CN112652693A - Quantum dot optical layer and preparation method and application thereof - Google Patents
Quantum dot optical layer and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L33/005—Processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a quantum dot optical layer and a preparation method and application thereof, wherein the preparation method comprises the following steps: coating a conductive film on a transparent insulating base material, coating an anti-etching material on at least one red light quantum dot deposition area and at least one green light quantum dot deposition area, and etching to obtain a quantum dot deposition substrate; synchronously electrodepositing a red light quantum dot material and a green light quantum dot material to the red light quantum dot deposition area and the green light quantum dot deposition area to obtain a red light quantum dot deposition layer and a green light quantum dot deposition layer which are deposited on the transparent insulating substrate; and finally, respectively connecting the red light quantum dot deposition layer and the green light quantum dot deposition layer with a blue light source to obtain the quantum dot optical layer. The preparation method is simple in process and low in preparation cost, and the quantum dot optical layer obtained by the method is high in display luminous efficiency.
Description
Technical Field
The invention relates to the field of LED display, in particular to a quantum dot optical layer and a preparation method and application thereof.
Background
In the field of LED display, a quantum dot color film is a key component for realizing ultra-high color gamut full-color display, because the quantum dot material excites green light and red light of partial wavelength bands by absorbing blue light of partial wavelength bands, the color gamut of a display screen can be effectively improved, and the requirement of high-quality display application is met. At present, quantum dots are mainly dispersed in photoresist, and then the quantum dot light conversion material is coated on a specific area of a substrate in a light curing and etching mode.
CN105098002A discloses a method for patterning a photoresist layer, a quantum dot layer, a QLED, a quantum dot color film and a display device, where the method for patterning a quantum dot layer includes forming a photoresist material layer on a substrate, patterning the photoresist, performing hydrophilic treatment on the photoresist, coating quantum dots, removing the quantum dots on the remaining photoresist and stripping the photoresist. The quantum dot layer patterning method can improve the hydrophilic performance of the photoresist and reduce the adhesive force of the quantum dots with lipophilicity on the photoresist. When the photoresist is stripped, the quantum dots at the target position of the substrate can not fall off.
CN105242442A discloses a method for preparing a quantum dot color film, in which a blue sub-pixel portion of a quantum dot color film is formed by a photolithography process using a transparent organic photoresist material, a transparent organic photoresist layer is subjected to a hydrophobic treatment, a green quantum dot cured resin and a red quantum dot photoresist are sequentially coated on corresponding regions by virtue of the hydrophobic property, so as to sequentially obtain a green quantum dot cured resin layer and a red quantum dot photoresist layer thereon, and then a part of the red quantum dot photoresist layer is etched by the photolithography process, so as to obtain the green sub-pixel portion and the red sub-pixel portion of the quantum dot color film. Compared with the traditional manufacturing method of the quantum dot color film, the manufacturing method of the invention at least reduces one photoetching process.
In the prior art, the preparation process of the quantum dot optical layer is complex, the production cost is high, the requirements on the equipment capacity and precision are high, and the pixel-level arrangement is difficult to realize.
Therefore, the research at present focuses on developing a preparation method of a quantum dot optical layer with simple process and low preparation cost, and the quantum dot optical layer obtained by the method has high luminous efficiency.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the quantum dot optical layer, the preparation method and the 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 producing a quantum dot optical layer, the method comprising the steps of:
(1) coating a conductive film on a transparent insulating substrate, then coating an etching-resistant material on at least one red light quantum dot deposition area (such as 3, 5, 10 and the like) and at least one green light quantum dot deposition area (such as 3, 5, 10 and the like), and etching to obtain a quantum dot deposition substrate;
(2) synchronously electrodepositing a red light quantum dot material and a green light quantum dot material to the red light quantum dot deposition area and the green light quantum dot deposition area to obtain a red light quantum dot deposition layer and a green light quantum dot deposition layer which are deposited on the transparent insulating base material;
(3) and respectively connecting the red light quantum dot deposition layer and the green light quantum dot deposition layer with a blue light source to obtain the quantum dot optical layer.
The preparation method of the quantum dot optical layer provided by the invention adopts an electrodeposition mode and mainly has the following advantages:
(1) the pixel-level coating of the quantum dot luminescent material is realized, the process is simple, and the manufacturing cost is low;
(2) red light quantum dot deposition area and green glow quantum dot deposition area can carry out accurate division according to practical application demand in the quantum dot deposition base plate, and the quantum dot material can selectively deposit in appointed area, and the coating effect is good, can realize mass production.
Preferably, in the step (1), the conductive film includes an ITO film, and the transparent insulating substrate of the present invention includes any one of polyethylene terephthalate (PET), Polyimide (PI), polypropylene (PP), or inorganic glass.
Preferably, the coating method includes any one of magnetron sputtering, vacuum evaporation or sol-gel spin coating.
