WO2017074048A1 - Light-transmissive substrate manufacturing method and light-transmissive substrate manufactured using same - Google Patents

Abstract

The present invention relates to a light-transmissive substrate manufacturing method comprising: a first step of preparing a release layer; a (2-1)^th 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, and the present invention can provide a process for manufacturing a more simplified and cost-saving light-transmissive substrate by forming the first transparent conductive layer, the base polymer layer, and the like on the release layer in reverse order and then separating the release layer therefrom, wherein when a flexible plastic substrate or buffer layer is used, a flexible light-transmissive substrate usable for a flexible substrate can be manufactured, and each of the steps continue by a roll-to-roll scheme, thereby enabling high productivity, reliability, and economic feasibility to be provided.

Description

Method for manufacturing light-transmissive substrate and light-transmissive substrate manufactured

The present invention relates to a method of manufacturing a light-transmissive substrate and a light-transmissive substrate produced through the same. The present invention also relates to a display device, a lighting device, and the like to which a translucent substrate is applied.

The light transmissive substrate is a substrate including a transparent conductive layer having both electrical conductivity and light transparency. The light transmissive substrate provided in the light emitting device is configured to minimize the loss of generated light. For example, an organic light-emitting diode (OLED) is a device composed of luminescent organic materials, and light emitted from the organic luminescent layer is emitted to the outside via an electrode and a light transmissive substrate. Such translucent substrates include liquid crystal displays, electrochromic displays (ECDs), organic electroluminescent devices, solar cells, plasma display panels, flexible displays, electronic papers, It can be applied to display devices such as touch panels, lighting devices, or solar cells.

The light transmissive substrate includes a base substrate and a light transmissive electrode that performs an electrode function of a light emitting element attached to the substrate. The translucent electrode is mainly formed in a thin film form using a conductive material such as tin-doped indium oxide (ITO) on a base substrate made of plastic, but recently, carbon that can replace ITO containing indium, which is an unstable supply and demand, is used. Research and development on nanotubes (CNT), metal nanostructures, etc. are being actively made.

As described in Korean Patent Application Laid-Open No. 10-2014-0089670, a method of stacking transmissive substrates having different refractive indices is used to minimize light loss in the transparent substrate, or as disclosed in Korean Patent Publication No. 10-2014-0076268. As a method of applying to a flexible display using a memory polymer, development for improving the flexibility of a light-transmissive substrate is being made.

The present invention relates to a method of manufacturing a light-transmissive substrate including a first transparent conductive layer, a second transparent conductive layer, and a light extraction layer, and a light-transmissive substrate prepared through the same, and an organic light emitting device including the same. By forming and separating the conductive layer, the base polymer layer, and the like, there is provided a process for manufacturing a light transmissive substrate which is more simplified and reduced in cost.

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

The present invention provides a method of manufacturing a light-transmitting substrate comprising a first transparent conductive layer and a base polymer layer, comprising: a first step of preparing a release layer; Forming a first transparent conductive layer on the release layer; 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 light-transmissive substrate including a first transparent conductive layer and a base polymer layer.

In addition, the release layer provides a light-transmitting substrate manufacturing method comprising a substrate, a buffer substrate or a substrate including a buffer layer on one surface.

In addition, the fourth step provides a method of manufacturing a light-transmitting substrate, which is a step of separating the release layer from the first transparent conductive layer by changing the properties of materials constituting the release layer by irradiating light energy to the release layer.

In addition, the substrate provides a method of manufacturing a light-transmitting substrate including a polytetrafluoroetylene substrate or a bulk polymerized polymethyl methacrylate (PMMA) substrate.

In addition, the buffer substrate provides a light-transmitting substrate manufacturing method which is a substrate formed by containing a carbon compound containing fluorine (F).

In addition, the carbon compound containing fluorine (F) is methyltrifluoropropyl siloxane (Methyltrifluoropropyl siloxane), methylfluoro (Methylfluoro), C ₈ F ₁₇ C ₂ H ₄ Si (NH) _3/2 , C ₄ F ₉ provides a _{C 2 H 4 Si (NH)} 3/2 and a poly siloxane Southern any one method of manufacturing a transparent substrate a carbon compound selected from the group consisting of (poly siloxazane).

In addition, the buffer layer is a layer formed using any one or more selected from the group consisting of a first carbon compound, a second carbon compound and a metal oxide, the first carbon compound has a glass transition temperature (Tg) of 200 ℃ or less It includes a carbon compound, the second carbon compound provides a method for producing a light-transmitting substrate comprising a carbon compound that is decomposed by ultraviolet light.

In addition, the first carbon compound includes at least one selected from the group consisting of polycarbonate (PC), polymethyl methacrylate (PMMA), polytetrafluoroethylene (PTFE), polyvinylchloride (PVC), polystyrene (PS), and polyethyl methacrylate (PEMA). Provided is a method for manufacturing a light transmissive substrate.

In addition, the second carbon compound is a light-transmitting substrate including any one or more selected from the group consisting of a metal ion polymer, a vinyl-ketone copolymer and an ethylene-CO copolymer. It provides a manufacturing method.

In addition, the metal oxide is a 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 ). It provides a light-transmissive substrate manufacturing method comprising any one or more selected from.

The first step also provides a method of manufacturing a light-transmissive substrate, which is a step of preparing a release layer having a concave or convex surface pattern formed thereon.

