WO2024259820A1 - 发光器件及显示装置 - Google Patents

发光器件及显示装置 Download PDF

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WO2024259820A1
WO2024259820A1 PCT/CN2023/121754 CN2023121754W WO2024259820A1 WO 2024259820 A1 WO2024259820 A1 WO 2024259820A1 CN 2023121754 W CN2023121754 W CN 2023121754W WO 2024259820 A1 WO2024259820 A1 WO 2024259820A1
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light
emitting device
layer
transport layer
doped
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聂志文
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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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays

Definitions

  • the present application relates to the field of display, and in particular to a light-emitting device and a display apparatus.
  • Quantum dot light-emitting diodes constructed with quantum dots as the light-emitting layer have become one of the most active scientific research topics due to their many advantages such as low cost, high brightness, wide color gamut, and excellent solution processability, and have shown great competitive potential in the next generation of flat panel display and solid-state lighting applications.
  • QLED devices high-efficiency and long-life devices are the basis for promoting the industrialization of QLED products.
  • the present application provides a light emitting device and a display apparatus.
  • the present application provides a light-emitting device, comprising an anode, a hole transport layer, a light-emitting layer and a cathode stacked in sequence, wherein the material of the light-emitting layer comprises quantum dots, and the thickness of the light-emitting layer is 1 to 1.5 times the average particle size of the quantum dots;
  • the material of the hole transport layer has a mobility of 0.1 ⁇ 10 -3 to 2 ⁇ 10 -3 cm 2 /Vs.
  • the mobility of the material of the hole transport layer is 0.5 ⁇ 10 ⁇ 3 ⁇ 1 ⁇ 10 ⁇ 3 cm 2 /Vs.
  • the energy levels of the hole transport layer and the light emitting layer are The absolute value of the difference is 0.1 to 1.6 eV.
  • the HOMO energy level of the material of the hole transport layer is -5 eV to -6 eV.
  • the material of the hole transport layer includes any one of CBP, NPB, a first compound and a second compound, the first compound has a structural formula as shown in formula (I), and the second compound has a structural formula as shown in formula (II).
  • the average particle size of the quantum dots is 11 to 16 nm.
  • the fluorescence quantum yield of the quantum dots is greater than or equal to 70%.
  • a ligand is connected to the surface of the quantum dot; the ligand includes a first ligand, the raw material of the first ligand is selected from one or more of substituted or unsubstituted C1 ⁇ C24 chain thiols and halides, and the substituent when substituted is selected from at least one of C1 ⁇ C8 alkyl, C1 ⁇ C8 alkoxy and halogen; the mass of the first ligand accounts for 15 ⁇ 20% of the total mass of the quantum dot and the ligand.
  • the quantum dots are core-shell structured quantum dots, and the quantum dots have a first shell and a second shell from the inside to the outside, wherein the material of the first shell is ZnSe, and the material of the second shell is CdZnS.
  • the ratio of the thickness of the first shell layer to the radius of the core of the quantum dot is 0.5 to 2:1.
  • the ratio of the thickness of the second shell layer to the radius of the core of the quantum dot is 0.4 to 2:1.
  • the material of the core is selected from at least one of a II-VI group compound, an IV-VI group compound, a III-V group compound and an I-III-VI group compound;
  • the II-VI group compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZ nTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgS, CdHgSe, C
  • the light-emitting device further includes an electron transport layer disposed between the cathode and the light-emitting layer.
  • the mobility of the material of the electron transport layer is 0.5 ⁇ 10 ⁇ 3 ⁇ 1 ⁇ 10 ⁇ 3 cm 2 /Vs.
  • the average particle size of the material of the electron transport layer is 2 to 12 nm.
  • the material of the electron transport layer includes one or more of metal oxides and doped metal oxides;
  • the metal oxide includes one or more of ZnO, TiO 2 , SnO 2 , ZrO, Al 2 O 3 , WO 3 , HfO 3 , Ta 2 O 3 , ZrSiO 4 , BaTiO 3 , and BaZrO 3 ;
  • the metal oxide in the doped metal oxide includes multiple of ZnO, TiO 2 , SnO 2 , ZrO, Al 2 O 3 , WO 3 , HfO 3 , Ta 2 O 3 , ZrSiO 4 , BaTiO 3 , and BaZrO 3
  • the doping elements include one or more of Al, Mg, Li, In, Ga, Cd, Cs, and Cu.
  • the anode and the cathode are independently selected from 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, and the material of the doped metal oxide particle electrode is selected from indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, One or more of 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/ZnO, TiO 2 /Ag/TiO 2 , TiO
  • the light-emitting device further comprises a hole injection layer disposed between the anode and the hole transport layer, wherein the material of the hole injection layer comprises poly(ethylenedioxythiophene): polystyrene sulfonate, poly[(9,9'-dioctylfluorenyl-2,7-diyl)-CO-(4,4'-(N-(p-butylphenyl))diphenylamine)], polyarylamine, poly(N-vinylcarbazole), polyaniline, polypyrrole, N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine, 4-bis[N-(1-naphthyl)-N-phenyl-amino]- One or more of: 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine, 4,4',4"-tri(carbazole-9-y
  • the thickness of the anode is 20 to 200 nm; and/or,
  • the thickness of the cathode is 40 to 190 nm; and/or,
  • the thickness of the hole transport layer is 30 to 180 nm; and/or,
  • the thickness of the electron transport layer is 20 to 180 nm.
  • the light-emitting device further includes a hole injection layer disposed between the anode and the hole transport layer, and the hole injection layer has a thickness of 20 to 200 nm.
  • the present application further proposes a display device, which includes the light-emitting device described above.
  • FIG1 is a schematic structural diagram of a light emitting device proposed in the first embodiment of the present application.
  • FIG2 is a schematic structural diagram of a light emitting device proposed in a second embodiment of the present application.
  • FIG3 is a schematic structural diagram of a light emitting device proposed in the third embodiment of the present application.
  • FIG4 is a schematic structural diagram of a light emitting device proposed in a fourth embodiment of the present application.
  • Reference numerals 100 - light-emitting device; 10 - anode; 20 - light-emitting layer; 30 - cathode; 40 - electron transport layer; 50 - hole transport layer; 60 - hole injection layer; 201 - quantum dots.
  • 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, and “more than one” means two or more.
  • At least one means two or more.
  • At least one means at least one of the following or similar expressions refer to any combination of these items, including any combination of single or plural items.
  • at least one of a, b, or c or “at least one of a, b, and c” can all mean: a, b, c, ab (i.e. a and b), ac, bc, or abc, where a, b, and c can be single or plural, respectively.
  • the present application provides a light-emitting device 100, which can be a quantum dot light-emitting diode (QLED) or the like.
  • the light-emitting device 100 includes an anode 10, a hole transport layer 50, a light-emitting layer 20, and a cathode 30 stacked in sequence, the material of the light-emitting layer 20 includes quantum dots 201, and the thickness of the light-emitting layer 20 is 1 to 1.5 times the average particle size of the quantum dots 201; for example, it can be 1 times, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, and a value between any two of the above values.
  • QLED quantum dot light-emitting diode
  • the light-emitting layer 20 obtained is roughly a single-layer film.
  • the single-layer film refers to a thin film roughly formed by a single layer of core-shell quantum dots 201 in the thickness direction of the device, and its overall embodiment is: the thickness of the film is 1 to 1.5 times the average particle size of the quantum dots 201 used to prepare the film.
  • the surface of the quantum dot 201 is connected with a ligand;
  • the ligand includes a first ligand, the raw material of the first ligand is selected from one or more of substituted or unsubstituted C1-C24 chain thiols and halides, and the substituent when substituted is selected from at least one of C1-C8 alkyl, C1-C8 alkoxy and halogen;
  • the mass of the first ligand accounts for 15-20% of the total mass of the quantum dot 201 and the ligand;
  • the thickness of the light-emitting layer 20 is 1-1.5 times the average particle size of the quantum dot 201.
  • the raw material of the ligand includes at least one of substituted or unsubstituted C10-C24 chain organic carboxylic acids, substituted or unsubstituted C10-C24 chain organic amines, substituted or unsubstituted C1-C24 chain thiols, substituted or unsubstituted C10-C24 chain organic phosphines, substituted or unsubstituted C10-C24 chain organic phosphine oxides, and halides.
  • substituted or unsubstituted means that the defined group may be substituted or not.
  • the defined group may be substituted by one or more substituents; the substituents are selected from at least one of C1-C8 alkyl, C1-C8 alkoxy, and halogen; optionally, the substituents are selected from at least one of C1-C5 alkyl, C1-C5 alkoxy, and halogen; or the substituents are selected from at least one of C1-C3 alkyl, C1-C3 alkoxy, and halogen.
  • the halogen refers to -F, -Cl, -Br or -I.
  • the organic carboxylic acid includes one or more of decadecanoic acid (CAS: 334-48-5), undecenoic acid (CAS: 112-38-9), tetradecanoic acid (CAS: 544-63-8), oleic acid (CAS: 112-80-1) and stearic acid (CAS: 57-11-4);
  • the organic amine includes one or more of oleylamine (CAS: 112-90-3) and octadecylamine (CAS: 124-30-1);
  • the organic (oxygen) phosphine includes trioctylphosphine (CAS: 4731-53-7), trioctylphosphine oxide (CAS: 78-50-2) or more;
  • the thiol includes one or more of n-octyl mercaptan (CAS: 111-88-6), dodecanethiol (CAS: 112-55-0) and octadecanethiol (CAS: 2885-00-9);
  • the halide is
  • the mass of the ligand accounts for 15% to 20% of the total mass of the quantum dots 201 and the ligand, for example, it can be 15%, 16%, 17%, 18%, 19%, 20% and values between any two of the above values. Within this range, it helps to improve the dispersibility of the quantum dots 201 and enhance its film-forming effect.
  • the ligand includes a first ligand
  • the first ligand is selected from one or more of substituted or unsubstituted C1-C24 chain thiols and halides
  • the first ligand can form a strong coordination bond with the surface cations of the quantum dot 201, is not easy to fall off, and helps to improve the film-forming effect of the light-emitting layer 20.
  • the mass percentage of the first ligand is 15% to 20%, for example, it can be 15%, 16%, 17%, 18%, 19%, 20% and a value between any two of the above values.
