CN112234149B - 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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- CN112234149B CN112234149B CN202011095919.5A CN202011095919A CN112234149B CN 112234149 B CN112234149 B CN 112234149B CN 202011095919 A CN202011095919 A CN 202011095919A CN 112234149 B CN112234149 B CN 112234149B
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Classifications
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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
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses 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. The display panel includes: a substrate, electrodes positioned on one side of the substrate in sequence, and a quantum dot film layer; wherein, the quantum dot film layer includes: the quantum dot structure comprises a quantum dot body and a charged connection structure connected with the quantum dot body, wherein the charged connection structure is formed by reacting a charged precursor structure with opposite electrical property with first ions, the electrical 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 a quantum dot film layer under preset conditions.
Description
Technical Field
The present invention relates to the field of display technologies, and in particular, to a display panel, a display device, and a method for manufacturing the display panel.
Background
Active-matrix organic light emitting diodes (AMOLED) have been recognized as promising next generation displays for replacing liquid crystal display panels, but with the increase of consumer consumption level, high resolution products become important development directions of display products, while high resolution AMOLED products are difficult to compete with liquid crystal display panels, because organic layer structures of organic light emitting displays are usually prepared by a mask evaporation method, but the mask evaporation method has defects of difficult alignment, low yield and incapability of realizing smaller area light emission; the problem of insufficient capability of accurately controlling the evaporation area cannot meet the current rapidly-developed requirement for high-resolution display; instead of the process of preparing an organic light emitting layer by mask evaporation, printing and printing methods are used, which also have extremely limited resolution. Therefore, the high-resolution AMOLED products face the serious problems of high technical difficulty, low product yield and high commodity price.
On the other hand, with the deep development of 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 further, the industrialization of the electroluminescent quantum dot light emitting diode is realized by adopting new technology and technology, so that the future trend is realized. Patterning with quantum dots to produce high resolution quantum dot light emitting diodes (Quantum Dot Light Emitting Diodes, QLED) 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: a substrate, electrodes positioned on one side of the substrate in sequence, and a quantum dot film layer; wherein, the quantum dot film layer includes: the quantum dot structure comprises a quantum dot body and a charged connection structure connected with the quantum dot body, wherein the charged connection structure is formed by reacting a charged precursor structure with opposite electrical property with first ions, the electrical 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 a quantum dot film layer under preset conditions.
In one possible embodiment, the charged precursor structure is negatively charged; the charged precursor structure includes a negatively charged weakly acidic group and a positively charged weakly basic group, and the number of weakly acidic groups is greater than the number of weakly basic groups.
In one possible embodiment, the weakly acidic group comprises 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:
primary amine groups;
a secondary amine group;
and a tertiary amine group.
In one possible embodiment, the charged linking structure further comprises a crosslinking group.
In one possible embodiment, the crosslinking group is a thermal crosslinking group comprising: an epoxy group;
alternatively, the crosslinking group is a photocrosslinking group comprising one of:
an epoxy group;
an acrylate group;
an isoprene group;
a mercapto group;
an olefin;
alkynes;
and (3) azides.
In one possible embodiment, the quantum dot film layer includes the following structure:
wherein R1 is- (CH) 2 )- m Or, alternatively,
r2 is- (CH) 2 )- n Or, alternatively,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 comprising 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, and repeating at least once;
forming a patterned quantum dot film layer on one side of the electrode, which is far away from the substrate base plate, wherein the quantum dot film layer comprises the following components:
forming a quantum dot film on one side of the electrode, which is away from the substrate, wherein the quantum dot film comprises: a quantum dot body, a charged precursor structure connected to the quantum dot body, and a first substance;
under a preset condition, the quantum dot film in a reserved area is processed, so that the first substance in the reserved area is decomposed to generate first ions, the charged precursor structure reacts with the first ions to form a charged connection structure with opposite electrical property to the charged precursor structure, and the first ions are opposite to the charged precursor structure in electrical property;
and loading voltage opposite to the electrical property of the charged connection structure on the electrode, cleaning the electrode by using a developing solution to enable the charged connection structure of the reserved area to be attracted with the electrode, and electrically repelling the charged precursor structure of the area outside the reserved area from the electrode to be cleaned and removed.
