WO2023116207A1 - 组合物、组合物的制备方法及发光器件 - Google Patents

组合物、组合物的制备方法及发光器件 Download PDF

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WO2023116207A1
WO2023116207A1 PCT/CN2022/128844 CN2022128844W WO2023116207A1 WO 2023116207 A1 WO2023116207 A1 WO 2023116207A1 CN 2022128844 W CN2022128844 W CN 2022128844W WO 2023116207 A1 WO2023116207 A1 WO 2023116207A1
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ylide
light
composition
poly
emitting device
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PCT/CN2022/128844
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French (fr)
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夏思雨
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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]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application relates to the field of optoelectronic technology, in particular to a composition, a preparation method of the composition and a light-emitting device.
  • PEDOT:PSS poly(styrene sulfonate) referred to as PEDOT:PSS
  • PEDOT:PSS poly(styrene sulfonate)
  • PSS poly(styrene sulfonate)
  • PEDOT poly(styrene sulfonate)
  • PEDOT:PSS is a high molecular polymer, usually in the form of aqueous solution, with high conductivity and adjustable conductivity characteristics.
  • PEDOT:PSS is composed of two compounds, PEDOT and PSS.
  • PEDOT is a polymer of 3,4-ethylenedioxythiophene monomer (EDOT), and PSS is polystyrene sulfonate.
  • PSS can not only be used as a dispersion of PEDOT agent to improve the solubility of PEDOT in aqueous solution, and can be used as a charge-balancing dopant to increase the conductivity of PEDOT.
  • PEDOT:PSS has high conductivity, narrow energy band width, good light transmittance, and high stability. , solution processing into film, heat resistance, green environmental protection and other advantages, so it is widely used in the preparation of hole functional layers, antistatic coatings, anti-corrosion coatings, electrodes, sensing materials, etc.
  • PEDOT:PSS In the preparation process of PEDOT:PSS, since the surface free energy of PSS is higher than that of PEDOT, when PSS is incorporated into PEDOT, PSS tends to gather on the top of PEDOT, and PSS has a higher insulation Therefore, the conductivity of PEDOT:PSS is significantly lower than that of PEDOT, and there is a problem of conduction inhomogeneity, which in turn has a negative impact on the performance of devices using PEDOT:PSS.
  • the accumulation of PSS on the top of PEDOT will reduce the hole conduction ability of the light-emitting device, which is not conducive to the electron-hole transport balance of the light-emitting device, and reduces the electron and hole in the light-emitting device.
  • the recombination efficiency of the light-emitting layer reduces the luminous efficiency of the light-emitting device.
  • the present application provides a composition, a preparation method of the composition and a light-emitting device, so as to improve the conductivity of PEDOT:PSS and promote the uniformity of conductivity of PEDOT:PSS.
  • the present application provides a composition comprising poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) and sulfur ylide.
  • the composition consists of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and sulfur ylide.
  • the mass ratio of the sulfur ylide: the poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) is 1: (50-1000).
  • the total number of carbon atoms in the sulfur ylide is not more than 10.
  • the sulfur ylide is selected from 1-allyl-3-methylsulfur ylide, 1-benzyl-3-methylsulfur ylide, 1-butyl-2,3-dimethyl Oxysulfur ylide, 1-butyl-3-methyloxysulfide ylide, 1-octyl-3-methyloxysulfide ylide, 1,3-diethoxyoxysulfide ylide, l-hexyl-3-methyl One or more of oxysulfide ylide, l-methyl-3-octyloxysulfide ylide and l-octyl-3-methyloxysulfide ylide.
  • the present application provides a method for preparing a composition, the preparation method comprising the following steps:
  • the mixture is heat-treated to obtain a composition.
  • the mass ratio of the sulfur ylide: the poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) is 1: (50-1000).
  • the first organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, dimethylsulfoxide and dimethyldimethylformamide.
  • the mixing step 3 mL to 10 mL of the first organic solvent is added per 100 mg of PEDOT:PSS.
  • the temperature of the heat treatment is 70°C to 150°C, and the time of the heat treatment is 30min to 90min.
  • the preparation method also includes the steps of:
  • the second organic solvent is selected from one or more of chloroform, toluene, diethyl ether and dichloromethane.
  • the present application provides a light emitting device, comprising:
  • a hole injection layer disposed between the anode and the light-emitting layer
  • the material of the hole injection layer includes a composition
  • the composition includes poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and sulfur ylide.
  • the material of the hole injection layer is composed of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and sulfur ylide.
  • the mass ratio of the sulfur ylide: the poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) is 1: (50-1000).
  • preparation method of the composition comprises the following steps:
  • the mixture is heat-treated to obtain a composition.
  • the first organic solvent is selected from one or more of methanol, ethanol, ethylene glycol, dimethylsulfoxide and dimethyldimethylformamide;
  • the total number of carbon atoms in the sulfur ylide is not more than 10.
  • the sulfur ylide is selected from 1-allyl-3-methylsulfur ylide, 1-benzyl-3-methylsulfur ylide, 1-butyl-2,3-dimethyl Oxysulfur ylide, 1-butyl-3-methyloxysulfide ylide, 1-octyl-3-methyloxysulfide ylide, 1,3-diethoxyoxysulfide ylide, l-hexyl-3-methyl One or more of oxysulfide ylide, l-methyl-3-octyloxysulfide ylide and l-octyl-3-methyloxysulfide ylide.
  • the material of the light-emitting layer is an organic light-emitting material or quantum dots
  • the organic luminescent material is selected from one of diaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials or DBP fluorescent materials. one or more kinds;
  • the quantum dots are selected from one or more of single component quantum dots, core-shell quantum dots, inorganic perovskite quantum dots or organic-inorganic hybrid perovskite quantum dots; when the quantum dots are selected from a single
  • the components of the quantum dots are selected from II-VI group compounds, III-V group compounds, IV-VI group compounds or I-III-VI group compounds or more, wherein the II-VI group compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe , HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdH
  • the materials of the anode and the cathode are independently selected from one or more of metals, carbon materials or metal oxides, wherein the metals are selected from Al, Ag, Cu, Mo, Au, Ba, Ca or one or more of Mg; the carbon material is selected from one or more of graphite, carbon nanotubes, graphene or carbon fibers; the metal oxide is selected from indium tin oxide, fluorine-doped tin oxide , tin antimony oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, or magnesium-doped zinc oxide.
  • the light-emitting device further includes an electron transport layer, the electron transport layer is arranged between the cathode and the light-emitting layer, the material of the electron transport layer includes nano-metal oxide, and the nano-metal oxide
  • the compound is selected from one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO or AlZnO.
  • the light-emitting device further includes a hole transport layer, the hole transport layer is arranged between the anode and the hole injection layer, and the material of the hole transport layer is selected from NiO, WO 3 , MoO 3 , CuO, poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), 3-hexyl substituted polythiophene, poly(9-vinylcarbazole), poly [Bis(4-phenyl)(4-butylphenyl)amine], poly(N,N'-bis(4-butylphenyl)-N,N'-diphenyl-1,4-benzene Diamine-CO-9,9-dioctylfluorene), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl
  • composition of the present application includes sulfur ylide and PEDOT:PSS, and sulfur ylide is used to modify PEDOT:PSS, that is, the sulfur cation generated by the hydrolysis of sulfur ylide will be electrostatically combined with PSS-, and the surface free energy of PSS- will be combined with the sulfur cation. will be reduced, thereby promoting the separation of PSS- and PEDOT+ accumulated at the top in PEDOT:PSS, effectively improving the conductivity of PEDOT:PSS, and benefiting the uniformity of PEDOT:PSS conductivity.
  • the preparation method of the composition in the present application is to first mix PEDOT:PSS, sulfur ylide and the first organic solvent to obtain a mixture, then place the mixture at a preset temperature for a specific time, and finally purify to obtain a purified composition, which has a simple preparation process , easy to control and suitable for industrial production.
  • the material of the hole injection layer includes the composition, because compared with PEDOT:PSS, sulfur ylide modified PEDOT:PSS has higher conductivity and stability, and sulfur ylide modified
  • the conductivity uniformity of the hole injection layer made of PEDOT:PSS is better than that of the hole injection layer made of PEDOT:PSS, so under the premise of the same structure and composition of other layers, compared with the use of PEDOT : PSS is used as a light-emitting device of a hole-injecting material.
  • the light-emitting device of the embodiment of the present application has a stronger hole conduction ability and is more conducive to the balance of hole-electron transport, so that the photoelectric performance and service life have obvious advantages. Applying the light-emitting device of the present application to a display device is beneficial to improving the display effect and service life of the display device.
  • Fig. 1 is a schematic flow chart of a preparation method of a composition provided in the examples of the present application.
  • Fig. 2 is a schematic flow chart of a preparation method of a composition provided in the examples of the present application.
  • Fig. 3 is a schematic structural diagram of the first light emitting device provided in the embodiment of the present application.
  • Fig. 4 is a schematic structural diagram of a second light emitting device provided in an embodiment of the present application.
  • Fig. 5 is a schematic structural diagram of a third light emitting device provided in an embodiment of the present application.
  • Fig. 6 is a schematic structural diagram of a fourth light emitting device provided in an embodiment of the present application.
