Composite film, photoelectric device and display device

Abstract

The invention discloses a composite film, a photoelectric device and a display device.The composite film comprises a second functional layer and a first functional layer, the first functional layer comprises a functional unit, and the functional unit comprises a first N-type semiconductor layer, a P-type semiconductor layer and a second N-type semiconductor layer which are stacked in sequence; the first N-type semiconductor layer is arranged close to the second functional layer; wherein the material of the second functional layer comprises a first material or a second material, the first material comprises at least one of an N-type metal oxide, a doped N-type metal oxide, a II-VI group semiconductor material, a III-V group semiconductor material and a I-III-VI group semiconductor material, and the second material comprises at least one of an N-type metal oxide, a doped N-type metal oxide, a doped II-VI group semiconductor material and a doped II-VI group semiconductor material. The second material comprises at least one of cesium carbonate, cesium fluoride, cesium azide and lithium fluoride. According to the invention, the first functional layer is arranged on one side of the second functional layer, and the first functional layer is provided with the NPN tube structure, so that the current can be expanded, and the electron transmission performance can be improved.

Description

Technical Field

[0001] The present application relates to the field of optoelectronic devices, and in particular to a composite film, an optoelectronic device and a display device. Background Art

[0002] Some inorganic semiconductor nanomaterials, such as nano ZnO, nano TiO2, nano SnO2, etc., have unique electron transport properties. When these materials are used to make thin films, when electrons are injected, they can achieve directional electron migration under the action of the electric field, thereby achieving charge transport. At present, the electron transport properties of thin films made of these inorganic semiconductor materials still need to be further improved. Summary of the invention

[0003] In view of this, the present application provides a composite film, an optoelectronic device and a display device, aiming to provide a film with high electron transport performance.

[0004] The embodiment of the present application is implemented as follows:

[0005] In a first aspect, the present application provides a composite film, comprising a stacked second functional layer and a first functional layer, wherein the first functional layer comprises a functional unit, wherein the functional unit comprises a first N-type semiconductor layer, a P-type semiconductor layer, and a second N-type semiconductor layer stacked in sequence, and the first N-type semiconductor layer is disposed close to the second functional layer;

[0006] Among them, the material of the second functional layer includes a first material or a second material, the first material includes at least one of N-type metal oxide, doped N-type metal oxide, II-VI semiconductor material, III-V semiconductor material and I-III-VI semiconductor material, and the second material includes at least one of cesium carbonate, cesium fluoride, cesium azide and lithium fluoride.

[0007] Optionally, in some embodiments of the present application, the first functional layer includes at least one functional unit. When the first functional layer includes multiple functional units, the multiple functional units are arranged in parallel on one side of the second functional layer, and the thicknesses of any two functional units are equal.

[0008] Optionally, in some embodiments of the present application, an insulating unit is provided between two adjacent functional units.

[0009] Optionally, in some embodiments of the present application, the material of the insulating unit includes an organic insulating material or an inorganic insulating material, the organic insulating material includes one or more of polystyrene, polypropylene, polyester, polycarbonate, polytetrafluoroethylene, and polyimide; the inorganic insulating material includes one or more of silicon dioxide and aluminum oxide; and / or,

[0010] The insulating unit has two side surfaces facing two adjacent functional units respectively, and a distance between the two side surfaces is 5-10 nm.

[0011] Optionally, in some embodiments of the present application, the thickness of the first N-type semiconductor layer is 5 to 24 nm; and / or,

[0012] The thickness of the P-type semiconductor layer is 11 to 50 nm; and / or,

[0013] The thickness of the second N-type semiconductor layer is 5-24 nm.

[0014] Optionally, in some embodiments of the present application, the first N-type semiconductor layer includes a first main material doped with a first N-type doping element, the first main material includes silicon or germanium, and the first N-type doping element includes one or more of phosphorus, arsenic, and antimony; and / or,

[0015] The material of the second N-type semiconductor layer includes a second main material doped with a second N-type doping element, the second main material includes silicon or germanium, and the second N-type doping element includes one or more of phosphorus, arsenic, and antimony; and / or,

[0016] The material of the P-type semiconductor layer includes a third main material doped with a P-type doping element, the third main material includes silicon or germanium, and the P-type doping element includes one or more of boron, indium, and gallium; and / or,

[0017] The N-type metal oxide includes at least one of ZnO, BaO, TiO2, and SnO2; the metal oxide in the doped N-type metal oxide includes at least one of ZnO, TiO2, and SnO2, the doping element includes at least one of Al, Mg, Li, In, and Ga, the II-VI group semiconductor material includes at least one of ZnS, ZnSe, and CdS; the III-V group semiconductor material includes at least one of InP and GaP; the I-III-VI group semiconductor material includes at least one of CuInS and CuGaS.

[0018] Optionally, in some embodiments of the present application, in the material of the first N-type semiconductor layer, the mass percentage of the first N-type doping element is 5-19%; and / or,

[0019] In the material of the second N-type semiconductor layer, the mass percentage of the second N-type doping element is 5-19%; and / or,

[0020] In the material of the P-type semiconductor layer, the mass percentage of the P-type doping element is 5-19%.

[0021] In a second aspect, the present application provides a photoelectric device, comprising a cathode and an anode, and further comprising a composite film disposed between the cathode and the anode, wherein the composite film comprises a stacked second functional layer and a first functional layer, wherein the first functional layer comprises a functional unit, wherein the functional unit comprises a first N-type semiconductor layer, a P-type semiconductor layer, and a second N-type semiconductor layer stacked in sequence, and the first N-type semiconductor layer is disposed close to the second functional layer;

[0022] Among them, the material of the second functional layer includes a first material or a second material, the first material includes at least one of N-type metal oxide, doped N-type metal oxide, II-VI semiconductor material, III-V semiconductor material and I-III-VI semiconductor material, and the second material includes at least one of cesium carbonate, cesium fluoride, cesium azide and lithium fluoride.

[0023] Optionally, in some embodiments of the present application, the first functional layer includes at least one functional unit. When the first functional layer includes multiple functional units, the multiple functional units are arranged in parallel on one side of the second functional layer, and the thicknesses of any two functional units are equal.

[0024] Optionally, in some embodiments of the present application, two first functional layers are provided.

[0025] Optionally, in some embodiments of the present application, an insulating unit is provided between two adjacent functional units.

[0026] Optionally, in some embodiments of the present application, the material of the insulating unit includes an organic insulating material or an inorganic insulating material, the organic insulating material includes one or more of polystyrene, polypropylene, polyester, polycarbonate, polytetrafluoroethylene, and polyimide; the inorganic insulating material includes one or more of silicon dioxide and aluminum oxide; and / or,

[0027] The insulating unit has two side surfaces facing two adjacent functional units respectively, and a distance between the two side surfaces is 5-10 nm.

[0028] Optionally, in some embodiments of the present application, the thickness of the first N-type semiconductor layer is 5 to 24 nm; and / or,

[0029] The thickness of the P-type semiconductor layer is 11 to 50 nm; and / or,

[0030] The thickness of the second N-type semiconductor layer is 5-24 nm.

[0031] Optionally, in some embodiments of the present application, the first N-type semiconductor layer includes a first main material doped with a first N-type doping element, the first main material includes silicon or germanium, and the first N-type doping element includes one or more of phosphorus, arsenic, and antimony; and / or,

[0032] The material of the second N-type semiconductor layer includes a second main material doped with a second N-type doping element, the second main material includes silicon or germanium, and the second N-type doping element includes one or more of phosphorus, arsenic, and antimony; and / or,

[0033] The material of the P-type semiconductor layer includes a third main material doped with a P-type doping element, the third main material includes silicon or germanium, and the P-type doping element includes one or more of boron, indium, and gallium.

[0034] Optionally, in some embodiments of the present application, in the material of the first N-type semiconductor layer, the mass percentage of the first N-type doping element is 5-19%; and / or,

[0035] In the material of the second N-type semiconductor layer, the mass percentage of the second N-type doping element is 5-19%; and / or,

[0036] In the material of the P-type semiconductor layer, the mass percentage of the P-type doping element is 5-19%.

[0037] Optionally, in some embodiments of the present application, the cathode and the anode independently include a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode includes 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 and aluminum-doped magnesium oxide, the composite electrode of metal and metal oxide includes AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, the material of the metal electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba; and / or,

[0038] The optoelectronic device further includes a light-emitting layer, which is disposed between the first functional layer and the anode. The material of the light-emitting layer includes one or more of an organic light-emitting material and a quantum dot light-emitting material. The organic light-emitting material includes 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 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 or more, the quantum dot luminescent material includes at least one of single structure quantum dots, core-shell structure quantum dots and perovskite semiconductor material; the material of the single structure quantum dot, the core material of the core-shell structure quantum dot and the shell material of the core-shell structure quantum dot include II-VI group compounds, IV-VI group compounds, III-V group compounds and I-II At least one of the I-VI group compounds; the II-VI group compounds include 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, Cd At least one of ZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compound includes at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe;The III-V compounds include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, and AlN P, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInN P, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound includes at least one of CuInS2, CuInSe2 and AgInS2; the perovskite semiconductor material includes a doped or undoped inorganic perovskite semiconductor, or an organic-inorganic hybrid perovskite semiconductor; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs; + ions, M is a divalent metal cation, including Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of X is a halogen anion including Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation, including CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation, including Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu2+ At least one of X is a halogen anion including Cl - Br - ,I - At least one of .

