WO2022143557A1 - Solution composition, preparation method therefor, film layer, and light-emitting diode - Google Patents

Solution composition, preparation method therefor, film layer, and light-emitting diode Download PDF

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Publication number
WO2022143557A1
WO2022143557A1 PCT/CN2021/141747 CN2021141747W WO2022143557A1 WO 2022143557 A1 WO2022143557 A1 WO 2022143557A1 CN 2021141747 W CN2021141747 W CN 2021141747W WO 2022143557 A1 WO2022143557 A1 WO 2022143557A1
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layer
solution composition
magnesium
light
zinc oxide
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PCT/CN2021/141747
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French (fr)
Chinese (zh)
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姚振垒
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Tcl科技集团股份有限公司
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Publication of WO2022143557A1 publication Critical patent/WO2022143557A1/en

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    • 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
    • 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
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers

Definitions

  • the present application belongs to the field of display technology, and particularly relates to a solution composition and a preparation method thereof, a film layer and a light emitting diode.
  • the typical structure of Diode, QLED is a "sandwich” structure, which is mainly composed of an anode, a hole injection layer (HIL), a hole transport layer (HTL), a quantum dot light-emitting layer, an electron transport layer (ETL), and a cathode. Due to the advantages of large-area preparation and simple process, the use of solution methods such as spin coating and inkjet printing to prepare various functional layers in QLED is favored by technical workers.
  • the purpose of the present application is to provide a solution composition and a preparation method thereof, aiming at solving the problem of poor stability of the existing magnesium-doped zinc oxide-ethanol solution.
  • One aspect of the present application provides a solution composition comprising magnesium-doped zinc oxide, ethanol, and a halogenated hydrocarbon.
  • halogen atom in the halogenated hydrocarbon includes at least one of F, Cl, Br and I.
  • halogenated hydrocarbons include chlorinated aromatic hydrocarbons and/or chlorinated alkanes.
  • the chlorinated aromatic hydrocarbon includes at least one of chlorobenzene, dichlorobenzene, chlorotoluene, dichlorotoluene and benzyl chloride.
  • the chlorinated alkane includes at least one of dichloromethane, chloroform, dichloroethane, dichloropropane, dichlorobutane and chlorocyclohexane.
  • magnesium-doped zinc oxide is dispersed in the solution composition as sol particles.
  • volume ratio of halohydrocarbon and ethanol is 1:(2-4).
  • the halogenated hydrocarbon is chlorobenzene
  • the magnesium-doped zinc oxide is dissolved in ethanol in the form of sol particles.
  • mass-volume ratio of magnesium-doped zinc oxide to ethanol is (20-60) mg: 1 mL.
  • the solution composition provided in the present application uses halogenated hydrocarbons as stability additives to be mixed with magnesium-doped zinc oxide and ethanol. Since the lone pair electrons of halogen atoms of halogenated hydrocarbons can interact with Zn atoms with empty orbitals, Halogenated hydrocarbons combine with magnesium-doped zinc oxide to form complexes, which can effectively prevent the aggregation of magnesium-doped zinc oxide sol particles dissolved in ethanol, improve the stability of magnesium-doped zinc oxide-ethanol solution at room temperature, and make the
  • the solution composition provided by the application has a longer storage time at normal temperature. After testing, compared with the magnesium-doped zinc oxide-ethanol solution, the storage time of the solution composition at room temperature is significantly prolonged, which is beneficial to promote the wide application of magnesium-doped zinc oxide in the QLED industry.
  • the present application provides a method for preparing a solution composition.
  • the preparation method of the solution composition of the present application comprises the following steps:
  • Magnesium-doped zinc oxide, ethanol, and halogenated hydrocarbons are mixed until a clear solution is formed.
  • the method for mixing magnesium-doped zinc oxide, ethanol and halogenated hydrocarbons includes the following steps:
  • the halogenated hydrocarbons were added to the magnesium-doped zinc oxide-ethanol solution for mixing treatment.
  • the preparation method of the solution composition of the present application can disperse the magnesium-doped zinc oxide, such as being dissolved in ethanol in the form of sol particles, and make the components mix uniformly.
  • the present application provides a film layer, which is formed from the above-mentioned solution composition through film-forming treatment.
  • the film layer provided by the present application is formed by the above-mentioned solution composition through film-forming treatment. Due to the good stability of the above-mentioned solution composition, the quality of the film layer is improved to a certain extent, which is conducive to obtaining a flat and dense film layer on the surface.
  • the present application provides a light emitting diode, comprising an electronic functional layer, and the electronic functional layer includes the above-mentioned film layer.
  • the electronic functional layer is an electron transport layer.
  • the light emitting diode also includes an anode, a hole injection layer, a hole transport layer, a light emitting layer and a cathode, wherein the anode is connected to the substrate as a bottom electrode, the hole injection layer is arranged between the anode and the light emitting layer, and the hole transports The layer is disposed between the hole injection layer and the light-emitting layer, and the electron transport layer is disposed between the light-emitting layer and the cathode.
  • the light-emitting diode also includes an anode, a hole injection layer, a hole transport layer, a light-emitting layer and a cathode, wherein the cathode is connected to the substrate as a bottom electrode, the electron transport layer is arranged between the cathode and the light-emitting layer, and the hole injection layer is It is provided between the anode and the light-emitting layer, and the hole transport layer is provided between the light-emitting layer and the hole injection layer.
  • the anode includes conductive metal and/or conductive metal oxide
  • the conductive metal is selected from at least one of nickel, platinum, vanadium, chromium, copper, zinc and gold
  • the conductive metal oxide includes zinc oxide, indium oxide, At least one of tin, indium tin oxide, indium zinc oxide, and fluorine-doped tin oxide.
  • the material of the hole injection layer includes at least one of PEDOT:PSS, CuPc, F4-TCNQ, HATCN, doped or undoped transition metal oxide, and doped or undoped metal chalcogenide ; wherein, the transition metal oxide includes at least one of MoO 3 , VO 2 , WO 3 , and CuO, and the metal chalcogenide compound includes at least one of MoS 2 , MoSe 2 , WS 2 , WSe 2 , and CuS.
  • the thickness of the hole injection layer is preferably 10-150 nm.
  • the material of the hole transport layer includes at least one of TFB, PVK, Poly-TPD, PFB, TCTA, CBP, TPD, NPB, doped graphene, undoped graphene, and C60.
  • the thickness of the hole transport layer is preferably 10-150 nm.
  • the material of the light-emitting layer includes semiconductor quantum dots and perovskite quantum dots; wherein, the semiconductor quantum dots are 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, CdHgSeS, CdHgSeTe, CdZnSeTe, HgZnSeTe, Hg
  • the cathode is selected from at least one of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, and barium; or, the cathode is a multilayer Structural material, selected from at least one of alkali metal halides, alkaline earth metal halides, and alkali metal oxides; or, the cathode is a combination of a multilayer structural material and a metal layer, and the metal layer is selected from LiF At least one of /Al, LiO 2 /Al, LiF/Ca, Liq/Al, and BaF 2 /Ca.
  • the electronic functional layer is the above-mentioned film layer, and has good luminous efficiency.
  • the present application provides a method for manufacturing a light emitting diode.
  • the preparation method of the light-emitting diode of the present application comprises the following steps:
  • the solution composition is subjected to film-forming treatment on the cathode to obtain an electronic functional layer.
  • the present application provides another method for preparing a light emitting diode.
  • the preparation method of the light-emitting diode of the present application comprises the following steps:
  • solution composition of the present application or the solution composition prepared by the preparation method of the solution composition of the present application and an anode with a light-emitting layer formed on the surface;
  • the solution composition is subjected to film-forming treatment on the side of the anode near the light-emitting layer to obtain an electronic functional layer.
  • the light-emitting diode prepared by the light-emitting diode preparation method of the present application has good luminous efficiency and stable performance.
  • FIG. 1 is a schematic structural diagram of a light emitting diode according to an embodiment of the present application
  • Fig. 2 is the solution state of the solutions provided in Examples 1-1 to 1-3 and Comparative Example 1 on the 1st, 2nd, 3rd, 4th and 6th days, respectively.
  • the solutions in each picture are classified according to halogenated hydrocarbon and ethanol
  • the volume ratios of 0, 1:4, 1:2 and 1:1 are arranged in order from left to right;
  • Fig. 3 is the solution state of the solutions provided in Examples 2-1 to 2-3 and Comparative Example 2 on the 1st, 2nd, 3rd, 4th and 6th days, respectively.
  • the volume ratios of 0, 1:4, 1:2 and 1:1 are arranged in order from left to right;
  • Fig. 4 is the solution state of the solutions provided in Examples 3-1 to 3-3 and Comparative Example 3 on the 1st, 2nd, 3rd, 4th and 6th days, respectively.
  • the volume ratios of 0, 1:4, 1:2 and 1:1 are arranged in order from left to right.
  • Fig. 5 is the process flow diagram of the preparation method of solution composition
  • FIG. 6 is a process flow diagram of a preparation method of a light-emitting diode
  • FIG. 7 is a process flow diagram of another method for manufacturing a light emitting diode.
