WO2018233355A1 - Mixed film and preparation method therefor, and preparation method for oled device - Google Patents

Abstract

A mixed film and a preparation method therefor, and a preparation method for an OLED device. The preparation method for a mixed film comprises: mixing quantum dots and a carrier in a solvent to obtain a mixed solution; preparing the mixed solution into a mixed film containing the quantum dots and the carrier through a solution method; and subjecting the mixed film containing the quantum dots and the carrier to cross-linking by using an HHIC technology, so that crosslinking occurs between the quantum dots and the carrier, to obtain a cross-linked mixed film. The HHIC technology enables independent quantum dots to be cross-linked with a carrier, thereby obtaining a mixed film in which the quantum dots are cross-linked with the carrier. In addition, an HHIC cross-linking method requires no cross-linking group, and thus can greatly reduce the quenching of the quantum dots by the cross-linking group and improve the luminous efficiency of the quantum dots. Furthermore, a large number of free radicals are generated during the HHIC cross-linking process, and the free radicals can be migrated to passivate the quenching of the quantum dots by the impurities, the luminous efficiency of the quantum dots is further improved.

Description

Mixed film and preparation method and QLED device preparation method Technical field

The invention relates to the technical field of light-emitting diodes, in particular to a mixed film and a preparation method thereof and a method for preparing a QLED device.

Background technique

Colloid quantum dots are nanomaterial systems based on liquid phase distribution. Colloidal quantum dots are prepared by different preparation processes (spin coating, printing, transfer or coating, etc.) to prepare quantum dot multilayer or single layer films. In the colloidal quantum dot system, the quantum dots are dispersed in a solvent, and the solvent evaporates after film formation, forming a solid film in which only quantum dots are deposited. Quantum dots are linked by weak Van der Waals forces. Under external action (mechanical force, solvent, etc.), the morphology of the film cannot be maintained, so the application of colloidal quantum dots is greatly limited. For example, in the preparation of quantum dot light-emitting diodes (QLEDs), since quantum dots cannot be cross-linked, they may be washed away by the solvent used in the preparation process on the quantum dot layer, thereby limiting the preparation process and material selection of QLEDs, thereby restricting The nature and application of QLED.

At present, the solution of quantum dot cross-linking mainly uses a chemical method, that is, adding a chemical crosslinking group in the process of preparing a quantum dot, and forming a film, and then crosslinking the quantum dot by heat treatment or light treatment to react the crosslinking group. The problem with this method is that the cross-linking groups are usually chemically active groups, such as: -CH=O and -OH groups, which crosslink the quantum dots and affect the luminescence of the quantum dots. Efficiency and electron mobility. Secondly, in the mixed film of the content sub-dots and the carrier, the general carrier is not crosslinked with the quantum dots, that is, only the carrier is crosslinked because the carrier has a crosslinking group.

Therefore, the prior art has yet to be improved and developed.

Summary of the invention

In view of the above deficiencies of the prior art, the object of the present invention is to provide a mixed film and a preparation method thereof and a QLED device, which aim to solve the problem that the crosslinking group in the existing crosslinking method quenches the quantum dots and affects the luminous efficiency of the quantum dots; In the mixed film containing the quantum dots and the carrier, cross-linking easily occurs between the carriers, and crosslinking between the carrier and the quantum dots is difficult.

The technical solution of the present invention is as follows:

A method for preparing a mixed film, comprising:

Mixing the quantum dots with the carrier in a solvent to obtain a mixed solution;

The mixed solution is prepared into a mixed film of the content sub-point and the carrier by a solution method;

The mixed film of the content sub-dots and the carrier is cross-linked by HHIC technology to crosslink the quantum dots and the carrier to obtain a crosslinked mixed film.

The invention utilizes the HHIC technology to cross-link the mixed film containing the quantum dots and the carrier, so that the independent quantum dots in the mixed film are cross-linked with the carrier to obtain a crosslinked mixed film. In addition, the HHIC crosslinking method of the present invention does not require a crosslinking group, and the quenching of the quantum dots by the crosslinking group can be greatly reduced, thereby improving the luminous efficiency of the quantum dots. In addition, due to the large amount of free radicals generated during the HHIC cross-linking process, the free radicals can migrate to the impurities, and the quenching impurities quench the quantum dots, thereby further improving the luminous efficiency of the quantum dots.

A mixed film in which the mixed film is prepared by the production method described in the present invention.

The mixed film obtained by cross-linking by the HHIC method of the invention is superior in stability to the conventional heat-crosslinked mixed film, and its electrical properties are not changed, and the application of the solution method and the range of material selection can be expanded.

A QLED device, wherein the QLED device comprises a hybrid film as described above.

A method for preparing a quantum dot light emitting diode device, comprising the steps of:

Depositing a first functional layer on a surface of the bottom electrode substrate;

Putting the first functional layer into the HHIC reactor and introducing H ₂ , the H _{2 is} ionized to form H plasma, and the solute component in the first functional layer is cross-linked by the H plasma;

Depositing a quantum dot luminescent layer on the surface of the first functional layer after crosslinking, and crosslinking the quantum dots in the quantum dot luminescent layer by H plasma;

Depositing a second functional layer on the surface of the cross-linked quantum dot light-emitting layer, and crosslinking the solute component in the second functional layer by H plasma;

A top electrode is deposited on the second functional layer after crosslinking to obtain a quantum dot light emitting diode.

The invention processes the first functional layer deposited on the bottom electrode substrate by H plasma to crosslink the solute components in the first functional layer; and then deposits quantum dots sequentially in the first functional layer after crosslinking a light-emitting layer, a second functional layer and a top electrode layer, and respectively performing cross-linking treatment on the quantum dot light-emitting layer and the second functional layer, thereby preparing a quantum dot light-emitting diode; by the method provided by the present invention, due to the functional layer and The quantum dot luminescent layer is cross-linked, so there is no need to consider the orthogonality of the solvent between the functional layer and the quantum dot luminescent layer in the process of preparing the QLED device, which greatly expands the material of the photovoltaic device such as QLED. The selection and process; and the method of the invention does not alter the nature of the crosslinking groups, nor does it produce by-products, greatly improving the stability and lifetime of the QLED device and the luminous efficiency.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing a preferred embodiment of a method for preparing a hybrid film of the present invention.

2 is a flow chart of a preferred embodiment of a method of fabricating a quantum dot light emitting diode device of the present invention.

3 is an interface optical micrograph of a preferred embodiment of a positive quantum dot light emitting diode device.

4 is a comparison chart of the ultraviolet spectrum of the mixed film of QD and TFB crosslinked in Example 1 and the ultraviolet spectrum of the mixed film of QD and TFB uncrosslinked, respectively.

