Photoelectric device, preparation method thereof and display device

Abstract

The invention discloses a photoelectric device, a preparation method thereof and a display device, and relates to the technical field of display. The photoelectric device comprises an anode, a functional layer and a cathode which are sequentially stacked. The photoelectric device further comprises a first stable layer located on the side, away from the functional layer, of the anode, and / or a second stable layer located on the side, away from the functional layer, of the cathode, and / or a third stable layer located between the anode and the functional layer. Wherein the materials of each stable layer respectively and independently comprise one or more of 2-mercaptothiazoline and derivatives thereof, and 2-mercaptobenzothiazole and derivatives thereof. According to the photoelectric device provided by the invention, the electrochemical corrosion resistance of the electrode can be enhanced, the stability of the electrode is improved, the photoelectric efficiency of the photoelectric device is further improved, and the service life of the photoelectric device is prolonged.

Description

Technical Field

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

[0002] Currently, the widely used optoelectronic devices are organic light-emitting diodes (OLEDs) and quantum dot light-emitting diodes (QLEDs). OLEDs have become the mainstream technology in the field of display technology due to their excellent display performance, such as self-luminescence, simple structure, ultra-thinness, fast response speed, wide viewing angle, low power consumption, and flexible display. QLEDs have the advantages of saturated color and adjustable wavelength of emitted light, and high quantum yield of photoluminescence and electroluminescence, and have become a strong competitor to OLEDs in recent years.

[0003] The structure of traditional OLED and QLED devices generally includes an anode, a hole injection layer, a hole transport layer, an active layer, an electron transport layer, an electron injection layer, and a cathode. Under the action of the electric field, the holes generated by the anode of the light-emitting diode and the electrons generated by the cathode move and are injected into the hole transport layer and the electron transport layer respectively, and finally migrate to the active layer. When the two meet in the active layer, energy excitons are generated, thereby exciting the luminescent molecules and finally producing visible light. At present, the electrodes of optoelectronic devices are susceptible to corrosion, which causes the optoelectronic devices to age rapidly and affects the optoelectronic performance of the optoelectronic devices.

[0004] Therefore, the corrosion phenomenon of the electrode needs to be further improved. Summary of the invention

[0005] In view of this, the present application provides an optoelectronic device and a method for manufacturing the same, and a display device.

[0006] The embodiment of the present application is implemented as follows: a photoelectric device includes an anode, a functional layer and a cathode stacked in sequence;

[0007] The optoelectronic device further comprises a first stabilization layer located on a side of the anode away from the functional layer, and / or a second stabilization layer located on a side of the cathode away from the functional layer, and / or a third stabilization layer located between the anode and the functional layer;

[0008] Among them, the material of the first stabilization layer includes a first stabilizer, the material of the second stabilization layer includes a second stabilizer, and the material of the third stabilization layer includes a third stabilizer. The first stabilizer, the second stabilizer, and the third stabilizer each independently include one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

[0009] Accordingly, an embodiment of the present application further provides a method for preparing a photoelectric device, comprising:

[0010] providing a substrate;

[0011] Forming a stabilizing layer and a functional layer on a substrate, including:

[0012] Providing a first stabilizing layer material, wherein the first stabilizing layer material includes a first stabilizer, and disposing the first stabilizing layer material on the substrate to form a first stabilizing layer; sequentially forming an anode, a functional layer and a cathode on the first stabilizing layer to obtain a photoelectric device; and / or

[0013] An anode, a functional layer and a cathode are sequentially formed on the substrate; a second stabilizing layer material is provided, wherein the second stabilizing layer material includes a second stabilizer, and the second stabilizing layer material is disposed on the cathode to form a second stabilizing layer, thereby obtaining a photoelectric device; and / or

[0014] An anode is formed on the substrate, a third stabilizer is provided, and the third stabilizer is disposed on the anode to form a third stabilizing layer; a functional layer and a cathode are sequentially formed on the third stabilizing layer to obtain a photoelectric device;

[0015] or,

[0016] providing a substrate;

[0017] Forming a stabilizing layer and a functional layer on a substrate, including:

[0018] Providing a second stabilizing layer material, wherein the second stabilizing layer material includes a second stabilizer, and disposing the second stabilizing layer material on the substrate to form a second stabilizing layer; sequentially forming a cathode, a functional layer and an anode on the second stabilizing layer to obtain a photoelectric device; and / or

[0019] forming a cathode, a functional layer and an anode on the substrate in sequence; providing a first stabilizing layer material, wherein the first stabilizing layer material comprises a first stabilizer, and disposing the first stabilizing layer material on the anode to form a first stabilizing layer, thereby obtaining a photoelectric device; and / or

[0020] A cathode and a functional layer are sequentially formed on the substrate, a third stabilizer is provided, and the third stabilizer is disposed on the functional layer to form a third stabilizer layer; an anode is formed on the third stabilizer layer to obtain a photoelectric device;

[0021] Wherein, the first stabilizer, the second stabilizer, the third stabilizer and the fourth stabilizer each independently include one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

[0022] Correspondingly, an embodiment of the present application further provides a display device, which includes the above-mentioned optoelectronic device.

[0023] The photoelectric device provided in the present application can enhance the electrode's resistance to electrochemical corrosion, improve the electrode's stability, and thereby improve the photoelectric efficiency of the photoelectric device and extend the service life of the photoelectric device. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0025] Figure 1 is a schematic diagram of the structure of the optoelectronic device provided in an embodiment of the present application;

[0026] Figure 2 is a schematic structural diagram of another optoelectronic device provided in an embodiment of the present application;

[0027] Figure 3 is a schematic structural diagram of another optoelectronic device provided in an embodiment of the present application;

[0028] Figure 4 is a schematic structural diagram of another optoelectronic device provided in an embodiment of the present application;

[0029] Figure 5 is a schematic structural diagram of another optoelectronic device provided in an embodiment of the present application;

[0030] Figure 6 is a flow chart of a method for preparing a photoelectric device provided in an embodiment of the present application;

[0031] Figure 7 This is a flow chart of another method for preparing an optoelectronic device provided in an embodiment of the present application.

[0032] Reference numerals:

[0033] Anode 10 ; active layer 20 ; cathode 30 ; hole functional layer 40 ; electron functional layer 50 ; first stabilizing layer 60 ; second stabilizing layer 70 ; third stabilizing layer 80 ; fourth stabilizing layer 90 . DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application will be clearly and completely described 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 making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0035] In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

[0036] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0037] In the present application, "at least one" means one or more, and "plurality" means two or more. "One or several", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0038] 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 brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have 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 herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0039] Optoelectronic devices often face serious device aging. The aging of optoelectronic devices causes the performance of optoelectronic devices to gradually decay over time, which greatly affects the service life of optoelectronic devices. There are many factors that lead to the aging of optoelectronic devices, such as the decline in film quality and the increase in impurities caused by the diffusion of elements in the film. Among them, the corrosion of optoelectronic device electrodes, which leads to the decline in the electrical performance of the electrodes and the overall stability of the device, is one of the main reasons for the rapid aging of the device. Inhibiting the corrosion of electrodes is the main way to improve device stability, improve aging phenomena, and increase service life.