  • each reference number in the figure 1-anode, 21-hole injection layer, 22-hole transport layer, 3-light-emitting layer, 4-electron functional layer, 42-electron transport layer, 5-cathode.
  • the embodiments of the present application provide a solution composition including magnesium-doped zinc oxide, ethanol and halogenated hydrocarbons.
  • magnesium-doped zinc oxide is a ZnO nanomaterial doped with Mg metal element, also known as magnesium-doped zinc oxide or zinc-magnesium oxide. Due to its good electron transport properties, magnesium-doped ZnO is often used as a material for forming an electron transport layer to fabricate QLEDs.
  • adding chlorinated hydrocarbons in a ratio of 1: (2-4) according to the volume ratio of halogenated hydrocarbons and ethanol can significantly improve the stability of the solution at room temperature and prolong its storage time at room temperature.
  • Ethanol was used as a solvent to dissolve magnesium-doped zinc oxide.
  • the mass-to-volume ratio of magnesium-doped zinc oxide to ethanol is (20-60) mg: 1 mL, which ensures that magnesium-doped zinc oxide can be dissolved in ethanol in the form of sol particles, and when magnesium-doped zinc oxide is oxidized
  • zinc and ethanol are mixed at this ratio and an appropriate amount of halogenated hydrocarbons are added, for example, adding chlorinated hydrocarbons in a ratio of 1: (2-4) according to the volume ratio of halogenated hydrocarbons and ethanol, can significantly improve the solution at room temperature. stability and prolong its storage time at room temperature.
  • Halogenated hydrocarbons are used as additives to improve solution stability.
  • the amount of halogenated hydrocarbons affects the stability of the solution at room temperature.
  • the volume ratio of halogenated hydrocarbons to ethanol is 1: (2-4) to ensure that the solutions provided in the embodiments of the present application are more magnesium-doped Hetero zinc oxide-ethanol has a longer storage time at room temperature.
  • Halogenated hydrocarbons are a class of compounds containing halogen atoms.
  • the halogen atoms contain lone pairs of electrons that can interact with the empty orbitals of Zn atoms of magnesium-doped zinc oxide in solution, so that halogenated hydrocarbons combine with magnesium-doped zinc oxide. doped with zinc oxide to form complexes, preventing the aggregation of magnesium-doped zinc oxide sol particles dissolved in ethanol, thereby improving the stability of magnesium-doped zinc oxide-ethanol solution at room temperature, and effectively prolonging the storage time of the solution at room temperature .
  • the halogen atoms in the halohydrocarbon include at least one of F, Cl, Br, and I.
  • the halogenated hydrocarbons include chlorinated aromatic hydrocarbons and/or chlorinated alkanes, such halogenated hydrocarbons are soluble in ethanol, and added to a solution comprising magnesium doped zinc oxide and ethanol, can result in magnesium The storage time of the solution doped with zinc oxide and ethanol at room temperature was significantly prolonged.
  • the chlorinated aromatic hydrocarbon includes at least one of chlorobenzene, dichlorobenzene, chlorotoluene, dichlorotoluene and benzyl chloride
  • the chlorinated alkane includes dichloromethane, chloroform, dichloroethane, dichloropropane, At least one of dichlorobutane and chlorocyclohexane.
  • the embodiment of the present application achieves the purpose of effectively prolonging the storage time of the solution at room temperature by adding halogenated hydrocarbons to the solution containing magnesium-doped zinc oxide and ethanol.
  • the halogenated hydrocarbon is selected as chlorobenzene
  • the volume ratio of chlorobenzene and ethanol is 1: (2-4)
  • magnesium-doped zinc oxide can be dissolved in ethanol in the form of sol particles, and the components are mixed evenly to obtain a clear solution.
  • the preparation method of the above solution composition includes: mixing and stirring magnesium-doped zinc oxide, ethanol and halogenated hydrocarbon until a clear solution is formed.
  • the embodiments of the present application further provide a film layer and a light emitting diode.
  • a film layer is formed from the above solution composition through film forming treatment.
  • the film layer provided by the examples of the present application is formed by the above-mentioned solution composition after film-forming treatment. Due to the good stability of the above-mentioned solution composition, the quality of the film layer provided by the present application is improved to a certain extent, which is beneficial to obtain the surface Flat and dense film layer.
  • the method of film-forming treatment can refer to conventional techniques in the art, for example, the above solution composition is deposited on the substrate by a solution method such as spin coating method, inkjet printing method, etc., and then drying treatment is performed to obtain magnesium-doped zinc oxide. film layer.
  • a solution method such as spin coating method, inkjet printing method, etc.
  • the substrate is used as a carrier for the grade solution composition, and its material type and structural composition can refer to conventional techniques in the art.
  • the substrate is a rigid substrate, a flexible substrate or a metal electrode, including but not limited to glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone, magnesium, calcium, sodium , potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, etc.
  • the matrix can also be a multi-layer structural material formed with a specific functional film layer, such as a negative electrode formed with an electronic functional layer or an anode formed with a light-emitting functional layer, which can be flexibly adjusted according to the actual production conditions and the target product to be prepared. .
  • a light emitting diode includes an electronic functional layer, and the electronic functional layer includes the above-mentioned film layer.
  • the electronic functional layer is the above-mentioned film layer, and has good luminous efficiency.
  • the electronic functional layer is a general term for functional film layers such as an electron injection layer, an electron transport layer, and an electron blocking layer. In some embodiments, the electronic functional layer is an electron transport layer.
  • the structures of the light emitting diodes in the embodiments of the present application may refer to conventional technologies in the art.
  • the light emitting diodes are of an upright structure, and the anode is connected to the substrate as a bottom electrode; in other embodiments, the light emitting diodes are of an inverted structure.
  • the cathode is connected to the substrate as the bottom electrode.
  • a hole functional layer can also be provided between the anode and the light-emitting layer, and the hole functional layer includes a hole injection layer, A hole transport layer and a hole blocking layer.
  • the light emitting diode includes: an anode 1 , a hole injection layer 21 , a hole transport layer 22 , a light emitting layer 3 , an electron transport layer 42 and a cathode 5 , wherein the anode 1 is connected to the substrate as a Bottom electrode, the hole injection layer 21 is arranged between the anode 1 and the light-emitting layer 3, the hole transport layer 22 is arranged between the hole injection layer 21 and the light-emitting layer 3, and the electron transport layer 42 is arranged between the light-emitting layer 3 and the cathode 5 between.
  • the materials and thicknesses of the anode, the hole injection layer, the hole transport layer, the light emitting layer and the cathode may refer to conventional techniques in the art.
  • the substrate includes a rigid substrate and a flexible substrate.
  • the substrate is selected from glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate At least one of ethylene formate, polyamide, and polyethersulfone.
  • the anode includes conductive metals and/or conductive metal oxides
  • conductive metals include but are not limited to nickel, platinum, vanadium, chromium, copper, zinc and gold, etc. or their alloys
  • conductive metal oxides include but are not limited to zinc oxide, indium oxide, Tin oxide, indium tin oxide (ITO), indium zinc oxide (IZO), fluorine doped tin oxide, etc.
  • the material of the hole injection layer is selected as a material with good hole injection performance, including but not limited to poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), copper phthalocyanine (CuPc) , 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano- 1,4,5,8,9,12-hexaazatriphenylene (HATCN), doped or undoped transition metal oxides, doped or undoped metal chalcogenides, etc.; Metal oxides include but are not limited to MoO 3 , VO 2 , WO 3 , CuO, etc., and metal chalcogenides include but are not limited to MoS 2 , MoSe 2 , WS 2 , WSe 2 , CuS and the like.
  • the thickness of the hole injection layer
  • the material of the hole transport layer is selected as an organic material with good hole transport ability, including but not limited to poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB ), polyvinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (Poly-TPD), poly(9,9 -Dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4''-tris(carbazol-9-yl)triphenylamine ( TCTA), 4,4'-bis(9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- Biphenyl-4,4'-d
  • the material of the light-emitting layer can be selected from conventional materials in the art, including but not limited to semiconductor quantum dots, perovskite quantum dots, and the like. In some embodiments, the material of the light-emitting layer is selected as semiconductor quantum dots. In a specific embodiment, the material of the light-emitting layer is selected from at least one of group II-VI semiconductor quantum dots, group III-V semiconductor quantum dots, and group IV-VI semiconductor quantum dots.
  • group II-VI semiconductor quantum dots include but are not limited to 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, HgZnSTe, etc., III-
  • IV-VI semiconductor quantum dots include but are not limited to SnS, SnSe, SnTe , PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, etc.
  • the cathode can be selected from a single metal or an alloy thereof, including but not limited to at least one of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium; or , the cathode is selected as a multilayer structure material, including but not limited to alkali metal halides, alkaline earth metal halides, alkali metal oxides, etc.; or, the cathode is selected as a combination of a multilayer structure material and a metal layer, and the metal layer is selected as an alkaline earth metal and/or Group IIIA metals, including but not limited to LiF/Al, LiO 2 /Al, LiF/Ca, Liq/Al, and BaF 2 /Ca, etc.
  • the process flow of the above light-emitting diode manufacturing method is shown in FIG. 6 , including the following steps:
  • the solution composition is subjected to film forming treatment on the cathode to obtain an electronic functional layer.
