WO2020107978A1 - 量子点发光二极管及其制备方法 - Google Patents

量子点发光二极管及其制备方法 Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
cation
ionic liquid
quantum dot
liquid material
dot light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/103478
Other languages
English (en)
French (fr)
Inventor
梁柱荣
曹蔚然
钱磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TCL Technology Group Co Ltd
Original Assignee
TCL Technology Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from 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/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • 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:

Landscapes

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

Abstract

一种量子点发光二极管及其制备方法，该量子点发光二极管包括阳极、阴极以及设置在所述阳极和所述阴极之间的量子点发光层，所述量子点发光层与所述阴极之间设置有电子传输层，所述电子传输层的表面设置有离子液体材料。因离子液体材料具有化学性质稳定、黏结度大、阻隔水氧能力强等特点，其可以形成一层致密的离子液体材料层，一方面能够提高载流子传输，钝化该电子传输层表面的缺陷，从而降低器件内部载流子的传输势垒，提高器件的发光性能；同时离子液体材料覆盖在电子传输层表面，有效地克服了电子传输层表面覆盖不全或存在针孔或表面不平整的缺陷。

Description

量子点发光二极管及其制备方法
本申请要求于2018年11月29日在中国专利局提交的、申请号为2018114430376、发明名称为“量子点发光二极管及其制备方法”，以及申请号为2018114430130、发明名称为“量子点发光二极管及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及显示技术领域，具体涉及一种量子点发光二极管及其制备方法。
 背景技术
量子点发光二极管（Quantum dots light-emitting diode, QLED），是一种新兴的显示器件，其原理和结构与有机发光二极管（Organic light-emitting diode, OLED）相似：即量子点和有机/无机半导体在外加直流电场驱动下，激子复合发光的一种平板显示器件。对比OLED，QLED的特点在于其发光材料采用胶体法制备的量子点。量子点独特的量子尺寸效应、宏观量子隧道效应、量子尺寸效应和表面效应使其展现出出色的物理性质，尤其是优异的光学性能。相对于有机荧光染料，胶体量子点具有光谱可调，发光强度大、色纯度高、单光源可激发多色荧光等优势，有望成为下一代的平板显示器，具有广阔发展前景。
然而，相关技术还有待进一步的研究和发展。
 技术问题
发明人发现，由于QLED器件中，量子点和器件内部常用的金属纳米颗粒传输层材料一般采用溶液法制备，因此业内对QLED的产业化的合适工艺普遍认为是溶液法中的喷墨打印法，该制备工艺简单，材料利用率低，制备效率高，被认为是未来平板显示非常有潜力的新技术。虽然QLED与OLED相比具有众多优势，但是由于QD及部分传输层材料等都是溶液相的纳米颗粒，与OLED膜层的成熟蒸镀工艺相比，成膜性能不容易控制，容易出现覆盖不全或者“针孔”等膜层问题，这不仅会对器件产生漏电流，降低器件的发光性能，并且最重要的是这些缺陷区域会极大地影响器件的寿命。而根据目前业内的研究进展，QLED的器件效率已经达到市场化水平，但是器件寿命短的问题是制约QLED商业化的最大瓶颈，而此问题也是业内一致在努力解决的关键突破点。目前有报道通过改善封装方法、在ETL/Cathode界面引入绝缘高分子修饰层等途径提高器件寿命，但是提高效果不明显，且绝缘高分子层的引入反而会降低载流子的迁移率，以牺牲部分器件性能的基础上获得载流子的平衡和寿命的提高，这些方法虽然有一定效果但是并未能很好提高器件的寿命。
本申请实施例的目的之一在于：提供一种量子点发光二极管及其制备方法，旨在解决现有器件的电子传输层的界面不均匀，膜层出现“针孔”现象，从而降低器件的发光效率和使用寿命的技术问题。
 技术解决方案
为解决上述技术问题，本申请实施例采用的技术方案是：
第一方面，提供了一种量子点发光二极管，包括阳极、阴极以及设置在所述阳极和所述阴极之间的量子点发光层，所述量子点发光层与所述阴极之间设置有电子传输层，所述电子传输层的表面设置有离子液体材料。
在一个实施例中，所述电子传输层靠近所述阴极的表面设置有由所述离子液体材料组成的第一离子液体材料层。
在一个实施例中，所述阴极、所述第一离子液体材料层与所述电子传输层层叠形成。
在一个实施例中，所述第一离子液体材料层的厚度为：5-80nm。
在一个实施例中，所述电子传输层靠近所述量子点发光层的表面设置有由所述离子液体材料组成的第二离子液体材料层。
在一个实施例中，所述电子传输层、所述第二离子液体材料层与所述量子点发光层层叠形成。
在一个实施例中，所述第一离子液体材料层的厚度为：5-80nm。
在一个实施例中，所述电子传输层的材料选自过渡金属氧化物和过渡金属硫系化合物中的一种或多种纳米颗粒。
在一个实施例中，所述电子传输层的表面包括一种或多种所述离子液体材料，所述离子液体材料为有机阳离子和无机阴离子组成的盐；其中，