In addition, the first step provides a method of manufacturing a light-transmitting substrate, the method including forming a surface pattern on the surface of the release layer through a mask etching using an oxygen plasma or a wet etching using an etching solution.

In another aspect, the present invention provides a method of manufacturing a light-transmissive substrate comprising a first transparent conductive layer, a second transparent conductive layer and a base polymer layer, the first step of preparing a release layer; Forming a first transparent conductive layer on the release layer; Forming a second transparent conductive layer on the first transparent conductive layer, the second transparent conductive layer including a conductor and a polymer coating layer covering the conductor; 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 light-transmissive substrate including a first transparent conductive layer and a base polymer layer.

The present invention also provides a method of manufacturing a light-transmitting substrate comprising a first transparent conductive layer, a second transparent conductive layer, a light extraction layer and a base polymer layer, the first step of preparing a release layer; Forming a first transparent conductive layer on the release layer; Forming a second transparent conductive layer on the first transparent conductive layer, the second transparent conductive layer including a conductor and a polymer coating layer covering the conductor; Forming a light extraction layer on the second transparent conductive layer; Forming a base polymer layer on the light extraction layer; And a fourth step of separating the release layer from the first transparent conductive layer to obtain a light-transmissive substrate including a first transparent conductive layer and a base polymer layer.

In addition, after the fourth step, there is provided a light-transmitting substrate manufacturing method further comprising a fifth step of removing the remaining release layer components by plasma treatment on the separated first transparent conductive layer.

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

Also, by forming the first transparent conductive layer on the release layer, the first transparent conductive layer having excellent flatness can be formed, and it can be detached from the substrate without complicated energy or high energy due to the characteristics of the material of the buffer layer. Thus, it is possible to provide a process for manufacturing a light-transmissive substrate that is more simplified and the manufacturing cost is reduced.

In addition, by controlling the surface shape when forming the release layer, the surface shape of the first transparent conductive layer of the finally transferred light-transmitting substrate may be controlled through the light-transmissive substrate manufacturing method according to an embodiment of the present invention. When the organic light emitting device is manufactured by stacking a light emitting layer and a reflective electrode on a light transmissive 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 and to extract light. It can provide the effect of improving the luminous efficiency by the role, when the organic solar cell is manufactured by stacking a photoactive layer and a metal electrode on the light-transmissive substrate, increases the light receiving area of the sunlight, and also acts as a light collection It can provide the effect of improving the power generation efficiency.

In addition, by sequentially forming a second transparent conductive layer on the first transparent conductive layer, since the metal nanowires of the second transparent conductive layer is located more adjacent to the first transparent conductive layer, an electrically conductive improved light-transmitting substrate and comprising the same It is possible to provide a process for manufacturing an organic light emitting device.

In addition, a light extraction layer is formed on the second transparent conductive layer, so that light extraction through light absorption and reflection is possible, and thus the second transparent conductive layer mainly having a function of a conductor can be complemented in terms of function. The metal nanowires included in the transparent conductive layer have an effect of being impregnated or coated by the light extraction layer, thereby solving the problem of reliability degradation caused by sulfation and oxidation between the metal nanowires.

1, 2, 4, 6 to 8, 14, and 15 illustrate a method of manufacturing a light transmissive substrate according to an embodiment of the present invention.

3, 5, 9, 10, and 16 illustrate a light-transmissive substrate manufactured by a light-transmissive substrate manufacturing method according to an embodiment of the present invention.

11 to 13 and 20 show a second transparent conductive layer according to an embodiment of the present invention.

FIG. 17 is a SEM image photograph of scattering particles inserted as a light extraction layer on a second transparent conductive layer according to an embodiment of the present invention.

18 illustrates a roll-to-roll manufacturing method of a light transmissive substrate according to an embodiment of the present invention.

19 illustrates an organic light emitting diode according to another embodiment of the present invention.

21 is a photograph visually showing the flexibility of the light-transmissive substrate prepared according to the embodiment of the present invention.

22 illustrates a surface optical image photograph taken in the direction of the first transparent conductive layer of the light transmissive substrate manufactured according to the embodiment of the present invention.

FIG. 23 shows SEM images of the metal nanowires of the second transparent conductive layer prepared according to the embodiment of the present invention.

24 illustrates a SEM image photograph in which the surface shape of the first transparent conductive layer of the light transmissive substrate manufactured according to the embodiment of the present invention is controlled by a wave pattern.

FIG. 25 and FIG. 26 show XRD measurement data of a light transmissive substrate prepared according to an embodiment of the present invention.

Figure 27 shows the component analysis data through the EDX of the light-transmissive substrate prepared according to an embodiment of the present invention.

28 illustrates the surface AFM profile of the first transparent conductive layer of the light transmissive substrate prepared according to the embodiment of the present invention.

29 shows an AFM image of a translucent electrode having a shape of a wave pattern manufactured according to an embodiment of the present invention.

30 shows optical performance and electrical conductivity data according to the average thickness of the light extracting layer of the translucent electrode manufactured according to the embodiment of the present invention.

Prior to describing the present invention in detail below, it is 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 limited only by the scope of 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 indicated.

Throughout this specification and claims, unless otherwise indicated, the termcomprise, constitutes, and configure means to include the referenced article, step, or group of articles, and step, and any other article It is not intended to exclude a stage or group of things or groups of stages.

