CN112410932B - Nano material and preparation method thereof - Google Patents

Nano material and preparation method thereof Download PDF

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CN112410932B
CN112410932B CN201910769615.3A CN201910769615A CN112410932B CN 112410932 B CN112410932 B CN 112410932B CN 201910769615 A CN201910769615 A CN 201910769615A CN 112410932 B CN112410932 B CN 112410932B
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zinc
zinc sulfide
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sulfur
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CN112410932A (en
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吴劲衡
吴龙佳
何斯纳
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TCL Technology Group Co Ltd
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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    • H10K50/00—Organic light-emitting devices
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    • 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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    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
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Abstract

The invention belongs to the technical field of panel display, and particularly relates to a nano material, a preparation method thereof and a quantum dot light-emitting diode. The preparation method of the nano material provided by the invention comprises the following steps: dissolving a zinc precursor and a polymer in a solvent to prepare a spinning solution; spinning the spinning solution to prepare zinc precursor fiber; dispersing zinc precursor fibers in a sulfur precursor solution, drying, and performing high-temperature sintering treatment in an inert gas atmosphere to prepare zinc sulfide nanofibers; dispersing zinc sulfide nanofibers in a solvent, adding mercaptan, mixing uniformly, and carrying out heating reaction to prepare the mercaptan surface modified zinc sulfide nanofibers. The nano material has the characteristic of slender fiber and staggered appearance, and the surface of the nano material is bonded and connected with a thiol ligand, so that the electron transmission efficiency of zinc sulfide as a QLED electron transmission layer can be effectively improved.

Description

Nano material and preparation method thereof
Technical Field
The invention belongs to the technical field of panel display, and particularly relates to a nano material and a preparation method thereof.
Background
Quantum Dot Light Emitting Diodes (QLEDs) are an electroluminescent device, and have advantages of high luminous efficiency, high color purity, narrow Light emission spectrum, adjustable emission wavelength, and the like, so that the Quantum Dot Light Emitting Diodes (QLEDs) become a new generation of excellent display technology, and the technical level thereof is continuously improved. The optimization of the device structure is a large direction for improving the performance of the QLED, and how to improve the luminous efficiency of the light-emitting layer by optimizing the electron transport layer is the most important link.
Zinc sulfide is a wide band gap semiconductor material, which has a high electron transport matching degree with quantum dot materials and can be used for preparing a QLED electron transport layer, however, the conductivity of zinc sulfide is low, which results in low electron transport efficiency when the zinc sulfide is used as the electron transport layer of the QLED.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a nano material and the nano material obtained by the preparation method, and aims to improve the electron transmission efficiency when zinc sulfide is used as an electron transmission layer of a QLED so as to improve the luminous performance of the QLED.
Another object of the present invention is to provide a quantum dot light emitting diode.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a nano material comprises the following steps:
providing a zinc precursor, a polymer and a solvent, and dissolving the zinc precursor and the polymer in the solvent to prepare a spinning solution;
spinning the spinning solution to prepare zinc precursor fiber;
providing a sulfur precursor solution, dispersing the zinc precursor fiber in the sulfur precursor solution, drying, and performing high-temperature sintering treatment under an inert gas atmosphere to prepare the zinc sulfide nanofiber;
providing mercaptan, dispersing the zinc sulfide nanofiber in the solvent, adding the mercaptan, uniformly mixing, and carrying out heating reaction to prepare the mercaptan surface modified zinc sulfide nanofiber.
According to the preparation method of the nano material, provided by the invention, the zinc sulfide nano fiber is synthesized by combining the technologies of spinning treatment, high-temperature sintering and chemical surface modification, has the characteristics of slender fiber and staggered appearance, and is bonded and connected with mercaptan on the surface, so that the surface of the zinc sulfide nano fiber is provided with a mercapto active group, and the electron cloud density of the material is improved, thereby the electron transmission efficiency of the zinc sulfide nano material when the zinc sulfide nano material is used as an electron transmission layer is improved.
