WO2020108068A1 - 一种量子点发光二极管及其制备方法 - Google Patents

一种量子点发光二极管及其制备方法 Download PDF

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WO2020108068A1
WO2020108068A1 PCT/CN2019/108324 CN2019108324W WO2020108068A1 WO 2020108068 A1 WO2020108068 A1 WO 2020108068A1 CN 2019108324 W CN2019108324 W CN 2019108324W WO 2020108068 A1 WO2020108068 A1 WO 2020108068A1
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quantum dot
dot light
layer
pamam
emitting diode
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梁柱荣
曹蔚然
钱磊
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TCL Technology Group Co Ltd
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    • C09K11/88—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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    • 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
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Definitions

  • the present disclosure relates to the field of quantum dot light-emitting devices, and in particular to a quantum dot light-emitting diode and a preparation method thereof.
  • Colloidal quantum dots are semiconductor nanocrystals synthesized on the basis of solution. Colloidal quantum dots have the characteristics of narrow luminous line width, high luminous efficiency, and quantum dots of different sizes can be excited by a single wavelength of light to emit different colors of light, etc., driving the development of next-generation optoelectronic display technology. Quantum dot light-emitting diode (QLED) with colloidal quantum dots as the light-emitting layer is a promising next-generation display and solid-state lighting source.
  • QLED Quantum dot light-emitting diode
  • QLED is a multilayer structure composed of multiple thin films, including a cathode, a quantum dot light emitting layer, an anode, and an electron transport layer (and/or electron injection layer) provided between the cathode and the quantum dot light emitting layer and The hole transport layer (and/or hole injection layer) provided between the anode and the quantum dot light emitting layer.
  • the purpose of providing the carrier transport layer and the injection layer is mainly because the energy level difference between the electrode and the quantum dot light emitting layer is too large, resulting in that the carriers cannot be effectively injected into the quantum dot light emitting layer from the electrode.
  • the introduction of the carrier transport layer can facilitate the injection of carriers
  • different carrier transport layer materials have a relatively fixed energy band structure, so for certain electrode materials and quantum dot luminescent materials, Need to find a specific energy band matching material as the carrier transport layer. Therefore, high-performance QLED devices have very high requirements on the material of the carrier transport layer, the use of the material is relatively simple, and the material types of the electron transport layer and the hole transport layer are often very different.
  • the purpose of the present disclosure is to provide a quantum dot light emitting diode and a preparation method thereof, aiming to solve the current high-performance quantum dot light emitting diodes that have high requirements for the material of the carrier transport layer. Is relatively simple to use, and the material types of the electron transport layer and the hole transport layer are often very different.
  • a quantum dot light-emitting diode includes an anode, a quantum dot light-emitting layer and a cathode, the quantum dot light-emitting layer is disposed between the anode and the cathode, and further includes the anode and the quantum dot emitting A first modified layer between the layers.
  • the first modified layer includes PAMAM (polyamide-amine dendrimer), and the PAMAM is doped with a transition metal cation.
  • a quantum dot light-emitting diode includes an anode, a quantum dot light-emitting layer and a cathode, the quantum dot light-emitting layer is disposed between the anode and the cathode, and further includes the cathode and the quantum dot emitting light
  • a preparation method of quantum dot light-emitting diode which includes the steps of:
  • a first modified layer is prepared on the anode, the first modified layer includes PAMAM, and the PAMAM is doped with transition metal cations;
  • a cathode is prepared on the quantum dot light-emitting layer.
  • the present disclosure can improve the work function of the anode by setting the first modification layer between the anode and the quantum dot light-emitting layer to modify the anode, thereby improving the hole injection effect, and thereby improving the performance of the device.
  • the present disclosure can also be used to modify the cathode by disposing the second modification layer between the cathode and the quantum dot light-emitting layer, the work function of the modified cathode will be reduced, thereby improving the electron injection effect and thereby improving the performance of the device .
  • FIG. 2 is a schematic flowchart of a method for preparing a quantum dot light emitting diode provided by the present disclosure
  • FIG. 3 is a schematic structural diagram of a quantum dot light-emitting diode according to Embodiment 1 of the present disclosure
  • FIG. 4 is a schematic structural diagram of a quantum dot light-emitting diode according to Embodiment 2 of the present disclosure
  • FIG. 5 is a schematic structural diagram of a quantum dot light-emitting diode according to Embodiment 3 of the present disclosure.
  • FIG. 6 is a schematic structural diagram of a quantum dot light-emitting diode according to Embodiment 4 of the present disclosure.
  • FIG. 7 is a schematic structural diagram of a quantum dot light-emitting diode according to Embodiment 5 of the present disclosure.
  • FIG. 8 is a schematic structural diagram of a quantum dot light-emitting diode according to Embodiment 6 of the present disclosure.
  • Example 9 is a schematic structural view of a quantum dot light-emitting diode of Example 7 of the present disclosure.
  • FIG. 10 is a schematic structural diagram of a quantum dot light-emitting diode according to Embodiment 8 of the present disclosure.
  • the present disclosure provides a quantum dot light emitting diode and a manufacturing method thereof.
  • a quantum dot light emitting diode and a manufacturing method thereof.
  • the present disclosure will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.
  • An embodiment of the present disclosure provides a quantum dot light-emitting diode, including an anode, a quantum dot light-emitting layer and a cathode, the quantum dot light-emitting layer is disposed between the anode and the cathode, and further includes the anode and the cathode A first modified layer between the quantum dot light-emitting layers, the first modified layer includes PAMAM, and the PAMAM is doped with a transition metal cation.
  • the work function of the anode can be improved, thereby improving the hole injection effect To further improve the performance of the device.
  • the reason why the work function of the anode changes after being modified by the first modification layer is that because PAMAM is a dendritic polymer material, its surface has a large number of amino groups and carbonyl groups (see Figure 1). After the metal cation, these groups will form a complex with the transition metal cation, so that the transition metal cation forms a covalent bond with the N and O atoms in the PAMAM, thereby changing the dipole moment of the PAMAM material and facilitating the injection of holes. Therefore, when the anode is modified with PAMAM doped with transition metal cations, the work function of the anode will increase.
  • the PAMAM in addition to the PAMAM in the first modification layer, the PAMAM is doped with transition metal cations, and other impurities may be present in the first modification layer, such as Li/Na/Al /Mg and other non-transition metal ions, these impurities will not have a beneficial or harmful effect on the function of the first modification layer.
  • the first modification layer is composed of PAMAM doped with transition metal cations, and does not contain other impurities, so that those skilled in the art can better adjust the content ratio of transition metal cations to PAMAM. Change the work function of the anode in a targeted manner.
  • the first modified layer is further doped with anions, and the anions and the transition metal cation constitute a metal salt.
  • the anions are adsorbed on the surface of the anode, and because of their electron-pushing effect, the injection of holes can be further promoted.
  • the molar ratio of the transition metal cation to the PAMAM in the first modified layer is 0.01-720.
  • the work function of the anode can be easily increased to different degrees, thereby improving the hole injection effect, and the material selectivity and device structure design of the quantum dot light-emitting diode can be enriched.
  • More diverse For example, when the Cu 2+ doping amount (molar ratio) is increased from 0 to 325, the work function of the ITO anode gradually increases from 4.07 eV to 4.97 eV.
  • the commonly used hole injection layer material of quantum dot light-emitting diodes is PEDOT:PSS, and its work function is 5.05eV, indicating that after the high concentration of Cu 2+ is incorporated into PAMAM, its modified ITO work function is close to PEDOT:PSS The work function of the material, that is, it has good hole injection performance.
