WO2024255862A1 - 薄膜及其制备方法及光电器件 - Google Patents

薄膜及其制备方法及光电器件 Download PDF

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WO2024255862A1
WO2024255862A1 PCT/CN2024/099305 CN2024099305W WO2024255862A1 WO 2024255862 A1 WO2024255862 A1 WO 2024255862A1 CN 2024099305 W CN2024099305 W CN 2024099305W WO 2024255862 A1 WO2024255862 A1 WO 2024255862A1
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preparation
hole
electrode
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additive
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曹聪聪
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TCL Technology Group Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application relates to the field of semiconductors, and in particular to a thin film and a preparation method thereof, and a photoelectric device.
  • Some organic materials such as polystyrene sulfonate (PEDOT:PSS), poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4′-(N-(4-sec-butylphenyl)diphenylamine)] (TFB), etc., usually have hole injection and hole transport properties and are suitable for preparing hole functional film layers. However, the hole mobility of the films made of these materials is usually low, which is not suitable for occasions with high requirements for hole injection and transport properties.
  • the present application provides a thin film, a preparation method thereof, and a photoelectric device.
  • the present application provides a method for preparing a thin film, comprising the following steps:
  • the mixed solution comprising a hole functional material and an additive
  • the additive includes a compound having a structure shown in formula (1):
  • ring A includes one or more of an aromatic ring having 6 to 40 ring carbon atoms and a heteroaromatic ring having 6 to 40 ring atoms, and n is a positive integer;
  • Each occurrence of X is independently selected from one or more of hydrogen, deuterium, and an electron donating group.
  • the electron donating group includes -NH 2 , A combination of one or more of C1-C3 alkyl and C1-C3 alkoxy.
  • ring A includes one or more of an aromatic ring having 6 to 20 ring carbon atoms and a heteroaromatic ring having 6 to 20 ring atoms.
  • ring A is selected from one or more of the rings of any structure shown in formula (2) to (7):
  • n is 1-4.
  • n 1 or 2.
  • the boiling point of the additive is greater than or equal to 100°C and less than 200°C.
  • the additive includes one or more compounds having a structure shown in any one of the following formulae (8) to (16):
  • X is independently selected from the electron donating group each time it appears.
  • the additive includes one or more compounds having a structure shown in any one of formulas (11) to (16):
  • the mass of the additive accounts for 5-10% of the total mass of the additive and the hole functional material.
  • the hole functional material includes a hole transport material or a hole injection material
  • the hole transport material is selected from poly [(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl) diphenylamine))], poly (4-butylphenyl-diphenylamine), poly (triarylamine), polypyrrole, poly [N,N'-bis (4-butylphenyl) -N,N'-bis (phenyl) - benzidine], poly (p-) phenylene vinylene, poly [2-methoxy- At least one of poly[5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], PEDOT:PSS and its
  • the annealing temperature is 200-230°C.
  • the annealing time is 15 to 45 minutes.
  • the mixed solution further includes a solvent
  • the solvent includes one or more of an alcohol solvent, chloroform, chlorobenzene, and dichlorobenzene.
  • the concentration of the hole functional material is 2 to 15 mg/ml.
  • the present application proposes a thin film, wherein the material of the thin film includes a hole functional material, and the root mean square roughness of the thin film is 0.3 to 1.5.
  • the hole mobility of the film is 10 -3 to 10 -1 cm 2 V -1 s -1 .
  • the present application provides an optoelectronic device, comprising a first electrode, a hole functional layer and a second electrode, wherein the hole functional layer comprises one or two layers of a hole injection layer and a hole transport layer, and the At least one of the hole functional layers includes the film as described above, or includes a film prepared by the preparation method described above.
  • the first electrode and the second electrode are each independently selected from 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 is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide;
  • the composite electrode of metal and metal oxide is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , TiO 2
  • the optoelectronic device further comprises a light-emitting layer, the light-emitting layer is disposed between the first electrode and the hole functional layer, or the light-emitting layer is disposed between the second electrode and the hole functional layer, the material of the light-emitting layer is selected from one or more of an organic light-emitting material and a quantum dot light-emitting material, the organic light-emitting material is selected from 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridine iridium(III), 4,4',4"-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl) One or more of iridium pyridine, diaromatic anthracene derivatives, aromatic distilbene derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, T
  • FIG1 is a schematic flow chart of a method for preparing a thin film according to an embodiment of the present application
  • FIG2 is a schematic diagram of the structure of an optoelectronic device proposed in one embodiment of the present application.
  • FIG3 is a schematic structural diagram of an optoelectronic device proposed in another embodiment of the present application.
  • FIG4 is an AFM image of the control group in Experimental Example 1;
  • FIG5 is an AFM image of the experimental group in Experimental Example 1;
  • 100 - photoelectric device 10 - anode; 20 - light-emitting layer; 30 - electron transport layer; 40 - cathode; 50 - hole transport layer; 60 - hole injection layer.
  • 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.
  • At least one means one or more
  • plural means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • 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.
  • “at least one of a, b, or c” can all mean: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, c can be single or multiple, respectively.
  • ring-joined refers to a situation in which two rings in a compound share two directly connected carbon atoms and are bonded to each other, wherein the two shared carbon atoms are common carbon atoms.
  • the total number of common carbon atoms is the number of common carbon atoms; for example, naphthalene is a cyclic ring of two benzene rings, and the number of common carbon atoms is 2.
  • the "number of ring atoms” refers to the number of atoms among the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) obtained by bonding atoms to form a ring.
  • a structural compound e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound
  • the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.
  • the "number of ring carbon atoms" refers to the number of atoms among the carbon atoms constituting the ring itself.
  • the number of ring carbon atoms of a benzene ring is 6, and the number of ring carbon atoms of a thienyl group is 4.
  • aromatic ring or aromatic ring refers to a cyclic compound containing a benzene ring, which can be a single ring or a condensed ring formed by multiple rings.
  • aromatic ring system For a polycyclic ring, at least one is an aromatic ring system.
  • aromatic ring with 6 to 40 ring atoms refers to an aromatic ring containing 6 to 40 ring atoms, preferably an aromatic ring with 6 to 30 ring atoms, more preferably an aromatic ring with 6 to 18 ring atoms, and particularly preferably an aromatic ring with 6 to 14 ring atoms; suitable examples include, but are not limited to: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, fluorene ring, indene ring, etc.
  • heteromatic ring or heteroaromatic ring means that at least one carbon atom on the basis of an aromatic ring is replaced by a non-carbon atom, and the non-carbon atom can be an N atom, an O atom, an S atom, etc.
  • Suitable examples include, but are not limited to, thiophene, furan, pyrrole, imidazole, diazole, triazole, pyridine, bipyridine, pyrimidine, triazine, acridine, pyridazine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, phthalazine, pyridopyrimidine, pyridopyrazine, benzothiophene, benzofuran, indole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, o-naphthyridine, phenanthridine, primary idine, quinazolinone, dibenzothiophene, dibenzo
  • alkyl may mean a straight chain alkyl or a branched chain alkyl.
  • C1-3 alkyl refers to an alkyl group containing 1 to 3 carbon atoms, and each occurrence may be independently a C1 alkyl, a C2 alkyl or a C3 alkyl.
  • Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, etc.
  • an alkoxy group has a structural feature of the formula -OR, wherein R refers to an alkyl group.
  • -(X) n means that there are n substitutable sites on the main structure ring connected to a substituent X, that is, n Xs are connected one by one to any substitutable site on the ring, and each site has a
  • the connected X can be independently selected from the group type, and n X can be the same or different.
  • the present application provides a method for preparing a thin film, which can be used to prepare a P-type semiconductor thin film, such as a hole transport layer 50 and/or a hole injection layer 60 of an optoelectronic device 100.
  • a P-type semiconductor thin film such as a hole transport layer 50 and/or a hole injection layer 60 of an optoelectronic device 100.
  • the method for preparing the thin film includes the following steps:
  • the additive includes a compound having a structure shown in formula (1):
  • ring A includes one or more of an aromatic ring having 6 to 40 ring carbon atoms and a heteroaromatic ring having 6 to 40 ring atoms, and n is a positive integer;
  • Each occurrence of X is independently selected from one or more of hydrogen, deuterium, and an electron donating group.
  • the additives when depositing thin film materials, specific additives are added, and the additives can form intermolecular ⁇ - ⁇ interactions with the hole functional material or induce local crystallization of the hole functional material.
  • the morphological regularity of the thin film is improved, the film morphology is improved, the intermolecular aggregation behavior is enhanced, the crystallinity is enhanced, and the hole injection and transmission capabilities are improved.
  • ring A includes one or more of an aromatic ring having 6 to 20 ring carbon atoms and a heteroaromatic ring having 6 to 20 ring atoms; in other embodiments, ring A is selected from one or more of the rings of any one of the structures shown in formulas (2) to (7):
  • n is 1 to 4, for example, 1, 2, 3 or 4; in other embodiments, n is 1 or 2, which helps to give full play to the intermolecular forces and improve the steric effect.
  • the boiling point of the additive is lower than the annealing temperature, for example, the boiling point of the additive is greater than or equal to 100°C and less than 200°C.
  • the boiling point may be 200°C to 190°C, 190°C to 150°C, 160°C to 130°C, 140°C to 110°C, 120°C to 100°C, and so on.
  • the annealing temperature of the multi-hole functional material is between 200°C and 230°C. When annealing is performed after the mixed solution is deposited, the additives will also be removed during the thermal annealing process.
  • the mass of the additive accounts for 5-10% of the total mass of the additive and the hole functional material; for example, it can be 5%, 6%, 7%, 8%, 9%, 10% and values between any two of the values listed above. Within this range, it can effectively improve the stability and electrical properties of semiconductor materials and ensure that the material has good film-forming properties.
