WO2023093494A1 - Dispositif électroluminescent et son procédé de préparation, et appareil photoélectrique - Google Patents

Dispositif électroluminescent et son procédé de préparation, et appareil photoélectrique Download PDF

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WO2023093494A1
WO2023093494A1 PCT/CN2022/129710 CN2022129710W WO2023093494A1 WO 2023093494 A1 WO2023093494 A1 WO 2023093494A1 CN 2022129710 W CN2022129710 W CN 2022129710W WO 2023093494 A1 WO2023093494 A1 WO 2023093494A1
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layer
functional layer
functional
doped
light
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Chinese (zh)
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敖资通
严怡然
洪佳婷
杨帆
莫新娣
马松
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Tcl科技集团股份有限公司
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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
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • 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
    • 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

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  • the present application relates to the field of photoelectric devices, in particular to an electroluminescence device, a preparation method thereof, and a photoelectric device.
  • Electroluminescence also known as electric field luminescence, is a physical phenomenon in which electrons excited by the electric field hit the luminescence center by applying a voltage to two electrodes to generate an electric field, which causes the transition, change, and recombination of electrons between energy levels to cause luminescence.
  • QLED Quantum Dots Light-Emitting Diode, Quantum Dot Light-Emitting Diode
  • QLED Quantum Dots Light-Emitting Diode
  • Quantum dots are composed of zinc, cadmium, selenium and sulfur atoms, and are particles with a particle diameter of less than 10nm. This substance has a very special property: when the quantum dot is stimulated by light, it will emit colored light, and the color is determined by the material making up the quantum dot and its size and shape. Because it has this property, it is able to change the color of the light emitted by the light source.
  • the emission wavelength range of quantum dots is very narrow, and the color is relatively pure and can be adjusted. Therefore, the picture of quantum dot display will be clearer and brighter than that of liquid crystal display. It is expected to become the next generation of flat panel display with broad development prospects.
  • the present application provides an electroluminescent device, a preparation method thereof, and a photoelectric device.
  • An embodiment of the present application provides an electroluminescent device, including: a first electrode, a second electrode, and a functional layer arranged between the first electrode and the second electrode, the functional layer has at least two layers, one of which is The functional layer is a light-emitting layer, and at least two layers of the functional layer are doped with a photocrosslinking agent and arranged adjacent to each other.
  • the photocrosslinking agent is selected from: coumarin, coumarin derivatives, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene , one or more of N-methylolacrylamide or diacetone acrylamide, the photocrosslinking agent is combined with the material of the functional layer through a chemical bond, and a crosslinking structure is formed between the photocrosslinking agents .
  • the photocrosslinking agent when the photocrosslinking agent is selected from coumarins, the coumarins are crosslinked to form a four-membered ring.
  • the mass ratio of the photocrosslinking agent to the functional layer material is (1-3): 4.
  • the functional layer doped with the photocrosslinking agent is composed of a functional layer material and a photocrosslinking agent, and the photocrosslinking agent is mixed and dispersed in the functional layer material middle.
  • each functional layer is doped with the photocrosslinking agent
  • each of the functional layers is composed of a functional layer material and the photocrosslinking agent
  • each In the functional layer the photocrosslinking agent is mixed and dispersed in the corresponding material of the functional layer.
  • one of the functional layers includes a hole functional layer, and the hole functional layer is disposed between the light-emitting layer and the second electrode, and the phototransmitter The coupling agent is mixed and dispersed in the hole functional layer and the light-emitting layer.
  • one of the functional layers includes an electronic functional layer, and the electronic functional layer is disposed between the light-emitting layer and the first electrode, and the photocrosslinking agent mixed and dispersed in the light-emitting layer and the electronic functional layer.
  • one layer of the functional layer includes a first film layer away from the adjacent functional layer, and a second film layer and a third film layer close to the adjacent functional layer; wherein, The second film layer is close to the adjacent lower functional layer, the third film layer is close to the adjacent upper functional layer, and the photocrosslinking agent is mixed and dispersed in the second film layer and the third film layer.