  • the transition metal in the transition metal cation may include but is not limited to Cu, Ni, Zn, Co, Fe, Mn, Cr, V, Ti, Sc, Y, Zr, Nb, Mo, Tc, One or more of Ru, Rh, Pb, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Hg.
  • the transition metal in the transition metal cation may be selected from but not limited to one of Cu, Ni, Co, Fe, Mn, Cr, V, Ti, Y, Zr, Mo, Zr, and Ru One or more.
  • the anion can include but are not limited to, Cl -, CO 3 -, S 2-, SO 4 2-, SO 3 2-, MnO 4 2-, MnO 4 -, PO 4 3-, NO 3 -, NO 2 -, ClO 3 -, ClO -, ClO 2 -, ClO 4 -, CN -, AlO 2 -, AlO 3 3-, C 2 O 4 2-, FeO 4 2-, Cr 2 O One or more of 7 2- , CrO 4 2- and SeO 4 2- .
  • the thickness of the first modified layer is 2 ⁇ 110 nm.
  • the quantum dot light emitting diode further includes a second modified layer disposed between the cathode and the quantum dot light emitting layer, and the second modified layer includes PAMAM.
  • the second modification layer is provided between the cathode and the quantum dot light-emitting layer to modify the cathode, and the work function of the modified cathode will be reduced, thereby improving the electron injection effect and thereby improving the performance of the device.
  • the work function will change because PAMAM is a dendrimer material with a large number of amino groups and carbonyl groups on its surface (see Figure 1).
  • PAMAM is used for modification
  • the dipole moment formed will reduce the work function of the cathode, so it is conducive to the injection of electrons.
  • impurities may exist in the second modification layer, and these impurities will not have a beneficial or harmful effect on the function of the second modification layer.
  • the second modification layer is PAMAM, so that those skilled in the art only need to adjust PAMAM to adjust the cathode work function.
  • the thickness of the second modified layer is 5 to 96 nm.
  • the anode material may include, but is not limited to, one or more of metal materials, carbon materials, metal oxides, and hole injection materials.
  • the metal material may include one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg.
  • the carbon material may include one or more of graphite, carbon nanotubes, graphene, and carbon fiber.
  • the metal oxide may be a doped or undoped metal oxide, which may include one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO; the metal oxide may also It is a composite electrode with a metal sandwiched between doped or undoped transparent metal oxides, wherein the composite electrode may include AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 and One or more of TiO 2 /Al/TiO 2 .
  • the hole injection material may include, but is not limited to, one or more of PEDOT: PSS, CuPc, F4-TCNQ, HATCN, transition metal oxide, and transition metal chalcogenide compound.
  • the transition metal oxide may include one or more of NiO x , MoO x , WO x , CrO x and CuO;
  • the metal chalcogenide compound may include MoS x , MoSe x , WS x , WSe x And one or more of CuS.
  • the work function of the anode can be easily increased to different degrees, thereby improving the hole injection effect.
  • the work functions of the modified gold anode (Au), silver anode (Ag), and reduced graphene anode (RGO) are respectively from 4.98eV and 4.45eV , 5.20eV increased to 5.14eV, 4.87eV, 5.42eV.
  • the cathode material may include, but is not limited to, one or more of metal materials, carbon materials, and metal oxides.
  • the metal material may include one or more of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg.
  • the carbon material may include one or more of graphite, carbon nanotubes, graphene, and carbon fiber.
  • the metal oxide may be a doped or undoped metal oxide, for example, it may include one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO; the metal oxide may also It is a composite electrode with a metal sandwiched between doped or undoped transparent metal oxides, such as AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag /ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 and TiO 2 /Al/ One or more of TiO 2 .
  • doped or undoped transparent metal oxides such as AZO/Ag/AZO, AZ
  • the work function of the cathode can be easily reduced to different degrees, thereby improving the electron injection effect, and the material selectivity and device structure design of the quantum dot light-emitting diode can be richer and more diverse.
  • Au gold cathode
  • Ag silver cathode
  • RGO reduced graphene cathode
  • their work functions are reduced from 4.98eV, 4.45eV, 5.20eV to 3.66eV, 3.74eV, 4.27, respectively eV.
  • the quantum dot light emitting diode may further include a hole function layer disposed between the first modification layer and the quantum dot light emitting layer.
  • the hole functional layer may include one or both of a hole injection layer and a hole transport layer.
  • the hole functional layer is two kinds of a hole injection layer and a hole transport layer, the hole transport layer and the quantum dot light emitting layer are provided in close contact with each other.
  • the material of the hole injection layer is a material with good hole injection performance, such as, but not limited to, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT: PSS), copper phthalocyanine (CuPc), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinodimethane (F4-TCNQ), 2,3,6,7 ,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN), transition metal oxides, transition metal chalcogenide compounds; or ,
  • the transition metal oxide may include one or more of NiO x , MoO x , WO x , CrO x, and CuO; the metal chalcogenide compound may include MoS x , MoSe x , WS x , WSe x, and One or more of CuS.
  • the material of the hole transport layer is an organic material with good hole transport capabilities, which may include, but is not limited to, poly(9,9-dioctylfluorene-CO-N-(4-butane (Phenyl) diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (Poly -TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4"-tri(carbazole -9-yl) triphenylamine (TCTA), 4,4'-bis(9-carbazole) biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylbenzene Group)-1,1'-bipheny
  • TTB
  • the hole transport layer may also be selected from inorganic materials with hole transport capabilities, such as may include but are not limited to, NiO x, MoO x, WO x , CrO x, CuO, MoS x, MoSe x, WS x, WSe x CuS and of one or more.
  • the quantum dot light emitting diode may further include an electronic function layer disposed between the cathode and the quantum dot light emitting layer.
  • the electronic functional layer is disposed between the second modified layer and the quantum dot light emitting layer.
  • the electronic functional layer may be selected from one or both of an electron injection layer and an electron transport layer.
  • the electron functional layer is two kinds of an electron injection layer and an electron transport layer, the electron transport layer and the quantum dot light emitting layer are provided in close contact.
  • the material of the electron transport layer and the material of the electron injection layer are both inorganic materials and/or organic materials with electron transport capabilities, for example, the inorganic materials with electron transport capabilities may be selected from doped or One or more of undoped metal oxides, doped or undoped metal sulfides.
  • the doped or undoped metal oxide may include one or more of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, and InSnO Species.
  • the doped or undoped metal sulfide may include one or more of CdS, ZnS, MoS, WS, and CuS.
  • the materials of the quantum dot light-emitting layer may include, but are not limited to, II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III -One or more of a group VI compound, a group II-IV-VI compound, or a group IV elemental substance.
  • the materials of the quantum dot light-emitting layer may include, but are not limited to, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, and other binary, ternary, and quaternary One or more of II-VI compounds;
  • the material of the quantum dot light-emitting layer may include, but is not limited to, GaP, GaAs, InP, InAs, and other binary, ternary, and quaternary III-V compounds One or more of them.
  • the material of the quantum dot light-emitting layer may also be a doped or undoped inorganic perovskite type semiconductor, and/or an organic-inorganic hybrid perovskite type semiconductor.
  • the structural formula of the inorganic perovskite semiconductor is AMX 3 , where A is Cs + ion; M is a divalent metal cation, which may include but not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+, Cd 2+, Cr 2+, Mn 2+, Co 2+, Fe 2+, Ge 2+, Yb 2+ or Eu 2+; X is a halogen anion, may include, but are not limited to, Cl -, Br - or I -.