Fig. 5 is a luminescence spectrum of a mixed film in which green light QD, blue light QD, red light QD, OXD-7 and Liq are crosslinked in Example 3.

6 is a luminescence spectrum test of a QD-PVC crosslinked mixed film prepared by the HHIC method in Example 4, and a luminescence spectrum test of a QD-PVC crosslinked mixed film prepared by the chemical crosslinking method in Comparative Example 5, respectively. Figure.

7 is a SEM electron micrograph of a mixed film in which QD and ZnO nanoparticles are crosslinked in Example 7.

Detailed ways

The present invention provides a mixed film, a preparation method and a method for preparing a QLED device. In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be further described in detail below. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The HHIC (Hyperthermal hydrogen induced cross-linking) technique uses H ₂ as a starting reactant, then converts H ₂ to H plasma, and then opens CH, HO, SH, HN and other chemical bonds with H plasma suitable for energy. These open chemical bonds are then rejoined to crosslink the chemicals together. This method is short in time, low in requirements (room temperature), no special requirements on the reactants, and no new substances are produced.

Specifically, in the HHIC reactor, the ion source is accelerated by electron cyclotron, and the plasma is ionized by electron cyclotron resonance. The microwave is injected into the electron cyclotron resonance corresponding to a certain volume of frequency. This volume contains a low pressure gas such as hydrogen, helium or the like. The alternating electric field of the microwave is set to synchronize with the revolution period of the gas free electrons and increase its vertical kinetic energy. Subsequently, when the charged free electrons collide with the gas in the volume, if their kinetic energy is greater than the ionization energy of the atom or molecule, they cause ionization. The ionized particles are accelerated by the electric field to obtain a certain kinetic energy, and the kinetic energy particles are passed through the collision to transfer the energy to the uncharged particles. The kinetic energy of the particles is controlled by adjusting the magnitude of the electric field. A particle having a certain kinetic energy such as H _{2 is} used as a starting reactant to crosslink the target film. In general, the key with the H bond can be as shown in Table 1 below.

Table 1

Chemical bond	H-H	H-C	N-H	O-H	Si-H	P-H	S-H
Key energy (eV)	18.9	18	16.9	20.2	13.9	13.8	15.8

Therefore, with a certain energy of H ₂ , the H bond can be turned on. The free radicals that form hydrogen and other groups are involved in the following reactions:

-C-H→-C·+H·· (1);

-N-H→-N·+H·· (2);

-O-H→-O·+H·· (3);

-Si-H→-Si·+H·· (4);

-P-H→-P·+H·· (5);

-S-H→-S·+H·· (6);

=C-H→=C·+H·· (7).

The above radicals may be combined with each other to crosslink the substances together. In the organic matter, the -CH bond is abundantly present, and the bond energy of -CH is very close to the bond energy of the HH bond, and therefore -CH is most likely to undergo a cross-linking reaction. By adjusting the electric field, the reaction energy can be controlled to open different chemical bonds in a targeted manner. The use of H ₂ as a reactant does not produce new by-products. The generated H _{2 is} returned by the airflow.

When free radicals are formed, they can diffuse in the film:

·C-C-C-......-C-C-C-H→H-C-C-C-......-C-C-C· (8)

At the beginning, the radical has a large concentration on the surface of the film. By diffusion, the radical can migrate into the interior of the film, so that the crosslinking reaction takes place inside the film, thereby crosslinking the entire film.

At the same time, free radicals are very active, and different free radicals can react with each other. Free radicals and non-free radicals can undergo proton exchange, such as the following formula (9):

-X·+H-R-→-X-H+·R (9); wherein H-R- is an alkane group and X is another factor, so this proton exchange reaction can broaden the range of crosslinked substances.

The surface of the quantum dot contains various organic ligands, and the present invention can crosslink the organic ligand and other organic/inorganic groups by the HHIC method, and the reaction formulas involved are mainly the formulas (1) and (8), which is Because the polymer or small molecule contains a large amount of unsaturated carbon bonds, the HHIC method opens the -CH of the organic ligand on the surface of the quantum dot, and then the carbon radical recombines with the H radical, thereby allowing the polymer or small molecule to cross with the quantum dot. Linked together.

1 is a flow chart of a preferred embodiment of a method for preparing a mixed film according to the present invention, as shown in the figure, including the steps:

Step S11, mixing the quantum dots and the carrier in a solvent to obtain a mixed solution;

Step S12, the mixed solution is prepared into a mixed film of the content sub-point and the carrier by a solution method;

Step S13, cross-linking the mixed film of the content sub-point and the carrier by HHIC technology, so that cross-linking occurs between the quantum dot and the carrier to obtain a cross-linked mixed film.

In the prior art, cross-linking of multiple components requires different cross-linking agents or cross-linking functional groups, which have an effect on quantum dots, such as the presence of cross-linking groups -CH=O, -OH, quenching quantum dots, serious Affect the luminous efficiency of quantum dots. The invention improves the prior art, and the core of the improvement is that the hybrid film containing the quantum dots and the carrier is cross-linked by the HHIC technology, so that the independent quantum dots and the carrier are cross-linked together in the mixed film to form Crosslinked mixed film. The present invention utilizes HHIC technology without the need for a crosslinking agent or a crosslinking functional group, which facilitates multi-component mixing to maintain group properties. In addition, in a mixed film of a quantum dot and a carrier, it is generally difficult for the carrier to crosslink with the quantum dot, that is, only the carrier is crosslinked because the carrier has a crosslinking group. The invention utilizes HHIC technology to crosslink quantum dots and carriers, in particular to crosslink organic ligands on the surface of quantum dots with other organic/inorganic groups by HHIC technology. In addition, the present invention utilizes the HHIC technology, does not require a crosslinking agent or a cross-linking functional group, and can greatly reduce quenching of quantum dots, thereby improving the luminous efficiency of quantum dots. Moreover, due to the large amount of free radicals generated during the HHIC cross-linking process, the free radicals can migrate to the impurities, and the quenching impurities quench the quantum dots, thereby further improving the luminous efficiency of the quantum dots.

Hereinafter, the preparation method of the above mixed film will be described in detail by using the carrier as one or more of a polymer and a small molecule.

In the step S11, the carrier may be one or more of a polymer and a small molecule. The quantum dots of the present invention are dispersed into a polymer or a small molecule, and the distance between the quantum dots can be increased, thereby improving the luminous efficiency of the quantum dots.

Specifically, the polymer may be one or more of a first p-type semiconductor material, a first n-type semiconductor material, a first insulator material, a first luminescent material, and the like. For example, the first p-type semiconductor material may be, but not limited to, one or more of PVK (polyvinylcarbazole), TFB, poly-TPD, P3HT (poly-3 hexylthiophene). The first n-type semiconductor material can be, but is not limited to, OXD-7. The first insulator material may be, but not limited to, PMMA (polymethyl methacrylate), PVP (polyvinylpyrrolidone), PEN (polyethylene naphthalate), PET (polyethylene terephthalate) One or more of the esters. The first luminescent material may be, but not limited to, MEH-PPV (red-emitting material - photovoltaic material). Preferably, the polymer is TFB.