  • the two functional layers are a hole functional layer and an electron functional layer
  • the hole functional layer is disposed between the light-emitting layer and the second electrode
  • the electronic functional layer is arranged between the light-emitting layer and the first electrode; wherein, the side of the hole functional layer close to the light-emitting layer is doped with the photocrosslinking agent, and the light-emitting layer
  • the photo-crosslinking agent is doped on the side close to the hole function; the photo-crosslinking agent is doped on the side of the electronic functional layer close to the light-emitting layer, and the light-emitting layer is close to the electronic functional layer
  • One side is doped with the photocrosslinker.
  • the two functional layers are a hole functional layer and an electron functional layer
  • the hole functional layer is disposed between the light-emitting layer and the second electrode
  • the electron functional layer is disposed between the light emitting layer and the first electrode
  • the functional layer further includes a hole functional layer and an electron functional layer
  • the hole functional layer includes a hole injection layer
  • the The electronic functional layer includes an electron injection layer
  • the material of the hole injection layer is selected from: poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), polyvinylcarbazole , polymerized triarylamine, poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis- N,N-phenyl-1,4-phenylenediamine), 4,4',4"-tris(
  • the material of the light-emitting layer is selected from one of direct bandgap compound semiconductors and perovskite semiconductors with luminescence ability, and the direct bandgap compound semiconductors with luminescence ability are selected from group II-VI compounds, III-V Group compound, II-V group compound, III-VI compound, IV-VI group compound, I-III-VI group compound, II-IV-VI group compound, IV group simple substance;
  • the II-VI compound is selected from One or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe or PbTe
  • the III-V group compound is selected from one of GaP, GaAs, InP or InAs one or more
  • the perovskite semiconductor is selected from one or more of doped or non-doped inorganic perovskite semiconductors, and organic-inorganic hybrid perovskite semiconductors;
  • the material of the electron injection layer is selected from one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO or InSnO;
  • the second electrode material is selected from: metal or non-metallic materials, the metal or non-metallic materials are selected from nickel, platinum, gold, silver, iridium or carbon nanotubes; or selected from doped or undoped Metal oxides, the doped or undoped metal oxides are selected from the group consisting of indium tin oxide, indium zinc oxide, indium tin zinc oxide, indium copper oxide, tin oxide, indium oxide, cadmium:zinc oxide, fluorine : tin oxide, indium: zinc oxide, gallium: tin oxide or zinc: aluminum oxide;
  • the material of the first electrode is selected from one or more of metal materials, carbon materials, and metal oxides.
  • the metal material includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Mg
  • the carbon material includes one or more of graphite, carbon nanotube, graphene, carbon fiber
  • the metal oxide is selected from doped/non-doped metal oxide, or a composite electrode with metal sandwiched between doped/non-doped transparent metal oxide, the doped/non-doped metal oxide
  • the material includes one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO
  • the composite electrode includes 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/T
  • the embodiment of the present application also provides a method for manufacturing an electroluminescent device, the method comprising:
  • One of the functional layers is a light-emitting layer, and at least two layers of the functional layer are doped with a photocrosslinking agent and arranged adjacent to each other.
  • the photocrosslinking agent is selected from: coumarin, coumarin derivatives, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene , one or more of N-methylolacrylamide or diacetoneacrylamide.
  • the photocrosslinking agent when the photocrosslinking agent is selected from coumarins, the coumarins are crosslinked to form a four-membered ring.
  • the preparation method of the at least two functional layers includes:
  • Each of the functional layers is subjected to ultraviolet light irradiation treatment.
  • the preparation method of the at least two functional layers comprises:
  • Each of the functional layers is subjected to ultraviolet light irradiation treatment.
  • the mass ratio of the photocrosslinking agent to the functional layer material is (1 ⁇ 3):4.
  • the embodiment of the present application also provides a photoelectric device, including the electroluminescent device as described above, or an electroluminescent device prepared by the manufacturing method as described above.
  • the present application mixes a photocrosslinking agent in the materials of at least two adjacent functional layers.
  • the photocrosslinking agent can be combined with each functional layer material through a chemical bond. It can also form a cross-linked structure to make the bonding between adjacent functional layers more firm, avoiding the cracking of the film layer and the overall shedding of the film layer during the use of flexible devices, thereby improving the problem that the device is prone to failure .