所述有机阳离子选自烷基季铵离子、烷基季磷离子、烷基取代的咪唑离子、烷基取代的吡啶离子中的一种，所述无机阴离子选自卤素离子和无机酸阴离子中的一种。
在一个实施例中，所述烷基季铵离子选自N,N-二乙基-N-甲基-N-(n-丙基)铵阳离子和N,N-二乙基-N-甲基-(2-甲氧乙基)铵阳离子中的一种；或者，
所述烷基季磷离子选自十四烷基三丁基磷阳离子、四羟甲基磷阳离子、乙基三丁基磷阳离子和四丁基磷阳离子中的一种；或者，
所述烷基取代的咪唑离子选自1-丁基-3-甲基咪唑阳离子、1-乙基-3-甲基咪唑阳离子、1-辛基-3-甲基咪唑阳离子、1-癸基-3-甲基咪唑阳离子、1-己基-3-甲基咪唑阳离子和1-甲基-3-正辛基咪唑阳离子中的一种；或者，
所述烷基取代的吡啶离子选自N-乙基吡啶阳离子、N-丁基吡啶阳离子、N-己基吡啶阳离子、N-辛基吡啶阳离子和N-甲基-N-丙基吡啶阳离子中的一种；或者，
所述卤素离子选自F -、Cl -、Br -和I -中的一种；或者，
所述无机酸阴离子选自BF 4 -、PF 6 -、CF 3SO 3 -、CF 3COO -、(CF 3SO 2) 3C -、(C 2F 5SO 2) 3C -、(CF 3SO 2) 2N -、NO 2 -、NO 3 -、ClO 4 -和C 8H 17SO 4 -中的一种。
在一个实施例中，所述离子液体材料中的有机阳离子选自烷基季铵离子和烷基取代的咪唑离子中的一种。
在一个实施例中，所述离子液体材料中的有机阳离子为非对称阳离子；和/或
所述离子液体材料中的有机阳离子和无机阴离子之间形成有氢键。
在一个实施例中，所述离子液体材料选自1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐、氯化1-乙基-3-甲基咪唑、1-癸基-3-甲基咪唑六氟磷酸盐、1-己基-3-甲基咪唑四氟硼酸盐、1-甲基-3-正辛基咪唑四氟硼酸盐和N,N-二乙基-N-甲基-N-(2-甲氧基乙基)四氟硼酸季铵盐中的至少一种。
第二方面，提供了一种量子点发光二极管的制备方法，包括如下步骤：
提供基底；
在所述基底上制备离子液体材料。
在一个实施例中，在所述基底上制备离子液体材料的步骤包括：直接将一种或多种离子液体材料沉积在所述基底上，进行退火处理；
在一个实施例中，所述退火处理的温度为40~220℃；和/或，
所述退火处理的时间为5~240min。
在一个实施例中，在所述基底上制备离子液体材料的步骤包括：配制含有一种或多种离子液体材料的溶液，将所述溶液沉积在所述基底上后，进行退火处理。
在一个实施例中，所述溶液中离子液体的浓度为0.2~60mg/mL；和/或，
所述退火处理的温度为40~220℃；和/或，
所述退火处理的时间为5~240min。
在一个实施例中，所述离子液体材料为有机阳离子和无机阴离子组成的盐；其中，所述有机阳离子选自烷基季铵离子、烷基季磷离子、烷基取代的咪唑离子、烷基取代的吡啶离子中的一种，所述无机阴离子选自卤素离子和无机酸阴离子中的一种。
在一个实施例中，所述烷基季铵离子选自N,N-二乙基-N-甲基-N-(n-丙基)铵阳离子和N,N-二乙基-N-甲基-(2-甲氧乙基)铵阳离子中的一种；或者，
所述烷基季磷离子选自十四烷基三丁基磷阳离子、四羟甲基磷阳离子、乙基三丁基磷阳离子和四丁基磷阳离子中的一种；或者，
所述烷基取代的咪唑离子选自1-丁基-3-甲基咪唑阳离子、1-乙基-3-甲基咪唑阳离子、1-辛基-3-甲基咪唑阳离子、1-癸基-3-甲基咪唑阳离子、1-己基-3-甲基咪唑阳离子和1-甲基-3-正辛基咪唑阳离子中的一种；或者，
所述烷基取代的吡啶离子选自N-乙基吡啶阳离子、N-丁基吡啶阳离子、N-己基吡啶阳离子、N-辛基吡啶阳离子和N-甲基-N-丙基吡啶阳离子中的一种；或者，
所述卤素离子选自F -、Cl -、Br -和I -中的一种；或者，
所述无机酸阴离子选自BF 4 -、PF 6 -、CF 3SO 3 -、CF 3COO -、(CF 3SO 2) 3C -、(C 2F 5SO 2) 3C -、(CF 3SO 2) 2N -、NO 2 -、NO 3 -、ClO 4 -和C 8H 17SO 4 -中的一种。.
有益效果
本申请实施例提供的量子点发光二极管的有益效果在于：该量子点发光二极管在电子传输层表面设置有离子液体材料，因离子液体材料具有化学性质稳定、黏结度大、阻隔水氧能力强等特点，其可以形成一层致密的离子液体材料层，一方面能够提高载流子传输，钝化该电子传输层表面的缺陷，从而降低器件内部载流子的传输势垒，提高器件的发光性能；同时离子液体材料覆盖在电子传输层表面，有效地克服了电子传输层表面覆盖不全或存在针孔或表面不平整的缺陷，同时当量子点发光二极管为柔性器件时，通过引入离子液体材料能够在器件弯曲折叠过程中有效地保护电子传输层，并实现裂缝的自修复功能，从而提高器件的可设计性和使用寿命。
本申请实施例提供的量子点发光二极管的制备方法的有益效果在于：该制备方法工艺简单成本低，在所述基底上直接制备离子液体材料，该离子液体材料不仅具有导电性强、性质稳定、可设计性好、蒸气压小、黏结度大、绿色无污染的突出优点，而且具有结构致密，热稳定性和阻隔水氧能力好的特点，因此可以通过在基底表面不同的功能层，即可直接将制备的离子液体材料用与修饰该功能层，从而可以提高器件的发光性能和使用寿命。
 附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例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。
图1为本申请一实施例的量子点发光二极管的制备方法流程示意图；
图2为本申请一实施例的量子点发光二极管的结构示意图。
 本发明的实施方式
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，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用以解释本申请，并不用于限定本申请。
需说明的是，术语“第一”、“第二”仅用于便于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明技术特征的数量。“多个”的含义是两个或两个以上，除非另有明确具体的限定。
