WO2020227890A1 - 发光器件及其制作方法 - Google Patents

发光器件及其制作方法 Download PDF

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WO2020227890A1
WO2020227890A1 PCT/CN2019/086646 CN2019086646W WO2020227890A1 WO 2020227890 A1 WO2020227890 A1 WO 2020227890A1 CN 2019086646 W CN2019086646 W CN 2019086646W WO 2020227890 A1 WO2020227890 A1 WO 2020227890A1
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layer
perovskite
light
emitting device
plasma treatment
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French (fr)
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韩登宝
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BOE Technology Group Co Ltd
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BOE Technology Group Co Ltd
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Priority to JP2020572857A priority Critical patent/JP2022539623A/ja
Priority to US16/765,609 priority patent/US11355709B2/en
Priority to CN201980000630.XA priority patent/CN112292769B/zh
Priority to PCT/CN2019/086646 priority patent/WO2020227890A1/zh
Priority to EP19929088.3A priority patent/EP3972002A4/en
Publication of WO2020227890A1 publication Critical patent/WO2020227890A1/zh
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    • 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
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/421—Thermal treatment, e.g. annealing in the presence of a solvent vapour using coherent electromagnetic radiation, e.g. laser annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers

Definitions

  • At least one embodiment of the present disclosure relates to a light emitting device and a manufacturing method thereof.
  • Perovskite materials generally refer to materials with a molecular formula of ABX 3 , which have excellent optical and optoelectronic properties.
  • Perovskite electroluminescent devices made of perovskite materials have high external quantum efficiency and continuously adjustable emission spectra. The characteristics of high color purity and low cost make it widely used in fields such as display and lighting.
  • the current Perovskite light-emitting diodes (PeLEDs) prepared based on perovskite materials have disadvantages such as more complex structure and lower external quantum efficiency. Compared with the currently widely used organic electroluminescence Devices (Organic light-emitting diodes, OLED) still have a lot of room for improvement.
  • the formation of a high-quality perovskite luminescent film has strict requirements on the surface flatness and wettability of the underlying substrate, which limits the choice of underlying substrate material, which further limits the perovskite power Design of the structure of the electroluminescent device.
  • At least one embodiment of the present disclosure provides a method for manufacturing a light emitting device, the method includes: forming a functional layer, wherein the functional layer has a first surface; performing plasma treatment on the first surface of the functional layer; A perovskite-type light-emitting layer is formed on the second surface.
  • the plasma treatment includes at least one of oxygen plasma treatment, nitrogen plasma treatment, and argon plasma treatment.
  • the gas pressure for the plasma treatment is 20 Pa-50 Pa, and the plasma treatment time is 2-5 minutes.
  • the functional layer is a hole injection layer
  • the material of the functional layer includes poly(3,4-ethylenedioxythiophene)-polystyrene Sulfonic acid (PEDOT:PSS), polyvinylcarbazole (PVK), poly((9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(on At least one of (butylphenyl)) diphenylamine)] (TFB) and poly[bis(4-phenyl)(4-butylphenyl)amine] (Poly-TPD).
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene)-polystyrene Sulfonic acid
  • PVK polyvinylcarbazole
  • PVK poly((9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(on At least one
  • the functional layer is an electron injection layer
  • the material of the functional layer includes zinc oxide (ZnO).
  • the perovskite-type light-emitting layer includes a material with a molecular formula of ABX 3 ;
  • A is a metal cation or an alkylammonium salt ion, and B is a metal cation, X is a halogen anion.
  • A includes at least one of an organic amine group, an amidine group, Cs + , K + , and Rb + ;
  • B includes Pb 2+ , Sn 2+, Ge 2+, Ga 2+, in 3+, Cd 2+, Hg 2+, Ni 2+, Mn 2+, Bi 3+, Sb 3+, at least one of;
  • forming the perovskite-type light-emitting layer on the first surface after the plasma treatment includes: using AX n , BX m As a solute dissolved in the first solvent to form a precursor solution of the perovskite-type light-emitting layer; and using the precursor solution of the perovskite-type light-emitting layer on the first surface after the plasma treatment
  • AX n reacts with BX m to generate ABX 3
  • both m and n are positive integers.
  • the precursor solution of the titanium ore-type light-emitting layer is used to form the titanium ore on the first surface after the plasma treatment.
  • the type light emitting layer includes: spin-coating the precursor solution of the perovskite type light emitting layer on the first surface after the plasma treatment; A second solvent is added to the precursor solution of the light-emitting layer, wherein the second solvent and the first solvent are immiscible; and annealing treatment is performed to obtain the perovskite-type light-emitting layer.
  • the first solvent is anhydrous N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), ⁇ - At least one of butyrolactone (GBL) and acetonitrile (ACN), and the second solvent includes at least one of toluene, chloroform, chlorobenzene, and acetone.
  • DMF N,N-dimethylformamide
  • DMSO dimethylsulfoxide
  • GBL butyrolactone
  • ACN acetonitrile
  • the second solvent includes at least one of toluene, chloroform, chlorobenzene, and acetone.
  • the temperature of the annealing treatment is 70° C. to 80° C.
  • the time of the annealing treatment is 20 to 40 min.
  • the contact angle between the precursor solution of the perovskite-type light-emitting layer and the first surface after the plasma treatment is less than 16° .
  • the method for manufacturing a light emitting device further includes: dissolving AI and B(I) m as solutes in the first solvent to form a first precursor solution, and using the first precursor
  • the body solution forms a red light-emitting perovskite-type luminescent layer on the first surface after the plasma treatment, wherein AI reacts with B(I) m to form ABI 3 .
  • the method for manufacturing a light-emitting device further includes: dissolving ABr and B(Br) m as solutes in the first solvent to form a second precursor solution, and using the The second precursor solution forms a perovskite-type luminescent layer emitting green light on the first surface after the plasma treatment, and ABr reacts with B(Br) m to form AB(Br) 3 .
  • the method for manufacturing a light-emitting device further includes: dissolving ACl and B(Br) m as solutes in the first solvent to form a third precursor solution, and after passing through the plasma A perovskite-type light emitting layer emitting blue light is formed on the treated first surface, and ACl reacts with B(Br) m to form AB(Br) 2 Cl.
  • the method for manufacturing a light emitting device provided by at least one embodiment of the present disclosure further includes: before performing the plasma treatment, performing annealing treatment on the functional layer.
  • At least one embodiment of the present disclosure further provides a light-emitting device, which includes a functional layer and a perovskite-type light-emitting layer.
  • the functional layer has a first surface; the perovskite-type light-emitting layer is in direct contact with the first surface of the functional layer; and the first surface of the functional layer has hydrophilic groups.
  • the plasma includes at least one of oxygen plasma, nitrogen plasma, and argon plasma.
  • the surface roughness of the perovskite-type light-emitting layer is less than 2 nm.
  • the functional layer is a hole injection layer
  • the material of the functional layer includes poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), polyvinylcarbazole (PVK), poly((9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylbenzene) Yl)) diphenylamine)] (TFB), at least one of poly[bis(4-phenyl)(4-butylphenyl)amine] (Poly-TPD).
  • the material of the functional layer is poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), and the PEDOT:PSS
  • the surface close to the perovskite-type light-emitting layer has the hydrophilic group and is in direct contact with the perovskite-type light-emitting layer.
  • the light emitting device further includes: an electron injection layer, a modified electrode, a first electrode, and a second electrode.
  • the electron injection layer is located on the side of the perovskite type light-emitting layer away from the hole injection layer;
  • the modified electrode is located on the side of the electron injection layer away from the perovskite type light-emitting layer; the hole injection layer ,
  • the perovskite-type light-emitting layer, the electron injection layer and the modified electrode are sandwiched between the first electrode and the second electrode.
  • the functional layer is an electron injection layer
  • the material of the functional layer includes zinc oxide (ZnO)
  • the ZnO is close to the perovskite light-emitting layer.
  • the surface has the hydrophilic group and is in direct contact with the perovskite-type light-emitting layer.
  • the light-emitting device further includes: a hole injection layer, a modified electrode, a first electrode, and a second electrode.
  • the hole injection layer is located on the side of the perovskite light emitting layer away from the electron injection layer;
  • the modified electrode is located on the side of the electron injection layer away from the perovskite light emitting layer;
  • the hole injection layer The perovskite-type light-emitting layer, the electron injection layer and the modified electrode are sandwiched between the first electrode and the second electrode.
  • FIGS. 1A-1F are schematic diagrams of a method for manufacturing a light-emitting device according to an embodiment of the disclosure.
  • 1G-1K are schematic diagrams of another method for manufacturing a light-emitting device according to an embodiment of the disclosure.
  • 2A is a flowchart of a method for manufacturing a light emitting device according to an embodiment of the present disclosure
  • 2B is a flowchart of another method for manufacturing a light-emitting device according to an embodiment of the present disclosure
  • 3A-3B are comparison diagrams of the contact angle measurement results of the first surface of the functional layer before and after plasma treatment in an embodiment of the disclosure
  • FIG. 4 is a graph showing a comparison of transmittance before and after plasma treatment of the functional layer in an embodiment of the disclosure
  • Fig. 5 is a surface SEM image of a red-emitting perovskite light-emitting layer in an embodiment of the disclosure
  • Fig. 6 is an AFM image of the surface of the red-emitting perovskite light-emitting layer in an embodiment of the disclosure
  • Fig. 7 is an absorption and photoluminescence spectrum curve of a red-emitting perovskite light-emitting layer in an embodiment of the disclosure
  • FIG. 8 is a surface SEM image of a perovskite light emitting layer emitting green light in an embodiment of the disclosure
  • FIG. 9 is an AFM image of the surface of the perovskite light-emitting layer emitting green light in an embodiment of the disclosure.