Specifically, the small molecule is one or more of a second p-type semiconductor material, a second n-type semiconductor material, a second insulator material, and a second luminescent material. For example, the second p-type semiconductor material can be, but is not limited to, one or more of NPB, CBP, TCTA. The second n-type semiconductor material may be, but not limited to, one or more of Bphen (phenanthroline), Alq, Liq. The second insulator material can be, but is not limited to, UGH1. The second luminescent material may be, but not limited to, Ir(ppy)3 (tris(2-phenylpyridine) ruthenium), and Firpic (bis(4,6-difluorophenylpyridine-N, C2) pyridine formyl One or more of the combinations. Preferably, the small molecule is NPB.

Specifically, the solvent may be, but not limited to, toluene, benzene, chlorobenzene, xylene, chloroform, acetone, n-octane, isooctane, cyclohexane, n-hexane, n-pentane, isopentane, N, N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, n-butyl ether, anisole, phenylethyl ether, acetophenone One or more of aniline and diphenyl ether. Preferably, the chlorobenzene is.

Specifically, the quantum dots (QD) may be, but not limited to, red light quantum dots, green light quantum dots, blue quantum dots, and yellow light quantum dots, and one or more of infrared light quantum dots and ultraviolet light quantum dots. For example, the quantum dots may be red light quantum dots, green light quantum dots or blue light quantum, and may also be mixed quantum dots of red light quantum dots, green light quantum dots, and blue light quantum dots. That is, the present invention can mix a quantum dot of one color with a carrier of a polymer or a small molecule, or can mix quantum dots of different colors with a polymer carrier or a small molecule carrier.

The step S12 is specifically: spin coating the mixed liquid, forming the mixed liquid into a mixed film, forming a film, vacuum drying or heating (the heating temperature is 0-120 ° C, such as 120 ° C) to volatilize the solvent. Forming a mixed film containing only quantum dots and polymers or small molecules.

The step S13 specifically includes: placing a mixed film of a content sub-point and a polymer or a small molecule in an HHIC reactor, introducing H ₂ , and converting H ₂ into H plasma, and passing the H plasma pair content point and polymerization. The mixed film of the object or the small molecule is cross-linked to crosslink the quantum dot with the polymer or the small molecule to obtain a mixed film in which the quantum dot is crosslinked with the polymer or the small molecule. Preferably, the energy of the H plasma is controlled to be 1 to 100 eV, and more preferably the energy of the H plasma is 5 to 70 eV. In this range, a mixed film of a suitable degree of crosslinking can be prepared, and the film uniformity is good. Preferably, the time for controlling the crosslinking treatment is from 1 to 30 min, and the more preferred crosslinking treatment time is from 1 to 10 min.

Hereinafter, the preparation method of the above mixed film will be described in detail by using the carrier as an inorganic precursor.

In the step S11, the carrier is an inorganic precursor. Specifically, the inorganic precursor may be one or two of zinc acetate, molybdenum acetate, nickel acetate, titanium acetate, tungsten acetate, and the like. Preferably, the inorganic precursor is zinc acetate.

Specifically, the solvent may be, but not limited to, methoxyethanol.

Specifically, the quantum dots (QD) may be, but not limited to, red light quantum dots, green light quantum dots, blue quantum dots, and yellow light quantum dots, and one or more of infrared light quantum dots and ultraviolet light quantum dots. For example, the quantum dots may be red light quantum dots, green light quantum dots or blue light quantum, and may also be mixed quantum dots of red light quantum dots, green light quantum dots, and blue light quantum dots. That is, the present invention can mix a quantum dot of one color with an inorganic precursor, or can mix quantum dots of different colors with an inorganic precursor.

The step S12 is specifically: spin coating the mixed liquid, forming the mixed liquid into a mixed film, forming a film, vacuum drying or heating (the heating temperature is 60-100 ° C, such as 80 ° C) to volatilize the solvent. The heating time is 10-20 min (such as 15 min) to form a mixed film containing only the inorganic precursor and quantum dots.

The step S13 specifically includes: placing a mixed film containing an inorganic precursor and a quantum dot in an HHIC reactor, introducing H ₂ , and converting H ₂ into H plasma, and passing the inorganic precursor with H plasma. The mixed film of the quantum dots is cross-linked to cause cross-linking between the inorganic precursor and the quantum dots, and the inorganic precursor reacts to form an inorganic substance during the cross-linking process, thereby obtaining a mixed film of inorganic-encapsulated quantum dots. After the inorganic precursor and the quantum dots are cross-linked, a structure of inorganic-encapsulated quantum dots may be formed, and the inorganic substances may be molybdenum oxide (MoO _x ), tungsten oxide (WO), nickel oxide (NiO), or zinc oxide ( One or more of ZnO), titanium oxide (TiO), and the like. Preferably, the energy of the H plasma is controlled to be 1 to 100 eV, and more preferably the energy of the H plasma is 5 to 70 eV. Within this range, a mixed film of a suitable degree of crosslinking can be prepared, and the film uniformity is good. Preferably, the time for controlling the crosslinking treatment is from 1 to 30 min, and the more preferred crosslinking treatment time is from 1 to 10 min.

In the prior art, inorganic physical materials can be well wrapped by quantum physical deposition, PECVD, etc., but these methods are limited by the vacuum process and cannot be applied to the solution method. The invention improves the prior art, and the core of the improvement is that a mixed liquid containing an inorganic precursor and a quantum dot is prepared into a mixed film containing an inorganic precursor and a quantum dot by a solution method, and then HHIC technology is utilized. The mixed film containing the inorganic precursor and the quantum dots is cross-linked to crosslink the inorganic substances and quantum dots formed in the mixed film to obtain a mixed film of inorganic-encapsulated quantum dots. The invention utilizes the HHIC technology to realize a mixed film of an inorganic precursor and a quantum dot by a solution method to form a mixed film of an inorganic substance and a quantum dot cross-linking, thereby forming a structure in which an inorganic substance encapsulates a quantum dot.

Furthermore, the present invention can also add an organic substance to a system of an inorganic precursor and a quantum dot, and then form a mixed film containing an inorganic precursor, an organic substance and a quantum dot by a solution method, and finally make an inorganic precursor by HHIC technology. The cross-linking between the body, the organic matter and the quantum dot forms a structure in which the inorganic substance and the organic substance wrap the quantum dot. The steps for cross-linking specific inorganic, organic and quantum dots are as follows:

The step S11 is specifically: mixing an inorganic precursor, an organic substance, and a quantum dot in a solvent to obtain a mixed liquid containing an inorganic precursor, an organic substance, and a quantum dot;

Preferably, the organic substance may be one or more of ethanolamine, 2-phenoxyethanol, ethylene glycol butyl ether and the like.

