WO2023202142A1 - 空穴传输薄膜、电致发光器件及其制备方法 - Google Patents

空穴传输薄膜、电致发光器件及其制备方法 Download PDF

Info

Publication number
WO2023202142A1
WO2023202142A1 PCT/CN2022/142639 CN2022142639W WO2023202142A1 WO 2023202142 A1 WO2023202142 A1 WO 2023202142A1 CN 2022142639 W CN2022142639 W CN 2022142639W WO 2023202142 A1 WO2023202142 A1 WO 2023202142A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
film layer
hole transport
film
conductive polymer
Prior art date
Application number
PCT/CN2022/142639
Other languages
English (en)
French (fr)
Inventor
侯文军
Original Assignee
Tcl科技集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN202210420916.7A external-priority patent/CN116997199A/zh
Priority claimed from CN202210420931.1A external-priority patent/CN116981279A/zh
Application filed by Tcl科技集团股份有限公司 filed Critical Tcl科技集团股份有限公司
Publication of WO2023202142A1 publication Critical patent/WO2023202142A1/zh

Links

Images

Classifications

    • 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]

Definitions

  • the present application relates to the field of display technology, and in particular to a hole transport film, an electroluminescent device and a preparation method thereof.
  • QLED Quantum Dot Light Emitting Diodes
  • OLED organic light-emitting diode
  • the present application provides a hole transport film, an electroluminescent device and a preparation method thereof.
  • Embodiments of the present application provide a hole transport film, including a first film layer and a second film layer arranged in a stack.
  • the first film layer is a conductive polymer layer or an inorganic material layer
  • the second film layer is a conductive polymer layer. Polymer layer.
  • the conductive polymer used in the conductive polymer layer includes a homopolymer formed from any one of aniline monomers, thiophene monomers and fluorene monomers or a copolymer formed from any combination; and/or ,
  • the inorganic material used in the inorganic material layer includes any one of molybdenum oxide, vanadium oxide, tungsten oxide and nickel oxide.
  • inorganic nanoparticles are spacedly distributed inside the conductive polymer layer of the second film layer.
  • the inorganic nanoparticles include any one of silica particles, titanium dioxide particles, zinc sulfide particles and zinc oxide particles.
  • the conductive polymer of the first film layer is a cross-linkable polymer; and/or the conductive polymer of the second film layer is a non-cross-linked polymer.
  • the diameter of the inorganic nanoparticles is 2 nm to 10 nm; and/or the distribution spacing of the inorganic nanoparticles in the second film layer is 2 nm to 15 nm.
  • the thickness of the first film layer 110 is 5 nm to 50 nm, and/or the thickness of the second film layer is 1 to 15 nm.
  • the first film layer is a conductive polymer layer or an inorganic material layer
  • the second film layer is a conductive polymer layer
  • the conductive polymer layer of the second film layer has a number of inorganic materials spaced apart inside. Nanoparticles, the thickness of the first film layer is 5nm ⁇ 35nm; and/or the thickness of the second film layer is 5nm ⁇ 15nm;
  • Both the first film layer and the second film layer are conductive polymer layers, the thickness of the first film layer is 10 nm to 50 nm, and the thickness of the second film layer is 1 nm to 10 nm.
  • the present application also provides an electroluminescent device, including a stacked anode, a hole transport layer, a luminescent layer, and a cathode, wherein the hole transport layer is the above hole transport film, and the luminescent layer is adjacent to One side of the hole transport layer is partially embedded in the second film layer.
  • one side of the second film layer of the light-emitting layer adjacent to the hole transport layer is partially embedded in the hole transport layer.
  • the luminescent layer includes quantum dots, the quantum dots are selected from one or more of single structure quantum dots and core-shell structure quantum dots, the single structure quantum dots are selected from II-VI group compounds, One or more of Group III-V compounds and Group I-III-VI compounds, the Group II-VI compounds are selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, One or more of ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe, the III-V compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, One or more of InNP, InNSb, GaAlNP and InAlNP, the I-
  • the electroluminescent device is further provided with a hole injection layer between the anode and the hole transport layer; and or, the electroluminescent device is provided with a hole injection layer between the cathode and the light-emitting layer. There is also an electron transport layer between them.
  • this application also provides a method for preparing an electroluminescent device, which includes the following steps:
  • a hole transport layer is provided on the anode substrate
  • a cathode is provided on the light-emitting layer
  • the setting of the hole transport layer includes: setting a first film layer on the anode substrate, and setting a second film layer on the first film layer;
  • the first film layer is a conductive polymer layer or an inorganic material layer
  • the second film layer is a conductive polymer layer
  • disposing the first film layer on the anode substrate includes: disposing a chemical solution containing conductive polymer or inorganic material on the anode of the anode substrate, and performing a drying process, wherein the specific temperature of the drying process is 130°C. ⁇ 200°C.
  • arranging the second film layer on the first film layer includes placing a conductive polymer or a chemical solution containing inorganic nanoparticles and a conductive polymer on the first film layer, and performing a drying process,
  • the specific temperature for the above-mentioned drying treatment is 130°C to 200°C.
  • the step of providing a hole transport layer on the anode substrate specifically includes:
  • a second film layer is provided on the first film layer, wherein 5% to 10% of the organic solution remains in the second film layer based on the total mass of the second film layer, so that the second film layer
  • the two film layers form the semi-humid zone.
  • the first film layer when the first film layer is disposed on the anode substrate, the first film layer is subjected to a first vacuum reduced pressure drying process, and when the second film layer is disposed on the first film layer, the first film layer is The second film layer undergoes a second vacuum reduced pressure drying process; the first pressure during the first vacuum reduced pressure drying process is less than the second pressure during the second vacuum reduced pressure drying process, and/or, the The first duration of the first vacuum reduced pressure drying process is greater than the second duration of the second vacuum reduced pressure drying process.
  • the first pressure is less than 10 Pa
  • the second pressure is 1000 Pa ⁇ 10000 Pa
  • the first duration is greater than 5 min
  • the second duration is The time is less than 5min.
  • the first film layer on the anode substrate when disposing the first film layer on the anode substrate, perform a first baking and drying process on the first film layer, and when disposing the second film layer on the first film layer, perform a first baking and drying process on the first film layer.
  • the second film layer undergoes a second baking and drying process; the first temperature during the first baking and drying process is higher than the second temperature during the second baking and drying process, and/or the first baking and drying process
  • the third duration of the bake-drying process is greater than the fourth duration of the second bake-drying process.
  • the first temperature is 150°C to 300°C
  • the second temperature is 50°C to 150°C
  • the third duration is 15min to 60min
  • the fourth duration is 1min ⁇ 15min.
  • Figure 1 is a schematic structural diagram of a hole transport film provided by an embodiment of the present application.
  • Figure 2 is a schematic structural diagram of another hole transport film provided by an embodiment of the present application.
  • Figure 3 is a flow chart of a method for preparing a hole transport film provided by an embodiment of the present application.
  • Figure 4 is a schematic structural diagram of an electroluminescent device provided by an embodiment of the present application.
  • FIG. 5 is a schematic structural diagram of another electroluminescent device provided by an embodiment of the present application.
  • Figure 6 is a schematic structural diagram of yet another electroluminescent device provided by an embodiment of the present application.
  • FIG. 7 is a schematic structural diagram of yet another electroluminescent device provided by an embodiment of the present application.
  • Figure 8 is a flow chart of a method for manufacturing an electroluminescent device provided by an embodiment of the present application.
  • Figure 9 is a flow chart of another method for preparing an electroluminescent device provided by an embodiment of the present application.
  • Figure 10 is a flow chart of yet another method for preparing an electroluminescent device provided by an embodiment of the present application.
  • Expressions such as "one or more” in this application refer to one or more of the listed items, and “multiple” refers to any combination of two or more of these items, including a single item (species). ) or any combination of plural items (kinds), for example, “at least one (kind) of a, b, or c" or “at least one (kind) 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 respectively.
  • Existing QLED devices/OLED devices are all organic-inorganic composite devices, that is, hole injection and transmission are organic materials, and electron injection and transmission are inorganic materials.
  • hole injection and transmission are organic materials
  • electron injection and transmission are inorganic materials.
  • forward bias is applied to both ends of the QLED device/OLED device, the electrons and holes enter the luminescent layer through the electron transport layer and hole transport layer respectively; and recombine in the luminescent layer to emit light.
  • the electron migration efficiency of inorganic nanoparticles is much greater than the hole migration efficiency, this will cause a large amount of charge to accumulate at the contact interface between the hole transport layer and the light-emitting layer, thus affecting device performance and service life.
  • this embodiment provides a hole transport film 100.
  • the hole transport film 100 includes a first film layer 110 and a second film layer 120 arranged in a stack, and the One film layer 110 is a conductive polymer layer or an inorganic material layer, and the second film layer 120 is a conductive polymer layer.
  • FIGS. 1-2 are only simple illustrations of the layout of each layer of the hole transport film 100, rather than the actual structure of the hole transport film 100.
  • the conductive polymer used in the conductive polymer layer may specifically include a homopolymer formed from any one of aniline monomers, thiophene monomers and fluorene monomers or a copolymer formed from any combination. It can be understood that the conductive polymer used in the first film layer 110 and the second film layer 120 may be the same or different.
  • the inorganic material used in the above-mentioned inorganic material layer may specifically include any one of molybdenum oxide, vanadium oxide, tungsten oxide and nickel oxide.
  • both the first film layer 110 and the second film layer 120 are conductive polymer layers.
  • the first film layer 110 is a conductive polymer layer or an inorganic material layer
  • the second film layer 120 is a conductive polymer layer
  • the inside of the conductive polymer layer of the second film layer 120 There are several inorganic nanoparticles 121 distributed at intervals.
  • the conductive polymer of the first film layer 110 may be a cross-linkable polymer, which means that the conductive polymer contains cross-linking groups (cross-linking groups are unreacted functional groups, that is, Network polymers formed by chain polymers under certain conditions through other functional groups can reduce the solubility of the polymer in solvents and can further undergo chemical reactions under high temperature and other conditions.
  • the cross-linking groups can be double bonds, rings, etc. butene, or epoxy group). Since there will be interfacial miscibility problems when preparing a double-layer film structure, the conductive polymer of the first film layer 110 is a cross-linkable polymer, which can effectively avoid the impact of the second film layer 120 on the first film layer when it is disposed. 110 surface damage.
  • the conductive polymer of the second film layer 120 may be a non-crosslinked polymer, which means that the conductive polymer does not contain crosslinking groups.
  • This structure of the second film layer 120 is beneficial to the subsequent preparation of the light-emitting layer (especially the quantum dot light-emitting layer of the QLED device) on the second film layer 120.
  • the light-emitting layer (especially the quantum dot light-emitting layer of the QLED device) is better.
  • the ground part is embedded into the second film layer 120, that is, the embedding effect is improved.
  • the particles in the light-emitting layer can also be effectively controlled.
  • the thickness of embedding for example, the total thickness of the hole transport film 100 is 25nm, and the thickness of the first film layer 110 is 20nm, then the maximum embedding thickness of quantum dots is 5nm.
  • the first method is to use monomers containing cross-linking groups before polymerization to prepare cross-linkable polymers.
  • Monomers with cross-linking groups prepare non-cross-linked polymers.
  • cross-linkable polymers conductive structural units without cross-linking groups (such as aniline monomers, thiophene units, or Fluorene units, etc.) and conductive structural units (such as aniline monomers, thiophene units, or fluorene units, etc.) containing cross-linking groups (such as double bonds, cyclobutene, or epoxy groups, etc.) or non-conductive structural units ( (such as styrene group or methylene group, etc.) are copolymerized to form the above-mentioned cross-linkable polymer, in which the proportion of structural units containing cross-linking groups in the corresponding polymer can be 1 to 5%; the second method is After the preparation of the conductive polymer is completed, cross-linking groups are introduced through subsequent reactions with side chains to turn the non-cross-linked polymer into a cross-linkable polymer.
  • cross-linking groups such as aniline monomers, thiophene units, or Fluorene units, etc.
  • the embodiment of the present application adds inorganic nanoparticles 121 to the second film layer 120 and controls the distribution of the inorganic nanoparticles 121 in the second film layer.
  • the distribution in 120 can effectively improve the hole transport performance of the hole transport film 100, and at the same time, when the hole transport film 100 is used as the hole transport layer of an electroluminescent device, the luminescent layer (especially The quantum dot light-emitting layer of the QLED device) is disposed on the second film layer 120.
  • inorganic nanoparticles 121 are distributed at intervals in the second film layer 120, they can interact closely with the nanoparticles in the surface of the adjacent light-emitting layer.
  • Contact so that the side of the light-emitting layer adjacent to the hole transport layer is partially embedded in the second film layer, thereby increasing the contact between the hole transport layer and the light-emitting layer (especially the quantum dot light-emitting layer of the QLED device) to increase hole injection.
  • the second film layer 120 may be a conductive polymer layer formed of the same conductive polymer as the first film layer 110 , or may be a conductive polymer layer. A conductive polymer layer formed of a conductive polymer different from the first film layer 110 .
  • the above-mentioned inorganic nanoparticles 121 may specifically include any one of silica particles, titanium dioxide particles, zinc sulfide particles, and zinc oxide particles.
  • the diameter of the inorganic nanoparticles 121 can specifically range from 2 nm to 10 nm, and the distribution spacing of the inorganic nanoparticles 121 in the second film layer 120 ranges from 2 nm to 15 nm. In this way, by adding these inorganic nanoparticles 121 in the second film layer 120 and controlling the corresponding layout of these inorganic nanoparticles 121 in the second film layer 120, the hole transport of the hole transport film 100 can be further improved. performance and increase the contact between the hole transport film 100 and the light-emitting layer (especially the quantum dot light-emitting layer of the QLED device) when used as a hole transport layer.
  • the thickness of the first film layer 110 may be 5 nm ⁇ 50 nm, and the thickness of the second film layer 120 may be 1 ⁇ 15 nm.
  • the thickness of the first film layer 110 may be 10 nm to 50 nm, and the thickness of the second film layer 120 may be 1 nm to 1 nm. 10nm, so that the total thickness of the hole transporting film 100 formed by stacking the two can specifically range from 11nm to 60nm, so as to meet the requirements of the electroluminescent device for the hole transporting film 100.
  • the first film layer 110 is a conductive polymer layer or an inorganic material layer
  • the second film layer 120 is a conductive polymer layer
  • the conductive polymer layer of the second film layer 120 is internally spaced with a plurality of
  • the thickness of the first film layer 110 can be specifically 5nm-35nm
  • the thickness of the second film layer 120 can be specifically 5nm-15nm, so that the total thickness of the hole transport film 100 formed by stacking the two layers can be specifically 5nm-35nm. In 10nm ⁇ 50nm, to meet the requirements of the corresponding electroluminescent device for the hole transport layer.
  • this embodiment provides a method for preparing a hole transport film.
  • the preparation method includes the following steps:
  • Step S110 Provide a substrate.
  • the preparation method of this embodiment is mainly used in the preparation process of the hole transport film 100 in the above embodiment. Therefore, taking the hole transport film 100 in FIG. 1 as an example, each method step of this embodiment will be described accordingly.
  • the substrate is mainly used as a carrier for preparing the hole transport film 100, so the completed hole transport film 100 shown in FIG. 1 does not show the substrate.
  • Step S120 Set a first film layer on the substrate.
  • the first film layer 110 is disposed on the substrate.
  • a chemical solution containing a conductive polymer or inorganic material is spin-coated, ink-jet printed, or slit-coated on the substrate.
  • a drying process (which may be a vacuum drying process or a baking drying process) to obtain the first film layer 110 .
  • the specific temperature of the above-mentioned drying process may be 130°C to 200°C, so that the first film layer 110 is completely dried.
  • the above-mentioned conductive polymer may specifically include a homopolymer formed from any one of aniline monomers, thiophene monomers and fluorene monomers or a copolymer formed from any combination.
  • the above-mentioned inorganic material may specifically include any one of molybdenum oxide, vanadium oxide, tungsten oxide and nickel oxide.
  • the first film layer 110 prepared in this way can be a conductive polymer layer or an inorganic material layer.
  • the thickness of the finally prepared first film layer 110 may specifically range from 5 nm to 35 nm.
  • Step S130 Set a second film layer on the first film layer.
  • the second film layer 120 is disposed on the first film layer 110 , which may be a chemical solution of a conductive polymer, or a chemical solution mixed with a number of inorganic nanoparticles and a conductive polymer.
  • the solution is spin-coated, ink-jet printed or slit-coated on the first film layer 110 and dried to obtain a second film layer 120 in which a number of inorganic nanoparticles 121 are spacedly distributed.
  • the specific temperature of the above-mentioned drying process may be 130°C to 200°C, so that the second film layer 120 is completely dried.
  • the above-mentioned conductive polymer may specifically include a homopolymer formed from any one of aniline monomers, thiophene monomers and fluorene monomers or a copolymer formed from any combination.
  • the above-mentioned inorganic nanoparticles 121 may specifically include any one of silica particles, titanium dioxide particles, zinc sulfide particles, and zinc oxide particles.
  • the diameter of the above-mentioned inorganic nanoparticles 121 is 2nm-10nm.
  • the distribution spacing of the inorganic nanoparticles 121 in the second film layer 120 can be 2nm-15nm.
  • the thickness of the finally prepared second film layer 120 can be 5nm-15nm. .
  • the hole transport film 100 prepared in the embodiment of the present application adds these inorganic nanoparticles 121 in the second film layer 120 and controls the corresponding layout of these inorganic nanoparticles 121 in the second film layer 120. It is possible to further increase and improve the hole transport performance of the hole transport film 100 and the contact between the hole transport film 100 and the light-emitting layer (especially the quantum dot light-emitting layer of the QLED device) when used as a hole transport layer.