Preferably, the etching comprises chemical etching or physical etching.
Preferably, the etch-resistant material comprises any one or at least two combinations of a metal plating, an oxide plating or an organic masking layer, wherein typical but non-limiting combinations include: a combination of a metal plating layer and an oxide plating layer, a combination of an oxide plating layer and an organic masking layer, a combination of a metal plating layer, an oxide plating layer and an organic masking layer, and the like.
Preferably, step (1) further comprises: after the etching, the etching resist material is stripped and the substrate is cleaned.
Preferably, the method of cleaning comprises any one or at least two combinations of organic solution cleaning, water cleaning or plasma cleaning, wherein typical but non-limiting combinations include: a combination of organic solution cleaning and water cleaning, a combination of water cleaning and plasma cleaning, a combination of organic solution cleaning, water cleaning and plasma cleaning, and the like.
Preferably, step (1) further comprises: after the etching, a circuit is mounted on the conductive film to connect the red quantum dot deposition regions to each other and the green quantum dot deposition regions to each other.
Preferably, the red light quantum dot material and the green light quantum dot material are opposite in charge, and the red light quantum dot material and the green light quantum dot material are opposite in charge, so that the red light quantum dot material and the green light quantum dot material can be synchronously deposited in the electrodeposition process, the preparation process is shortened, and the cost is saved.
Preferably, the red light quantum dot material and the green light quantum dot material each independently comprise AxMyEzSystem material and coating in sequence AxMyEzA coating material and a ligand material on the surface of the system material, wherein x is 0.3-2.0, such as 0.5, 1.0, 1.5 and the like, y is 0.5-3.0, such as 1.0, 1.5, 2.0, 2.5 and the like, and z is 0-4.0, such as 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 and the like;
a is any one of Ba, Ag, Na, Fe, In, Cd, Zn, Ga, Mg, Pb or Cs;
m is any one of S, Cl, O, As, N, P, Se, Te, Ti, Zr or Pb;
and E is any one of S, As, Se, O, Cl, Br or I.
Preferably, A isxMyEzThe system material comprises GaN, CdSe, InP or CsPbBr3Any one or at least two combinations thereof, wherein typical but non-limiting combinations include: combination of CdSe and InP, CdSe, InP and CsPbBr3GaN, CdSe, InP and CsPbBr3Combinations of (a), (b), and the like.
Preferably, the coating material includes an organic polymer solution and/or an inorganic compound.
Preferably, the organic polymer solution comprises any one or at least two combinations of poly-octadecene, polypropylene glycol methyl ether acetate (PMA) or polyvinylidene fluoride (PVDF), wherein typical but non-limiting combinations include combinations of octadecene and PMA, PMA and PVDF, octadecene, PMA and PVDF, and the like.
Preferably, the inorganic compound comprises silicon dioxide (SiO)2) Titanium dioxide (TiO)2) Zirconium dioxide (ZrO)2) Any one or a combination of at least two of zinc oxide (ZnO) or zinc sulfide (ZnS), wherein typical but non-limiting combinations include: SiO 22ZnO and ZnS, TiO2And ZrO2Combination of (A) and (B), ZrO2And ZnO combination, TiO2、ZrO2Or a combination of ZnO, and the like.
Preferably, the ligand material comprises an organic salt.
Preferably, the organic salt comprises any one or a combination of at least two of sodium acetate, picolinate, sodium ethoxide, tetrabutylammonium bromide, ammonium chloride or ammonium sulfate, wherein typical but non-limiting combinations include: combinations of sodium acetate and picolinate, sodium ethoxide, tetrabutylammonium bromide and ammonium bromide, tetrabutylammonium bromide, ammonium chloride and ammonium sulfate, picolinate, sodium ethoxide, tetrabutylammonium bromide, ammonium bromide and ammonium chloride, sodium acetate, picolinate, sodium ethoxide, tetrabutylammonium bromide, ammonium bromide and ammonium chloride, ammonium acetate, pyridinium, sodium ethoxide, tetrabutylammonium bromide, ammonium chloride and ammonium sulfate, and the like.
The ligand materials used by the red light quantum dot material and the green light quantum dot material are opposite in acid-base property, so that the quantum dot material with opposite electrical property is obtained.
Preferably, the particle size of the red light quantum dot material is 7-12nm, such as 8nm, 9nm, 10nm, 11nm, 12nm and the like.
Preferably, the particle size of the green light quantum dot material is 3-7nm, such as 4nm, 5nm, 6nm, etc.
Preferably, the emission peak wavelength of the red light quantum dot material is 600-660nm, such as 610nm, 620nm, 630nm, 640nm, 650nm and the like.
Preferably, the luminescence peak wavelength of the green light quantum dot material is 510-550nm, such as 520nm, 530nm, 540nm and the like.
