WO2014148792A1 - Film de conversion de couleur comprenant une couche de revêtement inorganique et une couche de revêtement polymère, et son procédé de fabrication - Google Patents

Film de conversion de couleur comprenant une couche de revêtement inorganique et une couche de revêtement polymère, et son procédé de fabrication Download PDF

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WO2014148792A1
WO2014148792A1 PCT/KR2014/002264 KR2014002264W WO2014148792A1 WO 2014148792 A1 WO2014148792 A1 WO 2014148792A1 KR 2014002264 W KR2014002264 W KR 2014002264W WO 2014148792 A1 WO2014148792 A1 WO 2014148792A1
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color conversion
coating layer
oxide
conversion film
layer
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PCT/KR2014/002264
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English (en)
Korean (ko)
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한창수
우주연
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고려대학교 산학협력단
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/44—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/507—Wavelength conversion elements the elements being in intimate contact with parts other than the semiconductor body or integrated with parts other than the semiconductor body

Definitions

  • the present invention relates to a color conversion film that can improve physical, chemical, thermal and moisture stability, a method for manufacturing the same, and a light emitting device using the same.
  • a quantum dot is a semiconductor material with a crystal structure of several nanoscales and is composed of hundreds to thousands of atoms. Because quantum dots are very small, they have a large surface area per unit volume, most atoms are present on the surface of nanocrystals, and exhibit quantum confinement effects. By the effect of the quantum confinement it is possible to control the emission wavelength only by controlling the size of the quantum dots, it may have characteristics such as excellent color purity and high photoluminescence (PL) emission efficiency.
  • PL photoluminescence
  • quantum dots Due to these characteristics, quantum dots have been of considerable commercial interest and can be applied to various devices such as photonic devices, LEDs, biolabels, solar cells, field-effect transistors (FETs), and the like.
  • LEDs are becoming more and more important in modern life for various purposes.
  • conventional inorganic phosphors have a low luminous efficiency and low color rendering index, which prevents them from emitting light of various wavelengths close to natural light.
  • white light emitting devices using blue LEDs in combination with phosphor materials have been actively pursued. Since white light emitting devices using LEDs as light sources are expected to consume less power and have a longer usable life than conventional white light sources, they are used as backlights for liquid crystal panels, indoor and outdoor lighting fixtures, automotive panel backlights and automotive front lights. Development is underway toward applications in signal light sources, light sources in projection devices, and the like.
  • the quantum dots are dispersed in optically transparent LED encapsulants and then placed on top of the solid state LEDs.
  • the quantum dots must remain sufficiently dispersed in a single, and combined within the LED encapsulant without optical loss.
  • aggregation and quantification of quantum dots and oxidation and decomposition due to infiltration of harmful species may occur, resulting in reduced optical characteristics and lifespan.
  • An object of the present invention is to provide a color conversion film that can prevent the penetration of moisture and harmful species to improve physical, chemical, thermal and moisture stability.
  • Another object of the present invention to provide a method for producing the color conversion film.
  • Another object of the present invention to provide a light emitting device using the color conversion film.
  • Color conversion film of the present invention for achieving the above object is a transparent substrate; A color conversion emission layer coated with a color conversion emission material on an upper surface of the transparent substrate; And an inorganic coating layer coating a surface of the color conversion light emitting material and filling gaps between the color conversion light emitting materials.
  • a polymer coating layer may be further formed on the upper surface of the inorganic coating layer.
  • the transparent substrate may be one selected from the group consisting of a plastic substrate, a quartz substrate, and a glass substrate, and the color conversion light emitting material may be formed of a quantum dot (QD), an inorganic fluorescent material, an organic fluorescent material, an organic light emitting material, and a phosphorescent material. It may be one or more selected from the group.
  • QD quantum dot
  • the color conversion emission layer may have a thickness of about 10 nm to about 1000 nm.
  • the inorganic coating layer may be formed by ALD (Atomic Layer Deposition) deposition method.
  • ALD Atomic Layer Deposition
  • the inorganic coating layer is selected from the group consisting of aluminum oxide, silicon oxide, silicon nitride, silicon oxynitride, magnesium oxide, indium oxide, hafnium oxide, zinc oxide, tin oxide, titanium oxide, manganese oxide, tungsten oxide and magnesium fluoride 1 It may be a species, the thickness of the inorganic coating layer may be 0.5 to 500 nm.
  • the polymer coating layer may be formed of at least one polymer resin selected from the group consisting of silicone resins, epoxy resins, acrylic resins, polyurethane resins, and polyimide resins, and the thickness of the polymer coating layer may be 50 nm to 50 ⁇ m. have.
