Photoelectric device, preparation method of photoelectric device and electronic equipment

Abstract

The invention discloses a photoelectric device, a preparation method of the photoelectric device and electronic equipment, and the photoelectric device comprises an anode and a cathode which are oppositely arranged, a light-emitting layer arranged between the anode and the cathode, and an electronic function layer arranged between the light-emitting layer and the cathode, materials of the electronic function layer comprise a metal oxide material and an organic electron blocking material, the electronic function layer comprises a first surface layer and a second surface layer which are oppositely arranged in the direction from the anode to the cathode, the second surface layer is closer to the light-emitting layer than the first surface layer, and the first surface layer does not contain the organic electron blocking material. Or the content of the organic electron blocking material in the first surface layer is smaller than the content of the organic electron blocking material in the second surface layer, so that the photoelectric performance and the service life of the photoelectric device are improved.

Description

Technical Field

[0001] The present application relates to the field of optoelectronic technology, and in particular to an optoelectronic device, a method for preparing an optoelectronic device, and an electronic device. Background Art

[0002] Photoelectric devices refer to a type of device made using the photoelectric effect of semiconductors, including but not limited to photoelectric devices, solar cells or photodetectors. Taking light-emitting devices as an example, light-emitting devices include but are not limited to organic light-emitting diodes 10 (Organic Light-Emitting Diode, OLED) and quantum dot light-emitting diodes (Quantum Dot Light-Emitting Diodes, QLED). OLED / QLED has a "sandwich" structure, that is, it includes an anode, a cathode and a light-emitting layer, wherein the anode and the cathode are arranged opposite to each other, and the light-emitting layer is arranged between the anode and the cathode. The light-emitting principle of OLED / QLED is: electrons are injected from the cathode of the device into the light-emitting area, and holes are injected from the anode of the device into the light-emitting area. Electrons and holes are recombined in the light-emitting area to form excitons, and the recombined excitons release photons in the form of radiation transition, thereby emitting light.

[0003] After years of development, optoelectronic devices have made great progress in performance indicators and have shown great potential for application development. However, there are still some shortcomings, such as the device life of optoelectronic devices needs to be further improved. Therefore, how to further improve the device life of optoelectronic devices is of great significance to the application and development of optoelectronic devices. Summary of the invention

[0004] The present application provides a photoelectric device, a method for preparing the photoelectric device, and an electronic device to improve the device life of the photoelectric device.

[0005] In a first aspect, an embodiment of the present application provides an optoelectronic device, including:

[0006] an anode and a cathode disposed opposite to each other; and

[0007] A functional layer, disposed between the cathode and the cathode, the functional layer comprising an electronic functional layer;

[0008] Wherein, the material of the electronic functional layer includes metal oxide material and organic electron blocking material;

[0009] Along the direction from the anode to the cathode, the electronic functional layer includes a first surface layer and a second surface layer arranged opposite to each other, and the second surface layer is closer to the anode than the first surface layer;

[0010] The first surface layer does not contain the organic electron blocking material, or the content of the organic electron blocking material in the first surface layer is less than the content of the organic electron blocking material in the second surface layer.

[0011] In a second aspect, the present application provides a method for preparing a photoelectric device, comprising the following steps:

[0012] providing a bottom electrode, and forming a functional layer on one side of the bottom electrode; and

[0013] forming a top electrode on a side of the functional layer away from the bottom electrode;

[0014] Wherein, one of the bottom electrode and the top electrode is an anode, and the other is a cathode; forming the functional layer comprises the steps of: forming an electronic functional layer on one side of the bottom electrode; forming the top electrode on a side of the electronic functional layer away from the bottom electrode;

[0015] Among them, the material of the electronic functional layer includes a metal oxide material and an organic electron blocking material; along the direction from the anode to the cathode, the electronic functional layer includes a first surface layer and a second surface layer arranged opposite to each other, and the second surface layer is closer to the anode than the first surface layer; the first surface layer does not contain the organic electron blocking material, or the content of the organic electron blocking material in the first surface layer is less than the content of the organic electron blocking material in the second surface layer.

[0016] In a third aspect, the present application further provides an electronic device, comprising the optoelectronic device as described in any one of the first aspects, or the optoelectronic device manufactured by the preparation method as described in any one of the second aspects.

[0017] The present application provides an optoelectronic device, a method for preparing an optoelectronic device, and an electronic device, which have the following technical effects:

[0018] In the optoelectronic device, the material of the electronic functional layer includes a metal oxide material and an organic electron blocking material, which can improve the thickness uniformity of the electronic functional layer, and is beneficial to optimizing the interface between the electronic functional layer and the cathode, thereby improving the optoelectronic performance and device life of the optoelectronic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The technical solution and other beneficial effects of the present application will be made apparent by describing in detail the specific implementation methods of the present application in conjunction with the accompanying drawings.

[0020] Figure 1 A schematic diagram of the structure of a first optoelectronic device provided in an embodiment of the present application;

[0021] Figure 2A schematic diagram of the structure of a second optoelectronic device provided in an embodiment of the present application;

[0022] Figure 3 The current density-voltage characteristic curve of the photoelectric device of Examples 1 to 3 and the comparative example in the experimental example of this application is

[0023] Figure 4 It is a current efficiency-brightness characteristic curve diagram of the photoelectric devices of Examples 1 to 3 and the comparative example in the experimental examples of this application.

[0024] The reference numerals are as follows:

[0025] 10: Photoelectric device, 11: Anode, 12: Cathode, 13: Functional layer, 131: Electronic functional layer, 132: Hole functional layer, 133: Light-emitting layer, 101: First surface layer, 102: Second surface layer, 131-1: First sublayer, 131-N: Nth sublayer, 1321: Hole injection layer, 1322: Hole transport layer. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.

[0027] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.

[0028] It should be noted that the description order of the following embodiments is not intended to limit the preferred order of the embodiments. The various embodiments of the present application may be presented in the form of a range. It should be understood that the description in the form of a range is only for convenience and simplicity and should not be understood as a rigid limitation on the scope of the present invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single values ​​within the range. For example, it should be considered that the range description 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 range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated in this article, it is meant to include any cited numbers (fractions or integers) within the indicated range.

[0029] In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the optoelectronic device in actual use or working state, specifically the drawing direction in the attached drawings; while "inner" and "outer" refer to the outline of the optoelectronic device. The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish a sequence.

[0030] In the present application, “layer A is formed on one side of layer B”, “layer A is formed on the side of layer B away from layer C” or similar descriptions can be expressed as layer A is directly formed on one side of layer B or on the side of layer B away from layer C, that is, layer A is in direct contact with layer B, or as layer A is indirectly formed on one side of layer B or on the side of layer B away from layer C, that is, other spacing structure layers can be formed between layer A and layer B. Similarly, “layer A is arranged on one side of layer B”, “layer A is arranged on the side of layer B away from layer C” can be expressed as layer A is in direct contact with layer B, or as other spacing structure layers are arranged between layer A and layer B; “layer A is arranged between layer B and layer C” can be expressed as layer A is in direct contact with layer B and layer A is in direct contact with layer C, or layer A is in direct contact with layer B and one or more spacing structure layers are arranged between layer A and layer C, or one or more spacing structure layers are arranged between layer A and layer B and one or more spacing structure layers are arranged between layer A and layer C, or one or more spacing structure layers are arranged between layer A and layer B and layer A is in direct contact with layer C.

[0031] As used in this application, the term "including" means "including but not limited to".

[0032] As used in this application, the term "and / or" is used to describe the association relationship of associated objects, indicating that there may be three relationships, for example, A and / or B, which may indicate: A exists alone, A and B exist at the same time, and B exists alone. A and B may be singular or plural.

[0033] As used in this application, the term "at least one" refers to one or more, and "multiple" refers to two or more. The term "at least one", "the following at least one" or similar expressions refer to any combination of these items, including any combination of a single or multiple. For example, "at least one of a, b or c" or "at least one of a, b and c" can be expressed as: a, b, c, ab (i.e., a and b), ac, bc or abc, where a, b and c can be single or multiple, respectively.

[0034] As used in this application, the term "gradually decrease" or similar expressions should be understood in a broad sense, that is, it can be a continuous gradual change or a discontinuous change, wherein the discontinuous change can be, for example, a step-like gradual change.

[0035] In optoelectronic devices, metal oxides (such as metal oxide nanoparticles) are usually used as materials for electronic functional layers. However, metal oxide nanoparticles have an "agglomeration" problem in solutions. Therefore, the carrier functional layer prepared using metal oxide nanoparticles as raw materials and a solution method has an uneven distribution of nanoparticles. In particular, when the solution method is an inkjet printing method, nanoparticles are easily accumulated after the ink droplets spread over the pixel area, resulting in poor film quality of the electronic functional layer and poor thickness uniformity of the electronic functional layer, which has a negative impact on electron transmission, and further causes poor optoelectronic performance and device life of the optoelectronic device. In addition, metal oxide nanoparticles are usually synthesized in low-boiling alcohol solvents so that the surface of the metal oxide nanoparticles is connected with a large number of hydroxyl and carboxyl ligands, which can not only passivate the surface defect state of the metal oxide nanoparticles, but also improve the solution processing performance of the metal oxide nanoparticles. When the metal oxide nanoparticles are used as raw materials and the electronic functional layer is prepared by inkjet printing, the metal oxide nanoparticles need to be dispersed in a high boiling point solvent. These high boiling point solvents will change the surface state of the metal oxide nanoparticles. For example, the surface of the metal oxide nanoparticles will chemically coordinate with the high boiling point solvent, that is, the high boiling point solvent can be coordinated and connected to the surface of the metal oxide nanoparticles. The high boiling point solvent coordinated and connected to the surface of the metal oxide nanoparticles cannot be removed by a simple low-pressure and / or low-temperature (for example, less than 150° C.) heating process, and this type of high boiling point solvent usually has poor conductivity, resulting in a large potential barrier between the cathode and the electronic functional layer, which greatly reduces the electron injection level of the optoelectronic device, which is not conducive to improving the optoelectronic performance and device life of the optoelectronic device.

[0036] Based on this, the present application provides a photoelectric device, which can be a positive structure or an inverted structure, such as Figure 1 and Figure 2 As shown, the photoelectric device 10 includes an anode 11, a cathode 12 and a functional layer 13, wherein the anode 11 and the cathode 12 are arranged opposite to each other, and the electronic functional layer 131 is arranged between the anode 11 and the cathode 12. The material of the electronic functional layer 131 includes a metal oxide material and an organic electron blocking material. The electronic functional layer 131 includes a first surface layer 101 and a second surface layer 102 that are arranged opposite to each other, and the second surface layer 102 is closer to the anode 11 than the first surface layer 101; the first surface layer 101 does not contain an organic electron blocking material, or the content of the organic electron blocking material in the first surface layer 101 is less than the content of the organic electron blocking material in the second surface layer 102.

