CN117117061A - Quantum dot light conversion device and preparation method thereof - Google Patents
Quantum dot light conversion device and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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Abstract
The present disclosure provides a quantum dot light conversion device and a method of fabricating the same. The quantum dot light conversion device comprises a substrate, a quantum dot layer and a packaging adhesive layer, wherein the quantum dot layer and the packaging adhesive layer are positioned on the substrate, the packaging adhesive layer covers at least one surface of the quantum dot layer, the quantum dot layer comprises a plurality of nano oxide particles and a plurality of quantum dots, the average size of the nano oxide particles is larger than that of the quantum dots, the nano oxide particles are in a stacked state, the stacked nano oxide particles form a plurality of gaps, the average n quantum dots are positioned in the gaps, n is more than 0 and less than 2, and the number of the quantum dots is less than that of the nano oxide particles.
Description
Technical Field
The disclosure relates to the field of quantum dots, in particular to a quantum dot light conversion device and a preparation method thereof.
Background
The conventional lighting and display light emitting device is generally that a blue InGaN chip excites phosphor powder (YAG powder, new red powder-KSF, green powder (β -Sialon) or the like) containing red and green components to form white light, and the half-wavelength FWHM of the phosphor powder is generally between 40 and 60nm, and the light emitting characteristic is single and the spectrum adjustability is poor. Quantum Dots (QDs) as a novel nano-fluorescent material exhibit their special optical properties that are strongly dependent on size. Compared with the traditional fluorescent material, the quantum dot has a series of unique optical properties such as adjustable spectrum, narrow half-wave width of emission peak, large Stokes shift, high excitation efficiency and the like, but the quantum dot is a luminescent nanocrystalline with nanometer size, has very high specific surface area, higher chemical reaction activity, is sensitive to external environment, and has insufficient stability in commercial application and needs to be promoted by external materials. The quantum dots are usually packaged by adopting a high-barrier film (mainly imported), the barrier film has excellent performance of isolating water and oxygen, the photoetching phenomenon of the quantum dots can be delayed, the photoluminescence life of the quantum dots is kept, but the cost of the barrier film is higher, so that the quantum dots can only be applied to high-end display products at present.
Disclosure of Invention
An object of the present disclosure is to provide a quantum dot light conversion device having improved light emission stability, and a method of manufacturing the same.
In a first aspect of the present disclosure, a quantum dot light conversion device is provided, the quantum dot light conversion device includes a substrate, a quantum dot layer and a packaging adhesive layer on the substrate, the packaging adhesive layer covers at least one surface of the quantum dot layer, the quantum dot layer includes a plurality of nano oxide particles and a plurality of quantum dots, an average size of the nano oxide particles is larger than an average size of the quantum dots, the plurality of nano oxide particles present a stacked state, the stacked nano oxide particles form a plurality of gaps, an average n number of quantum dots are located in the gaps, 0 < n < 2, and a number of the quantum dots is smaller than a number of the nano oxide particles.
Alternatively, the plurality of nano-oxide particles are stacked into a plurality of nano-oxide particle layers, and the horizontal spacing between adjacent nano-oxide particles on the same layer is smaller than the average size of the quantum dots, preferably the horizontal spacing is smaller than one quarter of the average size of the quantum dots.
Alternatively, the molar ratio of quantum dots to nano-oxide particles ranges from 0.01 to less than 1, preferably from 0.02 to 0.5.
Alternatively, the ratio of the average size of the quantum dots to the nano-oxide particles is 0.207 to 0.414.
Alternatively, the average size of the nano oxide particles ranges from 10 to 200nm, and the average size of the quantum dots ranges from 6 to 40nm.
Alternatively, the quantum dot surface ligands are inorganic ligands.
Alternatively, the inorganic ligand is a metal oxide ligand, preferably an oxide ligand selected from (Al 2 O 3 ) n -OH、(ZnO) n -OH、(SiO 2 ) n -OH、(ZrO 2 ) n -OH、Ca(OH) 2 、NaOH、Mg(OH) 2 、(ZnMgO) n -OH、(SnO 2 ) n -one or more of OH, silicate, aluminosilicate.
Optionally, the quantum dot surface ligand is selected from one or more of metal halides, metal sulfides, metal carbonates, metal sulfates, and metal phosphates.