本申请实施例中，所述离子液体是指在室温或接近室温下呈现液态的、完全由阴阳离子所组成的盐，也称为低温熔融盐，该离子液体具有导电性强、性质稳定、耐热性高、蒸气压低、不易燃、绿色无污染、通过阴阳离子的设计可以调节材料的各方面性能等突出优点。利用离子液体材料的特有性能，在器件电子传输层表面设置离子液体材料。
本申请一些实施例提供一种量子点发光二极管，包括阳极、阴极以及设置在所述阳极和所述阴极之间的量子点发光层，所述量子点发光层与所述阴极之间设置有电子传输层，所述电子传输层的表面设置有离子液体材料。
本申请实施例提供的量子点发光二极管在电子传输层表面设置有离子液体材料，因离子液体材料具有化学性质稳定、黏结度大、阻隔水氧能力强等特点，其可以形成一层致密的离子液体材料层，一方面能够提高载流子传输，钝化该电子传输层表面的缺陷，从而降低器件内部载流子的传输势垒，提高器件的发光性能；同时离子液体材料覆盖在电子传输层表面，有效地克服了电子传输层表面覆盖不全或存在针孔或表面不平整的缺陷，同时当量子点发光二极管为柔性器件时，通过引入离子液体材料能够在器件弯曲折叠过程中有效地保护电子传输层，并实现裂缝的自修复功能，从而提高器件的可设计性和使用寿命。
本申请实施例中，所述电子传输层的表面包括一种或多种所述离子液体材料，所述离子液体材料为有机阳离子和无机阴离子组成的盐；其中，所述有机阳离子选自烷基季铵离子[NR xH 4-x] +、烷基季磷离子[PR xH 4-x] +、烷基取代的咪唑离子[R 1R 3im] +、烷基取代的吡啶离子[RPy] +中的一种，所述无机阴离子选自卤素离子和无机酸阴离子中的一种。
具体地，所述烷基季铵离子选自N,N-二乙基-N-甲基-N-(n-丙基)铵阳离子和N,N-二乙基-N-甲基-(2-甲氧乙基)铵阳离子中的一种；所述烷基季磷离子选自十四烷基三丁基磷阳离子、四羟甲基磷阳离子、乙基三丁基磷阳离子和四丁基磷阳离子中的一种；所述烷基取代的咪唑离子选自1-丁基-3-甲基咪唑阳离子、1-乙基-3-甲基咪唑阳离子、1-辛基-3-甲基咪唑阳离子、1-癸基-3-甲基咪唑阳离子、1-己基-3-甲基咪唑阳离子和1-甲基-3-正辛基咪唑阳离子中的一种；所述烷基取代的吡啶离子选自N-乙基吡啶阳离子、N-丁基吡啶阳离子、N-己基吡啶阳离子、N-辛基吡啶阳离子和N-甲基-N-丙基吡啶阳离子中的一种；所述卤素离子选自F -、Cl -、Br -和I -中的一种；所述无机酸阴离子选自BF 4 -、PF 6 -、CF 3SO 3 -、CF 3COO -、(CF 3SO 2) 3C -、(C 2F 5SO 2) 3C -、(CF 3SO 2) 2N -、NO 2 -、NO 3 -、ClO 4 -和C 8H 17SO 4 -中的一种。
因为烷基季铵类离子液体和烷基取代的咪唑类离子液体的电化学稳定性更好，因此，本申请一实施例中，有机阳离子为烷基季铵离子、烷基取代的咪唑离子。
再一实施例中，所述有机阳离子为非对称阳离子；和/或，所述有机阳离子和无机阴离子之间形成有氢键。
评价离子液体实用性的重要指标是它的熔点，离子液体的结构与其熔点之间有着决定性的关系，直接关系到离子液体的使用温度范围。在阳离子相同的情况下，随着阴离子体积的增大熔点逐渐降低，比较不同的氯化物的熔点可以了解阳离子对熔点的影响。在阴离子相同的情况下，随着阳离子体积的增大熔点逐渐降低。并且，为了在室温下保持液态，离子液体为非对称的。离子液体的结构对称性越低,分子间作用力越弱，阳离子或阴离子电荷分布越均匀，离子液体的熔点就越低。
阴离子生成化合物的熔点由大到小的顺序为：Cl ->NO 2 ->NO 3 ->AlCl 4 ->BF 4 ->CF 3SO 3>CF 3CO 2 -。
常温下离子液体的黏度是水的黏度的几十倍到上百倍。阴阳离子的结构对离子液体黏度有很大影响：阳离子的取代基的碳链长增加离子液体的黏度增加，如阳离子为[bmin]的离子液体比[emin]的黏度大得多；取代基的烷基支化使离子液体的黏度增加，如阳离子为[ibmin]的离子液体比[bmin]的黏度大；另外，离子液体的黏度主要有范德华力和氢键作用决定，阴离子的体积减小，使范德华力减小，静电作用增大，而黏度变小；阴离子碱性大，黏度小，如[emin]F(HF)n的阴离子碱性大，黏度最小。因此，阴阳离子形成氢键后，离子液体的黏度增大；离子液体的黏度与温度的关系福成Vogel-Tammann-Fulchers方程。
综上，有机阳离子为非对称阳离子，且所述有机阳离子和无机阴离子之间形成有氢键的离子液体材料既保证熔点低，又具有很好的粘度。
在本申请实施例中，所述离子液体材料选自1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐、氯化1-乙基-3-甲基咪唑、1-癸基-3-甲基咪唑六氟磷酸盐、1-己基-3-甲基咪唑四氟硼酸盐、1-甲基-3-正辛基咪唑四氟硼酸盐和N,N-二乙基-N-甲基-N-(2-甲氧基乙基)四氟硼酸季铵盐中的至少一种。
在一实施例中，所述电子传输层靠近所述阴极的表面设置有由所述离子液体材料组成的第一离子液体材料层。在阴极、电子传输层之间的表面设置有第一离子液体材料层，这样不仅可以钝化电子传输层，而且可以改善阴极。因离子液体材料具有化学性质稳定、黏结度大、阻隔水氧能力强等特点，其形成一层致密的第一离子液体材料层后，一方面能够提高载流子传输，钝化阴极表面缺陷，从而降低器件内部载流子的传输势垒，提高器件的发光性能；同时第一离子液体材料层覆盖在阴极表面，有效地克服了阴极表面覆盖不全或存在针孔或表面不平整等导致的器件漏电流严重、器件寿命衰减迅速的问题，从而提高器件的使用寿命。具体地，所述阴极、所述第一离子液体材料层与所述电子传输层层叠形成。这样第一离子液体材料层不仅可以很好地改善阴极表面，还可以很好地钝化电子传输层叠，有效地克服了电子传输层叠靠近阴极表面覆盖不全或存在针孔或表面不平整的缺陷，即可以更好地对阴极和电子传输层之间的界面改善。
在一实施例中，所述第一离子液体材料层的厚度为：5-80nm。