  • the process flow of the above light-emitting diode manufacturing method is shown in FIG. 7 , and may further include the following steps:
  • Examples 1-8 and Comparative Examples 1-3 provide a solution composition, the composition of which is shown in Table 1.
  • the preparation method of above-mentioned solution composition comprises the following steps:
  • magnesium-doped zinc oxide 1) adding magnesium-doped zinc oxide into ethanol, stirring until magnesium-doped zinc oxide is dissolved in the ethanol solvent in the form of colloidal particles to obtain magnesium-doped zinc oxide-ethanol solution;
  • Example 1-1 to Example 3-3 and Comparative Example 1-3 were placed in the air at room temperature respectively, and then the changes in the state of the solution were observed.
  • the results are shown in Table 2 and Figure 2-4.
  • the stability of the solution composition provided in this embodiment at room temperature can be enhanced to varying degrees, and when the volume ratio of halogenated hydrocarbons and ethanol is controlled at 1: (2- 4), it can ensure that the solution remains clear after being placed in the air for 4 days.

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Abstract

The present application relates to the technical field of display, and provided therein are a solution composition, a preparation method therefor, a film layer, and a light-emitting diode. The solution composition provided in the present application comprises: magnesium-doped zinc oxide, ethanol, and a halogenated hydrocarbon. In the solution composition, the halogenated hydrocarbon is used as a stabilizing additive and mixed with magnesium-doped zinc oxide and ethanol. The lone pair of the halogen atom of the halogenated hydrocarbon may interact with a Zn atom having an empty orbital, such that the halogenated hydrocarbon is bonded to the magnesium-doped zinc oxide to form a coordination complex.

Description

溶液组合物及其制备方法、膜层和发光二极管Solution composition and preparation method thereof, film layer and light emitting diode
本申请要求于2020年12月30日在中国专利局提交的、申请号为202011616819.2、申请名称为“溶液组合物、膜层和发光二极管”的中国申请专利的优先权。This application claims the priority of the Chinese patent application filed on December 30, 2020 with the application number 202011616819.2 and the application name is "solution composition, film layer and light-emitting diode".
技术领域technical field
本申请属于显示技术领域，尤其涉及一种溶液组合物及其制备方法和一种膜层以及发光二极管。The present application belongs to the field of display technology, and particularly relates to a solution composition and a preparation method thereof, a film layer and a light emitting diode.
背景技术Background technique
量子点发光二极管（Quantum Dot Light Emitting Diode，QLED）的典型结构是“三明治”结构，主要由阳极、空穴注入层（HIL）、空穴传输层（HTL）、量子点发光层、电子传输层（ETL）和阴极组成。由于具有可大面积制备、工艺简便等优点，采用旋涂、喷墨打印等溶液法制备QLED中的各功能膜层深受技术工作者的青睐。Quantum Dot Light Emitting The typical structure of Diode, QLED) is a "sandwich" structure, which is mainly composed of an anode, a hole injection layer (HIL), a hole transport layer (HTL), a quantum dot light-emitting layer, an electron transport layer (ETL), and a cathode. Due to the advantages of large-area preparation and simple process, the use of solution methods such as spin coating and inkjet printing to prepare various functional layers in QLED is favored by technical workers.
技术问题technical problem
本申请的目的在于提供一种溶液组合物及其制备方法，旨在解决现有镁掺杂氧化锌-乙醇溶液稳定性差的问题。The purpose of the present application is to provide a solution composition and a preparation method thereof, aiming at solving the problem of poor stability of the existing magnesium-doped zinc oxide-ethanol solution.
技术解决方案technical solutions
本申请的一方面提供了一种溶液组合物，包括镁掺杂氧化锌、乙醇和卤代烃。One aspect of the present application provides a solution composition comprising magnesium-doped zinc oxide, ethanol, and a halogenated hydrocarbon.
进一步地，卤代烃中的卤素原子包括F、Cl、Br和I中的至少一种。Further, the halogen atom in the halogenated hydrocarbon includes at least one of F, Cl, Br and I.
更进一步地，卤代烃包括氯代芳烃和/或氯代烷烃。Still further, halogenated hydrocarbons include chlorinated aromatic hydrocarbons and/or chlorinated alkanes.
具体地，氯代芳烃包括氯苯、二氯苯、氯甲苯、二氯甲苯和苄氯中的至少一种。Specifically, the chlorinated aromatic hydrocarbon includes at least one of chlorobenzene, dichlorobenzene, chlorotoluene, dichlorotoluene and benzyl chloride.
具体地，氯代烷烃包括二氯甲烷、氯仿、二氯乙烷、二氯丙烷、二氯丁烷和氯代环己烷中的至少一种。Specifically, the chlorinated alkane includes at least one of dichloromethane, chloroform, dichloroethane, dichloropropane, dichlorobutane and chlorocyclohexane.
进一步地，镁掺杂氧化锌在溶液组合物中是以溶胶颗粒分散。Further, the magnesium-doped zinc oxide is dispersed in the solution composition as sol particles.
进一步地，卤代烃和乙醇的体积比为1 : (2-4)。Further, the volume ratio of halohydrocarbon and ethanol is 1:(2-4).
更进一步地，卤代烃为氯苯，镁掺杂氧化锌以溶胶颗粒形式溶解在乙醇中。Furthermore, the halogenated hydrocarbon is chlorobenzene, and the magnesium-doped zinc oxide is dissolved in ethanol in the form of sol particles.
进一步地，镁掺杂氧化锌的化学式为Zn 1-xMg xO，x = 0.025-0.075。 Further, the chemical formula of magnesium-doped zinc oxide is Zn 1-x Mg x O, x = 0.025-0.075.
进一步地，镁掺杂氧化锌与乙醇的质量体积比为(20-60) mg: 1 mL。Further, the mass-volume ratio of magnesium-doped zinc oxide to ethanol is (20-60) mg: 1 mL.
本申请所提供的溶液组合物，以卤代烃为稳定性添加剂与镁掺杂氧化锌和乙醇混合，由于卤代烃的卤原子的孤对电子可以与具有空轨道的Zn原子相互作用而使得卤代烃与镁掺杂氧化锌结合形成配合物，可有效防止溶解在乙醇中的镁掺杂氧化锌溶胶颗粒聚集，提高了镁掺杂氧化锌-乙醇溶液在常温下的稳定性，使得本申请提供的溶液组合物在常温下具有较长的保存时间。经测试，相对于镁掺杂氧化锌-乙醇溶液，该溶液组合物在常温下的保存时间明显延长，这有利于促进镁掺杂氧化锌在QLED产业中的广泛应用。The solution composition provided in the present application uses halogenated hydrocarbons as stability additives to be mixed with magnesium-doped zinc oxide and ethanol. Since the lone pair electrons of halogen atoms of halogenated hydrocarbons can interact with Zn atoms with empty orbitals, Halogenated hydrocarbons combine with magnesium-doped zinc oxide to form complexes, which can effectively prevent the aggregation of magnesium-doped zinc oxide sol particles dissolved in ethanol, improve the stability of magnesium-doped zinc oxide-ethanol solution at room temperature, and make the The solution composition provided by the application has a longer storage time at normal temperature. After testing, compared with the magnesium-doped zinc oxide-ethanol solution, the storage time of the solution composition at room temperature is significantly prolonged, which is beneficial to promote the wide application of magnesium-doped zinc oxide in the QLED industry.
第二方面，本申请提供了一种溶液组合物的制备方法。本申请溶液组合物的制备方法包括如下步骤：In a second aspect, the present application provides a method for preparing a solution composition. The preparation method of the solution composition of the present application comprises the following steps:
将镁掺杂氧化锌、乙醇和卤代烃进行混合处理，直至形成澄清溶液。Magnesium-doped zinc oxide, ethanol, and halogenated hydrocarbons are mixed until a clear solution is formed.
进一步地，将镁掺杂氧化锌、乙醇和卤代烃进行混合处理的方法包括如下步骤：Further, the method for mixing magnesium-doped zinc oxide, ethanol and halogenated hydrocarbons includes the following steps:
将镁掺杂氧化锌溶解在乙醇中，获得镁掺杂氧化锌-乙醇溶液；Dissolving magnesium-doped zinc oxide in ethanol to obtain magnesium-doped zinc oxide-ethanol solution;
将卤代烃加入镁掺杂氧化锌-乙醇溶液中进行混合处理。The halogenated hydrocarbons were added to the magnesium-doped zinc oxide-ethanol solution for mixing treatment.
本申请溶液组合物的制备方法能够使镁掺杂氧化锌分散如具体以溶胶颗粒的形式溶解在乙醇中，且使得各成分之间混合均匀。The preparation method of the solution composition of the present application can disperse the magnesium-doped zinc oxide, such as being dissolved in ethanol in the form of sol particles, and make the components mix uniformly.
第三方面，本申请提供了一种膜层，由上述溶液组合物经过成膜处理而成。In a third aspect, the present application provides a film layer, which is formed from the above-mentioned solution composition through film-forming treatment.