In one possible embodiment, the charged linking structure further comprises a thermal crosslinking group or a photocrosslinking group;
after being washed by a developing solution, the forming a patterned quantum dot film layer on one side of the electrode, which is away from the substrate, further comprises:
and heating and annealing the quantum dot film layer to enable the charged connecting structure to generate a crosslinking reaction.
In one possible embodiment, the first substance is a photoacid generator;
and under the preset condition, processing the quantum dot film in the reserved area, wherein the processing comprises the following steps:
irradiating the quantum dot film in the reserved area through ultraviolet light so as 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: according to 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 through preset conditions for the reserved area where the quantum dot film is required to be reserved, first ions are formed, the charged precursor structure reacts with the first ions to generate a charged connection structure with opposite electrical property to the charged precursor structure, the area where the quantum dot film is required to be removed is still a non-reacted charged precursor structure, the chargeability of different areas is further different, when the development and removal are carried out, the charged connection structure is adsorbed through the electrode, the area where the quantum dot film is not required to be reserved is repelled by the electrode, the quantum dot film outside the reserved area is 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 diagram of a quantum dot structure connected with a charged connection structure according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a reaction process of a quantum dot film according to an embodiment of the present invention;
fig. 4 is a schematic diagram of another quantum dot structure connected with a charged connection structure according to an embodiment of the present invention;
fig. 5 is a schematic diagram of a manufacturing process of a display panel according to an embodiment of the present invention;
fig. 6 is a schematic diagram of a manufacturing process of a specific display panel according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present disclosure. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present disclosure. All other embodiments, which can be made by one of ordinary skill in the art without the need for inventive faculty, are within the scope of the present disclosure, based on the described embodiments of the present disclosure.
Unless defined otherwise, technical or scientific terms used in this disclosure should be given the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs. The terms "first," "second," and the like, as used in this disclosure, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The word "comprising" or "comprises", and the like, means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof, but does not exclude other elements or items. The terms "connected" or "connected," and the like, are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "upper", "lower", "left", "right", etc. are used merely to indicate relative positional relationships, which may also be changed when the absolute position of the object to be described is changed.
In order to keep the following description of the embodiments of the present disclosure clear and concise, the present disclosure omits detailed description of known functions and known components.
Referring to fig. 1, an embodiment of the present invention provides a display panel, including: a substrate 1, an electrode 2 positioned on one side of the substrate 1 in sequence, and a quantum dot film layer 3; 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 electrical properties with a first ion, the first ion is generated by decomposing a first substance mixed in the quantum dot film layer 3 under a preset condition, and the first ion is opposite to the charged precursor structure X in electrical properties. Specifically, the first substance may be a photoacid generator PAG, the first ion may be a hydrogen ion, the preset condition may be ultraviolet irradiation, and the photoacid generator PAG may generate a hydrogen ion when irradiated with ultraviolet light.
According to 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 through preset conditions for the reserved area where the quantum dot film is required to be reserved, first ions are formed, the charged precursor structure reacts with the first ions to generate a charged connection structure with opposite electrical property to the charged precursor structure, the area where the quantum dot film is required to be removed is still a non-reacted charged precursor structure, the chargeability of different areas is further different, when the development and removal are carried out, the charged connection structure is adsorbed through the electrode, the area where the quantum dot film is not required to be reserved is repelled by the electrode, the quantum dot film outside the reserved area is 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-emitting display panel, the quantum dot film layer can be used as a quantum dot light-emitting layer, and the display panel can be provided with another electrode on one side of the quantum dot film layer, which is far away from the substrate; as shown in fig. 1, the quantum dot light-emitting layer may specifically have light-emitting portions emitting different light colors, for example, a red light-emitting portion emitting red light, a green light-emitting portion emitting green light, and a blue light-emitting portion emitting blue light; a pixel limiting layer 4 can be further arranged between the light emitting parts with different light emitting colors, a front film layer can be further arranged between the electrode 2 and the quantum dot film layer 3, the display panel can be in an inverted structure, the electrode 2 can be a cathode, and the front film layer 5 can be an electron transmission layer. The quantum dot film layer in the embodiment of the invention can also be used as a film layer with other functions, for example, the quantum dot film layer can also be used as a quantum dot color film layer, for example, the display panel can be a liquid crystal panel, the quantum dot color film layer can be a color film layer of a color film substrate arranged on the liquid crystal panel, and the color film substrate can be provided with an electrode (can be a public electrode).
