WO2019105431A1 - Quantum dot electroluminescent component and display - Google Patents

Quantum dot electroluminescent component and display Download PDF

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Publication number
WO2019105431A1
WO2019105431A1 PCT/CN2018/118273 CN2018118273W WO2019105431A1 WO 2019105431 A1 WO2019105431 A1 WO 2019105431A1 CN 2018118273 W CN2018118273 W CN 2018118273W WO 2019105431 A1 WO2019105431 A1 WO 2019105431A1
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layer
transport layer
electron transport
quantum dot
electroluminescent device
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PCT/CN2018/118273
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French (fr)
Chinese (zh)
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魏雄伟
李哲
谢相伟
黄航
宋晶尧
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广东聚华印刷显示技术有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/166—Electron transporting layers comprising a multilayered structure

Definitions

  • the present invention relates to the field of quantum dots, and more particularly to quantum dot electroluminescent devices and displays.
  • Quantum dots are nano-sized semiconductor materials with quantum confinement effects. When excited by light or electricity, quantum dots emit very pure light, featuring high luminous efficiency and stable performance.
  • Quantum Dot Light Emitting Diode (QLED) devices fabricated by quantum dot electroluminescence properties have received extensive attention in recent years. Compared with traditional organic light-emitting diodes (OLEDs), QLEDs have superior color purity, brightness and viewing angle.
  • the quantum dot light-emitting diodes using quantum dot materials as light-emitting layers have broad application prospects in the fields of solid-state illumination and flat panel display, and have attracted extensive attention in academia and industry.
  • the performance of existing QLED devices has been greatly improved, but there is still a gap between the luminous efficiency and the requirements of industrial production.
  • the structure of a typical quantum dot light-emitting diode is a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer.
  • the electron and hole transport rates are different, resulting in an imbalance of positive load carriers.
  • Carrier imbalance is one of the important factors affecting the performance of QLED devices, especially the luminous efficiency and lifetime of QLED devices. How to obtain effective carrier balance and further improve the performance of QLED devices is still the focus of current academic and industrial research and development.
  • the present invention provides a quantum dot electroluminescent device comprising a first electrode layer and a second electrode layer disposed opposite to each other, and a light emitting layer disposed between the first electrode layer and the second electrode layer. a first electron transport layer between the light emitting layer and the second electrode layer, and a second electron transport layer disposed between the first electron transport layer and the second electrode layer;
  • the material of the first electron transport layer includes an inorganic metal oxide, and the material of the second electron transport layer includes an organic electron transport material.
  • the inorganic metal oxide is one or more of a monovalent metal oxide and a multi-metal oxide.
  • the multi-metal oxide is selected from the group consisting of zinc magnesium oxide, zinc tin oxide, zinc aluminum oxide, calcium zinc oxide, zinc tungsten oxide, zinc zinc oxide, zinc zinc oxide, and ZnO-TiO 2 -SnO 2 . And one or more of ZnO-MgO-TiO 2 ; and/or
  • the monobasic metal oxide is selected from one or more of ZnO, MgO, TiO 2 , SnO 2 , ZrO 2 , HfO 2 or Ta 2 O 3 .
  • the first electron transport layer further comprises a polymer material PEIE.
  • the organic electron transporting material is selected from one or more of the group consisting of NBphen, TPBi, Bpy-FOXD, BP4mPy, BTB, BIPO, 3TPYMB, PBD, BAlq, PEIE, Bphen, TmPyPB, and BCP.
  • the second electron transport layer further includes a dopant material selected from the group consisting of a metal, a metal inorganic salt or an organometallic complex; and/or
  • the dopant material accounts for 1% to 60% of the total mass of the second electron transport layer.
  • the metal is selected from the group consisting of Li, Na, K, Rb, Cs, or Yb; and/or
  • the metal inorganic salt is selected from the group consisting of Li 2 CO 3 , K 2 SiO 3 , Rb 2 CO 3 or Cs 2 CO 3 ; and/or
  • the organometallic complex is selected from the group consisting of LiQ, AlQ 3 .
  • the dopant material comprises from 40% to 60% of the total mass of the second electron transport layer.
  • the first electron transport layer has a thickness of 1-150 nm; and/or
  • the second electron transport layer has a thickness of 1 to 150 nm.
  • the material of the first electron transport layer is a composite material of an inorganic metal oxide or an inorganic metal oxide and a polymer material PEIE
  • the material of the second electron transport layer is an organic electron transport material.
  • a composite of an organic electron transport material and a dopant material is also included in the material of the first electron transport layer.
  • one or more of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, and an electron injection layer are further included.
  • the electroluminescent device comprises one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer or an electron injection layer, the hole injection layer, the hole a transport layer or an electron blocking layer is disposed between the first electrode layer and the light emitting layer, or the electron injection layer is disposed between the second electrode layer and the second electron transport layer, or An electron blocking layer is disposed between the light emitting layer and the second electron transport layer.
  • the electroluminescent device includes a hole injection layer, a hole transport layer, and an electron blocking layer, and the hole injection layer, the hole transport layer, and the electron blocking layer are stacked on The first electrode layer and the light emitting layer are disposed, and the hole injection layer is laminated with the first electrode.
  • the electroluminescent device includes a hole injection layer and a hole transport layer, and the hole injection layer and the hole transport layer are stacked on the first electrode layer and the light emitting layer Between the layers, the hole injection layer is laminated with the first electrode.
  • the electroluminescent device includes a hole transport layer and an electron blocking layer, and the hole transport layer and the electron blocking layer are stacked on the first electrode layer and the light emitting layer And the hole transport layer is laminated with the first electrode.
  • the electroluminescent device includes an electron blocking layer and an electron injection layer disposed between the second electrode layer and the second electron transport layer, the electron blocking A layer is disposed between the light emitting layer and the second electron transport layer.
  • Another object of the present invention is to provide a display comprising the above quantum dot electroluminescent device.
  • the present invention has the following beneficial effects:
  • the first electron transport layer includes an inorganic metal oxide material
  • the second electron transport layer includes an organic electron transport material.
  • the electron transport layers of two different materials are superimposed to effectively control the electron mobility.
  • the difference between the hole mobility and the electron mobility is weakened, the carrier balance is achieved, and the current efficiency is greatly improved.
  • the inorganic metal oxide material or the organic electron transport material is used alone, the current efficiency cannot be effectively improved. If the metal oxide and the organic electron transport material are mixed in proportion, the mixed material is used as the electron transport layer material, and a suitable one is sought. There are great difficulties in the selection of solvent and electron transport layer film-forming preparation processes, and the efficiency of the device is low.
  • the present application preferably uses a multi-element metal oxide zinc magnesium oxide as the first electron transporting material, preferably an organic electron transporting material doped with the organometallic complex LiQ as the second electron transporting layer, so that the electron mobility and the quantum dot electroluminescent device are empty.
  • the hole migration rate is balanced and good current efficiency is obtained.
  • the space charge accumulation in the device is reduced, the quantum dot is better in electrical neutrality, and the efficiency of quantum dot electroluminescence is improved, which can be applied to solid-state illumination, flat panel display and the like.
  • FIG. 1 is a schematic structural view of Embodiment 1 of the present invention.
  • quantum dot electroluminescent device of the present invention will be further described in detail below in conjunction with specific embodiments.
  • a structure of a quantum dot electroluminescent device includes a first electrode layer, a light emitting layer, a first electron transport layer, a second electron transport layer, and a second electrode layer which are laminated.
  • the first electrode layer is an anode layer.
  • the anode material may be transparent or opaque, and may be selected from ITO, AZO, TZO, nano silver wire film or graphene.
  • the anode material is ITO and has a thickness of 100-150 nm.
  • the luminescent layer is a quantum dot luminescent layer, and electrons transported from the anode direction and electrons transported in the cathode direction converge in the quantum dot layer to form photons, which are recombined by photons. Therefore, whether the mobility of holes and the mobility of electrons are balanced have a large influence on the luminous efficiency of the quantum dot electroluminescent device. Understandably, the quantum dot material may be selected from CdSe (cadmium selenide), CdS (cadmium sulfide), CdTe (cadmium telluride), ZnSe (zinc selenide), ZnTe (zinc telluride), ZnS (zinc sulfide), etc. .
  • quantum dots can be regulated by changing the particle size and chemical composition.
  • quantum dots of a core/shell structure have been developed.
  • the quantum dot material is a CdSe/CdS core-shell structure, that is, a nanocrystalline semiconductor material having CdSe as a core and CdS as a shell. Improve quantum dot stability and quantum yield.
  • the first electron transport layer is located on the light-emitting layer, and the material comprises an inorganic metal oxide.
  • the addition of the metal oxide is advantageous for improving the stability of the quantum dot electroluminescent device due to its photochemical stability, and the electron mobility of the metal oxide is high. , matching the energy level of the quantum dot.
  • the inorganic metal oxide may be a monovalent metal oxide such as one or more of ZnO, MgO, TiO 2 , SnO 2 , ZrO 2 , HfO 2 or Ta 2 O 3 .
  • the inorganic metal oxide may also be a multi-metal oxide such as zinc magnesium oxide, zinc tin oxide, zinc aluminum oxide, zinc calcium oxide, zinc tungsten oxide, zinc zinc oxide, zinc oxide nickel, ZnO-TiO 2 -SnO 2 and ZnO.
  • a multi-metal oxide such as zinc magnesium oxide, zinc tin oxide, zinc aluminum oxide, zinc calcium oxide, zinc tungsten oxide, zinc zinc oxide, zinc oxide nickel, ZnO-TiO 2 -SnO 2 and ZnO.
  • the material of the first electron transport layer is a multi-element metal oxide zinc magnesium oxide.
  • the first electron transport layer may also be a combination of an inorganic metal oxide and a polymer material PEIE.
  • PEIE is a polyethoxyethyleneimine.
  • the second electron transport layer is on the first electron transport layer, and the material includes an organic electron transport material.
  • the organic electron transporting material is selected from the group consisting of organic small molecule materials NBphen (2,9-Bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline, 2,9-bis(naphthalene-2) -yl)-4,7-diphenyl-1,10-phenanthroline), Bphen(4,7-Diphenyl-1,10-phenanthroline,4,7-diphenyl-1,10-phenanthroline ), TPBi (1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene ), Bpy-FOXD(2,7-Bis[2-(2,2'-bipyridine-6-yl)-1,3,4-oxadiaz
  • TmPyPB is 1,3,5-tris(m-pyridin-3-ylphenyl)benzene
  • BCP is bathing copper
  • the organic electron transporting material may also be organic polymeric material PEIE.
