WO2020107978A1 - Diode électroluminescente à points quantiques et son procédé de préparation - Google Patents

Diode électroluminescente à points quantiques et son procédé de préparation Download PDF

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Publication number
WO2020107978A1
WO2020107978A1 PCT/CN2019/103478 CN2019103478W WO2020107978A1 WO 2020107978 A1 WO2020107978 A1 WO 2020107978A1 CN 2019103478 W CN2019103478 W CN 2019103478W WO 2020107978 A1 WO2020107978 A1 WO 2020107978A1
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Prior art keywords
cation
ionic liquid
quantum dot
liquid material
dot light
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Chinese (zh)
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梁柱荣
曹蔚然
钱磊
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TCL Technology Group Co Ltd
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TCL Technology Group Co Ltd
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Priority claimed from CN201811443013.0A external-priority patent/CN111244301A/zh
Priority claimed from CN201811443037.6A external-priority patent/CN111244302B/zh
Application filed by TCL Technology Group Co Ltd filed Critical TCL Technology Group Co Ltd
Publication of WO2020107978A1 publication Critical patent/WO2020107978A1/fr
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour

Definitions

  • the present application relates to the field of display technology, in particular to a quantum dot light-emitting diode and a preparation method thereof.
  • Quantum dots light-emitting diode is an emerging display device, its principle and structure are similar to organic light-emitting diode (OLED): namely quantum dots and organic/inorganic semiconductor Driven by an external DC electric field, excitons recombine and emit light.
  • OLED organic light-emitting diode
  • QLED is characterized by quantum dots whose luminescent material is prepared by colloid method.
  • the unique quantum size effect, macroscopic quantum tunneling effect, quantum size effect and surface effect of quantum dots make it exhibit excellent physical properties, especially excellent optical properties.
  • colloidal quantum dots have the advantages of adjustable spectrum, large luminous intensity, high color purity, and single-light source can excite multi-color fluorescence. It is expected to become the next generation of flat panel displays and has broad development prospects.
  • the preparation process is simple, the material utilization rate is low, and the preparation efficiency is high, and it is considered to be a new technology with great potential for flat panel displays in the future.
  • QLED has many advantages over OLED, QD and some of the transport layer materials are nanoparticles in solution phase. Compared with the mature evaporation process of OLED film, the film formation performance is not easy to control, and it is prone to incomplete coverage.
  • One of the purposes of the embodiments of the present application is to provide a quantum dot light-emitting diode and a preparation method thereof, aiming to solve the uneven interface of the electron transport layer of the existing device and the phenomenon of "pinhole" in the film layer, thereby reducing the device Technical issues of luminous efficiency and service life.
  • a quantum dot light emitting diode including an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode, and electrons are provided between the quantum dot light emitting layer and the cathode A transport layer.
  • the surface of the electron transport layer is provided with an ionic liquid material.
  • a surface of the electron transport layer near the cathode is provided with a first ionic liquid material layer composed of the ionic liquid material.
  • the cathode, the first ionic liquid material layer, and the electron transport layer are stacked.
  • the thickness of the first ionic liquid material layer is 5-80 nm.
  • a surface of the electron transport layer near the quantum dot light emitting layer is provided with a second ionic liquid material layer composed of the ionic liquid material.
  • the electron transport layer, the second ionic liquid material layer, and the quantum dot light-emitting layer are stacked.
  • the thickness of the first ionic liquid material layer is 5-80 nm.
  • the material of the electron transport layer is one or more nanoparticles selected from transition metal oxides and transition metal chalcogenide compounds.
  • the surface of the electron transport layer includes one or more of the ionic liquid materials, and the ionic liquid materials are salts composed of organic cations and inorganic anions; wherein,
  • the organic cation is selected from one of alkyl quaternary ammonium ions, alkyl quaternary phosphorus ions, alkyl substituted imidazole ions, alkyl substituted pyridine ions, and the inorganic anion is selected from halogen ions and inorganic acid anions One kind.
