WO2023202146A1 - Film mince à transport de trous, dispositif photoélectrique et procédé de préparation d'un dispositif photoélectrique - Google Patents

Film mince à transport de trous, dispositif photoélectrique et procédé de préparation d'un dispositif photoélectrique Download PDF

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WO2023202146A1
WO2023202146A1 PCT/CN2022/142837 CN2022142837W WO2023202146A1 WO 2023202146 A1 WO2023202146 A1 WO 2023202146A1 CN 2022142837 W CN2022142837 W CN 2022142837W WO 2023202146 A1 WO2023202146 A1 WO 2023202146A1
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hole transport
compound
transport film
tio
group
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PCT/CN2022/142837
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Chinese (zh)
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侯文军
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Tcl科技集团股份有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour

Definitions

  • the present application relates to the field of display technology, and in particular to a hole transport film, an optoelectronic device, and a method for preparing an optoelectronic device.
  • Optoelectronic devices have a wide range of applications in new energy, sensing, communications, display, lighting and other fields, such as solar cells, photodetectors, and organic electroluminescent devices (OLED or quantum dot electroluminescent devices (QLED)).
  • solar cells photodetectors
  • organic electroluminescent devices OLED or quantum dot electroluminescent devices (QLED)
  • the structure of a traditional optoelectronic device mainly includes an anode, a hole injection layer, a hole transport film (i.e., a hole transport film), a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode.
  • a hole transport film i.e., a hole transport film
  • the holes generated by the anode and the electrons generated by the cathode of the optoelectronic device move and are injected into the hole transport film and electron transport layer respectively, and finally migrate to the light-emitting layer.
  • an Energy excitons which excite light-emitting molecules and ultimately produce visible light.
  • hole transport is an organic material and electron transport is an inorganic material
  • electron migration efficiency of inorganic nanoparticles is much greater than that of holes, which will cause a large amount of charge to accumulate at the interface between the hole transport film and the light-emitting layer, resulting in a small amount of electrons in the electric field. Under the action, it transitions to the hole transport film to form excitons, which in turn accelerates the aging of the hole transport material and affects the efficiency and life of the optoelectronic device.
  • this application provides a hole transport film, an optoelectronic device, and a method for preparing an optoelectronic device.
  • Embodiments of the present application provide a hole transport film.
  • the material of the hole transport film includes a conductive polymer and a first compound.
  • the first compound has a hole transport group. In the direction of film thickness, the content of the first compound gradually increases or decreases, wherein the LUMO energy level of the first compound is greater than the LUMO energy level of the conductive polymer.
  • the first compound contains one or more flexible alkyl groups, and the general formula of the first compound is R-A, where R is the flexible alkyl group. group, A is a hole-transporting group that does not contain the flexible alkyl group and correspondingly loses one or more hydrogen atoms, and R and A are connected through a chemical bond.
  • the flexible alkyl group is an alkyl group with 1 to 20 carbon atoms.
  • the hole transporting group is selected from 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine group, 4,4',4"-tris(carbazol-9-yl)triphenylamine group, 9, One or more types of 9-diphenylfluorenyl.
  • the first compound is a fluorine-containing compound; and/or the first compound is soluble in aromatic hydrocarbons or aromatic hydrocarbon derivatives; and/or the first compound is The LUMO energy level is greater than -2.5eV.
  • the conductive polymer includes a homopolymer of any one of aniline monomer, thiophene monomer or fluorene monomer, or includes aniline monomer, thiophene monomer or A copolymer formed from one or more fluorene monomers.
  • the weight percentage of the conductive polymer is 60% to 95%, and the weight percentage of the first compound is 5% to 40%.
  • the conductive polymer is polyaniline
  • the first compound contains one or more flexible alkyl groups
  • the general formula of the first compound is R-A , wherein R is the flexible alkyl group, A is 4,4'-bis(9-carbazole)biphenyl, R and A are connected through chemical bonds, wherein some of the hydrogen atoms in the first compound Replaced by fluorine atoms.
  • the weight percentage of the conductive polymer is 60%, and the weight percentage of the first compound is 40%; or the weight percentage of the conductive polymer is 95%, The weight percentage of the first compound is 5%; or the weight percentage of the conductive polymer is 20%, and the weight percentage of the first compound is 80%.
  • the present application provides an optoelectronic device, including a stacked cathode, a luminescent layer, a hole transport film and an anode.
  • the hole transport film is located between the luminescent layer and the anode.
