CN110752301A - Composite material, preparation method thereof and quantum dot light-emitting diode - Google Patents

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

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CN110752301A
CN110752301A CN201810818777.7A CN201810818777A CN110752301A CN 110752301 A CN110752301 A CN 110752301A CN 201810818777 A CN201810818777 A CN 201810818777A CN 110752301 A CN110752301 A CN 110752301A
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zinc
gallium
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CN110752301B (en
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何斯纳
吴龙佳
吴劲衡
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TCL Corp
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    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
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    • H10K50/165—Electron transporting layers comprising dopants
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    • 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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Abstract

The invention belongs to the technical field of nano materials, and particularly relates to a composite material, a preparation method thereof and a quantum dot light-emitting diode. The composite material comprises ZnS nano-particles and Se and Ga doped in the ZnS nano-particles. The composite material is ZnS nano particles codoped with an acceptor (Se) -donor (Ga), the Se-Ga doping in the composite material can improve the free carrier concentration of ZnS, the resistance of ZnS is reduced, the conductivity is increased, the electron transmission capability of the composite material is finally improved, and the composite material can be used as a QLED electron transmission material, can promote the effective recombination of electrons and holes in a quantum dot light emitting layer, reduce the influence of exciton accumulation on the performance of a device, and improve the performance of the device and display performance.

Description

Composite material, preparation method thereof and quantum dot light-emitting diode
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a composite material, a preparation method thereof and a quantum dot light-emitting diode.
Background
The semiconductor quantum dots have quantum size effect, people can realize the required light emission with specific wavelength by regulating and controlling the size of the quantum dots, and the tuning range of the light emission wavelength of the CdSe QDs can be from blue light to red light. In the conventional inorganic electroluminescent device, electrons and holes are injected from a cathode and an anode, respectively, and then recombined in a light emitting layer to form excitons for light emission. Conduction band electrons in wide bandgap semiconductors can be accelerated under high electric fields to obtain high enough energy to strike QDs to cause it to emit light.
In recent years, inorganic semiconductors have been studied as an electron transport layer in a relatively hot manner. Nanometer ZnO and ZnS are wide bandgap semiconductor materials, and attract the attention of a plurality of researchers due to the advantages of quantum confinement effect, size effect, excellent fluorescence characteristic and the like. Therefore, in the last ten years, ZnO and ZnS nanomaterials have shown great potential for development in the fields of photocatalysis, sensors, transparent electrodes, fluorescent probes, diodes, solar cells, and lasers.
ZnO is an n-type semiconductor material with a direct band gap, has a wide forbidden band of 3.37eV and a low work function of 3.7eV, and the structural characteristics of the energy band determine that ZnO can become a proper electron transport layer material. Meanwhile, ZnS is a II-VI semiconductor material, has two different structures of sphalerite and wurtzite, has stable chemical property of forbidden bandwidth (3.62eV), and is rich in resources and low in price. The n-type doping of ZnS is affected by factors such as the generally high ionization energy of donor impurities and the compensation of intrinsic acceptor defects, and the doping of n-type ZnS has not been satisfactorily progressed. Most donor elements in ZnS have larger ionization energy and are difficult to ionize into effective donors at room temperature, so that n-type ZnS with good performance is difficult to prepare by single element doping. Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a composite material, a preparation method thereof and a quantum dot light-emitting diode, and aims to solve the technical problem that the effect of the existing n-type ZnS as an electron transport material is not ideal.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aspect of the present invention provides a composite material including ZnS nanoparticles, and Se and Ga elements doped in the ZnS nanoparticles.