在一实施例中，所述电子传输层靠近所述量子点发光层的表面设置有由所述离子液体材料组成的第二离子液体材料层。第二离子液体材料层一方面能够提高载流子传输，钝化功能层表面（即电子传输层的表面）的缺陷，从而降低器件内部载流子的传输势垒，提高器件的发光性能；同时第二离子液体材料层覆盖在电子传输层表面，有效地克服了电子传输层表面覆盖不全或存在针孔或表面不平整的缺陷，同时当量子点发光二极管为柔性器件时，通过引入离子液体材料层，能够在器件弯曲折叠过程中有效地保护电子传输层，并实现裂缝的自修复功能，从而提高器件的可设计性和使用寿命。具体地，所述电子传输层、所述第二离子液体材料层与所述量子点发光层层叠形成。这样第二离子液体材料层在改善电子传输层表面的同时，还可以进一步钝化量子点发光层，有效地克服了量子点发光层靠近电子传输层表面覆盖不全或存在针孔或表面不平整的缺陷。
在一实施例中，所述第一离子液体材料层的厚度为：5-80nm。
在一实施例中，阳极和量子点发光层之间设有空穴功能层。如空穴注入层，或层叠的空穴注入层和空穴传输层，其中空穴传输层与量子点发光层相邻。
本申请一实施例中，提供一种量子点发光二极管，包括阳极、阴极以及设置在所述阳极和所述阴极之间的量子点发光层，所述量子点发光层与所述阴极之间设置有电子传输层，所述电子传输层靠近所述阴极的表面设置有第一离子液体材料层，且所述电子传输层靠近所述量子点发光层的表面设置有第二离子液体材料层。离子液体材料层作为界面修饰层，设置在阴极靠近所述电子传输层的表面和电子传输层靠近所述量子点发光层的表面，从而形成两层离子液体材料层，通过协同效果作用，进一步增加注入到量子点发光层中的电子数量，从而进一步提高器件发光效率。
本申请实施例中，上述第一离子液体材料层和第二离子液体材料层中的离子液体材料为有机阳离子和无机阴离子组成的盐；其中，所述有机阳离子选自烷基季铵离子[NR xH 4-x] +、烷基季磷离子[PR xH 4-x] +、烷基取代的咪唑离子[R 1R 3im] +、烷基取代的吡啶离子[RPy] +中的一种，所述无机阴离子选自卤素离子和无机酸阴离子中的一种。所述第二离子液体材料层中的离子液体材料可以与所述第一离子液体材料层中的离子液体材料相同或不同，具体可以在上述阐明的的离子液体材料选择范围内进行选择。具体地，第一离子液体材料和第二离子液体材料层中的离子液体材料选自1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐、氯化1-乙基-3-甲基咪唑、1-癸基-3-甲基咪唑六氟磷酸盐、1-己基-3-甲基咪唑四氟硼酸盐、1-甲基-3-正辛基咪唑四氟硼酸盐和N,N-二乙基-N-甲基-N-(2-甲氧基乙基)四氟硼酸季铵盐中的至少一种。
在一实施例中，所述电子传输层的材料为过渡金属氧化物和过渡金属硫系化合物中的一种或多种纳米颗粒。所述过渡金属氧化物包括ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、NiO、TiLiO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO中的一种或多种，所述金属硫系化合物包括CdS、ZnS、MoS、WS、CuS。在做成柔性器件的时候，这些纳米颗粒组成的膜层极易出现裂缝等问题导致器件失效，而通过引入离子液体材料层能够在器件弯曲折叠过程中有效地保护纳米颗粒组成电子传输层并实现裂缝的自修复功能，提高器件的可设计性和使用寿命。
另一方面，本申请实施例还提供一种量子点发光二极管的制备方法，如图1所示，包括如下步骤：
S01：提供基底；
S02：在所述基底上制备离子液体材料。
本申请实施例提供的量子点发光二极管的制备方法，工艺简单成本低，在所述基底上直接制备离子液体材料，该离子液体材料层不仅具有导电性强、性质稳定、可设计性好、蒸气压小、黏结度大、绿色无污染的突出优点，而且具有结构致密，热稳定性和阻隔水氧能力好的特点，因此可以在基底表面覆载不同的功能层，直接将制备的离子液体材料层用与修饰该功能层，从而可以提高器件的发光性能和使用寿命。
具体地，在基底上制备离子液体材料形成第一离子液体材料层或第二离子液体材料层。
对于第一离子液体材料层，位置在所述电子传输层靠近阴极的表面：具体地，上述步骤S01中；如基底表面设置有阴极，则直接在阴极表面制备第一离子液体材料层，再于第一离子液体材料层上制备电子传输层；如基底表面设置有电子传输层（此时基底为阳极基底），则直接在电子传输层表面制备第一离子液体材料层，再在第一离子液体材料层表面制备阴极。
对于第二离子液体材料层：其制备工艺基本与第一离子液体材料层相同，而位置在所述电子传输层靠近所述量子点发光层的表面。
在一实施例中，上述步骤S02中：在所述基底上制备离子液体材料层的步骤包括：可以直接将离子液体材料沉积在所述基底上，进行退火处理；或者，可以配制含有离子液体材料的溶液后，将所述溶液沉积在所述基底上，然后进行退火处理。其中，溶液中的溶剂为有机溶剂。
其中，溶解在有机溶剂中的离子液体的浓度为0.2~60mg/mL。有机溶剂包括但不限于饱和烃、不饱和烃、芳香烃、醇类溶剂、醚类溶剂、酮类溶剂、腈类溶剂、酯类溶剂、以及它们的衍生物中的一种或者是多种组成的混合有机溶剂。特别地，所述的溶解离子液体的溶剂为醇类溶剂，包括但不限于一元醇、多元醇和芳香醇中的一种或多种，具体包括但不限于甲醇、乙醇、乙二醇、丙醇、丙二醇、丙三醇、异丙醇、丁醇、戊醇、己醇、环己醇、正丁醇、苯甲醇、苯乙醇中的一种或多种。上述制备离子液体材料层的方法即为溶液成膜法，包括但不限于旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法、条状涂布法中的一种或多种。
而上述退火处理的温度为40~220℃；所述退火处理的时间为5~240min。
具体一实施例中，一种正型结构量子点发光二极管的制备包括以下步骤：
步骤S1：在衬底上制备阳极；
步骤S2：在阳极上制备空穴功能层（具体可以是空穴注入层，或依次层叠的空穴注入层和空穴传输层）；
步骤S3：在空穴功能层上制备量子点发光层；
步骤S4：在量子点发光层上制备电子传输层；
步骤S5：在电子传输层上制备第一离子液体材料层；
