CN112802947A - Quantum dot display device and preparation method thereof - Google Patents
Quantum dot display 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
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- H01L25/16—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits
- H01L25/167—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different main groups of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. forming hybrid circuits comprising optoelectronic devices, e.g. LED, photodiodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
- H01L25/50—Multistep manufacturing processes of assemblies consisting of devices, each device being of a type provided for in group H01L27/00 or H01L29/00
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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
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Abstract
The invention provides a quantum dot display device and a preparation method thereof. The quantum dot display device includes: the LED array substrate comprises a substrate, a driving circuit, an LED array layer and a pixel array layer which are sequentially stacked; the LED array layer comprises a plurality of LED light sources which are arranged in a pixel array; the pixel array layer comprises a red pixel layer, a green pixel layer and a blue pixel layer, and is respectively positioned on the surfaces of the LED light sources in the red pixel area, the green pixel area and the blue pixel area; the red pixel layer and the green pixel layer are made of red light composite quantum dots and green light composite quantum dots respectively, and the blue pixel layer is a blue light transmission layer or a blue light composite quantum dot layer. The quantum dot display device is prepared by combining composite quantum dots with an electrodeposition process. The quantum dot display device provided by the invention has higher resolution and can realize high color gamut full-color display; the optical filter can be eliminated, the light passing rate is improved, and the power consumption of the device is reduced; the process is simple, the precision is high, and batch production can be realized.
Description
Technical Field
The invention belongs to the technical field of quantum dot display, and particularly relates to a quantum dot display device and a preparation method thereof.
Background
Quantum Dot materials (QDs) can excite a partial band of red, green, or blue light by absorbing the partial band of blue or ultraviolet light. The particle size of the quantum dot material is generally between 1-10 nm, and because electrons and holes are limited by quanta, a continuous energy band structure is changed into a discrete energy level structure, so that the luminescent spectrum is very narrow (20-30nm), the chromaticity is high, the display color gamut is wide, and the display color gamut can greatly exceed the color gamut range of NTSC (100%); meanwhile, the light absorption loss of the color filter is small, and low-power-consumption display can be realized. Due to its special characteristics, quantum dots are emerging as a new generation of luminescent materials in display applications.
The quantum dot color film is a key component for realizing ultrahigh color gamut full-color display of a display device, and quantum dots are dispersed in photoresist in the prior art, and then quantum dot material coating is realized on a specific area of a substrate in the modes of photocuring, etching and the like.
CN 105242442a discloses a method for preparing a quantum dot color film, in which a blue sub-pixel portion is a transparent organic photoresist layer, a green sub-pixel portion is a green quantum dot cured adhesive layer, and a red sub-pixel portion is a lamination of the green quantum dot cured adhesive layer and a red quantum dot cured adhesive layer. The quantum dot color film is matched with a blue light backlight source for use, and because the red sub-pixel part simultaneously contains green quantum dots and red quantum dots, a red color resistance layer is required to be arranged on the red sub-pixel to filter out green light. This reduces the light throughput, resulting in higher overall power consumption of the device.
CN 105242449a discloses a method for preparing a quantum dot color film substrate, which comprises forming a red color resist layer, a green color resist layer, and an organic transparent resist layer on a substrate, wherein the red color resist layer, the green color resist layer, and the organic transparent resist layer respectively correspond to red, green, and blue sub-pixel regions, coating a curing adhesive containing red quantum dots and green quantum dots, and irradiating the blue sub-pixel region with ultraviolet light for a long time to quench the fluorescence of the quantum dots in the region. The quantum dot color film is matched with a blue light backlight source for use, but because the red sub-pixel area and the green sub-pixel area both contain green quantum dots and red quantum dots, the red color resistance layer and the green color resistance layer are required to respectively filter green light and red light, so that the light passing rate is low.
CN 105278153a discloses a method for manufacturing a quantum dot color film substrate, which quenches red and green quantum dots in a blue sub-pixel region by using a quencher. CN 105301827a discloses a method for preparing a quantum dot color film substrate, which quenches red and green quantum dots in a blue sub-pixel region by using an ultraviolet initiator. However, the scheme also has the defects of complex process, difficulty in realizing pixel-level quantum dot arrangement, need of using an optical filter, low light passing rate and high overall power consumption of the device, and needs to be improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a quantum dot display device and a preparation method thereof. The quantum dot display device provided by the invention has higher resolution and can realize high color gamut full-color display; each pixel layer only emits light with a single color, and the light filter can be eliminated, so that the light passing rate and the display light effect are improved, and the overall power consumption of the device is reduced; and the process is simple, the manufacturing cost is low, the precision is high, and batch production can be realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a quantum dot display device comprising: the LED array substrate comprises a substrate, a driving circuit, an LED array layer and a pixel array layer which are sequentially stacked;
the display area of the quantum dot display device comprises a red pixel area, a green pixel area and a blue pixel area;
the LED array layer comprises a plurality of LED light sources which are arranged in a pixel array, the driving circuit is used for driving the LED light sources, and the LED light sources are blue LEDs or ultraviolet LEDs;
the pixel array layer comprises a red pixel layer, a green pixel layer and a blue pixel layer;
the red pixel layer is positioned on the surface of the LED light source in the red pixel area;
the green pixel layer is positioned on the surface of the LED light source in the green pixel area;
the blue pixel layer is positioned on the surface of the LED light source in the blue pixel area;
the red pixel layer is made of red light composite quantum dots;
the green pixel layer is made of green light composite quantum dots;
the LED light source is a blue LED, and the blue pixel layer is a blue light transmission layer; when the LED light source is an ultraviolet LED, the blue pixel layer is made of a blue light composite quantum dot;
the red light composite quantum dot, the green light composite quantum dot and the blue light composite quantum dot respectively comprise an inner core, a coating layer wrapping the inner core and a ligand connected to the outer surface of the coating layer;
the inner core is a red light quantum dot, a green light quantum dot or a blue light quantum dot, the ligand is organic salt with an ionic bond, and the red light composite quantum dot, the green light composite quantum dot and the blue light composite quantum dot are positively or negatively charged in a ligand dissociation state.
It should be noted that, in the present invention, the LED light sources are arranged in a pixel array, which means that the LED light sources are arranged according to the arrangement of the pixels, each LED light source corresponds to a pixel region, and the size of the LED light source is equivalent to the size of a conventional pixel in the art. The blue light transmission layer refers to a layer that transmits blue light, and in an embodiment of the present invention, it may be a layer where no entity exists, i.e., no material is deposited on the surface of the LED light source in the blue pixel region.
In the invention, the red light composite quantum dot and the green light composite quantum dot can respectively emit red light and green light under the excitation of blue light or ultraviolet light; the blue light composite quantum dot can emit blue light under the excitation of ultraviolet light. When the LED light source is a blue LED, a blue light composite quantum dot layer is not needed, and the red light and the green light emitted by exciting the red light and green light composite quantum dots are compounded with the blue light of the LED light source transmitted by the blue light transmission layer, so that the full-color display of the quantum dot display device is realized. When the LED light source is an ultraviolet LED, the red light, the green light and the blue light emitted by the excited composite quantum dots are compounded by utilizing the red light, the green light and the blue light, so that the full-color display of the quantum dot display device is realized.
The composite quantum dot has positive electricity or negative electricity in the ligand dissociation state, and a quantum dot layer can be formed by an electrodeposition method, so that the quantum dot display device is prepared. Wherein the coating layer is for binding a ligand on the one hand; on the other hand, the quantum dots can be protected, the quantum dots are prevented from being invaded by water and oxygen, and the quantum dots are prevented from being agglomerated.
In the invention, the composite quantum dot layer is directly deposited on the pixel-level LED light source, so that the composite quantum dot layer is also arranged in a pixel level manner, and the obtained quantum dot display device has higher resolution; and because each pixel layer only emits light with a single color, an optical filter is not needed, the light passing rate and the display light effect are improved, and the overall power consumption of the device is reduced.
