KR101733656B1 - Functional particle layer including quantum dot and preparing method thereof - Google Patents

Abstract

A functional particle layer containing quantum dots for next generation flexible solid state lighting, and a method for producing a functional particle layer containing the quantum dots.

Description

TECHNICAL FIELD [0001] The present invention relates to a functional particle layer containing quantum dots,

The present invention relates to a functional particle layer comprising quantum dots for next generation flexible solid state lighting and a method for producing functional particle layers comprising said quantum dots.

The development of the next generation display is being done through various efforts based on the development of technology for eco-friendliness, saving energy consumption and improvement of human life style.

Liquid-emitting displays (LEDs) and organic light emitting diodes (OLEDs) have been attracting attention as eco-friendly next-generation lights that replace existing incandescent lamps and fluorescent lamps.

In particular, since OLEDs are based on the realization of flexible lighting, wearable lighting, cut-off lighting, and transparent lighting technology, OLED demand and technology development for next-generation lighting devices is expanding.

However, in order to manufacture a lighting apparatus using a conventional OLED, a complicated long time manufacturing process is required under a high vacuum. As a result, not only the process cost is increased but also the lifetime and the quantum efficiency of the respective light emitting layers are different in the structure in which the multiple light emitting layers mixed with the three primary colors are used, so that the quality of the illumination depending on the use time of the product may be deteriorated.

In Korean Patent No. 10-1268532, a transparent first electrode, a first organic light emitting layer, and a transparent second electrode are stacked to form a first light emitting portion emitting light of a first wavelength, a transparent third electrode, a second organic light emitting layer, A second light emitting portion for emitting a second wavelength of light and stacked on the first light emitting portion, and a substrate surface, between the substrate and the light emitting body, and between the light emitting portions, And a phosphor that generates light of a different wavelength by receiving a wavelength of light generated in each of the light emitting units. However, the disadvantages of the conventional phosphor film are demanded to be added to the manufacturing process and the product; That is, the conventional method for producing a phosphor film is not preferable in terms of color rendering index, optical efficiency, optical characteristics, and warpability due to its thick thickness and non-uniformity.

The present invention is directed to a functional particle layer comprising quantum dots that can be used for next generation flexible solid state lighting and a method of making the same. In one embodiment of the present invention, the functional particle layer containing the quantum dots may include phosphor particles, non-fluorescent particles, or a mixture of phosphor particles and non-fluorescent particles. The light conversion layer used for illumination may include the quantum dot And a quantum dot capable of exhibiting white light having a high color rendering index (CRI), a large scattering angle and a high efficiency, and a method for producing the functional particle layer.

When a blue OLED device is manufactured using a functional particle layer or a film including a quantum dot according to an embodiment of the present invention, efficient white light or monochromatic light can be realized by a simple manufacturing method; The color rendering index, the optical characteristic and the light efficiency are significantly improved in comparison with the light of the OLED manufactured through the conventional phosphor film.

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

The first aspect of the present application provides a functional particle layer comprising quantum dots comprising a particle layer formed on a sticky polymer layer containing a quantum dot, wherein the particle comprises a fluorescent substance, a non-fluorescent substance, or a mixture of a fluorescent substance and a non- do.

According to a second aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising: applying a sticky polymer material mixed with quantum dots to a substrate to form a sticky polymer layer containing quantum dots; And forming a particle layer by arranging particles in the adhesive polymer layer containing the quantum dots, wherein the particles include a fluorescent substance, a non-fluorescent substance, or a mixture of a fluorescent substance and a non-fluorescent substance. And a manufacturing method thereof.

In one embodiment of the present invention, the effect of raising the light extraction efficiency in the OLED can be achieved by optimizing the light conversion layer used for illumination as the phosphor particle layer, and a uniform color conversion layer having a large area can be completed. In addition, the OLED can be manufactured by roll-to-roll through the functional particle layer according to an embodiment of the present invention, and the manufacturing cost can be reduced. Light having a high CRI value can be obtained by controlling the final wavelength depending on the type of phosphor such as yellow, green, and red, and the number of layers of the phosphor, and uniform scattering can be obtained by a uniform particle layer of the phosphor.

The adhesive polymer material including the quantum dot according to an embodiment of the present invention can be applied to a back light unit (BLU) of a LCD, an OLED, an LED, and a device in which they are used.

1 is a cross-sectional view of a functional particle layer including quantum dots in which particles are arranged in a sticking polymer material containing quantum dots according to an embodiment of the present invention.
FIGS. 2A to 2F are cross-sectional views of a particle layer including a green phosphor / red quantum dot according to one embodiment of the present invention, field emission scanning electron microscope (FE-SEM) photographs, electro luminescence EL) graph, and CIE (commission internationale de i'eclairage) values.
FIG. 3 shows optical spectra (optical spectrum) of a particle layer including a green phosphor / red quantum dot according to an embodiment of the present invention.
4A to 4D are coordinate diagrams of a cross-sectional view, a FE-SEM photograph, an EL graph, and a CIE value of a particle layer including a yellow phosphor / red quantum dot according to one embodiment of the present invention, respectively.
5A and 5B are cross-sectional and EL graphs of a tacky polymer layer comprising red and green quantum dots, respectively, according to one embodiment of the present application.
6A and 6B are cross-sectional and EL graphs of a particle layer comprising red and green quantum dots, respectively, according to one embodiment of the present application.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

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

Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms " about ", " substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) " or " step " used to the extent that it is used throughout the specification does not mean " step for.