  • FIG. 7 is a graph showing the luminance-voltage characteristic curves of the light emitting devices of Examples 8 to 11 and Comparative Examples in the experimental examples of the present application.
  • FIG. 8 is a graph showing the luminance-voltage characteristic curves of the light emitting devices of Examples 12 to 14 and Comparative Examples in the experimental examples of the present application.
  • Fig. 9 is a graph showing the external quantum efficiency-voltage characteristic curves of the light-emitting devices of Examples 8 to 11 and comparative examples in the experimental examples of the present application.
  • Fig. 10 is a graph showing the external quantum efficiency-voltage characteristic curves of the light-emitting devices of Examples 12 to 14 and Comparative Examples in the experimental examples of the present application.
  • the embodiments of the present application provide a composition, a preparation method of the composition, and a light emitting device. Each will be described in detail below. It should be noted that the description sequence of the following embodiments is not intended to limit the preferred sequence of the embodiments.
  • a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range.
  • a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
  • the term "and/or” is used to describe the relationship between associated objects, indicating that there may be three relationships, for example, "A and/or B" may indicate three situations: the first situation is that A exists alone ; The second case is the presence of A and B at the same time; the third case is the case of B alone, wherein A and B can be singular or plural respectively.
  • the term "at least one” means one or more, and “multiple” means two or more.
  • the term “at least one (individual)” or similar expressions thereof refers to any combination of these species (individuals), including any combination of a single species (individuals) or a plurality of species (individuals).
  • “at least one (one) of a, b, or c” or “at least one (one) of a, b, and c” can be expressed as: a, b, c, a-b (that is, a and b ), a-c, b-c or a-b-c, wherein, a, b and c can be single (one) or multiple (one) respectively.
  • the embodiment of the present application provides a composition comprising poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) and sulfur ylide.
  • sulfur ylide is used to modify PEDOT:PSS, because the Lewis structure of sulfur ylide itself will generate carbanion and sulfide ion after hydrolysis, and sulfide cation and PSS - will pass through
  • the electrostatic interaction is combined, and the surface free energy is low after the sulfide ion is combined with the PSS- , so it can promote the separation of the PSS- and PEDOT + that gather at the top in PEDOT:PSS, that is, inhibit the PSS from gathering on the top of PEDOT, thereby improving
  • the conductivity of PEDOT:PSS is beneficial to the uniformity of conductivity of PEDOT:PSS.
  • the composition consists of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and sulfur ylide.
  • the mass ratio of sulfur ylide:PEDOT:PSS is 1:(50-1000).
  • the total number of carbon atoms of the sulfur ylide is not greater than 10.
  • Sulfur ylides with a total number of carbon atoms not greater than 10 have the characteristics of less steric hindrance and lower activity.
  • the sulfur ylide is selected from 1-allyl-3-methyloxythioylide, 1-benzyl-3-methyloxythioylide, 1-butyl-2,3- Dimethylsulfur ylide, 1-butyl-3-methylsulfur ylide, 1-octyl-3-methylsulfur ylide, 1,3-diethoxysulfur ylide, l-hexyl-3 - at least one of methyl oxysulfide, l-methyl-3-octyl oxysulfide, or l-octyl-3-methyloxysulfide ylide.
  • the embodiment of the present application also provides a preparation method of the composition, as shown in Figure 1, the preparation method includes the following steps:
  • the mass ratio of sulfur ylide:PEDOT:PSS is 1:(50-1000), and the amount of the first organic solvent added is: 3mL to 10mL per 100mg of PEDOT:PSS the first organic solvent.
  • the "first organic solvent” in step S10 refers to one or more organic solvents that can dissolve sulfur ylides and have good miscibility with PEDOT:PSS.
  • the first organic solvent is at least one selected from methanol, ethanol, ethylene glycol, dimethyl alum and dimethyl diformamide.
  • step S20 heat-treating the mixture in step S10 to obtain a composition.
  • the temperature of the heat treatment is 70° C. to 150° C.
  • the time of the heat treatment is 30 minutes to 90 minutes.
  • the preparation method of the composition further includes the steps:
  • step S30 adding water to the composition in step S20, and adjusting the pH to 6.0 to 8.0 to obtain a mixed system;
  • step S30 it should be noted that the reason for "adjusting the pH to 6.0 to 8.0" is that the PSS in PEDOT:PSS is weakly acidic, and over-basicity will destroy the structure of PSS. When injecting material, it is easy to corrode the anode. In an example of the present application, it is 7.0 to adjust the pH of the mixed system with a concentration of 0.1mol/L ethanolamine solution.
  • step S40 the number of extraction times is not specifically limited, and can be selected according to actual needs.
  • “Second organic solvent” refers to all one or more organic solvents with ideal miscibility with the first organic solvent.
  • the second organic solvent is selected from chloroform, toluene, ether and at least one of dichloromethane.
  • the embodiment of the present application also provides a light-emitting device.
  • the light-emitting device 1 includes an anode 11, a cathode 12, a light-emitting layer 13, and a hole injection layer 14.
  • the hole injection layer 14 is disposed between the anode 11 and the light-emitting layer 13, wherein the material of the hole injection layer 14 includes any one of the compositions or compositions described in the embodiments of the present application.
  • the materials of the anode 11 and the cathode 12 can be common materials in the art, for example: the materials of the anode 11 and the cathode 12 are independently selected from one or more of metals, carbon materials or metal oxides
  • the metal is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca or Mg
  • the carbon material is selected from at least one of graphite, carbon nanotubes, graphene or carbon fiber
  • the metal oxide can be are doped or undoped metal oxides, for example selected from indium tin oxide (ITO), fluorine doped tin oxide (FTO), antimony tin oxide (ATO), aluminum doped zinc oxide (AZO), gallium doped At least one of zinc oxide (GZO), indium doped zinc oxide (IZO) or magnesium doped zinc oxide (MZO).
  • the anode 11 or the cathode 12 can also be selected from composite electrodes sandwiching metal 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 or at least one of TiO 2 /Al/TiO 2 .
  • the thickness of the anode can be, for example, 40 nm to 160 nm, and the thickness of the cathode can be, for example, 20 nm to 120 nm.
  • the material of the light-emitting layer 13 includes but not limited to organic light-emitting materials or quantum dots, and the thickness of the light-emitting layer 13 may be, for example, 20 nm to 60 nm.
  • Organic luminescent materials include but are not limited to at least one of diaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPA fluorescent materials, TBRb fluorescent materials or DBP fluorescent materials kind.
  • Quantum dots include but are not limited to at least one of red quantum dots, green quantum dots or blue quantum dots, and quantum dots include but are not limited to single component quantum dots, core-shell quantum dots, inorganic perovskite quantum dots dots or at least one of organic-inorganic hybrid perovskite quantum dots.
  • the particle size of the quantum dots may be, for example, 5 nm to 10 nm.
  • the components of quantum dots include, but are not limited to, those in II-VI group compounds, III-V group compounds, IV-VI group compounds or I-III-VI group compounds.
  • the group II-VI compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe , HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe,
  • CdZnSe only means that it is composed of three elements: Cd, Zn and Se. If it indicates the content of each element, it corresponds to Cd x Zn 1-x Se, 0 ⁇ x ⁇ 1.
  • inorganic perovskite quantum dots the general structural formula of inorganic perovskite quantum dots is AMX 3 , where A is a Cs + ion, M is a divalent metal cation, and M includes but is not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - , Br - or I - .
  • organic-inorganic hybrid perovskite quantum dots the general structural formula of organic-inorganic hybrid perovskite quantum dots is BMX 3 , where B is an organic amine cation, including but not limited to CH 3 (CH 2 ) n - 2NH 3+ (n ⁇ 2) or NH 3 (CH 2 ) n NH 3 2+ (n ⁇ 2), M is a divalent metal cation, M includes but not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ or Eu 2+ , X is a halogen anion, including but not limited to Cl - , Br - or I - .
  • the light-emitting device further includes an electron transport layer, the electron transport layer is disposed between the cathode and the light-emitting layer, and the material of the electron transport layer includes a nano-metal oxide, and the nano-metal oxide is selected from ZnO, At least one of TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO or AlZnO.
  • the light emitting device further includes a hole transport layer, and the hole transport layer is disposed between the anode and the hole injection layer.
  • the material of the hole transport layer includes but is not limited to poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (referred to as TFB, CAS No. 220797-16-0 ), 3-hexyl substituted polythiophene (CAS No. 104934-50-1), poly(9-vinylcarbazole) (abbreviated as PVK, CAS No.
  • Poly-TPD poly[bis(4-phenyl )(4-butylphenyl)amine]
  • Poly-TPD poly[bis(4-phenyl )(4-butylphenyl)amine]
  • Poly-TPD poly[bis(4-phenyl )(4-butylphenyl)amine]
  • PFB poly(N,N'-bis(4-butylphenyl)-N,N'- Diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene)
  • PFB poly(N,N'-bis(4-butylphenyl)-N,N'- Diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene)
  • PFB poly(N,N'-bis(4-butylphenyl)-N,N'- Diphenyl-1,4-phenylenediamine-CO-9,9-d
  • the material of the hole transport layer can also be selected from inorganic materials with hole transport capability, including but not limited to at least one of NiO, WO 3 , MoO 3 or CuO.
  • the thickness of the hole transport layer 15 may be, for example, 10 nm to 50 nm.