[0039] Optionally, in some embodiments of the present application, the material of the light-emitting layer includes a first quantum dot material, and the first quantum dot material is a blue quantum dot having an emission wavelength of 435 to 470 nm.

[0040] Optionally, in some embodiments of the present application, the photoelectric device further includes a hole functional layer, wherein the hole functional layer is disposed between the first functional layer and the anode, and the hole functional layer includes one or two layers of a hole transport layer and a hole injection layer, and the material of the hole transport 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'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine, -bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 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), polyaniline, polypyrrole, poly(p-phenylenevinylene), poly(phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] and 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:PSS and its derivatives, 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, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, doped or undoped P-type gallium nitride, doped or undoped CrO3, doped or undoped CuO; the material of the hole injection layer includes at least one of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with s-MoO3 derivatives, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, tetracyanoquinodimethane, copper phthalocyanine, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, molybdenum sulfide, tungsten sulfide and copper oxide.

[0041] In a third aspect, the present application further proposes a display device, comprising the optoelectronic device as described above.

[0042] The present application provides a composite film, in which a first functional layer is arranged on one side of a second functional layer, and the first functional layer has an NPN tube structure, which can expand the current and help improve the electron transmission performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] 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 creative work.

[0044] Figure 1 is a schematic structural diagram of an optoelectronic device proposed in one embodiment of the present application;

[0045] Figure 2 is a schematic structural diagram of a photoelectric device proposed in another embodiment of the present application;

[0046] Reference numerals:

[0047] 100-photoelectric device; 10-anode; 20-electron transport layer; 30-light-emitting layer; 40-cathode; 50-hole injection layer; 60-hole transport layer; 70-first functional layer; 70a-first NPN unit; 70b-second NPN unit; 71-first N-type semiconductor layer; 72-P-type semiconductor layer; 73-second N-type semiconductor layer; 74-insulating unit. DETAILED DESCRIPTION

[0048] 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.

[0049] In this application, unless otherwise specified, the directional words used, such as "upper" and "lower", refer specifically to the directions of the drawings in the accompanying drawings. In addition, in the description of the specification of this application, the term "including" means "including but not limited to".

[0050] 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.

[0051] 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.

[0052] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one", "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.

[0053] In the first aspect, the embodiment of the present application proposes a composite film, the composite film includes a stacked second functional layer and a first functional layer 70, the first functional layer 70 includes a functional unit, the functional unit includes a first N-type semiconductor layer 71, a P-type semiconductor layer 72, and a second N-type semiconductor layer 73 stacked in sequence; wherein the first N-type semiconductor layer 71 is arranged close to the second functional layer, that is, the second functional layer, the first N-type semiconductor layer 71, the P-type semiconductor layer 72, and the second N-type semiconductor layer 73 are stacked in sequence. Wherein, the second functional layer refers to a film layer made of a material having electron transport properties or electron injection properties, the material of the second functional layer includes but is not limited to the first material or the second material, the first material includes at least one of N-type metal oxide, doped N-type metal oxide, II-VI semiconductor material, III-V semiconductor material, and I-III-VI semiconductor material, and the second material includes at least one of cesium carbonate, cesium fluoride, cesium azide, and lithium fluoride.

[0054] The present application provides a composite film, in which a first functional layer 70 is arranged on one side of a second functional layer. The first functional layer 70 has an NPN tube structure, which can expand the current and help improve the electron transmission performance.

[0055] In some embodiments, the first functional layer 70 may be composed of one functional unit or two or more functional units. It should be noted that when the first functional layer 70 includes a plurality of the functional units, the plurality of the functional units are arranged in parallel, and the film layer structure is manifested as the plurality of the functional units being arranged in parallel on one side of the second functional layer. At this time, the thickness of any two of the plurality of the functional units is equal. When a plurality of the functional units are provided, the plurality of the functional units are arranged in parallel, and the film layer structure formed by the plurality of the functional units as a whole has a greater current amplification efficiency, which helps to further enhance the electron injection in the thin film.

[0056] In some embodiments, the functional unit is provided with two, for example, the two functional units are composed of a first NPN unit 70a and a second NPN unit 70b connected in parallel, which can not only enhance electron injection but also help reduce the film design cost and manufacturing difficulty.

[0057] In some embodiments, when a plurality of first functional layers 70 are provided, any two adjacent functional units 70 are spaced apart from each other and insulated and connected. Specifically, an insulating unit 74 may be provided between two adjacent functional units. The insulating unit 74 refers to a thin film made of an insulating material, and the material may include but is not limited to an organic insulating material or an inorganic insulating material. The organic insulating material includes one or more of polystyrene, polypropylene, polyester, polycarbonate, polytetrafluoroethylene, and polyimide; the inorganic insulating material includes at least one of one or more of silicon dioxide and aluminum oxide.

[0058] In some embodiments, the dimension D of the insulating unit 74 in the spacing direction between two adjacent functional units is 5 to 10 nm, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, and a value between any two of the above values. Specifically, in two adjacent functional units, the insulating unit 74 has a first side facing one of the functional units and a second side facing the other functional unit, and the spacing between the first side and the second side is the dimension D of the insulating unit 74 in the spacing direction between the two adjacent functional units.

[0059] In some embodiments, the thickness of the first N-type semiconductor layer 71 is 5 to 24 nm; for example, it can be 5 nm, 6 nm, 7 nm, 10 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 20 nm, 24 nm, and a value between any two of the above values.

[0060] In some embodiments, the thickness of the P-type semiconductor layer 72 is 11 to 50 nm; for example, it can be 11 nm, 15 nm, 20 nm, 25 nm, 28 nm, 29 nm, 30 nm, 31 nm, 32 nm, 35 nm, 40 nm, 45 nm, 50 nm, and a value between any two of the above values.

[0061] In some embodiments, the thickness of the second N-type semiconductor layer 73 is 5 to 24 nm; for example, it can be 5 nm, 6 nm, 7 nm, 10 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 20 nm, 24 nm, and a value between any two of the above values.

[0062] In some embodiments, the thickness of the first N-type semiconductor is equal to the thickness of the second N-type semiconductor; in another embodiment, the thickness of the first N-type semiconductor is 13-17 nm, the thickness of the P-type semiconductor is 18-32 nm, and the thickness of the second N-type semiconductor is 13-17 nm; this helps to further improve electron injection.

[0063] In some embodiments, the first N-type semiconductor layer 71 includes a first main body material doped with a first N-type doping element, the first main body material includes silicon (Si) or germanium (Ge), and the first N-type doping element includes one or more of phosphorus (P), arsenic (As), and antimony (Sb). It is understandable that the first main body material can be pure silicon or pure germanium, or a silicon-based material with silicon as the main component such as silicon oxide, silicon carbide, and silicon nitride, or a germanium-based material with germanium as the main component such as germanium oxide, germanium carbide, and germanium nitride.

[0064] In some embodiments, the material of the second N-type semiconductor layer 73 includes a second main material doped with an N-type doping element, the second main material includes silicon or germanium, and the second N-type doping element includes one or more of phosphorus, arsenic, and antimony. It is understandable that the second main material can be pure silicon or pure germanium, or a silicon-based material with silicon as a main component, such as silicon oxide, silicon carbide, and silicon nitride, or a germanium-based material with germanium as a main component, such as germanium oxide, germanium carbide, and germanium nitride.

[0065] In some embodiments, the material of the P-type semiconductor layer 72 includes a third main material doped with a P-type doping element, the third main material includes silicon or germanium, and the P-type doping element includes one or more of boron (B), indium (In), and gallium (Ga). It is understandable that the third main material can be pure silicon or pure germanium, or a silicon-based material with silicon as the main component, such as silicon oxide, silicon carbide, and silicon nitride, or a germanium-based material with germanium as the main component, such as germanium oxide, germanium carbide, and germanium nitride.

[0066] In some embodiments, the mass percentage of the first N-type doping element in the material of the first N-type semiconductor layer 71 is 5-19%, for example, 5%, 6%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 19% and any value between the above two values. In some embodiments, the mass percentage of the first N-type doping element is 8-12%, which helps to further improve electron injection.

[0067] In some embodiments, the mass percentage of the second N-type doping element in the material of the second N-type semiconductor layer 73 is 5-19%, for example, 5%, 6%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 19% and any value between the above two values. In some embodiments, the mass percentage of the second N-type doping element is 8-12%, which helps to further improve electron injection.

