CN117998950A - Composite material, preparation method of composite material, photoelectric device and electronic equipment - Google Patents

Composite material, preparation method of composite material, photoelectric device and electronic equipment Download PDF

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Publication number
CN117998950A
CN117998950A CN202211354307.2A CN202211354307A CN117998950A CN 117998950 A CN117998950 A CN 117998950A CN 202211354307 A CN202211354307 A CN 202211354307A CN 117998950 A CN117998950 A CN 117998950A
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metal oxide
transport layer
composite material
electron transport
chitosan
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吴劲衡
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TCL Technology Group Co Ltd
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TCL Technology Group Co Ltd
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Priority to CN202211354307.2A priority Critical patent/CN117998950A/en
Priority to PCT/CN2023/126348 priority patent/WO2024093747A1/en
Publication of CN117998950A publication Critical patent/CN117998950A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)
  • Luminescent Compositions (AREA)

Abstract

The application discloses a composite material, a preparation method of the composite material, a photoelectric device and electronic equipment, wherein the composite material comprises chitosan and metal oxide, and the chitosan is coordinately combined on the surface of the metal oxide, so that the surface defect state of the metal oxide is reduced, the stability of the metal oxide and the performance stability of the composite material are improved, the composite material can be used for preparing an electron transport layer of the photoelectric device to optimize the electron injection level of the photoelectric device, and the photoelectric device containing the composite material is applied to the electronic equipment, thereby being beneficial to improving the working stability, the photoelectric performance and the service life of the electronic equipment.

Description

Composite material, preparation method of composite material, photoelectric device and electronic equipment
Technical Field
The application relates to the technical field of photoelectricity, in particular to a composite material, a preparation method of the composite material, a photoelectric device and electronic equipment.
Background
The metal oxide is a compound formed by combining metal elements and oxygen elements, and after the metal oxide is nanocrystallized, the metal oxide has small-size effect, surface and interface effect, quantum dot size effect and macroscopic quantum tunnel effect due to the characteristics of small size, large specific surface area and many surface active centers, so that the metal oxide is widely applied to high-efficiency catalysts, batteries, photoelectric devices, super capacitors, energy storage devices, magnetic devices and optical devices.
The surface of the metal oxide has many defect states caused by oxygen vacancies, and the environmental condition is one of the main influencing factors of the number of defect states, resulting in poor stability of the metal oxide. Therefore, how to improve the stability of the metal oxide is of great importance for the application and development of the metal oxide.
Disclosure of Invention
The application provides a composite material, a preparation method of the composite material, a photoelectric device and electronic equipment, so as to improve the stability of metal oxide.
The technical scheme of the application is as follows:
In a first aspect, the present application provides a composite material comprising a chitosan and a metal oxide, the chitosan being coordinately bound to the surface of the metal oxide.
Optionally, in the composite material, the metal oxide: the mass ratio of the chitosan is 1: (0.05-0.1).
Optionally, the metal oxide is selected from at least one of ZnO、TiO2、SnO2、BaO、Ta2O3、Al2O3、ZrO2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl、ZnOF or ZnMgLiO;
And/or the metal oxide has an average particle diameter of 2nm to 5nm;
and/or, the forbidden band width of the metal oxide is 2.0eV to 6.0eV.
Optionally, the composite material is composed of chitosan and a metal oxide.
In a second aspect, the present application also provides a method for preparing a composite material, comprising the steps of: providing a metal oxide solution and chitosan, and mixing the metal oxide solution and the chitosan for reaction to obtain the composite material.
Alternatively, the temperature of the mixing reaction is 15 ℃ to 35 ℃, and the time of the mixing reaction is 30 minutes to 60 minutes.
Optionally, the metal oxide in the metal oxide solution: the mass ratio of the chitosan is 1: (0.05-0.1);
and/or the solvent of the metal oxide solution is selected from at least one of methanol, ethanol, glycol, glycerol, isopropanol, butanol, amyl alcohol, octanol, 2-methoxyethanol, 2-ethoxyethanol or 2-methoxybutanol.
In a third aspect, the present application also provides an optoelectronic device comprising:
An anode;
A cathode disposed opposite the anode; and
An electron transport layer disposed between the anode and the cathode;
Wherein the electron transport layer comprises the composite material according to any one of the first aspects or the composite material produced by the production method according to any one of the second aspects.
Optionally, the optoelectronic device further comprises a light emitting layer disposed between the anode and the electron transport layer; the material of the light-emitting layer is an organic light-emitting material or quantum dots;
Wherein the organic luminescent material is selected from at least one of a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material or a DBP fluorescent material;
The quantum dots are selected from at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots or organic-inorganic hybrid perovskite quantum dots; when the quantum dot is selected from a single component quantum dot or a core-shell structure quantum dot, the material of the single component quantum dot, the material of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected from at least one of group II-VI compound, group III-V compound, group IV-VI compound, or group I-III-VI compound, independently of each other, wherein the group II-VI compound is selected from at least one of CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe or HgZnSTe, the group III-V compound is selected from at least one of GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs or InAlPSb, the group IV-VI compound is selected from at least one of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe or SnPbSTe, and the group I-III-VI compound is selected from at least one of CuInS, cuInSe, or AgInS;
and/or the materials of the anode and the cathode are selected from at least one of metal, carbon material or metal oxide material independently of each other, the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg, the carbon material is selected from at least one of graphite, carbon nanotube, graphene or carbon fiber, and the metal oxide material is selected from at least one of indium tin oxide, fluorine doped tin oxide, tin antimony oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide or magnesium doped zinc oxide.
Optionally, the optoelectronic device further comprises a hole functional layer, the hole functional layer is arranged between the light emitting layer and the anode, and the hole functional layer comprises a hole injection layer and/or a hole transport layer;
For the hole functional layer including the hole injection layer and the hole transport layer, the hole injection layer is closer to the anode than the hole transport layer, and the hole transport layer is closer to the light emitting layer than the hole injection layer;
The hole injection layer is made of poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), copper phthalocyanine, titanyl phthalocyanine, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4' -tris [ 2-naphthylphenylamino ] triphenylamine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide selected from at least one of an oxide of nickel, an oxide of molybdenum, an oxide of tungsten, an oxide of chromium, an oxide of copper, or an oxide of vanadium, or transition metal chalcogenide selected from at least one of MoS x、MoSex、WSx、WSex or CuS x;
And/or the material of the hole transport layer is selected from at least one of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonic acid), doped or undoped graphene, C60, niO, moO 3、WO3、V2O5、CrO3, cuO, or P-type gallium nitride.
In a fourth aspect, the present application provides a method for manufacturing an optoelectronic device, comprising the steps of:
providing a metal oxide solution and chitosan, and mixing the metal oxide solution and the chitosan for reaction to obtain a composite material; and
Providing a prefabricated device, applying the composite material on one side of the prefabricated device, and then drying to form an electron transport layer.
Optionally, after the step of drying to form an electron transport layer, the preparation method further includes the step of: and carrying out acid treatment on the electron transport layer.
Optionally, the acid treatment comprises the steps of: applying an acidic solution to a side of the electron transport layer remote from the preformed device;
And/or the acid treatment time is 5 seconds to 10 seconds.
