CN113831910B - Quantum dot material, quantum dot light-emitting device and manufacturing method thereof - Google Patents
Quantum dot material, quantum dot light-emitting device and manufacturing method thereof Download PDFInfo
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- 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
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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
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
Abstract
The present disclosure provides a quantum dot material including a plurality of quantum dots, characterized in that the quantum dots include a quantum dot body, a first ligand formed on the quantum dot body through a coordinate bond, a second ligand formed on the quantum dot body through a coordinate bond, the first ligand having one of acidity and basicity, the second ligand being capable of forming a third ligand having the other one of acidity and basicity after being treated under a predetermined condition, a salt formation reaction being capable of occurring between the first ligand and the third ligand, the solubility of the quantum dot in which the salt formation reaction occurs in a predetermined solvent being different from the solubility of the quantum dot including the first ligand and the second ligand in the predetermined solvent. The disclosure also provides a quantum dot light emitting device and a method of manufacturing the quantum dot light emitting device.
Description
Technical Field
The present disclosure relates to the field of quantum dot light emitting diodes, and in particular, to a quantum dot material, a quantum dot light emitting device, and a method of fabricating the quantum dot light emitting device.
Background
The quantum dot light emitting diode (QLED, quantum Dot Light Emitting Diodes) has been widely used because of its characteristics of narrow emission spectrum, wide color gamut, good stability, long lifetime, low manufacturing cost, and the like.
In the process of manufacturing the quantum dot light emitting diode, a quantum dot material layer made of a quantum dot material needs to be patterned by utilizing a photoetching process, and a quantum dot light emitting layer of the quantum dot light emitting diode is obtained. However, when the patterning photoetching and patterning process is carried out on the quantum dot material layer, the process requirement is high, and the manufacturing cost of the quantum dot light emitting diode is increased.
Disclosure of Invention
The invention aims to provide a quantum dot material, a quantum dot light emitting device and a manufacturing method of the quantum dot light emitting device.
As a first aspect of the present disclosure, there is provided a quantum dot material including a plurality of quantum dots, wherein the quantum dots include a quantum dot body, a first ligand formed on the quantum dot body through a coordinate bond, the first ligand having one of acidity and basicity, and a second ligand formed on the quantum dot body through a coordinate bond, the second ligand being capable of forming a third ligand having the other of acidity and basicity after being treated under a predetermined condition, wherein a salt formation reaction can occur between the first ligand and the third ligand, and a solubility of the quantum dots including the first ligand and the second ligand in a predetermined solvent is different from a solubility of the quantum dots including the first ligand and the second ligand in the predetermined solvent.
Optionally, the first ligand has a basic character and the third ligand has an acidic character.
Optionally, the predetermined condition is to irradiate with light having a predetermined wavelength.
Optionally, the second ligand includes a second coordination group, a second connection chain, and an acid generating group, the second coordination group is formed on the quantum dot body through a coordination bond, the second connection chain is connected between the acid generating group and the second coordination group, and the acid generating group can generate hydrogen ions under the irradiation of light with the predetermined wavelength.
Alternatively, the acid generating group is selected from any one of a diazonaphthoquinone group, a phenolic hydroxyl group containing an electron withdrawing group as a protecting group, and a triazine group.
Optionally, the acid generating group is selected from any one of the following groups:
optionally, the second linking chain comprises a fatty chain or an aromatic chain.
Optionally, the second coordinating group is selected from any one of mercapto, amino, carboxyl.
Optionally, the second ligand has the formula:
optionally, the first ligand includes a first coordinating group formed on the quantum dot body by a coordination bond, a first connecting chain connected between the first coordinating group and the basic group, and a basic group.
Alternatively, the basic group is selected from any one of primary amine, secondary amine, tertiary amine, and the like.
Optionally, the first linking chain comprises a fatty chain or an aromatic chain.
Optionally, the number of first ligands on the quantum dot body is not less than the number of second ligands.
Optionally, the first ligand has the following formula:
optionally, the quantum dot further comprises an alkyl chain ligand formed on the quantum dot body through coordination bonds, and the number of carbon atoms in the alkyl chain ligand is not less than 8.
Optionally, at least one of the first ligand and the second ligand has not less than 8 carbon atoms.
