WO2019128992A1 - 电子传输薄膜及其制备方法和应用 - Google Patents

电子传输薄膜及其制备方法和应用 Download PDF

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WO2019128992A1
WO2019128992A1 PCT/CN2018/123505 CN2018123505W WO2019128992A1 WO 2019128992 A1 WO2019128992 A1 WO 2019128992A1 CN 2018123505 W CN2018123505 W CN 2018123505W WO 2019128992 A1 WO2019128992 A1 WO 2019128992A1
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zinc oxide
doped
metal ion
electron transporting
metal
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French (fr)
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吴龙佳
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TCL Corp
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TCL Corp
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Priority to KR1020217040602A priority Critical patent/KR20210154876A/ko
Priority to JP2020535041A priority patent/JP2021507541A/ja
Priority to KR1020207017725A priority patent/KR20200087847A/ko
Priority to KR1020237011911A priority patent/KR20230053706A/ko
Priority to EP18896954.7A priority patent/EP3734679B1/en
Publication of WO2019128992A1 publication Critical patent/WO2019128992A1/zh
Priority to US16/906,727 priority patent/US11329245B2/en
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    • H—ELECTRICITY
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H—ELECTRICITY
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    • 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
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    • 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
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/30—Doping active layers, e.g. electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating

Definitions

  • the invention belongs to the technical field of display, and in particular relates to an electron transport film and a preparation method and application thereof.
  • QLEDs quantum dot light-emitting diodes
  • the nano-zinc oxide electron transport layer prepared by depositing a zinc oxide colloid solution has become the main electron transport layer scheme used in quantum dot light-emitting diodes. It has a good energy level matching relationship with the cathode and the quantum dot luminescent layer, which significantly reduces the injection barrier of electrons from the cathode to the quantum dot luminescent layer, and its deep valence band energy level can effectively block the empty space. The function of the hole.
  • the nano-zinc oxide electron transport layer also has excellent electron transport capability, and its electron mobility is as high as 10 -3 cm 2 /V ⁇ S or more. These characteristics make the nano-zinc oxide electron transport layer the first choice for quantum dot light-emitting diode devices, which significantly improves the stability and luminous efficiency of the device.
  • nano-zinc oxide materials provide excellent performance for quantum dot light-emitting diodes, the problems caused by the properties of the materials themselves cannot be ignored.
  • the particle diameter of the zinc oxide nanoparticles used for preparing the nano zinc oxide electron transport layer is generally close to or less than 5 nm, the zinc oxide nanoparticles have a very large specific surface area in this case. The resulting large surface energy makes the zinc oxide nanoparticles very unstable and prone to agglomeration to reduce the effects of surface energy. If agglomeration occurs, it will inevitably have a devastating effect on the film formation of the zinc oxide colloidal solution and the electrical conductivity after film formation.
  • surface ligands are often added to the zinc oxide colloid solution and adsorbed on the zinc oxide nanoparticles to ensure the stability of the nanoparticles.
  • the presence of surface ligands increases the distance of electron transitions in the nano-zinc oxide electron transport layer after film formation, which hinders the transport of electrons in the zinc oxide material, which affects the conductivity of the nano-zinc oxide electron transport layer.
  • the effects of surface defects on nanomaterials cannot be ignored.
  • the surface of the material has a very large number of defects compared to the bulk of the material, which is the accumulation of defects (eg, vacancies, interstitial atoms, etc.).
  • the invention provides an electron transporting film and a preparation method thereof, and a QLED device comprising the above electron transporting film, which aims to solve the problem that the nano-zinc oxide surface ligand has an obstructive effect on electron transport in the electron transporting layer of the existing zinc oxide material. And the problem that the surface defects of nano zinc oxide cause quenching of excitons.
  • the embodiment of the present invention is achieved by the first aspect, and provides an electron transport film composed of nano zinc oxide containing doped metal ions, wherein the metal ion doped nano zinc oxide is a surface The nano zinc oxide enriched in the metal ion.
  • a method of preparing an electron transporting film comprising the steps of:
  • a solution containing the metal ion doped zinc oxide nanoparticles is deposited on the substrate and dried to form an electron transporting film.
  • a light emitting diode device wherein the electron transporting film is composed of nano zinc oxide containing doped metal ions, and the nano zinc oxide doped with metal ions is Surface-enriched nano-zinc oxide of the metal ion; or
  • a method of preparing the electron transporting film comprising the steps of:
  • the solution of the doped metal ion-containing zinc oxide nanoparticle is deposited on the substrate and dried to form an electron transporting film.
  • the electron transporting film provided by the present invention is composed of nano zinc oxide containing doped metal ions, and the nano-zinc oxide doped with metal ions is nano zinc oxide whose surface is enriched with the metal ions.
  • zinc oxide nanomaterials can significantly increase the stability of zinc oxide nanoparticles by enriching the doped metal ions on the surface of the nano zinc oxide material, thereby avoiding the use of surface ligands in the zinc oxide nanomaterials, thereby avoiding surface matching.
  • the introduction of the body hinders the transmission of electrons in the zinc oxide material, and further optimizes the conductivity of the nano zinc oxide electron transport layer.
  • the doping method of metal ions enriched on the surface of the nano zinc oxide greatly reduces the surface defects of the nano zinc oxide material, thereby reducing the quenching effect of the surface defects of the material on the excitons, thereby improving the overall use.
  • Light-emitting diodes of electron transport films such as QLED (quantum dot light-emitting diode) devices have luminous efficiency and device performance.
  • the method for preparing an electron transporting film only needs to react a zinc salt, a metal salt containing a metal ion doped with a mixed solution of a base, to prepare a zinc oxide nanoparticle containing a doped metal ion, and then pass the solution method. It can be formed into a film.
  • the method is very simple, low in cost, easy to operate, low in equipment requirements, and repeatable, enabling large-scale production.
  • the light-emitting diode provided by the present invention contains the above-mentioned electron transporting film, the luminous efficiency and device performance of the device can be remarkably improved.
  • FIG. 1 is a schematic view showing a surface enrichment phenomenon of a doped metal according to an embodiment of the present invention
  • FIG. 2 is a schematic flow chart of a method for preparing an electron transporting film according to an embodiment of the present invention
  • FIG. 3 is a schematic structural diagram of a light emitting diode device according to an embodiment of the present invention.
  • first and second are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated.
  • features defining “first” and “second” may include one or more of the features either explicitly or implicitly.
  • the meaning of "a plurality" is two or more unless specifically and specifically defined otherwise.
  • Embodiments of the present invention provide an electron transporting film, which is composed of nano zinc oxide containing doped metal ions, and the nano-zinc oxide doped with metal ions is nano-oxidized for surface enrichment of the metal ions. Zinc.
  • the first doping structure is: doping metal ions into the crystal structure of the host material, occupying a site of the main metal ions to form a solid solution (such as patent document CN201610939765.0, doping metal elements in the metal oxide host material, doping The impurity ions enter the crystal structure of the host material and occupy the site of the host metal ion). The more metal elements are doped, the higher the concentration of free electrons, and the stronger the conductivity.
  • the second doping structure is that the doped metal ions are precipitated from the host material in the form of impurities, and a uniform structure cannot be formed.
  • the third doping structure is that the doped metal ions are focused on the surface region of the metal oxide host material to constitute a surface enrichment phenomenon.
  • Surface enrichment refers to the metal oxide system doped with metal ions.
  • the doped metal ions accumulate in the surface region of the metal oxide, resulting in the concentration of metal ions in the surface region of the metal oxide is higher than that in the bulk phase of the metal oxide. The phenomenon.
  • the doped metal ions enter the surface region of the metal oxide host material, occupying the defect position mainly composed of the main metal ion vacancies, and maintaining the host material. Crystal structure. That is to say, for the metal oxide host material in which the doping ion surface enrichment phenomenon occurs, the entire host material includes only a single crystal phase including the surface region, and there is no crystal phase structure other than the metal oxide host material. The second phase. Thereby, the uniformity of the overall material properties can be ensured. At the same time, when surface enrichment occurs, the surface properties of the material are bound to change significantly.
  • the surface enrichment phenomenon of doped metal ions can significantly reduce the surface energy of the metal oxide host material, thereby significantly enhancing the stability of the metal oxide host material, especially with a large ratio.
  • the stability of the surface area of the nano metal oxide host material since the doped metal ions enriched on the surface occupy a large amount of defects on the surface of the metal oxide host material, the defects are passivated, so that the metal oxide host material The concentration of defects on the surface is greatly reduced.
  • the nano zinc oxide material is doped by selecting a suitable doping metal ion, so that the surface enrichment phenomenon occurs on the surface of the nano zinc oxide particles, thereby significantly improving the stability of the zinc oxide nanoparticles. Avoiding the use of surface ligands and thereby causing damage to the electrical conductivity of the nano-zinc oxide electron transport layer; simultaneously reducing the surface defect concentration of the nano zinc oxide material and reducing the quenching effect of the surface defects of the nano zinc oxide material on excitons, Thereby, the luminous efficiency of the light emitting diode such as the QLED device is improved.
  • the electron transporting film provided by the embodiment of the invention is composed of nano-zinc oxide containing doped metal ions, and the nano-zinc oxide doped with metal ions is nano-zinc oxide whose surface is enriched with the metal ions.
  • zinc oxide nanomaterials can significantly increase the stability of zinc oxide nanoparticles by enriching the doped metal ions on the surface of the nano zinc oxide material, thereby avoiding the use of surface ligands in the zinc oxide nanomaterials, thereby avoiding surface matching.
  • the introduction of the body hinders the transmission of electrons in the zinc oxide material, and further optimizes the conductivity of the nano zinc oxide electron transport layer.
  • the doping method of metal ions enriched on the surface of the nano zinc oxide greatly reduces the surface defects of the nano zinc oxide material, thereby reducing the quenching effect of the surface defects of the material on the excitons, thereby improving the overall use.
  • Light-emitting diodes of electron transport films such as QLED (quantum dot light-emitting diode) devices have luminous efficiency and device performance.
  • the selection of the doping metal ions satisfies two requirements.
  • the valence state of the doped metal ion is not positive divalent, that is, the valence state of the doped metal ion is different from the valence state of Zn 2+ . Since the surface of the zinc oxide nanomaterial is not electrically neutral due to the presence of a large number of defects, a certain amount of electric charge is locally accumulated.