[0040] The technical solution of this application is as follows:

[0041] First, see Figures 1 to 4 , the embodiment of the present application provides a photoelectric device, comprising an anode 10, a functional layer and a cathode 30 which are stacked in sequence;

[0042] The optoelectronic device further comprises a first stabilization layer 60 located on a side of the anode 10 away from the functional layer, and / or a second stabilization layer 70 located on a side of the cathode 30 away from the functional layer, and / or a third stabilization layer 80 located between the anode 10 and the functional layer;

[0043] Among them, the material of the first stabilization layer 60 includes a first stabilizer, the material of the second stabilization layer 70 includes a second stabilizer, and the material of the third stabilization layer 80 includes a third stabilizer. The first stabilizer, the second stabilizer, and the third stabilizer each independently include one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

[0044] In the optoelectronic device provided by the present application, the N atoms in each stabilizer and the S atoms in the mercapto group have a strong coordination ability with the metal or metal alloy of the adjacent electrode, and can form a strong bond with it, thereby forming a metal-organic chain on the electrode surface, thereby effectively stabilizing the diffusion and movement of metal elements, improving the corrosion potential, reducing the corrosion current, and significantly enhancing the electrode's resistance to electrochemical corrosion; in addition, due to the coverage of the electrode by the stabilization layer and the element coordination, it is beneficial to prevent the oxidation of the electrode by oxidizing factors such as external impurity free radicals, further improving the stability of the electrode, thereby improving the photoelectric efficiency of the optoelectronic device and extending the service life of the optoelectronic device.

[0045] Specifically, see Figure 1 In some embodiments, the optoelectronic device includes a first stabilizing layer 60, an anode 10, a functional layer and a cathode 30 which are stacked in sequence.

[0046] In some other embodiments, see Figure 2 The photoelectric device includes an anode 10, a functional layer, a cathode 30 and a second stabilizing layer 70 which are stacked in sequence.

[0047] In some other embodiments, see Figure 3 The photoelectric device includes an anode 10, a third stabilizing layer 80, a functional layer, and a cathode 30 which are stacked in sequence.

[0048] In some other embodiments, see Figure 4The photoelectric device includes a first stabilizing layer 60, an anode 10, a third stabilizing layer 80, a functional layer, a cathode 30 and a second stabilizing layer 70 which are stacked in sequence.

[0049] In some embodiments, the materials of the anode 10 and the cathode 30 independently include one or more of metals and alloys.

[0050] In some embodiments, the metal includes a low work function metal. The low work function metal has a lower electron affinity and a higher ion affinity, so that the ability of electrons to transfer from the electrode to the electrolyte is weaker, thereby reducing the potential difference and facilitating the equilibrium potential of the electrode surface.

[0051] Furthermore, the work function of the low work function metal does not exceed 4.5 eV.

[0052] The low work function metal includes one or more of alkali metals, alkaline earth metals, transition metals, lanthanide metals, and actinide metals.

[0053] Furthermore, the alkali metal includes one or more of lithium, sodium, potassium, rubidium, cesium, and francium.

[0054] The alkaline earth metal includes one or more of beryllium, magnesium, calcium, strontium, barium and radium.

[0055] The transition metal includes one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, rhodium, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, tantalum, tungsten, rhenium, tungsten ...

[0056] The lanthanide metal includes one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

[0057] The actinide metal includes one or more of actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and lawrencium.

[0058] The alloy includes a substance with metallic properties composed of two or more metal or non-metal elements. For example, the alloy includes silver-copper alloy, silver-magnesium alloy, gold-iron alloy, rhodium-platinum alloy, etc.

[0059] It should be noted that, when the optoelectronic device includes the first stabilization layer 60 and / or the third stabilization layer 80, the material of the cathode 30 includes one or more of a metal, a carbon material, and a metal oxide; the metal includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Yb, and Mg; the carbon material includes one or more of graphite, carbon nanotubes, graphene, and carbon fiber; the metal oxide includes a metal oxide electrode or a composite electrode in which a metal is arranged between doped or non-doped transparent metal oxides; the metal The material of the oxide electrode includes one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, MoO3 and AMO, and the composite electrode includes one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2 and TiO2 / Al / TiO2. Accordingly, when the optoelectronic device includes the second stabilization layer 70, the material of the anode 10 may also include the above materials.

[0060] In some embodiments, the thickness of the anode 10 and the cathode 30 is 1 nm to 60 nm, for example, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, etc. Within the thickness range, the electrode can provide a higher load and conductivity. It can be understood that thin electrodes are more susceptible to corrosion by external oxidative free radicals and other factors, but the metal elements of the thin electrode are easily bonded with the stabilizer of the stabilization layer, thereby inhibiting the corrosion of the electrode.

[0061] In some embodiments, the structural formula of the 2-mercaptothiazoline and its derivatives is as shown in formula (I):

[0062]

[0063] In some embodiments, the structural formula of the 2-mercaptobenzothiazole and its derivatives is as shown in formula (II):

[0064]

[0065] It can be understood that R1, R2, R3, R4, R5, and R6 can be selected from any chemical elements, groups, etc.

[0066] For example, in some embodiments, R1, R2, R3, R4, R5, and R6 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C20 Alkoxy, substituted or unsubstituted C1-C 20 substituted or unsubstituted C1-C 20 Alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C3-C 20 heterocyclic group, substituted or unsubstituted C2-C 20 alkenyl, substituted or unsubstituted C2-C 20 One or more of the alkynyl groups.

[0067] Preferably, R1, R2, R3, R4, R5, and R6 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C5-C 10 Alkyl, substituted or unsubstituted C5-C 10 Alkoxy, substituted or unsubstituted C5-C 10 substituted or unsubstituted C5-C 10 Alkoxycarbonyl, substituted or unsubstituted C8-C 15 Aryl, substituted or unsubstituted C5-C 10 heterocyclic group, substituted or unsubstituted C5-C 10 Alkenyl, substituted or unsubstituted C5-C 10 One or more of the alkynyl groups.

[0068] The halogen includes one or more of fluorine, chlorine, bromine and iodine.

[0069] The alkyl group includes one or more of methyl, ethyl, isopropyl and tert-butyl.

[0070] The alkoxy group includes one or more of methoxy, ethoxy and propoxy.

[0071] The acyloxy group includes one or more of formyloxy, acetyloxy, propionyloxy, butyryloxy, octanoyloxy, palmitoyloxy, and stearoyloxy.

[0072] The alkoxycarbonyl group includes one or more of methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, palmityloxycarbonyl and stearyloxycarbonyl.

[0073] The aryl group includes one or more of phenyl, p-tolyl, p-nitrophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, and p-nitromethoxyphenyl.

[0074] The alkenyl group includes one or more of vinyl, propenyl and butenyl.

[0075] The alkynyl group includes one or more of ethynyl, propynyl, pentynyl and heptynyl.

[0076] The substituted groups include one or more of amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, mercapto, and cyano.

[0077] The heteroatom in the heterocyclic group includes one or more of O, P, N and S.

