Composition, film, and optoelectronic device

Abstract

The invention discloses a composition, a thin film and a photoelectric device, the composition comprises a first material and a second material, the first material is selected from an organic P-type semiconductor material, the existence of the first material is beneficial for improving the film forming quality of the composition, the second material is selected from undoped or first metal element doped phosphorene, and the second material is selected from organic P-type semiconductor materials. The existence of the second material is beneficial to improving the conductivity of the composition and reducing the band gap of the composition, and the composition has good conductivity and film forming quality, can be applied to a photoelectric device, and is beneficial to improving the device efficiency and prolonging the device life of the photoelectric device.

Description

Technical Field

[0001] This application relates to the field of optoelectronic technology, specifically to a composition, a thin film, and an optoelectronic device. Background Technology

[0002] Hole functional materials refer to a class of materials that readily lose electrons to form positively charged vacancies (holes), and under the influence of an electric field, enable the directional and controlled migration of holes to transport charge, and / or reduce the hole injection energy barrier. Based on function, hole functional materials include hole transport materials and hole injection materials.

[0003] Hole functional materials can be organic or inorganic. Organic hole functional materials have the advantage of high film quality, but their conductivity is limited. Inorganic hole functional materials have good conductivity, but they suffer from poor film quality, resulting in poor performance of devices using hole functional materials. Summary of the Invention

[0004] In view of the shortcomings of the prior art, this application provides a composition, a thin film, and an optoelectronic device.

[0005] The technical solution of this application is as follows:

[0006] In a first aspect, this application provides a composition comprising a first material and a second material, wherein the first material is selected from organic p-type semiconductor materials, and the second material is selected from one or more of undoped phosphorene and phosphorene doped with a first metal element.

[0007] In a second aspect, this application provides a thin film, the material of which comprises a composition, the composition comprising a first material and a second material, wherein the first material is selected from organic p-type semiconductor materials, and the second material is selected from one or more of undoped phosphorene and phosphorene doped with a first metal element.

[0008] Thirdly, this application provides an optoelectronic device, including an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode. The functional layer includes a plurality of functional sublayers stacked together, and at least one of the functional sublayers is made of a second material selected from one or more of first metal-doped phosphorene and undoped phosphorene.

[0009] This application provides a composition, a thin film, and an optoelectronic device, which have the following technical effects:

[0010] The composition of this application includes a first material and a second material. The first material is selected from organic p-type semiconductor materials. The presence of the first material is beneficial to improving the film formation quality of the composition. The second material is selected from one or more of first metal-doped phosphorene and undoped phosphorene. The presence of the second material is beneficial to improving the conductivity of the composition and reducing the band gap of the composition. The composition has good conductivity and film formation quality. The composition can be applied to optoelectronic devices, which is beneficial to improving the device efficiency and device life of optoelectronic devices. Attached Figure Description

[0011] The technical solution and other beneficial effects of this application will become apparent from the following detailed description of specific embodiments in conjunction with the accompanying drawings.

[0012] Figure 1 This application provides a schematic diagram of the structure of an optoelectronic device. Detailed Implementation

[0013] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to this invention. The preferred embodiments and materials described herein are for illustrative purposes only and do not limit the scope of this application.

[0015] It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of embodiments. Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0016] In the description of this application, the term "comprising" means "including but not limited to".

[0017] The term "at least one" refers to one or more items, while "multiple" or "multi-item" refers to two or more items. The terms "at least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can be expressed as: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0018] The term "and / or" encompasses any one of two or more of the listed items, as well as any and all combinations of the listed items. These combinations include any two listed items, any number of listed items, or a combination of all listed items. For example, "A and / or B" includes three parallel solutions: A, B, and A+B. Similarly, the technical solution "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (i.e., all connected by "logical OR"), any and all combinations of A, B, C, and D, including combinations of any two or three of A, B, C, and D, and combinations of all four of A, B, C, and D (i.e., all connected by "logical AND").

[0019] In this application, descriptions such as "layer A is formed on one side of layer B," "layer A is formed on the side of layer B away from layer C," or similar expressions can mean that layer A is directly formed on one side of layer B or on the side of layer B away from layer C, i.e., layer A and layer B are in direct contact; or they can mean that layer A is indirectly formed on one side of layer B or on the side of layer B away from layer C, i.e., other spacer structures can be formed between layer A and layer B. Similarly, "layer A is disposed on one side of layer B" or "layer A is disposed on the side of layer B away from layer C" can mean that layer A and layer B are in direct contact, or that other spacer structures are provided between layer A and layer B; "layer A is disposed between layer B and layer C" can mean that layer A and layer B are in direct contact and layer A and layer C are in direct contact, or layer A and layer B are in direct contact and one or more spacer structures are provided between layer A and layer C, or layer A and layer B are provided and one or more spacer structures are provided between layer A and layer C, or layer A and layer B are provided and layer A and layer C are in direct contact.

[0020] The term "particle size" refers to the diameter of nanoparticles.

[0021] This application provides a composition comprising a first material and a second material, wherein the first material is selected from organic p-type semiconductor materials and the second material is selected from undoped phosphorene or phosphorene doped with a first metal element.

[0022] "Organic hole transport materials" refer to a class of organic compounds that easily lose electrons to form positively charged vacancies (holes), and can achieve directional and orderly controllable migration of holes to transport charges under the action of an electric field.

[0023] "Organic hole injection materials" refer to a class of organic compounds that easily lose electrons to form positively charged vacancies (holes), and can achieve directional and orderly controllable injection of holes under the action of an electric field to transfer charge.

[0024] "Phosphine" refers to black phosphorus or two-dimensional black phosphorus, a two-dimensional semiconductor material with a direct band gap, consisting of a single atomic layer of ordered phosphorus atoms stripped from black phosphorus. In some embodiments of this application, the phosphorus was purchased from Aladdin, catalog number B196539.

[0025] The composition in this application embodiment includes a first material and a second material. The first material is selected from organic p-type semiconductor materials. The presence of the first material is beneficial to improving the film formation quality of the composition. The second material is selected from one or more of undoped phosphorene and phosphorene doped with a first metal element. The presence of the second material is beneficial to improving the conductivity of the composition and reducing the band gap of the composition. The composition has good conductivity and film formation quality.

[0026] In order to further improve the film-forming quality of the composition and ensure that the composition has good hole transport performance, in some embodiments of this application, the mass ratio of the second material to the first material is 1:(30-70), for example, it can be 1:30, 1:40, 1:50, 1:60, 1:70 or any two of the foregoing values.

[0027] In some embodiments of this application, the first metal element is selected from one or more of Group IA, Group IIA, Group IIIA, Group IVA, Group VA, and transition metal elements. For example, the first metal element is selected from one or more of Cr, Mg, Fe, Co, and Ni. Further, the band gap of the phosphorene doped with the first metal element is 0.4 eV to 2 eV, for example, it can be 0.4 eV, 0.5 eV, 0.8 eV, 1.0 eV, 1.5 eV, 2.0 eV, or any value between any two of the aforementioned values. It should be noted that the band gap of the phosphorene doped with the first metal element is calculated using first-principles methods, and the sub-exchange correlation energy is approximated using the generalized gradient approximation of Perdew-Burke-Ernzerh (GGA-PBE); the thickness of the vacuum region is greater than... To avoid interlayer interactions, a 5×7×1 Monkhorst-packk-point network was used for structural relaxation, while a denser 7×10×1 grid was used to calculate the band structure. All doped architectures were optimized, with a plane wave stage energy of 500 eV and a convergence energy less than 5×10 eV. - 6 eV / atom, the force on each atom is less than eV / atom The calculated BP lattice constant is as follows:

[0028] In order to further improve the structural stability and conductivity of the phosphorene doped with the first metal element, in some embodiments of this application, the atomic percentage of the first metal element in the phosphorene doped with the first metal element is 1% to 5%, for example, it can be 1%, 2%, 3%, 4%, 5% or any value between the two aforementioned values.