Accordingly, a nanomaterial comprising: thiol surface modified zinc sulfide nanofibers.
The nano material provided by the invention is the mercaptan surface modified zinc sulfide nano fiber, and on one hand, the nano material has the characteristics of slender fiber and staggered network morphology, and is beneficial to electron transmission; on the other hand, the surface of the material is connected with a plurality of thiol ligands, and the thiol ligands are connected with zinc atoms through mercapto groups in a bonding way by coordination bonds, so that electron-donating groups of the network-staggered fiber material can be formed on the surface of the zinc sulfide nano-fibers, the electron cloud density of the material is improved, an electron high-flux channel is formed, the bottleneck effect of electron transmission among the network-staggered fibers is reduced, and the electron transmission efficiency of the zinc sulfide nano-material is improved.
Correspondingly, a quantum dot light emitting diode comprises a cathode and an anode which are oppositely arranged, a quantum dot light emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the quantum dot light emitting layer, wherein the electron transport layer comprises the following materials: the nano material prepared by the preparation method or the nano material.
The electron transport layer of the quantum dot light-emitting diode provided by the invention is made of the nano material prepared by the preparation method, has good electron transport performance, good water solubility, easy film formation and high stability, and can integrally improve the light-emitting performance of the quantum dot light-emitting diode.
Drawings
FIG. 1 is a flow chart of a method for preparing a nanomaterial provided by an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a nanomaterial provided in an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Reference numerals are as follows: the light-emitting diode comprises a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light-emitting layer 4, an electron transport layer 5 and a cathode 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The mass of each component mentioned in the description of the embodiment of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the mass between each component, therefore, it is within the scope of the disclosure of the description of the embodiment of the present invention to scale up or down the content of each component of the composition according to the description of the embodiment of the present invention. Specifically, the mass described in the description of the embodiments of the present invention may be a unit of weight known in the chemical field, such as μ g, mg, g, kg, etc.
Referring to fig. 1, a method for preparing a nano material includes the following steps:
s01, providing a zinc precursor, a polymer and a solvent, and dissolving the zinc precursor and the polymer in the solvent to prepare a spinning solution;
s02, spinning the spinning solution to prepare zinc precursor fiber;
s03, providing a sulfur precursor solution, dispersing the zinc precursor fiber in the sulfur precursor solution, drying, and performing high-temperature sintering treatment in an inert gas atmosphere to prepare the zinc sulfide nanofiber;
and S04, providing mercaptan, dispersing the zinc sulfide nanofiber in the solvent, adding the mercaptan, uniformly mixing, and carrying out heating reaction to prepare the mercaptan surface modified zinc sulfide nanofiber.
According to the preparation method of the nano material provided by the embodiment of the invention, the mercaptan surface modified zinc sulfide nano fiber is synthesized by combining the technologies of spinning treatment, high-temperature sintering and chemical surface modification, has the characteristics of slender fiber and staggered appearance, and is bonded and connected with mercaptan on the surface, so that the surface of the zinc sulfide nano fiber is provided with a mercapto active group, and the electron cloud density of the material is improved, thereby improving the electron transmission efficiency of the zinc sulfide nano material when the zinc sulfide nano material is used as an electron transmission layer.
Specifically, in step S01, the zinc precursor is a precursor material that provides a zinc atom through a reaction, including but not limited to an inorganic substance of zinc or an organic substance of zinc. In some embodiments, the zinc precursor is preferably at least one of zinc chloride, zinc sulfate, zinc acetate, dimethyl zinc, diethyl zinc, and zinc acetylacetonate. The substances can be dissolved in different polar solvents, and are suitable for various polar solvent systems.
In one embodiment, the concentration of the zinc precursor in the spinning solution is 100 to 300mg/mL. When the concentration of the zinc precursor is less than 100mg/mL, after subsequent high-temperature sintering treatment, the zinc sulfide nano-fibers can be directly broken to form nano-rods, nano-particles and the like, and fibrous zinc sulfide nano-materials cannot be formed; when the concentration of the zinc precursor is more than 300mg/mL, the spinning solution is emulsion, and uniform and continuous zinc precursor fibers cannot be formed.