  • the manufacturing method of the color conversion film of the present invention for achieving the above another object comprises the steps of providing a transparent substrate; Forming a color conversion emission layer by coating a color conversion emission material dispersed in a solvent on an upper surface of the transparent substrate while heating the transparent substrate to a temperature below a phase change temperature of the substrate; And forming an inorganic coating layer on the color conversion emission layer by an atomic layer deposition (ALD) deposition method.
  • ALD atomic layer deposition
  • the method may further include forming a polymer coating layer by mixing one or more polymer resins on the inorganic coating layer and then coating the mixed polymer material.
  • the color conversion light emitting material may be at least one selected from the group consisting of quantum dots (QD), inorganic fluorescent materials, organic fluorescent materials, organic light emitting materials, and phosphorescent materials, and the inorganic coating layer may include aluminum oxide, silicon oxide, silicon nitride, and silicon oxynitride. It may be one selected from the group consisting of magnesium oxide, indium oxide, hafnium oxide, zinc oxide, tin oxide, tanitanium oxide, manganese oxide, tungsten oxide and magnesium fluoride.
  • QD quantum dots
  • inorganic fluorescent materials organic fluorescent materials
  • organic light emitting materials organic light emitting materials
  • phosphorescent materials and the inorganic coating layer may include aluminum oxide, silicon oxide, silicon nitride, and silicon oxynitride. It may be one selected from the group consisting of magnesium oxide, indium oxide, hafnium oxide, zinc oxide, tin oxide, tanitanium oxide, manganese oxide, tungsten oxide and magnesium fluoride
  • the polymer resin may be at least one selected from the group consisting of silicone resins, epoxy resins, acrylic resins, polyurethane resins, and polyimide resins.
  • the light emitting device of the present invention for achieving the above another object may include a color conversion film prepared above.
  • the color converting film of the present invention forms an inorganic coating layer on the color converting light emitting layer coated with the color converting light emitting material, thereby preventing diffusion and decomposition of the color converting light emitting material and effectively dissipating heat, and a polymer coating layer on the upper surface of the inorganic coating layer. It can improve the physical, chemical, thermal and moisture stability by forming a role as a secondary protective barrier to prevent the passage or diffusion of harmful species (eg oxygen, moisture, oxidant, free radicals, etc.). The two coatings make them less sensitive to the external environment and subsequent process steps.
  • harmful species eg oxygen, moisture, oxidant, free radicals, etc.
  • the color conversion film of the present invention to the light emitting device can be used to emit high brightness, long life, excellent long-term stability and various colors.
  • 1A is a cross-sectional view of depositing an alumina coating layer on a QD layer using an ALD deposition method according to an embodiment of the present invention.
  • 1B is a TEM image of a QD layer before the alumina coating layer is deposited.
  • Figure 1c is a TEM image after depositing an alumina coating layer in accordance with an embodiment of the present invention.
  • 1D is the EDX profile of the QD layer before the alumina coating layer is deposited.
  • 1E is an EDX profile after depositing an alumina coating layer in accordance with one embodiment of the present invention.
  • 1F is a cross-sectional TEM image after depositing an alumina coating layer in accordance with an embodiment of the present invention.
  • 1G is Al element EDX mapping after depositing an alumina coating layer in accordance with one embodiment of the present invention.
  • 2A to 2C are quantum yield graphs in which a color conversion film prepared according to an embodiment of the present invention and a film having only a QD layer before the alumina coating layer is deposited are changed according to various surrounding environments.
  • 3A to 3F are PL emission graphs in which a film including only a QD layer before the color conversion film and the alumina coating layer prepared according to an embodiment of the present invention is deposited is changed according to various surrounding environments.
  • 4A is a cross-sectional view of depositing an alumina coating layer and a polymer coating layer on a QD layer according to another embodiment of the present invention.
  • 4B is an optical absorption spectrum of the color conversion film prepared according to another embodiment of the present invention when changed to UV light.
  • Figure 4c is a PL emission graph that changes when the color conversion film prepared according to another embodiment of the present invention to UV light.
  • Figure 4d is a graph of quantum yield that is changed according to various environments the color conversion film prepared according to another embodiment of the present invention.
  • 5A is a graph of quantum yield in which the color change film prepared according to Comparative Example 1 is changed according to various environments.
  • 5b to 5d are PL emission graphs in which the color change film prepared according to Comparative Example 1 is changed according to various environments.
  • 6A is a perspective view of a structure of an LED device using a color conversion film manufactured according to another embodiment of the present invention.
  • Figure 6b is a display image and lighting characteristics of the LED device to which the color conversion film prepared according to another embodiment of the present invention.