[0029] To further improve the structural stability and conductivity of the phosphorene doped with the first metal element, in some embodiments of this application, the phosphorene doped with the first metal element has a layered structure, wherein the number of layers in the layered structure is 1 to 10, for example, 1, 3, 5, 7, 10 layers or any value between the aforementioned two. The average sheet diameter of the phosphorene doped with the first metal element is, for example, 100 nm to 200 nm. It should be noted that the average sheet diameter of the phosphorene doped with the first metal element is detected using a transmission electron microscope (TEM).

[0030] In some embodiments of this application, the organic P-type semiconductor material is selected from one or more of organic hole transport materials and organic hole injection materials.

[0031] The organic hole injection material is selected from one or more of the following: poly(3,4-vinyldioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS, CAS No. 155090-83-8), copper phthalocyanine (CAS No. 147-14-8), titanium phthalocyanine (CAS No. 26201-32-1), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (CAS No. 29261-33-4), and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (CAS No. 105598-27-4).

[0032] In some embodiments of this application, the organic hole transport material is selected from polyaniline (CAS No. 25233-30-1), polypyrrole (CAS No. 30604-81-0), 3-hexyl-substituted polythiophene (CAS No. 104934-50-1), poly(9-vinylcarbazole) (abbreviated as PVK, CAS No. 25067-59-8), 4,4'-bis(9-carbazole)biphenyl (abbreviated as CBP, CAS No. 58328-31-7), poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline] (abbreviated as TAPC, CAS No. 58473-78-2), poly[(9 9-Dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)] (abbreviated as TFB, CAS No. 220797-16-0), poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-di-n-octylfluorenyl-2,7-diyl)] (CAS No. 223569-31-1), 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (CAS No. 124729-98-2), 4,4',4”-tris(carbazole-9-yl)triphenylamine (abbreviated as TCTA, CAS No. 139092-78-7), 4,4',4'-Tris(2-naphthylphenylamino)triphenylamine (CAS No. 185690-41-9), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as NPB, CAS No. 123847-85-8), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (abbreviated as TPD, CAS No. 65181-78-4), N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine (CAS No. 209980-53-0), N,N'-bis(3-methylphenyl)-N,N'-diphenyl One or more of the following: 9,9-spirodifluorene-2,7-diamine (Spiro-TPD, CAS No. 1033035-83-4), N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirodi[9H-fluorene]-2,7-diamine (CAS No. 932739-76-9), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTTA, CAS No. 1333317-99-9), and 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-omeTAD, CAS No. 207739-72-8).

[0033] To further improve the film-forming quality and conductivity of the composition, in some embodiments of this application, the first material is selected from one or more of TFB, polypyrrole and polyaniline, and the second material is selected from Fe-doped phosphorene.

[0034] It should be noted that the preparation method of phosphorene doped with the first metal element includes, for example, the steps of: mixing solid phosphorene and powdered metal according to the atomic percentage of the first metal element doping to obtain a mixture; and then, placing the mixture in a ball mill for ball milling to obtain phosphorene doped with the first metal element.

[0035] This application also provides a thin film, the material of which includes any of the compositions described above, wherein the first material and the second material are described above, and the thin film has good surface flatness and hole mobility.

[0036] This application also provides a method for preparing a thin film, the method comprising the steps of: depositing a dispersion containing a composition, and then drying the deposited dispersion to obtain a thin film.

[0037] The dispersion medium of the dispersion includes, but is not limited to, one or more of alkanes, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ethers, ketones, esters, furans, pyridines, amides, and sulfones. Specifically, the alkanes include, but are not limited to, one or more of nonane, decane, dodecane, terpenes, butylcyclohexane, n-octane, n-hexane, n-heptane, n-nonane, n-decane, cyclohexane, and cyclopentane; and / or the aromatic hydrocarbons include, but are not limited to, one or more of diethylbenzene, trimethylbenzene, propylbenzene, isopropylbenzene, p-toluene, butylbenzene, and 1-methylnaphthalene or indene; and / or the halogenated hydrocarbons include, but are not limited to, one or more of dichloromethane, chloroform, and carbon tetrachloride; and / or the alcohols include, but are not limited to, one or more of methanol, ethanol, propanol, butanol, ethylene glycol, and glycerol; and / or the ethers include... However, it is not limited to one or more of ethylene glycol monomethyl ether, diethyl ether, and propylene oxide, and / or the ketone compounds include, but are not limited to, one or more of acetone, butanone, and N-methylpyrrolidone, and / or the ester compounds include, but are not limited to, one or more of ethyl formate, ethyl acetate, and propyl acetate, and / or the furan compounds include, but are not limited to, one or more of tetrahydrofuran and 2-methylfuran, and / or the pyridine compounds include, but are not limited to, pyridine, and / or the amide compounds include, but are not limited to, N,N-dimethylformamide, and / or the sulfone compounds include, but are not limited to, dimethyl sulfoxide.

[0038] In some embodiments of this application, the total concentration of the first material and the second material in the dispersion containing the composition is 5 mg / mL to 30 mg / mL.

[0039] In some embodiments of this application, the method for preparing a dispersion containing the composition includes the step of mixing and dispersing a first material and a second material in a dispersion medium. In other embodiments of this application, the method for preparing a dispersion containing the composition includes the step of providing a dispersion containing the first material, and then dispersing the second material in the dispersion containing the first material. In still other embodiments of this application, the method for preparing a dispersion containing the composition includes the step of providing a dispersion containing the second material, and then dispersing the first material in the dispersion containing the second material. The dispersion method includes, but is not limited to, one or more of the following: thermal dispersion (temperature, for example, 50°C to 80°C), ultrasonic dispersion, and stirring dispersion. The dispersion containing the second material is commercially available.

[0040] The deposition methods of the dispersion include, but are not limited to, one or more of the following: spin coating deposition, printing deposition, inkjet printing deposition, blade coating deposition, printing deposition, dip-coating deposition, immersion deposition, spraying deposition, roller coating deposition, casting deposition, slot coating deposition, and strip coating deposition.

[0041] The drying process includes, but is not limited to, one or more of the following: heat treatment and vacuum drying.

[0042] This application also provides an optoelectronic device, which includes, but is not limited to, light-emitting devices, solar cells, or photodetectors, such as... Figure 1 As shown, the optoelectronic device 10 includes an anode 101, a cathode 102, and a functional layer 103. The anode 101 and cathode 102 are disposed opposite to each other, and the functional layer 103 is disposed between the anode 101 and cathode 102. The functional layer 103 includes a plurality of stacked functional sublayers, and at least one functional sublayer is made of a second material. The second material is selected from one or more of a first metal-doped phosphorene and undoped phosphorene. The first metal-doped phosphorene is described above.

[0043] In some embodiments of this application, the materials of the anode 101 and the cathode 102 are independently selected from one or more of metals, carbon materials, and first metal oxide materials. The metals include, but are not limited to, one or more of Al, Ag, Cu, Mo, Au, Ba, Pt, Ca, Ir, Ni, and Mg. The carbon materials include, but are not limited to, one or more of graphite, carbon nanotubes, graphene, and carbon fibers. The first metal oxide materials include, but are not limited to, one or more of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), TiO2, SnO2, ZnO, and In2O3.