[0037] It should be noted that the "first surface layer" refers to the outer layer of the electronic functional layer 131 closest to the cathode 12, and its thickness is, for example, no more than 10nm, and examples are no more than 8nm, no more than 6nm, no more than 4nm, no more than 3nm, or no more than 1nm; the "second surface layer" refers to the outer layer of the electronic functional layer 131 closest to the anode 11, and its thickness is, for example, no more than 10nm, and examples are no more than 8nm, no more than 6nm, no more than 4nm, no more than 3nm, or no more than 1nm. In some embodiments of the present application, the thickness of the first surface layer 101 is equal to the thickness of the second surface layer 102.

[0038] “The content of the organic electron blocking material in the first surface layer 101” refers to the percentage of the mass of the organic electron blocking material in the first surface layer 101 to the total mass of the first surface layer 101. Similarly, “the content of the organic electron blocking material in the second surface layer 102” refers to the percentage of the mass of the organic electron blocking material in the second surface layer 102 to the total mass of the second surface layer 102.

[0039] In the optoelectronic device 10 of the embodiment of the present application, the material of the electronic functional layer 131 includes a metal oxide material and an organic electron blocking material. The organic electron blocking material is an organic compound. Since the organic compound has the advantage of good uniformity of film formation by a solution method, the thickness uniformity of the electronic functional layer 131 can be effectively improved, and the surface roughness of the electronic functional layer 131 can be reduced, which is beneficial to optimizing the interface between the electronic functional layer 131 and the cathode 12 and the interface between the electronic functional layer 131 and the anode 11, thereby improving the photoelectric performance and device life of the optoelectronic device 10.

[0040] In order to further improve the thickness uniformity of the electronic functional layer 131 and ensure that the optoelectronic device 10 has a good electron injection level, in some embodiments of the present application, in the electronic functional layer 131, the mass ratio of the metal oxide material to the organic electron blocking material is 1:(0.01~0.4), for example, it can be 1:0.01, 1:0.03, 1:0.05, 1:0.1, 1:0.3, 1:0.4 or a value between any two of the foregoing ratios.

[0041] In order to further improve the electron transport performance of the electronic functional layer 131, in some embodiments of the present application, the metal oxide material is selected from a non-doped first metal oxide and / or a doped second metal oxide. The non-doped first metal oxide includes, but is not limited to, one or more of ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3 and ZrO2; the doped second metal oxide is a main metal oxide doped with a first doping element, the main metal oxide includes, but is not limited to, ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3 or ZrO2, the first doping element includes, but is not limited to, one or more of Mg, Ca, Zr, W, Ga, Li, Al, Ti, Y, In and Sn, and the molar percentage of the first doping element in the doped second metal oxide is, for example, not higher than 5%, not higher than 10%, not higher than 20%, not higher than 30% or not higher than 50%. The doped second metal oxide includes, but is not limited to, one or more of zinc magnesium oxide, zinc calcium oxide, zinc zirconium oxide, zinc gallium oxide, zinc aluminum oxide, zinc lithium oxide, zinc titanium oxide, yttrium zinc oxide, indium tin oxide, and titanium lithium oxide, for example, Zn (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) W x O, Zn (1-x) Y x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O、Al (1-x) Zn x O, Zn (1-x) Ti x O, Zn (1-x) Y x O、In (1-x) Sn x O and Ti (1-x) Li x O, wherein 0<x≤0.5. The metal oxide material is in the form of nanoparticles, for example, and the average particle size of the metal oxide material is, for example, 2 nm to 20 nm.

[0042] In order to further improve the electron transport performance of the electronic functional layer 131, in some embodiments of the present application, the organic electron blocking material is selected from one or more of polyaniline (CAS No. 5612-44-2), polyethyleneimine (CAS No. 9002-98-6), polystyrene (CAS No. 9003-53-6), polypropylene (CAS No. 9003-07-0), polymethyl methacrylate (CAS No. 9010-88-2) and polyacrylonitrile (CAS No. 25014-41-9).

[0043] In some embodiments of the present application, the thickness of the electronic functional layer 131 is 10 nm to 60 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm or a value between any two of the aforementioned values.

[0044] In order to further improve the electron injection level of the photoelectric device 10 and improve the matching degree between the electron injection level and the hole injection level of the photoelectric device 10, in some embodiments of the present application, the electronic functional layer 131 is a single-layer structure, and the content of the organic electron blocking material in the electronic functional layer 131 gradually decreases in the direction from the anode 11 to the cathode 12.

[0045] As an alternative embodiment, in some other embodiments of the present application, the electronic functional layer 131 is a multi-layer structure, and the electronic functional layer 131 includes a first sublayer to an Nth sublayer stacked in sequence, where N is a positive integer greater than or equal to 2. Figure 2 The structure of the optoelectronic device when N is 3 is illustrated. Along the direction from the anode 11 to the cathode 12, the first sublayer to the Nth sublayer are arranged in sequence, each sublayer includes the metal oxide material, and the content of the organic electron blocking material in the first sublayer to the Nth sublayer decreases in sequence. It should be noted that in the first sublayer to the Nth sublayer, the material of each sublayer may include the metal oxide material and the organic electron blocking material, or some sublayers may not contain the organic electron blocking material. In a specific example, the content of the organic electron blocking material in the Nth sublayer is zero; in addition, the metal oxide materials in the first sublayer to the Nth sublayer may be the same or different, the thickness of the first sublayer to the Nth sublayer may be the same or different, and the materials of the first sublayer to the Nth sublayer may be composed of the metal oxide material and the organic electron blocking material respectively; in order to facilitate the regulation of the performance of the optoelectronic device and simplify the preparation process, the metal oxide materials in the first sublayer to the Nth sublayer are the same, and the thickness of the first sublayer to the Nth sublayer is the same.

[0046] Furthermore, in order to further improve the overall thickness uniformity of the electronic functional layer 131 and reduce manufacturing costs, in some embodiments of the present application, the thickness of each sublayer is 5nm to 20nm, for example, 5nm, 8nm, 10nm, 12nm, 15nm, 18nm, 20nm or a value between any two of the foregoing values.

[0047] In some embodiments of the present application, the optoelectronic device 10 is a light emitting device. Figure 1 and Figure 2 , the functional layer 13 further includes a light-emitting layer 133, and the light-emitting layer 133 is arranged between the anode 11 and the electronic functional layer 131. The light-emitting layer 133 can be a single-layer structure or a multi-layer structure, and the thickness of the light-emitting layer 133 is, for example, 10nm to 100nm. It should be noted that the forward projection of the first surface layer 101 on the anode 11 and the forward projection of the light-emitting area of ​​the light-emitting layer 133 on the anode 11 at least partially overlap, and the forward projection of the second surface layer 102 on the anode 11 and the forward projection of the light-emitting area of ​​the light-emitting layer 133 on the anode 11 at least partially overlap.

[0048] In some embodiments of the present application, the material of the light-emitting layer 133 includes one or more of organic light-emitting materials and quantum dots. Among them, the organic light-emitting material includes, but is not limited to, 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridine iridium(III), 4,4',4"-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridine iridium, diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing BN covalent bonds, hybrid localized charge transfer excited state materials, exciplex luminescent materials, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives. One or more.

[0049] The quantum dots include, but are not limited to, one or more of red quantum dots, green quantum dots, and blue quantum dots, and the quantum dots include, but are not limited to, one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots. The average particle size of the quantum dots can be 2nm to 20nm, for example, 2nm, 4nm, 6nm, 8nm, 10nm, 12nm, 15nm, 20nm, or a value between any two of the foregoing values.

[0050] For single-component quantum dots and core-shell structure quantum dots, the material of the single-component quantum dots, the material of the core of the core-shell structure quantum dots or the material of the shell of the core-shell structure quantum dots is, but is not limited to, at least one of a II-VI group compound, a III-V group compound, a IV-VI group compound or a I-III-VI group compound, wherein the II-VI group compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, Zn One or more of CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe, and the III-V compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, Al As, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, I nPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNA s, InAlNSb, InAlPAs and InAlPSb, the IV-VI group compound is selected from one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe, and the I-III-VI group compound is selected from one or more of CuInS, CuInSe and AgInS. It should be noted that for the material of the aforementioned single-component quantum dots, or the material of the core of the core-shell structure quantum dots, or the material of the shell of the core-shell structure quantum dots, the chemical formula provided only indicates the elemental composition, and does not indicate the content of each element. For example: CdZnSe only indicates that it is composed of three elements: Cd, Zn and Se. If the content of each element is indicated, it corresponds to Cd x Zn 1-x Se,0 <x<1。

[0051] For inorganic perovskite quantum dots, the general structural formula of inorganic perovskite quantum dots is AMX3, where A is Cs + , M is a divalent metal cation, including but not limited to Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - Br - or I - .

[0052] For organic perovskite quantum dots, the general structural formula of organic perovskite quantum dots is CMX3, wherein C is a carboxamidine group, and M is a divalent metal cation, and M includes but is not limited to Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - Br - or I - .

[0053] For organic-inorganic hybrid perovskite quantum dots, the general structural formula of organic-inorganic hybrid perovskite quantum dots is BMX3, wherein B is selected from organic amine cations, and the organic amine cations include but are not limited to CH3(CH2) n-2 NH 3+ (n≥2) or NH3(CH2) n NH3 2+ (n≥2), M is a divalent metal cation, including but not limited to Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe2+ ,Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl-, Br - or I-.

[0054] It should be noted that when the material of the light-emitting layer 133 includes quantum dots, the surface of the quantum dots may also be connected with ligands. The ligands include but are not limited to C1~C 30 Fatty carboxylic acid ligands, C6~C 30 Aromatic carboxylic acid ligands, C1~C 30 Aliphatic thiol ligands, C6~C 30 Thiol aromatic ligands, C1~C 30 Fatty amine ligands, C6~C 30 Aromatic amine ligands, C1~C 30 Aliphatic phosphine ligands, C6~C 30 Aromatic phosphine ligands and C6~C 30 One or more of aromatic phosphate ligands and halogen ligands.