  • the quantum dot light emitting diode may further include an interface modification layer, and the interface modification layer may be selected from one of an electron blocking layer, a hole blocking layer, an electron injection layer, an electrode modification layer, and an isolation protection layer Or multiple layers.
  • the quantum dot light emitting diode may be partially encapsulated, fully encapsulated or not encapsulated.
  • An embodiment of the present disclosure provides a quantum dot light emitting diode, including an anode, a quantum dot light emitting layer, and a cathode.
  • the quantum dot light emitting layer is disposed between the anode and the cathode.
  • a second modified layer between the quantum dot light-emitting layers, the second modified layer including PAMAM.
  • the second modification layer is provided between the cathode and the quantum dot light-emitting layer to modify the cathode, and the work function of the modified cathode will be reduced, thereby improving the electron injection effect and thereby improving the performance of the device.
  • the work function will change because PAMAM is a dendrimer material with a large number of amino groups and carbonyl groups on its surface (see Figure 1).
  • PAMAM is a dendrimer material with a large number of amino groups and carbonyl groups on its surface
  • An embodiment of the present disclosure also provides a method for manufacturing a quantum dot light emitting diode, as shown in FIG. 2, including the following steps:
  • a first modified layer is prepared on the anode, the first modified layer includes PAMAM, and the PAMAM is doped with transition metal cations;
  • a cathode is prepared on the quantum dot light-emitting layer.
  • each layer deposition method may be a chemical method or a physical method, wherein the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, and co-precipitation method One or more; physical methods include but are not limited to spin coating method, printing method, blade coating method, dipping method, dipping method, spraying method, roll coating method, casting method, slot coating method, strip coating One or more of cloth method, thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, atomic layer deposition method, pulse laser deposition method.
  • the chemical method includes but is not limited to one of chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, and co-precipitation method One or more
  • physical methods include but are not limited to spin coating method, printing method,
  • the PAMAM in addition to the PAMAM in the first modification layer, the PAMAM is doped with transition metal cations, and other impurities may be present in the first modification layer, such as Li/Na/Al /Mg and other non-transition metal ions, these impurities will not have a beneficial or harmful effect on the function of the first modification layer.
  • the first modification layer is composed of PAMAM doped with transition metal cations, and does not contain other impurities, so that those skilled in the art can better adjust the content ratio of transition metal cations to PAMAM. Change the work function of the anode in a targeted manner.
  • the first modified layer is further doped with anions, and the anions and the transition metal cation constitute a metal salt.
  • the anions are adsorbed on the surface of the anode, and because of their electron-pushing effect, the injection of holes can be further promoted.
  • the steps of preparing a quantum dot light emitting layer on the first modified layer and preparing a cathode on the quantum dot light emitting layer specifically include: preparing quantum dot light emitting on the first modified layer Layer, a second modified layer is prepared on the quantum dot light emitting layer, and a cathode is prepared on the second modified layer, the second modified layer includes PAMAM.
  • the second modification layer is provided between the cathode and the quantum dot light-emitting layer to modify the cathode, and the work function of the modified cathode will be reduced, thereby improving the electron injection effect and thereby improving the performance of the device.
  • the work function will change because PAMAM is a dendrimer material with a large number of amino groups and carbonyl groups on its surface (see Figure 1).
  • PAMAM is a dendrimer material with a large number of amino groups and carbonyl groups on its surface
  • impurities may exist in the second modification layer, and these impurities will not have a beneficial or harmful effect on the function of the second modification layer.
  • the second modification layer is PAMAM, so that those skilled in the art only need to adjust PAMAM to adjust the cathode work function.
  • the thickness of the second modified layer is 5 to 96 nm.
  • the molar ratio of the transition metal cation to the PAMAM in the first modified layer is 0.01-720.
  • the work function of the anode can be easily increased to different degrees, thereby improving the hole injection effect, and the material selectivity and device structure design of the quantum dot light-emitting diode can be enriched.
  • More diverse For example, when the Cu 2+ doping amount (molar ratio) is increased from 0 to 325, the work function of the ITO anode gradually increases from 4.07 eV to 4.97 eV.
  • the commonly used hole injection layer material of quantum dot light-emitting diodes is PEDOT:PSS, and its work function is 5.05eV, indicating that after high concentration of Cu 2+ is incorporated into PAMAM, its modified ITO work function is close to PEDOT:PSS The work function of the material, that is, it has good hole injection performance.
  • the transition metal in the transition metal cation may include but is not limited to Cu, Ni, Zn, Co, Fe, Mn, Cr, V, Ti, Sc, Y, Zr, Nb, Mo, Tc, One or more of Ru, Rh, Pb, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Hg.
  • the transition metal in the transition metal cation may be selected from but not limited to one or more of Cu, Ni, Co, Fe, Mn, Cr, V, Ti, Y, Zr, Mo, Zr, and Ru.
  • the anion can include but are not limited to, Cl -, CO 3 -, S 2-, SO 4 2-, SO 3 2-, MnO 4 2-, MnO 4 -, PO 4 3-, NO 3 -, NO 2 -, ClO 3 -, ClO -, ClO 2 -, ClO 4 -, CN -, AlO 2 -, AlO 3 3-, C 2 O 4 2-, FeO 4 2-, Cr 2 O One or more of 7 2- , CrO 4 2- and SeO 4 2- .
  • the thickness of the first modified layer is 2 ⁇ 110 nm.
  • a quantum dot light emitting diode is prepared as follows:
  • a CdSe/ZnS quantum dot light-emitting layer is spin-coated on the Cu 2+ doped PAMAM modified ITO anode;
  • An Al cathode layer was vapor-deposited on the PAMAM modified layer to obtain a quantum dot light-emitting diode.
  • a quantum dot light emitting diode is prepared as follows:
  • a CdSe/ZnS quantum dot light-emitting layer is spin-coated on the Cu 2+ doped PAMAM modified ITO anode;
  • An Al cathode layer was evaporated on the ZnO electron transport layer to obtain a quantum dot light-emitting diode.
  • a quantum dot light-emitting diode is prepared as follows:
  • a layer of TFB hole transport layer is spin-coated on the Cu 2+ doped PAMAM modified ITO anode
  • a CdSe/ZnS quantum dot light-emitting layer is spin-coated on the TFB hole transport layer;
  • An Al cathode layer was vapor-deposited on the PAMAM modified layer to obtain a quantum dot light-emitting diode.
  • a quantum dot light-emitting diode is prepared as follows:
  • a layer of TFB hole transport layer is spin-coated on the Cu 2+ doped PAMAM modified ITO anode
  • a CdSe/ZnS quantum dot light-emitting layer is spin-coated on the TFB hole transport layer;
  • An Al cathode layer was vapor-deposited on the PAMAM modified layer to obtain a quantum dot light-emitting diode.
  • a quantum dot light emitting diode is prepared as follows:
  • a layer of CdSe/ZnS quantum dot light-emitting layer is spin-coated on the PAMAM modified ITO cathode;
  • An Au anode layer was vapor-deposited on the Cu 2+ doped PAMAM modified layer to obtain a quantum dot light-emitting diode.
  • a quantum dot light-emitting diode is prepared as follows:
  • a CdSe/ZnS quantum dot light-emitting layer is spin-coated on the zinc oxide electron transport layer;
  • An Au anode layer was vapor-deposited on the Cu 2+ doped PAMAM modified layer to obtain a quantum dot light-emitting diode.