[0044] The anode 101 or cathode 102 can also be a composite electrode with a sandwich-like structure. The upper and lower layers are independently selected from a first metal oxide material or a metal sulfide, and the middle layer is a metal, such as one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2. The thickness of the middle layer does not exceed 35 nm. The thickness of the anode 101 can be, for example, 20 nm to 300 nm, and the thickness of the cathode 102 can be, for example, 20 nm to 300 nm.

[0045] To further improve the overall performance of the optoelectronic device 10, in some embodiments of this application, at least one of the functional sublayers further includes a first material, which is selected from organic p-type semiconductor materials. The organic p-type semiconductor material can be referred to the description of organic p-type semiconductor materials above.

[0046] To improve the hole transport efficiency of the optoelectronic device 10, further reference is made to some embodiments of this application. Figure 1The system comprises multiple functional sublayers, including a hole functional layer 1032. The hole functional layer 1032 includes a hole injection layer 10321 and / or a hole transport layer 10322. For the hole functional layer 1032 including both the hole injection layer 10321 and the hole transport layer 10322, the hole injection layer 10321 is closer to the anode 101 than the hole transport layer 10322. The hole injection layer 10321 is made of a second material, or the material is composed of the first material and the second material, wherein the first material is selected from organic hole injection materials; and / or, the hole transport layer 10322 is made of a second material, or the material is composed of the first material and the second material, wherein the second material is selected from organic hole transport materials.

[0047] It should be noted that the hole functional layer 1032 can be a single-layer or multi-layer structure, and the thickness of the hole functional layer 1032 is, for example, 10 nm to 100 nm. In addition to the aforementioned organic hole transport materials and organic hole injection materials, commonly used hole functional materials in this field also include at least one first inorganic compound and / or at least one doped second inorganic compound. The first inorganic compound includes, but is not limited to, graphene, C60, nickel oxide (e.g., NiO), molybdenum oxide (e.g., MoO3), tungsten oxide (e.g., WO3), vanadium oxide (e.g., V2O5), p-type gallium nitride, chromium oxide (e.g., Cr2O3), copper oxide (e.g., CuO or Cu2O), copper sulfide (e.g., CuS), molybdenum sulfide (e.g., MoS2), or tungsten sulfide (e.g., WS2). The doped second inorganic compound... The doping element is selected from one or more of nickel, molybdenum, tungsten, vanadium, chromium, copper, and platinum group metals. The molar amount of the doping element accounts for no more than 50% of the total molar amount of the doped second inorganic compound. The main compound of the doped second inorganic compound includes, but is not limited to, graphene, C60, nickel oxide (e.g., NiO), molybdenum oxide (e.g., MoO3), tungsten oxide (e.g., WO3), vanadium oxide (e.g., V2O5), p-type gallium nitride, chromium oxide (e.g., Cr2O3), copper oxide (e.g., CuO or Cu2O), copper sulfide (e.g., CuS), molybdenum sulfide (e.g., MoS2), or tungsten sulfide (e.g., WS2).

[0048] In some embodiments of this application, see further reference. Figure 1 The multiple functional sublayers also include a light-emitting layer 1031, which is disposed between the hole functional layer 1032 and the cathode. The material of the light-emitting layer 1031 includes one or more of organic light-emitting materials and light-emitting quantum dots. The average thickness of the light-emitting layer 1031 is, for example, 10 nm to 100 nm.

[0049] Among them, organic light-emitting materials include, but are not limited to, one or more of the following: 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridinium(III), 4,4',4”-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridinium, diaromatic anthracene derivatives, stilbene 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 local charge transfer excited state materials, excitopolymer light-emitting materials, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, and polyfluorene and its derivatives.

[0050] The luminescent quantum dots include, but are not limited to, one or more of red, green, and blue quantum dots. Furthermore, the luminescent quantum dots include, but are not limited to, one or more of single-component quantum dots, core-shell quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots, and organic-inorganic hybrid perovskite quantum dots, wherein the core-shell quantum dots have one or more shells. The average particle size of the luminescent quantum dots can be, for example, 2 nm to 20 nm, with examples being 2 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 15 nm, 20 nm, or any value between any two of the aforementioned values.

[0051] For single-component quantum dots and core-shell quantum dots, the material of the single-component quantum dot, the material of the core of the core-shell quantum dot, or the material of the shell of the core-shell quantum dot includes, but is not limited to, at least one of group II-VI compounds, group III-V compounds, group III-VI compounds, group IV-VI compounds, or group I-III-VI compounds. Among them, the II-VI group compounds include, but are not limited to, one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe. III-VI group compounds include, but are not limited to, one or more of In2S3, In2Se3, InGaS3, and InGaSe3. III-V group compounds include, but are not limited to, one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb. Group IV-VI compounds include, but are not limited to, one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe. Group I-III-VI compounds include, but are not limited to, one or more of AgInS, AgInS2, CuInS, CuInS2, AgGaS2, CuGaS2, CuGaO2, AgGaO2, AgAlO2, AgInGaS2, and CuInGaS2.

[0052] For inorganic perovskite quantum dots, the general structural formula is AMX3, where A is Cs. + M is a divalent metal cation, and M includes, but is not limited to, Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - Or I - .

[0053] For organic perovskite quantum dots, the general structural formula is CMX3, where C is a formamidinyl group and M is a divalent metal cation, which may include, but is not limited to, Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - Or I - .

[0054] For organic-inorganic hybrid perovskite quantum dots, the general structural formula is BMX3, where B is selected from organic amine cations, including but not limited to CH3(CH2). n-2 NH 3+ (n≥2) or NH3(CH2) n NH3 2+ (n≥2), M is a divalent metal cation, and M includes, but is not limited to, Pb. 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe2+ 、Ge 2+ Yb 2+ Or Eu 2+ X is a halide anion, including but not limited to Cl. - ,Br - Or I - .

[0055] When the material of the light-emitting layer 1031 includes light-emitting quantum dots, in order to improve the solution processing performance of the light-emitting quantum dots and further enhance the device efficiency of the optoelectronic device 10, in some embodiments of this application, ligands are also attached to the surface of the light-emitting quantum dots. The ligands can be common ligands in the art, including but not limited to C1 to C2. 30 aliphatic carboxylic acid ligands, C6-C 30 Aromatic carboxylic acid ligands, C1-C 30 Aliphatic thiol ligands, C6-C 30 Thiol aromatic ligands, C1-C 30 fatty amine ligands, C6-C 30 Aromatic amine ligands, C1-C 30 Aliphatic phosphine ligands, C6~C 30 Aromatic phosphine ligands and C6-C 30 One or more of aromatic phosphate ligands and halogen ligands.

[0056] Among them, C1~C 30 The aliphatic carboxylic acid ligands include, but are not limited to, one or more of the following: octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, teicosanoic acid, oleic acid, linoleic acid, arachidic acid, arachidonic acid, erucic acid, and docosahexaenoic acid; C6~C 30 Aromatic carboxylic acid ligands include, but are not limited to, one or more of benzoic acid, biphenylic acid, and 1-naphthoic acid. (C1-C2) 30 The aliphatic thiol ligands include, but are not limited to, one or more of hexamethylenetetramine, octanethiol, nonanethiol, decanethiol, undecylthiol, dodecathiol, hexadecylthiol, and octadecylthiol, C6–C6. 30 Thiol aromatic ligands include, but are not limited to, one or more of benzenethiol, triphenylmethanethiol, and p-terphenyl-4,4”-dithiol. C1~C 30 The aliphatic amine ligands include, but are not limited to, one or more of hexylamine, octylamine, dioctylamine, trioctylamine, nonylamine, decylamine, dodecylamine, trideamine, tetradeamine, pentadecylamine, hexadecylamine, heptadecanamine, octadecylamine, and oleylamine, C6-C6. 30 The aromatic amine ligands include, but are not limited to, one or more of aniline, indenepropylamine, 4-octylaniline, and benzidine. (C1-C2)30 The aliphatic phosphine ligands include, but are not limited to, one or more of trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, tridecylphosphine, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide, and tridecylphosphine oxide, C6–C6. 30 Aromatic phosphine ligands include, but are not limited to, one or more of bis(2-diphenylphosphineethyl)phenylphosphine and triphenylphosphine oxide, C6-C6. 30 The aromatic phosphate ligands include, but are not limited to, one or more of tetraethyl p-xylene diphosphate and ethyl diphenyl phosphate. Halogen ligands include, but are not limited to, -Cl, -F, -I, or -Br.