Preferably, the half-peak width of the emitted light of the red light quantum dot material is less than 35nm, such as 30nm, 25nm, 20nm, 15nm and the like.
Preferably, the green light quantum dot material has an emission peak width at half maximum of < 35nm, such as 30nm, 25nm, 20nm, 15nm, etc.
Preferably, the step (2) specifically comprises: placing the quantum dot deposition substrate obtained in the step (1) in an electrodeposition solution containing a red light quantum dot material and a green light quantum dot material, respectively connecting a red light quantum dot deposition area and a green light quantum dot deposition area with two electrodes of a direct current power supply, electrifying, and synchronously electrodepositing the red light quantum dot material and the green light quantum dot material to the red light quantum dot deposition area and the green light quantum dot deposition area;
the red light quantum dot material and the green light quantum dot material are opposite in charge.
Preferably, in step (2), the current for electrodeposition is 1 to 20mA, such as 5mA, 10mA, 15mA, and the like.
Preferably, in the step (2), the voltage of the dc power supply is 1-12V, such as 2V, 4V, 6V, 8V, 10V, etc.
Preferably, in step (2), the electrodeposition time is 0.5-30min, such as 5min, 10min, 15min, 20min, 25min, and the like.
Preferably, in the step (2), the electrodeposition solution containing the red light quantum dot material and the green light quantum dot material is formed by mixing the red light quantum dot electrodeposition solution and the green light quantum dot electrodeposition solution.
Preferably, the preparation method of the red light quantum dot electrodeposition solution comprises the following steps: synthesis of A by solution Process in reaction solventxMyEzAnd (3) dropwise adding a coating layer material to the system material to obtain a red light quantum dot material with a core-shell structure, purifying, placing the red light quantum dot material with the core-shell structure in a solvent, adding a ligand material, and carrying out a bonding reaction to obtain a red light quantum dot electrodeposition solution.
Preferably, the preparation method of the electrodeposition solution of the green light quantum dots comprises the following steps: synthesis of A by solution Process in reaction solventxMyEzAnd (3) dropwise adding a coating layer material to the system material to obtain a green light quantum dot material with a core-shell structure, purifying, placing the core-shell structure green light quantum dot material in a solvent, adding a ligand material, and carrying out a bonding reaction to obtain a green light quantum dot electrodeposition solution.
Preferably, the reaction solvent comprises any one or a combination of at least two of oleylamine, oleic acid or long chain phosphonic acids, with typical but non-limiting combinations including: combinations of oleylamine and oleic acid, oleylamine and long chain phosphonic acid, oleylamine, oleic acid and long chain phosphonic acid, and the like.
Preferably, the pH of the bonding reaction is in the range of 5.5 to 11, e.g., 6, 7, 8, 9, 10, etc.
Preferably, the temperature of the bonding reaction is 120-320 ℃, such as 150 ℃, 200 ℃, 250 ℃, 300 ℃ and the like.
Preferably, the time of the bonding reaction is 0.5-35min, such as 5min, 10min, 15min, 20min, 25min, and the like.
Preferably, step (2) further comprises: and after the electrodeposition, taking out the deposited quantum dot deposition substrate, drying, spraying and coating packaging glue, and curing to obtain a red light quantum dot deposition layer and a green light quantum dot deposition layer deposited on the transparent insulating base material.
Preferably, in step (3), the blue light source includes a blue light driving circuit and at least three blue light source layers, for example, 3, 6, 12, 24, etc., arranged side by side on the blue light driving circuit.
Preferably, in the step (3), the red light quantum dot material and the green light quantum dot material are respectively connected with the blue light source layer.
The number of the blue light source layers is at least three because the red light quantum dot material, the green light quantum dot material and the blue light source form a light-emitting display unit, and the red light quantum dot material and the green light quantum dot material are respectively connected with the blue light source layer, so that each quantum dot optical layer needs at least three blue light source layers.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) preparation of quantum dot deposition substrate
a. Coating the ITO film on a transparent insulating substrate, and curing to obtain a cured ITO film;
b. coating an anti-etching material on at least one red light quantum dot deposition area and at least one green light quantum dot deposition area, and etching;
c. stripping and cleaning the etching-resistant material on the etched ITO film;
d. c, mounting a circuit on the ITO film obtained in the step c, enabling the red light quantum dot deposition areas to be mutually connected to realize electric conduction, enabling the green light quantum dot deposition areas to be mutually connected to realize electric conduction, and obtaining a quantum dot deposition substrate;
(2) preparation of red light quantum dot deposition layer and green light quantum dot deposition layer
e. Synthesis of A by solution Process in reaction solventxMyEzThe method comprises the following steps of (1) dropwise adding a coating material to a system material to obtain a red light quantum dot material with a core-shell structure, purifying, placing the red light quantum dot material with the core-shell structure in a solvent, adding a ligand material, and carrying out a bonding reaction to obtain an electrified red light quantum dot electrodeposition solution;
f. synthesis of A by solution Process in reaction solventxMyEzThe system material is added with the cladding layer material dropwise to obtain a green light quantum dot material with a core-shell structure, the green light quantum dot material with the core-shell structure is placed in a solvent after purification, a ligand material is added, and a bonding reaction is carried out to obtain a green light quantum dot electrodeposition solution with charges opposite to those of the red light quantum dot electrodeposition solution;
g. mixing the quantum dot electrodeposition solutions obtained in the steps e and f;
h. placing the quantum dot deposition substrate in a charged core-shell quantum dot solution;
i. connecting the red light quantum dot deposition area and the green light quantum dot deposition area with the positive electrode or the negative electrode of a direct current power supply respectively, electrifying, synchronously and automatically depositing red and green quantum dot materials in the corresponding areas under the action of an electric field, taking out the deposited quantum dot deposition substrate, drying, spraying packaging glue, and curing to obtain the red light quantum dot deposition layer and the green light quantum dot deposition layer;
(3) preparation of quantum dot optical layers
j. And arranging at least three blue light source layers on a blue light drive circuit side by side, and respectively installing a green light quantum dot deposition layer and a red light quantum dot deposition layer on the blue light source layers to obtain the quantum dot optical layers.
