CN112186115B - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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CN112186115B
CN112186115B CN202011043094.2A CN202011043094A CN112186115B CN 112186115 B CN112186115 B CN 112186115B CN 202011043094 A CN202011043094 A CN 202011043094A CN 112186115 B CN112186115 B CN 112186115B
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metal fullerene
fullerene derivative
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mixed solution
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CN112186115A (en
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卢志高
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BOE Technology Group Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers

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  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本发明实施例提供一种有机电致发光器件及其制备方法，有机电致发光器件包括阳极、阴极以及设置在所述阳极和阴极之间的发光层，所述阳极和所述发光层之间设置有空穴注入层，所述空穴注入层包括主体材料和掺杂在所述主体材料中的掺杂材料，所述主体材料包括聚3,4‑亚乙基二氧噻吩和聚苯乙烯磺酸盐，所述掺杂材料包括金属富勒烯衍生物，所述掺杂材料满足：‑3.4eV＜HOMO＜3.6eV；其中，HOMO为所述掺杂材料的最高占据分子轨道HOMO能级。

The embodiment of the present invention provides an organic electroluminescent device and a preparation method thereof. The organic electroluminescent device includes an anode, a cathode and a light-emitting layer arranged between the anode and the cathode. A hole injection layer is arranged between the anode and the light-emitting layer. The hole injection layer includes a main material and a doping material doped in the main material. The main material includes poly (3,4-ethylenedioxythiophene) and polystyrene sulfonate. The doping material includes a metal fullerene derivative. The doping material satisfies: -3.4eV＜HOMO＜3.6eV; wherein HOMO is the highest occupied molecular orbital HOMO energy level of the doping material.

Description

Organic electroluminescent device and preparation method thereof
Technical Field
The invention relates to the technical field of display, in particular to an organic electroluminescent device and a preparation method thereof.
Background
The full solution processing quantum dot light Emitting diode (Quantum Dot Light-emission Diodes, QLEDs) has great potential application value in the future display and illumination fields. Currently, a full solution process quantum dot light emitting diode includes an anode, a cathode, and a light emitting layer disposed between the anode and the cathode, and light emitting principle thereof is to inject holes and electrons from the anode and the cathode into the light emitting layer, respectively, and when the electrons and holes meet in the light emitting layer, the electrons and holes are recombined to generate excitons (exciton), which emit light while being converted from an excited state to a ground state. In order to smoothly inject electrons and holes from the electrode to the light-emitting layer at a low driving voltage, a hole injection layer and a hole transport layer are disposed between the anode and the light-emitting layer, and an electron injection layer and an electron transport layer are disposed between the cathode and the light-emitting layer.
The imbalance in hole and electron injection caused by the difficulty in hole injection remains a major factor impeding the implementation of efficient full solution processing QLEDs. Therefore, how to lower the hole injection barrier and improve the hole injection efficiency is the first problem to be considered in preparing the efficient full solution plus QLEDs.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
The embodiment of the invention provides an organic electroluminescent device, which comprises an anode, a cathode and a light-emitting layer arranged between the anode and the cathode, wherein a hole injection layer is arranged between the anode and the light-emitting layer, the hole injection layer comprises a main body material and a doping material doped in the main body material, the main body material comprises poly 3, 4-ethylenedioxythiophene and polystyrene sulfonate, the doping material comprises a metal fullerene derivative, and the doping material satisfies the following conditions:
-3.4eV＜HOMO＜3.6eV；
wherein HOMO is the highest occupied molecular orbital HOMO energy level of the doped material.
In an exemplary embodiment, the metal fullerene derivative includes a metal fullerene and a derivative based on a metal fullerene.
In an exemplary embodiment, the metal fullerene includes one or a combination of several of gd@c82, dy@c82, sc3c2@c80, y2@c79n and dysc2n@c80.
In an exemplary embodiment, the metallofullerene-based derivative has the chemical structural formula MCn-X, wherein M is Gd, dy or Yb; x is ethylenediamine or beta-alanine, and n is not less than 60.
In an exemplary embodiment, the molar ratio of the poly 3, 4-ethylenedioxythiophene to the polystyrene sulfonate is 1:2 to 1:5.
In an exemplary embodiment, the hole injection layer has a roughness Ra <0.1 microns.