Throughout this specification, the term " combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments and examples and drawings.

The first aspect of the present application provides a functional particle layer comprising quantum dots comprising a particle layer formed on a sticky polymer layer containing a quantum dot, wherein the particle comprises a fluorescent substance, a non-fluorescent substance, or a mixture of a fluorescent substance and a non- do.

In one embodiment of the present invention, the quantum dot may include, but is not limited to, an inorganic nanostructure.

In one embodiment of the present invention, the inorganic nanostructure may be a core-shell-ligand structure, but may not be limited thereto.

In one embodiment herein, the core-shell structures may be obtained by adding precursors of organometallics comprising shell materials to a reaction mixture comprising core nanocrystals, but are not limited thereto. In this case, the cores act as nuclei rather than growth after the nucleation-event, and the shells grow from their surface. The temperature of the reaction is kept low to favor the addition of shell material monomers to the core surface while preventing independent nucleation of the nanocrystals of the shell materials. Surfactants in the reaction mixture are present to induce controlled growth of the shell material and to ensure solubility. A uniform and epitaxially grown shell is obtained when there is a low lattice mismatch between the two materials.

For example, the material for preparing the core-shell luminescent nanocrystals may be Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaS, GaN, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4, Ge ₃ N ₄ , Al ₂ O ₃ , (Al, Ga, In) ₂ (S, Se, Te) ₃ , Al ₂ CO and combinations thereof. .

For example, the core-shell luminescent nanocrystals may comprise CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, or CdTe / ZnS , But may not be limited thereto. For example, the quantum dot may be a core-shell quantum dot having a core comprising CdSe and at least one encapsulating shell layer comprising CdS or ZnS, preferably at least one encapsulating shell layer comprising CdS and ZnS But is not limited to, at least one encapsulating shell layer comprising at least one encapsulating shell layer.

In one embodiment of the present invention, the ligands of the quantum dots include at least one selected from the group consisting of a glassy polymer, a silicone, a carboxylic acid, a dicarboxylic acid, a polycarboxylic acid, an acrylic acid, a phosphonic acid, a phosphonate, But are not limited to, those selected from the group consisting of a transition metal oxide, a transition metal oxide, a transition metal oxide, a transition metal oxide, a transition metal oxide, a transition metal oxide, an oxide semiconductor, a sulfide oxide, an amine oxide and an epoxide.

In one embodiment of the present invention, the half width of the light emitted from the quantum dot may be about 20 nm to about 80 nm, but may not be limited thereto. For example, the full width of the light emitted from the quantum dots may be from about 20 nm to about 80 nm, from about 20 nm to about 70 nm, from about 20 nm to about 60 nm, from about 20 nm to about 50 nm, nm, about 20 nm to about 30 nm, about 30 nm to about 80 nm, about 40 nm to about 80 nm, about 50 nm to about 80 nm, about 60 nm to about 80 nm, or about 70 nm to about 80 nm But may not be limited thereto.

In one embodiment of the present invention, the particle layer may include, but is not limited to, a monolayer or multilayer of particle layers arranged uniformly and densely.

In one embodiment of the present invention, the particles may include, but are not limited to, a phosphor, a non-phosphor, or a mixture of a phosphor and a non-phosphor.

For example, when the particles include a phosphor, the functional phosphor layer or film in which the phosphor particles are uniformly and densely arranged in a single layer can be formed. The surface of such a single-layer phosphor functional particle layer is covered with very densely arranged phosphor particles, and the amount of emitted light of the phosphor can be increased. In addition, the surface of the single-layer phosphor functional particle layer may have a curved or spherical surface of the phosphor particles themselves, thereby increasing the light scattering, thereby increasing light extraction from the fluorescent layer.

For example, when the particle contains a non-fluorescent substance, a functional non-fluorescent substance layer or film in which non-fluorescent substance particles are uniformly and densely arranged as a single layer can be formed. The surface of such monolayer non-fluorescent functional particle layer is covered by very densely arranged non-fluorescent particles and has a curved or spherical surface of the non-fluorescent particles themselves, thereby increasing the light scattering, thereby increasing the light extraction .

For example, the phosphor may be constituted by a rare earth metal element as a dopant in the inorganic nanostructure. At this time, the phosphor may include, but not limited to, a sulfide-based, an oxide-based, an oxynitride-based, or a nitride-based. In addition, the phosphor may include, but is not limited to, non-luminescent particles. The phosphors absorb blue light and emit other light except for blue light in the form of down-conversion, and the phosphor particles are placed in the outermost or inside of the adhesive polymer layer containing the quantum dots in a single layer or multilayer form Scattering, light extraction, and color conversion characteristics. In addition, the quantum dot may assist the light emitted from the phosphor to realize white light having high color purity or a high color rendering index of high quality.