The step S12 is specifically: preparing the mixed liquid into a mixed film containing an inorganic precursor, an organic substance, and a quantum dot by a solution method;

Specifically, in the above step S13, a mixed film containing an inorganic precursor, an organic substance, and a quantum dot is cross-linked by a HHIC technique to obtain a mixed film of an inorganic substance and an organic substance-coated quantum dot.

The step S13 specifically includes: placing a mixed film containing inorganic substances, organic matters, and quantum dots in an HHIC reactor, introducing H ₂ , and converting H ₂ into H plasma, and passing the inorganic precursor by H plasma, The mixed film of the organic substance and the quantum dot is cross-linked to crosslink the inorganic substance, the organic substance and the quantum dot to obtain a mixed film of the inorganic substance and the organic substance-encapsulated quantum dot.

By the vacuum method, the inorganic precursor and the organic matter are more difficult to better encapsulate the quantum dots, because the general vacuum physical deposition, PECVD and the like cannot deposit organic matter because the energy is too high. The vapor deposition method in which an organic substance can be deposited, because the vaporization temperature of the inorganic precursor is too high, the inorganic precursor cannot be well deposited. The invention improves the prior art, and the core of the improvement is that the hybrid film containing the inorganic precursor, the organic substance and the quantum dot is cross-linked by the HHIC technology, so that the inorganic and organic substances in the mixed film are independent. The quantum dots are cross-linked to form a mixed film of inorganic and organic-encapsulated quantum dots. The invention cross-links quantum dots with inorganic substances and organic substances through HHIC technology, and ensures that inorganic materials and organic materials better encapsulate quantum dots.

Hereinafter, the preparation method of the above mixed film will be described in detail by using the carrier as an inorganic nanoparticle containing an organic ligand. In the step S11, the carrier of the present invention is an inorganic nanoparticle containing an organic ligand, wherein the inorganic nanoparticle is one or more of MoO _x , WO, NiO, ZnO, and TiO. The organic ligand is one or more of octyl thiol and ethanolamine. These ligands are distributed on the surface of the quantum dots and do not affect the properties of the nanoparticles, but can be exchanged by HHIC and other organic/inorganic groups. In addition, this process does not require the introduction of crosslinking groups, thereby minimizing the generation of impurities.

Specifically, the solvent may be, but not limited to, toluene, benzene, chlorobenzene, xylene, chloroform, acetone, n-octane, isooctane, cyclohexane, n-hexane, n-pentane, isopentane, N, N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, n-butyl ether, anisole, phenylethyl ether, acetophenone One or more of aniline and diphenyl ether. Preferably, the solvent is chlorobenzene.

Specifically, the quantum dots (QD) may be, but not limited to, red light quantum dots, green light quantum dots, blue quantum dots, and yellow light quantum dots, and one or more of infrared light quantum dots and ultraviolet light quantum dots. For example, the quantum dots may be red light quantum dots, green light quantum dots or blue light quantum, and may also be mixed quantum dots of red light quantum dots, green light quantum dots, and blue light quantum dots. That is, the present invention can mix quantum dots of one color with inorganic nanoparticles, and can also mix quantum dots of different colors with inorganic nanoparticles.

The step S12 is specifically: spin coating the mixed liquid, forming the mixed liquid into a mixed film, forming a film, vacuum drying or heating (the heating temperature is 0-120 ° C, such as 120 ° C) to volatilize the solvent. A mixed film containing only quantum dots and inorganic nanoparticles is formed.

The step S13 specifically includes: placing the mixed film in the HHIC reactor, introducing H ₂ , and converting the H ₂ into H plasma, and crosslinking the mixed film by H plasma to make the quantum dots and the inorganic nanoparticles. Cross-linking occurs to obtain a mixed film in which quantum dots are crosslinked with inorganic nanoparticles. Preferably, the energy of the H plasma is controlled to be 1 to 100 eV, and more preferably the energy of the H plasma is 5 to 70 eV. Within this range, a mixed film of a suitable degree of crosslinking can be prepared, and the film uniformity is good. Preferably, the time for controlling the crosslinking treatment is from 1 to 30 min, and the more preferred crosslinking treatment time is from 1 to 10 min.

In the prior art, cross-linking of multiple components requires different cross-linking agents or cross-linking functional groups, which have an effect on quantum dots. Due to the different substances in the multiple components, the properties are different, and the crosslinking agent and the functional group are easily reacted with the functional groups of the different components. The invention improves the prior art, and the core of the improvement is that the hybrid film containing the quantum dots and the inorganic nanoparticles is cross-linked by the HHIC technology, so that the independent quantum dots and the inorganic nanoparticles are cross-linked in the mixed film. Together, a mixed film of quantum dots and inorganic nanoparticles is formed. The present invention utilizes HHIC technology without the need for a crosslinking agent or a crosslinking functional group, which facilitates multi-component mixing to maintain group properties. In addition, in the mixed film of quantum dots and inorganic nanoparticles, inorganic nanoparticles and luminescent quantum dots generally have no crosslinking groups. The invention utilizes HHIC technology to crosslink quantum dots and inorganic nanoparticles, in particular to crosslink organic ligands on the surface of quantum dots with other organic/inorganic groups by HHIC technology, since this process does not require introduction of crosslinking groups, thereby Minimize the prevention of the generation of impurities. Further, the inorganic nanoparticles may also be mixed with a polymer having no crosslinking group, a small molecule, and crosslinked by HHIC. The present invention utilizes the HHIC technology without changing the properties of the non-crosslinking groups and does not produce by-products.

The surface of the quantum dot contains various organic ligands, and the present invention can crosslink the organic ligand and other organic/inorganic groups by the HHIC method. The HHIC method does not alter the nature of the non-crosslinking groups and does not produce by-products. The invention can greatly expand the material selection and process of photoelectric devices such as QLEDs by the HHIC method. The HHIC method is a non-selective cross-linking method for quantum dots (quantum dots of different solvents, quantum dots of different surface ligands, etc.), and the HHIC method will expand the application range of quantum dots and reduce the requirements on the process. The HHIC method does not affect or slightly affect the properties of quantum dots (luminescence, conductivity, etc.) compared to other methods. The film crosslinked by the HHIC method is superior in stability to the conventional heat-crosslinked film, and its electrical properties. no change. HHIC can expand the application of the solution method and the range of materials selected.