本申请所提供的膜层，由上述溶液组合物经过成膜处理而成，由于上述溶液组合物稳定性好，使得膜层的质量得到一定程度的改善，有利于获得表面平整致密的膜层。The film layer provided by the present application is formed by the above-mentioned solution composition through film-forming treatment. Due to the good stability of the above-mentioned solution composition, the quality of the film layer is improved to a certain extent, which is conducive to obtaining a flat and dense film layer on the surface.
第四方面，本申请提供了一种发光二极管，包括电子功能层，电子功能层包括上述膜层。In a fourth aspect, the present application provides a light emitting diode, comprising an electronic functional layer, and the electronic functional layer includes the above-mentioned film layer.
进一步地，电子功能层为电子传输层。Further, the electronic functional layer is an electron transport layer.
进一步地，发光二极管还包括阳极、空穴注入层、空穴传输层、发光层和阴极，其中，阳极连接衬底作为底电极，空穴注入层设置在阳极和发光层之间，空穴传输层设置在空穴注入层和发光层之间，电子传输层设置在发光层和阴极之间。Further, the light emitting diode also includes an anode, a hole injection layer, a hole transport layer, a light emitting layer and a cathode, wherein the anode is connected to the substrate as a bottom electrode, the hole injection layer is arranged between the anode and the light emitting layer, and the hole transports The layer is disposed between the hole injection layer and the light-emitting layer, and the electron transport layer is disposed between the light-emitting layer and the cathode.
进一步地，发光二极管还包括阳极、空穴注入层、空穴传输层、发光层和阴极，其中，阴极连接衬底作为底电极，电子传输层设置在阴极和发光层之间，空穴注入层设置在阳极和发光层之间，空穴传输层设置在发光层和空穴注入层之间。Further, the light-emitting diode also includes an anode, a hole injection layer, a hole transport layer, a light-emitting layer and a cathode, wherein the cathode is connected to the substrate as a bottom electrode, the electron transport layer is arranged between the cathode and the light-emitting layer, and the hole injection layer is It is provided between the anode and the light-emitting layer, and the hole transport layer is provided between the light-emitting layer and the hole injection layer.
更进一步地，阳极包括导电金属和/或导电金属氧化物，导电金属选自镍、铂、钒、铬、铜、锌和金的至少之一，导电金属氧化物包括氧化锌、氧化铟、氧化锡、氧化铟锡、氧化铟锌、氟掺杂的氧化锡的至少之一。Further, the anode includes conductive metal and/or conductive metal oxide, the conductive metal is selected from at least one of nickel, platinum, vanadium, chromium, copper, zinc and gold, and the conductive metal oxide includes zinc oxide, indium oxide, At least one of tin, indium tin oxide, indium zinc oxide, and fluorine-doped tin oxide.
更进一步地，空穴注入层的材料包括PEDOT:PSS、CuPc、F4-TCNQ、HATCN、掺杂或非掺杂的过渡金属氧化物、掺杂或非掺杂的金属硫系化合物的至少之一；其中，过渡金属氧化物包括MoO 3、VO 2、WO 3、CuO至少之一，金属硫系化合物包括MoS 2、MoSe 2、WS 2、WSe 2、CuS至少之一。 Further, the material of the hole injection layer includes at least one of PEDOT:PSS, CuPc, F4-TCNQ, HATCN, doped or undoped transition metal oxide, and doped or undoped metal chalcogenide ; wherein, the transition metal oxide includes at least one of MoO 3 , VO 2 , WO 3 , and CuO, and the metal chalcogenide compound includes at least one of MoS 2 , MoSe 2 , WS 2 , WSe 2 , and CuS.
更进一步地，空穴注入层的厚度优选为10-150nm。Further, the thickness of the hole injection layer is preferably 10-150 nm.
更进一步地，空穴传输层的材料包括TFB、PVK、Poly-TPD、PFB、TCTA、CBP、TPD、NPB、掺杂石墨烯、非掺杂石墨烯、C60的至少之一。Further, the material of the hole transport layer includes at least one of TFB, PVK, Poly-TPD, PFB, TCTA, CBP, TPD, NPB, doped graphene, undoped graphene, and C60.
更进一步地，空穴传输层的厚度优选为10-150nm。Further, the thickness of the hole transport layer is preferably 10-150 nm.
更进一步地，发光层的材料包括半导体量子点和钙钛矿量子点；其中，所述半导体量子点选自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、HgZnSTe、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、InAlPSb、SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTe中的至少之一。Further, the material of the light-emitting layer includes semiconductor quantum dots and perovskite quantum dots; wherein, the semiconductor quantum dots are 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, CdHgSeS, CdHgSeTe, CdZnSeTe, HgZnSeTe HgZnSTe, 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, InAlPSb, SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, At least one of SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe.
更进一步地，阴极选自镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡、铅、铯、钡中的至少一种；或者，所述阴极为多层结构材料，选自碱金属卤化物、碱土金属卤化物、碱金属氧化物中的至少一种；或者，所述阴极为多层结构材料和和金属层的组合，所述金属层为选自LiF/Al、LiO 2/Al、LiF/Ca、Liq/Al、和BaF 2/Ca中的至少一种。 Further, the cathode is selected from at least one of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, and barium; or, the cathode is a multilayer Structural material, selected from at least one of alkali metal halides, alkaline earth metal halides, and alkali metal oxides; or, the cathode is a combination of a multilayer structural material and a metal layer, and the metal layer is selected from LiF At least one of /Al, LiO 2 /Al, LiF/Ca, Liq/Al, and BaF 2 /Ca.
本申请所提供的发光二极管，其电子功能层为上述膜层，具有良好的发光效率。In the light-emitting diode provided by the present application, the electronic functional layer is the above-mentioned film layer, and has good luminous efficiency.
第五方面，本申请提供了一种发光二极管的制备方法。本申请发光二极管的制备方法包括如下步骤：In a fifth aspect, the present application provides a method for manufacturing a light emitting diode. The preparation method of the light-emitting diode of the present application comprises the following steps:
提供本申请溶液组合物或由本申请溶液组合物制备方法制备的溶液组合物以及阴极；Provide the solution composition of the present application or the solution composition prepared by the preparation method of the solution composition of the present application and a cathode;
将溶液组合物在阴极上进行成膜处理，获得电子功能层。The solution composition is subjected to film-forming treatment on the cathode to obtain an electronic functional layer.
本申请提供了另一种发光二极管的制备方法。本申请发光二极管的制备方法包括如下步骤：The present application provides another method for preparing a light emitting diode. The preparation method of the light-emitting diode of the present application comprises the following steps:
提供本申请溶液组合物或由本申请溶液组合物制备方法制备的溶液组合物以及表面形成有发光层的阳极；Provide the solution composition of the present application or the solution composition prepared by the preparation method of the solution composition of the present application and an anode with a light-emitting layer formed on the surface;
将溶液组合物在阳极上靠近发光层的一侧进行成膜处理，获得电子功能层。The solution composition is subjected to film-forming treatment on the side of the anode near the light-emitting layer to obtain an electronic functional layer.
本申请发光二极管制备方法制备的发光二极管具有良好的发光效率，而且性能稳定。The light-emitting diode prepared by the light-emitting diode preparation method of the present application has good luminous efficiency and stable performance.
附图说明Description of drawings
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或示范性技术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，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。In order to illustrate the technical solutions in the embodiments of the present application more clearly, the following briefly introduces the accompanying drawings that are used in the description of the embodiments or exemplary technologies. Obviously, the drawings in the following description are only for the present application. In some embodiments, for those of ordinary skill in the art, other drawings can also be obtained according to these drawings without any creative effort.
图1是本申请一实施例提供的一种发光二极管的结构示意图；FIG. 1 is a schematic structural diagram of a light emitting diode according to an embodiment of the present application;
图2是实施例1-1至1-3和对比例1提供的溶液分别在第1、2、3、4和6天时的溶液状态，每一幅图中的各溶液按照卤代烃和乙醇的体积比分别为0、1:4、1:2和1:1从左到右依次排列；Fig. 2 is the solution state of the solutions provided in Examples 1-1 to 1-3 and Comparative Example 1 on the 1st, 2nd, 3rd, 4th and 6th days, respectively. The solutions in each picture are classified according to halogenated hydrocarbon and ethanol The volume ratios of 0, 1:4, 1:2 and 1:1 are arranged in order from left to right;
图3是实施例2-1至2-3和对比例2提供的溶液分别在第1、2、3、4和6天时的溶液状态，每一幅图中的各溶液按照卤代烃和乙醇的体积比分别为0、1:4、1:2和1:1从左到右依次排列；Fig. 3 is the solution state of the solutions provided in Examples 2-1 to 2-3 and Comparative Example 2 on the 1st, 2nd, 3rd, 4th and 6th days, respectively. The volume ratios of 0, 1:4, 1:2 and 1:1 are arranged in order from left to right;
图4是实施例3-1至3-3和对比例3提供的溶液分别在第1、2、3、4和6天时的溶液状态，每一幅图中的各溶液按照卤代烃和乙醇的体积比分别为0、1:4、1:2和1:1从左到右依次排列。Fig. 4 is the solution state of the solutions provided in Examples 3-1 to 3-3 and Comparative Example 3 on the 1st, 2nd, 3rd, 4th and 6th days, respectively. The volume ratios of 0, 1:4, 1:2 and 1:1 are arranged in order from left to right.