Alternatively, the molecular weight of the inorganic ligand is 10000 or less, preferably 500 to 5000.
Optionally, the inorganic ligand is coated with an inorganic oxide shell, preferably alumina.
Alternatively, the thickness of the inorganic oxide shell layer is 0.5 to 30nm, preferably 1 to 5nm.
Alternatively, the nano-oxide particles are selected from SnO 2 、ZnO、SiO 2 、In 2 O 3 、GeO 2 、MgO、ZnMgO、Al 2 O 3 And ZrO(s) 2 One or more of the following.
Alternatively, the variance of the size distribution of the nano-oxide particles is 20% or less, preferably 15% or less.
Optionally, the quantum dot light conversion device further comprises at least one LED chip on the substrate, and the quantum dot layer covers the LED chip.
According to another aspect of the present disclosure, there is provided a method of manufacturing a quantum dot light conversion device, the method comprising:
preparing a substrate;
preparing a dispersion liquid containing nano oxide particles, and preparing a dispersion liquid containing quantum dots, wherein the average size of the nano oxide particles is larger than that of the quantum dots, and the number of the quantum dots in the dispersion liquid of the quantum dots is smaller than that of the nano oxide particles;
mixing the dispersion liquid containing the nano oxide particles and the dispersion liquid containing the sub-points to obtain mixed dispersion liquid;
setting the mixed dispersion liquid on a substrate, volatilizing a solvent in the mixed dispersion liquid to obtain a quantum dot layer, wherein the stacked nano oxide particles form a plurality of gaps in the quantum dot layer, and n quantum dots are positioned in one gap on average, wherein n is more than 0 and less than 2;
and coating the packaging glue on the quantum dot layer and curing to obtain the packaging glue layer.
Optionally, the molar ratio of the quantum dots to the nano-oxide particles ranges from 0.01 to less than 1.
Alternatively, the concentration of the nano-oxide particles is in the range of 0.1umol/L to 20mmol/L.
According to the technical scheme, the quantum dots are packaged through gaps among the nano oxide particles and fixed through the packaging adhesive, so that the product cost is reduced, and the stability of the quantum dots can be effectively improved due to the oxidation resistance of the nano oxide particles, so that the service life of the quantum dot light conversion device is prolonged.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure, illustrate and explain the exemplary embodiments of the disclosure and together with the description serve to explain the disclosure, and do not constitute an undue limitation on the disclosure. In the drawings:
fig. 1 is a schematic structural diagram of a quantum dot light conversion device according to an embodiment of the present disclosure.
Fig. 2 is a schematic structural diagram of a quantum dot light conversion device according to another embodiment of the present disclosure.
Fig. 3 is a TEM top view of one quantum dot layer of the present disclosure.
Fig. 4 is a graph of the quantum efficiency of a quantum dot light conversion device of one embodiment of the present disclosure over time for a particular aging condition.
1. A substrate; 2. a quantum dot layer; 21. nano-oxide particles; 22. a first quantum dot; 23. a second quantum dot; 3. packaging adhesive layers; 4. an LED chip.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present disclosure are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate in order to describe the embodiments of the disclosure herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The "average size" is the statistical result of the nanoparticles, typically based on the statistics of 50-100 particles in the TEM image. For spherical quantum dots, the average size is the diameter, and for non-spherical nanoparticles, the diameter is calculated from a two-dimensional region of the TEM image (e.g., assuming that the two-dimensional region forms a circle). The thickness is obtained by subtracting the average sizes of the nano particles at different stages, and is mainly counted based on the result of an electron microscope image of TEM in the preparation process of the nano particles.
The quantum dot light conversion device comprises a substrate, a quantum dot layer and a packaging adhesive layer, wherein the quantum dot layer and the packaging adhesive layer are arranged on the substrate, the packaging adhesive layer covers at least one surface of the quantum dot layer, the quantum dot layer comprises a plurality of nano oxide particles and a plurality of quantum dots, the average size of the nano oxide particles is larger than that of the quantum dots, the nano oxide particles are in a stacked state, the stacked nano oxide particles form a plurality of gaps, the average n quantum dots are positioned in the gaps, n is more than 0 and less than 2, and the number of the quantum dots is less than that of the nano oxide particles. The packaging of the quantum dots is realized through gaps among the nano oxide particles and the quantum dots are fixed through the packaging adhesive, so that the product cost is reduced compared with a high-barrier film, and the stability of the quantum dots can be effectively improved due to the fact that the quantum dots are surrounded by the nano oxide particles due to the oxidation resistance of the nano oxide particles, and the service life of the quantum dot light conversion device is prolonged. The voids have 0, 1, 2 quantum dots randomly distributed therein.
