CN112635695A - Quantum dot light-emitting layer and preparation method and application thereof - Google Patents
Quantum dot light-emitting layer and preparation method and application thereof Download PDFInfo
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- CN112635695A CN112635695A CN202011518775.XA CN202011518775A CN112635695A CN 112635695 A CN112635695 A CN 112635695A CN 202011518775 A CN202011518775 A CN 202011518775A CN 112635695 A CN112635695 A CN 112635695A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Nanotechnology (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a quantum dot light-emitting layer and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) reacting the core quantum dot solution with a silane coupling agent to obtain an intermediate product, and reacting the intermediate product with an organic salt to obtain a charged core quantum dot deposition solution; (2) placing the substrate in the charged core quantum dot deposition solution obtained in the step (1) for electrodeposition to obtain a core quantum dot deposition substrate; (3) and (3) reacting the core quantum dot deposition substrate obtained in the step (2) to obtain the quantum dot light-emitting layer. The preparation method has simple integral process and low manufacturing cost; the obtained quantum dot light-emitting layer can realize pixel-level quantum dot arrangement, has the advantages of high display resolution, high light conversion efficiency, high light-emitting efficiency and the like, and can realize batch production.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a quantum dot light-emitting layer and a preparation method and application thereof.
Background
With the continuous development of display technology, people have higher and higher requirements on the display quality of display devices. The particle size of a Quantum Dot (QD) material is generally between 1 nm and 10nm, and because electrons and holes are Quantum confined, a continuous energy band structure is changed into a discrete energy level structure, so that the luminescent spectrum is very narrow (20 nm to 30nm), the chromaticity is high, the display color gamut is wide, and the color gamut can greatly exceed the color gamut range of National Television Standards Committee (NTSC); meanwhile, the quantum dot material has small light absorption loss through the color filter, and low-power-consumption display can be realized. Therefore, quantum dot materials are emerging as a new generation of luminescent materials in LED display applications.
The quantum dot light emitting layer excites the green light and the red light of partial wave bands by absorbing the blue light of the partial wave bands, so that the color gamut of the display screen can be effectively improved, and the requirement of high-quality display application is met. CN102944943A discloses a quantum dot color filter, a liquid crystal panel, and a display device, where the color filter includes a quantum dot material to form a color filter of a display, and the red, green, or blue light filter adopts a quantum dot material capable of generating red, green, or blue light through light excitation, so as to improve the utilization rate of a backlight source and obtain color light with higher purity, so that the quantum dot display can achieve high color gamut and low power consumption of color display, but the method of quantum dot layer patterning is not described.
At present, most quantum dot layer imaging methods are to disperse quantum dots in photoresist, and then to realize quantum dot photoconversion material coating on a specific area of a substrate by means of photocuring, etching and the like. CN103226260A discloses a liquid crystal display screen, a display device and a method for patterning a quantum dot layer, which provides a method for dispersing quantum dots in a photoresist and patterning the quantum dot layer by a photolithography process, the prepared quantum dot layer replaces the existing color resin to be used as a color filter to convert background light into monochromatic light, and has the advantages of high luminous efficiency, wide color gamut, high color saturation and the like; however, the quantum dots are dispersed in the photoresist, and the photoresist contains various high molecular materials such as an initiator, a polymer monomer, a polymer, an additive and the like, so that the surface chemical environment of the quantum dots is complex, and the luminous efficiency of the quantum dots is greatly influenced. CN105355726A discloses a method for patterning a quantum dot layer and a method for preparing a quantum dot color film, wherein a photoresist layer with a pattern structure is used as a shielding layer, and a monochromatic quantum dot layer is etched to obtain a patterned quantum dot layer, and the method can be used for preparing a fine quantum dot pattern, thereby greatly improving the display resolution of the patterned quantum dot layer; the quantum dot color film is prepared according to the quantum dot layer patterning method, the prepared quantum dot color film has fine quantum dot patterns, the luminous efficiency of quantum dots is high, and the resolution and the backlight utilization rate of a display device are further effectively improved.
Therefore, developing a method for preparing a quantum dot light-emitting layer with simple process and low production cost to obtain a quantum dot light-emitting layer with high light conversion efficiency, high display resolution and low efficacy is the key point of research of technicians in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a quantum dot light-emitting layer and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a quantum dot light-emitting layer, the method comprising the steps of:
(1) reacting the core quantum dot solution with a silane coupling agent to obtain an intermediate product, and reacting the intermediate product with an organic salt to respectively obtain a charged red light core quantum dot deposition solution, a charged green light core quantum dot deposition solution and a charged blue light core quantum dot deposition solution;
(2) respectively placing the substrate in the charged red light core quantum dot deposition solution, the charged green light core quantum dot deposition solution and the charged blue light core quantum dot deposition solution obtained in the step (1) for electrodeposition to obtain a core quantum dot deposition substrate;
(3) and (3) reacting the core quantum dot deposition substrate obtained in the step (2) to obtain the quantum dot light-emitting layer.
