CN112410933B - Nano material and preparation method thereof and quantum dot light-emitting diode - Google Patents

Nano material and preparation method thereof and quantum dot light-emitting diode Download PDF

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CN112410933B
CN112410933B CN201910769636.5A CN201910769636A CN112410933B CN 112410933 B CN112410933 B CN 112410933B CN 201910769636 A CN201910769636 A CN 201910769636A CN 112410933 B CN112410933 B CN 112410933B
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phosphorus
precursor
nickel
quantum dot
nickel oxide
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CN112410933A (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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    • D—TEXTILES; PAPER
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • 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
    • 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

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: providing a nickel precursor, a phosphorus precursor, a polymer and a solvent, and dissolving the nickel precursor, the phosphorus precursor and the polymer in the solvent to prepare a spinning solution; spinning the spinning solution to prepare precursor fiber; and (3) carrying out high-temperature sintering treatment on the precursor fiber in an oxygen-containing atmosphere to obtain the phosphorus-doped nickel oxide nanofiber. The nickel oxide nanofiber is synthesized by combining spinning treatment and high-temperature sintering technologies, has the characteristics of slender fibers and staggered morphology, and is synchronously subjected to phosphorus doping modification in the synthesis process, so that the electron transmission efficiency of the nickel oxide nanomaterial is greatly improved.

Description

Nano material and preparation method thereof and quantum dot light-emitting diode
Technical Field
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.
Background
Quantum Dot Light Emitting Diodes (QLEDs) are an electroluminescent device, and have the advantages of high luminous efficiency, high color purity, narrow Light emission spectrum, adjustable emission wavelength, and the like, so that they are a new generation of excellent display technology. At present, the main problems limiting the large-scale commercial application of the QLED are that the lifetime of the device is low and the stability is poor, and the most important problem is that the hole transport efficiency in the device structure is too low to balance with the electron transport efficiency, which affects the effective recombination of the hole and the electron in the quantum dot light emitting layer.
The nanometer material of the QLED comprises organic polymer and metal oxide, and compared with the organic polymer, the metal oxide has better stability, does not corrode an ITO substrate, is beneficial to preparing the QLED with longer service life, and is commonly used for preparing a hole injection layer and/or a hole transmission layer of the QLED. However, the hole mobility of metal oxides is lower than that of organic polymers, and device stability and hole transport performance cannot be both achieved. Therefore, it is a research focus of those skilled in the art to provide a nanomaterial having high hole transport efficiency.
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 hole transmission efficiency of the existing metal oxide nano material.
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 nickel precursor, a phosphorus precursor, a polymer and a solvent, and dissolving the nickel precursor, the phosphorus precursor and the polymer in the solvent to prepare a spinning solution;
spinning the spinning solution to prepare precursor fiber;
and (3) carrying out high-temperature sintering treatment on the precursor fiber in an oxygen-containing atmosphere to obtain the phosphorus-doped nickel oxide nanofiber.
According to the preparation method of the nano material, provided by the invention, the nickel oxide nano fiber is synthesized by combining spinning treatment and high-temperature sintering technologies, has the characteristics of slender fiber and staggered appearance, and phosphorus atoms replace part of oxygen sites of nickel oxide in the synthesis process, so that phosphorus doping modification of nickel oxide is synchronously realized, the electron transmission efficiency of the nickel oxide nano material is greatly improved, and the preparation method is simple, easy and convenient to operate, easy to control, safe and stable.
Accordingly, a nanomaterial comprising: phosphorus doped nickel oxide nanofibers.
The nano material provided by the invention is a phosphorus-doped nickel oxide nano fiber, on one hand, phosphorus atoms replace part of oxygen sites of nickel oxide to form p-type doping, more hole sites can be provided, and the hole mobility of the material is improved, on the other hand, the phosphorus atoms replacing the oxygen sites on the surface of the nickel oxide nano fiber can become hole activation sites when the zinc oxide nano fiber forms a film layer and serve as a bridge for hole migration in the film layer, and the hole transmission flux between the nickel oxide nano fibers is improved; meanwhile, the phosphorus-doped nickel oxide nanofiber has the characteristic of slender fibers, so that the transmission of charges in a transmission film layer is facilitated, and the hole transmission efficiency of the nano material is effectively 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 a hole transport layer arranged between the anode and the quantum dot light emitting layer, wherein the material of the hole transport layer comprises: the nano material prepared by the preparation method or the nano material.