Optionally, the solute of the acidic solution is selected from an organic acid or an inorganic acid;
And/or the solvent of the acidic solution is selected from a polar organic solvent, wherein the polar organic solvent is selected from at least one of methanol, ethanol, glycol, glycerol, isopropanol, butanol, amyl alcohol, octanol, 2-methoxyethanol, 2-ethoxyethanol or 2-methoxybutanol.
Optionally, the solute of the acidic solution is selected from at least one of hydrochloric acid, acetic acid or acrylic acid;
and/or the volume concentration of the solute in the acidic solution is 0.1% to 1.0%.
Alternatively, the temperature of the mixing reaction is 15 ℃ to 35 ℃, and the time of the mixing reaction is 30 minutes to 60 minutes;
And/or, a metal oxide in the metal oxide solution: the mass ratio of the chitosan is 1: (0.05-0.1);
and/or the solvent of the metal oxide solution is selected from at least one of methanol, ethanol, glycol, glycerol, isopropanol, butanol, amyl alcohol, octanol, 2-methoxyethanol, 2-ethoxyethanol or 2-methoxybutanol.
Optionally, after the step of acid-treating the electron transport layer, the preparation method further includes the steps of: heating the acidic solution on the side of the electron transport layer away from the prefabricated device to remove the acidic solution;
And/or, the prefabricated device comprises a bottom electrode, the electron transport layer is formed on one side of the bottom electrode, and the preparation method further comprises the steps of: forming a top electrode on a side of the electron transport layer away from the bottom electrode; one of the bottom electrode and the top electrode is an anode, and the other is a cathode.
In a fifth aspect, the present application provides an electronic device comprising an optoelectronic device according to any one of the third aspects, or an optoelectronic device produced by any one of the production methods according to the fourth aspects.
The application provides a composite material, a preparation method of the composite material, a photoelectric device and electronic equipment, and the preparation method has the following technical effects:
The composite material comprises metal oxide and chitosan, wherein hydroxyl and amino carried by the chitosan can be coordinated and combined at the oxygen vacancy of the metal oxide, so that the number of the oxygen vacancies is effectively reduced, the surface defect state of the metal oxide is reduced, the stability of the metal oxide is improved, and the performance stability of the composite material is further improved.
The preparation method of the composite material is a solution method, the chitosan can improve the dispersion performance of the metal oxide in the solution, effectively improve the agglomeration problem of the metal oxide in the solution, and effectively improve the film forming quality when the composite material is in a film form, and the preparation method has the advantages of simple operation, easy control of process conditions and convenient batch production.
The electron transport layer in the photoelectric device comprises the composite material or the composite material prepared by the preparation method, and the composite material has ideal performance stability and film forming quality, so that the electron migration capacity of the electron transport layer can be optimized, the electron transport efficiency of the photoelectric device is improved, the electroluminescent uniformity is effectively improved, and the photoelectric performance and the service life of the photoelectric device are further improved.
The photoelectric device is applied to electronic equipment, and is beneficial to improving the photoelectric performance, the working stability and the service life of the electronic equipment.
Drawings
The technical solution and other advantageous effects of the present application will be made apparent by the following detailed description of the specific embodiments of the present application with reference to the accompanying drawings.
Fig. 1 is a schematic structural diagram of a first photoelectric device according to an embodiment of the present application;
fig. 2 is a schematic structural diagram of a second photoelectric device according to an embodiment of the present application;
Fig. 3 is a schematic flow chart of a method for manufacturing an optoelectronic device according to an embodiment of the present application;
Fig. 4 is a schematic structural diagram of a third photoelectric device according to an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present application. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the application.
The following description of the embodiments is not intended to limit the preferred embodiments. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the ranges, such as 1, 2,3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The embodiment of the application provides a composite material, which comprises chitosan and metal oxide, wherein the chitosan is coordinately combined with the surface of the metal oxide.
As used herein, "chitosan" refers to a polysaccharide composed of glucosamine and acetamido-glucose polymers, which are polymers that are obtainable by partial deacetylation of chitin in the crustaceans, naturally occurring in some microorganisms (e.g., yeasts), which themselves carry a large number of hydroxyl and amino groups. The molecular weight of the chitosan is, for example, 50kDa to 2000kDa, and the degree of deacetylation is, for example, 40% to 98%.
In the composite material, the metal oxide may be undoped metal oxide or doped metal oxide. In some embodiments of the application, the metal oxide is selected from at least one of ZnO、TiO2、SnO2、BaO、Ta2O3、ZrO2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl or ZnOF. It should be noted that, for the doped metal oxide, the chemical formula provided only shows the elemental composition, and does not show the content of each element, for example: znMgO is composed of three elements, zn, mg and O.
In some embodiments of the application, the average particle size of the metal oxide is from 2nm to 5nm, for example in the range of from 2nm to 3nm, from 3nm to 4nm, from 4nm to 5nm, from 2nm to 4nm, or from 3nm to 5nm, with the average particle size of the example metal oxide being 2nm, 3nm, 4nm, or 5nm. It is understood that the metal oxide in the composite material may be a collection of a plurality of metal oxide nanoparticles of the same size and shape, or a collection of metal oxide nanoparticles of a plurality of different sizes and shapes.
In order to provide the composite with desirable electron mobility, in some embodiments of the present application, the energy gap of the metal oxide is from 2.0eV to 6.0eV, such as from 2.0eV to 3.0eV, from 3.0eV to 4.0eV, from 4.0eV to 5.0eV, or from 5.0eV to 6.0eV, and exemplified by 2.0eV, 3.0eV, 4.0eV, 5.0eV, or 6.0eV.
In some embodiments of the application, in the composite material, the metal oxide: the mass ratio of the chitosan is 1: (0.05 to 0.1), metal oxide: the mass ratio of the chitosan may be, for example, 1: (0.05-0.06), 1: (0.06-0.07), 1: (0.07-0.08), 1: (0.08 to 0.09), or 1: (0.09-0.1), metal oxide: the mass ratio of the chitosan is exemplified as 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, or 1:0.1.
In the composite material, hydroxyl and amino carried by the chitosan have the function of an 'ionic ligand', and the specific expression is as follows: the surface of the metal oxide has a large number of defects, such as oxygen defects, and the hydroxyl and amino groups carried by the chitosan can be coordinated and combined at the oxygen vacancies of the metal oxide, so that the number of the oxygen vacancies is effectively reduced, the surface defect state of the metal oxide is reduced, the stability of the metal oxide is improved, and the performance stability of the composite material is further improved.
The embodiment of the application also provides a preparation method of the composite material, which comprises the following steps: providing a metal oxide solution and chitosan, mixing the metal oxide solution and the chitosan, and reacting to obtain the composite material.
In some embodiments of the application, the temperature of the mixing reaction is 15 ℃ to 35 ℃, e.g., can be 15 ℃ to 20 ℃, 20 ℃ to 25 ℃,25 ℃ to 30 ℃, or 30 ℃ to 35 ℃, exemplified by 15 ℃, 18 ℃, 20 ℃, 23 ℃,25 ℃,30 ℃, or 35 ℃; the mixing reaction time is 30min to 60min, and may be, for example, 30min to 40min, 40min to 50min, or 50min to 60min.
In order to ensure good dispersion properties of the chitosan and the metal oxide in the solution and not to affect physicochemical properties of the chitosan and the metal oxide, in some embodiments of the present application, the solvent of the metal oxide solution is selected from at least one of methanol, ethanol, ethylene glycol, glycerol, isopropanol, butanol, pentanol, octanol, 2-methoxyethanol, 2-ethoxyethanol, or 2-methoxybutanol.