  • the hole transport film The film is the above-mentioned hole transport film, wherein the content of the first compound in the hole transport film gradually increases in the direction from the anode to the light-emitting layer.
  • the thickness of the hole transport film is 10 nm to 50 nm.
  • the material quantum dots of the light-emitting layer 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 -One or more of Group 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 , AlP, InAsP, InNP, InNSb, GaAlNP and
  • the material of the carbon electrode is selected from one or more of graphite, carbon nanotubes, graphene and carbon fiber;
  • the material of the metal oxide electrode is selected from doped or non-doped ITO , FTO, ATO, AZO, GZO, IZO, MZO and one or more of AMO;
  • the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 and One or more of TiO 2 /Al/TiO 2 .
  • the optoelectronic device further includes a hole injection layer located between the hole transport film and the anode, and the hole injection layer
  • the material is selected from one or more of PEDOT: PSS, MCC, CuPc, F4-TCNQ, HATCN, transition metal oxides, and transition metal chalcogenide compounds; and/or the optoelectronic device also includes an electron transport layer, so The electron transport layer is located between the cathode and the light-emitting layer, and the material of the electron transport layer is selected from ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO2, NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, One or more of ZnLiO and InSnO.
  • the thickness of the cathode is 80 nm to 150 nm; the optoelectronic device is a top-emitting device, and the thickness of the anode is 5 nm to 5 nm. 40nm.
  • the present application provides a method for preparing an optoelectronic device, including the following steps: providing a material solution including a conductive polymer and a first compound, the LUMO energy level of the first compound being greater than the LUMO energy level of the conductive polymer. ; Provide an anode, and place the material solution on the anode;
  • the temperature of the first heat treatment is less than 100°C; and/or the temperature of the second heat treatment is greater than or equal to 100°C and less than or equal to 250°C.
  • the temperature of the first heat treatment is 40°C; and/or the temperature of the second heat treatment is 230°C.
  • the thickness of the hole transport film is 10 nm to 50 nm.
  • the method after providing the anode, includes: forming a hole injection layer on the anode; disposing the material solution on the hole injection layer; and/or Forming a cathode on the light-emitting layer includes: forming an electron transport layer and a cathode on the light-emitting layer.
  • the material quantum dots of the light-emitting layer 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 -One or more of Group 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 , AlP, InAsP, InNP, InNSb, GaAlNP and
  • the materials of the cathode and the anode are selected from one or more of metal electrodes, carbon electrodes, metal oxide electrodes or composite electrodes, and the materials of the metal electrode are selected from the group consisting of Al, Ag, Cu, Mo, Au, One or more of Ba, Ca and Mg; the material of the carbon electrode is selected from one or more of graphite, carbon nanotubes, graphene and carbon fiber; the material of the metal oxide electrode is selected from doped One or more of doped or non-doped ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO; the composite electrode is selected from AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag /ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/A
  • Figure 1 is a schematic structural diagram of an optoelectronic device provided by an embodiment of the present application.
  • Figure 2 is a schematic flow chart of a method for preparing an optoelectronic device provided by an embodiment of the present application
  • Figure 3 is a schematic diagram of energy levels of each functional layer of an optoelectronic device provided by an embodiment of the present application
  • Figure 4 is a schematic diagram of energy levels of each functional layer of an optoelectronic device provided by another embodiment of the present application.
  • Figure 5 is a schematic diagram of energy levels of each functional layer of an optoelectronic device provided by another embodiment of the present application.
  • FIG. 6 is a schematic diagram of energy levels of each functional layer of an optoelectronic device according to yet another embodiment of the present application.
  • a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and A single number within the stated range, such as 1, 2, 3, 4, 5, and 6, applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it is intended to include any cited number (fractional or whole) within the indicated range.
  • At least one means one or more, and “plurality” means two or more.
  • At least one means one or more, and “plurality” means two or more.
  • At least one means one of the following” or similar expressions thereof refers to any combination of these items, including any combination of a single item (items) or a plurality of items (items).
  • at least one of a, b, or c or “at least one 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.
  • Figure 1 is a schematic structural diagram of an optoelectronic device 100 provided by an embodiment of the present application.
  • the optoelectronic device 100 includes layers stacked in sequence.
  • the material of the hole transport film 10 includes a conductive polymer and a first compound.
  • the LUMO (Lowest Unoccupied Molecular Orbital, lowest unoccupied molecular orbital) energy level of the first compound is greater than the LUMO energy level of the conductive polymer.
  • the content of the first compound gradually increases or decreases.
  • the content of the first compound gradually increases in the thickness direction of the hole transport film 10 from bottom to top.