  • FIG. 10 is an absorption and electroluminescence spectrum curve of a perovskite luminescent layer emitting green light in an embodiment of the disclosure
  • FIG. 11 is a current density/luminance-voltage relationship curve of a green light emitting device manufactured according to a method provided by an embodiment of the present disclosure
  • FIG. 12 is an external quantum efficiency/current efficiency-current density relationship curve of a green light emitting device manufactured according to a method provided by an embodiment of the present disclosure
  • FIG. 13 is an electroluminescence spectrum of a light emitting device emitting green light provided by an embodiment of the present disclosure
  • FIG. 14 is a schematic structural diagram of a light emitting device provided by an embodiment of the disclosure.
  • FIG. 15 is a schematic structural diagram of another light-emitting device provided by an embodiment of the disclosure.
  • An embodiment of the present disclosure provides a method for manufacturing a light emitting device, the method includes: forming a functional layer, wherein the functional layer has a first surface; performing plasma treatment on the first surface of the functional layer; and after the plasma treatment A perovskite-type light-emitting layer is formed on the first surface of the device.
  • FIGS. 1A-1F are schematic diagrams of a manufacturing method of a light-emitting device provided by an embodiment of the present disclosure
  • FIG. 2A is a flowchart of a manufacturing method of a light-emitting device provided by an embodiment of the present disclosure.
  • the manufacturing method of the light emitting device provided in this embodiment includes the following steps.
  • a base substrate 1 is provided.
  • the base substrate 1 is cleaned.
  • deionized water, acetone solution, ethanol solution, and isopropanol solution are used to wipe and ultrasonically clean the base substrate 1 in sequence.
  • nitrogen is used to blow dry; the cleaned base substrate 1 is subjected to plasma pretreatment, In order to enhance the wettability of the surface of the base substrate 1.
  • the plasma treatment includes at least one of oxygen plasma treatment, nitrogen plasma treatment, and argon plasma treatment.
  • the material of the base substrate 1 may be inorganic materials such as glass, quartz, indium tin oxide (ITO), or organic materials such as polyimide, which is not limited in the embodiments of the present disclosure.
  • the electrode 21 is formed on the base substrate 1.
  • the electrode is, for example, a transparent electrode or an opaque electrode.
  • a functional layer 3 is formed on the side of the first electrode 21 away from the base substrate 1, and the functional layer 3 has a first surface 31.
  • the functional layer 3 is a hole injection layer, and the material of the functional layer 3 includes poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), polyvinylcarbazole (PVK), poly((9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine))(TFB ) At least one of.
  • the first surface 31 of the functional layer 3 is plasma treated.
  • the plasma treatment includes at least one of oxygen plasma treatment, nitrogen plasma treatment, and argon plasma treatment.
  • the material of the functional layer 3 is poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), and oxygen plasma treatment is performed on the first surface 31 of the functional layer 3 as an example.
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid
  • oxygen plasma treatment is performed on the first surface 31 of the functional layer 3 as an example.
  • the device with the functional layer 3 prepared is moved to the cavity of the plasma cleaning machine, and after multiple vacuum/oxygen operations, an oxygen environment is ensured in the cavity. Then, the treatment effect is adjusted by adjusting parameters such as the power of the oxygen plasma treatment, the gas pressure in the cavity, and the oxygen plasma treatment time.
  • the gas pressure for plasma treatment is 20 Pa-50 Pa to obtain a suitable plasma concentration; the plasma treatment time is 2-5 minutes; the plasma treatment power is 30W-40W.
  • the power refers to the power of the plasma processing equipment. The time and power of the plasma treatment will affect the amount of protrusions on the first surface 31 and thus the specific surface area.
  • the first surface 31 of the functional layer 3 can have an appropriate specific surface area and hydrophilic groups such as nitrogen or oxygen, so that the first surface 31 of the functional layer 3 is better modified, which is beneficial to improve The performance of the perovskite-type light-emitting layer formed on the first surface 31 of the functional layer 3 subsequently.
  • a perovskite-type light-emitting layer 4 is formed on the first surface 31 after plasma treatment.
  • a precursor solution of the perovskite-type light-emitting layer is first prepared, and then the precursor solution of the perovskite-type light-emitting layer is used to form the perovskite-type light-emitting layer 4 on the first surface 31 after plasma treatment.
  • the wettability of the precursor solution of the perovskite-type light-emitting layer to the first surface 31 is improved, and the contact angle is reduced, thereby forming a perovskite-type
  • the light-emitting layer 4 is flatter, for example, the surface roughness of the perovskite-type light-emitting layer is less than 2 nm, so that the light-emitting performance is improved, such as the external quantum efficiency of the light-emitting device.
  • the light transmittance of the functional layer 3 after plasma treatment is improved, which is beneficial to improve the light utilization efficiency of the light emitting device.
  • the perovskite-type light-emitting layer 4 in the present disclosure is different from the organic light-emitting diode (OLED) light-emitting layer.
  • the perovskite-type light-emitting layer 4 includes a material with a molecular formula of ABX 3 .
  • A is a metal cation or an alkylammonium salt ion
  • B is a metal cation
  • X is a halogen anion.
  • B includes Pb 2+ , Sn 2+ , Ge 2+ , Ga 2+ , In 3+ , Cd 2+ , Hg 2+ , Ni 2+, Mn 2+, Bi 3+, Sb 3+, at least one of; comprising X-Cl - at least one of -, Br -, I.
  • forming the perovskite-type light-emitting layer 4 on the first surface 31 after plasma treatment includes: using AX n and BX m as solutes to be dissolved in a first solvent to form a precursor solution of the perovskite-type light-emitting layer And using the precursor solution of the perovskite-type light-emitting layer to form the perovskite-type light-emitting layer 4 on the first surface 31 after plasma treatment.
  • AX n reacts with BX m to form ABX 3 , and both m and n are positive integers.
  • using the precursor solution of the ilmenite luminescent layer to form the ilmenite luminescent layer 3 on the plasma-treated first surface 31 includes: spin coating the precursor solution of the perovskite luminescent layer on the plasma On the treated first surface 31; adding a second solvent to the precursor solution of the perovskite-type luminescent layer during the spin coating process, wherein the second solvent and the first solvent are immiscible; and performing annealing treatment to obtain calcium Titanite type luminescent layer 4.
  • the first solvent is at least one of anhydrous N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ⁇ -butyrolactone (GBL), and acetonitrile (ACN).
  • the two solvents include at least one of toluene, chloroform, chlorobenzene, and acetone.
  • the first solvent and the second solvent are not limited to the above types, and can be specifically determined according to the formed titanium ore material.
  • the method for manufacturing a light-emitting device further includes: adding a halogenated amine ligand material to the precursor solution for forming the perovskite light-emitting layer; and adding the halogenated amine ligand material
  • the precursor solution of the perovskite luminescent layer is spin-coated on the first surface 31 after plasma treatment.
  • the halogenated amine ligand material is a brominated ammonium ligand material.
  • a chlorinated ammonium ligand material or an iodinated amine ligand material can also be used.
  • brominated ammonium ligand materials include: brominated 3,3-diphenylpropylamine, ethylamine bromide, butylamine bromide, octylamine bromide, phenethylamine bromide, and amphetamine bromide Any one or more.
  • brominated ammonium ligand material as brominated 3,3-diphenylpropylamine (DPPA-Br) as an example, the preparation of this ligand material will be described.
  • DPPA 3,3,diphenylpropylamine
  • the second solvent is added to the precursor solution of the perovskite-type light-emitting layer to crystallize the perovskite material, and the halogenated amine ligand material is grafted onto the crystalline calcium.
  • a perovskite film is formed.
  • the second solvent is added dropwise at 6 seconds, for example, the second solvent is added dropwise within 1 minute to obtain a better crystallization effect of the perovskite material.
  • the temperature of the annealing treatment is 70°C to 80°C, and the time of the annealing treatment is 20 to 40 minutes, which has achieved the desired effect.
  • the contact angle between the precursor solution of the perovskite-type light-emitting layer and the plasma-treated first surface is less than 16°.
  • 3A-3B are comparison diagrams of the contact angle measurement results before and after plasma treatment of the first surface of the functional layer in an embodiment of the disclosure.
  • plasma treatment of the first surface 31 of the functional layer 3 can improve the wettability of the precursor solution of the perovskite-type light-emitting layer to the first surface 31, and reduce the formation of the precursor solution on the plasma
  • the contact angle of the first surface 31 of the functional layer 3 is bulk-treated, so that the perovskite-type light-emitting layer 4 obtained after the annealing treatment is flatter and the light-emitting performance is improved, for example, the external quantum efficiency of the light-emitting device is improved. Therefore, when the functional layer 3 is the above-mentioned hole injection layer, it also has the function of a hole transport layer, and there is no need to separately provide a hole transport layer, which simplifies the manufacturing process and structure of the light emitting device.
  • FIG. 4 is a graph showing a comparison of transmittance before and after plasma treatment of the functional layer in an embodiment of the disclosure.
  • the light transmittance of the functional layer 3 after plasma treatment is higher than that before the plasma treatment.
  • the light transmittance of the functional layer 3 after plasma treatment can reach 96% or more. It can be proved that plasma treatment of the first surface 31 of the functional layer 3 can increase the light transmittance of the functional layer 3, thereby improving the light utilization efficiency of the light emitting device.
