WO2017074051A1 - Substrat transmettant la lumière et son procédé de fabrication - Google Patents

Substrat transmettant la lumière et son procédé de fabrication Download PDF

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Publication number
WO2017074051A1
WO2017074051A1 PCT/KR2016/012142 KR2016012142W WO2017074051A1 WO 2017074051 A1 WO2017074051 A1 WO 2017074051A1 KR 2016012142 W KR2016012142 W KR 2016012142W WO 2017074051 A1 WO2017074051 A1 WO 2017074051A1
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Prior art keywords
transparent conductive
conductive layer
layer
light
substrate
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PCT/KR2016/012142
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English (en)
Korean (ko)
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유영조
최윤수
박태헌
손윤상
장진탁
임영진
오희봉
김다은
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덕산하이메탈(주)
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Publication of WO2017074051A1 publication Critical patent/WO2017074051A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2105/00—Planar light sources
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2115/00—Light-generating elements of semiconductor light sources
    • F21Y2115/10—Light-emitting diodes [LED]
    • F21Y2115/15—Organic light-emitting diodes [OLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a light transmissive substrate and a method of manufacturing 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.
  • an organic light-emitting diode OLED
  • 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.
  • ITO tin-doped indium oxide
  • CNT nanotubes
  • metal nanostructures etc.
  • the present invention relates to a light transmissive substrate including a first transparent conductive layer, a second transparent conductive layer, and a light extraction layer, and an organic light emitting device including the same, and to a second transparent conductive layer including a conductor and a polymer coating layer covering the conductor. It is to provide a light-transmitting substrate having an improved light extraction function through the excellent electrical conductivity and light scattering effect by the layer structure and an organic light emitting device comprising the same.
  • the present invention is a light transmissive substrate comprising a transparent conductive layer, the light transmissive substrate, the base polymer layer; A second transparent conductive layer provided on the base polymer layer and including a conductor and a polymer coating layer covering the conductor; A first transparent conductive layer provided on the second transparent conductive layer, wherein a half of the second transparent conductive layer adjacent to the first transparent conductive layer is called an A region, and is adjacent to the base polymer layer. When half is referred to as a B region, a translucent substrate is provided in which 60% or more of the conductors are distributed in the A region.
  • the conductor provides a light transmissive substrate including a metal nanowire or a metal mesh pattern.
  • the polymer coating layer of the second transparent conductive layer provides a light-transmitting substrate further comprising metal particles or metal oxide particles.
  • the second transparent conductive layer may provide a light-transmissive substrate in which the metal mesh pattern portion is first coated by a polymer having a shape having irregularities on a surface thereof and secondly coated by a polymer coating layer.
  • the second transparent conductive layer provides a coated light-transmitting substrate in which the metal mesh pattern portion is first coated with a polymer including metal particles or metal oxide particles, and second coated with a polymer coating layer.
  • the second transparent conductive layer also provides a coated light-transmissive substrate, wherein the metal mesh pattern portion is first coated by a polymer including pores and secondly coated by a polymer coating layer.
  • a light transmissive substrate having a concave or convex surface pattern is provided on the surface of the first transparent conductive layer.
  • the present invention provides a display device including the light-transmitting substrate.
  • the present invention A light emitting material layer provided on the first transparent conductive layer of the light transmissive substrate; And a reflective metal layer provided on the light emitting material layer.
  • the present invention In another aspect, the present invention. A photoactive layer provided on the first transparent conductive layer of the light transmissive substrate; And a metal electrode layer provided on the photoactive layer.
  • the present invention relates to a light transmissive substrate including a first transparent conductive layer, a second transparent conductive layer and a light extraction layer and an organic light emitting device including the same, and a polymer covering a conductor and a conductor such as a metal nanowire or a metal mesh.
  • the metal nanowires and the metal particles of the second transparent conductive layer are located closer to the first transparent conductive layer, it is possible to provide a transparent electrode having improved electrical conductivity and excellent light extraction efficiency.
  • the second transparent conductive layer may further include metal particles to increase light extraction efficiency, and the metal particles may have projections on the outer surface to scatter light having a wider range.
  • a second transparent conductive layer between the first transparent conductive layer and the base polymer layer to complement the conductivity of the first transparent conductive layer, and having a light extraction function can be excellently used not only for display but also for lighting. It provides a transparent substrate.
  • the present invention can provide a process for manufacturing a light-transmitting substrate having a simpler and less cost by forming and separating the first transparent conductive layer, the base polymer layer, and the like on the release layer in the reverse order.
  • a flexible plastic substrate or a buffer layer 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. .
  • 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.
  • 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.
  • 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.
  • FIG. 18 illustrates a roll-to-roll manufacturing method of a light transmissive substrate according to an embodiment of the present invention.
  • FIG 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.
  • FIG. 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.
  • FIG. 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.
  • FIG. 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.
  • FIG 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.
  • the first step of preparing the release layer 10 is performed by using the first transparent conductive layer 20 on the release layer 10.