As a second aspect of the present disclosure, there is provided a method of manufacturing a quantum dot light emitting device, wherein the method of manufacturing includes:
providing an initial substrate;
forming a pattern including a quantum dot light emitting layer corresponding to at least one color, wherein the forming a pattern including a quantum dot light emitting layer corresponding to at least one color includes:
coating a quantum dot solution on an initial substrate to obtain a quantum dot solution layer, wherein the quantum dot material provided by the solute first aspect of the quantum dot solution;
processing a preset position on the quantum dot solution layer by using preset processing conditions so that a second ligand at the preset position forms a third ligand;
developing the quantum dot solution layer processed by the preset processing conditions to obtain a pattern of the quantum dot luminescent layer comprising the luminescent device.
Optionally, the developing the quantum dot solution layer after being treated by the preset treatment conditions includes:
applying the preset solvent to the quantum dot solution layer treated by the preset treatment conditions, so that the first ligand and the third ligand of the quantum dot treated by the preset conditions react to generate salt, and the polarity of the preset solvent is the same as that of the quantum dot subjected to the salt generation reaction;
and dissolving the quantum dots which are at the preset positions and generate salt reaction by using the preset solvent, and obtaining a pattern of the quantum dot luminescent layer comprising the luminescent device.
Optionally, the developing the quantum dot solution layer after being treated by the preset treatment conditions includes:
applying the preset solvent to the quantum dot solution layer treated by the preset treatment conditions, so that the first ligand and the third ligand of the quantum dot treated by the preset conditions react to generate salt, and the polarity of the preset solvent is the same as that of the quantum dot subjected to the salt generation reaction;
and developing the part except the preset position on the quantum dot solution layer by using a developing solution to remove the part except the preset position on the quantum dot solution layer, wherein the polarity of the developing solution is different from that of the quantum dot subjected to salt forming reaction.
Alternatively, the preset processing condition is irradiation with light having a predetermined wavelength.
As a third aspect of the present disclosure, there is provided a quantum dot light emitting device, the quantum dot light emitting device includes at least one quantum dot light emitting diode, the quantum dot light emitting diode includes a quantum dot light emitting layer, wherein a material of the quantum dot light emitting layer is the quantum dot material provided in the first aspect of the present disclosure, or the quantum dot light emitting layer is a product of the quantum dot material provided in the first aspect of the present disclosure after the quantum dot material is subjected to the preset condition treatment and concurrently generates a salt reaction.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
fig. 1 is a schematic diagram of a quantum dot material provided in the present disclosure, wherein the quantum dot material is treated under a preset condition and reacts with a preset polar solution;
FIG. 2 is a flow diagram of one embodiment of patterning the quantum dot material;
FIG. 3 is a flow diagram of another embodiment of patterning the quantum dot material;
FIG. 4 is a flow chart of a method of fabrication provided by the present disclosure;
FIG. 5 is a schematic diagram of one embodiment of a light emitting unit of a quantum dot light emitting device provided by the present disclosure;
fig. 6 is a schematic diagram of another embodiment of a light emitting unit of a quantum dot light emitting device provided by the present disclosure;
fig. 7 is a schematic diagram of yet another embodiment of a light emitting unit of a quantum dot light emitting device provided by the present disclosure;
FIG. 8 is a schematic diagram of one embodiment of step S140;
fig. 9 is a schematic diagram of another embodiment of step S140.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In the related art, in the process of manufacturing a quantum dot light emitting layer of a quantum dot light emitting diode, it is necessary to expose the quantum dot material layer using a photolithography process. The exposed portions of the quantum dot material layer crosslink the ligands of the quantum dot material. Thus, in a particular developing solvent, the solubility of the exposed and unexposed portions of the quantum dot material layer is different for a particular organic solvent. However, the degree of crosslinking is affected by the degree of exposure, and in order to achieve accurate development, strict control of the exposure amount is required, and the process requirements are high.
In view of this, as one aspect of the present disclosure, there is provided a quantum dot material including a plurality of quantum dots, wherein the quantum dots include a quantum dot body (shown in fig. 1 is a quantum dot body 110), a first ligand 121 formed on the quantum dot body by a coordination bond, a second ligand 122 formed on the quantum dot body by a coordination bond, the first ligand 121 having one of an acidic property and an alkaline property, the second ligand 122 being capable of being formed into a third ligand 123 after being subjected to a predetermined condition, the third ligand 123 having the other of an acidic property and an alkaline property, a reaction being able to occur between the first ligand and the third ligand, and a solubility of the quantum dot in a predetermined solvent in which a salification reaction occurs is different from a solubility of the quantum dot including the first ligand and the second ligand (i.e., a quantum dot in which a salt reaction does not occur) in a predetermined solvent.
