WO2021143653A1 - Qled器件、空穴传输材料及其制作方法、显示装置 - Google Patents

Qled器件、空穴传输材料及其制作方法、显示装置 Download PDF

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WO2021143653A1
WO2021143653A1 PCT/CN2021/071135 CN2021071135W WO2021143653A1 WO 2021143653 A1 WO2021143653 A1 WO 2021143653A1 CN 2021071135 W CN2021071135 W CN 2021071135W WO 2021143653 A1 WO2021143653 A1 WO 2021143653A1
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metal compound
hole transport
nio
metal
transport material
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French (fr)
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冯靖雯
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京东方科技集团股份有限公司
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    • 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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    • H10K2102/351—Thickness

Definitions

  • the present invention relates to the technical field of display equipment, in particular to a QLED device, a hole transport material and a manufacturing method thereof, and a display device.
  • QLED display device Quantum dot light-emitting diode, quantum dot electroluminescent diode
  • QLED Quantum dot light-emitting diode, quantum dot electroluminescent diode
  • QLED Quantum Dot Light Emitting Diode, Quantum Dot Electroluminescent Diode
  • each functional layer includes a hole injection layer, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer, and an electrode.
  • most functional layers are made of organic materials. Because organic materials are easily corroded by water and oxygen, which reduces the life of the device, the development of inorganic functional layer materials has become a research focus.
  • the introduction of the ZnO electron transport layer greatly improves the electron injection efficiency, and hole injection needs to overcome a large barrier, which causes electrons to become multitons in the device and makes the electron-hole injection imbalance, which will also affect the device Efficiency and longevity.
  • the first aspect of the embodiments of the present invention provides a hole transport material, including: a polymer, the polymer is a single nanoparticle including at least a first metal compound and a second metal compound, the first metal compound It is connected to the second metal compound through a covalent bond or van der Waals force, and the valence band energy levels of the first metal compound and the second metal compound are different.
  • the multimer of the present invention may be a dimer, a trimer, a tetramer, a pentamer or a hexamer, or a single nanoparticle including more metal compounds.
  • the multimer is a dimer, the multimer is a single nanoparticle including a first metal compound and a second metal compound, and the first metal compound and the second metal compound are covalently bonded. Or van der Waals force connection, the valence band energy levels of the first metal compound and the second metal compound are different.
  • a second aspect of the embodiments of the present invention provides a method for manufacturing a hole transport material, including: providing a precursor solution and a reaction solution, respectively, the precursor solution is used to provide at least a first metal source and a second metal source; The reaction solution is added to the precursor solution, and the composite compound of the first metal and the second metal is obtained after the reaction; the composite compound is heated to obtain a polymer, and the polymer comprises at least the first metal compound and the second metal.
  • a single nanoparticle of a metal compound, the first metal compound and the second metal compound are connected by a covalent bond or van der Waals force, and the valence band energy levels of the first metal compound and the second metal compound are different.
  • a third aspect of the embodiments of the present invention provides a QLED device, which includes a hole transport layer formed of any of the above hole transport materials.
  • a fourth aspect of the embodiments of the present invention provides a method for fabricating a QLED device, including: forming a hole injection layer on a first electrode; forming hole transport on a side of the hole injection layer away from the first electrode
  • the hole transport layer includes a hole transport material prepared by any of the above-mentioned manufacturing methods; a quantum dot layer is formed on the side of the hole transport layer away from the hole injection layer; and the quantum dot layer is away from An electron transport layer is formed on one side of the hole transport layer; a second electrode is formed on the side of the electron transport layer away from the quantum dot layer.
  • a fifth aspect of the embodiments of the present invention provides a display device, including: the QLED device described in any one of the above.
  • Fig. 1 is a schematic diagram showing the structure of a polymer in a hole transport material according to an embodiment of the present invention
  • Fig. 2 is a flow chart of a method for producing the polymer in Fig. 1;
  • 3A is a schematic diagram showing the structure of a polymer in a hole transport material according to an embodiment of the present invention
  • 3B is a schematic diagram showing the structure of a polymer in a hole transport material according to an embodiment of the present invention.
  • Fig. 4 is a schematic structural diagram of a QLED device according to an embodiment of the present invention.
  • Figure 5 is a schematic diagram of the energy level structure of a QLED device
  • Fig. 6 is a flow chart of a manufacturing method of the QLED device in Fig. 4.
  • Fig. 1 is a schematic diagram showing the structure of a polymer in a hole transport material according to an embodiment of the present invention.
  • the hole transport material includes: a polymer 10, the polymer 10 is a single nanoparticle including a first metal compound 10a and a second metal compound 10b, the first metal compound 10a and the second metal The compound 10b is connected by a covalent bond, and the valence band energy levels of the first metal compound 10a and the second metal compound 10b are different.
  • first metal compound 10a and the second metal compound 10b in the multimer 10 may also be connected by van der Waals force.
  • the first metal compound 10a may be one of NiO, WO 3 , V 2 O 5 , CuGaO 2 , FeS 2 , and TiS 2
  • the second metal compound 10 b may be NiO, WO 3 , V 2 O 5. Another one of CuGaO 2 , FeS 2 , and TiS 2.
  • the polymer may be a dimer, such as NiO/WO 3 , NiO/V 2 O 5 , NiO/CuGaO 2 , NiO/FeS 2 , NiO/TiS 2 , WO 3 /V 2 O 5 , WO 3 /CuGaO 2 , WO 3 /FeS 2 , WO 3 /TiS 2 , V 2 O 5 /CuGaO 2 , V 2 O 5 /FeS 2 , V 2 O 5 /TiS 2 , CuGaO 2 /FeS 2 , CuGaO 2 /TiS 2 or FeS 2 /TiS 2 .
  • a dimer such as NiO/WO 3 , NiO/V 2 O 5 , NiO/CuGaO 2 , NiO/FeS 2 , NiO/TiS 2 , WO 3 /V 2 O 5 , WO 3 /CuGaO 2 , WO 3 /
  • the polymer 10 is used as the hole transport material.
  • the polymer 10 is a single nanoparticle including at least the first metal compound 10a and the second metal compound 10b, the first metal compound 10a and the second metal compound 10b.
  • the valence band energy levels of the first metal compound 10a and the second metal compound 10b are different, and a multi-level gradient is constructed using the difference in the position of the valence band of the single nanoparticle.
  • the hole can first transition to a low energy level, and then transition to a high energy level after being buffered by the low energy level.
  • the hole injection barrier can be reduced, the hole injection ability can be improved, and the electron-hole balance can be further improved, thereby improving the luminous efficiency and lifespan of the QLED device.
  • the NiO/WO 3 dimer when used as the hole transport layer, because the NiO/WO 3 dimer is NiO and WO 3 are in close contact and are connected by covalent bonds or van der Waals forces. Therefore , the transport of holes in the NiO/WO 3 dimer is more effective, and the transport performance of holes in the QLED device can be improved.