In the present invention, the red light composite quantum dot layers each refer to a layer composed of a red light composite quantum dot, the green light composite quantum dot layers each refer to a layer composed of a green light composite quantum dot, and the blue light composite quantum dot layers each refer to a layer composed of a blue light composite quantum dot.
In the present invention, in order to briefly describe the quantum dot display device and the method for manufacturing the same, a pixel region, a pixel layer, a composite quantum dot, and a composite quantum dot layer are partially used to refer to any one of a pixel region of different emission colors, a pixel layer of different emission colors, a composite quantum dot layer of different emission colors, or the whole.
As a preferred technical solution of the present invention, the display area of the quantum dot display device further includes a white pixel region, and the pixel array layer further includes a white pixel layer located on the surface of the LED light source in the white pixel region;
when the LED light source is a blue LED, the white pixel layer is a mixed layer of the red light composite quantum dots and the green light composite quantum dots, or a laminated layer of the red light composite quantum dot layer and the green light composite quantum dot layer;
when the LED light source is an ultraviolet LED, the white pixel layer is a mixed layer of the red light composite quantum dot, the green light composite quantum dot and the blue light composite quantum dot, or a laminated layer of the red light composite quantum dot layer, the green light composite quantum dot layer and the blue light composite quantum dot layer.
In the invention, when the LED light source is a blue LED, the intensities of red light, green light and transmitted blue light emitted by the red light and green light composite quantum dots in the white pixel layer respectively under excitation need to be controlled to be basically equal so as to ensure that the red light, the green light and the transmitted blue light can be compounded into white light. When the LED light source is an ultraviolet LED, the intensities of red light, green light, and blue light respectively emitted by the red light, green light, and blue light composite quantum dots in the white pixel layer need to be controlled to be substantially equal, so as to ensure that the three can be composited into white light.
By additionally arranging the white pixel layer outside the red, green and blue pixel layers, the full-color display of the quantum dot display device can be ensured, and meanwhile, the brightness is improved.
As a preferred technical solution of the present invention, the quantum dot display device further includes an encapsulation layer that encapsulates the driving circuit, the LED array layer, and the pixel array layer.
As a preferred technical scheme of the invention, the red light quantum dots, the green light quantum dots and the blue light quantum dots are AxMyEzA system material;
wherein, the element A is selected from one or the combination of at least two of Ba, Ag, Na, Fe, In, Cd, Zn, Ga, Mg, Pb and Cs;
m element is selected from one or the combination of at least two of S, Cl, O, As, N, P, Se, Te, Ti, Zr and Pb;
the E element is selected from one or the combination of at least two of S, As, Se, O, Cl, Br and I;
x is 0.3 to 2.0, and may be, for example, 0.3, 0.5, 0.8, 1, 1.2, 1.3, 1.5, 1.6, 1.8 or 2;
y is 0.5 to 3.0, and may be, for example, 0.5, 0.8, 1, 1.2, 1.3, 1.5, 1.6, 1.8, 2, 2.2, 2.3, 2.5, 2.6, 2.8 or 3;
z is 0 to 4.0, and may be, for example, 0, 0.2, 0.3, 0.5, 0.8, 1, 1.2, 1.3, 1.5, 1.6, 1.8, 2, 2.2, 2.3, 2.5, 2.6, 2.8, 3, 3.2, 3.3, 3.5, 3.6, 3.8 or 4.
In a preferred embodiment of the present invention, the material of the coating layer is a polymer material, a metal oxide, a metal sulfide, a metal, or a metal alloy.
Preferably, the polymer material is selected from one or a combination of at least two of PMA, PVDF and long-chain phosphate.
Preferably, the long-chain phosphate is a phosphate with 16-18 carbon atoms.
Preferably, the metal oxide is selected from ZnO, SiO2、TiO2Or MgO or a combination of at least two thereof.
Preferably, the metal sulfide is selected from one or a combination of at least two of ZnS, CdS or TeS.
Preferably, the metal is selected from one or a combination of at least two of Ti, Zr, Zn, Cd or Te.
Preferably, the organic salt having an ionic bond includes an organic negative ion salt or an organic positive ion salt.
Preferably, the organic negative ion salt includes an organic acid salt.
Preferably, the organic acid salt comprises one or a combination of at least two of sodium acetate, picolinate or sodium ethoxide.
Preferably, the organic cationic salt comprises an organic ammonium salt.
Preferably, the organic ammonium salt comprises one or a combination of at least two of tetrabutylammonium bromide, ammonium chloride or ammonium sulfate.
As a preferable technical scheme of the invention, the particle size of the red light quantum dots is 6-12nm, the particle size of the green light quantum dots is 3-6nm, and the particle size of the blue light quantum dots is 1-3 nm.
As a preferred technical scheme of the invention, the preparation method of the red light composite quantum dot, the green light composite quantum dot and the blue light composite quantum dot comprises the following steps:
a: dripping a coating layer material into the red light quantum dots, the green light quantum dots or the blue light quantum dots, controlling the pH value, the reaction temperature and the reaction time, and coating the coating layer material on the surfaces of the red light quantum dots, the green light quantum dots or the blue light quantum dots to form a coating layer to obtain a quantum dot/coating layer core-shell material;
b: and b, dispersing the quantum dot/coating core-shell material obtained in the step a and a ligand in a solvent, and controlling the pH, the reaction temperature and the reaction time to enable the ligand to be connected to the surface of the coating to obtain a solution of the red light composite quantum dot, the green light composite quantum dot or the blue light composite quantum dot.
As a preferred embodiment of the present invention, the pH in step a is 5.5 to 11, such as 5, 6, 7, 8, 9, 10 or 11; the reaction temperature in step a is 240-320 ℃ (for example, 240 ℃, 250 ℃, 270 ℃, 280 ℃, 300 ℃ or 320 ℃), and the reaction time is 0.5-10 min (for example, 0.5min, 0.8min, 1min, 3min, 5min, 7min, 9min or 10 min).
Preferably, the pH in step b is 7-10, e.g. 7, 7.4, 7.8, 8, 8.3, 8.5, 8.8, 9, 9.4, 9.7 or 10; the reaction temperature in step b is 120-.
Preferably, the solvent in step b is one or a combination of at least two of octadecene, n-hexane, n-octane, oily ammonia, n-dodecyl mercaptan, 1-octyl mercaptan or trioctyl amine.
In a second aspect, the present invention provides a method for manufacturing a quantum dot display device according to the first aspect, the method comprising the steps of:
providing a laminated structure of a substrate, a driving circuit and an LED array layer, and depositing a red light composite quantum dot layer on the surface of an LED light source in a red pixel region through electrodeposition to serve as a red pixel layer; depositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region to serve as a green pixel layer; depositing a blue light composite quantum dot layer on the surface of the LED light source in the blue pixel region or not, and taking the blue light composite quantum dot layer as a blue pixel layer; obtaining the quantum dot display device;
the electrodeposition method is a separate deposition method, and the separate deposition method comprises the following steps: selecting one of a red light composite quantum dot layer, a green light composite quantum dot layer and a blue light composite quantum dot layer, placing the laminated structure in a solution of composite quantum dots to be deposited, applying a voltage opposite to the electrical property of the composite quantum dots to be deposited to an LED light source to be deposited through the driving circuit, applying a voltage identical to the electrical property of the composite quantum dots to be deposited to the solution of the composite quantum dots to be deposited, and depositing.
In the stacked structure of the substrate, the driving circuit, and the LED array layer, the LED light source is soldered to the substrate and the driving circuit by a conductive solder material, and the solder material serves only for connection and fixation and does not have a light emitting function, so the structure of the quantum dot display device is not limited.
The invention adopts the composite quantum dot combined with the electrodeposition process, and can directly deposit the red light, green light or blue light composite quantum dot layers on each LED light source independently, so that each pixel layer only emits light with single color without using an optical filter, thereby being beneficial to improving the light passing rate and the display light effect and reducing the integral power consumption of the device. Compared with the existing complex photoetching process, the method provided by the invention is simple, low in cost and high in precision, and is beneficial to batch production of quantum dot color films.