  • the unequal doping metal ions will bring a large amount of free electrons or holes, and the free electrons or holes generated will tend to be rich.
  • the surface of the nanomaterial is concentrated to neutralize the surface charge, thereby promoting the enrichment of the doped metal ions on the surface of the nano zinc oxide.
  • the ionic radius of the doped metal ion is significantly larger than the ionic radius of Zn 2+ . Specifically, the ionic radius of the doped metal ion is 130%-200% of the Zn 2+ radius, that is, the doping.
  • the radius difference between the metal ions needs to be more than 30% of the radius of the zinc ion and not more than twice the radius of the Zn 2+ .
  • the resulting severe kinetic instability causes the doped metal ions to be enriched on the surface of the nano zinc oxide, occupying the defect sites dominated by zinc ion vacancies, rather than entering the interior of the crystal structure to replace the zinc ion sites, thereby
  • the metallurgical structure of the nano-zinc oxide of the host material is ensured to ensure the uniformity of material properties.
  • the doped metal ion When the ionic radius of the doped metal ion is close to the ionic radius of Zn 2+ , the doped metal ion can easily enter the crystal structure of the zinc oxide material, replacing the Zn 2+ site to form a solid solution, affecting the original Electrical properties of nano zinc oxide.
  • the radius of the doped metal ions reaches twice or more of the Zn 2+ ion radius, the excessively doped metal ions hardly enter the zinc ion vacancies on the surface of the zinc oxide material, but directly oxidize in the form of the second phase. The precipitation of the surface of the zinc material causes severe damage to the electrical conductivity of the nano-zinc oxide electron transport layer.
  • the doping metal ion of the embodiment of the invention has wide selectivity, as long as the valence state of the doped metal ion is different from the valence state of Zn 2+ and the ion radius of the doped metal ion is significantly larger than that of the Zn 2+ ion.
  • the radius is sufficient, so that it can be targeted according to the specific requirements of the electron transport film in practical applications, and has strong applicability and practicability.
  • the doped metal ion is a rare earth metal ion, and the rare earth metal ion can satisfy the above two conditions as a doping material, and has a good surface enrichment phenomenon for the nano zinc oxide host material.
  • the doping metal ion is selected from at least one of La 3+ , Y 3+ , Gd 3+ , and Ce 4+ , and the electron transporting film is prepared by using a preferred doping metal ion, which can be successfully
  • the doping ions are concentrated in the surface region of the nano zinc oxide material.
  • the difference in ionic radius of La 3+ , Y 3+ , Gd 3+ , Ce 4+ and zinc ions is as shown in Table 1 below, and the calculation formula of the ionic radius difference is: Wherein r represents a radius and Mn + represents a doped metal ion.
  • the surface enrichment phenomenon of the doping ions is determined, and the doping molar concentration of the metal ions also affects the surface enrichment phenomenon of the doped ions.
  • the defect sites such as the bulk metal ion vacancies in the surface region of the material are relatively limited.
  • the larger the ionic radius of the doped metal ions the less the defect positions such as the host metal ion vacancies that can be occupied in the surface region of the host material, and the molar concentration that can be used for doping without generating the second phase. The lower it is.
  • the amount of doped metal ions is extremely small, since the amount of doping ions does not cause significant lattice distortion, the doped metal ions can still enter the bulk phase of the zinc oxide material to form a solid solution. Without enrichment of doped metal ions on the surface of the zinc oxide material. Therefore, control of the molar concentration of doped metal ions is important.
  • the doping metal ion accounts for 0.05%-10% of the total molar concentration of the metal element in the electron transporting film, but specifically, it is determined by the type of the doping metal ion.
  • the doping molar concentration of the doping metal ions is too low, a part of the doped metal ions may enter the bulk phase of the zinc oxide nanoparticles to form a solid solution, and the amount and body of the doped metal ions in the surface region at this time
  • the number of phases is relatively close, which is not conducive to the formation of doping ion surface enrichment phenomenon; when the doping molar concentration of the doping metal ions is too high, the doped metal ions enter the zinc oxide nanoparticle bulk phase
  • the intense lattice distortion produced will cause the excess newly added doping metal ions to be concentrated on the surface of the zinc oxide nanoparticles.
  • the doping of metal ions on the surface of the zinc oxide material will precipitate in the form of the second phase, which seriously affects Electrical properties of zinc
  • the embodiment of the invention only needs to dope a metal ion to realize the two functions of improving the conductivity of the zinc oxide electron transport layer and improving the luminous efficiency of the quantum dot light emitting diode device, and the doping effect is very good.
  • the electron transporting film as a nano-zinc oxide electron transporting film containing a doping metal ion as an example, and specifically,
  • the doping molar concentration of the La 3+ is 0.05% to 5% based on 100% of the total molar concentration of the metal elements in the electron transporting film.
  • the molar concentration of the dopant in the La 3+ this range, the number of moles of zinc oxide La 3+ nanoparticle surface area ratio of the number of moles of 3+ and zinc oxide nanoparticles in the bulk phase of La 4: 1
  • the ratio of the number of La 3+ in the surface region to the number in the bulk phase is 4:1 to 30:1, which can form a surface enrichment phenomenon of doping ions.
  • the higher the content of doped metal ions the more pronounced the surface enrichment phenomenon.
  • the doping molar concentration of the Y 3+ is 0.1% to 10% based on 100% of the total molar concentration of the metal elements in the electron transporting film.
  • the molar concentration of the dopant in the range of Y 3+, Y 3+ molar ratio of the number of moles of zinc oxide nanoparticles in the surface region of Y 3+ and zinc oxide nanoparticles in the bulk phase is 2: 1
  • the ratio of the number of 40:1, Y 3+ in the surface region to the number in the bulk phase is 2:1 to 40:1, which can form a surface enrichment phenomenon of doping ions. Within this range, the higher the content of doped metal ions, the more pronounced the surface enrichment phenomenon.
  • the doping molar concentration of the Gd 3+ is 0.1% to 8% based on 100% of the total molar concentration of the metal element in the electron transporting film.
  • Gd 3+ moles of zinc oxide nanoparticles with a surface area ratio of the number of moles of Gd 3+ zinc oxide nanoparticles in the bulk phase is 3: 1
  • the ratio of the number of Gd 3+ in the surface region to the number in the bulk phase is 3:1 to 35:1, which can form a surface enrichment phenomenon of doping ions.
  • the higher the content of doped metal ions the more pronounced the surface enrichment phenomenon.
  • the doping molar concentration of the Ce 4+ is 0.2% to 10% based on 100% of the total molar concentration of the metal elements in the electron transporting film.
  • the molar concentration of the Ce doping in the range 4+ Ce 4+ moles of zinc oxide nanoparticles with a surface area ratio of the number of moles of zinc oxide nanoparticles 4+ bulk phase Ce 2: 1 40:1, that is, the ratio of the number of Ce 4+ in the surface region to the number in the bulk phase is 2:1 to 40:1, which can form a surface enrichment phenomenon of doping ions.
  • the higher the content of doped metal ions the more pronounced the surface enrichment phenomenon.
  • the electron transporting film has a thickness of 10 to 100 nm.
  • the thickness of the electron transporting film is less than 10 nm, the film layer is easily broken down by electrons, and the injection performance of the carrier cannot be ensured; when the thickness of the electron transporting film is more than 100 nm, the injection of electrons is hindered, and the influence is affected. The charge injection balance of the device.
  • the electron transporting film according to the embodiment of the present invention can be obtained by the following method.
  • an embodiment of the present invention provides a method for preparing an electron transporting film, which includes the following steps:
  • the method for preparing an electron transporting film only needs to react a zinc salt, a metal salt containing a metal ion doped, and a mixed solution of a base to prepare a zinc oxide nanoparticle containing a doped metal ion, and then pass through
  • the solution method can be formed into a film.
  • the method is very simple, low in cost, easy to operate, low in equipment requirements, and repeatable, and can realize mass production.
  • the zinc salt, the metal salt containing the doped metal ion, and the mixed solution of the alkali are formed by dissolving a zinc salt, a metal salt containing a doped metal ion, and an alkali in a solvent.
  • the zinc salt is used as a zinc source to provide zinc for preparing zinc oxide nanoparticles containing doped metal ions
  • the zinc salt includes, but not limited to, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, etc. One of them.
  • the metal salt containing doped metal ions prepares zinc oxide nanoparticles containing doped metal ions to provide doped metal ions, and the type of the doping metal ions satisfies: the valence state of the doped metal ions is not positive divalent And the ionic radius of the doped metal ion is 130%-200% of the radius of Zn 2+ , as described above.
  • the doping metal ion is selected from the group consisting of rare earth metal ions, and particularly preferably at least one of La 3+ , Y 3+ , Gd 3+ , and Ce 4+ .
  • the metal salt containing a doping metal ion may be selected from barium sulfate, barium chloride, barium nitrate, barium acetate, barium sulfate, barium chloride, barium acetate, barium nitrate, barium nitrate, barium acetate, barium sulfate. At least one of barium chloride, barium chloride, barium acetate, barium sulfate, barium chloride and a metal salt thereof, but is not limited thereto.
  • a zinc oxide salt, a metal salt containing a metal ion doped, and a mixed solution of a base are used to prepare a zinc oxide nanoparticle containing doped metal ions, and the reaction course is: zinc ion in the zinc salt and doping in the metal salt
  • the metal ions react with the lye to form a hydroxide intermediate, and then the hydroxide intermediate undergoes a polycondensation reaction to gradually form doped zinc oxide nanoparticles.
  • the base provides a hydroxide ion for the reaction, and specifically, the base is at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, TMAH, ammonia water, ethanolamine, and ethylenediamine.
  • the solvent for forming a mixed solution of a zinc salt, a metal salt doped with a metal ion, and a base may be an organic solvent or an inorganic solvent, and may be specifically selected from the group consisting of water, methanol, ethanol, propanol, butanol, and the like. At least one of ethylene glycol, ethylene glycol monomethyl ether, and DMSO, but is not limited thereto.
  • the doping metal ion accounts for 0.05%-10% of the total molar concentration of the metal ion.
