KR101862760B1 - Method for manufacturing composite substrate and composite substrate manufactured using thereof - Google Patents

Abstract

The present invention provides a method of manufacturing a semiconductor device, comprising: a first step of preparing a release layer; A second step of forming a first transparent conductive layer on the release layer; A third step of forming a base polymer layer on the first transparent conductive layer; And a fourth step of separating the release layer and the first transparent conductive layer from each other,
By forming the first transparent conductive layer, the base polymer layer, and the like in the reverse order on the release layer and separating them in the reverse order, it is possible to provide a process for manufacturing a simpler and less costly translucent substrate, wherein the flexible plastic substrate or buffer layer A flexible translucent substrate which can be used in a flexible substrate can be manufactured, and each of the step processes can be continuously performed in a roll-to-roll process, thereby providing a method of manufacturing a translucent substrate with enhanced productivity, reliability and economy.

Description

TECHNICAL FIELD The present invention relates to a method of manufacturing a transparent substrate,

The present invention relates to a method of manufacturing a transparent substrate and a transparent substrate produced thereby. A display device to which a light-transmitting substrate is applied, a lighting device, and the like.

The translucent substrate is a substrate including a transparent conductive layer having both electrical conductivity and light transmittance. The translucent substrate provided in the light emitting element is configured to minimize loss of generated light. For example, an organic light-emitting diode (OLED) is a device composed of a luminescent organic material. Light emitted from the organic luminescent layer is emitted to the outside through the electrode and the light-transmitting substrate. Such a transparent substrate may be a liquid crystal display, an electrochromic display (ECD), an organic electroluminescence, a solar cell, a plasma display panel, a flexible display, an electronic paper, A display device such as a touch panel, a lighting device, a solar cell, or the like.

The translucent substrate comprises a base substrate and a translucent electrode that performs an electrode function of a light emitting element attached to the substrate. Transparent electrodes are mainly formed on a plastic base substrate by using a conductive material such as ITO (tin-doped indium oxide) to form a thin film. However, in recent years, carbon that can replace ITO, which is indium- Research and development on nanotubes (CNTs), metal nanostructures, etc. have been actively conducted.

As disclosed in Korean Patent Laid-Open No. 10-2014-0089670, a method of laminating a light-transmissive substrate having another refractive index may be used to minimize light loss in a light-transmitting substrate, Development is being conducted to improve the flexibility of the light-transmitting substrate by applying the memory polymer to a flexible display.

The present invention relates to a method of manufacturing a transparent substrate including a first transparent conductive layer, a second transparent conductive layer, and a light extracting layer, and a transparent substrate prepared thereby and an organic light emitting device including the transparent substrate. A conductive layer, a base polymer layer, and the like are formed and then separated, thereby providing a process for manufacturing a more simplified and cost-reduced translucent substrate.

However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

The present invention provides a method of manufacturing a transparent substrate comprising a first transparent conductive layer and a base polymer layer, the method comprising: a first step of preparing a release layer; A second step of forming a first transparent conductive layer on the release layer; A third step of forming a base polymer layer on the first transparent conductive layer; And a fourth step of separating the release layer from the first transparent conductive layer to obtain a translucent substrate including a first transparent conductive layer and a base polymer layer.

Further, the release layer comprises a substrate, a buffer substrate, or a substrate including a buffer layer on one surface thereof.

In addition, the fourth step may include irradiating the release layer with light energy to change properties of the material forming the release layer to separate the release layer from the first transparent conductive layer.

The substrate may also include a polytetrafluoroetylene substrate or a bulk polymerized polymethyl methacrylate (PMMA) substrate.

Also, the buffer substrate is a substrate formed by including a carbon compound containing fluorine (F).

In addition, the fluorine (F) carbon compounds, including the profile siloxane with methyl trifluoroacetate (Methyltrifluoropropyl siloxane), (Methylfluoro) methyl _{fluoro, C 8 F 17 C 2 H} 4 Si (NH) 3/2, C 4 F 9 C ₂ H ₄ Si (NH ₃ ) 2/2, and poly siloxazane. The present invention also provides a method of manufacturing a transparent substrate.

Also, the buffer layer is a layer formed using at least one selected from the group consisting of a first carbon compound, a second carbon compound, and a metal oxide, and the first carbon compound has a glass transition temperature (Tg) Wherein the second carbon compound comprises a carbon compound which is decomposed by ultraviolet rays.

The first carbon compound may include at least one selected from the group consisting of polycarbonate, polymethyl methacrylate (PTFE), polyvinylchloride (PVC), polystyrene (PS), and polyethyl methacrylate (PEMA) A method for manufacturing a transparent substrate is provided.

The second carbon compound may be at least one selected from the group consisting of a metal ion-based polymer, a vinyl-ketone copolymer and an ethylene-CO (ethylene-CO) ≪ / RTI >

In addition, the metal oxide group consisting of yttrium oxide (Y ₂ O _3), zirconia (ZrO _2), alumina (Al ₂ O _3), boron nitride (BN), titanium nitride (TiN) and silicon oxide (SiO ₂₎ The method comprising the steps of:

The first step is a step of preparing a release layer on which a concave or convex surface pattern is formed.

In addition, the first step includes a step of forming a surface pattern on the surface of the release layer by mask etching using oxygen plasma or wet etching using an etching solution.

The present invention also provides a method of manufacturing a transparent substrate comprising a first transparent conductive layer, a second transparent conductive layer and a base polymer layer, the method comprising: a first step of preparing a release layer; A second step of forming a first transparent conductive layer on the release layer; A second transparent conductive layer formed on the first transparent conductive layer and including a conductor and a polymer coating layer covering the conductor; A third step of forming a base polymer layer on the second transparent conductive layer; And a fourth step of separating the release layer from the first transparent conductive layer to obtain a translucent substrate including a first transparent conductive layer and a base polymer layer.

