CN112234149A - Display panel, display device and manufacturing method of display panel - Google Patents
Display panel, display device and manufacturing method of display panel Download PDFInfo
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- CN112234149A CN112234149A CN202011095919.5A CN202011095919A CN112234149A CN 112234149 A CN112234149 A CN 112234149A CN 202011095919 A CN202011095919 A CN 202011095919A CN 112234149 A CN112234149 A CN 112234149A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
- H10K59/12—Active-matrix OLED [AMOLED] displays
-
- 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
- H10K59/12—Active-matrix OLED [AMOLED] displays
- H10K59/1201—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
Abstract
The invention discloses a display panel, a display device and a manufacturing method of the display panel, and aims to provide a novel patterning method of a quantum dot film layer. The display panel includes: the quantum dot array substrate comprises a substrate base plate, an electrode and a quantum dot film layer, wherein the electrode and the quantum dot film layer are sequentially positioned on one side of the substrate base plate; wherein the quantum dot film layer comprises: the quantum dot film comprises a quantum dot body and a charged connecting structure connected with the quantum dot body, wherein the charged connecting structure is formed by reacting a charged precursor structure with opposite electric property with first ions, the electric property of the first ions is opposite to that of the charged precursor structure, and the first ions are generated by decomposing a first substance mixed in the quantum dot film under a preset condition.
Description
Technical Field
The invention relates to the technical field of display, in particular to a display panel, a display device and a manufacturing method of the display panel.
Background
An Active-matrix organic light-emitting diode (AMOLED) is known to be a promising next generation display to replace a liquid crystal display panel, but with the increase of consumer consumption level, a high resolution product becomes a key development direction of a display product, and a high resolution AMOLED product is difficult to compete with a liquid crystal display panel because an organic layer structure of an organic light-emitting display is generally prepared by a mask evaporation method, but the mask evaporation method has the defects of difficult alignment, low yield and incapability of realizing smaller area light emission; the problem of insufficient ability to precisely control the evaporation region cannot meet the rapidly developing requirements for high-resolution display at present; the printing and printing methods are adopted to replace the mask evaporation process for preparing the organic light-emitting layer, and the obtained resolution is also extremely limited. Therefore, the AMOLED product with high resolution has the serious problems of high technical difficulty, low product yield and high commodity price.
On the other hand, with the deep development of the quantum dot technology, the research of the electroluminescent quantum dot light emitting diode is increasingly deep, the quantum efficiency is continuously improved, the level of industrialization is basically reached, and the trend of realizing the industrialization by further adopting a new process and technology becomes the future. The use of Quantum dots for patterning to prepare high-resolution Quantum Dot Light Emitting Diodes (QLEDs) has become an important issue.
Disclosure of Invention
The invention provides a display panel, a display device and a manufacturing method of the display panel, and provides a novel patterning method of a quantum dot film layer.
An embodiment of the present invention provides a display panel, including: the quantum dot array substrate comprises a substrate base plate, an electrode and a quantum dot film layer, wherein the electrode and the quantum dot film layer are sequentially positioned on one side of the substrate base plate; wherein the quantum dot film layer comprises: the quantum dot film comprises a quantum dot body and a charged connecting structure connected with the quantum dot body, wherein the charged connecting structure is formed by reacting a charged precursor structure with opposite electric property with first ions, the electric property of the first ions is opposite to that of the charged precursor structure, and the first ions are generated by decomposing a first substance mixed in the quantum dot film under a preset condition.
In one possible embodiment, the charged precursor structure is negatively charged; the charged precursor structure comprises a negatively charged weakly acidic group and a positively charged weakly basic group, and the number of the weakly acidic groups is more than that of the weakly basic groups.
In one possible embodiment, the weakly acidic groups comprise one or a combination of the following groups:
a carboxylic acid group;
a phenolic hydroxyl group;
the weakly basic groups include one or a combination of the following groups:
a primary amine group;
a secondary amino group;
a tertiary amine group.
In one possible embodiment, the charged connecting structure further comprises a crosslinking group.
In one possible embodiment, the crosslinking group is a thermal crosslinking group comprising: an epoxy group;
or, the crosslinking group is a photocrosslinking group comprising one of:
an epoxy group;
an acrylate group;
an isoprene group;
a mercapto group;
an olefin;
an alkyne;
and (4) nitrizing.