[0055] Among them, the fatty carboxylic acid ligands include but are not limited to one or more of octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, tetracosanoic acid, hexacosanoic acid, oleic acid, linoleic acid, arachidic acid, arachidonic acid, erucic acid and docosahexaenoic acid; the aromatic carboxylic acid ligands include but are not limited to one or more of benzoic acid, dibenzoic acid and 1-naphthoic acid. The fatty thiol ligands include, but are not limited to, one or more of hexyl mercaptan, octyl mercaptan, nonyl mercaptan, decanyl mercaptan, undecanyl mercaptan, dodecanyl mercaptan, hexadecanyl mercaptan and octadecyl mercaptan. The thiol aromatic ligands include, but are not limited to, one or more of benzene mercaptan, triphenylmethyl mercaptan and p-terphenyl-4,4"-dithiol. The fatty amine ligands include, but are not limited to, one or more of hexylamine, octylamine, dioctylamine, trioctylamine, nonylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecanylamine, octadecylamine and oleylamine. The aromatic amine ligands include, but are not limited to, aniline, indenepropylamine, 4-octylaniline and and one or more of benzidine. Aliphatic phosphine ligands include but are not limited to one or more of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, tridecylphosphine, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide and tridecylphosphine oxide, aromatic phosphine ligands include but are not limited to one or more of bis(2-diphenylphosphinoethyl)phenylphosphine and triphenylphosphine oxide, aromatic phosphate ligands include but are not limited to one or more of tetraethyl p-xylene diphosphate and diphenylethyl phosphate. Halogen ligands include but are not limited to -Cl, -F, -I or -Br.

[0056] For the optoelectronic device 10 in which the electron injection level is greater than the hole injection level, since the first surface layer 101 does not contain the organic electron blocking material or the content of the organic electron blocking material in the first surface layer 101 is less than the content of the organic electron blocking material in the second surface layer 102, on the one hand, it can effectively reduce the potential barrier between the electronic functional layer 131 and the cathode 12, promote the injection of electrons from the cathode to the electronic functional layer, and effectively improve the electron injection level of the optoelectronic device 10; on the other hand, it is possible to have a certain electron injection barrier between the electronic functional layer 131 and the light-emitting layer 133, which can slow down the rate of electron injection into the light-emitting layer 133, thereby promoting the electron-hole transfer balance of the optoelectronic device 10, and further improving the photoelectric performance and device life of the optoelectronic device 10.

[0057] In order to further improve the photoelectric performance and device life of the photoelectric device 10, in some embodiments of the present application, the material of the anode 11 and the material of the cathode 12 independently include one or more of a metal, a carbon material and a third metal oxide. Among them, the metal includes but is not limited to one or more of Al, Ag, Cu, Mo, Au, Ba, Pt, Ca, Ir, Ni and Mg; the carbon material includes but is not limited to one or more of graphite, carbon nanotubes, graphene and carbon fiber; the fifth metal oxide can be doped or undoped, and the doped third metal oxide includes but is not limited to one or more of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO) and magnesium-doped zinc oxide (MZO), and the undoped third metal oxide includes but is not limited to one or more of TiO2, SnO2, ZnO and In2O3.

[0058] It should be noted that the anode 11 and the cathode 12 may also be composite electrodes, respectively, and the composite electrode has a structure similar to a "sandwich", wherein the materials of the upper and lower layers are respectively doped or undoped third metal oxides, and the material of the middle layer is metal, examples of which are one or more 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, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2. The thickness of the anode 11 and the cathode 12 are, for example, independently selected from 20 nm to 300 nm.

[0059] In order to further improve the comprehensive performance of the optoelectronic device 10, in some embodiments of the present application, continue to refer to Figure 1 and Figure 2 , the functional layer 13 also includes a hole functional layer 132, and the hole functional layer 132 is arranged between the anode 11 and the electron functional layer 131; when the functional layer 13 also includes a light-emitting layer 133, the hole functional layer 132 is arranged between the anode 11 and the light-emitting layer 133. The hole functional layer 132 can be a single-layer structure or a multi-layer structure, and the thickness of the hole functional layer 132 is, for example, 10nm to 100nm. The hole functional layer 132, for example, includes one or more of a hole injection layer, a hole transport layer and an electron blocking layer. For the hole functional layer 132 including the hole injection layer, the hole transport layer and the electron blocking layer, the hole transport layer is located between the hole injection layer and the electron blocking layer, and the hole injection layer is closer to the anode 11 than the electron blocking layer; for the hole functional layer 132 including the hole transport layer and the electron blocking layer, the hole transport layer is closer to the anode 11 than the electron blocking layer. As an example, please refer to Figure 1 and Figure 2 The hole function layer 132 includes a hole injection layer 1321 and a hole transport layer 1322 which are stacked together. The hole injection layer 1321 is closer to the anode 11 than the hole transport layer 1322 .

[0060] The material of the hole function layer 132 includes, but is not limited to, one or more of a non-doped first inorganic compound, a doped second inorganic compound, and an organic compound. The organic compound includes, but is not limited to, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS, CAS No. 155090-83-8), copper phthalocyanine (CAS No. 147-14-8), titanium phthalocyanine (CAS No. 26201-32-1), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (CAS No. 29261-33-4), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (CAS No. 105598-27-4), polyaniline (CAS No. 25233-30-1), Polypyrrole (CAS No. 30604-81-0), 3-hexyl substituted polythiophene (CAS No. 104934-50-1), poly (9-vinyl carbazole) (abbreviated as PVK, CAS No. 25067-59-8), 4,4'-bis (9-carbazole) biphenyl (abbreviated as CBP, CAS No. 58328-31-7), poly [bis (4-phenyl) (4-butylphenyl) amine], 4,4'-cyclohexyl bis [N,N-bis (4-methylphenyl) aniline] (abbreviated as TAPC, CAS No. 58473-78-2), poly [(9,9-dioctylfluorenyl-2,7-diyl)-co- (4,4'-(N-(4-sec-butylphenyl) diphenyl) aniline)] (abbreviated as TFB, CAS No. 220797-16-0), poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-di-n-octylfluorenyl-2,7-diyl)] (CAS No. 223569-31-1), 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (CAS No. 124729-98-2), 4,4',4"-tris(carbazol-9-yl)triphenylamine (abbreviated as TCTA, CAS No. 139092-78-7), 4,4',4'-tris(2-naphthylphenylamino)triphenylamine (CAS No. 185 690-41-9), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as NPB, CAS No. 123847-85-8), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as TPD, CAS No. 65181-78-4), N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine (CAS No. 209980-53-0), N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirobifluorene-2,7-diamine (abbreviated as Spiro-TPD, CAS No. 65181-78-4),CAS No. 1033035-83-4), N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirobi[9H-fluorene]-2,7-diamine (CAS No. 932739-76-9), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTTA, CAS No. 1333317-99-9) and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-omeTAD, CAS No. 207739-72-8) are selected from one or more of the following: and / or, the non-doped first inorganic compound includes but is not limited to graphene, C60, nickel oxide (such as NiO), molybdenum oxide (such as MoO3), tungsten oxide (such as WO3), vanadium oxide (such as V2O5), P-type nitride Gallium, chromium oxide (such as Cr2O3), copper oxide (such as CuO or Cu2O), copper sulfide (such as CuS), molybdenum sulfide (such as MoS2) and tungsten sulfide (such as WS2) One or more; and / or, the doped second inorganic compound is a host inorganic compound doped with a second doping element, the host inorganic compound includes but is not limited to graphene, C60, nickel oxide (such as NiO), molybdenum oxide (such as MoO3), tungsten oxide (such as WO3), vanadium oxide (such as V2O5), P-type gallium nitride, chromium oxide (such as Cr2O3), copper oxide (such as CuO or Cu2O), copper sulfide (such as CuS), molybdenum sulfide (such as MoS2) and tungsten sulfide (such as WS2) One or more, and / or the second doping element includes but is not limited to nickel, molybdenum, tungsten, vanadium, chromium, copper and one or more of platinum group metal elements. ,

[0061] It is understood that when the hole functional layer 132 includes multiple materials and the hole functional layer 132 is a multi-layer structure, the multiple materials may all be in the same layer, or in different layers, or partially in the same layer. For example, when the second carrier functional layer 15 is composed of a stacked hole injection layer and a hole transport layer, the material of the second carrier functional layer 15 includes PEDOT:PSS and TFB, PEDOT:PSS and TFB are in different layers, the material of the hole injection layer is PEDOT:PSS, and the material of the hole transport layer is TFB.

[0062] The present application also provides a method for preparing a photoelectric device, which can be used to prepare any of the photoelectric devices described above. The method for preparing the photoelectric device comprises the following steps:

[0063] S1. providing a bottom electrode, and forming a functional layer on one side of the bottom electrode;

[0064] S2. Form a top electrode on a side of the functional layer away from the bottom electrode.

[0065] Among them, one of the bottom electrode and the top electrode is an anode, and the other is a cathode; forming the functional layer includes the steps of: forming an electronic functional layer on one side of the bottom electrode; forming the top electrode on the side of the electronic functional layer away from the bottom electrode. The structural composition of the anode, cathode, light-emitting layer and electronic functional layer are all described above.

[0066] In some embodiments of the present application, the bottom electrode is an anode and the top electrode is a cathode, and the method for forming the electronic functional layer comprises the following steps:

[0067] S11, providing a cured film layer including a metal oxide material and an organic electron blocking material, wherein the cured film layer includes a first surface layer and a second surface layer arranged opposite to each other, and the second surface layer is closer to the anode than the first surface layer;

[0068] S12, performing active oxygen treatment on the cured film layer so that the first surface layer does not contain organic electron blocking material, or the content of organic electron blocking material in the first surface layer is less than the content of organic electron blocking material in the second surface layer, to obtain an electronic functional layer.

[0069] In the above-mentioned method for forming the electronic functional layer, the electronic functional layer can be a single-layer structure or a multi-layer structure, and active oxygen is introduced into the cured film layer so that the organic electron blocking material is oxidized to generate carbon dioxide, thereby achieving the purpose of reducing the content of the organic electron blocking material in the electronic functional layer, and the distribution of the organic electron blocking material in the electronic functional layer can be controlled by adjusting the process parameters of the active oxygen treatment (such as the amount of active oxygen introduced, the depth of the active oxygen treatment, etc.), so that the first surface layer does not contain the organic electron blocking material, or the content of the organic electron blocking material in the first surface layer is less than the content of the organic electron blocking material in the second surface layer; in addition, when the electronic functional layer is formed by inkjet printing, the active oxygen treatment can also remove at least part of the high-boiling point solvent coordinated to the surface of the metal oxide material, thereby improving the conductivity of the electronic functional layer, which is conducive to further improving the photoelectric performance and device life of the optoelectronic device. The metal oxide material and the organic electron blocking material are both described above.

[0070] In some embodiments of the present application, the thickness of the cured film layer is 10 nm to 60 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm or a value between any two of the aforementioned values.

[0071] In order to further improve the film quality of the electronic functional layer and ensure that the optoelectronic device has a good electron injection level, in some embodiments of the present application, in the cured film layer, the mass ratio of the metal oxide material to the organic electron blocking material is 1:(0.01~0.4), for example, it can be 1:0.01, 1:0.03, 1:0.05, 1:0.1, 1:0.3, 1:0.4 or a value between any two of the foregoing ratios.