Also throughout this specification, when a member is located “on” another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

On the other hand, various embodiments of the present invention can be combined with any other embodiment unless clearly indicated to the contrary. Any feature indicated as particularly preferred or advantageous may be combined with any other feature and features indicated as preferred or advantageous. Hereinafter, with reference to the accompanying drawings will be described an embodiment of the present invention and the effects thereof.

In the method of manufacturing a light-transmissive substrate according to an embodiment of the present invention, as shown in FIGS. 1 and 2, the first step of preparing the release layer 10 is performed by using the first transparent conductive layer 20 on the release layer 10. Step 2-1 to form, the third step of forming the base polymer layer 50 on the second transparent conductive layer 30 and the fourth step of separating the release layer 10 and the first transparent conductive layer 20 Including the step, the light-transmissive substrate 100 including the base polymer layer 50 and the first transparent conductive layer 20 provided on the base polymer layer 50 as shown in FIG. 3 may be manufactured.

Translucent substrate manufacturing method according to an embodiment of the present invention by forming the first transparent conductive layer 20, the base polymer layer 50 and the like on the release layer 10 in the reverse order and then separated, more simplified and costly A process for manufacturing the reduced light transmissive substrate 100 may be provided.

The first step of manufacturing the light-transmissive 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, the release layer 10 is A substrate 11, a buffer substrate 12, or a substrate 13 including a buffer layer on one surface thereof is included.

The substrate 11 may be a Teflon (polytetrafluoroetylene) substrate, a bulk polymerized polymethyl methacrylate (PMMA) substrate, and when using a flexible substrate, a flexible light-transmissive substrate may be manufactured. Each step process can be made in a continuous roll-to-roll method to increase productivity, reliability, and economics. In addition, in the case of using a polytetrafluoroetylene substrate, the substrate itself may be used as the release layer 10 without providing a separate buffer layer.

The buffer substrate 12 may use a substrate containing a carbon compound containing fluorine (F), and the carbon compound containing fluorine (F) may be methyltrifluoropropyl siloxane or methylfluoro. ), and the like _{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 a poly siloxane Southern (poly siloxazane). Especially, it is preferable that it is a board | substrate containing tetrafluoroethylene.

When the substrate 13 including the buffer layer on one surface is used as the release layer 10, the buffer layer is a layer formed using various kinds of carbon compounds or metal oxides, and includes a first carbon compound, a second carbon compound, and a metal oxide. It can be formed on the substrate using any one or more materials selected from the group consisting of. The first carbon compound includes a carbon compound having a glass transition temperature (Tg) of 200 ° C. or less, the second carbon compound includes a carbon compound decomposed by ultraviolet rays, and the metal oxide includes a metal oxide having low adhesion.

The first carbon compound is composed of PC (Polycarbonate), PMMA (Polymethyl methacrylate) PTFE (Polytetrafluoroethylene), Polyvinylchloride (PVC), Polystyrene (PS) and Polyethyl methacrylate (PEMA) among carbon compounds having a glass transition temperature (Tg) of 200 ° C or less. It is preferable to include any one or more selected from the group to be. More preferably, the use of a carbon compound having a glass transition temperature (Tg) of 100 to 150 ° C, polymethylmethacrylate (PMMA), or polytetrafluoroethylene (PTFE) may lower the surface adhesion at the buffer layer interface.

Since the buffer layer includes a first carbon compound having a glass transition temperature (Tg) of 200 ° C. or lower, the buffer layer may be separated in the fourth step, which will be described later, in the separation process of the release layer 10 and the first transparent conductive layer 20. Good for changing properties and shapes. If the glass transition temperature exceeds 200 ℃ there is a problem that a relatively high temperature and time is required during curing. In addition, materials with low glass transition temperature are suitable for process price and yield during roll-to-roll and continuous process.

The second carbon compound is at least one selected from the group consisting of a metal ion polymer, a vinyl-ketone copolymer, and an ethylene-CO copolymer among the carbon compounds decomposed by ultraviolet rays. It is preferable to include.

In the separation process of the release layer 10 and the first transparent conductive layer 20 in the fourth step, which will be described later, the buffer layer contains a second carbon compound decomposed by ultraviolet light, the first transparent conductivity can be easily achieved by a simple treatment. There is an advantage in that the layer 20 can be separated.

The metal oxide has an advantage of easy control of surface tension and surface energy by atoms substituted at the interface, and can be easily controlled by UV / ozone and plasma treatment. Accordingly, the adhesiveness and adhesiveness of the interface can be controlled and exhibits the property of easily transferring different materials.

Metal oxides are thermodynamically very stable materials up to 2000 ° C in almost all low-adhesive atmospheres. Yttrium oxide (Y ₂ O ₃ ), zirconia (ZrO ₂ ), alumina (Al ₂ O ₃ ), and boron nitride ( It is preferable to include any one or more selected from the group consisting of BN), titanium nitride (TiN) and silicon oxide (SiO ₂ ).

In addition, the present invention is a concave or convex surface pattern on the surface of the first transparent conductive layer 20 through the release layer 10 including the substrate (11, 12, 13) patterned on the surface as shown in FIG. Can be formed. For example, the surface of the first transparent conductive layer of the transmissive substrate finally transferred through the fourth step of the method of manufacturing a translucent substrate by controlling the surface shape when the buffer layer is formed on the substrate 13. The shape can be controlled. For example, when a wave pattern is formed in the buffer layer to stack and separate the first transparent conductive layer or the like, the wave pattern is transferred to the first transparent conductive layer.