To further improve the performance stability of the composite, in some embodiments of the application, the metal oxide in the metal oxide solution: the mass ratio of the chitosan is 1: (0.05 to 0.1), for example, 1: (0.05-0.06), 1: (0.06-0.07), 1: (0.07-0.08), 1: (0.08 to 0.09), or 1: (0.09 to 0.1), an example is 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, or 1:0.1.
The embodiment of the present application further provides an optoelectronic device, as shown in fig. 1, the optoelectronic device 1 includes an anode 11, a cathode 12, and an electron transport layer 14, where the anode 11 and the cathode 12 are disposed opposite to each other, the electron transport layer 14 is disposed between the anode 11 and the cathode 12, and the electron transport layer 14 includes the composite material according to any one of the embodiments of the present application, or includes the composite material manufactured by any one of the manufacturing methods according to the embodiments of the present application.
As used herein, "optoelectronic device" refers to a class of devices made using the optoelectronic or thermoelectric effect of semiconductors, including but not limited to Light Emitting devices, photovoltaic cells, photodetectors, etc., wherein Light Emitting devices include but are not limited to Organic Light-Emitting Diodes (10 OLED) and Quantum Dot LIGHT EMITTING Diodes (QLED).
In the photoelectric device of the embodiment of the application, the material of the electron transport layer 14 comprises chitosan and metal oxide, wherein the chitosan is coordinated and combined on the surface of the metal oxide, and the surface defect state of the metal oxide is passivated by the chitosan, so that the stability of the metal oxide is improved, the electron migration capacity of the electron transport layer is further optimized, the electron transport efficiency of the photoelectric device is improved, and the photoelectric performance and the service life of the photoelectric device are improved. In addition, the composite material prepared by any one of the preparation methods is applied to the electron transport layer 14, so that the film forming quality of the electron transport layer 14 can be improved, the interface roughness between the electron transport layer 14 and the upper functional layer can be effectively reduced, and the surface flatness of the electron transport layer 14 and the upper functional layer can be improved. Taking a photoelectric device as an example of a light-emitting device, when the light-emitting device is of a positive structure, the upper functional layer can be a light-emitting layer, for example, so that the uniformity of electroluminescence is effectively improved; when the light emitting device is of an inverted structure, the upper functional layer may be, for example, a cathode, effectively improving electron injection efficiency.
In the optoelectronic device according to the embodiment of the present application, the materials of the anode 11 and the cathode 12 may be materials common in the art, for example:
The materials of the anode 11 and the cathode 12 are independently selected from at least one of metal, carbon material or metal oxide material, and the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg; the carbon material is at least one of graphite, carbon nano tube, graphene or carbon fiber; the metal oxide material may be a doped or undoped metal oxide, for example, at least one selected from Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), tin antimony oxide (ATO), aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), indium doped zinc oxide (IZO), or magnesium doped zinc oxide (MZO). The anode 11 or cathode 12 may also be selected from a composite electrode of doped or undoped transparent metal oxides with a metal sandwiched therebetween, the composite electrode including but not limited to at least one of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2 or TiO 2/Al/TiO2. The thickness of the anode 11 may be, for example, 20nm to 200nm, and the thickness of the cathode 12 may be, for example, 20nm to 200nm.
In some embodiments of the present application, the optoelectronic device 1 is a light emitting device, with continued reference to fig. 1, the optoelectronic device 1 further comprises a light emitting layer 13, the light emitting layer 13 being disposed between the anode 11 and the electron transporting layer 14.
The material of the light emitting layer 13 is for example selected from organic light emitting materials or quantum dots, the corresponding optoelectronic device 1 is an OLED or QLED, the thickness of the light emitting layer 13 may for example be 10nm to 50nm. Wherein the organic luminescent material comprises at least one of a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material or a DBP fluorescent material; the quantum dots include, but are not limited to, at least one of red, green, or blue quantum dots, and the quantum dots include, but are not limited to, at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, or organic-inorganic hybrid perovskite quantum dots, the average particle size of the quantum dots may be, for example, 5nm to 10nm, and the average particle size of the quantum dots is, for example, 5nm, 6nm, 7nm, 8nm, 9nm, or 10nm.
For single component quantum dots and core-shell structured quantum dots, the material of the single component quantum dot, the material of the core-shell structured quantum dot, or the material of the shell of the core-shell structured quantum dot includes, but is not limited to, at least one of a group II-VI compound selected from CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe or HgZnSTe, a group IV-VI compound selected from at least one of GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs or InAlPSb, or a group III-VI compound selected from at least one of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe or SnPbSTe selected from CuInS, cuInSe, or AgInS. The chemical formula provided for the material of the single component quantum dot, the material of the core of the quantum dot of the core-shell structure, or the material of the shell of the quantum dot of the core-shell structure shows only the elemental composition, and the content of each element is not shown, for example: cdZnSe is only composed of three elements Cd, zn and Se, and if the content of each element is expressed, the corresponding value is Cd xZn1-x Se,0< x <1.
For inorganic perovskite quantum dots, the structural formula of the inorganic perovskite quantum dots is AMX 3, wherein A is Cs + ion, M is divalent metal cation, M comprises, but is not limited to, Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+ or Eu 2+, and X is halogen anion, including, but not limited to, cl -、Br- or I -.
For the organic-inorganic hybrid perovskite quantum dots, the structural general formula of the organic-inorganic hybrid perovskite quantum dots is BMX 3, wherein B is an organic amine cation, including but not limited to CH 3(CH2)n-2NH3+ (n is more than or equal to 2) or NH 3(CH2)nNH3 2+ (n is more than or equal to 2), M is a divalent metal cation, M includes but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+ or Eu 2+, and X is a halogen anion, including but not limited to Cl -、Br- or I -.
It is understood that when the material of the light emitting layer includes quantum dots, the material of the light emitting layer further includes a ligand attached to the surface of the quantum dots, the ligand includes, but is not limited to, at least one of amine ligands, carboxylic acid ligands, thiol ligands, (oxy) phosphine ligands, phospholipids, soft phospholipids, or polyvinylpyridines, the amine ligands are selected from at least one of oleylamine, n-butylamine, n-octylamine, octaamine, 1, 2-ethylenediamine, or octadecylamine, the carboxylic acid ligands are selected from at least one of oleic acid, acetic acid, butyric acid, valeric acid, caproic acid, arachic acid, decanoic acid, undecylic acid, tetradecylic acid, or stearic acid, the thiol ligands are selected from at least one of ethanethiol, propanethiol, mercaptoethanol, benzenethiol, octanethiol, dodecyl mercaptan, or octadecylthiol, and the (oxy) phosphine ligands are selected from at least one of trioctylphosphine or trioctylphosphine.
In order to further enhance the optoelectronic performance and lifetime of the optoelectronic device, in some embodiments of the present application, as shown in fig. 2, the optoelectronic device 1 further comprises a hole-functional layer 15, the hole-functional layer 15 comprising a hole-injecting layer 151 and/or a hole-transporting layer 152.