According to the preparation method of the quantum dot light-emitting layer provided by the invention, exemplarily, a reaction structure schematic diagram of the step (1) is shown in fig. 1, wherein 1 represents a core quantum dot; 2 represents an intermediate product; 3 represents a charged core quantum dot; firstly, reacting a core quantum dot 1 with a silane coupling agent to obtain an intermediate product 2; then, the intermediate product 2 reacts with an organic salt to obtain the charged core quantum dot 3. Schematically, the electrodeposition process when the core quantum dot is positively charged is schematically shown in fig. 2: wherein 3 represents a charged core quantum dot, 4 represents a substrate, and 5 represents a reaction electrode; finally, the core quantum dots on the substrate react under specific conditions to obtain the quantum dot deposition layer, and a schematic diagram of a process of reacting the core quantum dots into a quantum dot material is shown in fig. 3: wherein 3 represents a charged core quantum dot, and 6 represents a charged quantum dot luminescent material. According to the invention, the core quantum dots and the silane coupling agent are selected to react reversely to obtain an intermediate product, then the intermediate product and the organic salt are subjected to bonding reaction, the core quantum dots with charges can be more easily obtained, then the core quantum dot deposition solution is electrodeposited on the substrate, and then the quantum dot luminescent material is generated by the core quantum dots in the reaction.
Preferably, the core quantum dot of step (1) comprises any one of or a combination of at least two of metal oxide, metal halide, metal nitride, metal sulfide, metal phosphide, metal selenide, metal telluride, metal arsenide, or organometallic compound.
Preferably, the metal In the metal oxide, metal halide, metal nitride, metal sulfide, metal phosphide, metal selenide, metal telluride, metal arsenide and organic metal compound each independently comprises any one or a combination of at least two of Ba, Ca, Ag, Na, Fe, In, Cd, Zn, Ga, Mg, Ti, Zr, Pb or Cs.
Preferably, the core quantum dots comprise CdS, CdTe, CdSe, ZnSe, ZnS, ZnTe, PbSe, PbS, CuInS2、AgInS2、CuZnInS2、InP、CsPbBr3、CsPbCl3、CsPbI3、CH3NH3PbBr3、MAPbCl3Or MAPbI3Any one or a combination of at least two of them.
Preferably, the core quantum dots are made by a solution process.
Preferably, the solvent of the core quantum dot solution in step (1) includes any one of octadecene, trioctylamine, oleylamine, liquid paraffin, dodecane, octane, or hexane, or a combination of at least two of them.
Preferably, the core quantum dots have a molar mass of 0.25 to 5mol, such as 0.5mol, 0.75mol, 1mol, 1.25mol, 1.5mol, 1.75mol, 2mol, 2.25mol, 2.5mol, 2.75mol, 3mol, 3.25mol, 3.5mol, 3.75mol, 4mol, 4.25mol, 4.5mol, 4.75mol, 5mol, 5.25mol, 5.5mol or 5.75mol, based on 1L of the core quantum dot solution, and specific values therebetween are not exhaustive and are not included in the range for brevity.
Preferably, the silane coupling agent in step (1) comprises any one of or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane or vinyltris (β -methoxyethoxy) silane.
Preferably, the organic salt of step (1) is an ionic bond organic salt.
Preferably, the organic salt in step (1) comprises any one of sodium acetate, tetrabutylammonium bromide, picolinate, sodium methyl or sodium ethoxide or a combination of at least two thereof.
Preferably, the molar ratio of the core quantum dots to the silane coupling agent in the step (1) is 1 (0.02-0.5), such as 1:0.05, 10.07, 10.1, 10.12, 1:0.15, 1:0.2, 1:0.22, 1:0.25, 1:0.27, 1:0.3, 1:0.32, 1:0.35, 1:0.38, 1:0.4, 1:0.42, 1:0.45, or 1: 0.5.
Preferably, the reaction time of the core quantum dot solution and the silane coupling agent in the step (1) is 0.3-15 min, such as 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min or 14min and specific values therebetween, and the invention is not exhaustive and specific values included in the range are not provided for the sake of brevity.
Preferably, the molar ratio of the intermediate product and the organic salt in step (1) is 1 (1-100), such as 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95, etc.
Preferably, the reaction of the intermediate product in step (1) with an organic salt is carried out at a pH of 5-11 (e.g., 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, or 10.5, etc.).