In the present invention, the electrodeposition method is a separate deposition method. For example, when there is no blue complex quantum dot layer, a red complex quantum dot layer and a green complex quantum dot layer are separately deposited using a separate deposition method. When the red light, green light and blue light composite quantum dot layers exist, the red light, green light and blue light composite quantum dot layers can be deposited one by adopting a single deposition method.
In the present invention, the conditions (voltage, deposition time) for electrodepositing the composite quantum dot layer need to be selected by comprehensively considering the charge amount of the composite quantum dots, the content of the quantum dots in the composite quantum dots, the luminous intensity of the LED light source, and the like. For the three pixel layers of red, green and blue, it is necessary to ensure that the quantum dots in the deposited composite quantum dot layer can completely absorb the light emitted by the LED light source.
Preferably, the electrodeposition voltage is 1 to 12V (e.g., 1V, 3V, 5V, 8V, 10V or 12V), and the current density is 5 to 10A/dm2(e.g., 5A/dm)2、6A/dm2、7A/dm2、8A/dm2、9A/dm2Consequence 10A/dm2) The deposition time is 0.5-30 min (e.g. 0.5min, 5min, 8min, 10min, 13min, 15min, 20min, 25min, 28min or 30 min).
As a preferred technical solution of the present invention, the preparation method further comprises depositing a white pixel layer on the surface of the LED light source in the white pixel region;
the deposition method of the white pixel layer comprises the following steps: placing the laminated structure in a mixed solution of red light composite quantum dots and green light composite quantum dots with the same electrical property, or in a mixed solution of red light composite quantum dots, green light composite quantum dots and blue light composite quantum dots with the same electrical property, applying a voltage with the electrical property opposite to that of the composite quantum dots to be deposited to an LED light source in a white pixel region through the driving circuit, and applying a voltage with the electrical property same as that of the composite quantum dots to be deposited to the mixed solution for deposition;
or according to the independent deposition method, the lamination of the red light composite quantum dot layer and the green light composite quantum dot layer is deposited on the surface of the LED light source in the white pixel region layer by layer, or the lamination of the red light composite quantum dot layer, the green light composite quantum dot layer and the blue light composite quantum dot layer is deposited layer by layer.
In the invention, the conditions for electrodepositing the white pixel layer need to be selected by comprehensively considering the charge quantity of the composite quantum dots, the content of the quantum dots in the composite quantum dots, the luminous intensity of the LED light source and other factors. When the LED light source is a blue LED, it is necessary to ensure that the intensities of red light, green light and transmitted blue light emitted by the red light and green light composite quantum dots in the deposited white pixel layer are respectively excited to be substantially equal, so as to ensure that the three can be composited into white light. When the LED light source is an ultraviolet LED, it is necessary to ensure that the intensities of red light, green light, and blue light respectively emitted by the red light, green light, and blue light composite quantum dots in the deposited white pixel layer are substantially equal, so as to ensure that the three can be composited into white light.
Considering that the deposition amount of different composite quantum dots is difficult to be precisely controlled when the white pixel layer is a mixed layer of red, green and blue composite quantum dots, the white pixel layer in the present invention is more preferably a stack of a red and green composite quantum dot layer or a stack of a red, green and blue composite quantum dot layer.
Preferably, the preparation method further comprises: after each electrodeposition, the deposited stack is removed, dried, and subjected to heating, freezing, or light irradiation. The purpose of this operation is to make the deposited composite quantum dots stably attached to the LED light source.
Preferably, the heating temperature is 80-150 ℃, such as 80 ℃, 85 ℃, 90 ℃, 100 ℃, 120 ℃, 140 ℃ or 150 ℃.
Preferably, the freezing is freezing below-40 ℃.
Preferably, the light irradiation is ultraviolet irradiation at 230-.
Preferably, the preparation method further comprises: and after the pixel array layer is prepared, coating packaging glue for coating the driving circuit, the LED array layer and the pixel array layer, and curing to form the packaging layer.
The type of the encapsulation glue is not particularly limited, and for example, one or more of epoxy glue, silicone glue and polyurethane glue may be selected and mixed, and the curing method may adopt thermal curing and/or light curing.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the composite quantum dot combined with the electrodeposition process, and can directly deposit the composite quantum dot layer on each pixel level LED light source independently, compared with the prior photoetching process, the method provided by the invention has the advantages of simplicity, low cost and high precision, and is beneficial to the batch production of quantum dot display devices;
(2) in the quantum dot display device provided by the invention, the composite quantum dot layer is directly deposited on the pixel-level LED light source, so that the composite quantum dot layer is also arranged at the pixel level, pixel-level light emission is realized, and the obtained quantum dot display device has higher resolution and can realize high-color-gamut full-color display;
(3) in the quantum dot display device provided by the invention, each pixel layer only emits light with a single color, so that an optical filter is not needed, the light passing rate and the display light effect are improved, and the overall power consumption of the device is reduced.
Drawings
Fig. 1 is a schematic cross-sectional structure diagram of a quantum dot display device provided in embodiment 1 of the present invention;
fig. 2 is a schematic top view of a quantum dot display device according to embodiment 1 or 2 of the present invention;
FIG. 3 is a schematic diagram of an LED light source according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a stacked structure of a substrate, a driving circuit and an LED array layer according to an embodiment of the invention;
FIG. 5 is a schematic diagram illustrating the deposition process of the red light recombination quantum dot layer in embodiment 1 of the present invention;
FIG. 6 is a schematic diagram of the deposition process of the green light composite quantum dot layer in example 1 of the present invention;
FIG. 7 is a schematic diagram of the deposition process of the blue light composite quantum dot layer in example 1 of the present invention;
fig. 8 is a schematic cross-sectional structure diagram of a quantum dot display device according to embodiment 2 of the present invention;
FIG. 9 is a schematic diagram of the deposition process of the red and green light composite quantum dot layer in example 2 of the present invention;
FIG. 10 is a schematic diagram of the deposition process of the blue light composite quantum dot layer in example 2 of the present invention;
fig. 11 is a schematic cross-sectional structure diagram of a quantum dot display device according to embodiment 3 of the present invention;
fig. 12 is a schematic top view of a quantum dot display device according to embodiment 3 or 4 of the present invention;
fig. 13 is a schematic cross-sectional structure view of a quantum dot display device provided in embodiment 4 of the present invention;
fig. 14 is a schematic cross-sectional structure view of a quantum dot display device according to embodiment 5 of the present invention;
fig. 15 is a schematic top view of a quantum dot display device according to embodiment 5 of the present invention;
fig. 16 is a schematic cross-sectional view of a quantum dot display device in a white pixel region according to embodiment 5 of the present invention;
fig. 17 is a schematic cross-sectional structure view of a quantum dot display device provided in embodiment 6 of the present invention;
fig. 18 is a schematic top view of a quantum dot display device according to embodiment 6 of the present invention;
fig. 19 is a schematic cross-sectional view of a quantum dot display device in a white pixel region according to embodiment 6 of the present invention;
wherein 10 is a substrate, 20 is a driving circuit, 30 is an LED array layer, 40 is a pixel array layer, 50 is a packaging layer, 301 is an LED light source, 3011 is a P electrode, 3012 is an N electrode, 3013 is a P-type semiconductor, 3014 is an N-type semiconductor, 3015 is a light emitting layer, 3016 is a substrate, 401 is a red pixel layer, 402 is a green pixel layer, 403 is a blue pixel layer, 404 is a white pixel layer, 4041 is a red light composite quantum dot sublayer, 4042 is a green light composite quantum dot sublayer, 4043 is a blue light composite quantum dot sublayer.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the specific embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
Providing a positively charged red light composite quantum dot solution, wherein the preparation method comprises the following steps:
a: dropwise adding a coating layer material PVDF into red light quantum dots (TeSe, the particle size is 11nm), reacting for 5mins under the conditions that the pH is 7.5 and the temperature is 290 ℃, and coating the coating layer material on the surfaces of the quantum dots to form a coating layer, so as to obtain a quantum dot/coating layer core-shell material;
b: and d, dispersing the quantum dot/coating core-shell material obtained in the step a in an octadecene solvent, adding ammonium sulfate serving as a ligand, reacting for 90mins at the temperature of 175 ℃ and the pH value of 8, and connecting the ligand to the surface of the coating to obtain a positively charged red light composite quantum dot solution with the concentration of 3.5%.