In one possible embodiment, the quantum dot film layer comprises the following structure:
wherein R1 is- (CH)2)-mEither, or,
r2 is- (CH)2)-nEither, or,
m+n≤12；
x is-NH 2, -COOH, or-SH;
r3 is the crosslinking group.
The embodiment of the invention also provides a display device which comprises the display panel provided by the embodiment of the invention.
The embodiment of the invention also provides a manufacturing method of the display panel, which comprises the following steps:
providing a substrate base plate;
forming an electrode on one side of the substrate base plate;
forming a patterned quantum dot film layer on one side of the electrode, which is far away from the substrate base plate, and repeating at least once;
wherein, form the quantum dot membranous layer of the patterning on the side of the said electrode far away from said substrate base plate, including:
forming a quantum dot film on a side of the electrode facing away from the substrate base plate, wherein the quantum dot film comprises: the quantum dot structure comprises a quantum dot body, a charged precursor structure connected with the quantum dot body, and a first substance;
under a preset condition, processing the quantum dot film in a reserved area so as to decompose the first substance in the reserved area to generate first ions, wherein the charged precursor structure reacts with the first ions to form a charged connection structure with an electric property opposite to that of the charged precursor structure, and the first ions and the charged precursor structure have an electric property opposite to that of the charged precursor structure;
and applying a voltage with the electrical property opposite to that of the charged connecting structure to the electrode, and cleaning the electrode by using a developing solution to enable the charged connecting structure in the reserved area and the electrode to attract each other, wherein the charged precursor structure in the area outside the reserved area and the electrode are electrically repelled and cleaned away.
In one possible embodiment, the charged connecting structure further comprises a thermal crosslinking group or a photo crosslinking group;
after being cleaned by the developing solution, the forming a patterned quantum dot film layer on the side of the electrode facing away from the substrate base plate further comprises:
and heating and annealing the quantum dot film layer to enable the charged connection structure to generate a crosslinking reaction.
In one possible embodiment, the first substance is a photoacid generator;
under the preset condition, the quantum dot film in the reserved area is processed, and the processing method comprises the following steps:
irradiating the quantum dot film of the reserved area by ultraviolet light to decompose the photoacid generator to generate hydrogen ions, and carrying out the following reactions:
the embodiment of the invention has the following beneficial effects: in the embodiment of the invention, the charged precursor structure connected with the quantum dot body and the first substance mixed in the quantum dot film layer are arranged on the quantum dot body, so that when the quantum dot film layer is patterned, the first substance can be decomposed to form first ions through preset conditions for the reserved area of the quantum dot film to be reserved, the charged precursor structure reacts with the first ions to generate a charged connecting structure with the electric property opposite to that of the charged precursor structure, and the area of the quantum dot film to be removed is still a non-reacted charged precursor structure, so that the electric properties of different areas are different, when the electrode is removed by development, the electrode is loaded with the electric property opposite to that of the charged connecting structure, the adsorption of the charged connecting structure of the reserved area through the electrode pair can be realized, and the area of the quantum dot film does not need to be reserved, the electrode pair repels the charged precursor structure, so that the quantum dot film outside the reserved area can be easily removed, and the patterning of the quantum dot film layer is realized.
Drawings
Fig. 1 is a schematic structural diagram of a display panel according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a quantum dot connected with a ribbon connection structure according to an embodiment of the present invention;
fig. 3 is a schematic view of a reaction process of a quantum dot film layer according to an embodiment of the present invention;
fig. 4 is a schematic structural diagram of another quantum dot structure connected with a ribbon electrical connection structure according to an embodiment of the present invention;
fig. 5 is a schematic view of a manufacturing process of a display panel according to an embodiment of the present invention;
fig. 6 is a schematic view of a specific manufacturing process of a display panel according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more clear, the technical solutions of the embodiments of the present disclosure will be described below clearly and completely with reference to the accompanying drawings of the embodiments of the present disclosure. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
Unless otherwise defined, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs. The use of "first," "second," and similar terms in this disclosure is not intended to indicate any order, quantity, or importance, but rather is used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that the element or item listed before the word covers the element or item listed after the word and its equivalents, but does not exclude other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", and the like are used merely to indicate relative positional relationships, and when the absolute position of the object being described is changed, the relative positional relationships may also be changed accordingly.