  • the thickness of the electron transport layer 16 may be, for example, 10 nm to 60 nm.
  • the light-emitting device in the embodiment of the present application may also include other layer structures, for example, the light-emitting device may also include an electron injection layer, the electron injection layer is arranged between the electron transport layer and the cathode, and the material of the electron injection layer includes but not Limited to at least one of alkali metal halides, alkali metal organic complexes or organic phosphine compounds, alkali metal halides include but not limited to LiF, alkali metal organic complexes include but not limited to 8-hydroxyquinoline Lithium, organic phosphine compounds include but not limited to one or more of organic phosphorus oxides, organic thiophosphine compounds or organic phosphine selenide compounds.
  • the preparation method of each layer in the light-emitting device includes but not limited to solution method and deposition method, and the solution method includes but not limited to spin coating, coating, inkjet printing, doctor blade coating, immersion pulling, soaking, spray coating, roll coating or Casting; deposition method includes chemical method and physical method, chemical method includes but not limited to chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodic oxidation method, electrodeposition method or co-precipitation method, physical method includes but not limited to is 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.
  • drying process includes all processes that can make the wet film obtain higher energy and convert it into a dry film.
  • the drying process can be, for example, heat treatment, standing and drying naturally, etc.
  • heat treatment may be a constant temperature heat treatment, or a non-constant temperature heat treatment (for example, the temperature changes in a gradient manner).
  • the material of the hole injection layer includes sulfur ylide-modified PEDOT:PSS, because compared with PEDOT:PSS, sulfur ylide-modified PEDOT:PSS has higher conductivity and stability, And the conductivity uniformity of the hole injection layer made by PEDOT:PSS modified by sulfur ylide is better than that of the hole injection layer made by PEDOT:PSS, so under the same premise of the structure of other layers, Compared with the light-emitting device using PEDOT:PSS as the hole injection material, the light-emitting device of the embodiment of the present application has stronger hole conduction ability, is more conducive to the hole-electron transport balance, and effectively improves the exciton recombination efficiency, thereby The photoelectric performance of the light emitting device of the embodiment of the present application has significant advantages.
  • An embodiment of the present application further provides a display device, the display device comprising any one of the electroluminescent devices described in the embodiments of the present application.
  • the display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, notebook computers, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, vehicle displays, televisions Or an e-book reader, wherein the smart wearable device may be, for example, a smart bracelet, a smart watch, a virtual reality (Virtual Reality, VR) helmet, and the like.
  • composition includes PEDOT:PSS and 1-benzyl-3-methylsulfuryl ylide.
  • the preparation method of described composition comprises the steps:
  • step S1.2 Put the mixture in step S1.1 at 70°C for 1 hour to obtain a solution containing the composition
  • step S1.3 Add 100 mL of deionized water to the solution containing the composition in step S1.2, and adjust the pH of the mixing system to 7.0 with an ethanolamine solution having a concentration of 0.1 mol/L to obtain a mixing system containing the composition;
  • step S1.4 use 50mL of chloroform to extract the mixed system of step S1.3 three times, remove the organic phase and collect the water phase for each extraction, combine the water phases collected by three extractions, and the water phase is the purified composition .
  • composition includes PEDOT:PSS and 1,3-diethoxysulfur ylide.
  • the preparation method of described composition comprises the steps:
  • step S2.2 Put the mixture in step S2.1 at 100° C. for 1.5 h to obtain a solution containing the composition
  • step S2.3 Add 100 mL of deionized water to the solution containing the composition in step S2.2, and adjust the pH of the mixing system to 7.0 by using an ethanolamine solution with a concentration of 0.1 mol/L to obtain a mixing system containing the composition;
  • step S2.4 use 50mL of chloroform to extract the mixed system of step S2.3 three times, remove the organic phase and collect the water phase for each extraction, combine the water phases collected by the three extractions, and the water phase is the purified composition .
  • composition includes PEDOT:PSS and 1,3-diethoxysulfur ylide.
  • the preparation method of described composition comprises the steps:
  • step S3.2 Put the mixture in step S3.1 at 80°C for 0.5h to obtain a solution containing the composition;
  • step S3.3 Add 100 mL of deionized water to the solution containing the composition in step S3.2, and adjust the pH of the mixing system to 7.0 by using an ethanolamine solution with a concentration of 0.1 mol/L to obtain a mixing system containing the composition;
  • step S3.4 use 50mL of chloroform to extract the mixed system of step S3.3 three times, remove the organic phase and collect the water phase for each extraction, combine the water phases collected by three extractions, and the water phase is the purified composition .
  • composition includes PEDOT:PSS and l-octyl-3-methylsulfuryl ylide.
  • the preparation method of described composition comprises the steps:
  • step S4.2 Place the mixture in step S4.1 at 150° C. for 0.5 h to obtain a solution containing the composition;
  • step S4.3 Add 100 mL of deionized water to the solution containing the composition in step S4.2, and adjust the pH of the mixing system to 7.0 by using an ethanolamine solution with a concentration of 0.1 mol/L to obtain a mixing system containing the composition;
  • step S4.4 use 50mL of chloroform to extract the mixed system of step S4.3 three times, remove the organic phase and collect the water phase for each extraction, combine the water phases collected by three extractions, and the water phase is the purified composition .
  • composition includes PEDOT:PSS and l-octyl-3-methylsulfuryl ylide.
  • the preparation method of described composition comprises the steps:
  • step S5.2 Put the mixture in step S5.1 at 100° C. for 1.5 h to obtain a solution containing the composition
  • step S5.3 Add 100 mL of deionized water to the solution containing the composition in step S5.2, and adjust the pH of the mixing system to 7.0 by using an ethanolamine solution with a concentration of 0.1 mol/L to obtain a mixing system containing the composition;
  • step S5.4 use 50mL of chloroform to extract the mixed system of step S5.3 three times, remove the organic phase and collect the water phase for each extraction, combine the water phases collected by three extractions, and the water phase is the purified composition .
  • composition includes PEDOT:PSS and 1,3-diethoxysulfur ylide.
  • the preparation method of described composition comprises the steps:
  • step S6.2 Put the mixture in step S6.1 at 100° C. for 1.5 h to obtain a solution containing the composition;
  • step S6.3 Add 100 mL of deionized water to the solution containing the composition in step S6.2, and adjust the pH of the mixing system to 7.0 by using an ethanolamine solution with a concentration of 0.1 mol/L to obtain a mixing system containing the composition;
  • step S6.4 use 50mL of chloroform to extract the mixed system of step S6.3 three times, remove the organic phase and collect the water phase for each extraction, combine the water phases collected by the three extractions, and the water phase is the purified composition .
  • composition includes PEDOT:PSS and 1-benzyl-3-methylsulfuryl ylide.
  • the light-emitting device is a quantum dot light-emitting diode with an upright structure.
  • the light-emitting device 1 includes a substrate The bottom 10, the anode 11, the hole injection layer 14, the hole transport layer 15, the light emitting layer 13, the electron transport layer 16 and the cathode 12, the material and thickness of each layer in the light emitting device 1 are respectively:
  • the material of the substrate 10 is glass with a thickness of 0.55mm;
  • the material of the anode 11 is ITO, and the thickness is 50nm;
  • the material of the cathode 12 is Ag, and the thickness is 80nm;
  • the material of the light-emitting layer 13 is CdZnSe/ZnS quantum dots, with a thickness of 30nm;
  • the material of the hole injection layer 14 is a thin film formed by drying the composition of Example 1, with a thickness of 30 nm;
  • the hole transport layer 15 is made of TFB with a thickness of 30nm;
  • the electron transport layer 16 is made of nano zinc oxide with a particle size of 6 nm and a thickness of 30 nm.
  • Ag is vapor-deposited on the side of the electron transport layer away from the light-emitting layer in step S8.5 to obtain a cathode, and then packaged to obtain a light-emitting device.
  • This embodiment provides a light-emitting device. Compared with the light-emitting device of Embodiment 8, the only difference of the light-emitting device of this embodiment is that the material of the hole injection layer is replaced with "the composition of Embodiment 2 is dried. formed film”.
  • This embodiment provides a light-emitting device. Compared with the light-emitting device in Embodiment 8, the light-emitting device in this embodiment is only different in that: the material of the hole injection layer is replaced with "the composition of Embodiment 3 is dried. formed film”.
  • This embodiment provides a light-emitting device. Compared with the light-emitting device of Embodiment 8, the only difference of the light-emitting device of this embodiment is that the material of the hole injection layer is replaced with "the composition of Embodiment 4 is dried. formed film”.
  • This embodiment provides a light-emitting device. Compared with the light-emitting device of Embodiment 8, the only difference of the light-emitting device of this embodiment is that the material of the hole injection layer is replaced with "the composition of Embodiment 5 is dried. formed film”.
  • This embodiment provides a light-emitting device. Compared with the light-emitting device of Embodiment 8, the only difference of the light-emitting device of this embodiment is that the material of the hole injection layer is replaced by "drying the composition of Embodiment 6.” formed film”.
  • This embodiment provides a light-emitting device. Compared with the light-emitting device of Embodiment 8, the only difference of the light-emitting device of this embodiment is that the material of the hole injection layer is replaced with "the composition of Embodiment 7 is dried. formed film”.