  • the additive includes terthiophene (CAS: 3593-75-7; boiling point 138°C; structural formula as shown in formula (8)), indene (CAS: 95-13-6; boiling point 182°C; structural formula as shown in formula (9)), benzofuran (CAS: 271-89-6; boiling point 173°C; structural formula as shown in formula (10)), 1-methoxynaphthalene (CAS: 2216-69-5; boiling point 135°C; structural formula as shown in formula (11)), p-methoxyacetophenone (CAS: 100-06-1; boiling point 152°C; structural formula as shown in formula (12)), aniline (CAS: 62-53-3; boiling point 184°C; structural formula as shown in formula (13)), N,N-dimethyl-1-phenylethylamine (CAS: 2449-49-2; boiling point 189°C; structural formula as shown in formula (14)), 1-methylindane (CAS: 27133-93-3; boiling point 193°C; structural formula as shown in formula (8)),
  • each occurrence of X is independently selected from the electron donating groups described herein, including -NH 2 (amino),
  • the combination of one or more of (keto), C1-C3 alkyl and C1-C3 alkoxy helps to enhance the interaction between the additive and the hole functional material and enhance the effect.
  • the additive includes one or more of 1-methoxynaphthalene, p-methoxyacetophenone, aniline, N,N-dimethyl-1-phenylethylamine, 1-methylindane and 2-methylindane.
  • the hole functional material can be selected from organic materials commonly used in the art for preparing the hole transport layer 50 or the hole injection layer 60.
  • the hole functional material is defined as a hole transport material; when selected from organic materials used to prepare the hole injection layer 60, the hole functional material is defined as a hole injection material.
  • the hole functional material is selected from hole transport materials, such as but not limited to poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))] (TFB), At least one of poly(4-butylphenyl-diphenylamine), poly(triarylamine) (PTAA), polypyrrole, poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)-benzidine] (polyTPD), poly(p-)phenylene vinylene (PPV), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene] and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], PEDOT:PSS and its derivatives
  • hole transport materials
  • the hole functional material is selected from hole injection materials, such as but not limited to at least one of PEDOT, PEDOT:PSS, and copper phthalocyanine; in actual application, the film obtained using the hole functional materials listed above can be used as the hole injection layer 60 for preparing the optoelectronic device 100.
  • hole injection materials such as but not limited to at least one of PEDOT, PEDOT:PSS, and copper phthalocyanine; in actual application, the film obtained using the hole functional materials listed above can be used as the hole injection layer 60 for preparing the optoelectronic device 100.
  • the mixed solution may further include a solvent
  • the solvent is used to disperse the hole functional material and the additive
  • the solvent may be any common solvent that can dissolve the hole functional material and the additive, for example, one or more of an alcohol solvent, chloroform, chlorobenzene, and dichlorobenzene.
  • the alcohol solvent includes but is not limited to one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, and pentanol.
  • the concentration of the hole functional material is 2 to 15 mg/ml, for example, it can be 2 mg/ml, 3 mg/ml, 4 mg/ml, 5 mg/ml, 8 mg/ml, 10 mg/ml, 12 mg/ml, 15 mg/ml and values between any two of the above values.
  • the annealing method in step S20, can be heat treatment annealing.
  • the annealing temperature can be 200-230°C, for example, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C and values between any two of the above values.
  • the annealing time may be 15 to 45 min, for example, 15 min, 20 min, 25 min, 27 min, 28 min, 29 min, 30 min, 31 min, 32 min, 33 min, 35 min, 40 min, 45 min, and values between any two of the above values.
  • the present application proposes a thin film, the material of which includes a hole functional material, and the root mean square roughness of the thin film is 0.3 to 1.5, for example, it can be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5 and values between any two of the above values.
  • the film has better morphology regularity and better hole injection and hole transport capabilities.
  • the hole mobility of the film is 10 -3 to 10 -1 cm 2 V -1 s -1 , for example, 1 ⁇ 10 -3 cm 2 V -1 s -1 , 2 ⁇ 10 -3 cm 2 V -1 s -1 , 3 ⁇ 10 -3 cm 2 V -1 s -1 , 4 ⁇ 10 -3 cm 2 V -1 s -1 .
  • the hole functional material may be selected from organic materials commonly used in the art for preparing the hole transport layer 50 or the hole injection layer 60 .
  • the materials are as described above and will not be described in detail herein.
  • the film can be prepared by the above preparation method.
  • the performance of the film varies accordingly.
  • the film when the hole functional material is the hole transport material, the film can be a hole transport film; in other embodiments, when the hole functional material is the hole injection material, the film can also be a hole injection film.
  • the present application also proposes a photoelectric device 100, which includes but is not limited to a light-emitting device, a photovoltaic cell and a photodetector, and the photoelectric device 100 includes a first electrode, a hole functional layer and a second electrode, wherein the first electrode is one of the cathode 40 and the anode 10, and the second electrode is the other of the cathode 40 and the anode 10.
  • the photoelectric device 100 includes a first electrode, a hole functional layer and a second electrode, wherein the hole functional layer includes one or two layers of a hole injection layer 60 and a hole transport layer 50, and the material of at least one layer of the hole functional layer includes the film described above.
  • One or two layers of the hole injection layer 60 and the hole transport layer 50 are the above-mentioned films, that is, one or two layers thereof are induced and adjusted by the additive during preparation, and have better morphology, higher hole injection and transport performance, thereby helping to improve the carrier balance of the device, thereby improving the performance of the device.
  • the hole functional material is selected from poly [(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly (4-butylphenyl-diphenylamine), poly (triarylamine), polypyrrole, poly [N, N'-bis (4-butylphenyl) -N, N'-bis (phenyl) - benzidine], poly (p) phenylene vinylene, poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylene vinylene] and poly [2-methoxy-5- (3',7'-dimethyloctyloxy) -1,4-phenylene vinylene], PEDOT:PSS and its derivatives,
  • the hole functional layer includes the stacked hole injection layer 60 and the hole transport layer 50, wherein the hole transport layer 50 and the hole injection layer 60 are both prepared by the above-mentioned thin film preparation method, and accordingly, the hole functional material of the hole injection layer 60 is selected from the above-mentioned hole injection material, and the hole functional material of the hole transport layer 50 is selected from the above-mentioned hole transport material.
  • the material of the hole transport layer 50 is poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))] and a first additive;
  • the material of the hole injection layer 60 is PEDOT:PSS and a second additive.
  • the first additive and the second additive are both the additives as described above, and are named only to distinguish each other. The two may be the same or different.
  • the hole functional layer includes the stacked hole injection layer 60 and the hole transport layer 50, wherein the hole transport layer 50 is prepared by the above-mentioned thin film preparation method, and the hole injection layer 60 can be realized by conventional techniques in the art.
  • the hole functional layer includes the stacked hole injection layer 60 and the hole transport layer 50, wherein the hole injection layer 60 is prepared by the above-mentioned thin film preparation method, and the hole transport layer 50 can be realized by conventional techniques in the art.
  • the conventional techniques in the art include but are not limited to chemical methods or physical methods. Among them, chemical methods include chemical vapor deposition, continuous ion layer adsorption and reaction method, anode 10 oxidation method, electrolytic deposition method, and coprecipitation method.
  • the physical method includes physical coating method and solution method.
  • the physical coating method includes: thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion plating method, physical vapor deposition method, atomic layer deposition method, pulsed laser deposition method, etc.;
  • the solution method can be spin coating, printing method, inkjet printing method, doctor blading method, printing method, dip pulling method, immersion method, spraying method, roll coating method, casting method, slit coating method and strip coating method, etc.
  • the respective materials are also materials commonly used in the art.
  • the material of the hole injection layer 60 can be selected from the materials conventionally used in the art for preparing the hole injection layer 60, such as but not limited to 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 at least one.
  • the material of the hole transport layer 50 is selected from the materials conventionally used in the art for preparing the hole injection layer 60.
  • the material of the hole transport layer 50 can be selected from, for example, but 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)-triphen
  • the anode 10 may be an anode 10 for a photoelectric device 100 known in the art, for example, may be selected from but 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 is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide.
  • the composite electrode of metal and metal oxide is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.
  • the cathode 40 may be a cathode 40 known in the art for the optoelectronic device 100, for example, it may be selected from but 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 is selected from one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide, the composite electrode of the metal and the metal oxide is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/Al/
  • the optoelectronic device 100 further includes a light-emitting layer 20, and the light-emitting layer 20 is disposed between the first electrode and the hole functional layer. Specifically, the light-emitting layer 20 is located between the cathode 40 and the hole functional layer.
  • the light-emitting layer 20 may be an organic light-emitting layer or a quantum dot light-emitting layer.
  • the optoelectronic device 100 may be an organic light-emitting device; when the light-emitting layer 20 is a quantum dot light-emitting layer, the optoelectronic device 100 may be a quantum dot light-emitting device.
  • 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 can be selected from but 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 B-N covalent bonds, hybrid localized charge transfer excited state materials, and exciplex light-emitting materials.
  • 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 can be selected from but 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 are respectively selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds; the II-VI group compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSe
  • the core-shell structured quantum dots may be selected from but 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.
  • the chemical formula provided only indicates the elemental composition, but does not indicate the content of each element.
  • 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.
  • the perovskite semiconductor material may be selected from, but 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 AMX 3 , wherein A is a Cs + ion, M is a divalent metal cation selected from at least one of Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , and Eu 2+ , and X is a halogen anion selected from at least one of Cl - , Br - , and I - ;
  • the organic-inorganic hybrid perovskite semiconductor has a general structural formula of BMX 3 , wherein B is an organic amine cation selected from CH 3 (CH 2 ) n-2
  • the optoelectronic device 100 further includes an electron transport layer 30, and the electron transport layer 30 is disposed between the first electrode and the hole functional layer. Specifically, the electron transport layer 30 is located between the hole functional layer and the cathode 40.
  • the electron transport layer 30 is located between the light-emitting layer 20 and the cathode 40.
  • the electron transport layer 30 can be prepared using materials with electron transport properties known in the art for optoelectronic devices 100.
  • the material of the electron transport layer 30 includes, but is not limited to, at least one of metal oxides, doped metal oxides, II-VI semiconductor materials, III-V semiconductor materials, and I-III-VI semiconductor materials.