Inorganic nanoparticles (such as MoO _x , WO, NiO, ZnO, TiO, etc.) and luminescent quantum dots generally have no crosslinking groups, and there are generally organic ligands for dispersion on the outside, such as octyl thiol, ethanolamine, etc. The group does not affect the properties of the nanoparticles. With these organic ligands, the inorganic nanoparticles can be crosslinked with luminescent quantum dots through HHIC, which mainly involves the reaction formulas (1)(3)(4)(8) and (9). Wherein Si in the reaction formula (4) may be Mo, W, Ni, Zn, Ti, and the H ₂ kinetic energy is changed to trigger the reaction by adjusting the electric field according to the bond energy. Further, the inorganic nanoparticles can also be cross-linked by HHIC after mixing with a polymer or a small molecule having no crosslinking group, and the process mainly involves the reverse process of the reaction formula (9):

-X-H+·R-→-X·+H-R- (10)

By reaction formula (10), free radicals are transferred to other factors by proton transfer.

A mixed film of the present invention, wherein the mixed film is prepared by the production method of the present invention. The mixed film obtained by cross-linking by the HHIC method of the invention is superior to the conventional heat-crosslinked mixed film of quantum dots and inorganic nanoparticles in stability, and its electrical properties are not changed, and the application of the solution method and the range of material selection can be expanded. Preferably, the crosslinked mixed film has a thickness of 10 to 100 nm, such as 40 nm, 50 nm or 100 nm.

The invention also provides an application of a crosslinked mixed film, wherein the crosslinked mixed film as described above is applied to a QLED device, as a functional layer of the QLED device, which can effectively improve the stability of the QLED device, and The electrical properties of the QLED device can be ensured; more specifically, the crosslinked hybrid film can be applied to a quantum dot luminescent layer, a hole transport layer, a hole injection layer, an electron transport layer, and an electron injection layer in a QLED device. .

2 is a flow chart of a preferred embodiment of a method for fabricating a quantum dot light emitting diode device according to the present invention, as shown in the figure, including the steps:

S21, depositing a first functional layer on a surface of the bottom electrode substrate;

S22, the first functional layer is placed in the HHIC reactor and H _{2 is introduced} , and the H _{2 is} ionized to form a H plasma, and the solute component in the first functional layer is cross-linked by the H plasma;

S23, depositing a quantum dot luminescent layer on the surface of the first functional layer after crosslinking, and crosslinking the quantum dots in the quantum dot luminescent layer by H plasma;

S24, depositing a second functional layer on the surface of the cross-linked quantum dot emitting layer, and crosslinking the solute component in the second functional layer by H plasma;

S25, depositing a cathode layer on the second functional layer after crosslinking to obtain a quantum dot light emitting diode.

Specifically, there is a huge barrier in the process of preparing a QLED device by using the prior art, which requires that the orthogonality of the solution be satisfied between different layers, that is, the solvent and solute of the adjacent layer are not compatible, which greatly limits the limitation. The selection of quantum dots and functional layers for the device and hinders the development of the QLED process;

In order to solve the above problems, the present invention processes the first functional layer deposited on the bottom electrode substrate by H plasma to crosslink the solute components in the first functional layer; then the first functional layer after crosslinking Depositing a quantum dot luminescent layer, a second functional layer and a top electrode layer in sequence, and respectively performing cross-linking treatment on the quantum dot luminescent layer and the second functional layer, thereby preparing a quantum dot light emitting diode; the method provided by the present invention Since the functional layer and the quantum dot luminescent layer are cross-linked, there is no need to consider the orthogonality of the solvent between the functional layer and the quantum dot luminescent layer in the process of preparing the QLED device, which greatly expands the QLED. The material selection and process of the optoelectronic device; and the method of the invention does not change the properties of the crosslinking group, nor does it produce by-products, which greatly improves the stability and service life of the QLED device and the luminous efficiency.

Further, for quantum dots, the solubility of a quantum dot in a solvent is determined by its ligand. If the ligand is hydrophilic, the quantum dot can be dissolved into a polar solvent such as water, ethanol, etc.; The ligand is hydrophobic, then the quantum dots can be dissolved in a non-polar solvent such as chlorobenzene or alkanes;

Since different ligands and solvent types affect the luminescence, electrical and film-forming properties of quantum dots, in order to ensure the specific properties of some QLED device structures, only the same solvent can be used to dissolve the quantum dot material and the functional layer material. Thus, a quantum dot luminescent layer and a functional layer having the same solvent are prepared; however, when the same solvent is used to prepare the quantum dot luminescent layer and the functional layer, the solute and solvent of the adjacent layer are mutually soluble, that is, quantum dot luminescence The quantum dots on the layer are easily washed away by the solvent used in the preparation of the functional layer, or the solute on the functional layer is easily washed away by the solvent used in the preparation of the quantum dot light-emitting layer, so that the QLED device fails to be prepared.

In order to solve the problem, the quantum dot light-emitting layer and the functional layer may be cross-linked by cross-linking, thereby ensuring that the solvent and the solute on the functional layer and the quantum dot light-emitting layer are not mutually soluble;

Taking quantum dot cross-linking as an example, the existing quantum dot cross-linking process is usually achieved by chemical methods, that is, adding chemical crosslinking groups during the preparation of quantum dots, and forming a film by heat treatment or light treatment to crosslink. The group reacts to crosslink the quantum dots; however, the method has problems in that the crosslinking group is usually a chemically active group, and its presence affects the luminous efficiency and electron mobility of the quantum dots; In the cross-linking process, by-products are easily generated, and these by-products are difficult to remove as quantum impurities from the quantum dot light-emitting layer. Therefore, chemical cross-linking is not a practical cross-linking scheme;

Another method capable of realizing cross-linking of quantum dots is heating cross-linking. The problem of the method is that heating easily breaks down the properties of the cross-linking substance, in particular, some functional groups are prone to chemical reactions at high temperatures; and liquid phase precursors There may also be phase separation problems, especially quantum dots and organic matter. Due to the difference in surface energy, the spatial physical distribution of the film after heating is easily uneven.

In order to solve the problems in the above cross-linking process, the present invention uses HHIC (Hyperthermal hydrogen induced cross-linking) technology to achieve cross-linking of quantum dots; the HHIC technology uses H ₂ as a starting reactant, and then makes H ₂ It is converted into H plasma, and then CH, CH, HO, SH, HN and other chemical bonds are opened with H plasma suitable for energy; these open chemical bonds are then rejoined to crosslink the chemicals together. Preferably, in the preparation of the quantum dot film, the energy of the H plasma is controlled to be 1 to 100 eV, and the energy of the H plasma is more preferably 5 to 70 eV. In this range, a mixed film of a suitable degree of crosslinking can be prepared. The film has good uniformity. Preferably, the time for controlling the crosslinking treatment is from 1 to 30 min, and the more preferred crosslinking treatment time is from 1 to 10 min.