Compounding of the inventionThe material is ZnS nano particles codoped with acceptor (Se) -donor (Ga), in the composite material, the acceptor (Se) -donor (Ga) codoped enables the donor level in ZnS to be shallow, the conduction band bottom of ZnS is effectively reduced, and n-type ZnS with good performance is formed. When Ga is doped, the doped Ga atoms are as Ga3+In a solid solution mode, Ga3+Occupying Zn in crystal lattice2+Two of three valence electrons of Ga are combined with sulfur to form saturated bonds, the third electron is separated from impurity atoms to form 1 redundant valence electron, the energy level of the electron is slightly lower than the bottom of a conduction band in an energy gap, and at normal temperature, enough energy can be obtained to jump to the conduction band to become free electrons, and the electrons directionally move under the action of an external electric field to conduct electricity. Therefore, doping Ga element results in increasing net electrons, decreasing ZnS resistance, and increasing conductivity. When Se is doped, the conduction band bottom (3.20eV) of ZnSe is lower than that (3.74eV) of ZnS, and Se replaces S to effectively reduce the conduction band bottom of ZnS, so that the aim of making the donor level shallow is fulfilled, and the ionization energy of a donor element is reduced. When Se-Ga is codoped, the donor ionization energy is obviously reduced due to the strong coupling effect between energy levels, and because the Se-Ga has strong affinity, a gap acceptor defect is not easy to form in doping, self-compensation energy is well inhibited, and the doping of the Se-Ga can enable the electronic Fermi level in ZnS to move to a conduction band, so that the forbidden bandwidth of the ZnS is narrowed, and electrons can be easily transited from an impurity level to enter the conduction band. Therefore, the Se-Ga doping can improve the free carrier concentration of ZnS, reduce the resistance of ZnS, increase the conductivity and finally improve the electron transmission capability of the composite material.
The invention also provides a preparation method of the composite material, which comprises the following steps:
providing zinc salt, gallium salt, selenium-containing element precursor salt and sulfur-containing element precursor salt;
dissolving the zinc salt, the gallium salt, the selenium-containing precursor salt and the sulfur-containing precursor salt in a solvent, and heating to obtain a precursor solution;
and annealing the precursor solution to obtain the composite material.
According to the composite preparation method provided by the invention, zinc salt, gallium salt, selenium-containing precursor salt and sulfur-containing precursor salt are firstly utilized to prepare precursor solution, and then the precursor solution is annealed to obtain a ZnS nano-particle composite material codoped by acceptor (Se) -donor (Ga); the preparation method is a simple sol-gel method, the preparation method is simple and easy to implement, and is suitable for large-area and large-scale preparation, and in the finally prepared composite material, the Se-Ga doping can improve the free carrier concentration of ZnS, so that the resistance of ZnS is reduced, the conductivity is increased, and the electron transmission capability of the composite material is finally improved.
Finally, the invention provides a quantum dot light-emitting diode, which comprises an anode, a cathode and a quantum dot light-emitting layer arranged between the anode and the cathode, wherein an electron transmission layer is also arranged between the cathode and the quantum dot light-emitting layer.
The electron transport layer in the quantum dot light emitting diode provided by the invention is composed of the special composite material of the invention, the composite material is ZnS nano particles codoped by an acceptor (Se) -donor (Ga), the Se-Ga doping in the composite material can enable the electronic Fermi level in ZnS to move to a conduction band, so that the forbidden bandwidth of ZnS is narrowed, electrons can be easily transited from an impurity level to the conduction band, the effective recombination of electron-holes in a quantum dot light emitting layer is promoted, the influence of exciton accumulation on the device performance is reduced, and the device and the display performance are improved.
Drawings
Fig. 1 is a schematic structural diagram of a QLED device in embodiment 4 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below 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.
In one aspect, embodiments of the present invention provide a composite material including ZnS nanoparticles, and Se and Ga elements doped in the ZnS nanoparticles.
The composite material is the ZnS nano-particles codoped by the acceptor (Se) -donor (Ga), in the composite material, the acceptor (Se) -donor (Ga) codoped enables the donor level in the ZnS to be shallow, the conduction band bottom of the ZnS is effectively reduced, and n-type ZnS with good performance is formed. When Ga is doped, the doped Ga atoms are as Ga3+In a solid solution mode, Ga3+Occupying Zn in crystal lattice2+Two of three valence electrons of Ga are combined with sulfur to form saturated bonds, the third electron is separated from impurity atoms to form 1 redundant valence electron, the energy level of the electron is slightly lower than the bottom of a conduction band in an energy gap, and at normal temperature, enough energy can be obtained to jump to the conduction band to become free electrons, and the electrons directionally move under the action of an external electric field to conduct electricity. Therefore, doping Ga element results in increasing net electrons, decreasing ZnS resistance, and increasing conductivity. When Se is doped, the conduction band bottom (3.20eV) of ZnSe is lower than that (3.74eV) of ZnS, and Se replaces S to effectively reduce the conduction band bottom of ZnS, so that the aim of making the donor level shallow is fulfilled, and the ionization energy of a donor element is reduced. When Se-Ga is codoped, the donor ionization energy is obviously reduced due to the strong coupling effect between energy levels, and because the Se-Ga has strong affinity, a gap acceptor defect is not easy to form in doping, self-compensation energy is well inhibited, and the doping of the Se-Ga can enable the electronic Fermi level in ZnS to move to a conduction band, so that the forbidden bandwidth of the ZnS is narrowed, and electrons can be easily transited from an impurity level to enter the conduction band. Therefore, the Se-Ga doping can improve the free carrier concentration of ZnS, reduce the resistance of ZnS, increase the conductivity and finally improve the electron transmission capability of the composite material.