  • the metal oxide is selected from at least one of ZnO, BaO, TiO2 , and SnO2 ; the metal oxide in the doped metal oxide is selected from at least one of ZnO, TiO2 , and SnO2 , the doping element is selected from at least one of Al, Mg, Li, In, and Ga, the II-VI semiconductor material is selected from at least one of ZnS, ZnSe, and CdS; the III-V semiconductor material is selected from at least one of InP and GaP; the I-III-VI semiconductor material is selected from at least one of CuInS and CuGaS.
  • the thickness of each layer in the optoelectronic device 100 is set as needed and is not limited here.
  • the thickness of the first electrode is 10-100nm
  • the thickness of the hole injection layer 60 is 30-100nm
  • the thickness of the hole transport layer 50 is 30-100nm
  • the thickness of the light-emitting layer 20 is 10-50nm
  • the thickness of the electron transport layer 30 is 20-50nm
  • the thickness of the second electrode is 30-100nm.
  • the film layer stacking order of the photoelectric device 100 is the anode 10, the hole injection layer 60, the hole transport layer 50, the light-emitting layer 20, the electron transport layer 30 and the cathode 40; it can be understood that the photoelectric device 100 can be a positive device or an inverted device.
  • the photoelectric device 100 is a positive device, and accordingly, the photoelectric device 100 includes the anode 10, the hole injection layer 60, the hole transport layer 50, the light-emitting layer 20, the electron transport layer 30 and the 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 the cathode 40, the electron transport layer 30, the light-emitting layer 20, the hole transport layer 50, the hole injection layer 60 and the anode 10 stacked in sequence from bottom to top.
  • 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 injection layer, an electron blocking layer, a hole blocking layer, an interface modification layer, etc.
  • each layer of the optoelectronic device 100 can be adjusted according to the actual requirements of the optoelectronic device 100 .
  • each film layer of the optoelectronic device 100 can be prepared by conventional techniques in the art, such as chemical methods or physical methods.
  • chemical methods include chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and coprecipitation.
  • Physical methods include physical coating and solution methods, among which physical coating includes: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, Physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method can be spin coating, printing, inkjet printing, doctor blading, printing, dip-coating, immersion, spraying, roll coating, casting, slit coating and strip coating, etc.
  • the present application further proposes a display device, which includes the optoelectronic device 100 as described above.
  • the display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, laptop computers, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, car displays, televisions or e-book readers, wherein the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (VR) helmet, etc.
  • VR virtual reality
  • the film preparation method is as follows:
  • the hole functional material is TFB; the additive is 1-methoxynaphthalene.
  • the mixed solution was spin-coated on a glass substrate at a rotation speed of 3000 r/min for 30 s, and then annealed at a temperature of 230° C. for 30 min to obtain a thin film with a thickness of 40 nm.
  • This film embodiment is substantially the same as film embodiment 1, except that, in this film embodiment:
  • the additive is naphthalene.
  • This film embodiment is substantially the same as film embodiment 1, except that, in this film embodiment:
  • the additive is terthiophene.
  • This film embodiment is substantially the same as film embodiment 1, except that, in this film embodiment:
  • the additive is a mixture of terthiophene and indene, and the molar ratio of the two is 1:1.
  • This film embodiment is substantially the same as film embodiment 1, except that, in this film embodiment:
  • the mass ratio of the hole functional material to the additive is 95:5.
  • This film embodiment is substantially the same as film embodiment 1, except that, in this film embodiment:
  • the mass ratio of the hole functional material to the additive is 90:10.
  • This film embodiment is substantially the same as film embodiment 1, except that, in this film embodiment:
  • the mass ratio of the hole functional material to the additive is 85:15.
  • This film embodiment is substantially the same as film embodiment 1, except that, in this film embodiment:
  • the mixed solution consists of a hole functional material and an additive, and the hole functional material is PEDOT:PSS; the annealing temperature is changed to 200°C.
  • TFB Take TFB and add it into chlorobenzene, stir and mix well to obtain a TFB solution with a concentration of 8 mg/ml.
  • the TFB solution was spin-coated on the glass substrate at a rotation speed of 3000 r/min for 30 seconds, and then annealed at a temperature of 230° C. for 30 minutes to obtain a film with a thickness of 40 nm.
  • the PEDOT:PSS solution was spin-coated on a glass substrate at a rotation speed of 3000 r/min for 30 seconds, and then annealed at a temperature of 200° C. for 30 minutes to obtain a film with a thickness of 40 nm.
  • the preparation method of the QLED device is as follows:
  • the patterned ITO glass substrate was placed in acetone, washing liquid, deionized water, and isopropanol for ultrasonic cleaning in order, and each ultrasonic cleaning time was 20 minutes. After cleaning, it was blown dry with a nitrogen gun. Then, the ITO glass substrate was placed in oxygen plasma for another 10 minutes, and then treated with UV-ozone. The surface of the ITO glass substrate was treated for 15 minutes to obtain an anode with a thickness of 10 nm.
  • a layer of PEDOT:PSS was spin-coated on the surface of the anode at a speed of 3000 r/min for 30 seconds, and then annealed at 150°C for 20 minutes to obtain a hole injection layer with a thickness of 80 nm. After annealing, the substrate was transferred to a glove box filled with nitrogen atmosphere.
  • Example 3 The mixed solution prepared in Example 1 was spin-coated on the surface of the hole injection layer at a speed of 3000 r/min for 30 s, and then annealed at 230° C. for 30 min to obtain a hole transport layer with a thickness of 40 nm.
  • step (3) After the semi-finished product obtained in step (3) is cooled, 40 mg/ml of blue quantum dot material CdZnSe/ZnSe/Cd/Cd 0.6 ZnS 2 is spin-coated on the surface of the hole transport layer at a speed of 1500 r/min for 30 s, and then annealed at 100° C. for 5 min to obtain a light-emitting layer with a thickness of 25 nm.
  • a 40 mg/ml ZnO ethanol solution was spin coated on the surface of the light-emitting layer at a speed of 3000 r/min for 30 s, and then annealed at a temperature of 100° C. for 15 min to obtain an electron transport layer with a thickness of 30 nm.
  • step (6) The semi-finished product obtained in step (5) is placed in a vacuum chamber, a layer of silver with a thickness of 100 nm is evaporated on the surface of the electron transport layer as a cathode, and encapsulated to obtain a QLED device.
  • the scheme of device embodiment m is basically the same as device embodiment 1, with the only difference being that in device embodiment m, in step (3), the mixed solution used to prepare the hole transport layer is changed to the mixed solution prepared in thin film embodiment m, wherein m is 2 to 7.
  • the device embodiment scheme is basically the same as the device embodiment 1, except that, in the device embodiment, the hole injection layer is doped with additives during preparation, and the hole transport layer is prepared by conventional methods, and accordingly:
  • step (3) the material used to prepare the hole transport layer is changed to a chlorobenzene solution of TFB with a concentration of 8 mg/ml;
  • step (2) the material used to prepare the hole injection layer is changed to the mixed solution prepared in thin film example 8.
  • the device embodiment scheme is basically the same as the device embodiment 1, except that in the device embodiment, the hole transport layer and the hole injection layer are both doped with additives during preparation:
  • step (2) the material used to prepare the hole injection layer is changed to the mixed solution prepared in Thin Film Example 8.
  • the device comparative example n is substantially the same as the device embodiment 1, except that in the device comparative example n:
  • step (3) the material used to prepare the hole transport layer is changed to the solution prepared in thin film comparative example n, wherein n is 1 or 2.
  • Hole transport performance test Control QE PRO and Keithley 2400 through LabView to build a QLED efficiency test system.
  • the system tests the current density-voltage curve of the single carrier transport thin film device (HOD/EOD). Compare the current density of the device under the working voltage (6V) and the working voltage in the steady state.
  • the working voltage in the steady state refers to the working voltage of the device in the device balance stage when the device runs for more than 4 hours during the device life test. Among them:
  • the preparation method of the single hole device is basically the same as the preparation method of its corresponding complete QLED device, the only difference is that the electron transport layer is subtracted.
  • the devices used are single-hole devices corresponding to the QLED devices in the above device embodiments 1 to 9 and device comparison examples 1-2.
  • device embodiments 1 to 7 and 9 all have higher current efficiency and lower operating voltage.
  • device embodiments 8 and 9 all have higher current efficiency and lower operating voltage, indicating that the addition of additives when preparing the hole functional layer helps to improve the hole transport and injection properties of the film layer, thereby improving the electrical properties of the device.
  • the quantum dot light-emitting diodes of device examples 1-9 and device comparative examples 1-2 were subjected to performance tests, and the test results are shown in Table 3.
  • the test method is as follows:
  • the detection method of external quantum efficiency EQE is: the ratio of the number of electron-hole pairs injected into quantum dots to the number of emitted photons, the unit is %, which is an important parameter for measuring the quality of electroluminescent devices and can be obtained by using EQE optical testing instruments.
  • the specific calculation formula is as follows:
  • ⁇ e is the light output coupling efficiency
  • ⁇ is the ratio of the number of recombined carriers to the number of injected carriers
  • x is the ratio of the number of excitons that generate photons to the total number of excitons
  • KR is the radiation process rate
  • KNR is the non-radiative process rate
  • Test conditions carried out at room temperature, air humidity is 30-60%.
  • the time it takes for the brightness to drop to 95% of the maximum brightness is defined as T95, and this life is the measured life.
  • the device life test is usually carried out at high brightness by accelerating device aging, and the life under high brightness is obtained by fitting the extended exponential decay brightness attenuation fitting formula. For example, the life under 1000nit is calculated as T95@1000nit.
  • the specific calculation formula is as follows:
  • T95 L is the lifespan at low brightness
  • T95 H is the measured lifespan at high brightness
  • L H is the device accelerated to the maximum brightness
  • L L is 1000nit
  • A is the acceleration factor.
  • the devices used in the external quantum efficiency test and the device life test are the QLED devices with complete structures in the above embodiments and comparative examples.
  • device embodiments 1 to 7 and 9 all have higher EQE and T95@1000nit.
  • device embodiments 8 and 9 all have higher EQE and T95@1000nit, indicating that the addition of additives during the preparation of the hole functional layer helps to improve the hole transport and injection performance of the film layer, improve the carrier balance of the device, and thereby improve the luminous efficiency and life of the device.