In one embodiment of the invention, the size of the particles may be from about 1 [mu] m to about 30 [mu] m, but is not limited thereto. For example, by including particles having various sizes ranging from about 1 탆 to about 30 탆 in size, the particles can be arranged more densely in the formed particle layer to form a uniform single-layer particle layer, Such a uniform and dense monolayer can be repeatedly formed to easily form a multilayered dense and uniform functional particle layer.

For example, the size of the particles may range from about 1 micron to about 30 microns, from about 1 micron to about 25 microns, from about 1 micron to about 20 microns, from about 1 micron to about 15 microns, from about 1 micron to about 10 microns, From about 5 microns to about 30 microns, from about 10 microns to about 30 microns, from about 15 microns to about 30 microns, from about 20 microns to about 30 microns, or from about 25 microns to about 30 microns However, the present invention is not limited thereto.

In one embodiment of the present invention, when the phosphor is a phosphor having a particle size of about 1 탆 or less, it is undesirable because a large amount of defects per volume of the phosphor crystal may exist as compared with a grain size of the phosphor of about 1 탆 or less. In the case of the particle size, the defect per volume is not so large as compared with the particle size below that, and it is not preferable because it is difficult to produce a phosphor having a particle size of about 30 탆 or more, but it is not limited thereto.

In one embodiment of the present invention, the phosphor particles are not particularly limited, and particles of a phosphor known in the art can be used.

In one embodiment of the present invention, the phosphor particles may include, but not limited to, particles of an inorganic phosphor. For example, BaY ₃ Al ₅ O ₁₂ : In, Tg ₃ Al ₅ O ₁₂ : In, M ₂ SiO ₄ : In, AAlSiO ₄ : In, MSi ₂ O ₂ N ₂ : In, M ₂ Si ₅ N ₈ : ln, MAlSiN _3: it may be selected from inorganic materials, comprising phosphor material consisting of ln, and combinations thereof, but may not be limited thereto.

In one embodiment of the present invention, the phosphor particles may be such that the center of the main excitation wavelength of the phosphor particles is close to the wavelength position of the blue light source so as to effectively excite the blue light source, but the present invention is not limited thereto.

In one embodiment of the present invention, if the ratio of the center excitation wavelength of the normalized phosphor to the center position of the blue light source is less than about 30%, the effect as the light conversion layer may become insignificant, but may not be limited thereto .

In one embodiment of the present invention, the excitation efficiency of the phosphor particles may include at least about 30% of the wavelength at which the blue light source is located in the highest wavelength based on the excitation wavelength at about 300 nm to about 500 nm, But may not be limited thereto.

In one embodiment of the present invention, the center emission wavelength of the phosphor particles may be about 480 nm to about 780 nm, but the present invention is not limited thereto. For example, the emission wavelength of the phosphor particles may range from about 480 nm to about 780 nm, from about 480 nm to about 700 nm, from about 480 nm to about 650 nm, from about 480 nm to about 600 nm, from about 480 nm to about 550 nm , About 480 nm to about 500 nm, about 500 nm to about 780 nm, about 550 nm to about 780 nm, about 600 nm to about 780 nm, about 650 nm to about 780 nm, or about 700 nm to about 780 nm And may include, but is not limited to, an emission wavelength range of from about 500 nm to about 540 nm, or from about 620 nm to about 660 nm, which exhibits high efficiency. For example, when the emission wavelength of the phosphor particles is less than about 480 nm, the excitation wavelength of the phosphor can be largely deviated from the position of the emission wavelength of the blue light source due to stokes movement, and the emission wavelength of the phosphor is about 780 nm or more In this case, since the region is a near-infrared region, the emission color may not be distinguished by humans, but may not be limited thereto.

In one embodiment of the present invention, the quantum efficiency of the phosphor particles may be about 60% or more, but the present invention is not limited thereto. For example, the quantum efficiency of the phosphor particles may be at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90% Or more, but the present invention is not limited thereto. For example, if the quantum efficiency of the phosphor particles is less than about 60%, the efficiency of the final flexible solid state illumination may be significantly reduced, but may not be limited thereto.

In one embodiment of the present invention, the refractive index of the phosphor or non-phosphor particles may be about 1.3 or more, but the present invention is not limited thereto. For example, the refractive index of the phosphor may be about 1.3 or more, about 1.6 or more, or about 1.9 or more, but may not be limited thereto. For example, when the refractive index of the phosphor particles is less than about 1.3, the refractive index of the blue light source and the light source is significantly lower than that of the blue light source, thereby reducing the efficiency of reflection and scattering in the light distribution process. . An example of a preferred refractive index control is a light-path way emitted from the interior of the OLED to the outside if the refractive index of indium tin oxide (ITO), which is a typical anode material used in OLEDs, is equal to or higher than about 1.9 If it is lower than the reference, however, the light path can be inefficient due to refraction and reflection. As another representative example, when the refractive index of a glass as a representative OLED substrate is equal to or higher than about 1.5 standard, a light-path way emitted from the inside of the OLED becomes efficient, but when it is lower than the reference Refraction and reflection can lead to inefficiencies in the optical path. Also as another example, one possible glass used as the OLED substrate (glass, SiO _2), aluminum oxide _{(Al 2 O 3), PET} (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), PES (polyethylene succinate) , And PI (polyimide) is about the same or higher than about 1.5, about 1.7, about 1.66, about 1.5 to about 1.75, about 1.5 to about 1.58, about 1.5 to about 1.66, and about 1.5 to about 1.66 A light-path way that is emitted from the inside of the OLED becomes efficient. However, if it is lower than the reference, the light path can be inefficient due to refraction and reflection.