According to the quantum dot light-emitting diode provided by the invention, the hole transport layer material comprises the nano material prepared by the preparation method, the hole transport layer material has good hole transport performance, good water solubility, easy film formation and high stability, and the light-emitting performance of the quantum dot light-emitting diode can be integrally improved.
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 nano material 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: 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 the nano material includes the following steps:
s01, providing a nickel precursor, a phosphorus precursor, a polymer and a solvent, and dissolving the nickel precursor, the phosphorus precursor and the polymer in the solvent to prepare a spinning solution;
s02, spinning the spinning solution to prepare precursor fiber;
and S03, sintering the precursor fiber at high temperature in an oxygen-containing atmosphere to obtain the phosphorus-doped nickel oxide nanofiber.
According to the preparation method of the nano material provided by the embodiment of the invention, the nickel oxide nano fiber is synthesized by combining spinning treatment and high-temperature sintering technologies, has the characteristics of slender fiber and staggered appearance, and phosphorus atoms replace part of oxygen sites of nickel oxide in the synthesis process, so that phosphorus doping modification of nickel oxide is synchronously realized, the electron transmission efficiency of the nickel oxide nano material is greatly improved, and the preparation method is simple, easy and convenient to operate, easy to control, safe and stable.
Specifically, in step S01, the nickel precursor is a precursor material that provides nickel atoms through reaction, including but not limited to inorganic nickel or organic nickel. In some embodiments, the nickel precursor is preferably at least one of nickel nitrate, nickel sulfate, nickel acetate, and nickel bromide.
As an embodiment, the concentration of the nickel precursor in the prepared spinning solution is 100 to 300mg/mL. When the concentration of the nickel precursor is less than 100mg/mL, precursor fibers can be directly broken to form nanorods, nanoparticles and the like after subsequent high-temperature sintering treatment, and fibrous nickel oxide nano materials cannot be formed; when the concentration of the nickel precursor is more than 300mg/mL, the spinning solution is emulsion, and uniform and continuous precursor fibers cannot be formed.
The phosphorus precursor is a phosphorus-containing compound and is used for realizing phosphorus doping modification of nickel oxide in the high-temperature sintering treatment process. In some embodiments, the phosphorus precursor is preferably at least one of elemental phosphorus, trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO), facilitating reaction in solution.
In one embodiment, in the step of preparing the spinning solution, the phosphorus precursor and the nickel precursor are dissolved in the solvent in such a ratio that the molar ratio of the phosphorus atoms in the phosphorus precursor to the nickel atoms in the nickel precursor is (0.005-0.01): 1. When the molar ratio of the phosphorus atoms to the nickel atoms is less than 0.005; when the molar ratio of phosphorus atoms to nickel atoms is greater than 0.01.
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 the nickel precursor, the phosphorus 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 nickel precursor and the phosphorus precursor. In some embodiments, the solvent is selected from at least one of ethanol, N-dimethylformamide, tetrahydrofuran (THF), and Dimethylsulfoxide (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 amount of the polymer is too low, a precursor fiber cannot be formed in the spinning treatment process; when the amount of the polymer is too high, the spinning solution is liable to be agglomerated.
As one embodiment, the step of dissolving the nickel precursor, the phosphorus precursor, and the polymer in the solvent includes: completely dissolving the nickel precursor and the phosphorus precursor in the solvent to obtain a mixed solution; then, the polymer is added to the mixed solution, and the mixture is stirred until the polymer is uniformly dispersed.
Specifically, in step S02, the spinning solution is subjected to a spinning process to prepare a precursor fiber, so that the nickel oxide 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 precursor fiber is subjected to high-temperature sintering treatment in an oxygen-containing atmosphere, the oxygen-containing atmosphere is used for providing oxygen, during the high-temperature sintering process, the nickel precursor reacts in the oxygen-containing atmosphere to generate nickel oxide grains, and meanwhile, phosphorus replaces oxygen sites of part of the nickel oxide grains to form p-type doping, so as to realize phosphorus doping modification of the nickel oxide.