Preparation example 2
Providing a negatively charged red light composite quantum dot solution, wherein the preparation method comprises the following steps:
a: dropwise adding tetrabutyl titanate serving as a coating material into red light quantum dots (CdSe with the particle size of 9nm), reacting for 5min under the conditions that the pH is 6 and the temperature is 300 ℃, so that the coating material is coated on the surfaces of the quantum dots to form a coating layer, and thus obtaining a quantum dot/coating layer core-shell material;
b: and d, dispersing the quantum dot/coating core-shell material obtained in the step a in a solvent n-hexane, adding a ligand sodium acetate, reacting for 10min at the temperature of 200 ℃ and the pH value of 7.4, and connecting the ligand to the surface of the coating to obtain a negatively charged red light composite quantum dot solution with the concentration of 3.8%.
Preparation example 3
Providing a positively charged green light composite quantum dot solution, and the preparation method comprises the following steps:
a: towards green quantum dots (CsPbBr)3Particle size of 5nm), and reacting for 10min at the temperature of 240 ℃ under the condition that the pH is 5.5, so that the coating layer material is coated on the surface of the quantum dot to form a coating layer, thereby obtaining the quantum dot/coating layer core-shell material;
b: and d, dispersing the quantum dot/coating core-shell material obtained in the step a in a solvent n-hexane, adding a ligand tetrabutylammonium bromide, reacting for 10min at the temperature of 300 ℃ under the condition that the pH is 9, and enabling the ligand to be connected to the surface of the coating to obtain a positively charged green light composite quantum dot solution with the concentration of 5%.
Preparation example 4
Providing a green light composite quantum dot solution with negative electricity, wherein the preparation method comprises the following steps:
a: dropwise adding a coating material PMA into green light quantum dots (InP, the particle size is 6nm), reacting for 2min under the conditions that the pH is 6 and the temperature is 320 ℃, so that the coating material is coated on the surfaces of the quantum dots to form a coating layer, and thus obtaining a quantum dot/coating layer core-shell material;
b: and d, dispersing the quantum dot/coating core-shell material obtained in the step a in a solvent n-hexane, adding a ligand sodium ethoxide, reacting for 60min at the pH of 8.5 and the temperature of 240 ℃, and connecting the ligand to the surface of the coating to obtain a green light composite quantum dot solution with negative electricity and the concentration of 4.5%.
Preparation example 5
Providing a positively charged blue light composite quantum dot solution, wherein the preparation method comprises the following steps:
a: quantum dots (CsPbCl) emitting blue light3Particle size of 3nm), and reacting for 10min at the temperature of 280 ℃ and the pH value of 10 to coat the coating material on the surface of the quantum dot to form a coating layer, so as to obtain the quantum dot/coating layer core-shell material;
b: and d, dispersing the quantum dot/coating core-shell material obtained in the step a in n-octane serving as a solvent, adding ammonium chloride serving as a ligand, reacting for 60min at the temperature of 150 ℃ at the pH value of 10, and connecting the ligand to the surface of the coating to obtain a positively charged blue light composite quantum dot solution with the concentration of 3.5%.
Preparation example 6
Providing a negatively charged blue light composite quantum dot solution, wherein the preparation method comprises the following steps:
a: quantum dots (CdS) emitting blue light0.2Se0.8And 2nm), dripping a coating material octadecyl phosphoric acid, reacting for 5min under the conditions that the pH value is 11 and the temperature is 300 ℃, so that the coating material is coated on the surface of the quantum dot to form a coating layer, and obtaining the quantum dot/coating layer core-shell material;
b: and d, dispersing the quantum dot/coating core-shell material obtained in the step a in n-dodecyl mercaptan solvent, adding ligand sodium sulfonate, reacting for 5min under the conditions that the pH value is 7 and the temperature is 320, and enabling the ligand to be connected to the surface of the coating layer to obtain a negatively charged blue light composite quantum dot solution with the concentration of 4%.
Example 1
The present embodiment provides a quantum dot display device, the structure of which is shown in fig. 1 and fig. 2, and includes: the LED display panel comprises a substrate 10, a driving circuit 20, an LED array layer 30, a pixel array layer 40 and an encapsulation layer 50 covering the driving circuit 20, the LED array layer 30 and the pixel array layer 40, wherein the substrate, the driving circuit 20, the LED array layer 30 and the pixel array layer 40 are sequentially stacked;
the display area of the quantum dot display device comprises a red pixel area, a green pixel area and a blue pixel area;
the LED array layer 30 includes a plurality of LED light sources 301 arranged in a pixel array (the LED light sources 301 are welded on the substrate 10 and the driving circuit 20 by conductive welding materials, the welding materials are not shown in the figure), the driving circuit 2 is configured to drive the LED light sources 301, and the LED light sources 301 are ultraviolet LEDs;
the LED light source 301 is shown in fig. 3, and includes a substrate 3016, an N-type semiconductor 3014, a light emitting layer 3015, a P-type semiconductor 3013, a P-electrode 3011, and an N-electrode 3012, where the substrate 3016 is connected to the pixel array layer 40, and the P-electrode 3011 and the N-electrode 3012 are connected to the driving circuit 20;
the pixel array layer 40 includes a red pixel layer 401, a green pixel layer 402, and a blue pixel layer 403;
the red pixel layer 401 is positioned on the surface of the LED light source in the red pixel area;
the green pixel layer 402 is located on the surface of the LED light source within the green pixel region;
the blue pixel layer 403 is positioned on the surface of the LED light source in the blue pixel region;
the material of the red pixel layer 401 is the red light composite quantum dot provided in preparation example 1;
the material of the green pixel layer 402 is the green light composite quantum dot provided by preparation example 4;
the material of the blue pixel layer 403 is the blue light composite quantum dot provided in preparation example 5.
The preparation method of the quantum dot display device provided by the embodiment is as follows:
(1) providing a laminated structure of a substrate, a driving circuit and an LED array layer (the structure is shown in FIG. 4), and depositing a red light composite quantum dot layer on the surface of an LED light source in a red pixel region through electrodeposition to form a red pixel layer 401; depositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region as a green pixel layer 402; depositing a blue light composite quantum dot layer on the surface of the LED light source in the blue pixel region as a blue pixel layer 403;
(2) coating packaging glue for coating the driving circuit 20, the LED array layer 30 and the pixel array layer 40, and curing to form a packaging layer 50 to obtain the quantum dot display device;
the electrodeposition method is to deposit the red light composite quantum dot layer, the green light composite quantum dot layer and the blue light composite quantum dot layer by adopting a single deposition method, and comprises the following specific steps:
as shown in fig. 5, the stacked structure was placed in the positively charged red light composite quantum dot solution provided in preparative example 1, a negative voltage was applied to the LED light source in the red pixel region through the driving circuit 20, and a positive voltage was applied to the positively charged red light composite quantum dot solution provided in preparative example 1, with a voltage difference of 8V and a current density of 5A/dm2Continuously depositing a red light composite quantum dot layer on the surface of the LED light source in the red pixel region for 10min to serve as a red pixel layer 401, taking out the laminated structure deposited with the red light composite quantum dot layer, drying, and heating at 100 ℃ to ensure that the deposited red light composite quantum dot is stably attached to the LED light source in the red pixel region;
as shown in FIG. 6, the stacked structure deposited with the red light composite quantum dot layer was placed in the negatively charged green light composite quantum dot solution provided in preparative example 4, a positive voltage was applied to the LED light source in the green pixel region through the driving circuit 20, and a negative voltage was applied to the negatively charged green light composite quantum dot solution provided in preparative example 4, at a voltage difference of 12V and a current density of 5A/dm2LED in green pixel region for 10minDepositing a green light composite quantum dot layer on the surface of the light source to serve as a green pixel layer 402, taking out the laminated structure deposited with the red light and green light composite quantum dot layer, drying, and freezing at-40 ℃ to ensure that the deposited green light composite quantum dot is stably attached to the LED light source in the green pixel region;
as shown in fig. 7, the stacked structure deposited with the red and green light composite quantum dot layers was placed in the positively charged blue light composite quantum dot solution provided in preparative example 5, a negative voltage was applied to the LED light source in the blue pixel region through the driving circuit 20, a positive voltage was applied to the positively charged blue light composite quantum dot solution provided in preparative example 5, a voltage difference was 3V, and a current density was 10A/dm2Continuously depositing a blue light composite quantum dot layer on the surface of the LED light source in the blue pixel region for 3min to serve as a blue pixel layer 403, taking out the laminated structure deposited with the red light, green light and blue light composite quantum dot layer, drying, and curing under the ultraviolet light of 230-395nm to ensure that the deposited blue light composite quantum dot is stably attached to the LED light source in the blue pixel region;
in this embodiment, since the deposition steps of the red light, green light, and blue light composite quantum dot layers are independent from each other, the deposition steps of the three composite quantum dot layers can be performed in any order, and the deposition order has no influence on the manufactured quantum dot display device.