  • the alkyl quaternary ammonium ion is selected from N,N-diethyl-N-methyl-N-(n-propyl) ammonium cation and N,N-diethyl-N-methyl One of the amine-(2-methoxyethyl) ammonium cations; or,
  • the alkyl quaternary phosphorus ion is selected from one of tetradecyl tributyl phosphorus cation, tetrahydroxymethyl phosphorus cation, ethyl tributyl phosphorus cation and tetrabutyl phosphorus cation; or,
  • the alkyl-substituted imidazole ion is selected from 1-butyl-3-methylimidazole cation, 1-ethyl-3-methylimidazole cation, 1-octyl-3-methylimidazole cation, 1-decyl One of -3-methylimidazole cation, 1-hexyl-3-methylimidazole cation and 1-methyl-3-n-octylimidazole cation; or,
  • the alkyl substituted pyridine ion is selected from the group consisting of N-ethylpyridine cation, N-butylpyridine cation, N-hexylpyridine cation, N-octylpyridine cation and N-methyl-N-propylpyridine cation One; or,
  • the halogen ion is selected from F -, Cl -, Br - and I - a medium; or
  • the inorganic acid anions selected from BF 4 -, PF 6 -, CF 3 SO 3 -, CF 3 COO -, (CF 3 SO 2) 3 C -, (C 2 F 5 SO 2) 3 C -, (CF 3 SO 2) 2 N -, NO 2 -, NO 3 -, ClO 4 - and C 8 H 17 SO 4 - in a medium.
  • the organic cation in the ionic liquid material is selected from one of alkyl quaternary ammonium ion and alkyl substituted imidazole ion.
  • the organic cation in the ionic liquid material is an asymmetric cation
  • a hydrogen bond is formed between the organic cation and the inorganic anion in the ionic liquid material.
  • the ionic liquid material is selected from 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3 -Methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole chloride, 1-decyl-3-methylimidazole hexafluorophosphate Salt, 1-hexyl-3-methylimidazole tetrafluoroborate, 1-methyl-3-n-octylimidazole tetrafluoroborate and N,N-diethyl-N-methyl-N-( 2-methoxyethyl) tetrafluoroborate quaternary ammonium salt.
  • a method for manufacturing a quantum dot light emitting diode including the following steps:
  • An ionic liquid material is prepared on the substrate.
  • the step of preparing an ionic liquid material on the substrate includes: directly depositing one or more ionic liquid materials on the substrate, and performing an annealing process;
  • the temperature of the annealing treatment is 40 ⁇ 220°C; and/or,
  • the annealing time is 5 ⁇ 240min.
  • the step of preparing the ionic liquid material on the substrate includes preparing a solution containing one or more ionic liquid materials, depositing the solution on the substrate, and performing an annealing process.
  • the concentration of the ionic liquid in the solution is 0.2-60 mg/mL; and/or,
  • the temperature of the annealing treatment is 40 ⁇ 220°C; and/or,
  • the annealing time is 5 ⁇ 240min.
  • the ionic liquid material is a salt composed of an organic cation and an inorganic anion; wherein, the organic cation is selected from alkyl quaternary ammonium ions, alkyl quaternary phosphorus ions, alkyl substituted imidazole ions, alkyl One of substituted pyridine ions, the inorganic anion is selected from one of halogen ions and inorganic acid anions.
  • the alkyl quaternary ammonium ion is selected from N,N-diethyl-N-methyl-N-(n-propyl) ammonium cation and N,N-diethyl-N-methyl One of the amine-(2-methoxyethyl) ammonium cations; or,
  • the alkyl quaternary phosphorus ion is selected from one of tetradecyl tributyl phosphorus cation, tetrahydroxymethyl phosphorus cation, ethyl tributyl phosphorus cation and tetrabutyl phosphorus cation; or,
  • the alkyl-substituted imidazole ion is selected from 1-butyl-3-methylimidazole cation, 1-ethyl-3-methylimidazole cation, 1-octyl-3-methylimidazole cation, 1-decyl One of -3-methylimidazole cation, 1-hexyl-3-methylimidazole cation and 1-methyl-3-n-octylimidazole cation; or,
  • the alkyl substituted pyridine ion is selected from the group consisting of N-ethylpyridine cation, N-butylpyridine cation, N-hexylpyridine cation, N-octylpyridine cation and N-methyl-N-propylpyridine cation One; or,
  • the halogen ion is selected from F -, Cl -, Br - and I - a medium; or
  • the inorganic acid anions selected from BF 4 -, PF 6 -, CF 3 SO 3 -, CF 3 COO -, (CF 3 SO 2) 3 C -, (C 2 F 5 SO 2) 3 C -, (CF 3 SO 2) 2 N -, NO 2 -, NO 3 -, ClO 4 - and C 8 H 17 SO 4 - in a medium. .