步骤S6：在第一离子液体材料层上制备阴极。
具体一实施例中，一种正型结构量子点发光二极管的制备包括以下步骤：
步骤S1：在衬底上制备阳极；
步骤S2：在阳极上制备空穴功能层（具体可以是空穴注入层，或依次层叠的空穴注入层和空穴传输层）；
步骤S3：在空穴功能层上制备量子点发光层；
步骤S4：在量子点发光层上制备第二离子液体材料层；
步骤S5：在第二离子液体材料层制备电子传输层；
步骤S6：在电子传输层上制备阴极。
具体一实施例中，一种正型结构量子点发光二极管的结构图1所示，其制备包括以下步骤：
步骤S1：在衬底上制备阳极；
步骤S2：在阳极上制备空穴功能层（具体可以是空穴注入层，或依次层叠的空穴注入层和空穴传输层）；
步骤S3：在空穴功能层上制备量子点发光层；
步骤S4：在量子点发光层上制备第二离子液体材料层；
步骤S5：在第二离子液体材料层上制备电子传输层；
步骤S6：在电子传输层上制备第一离子液体材料层；
步骤S7：在第一离子液体材料层上制备阴极。
具体一实施例中，一种反型结构量子点发光二极管的制备包括以下步骤：
步骤S1：在衬底上制备阴极；
步骤S2：在阴极上制备第一离子液体材料层；
步骤S3：在第一离子液体材料层上制备电子传输层；
步骤S4：在电子传输层上制备量子点发光层；
步骤S4：在量子点发光层上制备空穴功能层；
步骤S5：在空穴功能层上制备阳极。
具体一实施例中，一种反型结构量子点发光二极管的制备包括以下步骤：
步骤S1：在衬底上制备阴极；
步骤S2：在阴极上制备第一离子液体材料层；
步骤S3：在第一离子液体材料层上制备电子传输层；
步骤S4：在电子传输层上制备第二离子液体材料层；
步骤S5：在第二离子液体材料层上制备量子点发光层；
步骤S6：在量子点发光层上制备空穴传输层；
步骤S7：在空穴传输层上制备空穴注入层；
步骤S8：在空穴注入层上制备阳极，得到量子点发光二极管。
其中，上述制备方法中，所述阴极包括但不限于金属材料、碳材料、金属氧化物中的一种或多种。其中，所述金属材料包括Al、Ag、Cu、Mo、Au、Ba、Ca、Mg中的一种或多种。所述碳材料包括石墨、碳纳米管、石墨烯、碳纤维中的一种或多种。所述金属氧化物可以是掺杂或非掺杂金属氧化物，包括ITO、FTO、ATO、AZO、GZO、IZO、MZO、AMO中的一种或多种，也包括掺杂或非掺杂透明金属氧化物之间夹着金属的复合电极，其中，所述复合电极包括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中的一种或多种。
其中，所述电子传输层选自具有电子传输能力的无机材料和/或有机材料，其中，所述的无机电子传输层材料选自掺杂或非掺杂的金属氧化物、掺杂或非掺杂的金属硫化物中的一种或多种。其中，所述掺杂或非掺杂金属氧化物包括ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、NiO、TiLiO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO中的一种或多种。所述掺杂或非掺杂金属硫化物包括CdS、ZnS、MoS、WS、CuS中的一种或多种。
其中，所述量子点发光层的量子点材料为II-VI族化合物、III-V族化合物、II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物或IV族单质中的一种或多种。具体地，所述量子点发光层使用的半导体材料包括但不限于II-VI半导体的纳米晶，比如CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、HgS、HgSe、HgTe、PbS、PbSe、PbTe和其他二元、三元、四元的II-VI化合物；III-V族半导体的纳米晶，比如GaP、GaAs、InP、InAs和其他二元、三元、四元的III-V化合物；所述的用于电致发光的半导体材料还不限于II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物、IV族单质等。
其中，所述量子点发光层的量子点材料还可以为掺杂或非掺杂的无机钙钛矿型半导体、和/或有机-无机杂化钙钛矿型半导体；具体地，所述的无机钙钛矿型半导体的结构通式为AMX 3，其中A为Cs +离子，M为二价金属阳离子，包括但不限于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为卤素阴离子，包括但不限于Cl -、Br -、I -；所述的有机-无机杂化钙钛矿型半导体的结构通式为BMX 3，其中B为有机胺阳离子，包括但不限于CH 3(CH 2) n-2NH 3 + (n≥2)或NH 3(CH 2) nNH 3 2+ (n≥2)。当n=2时，无机金属卤化物八面体MX 6 4-通过共顶的方式连接，金属阳离子M位于卤素八面体的体心，有机胺阳离子B填充在八面体间的空隙内，形成无限延伸的三维结构；当n＞2时，以共顶的方式连接的无机金属卤化物八面体MX 6 4-在二维方向延伸形成层状结构，层间插入有机胺阳离子双分子层（质子化单胺）或有机胺阳离子单分子层（质子化双胺），有机层与无机层相互交叠形成稳定的二维层状结构；M为二价金属阳离子，包括但不限于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为卤素阴离子，包括但不限于Cl -、Br -、I。
其中，所述空穴传输层和/或空穴注入层的材料包括但不限于PEDOT:PSS、CuPc、F4-TCNQ、HATCN、过渡金属氧化物、过渡金属硫系化合物中的一种或多种。其中，所述过渡金属氧化物包括NiOx、MoOx、WOx、CrOx、CuO中的一种或多种。所述金属硫系化合物包括MoSx、MoSex、WSx、WSex、CuS中的一种或多种。所述的空穴传输层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)、聚乙烯咔唑、聚(N, N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)、4,4’,4’’-三(咔唑-9-基)三苯胺、 4,4'-二(9-咔唑)联苯、 N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-联苯-4,4’-二胺、15 N,N’-二苯基-N,N’-(1-萘基)-1,1’-联苯-4,4’-二胺、石墨烯、C60中的至少一种。作为另一个实施例，所述空穴传输层选自具有空穴传输能力的无机材料，包括但不限于NiOx、MoOx、WOx、CrOx、CuO、MoSx、MoSex、WSx、WSex、CuS中的至少一种。