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Abstract

一种薄膜及其制备方法及光电器件，方法包括：提供混合溶液，所述混合溶液包括空穴功能材料和添加剂；沉积所述混合溶液，然后退火以去除所述添加剂，得到薄膜。解决了现有空穴功能材料薄膜空穴迁移率较低的问题。

Description

薄膜及其制备方法及光电器件
本申请要求于2023年06月16日在中国专利局提交的、申请号为202310724008.1、申请名称为“薄膜及其制备方法、光电器件及显示装置”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及半导体领域，尤其涉及一种薄膜及其制备方法及光电器件。
背景技术
一些有机材料例如聚苯乙烯磺酸盐(PEDOT:PSS)、聚[(9,9-二辛基芴-2,7-二基)-共-(4,4′-(N-(4-仲丁基苯基)二苯胺)](TFB)等等，通常具有空穴注入、空穴传输性能，适用于制备空穴功能膜层。然而，采用这些材料制得的薄膜的空穴迁移率通常较低，不适配于对空穴注入、传输性能要求较高的场合。
技术解决方案
因此，本申请提供一种薄膜及其制备方法及光电器件。
第一方面，本申请提供一种薄膜的制备方法，包括以下步骤：
提供混合溶液，所述混合溶液包括空穴功能材料和添加剂；
沉积所述混合溶液，然后退火以去除所述添加剂，得到薄膜；
其中，所述添加剂包括具有式(1)所示结构的化合物：
其中，环A包括环碳原子数为6～40的芳环和环原子数为6～40的杂芳环中的一种或者多种，n为正整数；
X每次出现时独立的选自氢、氘、给电子基团中的一种或多种。
可选的，在本申请的一些实施例中，所述给电子基团包括-NH2、 C1～C3烷基以及C1～C3烷氧基中的一种或多种的组合。
可选的，在本申请的一些实施例中，环A包括环碳原子数为6～20的芳环和环原子数为6～20的杂芳环中的一种或者多种。
可选的，在本申请的一些实施例中，环A选自式(2)至(7)任一所示结构的环中的一种或多种：
可选的，在本申请的一些实施例中，n为1～4。
可选的，在本申请的一些实施例中，n为1或2。
可选的，在本申请的一些实施例中，所述添加剂的沸点大于等于100℃，且小于200℃。
可选的，在本申请的一些实施例中，所述添加剂包括具有如下式(8)至(16)任一项所示结构的化合物中的一种或多种：
可选的，在本申请的一些实施例中，X每次出现时独立的选自所述给电子基团。
可选的，在本申请的一些实施例中，所述添加剂包括具有所述式(11)至所述(16)任一项所示结构的化合物中的一种或多种：

可选的，在本申请的一些实施例中，所述添加剂的质量占所述添加剂和所述空穴功能材料的总质量的百分比为5～10％。
可选的，在本申请的一些实施例中，所述空穴功能材料包括空穴传输材料或空穴注入材料，所述空穴传输材料选自聚[(9,9'-二辛基芴-2,7-二基)-共-(4,4'-(N-(4-仲丁基苯基)二苯胺))]、聚(4-丁基苯基-二苯基胺)、聚(三芳胺)、聚吡咯、聚[N,N′-双(4-丁苯基)-N,N′-双(苯基)-联苯胺]、聚(对)亚苯基亚乙烯基、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-亚苯基亚乙烯基]和聚[2-甲氧基-5-(3',7'-二甲基辛氧基)-1,4-亚苯基亚乙烯基]、PEDOT:PSS及其衍生物、聚(N-乙烯基咔唑)及其衍生物、聚甲基丙烯酸酯及其衍生物、聚(9，9-辛基芴)及其衍生物、聚(螺芴)及其衍生物中的至少一种；所述空穴注入材料选自PEDOT、PEDOT:PSS、酞菁铜中的至少一种。
可选的，在本申请的一些实施例中，沉积所述混合溶液，然后退火以去除所述添加剂，得到薄膜的步骤中，所述退火的温度为200～230℃。
可选的，在本申请的一些实施例中，所述退火的时间为15～45min。
可选的，在本申请的一些实施例中，所述混合溶液还包括溶剂，所述溶剂包括醇类溶剂、氯仿、氯苯、二氯苯中的一种或多种。
可选的，在本申请的一些实施例中，所述混合溶液中，所述空穴功能材料的浓度为2～15mg/ml。
第二方面，本申请提出一种薄膜，所述薄膜的材料包括空穴功能材料，所述薄膜的均方根粗糙度为0.3～1.5。
可选的，在本申请的一些实施例中，所述薄膜的空穴迁移率为10-3～10-1cm2V–1s–1。
第三方面，本申请提出一种光电器件，包括第一电极、空穴功能层和第二电极，所述空穴功能层包括空穴注入层和空穴传输层中的一层或两层，且所述 空穴功能层中的至少一层包括如上文所述的薄膜，或者，包括上文所述的制备方法制得的薄膜。
可选的，在本申请的一些实施例中，所述第一电极和所述第二电极各自独立的选自掺杂金属氧化物颗粒电极、金属与金属氧化物的复合电极、石墨烯电极、碳纳米管电极、金属电极或合金电极，所述掺杂金属氧化物颗粒电极的材料选自铟掺杂氧化锡、氟掺杂氧化锡、锑掺杂氧化锡、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌及铝掺杂氧化镁中的一种或多种，所述金属与金属氧化物的复合电极选自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，所述金属电极的材料选自Ag、Al、Cu、Mo、Au、Pt、Si、Ca、Mg及Ba中的一种或多种。
可选的，在本申请的一些实施例中，所述光电器件还包括发光层，所述发光层设于所述第一电极和所述空穴功能层之间，或者所述发光层设于所述二电极和所述空穴功能层之间，所述发光层的材料选自有机发光材料及量子点发光材料中的一种或多种，所述有机发光材料选自4,4'-双(N-咔唑)-1,1'-联苯:三[2-(对甲苯基)吡啶合铱(III)、4,4',4”-三(咔唑-9-基)三苯胺:三[2-(对甲苯基)吡啶合铱、二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPX荧光材料、TBRb荧光材料、DBP荧光材料、延迟荧光材料、TTA材料、热活化延迟材料、含有B-N共价键合的聚合物、杂化局域电荷转移激发态材料、激基复合物发光材料中的一种或多种；所述量子点发光材料选自单一结构量子点、核壳结构量子点及钙钛矿型半导体材料中的至少一种；所述单一结构量子点的材料、核壳结构量子点的核材料及核壳结构量子点的壳层材料分别选自II-VI族化合物、IV-VI族化合物、III-V族化合物和I-III-VI族化合物中的至少一种；所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe及HgZnSTe中的至少一种；所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、 SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTe中的至少一种；所述III-V族化合物选自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及InAlPSb中的至少一种；所述I-III-VI族化合物选自CuInS2、CuInSe2及AgInS2中的至少一种；所述钙钛矿型半导体材料选自掺杂或非掺杂的无机钙钛矿型半导体、或有机-无机杂化钙钛矿型半导体；所述无机钙钛矿型半导体的结构通式为AMX3，其中A为Cs+离子，M为二价金属阳离子，选自Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+中的至少一种，X为卤素阴离子，选自Cl-、Br-、I-中的至少一种；所述有机-无机杂化钙钛矿型半导体的结构通式为BMX3，其中B为有机胺阳离子，选自CH3(CH2)n-2NH3 +或[NH3(CH2)nNH3]2+，其中n≥2，M为二价金属阳离子，选自Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+中的至少一种，X为卤素阴离子，选自Cl-、Br-、I-中的至少一种。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本申请实施例提出的一种薄膜的制备方法的流程示意图；
图2是本申请一实施例提出的一种光电器件的结构示意图；
图3是本申请另一实施例提出的一种光电器件的结构示意图；
图4是实验例一中对照组的AFM图；
图5是实验例一中实验组的AFM图；
附图标记：
100-光电器件；10-阳极；20-发光层；30-电子传输层；40-阴极；50-空穴传输层；60-空穴注入层。
本申请的实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域技术人员在没有作出创造性劳动的前提下所获得的所有其它实施例，都属于本申请保护的范围。此外，应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。在本申请中，在未作相反说明的情况下，使用的方位词如“上”和“下”具体为附图中的图面方向。另外，在本申请说明书的描述中，术语“包括”是指“包括但不限于”。本申请的各种实施例可以以一个范围的形式存在；应当理解，以一范围形式的描述仅仅是因为方便及简洁，不应理解为对本申请范围的硬性限制；因此，应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如，应当认为从1到6的范围描述已经具体公开子范围，例如从1到3，从1到4，从1到5，从2到4，从2到6，从3到6等，以及所述范围内的单一数字，例如1、2、3、4、5及6，此不管范围为何皆适用。另外，每当在本文中指出数值范围，是指包括所指范围内的任何引用的数字(分数或整数)。
在本申请中，“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。
在本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“至少一种”、“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，“a,b,或c中的至少一项(个)”，或，“a,b,和c中的至少一项(个)”，均可以表示：a,b,c,a-b(即a和b),a-c,b-c,或a-b-c，其中a,b,c分别可以是单个，也可以是多个。
