CN110289363B - Method for patterning nanoparticle layer, quantum dot light-emitting device and display device - Google Patents
Method for patterning nanoparticle layer, quantum dot light-emitting device and display device Download PDFInfo
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- CN110289363B CN110289363B CN201910576880.XA CN201910576880A CN110289363B CN 110289363 B CN110289363 B CN 110289363B CN 201910576880 A CN201910576880 A CN 201910576880A CN 110289363 B CN110289363 B CN 110289363B
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- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
Abstract
The invention relates to the field of display, in particular to a method for patterning a nanoparticle layer, a quantum dot light-emitting device and a display device. The method for patterning the nanoparticle layer comprises the following steps: forming a substrate modified with a first group; treating a preset area of the substrate by adopting illumination, wherein the first group in the preset area reacts under the illumination condition to generate a second group; forming a nanoparticle layer on the surface of the preset region, wherein the second group in the preset region is connected with a ligand of the nanoparticle; and removing the nanoparticles which are not combined with the second groups from the nanoparticle layer to complete the patterning of the nanoparticle layer. The invention can complete the patterning of the nano-particle layer, especially the quantum dot layer, without adopting an ink-jet printing method, and can form the nano-particle layer with high resolution and good performance.
Description
Technical Field
The invention relates to the field of display, in particular to a method for patterning a nanoparticle layer, a quantum dot light-emitting device and a display device.
Background
With the deep development of the Quantum dot preparation technology, the stability and the Light Emitting efficiency of the Quantum dots are continuously improved, the research on Quantum dot electroluminescent diodes (QLEDs) is continuously deep, and the application prospect of the QLEDs in the display field is gradually bright. However, the high resolution patterning (>300ppi) technology of QLEDs has not yet made a breakthrough, which hinders the commercialization of QLEDs.
The quantum dots are zero-dimensional nano semiconductor materials, the size of each of the three dimensions of the quantum dots is not more than twice the exciton Bohr radius of the corresponding semiconductor material, and when the patterned quantum dots are manufactured in the prior art, due to the characteristics of the inorganic nanoparticles of the quantum dots, the patterned quantum dots cannot be manufactured by an evaporation film-forming and patterning method.
The related art generally manufactures patterned quantum dots by an ink-jet printing method, and it is difficult to achieve a high resolution using this method.
Also, inorganic nanoparticles, which have similar properties to quantum dots, also cannot form a patterned high-resolution film layer according to the related art.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: providing a method for patterning a nanoparticle layer, a quantum dot light-emitting device and a display device; the patterning method can form a nano particle layer with high resolution, and when the nano particle layer is applied to a quantum dot light-emitting device, a quantum dot layer with high resolution can be formed.
The invention provides a method for patterning a nanoparticle layer, which comprises the following steps:
(S1) forming a substrate modified with a first group;
(S2) treating a preset area of the substrate by adopting light, wherein the first group in the preset area reacts under the condition of light to generate a second group;
(S3) forming a nanoparticle layer on the surface of the predetermined region, wherein the second group in the predetermined region is connected to a ligand of the nanoparticle;
(S4) removing the nanoparticles of the nanoparticle layer that are not bonded to the second group, thereby completing patterning of the nanoparticle layer.
Preferably, the step (S1) is specifically:
directly modifying the substrate to form a substrate modified with a first group; or
And coating a compound coating containing a first group on the surface of the substrate to form the substrate modified with the first group.
Preferably, the first group is a group that generates an amino group upon illumination or a group that generates a hydroxyl group upon illumination.
Preferably, in the step (S3), the second group in the predetermined region is linked to the ligand of the nanoparticle by light irradiation or heating.
Preferably, the ligand of the nanoparticle comprises a group reactive with an amino group or a hydroxyl group.
Preferably, the nanoparticle layer is a quantum dot layer.