  • the second electron transport layer further comprises a doping material selected from the group consisting of a metal, a metal inorganic salt or an organometallic complex.
  • the metal is selected from the group consisting of Li, Na, K, Rb, Cs or Yb; the metal inorganic salt is selected from Li 2 CO 3 , K 2 SiO 3 , Rb 2 CO 3 or Cs 2 CO 3 ; the organometallic complex is selected from LiQ , AlQ 3 (Tris-(8-hydroxyquinoline) aluminum, tris(8-hydroxyquinoline) aluminum).
  • the dopant material is LiQ and LiQ is lithium octahydroxyquinolate.
  • the doping material accounts for 1% to 60% of the total mass of the second electron transport layer.
  • the dopant material accounts for 40%-60% of the total mass of the second electron transport layer.
  • the above doping ratio is advantageous for increasing the carrier concentration, mobility, and conductivity of the second electron transport layer.
  • the quantum dot light-emitting layer is in direct contact with the pure organic electron transport layer, charge transfer occurs automatically when no external voltage is applied, and the quantum dots are charged, resulting in a decrease in luminous efficiency.
  • the second electrode layer is on the second electron transport layer. It can be understood that the second electrode layer is a cathode layer.
  • the material of the second electrode layer is selected from, but not limited to, silver, aluminum or a silver-based alloy.
  • the above embodiment can control the mobility of electrons by providing two layers of electron transport layers. Further, the difference in mobility between electrons and holes is weakened.
  • a structure of a quantum dot electroluminescent device includes the above first electrode layer, light emitting layer, first electron transport layer, second electron transport layer, and second electrode layer, and further includes substrate and hole transport Floor.
  • the substrate is used to carry other structural layers.
  • the substrate may be a rigid substrate or a flexible substrate.
  • the rigid substrate can be made of ceramic or various types of glass.
  • the flexible substrate may be a polyimide film (PI) and a derivative thereof, polyethylene naphthalate (PEN), phosphoenolpyruvate (PEP) or a diphenylene ether resin.
  • the hole transport layer is located above the first electrode layer to transport holes and allow holes to reach the light-emitting layer.
  • the material of the hole transport layer may be polytetraphenylbenzidine or polyvinylcarbazole.
  • the material of the hole transport layer is TFB, and the TFB is poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-) Phenyl)diphenylamine)];
  • the hole transport layer After the hole transport layer is added, the difference between the mobility of electrons and holes is further weakened, and the balance of carriers is better realized, and the current effect is better.
  • a structure of a quantum dot electroluminescent device includes a substrate, a first electrode layer, a hole transport layer, a light emitting layer, a first electron transport layer, a second electron transport layer, and a second electrode layer. Also included is one or more layers of a hole injection layer, a hole blocking layer, an electron blocking layer, and an electron injection layer, wherein the hole injection layer is disposed between the first electrode layer and the hole transport layer, and the electron blocking layer is disposed at Between the hole transport layer and the light emitting layer, an electron injection layer is disposed between the second electrode layer and the second electron transport layer, and a hole blocking layer is disposed on the light emitting layer and the first electron transport layer between.
  • the hole injection layer is located above the substrate and the first electrode layer, and the hole injection layer can provide holes.
  • the material of the hole injection layer is PEDOT:PSS
  • PEDOT:PSS is an aqueous solution of a high molecular polymer, and the conductivity is high. According to different formulations, an aqueous solution having different conductivity can be obtained.
  • This compound is composed of two substances, PEDOT and PSS.
  • PEDOT is a polymer of EDOT (3,4-ethylenedioxythiophene monomer)
  • PSS is a polystyrene sulfonate.
  • the hole injection layer, the hole blocking layer, the electron injection layer, and the electron blocking layer are auxiliary film layers in order to further improve the light-emitting efficiency of the light-emitting function layer.
  • Each functional layer of the above quantum dot electroluminescent device can be processed into a film by a solution method including, but not limited to, inkjet printing, spin coating, slit coating, and screen printing, in addition to quantum dots.
  • Other functional layers than others can be formed into a film by a vacuum hot-dip evaporation process.
  • the present embodiment provides a quantum dot electroluminescent device having a structure as shown in FIG. 1.
  • the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, and the light emitting layer 104 are laminated in this order from bottom to top.
  • the material of the first electron transport layer 105 is ZnO; the material of the second electron transport layer 106 is TmPyPB: LiQ.
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • first electron transport layer material depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes in a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being ZnO
  • the thickness of the first electron transport layer is 20 nm;
  • Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
  • the present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
  • the material of the first electron transport layer 105 is MgO; the material of the second electron transport layer 106 is TmPyPB: LiQ.
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • first electron transport layer material depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being MgO
  • the thickness of the first electron transport layer is 20 nm;
  • Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
  • the present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
  • the material of the first electron transport layer 105 is TiO 2 ; the material of the second electron transport layer 106 is Bphen:LiQ.
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • first electron transport layer material depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being TiO 2 , the thickness of the first electron transport layer is 20 nm;
  • Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
  • the present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
  • the material of the first electron transport layer 105 is ZnO; the material of the second electron transport layer 106 is BCP:LiQ.
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • first electron transport layer material depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes in a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being ZnO
  • the thickness of the first electron transport layer is 20 nm;
  • Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
  • the present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
  • the material of the first electron transport layer 105 is MgO; the material of the second electron transport layer 106 is BCP: LiQ.
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • first electron transport layer material depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being MgO
  • the thickness of the first electron transport layer is 20 nm;
  • Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
  • the present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
  • the material of the first electron transport layer 105 is ZnMgO; the material of the second electron transport layer 106 is BCP: LiQ.
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • first electron transport layer material depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being ZnMgO
  • the thickness of the first electron transport layer is 20 nm;
  • Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
  • the present embodiment provides a quantum dot electroluminescent device, sequentially stacking the first electrode layer 101, the light emitting layer 104, the first electron transport layer 105, the second electron transport layer 106, and the second electrode layer 107 from bottom to top;
  • the material of the first electron transport layer 105 is ZnO-TiO 2 -SnO 2 ; the material of the second electron transport layer 106 is TmPyPB:LiQ.
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • Al is evaporated on the second electron transport layer to form a second electrode having a thickness of 120 nm.
  • the present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
  • the material of the first electron transport layer 105 is ZnMgO and PEIE; the material of the second electron transport layer 106 is PEIE.
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
  • the embodiment provides a quantum dot electroluminescent device.
  • the structure of the electroluminescent device is basically the same as that of the embodiment 7. The difference is that a hole transport layer is disposed between the first electrode layer and the light emitting layer, and the hole is transported.
  • the material of the layer is TFB.
  • the present comparative example provides a quantum dot electroluminescent device comprising, in order from bottom to top, a substrate 100, a first electrode layer 101, a hole injection layer 102, a hole transport layer 103, a light emitting layer 104, an electron transport layer 105, and a Two electrode layer 107;
  • the material of the electron transport layer 105 is ZnO.
  • the preparation process of the quantum dot electroluminescent device of the present comparative example is as follows:
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • Al is evaporated on the electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
  • the present comparative example provides a quantum dot electroluminescent device comprising, in order from bottom to top, a substrate 100, a first electrode layer 101, a hole injection layer 102, a hole transport layer 103, a light emitting layer 104, an electron transport layer 106, and Two electrode layer 107;
  • the material of the electron transport layer 106 is TmPyPB: LiQ.
  • the preparation process of the quantum dot electroluminescent device of the present comparative example is as follows:
  • a glass substrate containing a transparent electrode of ITO 120 nm was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
  • the thickness is 40 nm;
  • Al was evaporated on the electron transport layer to form a second electrode, and the thickness of the second electrode was 120 nm.
  • the preparation process of the quantum dot electroluminescent device of the present comparative example was the same as in Example 8.
  • the present comparative example provides a quantum dot electroluminescent device.
  • the structure of the electroluminescent device is substantially the same as that of Comparative Example 3, except that the material of the second electron transporting layer is TmPyPB.
  • the present comparative example provides a quantum dot electroluminescent device.
  • the structure of the electroluminescent device is basically the same as that of Embodiment 7, except that it does not contain the first electron transport layer, only the second electron transport layer, and the second electron transport.
  • the material of the layer is TmPyPB: LiQ.
  • the preparation process of the quantum dot electroluminescent device of the present comparative example was the same as that of Example 7, and the preparation step of the first electron transport layer was not included.
  • the quantum dot electroluminescent device of the above examples and comparative examples were tested for device current efficiency at a current density of 10 mA/cm 2 , and the current efficiency of Comparative Example 3 was normalized to 1, and the corresponding current efficiency value was obtained.
  • the results are as follows:
  • Example 8 the organic polymer material PEIE was added to the first electron transport layer to increase the current effect.
  • Comparative Example 3 and Comparative Example 4 when the organic small molecule material TmPyPB was added to the first electron transport layer, the current effect was poor.

Abstract

The present invention relates to a quantum dot electroluminescent component, comprising a first electrode layer, a light-emitting layer, and a second electrode layer sequentially stacked. A first electron transport layer and a second electron transport layer are provided between the light-emitting layer and the second electrode layer. The materials of the first electron transport layer comprise an inorganic metal oxide transport material. The materials of the second electron transport layer comprise an organic electron transport material. The present invention stacks and uses the two electron transport layers of different materials, reduces the difference between hole mobility and electron mobility, implements a balance of carriers, significantly increases current efficiency, and is applicable in the fields of solid-state lighting and tablet displays.

Description

量子点电致发光器件及显示器Quantum dot electroluminescent device and display
本申请要求于2017年11月29日提交中国专利局、申请号为201711229119.6发明名称为“量子点电致发光器件及显示器”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。The present application claims priority to Chinese Patent Application No. 200911229119.6, entitled "Quantum Electroluminescent Device and Display", filed on November 29, 2017, the entire contents of which is incorporated herein by reference. .
技术领域Technical field
本发明涉及量子点领域，特别是涉及量子点电致发光器件及显示器。The present invention relates to the field of quantum dots, and more particularly to quantum dot electroluminescent devices and displays.