Further, in the composite material of the embodiment of the present invention: the ratio of the total molar amount of Se and Ga to the molar amount of Zn is (0.001-0.01): 1. specifically, when the doping amount of Se + Ga reaches a certain value (more than 10%), the solid solubility of Se + Ga in ZnS reaches saturation, and when the doping amount is continuously increased, Se + Ga is collected on the surface of ZnS crystal grains to form a new phase, so that the effective specific surface area of nano ZnS is reduced, and the electron transport capability of the nano ZnS is influenced. When the doping amount of Se + Ga is too low, Se + Ga cannot be effectively doped, and the electron transport performance of n-type ZnS cannot be effectively improved. Wherein, Ga element is key for adjusting the forbidden band width of ZnS, the doping amount of Ga element is more than Se doping amount, and the mol ratio of Se element to Ga element is preferably 1: (2-3), the effect of adjusting the forbidden band width of ZnS is optimal. More preferably, 2% Se-5% Ga/ZnS works best.
On the other hand, the embodiment of the invention also provides a preparation method of the composite material, which comprises the following steps:
s01: providing zinc salt, gallium salt, selenium-containing element precursor salt and sulfur-containing element precursor salt;
s02: dissolving the zinc salt, the gallium salt, the selenium-containing precursor salt and the sulfur-containing precursor salt in a solvent, and heating to obtain a precursor solution;
s03: and annealing the precursor solution to obtain the composite material.
According to the composite preparation method provided by the embodiment of the invention, a precursor solution is prepared by using zinc salt, gallium salt, selenium-containing precursor salt and sulfur-containing precursor salt, and then the precursor solution is annealed to obtain a ZnS nano-particle composite material codoped by an acceptor (Se) -donor (Ga); the preparation method is a simple sol-gel method, the preparation method is simple and easy to implement, and is suitable for large-area and large-scale preparation, and in the finally prepared composite material, the Se-Ga doping can improve the free carrier concentration of ZnS, so that the resistance of ZnS is reduced, the conductivity is increased, and the electron transmission capability of the composite material is finally improved.
Further, in the step S01, the zinc salt is a soluble inorganic zinc salt or an organic zinc salt, and is at least one selected from zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, and zinc acetate dihydrate. The gallium salt is selected from at least one of gallium nitrate, gallium chloride and gallium sulfate; the sulfur element precursor salt is selected from at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide; the selenium-containing precursor salt is selected from at least one of sodium selenide, potassium selenide and ammonium selenide; the solvent is at least one selected from organic solvents such as isopropanol, ethanol, propanol, butanol, pentanol, hexanol, etc.
Further, in the above step S02: the ratio of the total molar amount of Se and Ga to the molar amount of Zn is (0.001-0.01): 1, dissolving the zinc salt, the gallium salt and the precursor salt containing the selenium element in a solvent. Specifically, zinc ions and dopant ions (Se) in the mixed solution2-+Ga3+) The molar ratio of the zinc ions to the doping ions is controlled to be 1: (0.001-0.1). When the Se + Ga doping amount reaches a certain value (more than 10 percent), the solid solubility of Se + Ga in ZnS reaches saturation, and the Se + Ga is concentrated on the surface of ZnS crystal grains to form a new phase when the doping amount is continuously increased, so that the effective specific surface area of nano ZnS is reduced; se2-+Ga3+Entering into the crystal lattice of ZnS to cause the expansion of the crystal lattice and generate larger crystal lattice distortion and strain energy, namely, the increase of doping amount can cause the mutation of the crystal lattice to form new crystal lattice and Ga2S3/SeSxAnd (4) generating. When the doping amount of Se + Ga is too low, Se + Ga is lost during the reaction process, and effective doping cannot be achieved. Wherein, Ga plays a key role in adjusting the forbidden band width of ZnS, the doping amount of Ga is more than that of Se, and the molar ratio of Se to Ga is preferably 1: and (2-3) dissolving the zinc salt, the gallium salt and the selenium-containing precursor salt in a solvent. Optimally, 2% Se-5% Ga/ZnS works best.