  • This comparative example provides a light-emitting device. Compared with the light-emitting device of Example 8, the difference between the light-emitting device of this comparative example is that the material of the hole injection layer is replaced by "PEDOT:PSS (CAS No. 155090-83-8, available from Sigma-Aldrich) dry formed film".
  • PEDOT:PSS CAS No. 155090-83-8, available from Sigma-Aldrich
  • the light-emitting devices of Embodiment 8 to Example 14 and comparative examples were tested by using the Forsta FPD optical characteristic measuring equipment, wherein the Forstar FPD optical characteristic measuring equipment is controlled by LabView QE-PRO spectrometer, Keithley 2400 and Keithley
  • the efficiency test system built by 6485 can measure and obtain parameters such as voltage, current, brightness, and luminescence spectrum of light-emitting devices, and obtain key parameters such as external quantum dot efficiency and power efficiency through calculation.
  • Examples 8 to 14 and comparative examples The maximum external quantum efficiency (EQE max , %) and maximum luminance (L max , cd/m 2 ) of the light-emitting device are detailed in Table 1 below, and the luminance-voltage characteristic curves of the light-emitting devices of Examples 8 to 14 and comparative examples As shown in FIG. 7 and FIG. 8 , the external quantum efficiency-voltage characteristic curves of the light-emitting devices of Embodiment 8 to Embodiment 14 and the comparative example are shown in FIGS. 9 and 10 .
  • the EQE max of the light emitting device of Example 8 is 1.7 times the EQE max of the light emitting device of the comparative example, and the L max of the light emitting device of Example 8 is also 1.7 times of the L max of the light emitting device of the comparative example times.
  • the comprehensive performance of the light-emitting devices of Example 8 to Example 12 is more advantageous, which fully demonstrates that the mass ratio of sulfur ylide:PEDOT:PSS is preferably 1:(50 ⁇ 1000), the content of sulfur ylides is too much or too little to improve the overall performance of the light-emitting device, if the content of sulfur ylides is too little (such as embodiment 14), then the PSS gathered on the top in PEDOT:PSS - and The promotion of separation by PEDOT + is limited, and some PSS still accumulates on the top of PEDOT, so the improvement effect on the conductivity of PEDOT:PSS is limited.
  • the synthesis of the light-emitting device of Example 14 The degree of performance improvement is limited; if the content of sulfur ylide is too much (such as embodiment 13), then a large amount of PSS - is combined with sulfur ylide electrostatically, which will affect the solubility of PEDOT, thus the effect of improving the conductivity of PEDOT:PSS is not enough. Obviously, therefore, compared with the light-emitting device of the comparative example, the overall performance of the light-emitting device of Example 13 is limited.
  • sulfur ylide-modified PEDOT:PSS has higher conductivity and stability.
  • the hole conduction capability of the light-emitting device (Example 7 to Example 12) using sulfur ylide modified PEDOT:PSS as the hole injection material is stronger, which is more conducive to the hole-electron
  • the transmission balance effectively improves the exciton recombination efficiency, thereby significantly improving the external quantum efficiency and brightness.

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Abstract

本申请公开了一种组合物、组合物的制备方法及发光器件，组合物包括硫叶立德和PEDOT:PSS，有效提高PEDOT:PSS的导电率，并有利于PEDOT:PSS的导电均匀性，发光器件中空穴注入层的材料包括所述组合物，有利于提高发光器件的光电性能和使用寿命。

Description

组合物、组合物的制备方法及发光器件
本申请要求于2021年12月21日在中国专利局提交的、申请号为202111571774.6、申请名称为“组合物、组合物的制备方法、发光器件及显示装置”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及光电技术领域，具体涉及一种组合物、组合物的制备方法及发光器件。
背景技术
聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)简称PEDOT:PSS，其是一种高分子聚合物，通常以水溶液的形式存在，具有导电率高以及导电率可调的特性。PEDOT:PSS是由PEDOT和PSS两种化合物组成，其中，PEDOT是3,4-乙烯二氧噻吩单体(EDOT)的聚合物，PSS是聚苯乙烯磺酸盐，PSS不仅可以作为PEDOT的分散剂以提高PEDOT在水溶液中的溶解性，而且可以作为平衡电荷的掺杂剂以提高PEDOT的导电率，因此，PEDOT:PSS具有导电率高、能带宽度窄、透光性好、稳定性高、可溶液加工成膜、耐热、绿色环保等优点，从而广泛应用于制备空穴功能层、抗静电涂层、防腐涂层、电极、传感材料等。
技术问题
在PEDOT:PSS的制备过程中，由于PSS的表面自由能较PEDOT的表面自由能高，所以当将PSS掺入至PEDOT中时，PSS往往会聚集于PEDOT的顶部，而PSS具有较高的绝缘性，导致PEDOT:PSS的导电率明显低于PEDOT的导电率，并且存在导电不均匀性的问题，进而对应用有PEDOT:PSS的器件的性能造成负面影响。以采用PEDOT:PSS作为空穴功能层的发光器件为例，PSS聚集于PEDOT的顶部会降低发光器件的空穴传导能力，不利于发光器件的电子-空穴传输平衡，降低电子和空穴在发光层的复合效率，从而降低发光器件的发光效率。
因此，如何优化PEDOT:PSS以提高PEDOT:PSS的导电率，并促进PEDOT:PSS的导电均匀性具有重要意义。
技术解决方案
鉴于此，本申请提供了一种组合物、组合物的制备方法及发光器件，以提高PEDOT:PSS的导电率以及促进PEDOT:PSS的导电均匀性。
第一方面，本申请提供了一种组合物，所述组合物包括聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)和硫叶立德。