背景技术Background technique
量子点是具有量子限制效应的纳米尺寸半导体材料，受到光或电的激发，量子点便会发出非常纯净的光，具有发光量子效率高、性能稳定等特点。利用量子点电致发光特性制作的量子点发光二极管(Quantum Dot Light Emitting Diode，QLED)器件作为一种新兴的发光器件，近年来受到了广泛的关注。与传统的有机发光二极管(OLED)相比，QLED具有更加优异的色纯度、亮度和可视角等特点。使得以量子点材料作为发光层的量子点发光二极管在固态照明、平板显示等领域具有广泛的应用前景，受到了学术界以及产业界的广泛关注。Quantum dots are nano-sized semiconductor materials with quantum confinement effects. When excited by light or electricity, quantum dots emit very pure light, featuring high luminous efficiency and stable performance. As an emerging light-emitting device, Quantum Dot Light Emitting Diode (QLED) devices fabricated by quantum dot electroluminescence properties have received extensive attention in recent years. Compared with traditional organic light-emitting diodes (OLEDs), QLEDs have superior color purity, brightness and viewing angle. The quantum dot light-emitting diodes using quantum dot materials as light-emitting layers have broad application prospects in the fields of solid-state illumination and flat panel display, and have attracted extensive attention in academia and industry.
通过对量子点材料的改进以及QLED器件结构的不断优化，现有QLED器件的性能得到了大幅度的提高，但是其发光效率与产业化生产的要求还有一定差距。除了电极以外，目前典型的量子点发光二极管的结构是一个空穴传输层，一个量子点发光层，一个电子传输层。采用这种多层结构，电子与空穴传输速率不同，导致正负载流子的不平衡。载流子的不平衡是影响QLED器件性能的重要因素之一，特别是对QLED器件发光效率和寿命的影响。如何获得有效的载流子平衡，进一步提升QLED器件的性能，仍然是当前学术界和产业界研发的重点。Through the improvement of quantum dot materials and the continuous optimization of QLED device structure, the performance of existing QLED devices has been greatly improved, but there is still a gap between the luminous efficiency and the requirements of industrial production. In addition to the electrodes, the structure of a typical quantum dot light-emitting diode is a hole transport layer, a quantum dot light-emitting layer, and an electron transport layer. With this multilayer structure, the electron and hole transport rates are different, resulting in an imbalance of positive load carriers. Carrier imbalance is one of the important factors affecting the performance of QLED devices, especially the luminous efficiency and lifetime of QLED devices. How to obtain effective carrier balance and further improve the performance of QLED devices is still the focus of current academic and industrial research and development.
发明内容Summary of the invention
基于此，有必要针对上述问题，提供一种控制电子传输速率，进而实现载流子平衡的量子点电致发光器件及显示器。Based on this, it is necessary to provide a quantum dot electroluminescent device and a display that control the electron transport rate and thereby achieve carrier balance in view of the above problems.
本发明提供一种量子点电致发光器件，包括相对设置的第一电极层、第二电极层，设置于所述第一电极层与所述第二电极层之间的发光层，设置于所述发光层与所述第二电极层之 间的第一电子传输层，设置于所述第一电子传输层与所述第二电极层之间的第二电子传输层；；The present invention provides a quantum dot electroluminescent device comprising a first electrode layer and a second electrode layer disposed opposite to each other, and a light emitting layer disposed between the first electrode layer and the second electrode layer. a first electron transport layer between the light emitting layer and the second electrode layer, and a second electron transport layer disposed between the first electron transport layer and the second electrode layer;
所述第一电子传输层的材料包括无机金属氧化物，所述第二电子传输层的材料包括有机电子传输材料。The material of the first electron transport layer includes an inorganic metal oxide, and the material of the second electron transport layer includes an organic electron transport material.
在其中一个实施例中，所述无机金属氧化物为一元金属氧化物和多元金属氧化物中的一种或几种。In one embodiment, the inorganic metal oxide is one or more of a monovalent metal oxide and a multi-metal oxide.
在其中一个实施例中，所述多元金属氧化物选自氧化锌镁、氧化锌锡、氧化锌铝、氧化锌钙、氧化锌钨、氧化锌钛、氧化锌镍、ZnO-TiO 2-SnO 2和ZnO-MgO-TiO 2的一种或几种；和/或 In one embodiment, the multi-metal oxide is selected from the group consisting of zinc magnesium oxide, zinc tin oxide, zinc aluminum oxide, calcium zinc oxide, zinc tungsten oxide, zinc zinc oxide, zinc zinc oxide, and ZnO-TiO 2 -SnO 2 . And one or more of ZnO-MgO-TiO 2 ; and/or
所述一元金属氧化物选自ZnO、MgO、TiO 2、SnO 2、ZrO 2、HfO 2或Ta 2O 3的一种或几种。 The monobasic metal oxide is selected from one or more of ZnO, MgO, TiO 2 , SnO 2 , ZrO 2 , HfO 2 or Ta 2 O 3 .
在其中一个实施例中，所述第一电子传输层还包括高分子材料PEIE。In one embodiment, the first electron transport layer further comprises a polymer material PEIE.
在其中一个实施例中，所述有机电子传输材料选自NBphen、TPBi、Bpy-FOXD、BP4mPy、BTB、BIPO、3TPYMB、PBD、BAlq、PEIE、Bphen、TmPyPB和BCP的一种或几种。In one embodiment, the organic electron transporting material is selected from one or more of the group consisting of NBphen, TPBi, Bpy-FOXD, BP4mPy, BTB, BIPO, 3TPYMB, PBD, BAlq, PEIE, Bphen, TmPyPB, and BCP.
在其中一个实施例中，所述第二电子传输层还包括掺杂材料，所述掺杂材料选自金属、金属无机盐或有机金属配合物；和/或In one embodiment, the second electron transport layer further includes a dopant material selected from the group consisting of a metal, a metal inorganic salt or an organometallic complex; and/or
所述掺杂材料占所述第二电子传输层总质量的1％-60％。The dopant material accounts for 1% to 60% of the total mass of the second electron transport layer.
在其中一个实施例中，所述金属选自Li、Na、K、Rb、Cs或Yb；和/或In one embodiment, the metal is selected from the group consisting of Li, Na, K, Rb, Cs, or Yb; and/or
所述金属无机盐选自Li 2CO 3、K 2SiO 3、Rb 2CO 3或Cs 2CO 3；和/或 The metal inorganic salt is selected from the group consisting of Li 2 CO 3 , K 2 SiO 3 , Rb 2 CO 3 or Cs 2 CO 3 ; and/or
所述有机金属配合物选自LiQ、AlQ 3。 The organometallic complex is selected from the group consisting of LiQ, AlQ 3 .
在其中一个实施例中，所述掺杂材料占所述第二电子传输层总质量的40％-60％。In one embodiment, the dopant material comprises from 40% to 60% of the total mass of the second electron transport layer.
在其中一个实施例中，所述第一电子传输层的厚度为1-150nm；和/或In one embodiment, the first electron transport layer has a thickness of 1-150 nm; and/or
所述第二电子传输层的厚度为1-150nm。The second electron transport layer has a thickness of 1 to 150 nm.
在其中的一个实施例中，所述第一电子传输层的材料为无机金属氧化物或无机金属氧化物与高分子材料PEIE的复合材料，所述第二电子传输层的材料为有机电子传输材料或有机电子传输材料与掺杂材料的复合材料。In one embodiment, the material of the first electron transport layer is a composite material of an inorganic metal oxide or an inorganic metal oxide and a polymer material PEIE, and the material of the second electron transport layer is an organic electron transport material. Or a composite of an organic electron transport material and a dopant material.
在其中一个实施例中，还包括空穴注入层、空穴传输层、空穴阻挡层、电子阻挡层和电子注入层中的一层或多层。In one embodiment, one or more of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, and an electron injection layer are further included.
在其中一个实施例中，所述电致发光器件包括空穴注入层、空穴传输层、空穴阻挡层、 电子阻挡层或电子注入层中的一层，所述空穴注入层、空穴传输层或电子阻挡层设置在第一电极层与所述发光层之间，或者，所述电子注入层设置在所述第二电极层与所述第二电子传输层之间，或者，所述电子阻挡层设置在所述发光层与所述第二电子传输层之间。In one embodiment, the electroluminescent device comprises one of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer or an electron injection layer, the hole injection layer, the hole a transport layer or an electron blocking layer is disposed between the first electrode layer and the light emitting layer, or the electron injection layer is disposed between the second electrode layer and the second electron transport layer, or An electron blocking layer is disposed between the light emitting layer and the second electron transport layer.
在其中一个实施例中，所述电致发光器件包括空穴注入层、空穴传输层和电子阻挡层，所述空穴注入层、所述空穴传输层和所述电子阻挡层层叠设置在所述第一电极层与所述发光层之间，且所述空穴注入层与所述第一电极层叠设。In one embodiment, the electroluminescent device includes a hole injection layer, a hole transport layer, and an electron blocking layer, and the hole injection layer, the hole transport layer, and the electron blocking layer are stacked on The first electrode layer and the light emitting layer are disposed, and the hole injection layer is laminated with the first electrode.
在其中一个实施例中，所述电致发光器件包括空穴注入层和空穴传输层，所述空穴注入层和所述空穴传输层层叠设置在所述第一电极层与所述发光层之间，且所述空穴注入层与所述第一电极层叠设。In one embodiment, the electroluminescent device includes a hole injection layer and a hole transport layer, and the hole injection layer and the hole transport layer are stacked on the first electrode layer and the light emitting layer Between the layers, the hole injection layer is laminated with the first electrode.
在其中一个实施例中，所述电致发光器件包括空穴传输层和电子阻挡层，所述空穴传输层和所述电子阻挡层层叠设置在所述第一电极层与所述发光层之间，且所述空穴传输层与所述第一电极层叠设。In one embodiment, the electroluminescent device includes a hole transport layer and an electron blocking layer, and the hole transport layer and the electron blocking layer are stacked on the first electrode layer and the light emitting layer And the hole transport layer is laminated with the first electrode.
在其中一个实施例中，所述电致发光器件包括电子阻挡层和电子注入层，所述电子注入层设置在所述第二电极层与所述第二电子传输层之间，所述电子阻挡层设置在所述发光层与所述第二电子传输层之间。In one embodiment, the electroluminescent device includes an electron blocking layer and an electron injection layer disposed between the second electrode layer and the second electron transport layer, the electron blocking A layer is disposed between the light emitting layer and the second electron transport layer.