  • a quantum dot light emitting diode is prepared as follows:
  • a CdSe/ZnS quantum dot light-emitting layer is spin-coated on the ZnO electron transport layer;
  • An Au anode layer was vapor-deposited on the Cu 2+ doped PAMAM modified layer to obtain a quantum dot light-emitting diode.
  • a quantum dot light emitting diode is prepared as follows:
  • a CdSe/ZnS quantum dot light-emitting layer is spin-coated on the ZnO electron transport layer;
  • a TFB hole transport layer was spin-coated on the CdSe/ZnS quantum dot light-emitting layer
  • the above mixed solution was spin-coated on the TFB hole transport layer, and then heated at 90°C for 20 min after spin coating to form a Cu 2+ doped PAMAM modified layer;
  • An Au anode layer was vapor-deposited on the Cu 2+ doped PAMAM modified layer to obtain a quantum dot light-emitting diode.
  • the work function of the anode can be improved, thereby improving the hole Injection effect to further improve device performance.
  • the present disclosure can also be used to modify the cathode by disposing the second modification layer between the cathode and the quantum dot light-emitting layer, the work function of the modified cathode will be reduced, thereby improving the electron injection effect and thereby improving the performance of the device .

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Abstract

一种量子点发光二极管及其制备方法，其中所述量子点发光二极管，包括阳极、量子点发光层及阴极，所述量子点发光层设置在所述阳极与所述阴极之间，还包括设置于所述阳极与所述量子点发光层之间的第一修饰层，所述第一修饰层包括PAMAM，所述PAMAM中掺杂有过渡金属阳离子。通过将第一修饰层设置在阳极与量子点发光层之间，用于修饰阳极，可以提高阳极的功函数，从而提高空穴的注入效果，进而提高器件的性能。还通过将第二修饰层设置在阴极与量子点发光层之间，用于修饰阴极，经修饰后的阴极的功函数会有所降低，从而提高电子注入效果，进而提高器件的性能。

Description

一种量子点发光二极管及其制备方法 技术领域
本公开涉及量子点发光器件领域，尤其涉及一种量子点发光二极管及其制备方法。
背景技术
胶体量子点(Colloidal quantum dot，CQD)是在溶液的基础上合成出来的半导体纳米晶体。胶体量子点由于具有发光线宽窄、发光效率高，且不同大小的量子点能被单一波长的光激发而发出不同颜色的光等特点，推动着下一代光电显示技术的发展。以胶体量子点作为发光层的量子点发光二极管(Quantum dot light-emitting diode，QLED)是极具潜力的下一代显示和固态照明光源。
一般而言，QLED是由多层薄膜组成的多层结构，包括阴极、量子点发光层、阳极，以及设置在阴极与量子点发光层之间的电子传输层(和/或电子注入层)和设置在阳极与量子点发光层之间的空穴传输层(和/或空穴注入层)。其中，设置载流子传输层和注入层的目的，主要是因为电极与量子点发光层之间的能级差异太大，导致载流子不能有效地从电极注入到量子点发光层中。虽然引入载流子传输层后可以有利于载流子的注入，但是一般来说，不同载流子传输层材料具有相对固定的能带结构，所以针对某种的电极材料与量子点发光材料，需要寻找特定的能带相匹配的材料作为载流子传输层。因此，高性能的QLED器件对载流子传输层材料的要求很高，材料的使用也比较单一，并且电子传输层与空穴传输层的材料类型往往差异非常大。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本公开的目的在于提供一种量子点发光二极管及其制备方法，旨在解决现有高性能的量子点发光二极管对载流子传输层材料的要求很高，材料的使用也比较单一，并且电子传输层与空穴传输层的材料类型往往差异非常大的问题。
本公开的技术方案如下：
一种量子点发光二极管，包括阳极、量子点发光层及阴极，所述量子点发光层设置在所述阳极与所述阴极之间，其中，还包括设置于所述阳极与所述量子点发光层之间的第一修饰层，所述第一修饰层包括PAMAM(聚酰胺-胺型树枝状高分子)，所述PAMAM中掺杂有过渡金属阳离子。
一种量子点发光二极管，包括阳极、量子点发光层及阴极，所述量子点发光层设置在所述阳极与所述阴极之间，其中，还包括设置于所述阴极与所述量子点发光层之间的第二修饰层，所述第二修饰层包括PAMAM。
一种量子点发光二极管的制备方法，其中，包括步骤：
提供阳极；
在所述阳极上制备第一修饰层，所述第一修饰层包括PAMAM，所述PAMAM中掺杂有过渡金属阳离子；
在所述第一修饰层上制备量子点发光层；
在所述量子点发光层上制备阴极。
有益效果：本公开通过将第一修饰层设置在阳极与量子点发光层之间，用于修饰阳极，可以提高阳极的功函数，从而提高空穴的注入效果，进而提高器件的性能。本公开还可以通过将第二修饰层设置在阴极与量子点发光层之间，用于修饰阴极，经修饰后的阴极的功函数会有所降低，从而提高电子注入效果，进而提高器件的性能。
附图说明
图1为本公开实施例中PAMAM的化学结构式；
图2为本公开提供的一种量子点发光二极管的制备方法的流程示意图；
图3为本公开实施例1的量子点发光二极管的结构示意图；
图4为本公开实施例2的量子点发光二极管的结构示意图；
图5为本公开实施例3的量子点发光二极管的结构示意图；
图6为本公开实施例4的量子点发光二极管的结构示意图；
图7为本公开实施例5的量子点发光二极管的结构示意图；
图8为本公开实施例6的量子点发光二极管的结构示意图；
图9为本公开实施例7的量子点发光二极管的结构示意图；
图10为本公开实施例8的量子点发光二极管的结构示意图。
具体实施方式
本公开提供一种量子点发光二极管及其制备方法，为使本公开的目的、技术方案及效果更加清楚、明确，以下对本公开进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