  • the doping molar concentration of the doping metal ions is too low, a part of the doped metal ions may enter the bulk phase of the zinc oxide nanoparticles to form a solid solution, and the amount and body of the doped metal ions in the surface region at this time
  • the number of phases is relatively close, which is not conducive to the formation of doping ion surface enrichment phenomenon; when the doping molar concentration of the doping metal ions is too high, the doped metal ions enter the zinc oxide nanoparticle bulk phase
  • the intense lattice distortion produced will cause the excess newly added doping metal ions to be concentrated on the surface of the zinc oxide nanoparticles.
  • the doping of metal ions on the surface of the zinc oxide material will precipitate in the form of the second phase, which seriously
  • the molar ratio of the hydroxide ion to the metal ion is 1.5:1 to 2.5:1 to ensure doping of the zinc oxide nanoparticle. Formation and reduction of reaction by-product formation.
  • the metal salt is significantly excessive, resulting in a large amount of metal salt unable to form doped zinc oxide nanoparticles; and when the molar ratio of hydroxide ions to metal ions is greater than 2.5: At 1 o'clock, the lye is significantly excessive, and the excess hydroxide ions form a stable complex with the hydroxide intermediate, which cannot be polycondensed to form doped zinc oxide nanoparticles. More preferably, in the mixed solution of the zinc salt, the metal salt containing the doped metal ion, and the alkali, the molar ratio of the hydroxide ion to the metal ion is selected to be 1.7:1 to 1.9:1.
  • the mixed solution of the zinc salt, the metal salt containing the doped metal ion and the alkali in the embodiment of the invention can be prepared by adding a zinc salt, a metal salt containing a metal ion doped, and a base to a solvent.
  • the preparation method of the zinc salt, the metal salt containing the doped metal ion, and the alkali is prepared as follows:
  • An alkali solution is added to the salt solution to obtain a mixed solution of a zinc salt, a metal salt containing a doped metal ion, and a base.
  • the above steps can be carried out at room temperature (10-30 ° C).
  • the lye may be one in which the alkali is dissolved or the base is diluted in another solvent which is the same as or different from the solvent for dissolving the zinc salt or the metal salt containing the metal ion.
  • the zinc salt and the metal salt containing the doped metal ion can be sufficiently dissolved and uniformly mixed, and further adding the alkali solution under the conditions can promote the reaction to proceed uniformly.
  • the mixed solution was prepared at 0-70 ° C to prepare zinc oxide nanoparticles containing doped metal ions.
  • the above temperature can ensure the formation of zinc oxide nanoparticles containing doped metal ions and obtain good particle dispersibility.
  • the reaction temperature is lower than 0 ° C, the reaction temperature is too low, which will significantly slow down the formation of zinc oxide nanoparticles, and even can not form zinc oxide nanoparticles, but only the hydroxide intermediate; and when the reaction temperature is higher than 70 ° C The obtained nanoparticles have poor dispersibility and agglomeration, which affects the late film formation of the doped zinc oxide colloidal solution. More preferably, the reaction temperature is selected from room temperature of 10 to 60 °C. Further, the reaction time is 30-240 min to ensure the formation of doped zinc oxide nanoparticles and control the particle size of the nanoparticles.
  • the reaction time is less than 30 min, the reaction time is too short, the formation of doped zinc oxide nanoparticles is insufficient, and the obtained nanoparticles have poor crystallinity; and when the reaction time exceeds 4 h, the excessively long particles grow up to generate The nanoparticles are too large and the particle size is not uniform, which affects the late film formation of the doped zinc oxide colloid solution. More preferably, the reaction time is from 1 to 2 hours.
  • the volume ratio of the precipitating agent to the reaction system solution is 2:1 to 6:1 to ensure that excessive precipitant is destroyed to destroy the doped zinc oxide under the premise of sufficiently precipitating the zinc oxide nanoparticles containing the doped metal ions.
  • the solubility of the particles More preferably, the volume ratio of the precipitating agent to the reaction system solution is selected from 3:1 to 5:1.
  • the precipitant is one of the less polar solvents including, but not limited to, ethyl acetate, n-hexane, n-heptane, acetone, and the like.
  • the white precipitate obtained after centrifugation is again dissolved in the reaction solvent, and the washing is repeated several times to remove the reactants not involved in the reaction, and the finally obtained white precipitate is collected, which is soluble in the solvent to obtain an unequal metal ion having a larger ionic radius.
  • a doped zinc oxide colloidal solution that is, a colloidal solution containing zinc ion nanoparticles doped with metal ions.
  • the doped zinc oxide colloid solution is synthesized by the low temperature solution method, and the mixed solution of the zinc salt and the metal salt containing the doped metal ion reacts with the alkali solution to form a hydroxide in the whole reaction process of the low temperature solution method.
  • the body, then the polycondensation reaction of the hydroxide intermediate gradually forms doped zinc oxide nanoparticles, and the formation of the doped zinc oxide nanoparticles is carried out in the liquid phase.
  • the presence of the liquid phase provides an excellent medium for the mass transfer and diffusion of the doped metal ions in the zinc oxide nanoparticles, so that the metal doping ions meeting the two requirements described above can be diffused to the zinc oxide in a short time.
  • the surface of the nanoparticles ensures the occurrence of surface enrichment of the doped metal ions in terms of kinetics.
  • the solution containing the metal ion doped zinc oxide nanoparticles is deposited on the substrate, and the selection of the substrate is not strictly limited, and may be a common substrate for depositing an electron transport film, or may be deposited.
  • Other functional layers require a functional substrate for further depositing an electron transporting film, such as a functional substrate deposited with a laminated bonded anode, a light-emitting layer, which is deposited on the light-emitting layer.
  • the deposition method is not strictly limited, and the solution processing method may be based on the colloidal solution property of a solution containing zinc ion nanoparticles doped with metal ions. Specifically, it includes, but is not limited to, one of a spin coating method, a knife coating method, a printing method, a spray coating method, a roll coating method, and an electrodeposition method.
  • a film deposited with a solution containing zinc ion nanoparticles doped with metal ions is dried to form a film, and the drying is performed by low temperature annealing, and the low temperature annealing temperature selected here is only required to dope the solvent in the zinc oxide colloid solution. It can be volatilized and does not require a higher temperature, depending on the boiling point of the solvent in the doped zinc oxide colloidal solution.
  • the low temperature annealing is performed at a temperature of from room temperature to 150 °C. Higher annealing temperatures in turn can cause damage to the quantum dot luminescent layer that has been deposited on the substrate.
  • the low temperature annealing process needs to be performed under an inert atmosphere to protect the functional layer deposited on the substrate, such as the quantum dot luminescent layer, from damage.
  • the embodiment of the invention further provides an LED device, wherein the LED device comprises an electron transport film, the electron transport film is composed of nano zinc oxide containing doped metal ions, and the metal ion doped Nano zinc oxide is a nano zinc oxide whose surface is enriched with the metal ion; or
  • a method of preparing the electron transporting film comprising the steps of:
  • the solution of the doped metal ion-containing zinc oxide nanoparticle is deposited on the substrate and dried to form an electron transporting film.
  • the light emitting diode provided by the embodiment of the invention has an electron transporting film.
  • the electron transporting film is composed of nano zinc oxide containing doped metal ions, and the metal ion doped nano zinc oxide is nano zinc oxide whose surface is enriched with the metal ions.
  • zinc oxide nanomaterials can significantly increase the stability of zinc oxide nanoparticles by enriching the doped metal ions on the surface of the nano zinc oxide material, thereby avoiding the use of surface ligands in the zinc oxide nanomaterials, thereby avoiding surface matching.
  • the introduction of the body hinders the transmission of electrons in the zinc oxide material, and further optimizes the conductivity of the nano zinc oxide electron transport layer.
  • the doping method of metal ions enriched on the surface of the nano zinc oxide greatly reduces the surface defects of the nano zinc oxide material, thereby reducing the quenching effect of the surface defects of the material on the excitons, thereby improving the overall use. Luminous efficiency and device performance of light-emitting diodes for electron transport films.
  • the method for preparing the electron transporting film and the electron transporting film and the preferred situation thereof are as described above, and the details are not described herein again.
  • the illuminating layer may be an organic luminescent layer or a quantum dot luminescent layer.
  • the light emitting diode device is an organic light emitting diode (OLED) device; when the light emitting layer is a quantum dot light emitting layer, the light emitting diode is a quantum dot light emitting diode ( QLED) device.
  • the light emitting diode further comprises a hole transport layer to promote the transport of holes and promote carrier balance.
  • the light emitting diode comprises an anode 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5 and a cathode 6 laminated on the substrate 1, wherein the light is
  • the transport layer is a carrier transport film prepared by the above method.
  • the substrate may be a hard substrate or a flexible substrate, and specifically, a glass substrate may be selected.
  • the anode may be ITO, but is not limited thereto.
  • the hole transport layer may be made of a hole transporting material conventional in the art, including but not limited to TFB, PVK, Poly-TPD, TCTA, CBP, etc. or a mixture of any combination thereof, or other high performance. Hole transport material.
  • the light emitting layer material may be selected from a conventional organic light emitting material.
  • the quantum dots of the luminescent layer material may be one of red, green, and blue, specifically CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe.
  • the quantum dots may or may not contain cadmium.
  • the thickness of the light-emitting layer is preferably from 20 to 60 nm.
  • the electron transporting layer employs the above electron transporting film.
  • the cathode adopts a metal cathode material, such as metal silver or metal aluminum, or a nano silver wire or a nano copper wire, and the nano silver wire or the nano copper wire is used, which has a smaller electric resistance, and facilitates smooth injection of carriers.
  • the thickness of the cathode is preferably 15-30 nm.
  • the obtained light emitting diode can be packaged.
  • an embodiment of the present invention provides a method for fabricating a light emitting diode, including the following steps:
  • the light-emitting layer material solution is deposited on the anode surface.
  • the luminescent layer material solution may be deposited into a film by spin coating. Specifically, the anode substrate is placed on a homogenizer, and a solution of a certain concentration of the luminescent layer material is spin-coated to form a film, and the thickness of the luminescent layer is controlled by adjusting the concentration of the solution, the spin coating speed, and the spin coating time, and then Thermal annealing at a suitable temperature.
  • the method before preparing the luminescent layer, the method further comprises preparing a hole transport layer on the anode.
