CN110980634A - Nanoparticle patterning method, display screen and display device - Google Patents
Nanoparticle patterning method, display screen and display device Download PDFInfo
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- CN110980634A CN110980634A CN201911204441.2A CN201911204441A CN110980634A CN 110980634 A CN110980634 A CN 110980634A CN 201911204441 A CN201911204441 A CN 201911204441A CN 110980634 A CN110980634 A CN 110980634A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0061—Methods for manipulating nanostructures
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133614—Illuminating devices using photoluminescence, e.g. phosphors illuminated by UV or blue light
Abstract
The invention provides a method for patterning nanoparticles, a display screen and a display device, wherein the method for patterning the nanoparticles comprises the following steps: adopting illumination to enable the nanoparticles to form a cross-linked network containing the nanoparticles under the action of the diazonaphthoquinone unit; to achieve the pattern of nanoparticles.
Description
Technical Field
The invention relates to the technical field of display, in particular to a method for patterning nanoparticles, a display screen and a display device.
Background
An Organic Light Emitting Diode (OLED) is an active Light Emitting display device, and has the advantages of self-luminescence, wide viewing angle, high contrast, low power consumption, and fast response speed. With the continuous development of display technology, the OLED technology is more and more applied to various display devices, especially to smart terminal products such as mobile phones and tablet computers.
Through years of development, Organic Light Emitting Diodes (OLEDs) are now in the development stage of large-scale industrialization, and tend to gradually replace LCDs as mainstream display technologies. The preparation process of the OLED display mainly depends on evaporation, and has high difficulty in high-precision display, low material utilization rate and low yield, so that the commercial application of the large-size and high-resolution OLED display still faces a plurality of problems at present. However, the OLED process of the printing method is still not mature, and cannot be used as a mainstream to replace the evaporation method, and it is difficult to improve the high resolution.
Quantum Dots (QDs), also called nanocrystals, are nanoparticles composed of elements of groups II-VI or III-V. The particle size of the nano particles is generally between 1 nm and 20nm, and as electrons and holes are limited by quanta, a continuous energy band structure is changed into a discrete energy level structure with molecular characteristics, and the nano particles can emit fluorescence after being excited.
The emission spectrum of the quantum dots can be controlled by varying the size of the quantum dots. The emission spectrum of a quantum dot can be made to cover the entire visible region by varying its size and its chemical composition. In the case of CdTe quantum dots, their emission wavelength can be red-shifted from 510nm to 660nm as the particle size grows from 2.5nm to 4.0 nm.
At present, quantum dots can be used as molecular probes for fluorescent labeling by utilizing the light emitting characteristics of the quantum dots, and can also be used in display devices, wherein the monochromatic quantum dots are used as light emitting sources of a backlight module of a display screen, and the monochromatic quantum dots emit monochromatic light after being excited by a blue light LED and are mixed with the blue light to form white background light, so that the color gamut is larger, and the picture quality can be improved.
At present, the main patterning methods of qdled (quantity Dot Light Emitting diodes) include printing, photolithography, transfer printing and the like. Printing suffers from the same problems as OLED, with high resolution, which is currently no more than 300 ppi. Therefore, the development of a new nano particle patterning method has important value.
Disclosure of Invention
The technical problem to be solved by the embodiments of the present invention is to provide a method, a display screen, and a display device for patterning nanoparticles, so as to implement the patterning of nanoparticles.
In order to solve the above technical problem, an embodiment of the present invention provides a method for patterning nanoparticles, including:
and (3) irradiating by using light to enable the nanoparticles to form a cross-linked network containing the nanoparticles under the action of the diazonaphthoquinone unit.
Optionally, the forming, by using light irradiation, a crosslinked network including the nanoparticle under the action of the diazonaphthoquinone unit includes:
mixing the nanoparticles with a photosensitive compound containing at least two diazonaphthoquinone units;
and (3) under the action of the at least two diazonaphthoquinone units, the nanoparticles are linked with the photosensitive compound by adopting illumination to form a cross-linked network containing the nanoparticles.
Optionally, the photosensitive compound containing at least two diazonaphthoquinone units has a general formula of R- (C10ON2H5) n, wherein R is a linking group, C10ON2H5 is a diazonaphthoquinone unit, and n is greater than or equal to 2.
Optionally, the linking group comprises one or more of aliphatic hydrocarbon, aromatic hydrocarbon, heterocyclic compound, alcohol, aldehyde, ester, ether, ketone and amide.
Optionally, the mass ratio of the photosensitive compound to the nanoparticles is 1: 50-1: 10.
Optionally, the forming, by using light irradiation, a crosslinked network containing nanoparticles under the action of the diazonaphthoquinone unit includes:
dissolving the nanoparticles, wherein the nanoparticles contain ligands containing at least diazonaphthoquinone units;
and mutually linking the nanoparticles under the action of the ligands by adopting illumination to form a cross-linked network containing the nanoparticles.