[0078] The heterocyclic group includes one or more of thiazolyl, thienyl, furanyl, pyrrolyl, pyridyl, pyrimidinyl, imidazolyl, oxazolyl, pyrazinyl, indolyl, quinolyl, pteridinyl and acridinyl.

[0079] In some embodiments, the 2-mercaptothiazoline derivative is selected from one or more of the following structural formulas:

[0080]

[0081] In some embodiments, the derivative of 2-mercaptobenzothiazole is selected from one or more of the following structural formulas:

[0082]

[0083]

[0084] In some embodiments, the material of the first stabilization layer 60 includes 2-mercaptothiazoline and its derivatives and 2-mercaptobenzothiazole and its derivatives, and the molar ratio of the 2-mercaptothiazoline and its derivatives to the 2-mercaptobenzothiazole and its derivatives is (1-100):(1-100), for example, it can be 1:20, 1:50, 1:80, 20:1, 50:1, 80:1, etc.

[0085] Correspondingly, the material of the second stabilizing layer 70 includes 2-mercaptothiazoline and its derivatives and 2-mercaptobenzothiazole and its derivatives, and the molar ratio of the 2-mercaptothiazoline and its derivatives to the 2-mercaptobenzothiazole and its derivatives is (1 to 100): (1 to 100), for example, it can be 1:20, 1:50, 1:80, 20:1, 50:1, 80:1, etc.

[0086] In some embodiments, the material of the first stabilization layer 60 further includes a first light extraction material.

[0087] In some embodiments, the material of the second stabilization layer 70 further includes a second light extraction material.

[0088] Furthermore, the refractive indexes of the first light extraction material and the second light extraction material are 1.0 to 3.0, for example, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, etc. The light extraction material can adjust the optical interference distance, inhibit external light reflection, and inhibit the extinction reaction caused by the movement of surface plasma.

[0089] In some embodiments, the first light extraction material and the second light extraction material respectively include one or more of triarylamine compounds, cyclic urea compounds, acyl structure compounds, dibenzothiophene compounds, dibenzofuran compounds, and carbazole compounds.

[0090] In some embodiments, the first light extraction material and the second light extraction material respectively include one or more of N-methylpyrrolidone (NPB), triethoxypropylsilane (TAPC), triphenylbismuth (TPBI), trichloromethylsilane (TCTA), 1-methylcyclopropene (MCP), MoO3, WO3, V2O5, and LiF.

[0091] In some embodiments, in the first stabilizing layer 60 , the molar ratio of the first stabilizer to the first light extraction material is (1-50):(1-50), for example, 1:20, 1:30, 1:40, 20:1, 30:1, 40:1, etc.

[0092] In some embodiments, in the second stabilizing layer 70, the molar ratio of the second stabilizer to the second light extraction material is (1-50):(1-50), for example, 1:20, 1:30, 1:40, 20:1, 30:1, 40:1, etc.

[0093] In some embodiments, the thickness of the first stabilization layer 60 , the second stabilization layer 70 , and the third stabilization layer 80 are independently 5 nm to 90 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, etc.

[0094] It can be understood that the third stabilization layer 80 is provided inside the photoelectric device, and the stabilization layer is provided between the functional layer and the electrode, which can further prevent the aging corrosion of the electrode, and utilize the coordination effect between the stabilizer and the metal elements in the electrode to lock the metal atoms in the electrode, inhibit the diffusion of metal atoms, and prevent the corrosion of the electrode by oxidizing substances such as free radicals, thereby improving the life of the photoelectric device; in addition, the internal stabilization layer can improve the interface contact between the electrode and the functional layer inside the photoelectric device.

[0095] In some embodiments, the first stabilizer, the second stabilizer, and the third stabilizer are the same or different.

[0096] In some embodiments, the optoelectronic device further includes a fourth stabilization layer 90 located between the functional layer and the cathode 30, and the material of the fourth stabilization layer 90 includes a fourth stabilizer, and the fourth stabilizer includes one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

[0097] It can be understood that the fourth stabilization layer 90 can cooperate with the first stabilization layer 60 and / or the third stabilization layer 80 and / or the second stabilization layer 70 to jointly improve the stability of the optoelectronic device.

[0098] Specifically, see Figure 5 The photoelectric device includes a first stabilization layer 60, an anode 10, a third stabilization layer 80, a functional layer, a fourth stabilization layer 90, a cathode 30 and a second stabilization layer 70 which are stacked in sequence.

[0099] The thickness of the fourth stabilizing layer 80 may refer to the thickness of the third stabilizing layer 80 , and the material of the fourth stabilizer may refer to the above description, which will not be described in detail here.

[0100] In some embodiments, the functional layer includes one or more of a hole functional layer 40 , an active layer 20 , and an electron functional layer 50 , which are sequentially arranged from the anode 10 to the cathode 30 .

[0101] Furthermore, the hole functional layer includes one or more of a hole injection layer and a hole transport layer.

[0102] The electronic functional layer includes one or more of an electron injection layer and an electron transport layer.

[0103] In some embodiments, the material of the active layer 20 includes one or more of organic light-emitting materials and quantum dots.

[0104] The organic light-emitting material includes one or more of 4,4'-bis(N-carbazole)-1,1'-biphenyl:tris[2-(p-tolyl)pyridine iridium(III)], 4,4',4"-tris(carbazole-9-yl)triphenylamine:tris[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, TADF materials, polymers containing covalent bonding of BN, HLCT materials, and Exciplex light-emitting materials.

[0105] In some embodiments, the quantum dots may be selected from, but not limited to, one or more of, single structure quantum dots, core-shell structure quantum dots, and perovskite quantum dots.

[0106] The material of the single structure quantum dots, the core material of the core-shell structure quantum dots and the shell material of the core-shell structure quantum dots can be selected from but not limited to one or more of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds. The shell layer of the core-shell structure quantum dots is one or more layers; the II-VI group compounds can be selected from but not limited to one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe. The IV-VI group compound can be selected from but not limited to one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe. The III-V group compound may be selected from, but not limited to, one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb. The I-III-VI group compound may be selected from, but not limited to, one or more of CuInS2, CuInSe2, and AgInS2.

[0107] As an example, the core-shell structure quantum dots can be selected from but not limited to one or more of CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS and InP / ZnSe / ZnS. The “ / ” in the above expressions such as CdSe / ZnS means that the substance after the “ / ” (as a shell layer) covers the substance before the “ / ” (as a core layer).

[0108] The general structural formula of the perovskite quantum dot is AMX3, wherein A is selected from Cs + 、CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, 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+ 、Eu 2+ One or more of, X is selected from Cl - Br - ,I - One or more of the .

[0109] In some embodiments, the material of the electronic functional layer includes one or more of a first doped metal oxide particle, a first undoped metal oxide particle, a IIB-VIA semiconductor material, a IIIA-VA semiconductor material, and an IB-IIIA-VIA semiconductor material. The material of the first undoped metal oxide particle includes one or more of ZnO, TiO2, SnO2, ZrO2, and Ta2O5. The metal oxide in the first doped metal oxide particle includes one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, and Al2O3. The doping element in the first doped metal oxide particle includes one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, and Ga. The IIB-VIA semiconductor material includes one or more of ZnS, ZnSe, and CdS. The IIIA-VA semiconductor material includes one or more of InP and GaP. The IB-IIIA-VIA semiconductor material includes one or more of CuInS and CuGaS.