  • this embodiment provides an electroluminescent device 200.
  • the electroluminescent device 200 includes a stacked anode 210, a hole transport layer 220, a luminescent layer 230, and a cathode. 240, wherein the hole transport layer 220 can specifically be the hole transport film 100 in the above embodiment, the first film layer 110 is disposed adjacent to the anode 210, and the second film layer 120 is disposed adjacent to the light-emitting layer 230.
  • a side of the light-emitting layer 230 adjacent to the hole transport layer 220 is partially embedded in the second film layer 120 .
  • the first film layer 110 and the second film layer 120 are fabricated twice to jointly form the hole transport layer 220, only the manufacturing process of the second film layer 120 needs to be changed, so that the second film layer 120 is formed.
  • the layer 120 is in a semi-humid state (that is, based on the total mass of the second film layer 120, 5% to 10% of the organic solution remains in the second film layer 120), that is, on the second film layer 120 in the semi-humid state
  • a side of the prepared light-emitting layer 230 adjacent to the hole transport layer 220 is partially embedded in the second film layer 120.
  • FIG. 3 is only a simple illustration of the layout of each layer of the electroluminescent device, rather than the actual structure of the electroluminescent device.
  • the electroluminescent device may be a QLED device or an OLED device.
  • the above-mentioned anode 210 may be a metal oxide electrode or a composite electrode.
  • the metal oxide electrode is selected from one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO.
  • the composite electrode is AZO/ Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO2/Ag/TiO2, TiO 2 /Al/TiO 2 , ZnS/ Ag/ZnS or ZnS/Al/ZnS.
  • the luminescent layer 230 may specifically include quantum dots.
  • the quantum dots may be selected from one or more of single structure quantum dots and core-shell structure quantum dots.
  • the single structure quantum dots may be selected from One or more of Group II-VI compounds, Group III-V compounds and Group I-III-VI compounds, the Group II-VI compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS , one or more of CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe, the III-V compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, One or more of AlP, InAsP, InNP
  • the core of the quantum dots with a core-shell structure is selected from any one of the above-mentioned single-structure quantum dots, and the shell material of the quantum dots with a core-shell structure is selected from the group consisting of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, and ZnSeS. and one or more of ZnS.
  • the above-mentioned cathode 240 can specifically be selected from one or more types of Ag electrodes, Al electrodes, Au electrodes, Pt electrodes or alloy electrodes.
  • the side of the luminescent layer 20 adjacent to the hole transport layer 220 is partially embedded in the hole transport layer 220, so that the nanoparticles (especially the quantum dot luminescent layer) in the luminescent layer 230 Quantum dot nanoparticles) are partially embedded in the hole transport layer 220, thereby increasing the contact between the hole transport layer 220 and the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device), increasing hole injection, and reducing holes Charge accumulation at the contact interface between the transport layer 220 and the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device) improves device performance and service life.
  • the hole transport layer 220 of the electroluminescent device adopts the above-mentioned hole transport film 100, and can utilize the inorganic nanoparticles added in the second film layer 120 and control these inorganic nanoparticles.
  • the nanoparticles are arranged accordingly in the second film layer 120 to make close contact with the nanoparticles in the surface adjacent to the light-emitting layer 230, so that the side of the light-emitting layer 230 adjacent to the hole transport layer 220 is partially embedded in the second film layer 120, Furthermore, the contact between the hole transport layer 220 and the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device) is increased to increase hole injection, so as to reduce the number of holes between the hole transport layer 220 and the light-emitting layer 230 (especially the quantum dots of the QLED device). The charge accumulation at the contact interface between the light-emitting layers) further improves device performance and service life.
  • the electroluminescent device 200 may further be provided with a hole injection layer 250 between the anode 210 and the hole transport layer 220 ; and or, the electroluminescent device 200 may be provided with a hole injection layer 250 between the cathode and the cathode.
  • an electron transport layer 260 may be disposed between 240 and the light-emitting layer 230 to realize the basic light-emitting function of the electroluminescent device 200.
  • the material of the hole injection layer 250 can be one or more of TFB, PVK, poly-TPD, TCTA, and CBP.
  • the material of the electron transport layer 260 can be ZnO, ZnMgO, ZnMgLiO, ZnInO, ZrO, and ZrO 2 .
  • this embodiment provides a method for preparing an electroluminescent device.
  • the preparation method specifically includes the following steps:
  • Step S1 Provide an anode substrate
  • Step S2 Arrange a stacked first film layer and a second film layer on the anode substrate to obtain a hole transport layer;
  • Step S3 Set a light-emitting layer on the hole transport layer
  • Step S4 Set the cathode on the light-emitting layer.
  • this embodiment provides a method for preparing an electroluminescent device.
  • the preparation method specifically includes the following steps:
  • Step S210 Provide an anode substrate.
  • the preparation method of this embodiment is mainly used in the preparation process of the electroluminescent device in the above embodiment. Therefore, taking the electroluminescent device 200 in FIG. 4 as an example, each method step of this embodiment will be described accordingly.
  • an anode substrate is provided.
  • the anode substrate can be a substrate with an anode 210 evaporated or sputtered.
  • the anode can be ITO, IZO, AZO, Conductive transparent oxides such as IGZO
  • the anode when the prepared quantum dot electroluminescent device has a top-emission structure, can also be metals such as Ag, Au, Al, Mg, and metal alloys.
  • Step S220 Set the first film layer 110 and the second film layer 120 on the anode substrate to form the hole transport layer 220.
  • the hole transport layer 220 is provided on the anode substrate.
  • the specific arrangement method may be to provide the first film layer 110 on the anode 210 of the anode substrate, and to provide the third film layer 110 on the first film layer 110 .
  • the two film layers 120 are used to form the hole transport layer 220 through the first film layer 110 and the second film layer 120 .
  • the first film layer 110 is disposed on the anode 210 of the anode substrate.
  • a chemical solution containing a conductive polymer or inorganic material is spin-coated, ink-jet printed or slit-coated on the anode substrate. on the anode 210, and perform a drying process (which can be a vacuum drying process or a baking drying process) to obtain a conductive polymer layer or an inorganic material layer as the first film layer 110.
  • the specific temperature of the above-mentioned drying process may be 130°C to 200°C, so that the first film layer 110 is completely dried.
  • the above-mentioned conductive polymer may specifically include a homopolymer formed from any one of aniline monomers, thiophene monomers and fluorene monomers or a copolymer formed from any combination.
  • the above-mentioned inorganic material may specifically include any one of molybdenum oxide, vanadium oxide, tungsten oxide and nickel oxide.
  • the first film layer 110 prepared in this way can be a conductive polymer layer or an inorganic material layer.
  • the thickness of the finally prepared first film layer 110 may specifically range from 5 nm to 35 nm.
  • the second film layer 120 is disposed on the first film layer 110.
  • a chemical solution mixed with a number of inorganic nanoparticles and a conductive polymer is spin-coated, ink-jet printed or slit-coated on the first film layer. 110 and perform a drying process to obtain a conductive polymer layer with a number of inorganic nanoparticles spaced internally as the second film layer 120 .
  • the specific temperature of the above-mentioned drying process may be 130°C to 200°C, so that the second film layer 120 is completely dried.
  • the above-mentioned conductive polymer may specifically include a homopolymer formed from any one of aniline monomers, thiophene monomers and fluorene monomers or a copolymer formed from any combination.
  • the above-mentioned inorganic nanoparticles may specifically include any one of silica particles, titanium dioxide particles, zinc sulfide particles and zinc oxide particles.
  • the diameter of the above-mentioned inorganic nanoparticles is 2 nm to 10 nm.
  • the distribution spacing of the inorganic nanoparticles in the second film layer 120 can be 2 nm to 15 nm.
  • the thickness of the finally prepared second film layer 120 can be 5 nm to 15 nm.
  • Step S230 Provide a light-emitting layer on the second film layer of the hole transport layer.
  • the luminescent layer 230 is disposed on the hole transport layer 220 .
  • a chemical solution containing the luminescent layer material can be spin-coated, inkjet printed, or slit-coated on the hole transport layer.
  • a baking and drying process is performed to obtain the luminescent layer 230.
  • the contact between the hole transport layer 220 and the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device) can be increased, thereby increasing hole injection and reducing hole transmission.
  • Charge accumulation at the contact interface between layer 220 and the light-emitting layer 230 improves device performance and service life.
  • the above-mentioned light-emitting layer material may specifically include quantum dots.
  • the quantum dots may be selected from one or more of single-structure quantum dots and core-shell structure quantum dots.
  • the single-structure quantum dots may be selected from the group consisting of single-structure quantum dots and core-shell structure quantum dots.
  • Group II-VI compounds, Group III-V compounds and Group I-III-VI compounds is selected from the group consisting of CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, One or more of CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe
  • the III-V compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN , one or more of AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP
  • the Group I-III-VI compound is selected from one or more of CuInS 2 , CuInSe 2 and AgInS 2 .
  • the core of the quantum dots with a core-shell structure is selected from any one of the above-mentioned single-structure quantum dots, and the shell material of the quantum dots with the core-shell structure is selected from the group consisting of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, and ZnSeS. and one or more of ZnS.
  • the solvent of the above-mentioned chemical solution may specifically include any one of toluene, chlorobenzene, cyclohexylbenzene, or other compounds containing aromatic hydrocarbons, and the thickness of the finally prepared light-emitting layer 230 may specifically be 10 nm to 50 nm.
  • Step S240 Set a cathode on the light-emitting layer.
  • a cathode 240 is prepared on the light-emitting layer 230 .
  • the cathode 240 may be provided on the light-emitting layer 230 through an evaporation or sputtering process.
  • the cathode 240 may be a metal electrode such as Al, Ag, Mg, or the like.
  • the thickness of the cathode 240 may specifically range from 80 nm to 150 nm.
  • the thickness of the cathode 240 may specifically range from 5 nm to 40 nm.
  • the hole transport layer 220 of the electroluminescent device prepared can utilize a number of inorganic nanoparticles added to the second film layer 120 and control a number of The inorganic nanoparticles are arranged accordingly in the second film layer 120 to make close contact with the nanoparticles adjacent to the surface of the light-emitting layer 230 , so that the side of the light-emitting layer 230 adjacent to the hole transport layer 220 is partially embedded in the second film layer 120 , thereby increasing its contact with the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device) to increase hole injection, so as to reduce the contact with the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device).
  • Charge accumulation at the interface further improves device performance and service life.
  • this embodiment provides a method for preparing an electroluminescent device.
  • the preparation method specifically includes the following steps:
  • Step S310 Provide an anode substrate.
  • the preparation method of this embodiment is mainly used in the preparation process of the electroluminescent device in the above embodiment. Therefore, taking the electroluminescent device 200 in FIG. 5 as an example, each method step of this embodiment will be described accordingly.
  • an anode substrate is provided.
  • the anode substrate can be a substrate with an anode 210 evaporated or sputtered.
  • the anode can be ITO, IZO, AZO, Conductive transparent oxides such as IGZO
  • the anode when the prepared quantum dot electroluminescent device has a top-emission structure, can also be metals such as Ag, Au, Al, Mg, and metal alloys.
  • Step S320 A hole transport layer is provided on the anode substrate.
  • the hole transport layer is divided into a semi-moistened area, in which, based on the total mass of the semi-moistened area, 5% to 10% of the organic solution remains in the semi-moistened area. This semi-humid zone is formed.
  • a hole transport layer 220 is provided on the anode substrate.
  • the hole transport layer 220 is divided into semi-humid regions.
  • the specific arrangement method may be to first provide a first film layer on the anode 210 of the anode substrate. 110, and then dispose the second film layer 120 on the first film layer 110, so that the first film layer 110 and the second film layer 120 jointly form the hole transport layer 220 divided into semi-humid regions.
  • a first film layer 110 is provided on the anode 210 of the anode substrate.
  • the first film layer 110 can be prepared by a solution method, that is, spin coating, inkjet printing or slit printing of an organic solution containing a conductive polymer.
  • the film is coated on the substrate and subjected to drying treatment (which may be vacuum drying treatment or baking drying treatment) to obtain the first film layer 110 .
  • the above-mentioned conductive polymer may specifically include a homopolymer formed from any one of aniline monomers, thiophene monomers and fluorene monomers or a copolymer formed from any combination.
  • the thickness of the finally prepared first film layer 110 may specifically range from 10 nm to 50 nm.
  • the conductive polymer of the first film layer 110 is a cross-linkable polymer, that is, the conductive polymer contains cross-linked polymers. group.
  • the second film layer 120 is disposed on the first film layer 110.
  • the second film layer 120 can be prepared by a solution method, that is, spin coating, inkjet printing or slit printing of an organic solution containing a conductive polymer.
  • the formula is coated on the first film layer 110 and is dried (which can be a vacuum drying process or a baking drying process) to obtain the second film layer 120, and the total mass of the second film layer 120 is According to calculations, 5% to 10% of the organic solution remains in the second film layer 120, so that the second film layer 120 forms the semi-humid zone.
  • the above-mentioned conductive polymer may specifically include a homopolymer formed from any one of polyaniline, polythiophene and polyfluorene or a copolymer formed from any combination.
  • the thickness of the finally prepared second film layer 120 may specifically range from 1 nm to 10 nm.
  • the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device) on the second film layer 120, the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device) is better partially embedded in the second film layer 120.
  • the conductive polymer of the second film layer 120 is a non-crosslinked polymer, that is, the conductive polymer does not contain crosslinking groups.
  • the drying process can be a vacuum decompression drying process or a baking drying process.
  • the drying process can be a vacuum decompression drying process or a baking drying process.
  • the drying process steps of setting the first film layer 110 and setting the second film layer 120 can be adjusted as follows: When setting the first film layer 110 on the anode substrate , perform a first vacuum reduced pressure drying process on the first film layer 110, and when the second film layer 120 is disposed on the first film layer 110, perform a second vacuum reduced pressure drying process on the second film layer 120. At this time, it is necessary to ensure that the first pressure during the first vacuum reduced pressure drying process is less than the second pressure during the second vacuum reduced pressure drying process, and/or, the first duration of the first vacuum reduced pressure drying process is greater than the second vacuum reduced pressure drying process.
  • the second vacuum and reduced pressure drying process lasts for a second duration. That is, for those skilled in the art, either the pressure during the vacuum reduced pressure drying process can be simply controlled to be different, or the duration of the vacuum reduced pressure drying process can be simply controlled to be different, or both can be controlled simultaneously.
  • the pressure and duration of the vacuum drying process are different, so that when the first film layer 110 is completely dried, 5% to 10% of the total mass of the second film layer 120 remains in the second film layer 120 . % organic solution, so that the second film layer 120 is in a semi-wet state.
  • the above-mentioned first pressure may specifically be less than 10 Pa, and the above-mentioned second pressure may specifically be between 1000 Pa and 10000 Pa.
  • the above-mentioned first duration may specifically be greater than 5 min, and the above-mentioned second duration may specifically be less than 5 min.
  • performing the first vacuum depressurization drying process on the first film layer 110 can specifically maintain the first film layer 110 under a pressure of 10 Pa.
  • the vacuum drying process under reduced pressure is performed for 10 minutes, and the second vacuum reduced pressure drying process is performed on the second film layer 120.
  • the vacuum reduced pressure drying process is performed on the second film layer 120 under a pressure of 5000 Pa for 4 minutes, so that the first film layer When 110 is completely dry, about 8% of the organic solution remains in the second film layer 120 based on the total mass of the second film layer 120, making the second film layer 120 in a semi-humid state.
  • the drying process steps of setting the first film layer 110 and setting the second film layer 120 can be adjusted as follows: When setting the first film layer 110 on the anode substrate , perform a first baking and drying process on the first film layer 110, and when the second film layer 120 is disposed on the first film layer 110, perform a second baking and drying process on the second film layer 120. At this time, it is necessary to ensure that the first temperature during the first baking and drying process is higher than the second temperature during the second baking and drying process, and/or, the third duration of the first baking and drying process is longer than the second baking and drying process. The bake drying process lasts for a fourth duration.
  • the temperature of the two vacuum baking and drying processes can be simply controlled to be different, or the duration of the baking and drying processes of the two can be simply controlled to be different, or the two baking and drying processes can be controlled simultaneously.
  • the temperature and duration of the baking drying process are different, so that when the first film layer 110 is completely dried, 5% to 10% of the second film layer 120 remains in the second film layer 120 based on the total mass of the second film layer 120 .
  • the organic solution makes the second film layer 120 in a semi-humid state.
  • the above-mentioned first temperature may specifically range from 150°C to 300°C
  • the above-mentioned second temperature may specifically range from 50°C to 150°C.
  • the above-mentioned third duration time is specifically 15min-60min, and the above-mentioned fourth duration time is specifically 1min-15min.
  • the first baking and drying process for the first film layer 110 may be to maintain the first film layer 110 at a temperature of 250°C for 30 minutes.