  • 6C is an EL spectrum according to time when UV light is exposed to an LED device to which a color conversion film manufactured according to another embodiment of the present invention is applied.
  • 6D to 6F are graphs showing light emission intensity of the LED device to which three color conversion films are applied according to various environments.
  • the present invention relates to a color conversion film capable of improving physical, chemical, thermal and moisture stability, a method of manufacturing the same, and an LED using the same.
  • the color conversion film of the present invention is a transparent substrate; A color conversion emission layer coated with a color conversion emission material on an upper surface of the transparent substrate; And an inorganic coating layer coating a surface of the color conversion light emitting material constituting the color conversion light emitting layer and filling gaps between the color conversion light emitting materials.
  • a polymer coating layer may be further formed on the upper surface of the inorganic coating layer, and the polymer coating layer has a structure covering all of the inorganic coating layer in a capsule form.
  • the transparent substrate is not particularly limited as long as the transparency is greater than or equal to 30% and preferably 30 to 95% with respect to the irradiated light.
  • the transparent substrate is one selected from the group consisting of a plastic substrate, a quartz substrate, and a glass substrate.
  • the plastic substrate may include at least one selected from the group consisting of polyethylene terephthalate (PET), polyethylene (PE), polyimide (PI), polycarbonate (PC), and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • PE polyethylene
  • PI polyimide
  • PC polycarbonate
  • PEN polyethylene naphthalate
  • the color conversion light emitting layer is coated with a color conversion light emitting material that is nanoparticles on the upper surface of the transparent substrate, and is a layer in which voids are formed between the color conversion light emitting materials (left image of FIG. 1A). Since the color converting light emitting material emits light with a different color depending on the size, it is preferable to use a color converting light emitting material having a required size according to the color required for the device to be applied, but it is preferably nanoparticles having an average particle diameter of 3 to 15 nm.
  • the color conversion light emitting material may include at least one selected from the group consisting of quantum dots (QD), inorganic fluorescent materials, organic fluorescent materials, organic light emitting materials, and phosphorescent materials, and preferably QDs.
  • QD quantum dots
  • the method of coating the color conversion light emitting material on the upper surface of the transparent substrate may include spin coating, bar coating, dip coating, spray coating, etc., but it is preferable to spray coating in consideration of viscosity and uniformity.
  • the thickness of the color conversion light emitting layer is 10 to 1000 nm, preferably 50 to 200 nm. If the thickness of the color conversion light emitting layer is less than the lower limit, the light emission characteristics may be lowered. If the color conversion light emitting layer is greater than the upper limit, the inorganic material may not be sufficiently filled in the pores between the color conversion light emitting materials, This can take time and money.
  • the inorganic coating layer improves the conductivity and carrier mobility of the color conversion light emitting layer, suppresses diffusion and decomposition of the color conversion light emitting material, provides a rigid structure, and serves as a barrier for effectively dissipating heat, thereby improving heat resistance of the transparent substrate.
  • the group consisting of aluminum oxide, silicon oxide, silicon nitride, silicon oxynitride, magnesium oxide, indium oxide, hafnium oxide, zinc oxide, tin oxide, tanitanium oxide, manganese oxide, tungsten oxide and magnesium fluoride One kind selected from may be mentioned.
  • the thickness of the inorganic coating layer is 0.5 to 500 nm, preferably 5 to 100 nm, more preferably 5 to 20 nm. If the thickness of the inorganic coating layer is less than the lower limit, the inorganic material may not be filled in the pores between the color conversion light emitting materials. If the thickness is greater than the upper limit, the deposition time and the cost increase without improving the effect.
  • the inorganic coating layer may be coated using a conventional deposition method, but is preferably coated by ALD (Atomic Layer Deposition) deposition method.
  • ALD Atomic Layer Deposition
  • Conventional evaporation method is used to coat the surface of the color conversion material without filling the inorganic material in the pores between the color conversion materials, while ALD deposition method not only fills the pores between the color conversion material, but also the color conversion material This can be prevented from agglomeration.
  • ALD deposition The principle of ALD deposition is that one atomic layer is deposited by supplying a reactant carried by fluorinated gas (Ar) to a target to be deposited, and one reactant deposits a second reactant after chemisorption occurs on the deposition target. As a result of chemical adsorption, the thin film is formed.
  • the reactant A material when supplied, the reactant reacts with the surface of the deposition object to be chemisorbed.
  • the substance A reactant is deposited in the atomic layer on the surface of the object, the reaction is no longer performed even when a large amount of the substance A reactant gas is supplied by the self-limiting reaction.
  • a substance is removed to the outside by using a purge gas while the reactant of A substance no longer reacts.