Preferably, the temperature for reacting the intermediate product with the organic salt in the step (1) is 120-320 ℃, for example, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃ or 310 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction time of the intermediate product of step (1) with the organic salt is 0.5-90 min, such as 1min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min or 85min, and the specific values therebetween are limited to space and for brevity, the invention is not exhaustive.
Preferably, the substrate in step (2) comprises an insulating transparent bottom plate, a transparent conductive film and a circuit which are sequentially arranged from bottom to top.
Preferably, the thickness of the transparent substrate is 12-65 μm, such as 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, 32 μm, 34 μm, 36 μm, 38 μm, 40 μm, 42 μm, 44 μm, 46 μm, 48 μm, 50 μm, 52 μm, 54 μm, 56 μm, 58 μm, 60 μm, 62 μm or 64 μm, and the specific point values between the above point values are limited to space and the invention does not exhaustive list the specific point values included in the range for the sake of brevity.
Preferably, the material of the insulating transparent bottom plate comprises any one of or a combination of at least two of inorganic glass, polymethyl methacrylate, polystyrene, polycarbonate or polybisallyldiglycol carbonate.
Preferably, the transparent conductive film includes an ITO film.
Preferably, the transparent conductive film has a light transmittance of > 85%, such as 87%, 89%, 91%, 93%, 95%, 97%, 99%, or 100%, and specific values therebetween, not to be exhaustive or to limit the invention to the specific values included in the range for brevity.
Preferably, the transparent conductive film has a resistivity < 5 × 10-4Ω · m, e.g. 4.5X 10-4Ω·m、4×10-4Ω·m、3.5×10-4Ω·m、3×10-4Ω·m、2.5×10-4Ω·m、2×10-4Ω·m、1.5×10-4Omega m or 1X 10-4Ω · m, and the specific point values between the foregoing, are limited by space and for the sake of brevity and are not intended to be an exhaustive list of the specific point values encompassed by the scope.
Preferably, the thickness of the transparent conductive film is 150 to 1500nm, such as 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm, 1000nm, 1100nm, 1200nm, 1300nm or 1400nm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the substrate in step (2) is prepared by the following steps:
preparing a transparent conductive film on an insulating transparent bottom plate, coating an anti-etching material on the transparent conductive film according to pixel point arrangement, etching the transparent conductive film coated with the anti-etching material until the corresponding position is exposed out of the insulating transparent bottom plate, stripping and cleaning the residual anti-etching material, and mounting a circuit on the transparent conductive film to obtain the substrate.
The invention relates to a preparation method of a quantum dot light-emitting layer, which comprises the following steps: firstly, preparing a transparent conductive film on an insulating transparent bottom plate, and then coating an anti-etching material on the transparent conductive film according to pixel point arrangement, so that the anti-etching material covers an area where red light core quantum dots, green light core quantum dots and blue light core quantum dots are to be deposited; etching the transparent conductive film coated with the anti-etching material until the corresponding position leaks out of the insulating transparent bottom plate, stripping and cleaning the residual anti-etching material, finally installing a circuit on the transparent conductive film to interconnect the transparent conductive film regions of all red light core quantum dots to be deposited so as to realize electric conduction, interconnecting the transparent conductive film regions of all green light core quantum dots to be deposited so as to realize electric conduction, and interconnecting the transparent conductive film regions of all blue light core quantum dots to be deposited so as to realize electric conduction; and finally obtaining the substrate.
Preferably, the method for preparing the transparent conductive film comprises any one of magnetron sputtering, vacuum evaporation or sol-gel spin coating.
Preferably, the etching comprises physical etching and/or chemical etching.
Preferably, the etching material is coated in a thickness of 200 to 15000nm, such as 500nm, 1000nm, 1500nm, 2500nm, 3500nm, 5500nm, 6500nm, 7500nm, 8500nm, 9500nm, 10500nm, 11500nm, 12500nm, 13500nm or 14500nm, and specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
Preferably, the cleaning includes any one of organic solution cleaning, water cleaning, or plasma cleaning, or a combination of at least two thereof.
Preferably, the DC voltage for the electrodeposition in step (2) is 1-12V, such as 2V, 3V, 4V, 5V, 6V, 7V, 8V, 9V, 10V or 11V, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the deposited current is 0.5 to 30mA, such as 1mA, 2mA, 4mA, 6mA, 8mA, 10mA, 12mA, 14mA, 16mA, 18mA, 20mA, 22mA, 24mA, 26mA or 28mA, and specific point values therebetween, which are not exhaustive for the sake of brevity and brevity.
Preferably, the electrodeposition time is 1-30 min, such as 2min, 4min, 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min or 26min, 28min, and the specific values therebetween are limited for the sake of brevity and simplicity, and the invention is not intended to be exhaustive.
Preferably, the thickness of the electrodeposited deposition layer is 15 to 90 μm, such as 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm or 85 μm, and specific values therebetween, not to limit the disclosure and for the sake of brevity, the present invention is not exhaustive of the specific values included in the range.