  • the hole transport layer may be prepared by the same method as the light-emitting layer, preferably by a solution processing method such as spin coating, and further controlling the film thickness by adjusting the concentration of the solution, the spin coating speed, and the spin coating time, and then at a suitable temperature. Lower thermal annealing treatment.
  • An electron transport layer is prepared on the light-emitting layer, and is prepared by the method of using the above-mentioned electron transport film, and details are not described herein again.
  • a cathode is prepared on the electron transport layer.
  • the substrate on which the functional layers are deposited is placed in an evaporation chamber to thermally evaporate the cathode through a mask.
  • the device is packaged, and the encapsulation conditions are preferably performed under conditions of an oxygen content and a water content of less than 0.1 ppm to ensure the stability of the device.
  • the light-emitting diode can also be obtained by another method.
  • the method for preparing the light-emitting diode includes the following steps:
  • a cathode is prepared on the light-emitting layer.
  • a cerium ion doped nano zinc oxide electron transporting film the preparation method thereof comprises the following steps:
  • an appropriate amount of zinc acetate and barium sulfate were added to 50 ml of a methanol solvent to form a mixed salt solution having a total concentration of 0.1 mol/L, wherein the doping molar concentration of La 3+ was 3%.
  • an appropriate amount of potassium hydroxide powder was dissolved in another 50 ml of methanol solvent to form a lye having a concentration of 0.3 mol/L.
  • the mixed salt solution was then heated to 50 ° C, and the potassium hydroxide solution was added dropwise until the molar ratio of hydroxide ions to metal ions was 1.7:1.
  • the mixed solution was further stirred at 50 ° C for 2 hours to obtain a homogeneous transparent solution.
  • a heptane solvent having a volume ratio of 3:1 was added to the homogeneous transparent solution to produce a large amount of white precipitate in the transparent solution.
  • the cloudy solution was centrifuged at 7000 rpm, and the resulting white precipitate was again dissolved in a methanol solvent. This cleaning process is repeated four times.
  • the finally obtained white precipitate was dissolved in an appropriate amount of ethanol solvent to obtain a cerium ion doped zinc oxide colloid solution having a concentration of 30 mg/ml.
  • the obtained 30 mg/ml cesium ion doped zinc oxide colloid solution was deposited by spin coating on a substrate on which an anode, a hole transport layer, and a quantum dot luminescent layer were sequentially deposited, and was subjected to an argon atmosphere at 100 ° C. Annealing, that is, a nano-zinc oxide electron transport layer doped with cerium ions was prepared.
  • the spin coating speed is 3000 rpm, and the spin coating time is 30 s to control the thickness of the doped zinc oxide electron transport layer to be about 50 nm.
  • a cerium ion doped nano zinc oxide electron transporting film the preparation method thereof comprises the following steps:
  • an appropriate amount of zinc nitrate and cerium chloride were added to 50 ml of an ethanol solvent to form a mixed salt solution having a total concentration of 0.1 mol/L, wherein the molar concentration of Y3+ was 7%.
  • an appropriate amount of lithium hydroxide powder was dissolved in another 50 ml of ethanol solvent to form a lye having a concentration of 0.2 mol/L.
  • the mixed salt solution was then heated to 40 ° C and the lithium hydroxide solution was added dropwise until the molar ratio of hydroxide ions to metal ions was 1.9:1.
  • the mixed solution was further stirred at 30 ° C for 1 hour to obtain a uniform transparent solution.
  • a 4:1 volume ratio of ethyl acetate solvent was added to the homogeneous clear solution to produce a large amount of white precipitate in the clear solution.
  • the cloudy solution was centrifuged at 7000 rpm, and the resulting white precipitate was again dissolved in an ethanol solvent. This cleaning process is repeated four times.
  • the finally obtained white precipitate was dissolved in an appropriate amount of ethanol solvent to obtain a cerium ion doped zinc oxide colloid solution having a concentration of 30 mg/ml.
  • the obtained 30 mg/ml cesium ion doped zinc oxide colloid solution was deposited by spin coating on a substrate on which an anode, a hole transport layer, and a quantum dot luminescent layer were sequentially deposited, and was subjected to an argon atmosphere at 100 ° C. Annealing, that is, a nano-zinc oxide electron transport layer doped with cerium ions was prepared.
  • the spin coating speed was 1500 rpm and the spin coating time was 30 s to control the thickness of the doped zinc oxide electron transport layer to be about 80 nm.
  • a cerium ion doped nano zinc oxide electron transporting film the preparation method thereof comprises the following steps:
  • TMAH powder was dissolved in another 30 ml of ethanol solvent to form a lye having a concentration of 0.3 mol/L.
  • the mixed salt solution was then added dropwise to the TMAH solution at room temperature until the molar ratio of hydroxide ions to metal ions was 1.5:1. After the completion of the dropwise addition of the TMAH solution, the mixed solution was further stirred at room temperature for 2 hours to obtain a uniform transparent solution.
  • the obtained 30 mg/ml cesium ion doped zinc oxide colloid solution was deposited by spin coating on a substrate on which an anode, a hole transport layer, and a quantum dot luminescent layer were sequentially deposited, and annealed in a nitrogen atmosphere at 100 ° C. That is, a nano-zinc oxide electron transport layer doped with cerium ions is prepared.
  • the spin coating speed was 4500 rpm and the spin coating time was 30 s to control the thickness of the doped zinc oxide electron transport layer to be about 20 nm.
  • a cerium ion doped nano zinc oxide electron transporting film the preparation method thereof comprises the following steps:
  • an appropriate amount of zinc chloride and cerium nitrate were added to 50 ml of a methanol solvent to form a mixed salt solution having a total concentration of 0.1 mol/L, wherein the doping molar concentration of Ce4+ was 8%.
  • an appropriate amount of the ethylenediamine solution was diluted into another 50 ml of methanol solvent to form a lye having a concentration of 0.3 mol/L.
  • the mixed salt solution was then heated to 50 ° C, and the ethylenediamine solution was added dropwise until the molar ratio of hydroxide ions to metal ions was 1.8:1.
  • the mixed solution was further stirred at 50 ° C for 1 h to obtain a homogeneous transparent solution.
  • an acetone solvent having a volume ratio of 3:1 was added to the homogeneous transparent solution to produce a large amount of white precipitate in the transparent solution.
  • the cloudy solution was centrifuged at 7000 rpm, and the resulting white precipitate was again dissolved in a methanol solvent. This cleaning process is repeated four times.
  • the finally obtained white precipitate was dissolved in an appropriate amount of an ethanol solvent to obtain a cerium ion doped zinc oxide colloid solution having a concentration of 30 mg/ml.
  • the obtained 30 mg/ml cesium ion doped zinc oxide colloid solution was deposited by spin coating on a substrate on which an anode, a hole transport layer, and a quantum dot luminescent layer were sequentially deposited, and annealed in a nitrogen atmosphere at 50 ° C. That is, a nano-zinc oxide electron transport layer doped with cerium ions is prepared.
  • the spin coating speed is 3000 rpm, and the spin coating time is 30 s to control the thickness of the doped zinc oxide electron transport layer to be about 50 nm.
  • a positive type QLED device includes a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light-emitting layer 4, an electron transport layer 5, and a cathode 6 in this order from bottom to top.
  • the material of the substrate 1 is a glass piece
  • the material of the anode 2 is an ITO substrate
  • the material of the hole transport layer 3 is TFB
  • the material of the electron transport layer 5 is doped oxidation of an unequal metal ion having a large ionic radius.
  • the material of zinc and cathode 6 is Al.
  • the positive QLED device includes the following steps:
  • the doped zinc oxide colloid solution is spin-coated on the quantum dot luminescent layer and treated at a low temperature to obtain a nano zinc oxide electron transport layer;
  • the cathode is vapor deposited on the nano zinc oxide electron transport layer to obtain a quantum dot light emitting diode.
  • An OLED device comprising, in order, a substrate, an anode, a hole transport layer, an organic light emitting layer, an electron transport layer, and a cathode.
  • the material of the substrate is a glass piece
  • the material of the anode is an ITO substrate
  • the material of the hole transport layer is TFB
  • the material of the electron transport layer is an unequal metal ion doped with zinc oxide and a cathode having a larger ionic radius.
  • the material is Al.
  • the positive OLED device includes the following steps:
  • the doped zinc oxide colloid solution is spin-coated on the organic light-emitting layer and low-temperature treatment to obtain a nano zinc oxide electron transport layer;
  • the cathode is vapor deposited on the nano zinc oxide electron transport layer to obtain an organic light emitting diode.