  • Each energy level in the gradient energy level can be adjusted by controlling the size of the nanoparticles and/or the composition ratio of the first metal compound 10a and the second metal compound 10b.
  • the size of the polymer 10 can be between 1nm and 100nm. Since the energy level structure of the nanoparticle is determined by factors such as its size and defects, the energy level structure can be determined by the size (the size of the polymer 10), the first metal compound The adjustment of the composition ratio of 10a and the second metal compound 10b is realized.
  • FIG. 2 is a flow chart of the manufacturing method, which includes steps S11 to S13.
  • Step S11 Provide a precursor solution and a reaction solution respectively, and the precursor solution is used to provide the first metal source and the second metal source.
  • Step S11 may specifically include: weighing 1.82 g of Ni(NO 3 ) 2 and 5.56 g of W(NO 3 ) 6 respectively and dissolving them in 100 mL of deionized water, and transferring them into a 500 mL round bottom flask after they are completely dissolved; Stir in an oil bath at °C, condense and reflux, and react for 30 minutes.
  • the resulting solution is a precursor solution.
  • the precursor solution provides a source of nickel and tungsten for the chemical reaction.
  • Step S12 The reaction solution is added to the precursor solution, and the composite compound of the first metal and the second metal is obtained after the reaction.
  • the reaction solution is centrifuged, filtered, washed, and dried in an oven at 60° C. to obtain a nickel-tungsten composite hydroxide.
  • Step S13 heating the composite compound to obtain a polymer 10, as shown in FIG. 1, the polymer 10 is a single nanoparticle including a first metal compound 10a and a second metal compound 10b, the first metal compound 10a and the second metal compound 10b is connected by a covalent bond or van der Waals force, and the valence band energy levels of the first metal compound 10a and the second metal compound 10b are different.
  • Step S13 may specifically include: placing the above-mentioned nickel-tungsten composite hydroxide in a muffle furnace for calcination, at a calcination temperature of 400° C., a heating rate of 5° C./min, and a holding time of 4 hours to obtain a NiO/WO 3 dimer.
  • the reaction formula can be: W(OH) 6 +Ni(OH) 2 ⁇ WO 3 /NiO+4H 2 O.
  • NiO/WO 3 dimer is synthesized by hydrothermal reaction method.
  • the size of the nanoparticles and/or the composition ratio of the first metal compound 10a to the second metal compound 10b can be controlled by experimental conditions to further adjust each energy level in the gradient energy level.
  • the size of the polymer 10 can be between 1nm and 100nm. Since the energy level structure of the nanoparticle is determined by its size and defects and other factors, the energy level structure can be controlled by reaction kinetics and thermodynamics during the preparation process.
  • the size (the size of the polymer 10) and the composition ratio of the first metal compound 10a and the second metal compound 10b can be adjusted. This is because self-doping is an effective way to change the physical and chemical properties of semiconductors.
  • the adjustment of its size is generally adjusted by changing the reaction temperature and the amount of reagents added, while the reaction conditions are changed. It will cause a change in the concentration of oxygen vacancies in the semiconductor. A high concentration of oxygen vacancies can generate an energy level below the conduction band of the oxide semiconductor, thereby changing the energy level structure of the entire semiconductor.
  • Changes in the reaction time or temperature during the reaction can also cause changes in the concentration of defects in sulfides (such as changes in the concentration of Zn vacancies in ZnS), leading to changes in the energy level structure.
  • the composition of the precursor solution includes a salt solution of the first metal element and the second metal element, and the composition of the reaction solution includes (NH 4 ) 2 CO 3 or ammonia.
  • the metal source of NiO in the dimer may be nickel sulfate, chloride, etc.; the metal source of WO 3 may be tungsten sulfate, chloride, etc.
  • the reaction solution may include ammonia water and the like.
  • the metal source of V 2 O 5 in the dimer may be at least one of sodium vanadate and ammonium metavanadate; and/or the metal source of CuGaO 2 may be copper nitrate and gallium nitrate; and/ Or the metal source of FeS 2 can be iron sulfate, iron chloride or iron nitrate; and/or the metal source of TiS 2 can be titanium tetrachloride.
  • Fig. 3A is a schematic diagram showing the structure of a polymer in a hole transport material according to an embodiment of the present invention.
  • the polymer 20 of this embodiment is substantially the same as the polymer 10 in FIG. 1, except that the single nanoparticle also includes a third metal compound 10c.
  • the third metal compound 10c and the first metal compound 10a are connected by a covalent bond, or the third metal compound 10c and the second metal compound 10b are connected by a covalent bond, the first metal compound 10a, the second metal compound 10b and the third metal
  • the valence band energy levels of compound 10c are two different.
  • Fig. 3B is a schematic diagram showing the structure of a polymer in a hole transport material according to an embodiment of the present invention.
  • the single nanoparticle further includes a third metal compound 10c.
  • the third metal compound 10c and the first metal compound 10a are connected by a covalent bond, and the third metal compound 10c and the second metal compound 10b are connected by a covalent bond.
  • the first metal compound 10a, the second metal compound 10b and the third metal The valence band energy levels of compound 10c are two different.
  • the valence band energy levels of the first metal compound 10a, the second metal compound 10b, and the third metal compound 10c are two-by-two different means: assuming that the valence band energy level of the first metal compound 10a is A, the valence band of the second metal compound 10b The energy level is B, and the valence band energy level of the third metal compound 10c is C; then A ⁇ B, A ⁇ C, and B ⁇ C.
  • any two of the first metal compound 10a, the second metal compound 10b, and the third metal compound 10c are connected by a covalent bond or van der Waals force.
  • the third metal compound 10c and the first metal compound 10a are connected by van der Waals force, and/or the third metal compound 10c and the second metal compound 10b are connected by van der Waals force.
  • one of the third metal compound 10c and the first metal compound 10a, and between the third metal compound 10c and the second metal compound 10b is connected by a covalent bond, and the other is connected by van der Waals force.
  • the third metal compound may be one of NiO, WO 3 , V 2 O 5 , CuGaO 2 , FeS 2 , and TiS 2 and is different from the first metal compound and the second metal compound.
  • the polymer 20 is a trimer, such as NiO/WO 3 /V 2 O 5 , NiO/WO 3 /CuGaO 2 , NiO/WO 3 /FeS 2 , NiO/WO 3 /TiS 2 , NiO/V 2 O 5 /CuGaO 2 , NiO/V 2 O 5 /FeS 2 , NiO/V 2 O 5 /TiS 2 , NiO/CuGaO 2 /FeS 2 , NiO/CuGaO 2 /TiS 2 , NiO/FeS 2 /TiS 2 , WO 3 /V 2 O 5 /CuGaO 2 , WO 3 /V 2 O 5 /CuGaO 2 , WO 3 /V
  • the single nanoparticle further includes a fourth metal compound.