Preferably, the electrodeposition of step (2) further comprises a step of surface spraying.
As a preferred technical scheme of the invention, the method also comprises a surface spraying step after the electro-deposition is finished, and the quantum dot light-emitting layer with high luminous efficiency and high display resolution can be obtained after the surface spraying treatment; specifically, after the charged core quantum dots of one color light are electrodeposited on the substrate, the substrate deposited with the charged core quantum dots of one color light is taken out of the deposition solution, and spraying treatment is performed to protect and prevent unstable adhesion of the core quantum dots deposited on the substrate, so that the core quantum dots of the charged first color light deposited on the substrate are prevented from falling off when the charged core quantum dots of the second color light are electrodeposited.
Preferably, the sprayed material is an acrylate material.
Preferably, the reaction temperature in step (3) is 60-120 ℃, for example, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃ or 115 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction time in step (3) is 6-48 h, such as 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h or 46h, and the specific values therebetween are limited in space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the step (3) further comprises a step of curing the package after the reaction is completed.
As a preferred technical scheme of the invention, the step of curing and packaging is further included after the reaction in the step (3) is completed, so that the quantum dot material deposition layer can be included, and the quantum dot light-emitting layer with high light-emitting efficiency and high display resolution can be obtained.
Preferably, the curing package comprises a heat curing package and/or a light curing package.
Preferably, the glue material for curing and packaging comprises any one or a combination of at least two of epoxy materials, silicone materials or polyurethane materials.
Preferably, the preparation method specifically comprises the following preparation steps:
(1) reacting the core quantum dot solution with a silane coupling agent to obtain an intermediate product, mixing the intermediate product with an organic salt, and reacting at 120-320 ℃ for 0.5-90 min to respectively obtain a charged red light core quantum dot deposition solution, a charged green light quantum dot deposition solution and a charged blue light core quantum dot deposition solution; the organic salt comprises any one or a combination of at least two of sodium acetate, tetrabutylammonium bromide, picolinate, methyl sodium or sodium ethoxide; the core quantum dots comprise any one or a combination of at least two of metal oxide, metal halide, metal nitride, metal sulfide, metal phosphide, metal selenide, metal telluride, metal arsenide or organic metal compound;
(2) respectively placing the substrate in the red light core quantum dot deposition solution with charges, the green light core quantum dot deposition solution with charges and the blue light core quantum dot deposition solution with charges obtained in the step (1), and performing electrodeposition for 1-30 min under the conditions that the direct current voltage is 1-12V and the current is 0.5-30 mA to obtain a core quantum dot deposition substrate; the substrate comprises an insulating transparent bottom plate, a transparent conductive film and a circuit which are sequentially arranged from bottom to top;
(3) and (3) reacting the core quantum dot deposition substrate obtained in the step (2) for 6-48 h at the temperature of 60-120 ℃, and curing and packaging to obtain the quantum dot light-emitting layer.
In a second aspect, the present invention provides a quantum dot light-emitting layer produced by the production method according to the first aspect.
Preferably, the quantum dot light emitting layer includes a red light quantum dot material, a green light quantum dot material, and a blue light quantum dot material.
Preferably, the red light quantum dot material, the green light quantum dot material and the blue light quantum dot material comprise AxMyEzAnd (3) system materials.
Wherein A is selected from any one of Ba, Ag, Na, Fe, In, Cd, Zn, Ga, Mg, Pb or Cs.
M is selected from any one of S, Cl, O, As, N, P, Se, Te, Ti, Zr or Pb.
E is selected from any one of S, As, Se, O, Cl, Br or I.
x is 0.3 to 2, such as 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.4, 1.6, or 1.8, and the specific values therebetween are not exhaustive for the invention, including the specific values within the ranges, for reasons of brevity and clarity.
y is 0.5 to 3, such as 0.7, 0.9, 1.1, 1.3, 1.5, 1.7, 1.9, 2.1, 2.3, 2.5, 2.7, or 2.9, and the specific values therebetween are not exhaustive and are not intended to limit the invention to the specific values included in the ranges for brevity and conciseness.
z is 0 to 4, such as 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, or 3.8, and the specific values therebetween are not exhaustive and are not intended to limit the invention to the specific values encompassed by the scope, for brevity and clarity.