  • the baking and drying process, the second baking and drying process for the second film layer 120 can specifically be a baking and drying process for the second film layer 120 at 100°C for 8 minutes, so that the first film layer 110 is completely dry. In this case, based on the total mass of the second film layer 120, about 6% of the organic solution remains in the second film layer 120, so that the second film layer 120 is in a semi-humid state.
  • Step S330 Set a luminescent layer on the second film layer in a semi-moist state.
  • the luminescent layer 230 is disposed on the hole transport layer 220 .
  • the luminescent layer 230 can be prepared by a solution method, that is, spin coating, inkjet printing or slit coating of a compound solution containing the luminescent layer material.
  • a solution method that is, spin coating, inkjet printing or slit coating of a compound solution containing the luminescent layer material.
  • Distributed on the second film layer 120 in a semi-moist state At this time, since the second film layer 120 is in a semi-moist state, the light-emitting layer 230 to be formed (especially the quantum dot light-emitting layer of the QLED device) is partially embedded in the second film layer 120. In the second film layer 120, a baking and drying process is then performed to obtain the luminescent layer 230.
  • the baking temperature of the baking and drying process is 100°C to 180°C.
  • the luminescent layer 230 and the second film layer 120 are evenly spaced.
  • the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device) is partially embedded into the second film layer 120 of the hole transport layer 220 to increase the contact between the hole transport layer 220 and the light-emitting layer 230 and increase the number of holes. Injection reduces charge accumulation at the contact interface between the hole transport layer 220 and the light-emitting layer 230, thereby improving device performance and service life.
  • the above-mentioned light-emitting layer material may specifically include quantum dots.
  • the quantum dots may be selected from one or more of single-structure quantum dots and core-shell structure quantum dots.
  • the single-structure quantum dots may be selected from the group consisting of single-structure quantum dots and core-shell structure quantum dots.
  • Group II-VI compounds, Group III-V compounds and Group I-III-VI compounds is selected from the group consisting of CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, One or more of CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe
  • the III-V compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN , one or more of AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP
  • the Group I-III-VI compound is selected from one or more of CuInS 2 , CuInSe 2 and AgInS 2 .
  • the core of the quantum dots with a core-shell structure is selected from any one of the above-mentioned single-structure quantum dots, and the shell material of the quantum dots with the core-shell structure is selected from the group consisting of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, and ZnSeS. and one or more of ZnS.
  • the solvent of the above compound solution may specifically include any one of toluene, chlorobenzene, cyclohexylbenzene, or other compounds containing aromatic hydrocarbons, and the thickness of the finally prepared light-emitting layer 230 may specifically be 10 nm to 50 nm.
  • Step S340 Set a cathode on the light-emitting layer.
  • the cathode 240 is prepared on the light-emitting layer 230 .
  • the cathode 240 may be provided on the light-emitting layer 230 through an evaporation or sputtering process.
  • the cathode 240 may be a metal electrode such as Al, Ag, or Mg.
  • the thickness of the cathode 240 may specifically range from 80 nm to 150 nm.
  • the thickness of the cathode 240 may specifically range from 5 nm to 40 nm.
  • the prepared electroluminescent device optimizes the preparation process of the second film layer 120 of the hole transport layer 220 so that the second film layer 120 is in In the semi-moist state, when the luminescent layer 230 of the electroluminescent device 200 (especially the quantum dot luminescent layer of the QLED device) is prepared, the nanoparticles in the luminescent layer 230 (especially the quantum dot nanoparticles of the quantum dot luminescent layer) Partially embedded in the second film layer 120 in a semi-wet state, thereby increasing the contact between the hole transport layer 220 and the light-emitting layer 230 (especially the quantum dot light-emitting layer of the QLED device), thereby increasing hole injection to reduce holes.
  • Charge accumulation at the contact interface between the transport layer 220 and the light-emitting layer 230 improves device performance and service life.
  • a hole injection layer 250 can also be provided between the anode substrate and the hole transport layer 220.
  • the specific process can be as follows: First, the hole injection layer 250 is provided on the anode substrate 210 (the specific installation process may be to spin-coat, inkjet print or slit-coat a solution containing the hole injection material on the anode 210 of the anode substrate, and bake it. Baking and drying treatment is performed to obtain the hole injection layer. The baking temperature of the baking and drying treatment is 180°C to 250°C. The thickness of the hole injection layer can be specifically 10nm to 60nm.
  • the hole injection materials include polythiophene and polyaniline. conductive polymer materials and their derivatives), and then set the hole transport layer 220 on the hole injection layer 250 through the above method steps.
  • the above two electroluminescent device preparation methods of this embodiment can also provide an electron transport layer 260 between the cathode 240 and the luminescent layer 230.
  • the electron transport layer 260 is provided on the luminescent layer 230.
  • the specific setting process of the transmission layer 260 may be to spin-coat, ink-jet print or slit-coat a solution containing the electron transmission material on the light-emitting layer 230, and then perform a baking and drying process to obtain the electron transmission layer 260.
  • the electron transport material is metal oxide ZnxMgyO, where x is 0.9 and y is 0.1.
  • the baking temperature of the above baking and drying process can be specifically 60°C to 150°C, and the thickness of the finally prepared electron transport layer 260 can be specifically (10 nm to 100 nm), and then set the cathode 240 on the electron transport layer 260 through the above method steps.
  • This embodiment provides an electroluminescent device and a preparation method thereof.
  • the electroluminescent device of this embodiment includes an anode 210, a hole injection layer 250, and a hole injection layer 250, which are stacked in sequence.
  • a hole injection layer 250 is provided on the anode 210 of the anode substrate.
  • the material of the hole injection layer 250 is polythiophene, and the thickness of the hole injection layer 250 is 40 nm;
  • the hole transport layer 220 is provided on the hole injection layer 250.
  • the first film layer 110 is first provided on the hole injection layer 250, and then the second film layer 120 is provided on the first film layer 110 to pass through the first film layer 110.
  • the first film layer 110 and the second film layer 120 together form the hole transport layer 220, wherein the first film layer 110 is a homopolymer of aniline monomer, the thickness of the first film layer 110 is 35 nm, and the second film layer 120 is Aniline monomer forms a homopolymer.
  • the thickness of the second film layer 120 is 5 nm, and a number of inorganic nanoparticles TiO 2 are distributed in the second film layer 120 at intervals.
  • the diameter of the inorganic nanoparticles TiO 2 is 2 nm.
  • the inorganic nanoparticles TiO 2 are in The distribution pitch in the second film layer 120 is 2 nm;
  • a light-emitting layer 230 is provided on the hole transport layer 220.
  • the light-emitting layer 230 is specifically the quantum dot light-emitting layer of the QLED device.
  • the quantum dot material used is CdZnSe and the thickness is 40nm;
  • An electron transport layer 260 is prepared on the light emitting layer 230.
  • the material of the electron transport layer 260 is metal oxide ZnxMgyO, where x is 0.9 and y is 0.1.
  • the thickness of the electron transport layer 260 is 80 nm.
  • a cathode 240 is provided on the electron transport layer 260.
  • the cathode 240 is an Al cathode, and the thickness of the cathode 240 is 120 nm.
  • the electroluminescent device of Embodiment 2 is different from the electroluminescent device of Embodiment 1 only in the arrangement of the hole transport layer 220 provided therein, specifically, in the second film layer 120 of Embodiment 1
  • the diameter of the inorganic nanoparticles TiO 2 is 2 nm
  • the distribution spacing of the inorganic nanoparticles TiO 2 in the second film layer 120 is 2 nm
  • the diameter of the inorganic nanoparticles TiO 2 in the second film layer 120 of Example 2 is 5 nm.
  • the spacing of the inorganic nanoparticles TiO 2 in the second film layer 120 is 10 nm.
  • the electroluminescent device of Embodiment 3 is different from the electroluminescent device of Embodiment 1 only in the arrangement of the hole transport layer 220 provided therein, specifically, in the second film layer 120 of Embodiment 1
  • the diameter of the inorganic nanoparticles TiO 2 is 2 nm
  • the distribution spacing of the inorganic nanoparticles TiO 2 in the second film layer 120 is 2 nm
  • the diameter of the inorganic nanoparticles TiO 2 in the second film layer 120 of Example 3 is 10 nm.
  • the spacing of the inorganic nanoparticles TiO 2 distributed in the second film layer 120 is 15 nm.
  • the electroluminescent device of Embodiment 4 is different from the electroluminescent device of Embodiment 1 only in the arrangement of the hole transport layer 220 provided therein, specifically, in the second film layer 120 of Embodiment 1
  • the diameter of the inorganic nanoparticles TiO 2 is 2 nm
  • the distribution spacing of the inorganic nanoparticles TiO 2 in the second film layer 120 is 2 nm
  • the diameter of the inorganic nanoparticles TiO 2 in the second film layer 120 of Example 4 is 1 nm.
  • the spacing of the inorganic nanoparticles TiO2 distributed in the second film layer 120 is 1 nm.
  • the electroluminescent device of Embodiment 5 is different from the electroluminescent device of Embodiment 1 only in the arrangement of the hole transport layer 220 provided therein. Specifically, the arrangement of the first film layer 110 of Embodiment 1 is different. The thickness is 35 nm, the thickness of the second film layer 120 is 5 nm, and the thickness of the first film layer 110 in Embodiment 5 is 30 nm, and the thickness of the second film layer 120 is 10 nm.
  • the electroluminescent device of Embodiment 6 is different from the electroluminescent device of Embodiment 1 only in the arrangement of the hole transport layer 220 provided therein. Specifically, the arrangement of the first film layer 110 of Embodiment 1 is different. The thickness is 35 nm, the thickness of the second film layer 120 is 5 nm, and the thickness of the first film layer 110 in Embodiment 6 is 5 nm, and the thickness of the second film layer 120 is 15 nm.
  • the electroluminescent device of Embodiment 7 is different from the electroluminescent device of Embodiment 1 only in the arrangement of the hole transport layer 220 provided therein. Specifically, the arrangement of the first film layer 110 of Embodiment 1 is different. The thickness is 35 nm, the thickness of the second film layer 120 is 5 nm, and the thickness of the first film layer 110 in Embodiment 7 is 40 nm, and the thickness of the second film layer 120 is 20 nm.
  • This embodiment provides an electroluminescent device and a preparation method thereof.
  • the electroluminescent device of this embodiment includes an anode 210, a hole injection layer 250, and a hole injection layer 250, which are stacked in sequence.
  • a hole injection layer 250 is provided on the anode 210 of the anode substrate.
  • the material of the hole injection layer 250 is polythiophene, and the thickness of the hole injection layer 250 is 40 nm;
  • the hole transport layer 220 is provided on the hole injection layer 250. Specifically, the first film layer 110 is first provided on the hole injection layer 250, and then the second film layer 120 is provided on the first film layer 110 to pass through the first film layer 110. The first film layer 110 and the second film layer 120 together form the hole transport layer 220, wherein the first film layer 110 is a cross-linkable copolymer formed by copolymerization of aniline monomer and aniline monomer containing double bonds, which contains double bonds.
  • the molar ratio of the bonded aniline monomer in the copolymer is 3%, the thickness of the first film layer 110 is 50 nm, the second film layer 120 is a non-crosslinked homopolymer formed of aniline monomer, and the second film layer 120 is a non-crosslinked homopolymer formed of aniline monomer.
  • the thickness of 120 is 1 nm, and 10% of the total mass of organic solution remains in the second film layer 120;
  • a light-emitting layer 230 is provided on the hole transport layer 220.
  • the light-emitting layer 230 is specifically the quantum dot light-emitting layer of the QLED device.
  • the quantum dot material used is CdZnSe and the thickness is 40nm;
  • An electron transport layer 260 is prepared on the light emitting layer 230.
  • the material of the electron transport layer 260 is metal oxide ZnxMgyO, where x is 0.9 and y is 0.1.
  • the thickness of the electron transport layer 260 is 80 nm.
  • a cathode 240 is provided on the electron transport layer 260.
  • the cathode 240 is an Al cathode, and the thickness of the cathode 240 is 120 nm.
  • the electroluminescent device of Embodiment 9 is different from the electroluminescent device of Embodiment 8 only in the arrangement of the hole transport layer 220 provided therein, specifically, in the second film layer 120 of Embodiment 8. 10% of the total mass of the organic solution remains, and 5% of the total mass of the organic solution remains in the second film layer 120 of Example 9.
  • the electroluminescent device of Embodiment 10 is different from the electroluminescent device of Embodiment 8 only in the arrangement of the hole transport layer 220.
  • the first film layer 110 of Embodiment 8 is: Aniline monomer and aniline monomer containing double bonds are copolymerized to form a crosslinkable copolymer, and the first film layer 110 of this embodiment 10 is a non-crosslinked homopolymer formed from aniline monomer.
  • the electroluminescent device of Embodiment 11 is different from the electroluminescent device of Embodiment 8 only in the arrangement of the hole transport layer 220.
  • the second film layer 120 of Embodiment 8 is A non-crosslinked homopolymer formed by aniline monomer
  • the second film layer 120 of this embodiment 11 is a cross-linkable copolymer formed by copolymerization of aniline monomer and aniline monomer containing double bonds, in which The molar ratio of aniline monomer in the copolymer was 3%.
  • the electroluminescent device of Embodiment 12 is different from the electroluminescent device of Embodiment 8 only in the arrangement of the hole transport layer 220 provided therein. Specifically, the arrangement of the first film layer 110 of Embodiment 8 is different. The thickness is 50 nm, the thickness of the second film layer 120 is 1 nm, and the thickness of the first film layer 110 in Embodiment 12 is 30 nm, and the thickness of the second film layer 120 is 5 nm.
  • the electroluminescent device of Embodiment 13 is different from the electroluminescent device of Embodiment 8 only in the arrangement of the hole transport layer 220 provided therein. Specifically, the arrangement of the first film layer 110 of Embodiment 8 is different. The thickness is 50 nm, the thickness of the second film layer 120 is 1 nm, and the thickness of the first film layer 110 in Embodiment 13 is 10 nm, and the thickness of the second film layer 120 is 10 nm.
  • the electroluminescent device of Embodiment 14 is different from the electroluminescent device of Embodiment 8 only in the arrangement of the hole transport layer 220 provided therein, specifically, the arrangement of the first film layer 110 of Embodiment 8.
  • the thickness is 50 nm
  • the thickness of the second film layer 120 is 1 nm
  • the thickness of the first film layer 110 in Embodiment 14 is 60 nm
  • the thickness of the second film layer 120 is 15 nm.
  • the electroluminescent device of Embodiment 15 is different from the electroluminescent device of Embodiment 8 only in the arrangement of the hole transport layer 220.
  • the first film layer 110 of Embodiment 8 is A crosslinkable copolymer is formed by copolymerization of aniline monomer and aniline monomer containing double bonds
  • the first film layer 110 of this embodiment 15 is a crosslinkable copolymer formed by copolymerization of aniline monomer and thiophene monomer containing double bonds.
  • a copolymer in which the molar ratio of thiophene monomer containing double bonds in the copolymer is 3%.
  • the electroluminescent device of Embodiment 16 is different from the electroluminescent device of Embodiment 8 only in the arrangement of the hole transport layer 220.
  • the second film layer 120 of Embodiment 8 is: A non-crosslinked homopolymer formed by aniline monomer
  • the first film layer 110 and the second film layer 120 of this embodiment 16 are a non-crosslinked copolymer formed by copolymerization of aniline monomer and fluorene monomer.
  • the electroluminescent device of Comparative Example 1 is different from the electroluminescent device of Embodiment 1 only in the hole transport layer 220 provided therewith.
  • the hole transport layer 220 is provided in the following manner: during hole injection
  • the hole transport layer 220 is provided on the layer 250 by inkjet printing.
  • the material of the hole transport layer 220 is only a homopolymer formed of polyaniline.
  • the thickness of the hole transport layer 220 is 40 nm, which is the hole transport layer in Comparative Example 1.
  • the hole transport layer adopts a conventional structure that is conventionally prepared.
  • the electroluminescent device of Comparative Example 2 is different from the electroluminescent device of Embodiment 8 only in the hole transport layer 220 provided therewith.
  • the hole transport layer is provided in the following manner: during hole injection
  • the hole transport layer 220 is provided on the layer 250 by inkjet printing.
  • the material of the hole transport layer 220 is only a homopolymer formed of polyaniline.
  • the thickness of the hole transport layer 220 is 40 nm, which is the hole transport layer in Comparative Example 1.
  • the hole transport layer adopts a conventional structure that is conventionally prepared.
  • Comparative Example 1 and Examples 1-7 shows that the electroluminescent device prepared by the preparation method of the embodiment of the present application has better current efficiency (i.e. device performance) and service life than traditional electroluminescent devices. greatly improved.
  • Embodiments 1-7 it can be explained that the diameter of the inorganic nanoparticles TiO2 in the second film layer 120, the distribution spacing of the inorganic nanoparticles TiO2 in the second film layer 120, and the relationship between the first film layer 110 and the second film layer 110 can be explained.
  • the thickness of the film layer 120 is within the value range given in the above claims, its current efficiency (ie, device performance) and service life are greatly improved.
  • the diameter of the inorganic nanoparticles TiO2 in the second film layer 120, the distribution spacing of the inorganic nanoparticles TiO2 in the second film layer 120, and the thickness of the first film layer 110 and the second film layer 120 are not given in the above summary. Within the value range, its current efficiency (i.e. device performance) and service life improvement effects are reduced to varying degrees.
  • Comparative Example 2 and Examples 8-16 shows that the electroluminescent device prepared by the preparation method of the embodiment of the present application has better current efficiency (i.e. device performance) and service life than traditional electroluminescent devices. greatly improved.
  • Examples 8-16 it can be explained that when the first film layer 110 of the hole transport layer 220 is a cross-linkable polymer and the second film layer 120 is a non-cross-linked polymer, the first film layer When the thicknesses of 110 and the second film layer 120 are both within the value range given by the above claims, and the value of the organic solution remaining in the second film layer 120 is also within the value range given by the above claims, its current efficiency (i.e. device performance) and service life have been greatly improved.
  • the first film layer 110 is made of a non-crosslinked polymer, or the second film layer is made of a cross-linkable polymer, or the thicknesses of the first film layer 110 and the second film layer 120 are not the values given in the above paragraphs, Within the range, its current efficiency (i.e. device performance) and service life improvement effects are reduced to varying degrees.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