When the organic light emitting device is manufactured by stacking a light emitting layer and a reflective electrode on a light transmissive substrate including a first transparent conductive layer 20 having a concave or convex surface pattern as shown in FIG. Is increased to increase the light emitting area, and can also provide an effect of increasing the luminous efficiency by acting as a light extraction. In addition, when manufacturing an organic solar cell by stacking a photoactive layer and a metal electrode on the light-transmissive substrate, it is possible to increase the light receiving area of the sunlight, and also provide a light collecting role to provide an effect of improving the power generation efficiency.

As a method of forming the irregularities on the substrate or the buffer layer, a method of etching using a mask using atmospheric pressure and an 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 formed to 100nm to 10μm. When the buffer layer is formed below 100 nm, there is a problem of unstable chemical corrosion resistance and surface uniformity, and when the buffer layer is formed above 10 μm, surface unevenness and curing time are prolonged, thereby causing a process problem. More preferably, it is 400 nm-600 nm.

The first step of manufacturing a light-transmissive substrate according to an embodiment of the present invention is a bar coating, a slot die coating, a spray coating on the substrate 13 using a buffer solution. Buffer layer sheets are formed separately using a coating method such as spin coating, spin coating, or the like, or when the flexible substrate is used as the substrate 13, a coating and heat treatment method using a buffer solution in a roll-to-roll process The buffer layer can be formed, and the surface shape can be adjusted.

Step 2-1 of manufacturing the light transmissive substrate according to an embodiment of the present invention is a step of forming the first transparent conductive layer 20 on the release layer 10, the first according to an embodiment of the present invention 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 it may be formed using any one or more selected from ZnO (Zinc Oxide), SnO ₂ (Tin Oxide), TiO ₂ , Al ₂ O ₃ and a solid solution thereof, wherein F, Al, Ga, In , Si or the like is preferably used to form the first transparent conductive layer 20.

The thickness of the first transparent conductive layer 20 is preferably formed in 5nm to 100nm. If the thickness is less than 5nm, there is a problem in that the crystallinity of the thin film is inferior, and if the thickness is formed over 100nm, there is a problem in that surface cracks occur when folding or bending due to a decrease in flexibility. More preferably, it is 5 nm-20 nm.

In the second step of manufacturing the light transmissive substrate according to the embodiment of the present invention, the first transparent conductive layer 20 is formed on the release layer 10 by using spin coating, or the flexible substrate. When using may be formed through deposition on a roll-to-roll process (deposition), but is not limited thereto.

In the method of manufacturing a light-transmitting substrate according to the embodiment of the present invention, as shown in FIGS. 6 to 8, the second transparent conductive layer 30 is formed on the first transparent conductive layer 20. 9 and 10, a light transmissive substrate including a first transparent conductive layer 20, a second transparent conductive layer 30, and a base polymer layer 50 can be manufactured, and an organic light emitting device, etc. When used as a light-transmitting electrode of the electrical conductivity and light scattering effect.

In the method of manufacturing a light-transmissive substrate according to an embodiment of the present invention, the polymer coating layer 32 covering the conductor 31 and the conductor 31 after forming the first transparent conductive layer 20 on the release layer 10 is provided. Since the conductor 31 is connected to the first transparent conductive layer 20 by forming a second transparent conductive layer 30 including a) to prepare a light-transmissive substrate 100 having excellent electrical conductivity and even 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 the 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 size range, there is a problem that the electrical conductivity is lowered, and if it exceeds, there is a problem that the light transmittance is lowered. The metal mesh pattern 312 means a pattern in the form of a mesh of metal.

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 coating the polymer with a polymer. More specifically, when the metal nanowires 311 are included, the ink composition containing the metal nanowires 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 metal mesh pattern 312 may be formed by printing the metal on the first transparent conductive layer 20 using a metal paste or ink and then baking the same to form a metal mesh pattern 312. Can be.

The transparent substrate according to the present invention may include a second transparent conductive layer 30 between the first transparent conductive layer 20 and the base polymer layer 50 to compensate for the conductivity of the first transparent conductive layer 20. By having a light extraction function, it is possible to provide a light-transmissive substrate that can be excellently 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 metal particles 313 have a size of 100 to 600 nm. If it is less than 100nm, there is a problem that the scattering characteristics are lowered, and if it exceeds 600nm there is a problem of transmittance loss. The metal particles 313 are not limited in shape, such as spherical, elliptical, and amorphous, and may have protrusions on their outer surfaces. When the projections are provided on the outer surface, the projections have a size of 10 to 300 nm. If it is less than 10nm there is a problem of light scattering degradation, if it exceeds 300nm there is a problem of transmittance loss.

When the second transparent conductive layer 30 includes the metal nanowires 311 and the metal particles 313, an ink composition including the metal nanowires and the metal particles is coated on the first transparent conductive layer 20. After drying and curing, the second transparent conductive layer 30 as shown in FIG. 11 may 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 ( The ink composition containing the metal particles 313 is coated on the first transparent conductive layer 20 having the 312 formed thereon, dried and cured, and then coated with a polymer to form the second transparent conductive layer 30 as shown in FIG. 12. ) Can be formed.