其中，所述阳极包括但不限于金属材料、碳材料、金属氧化物、空穴注入材料中的一种或多种。其中，所述金属材料包括Al、Ag、Cu、Mo、Au、Ba、Ca、Mg中的一种或多种。所述碳材料包括石墨、碳纳米管、石墨烯、碳纤维中的一种或多种。所述金属氧化物可以是掺杂或非掺杂金属氧化物，包括ITO、FTO、ATO、AZO、GZO、IZO、MZO、AMO中的一种或多种，也包括掺杂或非掺杂透明金属氧化物之间夹着金属的复合电极，其中，所述复合电极包括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中的一种或多种。所述的空穴注入材料包括但不限于PEDOT:PSS、CuPc、F4-TCNQ、HATCN、过渡金属氧化物、过渡金属硫系化合物中的一种或多种。其中，所述过渡金属氧化物包括NiOx、MoOx、WOx、CrOx、CuO中的一种或多种。所述金属硫系化合物包括MoSx、MoSex、WSx、WSex、CuS中的一种或多种。
其中，所述衬底为刚性衬底或柔性衬底，其中，所述的刚性衬底包括但不限于玻璃、金属箔片中的一种或多种；所述的柔性衬底包括但不限于聚对苯二甲酸乙二醇酯（PET）、聚对苯二甲酸乙二醇酯（PEN）、聚醚醚酮（PEEK）、聚苯乙烯（PS）、聚醚砜（PES）、聚碳酸酯（PC）、聚芳基酸酯（PAT）、聚芳酯（PAR）、聚酰亚胺（PI）、聚氯乙烯（PV）、聚乙烯（PE）、聚乙烯吡咯烷酮（PVP）、纺织纤维中的一种或多种。
其中，上述制备量子点发光二极管，除了以上特殊说明外，各层的制备方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于物理镀膜法或溶液法，其中溶液法包括但不限于旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法、条状涂布法；物理镀膜法包括但不限于热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法中的一种或多种。
最后本申请实施例还提供一种印刷量子点显示屏，包括上述量子点发光二极管。
本申请先后进行过多次试验，现举一部分试验结果作为参考对本申请进行进一步详细描述，下面结合具体实施例进行详细说明。
实施例1
一种量子点发光二极管，其制备过程如下：
首先将[BMIM]BF4溶解在甲醇中，配制成5mg/mL的离子液体溶液，然后按以下步骤制备器件：
（1）在ITO导电玻璃上旋涂一层PEDOT:PSS空穴注入层；
（2）在PEDOT:PSS空穴注入层上旋涂一层TFB空穴传输层；
（3）在TFB空穴传输层上旋涂一层CdSe/ZnS量子点发光层；
（4）将上述离子液体溶液以3000rpm/s旋涂在CdSe/ZnS量子点发光层上，得到一层致密的[BMIM]BF4离子液体材料层；
（5）在[BMIM]BF4离子液体材料层上旋涂一层ZnO电子传输层；
（6）在ZnO电子传输层上蒸镀一层Al阴极层，得到量子点发光二极管。
实施例2
一种量子点发光二极管，其制备过程如下：
首先将[BMIM]BF4溶解在甲醇中，配制成2mg/mL的离子液体溶液，然后按以下步骤制备器件：
（1）在ITO导电玻璃上旋涂一层ZnO电子传输层；
（2）将上述离子液体溶液以5000rpm/s旋涂在ZnO电子传输层上，然后于80℃加热30min，得到一层致密的[BMIM]BF4离子液体材料层；
（3）在[BMIM]BF4离子液体材料层上旋涂一层CdSe/ZnS量子点发光层；
（4）在CdSe/ZnS量子点发光层上旋涂一层TFB层；
（5）在TFB层上旋涂一层NiO空穴注入层；
（6）在NiO空穴注入层上蒸镀一层Al阳极层，得到量子点发光二极管。
实施例3
一种量子点发光二极管，其制备过程如下：
首先将[BMIM]BF4溶解在甲醇中，配制成5mg/mL的离子液体溶液，然后按以下步骤制备器件：
（1）在ITO导电玻璃上旋涂一层PEDOT:PSS空穴注入层；
（2）在PEDOT:PSS空穴注入层上旋涂一层TFB空穴传输层；
（3）在TFB空穴传输层上旋涂一层CdSe/ZnS量子点发光层；
（4）在CdSe/ZnS量子点发光层上旋涂一层ZnO电子传输层；
（5）将上述离子液体溶液以5000rpm/s旋涂在ZnO电子传输层上，得到一层致密的[BMIM]BF4离子液体材料层；
（6）在[BMIM]BF4离子液体材料层上蒸镀一层Al阴极层，得到量子点发光二极管。
实施例4
一种量子点发光二极管，其制备过程如下：
首先将[BMIM]BF4溶解在甲醇中，配制成5mg/mL的离子液体溶液，然后按以下步骤制备器件：
（1）在ITO导电玻璃上旋涂一层PEDOT:PSS空穴注入层；
（2）在PEDOT:PSS空穴注入层上旋涂一层TFB空穴传输层；
（3）在TFB空穴传输层上旋涂一层CdSe/ZnS量子点发光层；
（4）将上述离子液体溶液以3000rpm/s旋涂在CdSe/ZnS量子点发光层上，得到一层致密的[BMIM]BF4离子液体材料层；
（5）在[BMIM]BF4离子液体材料层上旋涂一层ZnO电子传输层；
（6）将上述离子液体溶液以5000rpm/s旋涂在ZnO电子传输层上，然后于80℃加热30min，得到一层致密的[BMIM]BF4离子液体材料层；
（7）在[BMIM]BF4离子液体材料层上蒸镀一层Al阴极层，得到量子点发光二极管。
以上仅为本申请的可选实施例而已，并不用于限制本申请。对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。