本发明的另一个目的是提供一种显示器，包括上述量子点电致发光器件。Another object of the present invention is to provide a display comprising the above quantum dot electroluminescent device.
与现有方案相比，本发明具有以下有益效果：Compared with the existing solutions, the present invention has the following beneficial effects:
上述量子点电致发光器件，在发光层与第二电极层之间设置两层电子传输层，第一电子传输层包括无机金属氧化物材料，第二电子传输层包括有机电子传输材料。两种不同材料的电子传输层叠加使用，可有效的控制电子迁移率。In the above quantum dot electroluminescent device, two electron transport layers are disposed between the light emitting layer and the second electrode layer, the first electron transport layer includes an inorganic metal oxide material, and the second electron transport layer includes an organic electron transport material. The electron transport layers of two different materials are superimposed to effectively control the electron mobility.
通过上述对电子传输层的改进，减弱了空穴迁移率与电子迁移率之间的差异，实现了载流子的平衡，使电流效率得到了大幅提升。无机金属氧化物材料或有机电子传输材料单独使用时，均无法有效提升电流效率，若将金属氧化物和有机电子传输材料按比例混合，将混合后的材料作为电子传输层材料，在寻找合适的溶剂与电子传输层成膜制备工艺的选择上存在较大的困难，且器件的效率较低。Through the above improvement of the electron transport layer, the difference between the hole mobility and the electron mobility is weakened, the carrier balance is achieved, and the current efficiency is greatly improved. When the inorganic metal oxide material or the organic electron transport material is used alone, the current efficiency cannot be effectively improved. If the metal oxide and the organic electron transport material are mixed in proportion, the mixed material is used as the electron transport layer material, and a suitable one is sought. There are great difficulties in the selection of solvent and electron transport layer film-forming preparation processes, and the efficiency of the device is low.
本申请优选多元金属氧化物氧化锌镁作为第一电子传输材料，优选掺杂有机金属配合物LiQ的有机电子传输材料作为第二电子传输层，使量子点电致发光器件中电子迁移率与空穴迁移率达到平衡，获得较好的电流效率。同时，减少了器件中的空间电荷积累，保持量子点 较好的电中性，提高了量子点电致发光的效率，可应用于固态照明、平板显示等领域。The present application preferably uses a multi-element metal oxide zinc magnesium oxide as the first electron transporting material, preferably an organic electron transporting material doped with the organometallic complex LiQ as the second electron transporting layer, so that the electron mobility and the quantum dot electroluminescent device are empty. The hole migration rate is balanced and good current efficiency is obtained. At the same time, the space charge accumulation in the device is reduced, the quantum dot is better in electrical neutrality, and the efficiency of quantum dot electroluminescence is improved, which can be applied to solid-state illumination, flat panel display and the like.
附图说明DRAWINGS
图1为本发明实施例1的结构示意图。FIG. 1 is a schematic structural view of Embodiment 1 of the present invention.
具体实施方式Detailed ways
以下结合具体实施例对本发明的量子点电致发光器件作进一步详细的说明。The quantum dot electroluminescent device of the present invention will be further described in detail below in conjunction with specific embodiments.
本发明一个实施方式的量子点电致发光器件的结构包括层叠设置的第一电极层、发光层、第一电子传输层、第二电子传输层和第二电极层。A structure of a quantum dot electroluminescent device according to an embodiment of the present invention includes a first electrode layer, a light emitting layer, a first electron transport layer, a second electron transport layer, and a second electrode layer which are laminated.
第一电极层为阳极层。可以理解的，阳极材料可以是透明的，也可以是不透明的，可选自ITO、AZO、TZO、纳米银线薄膜或石墨烯等。优选的，阳极材料为ITO，厚度为100-150nm。The first electrode layer is an anode layer. It can be understood that the anode material may be transparent or opaque, and may be selected from ITO, AZO, TZO, nano silver wire film or graphene. Preferably, the anode material is ITO and has a thickness of 100-150 nm.
发光层为量子点发光层，从阳极方向传输的空穴与阴极方向传输来的电子在量子点层中汇聚后形成光子，通过光子的重组发光。因此，空穴的迁移率与电子的迁移率是否平衡，对量子点电致发光器件的发光效率有较大的影响。可以理解的，量子点材料可选择为CdSe(硒化镉)、CdS(硫化镉)、CdTe(碲化镉)、ZnSe(硒化锌)、ZnTe(碲化锌)、ZnS(硫化锌)等。可以通过改变粒径尺寸和化学成分对量子点的光谱进行调控。进一步的，为了增强量子点的发光效率和化学稳定性，发展了核/壳结构的量子点。优选的，量子点材料为CdSe/CdS核壳结构，即以CdSe为核、CdS为壳的纳米晶体半导体材料。可提高量子点的稳定性和量子产额。The luminescent layer is a quantum dot luminescent layer, and electrons transported from the anode direction and electrons transported in the cathode direction converge in the quantum dot layer to form photons, which are recombined by photons. Therefore, whether the mobility of holes and the mobility of electrons are balanced have a large influence on the luminous efficiency of the quantum dot electroluminescent device. Understandably, the quantum dot material may be selected from CdSe (cadmium selenide), CdS (cadmium sulfide), CdTe (cadmium telluride), ZnSe (zinc selenide), ZnTe (zinc telluride), ZnS (zinc sulfide), etc. . The spectrum of quantum dots can be regulated by changing the particle size and chemical composition. Further, in order to enhance the luminous efficiency and chemical stability of quantum dots, quantum dots of a core/shell structure have been developed. Preferably, the quantum dot material is a CdSe/CdS core-shell structure, that is, a nanocrystalline semiconductor material having CdSe as a core and CdS as a shell. Improve quantum dot stability and quantum yield.
第一电子传输层位于发光层上，材料包括无机金属氧化物，加入金属氧化物，由于其光化学性质稳定，有利于提高量子点电致发光器件的稳定性，且金属氧化物的电子迁移率高，与量子点的能级匹配。无机金属氧化物可以为一元金属氧化物，例如ZnO、MgO、TiO 2、SnO 2、ZrO 2、HfO 2或Ta 2O 3的一种或几种。无机金属氧化物也可以为多元金属氧化物，例如氧化锌镁、氧化锌锡、氧化锌铝、氧化锌钙、氧化锌钨、氧化锌钛、氧化锌镍、ZnO-TiO 2-SnO 2和ZnO-MgO-TiO 2的一种或几种。优选的，第一电子传输层的材料为多元金属氧化物氧化锌镁。 The first electron transport layer is located on the light-emitting layer, and the material comprises an inorganic metal oxide. The addition of the metal oxide is advantageous for improving the stability of the quantum dot electroluminescent device due to its photochemical stability, and the electron mobility of the metal oxide is high. , matching the energy level of the quantum dot. The inorganic metal oxide may be a monovalent metal oxide such as one or more of ZnO, MgO, TiO 2 , SnO 2 , ZrO 2 , HfO 2 or Ta 2 O 3 . The inorganic metal oxide may also be a multi-metal oxide such as zinc magnesium oxide, zinc tin oxide, zinc aluminum oxide, zinc calcium oxide, zinc tungsten oxide, zinc zinc oxide, zinc oxide nickel, ZnO-TiO 2 -SnO 2 and ZnO. One or more of -MgO-TiO 2 . Preferably, the material of the first electron transport layer is a multi-element metal oxide zinc magnesium oxide.
进一步的，第一电子传输层还可为无机金属氧化物与高分子材料PEIE的组合。PEIE为聚乙氧基乙烯亚胺。Further, the first electron transport layer may also be a combination of an inorganic metal oxide and a polymer material PEIE. PEIE is a polyethoxyethyleneimine.
第二电子传输层位于第一电子传输层上，材料包括有机电子传输材料。可以理解的，有 机电子传输材料选自有机小分子材料NBphen(2,9-Bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline，2,9-双(萘-2-基)-4,7-二苯基-1,10-菲咯啉)、Bphen(4,7-Diphenyl-1,10-phenanthroline，4,7-二苯基-1,10-菲咯啉)、TPBi(1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene，1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯)、Bpy-FOXD(2,7-Bis[2-(2,2'-bipyridine-6-yl)-1,3,4-oxadiazo-5-yl]-9,9-dimethylfluorene，2,7-双[2-(2,2'-联吡啶-6-基)-1,3,4-恶二唑-5-基]-9,9-二甲基芴)、BP4mPy(3,3',5,5'-Tetra[(m-pyridyl)-phen-3-yl]biphenyl，3,3',5,5'-四[(间-吡啶基)-苯-3-基]联苯)、BTB(4,4'-Bis(4,6-diphenyl-1,3,5-triazin-2-yl)biphenyl，4,4'-双(4,6-二苯基-1,3,5-三嗪-2-基)联苯)、BIPO(2,2'-(4,4'-(Phenylphosphoryl)bis(4,1-phenylene))bis(1-phenyl-1H-benzo[d]imidazole)，The second electron transport layer is on the first electron transport layer, and the material includes an organic electron transport material. It can be understood that the organic electron transporting material is selected from the group consisting of organic small molecule materials NBphen (2,9-Bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline, 2,9-bis(naphthalene-2) -yl)-4,7-diphenyl-1,10-phenanthroline), Bphen(4,7-Diphenyl-1,10-phenanthroline,4,7-diphenyl-1,10-phenanthroline ), TPBi (1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene, 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene ), Bpy-FOXD(2,7-Bis[2-(2,2'-bipyridine-6-yl)-1,3,4-oxadiazo-5-yl]-9,9-dimethylfluorene,2,7- Bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazol-5-yl]-9,9-dimethylhydrazine), BP4mPy(3,3', 5,5'-Tetra[(m-pyridyl)-phen-3-yl]biphenyl,3,3',5,5'-tetra[(m-pyridyl)-phenyl-3-yl]biphenyl), BTB(4,4'-Bis(4,6-diphenyl-1,3,5-triazin-2-yl)biphenyl,4,4'-bis(4,6-diphenyl-1,3,5- Triazine-2-yl)biphenyl), BIPO(2,2'-(4,4'-(Phenylphosphoryl)bis(4,1-phenylene))bis(1-phenyl-1H-benzo[d]imidazole) ,
2,2'-(4,4'-(苯基磷酰基)双(4,1-亚苯基)双(1-苯基-1H-苯并[d]咪唑))、3TPYMB(Tris(2,4,6-triMethyl-3-(pyridin-3-yl)phenyl)borane，三(2,4,6-三甲基-3-(吡啶-3-基)苯基)硼烷)、PBD(2-(4-Biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole，2-(4-联苯基)-5-(4-叔丁基苯基)-1,3,4-恶二唑)、BAlq(Bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium，2,2'-(4,4'-(phenylphosphoryl)bis(4,1-phenylene)bis(1-phenyl-1H-benzo[d]imidazole)), 3TPYMB (Tris(2) , 4,6-triMethyl-3-(pyridin-3-yl)phenyl)borane, tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane), PBD ( 2-(4-Biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1, 3,4-oxadiazole), BAlq(Bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium,
双(2-甲基-8-羟基喹啉)-4-(苯基苯酚)铝)、TmPyPB和BCP的一种或几种。其中，TmPyPB为1,3,5-三(间-吡啶-3-基苯基)苯；BCP为浴铜灵；进一步的，有机电子传输材料还可以为有机高分子材料PEIE。One or more of bis(2-methyl-8-hydroxyquinoline)-4-(phenylphenol)aluminum), TmPyPB and BCP. Wherein, TmPyPB is 1,3,5-tris(m-pyridin-3-ylphenyl)benzene; BCP is bathing copper; further, the organic electron transporting material may also be organic polymeric material PEIE.