Alternatively, the metal mesh pattern 312 may be first coated with a paste in which metal particles or metal oxide particles are dispersed, and then the entire layer including the first coated metal mesh pattern may be secondarily coated with a polymer. The second transparent conductive layer 30 as shown in 13 can be formed. In addition, when the metal mesh pattern 312 is coated, pores may be optionally formed in the paste to impart light extraction efficiency due to a change in scattering angle due to pores. In addition, by inserting the light extraction nanoparticles into the paste to place the light scattering particles around the metal mesh pattern 312, it is possible to increase the light extraction efficiency by the internal scattering. Light extraction nanoparticles, light scattering particles refers to metal particles or metal oxide particles.

When the second transparent conductive layer 30 includes the metal mesh pattern 312, the metal mesh pattern 312 may be coated using a paste without including the metal particles 313, but may have a light extraction function. That is, the light extraction effect can be provided by coating in a shape having irregularities on the surface.

In addition, by selectively coating the surface of the metal mesh pattern 312 using a metal oxide using xenon light, ZnO, TiO ₂ , SiO ₂ , SnO ₂ , Al ₂ O ₃ It is possible to provide a light extraction effect by coating various oxides.

The metal of the metal nanowires 311, the metal mesh pattern 312, and the metal particles 313 included in the second transparent conductive layer 30 may be any conductive material. More typically, silver (Ag), gold (Au), copper (Cu), platinum (Pt), iron (Fe), nickel (Ni), cobalt (Co), zinc (Zn), titanium (Ti), chromium And those selected from the group consisting of (Cr), aluminum (Al), palladium (Pd), and combinations thereof. Preferably silver (Ag) is used. Silver (Ag) reflects light as a metal and has a low transmittance, but corresponds to a reflective electrode (for example, an aluminum (Al) metal electrode) when the translucent substrate according to the present invention is used as a translucent electrode of an organic light emitting element. Because it reflects light to each other, it actually reduces the light loss inside the device.

The thickness of the second transparent conductive layer 30 is 100 nm to 10 μm. If it is less than 100nm, there is a problem of lowering the conductivity, and if it exceeds 10μm, there is a problem of loss of transmittance. When light reaches the surface of the metal nanowires and metal particles, the light may be scattered through the metal nanowires and the metal particles, so that when used as a light transmitting electrode of the organic light emitting device, the light extraction efficiency may be increased. In particular, the metal particles may have projections on the outer surface to scatter light having a wider band. In addition, the adhesion to the first transparent conductive layer 20 on which the second transparent conductive layer 30 is formed can be improved.

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

In the second step of manufacturing the light transmissive substrate according to the embodiment of the present invention, the second transparent conductive layer 30 is formed on the first transparent conductive layer 20 by using spin coating. In the case of using a flexible substrate, an ink composition including metal nanowires or metal particles may be coated and dried on a roll-to-roll process, but is not limited thereto. In addition, the metal mesh pattern may be formed as the second transparent conductive layer by using photolithography.

According to the method of manufacturing a light transmissive substrate according to an embodiment of the present invention, the first transparent conductive layer 20 is formed on the buffer layer, the second transparent conductive layer 30 sequentially on the first transparent conductive layer 20. By forming the metal nanowires 311 and the metal particles 313 of the second transparent conductive layer 30 is located closer to the first transparent conductive layer 20 by gravity, thereby improving electrical conductivity and light extraction. The light transmissive electrode which is excellent in efficiency can be provided.

The method of manufacturing the light transmissive electrode according to the embodiment of the present invention further includes a step 2-3 of manufacturing the light extraction layer 40 on the second transparent conductive layer 30 as shown in FIGS. 14 and 15. As shown in FIG. 16, the light transmissive substrate 100 including the first transparent conductive layer 20, the second transparent conductive layer 30, the light extraction layer 40, and the base polymer layer 50 may be manufactured. When used in a light-transmitting substrate of an organic light emitting device, the light extraction function is possible, and thus the second transparent conductive layer 30 having a function of a conductor can be complemented in terms of function, and the metal included in the second transparent conductive layer 30 The nanowires 311, the metal mesh pattern 312 or the metal particles 313 may be impregnated or coated by the light extraction layer 40, thereby providing the metal nanowires 311, the metal mesh pattern 312 or the metal particles. It is possible to solve the problem of deterioration in reliability caused by sulfidation and oxidation of 313.

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

In addition, the light extraction layer 40 may be formed on the metal mesh pattern 312 formed as the second transparent conductive layer 30, in this case, coated with an oxide, nitride or sulfide of a metal or the average diameter of 50 to 500nm It may be a layer in which the scattering particles of oxides, nitrides or sulfides of the metal of the compound are inserted. They can also be formed into a composite layer.

The light extraction layer 40 may have a protrusion shape or a pattern shape, and the thickness thereof is 100 nm to 600 nm. If it is less than 100nm there is a problem of low light scattering effect, if it is more than 600nm there is a problem of light transmittance reduction. More preferably, it is 100-300 nm.

In the second to third steps of manufacturing the light transmissive substrate according to the embodiment of the present invention, the light extraction layer 40 is formed on the second transparent conductive layer 30 using spin coating, In the case of using the flexible substrate, an ink composition including an oxide, a nitride, a sulfide, or a mixture of metals may be applied and heat-treated in a roll-to-roll process, but is not limited thereto.