Claims (20)

  1. 一种量子点发光二极管，包括阳极、阴极以及设置在所述阳极和所述阴极之间的量子点发光层，所述量子点发光层与所述阴极之间设置有电子传输层，其特征在于，所述电子传输层的表面设置有离子液体材料。
  2. 如权利要求1所述的量子点发光二极管，其特征在于，所述电子传输层靠近所述阴极的表面设置有由所述离子液体材料组成的第一离子液体材料层。
  3. 如权利要求2所述的量子点发光二极管，其特征在于，所述阴极、所述第一离子液体材料层与所述电子传输层层叠形成。
  4. 如权利要求2所述的量子点发光二极管，其特征在于，所述第一离子液体材料层的厚度为：5-80nm。
  5. 如权利要求1所述的量子点发光二极管，其特征在于，所述电子传输层靠近所述量子点发光层的表面设置有由所述离子液体材料组成的第二离子液体材料层。
  6. 如权利要求5所述的量子点发光二极管，其特征在于，所述电子传输层、所述第二离子液体材料层与所述量子点发光层层叠形成。
  7. 如权利要求5所述的量子点发光二极管，其特征在于，所述第一离子液体材料层的厚度为：5-80nm。
  8. 如权利要求1所述的量子点发光二极管，其特征在于，所述电子传输层的材料选自过渡金属氧化物和过渡金属硫系化合物中的一种或多种纳米颗粒。
  9. 如权利要求1所述的量子点发光二极管，其特征在于，所述电子传输层的表面包括一种或多种所述离子液体材料，所述离子液体材料为有机阳离子和无机阴离子组成的盐；其中，所述有机阳离子选自烷基季铵离子、烷基季磷离子、烷基取代的咪唑离子、烷基取代的吡啶离子中的一种，所述无机阴离子选自卤素离子和无机酸阴离子中的一种。
  10. 如权利要求9所述的量子点发光二极管，其特征在于，所述烷基季铵离子选自N,N-二乙基-N-甲基-N-(n-丙基)铵阳离子和N,N-二乙基-N-甲基-(2-甲氧乙基)铵阳离子中的一种；或者，所述烷基季磷离子选自十四烷基三丁基磷阳离子、四羟甲基磷阳离子、乙基三丁基磷阳离子和四丁基磷阳离子中的一种；或者，
    所述烷基取代的咪唑离子选自1-丁基-3-甲基咪唑阳离子、1-乙基-3-甲基咪唑阳离子、1-辛基-3-甲基咪唑阳离子、1-癸基-3-甲基咪唑阳离子、1-己基-3-甲基咪唑阳离子和1-甲基-3-正辛基咪唑阳离子中的一种；或者，
    所述烷基取代的吡啶离子选自N-乙基吡啶阳离子、N-丁基吡啶阳离子、N-己基吡啶阳离子、N-辛基吡啶阳离子和N-甲基-N-丙基吡啶阳离子中的一种；或者，
    所述卤素离子选自F -、Cl -、Br -和I -中的一种；或者，
    所述无机酸阴离子选自BF 4 -、PF 6 -、CF 3SO 3 -、CF 3COO -、(CF 3SO 2) 3C -、(C 2F 5SO 2) 3C -、(CF 3SO 2) 2N -、NO 2 -、NO 3 -、ClO 4 -和C 8H 17SO 4 -中的一种。
  11. 如权利要求9所述的量子点发光二极管，其特征在于，所述离子液体材料中的有机阳离子选自烷基季铵离子和烷基取代的咪唑离子中的一种。
  12. 如权利要求9所述的量子点发光二极管，其特征在于，所述离子液体材料中的有机阳离子为非对称阳离子；和/或所述离子液体材料中的有机阳离子和无机阴离子之间形成有氢键。
  13. 如权利要求1所述的量子点发光二极管，其特征在于，所述离子液体材料选自1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐、氯化1-乙基-3-甲基咪唑、1-癸基-3-甲基咪唑六氟磷酸盐、1-己基-3-甲基咪唑四氟硼酸盐、1-甲基-3-正辛基咪唑四氟硼酸盐和N,N-二乙基-N-甲基-N-(2-甲氧基乙基)四氟硼酸季铵盐中的至少一种。
  14. 一种量子点发光二极管的制备方法，其特征在于，包括如下步骤：
    提供基底；
    在所述基底上制备离子液体材料。
  15. 如权利要求14所述的制备方法，其特征在于，在所述基底上制备离子液体材料的步骤包括：直接将一种或多种离子液体材料沉积在所述基底上，进行退火处理；
  16. 如权利要求15所述的制备方法，其特征在于，所述退火处理的温度为40~220℃；和/或，
    所述退火处理的时间为5~240min。
  17. 如权利要求14所述的制备方法，其特征在于，在所述基底上制备离子液体材料的步骤包括：配制含有一种或多种离子液体材料的溶液，将所述溶液沉积在所述基底上后，进行退火处理。
  18. 如权利要求17所述的制备方法，其特征在于，所述溶液中离子液体的浓度为0.2~60mg/mL；和/或，
    所述退火处理的温度为40~220℃；和/或，
    所述退火处理的时间为5~240min。
  19. 如权利要求14所述的制备方法，其特征在于，所述离子液体材料为有机阳离子和无机阴离子组成的盐；其中，所述有机阳离子选自烷基季铵离子、烷基季磷离子、烷基取代的咪唑离子、烷基取代的吡啶离子中的一种，所述无机阴离子选自卤素离子和无机酸阴离子中的一种。
  20. 如权利要求14所述的制备方法，其特征在于，所述烷基季铵离子选自N,N-二乙基-N-甲基-N-(n-丙基)铵阳离子和N,N-二乙基-N-甲基-(2-甲氧乙基)铵阳离子中的一种；或者，
    所述烷基季磷离子选自十四烷基三丁基磷阳离子、四羟甲基磷阳离子、乙基三丁基磷阳离子和四丁基磷阳离子中的一种；或者，
    所述烷基取代的咪唑离子选自1-丁基-3-甲基咪唑阳离子、1-乙基-3-甲基咪唑阳离子、1-辛基-3-甲基咪唑阳离子、1-癸基-3-甲基咪唑阳离子、1-己基-3-甲基咪唑阳离子和1-甲基-3-正辛基咪唑阳离子中的一种；或者，
    所述烷基取代的吡啶离子选自N-乙基吡啶阳离子、N-丁基吡啶阳离子、N-己基吡啶阳离子、N-辛基吡啶阳离子和N-甲基-N-丙基吡啶阳离子中的一种；或者，
    所述卤素离子选自F -、Cl -、Br -和I -中的一种；或者，
    所述无机酸阴离子选自BF 4 -、PF 6 -、CF 3SO 3 -、CF 3COO -、(CF 3SO 2) 3C -、(C 2F 5SO 2) 3C -、(CF 3SO 2) 2N -、NO 2 -、NO 3 -、ClO 4 -和C 8H 17SO 4 -中的一种。
PCT/CN2019/103478 2018-11-29 2019-08-30 量子点发光二极管及其制备方法 Ceased WO2020107978A1 (zh)