In the photovoltaic device according to the embodiment of the present application, the hole function layer 15 may have a single-layer structure or a stacked-layer structure, and the thickness of the hole function layer 15 may be, for example, 10nm to 120nm. For example, the hole function layer 15 has a single-layer structure, and the hole function layer 15 is only the hole injection layer 151 or the hole transport layer 152. For another example, as shown in fig. 3, the hole functional layer 15 is formed by stacking a hole injection layer 151 and a hole transport layer 152, the hole injection layer 151 is closer to the anode 11 than the hole transport layer 152, and the hole transport layer 152 is closer to the light emitting layer 13 than the hole injection layer 151.
The thickness of the hole injection layer 151 is, for example, 10nm to 60nm, and the material of the hole injection layer 151 is, for example, selected from poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), copper phthalocyanine, titanyl phthalocyanine, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4' -tris [ 2-naphthylphenylamino ] triphenylamine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide, or transition metal chalcogenide, wherein the transition metal oxide is selected from at least one of an oxide of nickel, an oxide of molybdenum, an oxide of tungsten, an oxide of chromium, an oxide of copper, or an oxide of vanadium, and the transition metal chalcogenide is selected from at least one of MoS x、MoSex、WSx、WSex or CuS x.
The thickness of the hole transport layer 152 is, for example, 10nm to 60nm, and the material of the hole transport layer 152 is, for example, selected from Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (abbreviated as TFB, CAS No. 220797-16-0), 3-hexyl-substituted polythiophene (CAS No. 104934-50-1), poly (9-vinylcarbazole) (PVK, CAS No. 25067-59-8), poly [ bis (4-phenyl) (4-butylphenyl) amine ] (Poly-TPD, CAS No. 472960-35-3), poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene) (PFB, CAS No. 223569-28-6), 4',4 "-tris (carbazole-9-yl) triphenylamine (TCTA, CAS No. 139092-78-7), 4' -bis (9-carbazole) biphenyl (CBP, CAS No. 58328-7), N '-diphenyl-1, 4' -diphenyl-1, 9 '-dioctylfluorene (4-butylphenyl) -N, N' -diphenyl-1, 9 '-dioctylfluorene (4-phenylbiphenyl) (PFB, 4' -diphenyl-9-phenylbiphenyl), CAS number 123847-85-8), poly (3, 4-ethylenedioxythiophene): at least one of poly (styrenesulfonic acid), doped or undoped graphene, C60, niO, moO 3、WO3、V2O5、CrO3, cuO, or P-type gallium nitride.
It is understood that the optoelectronic device of the embodiments of the present application may further include other functional layers, such as an electron injection layer, for example, the thickness of which may be 10nm to 100nm, the material of the electron injection layer including but not limited to at least one of an alkali metal halide including but not limited to LiF, an alkali metal organic complex including but not limited to lithium 8-hydroxyquinoline, or an organic phosphine compound including but not limited to at least one of an organic phosphorus oxide, an organic thiophosphine compound, or an organic selenophosphine compound.
The embodiment of the application also provides a preparation method of the photoelectric device, as shown in fig. 3, the preparation method of the photoelectric device comprises the following steps:
s100, providing a metal oxide solution, mixing the metal oxide solution with chitosan, and reacting to obtain a composite material;
and S200, providing a prefabricated device, applying a composite material on one side of the prefabricated device, and then drying to form an electron transport layer.
Wherein step S100 refers to the description of the method for preparing the composite material described hereinabove.
In step S200, the prefabricated device means that the preparation of one or more functional layers has been completed, and the next process is to form a stacked structure of electron transport layers. When the optoelectronic device is a front-mounted structure, for example, the prefabricated device may be a stacked structure including an anode and a light-emitting layer, the electron transport layer being formed on a side of the light-emitting layer remote from the anode; for another example, the prefabricated device may be a stacked structure including an anode, a hole function layer, and a light emitting layer, with an electron transport layer formed on a side of the light emitting layer remote from the hole function layer. When the photovoltaic device is a positive structure, for example, the prefabricated device may be a stacked structure including a cathode, and an electron transport layer is formed on one side of the cathode.
In step S200, the application manner of the composite material includes, but is not limited to, at least one of spin coating, inkjet printing, doctor blading, dip-lift, dipping, spray coating, roll coating, or casting.
In step S200, the "drying process" includes all processes that enable the composite material on one side of the prefabricated device to be converted to a solid film layer by obtaining higher energy, including but not limited to a heat treatment or a vacuum drying process, wherein the heat treatment includes but is not limited to a constant temperature heat treatment process or a non-constant temperature heat treatment (e.g., a temperature gradient) process.
In some embodiments of the application, the drying process comprises a heat treatment and/or a vacuum drying process, the temperature of the heat treatment may be 80 ℃ to 180 ℃, the temperature of the heat treatment may be, for example, 80 ℃ to 100 ℃,100 ℃ to 120 ℃, 120 ℃ to 150 ℃, or 150 ℃ to 180 ℃; the heat treatment time may be 5 to 60 minutes, for example, 5 to 15 minutes, 15 to 30 minutes, 30 to 40 minutes, or 40 to 60 minutes. As an example, the drying process is a constant temperature heat process, the temperature of which is 80 ℃, and the time of which is 30min.
It should be noted that, for preparing the electron transport layer by using the solution method, if the solute of the electron transport material solution only contains the metal oxide, the metal oxide is easy to generate an agglomeration problem in the solution, so that the dispersion performance of the metal oxide in the solution is poor, and the film forming quality of the prepared electron transport layer is poor. In addition, the metal oxide has problems of non-uniform particle shape and non-uniform particle size, and further exacerbates non-uniformity of film formation.
In the preparation method of the embodiment of the application, the solute of the electron transport material solution contains the chitosan and the metal oxide, and the chitosan carries a large amount of hydroxyl groups and amino groups, so that the chitosan has ideal dispersion performance in the polar solvent, the amino groups endow the solution with weak alkalinity to improve the dispersion performance of the metal oxide in the solution, and the hydroxyl groups and the amino groups can be coordinately connected to the surface of the metal oxide, so that the surface defect state of the metal oxide is passivated. In addition, because the amino carried by the chitosan is easy to protonate, the chitosan in the solution carries positive charges, and the chitosan can be coordinately combined with the surface of the metal oxide, so that the metal oxide with the chitosan connected with the surface carries positive charges, after the surface of the metal oxide accumulates positive charges to a certain extent, electrostatic repulsion effect exists between adjacent metal oxide particles, so that the problem of 'agglomeration' of the metal oxide in the solution is solved, the dispersion performance of the metal oxide in the solution is further improved, the film forming quality of an electron transport layer is further improved, and the performance stability of the electron transport layer is effectively improved.
In order to improve the electrophilicity of the surface of the electron transport layer, in some embodiments of the present application, after the step S200, the method for manufacturing an optoelectronic device further includes the steps of: and S300, carrying out acid treatment on the electron transport layer to promote the protonation of the chitosan in the electron transport layer, so that the electron injection efficiency of a contact interface between the electron transport layer and the electrode can be improved when the electron transport layer is contacted with the cathode.
In some embodiments of the application, the acid treatment comprises, for example, the steps of: an acidic solution is applied to the side of the electron transport layer remote from the prefabricated device. The application means of the acidic solution includes, but is not limited to, at least one of spin coating, ink-jet printing, knife coating, dip-coating, dipping, spray coating, roll coating, or casting. Wherein the solute of the acidic solution is selected from organic acid or inorganic acid, and the solvent of the acidic solution is selected from polar organic solvent, and the polar organic solvent comprises at least one of methanol, ethanol, glycol, glycerol, isopropanol, butanol, amyl alcohol, octanol, 2-methoxyethanol, 2-ethoxyethanol or 2-methoxybutanol.