[0110] In some embodiments, the material of the hole functional layer includes 4,4'-N,N'-dicarbazolyl-biphenyl, N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(carbazol-9-yl)triphenylamine, trichloroisocyanuric acid, terbium-doped phosphate-based green emission Optical materials, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, 4,4',4'-tri(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(4-butylphenyl-diphenylamine), poly[bis(4-phenyl)(4-butylphenyl)amine], polyaniline, polypyrrole, poly(p-phenylene vinylene), poly(phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)- 1,4-phenylene vinylene], copper phthalocyanine, aromatic tertiary amine, polynuclear aromatic tertiary amine, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compound, N,N,N',N'-tetraaryl benzidine, PEDOT, PEDOT:PSS and its derivatives, PEDOT:PSS derivatives doped with s-MoO3, poly(N-vinyl carbazole) and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, N,N'-di(naphthalene-1-yl)-N,N'-diphenyl benzidine, spiro NPB, nano-polycrystalline diamond, microcrystalline cellulose and tetracyanoquinodimethane, doped graphene, undoped graphene, second doped metal oxide The invention relates to a method for preparing an aqueous solution of at least one doped metal oxide particle, a second non-doped metal oxide particle, a metal sulfide, a metal selenide and a metal nitride, wherein the metal oxide in the second doped metal oxide particle and the metal oxide in the second non-doped metal oxide particle independently include one or more of MoO3, WO3, NiO, CrO3, CuO and V2O5, the doping element in the second doped metal oxide particle includes one or more of Mo, W, Ni, Cr, Cu and V, the metal sulfide includes one or more of CuS, MoS3 and WS3, the metal selenide includes one or more of MoSe3 and WSe3, and the metal nitride includes P-type gallium nitride.

[0111] Second, see Figure 6-7 The present application also provides a method for preparing a photoelectric device, comprising:

[0112] S11, providing a substrate;

[0113] S12, forming a stabilizing layer and a functional layer on the substrate, including:

[0114] Providing a first stabilizing layer material, wherein the first stabilizing layer material includes a first stabilizer, and disposing the first stabilizing layer material on the substrate to form a first stabilizing layer 60; sequentially forming an anode 10, a functional layer and a cathode 30 on the first stabilizing layer 60 to obtain a photoelectric device; and / or

[0115] An anode 10, a functional layer and a cathode 30 are sequentially formed on the substrate; a second stabilizing layer material is provided, wherein the second stabilizing layer material includes a second stabilizer, and the second stabilizing layer material is disposed on the cathode 30 to form a second stabilizing layer 70, thereby obtaining a photoelectric device; and / or

[0116] An anode 10 is formed on the substrate, a third stabilizer is provided, and the third stabilizer is disposed on the anode 10 to form a third stabilizing layer 80; a functional layer and a cathode 30 are sequentially formed on the third stabilizing layer 80 to obtain a photoelectric device.

[0117] It can be understood that the optoelectronic device prepared by the above preparation method is an upright optoelectronic device. The present application also provides a method for preparing an inverted optoelectronic device, comprising:

[0118] S21, providing a substrate;

[0119] S22, forming a stabilizing layer and a functional layer on the substrate, comprising:

[0120] Providing a second stabilizing layer material, wherein the second stabilizing layer material includes a second stabilizer, and disposing the second stabilizing layer material on the substrate to form a second stabilizing layer 70; sequentially forming a cathode 30, a functional layer and an anode 10 on the second stabilizing layer 70 to obtain a photoelectric device; and / or

[0121] Sequentially forming a cathode 30, a functional layer and an anode 10 on the substrate; providing a first stabilizing layer material, wherein the first stabilizing layer material includes a first stabilizer, and disposing the first stabilizing layer 60 material on the anode 10 to form a first stabilizing layer 60, thereby obtaining a photoelectric device; and / or

[0122] A cathode 30 and a functional layer are sequentially formed on the substrate, a third stabilizer is provided, and the third stabilizer is disposed on the functional layer to form a third stabilizer layer 80; an anode 10 is formed on the third stabilizer layer 80 to obtain a photoelectric device.

[0123] Wherein, the first stabilizer, the second stabilizer, the third stabilizer and the fourth stabilizer each independently include one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

[0124] In the preparation method of the optoelectronic device provided in the present application, the first stabilizer and / or the third stabilizer can form an organic-metal chain with the metal element of the anode 10, and the second stabilizer can form an organic-metal chain with the metal element of the cathode 30, thereby effectively inhibiting the corrosion of the electrode, further inhibiting the aging of the optoelectronic device, effectively improving the optoelectronic performance of the optoelectronic device, and extending the service life of the optoelectronic device.

[0125] In some embodiments, the substrate may be a rigid substrate or a flexible substrate. Further, the material of the substrate may be selected from but not limited to at least one of glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide and polyether sulfone.

[0126] In some embodiments, the method of forming the first stabilization layer 60 includes:

[0127] providing a first stabilizer dispersion, wherein the first stabilizer dispersion includes a first stabilizer;

[0128] The first stabilizer dispersion is disposed on the substrate or the anode 10 to form a first stabilizing layer 60 .

[0129] In some embodiments, the first stabilizer dispersion also includes a first solvent, and the first solvent includes one or more of chlorobenzene, diethylene glycol monobutyl ether, trimethoxybutanol, triethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol, isopropanol, glycerol, dimethyl sulfoxide, acetone, acetophenone, tetrahydrofuran, N,N-dimethylformamide, ethyl acetate, pyrrole, butyric acid, and cresol.

[0130] In some embodiments, in the first stabilizer dispersion, the mass concentration of the first stabilizer is 5 mg / mL to 100 mg / mL, for example, 10 mg / mL, 20 mg / mL, 30 mg / mL, 40 mg / mL, 50 mg / mL, 60 mg / mL, 70 mg / mL, 80 mg / mL, 90 mg / mL, etc.

[0131] In some embodiments, after the first stabilizer dispersion is disposed on the substrate or the anode 10, annealing is further included. Further, the annealing temperature is 60°C to 180°C, for example, 80°C, 100°C, 120°C, 140°C, 160°C, etc.; the annealing time is 1min to 60min, for example, 10min, 20min, 30min, 40min, 50min, etc.

[0132] It can be understood that the preparation methods of the second stabilizing layer 70 and the third stabilizing layer 80 can refer to the preparation method of the first stabilizing layer 60 .

[0133] In some other embodiments, the first stabilizing material further includes a first light extraction material, and the method for forming the first stabilizing layer 60 includes:

[0134] Providing a mixed liquid, wherein the mixed liquid includes a first stabilizer and a first light extraction material;

[0135] The mixed solution is disposed on the substrate or the anode 10 to form a first stabilizing layer 60 .