  • Figure 1 is a schematic structural view of a positive-type electroluminescent device provided by an embodiment of the present application
  • Fig. 2 is a schematic structural diagram of a positive-type electroluminescent device provided by another embodiment of the present application.
  • Fig. 3 is a schematic structural diagram of an electroluminescent device with an inverse structure provided by an embodiment of the present application
  • Fig. 4 is a schematic flow chart of a method for preparing an electroluminescent device provided in an embodiment of the present application
  • Fig. 5 is a schematic flow chart of a method for preparing a positive-type structure electroluminescent device provided in an embodiment of the present application
  • Fig. 6 is a schematic flow chart of a method for preparing an electroluminescent device with an inverse structure provided in an embodiment of the present application
  • Fig. 7 is a photogram of the topography of each electroluminescent device provided in the embodiment of the present application.
  • a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
  • one or more means one or more, and “multiple” means two or more.
  • “One or more”, “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 item (unit) of a, b, or c”, or “at least one item (unit) of a, b, and c” can mean: a, b, c, a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.
  • an embodiment of the present application provides an electroluminescent device, including: a first electrode, a second electrode, and a functional layer arranged between the first electrode and the second electrode, and the functional layer has at least two layers, One of them is a light-emitting layer, and the materials of at least two functional layers are doped with a photocrosslinking agent and arranged adjacently.
  • the two or more functional layers there are two or more functional layers, one of which is a light-emitting layer.
  • the two or more functional layers there are at least two adjacent functional layers, and the materials of these two functional layers are all doped with a photocrosslinking agent.
  • the photo-crosslinking agent may be doped in both the light-emitting layer and its adjacent functional layers, or the cross-linking agent may be doped in other adjacent functional layers except the light-emitting layer.
  • the photocrosslinking agent in the materials of at least two adjacent functional layers, on the one hand, the photocrosslinking agent can be combined with each functional layer material through a chemical bond; on the other hand, the photocrosslinking agent A cross-linked structure can also be formed between them, so that the adjacent functional layers can be bonded more firmly, avoiding the cracking of the film layer and the overall shedding of the film layer during the use of the flexible device, thereby improving the ease of use of the device. failure problem.
  • the first electrode is a cathode and the second electrode is an anode; in other embodiments, the first electrode is an anode and the second electrode is a cathode.
  • the photocrosslinking agent is selected from: coumarin (2H-1-benzopyran-2-one), coumarin derivatives, hydroxyethyl methacrylate, hydroxyethyl methacrylate One or more of propyl ester, divinylbenzene, N-methylol acrylamide or diacetone acrylamide, the photocrosslinking agent is combined with the material of the functional layer through a chemical bond, and the photocrosslinking agent form a cross-linked structure between the agents.
  • the photocrosslinking agent is selected from coumarin or its derivatives
  • the coumarins in each functional layer are crosslinked to form a four-membered ring.
  • the chemical bonding mode of the material of each functional layer and coumarin or its derivatives is:
  • the cross-linking agent material is amino-substituted coumarin, carboxyl-substituted polymeric triarylamine and amino-substituted coumarin are combined through amide bonds to obtain reversible photoresponsive cross-linked holes Inject material.
  • the cross-linking agent material is coumarin, and the carbonyl group of coumarin is combined with ZnS through a coordination bond to obtain a reversible light-responsive cross-linked QD material.
  • the crosslinking agent material is coumarin, and the carbonyl group of coumarin is combined with ZnO through a coordination bond to obtain a reversible photoresponsive crosslinked electron injection layer material.
  • the mass ratio of the photocrosslinking agent to the material of the functional layer is (1-3):4. If the content of the photocrosslinking agent is too high, the carrier mobility of the crosslinked layer will be reduced, and if the content is too low, the functional layers cannot be effectively crosslinked. It can be understood that the mass ratio of the photocrosslinking agent to the functional layer material is any value within the range of (1-3):4, such as 1:4, 1.5:4, 2:4, 2.5:4 , 3:4, etc., or other unlisted values within the range of (1 ⁇ 3):4.