In a third aspect, the invention provides a use of the quantum dot light emitting layer of the second aspect in a display device or a lighting device.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the quantum dot light-emitting layer, the core quantum dots and the silane coupling agent are reacted to obtain an intermediate product, and the intermediate product is reacted with the organic salt to obtain the core quantum dots with charges; under the specific electrodeposition condition, the charged core quantum dots are electrodeposited on a substrate and react to obtain the quantum dot light-emitting layer, the whole preparation process is simple in process, simple to operate and low in cost, and batch production can be realized; the light conversion rate of the obtained quantum dot light emitting layer is 82-88%, the pixel density is 580-660 PPI, the display color gamut value is 112-120%, the light conversion rate is improved by 15-257% compared with that of a quantum dot light emitting layer or a quantum dot optical membrane in the prior art, the pixel density is improved by 61-106%, and the display color gamut value is improved by 5-18%.
Drawings
FIG. 1 is a schematic diagram of the reaction process of step (1) in the preparation method provided by the present invention;
FIG. 2 is a schematic diagram of a process of electrodeposition of core quantum dots on a substrate;
fig. 3 is a schematic diagram of a process of reacting charged core quantum dots on a substrate into a charged quantum dot material.
Wherein, 1-core quantum dot, 2-intermediate product, 3-charged core quantum dot, 4-substrate, 5 generation-reaction electrode, and 6-charged quantum dot luminescent material.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a quantum dot light-emitting layer specifically comprises the following steps:
(1) preparing a charged core quantum dot deposition solution: reacting an octadecene solution of an InP core with vinyl triethoxysilane for 6min to obtain an intermediate product; adding sodium acetate and mixing at 220 ℃, wherein the molar concentration of an InP core in the octadecene solution is 2.5mol/L, the concentration of vinyl triethoxysilane in the octadecene solution is 0.5mol/L, and the molar concentration of sodium acetate in the octadecene solution is 120 mol/L; reacting for 45min to obtain an InP core deposition solution (red light core quantum dot deposition solution) with charges; under the same conditions, the InP core is replaced by CsPbBr3Core, repeating the above steps to obtain CsPbBr with charge3Core deposition solution (green light core quantum dot deposition solution); changing the InP core into a CdSe core, and repeating the steps to obtain a charged InP core deposition solution (blue light core quantum dot deposition solution);
(2) preparing a substrate: firstly, Sn doped In is prepared on inorganic glass with the thickness of 250 mu m by a magnetron sputtering method2O3A transparent conductive film; coating a negative photoresist with the thickness of 750nm on the cured transparent conductive film according to the arrangement of the pixel points, so that the etching-resistant material alternately covers the InP core quantum dots to be deposited and the CsPbBr3A region of core quantum dots and CdSe core quantum dots; then, chemically etching the transparent conductive film coated with the etching-resistant material until inorganic glass leaks out of the corresponding position, and stripping and washing the residual etching-resistant material with water; finally, a circuit is arranged on the transparent conductive film to connect all transparent conductive film areas to be deposited with InP core quantum dots, and all areas to be deposited with CsPbBr3The transparent conductive film areas of the core quantum dots are mutually connected, and the transparent conductive film areas of all CdSe core quantum dots to be deposited are mutually connected to form a core quantum dot deposition substrate, so that the substrate is obtained;
(3) and (3) an electrodeposition process: placing the substrate obtained in the step (2) in the InP core deposition solution obtained in the step (1), adding a reaction electrode into the solution, and performing electrodeposition for 15min under the conditions that the direct-current voltage is 6V and the current is 15mA to obtain the InP core quantum dot deposition substrate with charges, wherein the thickness of the deposition layer is 42 microns, and thus completing the electrodeposition; taking the substrate deposited with the InP core quantum dots with charges out of the solution, spraying the substrate deposited with the InP core quantum dots with methacrylate, and respectively placing the substrate in the CsPbBr with charges obtained in the step (1)3Repeating the electrodeposition steps in the core quantum dot deposition solution and the CdSe core quantum dot deposition solution with charges to obtain InP core quantum dots with charges and CsPbBr with charges3A deposition substrate of core quantum dots and charged CdSe core quantum dots;
(4) reacting the deposition substrate obtained in the step (3) for 28 hours at the temperature of 90 ℃ to obtain the InP quantum deposited on the surfaceDot material, CsPbBr3And finally, encapsulating the substrate by using bisphenol A type epoxy resin to obtain the quantum dot light-emitting layer.
Example 2
A preparation method of a quantum dot light-emitting layer is different from that of example 1 only in that InP core quantum dots and CsPbBr are contained in an octadecene solution in the step (1)3The molar concentration of the core quantum dots and the CdSe core quantum dots is 0.25mol/L, and the molar concentration of sodium acetate in the octadecene solution is 12 mol/L; the amounts of other components and experimental conditions were the same as in example 1, and the quantum dot light-emitting layer was obtained.
Example 3
A preparation method of a quantum dot light-emitting layer is different from that of example 1 only in that InP core quantum dots and CsPbBr are contained in an octadecene solution in the step (1)3The molar concentration of the core quantum dots and the CdSe core quantum dots is 5mol/L, and the molar concentration of sodium acetate in the octadecene solution is 240 mol/L; the amounts of other components and experimental conditions were the same as in example 1, and the quantum dot light-emitting layer was obtained.