In an exemplary embodiment, the mass ratio of the doping material to the host material is 1:1 to 1:10.
The embodiment of the invention also provides a preparation method of the metal fullerene derivative, which comprises the following steps:
Mixing metal fullerene solid with ligand solution to form mixed solution;
adding an acid solution or an alkali solution into the mixed solution to form a metal fullerene derivative solution;
and dialyzing the metal fullerene derivative solution to obtain the metal fullerene derivative.
In an exemplary embodiment, adding an acid solution or an alkali solution to the mixed solution to form a metal fullerene derivative solution, comprising:
adding an alkali solution into the mixed solution to form a metal fullerene derivative mixed solution;
adding alcohol into the metal fullerene derivative mixed solution to precipitate the metal fullerene derivative in the metal fullerene derivative mixed solution;
separating the precipitated metal fullerene derivative by centrifugation;
And dissolving the separated metal fullerene derivative to form a metal fullerene derivative solution.
In an exemplary embodiment, adding an acid solution or an alkali solution to the mixed solution to form a metal fullerene derivative solution, comprising:
Drying the mixed solution to form a solid;
Adding the solid into an acid solution to form a metal fullerene derivative mixed solution;
And adjusting the PH value of the metal fullerene derivative mixed solution to be 4-6 to form the metal fullerene derivative solution.
The invention provides an organic electroluminescent device and a preparation method thereof, wherein a hole injection layer is formed by doping metal fullerene derivatives in poly-3, 4-ethylenedioxythiophene and polystyrene sulfonate, so that the hole injection potential barrier is reduced, and the hole injection efficiency is improved.
Of course, it is not necessary for any one product or method of practicing the invention to achieve all of the advantages set forth above at the same time. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of embodiments of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate and do not limit the application. The shapes and sizes of the various components in the drawings are not to scale, and are intended to illustrate the present application only.
Fig. 1 is a schematic diagram of an OLED structure according to an exemplary embodiment of the present disclosure.
Detailed Description
The embodiments herein may be embodied in a number of different forms. One of ordinary skill in the art will readily recognize the fact that the implementations and content may be transformed into a wide variety of forms without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure should not be construed as being limited to the following description of the embodiments. Embodiments of the present disclosure and features of embodiments may be combined with each other arbitrarily without conflict.
In the drawings, the size of constituent elements, thicknesses of layers, or regions may be exaggerated for clarity in some cases. Thus, any one implementation of the present disclosure is not necessarily limited to the dimensions shown in the figures, where the shapes and sizes of the components do not reflect true proportions. Further, the drawings schematically illustrate ideal examples, and any one implementation of the present disclosure is not limited to the shapes or the numerical values and the like shown in the drawings.
The ordinal numbers of "first", "second", "third", etc. in this document are provided to avoid intermixing of constituent elements and are not intended to be limiting in terms of number.
In this document, for convenience, terms such as "middle", "upper", "lower", "front", "rear", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like are used to describe the positional relationship of the constituent elements with reference to the accompanying drawings, only for convenience of description and simplicity of description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present disclosure. The positional relationship of the constituent elements may be appropriately changed according to the direction of the described constituent elements. Therefore, the present invention is not limited to the words described herein, and may be replaced as appropriate according to circumstances.
In this document, the terms "mounted," "connected," and "connected" are to be construed broadly, unless otherwise specifically indicated and defined. For example, it may be a fixed connection, a removable connection, or an integral connection; may be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intermediate members, or may be in communication with the interior of two elements. The meaning of the above terms in the present disclosure can be understood by one of ordinary skill in the art as appropriate.
Herein, a transistor refers to an element including at least three terminals of a gate electrode, a drain electrode, and a source electrode. The transistor has a channel region between a drain electrode (or a drain electrode terminal, a drain region, or a drain electrode) and a source electrode (or a source electrode terminal, a source region, or a source electrode), and a current can flow through the drain electrode, the channel region, and the source electrode. Herein, a channel region refers to a region through which current mainly flows.
Herein, the first electrode may be a drain electrode, the second electrode may be a source electrode, or the first electrode may be a source electrode, and the second electrode may be a drain electrode. In the case of using transistors having opposite polarities or in the case of a change in the direction of current during circuit operation, the functions of the "source electrode" and the "drain electrode" may be exchanged with each other. Thus, herein, the "source electrode" and the "drain electrode" may be interchanged.