  • the photocrosslinking agent can be dispersed in the material of the functional layer, or can be dispersed in each functional layer. contact interface.
  • the functional layer doped with the photocrosslinking agent is composed of a functional layer material and a photocrosslinking agent, and the photocrosslinking agent is mixed and dispersed in the functional layer material.
  • the photocrosslinking agent is doped in the material of each functional layer, each functional layer is composed of functional layer material and the photocrosslinking agent, and the photocrosslinking agent is mixed and dispersed in the corresponding functional layer material.
  • FIG. 1 shows an electroluminescent device, including a substrate 10, an anode 20 and a cathode 60, and a functional layer between the anode 20 and the cathode 60, so
  • the functional layer includes a hole injection layer 30, a light-emitting layer 40, and an electron injection layer 50 stacked in sequence from bottom to top, wherein the photocrosslinking agent is mixed and dispersed in the hole injection layer 30, the light-emitting layer 40, and the electron injection layer 50 of the material.
  • the functional layer includes a first film layer away from the adjacent functional layer, and a second film layer and a third film layer close to the adjacent functional layer; wherein, the second film layer Adjacent to the adjacent lower functional layer, the third film layer is adjacent to the adjacent upper functional layer, and the photocrosslinking agent is mixed and dispersed in the second film layer and the third film layer.
  • the precursor solution of the functional layer material and the precursor solution of the cross-linking material are only different in ligands, the first film layer, the second film layer or the third film layer will appear to be miscible. , forming a relatively stable whole. Devices with this structure can not only form a cross-linked structure with other functional layers at the interface, but also retain their excellent electrical properties to the greatest extent.
  • the functional layer may include a first film layer and a third film layer, the first film layer is located on a side of the functional layer away from the adjacent functional layer, The third film layer is located on a side of the functional layer close to the adjacent functional layer.
  • the functional layer may include a first film layer and a second film layer, the first film layer is located on the side of the functional layer away from the adjacent functional layer , the second film layer is located on a side of the functional layer close to the adjacent functional layer.
  • the functional layer may include a first film layer, a second film layer and a third film layer, and the second film layer is located close to the functional layer.
  • the third film layer is located on the side of the functional layer close to the adjacent functional layer above, the first film layer is located between the second film layer and between the third layer.
  • FIG. 2 shows an electroluminescent device, including a substrate 10, an anode 20 and a cathode 60, and a functional layer between the anode 20 and the cathode 60, so
  • the functional layer includes a hole injection layer 30 , a light emitting layer 40 and an electron injection layer 50 stacked in sequence from bottom to top.
  • the hole injection layer 30 in FIG. 2 includes a first hole injection layer 31 away from the light-emitting layer 40, and a third hole injection layer 32 close to the light-emitting layer 40, and the first hole injection layer layer 31 as the first film layer, and the third hole injection layer 32 as the third film layer;
  • the light emitting layer 40 includes a second light emitting layer 41 close to the hole injection layer 30, close to the electron injection layer 50 of the third light-emitting layer 43, and the first light-emitting layer 42 between the second light-emitting layer 41 and the third light-emitting layer 43, the first light-emitting layer 42 is used as the first film layer, and the second light-emitting layer 41 is used as the The second film layer, the third light-emitting layer 43 is used as the third film layer;
  • the electron injection layer 50 includes a second electron injection layer 51 close to the light-emitting layer 40, and a first electron injection layer far away from the light-emitting layer 40
  • the distribution of photocrosslinkers in a functional layer can be the same or different than that in an adjacent functional layer.
  • the photocrosslinking agent in the functional layer and the adjacent functional layer is evenly distributed; in other embodiments, the functional layer is divided into the first film layer, the second film layer film layer and the third film layer, and the photocrosslinking agent in the adjacent functional layer is evenly distributed.
  • the photocrosslinking agent can play a crosslinking effect, making the bonding between adjacent functional layers more perfect. firm.