优选的，第二电子传输层还包括掺杂材料，所述掺杂材料选自金属、金属无机盐或有机金属配合物。Preferably, the second electron transport layer further comprises a doping material selected from the group consisting of a metal, a metal inorganic salt or an organometallic complex.
优选的，金属选自Li、Na、K、Rb、Cs或Yb；金属无机盐选自Li 2CO 3、K 2SiO 3、Rb 2CO 3或Cs 2CO 3；有机金属配合物选自LiQ、AlQ 3(Tris-(8-hydroxyquinoline)aluminum，三(8-羟基喹啉)铝)。 Preferably, the metal is selected from the group consisting of Li, Na, K, Rb, Cs or Yb; the metal inorganic salt is selected from Li 2 CO 3 , K 2 SiO 3 , Rb 2 CO 3 or Cs 2 CO 3 ; the organometallic complex is selected from LiQ , AlQ 3 (Tris-(8-hydroxyquinoline) aluminum, tris(8-hydroxyquinoline) aluminum).
进一步优选的，掺杂材料为LiQ，LiQ为八羟基喹啉锂。Further preferably, the dopant material is LiQ and LiQ is lithium octahydroxyquinolate.
掺杂材料占所述第二电子传输层总质量的1％-60％。The doping material accounts for 1% to 60% of the total mass of the second electron transport layer.
优选的，掺杂材料占所述第二电子传输层总质量的40％-60％。上述掺杂比例有利于提高第二电子传输层的载流子浓度、迁移率和导电率。Preferably, the dopant material accounts for 40%-60% of the total mass of the second electron transport layer. The above doping ratio is advantageous for increasing the carrier concentration, mobility, and conductivity of the second electron transport layer.
需要注意的是，若量子点发光层若与纯有机电子传输层直接接触，在不施加外部电压的情况下，会自动发生电荷转移，使量子点带上电荷，造成其发光效率的下降。It should be noted that if the quantum dot light-emitting layer is in direct contact with the pure organic electron transport layer, charge transfer occurs automatically when no external voltage is applied, and the quantum dots are charged, resulting in a decrease in luminous efficiency.
第二电极层位于第二电子传输层上。可以理解的，第二电极层为阴极层。第二电极层的 材料选自但不限于银、铝或银基合金等。The second electrode layer is on the second electron transport layer. It can be understood that the second electrode layer is a cathode layer. The material of the second electrode layer is selected from, but not limited to, silver, aluminum or a silver-based alloy.
上述实施方式通过设置两层电子传输层，可控制电子的迁移率。进而减弱电子与空穴的迁移率的差异。The above embodiment can control the mobility of electrons by providing two layers of electron transport layers. Further, the difference in mobility between electrons and holes is weakened.
本发明的另一实施方式的量子点电致发光器件的结构包括上述第一电极层、发光层、第一电子传输层、第二电子传输层和第二电极层，还包括基板和空穴传输层。A structure of a quantum dot electroluminescent device according to another embodiment of the present invention includes the above first electrode layer, light emitting layer, first electron transport layer, second electron transport layer, and second electrode layer, and further includes substrate and hole transport Floor.
基板用于承载其他结构层。基板可以是刚性基板或柔性基板。刚性基板可以是陶瓷材质或各类玻璃材质等。柔性基板可以是聚酰亚胺薄膜(PI)及其衍生物、聚萘二甲酸乙二醇酯(PEN)、磷酸烯醇式丙酮酸(PEP)或二亚苯基醚树脂等。The substrate is used to carry other structural layers. The substrate may be a rigid substrate or a flexible substrate. The rigid substrate can be made of ceramic or various types of glass. The flexible substrate may be a polyimide film (PI) and a derivative thereof, polyethylene naphthalate (PEN), phosphoenolpyruvate (PEP) or a diphenylene ether resin.
空穴传输层位于第一电极层上方，作用是传输空穴，使空穴到达发光层，可以理解的，空穴传输层的材料可以为聚四苯基联苯胺或聚乙烯咔唑等。优选的，空穴传输层的材料为TFB，TFB为聚[(9,9-二辛基芴-2,7-二基)-共-(4,4'-(N-(4-仲丁基苯基)二苯胺)]；The hole transport layer is located above the first electrode layer to transport holes and allow holes to reach the light-emitting layer. It is understood that the material of the hole transport layer may be polytetraphenylbenzidine or polyvinylcarbazole. Preferably, the material of the hole transport layer is TFB, and the TFB is poly[(9,9-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-) Phenyl)diphenylamine)];
加入空穴传输层后，电子、空穴的迁移率之间的差异进一步减弱，更好的实现了载流子的平衡，电流效应更好。After the hole transport layer is added, the difference between the mobility of electrons and holes is further weakened, and the balance of carriers is better realized, and the current effect is better.
本发明的另一个实施方式的量子点电致发光器件的结构包括基板、第一电极层、空穴传输层、发光层、第一电子传输层、第二电子传输层和第二电极层。还包括空穴注入层、空穴阻挡层、电子阻挡层和电子注入层的一层或多层，其中空穴注入层设置在第一电极层与空穴传输层之间，电子阻挡层设置在空穴传输层与发光层之间，电子注入层设置在所述第二电极层与所述第二电子传输层之间，空穴阻挡层设置在所述发光层与所述第一电子传输层之间。A structure of a quantum dot electroluminescent device according to another embodiment of the present invention includes a substrate, a first electrode layer, a hole transport layer, a light emitting layer, a first electron transport layer, a second electron transport layer, and a second electrode layer. Also included is one or more layers of a hole injection layer, a hole blocking layer, an electron blocking layer, and an electron injection layer, wherein the hole injection layer is disposed between the first electrode layer and the hole transport layer, and the electron blocking layer is disposed at Between the hole transport layer and the light emitting layer, an electron injection layer is disposed between the second electrode layer and the second electron transport layer, and a hole blocking layer is disposed on the light emitting layer and the first electron transport layer between.
空穴注入层位于基板和第一电极层的上方，空穴注入层可提供空穴。优选的，空穴注入层的材料为PEDOT:PSS，PEDOT:PSS是一种高分子聚合物的水溶液，导电率很高，根据不同的配方，可以得到导电率不同的水溶液。该化合物是由PEDOT和PSS两种物质构成。PEDOT是EDOT(3，4-乙撑二氧噻吩单体)的聚合物，PSS是聚苯乙烯磺酸盐。The hole injection layer is located above the substrate and the first electrode layer, and the hole injection layer can provide holes. Preferably, the material of the hole injection layer is PEDOT:PSS, and PEDOT:PSS is an aqueous solution of a high molecular polymer, and the conductivity is high. According to different formulations, an aqueous solution having different conductivity can be obtained. This compound is composed of two substances, PEDOT and PSS. PEDOT is a polymer of EDOT (3,4-ethylenedioxythiophene monomer), and PSS is a polystyrene sulfonate.
空穴注入层、空穴阻挡层、电子注入层和电子阻挡层为辅助膜层，是为了更进一步提高发光功能层的发光效率。The hole injection layer, the hole blocking layer, the electron injection layer, and the electron blocking layer are auxiliary film layers in order to further improve the light-emitting efficiency of the light-emitting function layer.
上述量子点电致发光器件的各功能层均可通过溶液法进行加工成膜，所述溶液法包括但不限于喷墨打印、旋涂、狭缝涂布和丝网印刷等工艺，除量子点之外的其他功能层还能采用真空热镀蒸发工艺形成薄膜。Each functional layer of the above quantum dot electroluminescent device can be processed into a film by a solution method including, but not limited to, inkjet printing, spin coating, slit coating, and screen printing, in addition to quantum dots. Other functional layers than others can be formed into a film by a vacuum hot-dip evaporation process.
实施例1Example 1
本实施例提供一种量子点电致发光器件，结构如图1所示，从下而上依次层叠基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、第一电子传输层105、第二电子传输层106和第二电极层107；The present embodiment provides a quantum dot electroluminescent device having a structure as shown in FIG. 1. The substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, and the light emitting layer 104 are laminated in this order from bottom to top. a first electron transport layer 105, a second electron transport layer 106, and a second electrode layer 107;
第一电子传输层105的材料为ZnO；第二电子传输层106的材料为TmPyPB:LiQ。The material of the first electron transport layer 105 is ZnO; the material of the second electron transport layer 106 is TmPyPB: LiQ.
本实施例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of this embodiment is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上沉积第一电子传输层材料，然后在氮气氛围下120℃下烘烤30分钟，得到第一电子传输层，所述第一电子传输层的材料是ZnO，第一电子传输层的厚度为20nm；(5) depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes in a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being ZnO The thickness of the first electron transport layer is 20 nm;
(6)通过蒸镀的方式同时蒸镀有机电子传输材料TmPyPB和掺杂材料LiQ(TmPyPB:LiQ＝1:1)，在所述第一电子传输层上制作第二电子传输层，第二电子传输层的厚度为40nm；(6) simultaneously evaporating the organic electron transport material TmPyPB and the dopant material LiQ (TmPyPB: LiQ=1:1) by evaporation, and fabricating a second electron transport layer on the first electron transport layer, the second electron The thickness of the transport layer is 40 nm;
(7)在第二电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(7) Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
实施例2Example 2
本实施例提供一种量子点电致发光器件，从下而上依次层叠基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、第一电子传输层105、第二电子传输层106和第二电极层107；The present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
第一电子传输层105的材料为MgO；第二电子传输层106的材料为TmPyPB:LiQ。The material of the first electron transport layer 105 is MgO; the material of the second electron transport layer 106 is TmPyPB: LiQ.