图5是溶液组合物的制备方法工艺流程图；Fig. 5 is the process flow diagram of the preparation method of solution composition;
图6是发光二极管的一种制备方法工艺流程图；6 is a process flow diagram of a preparation method of a light-emitting diode;
图7是发光二极管的另一种制备方法工艺流程图。FIG. 7 is a process flow diagram of another method for manufacturing a light emitting diode.
其中，图中各附图标记：1-阳极，21-空穴注入层，22-空穴传输层，3-发光层，4-电子功能层，42-电子传输层，5-阴极。Wherein, each reference number in the figure: 1-anode, 21-hole injection layer, 22-hole transport layer, 3-light-emitting layer, 4-electron functional layer, 42-electron transport layer, 5-cathode.
本发明的实施方式Embodiments of the present invention
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clear, the present application will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, but not to limit the present application.
本申请实施例提供了一种溶液组合物，包括镁掺杂氧化锌、乙醇和卤代烃。The embodiments of the present application provide a solution composition including magnesium-doped zinc oxide, ethanol and halogenated hydrocarbons.
具体地，镁掺杂氧化锌为掺杂有Mg金属元素的ZnO纳米材料，又称为掺镁氧化锌或氧化锌镁。由于具有良好的电子传输性能，镁掺杂氧化锌常作为形成电子传输层的材料而应用于制备QLED。Specifically, magnesium-doped zinc oxide is a ZnO nanomaterial doped with Mg metal element, also known as magnesium-doped zinc oxide or zinc-magnesium oxide. Due to its good electron transport properties, magnesium-doped ZnO is often used as a material for forming an electron transport layer to fabricate QLEDs.
一些实施例中，镁掺杂氧化锌的化学式为Zn 1-xMg xO，x = 0.025-0.075，通过在由该类镁掺杂氧化锌与乙醇混合形成的溶液中加入适量的卤代烃，例如按照卤代烃和乙醇的体积比为1 : (2-4)的比例加入氯代烃，可显著提高溶液在常温下的稳定性，延长其在常温下的保存时间。 In some embodiments, the chemical formula of magnesium-doped zinc oxide is Zn 1-x Mg x O, x = 0.025-0.075, and an appropriate amount of halogenated hydrocarbon is added to a solution formed by mixing the magnesium-doped zinc oxide with ethanol. For example, adding chlorinated hydrocarbons in a ratio of 1: (2-4) according to the volume ratio of halogenated hydrocarbons and ethanol can significantly improve the stability of the solution at room temperature and prolong its storage time at room temperature.
乙醇作为溶剂，以溶解镁掺杂氧化锌。一些实施例中，镁掺杂氧化锌与乙醇的质量体积比为(20-60) mg: 1 mL，保证镁掺杂氧化锌能够以溶胶颗粒形式溶解在乙醇中，而且，当镁掺杂氧化锌与乙醇以该比例进行混合并加入适量的卤代烃时，例如按照卤代烃和乙醇的体积比为1 : (2-4)的比例加入氯代烃，可显著提高该溶液在常温下的稳定性，延长其在常温下的保存时间。Ethanol was used as a solvent to dissolve magnesium-doped zinc oxide. In some embodiments, the mass-to-volume ratio of magnesium-doped zinc oxide to ethanol is (20-60) mg: 1 mL, which ensures that magnesium-doped zinc oxide can be dissolved in ethanol in the form of sol particles, and when magnesium-doped zinc oxide is oxidized When zinc and ethanol are mixed at this ratio and an appropriate amount of halogenated hydrocarbons are added, for example, adding chlorinated hydrocarbons in a ratio of 1: (2-4) according to the volume ratio of halogenated hydrocarbons and ethanol, can significantly improve the solution at room temperature. stability and prolong its storage time at room temperature.
卤代烃作为添加剂，用于提高溶液的稳定性。卤代烃的用量影响着溶液的在常温下的稳定性，一些实施例中，卤代烃和乙醇的体积比为1 : (2-4)，以保证本申请实施例提供的溶液较镁掺杂氧化锌-乙醇具有更长的常温保存时间。Halogenated hydrocarbons are used as additives to improve solution stability. The amount of halogenated hydrocarbons affects the stability of the solution at room temperature. In some embodiments, the volume ratio of halogenated hydrocarbons to ethanol is 1: (2-4) to ensure that the solutions provided in the embodiments of the present application are more magnesium-doped Hetero zinc oxide-ethanol has a longer storage time at room temperature.
卤代烃为一类含有卤素原子的化合物，卤素原子含有孤对电子，该孤对电子可以与溶液中的镁掺杂氧化锌的Zn原子的空轨道相互作用，从而使得卤代烃结合镁掺杂氧化锌而形成配合物，防止溶解在乙醇中的镁掺杂氧化锌溶胶颗粒聚集，进而提高镁掺杂氧化锌-乙醇溶液在常温下的稳定性，并有效延长溶液在常温下的保存时间。Halogenated hydrocarbons are a class of compounds containing halogen atoms. The halogen atoms contain lone pairs of electrons that can interact with the empty orbitals of Zn atoms of magnesium-doped zinc oxide in solution, so that halogenated hydrocarbons combine with magnesium-doped zinc oxide. doped with zinc oxide to form complexes, preventing the aggregation of magnesium-doped zinc oxide sol particles dissolved in ethanol, thereby improving the stability of magnesium-doped zinc oxide-ethanol solution at room temperature, and effectively prolonging the storage time of the solution at room temperature .
一些实施例中，卤代烃中的卤素原子包括F、Cl、Br和I中的至少一种。进一步实施例中，卤代烃包括氯代芳烃和/或氯代烷烃，这类卤代烃能够溶解在乙醇中，而且，添加在包含镁掺杂氧化锌和乙醇的溶液中，可使得包含镁掺杂氧化锌和乙醇的溶液在常温下的保存时间明显延长。具体实施例中，氯代芳烃包括氯苯、二氯苯、氯甲苯、二氯甲苯和苄氯中的至少一种，氯代烷烃包括二氯甲烷、氯仿、二氯乙烷、二氯丙烷、二氯丁烷和氯代环己烷中的至少一种。In some embodiments, the halogen atoms in the halohydrocarbon include at least one of F, Cl, Br, and I. In further embodiments, the halogenated hydrocarbons include chlorinated aromatic hydrocarbons and/or chlorinated alkanes, such halogenated hydrocarbons are soluble in ethanol, and added to a solution comprising magnesium doped zinc oxide and ethanol, can result in magnesium The storage time of the solution doped with zinc oxide and ethanol at room temperature was significantly prolonged. In a specific embodiment, the chlorinated aromatic hydrocarbon includes at least one of chlorobenzene, dichlorobenzene, chlorotoluene, dichlorotoluene and benzyl chloride, and the chlorinated alkane includes dichloromethane, chloroform, dichloroethane, dichloropropane, At least one of dichlorobutane and chlorocyclohexane.
综上，本申请实施例通过在包含镁掺杂氧化锌和乙醇的溶液中添加卤代烃实现了有效延长溶液在常温下的保存时间的目的。一测试例中，卤化烃选为氯苯，镁掺杂氧化锌为Zn 1-xMg xO（x = 0.025-0.075），并按照氯苯和乙醇的体积比为1 : (2-4)的比例将氯苯和乙醇及镁掺杂氧化锌混合形成的溶液在常温下的保存时间在4天以上，甚至高达6天，然而镁掺杂氧化锌-乙醇溶液在常温下放置一天即出现明显沉淀。 To sum up, the embodiment of the present application achieves the purpose of effectively prolonging the storage time of the solution at room temperature by adding halogenated hydrocarbons to the solution containing magnesium-doped zinc oxide and ethanol. In a test example, the halogenated hydrocarbon is selected as chlorobenzene, the magnesium-doped zinc oxide is Zn 1-x Mg x O (x = 0.025-0.075), and the volume ratio of chlorobenzene and ethanol is 1: (2-4) The solution formed by mixing chlorobenzene with ethanol and magnesium-doped zinc oxide in the proportion of precipitation.
上述溶液组合物的制备方法可参考本领域的常规技术，使得镁掺杂氧化锌能够以溶胶颗粒的形式溶解在乙醇中，且使得各成分之间混合均匀，并获得澄清溶液即可。For the preparation method of the above solution composition, reference can be made to conventional techniques in the art, so that magnesium-doped zinc oxide can be dissolved in ethanol in the form of sol particles, and the components are mixed evenly to obtain a clear solution.
一些实施例中，上述溶液组合物的制备方法包括：将镁掺杂氧化锌、乙醇和卤代烃进行混合搅拌，直至形成澄清溶液。In some embodiments, the preparation method of the above solution composition includes: mixing and stirring magnesium-doped zinc oxide, ethanol and halogenated hydrocarbon until a clear solution is formed.
另一些实施例中，上述溶液组合物的制备方法工艺流程如图5所示，包括如下步骤：In other embodiments, the process flow of the preparation method of the above-mentioned solution composition is shown in Figure 5, and includes the following steps:
A 1、将镁掺杂氧化锌溶解在乙醇中，获得镁掺杂氧化锌-乙醇溶液； A1. Dissolving magnesium - doped zinc oxide in ethanol to obtain a magnesium-doped zinc oxide-ethanol solution;
A 2、将卤代烃加入镁掺杂氧化锌-乙醇溶液中，进行混合处理。 A2. Add halogenated hydrocarbons into magnesium- doped zinc oxide-ethanol solution, and carry out mixing treatment.