在本申请中，“并环”是指化合物中，两个环共用两直接相连的碳原子而相互结合的情况，其中，共用的两个碳原子即为公共碳原子，化合物中，属于公 共碳原子的原子总数为公共碳原子数；例如，萘为两个苯环的并环，其公共碳原子数为2。
在本申请中，“环原子数”表示原子键合成环状而得到的结构化合物(例如，单环化合物、稠环化合物、交联化合物、碳环化合物、杂环化合物)的构成该环自身的原子之中的原子数。该环被取代基所取代时，取代基所包含的原子不包括在成环原子内。关于以下所述的“环原子数”，在没有特别说明的条件下也是同样的。例如，苯环的环原子数为6，萘环的环原子数为10，噻吩基的环原子数为5。“环碳原子数”是指构成该环自身的碳原子之中的原子数。例如，苯环的环碳原子数为6，噻吩基的环碳原子数为4。
在本申请中，“芳环或芳香环”是指含苯环的环状化合物，可以为单环或多个环并环形成的稠环，对于多环的环中，至少一个是芳族环系。例如，“具有6至40个环原子的芳环”是指包含6至40个环原子的芳环，优选具有6至30个环原子的芳环，更优选具有6至18个环原子的芳环，特别优选具有6至14个环原子的芳环；合适的实例包括但不限于：苯环、萘环、蒽环、菲环、并四苯环、芴环、茚环等。
在本申请中，“杂芳环或杂芳香环”是指在芳环的基础上至少一个碳原子被非碳原子所替代，非碳原子可以为N原子、O原子、S原子等。合适的实例包括但不限于：噻吩、呋喃、吡咯、咪唑、二唑、三唑、吡啶、联吡啶、嘧啶、三嗪、吖啶、哒嗪、吡嗪、喹啉、异喹啉、喹唑啉、喹喔啉、酞嗪、吡啶并嘧啶、吡啶并吡嗪、苯并噻吩、苯并呋喃、吲哚、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、邻二氮萘、菲啶、伯啶、喹唑啉酮、二苯并噻吩、二苯并呋喃、咔唑及其衍生物。
在本申请中，“烷基”可以表示直链烷基或支链烷基。“C1～3烷基”是指包含1至3个碳原子的烷基，每次出现时，可以互相独立地为C1烷基、C2烷基或C3烷基。烷基的非限制性实例包括甲基、乙基、正丙基、异丙基等。
在本申请中，烷氧基具有式-OR的结构特征，其中，R是指烷基。
在本申请中，-(X)n是指主体结构环上有n个可取代位点上连接有取代基X，也就是说，n个X分别与环上的任一可取代位点一一连接，且每个位点上 连接的X均可独立的选择基团种类，n个X可以相同，也可以不同。
第一方面，本申请提出一种薄膜的制备方法，可以制备P型半导体薄膜，例如光电器件100的空穴传输层50和/或空穴注入层60。请参阅图1，所述薄膜的制备方法包括以下步骤：
S10，提供混合溶液，所述混合溶液包括空穴功能材料和添加剂；
S20，沉积所述混合溶液，然后退火以去除所述添加剂，得到薄膜；
其中，所述添加剂包括具有式(1)所示结构的化合物：
其中，环A包括环碳原子数为6～40的芳环和环原子数为6～40的杂芳环中的一种或者多种，n为正整数；
X每次出现时独立的选自氢、氘、给电子基团中的一种或多种。
本申请中，在沉积薄膜材料时，添加特定添加剂，所述添加剂可以和空穴功能材料之间形成分子间π-π相互作用或诱导空穴功能材料局部结晶，如此，在制成薄膜时，从而提升其薄膜的形貌规整度，改善薄膜形貌，增强分子间聚集行为，增强结晶性，从而提升空穴注入、传输能力。
在一些实施例中，环A包括环碳原子数为6～20的芳环和环原子数为6～20的杂芳环中的一种或者多种；在另一些实施例中，环A选自式(2)至(7)任一所示结构的环中的一种或多种：
在一些实施例中，n为1～4，例如可以是1、2、3或者4；在另一些实施例中，n为1或2，有助于充分发挥分子间作用力，改善位阻效应。
在一些实施例中，所述添加剂的沸点低于退火温度，例如，所述添加剂的沸点大于等于100℃，且小于200℃。例如，沸点可以为200℃至190℃，190℃至150℃，160℃至130℃，140℃至110℃，120℃至100℃，等等。由于大多 数空穴功能材料的退火温度在200℃～230℃，在沉积混合溶液后进行退火时，所述添加剂也会在热退火的过程中被除去，如此既让薄膜保留了添加剂诱导形成的规整形貌，提升了其性能，又避免了添加剂残留，防止添加剂影响薄膜，且由于不必担心因添加剂残留而可能造成的影响，从而扩展了添加剂材料的可选择种类，降低了其材料开发难度。
在一些实施例中，所述添加剂的质量占所述添加剂和所述空穴功能材料的总质量的百分比为5～10％；例如可以为5％、6％、7％、8％、9％、10％以及上述列举的任意两个值之间的值，在此范围内，既可以有效提升半导体材料的稳定性和电学性能，又可以确保材料具有良好的成膜性。
在一些具体实施例中，所述添加剂包括并三噻吩(CAS：3593-75-7；沸点138℃；结构式如式(8)所示)、茚(CAS：95-13-6；沸点182℃；结构式如式(9)所示)、苯并呋喃(CAS:271-89-6；沸点173℃；结构式如式(10)所示)、1-甲氧基萘(CAS：2216-69-5；沸点135℃；结构式如式(11)所示)、对甲氧基苯乙酮(CAS:100-06-1；沸点152℃；结构式如式(12)所示)、苯胺(CAS:62-53-3；沸点184℃；结构式如式(13)所示)、N,N-二甲基-1-苯乙胺(CAS：2449-49-2；沸点189℃；结构式如式(14)所示)、1-甲基茚满(CAS:27133-93-3；沸点193℃；结构式如式(15)所示)、2-甲基茚满(CAS:824-63-5；沸点195℃；结构式如式(16)所示)中的一种或多种。这些添加剂与P型半导体材料之间具有较强的相互作用，且具有相对较低的沸点，易于除去。具体的，上述化合物的结构式依次如下式(8)至(16)所示。
在一些实施例中，X每次出现时各自独立的选自所述给电子基团，所述给电子基团包括-NH2(氨基)、(酮基)、C1～C3烷基以及C1～C3烷氧基中的一种或多种的组合，如此有助于提升添加剂和空穴功能材料之间的相互作用，增强效果。相应的，所述添加剂包括1-甲氧基萘、对甲氧基苯乙酮、苯胺、N,N-二甲基-1-苯乙胺、1-甲基茚满、2-甲基茚满中的一种或多种。
在一些实施例中，所述空穴功能材料可以选自本领域常见的用于制备空穴传输层50或空穴注入层60的有机材料，选自用于制备空穴传输层50的有机材料时，空穴功能材料定义为空穴传输材料；选自用于制备空穴注入层60的有机材料时，空穴功能材料定义为空穴注入材料。
在一具体实施例中，所述空穴功能材料选自空穴传输材料，例如包括但不限于聚[(9,9'-二辛基芴-2,7-二基)-共-(4,4'-(N-(4-仲丁基苯基)二苯胺))](TFB)、 聚(4-丁基苯基-二苯基胺)、聚(三芳胺)(PTAA)、聚吡咯、聚[N,N′-双(4-丁苯基)-N,N′-双(苯基)-联苯胺](聚TPD)、聚(对)亚苯基亚乙烯基(PPV)、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-亚苯基亚乙烯基]和聚[2-甲氧基-5-(3',7'-二甲基辛氧基)-1,4-亚苯基亚乙烯基]、PEDOT:PSS及其衍生物、聚(N-乙烯基咔唑)(PVK)及其衍生物、聚甲基丙烯酸酯及其衍生物、聚(9，9-辛基芴)及其衍生物、聚(螺芴)及其衍生物中的至少一种；实际应用时，采用上述列举的空穴功能材料得到的薄膜可以作为光电器件100的空穴传输层50。
在另一实施例中，所述空穴功能材料选自空穴注入材料，例如包括但不限于PEDOT、PEDOT:PSS、酞菁铜中的至少一种；实际应用时，采用上述列举的空穴功能材料得到的薄膜可以作为制备光电器件100的空穴注入层60。
在一些实施例中，所述混合溶液还可以包括溶剂，所述溶剂用于分散空穴功能材料和添加剂，所述溶剂可以是任意能够溶解空穴功能材料及添加剂的常见溶剂，例如，醇类溶剂、氯仿、氯苯、二氯苯中的一种或多种。所述醇类溶剂包括但不限于甲醇、乙醇、异丙醇、正丙醇、正丁醇、戊醇中的一种或多种。
在一些实施例中，所述混合溶液中，所述空穴功能材料的浓度为2～15mg/ml，例如，可以是2mg/ml、3mg/ml、4mg/ml、5mg/ml、8mg/ml、10mg/ml、12mg/ml、15mg/ml以及上述任意两个值之间的值。
在一些实施例中，步骤S20中，所述退火的方式可以是热处理退火，具体的，所述退火的温度可以为200～230℃，例如，200℃、205℃、210℃、215℃、220℃、225℃、230℃以及上述任意两个值之间的值。
所述退火的时间可以为15～45min，例如可以是15min、20min、25min、27min、28min、29min、30min、31min、32min、33min、35min、40min、45min以及上述任意两个值之间的值。
第二方面，本申请提出一种薄膜，所述薄膜的材料包括空穴功能材料，所述薄膜的均方根粗糙度为0.3～1.5，例如可以是0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4、1.5以及上述任意两个值之间的值。
所述薄膜具有较佳的形貌规整度以及较好的空穴注入、空穴传输能力。
在一些实施例中，所述薄膜的空穴迁移率为10-3～10-1cm2 V–1s–1。例如可以是1×10-3cm2 V–1s–1、2×10-3cm2 V–1s–1、3×10-3cm2 V–1s–1、4×10-3cm2 V–1s –1、5×10-3cm2 V–1s–1、6×10-3cm2 V–1s–1、7×10-3cm2 V–1s–1、8×10-3cm2 V–1s–1、9×10-3cm2 V–1s–1、1×10-2cm2 V–1s–1、2×10-2cm2 V–1s–1、3×10-2cm2 V–1s–1、4×10-2cm2 V–1s–1、5×10-2cm2 V–1s–1、6×10-2cm2 V–1s–1、7×10-2cm2 V–1s–1、8×10-2cm2 V–1s–1、9×10-2cm2 V–1s–1、1×10-1cm2 V–1s–1以及上述任意两个值之间的值。
所述空穴功能材料可以选自本领域常见的用于制备空穴传输层50或空穴注入层60的有机材料，所述材料如上文所述，在此不作赘述。