In some embodiments of the application, the acid treatment is for a time of 5s to 10s, exemplified by 5s, 6s, 7s, 8s, 9s or 10s.
In order to further enhance the performance of the electron transport layer, in some embodiments of the present application, the solute of the acidic solution is at least one selected from hydrochloric acid, acetic acid or acrylic acid, and/or the volume concentration of the solute in the acidic solution is 0.1% to 1.0%, and the solid film layer is treated by the acidic solution with a low concentration, so that the electrophilicity of the surface of the electron transport layer can be enhanced, and the electron transport layer can be prevented from being damaged.
In order to further enhance the performance of the electron transport layer, in some embodiments of the present application, after step S300, the method for manufacturing an optoelectronic device further includes the steps of: and S400, heating the acidic solution on the side, far away from the prefabricated device, of the electron transport layer to remove the acidic solution. The temperature of the heat treatment may be 80 ℃ to 150 ℃, for example 80 ℃ to 90 ℃, 90 ℃ to 100 ℃, 100 ℃ to 110 ℃,110 ℃ to 120 ℃, 120 ℃ to 130 ℃,130 ℃ to 140 ℃, 140 ℃ to 150 ℃, correspondingly the boiling point of the solute in the acidic solution is not higher than 150 ℃. The time of the heat treatment may be 5 to 60 minutes, for example, 5 to 15 minutes, 15 to 30 minutes, 30 to 40 minutes, or 40 to 60 minutes. As an example, the temperature of the heat treatment is constant at 80 ℃ and the time of the heat treatment is 30min.
In some embodiments of the present application, the prefabricated device includes a bottom electrode, and the electron transport layer is formed on one side of the bottom electrode, and the method for manufacturing the optoelectronic device further includes the steps of: forming a top electrode on one side of the electron transport layer away from the bottom electrode; one of the bottom electrode and the top electrode is an anode, and the other is a cathode. For example, when the optoelectronic device is of a positive structure, the bottom electrode is an anode and the top electrode is a cathode; when the photoelectric device is of an inverted structure, the bottom electrode is a cathode and the top electrode is an anode.
Besides the electron transport layer (prepared by a solution method), the preparation method of each other film layer in the photoelectric device comprises, but is not limited to, a solution method and a deposition method, wherein the solution method comprises, but is not limited to, spin coating, ink-jet printing, knife coating, dip-coating, dipping, spraying, roll coating or casting; the deposition method includes a chemical method including, but not limited to, a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method, or a coprecipitation method, and a physical method including, but not limited to, a thermal evaporation plating method, an electron beam evaporation plating method, a magnetron sputtering method, a multi-arc ion plating method, a physical vapor deposition method, an atomic layer deposition method, or a pulsed laser deposition method. When the film layer is prepared by a solution method, a drying treatment process is added to convert the wet film into a dry film.
It will be appreciated that the method of manufacturing an optoelectronic device may also include other steps, such as: after each film layer of the photoelectric device is prepared, the photoelectric device needs to be packaged.
The embodiment of the application also provides electronic equipment which comprises the photoelectric device. The electronic device may be, for example, any electronic product with display function, including but not limited to, a smart phone, a tablet computer, a notebook computer, a digital camera, a digital video camera, a smart wearable device, a smart weighing electronic scale, a vehicle display, a television set, or an electronic book reader, where the smart wearable device may be, for example, a smart bracelet, a smart watch, a Virtual Reality (VR) helmet, or the like.
The technical solutions and effects of the present application will be described in detail by way of specific examples, comparative examples and experimental examples, which are only some examples of the present application, and are not intended to limit the present application in any way.
Example 1
The embodiment provides a preparation method of a composite material and the prepared composite material, wherein the composite material consists of chitosan and nano ZnO, the chitosan is coordinately combined on the surface of the nano ZnO, and the particle size distribution range of the nano ZnO is 2nm to 5nm.
The preparation method of the composite material comprises the following steps: dispersing nano ZnO with the particle size distribution range of 2nm to 5nm in ethanol to prepare a nano ZnO solution with the concentration of 30mg/mL, adding chitosan into the nano ZnO solution until the concentration of chitosan is 3mg/mL, and stirring and mixing for 30min at the temperature of 30 ℃ to obtain the composite material.
Example 2
The present embodiment provides a method for preparing a composite material and a composite material prepared by the method, and compared with the method for preparing a composite material in embodiment 1, the method for preparing a composite material in this embodiment is only different in that: and replacing the step of adding the chitosan into the nano ZnO solution until the concentration of the chitosan is 3mg/mL with the step of adding the chitosan into the nano ZnO solution until the concentration of the chitosan is 1.5 mg/mL.
Example 3
The present embodiment provides a method for preparing a composite material and a composite material prepared by the method, and compared with the method for preparing a composite material in embodiment 1, the method for preparing a composite material in this embodiment is only different in that: and replacing the step of adding the chitosan into the nano ZnO solution until the concentration of the chitosan is 3mg/mL with the step of adding the chitosan into the nano ZnO solution until the concentration of the chitosan is 2.4 mg/mL.
Example 4
The present embodiment provides a method for preparing a composite material and a composite material prepared by the method, and compared with the method for preparing a composite material in embodiment 1, the method for preparing a composite material in this embodiment is only different in that: and replacing the step of adding the chitosan into the nano ZnO solution until the concentration of the chitosan is 3mg/mL with the step of adding the chitosan into the nano ZnO solution until the concentration of the chitosan is 8 mg/mL.
Example 5
The present embodiment provides a method for preparing a composite material and a composite material prepared by the method, and compared with the method for preparing a composite material in embodiment 1, the method for preparing a composite material in this embodiment is only different in that: and replacing the step of adding the chitosan into the nano ZnO solution until the concentration of the chitosan is 3mg/mL with the step of adding the chitosan into the nano ZnO solution until the concentration of the chitosan is 1 mg/mL.
Example 6
The present embodiment provides a method for preparing a composite material and a composite material prepared by the method, and compared with the method for preparing a composite material in embodiment 1, the method for preparing a composite material in this embodiment is only different in that: "nano ZnO having a particle size distribution range of 2nm to 5 nm" is replaced with "nano TiO 2 having a particle size distribution range of 2nm to 5 nm".
Example 7
The present embodiment provides a method for preparing a composite material and a composite material prepared by the method, and compared with the method for preparing a composite material in embodiment 1, the method for preparing a composite material in this embodiment is only different in that: "nano ZnO having a particle size distribution range of 2nm to 5 nm" is replaced with "nano ZrO 2 having a particle size distribution range of 2nm to 5 nm".
Example 8
The embodiment provides a photoelectric device and a preparation method thereof, the photoelectric device is a quantum dot light emitting diode with a forward structure, as shown in fig. 4, in a bottom-up direction, the photoelectric device 1 includes a substrate 10, an anode 11, a hole functional layer 15, a light emitting layer 13, an electron transport layer 14 and a cathode 12, which are sequentially stacked, wherein the hole functional layer 15 is composed of a hole injection layer 151 and a hole transport layer 152 which are stacked, the hole injection layer 151 is closer to the anode 11 than the hole transport layer 152, and the hole transport layer 152 is closer to the light emitting layer 13 than the hole injection layer 151.