  • the beneficial effect of the quantum dot light-emitting diode is that the quantum dot light-emitting diode is provided with an ionic liquid material on the surface of the electron transport layer, because the ionic liquid material has stable chemical properties, large adhesion, and strong ability to block water and oxygen.
  • the ionic liquid material can form a dense layer of ionic liquid material, on the one hand, it can improve carrier transport, passivate the defects of the surface of the electron transport layer, thereby reducing the carrier transport barrier inside the device and improving the luminous performance of the device
  • the ionic liquid material covers the surface of the electron transport layer, which effectively overcomes the defects of incomplete coverage of the electron transport layer surface or the existence of pinholes or uneven surfaces.
  • the introduction of ionic liquid material can In the process of bending and folding the device, the electron transport layer is effectively protected, and the self-repairing function of the crack is realized, thereby improving the designability and service life of the device.
  • the beneficial effect of the preparation method of the quantum dot light-emitting diode is that the preparation method is simple in process and low in cost, and directly prepares an ionic liquid material on the substrate.
  • the ionic liquid material not only has strong conductivity, stable properties, It has the outstanding advantages of good designability, small vapor pressure, large adhesion, green and pollution-free, and has the characteristics of compact structure, good thermal stability and good ability to block water and oxygen, so it can be passed through different functional layers on the substrate surface.
  • the prepared ionic liquid material is directly used to modify the functional layer, so that the luminous performance and service life of the device can be improved.
  • FIG. 1 is a schematic flow chart of a method for manufacturing a quantum dot light-emitting diode according to an embodiment of the application;
  • FIG. 2 is a schematic structural diagram of a quantum dot light-emitting diode according to an embodiment of the application.
  • the ionic liquid refers to a salt that is liquid at room temperature or near room temperature and is composed entirely of anions and cations. It is also called a low-temperature molten salt.
  • the ionic liquid has strong conductivity, stable properties, and resistance. High heat, low vapor pressure, non-flammable, green and non-polluting, through the design of anions and cations, it can adjust all aspects of material performance and other outstanding advantages. Using the unique properties of ionic liquid materials, ionic liquid materials are provided on the surface of the device's electron transport layer.
  • Some embodiments of the present application provide a quantum dot light emitting diode, including an anode, a cathode, and a quantum dot light emitting layer disposed between the anode and the cathode, and electrons are provided between the quantum dot light emitting layer and the cathode A transport layer.
  • the surface of the electron transport layer is provided with an ionic liquid material.
  • the quantum dot light-emitting diode provided by the embodiment of the present application is provided with an ionic liquid material on the surface of the electron transport layer. Because the ionic liquid material has the characteristics of stable chemical properties, large adhesion, and strong ability to block water and oxygen, it can form a dense layer of ions The liquid material layer, on the one hand, can improve carrier transport, passivate defects on the surface of the electron transport layer, thereby reducing the carrier transport barrier inside the device, and improving the luminous performance of the device; at the same time, the ionic liquid material covers the electron transport layer The surface effectively overcomes the defects of incomplete coverage of the electron transport layer surface or the existence of pinholes or uneven surfaces.
  • the introduction of ionic liquid materials can effectively protect the electrons during the bending and folding process of the device The transmission layer, and realize the self-repair function of the crack, thereby improving the designability and service life of the device.
  • the surface of the electron transport layer includes one or more of the ionic liquid materials, and the ionic liquid materials are salts composed of organic cations and inorganic anions; wherein, the organic cations are selected from alkyl groups Quaternary ammonium ion [NR x H 4-x ] + , alkyl quaternary phosphorus ion [PR x H 4-x ] + , alkyl substituted imidazole ion [R 1 R 3 im] + , alkyl substituted pyridine ion [ One of RPy] + , the inorganic anion is selected from one of halogen ions and inorganic acid anions.
  • the organic cations are selected from alkyl groups Quaternary ammonium ion [NR x H 4-x ] + , alkyl quaternary phosphorus ion [PR x H 4-x ] + , alkyl substituted imidazole ion [R 1 R 3 im] + ,
  • the alkyl quaternary ammonium ion is selected from N,N-diethyl-N-methyl-N-(n-propyl) ammonium cation and N,N-diethyl-N-methyl-( 2-methoxyethyl) one of ammonium cations;
  • the alkyl quaternary phosphorus ion is selected from the group consisting of tetradecyl tributylphosphonium cation, tetrahydroxymethylphosphonium cation, ethyltributylphosphonium cation and tetrabutyl One of the basic phosphorus cations;
  • the alkyl-substituted imidazole ions are selected from 1-butyl-3-methylimidazole cation, 1-ethyl-3-methylimidazole cation, 1-octyl-3-methyl One of the imidazole cation, 1-decyl-3-methylimidazole c
  • the organic cation is an alkyl quaternary ammonium ion or an alkyl-substituted imidazole ion.