  • the manufacturing method of the light-emitting device includes: forming a perovskite-type light-emitting layer that emits red light, a perovskite-type light-emitting layer that emits green light, and a perovskite that emits blue light on the first surface 31 after plasma treatment.
  • Type light-emitting layer to achieve color lighting or color display.
  • Al and B(I) m are used as solutes to be dissolved in the first solvent to form a first precursor solution, and the first precursor solution is used to form red-emitting perovskite on the first surface after plasma treatment.
  • Mineral-type luminescent layer where AI reacts with B(I) m to form ABI 3 .
  • B(I) m is PbI 2
  • the first solvent is anhydrous DMF as an example.
  • the first precursor solution is spin-coated on the oxygen plasma-treated first surface 31.
  • the spin-coating speed reaches 4000 rpm, for example, in the 6th second after the start, the first precursor solution is quickly dropped.
  • the second solvent (anti-solvent) is added, and the second solvent is added dropwise within 1 second to quickly form a perovskite-type film and control the formation of perovskite crystal grains in the perovskite-type film.
  • a red-emitting perovskite luminescent layer is obtained after annealing at 80° C.
  • the surface morphology of the red-emitting perovskite luminescent layer is shown in Figures 5 and 6.
  • the prepared red-emitting perovskite luminescent layer is very dense without obvious defects, the surface is very flat and uniform, and the surface average roughness Low, only 0.57nm. Fig.
  • FIG. 7 shows the absorption and electroluminescence spectrum curves of the red-emitting perovskite light-emitting layer. It can be seen from Fig. 7 that the emission peak is located at 675 nm, and the half-peak width is only 50 nm.
  • the red-emitting perovskite luminescent layer can be used to obtain a higher color gamut.
  • ABr and B(Br) m are used as solutes to be dissolved in the first solvent to form a second precursor solution, and the second precursor solution is used to form green-emitting perovskite on the first surface after plasma treatment.
  • the mineral light-emitting layer ABr reacts with B(Br) m to form AB(Br) 3 .
  • B(Br) m is PbBr 2
  • the first solvent is anhydrous DMF as an example.
  • the second precursor solution is spin-coated on the first surface 31 treated by oxygen plasma.
  • the spin-coating speed reaches 4000 rpm, for example, in the 6th second after the start, the second precursor solution is sprayed quickly.
  • the second solvent (anti-solvent) is added, and the second solvent is added dropwise within 1 second to quickly form a perovskite-type film and control the formation of perovskite crystal grains in the perovskite-type film.
  • a perovskite luminescent layer emitting green light is obtained after annealing at 80°C.
  • the surface morphology of the green-emitting perovskite luminescent layer is shown in Figures 8 and 9.
  • the prepared green-emitting perovskite luminescent layer is very dense without obvious defects, the surface is very flat and uniform, and the surface average roughness Low, only 1.7nm.
  • Figure 10 shows the absorption and electroluminescence spectrum curves of the perovskite luminescent layer emitting green light. It can be seen from FIG. 10 that the emission peak is located at 526 nm, and the half-peak width is only 22 nm.
  • the green-emitting perovskite light-emitting layer can be used to obtain a higher color gamut.
  • ACl and B(Br) m are used as solutes to be dissolved in the first solvent to form a third precursor solution, and a perovskite-type light-emitting layer emitting blue light is formed on the first surface after plasma treatment.
  • ACl and B(Br) m reacts to form AB(Br) 2 Cl.
  • B(Br) m is PbBr 2
  • the first solvent is anhydrous DMF as an example.
  • NH 2 CH NH 2 Cl, PbBr 2 , and amine halide are dissolved in anhydrous DMF at a molar ratio of 1:1:0.8 to form a third precursor solution with a concentration of 0.2M.
  • the third precursor solution is spin-coated on the oxygen plasma treated first surface 31.
  • the second solvent antioxidant
  • the second solvent is added, and the second solvent is added dropwise within 1 second to quickly form a perovskite-type film and control the formation of perovskite crystal grains in the perovskite-type film.
  • a blue-emitting perovskite light-emitting layer is obtained.
  • the blue light-emitting perovskite light-emitting layer is very compact, has no obvious defects, has a very flat and uniform surface, and has a low average surface roughness, and the emission peak of the blue light emitted by the perovskite layer is located at 460nm-480nm.
  • FIG. 11 and 12 are the performance parameter curves of the green light perovskite electroluminescent device prepared according to the method provided by the above embodiment of the present disclosure.
  • the turn-on voltage of the light emitting device is 2.9V, and the maximum brightness exceeds 4.6V. 8000cd/m 2 .
  • the external quantum efficiency of the light-emitting device can reach more than 16%, and the current efficiency exceeds 60 cd/A.
  • Figure 13 is the curve of the electroluminescence spectrum of a light emitting device emitting green light with voltage. It can be seen from Figure 13 that at 526nm where the peak position is always maintained, the half-width of the spectrum is 23nm, which has very high color purity. It is consistent with the photoluminescence spectrum shown in FIG. 10. Moreover, the peak position does not change with the increase of the voltage applied to the light-emitting device, which has high spectral stability.
  • the perovskite-type light-emitting layer is composed of nano-sized perovskite nanocrystals, for example, the size of the crystalline perovskite material is greater than 20 nm.
  • the perovskite-type light-emitting layer can be composed of nano-sized perovskite quantum dots, for example, the size of the perovskite quantum dots is less than 20 nm.
  • the size of the formed perovskite material after crystallization can be controlled by controlling the amount of the halogenated ligand material added and the amount of the second solvent.
  • perovskite quantum dots have better luminous efficiency; if the amount of halogenated ligand material is small, it is easy to form perovskite nanometers. Crystal, perovskite nanocrystals have better carrier transport capabilities. Those skilled in the art can design as needed.
  • the manufacturing method of the light emitting device further includes: forming an electron injection layer located on the side of the perovskite light emitting layer 4 away from the hole injection layer 3. 5. As shown in Fig. 1D; forming a modified electrode 6, as shown in Fig. 1E; and forming a second electrode 22, as shown in Fig. 1F.
  • the hole injection layer 3, the perovskite type light emitting layer 4 and the electron injection layer 5 are sandwiched between the first electrode 21 and the second electrode 22.
  • the modified electrode 6 is located on the side of the electron injection layer 5 away from the perovskite light-emitting layer 4.
  • the material of the modified electrode 6 is LiF or CsCO 3 , to adjust the rate of electron injection, for example, to slow down the rate of electron injection, so as to balance the rate of hole injection and the rate of electron injection, so as to achieve better luminous effect and energy efficiency.
  • the second electrode 22 may include a plurality of parts arranged at intervals, as shown in FIG. 1F; the second electrode 22 may also be a whole surface electrode.
  • the material of the electron injection layer 5 includes zinc oxide (ZnO).
  • ZnO zinc oxide
  • the material of the electron injection layer 5 is ZnO.
  • ZnO has a good electron injection function and an electron transport function, so that the electron transport layer can be omitted.
  • the electron injection layer 5 includes a zinc oxide layer and a polyethyleneimine (PEI) layer that are stacked, and the polyethyleneimine layer is located on the side of the zinc oxide layer away from the perovskite light-emitting layer 4.
  • the PEI layer can adjust the energy level of ZnO and slow down the rate of electron injection, thereby balancing the rate of hole injection and the rate of electron injection to achieve better luminous effects and energy efficiency.
  • the method of manufacturing the light emitting device further includes: before plasma treatment, annealing the functional layer 3 to release the functional energy layer 3 and other base substrates
  • the stress of each structure on 1 further improves the stability of the perovskite-type luminescent layer formed on the functional layer 3 later.
  • the other steps of this embodiment are the same as those in the previous embodiment, please refer to the previous description, and will not be repeated here.
  • 1G-1K are schematic diagrams of another method for manufacturing a light-emitting device according to an embodiment of the disclosure.
  • the functional layer 30 is an electron injection layer.
  • the manufacturing method of the light emitting device includes: sequentially forming a first electrode 210, a modified electrode 60 and a functional layer 30 on a base substrate 10.
  • the functional layer 30 is an electron injection layer, and its material includes zinc oxide (ZnO).
  • the manufacturing method of the light emitting device further includes: performing plasma treatment on the first surface 301 of the functional layer 30 (ie, the electron injection layer), which is the same as the plasma treatment performed on the electron injection layer 30 in the previous embodiment.
  • the processing is the same, please refer to the previous description.
  • the manufacturing method of the light-emitting device further includes: forming a perovskite-type light-emitting layer 40 on the first surface 301 of the electron injection layer 30 that has undergone plasma treatment.
  • a perovskite-type light-emitting layer 40 For the specific method of forming the perovskite-type light-emitting layer 40, please refer to the previous description.
  • the manufacturing method of the light emitting device further includes: forming a hole injection layer 50 located on the side of the perovskite light emitting layer 40 away from the electron injection layer 30, as shown in FIG. 1J; and forming a second electrode 220, as shown in FIG. 1K Shown.
  • the hole injection layer 50, the perovskite type light emitting layer 40 and the electron injection layer 30 are sandwiched between the first electrode 21 and the second electrode 22.
  • the electron injection layer 30 is a zinc oxide layer
  • plasma treatment is performed on the first surface 301 of the zinc oxide layer
  • the calcium is formed on the first surface 301 of the zinc oxide layer after the plasma treatment.
  • Titanite type light-emitting layer 40 for example, in another example, the electron injection layer 30 includes a zinc oxide layer and a polyethylene imine (PEI) layer that are stacked, and the polyethylene imine layer is located near the base substrate of the zinc oxide layer
  • PEI polyethylene imine
  • plasma treatment is performed on the first surface 301 of the zinc oxide layer, and the perovskite-type light-emitting layer 40 is formed on the first surface 301 of the zinc oxide layer after the plasma treatment.