The present invention also provides a method of manufacturing a transparent substrate comprising a first transparent conductive layer, a second transparent conductive layer, a light extracting layer and a base polymer layer, the method comprising: a first step of preparing a release layer; A second step of forming a first transparent conductive layer on the release layer; A second transparent conductive layer formed on the first transparent conductive layer and including a conductor and a polymer coating layer covering the conductor; A second step of forming a light extracting layer on the second transparent conductive layer; A third step of forming a base polymer layer on the light extracting layer; And a fourth step of separating the release layer from the first transparent conductive layer to obtain a translucent substrate including a first transparent conductive layer and a base polymer layer.

And further comprising a fifth step of plasma-treating the separated first transparent conductive layer after the fourth step to remove the remaining release layer component.

The present invention can provide a process for producing a simpler and less costly translucent substrate by forming and separating the first transparent conductive layer, the base polymer layer and the like in the reverse order on the release layer. In this case, when a flexible plastic substrate or buffer layer is used, a flexible transparent substrate that can be used for a flexible substrate can be manufactured, and each step process can be continuously performed by a roll-to-roll method, thereby improving productivity, reliability and economy .

Further, by forming the first transparent conductive layer on the release layer, the first transparent conductive layer having excellent flatness can be formed. Due to the nature of the material forming the buffer layer, it is possible to detach from the substrate without complicated processes or much energy. Thereby providing a process for manufacturing a light-transmissive substrate that is simplified and has a reduced manufacturing cost.

In addition, the surface shape of the release layer can be controlled to control the surface shape of the first transparent conductive layer of the translucent substrate finally transferred through the method of manufacturing a transparent substrate according to an embodiment of the present invention. When an organic light emitting device is manufactured by laminating a light emitting layer and a reflective electrode on a transparent substrate including a first transparent conductive layer having a concave or convex surface pattern, the surface roughness is increased to increase the light emitting area, When the organic solar cell is manufactured by laminating the photoactive layer and the metal electrode on the transparent substrate, the light receiving area of the solar light is increased, It is possible to provide an effect of increasing power generation efficiency.

Further, by sequentially forming the second transparent conductive layer on the first transparent conductive layer, since the metal nanowires of the second transparent conductive layer are located closer to the first transparent conductive layer, the transparent conductive substrate having improved electrical conductivity and the A process for manufacturing an organic light emitting device can be provided.

And forming a light extracting layer on the second transparent conductive layer, light extraction through light absorption and reflection is possible, so that the second transparent conductive layer, which mainly functions as a conductor, can be complemented in terms of function, The metal nanowires included in the transparent conductive layer are impregnated or coated with the light extracting layer, thereby solving the problem of lowering the reliability caused by sulfurization and oxidation of the metal nanowires.

1, 2, 4, 6 to 8, 14, and 15 show a method of manufacturing a transparent substrate according to an embodiment of the present invention.
FIGS. 3, 5, 9, 10, and 16 show a light-transmitting substrate manufactured by the method of manufacturing a transparent substrate according to an embodiment of the present invention.
FIGS. 11 to 13 and FIG. 20 show a second transparent conductive layer according to an embodiment of the present invention.
FIG. 17 shows a SEM image of a scattering particle inserted as a light extracting layer on a second transparent conductive layer according to an embodiment of the present invention.
18 shows a method of manufacturing a roll-to-roll method of a transparent substrate according to an embodiment of the present invention.
FIG. 19 shows an organic light emitting device according to another embodiment of the present invention.
FIG. 21 shows a photograph visually showing the flexibility of the transparent substrate produced according to the embodiment of the present invention.
22 shows a photograph of a surface optical image taken in the direction of the first transparent conductive layer of the transparent substrate produced according to the embodiment of the present invention.
FIG. 23 is a SEM image showing a metal nanowire of a second transparent conductive layer manufactured according to an embodiment of the present invention.
FIG. 24 shows a SEM image of a transparent substrate prepared according to an embodiment of the present invention in which the surface shape of the first transparent conductive layer is controlled by a wave pattern.
FIGS. 25 and 26 show XRD measurement data of a transparent substrate manufactured according to an embodiment of the present invention.
FIG. 27 shows component analysis data of the transparent substrate manufactured according to an embodiment of the present invention through EDX.
28 shows the surface AFM profile of the first transparent conductive layer of the transparent substrate manufactured according to an embodiment of the present invention.
FIG. 29 shows an AFM image of a waveguide shape-controlled translucent electrode manufactured according to an embodiment of the present invention.
FIG. 30 shows optical performance and electrical conductivity data according to an average thickness of a light extracting layer of a light transmitting electrode manufactured according to an embodiment of the present invention.

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout this specification and claims, the word "comprise", "comprises", "comprising" means including a stated article, step or group of articles, and steps, , Step, or group of objects, or a group of steps.

Also throughout this specification, when a member is " on " another member, it includes not only a member in contact with another member, but also another member between the two members.

On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. Any feature that is specifically or advantageously indicated as being advantageous may be combined with any other feature or feature that is indicated as being preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

A method of manufacturing a transparent substrate according to an embodiment of the present invention includes a first step of preparing a release layer 10 as shown in FIGS. 1 and 2, a first step of forming a first transparent conductive layer 20 on a release layer 10 A third step of forming a base polymer layer 50 on the second transparent conductive layer 30 and a third step of forming a second transparent conductive layer 30 on the first transparent conductive layer 20, The transparent substrate 100 including the base polymer layer 50 as shown in Fig. 3 and the first transparent conductive layer 20 provided on the base polymer layer 50 can be manufactured.

A method of manufacturing a transparent substrate according to an embodiment of the present invention is a method of forming a transparent conductive layer 20, a base polymer layer 50 and the like in reverse order on a release layer 10, It is possible to provide a process for manufacturing the light-transmissive substrate 100 that has been reduced.