  • the organic cation is an asymmetric cation; and/or, a hydrogen bond is formed between the organic cation and the inorganic anion.
  • ionic liquid An important index for evaluating the practicality of ionic liquid is its melting point.
  • the structure of ionic liquid and its melting point have a decisive relationship, which is directly related to the use temperature range of ionic liquid.
  • the melting point gradually decreases as the anion volume increases, and the melting point of different chlorides can be compared to understand the effect of the cation on the melting point.
  • the melting point gradually decreases as the volume of the cation increases.
  • the ionic liquid is asymmetric. The lower the structural symmetry of the ionic liquid, the weaker the intermolecular force, the more uniform the cation or anion charge distribution, the lower the melting point of the ionic liquid.
  • M.p. descending order of anion generating compound is: Cl -> NO 2 -> NO 3 -> AlCl 4 -> BF 4 -> CF 3 SO 3> CF 3 CO 2 -.
  • the viscosity of ionic liquids is dozens to hundreds of times that of water.
  • the structure of anions and cations has a great influence on the viscosity of the ionic liquid: the carbon chain length of the cation substituent increases and the viscosity of the ionic liquid increases.
  • the ionic liquid with a cation of [bmin] has a much higher viscosity than [emin]; Alkyl branching increases the viscosity of ionic liquids.
  • the ionic liquid with cation [ibmin] has a higher viscosity than [bmin].
  • the viscosity of ionic liquids is mainly determined by van der Waals force and hydrogen bonding, and the volume of anions decreases.
  • the van der Waals force is reduced, the electrostatic effect is increased, and the viscosity is reduced; the anion basicity is large, and the viscosity is small, such as [emin]F(HF)n, the anion basicity is large, and the viscosity is the smallest. Therefore, after the anion and cation form a hydrogen bond, the viscosity of the ionic liquid increases; the relationship between the viscosity of the ionic liquid and the temperature becomes the Vogel-Tammann-Fulchers equation.
  • the organic cation is an asymmetric cation
  • the ionic liquid material that forms a hydrogen bond between the organic cation and the inorganic anion not only ensures a low melting point but also has a very good viscosity.
  • the ionic liquid material is selected from 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-ethyl- 3-Methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole chloride, 1-decyl-3-methylimidazole hexafluorophosphate Phosphate, 1-hexyl-3-methylimidazole tetrafluoroborate, 1-methyl-3-n-octylimidazole tetrafluoroborate and N,N-diethyl-N-methyl-N- At least one of (2-methoxyethyl) tetrafluoroborate quaternary ammonium salts.
  • a surface of the electron transport layer near the cathode is provided with a first ionic liquid material layer composed of the ionic liquid material.
  • a first ionic liquid material layer is provided on the surface between the cathode and the electron transport layer, which can not only passivate the electron transport layer, but also improve the cathode. Because the ionic liquid material has the characteristics of stable chemical properties, high adhesion, and strong ability to block water and oxygen, after forming a dense layer of the first ionic liquid material, on the one hand, it can improve carrier transmission and passivate the cathode surface defects.
  • the first ionic liquid material layer covers the surface of the cathode, which effectively overcomes the device caused by the incomplete coverage of the cathode surface or the presence of pinholes or uneven surfaces, etc.
  • the problems of serious leakage current and rapid decay of device life improve the life of device.
  • the cathode, the first ionic liquid material layer and the electron transport layer are stacked. In this way, the first ionic liquid material layer can not only improve the cathode surface well, but also passivate the electron transport stack well, effectively overcoming the defects of insufficient coverage of the electron transport stack near the cathode surface or the existence of pinholes or uneven surfaces. That is, the interface between the cathode and the electron transport layer can be better improved.
  • the thickness of the first ionic liquid material layer is: 5-80 nm.
  • a surface of the electron transport layer near the quantum dot light-emitting layer is provided with a second ionic liquid material layer composed of the ionic liquid material.