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Abstract

一种电子传输薄膜，所述电子传输薄膜由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌。所述电子传输薄膜，能够显著提高氧化锌纳米颗粒的稳定性，从而可以避免氧化锌纳米材料中表面配体的使用，进而避免表面配体的引入对电子在氧化锌材料中的传输造成的阻碍，优化纳米氧化锌电子传输层的导电性能。

Description

电子传输薄膜及其制备方法和应用 技术领域
本发明属于显示技术领域，尤其涉及一种电子传输薄膜及其制备方法和应用。
背景技术
近来，随着显示技术的不断发展，以量子点材料作为发光层的量子点发光二极管(QLED)展现出了巨大的应用前景。由于其发光效率高、发光颜色可控、色纯度高、器件稳定性好、可用于柔性用途等特点，使QLED在显示技术、固态照明等领域受到了越来越多的关注。
近年来，通过沉积氧化锌胶体溶液制得的纳米氧化锌电子传输层成为了量子点发光二极管中主要采用的电子传输层方案。其与阴极和量子点发光层之间具有良好的能级匹配关系，显著降低了电子从阴极到量子点发光层的注入势垒，并且其较深的价带能级又可以起到有效阻挡空穴的功能。此外，纳米氧化锌电子传输层还具有优良的电子传输能力，其电子迁移率高达10 -3cm 2/V·S以上。这些特性都使纳米氧化锌电子传输层成为了量子点发光二极管器件的首选，显著提升了器件的稳定性和发光效率。
在纳米氧化锌材料为量子点发光二极管带来优良性能的同时，其材料本身特性所带来的问题也是不容忽视的。一方面，由于用于制备纳米氧化锌电子传输层的氧化锌纳米颗粒的粒径一般都接近甚至小于5nm，在此情况下氧化锌纳米颗粒具有非常大的比表面积。由此带来的巨大的表面能使得氧化锌纳米颗粒变得非常不稳定，极易发生团聚以减小表面能带来的影响。如果团聚一旦发生，势必对氧化锌胶体溶液的成膜性和成膜后的导电性能产生毁灭性的影响。因此，为防止氧化锌颗粒发生团聚，表面配体往往会被加入到氧化锌胶体溶液中并吸附在氧化锌纳米颗粒上以确保纳米颗粒的稳定性。但与此同时，表面配体的存在会增加成膜后纳米氧化锌电子传输层中电子跃迁的距离，进而阻碍电子在氧化锌材料中的传输，使得纳米氧化锌电子传输层的导电性能受到影响。另一方面，纳米材料表面缺陷的影响也是不容忽视的。与材料的体相相比，材料的表面具有非常多的缺陷，是缺陷的聚集地(如，空位，间隙原子等等)。在量子点发光二极管器件发光的过程中，表面缺陷作为非复合辐射中心会对激子产生明显的淬灭作用。而由于纳米氧化锌材料具有非常大的比表面积，使得纳米氧化锌表面的缺陷淬灭作用变得越发明显，大大降低了量子点发光二极管器件的发光效率。
技术问题
本发明提供一种电子传输薄膜及其制备方法、一种含有上述电子传输薄膜的QLED器 件，旨在解决现有氧化锌材料的电子传输层中，纳米氧化锌表面配体对电子传输有阻碍作用、以及纳米氧化锌表面缺陷对激子造成淬灭的问题。
技术解决方案
本发明实施例是这样实现的，第一方面，提供了一种电子传输薄膜，所述电子传输薄膜由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌。
第二方面，提供了一种电子传输薄膜的制备方法，包括以下步骤：
提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒；
在基板上沉积所述含有掺杂金属离子的氧化锌纳米颗粒的溶液，干燥成膜，得到电子传输薄膜。
第三方面，提供了一种发光二极管器件，所述发光二极管器件中电子传输薄膜；所述电子传输薄膜由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌；或者，
制备所述电子传输薄膜的方法，包括以下步骤：
提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒溶液；
在基板上沉积所述含有掺杂金属离子的氧化锌纳米颗粒溶液，干燥成膜，得到电子传输薄膜。
有益效果
本发明提供的电子传输薄膜，由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌。一方面，氧化锌纳米材料通过在纳米氧化锌材料表面富集掺杂金属离子，能够显著提高氧化锌纳米颗粒的稳定性，从而可以避免氧化锌纳米材料中表面配体的使用，进而避免表面配体的引入对电子在氧化锌材料中的传输造成的阻碍，进一步优化纳米氧化锌电子传输层的导电性能。另一方面，金属离子富集在纳米氧化锌表面的这种掺杂方式极大地减少了纳米氧化锌材料的表面缺陷，从而降低材料表面缺陷对激子的淬灭作用，进而整体提高了使用上述电子传输薄膜的发光二极管如QLED(量子点发光二极管)器件的发光效率和器件性能。
本发明提供的电子传输薄膜的制备方法，只需将所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒后，通过溶液法成膜即可。该方法非常简单，成本低廉，易于操作，对设备要求较低，且可重复性好，可实现大 规模生产。
本发明提供的发光二极管，由于含有上述电子传输薄膜，因此，可以显著提高器件的发光效率和器件性能。
附图说明
图1是本发明实施例提供的掺杂金属表面富集现象示意图；
图2是本发明实施例提供的电子传输薄膜的制备方法流程示意图；
图3是本发明实施例提供的发光二极管器件结构示意图。
本发明的实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
在本发明的描述中，需要理解的是，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或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
本发明实施例提供了一种电子传输薄膜，所述电子传输薄膜由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌。
当把一种金属离子掺杂到另一种金属氧化物主体材料中时，掺杂金属离子与主体材料之间可能形成的结构共有三种。第一种掺杂结构为：掺杂金属离子进入主体材料晶体结构中，占据主体金属离子的位点以形成固溶体(如专利文献CN201610939765.0，在金属氧化物主体材料中掺杂金属元素，掺杂离子进入主体材料晶体结构中，占据主体金属离子的位点)。掺杂的金属元素越多，自由电子浓度越高，进而使其导电性越强。第二种掺杂结构为：掺杂金属离子以杂质的形式从主体材料中析出，无法形成统一的结构。第三种掺杂结构为：掺杂金属离子聚焦在金属氧化物主体材料的表面区域，构成表面富集现象。表面富集是指掺杂金属离子的金属氧化物体系中，掺杂金属离子在金属氧化物表面区域聚集，导致金属离子在金属氧化物表面区域中的浓度高于在金属氧化物体相中的浓度的现象。
对于表面富集现象而言，如图1所示，掺杂金属离子绝大部分都进入了金属氧化物主体材料的表面区域，占据以主体金属离子空位为主的缺陷位，并维持了主体材料的晶体结构。也就是说，对于发生掺杂离子表面富集现象的金属氧化物主体材料而言，整个主体材料包括表面区域在内只含有单一晶相，并不存在除金属氧化物主体材料晶相结构以外的第二相。由此，可以保证整体材料性能的均一性。同时，当表面富集现象发生时，材料的表 面性能势必会发生明显的改变。一方面，根据吉布斯表面吸附方程，掺杂金属离子的表面富集现象会明显降低金属氧化物主体材料的表面能，进而显著增强金属氧化物主体材料的稳定性，尤其是具有极大比表面积的纳米金属氧化物主体材料的稳定性；另一方面，由于富集在表面的掺杂金属离子大量占据了金属氧化物主体材料表面的缺陷位，钝化了缺陷，使得金属氧化物主体材料表面的缺陷浓度大大下降。
有鉴于此，本发明实施例通过选择合适的掺杂金属离子对纳米氧化锌材料进行掺杂，使表面富集现象发生在纳米氧化锌颗粒的表面，从而显著提高氧化锌纳米颗粒的稳定性，避免表面配体使用以及由此所造成得对纳米氧化锌电子传输层导电性能的破坏；同时明显减少纳米氧化锌材料的表面缺陷浓度，降低纳米氧化锌材料表面缺陷对激子的淬灭作用，进而提高发光二极管如QLED器件的发光效率。
本发明实施例提供的电子传输薄膜，由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌。一方面，氧化锌纳米材料通过在纳米氧化锌材料表面富集掺杂金属离子，能够显著提高氧化锌纳米颗粒的稳定性，从而可以避免氧化锌纳米材料中表面配体的使用，进而避免表面配体的引入对电子在氧化锌材料中的传输造成的阻碍，进一步优化纳米氧化锌电子传输层的导电性能。另一方面，金属离子富集在纳米氧化锌表面的这种掺杂方式极大地减少了纳米氧化锌材料的表面缺陷，从而降低材料表面缺陷对激子的淬灭作用，进而整体提高了使用上述电子传输薄膜的发光二极管如QLED(量子点发光二极管)器件的发光效率和器件性能。
具体的，为了使掺杂金属离子富集在纳米氧化锌材料的表面，形成表面富集现象，所述掺杂金属离子的选择要满足两个要求。首先，所述掺杂金属离子的价态不为正二价，即所述掺杂金属离子的价态要与Zn 2+的价态不同。由于氧化锌纳米材料的表面由于大量缺陷的存在使得其并不呈电中性，而是会局部聚集一定的电荷。因此，当不等价金属离子掺杂到纳米氧化锌材料中时，不等价的掺杂金属离子会带来大量的自由电子或者空穴，而这些产生的自由电子或者空穴会倾向于富集在纳米材料的表面以中和表面电荷，从而促进掺杂金属离子富集在纳米氧化锌的表面。其次，所述掺杂金属离子的离子半径要明显大于Zn 2+的离子半径，具体的，所述掺杂金属离子的离子半径为Zn 2+半径的130％-200％，即所述掺杂金属离子与的半径差距需要在锌离子半径的30％以上，且不超过Zn 2+半径的两倍。离子半径在此范围的所述掺杂金属离子，进入氧化锌晶体结构中所引起的晶格畸变会因为较大的离子半径差异而变得异常剧烈。由此引起得严重动力学不稳定性会促使掺杂金属离子富集在纳米氧化锌的表面，占据以锌离子空位为主的缺陷位，而不是进入晶体结构内部替换锌离子位点，从而可以保证主体材料纳米氧化锌的金相结构，从而保证材料性能的均一性。 当所述掺杂金属离子的离子半径与Zn 2+的离子半径较为接近时，掺杂金属离子会轻易的进入氧化锌材料的晶体结构中，替代Zn 2+位点形成固溶体，影响原有的纳米氧化锌的电学性能。而当掺杂金属离子的半径达到Zn 2+离子半径的两倍及以上时，过大的掺杂金属离子难以进入氧化锌材料表面的锌离子空位，而是直接以第二相的形式从氧化锌材料的表面析出，对纳米氧化锌电子传输层的导电性能产生严重的破坏。本发明实施例的掺杂金属离子的可选择性很广，只要符合掺杂金属离子的价态要与Zn 2+的价态不同且掺杂金属离子的离子半径要明显大于Zn 2+的离子半径即可，因此，可根据实际应用中对于电子传输薄膜的具体要求进行有针对性的选择，具有很强的适用性和实用性。