The first step of fabricating the transparent substrate 100 according to an embodiment of the present invention is to prepare a release layer 10 that is easily separated from the first transparent conductive layer 20, A substrate 11, a buffer substrate 12, or a substrate 13 including a buffer layer on one surface thereof.

The substrate 11 may be a polytetrafluoroetylene substrate or a bulk polymerized polymethyl methacrylate (PMMA) substrate. When a flexible substrate is used, a flexible transparent substrate may be manufactured. And each step process can be continuously performed in a roll-to-roll manner, thereby improving productivity, reliability, and economy. Also, when a polytetrafluoroethylene substrate is used, the substrate may be used as a release layer 10 without a separate buffer layer.

The buffer substrate 12 may be a substrate containing a carbon compound containing fluorine (F), and the carbon compound containing fluorine (F) may be selected from the group consisting of methyltrifluoropropyl siloxane, methylfluoro ), C ₈ F ₁₇ C ₂ H ₄ Si (NH) _3/2 , C ₄ F ₉ C ₂ H ₄ Si (NH) _3/2, or polysiloxazane. Among them, a substrate containing tetrafluoroethylene is preferable.

When the substrate 13 including the buffer layer on one side is used as the release layer 10, the buffer layer is a layer formed using various kinds of carbon compounds or metal oxides, and the first carbon compound, the second carbon compound, and the metal oxide May be formed on the substrate using any one or more materials selected from the group consisting of < RTI ID = 0.0 > The first carbon compound includes a carbon compound having a glass transition temperature (Tg) of 200 DEG C or lower, the second carbon compound includes a carbon compound decomposable by ultraviolet rays, and the metal oxide includes a metal oxide having low adhesiveness.

Among the carbon compounds having a glass transition temperature (Tg) of 200 ° C or less, the first carbon compound is composed of polycarbonate, PMMA (polymethyl methacrylate), PTFE (polytetrafluoroethylene), polyvinylchloride (PVC), polystyrene (PS) and polyethyl methacrylate , And the like. More preferably, the surface adhesion at the interface of the buffer layer may be lowered by using a carbon compound, a polymethylmethacrylate (PMMA) or a polytetrafluoroethylene (PTFE) having a glass transition temperature (Tg) of 100 to 150 ° C.

The buffer layer contains the first carbon compound having a glass transition temperature (Tg) of 200 DEG C or lower, so that in the step of separating the release layer 10 and the first transparent conductive layer 20 in the fourth step It is good for changing properties and shape. When the glass transition temperature is higher than 200 DEG C, a relatively high temperature and time are required for curing. Materials with low glass transition temperatures are also suitable for process cost and yield in roll-to-roll and continuous processes.

Among the carbon compounds decomposed by ultraviolet rays, the second carbon compound is preferably at least one selected from the group consisting of a metal ion polymer, a vinyl-ketone copolymer and an ethylene-CO (ethylene-CO) .

The buffer layer includes the second carbon compound which is decomposed by ultraviolet rays so that in the step of separating the release layer 10 and the first transparent conductive layer 20 in the fourth step to be described later, There is an advantage that the layer 20 can be separated.

The metal oxide has an advantage that the surface tension and the surface energy can be easily controlled by the atoms substituted at the interface and can be easily controlled by the UV / ozone and plasma treatment methods. As a result, it is possible to control the adhesiveness and adhesiveness of the interface and to exhibit the property of easily transferring the heterogeneous material.

The metal oxide is yttrium oxide from a material in virtually any environment with low tack having a thermodynamically highly stable down to _{2000 ℃ (Y 2 O 3)} , zirconia (ZrO _2), alumina (Al ₂ O _3), boron nitride ( BN), it is preferred to include any one or more selected from a group consisting of titanium nitride (TiN) and silicon oxide (SiO _2).

4, the surface of the first transparent conductive layer 20 is exposed to the surface of the first transparent conductive layer 20 through the release layer 10 including the substrates 11, 12, and 13 on which the patterns are formed, Can be formed. For example, by controlling the surface shape upon formation of the buffer layer on the substrate 13, the surface of the first transparent conductive layer of the translucent substrate finally transferred through the fourth step of the method for manufacturing a transparent substrate according to one embodiment of the present invention Shape can be controlled. For example, if a wave pattern is formed on the buffer layer to laminate and separate the first transparent conductive layer, the wave pattern is transferred to the first transparent conductive layer.

When an organic light emitting device is manufactured by laminating a light emitting layer and a reflective electrode on a transparent substrate including a first transparent conductive layer 20 having a concavo-convex surface pattern on its surface as shown in Fig. 5, The light emission area can be increased and the light extraction efficiency can be improved by performing the light extraction function. In addition, when an organic solar cell is manufactured by laminating the photoactive layer and the metal electrode on the transparent substrate, the light receiving area of the solar light can be increased and the effect of increasing the power generation efficiency can be provided.

As a method of forming the concave and convex on the substrate or the buffer layer, a method of etching using a mask using atmospheric pressure and oxygen plasma on the surface, and a method of wet etching using a chemical solution are used.

The thickness of the buffer substrate and the buffer layer is preferably 100 nm to 10 mu m. When the buffer layer is formed at less than 100 nm, the chemical corrosion resistance and the surface uniformity are unstable. When the buffer layer is formed in excess of 10 탆, the surface irregularities and the curing time are prolonged. And more preferably 400 nm to 600 nm.

The first step of fabricating a transparent substrate according to an embodiment of the present invention includes a step of applying a coating solution such as bar coating, slot die coating, spray coating, , Spin coating, or the like, and then a buffer layer sheet is separately formed and adhered to the substrate. Alternatively, when a flexible substrate is used as the substrate 13, a coating process using a buffer solution and a heat treatment process The buffer layer can be formed and the surface shape can be adjusted.