[0057] In some embodiments of this application, see further reference. Figure 1 The multiple functional sub-layers also include an electronic functional layer 1033, which is disposed between the hole functional layer 1032 and the cathode 102. When the optoelectronic device 10 includes a light-emitting layer 1031, the electronic functional layer 1033 is disposed between the light-emitting layer 1031 and the cathode 102.

[0058] The electronic functional layer 1033 can be a single-layer or multi-layer structure, and its thickness is, for example, 10 nm to 100 nm. When the electronic functional layer 1033 is a multi-layer structure, it may include one or more of an electron injection layer, an electron transport layer, and a hole blocking layer. For an electronic functional layer 1033 including an electron injection layer, an electron transport layer, and a hole blocking layer, the electron transport layer is located between the electron injection layer and the hole blocking layer, and the electron injection layer is closer to the cathode 102 than the hole blocking layer. For an electronic functional layer 1033 including an electron transport layer and a hole blocking layer, the electron transport layer is closer to the cathode 102 than the hole blocking layer. For an electronic functional layer 1033 including an electron injection layer and an electron transport layer, the electron injection layer is closer to the cathode 102 than the electron transport layer.

[0059] In some embodiments of this application, the material of the electronic functional layer 1033 includes one or more of the following: a second metal oxide material, a third metal oxide material, a group IIB-VIA semiconductor material, a group IIIA-VA semiconductor material, and a group IB-IIIA-VIA semiconductor material. The second metal oxide material includes, but is not limited to, one or more of ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, and ZrO2, and / or IIB-VIA group semiconductor materials include, but are not limited to, one or more of ZnS, ZnSe, and CdS, and / or IIIA-VA group semiconductor materials include, but are not limited to, one or more of InP and GaP, and / or IB-IIIA-VIA group semiconductor materials include, but are not limited to, one or more of CuInS and CuGaS; and / or the third metal oxide material includes one or more doped metal oxides, wherein the doping element of the doped metal oxide is selected from one or more of Mg, Ca, Zr, W, Ga, Li, Al, Ti, Y, In, and Sn, and the host compound of the doped metal oxide is selected, for example, ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, or ZrO2. Doped metal oxides are selected from one or more of zinc magnesium oxide, zinc calcium oxide, zinc zirconium oxide, zinc gallium oxide, zinc aluminum oxide, zinc lithium oxide, zinc titanium oxide, yttrium zinc oxide, indium tin oxide, and lithium titanium oxide, with examples including ZnO, TiO2, SnO2, BaO, Ta2O3, Al2O3, ZrO2, and Zn. (1-x) Mg x O, Zn (1-x) Ca x O, Zn (1-x) Zr x O, Zn (1-x) Ga x O, Zn (1-x) Al x O, Zn (1-x) Li x O, Al (1-x) Zn x O, Zn (1-x) Ti x O, Zn (1-x) Y x O、In (1-x) Sn x O and Ti (1-x) Li xOne or more of the following materials are selected: 0 < x ≤ 0.5. It is understood that when the electronic functional layer 1033 comprises multiple materials and the electronic functional layer 1033 has a multilayer structure, the multiple materials can all be located in the same layer, or in different layers, or partially in the same layer. It should be noted that the second metal oxide material and the doped metal oxide can be, for example, nanoparticles, nanosheets, nanoneedles, or nanorods, respectively; an example is nanoparticles, with an average particle size of, for example, 2 nm to 50 nm.

[0060] To further improve the device performance of the optoelectronic device 10, in some embodiments of this application, referring to 1, multiple functional layers are composed of a hole injection layer 10321, a hole transport layer 10322, a light-emitting layer 1031, and an electronic functional layer 1033 arranged sequentially. The electronic functional layer 1033 is, for example, an electronic transport layer with a single-layer structure. The material of the hole injection layer 10321 is any of the organic hole injection materials described above. The material of the hole transport layer 10322 is selected from any of the compositions described above or phosphorene doped with a first metal. The average thickness of the hole transport layer 10322 is 10 nm to 40 nm, and the average thickness of the light-emitting layer 1031 is 30 nm to 60 nm.

[0061] It should be noted that the preparation methods for each film layer in optoelectronic devices include, but are not limited to, chemical and / or physical methods. Chemical methods include, but are not limited to, one or more of chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation. Physical methods include, but are not limited to, physical deposition and solution methods. Physical deposition methods include, but are not limited to, one or more of thermal evaporation deposition, electron beam evaporation deposition, magnetron sputtering, multi-arc ion deposition, physical vapor deposition, atomic layer deposition, and pulsed laser deposition. Solution methods include, but are not limited to, one or more of spin coating, printing, inkjet printing, blade coating, dip coating, immersion coating, spraying, roller coating, casting, slot coating, and strip coating. After preparing each film layer of the optoelectronic device, an encapsulation process is required. Encapsulation can be performed using common machine encapsulation or manual encapsulation. In the encapsulation environment, the oxygen and water content are both below 0.1 ppm to ensure the stability of the optoelectronic device.

[0062] This application also provides an electronic device, which includes any of the optoelectronic devices described above, or optoelectronic devices prepared by any of the methods described above. The electronic device can be, for example, any electronic product with a display function, including but not limited to smartphones, tablet personal computers, mobile phones, video phones, e-book readers, laptop PCs, netbook computers, workstations, servers, personal digital assistants, portable multimedia players, MP3 players, mobile medical devices, cameras, game consoles, digital cameras, car navigation systems, electronic billboards, ATMs, smart bracelets, smartwatches, virtual reality (VR) devices, or wearable devices.

[0063] The technical solutions and effects of this application will be described in detail below through specific embodiments, comparative examples and experimental examples. The following embodiments are only some embodiments of this application and are not intended to limit this application.

[0064] Material Example 1

[0065] This embodiment provides a composition and a thin film, the composition being composed of TFB and iron-doped phosphorene, wherein the mass ratio of TFB to iron-doped phosphorene is 50:1, and the atomic percentage of iron in the iron-doped phosphorene is 2.78%.

[0066] The material of the thin film in this embodiment includes the composition of this embodiment. The thin film is prepared by the composition by solution method, including the following steps: providing a substrate, and spin-coating a material dispersion with a concentration of 10 mg / mL on one side of the substrate under a nitrogen atmosphere at room temperature and pressure. The material dispersion is prepared by dispersing the composition of this embodiment in chlorobenzene (TFB, iron-doped phosphorene and chlorobenzene are mixed and ultrasonically dispersed at 60°C for 3 h), and then placed in a constant temperature heat treatment at 170°C under a nitrogen atmosphere for 15 min to solidify into a film, thereby obtaining a thin film with an average thickness of 30 nm.