其中，将镁掺杂氧化锌溶解在乙醇中的方法以及进行混合处理的方法，可参考本领域的常规技术，例如机械搅拌和/或超声。Wherein, for the method of dissolving magnesium-doped zinc oxide in ethanol and the method of mixing treatment, reference may be made to conventional techniques in the art, such as mechanical stirring and/or ultrasound.
基于上述技术方案，本申请实施例还提供了一种膜层以及一种发光二极管。Based on the above technical solutions, the embodiments of the present application further provide a film layer and a light emitting diode.
相应地，一种膜层，由上述溶液组合物经过成膜处理而成。Correspondingly, a film layer is formed from the above solution composition through film forming treatment.
本申请实施例所提供的膜层，由上述溶液组合物经过成膜处理而成，由于上述溶液组合物稳定性好，使得本申请所提供的膜层质量得到一定程度的改善，有利于获得表面平整致密的膜层。The film layer provided by the examples of the present application is formed by the above-mentioned solution composition after film-forming treatment. Due to the good stability of the above-mentioned solution composition, the quality of the film layer provided by the present application is improved to a certain extent, which is beneficial to obtain the surface Flat and dense film layer.
其中，成膜处理的方法可参考本领域的常规技术，例如使用旋涂法、喷墨打印法等溶液法将上述溶液组合物沉积于基质上，然后进行干燥处理，从而获得镁掺杂氧化锌膜层。Wherein, the method of film-forming treatment can refer to conventional techniques in the art, for example, the above solution composition is deposited on the substrate by a solution method such as spin coating method, inkjet printing method, etc., and then drying treatment is performed to obtain magnesium-doped zinc oxide. film layer.
可以理解的是，基质作为用于成绩溶液组合物的载体，其材料种类和结构组成可参考本领域的常规技术，如一些实施例中，基质为刚性衬底、柔性衬底或金属电极，包括但不限于玻璃、硅晶片、聚碳酸酯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酰胺、聚醚砜、镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡、铅、铯、钡等。此外，基质还可以为形成有特定功能膜层的多层结构材料，例如形成有电子功能层的负极或形成有发光功能层的阳极，具体可根据实际生产条件以及所要制备的目标产物进行灵活调整。It can be understood that, the substrate is used as a carrier for the grade solution composition, and its material type and structural composition can refer to conventional techniques in the art. For example, in some embodiments, the substrate is a rigid substrate, a flexible substrate or a metal electrode, including but not limited to glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone, magnesium, calcium, sodium , potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, etc. In addition, the matrix can also be a multi-layer structural material formed with a specific functional film layer, such as a negative electrode formed with an electronic functional layer or an anode formed with a light-emitting functional layer, which can be flexibly adjusted according to the actual production conditions and the target product to be prepared. .
相应地，一种发光二极管，包括电子功能层，电子功能层包括上述膜层。Correspondingly, a light emitting diode includes an electronic functional layer, and the electronic functional layer includes the above-mentioned film layer.
本申请实施例所提供的发光二极管，其电子功能层为上述膜层，具有良好的发光效率。In the light-emitting diode provided by the embodiments of the present application, the electronic functional layer is the above-mentioned film layer, and has good luminous efficiency.
电子功能层为电子注入层、电子传输层和电子阻挡层等功能膜层的统称，一些实施例中，电子功能层为电子传输层。The electronic functional layer is a general term for functional film layers such as an electron injection layer, an electron transport layer, and an electron blocking layer. In some embodiments, the electronic functional layer is an electron transport layer.
本申请实施例的发光二极管的结构可参考本领域常规技术，在一些实施例中，发光二极管为正置型结构，阳极连接衬底作为底电极；在其他的实施例中，发光二极管为倒置型结构，阴极连接衬底作为底电极。进一步地，除了常规的阴极、阳极、发光层和电子功能层等基本功能膜层之外，在阳极和发光层之间还可以设置有空穴功能层，空穴功能层包括空穴注入层、空穴传输层和空子阻挡层。The structures of the light emitting diodes in the embodiments of the present application may refer to conventional technologies in the art. In some embodiments, the light emitting diodes are of an upright structure, and the anode is connected to the substrate as a bottom electrode; in other embodiments, the light emitting diodes are of an inverted structure. , the cathode is connected to the substrate as the bottom electrode. Further, in addition to the conventional basic functional film layers such as cathode, anode, light-emitting layer and electronic functional layer, a hole functional layer can also be provided between the anode and the light-emitting layer, and the hole functional layer includes a hole injection layer, A hole transport layer and a hole blocking layer.
一些实施例中，如图1所示，发光二极管包括：阳极1、空穴注入层21、空穴传输层22、发光层3、电子传输层42和阴极5，其中，阳极1连接衬底作为底电极，空穴注入层21设置在阳极1和发光层3之间，空穴传输层22设置在空穴注入层21和发光层3之间，电子传输层42设置在发光层3和阴极5之间。In some embodiments, as shown in FIG. 1 , the light emitting diode includes: an anode 1 , a hole injection layer 21 , a hole transport layer 22 , a light emitting layer 3 , an electron transport layer 42 and a cathode 5 , wherein the anode 1 is connected to the substrate as a Bottom electrode, the hole injection layer 21 is arranged between the anode 1 and the light-emitting layer 3, the hole transport layer 22 is arranged between the hole injection layer 21 and the light-emitting layer 3, and the electron transport layer 42 is arranged between the light-emitting layer 3 and the cathode 5 between.
在该发光二极管中，阳极、空穴注入层、空穴传输层、发光层和阴极的材料及其厚度可参考本领域的常规技术。In the light emitting diode, the materials and thicknesses of the anode, the hole injection layer, the hole transport layer, the light emitting layer and the cathode may refer to conventional techniques in the art.
衬底包括钢性衬底和柔性衬底，一些实施例中，衬底选为玻璃、硅晶片、聚碳酸酯、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚酰胺和聚醚砜中的至少一种。The substrate includes a rigid substrate and a flexible substrate. In some embodiments, the substrate is selected from glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate At least one of ethylene formate, polyamide, and polyethersulfone.
阳极包括导电金属和/或导电金属氧化物，导电金属包括但不限于镍、铂、钒、铬、铜、锌和金等或其合金，导电金属氧化物包括但不限于氧化锌、氧化铟、氧化锡、氧化铟锡(ITO)、氧化铟锌(IZO)、氟掺杂的氧化锡等。The anode includes conductive metals and/or conductive metal oxides, conductive metals include but are not limited to nickel, platinum, vanadium, chromium, copper, zinc and gold, etc. or their alloys, conductive metal oxides include but are not limited to zinc oxide, indium oxide, Tin oxide, indium tin oxide (ITO), indium zinc oxide (IZO), fluorine doped tin oxide, etc.
空穴注入层的材料选为具有良好空穴注入性能的材料，包括但不限于聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸（PEDOT:PSS）、酞菁铜（CuPc）、2,3,5,6-四氟-7,7',8,8'-四氰醌-二甲烷（F4-TCNQ）、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲（HATCN）、掺杂或非掺杂的过渡金属氧化物、掺杂或非掺杂的金属硫系化合物等；其中，过渡金属氧化物包括但不限于MoO 3、VO 2、WO 3、CuO等，金属硫系化合物包括但不限于MoS 2、MoSe 2、WS 2、WSe 2、CuS等。空穴注入层的厚度可以为10-150 nm。 The material of the hole injection layer is selected as a material with good hole injection performance, including but not limited to poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), copper phthalocyanine (CuPc) , 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano- 1,4,5,8,9,12-hexaazatriphenylene (HATCN), doped or undoped transition metal oxides, doped or undoped metal chalcogenides, etc.; Metal oxides include but are not limited to MoO 3 , VO 2 , WO 3 , CuO, etc., and metal chalcogenides include but are not limited to MoS 2 , MoSe 2 , WS 2 , WSe 2 , CuS and the like. The thickness of the hole injection layer may be 10-150 nm.
空穴传输层的材料选为具有良好空穴传输能力的有机材料，包括但不限于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)（TFB）、聚乙烯咔唑（PVK）、聚(N, N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)（Poly-TPD）、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)（PFB）、4,4',4''-三(咔唑-9-基)三苯胺（TCTA）、4,4'-二(9-咔唑)联苯（CBP）、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺（TPD）、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺（NPB）、掺杂石墨烯、非掺杂石墨烯、C60等。空穴传输层的厚度可以为10-150 nm。The material of the hole transport layer is selected as an organic material with good hole transport ability, including but not limited to poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB ), polyvinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (Poly-TPD), poly(9,9 -Dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4''-tris(carbazol-9-yl)triphenylamine ( TCTA), 4,4'-bis(9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- Biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), doped graphene, undoped graphene, C60, etc. The thickness of the hole transport layer may be 10-150 nm.