  • the above-mentioned hole transport film 10 the material of the hole transport film 10 includes a conductive polymer and a first compound, the first compound has a hole transport group, in the direction of the film thickness of the hole transport film 10, the first compound
  • the content gradually increases or decreases, wherein the LUMO energy level of the first compound is greater than the LUMO energy level of the conductive polymer, because the LUMO energy level of the first compound is greater than the LUMO energy level of the conductive polymer, and
  • the content of the first compound gradually increases or decreases, so that after further heat treatment of the hole transport film 10 as a whole, the hole transport film 10 as a whole becomes smaller along the thickness direction due to
  • the content of the first compound contained is relatively high, so the energy level on this side is higher and has a shallow energy level.
  • the other side of the entire hole transport film 10 along the thickness direction contains a relatively low content of the first compound. Therefore, the energy level corresponding to this side is lower and has a deep energy level, that is, the energy level of the hole transport film 10 as a whole along the thickness direction changes to a gradient state. Therefore, when electrons move from the shallow energy level side of the hole transport film 10 When entering, due to the energy level difference between the two sides of the hole transport film 10 along the thickness direction, electrons cannot enter the hole transport film 10 , that is, they cannot make a transition to the other side of the hole transport film 10 , thus causing the above-mentioned holes to enter.
  • the hole transport film 10 When the hole transport film 10 is used in the hole transport film 10 of an optoelectronic device, it can greatly reduce the number of electrons that jump to the hole transport film 10 to form excitons under the action of an electric field, thereby reducing the aging rate of the hole transport film 10. The life of the optoelectronic device 100 is improved.
  • the first compound contains a flexible alkyl group.
  • the number of flexible alkyl groups contained in the first compound may be one or multiple.
  • the group can greatly enhance the solubility of the first compound, laying the foundation for subsequent preparation of the hole transport film 10 using a solution method.
  • the above-mentioned first compound belongs to a small molecule compound
  • the conductive polymer belongs to a high molecular polymer.
  • the soluble first compound is obtained by converting insoluble small molecules and adding flexible groups.
  • the flexible groups usually include multi-carbon chain groups and double bond groups.
  • the first compound contains a flexible alkyl group.
  • the general formula of the first compound is R-A, where R is a flexible alkyl group, and A is a hole transporting group that does not contain a flexible alkyl group and correspondingly loses one or more hydrogen atoms, R and A are connected through chemical bonds, wherein the corresponding position in A that loses one or more hydrogen atoms is used to connect the corresponding flexible alkyl group.
  • the above-mentioned A is 4,4'-bis(9-carbazole)biphenyl, and the position marked "*" in the following corresponding structural formula is used to connect the corresponding flexible alkyl group,
  • the corresponding structural formula is as follows:
  • the above-mentioned A is N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, and the corresponding structure is The site marked with "*" in the formula is used to connect the corresponding flexible alkyl group, and the corresponding structural formula is as follows:
  • the above-mentioned A is 4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], and the position marked "*" in the corresponding structural formula is used Connect the corresponding flexible alkyl group, and the corresponding structural formula is as follows:
  • the above-mentioned A can also use 4,4',4"-tris(carbazol-9-yl)triphenylamine, and the position marked "*" in the corresponding structural formula is used to connect the corresponding flexible alkyl group Group, the corresponding general structural formula is as follows:
  • the above-mentioned flexible alkyl group is usually placed at a position where a hydrogen atom is lost in the para-position or meta-position of any benzene ring in the above-mentioned general structural formula.
  • the above-mentioned general structural formulas only shows the corresponding general structural formula when the site in A loses only one hydrogen atom.
  • A corresponds to the loss of multiple hydrogen atoms.
  • the corresponding principle can be referred to the situation when only one hydrogen atom is lost in the site in A, which will not be described again here.
  • the flexible alkyl group is an alkyl group with 1 to 20 carbon atoms.
  • the number of carbon atoms should not be too many, otherwise the molecular weight of the flexible alkyl group will be too large, which will lead to the molecular weight of the first compound being larger.
  • the first compound is a fluorine-containing compound.
  • adjacent fluorine atoms repel each other, so that the fluorine atoms are not in the same plane, but are distributed in a spiral along the carbon chain.
  • the sum of the van der Waals radii of two fluorine atoms is about 0.27nm, basically surrounding and filling the C-C-C bond. This almost void-free space barrier prevents any atoms or groups from entering and destroying the C-C bond.