  • the functional layer in addition to the light-emitting layer, the functional layer further includes a hole functional layer and an electron functional layer, and the hole functional layer is disposed between the light-emitting layer and the second electrode , the electronic functional layer is disposed between the light-emitting layer and the first electrode, and the photocrosslinking agent is mixed and dispersed in the electronic functional layer, hole functional layer and the light-emitting layer.
  • the functional layer in addition to the light emitting layer, the functional layer further includes a hole functional layer and an electron functional layer, and the hole functional layer is disposed between the light emitting layer and the second electrode
  • the electronic functional layer is arranged between the light-emitting layer and the first electrode, the side of the hole functional layer close to the light-emitting layer is doped with the photocrosslinking agent, and the light-emitting layer is close to
  • the side of the hole function is doped with the photocrosslinking agent, and/or, the side of the electronic functional layer close to the light-emitting layer is doped with the photocrosslinker, and the light-emitting layer is close to the light-emitting layer.
  • One side of the electronic functional layer is doped with the photocrosslinking agent.
  • the electroluminescent device described in the embodiment of the present application may be of a positive type structure or an inverse type structure.
  • the side of the first electrode or the second electrode away from the light-emitting layer also includes a substrate, the second electrode is arranged on the substrate in the positive structure, and the first electrode is arranged on the substrate in the inverse structure on the substrate.
  • hole functional layers such as a hole transport layer and an electron blocking layer can also be provided between the second electrode and the light-emitting layer, and between the first electrode and the Electronic functional layers such as hole blocking layers can also be arranged between the light emitting layers.
  • the functional layer further includes a hole functional layer and an electron functional layer, the hole functional layer includes a hole injection layer, and the electron functional layer includes an electron injection layer.
  • Figure 1 shows a schematic diagram of a positive structure of the electroluminescent device described in the embodiment of the present application.
  • the positive structure quantum dot device includes a substrate 10, and The anode 20, the hole injection layer 30 arranged on the surface of the anode 20, the light emitting layer 40 arranged on the surface of the hole injection layer 30, the electron injection layer 50 arranged on the surface of the light emitting layer 40, and the The cathode 60 on the surface of the electron injection layer 50, wherein the hole injection layer 30, the light emitting layer 40 and the electron injection layer 50 are all doped with a photocrosslinking agent.
  • Fig. 3 shows a schematic diagram of an inverse structure of the quantum dot device described in the embodiment of the present application.
  • the electronic light emitting device is an electroluminescent device (QLED).
  • QLED electroluminescent device
  • each functional layer may be the following materials, for example:
  • the substrate can be a rigid substrate or a flexible substrate.
  • Specific materials may include one of glass, silicon wafer, polycarbonate, polymethylmethacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone or more.
  • the second electrode material may be composed of nickel (Ni), platinum (Pt), gold (Au), silver (Ag), iridium (Ir) or carbon nanotube (CNT) metal or non-metal material.
  • the material of the hole injection layer is selected from: poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl) diphenylamine), polyvinylcarbazole, polymeric triarylamine, poly(N , N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1 ,4-phenylenediamine), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl Base-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, 15N,N'-diphenyl-N,N'-(1- One or more of naphthyl)
  • the material of the light-emitting layer is selected from: direct bandgap compound semiconductors with light-emitting ability, including but not limited to II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds One or more of compound, I-III-VI compound, II-IV-VI compound or IV element.
  • the semiconductor materials used in the light-emitting layer include but are not limited to nanocrystals of II-VI semiconductors, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe and other binary, ternary, and quaternary II-VI compounds; nanocrystals of III-V semiconductors, such as GaP, GaAs, InP, InAs, and other binary, ternary, and quaternary III-V compounds;
  • the materials used for the light-emitting layer are not limited to II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compounds, IV simple substances, etc.
  • the light-emitting layer material can also be one or more of doped or non-doped inorganic perovskite semiconductors and organic-inorganic hybrid perovskite semiconductors; specifically, the inorganic
  • the general structural formula of perovskite semiconductor is AMX 3 , where A is Cs + ion, M is a divalent metal cation, including but not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ , X is a halogen anion, including but not limited to Cl - , Br - , I - ;
  • the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX 3 , where B is an organic amine cation, including but not limited to
  • the inorganic metal halide octahedron MX 64 - is connected by a common top, the metal cation M is located at the body center of the halogen octahedron, and the organic amine cation B fills the gap between the octahedrons, forming an infinitely extending Three-dimensional structure;
  • M is a divalent metal cation
  • the material of the electron injection layer is selected from one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO or InSnO.