The HHIC method is short in time, low in requirements (room temperature), has no special requirements on the reactants, and does not produce new substances; and the HHIC crosslinking method is equally applicable to organic molecules and polymers.

The surface of the quantum dot contains various organic ligands. The HHIC method can crosslink the ligands on the surface of the quantum dots by the HHIC method, and the HHIC method does not change the properties of the non-crosslinking groups, and does not produce by-products; Through the HHIC method, the material selection and process of photoelectric devices such as QLEDs can be greatly expanded.

The HHIC method is a non-selective cross-linking method for quantum dots, organic molecules, and polymers (quantum dots, organic molecules and polymers for different solvents, quantum dots of different surface ligands, etc.), and the HHIC method will Expand the selection range of QLED device preparation and reduce the requirements of the process; HHIC method does not affect the properties of quantum dots (luminescence, conduction, etc.) compared with other methods, and the quantum dot luminescent layer crosslinked by HHIC method is stable. It is superior to the conventionally heated crosslinked quantum dot light-emitting layer, and its luminous efficiency will be improved.

Further, in the present invention, when the positive quantum dot light emitting diode device is prepared, it is one or more of a hole transport layer, a hole injection layer or an electron blocking layer, and the second functional layer is an electron transport layer. One or more of an electron injecting layer or a hole blocking layer;

Specifically, as shown in FIG. 3, when the prepared positive-type quantum dot device includes ITO/Poly-TPD/TFB/QD/ZnO/Al in order from bottom to top, the device can be prepared by the HHIC method; That is, when depositing the Poly-TPD/TFB/QD/ZnO layer, the problem of dissolving the previous layer in the next layer of solvent may be omitted, and the Poly-TPD, TFB, QD, and ZnO may use the same solvent; Figure 3 is an optical micrograph of the interface of ITO/Poly-TPD/TFB/QD/ZnO/Al devices prepared in the same solvent. It can be seen from the figure that the interface of each layer is very clear.

When preparing the inverse quantum dot light emitting diode device, the first functional layer is one or more of an electron transport layer, an electron injection layer or a hole blocking layer, and the second functional layer is a hole transport layer, One or more of a hole injection layer or an electron blocking layer.

Preferably, a hole injection layer may be disposed between the anode substrate and the hole transport layer, and an electron injection layer may be disposed between the cathode layer and the electron transport layer; In the process of the hole injection layer and the electron injection layer, the HHIC technique is also used for crosslinking treatment.

Further, in the present invention, the anode in the anode substrate may be selected from the group consisting of indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), and aluminum doping. One or more of zinc oxide (AZO); the hole injection layer is poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), undoped transition metal oxide Or one or more of a doped transition metal oxide, a metal sulfide, or a doped metal sulfide;

The hole transport layer material may be selected from organic materials having hole transporting ability, including but not limited to poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (poly-TPD), poly(9) ,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), 4,4'-bis(9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-di Amine (NPB), doped graphene, undoped graphene, C ₆₀ or a mixture thereof; the hole transport layer material may also be selected from inorganic materials having hole transporting ability, including but not limited to doping Or undoped NiO, WO ₃ , MoO ₃ , CuO or a mixture thereof;

The electron transport layer material is one or more of n-type ZnO, TiO ₂ , SnO, Ta ₂ O ₃ , AlZnO, ZnSnO, InSnO, Alq3, Ca, Ba, CsF, LiF, CsCO ₃ ; preferably The electron transport layer is n-type ZnO, n-type TiO ₂ ; the cathode layer is made of Al or Ag;

Further, in the present invention, the material of the quantum dot light-emitting layer is a II-VI compound, a III-V compound, a II-V compound, a III-VI compound, a IV-VI compound, and an I-III-VI. One or more of a group compound, a group II-IV-VI compound or a group IV element;

Specifically, the semiconductor material used in the quantum dot light-emitting layer includes, but is not limited to, nanocrystals of II-VI semiconductors, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, and Other binary, ternary, quaternary II-VI compounds; III-V semiconductor nanocrystals, such as GaP, GaAs, InP, InAs, and other binary, ternary, quaternary III-V compounds; The semiconductor material for electroluminescence is not limited to a group II-V compound, a III-VI compound, a group IV-VI compound, a group I-III-VI compound, a group II-IV-VI compound, a group IV element or the like.

Further, in the present invention, the deposition method of each layer may be a chemical method or a physical method, wherein the chemical method includes, but not limited to, chemical vapor deposition, continuous ion layer adsorption and reaction, anodization, electrolytic deposition, One or more of the coprecipitation methods; physical methods include, but are not limited to, spin coating, printing, knife coating, immersion pulling, soaking, spraying, rolling, casting, slit coating One of a cloth method, a strip coating method, a thermal evaporation coating method, an electron beam evaporation coating method, a magnetron sputtering method, a multi-arc ion plating method, a physical vapor deposition method, an atomic layer deposition method, and a pulse laser deposition method. Or a variety.

Based on the above method, the present invention also provides a quantum dot light emitting diode device, which is prepared by any of the above methods. The quantum dot light emitting diode device prepared by the invention has the characteristics of high luminous efficiency, stable performance and long service life.

The invention will now be described in detail by way of examples.

Example 1

The preparation steps of the mixed film in which QD and TFB are crosslinked are as follows:

10 mg of QD and 10 mg of TFB were mixed into 1 ml of chlorobenzene solvent to obtain a mixed solution. The mixed solution was spin-coated, and the mixed liquid was formed into a mixed film, and after film formation, it was vacuum dried to volatilize the solvent to form a mixed film of 40 nm. The mixed film was placed in a HHIC reactor, H _{2 was introduced} , H _{2 was} converted into H plasma, H plasma energy was adjusted to 10 eV, and cross-linking treatment was carried out for 10 min to obtain a mixed film in which QD and TFB were crosslinked.

The QD and TFB crosslinked mixed film prepared in this example and the QD and TFB uncrosslinked mixed film were respectively subjected to infrared test. The test results are shown in Fig. 4. The peak at 450 nm is the TFB peak, and the peak at 530 nm is QD peaks. The results showed that the luminescence spectrum of HHIC did not change after cross-linking, and the cross-linking of QD and TFB was successful.

Example 2

The preparation steps of the mixed film in which QD and NPB are crosslinked are as follows:

20 mg of QD and 5 mg of NPB were mixed into 1 ml of chlorobenzene solvent to obtain a mixed solution. The mixture was spin-coated, and the mixture was made into a mixed film. After film formation, the solvent was volatilized at 120 ° C to form a 50 nm mixed film. The mixed film was placed in a HHIC reactor, H _{2 was introduced} , H _{2 was} converted into H plasma, H plasma energy was adjusted to 10 eV, and cross-linking treatment was carried out for 10 min to obtain a mixed film in which QD and NPB were crosslinked.