本实施例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of this embodiment is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处 理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上沉积第一电子传输层材料，然后在氮气氛围下120℃下烘烤30分钟，得到第一电子传输层，所述第一电子传输层的材料是MgO，第一电子传输层的厚度为20nm；(5) depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being MgO The thickness of the first electron transport layer is 20 nm;
(6)通过蒸镀的方式同时蒸镀有机电子传输材料TmPyPB和掺杂材料LiQ(TmPyPB:LiQ＝1:1)，在所述第一电子传输层上制作第二电子传输层，第二电子传输层的厚度为40nm；(6) simultaneously evaporating the organic electron transport material TmPyPB and the dopant material LiQ (TmPyPB: LiQ=1:1) by evaporation, and fabricating a second electron transport layer on the first electron transport layer, the second electron The thickness of the transport layer is 40 nm;
(7)在第二电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(7) Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
实施例3Example 3
本实施例提供一种量子点电致发光器件，从下而上依次层叠基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、第一电子传输层105、第二电子传输层106和第二电极层107；The present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
第一电子传输层105的材料为TiO 2；第二电子传输层106的材料为Bphen:LiQ。 The material of the first electron transport layer 105 is TiO 2 ; the material of the second electron transport layer 106 is Bphen:LiQ.
本实施例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of this embodiment is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上沉积第一电子传输层材料，然后在氮气氛围下120℃下烘烤30分钟，得到第一电子传输层，所述第一电子传输层的材料是TiO 2，第一电子传输层的厚度为20nm； (5) depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being TiO 2 , the thickness of the first electron transport layer is 20 nm;
(6)通过蒸镀的方式同时蒸镀有机电子传输材料Bphen和掺杂材料LiQ(Bphen:LiQ＝1:1)，在所述第一电子传输层上制作第二电子传输层，第二电子传输层的厚度为40nm；(6) simultaneously evaporating the organic electron transporting material Bphen and the dopant material LiQ (Bphen: LiQ=1:1) by evaporation, and fabricating a second electron transport layer on the first electron transport layer, the second electron The thickness of the transport layer is 40 nm;
(7)在第二电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(7) Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
实施例4Example 4
本实施例提供一种量子点电致发光器件，从下而上依次层叠基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、第一电子传输层105、第二电子传输层106和第二电极层107；The present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
第一电子传输层105的材料为ZnO；第二电子传输层106的材料为BCP:LiQ。The material of the first electron transport layer 105 is ZnO; the material of the second electron transport layer 106 is BCP:LiQ.
本实施例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of this embodiment is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上沉积第一电子传输层材料，然后在氮气氛围下120℃下烘烤30分钟，得到第一电子传输层，所述第一电子传输层的材料是ZnO，第一电子传输层的厚度为20nm；(5) depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes in a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being ZnO The thickness of the first electron transport layer is 20 nm;
(6)通过蒸镀的方式同时蒸镀有机电子传输材料BCP和掺杂材料LiQ(BCP:LiQ＝1:1)， 在所述第一电子传输层上制作第二电子传输层，第二电子传输层的厚度为40nm；(6) simultaneously evaporating the organic electron transporting material BCP and the dopant material LiQ (BCP: LiQ=1:1) by evaporation, and fabricating a second electron transport layer on the first electron transport layer, the second electron The thickness of the transport layer is 40 nm;
(7)在第二电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(7) Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
实施例5Example 5
本实施例提供一种量子点电致发光器件，从下而上依次层叠基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、第一电子传输层105、第二电子传输层106和第二电极层107；The present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
第一电子传输层105的材料为MgO；第二电子传输层106的材料为BCP:LiQ。The material of the first electron transport layer 105 is MgO; the material of the second electron transport layer 106 is BCP: LiQ.
本实施例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of this embodiment is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上沉积第一电子传输层材料，然后在氮气氛围下120℃下烘烤30分钟，得到第一电子传输层，所述第一电子传输层的材料是MgO，第一电子传输层的厚度为20nm；(5) depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being MgO The thickness of the first electron transport layer is 20 nm;
(6)通过蒸镀的方式同时蒸镀有机电子传输材料BCP和掺杂材料LiQ(BCP:LiQ＝1:1)，在所述第一电子传输层上制作第二电子传输层，第二电子传输层的厚度为40nm；(6) simultaneously evaporating the organic electron transporting material BCP and the dopant material LiQ (BCP: LiQ=1:1) by evaporation, and fabricating a second electron transport layer on the first electron transport layer, the second electron The thickness of the transport layer is 40 nm;
(7)在第二电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(7) Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
实施例6Example 6
本实施例提供一种量子点电致发光器件，从下而上依次层叠基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、第一电子传输层105、第二电子传输层106和第二电极层107；The present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
第一电子传输层105的材料为ZnMgO；第二电子传输层106的材料为BCP:LiQ。The material of the first electron transport layer 105 is ZnMgO; the material of the second electron transport layer 106 is BCP: LiQ.
本实施例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of this embodiment is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上沉积第一电子传输层材料，然后在氮气氛围下120℃下烘烤30分钟，得到第一电子传输层，所述第一电子传输层的材料是ZnMgO，第一电子传输层的厚度为20nm；(5) depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being ZnMgO The thickness of the first electron transport layer is 20 nm;
(6)通过蒸镀的方式同时蒸镀有机电子传输材料BCP和掺杂材料LiQ(BCP:LiQ＝1:1)，在所述第一电子传输层上制作第二电子传输层，第二电子传输层的厚度为40nm；(6) simultaneously evaporating the organic electron transporting material BCP and the dopant material LiQ (BCP: LiQ=1:1) by evaporation, and fabricating a second electron transport layer on the first electron transport layer, the second electron The thickness of the transport layer is 40 nm;
(7)在第二电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(7) Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
实施例7Example 7
本实施例提供一种量子点电致发光器件，从下而上依次层叠第一电极层101、发光层104、第一电子传输层105、第二电子传输层106和第二电极层107；The present embodiment provides a quantum dot electroluminescent device, sequentially stacking the first electrode layer 101, the light emitting layer 104, the first electron transport layer 105, the second electron transport layer 106, and the second electrode layer 107 from bottom to top;
第一电子传输层105的材料为ZnO-TiO 2-SnO 2；第二电子传输层106的材料为TmPyPB:LiQ。 The material of the first electron transport layer 105 is ZnO-TiO 2 -SnO 2 ; the material of the second electron transport layer 106 is TmPyPB:LiQ.
本实施例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of this embodiment is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(2) depositing a quantum dot material on the glass substrate, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the thickness of the quantum dot light-emitting layer 40 nm;
(3)在所述量子点发光层上沉积第一电子传输层材料，然后在氮气氛围下120℃下烘烤 30分钟，得到第一电子传输层，所述第一电子传输层的材料是ZnO-TiO 2-SnO 2，第一电子传输层的厚度为20nm； (3) depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes in a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being ZnO -TiO 2 -SnO 2 , the thickness of the first electron transport layer is 20 nm;
(4)通过蒸镀的方式同时蒸镀有机电子传输材料TmPyPB和掺杂材料LiQ(TmPyPB:LiQ＝1:1)，在所述第一电子传输层上制作第二电子传输层，第二电子传输层的厚度为40nm；(4) simultaneously evaporating the organic electron transport material TmPyPB and the dopant material LiQ (TmPyPB: LiQ=1:1) by evaporation, and fabricating a second electron transport layer on the first electron transport layer, the second electron The thickness of the transport layer is 40 nm;
(5)在第二电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(5) Al is evaporated on the second electron transport layer to form a second electrode having a thickness of 120 nm.
实施例8Example 8
本实施例提供一种量子点电致发光器件，从下而上依次层叠基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、第一电子传输层105、第二电子传输层106和第二电极层107；The present embodiment provides a quantum dot electroluminescent device, which sequentially stacks the substrate 100, the first electrode layer 101, the hole injection layer 102, the hole transport layer 103, the light emitting layer 104, and the first electron transport layer 105 from bottom to top. a second electron transport layer 106 and a second electrode layer 107;
第一电子传输层105的材料为ZnMgO和PEIE；第二电子传输层106的材料为PEIE。The material of the first electron transport layer 105 is ZnMgO and PEIE; the material of the second electron transport layer 106 is PEIE.
本实施例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of this embodiment is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上沉积第一电子传输层材料，然后在氮气氛围下120℃下烘烤30分钟，得到第一电子传输层，所述第一电子传输层的材料是ZnMgO和PEIE(ZnMgO:PEIE＝1:9)，第一电子传输层的厚度为20nm；(5) depositing a first electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain a first electron transport layer, the material of the first electron transport layer being ZnMgO And PEIE (ZnMgO: PEIE = 1:9), the thickness of the first electron transport layer is 20 nm;
(6)通过蒸镀的方式蒸镀有机电子传输材料PEIE，在所述第一电子传输层上制作第二电子传输层，第二电子传输层的厚度为40nm；(6) evaporating the organic electron transport material PEIE by evaporation, forming a second electron transport layer on the first electron transport layer, the thickness of the second electron transport layer is 40 nm;
(7)在第二电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(7) Al is evaporated on the second electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
实施例9Example 9
本实施例提供一种量子点电致发光器件，电致发光器件的结构与实施例7基本相同，区别点在于，在第一电极层与发光层之间设置有空穴传输层，空穴传输层的材料为TFB。The embodiment provides a quantum dot electroluminescent device. The structure of the electroluminescent device is basically the same as that of the embodiment 7. The difference is that a hole transport layer is disposed between the first electrode layer and the light emitting layer, and the hole is transported. The material of the layer is TFB.