本申请公开一种空穴传输薄膜、电致发光器件及其制备方法。本申请的空穴传输薄膜包括层叠设置的第一膜层与第二膜层，第一膜层为导电聚合物层或无机材料层，第二膜层为导电聚合物层。本申请空穴传输薄膜具有较高的空穴注入效率，从而提升器件性能和使用寿命。

Description

空穴传输薄膜、电致发光器件及其制备方法
本申请要求于2022年04月20日在中国专利局提交的、申请号为202210420916.7、申请名称为“一种电致发光器件及其制备方法”的中国专利申请和于2022年04月20日在中国专利局提交的、申请号为202210420931.1、申请名称为“一种空穴传输薄膜、电致发光器件及其制备方法”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
本申请涉及显示技术领域，尤其涉及一种空穴传输薄膜、电致发光器件及其制备方法。
背景技术
现有量子点电致发光(Quantum Dot Light Emitting Diodes，简称QLED)器件/有机电激光显示(Organic Light-Emitting Diode，简称OLED)器件均为有机无机复合器件，即空穴注入与传输是有机材料，电子注入与传输为无机材料，当正向偏压加到QLED器件/OLED器件的两端时，电子和空穴分别通过电子传输层和空穴传输层进入发光层；并在发光层复合发光。这样一来，由于无机纳米颗粒的电子迁移效率是远大于空穴的迁移效率，这会引起电荷在空穴传输层与发光层之间的接触界面处大量积累，从而影响器件性能和使用寿命。
技术解决方案
因此，本申请提供一种空穴传输薄膜、电致发光器件及其制备方法。
本申请实施例提供一种空穴传输薄膜，包括层叠设置的第一膜层与第二膜层，所述第一膜层为导电聚合物层或无机材料层，所述第二膜层为导电聚合物层。
可选的，所述导电聚合物层所采用的导电聚合物包括苯胺单体、噻吩单体以及芴类单体中的任意一种形成的均聚物或任意组合形成的共聚物；和/或， 所述无机材料层所采用的无机材料包括钼氧化物、钒氧化物、钨氧化物以及镍氧化物中的任意一种。
可选的，所述第二膜层的导电聚合物层内部间隔分布有若干无机纳米颗粒。
可选的，所述无机纳米颗粒包括二氧化硅颗粒、二氧化钛颗粒、硫化锌颗粒以及氧化锌颗粒中的任意一种。
可选的，所述第一膜层的所述导电聚合物为可交联的聚合物；和/或，所述第二膜层的所述导电聚合物为非交联的聚合物。
可选的，所述无机纳米颗粒的直径为2nm～10nm；和/或，所述无机纳米颗粒在所述第二膜层内的分布间距为2nm～15nm。
可选的，所述第一膜层110的厚度为5nm～50nm，和/或，所述第二膜层的厚度为1～15nm。
可选的，所述第一膜层为导电聚合物层或无机材料层，所述第二膜层为导电聚合物层，且所述第二膜层的导电聚合物层内部间隔分布有若干无机纳米颗粒，所述第一膜层的厚度为5nm～35nm；和/或，所述第二膜层的厚度为5nm～15nm；
所述第一膜层和所述第二膜层均为导电聚合物层，所述第一膜层的厚度为10nm～50nm，所述第二膜层的厚度为1nm～10nm。
相应的，本申请还提供一种电致发光器件，包括层叠设置的阳极、空穴传输层、发光层、阴极，其中，所述空穴传输层为上述空穴传输薄膜，所述发光层邻近所述空穴传输层的一侧部分嵌入所述第二膜层。
可选的，所述发光层邻近所述空穴传输层的第二膜层的一侧部分嵌入所述空穴传输层。
可选的，所述发光层包括量子点，所述量子点选自单一结构量子点及核壳结构量子点中的一种或多种，所述单一结构量子点选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种，所述II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe及CdZnSTe中的一种或多种，所述III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、 AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的一种或多种，所述I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的一种或多种；所述核壳结构的量子点的核选自上述单一结构量子点中的任意一种，所述核壳结构的量子点的壳层材料选自CdS、CdTe、CdSeTe、CdZnSe、CdZnS、CdSeS、ZnSe、ZnSeS和ZnS中的一种或多种。
可选的，所述电致发光器件在所述阳极和所述空穴传输层之间还设置有空穴注入层；和或，所述电致发光器件在所述阴极和所述发光层之间还设置有电子传输层。
相应的，本申请还提供一种电致发光器件的制备方法，包括以下步骤：
提供阳极基板；
在所述阳极基板上设置空穴传输层；
在所述空穴传输层上设置发光层；
在所述发光层设置阴极；
其中，所述设置空穴传输层包括：在所述阳极基板上设置第一膜层，及在所述第一膜层上设置第二膜层；
其中，所述第一膜层为导电聚合物层或无机材料层，所述第二膜层为导电聚合物层。
可选的，所述在阳极基板上设置第一膜层包括：将含有导电聚合物或无机材料的化学溶液设置在阳极基板的阳极上，并进行干燥处理，其中干燥处理的具体温度是130℃～200℃。
可选的，所述第一膜层上设置第二膜层包括，将导电高聚合物、或者包含无机纳米颗粒和导电高聚物的化学溶液设置在第一膜层上，并进行干燥处理，其中上述干燥处理的具体温度是130℃～200℃。
可选的，所述在所述阳极基板上设置空穴传输层的步骤具体包括：
在所述阳极基板上设置第一膜层；
在所述第一膜层上设置第二膜层，其中，以所述第二膜层的总质量计，所述第二膜层内残留有5％～10％的有机溶液，使得所述第二膜层形成所述半湿润区。
可选的，在所述阳极基板上设置第一膜层时，对所述第一膜层进行第一真 空减压干燥处理，在所述第一膜层上设置第二膜层时，对所述第二膜层进行第二真空减压干燥处理；所述第一真空减压干燥处理时的第一压强小于所述第二真空减压干燥处理时的第二压强，和/或，所述第一真空减压干燥处理持续的第一持续时间大于所述第二真空减压干燥处理持续的第二持续时间。
可选的，所述第一压强为小于10pa，和/或，所述第二压强为1000pa～10000pa，和/或，所述第一持续时间为大于5min，和/或，所述第二持续时间为小于5min。
可选的，在所述阳极基板上设置第一膜层时，对所述第一膜层进行第一烘烤干燥处理，在所述第一膜层上设置第二膜层时，对所述第二膜层进行第二烘烤干燥处理；所述第一烘烤干燥处理时的第一温度高于所述第二烘烤干燥处理时的第二温度，和/或，所述第一烘烤干燥处理持续的第三持续时间大于所述第二烘烤干燥处理持续的第四持续时间。
可选的，所述第一温度为150℃～300℃，和/或，所述第二温度为50℃～150℃，和/或，所述第三持续时间为15min～60min，和/或，所述第四持续时间为1min～15min。
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它的附图。
图1是本申请实施例提供的一种空穴传输薄膜的结构示意图。
图2是本申请实施例提供的另一种空穴传输薄膜的结构示意图。
图3是本申请实施例提供的空穴传输薄膜的制备方法的流程框图。
图4是本申请实施例提供的一种电致发光器件的结构示意图。
图5是本申请实施例提供的另一种电致发光器件的结构示意图。
图6是本申请实施例提供的又一种电致发光器件的结构示意图。
图7是本申请实施例提供的再一种电致发光器件的结构示意图。
图8是本申请实施例提供的一种电致发光器件的制备方法的流程框图。
图9是本申请实施例提供的另一种电致发光器件的制备方法的流程框图。
图10是本申请实施例提供的又一种电致发光器件的制备方法的流程框图。
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做出创造性劳动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。
需说明的是，以下实施例的描述顺序不作为对实施例优选顺序的限定。另外，在本申请的描述中，术语“包括”是指“包括但不限于”。
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。
本申请中“一种或多种”等表述，是指所列举多项中的一种或者多种，“多种”是指这些项中两种或两种以上的任意组合，包括单项(种)或复数项(种)的任意组合，例如，“a、b或c中的至少一项(种)”或“a、b和c中的至少一项(种)”，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。
本申请的各种实施例可以以一个范围的型式存在；应当理解，以一范围型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)。
现有QLED器件/OLED器件均为有机无机复合器件，即空穴注入与传输是有机材料，电子注入与传输为无机材料，当正向偏压加到QLED器件/OLED 器件的两端时，电子和空穴分别通过电子传输层和空穴传输层进入发光层；并在发光层复合发光。这样一来，由于无机纳米颗粒的电子迁移效率是远大于空穴的迁移效率，这会引起电荷在空穴传输层与发光层之间的接触界面处大量积累，从而影响器件性能和使用寿命。
基于此，有必要提供一种新的电致发光器件的结构解决方案，以改善现有的电致发光器件结构容易影响器件性能的技术问题。
在一个实施例中，如图1-2所示，本实施例提供一种空穴传输薄膜100，该空穴传输薄膜100包括层叠设置的第一膜层110与第二膜层120，且第一膜层110为导电聚合物层或无机材料层，第二膜层120为导电聚合物层。
需要说明的是，图1-2仅为空穴传输薄膜100的各层布局的简单示意，而非空穴传输薄膜100的实际结构。
上述导电聚合物层所采用的导电聚合物具体可包括苯胺单体、噻吩单体以及芴类单体中的任意一种形成的均聚物或任意组合形成的共聚物。可以理解，第一膜层110及第二膜层120两者所采用的导电聚合物可以相同，亦可以不同。
上述无机材料层所采用的无机材料具体可包括钼氧化物、钒氧化物、钨氧化物以及镍氧化物中的任意一种。
请参阅图2，在一些实施例中，第一膜层110和第二膜层120均为导电聚合物层。
请参阅图1，在另一些实施例中，第一膜层110为导电聚合物层或无机材料层，第二膜层120为导电聚合物层，且第二膜层120的导电聚合物层内部间隔分布有若干无机纳米颗粒121。
在一些示例中，上述第一膜层110的导电聚合物具体可为可交联的聚合物，即表明该导电聚合物内含有交联基团(交联基团就是未发生反应的官能团，即链状高分子通过其它功能团在一定条件下形成的网状聚合物，可降低高分子在溶剂的可溶性，能够在高温等条件下进一步发生化学反应，交联基团具体可以是双键、环丁烯、或环氧基团)。由于制备双层膜层的薄膜结构时会有界面互溶问题，而上述第一膜层110的导电聚合物为可交联的聚合物则可有效避免第二膜层120设置时对第一膜层110的表面造成破坏。
在一些示例中，上述第二膜层120的导电聚合物具体可为非交联的聚合物，即表明该导电聚合物内不含交联基团。第二膜层120采用这种结构有利于后续在第二膜层120上制备发光层(尤其是QLED器件的量子点发光层)时，发光层(尤其是QLED器件的量子点发光层)更好地部分嵌入到第二膜层120内，即提升其嵌入效果。同时，上述第一膜层110的导电聚合物具体为可交联的聚合物，上述第二膜层120的导电聚合物具体为非交联的聚合物的情形，亦可以有效控制发光层内粒子(尤其是QLED器件的量子点发光层的量子点粒子)嵌入的厚度，比如说空穴传输薄膜100总的厚度为25nm，第一膜层110的厚度是20nm，那么量子点最大的嵌入厚度就是5nm。
另外，同一导电聚合物实现交联或非交联的方法一般有两种，第一种方法是在聚合前采用含有交联基团的单体制备的是可交联的聚合物，采用不含有交联基团的单体制备的则是非交联的聚合物，以形成可交联的聚合物为例：可通过不含交联基团的导电结构单元(如苯胺单体、噻吩单元、或者芴单元等)与含有交联基团(如双键、环丁烯、或者环氧基团等)的导电结构单元(如苯胺单体、噻吩单元、或者芴单元等)或非导电结构单元(如苯乙烯基或亚甲基等)共聚形成上述的可交联的聚合物，其中含有交联基团的结构单元在相应聚合物中的占比可以为1～5％；第二种方法是导电聚合物制备完成后通过后续与侧链反应引入交联基团，使非交联的聚合物变成可交联的聚合物。
当第二膜层120的导电聚合物层内部间隔分布有若干无机纳米颗粒121时，本申请实施例通过在第二膜层120中增加无机纳米颗粒121并控制无机纳米颗粒121在第二膜层120中的分布，可有效提升本空穴传输薄膜100的空穴传输性能，同时，使得当将该空穴传输薄膜100用作电致发光器件的空穴传输层时，可将发光层(尤其是QLED器件的量子点发光层)设置在该第二膜层120上，此时，由于第二膜层120内间隔分布有若干无机纳米颗粒121，可与邻近发光层表面内的纳米颗粒进行紧密接触，使得发光层邻近空穴传输层的一侧部分嵌入第二膜层，进而增加空穴传输层与发光层(尤其是QLED器件的量子点发光层)的接触，来增加空穴注入，以减少空穴传输层与发光层(尤其是QLED器件的量子点发光层)之间的接触界面处的电荷积累，从而提升器件性能和使用寿命。
在一些示例中，当第一膜层110具体为导电聚合物层时，第二膜层120具体可以是采用与第一膜层110相同的导电聚合物形成的导电聚合物层，亦可以是采用与第一膜层110不同的导电聚合物形成的导电聚合物层。
在一些示例中，上述提到的无机纳米颗粒121具体可包括二氧化硅颗粒、二氧化钛颗粒、硫化锌颗粒以及氧化锌颗粒中的任意一种。无机纳米颗粒121的直径具体可为2nm～10nm，且无机纳米颗粒121在第二膜层120内的分布间距为2nm～15nm。这样一来，通过在第二膜层120中增加这些无机纳米颗粒121并控制这些无机纳米颗粒121在第二膜层120中进行相应的布局，能够进一步提升本空穴传输薄膜100的空穴传输性能以及增加本空穴传输薄膜100用作空穴传输层时与发光层(尤其是QLED器件的量子点发光层)的接触。
第一膜层110的厚度可以为5nm～50nm，第二膜层120的厚度可以为1～15nm。
在一些实施例中，当第一膜层110和第二膜层120均为导电聚合物层时，第一膜层110的厚度可为10nm～50nm，第二膜层120的厚度可为1nm～10nm，使得两者层叠形成的空穴传输薄膜100的总厚度具体可在11nm～60nm，以满足电致发光器件对空穴传输薄膜100的要求。