  • the anions on the surface of the quantum dot 201 include sulfur atoms
  • the quantum dot 201 is CdS or CdSe/ZnSe/CdZnS
  • the ligand is a thiol ligand
  • the thiol compound when preparing the quantum dot 201, can be added as an anion source, and the S atoms on the ligand can be directly coordinated and connected with the cations on the surface of the quantum dot 201, or directly act as S atoms on the shell surface of the quantum dot 201 and be directly embedded in the shell, which helps to further improve the coordination effect of the ligand and reduce the probability of shedding.
  • the content of the ligand and the first ligand can be detected by nuclear magnetic resonance and thermal gravimetric test, and the amount of the first ligand on the surface of quantum dot 201 can be introduced during the synthesis process or introduced by ligand exchange.
  • nuclear magnetic resonance can measure the content of specific ligands on the surface of quantum dot 201.
  • thermal gravimetric test can determine the total content of ligands on the surface of quantum dot 201.
  • both The ligand difference is the content of other ligands.
  • the specific test method for measuring the content of specific ligands on the surface of quantum dot 201 by nuclear magnetic resonance is as follows: dissolve quantum dot 201 in a deuterated reagent, and add a specific amount of internal standard as a reference, and calculate the ratio of the chemical shift integral area of the ligand of quantum dot 201 to the chemical shift integral area of the internal standard, so as to quantify the content of the ligand to be measured.
  • the thermal gravimetric test detection method is as follows: heat the quantum dot 201 material until its mass no longer changes, record the weight loss W1 of the material when it starts to lose weight to the shedding temperature of the strongly coordinated ligand (i.e., the first ligand), and record the weight loss W2 of the material when it starts to lose weight to the time when its mass no longer changes, then W2 is the content of the ligand, and W2 - W1 is the content of the first ligand.
  • NMR and thermal gravimetric methods can also be used simultaneously, for example: to determine the content of specific quantum dot 201 surface ligands oleic acid (weak ligand) and thiol (where thiol is the first ligand).
  • the specific test method is as follows: First, dissolve quantum dot 201 in deuterated toluene, use ferrocene as an internal standard (the amount added is rated, the chemical shift is 3.8-4.0ppm), and measure the chemical shift of quantum dot 201 ligand at 5.4-5.8ppm.
  • the light-emitting layer 20 can be set as a single-layer film.
  • a single-layer film has a lower tunneling barrier and is convenient for carrier injection.
  • the mobility of the material of the hole transport layer 50 is greater than or equal to 0.1 ⁇ 10 -3 cm 2 /Vs and less than or equal to 2 ⁇ 10 -3 cm 2 /Vs, for example, 0.1 ⁇ 10 -3 cm 2 /Vs, 0.2 ⁇ 10 -3 cm 2 /Vs, 0.5 ⁇ 10 -3 cm 2 /Vs, 0.6 ⁇ 10 -3 cm 2 /Vs, 0.7 ⁇ 10 -3 cm 2 /Vs, 0.8 ⁇ 10 -3 cm 2 /Vs, 0.9 ⁇ 10 -3 cm 2 /Vs, 1 ⁇ 10 -3 cm 2 /Vs, 1.3 ⁇ 10 -3 cm 2 /Vs, 1.5 ⁇ 10 -3 cm 2 /Vs, 1.7 ⁇ 10 -3 cm 2 /Vs, 1.9 ⁇ 10 -3 cm 2 /Vs, /Vs, 2 ⁇ 10 -3 cm 2 /Vs, 2 ⁇ 10 -3 cm 2
  • the light-emitting layer 20 is set as a single-layer film constructed of a single-layer quantum dot, and
  • the hole transport layer with a hole mobility of 0.1 ⁇ 10 -3 ⁇ 2 ⁇ 10 -3 cm 2 /Vs can give full play to the advantage of relatively low tunneling barrier of single-layer film, effectively enhance hole injection, improve the injection balance of holes and electrons, and thus improve the efficiency and life of the device.
  • the mobility of the material of the hole transport layer 50 is 0.5 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 3 cm 2 /Vs, which helps to further improve the carrier balance.
  • the absolute value of the energy level difference between the hole transport layer 50 and the light emitting layer 20 is 0.1 to 1.6 eV, for example, 0.1 eV, 0.3 eV, 0.5 eV, 0.7 eV, 0.9 eV, 1.0 eV, 1.1 eV, 1.3 eV, 1.5 eV, 1.6 eV, and values between any two of the above values.
  • the hole injection barrier can be reduced, which helps to further enhance hole injection.
  • the HOMO energy level of the material of the hole transport layer 50 is -5eV to -6eV; for example, -5eV, -5.2eV, -5.3eV, -5.4eV, -5.5eV, -5.6eV, -5.7eV, -5.8eV, -5.9eV, -6eV and values between any two of the above values.
  • the material of the hole transport layer 50 includes CBP (4,4'-bis(9H-carbazole-9-yl)biphenyl, CAS: 58328-31-7), NPB (N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, CAS: 123847-85-8), any one of the first compound and the second compound, the first compound having a structural formula as shown in formula (I), and the second compound having a structural formula as shown in formula (II).
  • the preparation method and electrical properties of the first compound and the second compound can refer to Chinese patent CN110504379A-A composite electron blocking layer and OLED device thereof.
  • the HOMO energy level of CBP is -5.8eV, and the hole mobility is 1.0 ⁇ 10-3 cm2 /Vs;
  • the HOMO energy level of NPB is -5.5eV, and the hole mobility is 8.8 ⁇ 10-4 cm2 /Vs;
  • the HOMO energy level of the first compound is -5.49eV, and the hole mobility is 8.7 ⁇ 10-4 cm2 /Vs;
  • the HOMO energy level of the second compound is -5.6eV, and the hole mobility is 8.6 ⁇ 10-4 cm2 /Vs.
  • the fluorescence quantum yield (QY) of the quantum dots 201 is greater than or equal to 70%, for example, 70%, 75%, 80%, 85%, 90%, 92%, etc.
  • the quantum dots 201 usually have fewer defects, which can reduce the probability of non-radiative recombination and improve the recombination of carriers. Therefore, in some cases, it is inevitable to face the scenario of using high-luminescence efficiency quantum dots in the light-emitting layer and setting a single-layer film.
  • the quantum dots 201 with higher QY usually have higher shell coating quality and better exciton binding, so that the shell has a larger carrier injection barrier, making carrier injection relatively difficult.
  • the embodiment of the present application makes the light-emitting layer 20 a single-layer film, and matches it with a hole transport layer 50 with a hole mobility of 0.1 ⁇ 10-3 to 2 ⁇ 10-3 cm2 /Vs, which helps to enhance hole injection, overcome the problem of difficulty in external carrier injection in high-efficiency quantum dots 201, improve the effective injection and efficient recombination of carriers in the device, and improve the injection balance of holes and electrons, thereby improving the efficiency and life of the device.
  • the average particle size of the quantum dots 201 is 11-16 nm, for example, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, and values between any two of the above values, and a single layer of film is formed on the quantum dots 201, which helps to improve the film-forming effect.
  • the thickness of the light-emitting layer 20 is 11-24 nm, for example, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 20 nm, 22 nm, 23 nm, 24 nm, and values between any two of the above values.
  • the shape of the quantum dot 201 includes but is not limited to sphere, cube, tetrahedron, column, tetrapod, octapod, flake, etc.
  • the quantum dot 201 is a quantum dot 201 of a core-shell structure, and the quantum dot 201 has a first shell and a second shell from the inside to the outside.
  • the material of the first shell is ZnSe, and the shallow valence band helps to improve hole injection, but its own band gap is relatively moderate, and its ability to bind excitons is relatively weak;
  • the material of the second shell is CdZnS, which not only has a relatively wide band gap, but also has a relatively moderate position of the valence band, which can ensure that the hole injection into the luminescent core is improved under the premise of exciton binding, thereby improving the carrier recombination efficiency.
  • the two shells work together to effectively reduce the hole injection barrier, which helps to efficiently inject holes into the core of the quantum dot 201.
  • the ratio of the thickness of the first shell layer to the radius of the core of the quantum dot 201 is 0.5 to 2:1; for example, the ratio can be 0.5:1, 0.6:1, 0.8:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.5:1, etc.; this helps to effectively control the binding ability of excitons, which is not only beneficial to reduce the tunneling barrier during carrier injection and promote carrier injection, but also helps to effectively recombine the carriers injected into the core of the quantum dot 201.
  • the ratio of the thickness of the second shell layer to the radius of the core of the quantum dot 201 is 0.4 to 2:1; for example, the ratio can be 0.4:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.3:1, 1.5:1, 1.7:1, 1.8:1, 2:1, etc.; it helps to effectively control the binding ability of excitons and isolate the excitons from the outside world, thereby reducing the probability of excitons being captured by the outside world, while reducing the tunneling barrier during carrier injection and promoting carrier injection.
  • the core material of the quantum dot 201 may be selected from but not limited to at least one of a II-VI compound, an IV-VI compound, a III-V compound, and an I-III-VI compound; as an example, the II-VI compound is selected from but not limited to CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeT e, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnST
  • the core-shell structured quantum dots 201 may be selected from but not limited to at least one of CdZnSe/ZnSe/CdZnS, CdSe/ZnSe/CdZnS, InP/ZnSe/CdZnS, CdSeS/ZnSe/CdZnS, ZnSe/ZnSe/CdZnS, and ZnSeTe/ZnSe/CdZnS.
  • the provided chemical formula only indicates the elemental composition, but does not indicate the content of each element.
  • CdZnS only indicates that it is composed of three elements: Cd, Zn and S. If the content of each element is indicated, it corresponds to Cd x Zn 1-x S, 0 ⁇ x ⁇ 1.
  • the mobility of the material of the electron transport layer 40 is 0.5 ⁇ 10 -3 ⁇ 1 ⁇ 10 -3 cm 2 /Vs, for example, 0.5 ⁇ 10 -3 cm 2 /Vs, 0.6 ⁇ 10 -3 cm 2 /Vs, 0.7 ⁇ 10 -3 cm 2 /Vs , 0.8 ⁇ 10 -3 cm 2 /Vs, 0.9 ⁇ 10 -3 cm 2 / Vs , 1.0 ⁇ 10 -3 cm 2 /Vs, and any values between the above two values.
  • the electron injection can be precisely controlled to balance the electron injection with the hole injection in the device, thereby effectively improving the carrier balance of the device, avoiding the light-emitting layer 20 from being charged and inducing Auger recombination, thereby affecting the life and efficiency of the device.
