oxide layer by sputtering; forming an upper oxide layer on the metal layer by sputtering; and removing the photoresist in a lift-off manner on the substrate on which the upper oxide layer is formed and a transparent electrode mesh manufactured by using the same. With the present invention, the electrical characteristics and the mechanical flexibility and the transparency in the visible light region are improved as compared with the indium tin oxide transparent electrode according to the prior art.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a mesh for a transparent electrode having a laminated structure,

The present invention relates to a mesh for a transparent electrode, and more particularly to a mesh for a transparent electrode having an oxide-metal-oxide (OMO) structure for a transparent electrode applicable to plastics and flexible substrates, will be.

FIGS. 1 and 2 are cross-sectional views and a plan view of a nano-mesh transparent electrode according to the related art. A nano-mesh transparent electrode 10 having high conductivity and transparency is generally formed on a substrate 1, And a mesh metal film composed of a film 11 and a plurality of metal patterns 12.

The substrate 1 may be a glass substrate or a plastic substrate and the nano-mesh transparent electrode 10 may be formed on any electrode, line or layer as well as the substrate 1 .

The transparent conductive film 11 is formed of indium tin oxide (ITO), indium zinc oxide (IZO) or indium tin zinc oxide (ITZO) to have a thickness of 200 Å (0.02 μm) A plurality of metal patterns 12 are formed on the mesh metal film. The plurality of metal patterns 120 are formed in a mesh shape as shown in Fig.

Typically, a plurality of metal patterns 12 of a mesh metal film are formed of a metal material of aluminum (Al), molybdenum (Mo), or copper (Cu) with a thickness of 1,000 angstroms (0.10 um) and a line width of 0.1 um- do.

In the conventional nano-mesh transparent electrode 10 according to the prior art, a photo-resist (PR) pattern is formed by applying a temperature of 100 ° C. to 200 ° C. for several minutes to several hours to form a crack, A plurality of metal patterns 12 are formed by impregnating a crevice of a crack with a metal material using a plating method.

At this time, the line width of the plurality of metal patterns 12 can be freely adjusted within the range of 0.1 um-10 um by adjusting the interval of cracks in the cracks. The line width of the plurality of metal patterns 12 may be different depending on a metal material (aluminum (Al), molybdenum (Mo), or copper (Cu)) as a material. The line width and the density of the plurality of metal patterns 12 are adjusted.

Thus, by forming the mesh metal film with a plurality of metal patterns 12 on the transparent conductive film 11, the nano-mesh transparent electrode 10 has high conductivity and high transparency.

However, since the mesh-type transparent electrode, which forms the mesh metal film with a plurality of metal patterns according to the related art, forms a mesh metal film only with the metal, there is a problem that the electrical characteristics deteriorate after a lapse of a predetermined time.

KR 10-2013-0044058 A (Released May 1, 2013) KR 10-1661517 B1 (Registered on September 26, 2016) KR 10-1416438 B1 (Registered on July 1, 2014) KR 10-1219741 B1 (Registered on Mar. 1, 2013)

SUMMARY OF THE INVENTION It is an object of the present invention to solve the problems described above and to provide a transparent electrode mesh having a laminated structure that can be used as a transparent electrode applicable to plastics and flexible substrates, and a method of manufacturing the same.

Another object of the present invention is to provide a metal-oxide-oxide (OMO) stacked structure formed on the plastic and flexible substrate, wherein the upper and lower oxide layers of the mesh have a protection Layer, and the upper and lower oxide layers are in an amorphous form, so that a mesh having an OMO laminated structure can be expected to have higher flexibility than the conventional one, and a manufacturing method thereof.

According to an aspect of the present invention, there is provided a method of manufacturing a mesh for a transparent electrode, the method including: fabricating a mesh having an oxide-metal-oxide (OMO) The method of claim 1, further comprising: forming a photoresist layer on the substrate by spin coating; Patterning the photoresist layer using a mask; Forming a lower oxide layer by sputtering over the patterned photoresist layer; Forming a metal layer on the lower oxide layer by sputtering; Forming a top oxide layer on the metal layer by sputtering; And removing the photoresist in a lift-off manner on the substrate on which the upper oxide layer is formed.