  • the fluorine-containing compound tends to be enriched at the interface between the hole transport film 10 and the air (the side close to the light-emitting layer), and stretches into the air, so the hole transport film 10 is formed from the bottom layer (closer to the light-emitting layer).
  • the fluorine-containing compound has a lower surface energy
  • the first compound can migrate to the upper side of the hole transport film 10 more easily. and aggregation.
  • the conductive polymer compound can easily migrate and aggregate to the lower side of the hole transport film 10, eventually causing the hole transport film 10 to form a layer, that is, one side of the hole transport film 10 is laminated with the first
  • the other side of the hole transport film 10 is mainly composed of conductive polymers. In this way, both sides of the hole transport film 10 have different energy levels. One side has a shallow energy level, and the other side has a shallow energy level. One side has deep energy levels.
  • the first compound becomes a fluorine-containing compound, which further helps the hole transport film 10 to form shallow energy on both sides of the film thickness. level and deep energy level, that is, there is an energy level difference on both sides of the hole transport film 10 in the thickness direction.
  • the first compound is soluble in aromatic hydrocarbons or aromatic hydrocarbon derivatives.
  • aromatic hydrocarbons and aromatic hydrocarbon derivatives are polymer solvents with high boiling points. Select aromatic hydrocarbons and aromatic hydrocarbon derivatives as solvents, and select the first compound that is soluble in aromatic hydrocarbons or aromatic hydrocarbon derivatives to help with subsequent holes.
  • the transmission film is prepared to avoid evaporation of aromatic hydrocarbon compounds at high temperatures.
  • the LUMO energy level of the first compound is greater than -2.5 eV.
  • the LUMO energy level corresponding to the first compound usually has a shallow energy level, that is, the LUMO energy level is usually greater than -2.5eV, which can be used for conductive polymerization.
  • a larger energy level difference is formed on the other side of the material-based hole transport film 10, which is more helpful to reduce the number of excitons formed by electrons jumping to the hole transport film under the action of the electric field.
  • the conductive polymer includes a homopolymer of any one of aniline monomer, thiophene monomer or fluorene monomer, or includes at least one of aniline monomer, thiophene monomer or fluorene monomer.
  • a copolymer is a copolymer.
  • the weight percentage of the conductive polymer is 60% to 95%, and the weight percentage of the first compound is 5% to 40%.
  • the weight percentage of the first compound is too low, it will be difficult to form an energy level difference on both sides of the hole transport film 10 in the thickness direction, reducing the number of electrons that jump to the hole transport film to form excitons under the action of the electric field. The effect of reducing the aging rate of the hole transport film is not obvious.
  • the minimum weight percentage of the first compound is 5%, and at this time, the weight percentage of the conductive polymer is 95%.
  • the weight percentage of the first compound is too high, the conductive polymer content is too low, which will cause the hole mobility in the hole transport film 10 to be too low. Therefore, the minimum weight percentage of the conductive polymer is 60 %, at this time, the weight percentage of the first compound is 40%.
  • an embodiment of the present application also provides an optoelectronic device 100 .
  • the optoelectronic device 100 includes a cathode 20 , a luminescent layer 30 , a hole transport film 10 and an anode 40 stacked in sequence.
  • the material of cathode 20 is a material known in the art for cathodes
  • the material of anode 40 is a material known in the art for anodes.
  • the materials of the cathode 20 and the anode 40 may be, for example, one or more of metals, carbon materials, and metal oxides.
  • the metal may be, for example, one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg.
  • carbon materials can be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fibers
  • metal oxides can be doped or non-doped metal oxides, including ITO, FTO, ATO, AZO, One or more of GZO, IZO, MZO and AMO, including composite electrodes with metal sandwiched between doped or non-doped transparent metal oxides.
  • Composite electrodes include but are not limited to AZO/Ag/AZO, AZO /Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS , one or more of ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 and TiO 2 /Al/TiO 2 .
  • the thickness of the cathode 20 is a cathode thickness known in the art, for example, it can be 10 nm to 200 nm, such as 10 nm, 35 nm, 50 nm, 80 nm, 120 nm, 150 nm, 200 nm, etc.; the thickness of the anode 40 is an anode thickness known in the art, for example It can be 10nm to 200nm, such as 10nm, 50nm, 80nm, 100nm, 120nm, 150nm, 200nm, etc.
  • the light-emitting layer 30 may be a quantum dot light-emitting layer, and in this case, the optoelectronic device 100 may be a quantum dot optoelectronic device.