In some embodiments, the high-temperature sintering temperature is preferably 300-500 ℃, and the high-temperature sintering is performed in the temperature range, so that the comprehensive performance of the aminated nickel oxide 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.
In one embodiment, the precursor fiber is dried before the step of subjecting the precursor fiber to the high-temperature sintering treatment.
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 and a diameter of 5 to 10nm.
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 nano material obtained by the preparation method provided by the embodiment of the invention can be optimized.
Accordingly, a nanomaterial manufactured by the above manufacturing method, the nanomaterial comprising: phosphorus doped nickel oxide nanofibers.
The nano material provided by the embodiment of the invention is phosphorus-doped nickel oxide nano fiber, on one hand, phosphorus atoms replace part of oxygen sites of nickel oxide to form p-type doping, so that more hole sites can be provided, and the hole mobility of the material is improved, and on the other hand, the phosphorus atoms replacing the oxygen sites on the surface of the nickel oxide nano fiber can become hole activation sites when zinc oxide nano fiber forms a film layer and serve as a bridge for hole migration in the film layer, so that the hole transmission flux between the nickel oxide nano fibers is improved; meanwhile, the phosphorus-doped nickel oxide nanofiber has the characteristic of slender fiber, so that the transmission of holes in a transmission film layer is facilitated, and the hole transmission efficiency of the nano material is effectively improved.
Specifically, the nano material is a phosphorus-doped nickel oxide nanofiber, which is a nanofiber material, and as shown in fig. 2, the nano material has the characteristics of slender fibers and staggered morphology. Meanwhile, the doped P atoms replace part of oxygen atoms in the nickel oxide nano fibers to form P-type doping, so that more hole sites are provided, and the P atoms on the surface of the zinc oxide nano fibers replacing the oxygen sites can be used as a bridge for hole migration in the film layer, so that the hole transmission flux between the nano fibers is effectively improved. Compared with the undoped modified nickel oxide nanofiber, the hole transmission efficiency of the phosphorus-doped nickel oxide nanofiber provided by the embodiment of the invention is greatly improved.
In one embodiment, the phosphorus-doped nickel oxide nanofibers have a molar ratio of phosphorus atoms to nickel atoms of (0.005-0.01): 1. When the molar ratio of phosphorus atoms to nickel atoms is less than 0.005; when the molar ratio of phosphorus atoms to nickel atoms is greater than 0.01.
In one embodiment, the phosphorus-doped nickel oxide nanofibers have a diameter of 5 to 10nm and a length of 10 to 100 μm. The nickel 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 a hole transport layer arranged between the anode and the quantum dot light emitting layer, wherein the material of the hole transport layer comprises: the nano material or the nano material prepared by the preparation method.
According to the quantum dot light-emitting diode provided by the embodiment of the invention, the hole transport layer comprises the nano material prepared by the preparation method, the quantum dot light-emitting diode has good electron transport performance, good water solubility, easy film formation and high stability, and the light-emitting performance of the quantum dot light-emitting diode can be integrally improved.
In one embodiment, the hole transport layer has a thickness of 10 to 100nm, preferably 50nm.
In some embodiments, the quantum dot light emitting diode includes an anode, a quantum dot light emitting layer, a hole transport layer, and a cathode, which are sequentially stacked, and it is understood that the quantum dot light emitting diode may include other film layer structures besides the above quantum dot light emitting layer and hole transport layer, for example: a substrate, a hole injection layer, an electron 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 arranged on the surface of the substrate in a laminated mode by taking the anode as a bottom electrode; the cathode of the inverted 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, and referring to fig. 3, the quantum dot light emitting diode 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 on the substrate; then, the phosphorus-doped nickel oxide nanofiber is used as a hole transport layer material and is deposited on the anode to form a hole transport layer; then, depositing a quantum dot luminous layer and an electron transport layer on the hole transport layer in sequence;
2) And (4) evaporating and plating a cathode on the electron transmission 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 operation of the present invention clearly understood by those skilled in the art, and to make the advanced performance of the nanomaterial and the preparation method thereof and the quantum dot light emitting diode according to the embodiment of the present invention obviously apparent, the implementation of the present invention is illustrated by the following embodiments.