优选的，所述掺杂金属离子为稀土金属离子，所述稀土金属离子作为掺杂材料，可以满足上述两个条件，且对于纳米氧化锌主体材料而言，具有较好的表面富集现象。
具体优选的，所述掺杂金属离子选自La 3+、Y 3+、Gd 3+、Ce 4+中的至少一种，采用优选的掺杂金属离子制备所述电子传输薄膜，可以成功将掺杂离子富集在纳米氧化锌材料的表面区域。本发明实施例中，La 3+、Y 3+、Gd 3+、Ce 4+与锌离子的离子半径差异如下表1所示，离子半径差异的计算公式为：
Figure PCTCN2018123505-appb-000001
其中，r表示半径，M n+表示掺杂金属离子。
表1
Figure PCTCN2018123505-appb-000002
本发明实施例中，除了掺杂离子离子的价态和离子半径会决定掺杂离子表面富集现象的发生以外，金属离子的掺杂摩尔浓度也会影响掺杂离子的表面富集现象。与材料体相中主体金属离子的位点数量相比，材料表面区域的主体金属离子空位等缺陷位是较为有限的。一旦掺杂离子数量超过可以占据的表面缺陷位的数量，多余的掺杂金属离子仍会以第二相的形式从主体材料中析出，破坏主体材料的原有性能。此外，掺杂金属离子的离子半径越大，其在主体材料表面区域可以占据的主体金属离子空位等缺陷位也就越少，在不产生第二相的情况下可用于掺杂的摩尔浓度也就越低。而另一方面，当掺杂金属离子的数量极少时，由于极少的掺杂离子数量不会引起明显的晶格畸变，因此掺杂金属离子仍可以进入氧化锌材料的体相中形成固溶体，而不会产生掺杂金属离子在氧化锌材料表面的富集现象。因此，对掺杂金属离子摩尔浓度的控制较为重要。
优选的，所述掺杂金属离子占电子传输薄膜中金属元素摩尔总浓度为0.05％-10％以内，但具体的，需结合掺杂金属离子的类型确定。当所述掺杂金属离子的掺杂摩尔浓度过低时，仍有部分掺杂金属离子可以进入到氧化锌纳米颗粒的体相中形成固溶体，此时掺杂金属离子在表面区域中数量与体相中数量是相对比较接近的，不利于掺杂离子表面富集现象的形成；而当所述掺杂金属离子的掺杂摩尔浓度过高时，掺杂金属离子进入氧化锌纳米颗粒体相所产生的剧烈的晶格畸变会促使过量新加入的掺杂金属离子全部富集在氧化锌纳米颗粒的表面，此时在氧化锌材料表面掺杂金属离子会以第二相的形式析出，严重影响氧化锌材料的电学性能。
本发明实施例只需要掺杂一种金属离子即可以同时实现改善氧化锌电子传输层的导电性能和提高量子点发光二极管器件的发光效率这两大功能，掺杂效果非常好。以所述电子传输薄膜为含有一种掺杂金属离子的纳米氧化锌电子传输薄膜为例，具体优选的，
当掺杂金属离子为La 3+时，以所述电子传输薄膜中金属元素摩尔总浓度为100％计，所述La 3+的掺杂摩尔浓度为0.05％～5％。当La 3+的掺杂摩尔浓度在此范围时，La 3+在氧化锌纳米颗粒表面区域中的摩尔数与La 3+在氧化锌纳米颗粒体相中的摩尔数的比值为4:1～30:1，La 3+在表面区域中数量与体相中数量的比值为4:1～30:1，可以形成掺杂离子的表面富集现象。在此范围内，掺杂金属离子的含量越高，表面富集现象越明显。
当掺杂金属离子为Y 3+时，以所述电子传输薄膜中金属元素摩尔总浓度为100％计，所述Y 3+的掺杂摩尔浓度为0.1％～10％。当Y 3+的掺杂摩尔浓度在此范围时，Y 3+在氧化锌纳米颗粒表面区域中的摩尔数与Y 3+在氧化锌纳米颗粒体相中的摩尔数的比值为2:1～40:1，Y 3+在表面区域中数量与体相中数量的比值为2:1～40:1，可以形成掺杂离子的表面富集现象。在此范围内，掺杂金属离子的含量越高，表面富集现象越明显。
当掺杂金属离子为Gd 3+时，以所述电子传输薄膜中金属元素摩尔总浓度为100％计，所述Gd 3+的掺杂摩尔浓度为0.1％～8％。当Gd 3+的掺杂摩尔浓度在此范围时，Gd 3+在氧化锌纳米颗粒表面区域中的摩尔数与Gd 3+在氧化锌纳米颗粒体相中的摩尔数的比值为3:1～35:1，Gd 3+在表面区域中数量与体相中数量的比值为3:1～35:1，可以形成掺杂离子的表面富集现象。在此范围内，掺杂金属离子的含量越高，表面富集现象越明显。
当掺杂金属离子为Ce 4+时，以所述电子传输薄膜中金属元素摩尔总浓度为100％计，所述Ce 4+的掺杂摩尔浓度为0.2％～10％。当Ce 4+的掺杂摩尔浓度在此范围时，Ce 4+在氧化锌纳米颗粒表面区域中的摩尔数与Ce 4+在氧化锌纳米颗粒体相中的摩尔数的比值为2:1～40:1，即Ce 4+在表面区域中数量与体相中数量的比值为2:1～40:1，可以形成掺杂离子的表面富集现象。在此范围内，掺杂金属离子的含量越高，表面富集现象越明显。
本发明实施例中，所述电子传输薄膜的厚度为10-100nm。当所述电子传输薄膜的厚度小于10nm时，膜层很容易被电子击穿，无法保证载流子的注入性能；当所述电子传输薄膜的厚度大于100nm时，则会阻碍电子的注入，影响器件的电荷注入平衡。
本发明实施例所述电子传输薄膜，可以通过下述方法制备获得。
相应的，如图2所示，本发明实施例提供了一种电子传输薄膜的制备方法，包括以下步骤：
S01.提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒；
S02.在基板上沉积所述含有掺杂金属离子的氧化锌纳米颗粒的溶液，干燥成膜，得到电子传输薄膜。
本发明实施例提供的电子传输薄膜的制备方法，只需将所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒后，通过溶液法成膜即可。该方法非常简单，成本低廉，易于操作，对设备要求较低，且可重复性好，可实现大规模生产。
具体的，上述步骤S01中，所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，由锌盐、含有掺杂金属离子的金属盐、碱溶于溶剂中形成。
其中，所述锌盐作为锌源，为制备含有掺杂金属离子的氧化锌纳米颗粒提供锌，具体的，所述锌盐包括但不局限于醋酸锌、硝酸锌、硫酸锌、氯化锌等中的一种。
所述含有掺杂金属离子的金属盐制备含有掺杂金属离子的氧化锌纳米颗粒提供掺杂金属离子，所述掺杂金属离子的类型满足：所述掺杂金属离子的价态不为正二价，且所述掺杂金属离子的离子半径为Zn 2+半径的130％-200％，具体可参见上文。优选的，所述掺杂金属离子选自稀土金属离子，具体优选自La 3+、Y 3+、Gd 3+、Ce 4+中的至少一种。具体的，所述含有掺杂金属离子的金属盐可选自硫酸镧、氯化镧、硝酸镧、醋酸镧、硫酸钇、氯化钇、醋酸钇、硝酸钇、硝酸钆、醋酸钆、硫酸钆、氯化钆、氯化铈、醋酸铈、硫酸铈、氯化铈及其金属盐水合物中的至少一种，但不限于此。
本发明实施例采用锌盐、含有掺杂金属离子的金属盐、碱的混合溶液制备含有掺杂金属离子的氧化锌纳米颗粒的反应历程为：锌盐中的锌离子和金属盐中的掺杂金属离子与碱液反应生成氢氧化物中间体，随后，氢氧化物中间体发生缩聚反应逐步生成掺杂氧化锌纳米粒子。其中，所述碱为反应提供氢氧根离子，具体的，所述碱选自氢氧化锂、氢氧化钠、氢氧化钾、TMAH、氨水、乙醇胺、乙二胺中的至少一种。
本发明实施例用于形成锌盐、含有掺杂金属离子的金属盐、碱的混合溶液的溶剂，可 以为有机溶剂或无机溶剂，具体可选自水、甲醇、乙醇、丙醇、丁醇、乙二醇、乙二醇单甲醚、DMSO中的至少一种，但不限于此。
优选的，所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液中，所述掺杂金属离子占金属离子总摩尔浓度的0.05％-10％。当所述掺杂金属离子的掺杂摩尔浓度过低时，仍有部分掺杂金属离子可以进入到氧化锌纳米颗粒的体相中形成固溶体，此时掺杂金属离子在表面区域中数量与体相中数量是相对比较接近的，不利于掺杂离子表面富集现象的形成；而当所述掺杂金属离子的掺杂摩尔浓度过高时，掺杂金属离子进入氧化锌纳米颗粒体相所产生的剧烈的晶格畸变会促使过量新加入的掺杂金属离子全部富集在氧化锌纳米颗粒的表面，此时在氧化锌材料表面掺杂金属离子会以第二相的形式析出，严重影响氧化锌材料的电学性能。
优选的，所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液中，氢氧根离子与金属离子的摩尔比为1.5:1～2.5:1，以确保掺杂氧化锌纳米粒子的形成和减少反应副产物的生成。当氢氧根离子与金属离子的摩尔比小于1.5：1时，金属盐显著过量，导致大量金属盐无法生成掺杂氧化锌纳米粒子；而当氢氧根离子与金属离子的摩尔比大于2.5：1时，碱液显著过量，过量的氢氧根离子与氢氧化物中间体形成稳定的络合物，无法缩聚生成掺杂氧化锌纳米颗粒。更优的，所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液中，氢氧根离子与金属离子的摩尔比选为1.7:1～1.9:1。