Step 2-1 of manufacturing a transparent substrate according to an embodiment of the present invention is a step of forming a first transparent conductive layer 20 on a release layer 10, The transparent conductive layer 20 is not limited as long as it is a transparent and conductive material, but a transparent conductive oxide layer, a transparent conductive nitride layer, a transparent conductive sulfide layer, and a mixed layer thereof having excellent transparency, conductivity and heat resistance are used It is good. Preferably, _{ZnO (Zinc Oxide), SnO 2} (Tin Oxide), TiO 2, Al 2 O 3 , and can be formed using any one or more selected from those of the solid solution, and, where the F, Al, Ga, In , Si, or the like may be doped or solidified to form the first transparent conductive layer 20.

The thickness of the first transparent conductive layer 20 is preferably 5 nm to 100 nm. When the thickness is less than 5 nm, the crystallinity of the thin film is deteriorated. When the thickness is more than 100 nm, there is a problem that the flexibility is reduced and surface cracking occurs during the folding or rolling. More preferably 5 nm to 20 nm.

In step 2-1 of manufacturing a transparent substrate according to an embodiment of the present invention, a first transparent conductive layer 20 may be formed on the release layer 10 using spin coating, May be formed through deposition in a roll-to-roll process, but the present invention is not limited thereto.

6 to 8, the method for fabricating a transparent substrate according to an embodiment of the present invention further includes a second step 2-2 of forming a second transparent conductive layer 30 on the first transparent conductive layer 20 A transparent substrate including the first transparent conductive layer 20, the second transparent conductive layer 30, and the base polymer layer 50 as shown in FIGS. 9 and 10 can be manufactured. It has improved electrical conductivity and light scattering effect.

A method of manufacturing a transparent substrate according to an embodiment of the present invention includes forming a first transparent conductive layer 20 on a release layer 10 and then forming a polymer coating layer 32 covering the conductor 31 and the conductor 31 The transparent conductive substrate 30 is joined to the first transparent conductive layer 20 to form the transparent substrate 100 having excellent electrical conductivity and light scattering effect Process can be provided.

The second transparent conductive layer 30 includes a metal nanowire 311 or a metal mesh pattern 312 as a conductor 31. The metal nanowire 311 refers to a nano-sized structure having electrical conductivity. The average diameter of the metal nanowires 311 is 30 nm to 80 nm, and the length is preferably 10 μm to 80 μm. If it is less than the above-mentioned range, there is a problem that the electrical conductivity is lowered. The metal mesh pattern 312 is a metal mesh pattern.

The second transparent conductive layer 30 is formed by forming a metal nanowire 311 or a metal mesh pattern 312 on the first transparent conductive layer 20 and then covering the metal nanowire 311 with a polymer. More specifically, when the metal nanowire 311 is included, the ink composition containing the metal nanowire is coated on the first transparent conductive layer 20, dried and cured, and then coated with a polymer to form a metal mesh When the pattern 312 is included, the first transparent conductive layer 20 is printed on the first transparent conductive layer 20 in the form of a mesh using a metal paste or ink, and then fired to form a metal mesh pattern 312, .

The transparent substrate according to the present invention can complement the conductivity of the first transparent conductive layer 20 by including the second transparent conductive layer 30 between the first transparent conductive layer 20 and the underlying polymer layer 50 By providing a light extraction function, it is possible to provide a light-transmissible substrate which can be used not only for display but also for illumination.

In addition, the second transparent conductive layer 30 may further include metal particles 313 to increase light extraction efficiency. The size of the metal particles 313 is 100 to 600 nm. When the thickness is less than 100 nm, there is a problem that the scattering property is lowered, and when the thickness exceeds 600 nm, there is a problem of loss of transmittance. The shape of the metal particles 313 is not limited to a spherical shape, an elliptical shape, an amorphous shape, and may have projections on its outer surface. When a projection is provided on the outer surface, the size of the projection is 10 to 300 nm. If it is less than 10 nm, there is a problem of light scattering degradation, and if it exceeds 300 nm, there is a problem of loss of transmittance.

When the second transparent conductive layer 30 includes the metal nanowires 311 and the metal particles 313, the ink composition containing the metal nanowires and the metal particles is applied on the first transparent conductive layer 20 After drying and curing, the second transparent conductive layer 30 as shown in FIG. 11 can be formed by coating with a polymer.

When the second transparent conductive layer 30 includes the metal mesh pattern 312 and the metal particles 313, the metal mesh pattern 312 is formed on the first transparent conductive layer 20, and the metal mesh pattern 312 The ink composition containing the metal particles 313 is applied on the first transparent conductive layer 20 having the transparent conductive layer 30 formed thereon, dried and cured, and then coated with a polymer to form a second transparent conductive layer 30 ) Can be formed.

Or the metal mesh pattern 312 is first coated with a paste in which metal particles or metal oxide particles are dispersed, and then the entire layer including the metal mesh pattern coated with the primary is again coated with the polymer to form a secondary coating, The second transparent conductive layer 30 as shown in Fig. Also, when covering the metal mesh pattern 312, pores are optionally formed in the paste, so that the light extraction efficiency can be given by the scattering angle change caused by the pores. Also, a method of increasing light extraction efficiency by internal scattering is possible by arranging light scattering particles around the metal mesh pattern 312 by inserting arbitrary light extracting nanoparticles into the paste. Light extracting nanoparticles, light scattering particles mean metal particles or metal oxide particles.

In the case where the second transparent conductive layer 30 includes the metal mesh pattern 312, the metal mesh pattern 312 may be coated using the paste without the metal particles 313, That is, a shape having irregularities on the surface, thereby providing a light extracting effect.

In addition, the surface of the metal mesh pattern 312 is selectively coated with a metal oxide by using xenon light to cover various oxides such as ZnO, TiO ₂ , SiO ₂ , SnO ₂ , and Al ₂ O ₃ , .