In one embodiment of the present invention, the adhesive polymer may use any adhesive or adhesive polymer materials known in the art without particular limitation. For example, the adhesive polymer may include, but is not limited to, a silicone polymer, an epoxy polymer, an acrylic polymer, and combinations thereof.

In one embodiment of the present invention, the refractive index of the adhesive polymer layer may be about 1.0 or more, but may not be limited thereto.

In one embodiment of the present invention, the permeability of the adhesive polymer layer may be about 85% or more, but may not be limited thereto.

In one embodiment of the present invention, the thickness of the adhesive polymer layer may be from about 30% to about 300% of the particle size, but is not limited thereto. For example, the thickness of the adhesive polymer layer may range from about 30% to about 300%, from about 30% to about 250%, from about 30% to about 200%, from about 30% to about 150% About 50% to about 300%, about 50% to about 250%, about 50% to about 200%, about 50% to about 150%, or about 50% About 100%, but may not be limited thereto. When the thickness of the adhesive polymer layer is less than about 50% of the particle size, the thickness of the adhesive polymer layer is insufficient, and the thickness of the adhesive polymer layer is less than about 300% of the particle size, Which is undesirable. The thickness range of the adhesive polymer layer may be suitably selected in consideration of the refractive index and transmittance of the functional particle layer to be produced.

According to a second aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising: applying a sticky polymer material mixed with quantum dots to a substrate to form a sticky polymer layer containing quantum dots; And forming a particle layer by arranging particles in the adhesive polymer layer containing the quantum dots, wherein the particles include a fluorescent substance, a non-fluorescent substance, or a mixture of a fluorescent substance and a non-fluorescent substance. And a manufacturing method thereof.

In one embodiment of the present invention, the quantum dot may include, but is not limited to, an inorganic nanostructure.

In one embodiment of the present invention, the inorganic nanostructure may be a core-shell-ligand structure, but may not be limited thereto.

In one embodiment herein, the core-shell structures may be obtained by adding precursors of organometallics comprising shell materials to a reaction mixture comprising core nanocrystals, but are not limited thereto. In this case, the cores act as nuclei rather than growth after the nucleation-event, and the shells grow from their surface. The temperature of the reaction is kept low to favor the addition of shell material monomers to the core surface while preventing independent nucleation of the nanocrystals of the shell materials. Surfactants in the reaction mixture are present to induce controlled growth of the shell material and to ensure solubility. A uniform and epitaxially grown shell is obtained when there is a low lattice mismatch between the two materials.

For example, the material for preparing the core-shell luminescent nanocrystals may be Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaS, GaN, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4, Ge ₃ N ₄ , Al ₂ O ₃ , (Al, Ga, In) ₂ (S, Se, Te) ₃ , Al ₂ CO and combinations thereof. .

For example, the core-shell luminescent nanocrystals may comprise CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, or CdTe / ZnS , But may not be limited thereto. For example, the quantum dot may be a core-shell quantum dot having a core comprising CdSe and at least one encapsulating shell layer comprising CdS or ZnS, preferably at least one encapsulating shell layer comprising CdS and ZnS But is not limited to, at least one encapsulating shell layer comprising at least one encapsulating shell layer.

In one embodiment of the present invention, the ligands of the quantum dots include at least one selected from the group consisting of a glassy polymer, a silicone, a carboxylic acid, a dicarboxylic acid, a polycarboxylic acid, an acrylic acid, a phosphonic acid, a phosphonate, But are not limited to, those selected from the group consisting of a transition metal oxide, a transition metal oxide, a transition metal oxide, a transition metal oxide, a transition metal oxide, a transition metal oxide, an oxide semiconductor, a sulfide oxide, an amine oxide and an epoxide.

In one embodiment of the present invention, the quantum dot may be a solution colloid method for growing and growing the inorganic nanostructure, but the present invention is not limited thereto. The solution-based colloid method may include one or more ligands, and the ligand is capable of efficiently protecting the quantum dots from moisture and oxygen penetration, effectively forming a strong bond between the quantum dots and the ligand to encapsulate the quantum dots, Dispersed, and homogenized.

In one embodiment of the present invention, the method for producing a functional particle layer including the quantum dot may further comprise curing the polymeric adhesive layer.

In one embodiment of the present invention, the particle layer may include, but is not limited to, a monolayer or multilayer of particle layers arranged uniformly and densely.