  • the average particle size of the material of the electron transport layer 40 is 2 to 12 nm, for example, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 8 nm, 10 nm, 11 nm, 12 nm, and values between any two of the above values.
  • the electron transport material with such a particle size is easy to be made into a film with uniform film thickness and dense film during film formation, which helps to improve the film quality.
  • the material of the electron transport layer 40 includes, but is not limited to, one or more of metal oxides and doped metal oxides.
  • the metal oxide includes, but is not limited to, one or more of ZnO, TiO 2 , SnO 2 , ZrO, Al 2 O 3 , WO 3 , HfO 3 , Ta 2 O 3 , ZrSiO 4 , BaTiO 3 , and BaZrO 3 ;
  • the metal oxide in the doped metal oxide includes, but is not limited to, multiple of ZnO, TiO 2 , SnO 2 , ZrO, Al 2 O 3 , WO 3 , HfO 3 , Ta 2 O 3 , ZrSiO 4 , BaTiO 3 , and BaZrO 3
  • the doping element includes, but is not limited to, one or more of Al, Mg, Li, In, Ga, Cd, Cs, and Cu.
  • the surface of the electron transport material may be connected with a ligand, and the ligand is derived from one or more of an acid ligand, an amine ligand, and a thiol ligand.
  • the raw materials of the ligand include but are not limited to one or more of oleic acid, oleylamine, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, and octadecanoic acid.
  • the cation source is a metal salt that can provide the M metal element, such as zinc acetate, etc.
  • the cation source includes a metal salt that can provide the M metal element and a metal salt that can provide the A doping element, such as zinc acetate, magnesium acetate, etc.
  • the alkali source includes one or more of an organic base and an inorganic base, the organic base is selected from one or more of hexamethylenetetramine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and urea
  • the inorganic base is selected from one or
  • the mobility of the electron transport layer 40 material can be accurately controlled by adjusting the type and content of the doping element, the amount of alkali source added, the post-treatment conditions and other parameters. In actual operation, reference can be made to the following parameters:
  • the preparation is carried out according to the method commonly used in the art for regulating the mobility of the electron transport layer 40 material. Taking the method of regulating the amount of alkali source added to control the electron mobility as an example, in some embodiments, the electron transport layer 40 material is ZnO. In order to regulate its electron mobility, tetramethylammonium hydroxide can be used as an alkali source.
  • the molar ratio of ZnO and tetramethylammonium hydroxide is controlled to be 1:1.5, and ZnO nanoparticles with a mobility of 0.1 ⁇ 10-3 cm2 /Vs can be obtained; the molar ratio of ZnO and tetramethylammonium hydroxide can also be controlled to be 1:0.5, and ZnO nanoparticles with a mobility of 5 ⁇ 10-3 cm2 /Vs can be obtained.
  • the anode 10 is 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 , TiO2 /Ag/ TiO2 , TiO2 /Al/TiO2, 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 30 is 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 , TiO2 /Ag/ TiO2 , TiO2 /Al/TiO2, 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 light-emitting device 100 further includes a hole injection layer 60 disposed between the anode 10 and the hole transport layer 50.
  • the material of the hole injection layer 60 includes poly(ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), poly[(9,9'-dioctylfluorenyl-2,7-diyl)-CO-(4,4'-(N-(p-butylphenyl))diphenylamine)] (TFB), polyarylamine, poly(N-vinylcarbazole), polyaniline, polypyrrole, N,N,N',N'-tetrakis(4-methoxyphenyl)-benzidine (TPD), 4-bis[N-(1-naphthalene)]- One or more of 1,4',4"-tris[(phenyl(m-tolyl)amino]triphenylamine (m-
  • the thickness of the anode 10 is 20-200 nm; for example, it can be 20-40 nm, 30-60 nm, 50-80 nm, 55-90 nm, 70-100 nm, 90-120 nm, 110-140 nm, 130-150 nm, 140-170 nm, 160-200 nm, and the like.
  • the thickness of the cathode 30 is 40-190 nm; for example, it can be 40-60 nm, 50-80 nm, 55-90 nm, 70-100 nm, 90-120 nm, 110-140 nm, 130-150 nm, 140-170 nm, 160-190 nm, and the like.
  • the thickness of the hole transport layer 50 is 30 to 180 nm; for example, it can be 30 to 40 nm, 35 to 60 nm, 50 to 80 nm, 55 to 90 nm, 70 to 100 nm, 90 to 120 nm, 110 to 140 nm, 130 to 150 nm, 140 to 170 nm, 160 to 180 nm, and the like.
  • the thickness of the electron transport layer 40 is 20-180 nm; for example, it can be 20-40 nm, 30-60 nm, 50-80 nm, 55-90 nm, 70-100 nm, 90-120 nm, 110-140 nm, 130-150 nm, 140-170 nm, 160-180 nm, and the like.
  • the thickness of the hole injection layer 60 is 20-200 nm; for example, it can be 20-40 nm, 30-60 nm, 50-80 nm, 55-90 nm, 70-100 nm, 90-120 nm, 110-140 nm, 130-150 nm, 140-170 nm, 160-200 nm, and the like.
  • the light emitting device 100 may also be provided with some functional layers conventionally used in the light emitting device 100 to help improve the performance of the light emitting device 100, such as an electron blocking layer, a hole blocking layer, an interface modification layer, etc.
  • the light emitting device 100 can be an upright light emitting device or an inverted light emitting device.
  • the present application further proposes a method for preparing a light emitting device 100, which is used to prepare the above light emitting device 100.
  • the light emitting device 100 may be a positive light emitting device, and accordingly, the preparation method includes:
  • the light emitting device 100 may be an inverted light emitting device, and accordingly, the preparation method includes:
  • the hole functional layer includes the hole transport layer 50 , or includes the hole transport layer 50 and the hole injection layer 60 .
  • the hole injection layer 60 is disposed closer to the anode 10 .
  • the preparation method of the anode 10 the preparation method of the anode 10, the light-emitting layer 20, the electron transport layer 40, the hole transport layer 50, the hole injection layer 60 and the cathode 30 can be achieved by conventional techniques in the art, such as chemical methods or physical methods.
  • the chemical method includes chemical vapor deposition, continuous ion layer adsorption and reaction, anodization, electrolytic deposition, and coprecipitation.
  • the physical method includes physical plating and solution method, among which the physical plating method includes: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method can be spin coating, printing, inkjet printing, blade coating, printing, dip pulling, immersion, spraying, roll coating, casting, slit coating, and strip coating.
  • the physical plating method includes: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.
  • the solution method can be spin coating, printing, inkjet printing, blade coating, printing, dip pulling, immersion, spraying, roll coating, casting, slit coating, and strip coating.
  • the materials of the anode 10 , the light emitting layer 20 , the electron transport layer 40 , the hole transport layer 50 , the hole injection layer 60 and the cathode 30 are as described above and will not be described in detail here.
  • the step of packaging the light emitting device 100 is further included.
  • the packaging process can be performed by a common machine packaging or by manual packaging.
  • the oxygen content and the water content are both less than 0.1 ppm to ensure the stability of the light emitting device 100.
  • the present application also relates to a display device, which includes the light-emitting device 100.
  • 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 structure of the QLED device in this experimental group is: anode, hole injection layer, hole transport layer, light-emitting layer, electron transport layer and cathode stacked from bottom to top.
  • the thickness of each layer is: anode 110nm, hole injection layer 80nm, hole transport layer 70nm, light-emitting layer 12nm, electron transport layer 60nm, cathode 60nm.
  • a glass substrate is provided, and ITO is evaporated on the glass substrate to form an anode.
  • PEDOT:PSS material (a commercial product with a doping ratio of 1:6 and a solute content of 1.5 wt%) on the anode and heating at 150° C. for 15 min to obtain a hole injection layer.
  • step (3) Transferring the substrate prepared in step (2) into a nitrogen atmosphere, spin coating the hole transport material on the hole injection layer, and heating at 150° C. for 15 min to obtain a hole transport layer; wherein the hole transport material is CBP, whose HOMO energy level is -5.8 eV and mobility is 1.0 ⁇ 10 -3 cm 2 /Vs.
  • the hole transport material is CBP, whose HOMO energy level is -5.8 eV and mobility is 1.0 ⁇ 10 -3 cm 2 /Vs.
  • the quantum dot material includes red quantum dots CdSe/ZnSe/CdZnS, with a QY of 85%, an average particle size of 12 nm, a surface ligand of octanethiol, a mass content of octanethiol on the surface of the quantum dots of 16%, and a ratio of the thickness of the first shell layer ZnSe to the core radius of 1:1, and a ratio of the thickness of the second shell layer CdZnS to the core radius of 1:1; during spin coating, the spin coating speed is controlled to be 2000 rpm, the time is 30 s, and the concentration of the quantum dot material in the octane solution of the quantum dot material is 10 mg/ml, so as to control the light-emitting layer to be a single layer film.
  • the quantum dot material includes red quantum dots CdSe/ZnSe/CdZnS, with a QY of 85%, an average particle size of 12 nm,
  • An electron transport layer is prepared on the light-emitting layer; wherein the material of the electron transport layer is ZnMgO, and its electron mobility is 0.8 ⁇ 10-3 cm2 /Vs.
  • the preparation method of the electron transport layer with an electron mobility of 0.8 ⁇ 10-3 cm2 /Vs is as follows: weigh 0.85mmol of Zn(Ac) 2 ⁇ 2H2O , 0.15mmol of Mg(Ac) 2 ⁇ 4H2O and 10ml of DMSO and place them in a three-necked flask, then stir at 25°C until completely dissolved to obtain a first solution; dissolve 1.5mmol of tetramethylammonium hydroxide in 10ml of ethanol to obtain a second solution; then slowly add the second solution dropwise to the first solution; after the reaction is completed, add ethyl acetate to precipitate, centrifuge, and discard the supernatant; add anhydrous ethanol to dissolve, and then add ethyl acetate to precipitate
  • step (6) Placing the substrate obtained in step (5) in a vapor deposition chamber, vapor-depositing Ag on the electron transport layer to obtain a cathode, and encapsulating to obtain a QLED device.
  • control group 1 is basically the same as that of experimental group 1, except that in this control group, the light-emitting layer is a double-layer film, and accordingly, in step (4), the average particle size of the quantum dot material is 12 nm; during spin coating, the spin coating speed is controlled to be 2000 rpm, the time is 30 s, and the concentration of the quantum dot material in the n-octane solution of the quantum dot material is 20 mg/ml, so as to control the light-emitting layer to be a double-layer film.