本发明实施例所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，可以将锌盐、含有掺杂金属离子的金属盐、碱加入溶剂中制备获得。作为一种优选方式，所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液的制备方法如下：
将锌盐和含有掺杂金属离子的金属盐溶解在溶剂中，得到盐溶液；
在所述盐溶液中加入碱液，得到锌盐、含有掺杂金属离子的金属盐、碱的混合溶液。
上述步骤在室温(10-30℃)条件下完成即可。其中，所述碱液可以为将碱进行溶解或将碱稀释在另一份与锌盐、含有掺杂金属离子的金属盐的溶解用溶剂相同或不同的溶剂中。
通过这种方式，可以先将锌盐和含有掺杂金属离子的金属盐充分溶解，混合均匀，在此条件下进一步添加碱液，可以促使反应均匀进行。
提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒的步骤包括：将所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，在0-70℃条件下，制备含有掺杂金属离子的氧化锌纳米颗粒。上述温度可以确保含有掺杂金属离子的氧化锌纳米颗粒的形成和获得良好的颗粒分散性。当反应温度低于0℃时，反应温度过低会显著减缓氧化锌纳米粒子的生成，甚至无法生成氧化锌纳米粒子，而只能得 到氢氧化物中间体；而当反应温度高于70℃时，所得纳米粒子的分散性较差，团聚严重，影响掺杂氧化锌胶体溶液的后期成膜。更优的，反应温度选在室温10～60℃。进一步的，反应时间为30-240min，以确保掺杂氧化锌纳米粒子的形成和控制纳米粒子的粒径。当反应时间少于30min时，反应时间过短，掺杂氧化锌纳米粒子形成不充分，并且所得纳米粒子的结晶性较差；而当反应时间超过4h时，过长的颗粒长大时间使生成的纳米粒子过大并且粒径不均匀，影响掺杂氧化锌胶体溶液的后期成膜。更优选的，反应时间为1～2h。
进一步的，在反应结束后，还包括在反应后的反应液中加入沉淀剂，混合溶液中产生白色沉淀(沉淀过程)，经离心处理，得到含有掺杂金属离子的氧化锌纳米颗粒。其中，沉淀剂与反应体系溶液的体积比为2：1～6：1，以确保在充分沉淀含有掺杂金属离子的氧化锌纳米颗粒的前提下，避免过多的沉淀剂破坏掺杂氧化锌粒子的溶解性。更优的，沉淀剂与反应体系溶液的体积比选为3：1～5：1。所述沉淀剂是极性较弱的溶剂中的一种，包括但不局限于乙酸乙酯、正己烷、正庚烷、丙酮等。将离心处理后所得白色沉淀再次溶于反应溶剂中，重复清洗多次以去除没有参与反应的反应物，收集最终所得白色沉淀，可溶于溶剂中得到具有较大离子半径的不等价金属离子掺杂氧化锌胶体溶液，即含有掺杂金属离子的氧化锌纳米颗粒的胶体溶液。
本发明实施例利用低温溶液法合成掺杂氧化锌胶体溶液，在低温溶液法的整个反应历程中(锌盐和含有掺杂金属离子的金属盐构成的混合溶液与碱液反应生成氢氧化物中间体，随后氢氧化物中间体发生缩聚反应逐步生成掺杂氧化锌纳米粒子)，掺杂氧化锌纳米粒子的生成都是在液相中进行。而液相的存在为掺杂金属离子在氧化锌纳米颗粒中的传质和扩散提供了优良的介质，使得符合前文所述两个要求的金属掺杂离子在短时间内就可以扩散到氧化锌纳米颗粒的表面，从动力学方面确保了掺杂金属离子表面富集现象的发生。
上述步骤S02中，在基板上沉积所述含有掺杂金属离子的氧化锌纳米颗粒的溶液，所述基板的选择没有严格限定，可以为用于沉积电子传输薄膜的普通基板，也可以是沉积好其他功能层，需要进一步沉积电子传输薄膜的功能基板，如沉积有层叠结合的阳极、发光层的功能基板，所述电子传输薄膜沉积在发光层上。
沉积方式没有严格限制，基于含有掺杂金属离子的氧化锌纳米颗粒的溶液的胶体溶液性质，采用溶液加工法即可。具体的，包括但不局限于旋涂法、刮涂法、印刷法、喷涂法、滚涂法、电沉积法等中的一种。
进一步的，将沉积有含有掺杂金属离子的氧化锌纳米颗粒的溶液的片子干燥成膜，所述干燥采用低温退火，此处选择的低温退火温度只需将掺杂氧化锌胶体溶液中的溶剂挥发即可，并不需要较高温度，具体根据掺杂氧化锌胶体溶液中溶剂的沸点来决定。具体的， 所述低温退火在室温～150℃条件下进行。较高的退火温度反而会对已沉积在基片上的量子点发光层产生破坏。所述低温退火过程需要在惰性气氛下进行，以保护沉积在基片上的功能层如量子点发光层不被破坏。
以及，本发明实施例还提供了一种发光二极管器件，所述发光二极管器件中含有电子传输薄膜，所述电子传输薄膜由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌；或者，
制备所述电子传输薄膜的方法，包括以下步骤：
提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒溶液；
在基板上沉积所述含有掺杂金属离子的氧化锌纳米颗粒溶液，干燥成膜，得到电子传输薄膜。
本发明实施例提供的发光二极管，由于含有电子传输薄膜。。所述电子传输薄膜由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌。一方面，氧化锌纳米材料通过在纳米氧化锌材料表面富集掺杂金属离子，能够显著提高氧化锌纳米颗粒的稳定性，从而可以避免氧化锌纳米材料中表面配体的使用，进而避免表面配体的引入对电子在氧化锌材料中的传输造成的阻碍，进一步优化纳米氧化锌电子传输层的导电性能。另一方面，金属离子富集在纳米氧化锌表面的这种掺杂方式极大地减少了纳米氧化锌材料的表面缺陷，从而降低材料表面缺陷对激子的淬灭作用，进而整体提高了使用上述电子传输薄膜的发光二极管的发光效率和器件性能。
本发明实施例中，所述电子传输薄膜、电子传输薄膜的制备方法及其优选情形如上文所述，为了节约篇幅，此处不再赘述。
具体的，所述发光成可以为有机发光层，也可以为量子点发光层。对应的，当所述发光层为有机发光层时，所述发光二极管器件为有机发光二极管(OLED)器件；当所述发光层为量子点发光层时，所述发光二极管为量子点发光二极管(QLED)器件。
优选的，所述发光二极管还包括空穴传输层，从而促进空穴的传输，促进载流子平衡。作为一种具体实施例，如图3所示，所述发光二极管包括层叠结合在衬底1上的阳极2、空穴传输层3、发光层4、电子传输层5和阴极6，其中，电子传输层为5按照上述方法制备得到的载流子传输薄膜。
具体的，所述衬底可采用硬质衬底或柔性衬底，具体的，可选用玻璃衬底。
所述阳极可以为ITO，但不限于此。
所述空穴传输层可采用本领域常规的空穴传输材料制成，包括但不限于TFB、PVK、 Poly-TPD、TCTA、CBP等或者为其任意组合的混合物，亦可以是其它高性能的空穴传输材料。
所述发光层为有机发光层时，发光层材料可选自常规的有机发光材料。当所述发光层为量子点发光层时，发光层材料的量子点可以为红、绿、蓝三种中的一种量子点，具体可以为CdS、CdSe、CdTe、ZnO、ZnS、ZnSe、ZnTe、GaAs、GaP、GaSb、HgS、HgSe、HgTe、InAs、InP、InSb、AlAs、AlP、CuInS、CuInSe、以及各种核壳结构量子点或合金结构量子点中的至少一种；也可以为常见的红、绿、蓝三种的任意一种量子点或者其它颜色如黄光量子点混合得到。所述量子点可以含镉或者不含镉。所述发光层的厚度优选为20-60nm。
所述电子传输层采用上述电子传输薄膜。
所述阴极采用金属阴极材料，如金属银或金属铝，或纳米银线或纳米铜线、采用所述纳米银线或所述纳米铜线，具有更小的电阻，有利于载流子顺利注入。所述阴极的厚度优选为15-30nm。
进一步的，可对得到的发光二极管进行封装处理。
相应的，本发明实施例提供了一种发光二极管的制备方法，包括以下步骤：
Q01.在阳极上制备发光层；
具体的，可以采用溶液法加工实现，即将发光层材料溶解成发光层材料溶液后，将发光层材料溶液沉积在阳极表面。进一步的，可以通过旋涂的方式将所述发光层材料溶液沉积成膜。具体的，将阳极基片置于匀胶机上，将配制好一定浓度的发光层材料溶液旋涂成膜，通过调节溶液的浓度、旋涂速度和旋涂时间来控制发光层的厚度，然后在适当温度下热退火处理。
优选的，在制备发光层之前，还包括在阳极上制备空穴传输层。
所述空穴传输层可以采用与发光层相同的方法制备，优选采用溶液加工法，如旋涂，并进一步通过调节溶液的浓度、旋涂速度和旋涂时间来控制膜厚，然后在适当温度下热退火处理。
Q02.在所述发光层上制备电子传输层；
在所述发光层上制备电子传输层，采用上述电子传输薄膜的方法制备获得，此处不再赘述。
Q03.在所述电子传输层上制备阴极。
具体的，将沉积完各功能层的衬底置于蒸镀仓中通过掩膜板热蒸镀阴极。
进一步的，对器件进行封装处理，封装条件优选在氧含量和水含量均低于0.1ppm的条件下进行，以保证器件的稳定性。
当然，所述发光二极管也可以采用另一种方法制备获得，具体的，所述发光二极管的制备方法，包括以下步骤：
Q01.在阴极上制备电子传输层；
Q02.在所述电子传输层上制备发光层；
Q03.在所述发光层上制备阴极。
各层的制备方法参照同上一种实施方式。
下面结合具体实施例进行说明。
实施例1
一种镧离子掺杂的纳米氧化锌电子传输薄膜，其制备方法包括以下步骤：
首先将适量的醋酸锌和硫酸镧加入到50ml甲醇溶剂中形成总浓度为0.1mol/L的混合盐溶液，其中La 3+的掺杂摩尔浓度为3％。同时将适量的氢氧化钾粉末溶解到另一份50ml甲醇溶剂中形成浓度为0.3mol/L的碱液。随后将混合盐溶液加热至50℃，并逐滴加入氢氧化钾溶液直到氢氧根离子与金属离子的摩尔比为1.7:1时停止。氢氧化钾溶液滴注完成后，将混合溶液在50℃下继续搅拌2h，得到一均匀透明溶液。随后，向均匀透明溶液中加入体积比为3：1的庚烷溶剂，使透明溶液中产生大量白色沉淀。将浑浊溶液以7000rpm的速度进行离心，所得白色沉淀再次溶于甲醇溶剂中。此清洗过程重复进行四次。最终所得白色沉淀溶于适量乙醇溶剂中，得到浓度为30mg/ml的镧离子掺杂的氧化锌胶体溶液。