In particular toIn implementation, as shown in fig. 3, the charged precursor structure X may be a structure including a plurality of charged groups, where a portion of the groups may be positively charged, a portion of the groups may be negatively charged, and the total positive and negative charges are different, so that the charged precursor structure X is integrally embodied as one charge. Specifically, for example, the charged precursor structure X is negatively charged; the charged precursor structure X comprises a weakly acidic group (e.g., COO-) that is negatively charged and a weakly basic group (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 + ) Thereby realizing that the charged precursor structure X is negatively charged. In the embodiment of the invention, the charged precursor structure X comprises a negatively charged weak acidic group and a positively charged weak basic group, and in the subsequent reaction process with an electric ion (for example, hydrogen ion), the negatively charged weak acidic group can be positively charged and converted into neutral electricity, and the rest of the positively charged weak basic groups can be used for converting the whole negatively charged precursor structure X into the whole positively charged connecting structure Y, so that the whole charging change is realized.
The reaction of the charged linking structure Y with the first substance (e.g., photoacid generator PAG) under the preset conditions may specifically be as follows:
after the charged connecting structure Y is mixed with the photoacid generator, the PAG is illuminated to generate hydrogen ions, a large amount of hydrogen ions can inhibit dissociation of carboxylic acid hydrogen ions, so that carboxylic acid radical ions are converted into carboxylic acid radicals, and the charged radicals of the whole charged connecting structure Y only have positively charged amino groups, so that the charged connecting structure Y is converted into integrally positively charged from integrally negatively charged through the action of the PAG.
In particular embodiments, the weakly acidic groups include 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:
primary amine groups;
a secondary amine group;
and a tertiary amine group.
In specific implementation, as shown in fig. 4, the charged connecting structure X further includes a crosslinking group R3, where the crosslinking group R3 may specifically be a thermal crosslinking group or a photo crosslinking group. In the embodiment of the invention, the charged connection structure X further comprises a thermal crosslinking group or a photo crosslinking group, so that the formed charged connection structure Y can be subjected to further crosslinking reaction to have more stable adhesiveness, and the problem that the quantum dot film with one light-emitting color is dissolved and damaged when the quantum dot film with the other light-emitting color is developed if the former quantum dot film is not crosslinked and solidified after the patterning of the quantum dot film with the one light-emitting color is avoided.
In particular embodiments, the thermal crosslinking group includes: an epoxy group;
photocrosslinking groups include:
an epoxy group;
an acrylate group;
an isoprene group;
a mercapto group;
an olefin;
alkynes;
and (3) azides. Specifically, the thermal crosslinking groups (or photocrosslinking groups) included in different charged precursor structures X may be the same, for example, all the thermal crosslinking groups included in the charged precursor structures X may be epoxy groups; the thermally crosslinkable groups (or photocrosslinking groups) protected by the different charged precursor structures X may also be different, for example, the photocrosslinking groups comprised by the partially charged precursor structures X may be mercapto groups, the photocrosslinking groups comprised by the partially charged precursor structures X may be olefin groups, and the photocrosslinking groups comprised by the partially charged precursor structures X may be olefin groups, such as by mercapto groups and olefin groupsRealizing the cross-linking of the two charged connecting structures Y; for another example, the photocrosslinking groups comprised by the partially charged precursor structure X may be azides, the photocrosslinking groups comprised by the partially charged precursor structure X may be alkynes, via alkynes and azido +.>The cross-linking of the two charged connecting structures Y is achieved.