  • the material of the first electrode is selected from one or more of metal materials, carbon materials, and metal oxides.
  • the metal material includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, Mg
  • the carbon material includes one or more of graphite, carbon nanotube, graphene, carbon fiber
  • the metal oxide is selected from doped/non-doped metal oxide, or a composite electrode with metal sandwiched between doped/non-doped transparent metal oxide, the doped/non-doped metal oxide
  • the material includes one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO
  • the composite electrode includes 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/T
  • the present application also provides a method for preparing an electroluminescence device.
  • the preparation method of described electroluminescence device comprises the following steps:
  • One of the functional layers is a light-emitting layer, and at least two layers of the functional layer are doped with a photocrosslinking agent and arranged adjacent to each other.
  • the electroluminescent device is a positive structure, correspondingly, the first electrode is a cathode, and the second electrode is an anode; in other embodiments, the electroluminescent device is Negative structure, correspondingly, the first electrode is an anode, and the second electrode is a cathode.
  • Fig. 5 shows a method for preparing a positive structure of the electroluminescent device described in the embodiment of the present application.
  • the method for preparing the electroluminescent device of the positive structure includes the following step:
  • One of the functional layers is a light-emitting layer, and the materials of at least two functional layers are doped with a photocrosslinking agent and arranged adjacent to each other.
  • FIG. 6 shows a method for preparing an inverse structure of the electroluminescent device described in the embodiment of the present application.
  • the method for preparing an electroluminescent device with an inverse structure includes the following step:
  • One of the functional layers is a light-emitting layer, and the materials of at least two functional layers are doped with a photocrosslinking agent and arranged adjacent to each other.
  • each functional layer can be realized by methods known in the art.
  • each functional layer is prepared by a solution method, and the production cost can be greatly reduced by using this method.
  • solution methods include spin coating, printing, inkjet printing, blade coating, printing, dipping, soaking, spraying, roll coating, casting, slot coating method, strip coating method.
  • the preparation method of at least two functional layers in the step S1, S10 or S200 includes:
  • the preparation method of the two or more functional layers includes:
  • the mass ratio of the photocrosslinking agent to the functional layer material is (1 ⁇ 3):4.
  • the photocrosslinking agent is selected from: coumarin, coumarin derivatives, hydroxyethyl methacrylate, hydroxypropyl methacrylate, divinylbenzene, N-methylolpropylene One or more of amide or diacetone acrylamide.
  • each functional layer is mixed with coumarin or its derivatives.
  • the cross-linking agent material is amino-substituted coumarin
  • the two are mixed and then heated to cause amidation reaction of the two materials, as shown in formula 1, to obtain Backlight Responsive Crosslinked Hole Injection Materials.
  • the cross-linking agent material is coumarin, the two are mixed and heated, and the carbonyl group of coumarin forms a coordination bond with ZnS to obtain a reversible light-responsive cross-linked QD material.
  • the crosslinking agent material is coumarin, and the two are mixed and then heated.
  • the carbonyl group of coumarin forms a coordination bond with ZnO to obtain a reversible photoresponsive crosslinked electron injection material.
  • the cross-linked structure of the hole injection material and the light-emitting layer is shown in Formula 1
  • the cross-linked structure of the electron injection material and the light-emitting layer material is shown in Formula 2.
  • Zn in Formula 1 represents ZnS quantum dots of the light-emitting layer material
  • Zn in Formula 2 represents the electron injection material ZnO
  • the photocrosslinking agent can be combined with the materials of each functional layer through chemical bonds, and the double bond in coumarin can also undergo chemical crosslinking to form four layers under the irradiation of 365nm ultraviolet light.
  • This structure can make the bonding between adjacent functional layers more firm, avoiding the cracking of the film layer and the overall shedding of the film layer during the use of flexible devices, thereby improving the problem that the device is prone to failure .