In one embodiment of the present invention, the adhesive polymer may be a sticky or adhesive polymer material known in the art as a polymer for adhesion or adhesion of a phosphor or non-fluorescent particles, without any particular limitation. For example, the adhesive polymer can be classified into three types: first, it can be used in a method capable of fixing phosphor or nonphosphor particles on a polymer by sticking or adhering to the polymer through the adhesion or adhesion property of the polymer Polymer; Second, a polymer which can be used in a method of sticking or adhering the phosphor particles through the adhesion or adhesion property of the polymer and then completely curing the phosphor particles to fix the phosphor or the non-phosphor particles on the polymer; Third, the phosphor or nonphosphor particles are fixed or adhered to the polymer by sticking or adhering to the polymer through the adhesion or adhesion characteristic of the polymer, and then the hardening agent contained in the polymer naturally or externally stimulates (light, heat, vibration and chemical reaction) And then fixing the phosphor particles on the polymer.

In one embodiment of the present invention, the adhesive polymer may use any adhesive or adhesive polymer materials known in the art without particular limitation. For example, the adhesive polymer may be a silicone polymer, an epoxy polymer, an acrylic polymer, or a combination thereof, which may be used as an optically clear adhesive (OCA) or an optically clear resin (OCR) Preferred examples of the first type of the type may include PMMA dissolved in chloroform (methyl methacrylate), PS (polystyrene), and PC (polycarbonate) , Preferred examples of the second type may include acrylic adhesives, and preferred examples of the third type may include, but are not limited to, UV curable and PDMS (polydimethylsiloxane; including curing agent) materials.

In one embodiment of the present invention, the refractive index of the adhesive polymer layer may be about 1.0 or more, but the present invention is not limited thereto. For example, in the polymer material for arranging the particles in a single layer, the refractive index of the polymeric adhesive layer may be about 1.0 or more, about 1.3 or more, or about 1.5 or more, but the present invention is not limited thereto.

In one embodiment of the present invention, the permeability of the adhesive polymer layer may be about 85% or more, but may not be limited thereto. For example, the permeability of the polymeric adhesive layer may be about 85% or more, or about 90% or more, but the present invention is not limited thereto.

In one embodiment of the present invention, the thickness of the adhesive polymer layer may be from about 30% to about 300% of the particle size, but is not limited thereto. For example, the thickness of the adhesive polymer layer may range from about 30% to about 300%, from about 30% to about 250%, from about 30% to about 200%, from about 30% to about 150% About 50% to about 300%, about 50% to about 250%, about 50% to about 200%, about 50% to about 150%, or about 50% About 100%, but may not be limited thereto. The thickness range of the adhesive polymer layer may be suitably selected in consideration of the refractive index and transmittance of the functional particle layer to be produced.

In one embodiment of the invention, the thickness of the sticky or adhesive polymer layer is preferably D50 (Diameter 50) of the phosphor or non-phosphor particles (about 50% of the maximum value in the cumulative distribution of particles , But is not limited to, from about 50% to about 150% of the particle size. If the thickness of the sticky or adhesive polymer layer is less than about 30% of the D50 particle size of the phosphor or non-phosphor particles, the adhesive layer or adhesive layer is too thin compared to the particles to adhere, bond and fix phosphor or non- And it is not preferable because the amount of the pressure-sensitive adhesive or the adhesive is insufficient when forming the multi-layer phosphor or the nonphosphor particle layer. However, the present invention is not limited thereto. Further, when the thickness of the adhesive or adhesive polymer layer is about 300% or more of the D50 particle size of the phosphor or non-phosphor particle, several phosphors or non-phosphor particles may be completely buried in the same area of the adhesive or adhesive polymer layer The functional particle layer or the film is likely to be uneven, and the thickness of the whole phosphor or non-phosphor particle layer becomes thick, which is not preferable in terms of mechanical and optical properties, but may not be limited thereto.

1 is a cross-sectional view of a particle layer in which particles are uniformly and densely arranged in a sticky polymer layer containing quantum dots according to an embodiment of the present invention.

As shown in FIG. 1, a polymer material is used as an adhesive or a pressure-sensitive adhesive for particles to form a functional particle layer containing a quantum dot, and the fluorescent substance or non-fluorescent substance particles are uniformly and densely arranged in the polymer substance. The polymer material includes a quantum dot, and the polymer material including a quantum dot can be used on a substrate, a layer between particles and particles, or on a particle.

In one embodiment of the invention, the adhesive polymer layer comprising the quantum dot may be, but is not limited to, those produced by casting, spin coating, spray transfer, electron spinning, doctor blade, or R2R .

In one embodiment of the present invention, the phosphor particles are not particularly limited, and particles of a phosphor known in the art can be used.

In one embodiment of the present invention, the phosphor particles may include, but not limited to, particles of an inorganic phosphor. For example, BaY ₃ Al ₅ O ₁₂ : In, Tg ₃ Al ₅ O ₁₂ : In, M ₂ SiO ₄ : In, AAlSiO ₄ : In, MSi ₂ O ₂ N ₂ : In, M ₂ Si ₅ N ₈ : ln, MAlSiN _3: it may be selected from inorganic materials, comprising phosphor material consisting of ln, and combinations thereof, but may not be limited thereto.