[0068] In some embodiments, the mass percentage of the P-type doping element in the material of the P-type semiconductor layer 72 is 5-19%, for example, 5%, 6%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 19% and any value between the above two values. In some embodiments, the mass percentage of the P-type doping element is 8-12%, which helps to further improve electron injection.

[0069] In a second aspect, an embodiment of the present application proposes an optoelectronic device 100, which refers to a device made according to the photoelectric effect, including but not limited to an organic light emitting diode (OLED), a quantum dot light emitting diode (QLED), a solar cell, and the like.

[0070] The photoelectric device 100 includes a cathode 40 and an anode 10. When stimulated by light or electricity, electrons and holes are injected from the cathode 40 and the anode 10, respectively, and recombine to emit light. The balance between electron injection and hole injection is one of the important factors affecting the luminous efficiency and life of the device. However, some common light-emitting devices, especially blue light QLEDs (quantum dot light-emitting diodes), have the problem that hole injection is greater than electron injection, which greatly affects the service life and luminous efficiency of the device.

[0071] In view of this, the optoelectronic device 100 provided in the embodiment of the present application further includes a composite film disposed between the cathode 40 and the anode 10. Figure 1 The composite film includes a stacked second functional layer and a first functional layer 70, the first functional layer 70 includes a functional unit, the functional unit includes a first N-type semiconductor layer 71, a P-type semiconductor layer 72 and a second N-type semiconductor layer 73 stacked in sequence, and the first N-type semiconductor layer 71 is arranged close to the second functional layer.

[0072] The present application provides a photoelectric device 100, which is further provided with a composite film including a first functional layer 70 between the cathode 40 and the anode 10, wherein the first functional layer 70 includes a first N-type semiconductor layer 71, a P-type semiconductor layer 72 and a second N-type semiconductor layer 73, and the three film layers are stacked in sequence to form an NPN tube structure, which can expand the current, help increase electron injection, improve the injection balance of electrons and holes in the device, and help extend the service life of the device.

[0073] In some embodiments, the functional unit may be provided as one or more than one. It should be noted that when multiple functional units are provided, the multiple functional units are provided in parallel, such as Figure 2 As shown, the film layer structure is that multiple functional units are arranged in parallel on the second functional layer, and the thickness of any two functional units is equal. When multiple functional units are provided, the multiple functional units are arranged in parallel, and the film layer structure formed as a whole has a greater current amplification efficiency, which helps to further enhance the electron injection in the device and promote carrier balance.

[0074] In some embodiments, any two functional units not only have the same total thickness, but also have the same thickness of the first N-type semiconductor layer 71 , the same thickness of the P-type semiconductor layer 72 , and the same thickness of the second N-type semiconductor layer 73 .

[0075] In some embodiments, the functional unit is provided with two, for example, the two functional units are composed of a first NPN unit 70a and a second NPN unit 70b connected in parallel, which can not only enhance electron injection but also help reduce the film design cost and manufacturing difficulty.

[0076] In some embodiments, when multiple functional units are provided, any two adjacent functional units are spaced apart from each other and insulated and connected. Specifically, an insulating unit 74 may be provided between two adjacent functional units. The insulating unit 74 refers to a thin film made of an insulating material, and the material may include but is not limited to an organic insulating material or an inorganic insulating material. The organic insulating material includes one or more of polystyrene, polypropylene, polyester, polycarbonate, polytetrafluoroethylene, and polyimide; the inorganic insulating material includes at least one of one or more of silicon dioxide and aluminum oxide.

[0077] In some embodiments, the dimension D of the insulating unit 74 in the spacing direction between two adjacent functional units is 5 to 10 nm, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, and a value between any two of the above values. Specifically, in two adjacent functional units, the insulating unit 74 has a first side facing one of the functional units and a second side facing the other functional unit, and the spacing between the first side and the second side is the dimension D of the insulating unit 74 in the spacing direction between the two adjacent functional units.

[0078] In some embodiments, the thickness of the first N-type semiconductor layer 71 is 5 to 24 nm; for example, it can be 5 nm, 6 nm, 7 nm, 10 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 20 nm, 24 nm, and a value between any two of the above values.

[0079] In some embodiments, the thickness of the P-type semiconductor layer 72 is 11 to 50 nm; for example, it can be 11 nm, 15 nm, 20 nm, 25 nm, 28 nm, 29 nm, 30 nm, 31 nm, 32 nm, 35 nm, 40 nm, 45 nm, 50 nm, and a value between any two of the above values.

[0080] In some embodiments, the thickness of the second N-type semiconductor layer 73 is 5 to 24 nm; for example, it can be 5 nm, 6 nm, 7 nm, 10 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 20 nm, 24 nm, and a value between any two of the above values.

[0081] In some embodiments, the thickness of the first N-type semiconductor is equal to the thickness of the second N-type semiconductor; in another embodiment, the thickness of the first N-type semiconductor is 13-17 nm, the thickness of the P-type semiconductor is 18-32 nm, and the thickness of the second N-type semiconductor is 13-17 nm; this helps to further improve electron injection and further promote carrier balance.

[0082] In some embodiments, the first N-type semiconductor layer 71 includes a first main body material doped with a first N-type doping element, the first main body material includes silicon (Si) or germanium (Ge), and the first N-type doping element includes one or more of phosphorus (P), arsenic (As), and antimony (Sb). It is understandable that the first main body material can be pure silicon or pure germanium, or a silicon-based material with silicon as the main component such as silicon oxide, silicon carbide, and silicon nitride, or a germanium-based material with germanium as the main component such as germanium oxide, germanium carbide, and germanium nitride.

[0083] In some embodiments, the material of the second N-type semiconductor layer 73 includes a second main material doped with an N-type doping element, the second main material includes silicon or germanium, and the second N-type doping element includes one or more of phosphorus, arsenic, and antimony. It is understandable that the second main material can be pure silicon or pure germanium, or a silicon-based material with silicon as a main component, such as silicon oxide, silicon carbide, and silicon nitride, or a germanium-based material with germanium as a main component, such as germanium oxide, germanium carbide, and germanium nitride.

[0084] In some embodiments, the material of the P-type semiconductor layer 72 includes a third main material doped with a P-type doping element, the third main material includes silicon or germanium, and the P-type doping element includes one or more of boron (B), indium (In), and gallium (Ga). It is understandable that the third main material can be pure silicon or pure germanium, or a silicon-based material with silicon as the main component, such as silicon oxide, silicon carbide, and silicon nitride, or a germanium-based material with germanium as the main component, such as germanium oxide, germanium carbide, and germanium nitride.

[0085] In some embodiments, the mass percentage of the first N-type doping element in the material of the first N-type semiconductor layer 71 is 5-19%, for example, 5%, 6%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 19% and any value between the above two values. In some embodiments, the mass percentage of the first N-type doping element is 8-12%, which helps to further improve electron injection.

[0086] In some embodiments, the mass percentage of the second N-type doping element in the material of the second N-type semiconductor layer 73 is 5-19%, for example, 5%, 6%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 19% and any value between the above two values. In some embodiments, the mass percentage of the second N-type doping element is 8-12%, which helps to further improve electron injection.

[0087] In some embodiments, the mass percentage of the P-type doping element in the material of the P-type semiconductor layer 72 is 5-19%, for example, 5%, 6%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 19% and any value between the above two values. In some embodiments, the mass percentage of the P-type doping element is 8-12%, which helps to further improve electron injection.

[0088] In some embodiments, the anode 10 may be an anode 10 for a photoelectric device 100 known in the art, for example, may include but is not limited to a doped metal oxide particle electrode, a composite electrode of a metal and a metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode includes 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 and aluminum-doped magnesium oxide, the composite electrode of the metal and the metal oxide includes AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, the material of the metal electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0089] In some embodiments, the cathode 40 can be a cathode 40 for the optoelectronic device 100 known in the art, for example, it can include but is not limited to a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode includes 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 and aluminum-doped magnesium oxide, the composite electrode of metal and metal oxide includes AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, and the material of the metal electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0090] In some embodiments, the optoelectronic device 100 further includes a light-emitting layer 30, and the light-emitting layer 30 is disposed between the anode 10 and the first functional layer 70. The light-emitting layer 30 may be an organic light-emitting layer or a quantum dot light-emitting layer. When the light-emitting layer 30 is an organic light-emitting layer, the optoelectronic device 100 may be an organic light-emitting device; when the light-emitting layer 30 is a quantum dot light-emitting layer, the optoelectronic device 100 may be a quantum dot light-emitting device.

[0091] The material of the organic light-emitting layer is a material known in the art for the organic light-emitting layer of the optoelectronic device 100, for example, it may include 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, and exciplex luminescent materials. One or more of the following.