发光层的材料可选为本领域的常规材料，包括但不限于半导体量子点、钙钛矿量子点等。一些实施例中，发光层的材料选为半导体量子点。具体实施例中，发光层的材料选为II-VI族半导体量子点、III-V族半导体量子点和IV-VI族半导体量子点中的至少一种。其中，II-VI族半导体量子点包括但不限于CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe、HgZnSTe等，III-V族半导体量子点包括但不限于GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs、InAlPSb等，IV-VI族半导体量子点包括但不限于SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTe等。The material of the light-emitting layer can be selected from conventional materials in the art, including but not limited to semiconductor quantum dots, perovskite quantum dots, and the like. In some embodiments, the material of the light-emitting layer is selected as semiconductor quantum dots. In a specific embodiment, the material of the light-emitting layer is selected from at least one of group II-VI semiconductor quantum dots, group III-V semiconductor quantum dots, and group IV-VI semiconductor quantum dots. Among them, group II-VI semiconductor quantum dots include but are not limited to 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, HgZnSTe, etc., III-V semiconductor quantum dots including but not limited to GaN , GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaAs, 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, InAlPSb, etc. IV-VI semiconductor quantum dots include but are not limited to SnS, SnSe, SnTe , PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe, etc.
阴极可以选为单一金属或其合金，包括但不限于镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡、铅、铯、钡中的至少一种；或者，阴极选为多层结构材料，包括但不限于碱金属卤化物、碱土金属卤化物、碱金属氧化物等；或者，阴极选为多层结构材料和金属层的组合，金属层选为碱土金属和/或IIIA 族金属，包括但不限于LiF/Al、LiO 2/Al、LiF/Ca、Liq/Al、和BaF 2/Ca等。 The cathode can be selected from a single metal or an alloy thereof, including but not limited to at least one of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium; or , the cathode is selected as a multilayer structure material, including but not limited to alkali metal halides, alkaline earth metal halides, alkali metal oxides, etc.; or, the cathode is selected as a combination of a multilayer structure material and a metal layer, and the metal layer is selected as an alkaline earth metal and/or Group IIIA metals, including but not limited to LiF/Al, LiO 2 /Al, LiF/Ca, Liq/Al, and BaF 2 /Ca, etc.
上述发光二极管的制备方法可参考本领域的常规操作。For the preparation method of the above light-emitting diode, reference may be made to conventional operations in the art.
一些实施例中，上述发光二极管的制备方法工艺流程如图6所示，包括以下步骤：In some embodiments, the process flow of the above light-emitting diode manufacturing method is shown in FIG. 6 , including the following steps:
B 1、提供溶液组合物以及阴极； B 1 , providing a solution composition and a cathode;
B 2、将溶液组合物在阴极上进行成膜处理，获得电子功能层。 B2. The solution composition is subjected to film forming treatment on the cathode to obtain an electronic functional layer.
另一些实施例中，上述发光二极管的制备方法工艺流程如图7所示，还可以包括以下步骤：In other embodiments, the process flow of the above light-emitting diode manufacturing method is shown in FIG. 7 , and may further include the following steps:
B 1'、提供溶液组合物以及表面形成有发光层的阳极； B 1 ', providing a solution composition and an anode with a light-emitting layer formed on the surface;
B 2'、将溶液组合物在阳极上靠近发光层的一侧进行成膜处理，获得电子功能层。 B 2 ′, subjecting the solution composition to a film formation treatment on the side of the anode close to the light-emitting layer to obtain an electronic functional layer.
以下通过实施例对本申请所提供的溶液组合物的实施进行举例说明。The following examples illustrate the implementation of the solution composition provided by the present application.
实施例1-8和对比例1-3提供了一种溶液组合物，其组成如表1所示。Examples 1-8 and Comparative Examples 1-3 provide a solution composition, the composition of which is shown in Table 1.
表1Table 1
Figure dest_path_image001
Figure dest_path_image001
注：“-”表示无添加。Note: "-" means no addition.
上述溶液组合物的制备方法包括以下步骤：The preparation method of above-mentioned solution composition comprises the following steps:
1）将镁掺杂氧化锌加入乙醇中，搅拌直至镁掺杂氧化锌以胶体颗粒的形式溶解在乙醇溶剂中，获得镁掺杂氧化锌-乙醇溶液；1) adding magnesium-doped zinc oxide into ethanol, stirring until magnesium-doped zinc oxide is dissolved in the ethanol solvent in the form of colloidal particles to obtain magnesium-doped zinc oxide-ethanol solution;
2）将氯苯加入镁掺杂氧化锌-乙醇溶液中，搅拌直混合均匀。2) Add chlorobenzene to the magnesium-doped zinc oxide-ethanol solution, stir until it is evenly mixed.
将实施例1-1至实施例3-3和对比例1-3提供的溶液组合物，分别置于室温空气中，然后观察溶液状态的变化情况，结果如表2和图2-4所示，相对于镁掺杂氧化锌-乙醇溶液，本实施例提供的溶液组合物在常温下的稳定性可得到不同程度的增强，且当卤代烃和乙醇的体积比控制在1 : (2-4)的范围内时，可保证溶液在空气中放置第4天后依然保持澄清状态。The solution compositions provided by Example 1-1 to Example 3-3 and Comparative Example 1-3 were placed in the air at room temperature respectively, and then the changes in the state of the solution were observed. The results are shown in Table 2 and Figure 2-4. , relative to the magnesium-doped zinc oxide-ethanol solution, the stability of the solution composition provided in this embodiment at room temperature can be enhanced to varying degrees, and when the volume ratio of halogenated hydrocarbons and ethanol is controlled at 1: (2- 4), it can ensure that the solution remains clear after being placed in the air for 4 days.
表2Table 2
    第二天 the next day 第四天 fourth day 第六天 Day 6
对比例1 Comparative Example 1 出现明显沉淀 obvious precipitation - - - -
实施例1-1 Example 1-1 - - - - 溶液明显浑浊 The solution is visibly cloudy
实施例1-2 Example 1-2 - - - - 溶液明显浑浊 The solution is visibly cloudy
实施例1-3 Examples 1-3 出现明显沉淀 obvious precipitation - - - -
对比例2 Comparative Example 2 溶液明显浑浊 The solution is visibly cloudy - - - -
实施例2-1 Example 2-1 - - 溶液泛白 Solution blushing 溶液明显浑浊 The solution is visibly cloudy
实施例2-2 Example 2-2 - - - - 溶液澄清 solution clear
实施例2-3 Example 2-3 溶液明显浑浊 The solution is visibly cloudy - - - -
对比例3 Comparative Example 3 溶液明显浑浊 The solution is visibly cloudy - - - -
实施例3-1 Example 3-1 - - - - 溶液澄清 solution clear
实施例3-2 Example 3-2 - - - - 溶液澄清 solution clear
实施例3-3 Example 3-3 - - - - 溶液澄清 solution clear
注：“-”表示数据未记录。Note: "-" means that the data is not recorded.
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。The above descriptions are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the protection of the present application. within the range.

Claims (20)

  1. 一种溶液组合物，其特征在于，所述溶液组合物包括：镁掺杂氧化锌、乙醇和卤代烃。 A solution composition, characterized in that, the solution composition comprises: magnesium-doped zinc oxide, ethanol and halogenated hydrocarbons.
  2. 如权利要求1所述的溶液组合物，其特征在于，所述卤代烃中的卤素原子包括F、Cl、Br和I中的至少一种。 The solution composition of claim 1, wherein the halogen atoms in the halogenated hydrocarbon include at least one of F, Cl, Br and I.
  3. 如权利要求2所述的溶液组合物，其特征在于，所述卤代烃包括氯代芳烃和/或氯代烷烃。 The solution composition of claim 2, wherein the halogenated hydrocarbons comprise chlorinated aromatic hydrocarbons and/or chlorinated alkanes.
  4. 如权利要求3所述的溶液组合物，其特征在于，所述氯代芳烃包括氯苯、二氯苯、氯甲苯、二氯甲苯和苄氯中的至少一种。 The solution composition of claim 3, wherein the chlorinated aromatic hydrocarbon comprises at least one of chlorobenzene, dichlorobenzene, chlorotoluene, dichlorotoluene and benzyl chloride.
  5. 如权利要求3所述的溶液组合物，其特征在于，所述氯代烷烃包括二氯甲烷、氯仿、二氯乙烷、二氯丙烷、二氯丁烷和氯代环己烷中的至少一种。 The solution composition of claim 3, wherein the chlorinated alkane comprises at least one of dichloromethane, chloroform, dichloroethane, dichloropropane, dichlorobutane and chlorocyclohexane kind.
  6. 如权利要求1至5任一项所述的溶液组合物，其特征在于，所述镁掺杂氧化锌在溶液组合物中是以溶胶颗粒分散。 The solution composition according to any one of claims 1 to 5, wherein the magnesium-doped zinc oxide is dispersed as sol particles in the solution composition.
  7. 如权利要求1至5任一项所述的溶液组合物，其特征在于，所述卤代烃和所述乙醇的体积比为1 : (2-4)。 The solution composition according to any one of claims 1 to 5, wherein the volume ratio of the halogenated hydrocarbon to the ethanol is 1: (2-4).