In the embodiment, the composite quantum dots are combined with the electrodeposition process, so that the composite quantum dot layers can be directly deposited on each pixel-level LED light source independently, and high-color-gamut full-color display is realized; compared with the existing complex photoetching process, the method is simple, low in cost and high in precision, and is beneficial to batch production of quantum dot display devices; the prepared quantum dot display device has no optical filter, is beneficial to improving the light passing rate and the display light effect, and reduces the overall power consumption of the device.
Example 2
The present embodiment provides a quantum dot display device, the structure of which is shown in fig. 8 and fig. 2, including: a substrate 10, a driving circuit 20, an LED array layer 30, and a pixel array layer 40 sequentially stacked;
the display area of the quantum dot display device comprises a red pixel area, a green pixel area and a blue pixel area;
the LED array layer 30 includes a plurality of LED light sources 301 arranged in a pixel array (the LED light sources 301 are welded on the substrate 10 and the driving circuit 20 by conductive welding materials, the welding materials are not shown in the figure), the driving circuit 2 is configured to drive the LED light sources 301, and the LED light sources 301 are ultraviolet LEDs;
the LED light source 301 is shown in fig. 3, and includes a substrate 3016, an N-type semiconductor 3014, a light emitting layer 3015, a P-type semiconductor 3013, a P-electrode 3011, and an N-electrode 3012, where the substrate 3016 is connected to the pixel array layer 40, and the P-electrode 3011 and the N-electrode 3012 are connected to the driving circuit 20;
the pixel array layer 40 includes a red pixel layer 401, a green pixel layer 402, and a blue pixel layer 403;
the red pixel layer 401 is positioned on the surface of the LED light source in the red pixel area;
the green pixel layer 402 is located on the surface of the LED light source within the green pixel region;
the blue pixel layer 403 is positioned on the surface of the LED light source in the blue pixel region;
the material of the red pixel layer 401 is the red light composite quantum dot provided by preparation example 2;
the material of the green pixel layer 402 is the green light composite quantum dot provided by preparation example 3;
the material of the blue pixel layer 403 is the blue light composite quantum dot provided in preparation example 6.
The preparation method of the quantum dot display device provided by the embodiment is as follows:
providing a laminated structure of a substrate, a driving circuit and an LED array layer (the structure is shown in FIG. 4), and depositing a red light composite quantum dot layer on the surface of an LED light source in a red pixel region through electrodeposition to form a red pixel layer 401; depositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region as a green pixel layer 402; depositing a blue light composite quantum dot layer on the surface of the LED light source in the blue pixel region as a blue pixel layer 403; obtaining the quantum dot display device;
the electrodeposition method comprises the steps of simultaneously depositing a red light composite quantum dot layer and a green light composite quantum dot layer by adopting a one-step deposition method, and depositing a blue light composite quantum dot layer by adopting a single deposition method, and comprises the following specific steps:
as shown in fig. 9, the negatively charged red light composite quantum dot solution provided in preparation example 2 and the positively charged green light composite quantum dot solution provided in preparation example 3 were mixed, the stacked structure was placed in the mixed solution, a positive voltage was applied to the LED light source in the red pixel region and a negative voltage was applied to the LED light source in the green pixel region by the driving circuit 20, the voltage difference was 5V, and the current density was 8A/dm2Continuing for 10min, simultaneously depositing a red light composite quantum dot layer on the LED light source in the red pixel region to serve as a red pixel layer 401, depositing a green light composite quantum dot layer on the LED light source in the green pixel region to serve as a green pixel layer 402, taking out the laminated structure on which the red light and green light composite quantum dot layers are deposited, drying, and curing under ultraviolet light to ensure that the deposited red light and green light composite quantum dots are respectively and stably attached to the LED light sources in the red and green pixel regions;
as shown in fig. 10, the stacked structure deposited with the red and green light composite quantum dot layers was placed in the negatively charged blue light composite quantum dot solution provided in preparative example 6, a positive voltage was applied to the LED light source in the blue pixel region through the driving circuit 20, a negative voltage was applied to the negatively charged blue light composite quantum dot solution provided in preparative example 6, a voltage difference was 5V, and a current density was 8A/dm2Continuously depositing a blue light composite quantum dot layer on the surface of the LED light source in the blue pixel region for 10min to serve as a blue pixel layer 403, taking out the laminated structure deposited with the red light and green light composite quantum dot layer, drying, and curing under ultraviolet illumination to ensure that the deposited green light composite quantum dot is stably attached to the LED light source in the green pixel region;
in this embodiment, the blue light composite quantum dot layer may be deposited by a single deposition method, and then the red light composite quantum dot layer and the green light composite quantum dot layer may be deposited simultaneously by a one-step deposition method, where the deposition sequence has no influence on the prepared quantum dot display device.
In the embodiment, the composite quantum dots are combined with the electrodeposition process, so that the composite quantum dot layers can be directly deposited on each pixel-level LED light source independently, and high-color-gamut full-color display is realized; compared with the existing complex photoetching process, the method is simple, low in cost and high in precision, and is beneficial to batch production of quantum dot display devices; the prepared quantum dot display device has no optical filter, is beneficial to improving the light passing rate and the display light effect, and reduces the overall power consumption of the device.
Example 3
The present embodiment provides a quantum dot display device, the structure of which is shown in fig. 11 and 12, including: the LED display panel comprises a substrate 10, a driving circuit 20, an LED array layer 30, a pixel array layer 40 and an encapsulation layer 50 covering the driving circuit 20, the LED array layer 30 and the pixel array layer 40, wherein the substrate, the driving circuit 20, the LED array layer 30 and the pixel array layer 40 are sequentially stacked;
the display area of the quantum dot display device comprises a red pixel area, a green pixel area and a blue pixel area;
the LED array layer 30 includes a plurality of LED light sources 301 arranged in a pixel array (the LED light sources 301 are welded on the substrate 10 and the driving circuit 20 by conductive welding materials, the welding materials are not shown in the figure), the driving circuit 2 is configured to drive the LED light sources 301, and the LED light sources 301 are blue LEDs;
the LED light source 301 is shown in fig. 3, and includes a substrate 3016, an N-type semiconductor 3014, a light emitting layer 3015, a P-type semiconductor 3013, a P-electrode 3011, and an N-electrode 3012, where the substrate 3016 is connected to the pixel array layer 40, and the P-electrode 3011 and the N-electrode 3012 are connected to the driving circuit 20;
the pixel array layer 40 includes a red pixel layer 401, a green pixel layer 402, and a blue pixel layer;
the red pixel layer 401 is positioned on the surface of the LED light source in the red pixel area;
the green pixel layer 402 is located on the surface of the LED light source within the green pixel region;
the LED light source surface in the blue pixel region has no composite quantum dot layer, and can transmit blue light emitted by the LED light source 301, and for convenience of explaining the structure of the quantum dot display device, the region where there is no entity on the LED light source surface is referred to as a blue pixel layer;
the material of the red pixel layer 401 is the red light composite quantum dot provided in preparation example 1;
the material of the green pixel layer 402 is the green light composite quantum dot provided in preparation example 4.