Preferably, the method specifically comprises:
irradiating a first preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the first preset region under the illumination condition to generate a second group;
forming a first quantum dot layer on the surface of the first preset region, wherein a second group in the first preset region of the substrate is connected with a ligand of the first quantum dot;
removing first quantum dots of the first quantum dot layer that are not bound to the second group;
irradiating a second preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the second preset area under the illumination condition to generate a second group;
forming a second quantum dot layer on the surface of the second preset area, wherein a second group in the second preset area of the substrate is combined with the second quantum dot;
removing second quantum dots of the second quantum dot layer that are not bound to the second group;
wherein the color of light emitted by the first quantum dot is different from the color of light emitted by the second quantum dot.
Preferably, the method further comprises:
irradiating a third preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the third preset region under the illumination condition to generate a second group;
forming a third quantum dot layer, wherein second groups in a third preset area of the substrate are combined with the third quantum dots;
removing third quantum dots of the third quantum dot layer that are not bound to the second group;
wherein the color of light emitted by the third quantum dot is different from the color of light emitted by the first quantum dot and the color of light emitted by the second quantum dot.
Preferably, the first group is an o-nitrobenzyl carbamate, a benzenesulfonamide, a,
the ligand of the quantum dot is
The first group is
When the temperature of the water is higher than the set temperature,
the ligand of the quantum dot is
The quantum dots are first quantum dots, second quantum dots or third quantum dots.
The invention discloses a manufacturing method of a quantum dot light-emitting device, which comprises the steps of forming an anode, a quantum dot layer and a cathode, wherein the quantum dot layer is manufactured by adopting the patterning method of the technical scheme.
The invention discloses a quantum dot light-emitting device which is manufactured by adopting the manufacturing method of the quantum dot light-emitting device in the technical scheme.
The invention also discloses a display device which comprises the quantum dot light-emitting device in the technical scheme.
Compared with the prior art, the method can complete the patterning of the nanoparticle layer, particularly the quantum dot layer without adopting an ink-jet printing method, and can form the nanoparticle layer or the quantum dot layer with high resolution and good performance.
Drawings
Fig. 1 is a flow chart illustrating a method for patterning a quantum dot layer according to an embodiment of the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention in conjunction with the following examples, but it will be understood that the description is intended to illustrate the features and advantages of the invention further, and not to limit the invention.
The embodiment of the invention discloses a method for patterning a nanoparticle layer, which comprises the following steps:
(S1) forming a substrate modified with a first group;
(S2) treating a preset area of the substrate by adopting light, wherein the first group in the preset area reacts under the condition of light to generate a second group;
(S3) forming a nanoparticle layer on the surface of the predetermined region, wherein the second group in the predetermined region is connected to a ligand of the nanoparticle;
(S4) removing the nanoparticles of the nanoparticle layer that are not bonded to the second group, thereby completing patterning of the nanoparticle layer.
In fig. 1, 1 is a substrate, 2 is a first group, 3 is a second group, and 4 is a nanoparticle.
In the present invention, between the nanoparticle layers, first, a first group is modified on the substrate; then, treating a preset area of the substrate by adopting light, wherein the preset area is a corresponding area in which a nano particle layer pattern needs to be formed; and then, forming a nanoparticle layer, wherein the first group in the preset region can react under the condition of light treatment to generate a second group. The second group can react with the ligand of the nanoparticle to form a tight connection; in the non-irradiated area, the surface of the substrate is still modified with a first group, the first group cannot be effectively connected with the ligand of the nano particle, and the adhesion force is basically absent; and finally, removing the nanoparticles which are not combined with the second groups from the nanoparticle layer to complete the patterning of the nanoparticle layer.
The above steps are described in detail below.
(S1) forming a substrate modified with the first group.
Preferably, the step (S1) is specifically:
directly modifying the substrate to form a substrate modified with a first group; namely: reacting a compound containing a first group with a substrate material to enable the first group to be connected to the surface of the substrate, and forming the substrate modified with the first group;
or
And coating a compound coating containing a first group on the surface of the substrate to form the substrate modified with the first group.