The polymer is an organic macromolecule and is used for promoting the formation of precursor fiber. In some embodiments, the polymer is preferably at least one of polyvinylpyrrolidone (PVP), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), acrylonitrile-styrene-butadiene copolymer (ABS), polymethyl methacrylate (PMMA), ethylene vinyl acetate copolymer (EVA), polyethylene terephthalate (PET), polyamide (PA) and Polyphenylene Sulfide (PPs), and/or a polymerized monomer of at least one of PVP, PE, PP, PVC, ABS, PMMA, EVA, PET, PA, PPs.
The solvent is used to dissolve and disperse the zinc precursor and the polymer to prepare a uniform spinning solution. In some embodiments, the solvent is selected to be an organic solvent that has good solubility for at least the zinc precursor. In some embodiments, the solvent is selected from at least one of ethanol, methanol, N-dimethylformamide, tetrahydrofuran (THF), and Dimethylimides (DMSO).
As an embodiment, the added volume of the polymer is 10% to 30% of the volume of the solvent. Within this ratio range, the polymer can form a uniform solution in the solvent; when the dosage of the polymer is too low, the zinc precursor fiber cannot be formed in the subsequent spinning treatment process; when the amount of the polymer is too high, the spinning solution is liable to be agglomerated.
As an embodiment, the step of dissolving the zinc precursor, the polymer in the solvent includes: completely dissolving the zinc precursor in the solvent to prepare a zinc precursor solution; then, the polymer is added into the zinc precursor solution, and the mixture is stirred until the polymer is uniformly dispersed in the zinc precursor solution.
Specifically, in step S02, the spinning solution is spun to prepare a zinc precursor fiber, so that the zinc sulfide product has a staggered mesh-like morphology. In some embodiments, the spinning process is preferably a gas spinning process, which has the advantages of simplicity, rapidity, low energy consumption and low cost compared with the conventional electrospinning process. In some embodiments, the parameters of the gas spinning process are set as: the flow rate of the spinning solution is set to be 1.5-3.0mL/h, the air pressure is set to be 30-60MPa, and the humidity is set to be 10% -40%.
Specifically, in step S03, the sulfur precursor solution is a solution in which a sulfur precursor is dissolved, and the sulfur precursor is a precursor substance that provides a sulfur atom by a reaction. In some embodiments, the sulfur precursor solution comprises at least one of elemental sulfur, thiourea, and thiazole, preferably elemental sulfur, substantially without introducing impurities. In other embodiments, the sulfur precursor solution uses carbon disulfide as a solvent for dissolving the sulfur precursor. In still other embodiments, the concentration of sulfur precursor in the sulfur precursor solution is from 100 to 200mg/mL.
In one embodiment, the molar ratio of the sulfur atoms in the sulfur precursor solution to the zinc atoms in the zinc precursor fibers is (1-2): 1, preferably 1.5. When the molar ratio of sulfur atoms in the sulfur precursor solution to zinc atoms in the zinc precursor fiber is less than 1; when the molar ratio of the sulfur in the sulfur precursor solution to the zinc in the zinc precursor fiber is greater than 2.
And dispersing the zinc precursor fiber into the sulfur precursor solution, and drying to ensure that the sulfur precursor is attached to the surface of the zinc precursor fiber in the drying process, thereby promoting the subsequent preparation of the zinc sulfide nanofiber. In some embodiments, the step of dispersing the zinc precursor fibers in the sulfur precursor solution comprises: and mixing and stirring the zinc precursor and the sulfur precursor solution. In other embodiments, the temperature of the drying is less than 300 ℃, e.g., 100 ℃, to completely remove the solvent of the sulfur precursor solution.
The high-temperature sintering treatment is carried out in the inert gas atmosphere, so that the zinc precursor fiber and the sulfur precursor can be ensured to react to generate the zinc sulfide nanofiber, and the generation of other byproducts, such as zinc oxide, can be avoided.