In one embodiment of the present invention, in forming the phosphor or the non-fluorescent functional particle layer, the shape of the particles may be spherical monodisperse, and the distribution of the particles may be about 30% or more, for example, about 50% or more, but may not be limited thereto. By using the particles having such a particle size distribution, the functional particle layer to be formed can be formed more uniformly and densely. For example, when the particle size distribution of the D50 of the particles is less than about 30%, there is a high possibility that the shape of the phosphor can be cohered, thereby causing internal diffuse reflection in the particle layer, but may not be limited thereto.

In one embodiment of the invention, the size of the phosphor or non-phosphor particles may be, but is not limited to, uniform distribution of the particles from about 1 [mu] m to about 30 [mu] m. For example, the size of the phosphor or non-phosphor particles may be in a range of about 1 탆 to about 30 탆, or about 2 탆 to about 10 탆, but the present invention is not limited thereto. For example, a phosphor or a non-phosphor powder having a particle size of about 1 탆 or less or about 30 탆 or more can be used, but when the particle size is about 1 탆 or less, the phosphor or non- Phosphor particles having a particle size of about 30 mu m or more and having a particle size of about 30 mu m or more and having a particle size of not more than 30 mu m are not preferable, But it may not be limited thereto.

In one embodiment of the present invention, the phosphor particles arranged in the adhesive polymer layer form a high density layer, and the phosphor aperture ratio (the ratio of the area of the phosphor exposed on the surface to the area of the polymer) on the surface on which the phosphor layer is formed is about But it may be not less than 70%, preferably not less than about 90%. In addition, the phosphor particles act as light scattering particles, and the light extraction efficiency of the electroluminescent device can be increased by about 5% or more based on the single-layer phosphor particle layer.

In one embodiment of the invention, the phosphor particle layer may comprise a non-luminescent particle layer. The definition of the non-luminescent particle layer is a comparison of the intensity of luminescence brightness under the same amount of blue light based on the monolayer phosphor layer and the monolayer non-luminescent particle layer, .

The difference in the intensity of the luminescence intensity includes the element of the luminescence center (rare earth element, transition metal, interstitial impurity element, substitutional impurity element and defect, etc.) in the excessive amount of concentration in the inside of the crystal grains of the phosphor, Because it contains a light emitting element. In addition, the non-luminescent particles containing a very small amount of the light emitting element have little stoke-shift phenomenon, so that the light loss is minimized and the light extraction efficiency of the electroluminescent element acts mainly as optical scattering particles, Of the non-luminescent particle layer, and preferably about 40% or more. In addition, it is possible to control the color temperature of fine white light by forming a phosphor film containing phosphor particles and non-luminescent particles. Further, the color temperature can be controlled by controlling the concentration of the light emitting element in the crystal grains of the phosphor, the number of phosphor particle layers, and the combination of phosphors of different colors (the same phosphor particle layer).

In one embodiment of the invention, the phosphor or nonphosphor functional layer or film may be prepared by spin coating, doctor blade, spray transfer, or R2R process.

In one embodiment, the phosphor or non-phosphor functional layer or film can be applied to LCD BLU, LED lighting, LED display, OLED lighting, OLED display, billboard film, or plant factory LED.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto.

[ Example ]

Example  1: Green phosphor / Red Qdot Particle layer  Produce

A poly acrylate adhesive was coated on the substrate of the OLED of ITO / NPB / blue emitter / Alq ₃ / LiF / Al to a thickness of 10 μm and the Lu ₃ Al ₅ O ₁₀ : Ce green phosphor was coated with a small amount of pressure Was adhered to the adhesive polymer. The phosphor particles not bonded through the gas purging were removed to prepare a single-layer phosphor particle layer. In addition, the above process was repeated twice to prepare a double-layered phosphor particle layer (the coating of the adhesive polymer on the single-layer phosphor particle layer was 50 탆 in the second process).

Red quantum dots dispersed with TOP (trioctylphosphine) and OA (oleic acid) ligands in a CdSe / ZnS multishell were used. The red quantum dot had an optical density of 2, and silicone (PDMS) and the red quantum dot were mixed at a ratio of 9: 1. The green (red) quantum dot-containing polymer layer (silicon) was spin coated on the prepared single layer and double layer phosphor particle layers to prepare a green phosphor / red quantum dot layer of a single layer (Sample 1) and a double layer (Sample 2).

The prepared sample 1 and sample 2 were placed on a bottom blue OLED to obtain a high-quality white light OLED.

A cross-sectional view of the green phosphor / red quantum dot particle layer obtained through the above process is shown in FIG.

As shown in FIG. 2A, the fluorescent layer includes a double-layered phosphor particle layer and a polymer layer including quantum dots on the fluorescent particle layer by a sticky polymer.