The materials and thicknesses of the respective layers in the optoelectronic device 1 are as follows:
The material of the substrate 10 is glass, and the thickness of the substrate 10 is 2mm;
The anode 11 is made of ITO, and the thickness of the anode 11 is 120nm;
the cathode 12 is made of Ag, and the thickness of the cathode 12 is 60nm;
The luminescent layer 13 is made of CdSeS/ZnS green quantum dots, the surface of the CdSeS/ZnS green quantum dots is connected with octathiol ligand, each 1mg of CdSeS/ZnS green quantum dots is correspondingly connected with 0.2mmol of octathiol ligand, and the thickness of the luminescent layer 13 is 70nm;
The material of the electron transport layer 14 was the composite material prepared in example 1, and the thickness of the electron transport layer 14 was 50nm;
The hole injection layer 151 is made of PEDOT PSS, and the thickness of the hole injection layer 151 is 80nm;
the material of the hole transport layer 152 is TFB, and the thickness of the hole transport layer 152 is 70nm.
The preparation method of the photoelectric device in the embodiment comprises the following steps:
S8.1, providing a substrate, sputtering ITO on one side of the substrate to obtain an ITO layer, dipping a small amount of soapy water on the surface of the ITO layer by using a cotton swab to wipe the surface of the ITO layer so as to remove impurities visible to the naked eyes on the surface, sequentially ultrasonically cleaning the substrate comprising the ITO by using deionized water for 15min, acetone for 15min, ethanol for 15min and isopropanol for 15min, and performing ultraviolet-ozone surface treatment for 5min after drying to obtain the substrate comprising an anode;
S8.2, spin-coating PEDOT on one side of the anode far away from the substrate in the step S8.1 under the argon atmosphere at normal temperature and normal pressure: performing constant temperature heat treatment on the PSS aqueous solution at 150 ℃ for 30min to obtain a hole injection layer;
S8.3, spin-coating TFB-chlorobenzene solution on one side of the hole injection layer far away from the anode in the step S8.2 under the argon environment of normal temperature and normal pressure, and then placing the film at a constant temperature of 150 ℃ for heat treatment for 30min to obtain a hole transport layer;
s8.4, spin-coating a CdSeS/ZnS green quantum dot-n-octane solution with the concentration of 30mg/mL on one side of the hole transport layer far away from the hole injection layer in the step S8.3 under the argon environment of normal temperature and normal pressure, and then placing the solution in the constant temperature heat treatment for 10min at the temperature of 80 ℃ to obtain a luminescent layer;
S8.5, spin-coating the composite material prepared in the example 1 on one side of the luminescent layer far away from the hole transport layer in the step S8.4 under the argon environment of normal temperature and normal pressure, and then performing constant-temperature heat treatment for 30min at 80 ℃ to form an electron transport layer; spin-coating hydrochloric acid-ethanol solution (the volume percentage of hydrochloric acid is 0.5%) on one side of the electron transport layer far away from the light-emitting layer in an air environment of normal temperature and normal pressure, and then placing the solution at a constant temperature of 80 ℃ for heat treatment for 30min so as to volatilize and remove the hydrochloric acid-ethanol solution on one side of the electron transport layer far away from the light-emitting layer;
And S8.6, placing the prefabricated device containing the electron transport layer in an evaporation bin with the air pressure of 4 multiplied by 10 -6 mbar, thermally evaporating Ag on one side of the electron transport layer far away from the light-emitting layer in the step S8.5 through a mask plate to obtain a cathode, and then packaging by adopting ultraviolet curing glue to obtain the photoelectric device.
Example 9
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and compared with the optoelectronic device of embodiment 8, the optoelectronic device of the present embodiment is only different in that: the material of the electron transport layer was the composite material prepared in example 2.
Compared with the preparation method of the photoelectric device in example 1, the preparation method of this example only differs in that: the composite material prepared in example 2 was spin-coated on the side of the light-emitting layer away from the hole transport layer "in step S8.5.
Example 10
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and compared with the optoelectronic device of embodiment 8, the optoelectronic device of the present embodiment is only different in that: the material of the electron transport layer was the composite material prepared in example 3.
Compared with the preparation method of the photoelectric device in example 1, the preparation method of this example only differs in that: the composite material prepared in example 3 was spin-coated on the side of the light-emitting layer away from the hole transport layer "in step S8.5.
Example 11
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and compared with the optoelectronic device of embodiment 8, the optoelectronic device of the present embodiment is only different in that: the material of the electron transport layer was the composite material prepared in example 4.
Compared with the preparation method of the photoelectric device in example 1, the preparation method of this example only differs in that: the composite material produced in example 4 was spin-coated on the side of the light-emitting layer away from the hole transport layer "in step S8.5.
Example 12
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and compared with the optoelectronic device of embodiment 8, the optoelectronic device of the present embodiment is only different in that: the material of the electron transport layer was the composite material prepared in example 5.
Compared with the preparation method of the photoelectric device in example 1, the preparation method of this example only differs in that: the composite material prepared in example 5 was spin-coated on the side of the light-emitting layer away from the hole transport layer "in step S8.5.
Example 13
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and compared with the optoelectronic device of embodiment 8, the optoelectronic device of the present embodiment is only different in that: the material of the electron transport layer was the composite material prepared in example 6.
Compared with the preparation method of the photoelectric device in example 1, the preparation method of this example only differs in that: the composite material prepared in example 6 was spin-coated on the side of the light-emitting layer away from the hole transport layer "in step S8.5.
Example 14
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and compared with the optoelectronic device of embodiment 8, the optoelectronic device of the present embodiment is only different in that: the material of the electron transport layer was the composite material prepared in example 7.
Compared with the preparation method of the photoelectric device in example 1, the preparation method of this example only differs in that: the composite material prepared in example 7 was spin-coated on the side of the light-emitting layer away from the hole transport layer "in step S8.5.
Example 15
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and the structural composition of the optoelectronic device in the present embodiment is the same as that of the optoelectronic device in embodiment 1.
Compared with the preparation method of the photoelectric device in example 8, the preparation method of this example only differs in that: the composite material prepared in example 1 was spin-coated on the side of the light-emitting layer far from the hole transport layer in step S8.4 under an argon atmosphere at normal temperature and normal pressure instead of step S8.5, and then subjected to constant temperature heat treatment at 80 ℃ for 30min to obtain an electron transport layer.
Example 16
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and the structural composition of the optoelectronic device in the present embodiment is the same as that of the optoelectronic device in embodiment 8.
Compared with the preparation method of the photoelectric device in example 8, the preparation method of this example only differs in that: the "hydrochloric acid-ethanol solution (0.5% by volume of hydrochloric acid)" in step S8.5 was replaced with "acetic acid-ethanol solution (0.5% by volume of hydrochloric acid)".
Example 17
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and the structural composition of the optoelectronic device in the present embodiment is the same as that of the optoelectronic device in embodiment 8.
Compared with the preparation method of the photoelectric device in example 8, the preparation method of this example only differs in that: the "hydrochloric acid-ethanol solution (0.5% by volume of hydrochloric acid)" in step S8.5 was replaced with "hydrochloric acid-ethanol solution (0.1% by volume of hydrochloric acid)".
Example 18
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and the structural composition of the optoelectronic device in the present embodiment is the same as that of the optoelectronic device in embodiment 8.