The metal nanowires 311 included in the second transparent conductive layer 30 and the metal of the metal mesh pattern 312 and the metal particles 313 may be any conductive material. More typically, a metal such as Ag, Au, Cu, Pt, Fe, Ni, Cb, Zn, Ti, But are not limited to, those selected from the group consisting of chromium (Cr), aluminum (Al), palladium (Pd), and combinations thereof. Silver (Ag) is preferably used. Silver (Ag) reflects light as a metal and has a low transmittance. However, when the translucent substrate according to the present invention is used as a translucent electrode of an organic light emitting device, a reflective electrode (for example, an aluminum And reflects light to each other, so that light loss inside the device is actually reduced.

The thickness of the second transparent conductive layer 30 is 100 nm to 10 占 퐉. If it is less than 100 nm, there is a problem of lowering the electrical conductivity, and if it is more than 10 μm, there is a problem of loss of transmittance. When light reaches the surface of the metal nanowires and the metal particles, light can be scattered through the metal nanowires and the metal particles. Therefore, when used as a light-transmitting electrode of an organic light emitting device, the light extraction efficiency can be increased. Particularly, the metal particles are provided with protrusions on the outer surface to scatter light of a wavelength having a larger area band. The bonding property with the first transparent conductive layer 20 in which the second transparent conductive layer 30 is formed can be enhanced.

The second transparent conductive layer 30 may be a layer including a metal mesh pattern having various patterns and line widths. In the case where a metal mesh pattern is included, the layer is arranged in an orthogonal form using silver (Ag), copper (Cu), aluminum (Al), an alloy or the like. And thus can be formed with various patterns and line widths. For example, when it is used in an organic light emitting device for illumination, it is preferable to form it with a line width of 100 nm to 10 μm because it exhibits a haze value of about 2% to 15% and a transmittance of about 70% to 90%.

In step 2-2 of manufacturing a transparent substrate according to an embodiment of the present invention, a second transparent conductive layer 30 is formed on the first transparent conductive layer 20 using spin coating When a flexible substrate is used, it may be formed by applying an ink composition containing a metal nanowire or metal particles in a roll-to-roll process and drying, but the present invention is not limited thereto. Further, a metal mesh pattern can be formed as a second transparent conductive layer by photolithography or the like.

The first transparent conductive layer 20 is formed on the buffer layer and the second transparent conductive layer 30 is sequentially formed on the first transparent conductive layer 20. In the method of manufacturing the transparent conductive substrate according to the embodiment of the present invention, The metal nanowires 311 and the metal particles 313 of the second transparent conductive layer 30 are positioned closer to the first transparent conductive layer 20 by gravity so that the electrical conductivity is improved and the light extraction It is possible to provide a light-transmitting electrode excellent in efficiency.

The method of manufacturing a transparent electrode according to an embodiment of the present invention may further include a step 2-3 of manufacturing a light extracting layer 40 on the second transparent conductive layer 30 as shown in FIGS. 14 and 15 The transparent substrate 100 including the first transparent conductive layer 20, the second transparent conductive layer 30, the light extracting layer 40 and the base polymer layer 50 as shown in Fig. 16 can be manufactured The second transparent conductive layer 30 having a function of a conductor can be complemented in terms of its function, and the metal contained in the second transparent conductive layer 30 can be used as a light- The metal nanowire 311, the metal mesh pattern 312 or the metal particles 313 are impregnated or coated with the light extracting layer 40, so that the metal nanowires 311, the metal mesh pattern 312, It is possible to solve the problem of reduction in reliability caused by sulfidation and oxidation between the electrodes 313.

The light extracting layer 40 may be a layer 41 coated with an oxide, a nitride or a sulfide of a metal formed on the second transparent conductive layer 30 and may be a layer 41 having scattered particles of an average diameter of 50 nm to 500 nm 42). They may also be coated with oxides, nitrides or sulfides of complex metals, and scattering particles may also be intercalated layers. FIG. 17 shows a SEM image photograph in which scattering particles are inserted as a light extracting layer on the second transparent conductive layer.

The light extracting layer 40 may be formed on the metal mesh pattern 312 formed as the second transparent conductive layer 30. In this case, the light extracting layer 40 may be coated with an oxide, a nitride, a sulfide, Or a layer in which scattering particles of a metal oxide, nitride, or sulfide are inserted. They may also be formed as a composite layer.

The light extracting layer 40 may have a protrusion shape or a pattern shape, and its thickness is 100 nm to 600 nm. When the thickness is less than 100 nm, the light scattering effect is low. When the thickness exceeds 600 nm, there is a problem in that the light transmittance is decreased. More preferably 100 to 300 nm.

Step 2-3 of fabricating the transparent substrate according to an exemplary embodiment of the present invention may include forming a light extracting layer 40 on the second transparent conductive layer 30 using spin coating, When a substrate is used, it may be formed by applying an ink composition containing a metal oxide, a nitride, a sulfide, or a mixture thereof, and heat-treating it in a roll-to-roll process, but is not limited thereto.

The third step of fabricating the transparent substrate according to an embodiment of the present invention includes forming a base polymer layer 50 on the first transparent conductive layer 20, the second transparent conductive layer 30, or the light extracting layer 40, A flexible translucent substrate 100 can be manufactured through a roll-to-roll process which is simplified and cost-reduced.

The base polymer layer 50 may be formed of a material selected from the group consisting of polyimide (PI), polyethylene terephthalate (PET), polycarbonate (PC), polyether sulfone (PES), polyethylene naphthalate (PEN), polyacrylate polydimethyl siloxane), and a metal thin film. It is preferable to use PI having excellent chemical resistance, heat resistance and the like.

The thickness of the base polymer layer 50 is preferably 0.1 mm to 3 mm. When it is formed to be less than 0.1 mm, there is a problem that the supporting force is low as a mother board, and when it is formed more than 3 mm, flexibility is reduced. More preferably 0.2 mm to 0.5 mm.