  • the B material reactant when supplied in the same manner as the A material, the A material and the B material react with each other and are chemically adsorbed, and the reaction is no longer performed by the self-limiting reaction. At this time, remove the B substance to the outside through the removal gas. This process is called one cycle, and the cycle is repeated to deposit a film having a desired thickness.
  • the polymer coating layer serves as a secondary protective barrier to prevent the passage or diffusion of harmful species (eg, oxygen, moisture, oxidizing agents, free radicals, etc.) from the external environment. By effectively blocking the contact can ensure the stability and reliability of the color conversion film.
  • the polymer coating layer is formed of at least one polymer resin selected from the group consisting of silicone resins, epoxy resins, acrylic resins, polyurethane resins, and polyimide resins.
  • the thickness of the polymer coating layer is 50 nm to 50 ⁇ m, preferably 100 nm to 5 ⁇ m, more preferably 500 to 900 nm.
  • the thickness of the polymer coating layer is less than the lower limit, the performance as a secondary protective barrier may be reduced.
  • the thickness is greater than the upper limit, the deposition time and cost increase without improving the effect.
  • the polymer coating layer may be formed by spin coating, bar coating, dip coating, spray coating, etc., but is preferably formed by spin coating in consideration of viscosity and uniformity.
  • the most stable structure of the color conversion film thus prepared is a transparent substrate / color conversion light emitting layer / inorganic coating layer / polymer coating layer, and the next stable structure is a transparent substrate / color conversion light emitting layer / inorganic coating layer.
  • the color conversion film of the transparent substrate / color conversion light emitting layer / inorganic coating layer / polymer coating layer structure does not show a decrease in photoluminescence (PL) or quantum yield (QY) during 28 days of testing in a very rough environment.
  • the color conversion film of the present invention is a light emitting diode (LED), semiconductor laser (LD: Laser Diode), solid-state laser (Solid Laser), photon device, biolabels, solar cells, transistors (TFTs) Applicable to the device. Especially when applied to LED, it can be mounted on the top of host encapsulant for high brightness, long life, excellent long-term stability, and emitting various colors.
  • LED light emitting diode
  • LD Laser Diode
  • Solid Laser Solid Laser
  • photon device biolabels
  • solar cells solar cells
  • TFTs transistors
  • Color conversion film manufacturing method of the present invention comprises the steps of providing a transparent substrate; Forming a color conversion emission layer by coating a color conversion emission material dispersed in a solvent on an upper surface of the transparent substrate while heating the transparent substrate to a temperature below a phase change temperature of the substrate; And forming an inorganic coating layer on the color conversion emission layer by an atomic layer deposition (ALD) deposition method.
  • the method may further include forming a polymer coating layer by mixing one or more polymer resins on the inorganic coating layer and then coating the mixed polymer material.
  • the transparent substrate is a phase change temperature of the film (for example, 40 to 200 °C for quartz substrate, 40 to 300 °C for quartz and glass substrate) using a heating pad during coating to accelerate the evaporation of the solvent It is heated below.
  • a phase change temperature of the film for example, 40 to 200 °C for quartz substrate, 40 to 300 °C for quartz and glass substrate
  • an inorganic coating layer is formed on the color conversion light emitting layer using an ALD system. While using the ALD system, the temperature of the transparent substrate is 90 to 110 ° C., the operating pressure is 0.1 to 0.3 Torr, the pulse time is 40 to 60 ms, the purge time is 5 to 20 seconds, and the flow rate of argon, the carrier gas, is 40 to 70. sccm.
  • At least one polymer resin is mixed on the upper surface of the inorganic coating layer to coat the mixed polymer material to form a polymer coating layer. It may also be treated in a vacuum oven for 5-20 minutes at 0.5-2 bar to remove the bubbles.
  • the formed color conversion film is preferably cured by heat treatment at 100 to 150 ° C for 1 to 4 hours.
  • Trimethylaluminum trimethylaluminium, TMA, 97%) and in ALD system oxygen (PLUS200, QUROS) depositing an amorphous Al 2 O 3 in the QD layer using, for example, QD particles depositing Al 2 O 3 on the surface and between the QD particles, Fill the pores of Al 2 O 3 to form an alumina coating layer of 5, 10 and 20 nm thickness (thickness coated on the surface of QD particles), respectively, and heat-process at 115 ° C for 2 hours to color the substrate / QD / alumina structure.
  • a conversion film was prepared.
  • a method of depositing Al 2 O 3 using the ALD system is as follows.
  • the pressure in the chamber is maintained at a few mTorr using a vacuum pump, and then the pressure inside the chamber is adjusted through the N 2 remover.
  • the pressure in the chamber is preferably set to 0.1 Torr and the temperature of the substrate is set to 100 °C.