[0136] In some embodiments, the mixed liquid also includes a second solvent, and the second solvent includes one or more of chlorobenzene, diethylene glycol monobutyl ether, trimethoxybutanol, triethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol, isopropanol, glycerol, dimethyl sulfoxide, acetone, acetophenone, tetrahydrofuran, N,N-dimethylformamide, ethyl acetate, pyrrole, butyric acid, and cresol.

[0137] In some embodiments, in the mixed solution, the mass concentration of the first stabilizer is 5 mg / mL to 50 mg / mL, for example, 15 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL, 40 mg / mL, 45 mg / mL, etc.

[0138] In some embodiments, the molar ratio of the first stabilizer to the first light extraction material is (1-50):(1-50), for example, it can be 1:20, 1:30, 1:40, 20:1, 30:1, 40:1, etc.

[0139] It can be understood that when the second stabilizing layer 70 further includes a second light extraction material, the preparation method of the first stabilizing layer 60 can be referred to.

[0140] In some embodiments, after forming the functional layer on the substrate and before forming the cathode 30 , the method further includes: providing a fourth stabilizer, disposing the fourth stabilizer on the functional layer to form a fourth stabilizer layer 90 .

[0141] In some other embodiments, after forming the cathode 30 on the substrate and before forming the functional layer, the method further includes: providing a fourth stabilizer, and disposing the fourth stabilizer on the cathode 30 to form a fourth stabilizer layer 90 .

[0142] The fourth stabilizer includes one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

[0143] The preparation method of the fourth stabilizing layer 90 is as described above and will not be repeated here.

[0144] In a third aspect, an embodiment of the present application further provides a display device, which includes the above-mentioned optoelectronic device.

[0145] The display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, laptops, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, car displays, televisions or e-book readers, among which smart wearable devices can be, for example, smart bracelets, smart watches, virtual reality (VR) helmets, etc.

[0146] The present application is described in detail below through specific embodiments. The following embodiments are only partial embodiments of the present application and are not limitations of the present application.

[0147] Example 1

[0148] This embodiment provides a photoelectric device, and the preparation method thereof is as follows:

[0149] Cleaning the substrate with the patterned electrode; treating the surface of the ITO substrate with UV-ozone for 5 minutes to further remove organic matter attached to the surface of the ITO substrate and to increase the work function of the ITO substrate, thereby forming an anode;

[0150] The PEDOT:PSS solution was spin-coated on the ITO substrate and annealed at 150 °C for 30 min to form a hole injection layer with a thickness of 30 nm;

[0151] The TFB solution was spin-coated on the hole injection layer and annealed at 150°C for 20 min to form a hole transport layer with a thickness of 40 nm;

[0152] Providing a CdZnS quantum dot dispersion and spin coating it on the hole transport layer to form an active layer;

[0153] Spin-coat ZnO ethanol dispersion on the quantum dot active layer and anneal at 80°C for 30 min to form an electron transport layer with a thickness of 30 nm.

[0154] Place it in a vapor deposition chamber and thermally evaporate a layer of silver through a mask plate to form a cathode;

[0155] A dispersion of a second stabilizer, 2-mercaptothiazoline, is placed on the cathode and annealed to form a second stabilizing layer with a thickness of 10 nm;

[0156] Encapsulation is performed to obtain an optoelectronic device.

[0157] Embodiment 2-3

[0158] Embodiments 2 to 3 are basically the same as embodiment 1, except that:

[0159] In Example 2, the second stabilizing layer is not included, and the first stabilizing layer is prepared on the substrate by the method of preparing the second stabilizing layer, the material of the first stabilizing layer includes the first stabilizer 2-mercaptothiazoline, and the Ag anode is prepared on the first stabilizing layer;

[0160] In Example 3, a first stabilizing layer is prepared on a substrate by using the method of preparing a second stabilizing layer. The material of the first stabilizing layer includes a first stabilizer, 2-mercaptothiazoline. An Ag anode is prepared on the first stabilizing layer.

[0161] Embodiments 4 to 8

[0162] Examples 4 to 8 are substantially the same as Example 1, except that the materials of the second stabilizer in Examples 4 to 8 are 2-mercaptobenzothiazole (Example 4), 2-mercaptothiazoline and 2-mercaptobenzothiazole (Example 5), respectively. (Example 6), (Example 7), (Example 8).

[0163] Example 9

[0164] This embodiment is substantially the same as Embodiment 1, except that the cathode material in this embodiment is a gold-iron alloy.

[0165] Example 10

[0166] This embodiment is substantially the same as the embodiment 1, except that the material of the second stabilization layer in this embodiment further includes a light extraction material NPB, wherein the molar ratio of 2-mercaptothiazoline to NPB is 1:1.

[0167] Embodiment 11

[0168] This embodiment is basically the same as Embodiment 10, with the only difference being that the light extraction material in this embodiment is MoO3.

[0169] Embodiments 12 to 13

[0170] Examples 12 to 13 are substantially the same as Example 10, except that the molar ratios of 2-mercaptothiazoline and NPB in Examples 12 to 13 are 50:1 and 1:50, respectively.

[0171] Embodiment 14

[0172] This embodiment is basically the same as Embodiment 1, except that, after the electron transport layer is formed, this embodiment further includes:

[0173] A dispersion of 2-mercaptothiazoline, a fourth stabilizer, was placed on the electron transport layer and annealed to form a fourth stabilizer layer with a thickness of 5 nm.

[0174] Embodiment 15

[0175] This embodiment is substantially the same as the embodiment 3, except that, after forming the anode, this embodiment further includes: placing a dispersion of a third stabilizer 2-mercaptothiazoline on the anode, annealing, and forming a third stabilizing layer with a thickness of 5 nm;

[0176] After the electron transport layer is formed, the method further includes: disposing a dispersion of a fourth stabilizer 2-mercaptothiazoline on the electron transport layer, and annealing to form a fourth stabilizer layer with a thickness of 5 nm.

[0177] Example 16

[0178] This embodiment is substantially the same as Embodiment 14, except that the material of the fourth stabilizer in this embodiment is 2-mercaptobenzothiazole.

[0179] Embodiment 17

[0180] This embodiment is basically the same as Embodiment 2, except that, in this embodiment, an inverted photoelectric device is prepared in the order of cathode, electron transport layer, quantum dot active layer, hole transport layer, hole injection layer, anode, and first stabilizing layer.

[0181] Embodiments 18 to 19

[0182] Embodiments 18 to 19 are substantially the same as Embodiment 1, except that:

[0183] In Example 18, the first stabilizing layer is not included, and a second stabilizing layer is prepared on the substrate by following the method for preparing the first stabilizing layer. The material of the second stabilizing layer includes a second stabilizer 2-mercaptothiazoline, and an Ag cathode is prepared on the second stabilizing layer.

[0184] In Example 19, a second stabilizing layer is prepared on a substrate by using the method for preparing a first stabilizing layer. The material of the second stabilizing layer includes a second stabilizer, 2-mercaptothiazoline. An Ag cathode is prepared on the second stabilizing layer.

[0185] Embodiment 20

[0186] This embodiment is basically the same as Embodiment 10, with the only difference being that in this embodiment, an inverted photoelectric device is prepared in the order of cathode, electron transport layer, quantum dot active layer, hole transport layer, hole injection layer, anode, and first stabilizing layer, and the first stabilizing layer also includes a light extraction material NPB.