The temperature of the heating treatment is 60-80 deg.C, and is lower than the boiling point of the solvent.
Furthermore, the step of dissolving the zinc salt, the gallium salt, the selenium-containing precursor salt and the sulfur-containing precursor salt in a solvent for heating treatment to obtain a precursor solution comprises:
t01: dissolving the zinc salt, the gallium salt and the precursor salt containing the selenium element in the solvent to obtain a first mixed solution;
t02: dissolving the sulfur-containing precursor salt in the solvent to obtain a second mixed solution;
t03: and mixing the first mixed solution and the second mixed solution, and heating to obtain a precursor solution.
Further, the ratio of the molar amount of the S element to the total molar amount of the Zn element and the Ga element is (0.8-1.2): 1, mixing the first mixed solution and the second mixed solution. Se and Ga are doped with ZnS, and the molar ratio of sulfur to metal ions (zinc ions and gallium ions) in the precursor solution of Se and Ga is (0.8-1.2): 1, when the ratio of the sum of the molar amounts of sulfur and metal ions is less than 0.8: 1, excessive metal salt in the precursor solution, and incomplete doping of the added Se + Ga; greater than 1.2: when 1, the sulfur element-containing precursor salt is excessive, and an impurity compound is easily formed and is not easily removed. Optimally, the ratio of the molar amount of the S element to the total molar amount of the Zn element and the Ga element is (0.8-1.2): 1, a compact Se-Ga/ZnS film can be obtained subsequently, and the particles on the surface of the film are uniformly distributed.
Further, in the above step S03: the temperature of the annealing treatment is 200-300 ℃.
Finally, an embodiment of the present invention provides a quantum dot light emitting diode, including an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode, and an electron transport layer disposed between the cathode and the quantum dot light emitting layer, where the electron transport layer is made of the composite material according to the embodiment of the present invention.
The electron transport layer in the quantum dot light emitting diode provided by the embodiment of the invention is composed of the composite material which is the ZnS nano particle codoped by an acceptor (Se) -donor (Ga), the Se-Ga doping in the composite material can move the electronic Fermi level in the ZnS to a conduction band, so that the forbidden bandwidth of the ZnS is narrowed, electrons can be easily transited from an impurity level to the conduction band, the electron-hole effective recombination in the quantum dot light emitting layer is promoted, the influence of exciton accumulation on the device performance is reduced, and the device and display performance are improved.
In a specific preferred embodiment, the preparation method of the QLED device with the electron transport layer made of the Se-Ga co-doped ZnS nanomaterial comprises the following steps:
a: firstly, growing a hole transport layer on a substrate;
b: then depositing a quantum dot light-emitting layer on the hole transport layer;
c: and finally, depositing an electron transmission layer on the quantum dot light-emitting layer, and evaporating a cathode on the electron transmission layer to obtain the light-emitting diode.
In order to obtain a high-quality Se-Ga co-doped ZnS nano material (Se-Ga/ZnS) thin film, the ITO substrate needs to be subjected to a pretreatment process. The basic specific processing steps include: cleaning the whole piece of ITO conductive glass with a cleaning agent to primarily remove stains on the surface, then sequentially carrying out ultrasonic cleaning in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min respectively to remove impurities on the surface, and finally blowing dry with high-purity nitrogen to obtain the ITO anode.