  • the multimer can also be a tetramer, such as NiO/WO 3 /V 2 O 5 /CuGaO 2 , NiO/WO 3 /V 2 O 5 /FeS 2 , NiO/WO 3 /V 2 O 5 /TiS 2.
  • the single nanoparticle further includes a fifth metal compound. It is a pentamer, such as NiO/WO 3 /V 2 O 5 /CuGaO 2 /FeS 2 , NiO/WO 3 /V 2 O 5 /CuGaO 2 /TiS 2 , NiO/WO 3 /V 2 O 5 / FeS 2 /TiS 2 , NiO/WO 3 /CuGaO 2 /FeS 2 /TiS 2 , NiO/V 2 O 5 /CuGaO 2 /FeS 2 /TiS 2 or WO 3 /V 2 O 5 /CuGaO / FeS 2 /TiS 2 .
  • a pentamer such as NiO/WO 3 /V 2 O 5 /CuGaO 2 /FeS 2 , NiO/WO 3 /V 2 O 5 /CuGaO 2 /FeS 2 /TiS 2 .
  • the single nanoparticle further includes a sixth metal compound. It is a hexamer, such as NiO/WO 3 /V 2 O 5 /CuGaO 2 /FeS 2 /TiS 2 .
  • the embodiments of the present invention do not limit the number of metal compounds.
  • the multimer in each of the foregoing embodiments includes metal compounds of different kinds of substances. Due to different substances, large energy level changes are caused, and it is easier to construct a multi-level gradient based on the difference in the position of the valence band.
  • the at least two metal compounds included in a single nanoparticle may be the same substance with different energy levels.
  • the energy levels of the same substance can be different by adjusting the size of the nanoparticles or the preparation method.
  • the first metal compound and the second metal compound are NiO with different energy levels, thereby forming a dimer NiO/NiO.
  • the first metal compound and the second metal compound are NiO with different energy levels, and the third metal compound is WO 3 , thereby forming a trimer NiO/NiO /WO 3 .
  • a single nanoparticle when a single nanoparticle also includes a fourth metal compound, the first metal compound and the second metal compound are NiO with different energy levels, and the third metal compound and the fourth metal compound are WO 3 with different energy levels. , Thereby forming a tetramer NiO/NiO/WO 3 /WO 3 .
  • a single nanoparticle when a single nanoparticle also includes a fifth metal compound, the first metal compound and the second metal compound are NiO with different energy levels, and the third metal compound, the fourth metal compound, and the fifth metal compound have different energy levels. Energy level of WO 3 , thereby forming a pentamer NiO/NiO/WO 3 /WO 3 /WO 3 .
  • a single nanoparticle when a single nanoparticle also includes a sixth metal compound, the first metal compound and the second metal compound are NiO with different energy levels, and the third metal compound and the fourth metal compound are WO 3 with different energy levels.
  • the fifth metal compound and the sixth metal compound are V 2 O 5 with different energy levels, thereby forming a hexamer NiO/NiO/WO 3 /WO 3 /V 2 O 5 /V 2 O 5 .
  • the energy levels of all metal compounds included in a single nanoparticle may be different from each other.
  • the multi-level gradient of the polymer 20 in the above embodiment can further reduce the hole injection barrier and improve the hole injection capability, thereby improving the luminous efficiency and lifetime of the QLED device.
  • the manufacturing method is roughly the same as the manufacturing method in FIG. 2, except that the precursor solution provided in step S11 is also used to provide a third metal source.
  • the size of the nanoparticles and/or the composition ratio of the first metal compound 10a, the second metal compound 10b and the third metal compound 10c can be controlled by experimental conditions to further adjust each energy level in the gradient energy level.
  • Fig. 4 is a schematic structural diagram of a QLED device according to an embodiment of the present invention.
  • the QLED device 1 includes a first electrode 11, a hole injection layer 12, a hole transport layer 13, a quantum dot layer 14, an electron transport layer 15 and a second electrode 16 in sequence.
  • the QLED device 1 may have a bottom emitting structure.
  • the first electrode 11 may be an anode, specifically a light-transmitting anode, and the material is such as indium tin oxide (ITO);
  • the second electrode 16 may be a cathode, which has a light-reflecting function, and the material is, for example, metal aluminum.
  • the QLED device 1 may have a top-emitting structure.
  • the first electrode 11 can be an anode, specifically a light-reflecting anode, and the material is silver metal;
  • the second electrode 16 can be a cathode, which has the function of partially transmitting and reflecting light, and the material is, for example, metallic magnesium and metallic aluminum.
  • the hole injection layer 12 may be a PEDOT:PSS thin film.
  • Polyethylenedioxythiophene Poly(3,4-ethylenedioxythiophene), PEDOT) and polybenzene sulfonate (Poly(sodium-p-styrenesulfonate), PSS) can be dissolved in water by mixing in a certain proportion, and can form a uniformly dispersed PEDOT: PSS solution.
  • the PEDOT:PSS film made of PEDOT:PSS solution has good flexibility, stability, and high transparency in the visible light range.
  • the work function of PEDOT:PSS is generally 5.0 to 5.1 eV, which is very conducive to hole injection.
  • the hole transport layer 13 may include any of the above-mentioned polymers 10 and 20.
  • the thickness of the hole transport layer 13 may range from 1 nm to 100 nm.
  • the quantum dot layer 14 may include group II-VI core-shell semiconductor materials, group IV-VI core-shell semiconductor materials, group I-III-VI semiconductor materials, and perovskite luminescent materials.
  • group II-VI core-shell semiconductor materials include but are not limited to CdSe/ZnS, CdZnS/ZnS, Cd x Zn 1-x SeyS 1-y /ZnS
  • group IV-VI core-shell semiconductor materials include but are not limited to PbSe, PbS, PbSe/CdS, PbSe/ZnS
  • I-III-VI semiconductor materials include but are not limited to Cu-In-S
  • perovskite luminescent materials include but are not limited to MAPbX 3 , CsPbX 3 .
  • the electron transport layer 15 may include at least one of ZnO nanoparticles and ZnMgO nanoparticles.
  • Figure 5 is a schematic diagram of the energy level structure of a QLED device.
  • the band gap E g of WO 3 is 2.7 eV
  • the conduction band energy level E CB is 0.74 eV
  • the valence band energy level E VB is 3.44 eV
  • the band gap E g of NiO is 3.5 eV
  • the band energy level E CB is -0.5 eV
  • the valence band energy level E VB is 3 eV.
  • the different valence band energy levels of NiO/WO 3 dimer 10 together construct a multi-level gradient.