[0067] The preparation method of iron-doped phosphorene includes the following steps: First, solid phosphorene (purchased from Aladdin, item number B196539) and iron powder are mixed at a phosphorene:iron powder mass ratio of 1:0.57 to obtain a mixture; then, the mixture is placed in a ball mill, with the weight of the milling media (agate balls) in the ball mill being 50 times the weight of the mixture, and the ball mill speed is set to 400 r / min for 70 min to obtain iron-doped phosphorene. According to first-principles calculations, the band gap of the iron-doped phosphorene in this embodiment is 0.48 eV.

[0068] Material Example 2

[0069] This embodiment provides a composition and a thin film. Compared with the composition in Material Example 1, the only difference in this embodiment is that the mass ratio of TFB to iron-doped phosphorene is 70:1.

[0070] Compared to the film in Material Example 1, the only difference in this embodiment is that the material of the film in this embodiment includes the composition of this embodiment. The preparation method of the film in this embodiment is the same as that in Material Example 1.

[0071] Material Example 3

[0072] This embodiment provides a composition and a thin film. Compared with the composition in Material Example 1, the only difference in this embodiment is that the mass ratio of TFB to iron-doped phosphorene is 30:1.

[0073] Compared to the film in Material Example 1, the only difference in this embodiment is that the material of the film in this embodiment includes the composition of this embodiment. The preparation method of the film in this embodiment is the same as that in Material Example 1.

[0074] Material Example 4

[0075] This embodiment provides a composition and a thin film. Compared with the composition in Material Example 1, the only difference in this embodiment is that the atomic percentage of iron in the iron-doped phosphorene is 1%.

[0076] Compared to the film in Material Example 1, the only difference in this embodiment is that the material of the film in this embodiment includes the composition of this embodiment. The preparation method of the film in this embodiment is the same as that in Material Example 1.

[0077] Compared to the preparation method of iron-doped phosphorene in Material Example 1, the difference in the preparation method of iron-doped phosphorene in this example is that: the phrase "mixing solid phosphorene (purchased from Aladdin, item number B196539) and iron powder at a mass ratio of phosphorene to iron powder of 1:0.57" is replaced with "mixing solid phosphorene (purchased from Aladdin, item number B196539) and iron powder at a mass ratio of phosphorene to iron powder of 1:0.204".

[0078] Material Example 5

[0079] This embodiment provides a composition and a thin film. Compared with the composition in Material Example 1, the only difference in this embodiment is that the atomic percentage of iron in the iron-doped phosphorene is 5%.

[0080] Compared to the film in Material Example 1, the only difference in this embodiment is that the material of the film in this embodiment includes the composition of this embodiment. The preparation method of the film in this embodiment is the same as that in Material Example 1.

[0081] Compared to the preparation method of iron-doped phosphorene in Material Example 1, the difference in the preparation method of iron-doped phosphorene in this example is that: the phrase "mixing solid phosphorene (purchased from Aladdin, item number B196539) and iron powder at a phosphorene:iron powder mass ratio of 1:0.57" is replaced with "mixing solid phosphorene (purchased from Aladdin, item number B196539) and iron powder at a phosphorene:iron powder mass ratio of 1:1.02".

[0082] Material Example 6

[0083] This embodiment provides a composition and a thin film. Compared with the composition in Material Example 1, the only difference in this embodiment is that the iron-doped phosphorene is replaced with manganese-doped phosphorene, and the atomic percentage of Mn in the manganese-doped phosphorene is 2.78%.

[0084] Compared to the film in Material Example 1, the only difference in this embodiment is that the material of the film in this embodiment includes the composition of this embodiment. The preparation method of the film in this embodiment is the same as that in Material Example 1.

[0085] The preparation method of manganese-doped phosphorene includes the following steps: First, solid phosphorene (purchased from Aladdin, item number B196539) and manganese powder (purchased from Aladdin, item number M118819) are mixed at a mass ratio of phosphorene to manganese powder of 1:0.58 to obtain a mixture; then, the mixture is placed in a ball mill, with the weight of the milling media (agate balls) in the ball mill being 50 times the weight of the mixture, and the ball mill speed is set to 400 r / min for 70 min to obtain manganese-doped phosphorene. According to first-principles calculations, the band gap of the manganese-doped phosphorene in this embodiment is 0.43 eV.

[0086] Material Example 7

[0087] This embodiment provides a composition and a thin film. Compared with the composition in Material Example 1, the only difference in this embodiment is that the iron-doped phosphorene is replaced with cobalt-doped phosphorene, and the atomic percentage of Co in the cobalt-doped phosphorene is 2.78%.

[0088] Compared to the film in Material Example 1, the only difference in this embodiment is that the material of the film in this embodiment includes the composition of this embodiment. The preparation method of the film in this embodiment is the same as that in Material Example 1.

[0089] The preparation method of cobalt-doped phosphorene includes the following steps: First, solid phosphorene (purchased from Aladdin, item number B196539) and cobalt powder (purchased from Aladdin, item number C104957) are mixed at a phosphorene:cobalt powder mass ratio of 1:0.54 to obtain a mixture; then, the mixture is placed in a ball mill, with the weight of the milling media (agate balls) in the ball mill being 50 times the weight of the mixture, and the ball mill speed is set to 400 r / min for 70 min to obtain manganese-doped phosphorene. Calculations using first-principles methods show that the band gap of the cobalt-doped phosphorene in this embodiment is 0.69 eV.

[0090] Material Example 8

[0091] This embodiment provides a composition and a thin film. Compared with the composition in Material Example 1, the only difference in this embodiment is that the iron-doped phosphorene is replaced with undoped phosphorene.

[0092] Compared to the film in Material Example 1, the only difference in this embodiment is that the material of the film in this embodiment includes the composition of this embodiment. The preparation method of the film in this embodiment is the same as that in Material Example 1.

[0093] Material Example 9

[0094] This embodiment provides a composition and a film. The only difference between the composition in Material Example 1 and the composition in this embodiment is that TFB is replaced with "polypyrrole".

[0095] Compared to the film in Material Example 1, the only difference in this embodiment is that the material of the film in this embodiment includes the composition of this embodiment. The preparation method of the film in this embodiment is the same as that in Material Example 1.

[0096] Material Comparison Example 1

[0097] This comparative example provides a thin film made of TFB material, and the average thickness of the thin film is 30 nm.

[0098] The preparation method of the thin film in this comparative example includes the following steps: providing a substrate, spin-coating a TFB-chlorobenzene dispersion with a concentration of 10 mg / mL on one side of the substrate under a nitrogen atmosphere at room temperature and pressure, and then placing it under a nitrogen atmosphere at 170°C for 15 min to cure and form a film.

[0099] Material Comparison Example 2

[0100] This comparative example provides a thin film made of phosphorene with an average thickness of 30 nm.

[0101] The preparation method of the thin film in this comparative example includes the following steps: providing a substrate, spin-coating a phosphorene dispersion (purchased from Aladdin, catalog number B463005) on one side of the substrate under a nitrogen atmosphere at room temperature and pressure, and then placing it under a nitrogen atmosphere at 170°C for 15 minutes to cure and form a film.

[0102] Material Comparison Example 3

[0103] This comparative example provides a composition and a film, the composition comprising NiO nanoparticles (average particle size of 5 nm) and phosphorene, wherein the mass ratio of NiO nanoparticles to phosphorene is 50:1.