(S2) processing a preset area of the substrate by adopting light, wherein the first group in the preset area reacts under the condition of light to generate a second group.
Preferably, the first group is a group that generates an amino group upon illumination or a group that generates a hydroxyl group upon illumination.
More preferably, the first group is an o-nitrobenzyl carbamate, a benzenesulfonamide, a,
The second group is preferably an amino group or a hydroxyl group.
(S3) forming a nanoparticle layer on the surface of the preset area, wherein the second group in the preset area is connected with the ligand of the nanoparticle.
The nanoparticle includes a group on the ligand capable of reacting with a second group. Preferably, the ligand of the nanoparticle comprises a group reactive with an amino group or a hydroxyl group.
If the second group is an amino group, it is preferred that the nanoparticle ligand comprises thereon
I.e., NHS.
The ligand of the nanoparticle is
If the second group is a hydroxyl group, it is preferred that the nanoparticle ligand comprises thereon
The ligand of the nanoparticle is
Preferably, the second group in the predetermined region is linked to the ligand of the nanoparticle by light irradiation or heating. More preferably, the second group within the predetermined region is linked to the ligand of the nanoparticle by illumination. Thereby making the patterning process more simplified.
Preferably, the illumination time is 20-30min, and the wavelength of the illumination is 254nm or 365 nm.
(S4) removing the nanoparticles of the nanoparticle layer that are not bonded to the second group, thereby completing patterning of the nanoparticle layer.
Preferably, the nanoparticles of the nanoparticle-removed layer that are not bound to the second group are removed with a solvent. And the solvent is adopted to remove the nano particles which are not combined with the second group in the nano particle layer, so that the method is simple and easy to implement in the actual production process and has lower production cost.
Preferably, the nanoparticle layer is a quantum dot layer.
Namely: an embodiment of the present invention discloses a method for patterning a quantum dot layer, comprising the following steps, with particular reference to fig. 1:
(S1') forming a substrate modified with a first group;
(S2') treating a predetermined area of the substrate with light, the first group in the predetermined area reacting under the light condition to generate a second group;
(S3') forming a quantum dot layer on the surface of the predetermined region, the second group in the predetermined region being connected to the ligand of the quantum dot;
(S4') removing the quantum dots of the quantum dot layer not bonded to the second group, completing patterning of the quantum dot layer.
The substrate may be a glass substrate, a hole injection layer, or an electron transport layer.
Preferably, different predetermined regions on the substrate may form different quantum dot layers. Therefore, the method specifically comprises:
irradiating a first preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the first preset region under the illumination condition to generate a second group;
forming a first quantum dot layer on the surface of the first preset region, wherein a second group in the first preset region of the substrate is connected with a ligand of the first quantum dot;
removing first quantum dots of the first quantum dot layer that are not bound to the second group;
irradiating a second preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the second preset region under the illumination condition to generate a second group;
forming a second quantum dot layer on the surface of the second preset area, wherein a second group in the second preset area of the substrate is combined with the second quantum dot;
removing second quantum dots of the second quantum dot layer that are not bound to the second group;
wherein the color of light emitted by the first quantum dot is different from the color of light emitted by the second quantum dot. In a specific implementation, the color of the light emitted by the first quantum dot may be red, green or blue, and the color of the light emitted by the second quantum dot may also be red, green or blue.
Further, in order to form full-color quantum dots, the method further includes:
irradiating a third preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the third preset region under the illumination condition to generate a second group;
forming a third quantum dot layer, wherein second groups in a third preset area of the substrate are combined with the third quantum dots;
removing third quantum dots of the third quantum dot layer that are not bound to the second group;
wherein the color of light emitted by the third quantum dot is different from the color of light emitted by the first quantum dot and the color of light emitted by the second quantum dot.