In a second aspect, the present invention provides a quantum dot optical layer prepared by the preparation method of the first aspect. The quantum dot optical layer can realize pixel-level quantum dot arrangement, has high display resolution, can eliminate the use of an optical filter, improves the light passing rate and the display light effect, and reduces the overall power consumption of the device.
In a third aspect, the present invention provides a display device in which the quantum dot optical layer of the second aspect is provided. The quantum dot optical layer can be applied to various display devices, and is good in application compatibility and high in color gamut of the display devices.
In a fourth aspect, the present invention provides a use of the display device of the third aspect in an LED display apparatus.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the quantum dot optical layer adopts an electrodeposition mode to realize pixel-level coating of the quantum dot luminescent material, and has the advantages of simple process and low manufacturing cost. And the red light quantum dot deposition area and the green light quantum dot deposition area in the quantum dot deposition substrate can be accurately divided according to the actual application requirements, the quantum dot material can be selectively deposited in the designated area, the coating effect is good, and batch production can be realized. The light conversion efficiency is more than 79%, the service life of the optical layer L70 is more than 20800 hours, the color gamut value of the display device is more than 116%, and the display device has the excellent characteristics of high reliability and durability.
Drawings
Fig. 1 is a schematic diagram of a process for preparing a red light quantum dot deposition layer and a green light quantum dot deposition layer in example 1 of the present invention;
wherein, 10-the first AxMyEzSystem material, 101-positively charged green quantum dot material, 20-second AxMyEzThe method comprises the following steps of system materials 102-red light quantum dot materials with negative electricity, 30-quantum dot electrodeposition solution containing the red light quantum dot materials and the green light quantum dot materials, 40-quantum dot deposition substrates and 50-deposited quantum dot deposition substrates.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. 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
As shown in fig. 1, a process for preparing a red light quantum dot deposition layer and a green light quantum dot deposition layer is shown in the figure, and the method for preparing a quantum dot optical layer provided in this embodiment includes the content shown in fig. 1, and specifically includes the following steps:
(1) preparation of quantum dot deposition substrate
a. Coating the ITO film on PET, and curing to obtain a cured ITO film;
b. coating an organic masking layer (quinacridone solution) on the red light quantum dot deposition area and the green light quantum dot deposition area, and etching;
c. stripping and washing the etching-resistant material on the etched ITO film with water;
d. c, mounting a circuit on the ITO film obtained in the step c, enabling the red light quantum dot deposition areas to be mutually connected to realize electric conduction, enabling the green light quantum dot deposition areas to be mutually connected to realize electric conduction, and obtaining a quantum dot deposition substrate 40;
(2) preparation of red light quantum dot deposition layer and green light quantum dot deposition layer
e. Synthesis of the second A by solution Process in oleic acidxMyEzThe preparation method comprises the following steps of (1) dropwise adding PVDF into a system material 20(CdSe), obtaining a red light quantum dot material with a core-shell structure (the particle size is 10nm, the wavelength of a light-emitting peak is 630nm), purifying, then placing the red light quantum dot material with the core-shell structure into a solvent, adding sodium ethoxide, adjusting the pH to be 6 and the temperature to be 200 ℃, and carrying out bonding reaction for 20min to obtain an electrodeposition solution containing the red light quantum dot material 102 with negative electricity;
f. synthesis of the first A by solution Process in oleylaminexMyEzThe method comprises the following steps of (1) dropwise adding a system material 10(CdSe) into a cladding material to obtain a green light quantum dot material (the particle size is 5nm, the wavelength of a luminescence peak is 530nm) with a core-shell structure, then placing the green light quantum dot material with the core-shell structure into a solvent, adding tetrabutyl ammonium bromide, adjusting the pH to be 8 and the temperature to be 200 ℃, and carrying out bonding reaction for 20min to obtain an electrodeposition solution containing the green light quantum dot material 101 with positive charges;
g. mixing the quantum dot electrodeposition solutions obtained in the steps e and f to obtain a quantum dot electrodeposition solution 30 containing a red light quantum dot material and a green light quantum dot material;