[0072] In some embodiments of the present application, the active oxygen treatment is selected from one or more of oxygen ion irradiation treatment, oxygen plasma treatment and atmosphere treatment.

[0073] In order to further improve the luminescent performance of the luminescent layer, in some embodiments of the present application, the active oxygen treatment of the cured film layer includes the steps of: placing the cured film layer in an ion irradiation device, wherein the first surface layer is configured to be closer to the ion source of the ion irradiation device than the second surface layer; in the oxygen ion irradiation treatment, the energy range of the injected oxygen ions is 0.2keV to 50keV, and the injected oxygen ion dose is 1×10 14 ions / cm 2 ~1×10 21 ions / cm 2 .

[0074] In order to further improve the luminescent performance of the luminescent layer, in other embodiments of the present application, the active oxygen treatment of the cured film layer includes the steps of: placing the cured film layer in a gas atmosphere for atmosphere treatment, the gas forming the gas atmosphere is selected from one or more of ozone and peroxide gas, the pressure of the gas atmosphere is 100KPa to 1000KPa, and the time of the atmosphere treatment is 20min to 300min. An example of peroxide gas is hydrogen peroxide gas. It should be noted that when the gas forming the gas atmosphere is a mixture of ozone and peroxide gas, the partial pressures of ozone and peroxide gas are respectively greater than 0.4KPa.

[0075] In order to further improve the luminescent performance of the luminescent layer, in other embodiments of the present application, the active oxygen treatment of the cured film layer includes the steps of: placing the cured film layer in a processing chamber of a plasma generator, and performing oxygen plasma treatment on the cured film layer using oxygen plasma generated by gas discharge, and the first surface layer is configured to be closer to the ion source of the plasma generator than the second surface layer; wherein the generated gas includes an oxygen-containing gas, and the oxygen-containing gas is selected from one or more of pure oxygen, water vapor, acid-containing vapor and alcohol-containing vapor, the pressure in the processing chamber is 0.1Pa~100Pa, the output frequency of the plasma generator is 100W~2000W, and the time of the active oxygen treatment is 5min~120min.

[0076] The acid in the acid-containing vapor is, for example, one or more selected from hydrogen halide, nitric acid, acetic acid and sulfuric acid, preferably a volatile acid, exemplified by acetic acid. In order to reduce damage to the cured film layer and / or other functional film layers located below the cured film layer, the concentration of hydrogen ions in the acid-containing vapor is 0.001 mol / L to 0.1 mol / L. The alcohol in the alcohol-containing vapor is, for example, selected from aliphatic alcohol compounds having 1 to 10 carbon atoms, exemplified by ethanol.

[0077] In some embodiments of the present application, the generating gas in the oxygen plasma treatment also includes an inert gas, which is selected from one or more of nitrogen, helium, neon, argon, krypton, xenon and radon, and / or the volume of the oxygen-containing gas accounts for 10% to 100% of the total volume of the generating gas.

[0078] It should be noted that when the active oxygen treatment is oxygen ion irradiation treatment, or oxygen plasma treatment (the generating gas is pure oxygen, or the luminescent gas is a mixture of pure oxygen and an inert gas), or ozone atmosphere treatment, the active oxygen treatment only introduces ·O into the cured film layer. After the introduced ·O oxidizes and removes part of the organic electron blocking material, the gap between adjacent metal oxide nanoparticles will increase, so that the density of the electronic functional layer is limited.

[0079] In order to further improve the density of the electronic functional layer, ·O and ·OH can be introduced into the cured film layer through active oxygen treatment. ·O and ·OH can be introduced into the cured film layer at the same time, or they can be introduced in sequence. The introduced ·O and ·OH can fully activate the surface of the metal oxide nanoparticles, allowing the metal oxide nanoparticles to grow and cross-link with each other, thereby improving the surface flatness and density of the electronic functional layer, and can improve the uniformity of carrier transmission in the electronic functional layer. In addition, ·O and ·OH can remove at least part of the organic ligands coordinated to the surface of the metal oxide nanoparticles, thereby improving the conductivity of the electronic functional layer. The method of simultaneously introducing ·O and ·OH into the cured film layer may, for example, be: placing the cured film layer in a processing chamber of a plasma generator, subjecting the cured film layer to oxygen plasma treatment using oxygen plasma generated by gas discharge, wherein the first surface layer is configured to be closer to the ion source of the plasma generator than the second surface layer, and the generated gas is water vapor; the method of separately introducing ·O and ·OH in sequence may, for example, be: first subjecting the cured film layer to oxygen ion irradiation treatment, and then subjecting the cured film layer that has undergone oxygen ion irradiation treatment to water plasma treatment.

[0080] In order to further improve the device life and performance stability of the optoelectronic device, in some embodiments of the present application, the active oxygen treatment includes the steps of: placing the cured film layer in a processing chamber of a plasma generator, and performing oxygen plasma treatment on the cured film layer using oxygen plasma generated by gas discharge, the first surface layer is configured to be closer to the ion source of the plasma generator than the second surface layer, the generated gas is formed by gasification of an acid-containing solution, the solute of the acid-containing solution includes one or more of hydrogen halide, nitric acid, acetic acid and sulfuric acid, the solvent of the acid-containing solution is a fatty alcohol compound with a carbon number of 1 to 10 (ethanol is an example), and the concentration of hydrogen ions in the acid-containing solution is 0.001 mol / L to 0.1 mol / L, which can improve the problem of corrosion of the film layer caused by the introduction of ·O and ·OH in the form of water molecules in the electronic functional layer, thereby further improving the interface stability between the electronic functional layer and the cathode, reducing the interface potential barrier while effectively stabilizing the interface reaction.

[0081] In some other embodiments of the present application, the electronic functional layer includes a first sublayer to an Nth sublayer stacked, N is a positive integer greater than or equal to 2, and when the bottom electrode is an anode and the top electrode is a cathode, the method for forming the electronic functional layer includes the steps of: sequentially forming the first sublayer to the Nth sublayer on one side of the bottom electrode; or, when the bottom electrode is a cathode and the top electrode is an anode, the method for forming the electronic functional layer includes the steps of: sequentially forming the Nth sublayer to the first sublayer on one side of the bottom electrode. The structural composition of the first sublayer to the Nth sublayer is described above.

[0082] The first to Nth sublayers can be prepared by solution methods, respectively. As an example, the method for preparing at least one of the first to Nth sublayers includes the steps of: depositing a dispersion liquid including the metal oxide material and the organic electron blocking material; and drying the deposited dispersion liquid to solidify it into a film.

[0083] The deposition method of the dispersion includes, but is not limited to, one or more of spin coating, printing, doctor blading, dip pulling, immersion, spraying, rolling, casting, slot coating, and strip coating. The dispersion medium of the dispersion liquid is, for example, selected from one or more of alkanes, aromatic hydrocarbons, halogenated alkanes, alcohol compounds, ether compounds, furan compounds, pyridine compounds, amide compounds and sulfone compounds, wherein alkanes include, but are not limited to, one or more of nonane, decane, dodecane, terpene, butylcyclohexane, n-octane, n-hexane, n-heptane, n-nonane, n-decane, cyclohexane and cyclopentane, aromatic hydrocarbons include, but are not limited to, one or more of diethylbenzene, trimethylbenzene, propylbenzene, isopropylbenzene, p-toluene isopropylbenzene, butylbenzene and 1-methylnaphthalene or indene, halogenated alkanes include, but are not limited to, one or more of dichloromethane, chloroform and carbon tetrachloride, alcohol compounds include, but are not limited to, one or more of methanol, ethanol, propanol, butanol, ethylene glycol and glycerol, ether compounds include, but are not limited to, ethylene glycol monomethyl ether, furan compounds include, but are not limited to, tetrahydrofuran, pyridine compounds include, but are not limited to, pyridine, amide compounds include, but are not limited to, N,N-dimethylformamide, and sulfone compounds include, but are not limited to, dimethyl sulfoxide. It is understood that the dispersion may also include one or more additives to promote dispersion or dissolution of the material, including but not limited to surfactants. The concentration of the metal oxide material in the dispersion is, for example, 0.5 mg / mL to 50 mg / mL, and the concentration of the organic electron blocking material in the dispersion is, for example, 0.25 mg / mL to 10 mg / mL.

[0084] The drying treatment includes, but is not limited to, one or more of natural air drying, heat treatment, vacuum drying, laser annealing, electron beam annealing, atomic annealing and microwave irradiation annealing.

[0085] In order to further improve the comprehensive performance of optoelectronic devices, in some embodiments of the present application, when the bottom electrode is an anode and the top electrode is a cathode, before the step of forming the electronic functional layer, the forming of the functional layer also includes the steps of: forming a light-emitting layer on one side of the bottom electrode; the electronic functional layer is formed on the side of the light-emitting layer away from the bottom electrode; when the bottom electrode is a cathode and the top electrode is an anode, after the step of forming the electronic functional layer, the forming of the functional layer also includes the steps of: forming a light-emitting layer on the side of the electronic functional layer away from the bottom electrode; the material of the light-emitting layer includes one or more of organic light-emitting materials and quantum dots, and the organic light-emitting materials and quantum dots are described with reference to the above.

[0086] In some embodiments of the present application, when the bottom electrode is an anode and the top electrode is a cathode, before the step of forming the electronic functional layer, forming the functional layer also includes the steps of: forming a hole functional layer on one side of the bottom electrode; the electronic functional layer is formed on the side of the hole functional layer away from the bottom electrode; when the bottom electrode is a cathode and the top electrode is an anode, after the step of forming the electronic functional layer, forming the functional layer also includes the steps of: forming a hole functional layer on the side of the electronic functional layer away from the bottom electrode.

[0087] Furthermore, when the optoelectronic device is a light-emitting device, before the step of forming the light-emitting layer, the method for preparing the optoelectronic device further includes the step of: forming a hole functional layer on one side of the bottom electrode, and the light-emitting layer is formed on the side of the hole functional layer away from the bottom electrode; or, when the bottom electrode is a cathode and the top electrode is an anode, after the step of forming the light-emitting layer and before the step of forming the top electrode, the method for preparing the optoelectronic device further includes the step of: forming a hole functional layer on the side of the light-emitting layer away from the bottom electrode, and the top electrode is formed on the side of the hole functional layer away from the light-emitting layer. The structural composition of the hole functional layer is described above.