In specific implementation, after the first preset area of the film layer is irradiated by light with a preset wavelength, the mask can be moved, so that the light-transmitting area of the mask corresponds to the second preset area, and the irradiation of the light with the preset wavelength on the second preset area is conveniently completed; then, the mask can be continuously moved, so that the light transmission area of the mask corresponds to a third preset area, and the irradiation of light with preset wavelength on the third preset area is conveniently completed; therefore, the specific embodiment of the invention can save the process time and reduce the production cost by shielding through the mask.
Preferably, in the embodiment of the present invention, the color of light emitted by the first quantum dot, the color of light emitted by the second quantum dot, and the color of light emitted by the third quantum dot are red, green, and blue, respectively, so that the embodiment of the present invention completes the patterning process of the full-color quantum dot by the above method. The specific embodiment of the invention can complete the patterning of the quantum dot layer without adopting an ink-jet printing method or a photoetching method, and can form quantum dots with high resolution and good performance.
Preferably, the first group is an o-nitrobenzyl carbamate, a benzenesulfonamide, a,
the second group generated by illumination is amino group, which corresponds to the amino group,
the ligand of the quantum dot is
The first group is
When the temperature of the water is higher than the set temperature,
the second group generated by illumination is hydroxyl group, which corresponds to the hydroxyl group,
the ligand of the quantum dot is
The quantum dots are first quantum dots, second quantum dots or third quantum dots.
The embodiment of the invention discloses a manufacturing method of a quantum dot light-emitting device, which comprises the step of forming an anode, a quantum dot layer and a cathode, wherein the quantum dot layer is manufactured by adopting the patterning method in the technical scheme.
Preferably, the method for manufacturing the quantum dot light emitting device specifically includes:
forming an anode on a substrate;
forming a hole transport layer modified with a first group on the anode;
treating a preset area of the hole transport layer by adopting illumination, wherein the first group in the preset area reacts under the illumination condition to generate a second group;
depositing quantum dots on the hole transport layer, wherein second groups in a preset area of the hole transport layer are combined with the quantum dots;
removing quantum dots which are not combined with the second groups to form a patterned quantum dot layer;
forming an electron transport layer on the quantum dot layer;
a cathode is formed on the electron transport layer.
The hole transport layer is preferably made of polyvinyl carbazole, and the method for forming the hole transport layer modified with the first group on the anode comprises the following steps:
forming a hole transport layer by adopting polyvinylcarbazole, and reacting a compound containing a first group with the polyvinylcarbazole to enable the polyvinylcarbazole on the surface of the hole transport layer to generate a block copolymer, wherein one part of the block is polyvinylcarbazole, and the other part of the block contains the first group;
or after the hole transport layer is formed by the polyvinyl carbazole, coating a layer of the block copolymer.
If the quantum dot light-emitting device is of an inverted structure, preferably, the method for manufacturing the quantum dot light-emitting device specifically includes:
forming a cathode on a substrate;
forming an electron transport layer modified with a first group on the cathode;
treating a preset area of the electron transport layer by adopting illumination, wherein the first group in the preset area reacts under the illumination condition to generate a second group;
depositing quantum dots on the electron transport layer, wherein second groups in a preset area of the hole transport layer are combined with the quantum dots;
removing the quantum dots which are not combined with the second groups to form a quantum dot layer;
forming a hole transport layer on the quantum dot layer;
an anode is formed on the hole transport layer.
The electron transport layer is preferably made of zinc oxide, and because the surface of the zinc oxide is provided with suspended hydroxyl groups, the electron transport layer can be modified by a compound with a silane coupling group and a first group, and the first group is connected to the surface of the electron transport layer through a modification reaction to form the electron transport layer modified with the first group.
Preferably, the compound is
Wherein R is carbamic acid-o-nitrobenzyl ester, benzene sulfonamide,
The embodiment of the invention also discloses a quantum dot light-emitting device which is manufactured by adopting the manufacturing method of the quantum dot light-emitting device in the technical scheme.