Shown in fig. 1 is a schematic diagram of a reaction occurring when quantum dots are subjected to preset conditions and a salt formation reaction of the quantum dots subjected to preset conditions.
As shown in fig. 1, after the quantum dot including the first ligand 121 and the second ligand 122 is subjected to a preset condition (herein, UV irradiation), the quantum dot including the first ligand 121 and the third ligand 123 is obtained.
After the quantum dots including the first ligand 121 and the third ligand 123 undergo a salt formation reaction, quantum dots including salts generated by the reaction of the first ligand 121 and the third ligand 123 are formed.
In the present disclosure, the reaction conditions for the salt formation reaction are not particularly limited. As an alternative embodiment, the reaction condition may be that the quantum dot including the first ligand 121 and the third ligand 123 is set in a preset solvent, so that one of the first ligand 121 and the third ligand 123 having acidity ionizes to generate hydrogen ions, and one of the first ligand 121 and the third ligand 123 having alkalinity generates a salt formation reaction (here, the salt formation reaction is an acid-base neutralization reaction).
When the quantum dot material is used for preparing the quantum dot luminescent layer, the quantum dot material is used for preparing a quantum dot solution, and the quantum dot solution is coated on an initial substrate to form a quantum dot material layer. And then processing the preset position of the quantum dot material layer by utilizing the preset condition.
In the present disclosure, the final "preset position" may be determined according to the manufacturing process. As an alternative embodiment, as shown in fig. 2, the portions of the quantum dot material layer that are not desired to remain may be treated. After the treatment of the predetermined condition, the second ligands (indicated by dotted lines) on the quantum dot material are converted into third ligands (indicated by bold black lines) in the treated portion. When the treated quantum dot material layer is soaked in the preset polar solvent, the first ligand and the third ligand undergo an acid-base neutralization reaction to generate salt (namely, the product in the above process), and as shown in fig. 2, the first ligand is combined with the third ligand. The finally generated salt is dissolved in the preset polar solvent, and finally the treated quantum dot material is removed from the whole quantum dot material layer to obtain a required quantum dot pattern, wherein the quantum dots in the quantum dot pattern comprise a quantum dot body, a first ligand 121 formed on the quantum dot body and a second ligand 122 formed on the quantum dot body.
The preset polar solvent only can dissolve salts, but does not dissolve untreated quantum dot materials, and is irrelevant to whether the quantum dot materials have a crosslinking reaction or not, so that when a quantum dot material layer formed by the quantum dot materials is developed, the process requirement is low, and the cost for manufacturing the quantum dot light emitting diode can be reduced.
Of course, the step of developing the quantum dot material layer after being treated by the preset conditions is not limited to the above-described treatment manner. For example, as shown in fig. 3, the portion of the quantum dot material layer that needs to be retained may be subjected to the preset condition, so that the second ligand of the quantum dot is modified into the third ligand in the portion of the quantum dot material layer that is processed. And processing the quantum dot layer subjected to the preset condition treatment by utilizing the preset polar solvent, so that the first ligand and the third ligand in the quantum dot with the first ligand and the third ligand are subjected to acid-base neutralization reaction, and salt is generated. After salt is generated, the quantum dots of which the first ligand and the third ligand form salt are not further processed, but the quantum dots which comprise the quantum dots which are not processed by preset conditions and the quantum dots of which the first ligand and the third ligand react to form salt are developed by utilizing a developing solution so as to remove the quantum dots which are not processed by the preset conditions, so that the quantum dots which are processed by the preset conditions finally remain on the initial substrate.
In the above embodiment, the cross-linking reaction is not required, and the degree of the cross-linking reaction is not required to be controlled, thereby reducing the cost of manufacturing the quantum dot pattern layer.
In the present disclosure, the specific types of the first ligand and the second ligand are not particularly limited. As an alternative embodiment, the first ligand has an alkaline nature. Accordingly, the second ligand is an acid generating ligand such that the third ligand has acidity. By "acid generating ligand" is meant a ligand capable of generating hydrogen ions, that is, a third ligand having hydrogen ions, after treatment under the predetermined conditions.
In order to facilitate control of the patterning process for patterning the quantum dot material layer, the predetermined condition is optionally treated to be irradiated with light having a predetermined wavelength. That is, when the quantum dot material is irradiated with light having a predetermined wavelength, the second ligand may undergo a photoreaction and generate hydrogen ions.
As an alternative embodiment, the second ligand includes a second coordination group formed on the quantum dot body through a coordination bond, a second connection chain connected between the acid generating group and the second coordination group, and an acid generating group capable of generating hydrogen ions under irradiation of light of the predetermined wavelength.