The hole transport layer of the present invention can be made of hole transport materials conventional in the art, including but not limited to TFB, PVK, Poly-TPD, TCTA, PEDOT: PSS, CBP, etc., or any combination thereof, as well as other high performance hole transport materials. Hole transport layer: placing the ITO substrate on a spin coater, and spin-coating a prepared solution of a hole transport material to form a film; the film thickness is controlled by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then a thermal annealing process is performed at an appropriate temperature.
The preparation method of the light-emitting diode comprises the step of depositing a quantum dot light-emitting layer on the light-emitting diode, wherein the quantum dot of the quantum dot light-emitting layer is one of red, green and blue. 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. Then the quantum dots can be any one of the three common red, green and blue quantum dots or other yellow light, and the quantum dots can be cadmium-containing or cadmium-free. The quantum dot light emitting layer of the material has the characteristics of wide and continuous excitation spectrum distribution, high emission spectrum stability and the like. Preparation of a light-emitting layer: spin-coating the prepared luminescent material solution with a certain concentration on a spin coater of a substrate with a spin-coated hole transport layer to form a film, controlling the thickness of the luminescent layer to be about 20-60nm by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and drying at a proper temperature.
The electron transport layer is a Se-Ga co-doped ZnS nano material (Se-Ga/ZnS) film: the substrate which is coated with the quantum dot light-emitting layer by spin coating is placed on a spin coater, a cadmium-doped zinc oxide precursor solution with a certain concentration is prepared to form a film by spin coating, the thickness of the light-emitting layer is controlled to be about 20-60nm by adjusting the concentration of the solution, the spin coating speed (preferably, the rotating speed is 2000-6000 rpm) and the spin coating time, and then the film is formed by annealing at the temperature of 200-300 ℃ (such as 250 ℃). The step can be annealing in air or in nitrogen atmosphere, and the annealing atmosphere is selected according to actual needs.
And then, the substrate deposited with the functional layers is placed in an evaporation bin, and a layer of 15-30nm metal silver or aluminum is thermally evaporated through a mask plate to serve as a cathode, or a nano Ag wire or a Cu wire is used, so that a carrier can be smoothly injected due to the small resistance.
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. Preferably, the oxygen content and the water content in the packaging treatment environment are both lower than 0.1ppm so as to ensure the stability of the device.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
The preparation method of the Se-Ga/ZnS composite material is described in detail below by taking zinc chloride, sodium selenide, gallium chloride, ethanol and sodium sulfide as examples.
1) Adding appropriate amounts of zinc chloride, sodium selenide and gallium chloride to 50ml of ethanol to form a solution with a total concentration of 0.5M, wherein the ratio of zinc: the molar ratio of selenium to gallium is 1: 0.005; selenium: the molar ratio of gallium is 1: 3. dissolved at 70 ℃ with stirring.
2) To the above solution was added a solution of sodium sulfide dissolved in 10ml of ethanol (molar ratio, S)2-：Mx+1: 1, M is zinc and gallium). Stirring was continued at 70 ℃ for 4h to give a homogeneous solution.
3) After the solution was cooled, spin-coated on the treated ITO with a spin coater and annealed at 250 ℃.
Example 2
The preparation method of the Se-Ga/ZnS composite material is described in detail below by taking zinc nitrate, potassium selenide, gallium nitrate, propanol and potassium sulfide as examples.
1) Appropriate amounts of zinc nitrate, potassium selenide and gallium nitrate were added to 50ml of propanol to form a solution with a total concentration of 0.5M, where zinc: the molar ratio of selenium to gallium is 1: 0.005; selenium: the molar ratio of gallium is 1: 3. dissolved at 80 ℃ with stirring.
2) To the above solution was added a solution of potassium sulfide dissolved in 10ml of propanol (molar ratio, S)2-：Mx+1.1: 1, M is zinc and gallium). Stirring was continued at 80 ℃ for 3h to give a homogeneous solution.
3) After the solution was cooled, spin-coated on the treated ITO with a spin coater and annealed at 250 ℃.
Example 3
The preparation method of the Se-Ga/ZnS composite material is described in detail below by taking zinc sulfate, ammonium selenide, gallium sulfate, methanol and thiourea as examples.
1) Appropriate amounts of zinc sulfate, ammonium selenide and gallium sulfate were added to 50ml of methanol to form a solution with a total concentration of 0.5M, where zinc: the molar ratio of selenium to gallium is 1: 0.005; selenium: the molar ratio of gallium is 1: 3. dissolved at 70 ℃ with stirring.