  • Translucent substrate manufacturing method 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 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.
  • Teflon (polytetrafluoroetylene) substrate a bulk polymerized polymethyl methacrylate (PMMA) substrate
  • PMMA polymethyl methacrylate
  • Each step process can be made in a continuous roll-to-roll method to increase productivity, reliability, and economics.
  • 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
  • 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
  • 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.
  • PC Polycarbonate
  • PMMA Polymethyl methacrylate
  • PTFE Polytetrafluoroethylene
  • PMMA Polymethyl methacrylate
  • PTFE Polytetrafluoroethylene
  • 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.
  • Tg glass transition temperature
  • the glass transition temperature exceeds 200 °C there is a problem that a relatively high temperature and time is required during curing.
  • 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.
  • 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.
  • 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.
  • 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.
  • the organic light emitting device 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.
  • 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.
  • 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 10 ⁇ m.
  • 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 ⁇ m, 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.
  • ZnO Zinc Oxide
  • SnO 2 Tin Oxide
  • TiO 2 Al 2 O 3
  • 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.
  • the first transparent conductive layer 20 is formed on the release layer 10 by using spin coating, or the flexible substrate.
  • spin coating or the flexible substrate.
  • the first transparent conductive layer 20 is formed on the release layer 10 by using spin coating, or the flexible substrate.
  • spin coating or the flexible substrate.
  • deposition may be formed through deposition on a roll-to-roll process (deposition), but is not limited thereto.
  • the second transparent conductive layer 30 is formed on the first transparent conductive layer 20.
  • 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.
  • an organic light emitting device etc.
  • 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 ⁇ m to 80 ⁇ m. 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.
  • 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.
  • 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.
  • 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.
  • the second transparent conductive layer 30 as shown in FIG. 11 may be formed by coating with a polymer.
  • 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.
  • 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.
  • pores may be optionally formed in the paste to impart light extraction efficiency due to a change in scattering angle due to pores.
  • Light extraction nanoparticles, light scattering particles refers to metal particles or metal oxide particles.
  • 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.
  • 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.
  • a reflective electrode for example, an aluminum (Al) metal electrode
  • the thickness of the second transparent conductive layer 30 is 100 nm to 10 ⁇ m. If it is less than 100nm, there is a problem of lowering the conductivity, and if it exceeds 10 ⁇ m, there is a problem of loss of transmittance.
  • the metal particles may have projections on the outer surface to scatter light having a wider band.
  • the adhesion to the first transparent conductive layer 20 on which the second transparent conductive layer 30 is formed can be improved.
  • the second transparent conductive layer 30 may be a layer including a metal mesh pattern having various patterns and line widths.
  • 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 ⁇ m is preferable because it exhibits a haze value of about 2% to 15% and a transmittance of about 70 to 90%.
  • the second transparent conductive layer 30 is formed on the first transparent conductive layer 20 by using spin coating.
  • 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.
  • the metal mesh pattern may be formed as the second transparent conductive layer by using photolithography.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the light extraction layer 40 is formed on the second transparent conductive layer 30 using spin coating,
  • 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
  • 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
  • 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 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.
  • 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.
  • 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.
  • a xenon lamp 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.
  • 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.
  • FIG. 18 illustrates a roll-to-roll manufacturing method of a light transmissive substrate according to an embodiment of the present invention.
  • 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.
  • 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).
  • ALD atomic layer deposition
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • the second transparent conductive layer 30 of the light transmissive substrate includes a structure for extracting light, for example, a shape including light scattering or extracting light may be included, including metal particles.
  • a shape including light scattering or extracting light may be included, including metal particles.
  • it contains a polymer containing it can be suitably used as an organic light emitting device for illumination.
  • 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.
  • 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.
  • a 0.2 mm 3 mm substrate film was wound on a roller to provide a continuous roll to roll process.
  • 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.
  • 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.
  • a 0.5 mm 3 mm substrate film was wound on a roller to provide a continuous roll to roll process.
  • 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.
  • 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.
  • PI polyimide
  • 21 is a photograph visually showing the flexibility of the light-transmissive substrate prepared according to the embodiment of the present invention.
  • Figure 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.
  • 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.
  • FIG. 29 shows an AFM image of a translucent electrode shape-controlled by a wave pattern.
  • 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. 230 show optical performance and electrical conductivity data according to the average thickness of the light extraction layer.