  • the present application also provides a photoelectric device, including the electroluminescent device described in any one of the above, or an electroluminescent device prepared by the preparation method described in any of the above, its structure, realization principle and effect similar and will not be repeated here.
  • the optoelectronic device is a QLED.
  • the optoelectronic device may be: a lighting fixture and a backlight, or any product or component with a display function such as a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, and a navigator.
  • a lighting fixture and a backlight or any product or component with a display function such as a mobile phone, a tablet computer, a television, a monitor, a notebook computer, a digital photo frame, and a navigator.
  • This embodiment provides an electroluminescent device with a positive top emission structure, and the preparation process of the device includes:
  • the material solution (8 mg/mL) of the cross-linked hole injection layer was spin-coated at 3000 rpm for 30 seconds, then heated at 80° C. for 10 minutes, and left to cool for 5 minutes.
  • Ultraviolet light is used for irradiation, the wavelength is 365nm, the pulse width of the ultraviolet laser is 22ns, the power is 5W, the frequency is 1.2Hz, and the time is 90s.
  • the vacuum degree is not higher than 3 ⁇ 10 -4 Pa, and Ag is evaporated at a speed of 1 angstrom/second, for 200 seconds, and a thickness of 20nm, to obtain a top-emitting positive electroluminescent device, and to The device is packaged.
  • This embodiment provides an electroluminescent device with a positive top emission structure, and the preparation process of the device includes:
  • the wavelength is 365nm
  • the pulse width of the ultraviolet laser is 22ns
  • the power is 5W
  • the frequency is 1.2Hz
  • the time is 90s.
  • the vacuum degree is not higher than 3 ⁇ 10 -4 Pa, and Ag is evaporated at a speed of 1 angstrom/second for 200 seconds and a thickness of 20 nm to obtain a top-emitting positive-type electroluminescent device, and Package the device.
  • This example is roughly the same as Example 1, except that the concentration of coumarin in the crosslinked hole transport layer is 2 mg/mL; the concentration of coumarin in the crosslinked light-emitting layer is 5 mg/mL; Soybean concentration is 8mg/mL.
  • This example is roughly the same as Example 1, except that the concentration of coumarin in the crosslinked hole transport layer is 6 mg/mL; the concentration of coumarin in the crosslinked light-emitting layer is 15 mg/mL; Soybean concentration is 20mg/mL.
  • This example is roughly the same as Example 1, except that the concentration of coumarin in the crosslinked hole transport layer is 0.2 mg/mL; the concentration of coumarin in the crosslinked light-emitting layer is 1 mg/mL; The concentration of coumarin was 1 mg/mL.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • This example is roughly the same as Example 1, except that the concentration of coumarin in the crosslinked hole transport layer is 12 mg/mL; the concentration of coumarin in the crosslinked light-emitting layer is 30 mg/mL; Soybean concentration is 50mg/mL.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • This example is roughly the same as Example 2, except that the concentration of coumarin in the crosslinked hole transport layer is 2 mg/mL; the concentration of coumarin in the crosslinked light-emitting layer is 5 mg/mL; Soybean concentration is 8mg/mL.
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • This example is roughly the same as Example 2, except that the concentration of coumarin in the crosslinked hole transport layer is 6 mg/mL; the concentration of coumarin in the crosslinked light-emitting layer is 15 mg/mL; Soybean concentration is 20mg/mL.
  • Embodiment 9 is a diagrammatic representation of Embodiment 9:
  • This example is roughly the same as Example 2, except that the concentration of coumarin in the crosslinked hole transport layer is 0.2 mg/mL; the concentration of coumarin in the crosslinked light-emitting layer is 1 mg/mL; The concentration of coumarin was 1 mg/mL.
  • This example is roughly the same as Example 2, except that the concentration of coumarin in the crosslinked hole transport layer is 12 mg/mL; the concentration of coumarin in the crosslinked light-emitting layer is 30 mg/mL; Soybean concentration is 50mg/mL.