In the method for manufacturing a transparent electrode mesh according to the present invention, the upper oxide layer and the lower oxide layer may be formed by a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, May be formed by any one of a printing process, a wet solution process, and a sputtering process.

Further, in the method of manufacturing a mesh for a transparent electrode according to the present invention, the metal layer may be formed by a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, a sputtering process It can be formed by any one method.

In addition, in the method of manufacturing a mesh for a transparent electrode according to the present invention, after removing the photoresist, heat-treating the mesh having an oxide-metal-oxide (OMO) structure at 50-900 ° C; .

In addition, the transparent electrode mesh applicable to the plastic and flexible substrate according to the present invention forms a laminated structure of an upper oxide layer, a metal layer, and a lower oxide layer on the substrate, and the upper oxide layer and the lower oxide layer are oxide semiconductors Wherein the SIZO thin film is formed of a silicon oxide (Si-In-ZnO) thin film, the content of silicon contained in the SIZO thin film is 0.001 wt% to 30 wt%, and the upper oxide layer and the lower oxide layer include aluminum (Al) It is preferable that elements such as Ga, Hf, Zr, Li, K, Ti, Ge, Nb, And the metal layer is formed of a silver (Ag) thin film.

In the transparent electrode mesh according to the present invention, the substrate may be at least one selected from the group consisting of polyimide (PI), polyamide (PA), polyamide-imide, polyurethane (PU) ), Polyurethane acrylate (PUA), polyacrylamide (PA), polyethyleneterephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN) Polymers such as polycarbonate (PC), polymethylmethacrylate (PMMA), polyetherimide (PEI), polydimethylsiloxane (PDMS), polyethylene (PE), polyvinyl alcohol Polyvinyl alcohol (PVA), polystyrene (PS), biaxially oriented PS, BOPS, acrylic resin, silicone resin, fluorine resin, modified epoxy resin, glass or hardened And is glass.

In the transparent electrode mesh according to the present invention, it is preferable that the upper oxide layer and the lower oxide layer have a thickness of 10-1000 nm, the metal layer has a thickness of 10-200 nm, The line width of the mesh is preferably 1-10 占 퐉.

Meanwhile, in the transparent electrode mesh according to the present invention, the metal layer may be formed of any one of copper (Cu) and aluminum (Al) thin films.

As described above, since the present invention is used as a transparent electrode using a mesh, it is possible to replace the material of the transparent electrode material having no flexibility such as conventional indium tin oxide.

In addition, unlike conventional metal meshes, since the oxide-metal-oxide (OMO) laminate structure having oxide layers on the upper and lower sides can be used, the upper and lower oxides can serve as a protective layer for protecting the middle metal layer. It can be expected to be used as a transparent electrode having less electrical property deterioration over time than an electrode.

1 is a cross-sectional view showing a nano-mesh transparent electrode according to the prior art,
2 is a plan view showing a nano-mesh transparent electrode according to the prior art,
3 is a view showing a manufacturing process of a mesh for a transparent electrode having a laminated structure shown in a sectional view of a mesh for a transparent electrode having a laminated structure according to the present invention,
4 is an AFM (atomic forced measurement) photograph of a single amorphous silicon indium zinc oxide film (SIZO) of a mesh for a transparent electrode having a laminated structure according to the present invention,
5 is a graph comparing the transmittance of a multilayer thin film of an oxide-metal-oxide with a mesh for a transparent electrode having a laminated structure according to the present invention.