In this context, "electrically connected" includes the case where constituent elements are connected together by an element having some electric action. The "element having a certain electric action" is not particularly limited as long as it can transmit and receive an electric signal between the constituent elements connected. The "element having some kind of electrical action" may be, for example, an electrode or a wiring, or a switching element such as a transistor, or other functional element such as a resistor, an inductor, or a capacitor.
As used herein, "parallel" refers to a state in which two straight lines form an angle of-10 ° or more and 10 ° or less, and thus, a state in which the angle is-5 ° or more and 5 ° or less is also included. The term "perpendicular" refers to a state in which the angle formed by two straight lines is 80 ° or more and 100 ° or less, and thus includes a state in which the angle is 85 ° or more and 95 ° or less.
In this context, "film" and "layer" may be interchanged. For example, the "conductive layer" may be sometimes replaced with a "conductive film". In the same manner, the "insulating film" may be replaced with the "insulating layer" in some cases.
By "about" herein is meant not strictly limited to numerical values which are within the limits of permitted process and measurement errors.
In the structure of the organic electroluminescent device, the hole injection layer (Hole Injection Layer, HIL for short) is made of a material similar to that of the hole transport layer (Hole Transport Layer, HTL for short), and the highest occupied molecular orbital (Highest Occupied Molecular Orbit, HOMO for short) energy level of the hole injection layer material is between the work function of the anode and the HOMO energy level of the hole transport layer material, so that the effect of hole injection is achieved by reducing the potential barrier between the anode and the hole transport layer. Research shows that potential barriers still exist among layers of the structure, the injection effect is general, and the charge transmission performance is poor. Although the injection effect can be improved by using a multi-layer structure with different HOMO levels, the multi-layer structure increases multiple interfaces, which negatively affects the performance of the OLED, and the use of multiple different materials results in the need for more evaporation sources and evaporation chambers, which does not allow for mass production feasibility.
In another organic electroluminescent device structure, the hole injection layer adopts a doped structure, the hole injection layer comprises a main body material and a doped material, the doped material is a P-type doped (P-doping) material, and the characteristic that the P-type doped material has strong electron withdrawing capability is utilized to enable electrons to rapidly move to the anode side under the action of an electric field, so that holes are rapidly transmitted to the hole transmission layer side, and high-efficiency hole injection performance is realized. Research shows that the P-type doped structure has poor thermal stability, is easy to crystallize, is unfavorable for preparation, and easily causes inter-subpixel crosstalk (cross talk) when the doping proportion is more than 5%, so that poor display is generated.
Exemplary embodiments of the present disclosure provide an organic electroluminescent device including an anode, a cathode, and a light emitting layer disposed between the anode and the cathode, a hole injection layer disposed between the anode and the light emitting layer, the hole injection layer including a host material including poly 3, 4-ethylenedioxythiophene and polystyrene sulfonate and a doping material doped in the host material, the doping material including a metal fullerene derivative, the doping material satisfying:
-3.4eV＜HOMO＜3.6eV；
wherein HOMO is the highest occupied molecular orbital HOMO energy level of the doped material.
Fig. 1 is a schematic view of an organic electroluminescent device structure according to an exemplary embodiment of the present disclosure. As shown in fig. 1, the organic electroluminescent device includes an anode 10, a cathode 90, and an organic light emitting layer disposed between the anode 10 and the cathode 90. In an exemplary embodiment, the organic light emitting layer includes a hole injection layer 20, a hole transport layer 30, an Electron Blocking Layer (EBL) 40, an emitting layer (EML) 50, a Hole Blocking Layer (HBL) 60, an Electron Transport Layer (ETL) 70, and an Electron Injection Layer (EIL) 80, which are stacked. In an exemplary embodiment, the hole injection layer 20 is a dual injection layer structure including a first hole injection layer 21 and a second hole injection layer 22 stacked, the first hole injection layer 21 being disposed between the anode 10 and the second hole injection layer 22, and the second hole injection layer 22 being disposed between the first hole injection layer 21 and the hole transport layer 30. In an exemplary embodiment, the hole injection layer 20 is configured to lower a potential barrier for injecting holes from the anode, so that holes can be efficiently injected from the anode into the light emitting layer 50. The hole transport layer 30 is configured to achieve controlled migration of injected holes in an orderly orientation. The electron blocking layer 40 is configured to form a transport barrier for electrons, preventing electrons from migrating out of the light emitting layer 50. The light emitting layer 50 is configured to recombine electrons and holes to emit light. The hole blocking layer 60 is configured to form a transport barrier for holes, preventing holes from migrating out of the light emitting layer 50. The electron transport layer 70 is configured to effect controlled migration of the injected electrons in an orderly orientation. The electron injection layer 80 is configured to lower a potential barrier of electrons injected from the cathode so that electrons can be efficiently injected from the cathode to the light emitting layer 50.