在另一些实施例中，当第一膜层110为导电聚合物层或无机材料层，第二膜层120为导电聚合物层，且第二膜层120的导电聚合物层内部间隔分布有若干无机纳米颗粒121时，第一膜层110的厚度具体可为5nm～35nm，第二膜层120的厚度具体可为5nm～15nm，使得两者层叠形成的空穴传输薄膜100的总厚度具体可在10nm～50nm，以满足相应电致发光器件对空穴传输层的要求。
在一个实施例中，如图3所示，本实施例提供一种空穴传输薄膜的制备方法，该制备方法包括以下步骤：
步骤S110：提供基板。
具体地，本实施例的制备方法主要应用于上述实施例中空穴传输薄膜100的制备过程中，因而，以图1的空穴传输薄膜100为例，对本实施例的各方法步骤进行相应说明。
需要说明的是，基板主要作为制备空穴传输薄膜100的载体，故图1所示制作完成的空穴传输薄膜100并未图示该基板。
步骤S120：在基板上设置第一膜层。
具体地，如图1所示，在基板上设置第一膜层110，具体可以是，将含有导电聚合物或无机材料的化学溶液旋涂、喷墨打印或狭缝式涂布在基板上，并进行干燥处理(可以是真空减压干燥处理或烘烤干燥处理)，以得到第一膜层110。上述干燥处理的具体温度可以是130℃～200℃，以使得第一膜层110完全干燥。同时，上述导电聚合物具体可包括苯胺单体、噻吩单体以及芴类单体中的任意一种形成的均聚物或任意组合形成的共聚物。上述无机材料具体可包括钼氧化物、钒氧化物、钨氧化物以及镍氧化物中的任意一种。通过这种方式制备出来的第一膜层110可以是导电聚合物层，亦可以是无机材料层。最终制备出来的第一膜层110的厚度具体可为5nm～35nm。
步骤S130：在第一膜层上设置第二膜层。
具体地，如图1所示，在第一膜层110上设置第二膜层120，具体可以是，将导电高聚合物的化学溶液、或者混合有若干无机纳米颗粒及导电高聚合物的化学溶液旋涂、喷墨打印或狭缝式涂布在第一膜层110上，并进行干燥处理，以得到第二膜层120，第二膜层内间隔分布有若干无机纳米颗粒121。上述干燥处理的具体温度可以是130℃～200℃，以使得第二膜层120完全干燥。同时，上述导电聚合物具体可包括苯胺单体、噻吩单体以及芴类单体中的任意一种形成的均聚物或任意组合形成的共聚物。上述无机纳米颗粒121具体可包括二氧化硅颗粒、二氧化钛颗粒、硫化锌颗粒以及氧化锌颗粒中的任意一种。上述无机纳米颗粒121的直径为2nm～10nm，无机纳米颗粒121在第二膜层120内的分布间距具体可为2nm～15nm，最终制备出来的第二膜层120的厚度具体可为5nm～15nm。
这样一来，本申请实施例制备出来的空穴传输薄膜100，通过在第二膜层120中增加这些无机纳米颗粒121并控制这些无机纳米颗粒121在第二膜层120中进行相应的布局，能够进一步增加提升本空穴传输薄膜100的空穴传输性能以及本空穴传输薄膜100用作空穴传输层时与发光层(尤其是QLED器件的量子点发光层)的接触。
在一个实施例中，如图4-5所示，本实施例提供一种电致发光器件200，该电致发光器件200包括层叠设置的阳极210、空穴传输层220、发光层230、阴极240，其中，空穴传输层220具体可为上述实施例中的空穴传输薄膜100，第一膜层110邻近阳极210设置，第二膜层120邻近发光层230设置。
请参阅图5，在一些实施例中，发光层230邻近空穴传输层220的一侧部分嵌入第二膜层120中。这样一来，在先后分两次制作第一膜层110与第二膜层120，来共同形成空穴传输层220时，只需改变第二膜层120的制作工艺，使得制作出来第二膜层120处于半湿润状态(即以第二膜层120的总质量计，第二膜层120内残留有5％～10％的有机溶液)，即可在半湿润状态的第二膜层120上制备发光层230时，使得制备出来的发光层230邻近空穴传输层220的一侧部分嵌入第二膜层120。
需要说明的是，图3仅为电致发光器件的各层布局的简单示意，而非电致发光器件的实际结构。该电致发光器件具体可以是QLED器件，亦可以是OLED器件。
上述阳极210具体可为金属氧化物电极或复合电极，该金属氧化物电极选自ITO、FTO、ATO、AZO、GZO、IZO、MZO及AMO中的一种或多种，该复合电极为AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO 2/Al/TiO 2、ZnS/Ag/ZnS或ZnS/Al/ZnS。
当该电致发光器件为QLED器件时，该发光层230具体可包括量子点，该量子点选自单一结构量子点及核壳结构量子点中的一种或多种，单一结构量子点选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种，该II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe及CdZnSTe中的一种或多种，该III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的一种或多种，该I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的一种或多种。该核壳结构的量子点的核选自上述单一结构量子点中的任意一种， 该核壳结构的量子点的壳层材料选自CdS、CdTe、CdSeTe、CdZnSe、CdZnS、CdSeS、ZnSe、ZnSeS和ZnS中的一种或多种。
上述阴极240具体可选自Ag电极、Al电极、Au电极、Pt电极或合金电极的一种或多种。
这样一来，本申请实施例的电致发光器件，其发光层20邻近空穴传输层220的一侧部分嵌入空穴传输层220，使得发光层230内的纳米颗粒(尤其是量子点发光层的量子点纳米颗粒)部分嵌入到空穴传输层220内，进而能够增加空穴传输层220与发光层230(尤其是QLED器件的量子点发光层)的接触，增加空穴注入，减少空穴传输层220与发光层230(尤其是QLED器件的量子点发光层)之间的接触界面处的电荷积累，从而提升器件性能和使用寿命。
请参阅图6，本申请实施例的电致发光器件，其空穴传输层220由于选用了上述的空穴传输薄膜100，可利用在第二膜层120中增加的无机纳米颗粒及控制这些无机纳米颗粒在第二膜层120中进行相应的布局，来与邻近发光层230表面内的纳米颗粒进行紧密接触，使得发光层230邻近空穴传输层220的一侧部分嵌入第二膜层120，进而增加空穴传输层220与发光层230(尤其是QLED器件的量子点发光层)的接触，来增加空穴注入，以减少空穴传输层220与发光层230(尤其是QLED器件的量子点发光层)之间的接触界面处的电荷积累，从而进一步提升器件性能和使用寿命。
在一些示例中，如图6-7所示，电致发光器件200在阳极210和空穴传输层220之间具体还可设置有空穴注入层250；和或，电致发光器件200在阴极240和发光层230之间具体还可设置有电子传输层260，以实现电致发光器件200的基本发光功能。
空穴注入层250的材料具体可为TFB、PVK、poly-TPD、TCTA、CBP中的一种或多种，电子传输层260的材料具体可为ZnO、ZnMgO、ZnMgLiO、ZnInO、ZrO、ZrO 2、TiO 2、TiO 2、SnO 2、Ta 2O 3、NiO、TiLiO、Alq 3、3-(联苯-4-基)-5-(4-叔丁基苯基)-4-苯基-4H-1,2,4-三唑、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯、2-(4'-叔丁苯基)-5-(4'-联苯基)-1,3,4-恶二唑、2,9-二甲基-4,7-二苯基-1,10-菲咯啉、4,7-二苯基-1,10-菲咯啉中的一种或多种。
在一个实施例中，如图8所示，本实施例提供一种电致发光器件的制备方法，该制备方法具体包括以下步骤：
步骤S1：提供阳极基板；
步骤S2：在阳极基板上设置层叠的第一膜层和第二膜层，得到空穴传输层；
步骤S3：在所述空穴传输层上设置发光层；
步骤S4：在发光层上设置阴极。
在一个实施例中，如图9所示，本实施例提供一种电致发光器件的制备方法，该制备方法具体包括以下步骤：
步骤S210：提供阳极基板。
具体地，本实施例的制备方法主要应用于上述实施例中电致发光器件的制备过程中，因而，以图4的电致发光器件200为例，对本实施例的各方法步骤进行相应说明。
如图4所示，提供阳极基板，该阳极基板具体可以是蒸镀或溅射有阳极210的基板，当制备的电致发光器件为底发射结构时，该阳极可以是ITO、IZO、AZO、IGZO等导电透明氧化物，当制备的量子点电致发光器件为顶发射结构时，该阳极也可以是Ag、Au、Al、Mg等金属以及金属合金。
步骤S220：在阳极基板上设置第一膜层110和第二膜层120，形成空穴传输层220。
具体地，如图4所示，在阳极基板上设置空穴传输层220，其具体设置方式可以是在阳极基板的阳极210上设置第一膜层110，及在第一膜层110上设置第二膜层120，以通过第一膜层110与第二膜层120共同形成空穴传输层220。
如图3所示，在阳极基板的阳极210上设置第一膜层110，具体可以是，将含有导电聚合物或无机材料的化学溶液旋涂、喷墨打印或狭缝式涂布在阳极基板的阳极210上，并进行干燥处理(可以是真空减压干燥处理或烘烤干燥处理)，以得到导电聚合物层或无机材料层来作为第一膜层110。上述干燥处理的具体温度可以是130℃～200℃，以使得第一膜层110完全干燥。同时，上述导电聚合物具体可包括苯胺单体、噻吩单体以及芴类单体中的任意一种形成的 均聚物或任意组合形成的共聚物。上述无机材料具体可包括钼氧化物、钒氧化物、钨氧化物以及镍氧化物中的任意一种。通过这种方式制备出来的第一膜层110可以是导电聚合物层，亦可以是无机材料层。最终制备出来的第一膜层110的厚度具体可为5nm～35nm。
在第一膜层110上设置第二膜层120，具体可以是，将混合有若干无机纳米颗粒及导电高聚合物的化学溶液旋涂、喷墨打印或狭缝式涂布在第一膜层110上，并进行干燥处理，以得到内部间隔分布有若干无机纳米颗粒的导电聚合物层来作为第二膜层120。上述干燥处理的具体温度可以是130℃～200℃，以使得第二膜层120完全干燥。同时，上述导电聚合物具体可包括苯胺单体、噻吩单体以及芴类单体中的任意一种形成的均聚物或任意组合形成的共聚物。上述无机纳米颗粒具体可包括二氧化硅颗粒、二氧化钛颗粒、硫化锌颗粒以及氧化锌颗粒中的任意一种。上述无机纳米颗粒的直径为2nm～10nm，无机纳米颗粒在第二膜层120内的分布间距具体可为2nm～15nm，最终制备出来的第二膜层120的厚度具体可为5nm～15nm。
步骤S230：在空穴传输层的第二膜层上设置发光层。
具体地，如图4所示，在空穴传输层220上设置发光层230，具体可以是将含有发光层材料的化学物溶液旋涂、喷墨打印或狭缝式涂布在空穴传输层220的第二膜层120上，进行烘烤干燥处理，来得到发光层230。当第二膜层120内间隔分布有若干无机纳米颗粒时，可增加空穴传输层220与发光层230(尤其是QLED器件的量子点发光层)的接触，增加空穴注入，减少空穴传输层220与发光层230(尤其是QLED器件的量子点发光层)之间的接触界面处的电荷积累，从而提升器件性能和使用寿命。
另外，上述电致发光器件为QLED器件时，上述发光层材料具体可包括量子点，该量子点选自单一结构量子点及核壳结构量子点中的一种或多种，单一结构量子点选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种，该II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe及CdZnSTe中的一种或多种，该III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP 中的一种或多种，该I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的一种或多种。该核壳结构的量子点的核选自上述单一结构量子点中的任意一种，该核壳结构的量子点的壳层材料选自CdS、CdTe、CdSeTe、CdZnSe、CdZnS、CdSeS、ZnSe、ZnSeS和ZnS中的一种或多种。上述化学物溶液的溶剂具体可包括甲苯、氯苯以及环己基苯中的任意一种，或者其它含有芳香烃的化合物，最终制备出来的发光层230的厚度具体可为10nm～50nm。
步骤S240：在发光层设置阴极。
具体地，如图4所示，在发光层230上制备阴极240，具体可以是通过蒸镀或溅射工艺在发光层230上设置阴极240，阴极240可以是Al、Ag、Mg等金属电极。当制备的电致发光器件为底发射结构时，该阴极240的厚度具体可为80nm～150nm，当制备的电致发光器件为顶发射结构时，该阴极240的厚度具体可为5nm～40nm。
这样一来，本申请实施例的电致发光器件的制备方法，其制备出来的电致发光器件，其空穴传输层220可利用在第二膜层120中增加的若干无机纳米颗粒及控制若干无机纳米颗粒在第二膜层120中进行相应的布局，来与邻近发光层230表面内的纳米颗粒进行紧密接触，使得发光层230邻近空穴传输层220的一侧部分嵌入第二膜层120，进而增加其与发光层230(尤其是QLED器件的量子点发光层)的接触，来增加空穴注入，以减少其与发光层230(尤其是QLED器件的量子点发光层)之间的接触界面处的电荷积累，从而进一步提升器件性能和使用寿命。
在另一个实施例中，如图10所示，本实施例提供一种电致发光器件的制备方法，该制备方法具体包括以下步骤：
步骤S310：提供阳极基板。
具体地，本实施例的制备方法主要应用于上述实施例中电致发光器件的制备过程中，因而，以图5的电致发光器件200为例，对本实施例的各方法步骤进行相应说明。
如图1所示，提供阳极基板，该阳极基板具体可以是蒸镀或溅射有阳极210的基板，当制备的电致发光器件为底发射结构时，该阳极可以是ITO、IZO、 AZO、IGZO等导电透明氧化物，当制备的量子点电致发光器件为顶发射结构时，该阳极也可以是Ag、Au、Al、Mg等金属以及金属合金。
步骤S320：在阳极基板上设置空穴传输层，空穴传输层划分有半湿润区，其中，以半湿润区的总质量计，半湿润区内残留有5％～10％的有机溶液，以形成该半湿润区。
具体地，如图5所示，在阳极基板上设置空穴传输层220，空穴传输层220划分有半湿润区，其具体设置方式可以是先在阳极基板的阳极210上设置第一膜层110，再在第一膜层110上设置第二膜层120，以通过第一膜层110与第二膜层120共同形成该划分有半湿润区的空穴传输层220。
如图5所示，在阳极基板的阳极210上设置第一膜层110，具体可以是，溶液法制备第一膜层110，即将含有导电聚合物的有机溶液旋涂、喷墨打印或狭缝式涂布在基板上，并进行干燥处理(可以是真空减压干燥处理或烘烤干燥处理)，以得到第一膜层110。上述导电聚合物具体可包括苯胺单体、噻吩单体以及芴类单体中的任意一种形成的均聚物或任意组合形成的共聚物。最终制备出来的第一膜层110的厚度具体可为10nm～50nm。同时，为有效避免第二膜层120设置时对第一膜层110的表面造成破坏，上述第一膜层110的导电聚合物为可交联的聚合物，即其导电聚合物内含有交联基团。