Specifically, the second ligand has a chemical formula of C-Y-D, wherein C is a second coordinating group, wherein C may be selected from any one of mercapto (-SH), amino (-NH 2), carboxyl (-COOH).
Optionally, the second linking chain comprises a fatty chain or an aromatic chain.
Alternatively, the acid generating group is selected from any one of a diazonaphthoquinone group, a phenolic hydroxyl group containing an electron withdrawing group as a protecting group, and a triazine group.
For example, the acid generating group may have one of the following formulas:
accordingly, the light of the predetermined wavelength may be UV light, and thus, the second ligand may transmit the following reaction under irradiation of UV light:
in the present disclosure, the first ligand may be a weakly basic ligand. Optionally, the first ligand includes a first coordinating group formed on the quantum dot body by a coordination bond, a first connecting chain connected between the first coordinating group and the basic group, and a basic group.
Alternatively, the basic group is selected from primary amines (-NH) 2 ) Any one of secondary amine (-NH-), tertiary amine (-n=), and the like.
Optionally, the first linking chain comprises a fatty chain or an aromatic chain.
As an alternative embodiment, the first ligand has the following formula:
in order to enable hydrogen ions generated by treatment (e.g., light irradiation of a predetermined wavelength) under preset conditions to be completely neutralized by the first ligands, the number of the first ligands on the quantum dot body is optionally not less than the number of the second ligands. In this embodiment, no hydrogen ions remain in the obtained quantum dot light emitting layer, so that the quantum dot light emitting diode including the quantum dot light emitting layer has good light emitting performance.
In order to improve the solubility of the quantum dot after the treatment under the predetermined condition in the predetermined polar solvent, optionally, the quantum dot before the treatment may further include an alkyl chain ligand formed on the quantum dot body through a coordination bond, and the number of carbon atoms in the alkyl chain ligand is not less than 8.
Of course, the present disclosure is not limited thereto, and the alkyl chain ligand may not be provided on the quantum dot body when the number of carbon atoms of at least one of the first ligand and the second ligand is not less than 8. Of course, the quantum dot body may be provided with the alkyl chain ligand, the first ligand having not less than 8 carbon atoms, and/or the second ligand having not less than 8 carbon atoms at the same time.
As a second aspect of the present disclosure, there is provided a manufacturing method of a light emitting device, wherein, as shown in fig. 4, the manufacturing method includes:
in step S110, an initial substrate is provided;
forming a pattern including a quantum dot light emitting layer corresponding to at least one color, wherein the forming a pattern including a quantum dot light emitting layer corresponding to at least one color includes:
in step S120, coating a quantum dot solution on an initial substrate to obtain a quantum dot solution layer, wherein a solute of the quantum dot solution is the quantum dot material provided in the first aspect of the present disclosure;
in step S130, processing the preset position on the quantum dot solution layer using preset processing conditions so that the second ligand at the preset position is formed into a third ligand;
in step S140, the quantum dot solution layer processed using the preset processing conditions is developed to obtain a pattern including the quantum dot light emitting layer of the light emitting device.
In the present disclosure, the quantum dot light emitting layer of one color is not formed, and steps S120 to S140 are performed once.
As described above, in the step of manufacturing the quantum dot light emitting layer, a cross-linking reaction is not required, nor is the degree of cross-linking reaction controlled, thereby reducing the cost of manufacturing the quantum dot pattern layer.
As an alternative embodiment, as shown in fig. 8, step S140 may specifically include:
in step S141a, applying the preset solvent to the quantum dot solution layer treated with the preset treatment conditions, so that the first ligand and the third ligand of the quantum dot treated with the preset conditions react to generate salt, wherein the polarity of the preset solvent is the same as that of the quantum dot subjected to the salt generation reaction;
in step S142a, the quantum dots at the preset positions, which react to generate salt, are dissolved using the preset solvent, and a pattern including a quantum dot light emitting layer of the light emitting device is obtained.
This embodiment is briefly described below in connection with fig. 2.