[0092] The material of the quantum dot light-emitting layer is a quantum dot material known in the art for the quantum dot light-emitting layer of the optoelectronic device 100, for example, it may include but is not limited to at least one of a single structure quantum dot, a core-shell structure quantum dot and a perovskite semiconductor material; the material of the single structure quantum dot, the core material of the core-shell structure quantum dot and the shell material of the core-shell structure quantum dot respectively include at least one of a II-VI group compound, a IV-VI group compound, a III-V group compound and a I-III-VI group compound; the II-VI group compound includes CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, Hg At least one of S, 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 compounds The compound includes at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe; the III-V compound includes GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, and 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 includes at least one of CuInS2, CuInSe2 and AgInS2.

[0093] As an example, the core-shell structured quantum dots may include but are not limited to at least one of CdZnSe / CdZnSe / ZnSe / CdZnS / ZnS, CdZnSe / CdZnSe / CdZnS / ZnS 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.

[0094] It should be noted that, for the material of the aforementioned single structure quantum dot, or the material of the core of the core-shell structure quantum dot, or the material of the shell of the core-shell structure quantum dot, the chemical formula provided only indicates the elemental composition, but 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。

[0095] The perovskite semiconductor material may include but is not limited to doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs + ions, M is a divalent metal cation, including Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of X is a halogen anion including Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation, including CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation, including Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of X is a halogen anion including Cl - Br - ,I - At least one of .

[0096] In some embodiments, the material of the light-emitting layer 30 includes a first quantum dot material, and the first quantum dot material is a blue quantum dot with an emission wavelength of 435 to 470 nm. Accordingly, the optoelectronic device 100 is a blue light device, and a blue light device generally has a problem that hole injection is greater than electron injection. The film structure of the optoelectronic device 100 proposed in this application is particularly suitable for blue light devices, which helps to improve their carrier balance, greatly improve their lifespan, and enhance their commercial application value.

[0097] In some embodiments, the second functional layer is disposed between the first functional layer 70 and the anode 10. Specifically, when the optoelectronic device 100 further includes a light-emitting layer 30, the second functional layer is located between the light-emitting layer 30 and the first functional layer 70. The second functional layer includes an electron transport layer 20 and an electron injection layer. When the device includes both the electron transport layer 20 and the electron injection layer, the electron injection layer is disposed closer to the cathode 40. The electron transport layer 20 can be prepared using a first material having electron transport properties for the optoelectronic device 100 known in the art. For example, the material of the electron transport layer 20 includes but is not limited to at least one of N-type metal oxide, doped N-type metal oxide, II-VI semiconductor material, III-V semiconductor material and I-III-VI semiconductor material, the N-type metal oxide includes at least one of ZnO, BaO, TiO2, SnO2; the metal oxide in the doped N-type metal oxide includes at least one of ZnO, TiO2, SnO2, the doping element includes at least one of Al, Mg, Li, In, Ga, the II-VI semiconductor material includes at least one of ZnS, ZnSe, CdS; the III-V semiconductor material includes at least one of InP and GaP; the I-III-VI semiconductor material includes at least one of CuInS and CuGaS. The electron injection layer can be prepared using a second material known in the art for the optoelectronic device 100 and having electron injection performance, for example, the second material includes but is not limited to at least one of cesium carbonate, cesium fluoride, cesium azide and lithium fluoride.

[0098] In some embodiments, the optoelectronic device 100 further includes a hole functional layer, and the hole functional layer is disposed between the first functional layer 70 and the anode 10. Specifically, when the optoelectronic device 100 further includes a light-emitting layer 30, the hole functional layer is located between the light-emitting layer 30 and the anode 10. The hole functional layer includes a hole transport layer 60 and a hole injection layer 50. When the device includes both the hole transport layer 60 and the hole injection layer 50, the hole injection layer 50 is disposed closer to the anode 10. The hole transport layer 60 can be prepared using a material with hole transport properties known in the art for use in optoelectronic devices 100.For example, the material of the hole transport layer 60 is not limited to 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(N-carbazolyl)-triphenylamine, 4,4'-tri(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine ... 4',4'-Tris(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), polyaniline, polypyrrole, poly(p-phenylenevinylene), poly(phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines , 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compounds, N,N,N',N'-tetraaryl benzidine, PEDOT:PSS and its derivatives, 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, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, doped or undoped P-type gallium nitride, doped or undoped CrO3, doped or undoped CuO; the material of the hole injection layer 50 includes but is not limited to at least one of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene, PEDOT, PEDOT:PSS, PEDOT:PSS doped with s-MoO3 derivatives, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, tetracyanoquinodimethane, copper phthalocyanine, nickel oxide, molybdenum oxide, tungsten oxide, vanadium oxide, molybdenum sulfide, tungsten sulfide and copper oxide.

[0099] It is understandable that the thickness of each layer in the optoelectronic device 100 is set as needed and is not limited here. In some embodiments, the thickness of the anode 10 is 7-20nm, the thickness of the hole injection layer 50 is 30-70nm, the thickness of the hole transport layer 60 is 20-50nm, the thickness of the light emitting layer 30 is 10-30nm, the thickness of the electron transport layer 20 is 15-50nm, the thickness of the electron injection layer is 15-50nm, and the thickness of the cathode 40 is 15-35nm.

[0100] When there are multiple film layers between the anode 10 and the cathode 40, and the multiple film layers include a light-emitting layer 30, an electron transport layer 20, a hole transport layer 60, and a hole injection layer 50, the film layers of the photoelectric device 100 are stacked in the order of anode 10, hole injection layer 50, hole transport layer 60, light-emitting layer 30, electron transport layer 20, electron injection layer, first functional layer 70 (second N-type semiconductor layer 73, P-type semiconductor layer 72 and first N-type semiconductor layer 71 are stacked in sequence), and cathode 40; it can be understood that the photoelectric device 100 can be an upright device or an inverted device. In some embodiments, the photoelectric device 100 is an upright device, and accordingly, the photoelectric device 100 includes an anode 10, a hole injection layer 50, a hole transport layer 60, a light-emitting layer 30, an electron transport layer 20, an electron injection layer, a second N-type semiconductor layer 73, a P-type semiconductor layer 72, a first N-type semiconductor layer 71, and a cathode 40 stacked in sequence from bottom to top; in other embodiments, the photoelectric device 100 is an inverted device, and accordingly, the photoelectric device 100 includes a cathode 40, a first N-type semiconductor layer 71, a P-type semiconductor layer 72, a second N-type semiconductor layer 73, an electron injection layer, an electron transport layer 20, a light-emitting layer 30, a hole transport layer 60, a hole injection layer 50 and an anode 10 stacked in sequence from bottom to top.

[0101] It is understandable that the optoelectronic device 100 may also be provided with some functional layers conventionally used in optoelectronic devices 100 that help improve the performance of the optoelectronic device 100, such as an electron blocking layer, a hole blocking layer, an interface modification layer, etc.

[0102] It can be understood that the materials of each layer of the optoelectronic device 100 can be adjusted according to the actual requirements of the optoelectronic device 100 .

[0103] In a second aspect, the present application also provides a method for preparing a photoelectric device 100, which can be used to prepare the above-mentioned photoelectric device 100. The preparation method comprises the following steps:

[0104] S100, providing a first electrode;

[0105] S200, disposing a composite film on the first electrode, wherein the composite film includes a first functional layer 70 and a second functional layer, and the first functional layer 70 includes one or more functional units;

[0106] S300, disposing a second electrode on the composite film.

[0107] In steps S100 and S300, the first electrode includes one of the anode 10 and the cathode 40, and the second electrode includes the other of the anode 10 and the cathode 40. In actual preparation, it is determined whether to prepare the anode 10 or the cathode 40 first according to the film layer design of the optoelectronic device 100. For example, when the optoelectronic device 100 is designed with the anode 10 at the bottom layer and the cathode 40 at the top layer, the anode 10 is prepared first, and the first electrode is the anode 10.

[0108] In step S200 , the functional unit may be manufactured by the following method: S21 , forming a first N-type semiconductor layer 71 ; S22 , forming a P-type semiconductor layer 72 on the first N-type semiconductor layer 71 ; S23 , forming a second N-type semiconductor layer 73 on the P-type semiconductor layer 72 .

[0109] In the three steps S21 to S23, when forming the film layer, the physical vapor deposition method can be used to form the film.

[0110] The physical vapor deposition method includes but is not limited to vacuum evaporation method, vacuum sputtering method, etc. In specific implementation, the conditions for the physical vapor deposition method may include: the radio frequency is 10 to 15 MHz; the sputtering gas is argon; the vacuum degree is 10 -3 ~10 -5 pa, for example, the vacuum degree can be 1×10 -5 pa, 1.5×10 -5 pa, 5×10 -5 pa, 1×10 -4 pa, 1.5×10 -4 pa, 5×10 -4 pa, 1×10 -3 pa and any value between any two values ​​listed above.