Applications Claiming Priority (4)

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

Publications (1)

Publication Number Publication Date
WO2020107978A1 true WO2020107978A1 (zh) 2020-06-04

Family

ID=70854430

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/103478 Ceased WO2020107978A1 (zh) 2018-11-29 2019-08-30 量子点发光二极管及其制备方法

Country Status (1)

Country Link
WO (1) WO2020107978A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114695708A (zh) * 2020-12-31 2022-07-01 Tcl科技集团股份有限公司 发光器件及其制备方法
CN114695735A (zh) * 2020-12-31 2022-07-01 Tcl科技集团股份有限公司 量子点发光二极管及其制备方法
CN115666194A (zh) * 2022-09-21 2023-01-31 无锡极电光能科技有限公司 一种电子传输层及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130092906A1 (en) * 2010-04-20 2013-04-18 Sumitomo Chemical Company, Limited Organic light-emitting element
CN104272485A (zh) * 2012-05-10 2015-01-07 默克专利有限公司 用于电子传输层中的包含离子有机化合物的配制剂
CN106062985A (zh) * 2014-02-24 2016-10-26 株式会社理光 光电转换元件和太阳能电池
CN108832010A (zh) * 2018-05-29 2018-11-16 合肥工业大学 一种离子液体作为电荷注入层的钙钛矿发光二极管及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130092906A1 (en) * 2010-04-20 2013-04-18 Sumitomo Chemical Company, Limited Organic light-emitting element
CN104272485A (zh) * 2012-05-10 2015-01-07 默克专利有限公司 用于电子传输层中的包含离子有机化合物的配制剂
CN106062985A (zh) * 2014-02-24 2016-10-26 株式会社理光 光电转换元件和太阳能电池
CN108832010A (zh) * 2018-05-29 2018-11-16 合肥工业大学 一种离子液体作为电荷注入层的钙钛矿发光二极管及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HICHAM BRINEA ET AL: "Ionic Liquid Modified Zinc Oxide Injection Layer for Inverted Organic Light-Emitting Diodes", ORGANIC ELECTRONICS, vol. 14, no. 1, 1 January 2013 (2013-01-01), pages 164 - 168, XP055711268, ISSN: 1566-1199, DOI: 10.1016/j.orgel.2012.09.027 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114695708A (zh) * 2020-12-31 2022-07-01 Tcl科技集团股份有限公司 发光器件及其制备方法
CN114695735A (zh) * 2020-12-31 2022-07-01 Tcl科技集团股份有限公司 量子点发光二极管及其制备方法
CN115666194A (zh) * 2022-09-21 2023-01-31 无锡极电光能科技有限公司 一种电子传输层及其制备方法和应用

Similar Documents

Publication Publication Date Title
CN105206718B (zh) 一种溶液法制备的CsPbX3无机钙钛矿量子点发光二极管
CN111384278B (zh) 一种量子点发光二极管及其制备方法
CN106549111B (zh) 交流电驱动的量子点发光二极管、其制备方法和应用
CN111244308B (zh) 量子点发光层和量子点发光二极管
CN108807720B (zh) 功能化阴极、qled及制备方法、发光模组与显示装置
CN105720204B (zh) 一种反置结构的无机钙钛矿量子点发光二极管
CN109326727B (zh) 一种qled器件及其制备方法
KR20130074815A (ko) 전 용액 공정이 가능한 유기발광소자
JP7640573B2 (ja) ナノ材料、その製造方法及び量子ドット発光ダイオード
US20210028384A1 (en) Quantum dot light-emitting diode and preparation method therefor
CN112018254A (zh) 一种基于苯硫醇衍生物的量子点发光二极管及其制备方法
CN111446378B (zh) 一种透明有机电致发光二极管的制作方法
Zhu et al. All-solution-processed high-performance quantum dot light emitting devices employing an inorganic thiocyanate as hole injection layer
WO2021253923A1 (zh) 量子点发光二极管器件及其制备方法和显示面板
CN109216566B (zh) 复合发光层、qled器件及其制备方法
Payandeh et al. High-brightness perovskite light-emitting diodes using a printable silver microflake contact
CN101373816A (zh) 一种有机电致发光器件的制备方法
CN111244302B (zh) 量子点发光二极管及其制备方法
CN111244301A (zh) 量子点发光二极管
CN111224017B (zh) 量子点发光二极管及其制备方法
Kim et al. Efficiency enhancement of InP‐based inverted QD‐LEDs by incorporation of a polyethylenimine modified Al: ZnO layer
CN110739408B (zh) 量子点发光二极管及其制备方法
Chang et al. ZnO nanocrystals incorporating PEIE and a fluorene-based polyelectrolyte as electron transport layers for pure cesium-containing perovskite light-emitting devices
CN109935670B (zh) 表面配体、量子点薄膜、qled器件及其制备方法
CN112582565A (zh) 发光器件及其制备方法

Legal Events

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

Ref document number: 19891001

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19891001

Country of ref document: EP

Kind code of ref document: A1