  • NiO/WO 3 dimer 10 When the holes of the ITO first electrode 11 transition, they can first transition to the low energy level of the NiO/WO 3 dimer 10, and then transition to the high energy level of the NiO/WO 3 dimer 10 after being buffered by the low energy level. Compared with hole transport materials that require direct transition of holes to high energy levels, NiO/WO 3 dimer 10 can reduce the hole injection barrier, improve hole injection ability, and further improve the electron-hole balance, thereby improving QLED devices1 The luminous efficiency and lifetime.
  • Fig. 6 is a flow chart of the production method, including steps S21 to S25.
  • Step S21 As shown in FIG. 4, a hole injection layer 12 is formed on the first electrode 11.
  • the QLED device 1 may have a bottom emitting structure.
  • the first electrode 11 may be an anode, specifically a light-transmitting anode, and the material may be, for example, indium tin oxide (ITO).
  • the QLED device 1 may have a top-emitting structure.
  • the first electrode 11 may be a light-reflecting anode, and the material is such as metallic silver.
  • step S21 spin-coating a PEDOT:PSS aqueous solution or ink-jet printing a PEDOT:PSS thin film can be used to form the hole injection layer 12.
  • Step S22 As shown in FIG. 4, a hole transport layer 13 is formed on the side of the hole injection layer 12 away from the first electrode 11.
  • the hole transport layer 13 includes the hole transport material prepared by any of the above-mentioned manufacturing methods.
  • the hole transport layer 13 may include any of the above-mentioned polymers 10 and 20.
  • step S22 in the process of forming the hole transport layer 13, a method of coating a hole transport material solution, or inkjet printing a hole transport material ink, or electrojet printing a hole transport material ink may be adopted.
  • coating the hole transport material solution includes coating by means of spin coating, knife coating or spray coating.
  • the hole transport material prepared by the above-mentioned manufacturing method can be dispersed in a volatile dispersant to form a solution or colloid.
  • the volatile dispersant is, for example, a solvent such as water or ethanol.
  • Step S23 As shown in FIG. 4, a quantum dot layer 14 is formed on the side of the hole transport layer 13 away from the hole injection layer 12.
  • the quantum dot layer 14 may include group II-VI core-shell semiconductor materials, group IV-VI core-shell semiconductor materials, group I-III-VI semiconductor materials, and perovskite luminescent materials.
  • step S23 spin coating of a quantum dot solution or inkjet printing of a quantum dot colloid can be used.
  • Step S24 As shown in FIG. 4, an electron transport layer 15 is formed on the side of the quantum dot layer 14 away from the hole transport layer 13.
  • the electron transport layer 15 may include at least one of ZnO nanoparticles and ZnMgO nanoparticles.
  • step S24 spin coating of a ZnO/ZnMgO nanoparticle solution or inkjet printing of a ZnO/ZnMgO nanoparticle colloid can be used.
  • Step S25 As shown in FIG. 4, a second electrode 16 is formed on the side of the electron transport layer 15 away from the quantum dot layer 14.
  • the QLED device 1 may have a bottom emitting structure.