FIG. 2B is an FE-SEM photograph of a sample 1 coated with a polymer containing a quantum dot on a single-layer phosphor particle layer, and FIG. 2C is an FE-SEM photograph of a sample 2 coated with a polymer containing a quantum dot on a double phosphor particle layer. to be. As shown in Figs. 2B and 2C, the thickness of the sample 1 was 80 mu m and the thickness of the sample 2 was 60 mu m.

2D and 2E are the results of analyzing the electro luminescence (EL) of the sample 1 and the sample 2, respectively, and FIG. 2F is a graph showing the results of analysis of the values of the CIE (commission internationale de i'eclairage) Coordinate diagram.

The EL analysis results (the respective light emission efficiencies, the respective light emission efficiency change rates, the CIE x, y coordinates, the color rendering index) of the particle layers of the sample 1 and the sample 2 were measured by operating the blue light source of the OLED at about 5 V and under about 10 mA, Are shown in Table 1 below.

As shown in FIG. 2F, since sample 1 and sample 2 are used on a blue OLED, white light has x: 0.250, y: 0.256 CIE coordinates and x: 0.254, y: 0.276 CIE coordinates in sample 1 and sample 2, respectively . The color rendering index (Ra) and R9 of Sample 1 were 76.6% and 50.8%, respectively, and the color rendering index (Ra) and R9 of Sample 2 were 74.6% and 63.9% (Table 1).

FIG. 3 shows the results of improving the light extraction and the Lambald's sphere using the sample 1 and the sample 2 on the blue OLED.

As shown in FIG. 3, the half-width of the scattering of the sample 1 and the sample 2 was increased by about 50 ° compared with the half-width of the scattering of the blue light source.

Example  2: yellow phosphor / red Qdot Particle layer  Produce

Red quantum dots dispersed with TOP and OA ligands in a CdSe / ZnS multishell were used. The red quantum dot having an optical density of 2 was used, and the acrylic adhesive polymer and the red quantum dot were mixed in a ratio of 9: 1 to prepare the adhesive polymer layer containing the red quantum dot. YAG: Ce particles, which are yellow phosphors, were applied to the adhesive polymer layer containing the quantum dots prepared above, and the above steps were repeated to prepare a dual phosphor particle layer (Sample 3).

A cross-sectional view of the yellow phosphor / red quantum dot particle layer obtained through the above process is shown in FIG. 4A.

As shown in FIG. 4A, a double fluorescent layer is included in the adhesive polymer layer containing quantum dots.

The prepared sample 3 was placed on a bottom blue OLED to obtain a high-quality white light OLED.

FIG. 4B is an FE-SEM photograph showing a color conversion layer of an OLED manufactured using a dual yellow phosphor / red quantum dot particle layer according to an embodiment of the present invention.

As shown in FIG. 4B, it was confirmed that the applied phosphor particle layer formed a bending (acid and valley) structure on the surface of the sample 3. The curved structure of the surface makes it possible to more effectively emit the blue light and the color conversion light of the OLED.

4C and 4D are the coordinates of the CIE value and the result of EL analysis of the sample 3, respectively.

The EL analysis results (the respective light emission efficiencies, the respective light emission efficiency change rates, the CIE x, y coordinates, and the color rendering index) of the particle layer of the sample 3 were measured by operating the blue light source of the OLED at about 5 V and under about 10 mA, Respectively.

As shown in FIG. 4D, the light using the sample 3 and the blue OLED was about 5,400 K located at the coordinates of x: 0.34, y: 0.37 CIE, and the color rendering index (Ra) and R9 were 94% and 85% (Table 1). By using the red quantum dot in the adhesive polymer, Ra and R9 can be greatly improved, and an effective color conversion film can be produced by using the same.

Comparative Example  1: Red and green Quantum dot  Preparation of an adhesive polymer layer containing

Red and green quantum dots of optical density 2 dispersed with TOP and OA ligands in a CdSe / CdS / ZnS multishell were used. The acrylic adhesive polymer and the red and green quantum dots were mixed at a ratio of 9: 1 to prepare the adhesive polymer layer containing the red and green quantum dots. Using the prepared adhesive polymer layer, a layer having a thickness of 50 탆 was formed on a blue OLED by a bar coater (sample 4). The prepared sample 4 was placed on a bottom blue OLED to obtain a high-quality white light OLED.

FIG. 5A is a cross-sectional view of the adhesive polymer layer including the red and green quantum dots obtained through the above-described manufacturing process.

The EL analysis results (the respective light emission efficiencies, the respective light emission efficiency change rates, the CIE x, y coordinates, and the color rendering index) of the particle layer of the sample 3 were measured by operating the blue light source of the OLED at about 5 V and under about 10 mA, Respectively.