Example 4
A method for producing a quantum dot light-emitting layer, which differs from example 1 only in that the molar concentration of sodium acetate in the octadecylene solution of step (1) is 2.5 mol/L; the amounts of other components and experimental conditions were the same as in example 1, and the quantum dot light-emitting layer was obtained.
Example 5
A method for producing a quantum dot light-emitting layer, which differs from example 1 only in that the molar concentration of sodium acetate in the octadecylene solution of step (1) is 250 mol/L; the amounts of other components and experimental conditions were the same as in example 1, and the quantum dot light-emitting layer was obtained.
Example 6
This example provides a method for preparing a quantum dot light-emitting layer, which is different from example 1 only in the InP core quantum dots, CsPbBr in step (1)3The core quantum dots and the CdSe core quantum dots are respectively replaced by PbSe core quantum dots, CdS core quantum dots and ZnS core quantum dots; other Components amounts and Experimental conditionsThe quantum dot light emitting layer was obtained in the same manner as in example 1.
Comparative example 1
A preparation method of a quantum dot luminescent layer comprises the following specific steps
(1) InP red light quantum dot glue with the concentration of 0.15mol/L and CsPbBr with the concentration of 0.50mol/L are respectively coated on inorganic glass3Performing photocuring on the green light quantum dot glue and the CdSe blue light quantum dot glue with the concentration of 0.73mol/L to obtain a photoresist substrate;
(2) covering a shielding cover on the position of the photoresist base plate obtained in the step (1) coated with the red light quantum dot glue, the green light quantum dot glue and the blue light quantum dot glue, and irradiating by using ultraviolet light to expose the irradiated part to obtain an exposed base plate;
(3) and (3) developing and cleaning the exposed substrate obtained in the step (2), and stripping the exposed part of the exposed substrate to obtain the quantum dot light-emitting layer.
Comparative example 2
A preparation method of a quantum dot luminescent layer comprises the following specific steps:
(1) MAPbI with the concentration of 0.22mol/L is prepared respectively3Red light quantum dot ink, InP green light quantum dot ink with the concentration of 0.62mol/L and PbS blue light quantum dot ink with the concentration of 0.80 mol/L;
(2) respectively coating the red light quantum dot ink, the green light quantum dot ink and the blue light quantum dot ink obtained in the step (1) on inorganic glass to obtain a deposition substrate;
(3) and (3) processing the deposition substrate obtained in the step (2) at 120 ℃ for 35min under the protection of a nitrogen atmosphere, so that the red light quantum dot ink, the green light quantum dot ink and the blue light quantum dot ink on the deposition substrate are volatilized, and the quantum dot light-emitting layer is obtained.
Comparative example 3
A quantum dot optical film is prepared by the following steps:
(1) mixing ZnS red light quantum dots with acrylic packaging glue in a mass ratio of 1:446.2, mixing InP green light quantum dots with acrylic packaging glue in a mass ratio of 3.2:446.2, and mixing the InP green light quantum dots with the acrylic packaging glue in a mass ratio of 5:446.2 CsPbCl3Mixing the blue light quantum dot material with acrylic packaging glue to obtain red light quantum dot glue, green light quantum dot glue and blue light quantum dot glue respectively;
(2) mixing the red light quantum dot glue, the green light quantum dot glue and the blue light quantum dot glue obtained in the step (1) to obtain mixed quantum dot glue, and adding silicon oxide into the mixed quantum dot glue to obtain mixed glue, wherein the mass percentage of the mixed quantum dot glue in the mixed glue is 1.5%;
(3) coating the mixed glue obtained in the step (2) on a substrate membrane, covering a layer of substrate membrane, controlling the thickness of a quantum dot layer by using a coating machine, packaging under the irradiation of ultraviolet light, and cutting to obtain the quantum dot optical membrane.
Application examples 1 to 6
A display device is provided with the quantum dot light-emitting layer obtained in the embodiment 1-6 and is applied to a display device, and the specific preparation method is as follows:
the quantum dot light-emitting layer prepared in the embodiment 1-6 is installed on an ultraviolet light Micro-LED backlight source, and can emit red light, green light and blue light under the excitation of the ultraviolet light Micro-LED light source.
Comparative application examples 1 to 2
A display device, the quantum dot luminescent layer obtained in comparative examples 1 and 2 is used as a luminescent device, and the specific preparation method is the same as application example 1.
Comparative application example 3:
a display device, which uses the quantum dot optical film obtained in the comparative example 3 as a light emitting device, is different from the comparison application example 1 in that a color filter is added to realize red, green and blue full color display.