In some embodiments, the temperature of the high-temperature sintering is preferably 300-500 ℃, and the high-temperature sintering is performed in the temperature range, so that the overall performance of the zinc sulfide nanofiber prepared by the method in the embodiment of the invention can be optimized. Furthermore, the high-temperature sintering time is 0.5-1 hour, so that the material is completely sintered, and the agglomeration of particles caused by overlong time is effectively avoided. In one embodiment, the high temperature sintering process comprises: heating from room temperature to 300-500 deg.c at the rate of 2-5 deg.c/min, and sintering for 0.5-1 hr.
As an embodiment, after the step of subjecting the precursor fiber to the high-temperature sintering treatment, the high-temperature sintered product is cooled to room temperature, and then ground to have a suitable length, for example, a fiber length of 10 to 100 μm.
In one embodiment, the inert gas is preferably argon and/or helium.
Specifically, in step S04, the thiol serves as a ligand for surface modification of the zinc sulfide nanofiber. Wherein the thiol is an organic compound containing a mercapto group (-SH). In some embodiments, the thiol has the structure of R-SH, wherein R is preferably a hydrocarbyl group having a carbon number of 1 to 8. It is understood that hydrocarbyl refers to groups containing only two atoms of carbon and hydrogen, including but not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like.
In one embodiment, the molar ratio of the thiol group of the thiol to the zinc atom in the zinc sulfide nanofiber is (0.01-0.1): 1. When the molar ratio of the sulfydryl to the zinc atoms is less than 0.01; when the molar ratio of the mercapto group to the zinc atom is more than 0.1, the polarity of the surface of the zinc sulfide nanofiber is easily changed, the zinc sulfide nanofiber is easily agglomerated, and the film forming property and the electron transport property of the electron transport layer material are reduced.
Dispersing the zinc sulfide nanofibers in the solvent, and adding the mercaptan, so that the mercaptan is in full contact with the zinc sulfide nanofibers, wherein the solvent is the solvent adopted in the step S01.
And uniformly mixing the mercaptan and the zinc sulfide nano-fibers, and carrying out heating reaction to ensure that the mercaptan is bonded and connected with zinc atoms of the zinc sulfide nano-fibers so as to realize surface modification of the zinc sulfide nano-fibers. Further, the temperature of the heating reaction is 75-85 ℃. In some embodiments, the heating is for a time of 2 hours or more until the thiol is sufficiently reacted. In other embodiments, the heating reaction is carried out with mixing with stirring.
Under the comprehensive action of the optimized condition parameters such as the molar ratio, the concentration, the temperature, the time and the like of the raw materials, the comprehensive performance of the material for the electron transport layer obtained by the preparation method provided by the embodiment of the invention can be optimized.
Accordingly, a nanomaterial prepared by the above preparation method, the nanomaterial comprising: thiol surface modified zinc sulfide nanofibers.
The nano material provided by the embodiment of the invention is the mercaptan surface modified zinc sulfide nano fiber, and on one hand, the nano material has the characteristics of slender fiber and staggered network appearance, and is beneficial to electron transmission; on the other hand, the surface of the material is connected with a plurality of mercaptan ligands, the mercaptan ligands are connected with zinc atoms through mercapto groups in a bonding mode through coordination bonds, electron-donating groups of the fiber material with staggered networks can be formed on the surface of the zinc sulfide nano fiber, the electron cloud density of the material is improved, an electron high-flux channel is formed, the bottleneck effect of electron transmission among the fibers with staggered networks is reduced, and therefore the electron transmission efficiency of the zinc sulfide nano material is improved.