The embodiment of the invention also discloses a display device which comprises the quantum dot light-emitting device in the technical scheme.
For further understanding of the present invention, the method for patterning a nanoparticle layer, the quantum dot light emitting device and the display device provided by the present invention are described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
And cleaning the substrate.
Modifying the substrate to make the substrate have a first group which is
And applying a mask to the substrate, wherein the mask covers the non-preset area, and the first preset area is not covered by the mask.
And (4) performing light treatment, and removing the protecting group of the first group on the surface of the first preset area which is not covered by the mask to generate an amino group.
Coating red quantum dots on the surface of the first preset area, wherein the ligands of the red quantum dots are
And the ligand of the red quantum dot reacts with amino to form chemical connection.
And washing away the unconnected red quantum dots by using a solvent to form a red quantum dot layer.
And moving the mask plate to enable the light transmission area of the mask plate to correspond to the second preset area.
And (4) carrying out light treatment, and removing the protecting group of the first group on the surface of the second preset area to generate an amino group.
Coating green quantum dots on the surface of the second preset area, wherein the ligands of the green quantum dots are
And the ligand of the green quantum dot reacts with amino to form chemical connection.
And washing away the unconnected green quantum dots by using a solvent to form a green quantum dot layer.
And moving the mask plate to enable the light-transmitting area of the mask plate to correspond to the third preset area.
And (4) performing light treatment, and removing the protecting group of the first group on the surface of the third preset area to generate an amino group.
Coating blue quantum dots on the surface of the third preset area, wherein the ligands of the blue quantum dots are
The unconnected blue quantum dots are washed away with a solvent to form a blue quantum dot layer, and patterning of the quantum dot layer is completed.
Example 2
Step 1, a TFT (Thin Film Transistor) backplane is prepared.
Specifically, the transparent substrate is cleaned by a standard method, and then the following steps are sequentially performedThe method comprises the following steps: depositing 200nm thick gate metal Mo, and patterning; depositing gate dielectric SiO with thickness of 150nm2(ii) a Depositing an active layer IGZO with the thickness of 40nm and patterning; depositing source and drain electrode metal Mo with the thickness of 200nm, and patterning; deposition of 300nm thick passivation layer SiO2And imaging; depositing a pixel electrode ITO with the thickness of 40nm and patterning; and finally, spin-coating an acrylic material, photoetching and curing to obtain a pixel defining layer with the thickness of about 1.5 microns to form the TFT back plate part.
And 2, preparing a hole injection layer on the TFT backboard by adopting a spin coating process.
And 3, spin-coating the polyvinyl carbazole material with the first group to form a hole transport layer modified with the first group.
The first group is
And 4, applying a mask to the substrate, wherein the mask covers the non-preset area, and the first preset area is not covered by the mask.
And (4) performing light treatment, and removing the protecting group of the first group on the surface of the preset area which is not covered by the mask to generate hydroxyl.
Coating quantum dots on the surface of a preset area, wherein the ligand of the quantum dots is
The ligand of the quantum dot reacts with hydroxyl to form chemical connection.
And washing away the unconnected quantum dots by using a solvent to complete the patterning of the quantum dot layer.
And 5, spin-coating zinc oxide nanoparticles on the quantum dot layer to form the electron transmission layer.
And 6, evaporating metal aluminum as a cathode.
And 7, packaging to obtain the AMQLED device.
The quantum dot layer and the display device formed by the invention are tested, and the resolution of the quantum dot layer can reach more than 1000ppi to the maximum. Whereas the resolution of a quantum dot layer formed by conventional ink jet printing is typically 300 ppi.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method of patterning a nanoparticle layer, comprising the steps of:
(S1) forming a substrate modified with a first group;
(S2) treating a preset area of the substrate by adopting light, wherein the first group in the preset area reacts under the condition of light to generate a second group;
(S3) forming a nanoparticle layer on the surface of the predetermined region, wherein the second group in the predetermined region is connected to a ligand of the nanoparticle;
(S4) removing the nanoparticles of the nanoparticle layer not combined with the second group, completing patterning of the nanoparticle layer;
the first group is a group which generates amino after illumination or a group which generates hydroxyl after illumination;
the ligands of the nanoparticles comprise groups that can react with amino groups or hydroxyl groups.