本公开实施例提供一种量子点发光二极管，包括阳极、量子点发光层及阴极，所述量子点发光层设置在所述阳极与所述阴极之间，其中，还包括设置于所述阳极与所述量子点发光层之间的第一修饰层，所述第一修饰层包括PAMAM，所述PAMAM中掺杂有过渡金属阳离子。
本实施例中，通过将第一修饰层(过渡金属阳离子掺杂的PAMAM)设置在阳极与量子点发光层之间，用于修饰阳极，可以提高阳极的功函数，从而提高空穴的注入效果，进而提高器件的性能。
具体地，阳极经过第一修饰层的修饰后，其功函数会发生变化的原因在于，由于PAMAM为树枝状高分子材料，其表面具有大量的氨基和羰基(见图1)，当掺入过渡金属阳离子后，这些基团会与过渡金属阳离子形成络合物，使过渡金属阳离子与PAMAM中的N和O原子形成共价键，从而改变了PAMAM材料的偶极矩，利于空穴的注入，因此，当用过渡金属阳离子掺杂的PAMAM修饰阳极后，阳极的功函数会提高。
需要说明的是，在本公开实施例中，第一修饰层中除了包括PAMAM，所述PAMAM中掺杂有过渡金属阳离子外，第一修饰层中可能还存在其他杂质，例如Li/Na/Al/Mg等非过渡金属离子，这些杂质对第一修饰层的作用不会产生有利或有害影响。
当然，在本公开的实施例中，第一修饰层由过渡金属阳离子掺杂的PAMAM组成，而不含其他杂质，以使得本领域技术人员更好地调控过渡金属阳离子和PAMAM的含量 比，有针对性的改变阳极的功函数。
在一些实施方式中，所述第一修饰层中还掺杂有阴离子，所述阴离子与所述过渡金属阳离子组成金属盐。所述阴离子会吸附在阳极表面，由于其具有推电子作用，可以进一步促进空穴的注入。
在一些实施方式中，所述过渡金属阳离子与第一修饰层中的PAMAM的摩尔比为0.01～720。通过调节PAMAM中过渡金属阳离子的掺入量，可以轻松地以不同程度提高阳极的功函数，从而提高空穴的注入效果，并且能够使的量子点发光二极管的材料选择性和器件结构设计更加丰富，更具有多样性。例如，Cu 2+的掺入量(摩尔比)从0提高到325时，ITO阳极的功函数从4.07eV逐渐提高到4.97eV。需要说明的是，量子点发光二极管常用的空穴注入层材料为PEDOT:PSS，其功函数为5.05eV，说明PAMAM中掺入高浓度Cu 2+后，其修饰的ITO功函数接近PEDOT:PSS材料的功函数，即其具有良好的空穴注入性能。
在一些实施方式中，所述过渡金属阳离子中的过渡金属可以包括但不限于Cu、Ni、Zn、Co、Fe、Mn、Cr、V、Ti、Sc、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pb、Ag、Cd、Hf、Ta、W、Re、Os、Ir、Pt、Au和Hg中的一种或多种。本实施例通过调节过渡金属阳离子的材料类型，可以轻松地以不同程度提高阳极的功函数，从而提高空穴的注入效果。进一步在一些实施方式中，所述过渡金属阳离子中的过渡金属可以选自但不限于Cu、Ni、Co、Fe、Mn、Cr、V、Ti、Y、Zr、Mo、Zr和Ru中的一种或多种。
进一步在一些实施方式中，所述阴离子可以包括但不限于Cl -、CO 3 -、S 2-、SO 4 2-、SO 3 2-、MnO 4 2-、MnO 4 -、PO 4 3-、NO 3 -、NO 2 -、ClO 3 -、ClO -、ClO 2 -、ClO 4 -、CN -、AlO 2 -、AlO 3 3-、C 2O 4 2-、FeO 4 2-、Cr 2O 7 2-、CrO 4 2-和SeO 4 2-中的一种或多种。
在一些实施方式中，所述第一修饰层的厚度为2～110nm。
在一些实施方式中，所述量子点发光二极管还包括设置于所述阴极与所述量子点发光层之间的第二修饰层，所述第二修饰层包括PAMAM。
本实施例通过将第二修饰层设置在阴极与量子点发光层之间，用于修饰阴极，经修饰后的阴极的功函数会有所降低，从而提高电子注入效果，进而提高器件的性能。具体 地，阴极经过第二修饰层的修饰后，其功函数会发生变化的原因在于，由于PAMAM为树枝状高分子材料，其表面具有大量的氨基和羰基(见图1)，当用PAMAM修饰阴极后，所形成的偶极矩会降低阴极的功函数，因此有利于电子的注入。
同样地，第二修饰层中除了包括PAMAM之外，可能还会存在其他杂质，这些杂质对第二修饰层的作用也不会产生有利或有害的影响。
当然，在本公开的实施例中，第二修饰层为PAMAM，以便本领域技术人员仅仅需要调控PAMAM便可实现阴极功函数的调整。
进一步在一些实施方式中，所述第二修饰层的厚度为5～96nm。通过调节第二修饰层的厚度，能够轻松地以不同程度降低阴极的功函数，从而提高电子的注入效果，并且能够使量子点发光二极管的材料选择性和器件结构设计更加丰富，更具有多样性。
在一些实施方式中，所述阳极材料可以包括但不限于金属材料、碳材料、金属氧化物和空穴注入材料中的一种或多种。进一步在一些实施方式中，所述金属材料可以包括Al、Ag、Cu、Mo、Au、Ba、Ca和Mg中的一种或多种。进一步在一些实施方式中，所述碳材料可以包括石墨、碳纳米管、石墨烯和碳纤维中的一种或多种。所述金属氧化物可以是掺杂或非掺杂金属氧化物，其可以包括ITO、FTO、ATO、AZO、GZO、IZO、MZO和AMO中的一种或多种；所述金属氧化物也可以是掺杂或非掺杂透明金属氧化物之间夹着金属的复合电极，其中，所述复合电极可以包括AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO 2/Ag/TiO 2、TiO 2/Al/TiO 2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2/Ag/TiO 2和TiO 2/Al/TiO 2中的一种或多种。进一步在一些实施方式中，所述空穴注入材料可以包括但不限于PEDOT:PSS、CuPc、F4-TCNQ、HATCN、过渡金属氧化物和过渡金属硫系化合物中的一种或多种。其中，所述过渡金属氧化物可以包括NiO x、MoO x、WO x、CrO x和CuO中的一种或多种；所述金属硫系化合物可以包括MoS x、MoSe x、WS x、WSe x和CuS中的一种或多种。本实施例通过调节过渡阳极的材料类型，可以轻松地以不同程度提高阳极的功函数，从而提高空穴的注入效果。例如，当Cu 2+的掺入量(摩尔比)为325时，所修饰的金阳极(Au)、银阳极(Ag)、还原石墨烯阳极(RGO)的功函数分别从4.98eV、4.45eV、5.20eV提高到5.14eV、 4.87eV、5.42eV。
在一些实施方式中，所述阴极材料可以包括但不限于金属材料、碳材料和金属氧化物中的一种或多种。作为举例，所述金属材料可以包括Al、Ag、Cu、Mo、Au、Ba、Ca和Mg中的一种或多种。作为举例，所述碳材料可以包括石墨、碳纳米管、石墨烯和碳纤维中的一种或多种。所述金属氧化物可以是掺杂或非掺杂金属氧化物，例如可以包括ITO、FTO、ATO、AZO、GZO、IZO、MZO和AMO中的一种或多种；所述金属氧化物还可以是掺杂或非掺杂透明金属氧化物之间夹着金属的复合电极，例如可以包括AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO 2/Ag/TiO 2、TiO 2/Al/TiO 2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2/Ag/TiO 2和TiO 2/Al/TiO 2中的一种或多种。通过修饰不同材料的阴极，能够轻松地以不同程度降低阴极的功函数，从而提高电子的注入效果，并且能够使量子点发光二极管的材料选择性和器件结构设计更加丰富，更具有多样性。例如，对金阴极(Au)、银阴极(Ag)、还原石墨烯阴极(RGO)，通过修饰PAMAM后，其功函数分别从4.98eV、4.45eV、5.20eV降低到3.66eV、3.74eV、4.27eV。