Example 1
The embodiment prepares the nano material, and the specific process flow is as follows:
s11, dissolving nickel nitrate in ethanol to prepare a nickel precursor solution with the concentration of 200 mg/mL; subsequently, adding phosphorus powder into the nickel precursor solution so that the molar ratio of nickel to phosphorus is 1; then, adding PP accounting for about 20% of the volume of the ethanol into the mixed solution, and stirring until the PP is uniformly dispersed in the mixed solution to prepare a spinning solution;
s12, spinning the spinning solution by adopting a gas spinning method to obtain cotton-shaped flocks and obtain precursor fibers;
s13, drying the precursor fiber, then sintering the precursor fiber at 400 ℃ for 2 hours at high temperature in an oxygen atmosphere, and then grinding the sintered product to the length of 10-100 mu m and the diameter of 5-10nm after the sintered product is cooled to room temperature to obtain the phosphorus-doped nickel oxide nanofiber with the staggered net-shaped morphology.
And (3) preparing the QLED luminescent device A by using the prepared phosphorus-doped nickel oxide nanofiber as a hole transport layer material. 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 ITO, the electron transport layer material is ZnO, the luminescent layer is CdSe @ ZnS green quantum dot, the negative pole is Al.
Example 2
The embodiment prepares the nano material, and the specific process flow is as follows:
s21, dissolving nickel sulfate in ethanol to prepare a nickel precursor solution with the concentration of 200 mg/mL; subsequently, adding phosphorus powder into the nickel precursor solution so that the molar ratio of nickel to phosphorus is 1; then, adding PVC which accounts for about 20% of the volume of the ethanol into the mixed solution, and stirring until the PVC is uniformly dispersed in the mixed solution to prepare a spinning solution;
s22, spinning the spinning solution by adopting an air spinning method to obtain cotton-shaped flocks and obtain precursor fibers;
s23, drying the precursor fiber, then sintering the precursor fiber at the high temperature of 400 ℃ for 2 hours in an oxygen atmosphere, and then grinding the sintered product to the fiber length of 10-100 mu m and the diameter of 5-10nm after the sintered product is cooled to the room temperature to obtain the phosphorus-doped nickel oxide nanofiber with the staggered net-shaped appearance.
And (3) preparing the QLED luminescent device B by using the prepared phosphorus-doped nickel oxide nanofiber as a hole transport layer material. 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 ITO, electron transport layer material is ZnO, the luminescent layer is CdSe @ ZnS green quantum dot, the negative pole is Al.
Example 3
The embodiment prepares the nano material, and the specific process flow is as follows:
s31, dissolving nickel nitrate in ethanol to prepare a nickel precursor solution with the concentration of 200 mg/mL; subsequently, adding phosphorus powder into the nickel precursor solution so that the molar ratio of nickel to phosphorus is 1; then, adding PVP (polyvinyl pyrrolidone) accounting for about 20% of the volume of the ethanol into the mixed solution, and stirring until the PVP is uniformly dispersed in the mixed solution to prepare a spinning solution;
s32, spinning the spinning solution by adopting a gas spinning method to obtain cotton-shaped floccules and obtain precursor fibers;
s33, drying the precursor fiber, then sintering the precursor fiber at the high temperature of 400 ℃ for 2 hours in an oxygen atmosphere, and then grinding the sintered product to the fiber length of 10-100 mu m and the diameter of 5-10nm after the sintered product is cooled to the room temperature to obtain the phosphorus-doped nickel oxide nanofiber with the staggered net-shaped appearance.
And (3) preparing the QLED light-emitting device C by using the prepared phosphorus-doped nickel oxide nanofiber as a hole transport layer material. QLED luminescent device C is inversion type structure, including positive pole, hole transport layer, luminescent layer, electron transport layer, negative pole, the anode material is ITO, the electron transport layer material is ZnO, the luminescent layer is CdSe @ ZnS green quantum dot, the negative pole is Al.