h. placing the quantum dot deposition substrate in a quantum dot electrodeposition solution 30 containing red light quantum dot material and green light quantum dot material;
i. connecting the red light quantum dot deposition area and the green light quantum dot deposition area with a positive electrode and a negative electrode of a direct current power supply respectively, electrifying, enabling the voltage to be 6V and the current to be 10mA, synchronously carrying out self-deposition on red and green quantum dot materials in corresponding areas for 20min under the action of an electric field, taking out the deposited quantum dot deposition substrate, drying, spraying methyl phenyl silicone resin, and curing to obtain a deposited quantum dot deposition substrate 50, wherein the deposited quantum dot deposition substrate comprises a red light quantum dot deposition layer and a green light quantum dot deposition layer;
(3) preparation of quantum dot optical layers
j. And arranging the blue light source layers on the blue light drive circuit side by side, and respectively installing the green light quantum dot deposition layer and the red light quantum dot deposition layer on the blue light source layers to obtain the quantum dot optical layers.
The embodiment also provides a QD-Micro-LED display device, which includes the obtained quantum dot optical layer, and the specific assembly method is as follows:
(1) preparing a display panel driving circuit;
(2) mounting a blue light Micro-LED chip on a driving circuit in a mass transfer mode;
(3) aligning the quantum dot optical layer to a Micro-LED chip;
(4) assembling the display panel and communicating the display panel with the circuit;
(5) under the excitation of a blue light Micro-LED, the quantum dot optical layer emits red light, green light and blue light, and the Micro-LED is compounded to realize full-color display.
Example 2
The embodiment provides a preparation method of a quantum dot optical layer, which specifically comprises the following steps:
(1) preparation of quantum dot deposition substrate
a. Coating an ITO film on PI, and curing to obtain a cured ITO film;
b. coating the metal coating on the red light quantum dot deposition area and the green light quantum dot deposition area, and etching;
c. stripping the etching-resistant material on the etched ITO film and cleaning the etching-resistant material by using an organic solution;
d. c, mounting a circuit on the ITO film obtained in the step c, enabling the red light quantum dot deposition areas to be mutually connected to realize electric conduction, and enabling the green light quantum dot deposition areas to be mutually connected to realize electric conduction to obtain a quantum dot deposition substrate;
(2) preparation of red light quantum dot deposition layer and green light quantum dot deposition layer
e. InP is synthesized in oleic acid by a solution method, PMA is dripped to obtain a red light quantum dot material with a core-shell structure (the particle size is 7nm, the wavelength of a light-emitting peak is 600nm), then the red light quantum dot material with the core-shell structure is placed in a solvent, picolinate is added, the pH is adjusted to 5.5, the temperature is 320 ℃, and bonding reaction is carried out for 0.5min to obtain a positively charged red light quantum dot electrodeposition solution;
f. InP is synthesized in oleylamine by a solution method, and SiO is dripped2Obtaining a green light quantum dot material with a core-shell structure (the particle size is 3nm, and the wavelength of a light-emitting peak value is 510nm), then placing the green light quantum dot material with the core-shell structure in a solvent, adding ammonium chloride, adjusting the pH to 11, and the temperature to 320 ℃, and carrying out bonding reaction for 0.5min to obtain a negative electricity green light quantum dot electrodeposition solution;
g. mixing the quantum dot electrodeposition solutions obtained in the steps e and f;
h. placing the quantum dot deposition substrate in a charged core-shell quantum dot solution;
i. connecting the red light quantum dot deposition area and the green light quantum dot deposition area with a negative electrode and a positive electrode of a direct current power supply respectively, electrifying, enabling the voltage to be 12V and the current to be 20mA, synchronously carrying out self-deposition on red and green quantum dot materials in corresponding areas for 0.5min under the action of an electric field, carrying out self-deposition on the red and green quantum dot materials in the corresponding areas, taking out the deposited quantum dot deposition substrate, drying, spraying glycidyl ether epoxy resin, and curing to obtain a red light quantum dot deposition layer and a green light quantum dot deposition layer;
(3) preparation of quantum dot optical layers
j. And arranging the blue light source layers on the blue light drive circuit side by side, and respectively installing the green light quantum dot deposition layer and the red light quantum dot deposition layer on the blue light source layers to obtain the quantum dot optical layers.