[0187] Embodiment 21

[0188] This embodiment is basically the same as Embodiment 14, with the only difference being that, in this embodiment, an inverted photoelectric device is prepared in the order of cathode, electron transport layer, quantum dot active layer, hole transport layer, hole injection layer, third stabilization layer, anode, and first stabilization layer, and the preparation method of the third stabilization layer refers to that of the fourth stabilization layer.

[0189] Embodiment 22

[0190] This embodiment is basically the same as Embodiment 15, with the only difference being that, in this embodiment, an inverted photoelectric device is prepared in the order of a second stabilizing layer, a cathode, a fourth stabilizing layer, an electron transport layer, a quantum dot active layer, a hole transport layer, a hole injection layer, a third stabilizing layer, an anode, and a first stabilizing layer.

[0191] Comparative Example 1

[0192] This comparative example is substantially the same as Example 1, except that no second stabilizing layer is provided in this comparative example.

[0193] Comparative Example 2

[0194] This comparative example is basically the same as Example 17, except that the first stabilizing layer is not provided in this comparative example.

[0195] The corrosion potentials of the electrodes of Examples 1 to 22 and Comparative Examples 1 to 2 (Examples 1, 4 to 8, 9 to 14, 18, and Comparative Example 1 are cathodes, and the rest are anodes) were tested respectively, and the external quantum efficiency EQE and lifespan T95@1000nit of the photoelectric devices were measured. The results are shown in Table 1.

[0196] Among them, the corrosion potential test method is based on electrochemical principles and evaluates the corrosion tendency of the electrode by measuring the potential change of the electrode in a specific electrolyte solution.

[0197] The test method for external quantum efficiency EQE is: the ratio of the number of electron-hole pairs injected into quantum dots to the number of emitted photons, the unit is %, which is an important parameter to measure the quality of electroluminescent devices and can be obtained by measuring with EQE optical test instruments. The specific calculation formula is as follows:

[0198]

[0199] Among them, η e is the light output coupling efficiency, ηr is the ratio of the number of recombined carriers to the number of injected carriers, χ is the ratio of the number of photon-generating excitons to the total number of excitons, K R is the radiation process rate, K NR is the rate of the non-radiative process.

[0200] Test conditions: carried out at room temperature, air humidity is 30-60%.

[0201] The test method for the life span T95@1000nit is: the time required for the device to reduce its brightness to a certain proportion of the maximum brightness under constant current or voltage driving. The time when the brightness drops to 95% of the maximum brightness is defined as T95, and this life span is the measured life span. In order to shorten the test cycle, the device life span test is usually carried out at high brightness by accelerating device aging, and the life span at high brightness is obtained by fitting the extended exponential decay brightness attenuation fitting formula. For example, the life span at 1000nit is calculated as T95@1000nit. The specific calculation formula is as follows:

[0202]

[0203] Among them, T95L is the lifespan at low brightness, T95H is the measured lifespan at high brightness, LH is the device accelerated to the maximum brightness, LL is 1000nit, and A is the acceleration factor. This experiment measured the lifespan of several groups of green QLED devices at rated brightness and obtained an A value of 1.7.

[0204] Table 1

[0205]

[0206]

[0207] From Table 1, we can see that:

[0208] It can be seen from Examples 1 to 3 and Comparative Example 1 that the stabilization layer is provided on the side of the anode and / or cathode away from the active layer in the upright photoelectric device, which can effectively improve the corrosion potential, external quantum efficiency and service life of the electrode. Among them, the stabilization layer is provided on the side of the anode and cathode away from the active layer at the same time, which has the most obvious effect on improving the corrosion potential and service life of the device;

[0209] It can be seen from Examples 1, 4 to 9 and Comparative Example 1 that the stabilizer, whether 2-mercaptothiazoline, 2-mercaptobenzothiazole or its derivatives, can effectively increase the corrosion potential of the electrode compared with Comparative Example 1, avoid corrosion of the electrode, and thus improve the external quantum efficiency and service life of the optoelectronic device. There is no significant difference in the improvement of the performance of the optoelectronic device between 2-mercaptothiazoline and its derivatives and 2-mercaptobenzothiazole and its derivatives. When the Ag electrode is replaced with a gold-iron alloy electrode, the performance of the optoelectronic device in Example 9 is slightly lower than that in Example 1, which may be due to the higher conductivity of Ag.

[0210] It can be seen from Examples 1, 10 to 13 and Comparative Example 1 that adding a light extraction material to the stabilizing layer has little effect on the corrosion potential of the device, but within a suitable addition range, the external quantum efficiency and service life of the optoelectronic devices of Examples 10 to 11 are better than those of Example 1. This may be because the light extraction material increases the light extraction rate, thereby significantly improving the external quantum efficiency of the optoelectronic device.

[0211] It can be seen from Examples 1, 14 to 16 and Comparative Example 1 that by providing a stabilizing layer on the side of the anode and / or cathode close to the active layer, the corrosion potential of the electrode, the external quantum efficiency and the service life of the photoelectric device can be further improved. Among them, Example 15 provides a stabilizing layer on both sides of the anode and the cathode at the same time, and the corrosion potential is the highest, which significantly inhibits the corrosion of the electrode, thereby extending the service life of the photoelectric device;

[0212] It can be seen from Examples 17 to 22 and Comparative Example 2 that, in an inverted photoelectric device, providing a stabilizing layer on the side of the anode and / or cathode close to and / or away from the active layer, and adding a light extraction material to the stabilizing layer, can effectively improve the corrosion potential, external quantum efficiency and service life of the photoelectric device; among them, in all inverted photoelectric devices, stabilizing layers are provided on both sides of the anode and cathode, and the photoelectric device of Example 22 has the highest corrosion potential and the longest service life, indicating that the use of a stabilizer to provide a stabilizing layer in this scheme can effectively prevent the corrosion of the photoelectric device, improve the external quantum efficiency of the photoelectric device, and extend the service life of the photoelectric device.

[0213] The optoelectronic devices and their preparation methods, and display devices provided in the embodiments of the present application are introduced in detail above. 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 methods and core ideas of the present application. At the same time, for technical personnel in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A photoelectric device, characterized in that: It includes an anode, a functional layer and a cathode which are stacked in sequence; The optoelectronic device further comprises a first stabilization layer located on a side of the anode away from the functional layer, and / or a second stabilization layer located on a side of the cathode away from the functional layer, and / or a third stabilization layer located between the anode and the functional layer; Among them, the material of the first stabilization layer includes a first stabilizer, the material of the second stabilization layer includes a second stabilizer, and the material of the third stabilization layer includes a third stabilizer. The first stabilizer, the second stabilizer, and the third stabilizer each independently include one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

2. The optoelectronic device according to claim 1, characterized in that The materials of the anode and the cathode independently include one or more of metals and alloys; and / or The structural formula of the 2-mercaptothiazoline and its derivatives is shown in formula (I): R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 substituted or unsubstituted C1-C 20 Alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C3-C 20 heterocyclic group, substituted or unsubstituted C2-C 20 alkenyl, substituted or unsubstituted C2-C 20 One or more of the alkynyl groups; and / or The structural formula of the 2-mercaptobenzothiazole and its derivatives is shown in formula (II): (II); R3, R4, R5 and R6 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 substituted or unsubstituted C1-C 20 Alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C3-C 20 heterocyclic group, substituted or unsubstituted C2-C 20 alkenyl, substituted or unsubstituted C2-C 20 One or more of the alkynyl groups.