Optionally, the general formula of the ligand is (X) n-R- (C10ON2H5) m, wherein X is a coordinating group, n is more than or equal to 1, R is a connecting group, C10ON2H5 is a diazonaphthoquinone unit, and m is more than or equal to 1.
Optionally, the coordinating group comprises one or more of carboxyl, sulfhydryl, amino, phosphorus atom and phosphinyl.
Optionally, the nanoparticles include metal nanoparticles, oxide nanoparticles, and quantum dots.
Optionally, the quantum dot includes one or more of cadmium selenide, indium phosphide, zinc selenide, lead sulfide, cesium lead halide, zinc oxide, titanium dioxide, a cadmium selenide/zinc selenide core-shell structure, an indium phosphide/zinc selenide core-shell structure, and a cadmium selenide/cadmium sulfide/zinc sulfide core-shell structure.
In order to solve the technical problem, an embodiment of the present invention further provides a display screen, which is prepared by the nanoparticle patterning method.
In order to solve the above technical problem, an embodiment of the present invention further provides a display device, including the display screen.
The embodiment of the invention provides a method for patterning nanoparticles, a display screen and a display device, wherein a diazonaphthoquinone unit is subjected to a photochemical reaction under illumination to form a unit containing carboxyl, so that the nanoparticles can be crosslinked through the carboxyl to form a crosslinked network containing the nanoparticles, namely the nanoparticles are crosslinked through the carboxyl to form the network, thereby realizing the patterning of the nanoparticles.
Of course, not all of the advantages described above need to be achieved at the same time in the practice of any one product or method of the invention. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the embodiments of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the example serve to explain the principles of the invention and not to limit the invention. The shapes and sizes of the various elements in the drawings are not to scale and are merely intended to illustrate the invention.
FIG. 1 is a flow chart of a method for patterning nanoparticles according to a first embodiment of the present invention;
FIG. 2 is a schematic structural diagram of nanoparticles before light irradiation in a second embodiment of the present invention;
FIG. 3 is a schematic structural diagram of nanoparticles after illumination according to a second embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The embodiment of the invention provides a method for patterning nanoparticles, which comprises the following steps: and (3) irradiating by using light to enable the nanoparticles to form a cross-linked network containing the nanoparticles under the action of the diazonaphthoquinone unit. The nanoparticles may have various structures, for example, the nanoparticles may be metal nanoparticles, oxide nanoparticles, quantum dots, or the like.
In the present embodiment, the diazonaphthoquinone unit has photosensitivity, and it undergoes a photochemical reaction under irradiation with light to become a unit including a carboxyl group. The carboxyl is a good coordination group of the nano particles, and can be connected with the nano particles to form a cross-linked network containing the nano particles, so that the patterning of the nano particles is realized.
Specifically, the photochemical reaction formula of the diazonaphthoquinone unit under Ultraviolet (UV) irradiation is as follows:
as can be seen from the above photochemical reaction formula, the diazonaphthoquinone unit becomes a unit containing a carboxyl group under irradiation of ultraviolet rays.
According to the method for patterning the nanoparticles, disclosed by the embodiment of the invention, the diazonaphthoquinone unit is subjected to a photochemical reaction under illumination to form a unit containing carboxyl, so that the nanoparticles can be crosslinked through the carboxyl to form a crosslinked network containing the nanoparticles, namely, the nanoparticles are crosslinked through the carboxyl to form the network, and thus the patterning of the nanoparticles is realized.
The technical solution of the present invention will be described in detail by the following specific examples.
First embodiment
FIG. 1 is a flowchart of a nanoparticle patterning method according to a first embodiment of the present invention. As shown in fig. 1, the nanoparticles are quantum dots.
The method for patterning nanoparticles comprises the following steps:
(1) a nanoparticle solution is formed. Forming the nanoparticle solution includes: forming a nanoparticle solution having a nanoparticle concentration of 20mg/mL, the nanoparticles containing a ligand. The ligand can adopt oleic acid or oleylamine and the like, and does not contain diazonaphthoquinone units; the nanoparticles may adopt cadmium selenide (CdSe), indium phosphide (InP), zinc selenide (ZnSe), lead sulfide (PbS), etc., may also adopt a core-shell structure, such as a cadmium selenide/zinc selenide core-shell structure (CdSe/ZnSe) or an indium phosphide/zinc selenide core-shell structure (InP/ZnSe), etc., and may also adopt alloy-type quantum dots, such as a cadmium selenide/cadmium zinc selenide/zinc selenide alloy-type quantum dot (CdSe/ZnSe) having a gradual change structure.