The embodiment also provides a QD-Micro-LED display device, which includes the obtained quantum dot optical layer, and the specific assembly method is as follows:
(1) preparing a display panel driving circuit;
(2) mounting a blue light Micro-LED chip on a driving circuit in a mass transfer mode;
(3) aligning the quantum dot optical layer to a Micro-LED chip;
(4) assembling the display panel and communicating the display panel with the circuit;
(5) under the excitation of a blue light Micro-LED, the quantum dot optical layer emits red light, green light and blue light, and the Micro-LED is compounded to realize full-color display.
Example 3
The embodiment provides a preparation method of a quantum dot optical layer, which specifically comprises the following steps:
(1) preparation of quantum dot deposition substrate
a. Coating the ITO film on PP, and curing to obtain a cured ITO film;
b. coating the oxide coating on the red light quantum dot deposition area and the green light quantum dot deposition area, and etching;
c. stripping and plasma cleaning the etching-resistant material on the etched ITO film;
d. c, mounting a circuit on the ITO film obtained in the step c, enabling the red light quantum dot deposition areas to be mutually connected to realize electric conduction, and enabling the green light quantum dot deposition areas to be mutually connected to realize electric conduction to obtain a quantum dot deposition substrate;
(2) preparation of red light quantum dot deposition layer and green light quantum dot deposition layer
e. In long chainSynthesis of CsPbBr in phosphonic acid by solution method3Dissolving and dripping TiO2And ZnS to obtain a red light quantum dot material with a core-shell structure (the particle size is 12nm, the wavelength of a luminescence peak is 660nm), then placing the red light quantum dot material with the core-shell structure in a solvent, adding sodium acetate, adjusting the pH to 6, and the temperature to 120 ℃, and carrying out bonding reaction for 35min to obtain a negatively charged red light quantum dot electrodeposition solution;
f. synthesizing GaN in oleylamine by a solution method, dissolving, dropwise adding ZnO to obtain a green light quantum dot material with a core-shell structure (the particle size is 3nm, the wavelength of a light-emitting peak is 550nm), placing the green light quantum dot material with the core-shell structure in a solvent, adding ammonium sulfate, adjusting the pH to be 8 and the temperature to be 120 ℃, and carrying out bonding reaction for 35min to obtain a green light quantum dot electrodeposition solution with positive electricity;
g. mixing the quantum dot electrodeposition solutions obtained in the steps e and f;
h. placing the quantum dot deposition substrate in a charged core-shell quantum dot solution;
i. connecting the red light quantum dot deposition area and the green light quantum dot deposition area with a positive electrode and a negative electrode of a direct current power supply respectively, electrifying, enabling the voltage to be 1V and the current to be 1mA, synchronously carrying out self-deposition on red and green quantum dot materials in corresponding areas for 30min under the action of an electric field, carrying out self-deposition on the red and green quantum dot materials in the corresponding areas, taking out the deposited quantum dot deposition substrate, drying, spraying polyurethane, and curing to obtain a red light quantum dot deposition layer and a green light quantum dot deposition layer;
(3) preparation of quantum dot optical layers
j. And arranging at least three blue light source layers on a blue light drive circuit side by side, and respectively installing a green light quantum dot deposition layer and a red light quantum dot deposition layer on the blue light source layers to obtain the quantum dot optical layers.
The embodiment also provides a QD-Micro-LED display device, which includes the obtained quantum dot optical layer, and the specific assembly method is as follows:
(1) preparing a display panel driving circuit;
(2) mounting a blue light Micro-LED chip on a driving circuit in a mass transfer mode;
(3) aligning the quantum dot optical layer to a Micro-LED chip;
(4) assembling the display panel and communicating the display panel with the circuit;
(5) under the excitation of a blue light Micro-LED, the quantum dot optical layer emits red light, green light and blue light, and the Micro-LED is compounded to realize full-color display.
Comparative example 1
The comparative example provides a preparation method of a quantum dot optical layer, which specifically comprises the following steps:
(1) mixing the red and green quantum dot materials into acrylic acid glue, and uniformly stirring;
(2) coating the obtained red and green quantum dot mixed glue between two layers of PET films, and attaching;
(3) placing the obtained PET film coated with the quantum dot glue in an ultraviolet curing box, and curing the acrylic glue under 385nm ultraviolet light;
(4) and cutting the film according to the size of the display screen to obtain the quantum dot optical layer.
The present comparative example also provides a QD-LCD display device comprising the resulting quantum dot optical layer, specifically assembled as follows: the red and green quantum dot optical layer is assembled in a QD-LCD display device, and full-color display is realized through wavelength selection of the optical filter.
Performance testing
And (3) testing the performance of the quantum dot optical film:
(1) testing the light conversion efficiency: the light conversion efficiency is the output light power/incident light power, and the standard spectrum of am1.5g is used.
(2) Optical film L70 lifetime: that is, the luminance parameter nit of the display device is used with an operating time which is maintained until the light emission intensity decays to 70% of the initial value at the normal temperature lighting (25 ℃).