在一些实施例中，所述薄膜可以由上述制备方法制得。根据混合溶液中空穴功能材料的种类不同，所述薄膜的性能随之变化，例如，在一些实施例中，所述空穴功能材料为所述空穴传输材料时，所述薄膜可以是空穴传输薄膜；在另一些实施例中，所述空穴功能材料为所述空穴注入材料时，所述薄膜也可以是空穴注入薄膜。
第三方面，本申请还提出一种光电器件100，所述光电器件100包括但不限于是发光器件、光伏电池和光电探测器，所述光电器件100包括第一电极、空穴功能层和第二电极，所述第一电极为阴极40和阳极10中的一个，所述第二电极为阴极40和阳极10中的另一个。请参阅图2，所述光电器件100包括第一电极、空穴功能层和第二电极，所述空穴功能层包括空穴注入层60和空穴传输层50中的一层或两层，且所述空穴功能层中的至少一层的材料包括如上文所述的薄膜。所述空穴注入层60和空穴传输层50中的一层或两层为上述薄膜，即其中的一层或两层在制备时经由所述添加剂诱导、调整过，具有较佳的形貌、较高的空穴注入、传输性能，从而有助于改善器件的载流子平衡，进而提升器件的性能。
可以理解，当空穴传输层50采用如上所述的薄膜时，制备薄膜的过程中，所采用的混合溶液中，空穴功能材料选自聚[(9,9'-二辛基芴-2,7-二基)-共-(4,4'-(N-(4-仲丁基苯基)二苯胺))]、聚(4-丁基苯基-二苯基胺)、聚(三芳胺)、聚吡咯、聚[N,N′-双(4-丁苯基)-N,N′-双(苯基)-联苯胺]、聚(对)亚苯基亚乙烯基、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-亚苯基亚乙烯基]和聚[2-甲氧基-5-(3',7'-二甲基辛氧基)-1,4-亚苯基亚乙烯基]、PEDOT:PSS及其衍生物、聚(N-乙烯基咔唑)及其衍生物、聚甲基丙烯酸酯及其衍生物、聚(9，9-辛基芴)及其衍生物、 聚(螺芴)及其衍生物中的至少一种；当空穴注入层60采用如上所述的薄膜时，制备薄膜的过程中，所采用的混合溶液中，空穴功能材料选自PEDOT、PEDOT:PSS、酞菁铜中的至少一种。
在一些实施例中，所述空穴功能层包括层叠的所述空穴注入层60和所述空穴传输层50，其中，空穴传输层50和空穴注入层60均采用上述薄膜制备方法进行制备，相应的，所述空穴注入层60的空穴功能材料选自上述空穴注入材料，所述空穴传输层50的空穴功能材料选自上述空穴传输材料，例如，空穴传输层50的材料为聚[(9,9'-二辛基芴-2,7-二基)-共-(4,4'-(N-(4-仲丁基苯基)二苯胺))]和第一添加剂；空穴注入层60的材料为PEDOT:PSS和第二添加剂。可以理解，所述第一添加剂和所述第二添加剂均为如上所述的添加剂，只是为了相互区别而做的命名，二者可以相同，也可以不同。
在另一些实施例中，所述空穴功能层包括层叠的所述空穴注入层60和所述空穴传输层50，其中，所述空穴传输层50采用上述薄膜制备方法进行制备，所述空穴注入层60可采用本领域常规技术实现。在又一些实施例中，所述空穴功能层包括层叠的所述空穴注入层60和所述空穴传输层50，其中，所述空穴注入层60采用上述薄膜制备方法进行制备，所述空穴传输层50可采用本领域常规技术实现。所述本领域常规技术包括但不限于化学法或物理法。其中，化学法包括化学气相沉积法、连续离子层吸附与反应法、阳极10氧化法、电解沉积法、共沉淀法。物理法包括物理镀膜法和溶液法，其中，物理镀膜法包括：热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法等；溶液法可以为旋涂法、印刷法、喷墨打印法、刮涂法、打印法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法及条状涂布法等。
采用常规技术制备空穴传输层50或空穴注入层60时，各自的材料也均采用本领域常用的材料。例如，所述空穴注入层60的材料可以选自本领域常规的用于制备空穴注入层60的材料，例如可以选自但不限于2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲、PEDOT、PEDOT:PSS、PEDOT:PSS掺有s-MoO3的衍生物、4,4',4'-三(N-3-甲基苯基-N-苯基氨基)三苯胺、四氰基醌二甲烷、酞菁铜中的至少一种。所述空穴传输层50的材料选自本领域常规的用于制备空 穴传输层50的材料，例如可以选自但不限于4,4'-N,N'-二咔唑基-联苯、N,N'-二苯基-N,N'-双(1-萘基)-1,1'-联苯-4,4”-二胺、N,N'-二苯基-N,N'-双(3-甲基苯基)-(1,1'-联苯基)-4，4'-二胺、N,N'-双(3-甲基苯基)-N,N'-双(苯基)-螺、N,N'-二(4-(N,N'-二苯基-氨基)苯基)-N,N'-二苯基联苯胺、4,4',4'-三(N-咔唑基)-三苯胺、4,4',4'-三(N-3-甲基苯基-N-苯基氨基)三苯胺、聚[(9,9'-二辛基芴-2,7-二基)-共-(4,4'-(N-(4-仲丁基苯基)二苯胺))]、聚(4-丁基苯基-二苯基胺)、聚(三芳胺)、聚吡咯、聚[N,N′-双(4-丁苯基)-N,N′-双(苯基)-联苯胺]、聚(对)亚苯基亚乙烯基、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-亚苯基亚乙烯基]和聚[2-甲氧基-5-(3',7'-二甲基辛氧基)-1,4-亚苯基亚乙烯基]、铜酞菁、芳香族叔胺、多核芳香叔胺、4,4'-双(对咔唑基)-1,1'-联苯化合物、N,N,N',N'-四芳基联苯胺、PEDOT:PSS及其衍生物、聚(N-乙烯基咔唑)及其衍生物、聚甲基丙烯酸酯及其衍生物、聚(9，9-辛基芴)及其衍生物、聚(螺芴)及其衍生物、N,N'-二(萘-1-基)-N,N'-二苯基联苯胺、螺NPB、掺杂石墨烯、非掺杂石墨烯、C60中的至少一种。
在一些实施例中，所述阳极10可以为本领域已知用于光电器件100的阳极10，例如，可以选自但不限于掺杂金属氧化物颗粒电极、金属与金属氧化物的复合电极、石墨烯电极、碳纳米管电极、金属电极或合金电极，所述掺杂金属氧化物颗粒电极的材料选自铟掺杂氧化锡、氟掺杂氧化锡、锑掺杂氧化锡、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌及铝掺杂氧化镁中的一种或多种，所述金属与金属氧化物的复合电极选自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，所述金属电极的材料选自Ag、Al、Cu、Mo、Au、Pt、Si、Ca、Mg及Ba中的一种或多种。
在一些实施例中，所述阴极40可以为本领域已知用于光电器件100的阴极40，例如，可以选自但不限于掺杂金属氧化物颗粒电极、金属与金属氧化物的复合电极、石墨烯电极、碳纳米管电极、金属电极或合金电极，所述掺杂金属氧化物颗粒电极的材料选自铟掺杂氧化锡、氟掺杂氧化锡、锑掺杂氧化锡、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌及铝掺杂氧化镁中的一种或多种，所述金属与金属氧化物的复合电极选自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，所述金属电极的材料选自Ag、Al、Cu、Mo、Au、Pt、Si、Ca、Mg及Ba中的一种或多种。
请参阅图3，在一些实施例中，所述光电器件100还包括发光层20，所述发光层20设于所述第一电极和所述空穴功能层之间，具体的，所述发光层20位于阴极40和空穴功能层之间。所述发光层20可以为有机发光层或量子点发光层。当所述发光层20为有机发光层时，所述光电器件100可为有机发光器件；当所述发光层20为量子点发光层时，所述光电器件100可以为量子点发光器件。
所述有机发光层的材料为本领域已知用于光电器件100的有机发光层的材料，例如，可以选自但不限于4,4'-双(N-咔唑)-1,1'-联苯:三[2-(对甲苯基)吡啶合铱(III)、4,4',4”-三(咔唑-9-基)三苯胺:三[2-(对甲苯基)吡啶合铱、二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPX荧光材料、TBRb荧光材料、DBP荧光材料、延迟荧光材料、TTA材料、热活化延迟材料、含有B-N共价键合的聚合物、杂化局域电荷转移激发态材料、激基复合物发光材料中的一种或多种。
所述量子点发光层的材料为本领域已知用于光电器件100的量子点发光层的量子点材料，例如，可以选自但不限于单一结构量子点、核壳结构量子点及钙钛矿型半导体材料中的至少一种；所述单一结构量子点的材料、核壳结构量子点的核材料及核壳结构量子点的壳层材料分别选自II-VI族化合物、IV-VI族化合物、III-V族化合物和I-III-VI族化合物中的至少一种；所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe及HgZnSTe中的至少一种；所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTe中的至少一种；所述III-V族化合物选自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及InAlPSb中的至少一种；所述I-III-VI族化合物选自CuInS2、CuInSe2及AgInS2中的至少一种。
作为示例，所述核壳结构的量子点可以选自但不限于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及InP/ZnSe/ZnS中的至少一种。
需要说明的是，对于前述单一结构量子点的材料、或者核壳结构量子点的核的材料、或者核壳结构量子点的壳的材料，提供的化学式仅示明了元素组成，并未示明各个元素的含量，例如：CdZnSe仅表示由Cd、Zn和Se三种元素组成，若表示各个元素的含量，则对应为CdxZn1-xSe，0<x<1。