Example  3: Red Qdot  Adhesive polymer layer / green Qdot  Containing a sticky polymer layer Particle layer  Produce

Red and green quantum dots of optical density 2 dispersed with TOP and OA ligands in a CdSe / CdS / ZnS multishell were used. The acrylic adhesive polymer, the red quantum dot, the acrylic adhesive polymer, and the green quantum dot were mixed at a ratio of 9: 1, respectively, to prepare the adhesive polymer layer containing the red quantum dot and the green quantum dot. Using the prepared polymer layer including red and green quantum dots, a sticky polymer layer containing the red quantum dot having a thickness of 50 mu m was formed on a blue OLED by a bar coater, And an adhesive polymer layer containing the green quantum dots was formed on the adhesive polymer layer. Y ₃ Al ₅ O ₁₂ particles were coated on the prepared adhesive polymer layer to form a particle layer (Sample 5).

The prepared sample 5 was placed on a bottom blue OLED to obtain a high-quality white light OLED.

FIG. 6A is a cross-sectional view of a particle layer including a red quantum dot and a sticky polymer containing a green quantum dot obtained through the above-described manufacturing process.

FIGS. 5B and 6B show EL measurement results of white light obtained by using the blue OLEDs of Sample 4 and Sample 5, respectively, in one embodiment of the present invention.

As shown in FIG. 5B and FIG. 6B, the white light of Sample 5 showed light extraction of the red light portion by 94% as compared with the blue OLED by the coated particles. This was significantly improved compared with 59% of the sample 4, and different spectral shapes were observed in the red light portion as compared with the white light of the sample 4 because of the particle layer used in the sample 5. The light using the sample 4 and the sample 5 in the blue OLED was located at the CIE coordinates of x: 0.305, y: 0.349, x: 0.235 and y: 0.310, the color rendering index (Ra) was 72% -88% and 65%, respectively (Table 1).

The EL analysis results (the respective light emission efficiencies, the respective light emission efficiency change rates, the CIE x, y coordinates, and the color rendering index) of the particle layer of the sample 5 were obtained by operating the blue light source of the OLED at about 5 V and under about 10 mA, Respectively.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (19)

A functional particle layer comprising quantum dots comprising a particle layer formed on a sticky polymer layer containing a quantum dot,
The particles of the particle layer include a fluorescent substance, a non-fluorescent substance, or a mixture of a fluorescent substance and a non-fluorescent substance,
Wherein the particle layer comprises a multilayered particle layer which is uniformly and densely arranged,
The particle layer including the phosphor includes a non-luminescent particle layer including a light emitting element, and the non-luminescent particle layer acts as an optical scattering particle to increase light scattering and light extraction efficiency,
The particle layer is capable of adjusting the color temperature of the white light according to the concentration of the light emitting element in the particle layer, the number of particle layers including the fluorescent substance, or the combination of the fluorescent materials having different light colors,
Wherein the thickness of the adhesive polymer layer is 30% to 300% of the particle size.
A functional particle layer comprising a quantum dot.
The method according to claim 1,
Wherein the quantum dot comprises an inorganic nanostructure.
3. The method of claim 2,
Wherein the inorganic nanostructure is a core-shell-ligand structure.
delete The method according to claim 1,
Wherein the particle size is from 1 mu m to 30 mu m.
The method according to claim 1,
Wherein the refractive index of the particles is 1.3 or more.
The method according to claim 1,
The adhesive polymer may be a silicone-based polymer or an epoxy-based polymer. An acrylic polymer, and combinations thereof. The functional particle layer includes quantum dots.
The method according to claim 1,
Wherein the refractive index of the adhesive polymer layer is 1.0 or more.
The method according to claim 1,
Wherein the adhesive polymer layer has a transmittance of 85% or more.
delete Applying a sticky polymer material mixed with quantum dots to a substrate to form a sticky polymer layer containing quantum dots; And
And arranging the particles in the adhesive polymer layer containing the quantum dots to form a particle layer
A method for producing a functional particle layer comprising a quantum dot,
The particles of the particle layer include a fluorescent substance, a non-fluorescent substance, or a mixture of a fluorescent substance and a non-fluorescent substance,
Wherein the particle layer comprises a multilayered particle layer which is uniformly and densely arranged,
The particle layer including the phosphor includes a non-luminescent particle layer including a light emitting element, the non-luminescent particle layer acts as an optical scattering particle to increase light scattering and light extraction efficiency,
The particle layer is capable of adjusting the color temperature of the white light according to the concentration of the light emitting element in the particle layer, the number of particle layers including the fluorescent substance, or the combination of the fluorescent materials having different light colors,
Wherein the adhesive polymer layer is 30% to 300% of the phosphor particle size.
A method for manufacturing a functional particle layer including a quantum dot.
12. The method of claim 11,
Wherein the quantum dot comprises an inorganic nanostructure.
13. The method of claim 12,
Wherein the inorganic nanostructure is a core-shell-ligand structure.
12. The method of claim 11,
Wherein the adhesive polymer comprises a polymer selected from the group consisting of a silicone polymer, an epoxy polymer, an acrylic polymer, and combinations thereof.
12. The method of claim 11,
Wherein the particles have a size of 1 占 퐉 to 30 占 퐉.
12. The method of claim 11,
Wherein the refractive index of the adhesive polymer layer is 1.0 or more.
12. The method of claim 11,
Wherein the adhesive polymer layer has a transmittance of 85% or more.
delete delete

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