In specific implementations, the quantum dot film layer includes the following structure:
wherein R1 is- (CH) 2 )- m Or, alternatively,
r2 is- (CH) 2 )- n Or, alternatively,m+n≤12；
x is-NH 2, -COOH, or-SH; x can be specifically used as a coordination group to connect the charged connecting structure Y with the quantum dot body QD;
r3 is a crosslinking group, R3 can be specifically a photocrosslinking or thermal crosslinking group, and in the final quantum dot film layer, the structure formed by crosslinking a plurality of charged connecting structures Y through photocrosslinking or thermal crosslinking groups can be specifically the following crosslinking reaction:
based on the same inventive concept, the embodiment of the invention also provides a display device, including 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 200, 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, and repeating at least once;
wherein, for step S300, forming a patterned quantum dot film layer on a side of the electrode facing away from the substrate, the method includes:
step S301, forming a quantum dot film on a side of the electrode facing away from the substrate, where the quantum dot film includes: a quantum dot body, a charged precursor structure connected to the quantum dot body, and a first substance;
step S302, under a preset condition, the quantum dot film in the reserved area is processed, so that a first substance in the reserved area is decomposed to generate first ions, the charged precursor structure reacts with the first ions to form a charged connection structure with opposite electrical property to the charged precursor structure, and the first ions are opposite to the charged precursor structure in electrical property;
step S303, loading voltage opposite to the electrical property of the charged connection structure on the electrode, and cleaning by using a developing solution to make the charged connection structure of the reserved area and the electrode attract each other, and making the charged precursor structure of the area outside the reserved area and the electrode repel each other, so that the charged precursor structure and the electrode are cleaned and removed.
In particular embodiments, the charged linking structure further comprises a thermal crosslinking group or a photocrosslinking group; after step S303, i.e. after cleaning by a developer, a patterned quantum dot film layer is formed on the side of the electrode facing away from the substrate, further comprising:
and S304, heating and annealing the quantum dot film layer to enable the charged connecting structure to generate a crosslinking reaction.
In a specific implementation, the first substance is a photoacid generator; processing the quantum dot film in the reserved area under the preset condition in the step S302 includes:
irradiating the quantum dot film in the reserved area through 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 uses the first substance as the photoacid generator PAG, and the first ion is a hydrogen ion as an example, which is further described below with reference to fig. 6:
the preparation of each front film layer of the patterned electrode and the quantum dot film layer is realized. The quantum dot adopts a special charged ligand, the quantum dot itself shows negative charge due to ligand ionic 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 where the quantum dot needs to be deposited after spin coating, hydrogen ions generated after the decomposition of PAG illumination react with the ligand groups, the change of the quantum dot from negative charge to positive charge is carried out, at the moment, the quantum dot in the pixel where the quantum dot needs to be deposited is positively charged, and the quantum dot in the pixel where the quantum dot needs to be washed out is negatively charged; electrifying the patterned electrode to show electronegativity; the quantum dots and the substrate have stronger acting force due to the mutual attraction of positive and negative charges in the pixel area where the quantum dots are required to be deposited, and the quantum dots in the charge repulsive area are washed away when the good solvent is used for development due to the like repulsion of the charges of the substrate and the charges of the quantum dots in other areas, so that the quantum dot areas with opposite charges are left, and the patterned quantum dots are formed.
When the patterning quantum dot deposition of other pixel areas is repeated, in order to avoid the influence on the deposited quantum dots during development, the quantum dot ligand contains thermally crosslinkable groups, and after the patterning deposition, the quantum dot ligand is crosslinked through thermal annealing to stabilize the quantum dot film layer.