  • the thickness of the luminescent layer 30 can be within the thickness range of the luminescent layer in quantum dot optoelectronic devices known in the art, for example, it can be 5 nm to 100 nm, such as 5 nm, 10 nm, 20 nm, 50 nm, 80 nm, 100 nm, etc.; or it can be 60 nm to 100 nm. .
  • the material of the quantum dot light-emitting layer is the quantum dots known in the art to be used in the quantum dot light-emitting layer, for example, one of red quantum dots, green quantum dots and blue quantum dots.
  • the quantum dots may be selected from, but are not limited to, at least one of single structure quantum dots and core-shell structure quantum dots.
  • the quantum dots can be selected from at least one of, but not limited to, II-VI compounds, III-V compounds and I-III-VI compounds;
  • the II-VI compounds are selected from CdSe, CdS, CdTe, At least one of ZnSe, ZnS, CdTe, ZnTe, 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, AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP;
  • the I-III-VI compound is at least one selected from CuInS 2 , CuInSe 2 and AgInS 2 .
  • the optoelectronic device 100 may further include a hole injection layer (HIL) 50 .
  • the hole injection layer 50 is located between the hole transport film 10 and the anode 40 .
  • the material of the hole injection layer 50 can be selected from materials with hole injection capabilities, including but not limited to one of PEDOT: PSS, MCC, CuPc, F4-TCNQ, HATCN, transition metal oxides, and transition metal chalcogenide compounds.
  • PEDOT:PSS is a high molecular polymer, and its Chinese name is poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid).
  • the optoelectronic device 100 may further include an electron transport layer 60 , and the electron transport layer 60 is located between the cathode 20 and the light-emitting layer 30 .
  • the electron transport layer 60 may be an oxide semiconductor nanomaterial with electron transport capability.
  • the oxide semiconductor nanomaterial may be selected from, but not limited to, ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO2, NiO, TiLiO, ZnAlO, and ZnMgO. , at least one of ZnSnO, ZnLiO and InSnO.
  • the optoelectronic device 100 can also add some functional layers that are commonly used in optoelectronic devices and help improve the performance of the optoelectronic device, such as electron blocking layers, hole blocking layers, electron injection layers, and interface modifications. layer etc. It can be understood that the materials and thickness of each layer of the optoelectronic device 100 can be adjusted according to the lighting requirements of the optoelectronic device 100 .
  • the optoelectronic device 100 is a quantum dot light-emitting diode
  • the structure may be a glass substrate-anode-(hole injection layer)-hole transport film-quantum dot light-emitting layer-electron transport layer-cathode.
  • the hole injection layer is optional, and the hole injection layer may or may not be included in the quantum dot light-emitting diode structure.
  • the thickness of the hole transport film 10 is 10 nm to 50 nm.
  • Figure 2 is a schematic flow chart of a method for manufacturing an optoelectronic device provided by an embodiment of the application.
  • the preparation method includes the following steps:
  • Step S110 Provide a material solution including a conductive polymer and a first compound, where the LUMO energy level of the first compound is greater than the LUMO energy level of the conductive polymer.
  • the conductive polymer and the first compound can be dissolved using a conventional organic solvent, such as toluene, chlorobenzene, cyclohexylbenzene, and methyl benzoate. , ethyl benzoate, anisole, aromatic hydrocarbons and aromatic hydrocarbon derivatives, etc., and the solvent can be a single type, or a mixed solvent formed by two or more different solvents.
  • a conventional organic solvent such as toluene, chlorobenzene, cyclohexylbenzene, and methyl benzoate.
  • ethyl benzoate ethyl benzoate, anisole, aromatic hydrocarbons and aromatic hydrocarbon derivatives, etc.
  • the solvent can be a single type, or a mixed solvent formed by two or more different solvents.
  • the order in which the conductive polymer, the first compound and the solvent are added is not limited, as long as the three can be fully mixed to obtain a polymer solution.
  • Step S120 Provide an anode and place the material solution on the anode.
  • the anode substrate can be a commonly used substrate, for example, it can be a rigid substrate made of glass; it can also be a flexible substrate made of polyimide.
  • the material of the anode can be, for example, one or more of metals, carbon materials, and metal oxides.
  • the metal can be, for example, one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg; carbon
  • the material can be, for example, one or more of graphite, carbon nanotubes, graphene, and carbon fiber; the metal oxide can be doped or non-doped metal oxides, including ITO, FTO, ATO, AZO, GZO, IZO, One or more of MZO and AMO, including composite electrodes with metal sandwiched between doped or non-doped transparent metal oxides.
  • Composite electrodes include but are not limited to AZO/Ag/AZO, AZO/Al/AZO , ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al /ZnS, TiO 2 /Ag/TiO 2 and one or more of TiO 2 /Al/TiO 2 .