Comparative example 1
This comparative example differs from example 1 in that: in the step of preparing the spinning solution, the addition of a phosphorus precursor is omitted; the prepared nickel oxide nanofiber is used as a hole transport layer material to prepare a QLED light-emitting device D;
the rest of the process is basically the same as that of embodiment 1, and the description thereof is omitted.
Comparative example 2
This comparative example differs from example 1 in that: and (3) omitting the spinning treatment process, directly adding a phosphorus precursor into a nickel precursor, uniformly stirring, centrifuging, taking out a precipitate, grinding the precipitate, placing the ground precipitate into a muffle furnace, heating to 400 ℃, calcining for 2 hours at a high temperature, and taking the prepared phosphorus-doped nano nickel oxide as a hole transport layer material to prepare the QLED light-emitting device E.
The hole transport layers prepared in examples 1 to 3, the hole transport layer in comparative example 1, and the quantum dot light emitting diode were subjected to performance tests, and the test indexes and the test methods were as follows:
(1) Hole mobility: testing the current density (J) -voltage (V) of the hole transport film, plotting a curve relationship, fitting the Space Charge Limited Current (SCLC) region in the relationship, and fitting according to the well-known Child , The hole mobility is calculated by the formula s law:
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 hole 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: and measuring the resistivity of the hole transport film by using the same resistivity measuring instrument.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
Note: the hole mobility and resistivity were tested as single layer thin film structure devices, i.e.: cathode/hole 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 BDA0002173130770000111
As can be seen from table 1 above, examples 1 to 3 of the present invention provided materials having a significantly lower resistivity than the hole transport films of comparative examples 1 and 2, and a significantly higher hole mobility than the hole transport films prepared in comparative examples 1 and 2.
The external quantum efficiency of the quantum dot light-emitting diode provided by the embodiments 1-3 of the invention is obviously higher than that of the quantum dot light-emitting diode in the comparative examples 1 and 2, which shows that the quantum dot light-emitting diode obtained by the embodiments has better luminous efficiency.
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 nickel precursor, a phosphorus precursor, a polymer and a solvent, and dissolving the nickel precursor, the phosphorus precursor and the polymer in the solvent to prepare a spinning solution;
spinning the spinning solution to prepare precursor fiber;
carrying out high-temperature sintering treatment on the precursor fiber in an oxygen-containing atmosphere to obtain phosphorus-doped nickel oxide nanofiber;
wherein phosphorus atoms replace part of the oxygen sites of the nickel oxide;
in the spinning solution, the concentration of the nickel precursor is 100-300mg/mL;
in the step of preparing the spinning solution, the phosphorus precursor and the nickel precursor are dissolved in the solvent in a ratio of a molar ratio of phosphorus atoms of the phosphorus precursor to nickel atoms of the nickel precursor of (0.005-0.01): 1.
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 production method according to claim 1, wherein in the step of subjecting the precursor fiber to a high-temperature sintering process, the temperature of the high-temperature sintering process is 300 to 500 ℃.
5. The method according to any one of claims 1 to 4, wherein after the step of subjecting the precursor fiber to a high temperature sintering treatment, the phosphorus-doped nickel oxide nanofibers are milled until the fiber length is 10-100 μm.
6. The production method according to any one of claims 1 to 4, wherein the nickel precursor includes at least one of nickel nitrate, nickel sulfate, nickel acetate, and nickel bromide; and/or
The phosphorus precursor comprises at least one of phosphorus simple substance, trioctylphosphine and trioctylphosphine oxide.
7. A nanomaterial prepared by the method of any one of claims 1 to 6, comprising: a phosphorus doped nickel oxide nanofiber; wherein phosphorus atoms replace part of the oxygen sites of the nickel oxide.
8. The nanomaterial according to claim 7, wherein the molar ratio of phosphorus atoms to nickel atoms in the phosphorus-doped nickel oxide nanofibers is (0.005-0.01): 1.
9. The nanomaterial according to claim 7, wherein the phosphorus-doped nickel oxide nanofibers 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 a hole transport layer disposed between the anode and the quantum dot light emitting layer, wherein the hole 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 8.
11. The quantum dot light-emitting diode of claim 10, wherein the hole transport layer has a thickness of 10-100nm.
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