Specifically, the quantum dot body is CdSe/ZnS red quantum dot, and the charged precursor structure X is formed by dissolving the quantum dot ligand A, so that the device structure can be an inverted device. Spin-coating a front film layer (specifically an electron transport layer, and a material of zinc oxide nano particles) of 30mg/ml at a rotating speed of 1500rpm on a substrate base plate after an electrode (specifically an indium tin oxide ITO) is deposited, and annealing at 120 ℃ for 5 minutes; and spin-coating the red light quantum dots with the rotation speed of 2500rpm and carrying out electrifying the ITO electrode to enable the electrode to be negatively charged after spin-coating, simultaneously developing the quantum dot film layer by using ethanol to remove the quantum dots in other areas, annealing for 120 degrees for 30 minutes, 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 material, which comprises the following specific synthetic routes:
reaction (1): 10mmol of 3, 5-dihydroxynitrobenzene was placed in a 100ml three-necked flask, 10.2mmol of N-bromosuccinimide (NBS) was added as a brominating reagent, and 40ml of N, N-Dimethylformamide (DMF) was added as a reaction solvent. Stir overnight for 24 hours. After the reaction is completed, pouring the reactant into water and extracting with dichloromethane three times, and collecting a dichloromethane phase; the dichloromethane phase was dried and then subjected to column chromatography (eluent V Dichloromethane (dichloromethane) ：V Petroleum ether =1: 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 tetrakis triphenylphosphine palladium was added as a catalyst, and 40ml of toluene was added as a reaction solvent. After the air in the bottle is replaced by argon through three times of pumping and discharging of the double-row pipes, stirring is started, the temperature is heated to 95 ℃, and condensation and reflux are carried out for 24 hours. Removing toluene from the reactant by rotary evaporation after the reaction is finished, dissolving solid substances by using dichloromethane, extracting three times by using water, and collecting a dichloromethane phase; the dichloromethane phase was dried and then subjected to column chromatography (eluent V Dichloromethane (dichloromethane) ：V Petroleum ether =3: 1) Finally, spin-drying the collected solution to obtain a product e;
reaction (3): 10mmol of product b and 10.5mmol of product e are placed in a 100ml three-necked flask, 0.01mmol of tetraphenylphosphine palladium is added as catalyst, and 40ml of toluene is added as reaction solvent. After the air in the bottle is replaced by argon through three times of pumping and discharging of the double-row pipes, stirring is started, the temperature is heated to 95 ℃, and condensation and reflux are carried out for 24 hours. After the reaction is completed, the reaction is reversedRemoving toluene from the reactant by rotary evaporation, dissolving solid substances by using dichloromethane, extracting three times by using water, and collecting a dichloromethane phase; the dichloromethane phase was dried and then subjected to column chromatography (eluent V Dichloromethane (dichloromethane) ：V Petroleum ether =1: 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-necked 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 is replaced by argon through three times of pumping and discharging of the double-row pipes, stirring is started, the temperature is heated to 120 ℃, and condensation and reflux are carried out for 24 hours. Pouring the reactant into water to precipitate solid after the reaction is finished, filtering, recrystallizing with DMF, and finally drying the precipitated solid to obtain 7.5mmol of product h; 7.5mmol of product h was placed in a 100ml three-necked flask, 8mmol of hydrazine hydrate was added and 40ml of N, N-Dimethylformamide (DMF) was added as a reaction solvent. After the air in the bottle is replaced by argon through three times of pumping and discharging of the double-row pipes, stirring is started, the temperature is heated to 80 ℃, and condensation and reflux are carried out for 24 hours. After the reaction is finished, pouring the reactant into water to precipitate solid, filtering, recrystallizing with ethanol, and finally drying the precipitated solid to obtain a final product k.