(2) Forming a mixed solution. Forming the mixed solution includes: and adding a photosensitive compound into the nanoparticle solution, wherein the mass ratio of the photosensitive compound to the nanoparticles is 1: 50-1: 10, so as to form a mixed solution. The photosensitive compound contains at least two diazonaphthoquinone units; the photosensitive compound has a general formula of R- (C)10ON2H5)n(ii) a Wherein, R is a connecting group and can adopt one or more of aliphatic hydrocarbon, aromatic hydrocarbon, heterocyclic compound, alcohol, aldehyde, ester, ether, ketone and amide. C10ON2H5Is diazonaphthoquinone unit, and n is not less than 2.
Specifically, the structural formula of the photosensitive compound is as follows:
alternatively, the photoactive compound has the formula:
(3) and irradiating the mixed solution by adopting ultraviolet rays. Irradiating the mixed solution with ultraviolet light includes: irradiating the mixed solution by using ultraviolet rays with the wavelength of 365nm, wherein the exposure amount is 20-200 mJ/cm2. Wherein, ultraviolet irradiation causes at least two diazonaphthoquinone units in the photosensitive compound to have photochemical reaction to form a functional group containing carboxyl, namely the photosensitive compound forms a compound containing at least two carboxyl; so that the nanoparticles in the mixed solution are respectively linked with the compounds under the action of carboxyl groups, thereby forming a cross-linked network containing quantum dots and realizing the patterning of the quantum dots.
The patterned nano particles of the embodiment of the invention can be used for electroluminescence and are mainly used for organic light emitting diode (QLED) display screens. The material can also be used for photoluminescence, is mainly used for quantum dot color films (QDPR) and is used as a color conversion layer. The blue light emitting diode can also be used for Liquid Crystal Displays (LCDs), or blue light micro light emitting diodes + quantum dot color films (QDPRs), blue light organic light emitting diodes (QLEDs) + quantum dot color films (QDPRs) and the like.
According to the method for preparing the nano-particles by patterning, provided by the embodiment of the invention, the photosensitive compound containing the diazonaphthoquinone unit is subjected to a photochemical reaction under illumination to form a cross-linked network containing the nano-particles, so that the nano-particles are patterned.
Second embodiment
FIG. 2 is a schematic structural diagram of nanoparticles before light irradiation in a second embodiment of the present invention; FIG. 3 is a schematic structural diagram of nanoparticles after illumination according to a second embodiment of the present invention. The nanoparticles may be oxide nanoparticles, such as zinc oxide or titanium dioxide; alternatively, the nanoparticles may be metal nanoparticles, such as silver nanoparticles or gold nanoparticles.
The method for patterning nanoparticles comprises the following steps:
(1) the nanoparticles 1 were dissolved to form a nanoparticle solution having a nanoparticle concentration of 20 mg/mL. Wherein the nanoparticle 1 contains a ligand 2, and the ligand 2 is at leastContains diazonaphthoquinone units, as shown in FIG. 2. Specifically, the ligand has the general formula (X)n-R-(C10ON2H5)mWherein, X is a coordination group, n is more than or equal to 1, and the coordination group can adopt one or more of carboxyl, sulfydryl, amino, phosphorus atom and phosphinyl; r is a connecting group, and can adopt one or more of aliphatic hydrocarbon, aromatic hydrocarbon, heterocyclic compound, alcohol, aldehyde, ester, ether, ketone and amide. C10ON2H5Is diazonaphthoquinone unit, and m is greater than or equal to 1.
Specifically, the structural formula of the diazonaphthoquinone unit-containing ligand is as follows:
Or
(2) And irradiating the nanoparticle solution by using ultraviolet rays. Specifically, the mixed solution is irradiated by ultraviolet with the wavelength of 365nm, and the exposure amount is 20-200 mJ/cm2. In which ultraviolet rays make diazonaphthoquinone units of ligands in the nanoparticles 1 undergo a photochemical reaction to form carboxyl-containing functional groups, i.e., the nanoparticles form carboxyl-containing compounds, so that other nanoparticles 1 can be linked with the nanoparticles 1 under the action of the carboxyl groups, thereby forming a crosslinked network including the nanoparticles 1, and realizing patterning of the nanoparticles 1, as shown in fig. 3.
As can be seen from the above patterning preparation method, in the method for patterning nanoparticles provided in the embodiment of the present invention, the ligand of the nanoparticles contains a diazonaphthoquinone unit, and the diazonaphthoquinone unit in the ligand undergoes a photochemical reaction under light irradiation to form a crosslinked network including the nanoparticles, thereby implementing patterning of the nanoparticles.
Third embodiment
Based on the technical concept of the embodiment of the invention, the embodiment of the invention also provides a display screen, and the display screen is prepared by the nanoparticle patterning method of the first embodiment.