Specifically, the nanomaterial is a zinc sulfide nanofiber with a thiol surface modified, as shown in fig. 2, the surface of the nanomaterial is connected with a thiol ligand, and the thiol ligand is bonded and connected with a zinc atom on the surface of zinc sulfide through a coordination bond. Due to the slender characteristic and the staggered appearance of the fiber and the sulfydryl active groups on the surface of the zinc sulfide fiber, compared with zinc sulfide nanoparticles, the electron transmission efficiency of the mercaptan surface modified zinc sulfide nanofiber is greatly improved. In some embodiments, the thiol ligand attached to the surface of the zinc sulfide nanofiber is a thiol compound containing a thiol group (-SH). In some embodiments, the thiol has the structure of R-SH, wherein R is preferably a hydrocarbyl group having a carbon number of 1 to 8. It is understood that hydrocarbyl refers to a group containing only two atoms of carbon and hydrogen, including but not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like.
According to one embodiment, the molar ratio of the sulfydryl to the zinc atoms in the mercaptan surface modified zinc sulfide nanofiber is (0.01-0.1): 1. When the molar ratio of sulfydryl to zinc atoms is less than 0.01; when the molar ratio of the sulfydryl to the zinc atoms is more than 0.1.
In one embodiment, the thiol surface-modified zinc sulfide nanofibers have a diameter of 5 to 10nm and a length of 10 to 100 μm. The zinc oxide nano fiber in the specification range can be prepared by adopting solution, is well dispersed in a solvent and is beneficial to film formation.
Correspondingly, a quantum dot light emitting diode comprises a cathode and an anode which are oppositely arranged, a quantum dot light emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the quantum dot light emitting layer, wherein the electron transport layer comprises the following materials: the electron transport layer material or the electron transport layer material prepared by the preparation method.
The quantum dot light-emitting diode provided by the embodiment of the invention has the advantages that the electron transport layer material comprises the electron transport layer material prepared by the preparation method, the electron transport layer material has good electron transport performance, the water solubility is good, the film is easy to form, the stability is high, and the light-emitting performance of the quantum dot light-emitting diode can be integrally improved.
In one embodiment, the thickness of the electron transport layer is 10 to 100nm, preferably 50nm.
Quantum dot light emitting diode all includes the positive pole, the quantum dot luminescent layer, electron transport layer and the negative pole that stack gradually the setting, can understand, except above-mentioned quantum dot luminescent layer and electron transport layer, quantum dot light emitting diode can also include other membranous layer structures, for example: a substrate, a hole injection layer, a hole transport layer, an electron injection layer, and the like. In some embodiments, the quantum dot light emitting diode may have a positive type structure and may also have an inversion type structure, wherein the positive type structure and the inversion type structure are different from each other mainly by: an anode of a positive structure is connected with the substrate and is used as a bottom electrode to be arranged on the surface of the substrate in a laminated mode; the cathode of the inversion structure is connected with the substrate, and is used as a bottom electrode to be stacked on the surface of the substrate.
In some embodiments, the quantum dot light emitting diode is a positive type structure, as shown in fig. 3, and includes a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5, and a cathode 6, which are sequentially stacked. The quantum dot material of the quantum dot light-emitting layer is one of red, green and blue quantum dot materials, and has the characteristics of wide and continuous distribution of an excitation spectrum, high stability of an emission spectrum and the like. Can be at least one of CdS, cdSe, cdTe, znO, znS, znSe, znTe, gaAs, gaP, gaSb, hgS, hgSe, hgTe, inAs, inP, inSb, alAs, alP, cuInS, cuInSe and various core-shell structure quantum dots or alloy structure quantum dots.
Correspondingly, the embodiment of the invention also provides a preparation method of the quantum dot light-emitting diode, which comprises the following steps:
1) Providing a substrate, and depositing an anode, a hole transport layer and a quantum dot light emitting layer on the substrate in sequence;
2) The mercaptan surface modified zinc sulfide nanofiber prepared by the method is used as an electron transport layer material and is deposited on the quantum dot light-emitting layer, and then a cathode is evaporated on the electron transport layer to obtain the quantum dot light-emitting diode.
Further, the obtained QLED is subjected to a packaging process, and the packaging process may be performed by a common machine or by a manual method. In some embodiments, the packaging process environment has an oxygen content and a water content of less than 0.1ppm to ensure device stability.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art, and to make the progress of the nanomaterial and the method for preparing the same apparent from the embodiments of the present invention, the implementation of the present invention is illustrated by the following examples.