Forming a red light quantum dot material layer on the front film layer 200, wherein the red light quantum dot material layer comprises a plurality of quantum dots, and quantum dot bodies of the quantum dots are red quantum dot bodies 110R;
exposing the quantum dot material layer by using a mask plate, and shielding the positions of the red quantum dot light emitting diodes by using the mask plate so that the quantum dots at the positions of the green quantum dot light emitting diodes and the quantum dots at the positions of the blue quantum dot light emitting diodes are irradiated by UV light;
the second ligand on the quantum dot at the position of the green quantum dot light emitting diode and the second ligand on the quantum dot at the position of the blue quantum dot light emitting diode become a third quantum dot ligand after being illuminated (as shown by the bold solid line);
processing the exposed quantum dot material layer by using a preset solvent to enable acid-base neutralization reaction of the first ligand and the third ligand on the quantum dot at the position of the green quantum dot light-emitting diode and enable acid-base neutralization reaction of the first ligand and the third ligand on the quantum dot at the position of the blue quantum dot light-emitting diode;
development is performed using a preset solvent to remove the quantum dot material at the green light emitting diode location and the quantum dot material at the blue light emitting diode location, leaving the unexposed quantum dot material corresponding to the red quantum dot light emitting diode location on the front film layer 200.
In the above manner, a quantum dot material corresponding to the position of the green quantum dot light emitting diode (the quantum dot body is the green quantum dot body 110G) and a quantum dot material corresponding to the position of the blue quantum dot light emitting diode (the quantum dot body is the blue quantum dot body 110B) can be obtained, respectively.
Of course, the present disclosure is not limited thereto. As another alternative embodiment, as shown in fig. 9, step S140 may include:
in step S141b, applying the preset solvent to the quantum dot solution layer treated with the preset treatment conditions, so that the first ligand and the third ligand of the quantum dot treated with the preset conditions react to generate salt, wherein the polarity of the preset solvent is the same as that of the quantum dot subjected to the salt generation reaction;
in step S142b, a portion of the quantum dot solution layer other than the predetermined position is developed with a developing solution, which is different in polarity from the quantum dots having undergone a salt formation reaction, to remove the portion of the quantum dot solution layer other than the predetermined position.
The above embodiment will be briefly described with reference to fig. 3.
Forming a red light quantum dot material layer on the front film layer 200, wherein the red light quantum dot material layer comprises a plurality of quantum dots, and quantum dot bodies of the quantum dots are red quantum dot bodies 110R;
exposing the quantum dot material layer at the position of the red quantum dot light emitting diode by using a mask plate, and shielding the position of the green quantum dot light emitting diode and the blue quantum dot light emitting diode by using the mask plate so that only the quantum dot material at the position of the red quantum dot light emitting diode is irradiated;
the second ligand on the quantum dot at the position of the red quantum dot light emitting diode becomes a third quantum dot ligand after being illuminated (as shown by the bold solid line);
processing the exposed quantum dot material layer by using a preset solvent to enable acid-base neutralization reaction of the first ligand and the third ligand on the quantum dot at the position of the red quantum light-emitting diode;
development is performed using a developing solution to remove the quantum dot material at the green light emitting diode location and the quantum dot material at the blue light emitting diode location, leaving the exposed quantum dot material corresponding to the red quantum dot light emitting diode location on the front film layer 200.
In the above manner, a quantum dot material corresponding to the position of the green quantum dot light emitting diode (the quantum dot body is the green quantum dot body 110G) and a quantum dot material corresponding to the position of the blue quantum dot light emitting diode (the quantum dot body is the blue quantum dot body 110B) can be obtained, respectively.
As a third aspect of the present disclosure, there is provided a quantum dot light emitting device, the quantum dot light emitting device including at least one quantum dot light emitting diode, the quantum dot light emitting diode including a quantum dot light emitting layer, wherein a material of the quantum dot light emitting layer is the above-mentioned quantum dot material provided by the present disclosure, or a product of the quantum dot light emitting layer obtained by subjecting the quantum dot material provided by the first aspect of the present disclosure to the preset condition and concurrently generating a salt reaction.
In the present disclosure, the quantum dot light emitting device may include a plurality of light emitting units, each of which has a plurality of quantum dot light emitting diodes disposed therein. And, the quantum dot light emitting diode in the same light emitting unit can emit light of different colors.
In the embodiments shown in fig. 5 to 7, one light emitting unit includes three quantum dot light emitting diodes capable of emitting red light, green light, and blue light, respectively.
In the present disclosure, the specific form of the quantum dot light emitting device is not particularly limited, and for example, the quantum dot light emitting device may be a display device.
Examples
The quantum dot material is a quantum dot with a core-shell structure, the original ligand is oleic acid, the final target ligand is a first ligand P1 and a second ligand Q1, the concentration is 20mg/ml, and the solvent is toluene.