The display screen of the embodiment of the invention can be an organic light emitting diode (QLED) display screen, a quantum dot color film (QDPR) or a Liquid Crystal Display (LCD), a blue light micro light emitting diode (MicroLED) + quantum dot color film (QDPR), a blue light organic light emitting diode (QLED) + quantum dot color film (QDPR) and other display screens.
Specifically, use the display screen as Liquid Crystal Display (LCD) as an example, this display screen includes subtend base plate, array substrate and is located subtend base plate with the liquid crystal layer between the array substrate, be provided with a plurality of pixel units on the array substrate, every the pixel unit has a plurality of sub pixel units that show different colours, and in the position of subtend base plate or array substrate that the sub pixel unit of at least one colour of each pixel unit corresponds, be provided with monochromatic quantum dot layer, monochromatic quantum dot layer sends out after receiving the background light excitation and corresponds the monochromatic light of sub pixel unit colour. Wherein, the monochromatic quantum dot layer is prepared by the nanoparticle patterning method of the previous embodiment.
Fourth embodiment
Based on the technical idea of the embodiment of the present invention, an embodiment of the present invention further provides a display device, including the display screen of the third embodiment. The display device may be: any product or component with a display function, such as a mobile phone, a tablet computer, a television, a display, a notebook computer, a digital photo frame, a navigator and the like.
In the description of the embodiments of the present invention, it should be understood that the terms "middle", "upper", "lower", "front", "rear", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the description of the embodiments of the present invention, it should be noted that, unless explicitly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (12)
1. A method of nanoparticle patterning, comprising:
and (3) irradiating by using light to enable the nanoparticles to form a cross-linked network containing the nanoparticles under the action of the diazonaphthoquinone unit.
2. The method for patterning nanoparticles according to claim 1, wherein the step of forming the nanoparticles into a cross-linked network containing the nanoparticles under the action of diazonaphthoquinone units by using light irradiation comprises:
mixing the nanoparticles with a photosensitive compound containing at least two diazonaphthoquinone units;
and (3) under the action of the at least two diazonaphthoquinone units, the nanoparticles are linked with the photosensitive compound by adopting illumination to form a cross-linked network containing the nanoparticles.
3. A method for nanoparticle patterning according to claim 2, wherein the photosensitive compound containing at least two diazonaphthoquinone units has the general formula R- (C)10ON2H5)nWherein R is a linking group, C10ON2H5Is diazonaphthoquinone unit, and n is not less than 2.
4. The method of claim 3, wherein the linking group comprises one or more of aliphatic hydrocarbon, aromatic hydrocarbon, heterocyclic compound, alcohol, aldehyde, ester, ether, ketone, and amide.
5. The method of claim 2, wherein the mass ratio of the photosensitive compound to the nanoparticles is 1:50 to 1: 10.
6. The method for patterning nanoparticles according to claim 1, wherein the step of forming the nanoparticles into a crosslinked network containing the nanoparticles under the action of diazonaphthoquinone units by using light irradiation comprises:
dissolving the nanoparticles, wherein the nanoparticles contain ligands containing at least diazonaphthoquinone units;
and mutually linking the nanoparticles under the action of the ligands by adopting illumination to form a cross-linked network containing the nanoparticles.
7. A method for nanoparticle patterning according to claim 6, wherein the ligand has the general formula (X)n-R-(C10ON2H5)mWherein X is a coordinating group, n is not less than 1, R is a linking group, C10ON2H5Is diazonaphthoquinone unit, and m is greater than or equal to 1.
8. A method for patterning nanoparticles according to claim 7, wherein the coordinating group comprises one or more of a carboxyl group, a thiol group, an amino group, a phosphorus atom and a phosphinyl group.
9. The method of nanoparticle patterning according to claim 1, wherein the nanoparticles comprise metal nanoparticles, oxide nanoparticles and quantum dots.
10. A method for nanoparticle patterning as claimed in claim 9, wherein the quantum dots comprise one or more of cadmium selenide, indium phosphide, zinc selenide, lead sulphide, cesium lead halides, zinc oxide, titanium dioxide, a cadmium selenide/zinc selenide core-shell structure, an indium phosphide/zinc selenide core-shell structure and a cadmium selenide/cadmium sulphide/zinc sulphide core-shell structure.
11. A display screen prepared by the method of patterning nanoparticles according to any one of claims 1 to 10.
12. A display device comprising the display screen of claim 11.
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| WO2023178852A1 (en) * | 2022-03-22 | 2023-09-28 | 清华大学 | Nanoparticle printing method and light-emitting element |
| WO2024045114A1 (en) * | 2022-09-01 | 2024-03-07 | 京东方科技集团股份有限公司 | Quantum dot material, light-emitting device and preparation method therefor, and display apparatus |
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