To maintain the following description of the embodiments of the present disclosure clear and concise, a detailed description of known functions and known components have been omitted from the present disclosure.
Referring to fig. 1, an embodiment of the present invention provides a display panel, including: the quantum dot array substrate comprises a substrate base plate 1, an electrode 2 and a quantum dot film layer 3, wherein the electrode 2 and the quantum dot film layer are sequentially positioned on one side of the substrate base plate 1; as shown in fig. 2, the quantum dot film layer 3 includes: as shown in fig. 3, the charged connection structure Y is formed by reacting a charged precursor structure X with opposite electric properties with a first ion, the first ion and the charged precursor structure X are opposite electric properties, and the first ion is generated by decomposing a first substance mixed in the quantum dot film layer 3 under a preset condition. Specifically, the first substance may be a photoacid generator PAG, the first ion may be a hydrogen ion, the predetermined condition may be ultraviolet light irradiation, and the photoacid generator PAG may generate a hydrogen ion when irradiated by ultraviolet light.
In the embodiment of the invention, the charged precursor structure connected with the quantum dot body and the first substance mixed in the quantum dot film layer are arranged on the quantum dot body, so that when the quantum dot film layer is patterned, the first substance can be decomposed to form first ions through preset conditions for the reserved area of the quantum dot film to be reserved, the charged precursor structure reacts with the first ions to generate a charged connecting structure with the electric property opposite to that of the charged precursor structure, and the area of the quantum dot film to be removed is still a non-reacted charged precursor structure, so that the electric properties of different areas are different, when the electrode is removed by development, the electrode is loaded with the electric property opposite to that of the charged connecting structure, the adsorption of the charged connecting structure of the reserved area through the electrode pair can be realized, and the area of the quantum dot film does not need to be reserved, the electrode pair repels the charged precursor structure, so that the quantum dot film outside the reserved area can be easily removed, and the patterning of the quantum dot film layer is realized.
In specific implementation, the display panel in the embodiment of the invention can be a quantum dot light display panel, the quantum dot film layer can be a quantum dot light emitting layer, and the display panel can be further provided with another electrode on the side of the quantum dot film layer departing from the substrate; with reference to fig. 1, the quantum dot light emitting layer may specifically have light emitting parts emitting different light colors, for example, a red light emitting part emitting red light, a green light emitting part emitting green light, and a blue light emitting part emitting blue light, and the quantum dot patterning manner in the embodiment of the present invention may be used in the process of patterning the red light emitting part, the process of patterning the green light emitting part, and the process of patterning the blue light emitting part; the display panel can be specifically of an inverted structure, the electrode 2 can be specifically a cathode, and the front film layer 5 can be specifically an electron transport layer. The quantum dot film layer in the embodiment of the present invention may also be used as a film layer for other functions, for example, a quantum dot color film layer may also be used, for example, the display panel may specifically be a liquid crystal panel, the quantum dot color film layer may specifically be a color film layer disposed on a color film substrate of the liquid crystal panel, and the color film substrate may also specifically be provided with an electrode (specifically, a common electrode).
In specific implementation, referring to fig. 3, the charged precursor structure X may be a structure including a plurality of charged groups, wherein a part of the charged groups may be positively charged, a part of the charged groups may be negatively charged, and total positive and negative charges are different, so that the charged precursor structure X as a whole is charged with one kind of charge. Specifically, for example, the charged precursor structure X is negatively charged; the charged precursor structure X includes negatively charged weakly acidic groups (e.g., COO-) and positively charged weakly basic groups (e.g., NH)3 +) And the number of weakly acidic groups (e.g., COO-) is greater than that of weakly basic groups (e.g., NH)3 +) And then the charged precursor structure X is negatively charged. In the embodiment of the present invention, the charged precursor structure X includes a negatively charged weak acidic group and a positively charged weak basic group, and in the subsequent reaction process with an electrically charged ion (e.g., a hydrogen ion), the negatively charged weak acidic group can be positively charged and converted into an electrically neutral, and the remaining positively charged weak basic group converts the overall negatively charged precursor structure X into the overall positively charged connecting structure Y, thereby realizing the change of the overall chargeability.