The third step of fabricating the transparent substrate according to an embodiment of the present invention may include laminating using a polymer solution or applying a polymer composition, followed by drying and curing or screen printing When the base polymer layer 50 is formed or a flexible substrate is used, the polymer composition may be applied and heat-treated in a roll-to-roll process, but is not limited thereto.

The fourth step of fabricating the transparent substrate according to an embodiment of the present invention is a step of detaching the release layer 10 and separating the release layer 10 and the first transparent conductive layer 20 The first transparent conductive layer 20, the second transparent conductive layer 30, and the base polymer layer 50 (including the first transparent conductive layer 20 and the base polymer layer 50) The transparent substrate 100 including the transparent substrate 100, the first transparent conductive layer 20, the second transparent conductive layer 30, the light extracting layer 40, and the base polymer layer 50, .

When the first transparent conductive layer 20 is formed so as to have a shape on the surface of the buffer layer on the substrate as the release layer 10 and the first transparent conductive layer 20 is transferred, the surface of the first transparent conductive layer 20, The surface shape of the manufactured transparent substrate 100 can be controlled.

In the fourth step of fabricating the transparent substrate according to an exemplary embodiment of the present invention, the buffer layer may be irradiated with light through a light source to selectively change the properties of the buffer layer to lower the adhesive force with the first transparent conductive layer 20, But are not limited thereto. The buffer layer according to an embodiment of the present invention may be formed of a material such as the first carbon compound, the second carbon compound, and the metal oxide, that is, a carbon compound having a glass transition temperature of 200 ° C or less, a carbon compound decomposable by ultraviolet rays, It is advantageous in that it can be easily separated (transferred) without a complicated process or low energy consumption due to low metal oxide.

A gas discharge lamp including a xenon lamp, a halogen lamp, a HID lamp, a fluorescent lamp, and a mercury lamp may be used as the light source that can be used for the light irradiation treatment. Any heat source can be used without limitation. Preferably, the use of Xenon lamps is good for local energy transfer for formation of a light extraction layer without damaging the transparent conductive oxide layer and other materials.

A method of manufacturing a roll-to-roll method of a transparent substrate according to an embodiment of the present invention is shown in Fig.

In addition, the method of manufacturing a transparent substrate according to an embodiment of the present invention may further include a fifth step of removing the release layer component remaining in the separated first transparent conductive layer after the fourth step. The buffer layer remaining on the surface of the transparent substrate including the separated first transparent conductive layer 20 may be removed by washing with a chemical such as acetone or ethanol or by plasma treatment.

19, the organic light emitting device 1000 according to another embodiment of the present invention may be formed as a light transmitting electrode 100 according to a method of manufacturing a light transmitting substrate according to an embodiment of the present invention, 1 stacking the organic light emitting layer 200 on the transparent conductive layer 20, and the reflective electrode 300 in this order.

The material and method for forming the organic light-emitting layer 200 are not particularly limited, and materials and forming methods well-known in the art can be used. Various organic materials can be used for the organic light-emitting layer 200 in a vapor deposition process, a solvent process, , Dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer.

The reflective electrode 300 may be formed by a sputtering method, an E-beam evaporation method, a thermal evaporation method, a laser molecular beam epitaxy (L-MBE) method, Pulsed Laser Deposition (PLD); physical vapor deposition (PVD); A thermal chemical vapor deposition method, a plasma chemical vapor deposition (PECVD) method, a light chemical vapor deposition method, a laser chemical vapor deposition method, a metal- A chemical vapor deposition method selected from the group consisting of metal organic chemical vapor deposition (MOCVD), and hydride vapor phase epitaxy (HVPE); Or atomic layer deposition (ALD).

The reflective electrode 300 may be formed of at least one selected from the group consisting of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, platinum, gold, tungsten, tantalum, have.

The transparent substrate 100 according to an embodiment of the present invention includes a base polymer layer 50, a second transparent conductive layer 30 provided on the base polymer layer, and a second transparent conductive layer 30 provided on the second transparent conductive layer. Layer (20).

20, the second transparent conductive layer 30 includes a conductor 31 and a polymer coating layer 32 covering the conductor, and the second transparent conductive layer 30 includes a first transparent conductive layer 20 are referred to as A regions, and a half adjacent to the base polymer layer 50 is referred to as a B region, at least 60% of the conductors 31 are distributed in the A region. More preferably, the conductor 31 is distributed at 70% or 80% or more, depending on the manufacturing characteristics of the second transparent conductive layer 30.

The conductor 31 includes a metal nanowire 311 or a metal mesh pattern 312. The second transparent conductive layer 30 may further include metal particles 313 distributed adjacent to the first transparent conductive layer 20. The metal particles 313 are distributed in the area A of the second transparent conductive layer by 50% or more. More preferably 60% or 70% or more, depending on the production characteristics of the second transparent conductive layer.

The polymer coating layer 32 covering the conductor 31 may be formed using polyimide (PI), polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), Resin resin for UV curing, Resin resin for thermal curing, have. Preferably, the conductive material 31 is coated with a resin for ultraviolet (UV) curing.

The transparent substrate 100 according to an embodiment of the present invention may include the second transparent conductive layer 30 to compensate the conductivity of the first transparent conductive layer 20. In particular, 1 transparent conductive layer 20, it is possible to exhibit more excellent characteristics of the auxiliary electrode. This is a possible structure because the second transparent conductive layer 30 is formed on the first transparent conductive layer 20 by the method of manufacturing a transparent substrate according to an embodiment of the present invention.

Also, the second transparent conductive layer 30 may be a layer in which the metal mesh pattern 312 is doubly coated with a polymer having a light extracting shape. A metal mesh pattern 312 joined on the first transparent conductive layer 20 is coated with a polymer having a light extracting shape, for example, a shape having irregularities on its surface, and then covered with a polymer coating layer 32, 2 transparent conductive layer is formed.