对比例1Comparative example 1
本对比例提供一种量子点电致发光器件，从下而上依次包括基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、电子传输层105和第二电极层107；The present comparative example provides a quantum dot electroluminescent device comprising, in order from bottom to top, a substrate 100, a first electrode layer 101, a hole injection layer 102, a hole transport layer 103, a light emitting layer 104, an electron transport layer 105, and a Two electrode layer 107;
电子传输层105的材料为ZnO。The material of the electron transport layer 105 is ZnO.
本对比例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of the present comparative example is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上沉积电子传输层材料，然后在氮气氛围下120℃下烘烤30分钟，得电子传输层，所述电子传输层的材料是ZnO，电子传输层的厚度为20nm；(5) depositing an electron transport layer material on the quantum dot light-emitting layer, and then baking at 120 ° C for 30 minutes under a nitrogen atmosphere to obtain an electron transport layer, the material of the electron transport layer being ZnO, the thickness of the electron transport layer 20 nm;
(6)在所述电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(6) Al is evaporated on the electron transport layer to form a second electrode, and the thickness of the second electrode is 120 nm.
对比例2Comparative example 2
本对比例提供一种量子点电致发光器件，从下而上依次包括基板100、第一电极层101、空穴注入层102、空穴传输层103、发光层104、电子传输层106和第二电极层107；The present comparative example provides a quantum dot electroluminescent device comprising, in order from bottom to top, a substrate 100, a first electrode layer 101, a hole injection layer 102, a hole transport layer 103, a light emitting layer 104, an electron transport layer 106, and Two electrode layer 107;
电子传输层106的材料为TmPyPB:LiQ。The material of the electron transport layer 106 is TmPyPB: LiQ.
本对比例的量子点电致发光器件的制备过程如下：The preparation process of the quantum dot electroluminescent device of the present comparative example is as follows:
(1)将含有ITO(120nm)透明电极的玻璃衬底用去离子水和异丙醇清洗且连续超声处理25分钟，然后用氮***吹干液体，在UV-O下处理20分钟，以清洁ITO的表面，并且提升ITO的功函数；(1) A glass substrate containing a transparent electrode of ITO (120 nm) was washed with deionized water and isopropyl alcohol and sonicated continuously for 25 minutes, and then the liquid was blown dry with a nitrogen gun and treated under UV-O for 20 minutes to clean The surface of the ITO and enhance the work function of the ITO;
(2)在所述玻璃衬底上沉积空穴注入层材料，然后在空气中145℃烘烤20分钟，得到 空穴注入层，所述空穴注入层的材料是PEDOT:PSS，空穴注入层的厚度为40nm；(2) depositing a hole injecting layer material on the glass substrate, followed by baking at 145 ° C for 20 minutes in the air to obtain a hole injecting layer, the material of which is PEDOT:PSS, hole injection The thickness of the layer is 40 nm;
(3)在所述空穴注入层上沉积空穴传输层材料，然后在氮气氛围下110℃烘烤30分钟，得到空穴传输层，所述空穴传输层的材料是TFB，空穴传输层的厚度为25nm；(3) depositing a hole transport layer material on the hole injection layer, and then baking at 110 ° C for 30 minutes under a nitrogen atmosphere to obtain a hole transport layer, the material of the hole transport layer being TFB, hole transport The thickness of the layer is 25 nm;
(4)在所述空穴传输层上沉积量子点材料，然后在氮气氛围下150℃烘烤20分，得到量子点发光层，其中量子点为CdSe/CdS核壳结构，量子点发光层的厚度为40nm；(4) depositing a quantum dot material on the hole transport layer, and then baking at a temperature of 150 ° C for 20 minutes in a nitrogen atmosphere to obtain a quantum dot light-emitting layer, wherein the quantum dot is a CdSe/CdS core-shell structure, and the quantum dot light-emitting layer The thickness is 40 nm;
(5)在所述量子点发光层上，通过蒸镀的方式同时蒸镀有机电子传输材料TmPyPB和掺杂材料LiQ(TmPyPB:LiQ＝1:1)，电子传输层的厚度为40nm；(5) on the quantum dot light-emitting layer, the organic electron transport material TmPyPB and the dopant material LiQ (TmPyPB: LiQ = 1:1) are simultaneously vapor-deposited, the thickness of the electron transport layer is 40 nm;
(6)在电子传输层上蒸镀Al，形成第二电极，第二电极的厚度为120nm。(6) Al was evaporated on the electron transport layer to form a second electrode, and the thickness of the second electrode was 120 nm.
对比例3Comparative example 3
本对比例提供一种量子点电致发光器件，电致发光器件的结构与实施例8基本相同，区别在于，第一电子传输层的材料为ZnMgO和TmPyPB(ZnMgO:TmPyPB＝1:9)。The present comparative example provides a quantum dot electroluminescent device having a structure substantially the same as that of Embodiment 8, except that the material of the first electron transporting layer is ZnMgO and TmPyPB (ZnMgO: TmPyPB = 1:9).
本对比例的量子点电致发光器件的制备过程与实施例8相同。The preparation process of the quantum dot electroluminescent device of the present comparative example was the same as in Example 8.
对比例4Comparative example 4
本对比例提供一种量子点电致发光器件，电致发光器件的结构与对比例3基本相同，区别点在于，第二电子传输层的材料为TmPyPB。The present comparative example provides a quantum dot electroluminescent device. The structure of the electroluminescent device is substantially the same as that of Comparative Example 3, except that the material of the second electron transporting layer is TmPyPB.
本对比例的量子点电致发光器件的制备过程与对比例3相同。The preparation process of the quantum dot electroluminescent device of this comparative example was the same as in Comparative Example 3.
对比例5Comparative example 5
本对比例提供一种量子点电致发光器件，电致发光器件的结构与实施例7基本相同，区别点在于，不含有第一电子传输层，仅含有第二电子传输层，第二电子传输层的材料为TmPyPB:LiQ。The present comparative example provides a quantum dot electroluminescent device. The structure of the electroluminescent device is basically the same as that of Embodiment 7, except that it does not contain the first electron transport layer, only the second electron transport layer, and the second electron transport. The material of the layer is TmPyPB: LiQ.
本对比例的量子点电致发光器件的制备过程与实施例7相同，不含第一电子传输层的制备步骤。The preparation process of the quantum dot electroluminescent device of the present comparative example was the same as that of Example 7, and the preparation step of the first electron transport layer was not included.
将上述实施例及对比例的量子点电致发光器件在电流密度为10mA/cm 2的条件下测试器件电流效率，并将对比例3的电流效率归一化为1，得到相应的电流效率值，其结果如下： The quantum dot electroluminescent device of the above examples and comparative examples were tested for device current efficiency at a current density of 10 mA/cm 2 , and the current efficiency of Comparative Example 3 was normalized to 1, and the corresponding current efficiency value was obtained. The results are as follows:
  电子传输层Electronic transport layer 相对电流效率Relative current efficiency
对比例1Comparative example 1 ZnOZnO 55
对比例2Comparative example 2 TmPyPB:LiQTmPyPB: LiQ 33
对比例3Comparative example 3 ZnMgO:TmPyPB/PEIEZnMgO: TmPyPB/PEIE 11
对比例4Comparative example 4 ZnMgO:TmPyPB/TmPyPBZnMgO: TmPyPB/TmPyPB 22
对比例5Comparative example 5 TmPyPB:LiQTmPyPB: LiQ 0.050.05
实施例1Example 1 ZnO/TmPyPB:LiQZnO/TmPyPB: LiQ 1212
实施例2Example 2 MgO/TmPyPB:LiQMgO/TmPyPB: LiQ 1111
实施例3Example 3 TiO 2/Bphen:LiQ TiO 2 /Bphen:LiQ 99
实施例4Example 4 ZnO/BCP:LiQZnO/BCP: LiQ 1111
实施例5Example 5 MgO/BCP:LiQMgO/BCP: LiQ 1010
实施例6Example 6 ZnMgO/BCP:LiQZnMgO/BCP: LiQ 1414
实施例7Example 7 ZnO-TiO 2-SnO 2/TmPyPB:LiQ ZnO-TiO 2 -SnO 2 /TmPyPB: LiQ 1.51.5
实施例8Example 8 ZnMgO:PEIE/PEIEZnMgO: PEIE/PEIE 99
实施例9Example 9 ZnO-TiO 2-SnO 2/TmPyPB:LiQ ZnO-TiO 2 -SnO 2 /TmPyPB: LiQ 55
由上表可知，单独使用无机金属氧化物材料与有机电子传输材料作为电子传输层材料时，电流效率相对较低，无机金属氧化物材料与有机电子传输材料两层电子传输层叠加使用，电流效率较高，特别的，ZnMgO对电流效率的提高作用明显。It can be seen from the above table that when the inorganic metal oxide material and the organic electron transport material are used as the electron transport layer material alone, the current efficiency is relatively low, and the inorganic metal oxide material and the organic electron transport material are stacked in two layers, and the current efficiency is used. Higher, in particular, ZnMgO has a significant effect on current efficiency.
实施例8中，在第一电子传输层中加入有机高分子材料PEIE，可提高电流效应。但是对比例3和对比例4中，在第一电子传输层中添加有机小分子材料TmPyPB时，电流效应较差。In Example 8, the organic polymer material PEIE was added to the first electron transport layer to increase the current effect. However, in Comparative Example 3 and Comparative Example 4, when the organic small molecule material TmPyPB was added to the first electron transport layer, the current effect was poor.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (19)

  1. 一种量子点电致发光器件，其特征在于，包括相对设置的第一电极层、第二电极层，设置于所述第一电极层与所述第二电极层之间的发光层，设置于所述发光层与所述第二电极层之间的第一电子传输层，设置于所述第一电子传输层与所述第二电极层之间的第二电子传输层；A quantum dot electroluminescent device, comprising: a first electrode layer and a second electrode layer disposed opposite to each other; and a light emitting layer disposed between the first electrode layer and the second electrode layer, disposed on a first electron transport layer between the light emitting layer and the second electrode layer, and a second electron transport layer disposed between the first electron transport layer and the second electrode layer;
    所述第一电子传输层的材料包括无机金属氧化物，所述第二电子传输层的材料包括有机电子传输材料。The material of the first electron transport layer includes an inorganic metal oxide, and the material of the second electron transport layer includes an organic electron transport material.
  2. 根据权利要求1所述的量子点电致发光器件，其特征在于，所述无机金属氧化物为一元金属氧化物和多元金属氧化物中的一种或几种。The quantum dot electroluminescent device according to claim 1, wherein the inorganic metal oxide is one or more of a monovalent metal oxide and a multi-metal oxide.