[0088] It should be noted that, in addition to the electronic functional layer, the preparation methods of other functional layers in the optoelectronic device include but are not limited to chemical methods and / or physical methods. Among them, the chemical method includes but is not limited to one or more of chemical vapor deposition, continuous ion layer adsorption and reaction, anodization, electrolytic deposition and co-precipitation. Physical methods include but are not limited to physical plating and solution methods. Physical plating methods include but are not limited to thermal evaporation, electron beam evaporation, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition and pulsed laser deposition. One or more of solution methods include but are not limited to spin coating, printing, blade coating, dip-coating, immersion, spraying, roll coating, casting, slit coating and strip coating.

[0089] After the preparation of each film layer of the optoelectronic device is completed, a packaging process is required. The packaging process can be performed by a commonly used machine packaging or manual packaging. In the packaging process environment, the oxygen content and the water content are both lower than 0.1ppm to ensure the stability of the optoelectronic device. It should be noted that in existing optoelectronic devices, organic acid resins (such as acrylic resins) are common optoelectronic device packaging materials. When the material of the electronic functional layer in the optoelectronic device includes a metal oxide, the organic acid resin causes the metal oxide to react continuously with the cathode, and the optoelectronic device exhibits a "positive aging effect" in the short term. However, there are a large number of hydroxyl ligands on the surface of the metal oxide, and the hydroxyl ligands also react continuously with the organic acid to generate water, resulting in a rapid attenuation of the device efficiency and device life of the optoelectronic device. Therefore, in order to further improve the performance stability of the optoelectronic device, in some embodiments of the present application, an acid-free organic packaging resin (such as an acid-free epoxy resin) is used for packaging.

[0090] The embodiment of the present application also provides an electronic device, wherein the electronic device includes any of the optoelectronic devices described above, or the electronic device includes an optoelectronic device prepared by any of the methods for preparing the optoelectronic devices described above. The electronic device may be, for example, any electronic product with a display function, including but not limited to a smartphone, a tablet personal computer, a mobile phone, a video phone, an e-book reader, a laptop PC, a netbook computer, a workstation, a server, a personal digital assistant, a portable multimedia player, an MP3 player, a mobile medical machine, a camera, a game console, a digital camera, a car navigation system, an electronic billboard, an ATM, a smart bracelet, a smart watch, a virtual reality (VR) device or a wearable device.

[0091] The technical scheme and technical effects of the present application are described in detail below through specific embodiments, comparative examples and experimental examples. The following embodiments are only some embodiments of the present application and do not specifically limit the present application.

[0092] Example 1

[0093] This embodiment provides a photoelectric device and a method for preparing the same. The photoelectric device is a quantum dot light emitting diode of an upright structure, such as Figure 1As shown, from bottom to top, the optoelectronic device 10 includes an anode 11, a hole functional layer 132, a light emitting layer 133, an electronic functional layer 131 and a cathode 12 stacked in sequence. The hole functional layer 132 is composed of a hole injection layer 1321 and a hole transport layer 1322 stacked in layers, and the electronic functional layer 131 is a single-layer structure. The light emitting area of ​​the optoelectronic device is 0.04 cm 2 .

[0094] The materials and thicknesses of the various layers in the optoelectronic device 10 are as follows:

[0095] The material of the anode 11 includes ITO, and the thickness of the anode 11 is 70 nm;

[0096] The material of the cathode 12 includes Al, and the thickness of the cathode 12 is 100 nm;

[0097] The material of the light emitting layer 133 includes Cd 0.09 Zn 0.91 Se(core) / ZnSe(first intermediate shell) / Cd 0.02 Zn 0.98 S (second intermediate shell) / ZnS (outer shell), the luminescent color is blue, and the thickness of the luminescent layer 133 is 30 nm;

[0098] The material of the hole injection layer 1321 includes PEDOT:PSS, and the thickness of the hole injection layer 1321 is 20 nm;

[0099] The material of the hole transport layer 1322 includes TFB, and the thickness of the hole transport layer 1322 is 25 nm;

[0100] The material of the electronic functional layer 131 includes Zn 0.9 Mg 0.1 O (average particle size of 5 nm) and polymethyl methacrylate, Zn in the electronic functional layer 131 0.9 Mg 0.1 The mass ratio of O: polymethyl methacrylate is 1:0.08. The content of polymethyl methacrylate in the electronic functional layer 131 gradually decreases in the direction from the light-emitting layer 133 to the cathode 12. The thickness of the electronic functional layer 131 is 30 nm.

[0101] The method for preparing the optoelectronic device in this embodiment comprises the following steps:

[0102] S1.1. Provide a substrate, sputter ITO on one side of the substrate to obtain an ITO layer, wipe the surface of the ITO layer with a cotton swab dipped in a small amount of soapy water to remove impurities visible to the naked eye, and then ultrasonically clean the substrate including the ITO with acetone for 15 minutes, ethanol for 15 minutes, and deionized water for 15 minutes, blow dry, place on a heating plate at 150° C. for 10 minutes, and then irradiate with ultraviolet light for 20 minutes to obtain a substrate including an anode;

[0103] S1.2, in an air environment at room temperature and pressure, inkjet print a 2.8% PEDOT:PSS aqueous solution on the side of the anode away from the substrate, and then heat treat it at 150°C for 20 minutes to obtain a hole injection layer;

[0104] S1.3. In a nitrogen environment at room temperature and pressure, inkjet print a TFB-N-methylpyrrolidone solution with a concentration of 8.5 mg / mL on the side of the hole injection layer away from the bottom electrode, and then place it in a nitrogen atmosphere at 170°C for 20 minutes to obtain a hole transport layer;

[0105] S1.4. Under nitrogen environment at room temperature and pressure, inkjet print Cd with a concentration of 30 mg / mL on the side of the hole transport layer away from the hole injection layer. 0.09 Zn 0.91 Se / ZnSe / Cd 0.02 Zn 0.98 The S / ZnS quantum dot-cyclooctane solution was then placed in a nitrogen atmosphere at 80°C for a constant temperature heat treatment (nitrogen environment at room temperature and pressure) for 5 minutes to obtain a light-emitting layer;

[0106] S1.5, provide Zn 0.9 Mg 0.1 O solution (the solvent is ethylene glycol monobutyl ether, glycerol and diethylene glycol mixed in a volume ratio of 1:1:1), polymethyl methacrylate is added thereto, and the mixture is fully dispersed to obtain an electronic material solution. The concentration of polymethyl methacrylate in the electronic material solution is 2 mg / mL. The concentration of Zn in the electronic material solution is 1.34 0.9 Mg 0.1The concentration of O is 25 mg / mL; then, in a nitrogen environment at room temperature and pressure, an electronic material solution is inkjet printed on the side of the light-emitting layer away from the hole transport layer to obtain a liquid film, and then the liquid film is placed in a 0.01 Pa, nitrogen atmosphere, vacuum drying treatment for 15 minutes, and then constant temperature heat treatment at 100 ° C. in a nitrogen atmosphere for 10 minutes to obtain a cured film; then, the prefabricated device including the cured film layer is placed in an ion irradiation device, the cured film layer includes a first surface layer and a second surface layer that are relatively arranged, the second surface layer is closer to the light-emitting layer than the first surface layer, and the first surface layer is configured as an ion source of the ion irradiation device that is closer to the second surface layer, and the cured film layer is subjected to oxygen ion irradiation treatment. In the oxygen ion irradiation treatment, the energy of the injected oxygen ions is 2 keV, and the injected oxygen ion dose is 1×10 18 ions / cm 2 , the oxygen ion irradiation treatment time is 10 minutes; finally, the prefabricated device that has completed the oxygen ion irradiation treatment is placed in the treatment chamber of the plasma generator, the first surface layer is configured to be closer to the ion source of the plasma generator than the second surface layer, the generating gas used by the plasma generator is a mixed gas of steam and nitrogen formed by gasification of the acid-containing solution (the volume ratio of the two is 1:1), the solute of the acid-containing solution is acetic acid, the solvent of the acid-containing solution is ethanol, the concentration of hydrogen ions in the acid-containing solution is 0.01 mol / L and the concentration of acetate ions is 0.01 mol / L, the distance between the nozzle of the plasma generator and the first surface layer is 5 cm, the plasma generator is turned on to discharge to generate oxygen plasma, the pressure in the treatment chamber is 1 Pa, the output frequency of the plasma generator is 500 W, the treatment time is 5 minutes, and the electronic functional layer is obtained;

[0107] S1.6, place the prefabricated device after step S1.6 in a vacuum no higher than 3×10 -4 In the Pa evaporation chamber, Al is thermally evaporated on the side of the electronic functional layer away from the light-emitting layer using a thermal evaporation process to obtain a cathode, and then the photoelectric device is encapsulated using acid-free epoxy resin LOCTITE 3335.

[0108] Example 2

[0109] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the method for preparing the photoelectric device in Example 1, the difference in the method for preparing the photoelectric device in this embodiment is that the "generating gas used by the plasma generating device is a mixture of steam and nitrogen formed by gasifying an acid-containing solution (the volume ratio of the two is 1:1)" in step S1.5 is replaced by "a mixture of water vapor and nitrogen (the volume ratio of the two is 1:1)".

[0110] Example 3

[0111] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the method for preparing the photoelectric device in Embodiment 1, the difference between the method for preparing the photoelectric device in this embodiment is that the plasma treatment process in step S1.5 is omitted, that is, step S1.5 is replaced by "providing Zn 0.9 Mg 0.1 O-ethanol solution, polymethyl methacrylate is added thereto and dispersed evenly to obtain an electronic material solution. The concentration of polymethyl methacrylate in the electronic material solution is 2 mg / mL. 0.9 Mg 0.1 The concentration of O is 25 mg / mL; then, in a nitrogen environment at room temperature and pressure, an electronic material solution is inkjet printed on the side of the light-emitting layer away from the hole transport layer to obtain a liquid film, and then the liquid film is placed in a 0.01 Pa, nitrogen atmosphere, vacuum drying treatment for 15 minutes, and then constant temperature heat treatment at 100 ° C. in a nitrogen atmosphere for 10 minutes to form a cured film; then, the prefabricated device including the cured film layer is placed in an ion irradiation device, the cured film layer includes a first surface layer and a second surface layer that are relatively arranged, the second surface layer is closer to the light-emitting layer than the first surface layer, and the first surface layer is configured as an ion source of the ion irradiation device that is closer to the second surface layer, and the cured film layer is subjected to oxygen ion irradiation treatment. In the oxygen ion irradiation treatment, the energy of the injected oxygen ions is 2 keV, and the injected oxygen ion dose is 1×10 18 ions / cm 2 The oxygen ion irradiation treatment time is 10 minutes to obtain an electronic functional layer."

[0112] Example 4

[0113] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the photoelectric device in Embodiment 1, the difference between the photoelectric device in this embodiment is that: Zn 0.9 Mg 0.1 The mass ratio of O: polymethyl methacrylate is 1:0.01.