[0104] The material of the thin film in this comparative example includes the composition of this comparative example. The thin film is prepared by the composition by a solution method, including the following steps: providing a substrate, and spin-coating a material dispersion with a concentration of 10 mg / mL on one side of the substrate under a nitrogen atmosphere at room temperature and pressure. The material dispersion is prepared by dispersing the composition of this comparative example in chlorobenzene (NiO nanoparticles, phosphorene and chlorobenzene are mixed and ultrasonically dispersed at 60°C for 3 h), and then placed in a constant temperature heat treatment at 170°C under a nitrogen atmosphere for 15 min to solidify into a film, thereby obtaining a thin film with an average thickness of 30 nm.

[0105] Device Example 1

[0106] This embodiment provides an optoelectronic device and its fabrication method. The optoelectronic device is a quantum dot light-emitting diode with a positive-position structure, such as... Figure 1 As shown, in the direction from bottom to top, the optoelectronic device 10 includes an anode 101, a functional layer 103, and a cathode 102 stacked sequentially. The functional layer 103 includes a hole functional layer 1032, a light-emitting layer 1031, and an electronic functional layer 1033 stacked sequentially. The electronic functional layer 1033 is closer to the cathode 102 than the hole functional layer 1032. The hole functional layer 1032 is composed of a hole injection layer 10321 and a hole transport layer 10322 stacked sequentially. The hole injection layer 10321 is closer to the anode 101 than the hole transport layer 10322. The electronic functional layer 1033 is a single-layer structure and is an electron transport layer.

[0107] The materials and thicknesses of each layer in optoelectronic device 10 are as follows:

[0108] The anode 101 is made of ITO and has an average thickness of 50 nm.

[0109] The cathode 102 is made of Ag and has an average thickness of 35 nm.

[0110] The material of the light-emitting layer 1031 is ZnCdS (core) / ZnS (shell) light-emitting quantum dots, the emission wavelength of the light-emitting quantum dots is 470nm, and the average thickness of the light-emitting layer 1031 is 40nm;

[0111] The electronic functional layer 1033 is made of nano-Zn. 0.85 Mg 0.15 O (average particle size is 5nm), and the average thickness of the electronic functional layer 1033 is 40nm;

[0112] The hole injection layer 10321 is made of PEDOT:PSS, and the average thickness of the hole injection layer 10321 is 100nm.

[0113] The hole transport layer 10322 is made of the composition in Material Example 1, and the average thickness of the hole transport layer 10322 is 30 nm.

[0114] The fabrication method of the light-emitting device in this embodiment includes the following steps:

[0115] S10.1 Provide a substrate (material is glass and average thickness is 1mm), sputter ITO on one side of the substrate to obtain an ITO layer, wipe the surface of the ITO layer with a cotton swab dipped in a small amount of soapy water to remove visible impurities, and then sequentially ultrasonically clean the substrate including ITO with deionized water for 15min, acetone for 15min, ethanol for 15min and isopropanol for 15min, dry it and then perform ultraviolet-ozone surface treatment for 15min to obtain a substrate containing an anode.

[0116] S10.2 Under normal temperature and pressure air environment, spin-coat PEDOT:PSS aqueous solution on the side of the anode away from the substrate, and then place it at 150℃ for constant temperature heat treatment for 15 min to solidify into a film to obtain a hole injection layer.

[0117] S10.3, Referring to the thin film preparation method in Example 1, a hole transport layer is formed on the side of the hole injection layer away from the anode;

[0118] S10.4 Under a nitrogen atmosphere at normal temperature and pressure, spin-coat a quantum dot-n-octane solution with a concentration of 40 mg / mL onto the side of the hole transport layer away from the hole injection layer, and then place it under a vacuum of no more than 3 × 10⁻⁶. -4 The light-emitting layer was vacuum dried in the vapor deposition chamber for 15 minutes, and then placed in a nitrogen atmosphere and constant temperature heat treatment at 100°C for 10 minutes to obtain the light-emitting layer.

[0119] S10.5 Under a nitrogen atmosphere at room temperature and pressure, spin-coat nano-Zn with a concentration of 30 mg / mL onto the side of the luminescent layer away from the hole transport layer. 0.85 Mg 0.15 O-ethanol solution, and then placed in a nitrogen atmosphere and heat-treated at 100°C for 15 min to solidify into a film to obtain an electronic functional layer;

[0120] S10.6 Place the prefabricated device after completing step S10.5 in a vacuum with a vacuum degree not exceeding 3×10⁻⁶. -4 In the vapor deposition chamber of Pa, Ag is thermally vaporized on the side of the electronic functional layer away from the light-emitting layer through a mask to obtain the cathode, and then encapsulated with epoxy resin to obtain the optoelectronic device.

[0121] Device Examples 2 to 9

[0122] Device Example n is essentially the same as Device Example 1, except that: in Device Example n, the material of the hole transport layer is the composition in Material Example n, and correspondingly, the preparation method of the hole transport layer in Device Example n is the same as the preparation method of the thin film in Material Example n, where n is a positive integer from 2 to 9. For example, in Device Example 2, the material of the hole transport layer is the composition in Material Example 2, and the preparation method of the hole transport layer in Device Example 2 is the same as the preparation method of the thin film in Material Example 2; in Device Example 3, the material of the hole transport layer is the composition in Material Example 3, and the preparation method of the hole transport layer in Device Example 3 is the same as the preparation method of the thin film in Material Example 3, and so on.

[0123] Device Example 10

[0124] This embodiment provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the hole transport layer is made of iron-doped phosphorene, and the atomic percentage of iron in the iron-doped phosphorene is 2.78%.

[0125] Compared with the method for preparing the optoelectronic device in Device Example 1, the method for preparing the optoelectronic device in this example differs in that step S10.3 is replaced with "under a nitrogen atmosphere at room temperature and pressure, spin-coating a 10 mg / mL iron-doped phosphorene-chlorobenzene dispersion onto the side of the hole injection layer away from the anode, and then heat-treating it at 170°C under a nitrogen atmosphere for 15 min to solidify it into a film, thereby obtaining the hole transport layer".

[0126] Device Example 11

[0127] This embodiment provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Embodiment 1, the difference of the optoelectronic device in this embodiment is that the average thickness of the hole transport layer is 10 nm and the average thickness of the light-emitting layer is 60 nm.

[0128] The fabrication method of the optoelectronic device in this embodiment is the same as that in Device Example 1.

[0129] Device Comparison Example 1

[0130] This comparative example provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this comparative example is that the material of the hole transport layer is replaced with "TFB".

[0131] Compared with the preparation method of the optoelectronic device in Material Example 1, the difference in the preparation method of the optoelectronic device in this comparative example is that step S10.3 is replaced with "In a nitrogen atmosphere at room temperature and pressure, spin-coating a TFB-chlorobenzene dispersion with a concentration of 10 mg / mL on the side of the hole injection layer away from the anode, and then placing it under a nitrogen atmosphere at 170°C for constant temperature heat treatment for 15 min to solidify into a film and obtain a hole transport layer".

[0132] Device Comparison Example 2

[0133] This comparative example provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this comparative example is that the material of the hole transport layer is replaced with "phosphene".

[0134] Compared with the preparation method of the optoelectronic device in Material Example 1, the difference in the preparation method of the optoelectronic device in this comparative example is that step S10.3 is replaced with "under a nitrogen atmosphere at room temperature and pressure, a phosphorene-chlorobenzene dispersion with a concentration of 10 mg / mL is spin-coated on the side of the hole injection layer away from the anode, and then placed in a nitrogen atmosphere at 170°C for constant temperature heat treatment for 15 min to solidify into a film and obtain a hole transport layer".

[0135] Device Comparison Example 3

[0136] This comparative example provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this comparative example is that the material of the hole transport layer is replaced with the composition in Material Comparative Example 3.