In an exemplary embodiment, the hole injection layer includes a host material including poly 3, 4-ethylenedioxythiophene (PEDOT) and polystyrene sulfonate (PPS), and a doping material doped in the host material, the doping material including a metal fullerene derivative, the doping material satisfying: -3.4eV < HOMO < 3.6eV; wherein HOMO is the highest occupied molecular orbital HOMO energy level of the doped material.
Wherein, the molecular structural formula of the poly 3, 4-ethylenedioxythiophene is as follows:
In an exemplary embodiment, the metal fullerene derivative includes a metal fullerene and a derivative based on a metal fullerene.
In an exemplary embodiment, the metallofullerene may be one or a combination of several of gd@c 82、Dy@C82、Sc3C2@C80、Y2@C79 N and DySc 2N@C80.
In an exemplary embodiment, the metal fullerene-based derivative has the chemical structural formula MC n -X, wherein M is Gd, dy or Yb; x is ethylenediamine or beta-alanine, and n is not less than 60.
According to the embodiment of the invention, after the ethylenediamine or beta-alanine is derivatized with the metal fullerene, the ethylenediamine or beta-alanine not only has excellent water dispersibility and film forming property, but also can be combined with the sulfonic acid group in the main material (PEDOT: PSS) through the action of a chemical bond due to the existence of amino, so that the effect is firmer.
Wherein, the molecular structural formula of the ethylenediamine is:
the molecular structural formula of the beta-alanine is as follows:
In an exemplary embodiment, the molar ratio of poly 3, 4-ethylenedioxythiophene to polystyrene sulfonate is from 1:2 to 1:5.
In an exemplary embodiment, the hole injection layer has a roughness Ra <0.1 microns. In this embodiment, the doped material in the hole injection layer is a metal fullerene derivative, and the film formation effect is smaller than that of a fullerene alone (film formation roughness Ra > 0.2).
The metal fullerene derivative in the embodiment is simple to prepare, has excellent water dispersibility, can be well dispersed in a main body material formed by poly (3, 4-ethylenedioxythiophene) and polystyrene sulfonate, and has a film forming effect which is much better than that of the fullerene and the metal fullerene.
The embodiment of the invention also provides a preparation method of the metal fullerene derivative, which comprises the following steps:
Mixing metal fullerene solid with ligand solution to form mixed solution;
adding an acid solution or an alkali solution into the mixed solution to form a metal fullerene derivative solution;
and dialyzing the metal fullerene derivative solution to obtain the metal fullerene derivative.
In an exemplary embodiment, adding an acid solution or an alkali solution to the mixed solution to form a metal fullerene derivative solution, comprising:
adding an alkali solution into the mixed solution to form a metal fullerene derivative mixed solution;
adding alcohol into the metal fullerene derivative mixed solution to precipitate the metal fullerene derivative in the metal fullerene derivative mixed solution;
separating the precipitated metal fullerene derivative by centrifugation;
And dissolving the separated metal fullerene derivative to form a metal fullerene derivative solution.
In an exemplary embodiment, adding an acid solution or an alkali solution to the mixed solution to form a metal fullerene derivative solution, comprising:
Drying the mixed solution to form a solid;
Adding the solid into an acid solution to form a metal fullerene derivative mixed solution;
And adjusting the PH value of the metal fullerene derivative mixed solution to be 4-6 to form the metal fullerene derivative solution.