3. The optoelectronic device according to claim 2, characterized in that R1, R2, R3, R4, R5, and R6 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C5-C 10 Alkyl, substituted or unsubstituted C5-C 10 Alkoxy, substituted or unsubstituted C5-C 10 substituted or unsubstituted C5-C 10 Alkoxycarbonyl, substituted or unsubstituted C8-C 15 Aryl, substituted or unsubstituted C5-C 10 heterocyclic group, substituted or unsubstituted C5-C 10 Alkenyl, substituted or unsubstituted C5-C 10 One or more of the alkynyl groups; and / or The halogen includes one or more of fluorine, chlorine, bromine and iodine; and / or The alkyl group includes one or more of methyl, ethyl, isopropyl and tert-butyl; and / or The alkoxy group includes one or more of methoxy, ethoxy and propoxy; and / or The acyloxy group includes one or more of formyloxy, acetyloxy, propionyloxy, butyryloxy, octanoyloxy, palmitoyloxy, and stearoyloxy; and / or The alkoxycarbonyl group includes one or more of methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, palmityloxycarbonyl and stearyloxycarbonyl; and / or The aryl group includes one or more of phenyl, p-tolyl, p-nitrophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, and p-nitromethoxyphenyl; and / or The alkenyl group includes one or more of vinyl, propenyl and butenyl; and / or The alkynyl group includes one or more of ethynyl, propynyl, pentynyl and heptynyl; and / or The substituted groups include one or more of amino, halogen, hydroxyl, carboxyl, nitro, sulfonic acid, aldehyde, thiol, and cyano; and / or The heteroatoms in the heterocyclic group include one or more of O, P, N, and S; and / or The heterocyclic group includes one or more of thiazolyl, thienyl, furanyl, pyrrolyl, pyridyl, pyrimidinyl, imidazolyl, oxazolyl, pyrazinyl, indolyl, quinolyl, pteridinyl and acridinyl.

4. The optoelectronic device according to claim 1, characterized in that The 2-mercaptothiazoline derivative is selected from one or more of the following structural formulas: and / or The derivative of 2-mercaptobenzothiazole is selected from one or more of the following structural formulas:

5. The optoelectronic device according to claim 2, characterized in that: The metal includes a low work function metal, the work function of the low work function metal does not exceed 4.5 eV, and the low work function metal includes one or more of alkali metals, alkaline earth metals, transition metals, lanthanide metals, and actinide metals; the alloy includes silver-copper alloy, silver-magnesium alloy, gold-iron alloy, rhodium-platinum alloy; and / or The thickness of the anode and the cathode are 1nm to 60nm respectively; and / or The thickness of the first stabilizing layer, the second stabilizing layer, and the third stabilizing layer are 5 nm to 90 nm respectively.

6. The optoelectronic device according to claim 5, characterized in that The alkali metal includes one or more of lithium, sodium, potassium, rubidium, cesium, and francium; and / or The alkaline earth metal includes one or more of beryllium, magnesium, calcium, strontium, barium and radium; and / or The transition metal includes one or more of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, rhodium, tungsten, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, tantalum, tungsten ... The lanthanide metal includes one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium; and / or The actinide metal includes one or more of actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and lawrencium.

7. The optoelectronic device according to claim 1, characterized in that The material of the first stabilization layer further includes a first light extraction material; and / or The material of the second stabilization layer further includes a second light extraction material.

8. The optoelectronic device according to claim 7, characterized in that The refractive indexes of the first light extraction material and the second light extraction material are respectively 1.0 to 3.0; and / or The first light extraction material and the second light extraction material respectively include one or more of N-methylpyrrolidone, triethoxypropylsilane, triphenylbismuth, trichloromethylsilane, 1-methylcyclopropene, MoO3, WO3, V2O5, and LiF; and / or In the first stabilizing layer, the molar ratio of the first stabilizer to the first light extraction material is (1-50): (1-50); and / or In the second stabilizing layer, a molar ratio of the second stabilizer to the second light extraction material is (1 to 50):(1 to 50).

9. The optoelectronic device according to claim 1, characterized in that The functional layer comprises one or more of a hole functional layer, an active layer, and an electron functional layer sequentially arranged from the anode to the cathode; and / or The photoelectric device further includes a fourth stabilization layer located between the functional layer and the cathode. The material of the fourth stabilization layer includes a fourth stabilizer. The fourth stabilizer includes one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

10. The optoelectronic device according to claim 9, characterized in that The material of the active layer includes a luminescent material, and the luminescent material includes one or more of an organic luminescent material and a quantum dot; the organic luminescent material includes 4,4'-bis(N-carbazole)-1,1'-biphenyl:tris[2-(p-tolyl)pyridine iridium(III)], 4,4',4"-tris(carbazole-9-yl)triphenylamine:tris[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. One or more of the following: optical materials, TTA materials, TADF materials, polymers containing BN covalent bonding, HLCT materials, and Exciplex luminescent materials; the quantum dots include one or more of single-structure quantum dots, core-shell structure quantum dots, and perovskite-type semiconductor materials, and the materials of the single-structure quantum dots, the core materials of the core-shell structure quantum dots, and the shell materials of the core-shell structure quantum dots are independently selected from one or more of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds; the core-shell structure quantum dots The shell layer of the dot is one or more layers; the II-VI group compounds include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeT e, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compound includes one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe;The III-V group compounds include one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compounds include one or more of CuInS2, CuInSe2 and AgInS2; the general structural formula of the perovskite semiconductor material is AMY3, wherein A is Cs; + 、CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, 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+ 、Eu 2+ One or more of, Y is selected from Cl - Br - ,I - One or more of; and / or The material of the electronic functional layer includes one or more of a first doped metal oxide particle, a first undoped metal oxide particle, a IIB-VIA semiconductor material, a IIIA-VA semiconductor material and an IB-IIIA-VIA semiconductor material, the material of the first undoped metal oxide particle includes one or more of ZnO, TiO2, SnO2, ZrO2, and Ta2O5, the metal oxide in the first doped metal oxide particle includes one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, and Al2O3, the doping element in the first doped metal oxide particle includes one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, and Ga, the IIB-VIA semiconductor material includes one or more of ZnS, ZnSe, and CdS, the IIIA-VA semiconductor material includes one or more of InP and GaP, and the IB-IIIA-VIA semiconductor material includes one or more of CuInS and CuGaS; and / or The materials of the hole functional layer include 4,4'-N,N'-dicarbazolyl-biphenyl, N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(carbazol-9-yl)triphenylamine, trichloroisocyanuric acid, terbium-doped phosphate-based green luminescent materials, 2, 3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, 4,4',4'-tri(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(4-butylphenyl-diphenylamine), poly[bis(4-phenyl)(4-butylphenyl)amine], polyaniline, polypyrrole, poly(p-phenylene vinylene), poly(phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4- Phenylene vinylene], copper phthalocyanine, aromatic tertiary amine, polynuclear aromatic tertiary amine, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compound, N,N,N',N'-tetraaryl benzidine, PEDOT, PEDOT:PSS and its derivatives, PEDOT:PSS derivatives doped with s-MoO3, poly(N-vinyl carbazole) and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, N,N'-di(naphthalene-1-yl)-N,N'-diphenyl benzidine, spiro NPB, nano-polycrystalline diamond, microcrystalline cellulose and tetracyanoquinodimethane, doped graphene, undoped graphene, second doped metal oxide Particles, one or more of the second non-doped metal oxide particles, metal sulfides, metal selenides and metal nitrides, the metal oxide in the second doped metal oxide particles and the metal oxide in the second non-doped metal oxide particles each independently include one or more of MoO3, WO3, NiO, CrO3, CuO, V2O5, the doping elements in the second doped metal oxide particles include one or more of Mo, W, Ni, Cr, Cu, V, the metal sulfide includes one or more of CuS, MoS3, WS3, the metal selenide includes one or more of MoSe3, WSe3, and the metal nitride includes P-type gallium nitride.