本实施例中，所述量子点发光二极管还可以包括设置于所述第一修饰层与所述量子点发光层之间的空穴功能层。其中所述空穴功能层可以包括空穴注入层和空穴传输层中的一种或两种。所述空穴功能层为空穴注入层和空穴传输层中的两种时，所述空穴传输层与所述量子点发光层贴合设置。
在一些实施方式中，所述空穴注入层的材料为具有良好空穴注入性能的材料，例如可以包括但不限于聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、酞菁铜(CuPc)、2,3,5,6-四氟-7,7',8,8'-四氰醌-二甲烷(F4-TCNQ)、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HATCN)、过渡金属氧化物、过渡金属硫系化合物中的一种或多种；其中，所述过渡金属氧化物可以包括NiO x、MoO x、WO x、CrO x和CuO中的一种或多种；所述金属硫系化合物可以包括MoS x、MoSe x、WS x、WSe x和CuS中的一种或多种。
在一些实施方式中，所述空穴传输层的材料为具有良好空穴传输能力的有机材料，例如可以包括但不限于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(TFB)、聚乙烯咔唑 (PVK)、聚(N,N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)(Poly-TPD)、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)(PFB)、4,4’,4”-三(咔唑-9-基)三苯胺(TCTA)、4,4'-二(9-咔唑)联苯(CBP)、N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-联苯-4,4’-二胺(TPD)、N,N’-二苯基-N,N’-(1-萘基)-1,1’-联苯-4,4’-二胺(NPB)、石墨烯和C60中的一种或多种。在一些实施方式中，所述空穴传输层还可以选自具有空穴传输能力的无机材料，例如可以包括但不限于NiO x、MoO x、WO x、CrO x、CuO、MoS x、MoSe x、WS x、WSe x和CuS中的一种或多种。
本实施例中，所述量子点发光二极管还可以包括设置于所述阴极与所述量子点发光层之间的电子功能层。当所述量子点发光二极管包括第二修饰层时，所述电子功能层设置于所述第二修饰层与所述量子点发光层之间。其中所述电子功能层可以选自电子注入层和电子传输层中的一种或两种。所述电子功能层为电子注入层和电子传输层中的两种时，所述电子传输层与所述量子点发光层贴合设置。
在一些实施方式中，所述电子传输层的材料和电子注入层的材料均为具有电子传输能力的无机材料和/或有机材料，例如所述具有电子传输能力的无机材料可以选自掺杂或非掺杂的金属氧化物、掺杂或非掺杂的金属硫化物中的一种或多种。其中，所述掺杂或非掺杂金属氧化物可以包括ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、NiO、TiLiO、ZnAlO、ZnMgO、ZnSnO、ZnLiO和InSnO中的一种或多种。所述掺杂或非掺杂金属硫化物可以包括CdS、ZnS、MoS、WS和CuS中的一种或多种。
本实施例中，所述量子点发光层的材料可以包括但不限于II-VI族化合物、III-V族化合物、II-V族化合物、III-VI化合物、IV-VI族化合物、I-III-VI族化合物、II-IV-VI族化合物或IV族单质中的一种或多种。作为举例，所述量子点发光层的材料可以包括但不限于CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、HgS、HgSe、HgTe、PbS、PbSe、PbTe和其他二元、三元、四元的II-VI化合物中的一种或多种；作为举例，所述量子点发光层的材料可以包括但不限于GaP、GaAs、InP、InAs和其他二元、三元、四元的III-V化合物中的一种或多种。
本实施例中，所述量子点发光层的材料还可以为掺杂或非掺杂的无机钙钛矿型半导 体、和/或有机-无机杂化钙钛矿型半导体。其中，所述无机钙钛矿型半导体的结构通式为AMX 3，其中A为Cs +离子；M为二价金属阳离子，可以包括但不限于Pb 2+、Sn 2+、Cu 2+、Ni 2+、Cd 2+、Cr 2+、Mn 2+、Co 2+、Fe 2+、Ge 2+、Yb 2+或Eu 2+；X为卤素阴离子，可以包括但不限于Cl -、Br -或I -。其中，所述有机-无机杂化钙钛矿型半导体的结构通式为BMX 3，其中B为有机胺阳离子，可以选自但不限于CH 3(CH 2) n-2NH 3 +(n≥2)或NH 3(CH 2) nNH 3 2+(n≥2)；当n＝2时，无机金属卤化物八面体MX 6 4-通过共顶的方式连接，金属阳离子M位于卤素八面体的体心，有机胺阳离子B填充在八面体间的空隙内，形成无限延伸的三维结构；当n＞2时，以共顶的方式连接的无机金属卤化物八面体MX 6 4-在二维方向延伸形成层状结构，层间插入有机胺阳离子双分子层(质子化单胺)或有机胺阳离子单分子层(质子化双胺)，有机层与无机层相互交叠形成稳定的二维层状结构；M为二价金属阳离子，可以选自但不限于Pb 2+、Sn 2+、Cu 2+、Ni 2+、Cd 2+、Cr 2+、Mn 2+、Co 2+、Fe 2+、Ge 2+、Yb 2+、Eu 2+；X为卤素阴离子，可以选自但不限于Cl -、Br -或I -。
需说明的是，所述量子点发光二极管还可以包括界面修饰层，所述界面修饰层可以选自电子阻挡层、空穴阻挡层、电子注入层、电极修饰层和隔离保护层中的一层或多层。
本实施例中，所述量子点发光二极管，其封装方式可以为部分封装、全封装或不封装。
本公开实施例提供一种量子点发光二极管，包括阳极、量子点发光层及阴极，所述量子点发光层设置在所述阳极与所述阴极之间，其中，还包括设置于所述阴极与所述量子点发光层之间的第二修饰层，所述第二修饰层包括PAMAM。本实施例通过将第二修饰层设置在阴极与量子点发光层之间，用于修饰阴极，经修饰后的阴极的功函数会有所降低，从而提高电子注入效果，进而提高器件的性能。具体地，阴极经过第二修饰层的修饰后，其功函数会发生变化的原因在于，由于PAMAM为树枝状高分子材料，其表面具有大量的氨基和羰基(见图1)，当用PAMAM修饰阴极后，所形成的偶极矩会降低阴极的功函数，因此有利于电子的注入。
本公开实施例还提供一种量子点发光二极管的制备方法，如图2所示，包括以下步骤：
提供阳极；
在所述阳极上制备第一修饰层，所述第一修饰层包括PAMAM，所述PAMAM中掺杂有过渡金属阳离子；
在所述第一修饰层上制备量子点发光层；
在所述量子点发光层上制备阴极。
本公开中，各层沉积方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法、条状涂布法、热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法中的一种或多种。
需要说明的是，在本公开实施例中，第一修饰层中除了包括PAMAM，所述PAMAM中掺杂有过渡金属阳离子外，第一修饰层中可能还存在其他杂质，例如Li/Na/Al/Mg等非过渡金属离子，这些杂质对第一修饰层的作用不会产生有利或有害影响。