  • At least one embodiment of the present disclosure further provides a light-emitting device, which is formed according to any method for manufacturing a light-emitting device provided in the embodiments of the present disclosure.
  • the light-emitting device includes a functional layer and a perovskite-type light-emitting layer.
  • the functional layer has a first surface; the perovskite-type light-emitting layer is in direct contact with the first surface of the functional layer; and the first surface of the functional layer has hydrophilic groups.
  • FIG. 14 is a schematic structural diagram of a light emitting device provided by an embodiment of the present disclosure.
  • the light-emitting device is formed according to any method for manufacturing a light-emitting device provided by the embodiments of the present disclosure.
  • the light-emitting device includes: a functional layer 3 and a perovskite-type light-emitting layer 4.
  • the functional layer 3 has a first surface 31; the perovskite-type light-emitting layer 4 is in direct contact with the first surface 31 of the functional layer 3; and the first surface 31 of the functional layer 3 has hydrophilic groups.
  • the hydrophilic group includes an oxygen-containing hydrophilic group or a nitrogen-containing hydrophilic group.
  • Oxygen-containing hydrophilic groups for example, hydroxyl (OH -), a nitrogen-containing hydrophilic groups such as amino groups.
  • the hydrophilic group is formed by plasma treatment on the first surface 31.
  • the plasma includes at least one of oxygen plasma, nitrogen plasma, and argon plasma.
  • the perovskite-type light-emitting layer 4 is in direct contact with the first surface 31 of the functional layer 3, which can make the first surface 31 rougher, thereby forming perovskite on the first surface 31 .
  • the wettability of the precursor solution for forming the perovskite-type light-emitting layer 4 to the first surface 31 is improved, so that the perovskite-type light-emitting layer 4 is more flat, for example, perovskite-type light-emitting layer 4
  • the surface roughness of the mineral type light-emitting layer is less than 2 nm, so its light-emitting performance is improved. For example, the external quantum efficiency of the light-emitting device is improved. With the change of the voltage applied to the perovskite-type light-emitting layer, the light-emitting performance remains stable.
  • the functional layer 3 is a hole injection layer, and the material of the functional layer 3 includes poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), polyvinylcarbazole (PVK), poly[ (9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(p-butylphenyl))diphenylamine))(TFB)poly(bis(4 -At least one of phenyl)(4-butylphenyl)amine](Poly-TPD).
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid
  • PVK polyvinylcarbazole
  • TFB bis(4 -At least one of phenyl)(4-butylphenyl)amine
  • the material of the functional layer 3 is poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), and the surface of PEDOT:PSS close to the perovskite-type light-emitting layer 4 has the plasma And it is in direct contact with the perovskite-type light-emitting layer 4.
  • the functional layer 3 also functions as a hole transport layer, and there is no need to separately provide a hole transport layer between the first surface 31 and the perovskite light-emitting layer 4, which simplifies the manufacturing process and structure of the light-emitting device.
  • the light-emitting device further includes: an electron injection layer 5, a modified electrode 6, a first electrode 21 and a second electrode 22.
  • the electron injection layer 5 is located on the side of the perovskite light emitting layer 4 away from the hole injection layer 3;
  • the modified electrode 6 is located on the side of the electron injection layer 5 away from the perovskite light emitting layer 4; the hole injection layer 3,
  • the perovskite light-emitting layer 4, the electron injection layer 5 and the modified electrode 6 are sandwiched between the first electrode 21 and the second electrode 22.
  • the material of the modified electrode 6 is LiF or CsCO 3 , to adjust the rate of electron injection, for example, to slow down the rate of electron injection, so as to balance the rate of hole injection and the rate of electron injection, so as to achieve better luminous effect and energy efficiency.
  • the perovskite-type light-emitting layer is composed of nano-sized perovskite nanocrystals, for example, the size of the crystalline perovskite material is greater than 20 nm.
  • the perovskite-type light-emitting layer can be composed of nano-sized perovskite quantum dots, for example, the size of the perovskite quantum dots is less than 20 nm. Those skilled in the art can design as needed.