Preparation of first ligand P1: 1mol of 1, 1-dimethyl-5-bromopentanamine and 1.1mol of ethylene disulfide are placed in a 250ml three-neck flask, 1.1mol of sodium hydride and 100ml of N, N-dimethylformamide are added to react for 12 hours at 160 ℃ under the protection of nitrogen, after the reaction is finished, the product is immersed in deionized water, filtered, extracted and washed three times by using methylene dichloride, and then separated by column chromatography to obtain a product P1.
Preparation of the second ligand Q1: 1mol of 2-diazonium-1-naphthoquinone-5-sulfonyl chloride and 1.1mol of 2-mercaptoethanol are taken to be placed in a 250ml three-neck flask, 1.01mol of sodium hydride and 100ml of N, N-dimethylformamide are added to react for 12 hours at 160 ℃ under the protection of nitrogen, after the reaction is finished, the product is immersed in deionized water, and the product is filtered and dried at 120 ℃ in vacuum to obtain the product Q1.
Ligand exchange: quantum dot ligand exchange
Taking 1ml of quantum dot solution (20/mg/ml) and adding 5mg of P1 and 5mgQ1 thereto, stirring at room temperature for 4 hours to complete ligand exchange, then precipitating the quantum dots by using 8ml of methanol, centrifuging and discarding the supernatant; the quantum dots were dissolved using 1ml chloroform, precipitated using 8ml methanol, centrifuged and the supernatant discarded, and the quantum dot powder was redissolved in toluene to form a 20mg/ml solution after vacuum drying at 80 ℃.
Shown below is the synthetic route for the first ligand P1:
shown below is the synthetic route for the second ligand Q1:
in this example 1, the first ligand P1 has the following chemical formula:
in this example 1, the second ligand Q1 has the following chemical formula:
in this example 1, the first ligand and the second ligand react as follows upon UV illumination:
in the above reaction scheme, the photoactive group of the predominantly second ligand breaks, forming a third ligand.
The third ligand and the first ligand can undergo a neutralization reaction to form the following groups:
production example
Production example 1
The fabrication of the inverted bottom emission quantum dot light emitting diode shown in fig. 5 includes the steps of:
forming a cathode 700 using an ITO material;
placing the substrate formed with the cathode 700 in a chamber filled with nitrogen, spin-coating zinc oxide nanoparticles (4000 rpm,30s,30 mg/ml) on the cathode 700, and annealing at 120 ℃ for 20 minutes to obtain an electron transport layer 600;
placing the substrate with the electron transport layer 600 formed in air, and spin-coating red quantum dot solution (3000 rpm,30 s) on the electron transport layer 600 to obtain a red quantum dot material layer;
carrying out UV exposure on the red quantum dot material layer by using a master mask plate (the mask plate shown in fig. 2) for 100mj, baking the red quantum dot material layer at 90 ℃ for 120s after exposure, developing the film layer by using deionized water, and annealing the film layer at 120 ℃ for 20 minutes after development is finished to obtain a red quantum dot pattern layer comprising a plurality of red quantum dot luminescent layers 100R, wherein quantum dots in the red quantum dot luminescent layers 100R comprise a first ligand and a second ligand;
repeating the patterning process of the red light quantum dot pattern layer to prepare a green light quantum dot pattern layer including a plurality of green light quantum dot light emitting layers 100G and a blue light quantum dot pattern layer including a plurality of blue light quantum dot light emitting layers 100B;
preparing the hole transport layer 500 and the hole injection layer 400 by evaporation;
silver is evaporated to 120nm to form an anode 300, and the device preparation is completed after packaging.
The red light quantum dots in the red light quantum dot solution, the green light quantum dots in the green light quantum dot solution and the blue light quantum dots in the blue light quantum dot solution are prepared according to the preparation methods provided in the embodiments, and the three quantum dot solutions are different in that quantum dot bodies in different quantum dot solutions are different.