  • One layer of TMA material flowed through the gas injector TMA pipe for 3 seconds while the pressure inside the chamber was stabilized, and the remaining TMA material after the deposition reaction was washed off by the purge gas and was in strong physical bonding with the substrate. Form a layer made of TMA material.
  • O 2 flows through the O 2 pipe to the layer made of the TMA material formed on the surface of the substrate and generates plasma.
  • the TMA material layer and O 2 is subjected to a chemisorption reaction to form an Al 2 O 3 layer.
  • the pulse time is 50 ms
  • the purge time is 10 seconds
  • the flow rate of argon is 50 sccm.
  • thermosetting silicone resin mixture (mixing OE-6630 A and B in a weight ratio of 1: 4) on the top surface of the alumina coating layer in a vacuum oven for 10 minutes at 1 bar was spun at 500 rpm using a spin coater (Ace-200, Dong Ah Trade Corp.) for 120 seconds to form a 900 nm thick silicon polymer coating layer, followed by heat treatment at 115 ° C. for 2 hours to provide substrate / QD / alumina / A color conversion film of silicon polymer structure was prepared.
  • a spin coater Ace-200, Dong Ah Trade Corp.
  • thermosetting silicone resin mixture (mixing OE-6630 A and B in a weight ratio of 1: 4), 0.15 g of the thermosetting silicone resin mixture and the CdSe / CdS / ZnS core-multishell QD (Nanodot HE series, QD Solutions Co.) 0.0003 g of a QD dispersion of 0.1% by weight dispersed in 99.9% by weight hexane is mixed, and then the mixture is placed in a vacuum chamber to foam at 1 bar for 30 minutes to remove hexane. The mixture was coated on a glass substrate with a spin coater and then the solution was removed, followed by heat treatment at 115 ° C. for 2 hours to prepare a color conversion film of substrate / QD / silicone polymer structure. Finally, the color conversion film of the QD / silicon polymer structure is separated from the glass substrate.
  • Test Example 1 TEM image and EDX profile before and after alumina coating layer formation
  • FIG. 1A is a cross-sectional view of depositing an alumina coating layer on a QD layer using the ALD deposition method according to Examples 1 to 3 of the present invention
  • FIG. 1B is a TEM image of a QD layer before the alumina coating layer is deposited
  • FIG. 1A is a cross-sectional view of depositing an alumina coating layer on a QD layer using the ALD deposition method according to Examples 1 to 3 of the present invention
  • FIG. 1B is a TEM image of a QD layer before the alumina coating layer is deposited
  • FIG. 1d is an energy dispersive spectroscopy (EDX) profile of the QD layer before the alumina coating layer is deposited
  • Figure 1e is an embodiment of the present invention EDX profile after depositing an alumina coating layer with a thickness of 10 nm according to 2
  • Figure 1f is a cross-sectional TEM image after depositing an alumina coating layer with a thickness of 10 nm according to Example 2 of the present invention (scale bar: 10 nm)
  • 1G is an Al element EDX mapping after depositing an alumina coating layer at a thickness of 10 nm in accordance with Example 2 of the present invention.
  • an alumina coating layer was deposited on the QD layer (FIG. 1C) as compared to the QD layer (FIG. 1B) to pack more densely and the thin coating thickness appeared to be uniform in all areas.
  • Cd, Se, Zn, and S were detected on the EDX profile before the alumina coating layer was deposited (FIG. 1D), but Al was detected after the alumina coating layer was deposited (FIG. 1E).
  • an alumina coating layer covering the surface of the QD particles and an alumina coating layer filled with alumina with pores between the QD particles were identified. At this time, the crystal structure of the QD is maintained. It was also confirmed that the alumina coating layer covering the surface of the QD particles from the Al element EDX mapping and the alumina coating layer filled in the pores between the QD particles were the same structure (FIG. 1G).
  • Test Example 2 QY Changes for Color Converting Films (QD / Alumina) and Films with Only QD Layers in Various Environments
  • FIG. 2A is a quantum yield graph in which a film formed only of a QD layer before deposition of a color conversion film and an alumina coating layer prepared according to Examples 1 to 3 of the present invention is changed according to humidity and a thermal environment
  • FIG. 2B is an embodiment of the present invention.
  • Color conversion film prepared according to Examples 1 to 3 and the film formed only QD layer before the alumina coating layer is deposited is a quantum yield graph that changes according to UV light
  • Figure 2c is a color produced according to Examples 1 to 3 of the present invention It is a quantum yield graph in which a film in which only a QD layer is formed before the conversion film and the alumina coating layer is deposited is changed according to the thermal environment.