[0114] Compared with the preparation method of the optoelectronic device in Example 1, the difference of the preparation method of the optoelectronic device in this embodiment is that: the "concentration of polymethyl methacrylate in the electronic material solution is 2 mg / mL" in step S1.5 is replaced by "the concentration of polymethyl methacrylate in the electronic material solution is 0.25 mg / mL".

[0115] Example 5

[0116] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the photoelectric device in Embodiment 1, the difference between the photoelectric device in this embodiment is that: Zn 0.9 Mg 0.1The mass ratio of O: polymethyl methacrylate is 1:0.4.

[0117] Compared with the preparation method of the optoelectronic device in Example 1, the difference of the preparation method of the optoelectronic device in this embodiment is that: the "concentration of polymethyl methacrylate in the electronic material solution is 2 mg / mL" in step S1.5 is replaced by "the concentration of polymethyl methacrylate in the electronic material solution is 10 mg / mL".

[0118] Example 6

[0119] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the method for preparing the photoelectric device in Example 1, the difference between the method for preparing the photoelectric device in this embodiment is that the "dosage of oxygen ions injected in step S1.5 is 1×10 18 ions / cm 2 " is replaced by "The implanted oxygen ion dose is 1×10 21 ions / cm 2 ”.

[0120] Example 7

[0121] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the method for preparing the photoelectric device in Example 1, the difference between the method for preparing the photoelectric device in this embodiment is that the "dosage of oxygen ions injected in step S1.5 is 1×10 18 ions / cm 2 " is replaced by "The implanted oxygen ion dose is 1×10 14 ions / cm 2 ”.

[0122] Example 8

[0123] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the method for preparing the photoelectric device in Embodiment 1, the method for preparing the photoelectric device in this embodiment is different in that: the oxygen ion irradiation treatment process in step S1.5 is omitted, that is, step S1.5 is replaced by "providing Zn 0.9 Mg 0.1 O-ethanol solution, polymethyl methacrylate is added thereto and dispersed evenly to obtain an electronic material solution. The concentration of polymethyl methacrylate in the electronic material solution is 2 mg / mL. 0.9 Mg 0.1The concentration of O is 25 mg / mL; then, under a nitrogen environment at room temperature and pressure, an electronic material solution is inkjet printed on a side of the light-emitting layer away from the hole transport layer to obtain a liquid film, and then the liquid film is placed in a 0.01 Pa, nitrogen atmosphere, vacuum drying treatment for 15 minutes, and then constant temperature heat treatment is performed at 100° C. in a nitrogen atmosphere for 10 minutes to form a cured film; then, a prefabricated device including a cured film layer is placed in a processing chamber of a plasma generating device, the cured film layer includes a first surface layer and a second surface layer that are relatively arranged, the second surface layer is closer to the light-emitting layer than the first surface layer, and the first surface layer is configured to be closer to the second surface layer than the second surface layer. The ion source of the plasma generator is used, the generating gas used by the plasma generator is a mixed gas of steam formed by gasification of an acid solution and nitrogen (the volume ratio of the two is 1:1), the solute of the acid solution is acetic acid, the solvent of the acid solution is ethanol, the concentration of hydrogen ions in the acid solution is 0.01 mol / L, the distance between the nozzle of the plasma generator and the first surface layer is 5 cm, the plasma generator is turned on to discharge to generate oxygen plasma, the pressure in the treatment chamber is 1 Pa, the output frequency of the plasma generator is 500 W, the treatment time is 5 minutes, and an electronic functional layer is obtained.

[0124] Example 9

[0125] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the method for preparing the photoelectric device in Embodiment 1, the method for preparing the photoelectric device in this embodiment is different in that: the oxygen ion irradiation treatment process in step S1.5 is omitted, that is, step S1.5 is replaced by "providing Zn 0.9 Mg 0.1 O-ethanol solution, polymethyl methacrylate is added thereto and dispersed evenly to obtain an electronic material solution. The concentration of polymethyl methacrylate in the electronic material solution is 2 mg / mL. 0.9 Mg 0.1The concentration of O is 25 mg / mL; then, in a nitrogen environment at room temperature and pressure, an electronic material solution is inkjet printed on the side of the light-emitting layer away from the hole transport layer to obtain a liquid film, and then the liquid film is placed in a 0.01 Pa, nitrogen atmosphere for vacuum drying for 15 minutes, and then is heat-treated at a constant temperature of 100°C and a nitrogen atmosphere for 10 minutes to form a cured film; then, a prefabricated device including a cured film layer is placed in a processing chamber of a plasma generator, the cured film layer includes a first surface layer and a second surface layer that are relatively arranged, the second surface layer is closer to the light-emitting layer than the first surface layer, the first surface layer is configured to be closer to the ion source of the plasma generator than the second surface layer, the generating gas used by the plasma generator is a mixed gas of water vapor and nitrogen (the volume ratio of the two is 1:1), the distance between the nozzle of the plasma generator and the first surface layer is 5 cm, the plasma generator is turned on to discharge to generate oxygen plasma, the pressure in the processing chamber is 1 Pa, the output frequency of the plasma generator is 500 W, the processing time is 5 minutes, and an electronic functional layer is obtained.

[0126] Example 10

[0127] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the method for preparing the photoelectric device in Example 1, the difference in the method for preparing the photoelectric device in this embodiment is that "the concentration of hydrogen ions in the acid-containing solution is 0.01 mol / L" in step S1.5 is replaced by "the concentration of hydrogen ions in the acid-containing solution is 0.1 mol / L".

[0128] Embodiment 11

[0129] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the method for preparing the photoelectric device in Example 1, the method for preparing the photoelectric device in this embodiment is different in that "the solute of the acid-containing solution is acetic acid" in step S1.5 is replaced by "the solute of the acid-containing solution is hydrochloric acid".

[0130] Example 12

[0131] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the photoelectric device in Embodiment 1, the difference of the photoelectric device in this embodiment is that the "polymethyl methacrylate" in the electronic functional layer is replaced by "polyaniline".

[0132] Compared with the method for preparing the optoelectronic device in Example 1, the method for preparing the optoelectronic device in this embodiment is different in that: "polymethyl methacrylate" in step S1.5 is replaced by "polyaniline".

[0133] Example 13

[0134] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the photoelectric device in Embodiment 1, the difference of the photoelectric device in this embodiment is that the "polymethyl methacrylate" in the electronic functional layer is replaced by "polyacrylonitrile".

[0135] Compared with the method for preparing the optoelectronic device in Example 1, the method for preparing the optoelectronic device in this embodiment is different in that: "polymethyl methacrylate" in step S1.5 is replaced by "polyacrylonitrile".

[0136] Embodiment 14

[0137] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the photoelectric device in Embodiment 1, the difference of the photoelectric device in this embodiment is that the "polymethyl methacrylate" in the electronic functional layer is replaced by "polystyrene".

[0138] Compared with the method for preparing the optoelectronic device in Example 1, the method for preparing the optoelectronic device in this embodiment is different in that: "polymethyl methacrylate" in step S1.5 is replaced by "polystyrene".

[0139] Embodiment 15

[0140] This embodiment provides a photoelectric device and a method for preparing the same. Compared with the photoelectric device in Embodiment 1, the photoelectric device in this embodiment is different in that the structure of the electronic functional layer is different, such as Figure 2 As shown, in the direction from bottom to top, the electronic functional layer 131 is composed of a first sublayer 131-1, a second sublayer 131-2 and a third sublayer 131-3 stacked in sequence, and the third sublayer 131-3 is closer to the cathode 12 than the first sublayer 131-1; wherein the material of the first sublayer 131-1 is Zn 0.9 Mg 0.1 O (average particle size is 5 nm) and polymethyl methacrylate, the mass of polymethyl methacrylate accounts for 20% of the total mass of the first sublayer 131-1, and the thickness of the first sublayer 131-1 is 10 nm; the material of the second sublayer 131-2 is Zn 0.9 Mg 0.1 O (average particle size is 5 nm) and polymethyl methacrylate, the mass of polymethyl methacrylate accounts for 5% of the total mass of the second sublayer 131-2, and the thickness of the second sublayer 14-1 is 10 nm; the material of the third sublayer 131-3 is Zn 0.9 Mg 0.1 O (average particle size is 5 nm).

[0141] Compared with the preparation method of the optoelectronic device in Example 1, the difference of the preparation method of the optoelectronic device in this embodiment is that: step S1.5 is replaced by "under a nitrogen environment at room temperature and pressure, inkjet printing a first electronic material solution on the side of the light-emitting layer away from the hole transport layer to obtain a first liquid film, and then placing the first liquid film in a 0.01Pa, nitrogen atmosphere, vacuum drying treatment for 15 minutes, and then heat treatment at a constant temperature of 100°C in a nitrogen atmosphere for 10 minutes to obtain a first sublayer, wherein the preparation method of the first electronic material solution is: providing Zn 0.9 Mg 0.1 O solution (the solvent is ethylene glycol monobutyl ether, glycerol and diethylene glycol mixed in a volume ratio of 1:1:1), polymethyl methacrylate is added thereto, and the mixture is fully dispersed to obtain a first electronic material solution, wherein the concentration of polymethyl methacrylate in the electronic material solution is 6.25 mg / mL, and the concentration of Zn in the electronic material solution is 1.375 mg / mL. 0.9 Mg 0.1 The concentration of O is 25 mg / mL; then, under a nitrogen environment at room temperature and pressure, a second electronic material solution is inkjet printed on a side of the first sublayer away from the light-emitting layer to obtain a second liquid film, and then the second liquid film is placed in a 0.01 Pa, nitrogen atmosphere, vacuum drying treatment for 15 minutes, and then constant temperature heat treatment at 100° C., nitrogen atmosphere for 10 minutes to obtain a second sublayer, wherein the preparation method of the second electronic material solution is: provide Zn 0.9 Mg 0.1 O solution (the solvent is ethylene glycol monobutyl ether, glycerol and diethylene glycol mixed in a volume ratio of 1:1:1), polymethyl methacrylate is added thereto, and the mixture is fully dispersed to obtain a first electronic material solution, wherein the concentration of polymethyl methacrylate in the electronic material solution is 1.32 mg / mL, and the concentration of Zn in the electronic material solution is 1.32 mg / mL. 0.9 Mg 0.1 O concentration is 25 mg / mL; finally, in a nitrogen environment at room temperature and pressure, a nano ZnO with a concentration of 25 mg / mL is inkjet printed on the side of the second sublayer away from the first sublayer. 0.9 Mg 0.1 O solution (the solvent is ethylene glycol monobutyl ether, glycerol and diethylene glycol mixed in a volume ratio of 1:1:1) to obtain a third liquid film, and then the third liquid film is placed in a 0.01Pa, nitrogen atmosphere, vacuum drying treatment for 15 minutes, and then heat-treated at 100°C in a nitrogen atmosphere for 10 minutes to obtain a third sublayer.