将所得30mg/ml镧离子掺杂的氧化锌胶体溶液以旋涂的方法沉积在已依次沉积有阳极、空穴传输层、量子点发光层的基片上，并在100℃的氩气气氛下进行退火，即制得了镧离子掺杂的纳米氧化锌电子传输层。其中旋涂转速为3000rpm，旋涂时间为30s，以控制掺杂氧化锌电子传输层的厚度在50nm左右。
实施例2
一种钇离子掺杂的纳米氧化锌电子传输薄膜，其制备方法包括以下步骤：
首先将适量的硝酸锌和氯化钇加入到50ml乙醇溶剂中形成总浓度为0.1mol/L的混合盐溶液，其中Y3+的掺杂摩尔浓度为7％。同时将适量的氢氧化锂粉末溶解到另一份50ml乙醇溶剂中形成浓度为0.2mol/L的碱液。随后将混合盐溶液加热至40℃，并逐滴加入氢氧化锂溶液直到氢氧根离子与金属离子的摩尔比为1.9:1时停止。氢氧化锂溶液滴注完成后，将混合溶液在30℃下继续搅拌1h，得到一均匀透明溶液。随后，向均匀透明溶液中加入体积比为4：1的乙酸乙酯溶剂，使透明溶液中产生大量白色沉淀。将浑浊溶液以7000rpm 的速度进行离心，所得白色沉淀再次溶于乙醇溶剂中。此清洗过程重复进行四次。最终所得白色沉淀溶于适量乙醇溶剂中，得到浓度为30mg/ml的钇离子掺杂的氧化锌胶体溶液。
将所得30mg/ml钇离子掺杂的氧化锌胶体溶液以旋涂的方法沉积在已依次沉积有阳极、空穴传输层、量子点发光层的基片上，并在100℃的氩气气氛下进行退火，即制得了钇离子掺杂的纳米氧化锌电子传输层。其中旋涂转速为1500rpm，旋涂时间为30s，以控制掺杂氧化锌电子传输层的厚度在80nm左右。
实施例3
一种钆离子掺杂的纳米氧化锌电子传输薄膜，其制备方法包括以下步骤：
首先将适量的硫酸锌和醋酸钆加入到50ml DMSO溶剂中形成总浓度为0.1mol/L的混合盐溶液，其中Gd3+的掺杂摩尔浓度为5％。同时将适量的TMAH粉末溶解到另一份30ml乙醇溶剂中形成浓度为0.3mol/L的碱液。随后将混合盐溶液保持在室温下逐滴加入TMAH溶液直到氢氧根离子与金属离子的摩尔比为1.5:1时停止。TMAH溶液滴注完成后，将混合溶液在室温下继续搅拌2h，得到一均匀透明溶液。随后，向均匀透明溶液中加入体积比为4：1的正己烷溶剂，使透明溶液中产生大量白色沉淀。将浑浊溶液以7000rpm的速度进行离心，所得白色沉淀再次溶于乙醇溶剂中。此清洗过程重复进行四次。最终所得白色沉淀溶于适量乙醇溶剂中，得到浓度为30mg/ml的钆离子掺杂的氧化锌胶体溶液。
将所得30mg/ml钆离子掺杂的氧化锌胶体溶液以旋涂的方法沉积在已依次沉积有阳极、空穴传输层、量子点发光层的基片上，并在100℃的氮气气氛下进行退火，即制得了钆离子掺杂的纳米氧化锌电子传输层。其中旋涂转速为4500rpm，旋涂时间为30s，以控制掺杂氧化锌电子传输层的厚度在20nm左右。
实施例4
一种铈离子掺杂的纳米氧化锌电子传输薄膜，其制备方法包括以下步骤：
首先将适量的氯化锌和硝酸铈加入到50ml甲醇溶剂中形成总浓度为0.1mol/L的混合盐溶液，其中Ce4+的掺杂摩尔浓度为8％。同时将适量的乙二胺溶液稀释到另一份50ml甲醇溶剂中形成浓度为0.3mol/L的碱液。随后将混合盐溶液加热至50℃，并逐滴加入乙二胺溶液直到氢氧根离子与金属离子的摩尔比为1.8:1时停止。乙二胺溶液滴注完成后，将混合溶液在50℃下继续搅拌1h，得到一均匀透明溶液。随后，向均匀透明溶液中加入体积比为3：1的丙酮溶剂，使透明溶液中产生大量白色沉淀。将浑浊溶液以7000rpm的速度进行离心，所得白色沉淀再次溶于甲醇溶剂中。此清洗过程重复进行四次。最终所得白色沉 淀溶于适量乙醇溶剂中，得到浓度为30mg/ml的铈离子掺杂的氧化锌胶体溶液。
将所得30mg/ml铈离子掺杂的氧化锌胶体溶液以旋涂的方法沉积在已依次沉积有阳极、空穴传输层、量子点发光层的基片上，并在50℃的氮气气氛下进行退火，即制得了铈离子掺杂的纳米氧化锌电子传输层。其中旋涂转速为3000rpm，旋涂时间为30s，以控制掺杂氧化锌电子传输层的厚度在50nm左右。
实施例5-8
结合图2，一种正型QLED器件，从下而上依次包括衬底1、阳极2、空穴传输层3、量子点发光层4、电子传输层5、阴极6。其中，衬底1的材料为玻璃片，阳极2的材料为ITO基板，空穴传输层3的材料为TFB，电子传输层5的材料为具有较大离子半径的不等价金属离子掺杂氧化锌及阴极6的材料为Al。
所述正型QLED器件包括以下步骤：
旋涂空穴传输层于ITO基板上；
在空穴传输层上旋涂量子点发光层；
分别按照实施例1-4的方法，旋涂掺杂氧化锌胶体溶液于量子点发光层上并低温处理，以制得纳米氧化锌电子传输层；
蒸镀阴极于纳米氧化锌电子传输层上，得到量子点发光二极管。
实施例9-12
一种OLED器件，依次包括衬底、阳极、空穴传输层、有机发光层、电子传输层、阴极。其中，衬底的材料为玻璃片，阳极的材料为ITO基板，空穴传输层的材料为TFB，电子传输层的材料为具有较大离子半径的不等价金属离子掺杂氧化锌及阴极的材料为Al。
所述正型OLED器件包括以下步骤：
旋涂空穴传输层于ITO基板上；
在空穴传输层上旋涂有机发光层；
分别按照实施例1-4的方法，旋涂掺杂氧化锌胶体溶液于有机发光层上并低温处理，以制得纳米氧化锌电子传输层；
蒸镀阴极于纳米氧化锌电子传输层上，得到有机发光二极管。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (15)

  1. 一种电子传输薄膜，其特征在于，所述电子传输薄膜由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌。
  2. 如权利要求1所述的电子传输薄膜，其特征在于，所述掺杂金属离子的价态不为正二价，且所述掺杂金属离子的离子半径为Zn 2+半径的130％-200％。
  3. 如权利要求1所述的电子传输薄膜，其特征在于，所述掺杂金属离子为稀土金属离子。
  4. 如权利要求3所述的电子传输薄膜，其特征在于，所述掺杂金属离子选自La 3+、Y 3+、Gd 3+、Ce 4+中的至少一种。
  5. 如权利要求4所述的电子传输薄膜，其特征在于，所述电子传输薄膜为含有一种掺杂金属离子的纳米氧化锌电子传输薄膜，且以所述电子传输薄膜中金属元素摩尔总浓度为100％计，所述La 3+的掺杂摩尔浓度为0.05％～5％；或
    所述Y 3+的掺杂摩尔浓度为0.1％～10％；或
    所述Gd 3+的掺杂摩尔浓度为0.1％～8％；或
    所述Ce 4+的掺杂摩尔浓度为0.2％～10％。
  6. 如权利要求1所述的电子传输薄膜，其特征在于，所述电子传输薄膜的厚度为10-100nm。
  7. 一种电子传输薄膜的制备方法，其特征在于，包括以下步骤：
    提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒；
    在基板上沉积所述含有掺杂金属离子的氧化锌纳米颗粒的溶液，干燥成膜，得到电子传输薄膜。
  8. 如权利要求7所述的电子传输薄膜的制备方法，其特征在于，所述掺杂金属离子的价态不为正二价，且所述掺杂金属离子的离子半径为Zn 2+半径的130％-200％。
  9. 如权利要求7所述的电子传输薄膜的制备方法，其特征在于，所述掺杂金属离子选自La 3+、Y 3+、Gd 3+、Ce 4+中的至少一种；和/或
    所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液中，所述掺杂金属离子占金属离子总摩尔浓度的0.05％-10％。
  10. 如权利要求7所述的电子传输薄膜的制备方法，其特征在于，所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液中，氢氧根离子与金属离子的摩尔比为1.5:1～2.5:1。
  11. 如权利要求7所述的电子传输薄膜的制备方法，其特征在于，提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒的步骤包括：将所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，在0-70℃条件下反应30-240min，制备含有掺杂金属离子的氧化锌纳米颗粒。
  12. 如权利要求7所述的电子传输薄膜的制备方法，其特征在于，所述含有掺杂金属离子的金属盐选自硫酸镧、氯化镧、硝酸镧、醋酸镧、硫酸钇、氯化钇、醋酸钇、硝酸钇、硝酸钆、醋酸钆、硫酸钆、氯化钆、氯化铈、醋酸铈、硫酸铈、氯化铈及其金属盐水合物中的至少一种；和/或
    所述碱选自氢氧化锂、氢氧化钠、氢氧化钾、TMAH、氨水、乙醇胺、乙二胺中的至少一种。
  13. 如权利要求7所述的电子传输薄膜的制备方法，其特征在于，所述锌盐、含有掺杂金属离子的金属盐、碱的混合溶液的制备方法如下：
    将锌盐和含有掺杂金属离子的金属盐溶解在溶剂中，得到盐溶液；
    在所述盐溶液中加入碱液，得到锌盐、含有掺杂金属离子的金属盐、碱的混合溶液。
  14. 如权利要求7所述的电子传输薄膜的制备方法，其特征在于，提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒的步骤中，还包括在反应后的反应液中加入沉淀剂，经沉淀、离心处理，得到含有掺杂金属离子的氧化锌纳米颗粒。
  15. 一种发光二极管器件，其特征在于，所述发光二极管器件中含有电子传输薄膜，所述电子传输薄膜由含有掺杂金属离子的纳米氧化锌组成，所述掺杂金属离子的纳米氧化锌为表面富集所述金属离子的纳米氧化锌；或者，
    制备所述电子传输薄膜的方法，包括以下步骤：
    提供锌盐、含有掺杂金属离子的金属盐、碱的混合溶液，反应制备含有掺杂金属离子的氧化锌纳米颗粒溶液；
    在基板上沉积所述含有掺杂金属离子的氧化锌纳米颗粒溶液，干燥成膜，得到电子传输薄膜。
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