In some embodiments, the plurality of nano-oxide particles are stacked into a plurality of nano-oxide particle layers, the horizontal spacing between adjacent nano-oxide particles positioned on the same layer is smaller than the average size of the quantum dots, and the smaller the horizontal spacing is, the denser the smaller the quantum dot particles therein can be protected. Preferably the horizontal spacing is less than one-fourth the average size of the quantum dots, more preferably 0.
In some embodiments, the quantum dot to nano-oxide particle molar ratio ranges from 0.01 to less than 1, preferably from 0.02 to 0.5. The relatively large number of nano oxide particles can reduce the probability of exposing the quantum dots to the outside, and meanwhile, the distribution density of the quantum dots in the quantum dot light conversion device is considered. In some embodiments, the quantum dots are group III-V, II-VI quantum dots, or a combination thereof. In some embodiments, the quantum dots are in the shape of spheres, cubes, or hexahedrons.
In some embodiments, the ratio of the average size of the quantum dots to the nano-oxide particles is from 0.207 to 0.414. According to theoretical geometrical calculation, when the encapsulation of 1 quantum dot is just realized in one gap formed between the nano oxide particles, the ratio is 0.414, and in order to not exceed 2 quantum dot encapsulation at most, the ratio is more than or equal to 0.207.
In some embodiments, the average size of the nano-oxide particles ranges from 10 to 200nm and the average size of the quantum dots ranges from 6 to 40nm. In some embodiments, the average size of the nano-oxide particles ranges from 20 to 100nm and the average size of the quantum dots ranges from 7 to 30nm.
In some embodiments, as shown in fig. 1, the quantum dot layer includes first and second quantum dots having different emission peak wavelengths, and in particular, may include red and green quantum dots. In some embodiments, the quantum dot has a quantum efficiency of 80% or greater and a half-width of 35nm or less; the quantum efficiency is preferably 90% or more and the half-width is 30nm or less.
In some embodiments, the encapsulation glue layer is a silicone, preferably a high barrier silicone.
In some embodiments, the quantum dot surface ligands are inorganic ligands. The inorganic ligand has stronger temperature stability and oxidation resistance than the organic ligand with common quantum dots.
In some embodiments, the inorganic ligand is a metal oxide ligand, preferably an oxide ligand selected from (Al 2 O 3 ) n -OH、(ZnO) n -OH、(SiO 2 ) n -OH、(ZrO 2 ) n -OH、Ca(OH) 2 、NaOH、Mg(OH) 2 、(ZnMgO) n -OH、(SnO 2 ) n OH, KOH, liOH, csOH, one or more of silicate, aluminosilicate.
In some embodiments, the quantum dot surface ligand is selected from one or more of a metal halide, a metal sulfide, a metal carbonate, a metal sulfate, a metal phosphate.
In some embodiments, the molecular weight of the inorganic ligand is 1 ten thousand or less, preferably 500 to 5000, more preferably 500 to 2000.
In some embodiments, the inorganic ligand is overcoated with an inorganic oxide shell, e.g., al 2 O 3 、ZnO、SnO 2 、In 2 O 3 、GeO 2 、MgO、ZnMgO、SiO 2 、ZrO 2 The shell layer further improves the water oxygen isolation capability of the quantum dot.
In some embodiments, the thickness of the inorganic oxide shell is from 0.5 to 30nm, preferably from 1 to 5nm. In some embodiments, the nano-oxide particles are selected from SnO 2 、ZnO、SiO 2 、In 2 O 3 、GeO 2 、MgO、ZnMgO、Al 2 O 3 、ZrO 2 One or more of the following. In some embodiments, the nano-oxide particles may be core-shell heterojunction structures.
In some embodiments, the variance of the size distribution of the nano-oxide particles is 20% or less, preferably 15% or less. The high uniformity of the nano-oxide particles can enable the nano-oxide particles to have less ineffective gaps when being piled up, and reduce the entry of water vapor and oxygen in the environment through the ineffective gaps (possibly in the presence of packaging glue) and attack the quantum dots.