Compared with the preparation method of the photoelectric device in example 8, the preparation method of this example only differs in that: the "hydrochloric acid-ethanol solution (0.5% by volume of hydrochloric acid)" in step S8.5 was replaced with "hydrochloric acid-ethanol solution (1.0% by volume of hydrochloric acid)".
Example 19
The present embodiment provides an optoelectronic device and a method for manufacturing the same, and the structural composition of the optoelectronic device in the present embodiment is the same as that of the optoelectronic device in embodiment 1.
Compared with the preparation method of the photoelectric device in example 1, the preparation method of this example only differs in that: the "hydrochloric acid-ethanol solution (the volume percentage of hydrochloric acid is 0.5%)" in step S8.5 was replaced with "hydrochloric acid-ethanol solution (the volume percentage of hydrochloric acid is 2.0%)".
Comparative example
The present comparative example provides an optoelectronic device and a method of manufacturing the same, which differs from the optoelectronic device of example 8 only in that: the material of the electron transport layer in example 8 was replaced with "nano ZnO having a particle size distribution ranging from 2nm to 5 nm".
The comparative example was different from the production method of the photovoltaic device in example 8 only in that: and replacing the step S1.5 with ' under the argon environment at normal temperature and normal pressure ', carrying out ink-jet printing on the side of the light-emitting layer far away from the hole transport layer by using a nano ZnO (the particle size distribution range is 2nm to 5 nm) -ethanol solution with the concentration of 30mg/mL ', and then carrying out constant-temperature heat treatment at 80 ℃ for 30min to obtain the electron transport layer.
Experimental example 1
The oxygen vacancy densities of the composite materials and nano ZnO (particle size distribution range of 2nm to 5 nm) in examples 1 to 7 were respectively measured by: and detecting the oxygen vacancy ratio Oy/O-X of the composite material by adopting X-ray photoelectron spectroscopy (XPS), wherein Oy is the number of oxygen vacancies, O-X is the number of oxygen-metal chemical bonds between oxygen and metal elements in the metal oxide, the smaller the ratio of Oy/O-X is, the higher the stability of the composite material is, and conversely, the larger the ratio of Oy/O-X is, the lower the stability of the composite material is. The test results are shown in table 1 below:
table 1A list of oxygen vacancy ratios Oy/O-X for the composites of examples 1-7 and comparative example 1
As can be seen from Table 1, the Oy/O-X ratios of the composite materials in examples 1 to 7 are smaller than those of nano ZnO having a particle size distribution ranging from 2nm to 5nm, and it is fully explained that: the stability of the composites in examples 1 to 7 is significantly better than nano ZnO with particle size distribution in the range of 2nm to 5 nm.
Experimental example 2
The performance of the optoelectronic devices of examples 8 to 19 and comparative examples was tested by using a Friedel-crafts FPD optical characteristic measuring device (including marine optical USB2000, labView control QE-PRO spectrometer, keithley 2400, high-precision digital source meter Keithley 6485, an optical fiber with an inner diameter of 50 μm, a device test probe and fixture, and an efficiency test system built by various connecting wires and elements such as a data card, an efficiency test cassette and a data acquisition system), to obtain parameters such as the lighting voltage, current, brightness, luminescence spectrum, etc., of each optoelectronic device, and then calculating to obtain key parameters such as external quantum efficiency, power efficiency, etc., and using a life test device to test the service life of each optoelectronic device.
The current efficiency testing method comprises the following steps: setting a light emitting area to be 2mm multiplied by 2 mm=4mm 2, intermittently collecting the brightness value of the photoelectric device in the range of 0V to 8V of driving voltage, collecting the brightness value of 3V at intervals of 0.2V, dividing the brightness value collected each time by the corresponding current density to obtain the current efficiency of the photoelectric device under the condition of the collection, and obtaining the maximum current efficiency value (CE max, cd/A).
The service life testing method comprises the following steps: under the drive of constant current (2 mA), carrying out electroluminescence service life analysis on each photoelectric device by adopting a 128-path QLED service life testing system, recording the time (T95, h) required by each photoelectric device for reducing the maximum brightness to 95 percent, and calculating the time (T95@1000nit, h) required by each photoelectric device for reducing the brightness from 100 percent to 95 percent under the brightness of 1000nit by a reduction fitting formula.
In the preparation process of each photoelectric device, after the electron transport layer is prepared, a Brookfield atomic force microscope is adopted to detect the average roughness (Ra, nm) of the electron transport layer according to the GB/T31227-2014 standard.
The performance test data for each optoelectronic device is detailed in table 2 below:
Table 2 list of performance test results for optoelectronic devices in examples 8-19 and comparative examples
As can be seen from table 1, the overall performance of the photovoltaic devices in examples 8 to 19 is significantly superior to that of the photovoltaic devices in comparative examples. Taking example 1 as an example, the average roughness of the electron transport layer surface of the photovoltaic device in example 1 is only 22% of the average roughness of the electron transport layer surface of the photovoltaic device in comparative example, and t95@1000nit of the photovoltaic device in example 8 is 1.9 times that of the photovoltaic device in comparative example, and the turn-on voltage of the photovoltaic device in example 8 is only 86% of that of the photovoltaic device in comparative example, and CE max of the photovoltaic device in example 8 is 1.6 times that of CE max of the photovoltaic device in comparative example, thereby illustrating that: compared with the material adopting metal oxide as the electron transport layer, the composite material formed by metal oxide and chitosan is adopted as the material of the electron transport layer, so that the surface evenness of the electron transport layer can be improved, the luminous efficiency of the photoelectric device can be effectively improved, the starting voltage of the photoelectric device can be reduced, and the service life of the photoelectric device can be prolonged.
As can be seen from the performance test data of the optoelectronic devices in examples 8 to 12, the overall performance of the optoelectronic devices in examples 11 and 12 is inferior to that of the optoelectronic devices in examples 8 to 10, and in the electron transport layer, when nano ZnO: the mass ratio of the chitosan is 1: (0.05-0.1), the photoelectric performance and the service life of the photoelectric device can be further improved.
From the performance test data of the optoelectronic devices in example 8 and example 15, it can be seen that the overall performance of the optoelectronic device in example 15 is inferior to that of the optoelectronic device in example 8, and thus it can be seen that: in the process of forming the electron transport layer, an acid treatment step is added to promote the protonation of the chitosan, so that the electrophilicity of the surface of the composite material can be enhanced, the electron injection efficiency of a contact interface between the electron transport layer and the cathode is improved, and the photoelectric performance and the service life of the photoelectric device are further improved.
From the performance detection data of the photoelectric devices in examples 8, 17 to 19, it is known that, in the acid treatment step, when the volume concentration of the solute in the acidic solution is 0.1% to 1.0%, the electrophilicity of the surface of the composite material can be enhanced, and the damage of the composite material can be avoided, thereby further improving the photoelectric performance and the service life of the photoelectric device.
The composite material, the preparation method of the composite material, the photoelectric device and the electronic equipment provided by the embodiment of the application are described in detail. The principles and embodiments of the present application have been described herein with reference to specific examples, the description of which is only for aiding in the understanding of the technical solution of the present application and its core ideas; those of ordinary skill in the art will appreciate that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the scope of the corresponding technical solutions of the embodiments of the present application.

Claims (18)

1. A composite material comprising a chitosan and a metal oxide, wherein the chitosan is coordinately bound to the surface of the metal oxide.