  • the other steps and parameters are the same as those of experimental group 1.
  • the control group 2 scheme is basically the same as the experimental group 1, except that in the control group, the light-emitting layer is a four-layer film, and accordingly, in step (4), the average particle size of the quantum dot material is 12 nm; during spin coating, the spin coating speed is controlled to be 2000 rpm, the time is 30 s, and the concentration of the quantum dot material in the n-octane solution of the quantum dot material is 35 mg/ml, so as to control the light-emitting layer to be a four-layer film.
  • the other steps and parameters are the same as those of the experimental group 1.
  • the preparation method of the single electron device is basically the same as the preparation method of its corresponding complete QLED device, the only difference is that the hole injection layer and the hole transport layer are subtracted.
  • 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 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 to measure the quality of electrophotoelectric devices and can be obtained by measuring with 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 for the external quantum efficiency test and the device life test are the QLED devices with complete structures in the above experimental group and the control group; the devices used for test item (ii) are the single-carrier devices corresponding to the QLED devices in the above experimental group and the control group.
  • experimental group 1 Compared with control groups 1 and 2, experimental group 1 also has better roughness, but at the same time, the current density of HOD and EOD of experimental group 1 at 4V is not only larger, but also closer, showing a longer life.
  • QY greater than or equal to 70% core-shell quantum dots with ZnSe as the first shell and CdZnS as the second shell, hole transport materials that meet the "HOMO energy level of -5eV to -6eV, mobility of 0.1 ⁇ 10 -3 to 2 ⁇ 10 -3 cm 2 /Vs" and electron transport materials that meet the "mobility of 0.5 ⁇ 10 -3 to 1 ⁇ 10 -3 cm 2 /Vs"; when other film layer conditions remain unchanged and other parameters of quantum dot materials remain unchanged, compared with double-layer or multi-layer films, the carrier injection in the light-emitting layer of the single-layer film is more balanced, showing a significantly longer service life.
  • the single-layer film is more compatible with the above collocation design, which helps to significantly
  • the current density of the HOD device in the experimental group 1 at a voltage of 4 V has a more obvious increase relative to that of the control group 1, indicating that the promoting effect of the single-layer film on hole injection is more obvious than that on electron injection.
  • This example aims to investigate the effect of the quantum dot shell structure on device performance.
  • control groups 3 to 6 are basically the same as those of experimental group 1, with the only difference being that in each control group, the quantum dot materials used in the light-emitting layer are changed to the materials listed in Table 2 below.
  • This example aims to investigate the effect of the size of the quantum dots QY on the device performance.
  • This embodiment also sets up experimental group 2, experimental group 3, and control group 7. Among them:
  • the experimental group or control group scheme is basically the same as experimental group 1, the only difference is that in each experimental group or control group, the quantum dot material used in the light-emitting layer is changed to the material with QY defined in the following Table 3.
  • QY can be changed by adjusting the thickness of the second shell layer.
  • experimental groups 1 to 3 have significantly higher lifespans and higher EQEs than control group 7, indicating that for devices with the same hole transport layer and electron transport layer design, when the luminescent layer material is changed from a material with a QY greater than or equal to 70% to a material with a QY less than 70%, the device lifespan and luminous efficiency drop significantly.
  • the optimization effect of device design is better, which helps to improve the EQE and life of the device.
  • This example aims to investigate the effect of the HOMO energy level of the hole transport material on the device performance.
  • This embodiment also sets up experimental group 4, experimental group 5, and control group 8. Among them:
  • the experimental group scheme is basically the same as the experimental group 1, except that the hole transport material used in the hole transport layer in each experimental group is changed to the material in the following Table 4.
  • the control group 8 scheme is basically the same as the experimental group 1, except that the hole transport layer is omitted in the control group 8.
  • This embodiment also sets up experimental group 6, experimental group 7, and control groups 9 to 11. Among them:
  • the experimental group or control group scheme is basically the same as that of experimental group 1, except that in each experimental group or control group, the hole transport material used in the hole transport layer is changed to the material in Table 5 below.
  • the control groups 9 to 11 have extremely low EQE and lifetime.
  • the experimental groups 1, 6, and 7 have high EQE and lifetime.
  • This example aims to investigate the effect of the mobility of the electron transport material on the device performance.