The final form of the photoluminescence of the quantum dot is that the quantum dot and the LED are directly packaged, and a packaging mode of the QD on chip is adopted, but the light intensity and the temperature damage to the quantum dot is great because the quantum dot and the LED are arranged in a fitting way, and no stable QD on chip product is found in the market. In some embodiments, the quantum dot light conversion device further comprises at least one LED chip on the substrate, the quantum dot layer covering one or more LED chips. The size of the LED chip is not limited. Because the quantum dot layer has higher stability, the quantum dot layer can bear high light intensity and temperature brought by the LED. As shown in fig. 2, the substrate is a support, which includes a bottom and a surrounding side, and the quantum dot layer is located in the space surrounded by the support.
According to another aspect of the present disclosure, there is provided a method of manufacturing a quantum dot light conversion device, the method comprising: preparing a substrate; preparing a dispersion liquid containing nano oxide particles, and preparing a dispersion liquid containing quantum dots, wherein the average size of the nano oxide particles is larger than that of the quantum dots, and the number of the quantum dots in the dispersion liquid of the quantum dots is smaller than that of the nano oxide particles; mixing the dispersion liquid containing the nano oxide particles and the dispersion liquid containing the sub-points to obtain mixed dispersion liquid; setting the mixed dispersion liquid on a substrate, volatilizing a solvent in the mixed dispersion liquid to obtain a quantum dot layer, wherein the stacked nano oxide particles form a plurality of gaps in the quantum dot layer, and n quantum dots are positioned in one gap on average, wherein n is more than 0 and less than 2; and coating the packaging glue on the quantum dot layer and curing to obtain the packaging glue layer. The preparation method does not involve expensive equipment and has relatively low production cost. After most or all of the solvent volatilizes, a plurality of nano oxide particles are in a stacked state, packaging of the quantum dots is realized through gaps among the nano oxide particles and further fixation is carried out through packaging glue, compared with high-barrier film packaging, the product cost is reduced, and the stability of the quantum dots can be effectively improved due to the oxidation resistance and the water vapor barrier property of the nano oxide particles and the quantum dots being surrounded by the nano oxide particles, so that the service life of the quantum dot light conversion device can be prolonged by the preparation method.
In some embodiments, the molar ratio of quantum dots to nano-oxide particles ranges from 0.01 to less than 1.
In some embodiments, the concentration of the nano-oxide particles ranges from 0.1umol/L to 20mmol/L. The concentration of the nano-oxide particles is in the aforementioned range, and it is easier to construct a compact stack of nano-oxide particles.
In some embodiments, the ratio of the average size of the quantum dots to the nano-oxide particles is from 0.207 to 0.414.
In some embodiments, the average size of the nano-oxide particles ranges from 10 to 200nm and the average size of the quantum dots ranges from 6 to 40nm. In some embodiments, the average size of the nano-oxide particles ranges from 20 to 100nm and the average size of the quantum dots ranges from 7 to 30nm.
In some embodiments, the quantum dot-containing dispersion includes first and second quantum dots having different emission peak wavelengths, and in particular, may include red and green quantum dots. In some embodiments, the quantum dot has a quantum efficiency of 80% or greater and a half-width of 35nm or less; the quantum efficiency is preferably 90% or more and the half-width is 30nm or less.
In some embodiments, the encapsulation glue layer is a silicone, preferably a high barrier silicone.
In some embodiments, the quantum dot surface ligands are inorganic ligands. The inorganic ligand has stronger temperature stability and oxidation resistance than the organic ligand.
In some embodiments, the inorganic ligand is a metal oxide ligand, preferably the oxide ligand is (Al 2 O 3 ) n -OH、(ZnO) n -OH、(SiO 2 ) n -OH、(ZrO 2 ) n -OH、Ca(OH) 2 、NaOH、Mg(OH) 2 、(ZnMgO) n OH, KOH, liOH, csOH or (SnO) 2 ) n -OH。
In some embodiments, the quantum dot surface ligand is selected from one or more of a metal halide, a metal sulfide, a metal carbonate, a metal sulfate, a metal phosphate.
In some embodiments, the molecular weight of the inorganic ligand is 10000 or less, preferably 500 to 5000, more preferably 500 to 2000.