  • the second ionic liquid material layer can improve carrier transport and passivate defects on the surface of the functional layer (ie, the surface of the electron transport layer), thereby reducing the carrier transport barrier inside the device and improving the luminous performance of the device;
  • the second ionic liquid material layer covers the surface of the electron transport layer, which effectively overcomes the defects of incomplete coverage of the electron transport layer surface or the presence of pinholes or uneven surfaces.
  • the introduction of ionic liquid material Layer which can effectively protect the electron transport layer during the bending and folding process of the device, and realize the self-repair function of the crack, thereby improving the designability and service life of the device.
  • the electron transport layer, the second ionic liquid material layer and the quantum dot light-emitting layer are formed by stacking.
  • the second ionic liquid material layer can further passivate the quantum dot light-emitting layer, effectively overcoming the quantum dot light-emitting layer close to the electron transport layer surface incomplete coverage or the presence of pinholes or uneven surface defect.
  • the thickness of the first ionic liquid material layer is: 5-80 nm.
  • a hole functional layer is provided between the anode and the quantum dot light-emitting layer.
  • a hole injection layer or a stacked hole injection layer and hole transport layer, where the hole transport layer is adjacent to the quantum dot light emitting layer.
  • a quantum dot light-emitting diode including an anode, a cathode, and a quantum dot light-emitting layer disposed between the anode and the cathode, the quantum dot light-emitting layer being disposed between the cathode
  • an electron transport layer a surface of the electron transport layer near the cathode is provided with a first ionic liquid material layer, and a surface of the electron transport layer near the quantum dot light emitting layer is provided with a second ionic liquid material layer.
  • the ionic liquid material layer is provided on the surface of the cathode close to the electron transport layer and the surface of the electron transport layer close to the quantum dot light-emitting layer, thereby forming two ionic liquid material layers, which are further increased by a synergistic effect
  • the number of electrons injected into the quantum dot light-emitting layer further improves the luminous efficiency of the device.
  • the ionic liquid materials in the first ionic liquid material layer and the second ionic liquid material layer are salts composed of organic cations and inorganic anions; wherein the organic cations are selected from alkyl quaternary ammonium ions [NR x H 4-x ] + , alkyl quaternary phosphorus ion [PR x H 4-x ] + , alkyl substituted imidazole ion [R 1 R 3 im] + , alkyl substituted pyridine ion [RPy] + One, the inorganic anion is selected from one of halogen ions and inorganic acid anions.
  • the organic cations are selected from alkyl quaternary ammonium ions [NR x H 4-x ] + , alkyl quaternary phosphorus ion [PR x H 4-x ] + , alkyl substituted imidazole ion [R 1 R 3 im] + , alkyl substituted pyridine i
  • the ionic liquid material in the second ionic liquid material layer may be the same as or different from the ionic liquid material in the first ionic liquid material layer, and may specifically be selected within the range of ionic liquid material selection as explained above.
  • the ionic liquid material in the first ionic liquid material and the second ionic liquid material layer is selected from 1-butyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole hexafluoro Phosphate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole chloride, 1-decyl -3-Methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole tetrafluoroborate, 1-methyl-3-n-octylimidazole t
  • the material of the electron transport layer is one or more nanoparticles in the transition metal oxide and the transition metal chalcogenide compound.
  • the transition metal oxide includes one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, and the metal sulfur compound Including CdS, ZnS, MoS, WS, CuS.
  • the film layer composed of these nanoparticles is prone to cracks and other problems that lead to device failure, and the introduction of an ionic liquid material layer can effectively protect the nanoparticles in the process of bending and folding the device to form an electron transport layer and achieve The self-repair function of the crack improves the designability and service life of the device.
  • the embodiments of the present application also provide a method for manufacturing a quantum dot light emitting diode, as shown in FIG. 1, including the following steps:
  • the preparation method of the quantum dot light-emitting diode provided by the embodiment of the present application has a simple process and low cost.
  • the ionic liquid material is directly prepared on the substrate.
  • the ionic liquid material layer not only has strong conductivity, stable properties, good designability, and steam. It has the outstanding advantages of small compaction, large adhesion, green and no pollution, and has the characteristics of compact structure, good thermal stability and good ability to block water and oxygen, so it can be coated with different functional layers on the surface of the substrate to directly prepare the prepared ionic liquid materials.
  • the layer is used to modify the functional layer, so that the light emitting performance and service life of the device can be improved.
  • an ionic liquid material is prepared on the substrate to form a first ionic liquid material layer or a second ionic liquid material layer.