如图5所示，在第一膜层110上设置第二膜层120，具体可以是，溶液法制备第二膜层120，即将含有导电聚合物的有机溶液旋涂、喷墨打印或狭缝式涂布在第一膜层110上，并进行干燥处理(可以是真空减压干燥处理或烘烤干燥处理)，以得到第二膜层120，且其中，以第二膜层120的总质量计，第二膜层120内残留有5％～10％的有机溶液，使得第二膜层120形成该半湿润区。上述导电聚合物具体可包括聚苯胺、聚噻吩以及聚芴中的任意一种形成的均聚物或任意组合形成的共聚物。最终制备出来的第二膜层120的厚度具体可为1nm～10nm。同时，为利于后续在第二膜层120上制备发光层230(尤其是QLED器件的量子点发光层)时，发光层230(尤其是QLED器件的量子点发光层)更好地部分嵌入到第二膜层120内，即提升其嵌入效果，上述第二膜层120的导电聚合物为非交联的聚合物，即其导电聚合物内不含交联基团。
基于上述可知，在设置第一膜层110及设置第二膜层120时，均需进行干燥处理，该干燥处理可以是真空减压干燥处理或烘烤干燥处理，此时，为使得第一膜层110完全干燥的情形下，以第二膜层120的总质量计，第二膜层120内残留有5％～10％的有机溶液，使得第二膜层120处于半湿润状态。
一方面以上述干燥处理均为真空减压干燥处理为例，可对设置第一膜层110及设置第二膜层120的干燥处理步骤作出如下调整：在阳极基板上设置第一膜层110时，对第一膜层110进行第一真空减压干燥处理，在第一膜层110上设置第二膜层120时，对第二膜层120进行第二真空减压干燥处理。此时，需确保第一真空减压干燥处理时的第一压强小于第二真空减压干燥处理时的第二压强，和/或，第一真空减压干燥处理持续的第一持续时间大于第二真空减压干燥处理持续的第二持续时间。即对于本领域技术人员而言，或者可通过单纯控制两者真空减压干燥处理时的压强不同，或者可通过单纯控制两者真空减压干燥处理的持续时间不同，或者可通过同时控制两者真空减压干燥处理时的压强及持续时间均不同，来使得第一膜层110完全干燥的情形下，以第二膜层120的总质量计，第二膜层120内残留有5％～10％的有机溶液，使得第二膜层120处于半湿润状态。上述第一压强具体可为小于10pa，上述第二压强具体为1000pa～10000pa。上述第一持续时间具体可为大于5min，上述第二持续时间具体为小于5min。以同时控制两者真空减压干燥处理时的压强及持续时间均不同为例，对第一膜层110进行第一真空减压干燥处理具体可为在10pa压强下对第一膜层110进行维持10min的真空减压干燥处理，对第二膜层120进行第二真空减压干燥处理具体可为在5000pa压强下对第二膜层120进行维持4min的真空减压干燥处理，使得第一膜层110完全干燥的情形下，以第二膜层120的总质量计，第二膜层120内残留有约8％的有机溶液，使得第二膜层120处于半湿润状态。
另一方面以上述干燥处理均为烘烤干燥处理为例，可对设置第一膜层110及设置第二膜层120的干燥处理步骤作出如下调整：在阳极基板上设置第一膜层110时，对第一膜层110进行第一烘烤干燥处理，在第一膜层110上设置第二膜层120时，对第二膜层120进行第二烘烤干燥处理。此时，需确保第一烘烤干燥处理时的第一温度高于第二烘烤干燥处理时的第二温度，和/或，第一 烘烤干燥处理持续的第三持续时间大于第二烘烤干燥处理持续的第四持续时间。即对于本领域技术人员而言，或者可通过单纯控制两者真空烘烤干燥处理时的温度不同，或者可通过单纯控制两者烘烤干燥处理的持续时间不同，或者可通过同时控制两者烘烤干燥处理时的温度及持续时间均不同，来使得第一膜层110完全干燥的情形下，以第二膜层120的总质量计，第二膜层120内残留有5％～10％的有机溶液，使得第二膜层120处于半湿润状态。上述第一温度具体可为150℃～300℃，上述第二温度具体为50℃～150℃。上述第三持续时间具体为15min～60min，上述第四持续时间具体为1min～15min。以同时控制两者烘烤干燥处理时的温度及持续时间均不同为例，对第一膜层110进行第一烘烤干燥处理具体可为在250℃温度下对第一膜层110进行维持30min的烘烤干燥处理，对第二膜层120进行第二烘烤干燥处理具体可为在100℃下对第二膜层120进行维持8min的烘烤干燥处理，使得第一膜层110完全干燥的情形下，以第二膜层120的总质量计，第二膜层120内残留有约6％的有机溶液，使得第二膜层120处于半湿润状态。
步骤S330：在半湿润状态的第二膜层上设置发光层。
具体地，如图5所示，在空穴传输层220上设置发光层230，具体可以是溶液法制备发光层230，即将含有发光层材料的化合物溶液旋涂、喷墨打印或狭缝式涂布在半湿润状态的第二膜层120上，此时，由于第二膜层120处于半湿润状态，会使得将要形成的发光层230(尤其是QLED器件的量子点发光层)部分嵌入到第二膜层120内，接着，进行烘烤干燥处理，来得到发光层230后，该烘烤干燥处理的烘烤温度为100℃～180℃，此时，发光层230与第二膜层120均完全干燥，发光层230(尤其是QLED器件的量子点发光层)部分嵌入到空穴传输层220的第二膜层120内，以增加空穴传输层220与发光层230的接触，增加空穴注入，减少空穴传输层220与发光层230之间的接触界面处的电荷积累，从而提升器件性能和使用寿命。
另外，上述电致发光器件为QLED器件时，上述发光层材料具体可包括量子点，该量子点选自单一结构量子点及核壳结构量子点中的一种或多种，单一结构量子点选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种，该II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、 CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe及CdZnSTe中的一种或多种，该III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的一种或多种，该I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的一种或多种。该核壳结构的量子点的核选自上述单一结构量子点中的任意一种，该核壳结构的量子点的壳层材料选自CdS、CdTe、CdSeTe、CdZnSe、CdZnS、CdSeS、ZnSe、ZnSeS和ZnS中的一种或多种。上述化合物溶液的溶剂具体可包括甲苯、氯苯以及环己基苯中的任意一种，或者其它含有芳香烃的化合物，最终制备出来的发光层230的厚度具体可为10nm～50nm。
步骤S340：在发光层设置阴极。
具体地，如图5所示，在发光层230上制备阴极240，具体可以是通过蒸镀或溅射工艺在发光层230上设置阴极240，阴极240可以是Al、Ag、Mg等金属电极。当制备的电致发光器件为底发射结构时，该阴极240的厚度具体可为80nm～150nm，当制备的电致发光器件为顶发射结构时，该阴极240的厚度具体可为5nm～40nm。
这样一来，本申请实施例的电致发光器件的制备方法，其制备出来的电致发光器件，通过优化空穴传输层220的第二膜层120的制备工艺，使得第二膜层120处于半湿润状态，可在电致发光器件200的发光层230(尤其是QLED器件的量子点发光层)制备时，使得发光层230内的纳米颗粒(尤其是量子点发光层的量子点纳米颗粒)部分嵌入到半湿润状态的第二膜层120内，进而能够增加空穴传输层220与发光层230(尤其是QLED器件的量子点发光层)的接触，来增加空穴注入，以减少空穴传输层220与发光层230(尤其是QLED器件的量子点发光层)之间的接触界面处的电荷积累，从而提升器件性能和使用寿命。
另外，请参阅图6-7，本实施例的上述两种电致发光器件的制备方法，还可在阳极基板和空穴传输层220之间设置空穴注入层250，其具体过程可以是，先在阳极基板210上设置空穴注入层250(具体设置过程可以是，将含有空穴注入材料的溶液旋涂、喷墨打印或狭缝式涂布在阳极基板的阳极210上，并进行烘烤干燥处理，以得到空穴注入层，烘烤干燥处理的烘烤温度为180℃～ 250℃，空穴注入层的厚度具体可为10nm～60nm。上述空穴注入材料包括聚噻吩、聚苯胺等导电高分子材料及其衍生物)，再通过上述方法步骤的方式在空穴注入层250上设置空穴传输层220。
还有，请参阅图6-7，本实施例的上述两种电致发光器件的制备方法，亦可在阴极240和发光层230之间设置电子传输层260，先在发光层230上设置电子传输层260(具体设置过程可以是，将含有电子传输材料的溶液旋涂、喷墨打印或狭缝式涂布在发光层230上，并进行烘烤干燥处理，以得到电子传输层260。其中，该电子传输材料为金属氧化物ZnxMgyO，其中x是0.9，y是0.1。上述烘烤干燥处理的烘烤温度具体可为60℃～150℃，最终制备出来的电子传输层260的厚度具体可为10nm～100nm)，再通过上述方法步骤的方式在电子传输层260上设置阴极240。
下面通过具体实施例、对比例和实验例对本申请的技术方案及技术效果进行详细说明，以下实施例仅仅是本申请的部分实施例，并非对本申请作出具体限定。
实施例1
本实施例提供了一种电致发光器件及其制备方法，电致发光器件结构组成参阅图4，本实施例的电致发光器件包括依次层叠设置的阳极210、空穴注入层250、空穴传输层220、发光层230、电子传输层260以及阴极240。
本实施例中电致发光器件的制备方法包括如下步骤：
在阳极基板的阳极210上设置空穴注入层250，该空穴注入层250的材料为聚噻吩，空穴注入层250的厚度为40nm；
在空穴注入层250上设置空穴传输层220，具体为，在空穴注入层250上先设置第一膜层110，再在第一膜层110上设置第二膜层120，以通过第一膜层110与第二膜层120共同形成空穴传输层220，其中，第一膜层110为苯胺单体形成均聚物，第一膜层110的厚度为35nm，第二膜层120为苯胺单体形成均聚物，第二膜层120的厚度为5nm，且第二膜层120间隔分布有若干无机纳米颗粒TiO 2，无机纳米颗粒TiO 2的直径为2nm，无机纳米颗粒TiO 2在第二膜层120中的分布的间距是2nm；
在空穴传输层220上设置发光层230，发光层230具体为QLED器件的量子点发光层，其采用的量子点材料为CdZnSe，厚度为40nm；
在发光层230上制备电子传输层260，该电子传输层260材料为金属氧化物ZnxMgyO，其中x是0.9，y是0.1，该电子传输层260的厚度为80nm。
在该电子传输层260上设置阴极240，该阴极240为Al阴极，该阴极240的厚度为120nm。
经实验测得，本实施例的电致发光器件在1000nits下电流效率是45cd/A，衰减5％的寿命是10000h。
实施例2
本实施例2的电致发光器件与实施例1的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例1的第二膜层120内无机纳米颗粒TiO 2的直径为2nm，无机纳米颗粒TiO 2在第二膜层120中的分布的间距是2nm，而本实施例2的第二膜层120内无机纳米颗粒TiO 2的直径为5nm，无机纳米颗粒TiO 2在第二膜层120中的分布的间距是10nm。
经实验测得，本实施例2的电致发光器件在1000nits下电流效率是46cd/A，衰减5％的寿命是1100h。
实施例3
本实施例3的电致发光器件与实施例1的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例1的第二膜层120内无机纳米颗粒TiO 2的直径为2nm，无机纳米颗粒TiO 2在第二膜层120中的分布的间距是2nm，而本实施例3的第二膜层120内无机纳米颗粒TiO 2的直径为10nm，无机纳米颗粒TiO 2在第二膜层120中的分布的间距是15nm。
经实验测得，本实施例2的电致发光器件在1000nits下电流效率是47cd/A，衰减5％的寿命是1200h。
实施例4
本实施例4的电致发光器件与实施例1的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例1的第二膜层120内无机纳米颗粒TiO 2的直径为2nm，无机纳米颗粒TiO 2在第二膜层120中的 分布的间距是2nm，而本实施例4的第二膜层120内无机纳米颗粒TiO 2的直径为1nm，无机纳米颗粒TiO2在第二膜层120中的分布的间距是1nm。
经实验测得，本实施例4的电致发光器件在1000nits下电流效率是39cd/A，衰减5％的寿命是7000h。
实施例5
本实施例5的电致发光器件与实施例1的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例1的第一膜层110的厚度为35nm，第二膜层120的厚度为5nm，而本实施例5的第一膜层110的厚度为30nm，第二膜层120的厚度为10nm。
经实验测得，本实施例5的电致发光器件在1000nits下电流效率是45cd/A，衰减5％的寿命是10000h。
实施例6
本实施例6的电致发光器件与实施例1的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例1的第一膜层110的厚度为35nm，第二膜层120的厚度为5nm，而本实施例6的第一膜层110的厚度为5nm，第二膜层120的厚度为15nm。
经实验测得，本实施例6的电致发光器件在1000nits下电流效率是44cd/A，衰减5％的寿命是9000h。
实施例7
本实施例7的电致发光器件与实施例1的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例1的第一膜层110的厚度为35nm，第二膜层120的厚度为5nm，而本实施例7的第一膜层110的厚度为40nm，第二膜层120的厚度为20nm。
经实验测得，本实施例7的电致发光器件在1000nits下电流效率是38cd/A，衰减5％的寿命是7000h。
实施例8
本实施例提供了一种电致发光器件及其制备方法，电致发光器件结构组成参阅图2，本实施例的电致发光器件包括依次层叠设置的阳极210、空穴注入层250、空穴传输层220、发光层230、电子传输层260以及阴极240。
本实施例中电致发光器件的制备方法包括如下步骤：
在阳极基板的阳极210上设置空穴注入层250，该空穴注入层250的材料为聚噻吩，空穴注入层250的厚度为40nm；