当然，在本公开的实施例中，第一修饰层由过渡金属阳离子掺杂的PAMAM组成，而不含其他杂质，以使得本领域技术人员更好地调控过渡金属阳离子和PAMAM的含量比，有针对性的改变阳极的功函数。
在一些实施方式中，所述第一修饰层中还掺杂有阴离子，所述阴离子与所述过渡金属阳离子组成金属盐。所述阴离子会吸附在阳极表面，由于其具有推电子作用，可以进一步促进空穴的注入。
在一些实施方式中，所述在所述第一修饰层上制备量子点发光层，在所述量子点发光层上制备阴极的步骤，具体包括：在所述第一修饰层上制备量子点发光层，在所述量子点发光层上制备第二修饰层，在所述第二修饰层上制备阴极，所述第二修饰层包括PAMAM。本实施例通过将第二修饰层设置在阴极与量子点发光层之间，用于修饰阴极，经修饰后的阴极的功函数会有所降低，从而提高电子注入效果，进而提高器件的性能。具体地，阴极经过第二修饰层的修饰后，其功函数会发生变化的原因在于，由于PAMAM 为树枝状高分子材料，其表面具有大量的氨基和羰基(见图1)，当用PAMAM修饰阴极后，所形成的偶极矩会降低阴极的功函数，因此有利于电子的注入。
同样地，第二修饰层中除了包括PAMAM之外，可能还会存在其他杂质，这些杂质对第二修饰层的作用也不会产生有利或有害的影响。
当然，在本公开的实施例中，第二修饰层为PAMAM，以便本领域技术人员仅仅需要调控PAMAM便可实现阴极功函数的调整。
进一步在一些实施方式中，所述第二修饰层的厚度为5～96nm。通过调节第二修饰层的厚度，能够轻松地以不同程度降低阴极的功函数，从而提高电子的注入效果，并且能够使量子点发光二极管的材料选择性和器件结构设计更加丰富，更具有多样性。
在一些实施方式中，所述过渡金属阳离子与第一修饰层中的PAMAM的摩尔比为0.01～720。通过调节PAMAM中过渡金属阳离子的掺入量，可以轻松地以不同程度提高阳极的功函数，从而提高空穴的注入效果，并且能够使的量子点发光二极管的材料选择性和器件结构设计更加丰富，更具有多样性。例如，Cu 2+的掺入量(摩尔比)从0提高到325时，ITO阳极的功函数从4.07eV逐渐提高到4.97eV。需要说明的是，量子点发光二极管常用的空穴注入层材料为PEDOT:PSS，其功函数为5.05eV，说明PAMAM中掺入高浓度Cu 2+后，其修饰的ITO功函数接近PEDOT:PSS材料的功函数，即其具有良好的空穴注入性能。
在一些实施方式中，所述过渡金属阳离子中的过渡金属可以包括但不限于Cu、Ni、Zn、Co、Fe、Mn、Cr、V、Ti、Sc、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pb、Ag、Cd、Hf、Ta、W、Re、Os、Ir、Pt、Au和Hg中的一种或多种。本实施例通过调节过渡金属阳离子的材料类型，可以轻松地以不同程度提高阳极的功函数，从而提高空穴的注入效果。所述过渡金属阳离子中的过渡金属可以选自但不限于Cu、Ni、Co、Fe、Mn、Cr、V、Ti、Y、Zr、Mo、Zr和Ru中的一种或多种。
进一步在一些实施方式中，所述阴离子可以包括但不限于Cl -、CO 3 -、S 2-、SO 4 2-、SO 3 2-、MnO 4 2-、MnO 4 -、PO 4 3-、NO 3 -、NO 2 -、ClO 3 -、ClO -、ClO 2 -、ClO 4 -、CN -、AlO 2 -、AlO 3 3-、C 2O 4 2-、FeO 4 2-、Cr 2O 7 2-、CrO 4 2-和SeO 4 2-中的一种或多种。
在一些实施方式中，所述第一修饰层的厚度为2～110nm。下面通过实施例对本公开进行详细说明。
实施例1
结合图3所示，一种量子点发光二极管，其制备过程如下：
首先将PAMAM溶解在甲醇中，然后加入CuCl 2，其中CuCl 2与PAMAM的摩尔比为275:1，然后将混合溶液搅拌8h，备用；另外再配制PAMAM的异丙醇溶液，备用；
将上述混合溶液旋涂在ITO导电玻璃上，旋涂后于100℃加热30min，得到Cu 2+掺杂的PAMAM修饰的ITO阳极；
在上述Cu 2+掺杂的PAMAM修饰的ITO阳极上旋涂一层CdSe/ZnS量子点发光层；
将上述PAMAM的异丙醇溶液旋涂在CdSe/ZnS量子点发光层上，旋涂后于80℃加热15min，形成一层PAMAM修饰层；
在PAMAM修饰层上蒸镀一层Al阴极层，得到量子点发光二极管。
实施例2
结合图4所示，一种量子点发光二极管，其制备过程如下：
首先将PAMAM溶解在甲醇中，然后加入CuCl 2，其中CuCl 2与PAMAM的摩尔比为275:1，然后将混合溶液搅拌8h，备用；
将上述混合溶液旋涂在ITO导电玻璃上，旋涂后于100℃加热30min，得到Cu 2+掺杂的PAMAM修饰的ITO阳极；
在上述Cu 2+掺杂的PAMAM修饰的ITO阳极上旋涂一层CdSe/ZnS量子点发光层；
在CdSe/ZnS量子点发光层上旋涂一层ZnO电子传输层；
在ZnO电子传输层上蒸镀一层Al阴极层，得到量子点发光二极管。
实施例3
结合图5所示，一种量子点发光二极管，其制备过程如下：
首先将PAMAM溶解在甲醇中，然后加入CuCl 2，其中CuCl 2与PAMAM的摩尔比为275:1，然后将混合溶液搅拌8h，备用；另外再配制PAMAM的异丙醇溶液，备用；
将上述混合溶液旋涂在ITO导电玻璃上，旋涂后于100℃加热30min，得到Cu 2+掺 杂的PAMAM修饰的ITO阳极；
在上述Cu 2+掺杂的PAMAM修饰的ITO阳极上旋涂一层TFB空穴传输层；
在TFB空穴传输层上旋涂一层CdSe/ZnS量子点发光层；
将上述PAMAM的异丙醇溶液旋涂在CdSe/ZnS量子点发光层上，旋涂后于80℃加热15min，形成一层PAMAM修饰层；
在PAMAM修饰层上蒸镀一层Al阴极层，得到量子点发光二极管。
实施例4
结合图6所示，一种量子点发光二极管，其制备过程如下：
首先将PAMAM溶解在甲醇中，然后加入CuCl 2，其中CuCl 2与PAMAM的摩尔比为275:1，然后将混合溶液搅拌8h，备用；另外再配制PAMAM的异丙醇溶液，备用；
将上述混合溶液旋涂在ITO导电玻璃上，旋涂后于100℃加热30min，得到Cu 2+掺杂的PAMAM修饰的ITO阳极；
在上述Cu 2+掺杂的PAMAM修饰的ITO阳极上旋涂一层TFB空穴传输层；
在TFB空穴传输层上旋涂一层CdSe/ZnS量子点发光层；
在CdSe/ZnS量子点发光层上旋涂一层ZnO电子传输层；
将上述PAMAM的异丙醇溶液旋涂在ZnO电子传输层上，旋涂后于80℃加热15min，形成一层PAMAM修饰层；
在PAMAM修饰层上蒸镀一层Al阴极层，得到量子点发光二极管。
实施例5
结合图7所示，一种量子点发光二极管，其制备过程如下：
首先将PAMAM溶解在甲醇中，然后加入CuCl 2，其中CuCl 2与PAMAM的摩尔比为275:1，然后将混合溶液搅拌8h，备用；另外再配制PAMAM的异丙醇溶液，备用；
将上述PAMAM的异丙醇溶液旋涂在ITO导电玻璃上，旋涂后于80℃加热15min，得到PAMAM修饰的ITO阴极；
在上述PAMAM修饰的ITO阴极上旋涂一层CdSe/ZnS量子点发光层；
将上述混合溶液旋涂旋涂在CdSe/ZnS量子点发光层上，旋涂后于90℃加热20min， 形成一层Cu 2+掺杂的PAMAM修饰层；
在Cu 2+掺杂的PAMAM修饰层上蒸镀一层Au阳极层，得到量子点发光二极管。
实施例6
结合图8所示，一种量子点发光二极管，其制备过程如下：
首先将PAMAM溶解在甲醇中，然后加入CuCl 2，其中CuCl 2与PAMAM的摩尔比为275:1，然后将混合溶液搅拌8h，备用；