The reaction between the charged linking structure Y and the first substance (e.g., photoacid generator PAG) under the predetermined conditions may specifically be as follows:
after the charged electrically-connected structure Y is mixed with the photo-acid generating agent, PAG is irradiated by light to generate hydrogen ions, a large number of hydrogen ions can inhibit the dissociation of carboxylic acid hydrogen ions, carboxylate radical ions are promoted to be changed into carboxylic acid radicals, only positively charged amino groups exist in the charged groups of the whole charged electrically-connected structure Y, and therefore the whole charged electrically-connected structure Y is changed from the whole negative charge to the whole positive charge through the action of PAG.
In specific embodiments, the weakly acidic groups include one or a combination of the following groups:
a carboxylic acid group;
a phenolic hydroxyl group;
weakly basic groups include one or a combination of the following groups:
a primary amine group;
a secondary amino group;
a tertiary amine group.
In one embodiment, as shown in FIG. 4, the electrically connecting structure X further comprises a cross-linking group R3, wherein the cross-linking group R3 may be a thermal cross-linking group or a photo-cross-linking group. In the embodiment of the invention, the charged connecting structure X further comprises a thermal crosslinking group or a photocrosslinking group, so that the formed charged connecting structure Y can further undergo a crosslinking reaction to have more stable adhesiveness, and the situation that the former quantum dot film layer is dissolved and damaged when the latter quantum dot film layer is developed if the former quantum dot film layer is not crosslinked and cured after the former quantum dot film layer with one light-emitting color is patterned is avoided.
In specific implementations, the thermally crosslinking group includes: an epoxy group;
the photo-crosslinking group includes:
an epoxy group;
an acrylate group;
an isoprene group;
a mercapto group;
an olefin;
an alkyne;
and (4) nitrizing. Specifically, the thermal crosslinking groups (or photo-crosslinking groups) included in the different charged precursor structures X may be the same, for example, all of the thermal crosslinking groups included in the charged precursor structures X may be epoxy groups; the thermally crosslinkable groups (or photocrosslinkable groups) protected by the different charged precursor structures X may also be different, for example, part of the charged precursor structures X may comprise a photocrosslinkable group which may be a thiol group, part of the charged precursor structures X may comprise a photocrosslinkable group which may be an olefin, via a thiol group and an olefin
Realizing the mutual cross-linking of the two charged connecting structures Y; as another example, the photocrosslinking group included in the partially charged precursor structure X can be an azide, and the photocrosslinking group included in the partially charged precursor structure X can be an alkyne, via the alkyne and the azide
The mutual cross-linking of the two live connection structures Y is realized.
In specific implementation, the quantum dot film layer comprises the following structure:
wherein R1 is- (CH)2)-mEither, or,
r2 is- (CH)2)-nEither, or,
m+n≤12；
x is-NH 2, -COOH, or-SH; x can be specifically used as a coordination group to connect the charged connection structure Y with the quantum dot body QD;
r3 is a crosslinking group, R3 may be a photo-crosslinking or a thermal-crosslinking group, and in the final quantum dot film layer, a structure formed by photo-crosslinking or thermal-crosslinking a plurality of charged connecting structures Y may be used, and the crosslinking reaction may be as follows:
based on the same inventive concept, the embodiment of the invention further provides a display device, which comprises the display panel provided by the embodiment of the invention.
Based on the same inventive concept, referring to fig. 5, an embodiment of the present invention further provides a method for manufacturing a display panel, including:
step S100, providing a substrate base plate;
step S200, forming an electrode on one side of a substrate;
step S300, forming a patterned quantum dot film layer on one side of the electrode, which is far away from the substrate base plate, and repeating at least once;
for step S300, forming a patterned quantum dot film layer on the side of the electrode away from the substrate includes:
step S301, forming a quantum dot film on one side of the electrode, which is far away from the substrate base plate, wherein the quantum dot film comprises: the quantum dot structure comprises a quantum dot body, a charged precursor structure connected with the quantum dot body, and a first substance;
step S302, under a preset condition, processing the quantum dot film in the reserved area to decompose a first substance in the reserved area to generate a first ion, so that the charged precursor structure reacts with the first ion to form a charged connection structure with opposite electrical property to the charged precursor structure, wherein the first ion is opposite to the charged precursor structure in electrical property;
step S303, a voltage opposite to the electrical property of the charged connection structure is applied to the electrode, and the electrode is cleaned by the developing solution, so that the charged connection structure in the reserved area and the electrode attract each other, and the charged precursor structure in the area outside the reserved area and the electrode repel each other electrically and are cleaned and removed.