在空穴注入层250上设置空穴传输层220，具体为，在空穴注入层250上先设置第一膜层110，再在第一膜层110上设置第二膜层120，以通过第一膜层110与第二膜层120共同形成空穴传输层220，其中，第一膜层110为苯胺单体与含有双键的苯胺单体共聚形成的可交联的共聚物，其中含有双键的苯胺单体在该共聚物中的摩尔比为3％，第一膜层110的厚度为50nm，第二膜层120为苯胺单体形成的非交联的均聚物，第二膜层120的厚度为1nm，且第二膜层120内残留有占总质量10％的有机溶液；
在空穴传输层220上设置发光层230，发光层230具体为QLED器件的量子点发光层，其采用的量子点材料为CdZnSe，厚度为40nm；
在发光层230上制备电子传输层260，该电子传输层260材料为金属氧化物ZnxMgyO，其中x是0.9，y是0.1，该电子传输层260的厚度为80nm。
在该电子传输层260上设置阴极240，该阴极240为Al阴极，该阴极240的厚度为120nm。
经实验测得，本实施例1的电致发光器件在1000nits下电流效率是44cd/A，衰减5％的寿命是9000h。
实施例9
本实施例9的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例8的第二膜层120内残留有占总质量10％的有机溶液，而本实施例9的第二膜层120内残留有占总质量5％的有机溶液。
经实验测得，本实施例9的电致发光器件在1000nits下电流效率是42cd/A，衰减5％的寿命是8500h。
实施例10
本实施例10的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例8的第一膜层110 为苯胺单体与含有双键的苯胺单体共聚形成的可交联的共聚物，而本实施例10的第一膜层110为苯胺单体形成的非交联的均聚物。
经实验测得，本实施例10的电致发光器件在1000nits下电流效率是36cd/A，衰减5％的寿命是6200h。
实施例11
本实施例11的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例8的第二膜层120为苯胺单体形成的非交联的均聚物，而本实施例11的第二膜层120为苯胺单体与含有双键的苯胺单体共聚形成可交联的共聚物，其中含有双键的苯胺单体在该共聚物中的摩尔比为3％。
经实验测得，本实施例11的电致发光器件在1000nits下电流效率是36cd/A，衰减5％的寿命是6500h。
实施例12
本实施例12的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例8的第一膜层110的厚度为50nm，第二膜层120的厚度为1nm，而本实施例12的第一膜层110的厚度为30nm，第二膜层120的厚度为5nm。
经实验测得，本实施例12的电致发光器件在1000nits下电流效率是42cd/A，衰减5％的寿命是8500h。
实施例13
本实施例13的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例8的第一膜层110的厚度为50nm，第二膜层120的厚度为1nm，而本实施例13的第一膜层110的厚度为10nm，第二膜层120的厚度为10nm。
经实验测得，本实施例13的电致发光器件在1000nits下电流效率是41cd/A，衰减5％的寿命是8000h。
实施例14
本实施例14的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例8的第一膜层110 的厚度为50nm，第二膜层120的厚度为1nm，而本实施例14的第一膜层110的厚度为60nm，第二膜层120的厚度为15nm。
经实验测得，本实施例14的电致发光器件在1000nits下电流效率是36cd/A，衰减5％的寿命是6500h。
实施例15
本实施例15的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例8的第一膜层110为苯胺单体与含有双键的苯胺单体共聚形成的可交联的共聚物，而本实施例15的第一膜层110为苯胺单体与含有双键的噻吩单体共聚形成的可交联的共聚物，其中含有双键的噻吩单体在该共聚物中的摩尔比为3％。
经实验测得，本实施例15的电致发光器件在1000nits下电流效率是44cd/A，衰减5％的寿命是8900h。
实施例16
本实施例16的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的膜层设置不同，具体为，实施例8的第二膜层120为苯胺单体形成的非交联的均聚物，而本实施例16的第一膜层110第二膜层120为苯胺单体与芴类单体共聚形成的非交联的共聚物。
经实验测得，本实施例16的电致发光器件在1000nits下电流效率是44cd/A，衰减5％的寿命是8900h。
对比例1
本对比例1的电致发光器件与实施例1的电致发光器件不同之处仅在与其设置的空穴传输层220的不同，同时，其空穴传输层的设置方式如下：在空穴注入层250上采用喷墨打印方式设置空穴传输层220，该空穴传输层220的材料仅为聚苯胺形成的均聚物，其空穴传输层220的厚度为40nm，即对比例1的空穴传输层采用的是常规制备的常规结构。
经实验测得，本对比例1的电致发光器件在1000nits下电流效率是35cd/A，衰减5％的寿命是6000h。
对比例2
本对比例2的电致发光器件与实施例8的电致发光器件不同之处仅在与其设置的空穴传输层220的不同，同时，其空穴传输层的设置方式如下：在空穴注入层250上采用喷墨打印方式设置空穴传输层220，该空穴传输层220的材料仅为聚苯胺形成的均聚物，其空穴传输层220的厚度为40nm，即对比例1的空穴传输层采用的是常规制备的常规结构。
经实验测得，本对比例2的电致发光器件在1000nits下电流效率是35cd/A，衰减5％的寿命是6000h。
通过对比例1与实施例1-7的比对，可说明本申请实施例的制备方法制备所得的电致发光器件相对于传统电致发光器件，其电流效率(即器件性能)及使用寿命均得到大大提高。通过实施例1-7的比对，可说明当第二膜层120内无机纳米颗粒TiO2的直径，无机纳米颗粒TiO2在第二膜层120中的分布的间距以及第一膜层110和第二膜层120的厚度均在上述权要给出的值范围内时，其电流效率(即器件性能)及使用寿命均得到大幅提高。而当第二膜层120内无机纳米颗粒TiO2的直径，无机纳米颗粒TiO2在第二膜层120中的分布的间距以及第一膜层110和第二膜层120的厚度不在上述权要给出的值范围内时，其电流效率(即器件性能)及使用寿命的提升效果均存在不同程度的下降。
通过对比例2与实施例8-16的比对，可说明本申请实施例的制备方法制备所得的电致发光器件相对于传统电致发光器件，其电流效率(即器件性能)及使用寿命均得到大大提高。通过实施例8-16的比对，可说明当其空穴传输层220的第一膜层110为可交联的聚合物，第二膜层120为非交联的聚合物，第一膜层110及第二膜层120的厚度均在上述权要给出的值范围内，第二膜层120内残留有的有机溶液的值亦在上述权要给出的值范围内时，其电流效率(即器件性能)及使用寿命均得到大幅提高。而当第一膜层110采用非交联的聚合物，或者第二膜层采用可交联的聚合物，或者第一膜层110及第二膜层120的厚度不在上述权要给出的值范围内时，其电流效率(即器件性能)及使用寿命的提升效果均存在不同程度的下降。
以上对本申请实施例所提供的空穴传输薄膜、电致发光器件及其制备方法进行了详细介绍，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. 一种空穴传输薄膜，其特征在于，包括层叠设置的第一膜层与第二膜层，所述第一膜层为导电聚合物层或无机材料层，所述第二膜层为导电聚合物层。
  2. 根据权利要求1所述的空穴传输薄膜，其特征在于，所述导电聚合物层所采用的导电聚合物包括苯胺单体、噻吩单体以及芴类单体中的任意一种形成的均聚物或任意组合形成的共聚物；和/或，所述无机材料层所采用的无机材料包括钼氧化物、钒氧化物、钨氧化物以及镍氧化物中的任意一种。
  3. 根据权利要求1所述的空穴传输薄膜，其特征在于，所述第二膜层的导电聚合物层内部间隔分布有若干无机纳米颗粒。
  4. 根据权利要求3所述的空穴传输薄膜，其特征在于，所述无机纳米颗粒包括二氧化硅颗粒、二氧化钛颗粒、硫化锌颗粒以及氧化锌颗粒中的任意一种。
  5. 根据权利要求1～4所述的空穴传输薄膜，其特征在于，所述第一膜层的所述导电聚合物为可交联的聚合物；和/或，所述第二膜层的所述导电聚合物为非交联的聚合物。
  6. 根据权利要求1所述的空穴传输薄膜，其特征在于，所述无机纳米颗粒的直径为2nm～10nm；和/或，所述无机纳米颗粒在所述第二膜层内的分布间距为2nm～15nm。
  7. 根据权利要求1～4任一项所述的空穴传输薄膜，其特征在于，所述第一膜层110的厚度为5nm～50nm，和/或，所述第二膜层的厚度为1～15nm。
  8. 根据权利要求1～4任一项所述的空穴传输薄膜，其特征在于，
    所述第一膜层为导电聚合物层或无机材料层，所述第二膜层为导电聚合物层，且所述第二膜层的导电聚合物层内部间隔分布有若干无机纳米颗粒，所述第一膜层的厚度为5nm～35nm；和/或，所述第二膜层的厚度为5nm～15nm；
    所述第一膜层和所述第二膜层均为导电聚合物层，所述第一膜层的厚度为10nm～50nm，所述第二膜层的厚度为1nm～10nm。
  9. 一种电致发光器件，其特征在于，包括层叠设置的阳极、空穴传输层、发光层、阴极，其中，所述空穴传输层为如权利要求1～8任一项所述的空穴 传输薄膜，所述发光层邻近所述空穴传输层的一侧部分嵌入所述第二膜层。
  10. 根据权利要求9所述的电致发光器件，其特征在于，所述发光层邻近所述空穴传输层的第二膜层的一侧部分嵌入所述空穴传输层。
  11. 根据权利要求9所述的电致发光器件，其特征在于，所述发光层包括量子点，所述量子点选自单一结构量子点及核壳结构量子点中的一种或多种，所述单一结构量子点选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的一种或多种，所述II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe及CdZnSTe中的一种或多种，所述III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的一种或多种，所述I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的一种或多种；所述核壳结构的量子点的核选自上述单一结构量子点中的任意一种，所述核壳结构的量子点的壳层材料选自CdS、CdTe、CdSeTe、CdZnSe、CdZnS、CdSeS、ZnSe、ZnSeS和ZnS中的一种或多种。
  12. 根据权利要求9所述的电致发光器件，其特征在于，所述电致发光器件在所述阳极和所述空穴传输层之间还设置有空穴注入层；和或，所述电致发光器件在所述阴极和所述发光层之间还设置有电子传输层。
  13. 一种电致发光器件的制备方法，其特征在于，包括以下步骤：
    提供阳极基板；
    在所述阳极基板上设置空穴传输层；
    在所述空穴传输层上设置发光层；
    在所述发光层设置阴极；
    其中，所述设置空穴传输层包括：在所述阳极基板上设置第一膜层，及在所述第一膜层上设置第二膜层；
    其中，所述第一膜层为导电聚合物层或无机材料层，所述第二膜层为导电聚合物层。
  14. 根据权利要求13所述的制备方法，其特征在于，所述在阳极基板上设置第一膜层包括：将含有导电聚合物或无机材料的化学溶液设置在阳极基板的阳极上，并进行干燥处理，其中干燥处理的具体温度是130℃～200℃。
  15. 根据权利要求13-14所述的制备方法，其特征在于，所述第一膜层上设置第二膜层包括，将导电高聚合物、或者包含无机纳米颗粒和导电高聚物的化学溶液设置在第一膜层上，并进行干燥处理，其中上述干燥处理的具体温度是130℃～200℃。
  16. 根据权利要求13所述的制备方法，其特征在于，所述在所述阳极基板上设置空穴传输层的步骤具体包括：
    在所述阳极基板上设置第一膜层；
    在所述第一膜层上设置第二膜层，其中，以所述第二膜层的总质量计，所述第二膜层内残留有5％～10％的有机溶液，使得所述第二膜层形成所述半湿润区。
  17. 根据权利要求16所述的制备方法，其特征在于，在所述阳极基板上设置第一膜层时，对所述第一膜层进行第一真空减压干燥处理，在所述第一膜层上设置第二膜层时，对所述第二膜层进行第二真空减压干燥处理；所述第一真空减压干燥处理时的第一压强小于所述第二真空减压干燥处理时的第二压强，和/或，所述第一真空减压干燥处理持续的第一持续时间大于所述第二真空减压干燥处理持续的第二持续时间。
  18. 根据权利要求17所述的制备方法，其特征在于，所述第一压强为小于10pa，和/或，所述第二压强为1000pa～10000pa，和/或，所述第一持续时间为大于5min，和/或，所述第二持续时间为小于5min。
  19. 根据权利要求16所述的制备方法，其特征在于，在所述阳极基板上设置第一膜层时，对所述第一膜层进行第一烘烤干燥处理，在所述第一膜层上设置第二膜层时，对所述第二膜层进行第二烘烤干燥处理；所述第一烘烤干燥处理时的第一温度高于所述第二烘烤干燥处理时的第二温度，和/或，所述第一烘烤干燥处理持续的第三持续时间大于所述第二烘烤干燥处理持续的第四持续时间。
  20. 根据权利要求19所述的制备方法，其特征在于，所述第一温度为150℃～300℃，和/或，所述第二温度为50℃～150℃，和/或，所述第三持续时间为15min～60min，和/或，所述第四持续时间为1min～15min。
PCT/CN2022/142639 2022-04-20 2022-12-28 空穴传输薄膜、电致发光器件及其制备方法 WO2023202142A1 (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN202210420931.1 2022-04-20
CN202210420916.7A CN116997199A (zh) 2022-04-20 2022-04-20 一种电致发光器件及其制备方法
CN202210420916.7 2022-04-20
CN202210420931.1A CN116981279A (zh) 2022-04-20 2022-04-20 一种空穴传输薄膜、电致发光器件及其制备方法