  • QY quantum yield
  • the QY of the film with only the QD layer (No ALD) before the alumina coating layer was deposited shows 55% less than that of the solution (QD dispersion, 74%) because the low QY is due to the surface oxidation and degradation of the QD. .
  • the QY is increased by 55% to 67% by increasing the excitation fluidity through passivation (covering the surface).
  • UV light When exposed to UV light (2 mW ⁇ cm ⁇ 2 at 352 nm), the QY of the color conversion film and the QD layer-only film (No ALD) according to the thickness of the alumina coating layer gradually decreases over time (FIG. 2B).
  • UV light can signal the thermal activation process by oxidation and maturation / sintering by electrons and holes that can participate in chemical reactions on the QD surface. This leads to morphological and chemical changes.
  • Test Example 3 PL Luminescence Changes for Color Converting Films (QD / Alumina) and Films with Only QD Layers in Various Environments
  • 3A is a PL emission graph in which a film in which only a QD layer is formed before the alumina coating layer is deposited is changed according to a thermal environment
  • FIG. 3B is a PL emission in which a color conversion film manufactured according to Example 2 of the present invention is changed according to a thermal environment
  • 3C is a graph showing a PL emission in which only the QD layer before the alumina coating layer is deposited is changed according to humidity and thermal environment
  • FIG. 3D is a color conversion film prepared according to Example 2 of the present invention.
  • 3E is a graph of PL emission changes according to the environment
  • FIG. 3E is a graph of PL emission in which a film formed only of a QD layer before the alumina coating layer is deposited is changed according to the UV light environment
  • FIG. 3F is a color manufactured according to Example 2 of the present invention. It is a PL emission graph in which the conversion film changes with the UV light environment.
  • 3A and 3B are PL emission graphs of a film having only a QD layer exposed to heat at 100 ° C. over time (No ALD) and a color conversion film prepared according to Example 2 coated with an alumina coating layer at a thickness of 10 nm.
  • 3C and 3D are PL emission graphs for a film formed only of a QD layer exposed to 85 ° C. heat and 85% relative humidity over time (No ALD) and a color conversion film prepared according to Example 2.
  • FIG. 1 ALD
  • PL strength of the film (No ALD) formed only QD layer was confirmed to decrease with time (Fig. 3c), PL strength of the color conversion film prepared according to Example 2 PL of the film (No ALD) formed only QD layer Although slightly increased compared to the strength, but not much improved stability (Fig. 3d).
  • 3E and 3F are PL emission graphs for a film formed only of a QD layer exposed to UV light over time (No ALD) and a color conversion film prepared according to Example 2.
  • the alumina coating layer provides strong passivation on the QD surface, but does not inhibit QD surface diffusion, oxidation or degradation in the color conversion film due to incomplete filling of the narrow gap space.
  • harmful species after alumina coating can be migrated to the surface of the QD through the alumina coating layer to cause consequent drops in oxidation, degradation and QY. Therefore, more surface coating is needed to produce a very stable color conversion film.
  • FIG. 4A is a cross-sectional view of depositing an alumina coating layer and a polymer coating layer on the QD layer according to Example 4 of the present invention
  • Figure 4b is an optical that the color conversion film prepared according to Example 4 of the present invention is changed when exposed to UV light
  • 4C is a graph showing the emission spectrum of the color conversion film prepared according to Example 4 of the present invention when exposed to UV light
  • FIG. 4D is a color conversion film prepared according to Example 4 of the present invention. It is a graph of quantum yield that changes according to various environments.
  • the color conversion film prepared according to Example 4 is formed so that the alumina coating layer is filled in the gap between the surface of the QD particles and the QD particles, covering the upper surface of the alumina coating layer, specifically the alumina coating layer A polymer coating layer is formed.
  • the QY of the color conversion film prepared according to Example 4 according to three different environments is about 66% of the trap passivation by the alumina coating layer, and the change to be ignored in QY is 28 Occurs after days.
  • the color conversion film prepared according to Example 4 is most stable with respect to the surrounding environment and is suitable for applications such as LED based light emitting devices. In addition, it was confirmed that the color conversion film prepared according to Example 4 is the most excellent than the color conversion film prepared according to Examples 1 to 3 and Comparative Example 1.
  • Test Example 5 QY and PL emission changes of the color change film prepared according to Comparative Example 1 in various environments
  • FIG. 5A is a graph of quantum yield in which the color change film prepared according to Comparative Example 1 is changed according to various environments
  • FIG. 5B is a PL emission graph in which the color change film prepared according to Comparative Example 1 is changed according to humidity and thermal environments
  • 5C is a PL emission graph in which the color change film manufactured according to Comparative Example 1 is changed according to a UV light environment
  • FIG. 5D is PL emission in which the color change film prepared according to Comparative Example 1 is changed according to a thermal environment. It is a graph.