  • the direct contact between the perovskite-type light-emitting layer and the first surface of the functional layer means that in a direction perpendicular to the base substrate, the first surface of the perovskite-type light-emitting layer and the functional layer There are no other layers or structures in between.
  • the surface roughness in the present disclosure refers to the small spacing and the unevenness of small peaks and valleys on the surface, that is, the difference between two peaks or two valleys on the surface is perpendicular to the surface.
  • FIG. 15 is a schematic structural diagram of another light-emitting device provided by an embodiment of the present disclosure.
  • the functional layer 30 is an electron injection layer.
  • the first surface 301 of the electron injection layer 30 has the hydrophilic group and the perovskite-type light-emitting layer 40 is in direct contact with the first surface 301.
  • the material of the electron injection layer 30 includes zinc oxide (ZnO), and the surface of ZnO close to the perovskite-type light-emitting layer 40 has the hydrophilic group and is compatible with the perovskite-type light-emitting layer 40. direct contact.
  • the material of the electron injection layer 5 is ZnO.
  • ZnO has a good electron injection function and an electron transport function, so that the electron transport layer can be omitted.
  • the electron injection layer 5 includes a zinc oxide layer and a polyethyleneimine (PEI) layer that are stacked, and the polyethyleneimine layer is located on the side of the zinc oxide layer away from the perovskite light-emitting layer 4.
  • the PEI layer can adjust the energy level of ZnO and slow down the rate of electron injection, thereby balancing the rate of hole injection and the rate of electron injection to achieve better luminous effects and energy efficiency.
  • the light emitting device further includes: a modified electrode 60, a hole injection layer 50, a first electrode 210 and a second electrode 220.
  • the hole injection layer 50 is located on the side of the perovskite light emitting layer 40 away from the electron injection layer 30; the hole injection layer 50, the perovskite light emitting layer 40, the functional layer 30 (that is, the electron injection layer), and the modified electrode 60 It is sandwiched between the first electrode 210 and the second electrode 220.
  • the modified electrode 60 is located on the side of the electron injection layer 30 away from the perovskite-type light-emitting layer 4.
  • the material of the modified electrode 60 is LiF or CsCO 3 , to adjust the rate of electron injection, for example, to slow down the rate of electron injection, so as to balance the rate of hole injection and the rate of electron injection to achieve better luminous effect and energy efficiency.

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Abstract

发光器件及其制作方法。该发光器件的制作方法包括：形成功能层，其中，功能层具有第一表面；对功能层的第一表面进行等离子体处理；以及在经等离子体处理后的第一表面上形成钙钛矿型发光层。

Description

发光器件及其制作方法 技术领域
本公开至少一实施例涉及一种发光器件及其制作方法。
背景技术
钙钛矿材料通常指包括分子式为ABX 3成分的材料，具有优异的光学和光电子特性，基于钙钛矿材料制成的钙钛矿电致发光器件具有外量子效率高、发射光谱连续可调、色纯度高、成本低等特点，使其可在显示和照明等领域得到广泛的应用。然而，目前基于钙钛矿材料制备的钙钛矿发光二极管器件(Perovskite light-emitting diodes，PeLED)存在结构较复杂、外量子效率较低等缺点，相比于目前已经广泛应用的有机电致发光器件(Organic light-emitting diodes，OLED)还有很大的提升空间。高质量的钙钛矿发光薄膜的形成对位于其下方的衬底的表面平整性和润湿性有较严格的要求，使得下层衬底材料的选择受到限制，从而进一步地限制了钙钛矿电致发光器件结构的设计。
发明内容
本公开至少一实施例提供一种发光器件的制作方法，该方法包括：形成功能层，其中，功能层具有第一表面；对功能层的第一表面进行等离子体处理；以及在经等离子体处理后的第一表面上形成钙钛矿型发光层。
例如，在本公开至少一实施例提供的发光器件的制作方法中，所述等离子体处理包括氧等离子体处理、氮等离子体处理和氩等离子体处理中的至少之一。
例如，在本公开至少一实施例提供的发光器件的制作方法中，用于进行所述等离子体处理的气体的气压为20Pa～50Pa，所述等离子体处理的时间为2～5分钟。
例如，在本公开至少一实施例提供的发光器件的制作方法中，所述功能层为空穴注入层，所述功能层的材料包括聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺 酸(PEDOT:PSS)、聚乙烯咔唑(PVK)、聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(对丁基苯基))二苯胺)](TFB)、聚[双(4-苯基)(4-丁基苯基)胺](Poly-TPD)中的至少之一。
例如，在本公开至少一实施例提供的发光器件的制作方法中，所述功能层为电子注入层，所述功能层的材料包括氧化锌(ZnO)。
例如，在本公开至少一实施例提供的发光器件的制作方法中，所述钙钛矿型发光层包括分子式为ABX 3的材料；A为金属阳离子或烷基铵盐离子，B为金属阳离子，X为卤素阴离子。
例如，在本公开至少一实施例提供的发光器件的制作方法中，A包括有机胺基团、脒基团、Cs +、K +、Rb +中的至少之一；B包括Pb 2+、Sn 2+、Ge 2+、Ga 2+、In 3+、Cd 2+、Hg 2+、Ni 2+、Mn 2+、Bi 3+、Sb 3+、中的至少之一；X包括Cl -、Br -、I -中的至少之一。
例如，在本公开至少一实施例提供的发光器件的制作方法中，在经所述等离子体处理后的所述第一表面上形成所述钙钛矿型发光层包括：以AX n、BX m作为溶质溶解于第一溶剂中以形成钙钛矿型发光层的前驱体溶液；以及利用所述钙钛矿型发光层的前驱体溶液在经所述等离子体处理后的所述第一表面上形成所述钙钛矿型发光层；AX n与BX m反应生成ABX 3，m和n均为正整数。
例如，在本公开至少一实施例提供的发光器件的制作方法中，利用所述钛矿型发光层的前驱体溶液在经所述等离子体处理后的所述第一表面上形成所述钛矿型发光层包括：将所述钙钛矿型发光层的前驱体溶液旋涂于经所述等离子体处理后的所述第一表面上；在所述旋涂过程中向所述钙钛矿型发光层的前驱体溶液中加入第二溶剂，其中，所述第二溶剂与所述第一溶剂不互溶；以及进行退火处理以得到所述钙钛矿型发光层。
例如，在本公开至少一实施例提供的发光器件的制作方法中，所述第一溶剂为无水N，N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、γ-丁内酯(GBL)、乙腈(ACN)中的至少之一，第二溶剂包括甲苯、氯仿、氯苯、丙酮中的至少之一。
例如，在本公开至少一实施例提供的发光器件的制作方法中，所述退火处理的温度为70℃～80℃，所述退火处理的时间为20～40min。
例如，在本公开至少一实施例提供的发光器件的制作方法中，所述钙钛矿型发光层的前驱体溶液与经所述等离子体处理后的所述第一表面的接触角小于16°。
例如，本公开至少一实施例提供的发光器件的制作方法还包括：以AI、B(I) m作为溶质溶解于所述第一溶剂中以形成第一前驱体溶液，利用所述第一前驱体溶液在经所述等离子体处理后的所述第一表面上形成发射红光的钙钛矿型发光层，其中，AI与B(I) m反应生成ABI 3。