Example 3

The preparation steps of the mixed film of green light QD, blue light QD, red light QD, OXD-7 and Liq crosslinked are as follows:

25 mg of green light QD, 10 mg of blue light QD, 2 mg of red light QD, 10 mg of OXD-7 and 15 mg of Liq were mixed into 1 ml of chlorobenzene solvent to obtain a mixed solution. The mixture was spin-coated, and the mixture was made into a mixed film. After the film formation, the solvent was volatilized at 120 ° C to form a mixed film of 100 nm. The mixed film is placed in a HHIC reactor, H _{2 is introduced} , H _{2 is} converted into H plasma, H plasma energy is adjusted to 10 eV, and cross-linking treatment is performed for 20 min to obtain green light QD, blue light QD, red light QD, A mixed film of OXD-7 crosslinked with Liq.

The prepared mixed film of green light QD, blue light QD, red light QD, OXD-7 and Liq was subjected to luminescence spectroscopy, and the test results are shown in FIG. 5.

Example 4

The steps of preparing a mixed film of QD and PVC crosslinked by the HHIC method are as follows:

20 mg of QD and 5 mg of PVC were mixed into 1 ml of chlorobenzene solvent to obtain a mixed solution. The mixed solution was spin-coated, and the mixed solution was made into a mixed film containing QD and PVC. After film formation, the solvent was evaporated under vacuum to form a 50 nm mixed film containing QD and PVC. The mixed film containing QD and PVC is placed in a HHIC reactor, H _{2 is introduced} , H _{2 is} converted into H plasma, H plasma energy is adjusted to 10 eV, and cross-linking treatment is carried out for 10 min to obtain cross-linking of QD and PVC. Mixed film.

Comparative Example 5

The steps of preparing a mixed film of QD and PVC crosslinked by a conventional chemical crosslinking method are as follows:

Mix 20mg QD with 5mg PVC and crosslink with appropriate amount of triazolyldiamine amine salt (FSH). The crosslinking mechanism is the combination of amine and sulfhydryl group to attack the carbon-carbon polar bond to obtain the cross-linking of QD and PVC. film.

The mixed film of QD and PVC cross-linked by the conventional chemical crosslinking method of Example 4HHIC method and Comparative Example 5 was respectively subjected to luminescence spectroscopy test. The test results are shown in Fig. 6. The luminescence of the mixed film of QD and PVC crosslinked by HHIC method was carried out. The strength is much greater than the mixed film luminescence intensity of QD and PVC crosslinked by the chemical crosslinking method. This is because the traditional chemical crosslinking method requires the addition of a triazole dimercaptoamine salt (FSH) cross-linking agent, and the crosslinking mechanism is a combination of an amine and a sulfhydryl group to attack the carbon-chloride polar bond. The amino group in this reaction affects the luminescent properties of the quantum dots, and the unreacted triazole dimercaptoamine salt is the main cause of quenching quantum dot luminescence. In summary, the present invention provides a hybrid film and a method for preparing a quantum dot and a carrier crosslinked with a QLED device. The invention utilizes the HHIC technology to cross-link the mixed film containing the quantum dots and the carrier, so that the independent quantum dots in the mixed film are cross-linked with the carrier to obtain a mixed film in which the quantum dots and the carrier are crosslinked. In a mixed film of quantum dots and a carrier, it is generally difficult for the carrier to crosslink with the quantum dots, that is, only the carriers are crosslinked because the carrier has a crosslinking group. The invention utilizes HHIC technology to crosslink quantum dots and carriers, in particular to crosslink organic ligands on the surface of quantum dots with other organic/inorganic groups by HHIC technology. In addition, the present invention utilizes the HHIC technology, does not require a crosslinking agent or a crosslinking functional group, and can greatly reduce quenching of quantum dots, thereby improving the luminous efficiency of quantum dots. Moreover, due to the large amount of free radicals generated during the HHIC cross-linking process, the free radicals can migrate to the impurities, and the quenching impurities quench the quantum dots, thereby further improving the luminous efficiency of the quantum dots. The film crosslinked by the HHIC method is superior in stability to the conventional heat-crosslinked film, and its electrical properties are not changed. HHIC can expand the application of the solution method and the range of materials selected.

Example 6

10 mg of zinc acetate was dissolved in 2 ml of methoxyethanol solvent and then heated at 60 ° C for 30 min. Then 200 μL of ethanolamine was added and heating was continued at 60 ° C for 30 min. Finally, 2 mg of QD was added, and the mixture was reacted at room temperature for 30 minutes, and allowed to stand for 24 hours to obtain a mixed solution. The mixed solution was spin-coated, and the mixed solution was made into a mixed film. After film formation, it was heated at 80 ° C for 15 minutes to volatilize the solvent to form a mixed film. The mixed film was placed in a HHIC reactor, H _{2 was introduced} , H _{2 was} converted into H plasma, H plasma energy was adjusted to 10 eV, and cross-linking treatment was carried out for 20 min to obtain a mixed film of zinc oxide and ethanolamine-coated QD.

Example 7

The preparation steps of the mixed film in which QD and ZnO nanoparticles are crosslinked are as follows:

8 mg of QD and 8 mg of octyl mercaptan-containing ZnO nanoparticles were mixed into 4 ml of ethanol solvent to obtain a mixed solution. The mixed solution was spin-coated, and the mixed liquid was formed into a mixed film, and after film formation, it was vacuum dried to volatilize the solvent to form a mixed film of 40 nm. The mixed film was placed in a HHIC reactor, H _{2 was introduced} , H _{2 was} converted into H plasma, H plasma energy was adjusted to 10 eV, and cross-linking treatment was carried out for 10 min to obtain a mixed film in which QD and ZnO nanoparticles were crosslinked.

The prepared mixed film of QD and ZnO nanoparticles was tested by scanning electron microscopy. The test results are shown in Fig. 7. The results show that QD and ZnO nanoparticles are uniformly bonded to the mixed film after HHIC cross-linking, QD and ZnO. Nanoparticle cross-linking was successful.

Example 8

The preparation steps of the mixed film in which QD and WO nanoparticles are crosslinked are as follows:

9 mg of QD was mixed with 7 mg of octyl mercaptan-containing WO nanoparticles to 4 ml of chlorobenzene solvent to obtain a mixed solution. The mixed solution was spin-coated, and the mixed solution was made into a mixed film, and after film formation, it was vacuum dried to volatilize the solvent to form a mixed film of 100 nm. The mixed film was placed in a HHIC reactor, H _{2 was introduced} , H _{2 was} converted into H plasma, H plasma energy was adjusted to 100 eV, and cross-linking treatment was carried out for 1 min to obtain a mixed film in which QD and WO nanoparticles were crosslinked.