[0142] Comparative Example

[0143] This comparative example provides a photoelectric device and a preparation method thereof. Compared with the photoelectric device in Example 1, the difference between the photoelectric device in this comparative example is that the material of the electronic functional layer is Zn 0.9 Mg 0.1O (average particle size is 5 nm).

[0144] Compared with the preparation method of the optoelectronic device in Example 1, the difference of the preparation method of the optoelectronic device in this comparative example is that step S1.5 is replaced by "inkjet printing 25 mg / mL of nano Zn on the side of the light-emitting layer away from the hole transport layer under a nitrogen environment at room temperature and pressure"; 0.9 Mg 0.1 O solution (the solvent is ethylene glycol monobutyl ether, glycerol and diethylene glycol mixed in a volume ratio of 1:1:1) to obtain a liquid film, and then the liquid film is placed in a 0.01Pa, nitrogen atmosphere, vacuum drying treatment for 15 minutes, and then constant temperature heat treatment at 100°C, nitrogen atmosphere for 10 minutes to obtain an electronic functional layer.

[0145] Experimental example

[0146] The encapsulated optoelectronic devices in Examples 1 to 15 were placed in a 120° C. atmospheric pressure environment for heat treatment for 30 min, and then the performance of each of the optoelectronic devices that completed the heat treatment was tested. The performance test included: electroluminescent morphology, maximum brightness (L max ,cd / m 2 ), maximum current efficiency (CE max ,cd / A) and device life. The test environment temperature is 25℃ and the relative humidity is 40%.

[0147] Among them, IVL optical property measurement equipment (including Ocean Optics USB2000, LabView controlled QE-PRO spectrometer, Keithley2400, high-precision digital source meter Keithley 6485, optical fiber with an inner diameter of 50μm, device test probes and fixtures, various related connecting wires and data cards, efficiency test cassettes and data acquisition systems, etc.) is used to detect and obtain the voltage, current, brightness, luminescence spectrum and other parameters of each optoelectronic device, and then calculate the maximum external quantum efficiency, power efficiency and other key parameters, and use life test equipment to test the device life of each optoelectronic device.

[0148] Maximum brightness (L max ,cd / m 2 ) is to intermittently collect the driving voltage and current, obtain the brightness value of the optoelectronic device in the current range of 0.001mA to 2.4mA, and collect the luminous area of ​​0.0314cm 2 The initial current value of the brightness collection is 0.2A, and the current is collected every 0.2A to obtain the maximum brightness (L max ,cd / m 2 ).

[0149] The current efficiency test method is: set the luminous area to 2mm×2mm=4mm 2 , intermittently collect the brightness value of the light-emitting device in the range of 0V to 8V. The initial voltage value of the brightness is 0.5V, and the brightness value collected each time is divided by the corresponding current density to obtain the current efficiency of the light-emitting device under the collection conditions, and the maximum current efficiency (CE max ,cd / A).

[0150] The device life test method includes the following steps: under the drive of a constant current (2mA), a 128-channel QLED life test system is used to perform electroluminescence life analysis on each photoelectric device, and the time required for each photoelectric device to decay from the maximum brightness to 95% (T95, h) is recorded. The time required for the brightness of each photoelectric device to decay from 100% to 95% at a brightness of 1000nit is calculated by a decay fitting formula (T95@1000nit, h).

[0151] During the performance test, three parallel samples were set for each photoelectric device, and the test average value of the three parallel samples was taken for each performance test parameter. The performance test results of each photoelectric device under 25°C environment are shown in Table 1 below:

[0152] Table 1 Summary of performance test results of optoelectronic devices in Examples 1 to 10, Comparative Examples 1 and 2

[0153]

[0154] From Table 1, Figure 3 and Figure 4 It can be seen that for the photoelectric device of the upright structure, compared with the photoelectric device in comparative example 1, the comprehensive performance of the photoelectric devices in Examples 1 to 9 has significant advantages, which is specifically manifested as follows: the CE max and L max Taking Example 1 and Comparative Example 1 as examples, the L max is the L of the optoelectronic device in Comparative Example 1 max The T95 of the optoelectronic device in Example 1 is 1.6 times that of the optoelectronic device in Comparative Example 1, T95 of the optoelectronic device in Example 1 is 3.1 times that of the T95 of the optoelectronic device in Comparative Example 1, and T95@1000nit of the optoelectronic device in Example 1 is 6.8 times that of the T95@1000nit of the optoelectronic device in Comparative Example 1.

[0155] It is thus shown that in the optoelectronic device, the material of the electronic functional layer includes a metal oxide material and an organic electron blocking material, which can improve the thickness uniformity of the electronic functional layer, and is conducive to optimizing the interface between the electronic functional layer and the cathode and the interface between the electronic functional layer and the light-emitting layer, thereby improving the optoelectronic performance and device life of the optoelectronic device; in addition, for QLEDs with an electron injection level greater than a hole injection level, the first surface layer does not contain the organic electron blocking material or the content of the organic electron blocking material in the first surface layer is less than the content of the organic electron blocking material in the second surface layer. On the one hand, it can effectively reduce the barrier between the electronic functional layer and the cathode, promote the injection of electrons from the cathode to the electronic functional layer, and effectively improve the electron injection level of the optoelectronic device; on the other hand, a certain electron injection barrier is provided between the electronic functional layer and the light-emitting layer, which can slow down the rate of electron injection into the light-emitting layer, thereby promoting the electron-hole transfer balance of the optoelectronic device, and then improving the optoelectronic performance and device life of the optoelectronic device. Further, along the direction from the anode to the cathode, the content of the organic electron blocking material in the electronic functional layer gradually decreases, which can form a gradual electron injection barrier, which is conducive to further improving the optoelectronic performance and device life of the optoelectronic device.

[0156] The above is a detailed introduction to an optoelectronic device, a method for preparing an optoelectronic device, and an electronic device provided in the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the technical solutions and core ideas of the present application; ordinary technicians in this field should understand that they can still modify the technical solutions recorded in the aforementioned embodiments, or replace some of the technical features therein by equivalents; and these modifications or replacements do not make the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A photoelectric device, characterized in that: include: An anode and a cathode arranged opposite to each other; as well as A functional layer, disposed between the cathode and the cathode, the functional layer comprising an electronic functional layer; The material of the electronic functional layer includes a metal oxide material and an organic electron blocking material; along the direction from the anode to the cathode, the electronic functional layer includes a first surface layer and a second surface layer arranged opposite to each other, and the second surface layer is closer to the anode than the first surface layer; The first surface layer does not contain the organic electron blocking material, or the content of the organic electron blocking material in the first surface layer is less than the content of the organic electron blocking material in the second surface layer.

2. The optoelectronic device according to claim 1, characterized in that: In the electronic functional layer, the mass ratio of the metal oxide material to the organic electron blocking material is 1:(0.01-0.4); and / or The metal oxide material is selected from an undoped first metal oxide and / or a doped second metal oxide, the undoped first metal oxide is selected from one or more of ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3 and ZrO2; and / or, the doped second metal oxide is a first main metal oxide doped with a first doping element, the first main metal oxide is selected from ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3 or ZrO2, and the first doping element is selected from one or more of Mg, Ca, Zr, W, Ga, Li, Al, Ti, Y, In and Sn; and / or The organic electron blocking material is selected from one or more of polyaniline, polyethyleneimine, polystyrene, polypropylene, polymethyl methacrylate and polyacrylonitrile; and / or The thickness of the electronic functional layer is 10nm to 60nm; and / or The thickness of the first surface layer is equal to the thickness of the second surface layer; and / or The thickness of the first surface layer does not exceed 10 nm, and / or the thickness of the second surface layer does not exceed 10 nm.

3. The optoelectronic device according to claim 1 or 2, characterized in that: The electronic functional layer is a single-layer structure, and the content of the organic electron blocking material in the electronic functional layer gradually decreases in the direction from the anode to the cathode.

4. The optoelectronic device according to claim 1 or 2, characterized in that: The electronic functional layer includes a first sublayer to an Nth sublayer stacked in sequence, N is a positive integer greater than or equal to 2, and the first sublayer to the Nth sublayer are arranged in sequence along the direction from the anode to the cathode, each sublayer includes the metal oxide material, and the content of the organic electron blocking material in the first sublayer to the Nth sublayer decreases in sequence.

5. The optoelectronic device according to claim 4, characterized in that: In each of the first sublayer to the Nth sublayer, the thickness of each sublayer is 5 nm to 20 nm; and / or The content of the organic electron blocking material in the Nth sublayer is zero.

6. The optoelectronic device according to claim 1 or 2, characterized in that: The functional layer also includes a light-emitting layer, which is arranged between the electronic functional layer and the anode. The material of the light-emitting layer includes one or more organic light-emitting materials and quantum dots; the organic light-emitting material is selected from 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridine iridium(III), 4,4',4"-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridine iridium, diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, T One or more of TPX fluorescent material, TBRb fluorescent material, DBP fluorescent material, delayed fluorescent material, TTA material, thermally activated delayed material, polymer containing BN covalent bond, hybrid localized charge transfer excited state material, exciplex luminescent material, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives; and / or, the quantum dots are selected from one or more of single component quantum dots, core-shell structure quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots and organic-inorganic hybrid perovskite quantum dots;The material of the single-component quantum dot, the material of the core of the core-shell structure quantum dot and the material of the shell of the core-shell structure quantum dot are independently selected from at least one of a II-VI group compound, a III-V group compound, a IV-VI group compound or a I-III-VI group compound, wherein the II-VI group compound is 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 and HgZnSTe, and the III-V group compound is selected from 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 and InAlPSb The group IV-VI compound is selected from one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe, and the group I-III-VI compound is selected from one or more of CuInS, CuInSe and AgInS; and / or the general structural formula of the inorganic perovskite quantum dots is AMX3, wherein A is Cs; + , M is a divalent metal cation, M is selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ and Eu 2+ One or more of, X is a halogen anion; and / or, the general structural formula of the organic perovskite quantum dot is CMX3, C is a carboxamidine group; and / or, the general structural formula of the organic-inorganic hybrid perovskite quantum dot is BMX3, B is an organic amine cation; and / or The material of the anode and the material of the cathode independently include one or more of a metal, a carbon material and a third metal oxide; wherein the metal is selected from one or more of Al, Ag, Cu, Mo, Au, Ba, Pt, Ca, Ir, Ni and Mg, and / or the carbon material is selected from one or more of graphite, carbon nanotubes, graphene and carbon fibers, and / or the third metal oxide is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, aluminum-doped magnesium oxide, SnO2, ZnO and In2O3; and / or The functional layer further comprises a hole functional layer, wherein the hole functional layer is arranged between the anode and the electron functional layer, and the material of the hole functional layer comprises one or more of an organic compound, a non-doped first inorganic compound and a doped second inorganic compound; wherein the organic compound is selected from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), copper phthalocyanine, titanium phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10,11-hexycyano-1,4,5,8,9,12-hexaazatriphenylene, polypyrrole, polyaniline, 3-hexyl substituted polythiophene, poly(9-vinyl carbazole), 4,4'-di(9- carbazole) biphenyl, poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-dioctylfluorenyl-2,7-diyl)], 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4"-tris(carbazole-9-yl)triphenylamine, 4,4',4'-tris(2-naphthylphenylamino)triphenylamine, N,N' -diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirobifluorene-2,7-diamine, N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirobi[9H-fluorene]-2,7-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)] Amino] one or more of -9,9'-spirobifluorene; and / or, the non-doped first inorganic compound is selected from one or more of graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, P-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide and tungsten sulfide; and / or, the doped second inorganic compound is a main inorganic compound doped with a second doping element, the main inorganic compound is selected from one or more of graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, P-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide and tungsten sulfide, and / or the second doping element is selected from one or more of nickel, molybdenum, tungsten, vanadium, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide and tungsten sulfide, and / or the second doping element is selected from one or more of nickel, molybdenum, tungsten, vanadium, chromium, copper and platinum group metal elements.