In specific implementation, the charged connecting structure further comprises a thermal crosslinking group or a photo crosslinking group; after step S303, i.e. after cleaning by the developing solution, forming a patterned quantum dot film layer on the side of the electrode facing away from the substrate base plate, further comprising:
and S304, heating and annealing the quantum dot film layer to enable the charged connection structure to generate a cross-linking reaction.
In particular implementations, the first substance is a photoacid generator; for the quantum dot thin film of the reserved area under the preset condition in the step S302, the processing includes:
irradiating the quantum dot film in the reserved area by ultraviolet light to decompose the photoacid generator to generate hydrogen ions, and carrying out the following reactions:
in order to more clearly understand the patterning process of the quantum dot film layer according to the embodiment of the present invention, the following description is further provided with reference to fig. 6, taking the first substance as the photoacid generator PAG and the first ion as the hydrogen ion as the example:
the preparation of the patterned electrode and each front film layer of the quantum dot film layer is firstly realized. The quantum dot adopts a special charged ligand, the quantum dot displays negative charge due to ligand ion groups, the quantum dot is mixed with a small amount of photoacid generator (PAG) during spin coating, ultraviolet light is used for irradiating a pixel area needing to deposit the quantum dot after spin coating, hydrogen ions generated after the PAG is decomposed by illumination interact with the ligand groups, the quantum dot is changed from negative charge to positive charge, the quantum dot in the pixel needing to deposit the quantum dot is positively charged, and the quantum dot in the pixel needing to wash out the quantum dot is negatively charged; electrifying the patterned electrode to present electronegativity; the quantum dots and the substrate have stronger acting force in a pixel area needing to deposit the quantum dots due to the mutual attraction of positive and negative charges, and the quantum dots in the charge-repellent area are washed away when a good solvent is used for development in other areas due to the fact that the substrate charges and the quantum dot charges are in the same polarity, and only the quantum dot area with opposite charges is left to form the patterned quantum dots.
When the deposition of the patterned quantum dots in other pixel regions is repeated, in order to avoid the influence on the deposited quantum dots during development, the quantum dot ligands contain groups capable of being crosslinked by heat, and the quantum dot film layer is stabilized by crosslinking through heat annealing after the patterned deposition.
Specifically, the quantum dot body is CdSe/ZnS red quantum dot, and a charged precursor structure X is formed by dissolving a quantum dot ligand A, so that the device structure can be an inverted device. Spin-coating a 30mg/ml front film layer (specifically, an electron transport layer, and a material of zinc oxide nanoparticles) on a substrate with an electrode (specifically, Indium Tin Oxide (ITO)) deposited thereon at 1500rpm, and annealing at 120 deg.C for 5 min; spin-coating 15mg/ml red light quantum dots at the rotation speed of 2500rpm, electrifying an ITO electrode to enable the electrode to be negatively charged after the spin-coating is finished, developing the quantum dot film layer by using ethanol, removing the quantum dots in other areas, annealing for 30 minutes at 120 ℃, and curing the quantum dots to form the patterned red light quantum dot film. Specifically, the quantum dot ligand a may have the following structure:
the embodiment of the invention also provides a preparation method of the quantum dot film layer material, and the specific synthetic route is as follows:
reaction (1): 10mmol of 3, 5-dihydroxynitrobenzene is placed in a 100ml three-neck flask, 10.2mmol of N-bromosuccinimide (NBS) is added as a brominating agent, and 40ml of N, N-Dimethylformamide (DMF) is added as a reaction solvent. Stir overnight for 24 hours. After the reaction is finished, pouring the reactant into water, extracting the reactant for three times by using dichloromethane, and collecting a dichloromethane phase; the methylene chloride phase was dried and then subjected to column chromatography (eluent V)Methylene dichloride：VPetroleum ether1: 2) finally, spin-drying the collected solution to obtain a product b, wherein the specific reaction is as follows;