  8. 如权利要求7所述的溶液组合物，其特征在于，所述卤代烃为氯苯，所述镁掺杂氧化锌以溶胶颗粒形式溶解在乙醇中。 The solution composition of claim 7, wherein the halogenated hydrocarbon is chlorobenzene, and the magnesium-doped zinc oxide is dissolved in ethanol in the form of sol particles.
  9. 如权利要求1至5、8任一项所述的溶液组合物，其特征在于，所述镁掺杂氧化锌的化学式为Zn 1-xMg xO，x = 0.025-0.075。 The solution composition according to any one of claims 1 to 5 and 8, wherein the chemical formula of the magnesium-doped zinc oxide is Zn 1-x Mg x O, and x = 0.025-0.075.
  10. 如权利要求1至5、8任一项所述的溶液组合物，其特征在于，所述镁掺杂氧化锌与所述乙醇的质量体积比为(20-60) mg : 1 mL。 The solution composition according to any one of claims 1 to 5 and 8, wherein the mass-volume ratio of the magnesium-doped zinc oxide to the ethanol is (20-60) mg: 1 mL.
  11. 一种溶液组合物的制备方法，其特征在于，包括如下步骤： A kind of preparation method of solution composition, is characterized in that, comprises the steps:
    将镁掺杂氧化锌、乙醇和卤代烃进行混合处理，直至形成澄清溶液。Magnesium-doped zinc oxide, ethanol, and halogenated hydrocarbons are mixed until a clear solution is formed.
  12. 如权利要求11所述的制备方法，其特征在于，将镁掺杂氧化锌、乙醇和卤代烃进行混合处理的方法包括如下步骤： The preparation method of claim 11, wherein the method for mixing magnesium-doped zinc oxide, ethanol and halogenated hydrocarbons comprises the following steps:
    将所述镁掺杂氧化锌溶解在所述乙醇中，获得镁掺杂氧化锌-乙醇溶液；Dissolving the magnesium-doped zinc oxide in the ethanol to obtain a magnesium-doped zinc oxide-ethanol solution;
    将所述卤代烃加入所述镁掺杂氧化锌-乙醇溶液中进行混合处理。The halogenated hydrocarbon is added to the magnesium-doped zinc oxide-ethanol solution for mixing treatment.
  13. 一种膜层，其特征在于，由权利要求1至10任一项所述的溶液组合物或由权利要求11至12任一项所述制备方法制备的溶液组合物经过成膜处理而成。 A film layer, characterized in that, the solution composition according to any one of claims 1 to 10 or the solution composition prepared by the preparation method according to any one of claims 11 to 12 is formed by film-forming treatment.
  14. 一种发光二极管，其特征在于，包括电子功能层，所述电子功能层包括权利要求13所述的膜层。 A light emitting diode is characterized by comprising an electronic functional layer, and the electronic functional layer comprises the film layer of claim 13 .
  15. 如权利要求14所述的发光二极管，其特征在于，所述电子功能层为电子传输层。 The light emitting diode of claim 14, wherein the electronic functional layer is an electron transport layer.
  16. 如权利要求15所述的发光二极管，其特征在于，所述发光二极管还包括阳极、空穴注入层、空穴传输层、发光层和阴极，其中，阳极连接衬底作为底电极，空穴注入层设置在阳极和发光层之间，空穴传输层设置在空穴注入层和发光层之间，电子传输层设置在发光层和阴极之间。 The light emitting diode of claim 15, wherein the light emitting diode further comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode, wherein the anode is connected to the substrate as a bottom electrode, and the hole injects The layer is disposed between the anode and the light-emitting layer, the hole-transporting layer is disposed between the hole-injection layer and the light-emitting layer, and the electron-transporting layer is disposed between the light-emitting layer and the cathode.
  17. 如权利要求15所述的发光二极管，其特征在于，所述发光二极管还包括阳极、空穴注入层、空穴传输层、发光层和阴极，其中，阴极连接衬底作为底电极，电子传输层设置在阴极和发光层之间，空穴注入层设置在阳极和发光层之间，空穴传输层设置在发光层和空穴注入层之间。 The light emitting diode of claim 15, wherein the light emitting diode further comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer and a cathode, wherein the cathode is connected to the substrate as a bottom electrode, and the electron transport layer It is arranged between the cathode and the light-emitting layer, the hole injection layer is arranged between the anode and the light-emitting layer, and the hole transport layer is arranged between the light-emitting layer and the hole injection layer.
  18. 如权利要求16或17所述的发光二极管，其特征在于，所述阳极包括导电金属和/或导电金属氧化物，导电金属选自镍、铂、钒、铬、铜、锌和金的至少之一，导电金属氧化物包括氧化锌、氧化铟、氧化锡、氧化铟锡、氧化铟锌、氟掺杂的氧化锡的至少之一；和/或， The light emitting diode according to claim 16 or 17, wherein the anode comprises a conductive metal and/or a conductive metal oxide, and the conductive metal is selected from at least one of nickel, platinum, vanadium, chromium, copper, zinc and gold 1. The conductive metal oxide includes at least one of zinc oxide, indium oxide, tin oxide, indium tin oxide, indium zinc oxide, and fluorine-doped tin oxide; and/or,
    所述空穴注入层的材料包括PEDOT:PSS、CuPc、F4-TCNQ、HATCN、掺杂或非掺杂的过渡金属氧化物、掺杂或非掺杂的金属硫系化合物的至少之一；其中，过渡金属氧化物包括MoO 3、VO 2、WO 3、CuO至少之一，金属硫系化合物包括MoS 2、MoSe 2、WS 2、WSe 2、CuS至少之一；和/或， The material of the hole injection layer includes at least one of PEDOT:PSS, CuPc, F4-TCNQ, HATCN, doped or undoped transition metal oxide, and doped or undoped metal chalcogenide; wherein , the transition metal oxide includes at least one of MoO 3 , VO 2 , WO 3 , and CuO, and the metal chalcogenide compound includes at least one of MoS 2 , MoSe 2 , WS 2 , WSe 2 , and CuS; and/or,
    所述空穴注入层的厚度优选为10-150nm；和/或，The thickness of the hole injection layer is preferably 10-150 nm; and/or,
    所述空穴传输层的材料包括TFB、PVK、Poly-TPD、PFB、TCTA、CBP、TPD、NPB、掺杂石墨烯、非掺杂石墨烯、C60的至少之一；和/或，The material of the hole transport layer includes at least one of TFB, PVK, Poly-TPD, PFB, TCTA, CBP, TPD, NPB, doped graphene, undoped graphene, and C60; and/or,
    所述空穴传输层的厚度优选为10-150nm；和/或，The thickness of the hole transport layer is preferably 10-150 nm; and/or,
    所述发光层的材料包括半导体量子点和钙钛矿量子点；其中，所述半导体量子点选自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、HgZnSTe、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、InAlPSb、SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTe中的至少之一；和/或，The material of the light-emitting layer includes semiconductor quantum dots and perovskite quantum dots; wherein, the semiconductor quantum dots are 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, CdHgSeS, CdHgSeTe, CdHgSTe, CdZnSte, HgZnSeS GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaAs, 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, InAlPSb, SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, at least one of SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; and/or,
    所述阴极选自镁、钙、钠、钾、钛、铟、钇、锂、钆、铝、银、锡、铅、铯、钡中的至少一种；或者，所述阴极为多层结构材料，选自碱金属卤化物、碱土金属卤化物、碱金属氧化物中的至少一种；或者，所述阴极为多层结构材料和和金属层的组合，所述金属层为选自LiF/Al、LiO 2/Al、LiF/Ca、Liq/Al、和BaF 2/Ca中的至少一种。 The cathode is selected from at least one of magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, and barium; or, the cathode is a multi-layer structural material , selected from at least one of alkali metal halides, alkaline earth metal halides, and alkali metal oxides; or, the cathode is a combination of a multi-layer structural material and a metal layer, and the metal layer is selected from LiF/Al , at least one of LiO 2 /Al, LiF/Ca, Liq/Al, and BaF 2 /Ca.
  19. 一种发光二极管的制备方法，其特征在于，包括如下步骤： A method for preparing a light-emitting diode, comprising the following steps:
    提供权利要求1至10任一项所述的溶液组合物或由权利要求11至12任一项所述制备方法制备的溶液组合物以及阴极；Provide the solution composition of any one of claims 1 to 10 or the solution composition prepared by the preparation method of any one of claims 11 to 12, and a cathode;
    将溶液组合物在阴极上进行成膜处理，获得电子功能层。The solution composition is subjected to film-forming treatment on the cathode to obtain an electronic functional layer.
  20. 一种发光二极管的制备方法，其特征在于，包括如下步骤： A method for preparing a light-emitting diode, comprising the following steps:
    提供权利要求1至10任一项所述的溶液组合物或由权利要求11至12任一项所述制备方法制备的溶液组合物以及表面形成有发光层的阳极；Provide the solution composition according to any one of claims 1 to 10 or the solution composition prepared by the preparation method according to any one of claims 11 to 12, and an anode with a light-emitting layer formed on the surface;
    将溶液组合物在阳极上靠近发光层的一侧进行成膜处理，获得电子功能层。The solution composition is subjected to film-forming treatment on the side of the anode near the light-emitting layer to obtain an electronic functional layer.
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