2) To the above solution was added a solution of thiourea in 10ml of methanol (molar ratio, S)2-：Mx+1.2: 1, M is zinc and gallium). Stirring was continued at 60 ℃ for 4h to give a homogeneous solution.
3) After the solution was cooled, spin-coated on the treated ITO with a spin coater and annealed at 250 ℃.
Example 4
A QLED device of positive configuration, whose structure is shown in fig. 1, 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 in this order from bottom to top. The substrate 1 is made of a glass sheet, the anode 2 is made of an ITO substrate, the hole transport layer 3 is made of TFB, the electron transport layer 5 is made of Se-Ga co-doped ZnS nano material (Se-Ga/ZnS), and the cathode 6 is made of Al.
The preparation method of the QLED device comprises the following steps:
a: firstly, growing a hole transport layer on an anode substrate;
b: then depositing a quantum dot light-emitting layer on the hole transport layer;
c: and finally, depositing an electron transmission layer on the quantum dot light-emitting layer, and evaporating a cathode on the electron transmission layer to obtain the quantum dot light-emitting diode.
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 (10)

1. A composite material, characterized in that the composite material comprises ZnS nanoparticles and an element Se and an element Ga doped in the ZnS nanoparticles.
2. The composite material according to claim 1, wherein, in the composite material,
the molar ratio of Se element to Ga element is 1: (2-3); and/or
The ratio of the total molar amount of Se and Ga to the molar amount of Zn is (0.001-0.1): 1.
3. the preparation method of the composite material is characterized by comprising the following steps:
providing zinc salt, gallium salt, selenium-containing element precursor salt and sulfur-containing element precursor salt;
dissolving the zinc salt, the gallium salt, the selenium-containing precursor salt and the sulfur-containing precursor salt in a solvent, and heating to obtain a precursor solution;
and annealing the precursor solution to obtain the composite material.
4. The production method according to claim 3, wherein the molar amount of the Zn element relative to the total molar amount of the Se element and the Ga element is (0.001-0.01): 1, dissolving the zinc salt, the gallium salt and the precursor salt containing the selenium element in a solvent.
5. The production method according to claim 4, wherein the molar ratio of Se element to Ga element is 1: and (2-3) dissolving the zinc salt, the gallium salt and the selenium-containing precursor salt in a solvent.
6. The preparation method according to claim 3, wherein the step of dissolving the zinc salt, the gallium salt, the selenium-containing precursor salt and the sulfur-containing precursor salt in a solvent to perform a heating treatment to obtain a precursor solution comprises:
dissolving the zinc salt, the gallium salt and the precursor salt containing the selenium element in the solvent to obtain a first mixed solution;
dissolving the sulfur-containing precursor salt in the solvent to obtain a second mixed solution;
and mixing the first mixed solution and the second mixed solution, and carrying out heating treatment to obtain the precursor solution.
7. The production method according to claim 6, wherein the ratio of the molar amount of the S element to the total molar amount of the Zn element and the Ga element is (0.8-1.2): 1, mixing the first mixed solution and the second mixed solution.
8. The method according to any one of claims 3 to 7, wherein the zinc salt is selected from at least one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate dihydrate; and/or
The gallium salt is selected from at least one of gallium nitrate, gallium chloride and gallium sulfate; and/or
The sulfur element precursor salt is selected from at least one of sodium sulfide, potassium sulfide, thiourea and amine sulfide; and/or
The selenium-containing precursor salt is selected from at least one of sodium selenide, potassium selenide and ammonium selenide; and/or
The solvent is selected from at least one of isopropyl alcohol, ethanol, propanol, butanol, pentanol and hexanol.
9. The production method according to any one of claims 3 to 7, wherein the temperature of the heat treatment is 60 to 80 ℃; and/or
The temperature of the annealing treatment is 200-300 ℃.
10. A quantum dot light-emitting diode comprising an anode, a cathode and a quantum dot light-emitting layer arranged between the anode and the cathode, wherein an electron transport layer is arranged between the cathode and the quantum dot light-emitting layer, and the electron transport layer is made of the composite material as claimed in claim 1 or 2.
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