例如，本公开至少一实施例提供的发光器件的制作方法还包括：还包括：以ABr、B(Br) m作为溶质溶解于所述第一溶剂中以形成第二前驱体溶液，利用所述第二前驱体溶液在经所述等离子体处理后的所述第一表面上形成发射绿光的钙钛矿型发光层，ABr与B(Br) m反应生成AB(Br) 3。
例如，本公开至少一实施例提供的发光器件的制作方法还包括：以ACl、B(Br) m作为溶质溶解于所述第一溶剂中以形成第三前驱体溶液，在经所述等离子体处理后的所述第一表面上形成发射蓝光的钙钛矿型发光层，ACl与B(Br) m反应生成AB(Br) 2Cl。
例如，本公开至少一实施例提供的发光器件的制作方法还包括：在进行所述等离子处理之前，对所述功能层进行退火处理。
本公开至少一实施例还提供一种发光器件，发光器件包括：功能层和钙钛矿型发光层。功能层具有第一表面；钙钛矿型发光层与所述功能层的所述第一表面直接接触；功能层的所述第一表面存在亲水基团。
例如，在本公开至少一实施例提供的发光器件中，所述等离子体包括氧等离子体、氮等离子体和氩等离子体中的至少之一。
例如，在本公开至少一实施例提供的发光器件中，所述钙钛矿型发光层的表面粗糙度小于2nm。
例如，在本公开至少一实施例提供的发光器件中，所述功能层为空穴注入层，所述功能层的材料包括聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、聚乙烯咔唑(PVK)、聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(对丁基苯基))二苯胺)](TFB)、聚[双(4-苯基)(4-丁基苯基)胺](Poly-TPD)中的至少之一。
例如，在本公开至少一实施例提供的发光器件中，所述功能层的材料为 聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)，所述PEDOT:PSS的靠近所述钙钛矿型发光层的表面具有所述亲水基团且与所述钙钛矿型发光层直接接触。
例如，本公开至少一实施例提供的发光器件还包括：电子注入层、修饰电极、第一电极和第二电极。电子注入层位于所述钙钛矿型发光层的远离所述空穴注入层的一侧；修饰电极位于所述电子注入层的远离钙钛矿型发光层的一侧；所述空穴注入层、所述钙钛矿型发光层、所述电子注入层和所述修饰电极夹置于所述第一电极与所述第二电极之间。
例如，在本公开至少一实施例提供的发光器件中，所述功能层为电子注入层，所述功能层的材料包括氧化锌(ZnO)，所述ZnO的靠近所述钙钛矿型发光层的表面具有所述亲水基团且与所述钙钛矿型发光层直接接触。
例如，本公开至少一实施例提供的发光器件还包括：空穴注入层、修饰电极、第一电极和第二电极。空穴注入层位于所述钙钛矿型发光层的远离所述电子注入层的一侧；修饰电极位于所述电子注入层的远离钙钛矿型发光层的一侧；所述空穴注入层、所述钙钛矿型发光层、所述电子注入层和所述修饰电极夹置于所述第一电极与所述第二电极之间。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对实施例的附图作简单地介绍，显而易见地，下面描述中的附图仅仅涉及本公开的一些实施例，而非对本公开的限制。
图1A-1F为本公开一实施例提供的一种发光器件的制作方法示意图；
图1G-1K为本公开一实施例提供的另一种发光器件的制作方法示意图；
图2A为本公开一实施例提供的一种发光器件的制作方法流程图；
图2B为本公开一实施例提供的另一种发光器件的制作方法流程图；
图3A-3B为本公开一实施例中的功能层的第一表面经等离子体处理前后的接触角测量结果对比图；
图4为本公开一实施例中的功能层经等离子体处理前后的透过率对比曲线图；
图5为本公开一实施例中的发射红光的钙钛矿发光层的表面SEM图像；
图6为本公开一实施例中的发射红光的钙钛矿发光层的表面AFM图像；
图7为本公开一实施例中的发射红光的钙钛矿发光层的吸收和光致发光光谱曲线；
图8为本公开一实施例中的发射绿光的钙钛矿发光层的表面SEM图像；
图9为本公开一实施例中的发射绿光的钙钛矿发光层的表面AFM图像；
图10为本公开一实施例中的发射绿光的钙钛矿发光层的吸收和电致发光光谱曲线；
图11为根据本公开一实施例提供的方法制得的发射绿光的发光器件的电流密度/亮度-电压关系曲线；
图12为根据本公开一实施例提供的方法制得的发射绿光的发光器件的外量子效率/电流效率-电流密度关系曲线；
图13本公开一实施例提供的发射绿光的发光器件的电致发光光谱；
图14为本公开一实施例提供的一种发光器件的结构示意图；
图15为本公开一实施例提供的另一种发光器件的结构示意图。
具体实施方式
为使本公开实施例的目的、技术方案和优点更加清楚，下面将结合本公开实施例的附图，对本公开实施例的技术方案进行清楚、完整地描述。以下所描述的实施例是本公开的一部分实施例，而不是全部的实施例。基于所描述的本公开的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其它实施例，都属于本公开保护的范围。
除非另作定义，此处使用的技术术语或者科学术语应当为本发明所属领域内具有一般技能的人士所理解的通常意义。本公开中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。同样，“包括”或者“包含”等类似的词语意指出现在该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。“连接”或者“相连”等类似的词语并非限定于物理的或者机械的连接，而是可以包括电性的连接，不管是直接的还是间接的。“上”、“下”、“左”、“右”等仅用于表示相对位置关系，当被描述对象的绝对位置改变后，则该相对位置关系也可能相应地改变。
本公开一实施例提供一种发光器件的制作方法，该方法包括：形成功能层，其中，功能层具有第一表面；对功能层的第一表面进行等离子体处理；以及在经等离子体处理后的第一表面上形成钙钛矿型发光层。
示例性地，图1A-1F为本公开一实施例提供的一种发光器件的制作方法示意图，图2A为本公开一实施例提供的一种发光器件的制作方法流程图。该实施例提供的发光器件的制作方法包括以下步骤。
如图1A所示，提供衬底基板1。对衬底基板1进行清洗。例如，依次使用去离子水、丙酮溶液、乙醇溶液、异丙醇溶液对衬底基板1进行擦拭和超声清洗，清洗后采用氮气吹干；将清洗好的衬底基板1进行等离子体预处理，以增强衬底基板1的表面的润湿性。例如，该离子体处理包括氧等离子体处理、氮等离子体处理和氩等离子体处理中的至少之一。例如，衬底基板1的材料可以是玻璃、石英、氧化铟锡(ITO)等无机材料，也可以是聚酰亚胺等有机材料，本公开实施例对此不作限定。
然后，在衬底基板1上形成第一电极21。该电极例如为透明电极或不透明电极。
如图1B所示，在第一电极21的远离衬底基板1的一侧形成功能层3，功能层3具有第一表面31。例如，在一个实施例中，功能层3为空穴注入层，功能层3的材料包括聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、聚乙烯咔唑(PVK)、聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(对丁基苯基))二苯胺)](TFB)中的至少之一。
如图1B所示，对功能层3的第一表面31进行等离子体处理。例如，该等离子体处理包括氧等离子体处理、氮等离子体处理和氩等离子体处理中的至少之一。本实施例以功能层3的材料为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、对功能层3的第一表面31进行氧等离子体处理为例对发光器件的制作方法及技术效果进行介绍。
例如，将制备好功能层3的器件移至等离子体清洗机的腔体中，经过多次抽真空/通氧气操作后，保证腔体内为氧气环境。然后，通过调节氧等离子体处理的功率、腔体内的气压和氧等离子体处理时间等参数对处理效果进行调整。例如，用于进行等离子体处理的气体的气压为20Pa～50Pa，以获得适宜的等离子体浓度；等离子体处理的时间为2～5分钟；等离子体处理的功率 为30W～40W。例如，该功率指等离子体处理设备的功率。等离子体处理的时间和功率会影响第一表面31突起物的量从而影响比表面面积，还会影响第一表面31含有的含氮或含氧等亲水基团的量，从而影响在经等离子体处理后的第一表面31上形成的钙钛矿型发光层的性能与第一表面31结合的效果。采用上述条件能够使功能层3的第一表面31具有合适的比表面积和含氮或含氧等亲水基团，从而，功能层3的第一表面31得到较好的改性，有利于提高后续在功能层3的第一表面31上形成的钙钛矿型发光层的性能。
如图1C所示，在经等离子体处理后的第一表面31上形成钙钛矿型发光层4。例如，先制备钙钛矿型发光层的前驱体溶液，再利用钙钛矿型发光层的前驱体溶液在经等离子体处理后的第一表面31上形成钙钛矿型发光层4。由于对功能层3的第一表面31进行了等离子体处理，钙钛矿型发光层的前驱体溶液对第一表面31的润湿性得到提高，接触角变小，从而形成的钙钛矿型发光层4更加平整，例如所述钙钛矿型发光层的表面粗糙度小于2nm，从而发光性能得到改善，例如该发光器件的外量子效率提高。并且，经等离子体处理后的功能层3的光透过率提高，有利于提高发光器件的光利用率。
需要说明的是，本公开中的钙钛矿型发光层4不同于有机发光二极管(OLED)发光层。例如，钙钛矿型发光层4包括分子式为ABX 3的材料。A为金属阳离子或烷基铵盐离子，B为金属阳离子，X为卤素阴离子。例如，A包括有机胺基团(例如烷胺基团RNH 4 +，R为烷基，例如烷胺基团为CH 3NH 4 +)、脒基团(例如甲脒基团NH 2CH＝NH 2 +等)、Cs +、K +、Rb +中的至少之一；B包括Pb 2+、Sn 2+、Ge 2+、Ga 2+、In 3+、Cd 2+、Hg 2+、Ni 2+、Mn 2+、Bi 3+、Sb 3+、中的至少之一；X包括Cl -、Br -、I -中的至少之一。
例如，在经等离子体处理后的第一表面31上形成钙钛矿型发光层4包括：以AX n、BX m作为溶质溶解于第一溶剂中以形成钙钛矿型发光层的前驱体溶液；以及利用钙钛矿型发光层的前驱体溶液在经等离子体处理后的第一表面31上形成钙钛矿型发光层4。AX n与BX m反应生成ABX 3，m和n均为正整数。例如，当A为一价离子、B为二价离子时，n＝1，m＝2；或者，当A为一价离子、B为三价离子时，n＝1，m＝3。
例如，利用钛矿型发光层的前驱体溶液在经等离子体处理后的第一表面31上形成钛矿型发光层3包括：将钙钛矿型发光层的前驱体溶液旋涂于经等 离子体处理后的第一表面31上；在旋涂过程中向钙钛矿型发光层的前驱体溶液中加入第二溶剂，其中，第二溶剂与第一溶剂不互溶；以及进行退火处理以得到钙钛矿型发光层4。
例如，第一溶剂为无水N，N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、γ-丁内酯(GBL)、乙腈(ACN)中的至少之一，第二溶剂包括甲苯、氯仿、氯苯、丙酮中的至少之一。当然，第一溶剂和第二溶剂不局限于以上几种，具体可以根据所形成的钛矿材料而定。
例如，本公开一实施例提供的发光器件的制作方法还包括：在用于形成钙钛矿发光层的前驱体溶液中添加卤化的胺配体材料；以及将添加有卤化的胺配体材料的钙钛矿发光层的前驱体溶液旋涂于经等离子体处理后的第一表面31上。例如，卤化的胺配体材料为溴化的铵配体材料，当然也可以采用氯化的铵配体材料或者碘化的胺配体材料等。