  • the second electrode 16 may be a cathode with a light-reflecting function, and the material is, for example, metallic aluminum.
  • the QLED device 1 may have a top-emitting structure.
  • the second electrode 16 may be a cathode with a function of partially transmitting and reflecting light, and the material is, for example, metallic magnesium and metallic aluminum.
  • step S25 vapor deposition of the second electrode material layer or inkjet printing of the second electrode material layer may be used.
  • an embodiment of the present invention also provides a display device including the above-mentioned QLED device 1.
  • the display device can be any product or component with display function, such as electronic paper, mobile phone, tablet computer, television, notebook computer, digital photo frame, navigator, etc.

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Abstract

本发明提供了一种QLED器件、空穴传输材料及其制作方法、显示装置，空穴传输材料包括：多聚体，多聚体为至少包括第一金属化合物与第二金属化合物的单一纳米颗粒，第一金属化合物与第二金属化合物通过共价键或范德华力连接，第一金属化合物与第二金属化合物的价带能级不同。

Description

QLED器件、空穴传输材料及其制作方法、显示装置
相关申请的交叉引用
本公开要求于2020年1月16日提交的、申请号为202010047324.6的中国专利申请的优先权，该申请的全文以引用的方式并入本文中。
技术领域
本发明涉及显示设备技术领域，尤其涉及一种QLED器件、空穴传输材料及其制作方法、显示装置。
背景技术
QLED显示器件(Quantum dot light-emitting diode，量子点电致发光二极管)是一种电致发光器件。在外界电场的驱动下，空穴和电子克服界面障碍分别进入量子点发光层的价带能级和导带能级，当从激发态而回到稳定的基态时，释放出光子。随着量子点材料的发展、器件结构的不断优化和电荷有效输运等研究的持续深入，QLED(Quantum Dot Light Emitting Diode，量子点电致发光二极管)显示将超越光致发光的量子点增亮膜和量子点彩色滤光片，有望成为下一代主流显示技术。
在QLED器件中，各个功能层包括空穴注入层、空穴传输层、量子点发光层、电子传输层和电极。而目前大多数功能层都为有机材料，由于有机材料容易受到水氧侵蚀，使器件寿命降低，因此开发无机功能层材料成为研究热点。在QLED器件中，ZnO电子传输层的引入使电子注入效率大幅提升，而空穴注入需要克服较大势垒，导致电子在器件中成为多子，使电子-空穴注入不平衡，也会影响器件效率和寿命。
发明内容
本发明实施例的第一方面提供一种空穴传输材料，包括：多聚体，所述多聚体为至少包括第一金属化合物与第二金属化合物的单一纳米颗粒，所述第一金属化合物与所述第二金属化合物通过共价键或范德华力连接，所述第一金属化合物与所述第二金属化合物的价带能级不同。
需要说明的是，本发明所述多聚体，可以是二聚体，三聚体、四聚体，五聚体或六聚体，也可以是包括更多金属化合物的单一纳米颗粒。当所述多聚体为二聚体时，所述 多聚体为包括第一金属化合物与第二金属化合物的单一纳米颗粒，所述第一金属化合物与所述第二金属化合物通过共价键或范德华力连接，所述第一金属化合物与所述第二金属化合物的价带能级不同。
本发明实施例的第二方面提供一种空穴传输材料的制作方法，包括：分别提供前驱体溶液与反应溶液，所述前驱体溶液至少用于提供第一金属源与第二金属源；将所述反应溶液加入所述前驱体溶液，反应后得到第一金属与第二金属的复合化合物；加热所述复合化合物得到多聚体，所述多聚体为至少包括第一金属化合物与第二金属化合物的单一纳米颗粒，所述第一金属化合物与所述第二金属化合物通过共价键或范德华力连接，所述第一金属化合物与所述第二金属化合物的价带能级不同。
本发明实施例的第三方面提供一种QLED器件，包括上述任一项所述的空穴传输材料形成的空穴传输层。
本发明实施例的第四方面提供一种QLED器件的制作方法，包括：在第一电极上形成空穴注入层；在所述空穴注入层远离所述第一电极的一侧形成空穴传输层，所述空穴传输层包括上述任一制作方法制备的空穴传输材料；在所述空穴传输层远离所述空穴注入层的一侧形成量子点层；在所述量子点层远离所述空穴传输层的一侧形成电子传输层；在所述电子传输层远离所述量子点层的一侧形成第二电极。
本发明实施例的第五方面提供一种显示装置，包括：上述任一项所述的QLED器件。
应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本发明。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本发明的实施例，并与说明书一起用于解释本发明的原理。
图1是根据本发明一实施例示出的空穴传输材料中的多聚体的结构示意图；
图2是图1中的多聚体的一种制作方法的流程图；
图3A是根据本发明一实施例示出的空穴传输材料中的多聚体的结构示意图；
图3B是根据本发明一实施例示出的空穴传输材料中的多聚体的结构示意图；
图4是根据本发明一实施例示出的QLED器件的结构示意图；
图5是一种QLED器件的能级结构示意图；
图6是图4中的QLED器件的一种制作方法的流程图。
附图标记列表：
多聚体10、20                           第一金属化合物10a
第二金属化合物10b                      第三金属化合物10c
QLED器件1                              第一电极11
空穴注入层12                           空穴传输层13
量子点层14                             电子传输层15
第二电极16
具体实施方式
这里将详细地对示例性实施例进行说明，其示例表示在附图中。下面的描述涉及附图时，除非另有表示，不同附图中的相同数字表示相同或相似的要素。以下示例性实施例中所描述的实施方式并不代表与本发明相一致的所有实施方式。相反，它们仅是与如所附权利要求书中所详述的、本发明的一些方面相一致的装置和方法的例子。
图1是根据本发明一实施例示出的空穴传输材料中的多聚体的结构示意图。
参照图1所示，该空穴传输材料，包括：多聚体10，多聚体10为包括第一金属化合物10a与第二金属化合物10b的单一纳米颗粒，第一金属化合物10a与第二金属化合物10b通过共价键连接，第一金属化合物10a与第二金属化合物10b的价带能级不同。