In an exemplary embodiment, a method for producing a metallofullerene derivative according to an embodiment of the present invention will be described by taking β -alanine as a ligand and metallofullerene M@C 82 as an example. The preparation method of the metal fullerene derivative comprises the following steps:
(1) The solid metal fullerenes are formed into a powder. Forming the solid metal fullerenes into a powder includes: grinding solid metal fullerene M@C 82 in grinder for 30-90s each time with grinding power of 40-100Hz and grinding times of 30-50 times to form metal fullerene M@C 82 powder from solid metal fullerene M@C 82.
(2) Solid metal fullerene powder is mixed with ligand. Mixing the solid metal fullerene powder with the ligand comprises: subsequently 50mg to 100mg of metallofullerene M@C 82 powder was added to the solution containing 3.6g to 10g of beta-alanine (Ala) to form a mixed solution.
(3) Forming a metal fullerene derivative. The formation of the metal fullerene derivative includes: adding 50-100 mL NaOH aqueous solution into the mixed solution, heating to 80-100 ℃ under stirring, and reacting metallo fullerene M@C 82 powder with beta-alanine (Ala) to form a metallo fullerene derivative mixed solution. Wherein the NaOH aqueous solution contains 14% -30% NaOH by mass. NaOH derivatizes metallo-fullerenes M@C 82, enabling metallo-fullerenes M@C 82 to react with beta-alanine (Ala) to form metallo-fullerene derivatives.
(4) Purifying the metal fullerene derivative. The purified metal fullerene derivative comprises: and (3) reducing the temperature to room temperature, adding ethanol into the metal fullerene derivative mixed solution, and precipitating the metal fullerene derivative in the metal fullerene derivative mixed solution, so that the metal fullerene derivative in the metal fullerene derivative mixed solution is separated from unreacted metal fullerene M@C 82, beta-alanine (Ala) and NaOH in the metal fullerene derivative mixed solution.
(5) Forming a solution of the metal fullerene derivative. Forming the metal fullerene derivative solution includes: separating the precipitated metal fullerene derivative from the metal fullerene derivative mixed solution by centrifugation (9000-12000 r/min); dissolving the separated metal fullerene derivative in water to form a metal fullerene derivative solution.
(6) Obtaining the metal fullerene derivative. The metal fullerene derivative is obtained by the following steps: and (3) placing the metal fullerene derivative solution in a dialysis bag for dialysis for three days, and filtering the dialyzed metal fullerene derivative solution through a 220nm filter membrane to obtain the metal fullerene derivative.
In an exemplary embodiment, a method for preparing a metal fullerene derivative according to an embodiment of the present invention will be described by taking Ethylenediamine (EDA) as a ligand and forming a metal fullerene derivative with a metal fullerene M@C 82 as an example. The preparation method of the metal fullerene derivative comprises the following steps:
(1) Forming a mixed solution. The forming of the mixed liquid comprises: 50mL of Ethylenediamine (EDA) was added to a 100mL conical flask with a stopper, and 50mg of solid fullerene M@C 82 was added to 50mL of Ethylenediamine (EDA) to form a mixed solution. Wherein, the Ethylenediamine (EDA) is analytically pure and is a Chinese medicine reagent, and the density of the Ethylenediamine (EDA) is 0.9mg/ml. The purity of the solid fullerene M@C 82 was 99%, which was obtained from the company of materials technology, ltd.
(2) The solid fullerenes M@C 82 in the mixture were filtered. Filtering the solid fullerenes M@C 82 in the mixed liquor includes: adding a magnetic stirrer into the mixed solution, stirring for 24 hours (temperature: room temperature, rotating speed 1000 r/min) by using a magnetic stirrer, forming solid fullerene M@C 82 in the mixed solution into powder, filtering the stirred mixed solution through a filter membrane (aperture: 200 nm), and filtering out solid fullerene M@C 82 powder with larger particle diameter.
(3) Forming a metal fullerene derivative mixed solution. The forming of the metal fullerene derivative mixture comprises: adding the filtered mixed solution into a 250ml round-bottom flask, and then using a rotary evaporator to spin-dry the mixed solution completely (the temperature is 70 ℃ C., the rotating speed is 80 r/min) to form a solid; adding the solid into hydrochloric acid, and vibrating to dissolve the solid to form a metal fullerene derivative mixed solution. Wherein the concentration of hydrochloric acid is less than 1mol/L. Hydrochloric acid derivatizes the metallofullerene M@C 82 to enable the metallofullerene M@C 82 to react with Ethylenediamine (EDA) to form a metallofullerene derivative.