可选地，所述组合物由聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)和硫叶立德组成。
可选地，在所述组合物中，所述硫叶立德：所述聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)的质量比为1：(50～1000)。
可选地，所述硫叶立德的碳原子总数不大于10。
可选地，所述硫叶立德选自1-烯丙基-3-甲基氧硫叶立德、1-苯甲基-3-甲基氧硫叶立德、1-丁基-2,3-二甲基氧硫叶立德、1-丁基-3-甲基氧硫叶立德、1-辛基-3-甲基氧硫叶立德、1,3-二乙氧基氧硫叶立德、l-己基-3-甲基氧硫叶立德、l-甲基-3-辛基氧硫叶立德以及l-辛基-3-甲基氧硫叶立德中的一种或多种。
第二方面，本申请提供了一种组合物的制备方法，所述制备方法包括如下步骤：
将聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)、硫叶立德和第一有机溶剂混合，获得混合物；以及
对所述混合物进行热处理，获得组合物。
可选地，在所述混合物中，所述硫叶立德：所述聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)的质量比为1：(50～1000)。
可选地，所述第一有机溶剂选自甲醇、乙醇、乙二醇、二甲基亚矾以及二甲基二甲酰胺中的一种或多种。
可选地，在所述混合的步骤中，每100mg的PEDOT:PSS加入3mL至10mL的所述第一有机溶剂。
可选地，所述热处理的温度为70℃至150℃，所述热处理的时间为30min 至90min。
可选地，所述制备方法还包括步骤：
向所述组合物中加入水，并调节pH为6.0至8.0，获得混合体系；以及
采用第二有机溶剂萃取所述混合体系，去除有机相并收集水相，所述水相为提纯的所述组合物；
其中，所述第二有机溶剂选自三氯甲烷、甲苯、乙醚以及二氯甲烷中的一种或多种。
第二方面，本申请提供了一种发光器件，包括：
阳极；
阴极，与所述阳极相对设置；
发光层，设置于所述阳极与所述阴极之间；以及
空穴注入层，设置于所述阳极与所述发光层之间；
其中，所述空穴注入层的材料包括组合物，所述组合物包括聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)和硫叶立德。
可选地，所述空穴注入层的材料由聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)和硫叶立德组成。
可选地，在所述组合物中，所述硫叶立德：所述聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)的质量比为1：(50～1000)。
可选地，所述组合物的制备方法包括如下步骤：
将聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)、硫叶立德和第一有机溶剂混合，获得混合物；以及
对所述混合物进行热处理，获得组合物。
可选地，所述第一有机溶剂选自甲醇、乙醇、乙二醇、二甲基亚矾以及二甲基二甲酰胺中的一种或多种；
所述硫叶立德的碳原子总数不大于10。
可选地，所述硫叶立德选自1-烯丙基-3-甲基氧硫叶立德、1-苯甲基-3-甲基氧硫叶立德、1-丁基-2,3-二甲基氧硫叶立德、1-丁基-3-甲基氧硫叶立德、1-辛基-3-甲基氧硫叶立德、1,3-二乙氧基氧硫叶立德、l-己基-3-甲基氧硫叶立德、l-甲基-3-辛基氧硫叶立德以及l-辛基-3-甲基氧硫叶立德中的一种或多种。
可选地，所述发光层的材料为有机发光材料或量子点；
其中，所述有机发光材料选自二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物或芴衍生物、TBPe荧光材料、TTPA荧光材料、TBRb荧光材料或DBP荧光材料中的一种或多种；
所述量子点选自单一组分量子点、核壳结构量子点、无机钙钛矿量子点或有机-无机杂化钙钛矿量子点的一种或多种；当所述量子点选自单一组分量子点或核壳结构量子点时，所述量子点的组分选自II-VI族化合物、III-V族化合物、IV-VI族化合物或I-III-VI族化合物中的一种或多种，其中，所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe或HgZnSTe中的一种或多种，所述III-V族化合物选自GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs或InAlPSb中的一种或多种，所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe或SnPbSTe中的一种或多种，所述I-III-VI族化合物选自CuInS、CuInSe或AgInS中的一种或多种；
所述阳极和所述阴极的材料彼此独立地选自金属、碳材料或金属氧化物中的一种或多种，其中，所述金属选自Al、Ag、Cu、Mo、Au、Ba、Ca或Mg中的一种或多种；所述碳材料选自石墨、碳纳米管、石墨烯或碳纤维中的一种或多种；所述金属氧化物选自氧化铟锡、氟掺杂氧化锡、氧化锡锑、铝掺杂的氧化锌、镓掺杂的氧化锌、铟掺杂的氧化锌或镁掺杂的氧化锌中的一种或多种。
可选地，所述发光器件还包括电子传输层，所述电子传输层设置于所述阴极与所述发光层之间，所述电子传输层的材料包括纳米金属氧化物，所述纳米 金属氧化物选自ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO或AlZnO中的一种或多种。
可选地，所述发光器件还包括空穴传输层，所述空穴传输层设置于所述阳极与所述空穴注入层之间，所述空穴传输层的材料选自NiO、WO 3、MoO 3、CuO、聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、3-己基取代聚噻吩、聚(9-乙烯咔唑)、聚[双(4-苯基)(4-丁基苯基)胺]、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)、4,4',4”-三(咔唑-9-基)三苯胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺或N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺的一种或多种。
有益效果
本申请的组合物包括硫叶立德和PEDOT:PSS，硫叶立德用于修饰PEDOT:PSS，即硫叶立德水解生成的硫正离子会与PSS-静电结合，并且PSS-与硫正离子结合后表面自由能会降低，从而促进PEDOT:PSS中聚集在顶部的PSS-与PEDOT+相分离，有效提高PEDOT:PSS的导电率，并有利于PEDOT:PSS的导电均匀性。
本申请中组合物的制备方法是先将PEDOT:PSS、硫叶立德和第一有机溶剂混合获得混合物，然后将混合物置于预设温度下特定时间，最后纯化获得提纯的组合物，具有制备工序简单、易于控制、适用于工业化生产的优点。
在本申请的发光器件中，空穴注入层的材料包括所述组合物，由于相较于PEDOT:PSS，硫叶立德修饰的PEDOT:PSS具有更高的导电率和稳定性，并且采用硫叶立德修饰的PEDOT:PSS制得的空穴注入层的导电均匀性优于采用PEDOT:PSS制得的空穴注入层的导电均匀性，所以在其他层的结构组成相同的前提下，相较于采用PEDOT:PSS作为空穴注入材料的发光器件，本申请实施例的发光器件的空穴传导能力更强，更有利于空穴-电子传输平衡，从而光电性能和使用寿命具有明显的优势。将本申请的发光器件应用于显示装置中，有利于提高显示装置的显示效果和使用寿命。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例中提供的一种组合物的制备方法的流程示意图。
图2为本申请实施例中提供的一种组合物的制备方法的流程示意图。
图3为本申请实施例中提供的第一种发光器件的结构示意图。
图4为本申请实施例中提供的第二种发光器件的结构示意图。
图5为本申请实施例中提供的第三种发光器件的结构示意图。
图6为本申请实施例中提供的第四种发光器件的结构示意图。
图7为本申请实验例中实施例8至实施例11以及对比例的发光器件的亮度-电压特性曲线图。
图8为本申请实验例中实施例12至实施例14以及对比例的发光器件的亮度-电压特性曲线图。
图9为本申请实验例中实施例8至实施例11以及对比例的发光器件的外量子效率-电压特性曲线图。
图10为本申请实验例中实施例12至实施例14以及对比例的发光器件的外量子效率-电压特性曲线图。
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。
本申请实施例提供一种组合物、组合物的制备方法及发光器件。以下分别进行详细说明。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。每当在本文中指出数值范围，是指包括所指范围内的任何引用的数字(分数或整数)。
在本申请中，术语“和/或”用于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”可以表示三种情况：第一种情况是单独存在A；第二种情况是同时存在A和B；第三种情况是单独存在B的情况，其中，A和B分别可以是单数或者复数。
在本申请中，术语“至少一种”是指一种或多种，“多种”是指两种或两种以上。术语“至少一种(个)”或其类似表达，指的是这些种(个)中的任意组合，包括单种(个)或复数种(个)的任意组合。例如，“a、b或c中的至少一种(个)”或“a,b和c中的至少一种(个)”均可表示为：a、b、c、a-b(即a和b)、a-c、b-c或a-b-c，其中，a,b和c分别可以是单种(个)或多种(个)。
本申请实施例提供了一种组合物，所述组合物包括聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)(PEDOT:PSS)和硫叶立德。
在本申请实施例的组合物中，采用硫叶立德修饰PEDOT:PSS，由于硫叶立德本身具有的路易斯(Lewis)结构水解后会生成负碳离子与硫正离子，而硫正离子与PSS -会通过静电作用相结合，并且硫正离子与PSS -结合后表面自由能较低，所以能够促进PEDOT:PSS中聚集在顶部的PSS -与PEDOT +相分离，即抑制PSS聚集于PEDOT的顶部，从而提高PEDOT:PSS的导电率，并有利于PEDOT:PSS的导电均匀性。
在本申请的一些实施例中，组合物由聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)(PEDOT:PSS)和硫叶立德组成。