[0137] Compared to the method for preparing the optoelectronic device in Material Example 1, the method for preparing the optoelectronic device in this comparative example differs in that: referring to the method for preparing the thin film in Material Comparative Example 3, a hole transport layer is formed on the side of the hole injection layer away from the anode.

[0138] Device Comparison Example 4

[0139] This comparative example provides an optoelectronic device and its fabrication method. Compared with the optoelectronic device in Device Example 1, the difference in the optoelectronic device in this comparative example is that the material of the hole transport layer is replaced with polypyrrole.

[0140] Compared with the preparation method of the optoelectronic device in Material Example 1, the difference in the preparation method of the optoelectronic device in this comparative example is that step S10.3 is replaced with "in a nitrogen atmosphere at room temperature and pressure, spin-coating a polypyrrole-chlorobenzene dispersion with a concentration of 10 mg / mL on the side of the hole injection layer away from the anode, and then placing it under a nitrogen atmosphere at 170°C for constant temperature heat treatment for 15 min to solidify into a film and obtain a hole transport layer".

[0141] Experimental Example

[0142] The performance of the optoelectronic devices in Device Examples 1 to 11 and Device Comparative Examples 1 to 4 after 1 hour of packaging was tested. The performance tests were conducted in an environment with a temperature of 25°C and a relative humidity of 50%.

[0143] The testing instruments include the Fostar FPD optical characteristic measurement equipment and the external quantum efficiency optical testing instrument. The Fostar FPD optical characteristic measurement equipment is an efficiency testing system constructed from components such as a Marine Optics USB2000, a LabVIEW-controlled QE-PRO spectrometer, a Keithley 2400, a high-precision digital source meter Keithley 6485, a 50μm inner diameter optical fiber, device test probes and fixtures, various connecting cables and data cards, an efficiency testing cassette, and a data acquisition system. This system acquires the turn-on voltage (Ub) of each optoelectronic device. T The parameters such as current, brightness, and emission spectrum are obtained, and then key parameters such as external quantum efficiency and power efficiency are calculated.

[0144] The current efficiency detection method includes the following steps: intermittently acquiring the brightness values ​​of the photoelectric device within the driving voltage range of 0V to 8V, with the acquired luminous area being 0.04cm². 2 The initial voltage for acquiring brightness is 3V, and measurements are taken every 0.2V. The brightness value acquired each time is divided by the corresponding current density to obtain the current efficiency of the optoelectronic device under that acquisition condition. The maximum current efficiency (CE) is then obtained. max The current density of the optoelectronic device at 1000 nits (J@1000nit, A / m) was obtained. 2 ).

[0145] The device lifetime testing method includes the following steps: Under constant current (2mA) driving, a 128-channel QLED lifetime testing system is used to perform electroluminescence lifetime analysis on each optoelectronic device, record the time (T95,h) required for each optoelectronic device to decay from maximum brightness to 95%, and calculate the time (T95@1000nit,h) required for each optoelectronic device to decay from 100% brightness to 95% brightness at 1000nit using the decay fitting formula.

[0146] The formula for calculating device lifetime is as follows:

[0147]

[0148] In the above formula, T95 L For longer lifespan at low brightness, T95 H For the measured lifetime under high brightness, L H To accelerate the device to its maximum brightness, L LThe value is 1000 nits, and A is the acceleration factor, which is usually between 1.6 and 2. In this experimental example, the value of A for the optoelectronic device is 1.7.

[0149] The performance test data for each optoelectronic device are detailed in Table 1 below:

[0150] Table 1

[0151]

[0152] As shown in Table 1, compared with the optoelectronic devices in Device Comparison Examples 1 to 4, the optoelectronic devices in Device Examples 1 to 9 and Device Example 11 have better overall performance; compared with the optoelectronic device in Device Comparison Example 2, the optoelectronic device in Device Example 9 has better overall performance.

[0153] Taking the optoelectronic devices in Device Example 1 and Device Comparative Example 1 as examples, the U of the optoelectronic device in Device Example 1 T Comparison of the U-type optoelectronic device in Example 1 T Low 1.1V, and the CE of the optoelectronic device in Device Example 1 max The CE of the optoelectronic device in Comparative Example 1 max The T95@1000nit of the optoelectronic device in Device Example 1 is 1.3 times that of the optoelectronic device in Device Example 1, and the T95@1000nit of the optoelectronic device in Device Example 1 is 1.9 times that of the optoelectronic device in Device Comparative Example 1. Furthermore, the J@1000nit of the optoelectronic device in Device Example 1 is 64.3% of the J@1000nit of the optoelectronic device in Device Comparative Example 1. The lower J@1000nit of the optoelectronic device in Device Example 1 compared to the J@1000nit of the optoelectronic device in Device Comparative Example 1 indicates that the optoelectronic device in Device Example 1 has higher device efficiency, requiring only a smaller current density to achieve a brightness of 1000nit. This demonstrates that the optoelectronic device in Device Example 1 has lower resistance and higher electron-hole recombination efficiency, further proving that the hole transport material in the optoelectronic device in Device Example 1 has higher conductivity.

[0154] This demonstrates that using the composition of this application as the hole transport layer material in optoelectronic devices can improve device efficiency and lifetime. In Comparative Example 1, the hole transport material is TFB, and in Comparative Example 4, the hole transport material is polypyrrole. Both TFB and polypyrrole are organic hole transport materials. Organic hole transport materials have the advantage of high film quality, but they also have low conductivity and a large band gap difference between the organic hole transport material and the luminescent quantum dots, resulting in low hole transport efficiency. Consequently, the overall performance of the optoelectronic devices in Comparative Examples 1 and 4 is poor. In Comparative Example 2, the hole transport material is phosphorene, which leads to a "darkening" problem in the optoelectronic device, thus reducing device efficiency and lifetime. In Comparative Example 3, the hole transport material is NiO nanoparticles and phosphorene. Due to the inclusion of NiO nanoparticles, the film quality of the hole transport layer is poor, resulting in the overall performance of the optoelectronic device being inferior to that of Device Examples 1 to 8 and Device Example 10.

[0155] The above provides a detailed description of a composition, thin film, and optoelectronic device provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the embodiments above are only for the purpose of helping to understand the technical solutions and core ideas of this application. Those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A composition, characterized in that, The composition includes a first material and a second material, wherein the first material is selected from organic p-type semiconductor materials, and the second material is selected from one or more of undoped phosphorene and phosphorene doped with a first metal element.

2. The composition according to claim 1, characterized in that, The mass ratio of the second material to the first material is 1:(30-70); And / or, in the phosphorene doped with the first metal element, the atomic percentage of the first metal element is 1% to 5%; And / or, the first metal element-doped phosphorene has a layered structure, and the number of layers in the layered structure is 1 to 10; optionally, the average sheet diameter of the first metal element-doped phosphorene is 100 nm to 200 nm.

3. The composition according to claim 1, characterized in that, The first metallic element is selected from one or more of Group IA metallic elements, Group IIA metallic elements, Group IIIA metallic elements, Group IVA metallic elements, Group VA metallic elements, and transition metal elements; Optionally, the first metal element is selected from one or more of Cr, Mg, Fe, Co and Ni, and / or the band gap of the phosphorene doped with the first metal element is 0.4 eV to 2 eV.