reaction (2): 10mmol of the reactant c and 12mmol of p-dichlorobenzene were placed in a 100ml three-necked flask, 0.01mmol of tetratriphenylphosphine palladium was added as a catalyst, and 40ml of toluene was added as a reaction solvent. After the air in the bottle was replaced with argon by three times of evacuation through the double calandria, the stirring was turned on and the temperature was heated to 95 ℃ and the condensation refluxed for 24 hours. After the reaction is finished, removing toluene from the reactant through rotary evaporation, dissolving solid substances with dichloromethane, extracting with water for three times, and collecting a dichloromethane phase; the methylene chloride phase was dried and then subjected to column chromatography (eluent V)Methylene dichloride：VPetroleum ether3: 1) finally, spin-drying the collected solution to obtain a product e;
reaction (3): 10mmol of the product b and 10.5mmol of the product e are taken and placed in a 100ml three-neck flask, 0.01mmol of tetratriphenylphosphine palladium is added as a catalyst, and 40ml of toluene is added as a reaction solvent. After the air in the bottle was replaced with argon by three times of evacuation through the double calandria, the stirring was turned on and the temperature was heated to 95 ℃ and the condensation refluxed for 24 hours. After the reaction is finished, removing toluene from the reactant through rotary evaporation, dissolving solid substances with dichloromethane, extracting with water for three times, and collecting a dichloromethane phase; the methylene chloride phase was dried and then subjected to column chromatography (eluent V)Methylene dichloride：VPetroleum ether1: 5) finally, spin-drying the collected solution to obtain a product f;
reaction (4): 10mmol of the product f and 12mmol of butanediol are placed in a 100ml three-neck flask, 0.1mmol of concentrated sulfuric acid is added as an esterification catalyst, and 40ml of N, N-Dimethylformamide (DMF) is added as a reaction solvent. After the air in the bottle was replaced with argon by three times of evacuation through the double calandria, the stirring was turned on and the temperature was heated to 120 ℃ and the reflux was condensed for 24 hours. After the reaction is finished, pouring the reactant into water to separate out solid, filtering, recrystallizing with DMF, and finally drying the separated solid to obtain 7.5mmol of product h; 7.5mmol of the product h are placed in a 100ml three-necked flask, 8mmol of hydrazine hydrate are added and 40ml of N, N-Dimethylformamide (DMF) are added as reaction solvent. After the air in the bottle was replaced with argon by three times of evacuation through the double calandria, the stirring was turned on and the temperature was heated to 80 ℃ and the reflux was condensed for 24 hours. And after the reaction is finished, pouring the reactant into water to separate out solid, filtering, recrystallizing by using ethanol, and finally drying the separated solid to obtain a final product k.
The specific processes of reaction (1), reaction (2), reaction (3) and reaction (4) may be as follows:
the embodiment of the invention has the following beneficial effects: in the embodiment of the invention, the charged precursor structure connected with the quantum dot body and the first substance mixed in the quantum dot film layer are arranged on the quantum dot body, so that when the quantum dot film layer is patterned, the first substance can be decomposed to form first ions through preset conditions for the reserved area of the quantum dot film to be reserved, the charged precursor structure reacts with the first ions to generate a charged connecting structure with the electric property opposite to that of the charged precursor structure, and the area of the quantum dot film to be removed is still a non-reacted charged precursor structure, so that the electric properties of different areas are different, when the electrode is removed by development, the electrode is loaded with the electric property opposite to that of the charged connecting structure, the adsorption of the charged connecting structure of the reserved area through the electrode pair can be realized, and the area of the quantum dot film does not need to be reserved, the electrode pair repels the charged precursor structure, so that the quantum dot film outside the reserved area can be easily removed, and the patterning of the quantum dot film layer is realized.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A display panel, comprising: the quantum dot array substrate comprises a substrate base plate, an electrode and a quantum dot film layer, wherein the electrode and the quantum dot film layer are sequentially positioned on one side of the substrate base plate; wherein the quantum dot film layer comprises: the quantum dot film comprises a quantum dot body and a charged connecting structure connected with the quantum dot body, wherein the charged connecting structure is formed by reacting a charged precursor structure with opposite electric property with first ions, the electric property of the first ions is opposite to that of the charged precursor structure, and the first ions are generated by decomposing a first substance mixed in the quantum dot film under a preset condition.