  • an anode and a hole injection layer are provided in a stacked arrangement, and a hole transport film including a conductive polymer and a first compound is arranged on the hole injection layer.
  • the first compound can more easily migrate to the upper side of the hole transport film. and aggregation.
  • the conductive polymer compound can easily migrate and aggregate to the lower side of the hole transport film, eventually causing the hole transport film to form a layer, that is, one side of the hole transport film is dominated by the first compound. , the other side of the hole transport film is dominated by conductive polymer.
  • the content of the first compound gradually increases or decreases, and the LUMO of the first compound
  • the energy level is greater than the LUMO energy level of the conductive polymer.
  • the higher the content of the first compound the higher the energy level at the corresponding position. In this way, both sides of the hole transport film have different energy levels, where One side has a shallow energy level, and the corresponding other side has a deep energy level.
  • a solution method may be used to dispose the material solution including the conductive polymer and the first compound on the anode.
  • the solution method includes but is not limited to spin coating, drip coating, coating, inkjet printing, blade coating, dipping and pulling, soaking, spray coating, roller coating, evaporation or casting, etc.
  • the wet film is prepared by the solution method.
  • Step S130 perform first heat treatment and second heat treatment in sequence to obtain a hole transport film, and the temperature of the first heat treatment is lower than the temperature of the second heat treatment.
  • the wet film on the anode can be first subjected to a first heat treatment to volatilize the organic solvent in the wet film to form a hole transport film, and then the hole transport film can be subjected to a second heat treatment.
  • the temperature of the first heat treatment is lower than that of the second heat treatment.
  • the second heat treatment is used to eliminate the residual stress inside the hole transport film, thereby reducing the risk of layer deformation and cracks in the hole transport film.
  • the temperature of the first heat treatment can be less than 100°C, such as 95°C, 80°C, 70°C, 60°C, 50°C, 40°C, etc. The higher the temperature, the faster the wet film will dry. Vacuum can also be performed at normal temperature. dry.
  • the temperature of the second heat treatment may be between 100°C and 250°C.
  • the temperature of the second heat treatment may be 100°C, 130°C, 160°C, 180°C, 200°C, 220°C, 240°C, 250°C, etc.
  • the second heat treatment can be an annealing process, which includes sequential heating, holding and cooling processes. For example, the dry hole transport film is heated to 220°C and kept for 30 minutes, and then heated at a speed of 5°C/min. Cool to room temperature.
  • Step S140 forming a light-emitting layer on the hole transport film.
  • Step S150 forming a cathode on the light-emitting layer.
  • the LUMO energy level of the first compound is greater than the LUMO energy level of the conductive polymer
  • an anode is provided, the material solution is placed on the anode, and the steps are performed in sequence
  • the first heat treatment and the second heat treatment are to obtain a hole transport film.
  • the temperature of the first heat treatment is lower than the temperature of the second heat treatment. Among them, due to the lighter molecular weight of the first compound, the first compound can more easily transfer to the hole transport film.
  • the conductive polymer compound can migrate and aggregate to the lower side of the hole transport film more easily, eventually causing the hole transport film to form layers, that is, one side of the hole transport film starts with the first The other side of the hole transport film is dominated by conductive polymers.
  • the content of the first compound in the hole transport film gradually increases or decreases in the direction of the film thickness, and the LUMO energy level of the first compound is greater than the LUMO of the conductive polymer.
  • Energy level The higher the content of the first compound, the higher the energy level at the corresponding position. In this way, both sides of the hole transport film have different energy levels. One side has a shallow energy level, and the corresponding other side has a shallow energy level.
  • One side has a deep energy level, and the increase in the LUMO energy level on the top layer of the hole transport film increases the difficulty for electrons to transition from the light-emitting layer to the hole transport film, thereby reducing the aging rate of the hole transport film and thereby improving the performance of optoelectronic devices. life.
  • step S120 is: providing an anode, sequentially forming stacked hole injection layers on the anode, and disposing the material solution on the hole injection layer.
  • step S150 is: forming an electron transport layer and a cathode on the light-emitting layer.
  • the thickness of the cathode electrode is 80nm ⁇ 150nm
  • the thickness of the anode electrode is 5nm ⁇ 40nm.
  • the method for preparing the optoelectronic device further includes the step of forming each of the functional layers.
  • anode, luminescent layer, cathode and other functional layers in this application can all be prepared using conventional techniques in the art, including but not limited to solution methods and deposition methods.