Hereinafter, embodiments of a mesh for a transparent electrode having a laminated structure according to the present invention and a method of manufacturing the same will be described in detail with reference to the drawings. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS The same features of the Figures represent the same reference symbols wherever possible. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. , ≪ / RTI > equivalents, and alternatives. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

Hereinafter, the attached drawings are exaggerated or simplified in order to facilitate understanding and clarification of the structure and operation of the technology, and it is to be understood that each component does not exactly coincide with the actual size.

The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

In addition, when a part includes an element, it does not exclude other elements unless specifically stated otherwise, but may include other elements.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is to be understood that the same terms as those defined in the commonly used terms are defined in consideration of the functions of the present invention and are to be construed in accordance with the technical idea of the present invention and the meaning commonly understood or commonly recognized in the technical field And is not to be construed as an ideal or overly formal sense unless expressly defined to the contrary.

3 (g), the transparent electrode thin film includes a substrate 101, a lower oxide layer 103 (see FIG. 3 (g)), and a transparent electrode thin film ), A metal layer 104, and a top oxide layer 105.

The type of the substrate 101 is not particularly limited and includes, for example, polyimide (PI), polyamide (PA), polyamide-imide, polyurethane (PU) (PU), polyacrylamide (PA), polyethyleneterephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethylmethacrylate (PMMA), polyetherimide (PEI), polydimethylsiloxane (PDMS), polyethylene (PE), polyvinyl alcohol , PVA), polystyrene (PS), biaxially oriented PS (BOPS), acrylic resin, silicone resin, fluorine resin, modified epoxy resin, There.

 Layer structure in which the lower oxide layer 103, the metal layer 104, and the upper oxide layer 105 are laminated on the substrate 101 at one time, but in another embodiment, it may be utilized as a heat- In this case, the structure in which the lower oxide layer 103, the metal layer 104, and the upper oxide layer 105 are stacked may be repeatedly formed.

As the lower oxide layer 103, an amorphous silicon oxide indium zinc layer (SIZO) in which silicon (Si) is included in indium zinc oxide (InZnO) can be applied.

The amorphous silicon oxide indium zinc layer (SIZO), which is the lower oxide layer 103, may be formed by a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, a printing process, a wet solution process, and a sputtering process. In one embodiment, the thickness of the lower oxide layer 103 may be from a few tens of nanometers to a few hundred nanometers. For example, the thickness of the first amorphous silicon indium zinc oxide layer (SIZO) may be between about 10 nm and 1000 nm.

The metal layer 104 is a layer that determines the electrical characteristics of the mesh structure. For example, the thin film of the metal layer 104 may be a silver (Ag) layer.

The deposition of the metal layer 104 may be performed by a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, or a sputtering process. In one embodiment, the thickness of the insulating layer 104 may be from a few tens of nanometers to a few hundred nanometers, and the thickness of the metal layer 104 may be between about 10 nm and 200 nm.

The upper oxide layer 105 may be an amorphous silicon oxide indium zinc layer (SIZO) in which silicon (Si) is included in indium zinc oxide (InZnO).

The amorphous silicon oxide indium zinc layer (SIZO), which is the upper oxide layer 105, may be formed by a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, a printing process, a wet solution process, and a sputtering process. In one embodiment, the thickness of the top oxide layer 105 may be from a few tens of nanometers to a few hundred nanometers, and the thickness of the first amorphous silicon indium zinc oxide layer (SIZO) may be between about 10 nm and 1000 nm.

The fabricated oxide-metal-oxide (OMO) structure meshes can be subjected to a heat treatment process in the range of 50-900 ° C.

Hereinafter, a method for manufacturing a transparent electrode mesh according to the present invention will be described in detail with reference to FIGS.

First, the substrate 101 is prepared in step (a). In the preparation of the substrate 101, the substrate 101 may be washed. If the substrate is glass, the substrate is cleaned by ultrasonic cleaning in the order of acetone, methanol, and DI-water, and DI water remaining on the substrate is removed using N2 gun.