 The second transparent conductive layer 30 may be a layer in which the metal mesh pattern is doubly coated with a polymer containing light extracting particles. The metal mesh pattern 312 connected to the first transparent conductive layer 20 is coated with the polymer including the metal particles 313 and then covered with the polymer coating layer 32 to form the second transparent conductive layer do.

The first transparent conductive layer 20 included in the transmissive substrate 100 according to an embodiment of the present invention may have a concave or convex surface pattern on the surface thereof.

A liquid crystal display, an electrochromic display (ECD), a plasma display panel (PDP), a flexible display, an electronic paper, a touch panel, etc., including a transparent substrate according to an embodiment of the present invention Can be provided.

Further, the transparent substrate according to an embodiment of the present invention can be used for an organic light emitting device or an organic solar battery. That is, the light emitting material layer 200 and the reflective metal layer 300 may be laminated on the first transparent conductive layer 20 of the translucent substrate 100 of the present invention to provide an organic light emitting device, An electrode layer may be laminated to provide an organic solar cell.

In the case where the second transparent conductive layer 30 of the transparent substrate according to the embodiment of the present invention includes a structure having a light extracting function, for example, a structure including metal particles to cause light scattering or a shape capable of light extraction , It can be suitably used as an organic light emitting element for illumination.

Example

Example 1

A buffer solution was spin-coated on a 0.6 mm glass substrate to form a 400 nm buffer layer. A 10 nm transparent oxide layer was formed on the buffer layer by a physical vapor deposition method, and a polymer including silver nanowires (Ag NW) The ink composition is applied and dried and cured at 80 to 150 DEG C for 5 to 10 minutes to form an AgNW layer of 200 nm or less. A transparent substrate was prepared by dissolving the polyimide (PI) solution or UV resin on the polymer layer to form a polymer layer, and then changing the properties of the buffer layer using latent heat by light (melting) to separate the transparent oxide layer.

Example 2

A 3 mm substrate film of 0.2 mm was wound on the rollers continuously to provide a roll-to-roll process. First, a buffer layer solution is coated on a flexible substrate film and heat treatment is performed to form a sacrifice layer. A first transparent conductive layer is deposited, a silver nanowire is deposited to form a second transparent conductive layer by coating at high temperature, Coating and heat treatment to form a base polymer layer. The transparent substrate was separated by irradiating light thereto to melt the buffer layer to continuously produce a transparent substrate. 18 shows the roll-to-roll manufacturing process of this embodiment.

Example 3

A 3 mm substrate film of 0.5 mm was wound on the rollers to continuously provide a roll-to-roll process. First, when a buffer solution is coated on a flexible substrate film and a heat treatment is performed, a buffer layer having a wavy pattern is formed by centrifugal force by solution coating. A first transparent conductive layer is deposited, silver nanowires are grown, 2 transparent conductive layer was formed, a polymer or UV resin solution was coated, and a base polymer layer was formed by UV treatment. The buffer layer was melted by using a xenon lamp to separate the flexible substrate, and the transparent substrate was continuously manufactured. The fabricated translucent substrate has the same wave pattern as that of the buffer layer, and FIG. 18 shows the roll-to-roll manufacturing process of this embodiment.

Comparative Example

A PI film was prepared by applying a polyimide (PI) solution to a carrier glass. A barrier coating film was formed on the PI film. A transparent electrode was manufactured by separating the barrier film from the carrier glass.

Experimental Example

(1) Image measurement

FIG. 21 shows a photograph visually showing the flexibility of the transparent substrate produced according to the embodiment of the present invention.

22 shows a surface optical image taken in the direction of the first transparent conductive layer of the transparent substrate manufactured according to the embodiment of the present invention, and FIG. 23 shows an SEM image photograph of the metal nanowire of the second transparent conductive layer Respectively.

FIG. 24 shows a SEM image photograph in which the surface shape of the first transparent conductive layer of the transparent substrate produced by controlling the surface shape of the buffer layer is controlled to a wavy pattern.

(2) X-ray diffraction pattern (XRD) and EDX measurement

Fig. 25 shows XRD measurement data of a transparent substrate including a first transparent conductive layer, a second transparent conductive layer, and a base polymer layer, and has a peak of ITO and a peak of Ag.

FIG. 26 shows XRD measurement data of a transparent substrate including a first transparent conductive layer, a second transparent conductive layer, a light extracting layer, and a base polymer layer, wherein the peak of ITO, the peak of ZnO, the peak of Ag, .

FIG. 27 shows component analysis data through EDX of a transparent substrate manufactured according to an embodiment of the present invention. It can be seen that components such as Si, C, O, Zn, Ag, In and Sn exist.

(3) Measurement of flatness (surface roughness)

R _PV and R _MS were measured when the surface roughness of the first transparent conductive layer of the transparent substrate prepared in the examples was observed using a AFM (Atomic Force Microscope) in a scan range of 10 μm × 10 μm. The measurement results are shown in Table 1 below, and the surface AFM profile is shown in FIG. FIG. 29 shows an AFM image of a translucent electrode whose shape is controlled in a wave pattern.

 (4) Transmittance and electrical conductivity measurement

The electrical conductivity was measured by measuring the surface resistance of a flexible translucent substrate having various light extracting layer thicknesses prepared in the examples. A 4-point probe (MCP-T610, manufactured by MITSUBISHI CHEMICAL ) Was used, and measurement was performed using an ESP type probe having a pin interval of 5 mm. The measurement results are shown in Table 1 below, and Table 2 and FIG. 30 show optical performance and electrical conductivity data according to the average thickness of the light extracting layer.