In some embodiments, the inorganic ligand is surrounded by an inorganic oxide shell, e.g., al 2 O 3 、ZnO、SnO 2 、In 2 O 3 、GeO 2 、MgO、ZnMgO、SiO 2 、ZrO 2 The shell layer further improves the water oxygen isolation capability of the quantum dot. Preferably, the inorganic oxide shell is alumina. The preparation method of the inorganic oxide shell refers to the prior art.
In some embodiments, the thickness of the inorganic oxide shell is from 0.5 to 30nm, preferably from 1 to 5nm.
In some embodiments, the nano-oxide particles are selected from SnO 2 、ZnO、SiO 2 、In 2 O 3 、GeO 2 、MgO、ZnMgO、Al 2 O 3 And ZrO(s) 2 One or more of the following.
In some embodiments, the variance of the size distribution of the nano-oxide particles in the nano-oxide particle-containing dispersion is 20% or less, preferably 15% or less. The high uniformity of the nano oxide particles can enable the ineffective gaps to be less when the nano oxide particles are stacked, and water vapor and oxygen in the environment are reduced to enter and erode the quantum dots through the ineffective gaps.
In some embodiments, the substrate has at least one LED chip thereon, and the mixed liquid dispersion is disposed on one or more of the LED chips. The quantum dots are protected by the nano oxide particles and have higher stability, so that the quantum dot layer can bear high light intensity and temperature brought by the working of the LED.
Hereinafter, the embodiments are described in more detail with reference to specific examples. However, they are illustrative examples of the present disclosure, and the present disclosure is not limited thereto.
Example 1
And (3) preparing tin dioxide nano particles with the average diameter of 25nm by adopting a microemulsion method, wherein the size distribution variance is less than 20%, and the purified tin dioxide nano particles are dispersed in toluene liquid, and the molar concentration of the tin dioxide nano particles is 20nmol/ml.
The preparation method comprises the steps of preparing red quantum dots and green quantum dots with inorganic ligands by ligand exchange, wherein the red quantum dots CdSeS/ZnS and the green quantum dots CdZnSeS/ZnS are all octadecylamine, and the preparation method is as follows: toluene solution of quantum dot was prepared, and 100mg (Al 2 O 3 ) n Dispersing OH ligand (molecular weight=1000-2000) in 100mL of isopropanol, uniformly mixing quantum dots and isopropanol liquid of inorganic ligand, then performing ultrasonic dispersion for 30min, performing high-speed centrifugation at 100W and 8000rpm to obtain precipitate of the quantum dots containing the inorganic ligand, then re-dispersing the precipitate in a polar solvent, slowly adding 1mL of aluminum isopropoxide and 0.05mL of ammonia water under ice bath condition, completing coating the quantum dots of the inorganic ligand with aluminum oxide (the shell thickness is 20 nm), performing centrifugation at 5000rpm, collecting precipitate, and baking at 180 ℃ for 5 hours to obtain quantum dot powder.
Dispersing red and green quantum dot powder coating an oxide shell layer in toluene liquid, wherein the molar ratio of the green quantum dot to the red quantum dot is 2:1, the average sizes of the red and green quantum dots of the coating oxide shell are respectively 20nm and 18nm, and the ratio of the sum of the mole numbers of the red and green quantum dots of the coating oxide shell to the mole number of the tin dioxide nano particles is 1:10.
and (3) putting the mixed solution of the red and green quantum dots and the tin dioxide nanoparticles into an LED chip bracket through a dispensing machine, slowly evaporating the solvent at normal temperature or by heating (40-130 ℃), depositing the quantum dots and the tin dioxide nanoparticles on the LED chip to form a stack of the quantum dots and the tin dioxide nanoparticles, aging at 100 ℃ for 2 hours to remove all the solvent as much as possible, dispensing, adding phenyl-methyl heat-curing tin resin to cover the stack of the quantum dots and the tin dioxide nanoparticles, and curing at 150 ℃ for 2 hours to obtain the quantum dot LED light-emitting device.
And (3) arranging the mixed solution of the red and green quantum dots and the tin dioxide nano particles on a copper mesh to obtain a overlooking transmission electron microscope TEM image, as shown in figure 3. Wherein the small black dots are quantum dots, and the large spheroids are tin dioxide nanoparticles.