The specific processes of the reactions (1), (2), (3) and (4) can be as follows:
the embodiment of the invention has the following beneficial effects: according to 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 through preset conditions for the reserved area where the quantum dot film is required to be reserved, first ions are formed, the charged precursor structure reacts with the first ions to generate a charged connection structure with opposite electrical property to the charged precursor structure, the area where the quantum dot film is required to be removed is still a non-reacted charged precursor structure, the chargeability of different areas is further different, when the development and removal are carried out, the charged connection structure is adsorbed through the electrode, the area where the quantum dot film is not required to be reserved is repelled by the electrode, the quantum dot film outside the reserved area is 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 modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. A display panel, comprising: a substrate, electrodes positioned on one side of the substrate in sequence, and a quantum dot film layer; wherein, the quantum dot film layer includes: the quantum dot comprises a quantum dot body and a charged connection structure connected with the quantum dot body, wherein the charged connection structure is formed by reacting a charged precursor structure with opposite electrical property with first ions, the electrical property of the first ions is opposite to that of the charged precursor structure, and the first ions are generated by decomposing a photoacid generator mixed in a quantum dot film layer under preset light irradiation conditions;
wherein the charged precursor structure comprises a plurality of negatively charged weakly acidic groups and a plurality of positively charged weakly basic groups; the charged connecting structure further comprises a crosslinking group; the quantum dot film layer comprises the following structures:
wherein R1 is
R2 isWherein m+n is less than or equal to 12;
x is-NH 2, -COOH, or-SH;
r3 is the crosslinking group.
2. The display panel of claim 1, wherein the charged precursor structure is negatively charged; the number of weakly acidic groups is greater than the number of weakly basic groups.
3. The display panel of claim 1, wherein 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:
primary amine groups;
a secondary amine group;
and a tertiary amine group.
4. The display panel of claim 1, wherein the crosslinking group is a thermal crosslinking group comprising: an epoxy group;
alternatively, the crosslinking group is a photocrosslinking group comprising one of:
an epoxy group;
an acrylate group;
an isoprene group;
a mercapto group;
an olefin;
alkynes;
and (3) azides.
5. A display device comprising the display panel according to any one of claims 1-4.
6. A method for manufacturing a display panel, comprising:
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, and repeating at least once;
forming a patterned quantum dot film layer on one side of the electrode, which is far away from the substrate base plate, wherein the quantum dot film layer comprises the following components:
forming a quantum dot film on one side of the electrode, which is away from the substrate, wherein the quantum dot film comprises: a quantum dot body, a charged precursor structure connected with the quantum dot body, and a photoacid generator; the charged precursor structure comprises a plurality of negatively charged weakly acidic groups and a plurality of positively charged weakly basic groups;
under the condition of preset light irradiation, the quantum dot film in a reserved area is processed, so that the photoacid generator in the reserved area is decomposed to generate first ions, the charged precursor structure reacts with the first ions to form a charged connection structure with opposite electrical property to the charged precursor structure, and the first ions are opposite to the charged precursor structure in electrical property;
loading voltage opposite to the electricity of the electrified connection structure on the electrode, cleaning the electrode through a developing solution to enable the electrified connection structure of the reserved area and the electrode to be attracted to each other, and enabling the electrified precursor structure of the area outside the reserved area and the electrode to be electrically repelled and cleaned;
wherein the charged connecting structure further comprises a crosslinking group; the quantum dot film layer comprises the following structures:
wherein R1 is
R2 isWherein m+n is less than or equal to 12;
x is-NH 2, -COOH, or-SH;
r3 is the crosslinking group.
7. The method of claim 6, wherein the charged connecting structure further comprises a thermal crosslinking group or a photocrosslinking group;
after being washed by a developing solution, the forming a patterned quantum dot film layer on one side of the electrode, which is away from the substrate, further comprises:
and heating and annealing the quantum dot film layer to enable the charged connecting structure to generate a crosslinking reaction.
8. The method of claim 7, wherein the processing the quantum dot film in the reserved area under the preset light irradiation condition comprises:
irradiating the quantum dot film in the reserved area through ultraviolet light so as to decompose the photoacid generator to generate hydrogen ions, and carrying out the following reactions:
。
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| CN110590549A (en) * | 2019-09-30 | 2019-12-20 | 京东方科技集团股份有限公司 | Ligand, quantum dot and patterning method of quantum dot layer |
| CN110832618A (en) * | 2017-04-18 | 2020-02-21 | 芝加哥大学 | Photoactive inorganic ligand-capped inorganic nanocrystals |
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| CN110590549A (en) * | 2019-09-30 | 2019-12-20 | 京东方科技集团股份有限公司 | Ligand, quantum dot and patterning method of quantum dot layer |
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