And (3) performance testing:
(1) light conversion efficiency: the light power of the sample emitted light after being excited by the backlight source/the light power of the sample emitted light by the backlight source is multiplied by 100 percent;
(2) pixel density: connecting the diagonal lines of the samples, wherein the number of pixel points existing in each inch of length is the resolution;
(3) displaying the color gamut value: the area of a triangle formed by connecting the color coordinate points of the red, the green and the blue of the display screen is compared with the area of a standard NTSC triangle.
The performance of the display devices obtained in application examples 1 to 6 and comparative application examples 1 to 3 was tested according to the test method, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1: the display device comprising the quantum dot light-emitting layer provided by the invention has higher light conversion efficiency and pixel density (PPI), and has wider display color gamut value; specifically, the light conversion rate of the quantum dot light emitting layer provided in embodiments 1 to 6 is 82 to 88%, the pixel density is 580 to 660PPI, and the display color gamut value is 112 to 120%, and compared with the light conversion efficiency of the quantum dot light emitting layer (comparative example 1 and comparative example 2) or the quantum dot optical film (comparative example 3) in the prior art, the light conversion efficiency is improved by 15 to 257%, the pixel density is improved by 61 to 106%, and the display color gamut value is improved by 5 to 18%, which indicates that the quantum dot light emitting layer provided by the present invention has higher light conversion efficiency and resolution.
The applicant states that the present invention describes a quantum dot light emitting layer and a preparation method and an applied process method thereof through the above embodiments, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A preparation method of a quantum dot light-emitting layer is characterized by comprising the following steps:
(1) reacting the core quantum dot solution with a silane coupling agent to obtain an intermediate product, and reacting the intermediate product with an organic salt to respectively obtain a charged red light core quantum dot deposition solution, a charged green light core quantum dot deposition solution and a charged blue light core quantum dot deposition solution;
(2) respectively placing the substrate in the charged red light core quantum dot deposition solution, the charged green light core quantum dot deposition solution and the charged blue light core quantum dot deposition solution obtained in the step (1) for electrodeposition to obtain a core quantum dot deposition substrate;
(3) and (3) reacting the core quantum dot deposition substrate obtained in the step (2) to obtain the quantum dot light-emitting layer.
2. The method according to claim 1, wherein the core quantum dot of step (1) comprises any one or a combination of at least two of a metal oxide, a metal halide, a metal nitride, a metal sulfide, a metal phosphide, a metal selenide, a metal telluride, a metal arsenide, or an organometallic compound;
preferably, the metal In the metal oxide, metal halide, metal nitride, metal sulfide, metal phosphide, metal selenide, metal telluride, metal arsenide and organic metal compound respectively and independently comprises any one or a combination of at least two of Ba, Ca, Ag, Na, Fe, In, Cd, Zn, Ga, Mg, Ti, Zr, Pb or Cs;
preferably, the core quantum dots comprise CdS, CdTe, CdSe, ZnSe, ZnS, ZnTe, PbSe, PbS, CuInS2、AgInS2、CuZnInS2、InP、CsPbBr3、CsPbCl3、CsPbI3、CH3NH3PbBr3、MAPbCl3Or MAPbI3Any one or a combination of at least two of;
preferably, the core quantum dots are made by a solution process.
3. The preparation method according to claim 1 or 2, wherein the solvent of the core quantum dot solution in step (1) comprises any one or a combination of at least two of octadecene, trioctylamine, oleylamine, liquid paraffin, dodecane, octane or hexane;
preferably, the molar mass of the core quantum dots is 0.25-5 mol based on 1L of the core quantum dot solution;
preferably, the silane coupling agent in step (1) comprises any one or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane or vinyltris (beta-methoxyethoxy) silane;
preferably, the organic salt of step (1) is an ionically bonded organic salt;
preferably, the organic salt in step (1) comprises any one of sodium acetate, tetrabutylammonium bromide, picolinate, sodium methyl or sodium ethoxide or a combination of at least two of them;
preferably, the molar ratio of the core quantum dots to the silane coupling agent in the step (1) is 1 (0.02-0.5);
preferably, the reaction time of the core quantum dot solution and the silane coupling agent in the step (1) is 0.3-15 min;
preferably, the molar ratio of the intermediate product and the organic salt in the step (1) is 1 (1-100);
preferably, the reaction of the intermediate product in the step (1) and an organic salt is carried out under the condition that the pH value is 5-11;
preferably, the temperature for the reaction of the intermediate product in the step (1) and the organic salt is 120-320 ℃;
preferably, the reaction time of the intermediate product in the step (1) and the organic salt is 0.5-90 min.