A third step of manufacturing a light transmissive substrate according to an embodiment of the present invention is the base polymer layer 50 on the first transparent conductive layer 20, the second transparent conductive layer 30 or the light extraction layer 40 As a step of forming a flexible light-transmitting substrate 100 can be manufactured through a roll-to-roll (roll to roll) process that is more simplified and reduced cost.

The base polymer layer 50 may be formed of polyimide (PI), polyethylene terephthalate (PET), polycarbonate (PC), polyether sulfone (PES), polyethylene naphthalate (PEN), poly acrylate (PA), polyurethane acrylate (PUA), and PDMS (PDMS). polydimethyl siloxane) and a metal thin film. It is preferable to form using PI which is excellent in chemical resistance, heat resistance, etc.

The base polymer layer 50 may have a thickness of 0.1 mm to 3 mm. In the case of forming less than 0.1mm, there is a problem in that the bearing capacity is low as a mother substrate, and in the case of forming more than 3mm, flexibility is reduced. More preferably, it is 0.2 mm-0.5 mm.

The third step of manufacturing a light-transmissive substrate according to an embodiment of the present invention is the step of 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 formed by applying and heat-treating the polymer composition in a roll-to-roll process, but is not limited thereto.

A fourth step of manufacturing a light transmissive substrate according to an embodiment of the present invention is a step of detaching the release layer 10, and separating the release layer 10 from the first transparent conductive layer 20 ( The light-transmitting substrate 100 including the first transparent conductive layer 20 and the base polymer layer 50, the first transparent conductive layer 20, the second transparent conductive layer 30 and the base polymer layer 50 are transferred to each other. A transparent substrate 100 including a transparent substrate 100, a first transparent conductive layer 20, a second transparent conductive layer 30, a light extraction layer 40 and a base polymer layer 50 To provide.

In addition, when the buffer layer is formed on the substrate as the release layer 10, the first transparent conductive layer 20 is transferred to the surface of the first transparent conductive layer 20 in the same manner as the surface of the buffer layer. Since the shape is transferred, the surface shape of the manufactured light-transmissive substrate 100 can be controlled.

In the fourth step of manufacturing a light-transmissive substrate according to an embodiment of the present invention can be stably separated by lowering the adhesive strength with the first transparent conductive layer 20 by selectively changing the properties by light irradiation treatment to the buffer layer through a light source. However, it is not limited thereto. The buffer layer according to an embodiment of the present invention is a material such as the first carbon compound, the second carbon compound, the metal oxide mentioned above, that is, the carbon compound having a glass transition temperature of 200 ° C. or less, the carbon compound decomposed by ultraviolet rays, and the adhesiveness. Due to the low metal oxides, there is an advantage that it can be easily separated (transferred) without complicated processes or using a lot of energy.

As a light source that can be used for the light irradiation treatment, a xenon lamp, a halogen lamp, a HID lamp, a fluorescent lamp, a gas discharge lamp including a mercury lamp, or the like can be used, and it is possible to change the properties by applying heat above the glass transition temperature of the buffer layer. Any heat source can be used without limitation. Preferably, the use of xenon lamps is good for local energy transfer to form the light extraction layer without damaging the transparent conductive oxide layer and other materials.

18 illustrates a roll-to-roll manufacturing method of a light transmissive substrate according to an embodiment of the present invention.

In addition, the method of manufacturing a light-transmitting 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 translucent substrate surface including the separated first transparent conductive layer 20 may be removed by washing or plasma treatment using chemicals such as acetone and ethanol.

In the organic light emitting device 1000 according to another embodiment of the present invention, as shown in FIG. 19, the light emitting substrate 100 is formed as a light transmitting electrode according to the method of manufacturing a light transmitting substrate according to the embodiment of the present invention. 1 may be manufactured by sequentially stacking the organic light emitting layer 200 and the reflective electrode 300 on the transparent conductive layer 20.

The organic light emitting layer 200 is not particularly limited in specific materials and formation methods, and materials and formation methods well known in the art may be used, and deposition methods, solvent processes such as spin coating using various polymer materials. , Dip coating, doctor blading, screen printing, inkjet printing or thermal transfer.

The reflective electrode 300 may be formed by sputtering, e-beam evaporation, thermal evaporation, laser molecular beam epitaxy (L-MBE), and pulsed laser evaporation ( Pulsed Laser Deposition (PLD), any one of the physical vapor deposition (Physical Vapor Deposition, PVD); Thermal Chemical Vapor Deposition, Plasma-Enhanced Chemical Vapor Deposition (PECVD), Light Chemical Vapor Deposition, Laser Chemical Vapor Deposition, Metal- Chemical Vapor Deposition selected from any one of an Organic Chemical Vapor Deposition (MOCVD) and a Hydride Vapor Phase Epitaxy (HVPE); Alternatively, the layer may be formed using atomic layer deposition (ALD).

The reflective electrode 300 may be formed of one or more selected from magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, platinum, gold, tungsten, tantalum, copper, silver, tin, and lead. have.

The light transmissive substrate 100 according to the 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 first transparent conductive layer provided on the second transparent conductive layer. Layer 20.