[0111] In some embodiments, after the film is formed by physical vapor deposition, the step of annealing the film layer is also included. During annealing, the temperature is 110-130°C, for example, it can be 110°C, 115°C, 120°C, 125°C, 130°C and any values ​​between the above-mentioned values; the annealing time is 8-15min, for example, it can be 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min and any values ​​between the above-mentioned values.

[0112] When the first functional layer 70 is provided with a plurality of functional units, the plurality of functional units may be prepared by referring to the above-mentioned method for preparing a single functional unit, and an insulating unit 74 may be evaporated between two adjacent functional units.

[0113] It can be understood that when the optoelectronic device 100 further includes functional film layers such as the light-emitting layer 30 , steps of sequentially preparing other functional film layers according to the design sequence of the film layers of the optoelectronic device 100 are included between steps S100 and S200 .

[0114] In actual preparation, each film layer of the optoelectronic device 100, such as the anode 10, the light-emitting layer 30, the second functional layer, the hole functional layer and the cathode 40, can be prepared by conventional techniques in the art, such as chemical methods or physical methods. Among them, the chemical method includes chemical vapor deposition, continuous ion layer adsorption and reaction, anodization, electrolytic deposition, and coprecipitation. The physical method includes physical plating and solution method, among which the physical plating method includes: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method can be spin coating, printing, inkjet printing, doctor blade coating, printing, dip-coating, immersion, spraying, roll coating, casting, slit coating, strip coating, etc.

[0115] In some embodiments, after step S300, the step of packaging the optoelectronic device 100 is also included. The packaging process can be a common machine packaging or a manual packaging. Preferably, in the packaging process environment, the oxygen content and the water content are both less than 0.1ppm to ensure the stability of the optoelectronic device 100.

[0116] In a third aspect, the present application further proposes a display device, which may be a smart phone, a portable phone, a tablet computer, a personal digital assistant (PDA), a portable multimedia player (Portable Multimedia Player), a television, a game console, a watch-type electronic device, a head-mounted display, a display of a personal computer, a notebook computer, a car navigation system, a car dashboard, a digital camera, a portable camera, an external advertising board, an electro-optical board, a medical device, a detection device, a refrigerator, a washing machine, etc. The display device includes the optoelectronic device 100 as described above.

[0117] The technical scheme and technical effects of the present application are described in detail below through specific embodiments and comparative examples. The following embodiments are only some embodiments of the present application and do not specifically limit the present application.

[0118] Film Example 1

[0119] (1) A glass substrate was provided, and a ZnO ethanol solution was spin-coated on the substrate at a rotation speed of 3000 rpm for 30 seconds, and annealed at 80° C. for 30 minutes to obtain an electron transport layer with a thickness of 30 nm.

[0120] (2) Set the evaporation conditions as follows: vacuum degree is 10 -4 Pa, the radio frequency is 13MHz, the first N-type semiconductor material is used as the target material, two thin films with an interval of 8nm are evaporated on the electron transport layer, and then annealed at 120℃ for 10min to obtain two independent and spaced first N-type semiconductor layers; P-type semiconductor material is evaporated on each first N-type semiconductor layer, and then annealed at 120℃ for 10min to obtain a P-type semiconductor layer; the second N-type semiconductor material is evaporated on the P-type semiconductor layer, and then annealed at 120℃ for 10min to obtain a second N-type semiconductor layer. The first NPN unit and the second NPN unit are spaced from each other. Polyimide is deposited between the first NPN unit and the second NPN unit to form an insulating unit. The first functional layer of the parallel NPN-NPN structure (phosphorus-doped silicon / boron-doped silicon / phosphorus-doped silicon-phosphorus-doped silicon / boron-doped silicon / phosphorus-doped silicon) is obtained. The electron transport layer and the first functional layer together constitute a composite film.

[0121] Among them, the first N-type semiconductor material and the second N-type semiconductor material are both phosphorus-doped silicon, and the concentration of phosphorus doping in the material is 5wt%; the P-type semiconductor material is boron-doped silicon, and the concentration of boron doping in the material is 5wt%; the film thickness of each NPN unit is 5nm / 50nm / 5nm.

[0122] Film Example 2

[0123] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 1, with the only difference being that in this thin film embodiment, in step (2), the boron doping concentration is changed to 10%.

[0124] Film Example 3

[0125] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 1, with the only difference being that in this thin film embodiment, in step (2), the boron doping concentration is changed to 15%.

[0126] Film Example 4

[0127] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 1, with the only difference being that in this thin film embodiment, in step (2), the boron doping concentration is changed to 20%.

[0128] Film Example 5

[0129] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 2, with the only difference being that in this thin film embodiment, in step (2), the phosphorus doping concentration is changed to 10%.

[0130] Film Example 6

[0131] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 5, with the only difference being that in this thin film embodiment, in step (2), the film thickness of each NPN unit is changed to 10nm / 40nm / 10nm.

[0132] Film Example 7

[0133] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 5, with the only difference being that in this thin film embodiment, in step (2), the film thickness of each NPN unit is changed to 15nm / 30nm / 15nm.

[0134] Film Example 8

[0135] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 5, with the only difference being that in this thin film embodiment, in step (2), the film thickness of each NPN unit is changed to 20nm / 20nm / 20nm.

[0136] Film Example 9

[0137] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 5, with the only difference being that in this thin film embodiment, in step (2), the film thickness of each NPN unit is changed to 25nm / 10nm / 25nm.

[0138] Film Example 10

[0139] The scheme of this thin film embodiment is basically the same as that of thin film embodiment 7, with the only difference being that, in this thin film embodiment, in step (2), the main materials of the first N-type semiconductor material, the P-type semiconductor material and the second N-type semiconductor material are all changed from silicon to germanium, that is, the first N-type semiconductor material and the second N-type semiconductor material are both phosphorus-doped germanium; and the P-type semiconductor material is boron-doped germanium.

[0140] Film Example 11

[0141] The scheme of this film embodiment is basically the same as that of film embodiment 7, except that, in this film embodiment, in step (2), there is only one first functional layer, and the corresponding step (2) is changed to:

[0142] Set the evaporation conditions as follows: vacuum degree is 10 -4Pa, the radio frequency frequency is 13MHz, the first N-type semiconductor material is used as the target material, a thin film is evaporated on the electron transport layer, and then annealed at 120°C for 10 minutes to obtain the first N-type semiconductor layer; a P-type semiconductor material is evaporated on the first N-type semiconductor layer, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer; a second N-type semiconductor material is evaporated on the P-type semiconductor layer, and then annealed at 120°C for 10 minutes to obtain a second N-type semiconductor layer, and the first functional layer of the NPN structure is obtained. Among them, the first N-type semiconductor material and the second N-type semiconductor material are both phosphorus-doped silicon, and the concentration of phosphorus doping in the material is 10wt%; the P-type semiconductor material is boron-doped silicon, and the concentration of boron doping in the material is 10wt%; the film thickness of each NPN unit is 15nm / 30nm / 15nm.

[0143] Film Example 12

[0144] The scheme of this film embodiment is basically the same as that of film embodiment 1, except that, in this film embodiment, in step (2),

[0145] Set the evaporation conditions as follows: vacuum degree is 10 -4 Pa, the radio frequency frequency is 13MHz, phosphorus-doped silicon is used as the target material, and the concentration of phosphorus doping in the material is 5wt%, a thin film A is evaporated on the electron transport layer, and then annealed at 120℃ for 10min to obtain a first N-type semiconductor layer A with a thickness of 5nm; then antimony-doped silicon is used as the target material, and the concentration of antimony doping in the material is 5wt%, a thin film B is evaporated on the electron transport layer, and then annealed at 120℃ for 10min to obtain a first N-type semiconductor layer B with a thickness of 5nm, and the first N-type semiconductor layer A and the first N-type semiconductor layer B are spaced 8nm apart.

[0146] Boron-doped silicon is evaporated on the first N-type semiconductor layer A, and the concentration of boron doping in the material is 5wt%, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer A with a thickness of 50nm; gallium-doped silicon is evaporated on the first N-type semiconductor layer B, and the concentration of gallium doping in the material is 5wt%, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer B with a thickness of 50nm.

[0147] Antimony-doped silicon was evaporated on the P-type semiconductor layer A, and the concentration of antimony doping in the material was 5wt%, and then annealed at 120°C for 10min to obtain a second N-type semiconductor layer A with a thickness of 5nm; phosphorus-doped silicon was evaporated on the P-type semiconductor layer B, and the concentration of phosphorus doping in the material was 5wt%, and then annealed at 120°C for 10min to obtain a second N-type semiconductor layer B with a thickness of 5nm. A first NPN unit and a second NPN unit spaced from each other were obtained.

[0148] Polyimide is deposited between the first NPN unit and the second NPN unit to form an insulating unit. The first functional layer of the parallel NPN-NPN structure (phosphorus-doped silicon / boron-doped silicon / antimony-doped silicon-antimony-doped silicon / gallium-doped silicon / phosphorus-doped silicon) is obtained. The electron transport layer and the first functional layer together constitute a composite film.