  • This embodiment further sets up a control group 12 and a control group 13. Among them:
  • control group scheme is basically the same as the experimental group 1, the only difference is that in each control group, the electron transport material used in the electron transport layer is changed to the material in the following Table 6.
  • the preparation method of ZnMgO with a mobility of 0.01 ⁇ 10 -3 is as follows: 0.9mmol of Zn(Ac) 2 ⁇ 2H 2 O, 0.1mmol of Mg(Ac) 2 ⁇ 4H 2 O and 10ml of DMSO are weighed and placed in a three-necked flask, and then stirred at 25°C until completely dissolved to obtain a first solution; 1.5mmol of tetramethylammonium hydroxide is dissolved in 10ml of ethanol to obtain a second solution; then the second solution is slowly added dropwise to the first solution; after the reaction is completed, ethyl acetate is added thereto for precipitation, centrifugation is performed, and the supernatant is discarded; anhydrous ethanol is added to dissolve, and then ethyl acetate is added again for precipitation and centrifugation.
  • ZnMgO nanoparticles are dispersed in ethanol to prepare a ZnMgO ethanol solution with a concentration of 30mg/ml, which is spin-coated on the light-emitting layer and heated at 100°C for 8min to form an electron transport layer.
  • the preparation method of ZnO with a mobility of 5 ⁇ 10 -3 is as follows: 1mmol of Zn(Ac) 2 ⁇ 2H 2 O and 10ml of DMSO are weighed and placed in a three-necked flask, and then stirred at 25°C until completely dissolved to obtain a first solution; 0.5mmol of tetramethylammonium hydroxide is dissolved in 10ml of ethanol to obtain a second solution; then the second solution is slowly added dropwise to the first solution; after the reaction is completed, ethyl acetate is added thereto for precipitation, centrifugation is performed, and the supernatant is discarded; anhydrous ethanol is added to dissolve, and then ethyl acetate is added again for precipitation and centrifugation.
  • ZnO nanoparticles with an electron mobility of 5 ⁇ 10 -3 cm 2 /Vs.
  • ZnO nanoparticles are dispersed in ethanol to prepare a ZnO ethanol solution with a concentration of 30mg/ml, which is spin-coated on the light-emitting layer and heated at 100°C for 8min to form an electron transport layer.
  • the control groups 12 to 13 have extremely low EQE and lifetime.
  • the experimental group 1 has high EQE and lifetime, which means that when the light-emitting layer adopts a single-layer film design and is prepared using core-shell quantum dots with a QY greater than or equal to 70%, a first shell layer of ZnSe, and a second shell layer of CdZnS, and the hole transport layer selects a material with a HOMO energy level of -5eV to -6eV and a mobility in the range of 0.1 ⁇ 10 -3 to 2 ⁇ 10 -3 cm 2 /Vs, and the electron transport layer uses an electron transport material with a mobility of "0.5 ⁇ 10 -3 to 1 ⁇ 10 -3 cm 2 /Vs", it is helpful to improve the carrier balance of the device and enhance the efficiency and lifetime of the device.

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Abstract

本申请公开了一种发光器件及显示装置，发光器件包括依次层叠设置的阳极、空穴传输层、发光层以及阴极，所述发光层的材料包括量子点，所述发光层的厚度为所述量子点的平均粒径的1～1.5倍；所述空穴传输层的材料的迁移率为0.1×10-3～2×10-3cm2/Vs。本申请旨在提升发光器件的发光效率和使用寿命。

Description

发光器件及显示装置
本申请要求于2023年06月21日在中国专利局提交的、申请号为202310750479.X、申请名称为“发光器件及显示装置”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
本申请涉及显示领域，尤其涉及一种发光器件及显示装置。
背景技术
发光器件通过电子与空穴复合释放能量发光，在照明领域应用广泛。近年来，量子点(QDs)因具有荧光量子产率高、单色性佳、发射光谱随尺寸连续可调、光化学稳定性和热稳定性强的优点引起了产学研界的广泛关注。以量子点作为发光层所构筑的量子点发光器件(Quantum Dot Light Emitting Diodes，QLED)因其具有低成本、高亮度、广色域、优异的可溶液加工等诸多优点已成为了最活跃的科学研究主题之一，在下一代平板显示和固态照明应用中表现出极具竞争潜力。
在QLED器件中，高效率及长寿命的器件是推动QLED产品产业化的基础。
技术解决方案
因此，本申请提供一种发光器件及显示装置。
第一方面，本申请提供一种发光器件，包括依次层叠设置的阳极、空穴传输层、发光层以及阴极，所述发光层的材料包括量子点，所述发光层的厚度为所述量子点的平均粒径的1～1.5倍；
所述空穴传输层的材料的迁移率为0.1×10-3～2×10-3cm2/Vs。
可选的，在本申请的一些实施例中，所述空穴传输层的材料的迁移率为0.5×10-3～1×10-3cm2/Vs。
可选的，在本申请的一些实施例中，所述空穴传输层与所述发光层的能级 差的绝对值为0.1～1.6eV。
可选的，在本申请的一些实施例中，所述空穴传输层的材料的HOMO能级为-5eV～-6eV。
可选的，在本申请的一些实施例中，所述空穴传输层的材料包括CBP、NPB、第一化合物和第二化合物中的任意一种，所述第一化合物具有如式(Ⅰ)所示的结构式，所述第二化合物具有如式(Ⅱ)所示的结构式。
可选的，在本申请的一些实施例中，所述量子点的平均粒径为11～16nm。
可选的，在本申请的一些实施例中，所述量子点的荧光量子产率大于等于70％。
可选的，在本申请的一些实施例中，所述量子点的表面连接有配体；所述配体包括第一配体，所述第一配体的原料选自取代的或未取代的C1～C24的链状硫醇、卤化物中的一种或多种，取代时的取代基选自C1～C8烷基、C1～C8烷氧基以及卤素中的至少一种；所述第一配体的质量占所述量子点和所述配体的总质量的百分比为15～20％。
可选的，在本申请的一些实施例中，所述量子点为核壳结构量子点，且所述量子点具有自内而外的第一壳层和第二壳层，其中，所述第一壳层的材料为ZnSe，所述第二壳层的材料为CdZnS。
可选的，在本申请的一些实施例中，所述第一壳层的厚度与所述量子点的核的半径的比值为0.5～2:1。
可选的，在本申请的一些实施例中，所述第二壳层的厚度与所述量子点的核的半径的比值为0.4～2:1。
可选的，在本申请的一些实施例中，所述核的材料选自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。
可选的，在本申请的一些实施例中，所述发光器件还包括设于所述阴极和所述发光层之间的电子传输层。
可选的，在本申请的一些实施例中，所述电子传输层的材料的迁移率为0.5×10-3～1×10-3cm2/Vs。
可选的，在本申请的一些实施例中，所述电子传输层的材料的平均粒径为2～12nm。
可选的，在本申请的一些实施例中，所述电子传输层的材料包括金属氧化物、掺杂金属氧化物中的一种或多种；所述金属氧化物包括ZnO、TiO2、SnO2、ZrO、Al2O3、WO3、HfO3、Ta2O3、ZrSiO4、BaTiO3、BaZrO3中的一种或多种；所述掺杂金属氧化物中的金属氧化物包括ZnO、TiO2、SnO2、ZrO、Al2O3、WO3、HfO3、Ta2O3、ZrSiO4、BaTiO3、BaZrO3中的多种，掺杂元素包括Al、Mg、Li、In、Ga、Cd、Cs、Cu中的一种或多种。
可选的，在本申请的一些实施例中，所述阳极和所述阴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，所述发光器件还包括设于所述阳极和所述空穴传输层之间的空穴注入层，所述空穴注入层的材料包括聚(亚乙基二氧噻吩):聚苯乙烯磺酸盐、聚[(9,9'-二辛基芴基-2,7-二基)-CO-(4,4'-(N-(对丁基苯基))二苯胺)]、多芳基胺、聚(N-乙烯基咔唑)、聚苯胺、聚吡咯、N,N,N',N'-四(4-甲氧基苯基)-联苯胺、4-双[N-(1-萘基)-N-苯基-氨基]联苯、4,4',4”-三[苯基(间-甲苯基)氨基]三苯基胺、4,4',4”-三(咔唑-9-基)三苯胺、1,1-双[(二-4-甲苯基氨基)苯基环己烷、掺杂有四氟-四氰基-醌二甲烷的4,4',4”-三(二苯基氨基)三苯胺、p-掺杂酞菁、F4-TCNQ掺杂的N,N′-二苯基-N,N′-二(1-萘基)-1,1′-联苯-4,4″-二胺、六氮杂苯并菲-己腈中的一种或多种。
可选的，在本申请的一些实施例中，所述阳极的厚度为20～200nm；和/或，
所述阴极的厚度为40～190nm；和/或，