Example 1
The embodiment prepares an electron transport layer material, which is thiol surface modified zinc sulfide nanofiber prepared by using butanethiol as a ligand, and the specific process flow is as follows:
s11, dissolving zinc sulfate powder in ethanol to prepare a zinc precursor solution with the concentration of 200 mg/mL; then, adding PVP (polyvinyl pyrrolidone) accounting for about 20% of the volume of the ethanol into the zinc precursor solution, and stirring to uniformly disperse the PVP into the zinc precursor solution to prepare a spinning solution;
s12, spinning the spinning solution by adopting a gas spinning method to obtain cotton-shaped flocks and obtain zinc precursor fibers;
s13, dissolving sulfur powder in carbon disulfide to prepare a sulfur precursor solution with the concentration of 150 mg/mL; uniformly dispersing zinc precursor fibers in a sulfur precursor solution, enabling the molar ratio of zinc of the zinc precursor fibers to sulfur of the sulfur precursor to be 1.5, then drying, placing the dried product in an argon atmosphere, calcining at 350 ℃ for 2 hours, naturally cooling the high-temperature sinter to room temperature, grinding to enable the length of the fibers to be 10-100 mu m and the diameter to be 5-10nm, and obtaining zinc sulfide nanofibers with the shape of a staggered network;
s14, re-dispersing the zinc sulfide nanofibers in ethanol, heating to 80 ℃, adding butanethiol, enabling the molar ratio of zinc to thiol of the zinc sulfide nanofibers to be 1.05, stirring for reaction, filtering reaction liquid after the reaction is finished, and drying to obtain the thiol surface modified zinc sulfide nanofibers.
And (3) taking the prepared mercaptan surface modified zinc sulfide nano-fiber as a QLED electron transport layer material to prepare the QLED luminescent device A. QLED luminescent device A is positive type structure, including positive pole, hole transport layer, luminescent layer, electron transport layer, negative pole, the anode material is the ITO electrode, the hole transport layer material is nickel oxide, the luminescent layer is CdSe @ ZnS green quantum dot, the negative pole is Al.
Example 2
The embodiment prepares an electron transport layer material, which is thiol surface modified zinc sulfide nanofiber prepared by using hexanethiol as a ligand, and the specific process flow is as follows:
s21, dissolving zinc chloride powder in ethanol to prepare a zinc precursor solution with the concentration of 200 mg/mL; then, adding PVC which accounts for about 20% of the volume of the ethanol into the zinc precursor solution, and stirring to uniformly disperse the PVC in the zinc precursor solution to prepare a spinning solution;
s22, spinning the spinning solution by adopting a gas spinning method to obtain cotton-shaped floccules and obtain zinc precursor fibers;
s23, dissolving sulfur powder in carbon disulfide to prepare a sulfur precursor solution with the concentration of 150 mg/mL; uniformly dispersing zinc precursor fibers in a sulfur precursor solution, enabling the molar ratio of zinc of the zinc precursor fibers to sulfur of the sulfur precursor to be 1;
s24, re-dispersing the zinc sulfide nanofibers in ethanol, heating to 80 ℃, adding butanethiol, enabling the molar ratio of zinc to thiol of the zinc sulfide nanofibers to be 1.05, stirring for reaction, filtering reaction liquid after the reaction is finished, and drying to obtain the thiol surface modified zinc sulfide nanofibers.
And (3) taking the prepared mercaptan surface modified zinc sulfide nano-fiber as a QLED electron transport layer material to prepare a QLED luminescent device B. QLED luminescent device B is just putting type structure, including positive pole, hole transport layer, luminescent layer, electron transport layer, negative pole, the anode material is the ITO electrode, hole transport layer material is nickel oxide, the luminescent layer is CdSe @ ZnS green quantum dot, the negative pole is Al.