Production example 2
The fabrication of the front-end bottom emission quantum dot light emitting diode shown in fig. 6 includes the steps of:
forming a cathode 700 using an ITO material;
placing the substrate formed with the cathode 700 in a chamber filled with nitrogen, spin-coating nickel oxide nanoparticles (2000 rpm,30s,25 mg/ml) on the cathode 700, and annealing at 120 ℃ for 20 minutes to obtain a hole injection and transport layer 510;
placing the substrate with the hole injection and transport layer 510 formed in air, and spin-coating red quantum dot solution (3000 rpm,30 s) on the hole injection and transport layer 510 to obtain a red quantum dot material layer;
carrying out UV exposure on the red quantum dot material layer by using a master mask plate (the mask plate shown in fig. 2) for 100mj, baking the red quantum dot material layer at 90 ℃ for 120s after exposure, developing the film layer by using deionized water, and annealing the film layer at 120 ℃ for 20 minutes after development is finished to obtain a red quantum dot pattern layer comprising a plurality of red quantum dot luminescent layers 100R, wherein quantum dots in the red quantum dot luminescent layers 100R comprise a first ligand and a second ligand;
repeating the patterning process of the red light quantum dot pattern layer to prepare a green light quantum dot pattern layer comprising a plurality of green light quantum dot light emitting layers and a blue light quantum dot pattern layer comprising a plurality of blue light quantum dot light emitting layers;
continuing spin-coating the zinc oxide nanoparticle solution (3000 rpm,30s,30 mg/ml), annealing at 120 ℃ for 20 minutes to obtain an electron injection layer 610;
aluminum was evaporated 120nm to obtain anode 300, and the device fabrication was completed after packaging.
The red light quantum dots in the red light quantum dot solution, the green light quantum dots in the green light quantum dot solution and the blue light quantum dots in the blue light quantum dot solution are prepared according to the preparation methods provided in the embodiments, and the three quantum dot solutions are different in that quantum dot bodies in different quantum dot solutions are different.
Production example 3
The fabrication of the front-mounted top-emitting quantum dot light emitting diode shown in fig. 7 includes the steps of:
sequentially forming an ITO layer, an Ag layer and an ITO layer on a substrate, and finally obtaining an anode 300;
placing the substrate formed with the anode 300 in a chamber filled with nitrogen gas, spin-coating nickel oxide nanoparticles (2000 rpm,30s,25 mg/ml) on the anode 300, and annealing at 120 ℃ for 20 minutes to obtain a hole injection and transport layer 510;
placing the substrate with the hole injection and transport layer 510 formed in air, and spin-coating red quantum dot solution (3000 rpm,30 s) on the hole injection and transport layer 510 to obtain a red quantum dot material layer;
carrying out UV exposure on the red quantum dot material layer by using a master mask plate for 100mj;
baking for 120s at 90 ℃ after exposure, developing the film layer by using deionized water, and annealing for 20 minutes at 120 ℃ after development is completed to obtain a red light quantum dot pattern layer comprising a plurality of red light quantum dot luminescent layers 100R, wherein quantum dots in the red light quantum dot luminescent layers 100R comprise a first ligand and a second ligand;
repeating the patterning process of the red light quantum dot pattern layer to prepare a green light quantum dot pattern layer comprising a plurality of green light quantum dot light emitting layers and a blue light quantum dot pattern layer comprising a plurality of blue light quantum dot light emitting layers;
the spin-coating of the zinc oxide nanoparticle solution (3000 rpm,30s,30 mg/ml) was continued and annealed at 120 ℃ for 20 minutes to obtain an electron injection layer 610;
sputtering Indium Gallium Zinc Oxide (IGZO) on the electron injection layer 610, and obtaining a cathode 700 with the thickness of 50nm, and packaging to finish the device preparation.
The red light quantum dots in the red light quantum dot solution, the green light quantum dots in the green light quantum dot solution and the blue light quantum dots in the blue light quantum dot solution are prepared according to the preparation methods provided in the embodiments, and the three quantum dot solutions are different in that quantum dot bodies in different quantum dot solutions are different.
Example embodiments have been disclosed herein, and although specific terms are employed, they are used and should be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some instances, it will be apparent to one skilled in the art that features, characteristics, and/or elements described in connection with a particular embodiment may be used alone or in combination with other embodiments unless explicitly stated otherwise. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the disclosure as set forth in the appended claims.
It is to be understood that the above embodiments are merely exemplary embodiments employed to illustrate the principles of the present disclosure, however, the present disclosure is not limited thereto. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the disclosure, and are also considered to be within the scope of the disclosure.