2. The method according to claim 1, wherein the step (S1) is embodied as:
directly modifying the substrate to form a substrate modified with a first group; or
And coating a compound coating containing a first group on the surface of the substrate to form the substrate modified with the first group.
3. The method of claim 1, wherein in step (S3), the second groups in the predetermined region are linked to the ligands of the nanoparticles by irradiation of light or heating.
4. The method of claim 1, wherein the nanoparticle layer is a quantum dot layer.
5. The method according to claim 4, characterized in that it comprises in particular:
irradiating a first preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the first preset region under the illumination condition to generate a second group;
forming a first quantum dot layer on the surface of the first preset region, wherein a second group in the first preset region of the substrate is connected with a ligand of the first quantum dot;
removing first quantum dots of the first quantum dot layer that are not bound to the second group;
irradiating a second preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the second preset area under the illumination condition to generate a second group;
forming a second quantum dot layer on the surface of the second preset region, wherein a second group in the second preset region of the substrate is connected with a ligand of the second quantum dot;
removing second quantum dots of the second quantum dot layer that are not bound to the second group;
wherein the color of light emitted by the first quantum dot is different from the color of light emitted by the second quantum dot.
6. The method of claim 5, further comprising:
irradiating a third preset area of the substrate by adopting light with a preset wavelength; reacting the first group in the third preset region under the illumination condition to generate a second group;
forming a third quantum dot layer, wherein second groups in a third preset area of the substrate are connected with ligands of the third quantum dots;
removing third quantum dots of the third quantum dot layer that are not bound to the second group;
wherein the color of light emitted by the third quantum dot is different from the color of light emitted by the first quantum dot and the color of light emitted by the second quantum dot.
7. The method of claim 5 or 6, wherein the first group is an o-nitrobenzyl carbamate, a benzenesulfonamide, a,
the ligand of the quantum dot is
The first group is
When the temperature of the water is higher than the set temperature,
the ligand of the quantum dot is
The quantum dots are first quantum dots, second quantum dots or third quantum dots.
8. A method for manufacturing a quantum dot light emitting device, comprising forming an anode, a quantum dot layer and a cathode, wherein the quantum dot layer is manufactured by the patterning method according to any one of claims 4 to 7.
9. A quantum dot light-emitting device, characterized in that it is manufactured by the method of claim 8.
10. A display device comprising the quantum dot light-emitting device according to claim 9.
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| CN110980634B (en) * | 2019-11-29 | 2021-03-02 | 京东方科技集团股份有限公司 | Nanoparticle patterning method, display screen and display device |
| CN111769200B (en) * | 2020-07-09 | 2024-04-16 | 京东方科技集团股份有限公司 | Quantum dot light emitting device, quantum dot layer patterning method and display device |
| CN111900269A (en) * | 2020-07-15 | 2020-11-06 | 京东方科技集团股份有限公司 | Quantum dot layer patterning method and quantum dot light-emitting device manufacturing method |
| CN111863917B (en) * | 2020-07-29 | 2022-11-01 | 京东方科技集团股份有限公司 | Display substrate, manufacturing method thereof and display panel |
| CN112310330A (en) * | 2020-10-30 | 2021-02-02 | 北京京东方技术开发有限公司 | Quantum dot material, quantum dot light-emitting device, display device and manufacturing method |
| CN114574187B (en) * | 2020-11-30 | 2024-03-05 | 北京京东方技术开发有限公司 | Nanoparticle, method for patterning nanoparticle layer and related application |
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