所述空穴传输层的厚度为30～180nm；和/或，
所述电子传输层的厚度为20～180nm。
可选的，在本申请的一些实施例中，所述发光器件还包括设于所述阳极和所述空穴传输层之间的空穴注入层，所述空穴注入层的厚度为20～200nm。
第二方面，本申请还提出一种显示装置，所述显示装置包括上文所述的发光器件。
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是本申请第一实施例提出的一种发光器件的结构示意图；
图2是本申请第二实施例提出的一种发光器件的结构示意图；
图3是本申请第三实施例提出的一种发光器件的结构示意图；
图4是本申请第四实施例提出的一种发光器件的结构示意图；
附图标记：
100-发光器件；10-阳极；20-发光层；30-阴极；40-电子传输层；50-空穴
传输层；60-空穴注入层；201-量子点。
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。
本申请提供一种发光器件100，所述发光器件100可以为量子点发光二极管(QLED)等。请参阅图1和图4，所述发光器件100包括依次层叠设置的阳极10、空穴传输层50、发光层20以及阴极30，所述发光层20的材料包括量子点201，所述发光层20的厚度为所述量子点201的平均粒径的1～1.5倍；例如，可以是1倍、1.1倍、1.2倍、1.3倍、1.4倍、1.5倍以及上述任意两个数值之间的值。在此范围内，制得的发光层20大致为单层膜。如图4所示，所述单层膜是指在器件的厚度方向上，大致由单独一层核壳量子点201形成的薄膜，其整体体现为：薄膜的厚度为制备薄膜的量子点201的平均粒径的1～1.5倍。
实际生产过程中，面对不同的量子点材料，往往存在需要制备不同层数的量子点薄膜以满足器件对发光层20的成膜需求。例如，在一些情况下，所述量子点201表面连接有配体；所述配体包括第一配体，所述第一配体的原料选自取代的或未取代的C1～C24的链状硫醇、卤化物中的一种或多种，所述取代时的取代基选自C1～C8烷基、C1～C8烷氧基以及卤素中的至少一种；所述第一配体的质量占所述量子点201和所述配体的总质量的百分比为15～20％；所述发光层20的厚度为所述量子点201的平均粒径的1～1.5倍。
在一些实施例中，所述配体的原料包括取代的或未取代的C10～C24链状有机羧酸、取代的或未取代的C10～C24链状有机胺、取代的或未取代的C1～C24的链状硫醇、取代的或未取代的C10～C24的链状有机膦、取代的或未取代的C10～C24的链状有机氧膦、卤化物中的至少一种。其中，“取代或未取代”表示所定义的基团可以被取代，也可以不被取代。当所定义的基团为被取代时，应理解为所定义的基团可以被一个或多个取代基取代；取代基选自C1～C8烷基、C1～C8烷氧基以及卤素中的至少一种；可选地，取代基选自C1～C5烷基、C1～C5烷氧基以及卤素中的至少一种；或取代基选自C1～C3烷基、C1～C3烷氧基以及卤素中的至少一种。所述卤素是指-F、-Cl、-Br或-I。具体的，所 述有机羧酸包括十酸(CAS：334-48-5)、十一烯酸(CAS：112-38-9)、十四酸(CAS：544-63-8)、油酸(CAS：112-80-1)和硬脂酸(CAS：57-11-4)中的一种或多种；所述有机胺包括油胺(CAS:112-90-3)、十八胺(CAS：124-30-1)中的一种或多种；所述有机(氧)膦包括三辛基膦(CAS:4731-53-7)、三辛基氧膦(CAS：78-50-2)的一种或多种；所述硫醇包括正辛硫醇(CAS：111-88-6)、十二硫醇(CAS：112-55-0)和十八硫醇(CAS:2885-00-9)中的一种或多种；所述卤化物选自氢氟酸、盐酸、氢碘酸、氢溴酸、金属氟化物、金属氯化物、金属碘化物、金属溴化物中的一种或多种。
所述配体的质量占所述量子点201和所述配体的总质量的百分比为15％～20％，例如可以为15％、16％、17％、18％、19％、20％以及上述任意两个数值之间的值，在此范围内，有助于改善量子点201的分散性，提高其成膜效果。
在另一些实施例中，所述配体包括第一配体，所述第一配体选自取代的或未取代的C1～C24的链状硫醇、卤化物中的一种或多种，所述第一配体可以和量子点201表面阳离子形成较强的配位键，不易脱落，有助于提高发光层20的成膜效果。进一步地，所述第一配体的质量百分含量为15％～20％，例如可以为15％、16％、17％、18％、19％、20％以及上述任意两个数值之间的值，当量子点201表面连接有上述含量的配体时，只需制备成单层膜即可实现较好的成膜效果。
在又一些实施例中，当量子点201表面的阴离子包括硫原子时，例如量子点201为CdS或者CdSe/ZnSe/CdZnS时，所述配体为硫醇配体时，如此，在制备量子点201时，可以将硫醇化合物作为阴离子源加入，配体上的S原子可以直接与量子点201表面的阳离子进行配位连接，或者直接充当量子点201壳层表面S原子而直接嵌入至壳层中，有助于进一步提高配体的配位效果，降低脱落几率。
可以理解，所述配体和所述第一配体的含量可以通过核磁共振与热失重试验检测得到，量子点201表面第一配体的数量可以通过合成过程中引入，也可以通过配体交换的方式引入。首先，核磁共振可以测量量子点201表面特定配体含量。其次，热失重试验可以测定量子点201表面配体总含量。最后，两者 的配体差值即为其他配体含量。核磁共振测定量子点201表面特定配体含量的具体测试方法如下：将量子点201溶解在氘代试剂中，并加入特定量的内标物作为参照，通过计算量子点201配体的化学位移积分面积与内标物的化学位移积分面积之比，从而定量出所需要测定的配体含量。热失重试验检测方法如下：加热量子点201材料直至其质量不再发生变化，记录其开始失重到强配位配体(即第一配体)脱落温度时，材料的失重W1，并记录其开始失重到其质量不再发生变化时，材料的失重W2，则W2为配体的含量，W2-W1为第一配体的含量。
也可以将核磁共振与热失重方法同时使用，比如：为了测定特定的量子点201表面配体油酸(弱配体)和硫醇的含量(其中硫醇做为第一配体)。具体测试方法如下：第一、将量子点201溶解在氘代甲苯中，以采用二茂铁做为内标物(加入的量为额定，化学位移为3.8～4.0ppm)，测定量子点201配体在5.4～5.8ppm处的化学位移。最后，将配体在5.4～5.8ppm处的化学位移积分面积除以内标物在3.8～4.0ppm的化学位移积分面积，即可得到油酸配体的含量。第二、采用比如：测定量子点201在20～600℃的热失重，记录100℃～500℃的重量损失即为量子点201表面配体总含量。最后，将配体总含量减去油酸配体含量，即可得到硫醇配体含量。
当设置单层膜即可获得较好的成膜效果时，发光层20可以设置为单层膜。相较双层膜和多层膜，单层膜具有较低的隧穿势垒，便于载流子注入。
同时，为了提升器件的效率和寿命，可以搭配具有较高空穴注入水平的空穴传输材料，具体的，所述空穴传输层50的材料的迁移率大于等于0.1×10-3cm2/Vs，且小于等于2×10-3cm2/Vs，例如，0.1×10-3cm2/Vs、0.2×10-3cm2/Vs、0.5×10-3cm2/Vs、0.6×10-3cm2/Vs、0.7×10-3cm2/Vs、0.8×10-3cm2/Vs、0.9×10-3cm2/Vs、1×10-3cm2/Vs、1.3×10-3cm2/Vs、1.5×10-3cm2/Vs、1.7×10-3cm2/Vs、1.9×10-3cm2/Vs、2×10-3cm2/Vs以及上述任意两个数值之间的值。在此范围内，有助于在一定程度上增加空穴注入，改善器件中空穴和电子的注入平衡，从而避免发光层20带电，引发俄歇复合，进而影响到器件的寿命和效率。
本申请提供的技术方案，发光层20设置为单层量子点构建的单层膜，并 搭配材料空穴迁移率为0.1×10-3～2×10-3cm2/Vs的空穴传输层，可以很好地发挥单层膜隧穿势垒相对较低的优势，有效增强空穴注入，改善空穴和电子的注入平衡，从而提升器件的效率和寿命。
进一步地，在一些实施例中，所述空穴传输层50的材料的迁移率为0.5×10-3～1×10-3cm2/Vs，有助于进一步提升载流子平衡性。
在一些实施例中，所述空穴传输层50与所述发光层20的能级差的绝对值为0.1～1.6eV，例如，0.1eV、0.3eV、0.5eV、0.7eV、0.9eV、1.0eV、1.1eV、1.3eV、1.5eV、1.6eV以及上述任意两个数值之间的值。在该能级差范围内可以降低空穴注入势垒，有助于进一步增强空穴注入。
在一些实施例中，所述空穴传输层50的材料的HOMO能级为-5eV～-6eV；例如，-5eV、-5.2eV、-5.3eV、-5.4eV、-5.5eV、-5.6eV、-5.7eV、-5.8eV、-5.9eV、-6eV以及上述任意两个数值之间的值。
具体的，在一些实施例中，所述空穴传输层50的材料包括CBP(4,4'-双(9H-咔唑-9-基)联苯，CAS：58328-31-7)、NPB(N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺，CAS：123847-85-8)、第一化合物和第二化合物中的任意一种，所述第一化合物具有如式(Ⅰ)所示的结构式，所述第二化合物具有如式(Ⅱ)所示的结构式。所述第一化合物和所述第二化合物的制备方法和电学性能可参考中国专利CN110504379A-一种复合电子阻挡层及其OLED器件。
上述材料中，CBP的HOMO能级为-5.8eV，空穴迁移率为1.0×10-3cm2/Vs；NPB的HOMO能级为-5.5eV，空穴迁移率为8.8×10-4cm2/Vs；第一化合物的HOMO能级为-5.49eV，空穴迁移率为8.7×10-4cm2/Vs；第二化合物的HOMO能级为-5.6eV，空穴迁移率为8.6×10-4cm2/Vs。
在一些实施例中，所述量子点201的荧光量子产率(QY)大于等于70％，例如可以是70％、75％、80％、85％、90％、92％等等。具有较高的QY的量 子点201通常具有较少的缺陷，能够降低非辐射复合的概率，提高载流子的复合。因此，在一些情况下，难免面临发光层采用高发光效率量子点，并设置单层膜的场景。然而，较高QY的量子点201通常壳层包覆质量较高，激子束缚较好，使得壳层具有较大的载流子注入势垒，使得载流子注入相对困难。对此，本申请实施例将发光层20为单层膜，并搭配材料空穴迁移率为0.1×10-3～2×10-3cm2/Vs的空穴传输层50，有助于增强空穴注入，克服高效率量子点201存在的外界载流子注入困难的问题，提升载流子在器件中的有效注入和高效复合，改善空穴和电子的注入平衡，从而提升器件的效率和寿命。
在一些实施例中，所述量子点201的平均粒径为11～16nm，例如可以是11nm、12nm、13nm、14nm、15nm、16nm以及上述任意两个数值之间的值，在量子点201形成单层膜，有助于提高成膜效果。相应的，所述发光层20的厚度为11～24nm。例如可以是11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm、20nm、22nm、23nm、24nm以及上述任意两个数值之间的值。
在一些实施例中，所述量子点201的形态包括但不限于球形、立方体、四面体、柱状、四足状、八足状、片状等。
在一些实施例中，所述量子点201为核壳结构的量子点201，所述量子点201具有自内而外的第一壳层和第二壳层。所述第一壳层的材料为ZnSe，较浅的价带有助于提升空穴注入，但自身带隙相对适中，对激子的束缚能力相对较弱；所述第二壳层的材料为CdZnS，该壳层不但自身的带隙相对较宽，而且价带的位置相对适中，能够保证激子束缚的前提下，提升空穴注入至发光核中，从而提高载流子复合效率。两个壳层共同作用，有效降低了空穴注入势垒，有助于空穴高效注入量子点201的核中。
在一些实施例中，所述第一壳层的厚度与所述量子点201的核的半径的比值为0.5～2:1；例如，比值可以为0.5:1、0.6:1、0.8:1、1:1、1.1:1、1.2:1、1.3:1、1.5:1等等；有助于有效控制对激子的束缚能力，不仅有利于降低载流子注入时的隧穿势垒，促进载流子注入，而且有助于注入到量子点201核中的载流子有效复合。
在一些实施例中，所述第二壳层的厚度与所述量子点201的核的半径的比值为0.4～2:1；例如，比值可以为0.4:1、0.6:1、0.8:1、1:1、1.2:1、1.3:1、1.5:1、 1.7:1、1.8:1、2:1等等；有助于有效控制对激子的束缚能力，并将激子与外界隔离，从而降低激子被外界捕获的概率，同时降低载流子注入时的隧穿势垒，促进载流子注入。