为了进一步地提高PEDOT:PSS中聚集在顶部的PSS -与PEDOT +的分离程度以进一步地改善PSS聚集于PEDOT顶部的现象，并不会对PEDOT的溶解性造成负面影响，从而进一步地提高PEDOT:PSS的导电率，在本申请的一些实施例中，在组合物中，硫叶立德：PEDOT:PSS的质量比为1：(50～1000)。
为了进一步地促进PEDOT:PSS中聚集在顶部的PSS -与PEDOT +相分离，在本申请的一些实施例中，硫叶立德的碳原子总数不大于10。碳原子总数不大于10的硫叶立德具有空间位阻较小且活性较低的特性，当其水解生成的硫正离子与PSS -结合后可以进一步地降低PSS的表面自由能，避免PSS聚集于PEDOT的顶部。
在本申请的一些实施例中，硫叶立德选自1-烯丙基-3-甲基氧硫叶立德、1-苯甲基-3-甲基氧硫叶立德、1-丁基-2,3-二甲基氧硫叶立德、1-丁基-3-甲基氧硫叶立德、1-辛基-3-甲基氧硫叶立德、1,3-二乙氧基氧硫叶立德、l-己基-3-甲基氧硫叶立德、l-甲基-3-辛基氧硫叶立德或l-辛基-3-甲基氧硫叶立德中的至少一种。
本申请实施例还提供了一种组合物的制备方法，如图1所示，所述制备方法包括如下步骤：
S10、将PEDOT:PSS、硫叶立德和第一有机溶剂混合，获得混合物；
对于步骤S10，在本申请的一些实施例中，硫叶立德：PEDOT:PSS的质量比为1：(50～1000)，第一有机溶剂的添加量为：每100mg的PEDOT:PSS加入3mL至10mL的第一有机溶剂。
步骤S10中“第一有机溶剂”是指既能够溶解硫叶立德，又与PEDOT:PSS互溶性良好的一种或多种有机溶剂。在本申请的一些实施例中，第一有机溶剂选自甲醇、乙醇、乙二醇、二甲基亚矾以及二甲基二甲酰胺中的至少一种。
S20、对步骤S10的混合物进行热处理，获得组合物。
在本申请的一些实施例中，所述热处理的温度为70℃至150℃，所述热处理的时间为30min至90min。
在本申请的一些实施例中，如图2所示，在图1所示的制备方法的基础上，所述组合物的制备方法还包括步骤：
S30、向步骤S20的组合物中加入水，并调节pH为6.0至8.0，获得混合体系；
对步骤S30需要说明的是，“调节pH为6.0至8.0”的原因在于：PEDOT:PSS中的PSS呈弱酸性，过碱会破坏PSS的结构，而若过酸，当组合物用作空穴注入材料时，易腐蚀阳极。在本申请的一示例中，是采用浓度为0.1mol/L的 乙醇胺溶液调节混合体系的pH为7.0。
S40、采用第二有机溶剂萃取步骤S30的混合体系，去除有机相并收集水相，所述水相为提纯的组合物。
对步骤S40需要说明的是，萃取次数不作具体限定，可以依据实际需要自行选择。“第二有机溶剂”是指所有的与第一有机溶剂互溶性理想的一种或多种有机溶剂，在本申请的一些实施例中，第二有机溶剂选自三氯甲烷、甲苯、乙醚以及二氯甲烷中的至少一种。
本申请实施例还提供了一种发光器件，如图3所示，发光器件1包括阳极11、阴极12、发光层13以及空穴注入层14，阳极11与阴极12相对设置，发光层13设置于阳极11与阴极12之间，空穴注入层14设置于阳极11与发光层13之间，其中，空穴注入层14的材料包括如本申请实施例中任意一种所述的组合物或如本申请实施例中任意一种所述的制备方法制得的组合物。
在本申请实施例中，阳极11和阴极12的材料可以是本领域常见的材料，例如：阳极11和阴极12的材料彼此独立地选自金属、碳材料或金属氧化物中的一种或多种，金属选自Al、Ag、Cu、Mo、Au、Ba、Ca或Mg中的至少一种；碳材料选自石墨、碳纳米管、石墨烯或碳纤维中的至少一种；金属氧化物可以是掺杂或非掺杂金属氧化物，例如选自氧化铟锡(ITO)、氟掺杂氧化锡(FTO)、氧化锡锑(ATO)、铝掺杂的氧化锌(AZO)、镓掺杂的氧化锌(GZO)、铟掺杂的氧化锌(IZO)或镁掺杂的氧化锌(MZO)中的至少一种。阳极11或阴极12也可以选自掺杂或非掺杂透明金属氧化物之间夹着金属的复合电极，复合电极包括但不限于是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或TiO 2/Al/TiO 2中的至少一种。阳极的厚度例如可以是40nm至160nm，阴极的厚度例如可以是20nm至120nm。
在本申请实施例中，发光层13的材料包括但不限于是有机发光材料或量子点，发光层13的厚度例如可以是20nm至60nm。
有机发光材料包括但不限于是二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物、芴衍生物、TBPe荧光材料、TTPA荧光材料、TBRb荧光材料或DBP荧光材料中的至少一种。
量子点包括但不限于是红色量子点、绿色量子点或蓝色量子点中的至少一种，并且量子点包括但不限于是单一组分量子点、核壳结构量子点、无机钙钛矿量子点或有机-无机杂化钙钛矿量子点的至少一种。量子点的粒径例如可以是5nm至10nm。
对于单一组分量子点和核壳结构量子点，量子点的组分包括但不限于是II-VI族化合物、III-V族化合物、IV-VI族化合物或I-III-VI族化合物中的至少一种，其中，所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe或HgZnSTe中的至少一种，所述III-V族化合物选自GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs或InAlPSb中的至少一种，所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe或SnPbSTe中的至少一种，所述I-III-VI族化合物选自CuInS、CuInSe或AgInS中的至少一种。需要说明的是，对于前述单一组分量子点的材料、或者核壳结构量子点的核的材料、或者核壳结构量子点的壳的材料，提供的化学式仅示明了元素组成，并未示明各个元素的含量，例如：CdZnSe仅表示由Cd、Zn和Se三种元素组成，若表示各个元素的含量，则对应为Cd xZn 1-xSe，0<x<1。
对于无机钙钛矿量子点，无机钙钛矿量子点的结构通式为AMX 3，其中A为Cs +离子，M为二价金属阳离子，M包括但不限于是Pb 2+、Sn 2+、Cu 2+、Ni 2+、Cd 2+、Cr 2+、Mn 2+、Co 2+、Fe 2+、Ge 2+、Yb 2+或Eu 2+，X为卤素阴离子，包括但不限于Cl -、Br -或I -。
对于有机-无机杂化钙钛矿量子点，有机-无机杂化钙钛矿量子点的结构通 式为BMX 3，其中B为有机胺阳离子，包括但不限于是CH 3(CH 2) n-2NH 3+(n≥2)或NH 3(CH 2) nNH 3 2+(n≥2)，M为二价金属阳离子，M包括但不限于是Pb 2+、Sn 2+、Cu 2+、Ni 2+、Cd 2+、Cr 2+、Mn 2+、Co 2+、Fe 2+、Ge 2+、Yb 2+或Eu 2+，X为卤素阴离子，包括但不限于Cl -、Br -或I -。
在本申请的一些实施例中，发光器件还包括电子传输层，电子传输层设置于阴极与发光层之间，电子传输层的材料包括纳米金属氧化物，所述纳米金属氧化物选自ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO或AlZnO中的至少一种。
在本申请的一些实施例中，发光器件还包括空穴传输层，空穴传输层设置于阳极与空穴注入层之间。空穴传输层的材料包括但不限于是聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(简称为TFB，CAS号为220797-16-0)、3-己基取代聚噻吩(CAS号为104934-50-1)、聚(9-乙烯咔唑)(简称为PVK，CAS号为25067-59-8)、聚[双(4-苯基)(4-丁基苯基)胺](简称为Poly-TPD，CAS号为472960-35-3)、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)(简称为PFB，CAS号为223569-28-6)、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(简称NPB，CAS号为123847-85-8)、4,4'-二(9-咔唑)联苯(简称为CBP，CAS号为58328-31-7)、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺(简称TPD，CAS号为65181-78-4)或4,4',4”-三(咔唑-9-基)三苯胺(简称为TCTA，CAS号为139092-78-7)中的至少一种。此外，空穴传输层的材料还可以选自具有空穴传输能力的无机材料，包括但不限于是NiO、WO 3、MoO 3或CuO中的至少一种。
在本申请的一示例中，如图4所示，在图3所示发光器件1的基础上，发光器件1还包括空穴传输层15，空穴传输层15设置于空穴注入层14与发光层13之间。空穴传输层15的厚度例如可以是10nm至50nm。
在本申请的另一示例中，如图5所示，在图4所示发光器件1的基础上，发光器件1还包括电子传输层16，电子传输层16设置于阴极12与发光层13之间。电子传输层16的厚度例如可以是10nm至60nm。
需要说明的是，本申请实施例的发光器件还可以包括其他层结构，例如发光器件还可以包括电子注入层，电子注入层设置于电子传输层与阴极之间，电 子注入层的材料包括但不限于是碱金属卤化物、碱金属有机络合物或有机膦化合物中的至少一种，碱金属卤化物包括但不限于是LiF，碱金属有机络合物包括但不限于是8-羟基喹啉锂，有机膦化合物包括但不限于是有机氧化磷、有机硫代膦化合物或有机硒代膦化合物中的一种或多种。
发光器件中各个层的制备方法包括但不限于是溶液法和沉积法，溶液法包括但不限于是旋涂、涂布、喷墨打印、刮涂、浸渍提拉、浸泡、喷涂、滚涂或浇铸；沉积法包括化学法和物理法，化学法包括但不限于是化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法或共沉淀法，物理法包括但不限于是热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法或脉冲激光沉积法。可以理解的是，溶液法制得湿膜后需增加干燥工序，干燥工序包括所有能使湿膜获得更高能量而转变为干膜的工序，干燥工序例如可以是热处理、静置自然晾干等，其中，“热处理”可以是恒温式热处理，也可以是非恒温式热处理(例如温度呈梯度式变化)。
在本申请实施例的发光器件中，空穴注入层的材料包括硫叶立德修饰的PEDOT:PSS，由于相较于PEDOT:PSS，硫叶立德修饰的PEDOT:PSS具有更高的导电率和稳定性，并且采用硫叶立德修饰的PEDOT:PSS制得的空穴注入层的导电均匀性优于采用PEDOT:PSS制得的空穴注入层的导电均匀性，所以在其他层的结构组成相同的前提下，相较于采用PEDOT:PSS作为空穴注入材料的发光器件，本申请实施例的发光器件的空穴传导能力更强，更有利于空穴-电子传输平衡，有效提高了激子复合效率，从而本申请实施例的发光器件的光电性能具有显著的优势。