一些实施例中，多聚体10中的第一金属化合物10a与第二金属化合物10b还可以通过范德华力连接。
一些实施例中，第一金属化合物10a可以为NiO、WO 3、V 2O 5、CuGaO 2、FeS 2、TiS 2中的一种，第二金属化合物10b可以为NiO、WO 3、V 2O 5、CuGaO 2、FeS 2、TiS 2中的另一种。换言之，多聚体可以为二聚体，例如为NiO/WO 3、NiO/V 2O 5、NiO/CuGaO 2、NiO/FeS 2、NiO/TiS 2、WO 3/V 2O 5、WO 3/CuGaO 2、WO 3/FeS 2、WO 3/TiS 2、V 2O 5/CuGaO 2、V 2O 5/FeS 2、V 2O 5/TiS 2、CuGaO 2/FeS 2、CuGaO 2/TiS 2或FeS 2/TiS 2。
上述实施例中，采用多聚体10作为空穴传输材料，多聚体10为至少包括第一金属 化合物10a与第二金属化合物10b的单一纳米颗粒，第一金属化合物10a与第二金属化合物10b通过共价键或范德华力连接，第一金属化合物10a与第二金属化合物10b的价带能级不同，利用该单一纳米颗粒的价带位置差异构建了多能级梯度。空穴在跃迁时，可先跃迁到低能级，在低能级缓冲后再跃迁到高能级。相对于空穴需直接跃迁到高能级的空穴传输材料，可降低空穴注入势垒，提高空穴注入能力，进一步提升电子空穴平衡，从而提高QLED器件的发光效率和寿命。
此外，相比直接混合第一金属化合物10a与第二金属化合物10b，例如直接混合NiO和WO 3，将NiO/WO 3二聚体作为空穴传输层时，由于NiO/WO 3二聚体中NiO与WO 3之间是紧密接触并通过共价键或范德华力连接的，因此空穴在NiO/WO 3二聚体中传输更为有效，更能够提高空穴在QLED器件中的传输性能。
可通过控制纳米颗粒的大小、和/或第一金属化合物10a与第二金属化合物10b的组分比，来调整梯度能级中的各能级。多聚体10的大小可以在1nm～100nm之间，由于纳米颗粒的能级结构由其尺寸以及缺陷等因素决定，因此能级结构可以通过尺寸(多聚体10的大小)、第一金属化合物10a与第二金属化合物10b的组分比的调控实现。
对于图1中的空穴传输材料中的多聚体10，本发明一实施例提供了一种制作方法。图2是制作方法的流程图，其包括步骤S11～S13。
步骤S11：分别提供前驱体溶液与反应溶液，前驱体溶液用于提供第一金属源与第二金属源。
步骤S11具体可以包括：分别称取1.82g的Ni(NO 3) 2和5.56g的W(NO 3) 6溶于100mL去离子水中，待其完全溶解后转入500mL圆底烧瓶中；在100℃油浴中搅拌，冷凝回流，反应30min，所得溶液为前驱体溶液。前驱体溶液为化学反应提供镍源和钨源。再称取19.2g(NH 4) 2CO 3完全溶解于50mL去离子水中，所得溶液为反应溶液。
步骤S12：将反应溶液加入前驱体溶液，反应后得到第一金属与第二金属的复合化合物。
步骤S12具体可以包括：将反应溶液逐滴滴加到前驱体溶液中，搅拌反应5h；反应式可以为：
Ni(NO 3) 2+(NH 4) 2CO 3+H 2O→Ni(OH) 2+2NH 4NO 3+CO 2↑；
W(NO 3) 6+3(NH 4) 2CO 3+3H 2O→W(OH) 6+6NH 4NO 3+3CO 2↑；
反应结束后将反应液离心，过滤，洗涤，置于60℃烘箱中干燥，得到镍钨复合氢氧化物。
步骤S13：加热复合化合物得到多聚体10，如图1所示，多聚体10为包括第一金属化合物10a与第二金属化合物10b的单一纳米颗粒，第一金属化合物10a与第二金属化合物10b通过共价键或范德华力连接，第一金属化合物10a与第二金属化合物10b的价带能级不同。
步骤S13具体可以包括：将上述镍钨复合氢氧化物置于马弗炉中进行焙烧，焙烧温度为400℃，升温速率为5℃/min，保温时间4h，得到NiO/WO 3二聚体。反应式可以为：W(OH) 6+Ni(OH) 2→WO 3/NiO+4H 2O。
可以看出，NiO/WO 3二聚体是通过水热反应法合成。
可通过实验条件控制纳米颗粒的大小、和/或第一金属化合物10a与第二金属化合物10b的组分比，进一步调整梯度能级中的各能级。多聚体10的大小可以在1nm～100nm之间，由于纳米颗粒的能级结构由其尺寸以及缺陷等因素决定，因此能级结构可以通过制备过程中反应动力学和热力学进行调控，具体可以通过尺寸(多聚体10的大小)、第一金属化合物10a与第二金属化合物10b的组分比的调控来实现。这是因为：自掺杂是一种改变半导体物理化学性质的有效方式，在氧化物合成过程中，对于其大小的调控一般会通过改变反应温度以及加入试剂的量进行调控，而反应条件的改变会造成半导体中氧空位浓度的改变，高浓度的氧空位能够在氧化物半导体导带下方产生一个能级，从而改变整个半导体的能级结构。对于硫化物也一样，反应过程中反应时间或温度的改变也能够引起硫化物中缺陷浓度的改变(如ZnS中Zn空位浓度的变化)，导致能级结构的变化。
一些实施例中，前驱体溶液的成分包括第一金属元素与第二金属元素的盐溶液，反应溶液的成分包括(NH 4) 2CO 3或氨水。
以二聚体包含NiO和WO 3为例，该二聚体中NiO的金属源可以为镍的硫酸盐、氯化盐等；WO 3的金属源可以为钨的硫酸盐、氯化盐等。反应溶液可以包括氨水等。
一些实施例中，二聚体中V 2O 5的金属源可以为钒酸钠、偏钒酸铵中的至少一种；和/或CuGaO 2的金属源可以为硝酸铜和硝酸镓；和/或FeS 2的金属源为硫酸铁、氯化铁或硝酸铁；和/或TiS 2的金属源可为四氯化钛。
图3A是根据本发明一实施例示出的空穴传输材料中的多聚体的结构示意图。参照图3A所示，本实施例的多聚体20与图1中的多聚体10大致相同，区别仅在于：单一 纳米颗粒还包括第三金属化合物10c。第三金属化合物10c与第一金属化合物10a通过共价键连接，或第三金属化合物10c与第二金属化合物10b通过共价键连接，第一金属化合物10a、第二金属化合物10b与第三金属化合物10c的价带能级两两不同。
图3B是根据本发明一实施例示出的空穴传输材料中的多聚体的结构示意图。参照图3B所示，单一纳米颗粒还包括第三金属化合物10c。第三金属化合物10c与第一金属化合物10a通过共价键连接，且第三金属化合物10c与第二金属化合物10b通过共价键连接，第一金属化合物10a、第二金属化合物10b与第三金属化合物10c的价带能级两两不同。
第一金属化合物10a、第二金属化合物10b与第三金属化合物10c的价带能级两两不同是指：假设第一金属化合物10a的价带能级为A，第二金属化合物10b的价带能级为B，第三金属化合物10c的价带能级为C；则A≠B，A≠C，B≠C。
一些实施例中，第一金属化合物10a、第二金属化合物10b与第三金属化合物10c中的任意两个通过共价键或范德华力连接。
一些实施例中，第三金属化合物10c与第一金属化合物10a通过范德华力连接，和/或第三金属化合物10c与第二金属化合物10b通过范德华力连接。
一些实施例中，第三金属化合物10c与第一金属化合物10a之间、第三金属化合物10c与第二金属化合物10b之间中的一个通过共价键连接，另一个通过范德华力连接。
第三金属化合物可以为NiO、WO 3、V 2O 5、CuGaO 2、FeS 2、TiS 2中的一种、且不同于第一金属化合物和第二金属化合物。换言之，多聚体20为三聚体，例如为NiO/WO 3/V 2O 5、NiO/WO 3/CuGaO 2、NiO/WO 3/FeS 2、NiO/WO 3/TiS 2、NiO/V 2O 5/CuGaO 2、NiO/V 2O 5/FeS 2、NiO/V 2O 5/TiS 2、NiO/CuGaO 2/FeS 2、NiO/CuGaO 2/TiS 2、NiO/FeS 2/TiS 2、WO 3/V 2O 5/CuGaO 2、WO 3/V 2O 5/FeS 2、WO 3/V 2O 5/TiS 2、V 2O 5/CuGaO 2/FeS 2、V 2O 5/CuGaO 2/TiS 2或CuGaO 2/FeS 2/TiS 2。