As shown in FIG. 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 the first transparent conductive layer ( When the half adjacent to 20) is called the A region and the half adjacent to the base polymer layer 50 is called the B region, 60% or more of the conductors 31 are distributed in the A region. In particular, the conductor 31 is more preferably distributed in 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. In addition, the second transparent conductive layer 30 may further include metal particles 313 disposed adjacent to the first transparent conductive layer 20. The metal particles 313 are distributed at least 50% in region A of the second transparent conductive layer. More preferably, it may be formed to be distributed in 60% or 70% or more according to the manufacturing 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 for UV curing, resin for thermal curing, epoxy resin, or the like. have. Preferably, the conductor 31 may be coated using a resin for curing UV light.

The translucent substrate 100 according to the embodiment of the present invention may include the second transparent conductive layer 30 to compensate for the conductivity of the first transparent conductive layer 20. 1 Since it is disposed adjacent to the transparent conductive layer 20, it is possible to exhibit better characteristics of the auxiliary electrode. This is possible 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 the embodiment of the present invention.

In addition, the second transparent conductive layer 30 may be a layer in which the metal mesh pattern 312 is double coated with a polymer having a light extraction shape. The metal mesh pattern 312 joined on the first transparent conductive layer 20 is coated with a polymer having a light extraction shape, for example, a shape having irregularities on the surface thereof, and then double coated with a polymer coating layer 32. 2 form a transparent conductive layer.

 In addition, the second transparent conductive layer 30 may be a layer in which the metal mesh pattern is double coated with a polymer including light extraction particles. Therefore, the metal mesh pattern 312 joined on the first transparent conductive layer 20 is coated with a polymer including metal particles 313, and then double coated with a polymer coating layer 32 to form a second transparent conductive layer. do.

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

Liquid crystal display, electrochromic display (ECD), plasma display panel, flexible display, electronic paper, touch panel, etc., including a transparent substrate according to an embodiment of the present invention It is possible to provide a display device.

In addition, the light transmissive substrate according to an embodiment of the present invention can be used in an organic light emitting device or an organic solar cell. That is, the organic light emitting device may be provided by stacking the light emitting material layer 200 and the reflective metal layer 300 on the first transparent conductive layer 20 of the light transmissive substrate 100 of the present invention. An organic solar cell may be provided by stacking electrode layers.

When the second transparent conductive layer 30 of the light transmissive substrate according to the embodiment of the present invention includes a structure for extracting light, for example, a shape including light scattering or extracting light may be included, including metal particles. When it contains a polymer containing, it can be suitably used as an organic light emitting device for illumination.

Example

Example 1

Spin coating a buffer solution on a 0.6 mm glass substrate to form a buffer layer of 400 nm, forming a 10 nm transparent oxide layer by physical vapor deposition on the buffer layer, and a polymer including silver nanowires (Ag NW) on the transparent oxide. The ink composition is applied, dried and cured at 80 to 150 ° C. for 5 to 10 minutes to form an AgNW layer of 200 nm or less. After coating and drying a polyimide (PI) solution or a UV resin to form a polymer layer, a light-transmissive substrate was prepared by separating from the transparent oxide layer by changing (melting) the properties of the buffer layer using latent heat by light.

Example 2

A 0.2 mm 3 mm substrate film was wound on a roller to provide a continuous roll to roll process. First, the buffer layer solution was coated on the flexible substrate film, followed by heat treatment to form a sacrificial layer. The first transparent conductive layer was deposited, the silver nanowires were deposited and coated, and then dried at high temperature to form a second transparent conductive layer. Coating and heat treatment formed a base polymer layer. By irradiating light thereto, the flexible substrate was separated by melting the buffer layer to continuously prepare a light-transmissive substrate. 18 shows a roll-to-roll manufacturing process of this example.

Example 3

A 0.5 mm 3 mm substrate film was wound on a roller to provide a continuous roll to roll process. First, when the buffer solution is coated on the flexible substrate film and subjected to heat treatment, a buffer layer having a wave pattern is formed by centrifugal force by solution coating. 2, a transparent conductive layer was formed, and a polymer or UV resin solution was coated and a base polymer layer was formed by UV treatment. Here, the flexible substrate was separated by melting the buffer layer using a xenon lamp to continuously manufacture a light-transmissive substrate. The prepared light-transmitting substrate exhibited the same wave pattern as the surface shape of the buffer layer, and FIG. 18 shows a roll-to-roll manufacturing process of this example.

Comparative example

After coating and drying a polyimide (PI) solution on a carrier glass to prepare a PI film, a barrier coating film was formed thereon, and an ITO transparent electrode manufacturing process was performed to make a device, and then separated from the carrier glass to prepare a translucent electrode.

Experimental Example

(1) image measurement

21 is a photograph visually showing the flexibility of the light-transmissive substrate prepared according to the embodiment of the present invention.

22 is a surface optical image photograph taken in the direction of the first transparent conductive layer of the light-transmissive substrate prepared according to the embodiment of the present invention, Figure 23 is a SEM image photograph of the metal nanowires of the second transparent conductive layer can be confirmed Indicated.

FIG. 24 shows a SEM image photograph in which the surface shape of the first transparent conductive layer of the light transmissive substrate manufactured by controlling the surface shape of the buffer layer is controlled by a wave pattern.