[0149] Film Comparative Example 1

[0150] The solution of the film comparative example is basically the same as that of film embodiment 1, with the only difference being that, in the film comparative example, the first functional layer is not provided, and accordingly, step (2) is omitted in the preparation method.

[0151] Film Comparative Example 2

[0152] The scheme of this film comparative example is basically the same as that of film embodiment 7, except that in this film comparative example, the first functional layer is changed to an NP silicon tube layer, and accordingly, step (6) is changed to:

[0153] Set the evaporation conditions as follows: vacuum degree is 10 -4 Pa, the radio frequency frequency is 13MHz, and the N-type semiconductor material is used as the target material. A thin film is evaporated on the electron transport layer, and then annealed at 120°C for 10 minutes to obtain an N-type semiconductor layer; a P-type semiconductor material is evaporated on the N-type semiconductor layer, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer; and an NP silicon tube layer with an NP structure is obtained. Among them, the N-type semiconductor material is phosphorus-doped silicon, and the concentration of phosphorus doping in the material is 10wt%; the P-type semiconductor material is boron-doped silicon, and the concentration of boron doping in the material is 10wt%; the film thickness of the NP silicon tube layer is 30nm / 30nm.

[0154] Film Comparative Example 3

[0155] The scheme of this film comparative example is basically the same as that of film embodiment 7, except that in this film comparative example, the first functional layer is changed to a PN silicon tube layer, and accordingly, step (6) is changed to:

[0156] Set the evaporation conditions as follows: vacuum degree is 10 -4 Pa, the radio frequency frequency is 13MHz, and a P-type semiconductor material is used as a target material. A thin film is evaporated on the electron transport layer, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer; an N-type semiconductor material is evaporated on the P-type semiconductor layer, and then annealed at 120°C for 10 minutes to obtain an N-type semiconductor layer; and a PN silicon tube layer of a PN structure is obtained. Among them, the N-type semiconductor material is phosphorus-doped silicon, and the concentration of phosphorus doping in the material is 10wt%; the P-type semiconductor material is boron-doped silicon, and the concentration of boron doping in the material is 10wt%; the film thickness of the PN silicon tube layer is 30nm / 30nm.

[0157] Film Comparative Example 4

[0158] The scheme of this film comparative example is basically the same as that of film comparative example 2, except that in this film comparative example, the NP silicon tube layer is replaced by the NP germanium tube layer. Accordingly, in step (6):

[0159] The main materials of both P-type semiconductor materials and N-type semiconductor materials are changed from silicon to germanium, that is, the N-type semiconductor material is germanium phosphide; and the P-type semiconductor material is germanium boride.

[0160] Film Comparative Example 5

[0161] The scheme of this film comparative example is basically the same as that of film comparative example 3, except that in this film comparative example, the NP silicon tube layer is replaced by the NP germanium tube layer. Accordingly, in step (6):

[0162] The main materials of both P-type semiconductor materials and N-type semiconductor materials are changed from silicon to germanium, that is, the N-type semiconductor material is germanium phosphide; and the P-type semiconductor material is germanium boride.

[0163] Device Example 1

[0164] (1) Provide an ITO anode, wipe the ITO surface with a cotton swab dipped in a small amount of soapy water to remove impurities visible to the naked eye, then ultrasonically clean it with deionized water, acetone, anhydrous ethanol, and deionized water for 20 minutes, and then blow dry it with nitrogen for later use.

[0165] (2) Spin coating the PEDOT:PSS material on the anode at a rotation speed of 3000 rpm for 30 seconds and annealing at 100° C. for 10 minutes to obtain a hole injection layer with a thickness of 50 nm.

[0166] (3) The surface of the hole injection layer was spin-coated with TFB chlorobenzene solution at a speed of 3000 r / min for 30 s and annealed at 150° C. for 30 min to obtain a hole transport layer with a thickness of 40 nm.

[0167] (4) Spin coating a hexane solution of CdSe blue quantum dots on the hole transport layer at a rotation speed of 3000 rpm for 30 s and annealing at 80° C. for 30 min to obtain a light-emitting layer with a thickness of 20 nm.

[0168] (5) Spin-coat a ZnO ethanol solution on the light-emitting layer at a rotation speed of 3000 rpm for 30 seconds and anneal at 80° C. for 30 minutes to obtain an electron transport layer with a thickness of 30 nm.

[0169] (6) Set the evaporation conditions as follows: vacuum degree is 10 -4Pa, the radio frequency is 13MHz, the first N-type semiconductor material is used as the target material, two thin films with an interval of 8nm are evaporated on the electron transport layer, and then annealed at 120℃ for 10min to obtain two independent and spaced first N-type semiconductor layers; P-type semiconductor material is evaporated on each first N-type semiconductor layer, and then annealed at 120℃ for 10min to obtain a P-type semiconductor layer; the second N-type semiconductor material is evaporated on the P-type semiconductor layer, and then annealed at 120℃ for 10min to obtain a second N-type semiconductor layer. The first NPN unit and the second NPN unit are obtained. Polyimide is deposited between the first NPN unit and the second NPN unit to form an insulating unit. A parallel NPN-NPN structure is obtained. Among them, the first N-type semiconductor material and the second N-type semiconductor material are both phosphorus-doped silicon, and the concentration of phosphorus doping in the material is 5wt%; the P-type semiconductor material is boron-doped silicon, and the concentration of boron doping in the material is 5wt%; the film thickness of each NPN unit is 5nm / 50nm / 5nm.

[0170] (7) Place the sheet prepared in step (6) into a vacuum coating machine and set the evaporation conditions to: vacuum degree 4×10 - 6 mbar, the evaporation temperature was 350°C, the evaporation rate was 3 angstroms / min, and the electrode was evaporated with an Ag target to obtain a cathode with a thickness of 30 nm. The device was then packaged in an environment where the oxygen and water contents were both lower than 0.1 ppm to obtain a QLED device.

[0171] Device Example 2

[0172] The scheme of this device embodiment is basically the same as that of device embodiment 1, with the only difference being that in this device embodiment, in step (6), the boron doping concentration is changed to 10%.

[0173] Device Example 3

[0174] The scheme of this device embodiment is basically the same as that of device embodiment 1, with the only difference being that in this device embodiment, in step (6), the boron doping concentration is changed to 15%.

[0175] Device Example 4

[0176] The scheme of this device embodiment is basically the same as that of device embodiment 1, with the only difference being that in this device embodiment, in step (6), the boron doping concentration is changed to 20%.

[0177] Device Example 5

[0178] The scheme of this device embodiment is basically the same as that of device embodiment 2, with the only difference being that in this device embodiment, in step (6), the phosphorus doping concentration is changed to 10%.

[0179] Device Example 6

[0180] The scheme of this device embodiment is basically the same as that of device embodiment 5, with the only difference being that in this device embodiment, in step (6), the film thickness of each NPN unit is changed to 10nm / 40nm / 10nm.

[0181] Device Example 7

[0182] The scheme of this device embodiment is basically the same as that of device embodiment 5, with the only difference being that in this device embodiment, in step (6), the film thickness of each NPN unit is changed to 15nm / 30nm / 15nm.

[0183] Device Example 8

[0184] The scheme of this device embodiment is basically the same as that of device embodiment 5, with the only difference being that in this device embodiment, in step (6), the film thickness of each NPN unit is changed to 20nm / 20nm / 20nm.

[0185] Device Example 9

[0186] The scheme of this device embodiment is basically the same as that of device embodiment 5, with the only difference being that in this device embodiment, in step (6), the film thickness of each NPN unit is changed to 25nm / 10nm / 25nm.

[0187] Device Example 10

[0188] The scheme of the present device embodiment is basically the same as that of device embodiment 7, with the only difference being that, in the present device embodiment, in step (6), the main materials of the first N-type semiconductor material, the P-type semiconductor material and the second N-type semiconductor material are all changed from silicon to germanium, that is, the first N-type semiconductor material and the second N-type semiconductor material are both germanium phosphide; and the P-type semiconductor material is germanium boride.

[0189] Device Example 11

[0190] The scheme of this device embodiment is basically the same as that of device embodiment 7, except that, in this device embodiment, in step (6), there is only one first functional layer, and the corresponding step (6) is changed to:

[0191] Set the evaporation conditions as follows: vacuum degree is 10 -4Pa, the radio frequency frequency is 13MHz, the first N-type semiconductor material is used as the target material, a thin film is evaporated on the electron transport layer, and then annealed at 120°C for 10 minutes to obtain the first N-type semiconductor layer; a P-type semiconductor material is evaporated on the first N-type semiconductor layer, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer; a second N-type semiconductor material is evaporated on the P-type semiconductor layer, and then annealed at 120°C for 10 minutes to obtain a second N-type semiconductor layer, and the first functional layer of the NPN structure is obtained. Among them, the first N-type semiconductor material and the second N-type semiconductor material are both phosphorus-doped silicon, and the concentration of phosphorus doping in the material is 10wt%; the P-type semiconductor material is boron-doped silicon, and the concentration of boron doping in the material is 10wt%; the film thickness of each NPN unit is 15nm / 30nm / 15nm.