2. The display panel of claim 1, wherein the charged precursor structure is negatively charged; the charged precursor structure comprises a negatively charged weakly acidic group and a positively charged weakly basic group, and the number of the weakly acidic groups is more than that of the weakly basic groups.
3. A display panel as claimed in claim 2 wherein the weakly acidic groups comprise one or a combination of:
a carboxylic acid group;
a phenolic hydroxyl group;
the weakly basic groups include one or a combination of the following groups:
a primary amine group;
a secondary amino group;
a tertiary amine group.
4. The display panel of claim 2, wherein the strap electrical connection structure further comprises a crosslinking group.
5. The display panel according to claim 4, wherein the crosslinking group is a thermal crosslinking group comprising: an epoxy group;
or, the crosslinking group is a photocrosslinking group comprising one of:
an epoxy group;
an acrylate group;
an isoprene group;
a mercapto group;
an olefin;
an alkyne;
and (4) nitrizing.
6. The display panel of claim 4, wherein the quantum dot film layer comprises the structure:
wherein R1 is- (CH)2)-mEither, or,
r2 is- (CH)2)-nEither, or,
wherein m + n is less than or equal to 12;
x is-NH 2, -COOH, or-SH;
r3 is the crosslinking group.
7. A display device comprising the display panel according to any one of claims 1 to 6.
8. A method for manufacturing a display panel is characterized by comprising the following steps:
providing a substrate base plate;
forming an electrode on one side of the substrate base plate;
forming a patterned quantum dot film layer on one side of the electrode, which is far away from the substrate base plate, and repeating at least once;
wherein, form the quantum dot membranous layer of the patterning on the side of the said electrode far away from said substrate base plate, including:
forming a quantum dot film on a side of the electrode facing away from the substrate base plate, wherein the quantum dot film comprises: the quantum dot structure comprises a quantum dot body, a charged precursor structure connected with the quantum dot body, and a first substance;
under a preset condition, processing the quantum dot film in a reserved area so as to decompose the first substance in the reserved area to generate first ions, wherein the charged precursor structure reacts with the first ions to form a charged connection structure with an electric property opposite to that of the charged precursor structure, and the first ions and the charged precursor structure have an electric property opposite to that of the charged precursor structure;
and applying a voltage with the electrical property opposite to that of the charged connecting structure to the electrode, and cleaning the electrode by using a developing solution to enable the charged connecting structure in the reserved area and the electrode to attract each other, wherein the charged precursor structure in the area outside the reserved area and the electrode are electrically repelled and cleaned away.
9. The method of claim 8, wherein the strap connection structure further comprises a thermally or photo-crosslinking group;
after being cleaned by the developing solution, the forming a patterned quantum dot film layer on the side of the electrode facing away from the substrate base plate further comprises:
and heating and annealing the quantum dot film layer to enable the charged connection structure to generate a crosslinking reaction.
10. The method of claim 9, wherein the first substance is a photoacid generator;
under the preset condition, the quantum dot film in the reserved area is processed, and the processing method comprises the following steps:
irradiating the quantum dot film of the reserved area by ultraviolet light to decompose the photoacid generator to generate hydrogen ions, and carrying out the following reactions:
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| CN113088279A (en) * | 2021-04-15 | 2021-07-09 | 京东方科技集团股份有限公司 | Quantum dot material, light-emitting diode substrate, manufacturing method and display device |
| CN113337274A (en) * | 2021-05-31 | 2021-09-03 | 深圳市华星光电半导体显示技术有限公司 | Quantum dot module, quantum dot film patterning method and display device |
| CN113838990A (en) * | 2021-09-26 | 2021-12-24 | 北京京东方技术开发有限公司 | Quantum dot light-emitting device, manufacturing method thereof and display device |
| WO2023050214A1 (en) * | 2021-09-29 | 2023-04-06 | 京东方科技集团股份有限公司 | Quantum dot ligand, quantum dot-ligand system, and quantum dot material |
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| CN113838990B (en) * | 2021-09-26 | 2024-04-09 | 北京京东方技术开发有限公司 | Quantum dot light emitting device, manufacturing method thereof and display device |
| WO2023050214A1 (en) * | 2021-09-29 | 2023-04-06 | 京东方科技集团股份有限公司 | Quantum dot ligand, quantum dot-ligand system, and quantum dot material |
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