Example 3
The embodiment prepares an electron transport layer material, which is thiol surface modified zinc sulfide nanofiber prepared by using octyl thiol as a ligand, and the specific process flow is as follows:
s31, dissolving zinc nitrate hexahydrate powder in methanol to prepare a zinc precursor solution with the concentration of 300mg/mL; then, PVP which accounts for about 30% of the volume of the methanol is added into the zinc precursor solution, and the mixture is stirred to enable the PVP to be uniformly dispersed in the zinc precursor solution to prepare a spinning solution;
s32, spinning the spinning solution by adopting an air spinning method to obtain cotton-shaped flocks and obtain zinc precursor fibers;
s33, dissolving sulfur powder in carbon disulfide to prepare a sulfur precursor solution with the concentration of 150 mg/mL; uniformly dispersing zinc precursor fibers in a sulfur precursor solution, enabling the molar ratio of zinc of the zinc precursor fibers to sulfur of the sulfur precursor to be 1;
s34, re-dispersing the zinc sulfide nanofibers in ethanol, heating to 80 ℃, adding butanethiol, enabling the molar ratio of zinc to thiol of the zinc sulfide nanofibers to be 1.05, stirring for reaction, filtering reaction liquid after the reaction is finished, and drying to obtain the thiol surface modified zinc sulfide nanofibers.
And (3) taking the prepared mercaptan surface modified zinc sulfide nano-fiber as a QLED electron transport layer material to prepare a QLED light-emitting device C. QLED luminescent device C is the inversion type structure, including positive pole, hole transport layer, luminescent layer, electron transport layer, negative pole, the anode material is the Al electrode, the hole transport layer material is nickel oxide, the luminescent layer is CdSe @ ZnS green quantum dot, the negative pole is the ITO base plate.
Comparative example 1
1. Dissolving zinc sulfate powder in ethanol to prepare a zinc precursor solution;
2. dissolving sulfur powder in carbon disulfide to prepare a sulfur precursor solution;
3. mixing a zinc precursor solution and a sulfur precursor solution to ensure that the molar ratio of zinc to sulfur is 1; stirring the mixed solution at 80 ℃ for 4 hours to obtain uniform and transparent reaction solution; then, after the reaction solution is cooled, ethyl acetate is used for separation, after centrifugation, a small amount of ethanol is used for fully washing for 3 times, and the ZnS nano-particles are prepared through drying;
and (3) taking the prepared zinc sulfide nanoparticles as a material of the QLED electron transmission layer to prepare the QLED light-emitting device D.
Comparative example 2
This comparative example differs from example 2 in that: step S24 is omitted, and a QLED light-emitting device E is prepared;
the rest of the process is basically the same as that of embodiment 2, and the description thereof is omitted.
Comparative example 3
This comparative example differs from example 3 in that: step S34 is omitted, and a QLED light-emitting device F is prepared;
the rest of the process is basically the same as that of embodiment 3, and the description thereof is omitted.
The electron transport films prepared in examples 1 to 3, the electron transport films in comparative examples 1 to 3, and the quantum dot light emitting diodes were subjected to performance tests, and the test indexes and the test methods were as follows:
(1) Electron mobility: testing the current density (J) -voltage (V) of the quantum dot light emitting diode, drawing a curve relation diagram, fitting a Space Charge Limited Current (SCLC) area in the relation diagram, and then calculating the electron mobility according to a well-known Child's law formula:
J＝(9/8)ε r ε 0 μ e V 2 /d 3
wherein J represents current density in mAcm -2 ；ε r Denotes the relative dielectric constant,. Epsilon 0 Represents the vacuum dielectric constant; mu.s e Denotes the electron mobility in cm 2 V -1 s -1 (ii) a V represents the drive voltage, in units of V; d represents the film thickness in m.
(2) Resistivity: the resistivity of the electron transport film is measured by the same resistivity measuring instrument.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
Note: the electron mobility and resistivity are tested as single-layer thin film structure devices, namely: cathode/electron transport film/anode. The external quantum efficiency test is the QLED device, namely: anode/hole transport film/quantum dot/electron transport film/cathode, or cathode/electron transport film/quantum dot/hole transport film/anode.