The preparation method of the quantum dot display device provided by the embodiment is as follows:
(1) providing a laminated structure of a substrate, a driving circuit and an LED array layer (the structure is shown in FIG. 4), and depositing a red light composite quantum dot layer on the surface of an LED light source in a red pixel region through electrodeposition to form a red pixel layer 401; depositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region as a green pixel layer 402; no material is deposited on the surface of the LED light source in the blue pixel area, and the area without solid bodies is used as a blue pixel layer;
(2) coating packaging glue for coating the driving circuit 20, the LED array layer 30 and the pixel array layer 40, and curing to form a packaging layer 50 to obtain the quantum dot display device;
the electrodeposition method is characterized in that a red light composite quantum dot layer and a green light composite quantum dot layer are simultaneously deposited by adopting a one-step deposition method, and the electrodeposition method comprises the following specific steps:
mixing the positively charged red light composite quantum dot solution provided in preparation example 1 and the negatively charged green light composite quantum dot solution provided in preparation example 4, placing the laminated structure in the mixed solution, applying a negative voltage to the LED light source in the red pixel region and applying a positive and negative voltage to the LED light source in the green pixel region through the driving circuit 20, wherein the voltage difference is 2V and the current density is 5A/dm2Continuing for 30min, simultaneously depositing a red light composite quantum dot layer on the LED light source in the red pixel area to serve as a red pixel layer 401, depositing a green light composite quantum dot layer on the LED light source in the green pixel area to serve as a green pixel layer 402, and not depositing the LED light source in the blue pixel area; taking out the laminated structure with the deposited red light and green light composite quantum dot layers, drying, heating at 100 deg.C to make the deposited red light and green light composite quantum dots stably attached to red light and green light respectivelyAnd the LED light sources in the color and green pixel areas.
In the embodiment, the composite quantum dots are combined with the electrodeposition process, so that the composite quantum dot layers can be directly deposited on each pixel-level LED light source independently, and high-color-gamut full-color display is realized; compared with the existing complex photoetching process, the method is simple, low in cost and high in precision, and is beneficial to batch production of quantum dot display devices; the prepared quantum dot display device has no optical filter, is beneficial to improving the light passing rate and the display light effect, and reduces the overall power consumption of the device.
Example 4
The present embodiment provides a quantum dot display device, the structure of which is shown in fig. 13 and 12, including: a substrate 10, a driving circuit 20, an LED array layer 30, and a pixel array layer 40 sequentially stacked;
the display area of the quantum dot display device comprises a red pixel area, a green pixel area and a blue pixel area;
the LED array layer 30 includes a plurality of LED light sources 301 arranged in a pixel array (the LED light sources 301 are welded on the substrate 10 and the driving circuit 20 by conductive welding materials, the welding materials are not shown in the figure), the driving circuit 2 is configured to drive the LED light sources 301, and the LED light sources 301 are blue LEDs;
the LED light source 301 is shown in fig. 3, and includes a substrate 3016, an N-type semiconductor 3014, a light emitting layer 3015, a P-type semiconductor 3013, a P-electrode 3011, and an N-electrode 3012, where the substrate 3016 is connected to the pixel array layer 40, and the P-electrode 3011 and the N-electrode 3012 are connected to the driving circuit 20;
the pixel array layer 40 includes a red pixel layer 401, a green pixel layer 402, and a blue pixel layer;
the red pixel layer 401 is positioned on the surface of the LED light source in the red pixel area;
the green pixel layer 402 is located on the surface of the LED light source within the green pixel region;
the LED light source surface in the blue pixel region has no composite quantum dot layer, and can transmit blue light emitted by the LED light source 301, and for convenience of explaining the structure of the quantum dot display device, the region where there is no entity on the LED light source surface is referred to as a blue pixel layer;
the material of the red pixel layer 401 is the red light composite quantum dot provided in preparation example 1;
the material of the green pixel layer 402 is the green light composite quantum dot provided in preparation example 3.
The preparation method of the quantum dot display device provided by the embodiment is as follows:
providing a laminated structure of a substrate, a driving circuit and an LED array layer (the structure is shown in FIG. 4), and depositing a red light composite quantum dot layer on the surface of an LED light source in a red pixel region through electrodeposition to form a red pixel layer 401; depositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region as a green pixel layer 402; no material is deposited on the surface of the LED light source in the blue pixel area, and the area without solid bodies is used as a blue pixel layer; obtaining the quantum dot display device;
the electrodeposition method is to respectively deposit the red light composite quantum dot layer and the green light composite quantum dot layer by adopting a single deposition method, and comprises the following specific steps:
the stacked structure was placed in the positively charged red light composite quantum dot solution provided in preparative example 1, a negative voltage was applied to the LED light source in the red pixel region by the driving circuit 20, and a positive voltage was applied to the positively charged red light composite quantum dot solution provided in preparative example 1, with a voltage difference of 12V and a current density of 5A/dm2Continuously depositing a red light composite quantum dot layer on the surface of the LED light source in the red pixel region for 10min to serve as a red pixel layer 401, taking out the laminated structure deposited with the red light composite quantum dot layer, drying, and curing under ultraviolet illumination to enable the deposited red light composite quantum dot to be stably attached to the LED light source in the red pixel region;
the stacked structure deposited with the red light composite quantum dot layer was placed in the positively charged green light composite quantum dot solution provided in preparative example 3, a negative voltage was applied to the LED light source in the green pixel region through the driving circuit 20, a positive voltage was applied to the positively charged green light composite quantum dot solution provided in preparative example 3, the voltage difference was 2V, and the current density was 5A/dm2Lasting for 20minDepositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region to serve as a green pixel layer 402, taking out the laminated structure deposited with the red light and green light composite quantum dot layer, drying, and curing under ultraviolet illumination to ensure that the deposited green light composite quantum dot is stably attached to the LED light source in the green pixel region;
the LED light sources in the blue pixel area are not deposited.
In this embodiment, the green light composite quantum dot layer may be deposited first, and then the red light composite quantum dot layer may be deposited, and the deposition sequence has no influence on the prepared quantum dot display device.
In the embodiment, the composite quantum dots are combined with the electrodeposition process, so that the composite quantum dot layers can be directly deposited on each pixel-level LED light source independently, and high-color-gamut full-color display is realized; compared with the existing complex photoetching process, the method is simple, low in cost and high in precision, and is beneficial to batch production of quantum dot display devices; the prepared quantum dot display device has no optical filter, is beneficial to improving the light passing rate and the display light effect, and reduces the overall power consumption of the device.