  • the position is on the surface of the electron transport layer close to the cathode: specifically, in the above step S01; if a cathode is provided on the surface of the substrate, the first ionic liquid material layer is directly prepared on the cathode surface, and then An electron transport layer is prepared on the first ionic liquid material layer; if an electron transport layer is provided on the surface of the substrate (in this case, the substrate is an anode substrate), the first ionic liquid material layer is directly prepared on the surface of the electron transport layer, and then on the first ionic liquid The cathode is prepared on the surface of the material layer.
  • the preparation process is basically the same as the first ionic liquid material layer, and the position is on the surface of the electron transport layer close to the quantum dot light-emitting layer.
  • the step of preparing an ionic liquid material layer on the substrate includes: the ionic liquid material can be directly deposited on the substrate for annealing treatment; or, the ionic liquid-containing material can be formulated After the solution, the solution is deposited on the substrate and then annealed.
  • the solvent in the solution is an organic solvent.
  • Organic solvents include but are not limited to one or more of saturated hydrocarbons, unsaturated hydrocarbons, aromatic hydrocarbons, alcohol solvents, ether solvents, ketone solvents, nitrile solvents, ester solvents, and derivatives thereof Of mixed organic solvents.
  • the solvent for dissolving the ionic liquid is an alcoholic solvent, including but not limited to one or more of monohydric alcohol, polyhydric alcohol and aromatic alcohol, specifically including but not limited to methanol, ethanol, ethylene glycol, propanol , Propylene glycol, glycerol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, n-butanol, benzyl alcohol, phenethyl alcohol one or more.
  • alcoholic solvent including but not limited to one or more of monohydric alcohol, polyhydric alcohol and aromatic alcohol, specifically including but not limited to methanol, ethanol, ethylene glycol, propanol , Propylene glycol, glycerol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, n-butanol, benzyl alcohol, phenethyl alcohol one or
  • the above method for preparing the ionic liquid material layer is a solution film forming method, including but not limited to spin coating method, printing method, blade coating method, dipping and pulling method, dipping method, spraying method, roll coating method, casting method, slit One or more of the coating method and the strip coating method.
  • the temperature of the above annealing treatment is 40 ⁇ 220°C; the time of the above annealing treatment is 5 ⁇ 240min.
  • the preparation of a positive-structure quantum dot light-emitting diode includes the following steps:
  • Step S1 preparing an anode on the substrate
  • Step S2 preparing a hole functional layer on the anode (specifically, a hole injection layer, or a hole injection layer and a hole transport layer stacked in sequence);
  • Step S3 preparing a quantum dot light-emitting layer on the hole functional layer
  • Step S4 preparing an electron transport layer on the quantum dot light-emitting layer
  • Step S5 preparing a first ionic liquid material layer on the electron transport layer
  • Step S6 prepare a cathode on the first ionic liquid material layer.
  • the preparation of a positive-structure quantum dot light-emitting diode includes the following steps:
  • Step S1 preparing an anode on the substrate
  • Step S2 preparing a hole functional layer on the anode (specifically, a hole injection layer, or a hole injection layer and a hole transport layer stacked in sequence);
  • Step S3 preparing a quantum dot light-emitting layer on the hole functional layer
  • Step S4 preparing a second ionic liquid material layer on the quantum dot light-emitting layer
  • Step S5 preparing an electron transport layer on the second ionic liquid material layer
  • Step S6 preparing a cathode on the electron transport layer.
  • FIG. 1 the structure of a positive-type quantum dot light-emitting diode is shown in FIG. 1, and its preparation includes the following steps:
  • Step S1 preparing an anode on the substrate
  • Step S2 preparing a hole functional layer on the anode (specifically, a hole injection layer, or a hole injection layer and a hole transport layer stacked in sequence);
  • Step S3 preparing a quantum dot light-emitting layer on the hole functional layer
  • Step S4 preparing a second ionic liquid material layer on the quantum dot light-emitting layer
  • Step S5 preparing an electron transport layer on the second ionic liquid material layer
  • Step S6 preparing a first ionic liquid material layer on the electron transport layer
  • Step S7 prepare a cathode on the first ionic liquid material layer.