  • the solution methods include but are not limited to spin coating, Coating, inkjet printing, scraping, dipping, soaking, spraying, roller coating or casting; deposition methods include chemical methods and physical methods.
  • Chemical methods include but are not limited to chemical vapor deposition, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method or co-precipitation method.
  • Physical methods include but are not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, atomic layer deposition method or pulsed laser deposition method.
  • the preparation method of the optoelectronic device can also include a packaging step.
  • the packaging material can be acrylic resin or epoxy resin.
  • the packaging can be machine packaging or manual packaging. UV curing glue can be used.
  • the environment in which the packaging step is performed contains oxygen. The concentrations of water and water are both lower than 0.1ppm to ensure the stability of photovoltaic devices.
  • the temperature of the first heat treatment is less than 100°C.
  • the temperature of the first heat treatment is less than 100° C., which helps the first compound to migrate and accumulate to the upper side of the hole transport film more easily.
  • the temperature of the second heat treatment is greater than or equal to 100°C and less than or equal to 250°C.
  • the temperature of the second heat treatment is set at 100°C to 250°C, which is helpful for thermal curing of the hole transport film.
  • the thickness of the finally formed hole transport film can be controlled and adjusted by controlling and adjusting the solution concentration and other conditions used in the solution method.
  • the thickness of the hole transport film may range from 10 to 50nm, such as 10nm, 15nm, 20nm, 25nm, 30nm, 40nm, 50nm, etc. Taking spin coating as an example, the thickness of the hole transport film can be controlled by adjusting the concentration of the solution, the spin coating speed and the spin coating time.
  • embodiments of the present application also provide a display device, including the optoelectronic device 100 provided by the present application.
  • the display device can be any electronic product with a display function. Electronic products include but are not limited to smartphones, tablets, laptops, digital cameras, digital camcorders, smart wearable devices, smart weighing scales, vehicle monitors, and televisions. Or an e-book reader, wherein the smart wearable device can be, for example, a smart bracelet, a smart watch, or a virtual reality (Virtual Reality).
  • An embodiment of the present application also provides a method for preparing an optoelectronic device 100, including the step of preparing a hole transport film. , prepare a hole transport film using the preparation method shown in step S31 to step S33.
  • This embodiment provides a quantum dot light-emitting diode and a preparation method thereof.
  • the structural composition of the quantum dot light-emitting diode is shown in Figure 1.
  • the quantum dot light-emitting diode of this embodiment includes a cathode 20 and an electron transport layer that are stacked sequentially from top to bottom. 60.
  • each layer structure in quantum dot light-emitting diodes are:
  • the material of the cathode 20 is Al.
  • the material of the electron transport layer 60 is Zn 0.7 Mg 0.3 O.
  • the material of the light-emitting layer 30 is nano-ZnS.
  • the material of the hole transport film 10 is: including the conductive polymer (95% wt) of the present application and the first compound (5% wt), wherein the conductive polymer is polyaniline and the first compound contains flexible alkyl groups. 4,4'-bis(9-carbazole)biphenyl, some H atoms are replaced by fluorine atoms.
  • the material of the hole injection layer 50 is PEDOT:PSS.
  • the anode 40 is made of ITO with a thickness of 100 nm, and a glass substrate is provided on one side of the anode 40 .
  • Materials for preparing the hole transport film 10 The conductive polymer and the first compound are dissolved in aromatic hydrocarbons to obtain a hole transport material solution.
  • Anode 40 is prepared on a glass substrate.
  • PEDOT:PSS was spin-coated on the side of the anode 40 away from the glass substrate at a rotation speed of 5000 rpm for 30 seconds, and then annealed at 200° C. for 15 minutes to obtain the hole injection layer 50 .
  • the hole transport material solution was spin-coated on the side of the hole injection layer 50 away from the anode 40 at a rotation speed of 3000 rpm for 30 seconds, followed by drying at 40°C and annealing at 230°C to obtain the hole transport film 10 .
  • CdZnSe quantum dots are spin-coated on the side of the hole transport film 10 away from the hole injection layer 50 , and then annealed to obtain the light-emitting layer 30 .
  • Zn 0.9 Mg 0.1 O is spin-coated on the side of the light-emitting layer 30 away from the hole transport film 10 , and then annealed to obtain the electron transport layer 60 .
  • the Al cathode 20 is prepared by evaporation on the side of the electron transport layer 60 away from the light-emitting layer 30 .
  • the LUMO energy level becomes a gradient energy level, and on the side close to the light-emitting layer 30, the LUMO energy level of the hole transport film 10 can reach -2.1 eV.