Claims (15)
1. A quantum dot material comprising a plurality of quantum dots, wherein the quantum dots comprise a quantum dot body, a first ligand formed on the quantum dot body by a coordinate bond, a second ligand formed on the quantum dot body by a coordinate bond, the first ligand having one of an acidic property and an alkaline property, the second ligand being capable of forming a third ligand having the other of the acidic property and the alkaline property after being subjected to a predetermined condition, wherein a salt formation reaction is capable of occurring between the first ligand and the third ligand, and a solubility of the quantum dot in a predetermined solvent in which the salt formation reaction occurs is different from a solubility of the quantum dot comprising the first ligand and the second ligand in a predetermined solvent;
the second ligand is an acid generating ligand, so that the third ligand has acidity, and the second ligand at least comprises an acid generating group, wherein the acid generating group is selected from any one of a diazonaphthoquinone group, a phenolic hydroxyl group containing an electron withdrawing group as a protecting group and a triazine group;
the acid generating group is selected from any one of the following groups:
the first ligand comprises a first coordination group, a first connecting chain and a basic group, wherein the first coordination group is formed on the quantum dot body through a coordination bond, and the first connecting chain is connected between the first coordination group and the basic group;
the basic group is selected from any one of primary amine, secondary amine and tertiary amine;
the first connecting chain comprises a fatty chain or an aromatic chain;
the first ligand has the following chemical formula:
2. the quantum dot material of claim 1, wherein the first ligand has an alkaline character and the third ligand has an acidic character.
3. The quantum dot material of claim 2, wherein the predetermined condition is treatment with light having a predetermined wavelength.
4. The quantum dot material of claim 3, wherein the second ligand further comprises a second coordinating group formed on the quantum dot body by a coordination bond, a second linking chain connected between the acid generating group and the second coordinating group, the acid generating group capable of generating hydrogen ions upon irradiation with light of the predetermined wavelength.
5. The quantum dot material of claim 4, wherein the second linking chain comprises a fatty chain or an aromatic chain.
6. The quantum dot material of claim 4, wherein the second coordinating group is selected from any one of thiol, amino, carboxyl.
7. The quantum dot material of any one of claim 6, wherein the second ligand has the formula:
8. the quantum dot material of any one of claim 1, wherein the number of first ligands on the quantum dot body is not less than the number of second ligands.
9. The quantum dot material of any one of claims 1 to 8, wherein the quantum dot further comprises an alkyl chain ligand formed on the quantum dot body by a coordination bond, and the number of carbon atoms in the alkyl chain ligand is not less than 8.
10. The quantum dot material of any one of claims 1 to 8, wherein the number of carbon atoms in at least one of the first ligand and the second ligand is not less than 8.
11. A method for fabricating a quantum dot light emitting device, the method comprising:
providing an initial substrate;
forming a pattern including a quantum dot light emitting layer corresponding to at least one color, wherein the forming a pattern including a quantum dot light emitting layer corresponding to at least one color includes:
coating a quantum dot solution on an initial substrate to obtain a quantum dot solution layer, wherein the solute of the quantum dot solution is the quantum dot material according to any one of claims 1 to 10;
processing a preset position on the quantum dot solution layer by using preset processing conditions so that a second ligand at the preset position forms a third ligand;
developing the quantum dot solution layer processed by the preset processing conditions to obtain a pattern of the quantum dot luminescent layer comprising the luminescent device.
12. The method of claim 11, wherein developing the quantum dot solution layer treated with the preset treatment conditions comprises:
applying the preset solvent to the quantum dot solution layer treated by the preset treatment conditions, so that the first ligand and the third ligand of the quantum dot treated by the preset conditions react to generate salt, and the polarity of the preset solvent is the same as that of the quantum dot subjected to the salt generation reaction;
and dissolving the quantum dots which are at the preset positions and generate salt reaction by using the preset solvent, and obtaining a pattern of the quantum dot luminescent layer comprising the luminescent device.
13. The method of claim 11, wherein developing the quantum dot solution layer treated with the preset treatment conditions comprises:
applying the preset solvent to the quantum dot solution layer treated by the preset treatment conditions, so that the first ligand and the third ligand of the quantum dot treated by the preset conditions react to generate salt, and the polarity of the preset solvent is the same as that of the quantum dot subjected to the salt generation reaction;
and developing the part except the preset position on the quantum dot solution layer by using a developing solution to remove the part except the preset position on the quantum dot solution layer, wherein the polarity of the developing solution is different from that of the quantum dot subjected to salt forming reaction.
14. The method of any one of claims 11 to 13, wherein the predetermined processing condition is irradiation with light having a predetermined wavelength.
15. A quantum dot light emitting device comprising at least one quantum dot light emitting diode comprising a quantum dot light emitting layer, characterized in that the material of the quantum dot light emitting layer is the quantum dot material according to any one of claims 1 to 10, or the quantum dot light emitting layer is a product of the quantum dot material according to any one of claims 1 to 10 after the quantum dot material is subjected to the preset condition and concurrently subjected to a salt reaction.
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