Publications (1)

Publication Number Publication Date
WO2023202142A1 true WO2023202142A1 (zh) 2023-10-26

Family

ID=88419041

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/142639 WO2023202142A1 (zh) 2022-04-20 2022-12-28 空穴传输薄膜、电致发光器件及其制备方法

Country Status (1)

Country Link
WO (1) WO2023202142A1 (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105895816A (zh) * 2016-04-07 2016-08-24 上海大学 一种倒置蓝光量子点薄膜电致发光器件及其制造方法
CN106784357A (zh) * 2017-01-04 2017-05-31 纳晶科技股份有限公司 发光器件、含其的显示装置及照明装置、和太阳能电池
CN108447998A (zh) * 2018-03-19 2018-08-24 京东方科技集团股份有限公司 量子点发光器件及制备方法、量子点发光显示装置
US20200161577A1 (en) * 2018-11-21 2020-05-21 Lg Display Co., Ltd. Quantum dot light emitting diode and quantum dot light emitting display device including the same
CN113224245A (zh) * 2020-06-15 2021-08-06 广东聚华印刷显示技术有限公司 量子点发光二极管器件及其制备方法和显示面板
CN113258011A (zh) * 2020-06-01 2021-08-13 广东聚华印刷显示技术有限公司 电致发光二极管和显示装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105895816A (zh) * 2016-04-07 2016-08-24 上海大学 一种倒置蓝光量子点薄膜电致发光器件及其制造方法
CN106784357A (zh) * 2017-01-04 2017-05-31 纳晶科技股份有限公司 发光器件、含其的显示装置及照明装置、和太阳能电池
CN108447998A (zh) * 2018-03-19 2018-08-24 京东方科技集团股份有限公司 量子点发光器件及制备方法、量子点发光显示装置
US20200161577A1 (en) * 2018-11-21 2020-05-21 Lg Display Co., Ltd. Quantum dot light emitting diode and quantum dot light emitting display device including the same
CN113258011A (zh) * 2020-06-01 2021-08-13 广东聚华印刷显示技术有限公司 电致发光二极管和显示装置
CN113224245A (zh) * 2020-06-15 2021-08-06 广东聚华印刷显示技术有限公司 量子点发光二极管器件及其制备方法和显示面板

Similar Documents

Publication Publication Date Title
CN109256476B (zh) 量子点发光层、量子点发光器件及制备方法
US20100330716A1 (en) Electroluminescent device having improved light output
WO2023202142A1 (zh) 空穴传输薄膜、电致发光器件及其制备方法
US20220359845A1 (en) Light-emitting element, light-emitting device, and method for manufacturing light-emitting element
WO2022143822A1 (zh) 光电器件
WO2023202144A1 (zh) 薄膜、电致发光器件及其制备方法
CN116997199A (zh) 一种电致发光器件及其制备方法
CN116981279A (zh) 一种空穴传输薄膜、电致发光器件及其制备方法
WO2022143823A1 (zh) 光电器件
WO2022143829A1 (zh) 光电器件
WO2022143821A1 (zh) 光电器件
WO2022143828A1 (zh) 光电器件
WO2022143827A1 (zh) 光电器件
WO2022143831A1 (zh) 光电器件
WO2022143824A1 (zh) 光电器件
WO2022143830A1 (zh) 光电器件
WO2022143960A1 (zh) 光电器件
WO2022143825A1 (zh) 光电器件
WO2022143826A1 (zh) 光电器件
WO2022143832A1 (zh) 光电器件
WO2023202146A1 (zh) 空穴传输薄膜、光电器件和光电器件的制备方法
WO2022143556A1 (zh) 光电器件
CN114695713A (zh) 一种量子点发光二极管及其制备方法
CN116940160A (zh) 一种电致发光器件、电致发光显示屏及其制备方法
CN114695703A (zh) 一种量子点发光二极管及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22938360

Country of ref document: EP

Kind code of ref document: A1