  • Figure 3 for the energy level diagram.
  • This embodiment provides a quantum dot light-emitting diode and a preparation method thereof.
  • the only difference between the quantum dot light-emitting diode of this embodiment is the material of the hole transport film 10 It is: containing the conductive polymer of the present application (80% wt) and the first compound (20% wt).
  • the LUMO energy level becomes a gradient energy level, and on the side close to the light-emitting layer 30, the LUMO energy level of the hole transport film 10 can reach -1.6 eV.
  • Figure 4 for the energy level diagram.
  • This embodiment provides a quantum dot light-emitting diode and a preparation method thereof.
  • the only difference between the quantum dot light-emitting diode of this embodiment is the material of the hole transport film 10 It is: containing the conductive polymer of the present application (60% wt) and the first compound (40% wt).
  • the LUMO energy level becomes a gradient energy level, and on the side close to the light-emitting layer 30, the LUMO energy level of the hole transport film 10 can reach -1.3 eV.
  • Figure 5 for the energy level diagram.
  • This embodiment provides a quantum dot light-emitting diode and a preparation method thereof. Compared with the quantum dot light-emitting diode of Embodiment 1, the only difference between the quantum dot light-emitting diode of this embodiment is the material of the hole transport film 10 For: containing the conductive polymer of this application, please see Figure 6 for the energy level diagram.
  • Example 1 Analyzing with reference to Figures 3 to 6, in Example 1, the LUMO energy level of the hole transport film 10 is increased from -3.7eV to -2.1eV, so that the LUMO energy level difference between the hole transport film 10 and the light-emitting layer increases to 2.0 eV; In Example 2, the LUMO energy level of the hole transport film 10 is increased from -3.7eV to -1.6eV, so that the LUMO energy level difference between the hole transport film 10 and the light-emitting layer is increased to 2.5eV; in Example 3, The LUMO energy level of the hole transport film 10 is increased from -3.7eV to -1.3eV, which increases the LUMO energy level difference between the hole transport film 10 and the light-emitting layer to 2.8eV.
  • the LUMO energy level difference between the hole transport film 10 and the light-emitting layer increases, which increases the difficulty for electrons to transition from the light-emitting layer to the hole transport film, thereby reducing the aging of the hole transport film. rate, thereby improving the life of optoelectronic devices.

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Abstract

La présente invention concerne un film mince à transport de trous, un dispositif photoélectrique et un procédé de préparation pour le dispositif photoélectrique. Le matériau du film mince à transport de trous comprend un polymère conducteur et un premier composé ayant un groupe de transport de trous ; la teneur du premier composé dans le sens de l'épaisseur du film mince à transport de trous est progressivement augmentée ou progressivement diminuée ; le niveau d'énergie LUMO du premier composé est supérieur à celui du polymère conducteur, afin de réduire le taux de vieillissement du film mince et de prolonger la durée de vie du dispositif photoélectrique.
PCT/CN2022/142837 2022-04-20 2022-12-28 Film mince à transport de trous, dispositif photoélectrique et procédé de préparation d'un dispositif photoélectrique WO2023202146A1 (fr)

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CN202210419130.3A CN116981282A (zh) 2022-04-20 2022-04-20 空穴传输薄膜、光电器件和光电器件的制备方法
CN202210419130.3 2022-04-20

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105514290A (zh) * 2015-12-28 2016-04-20 Tcl集团股份有限公司 一种量子点发光二极管及其制备方法
US20160293902A1 (en) * 2015-04-06 2016-10-06 Japan Display Inc. Display device and method of manufacturing a display device
CN109768177A (zh) * 2019-01-10 2019-05-17 云谷（固安）科技有限公司 一种有机发光显示面板及其制作方法
CN110957436A (zh) * 2019-11-25 2020-04-03 苏州欧谱科显示科技有限公司 耐溶剂混合型空穴传输材料组合物及量子点发光二极管

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160293902A1 (en) * 2015-04-06 2016-10-06 Japan Display Inc. Display device and method of manufacturing a display device
CN105514290A (zh) * 2015-12-28 2016-04-20 Tcl集团股份有限公司 一种量子点发光二极管及其制备方法
CN109768177A (zh) * 2019-01-10 2019-05-17 云谷（固安）科技有限公司 一种有机发光显示面板及其制作方法
CN110957436A (zh) * 2019-11-25 2020-04-03 苏州欧谱科显示科技有限公司 耐溶剂混合型空穴传输材料组合物及量子点发光二极管

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