2. The composite of claim 1, wherein in the composite the metal oxide: the mass ratio of the chitosan is 1: (0.05-0.1).
3. The composite of claim 1, wherein the metal oxide is selected from at least one of ZnO、TiO2、SnO2、BaO、Ta2O3、Al2O3、ZrO2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、ZnOCl、ZnOF or ZnMgLiO;
And/or the metal oxide has an average particle diameter of 2nm to 5nm;
and/or, the forbidden band width of the metal oxide is 2.0eV to 6.0eV.
4. A composite material according to any one of claims 1 to 3, characterized in that the composite material consists of chitosan and a metal oxide.
5. A method of preparing a composite material, comprising the steps of: providing a metal oxide solution and chitosan, mixing the metal oxide solution and the chitosan, and reacting to obtain the composite material.
6. The method according to claim 5, wherein the temperature of the mixing reaction is 15 ℃ to 35 ℃ and the time of the mixing reaction is 30 minutes to 60 minutes.
7. The method of claim 5, wherein the metal oxide in the metal oxide solution is: the mass ratio of the chitosan is 1: (0.05-0.1);
and/or the solvent of the metal oxide solution is selected from at least one of methanol, ethanol, glycol, glycerol, isopropanol, butanol, amyl alcohol, octanol, 2-methoxyethanol, 2-ethoxyethanol or 2-methoxybutanol.
8. An optoelectronic device, comprising:
An anode;
A cathode disposed opposite the anode; and
An electron transport layer disposed between the anode and the cathode;
Wherein the electron transport layer comprises the composite material as claimed in any one of claims 1 to 4 or comprises the composite material produced by the production method as claimed in any one of claims 5 to 7.
9. The optoelectronic device of claim 8, further comprising a light emitting layer disposed between the anode and the electron transport layer; the material of the light-emitting layer is an organic light-emitting material or quantum dots;
Wherein the organic luminescent material is selected from at least one of a biaryl anthracene derivative, a stilbene aromatic derivative, a pyrene derivative or a fluorene derivative, a TBPe fluorescent material, a TTPA fluorescent material, a TBRb fluorescent material or a DBP fluorescent material;
The quantum dots are selected from at least one of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots or organic-inorganic hybrid perovskite quantum dots; when the quantum dot is selected from a single component quantum dot or a core-shell structure quantum dot, the material of the single component quantum dot, the material of the core-shell structure quantum dot, and the material of the shell of the core-shell structure quantum dot are selected from at least one of group II-VI compound, group III-V compound, group IV-VI compound, or group I-III-VI compound, independently of each other, wherein the group II-VI compound is selected from at least one of CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe or HgZnSTe, the group III-V compound is selected from at least one of GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs or InAlPSb, the group IV-VI compound is selected from at least one of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe or SnPbSTe, and the group I-III-VI compound is selected from at least one of CuInS, cuInSe, or AgInS;
and/or the materials of the anode and the cathode are selected from at least one of metal, carbon material or metal oxide material independently of each other, the metal is selected from at least one of Al, ag, cu, mo, au, ba, ca or Mg, the carbon material is selected from at least one of graphite, carbon nanotube, graphene or carbon fiber, and the metal oxide material is selected from at least one of indium tin oxide, fluorine doped tin oxide, tin antimony oxide, aluminum doped zinc oxide, gallium doped zinc oxide, indium doped zinc oxide or magnesium doped zinc oxide.
10. The optoelectronic device of claim 9, further comprising a hole-functional layer disposed between the light-emitting layer and the anode, the hole-functional layer comprising a hole-injection layer and/or a hole-transport layer;
For the hole functional layer including the hole injection layer and the hole transport layer, the hole injection layer is closer to the anode than the hole transport layer, and the hole transport layer is closer to the light emitting layer than the hole injection layer;
The hole injection layer is made of poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid), copper phthalocyanine, titanyl phthalocyanine, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4' -tris [ 2-naphthylphenylamino ] triphenylamine, 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, transition metal oxide selected from at least one of an oxide of nickel, an oxide of molybdenum, an oxide of tungsten, an oxide of chromium, an oxide of copper, or an oxide of vanadium, or transition metal chalcogenide selected from at least one of MoS x、MoSex、WSx、WSex or CuS x;
And/or the material of the hole transport layer is selected from at least one of poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine), 3-hexyl substituted polythiophene, poly (9-vinylcarbazole), poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (N, N '-bis (4-butylphenyl) -N, N' -diphenyl-1, 4-phenylenediamine-CO-9, 9-dioctylfluorene), 4',4 "-tris (carbazole-9-yl) triphenylamine, 4' -bis (9-carbazole) biphenyl, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonic acid), doped or undoped graphene, C60, niO, moO 3、WO3、V2O5、CrO3, cuO, or P-type gallium nitride.
11. A method of fabricating an optoelectronic device comprising the steps of:
Providing a metal oxide solution and chitosan, mixing the metal oxide solution and the chitosan, and reacting to obtain a composite material; and
Providing a prefabricated device, applying the composite material on one side of the prefabricated device, and then drying to form an electron transport layer.
12. The method according to claim 11, characterized in that after the step of drying treatment to form an electron transport layer, the method further comprises the step of: and carrying out acid treatment on the electron transport layer.
13. The method of producing according to claim 12, wherein the acid treatment comprises the steps of: applying an acidic solution to a side of the electron transport layer remote from the preformed device;
And/or the acid treatment time is 5 seconds to 10 seconds.
14. The method of claim 13, wherein the solute of the acidic solution is selected from an organic acid or an inorganic acid;
And/or the solvent of the acidic solution is selected from a polar organic solvent, wherein the polar organic solvent is selected from at least one of methanol, ethanol, glycol, glycerol, isopropanol, butanol, amyl alcohol, octanol, 2-methoxyethanol, 2-ethoxyethanol or 2-methoxybutanol.
15. The method of claim 14, wherein the acidic solution has a solute selected from at least one of hydrochloric acid, acetic acid, or acrylic acid;
and/or the volume concentration of the solute in the acidic solution is 0.1% to 1.0%.
16. The method of claim 11, wherein the temperature of the mixing reaction is 15 ℃ to 35 ℃ and the time of the mixing reaction is 30 minutes to 60 minutes;
And/or, a metal oxide in the metal oxide solution: the mass ratio of the chitosan is 1: (0.05-0.1);
and/or the solvent of the metal oxide solution is selected from at least one of methanol, ethanol, glycol, glycerol, isopropanol, butanol, amyl alcohol, octanol, 2-methoxyethanol, 2-ethoxyethanol or 2-methoxybutanol.
17. The method according to any one of claims 11 to 16, wherein after the step of acid-treating the electron transport layer, the method further comprises the step of: heating the acidic solution on the side of the electron transport layer away from the prefabricated device to remove the acidic solution;
And/or, the prefabricated device comprises a bottom electrode, the electron transport layer is formed on one side of the bottom electrode far away from the prefabricated device, and the preparation method further comprises the steps of: forming a top electrode on a side of the electron transport layer away from the bottom electrode; one of the bottom electrode and the top electrode is an anode, and the other is a cathode.
18. An electronic device comprising an optoelectronic device as claimed in any one of claims 8 to 10 or an optoelectronic device produced by a method of production as claimed in any one of claims 11 to 17.
CN202211354307.2A 2022-11-01 2022-11-01 Composite material, preparation method of composite material, photoelectric device and electronic equipment Pending CN117998950A (en)

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