在一些实施例中，所述量子点201的核材料可以选自但不限于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；作为示例，所述II-VI族化合物选自但不限于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族化合物选自但不限于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族化合物选自但不限于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201可以选自但不限于CdZnSe/ZnSe/CdZnS、CdSe/ZnSe/CdZnS、InP/ZnSe/CdZnS、CdSeS/ZnSe/CdZnS、ZnSe/ZnSe/CdZnS、ZnSeTe/ZnSe/CdZnS中的至少一种。
需要说明的是，对于前述核壳结构的量子点201的核的材料、或者核壳结构的量子点201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：CdZnS仅表示由Cd、Zn和S三种元素组成，若表示各个元素的含量，则对应为CdxZn1-xS，0<x<1。
请参阅图2，在一些实施例中，所述电子传输层40的材料的迁移率为0.5×10-3～1×10-3cm2/Vs，例如，0.5×10-3cm2/Vs、0.6×10-3cm2/Vs、0.7×10-3cm2/Vs、0.8×10-3cm2/Vs、0.9×10-3cm2/Vs、1.0×10-3cm2/Vs以及上述任意两个数值之间的 值。在此范围内，可以精确控制电子注入，使其和器件中空穴注入趋于平衡，从而有效改善器件的载流子平衡性，避免发光层20带电，引发俄歇复合，进而影响到器件的寿命和效率。
在一些实施例中，所述电子传输层40的材料的平均粒径为2～12nm，例如，可以是2nm、3nm、4nm、5nm、6nm、8nm、10nm、11nm、12nm以及上述任意两个数值之间的值。这种粒径尺寸下的电子传输材料在成膜时易于制成膜层厚度均一、致密的薄膜，有助于提高成膜质量。
在一些实施例中，所述电子传输层40的材料包括但不限于金属氧化物、掺杂金属氧化物中的一种或多种。作为示例，所述金属氧化物包括但不限于ZnO、TiO2、SnO2、ZrO、Al2O3、WO3、HfO3、Ta2O3、ZrSiO4、BaTiO3、BaZrO3中的一种或多种；所述掺杂金属氧化物中的金属氧化物包括但不限于ZnO、TiO2、SnO2、ZrO、Al2O3、WO3、HfO3、Ta2O3、ZrSiO4、BaTiO3、BaZrO3中的多种，掺杂元素包括但不限于Al、Mg、Li、In、Ga、Cd、Cs、Cu中的一种或多种。
此外，在一些实施例中，所述电子传输材料表面还可以连接有配体，所述配体来源于酸配体、胺配体、硫醇配体中的一种或多种。具体的，所述配体的原料包括并不限于油酸、油胺、十二烷酸、十四烷酸、十六烷酸、十八烷酸中的一种或多种。
将阳离子源、碱源、溶剂混合，即可反应得到金属氧化物MO或掺杂金属氧化物MAO，其中，M为金属元素，A为掺杂元素。具体的，当要制备的材料为金属氧化物时，阳离子源即能够提供M金属元素的金属盐，例如醋酸锌等；当要制备的材料为掺杂金属氧化物时，阳离子源包括能够提供M金属元素的金属盐以及能够提供A掺杂元素的金属盐，例如醋酸锌、醋酸镁等；所述碱源包括有机碱和无机碱中的一种或多种，所述有机碱选自六亚甲基四胺、四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、尿素中的一种或多种，所述无机碱选自氢氧化钠、氢氧化锂、氢氧化钾、氢氧化钙、氢氧化铵、碳酸钠、碳酸钾中的一种或多种；溶剂包括醇类或二甲基亚砜(DMSO)。在制备电子传输材料时，通过调整掺杂元素的种类和含量、碱源添加量、后处理条件等参数条件，可以精确控制电子传输层40材料的迁移率，实际操作时可以参 考本领域常用的调控电子传输层40材料迁移率的方法进行制备。以调节碱源添加量控制电子迁移率的方法为例，在一些实施例中，电子传输层40材料为ZnO，为了调节其电子迁移率，可以采用四甲基氢氧化铵为碱源，在制备ZnO时，控制ZnO和四甲基氢氧化铵的投料摩尔比为1:1.5，可以得到迁移率为0.1×10-3cm2/Vs的ZnO纳米颗粒；也可以控制ZnO和四甲基氢氧化铵的投料摩尔比为1:0.5，可以得到迁移率为5×10-3cm2/Vs的ZnO纳米颗粒。
在一些实施例中，所述阳极10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。
在一些实施例中，所述阴极30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。
请参阅图3，在一些实施例中，所述发光器件100还包括设于所述阳极10和所述空穴传输层50之间的空穴注入层60，所述空穴注入层60的材料包括聚(亚乙基二氧噻吩):聚苯乙烯磺酸盐(PEDOT:PSS)、聚[(9,9'-二辛基芴基-2,7-二基)-CO-(4,4'-(N-(对丁基苯基))二苯胺)](TFB)、多芳基胺、聚(N-乙烯基咔唑)、聚苯胺、聚吡咯、N,N,N',N'-四(4-甲氧基苯基)-联苯胺(TPD)、4-双[N-(1-萘 基)-N-苯基-氨基]联苯(α-NPD)、4,4',4”-三[苯基(间-甲苯基)氨基]三苯基胺(m-MTDATA)、4,4',4”-三(咔唑-9-基)三苯胺(TCTA)、1,1-双[(二-4-甲苯基氨基)苯基环己烷(TAPC)、掺杂有四氟-四氰基-醌二甲烷(F4-TCNQ)的4,4',4”-三(二苯基氨基)三苯胺(TDATA)、p-掺杂酞菁(例如，F4-TCNQ-掺杂的锌酞菁(ZnPc))、F4-TCNQ掺杂的N,N′-二苯基-N,N′-二(1-萘基)-1,1′-联苯-4,4″-二胺(α-NPD)、六氮杂苯并菲-己腈(HAT-CN)中的一种或多种。
在一些实施例中，所述阳极10的厚度为20～200nm；例如可以为20～40nm、30～60nm、50～80nm、55～90nm、70～100nm、90～120nm、110～140nm、130～150nm、140～170nm、160～200nm，等等。
在一些实施例中，所述阴极30的厚度为40～190nm；例如可以为40～60nm、50～80nm、55～90nm、70～100nm、90～120nm、110～140nm、130～150nm、140～170nm、160～190nm，等等。
在一些实施例中，所述空穴传输层50的厚度为30～180nm；例如可以为30～40nm、35～60nm、50～80nm、55～90nm、70～100nm、90～120nm、110～140nm、130～150nm、140～170nm、160～180nm，等等。
在一些实施例中，所述电子传输层40的厚度为20～180nm；例如可以为20～40nm、30～60nm、50～80nm、55～90nm、70～100nm、90～120nm、110～140nm、130～150nm、140～170nm、160～180nm，等等。
在一些实施例中，所述空穴注入层60的厚度为20～200nm；例如可以为20～40nm、30～60nm、50～80nm、55～90nm、70～100nm、90～120nm、110～140nm、130～150nm、140～170nm、160～200nm，等等。
可以理解，所述发光器件100还可以增设一些常规用于发光器件100的有助于提升发光器件100性能的功能层，例如电子阻挡层、空穴阻挡层、界面修饰层等。
可以理解，所述发光器件100可以为正置发光器件或倒置发光器件。
基于上述实施例，本申请还提出发光器件100的制备方法，用于制备上述发光器件100。在一些实施例中，所述发光器件100可以为正置发光器件，相应的，所述制备方法包括：
S10a，提供阳极10；
S20a，在阳极10上依次设置空穴功能层、发光层20和电子传输层40；
S30a，在电子传输层40上设置阴极30。
在另一些实施例中，所述发光器件100可以为倒置发光器件，相应的，所述制备方法包括：
S10b，提供阴极30；
S20b，在阳极10上依次设置电子传输层40、发光层20和空穴功能层；
S30b，在电子传输层40上设置阳极10。
步骤S20a和S20b中，空穴功能层包括空穴传输层50，或者包括空穴传输层50和空穴注入层60，当空穴功能层包括空穴传输层50和空穴注入层60时，空穴注入层60更靠近阳极10设置。
所述发光器件100的制备方法中，所述阳极10、发光层20、电子传输层40、空穴传输层50、空穴注入层60及阴极30的制备方法可采用本领域常规技术实现，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。
所述阳极10、发光层20、电子传输层40、空穴传输层50、空穴注入层60及阴极30的材料参上文所述，在此不在赘述。
在一些实施例中，在制备得到发光器件100后还包括对所述发光器件100进行封装的步骤。所述封装处理可采用常用的机器封装，也可以采用手动封装。优选的，所述封装处理的环境中，氧含量和水含量均低于0.1ppm，以保证发光器件100的稳定性。
此外，本申请还涉及一种显示装置，所述显示装置包括所述发光器件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。
实施例1
本实施例旨在考察量子点层数对器件性能的影响
实验组1
本实验组QLED器件的结构为：自下而上依次层叠的阳极、空穴注入层、空穴传输层、发光层、电子传输层和阴极。各层厚度依次为：阳极110nm、空穴注入层80nm、空穴传输层70nm、发光层12nm、电子传输层60nm、阴极60nm。
(1)提供玻璃衬底，在玻璃衬底上蒸镀ITO，形成阳极。
(2)在所述阳极上旋涂PEDOT:PSS材料(掺杂比为1：6的商用产品，溶质含量为1.5wt％)，150℃加热15min，得到空穴注入层。
(3)将步骤(2)制得的基板转移至氮气气氛中，在所述空穴注入层上旋涂空穴传输材料，150℃加热15min，得到空穴传输层；其中，空穴传输材料为CBP，其HOMO能级为-5.8eV，迁移率为1.0×10-3cm2/Vs。
(4)在空穴传输层上旋涂量子点材料的正辛烷溶液，80℃加热10min，得到发光层；其中，量子点材料包括红色量子点CdSe/ZnSe/CdZnS，QY为85％，平均粒径为12nm，表面配体为辛硫醇，量子点表面的辛硫醇的质量含量为16％，且第一壳层ZnSe的厚度与核半径的比值为1:1，第二壳层CdZnS的厚度与核半径的比值为1:1；在旋涂时，控制旋涂转速为2000rpm，时间为30s，量子点材料的正辛烷溶液中量子点材料的浓度为10mg/ml，以控制发光层为单层膜。
(5)在发光层上制备电子传输层；其中，电子传输层的材料为ZnMgO，且其电子迁移率为0.8×10-3cm2/Vs。电子迁移率为0.8×10-3cm2/Vs的电子传输层的制备方法为：称取0.85mmol的Zn(Ac)2·2H2O、0.15mmol的Mg(Ac)2·4H2O和10ml DMSO置于三口烧瓶，然后置于25℃下搅拌直至完全溶解，得到第一溶液；将1.5mmol四甲基氢氧化铵溶于10ml的乙醇，得到第二溶液；然后将第二溶液缓慢滴加至第一溶液中；待反应结束后，向其中加入乙酸乙酯进行沉淀，离心，弃上清液；加入无水乙醇溶解，然后再加入乙酸乙酯进行沉淀、离心。重复上述步骤2次，得到ZnMgO纳米颗粒。将ZnMgO纳米颗粒分散在乙醇 中，旋涂在发光层上，形成固态膜，然后置于氧气气氛中，并于365nm，1200W功率下的紫外光下UV 5min，得到电子迁移率为0.8×10-3cm2/Vs的ZnMgO电子传输层。
(6)将步骤(5)制得的基板置于蒸镀舱中，在所述电子传输层上蒸镀Ag，得到阴极，封装，得到QLED器件。
对照组1
对照组1方案与实验组1基本相同，区别仅在于，本对照组中，发光层为双层膜，相应的，步骤(4)中，量子点材料的平均粒径为12nm；在旋涂时，控制旋涂转速为2000rpm，时间为30s，量子点材料的正辛烷溶液中量子点材料的浓度为20mg/ml，以控制发光层为双层膜。其它步骤和参数均与实验组1相同。
对照组2
对照组2方案与实验组1基本相同，区别仅在于，本对照组中，发光层为四层膜，相应的，步骤(4)中，量子点材料的平均粒径为12nm；在旋涂时，控制旋涂转速为2000rpm，时间为30s，量子点材料的正辛烷溶液中量子点材料的浓度为35mg/ml，以控制发光层为四层膜。其它步骤和参数均与实验组1相同。
(一)取实验组1、对照组1和对照组2制备过程中步骤(4)制得的半成品器件，所述半成品器件的最上层为发光层。通过AFM考察发光层的粗糙度，以评估其成膜效果，结果记入表1中。
(二)对应实验组1、对照组1和对照组2分别制备其各自的单载流子器件，并测试单载流子传输薄膜器件(HOD/EOD)的电流密度-电压曲线。取器件在4V下的电流密度进行比较。其中：
单电子器件(EOD)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，减去空穴注入层和空穴传输层。