Example 5
The present embodiment provides a quantum dot display device, the structure of which is shown in fig. 14 and 15, including: the LED display panel comprises a substrate 10, a driving circuit 20, an LED array layer 30, a pixel array layer 40 and an encapsulation layer 50 covering the driving circuit 20, the LED array layer 30 and the pixel array layer 40, wherein the substrate, the driving circuit 20, the LED array layer 30 and the pixel array layer 40 are sequentially stacked;
the display area of the quantum dot display device comprises a red pixel area, a green pixel area, a blue pixel area and a white pixel area;
the LED array layer 30 includes a plurality of LED light sources 301 arranged in a pixel array (the LED light sources 301 are welded on the substrate 10 and the driving circuit 20 by conductive welding materials, the welding materials are not shown in the figure), the driving circuit 2 is configured to drive the LED light sources 301, and the LED light sources 301 are ultraviolet LEDs;
the LED light source 301 is shown in fig. 3, and includes a substrate 3016, an N-type semiconductor 3014, a light emitting layer 3015, a P-type semiconductor 3013, a P-electrode 3011, and an N-electrode 3012, where the substrate 3016 is connected to the pixel array layer 40, and the P-electrode 3011 and the N-electrode 3012 are connected to the driving circuit 20;
the pixel array layer 40 includes a red pixel layer 401, a green pixel layer 402, a blue pixel layer 403, and a white pixel layer 404; every two red pixel layers 401, two green pixel layers 402, one blue pixel layer 403 and one white pixel layer 404 constitute one display unit;
the red pixel layer 401 is positioned on the surface of the LED light source in the red pixel area;
the green pixel layer 402 is located on the surface of the LED light source within the green pixel region;
the blue pixel layer 403 is positioned on the surface of the LED light source in the blue pixel region;
the white pixel layer 404 is located on the surface of the LED light source in the white pixel region;
the material of the red pixel layer 401 is the red light composite quantum dot provided in preparation example 1;
the material of the green pixel layer 402 is the green light composite quantum dot provided by preparation example 4;
the material of the blue pixel layer 403 is the blue light composite quantum dot provided in preparation example 5;
the white pixel layer 404 is a laminated layer of a red light composite quantum dot sublayer 4041, a green light composite quantum dot sublayer 4042 and a blue light composite quantum dot sublayer 4043, and the structure of the quantum dot display device located in the white pixel region is as shown in fig. 16;
the materials of the red light composite quantum dot sublayer 4041, the green light composite quantum dot sublayer 4042 and the blue light composite quantum dot sublayer 4043 are the red light composite quantum dot provided in preparation example 1, the green light composite quantum dot provided in preparation example 4 and the blue light composite quantum dot provided in preparation example 5, respectively.
The preparation method of the quantum dot display device provided by the embodiment is as follows:
(1) providing a stacked structure of a substrate, a driving circuit and an LED array layer (the structure of which is shown in fig. 4), and depositing a red light composite quantum dot layer on the surface of the LED light source in the red pixel region as a red pixel layer 401 according to the method of embodiment 1; depositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region as a green pixel layer 402; depositing a blue light composite quantum dot layer on the surface of the LED light source in the blue pixel region as a blue pixel layer 403;
(2) depositing a lamination of a red light composite quantum dot sublayer 4041, a green light composite quantum dot sublayer 4042 and a blue light composite quantum dot sublayer 4043 layer by layer on the surface of the LED light source in the white pixel region by adopting an independent deposition method to serve as a white pixel layer 404;
wherein, the deposition conditions of the red light composite quantum dot sublayer 4041 are that the voltage difference is 10V and the current density is 7A/dm2Lasting for 10 min; the green light composite quantum dot sublayer 4042 is deposited under the conditions of a voltage difference of 8V and a current density of 5A/dm2Lasting for 20 min; the blue light composite quantum dot sublayer 4043 is deposited under the conditions of a voltage difference of 8V and a current density of 10A/dm2Lasting for 5 min;
(3) and coating the packaging glue for coating the driving circuit 20, the LED array layer 30 and the pixel array layer 40, and curing to form a packaging layer 50 to obtain the quantum dot display device.
In the embodiment, the composite quantum dots are combined with the electrodeposition process, so that the composite quantum dot layers can be directly deposited on each pixel-level LED light source independently, and high-color-gamut full-color display is realized; compared with the existing complex photoetching process, the method is simple, low in cost and high in precision, and is beneficial to batch production of quantum dot display devices; the prepared quantum dot display device has no optical filter, is beneficial to improving the light passing rate and the display light effect, and reduces the overall power consumption of the device.
Example 6
The present embodiment provides a quantum dot display device, the structure of which is shown in fig. 17 and 18, including: the LED display panel comprises a substrate 10, a driving circuit 20, an LED array layer 30, a pixel array layer 40 and an encapsulation layer 50 covering the driving circuit 20, the LED array layer 30 and the pixel array layer 40, wherein the substrate, the driving circuit 20, the LED array layer 30 and the pixel array layer 40 are sequentially stacked;
the display area of the quantum dot display device comprises a red pixel area, a green pixel area, a blue pixel area and a white pixel area;
the LED array layer 30 includes a plurality of LED light sources 301 arranged in a pixel array (the LED light sources 301 are welded on the substrate 10 and the driving circuit 20 by conductive welding materials, the welding materials are not shown in the figure), the driving circuit 2 is configured to drive the LED light sources 301, and the LED light sources 301 are blue LEDs;
the LED light source 301 is shown in fig. 3, and includes a substrate 3016, an N-type semiconductor 3014, a light emitting layer 3015, a P-type semiconductor 3013, a P-electrode 3011, and an N-electrode 3012, where the substrate 3016 is connected to the pixel array layer 40, and the P-electrode 3011 and the N-electrode 3012 are connected to the driving circuit 20;
the pixel array layer 40 includes a red pixel layer 401, a green pixel layer 402, a blue pixel layer, and a white pixel layer 404; every two red pixel layers 401, two green pixel layers 402, one blue pixel layer and one white pixel layer 404 constitute one display unit;
the red pixel layer 401 is positioned on the surface of the LED light source in the red pixel area;
the green pixel layer 402 is located on the surface of the LED light source within the green pixel region;
the LED light source surface in the blue pixel region has no composite quantum dot layer, and can transmit blue light emitted by the LED light source 301, and for convenience of explaining the structure of the quantum dot display device, the region where there is no entity on the LED light source surface is referred to as a blue pixel layer;
the white pixel layer 404 is located on the surface of the LED light source in the white pixel region;
the material of the red pixel layer 401 is the red light composite quantum dot provided in preparation example 1;
the material of the green pixel layer 402 is the green light composite quantum dot provided by preparation example 4;
the white pixel layer 404 is a lamination of a red light composite quantum dot sublayer 4041 and a green light composite quantum dot sublayer 4042, and the structure of the quantum dot display device located in the white pixel region is shown in fig. 19;
the materials of the red light composite quantum dot sublayer 4041 and the green light composite quantum dot sublayer 4042 are the red light composite quantum dot provided in preparation example 1 and the green light composite quantum dot provided in preparation example 4, respectively.
The preparation method of the quantum dot display device provided by the embodiment is as follows:
(1) providing a stacked structure of a substrate, a driving circuit and an LED array layer (the structure of which is shown in fig. 4), and depositing a red light composite quantum dot layer on the surface of the LED light source in the red pixel region as a red pixel layer 401 according to the method of embodiment 3; depositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region as a green pixel layer 402; no material is deposited on the surface of the LED light source in the blue pixel area, and the area without solid bodies is used as a blue pixel layer;
(2) depositing a lamination of a red light composite quantum dot sublayer 4041 and a green light composite quantum dot sublayer 4042 layer by layer on the surface of the LED light source in the white pixel region by adopting an independent deposition method to serve as a white pixel layer 404;
wherein, the deposition conditions of the red light composite quantum dot sublayer 4041 are that the voltage difference is 10V and the current density is 6A/dm2Lasting for 10 min; the green light composite quantum dot sublayer 4042 is deposited under the conditions of a voltage difference of 1V and a current density of 10A/dm2Lasting for 10 min;
(3) and coating the packaging glue for coating the driving circuit 20, the LED array layer 30 and the pixel array layer 40, and curing to form a packaging layer 50 to obtain the quantum dot display device.