4. The composition according to any one of claims 1 to 3, characterized in that, The organic P-type semiconductor material is selected from one or more of organic hole transport materials and organic hole injection materials; The organic hole injection material is selected from one or more of poly(3,4-vinyldioxythiophene):poly(styrene sulfonic acid), copper phthalocyanine, titanium phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene; And / or, the organic hole transport material is selected from polypyrrole, polyaniline, 3-hexyl-substituted polythiophene, poly(9-vinylcarbazole), 4,4'-bis(9-carbazole)biphenyl, poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N... -(4-sec-butylphenyl)diphenylamine)], poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-di-n-octylfluorenyl-2,7-diyl)], 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4”-tris(carbazole-9-yl)triphenylamine, 4,4',4’-tris(2 N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine, N,N'-bis(3-methylphenyl)-N One or more of N'-diphenyl-9,9-spirodifluorene-2,7-diamine, N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirodi[9H-fluorene]-2,7-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene.

5. The composition according to claim 4, characterized in that, The first material is selected from one or more of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], polypyrrole, and polyaniline, and the second material is selected from Fe-doped phosphorene.

6. A thin film, characterized in that, The material of the thin film includes a composition comprising a first material and a second material, wherein the first material is selected from organic p-type semiconductor materials and the second material is selected from one or more of undoped phosphorene and phosphorene doped with a first metal element.

7. The thin film according to claim 6, characterized in that, The mass ratio of the second material to the first material is 1:(30-70); And / or, in the phosphorene doped with the first metal element, the atomic percentage of the first metal element is 1% to 5%; And / or, the first metal element-doped phosphorene has a layered structure, and the number of layers in the layered structure is 1 to 10; optionally, the average sheet diameter of the first metal element-doped phosphorene is 100 nm to 200 nm. And / or, the first metal element is selected from one or more of Group IA metal elements, Group IIA metal elements, Group IIIA metal elements, Group IVA metal elements, Group VA metal elements and transition metal elements; optionally, the first metal element is selected from one or more of Cr, Mg, Fe, Co and Ni, and / or the band gap of the phosphorene doped with the first metal element is 0.4 eV to 2 eV. And / or, the organic p-type semiconductor material is selected from one or more of organic hole transport materials and organic hole injection materials; wherein, the organic hole injection material is selected from one or more of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), copper phthalocyanine, titanium phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, and / or the organic hole transport material Selected from polypyrrole, polyaniline, 3-hexyl-substituted polythiophene, poly(9-vinylcarbazole), 4,4'-bis(9-carbazole)biphenyl, poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT- (9,9-Di-n-octylfluorenyl-2,7-diyl)], 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4”-tris(carbazole-9-yl)triphenylamine, 4,4',4'-tris(2-naphthylphenylamino)triphenylamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-bis[ [4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirodifluorene-2,7-diamine, N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirodi[9H-fluorene]-2,7-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and 2,2',7,7'-tetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene, one or more of these.

8. The thin film according to claim 7, characterized in that, The first material is selected from one or more of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], polypyrrole, and polyaniline, and the second material is selected from Fe-doped phosphorene.

9. A photoelectric device, comprising an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode, characterized in that, The functional layer includes a plurality of functional sublayers stacked together, and at least one of the functional sublayers is made of a second material, the second material being selected from one or more of first metal-doped phosphorene and undoped phosphorene.

10. The optoelectronic device according to claim 9, characterized in that, The material of at least one of the functional sublayers further includes a first material, the first material being selected from organic p-type semiconductor materials; And / or, in the phosphorene doped with the first metal element, the atomic percentage of the first metal element is 1% to 5%; And / or, the phosphorene doped with the first metal element has a layered structure, and the number of layers in the layered structure is from 1 to 10. And / or, the first metallic element is selected from one or more of Group IA metallic elements, Group IIA metallic elements, Group IIIA metallic elements, Group IVA metallic elements, Group VA metallic elements, and transition metallic elements; And / or, the first metal element is selected from one or more of Group IA metals, Group IIA metals, Group IIIA metals, Group IVA metals, Group VA metals, and transition metals.

11. The optoelectronic device according to claim 10, characterized in that, The average sheet diameter of the phosphorene doped with the first metal element is 100 nm to 200 nm. And / or, the first metallic element is selected from one or more of Cr, Mg, Fe, Co and Ni; And / or, the band gap of the phosphorene doped with the first metal element is 0.4 eV to 2 eV; And / or, the organic p-type semiconductor material is selected from one or more of organic hole transport materials and organic hole injection materials; wherein, the organic hole injection material is selected from one or more of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), copper phthalocyanine, titanium phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene, and / or the organic hole transport material Selected from polypyrrole, polyaniline, 3-hexyl-substituted polythiophene, poly(9-vinylcarbazole), 4,4'-bis(9-carbazole)biphenyl, poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT- (9,9-Di-n-octylfluorenyl-2,7-diyl)], 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4”-tris(carbazole-9-yl)triphenylamine, 4,4',4'-tris(2-naphthylphenylamino)triphenylamine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-bis[ [4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirodifluorene-2,7-diamine, N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirodi[9H-fluorene]-2,7-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] and 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene; And / or, the mass ratio of the second material to the first material is 1:(30-70).

12. The optoelectronic device according to claim 10, characterized in that, The plurality of said functional sublayers include a hole functional layer, the hole functional layer including a hole injection layer and / or a hole transport layer, wherein for a hole functional layer including the hole injection layer and the hole transport layer, the hole injection layer is closer to the anode than the hole transport layer; The hole injection layer is made of a second material, or the hole injection layer is composed of a first material and a second material. The first material is selected from organic hole injection materials, and the organic hole injection material is selected from one or more of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid), copper phthalocyanine, titanium phthalocyanine, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene. And / or, the material of the hole transport layer includes a second material, or the material of the hole transport layer is composed of the first material and the second material, wherein the first material is selected from organic hole transport materials, and the organic hole transport material is selected from polypyrrole, polyaniline, 3-hexyl-substituted polythiophene, poly(9-vinylcarbazole), 4,4'-bis(9-carbazole)biphenyl, poly[bis(4-phenyl)(4-butylphenyl)amine], 4,4'-cyclohexylbis[N [N-Di(4-methylphenyl)aniline], poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)], poly[(N,N'-(4-n-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine)-ALT-(9,9-di-n-octylfluorenyl-2,7-diyl)], 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4”-Tris(carbazole-9-yl)triphenylamine, 4,4',4'-Tris(2-naphthylphenylamino)triphenylamine, N,N'-Diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, N,N'-Diphenyl-N,N'-Di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-Bis[4-(diphenylamino)phenyl]-N,N'-diphenylbenzidine, One or more of N,N'-bis(3-methylphenyl)-N,N'-diphenyl-9,9-spirodifluorene-2,7-diamine, N2,N7-di-1-naphthyl-N2,N7-diphenyl-9,9'-spirodi[9H-fluorene]-2,7-diamine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene.

13. The optoelectronic device according to claim 12, characterized in that, The plurality of functional sublayers further include a light-emitting layer disposed between the hole functional layer and the cathode, wherein the material of the light-emitting layer includes one or more of organic light-emitting materials and light-emitting quantum dots; And / or, the plurality of said functional sublayers further include an electronic functional layer disposed between the hole functional layer and the cathode, the electronic functional layer including an electron injection layer and / or an electron transport layer, wherein for an electronic functional layer including the electron injection layer and the electron transport layer, the electron injection layer is closer to the cathode than the electron transport layer; And / or, the plurality of functional layers are composed of a hole injection layer, a hole transport layer, a light-emitting layer and an electronic functional layer arranged sequentially; wherein, the material of the hole injection layer is the organic hole injection material, and the material of the hole transport layer is selected from one or more of the composition and the first metal-doped phosphorene; optionally, the average thickness of the hole transport layer is 10nm to 40nm, and / or the average thickness of the light-emitting layer is 30nm to 60nm.

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