具体的，溴化的铵配体材料包括：溴化的3,3-二苯基丙胺、溴化乙胺、溴化丁胺、溴化辛胺、溴化苯乙胺、溴化苯丙胺中的任意一种或者多种。以溴化的铵配体材料为溴化的3,3-二苯基丙胺(DPPA-Br)为例，对该种配体材料的制备进行说明。将一定量的3,3,二苯基丙胺(DPPA)与乙醇以体积比1:1共混，使用冰水浴降温至10℃以下后，逐滴加入稍过量的HBr水溶液，反应两个小时。通过旋蒸干燥后，再用乙醇进行重结晶，最后进行抽滤并用无水乙醚洗涤3次，最后50℃温度下真空干燥12小时。得到溴化的铵配体材料。
例如，在旋涂过程中向钙钛矿型发光层的前驱体溶液中加入一定量的所述第二溶剂以使钙钛矿材料结晶，且使卤化的胺配体材料接枝在结晶的钙钛矿材料上，形成钙钛矿薄膜。例如，开始旋涂后，第6秒滴加第二溶剂，例如1分钟内滴加完毕第二溶剂，以获得较好的钙钛矿材料结晶效果。
例如，所述退火处理的温度为70℃～80℃，退火处理的时间为20～40min，已达到理想的效果。
例如，钙钛矿型发光层的前驱体溶液与经等离子体处理后的第一表面的接触角小于16°。图3A-3B为本公开一实施例中的功能层的第一表面经等离子体处理前后的接触角测量结果对比图。图3A所示的角α为在不经等离子处理的功能层的第一表面上旋涂钙钛矿型发光层的前驱体溶液的情况下的接 触角，α＝16°。图3B所示的角β为在经等离子处理的功能层的第一表面31上旋涂钙钛矿型发光层的前驱体溶液的情况下的接触角，α＝12.5°。由此可见，对功能层3的第一表面31进行等离子体处理能够提高钙钛矿型发光层的前驱体溶液对第一表面31的润湿性，减小将该前驱体溶液形成于经等离子体处理的功能层3的第一表面31时的接触角，从而经退火处理后得到的钙钛矿型发光层4更加平整，发光性能得到改善，例如该发光器件的外量子效率提高。从而，当功能层3为上述空穴注入层时，其兼具空穴传输层的功能，无需再单独设置空穴传输层，简化了该发光器件的制作工艺及结构。
另外，图4为本公开一实施例中的功能层经等离子体处理前后的透过率对比曲线图。经等离子体处理后的功能层3的光透过率高于进行等离子处理之前的光透过，例如经等离子体处理后的功能层3的光透过率可达到96％以上。由此可以证明，对功能层3的第一表面31进行了等离子体处理能够提高功能层3的光透过率，从而提高发光器件的光利用率。
例如，发光器件的制作方法包括：在经等离子体处理后的第一表面31上形成发射红光的钙钛矿型发光层、发射绿光的钙钛矿型发光层以及发射蓝光的钙钛矿型发光层，以实现彩色照明或彩色显示。
例如，以AI、B(I) m作为溶质溶解于第一溶剂中以形成第一前驱体溶液，利用第一前驱体溶液在经等离子体处理后的第一表面上形成发射红光的钙钛矿型发光层，其中，AI与B(I) m反应生成ABI 3。本实施例以AI为NH 2CH＝NH 2I、B(I) m为PbI 2、第一溶剂为无水DMF为例。
例如，将NH 2CH＝NH 2I、PbI 2、胺的卤化物以一定比例溶于第一溶剂中得到第一前驱体溶液。例如，将NH 2CH＝NH 2I、PbI 2、胺的卤化物以摩尔比1:1:0.5的比例溶于无水DMF中配成浓度为0.2M的第一前驱体溶液。通过0.22um的尼龙滤头后备用，将第一前驱体溶液旋涂到经过氧等离子体处理的第一表面31上，当旋涂转速达到4000rpm时，例如在开始后的第6秒，快速滴加第二溶剂(反溶剂)，1秒内将第二溶剂滴加完毕，以快速形成钙钛矿型薄膜，并控制钙钛矿型薄膜中钙钛矿晶粒的形成。例如，再经过80℃退火后得到发射红光的钙钛矿发光层。发射红光的钙钛矿发光层的表面形貌如图5和图6所示，所制备的发射红光的钙钛矿发光层非常致密，无明显缺陷，表面非常平整均一，表面平均粗糙度低，仅为0.57nm。图7为发射红光的钙 钛矿发光层的吸收和电致发光光谱曲线。从图7中可以看出发射峰位于675nm，半峰宽仅为50nm，可利用该发射红光的钙钛矿发光层获得较高的色域。
例如，以ABr、B(Br) m作为溶质溶解于第一溶剂中以形成第二前驱体溶液，利用第二前驱体溶液在经等离子体处理后的第一表面上形成发射绿光的钙钛矿型发光层，ABr与B(Br) m反应生成AB(Br) 3。本实施例以ABr为NH 2CH＝NH 2Br、B(Br) m为PbBr 2、第一溶剂为无水DMF为例。
例如，将NH 2CH＝NH 2Br、PbBr 2、胺的卤化物以一定比例溶于第一溶剂中得到第二前驱体溶液。例如，将NH 2CH＝NH 2Br、PbBr 2、胺的卤化物以摩尔比1:1:0.35的比例溶于无水DMF中配成浓度为0.2M的第二前驱体溶液。通过0.22um的尼龙滤头后备用，将第二前驱体溶液旋涂到经过氧等离子体处理的第一表面31上，当旋涂转速达到4000rpm时，例如在开始后的第6秒，快速滴加第二溶剂(反溶剂)，1秒内将第二溶剂滴加完毕，以快速形成钙钛矿型薄膜，并控制钙钛矿型薄膜中钙钛矿晶粒的形成。例如，再经过80℃退火后得到发射绿光的钙钛矿发光层。发射绿光的钙钛矿发光层的表面形貌如图8和图9所示，所制备的发射绿光的钙钛矿发光层非常致密，无明显缺陷，表面非常平整均一，表面平均粗糙度低，仅为1.7nm。图10为发射绿光的钙钛矿发光层的吸收和电致发光光谱曲线。从图10中可以看出发射峰位于526nm，半峰宽仅为22nm，可利用该发射绿光的钙钛矿发光层获得较高的色域。
例如，以ACl、B(Br) m作为溶质溶解于第一溶剂中以形成第三前驱体溶液，在经等离子体处理后的第一表面上形成发射蓝光的钙钛矿型发光层，ACl与B(Br) m反应生成AB(Br) 2Cl。本实施例以ABr为NH 2CH＝NH 2Cl、B(Br) m为PbBr 2、第一溶剂为无水DMF为例。将NH 2CH＝NH 2Cl、PbBr 2、胺的卤化物以摩尔比1:1:0.8的比例溶于无水DMF中配成浓度为0.2M的第三前驱体溶液。通过0.22um的尼龙滤头后备用，将第三前驱体溶液旋涂到经过氧等离子体处理的第一表面31上，当旋涂转速达到4000rpm时，例如在开始后的第6秒，快速滴加第二溶剂(反溶剂)，1秒内将第二溶剂滴加完毕，以快速形成钙钛矿型薄膜，并控制钙钛矿型薄膜中钙钛矿晶粒的形成。例如，再经过80℃退火后得到发射蓝光的钙钛矿发光层。该发射蓝光的钙钛矿发光层 非常致密，无明显缺陷，表面非常平整均一，表面平均粗糙度低，其发射的蓝光的发射峰位于460nm～480nm。
图11和图12为根据本公开上述实施例提供的方法所制备的绿光钙钛矿电致发光器件的性能参数曲线，该发光器件的开启电压为2.9V，在4.6V时达到最大亮度超过8000cd/m 2。同时，该发光器件的外量子效率可达16％以上，电流效率超过60cd/A。图13为发射绿光的发光器件的电致发光光谱随电压变化的曲线，由图13可以看出，峰位始终维持的526nm处，光谱的半峰宽为23nm，具有非常高的色纯度，与图10所示的光致发光光谱一致。并且，峰位不随作用于发光器件的电压的升高而改变，具有较高的光谱稳定性。
钙钛矿型发光层由纳米尺寸的钙钛矿纳米晶组成，例如，结晶的钙钛矿材料的尺寸大于20nm。当然，钙钛矿型发光层与可以由纳米尺寸的钙钛矿量子点，例如钙钛矿量子点的尺寸小于20nm。在本实施例的钙钛矿型发光层的制备方法中，通过控制所添加的卤化的配体材料的量，以及第二溶剂的量则可以控制所形成钙钛矿材料结晶后的尺寸。通常情况下，卤化的配体材料的量多，则容易形成钙钛矿量子点，钙钛矿量子点具有较优的发光效率；卤化的配体材料的量少，则容易形成钙钛矿纳米晶，钙钛矿纳米晶具有较优的载流子传输能力。本领域技术人员可以根据需要进行设计。
如图1D所示，在功能层3为空穴注入层的情况下，发光器件的制作方法还包括：形成位于钙钛矿型发光层4的远离空穴注入层3的一侧的电子注入层5，如图1D所示；形成修饰电极6，如图1E所示；以及形成第二电极22，如图1F所示。空穴注入层3、钙钛矿型发光层4和电子注入层5夹置于第一电极21与第二电极22之间。修饰电极6位于电子注入层5的远离钙钛矿型发光层4的一侧。修饰电极6的材料为LiF或CsCO 3，以调节电子注入的速率例如减缓电子注入的速率，从而平衡空穴注入的速率与电子注入的速率，达到较优的发光效果和能效。例如，第二电极22可以包括间隔设置的多个部分，如图1F所示的；第二电极22也可以为整面的电极。
例如，电子注入层5的材料包括氧化锌(ZnO)。例如，电子注入层5的材料为ZnO。ZnO具有良好的电子注入功能，兼具电子传输功能，从而可以省略电子传输层。或者，电子注入层5包括堆叠设置的氧化锌层和聚乙烯亚胺(PEI)层，聚乙烯亚胺层位于氧化锌层的远离钙钛矿型发光层4的一侧。 PEI层能够调节ZnO的能级，减缓电子注入的速率，从而平衡空穴注入的速率与电子注入的速率，达到较优的发光效果和能效。
在本公开又一实施例中，例如，参考图2B和图1B，发光器件的制作方法还包括：在进行等离子处理之前，对功能层3进行退火处理，以释放功能能层3等衬底基板1上的各个结构的应力，进一步提高后期在功能层3上形成的钙钛矿型发光层的稳定性。本实施例的其他步骤均与之前的实施例中的相同，请参考之前的描述，在此不再赘述。
图1G-1K为本公开一实施例提供的另一种发光器件的制作方法示意图。例如，在图1G-1K所示的发光器件的制作方法中，功能层30为电子注入层。
如图1G所示，发光器件的制作方法包括：在衬底基板10上依次形成第一电极210、修饰电极60和功能层30。功能层30为电子注入层，其材料包括氧化锌(ZnO)。
如图1H所示，发光器件的制作方法还包括：对功能层30(即电子注入层)的第一表面301进行等离子处理，该等离子处理与之前实施例中对电子注入层30所进行的等离子处理相同，请参考之前的描述。
如图1I所示，发光器件的制作方法还包括：在经过等离子处理的电子注入层30的第一表面301上形成钙钛矿型发光层40。形成钙钛矿型发光层40的具体方法请参考之前的描述。
该发光器件的制作方法还包括：形成位于钙钛矿型发光层40的远离电子注入层30的一侧的空穴注入层50，如图1J所示；以及形成第二电极220，如图1K所示。空穴注入层50、钙钛矿型发光层40和电子注入层30夹置于第一电极21与第二电极22之间。
例如，在一个示例中，电子注入层30为氧化锌层，则对氧化锌层的第一表面301进行等离子体处理，在经等离子处理后的氧化锌层的第一表面301上形成所述钙钛矿型发光层40；例如，在另一个示例中，电子注入层30包括堆叠设置的氧化锌层和聚乙烯亚胺(PEI)层，聚乙烯亚胺层位于氧化锌层的靠近衬底基板10的一侧，则对氧化锌层的第一表面301进行等离子体处理，在经等离子处理后的氧化锌层的第一表面301上形成所述钙钛矿型发光层40。
图1G-1K所示的实施例提供的制作方法的其他特征与之前的实施例中 的描述相同，能够达到与之前的实施例相同或相似的技术效果。
本公开至少一实施例还提供一种发光器件，该发光器件根据本公开实施例提供的任意一种发光器件的制作方法形成。该发光器件包括：功能层和钙钛矿型发光层。功能层具有第一表面；钙钛矿型发光层与所述功能层的第一表面直接接触；功能层的第一表面存在亲水基团。