所述钙钛矿型半导体材料可以选自但不限于掺杂或非掺杂的无机钙钛矿型半导体、或有机-无机杂化钙钛矿型半导体；所述无机钙钛矿型半导体的结构通式为AMX3，其中A为Cs+离子，M为二价金属阳离子，选自Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+中的至少一种，X为卤素阴离子，选自Cl-、Br-、I-中的至少一种；所述有机-无机杂化钙钛矿型半导体的结构通式为BMX3，其中B为有机胺阳离子，选自CH3(CH2)n-2NH3 +或[NH3(CH2)nNH3]2+，其中n≥2，M为二价金属阳离子，选自Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+中的至少一种，X为卤素阴离子，选自Cl-、Br-、I-中的至少一种。
在一些实施例中，所述光电器件100还包括电子传输层30，所述电子传输层30设于所述第一电极和所述空穴功能层之间，具体的，所述电子传输层30位于空穴功能层和阴极40之间，在光电器件100还包括发光层20时，所述电子传输层30位于发光层20和阴极40之间。所述电子传输层30可以采用本领域已知的用于光电器件100的、具有电子传输性能的材料制备。例如，所述电子传输层30的材料包括但不限于金属氧化物、掺杂金属氧化物、II-VI族半导体材料、III-V族半导体材料及I-III-VI族半导体材料中的至少一种，所述 金属氧化物选自ZnO、BaO、TiO2、SnO2中的至少一种；所述掺杂金属氧化物中的金属氧化物选自ZnO、TiO2、SnO2中的至少一种，掺杂元素选自Al、Mg、Li、In、Ga中的至少一种，所述II-VI族半导体材料选自ZnS、ZnSe、CdS中的至少一种；所述III-V族半导体材料选自InP、GaP中的至少一种；所述I-III-VI族半导体材料选自CuInS、CuGaS中的至少一种。
可以理解的，所述光电器件100中各层的厚度根据需要设定，在此不做限制。在一些实施例中，所述第一电极的厚度为10-100nm，所述空穴注入层60的厚度为30～100nm，所述空穴传输层50的厚度为30～100nm，所述发光层20的厚度为10～50nm，所述电子传输层30的厚度为20～50nm，所述第二电极的厚度为30～100nm。
当阳极10和阴极40之间的膜层设有多个，且多个膜层选自发光层20、电子传输层30、空穴传输层50、空穴注入层60时，所述光电器件100的膜层层叠顺序为阳极10、空穴注入层60、空穴传输层50、发光层20、电子传输层30和阴极40；可以理解，所述光电器件100可以为正置型器件或倒置型器件。在一些实施例中，所述光电器件100为正置型器件，相应的，所述光电器件100包括自下而上依次层叠的阳极10、空穴注入层60、空穴传输层50、发光层20、电子传输层30和阴极40；在另一些实施例中，所述光电器件100为倒置型器件，相应的，所述光电器件100包括自下而上依次层叠的阴极40、电子传输层30、发光层20、空穴传输层50、空穴注入层60和阳极10。
可以理解，所述光电器件100还可以增设一些常规用于光电器件100的有助于提升光电器件100性能的功能层，例如电子注入层、电子阻挡层、空穴阻挡层、界面修饰层等。
可以理解，所述光电器件100的各层的材料可以依据光电器件100的实际需求进行调整。
实际制备时，所述光电器件100的各个膜层，例如所述阳极10、发光层20、电子传输层30及阴极40可采用本领域常规技术制备，例如化学法或物理法。其中，化学法包括化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法。物理法包括物理镀膜法和溶液法，其中，物理镀膜法包括：热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、 物理气相沉积法、原子层沉积法、脉冲激光沉积法等；溶液法可以为旋涂法、印刷法、喷墨打印法、刮涂法、打印法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法及条状涂布法等。
第四方面，本申请还提出一种显示装置，所述显示装置包括如上所述的光电器件100。所述显示装置可以为任何具有显示功能的电子产品，电子产品包括但不限于是智能手机、平板电脑、笔记本电脑、数码相机、数码摄像机、智能可穿戴设备、智能称重电子秤、车载显示器、电视机或电子书阅读器，其中，智能可穿戴设备例如可以是智能手环、智能手表、虚拟现实(Virtual Reality，VR)头盔等。
下面通过具体实施例、对比例和实验例对本申请的技术方案及技术效果进行详细说明，以下实施例仅仅是本申请的部分实施例，并非对本申请作出具体限定。
薄膜实施例1
薄膜的制备方法如下：
(1)按照空穴功能材料和添加剂的质量比为92：8，称取材料备用。其中，空穴功能材料为TFB；添加剂为1-甲氧基萘。
(2)取上述材料加入到氯苯中，搅拌混匀，得到空穴功能材料浓度为8mg/ml的混合溶液。
(3)以3000r/min的转速，将混合溶液旋涂在玻璃基板上，旋涂时间30s，然后，进行退火处理，退火温度为230℃，退火温度为30min，得到厚度为40nm的薄膜。
薄膜实施例2
本薄膜实施例与薄膜实施例1基本相同，区别仅在于，本薄膜实施例中：
添加剂为萘。
薄膜实施例3
本薄膜实施例与薄膜实施例1基本相同，区别仅在于，本薄膜实施例中：
添加剂为并三噻吩。
薄膜实施例4
本薄膜实施例与薄膜实施例1基本相同，区别仅在于，本薄膜实施例中：
添加剂为并三噻吩和茚的混合物，二者的摩尔比为1:1。
薄膜实施例5
本薄膜实施例与薄膜实施例1基本相同，区别仅在于，本薄膜实施例中：
空穴功能材料和添加剂的质量比为95：5。
薄膜实施例6
本薄膜实施例与薄膜实施例1基本相同，区别仅在于，本薄膜实施例中：
空穴功能材料和添加剂的质量比为90：10。
薄膜实施例7
本薄膜实施例与薄膜实施例1基本相同，区别仅在于，本薄膜实施例中：
空穴功能材料和添加剂的质量比为85：15。
薄膜实施例8
本薄膜实施例与薄膜实施例1基本相同，区别仅在于，本薄膜实施例中：
混合溶液由空穴功能材料和添加剂组成，且空穴功能材料为PEDOT:PSS；退火温度改为200℃。
薄膜对比例1
取TFB加入到氯苯中，搅拌混匀，得到浓度为8mg/ml的TFB溶液。
以3000r/min的转速，将TFB溶液旋涂在玻璃基板上，旋涂时间30s，然后，进行退火处理，退火温度为230℃，退火温度为30min，得到厚度为40nm的薄膜。
薄膜对比例2
以3000r/min的转速，将PEDOT:PSS溶液旋涂在玻璃基板上，旋涂时间30s，然后，进行退火处理，退火温度为200℃，退火温度为30min，得到厚度为40nm的薄膜。
器件实施例1
该QLED器件的制备方法如下：
(1)将图案化的ITO玻璃基板按次序置于丙酮、洗液、去离子水、异丙醇中进行超声清洗，且每一次超声时间为20min。清洗完成后，用氮气枪吹干。然后，将ITO玻璃基板放在氧气等离子体中继续清洗10min，再用紫外-臭氧处 理ITO玻璃基板表面15min，得到阳极，阳极厚度为10nm。
(2)在空气中，在阳极表面以3000r/min的转速旋涂一层PEDOT:PSS，旋涂时间30s，然后，进行退火处理，退火温度为150℃，退火温度为20min，得到厚度为80nm的空穴注入层。退火结束后将基板转移至充满氮气气氛的手套箱中。
(3)在空穴注入层的表面以3000r/min的转速旋涂薄膜实施例1中制得的混合溶液，旋涂时间30s，然后，进行退火处理，退火温度为230℃，退火温度为30min，得到厚度为40nm的空穴传输层。
(4)待步骤(3)制得的半成品冷却后，在空穴传输层表面，以1500r/min的转速旋涂40mg/ml的蓝色量子点材料CdZnSe/ZnSe/Cd/Cd0.6ZnS2，旋涂时间30s，然后，进行退火处理，退火温度为100℃，退火温度为5min，得到厚度为25nm的发光层。
(5)在发光层表面以3000r/min转速40mg/ml的ZnO乙醇溶液，旋涂时间30s，然后，进行退火处理，退火温度为100℃，退火时间为15min，得到厚度为30nm的电子传输层。
(6)将步骤(5)制得的半成品放入真空腔体中，在电子传输层表面蒸镀一层厚度为100nm的银作为阴极，封装，得到QLED器件。
器件实施例2～7
器件实施例m方案与器件实施例1基本相同，区别仅在于，器件实施例m中，步骤(3)中，用于制备空穴传输层的混合溶液改为薄膜实施例m制得的混合溶液，其中，m为2～7。
器件实施例8
本器件实施例方案与器件实施例1基本相同，区别仅在于，本器件实施例中，空穴注入层制备时掺入添加剂，空穴传输层采用常规方法，相应的：
1、步骤(3)中，用于制备空穴传输层的材料改为浓度为8mg/ml的TFB的氯苯溶液；
2、步骤(2)中，用于制备空穴注入层的材料改为薄膜实施例8制得的混合溶液。
器件实施例9
本器件实施例方案与器件实施例1基本相同，区别仅在于，本器件实施例中，空穴传输层和空穴注入层均在制备时掺入添加剂：
步骤(2)中，用于制备空穴注入层的材料改为薄膜实施例8制得的混合溶液。
器件对比例1和2
器件对比例n方案与器件实施例1基本相同，区别仅在于，器件对比例n中：
步骤(3)中，用于制备空穴传输层的材料改为薄膜对比例n制得的溶液，其中，n为1或2。
实验例一
(1)取薄膜实施例1制得的薄膜作为实验组，取薄膜对比例1制得的薄膜作为对照组，使用原子力显微镜(Atomic Force Microscope，AFM)观察实验组和对照组的薄膜，结果如图4和5所示。
(2)取薄膜实施例1至8以及薄膜对比例1至2制得的薄膜，使用原子力显微镜(Atomic Force Microscope，AFM)检测薄膜的均方根粗糙度Rq，记录在表1中。
表1
从图4和图5中，可以看出实验组薄膜更加均匀，表面粗糙度也更小，具有 更好的表面形貌；从表1的数据可以看出，实施例1至7的薄膜具有比薄膜对比例1更低的均方根粗糙度Rq，实施例8薄膜具有比薄膜对比例2更低的均方根粗糙度Rq，说明添加剂的加入使空穴功能材料之间的排列更加规整，减少了不规则的局部过度团聚，从而显著改善了薄膜形貌。
实验例二