In the embodiment, the composite quantum dots are combined with the electrodeposition process, so that the composite quantum dot layers can be directly deposited on each pixel-level LED light source independently, and high-color-gamut full-color display is realized; compared with the existing complex photoetching process, the method is simple, low in cost and high in precision, and is beneficial to batch production of quantum dot display devices; the prepared quantum dot display device has no optical filter, is beneficial to improving the light passing rate and the display light effect, and reduces the overall power consumption of the device.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A quantum dot display device, comprising: the LED array substrate comprises a substrate, a driving circuit, an LED array layer and a pixel array layer which are sequentially stacked;
the display area of the quantum dot display device comprises a red pixel area, a green pixel area and a blue pixel area;
the LED array layer comprises a plurality of LED light sources which are arranged in a pixel array, the driving circuit is used for driving the LED light sources, and the LED light sources are blue LEDs or ultraviolet LEDs;
the pixel array layer comprises a red pixel layer, a green pixel layer and a blue pixel layer;
the red pixel layer is positioned on the surface of the LED light source in the red pixel area;
the green pixel layer is positioned on the surface of the LED light source in the green pixel area;
the blue pixel layer is positioned on the surface of the LED light source in the blue pixel area;
the red pixel layer is made of red light composite quantum dots;
the green pixel layer is made of green light composite quantum dots;
the LED light source is a blue LED, and the blue pixel layer is a blue light transmission layer; when the LED light source is an ultraviolet LED, the blue pixel layer is made of a blue light composite quantum dot;
the red light composite quantum dot, the green light composite quantum dot and the blue light composite quantum dot respectively comprise an inner core, a coating layer wrapping the inner core and a ligand connected to the outer surface of the coating layer;
the inner core is a red light quantum dot, a green light quantum dot or a blue light quantum dot, the ligand is organic salt with an ionic bond, and the red light composite quantum dot, the green light composite quantum dot and the blue light composite quantum dot are positively or negatively charged in a ligand dissociation state.
2. The quantum dot display device of claim 1, wherein the display area of the quantum dot display device further comprises a white pixel region, the pixel array layer further comprising a white pixel layer located at a surface of the LED light source within the white pixel region;
when the LED light source is a blue LED, the white pixel layer is a mixed layer of the red light composite quantum dots and the green light composite quantum dots, or a laminated layer of the red light composite quantum dot layer and the green light composite quantum dot layer;
when the LED light source is an ultraviolet LED, the white pixel layer is a mixed layer of the red light composite quantum dot, the green light composite quantum dot and the blue light composite quantum dot, or a laminated layer of the red light composite quantum dot layer, the green light composite quantum dot layer and the blue light composite quantum dot layer.
3. The quantum dot display device according to claim 1 or 2, further comprising an encapsulation layer encapsulating the driving circuit, the LED array layer, and the pixel array layer.
4. The quantum dot display device according to any one of claims 1 to 3, wherein the red, green and blue quantum dots are AxMyEzA system material;
wherein, the element A is selected from one or the combination of at least two of Ba, Ag, Na, Fe, In, Cd, Zn, Ga, Mg, Pb and Cs;
m element is selected from one or the combination of at least two of S, Cl, O, As, N, P, Se, Te, Ti, Zr and Pb;
the E element is selected from one or the combination of at least two of S, As, Se, O, Cl, Br and I;
x is 0.3 to 2.0, y is 0.5 to 3.0, and z is 0 to 4.0.
5. The quantum dot display device according to any one of claims 1 to 4, wherein the material of the clad is a polymer material, a metal oxide, a metal sulfide, a metal or a metal alloy;
preferably, the polymer material is selected from one or a combination of at least two of PMA, PVDF and long-chain phosphate;
preferably, the long-chain phosphate is phosphate with 16-18 carbon atoms;
preferably, the metal oxide is selected from ZnO, SiO2、TiO2Or one or a combination of at least two of MgO;
preferably, the metal sulfide is selected from one or a combination of at least two of ZnS, CdS or TeS;
preferably, the metal is selected from one or a combination of at least two of Ti, Zr, Zn, Cd or Te;
preferably, the organic salt having an ionic bond includes an organic negative ion salt or an organic positive ion salt;
preferably, the organic negative ion salt includes an organic acid salt;
preferably, the organic acid salt comprises one or a combination of at least two of sodium acetate, picolinate or sodium ethoxide;
preferably, the organic cationic salt comprises an organic ammonium salt;
preferably, the organic ammonium salt comprises one or a combination of at least two of tetrabutylammonium bromide, ammonium chloride or ammonium sulfate.
6. The quantum dot display device according to any one of claims 1 to 5, wherein the particle size of the red light quantum dot is 6 to 12nm, the particle size of the green light quantum dot is 3 to 6nm, and the particle size of the blue light quantum dot is 1 to 3 nm.
7. The quantum dot display device according to any one of claims 1 to 6, wherein the red light composite quantum dot, the green light composite quantum dot and the blue light composite quantum dot are prepared by the following steps:
a: dripping a coating layer material into the red light quantum dots, the green light quantum dots or the blue light quantum dots, controlling the pH value, the reaction temperature and the reaction time, and coating the coating layer material on the surfaces of the red light quantum dots, the green light quantum dots or the blue light quantum dots to form a coating layer to obtain a quantum dot/coating layer core-shell material;
b: and b, dispersing the quantum dot/coating core-shell material obtained in the step a and a ligand in a solvent, and controlling the pH, the reaction temperature and the reaction time to enable the ligand to be connected to the surface of the coating to obtain a solution of the red light composite quantum dot, the green light composite quantum dot or the blue light composite quantum dot.
8. The quantum dot display device according to claim 7, wherein the pH in step a is 5.5-11, the reaction temperature is 240-320 ℃, and the reaction time is 0.5-10 min;
preferably, the pH value in the step b is 7-10, the reaction temperature is 120-320 ℃, and the reaction time is 3-120 min;
preferably, the solvent in step b is one or a combination of at least two of octadecene, n-hexane, n-octane, oily ammonia, n-dodecyl mercaptan, 1-octyl mercaptan or trioctyl amine.
9. A method of manufacturing a quantum dot display device according to any of claims 1 to 8, comprising the steps of:
providing a laminated structure of a substrate, a driving circuit and an LED array layer, and depositing a red light composite quantum dot layer on the surface of an LED light source in a red pixel region through electrodeposition to serve as a red pixel layer; depositing a green light composite quantum dot layer on the surface of the LED light source in the green pixel region to serve as a green pixel layer; depositing a blue light composite quantum dot layer on the surface of the LED light source in the blue pixel region or not, and taking the blue light composite quantum dot layer as a blue pixel layer; obtaining the quantum dot display device;
the electrodeposition method is a separate deposition method, and the separate deposition method comprises the following steps: selecting one of a red light composite quantum dot layer, a green light composite quantum dot layer and a blue light composite quantum dot layer, placing the laminated structure in a solution of composite quantum dots to be deposited, applying a voltage opposite to the electrical property of the composite quantum dots to be deposited to an LED light source to be deposited through the driving circuit, applying a voltage identical to the electrical property of the composite quantum dots to be deposited to the solution of the composite quantum dots to be deposited, and depositing;
preferably, the electrodeposition voltage is 1-12V, and the current density is 5-10A/dm2The deposition time is 0.5-30 min.
10. A method of manufacturing as claimed in claim 9, further comprising depositing a white pixel layer on a surface of the LED light source within the white pixel area;
the deposition method of the white pixel layer comprises the following steps: placing the laminated structure in a mixed solution of red light composite quantum dots and green light composite quantum dots with the same electrical property, or in a mixed solution of red light composite quantum dots, green light composite quantum dots and blue light composite quantum dots with the same electrical property, applying a voltage with the electrical property opposite to that of the composite quantum dots to be deposited to an LED light source in a white pixel region through the driving circuit, and applying a voltage with the electrical property same as that of the composite quantum dots to be deposited to the mixed solution for deposition;
or according to the single deposition method, depositing a lamination of the red light composite quantum dot layer and the green light composite quantum dot layer by layer on the surface of the LED light source in the white pixel region, or depositing a lamination of the red light composite quantum dot layer, the green light composite quantum dot layer and the blue light composite quantum dot layer by layer;
preferably, the preparation method further comprises: after each electrodeposition, taking out the deposited laminated structure, drying, and heating, freezing or illuminating;
preferably, the heating temperature is 80-150 ℃;
preferably, the freezing is freezing below-40 ℃;
preferably, the light irradiation is carried out under the ultraviolet irradiation of 230-;
preferably, the preparation method further comprises: and after the pixel array layer is prepared, coating packaging glue for coating the driving circuit, the LED array layer and the pixel array layer, and curing to form the packaging layer.
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Application publication date: 20210514 |