[0192] Device Example 12

[0193] The scheme of the device embodiment is basically the same as that of the device embodiment 1, except that, in the device embodiment, in step (6), the first functional layer is a parallel NPN-NPN structure (phosphorus-doped silicon / boron-doped silicon / antimony-doped silicon-antimony-doped silicon / gallium-doped silicon / phosphorus-doped silicon); accordingly, step (6) is changed to:

[0194] Set the evaporation conditions as follows: vacuum degree is 10 -4 Pa, the radio frequency is 13MHz. Using phosphorus-doped silicon as the target material, and the concentration of phosphorus doping in the material is 5wt%, a thin film A is evaporated on the electron transport layer, and then annealed at 120°C for 10min to obtain a first N-type semiconductor layer A with a thickness of 5nm; using antimony-doped silicon as the target material, and the concentration of antimony doping in the material is 5wt%, a thin film B is evaporated on the electron transport layer, and then annealed at 120°C for 10min to obtain a first N-type semiconductor layer B with a thickness of 5nm, and the first N-type semiconductor layer A and the first N-type semiconductor layer B are separated by 8nm.

[0195] Boron-doped silicon is evaporated on the first N-type semiconductor layer A, and the concentration of boron doping in the material is 5wt%, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer A with a thickness of 50nm; gallium-doped silicon is evaporated on the first N-type semiconductor layer B, and the concentration of gallium doping in the material is 5wt%, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer B with a thickness of 50nm.

[0196] Antimony-doped silicon was evaporated on the P-type semiconductor layer A, and the concentration of antimony doping in the material was 5wt%, and then annealed at 120°C for 10min to obtain a second N-type semiconductor layer A with a thickness of 5nm; phosphorus-doped silicon was evaporated on the P-type semiconductor layer B, and the concentration of phosphorus doping in the material was 5wt%, and then annealed at 120°C for 10min to obtain a second N-type semiconductor layer B with a thickness of 5nm. A first NPN unit and a second NPN unit spaced from each other were obtained.

[0197] Polyimide is deposited between the first NPN unit and the second NPN unit to form an insulating unit. The first functional layer of the parallel NPN-NPN structure (phosphorus-doped silicon / boron-doped silicon / antimony-doped silicon-antimony-doped silicon / gallium-doped silicon / phosphorus-doped silicon) is obtained. The electron transport layer and the first functional layer together constitute a composite film.

[0198] Device Comparative Example 1

[0199] The scheme of the device comparative example is basically the same as that of device embodiment 1, except that, in the device comparative example, the first functional layer is not provided, and accordingly, in the preparation method, step (6) is omitted, and in step (7), the cathode is prepared directly on the electron transport layer.

[0200] Device Comparison Example 2

[0201] The scheme of the device comparative example is basically the same as that of device embodiment 7, except that, in the device comparative example, the first functional layer is changed to an NP silicon tube layer, and accordingly, step (6) is changed to:

[0202] Set the evaporation conditions as follows: vacuum degree is 10 -4 Pa, the radio frequency frequency is 13MHz, and the N-type semiconductor material is used as the target material. A thin film is evaporated on the electron transport layer, and then annealed at 120°C for 10 minutes to obtain an N-type semiconductor layer; a P-type semiconductor material is evaporated on the N-type semiconductor layer, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer; and an NP silicon tube layer with an NP structure is obtained. Among them, the N-type semiconductor material is phosphorus-doped silicon, and the concentration of phosphorus doping in the material is 10wt%; the P-type semiconductor material is boron-doped silicon, and the concentration of boron doping in the material is 10wt%; the film thickness of the NP silicon tube layer is 30nm / 30nm.

[0203] Device Comparison Example 3

[0204] The scheme of the device comparative example is basically the same as that of device embodiment 7, except that, in the device comparative example, the first functional layer is changed to a PN silicon tube layer, and accordingly, step (6) is changed to:

[0205] Set the evaporation conditions as follows: vacuum degree is 10 -4Pa, the radio frequency frequency is 13MHz, and a P-type semiconductor material is used as a target material. A thin film is evaporated on the electron transport layer, and then annealed at 120°C for 10 minutes to obtain a P-type semiconductor layer; an N-type semiconductor material is evaporated on the P-type semiconductor layer, and then annealed at 120°C for 10 minutes to obtain an N-type semiconductor layer; and a PN silicon tube layer of a PN structure is obtained. Among them, the N-type semiconductor material is phosphorus-doped silicon, and the concentration of phosphorus doping in the material is 10wt%; the P-type semiconductor material is boron-doped silicon, and the concentration of boron doping in the material is 10wt%; the film thickness of the PN silicon tube layer is 30nm / 30nm.

[0206] Device Comparison Example 4

[0207] The scheme of the device comparative example is basically the same as that of the device comparative example 2, except that in the device comparative example, the NP silicon tube layer is replaced by the NP germanium tube layer. Accordingly, in step (6):

[0208] The main materials of both the P-type semiconductor material and the N-type semiconductor material are changed from silicon to germanium, that is, the N-type semiconductor material is germanium phosphide; and the P-type semiconductor material is germanium boride.

[0209] Device Comparison Example 5

[0210] The scheme of the device comparative example is basically the same as that of the device comparative example 3, except that in the device comparative example, the NP silicon tube layer is replaced by the NP germanium tube layer. Accordingly, in step (6):

[0211] The main materials of both the P-type semiconductor material and the N-type semiconductor material are changed from silicon to germanium, that is, the N-type semiconductor material is germanium phosphide; and the P-type semiconductor material is germanium boride.

[0212] Experimental example

[0213] (I) Prepare the respective single electron devices (EOD) corresponding to the above-mentioned film examples and film comparison examples, and test the current density-voltage curve of the device. Take the current density of the device at 4V for comparison. The preparation method of the single electron device (EOD) is as follows:

[0214] (1) Provide an ITO anode, wipe the ITO surface with a cotton swab dipped in a small amount of soapy water to remove impurities visible to the naked eye, then ultrasonically clean it with deionized water, acetone, anhydrous ethanol, and deionized water for 20 minutes, and then blow dry it with nitrogen for later use.

[0215] (2) A composite film is prepared on the anode, wherein the electron transport layer in the composite film is arranged close to the anode.

[0216] (3) Place the sheet prepared in step (2) into a vacuum coating machine and set the evaporation conditions to: vacuum degree of 4×10 - 6mbar, the evaporation temperature was 350°C, the evaporation rate was 3 angstroms / min, and the electrode was evaporated with an Ag target to obtain a cathode with a thickness of 30 nm. The device was then packaged in an environment where the oxygen and water contents were both lower than 0.1 ppm to obtain a QLED device.

[0217] Wherein, the composite film in step (2) corresponds to the film prepared in the above-mentioned film embodiment or film comparison example.

[0218] The results are recorded in Table 1.

[0219] Table 1

[0220]

[0221]

[0222] As can be seen from the above table, the film examples 1 to 12 have a current density significantly higher than that of the film comparative example 1, that is, compared with the single electron transport layer, the composite film has a higher current density at 4V, indicating that the composite film has a higher electron transport performance;

[0223] In addition, among thin film comparison examples 2 to 5, thin film comparison examples 2 and 4 remain basically unchanged, while the current density of thin film comparison examples 3 and 5 decreases, indicating that setting up NP tubes or PN tubes cannot amplify the current. On the contrary, setting an NPN structure on one side of the electron transport layer helps to improve the electron transport performance of the film.

[0224] (II) The devices prepared in the above device embodiments and device comparative examples were tested for CE (current efficiency), life T95 and T95@1000nit. The detection method was based on the conventional method in the art, and the results were recorded in Table 2. Wherein:

[0225] The lifespan T95@1000nit indicates the time required for the brightness of the device to decrease to a certain percentage of the maximum brightness when driven by a constant current or voltage. The time when the brightness drops to 95% of the maximum brightness is defined as T95, and this lifespan is the measured lifespan. In order to shorten the test cycle, the device lifespan test is usually carried out at high brightness by accelerating device aging, and the lifespan at high brightness is obtained by fitting the extended exponential decay brightness attenuation fitting formula. For example, the lifespan at 1000nit is calculated as T95@1000nit. The specific calculation formula is as follows:

[0226]

[0227] Among them, T95 L For lifespan at low brightness, T95 H is the measured lifetime under high brightness, L H To accelerate the device to the highest brightness, LL is 1000nit, A is the acceleration factor, and this experiment measured the lifespan of several groups of QLED devices at rated brightness and found that the A value was 1.7.