Next, a photoresist layer 102 is formed on the substrate 101 by spin coating in step (b), patterning is performed on the photoresist layer 102 using the mask 200 in step (c) Leaving only the patterned photoresist layer 102a.

Next, in the step (d), a lower oxide layer 103 is formed on the substrate 101. The lower oxide layer 103 may be formed by a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, a printing process, a wet solution process, a sputtering process sputtering < / RTI > process.

After the lower oxide layer 103 is formed in step (d), a silver (Ag) thin film is formed as a metal layer 104 on the lower oxide layer 103 in step (e). At this time, the metal layer 104 may be formed by a sputtering method or a thermal evaporation method. Meanwhile, copper (Cu) and aluminum (Al) thin films may be formed on the metal layer 104.

After the metal layer 104 is formed in step (e), a top oxide layer 105 is formed on the metal layer 104 in step (f). The upper oxide layer 105 may also be formed by a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, a printing process, a wet process solution process, and a sputtering process.

Each of the lower oxide layer 103 and the upper oxide layer 105 stacked on the lower and upper portions of the metal layer 104 is formed of an amorphous silicon oxide indium zinc layer SIZO wherein the silicon content is 0.01 - 30 wt%.

After forming the upper oxide layer 105 in step (f), finally, the substrate on which the upper oxide layer 105 is formed in step (g) is removed by removing the photoresist layer 102a in a lift-off manner , The manufacturing process of the mesh for a transparent electrode having an oxide-metal-oxide structure according to the present invention is completed.

4 is an AFM (Atomic Forced Measurement) picture of a single amorphous silicon oxide zinc oxide film structure of a laminated mesh having an oxide-metal-oxide structure according to the present invention.

The roughness of the surface of the single amorphous silicon oxide indium zinc oxide film of the thermal oxidation prevention film according to one embodiment can be determined using the AFM results shown in FIG. AFM photographs are taken at the atomic level of the surface to reveal the bend of the surface. When the surface curvature is obtained through the mean value, it becomes zero and it is difficult to obtain an accurate value for the actual bending. Therefore, it is possible to know what the actual roughness is by calculating the average of only the upper side rather than the lower side based on the root mean square (RMS). It can be seen that the square mean of the amorphous silicon indium zinc oxide single layer of the laminated mesh having the oxide-metal-oxide structure according to the embodiment of FIG. 2 is 0.23 nm and has a considerably flat surface.

FIG. 5 is a graph showing the transmittance of an oxide-metal-oxide laminated thin film according to the present invention in comparison with a mesh having an oxide-metal-oxide (OMO) structure.

5 is a schematic diagram illustrating the use of a silver (Ag) layer as the metal layer 104 and an amorphous silicon indium zinc (SIZO) containing silicon as the lower oxide layer 103 and the upper oxide layer 105 and an amorphous silicon zinc tin oxide As a result of measurement of a mesh having an oxide-metal-oxide (OMO) structure made of a metal oxide-metal-oxide laminate structure and a thin film having an oxide-metal-oxide laminate structure, graphs 111 and 112 show Graphs 113 and 114 show the transmittances of the oxide structures of oxide-metal-oxide-oxide (OMO) structures using SIZO and SZTO as oxide layers, - a thin film having an oxide-metal-oxide (OMO) structure.

Referring to FIG. 5, it can be seen that the thin film of the simple laminated structure has a low transmittance of less than about 10% at 380 - 780 nm in the visible light region, but has a transmittance of about 90% at the mesh structure, .

The electrical characteristics of the meshes having an oxide-metal-oxide laminated structure according to an embodiment of the present invention are analyzed and are summarized in Table 1 below.

The sample was 2.42 × 10 ^-5 , glass (12 × 12 mm glass) -SZTO (80 nm) -Ag (100 nm) at the glass (12 × 12 mm, glass) -SIZO (80 nm) when -SZTO (80nm) 2.55 × 10 ^- it can be confirmed that ⁵ has a low resistance.