Example 2
The difference from example 1 is that the molar ratio of quantum dots coating the oxide shell layer to the nano-oxide particles ranges from 1:100.
example 3
The difference from example 1 is that the molar ratio of quantum dots coating the oxide shell layer to the nano-oxide particles ranges from 1:1.
example 4
The difference from example 1 is that tin dioxide nano particles with the average size of 80nm are prepared by adopting a microemulsion method, the size distribution variance is less than 15%, the purified tin dioxide nano particles are dispersed in toluene liquid, and the mass concentration of the tin dioxide nano particles is 200mg/mL.
The average size of the red-green quantum dots is 17nm.
Example 5
The difference from example 1 is that the inorganic ligand is Ca (OH) 2 。
Example 6
The difference from example 1 is that the inorganic ligand is NaOH.
Example 7
The difference from example 1 is that the inorganic ligand is a metal carbonate.
Example 8
Differing from example 1 in that the inorganic ligand isZn(OH) 2 。
Example 9
The difference from example 1 is that the inorganic ligand is not coated with the alumina shell, and the precipitate of the quantum dot containing the inorganic ligand obtained by high-speed centrifugation at 8000rpm is baked at 180℃for 5 hours to obtain the quantum dot powder.
Example 10
In contrast to example 1, al having an average size of 30nm was produced by the microemulsion method 2 O 3 The variance of the size distribution of the nano particles is less than 15%, the nano particles are dispersed in toluene after purification, and Al 2 O 3 The mass concentration of the nano particles is 200mg/mL.
The average size of the red and green quantum dots coated with the oxide shell layers is 12.5nm.
Example 11
The difference from example 1 is that no inorganic ligand exchange and no oxide shell coating were performed.
Example 12
The difference from example 1 is that the inorganic ligand exchange is not performed but the inorganic oxide shell coating is performed, toluene liquid of the quantum dot is redispersed in 100mL cyclohexane, 8mL triton X-100 is added, stirring reaction is performed for 30min, 0.5mL aluminum isopropoxide and 0.01mL ammonia water are added under ice bath, the coating of alumina (shell thickness 10 nm) on the quantum dot of the inorganic ligand is completed, then methanol demulsification, centrifugation at 5000rpm is performed, precipitation is collected, and baking is performed at 180 ℃ for 5 hours, thus obtaining quantum dot powder.
Example 13
Unlike example 1, the inorganic ligand was (Al 2 O 3 ) n -OH (molecular weight=1000-2000).
Example 14
The difference from example 1 is that the inorganic ligand is sodium silicate.
Example 15
The difference from example 1 is that the inorganic ligand is an aluminosilicate.
Example 16
The difference from example 1 is that the inorganic ligand is a metal nitrate.
Comparative example
Taking red quantum dots and green quantum dot powder prepared in the embodiment 1, dispersing the red quantum dots and the green quantum dot powder in toluene liquid, adding the red quantum dot powder and the green quantum dot powder into the same silica gel as in the embodiment 1, uniformly mixing, drying to remove toluene, putting the quantum dot glue into an LED chip bracket through a glue dispenser, and curing at 150 ℃ for 2 hours to obtain the quantum dot LED light-emitting device.
The above examples and comparative examples were conducted using 4014 blue light chip, and the quantum efficiency was measured and recorded in a divided manner using a spectroradiometer by lighting for a specific period of time up to 2000 hours at a normal temperature of 80 mA. The aging curve obtained in example 1 is shown in FIG. 4. It can be seen that the quantum efficiency decay rate of example 1 is significantly lower than that of the comparative example. T (T) 90 Refers to the time required for the quantum efficiency to decay to 90% of the initial quantum efficiency, T 95 And so on.
The aging results for each example and comparative example are shown in table 1 below:
from the above table, it can be seen that the packaging manner of the quantum dots in the above embodiment significantly improves the stability, thereby improving the lifetime of the quantum dot LED light conversion device. The service life of the quantum dot LED photoconversion device can show that the stability of the quantum dot containing the inorganic ligand is higher than that of the quantum dot containing the common organic ligand, and the stability of the quantum dot containing the inorganic oxide shell layer is higher than that of the quantum dot containing no inorganic oxide shell layer.