在ITO导电玻璃上旋涂一层氧化锌电子传输层；
在氧化锌电子传输层上旋涂一层CdSe/ZnS量子点发光层；
将上述混合溶液旋涂旋涂在CdSe/ZnS量子点发光层上，旋涂后于90℃加热20min，形成一层Cu 2+掺杂的PAMAM修饰层；
在Cu 2+掺杂的PAMAM修饰层上蒸镀一层Au阳极层，得到量子点发光二极管。
实施例7
结合图9所示，一种量子点发光二极管，其制备过程如下：
首先将PAMAM溶解在甲醇中，然后加入CuCl 2，其中，CuCl 2与PAMAM的摩尔比为275:1，然后将混合溶液搅拌8h，备用；另外再配制PAMAM的异丙醇溶液，备用。
将上述PAMAM的异丙醇溶液旋涂在ITO导电玻璃上，旋涂后于80℃加热15min，得到PAMAM修饰的ITO阴极；
在上述PAMAM修饰的ITO阴极上旋涂一层ZnO电子传输层；
在ZnO电子传输层上旋涂一层CdSe/ZnS量子点发光层；
将上述混合溶液旋涂旋涂在CdSe/ZnS量子点发光层上，旋涂后于90℃加热20min，形成一层Cu 2+掺杂的PAMAM修饰层；
在Cu 2+掺杂的PAMAM修饰层上蒸镀一层Au阳极层，得到量子点发光二极管。
实施例8
结合图10所示，一种量子点发光二极管，其制备过程如下：
首先将PAMAM溶解在甲醇中，然后加入CuCl 2，其中CuCl 2与PAMAM的摩尔比为275:1，然后将混合溶液搅拌8h，备用；另外再配制PAMAM的异丙醇溶液，备用；
将上述PAMAM的异丙醇溶液旋涂在ITO导电玻璃上，旋涂后于80℃加热15min，得到PAMAM修饰的ITO阴极；
在上述PAMAM修饰的ITO阴极上旋涂一层ZnO电子传输层；
在ZnO电子传输层上旋涂一层CdSe/ZnS量子点发光层；
在CdSe/ZnS量子点发光层上旋涂一层TFB空穴传输层；
将上述混合溶液旋涂旋涂在TFB空穴传输层上，旋涂后于90℃加热20min，形成一层Cu 2+掺杂的PAMAM修饰层；
在Cu 2+掺杂的PAMAM修饰层上蒸镀一层Au阳极层，得到量子点发光二极管。
综上所述，本公开通过将第一修饰层(过渡金属阳离子掺杂的PAMAM)设置在阳极与量子点发光层之间，用于修饰阳极，可以提高阳极的功函数，从而提高空穴的注入效果，进而提高器件的性能。本公开还可以通过将第二修饰层设置在阴极与量子点发光层之间，用于修饰阴极，经修饰后的阴极的功函数会有所降低，从而提高电子注入效果，进而提高器件的性能。
应当理解的是，本公开的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本公开所附权利要求的保护范围。

Claims (20)

  1. 一种量子点发光二极管，包括阳极、量子点发光层及阴极，所述量子点发光层设置在所述阳极与所述阴极之间，其特征在于，还包括设置于所述阳极与所述量子点发光层之间的第一修饰层，所述第一修饰层包括PAMAM，所述PAMAM中掺杂有过渡金属阳离子。
  2. 根据权利要求1所述的量子点发光二极管，其特征在于，所述第一修饰层由过渡金属阳离子掺杂的PAMAM组成。
  3. 根据权利要求1或2所述的量子点发光二极管，其特征在于，所述PAMAM中还掺杂有阴离子。
  4. 根据权利要求1所述的量子点发光二极管，其特征在于，还包括设置于所述阴极与所述量子点发光层之间的第二修饰层，所述第二修饰层包括PAMAM。
  5. 根据权利要求1所述的量子点发光二极管，其特征在于，所述过渡金属阳离子与所述第一修饰层中的PAMAM的摩尔比为0.01～720。
  6. 根据权利要求1所述的量子点发光二极管，其特征在于，所述过渡金属阳离子中的过渡金属包括Cu、Ni、Zn、Co、Fe、Mn、Cr、V、Ti、Sc、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pb、Ag、Cd、Hf、Ta、W、Re、Os、Ir、Pt、Au和Hg中的一种或多种。
  7. 根据权利要求3所述的量子点发光二极管，其特征在于，所述阴离子包括Cl -、CO 3 -、S 2-、SO 4 2-、SO 3 2-、MnO 4 2-、MnO 4 -、PO 4 3-、NO 3 -、NO 2 -、ClO 3 -、ClO -、ClO 2 -、ClO 4 -、CN -、AlO 2 -、AlO 3 3-、C 2O 4 2-、FeO 4 2-、Cr 2O 7 2-、CrO 4 2-、SeO 4 2-中的一种或多种。
  8. 根据权利要求1所述的量子点发光二极管，其特征在于，所述阳极材料包括金属材料、碳材料、金属氧化物和空穴注入材料中的一种或多种；和/或
    所述阴极材料包括金属材料、碳材料和金属氧化物中的一种或多种。
  9. 根据权利要求1所述的量子点发光二极管，其特征在于，所述第一修饰层的厚度为2～110nm。
  10. 根据权利要求4所述的量子点发光二极管，其特征在于，所述第二修饰层的厚度为5～96nm。
  11. 一种量子点发光二极管，包括阳极、量子点发光层及阴极，所述量子点发光层 设置在所述阳极与所述阴极之间，其特征在于，还包括设置于所述阴极与所述量子点发光层之间的第二修饰层，所述第二修饰层包括PAMAM。
  12. 一种量子点发光二极管的制备方法，其特征在于，包括步骤：
    提供阳极；
    在所述阳极上制备第一修饰层，所述第一修饰层包括PAMAM，所述PAMAM中掺杂有过渡金属阳离子；
    在所述第一修饰层上制备量子点发光层；
    在所述量子点发光层上制备阴极。
  13. 根据权利要求12所述的量子点发光二极管的制备方法，其特征在于，所述第一修饰层由过渡金属阳离子掺杂的PAMAM组成。
  14. 根据权利要求12或13所述的量子点发光二极管的制备方法，其特征在于，所述PAMAM中还掺杂有阴离子。
  15. 根据权利要求12所述的量子点发光二极管的制备方法，其特征在于，所述在所述第一修饰层上制备量子点发光层，在所述量子点发光层上制备阴极的步骤，具体包括：在所述第一修饰层上制备量子点发光层，在所述量子点发光层上制备第二修饰层，在所述第二修饰层上制备阴极，所述第二修饰层包括PAMAM。
  16. 根据权利要求12所述的量子点发光二极管的制备方法，其特征在于，所述过渡金属阳离子与所述第一修饰层中的PAMAM的摩尔比为0.01～720。
  17. 根据权利要求12所述的量子点发光二极管的制备方法，其特征在于，所述过渡金属阳离子中的过渡金属包括Cu、Ni、Zn、Co、Fe、Mn、Cr、V、Ti、Sc、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pb、Ag、Cd、Hf、Ta、W、Re、Os、Ir、Pt、Au和Hg中的一种或多种。
  18. 根据权利要求14所述的量子点发光二极管的制备方法，其特征在于，所述阴离子包括Cl -、CO 3 -、S 2-、SO 4 2-、SO 3 2-、MnO 4 2-、MnO 4 -、PO 4 3-、NO 3 -、NO 2 -、ClO 3 -、ClO -、ClO 2 -、ClO 4 -、CN -、AlO 2 -、AlO 3 3-、C 2O 4 2-、FeO 4 2-、Cr 2O 7 2-、CrO 4 2-、SeO 4 2-中的一种或多种。
  19. 根据权利要求12所述的量子点发光二极管的制备方法，其特征在于，所述第一修饰层的厚度为2～110nm。
  20. 根据权利要求15所述的量子点发光二极管的制备方法，其特征在于，所述第二修饰层的厚度为5～96nm。
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