  • 5A is a graph of quantum yield (QY) over time for a color change film prepared according to Comparative Example 1 exposed to various environments.
  • the initial QY of the color change film produced according to Comparative Example 1 is reduced to 43% due to the aggregation of QD and other side reactions in the silicone resin at a high temperature of 100 ° C. during film formation. Over time, the QY of the color change film prepared according to Comparative Example 1 exposed to 85 ° C. heat and 85% humidity and UV light did not significantly decrease. On the other hand, the QY of the color change film prepared according to Comparative Example 1 exposed at 100 ° C. was lowered by 30% or more after 28 days.
  • 5b to 5d are PL emission graphs for the color change film prepared according to Comparative Example 1 exposed to various environments over time.
  • the use of QDs has potential important advantages such as the emission wavelength, broad absorption characteristics, narrow emission band and the ability to adjust low dispersion. It is preferable to use the color conversion film (FIG. 4D) prepared in Example 4, which has less quantum efficiency than directly applying quantum dots to the LED capsule medium. Applying the color conversion film prepared in Example 4 as described above can provide a bright, long life, less sensitive LED under a variety of environmental conditions.
  • Figure 6a is a perspective view of the LED device structure using a color conversion film prepared according to Example 4 of the present invention.
  • the color conversion film prepared according to Example 4 used as a color conversion object was prepared using a blue LED chip (TKF 01B450 blue power die, a silicon sealant (30SHM, Okong)).
  • ⁇ max 455 nm, non-epoxy molding packages, Trikaiser).
  • Figure 6b shows the display image and the illumination characteristics of the LED device to which the color conversion film prepared according to Example 4 applied.
  • the color conversion film prepared according to Example 4 exhibits pale orange light, and the emitted light emits bright purple-red in combination with a blue LED chip and a red color conversion film.
  • FIG. 6C shows the EL spectrum over time when the LED device is fed 80 mA of forward current and exposed to UV light. After 28 days, it was confirmed that the red LED device based on the color conversion film prepared according to Example 4 was continuously shining brightly without decreasing the EL intensity.
  • Figure 6d shows the luminescence change over time for the three QD-LED exposed to UV light.
  • the initial light emission of the film (No ALD) based LED device having only the QD layer was 21 lm ⁇ W ⁇ 1, and the emission intensity greatly decreased over time.
  • the color conversion film-based LED device (red line) manufactured in Example 2 when the color conversion film-based LED device (red line) manufactured in Example 2 is used, the emission of light is increased than that of the film (No ALD) -based LED device having only a QD layer, but the emission intensity decreases with time.
  • the emission intensity (blue line) of the color conversion film-based LED device manufactured in Example 4 is increased compared to the color conversion film-based LED device manufactured in Example 2, and light emission is maintained for 28 days without change.
  • 6E is EL spectrum over time when exposed to 85 ° C. heat and 85% humidity.
  • the film (No ALD) -based LED device and the color conversion film-based LED device prepared in Example 2 decreased only with time, but the emission intensity decreased over time, but the color conversion film-based LED device manufactured in Example 4
  • the luminous intensity is the best of the three LED devices and lasts for 28 days without change.
  • 6F is the EL spectrum over time when exposed to 100 ° C. heat.
  • the film (No ALD) -based LED device and the color conversion film-based LED device prepared in Example 2 decreased only with time, but the emission intensity decreased over time, but the color conversion film-based LED device manufactured in Example 4
  • the luminous intensity is the best of the three LED devices and lasts for 28 days without change.
  • the color conversion film prepared in Example 4 greatly improves the long term stability of the light emission of the LED device.
  • the most stable color conversion film based LED device can be achieved by using the color conversion film prepared in Example 4.
  • TEM photographs were obtained using a TEM system (Tecnai G2 F30 STwin, FEI) at 300 kV, and cross-sectional TEM samples of color conversion films were prepared using dual-beams focused on ion-beam systems (NOVA200, FEI). It was.
  • EDS data were obtained from various parts of the total particle represented in the TEM image.
  • UV-vis spectrophotometer SD-1000, Scinco
  • fluorometer Fluorolog, Horiba Jobin Yvon
  • C-9920-02 Hamamatsu
  • the temperature and humidity chamber (TH-ME-065, JEIO Tech) is used to study the effects of heat and moisture on the color conversion film, and the color conversion film is a vacuum oven (OV-11, JEIO Tech) for thermal studies. ) Is provided inside.
  • UV lamps are used to illuminate the color conversion film with 352 nm light of 2 mW ⁇ cm ⁇ 2 .