一些实施例中，单一纳米颗粒还包括第四金属化合物。即多聚体还可以为四聚体，例如为NiO/WO 3/V 2O 5/CuGaO 2、NiO/WO 3/V 2O 5/FeS 2、NiO/WO 3/V 2O 5/TiS 2、NiO/WO 3/CuGaO 2/FeS 2、NiO/WO 3/CuGaO 2/TiS 2、NiO/WO 3/FeS 2/TiS 2、NiO/V 2O 5/CuGaO 2/FeS 2、NiO/V 2O 5/CuGaO 2/TiS 2、NiO/V 2O 5/FeS 2/TiS 2、NiO/CuGaO 2/FeS 2/TiS 2、WO 3/V 2O 5/CuGaO 2/FeS 2、WO 3/V 2O 5/CuGaO 2/TiS 2、WO 3/V 2O 5/FeS 2/TiS 2、WO 3/CuGaO 2/FeS 2/TiS 2或V 2O 5/CuGaO 2/FeS 2/TiS 2。
再一些实施例中，单一纳米颗粒还包括第五金属化合物。即为五聚体，例如为NiO/WO 3/V 2O 5/CuGaO 2/FeS 2、NiO/WO 3/V 2O 5/CuGaO 2/TiS 2、NiO/WO 3/V 2O 5/FeS 2/TiS 2、NiO/WO 3/CuGaO 2/FeS 2/TiS 2、NiO/V 2O 5/CuGaO 2/FeS 2/TiS 2或WO 3/V 2O 5/CuGaO /FeS 2/TiS 2。
又一些实施例中，单一纳米颗粒还包括第六金属化合物。即为六聚体，例如为NiO/WO 3/V 2O 5/CuGaO 2/FeS 2/TiS 2。本发明实施例不限定金属化合物的数量。
上述各实施例中的多聚体包括不同种物质的金属化合物，由于物质不同引起较大的能级变化，更容易利用价带位置差异构建的多能级梯度。
在一些实施例中，单一纳米颗粒所包括的至少两种金属化合物可以是能级不同的同种物质。通过调控纳米粒子的尺寸或制备方法可以造成同种物质的能级不同。举例而言，单一纳米颗粒包括第一金属化合物和第二金属化合物的情况下，第一金属化合物和第二金属化合物为具有不同能级的NiO，由此形成二聚体NiO/NiO。又例如，单一纳米颗粒还包括第三金属化合物的情况下，第一金属化合物和第二金属化合物为具有不同能级的NiO，第三金属化合物为WO 3，由此形成三聚体NiO/NiO/WO 3。再例如，单一纳米颗粒还包括第四金属化合物的情况下，第一金属化合物和第二金属化合物为具有不同能级的NiO，第三金属化合物和第四金属化合物为具有不同能级的WO 3，由此形成四聚体NiO/NiO/WO 3/WO 3。又例如，单一纳米颗粒还包括第五金属化合物的情况下，第一金属化合物和第二金属化合物为具有不同能级的NiO，第三金属化合物、第四金属化合物和第五金属化合物为具有不同能级的WO 3，由此形成五聚体NiO/NiO/WO 3/WO 3/WO 3。又例如，单一纳米颗粒还包括第六金属化合物的情况下，第一金属化合物和第二金属化合物为具有不同能级的NiO，第三金属化合物和第四金属化合物为具有不同能级的WO 3，第五金属化合物和第六金属化合物为具有不同能级的V 2O 5，由此形成六聚体NiO/NiO/WO 3/WO 3/V 2O 5/V 2O 5。上述实施例中，单一纳米颗粒所包括的所有金属化合物能级可以各不相同。
上述实施例中多聚体20的多能级梯度，可以进一步降低空穴注入势垒，提高空穴注入能力，从而能提高QLED器件的发光效率和寿命。
相应地，对于制作方法，与图2中的制作方法大致相同，区别仅在于：步骤S11中，提供的前驱体溶液还用于提供第三金属源。
可通过实验条件控制纳米颗粒的大小、和/或第一金属化合物10a、第二金属化合物10b与第三金属化合物10c的组分比，进一步调整梯度能级中的各能级。
图4是根据本发明一实施例示出的QLED器件的结构示意图。参照图4所示，QLED器件1依次包括：第一电极11、空穴注入层12、空穴传输层13、量子点层14、电子传输层15以及第二电极16。
一些实施例中，QLED器件1可以为底发光结构。此时，第一电极11可以为阳极，具体可以为透光阳极，材料例如氧化铟锡(Indium Tin Oxide，ITO)；第二电极16可以为阴极，具有反光的功能，材料例如为金属铝。
另一些实施例中，QLED器件1可以为顶发光结构。此时，第一电极11可以为阳极，具体可以为反光阳极，材料例如金属银；第二电极16可以为阴极，具有部分透光部分反光的功能，材料例如为金属镁与金属铝。
空穴注入层12可以为PEDOT:PSS薄膜。聚乙撑二氧噻吩(Poly(3,4-ethylenedioxythiophene)，PEDOT)和聚苯磺酸盐(Poly(sodium-p-styrenesulfonate)，PSS)通过一定比例混合而溶于水，可以形成均一分散的PEDOT:PSS溶液。由PEDOT:PSS溶液制成的PEDOT:PSS薄膜具有很好的柔性、稳定性，且在可见光范围具有很高的透明度。而且PEDOT:PSS的功函数一般在5.0～5.1eV，非常有利于注入空穴。
空穴传输层13可以包括上述任一多聚体10、20。
空穴传输层13的厚度范围可以为1nm～100nm。
量子点层14可包括Ⅱ-Ⅵ族核壳半导体材料、Ⅳ-Ⅵ族核壳半导体材料、Ⅰ-Ⅲ-Ⅵ族半导体材料、钙钛矿发光材料。具体的，Ⅱ-Ⅵ族核壳半导体材料包括但不限于CdSe/ZnS、CdZnS/ZnS、Cd xZn 1-xSeyS 1-y/ZnS；Ⅳ-Ⅵ族核壳半导体材料包括但不限于PbSe、PbS、PbSe/CdS、PbSe/ZnS；Ⅰ-Ⅲ-Ⅵ族半导体材料包括但不限于Cu-In-S；钙钛矿发光材料包括但不限于MAPbX 3、CsPbX 3。
电子传输层15可以包括ZnO纳米颗粒、ZnMgO纳米颗粒中的至少一种。
图5是一种QLED器件的能级结构示意图。
参照图5所示，WO 3的禁带宽度E g为2.7eV，导带能级E CB为0.74eV，价带能级E VB为3.44eV；NiO的禁带宽度E g为3.5eV，导带能级E CB为-0.5eV，价带能级E VB为3eV。QLED器件1中，NiO/WO 3二聚体10的不同价带能级一起构建了多能级梯度。ITO第一电极11的空穴在跃迁时，可先跃迁到NiO/WO 3二聚体10的低能级，在低能级缓冲后再跃迁到NiO/WO 3二聚体10的高能级。相对于空穴需直接跃迁到高能级的空穴传输材料，NiO/WO 3二聚体10可降低空穴注入势垒，提高空穴注入能力，进一步提 升电子空穴平衡，从而提高QLED器件1的发光效率和寿命。
相比于一层NiO空穴传输层结合于一层WO 3空穴传输层，用二聚体空穴传输层制备QLED器件更为简便，能够简化QLED器件结构。此外，还能消除两层空穴传输层界面因素所带来的对于QLED器件性能的影响。
对于图4中的QLED器件1，本发明一实施例提供了一种制作方法。图6是制作方法的流程图，包括步骤S21～S25。
步骤S21：如图4所示，在第一电极11上形成空穴注入层12。
一些实施例中，QLED器件1可以为底发光结构。此时，第一电极11可以为阳极，具体可以为透光阳极，材料例如氧化铟锡(ITO)。另一些实施例中，QLED器件1可以为顶发光结构。此时，第一电极11可以为反光阳极，材料例如金属银。
步骤S21可以采用旋涂PEDOT:PSS水溶液，或喷墨打印PEDOT:PSS薄膜以形成空穴注入层12。
步骤S22：如图4所示，在空穴注入层12远离第一电极11的一侧形成空穴传输层13，空穴传输层13包括上述任一制作方法制备的空穴传输材料。