The foregoing description of the preferred embodiments of the present disclosure is provided only and not intended to limit the disclosure so that various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (15)
1. The quantum dot light conversion device is characterized by comprising a substrate, a quantum dot layer and an encapsulation adhesive layer, wherein the quantum dot layer and the encapsulation adhesive layer are arranged on the substrate, the encapsulation adhesive layer covers at least one surface of the quantum dot layer, the quantum dot layer comprises a plurality of nano oxide particles and a plurality of quantum dots, the average size of the nano oxide particles is larger than that of the quantum dots, the nano oxide particles are in a stacked state, the stacked nano oxide particles form a plurality of gaps, n average quantum dots are arranged in the gaps, n is more than 0 and less than 2, and the number of the quantum dots is less than that of the nano oxide particles.
2. The quantum dot light conversion device according to claim 1, wherein the plurality of nano-oxide particles are stacked in a plurality of nano-oxide particle layers, wherein the horizontal pitch of adjacent nano-oxide particles on the same layer is smaller than the average size of the quantum dots, preferably the horizontal pitch is smaller than one quarter of the average size of the quantum dots.
3. The quantum dot light conversion device according to claim 1, wherein the molar ratio of the quantum dot to the nano-oxide particle is 0.01 or more and less than 1, preferably 0.02 to 0.5.
4. The quantum dot light conversion device of claim 1, wherein a ratio of the average size of the quantum dot to the nano-oxide particles is 0.207 to 0.414.
5. The quantum dot light conversion device according to claim 1, wherein the average size of the nano-oxide particles is in the range of 10 to 200nm and the average size of the quantum dots is in the range of 6 to 40nm.
6. The quantum dot light conversion device according to claim 1, wherein the quantum dot surface ligand is an inorganic ligand, preferably the molecular weight of the inorganic ligand is 10000 or less, more preferably 500 to 5000.
7. The quantum dot light-converting device according to claim 6, wherein the inorganic ligand is a metal oxide ligand, preferably the oxide ligand is selected from (Al 2 O 3 ) n -OH、(ZnO) n -OH、(SiO 2 ) n -OH、(ZrO 2 ) n -OH、Ca(OH) 2 、NaOH、Mg(OH) 2 、(ZnMgO) n -OH、(SnO 2 ) n -one or more of OH, silicate, aluminosilicate.
8. The quantum dot light conversion device of claim 6, wherein the quantum dot surface ligand is selected from one or more of a metal halide, a metal sulfide, a metal carbonate, a metal sulfate, and a metal phosphate.
9. The quantum dot light conversion device of claim 6, wherein the inorganic ligand is surrounded by an inorganic oxide shell, preferably the inorganic oxide shell is alumina.
10. The quantum dot light conversion device according to claim 6, wherein the thickness of the inorganic oxide shell layer is 0.5-30 nm, preferably 1-5 nm.
11. The quantum dot light conversion device of claim 1, wherein the nano-oxide particles are selected from SnO 2 、ZnO、SiO 2 、In 2 O 3 、GeO 2 、MgO、ZnMgO、Al 2 O 3 And ZrO(s) 2 One or more of the following.
12. The quantum dot light conversion device according to claim 1, wherein the variance of the size distribution of the nano-oxide particles is 20% or less, preferably 15% or less.
13. The quantum dot light conversion device of claim 1, further comprising at least one LED chip on the substrate, the quantum dot layer covering the LED chip.
14. A method of fabricating a quantum dot light conversion device, the method comprising:
preparing a substrate;
preparing a dispersion liquid containing nano oxide particles, wherein the average size of the nano oxide particles is larger than that of the quantum dots, and the number of the quantum dots in the dispersion liquid of the quantum dots is smaller than that of the nano oxide particles;
mixing the dispersion liquid containing the nano oxide particles and the dispersion liquid containing the quantum dots to obtain a mixed dispersion liquid; setting the mixed dispersion liquid on the substrate, volatilizing a solvent in the mixed dispersion liquid to obtain a quantum dot layer, wherein the stacked nano oxide particles in the quantum dot layer form a plurality of gaps, and n quantum dots are positioned in one gap, wherein n is more than 0 and less than 2;
and coating packaging glue on the quantum dot layer and curing to obtain a packaging glue layer.
15. The method of manufacturing a quantum dot light conversion device according to claim 14, wherein a molar ratio of the quantum dot to the nano-oxide particle is 0.01 or more and less than 1, and preferably, a concentration of the nano-oxide particle is in a range of 0.1umol/L to 20mmol/L.
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