Performance test of the display device:
(3) display device color gamut value: according to the NTSC standard.
The above test results are shown in table 1:
TABLE 1
| Light conversion efficiency/%) | Lifetime of light-emitting layer L70/hr | Display device color gamut value/%) | |
| Example 1 | 82％ | 22000 | 116％ |
| Example 2 | 79％ | 21600 | 122％ |
| Example 3 | 84％ | 20800 | 121％ |
| Comparative example 1 | 28％ | 14500 | 105％ |
Compared with the conventional method, the preparation method of the quantum dot optical layer provided by the invention is simpler, more convenient and easier, and is easy to realize industrialization, and the obtained quantum dot light-emitting layer does not need to use an optical filter, so that the light passing rate and the display light effect are improved, and the overall power consumption of the device is reduced. From the data in table 1, the light conversion efficiency is 79% or more, the life of the optical layer L70 is 20800 hours or more, the color gamut value of the display device is 116% or more, and the display device has the excellent characteristics of high reliability and durability.
Analysis of comparative example 1 and example 1 revealed that the performance of the display device composed of the optical layer obtained by the conventional method was inferior to that of example 1.
In conclusion, the preparation method of the quantum dot optical layer provided by the invention is simpler, easier and more convenient than the conventional method, is beneficial to improving the light passing rate and the display light effect, and reduces the overall power consumption of the device.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for producing a quantum dot optical layer, comprising the steps of:
(1) coating a conductive film on a transparent insulating base material, then coating an anti-etching material on at least one red light quantum dot deposition area and at least one green light quantum dot deposition area, and etching to obtain a quantum dot deposition substrate;
(2) synchronously electrodepositing a red light quantum dot material and a green light quantum dot material to the red light quantum dot deposition area and the green light quantum dot deposition area to obtain a red light quantum dot deposition layer and a green light quantum dot deposition layer which are deposited on the transparent insulating base material;
(3) and respectively connecting the red light quantum dot deposition layer and the green light quantum dot deposition layer with a blue light source to obtain the quantum dot optical layer.
2. The production method according to claim 1, wherein in the step (1), the conductive film comprises an ITO film;
preferably, the coating method comprises any one of magnetron sputtering, vacuum evaporation or sol-gel spin coating;
preferably, the etching comprises chemical etching or physical etching;
preferably, step (1) further comprises: stripping the etching-resistant material after the etching, and cleaning the substrate;
preferably, the cleaning method comprises any one or at least two combinations of organic solution cleaning, water cleaning or plasma cleaning;
preferably, step (1) further comprises: after the etching, a circuit is mounted on the conductive film to connect the red quantum dot deposition regions to each other and the green quantum dot deposition regions to each other.
3. The method of manufacturing according to claim 1 or 2, wherein the red and green quantum dot materials are oppositely charged;
preferably, the red light quantum dot material and the green light quantum dot material each independently comprise AxMyEzSystem material and coating in sequence AxMyEzA coating layer material and a ligand material on the surface of the system material, wherein x is 0.3-2.0, y is 0.5-3.0, and z is 0-4.0;
a is any one of Ba, Ag, Na, Fe, In, Cd, Zn, Ga, Mg, Pb or Cs;
m is any one of S, Cl, O, As, N, P, Se, Te, Ti, Zr or Pb;
e is any one of S, As, Se, O, Cl, Br or I;
preferably, A isxMyEzThe system material comprises GaN, CdSe, InP or CsPbBr3Any one or a combination of at least two of;
preferably, the coating material includes an organic polymer solution and/or an inorganic compound;
preferably, the ligand material comprises an organic salt;
preferably, the organic salt comprises any one or at least two of sodium acetate, picolinate, sodium ethoxide, tetrabutylammonium bromide, ammonium chloride or ammonium sulfate;
preferably, the particle size of the red light quantum dot material is 7-12 nm;
preferably, the particle size of the green light quantum dot material is 3-7 nm;
preferably, the emission peak wavelength of the red light quantum dot material is 600-660 nm;
preferably, the luminescence peak wavelength of the green light quantum dot material is 510-550 nm;
preferably, the half-peak width of the emitted light of the red light quantum dot material is less than 35 nm;
preferably, the emission peak width at half maximum of the green light quantum dot material is less than 35 nm.
4. The method according to any one of claims 1 to 3, wherein the step (2) specifically comprises: placing the quantum dot deposition substrate obtained in the step (1) in an electrodeposition solution containing a red light quantum dot material and a green light quantum dot material, respectively connecting a red light quantum dot deposition area and a green light quantum dot deposition area with two electrodes of a direct current power supply, electrifying, and synchronously electrodepositing the red light quantum dot material and the green light quantum dot material to the red light quantum dot deposition area and the green light quantum dot deposition area;
the red light quantum dot material and the green light quantum dot material have opposite charges;
preferably, in the step (2), the electric current of the electrodeposition is 1-20 mA;
preferably, in the step (2), the voltage of the direct current power supply is 1-12V;
preferably, in the step (2), the electrodeposition time is 0.5-30 min.