示范性地，图14为本公开一实施例提供的一种发光器件的结构示意图。如图14所示，该发光器件根据本公开实施例提供的任意一种发光器件的制作方法形成。该发光器件包括：功能层3和钙钛矿型发光层4。功能层3具有第一表面31；钙钛矿型发光层4与功能层3的第一表面31直接接触；功能层3的第一表面31存在亲水基团。例如，该亲水基团包括含氧亲水基团或含氮亲水基团。含氧亲水基团例如为羟基(OH -)，含氮亲水基团例如氨基。例如，该亲水基团是对第一表面31进行等离子体处理而形成的。例如，该等离子体包括氧等离子体、氮等离子体和氩等离子体中的至少之一。第一表面31上存在亲水基团且钙钛矿型发光层4与功能层3的第一表面31直接接触，这能够使得第一表面31更加粗糙，从而在第一表面31上形成钙钛矿型发光层4的过程中，用于形成钙钛矿型发光层4的前驱体溶液对第一表面31的润湿性得到提高，从而钙钛矿型发光层4更加平整，例如，钙钛矿型发光层的表面粗糙度小于2nm，从而其发光性能得到改善，例如该发光器件的外量子效率提高，随着作用于钙钛矿型发光层的电压的变化，发光性能保持稳定。
例如，功能层3为空穴注入层，功能层3的材料包括聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、聚乙烯咔唑(PVK)、聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(对丁基苯基))二苯胺)](TFB)聚[双(4-苯基)(4-丁基苯基)胺](Poly-TPD)中的至少之一。
例如，功能层3的材料为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)，PEDOT:PSS的靠近钙钛矿型发光层4的表面具有所述等离子体且与钙钛矿型发光层4直接接触。此时，功能层3兼具空穴传输层的功能，无需在第一表面31与钙钛矿型发光层4之间再单独设置空穴传输层，简化了该发光器件的制作工艺及结构。
例如，如图14所示，该发光器件还包括：电子注入层5、修饰电极6、第一电极21以及第二电极22。电子注入层5位于钙钛矿型发光层4的远离 空穴注入层3的一侧；修饰电极6位于电子注入层5的远离钙钛矿型发光层4的一侧；空穴注入层3、钙钛矿型发光层4、电子注入层5和修饰电极6夹置于第一电极21与第二电极22之间。修饰电极6的材料为LiF或CsCO 3，以调节电子注入的速率例如减缓电子注入的速率，从而平衡空穴注入的速率与电子注入的速率，达到较优的发光效果和能效。
钙钛矿型发光层由纳米尺寸的钙钛矿纳米晶组成，例如，结晶的钙钛矿材料的尺寸大于20nm。当然，钙钛矿型发光层与可以由纳米尺寸的钙钛矿量子点，例如钙钛矿量子点的尺寸小于20nm。本领域技术人员可以根据需要进行设计。
该发光器件的其他未提及的特征请参考之前与制作方法相关的实施例中的描述。
需要说明的是，在本公开中，钙钛矿型发光层与功能层的第一表面直接接触是指在垂直于衬底基板的方向上，钙钛矿型发光层与功能层的第一表面之间不存在其他的任何层或结构。
需要说明的是，本公开中的表面粗糙度(surface roughness)是指表面具有的较小间距和微小峰谷的不平度，即表面上两波峰或两波谷之间的在垂直于该表面方向上的距离(波距)。表面粗糙度越小，则表面越光滑。
例如，图15是本公开一实施例提供的另一种发光器件的结构示意图。该发光器件中，功能层30为电子注入层。电子注入层30的第一表面301具有所述亲水基团且钙钛矿型发光层40与第一表面301直接接触。
例如，电子注入层30(即电子注入层)的材料包括氧化锌(ZnO)，且ZnO的靠近钙钛矿型发光层40的表面具有所述亲水基团且与钙钛矿型发光层40直接接触。例如，电子注入层5的材料为ZnO。ZnO具有良好的电子注入功能，兼具电子传输功能，从而可以省略电子传输层。或者，电子注入层5包括堆叠设置的氧化锌层和聚乙烯亚胺(PEI)层，聚乙烯亚胺层位于氧化锌层的远离钙钛矿型发光层4的一侧。PEI层能够调节ZnO的能级，减缓电子注入的速率，从而平衡空穴注入的速率与电子注入的速率，达到较优的发光效果和能效。
例如，如图15所示，该发光器件还包括：修饰电极60、空穴注入层50、第一电极210以及第二电极220。空穴注入层50位于钙钛矿型发光层40的 远离电子注入层30的一侧；空穴注入层50、钙钛矿型发光层40、功能层30(即电子注入层)和修饰电极60夹置于第一电极210与第二电极220之间。修饰电极60位于电子注入层30的远离钙钛矿型发光层4的一侧。修饰电极60的材料为LiF或CsCO 3，以调节电子注入的速率例如减缓电子注入的速率，从而平衡空穴注入的速率与电子注入的速率，达到较优的发光效果和能效。
图15所示的实施例提供的发光器件的其他特征与之前的实施例中的描述相同，能够达到与之前的实施例相同或相似的技术效果。
以上所述仅是本公开的示范性实施方式，而非用于限制本公开的保护范围，本公开的保护范围根据权利要求书所界定的范围确定。

Claims (24)

  1. 一种发光器件的制作方法，包括：
    形成功能层，其中，所述功能层具有第一表面；
    对所述功能层的所述第一表面进行等离子体处理；
    在经等离子体处理后的所述第一表面上形成钙钛矿型发光层。
  2. 根据权利要求1所述的发光器件的制作方法，其中，所述等离子体处理包括氧等离子体处理、氮等离子体处理和氩等离子体处理中的至少之一。
  3. 根据权利要求1或2所述的发光器件的制作方法，其中，用于进行所述等离子体处理的气体的气压为20Pa～50Pa，所述等离子体处理的时间为2～5分钟。
  4. 根据权利要求1-3任一所述的发光器件的制作方法，其中，所述功能层为空穴注入层，所述功能层的材料包括聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、聚乙烯咔唑(PVK)、聚[(9,9-二辛基芴基-2,7-二基)-co-(4,4'-(N-(对丁基苯基))二苯胺)](TFB)聚[双(4-苯基)(4-丁基苯基)胺](Poly-TPD)中的至少之一。
  5. 根据权利要求1-3任一所述的发光器件的制作方法，其中，所述功能层为电子注入层，所述功能层的材料包括氧化锌(ZnO)。
  6. 根据权利要求1-5任一所述的发光器件的制作方法，其中，所述钙钛矿型发光层包括分子式为ABX 3的材料，其中，
    A为金属阳离子或烷基铵盐离子，B为金属阳离子，X为卤素阴离子。
  7. 根据权利要求6所述的发光器件的制作方法，其中，A包括有机胺基团、脒基团、Cs +、K +、Rb +中的至少之一；
    B包括Pb 2+、Sn 2+、Ge 2+、Ga 2+、In 3+、Cd 2+、Hg 2+、Ni 2+、Mn 2+、Bi 3+、Sb 3+、中的至少之一；X包括Cl -、Br -、I -中的至少之一。
  8. 根据权利要求6或7所述的发光器件的制作方法，其中，在经所述等离子体处理后的所述第一表面上形成所述钙钛矿型发光层包括：
    以AX n、BX m作为溶质溶解于第一溶剂中以形成钙钛矿型发光层的前驱体溶液；以及
    利用所述钙钛矿型发光层的前驱体溶液在经所述等离子体处理后的所述 第一表面上形成所述钙钛矿型发光层；其中，AX n与BX m反应生成ABX 3，m和n均为正整数。
  9. 根据权利要求8所述的发光器件的制作方法，其中，利用所述钛矿型发光层的前驱体溶液在经所述等离子体处理后的所述第一表面上形成所述钛矿型发光层包括：
    将所述钙钛矿型发光层的前驱体溶液旋涂于经所述等离子体处理后的所述第一表面上；
    在所述旋涂过程中向所述钙钛矿型发光层的前驱体溶液中加入第二溶剂，其中，所述第二溶剂与所述第一溶剂不互溶；以及
    进行退火处理以得到所述钙钛矿型发光层。
  10. 根据权利要求9所述的发光器件的制作方法，其中，所述第一溶剂为无水N，N-二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、γ-丁内酯(GBL)、乙腈(ACN)中的至少之一，第二溶剂包括甲苯、氯仿、氯苯、丙酮中的至少之一。
  11. 根据权利要求9或10所述的发光器件的制作方法，其中，所述退火处理的温度为70℃～80℃，所述退火处理的时间为20～40min。
  12. 根据权利要求8-11任一所述的发光器件的制作方法，其中，所述钙钛矿型发光层的前驱体溶液与经所述等离子体处理后的所述第一表面的接触角小于16°。
  13. 根据权利要求8-12任一所述的发光器件的制作方法，还包括：以AI、B(I) m作为溶质溶解于所述第一溶剂中以形成第一前驱体溶液，利用所述第一前驱体溶液在经所述等离子体处理后的所述第一表面上形成发射红光的钙钛矿型发光层，其中，AI与B(I) m反应生成ABI 3。
  14. 根据权利要求8-13任一所述的发光器件的制作方法，还包括：以ABr、B(Br) m作为溶质溶解于所述第一溶剂中以形成第二前驱体溶液，利用所述第二前驱体溶液在经所述等离子体处理后的所述第一表面上形成发射绿光的钙钛矿型发光层，ABr与B(Br) m反应生成AB(Br) 3。
  15. 根据权利要求8-14任一所述的发光器件的制作方法，还包括：以ACl、B(Br) m作为溶质溶解于所述第一溶剂中以形成第三前驱体溶液，在经所述等离子体处理后的所述第一表面上形成发射蓝光的钙钛矿型发光层， ACl与B(Br) m反应生成AB(Br) 2Cl。
  16. 根据权利要求1-15任一所述的发光器件的制作方法，还包括：
    在进行所述等离子处理之前，对所述功能层进行退火处理。
  17. 一种发光器件，包括：
    功能层，其中，所述功能层具有第一表面；以及
    钙钛矿型发光层，与所述功能层的所述第一表面直接接触；其中，
    所述功能层的所述第一表面存在亲水基团。
  18. 根据权利要求17所述的发光器件，其中，所述等离子体包括氧等离子体、氮等离子体和氩等离子体中的至少之一。
  19. 根据权利要求17或18所述的发光器件，其中，所述钙钛矿型发光层的表面粗糙度小于2nm。
  20. 根据权利要求17-19任一所述的发光器件，其中，所述功能层为空穴注入层，所述功能层的材料包括聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、聚乙烯咔唑(PVK)、五氟苯甲基(PFB)中的至少之一。
  21. 根据权利要求20所述的发光器件，其中，所述功能层的材料为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)，所述PEDOT:PSS的靠近所述钙钛矿型发光层的表面具有所述亲水基团且与所述钙钛矿型发光层直接接触。
  22. 根据权利要求20或21所述的发光器件，还包括：
    电子注入层，位于所述钙钛矿型发光层的远离所述空穴注入层的一侧；
    修饰电极，位于所述电子注入层的远离钙钛矿型发光层的一侧；以及
    第一电极和第二电极；其中，所述空穴注入层、所述钙钛矿型发光层、所述电子注入层和所述修饰电极夹置于所述第一电极与所述第二电极之间。
  23. 根据权利要求17-19任一所述的发光器件，其中，所述功能层为电子注入层，所述功能层的材料包括氧化锌(ZnO)，所述ZnO的靠近所述钙钛矿型发光层的表面具有所述亲水基团且与所述钙钛矿型发光层直接接触。
  24. 根据权利要求23所述的发光器件，还包括：
    空穴注入层，位于所述钙钛矿型发光层的远离所述电子注入层的一侧；
    修饰电极，位于所述电子注入层的远离钙钛矿型发光层的一侧；以及
    第一电极和第二电极；其中，所述空穴注入层、所述钙钛矿型发光层、 所述电子注入层和所述修饰电极夹置于所述第一电极与所述第二电极之间。
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