本申请实施例还提供了一种显示装置，所述显示装置包括本申请实施例中任意一种所述的电致发光器件。所述显示装置可以是任何具有显示功能的电子产品，包括但不限于是智能手机、平板电脑、笔记本电脑、数码相机、数码摄像机、智能可穿戴设备、智能称重电子秤、车载显示器、电视机或电子书阅读器，其中，智能可穿戴设备例如可以是智能手环、智能手表、虚拟现实(Virtual Reality,VR)头盔等。
下面通过具体实施例、对比例和实验例对本申请的技术方案及技术效果进行详细说明，以下实施例仅仅是本申请的部分实施例，并非对本申请作出具体 限定。
实施例1
本实施例提供了一种组合物及其制备方法，所述组合物包括PEDOT:PSS和1-苯甲基-3-甲基氧硫叶立德。
所述组合物的制备方法包括如下步骤：
S1.1、将300mg的PEDOT:PSS(CAS号为155090-83-8，购自Sigma-Aldrich)、5mg的1-苯甲基-3-甲基氧硫叶立德以及20mL的乙醇混合，获得混合物；
S1.2、将步骤S1.1的混合物置于70℃下1h，获得包含组合物的溶液；
S1.3、向步骤S1.2的包含组合物的溶液中加入100mL的去离子水，采用浓度为0.1mol/L的乙醇胺溶液调节混合体系的pH为7.0，获得包含组合物的混合体系；
S1.4、采用50mL的三氯甲烷分三次萃取步骤S1.3的混合体系，每次萃取均去除有机相并收集水相，合并三次萃取收集的水相，所述水相即为提纯的组合物。
实施例2
本实施例提供了一种组合物及其制备方法，所述组合物包括PEDOT:PSS和1,3-二乙氧基氧硫叶立德。
所述组合物的制备方法包括如下步骤：
S2.1、将500mg的PEDOT:PSS(与实施例1相同)、5mg的1,3-二乙氧基氧硫叶立德以及50mL的二甲基亚矾混合，获得混合物；
S2.2、将步骤S2.1的混合物置于100℃下1.5h，获得包含组合物的溶液；
S2.3、向步骤S2.2的包含组合物的溶液中加入100mL的去离子水，采用浓度为0.1mol/L的乙醇胺溶液调节混合体系的pH为7.0，获得包含组合物的混合体系；
S2.4、采用50mL的三氯甲烷分三次萃取步骤S2.3的混合体系，每次萃取均去除有机相并收集水相，合并三次萃取收集的水相，所述水相即为提纯的组合物。
实施例3
本实施例提供了一种组合物及其制备方法，所述组合物包括PEDOT:PSS和1,3-二乙氧基氧硫叶立德。
所述组合物的制备方法包括如下步骤：
S3.1、将200mg的PEDOT:PSS(与实施例1相同)、1mg的1,3-二乙氧基氧硫叶立德(与实施例2相同)以及10mL的乙二醇混合，获得混合物；
S3.2、将步骤S3.1的混合物置于80℃下0.5h，获得包含组合物的溶液；
S3.3、向步骤S3.2的包含组合物的溶液中加入100mL的去离子水，采用浓度为0.1mol/L的乙醇胺溶液调节混合体系的pH为7.0，获得包含组合物的混合体系；
S3.4、采用50mL的三氯甲烷分三次萃取步骤S3.3的混合体系，每次萃取均去除有机相并收集水相，合并三次萃取收集的水相，所述水相即为提纯的组合物。
实施例4
本实施例提供了一种组合物及其制备方法，所述组合物包括PEDOT:PSS和l-辛基-3-甲基氧硫叶立德。
所述组合物的制备方法包括如下步骤：
S4.1、将500mg的PEDOT:PSS(与实施例1相同)、8mg的l-辛基-3-甲基氧硫叶立德以及40mL的二甲基二甲酰胺混合，获得混合物；
S4.2、将步骤S4.1的混合物置于150℃下0.5h，获得包含组合物的溶液；
S4.3、向步骤S4.2的包含组合物的溶液中加入100mL的去离子水，采用浓度为0.1mol/L的乙醇胺溶液调节混合体系的pH为7.0，获得包含组合物的混合体系；
S4.4、采用50mL的三氯甲烷分三次萃取步骤S4.3的混合体系，每次萃取均去除有机相并收集水相，合并三次萃取收集的水相，所述水相即为提纯的组合物。
实施例5
本实施例提供了一种组合物及其制备方法，所述组合物包括PEDOT:PSS和l-辛基-3-甲基氧硫叶立德。
所述组合物的制备方法包括如下步骤：
S5.1、将1000mg的PEDOT:PSS(与实施例1相同)、1mg的l-辛基-3-甲基氧硫叶立德(与实施例4相同)以及50mL的二甲基亚矾混合，获得混合物；
S5.2、将步骤S5.1的混合物置于100℃下1.5h，获得包含组合物的溶液；
S5.3、向步骤S5.2的包含组合物的溶液中加入100mL的去离子水，采用浓度为0.1mol/L的乙醇胺溶液调节混合体系的pH为7.0，获得包含组合物的混合体系；
S5.4、采用50mL的三氯甲烷分三次萃取步骤S5.3的混合体系，每次萃取均去除有机相并收集水相，合并三次萃取收集的水相，所述水相即为提纯的组合物。
实施例6
本实施例提供了一种组合物及其制备方法，所述组合物包括PEDOT:PSS和1,3-二乙氧基氧硫叶立德。
所述组合物的制备方法包括如下步骤：
S6.1、将200mg的PEDOT:PSS(与实施例1相同)、5mg的1,3-二乙氧基氧硫叶立德(与实施例2相同)以及50mL的二甲基亚矾混合，获得混合物；
S6.2、将步骤S6.1的混合物置于100℃下1.5h，获得包含组合物的溶液；
S6.3、向步骤S6.2的包含组合物的溶液中加入100mL的去离子水，采用浓度为0.1mol/L的乙醇胺溶液调节混合体系的pH为7.0，获得包含组合物的混合体系；
S6.4、采用50mL的三氯甲烷分三次萃取步骤S6.3的混合体系，每次萃取均去除有机相并收集水相，合并三次萃取收集的水相，所述水相即为提纯的组合物。
实施例7
本实施例提供了一种组合物及其制备方法，所述组合物包括PEDOT:PSS和1-苯甲基-3-甲基氧硫叶立德。
相较于实施例7中组合物的制备方法，本实施例的制备方法的区别之处仅在于：将步骤S6.1替换为“将1100mg的PEDOT:PSS(与实施例1相同)、1mg的1,3-二乙氧基氧硫叶立德(与实施例2相同)以及50mL的二甲基亚矾混合，获得混合物”。
实施例8
本实施例提供了一种发光器件及其制备方法，所述发光器件为正置型结构的量子点发光二极管，如图6所示，在由下至上的方向上，发光器件1包括依次设置的衬底10、阳极11、空穴注入层14、空穴传输层15、发光层13、电子传输层16以及阴极12，发光器件1中各个层的材料与厚度分别为：
衬底10的材料为玻璃，厚度为0.55mm；
阳极11的材料为ITO，厚度为50nm；
阴极12的材料为Ag，厚度为80nm；
发光层13的材料为CdZnSe/ZnS量子点，厚度为30nm；
空穴注入层14的材料为实施例1的组合物干燥形成的薄膜，厚度为30nm；
空穴传输层15的材料为TFB，厚度为30nm；
电子传输层16的材料为粒径为6nm的纳米氧化锌，厚度为30nm。
本实施例中发光器件的制备方法包括如下步骤：
S8.1、提供衬底，在衬底的一侧溅射ITO以获得ITO层，然后将包含ITO的衬底依次采用丙酮超声清洗15min、清洁剂超声清洗15min、去离子水超声清洗15min以及异丙醇超声清洗15min，烘干后采用紫外-臭氧表面处理5min，获得包含阳极的衬底；
S8.2、在常温常压的空气环境下，在阳极远离衬底的一侧旋涂实施例1制得的组合物，随后置于150℃下热处理30min，获得空穴注入层；
S8.3、在常温常压的氮气环境下，在步骤S8.2的空穴注入层远离阳极的一侧旋涂浓度为9mg/mL的TFB(CAS号为223569-31-1)-氯苯溶液，然后置于150℃下恒温热处理30min，获得空穴传输层；
S8.4、在常温常压的氮气环境下，在步骤S8.3的空穴传输层远离空穴注入层的一侧旋涂浓度为20mg/mL的CdZnSe/ZnS量子点-正辛烷溶液，然后置于100℃下热处理10min，获得发光层；
S8.5、在常温常压的氮气环境下，在步骤S8.4的发光层远离空穴传输层一侧旋涂浓度为30mg/mL的纳米氧化锌-乙醇溶液，然后置于80℃下热处理30min，获得电子传输层；
S8.6、在步骤S8.5的电子传输层远离发光层的一侧蒸镀Ag，获得阴极， 然后封装获得发光器件。
实施例9
本实施例提供了一种发光器件，相较于实施例8的发光器件，本实施例的发光器件的区别之处仅在于：将空穴注入层的材料替换为“实施例2的组合物干燥形成的薄膜”。
本实施例的发光器件的制备方法参照实施例8进行。
实施例10
本实施例提供了一种发光器件，相较于实施例8的发光器件，本实施例的发光器件的区别之处仅在于：将空穴注入层的材料替换为“实施例3的组合物干燥形成的薄膜”。
本实施例的发光器件的制备方法参照实施例8进行。
实施例11
本实施例提供了一种发光器件，相较于实施例8的发光器件，本实施例的发光器件的区别之处仅在于：将空穴注入层的材料替换为“实施例4的组合物干燥形成的薄膜”。
本实施例的发光器件的制备方法参照实施例8进行。
实施例12
本实施例提供了一种发光器件，相较于实施例8的发光器件，本实施例的发光器件的区别之处仅在于：将空穴注入层的材料替换为“实施例5的组合物干燥形成的薄膜”。
本实施例的发光器件的制备方法参照实施例8进行。
实施例13
本实施例提供了一种发光器件，相较于实施例8的发光器件，本实施例的发光器件的区别之处仅在于：将空穴注入层的材料替换为“实施例6的组合物干燥形成的薄膜”。
本实施例的发光器件的制备方法参照实施例8进行。
实施例14
本实施例提供了一种发光器件，相较于实施例8的发光器件，本实施例的发光器件的区别之处仅在于：将空穴注入层的材料替换为“实施例7的组合物 干燥形成的薄膜”。
本实施例的发光器件的制备方法参照实施例8进行。
对比例
本对比例提供了一种发光器件，相较于实施例8的发光器件，本对比例的发光器件的区别之处仅在于：将空穴注入层的材料替换为“PEDOT:PSS(CAS号为155090-83-8，购自Sigma-Aldrich)干燥形成的薄膜”。
本对比例的发光器件的制备方法参照实施例8进行。
实验例
采用弗士达FPD光学特性测量设备对实施例8至实施例14以及对比例的发光器件进行性能检测，其中，弗士达FPD光学特性测量设备是由LabView控制QE-PRO光谱仪、Keithley 2400以及Keithley 6485搭建的效率测试系统，能够测量获得发光器件的电压、电流、亮度、发光光谱等参数，并通过计算获得外量子点效率、功率效率等关键参数，实施例8至实施例14以及对比例的发光器件的最大外量子效率(EQE max,％)和最大亮度(L max,cd/m 2)详见下表1，实施例8至实施例14以及对比例的发光器件的亮度-电压特性曲线如图7和图8所示，实施例8至实施例14以及对比例的发光器件的外量子效率-电压特性曲线如图9和10所示。