5. The preparation method according to any one of claims 1 to 4, wherein in the step (2), the electrodeposition solution containing the red light quantum dot material and the green light quantum dot material is formed by mixing the red light quantum dot electrodeposition solution and the green light quantum dot electrodeposition solution;
preferably, the preparation method of the red light quantum dot electrodeposition solution comprises the following steps: synthesis of A by solution Process in reaction solventxMyEzDropwise adding a coating layer material to the system material to obtain a red light quantum dot material with a core-shell structure, purifying, then placing the core-shell structure red light quantum dot material in a solvent, adding a ligand material, and carrying out a bonding reaction to obtain a red light quantum dot electrodeposition solution;
preferably, the preparation method of the electrodeposition solution of the green light quantum dots comprises the following steps: synthesis of A by solution Process in reaction solventxMyEzThe method comprises the following steps of (1) dropwise adding a coating layer material to a system material to obtain a green light quantum dot material with a core-shell structure, purifying, placing the core-shell structure green light quantum dot material in a solvent, adding a ligand material, and carrying out a bonding reaction to obtain a green light quantum dot electrodeposition solution;
preferably, the reaction solvent comprises any one of oleylamine, oleic acid or long chain phosphonic acid, or a combination of at least two thereof;
preferably, the pH of the bonding reaction is 5.5 to 11;
preferably, the temperature of the bonding reaction is 120-320 ℃;
preferably, the time of the bonding reaction is 0.5-35 min;
preferably, step (2) further comprises: and after the electrodeposition, taking out the deposited quantum dot deposition substrate, drying, spraying and coating packaging glue, and curing to obtain a red light quantum dot deposition layer and a green light quantum dot deposition layer deposited on the transparent insulating base material.
6. The production method according to any one of claims 1 to 5, wherein in the step (3), the blue light source comprises a blue light drive circuit and at least three blue light source layers arranged side by side on the blue light drive circuit;
preferably, in the step (3), the red light quantum dot material and the green light quantum dot material are respectively connected with the blue light source layer.
7. The production method according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) preparation of quantum dot deposition substrate
a. Coating the ITO film on a transparent insulating substrate, and curing to obtain a cured ITO film;
b. coating an anti-etching material on at least one red light quantum dot deposition area and at least one green light quantum dot deposition area, and etching;
c. stripping and cleaning the etching-resistant material on the etched ITO film;
d. c, mounting a circuit on the ITO film obtained in the step c, enabling the red light quantum dot deposition areas to be mutually connected to realize electric conduction, enabling the green light quantum dot deposition areas to be mutually connected to realize electric conduction, and obtaining a quantum dot deposition substrate;
(2) preparation of red light quantum dot deposition layer and green light quantum dot deposition layer
e. Synthesis of A by solution Process in reaction solventxMyEzThe method comprises the following steps of (1) dropwise adding a coating material to a system material to obtain a red light quantum dot material with a core-shell structure, purifying, placing the red light quantum dot material with the core-shell structure in a solvent, adding a ligand material, and carrying out a bonding reaction to obtain an electrified red light quantum dot electrodeposition solution;
f. synthesis of A by solution Process in reaction solventxMyEzThe system material is added with the cladding layer material dropwise to obtain a green light quantum dot material with a core-shell structure, the green light quantum dot material with the core-shell structure is placed in a solvent after purification, a ligand material is added, and a bonding reaction is carried out to obtain a green light quantum dot electrodeposition solution with charges opposite to those of the red light quantum dot electrodeposition solution;
g. mixing the quantum dot electrodeposition solutions obtained in the steps e and f;
h. placing the quantum dot deposition substrate in a charged core-shell quantum dot solution;
i. connecting the red light quantum dot deposition area and the green light quantum dot deposition area with the positive electrode or the negative electrode of a direct current power supply respectively, electrifying, synchronously and automatically depositing red and green quantum dot materials in corresponding areas under the action of an electric field, taking out the deposited quantum dot deposition substrate, drying, spraying packaging glue, and curing to obtain a red light quantum dot deposition layer and a green light quantum dot deposition layer;
(3) preparation of quantum dot optical layers
j. And arranging at least three blue light source layers on a blue light drive circuit side by side, and respectively installing a green light quantum dot deposition layer and a red light quantum dot deposition layer on the blue light source layers to obtain the quantum dot optical layers.
8. A quantum dot optical layer produced by the production method according to any one of claims 1 to 7.
9. A display device comprising the quantum dot optical layer of claim 8.
10. Use of a display device according to claim 9 in a LED display device.
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Application publication date: 20210413 |