  • the preparation of an inverse structure quantum dot light-emitting diode includes the following steps:
  • Step S1 preparing a cathode on the substrate
  • Step S2 preparing a first ionic liquid material layer on the cathode
  • Step S3 preparing an electron transport layer on the first ionic liquid material layer
  • Step S4 preparing a quantum dot light-emitting layer on the electron transport layer
  • Step S4 preparing a hole function layer on the quantum dot light-emitting layer
  • Step S5 prepare an anode on the hole functional layer.
  • the preparation of an inverse structure quantum dot light-emitting diode includes the following steps:
  • Step S1 preparing a cathode on the substrate
  • Step S2 preparing a first ionic liquid material layer on the cathode
  • Step S3 preparing an electron transport layer on the first ionic liquid material layer
  • Step S4 preparing a second ionic liquid material layer on the electron transport layer
  • Step S5 preparing a quantum dot light-emitting layer on the second ionic liquid material layer
  • Step S6 preparing a hole transport layer on the quantum dot light emitting layer
  • Step S7 preparing a hole injection layer on the hole transport layer
  • Step S8 preparing an anode on the hole injection layer to obtain a quantum dot light emitting diode.
  • the cathode includes but is not limited to one or more of metal materials, carbon materials, and metal oxides.
  • the metal material includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg.
  • the carbon material includes one or more of graphite, carbon nanotubes, graphene, and carbon fiber.
  • the metal oxide may be a doped or undoped metal oxide, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, and also includes doped or undoped transparent Composite electrode with metal sandwiched between metal oxides, wherein the composite electrode includes AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO /Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 One or more.
  • the electron transport layer is selected from inorganic materials and/or organic materials with electron transport capability, wherein the inorganic electron transport layer material is selected from doped or undoped metal oxides, doped or undoped One or more of the mixed metal sulfides.
  • the doped or undoped metal oxide includes one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO .
  • the doped or undoped metal sulfide includes one or more of CdS, ZnS, MoS, WS, and CuS.
  • the quantum dot materials of the quantum dot light-emitting layer are group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, One or more of Group II-IV-VI compounds or Group IV elements.
  • the semiconductor materials used in the quantum dot light-emitting layer include, but are not limited to, nanocrystals of II-VI semiconductors, such as CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe and Other binary, ternary, and quaternary II-VI compounds; III-V semiconductor nanocrystals, such as GaP, GaAs, InP, InAs, and other binary, ternary, and quaternary III-V compounds;
  • the semiconductor materials used for electroluminescence are not limited to group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, group IV simple substances, and the like.
  • the quantum dot material of the quantum dot light-emitting layer may also be a doped or undoped inorganic perovskite semiconductor, and/or an organic-inorganic hybrid perovskite semiconductor; specifically, the inorganic
  • the structural formula of the perovskite semiconductor is AMX 3 , where A is Cs + ion and M is a divalent metal cation, including but not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+, Mn 2+, Co 2+, Fe 2+, Ge 2+, Yb 2+, Eu 2+, X is a halogen anion, including but not limited to, Cl -, Br -, I - ; the
  • the structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX 3 , where B is an organic amine cation, including but not limited to CH 3 (CH 2 ) n-2 NH 3 + (n ⁇
  • the inorganic metal halide octahedron MX 6 4- is connected by co-topping, the metal cation M is located at the body center of the halogen octahedron, and the organic amine cation B is filled in the gap between the octahedron to form an infinite extension Three-dimensional structure; when n>2, the inorganic metal halide octahedral MX 6 4- connected in a co-topping manner extends in a two-dimensional direction to form a layered structure, and an organic amine cation bimolecular layer (protonated single Amine) or organic amine cation monolayer (protonated diamine), organic layer and inorganic layer overlap to form a stable two-dimensional layered structure; M is a divalent metal cation, including but not limited to Pb 2+ , Sn 2 + , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ ,
  • the material of the hole transport layer and/or hole injection layer includes but is not limited to one or more of PEDOT: PSS, CuPc, F4-TCNQ, HATCN, transition metal oxide, transition metal chalcogenide compound .
  • the transition metal oxide includes one or more of NiOx, MoOx, WOx, CrOx, CuO.
  • the metal sulfur-based compound includes one or more of MoSx, MoSex, WSx, WSex, and CuS.
  • the hole transport layer materials include but are not limited to poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), polyvinylcarbazole, poly(N, N' Bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4- Phenylenediamine), 4,4',4''-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl- N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, 15 N,N'-diphenyl-N,N'-(1-naphthalene Radical)-1,1'-bipheny
  • the hole transport layer is selected from inorganic materials having hole transport capabilities, including but not limited to at least one of NiOx, MoOx, WOx, CrOx, CuO, MoSx, MoSex, WSx, WSex, CuS Species.