7. A method for preparing a photoelectric device, characterized in that: The steps include: providing a bottom electrode, and forming a functional layer on one side of the bottom electrode; and forming a top electrode on a side of the functional layer away from the bottom electrode; Wherein, one of the bottom electrode and the top electrode is an anode, and the other is a cathode; forming the functional layer comprises the steps of: forming an electronic functional layer on one side of the bottom electrode; forming the top electrode on a side of the electronic functional layer away from the bottom electrode; Among them, the material of the electronic functional layer includes a metal oxide material and an organic electron blocking material; along the direction from the anode to the cathode, the electronic functional layer includes a first surface layer and a second surface layer arranged relatively to each other, the second surface layer is closer to the anode than the first surface layer, the first surface layer does not contain the organic electron blocking material, or the content of the organic electron blocking material in the first surface layer is less than the content of the organic electron blocking material in the second surface layer.

8. The method for preparing a photoelectric device according to claim 7, characterized in that: The bottom electrode is an anode and the top electrode is a cathode, and the method for forming the electronic functional layer comprises the following steps: Providing a cured film layer including a metal oxide material and an organic electron blocking material, wherein the cured film layer includes a first surface layer and a second surface layer arranged opposite to each other, wherein the second surface layer is closer to the anode than the first surface layer; as well as The cured film layer is subjected to active oxygen treatment so that the first surface layer does not contain the organic electron blocking material, or the content of the organic electron blocking material in the first surface layer is less than the content of the organic electron blocking material in the second surface layer, thereby obtaining an electronic functional layer.

9. The preparation method according to claim 8, characterized in that: The active oxygen treatment is selected from one or more of oxygen ion irradiation treatment, oxygen plasma treatment and atmosphere treatment; and / or The thickness of the cured film layer is 10nm to 60nm; and / or The content of the organic electron blocking material in the electronic functional layer gradually decreases in a direction from the anode to the cathode. In the cured film layer, the mass ratio of the metal oxide material to the organic electron blocking material is 1:(0.01-1).

10. The preparation method according to claim 9, characterized in that: The active oxygen treatment of the cured film layer comprises the steps of: placing the cured film layer in an ion irradiation device, wherein the first surface layer is configured to be closer to an ion source of the ion irradiation device than the second surface layer; In the oxygen ion irradiation treatment, the energy range of the injected oxygen ions is 0.2keV to 50keV, and the injected oxygen ion dose is 1×10 15 ions / cm 2 ~1×10 21 ions / cm 2 ; and / or The active oxygen treatment of the cured film layer comprises the following steps: placing the cured film layer in a treatment chamber of a plasma generator, and performing oxygen plasma treatment on the cured film layer by using oxygen plasma generated by gas discharge, wherein the first surface layer is configured to be closer to the ion source of the plasma generator than the second surface layer; wherein the generated gas comprises an oxygen-containing gas, and the oxygen-containing gas is selected from one or more of pure oxygen, water vapor, acid-containing vapor, and alcohol-containing vapor, the pressure in the treatment chamber is 0.1 Pa to 100 Pa, the output frequency of the plasma generator is 100 W to 2000 W, and the time of the active oxygen treatment is 5 min to 120 min; and / or The active oxygen treatment of the cured film layer includes the steps of: placing the cured film layer in a gas atmosphere for atmosphere treatment; wherein the gas forming the gas atmosphere is selected from one or more of ozone and peroxide gas, the pressure of the gas atmosphere is 100KPa~1000KPa, and the time of the atmosphere treatment is 20min~300min.

11. The preparation method according to claim 10, characterized in that: In the oxygen plasma treatment, the generating gas further comprises an inert gas, the inert gas is selected from one or more of nitrogen, helium, neon, argon, krypton, xenon and radon, and / or the volume of the oxygen-containing gas accounts for 10% to 100% of the total volume of the generating gas; and / or The acid in the acid-containing vapor is selected from one or more of hydrogen halide, nitric acid, acetic acid and sulfuric acid, and the concentration of hydrogen ions in the acid-containing vapor is 0.001 mol / L to 0.1 mol / L; and / or The alcohol in the alcohol-containing vapor is selected from fatty alcohol compounds having 1 to 10 carbon atoms.

12. The preparation method according to claim 10, characterized in that: In the oxygen plasma treatment, the generated gas is water vapor; or, the generated gas is formed by gasification of an acid-containing solution, the solute of the acid-containing solution includes one or more of hydrogen halide, nitric acid, acetic acid and sulfuric acid, the solvent of the acid-containing solution is a fatty alcohol compound with a carbon number of 1 to 10, and the concentration of hydrogen ions in the acid-containing solution is 0.001 mol / L to 0.1 mol / L.

13. The method for preparing a photoelectric device according to claim 7, characterized in that: The electronic functional layer includes a first sublayer to an Nth sublayer stacked in layers, where N is a positive integer greater than or equal to 2; when the bottom electrode is an anode and the top electrode is a cathode, the method for forming the electronic functional layer includes the steps of: sequentially forming the first sublayer to the Nth sublayer on one side of the bottom electrode; or, when the bottom electrode is a cathode and the top electrode is an anode, the method for forming the electronic functional layer includes the steps of: sequentially forming the Nth sublayer to the first sublayer on one side of the bottom electrode; Each of the first to Nth sublayers includes the metal oxide material, and the content of the organic electron blocking material in the first to Nth sublayers decreases sequentially.

14. The method for preparing a photoelectric device according to claim 13, characterized in that: The method for preparing at least one of the first to Nth sublayers comprises the steps of: depositing a dispersion liquid comprising the metal oxide material and the organic electron blocking material; and drying the deposited dispersion liquid to solidify it into a film; and / or The thickness of each of the N sub-layers is 5 nm to 20 nm; and / or The content of the organic electron blocking material in the Nth sublayer is zero; and / or In the electronic functional layer, the mass ratio of the metal oxide material to the organic electron blocking material is 1:(0.01-1).

15. The preparation method according to any one of claims 7 to 14, characterized in that: The bottom electrode is an anode and the top electrode is a cathode. Before the step of forming the electronic functional layer, forming the functional layer further comprises the steps of: forming a light-emitting layer on one side of the bottom electrode; the electronic functional layer is formed on a side of the light-emitting layer away from the bottom electrode; the bottom electrode is a cathode and the top electrode is an anode. After the step of forming the electronic functional layer, forming the functional layer further comprises the steps of: forming a light-emitting layer on a side of the electronic functional layer away from the bottom electrode; the material of the light-emitting layer comprises one or more of an organic light-emitting material and quantum dots; and / or The bottom electrode is an anode and the top electrode is a cathode. Before the step of forming the electronic functional layer, forming the functional layer further comprises the steps of: forming a hole functional layer on one side of the bottom electrode; the electronic functional layer is formed on the side of the hole functional layer away from the bottom electrode; the bottom electrode is a cathode and the top electrode is an anode. After the step of forming the electronic functional layer, forming the functional layer further comprises the steps of: forming a hole functional layer on the side of the electronic functional layer away from the bottom electrode; The material of the hole functional layer includes one or more of an organic compound, a non-doped first inorganic compound, and a doped second inorganic compound; wherein the organic compound is selected from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), copper phthalocyanine, titanium phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, 2,3,6,7,10,11-hexycyano-1,4,5,8,9,12-hexaazatriphenylene, polypyrrole, polyaniline, 3-hexyl substituted polythiophene, poly(9-vinyl carbazole), 4,4'-bis(9-carbazole)biphenyl, poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4' -cyclohexylbis[N,N-di(4-methylphenyl)aniline], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-dioctylfluorenyl-2,7-diyl)], 4,4',4'-tri(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4"-tri(carbazol-9-yl)triphenylamine, 4,4',4'-tri(2-naphthylphenylamino)triphenylamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1' -biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirobifluorene-2,7-diamine, N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirobi[9H-fluorene]-2,7-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene One or more of; and / or, the non-doped first inorganic compound is selected from one or more of graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, P-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide and tungsten sulfide; and / or, the doped second inorganic compound is a main inorganic compound doped with a second doping element, the main inorganic compound is selected from one or more of graphene, C60, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, P-type gallium nitride, chromium oxide, copper oxide, copper sulfide, molybdenum sulfide and tungsten sulfide, and / or the second doping element is selected from one or more of nickel, molybdenum, tungsten, vanadium, chromium, copper and platinum group metal elements; and / or The metal oxide material is selected from an undoped first metal oxide and / or a doped second metal oxide, the undoped first metal oxide is selected from one or more of ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3 and ZrO2; and / or, the doped second metal oxide is a first main metal oxide doped with a first doping element, the first main metal oxide is selected from ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3 or ZrO2, and the first doping element is selected from one or more of Mg, Ca, Zr, W, Ga, Li, Al, Ti, Y, In and Sn; and / or The organic electron blocking material is selected from one or more of polyaniline, polyethyleneimine, polystyrene, polypropylene, polymethyl methacrylate and polyacrylonitrile; and / or The thickness of the electronic functional layer is 10nm-60nm.

16. An electronic device, characterized in that: The invention comprises a photoelectric device as claimed in any one of claims 1 to 6, or a photoelectric device prepared by the preparation method as claimed in any one of claims 7 to 15.

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