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。
结果记入表1中。
(三)取实验组1、对照组1和对照组2制得的器件，将器件置于120℃下热 处理15min来加速器件正向老化。然后在对完成热处理后的器件进行后续性能测试，结果记入表1中。检测方法如下：
(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％，是衡量电致光电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红色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验组和对照组中完整结构的QLED器件；测试项目(二)所使用的器件为上述实验组和对照组中QLED器件对应的单载流子器件。
表1

由上表可以看出：
相较对照组1和2，实验组1同样具有较好的粗糙度，但同时，实验组1在4V下HOD和EOD不但电流密度较大，且电流密度较为接近，表现为寿命更长，说明，对于采用下述搭配设计的器件：QY大于等于70％、第一壳层为ZnSe、第二壳层为CdZnS的核壳量子点，满足“HOMO能级为-5eV～-6eV，迁移率为0.1×10-3～2×10-3cm2/Vs”的空穴传输材料以及满足“迁移率为0.5×10-3～1×10-3cm2/Vs”的电子传输材料；在其它膜层条件不变且量子点材料其它参数不变的情况下，相较于双层膜或多层膜，单层膜发光层中载流子注入更为平衡，表现出明显更长的使用寿命。说明单层膜与上述搭配设计更为匹配，有助于在确保发光效率的同时，明显提高器件的寿命。
除此之外，相较EOD器件，实验组1的HOD器件在4V电压下的电流密度相对对照组1具有更明显的增幅，说明单层膜对空穴注入的促进效果比对电子注入的促进效果更明显。
实施例2
本实施例旨在考察量子点壳层结构对器件性能的影响。
对照组3～6方案与实验组1基本相同，区别仅在于，各对照组中，发光层中采用的量子点材料改为下述表2中的材料。
对实验组1、对照组3～6进行性能测试，结果记入表2中。
表2

由上表可以看出，对于采用同样空穴传输层和电子传输层设计的器件，当将其发光层材料的壳层结构由ZnSe/CdZnS改为其它壳层结构后，器件寿命大幅度下降，由此可见，相较其他宽带隙的壳层材料，选择第一壳层为ZnSe和第二壳层CdZnS时，空穴能够更好的注入至壳层中进行有效复合，表现为具有更高的EQE及更长的器件寿命。
实施例3
本实施例旨在考察量子点QY的大小对器件性能的影响。
本实施例另外设置实验组2、实验组3、对照组7。其中：
实验组或对照组方案与实验组1基本相同，区别仅在于，各实验组或对照组中，发光层中采用的量子点材料改为下述表3中限定QY的材料，具体实施时可通过调整第二壳层的厚度改变QY。
对实验组1～3、对照组7进行性能测试，结果记入表3中。
表3
由上表可以看出，实验组1～3具有较对照组7明显更高的寿命，以及较高的EQE，说明：对于采用同样空穴传输层和电子传输层设计的器件，当将其发光层材料由QY大于等于70％的材料改为QY低于70％的材料后，器件寿命和发光效率大幅度下降，由此可见，相较QY低于70％的量子点材料，选择QY大于等 于70％的材料时，器件设计的优化效果更好，有助于提高器件的EQE及寿命。
实施例4
本实施例旨在考察空穴传输材料的HOMO能级大小对器件性能的影响。
本实施例另外设置实验组4、实验组5、对照组8。其中：
实验组方案与实验组1基本相同，区别仅在于，各实验组中，空穴传输层中采用的空穴传输材料改为下述表4中的材料。对照组8方案与实验组1基本相同，区别仅在于，对照组8中省略空穴传输层。
对实验组1、4、5以及对照组8进行性能测试，结果记入表4中。
表4
由上表可以看出，对照组8由于缺少空穴传输层，发光层和空穴传输层间的能级差达到最大，空穴注入最难，表现为EQE很低，器件几乎无寿命。相反，实验组1、4和5则表现出较高的EQE和较长的寿命，显然，采用发光层和空穴传输材料间的能级差在0.1～1.6eV之间的空穴传输材料，有助于提高空穴注入，且当能级差越小时，空穴注入水平提升幅度相对越高，器件具有越好的性能。
实施例5
本实施例旨在考察空穴传输材料的迁移率大小对器件性能的影响。
本实施例另外设置实验组6、实验组7、对照组9～11。其中：
实验组或对照组方案与实验组1基本相同，区别仅在于，各实验组或对照组中，空穴传输层中采用的空穴传输材料改为下述表5中的材料。
对实验组1、6、7以及对照组9～11进行性能测试，结果记入表5中。
表5
由上表可以看出，对照组9～11具有极低的EQE和寿命，相反，实验组1、6、7具有高EQE和寿命，说明：当发光层采用单层膜设计，并采用QY大于等于70％、第一壳层为ZnSe、第二壳层为CdZnS的核壳量子点制备，同时电子传输层采用迁移率为“0.5×10-3～1×10-3cm2/Vs”的电子传输材料时，空穴传输层选择空穴迁移率在0.1×10-3～2×10-3cm2/Vs范围内的材料，有助于改善器件的载流子平衡，提升器件的效率及寿命。
实施例6
本实施例旨在考察电子传输材料的迁移率大小对器件性能的影响。
本实施例另外设置对照组12和对照组13。其中：
对照组方案与实验组1基本相同，区别仅在于，各对照组中，电子传输层中采用的电子传输材料改为下述表6中的材料。
迁移率为0.01×10-3的ZnMgO的制备方法为：称取0.9mmol的Zn(Ac)2·2H2O、0.1mmol的Mg(Ac)2·4H2O和10ml DMSO置于三口烧瓶，然后置于25℃下搅拌直至完全溶解，得到第一溶液；将1.5mmol四甲基氢氧化铵溶于10ml的乙醇，得到第二溶液；然后将第二溶液缓慢滴加至第一溶液中；待反应结束后，向其中加入乙酸乙酯进行沉淀，离心，弃上清液；加入无水乙醇溶解，然后再加入乙酸乙酯进行沉淀、离心。重复上述步骤2次，得到迁移率为0.01×10-3的ZnMgO纳米颗粒。将ZnMgO纳米颗粒分散在乙醇中，制成浓度为30mg/ml的ZnMgO乙醇溶液，将其旋涂在发光层上，100℃加热8min，形成电子传输层。
迁移率为5×10-3的ZnO的制备方法为：称取1mmol的Zn(Ac)2·2H2O和10ml DMSO置于三口烧瓶，然后置于25℃下搅拌直至完全溶解，得到第一溶液；将0.5mmol四甲基氢氧化铵溶于10ml的乙醇，得到第二溶液；然后将第二溶液缓慢滴加至第一溶液中；待反应结束后，向其中加入乙酸乙酯进行沉淀，离心，弃上清液；加入无水乙醇溶解，然后再加入乙酸乙酯进行沉淀、离心。重复上述步骤2次，得到电子迁移率为5×10-3cm2/Vs的ZnO纳米颗粒。将ZnO纳米颗粒分散在乙醇中，制成浓度为30mg/ml的ZnO乙醇溶液，将其旋涂在发光层上，100℃加热8min，形成电子传输层。
对实验组1、对照组12和对照组13进行性能测试，结果记入表6中。
表6

由上表可以看出，对照组12～13具有极低的EQE和寿命，相反，实验组1具有高EQE和寿命，说明：当发光层采用单层膜设计，并采用QY大于等于70％、第一壳层为ZnSe、第二壳层为CdZnS的核壳量子点制备，同时空穴传输层选择HOMO能级为-5eV～-6eV，迁移率在0.1×10-3～2×10-3cm2/Vs范围内的材料时，电子传输层采用迁移率为“0.5×10-3～1×10-3cm2/Vs”的电子传输材料，有助于改善器件的载流子平衡，提升器件的效率及寿命。
以上对本申请实施例所提供的发光器件及显示装置进行了详细介绍，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. 一种发光器件，其中，包括依次层叠设置的阳极、空穴传输层、发光层以及阴极，所述发光层的材料包括量子点，所述发光层的厚度为所述量子点的平均粒径的1～1.5倍；
    所述空穴传输层的材料的迁移率为0.1×10-3～2×10-3cm2/Vs。
  2. 根据权利要求1所述的发光器件，其中，所述空穴传输层的材料的迁移率为0.5×10-3～1×10-3cm2/Vs。
  3. 根据权利要求1或2所述的发光器件，其中，所述空穴传输层与所述发光层的能级差的绝对值为0.1～1.6eV。
  4. 根据权利要求1至3任一项所述的发光器件，其中，所述空穴传输层的材料的HOMO能级为-5eV～-6eV。
  5. 根据权利要求1至4任一项所述的发光器件，其中，所述空穴传输层的材料包括CBP、NPB、第一化合物和第二化合物中的任意一种，所述第一化合物具有如式(Ⅰ)所示的结构式，所述第二化合物具有如式(Ⅱ)所示的结构式。
  6. 根据权利要求1至5任一项所述的发光器件，其中，所述量子点的荧光量子产率大于等于70％。
  7. 根据权利要求1至6任一项所述的发光器件，其中，所述量子点的平均粒径为11～16nm。
  8. 根据权利要求1至7任一项所述的发光器件，其中，所述量子点的表面连接有配体；所述配体包括第一配体，所述第一配体的原料选自取代的或未取代的C1～C24的链状硫醇、卤化物中的一种或多种，取代时的取代基选自C1～C8烷基、C1～C8烷氧基以及卤素中的至少一种；所述第一配体的质量占所述量子点和所述 配体的总质量的百分比为15～20％。
  9. 根据权利要求1至8任一项所述的发光器件，其中，所述量子点为核壳结构量子点，且所述量子点具有自内而外的第一壳层和第二壳层，其中，所述第一壳层的材料为ZnSe，所述第二壳层的材料为CdZnS。
  10. 根据权利要求9所述的发光器件，其中，所述第一壳层的厚度与所述量子点的核的半径的比值为0.5～2:1。
  11. 根据权利要求9或10所述的发光器件，其中，所述第二壳层的厚度与所述量子点的核的半径的比值为0.4～2:1。
  12. 根据权利要求9至11任一项所述的发光器件，其中，所述核的材料选自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。
  13. 根据权利要求1至12任一项所述的发光器件，其中，所述发光器件还包括设于所述阴极和所述发光层之间的电子传输层。
  14. 根据权利要求13所述的发光器件，其中，所述电子传输层的材料的迁移率为0.5×10-3～1×10-3cm2/Vs。
  15. 根据权利要求13或14所述的发光器件，其中，所述电子传输层的材料的平均粒径为2～12nm。
  16. 根据权利要求13至15任一项所述的发光器件，其中，所述电子传输层的材料包括金属氧化物、掺杂金属氧化物中的一种或多种；所述金属氧化物包括ZnO、TiO2、SnO2、ZrO、Al2O3、WO3、HfO3、Ta2O3、ZrSiO4、BaTiO3、BaZrO3中的一种或多种；所述掺杂金属氧化物中的金属氧化物包括ZnO、TiO2、SnO2、ZrO、Al2O3、WO3、HfO3、Ta2O3、ZrSiO4、BaTiO3、BaZrO3中的多种，掺杂元素包括Al、Mg、Li、In、Ga、Cd、Cs、Cu中的一种或多种。
  17. 根据权利要求1至16任一项所述的发光器件，其中，所述阳极和所述阴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，所述发光器件还包括设于所述阳极和所述空穴传输层之间的空穴注入层，所述空穴注入层的材料包括聚(亚乙基二氧噻吩):聚苯乙烯磺酸盐、聚[(9,9'-二辛基芴基-2,7-二基)-CO-(4,4'-(N-(对丁基苯基))二苯胺)]、多芳基胺、聚(N-乙烯基咔唑)、聚苯胺、聚吡咯、N,N,N',N'-四(4-甲氧基苯基)-联苯胺、4-双[N-(1-萘基)-N-苯基-氨基]联苯、4,4',4”-三[苯基(间-甲苯基)氨基]三苯基胺、4,4',4”-三(咔唑-9-基)三苯胺、1,1-双[(二-4-甲苯基氨基)苯基环己烷、掺杂有四氟-四氰基-醌二甲烷的4,4',4”-三(二苯基氨基)三苯胺、p-掺杂酞菁、F4-TCNQ掺杂的N,N′-二苯基-N,N′-二(1-萘基)-1,1′-联苯-4,4″-二胺、六氮杂苯并菲-己腈中的一种或多种。
  18. 根据权利要求17所述的发光器件，其中，所述空穴注入层的厚度为20～200nm。
  19. 根据权利要求13至16任一项所述的发光器件，其中，所述阳极的厚度为20～200nm；和/或，
    所述阴极的厚度为40～190nm；和/或，
    所述空穴传输层的厚度为30～180nm；和/或，
    所述电子传输层的厚度为20～180nm。
  20. 一种显示装置，其中，所述显示装置包括权利要求1至19任一项所述的发光器件。
PCT/CN2023/121754 2023-06-21 2023-09-26 发光器件及显示装置 Ceased WO2024259820A1 (zh)

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