空穴传输层13可以包括上述任一多聚体10、20。
步骤S22在形成空穴传输层13的过程中可以采用涂覆空穴传输材料溶液，或喷墨打印空穴传输材料墨水，或电喷印空穴传输材料墨水的的方式。其中，涂覆空穴传输材料溶液包括利用旋涂、刮涂或喷涂等方式进行涂覆。
旋涂前，可先将上述制作方法制备的空穴传输材料分散在可挥发分散剂中以形成溶液或胶体。可挥发分散剂例如为水或乙醇等溶剂。
步骤S23：如图4所示，在空穴传输层13远离空穴注入层12的一侧形成量子点层14。
量子点层14可包括Ⅱ-Ⅵ族核壳半导体材料、Ⅳ-Ⅵ族核壳半导体材料、Ⅰ-Ⅲ-Ⅵ族半导体材料、钙钛矿发光材料。
步骤S23可以采用旋涂量子点溶液，或喷墨打印量子点胶体。
步骤S24：如图4所示，在量子点层14远离空穴传输层13的一侧形成电子传输层15。
电子传输层15可以包括ZnO纳米颗粒、ZnMgO纳米颗粒中的至少一种。
步骤S24可以采用旋涂ZnO/ZnMgO纳米颗粒溶液，或喷墨打印ZnO/ZnMgO纳米颗粒胶体。
步骤S25：如图4所示，在电子传输层15远离量子点层14的一侧形成第二电极16。
一些实施例中，QLED器件1可以为底发光结构。此时，第二电极16可以为具有反光的功能的阴极，材料例如为金属铝。
另一些实施例中，QLED器件1可以为顶发光结构。此时，第二电极16可以为具有部分透光部分反光功能的阴极，材料例如为金属镁与金属铝。
步骤S25可以采用蒸镀第二电极材料层，或喷墨打印第二电极材料层。
基于上述QLED器件1，本发明一实施例还提供一种包括上述QLED器件1的显示装置。显示装置可以为：电子纸、手机、平板电脑、电视机、笔记本电脑、数码相框、导航仪等任何具有显示功能的产品或部件。
需要指出的是，在附图中，为了图示的清晰可能夸大了层和区域的尺寸。而且可以理解，当元件或层被称为在另一元件或层“上”时，它可以直接在其他元件上，或者可以存在中间的层。另外，可以理解，当元件或层被称为在另一元件或层“下”时，它可以直接在其他元件下，或者可以存在一个以上的中间的层或元件。另外，还可以理解，当层或元件被称为在两层或两个元件“之间”时，它可以为两层或两个元件之间唯一的层，或还可以存在一个以上的中间层或元件。通篇相似的参考标记指示相似的元件。
在本发明中，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性。
本领域技术人员在考虑说明书及实践这里公开的公开后，将容易想到本发明的其它实施方案。本发明旨在涵盖本发明的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明未公开的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的，本发明的真正范围和精神由下面的权利要求指出。
应当理解的是，本发明并不局限于上面已经描述并在附图中示出的精确结构，并且可以在不脱离其范围进行各种修改和改变。本发明的范围仅由所附的权利要求来限制。

Claims (17)

  1. 一种空穴传输材料，包括：多聚体，所述多聚体为至少包括第一金属化合物与第二金属化合物的单一纳米颗粒，所述第一金属化合物与所述第二金属化合物通过共价键或范德华力连接，所述第一金属化合物与所述第二金属化合物的价带能级不同。
  2. 根据权利要求1所述的空穴传输材料，其特征在于，所述第一金属化合物为NiO、WO 3、V 2O 5、CuGaO 2、FeS 2、TiS 2中的一种，所述第二金属化合物为NiO、WO 3、V 2O 5、CuGaO 2、FeS 2、TiS 2中的另一种。
  3. 根据权利要求1或2所述的空穴传输材料，其特征在于，所述单一纳米颗粒还包括第三金属化合物，所述第三金属化合物与所述第一金属化合物通过共价键或范德华力连接，和/或所述第三金属化合物与所述第二金属化合物通过共价键或范德华力连接，所述第一金属化合物、所述第二金属化合物与所述第三金属化合物的价带能级两两不同。
  4. 根据权利要求3所述的空穴传输材料，其特征在于，所述第三金属化合物为NiO、WO 3、V 2O 5、CuGaO 2、FeS 2、TiS 2中的一种。
  5. 根据权利要求3所述的空穴传输材料，其特征在于，所述第三金属化合物为NiO、WO 3、V 2O 5、CuGaO 2、FeS 2、TiS 2中的一种、且不同于所述第一金属化合物和所述第二金属化合物。
  6. 一种空穴传输材料的制作方法，包括：
    分别提供前驱体溶液与反应溶液，所述前驱体溶液至少用于提供第一金属源与第二金属源；
    将所述反应溶液加入所述前驱体溶液，反应后得到第一金属与第二金属的复合化合物；
    加热所述复合化合物得到多聚体，所述多聚体为至少包括第一金属化合物与第二金属化合物的单一纳米颗粒，所述第一金属化合物与所述第二金属化合物通过共价键或范德华力连接，所述第一金属化合物与所述第二金属化合物的价带能级不同。
  7. 根据权利要求6所述的空穴传输材料的制作方法，其特征在于，所述前驱体溶液的成分包括第一金属元素与第二金属元素的盐溶液，所述反应溶液的成分包括(NH 4) 2CO 3或氨水。
  8. 根据权利要求7所述的空穴传输材料的制作方法，其特征在于，制作NiO/WO 3二聚体的情况下，所述二聚体中，用于NiO的金属元素来自镍的硫酸盐和镍的氯化盐中的至少一种；用于WO 3的金属元素来自钨的硫酸盐和钨的氯化盐中的至少一种。
  9. 根据权利要求7所述的空穴传输材料的制作方法，其特征在于，
    制作的二聚体包括V 2O 5的情况下，用于V 2O 5的金属元素来自钒酸钠、偏钒酸铵中的至少一种；
    制作的二聚体包括CuGaO 2的情况下，用于CuGaO 2的金属元素来自硝酸铜和硝酸镓；
    制作的二聚体包括FeS 2的情况下，用于FeS 2的金属元素来自硫酸铁、氯化铁和硝酸铁中的至少一种；
    制作的二聚体包括TiS 2的情况下，用于TiS 2的金属元素来自四氯化钛。
  10. 一种量子点电致发光二极管QLED器件，包括权利要求1至3任一项所述的空穴传输材料形成的空穴传输层。
  11. 根据权利要求10所述的QLED器件，其特征在于，还包括：第一电极、空穴注入层、量子点层、电子传输层以及第二电极。
  12. 根据权利要求11所述的QLED器件，其特征在于，所述空穴注入层为PEDOT:PSS薄膜，和/或所述电子传输层包括ZnO纳米颗粒、ZnMgO纳米颗粒中的至少一种。
  13. 根据权利要求12所述的QLED器件，其特征在于，所述PEDOT:PSS薄膜的功函数在5.0eV～5.1eV的范围内。
  14. 根据权利要求10所述的QLED器件，其特征在于，所述空穴传输层的厚度范围为1nm～100nm。
  15. 一种量子点电致发光二极管QLED器件的制作方法，包括：
    在第一电极上形成空穴注入层；
    在所述空穴注入层远离所述第一电极的一侧形成空穴传输层，所述空穴传输层包括权利要求5至8任一项所述的制作方法制备的空穴传输材料；
    在所述空穴传输层远离所述空穴注入层的一侧形成量子点层；
    在所述量子点层远离所述空穴传输层的一侧形成电子传输层；
    在所述电子传输层远离所述量子点层的一侧形成第二电极。
  16. 根据权利要求15所述的QLED器件，其特征在于，在形成所述空穴传输层的过程中采用涂覆空穴传输材料溶液，或喷墨打印空穴传输材料墨水，或电喷印空穴传输材料墨水的方式。
  17. 一种显示装置，包括：权利要求10至14任一项所述的QLED器件。
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