空穴传输性能测试：通过LabView控制QE PRO和Keithley 2400，搭建一套QLED效率测试系统。由该系统测试单载流子传输薄膜器件(HOD/EOD)的电流密度-电压曲线。取器件的工作电压(6V)下的电流密度和稳定状态下的工作电压进行比较，稳定状态下的工作电压是指器件寿命测试过程中，器件运行4小时以上，器件平衡阶段的工作电压。其中：
单空穴器件(HOD)的制备方法与其对应的完整的QLED器件的制备方法基本相同，区别仅在于，减去电子传输层。
上述测试中，所使用的器件为上述器件实施例1至9和器件对比例1-2中QLED器件对应的单空穴器件。
表2

由上表可以看出：
相较器件对比例1的单空穴器件，器件实施例1至7、9均具有更高的电流效率和更低的工作电压，同时，相较器件对比例2，器件实施例8和9均具有更高的电流效率和更低的工作电压，说明在制备空穴功能层时掺入添加剂，有助于提高膜层的空穴传输、注入性能，进而提升器件的电学性能。
实验例三
对器件实施例1-9及器件对比例1-2的量子点发光二极管进行性能测试，测试结果参表3。测试方法如下：
(1)外量子效率EQE的检测方法为：注入到量子点中的电子-空穴对数转化为出射的光子数的比值，单位是％，是衡量电致发光器件优劣的一个重要参数，采用EQE光学测试仪器测定即可得到。具体计算公式如下：
其中，ηe为光输出耦合效率，ηγ为复合的载流子数与注入载流子数的比值，x为产生光子的激子数与总激子数的比值，KR为辐射过程速率，KNR为非辐射过程速率。
测试条件：在室温下进行，空气湿度为30～60％。
(2)寿命T95@1000nit的测试方法为：
器件在恒定电流或电压驱动下，亮度减少至最高亮度的一定比例时所需的时间，亮度下降至最高亮度的95％的时间定义为T95，该寿命为实测寿命。为缩短测试周期，器件寿命测试通常是在高亮度下通过加速器件老化进行，并通过延伸型指数衰减亮度衰减拟合公式拟合得到高亮度下的寿命，比如：1000nit下的寿命计为T95@1000nit。具体计算公式如下：
其中，T95L为低亮度下的寿命，T95H为高亮度下的实测寿命，LH为器件加速至最高亮度，LL为1000nit，A为加速因子，本实验通过测得若干组QLED器件在额定亮度下的寿命得出A值为1.7。
上述测试中，外量子效率测试和器件寿命测试所使用的器件为上述实施例和对比例中完整结构的QLED器件。
表3
由表3可知：
相较器件对比例1的单空穴器件，器件实施例1至7、9均具有更高的EQE和T95@1000nit，同时，相较器件对比例2，器件实施例8和9均具有更高的EQE和T95@1000nit，说明在制备空穴功能层时掺入添加剂，有助于提高膜层的空穴传输、注入性能，改善器件的载流子平衡，进而提升器件的发光效率和寿命。
以上对本申请实施例所提供的薄膜及其制备方法及光电器件进行了详细介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本申请的方法及其核心思想；同时，对于本领域的技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本申请的限制。

Claims (20)

  1. 一种薄膜的制备方法，其中，包括以下步骤：
    提供混合溶液，所述混合溶液包括空穴功能材料和添加剂；
    沉积所述混合溶液，然后退火以去除所述添加剂，得到薄膜；
    其中，所述添加剂包括具有式(1)所示结构的化合物：
    其中，环A包括环碳原子数为6～40的芳环和环原子数为6～40的杂芳环中的一种或者多种，n为正整数；
    X每次出现时独立的选自氢、氘、给电子基团中的一种或多种。
  2. 根据权利要求1所述的制备方法，其中，所述给电子基团包括-NH2、C1～C3烷基以及C1～C3烷氧基中的一种或多种的组合。
  3. 根据权利要求1或2所述的制备方法，其中，环A包括环碳原子数为6～20的芳环和环原子数为6～20的杂芳环中的一种或者多种。
  4. 根据权利要求3所述的制备方法，其中，环A选自式(2)至(7)任一所示结构的环中的一种或多种：
  5. 根据权利要求1至4任一项所述的制备方法，其中，n为1～4。
  6. 根据权利要求5所述的制备方法，其中，n为1或2。
  7. 根据权利要求1至6任一项所述的制备方法，其中，所述添加剂的沸点大于等于100℃，且小于200℃。
  8. 根据权利要求7所述的制备方法，其中，所述添加剂包括具有如下式 (8)至(16)任一项所示结构的化合物中的一种或多种：
  9. 根据权利要求1至7任一项所述的制备方法，其中，X每次出现时独立的选自所述给电子基团。
  10. 根据权利要求1至7任一项所述的制备方法，其中，所述添加剂包括具有所述式(11)至所述(16)任一项所示结构的化合物中的一种或多种：

  11. 根据权利要求1至10任一项所述的制备方法，其中，所述添加剂的质量占所述添加剂和所述空穴功能材料的总质量的百分比为5～10％。
  12. 根据权利要求1至11任一项所述的制备方法，其中，所述空穴功能材料包括空穴传输材料或空穴注入材料，所述空穴传输材料选自聚[(9,9'-二辛基芴-2,7-二基)-共-(4,4'-(N-(4-仲丁基苯基)二苯胺))]、聚(4-丁基苯基-二苯基胺)、聚(三芳胺)、聚吡咯、聚[N,N′-双(4-丁苯基)-N,N′-双(苯基)-联苯胺]、聚(对)亚苯基亚乙烯基、聚[2-甲氧基-5-(2-乙基己氧基)-1,4-亚苯基亚乙烯基]和聚[2-甲氧基-5-(3',7'-二甲基辛氧基)-1,4-亚苯基亚乙烯基]、PEDOT:PSS及其衍生物、聚(N-乙烯基咔唑)及其衍生物、聚甲基丙烯酸酯及其衍生物、聚(9，9-辛基芴)及其衍生物、聚(螺芴)及其衍生物中的至少一种；所述空穴注入材料选自PEDOT、PEDOT:PSS、酞菁铜中的至少一种。
  13. 根据权利要求1至12任一项所述的制备方法，其中，所述沉积所述混合溶液，然后退火以去除所述添加剂，得到薄膜的步骤中，所述退火的温度为200～230℃。
  14. 根据权利要求1至13任一项所述的制备方法，其中，所述退火的时间为15～45min。
  15. 根据权利要求1至14任一项所述的制备方法，其中，所述混合溶液还包括溶剂，所述溶剂包括醇类溶剂、氯仿、氯苯、二氯苯中的一种或多种。
  16. 根据权利要求1至15任一项所述的制备方法，其中，所述混合溶液中，所述空穴功能材料的浓度为2～15mg/ml。
  17. 一种薄膜，其中，所述薄膜的材料包括空穴功能材料，所述薄膜的均方根粗糙度为0.3～1.5。
  18. 根据权利要求17所述的薄膜，其中，所述薄膜的空穴迁移率为10-3～10-1cm2 V–1s–1。
  19. 一种光电器件，其中，包括第一电极、空穴功能层和第二电极，所述空穴功能层包括空穴注入层和空穴传输层中的一层或两层，且所述空穴功能层中的至少一层包括如权利要求17或18所述的薄膜，或者，包括权利要求1至16任一项所述的制备方法制得的薄膜。
  20. 根据权利要求19所述的光电器件，其中，所述第一电极和所述第二电极各自独立的选自掺杂金属氧化物颗粒电极、金属与金属氧化物的复合电极、石墨烯电极、碳纳米管电极、金属电极或合金电极，所述掺杂金属氧化物颗粒电极的材料选自铟掺杂氧化锡、氟掺杂氧化锡、锑掺杂氧化锡、铝掺杂氧化锌、镓掺杂氧化锌、铟掺杂氧化锌、镁掺杂氧化锌及铝掺杂氧化镁中的一种或多种，所述金属与金属氧化物的复合电极选自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，所述金属电极的材料选自Ag、Al、Cu、Mo、Au、Pt、Si、Ca、Mg及Ba中的一种或多种；和/或，
    所述光电器件还包括发光层，所述发光层设于所述第一电极和所述空穴功能层之间，或者所述发光层设于所述二电极和所述空穴功能层之间，所述发光层的材料选自有机发光材料及量子点发光材料中的一种或多种，所述有机发光材料选自4,4'-双(N-咔唑)-1,1'-联苯:三[2-(对甲苯基)吡啶合铱(III)、4,4',4”-三(咔唑-9-基)三苯胺:三[2-(对甲苯基)吡啶合铱、二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPX荧光材料、TBRb荧光材料、DBP荧光材料、延迟荧光材料、TTA材料、热活化延迟材料、含有B-N共价键合的聚合物、杂化局域电荷转移激发态材料、激基复合物发光材料中的一种或多种；所述量子点发光材料选自单一结构量子点、核壳结构量子点及钙钛矿型半导体材料中的至少一种；所述单一结构量子点的材料、核壳结构量子点的核材料及核壳结构量子点的壳层材料分别选自II-VI族化合物、IV-VI族化合物、III-V族化合物和I-III-VI族化合物中的至少一种；所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、 HgZnSeS、HgZnSeTe及HgZnSTe中的至少一种；所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTe中的至少一种；所述III-V族化合物选自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及InAlPSb中的至少一种；所述I-III-VI族化合物选自CuInS2、CuInSe2及AgInS2中的至少一种；所述钙钛矿型半导体材料选自掺杂或非掺杂的无机钙钛矿型半导体、或有机-无机杂化钙钛矿型半导体；所述无机钙钛矿型半导体的结构通式为AMX3，其中A为Cs+离子，M为二价金属阳离子，选自Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+中的至少一种，X为卤素阴离子，选自Cl-、Br-、I-中的至少一种；所述有机-无机杂化钙钛矿型半导体的结构通式为BMX3，其中B为有机胺阳离子，选自CH3(CH2)n-2NH3 +或[NH3(CH2)nNH3]2+，其中n≥2，M为二价金属阳离子，选自Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+中的至少一种，X为卤素阴离子，选自Cl-、Br-、I-中的至少一种。
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