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Abstract

La présente invention concerne un substrat transmettant la lumière qui comprend : une couche conductrice transparente ; une couche polymère de base ; une seconde couche conductrice transparente disposée sur la couche polymère de base et comprenant un conducteur et une couche de revêtement polymère pour recouvrir le conducteur ; une première couche conductrice transparente disposée sur la seconde couche conductrice transparente. Si la moitié de la seconde couche conductrice transparente, adjacente à la première couche conductrice transparente, est appelée région A et la moitié adjacente à la couche polymère de base est appelée région B, au moins 60 % du conducteur est réparti dans la région A.
PCT/KR2016/012142 2015-10-28 2016-10-27 Substrat transmettant la lumière et son procédé de fabrication WO2017074051A1 (fr)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
KR100902561B1 (ko) * 2008-01-04 2009-06-11 한국기계연구원 투명 전극 제조방법
US20110197966A1 (en) * 2008-10-15 2011-08-18 Konica Minolta Holdings, Inc. Organic photoelectric conversion element and organic photoelectric conversion element manufacturing method
KR20130010471A (ko) * 2010-02-27 2013-01-28 이노바 다이나믹스, 인코포레이티드 표면 임베디드 첨가물을 갖는 구조 및 관련 제조 방법
KR20140118513A (ko) * 2013-03-29 2014-10-08 삼성전기주식회사 플렉서블/스트레처블 투명도전성 필름 및 그 제조방법
KR20150024184A (ko) * 2013-08-26 2015-03-06 제일모직주식회사 투명 도전체 및 이를 포함하는 광학표시 장치

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100902561B1 (ko) * 2008-01-04 2009-06-11 한국기계연구원 투명 전극 제조방법
US20110197966A1 (en) * 2008-10-15 2011-08-18 Konica Minolta Holdings, Inc. Organic photoelectric conversion element and organic photoelectric conversion element manufacturing method
KR20130010471A (ko) * 2010-02-27 2013-01-28 이노바 다이나믹스, 인코포레이티드 표면 임베디드 첨가물을 갖는 구조 및 관련 제조 방법
KR20140118513A (ko) * 2013-03-29 2014-10-08 삼성전기주식회사 플렉서블/스트레처블 투명도전성 필름 및 그 제조방법
KR20150024184A (ko) * 2013-08-26 2015-03-06 제일모직주식회사 투명 도전체 및 이를 포함하는 광학표시 장치

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