  • This embodiment provides an electroluminescent device with a positive top emission structure, and the preparation process of the device includes:
  • the vacuum degree is not higher than 3 ⁇ 10 -4 Pa, and Ag is evaporated at a speed of 1 angstroms/second, for 200 seconds, and a thickness of 20nm, to obtain a top-emitting positive electroluminescent device, and to The device is packaged.
  • the data in the table is the working life test data of the flexible QLED device after the mechanical stress test. Due to the cracking of the device film prepared by the process of Comparative Example 1, there is no test data.
  • L represents the brightness of the device. Under the same current, the higher the brightness of the device, the better the efficiency of the device; T95 represents the time it takes for the brightness of the device to decay from 100% to 95%. Under the same current, the longer the T95 time of the device, it means the performance of the device The better the stability, the better the stability; T95-1K means when the device is under 1000nit brightness, the time it takes for the brightness to decay from 100% to 95%. This value is calculated from the value of L and T95; C.E indicates the current efficiency of the device.
  • C.E-1000nit indicates the current of the device at a brightness of 1000nit Efficiency, under the premise that the area of the light-emitting area and the driving current are consistent, the higher the C.E-1000nit, the better the performance of the device.
  • Comparing the morphology and performance of Example 1, Example 2 and Comparative Example 1 it can be seen from Figure 7 that the morphology of Embodiment 1 and Example 2 is obviously better than that of Comparative Example, and in Table 1, Comparative Example
  • the device of 1 failed due to cracking of the film layer, indicating that doping a crosslinking agent in the material of the functional layer of the device can avoid cracking of the functional layer, improve the yield of the device, and improve the problem of device failure. This is due to the formation of a cross-linking structure between the photo-crosslinking agents, which makes the bonding between adjacent functional layers more firm, and prevents the cracking of the film layer and the overall shedding of the film layer during the use of the flexible device.
  • Embodiment 1, embodiment 3 to embodiment 6 are respectively compared with embodiment 2, embodiment 7 to embodiment 10 correspondingly, as can be seen from table 1, the device performance of embodiment 2, embodiment 7 to embodiment 10 and life are significantly better than the corresponding examples 1, 3 to 6, indicating that a cross-linked structure is formed at the interface where each functional layer contacts, and the excellent electrical properties of the device itself are preserved to the greatest extent.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente demande divulgue un dispositif électroluminescent et son procédé de préparation, et un appareil photoélectrique. Le dispositif électroluminescent comprend : une première électrode, une seconde électrode et des couches fonctionnelles, qui sont disposées entre la première électrode et la seconde électrode, au moins deux couches fonctionnelles étant présentes, l'une des couches fonctionnelles étant une couche électroluminescente, et le matériau des au moins deux couches fonctionnelles étant dopé avec un agent de photo-réticulation ; et les au moins deux couches fonctionnelles étant disposées adjacentes l'une à l'autre.
PCT/CN2022/129710 2021-11-24 2022-11-04 Dispositif électroluminescent et son procédé de préparation, et appareil photoélectrique WO2023093494A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW498703B (en) * 2000-11-30 2002-08-11 Hitachi Ltd Organic electroluminesce device, its production method and liquid crystal display device using it
JP2004303741A (ja) * 2004-07-29 2004-10-28 Pioneer Electronic Corp 有機エレクトロルミネセンス表示装置
CN101048827A (zh) * 2004-08-26 2007-10-03 精工爱普生株式会社 导电材料用组合物、导电材料、导电层、电子器件和电子装置
CN104600203A (zh) * 2014-12-26 2015-05-06 合肥京东方光电科技有限公司 发光层及其制备方法、有机电致发光器件、显示装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW498703B (en) * 2000-11-30 2002-08-11 Hitachi Ltd Organic electroluminesce device, its production method and liquid crystal display device using it
JP2004303741A (ja) * 2004-07-29 2004-10-28 Pioneer Electronic Corp 有機エレクトロルミネセンス表示装置
CN101048827A (zh) * 2004-08-26 2007-10-03 精工爱普生株式会社 导电材料用组合物、导电材料、导电层、电子器件和电子装置
CN104600203A (zh) * 2014-12-26 2015-05-06 合肥京东方光电科技有限公司 发光层及其制备方法、有机电致发光器件、显示装置

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