11. A method for preparing a photoelectric device, characterized in that: include: providing a substrate; Forming a stabilizing layer and a functional layer on a substrate, including: Providing a first stabilizing layer material, wherein the first stabilizing layer material includes a first stabilizer, and disposing the first stabilizing layer material on the substrate to form a first stabilizing layer; sequentially forming an anode, a functional layer and a cathode on the first stabilizing layer to obtain a photoelectric device; and / or An anode, a functional layer and a cathode are sequentially formed on the substrate; a second stabilizing layer material is provided, wherein the second stabilizing layer material includes a second stabilizer, and the second stabilizing layer material is disposed on the cathode to form a second stabilizing layer, thereby obtaining a photoelectric device; and / or An anode is formed on the substrate, a third stabilizer is provided, and the third stabilizer is disposed on the anode to form a third stabilizing layer; a functional layer and a cathode are sequentially formed on the third stabilizing layer to obtain a photoelectric device; or, providing a substrate; Forming a stabilizing layer and a functional layer on a substrate, including: Providing a second stabilizing layer material, wherein the second stabilizing layer material includes a second stabilizer, and disposing the second stabilizing layer material on the substrate to form a second stabilizing layer; sequentially forming a cathode, a functional layer and an anode on the second stabilizing layer to obtain a photoelectric device; and / or forming a cathode, a functional layer and an anode on the substrate in sequence; providing a first stabilizing layer material, wherein the first stabilizing layer material comprises a first stabilizer, and disposing the first stabilizing layer material on the anode to form a first stabilizing layer, thereby obtaining a photoelectric device; and / or A cathode and a functional layer are sequentially formed on the substrate, a third stabilizer is provided, and the third stabilizer is disposed on the functional layer to form a third stabilizer layer; an anode is formed on the third stabilizer layer to obtain a photoelectric device; Wherein, the first stabilizer, the second stabilizer, the third stabilizer and the fourth stabilizer each independently include one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

12. The preparation method according to claim 11, characterized in that: The materials of the anode and the cathode independently include one or more of metals and alloys; and / or The structural formula of the 2-mercaptothiazoline and its derivatives is shown in formula (I): R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 substituted or unsubstituted C1-C 20 Alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C3-C 20 heterocyclic group, substituted or unsubstituted C2-C 20 alkenyl, substituted or unsubstituted C2-C 20 One or more of the alkynyl groups; and / or The structural formula of the 2-mercaptobenzothiazole and its derivatives is shown in formula (II): (II); R3, R4, R5 and R6 are independently selected from hydrogen, deuterium, halogen, cyano, hydroxyl, carboxyl, aldehyde, nitro, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 substituted or unsubstituted C1-C 20 Alkoxycarbonyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C3-C 20 heterocyclic group, substituted or unsubstituted C2-C 20 alkenyl, substituted or unsubstituted C2-C 20 One or more of the alkynyl groups.

13. The preparation method according to claim 12, characterized in that: The metal includes a low work function metal, the work function of the low work function metal does not exceed 4.5 eV, and the low work function metal includes one or more of alkali metals, alkaline earth metals, transition metals, lanthanide metals, and actinide metals; the alloy includes silver-copper alloy, silver-magnesium alloy, gold-iron alloy, rhodium-platinum alloy; and / or The 2-mercaptothiazoline derivative is selected from one or more of the following structural formulas: and / or The derivative of 2-mercaptobenzothiazole is selected from one or more of the following structural formulas:

14. The preparation method according to claim 11, characterized in that: The method for forming the first stabilizing layer comprises: providing a first stabilizer dispersion, wherein the first stabilizer dispersion comprises a first stabilizer; placing the first stabilizer dispersion on the substrate or the anode to form the first stabilizing layer; or The first stabilizing material also includes a first light extraction material. The method for forming the first stabilizing layer includes: providing a mixed liquid, wherein the mixed liquid includes a first stabilizer and a first light extraction material; and disposing the mixed liquid on the substrate or the anode to form a first stabilizing layer.

15. The preparation method according to claim 14, characterized in that: The first stabilizer dispersion also includes a first solvent, and / or the mixed solution also includes a second solvent, and the first solvent and the second solvent independently include one or more of chlorobenzene, diethylene glycol monobutyl ether, trimethoxybutanol, triethylene glycol monobutyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol, isopropanol, glycerol, dimethyl sulfoxide, acetone, acetophenone, tetrahydrofuran, N,N-dimethylformamide, ethyl acetate, pyrrole, butyric acid, and cresol; and / or The mass concentration of the first stabilizer in the first stabilizer dispersion and / or the mass concentration of the first stabilizer in the mixed solution are independently 5 mg / mL to 100 mg / mL; and / or In the mixed solution, the molar ratio of the first stabilizer to the first light extraction material is (1-50): (1-50); and / or After the first stabilizer dispersion and / or the mixed solution is disposed on the substrate or the anode, annealing is further performed; the annealing temperature is 60° C. to 180° C., and the annealing time is 1 min to 60 min.

16. The preparation method according to claim 11, characterized in that: After forming the functional layer on the substrate and before forming the cathode, the method further includes: providing a fourth stabilizer, and disposing the fourth stabilizer on the functional layer to form a fourth stabilizer layer; or After forming a cathode on the substrate and before forming a functional layer, the method further includes: providing a fourth stabilizer, and disposing the fourth stabilizer on the cathode to form a fourth stabilizer layer; The fourth stabilizer includes one or more of 2-mercaptothiazoline and its derivatives, 2-mercaptobenzothiazole and its derivatives.

17. A display device, characterized in that: The invention comprises a photoelectric device as claimed in any one of claims 1 to 10, or a photoelectric device prepared by the preparation method as claimed in any one of claims 11 to 16.

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