Example 9

The preparation steps of the mixed film in which QD and NiO nanoparticles are crosslinked are as follows:

8 mg of QD was mixed with 6 mg of NiO nanoparticles containing ethanolamine on the surface into 5 ml of n-octane solvent to obtain a mixed solution. The mixture was spin-coated, and the mixture was formed into a mixed film. After film formation, the solvent was evaporated in vacuo to form a 60 nm mixed film. The mixed film was placed in a HHIC reactor, H _{2 was introduced} , H _{2 was} converted into H plasma, H plasma energy was adjusted to 50 eV, and cross-linking treatment was carried out for 5 min to obtain a mixed film in which QD and NiO nanoparticles were crosslinked.

Example 10

The preparation steps of the mixed film in which QD and TiO nanoparticles are crosslinked are as follows:

8 mg of QD and 6 mg of ethanolamine-containing TiO nanoparticles were mixed into 4 ml of acetone solvent to obtain a mixed solution. The mixed solution was spin-coated, and the mixed liquid was formed into a mixed film, and after film formation, it was vacuum dried to volatilize the solvent to form a mixed film of 40 nm. The mixed film was placed in a HHIC reactor, H _{2 was introduced} , H _{2 was} converted into H plasma, H plasma energy was adjusted to 1 eV, and cross-linking treatment was carried out for 30 min to obtain a mixed film in which QD and TiO nanoparticles were crosslinked.

It is to be understood that the application of the present invention is not limited to the above-described examples, and those skilled in the art can make modifications and changes in accordance with the above description, all of which are within the scope of the appended claims.

Claims (20)

1. A method for preparing a mixed film, comprising:

   Mixing the quantum dots with the carrier in a solvent to obtain a mixed solution;

   The mixed solution is prepared into a mixed film of the content sub-point and the carrier by a solution method;

   The mixed film of the content sub-dots and the carrier is cross-linked by HHIC technology to crosslink the quantum dots and the carrier to obtain a crosslinked mixed film.
2. The method of producing a mixed film according to claim 1, wherein the carrier is one or both of a polymer and a small molecule.
3. The method of preparing a mixed film according to claim 2, wherein the polymer is one of a first p-type semiconductor material, a first n-type semiconductor material, a first insulator material, and a first luminescent material. The small molecule is one or more of a second p-type semiconductor material, a second n-type semiconductor material, a second insulator material, and a second luminescent material.
4. The method for preparing a mixed film according to claim 3, wherein the first p-type semiconductor material is one or more of PVK, TFB, poly-TPD, and P3HT, and the first n-type semiconductor The material is OXD-7, the first insulator material is one or more of PMMA, PVP, PEN, PET, and the first luminescent material is MEH-PPV.
5. The method for preparing a mixed film according to claim 3, wherein the second p-type semiconductor material is one or more of NPB, CBP, and TCTA, and the second n-type semiconductor material is Bphen. One or more of Alq and Liq, the second insulator material is UGH1, and the second luminescent material is one or both of Irppy3 and Firpic.
6. The method for producing a mixed film according to claim 1, wherein the carrier is an inorganic precursor, and a mixed film in which an inorganic substance and a quantum dot are crosslinked is obtained.
7. The method for preparing a mixed film according to claim 6, wherein the inorganic precursor is one or more selected from the group consisting of zinc acetate, molybdenum acetate, nickel acetate, titanium acetate, and tungsten acetate.
8. The method for producing a mixed film according to claim 6 or 7, wherein an organic substance is added to the mixed liquid to obtain a mixed film in which an inorganic substance, an organic substance and a quantum dot are crosslinked.
9. The method for producing a mixed film according to claim 8, wherein the organic substance is one or more selected from the group consisting of ethanolamine, 2-phenoxyethanol, and ethylene glycol butyl ether.
10. The method for producing a mixed film according to claim 1, wherein the carrier is an inorganic nanoparticle having an organic ligand on its surface.
11. The method for preparing a mixed film according to claim 10, wherein the inorganic nanoparticles are one or more of MoO _x , WO, NiO, ZnO, and TiO;

    And/or the organic ligand is one or more of octyl mercaptan and ethanolamine.
12. The method for preparing a mixed film according to claim 1, wherein the mixed film of the content sub-dots and the carrier is cross-linked by HHIC technology to crosslink the quantum dots and the carrier to obtain cross-linking. The step of mixing the film comprises: placing a mixed film of the content sub-point and the carrier in a HHIC reactor, introducing H ₂ , and converting H ₂ into H plasma, and performing a mixed film of the content sub-point and the carrier by H plasma. Cross-linking treatment causes cross-linking between the quantum dots and the carrier to obtain a crosslinked mixed film.
13. The method of producing a mixed film according to claim 12, wherein the energy of the H plasma is from 1 to 100 eV.
14. The method for preparing a mixed film according to claim 12, wherein the crosslinking treatment time is from 1 to 30 min.
15. A mixed film characterized in that the mixed film is prepared by the production method according to any one of claims 1 to 14.
16. A method for preparing a quantum dot light emitting diode device, comprising the steps of:

    Depositing a first functional layer on a surface of the bottom electrode substrate;

    Putting the first functional layer into the HHIC reactor and introducing H ₂ , the H _{2 is} ionized to form H plasma, and the solute component in the first functional layer is cross-linked by the H plasma;

    Depositing a quantum dot luminescent layer on the surface of the first functional layer after crosslinking, and crosslinking the quantum dots in the quantum dot luminescent layer by H plasma;

    Depositing a second functional layer on the surface of the cross-linked quantum dot light-emitting layer, and crosslinking the solute component in the second functional layer by H plasma;

    A top electrode is deposited on the second functional layer after crosslinking to obtain a quantum dot light emitting diode.
17. The method of fabricating a quantum dot light emitting diode device according to claim 16, wherein the energy of the H plasma is 1-100 eV.
18. The method of preparing a quantum dot light emitting diode device according to claim 16, wherein the crosslinking reaction time is 1-30 min.
19. The method of fabricating a quantum dot light emitting diode device according to claim 16, wherein when the quantum dot light emitting diode device is of an inverted structure, the first functional layer is an electron transport layer, an electron injection layer or an empty One or more of the hole blocking layers, the second functional layer being one or more of a hole transport layer, a hole injection layer or an electron blocking layer.
20. The method of fabricating a quantum dot light emitting diode device according to claim 16, wherein when the quantum dot light emitting diode device has a positive structure, the first functional layer is a hole transport layer and a hole injection layer. Or one or more of the electron blocking layers, the second functional layer being one or more of an electron transport layer, an electron injection layer or a hole blocking layer.

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