The resistance change according to the banding test of the mesh having the oxide-metal-oxide laminated structure according to an embodiment of the present invention formed on the PET substrate was analyzed and is summarized in Table 2 below.

It can be seen that there is no large change in resistance even after testing 100 times of bending, so that it can be applied to a flexible substrate.

In one embodiment, only a multi-layer structure is shown in which a lower oxide layer 103, a metal layer 104, and a top oxide layer 105 are deposited on a substrate once, but an oxide-metal- A structure having a structure can be repeatedly formed with a multilayer structure in which a lower oxide layer 103, a metal layer 104, and an upper oxide layer 105 are laminated.

As described above, the mesh for a transparent electrode and the method of manufacturing the same according to the present invention can provide a mesh for a transparent electrode having a laminated structure that can be used as a transparent electrode applicable to plastics and flexible substrates, And the upper and lower oxide layers of the mesh having an oxide-metal-oxide (OMO) laminate structure formed on the flexible substrate are not only functions as a protective layer for preventing oxidation of the intermediate metal layer, Because the layer is amorphous, it offers greater flexibility than previously possible.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.

Claims (10)

A method of manufacturing a mesh having a stacked oxide-metal-oxide (OMO) structure for a transparent electrode applicable to plastic and flexible substrates,
Forming a photoresist layer on the substrate by spin coating;
Patterning the photoresist layer using a mask;
Forming a lower oxide layer by sputtering over the patterned photoresist layer;
Forming a metal layer on the lower oxide layer by sputtering;
Forming a top oxide layer on the metal layer by sputtering;
And removing the photoresist in a lift-off manner on the substrate on which the upper oxide layer is formed.
The method of claim 1, wherein the top oxide layer
A method such as a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, a printing process, a wet solution process, or a sputtering process And forming a transparent electrode on the transparent electrode.
The semiconductor device according to claim 1,
Wherein the transparent electrode is formed by any one of a pulsed laser deposition (PLD) process, a thermal deposition process, an electron beam deposition process, and a sputtering process.
The method of claim 1, further comprising, after removal of the photoresist,
Further comprising the step of heat treating the mesh having an oxide-metal-oxide (OMO) structure at a temperature of 50-900 占 폚.
1. A mesh for a transparent electrode applicable on plastic and flexible substrates,
Forming a laminated structure of a top oxide layer, a metal layer, and a bottom oxide layer on the substrate,
The upper oxide layer and the lower oxide layer are made of a silicon-oxide-zinc (Si-In-ZnO) thin film as an oxide semiconductor,
The content of silicon contained in the SIZO thin film is 0.001 wt% to 30 wt%
(Al), gallium (Ga), hafnium (Hf), zirconium (Zr), lithium (Li), potassium (K), titanium (Ti), germanium And further includes elements such as niobium (Nb) and tin (Sn)
Wherein the metal layer is made of a silver (Ag) thin film.
6. The method of claim 5,
Polyimide (PI), polyamide (PA), polyamide-imide, polyurethane (PU), polyurethane acrylate (PUA), polyacrylamide , PA), polyethylene terephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN), polycarbonate (PC), polymethylmethacrylate ), Polyetherimide (PEI), polydimethylsiloxane (PDMS), polyethylene (PE), polyvinyl alcohol (PVA), polystyrene (PS), biaxially oriented polystyrene biaxially oriented PS, BOPS), an acrylic resin, a silicone resin, a fluororesin, a modified epoxy resin, a glass or a tempered glass.
6. The method of claim 5, wherein the top oxide layer and the bottom oxide layer comprise a < RTI ID =
Wherein the transparent electrode has a thickness of 10-1000 nm.
6. The semiconductor device according to claim 5,
Wherein the transparent electrode has a thickness of 10 to 200 nm.
6. The method of claim 5,
Wherein the transparent electrode mesh has a line width of 1-10 占 퐉.
6. The semiconductor device according to claim 5,
Copper (Cu), and aluminum (Al) thin film.

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