  3. 根据权利要求2所述的量子点电致发光器件，其特征在于，所述多元金属氧化物选自氧化锌镁、氧化锌锡、氧化锌铝、氧化锌钙、氧化锌钨、氧化锌钛、氧化锌镍、ZnO-TiO 2-SnO 2和ZnO-MgO-TiO 2中的一种或几种；和/或 The quantum dot electroluminescent device according to claim 2, wherein the multi-metal oxide is selected from the group consisting of zinc magnesium oxide, zinc tin oxide, zinc aluminum oxide, calcium zinc oxide, zinc tungsten oxide, zinc zinc oxide, One or more of zinc oxide nickel, ZnO-TiO 2 -SnO 2 and ZnO-MgO-TiO 2 ; and/or
    所述一元金属氧化物选自ZnO、MgO、TiO 2、SnO 2、ZrO 2、HfO 2和Ta 2O 3的一种或几种。 The monobasic metal oxide is selected from one or more of ZnO, MgO, TiO 2 , SnO 2 , ZrO 2 , HfO 2 and Ta 2 O 3 .
  4. 根据权利要求1所述的量子点电致发光器件，其特征在于，所述第一电子传输层还包括高分子材料PEIE。The quantum dot electroluminescent device according to claim 1, wherein the first electron transport layer further comprises a polymer material PEIE.
  5. 根据权利要求1所述的量子点电致发光器件，其特征在于，所述有机电子传输材料选自NBphen、TPBi、Bpy-FOXD、BP4mPy、BTB、BIPO、3TPYMB、PBD、BAlq、PEIE、Bphen、TmPyPB和BCP的一种或几种。The quantum dot electroluminescent device according to claim 1, wherein the organic electron transporting material is selected from the group consisting of NBphen, TPBi, Bpy-FOXD, BP4mPy, BTB, BIPO, 3TPYMB, PBD, BAlq, PEIE, Bphen, One or several of TmPyPB and BCP.
  6. 根据权利要求1所述的量子点电致发光器件，其特征在于，所述第二电子传输层还包括掺杂材料，所述掺杂材料选自金属、金属无机盐或有机金属配合物；和/或The quantum dot electroluminescent device according to claim 1, wherein the second electron transport layer further comprises a dopant material selected from the group consisting of a metal, a metal inorganic salt or an organometallic complex; /or
    所述掺杂材料占所述第二电子传输层总质量的1％-60％。The dopant material accounts for 1% to 60% of the total mass of the second electron transport layer.
  7. 根据权利要求6所述的量子点电致发光器件，其特征在于，所述金属选自Li、Na、K、Rb、Cs或Yb；和/或The quantum dot electroluminescent device according to claim 6, wherein the metal is selected from the group consisting of Li, Na, K, Rb, Cs or Yb; and/or
    所述金属无机盐选自Li 2CO 3、K 2SiO 3、Rb 2CO 3或Cs 2CO 3；和/或 The metal inorganic salt is selected from the group consisting of Li 2 CO 3 , K 2 SiO 3 , Rb 2 CO 3 or Cs 2 CO 3 ; and/or
    所述有机金属配合物选自LiQ、AlQ 3。 The organometallic complex is selected from the group consisting of LiQ, AlQ 3 .
  8. 根据权利要求6所述的量子点电致发光器件，其特征在于，所述掺杂材料占所述第二电子传输层总质量的40％-60％。The quantum dot electroluminescent device according to claim 6, wherein the dopant material accounts for 40% to 60% of the total mass of the second electron transport layer.
  9. 根据权利要求1所述的量子点电致发光器件，其特征在于，所述第一电子传输层的厚 度为1-150nm；和/或The quantum dot electroluminescent device according to claim 1, wherein said first electron transport layer has a thickness of from 1 to 150 nm; and/or
    所述第二电子传输层的厚度为1-150nm。The second electron transport layer has a thickness of 1 to 150 nm.
  10. 根据权利要求1所述的量子点电致发光器件，其特征在于，所述第一电子传输层的材料为无机金属氧化物或无机金属氧化物与高分子材料PEIE的复合材料，所述第二电子传输层的材料为有机电子传输材料或有机电子传输材料与掺杂材料的复合材料。The quantum dot electroluminescent device according to claim 1, wherein the material of the first electron transport layer is an inorganic metal oxide or a composite material of an inorganic metal oxide and a polymer material PEIE, the second The material of the electron transport layer is an organic electron transport material or a composite material of an organic electron transport material and a dopant material.
  11. 根据权利要求10所述的量子点电致发光器件，其特征在于，所述无机金属氧化物为一元金属氧化物和多元金属氧化物中的一种或几种。The quantum dot electroluminescent device according to claim 10, wherein the inorganic metal oxide is one or more of a monovalent metal oxide and a multi-metal oxide.
  12. 根据权利要求11所述的量子点电致发光器件，其特征在于，所述多元金属氧化物选自氧化锌镁、氧化锌锡、氧化锌铝、氧化锌钙、氧化锌钨、氧化锌钛、氧化锌镍、ZnO-TiO 2-SnO 2和ZnO-MgO-TiO 2中的一种或几种；和/或 The quantum dot electroluminescent device according to claim 11, wherein the multi-metal oxide is selected from the group consisting of zinc magnesium oxide, zinc tin oxide, zinc aluminum oxide, calcium zinc oxide, zinc tungsten oxide, zinc zinc oxide, One or more of zinc oxide nickel, ZnO-TiO 2 -SnO 2 and ZnO-MgO-TiO 2 ; and/or
    所述一元金属氧化物选自ZnO、MgO、TiO 2、SnO 2、ZrO 2、HfO 2和Ta 2O 3的一种或几种。 The monobasic metal oxide is selected from one or more of ZnO, MgO, TiO 2 , SnO 2 , ZrO 2 , HfO 2 and Ta 2 O 3 .
  13. 根据权利要求10所述的量子点电致发光器件，其特征在于，所述有机电子传输材料选自NBphen、TPBi、Bpy-FOXD、BP4mPy、BTB、BIPO、3TPYMB、PBD、BAlq、PEIE、Bphen、TmPyPB和BCP的一种或几种。The quantum dot electroluminescent device according to claim 10, wherein the organic electron transporting material is selected from the group consisting of NBphen, TPBi, Bpy-FOXD, BP4mPy, BTB, BIPO, 3TPYMB, PBD, BAlq, PEIE, Bphen, One or several of TmPyPB and BCP.
  14. 根据权利要求10所述的量子点电致发光器件，其特征在于，所述掺杂材料选自金属、金属无机盐或有机金属配合物；和/或The quantum dot electroluminescent device according to claim 10, wherein the dopant material is selected from the group consisting of a metal, a metal inorganic salt or an organometallic complex; and/or
    所述掺杂材料占所述第二电子传输层总质量的1％-60％。The dopant material accounts for 1% to 60% of the total mass of the second electron transport layer.
  15. 根据权利要求14所述的量子点电致发光器件，其特征在于，所述金属选自Li、Na、K、Rb、Cs或Yb；和/或The quantum dot electroluminescent device according to claim 14, wherein the metal is selected from the group consisting of Li, Na, K, Rb, Cs or Yb; and/or
    所述金属无机盐选自Li 2CO 3、K 2SiO 3、Rb 2CO 3或Cs 2CO 3；和/或 The metal inorganic salt is selected from the group consisting of Li 2 CO 3 , K 2 SiO 3 , Rb 2 CO 3 or Cs 2 CO 3 ; and/or
    所述有机金属配合物选自LiQ、AlQ 3。 The organometallic complex is selected from the group consisting of LiQ, AlQ 3 .
  16. 根据权利要求14所述的量子点电致发光器件，其特征在于，所述掺杂材料占所述第二电子传输层总质量的40％-60％。The quantum dot electroluminescent device according to claim 14, wherein the dopant material accounts for 40% to 60% of the total mass of the second electron transport layer.
  17. 根据权利要求7所述的量子点电致发光器件，其特征在于，还包括空穴注入层、空穴传输层、空穴阻挡层、电子阻挡层和电子注入层中的一层或多层。The quantum dot electroluminescent device according to claim 7, further comprising one or more of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, and an electron injection layer.
  18. 根据17所述的量子点电致发光器件，其特征在于，所述电致发光器件包括空穴注入层、空穴传输层和电子阻挡层，所述空穴注入层、所述空穴传输层和所述电子阻挡层层叠设置在所述第一电极层与所述发光层之间，且所述空穴注入层与所述第一电极层叠设；或者The quantum dot electroluminescent device according to 17, wherein the electroluminescent device comprises a hole injection layer, a hole transport layer, and an electron blocking layer, the hole injection layer, the hole transport layer And the electron blocking layer is disposed between the first electrode layer and the light emitting layer, and the hole injection layer is laminated with the first electrode; or
    所述电致发光器件包括空穴注入层和空穴传输层，所述空穴注入层和所述空穴传输层层叠设置在所述第一电极层与所述发光层之间，且所述空穴注入层与所述第一电极层叠设；或者The electroluminescent device includes a hole injection layer and a hole transport layer, and the hole injection layer and the hole transport layer are stacked between the first electrode layer and the light emitting layer, and a hole injection layer is laminated with the first electrode; or
    所述电致发光器件包括空穴传输层和电子阻挡层，所述空穴传输层和所述电子阻挡层层叠设置在所述第一电极层与所述发光层之间，且所述空穴传输层与所述第一电极层叠设；或者The electroluminescent device includes a hole transport layer and an electron blocking layer, and the hole transport layer and the electron blocking layer are stacked between the first electrode layer and the light emitting layer, and the holes a transport layer is stacked on the first electrode; or
    所述电致发光器件包括电子阻挡层和电子注入层，所述电子注入层设置在所述第二电极层与所述第二电子传输层之间，所述电子阻挡层设置在所述发光层与所述第二电子传输层之间。The electroluminescent device includes an electron blocking layer disposed between the second electrode layer and the second electron transport layer, and an electron injection layer disposed on the light emitting layer Between the second electron transport layer and the second electron transport layer.
  19. 一种显示器，包括权利要求1所述的量子点电致发光器件。A display comprising the quantum dot electroluminescent device of claim 1.
PCT/CN2018/118273 2017-11-29 2018-11-29 Quantum dot electroluminescent component and display WO2019105431A1 (en)

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