[0228] Table 2

[0229] CE@1Knit T95 LT95@1Knit Device Example 1 20 5.5 15000 Device Example 2 22 8.8 25000 Device Example 3 20 5.8 20000 Device Example 4 15 3.4 12200 Device Example 5 22 9.0 25300 Device Example 6 23 9.6 26000 Device Example 7 25 11.2 27000 Device Example 8 24 10 26500 Device Example 9 20 5.5 18600 Device Example 10 23.5 10.9 26600 Device Example 11 14.4 4.4 9900 Device Example 12 19 5.4 14500 Device Comparative Example 1 12.5 3.5 8000 Device Comparison Example 2 11.5 6 7800 Device Comparison Example 3 5 0.1 0 Device Comparison Example 4 11 6.2 7500 Device Comparison Example 5 4 0.1 0

[0230] Compared with device comparative example 1, each device embodiment has higher CE, T95 and T95@1000nit, indicating that the present application facilitates electron injection and improves carrier balance by setting an NPN layer between the electron transport layer and the cathode, which is macroscopically manifested as improving its current efficiency and extending its life;

[0231] Device Example 7, device comparison examples 2 and 3 are compared with device comparison example 1, and device Example 10, device comparison examples 4 and 5 are compared with device comparison example 1. CE, T95 and T95@1000nit of device Example 7 and device Example 10 are improved, device comparison examples 2 and 4 remain basically unchanged, and device comparison examples 3 and 5 decrease significantly. This may be because both NP tubes and PN tubes can only conduct electricity unidirectionally and cannot amplify current. The PN tube is instead arranged between the electron transport layer and the cathode, blocking the current.

[0232] The composite film, optoelectronic device and display device provided in the embodiments of the present application are introduced in detail above. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for technical personnel in this field, according to the idea of ​​the present application, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A composite film, characterized in that: It includes a stacked second functional layer and a first functional layer, wherein the first functional layer includes a functional unit, and the functional unit includes a first N-type semiconductor layer, a P-type semiconductor layer, and a second N-type semiconductor layer stacked in sequence, and the first N-type semiconductor layer is arranged close to the second functional layer; Among them, the material of the second functional layer includes a first material or a second material, the first material includes at least one of N-type metal oxide, doped N-type metal oxide, II-VI semiconductor material, III-V semiconductor material and I-III-VI semiconductor material, and the second material includes at least one of cesium carbonate, cesium fluoride, cesium azide and lithium fluoride.

2. The composite film according to claim 1, characterized in that The first functional layer includes at least one functional unit. When the first functional layer includes a plurality of functional units, the plurality of functional units are arranged in parallel on one side of the second functional layer, and thicknesses of any two functional units are equal.

3. The composite film according to claim 2, characterized in that: An insulating unit is arranged between two adjacent functional units.

4. The composite film according to claim 3, characterized in that: The material of the insulating unit includes an organic insulating material or an inorganic insulating material, wherein the organic insulating material includes one or more of polystyrene, polypropylene, polyester, polycarbonate, polytetrafluoroethylene, and polyimide; the inorganic insulating material includes one or more of silicon dioxide and aluminum oxide; and / or, The insulating unit has two side surfaces facing two adjacent functional units respectively, and a distance between the two side surfaces is 5-10 nm.

5. The composite film according to claim 1, characterized in that The thickness of the first N-type semiconductor layer is 5 to 24 nm; and / or, The thickness of the P-type semiconductor layer is 11 to 50 nm; and / or, The thickness of the second N-type semiconductor layer is 5-24 nm.

6. The composite film according to claim 1, characterized in that: The first N-type semiconductor layer includes a first main material doped with a first N-type doping element, the first main material includes silicon or germanium, and the first N-type doping element includes one or more of phosphorus, arsenic, and antimony; and / or, The material of the second N-type semiconductor layer includes a second main material doped with a second N-type doping element, the second main material includes silicon or germanium, and the second N-type doping element includes one or more of phosphorus, arsenic, and antimony; and / or, The material of the P-type semiconductor layer includes a third main material doped with a P-type doping element, the third main material includes silicon or germanium, and the P-type doping element includes one or more of boron, indium, and gallium; and / or, The N-type metal oxide includes at least one of ZnO, BaO, TiO2, and SnO2; the metal oxide in the doped N-type metal oxide includes at least one of ZnO, TiO2, and SnO2, the doping element includes at least one of Al, Mg, Li, In, and Ga, the II-VI group semiconductor material includes at least one of ZnS, ZnSe, and CdS; the III-V group semiconductor material includes at least one of InP and GaP; the I-III-VI group semiconductor material includes at least one of CuInS and CuGaS.

7. The composite film according to claim 6, characterized in that: In the material of the first N-type semiconductor layer, the mass percentage of the first N-type doping element is 5-19%; and / or, In the material of the second N-type semiconductor layer, the mass percentage of the second N-type doping element is 5-19%; and / or, In the material of the P-type semiconductor layer, the mass percentage of the P-type doping element is 5-19%.

8. A photoelectric device comprising a cathode and an anode, characterized in that: Also included is a composite film disposed between the cathode and the anode, the composite film comprising a stacked second functional layer and a first functional layer, the first functional layer comprising a functional unit, the functional unit comprising a first N-type semiconductor layer, a P-type semiconductor layer and a second N-type semiconductor layer stacked in sequence, and the first N-type semiconductor layer is disposed close to the second functional layer; Among them, the material of the second functional layer includes a first material or a second material, the first material includes at least one of N-type metal oxide, doped N-type metal oxide, II-VI semiconductor material, III-V semiconductor material and I-III-VI semiconductor material, and the second material includes at least one of cesium carbonate, cesium fluoride, cesium azide and lithium fluoride.

9. The optoelectronic device according to claim 8, characterized in that: The first functional layer includes at least one functional unit. When the first functional layer includes a plurality of functional units, the plurality of functional units are arranged in parallel on one side of the second functional layer, and thicknesses of any two functional units are equal.

10. The optoelectronic device according to claim 9, characterized in that: An insulating unit is arranged between two adjacent functional units.

11. The optoelectronic device according to claim 8, characterized in that: The thickness of the first N-type semiconductor layer is 5 to 24 nm; and / or, The thickness of the P-type semiconductor layer is 11 to 50 nm; and / or, The thickness of the second N-type semiconductor layer is 5 to 24 nm; and / or, The first N-type semiconductor layer includes a first main material doped with a first N-type doping element, the first main material includes silicon or germanium, and the first N-type doping element includes one or more of phosphorus, arsenic, and antimony; and / or, The material of the second N-type semiconductor layer includes a second main material doped with a second N-type doping element, the second main material includes silicon or germanium, and the second N-type doping element includes one or more of phosphorus, arsenic, and antimony; and / or, The material of the P-type semiconductor layer includes a third main material doped with a P-type doping element, the third main material includes silicon or germanium, and the P-type doping element includes one or more of boron, indium, and gallium.

12. The optoelectronic device according to claim 11, characterized in that: In the material of the first N-type semiconductor layer, the mass percentage of the first N-type doping element is 5-19%; and / or, In the material of the second N-type semiconductor layer, the mass percentage of the second N-type doping element is 5-19%; and / or, In the material of the P-type semiconductor layer, the mass percentage of the P-type doping element is 5-19%.

13. The optoelectronic device according to claim 8, characterized in that: The cathode and the anode independently include a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode includes 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 and aluminum-doped magnesium oxide, the composite electrode of metal and metal oxide includes AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, the material of the metal electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba; and / or, The optoelectronic device further includes a light-emitting layer, which is disposed between the second functional layer and the anode. The material of the light-emitting layer includes one or more of an organic light-emitting material and a quantum dot light-emitting material. The organic light-emitting material includes 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 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 or more, the quantum dot luminescent material includes at least one of single structure quantum dots, core-shell structure quantum dots and perovskite semiconductor material; the material of the single structure quantum dot, the core material of the core-shell structure quantum dot and the shell material of the core-shell structure quantum dot include II-VI group compounds, IV-VI group compounds, III-V group compounds and I-II At least one of the I-VI group compounds; the II-VI group compounds include 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, Cd At least one of ZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compound includes at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe;The III-V compounds include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, and AlN P, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInN P, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound includes at least one of CuInS2, CuInSe2 and AgInS2; the perovskite semiconductor material includes a doped or undoped inorganic perovskite semiconductor, or an organic-inorganic hybrid perovskite semiconductor; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs; + ions, M is a divalent metal cation, including Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of X is a halogen anion including Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation, including CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation, including Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of X is a halogen anion including Cl - Br - ,I - At least one of .

14. The optoelectronic device according to claim 13, characterized in that: The material of the light-emitting layer includes a first quantum dot material, and the first quantum dot material is a blue quantum dot having an emission wavelength of 435 to 470 nm.

15. A display device, characterized in that: The optoelectronic device comprises the optoelectronic device according to any one of claims 8 to 14.

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