4. The manufacturing method according to any one of claims 1 to 3, wherein the substrate of the step (2) comprises an insulating transparent bottom plate, a transparent conductive film and a circuit which are arranged in sequence from bottom to top;
preferably, the thickness of the insulating transparent bottom plate is 12-65 μm;
preferably, the material of the insulating transparent bottom plate comprises any one or a combination of at least two of inorganic glass, polymethyl methacrylate, polystyrene, polycarbonate or polydiallyl diglycol carbonate;
preferably, the transparent conductive thin film includes an ITO film;
preferably, the transparent conductive film has a light transmittance of > 85%;
preferably, the transparent conductive film has a resistivity < 5 × 10-4Ω·m；
Preferably, the thickness of the transparent conductive film is 150-1500 nm.
5. The production method according to any one of claims 1 to 4, wherein the substrate of the step (2) is produced by:
preparing a transparent conductive film on an insulating transparent bottom plate, coating an anti-etching material on the transparent conductive film according to pixel point arrangement, etching the transparent conductive film coated with the anti-etching material until the corresponding position leaks out of the insulating transparent bottom plate, stripping and cleaning the residual anti-etching material, and mounting a circuit on the transparent conductive film to obtain the substrate;
preferably, the method for preparing the transparent conductive film comprises any one of magnetron sputtering, vacuum evaporation or sol-gel spin coating;
preferably, the etching comprises physical etching and/or chemical etching;
preferably, the coating thickness of the etching material is 200-15000 nm;
preferably, the cleaning includes any one of organic solution cleaning, water cleaning, or plasma cleaning, or a combination of at least two thereof.
6. The method according to any one of claims 1 to 5, wherein the DC voltage for the electrodeposition in the step (2) is 1 to 12V;
preferably, the deposited current is 0.5-30 mA;
preferably, the time of the electrodeposition is 1-30 min;
preferably, the thickness of the electrodeposited deposition layer is 15-90 μm;
preferably, the electrodeposition of the step (2) further comprises a step of surface spraying;
preferably, the sprayed material is an acrylate material.
7. The method according to any one of claims 1 to 6, wherein the temperature of the reaction in step (3) is 60 to 120 ℃;
preferably, the reaction time in the step (3) is 6-48 h;
preferably, the step (3) further comprises a step of curing the package after the reaction is completed;
preferably, the curing package comprises a heat curing package and/or a light curing package;
preferably, the glue material for curing and packaging comprises any one or a combination of at least two of epoxy materials, silicone materials or polyurethane materials.
8. The preparation method according to any one of claims 1 to 7, characterized by specifically comprising the following preparation steps:
(1) mixing the core quantum dot solution with a silane coupling agent to obtain an intermediate product, mixing the intermediate product with an organic salt, and reacting at 120-320 ℃ for 0.5-90 min to respectively obtain a charged red light core quantum dot deposition solution, a charged green light core quantum dot deposition solution and a charged blue light core quantum dot deposition solution; the organic salt comprises any one or a combination of at least two of sodium acetate, tetrabutylammonium bromide, picolinate, methyl sodium or sodium ethoxide; the core quantum dots comprise any one or a combination of at least two of metal oxide, metal halide, metal nitride, metal sulfide, metal phosphide, metal selenide, metal telluride, metal arsenide or organic metal compound;
(2) respectively placing the substrate in the red light core quantum dot deposition solution with charges, the green light core quantum dot deposition solution with charges and the blue light core quantum dot deposition solution with charges obtained in the step (1), and performing electrodeposition for 1-30 min under the conditions that the direct current voltage is 1-12V and the current is 0.5-30 mA to obtain a core quantum dot deposition substrate; the substrate comprises an insulating transparent bottom plate, a transparent conductive film and a circuit which are sequentially arranged from bottom to top;
(3) and (3) reacting the core quantum dot deposition substrate obtained in the step (2) for 6-48 h at the temperature of 60-120 ℃, and curing and packaging to obtain the quantum dot light-emitting layer.
9. A quantum dot light-emitting layer, wherein the quantum dot light-emitting layer is produced by the production method according to any one of claims 1 to 8;
preferably, the quantum dot light-emitting layer comprises a red light quantum dot material, a green light quantum dot material and a blue light quantum dot material;
preferably, the red light quantum dot material, the green light quantum dot material and the blue light quantum dot material comprise AxMyEzA system material;
wherein A is selected from any one of Ba, Ag, Na, Fe, In, Cd, Zn, Ga, Mg, Pb or Cs;
m is selected from any one of S, Cl, O, As, N, P, Se, Te, Ti, Zr or Pb;
e is selected from any one of S, As, Se, O, Cl, Br or I;
x is 0.3-2;
y is 0.5 to 3;
z is 0 to 4.
10. Use of a quantum dot light emitting layer according to claim 9 in a display device or a lighting device.
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Citations (5)
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