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

FIG. 25 shows XRD measurement data of a light transmissive 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 light transmissive substrate including a first transparent conductive layer, a second transparent conductive layer, a light extraction layer, and a base polymer layer. The peak of ITO, ZnO peak, Ag peak, and CH peak Has

Figure 27 shows the component analysis data through the EDX of the light-transmissive substrate prepared according to an embodiment of the present invention, it can be seen that the components such as Si, C, O, Zn, Ag, In, Sn.

(3) Flatness (surface roughness) measurement

R _PV and R _MS were measured when the surface roughness of the first transparent conductive layer of the light-transmissive substrate prepared in Example was observed in a scan range of 10 μm × 10 μm using AFM (Atomic Force Microscope). The measurement results are shown in Table 1 below, and the surface AFM profiles are shown in FIG. 28. In addition, FIG. 29 shows an AFM image of a translucent electrode shape-controlled by a wave pattern.

 (4) Transmittance and Electrical Conductivity Measurement

The electrical conductivity was measured by measuring the surface resistance of the flexible light-transmitting substrate having various light extraction layer thicknesses prepared in Examples. ) Was measured using an ESP type probe having an inter-pin spacing 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 extraction 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
AverageThickness (nm)	124	186	214	256
Transmittance (%)	77.9	70.8	70.3	69.8
Haze (%)	10.3	47	49.8	54.6
SheetResistance (Ω / □)	5.88	55.35	30.4	13.9

Features, structures, effects, and the like illustrated in the above-described embodiments may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

Claims (15)

1. A method of manufacturing a light transmissive substrate comprising a first transparent conductive layer and a base polymer layer,

   A first step of preparing a release layer;

   Forming a first transparent conductive layer on the release layer;

   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 light transmissive substrate including a first transparent conductive layer and a base polymer layer.
2. The method of claim 1,

   The release layer is a transparent substrate manufacturing method comprising a substrate, a buffer substrate or a substrate including a buffer layer on one surface.
3. The method of claim 2,

   The fourth step is a step of separating the release layer from the first transparent conductive layer by changing the properties of the material constituting the release layer by irradiating light energy to the release layer.
4. The method of claim 2,

   The substrate is a method of manufacturing a light-transmitting substrate comprising a polytetrafluoroetylene substrate or a bulk polymerized polymethyl methacrylate (PMMA) substrate.
5. The method of claim 2,

   The buffer substrate is a light-transmissive substrate manufacturing method of a substrate formed by containing a carbon compound containing fluorine (F).
6. The method of claim 5,

   The carbon compound containing fluorine (F) is methyltrifluoropropyl siloxane (Methyltrifluoropropyl siloxane), methylfluoro (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 and a poly siloxane Southern any one method of manufacturing a transparent substrate a carbon compound selected from the group consisting of (poly siloxazane).
7. The method of claim 2,

   The buffer layer is a layer formed using any one or more selected from the group consisting of a first carbon compound, a second carbon compound, and a metal oxide,

   The first carbon compound includes a carbon compound having a glass transition temperature (Tg) of 200 ° C. or less,

   The second carbon compound is a method of manufacturing a light-transmitting substrate comprising a carbon compound decomposed by ultraviolet light.
8. The method of claim 7, wherein

   The first carbon compound is a light transmitting material including any one or more selected from the group consisting of polycarbonate (PC), polymethyl methacrylate (PMMA) polytetrafluoroethylene (PTFE), polyvinylchloride (PVC), polystyrene (PS), and polyethyl methacrylate (PEMA) Substrate manufacturing method.
9. The method of claim 7, wherein

   The second carbon compound is a method of manufacturing a light-transmitting substrate comprising at least one selected from the group consisting of a metal ion polymer, a vinyl-ketone copolymer and an ethylene-CO copolymer. .
10. The method of claim 7, wherein

    The metal oxide is in the 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 ) Translucent substrate manufacturing method comprising any one or more selected.
11. The method of claim 1,

    The first step is to prepare a release layer having a concave or convex surface pattern formed method.
12. The method of claim 1,

    Wherein the first step comprises the step of forming a surface pattern on the surface of the release layer through a mask etching using an oxygen plasma or a wet etching using an etching solution.
13. A method of manufacturing a light transmissive substrate comprising a first transparent conductive layer, a second transparent conductive layer, and a base polymer layer,

    A first step of preparing a release layer;

    Forming a first transparent conductive layer on the release layer;

    Forming a second transparent conductive layer on the first transparent conductive layer, the second transparent conductive layer including a conductor and a polymer coating layer covering the conductor;

    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 light transmissive substrate including a first transparent conductive layer and a base polymer layer.
14. A method of manufacturing a light transmissive substrate comprising a first transparent conductive layer, a second transparent conductive layer, a light extraction layer, and a base polymer layer,

    A first step of preparing a release layer;

    Forming a first transparent conductive layer on the release layer;

    Forming a second transparent conductive layer on the first transparent conductive layer, the second transparent conductive layer including a conductor and a polymer coating layer covering the conductor;

    Forming a light extraction layer on the second transparent conductive layer;

    Forming a base polymer layer on the light extraction layer; And

    And a fourth step of separating the release layer from the first transparent conductive layer to obtain a light-transmissive substrate including a first transparent conductive layer and a base polymer layer.
15. The method according to claim 1, 13 or 14,

    And a fifth step of removing the remaining release layer components by plasma treatment on the separated first transparent conductive layer after the fourth step.

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