表1实施例8至实施例14以及对比例的发光器件的性能检测结果
Figure PCTCN2022128844-appb-000001
Figure PCTCN2022128844-appb-000002
由表1以及图7至图10可知，实施例8至实施例14的发光器件的综合性能明显优于对比例的发光器件，在驱动电压为0V至4V的范围内，随着驱动电压的升高，实施例8至实施例14以及对比例的发光器件的亮度随之升高，但实施例8至实施例14的发光器件的亮度增涨幅度显著高于对比例的发光器件；在驱动电压为0V至5V的范围内，实施例8至实施例14的发光器件的外量子效率均显著高于对比例的发光器件，并且在驱动电压为2V至3V的范围内，实施例8至实施例14的发光器件的外量子效率的增涨幅度显著高于对比例的发光器件。以实施例8为例，实施例8的发光器件的EQE max是对比例的发光器件的EQE max的1.7倍，实施例8的发光器件的L max同样是对比例的发光器件的L max的1.7倍。
相较于实施例13和实施例14的发光器件，实施例8至实施例12的发光器件的综合性能更具优势，充分说明：硫叶立德：PEDOT:PSS的质量比优选为1：(50～1000)，硫叶立德的含量过多或过少均对发光器件的综合性能改善效果有限，若硫叶立德的含量过少(例如实施例14)，则对PEDOT:PSS中聚集在顶部的PSS -与PEDOT +的促进分离程度有限，仍有部分PSS聚集于PEDOT的顶部，从而对PEDOT:PSS的导电性能的改善效果有限，因此，相较于对比例的发光器件，实施例14的发光器件的综合性能提升程度有限；若硫叶立德的含量过多(例如实施例13)，则大量的PSS -与硫叶立德静电结合，会对PEDOT的溶解性造成影响，从而PEDOT:PSS的导电率的提高效果不明显，因此，相较于对比例的发光器件，实施例13的发光器件的综合性能提升程度有限。
综上所述，相较于PEDOT:PSS，硫叶立德修饰的PEDOT:PSS具有更高的导电率和稳定性，在其他层的结构组成相同的前提下，相较于采用PEDOT:PSS作为空穴注入材料的发光器件(对比例)，采用硫叶立德修饰的PEDOT:PSS作为空穴注入材料的发光器件(实施例7至实施例12)的空穴传导能力更强，更有利于空穴-电子传输平衡，有效提高了激子复合效率，从而外量子效率和亮度显著提升。
在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详述的部分，可以参见其他实施例的相关描述。
以上对本申请实施例所提供的一种组合物、组合物的制备方法及发光器件进行了详细介绍，本文中应用了具体个例对本申请的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本申请的方法及其核心思想；同时，对于本领域的技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本申请的限制。

Claims (20)

  1. 一种组合物，其中，所述组合物包括聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)和硫叶立德。
  2. 根据权利要求1所述的组合物，其中，所述组合物由聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)和硫叶立德组成。
  3. 根据权利要求1或2所述的组合物，其中，在所述组合物中，所述硫叶立德：所述聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)的质量比为1：(50～1000)。
  4. 根据权利要求1至3任一项中所述的组合物，其中，所述硫叶立德的碳原子总数不大于10。
  5. 根据权利要求1至4任一项中所述的组合物，其中，所述硫叶立德选自1-烯丙基-3-甲基氧硫叶立德、1-苯甲基-3-甲基氧硫叶立德、1-丁基-2,3-二甲基氧硫叶立德、1-丁基-3-甲基氧硫叶立德、1-辛基-3-甲基氧硫叶立德、1,3-二乙氧基氧硫叶立德、l-己基-3-甲基氧硫叶立德、l-甲基-3-辛基氧硫叶立德以及l-辛基-3-甲基氧硫叶立德中的一种或多种。
  6. 一种组合物的制备方法，其中，所述制备方法包括如下步骤：
    将聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)、硫叶立德和第一有机溶剂混合，获得混合物；以及
    对所述混合物进行热处理，获得组合物。
  7. 根据权利要求6所述的制备方法，其中，在所述混合物中，所述硫叶立德：所述聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)的质量比为1：(50～1000)。
  8. 根据权利要求6或7所述的制备方法，其中，所述第一有机溶剂选自甲醇、乙醇、乙二醇、二甲基亚矾以及二甲基二甲酰胺中的一种或多种。
  9. 根据权利要求6至8任一项中所述的制备方法，其中，在所述混合的步骤中，每100mg的PEDOT:PSS加入3mL至10mL的所述第一有机溶剂。
  10. 根据权利要求6至9任一项中所述的制备方法，其中，所述热处理的温度为70℃至150℃，所述热处理的时间为30min至90min。
  11. 根据权利要求6至10任一项中所述的制备方法，其中，所述制备方 法还包括步骤：
    向所述组合物中加入水，并调节pH为6.0至8.0，获得混合体系；以及
    采用第二有机溶剂萃取所述混合体系，去除有机相并收集水相，所述水相为提纯的所述组合物；
    其中，所述第二有机溶剂选自三氯甲烷、甲苯、乙醚以及二氯甲烷中的一种或多种。
  12. 一种发光器件，其中，包括：
    阳极；
    阴极，与所述阳极相对设置；
    发光层，设置于所述阳极与所述阴极之间；以及
    空穴注入层，设置于所述阳极与所述发光层之间；
    其中，所述空穴注入层的材料包括组合物，所述组合物包括聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)和硫叶立德。
  13. 根据权利要求12所述的发光器件，其中，所述空穴注入层的材料由聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)和硫叶立德组成。
  14. 根据权利要求12或13所述的发光器件，其中，在所述组合物中，所述硫叶立德：所述聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)的质量比为1：(50～1000)。
  15. 根据权利要求12至14任一项中所述的发光器件，其中，所述组合物的制备方法包括如下步骤：
    将聚(3,4-乙烯二氧噻吩):聚(苯乙烯磺酸盐)、硫叶立德和第一有机溶剂混合，获得混合物；以及
    对所述混合物进行热处理，获得组合物。
  16. 根据权利要求15所述的发光器件，其中，所述第一有机溶剂选自甲醇、乙醇、乙二醇、二甲基亚矾以及二甲基二甲酰胺中的一种或多种；
    所述硫叶立德的碳原子总数不大于10。
  17. 根据权利要求12至16任一项中所述的发光器件，其中，所述硫叶立德选自1-烯丙基-3-甲基氧硫叶立德、1-苯甲基-3-甲基氧硫叶立德、1-丁基-2,3-二甲基氧硫叶立德、1-丁基-3-甲基氧硫叶立德、1-辛基-3-甲基氧硫叶立德、1,3- 二乙氧基氧硫叶立德、l-己基-3-甲基氧硫叶立德、l-甲基-3-辛基氧硫叶立德以及l-辛基-3-甲基氧硫叶立德中的一种或多种。
  18. 根据权利要求12至17任一项中所述的发光器件，其中，所述发光层的材料为有机发光材料或量子点；
    其中，所述有机发光材料选自二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物或芴衍生物、TBPe荧光材料、TTPA荧光材料、TBRb荧光材料或DBP荧光材料中的一种或多种；
    所述量子点选自单一组分量子点、核壳结构量子点、无机钙钛矿量子点或有机-无机杂化钙钛矿量子点的一种或多种；当所述量子点选自单一组分量子点或核壳结构量子点时，所述量子点的组分选自II-VI族化合物、III-V族化合物、IV-VI族化合物或I-III-VI族化合物中的一种或多种，其中，所述II-VI族化合物选自CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe或HgZnSTe中的一种或多种，所述III-V族化合物选自GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs或InAlPSb中的一种或多种，所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe或SnPbSTe中的一种或多种，所述I-III-VI族化合物选自CuInS、CuInSe或AgInS中的一种或多种；
    所述阳极和所述阴极的材料彼此独立地选自金属、碳材料或金属氧化物中的一种或多种，其中，所述金属选自Al、Ag、Cu、Mo、Au、Ba、Ca或Mg中的一种或多种；所述碳材料选自石墨、碳纳米管、石墨烯或碳纤维中的一种或多种；所述金属氧化物选自氧化铟锡、氟掺杂氧化锡、氧化锡锑、铝掺杂的氧 化锌、镓掺杂的氧化锌、铟掺杂的氧化锌或镁掺杂的氧化锌中的一种或多种。
  19. 根据权利要求12至18任一项中所述的发光器件，其中，所述发光器件还包括电子传输层，所述电子传输层设置于所述阴极与所述发光层之间，所述电子传输层的材料包括纳米金属氧化物，所述纳米金属氧化物选自ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO或AlZnO中的一种或多种。
  20. 根据权利要求12至19任一项中所述的发光器件，其中，所述发光器件还包括空穴传输层，所述空穴传输层设置于所述阳极与所述空穴注入层之间，所述空穴传输层的材料选自NiO、WO 3、MoO 3、CuO、聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、3-己基取代聚噻吩、聚(9-乙烯咔唑)、聚[双(4-苯基)(4-丁基苯基)胺]、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)、4,4',4”-三(咔唑-9-基)三苯胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺或N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺的一种或多种。
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