R _PV (nm) R _MS (nm) Sheet resistance (Ω / □) Example 1 5.769 0.6217 3.09 Example 2 31.9 2.008 8.77

Property Light extraction layer thickness Average
Thickness (nm) 124 186 214 256 Transmittance (%) 77.9 70.8 70.3 69.8 Haze (%) 10.3 47 49.8 54.6 Sheet
Resistance (Ω / □) 5.88 55.35 30.4 13.9

The features, structures, effects, and the like illustrated in the above-described embodiments can be combined and modified in other embodiments by those skilled in the art to which the embodiments belong. Therefore, it should be understood that the present invention is not limited to these combinations and modifications.

Claims (15)

A transparent substrate manufacturing method comprising a first transparent conductive layer and a base polymer layer,
A first step of preparing a release layer;
A second step of forming a first transparent conductive layer on the release layer;
A third step of forming a base polymer layer on the first transparent conductive layer; And
And a fourth step of separating the release layer from the first transparent conductive layer to obtain a transparent substrate including a first transparent conductive layer and a base polymer layer,
The first step may be a first carbon compound having a glass transition temperature (Tg) of 200 ° C or less as a first carbon compound such as PC (Polycarbonate), PMMA (Polymethyl methacrylate), PTFE (Polytetrafluoroethylene), Polyvinylchloride (PVC), Polystyrene , And a buffer layer formed to a thickness of 100 nm to 10 mu m,
In the step 2-1, the first transparent conductive layer may be formed on the release layer at a thickness of 5 nm to 100 nm by including at least one selected from the group consisting of a transparent conductive oxide, a transparent conductive nitride, a transparent conductive sulfide, Wherein the step of forming the transparent substrate comprises the steps of:
delete The method according to claim 1,
Wherein the fourth step is a step of separating the release layer from the first transparent conductive layer by irradiating the release layer with light energy to change the property of the material forming the release layer.
delete delete The method according to claim 1,
The first step may be a carbon compound containing fluorine (F), such as methyltrifluoropropyl siloxane, Methylfluoro, C ₈ F ₁₇ C ₂ H ₄ Si (NH) _3/2 , C ₄ F ₉ C ₂ H ₄ Si (NH ₃ ) 2/2, and poly siloxazane, and having a thickness of 100 nm to 10 μm, Wherein the step of preparing the transparent substrate comprises the steps of:
delete delete The method according to claim 1,
The first step is a carbon compound which is decomposed by ultraviolet rays and contains at least one carbon compound selected from the group consisting of a vinyl-ketone copolymer and an ethylene-CO (ethylene-CO) copolymer To form a release layer comprising a buffer layer formed to a thickness of 100 nm to 10 mu m.
The method according to claim 1,
The first stage is a metal oxide, yttrium oxide (Y ₂ O _3), zirconia (ZrO _2), alumina (Al ₂ O ₃₎ and silicon oxide (SiO ₂₎ one or more metal oxides selected from a group consisting of And a buffer layer formed to a thickness of 100 nm to 10 占 퐉, wherein the buffer layer is formed.
The method according to claim 1,
Wherein the first step is a step of preparing a release layer on which a concave or convex surface pattern is formed.
The method according to claim 1,
Wherein the first step comprises a step of forming a surface pattern on the surface of the release layer by mask etching using oxygen plasma or wet etching using an etching solution.
A transparent substrate manufacturing method comprising a first transparent conductive layer, a second transparent conductive layer, and a base polymer layer,
A first step of preparing a release layer;
A second step of forming a first transparent conductive layer on the release layer;
A second transparent conductive layer formed on the first transparent conductive layer and including a conductor and a polymer coating layer covering the conductor;
A third step of forming a base polymer layer on the second transparent conductive layer; And
And a fourth step of separating the release layer from the first transparent conductive layer to obtain a transparent substrate including a first transparent conductive layer and a base polymer layer,
The first step may be a first carbon compound having a glass transition temperature (Tg) of 200 ° C or less as a first carbon compound such as PC (Polycarbonate), PMMA (Polymethyl methacrylate), PTFE (Polytetrafluoroethylene), Polyvinylchloride (PVC), Polystyrene ), And a buffer layer formed to a thickness of 100 nm to 10 mu m, the method comprising the steps of: preparing a release layer comprising at least one carbon compound selected from the group consisting of
In the step 2-1, the first transparent conductive layer may be formed on the release layer at a thickness of 5 nm to 100 nm by including at least one selected from the group consisting of a transparent conductive oxide, a transparent conductive nitride, a transparent conductive sulfide, Wherein the step of forming the transparent substrate comprises the steps of:
A method of manufacturing a transparent substrate comprising a first transparent conductive layer, a second transparent conductive layer, a light extracting layer, and a base polymer layer,
A first step of preparing a release layer;
A second step of forming a first transparent conductive layer on the release layer;
A second transparent conductive layer formed on the first transparent conductive layer and including a conductor and a polymer coating layer covering the conductor;
A second step of forming a light extracting layer on the second transparent conductive layer;
A third step of forming a base polymer layer on the light extracting layer; And
And a fourth step of separating the release layer from the first transparent conductive layer to obtain a transparent substrate including a first transparent conductive layer and a base polymer layer,
The first step may be a first carbon compound having a glass transition temperature (Tg) of 200 ° C or less as a first carbon compound such as PC (Polycarbonate), PMMA (Polymethyl methacrylate), PTFE (Polytetrafluoroethylene), Polyvinylchloride (PVC), Polystyrene And a buffer layer formed on the buffer layer, wherein the buffer layer comprises at least one carbon compound selected from the group consisting of (i)
In the step 2-1, the first transparent conductive layer may be formed on the release layer at a thickness of 5 nm to 100 nm by including at least one selected from the group consisting of a transparent conductive oxide, a transparent conductive nitride, a transparent conductive sulfide, Wherein the step of forming the transparent substrate comprises the steps of:
15. The method of claim 1, 13 or 14,
And a fifth step of removing the remaining release layer components by plasma-treating the separated first transparent conductive layer after the fourth step.

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