(4) Forming a solution of the metal fullerene derivative. Forming the metal fullerene derivative solution includes: and adjusting the PH value of the metal fullerene derivative mixed solution to be 4-6 to form a metal fullerene derivative solution. The pH is adjusted to ensure that excess ethylenediamine is present in the form of chloride salts that can be adequately removed in a subsequent dialysis step.
(5) Obtaining the metal fullerene derivative. The metal fullerene derivative is obtained by the following steps: and (3) filling the metal fullerene derivative solution into a dialysis bag (with a cut-off molecular weight of 3500), dialyzing in ultrapure water until the conductivity of the ultrapure water is less than 1 mu s/cm, and thus obtaining the metal fullerene derivative.
While the embodiments disclosed in the present disclosure are described above, the embodiments are only employed for facilitating understanding of the present disclosure, and are not intended to limit the present disclosure. Any person skilled in the art will recognize that any modifications and variations can be made in the form and detail of the present disclosure without departing from the spirit and scope of the disclosure, which is defined by the appended claims.

Claims (10)

1. An organic electroluminescent device comprising an anode, a cathode, and a light emitting layer disposed between the anode and the cathode, a hole injection layer disposed between the anode and the light emitting layer, the hole injection layer comprising a host material and a dopant material doped in the host material, the host material comprising poly-3, 4-ethylenedioxythiophene and polystyrene sulfonate, the dopant material comprising a metallofullerene derivative, the dopant material satisfying:
-3.4eV＜HOMO＜3.6eV；
wherein HOMO is the highest occupied molecular orbital HOMO energy level of the doped material.
2. The organic electroluminescent device of claim 1, wherein the metal fullerene derivative comprises a metal fullerene-based derivative.
3. The organic electroluminescent device of claim 2, wherein the metallofullerene comprises one or a combination of several of gd@c 82、Dy@C82、Sc3C2@C80、Y2@C79 N and DySc 2N@C80.
4. The organic electroluminescent device according to claim 2, wherein the derivative based on metallofullerene has a chemical structural formula of MC n -X, wherein M is Gd, dy or Yb; x is ethylenediamine or beta-alanine, and n is not less than 60.
5. The organic electroluminescent device of claim 1, wherein a molar ratio of the poly 3, 4-ethylenedioxythiophene to the polystyrene sulfonate is from 1:2 to 1:5.
6. The organic electroluminescent device of claim 1, wherein the hole injection layer has a roughness Ra <0.1 microns.
7. The organic electroluminescent device of claim 1, wherein a mass ratio of the dopant material to the host material is from 1:1 to 1:10.
8. A method for producing a metal fullerene derivative, comprising:
Mixing metal fullerene solid with ligand solution to form mixed solution;
adding an acid solution or an alkali solution into the mixed solution to form a metal fullerene derivative solution;
dialyzing the metal fullerene derivative solution to obtain a metal fullerene derivative;
the metal fullerene derivative forms a doping material of the hole injection layer; the doping material satisfies the following conditions:
-3.4eV＜HOMO＜3.6eV；
wherein HOMO is the highest occupied molecular orbital HOMO energy level of the doped material.
9. The method of preparing a metal fullerene derivative according to claim 8, wherein adding an acid solution or an alkali solution to the mixed solution to form a metal fullerene derivative solution comprises:
adding an alkali solution into the mixed solution to form a metal fullerene derivative mixed solution;
adding alcohol into the metal fullerene derivative mixed solution to precipitate the metal fullerene derivative in the metal fullerene derivative mixed solution;
separating the precipitated metal fullerene derivative by centrifugation;
And dissolving the separated metal fullerene derivative to form a metal fullerene derivative solution.
10. The method of preparing a metal fullerene derivative according to claim 8, wherein adding an acid solution or an alkali solution to the mixed solution to form a metal fullerene derivative solution comprises:
Drying the mixed solution to form a solid;
Adding the solid into an acid solution to form a metal fullerene derivative mixed solution;
And adjusting the PH value of the metal fullerene derivative mixed solution to be 4-6 to form the metal fullerene derivative solution.
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