  • the anode includes but is not limited to one or more of metal materials, carbon materials, metal oxides, and hole injection materials.
  • the metal material includes one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg.
  • the carbon material includes one or more of graphite, carbon nanotubes, graphene, and carbon fiber.
  • the metal oxide may be a doped or undoped metal oxide, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO, and also includes doped or undoped transparent Composite electrode with metal sandwiched between metal oxides, wherein the composite electrode includes AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO /Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 One or more.
  • the hole injection material includes but is not limited to one or more of PEDOT: PSS, CuPc, F4-TCNQ, HATCN, transition metal oxide, and transition metal chalcogenide compound.
  • the transition metal oxide includes one or more of NiOx, MoOx, WOx, CrOx, CuO.
  • the metal sulfur-based compound includes one or more of MoSx, MoSex, WSx, WSex, and CuS.
  • the substrate is a rigid substrate or a flexible substrate, wherein the rigid substrate includes but is not limited to one or more of glass and metal foil;
  • the flexible substrate includes but is not limited to Polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polyetheretherketone (PEEK), polystyrene (PS), polyethersulfone (PES), polycarbonate Ester (PC), polyarylate (PAT), polyarylate (PAR), polyimide (PI), polyvinyl chloride (PV), polyethylene (PE), polyvinylpyrrolidone (PVP), textile One or more of the fibers.
  • PET Polyethylene terephthalate
  • PEN polyethylene terephthalate
  • PEEK polyetheretherketone
  • PS polystyrene
  • PS polyethersulfone
  • PC polycarbonate Ester
  • PAT polyarylate
  • PAR polyarylate
  • PI polyimide
  • PV polyvinyl chloride
  • PE polyethylene
  • the preparation method of each layer can be a chemical method or a physical method, wherein the chemical method includes but is not limited to chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing One or more of method, electrolytic deposition method, co-precipitation method; physical method includes but not limited to physical coating method or solution method, wherein solution method includes but not limited to spin coating method, printing method, blade coating method, dip extraction Pulling method, dipping method, spraying method, roll coating method, casting method, slot coating method, strip coating method; physical coating method includes but not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering One or more of spray method, multi-arc ion coating method, physical vapor deposition method, atomic layer deposition method, pulse laser deposition method.
  • the chemical method includes but is not limited to chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing One or more of method, electrolytic deposition method, co-
  • an embodiment of the present application further provides a printed quantum dot display screen, including the foregoing quantum dot light-emitting diode.
  • a quantum dot light emitting diode the preparation process is as follows:
  • a quantum dot light emitting diode the preparation process is as follows:
  • a quantum dot light emitting diode the preparation process is as follows:
  • a quantum dot light emitting diode the preparation process is as follows:

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

Abstract

Diode électroluminescente à points quantiques et son procédé de préparation. La diode électroluminescente à points quantiques comprend une anode, une cathode et une couche électroluminescente à points quantiques disposée entre l'anode et la cathode, une couche de transport d'électrons étant disposée entre la couche électroluminescente à points quantiques et la cathode, et la couche de transport d'électrons étant pourvue d'un matériau liquide ionique sur une surface de celle-ci. Le matériau liquide ionique présente des caractéristiques telles que des propriétés chimiques stables, un degré élevé de liaison et une forte résistance contre l'eau et l'oxygène, et peut former une couche de matériau liquide ionique dense pour améliorer le transport de porteurs et atténuer des défauts sur la surface d'une couche de transport d'électrons, ce qui permet de réduire la barrière de potentiel de transfert de porteurs à l'intérieur du dispositif et d'améliorer les propriétés d'émission de lumière du dispositif. Le matériau liquide ionique recouvre également la surface de la couche de transport d'électrons de façon à résoudre efficacement le problème selon lequel la surface d'une couche de transport d'électrons n'est pas complètement recouverte, comporte des trous, ou est irrégulière.
PCT/CN2019/103478 2018-11-29 2019-08-30 Diode électroluminescente à points quantiques et son procédé de préparation Ceased WO2020107978A1 (fr)

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CN201811443013.0A CN111244301A (zh) 2018-11-29 2018-11-29 量子点发光二极管
CN201811443037.6A CN111244302B (zh) 2018-11-29 2018-11-29 量子点发光二极管及其制备方法

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