  • EL and luminance are evaluated in the integrating sphere using an LED spectral light measurement system (CSLMS LED 1060, Labsphere) at 4V and 80 mA controlled by a Keithley 2400 digital source meter.
  • CSLMS LED 1060, Labsphere LED spectral light measurement system
  • the color change film of the present invention can act on liquid crystal panels, polarizers, backlight units, liquid crystal cells, and the like.

Abstract

La présente invention concerne un film de conversion de couleur comprenant une couche de revêtement inorganique et une couche de revêtement polymère, et son procédé de fabrication. La présente invention peut fournir un film de conversion de couleur qui comprend un substrat transparent, une couche luminescente de conversion de couleur formée par un matériau luminescent de conversion de couleur revêtu sur la surface supérieure du substrat transparent, et une couche de revêtement inorganique permettant de remplir des pores et des vides entre la surface du matériau luminescent de conversion de couleur formant la couche luminescente de conversion de couleur et le matériau luminescent de conversion de couleur, possédant de ce fait une excellente stabilité à l'air, à l'humidité, à la photo-oxydation et analogue.
PCT/KR2014/002264 2013-03-18 2014-03-18 Film de conversion de couleur comprenant une couche de revêtement inorganique et une couche de revêtement polymère, et son procédé de fabrication WO2014148792A1 (fr)

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KR1020130028648A KR101459718B1 (ko) 2013-03-18 2013-03-18 무기 코팅층 및 고분자 코팅층을 포함하는 색변환 필름 및 이의 제조방법
KR10-2013-0028648 2013-03-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018002809A1 (fr) * 2016-06-29 2018-01-04 Sabic Global Technologies B.V. Fabrication d'une bande de phosphore avec bande de dissipation de chaleur
CN111902745A (zh) * 2018-11-12 2020-11-06 株式会社Lg化学 色彩转换膜、以及包括其的背光单元和显示装置

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101642131B1 (ko) * 2014-12-09 2016-07-22 한국기계연구원 양자점 트랜지스터의 제조 방법
KR101748991B1 (ko) * 2015-03-27 2017-06-21 주식회사 엘지화학 발광 필름
US11024778B2 (en) 2015-06-10 2021-06-01 Research & Business Foundation Sungkyunkwan University Large scale film containing quantum dots or dye, and production method therefor
KR102544328B1 (ko) * 2017-12-22 2023-06-19 삼성디스플레이 주식회사 표시 장치 및 표시 장치의 제조 방법
TWI728546B (zh) 2018-11-12 2021-05-21 南韓商Ｌｇ化學股份有限公司 色彩轉換膜、製造其的方法、包含其的背光單元以及顯示器裝置
TW202024282A (zh) * 2018-11-12 2020-07-01 南韓商Ｌｇ化學股份有限公司 色彩轉換膜、製備其的方法、包含其的背光單元以及顯示器裝置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080068526A (ko) * 2007-01-19 2008-07-23 키스마트 코포레이션 파장 변환 구조 및 그의 제조방법과 용도
KR20090091552A (ko) * 2008-02-25 2009-08-28 한국과학기술연구원 백색 및 컬러 광 여기 발광시트 및 그의 제조방법
KR20120067167A (ko) * 2010-12-15 2012-06-25 한국과학기술연구원 색변환 발광시트 및 이의 제조 방법
KR20120074899A (ko) * 2010-12-28 2012-07-06 엘지전자 주식회사 광소자 및 이를 이용한 발광 다이오드 패키지, 백라이트 장치

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080068526A (ko) * 2007-01-19 2008-07-23 키스마트 코포레이션 파장 변환 구조 및 그의 제조방법과 용도
KR20090091552A (ko) * 2008-02-25 2009-08-28 한국과학기술연구원 백색 및 컬러 광 여기 발광시트 및 그의 제조방법
KR20120067167A (ko) * 2010-12-15 2012-06-25 한국과학기술연구원 색변환 발광시트 및 이의 제조 방법
KR20120074899A (ko) * 2010-12-28 2012-07-06 엘지전자 주식회사 광소자 및 이를 이용한 발광 다이오드 패키지, 백라이트 장치

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018002809A1 (fr) * 2016-06-29 2018-01-04 Sabic Global Technologies B.V. Fabrication d'une bande de phosphore avec bande de dissipation de chaleur
US10553830B2 (en) 2016-06-29 2020-02-04 Sabic Global Technologies B.V. Fabrication of phosphor film with heat dissipation film
CN111902745A (zh) * 2018-11-12 2020-11-06 株式会社Lg化学 色彩转换膜、以及包括其的背光单元和显示装置

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