The test results are shown in table 1 below:
TABLE 1
Figure BDA0002173134790000131
As can be seen from table 1 above, examples 1 to 3 of the present invention provide materials having significantly lower resistivity than the electron transport thin films made of nanomaterials in comparative examples 1 to 3, and significantly higher electron mobility than the electron transport layer materials in comparative examples 1 to 3, and significantly higher EQE than the quantum dot light emitting diode devices in comparative examples 1 to 3.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (11)

1. The preparation method of the nano material is characterized by comprising the following steps of:
providing a zinc precursor, a polymer and a solvent, and dissolving the zinc precursor and the polymer in the solvent to prepare a spinning solution; wherein, in the spinning solution, the concentration of the zinc precursor is 100-300mg/mL;
spinning the spinning solution to prepare zinc precursor fiber;
providing a sulfur precursor solution, dispersing the zinc precursor fiber in the sulfur precursor solution according to the proportion that the molar ratio of sulfur atoms in the sulfur precursor solution to zinc atoms in the zinc precursor fiber is (1-2): 1, drying, and performing high-temperature sintering treatment in an inert gas atmosphere, wherein the zinc precursor fiber reacts with the sulfur precursor to prepare the zinc sulfide nanofiber;
providing mercaptan, dispersing the zinc sulfide nanofibers in the solvent, adding the mercaptan, uniformly mixing the zinc sulfide nanofibers and the mercaptan in the solvent according to the molar ratio of (0.01-0.1) to 1 of the mercapto group of the mercaptan to the zinc atoms in the zinc sulfide nanofibers, and carrying out heating reaction to prepare the mercaptan surface modified zinc sulfide nanofibers.
2. The method of claim 1, wherein the polymer is added in an amount of 10 to 30% by volume based on the volume of the solvent in the step of preparing the spinning solution.
3. The method according to claim 1, wherein the step of subjecting the spinning solution to a spinning treatment employs a gas spinning method.
4. The preparation method according to claim 1, wherein in the step of preparing the zinc sulfide nanofibers, the temperature of the high-temperature sintering treatment is 300-500 ℃; and/or
In the step of preparing the mercaptan surface modified zinc sulfide nanofiber, the heating reaction temperature is 75-85 ℃.
5. The production method according to any one of claims 1 to 4, characterized in that, after the step of high-temperature sintering treatment under an inert atmosphere, the zinc sulfide nanofibers are ground until the length of the zinc sulfide nanofibers is 10-100 μm.
6. The production method according to any one of claims 1 to 4, wherein the zinc precursor includes at least one of zinc chloride, zinc sulfate, zinc acetate, dimethyl zinc, diethyl zinc, and zinc acetylacetonate; and/or
The sulfur precursor solution contains at least one of elemental sulfur, thiourea and thiazole; and/or
The thiol is selected from mercapto compounds with carbon number of 1-8.
7. A nanomaterial manufactured by the manufacturing method of any one of claims 1 to 6, comprising: thiol surface modified zinc sulfide nanofibers.
8. The nanomaterial according to claim 7, wherein the molar ratio of the mercapto group to the zinc atom of the thiol in the thiol surface-modified zinc sulfide nanofiber is (0.01-0.1): 1.
9. Nanomaterial according to claim 7, characterized in that the thiol surface-modified zinc sulphide nanofibres have a diameter of 5-10nm and a length of 10-100 μm.
10. A quantum dot light emitting diode comprising a cathode and an anode disposed opposite to each other, a quantum dot light emitting layer disposed between the cathode and the anode, and an electron transport layer disposed between the cathode and the quantum dot light emitting layer, wherein the electron transport layer is made of a material comprising: nanomaterial produced by the production method according to any one of claims 1 to 6 or nanomaterial according to any one of claims 7 to 9.
11. The quantum dot light-emitting diode of claim 10, wherein the electron transport layer has a thickness of 10-100nm.
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